Organometallic monoacylalkylphosphines

ES 2 194 584 A1

DESCRIPTION

Organometallic monoacylalkylphosphines.

The present invention relates to organometallic monoacylalkylphosphines, their preparation as well as their use as starting products for obtaining asymmetric mono- and bisacylphosphines, asymmetric mono- and bisacylphosphines oxides and sulfides.

Various metal phosphines have been known as intermediates for the synthesis of acylphosphine oxides. Thus, for example, document EP-40721 describes the production of acylphosphines by reacting acyl halides with metalated diorganylphosphines or with silylated phosphines or with diorganylphosphines.

By oxidation of acyldiorganylphosphines the corresponding acylphosphine oxide photoinitiators can be obtained. Document WO 00/32612 publishes a process to be carried out in a single reactor to obtain oxides of bisacylphosphines, in said process dichloroorganylphosphines are metalan, then they are reacted with acyl halides to obtain the corresponding acylphosphines and finally by oxidation or sulfuration are converted to oxides or bisacylphosphine sulfides.

Alkylacylphosphines and the corresponding metal compounds are not known in the current state of the art.

In document US-5 399 770 a bisacylphosphine ooxide is described that has two different acyl groups, in US-5 218 009 a monoacylphosphine ooxide is specifically published that has two different non-acyl substituents, attached to the phosphorus atom.

For the technique, with a view to the synthesis of oxides or acylphosphine sulphides, readily accessible starting materials are very important. Particularly interesting are the starting materials that make it possible to easily obtain "asymmetric" oxides and sulfides of bisacylphosphine, that is, those that have two different acyl groups.

Now a process has been found for the obtaining of metalated alkylacylphosphines that are suitable as starting products for the synthesis of photoinitiators of the acylphosphine oxide or acylphosphine sulfide type. The phosphines, phosphine oxides and phosphine sulfides obtained are new for the most part.

The compounds of the formula I are the object of the invention.

<img file="ES2194584A1_D0001.tif" />

in which

AesOoS;

xes0o1;

OR

II

ResM, or —C — Y₁ oZi, except that if R is M x it is 0; Ar is a group

ES 2 194 584 A1

R, • β

R

R

<img file="ES2194584A1_D0002.tif" />

or Ar signifies cyclopentyl, cyclohexyl, naphthyl, anthracyl, biphenylyl or a 5- or 6-membered heterocyclic ring containing O, S or N atoms, the cyclopentyl, cyclohexyl, naphthyl, anthracyl, biphenylyl and the 5-ring heterocyclic moieties being or 6 links unsubstituted or substituted by halogen, C alkyl₁-C4 and / or C1-C4 alkoxy;

R1 and R2 independently of each other signify C1-C20 alkyl, OR11, CF3 or halogen;

R3, R4 and R5, regardless of solid, are hydrogenic, C1-C20 alkyl, OR11 or halogen;

or in each case two of the radicals R1, R2, R3, R4 and R5 together form a C1-C20 alkylene radical which can be interrupted by O, S or NR14;

R6 means C1-C24 alkyl, unsubstituted or substituted by cycloalkenyl, phenyl, CN, C (O) R11, C (O) OR11, C (O) N (R14) 2, OC (O) R11, OC (O) OR11, N (R14) C (O) N (R14), OC (O) NR14, N (R14) C (O) OR11, cycloalkyl, halogen, OR11,

SR11, N (R12) (R13) or

<img file="ES2194584A1_D0003.tif" />

<img file="ES2194584A1_D0004.tif" />

C alkyl₂-C₂₄ that is interrupted one or more times by groups O, S or NR₁₄ non-consecutive and is unsubstituted or substituted by OR11, SR11, N (R12) (R13), CN, C (O) R11, C (O) OR11 or / and C (O) N (R14) 2; and / or / ° x —C-CH „.

H ² alkenyl C₂-C₂₄ that is uninterrupted or interrupted one or several times by groups O, S or NR₁₄ not consecutive and is unsubstituted or substituted by OR₁₁, MR₁₁ or N (R₁₂) (R₁₃);

C5-C24 cycloalkenyl that is uninterrupted or interrupted one or more times by non-consecutive O, S or NR14 groups and is unsubstituted or substituted by OR11, SR11 or N (R12) (R13);

arylalkyl C₇-C₂₄ unsubstituted or substituted on the aryl group by C alkyl₁-C₁₂, C alkoxy₁-C₁₂ or halogen;

C4-C24 cycloalkyl which is uninterrupted or interrupted one or more times by O, S and / or NR14 groups and is unsubstituted or substituted by OR11, SR11 or N (R12) (R13); or C8-C24 arylcycloalkyl or C8-C24 arylcycloalkenyl;

R11 signifies H, C1-C20 alkyl, C3-C8 cycloalkyl, phenyl, benzyl or C2-C20 alkyl, which is interrupted one or more times by O or S and which is unsubstituted or substituted by OH and / or SH;

R12 and R13, independently of each other, signify hydrogen, C1-C20 alkyl, C3-C8 cycloalkyl, phenyl, benzyl or C alkyl₂-C₂₀, which is interrupted one or more times by O or S and which is unsubstituted or substituted by OH and / or SH; or else R12 and R13 together form a C3-C5 alkylene group which can optionally be interrupted by O, S or NR14;

R14 signifies hydrogen, phenyl, C1-C12 alkyl or C2-C12 alkyl which is interrupted one or more times by O or S and which is optionally substituted by OH and / or SH; and M is hydrogen, Li, Na or K.

Y₁ is C alkyl₁-C₁₈ that it is unsubstituted or substituted by one or more phenyl; halogenoalkyl C₁-C₁₈; C2-C18 alkyl that is interrupted one or more times by O or S and that can be substituted by OH

ES 2 194 584 A1 and / or SH; unsubstituted C3-C18 cycloalkyl or C3-C18 cycloalkyl substituted by C1-C20 alkyl, OR11, CF3 or halogen; or C alkenyl₂-C₁₈; or Y₁ is OR₁₁, N (R₁₂) (R₁₃) or one of the remains

<img file="ES2194584A1_D0005.tif" />

or Y₁ is cyclopentyl, cyclohexyl, naphthyl, anthracyl or biphenylyl or a 5- or 6-membered heterocyclic ring containing O, S, or N, the moieties cyclopentyl, cyclohexyl, naphthyl, anthracil, biphenylyl or the 5 or 6-membered heterocyclic ring being unsubstituted or substituted by halogen, C1-C4 alkyl and / or C1-C4 alkoxy;

Y2 is a direct link; C 1 -C 18 alkylene unsubstituted or substituted by phenyl; unsubstituted C4-C18 cycloalkylene or C4-C18 cycloalkylene substituted by C1-C12 alkyl, OR11, halogen and / or phenyl; unsubstituted C5-C18 cycloalkenylene or C5-C18 cycloalkenylene substituted by C1-C12 alkyl, OR11, halogen and / or phenyl; unsubstituted phenylene or phenylene substituted one to four times by C1-C12 alkyl, OR11, halogen, - (CO) OR14, - (CO) N (R12) (R13) and / or phenyl;

obienY2 is a remainder

<img file="ES2194584A1_D0006.tif" />

or

<img file="ES2194584A1_D0007.tif" />

these residues being unsubstituted or substituted from one to four times on one or both aromatic rings by C1-C12 alkyl, OR11, halogen and / or phenyl;

Y3 is O, S, SO, SO2, CH2, C (CH3) 2, CHCH3, C (CF3) 2, CO or a direct bond;

R1' and R2 'independently of each other have the same meanings attributed to R1 and R2, and

R3 ', R4' and R5 'independently of each other have the same meanings attributed to R3, R4 and R5;

or in each case two of the radicals R1 ', R2', R3 ', R4' and R5 'together form a C1-C20 alkylene, which is optionally interrupted by O, S or -NR14; with the condition that Y1 is not identical with Ar;

Z1 is C1-C24 alkyl that is unsubstituted or substituted one or more times by OR15, SR15,

<img file="ES2194584A1_D0008.tif" />

N (R₁₆) (R17), phenyl, halogen, CN, -N = C = A, _ and / or

<img file="ES2194584A1_D0009.tif" />

; ObienZ1 is C2-C24 alkyl which is interrupted one or more times by O, S or NR14 and which is unsubstituted or substituted by OR15, SR15, N (R16) (R17), phenyl, halogen _F ^x

<img file="ES2194584A1_D0010.tif" />

me

<img file="ES2194584A1_D0011.tif" />

; or Z1 is

ES 2 194 584 A1 Ci -C24 alkoxy which is substituted one or more times by phenyl, CN, -N = C = A,

O / \ c — CH H

TO

II - c — R

TO

II

-C — OR and / or

<img file="ES2194584A1_D0012.tif" />

; obienZi is

TO

II —c — OR ,,

<img file="ES2194584A1_D0013.tif" />

obienZi is unsubstituted C3-C24 cycloalkyl or C3-C24 cycloalkyl substituted by Ci-C20 alkyl, ORii, CF3 or halogen; unsubstituted C2-C24 alkenyl or C2-C24 alkenyl substituted by C6-Ci2 aryl, CN, (CO) ORi5 or (CO) N (Ri8) 2; or Zi is C3-C24 cycloalkenyl or one of the moieties

<img file="ES2194584A1_D0014.tif" />

ES 2 194 584 A1

<img file="ES2194584A1_D0015.tif" />

or Z1 is C1-C24 alkylthio whose alkyl moiety was uninterrupted or interrupted one or more times by non-consecutive O or S atoms and was unsubstituted or substituted by OR15, SR15 and / or halogen; with the condition that Z1 and R6 are not identical;

A1 is O, S, or NR18a;

Z2 is C1-C24 alkylene, C2-C24 alkylene interrupted one or more times by O, S or NR14; C2-C24 alkenylene; C2-C24 alkenylene interrupted one or more times by O, S or NR14; C3-C24 cycloalkylene; C3-C24 cycloalkylene interrupted one or more times by O, S or NR14; C3-C24 cycloalkylene; C3-C24 cycloalkenylene interrupted one or more times by O, S or NR14;

the radicals being C1-C24 alkylene, C2-C24 alkylene, C2-C24 alkenylene, C3-C24 cycloalkylene and C3-C24 cycloalkenylene unsubstituted or substituted by OR11, SR11, N (R12) (R13) and / or halogen; or Z2 is one of the remains

<img file="ES2194584A1_D0016.tif" />

these moieties being unsubstituted or substituted on the aromatic ring by C1-C20 alkyl; C2-C20 alkyl interrupted one or more times by non-consecutive O atoms and which is unsubstituted or substituted by OH and / or SH; OR11, SR11, N (R12) (R13), phenyl, halogen, NO2, CN, (CO) -OR11, (CO) -R11, (CO) N (R12) (R13) SO2R24, OSO2R24, CF3 and / or CCl3;

obienZ2 is a group

<img file="ES2194584A1_D0017.tif" />

ES 2 194 584 A1

Z3 is CH2, CH (OH), CHCH3 or C (CH3) 2;

Z4 is S, O, CH2, C = O, NRi4 or a direct bond;

<img file="ES2194584A1_D0018.tif" />

Z₆ and Z7 independently of each other are CH₂, CHCH₃ or C (CH₃)₂;

reselnumer 0, 1 or 2;

ses a number from 1 to 12;

q is a number from 0 to 50;

typ are in each case a number from 0 to 20;

E, G, G₃ and G₄ regardless of whether they are C alkyl₁-C₁₂ unsubstituted or C alkyl₁-C₁₂ substituted by halogen or unsubstituted phenyl or phenyl substituted by one or more Ci-C4 alkyl; or are C2-C12 alkenyl;

OR

R_11a is C alkyl₁-C₂₀ replaced one or more times by OR₁₅ or _C ~ CH or it is C2-C20 alkyl interrupted one or more times by non-consecutive O atoms and which is unsubstituted, &amp;

or replaced one or more times by OR₁₅, halogen or _C ~ 'CH

H ^: obienR11a is C2-C20 alkenyl or C3-C12 alkynyl, obienR11a is C3-C12 cycloalkenyl substituted one or more times by halogen, NO2, C1-C6 alkyl, OR11 or C (O) OR18; or is C7-C16 arylalkyl or C arylcycloalkyl₈ -C₁₆;

R15 has one of the meanings of R11 or else

TO

<img file="ES2194584A1_D0019.tif" />

—C — 0R₁₈ or

<img file="ES2194584A1_D0020.tif" />

R16 and R17, independently of each other, have one of the meanings of R12 or are a remainder

II —CR₁₈ , - C-OR₁₈ c - CN (R_ia)₂ ;

R18 is hydrogen, C1-C24 alkyl, C2-C12 alkenyl, C3-C8 cycloalkyl, phenyl, benzyl, C2-C20 alkyl interrupted one or more times by O or S and which is unsubstituted or substituted by OH;

R18a and R18b independently of whether they are hydrogen, C1-C20 alkyl substituted one or more times by

ES 2 194 584 A1, or

OR-15, halogen, styryl, methylstyryl, -N = C = A or _C^_CH

H ^{2 ;} or they are C₂-C₂₀ interrupted one or more times by non-consecutive O atoms and is without

Or substitute or substituted one or more times by OR₁₅, halogen, styryl, methylstyryl, or —C^_CH;

H ² obien R18a and R18b are C2-C12 alkenyl; C5-C12 cycloalkyl substituted by -N = C = A or -CH2-N = C = A and are also unsubstituted or substituted one or more times by C1-C4 alkyl; or R18a and R18b are unsubstituted or substituted C6-C12 aryl a or several times by halogen, NO2, C1-C6 alkyl, C2-C4 alkenyl, OR11, -N = C = A, -CH2-N = C = A or C (O) OR18, or R18a and R18b are C7-C16 arylalkyl; or R18a and R₁₈b together are arylcycloalkyl C₈-C₁₆; or R1_8a and R₁₈b independently of each other are

<img file="ES2194584A1_D0021.tif" />

Y3 is O, S, SO, SO2, CH2, C (CH3) 2, CHCH3, C (CF3) 2, (CO), or a direct bond;

R₁₉, R₂₀, R₂₁, R₂₂ and R₂₃ independently of each other are hydrogen, C alkyl₁ -C₂₀; C alkyl₂-C₂₀ that it is interrupted one or more times by non-consecutive O atoms and is unsubstituted or substituted by OH and / or SH; or R19, R20, R21, R22 and R23 are OR11, SR11, N (R12) - (R13), NO2, CN, SO2R24, OSO2R24, CF3, CCl3, halogen; or phenyl which is unsubstituted or substituted one or more times by C1-C4 alkyl or C1-C4 alkoxy;

or in each case two of the residues R19, R20, R21, R22 and R23 together form a C1-C20 alkylene that is uninterrupted or interrupted by O, S or -NR14;

R24 is C1-C12 alkyl, C1-C12 alkyl substituted by halogen; phenyl or phenyl substituted by OR11 and / or SR11; with the condition that R6 and Z1 are not identical.

C1-C24 alkyl is straight or branched and can be for example C2-C24 alkyl, C1-C20 alkyl, C1-C18 alkyl, C1-C12 alkyl, C1-C8 alkyl, C1-C6 alkyl or C1-C4 alkyl. Examples are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl , tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl or tetraicosyl.

R1, R2, R3, R1 ', R2' and R3 'are for example C1-C8 alkyl, especially C1-C6 alkyl, preferably C1-C4 alkyl, especially preferably methyl.

Alkyl C₁-C₂₀, C alkyl₁-C₁₈, C alkyl₁-C₁₂, C alkyl₁-C₆ and C alkyl₁-C₄ they are also linear or branched and have, for example, the meanings defined above up to the corresponding number of C atoms. R5, R6, R7, R8, R9, R10, R11, R12, R13, R19, R20, R21, R22 and R23 are eg C1-C8 alkyl, in particular C1-C6, preferably C1-C4, for example methyl or butyl.

C2-C24 alkyl interrupted one or more times by O, S or NR14 is interrupted for example 1 to 9 times, eg 1 to 7 times or 1 to 2 times by O, S or NR14. If the remains are interrupted by several O, S or NR₁₄, then O atoms, S atoms, or NR groups₁₄ they are separated from each other in each case, at least by one methylene group. Thus, the O atoms, S atoms, or NR14 groups are not directly consecutive. The alkyl moiety can be straight or branched. For example, structural units of the type -CH2-O-CH3, -CH2CH2-O-CH2CH3, - [CH2CH2O] z-CH3 are formed, where z is a number from 1 to 9, - (CH2CH2O) 7CH2CH3, -CH2-CH ( CH3) -O- -CH2-CH2CH3, -CH2-CH (CH3) -O-CH2CH3, -CH2SCH3 or -CH2-N (CH3) 2.

The C2-C20 alkyl, C2-C18 alkyl, C2-C12 alkyl that are interrupted by O and eventually

ES 2 194 584 A1 by S are for example linear or branched and can have, for example, the meanings indicated above depending on the number of carbon atoms that correspond. Also in this case, the O atoms must not be consecutive.

C1-C18 haloalkyl are C1-C18 alkyl described above which are substituted one or more times by halogen. Such is for example perfluorinated C1-C18 alkyl. Examples are chloromethyl, trichloromethyl, trifluoromethyl or 2-bromopropyl, especially trifluoromethyl or trichloromethyl.

C3-C24 cycloalkyl, eg C4- -C24 cycloalkyl, C5-C12 cycloalkyl, C4-C12 cycloalkyl, C3-C12 cycloalkyl, C cycloalkyl₃-C₈, means individual cyclic alkyl systems or even bridged cyclic alkyl systems. The moieties may also contain linear or branched alkyl groups (such as those described above based on the number of carbon atoms). Examples are cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, cycloicosyl, in particular cyclopentyl and cyclohexyl, preferably cyclohexyl. Other examples are

<img file="ES2194584A1_D0022.tif" />

Cycloalkyl C₃-C₈, eg C cycloalkyl₃-C₆, can have the meanings indicated above, taking into account the corresponding number of carbon atoms.

C3-C18 cycloalkyl substituted by C1-C20 alkyl, OR11, CF3 or halogen is preferably substituted in the ortho positions of the cycloalkyl ring. 2,4,6-trimethylcyclohexyl and 2,6-dimethoxyclohexyl are preferred.

C2-C24 alkenyl moieties are mono- or polyunsaturated and are linear or branched, being for example C2-C18 alkenyl, C2-C8 alkenyl, C2-C6 alkenyl or C2-C4 alkenyl. Examples are vinyl, allyl, methallyl, 1,1-dimethylallyl, 1-butenyl, 2-butenyl, 1,3-pentadienyl, 1-hexenyl, 1-octenyl, decenyl or dodecenyl, especially allyl. C2-C18 alkenyl has the same meanings indicated above, taking into account the corresponding carbon atom number.

If the C2-C24 alkenyl residues are interrupted, for example by O, then the following structures are included, for example: - (CH2) yO- (CH2) x-CH = CH2, - (CH2) yO- (CH2) xC (CH3) = CH2 or - (CH2) y-OCH = CH2, in which x and y, independently of each other, represent a number from 1 to 21.

C3-C24 cycloalkenyl, eg C5-C12 cycloalkenyl, C3-C12 cycloalkenyl, C3-C8 cycloalkenyl, means individual coyclic alkyl systems and also in bridge-type coyclic alkyl systems and can be mono- or polyunsaturated, eg mono- or diunsaturated. The moieties may also contain linear or branched alkyl groups (described above, depending on the corresponding carbon atom number). Examples are cyclopropenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, cyclododecenyl, cycloicosenyl, especially cyclopentenyl and cyclohexenyl, preferably cyclohexenyl.

C7-C24 arylalkyl is for example C7-C16 arylalkyl or C7-C11 arylalkyl. The alkyl moiety in this group can be straight or branched. Examples are benzyl, phenylethyl, α-methylbenzyl, phenylpentyl, phenylhexyl, α, α-dimethylenezyl, naphthylmethyl, naphthylethyl, naphthyle-1-yl, or naphthyl-1-methyleth-1-yl, in particular benzyl. Substituted C7-C24 arylalkyl was substituted on the aryl ring one to four times, eg once, twice or three times, in particular once or twice.

C8-C24 arylcycloalkyl is, for example, C9-C16 arylcycloalkyl, C9-C13 arylcycloalkyl and is a cycloalkyl fused to one or more aryl rings. They are examples of it

ES 2 194 584 A1

<img file="ES2194584A1_D0023.tif" />

<img file="ES2194584A1_D0024.tif" />

etc.

C1-C12 alkylthio means straight or branched moieties and is, for example, C1-C8 alkylthio, C1-C6 alkylthio or C1-C4 alkylthio. Examples are methylthio, ethylthio, propylthio, isopropylthio, n-butylthio.

Sec-butylthio, isobutylthio, tert-butylthio, pentylthio, hexylthio, heptylthio, 2,4,4-trimethylpentylthio, 2-ethylhexylthio, octylthio, nonylthio, decylthio or dodecylthio, in particular methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, sec-butylthio, isobutylthio, tert-butylthio, preferably methylthio.

C1-C8 alkylthio is, for example, linear or branched and has, for example, the meanings indicated above, depending on the corresponding number of carbon atoms.

C1-C24 alkylene is linear or branched and means for example C1 -C20 alkylene, C1- -C12 alkylene, C1-C8 alkylene, C2-C8 alkylene, C1-C4 alkylene, for example methylene, ethylene, propylene, isopropylene, n- butylene, sec-butylene, isobutylene, tert-butylene, pentylene, hexylene, heptylene, octylene, nonylene, deylene, dodecylene, tetradecylene, heptadecylene, octadecylene, icosylene or, eg, C1-C12 alkylene, for example ethylene, decylene , - CH —CH-CH, I ² —CH- (CH₂)₂-, —CH- (CH₂)₃-, -C (CH₃)₂-CH₂- or -ch_:

<img file="ES2194584A1_D0025.tif" />

C2-C18 alkylene is also linear or branched, eg C2-C8 alkylene or C2-C4 alkylene and has the meanings defined above, depending on the number of carbon atoms that correspond.

If the C2-C18 alkylene is interrupted once or several times by O, S or NR14, then it will be interrupted 1 to 9 times, e.g. 1 to 7 times or once or twice by O, S or NR14, and structural units of the type -CH2-O-CH2-, -CH2CH2-O-CH2CH2-, - [CH2-CH2O) z - will be formed, in which

<img file="ES2194584A1_D0026.tif" />

or -CH2 CH2 - (NR14) -CH2 -CH2 -. The alkylene residues can be linear or branched and, if the alkylene residues are interrupted by two or more groups O, S or NR14, then the groups O, S and NR14 would not be consecutive, but in each case would be separated from each other by less for a methylene group.

C2-C24 alkenylene is mono- or polyunsaturated and is linear or branched, eg being C2-C18 alkenylene or C2-C8 alkenylene. Examples are ethenylene, propenylene, butenylene, pentenylene, hexenylene, octenylene, eg 1-propenylene, 1-butenylene, 3-butenylene, 2-butenylene, 1,3-pentadienylene, 5-hexenylene or 7-octenylene .

C2-C24 alkenylene interrupted one or more times by O, S, NR14, is mono- or polyunsaturated and is linear or branched, being interrupted for example 1 to 9 times, eg 1 to 7 times or 1 time or 2 times by O, S, NR14, but in the case of having several O, S or NR14 groups, these would be separated from each other by at least one methylene group. The meanings of C2-C24 alkenylene are as defined above.

C4-C18 cycloalkylene is straight or branched and can be a single ring or several alkyl rings linked together, eg adamantyl. They are eg cycloalkylene C₄-C₁₂ or cycloalkylene C₄ -C₈, for example cyclopentylene, cyclohexylene, cyclooctylene, cyclododecylene, in particular cyclopentylene and cyclohexylene, preferably cyclohexylene. However, C4-C18 cycloalkylene means for example structural units of the type

ES 2 194 584 A1

<img file="ES2194584A1_D0027.tif" />

where r and s, independently of each other, signify a number from 0 to 12, and the sum of r + s is &lt;12, or

<img file="ES2194584A1_D0028.tif" />

where r and s, independently of each other, signify a number from 0 to 13, and the sum of r + s is &lt;13.

C4-C18 cycloalkylene interrupted one or more times by O, S or NR14, means cycloalkylene groups such as those described above that are interrupted either in the ring or in the side chain, for example 1 to 9 times, p. eg 1 to 7 times or once or twice for O, S, NR14.

C3-C24 cycloalkenylene is linear or branched and can be a single ring or several alkyl rings linked together, being mono- or polyunsaturated. Eg. C3-C12 cycloalkenylene or C3-C8 cycloalkenylene, for example cyclopentenylene, cyclohexenylene, cyclooctenylene, cyclododecenylene, in particular cyclopentenylene and cyclohexenylene, preferably cyclohexenylene. However, C3-C24 cycloalkenylene means for example structural units of the type

<img file="ES2194584A1_D0029.tif" />

where r and s, independently of each other, signify a number from 0 to 12, and the sum + ses &lt;12, or

<img file="ES2194584A1_D0030.tif" />

where r and s, independently of each other, signify a number from 0 to 13, and the sum of r + s is &lt;13.

C5-C18 cycloalkenylene has the meanings defined above for C3-C24 cycloalkenylene, but according to the corresponding carbon atom number.

C3-C24 cycloalkenylene interrupted one or more times by O, S or NR14, means cycloalkenylene groups such as those described above that are interrupted either in the ring or in the side chain, for example 1 to 9 times, p. eg 1 to 7 times or 1 time or 2 times for O, S, NR14. They are examples of it

<img file="ES2194584A1_D0031.tif" />

Halogen is fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine and bromine, preferably chlorine. In their halogen condition, R1, R1 ', R2, R2', R3 and R3 'are in particular chlorine.

If in each case two of the residues R1, R2, R3, R4 or R5 or in each case two of the residues R19, R20, R21, R22 or R23 form a C1-C12 alkylene, then, for example, the following structures result

ES 2 194 584 A1

<img file="ES2194584A1_D0032.tif" />

In relation to the present application, the term "and / or" means that not only one of the defined alternatives (substituents) can be present at the same time, but for example two or more defined alternatives (substituents), that is, mixtures of different alternatives (substituents).

The term "at least" means to define one or more of one, for example one or two or three, preferably one or two.

As a 5- or 6-membered heterocyclic ring containing O, S or N, Ar is eg furyl, thienyl, pyrrolyl, oxynyl, dioxynyl or pyridyl. Such heterocyclic moieties can be mono- or polysubstituted, eg monosubstituted or disubstituted, by halogen, linear or branched C1-C4 alkyl, for example methyl, ethyl, propyl, butyl and / or C1-C4 alkoxy. Examples are dimethylpyridyl, dimethylpyrrolyl or methylfuryl.

Ar is for example 2-methylnaphth-2-yl, 2-methoxynaphth-2-yl, 1,3-dimethylnaphth-2-yl, 2,8-dimethylnaphth-1-yl, 1,3-dimethoxynaphth-2-yl, 1, 3-dichloronaphth-2-yl, 2,8-dimethoxynaphth-1-yl, 2,4,6-trimethylpyrid-3-yl, 2,4-dimethoxyfuran-3-yl or 2,4,5-trimethylthien-3-yl.

Compounds of formula I in which Ar is a moiety are preferred.

<img file="ES2194584A1_D0033.tif" />

The compounds of formula I in which R₁ yR₂, independently of one another, they are C1-C4 alkyl, C1-C4 alkoxy, CloCF3, in particular methyl or methoxy.

R1 and R2 are preferably identical.

R1 and R2 are preferably C1-C4 alkyl or C1-C4 alkoxy.

In the compounds of formula I, R3, R4 and R5 are, in particular, independently of one another, hydrogenic, C1-C4 alkyl, Cl or C1-C4 alkoxy, especially hydrogenic or methoxy.

R3 is preferably C1-C4 alkyl or C1-C4 alkoxy, especially methyl, methoxy or hydrogen, and R4 and R5 are hydrogen.

In the compounds of formula I, R6 is especially C1-C24 alkyl, unsubstituted or substituted by cycloalkenyl, CN, C (O) R11, C (O) OR11, C (O) N (R14) 2, cycloalkyl, halogen; C2-C24 alkyl that was interrupted one or more times by non-consecutive O, S or NR14 groups and that was eventually substituted by OR11, SR11, N (R12) (R13), CN, C (O) R11, C (O) OR11 and / or C (O) N- (R14) 2; C2-C24 alkenyl that was interrupted one or more times by non-consecutive O, S or NR14 groups and that was eventually substituted by OR11, SR11, N (R12) - (R13); benzyl, cyclopentyl, cyclohexyl, C4-C24 cycloalkyl which is interrupted one or more times by groups O, S or NR14; or C8-C24 arylcycloalkyl.

Also of interest are compounds of formula I in which R12 and R13 are eg. hydrogenic, C alkyl₁-C₄, phenyl or benzyl or C alkyl₂-C₁₂ that it was interrupted one or more times by non-consecutive O atoms and that it was unsubstituted or substituted by OH and / or SH; or R12 and R13 together form a piperidino, morpholino, or piperazino. R12 and R13 are preferably C1-C4 alkyl or R12 and R13 together form a morpholino.

R14 of the compounds of formula I is in particular hydrogenic, phenyl, C1-C4 alkyl or C2-C4 alkyl which was interrupted one or more times by O or S and which was unsubstituted or substituted by OH and / or SH; it is preferably hydrogen or C1-C4 alkyl.

ES 2 194 584 A1

In the compounds of formula I, M is preferably hydrogen or Li, in particular Li.

Of special interest are the compounds of formula I, where R is M, in which

R1 and R2 are independently C1-C12 alkyl, OR11, CF3 or halogen;

R3, R4 and R5 independently of whether or not are hydrogen, C1-C12 alkyl, OR11 or halogen;

R6 is C1-C12 alkyl, unsubstituted or substituted by cycloalkenyl, CN, C (O) R11, C (O) OR11, C (O) N (R14) 2, cycloalkyl; C2-C12 alkyl that is interrupted one or more times by non-consecutive O, S or NR14 groups and that is eventually substituted by OR11, SR11, N (R12) (R13), CN, C (O) R11, C (O) OR11 and / or C (O) N (R14) 2; C2-C12 alkenyl which is interrupted one or more times by non-consecutive O, S or NR14 groups and which is optionally substituted by OR11, SR11, N (R12) (R13); benzyl, cyclopentyl, cyclohexyl, C4 -C12 cycloalkyl which is interrupted one or more times by O, S and / or NR14 groups, or C8 -C12 arylcycloalkyl;

R11 is H, C1-C12 alkyl, cyclohexyl, cyclopentyl, phenyl, or benzyl;

R12 and R13 independently of whether they are C1-C12 alkyl, cyclopentyl, cyclohexyl, phenyl, benzyl or C2-C12 alkyl that is interrupted one or more times by non-consecutive O atoms and that is unsubstituted or substituted by OH and / or SH ; either R12 and R13 together form a piperazino, morpholino, or piperazino;

R14 is hydrogen or C1-C12 alkyl; Y

Hydrogen month or Li.

Of special interest are the compounds of formula I, where R is M, in which R1 and R2 independently of whether they are C1-C4 alkyl or OR11;

R3, R4 and R5 independently of whether or not are hydrogen, C1-C4 alkyl or OR11;

R6 is C1-C12 alkyl, unsubstituted or substituted by CN, C (O) R11, C (O) OR11, C (O) N (R14) 2; C2-C12 alkyl that is interrupted one or more times by non-consecutive O and that is eventually substituted by OR11, SR11, N (R12) (R13), CN, C (O) R11, C (O) OR11 or C (O ) N (R14) 2; C2 -C8 alkenyl which is interrupted one or more times by non-consecutive O and which is optionally substituted by OR11; benzyl, cyclopentyl, cyclohexyl, C4-C8 cycloalkyl which is optionally interrupted by O, S and / or NR14 groups; or C8-C12 arylcycloalkyl;

R11 is H or C1-C12 alkyl;

R14 is hydrogen or C1-C8 alkyl; and

M stands for Li.

Examples of compounds of formula I, where R is M, are lithium (2,6-dimethylbenzoyl) ethylphosphine; Lithium (2,6-diethylbenzoyl) ethylphosphine; Lithium (2,4,6-trimethylbenzoyl) ethylphosphine; Lithium (2,3,4,5,6-pentamethylbenzoyl) ethylphosphine; Lithium (2,3,5,6-tetramethylbenzoyl) ethylphosphine; Lithium (2,4,6-triisopropylbenzoyl) ethylphosphine; Lithium (2,4,5,6-tetramethylbenzoyl) ethylphosphine; Lithium (2,4,6-tri-tert-butylbenzoyl) ethylphosphine; Lithium (2,6-dimethyl-4-tert-butylbenzoyl) ethylphosphine; Lithium (2,6-diphenoxymethylbenzoyl) ethylphosphine; Lithium (2,3,6-trimethylbenzoyl) ethylphosphine; Lithium (2,3,4,6 tetramethylbenzoyl) ethylphosphine; Lithium (2-phenyl-6-methylbenzoyl) ethylphosphine; Lithium (2,4,6-trimethoxybenzoyl) ethylphosphine; Lithium (2,4-dimethoxybenzoyl) ethylphosphine; Lithium (2,3, -6-trimethoxybenzoyl) ethylphosphine; Lithium (2,6-diethoxybenzoyl) ethylphosphine; Lithium (2,6-dimethoxy-3,5-dimethylbenzoyl) ethylphosphine; Lithium (2,6-dimethoxy-4-methylbenzoyl) ethylphosphine; Lithium (2,6-dimethoxy-3-bromobenzoyl) ethylphosphine; Lithium (2,6-dimethoxy-3-chlorobenzoyl) ethylphosphine; Lithium (2,6-dimethoxy-3-chloro-5-bromobenzoyl) ethylphosphine; Lithium (2,6-dimethoxy-3,5-dichlorobenzoyl) ethylphosphine; Lithium (2,3,6-trimethoxy-5-bromobenzoyl) ethylphosphine; Lithium (2,6-dichlorobenzoyl) -ethylphosphine; Lithium (2,4,6-trichlorobenzoyl) ethylphosphine; Lithium (2,3,6-trichlorobenzoyl) ethylphosphine; Lithium (2,3,5,6-tetrachlorobenzoyl) ethylphosphine; Lithium (2,3, -4,5,6-pentachlorobenzoyl) ethylphosphine; Lithium (2,6-dichloro-3-methylbenzoyl) ethylphosphine; Lithium (2-chloro-6-methylbenzoyl) ethylphosphine; Lithium (2-methoxy-3,6-dichlorobenzoyl) ethylphosphine; (2-methoxy-6-chlorobenzoyl)

ES 2 194 584 A1 lithium ethylphosphine; Lithium (2,6-bis (trifluoromethyl) -benzoyl) ethylphosphine; Lithium (2-chloro-6-methylthiobenzoyl) ethylphosphine; Lithium (2,6-dibromobenzoyl) ethylphosphine; Lithium (2,6-dimethylbenzoyl) -n-butylphosphine; Lithium (2,6-diethylbenzoyl) -n-butylphosphine; Lithium (2,4,6-trimethylbenzoyl) -n-butylphosphine; Lithium (2,3,4,5,6-pentamethylbenzoyl) -n-butylphosphine; Lithium (2,3,5,6-tetramethylbenzoyl) -n-butylphosphine; (2,4,6-triisopropylbenzoyl) -n-butylphosphine lithium; (2,4,5,6-tetramethylbenzoyl) -n-butylphosphine lithium; Lithium (2,4,6-tri-tert-butylbenzoyl) -n-butylphosphine; Lithium (2,6-dimethyl-4-tert-butylbenzoyl) -n-butylphosphine; Lithium (2,6-diphenoxymethylbenzoyl) -n-butylphosphine; Lithium (2,3,6-trimethylbenzoyl) -n-butylphosphine; Lithium (2,3,4,6-tetramethylbenzoyl) -n-butylphosphine; Lithium (2-phenyl-6-methylbenzoyl) -n-butylphosphine; Lithium (2,4,6-trimethoxybenzoyl) -n-butylphosphine; Lithium (2,4-dimethoxybenzoyl) -n-butylphosphine; Lithium (2,3,6-trimethoxybenzoyl) -n-butylphosphine; Lithium (2,6-diethoxybenzoyl) -n-butylphosphine; Lithium (2,6-dimethoxy-3,5-dimethylbenzoyl) -n-butylphosphine; Lithium (2,6-dimethoxy-4-methylbenzoyl) -n-butylphosphine; Lithium (2,6-dimethoxy-3-bromobenzoyl) -n-butylphosphine; Lithium (2,6-dimethoxy-3-chlorobenzoyl) n-butylphosphine; Lithium (2,6-dimethoxy-3-chloro-5-bromobenzoyl) -n-butylphosphine; Lithium (2,6-dimethoxy-3,5-dichlorobenzoyl) -n-butylphosphine; Lithium (2,3,6-trimethoxy-5-bromobenzoyl) -n-butylphosphine; Lithium (2,6-dichlorobenzoyl) -n-butylphosphine; Lithium (2,4,6-trichlorobenzoyl) -n-butylphosphine; Lithium (2,3,6-trichlorobenzoyl) -n-butylphosphine; Lithium (2,3,5,6-tetrachlorobenzoyl) -n-butylphosphine; Lithium (2,3,4,5,6-pentachlorobenzoyl) -n-butylphosphine; lithium (2,6-dichloro-3-methylbenzoyl) -n-butylphosphine; Lithium (2-chloro-6-methylbenzoyl) -n-butylphosphine; Lithium (2-methoxy-3,6-dichlorobenzoyl) -n-butylphosphine; Lithium (2-methoxy-6-chlorobenzoyl) -n-butylphosphine; Lithium (2,6-bis (trifluoromethyl) -benzoyl) -n butylphosphine; Lithium (2-chloro-oo-methylthiobenzoyl) -n-butylphosphine; Lithium (2,6-dibromobenzoyl) n-butylphosphine; Lithium (2,6-dimethylbenzoyl) isobutylphosphine; lithium (2,6-diethylbenzoyl) -isobutylphosphine; Lithium (2,4,6-trimethylbenzoyl) isobutylphosphine; Lithium (2,3,4,5,6-pentamethylbenzoyl) isobutylphosphine; Lithium (2,3,5,6-tetramethylbenzoyl) isobutylphosphine; Lithium (2,4,6-triisopropylbenzoyl) isobutylphosphine; Lithium (2,4,5,6-tetramethylbenzoyl) isobutylphosphine; Lithium (2,4,6-tri-tert-butylbenzoyl) isobutylphosphine; Lithium (2,6-dimethyl-4-tert-butylbenzoyl) -isobutylphosphine; Lithium (2,6-diphenoxymethylbenzoyl) isobutylphosphine; Lithium (2,3,6-trimethylbenzoyl) isobutylphosphine; Lithium (2,3,4,6-tetramethylbenzoyl) isobutylphosphine; Lithium (2-phenyl-6-methylbenzoyl) isobutylphosphine; Lithium (2,4,6-trimethoxybenzoyl) isobutylphosphine; Lithium (2,4-dimethoxybenzoyl) isobutylphosphine; Lithium (2,3,6-trimethoxybenzoyl) isobutylphosphine; Lithium (2,6-diethoxybenzoyl) isobutylphosphine; Lithium (2,6-dimethoxy-3,5-dimethylbenzoyl) isobutylphosphine; Lithium (2,6-dimethoxy-4-methylbenzoyl) isobutylphosphine; Lithium (2,6-dimethoxy-3-bromobenzoyl) isobutylphosphine; Lithium (2,6-dimethoxy-3-chlorobenzoyl) isobutylphosphine; Lithium (2,6-dimethoxy-3-chloro-5-bromobenzoyl) isobutylphosphine; Lithium (2,6-dimethoxy-3,5-dichlorobenzoyl) isobutylphosphine; Lithium (2,3,6-trimethoxy-5-bromobenzoyl) isobutylphosphine; Lithium (2,6-dichlorobenzoyl) isobutylphosphine; Lithium (2,4,6-trichlorobenzoyl) isobutylphosphine; Lithium (2,3,6-trichlorobenzoyl) isobutylphosphine; Lithium (2,3,5,6-tetrachlorobenzoyl) isobutylphosphine; Lithium (2,3,4,5,6-pentachlorobenzoyl) isobutylphosphine; Lithium (2,6-dichloro 3-methylbenzoyl) isobutylphosphine; Lithium (2-chloro-6-methylbenzoyl) isobutylphosphine; Lithium (2-methoxy-3,6-dichlorobenzoyl) isobutylphosphine; Lithium (2-methoxy-6-chlorobenzoyl) isobutylphosphine; Lithium (2,6-bis (trifluoromethyl) -benzoyl) isobutylphosphine; Lithium (2-chloro-6-methylthiobenzoyl) isobutylphosphine; Lithium (2,6-dibromobenzoyl) isobutylphosphine; Lithium (2,6-dimethylbenzoyl) -1-methylpropylphosphine; Lithium (2,6-diethylbenzoyl) -1-methylpropylphosphine; Lithium (2,4,6-trimethylbenzoyl) -1-methylpropylphosphine; Lithium (2,3,4,5,6-pentamethylbenzoyl) -1-methylpropylphosphine; Lithium (2,3,5,6-tetramethylbenzoyl) -1 methylpropylphosphine; Lithium (2,4,6-triisopropylbenzoyl) -1-methylpropylphosphine; Lithium (2,4, -5,6-tetramethylbenzoyl) -1-methylpropylphosphine; Lithium (2,4,6-tri-tert-butylbenzoyl) -1-methylpropylphosphine; Lithium (2,6-dimethyl-4-tert-butylbenzoyl) -1-methylpropylphosphine; Lithium (2,6-diphenoxymethylbenzoyl) 1-methylpropylphosphine; Lithium (2,3,6-trimethylbenzoyl) -1-methylpropylphosphine; Lithium (2,3,4,6-tetramethylbenzoyl) -1-methylpropylphosphine; Lithium (2-phenyl-6-methylbenzoyl) -1-methylpropylphosphine; Lithium (2,4,6-trimethoxybenzoyl) -1-methylpropylphosphine; Lithium (2,4-dimethoxybenzoyl) -1-methylpropylphosphine; Lithium (2,3,6-trimethoxybenzoyl) -1-methylpropylphosphine; Lithium (2,6-diethoxybenzoyl) -1-methylpropylphosphine; Lithium (2,6-dimethoxy-3,5-dimethylbenzoyl) -1-methylpropylphosphine; Lithium (2,6-dimethoxy-4-methylbenzoyl) -1-methylpropylphosphine; Lithium (2,6-dimethoxy-3-bromobenzoyl) -1-methylpropylphosphine; Lithium (2,6-dimethoxy-3-chlorobenzoyl) -1-methylpropylphosphine; Lithium (2,6-dimethoxy-3-chloro-5-bromobenzoyl) -1-methylpropylphosphine; Lithium (2,6-dimethoxy-3,5-dichlorobenzoyl) -1-methylpropylphosphine; Lithium (2,3,6-trimethoxy-5-bromobenzoyl) -1-methylpropylphosphine; Lithium (2,6-dichlorobenzoyl) 1-methylpropylphosphine; Lithium (2,4,6-trichlorobenzoyl) -1-methylpropylphosphine; Lithium (2,3,6-trichlorobenzoyl) -1-methylpropylphosphine; Lithium (2,3,5,6-tetrachlorobenzoyl) -1-methylpropylphosphine; Lithium (2,3,4,5,6-pentachlorobenzoyl) -1-methylpropylphosphine; Lithium (2,6-dichloro-3-methylbenzoyl) -1-methylpropylphosphine; Lithium (2-chloro-6-methylbenzoyl) -1-methylpropylphosphine; Lithium (2-methoxy-3,6 dichlorobenzoyl) -1-methylpropylphosphine; Lithium (2-methoxy-6-chlorobenzoyl) -1-methylpropylphosphine; Lithium (2,6-bis (trifluoromethyl) -benzoyl) -1-methylpropylphosphine; Lithium (2-chloro-6-methylthiobenzoyl) -1-methylpropylphosphine; Lithium (2,6-dibromobenzoyl) -1-methylpropylphosphine; Lithium (2,6-dimethylbenzoyl) -2,4,4-trimethylpentylphosphine; Lithium (2,6-diethylbenzoyl) -2,4,4-trimethylpentylphosphine; Lithium (2,4,6-trimethylbenzoyl) -2,4,4-trimethylpentylphosphine; (2,3,4,5,6-pentamethylbenzoyl) -2,4,4-tri14

ES 2 194 584 A1 lithium methylpentylphosphine; Lithium (2,3,5,6-tetramethylbenzoyl) -2,4,4-trimethylpentylphosphine; Lithium (2,4,6-triisopropylbenzoyl) -2,4,4-trimethylpentylphosphine; Lithium (2,4,5,6-tetramethylbenzoyl) -2,4,4-trimethylpentylphosphine; Lithium (2,4,6-tri-tert-butylbenzoyl) -2,4,4-trimethylpentylphosphine; Lithium (2,6-dimethyl-4-tert-butylbenzoyl) -2,4,4-trimethylpentylphosphine; Lithium (2,6-diphenoxymethylbenzoyl) -2,4,4-trimethylpentylphosphine; Lithium (2,3,6-trimethylbenzoyl) -2,4,4-trimethylpentylphosphine; Lithium (2,3,4,6-tetramethylbenzoyl) -2,4,4-trimethylpentylphosphine; Lithium (2-phenyl-6-methylbenzoyl) -2,4,4-trimethylpentylphosphine; Lithium (2,4,6-trimethoxybenzoyl) -2,4,4-trimethylpentylphosphine; Lithium (2,4-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine; Lithium (2,3,6-trimethoxybenzoyl) -2,4,4-trimethylpentylphosphine; Lithium (2,6-diethoxybenzoyl) -2,4,4 trimethylpentylphosphine; Lithium (2,6-dimethoxy-3,5-dimethylbenzoyl) -2,4,4-trimethylpentylphosphine; Lithium (2,6-dimethoxy-4-methylbenzoyl) -2,4,4-trimethylpentylphosphine; Lithium (2,6-dimethoxy-3-bromobenzoyl) 2,4,4-trimethylpentylphosphine; Lithium (2,6-dimethoxy-3-chlorobenzoyl) -2,4,4-trimethylpentylphosphine; Lithium (2,6-dimethoxy-3-chloro-5-bromobenzoyl) -2,4,4-trimethylpentylphosphine; Lithium (2,6-dimethoxy-3,5-dichlorobenzoyl) -2,4,4-trimethylpentylphosphine; Lithium (2,3,6-trimethoxy-5-bromobenzoyl) -2,4,4-trimethylpentylphosphine; Lithium (2,6-dichlorobenzoyl) -2,4,4-trimethylpentylphosphine; Lithium (2,4,6-trichlorobenzoyl) -2,4,4 trimethylpentylphosphine; Lithium (2,3,6-trichlorobenzoyl) -2,4,4-trimethylpentylphosphine; Lithium (2,3,5,6-tetrachlorobenzoyl) -2,4,4-trimethylpentylphosphine; Lithium (2,3,4,5,6-pentachlorobenzoyl) -2,4,4-trimethylpentylphosphine; Lithium (2,6-dichloro-3-methylbenzoyl) -2,4,4-trimethylpentylphosphine; Lithium (2-chloro-6-methylbenzoyl) -2,4,4-trimethylpentylphosphine; Lithium (2-methoxy-3,6-dichlorobenzoyl) -2,4,4-trimethylpentylphosphine; Lithium (2-methoxy-6-chlorobenzoyl) -2,4,4-trimethylpentylphosphine; Lithium (2,6-bis (trifluoromethyl) -benzoyl) -2,4,4-trimethylpentylphosphine; Lithium (2-chloro-6-methylthiobenzoyl) -2,4,4-trimethylpentylphosphine; Lithium (2,6-dibromobenzoyl) -2,4,4-trimethylpentylphosphine; Lithium (2,6-dimethylbenzoyl) cyclopentylphosphine; Lithium (2,6-diethylbenzoyl) cyclopentylphosphine; Lithium (2,4,6-trimethylbenzoyl) cyclopentylphosphine; Lithium (2,3,4,5,6-pentamethylbenzoyl) cyclopentylphosphine; Lithium (2,3,5,6-tetramethylbenzoyl) cyclopentylphosphine; Lithium (2,4,6-triisopropylbenzoyl) cyclopentylphosphine; Lithium (2,4,5,6-tetramethylbenzoyl) cyclopentylphosphine; Lithium (2,4,6-tri-tert-butylbenzoyl) cyclopentylphosphine; Lithium (2,6-dimethyl-4-tert-butylbenzoyl) cyclopentylphosphine; Lithium (2,6-diphenoxymethylbenzoyl) cyclopentylphosphine; Lithium (2,3,6-trimethylbenzoyl) cyclopentylphosphine; Lithium (2,3,4,6-tetramethylbenzoyl) cyclopentylphosphine; Lithium (2-phenyl-6-methylbenzoyl) cyclopentylphosphine; Lithium (2,4,6-trimethoxybenzoyl) cyclopentylphosphine; Lithium (2,4-dimethoxybenzoyl) cyclopentylphosphine; Lithium (2,3, -6-trimethoxybenzoyl) cyclopentylphosphine; Lithium (2,6-diethoxybenzoyl) cyclopentylphosphine; Lithium (2,6-dimethoxy-3,5-dimethylbenzoyl) cyclopentylphosphine; Lithium (2,6-dimethoxy-4-methylbenzoyl) cyclopentylphosphine; Lithium (2,6-dimethoxy-3-bromobenzoyl) cyclopentylphosphine; Lithium (2,6-dimethoxy-3-chlorobenzoyl) cyclopentylphosphine; Lithium (2,6-dimethoxy-3-chloro-5-bromobenzoyl) cyclopentylphosphine; Lithium (2,6-dimethoxy-3,5-dichlorobenzoyl) cyclopentylphosphine; Lithium (2,3,6-trimethoxy-5-bromobenzoyl) cyclopentylphosphine; Lithium (2,6-dichlorobenzoyl) -cyclopentylphosphine; Lithium (2,4,6-trichlorobenzoyl) cyclopentylphosphine; Lithium (2,3,6-trichlorobenzoyl) cyclopentylphosphine; Lithium (2,3,5,6-tetrachlorobenzoyl) cyclopentylphosphine; Lithium (2,3,4,5,6-pentachlorobenzoyl) cyclopentylphosphine; Lithium (2,6-dichloro-3-methylbenzoyl) cyclopentylphosphine; Lithium (2-chloro-6-methylbenzoyl) cyclopentylphosphine; Lithium (2-methoxy-3,6-dichlorobenzoyl) cyclopentylphosphine; Lithium (2-methoxy 6-chlorobenzoyl) cyclopentylphosphine; Lithium (2,6-bis (trifluoromethyl) -benzoyl) cyclopentylphosphine; Lithium (2-chloro-6-methylthiobenzoyl) cyclopentylphosphine; Lithium (2,6-dibromobenzoyl) cyclopentylphosphine; Lithium (2,6-dimethylbenzoyl) cyclohexylphosphine; Lithium (2,6-diethylbenzoyl) cyclohexylphosphine; Lithium (2,4,6-trimethylbenzoyl) cyclohexylphosphine; Lithium (2,3,4,5,6-pentamethylbenzoyl) cyclohexylphosphine; Lithium (2,3,5,6 tetramethylbenzoyl) cyclohexylphosphine; Lithium (2,4,6-triisopropylbenzoyl) cyclohexylphosphine; lithium (2,4,5,6 tetramethylbenzoyl) cyclohexylphosphine; Lithium (2,4,6-tri-tert-butylbenzoyl) cyclohexylphosphine; Lithium (2,6-dimethyl-4-tert-butylbenzoyl) cyclohexylphosphine; Lithium (2,6-diphenoxymethylbenzoyl) cyclohexylphosphine; Lithium (2,3,6-trimethylbenzoyl) cyclohexylphosphine; Lithium (2,3,4,6-tetramethylbenzoyl) cyclohexylphosphine; Lithium (2-phenyl-6-methylbenzoyl) cyclohexylphosphine; Lithium (2,4,6-trimethoxybenzoyl) cyclohexylphosphine; Lithium (2,4-dimethoxybenzoyl) cyclohexylphosphine; Lithium (2,3,6-trimethoxybenzoyl) cyclohexylphosphine; Lithium (2,6-diethoxybenzoyl) cyclohexylphosphine; Lithium (2,6-dimethoxy-3,5-dimethylbenzoyl) cyclohexylphosphine; Lithium (2,6-dimethoxy-4-methylbenzoyl) cyclohexylphosphine; Lithium (2,6-dimethoxy-3-bromobenzoyl) cyclohexylphosphine; Lithium (2,6-dimethoxy-3-chlorobenzoyl) cyclohexylphosphine; Lithium (2,6-dimethoxy-3-chloro-5-bromobenzoyl) cyclohexylphosphine; Lithium (2,6-dimethoxy-3,5-dichlorobenzoyl) cyclohexylphosphine; Lithium (2,3,6-trimethoxy-5-bromobenzoyl) cyclohexylphosphine; Lithium (2,6-dichlorobenzoyl) cyclohexylphosphine; Lithium (2,4,6-trichlorobenzoyl) cyclohexylphosphine; Lithium (2,3,6-trichlorobenzoyl) cyclohexylphosphine; Lithium (2,3,5,6 tetrachlorobenzoyl) cyclohexylphosphine; Lithium (2,3,4,5,6-pentachlorobenzoyl) cyclohexylphosphine; Lithium (2,6 dichloro-3-methylbenzoyl) cyclohexylphosphine; Lithium (2-chloro-6-methylbenzoyl) cyclohexylphosphine; Lithium (2-methoxy-3,6-dichlorobenzoyl) cyclohexylphosphine; Lithium (2-methoxy-6-chlorobenzoyl) cyclohexylphosphine; Lithium (2,6-bis (trifluoromethyl) -benzoyl) cyclohexylphosphine; Lithium (2-chloro-6-methylthiobenzoyl) cyclohexylphosphine; Lithium (2,6-dibromobenzoyl) cyclohexylphosphine.

ES 2 194 584 A1

The compounds of the formula (I ') are obtained selectively, for example, by reacting acyl halides (IV) with dimethalated organylphosphines (V):

<img file="ES2194584A1_D0034.tif" />

Ar and R6 have the meanings described above. X is Cl or Er and Ml is Na, Li, or K.

The starting materials are advantageously reacted in a 1: 1 molar ratio. However, it is not problematic to use a slight excess of one of the two components, e.g. ex. up to 20%. In this case, the desired product is also formed, although there may be variations in the presence of the troublesome by-product.

The reaction is advantageously carried out in a solvent. Specifically, ethers that are liquid at room temperature and atmospheric pressure can be used as solvents. Examples are dimethyl ether, diethyl ether, methylpropyl ether, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, dioxane and tetrahydrofuran. The use of tetrahydrofuran is preferred.

The reaction temperature is advantageously between -60 and + 120 ° C, eg between -40 and 100 C, for example between -20 and + 80 ° C.

It is advisable to stir the reaction mixture.

It is advantageous to introduce the compound of the formula V initially and then drop-load the compound of the formula IV at the temperature indicated above. For this, the compound of formula IV can be added without solvent or diluted in the reaction solvent.

If desired, the course of the reaction can be monitored by standard methods, eg NMR, eg P-NMR.³¹, chromatography (thin layer, HPLC, GC), etc.

In the reactions described above, it is very important to work in an inert gas atmosphere, eg a protective gas such as argoon or nitrogen, in order to prevent the entry of oxygen from the atmosphere.

I know

In order to obtain compounds of the formula I in which M is hydrogenic, the reaction described above continued with a hydrolysis step:

<img file="ES2194584A1_D0035.tif" />

The procedure for carrying out said hydroolysis reactions is already known to the technician in the field, and is carried out under the usual conditions. The hydroolysis of metalated primary and secondary phosphines is described for example in Houben-Weyl XII / 1, pages 56-57.

Equally imaginable is the obtaining of compounds of the formula (I) by reaction between a compound of the formula (IV) and an alkylphosphine compound in the presence of an acid binding agent, for example a barium carbonate, calcium carbonate or potassium carbonate. , as described eg in Houben-Weyl XII / 1, pages 73-74 or in K. Issleib and R. Kummel, Z. Naturf. B (1967), 22, 784.

The compounds of formula I, where R is M, according to the invention are identified by P-NMR spectroscopy.³¹ and are stable in solution in an inert gas atmosphere and at room temperature for several

ES 2 194 584 A1 weeks.

The invention further provides a process for the selective obtaining of compounds of formula I, where R is M, by (1) reaction of an acyl halide of formula IV or

II

Ar — C — X (IV), where Ar has the meaning defined before and

XesCl oBr;

with a dimethalated organylphosphine from phaormula V

<img file="ES2194584A1_D0036.tif" />

in which R6 has the meaning defined before and

M1 is Na, LioK;

in a molar ratio of 1: 1; and (2) if applicable, subsequent hydroalysis if the compounds of formula I are to be obtained, in which M is hydrogen.

The acyl halides (IV) used as starting material are known substances, some are commercial products, or they can be obtained by methods similar to those used to obtain known compounds.

A method for obtaining metalated alkylphosphines consists for example in the reaction of suitable alkylphosphines with the alkali metal, corresponding alkali metal hydride or alkyl lithium compound:

<img file="ES2194584A1_D0037.tif" />

ES 2 194 584 A1 (M1 has the meanings defined above)

The reaction is conveniently carried out with the exclusion of air in an inert solvent and at a temperature of, for example, between -80 and + 120 ° C. 2 to 4 molar equivalents of the alkali metal, alkali metal hydride or alkyl lithium compound are advantageously used. They are idoine solvents

eg the ethers described above, or inert solvents, such as alkanes, cycloalkanes or aromatic solvents such as toluene, xylene or mesitylene.

The production of alkylphosphines R6-PH2 is generally known. In this way, compounds can be obtained, for example, by reaction of PH₃ with alkenes in the presence of a radical former or by reduction with alkylphosphine chlorides, eg with lithium aluminum hydride. These and other methods are described for example in "Organic Phospllorous Compounds", vol. 1-7, Wiley-Interscience 1972, coordinators RM Kosalapoff and L. Maier.

The compounds of formula I, where R is M, are especially suitable for obtaining mono- and bisacylphosphines, mono- and bisacylphosphine oxides and asymmetric mono- and bisacylphosphine sulphides. In this context, "asymmetric" means that in bisacylphosphines, oxides of bisacylphosphine and sulfides of bisacylphosphine there are two different acyl groups and that in monoacylphosphines, monoacylphosphine ioxides and monoacylphosphine sulfides there are two different residues attached to the atom of phosphorus.

Such "asymmetric" mono- and bisacylphosphines, mono- and bisacylphosphine ioxides and "asymmetric" mono- and bisacylphosphine sulfides are new, with a few exceptions.

OR

II

In compounds of formula I, where R is C — Y₁ x is preferably 1. In particular, A is oxygen and Ar is a group

<img file="ES2194584A1_D0038.tif" />

OR _z II

Of special importance are compounds of formula I where R is —C — Yj where Y₁ is C alkyl₁ -C₁₂, in particular C alkyl₁-C₁₂ branched; cycloalkyl C₃-C₁₈ unsubstituted or C3-C18 cycloalkyl substituted by C1-C20 alkyl, OR11, CF3 or halogen; or it is

<img file="ES2194584A1_D0039.tif" />

As C1-C12 alkyl, Y1 is preferably branched at the α position with respect to the bond with the CO group. The carbon atom in position α with respect to the CO group is preferably a tertiary carbon atom.

The preferred meanings of R1 ', R2', R3 ', R4' and R5 'are similar to the meanings ascribed above to R1, R2, R3, R4 and R5.

OR

II

Also of interest are compounds of formula I where R is —C - Y, where R₁, R₂and R₃, are C alkyl₁ -C₄, in particular methyl; R₁'and R₂'are C alkoxy₁-C₄, in particular methoxy or chlorine;

ES 2 194 584 A1 and R4, R5, R3 ', R4' and R5 'are hydrogenic.

In the preferred compounds of formula I, where

OR

Res —C — Y

Aesoxigenoyxes1;

R1 and R2 are C1-C4 alkyl, C1-C4 alkoxy, CloCF3;

R3 is hydrogen, C1-C4 alkyl or C1-C4 alkoxy;

R4 and R5 are hydrogen;

R6 is C1-C12 alkyl, unsubstituted or substituted by cycloalkenyl, CN, C (O) R11, C (O) OR11, C (O) N (R14) 2, cycloalkyl; C2-C12 alkyl that was interrupted one or more times by non-consecutive O, S or NR14 groups and that is unsubstituted or substituted by OR11, SR11, N (R12) (R13), CN, C (O) R11, C ( O) OR11 and / or C (O) N (R₁₄)₂; alkenyl C₂-C₁₂ that it was uninterrupted or interrupted one or more times by non-consecutive O, S or NR14 groups and is unsubstituted or substituted by OR11, SR11, N (R12) (R13); benzyl, cyclopentyl, cyclohexyl, C4-C12 cycloalkyl that was uninterrupted or interrupted one or more times by O, S and / or NR14 groups; or C8-C12 arylcycloalkyl;

R11 is H, C1-C12 alkyl, cyclohexyl, cyclopentyl, phenyl, or benzyl;

R12 and R13 independently of each other are C1-C12 alkyl, cyclopentyl, cyclohexyl, phenyl, benzyl or C2-C12 alkyl that was interrupted one or more times by non-consecutive O atoms and that was unsubstituted or substituted by OH and / or SH ; either R12 and R13 together form a piperidino, morpholino, or piperazino;

R14 is hydrogen or C1-C12 alkyl; and

Y1 is C1-C12 alkyl or

<img file="ES2194584A1_D0040.tif" />

R1 'and R2' have the same meanings as R1 and R2; and R3 ', R4' and R5 'independently of each other have the same meanings attributed to R3, R4 and R5.

or ιι

Examples of preferred compounds of formula I, where R is CY, are as follows:

(2,4,6-trimethylbenzoyl) - (2,6-dimethylbenzoyl) -ethylphosphine ooxide; (2,4,6-trimethylbenzoyl) (2,6-diethylbenzoyl) ethylphosphine oxide; (2,4,6-trimethylbenzoyl) - (2,6-dimethyl-4-tert-butylbenzoyl) ethylphosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,6-trimethoxybenzoyl) -ethylphosphine oxide; (2,4,6-trimethylbenzoyl) - (2,4-dimethoxybenzoyl) ethylphosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,6-diethoxybenzoyl) ethylphosphine oxide; (2,4,6-trimethylbenzoyl) - (2,6-dimethoxy-4-methylbenzoyl) ethylphosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,6-dichlorobenzoyl) ethylphosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,6-trichlorobenzoyl) ethylphosphine ooxide; (2,4,6-trimethylbenzoyl) -2,6-bis (trifluoromethyl) benzoylethylphosphine oxide; (2,6-Dimethoxybenzoyl) - (2,6-dimethylbenzoyl) -ethylphosphine oxide; (2,6-dimethoxybenzoyl) - (2,6-diethylbenzoyl) ethylphosphine ooxide; (2,6-dimethoxybenzoyl) - (2,4,6-trimethylbenzoyl) ethylphosphine ooxide; (2,6-dimethoxybenzoyl) - (2,6-dimethyl-4-tert-butylbenzoyl) ethylphosphine oxide; (2,6-dimethoxybenzoyl) (2,4,6-trimethoxybenzoyl) ethylphosphine ooxide; (2,6-Dimethoxybenzoyl) - (2,4-dimethoxybenzoyl) ethylphosphine ooxide, (2,6-dimethoxybenzoyl) - (2,6-diethoxybenzoyl) ethylphosphine ooxide, (2,6-dimethoxybenzoyl) ooxide 19

ES 2 194 584 A1

- (2,6-dimethoxy-4-methylbenzoyl) ethylphosphine; (2,6-dimethoxybenzoyl) - (2,6-dichlorobenzoyl) ethylphosphine ooxide; (2,6-dimethoxybenzoyl) - (2,4,6-trichloro-benzoyl) ethylphosphine oxide; (2,6-Dimethoxybenzoyl) -2,6-bis (trifluoromethyl) benzoylethylphosphine oxide; (2,6-dimethylbenzoyl) - (2,6-diethylbenzoyl) ethylphosphine ooxide; (2,6-Dimethylbenzoyl) - (2,4,6-trimethylbenzoyl) -ethylphosphine oxide; (2,6-dimethylbenzoyl) - (2,6-dimethyl 4-tert-butylbenzoyl) ethylphosphine ooxide; (2,6-dimethylbenzoyl) - (2,4,6-trimethoxybenzoyl) ethylphosphine ooxide; (2,6-dimethylbenzoyl) - (2,4-dimethoxybenzoyl) ethylphosphine oxide; (2,6-dimethylbenzoyl) - (2,6-diethoxybenzoyl) ethylphosphine ooxide; (2,6-dimethylbenzoyl) - (2,6-dimethoxy-4-methylbenzoyl) ethylphosphine oxide; (2,6-dimethylbenzoyl) - (2,6-dichlorobenzoyl) ethylphosphine ooxide; (2,6-dimethylbenzoyl) - (2,4,6-trichlorobenzoyl) ethylphosphine oxide; (2,6-dimethylbenzoyl) -2,6 bis (trifluoromethyl) benzoylethylphosphine ooxide; (2,4,6-trimethoxybenzoyl) - (2,6-dimethylbenzoyl) ethylphosphine ooxide; (2,4,6-trimethoxybenzoyl) - (2,6-diethylbenzoyl) ethylphosphine oxide; (2,4,6-trimethoxybenzoyl) (2,4,6-trimethylbenzoyl) ethylphosphine ooxide; (2,4,6-trimethoxybenzoyl) - (2,6-dimethyl-4-tertbutylbenzoyl) ethylphosphine ooxide; (2,4,6-trimethoxybenzoyl) - (2,4-dimethoxybenzoyl) ethylphosphine oxide; (2,4,6-trimethoxybenzoyl) - (2,6-diethoxybenzoyl) ethylphosphine oxide; (2,4,6-trimethoxybenzoyl) - (2,6-dichlorobenzoyl) ethylphosphine ooxide; (2,4,6-trimethoxybenzoyl) -2,6-bis (trifluoromethyl) benzoylethylphosphine oxide; (2,6-Dimethyl-4tert-butylbenzoyl) - (2,6-dimethylbenzoyl) ethylphosphine ooxide; (2,6-Dimethyl-4-tert-butylbenzoyl) - (2,6-diethylbenzoyl) ethylphosphine oxide; (2,6-Dimethyl-4-tert-butylbenzoyl) - (2,4,6-trimethylbenzoyl) ethylphosphine ooxide; (2,6-dimethyl-4-tert-butylbenzoyl) - (2,6-dimethyl-4-tert-butylbenzoyl) ethylphosphine oxide; (2,6-Dimethyl-4-tert-butylbenzoyl) - (2,4,6-trimethoxybenzoyl) ethylphosphine oxide; (2,6-Dimethyl-4-tert-butylbenzoyl) - (2,4-dimethoxybenzoyl) -ethylphosphine oxide; (2,6-Dimethyl-4-tert-butylbenzoyl) (2,6-diethoxybenzoyl) ethylphosphine oxide; (2,6-dimethyl-4-tert-butylbenzoyl) - (2,6-dimethoxy-4-methylbenzoyl) ethylphosphine oxide; (2,6-Dimethyl-4-tert-butylbenzoyl) (2,6-dichlorobenzoyl) ethylphosphine oxide; (2,6-Dimethyl-4-tert-butylbenzoyl) - (2,4,6-trichlorobenzoyl) ethylphosphine oxide; (2,6-Dimethyl-4-tert-butylbenzoyl) -2,6-bis (trifluoromethyl) benzoylethylphosphine oxide; (2,4,6-trimethylbenzoyl) - (2,6-dimethylbenzoyl) -n-butylphosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,6-diethylbenzoyl) -n-butylphosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,6-dimethyl-4-tert-butylbenzoyl) -n-butylphosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,6-trimethoxybenzoyl) -n-butylphosphine oxide; (2,4,6-trimethylbenzoyl) - (2,4-dimethoxybenzoyl) -n-butylphosphine oxide; (2,4,6-trimethylbenzoyl) - (2,6-diethoxybenzoyl) -n-butylphosphine oxide; (2,4,6-trimethylbenzoyl) - (2,6-dimethoxy-4-methylbenzoyl) -n-butylphosphine oxide, (2,4,6-trimethylbenzoyl) - (2,6-dichlorobenzoyl) -n - oxide butylphosphine; (2,4,6-trimethylbenzoyl) - (2,4,6-trphichlorobenzoyl) -n-butylphosphine oxide; (2,4,6-trimethylbenzoyl) -2,6-bis (trifluoromethyl) benzoyl-n-butylphosphine ooxide; (2,6-dimethoxybenzoyl) - (2,6-dimethylbenzoyl) -n-butylphosphine ooxide; (2,6-dimethoxybenzoyl) - (2,6-diethylbenzoyl) -n-butylphosphine ooxide; (2,6-dimethoxybenzoyl) - (2,4,6-trimethylbenzoyl) -n-butylphosphine ooxide; (2,6-dimethoxybenzoyl) - (2,6 dimethyl-4-tert-butylbenzoyl) -n-butylphosphine ooxide; (2,6-dimethoxybenzoyl) (2,4,6-trimethoxybenzoyl) -n-butylphosphine ooxide; (2,6-dimethoxybenzoyl) - (2,4-dimethoxybenzoyl) -n-butylphosphine ooxide; (2,6-dimethoxybenzoyl) - (2,6-diethoxybenzoyl) -n-butylphosphine oxide; (2,6-dimethoxybenzoyl) (2,6-dimethoxy-4-methylbenzoyl) -n-butylphosphine oxide; (2,6-dimethoxybenzoyl) - (2,6-dichlorobenzoyl) n-butylphosphine oxide; (2,6-dimethoxybenzoyl) - (2,4,6-trichlorobenzoyl) -n-butylphosphine oxide; (2,6-Dimethoxybenzoyl) -2,6-bis (trifluoromethyl) benzoyl-n-butylphosphine ooxide; (2,6-Dimethylbenzoyl) (2,6-diethylbenzoyl) -n-butylphosphine ooxide; (2,6-dimethylbenzoyl) - (2,4,6-trimethylbenzoyl) -n-butylphosphine oxide; (2,6-dimethylbenzoyl) - (2,6-dimethyl-4-tert-butylbenzoyl) -n-butylphosphine ooxide; (2,6-dimethylbenzoyl) - (2,4,6-trimethoxybenzoyl) -n-butylphosphine ooxide; (2,6-dimethylbenzoyl) - (2,4-dimethoxybenzoyl) -n-butylphosphine ooxide; (2,6-dimethylbenzoyl) - (2,6-diethoxybenzoyl) -n-butylphosphine ooxide; (2,6-Dimethylbenzoyl) - (2,6-dimethoxy-4-methylbenzoyl) -n-butylphosphine ooxide; (2,6-dimethylbenzoyl) - (2,6-dichlorobenzoyl) -n-butylphosphine ooxide; (2,6-dimethylbenzoyl) - (2,4,6-trichlorobenzoyl) -n-butylphosphine ooxide; (2,6-Dimethylbenzoyl) -2,6-bis (trifluoromethyl) benzoyl-n-butylphosphine oxide; (2,4,6-trimethoxybenzoyl) - (2,6-dimethylbenzoyl) -n-butylphosphine oxide; (2,4,6-trimethoxybenzoyl) - (2,6-diethylbenzoyl) -n-butylphosphine oxide; (2,4,6-trimethoxybenzoyl) (2,4,6-trimethylbenzoyl) -n butylphosphine ooxide; (2,4,6-trimethoxybenzoyl) - (2,6-dimethyl-4-tert-butylbenzoyl) -n-butylphosphine ooxide; (2,4,6-trimethoxybenzoyl) - (2,4-dimethoxybenzoyl) -n-butylphosphine oxide; (2,4,6-trimethoxybenzoyl) - (2,6-diethoxybenzoyl) -n-butylphosphine ooxide; (2,4,6-trimethoxybenzoyl) - (2,6-dichlorobenzoyl) -n-butylphosphine ooxide; (2,4,6-trimethoxybenzoyl) -2,6-bis (trifluoromethyl) benzoyl-n-butylphosphine oxide; (2,6-Dimethyl-4-tert-butylbenzoyl) - (2,6-dimethylbenzoyl) -n-butylphosphine ooxide; (2,6-Dimethyl-4-tert-butylbenzoyl) - (2,6-diethylbenzoyl) -n-butylphosphine ooxide; (2,6-Dimethyl-4-tert-butylbenzoyl) - (2,4,6-trimethylbenzoyl) -n-butylphosphine oxide; (2,6-Dimethyl-4-tert-butylbenzoyl) - (2,6-dimethyl-4-tert-butylbenzoyl) -n-butylphosphine ooxide; (2,6-Dimethyl-4-tert-butylbenzoyl) - (2,4,6-trimethoxybenzoyl) -n-butylphosphine ooxide; (2,6-Dimethyl-4-tert-butylbenzoyl) - (2,4-dimethoxybenzoyl) -n-butylphosphine ooxide; (2,6-Dimethyl-4-tert-butylbenzoyl) - (2,6-diethoxybenzoyl) -n-butylphosphine oxide; (2,6-Dimethyl-4-tert-butylbenzoyl) - (2,6-dimethoxy-4-methylbenzoyl) n-butylphosphine oxide; (2,6-Dimethyl-4-tert-butylbenzoyl) - (2,6-dichlorobenzoyl) -n-butylphosphine oxide; (2,6-Dimethyl-4-tert-butylbenzoyl) - (2,4,6-trichlorobenzoyl) -n-butylphosphine ooxide; oxide

ES 2 194 584 A1 (2,6-dimethyl-4-tert-butylbenzoyl) - (2,6-bis - (trofluoromethyl) benzoyl) -n-butylphosphine; (2,4,6-trimethylbenzoyl) - (2,6-dimethylbenzoyl) isobutylphosphine oxide; (2,4,6-trimethylbenzoyl) (2,6-diethylbenzoyl) isobutylphosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,6-dimethyl-4-tert-butolbenzoyl) isobutylphosphine oxide; (2,4,6-trimethylbenzoyl) - (2,4,6-trimethoxybenzoyl) isobutylphosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4-dimethoxybenzoyl) isobutylphosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,6-dichlorobenzoyl) isobutylphosphine ooxide; (2,4,6-Trimethylbenzoyl) - (2,6-dimethoxy-4-methylbenzoyl) -isobutylphosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,6-dichlorobenzoyl) isobutylphosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,6-trichlorobenzoyl) isobutylphosphine ooxide; (2,4,6-Trimethylbenzoyl) -2,6-bis (trifluoromethyl) -benzoylisobutylphosphine ooxide; (2,6-dimethoxybenzoyl) (2,6-dimethylbenzoyl) isobutylphosphine ooxide; (2,6-dimethoxybenzoyl) - (2,6-diethylbenzoyl) isobutylphosphine ooxide; (2,6-dimethoxybenzoyl) - (2,4,6-trimethylbenzoyl) isobutylphosphine oxide; (2,6-dimethoxybenzoyl) (2,6-dimethyl-4-tert-butylbenzoyl) isobutylphosphine ooxide; (2,6-dimethoxybenzoyl) - (2,4,6-trimethoxybenzoyl) isobutylphosphine ooxide; (2,6-dimethoxybenzoyl) - (2,4-dimethoxybenzoyl) isobutylphosphine oxide; (2,6-dimethoxybenzoyl) - (2,6-diethoxybenzoyl) isobutylphosphine ooxide, (2,6-dimethoxybenzoyl) (2,6-dimethoxy-4-methylbenzoyl) isobutylphosphine ooxide; (2,6-dimethoxybenzoyl) - (2,6-dichlorobenzoyl) isobutylphosphine ooxide; (2,6-dimethoxybenzoyl) - (2,4,6-trichlorobenzoyl) isobutylphosphine oxide; (2,6-dimethoxybenzoyl) - (2,6-bis (trifluoromethyl) benzoyl) isobutylphosphine ooxide; (2,6-Dimethylbenzoyl) (2,6-diethylbenzoyl) isobutylphosphine ooxide; (2,6-dimethylbenzoyl) - (2,4,6-trimethylbenzoyl) isobutylphosphine ooxide; (2,6-dimethylbenzoyl) - (2,6-dimethyl-4-tert-butylbenzoyl) isobutylphosphine oxide; (2,6-dimethylbenzoyl) - (2,4,6-trimethoxybenzoyl) -isobutylphosphine ooxide; (2,6-dimethylbenzoyl) - (2,4-dimethoxybenzoyl) isobutylphosphine ooxide; (2,6-dimethylbenzoyl) - (2,6-dichlorobenzoyl) isobutylphosphine ooxide; (2,6-dimethylbenzoyl) - (2,6-dimethoxy-4-methylbenzoyl) isobutylphosphine oxide; (2,6-dimethylbenzoyl) (2,6-dichlorobenzoyl) isobutylphosphine oxide; (2,6-dimethylbenzoyl) - (2,4,6-trichlorobenzoyl) isobutylphosphine ooxide; (2,6-Dimethylbenzoyl) -2,6-bis (trifluoromethyl) benzoylisobutylphosphine ooxide; (2,4,6-trimethoxybenzoyl) - (2,6-dimethylbenzoyl) isobutylphosphine ooxide; (2,4,6-trimethoxybenzoyl) - (2,6-diethylbenzoyl) isobutylphosphine ooxide; (2, -4,6-trimethoxybenzoyl) - (2,4,6-trimethylbenzoyl) isobutylphosphine oxide; (2,4,6-trimethoxybenzoyl) - (2,6-dimethyl-4-tert-butylbenzoyl) isobutylphosphine oxide; (2,4,6-trimethoxybenzoyl) - (2,4-dimethoxybenzoyl) isobutylphosphine ooxide; (2,4,6-Trimethoxybenzoyl) - (2,6-diethoxybenzoyl) -isobutylphosphine oxide; (2,4,6-trimethoxybenzoyl) - (2,6-dichlorobenzoyl) isobutylphosphine ooxide; (2,4,6-trimethoxybenzoyl) -2,6-bis (trifluoromethyl) benzoylisobutylphosphine ooxide; (2,6-Dimethyl-4-tert-butylbenzoyl) - (2,6-dimethylbenzoyl) isobutylphosphine ooxide; (2,6-Dimethyl-4-tert; -butylbenzoyl) - (2,6-diethylbenzoyl) isobutylphosphine ooxide; (2,6-Dimethyl-4-tert-butylbenzoyl) - (2,4,6-trimethylbenzoyl) isobutylphosphine ooxide; (2,6-Dimethyl-4-tert-butylbenzoyl) - (2,6-dimethyl-4-tertutylbenzoyl) isobutylphosphine ooxide; (2,6-Dimethyl-4-tert-butylbenzoyl) - (2,4,6-trimethoxybenzoyl) isobutylphosphine oxide; (2,6-dimethyl-4-tert-butylbenzoyl) - (2,4-dimethoxybenzoyl) isobutylphosphine ooxide; (2,6-Dimethyl 4-tert-butylbenzoyl) - (2,6-diethoxybenzoyl) isobutylphosphine ooxide; (2,6-Dimethyl-4-tert-butylbenzoyl) - (2,6-dimethoxy-4-methylbenzoyl) isobutylphosphine ooxide; (2,6-Dimethyl-4-tertbutylbenzoyl) - (2,6 dichlorobenzoyl) isobutylphosphine ooxide; (2,6-Dimethyl-4-tert-butylbenzoyl) - (2,4,6-trichlorobenzoyl) isobutylphosphine oxide; (2,6-Dimethyl-4-tert-butylbenzoyl) -2,6-bis (trifluoromethyl) benzoyl isobutylphosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,6-dimethylbenzoyl) - (1-methylpropyl) phosphine oxide; (2,4,6-trimethylbenzoyl) - (2,6-diethylbenzoyl) - (1-methylpropyl) phosphine ooxide; (2,4,6-trimethylbenzoyl) (2,6-dimethyl-4-tert-butylbenzoyl) - (1-methylpropyl) phosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,6-trimethoxybenzoyl) - (1-methylpropyl) -phosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4-dimethoxybenzoyl) (1-methylpropyl) phosphine oxide; (2,4,6-trimethylbenzoyl) - (2,6-diethoxybenzoyl) - (1-methylpropyl) phosphine oxide; (2,4,6-trimethylbenzoyl) - (2,6-dimethoxy-4-methylbenzoyl) - (1-methylpropyl) phosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,6-dichlorobenzoyl) - (1-methylpropyl) phosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,6-trichlorobenzoyl) - (1-methylpropyl) phosphine ooxide; (2,4,6-trimethylbenzoyl) -2,6 bis (trifluoromethyl) benzoyl - (1-methylpropyl) phosphine ooxide; (2,6-dimethoxybenzoyl) - (2,6-dimethylbenzoyl) - (1-methylpropyl) phosphine ooxide; (2,6-dimethoxybenzoyl) - (2,6-diethylbenzoyl) - (1-methylpropyl) phosphine ooxide; (2,6-dimethoxybenzoyl) - (2,4,6-trimethylbenzoyl) - (1-methylpropyl) phosphine ooxide; (2,6-dimethoxybenzoyl) - (2,6-dimethyl-4-tert-butylbenzoyl) - (1-methylpropyl) phosphine ooxide; (2,6-dimethoxybenzoyl) - (2,4,6-trimethoxybenzoyl) - (1-methylpropyl) phosphine ooxide; (2,6-dimethoxybenzoyl) - (2,4-dimethoxybenzoyl) - (1-methylpropyl) phosphine oxide; (2,6-dimethoxybenzoyl) - (2,6-diethoxybenzoyl) - (1-methylpropyl) phosphine ooxide; (2,6-dimethoxybenzoyl) - (2,6-dimethoxy-4-methylbenzoyl) (1-methylpropyl) phosphine ooxide; (2,6-dimethoxybenzoyl) - (2,6-dichlorobenzoyl) - (1-methylpropyl) phosphine oxide; (2,6-dimethoxybenzoyl) - (2,4,6-trichlorobenzoyl) - (1-methylpropyl) phosphine oxide ; (2,6-Dimethoxybenzoyl) -2,6-bis (trifluoromethyl) benzoyl - (1-methylpropyl) phosphine oxide; (2,6-dimethylbenzoyl) (2,6-diethylbenzoyl) - (1-methylpropyl) phosphine ooxide; (2,6-dimethylbenzoyl) - (2,4,6-trimethylbenzoyl) (1-methylpropyl) -phosphine ooxide; (2,6-Dimethylbenzoyl) - (2,6-dimethyl-4tert-butylbenzoyl) - (1-methylpropyl) phosphine oxide; (2,6-dimethylbenzoyl) - (2,4,6-trimethoxybenzoyl) - (1-methylpropyl) phosphine oxide; (2,6-dimethylbenzoyl) - (2,4-dimethoxybenzoyl) - (1-methylpropyl) phosphine ooxide; (2,6-dimethyl21 ooxide

ES 2 194 584 A1 benzoyl) - (2,6-diethoxybenzoyl) - (1-methylpropyl) phosphine; (2,6-Dimethylbenzoyl) - (2,6-dimethoxy-4-methylbenzoyl) - (1-methylpropyl) phosphine ooxide; (2,6-dimethylbenzoyl) - (2,6-dichlorobenzoyl) - (1-methylpropyl) phosphine oxide; (2,6-dimethylbenzoyl) - (2,4,6-trichlorobenzoyl) - (1-methylpropyl) phosphine oxide; (2,6-Dimethylbenzoyl) -2,6-bis (trifluoromethyl) benzoyl - (1-methylpropyl) phosphine oxide; (2,4,6-trimethoxybenzoyl) - (2,6-dimethylbenzoyl) - (1-methylpropyl) phosphine ooxide; (2,4,6-trimethoxybenzoyl) - (2,6-diethylbenzoyl) - (1-methylpropyl) phosphine ooxide; (2,4,6-trimethoxybenzoyl) (2,4,6-trimethylbenzoyl) - (1-methylpropyl) phosphine ooxide; (2,4,6-trimethoxybenzoyl) - (2,6-dimethyl 4-tert-butylbenzoyl) - (1-methylpropyl) phosphine ooxide; (2,4,6-trimethoxybenzoyl) - (2,4-dimethoxybenzoyl) - (1-methylpropyl) phosphine oxide; (2,4,6-trimethoxybenzoyl) - (2,6-diethoxybenzoyl) - (1 methylpropyl) phosphine ooxide; (2,4,6-trimethoxybenzoyl) - (2,6-dichlorobenzoyl) - (1-methylpropyl) phosphine oxide; (2,4,6-trimethoxybenzoyl) 2,6-bis (trifluoromethyl) benzoyl - (1-methylpropyl) -phosphine ooxide; (2,6-Dimethyl-4-tert-butylbenzoyl) - (2,6-dimethylbenzoyl) - (1-methylpropyl) phosphine ooxide; (2,6-dimethyl-4-tert-butylbenzoyl) - (2,6-diethylbenzoyl) - (1-methylpropyl) phosphine ooxide; (2,6-Dimethyl-4-tert-butylbenzoyl) - (2,4,6-trimethylbenzoyl) - (1-methylpropyl) phosphine ooxide; (2,6-Dimethyl-4-tert-butylbenzoyl) - (2,6-dimethyl-4-tert-butylbenzoyl) - (1-methylpropyl) phosphine ooxide; (2,6-dimethyl-4-tert-butylbenzoyl) - (2,4,6-trimethoxybenzoyl) - (1-methylpropyl) phosphine ooxide; (2,6-Dimethyl-4-tert-butylbenzoyl) - (2,4-dimethoxybenzoyl) - (1-methylpropyl) phosphine ooxide; (2,6-Dimethyl-4-tert-butylbenzoyl) - (2,6-diethoxybenzoyl) - (1-methylpropyl) phosphine ooxide; (2,6-dimethyl-4-tert-butylbenzoyl) - (2,6-dimethoxy-4-methylbenzoyl) - (1-methylpentyl) phosphine ooxide; (2,6-Dimethyl-4-tert-butylbenzoyl) - (2,6-dichlorobenzoyl) - (1-methylpropyl) phosphine ooxide; (2,6-Dimethyl-4-tert-butylbenzoyl) - (2,4,6-trichlorobenzoyl) - (1-methylpentyl) phosphine ooxide; (2,6-dimethyl-4-tert-butylbenzoyl) -2,6-bis (trifluoromethyl) benzoyl - (1-methylpentyl) phosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,6-dimethylbenzoyl) - (2,4,4-trimethylpentyl) phosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,6-diethylbenzoyl) - (2,4,4-trimethylpentyl) phosphine ooxide; (2,4,6-trimethylbenzoyl) (2,6-dimethyl-4-tert-butylbenzoyl) - (2,4,4-trimethylpentyl) phosphine ooxide; (2,4,6-trimethylbenzoyl) (2,4,6-trimethoxybenzoyl) - (2,4,4-trimethylpentyl) phosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4-dimethoxybenzoyl) - (2,4,4-trimethylpentyl) phosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,6-diethoxybenzoyl) (2,4,4-trimethylpentyl) phosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,6-dimethoxy-4-methylbenzoyl) (2,4,4-trimethylpentyl) phosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,6-dichlorobenzoyl) - (2,4,4-trimethylpentyl) phosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,6-trichlorobenzoyl) - (2,4,4-trimethylpentyl) phosphine oxide; (2,4,6-trimethylbenzoyl) -2,6-bis (trifluoromethyl) benzoyl - (2,4,4-trimethylpentyl) phosphine ooxide; (2,6-dimethoxybenzoyl) - (2,6-dimethylbenzoyl) - (2,4,4-trimethylpentyl) phosphine ooxide; (2,6-dimethoxybenzoyl) - (2,6-diethylbenzoyl) - (2,4,4-trimethylpentyl) phosphine oxide; (2,6-dimethoxybenzoyl) - (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) phosphine ooxide; (2,6-dimethoxybenzoyl) - (2,6-dimethyl 4-tert-butylbenzoyl) - (2,4,4-trimethylpentyl) phosphine ooxide; (2,6-dimethoxybenzoyl) - (2,4,6-trimethoxybenzoyl) - (2,4,4-trimethylpentyl) phosphine ooxide; (2,6-dimethoxybenzoyl) - (2,4-dimethoxybenzoyl) (2,4,4-trimethylpentyl) phosphine ooxide; (2,6-dimethoxybenzoyl) - (2,6-diethoxybenzoyl) - (2,4,4-trimethylpentyl) phosphine ooxide; (2,6-dimethoxybenzoyl) - (2,6-dimethoxy-4-methylbenzoyl) - (2,4,4-trimethylpentyl) phosphine oxide; (2,6-dimethoxybenzoyl) - (2,6-dichlorobenzoyl) - (2,4,4-trimethylpentyl) phosphine oxide; (2,6-dimethoxybenzoyl) - (2,4,6-trichlorobenzoyl) - (2,4,4-trimethylpentyl) -phosphine ooxide; (2,6-dimethoxybenzoyl) -2,6-bis (trifluoromethyl) benzoyl - (2,4,4-trimethylpentyl) phosphine oxide; (2,6-dimethylbenzoyl) - (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylbenzoyl) phosphine ooxide; (2,6-Dimethylbenzoyl) (2,6-dimethyl-4-tert-butylbenzoyl) - (2,4,4-trimethylpentyl) phosphine oxide; (2,6-dimethylbenzoyl) (2,4,6-trimethoxybenzoyl) - (2,4,4-trimethylpentyl) phosphine ooxide; (2,6-dimethylbenzoyl) - (2,4-dimethoxybenzoyl) - (2,4,4-trimethylpentyl) phosphine ooxide; (2,6-dimethylbenzoyl) - (2,6-diethoxybenzoyl) - (2,4,4-trimethylpentyl) phosphine ooxide; (2,6-dimethylbenzoyl) - (2,6-dimethoxy-4-methylbenzoyl) - (2,4,4-trimethylpentyl) phosphine oxide; (2,6-dimethylbenzoyl) - (2,6-dichlorobenzoyl) - (2,4,4-trimethylpentyl) phosphine ooxide; (2,6-dimethylbenzoyl) - (2,4,6-trichlorobenzoyl) - (2,4,4-trimethylpentyl) phosphine oxide; (2,6-dimethylbenzoyl) -2,6-bis (trifluoromethyl) benzoyl - (2,4,4-trimethylpentyl) phosphine ooxide; (2,4,6-trimethoxybenzoyl) - (2,6-dimethylbenzoyl) - (2,4,4-trimethylpentyl) phosphine ooxide; (2,4,6-trimethoxybenzoyl) (2,6-diethylbenzoyl) - (2,4,4-trimethylpentyl) phosphine ooxide; (2,4,6-trimethoxybenzoyl) - (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) phosphine ooxide; (2,4,6-trimethoxybenzoyl) - (2,6-dimethyl-4-tert-butylbenzoyl) - (2,4,4-trimethylpentyl) phosphine ooxide; (2,4,6-trimethoxybenzoyl) - (2,4-dimethoxybenzoyl) (2,4,4-trimethylpentyl) phosphine ooxide; (2,4,6-trimethoxybenzoyl) - (2,6-diethoxybenzoyl) - (2,4,4-trimethylpentyl) phosphine ooxide; (2,4,6-trimethoxybenzoyl) - (2,6-dichlorobenzoyl) - (2,4,4-trimethylpentyl) phosphine oxide; (2,4,6-trimethoxybenzoyl) -2,6-bis (trifluoromethyl) benzoyl - (2,4,4-trimethylpentyl) phosphine oxide; (2,6-dimethyl-4-tert-butylbenzoyl) - (2,6-dimethylbenzoyl) - (2,4,4-trimethylpentyl) phosphine ooxide; (2,6-Dimethyl-4-tert-butylbenzoyl) - (2,6-diethylbenzoyl) - (2,4,4-trimethylpentyl) phosphine ooxide, (2,6-dimethyl-4-tert-butylbenzoyl) ooxide - (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) phosphine; (2,6-dimethyl-4-tert-butylbenzoyl) - (2,6-dimethyl-4-tert-butylbenzoyl) - (2,4,4-trimethylpentyl) phosphine ooxide; (2,6-dimethyl-4-tert-butylbenzoyl) - (2,4,6-trimethoxybenzoyl) - (2,4,4-trimethylpentyl) phosphine ooxide;

ES 2 194 584 A1 (2,6-dimethyl-4-tert-butylbenzoyl) - (2,4-dimethoxybenzoyl) (2,4,4-trimethylpentyl) phosphine oxide; (2,6-dimethyl-4-tert-butylbenzoyl) - (2,6-diethoxybenzoyl) - (2,4,4-trimethylpentyl) phosphine ooxide; (2,6-Dimethyl-4-tert-butylbenzoyl) - (2,6-dimethoxy-4-methylbenzoyl) - (2,4,4-trimethylpentyl) phosphine ooxide, (2,6-dimethyl-4 - tert-butylbenzoyl) - (2,6-dichlorobenzoyl) - (2,4,4-trimethylpentyl) phosphine; (2,6-dimethyl-4-tert-butylbenzoyl) - (2,4,6-trichlorobenzoyl) - (2,4,4-trimethylpentyl) phosphine oxide; (2,6-Dimethyl-4-tert-butylbenzoyl) -2,6-bis (trifluoromethyl) benzoyl - (2,4,4-trimethylpentyl) phosphine oxide; (2,4,6-trimethylbenzoyl) - (2,6-dimethylbenzoyl) cyclopentylphosphine oxide; (2,4,6-trimethylbenzoyl) - (2,6-diethylbenzoyl) cyclopentylphosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,6-dimethyl-4-tert-butylbenzoyl) cyclopentylphosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,6-rimethoxybenzoyl) cyclopentylphosphine oxide; (2,4,6-trimethylbenzoyl) - (2,4-dimethoxybenzoyl) cyclopentylphosphine oxide; (2,4,6-trimethylbenzoyl) - (2,6-diethoxybenzoyl) cyclopentylphosphine oxide; (2,4,6-trimethylbenzoyl) (2,6-dimethoxy-4-methylbenzoyl) cyclopentylphosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,6-dichlorobenzoyl) cyclopentylphosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,6-trichlorobenzoyl) cyclopentylphosphine oxide; (2,4,6-trimethylbenzoyl) -2,6-bis (trifluoromethyl) benzoylcyclopentylphosphine oxide; (2,6-dimethoxybenzoyl) - (2,6-dimethylbenzoyl) cyclopentylphosphine ooxide; (2,6-dimethoxybenzoyl) - (2,6-diethylbenzoyl) cyclopentylphosphine oxide; (2,6-dimethoxybenzoyl) - (2,4,6-trimethylbenzoyl) cyclopentylphosphine oxide; (2,6-dimethoxybenzoyl) - (2,6-dimethyl-4-tert-butylbenzoyl) cyclopentylphosphine oxide; (2,6-dimethoxybenzoyl) - (2,4,6-trimethoxybenzoyl) cyclopentylphosphine ooxide; (2,6-dimethoxybenzoyl) - (2,4-dimethoxybenzoyl) cyclopentylphosphine oxide; (2,6-dimethoxybenzoyl) - (2,6-diethoxybenzoyl) cyclopentylphosphine oxide; (2,6-dimethoxybenzoyl) - (2,6-dimethoxy-4-methylbenzoyl) cyclopentylphosphine ooxide; (2,6-dimethoxybenzoyl) - (2,6-dichlorobenzoyl) cyclopentylphosphine ooxide; (2,6-dimethoxybenzoyl) - (2,4,6-trichlorobenzoyl) cyclopentylphosphine oxide; (2,6-dimethoxybenzoyl) -2,6-bis (trifluoromethyl) benzoylcyclopentylphosphine oxide; (2,6-dimethylbenzoyl) - (2,6-diethylbenzoyl) cyclopentylphosphine ooxide; (2,6-dimethylbenzoyl) - (2,4,6-trimethylbenzoyl) cyclopentylphosphine oxide; (2,6-dimethylbenzoyl) - (2,6-dimethyl 4-tert-butylbenzoyl) cyclopentylphosphine oxide; (2,6-dimethylbenzoyl) - (2,4, -6-trimethoxybenzoyl) cyclopentylphosphine oxide; (2,6-dimethylbenzoyl) - (2,4-dimethoxybenzoyl) cyclopentylphosphine oxide; (2,6-dimethylbenzoyl) - (2,6-diethoxybenzoyl) cyclopentylphosphine oxide; (2,6-dimethylbenzoyl) (2,6-dimethoxy-4-methylbenzoyl) cyclopentylphosphine ooxide; (2,6-dimethylbenzoyl) - (2,6-dichlorobenzoyl) cyclopentylphosphine oxide; (2,6-dimethylbenzoyl) - (2,4,6-trichlorobenzoyl) cyclopentylphosphine oxide; (2,6-Dimethylbenzoyl) -2,6-bis (trifluoromethyl) benzoylcyclopentylphosphine ooxide; (2,4,6-trimethoxybenzoyl) - (2,6-dimethylbenzoyl) cyclopentylphosphine ooxide; (2,4,6-trimethoxybenzoyl) - (2,6-diethylbenzoyl) cyclopentylphosphine oxide; (2,4,6-trimethoxybenzoyl) - (2,4,6-trimethylbenzoyl) cyclopentylphosphine oxide; (2,4,6-trimethoxybenzoyl) - (2,6-dimethyl-4-tertbutylbenzoyl) cyclopentylphosphine oxide; (2,4,6-trimethoxybenzoyl) - (2,4-dimethoxybenzoyl) cyclopentylphosphine oxide; (2,4,6-trimethoxybenzoyl) - (2,6-diethoxybenzzyl) cyclopentylphosphine oxide; (2,4,6-trimethoxybenzoyl) - (2,6-dichlorobenzoyl) cyclopentylphosphine oxide; (2,4,6-trimethoxybenzoyl) -2,6-bis (trifluoromethyl) benzoylcyclopentylphosphine oxide; (2,6-dimethyl-4-tert-butylbenzoyl) - (2,6-dimethylbenzoyl) cyclopentylphosphine ooxide; (2,6-dimethyl-4-tert-butylbenzoyl) - (2,6-diethylbenzoyl) cyclopentylphosphine ooxide; (2,6-dimethyl-4-tertbutylbenzoyl) - (2,4,6-trimethylbenzoyl) cyclopentylphosphine ooxide; (2,6-dimethyl-4tert-butylbenzoyl) - (2,6-dimethyl-4-tert-butylbenzoyl) cyclopentylphosphine ooxide; (2,6-dimethyl-4-tert-butylbenzoyl) - (2,4,6-trimethoxybenzoyl) cyclopentylphosphine ooxide; (2,6-Dimethyl-4-tert-butylbenzoyl) - (2,4-dimethoxybenzoyl) cyclopentylphosphine ooxide; (2,6-dimethyl-4tert-butylbenzoyl) - (2,6-diethoxybenzoyl) cyclopentylphosphine ooxide; (2,6-Dimethyl-4-tert-butylbenzoyl) - (2,6-dimethoxy-4-methylbenzoyl) cyclopentylphosphine oxide; (2,6-dimethyl-4-tert-butylbenzoyl) - (2,6-dichlorobenzoyl) cyclopentylphosphine ooxide; (2,6-dimethyl-4-tert-butylbenzoyl) - (2,4,6-trichlorobenzoyl) cyclopentylphosphine ooxide; (2,6-Dimethyl-4-tert-butylbenzoyl) -2,6-bis (trifluoromethyl) benzoylcyclopentylphosphine oxide; (2,4,6-trimethylbenzoyl) - (2,6-dimethylbenzoyl) cyclohexylphosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,6-diethylbenzoyl) cyclohexylphosphine oxide; (2,4,6-triinethylbenzoyl) - (2,6-dimethyl-4-tert-butylbenzoyl) cyclohexylphosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,6-trimethoxybenzoyl) cyclohexylphosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4-dimethoxybenzoyl) cyclohexylphosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,6-diethoxybenzoyl) cyclohexylphosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,6-dimethoxy-4-methylbenzoyl) cyclohexylphosphine oxide; (2,4,6-trimethylbenzoyl) - (2,6-dichlorobenzoyl) cyclohexylphosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,6-trichlorobenzoyl) cyclohexylphosphine ooxide; (2,4,6-trimethylbenzoyl) -2,6-bis - (trifluoromethyl) benzoylcyclohexylphosphine oxide; (2,6-dimethoxybenzoyl) - (2,6-dimethylbenzoyl) cyclohexylphosphine ooxide; (2,6-dimethoxybenzoyl) - (2,6-diethylbenzoyl) cyclohexylphosphine oxide; (2,6-dimethoxybenzoyl) - (2,4,6-trimethylbenzoyl) cyclohexylphosphine ooxide; (2,6-dimethoxybenzoyl) - (2,6-dimethyl-4-tert-butylbenzoyl) cyclohexylphosphine oxide; (2,6-dimethoxybenzoyl) - (2,4,6-trimethoxybenzoyl) cyclohexylphosphine oxide; (2,6-dimethoxybenzoyl) - (2,4-dimethoxybenzoyl) cyclohexylphosphine oxide; (2,6-dimethoxybenzoyl) (2,6-diethoxybenzoyl) cyclohexylphosphine ooxide; (2,6-dimethoxybenzoyl) - (2,6-dimethoxy-4-methylbenzoyl) cyclohexylphosphine ooxide; (2,6-dimethoxybenzoyl) - (2,6-dichlorobenzoyl) cyclohexylphosphine oxide; oxide

ES 2 194 584 A1 (2,6-dimethoxybenzoyl) - (2,4,6-trichlorobenzoyl) cyclohexylphosphine; (2,6-dimethoxybenzoyl) 2,6-bis (trifluoromethyl) benzoylcyclohexylphosphine ooxide; (2,6-dimethylbenzoyl) - (2,6-diethylbenzoyl) cyclohexylphosphine ooxide; (2,6-dimethylbenzoyl) - (2,4,6-trimethylbenzoyl) cyclohexylphosphine oxide; (2,6-dimethylbenzoyl) - (2,6-dimethyl-4-tert-butylbenzoyl) cyclohexylphosphine oxide; (2,6-dimethylbenzoyl) - (2,4,6-trimethoxybenzoyl) cyclohexylphosphine ooxide; (2,6-dimethylbenzoyl) - (2,4-dimethoxybenzoyl) cyclohexylphosphine ooxide; (2,6-dimethylbenzoyl) (2,6-diethoxybenzoyl) cyclohexylphosphine oxide; (2,6-dimethylbenzoyl) - (2,6-dimethoxy-4-methylbenzoyl) cyclohexylphosphine ooxide; (2,6-dimethylbenzoyl) - (2,6-dichlorobenzoyl) cyclohexylphosphine oxide; (2,6-dimethylbenzoyl) - (2,4,6-trichlorobenzoyl) cyclohexylphosphine oxide; (2,6-dimethylbenzoyl) - (2,6-bis (trifluoromethyl) benzoyl) cyclohexylphosphine oxide; (2,4,6-trimethoxybenzoyl) - (2,6-dimethylbenzoyl) cyclohexylphosphine oxide; (2,4,6-trimethoxybenzoyl) - (2,6-diethylbenzoyl) cyclohexylphosphine oxide; (2,4,6-trimethoxybenzoyl) - (2,4,6-trimethylbenzoyl) cyclohexylphosphine oxide; (2,4,6-trimethoxybenzoyl) - (2,6-dimethyl-4-tert-butylbenzoyl) cyclohexylphosphine oxide; (2,4,6-trimethoxybenzoyl) - (2,4-dimethoxybenzoyl) cyclohexylphosphine oxide; (2,4,6-trimethoxybenzoyl) - (2,6-diethoxybenzoyl) cyclohexylphosphine oxide; (2,4,6-trimethoxybenzoyl) - (2,6-dichlorobenzoyl) cyclohexylphosphine oxide; (2,4,6-trimethoxybenzoyl) -2,6-bis (trifluoromethyl) benzoylcyclohexylphosphine ooxide; (2,6-Dimethyl-4-tert-butylbenzoyl) - (2,6-dimethylbenzoyl) cyclohexylphosphine ooxide; (2,6-dimethyl-4-tert-butylbenzoyl) - (2,6-diethylbenzoyl) cyclohexylphosphine ooxide; (2,6-Dimethyl-4-tert-butylbenzoyl) (2,4,6-trimethylbenzoyl) cyclohexylphosphine oxide; (2,6-Dimethyl-4-tert-butylbenzoyl) - (2,6-dimethyl-4-tert-butylbenzoyl) cyclohexylphosphine ooxide; (2,6-Dimethyl-4-tert-butylbenzoyl) - (2,4,6-trimethoxybenzoyl) cyclohexylphosphine ooxide; (2,6-Dimethyl-4-tert-butylbenzoyl) - (2,4-dimethoxybenzoyl) cyclohexylphosphine oxide; (2,6-dimethyl-4-tert-butylbenzoyl) - (2,6-diethoxybenzoyl) cyclohexylphosphine oxide; (2,6-Dimethyl-4-tert-butylbenzoyl) - (2,6-dimethoxy-4-methylbenzoyl) cyclohexylphosphine oxide; (2,6-Dimethyl-4-tert-butylbenzoyl) - (2,6-dichlorobenzoyl) cyclohexylphosphine ooxide; (2,6-Dimethyl 4-tert-butylbenzoyl) - (2,4,6-trichlorobenzoyl) cyclohexylphosphine oxide; (2,6-Dimethyl-4-tert-butylbenzoyl) -2,6-bis (trifluoromethyl) benzoylcyclohexylphosphine ooxide.

Compounds of formula I, where R is o

II

<img file="ES2194584A1_D0041.tif" />

in which x = 0 (formula II '), are obtained by reacting an alkylacylphosphine of formula I with an acid halide of formula (IV):

II ll (I) ñ₆ + Y, - c — X (IV)

II II

Ar — C — PCY

R, '6 (ll¹)

The meanings of the residues Ar, R6, M, XeY1 are the same as those described above.

The starting materials are advantageously reacted in a molar ratio of 1: 1. The use of a slight excess of one of the components, eg up to 20%, does not create problems. The desired product is also obtained in this case, although such an excess may affect the portion of the troublesome by-product. The reaction conditions are the same as those indicated above for obtaining the compounds of formula I.

Compounds of formula I, where R is o

II

<img file="ES2194584A1_D0042.tif" />

in which x = 1 and A is oxygen, are obtained by oxidation of the compounds of formula (II ') and the compounds of formula I, where R is

ES 2 194 584 A1 ¿? ,

-c-η in which A is sulfur, are obtained by sulfidation of the compounds of formula II ':

<img file="ES2194584A1_D0043.tif" />

Before oxidizing or sulfurizing, the phosphine II 'can be isolated by the usual separation methods already known to the technician in the field, although it is also possible to carry out the reaction immediately after the previous steps without the need to isolate the phosphine.

To obtain the oxide, the oxidation of the phosphine was carried out using oxidants customary in the art. Hydrogen peroxide and peroxyorganic compounds, for example peracetic acid or t-butyl hydroperoxide, air or pure oxygen are ionic oxidants.

The oxidation is advantageously carried out in solution. Idoone solvents are aromotic hydrocarbons, for example benzene, toluene, m-xylene, p-xylene, ethylbenzene or mesitylene, or aliphatic hydrocarbons, e.g. alkanes and alkane mixtures, such as petroleum ether, hexane or cyclohexane. Also suitable examples are dimethyl ether, diethyl ether, methylpropyl ether, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, dioxane or tetrahydrofuran. Toluene is preferably used.

The reaction temperature during the oxidation is advantageously kept between 0 and 120 ° C, preferably between 20 and 80 ° C.

The reaction products of formula (II) can be isolated and purified by standard methods, with which the person skilled in the art is already familiar.

Obtaining the corresponding sulfur was carried out by reaction with sulfur. The bisacylphosphines (II ') are reacted with a 2-molar quantity of elemental sulfur, that is to say without diluent or optionally with an inert ionic organic solvent. Examples of suitable solvents are those described following the oxidation reaction. It is also possible to use aliphatic or aromotic ethers, for example dibutyl ether, dioxane, diethylene glycol dimethyl ether, or diphenyl ether, at a temperature between 20 and 250^°C, preferably between 60 and 120^°C. It is advantageous to purify the resulting bisacylphosphine sulfide or its solution by filtration in order to remove elemental sulfur that may still be present in the mixture. Once the solvent has been removed, the bisacylphosphine sulfide can be isolated in pure form by selective methods such as distillation, recrystallization or chromatography.

It is advantageous to carry out all the reactions described above with the exclusion of air, in an inert gas atmosphere, eg in a nitrogen or argon atmosphere. Furthermore, it is advantageous to stir the reaction mixture in question.

The invention also provides a process for obtaining the compounds of formula I,

<img file="ES2194584A1_D0044.tif" />

ES 2 194 584 A1 starting from the compounds of formula I, where R is t? ,

-C-γ, by (1) reaction of an acyl halide of formula IV

II

Ar — C — X (IV) where Ar has the meaning defined above and XesCloBr;

with a dimethalated organylphosphine from phaormula V

<img file="ES2194584A1_D0045.tif" />

in which R6 has the meaning defined before and

M1 is Na, LioK;

in a molar ratio of 1: 1;

(2) subsequent reaction of the product with an acyl halide of the formula IVa

<img file="ES2194584A1_D0046.tif" />

where Yl has the meaning defined before and

X has the meaning defined above;

provided that the acyl halide of formula IV is not identical to the acyl halide of formula IVa;

in an approximate molar ratio of 1: 1 and (3) if you want to obtain the compounds of formula I where R is

OR

II '

-C- © where A is oxygen or sulfur, subsequent oxidation or sulfuration of the resulting phosphine compounds.

Compounds of formula I, where R is

<img file="ES2194584A1_D0047.tif" />

ES 2 194 584 A1 can also be obtained by reacting the compound of formula I, where R is M, with phosgene according to the description of "WA Henderson et al. in J. Am. Chem. Soc. 1960, 82, 5794 "or from" GB 904 086 "or from" Organic Phosphorous Compounds ", coordinators: RM Kosolapoff and L. Maier, Wiley-Interscience 1972, vol. 1, page 28 or from "Houben-Weyl, Methoden der Organischen Chemie", vol. XII / 1, page 201, obtaining the corresponding phosphine chloride (Ii). As described in "Organic Phosphorous Compounds", coordinators: RM Kosolapoff and L. Maier, WileyInterscience 1972, vol. 4, pages 268-269, the compounds of the formula (Ii) can be reacted with alcohols to obtain the compounds of the formula (Iii) which then react with an acyl halide of the formula IVa by a method similar to that described in US -4324744 (Michaelis-Arbuzov reaction) to yield the compounds of formula I, where R is o

II

-c-η

In this case the oxidation step is not required.

structure (II).

<img file="ES2194584A1_D0048.tif" />

Ar and Ar 'have the meanings defined in claim 1 for Ar, but Ar and Ar' do not mean the same aryl residue; X is Cl or Br; M and R6 have the meanings defined in claim 1 and R is any alcohol residue, eg C1-C12 alkyl, C5-C8 cycloalkyl, eg cyclopentyl or cyclohexyl, or benzyl.

Chlorination with phosgene with removal of carbon monoxide is advantageously carried out by introducing the phosgene with stirring in a solution of (I) in an inert solvent. For example, phosgene is introduced at a temperature between -70 and + 20 ° C, especially between -40 and 0 ° C. The solvents that can be used are, for example, chlorinated alkanes, for example dichloromethane, dichloroethane or tetrachloromethane; alkanes, for example hexane; cycloalkanes, for example cyclohexane, or aromatic solvents, for example toluene. The isolation of (II) was carried out, for example, by distillation under reduced pressure.

Such reactions are also described eg in R. Schmutzler et al., Z. Anorg. Allg. Chemie 1999, 625, pages 1979-1984.

The conversion of (Ii) to (Iii) was carried out for example in an inert solvent in the presence of a tertiary amine, for example triethylamine, tributylamine or pyridine. In this case, the alcohol (ROH) is advantageously added by virtue of the solution (Ii) and the tertiary amine in the solvent. The addition is advantageously carried out at a temperature between 60 and 140 ° C. The solvents that can be used are, for example, chlorinated alkanes, eg. tetrachloromethane, dichloromethane, dichloroethane; alkanes, for example hexane; cycloalkanes, for example cyclohexane; or aromatic solvents, for example toluene. The isolation of (III) can be effected, for example, by distillation under reduced pressure. Such reactions have been published eg by YA Veits et al., In J. Gen. Chem. (URRS) 1991, 61, pages 108 ff.

The conversion of the compounds of the formula (Iii) into compounds of the formula I, where

<img file="ES2194584A1_D0049.tif" />

ES 2 194 584 A1 is carried out by adding the corresponding acyl halides (IVa) to a solution of (Iii) in an inert solvent. In this case, the acyl halide is advantageously dissolved in the same solvent used for the previous reaction step. The addition is carried out, for example, at a temperature between 40 and 140 ° C, preferably between 60 and 120 ° C, the alkyl halide (RCI) evolved during the reaction is advantageously removed by distillation, separating it from the reacting solution. The solvents that can be used in this case are for example alkanes, for example hexane, octane; cycloalkanes, for example cyclohexane; ethers, for example methyl tert-butyl ether, tetrahydrofuran, dioxane; or aromatic solvents, for example toluene or xylene. It is advantageous to isolate and purify the compounds of structure (II), for example by distillation under reduced pressure, crystallization or by chromatography.

The compounds of phaormula (Iii) can be oxidized using suitable oxidants, for example peroxoacids, hydrogen peroxide or hydrogen peroxide / urea, to obtain the corresponding phosphainic asters (Iiii):

Ar-CP-OR (li¡¡).

©

This process of obtaining is new. The compounds thus obtained constitute photoinitiators and as such are described for example in US-4324744.

The invention thus provides a process for obtaining compounds of the formula I, where Res

OR

II

-cY, where A is oxygen and x is 1, by (1) reaction of a compound of formula I, where R is M, described above, ¿? /^M

Ar — CP (|) ©

in which Ar, M and R6 have the definitions indicated above, with phosgene to obtain the corresponding phosphine chloride (Ii)

<img file="ES2194584A1_D0050.tif" />

(2) later they react with an alcohol to obtain the compound of the formula (Iii)

<img file="ES2194584A1_D0051.tif" />

ES 2 194 584 A1 in which R is a residue of an alcohol, in particular C1-C12 alkyl, C5-C8 cycloalkyl or benzyl; and (3) reaction of the resulting compound of formula (Iii) with an acyl halide or

II

-c-η where Y₁ has the meaning defined before

XesCl oBr, to obtain the compound of formula I, where R is

II '

-C-_Yl in which Y₁ and Ar do not necessarily have to be different.

As mentioned above, asymmetric monoacylphosphines, oxides and sulfides of monoacylphosphines can also be easily obtained from the compounds of formula I.

In the compounds of the formula I, where R is Z1 the preferred meanings of the residues Ar, R1, R2, R3, R4, R5 and R6 are similar to those attributed above to the compounds of the formula I, where R is M.

In formula I, where R is Z1 A is in particular oxygen, x is preferably the nuomer1 and Ar preferably represents a group

<img file="ES2194584A1_D0052.tif" />

Compounds of formula I are preferred, where R is Z, where Ar is a group

<img file="ES2194584A1_D0053.tif" />

AesO, yxes1, R1 and R2 are independently C1-C12 alkyl, C1-C12 alkoxy, CF3 or halogen; R3, R4 and R5 are independently hydrogenic, C1-C12 alkyl, C1-C12 alkoxy or halogen; R6 is C1-C12 alkyl, unsubstituted or substituted by OR11, cycloalkenyl, CN, C (O) R11, C (O) OR 11, C (O) N (R14) 2, phenyl, cycloalkyl; C2-C12 alkyl that is interrupted one or more times by non-consecutive O, S or NR14 groups and that is unsubstituted or substituted by OR11, SR11, N (R12) (R13), CN, C (O) R11, C ( O) OR11 and / or C (O) N (R14) 2; C2-C12 alkenyl which is uninterrupted or interrupted one or more times by non-consecutive O, S or NR14 groups and which is unsubstituted or substituted by OR11, SR11, N (R12) (R13); benzyl, cyclopentyl, cyclohexyl, C4-C12 cycloalkyl that was uninterrupted or interrupted one or more times by O, S and / or NR14 groups; or C9-C12 arylcycloalkyl; R12 and R13 independently of each other are hydrogen, C1-C4 alkyl, C3-C6 cycloalkyl, phenyl, benzyl or C2-C12 alkyl interrupted one or more times by O or S and which is unsubstituted or substituted by OH and / or SH; or R12 and R13 together are piperidino, morpholino or piperazino; Z1 has the same meaning as R6, provided that Z1 and R6 are not identical, or Z1 is C3-C12 cycloalkyl unsubstituted or substituted by C1-C20 alkyl, OR11, CF3 or halogen;

ES 2 194 584 A1 C2-C12 alkenyl or C3 -C12 cycloalkenyl, or Z1 is one of the radicals (g), (h), (i) (k), (l), (m), (n), (o), (p) (q), (t), (u), (v) or (w); Z2 is C1-C18 alkylene, C2-C12 alkylene interrupted one or more times by O, S or NR14; C2 -C12 alkenylene, C2 -C12 alkenylene interrupted one or more times by O, S or NR14; C3-C12 cycloalkylene, C3-C12 cycloalkylene interrupted one or more times by O, SoNR14; C3 -C12 cycloalkenylene, C3 -C12 cycloalkenylene interrupted one or more times by O, S or NR14; the radicals being C1-C18 alkylene, C2-C12 alkylene, C2 -C12 alkenylene, C3-C12 cycloalkylene and C3-C12 cycloalkenylene unsubstituted or substituted by OR11, SR11, N (R12) (R13) and / or halogen; or Z2 is one of the remains

<img file="ES2194584A1_D0054.tif" />

these moieties may be unsubstituted or substituted on the aromatic ring by C1-C12 alkyl; C2-C12 alkyl interrupted one or more times by non-consecutive O atoms and which was unsubstituted or substituted by OH and / or SH; OR11, SR11, N (R12) (R13), phenyl, halogen, NO2, CN, (CO) -OR18, (CO) -R18, (CO) -N (R18) 2, SO2 R24 and / or CF3; or Z2 is a group (r); Z3 is CH2, CHCH3 or C (CH3) 2, Z4 is S, O, CH2, C = O, NR14 or a direct bond; Z5 is S, O, CH2, CHCH3, C (CH3) 2, C (CF3) 2, SO, SO2; Z6 and Z7 independently of each other are CH2, CHCH3 or C (CH3) 2; res0,1oo2; sesunnuomer of 1 to 12; q is a number from 0 to 50; typ are in each case a number from 0 to 20; E, G, G3 and G4 independently of each other are C1-C12 alkyl or are phenyl unsubstituted or substituted by one or more C1-C4 alkyl; R14 is hydrogenic, phenyl, C1-C4 alkyl or C1-C4 alkoxy; R19, R20 , R21, R22 and R23 have one of the meanings defined for R6 or are NO2, CN, SO2, R24, CF3 or halogen; R24 is C1-C12 alkyl, C1-C12 alkyl substituted by halogen; phenyl or phenyl substituted by OR11 and / or SR11.

The preferred meanings of R6 have been defined above.

In compounds of formula I, where R is Z₁ , R₁₂ yR₁₃ are preferably C alkyl₁-C₄ , C1-C4 alkoxy or R12 and R13 together form a morpholino ring.

Also of interest are the compounds of the formula I, where R is Z1, where A is a group

<img file="ES2194584A1_D0055.tif" />

AesO, yxes1, R1 and R2 independently of one another are C1-C4 alkyl, C1-C4 alkoxy, CF3 or halogen; R3, R4 and R5 are independently hydrogenic, C1-C4 alkyl, C1-C4 alkoxy or chloro; R6 is C1-C12 alkyl unsubstituted or substituted by OR11, cycloalkenyl, CN, C (O) R11, C (O) OR11, C (O) N (R14) 2, phenyl, cycloalkyl; C2-C12 alkyl that was interrupted one or more times by non-consecutive O, S or NR14 groups and that is unsubstituted or substituted by OR11, SR11, N (R12) (R13), CN, C (O) R11, C ( O) OR11 and / or C (O) N (R14) 2; C2 -C12 alkenyl that is uninterrupted or interrupted one or more times by non-consecutive O, S or NR14 groups and that was unsubstituted or substituted by OR11, SR11, N (R12) (R13); benzyl, cyclopentyl, cyclohexyl, C4-C12 cycloalkyl that is uninterrupted or interrupted one or more times by O, S and / or NR14 groups; or C8-C12 arylcycloalkyl; R11 is H, C1-C8 alkyl, cyclopentyl, cyclohexyl, phenyl, benzyl or C2-C6 alkyl which is interrupted by one or two non-consecutive O-atoms and is unsubstituted or substituted by OH; R12 and R13 independently of one another are hydrogenic, C1-C4 alkyl, cyclopentyl, cyclohexyl, phenyl, benzyl or C2-C6 alkyl interrupted once or twice by atoms of 0 and which is unsubstituted or substituted by OH; or R₁₂ yR₁₃ together they form a morpholino; Z₁has the same meaning as R6, provided that Z1 and R6 are not identical, or Z1 is one of the remainders (g), (h), (i), (k), (l), (m), (n), (o), (p), (q), (t), (u), (v) or (w); Z2 is C1-C12 alkylene, C2-C12 alkylene interrupted one or more times by O; C2-C12 alkenylene, C2-C12 alkenylene interrupted one or more times by O; C5-C8 cycloalkylene, C3-C5 cycloalkylene interrupted by O, S or NR14; C5-C8 cycloalkenylene, C3-C5 cycloalkenylene interrupted by O, S or NR14; the radicals being C1-C12 alkylene, C2 -C12 alkylene, C2 -C12 alkenylene, C5 -C8 cycloalkylene and C3 -C8 cycloalkenylene unsubstituted or substituted by OR11; or Z2 is one of the radicals

ES 2 194 584 A1

<img file="ES2194584A1_D0056.tif" />

these moieties are unsubstituted or substituted on the aromatic ring by C1-C4 alkyl, OR11, phenyl, (CO) -OR18, (CO) -R18 and / or (CO) -N (R18) 2; or Z2 is a group (r); Z3 is CH2, CHCH3 or C (CH3) 2, Z4 is S, O, CH2, C = O, NR14 or a direct bond; Z5 is O, CH2, CHCH3, C (CH3) 2, C (CF3) 2; Z6 and Z7 regardless of whether they are CH2, CHCH3 or C (CH3) 2; res0.1ao2; sesunumer from 1 to 12; q is a number from 0 to 50; typ are in each case a number from 0 to 20; E, G, G3 and G4 independently of whether they are C1-C12 alkyl or are phenyl unsubstituted or substituted by one or more C1-C4 alkyl, R14 is hydrogen, phenyl or C1-C4 alkyl.

Examples of compounds of formula I, where R is Z1, of the present invention are the following:

2,4,6-trimethylbenzoyl-n-butyl-methylphosphine oxide; 2,4,6-trimethylbenzoyl-n-butyl ethylphosphine oxide; 2,4,6-trimethylbenzoyl-n-butyl-propylphosphine oxide; 2,4,6-trimethylbenzoyl di (n-butyl) phosphine ooxide; 2,4,6-trimethylbenzoyl-n-butyl-pentylphosphine oxide; 2,4,6-trimethylbenzoyl-n-butyl-hexylphosphine ooxide; 2,4,6-trimethylbenzoyl-n-butyl-heptylphosphine ooxide; ooxide

2,4,6-trimethylbenzoyl-n-butyl-octylphosphine; 2,4,6-trimethylbenzoyl-n-butyl-dodecylphosphine ooxide; 2,4,6-trimethylbenzoyl-n-butyl-isopropylphosphine oxide; 2,4,6-trimethylbenzoyl-n-butyl-isobutylphosphine ooxide; 2,4,6-trimethylbenzoyl-n-butyl-amylphosphine oxide; 2,4,6-trimethylbenzoyl-n-butyl - (2-ethylhexyl) phosphine oxide; (2,4,6-trimethylbenzoyl) -n-butyl - (tert-butyl) phosphine ooxide; (2,4,6-trimethylbenzoyl) -n-butyl - (1-methyl-propyl) phosphine ooxide; 2,4,6-trimethylbenzoyl n-butyl-isopentylphosphine oxide; 2,4,6-trimethylbenzoyl-n-butyl-methoxyethoxyphosphine ooxide; oxide

2,4,6-trimethylbenzoyl-n-butyl-benzylphosphine; (2,4,6-trimethylbenzoyl) -n-butyl- (2,4,4-trimethylpentyl) phosphine oxide; (2,4,6-trimethylbenzoyl) -n-butyl - (methyl 2-propionate) phosphine oxide; (2,4,6-trimethylbenzoyl) -n-butyl- (2-ethyl propionate) phosphine oxide; (2,4,6-trimethylbenzoyl) n-butyl - (2-propyl propionate) phosphine ooxide; (2,4,6-trimethylbenzoyl) -n-butyl - (2-butyl propionate) phosphine ooxide; (2,4,6-trimethylbenzoyl) -n-butyl - (2-pentyl propionate) phosphine ooxide; (2,4,6-trimethylbenzoyl) -n-butyl- (hexyl 2-propionate) phosphine ooxide; (2,4,6-trimethylbenzoyl) -nbutyl- (octyl 2-propionate) phosphine oxide; (2,4,6-trimethylbenzoyl) -n-butyl - (decyl 2-propionate) phosphine ooxide; (2,4,6-trimethylbenzoyl) -n-butyl- (2-dodecyl propionate) phosphine oxide; (2,4,6-trimethylbenzoyl) -n-butyl - (isopropyl 2-propionate) phosphine ooxide; (2,4,6-trimethylbenzoyl) n-butyl - (2-isobutyl propionate) phosphine ooxide; (2,4,6-Trimethylbenzoyl) -n-butyl- (2-amyl propionate) -phosphine oxide; (2,4,6-trimethylbenzoyl) -n-butyl - (2-ethylhexyl 2-propionate) phosphine oxide; (2,4,6-trimethylbenzoyl) -n-butyl - (tert-butyl 2-propionate) phosphine oxide; (2,4,6-trimethylbenzoyl) -n-butyl - (1-methylpropyl 2-propionate) phosphine ooxide; (2,4,6-trimethylbenzoyl) -n butyl- (isopentyl 2-propionate) phosphine ooxide; (2,4,6-trimethylbenzoyl) -n-butyl - (2-methoxyethoxy propionate) phosphine oxide; (2,4,6-trimethylbenzoyl) -n-butyl- (2-benzyl propionate) phosphine oxide; (2,4,6-trimethylbenzoyl) -n-butyl - (2,4,4-trimethylpentyl 2-propionate) phosphine oxide; ooxide

2,4,6-trimethylbenzoyl-n-butyl - (methyl acetate) phosphine; 2,4,6-trimethylbenzoyl-n-butyl (ethyl acetate) phosphine oxide; 2,4,6-trimethylbenzoyl-n-butyl- (propyl acetate) phosphine ooxide; ooxide

2.4.6-trimethylbenzoyl-n-butyl - (butyl acetate) phosphine; 2,4,6-trimethylbenzoyl-n-butyl (pentyl acetate) phosphine ooxide; 2,4,6-trimethylbenzoyl-n-butyl- (hexyl acetate) phosphine oxide; 2,4,6-trimethylbenzoyl-n-butyl- (octyl acetate) phosphine ooxide; 2,4,6-trimethylbenzoyl-n-butyl (decyl acetate) phosphine ooxide; 2,4,6-trimethylbenzoyl-n-butyl- (dodecyl acetate) phosphine oxide; 2,4,6-trimethylbenzoyl-n-butyl- (isopropyl acetate) phosphine oxide; 2,4,6-trimethylbenzoyl-n butyl- (isobutyl acetate) phosphine ooxide; 2,4,6-trimethylbenzoyl-n-butyl- (amyl acetate) phosphine ooxide; (2,4,6-trimethylbenzoyl) -n-butyl - (2-ethylhexyl acetate) phosphine ooxide; (2,4,6-trimethylbenzoyl) -n-butyl- (tert-butyl acetate) phosphine ooxide; (2,4,6-trimethylbenzoyl) -n-butyl- (1-methylpropyl acetate) phosphine oxide; 2,4,6-trimethylbenzoyl-n-butyl- (isopentyl acetate) phosphine ooxide; 2,4,6-trimethylbenzoyl-n-butyl- (methoxyethoxy acetate) phosphine ooxide; 2,4,6-trimethylbenzoyl-n-butyl- (benzyl acetate) phosphine ooxide; (2,4,6-trimethylbenzoyl) -n-butyl- (acetate)

2,4,4-trimethylpentyl) -phosphine; 2,6-dimethoxybenzoyl-n-butyl-methylphosphine ooxide; 2,6-dimethoxybenzoyl-n-butyl-ethylphosphine ooxide; 2,6-dimethoxybenzoyl-n-butyl-propylphosphine ooxide; oxide

2.6-dimethoxybenzoyl-di (n-butyl) phosphine; 2,6-dimethoxybenzoyl-n-butyl-pentylphosphine ooxide; oxide

2,6-dimethoxybenzoyl-n-butyl-hexylphosphine; 2,6-dimethoxybenzoyl-n-butyl-heptylphosphine ooxide; 2,6-dimethoxybenzoyl-n-butyl-octylphosphine ooxide; 2,6-dimethoxybenzoyl-n-butyl-dodecylphosphine oxide; 2,6-dimethoxybenzoyl-n-butyl-isopropylphosphine oxide; 2,6-dimethoxybenzoyl-n-butyl-isobutylphosphine oxide; 2,6-dimethoxybenzoyl-n-butyl-amylphosphine oxide; (2,6-dimethoxybenzoyl) -noxide n 31

ES 2 194 584 A1

- butyl - (2-ethylhexyl) phosphine; 2,6-dimethoxybenzoyl-n-butyl - (tert-butyl) phosphine ooxide; (2,6-dimethoxybenzoyl) -n-butyl - (1-methylpropyl) phosphine ooxide; 2,6-dimethoxybenzoyl-n-butyl-isopentylphosphine ooxide; 2,6-dimethoxybenzoyl-n-butyl-methoxyethoxyphosphine oxide; 2,6-dimethoxybenzoyl-n-butyl-benzylphosphine ooxide; (2,6-dimethoxybenzoyl) -n-butyl - (2,4,4-trimethylpentyl) phosphine ooxide; (2,6-dimethoxybenzoyl) -n-butyl- (methyl 2-propionate) phosphine ooxide; (2,6-dimethoxybenzoyl) -n-butyl - (ethyl 2-propionate) phosphine ooxide; (2,6-dimethoxybenzoyl) -nbutyl- (propyl 2-propionate) phosphine oxide; (2,6-dimethoxybenzoyl) -n-butyl - (2-butyl propionate) phosphine ooxide; (2,6-dimethoxybenzoyl) -n-butyl - (2-pentyl propionate) phosphine oxide; (2,6-dimethoxybenzoyl) -n-butyl - (hexyl 2-propionate) phosphine ooxide; (2,6-dimethoxybenzoyl) -nbutyl- (octyl 2-propionate) phosphine ooxide; (2,6-dimethoxybenzoyl) -n-butyl - (decyl 2-propionate) phosphine ooxide; (2,6-dimethoxybenzoyl) -n-butyl- (2-dodecyl propionate) phosphine oxide; (2,6-dimethoxybenzoyl) -n-butyl- (isopropyl 2-propionate) phosphine ooxide; (2,6-dimethoxybenzoyl) n-butyl - (isobutyl 2-propionate) phosphine ooxide; (2,6-dimethoxybenzoyl) -n-butyl - (2-amyl propionate) phosphine oxide; (2,6-dimethoxybenzoyl) -n-butyl - (2-ethylhexyl 2-propionate) phosphine ooxide; (2,6-dimethoxybenzoyl) -n-butyl - (tert-butyl 2-propionate) phosphine oxide; (2,6-dimethoxybenzoyl) -n-butyl - (1-methylpropyl 2-propionate) phosphine ooxide; (2,6-dimethoxybenzoyl) -nbutyl- (isopentyl 2-propionate) phosphine ooxide; (2,6-dimethoxybenzoyl) -n-butyl - (2-methoxyethoxy propionate) phosphine ooxide; (2,6-dimethoxybenzoyl) -n-butyl - (benzyl 2-propionate) phosphine oxide; (2,6-Dimethoxybenzoyl) -n-butyl - (2,4,4-trimethylpentyl 2-propionate) phosphine ooxide; ooxide

2,6-dimethoxybenzoyl-n-butyl - (methyl acetate) phosphine; 2,6-dimethoxybenzoyl-n-butyl (ethyl acetate) phosphine ooxide; 2,6-dimethoxybenzoyl-n-butyl- (propyl acetate) phosphine oxide; ooxide

2,6-dimethoxybenzoyl-n-butyl - (butyl acetate) phosphine; 2,6-dimethoxybenzoyl-n-butyl (pentyl acetate) phosphine ooxide; 2,6-dimethoxybenzoyl-n-butyl- (hexyl acetate) phosphine oxide; 2,6-dimethoxybenzoyl-n-butyl- (octyl acetate) phosphine ooxide; 2,6-dimethoxybenzoyl-n-butyl- (decyl acetate) phosphine oxide; 2,6-dimethoxybenzoyl-n-butyl- (dodecyl acetate) phosphine oxide; 2,6-dimethoxybenzoyl-n-butyl- (isopropyl acetate) phosphine ooxide; 2,6-dimethoxybenzoyl-n-butyl- (isobutyl acetate) phosphine ooxide; 2,6-dimethoxybenzoyl-n-butyl- (amyl acetate) phosphine oxide; (2,6-dimethoxybenzoyl) -n-butyl- (2-ethylhexyl acetate) phosphine ooxide; ooxide

2,6-dimethoxybenzoyl-n-butyl - (tert-butyl acetate) phosphine; (2,6-dimethoxybenzoyl) n-butyl- (1-methylpropyl acetate) phosphine ooxide; 2,6-dimethoxybenzoyl-n-butyl- (isopentyl acetate) phosphine ooxide; 2,6-dimethoxybenzoyl-n-butyl- (methoxyethoxy acetate) phosphine ooxide; oxide

2.6-dimethoxybenzoyl-n-butyl - (benzyl acetate) phosphine; (2,6-Dimethoxybenzoyl) -n-butyl (2,4,4-trimethylpentyl acetate) phosphine oxide; 2,4,6-trimethylbenzoyl-isobutyl-methylphosphine oxide; 2,4,6-Trimethylbenzoyl-isobutyl-ethylphosphine ooxide; 2,4,6-trimethylbenzoyl-isobutyl-propylphosphine ooxide; 2,4,6-trimethylbenzoyl-isobutyl - (n-butyl) phosphine ooxide; 2,4,6-trimethylbenzoyl-isobutyl pentylphosphine ooxide; 2,4,6-trimethylbenzoyl-isobutyl-hexylphosphine ooxide; 2,4,6-trimethylbenzoyl isobutyl-heptylphosphine ooxide; 2,4,6-trimethylbenzoyl-isobutyl-octylphosphine oxide; 2,4,6-trimethylbenzoyl-isobutyl-dodecylphosphine ooxide; 2,4,6-trimethylbenzoyl-isobutyl-isopropylphosphine ooxide; ooxide

2.4.6-trimethylbenzoyl-di-isobutylphosphine; 2,4,6-trimethylbenzoyl-isobutylamilphosphine ooxide; ooxide

2,4,6-trimethylbenzoyl-isobutyl - (2-ethylhexyl) phosphine; (2,4,6-Trimethylbenzoyl) -isobutyl - (tert-butyl) -phosphine ooxide; (2,4,6-Trimethylbenzoyl) -isobutyl - (1-methylpropyl) phosphine ooxide; 2,4,6-trimethylbenzoyl-isobutyl-isopentylphosphine ooxide; 2,4,6-trimethylbenzoyl-isobutyl-methoxyethoxyphosphine oxide; 2,4,6-trimethylbenzoyl-isobutyl-benzylphosphine ooxide; (2,4,6-trimethylbenzoyl) -isobutyl - (2,4,4-trimethylpentyl) phosphine ooxide; (2,4,6-trimethylbenzoyl) -isobutyl - (methyl 2-propionate) phosphine ooxide; (2,4,6-trimethylbenzoyl) -isobutyl - (ethyl 2-propionate) phosphine ooxide; (2,4,6-trimethylbenzoyl) isobutyl - (propyl 2-propionate) phosphine ooxide; (2,4,6-Trimethylbenzoyl) -isobutyl - (butyl 2-propionate) phosphine ooxide; (2,4,6-Trimethylbenzoyl) -isobutyl - (2-pentyl propionate) phosphine oxide; (2,4,6-trimethylbenzoyl) -isobutyl - (hexyl 2-propionate) phosphine ooxide; (2,4,6-trimethylbenzoyl) isobutyl - (octyl 2-propionate) phosphine oxide; (2,4,6-Trimethylbenzoyl) -isobutyl - (decyl 2-propionate) phosphine ooxide; (2,4,6-Trimethylbenzoyl) -isobutyl - (2-dodecyl propionate) phosphine oxide; (2,4,6-trimethylbenzoyl) -isobutyl - (isopentyl 2-propionate) phosphine ooxide; (2,4,6-trimethylbenzoyl) isobutyl - (2-isobutyl propionate) phosphine ooxide; (2,4,6-Trimethylbenzoyl) -isobutyl - (2-amyl propionate) phosphine oxide; (2,4,6-Trimethyl-benzoyl) -isobutyl - (2-ethylhexyl 2-propionate) phosphine oxide; (2,4,6-trimethylbenzoyl) -isobutyl - (tert-butyl 2-propionate) phosphine oxide; (2,4,6-Trimethylbenzoyl) -isobutyl - (1-methylpropyl 2-propionate) phosphine ooxide; (2,4,6-trimethylbenzoyl) -isobutyl - (isopentyl 2-propionate) phosphine ooxide; (2,4,6-Trimethylbenzoyl) -isobutyl - (2-methoxyethoxy propionate) phosphine oxide; (2,4,6-Trimethylbenzoyl) -isobutyl - (2-benzyl propionate) phosphine oxide; (2,4,6-trimethylbenzoyl) -isobutyl - (2,4,4-trimethylpentyl 2-propionate) phosphine ooxide; 2,4,6-trimethylbenzoyl-isobutyl- (methyl acetate) phosphine ooxide; 2,4,6-trimethylbenzoyl-isobutyl- (ethyl acetate) phosphine oxide; 2,4,6-Trimethylbenzoyl-isobutyl- (propyl acetate) phosphine ooxide; 2,4,6-trimethylbenzoyl-isobutyl- (butyl acetate) phosphine ooxide; 2,4,6-trimethylbenzoyl-isobutyl- ooxide (acetate

ES 2 194 584 A1 pentyl) phosphine, 2,4,6-trimethylbenzoyl-isobutyl- (hexyl acetate) phosphine ooxide; 2,4,6-trimethylbenzoyl-isobutyl- (octyl acetate) phosphine ooxide; 2,4,6-trimethylbenzoyl-isobutyl - (decyl acetate) phosphine ooxide; 2,4,6-Trimethylbenzoyl-isobutyl- (dodecyl acetate) phosphine oxide; ooxide

2.4.6-trimethylbenzoyl-isobutyl - (isopropyl acetate) phosphine; 2,4,6-Trimethylbenzoyl-isobutyl- (isobutyl acetate) phosphine ooxide; 2,4,6-trimethylbenzoyl-isobutyl- (amyl acetate) phosphine oxide; (2,4,6-Trimethylbenzoyl) -isobutyl- (2-ethylhexyl acetate) phosphine oxide; (2,4,6-trimethylbenzoyl) -isobutyl- (tert-butyl acetate) phosphine oxide; (2,4,6-Trimethylbenzoyl) -isobutyl - (1-methylpropyl acetate) phosphine oxide; 2,4,6-trimethylbenzoyl-isobutyl- (isopentyl acetate) phosphine ooxide; 2,4,6-trimethylbenzoyl-isobutyl- (methoxyethoxy acetate) phosphine oxide; 2,4,6-trimethylbenzoyl-isobutyl- (benzyl acetate) phosphine ooxide; (2,4,6-trimethylbenzoyl) -isobutyl - (2,4,4-trimethylpentyl acetate) phosphine ooxide; 2,6-dimethoxybenzoyl-isobutyl-methylphosphine oxide; 2,6-dimethoxybenzoyl-isobutyl-ethylphosphine ooxide; 2,6-dimethoxybenzoyl-isobutyl-propylphosphine oxide; 2,6-dimethoxybenzoyl-isobutyl - (n-butyl) phosphine ooxide; 2,6-dimethoxybenzoyl-isobutyl-pentylphosphine ooxide; 2,6-dimethoxybenzoyl-isobutyl-hexylphosphine oxide; 2,6-dimethoxybenzoyl-isobutyl-heptylphosphine ooxide; 2,6-dimethoxybenzoyl-isobutyl-octylphosphine ooxide; 2,6-dimethoxybenzoyl-isobutyl-dodecylphosphine ooxide; 2,6-dimethoxybenzoyl-isobutyl-isopropylphosphine oxide; oxide

2.6-dimethoxybenzoyl-di-isobutylphosphine; 2,6-dimethoxybenzoyl-n-butylamylphosphine ooxide; (2,6-Dimethoxybenzoyl) -isobutyl - (2-ethylhexyl) phosphine ooxide; 2,6-dimethoxybenzoyl-isobutyl - (tert-butyl) phosphine ooxide; (2,6-Dimethoxybenzoyl) -isobutyl - (1-methylpropyl) phosphine oxide; 2,6-dimethoxybenzoyl-isobutyl-isopentylphosphine ooxide; 2,6-dimethoxybenzoyl-isobutyl-methoxyethoxyphosphine oxide; 2,6-dimethoxybenzoyl-isobutyl-benzylphosphine ooxide; (2,6-dimethoxybenzoyl) -isobutyl - (2,4,4-trimethylpentyl) phosphine ooxide; (2,6-dimethoxybenzoyl) -isobutyl - (methyl 2-propionate) phosphine oxide; (2,6-dimethoxybenzoyl) -isobutyl - (2-ethyl propionate) phosphine ooxide; (2,6-dimethoxybenzoyl) isobutyl - (propyl 2-propionate) phosphine oxide; (2,6-dimethoxybenzoyl) -isobutyl - (2-butyl propionate) phosphine ooxide; (2,6-Dimethoxybenzoyl) -isobutyl - (2-pentyl propionate) phosphine oxide; (2,6-dimethoxybenzoyl) -isobutyl - (hexyl 2-propionate) phosphine oxide; (2,6-dimethoxybenzoyl) -isobutyl - (octyl 2-propionate) phosphine oxide; (2,6-dimethoxybenzoyl) -isobutyl - (decyl 2-propionate) phosphine ooxide; (2,6-Dimethoxybenzoyl) -isobutyl - (2-dodecyl propionate) phosphine oxide; (2,6-dimethoxybenzoyl) -isobutyl - (isopropyl 2-propionate) phosphine ooxide; (2,6-dimethoxybenzoyl) isobutyl - (2-isobutyl propionate) phosphine ooxide; (2,6-Dimethoxybenzoyl) -isobutyl - (2-amyl propionate) phosphine oxide; (2,6-Dimethoxybenzoyl) -isobutyl - (2-ethylhexyl 2-propionate) phosphine oxide; (2,6-Dimethoxybenzoyl) -isobutyl - (tert-butyl 2-propionate) phosphine oxide; (2,6-Dimethoxybenzoyl) -isobutyl - (1-methylpropyl 2-propionate) phosphine ooxide; (2,6-dimethoxybenzoyl) -isobutyl - (isopentyl 2-propionate) phosphine oxide; (2,6-Dimethoxybenzoyl) -isobutyl - (2-methoxyethoxy propionate) phosphine oxide; (2,6-Dimethoxybenzoyl) -isobutyl - (2-benzyl propionate) phosphine oxide; (2,6-Dimethoxybenzoyl) -isobutyl - (2,4,4-trimethylpentyl 2-propionate) phosphine oxide; 2,6-dimethoxybenzoyl-isobutyl- (methyl acetate) phosphine ooxide; 2,6-dimethoxybenzoyl-isobutyl- (ethyl acetate) phosphine oxide; 2,6-dimethoxybenzoyl-isobutyl- (propyl acetate) phosphine ooxide; 2,6-dimethoxybenzoyl-isobutyl- (butyl acetate) phosphine ooxide; 2,6-dimethoxybenzoyl-isobutyl- (pentyl acetate) phosphine ooxide; 2,6-dimethoxybenzoyl-isobutyl- (hexyl acetate) phosphine ooxide; 2,6-dimethoxybenzoyl-isobutyl- (octyl acetate) phosphine ooxide; 2,6-dimethoxybenzoyl-isobutyl- (decyl acetate) phosphine oxide; 2,6-dimethoxybenzoyl-isobutyl- (dodecyl acetate) phosphine oxide; 2,6-dimethoxybenzoyl-isobutyl- (isopropyl acetate) phosphine oxide; 2,6-dimethoxybenzoyl-isobutyl- (isobutyl acetate) phosphine ooxide; 2,6-dimethoxybenzoyl-isobutyl- (amyl acetate) phosphine oxide; (2,6-Dimethoxybenzoyl) -isobutyl- (2-ethylhexyl acetate) phosphine ooxide; 2,6-dimethoxybenzoyl-isobutyl- (tert-butyl acetate) phosphine oxide; (2,6-Dimethoxybenzoyl) -isobutyl - (1-methylpropyl acetate) phosphine ooxide; 2,6-dimethoxybenzoyl-isobutyl- (isopentyl acetate) phosphine oxide; 2,6-dimethoxybenzoyl-isobutyl- (methoxyethoxy acetate) phosphine ooxide; 2,6-dimethoxybenzoyl-isobutyl- (benzyl acetate) phosphine oxide; (2,6-Dimethoxybenzoyl) -isobutyl - (2,4,4-trimethylpentyl) phosphine acetate; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) -methylphosphine ooxide; (2,4,6-Trimethylbenzoyl) - (2,4,4-trimethylpentyl) -ethylphosphine ooxide; (2,4,6-Trimethylbenzoyl) - (2,4,4-trimethylpentyl) -propylphosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) -butylphosphine ooxide; (2,4,6-Trimethylbenzoyl) - (2,4,4-trimethylpentyl) -pentylphosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) -hexylphosphine oxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) -heptylphosphine oxide; (2,4,6-trimethylbenzoyl) (2,4,4-trimethylpentyl) -octylphosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) -dodecylphosphine oxide; (2,4,6-Trimethylbenzoyl) - (2,4,4-trimethylpentyl) -isopropylphosphine ooxide; (2,4,6-Trimethylbenzoyl) - (2,4,4-trimethylpentyl) -isobutylphosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) -amylphosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) - (2-ethylhexyl) phosphine oxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) - (tert-butyl) phosphine ooxide; (2,4,6-trimethylbenzoyl) (2,4,4-trimethylpentyl) - (1-methylpropyl) phosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) -isopentylphosphine oxide; (2,4,6-Trimethylbenzoyl) - (2,4,4-trimethylpentyl) -methoxyethoxyphosphine ooxide;

ES 2 194 584 A1 (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) -benzylphosphine oxide; (2,4,6-trimethylbenzoyl) -bis - (2,4,4-trimethylpentyl) phosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) - (2 methyl propionate) phosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) - (2-ethyl propionate) phosphine oxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) - (2-propyl propyl pionate) phosphine oxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) - (2-butyl propionate) phosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) - (2-pentyl propionate) phosphine oxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) - (2-hexyl propionate) phosphine oxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) - (2-octyl propionate) phosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) - (2-decyl propionate) phosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,4 trimethylpentyl) - (2-dodecyl propionate) phosphine oxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) - (2-isopropyl propionate) phosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) - (2-isobutyl propionate) phosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) - (2-amyl propionate) phosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) - (2-ethylhexyl propionate) phosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) - (2-propionate tert-butyl) phosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) - (1-methylpropyl 2-propionate) phosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) - (2-isopentyl propionate) phosphine oxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) - (2-methoxyethoxy propionate) phosphine oxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) - (2-benzyl propionate) phosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) - (2,4,4-trimethylpentyl 2-propionate) phosphine oxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) - (methyl acetate) phosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) - (ethyl acetate) phosphine ooxide; (2,4,6-trimethylbenzoyl) (2,4,4-trimethylpentyl) - (propyl acetate) phosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) - (butyl acetate) phosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) - (pentyl acetate) phosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) - (hexyl acetate) phosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) - (octyl acetate) phosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) - (decyl acetate) phosphine oxide; (2,4,6-trimethylbenzoyl) (2,4,4-trimethylpentyl) - (dodecyl acetate) phosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) - (isopropyl acetate) phosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) - (isobutyl acetate) phosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) - (amyl acetate) phosphine oxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) - (2-ethylhexyl acetate) phosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) - (tert-butyl acetate) phosphine oxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) - (1-methylpropyl acetate) phosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) - (isopentyl acetate) phosphine ooxide; (2,4,6-trimethylbenzoyl) - (2,4,4 trimethylpentyl) - (methoxyethoxy acetate) phosphine oxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) - (benzyl acetate) phosphine oxide; (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) - (acetate

2,4,4-trimethylpentyl) phosphine; 2,6-dimethoxybenzoyl - (2,4,4-trimethylpentyl) -methylphosphine oxide; 2,6-dimethoxybenzoyl - (2,4,4-trimethylpentyl) -ethylphosphine ooxide; 2,6-dimethoxybenzoyl - (2,4,4-trimethylpentyl) -propylphosphine ooxide; 2,6-dimethoxybenzoyl - (2,4,4-trimethylpentyl) -butylphosphine ooxide; ooxide

2,6-dimethoxybenzoyl - (2,4,4-trimethylpentyl) -pentylphosphine; 2,6-dimethoxybenzoyl - (2,4,4-trimethylpentyl) -hexylphosphine ooxide; 2,6-Dimethoxybenzoyl - (2,4,4-trimethylpentyl) -hexylphosphine oxide; ooxide

2,6-dimethoxybenzoyl - (2,4,4-trimethylpentyl) -octylphosphine; 2,6-dimethoxybenzoyl - (2,4,4-trimethylpentyl) -dodecylphosphine ooxide; 2,6-dimethoxybenzoyl - (2,4,4-trimethylpentyl) -isopropylphosphine oxide; ooxide

2,6-dimethoxybenzoyl - (2,4,4-trimethylpentyl) -isobutylphosphine; 2,6-dimethoxybenzoyl - (2,4,4-trimethylpentyl) -amylphosphine ooxide; (2,6-dimethoxybenzoyl) - (2,4,4-trimethylpentyl) - (2-ethyl-hexyl) phosphine oxide; 2,6-dimethoxybenzoyl - (2,4,4-trimethylpentyl) - (tert-butyl) phosphine oxide; (2,6-dimethoxybenzoyl) - (2,4,4-trimethylpentyl) - (1-methylpropyl) phosphine ooxide; 2,6-dimethoxybenzoyl - (2,4,4-trimethylpentyl) -isopentylphosphine ooxide; 2,6-dimethoxybenzoyl - (2,4,4-trimethylpentyl) -methoxyethoxyphosphine ooxide; ooxide

2,6-dimethoxybenzoyl - (2,4,4-trimethylpentyl) -benzylphosphine; (2,6-dimethoxybenzoyl) - (2,4,4-trimethylpentyl) - (2,4,4-trimethylpentyl) phosphine ooxide; (2,6-dimethoxybenzoyl) - (2,4,4-trimethylpentyl) - (2 methyl propionate) phosphine ooxide; (2,6-dimethoxybenzoyl) - (2,4,4-trimethylpentyl) (ethyl 2-propionate) phosphine ooxide; (2,6-dimethoxybenzoyl) - (2,4,4-trimethylpentyl) - (propyl 2-propionate) phosphine ooxide; (2,6-dimethoxybenzoyl) - (2,4,4-trimethylpentyl) - (2-butyl propionate) phosphine oxide; (2,6-dimethoxybenzoyl) - (2,4,4-trimethylpentyl) - (2-pentyl propionate) phosphine ooxide; (2,6-dimethoxybenzoyl) - (2,4,4-trimethylpentyl) - (2-hexyl propionate) phosphine ooxide; (2,6-dimethoxybenzoyl) (2,4,4-trimethylpentyl) - (2-octyl propionate) phosphine oxide; (2,6-dimethoxybenzoyl) - (2,4,4-trimethylpentyl) - (decyl 2-propionate) phosphine oxide; (2,6-dimethoxybenzoyl) - (2,4,4-trimethylpentyl) - (2-dodecyl propionate) phosphine ooxide; (2,6-dimethoxybenzoyl) - (2,4,4-trimethylpentyl) - (2-isopropyl propionate) phosphine oxide; (2,6-dimethoxybenzoyl) - (2,4,4-trimethylpentyl) - (2-isobutyl propionate) phosphine oxide; (2,6-dimethoxybenzoyl) - (2,4,4-trimethylpentyl) - (2-amyl propionate) phosphine ooxide; (2,6-dimethoxybenzoyl) - (2,4,4-trimethylpentyl) - (2-ethylhexyl propionate) phosphine oxide; (2,6-dimethoxybenzoyl) - (2,4,4-trimethylpentyl) - (tert-butyl 2-propionate) phosphine oxide; ooxide

ES 2 194 584 A1 (2,6-dimethoxybenzoyl) - (2,4,4-trimethylpentyl) - (1-methylpropyl 2-propionate) phosphine; (2,6-dimethoxybenzoyl) - (2,4,4-trimethylpentyl) - (2-isopentyl propionate) phosphine ooxide; (2,6-dimethoxybenzoyl) - (2,4,4-trimethylpentyl) - (2-methoxyethoxy propionate) phosphine oxide; (2,6-dimethoxybenzoyl) - (2,4,4-trimethylpentyl) - (2-benzyl propionate) phosphine oxide; (2,6-dimethoxybenzoyl) (2,4,4-trimethylpentyl) - (2,4,4-trimethylpentyl 2-propionate) phosphine ooxide; 2,6-dimethoxybenzoyl - (2,4,4-trimethylpentyl) - (methyl acetate) phosphine oxide; 2,6-dimethoxybenzoyl - (2,4,4-trimethylpentyl) - (ethyl acetate) phosphine oxide; 2,6-dimethoxybenzoyl - (2,4,4-trimethylpentyl) - (propyl acetate) phosphine ooxide; 2,6-dimethoxybenzoyl - (2,4,4-trimethylpentyl) - (butyl acetate) phosphine oxide; 2,6-dimethoxybenzoyl - (2,4,4-trimethylpentyl) - (pentyl acetate) phosphine ooxide; 2,6-dimethoxybenzoyl - (2,4,4-trimethylpentyl) - (hexyl acetate) phosphine oxide; 2,6-dimethoxybenzoyl - (2,4,4-trimethylpentyl) - (octyl acetate) phosphine ooxide; 2,6-dimethoxybenzoyl - (2,4,4-trimethylpentyl) - (decyl acetate) phosphine oxide; 2,6-dimethoxybenzoyl - (2,4,4-trimethylpentyl) - (dodecyl acetate) phosphine oxide; 2,6-dimethoxybenzoyl - (2,4,4-trimethylpentyl) - (isopropyl acetate) phosphine oxide; 2,6-dimethoxybenzoyl - (2,4,4-trimethylpentyl) - (isobutyl acetate) phosphine ooxide; 2,6-dimethoxybenzoyl - (2,4,4-trimethylpentyl) - (amyl acetate) phosphine ooxide; (2,6-dimethoxybenzoyl) - (2,4,4-trimethylpentyl) - (2-ethylhexyl acetate) phosphine oxide; 2,6-dimethoxybenzoyl - (2,4,4-trimethylpentyl) - (tert-butyl acetate) phosphine ooxide; (2,6-dimethoxybenzoyl) - (2,4,4-trimethylpentyl) - (1-methylpropyl acetate) phosphine oxide; 2,6-dimethoxybenzoyl - (2,4,4-trimethylpentyl) - (isopentyl acetate) phosphine oxide; 2,6-dimethoxybenzoyl - (2,4,4-trimethylpentyl) (methoxyethoxy acetate) phosphine ooxide; 2,6-dimethoxybenzoyl - (2,4,4 trimethylpentyl) - (benzyl acetate) phosphine ooxide; (2,6-dimethoxybenzoyl) - (2,4,4-trimethylpentyl) (2,4,4-trimethylpentyl acetate) phosphine ooxide; (2,4,6-Trimethylbenzoyl) -cyclopentyl-methylphosphine oxide; (2,4,6-Trimethylbenzoyl) -cyclopentyl-ethylphosphine oxide; (2,4,6-trimethylbenzoyl) -cyclopentyl-propylphosphine ooxide; (2,4,6-trimethylbenzoyl) -cyclopentyl-butylphosphine ooxide; (2,4,6-trimethylbenzoyl) -cyclopentyl-pentylphosphine ooxide; (2,4,6-Trimethylbenzoyl) -cyclopentyl-hexylphosphine ooxide; (2,4,6-Trimethylbenzoyl) -cyclopentyl-heptylphosphine ooxide; (2,4,6-trimethylbenzoyl) -cyclopentyl octylphosphine ooxide; (2,4,6-trimethylbenzoyl) -cyclopentyl-dodecylphosphine oxide; (2,4,6-Trimethylbenzoyl) -cyclopentyl-isopropylphosphine ooxide; (2,4,6-Trimethylbenzoyl) -cyclopentyl-isobutylphosphine ooxide; (2,4,6-Trimethylbenzoyl) -cyclopentyl-amylphosphine ooxide; (2,4,6-Trimethylbenzoyl) -cyclopentyl - (2-ethyl-hexyl) phosphine ooxide; (2,4,6-trimethylbenzoyl) -cyclopentyl - (tert-butyl) phosphine oxide; (2,4,6-Trimethylbenzoyl) -cyclopentyl - (1-methylpropyl) phosphine ooxide; (2,4,6-trimethylbenzoyl) -cyclopentyl-isopentylphosphine ooxide; (2,4,6-Trimethylbenzoyl) -cyclopentyl-methoxyethoxyphosphine oxide; (2,4,6-Trimethylbenzoyl) -cyclopentyl-benzylphosphine ooxide; (2,4,6-Trimethylbenzoyl) -cyclopentyl- (2,4,4-trimethylpentyl) phosphine ooxide; (2,4,6-trimethylbenzoyl) -cyclopentyl - (methyl 2-propionate) phosphine ooxide; (2,4,6-Trimethylbenzoyl) -cyclopentyl - (2-ethyl propionate) phosphine ooxide; (2,4,6-Trimethylbenzoyl) -cyclopentyl - (2-propyl propionate) phosphine oxide; (2,4,6-trimethylbenzoyl) -cyclopentyl - (2-butyl propionate) phosphine ooxide; (2,4,6-Trimethylbenzoyl) -cyclopentyl- (2-pentyl propionate) phosphine ooxide; (2,4,6-Trimethylbenzoyl) -cyclopentyl - (hexyl 2-propionate) phosphine ooxide; (2,4,6-trimethylbenzoyl) -cyclopentyl - (octyl 2-propionate) phosphine oxide; (2,4,6-trimethylbenzoyl) cyclopentyl - (decyl 2-propionate) phosphine oxide; (2,4,6-trimethylbenzoyl) -cyclopentyl - (2-dodecyl propionate) phosphine ooxide; (2,4,6-Trimethylbenzoyl) -cyclopentyl - (isopropyl 2-propionate) phosphine oxide; (2,4,6-Trimethylbenzoyl) -cyclopentyl - (isobutyl 2-propionate) phosphine ooxide; (2,4,6-trimethylbenzoyl) -cyclopentyl - (2-amyl propionate) phosphine ooxide; (2,4,6-Trimethylbenzoyl) -cyclopentyl - (2-ethylhexyl 2-propionate) phosphine oxide; (2,4,6-Trimethylbenzoyl) -cyclopentyl - (tert-butyl 2-propionate) phosphine oxide; (2,4,6-Trimethylbenzoyl) -cyclopentyl - (1-methylpropyl 2-propionate) phosphine oxide; (2,4,6-trimethylbenzoyl) -cyclopentyl - (isopentyl 2-propionate) phosphine ooxide; (2,4,6-Trimethylbenzoyl) -cyclopentyl - (2-methoxyethoxy propionate) phosphine ooxide; (2,4,6-trimethylbenzoyl) -cyclopentyl - (2-benzyl propionate) phosphine ooxide; (2,4,6-Trimethylbenzoyl) -cyclopentyl- (2,4,4-trimethylpentyl-2-propionate) phosphine oxide; (2,4,6-Trimethylbenzoyl) -cyclopentyl- (methyl acetate) phosphine ooxide; 2,4,6-trimethylbenzoyl-cyclopentyl - (ethyl acetate) phosphine oxide; 2,4,6-trimethylbenzoyl-cyclopentyl- (propyl acetate) phosphine ooxide; 2,4,6-trimethylbenzoyl-cyclopentyl - (butyl acetate) phosphine ooxide; 2,4,6-trimethylbenzoyl-cyclopentyl - (pentyl acetate) phosphine ooxide; ooxide

2,4,6-trimethylbenzoyl-cyclopentyl - (hexyl acetate) phosphine; 2,4,6-trimethylbenzoyl-cyclopentyl - (octyl acetate) phosphine ooxide; 2,4,6-trimethylbenzoyl-cyclopentyl- (decyl acetate) phosphine ooxide; 2,4,6-trimethylbenzoyl-cyclopentyl - (dodecyl acetate) phosphine ooxide; 2,4,6-trimethylbenzoyl-cyclopentyl - (isopropyl acetate) phosphine ooxide; 2,4,6-trimethylbenzoyl-cyclopentyl - (isobutyl acetate) phosphine ooxide; 2,4,6-trimethylbenzoyl-cyclopentyl - (amyl acetate) phosphine ooxide; (2,4,6-Trimethylbenzoyl) -cyclopentyl- (2-ethylhexyl acetate) phosphine oxide; (2,4,6-trimethylbenzoyl) cyclopentyl - (tert-butyl acetate) phosphine ooxide; (2,4,6-Trimethylbenzoyl) -cyclopentyl - (1-methylpropyl acetate) phosphine oxide; 2,4,6-trimethylbenzoyl-cyclopentyl- (isopentyl acetate) phosphine oxide; 2,4,6-trimethylbenzoyl-cyclopentyl - (methoxyethoxy acetate) phosphine oxide; 2,4,6-trimethylbenzoyl cyclopentyl - (benzyl acetate) phosphine ooxide; (2,4,6-Trimethylbenzoyl) -cyclopentyl - (acetate

ES 2 194 584 A1

2,4,4-trimethylpentyl) phosphine; 2,6-dimethoxybenzoyl-cyclopentyl-methylphosphine ooxide; 2,6-dimethoxybenzoyl-cyclopentyl-ethylphosphine ooxide; 2,6-dimethoxybenzoyl-cyclopentyl-propylphosphine oxide; ooxide

2,6-dimethoxybenzoyl-cyclopentyl-butylphosphine; 2,6-dimethoxybenzoyl-cyclopentyl-pentylphosphine oxide; 2,6-dimethoxybenzoyl-cyclopentyl-hexylphosphine ooxide; 2,6-dimethoxybenzoyl-cyclopentyl heptylphosphine ooxide; 2,6-dimethoxybenzoyl-cyclopentyl-octylphosphine oxide; 2,6-dimethoxybenzoyl-cyclopentyl-dodecylphosphine ooxide; 2,6-dimethoxybenzoyl-cyclopentyl-isopropylphosphine ooxide; ooxide

2,6-dimethoxybenzoyl-cyclopentyl-isobutylphosphine; 2,6-dimethoxybenzoyl-n-butylamylphosphine oxide; (2,6-dimethoxybenzoyl) -cyclopentyl - (2-ethylhexyl) phosphine oxide; 2,6-dimethoxybenzoyl-cyclopentyl - (tert-butyl) phosphine ooxide; (2,6-Dimethoxybenzoyl) -cyclopentyl- (1-methylpropyl) phosphine ooxide; ooxide

2.6-dimethoxybenzoyl-cyclopentyl-isopentylphosphine; 2,6-dimethoxybenzoylcyclopentyl-methoxyethoxyphosphine oxide; 2,6-dimethoxybenzoyl-cyclopentyl-benzylphosphine oxide; (2,6-dimethoxybenzoyl) cyclopentyl - (2,4,4-trimethylpentyl) phosphine ooxide; (2,6-dimethoxybenzoyl) -cyclopentyl - (methyl 2-propionate) phosphine oxide; (2,6-dimethoxybenzoyl) -cyclopentyl - (2-ethyl propionate) phosphine ooxide; (2,6-dimethoxybenzoyl) -cyclopentyl- (2-propyl propionate) phosphine ooxide; (2,6-dimethoxybenzoyl) cyclopentyl - (2-butyl propionate) phosphine ooxide; (2,6-dimethoxybenzoyl) cyclopentyl - (2-pentyl propionate) phosphine ooxide; (2,6-Dimethoxybenzoyl) -cyclopentyl- (2-hexyl propionate) phosphine oxide; (2,6-dimethoxybenzoyl) -cyclopentyl (2-octyl propionate) phosphine ooxide; (2,6-dimethoxybenzoyl) -cyclopentyl - (decyl 2-propionate) phosphine ooxide; (2,6-dimethoxybenzoyl) -cyclopentyl - (2-dodecyl propionate) phosphine ooxide; (2,6-dimethoxybenzoyl) cyclopentyl - (isopropyl 2-propionate) phosphine ooxide; (2,6-Dimethoxybenzoyl) -cyclopentyl- (2-isobutyl propionate) phosphine oxide; (2,6-dimethoxybenzoyl) -cyclopentyl- (2-amyl propionate) phosphine ooxide; (2,6-Dimethoxybenzoyl) -cyclopentyl - (2-ethylhexyl 2-propionate) phosphine ooxide; (2,6-dimethoxybenzoyl) -cyclopentyl (tert-butyl 2-propionate) phosphine oxide; (2,6-Dimethoxybenzoyl) -cyclopentyl - (1-methylpropyl 2-propionate) phosphine oxide; (2,6-Dimethoxybenzoyl) -cyclopentyl- (2-isopentyl propionate) phosphine ooxide; (2,6-Dimethoxybenzoyl) -cyclopentyl - (2-methoxyethoxy propionate) phosphine ooxide; (2,6-Dimethoxybenzoyl) -cyclopentyl - (2-benzyl propionate) phosphine ooxide; (2,6-Dimethoxybenzoyl) -cyclopentyl (2,4,4-trimethylpentyl 2-propionate) phosphine ooxide; 2,6-dimethoxybenzoyl-cyclopentyl- (methyl acetate) phosphine ooxide; 2,6-dimethoxybenzoyl-cyclopentyl- (ethyl acetate) phosphine ooxide; 2,6-dimethoxybenzoyl-cyclopentyl- (propyl acetate) phosphine ooxide; 2,6-dimethoxybenzoyl-cyclopentyl (butyl acetate) phosphine ooxide; 2,6-dimethoxybenzoyl-cyclopentyl- (pentyl acetate) phosphine oxide; 2,6-dimethoxybenzoyl-cyclopentyl- (hexyl acetate) phosphine oxide; 2,6-dimethoxybenzoyl-cyclopentyl- (octyl acetate) phosphine oxide; 2,6-dimethoxybenzoyl-cyclopentyl- (decyl acetate) phosphine oxide; 2,6-dimethoxybenzoyl-cyclopentyl - (dodecyl acetate) phosphine ooxide; 2,6-dimethoxybenzoyl-cyclopentyl- (isopropyl acetate) phosphine ooxide; 2,6-dimethoxybenzoyl-cyclopentyl (isobutyl acetate) phosphine ooxide; 2,6-dimethoxybenzoyl-cyclopentyl- (amyl acetate) phosphine ooxide; (2,6-Dimethoxybenzoyl) -cyclopentyl- (2-ethylhexyl acetate) phosphine ooxide; 2,6-dimethoxybenzoyl cyclopentyl - (tert-butyl acetate) phosphine ooxide; (2,6-Dimethoxybenzoyl) -cyclopentyl- (1-methylpropyl acetate) phosphine oxide; 2,6-dimethoxybenzoyl-cyclopentyl- (isopentyl acetate) phosphine oxide; 2,6-dimethoxybenzoyl-cyclopentyl- (methoxyethoxy acetate) phosphine ooxide; 2,6-dimethoxybenzoyl-cyclopentyl- (benzyl acetate) phosphine ooxide; (2,6-dimethoxybenzoyl) -cyclopentyl- (acetate

2,4,4-trimethylpentyl) phosphine; 2,4,6-trimethylbenzoyl-cyclohexyl-methylphosphine oxide; 2,4,6-trimethylbenzoyl-cyclohexyl-ethylphosphine ooxide; 2,4,6-trimethylbenzoyl-cyclohexyl-propylphosphine oxide; oxide

2.4.6-trimethylbenzoyl-cyclohexyl-butylphosphine; 2,4,6-trimethylbenzoyl-cyclohexyl-pentylphosphine ooxide; 2,4,6-trimethylbenzoyl-cyclohexyl-hexylphosphine oxide; 2,4,6-trimethylbenzoyl-cyclohexyl heptylphosphine ooxide; 2,4,6-trimethylbenzoyl-cyclohexyl-octylphosphine ooxide; 2,4,6-trimethylbenzoyl-cyclohexyl-dodecylphosphine ooxide; 2,4,6-trimethylbenzoyl-cyclohexyl-isopropylphosphine oxide; ooxide

2,4,6-trimethylbenzoyl-cyclohexyl-isobutylphosphine; 2,4,6-trimethylbenzoyl-cyclohexyl-amylphosphine ooxide; (2,4,6-trimethylbenzoyl) -cyclohexyl - (2-ethylhexyl) phosphine ooxide; (2,4,6-trimethylbenzoyl) -cyclohexyl - (tert-butyl) phosphine ooxide; (2,4,6-trimethylbenzoyl) cyclohexyl - (1-methylpentyl) phosphine ooxide; ooxide

2,4,6-trimethylbenzoyl-cyclohexyl-isopentylphosphine; 2,4,6-trimethylbenzoyl-cyclohexyl-methoxyethoxyphosphine ooxide; 2,4,6-trimethylbenzoyl-cyclohexyl-benzylphosphine oxide; (2,4,6-trimethylbenzoyl) cyclohexyl - (2,4,4-trimethylpentyl) phosphine ooxide; (2,4,6-trimethylbenzoyl) cyclohexyl - (methyl 2-propionate) phosphine oxide; (2,4,6-trimethylbenzoyl) -cyclohexyl- (ethyl 2-propionate) phosphine ooxide; (2,4,6-Trimethylbenzoyl) -cyclohexyl - (2-propyl propionate) phosphine ooxide; (2,4,6-trimethylbenzoyl) cyclohexyl - (2-butyl propionate) phosphine ooxide; (2,4,6-trimethylbenzoyl) -cyclohexyl- (2-pentyl propionate) phosphine ooxide; (2,4,6-trimethylbenzoyl) cyclohexyl - (hexyl 2-propionate) phosphine ooxide; (2,4,6-trimethylbenzoyl) -cyclohexyl - (octyl 2-propionate) phosphine ooxide; (2,4,6-trimethylbenzoyl) cyclohexyl - (decyl 2-propionate) phosphine ooxide; (2,4,6-Trimethylbenzoyl) -cyclohexyl- (2-dodecyl propionate) phosphine oxide; (2,4,6-Trimethylbenzoyl) -cyclohexyl- (isopropyl 2-propionate) phosphine oxide; (2,4,6-trimethylbenzoyl) -cyclohexyl- (isobutyl 2-propionate) phosphine oxide; (2,4,6-trimethylbenzoyl) -cyclohexyl- (2-amyl propionate) phosphine ooxide; (2,4,6-trimethylbenzoyl) -cyclohe36 ooxide

ES 2 194 584 A1 xyl - (2-ethylhexyl 2-propionate) phosphine; (2,4,6-trimethylbenzoyl) -cyclohexyl - (tert-butyl 2-propionate) phosphine oxide; (2,4,6-Trimethylbenzoyl) -cyclohexyl - (1-methylpropyl 2-propionate) phosphine ooxide; (2,4,6-trimethylbenzoyl) -cyclohexyl - (isopentyl 2-propionate) phosphine ooxide; (2,4,6-trimethylbenzoyl) -cyclohexyl - (2-methoxyethoxy propionate) phosphine ooxide; (2,4,6-Trimethylbenzoyl) -cyclohexyl - (2-benzyl propionate) phosphine oxide; (2,4,6-trimethylbenzoyl) -cyclohexyl (2,4,4-trimethylpentyl 2-propionate) phosphine ooxide; 2,4,6-trimethylbenzoyl-cyclohexyl- (methyl acetate) phosphine ooxide; 2,4,6-trimethylbenzoyl-cyclohexyl- (ethyl acetate) phosphine oxide; 2,4,6-trimethylbenzoyl-cyclohexyl- (propyl acetate) phosphine oxide; 2,4,6-trimethylbenzoyl-cyclohexyl- (butyl acetate) phosphine oxide; 2,4,6-trimethylbenzoyl-cyclohexyl- (pentyl acetate) phosphine oxide; ooxide

2,4,6-trimethylbenzoyl-cyclohexyl - (hexyl acetate) phosphine; 2,4,6-trimethylbenzoyl-cyclohexyl (octyl acetate) phosphine oxide; 2,4,6-trimethylbenzoyl-cyclohexyl- (decyl acetate) phosphine oxide; oxide

2.4.6-trimethylbenzoyl-cyclohexyl - (dodecyl acetate) phosphine; 2,4,6-trimethylbenzoyl-cyclohexyl- (isopropyl acetate) phosphine oxide; 2,4,6-trimethylbenzoyl-cyclohexyl (isobutyl acetate) phosphine oxide; 2,4,6-trimethylbenzoyl-cyclohexyl- (amyl acetate) phosphine ooxide; (2,4,6-trimethylbenzoyl) cyclohexyl - (2-ethylhexyl acetate) phosphine oxide; (2,4,6-trimethylbenzoyl) -cyclohexyl- (tert-butyl acetate) phosphine oxide; (2,4,6-Trimethylbenzoyl) -cyclohexyl- (1-methylpropyl acetate) phosphine ooxide; 2,4,6-trimethylbenzoyl-cyclohexyl- (isopentyl acetate) phosphine oxide; 2,4,6-trimethylbenzoyl-cyclohexyl- (methoxyethoxy acetate) phosphine oxide; 2,4,6-trimethylbenzoyl-cyclohexyl- (benzyl acetate) phosphine oxide; (2,4,6-Trimethylbenzoyl) -cyclohexyl- (2,4,4-trimethylpentyl acetate) phosphine oxide; 2,6-dimethoxybenzoyl-cyclohexyl-methylphosphine ooxide; 2,6-dimethoxybenzoyl-cyclohexyl-ethylphosphine ooxide; 2,6-dimethoxybenzoyl-cyclohexyl-propylphosphine ooxide; 2,6-dimethoxybenzoyl-cyclohexyl-butylphosphine ooxide; 2,6-dimethoxybenzoyl-cyclohexyl-pentylphosphine ooxide; 2,6-dimethoxybenzoyl-cyclohexyl-hexylphosphine ooxide; 2,6-dimethoxybenzoyl-cyclohexyl-heptylphosphine oxide; ooxide

2.6-dimethoxybenzoyl-cyclohexyl-octylphosphine; 2,6-dimethoxybenzoyl-cyclohexyl-dodecylphosphine oxide; 2,6-dimethoxybenzoyl-cyclohexyl-isopropylphosphine ooxide; 2,6-dimethoxybenzoyl-cyclohexyl-isobutylphosphine ooxide; 2,6-dimethoxybenzoyl-n-butylamylphosphine oxide; (2,6-Dimethoxybenzoyl) -cyclohexyl - (2-ethylhexyl) phosphine ooxide; 2,6-dimethoxybenzoyl-cyclohexyl - (tert-butyl) phosphine ooxide; (2,6-Dimethoxybenzoyl) -cyclohexyl - (1-methylpropyl) phosphine oxide; 2,6-dimethoxybenzoyl cyclohexyl-isopentylphosphine ooxide; 2,6-dimethoxybenzoyl-cyclohexyl-methoxyethoxyphosphine oxide; ooxide

2,6-dimethoxybenzoyl-cyclohexyl-benzylphosphine; (2,6-Dimethoxybenzoyl) -cyclohexyl - (2,4,4-trimethylpentyl) phosphine oxide; (2,6-dimethoxybenzoyl) -cyclohexyl - (methyl 2-propionate) phosphine oxide; (2,6-dimethoxybenzoyl) -cyclohexyl - (ethyl 2-propionate) phosphine ooxide; (2,6-dimethoxybenzoyl) cyclohexyl - (propyl 2-propionate) phosphine ooxide; (2,6-Dimethoxybenzoyl) -cyclohexyl- (2-butyl propionate) phosphine ooxide; (2,6-Dimethoxybenzoyl) -cyclohexyl- (2-pentyl propionate ) phosphine ooxide; (2,6-dimethoxybenzoyl) -cyclohexyl - (hexyl 2-propionate) phosphine ooxide; (2,6-dimethoxybenzoyl) -cyclohexyl - (octyl 2-propionate) phosphine ooxide; (2,6-Dimethoxybenzoyl) -cyclohexyl - (decyl 2-propionate) phosphine ooxide; (2,6-Dimethoxybenzoyl) -cyclohexyl- (2-dodecyl propionate) phosphine ooxide; (2,6-dimethoxybenzoyl) -cyclohexyl - (isopropyl 2-propionate) phosphine ooxide; (2,6-dimethoxybenzoyl) cyclohexyl - (isobutyl 2-propionate) phosphine ooxide; (2,6-Dimethoxybenzoyl) -cyclohexyl - (2-amyl propionate) phosphine ooxide; (2,6-Dimethoxybenzoyl) -cyclohexyl - (2-ethylhexyl 2-propionate) phosphine oxide; (2,6-dimethoxybenzoyl) -cyclohexyl - (tertbutyl 2-propionate) phosphine oxide; (2,6-Dimethoxybenzoyl) -cyclohexyl - (1-methylpropyl 2-propionate) phosphine oxide; (2,6-dimethoxybenzoyl) -cyclohexyl- (isopentyl 2-propionate) phosphine ooxide; (2,6-Dimethoxybenzoyl) -cyclohexyl - (2-methoxyethoxy propionate) phosphine oxide; (2,6-Dimethoxybenzoyl) -cyclohexyl- (2-benzyl propionate) phosphine ooxide; (2,6-Dimethoxybenzoyl) -cyclohexyl - (2,4,4-trimethylpentyl 2-propionate) phosphine oxide; ooxide

2,6-dimethoxybenzoyl-cyclohexyl - (methyl acetate) phosphine; 2,6-dimethoxybenzoyl-cyclohexyl (ethyl acetate) phosphine oxide; 2,6-dimethoxybenzoyl-cyclohexyl- (propyl acetate) phosphine oxide; ooxide

2,6-dimethoxybenzoyl-cyclohexyl - (butyl acetate) phosphine; 2,6-dimethoxybenzoyl-cyclohexyl (pentyl acetate) phosphine oxide; 2,6-dimethoxybenzoyl-cyclohexyl- (hexyl acetate) phosphine oxide; 2,6-dimethoxybenzoyl-cyclohexyl- (octyl acetate) phosphine oxide; 2,6-dimethoxybenzoyl-cyclohexyl- (decyl acetate) phosphine oxide; 2,6-dimethoxybenzoyl-cyclohexyl- (dodecyl acetate) phosphine oxide; 2,6-dimethoxybenzoyl-cyclohexyl- (isopropyl acetate) phosphine ooxide; 2,6-dimethoxybenzoyl-cyclohexyl- (isobutyl acetate) phosphine oxide; 2,6-dimethoxybenzoyl-cyclohexyl- (amyl acetate) phosphine ooxide; (2,6-Dimethoxybenzoyl) -cyclohexyl- (2-ethylhexyl acetate) phosphine oxide; ooxide

2,6-dimethoxybenzoyl-cyclohexyl - (tert-butyl acetate) phosphine; (2,6-dimethoxybenzoyl) cyclohexyl- (1-methylpropyl acetate) phosphine oxide; 2,6-dimethoxybenzoyl-cyclohexyl- (isopentyl acetate) phosphine oxide; 2,6-dimethoxybenzoylcyclohexyl- (methoxyethoxy acetate) phosphine oxide; oxide

2,6-dimethoxybenzoyl-cyclohexyl - (benzyl acetate) phosphine; (2,6-Dimethoxybenzoyl) -cyclohexyl- (2,4,4-trimethylpentyl acetate) phosphine ooxide.

Compounds of formula I, where R is Z, are obtained by reaction of a corresponding compound37

ES 2 194 584 A1 tooth of formula I, where R is M, with a compound Z1 -X (VI), the compound of formula I being prepared first, where R is Z1, where x = 0 (III '):

<img file="ES2194584A1_D0057.tif" />

Ar, M, X and R6 have the meanings defined above and in the claims. Z1 has the meaning defined for Z1 in claim 1, with the exception of groups (v), (w) and C1-C24 alkylthio. (The obtaining of compounds of formula I, where R is Z1, where Z1 is a group (v), (w) or C1-C24 alkylthio is described later.)

If you want to obtain compounds of the formula I, where R is Z1, in which A = O or S, then an oxidation or sulfuration of the compound of the formula (III ') was carried out, either after having separated the compounds of the formula (III ') by usual methods, either without isolating them. The conditions of such reactions are similar to those described for obtaining the compounds of formula I, where R is or

II.

-c-η

If a compound of formula (III) is desired in which Z₁ be a rest

<img file="ES2194584A1_D0058.tif" />

or C1-C24 alkylthio, then the compound of the formula (I), where R is M, is reacted with a compound of the formula Z1-SO2-X, with which a compound of Formula I, where R is Z1, where A = O and x = 1. (Z1 has been defined above, X is defined in the claims.) Therefore, it is unnecessary to carry out the oxidation step.

Similar reactions are described for example in Houben-Weyl, E2, Methoden der organischen Chemie, 4^to edition, pages 222-225.

If compounds of the formula I are to be obtained, where R is Z1, where Z1 is a residue (v) or (w) or C1-C24 alkylthio, and where A is sulfur, then it is possible for example to convert the compound oxide in the corresponding sulfide, as described above. This is possible for example by reacting the corresponding phosphine oxide with an excess of P2S5 or with elemental sulfur in a high-boiling solvent. Such reactions, ie reactions in which the P = O bond is converted to a P = S bond, are described for example in L. Horner et al., Chem. Ber. 92, 2088 (1959) and in US-2642461. In principle it is also possible to first reduce the phosphine oxide compound in question to obtain the corresponding phosphine and then sulfurize the phosphine, that is, the P = O bond is reduced to obtain phosphine using an ideal reducing agent and then sulfurized. with elemental sulfur to obtain the P = S bond. Reducing agents which can be employed are for example LiAlH4, Ca (AlH4) 2, CaH2, AlH3, SiHCl3, PhSiH3 and the agents described in "Organic Phosphorus Compounds", Wiley-Interscience 1972, vol. 1, pages 45-46 and vol. 3, pages 408-413.

ES 2 194 584 A1

The object of the invention is a procedure for obtaining compounds of formula I, where R is Z1, starting from new materials of formula I, where R is M, (1) by reaction of an acyl halide of formula IV or

II

Ar — C — X (IV), where Ar has the meaning defined before and

XesCloBr;

with a dimethalated organylphosphine of the formula V

<img file="ES2194584A1_D0059.tif" />

in which R6 has the meaning defined before and

M1 is Na, LioK in an approximate molar ratio of 1: 1;

(2) subsequent reaction of the product with a compound of the formula VI or VI '

Z1 - X (VI) Z1 - X 'in which Z1 has the meaning defined above 3 and

X has the meaning defined before and (VI ')

OR

X 'is -N = C = A, -N = C = N = Zi, - C-CH H ² eight;

with the condition that Z1 is not identical to the rest R6; in an approximate molar ratio of 1: 1; and (3) in the case that Z1 is neither group (v), (w) nor C1-C12 alkylthio and if it is desired to obtain compounds of the formula I, where R is Z, in which A is oxygen or sulfur , subsequent oxidation or sulfuration of the resulting phosphine compounds.

Another object of the invention is a procedure for obtaining the compound of formula I, where R is Z1, by (1) reaction of an acyl halide of formula IV

OR

II

Ar — C — X (IV) where Ar has the meaning defined above and XesCloBr;

with an asymmetric phosphine of formula VII

ES 2 194 584 A1

<img file="ES2194584A1_D0060.tif" />

wherein R6 has the meaning defined above and Z1 has the meaning defined above, provided that R6 and Z1 are not identical;

in an approximate molar ratio of 1: 1, in the presence of a base or an organic lithium compound, to obtain the corresponding acylphosphine and (2) subsequent oxidation or sulfuration of the acylphosphine thus obtained.

This process of obtaining is new and constitutes also an object of the invention.

Suitable bases for this process are, for example, organic lithium compounds, such as butyllithium, or organic nitrogenous bases, for example tertiary amines or pyridine.

Compounds of formula I, where R is Z1, can also be obtained by reacting the compound of formula I, where R is M, with phosgene according to the description of "WA Henderson et al. in J. Am. Chem. Soc. 1960, 82, 5794 "or from" GB 904 086 "or from" Organic Phosphorous Compounds, coordinators: RM Kosolapoff and L. Maier, Wiley-Interscience 1972, vol. 1, page 28 "or from" Houben-Weyl, Methoden der Organischen Chemie, vol. XII / 1, page 201 ", obtaining the corresponding phosphine chloride (I i). As described in "Organic Phosphorous Compounds, coordinators: RM Kosolapoff and L. Maier, Wiley-Interscience 1972, vol. 4, pages 268-269 ", the compounds of the formula (Ii) can be reacted with alcohols to obtain the compounds of the formula (Iii) which then react directly with an organic halide of the formula VI by a method similar to that described in "K. Sasse in Houben-Weyl, Methoden der organischen Chemie, vol. XII / 1, page 433 ”(Michaelis-Arbuzov reaction) to yield the compounds of formula III. In this case, the oxidation or sulfurization stage is not required.

<img file="ES2194584A1_D0061.tif" />

Ar and Z1 have the meaning defined in claim 1; X is Cl or Br; R6 and M have the meaning defined in claim 1 and Ro is any alcohol residue, eg C1-C12 alkyl, C5-C8 cycloalkyl, eg cyclopentyl or cyclohexyl or benzyl.

The reaction conditions of the compounds of formula (I) and formula (Ii) formula (Iii) are similar to those described above for obtaining compounds of formula I by this procedure, where R is O.

-cY,

The conversion of the compounds of the formula (Iii) into the compounds of the formula (III) is carried out by adding the alkyl halides (Z1-X) corresponding to a solution of the compounds of the formula (Iii) in an inert solvent. In such a case, the alkyl halide is advantageously dissolved in, for example, the same solvent. The addition is carried out, for example, at a temperature between 40 and 140 ° C, preferably between 60 and 120 ° C, the low-boiling alkyl halide (RX) which

ES 2 194 584 A1 is released during the reaction and is advantageously removed from the reaction solution by distillation. The solvents that can be used are, for example, alkanes, for example octane; cycloalkanes, for example cyclohexane; ethers, for example methyl tert-butyl ether, tetrahydrofuran, dioxane; or aromatic solvents, for example toluene or xylene. The compounds of structure (II) are isolated and purified, for example, by distillation under reduced pressure, crystallization or chromatography.

The compounds of the formula (Iii) can be oxidized with suitable oxidizing agents, for example peroxo acids, hydrogen peroxide or hydrogen peroxide / urea to obtain the corresponding phosphonic osesters (Iiii):

<img file="ES2194584A1_D0062.tif" />

Another object of the invention is a procedure for obtaining compounds of the formula I, where R is Z, in which A is oxygen and x is the number 1, by (1) reaction of a compound of the formula (I), where R is M,

<img file="ES2194584A1_D0063.tif" />

<img file="ES2194584A1_D0064.tif" />

in which Ar, M and R6 have the meanings defined above, with phosgene to obtain the corresponding phosphine chloride (Ii)

<img file="ES2194584A1_D0065.tif" />

(2) subsequently reacted with an alcohol to obtain the compound of formula (Iii)

<img file="ES2194584A1_D0066.tif" />

<img file="ES2194584A1_D0067.tif" />

where Ro is the residue of an alcohol, especially C1-C12 alkyl, C5 -C8 cycloalkyl or benzyl; and (3) reaction of the compound resulting from formula (Iii) with an organyl halide

Z1 -X in which Z1 has the meaning defined above, but is not identical to R6 of formula I, where R is M, and X is Clo Br,

ES 2 194 584 A1 to obtain the compound of formula I, where R is Z1.

It is conceivable to obtain compounds of formula III following the invention by another method, eg. using the procedures described in US-4298738 or US-4324744.

The invention also relates to the use of the compounds of formula I, where R is M, as starting materials for obtaining mono- or bisacyl phosphines, mono- or bisacylphosphine oxides or mono- or bisacylphosphine sulfides. .

Also preferred are compounds of formula I, in which

Ar is a group

<img file="ES2194584A1_D0068.tif" />

AesO;

xeselnumer 1;

R1 and R2 signify methyl; R3 is methyl;

R 4 and R5 are hydrogen;

R6 is C1-C4 alkyl; MesLi;

Z1 is a remainder

<img file="ES2194584A1_D0069.tif" />

Z3 is CH2; and

R19, ​​R20, R21, R22 and R23 are hydrogen.

The compounds of formula I are particularly preferred,

<img file="ES2194584A1_D0070.tif" />

ES 2 194 584 A1 in which Ar is a group

<img file="ES2194584A1_D0071.tif" />

Rl and R₂ independently of each other with C alkyl₁ -C₈ or OR₁₁;

R₃, R₄ and R₅ independently of each other are hydrogen or C alkyl₁-C₈; R6 is Cl-Cl2 alkyl;

R₁₁ is H or C alkyl₁ -C₈;

R12 and R13 independently of each other are hydrogen or C1-C8 alkyl;

M is hydrogen or Li;

AesO;

xeselnumber 1;

Y1 is OR11, N (R12) (R13) or a moiety

<img file="ES2194584A1_D0072.tif" />

R1 'and R2' independently of each other have the same meanings attributed to R1 and R2; and R3 ', R4' and R5 'independently of each other have the same meanings attributed to R3, R4 and R5; provided that Y1 is not identical to Ar;

Z1 is C1-C12 alkyl which is unsubstituted or substituted one or more times by OR15, phenyl and / or; obienZ1 is C3-C24 cycloalkyl unsubstituted or substituted by OR11; or Z1 is one of the remains

<img file="ES2194584A1_D0073.tif" />

Z3 is CH2 or CH (OH);

res0;

ses1;

E, G and G3 independently of one another are unsubstituted C1-C4 alkyl; R15 has one of the meanings attributed to R11;

ES 2 194 584 A1

R18 is C1-C12 alkyl; Y

R₁₉, R₂₀, R₂₁, R₂₂ yR₂₃ independently of each other they are hydrogen or halogen; and with the condition that R6 and Z1 are not identical.

Following the invention, the compounds of the formula I, where R is o

-CY_x or Z₁₍ They can be used as photoinitiators in the photopolymerization of compounds with ethyloenic unsaturations or of mixtures of said compounds.

This use can take place in combination with another photoinitiator and / or other additives.

The invention also relates to photopolymerizable compositions containing (a) at least one photopolymerizable compound provided with ethyloenic unsaturations and (b) as photoinitiator, at least one compound of formula I where R is

OR

-C-Yi or Z_1; the composition being able to contain, apart from component (b), other photoinitiators (c) and / or other additives (d).

In these compositions compounds of formula I are preferred where R is or

-C-Yi or Z_lz where x is number 1, especially those compounds where x is number 1 and A is oxygen. Especially preferred within such compositions are those compounds of formula I where R is or

-C-Yi or Z₁₍ in which Ar is a group

<img file="ES2194584A1_D0074.tif" />

ES 2 194 584 A1

A is oxygen and x is number 1.

Unsaturated compounds can have one or more olefinic double bonds. They can be low molecular weight (monomeric) or high molecular weight (oligomeric). Examples of monomer bearing a double bond are alkyl or hydroxyalkyl acrylates or methacrylates, for example methyl, ethyl, butyl, 2-ethylhexyl, 2-hydroxyethyl acrylate, isobornyl acrylate, methyl or ethyl methacrylate. Silicon- or fluorine-modified resins, eg silicone acrylates, are also of interest. Other examples are acrylonitrile, acrylamide, methacrylamide, N-substituted (meth) acrylamides, vinyl esters, for example vinyl acetate, vinyl ethers, for example isobutyl vinyl ether, styrene, ñps alkylstyrenes and halogen styrenes, N-vinylpyrrolidone, vinyl chloride, or vinylidene chloride.

Examples of monoamers bearing several double bonds are ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, hexamethylene glycol diacrylate or bisphenol A diacrylate, 4,4'-bis (2-acryloyloxyethoxy) triphenyl triphenylpropane triphenylpropane , pentaerythritol triacrylate or tetraacrylate, vinyl acrylate, divinylbenzene, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate or tris (2-acryloylethyl) isocyanurate.

Examples of high molecular weight polyunsaturated compounds (oligaomers) are acrylated epoxy resins, acrylated polyesters, polyesters containing vinyl ether groups or epoxy groups, and polyurethanes and polyaethers as well. Other examples of unsaturated oligamers are unsaturated polyester resins which are normally made from maleic acid, phthalic acid and one or more diols and have molecular weights between 500 and 3,000. It is also possible to use vinyl ether monomer and oligoamers as well as oligamers with terminal maleate groups, the main chains being polyesters, polyurethanes, polyethers, polyvinyl ether or epoxy. Combinations of oligaomers bearing vinyl ether groups with polymers described in WO 90/01512 are especially suitable. However, copolymers of vinyl ether with maleic acid functionalized monomer are also suitable. Unsaturated oligoamers of this type can also be called prepolymers.

Especially suitable examples are the esters of carboxylic acids provided with ethylanic unsaturations with polyols or polyepoxides and polymers having unsaturated groups in the chain or on the side groups, for example unsaturated polyesters, polyamides and polyurethanes and copolymers thereof. alkadic resins, polybutanediene, butadiene copolymers, polyisoprene and isoprene copolymers, polymers and copolymers containing (meth) acrylic acid groups in the side chains and also in mixtures of one or more of such polymers.

Examples of unsaturated carboxylic acids are acrylic acid, methacrylic acid, crothaonic acid, itaconic acid, cinnaamic acid and unsaturated fatty acids, for example linolenic acid or oleic acid. Acrylic and methacrylic acid are preferred.

Suitable polyols are aromatic polyols and especially aliphatic and cycloaliphatic polyols. Examples of aromatic polyols are hydroquinone, 4,4'-dihydroxydiphenyl, 2,2-di (4-hydroxyphenyl) -propane and also novolaks and resols. Examples of polyepoxides are those based on the above-mentioned polyols, especially aromatic polyols, and on epichlorohydrin. Other suitable polyols are polymers and copolymers containing hydroxyl groups in the main chain or in the side chains, examples of which are polyvinyl alcohol and its copolymers or poly (hydroxyalkyl methacrylate) or its copolymers. Other suitable polyols are oligoasters having terminal hydroxyl groups.

Examples of aliphatic and cycloaliphatic polyols are alkylenediols preferably having 2 to 12 C atoms, for example ethylene glycol, 1,2- or 1,3-propanediol, 1,2-, 1,3- or 1,4 -butanediol, pentanediol, hexanediol, octanediol, dodecanediol, diethylene glycol, triethylene glycol, polyethylene glycols preferably having molecular weights between 200 and 1,500, 1,3-cyclopentanediol, 1,2, 1,3 or 1,4- cyclohexanediol, 1,4-dihydroxymethylcyclohexane, glycerin, tris (e-hydroxyethyl) amine, trimethylolethane, trimethylolpropane, pentaerythrite, dipentaerythritol and sorbitol.

The polyols can be totally or partially esterified with a carboxylic acid or with different unsaturated carboxylic acids and the free hydroxyl groups of the partial asters can be modified, for example etherified or else esterified with other carboxylic acids.

Examples of asters are the following:

It is 2194584 A1 trimethylolpropane triacrylate, triacrylate trimethylolethane, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, dimethacrylate and tetramethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol diacrylate, dipentaerythritol triacrylate dipentaerythrite, dipentaerythritol tetraacrylate, dipentaerythrite pentacrylate, dipentaerythritol hexaacrylate, octaacrylate of tripentaerythritol dimethacrylate, dipentaerythritol trimethacrylate, pentaerythritol dimethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol, octametracrilato of tripentaerythritol, diitaconate, pentaerythritol, tris-itaconate, dipentaerythritol pentaitaconate, dipentaerythritol hexaitaconate dipentaerythritol, ethylene glycol diacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diitaconate, Sorbitol triacrylate, sorbitol tetraacrylate, modified pentaerythritol triacrylate, sorbitol tetramethacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, oligoether acrylates and methacrylates, glycerine diacrylate and triacrylate, and bis-glycerin 1,4-cyclohengylethacrylate, bis-cyclohetacrylate and polyacrylate acrylates a molecular weight between 200 and 1,500 and mixtures thereof.

Also suitable as component (a) are polyamides of unsaturated carboxylic acids, identical or different, with aromatic, cycloaliphatic or aliphatic polyamines, preferably having 2 to 6, especially 2 to 4 amino groups. Examples of such amines are ethylenediamine, 1,2- and 1,3-propylenediamine, 1,2-, 1,3- and 1,4-butylenediamine, 1,5-pentylenediamine, 1,6- hexylenediamine, octylenediamine, dodecylenediamine, 1,4-diaminocyclohexane, isophorondiamine, phenylenediamine, bisphenylenediamine, di-e-aminoethyl ether, diethylenetriamine, triethylenetetraamine, άϊ (β-aminoethoxy- - or aminopropoxy) -ethane. Other suitable polyamines are polymers and copolymers, preferably provided with additional amino groups in the side chain, and oligoamines having terminal amino groups. Examples of such unsaturated amides are methylenebisacrylamide, 1,6-hexamethylenebisacrylamide, diethylenetriaminetrismethacrylamide, bis (methacrylamidopropoxy) ethane, β-methacrylamidoethyl methacrylate and N [(e-hydroxyethoxy) ethyl] acrylamide.

Unsaturated polyesters and idine polyamides are derived, for example, from maleic acid and from diols or diamines. A part of the maleic acid can be replaced by other dicarboxylic acids. They can be used together with unsaturated co-monoimers, for example styrene. Polyesters and polyamides can also be derived from dicarboxylic acids and from unsaturated diols or diamines, especially those with relatively long chains, for example 6 to 20 atoms of C. Examples of polyurethanes are those obtained from saturated or unsaturated diisocyanates and from unsaturated or saturated diols.

Polybutadiene and polyisoprene and copolymers thereof are known. Suitable comonomers are, for example, olefins, such as ethylene, propene, butene, hexene, (meth) acrylates, acrylonitrile, styrene and. vinyl chloride. Polymers having (meth) acrylate groups in the side chains are also known. They can be obtained, for example, by reacting epoxy resins based on novolacs with (meth) acrylic acid or they can be derived from homo- or copolymers of vinyl alcohol or from hydroxyalkyl derivatives thereof which are esterified with (meth) acrylic acid or they can be homo or copolymers of (meth) acrylates esterified with hydroxyalkyl (meth) acrylates.

The photopolymerizable compounds can be used alone or in any type of mixture. The use of mixtures of polyol (meth) acrylates is preferred.

Binders can be added to the new compositions, this is particularly convenient when the photopolymerizable compounds are liquid or viscous substances. The amount of binder can be, for example, between 5 and 95%, preferably between 10 and 90% and in particular between 40 and 90% by weight, based on total solids. The choice of the binder will depend on the field of application and the properties required in it, for example the development capacity in organic and aqueous solvent systems, the adherence to the substrate and the sensitivity to oxygen.

Examples of suitable binders are polymers having a molecular weight between 5,000 and 2,000,000, preferably between 10,000 and 1,000,000. Examples of this are: homo- and copolymers of acrylates and methacrylates, eg. methyl methacrylate / ethyl acrylate / methacrylic acid copolymers, poly (alkyl methacrylates), poly (alkyl acrylates), cellulose esters and cellulose ethers, for example cellulose acetate, acetobutyrate cellulose, methylcellulose, ethylcellulose; polyvinylbutyral, polyvinylformal, cyclized rubber, polyethers of the type poly (ethylene oxide), poly (propylene oxide) and polytetrahydrofuran; polystyrenes, polycarbonates, polyurethanes, chlorinated polyolefins, polyvinyl chloride, vinyl chloride / vinylidene chloride copolymers, vinylidene chloride copolymers with acrylonitrile, methylene methacrylate and vinyl acetate, poly (acetate of vinyl), copoly (ethylene / vinyl acetate), polymers of the polycaprolactam type and poly (hexamethylene46

ES 2 194 584 A1 dipamide) and polyesters of the type poly (ethylene glycol terephthalate) and poly (hexamethylene glycol succinate).

Unsaturated compounds can also be used as a mixture with non-photopolymerizable film-forming components. These can be, for example, phosphically dried polyomers or solutions thereof in organic solvents, for example nitrocellulose or cellulose acetobutyrate. However, they can also be chemically or chemically crosslinking resins, for example polyisocyanates, polyepoxides or melamine resins. The simultaneous use of thermic crosslinking resins is important in hybrid systems, which in a first stage are photopolymerized and then crosslinked by a subsequent thermic treatment.

The photoinitiators of the invention are also suitable as initiators of the crosslinking of oxidative drying systems, described for example in Lehrbuch der Lacke und Beschichtungen (= Manual of paints and coatings), volume 111, 296-328, publishing house WA Colomb de la Heenemann GmbH, Berlin-Oberschwandorf (1976).

In addition to the photoinitiator, the photopolymerizable mixtures can include various additives (d). Examples of this are the thymic inhibitors, the purpose of which is to prevent premature polymerization; examples are hydroquinone, hydroquinone derivatives, p-methoxyphenol, β-naphthol or stoerically hindered phenols, for example 2,6-di-tert-butyl-p-cresol. To maximize the storage stability in the dark, it is possible to use copper compounds, for example copper naphthenate, stearate or octoate, phosphorus compounds, for example triphenylphosphine, tributylphosphine, triethyl phosphite, triphenyl phosphite or tribenzyl phosphite , quaternary ammonium compounds, for example tetramethylammonium chloride or trimethylbenzylammonium chloride, or hydroxylamine derivatives, for example N-diethylhydroxylamine. To exclude oxygen from the atmosphere during polymerization, it is possible to add paraffin or similar acidic substances that, due to their poor solubility in the polymer, migrate to the surface when polymerization begins and form a transparent surface layer that prevents air from entering. It is also possible to apply an oxygen-impermeable layer on the surface of the coating. Light stabilizers that can be added are UV absorbers, for example those of the hydroxyphenylbenzotriazole, hydroxyphenylbenzophenone, oxalamides or hydroxyphenyl-S-triazines type. These compounds can be used individually or in mixtures, with or without hindered amines (HALS).

Examples of such UV absorbers and light stabilizers are the following:

1. 2- (2'-hydroxyphenyl) benzotriazoles for example 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2 - (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2 - (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2 - (2'-hydroxy-5 '- (1,1,3,3 tetramethylbutyl) phenyl) benzotriazole, 2 - (3'-5' - di-tert-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2 - (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 2 - (3'-sec-butyl-5'-tert-butyl-2'-hydroxy-phenyl) benzotriazole, 2 - (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2 - (3 ', 5'-di - tertamyl-2'-hydroxyphenyl) benzotriazole, 2 - (3 ', 5'-bis - (α, α-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, mixture of 2- (3'-tert-butyl-2 '- hydroxy-5' - (2-octyloxycarbonylethyl) -phenyl) -5-chlorobenzotriazole, 2 - (3'-tert-butyl-5 '- [2 - (2-ethylhexyloxy) -carbonylethyl] -2'-hydroxyphenyl) -5-chlorobenzotriazole, 2 - (3'-tert-butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2 - (3'-tert-butyl-2'-hydroxy-5' - (2-methoxycarbonylethyl) phenyl) benzotriazole, 2 - (3'-tert-butyl 2'-hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2 - (3'-tert-butyl-5' - [2 - (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2 - (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (3'- tert-butyl- 2'- hydroxy-5'- (2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2'-methylene - bis [4 - (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-yl-phenol]; the transesterification product of 2 - [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) - 2'-hydroxy-phenyl] benzotriazole with polyethylene glycol 300; [R-CH2CH2 -COO- (CH2) 3] 2 - where R is 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2 yl-phenyl.

2. 2-hydroxybenzophenones for example the 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy and 2'-hydroxy-4,4' derivatives - dimethoxy.

3. Possibly substituted benzoic acid esters, for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcin, bis - (4-tert-butylbenzoyl) resorcin, benzoylresorcin, 3,5-di-tert-butyl-4 - hydroxybenzoate

ES 2 194 584 A1 of 2,4-di-tert-butylphenyl, 3,5-di-tert-butyl-4-hydroxybenzoate of hexadecyl, 3,5-di-tert-butyl-4-hydroxybenzoate of octadecyl, 3,5 2-methyl-4,6 di-tert-butylphenyl di-tert-butyl-4-hydroxybenzoate.

Four. Acrylates for example α - cyano - β, β - ethyl diphenylacrylate, α - cyano - β, β - isooctyl diphenylacrylate, α - methyl carbomethoxycinnamate, α - cyano - β - methyl - p - methyl methoxycinnamate, α - cyano - β-methyl-p-butyl methoxycinnamate, α-carbomethoxy-p-methoxycinnamate, and N - (β-carbomethoxy-β-cyanovinyl) -2-methylindoline.

5. Sterically hindered amines for example bis (2,2,6,6-tetramethyl-piperidyl) sebacate, bis (2,2,6,6-tetramethyl piperidyl) succinate, bis- (1,2,2,6 , 6-pentamethylpiperidyl), n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl-malonate of bis (1,2,2,6,6-pentamethylpiperidyl), the condensation product of 1 - hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succonic acid, the condensation product of N, N'- bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro 1,3,5-s-triazine, nitrile - tris (2,2,6,6-tetramethyl-4-piperidyl) triacetate, 1,2,3,4-tetrakis (2,2,6,6-tetramethyl-4-piperidyl) butane tetraoate, 1 , 1 '- (1,2-ethanediyl) bis - (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6 - tetramethylpiperidine, 2 - n-butyl-2 - (2-hydroxy-3,5-di-tert-butyl-benzyl) -malonate of bis (1,2,2,6,6-pentamethylpiperidyl), 3-n-octyl-7.7 , 9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, bis (1-octyloxy 2,2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy succinate - 2,2,6,6-tetramethylpiperidyl), the condensation product of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylenediamine with 4-morpholino-2,6 - dichloro-1,3,5-triazine, the condensation product of 2-chloro-4,6-di (4-n-butylamino 2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine with 1,2-bis (3-aminopropylamino ) ethane, the condensation product of 2-chloro-4,6-di (4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine with 1,2 - bis (3-aminopropyl-amino) -ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, 3 - dodecyl-1 - (2,2,6,6-tetramethyl-4-piperidyl) pyrrolidine-2,5-dione, 3-dodecyl-1 - (1,2,2,6,6-pentamethyl-4-piperidyl ) - Pyrrolidine-2,5-dione, 2,4-bis [N - (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) -N-butylamino] -6 - (2-hydroxyethyl) - amino-1,3,5-triazine, the condensation product of 2,4-bis [1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] 6-chloro-s-triazine with N, N'-bis (3- aminopropyl) ethylenediamine.

6. Oxalamides for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-di-octyloxy-5,5'-ditert-butyloxanilide, 2,2'-didodecyloxy-5,5'-di-tert - butyloxanilide, 2-ethoxy-2'-ethyl-oxanilide, N, N 'bis - (3-di-methylaminopropyl) oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with 2-ethoxy - 2'-ethyl-5,4'-di-tert-butyloxanilide, and mixtures of o-yp-methoxy-disubstituted or uo-yp-ethoxy-disubstituted oxanilides.

7. 2- (2-hydroxyphenyl) -1,3,5-triazines for example 2,4,6-tris - (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2 - (2-hydroxy - 4-octyloxyphenyl) -4,6-bis - (2,4-dimethylphenyl) -1,3,5-triazine, 2 - (2,4-dihydroxyphenyl) -4,6-bis (2,5-dimethylphenyl) - 1,3,5-triazine, 2,4-bis - (2-hydroxy-4-propyloxyphenyl) -6 - (2,4-dimethylphenyl) -1,3,5-triazine, 2 - (2-hydroxy-4 - octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2 - (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2 - [2-hydroxy-4 - (2-hydroxy-3-butyloxy - propoxy) phenyl] -4,6-bis - (2,4-dimethylphenyl) -1,3,5-triazine, 2 - [2-hydroxy-4 - (2-hydroxy-3-octyloxypropyloxy) phenyl] -4, 6-bis - (2,4-dimethyl) -1,3,5-triazine and 2 - [4-dodecyloxy / tridecyloxy - (2-hydroxypropoxy) -2-hydroxyphenyl] -4,6-bis (2,4 - dimethylphenyl) -1,3,5-triazine.

8. Phosphites and phosphonites for example triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris (2,4-di-tert phosphite) phenyl), diisodecylpentaerythrite diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythrite diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) -pentaerythrite diphosphite, bisisodecyloxy-pentaerythrite diphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) pentaerythrite diphosphite, bis - (2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, tristearylsorbitol triphosphite, 4 , 4 '- biphenylene diphosphonite

ES 2 194 584 A1 of tetrakis - (2,4-di-tert-butylphenyl), 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo [d, g] 1,3, 2-dioxaphosphokin, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo [d, g] -1,3,2-dioxaphosphokin, bis (2,4-di - tert-butyl-6-methylphenyl) methyl and bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite.

Examples of UV absorbers and light protection agents suitable as components (d) are also the "crypto-UVA" described for example in EP-180548. It is also possible to use latent UV absorbers described for example by Hida et al., In RadTech Asia 97, 1997, page 212.

Other additives known in the art may also be added, eg unsightly, leveling and tackifying.

To accelerate the photopolymerization, as supplementary additives (d), a large number of amines can be added, for example triethanolamine, N-methyldiethanolamine, ethyl p-dimethylaminobenzoate or Michler's ketone. The effect of the amines can be enhanced with the addition of aromatic ketones, eg of the benzophenone type. Amines which can be used as oxygen scavengers are, for example, the N, N-dialkylanilines, described for example in EP-339841. Other accelerators, co-initiators and autoxidants are thiols, thioethers, disulfides and phosphines, described eg in EP-438123 and GB-2180358.

It is also possible to add to the compositions of the invention the chain transfer reagents, usual in the art. Examples are mercaptans, amines, and benzothiazole.

The acceleration of photopolymerization can be further achieved by adding photosensitizers as additives (d), which shift the spectral sensitivity or amplify it. These are in particular aromatic carbonyl compounds, for example derivatives of benzophenone, thioxanthone, especially isopropyl thioxanthone, anthraquinone and derivatives 3-acylcoumarin, terphenyls, styryl ketones and 3- (aroylmethylene) thiazolines, camphorquinone, as well as dyes of the type eosin, rhodamine and erythrosine.

As photosensitizers it is also possible to consider the amines mentioned above.

Additional examples of such photosensitizers are the following:

1. Thioxanthones thioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-dodecylthioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 1-methoxycarbonylthioxanthone, 2-ethoxycarbonylthioxanthone, 3 - (2-methoxyethoxanthone, 3 - (2-methoxyethoxycarbonyl) butoxycarbonyl-7-methylthioxanthone, 1-cyano 3-chlorothioxanthone, 1-ethoxycarbonyl-3-chlorothioxanthone, 1-ethoxycarbonyl-3-ethoxythioxanthone,

- ethoxycarbonyl-3-aminothioxanthone, 1-ethoxycarbonyl-3-phenylsulfurylthioxanthone, 3,4-di - [2 - (2-methoxyethoxy) ethoxycarbonyl] -thioxanthone, 1-ethoxycarbonyl-3 - (1-methyl-l-morpholinoethyl) -thioxanthone ,

- methyl-6-dimethoxymethylthioxanthone, 2-methyl-6 - (1,1-dimethoxybenzyl) thioxanthone, 2-morpholinomethylthioxanthone, 2-methyl-6-morpholinomethylthioxanthone, N-alylthioxanthone-3,4-dicarboximide, N-octylthioxanthone-3, 4-dicarboximide, N - (1,1,3,3-tetramethylbutyl) thioxanthone-3,4-dicarboximide, 1-phenoxythioxanthone, 6-ethoxycarbonyl-2-methoxythioxanthone, 6-ethoxycarbonyl-2-methylthioxanthone, thioxanthone-2-carboxylate polyethylene glycol, 2-Hydroxy-3 - (3,4-dimethyl-9-oxo-9H thioxanthon-2-yloxy) -N, N, N-trimethyl-1-propanoaminium chloride;

2. Benzophenones benzophenone, 4-phenylbenzophenone, 4-methoxybenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-dimethylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dimethylaminobenzophenone, 4,4'diethylaminobenzophenone, 4-methylophenone, 4,4'-ethylaminobenzophenone, 2-benzophenone 4,6-trimethylbenzophenone, 4 - (4-methylthiophenyl) benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, methyl 2-benzoylbenzoate, 4 - (2-hydroxyethylthio) benzophenone, 4 - (4-tolylthio) benzophenone, chloride of 4-benzoyl-N, N, N-trimethylbenzenemethanaminium, 2-Hydroxy-3 (4-benzoylphenoxy) -N, N, N-trimethyl-1-propanoaminium monohydrate chloride, 4 - (13-acryloyl-1,4,7,10,13-pentaoxatridecyl) benzophenone, 4-benzoyl-N chloride , N-dimethyl-N- [2- (1-oxo-2-propenyl) oxy] ethylbenzenemethanaminium;

3. 3-Acylcoumarins

- benzoylcoumarin, 3-benzoyl-7-methoxycoumarin, 3-benzoyl-5,7-di (propoxy) coumarin, 3-benzoyl 6,8-dichlorocoumarin, 3-benzoyl-6-chlorocoumarin, 3,3'-carbonyl-bis [5,7-di (propoxy) coumarin],

ES 2 194 584 A1

3,3'-carbonyl-bis (7-methoxycoumarin), 3,3'-carbonyl-bis (7-diethylaminocoumarin), 3-isobutyroylcoumarin, 3-benzoyl-5,7-dimethoxycoumarin, 3-benzoyl-5,7 - Diethoxycoumarin, 3-benzoyl 5,7-dibutoxycoumarin, 3-benzoyl-5,7-di (methoxyethoxy) coumarin, 3-benzoyl5,7-di (allyloxy) coumarin, 3-benzoyl-7-dimethylaminocoumarin, 3-benzoyl-7 - diethylaminocoumarin, 3-isobutyroyl-7-dimethylaminocoumarin, 5,7-dimethoxy-3 - (1-naphthoyl) coumarin, 5,7-diethoxy-3 - (1-naphthoyl) coumarin, 3-benzoylbenzo [f] coumarin, 7-diethylamino-3-thienoylcoumarin, 3- (4-cyanobenzoyl) -5,7-dimethoxycoumarin;

Four. 3- (Aroylmethylene) thiazolines

- methyl-2-benzoylmethylene-β-naphthothiazoline, 3-methyl-2-benzoylmethylenebenzothiazoline, 3-ethyl-2-propionylmethylene-β-naphthothiazoline;

5. Other carbonyl compounds acetophenone, 3-methoxyacetophenone, 4-phenylacetophenone, benzyl, 2-acetylnaphthalene, 2-naphthaldehode, 9,10-anthraquinone, 9-fluorenone, dibenzosuberone, xanthone, 2,5-bis (4-diethylaminobenzylidene) cyclopentanone - (para-dimethylaminobenzylidene) ketones, eg. 2 - (4-dimethylaminobenzylene) indan-1-one or 3- (4-dimethylamino-phenyl) -1-indan-5-yl-propenone, 3-phenylthiophthalimide, N-methyl-3,5-di (ethylthio ) - phthalimide.

In particular, the crosslinking process of pigmented compositions (for example with titanium dioxide) can be enhanced by adding an additive (d) which under ideal theoretical conditions forms radicals, for example an azo compound, such as 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), a triacene, a diazosulfide, a pentazadiene or a peroxy compound, eg a hydroperoxide or a peroxycarbonate, eg t-butyl hydroperoxide, as described eg in EP-245639.

The compositions of the invention may also contain as complementary additives (d) a photoreproducible dye, eg a xanthene, benzoxanthene, benzothioxanthene, thiazine, pyronine, porphyrin or acridine dye and / or a trihalogenomethyl compound which can be decomposed by radiation. Similar compositions are described in EP-445624.

Other common additives (d) are, according to the intended purpose, ooptic bleaches, fillers, both white and colored pigments, colorants, antistatics, humectants and leveling agents.

For the crosslinking of thick and pigmented coatings, the addition of glass microspheres or powdered glass fibers is suitable, as described eg in US Pat. No. 5013768.

The formulations may also contain colorants and / or white or colored pigments. Depending on the intended use, it is possible to use inorganic and orgaonic pigments at the same time. Such additives are known to those skilled in the art, examples of which are titanium dioxide pigments, eg. those of the rutile and anatase type, carbon black, zinc oxides, such as zinc white, iron oxides, for example iron oxide yellow, iron oxide red, chromium yellow, chrome green, nickel-titanium yellow, ultramarine blue, cobalt blue, bismuth vanadate, cadmium yellow, or cadmium red. Examples of organic pigments are mono- and diazo pigments and their metal complexes, phthalocyanine pigments, polycoclic pigments, for example perylene, anthraquinone, thioindigo, quinacridone or triphenylmethane pigments, and diketopyrrolopyrroles, isoindolinones, e.g. the tetrachloroisoindoline, isoindoline, dioxazine, benzimidazolone and quinophthalone pigments. The pigments can be used in the formulations individually or as mixtures of several.

Depending on the intended use, the pigments are added to the formulations in amounts customary in the art, for example in an amount between 0.1 and 60% by weight, for example between 0.1 and 30% by weight. weight or between 10 and 30% by weight, percentage based on the total composition.

The formulations can contain, for example, organic colorants of very different kinds. Examples are azo dyes, methine dyes, anthraquinone dyes or metal complex dyes. The usual concentrations range, for example, between 0.1 and 20%, in particular between 1 and 5%, a percentage based on the total weight of the composition.

The choice of additives will depend on the corresponding field of application and the properties required in that field. The additives (d) described above are familiar to the skilled person and are used in

ES 2 194 584 A1 the compositions of the present invention in amounts customary in the art.

Also subject to the invention are compositions which, as component (a), contain at least one photopolymerizable unsaturated compound, dissolved or emulsified in water.

Such aqueous dispersions of radiation crosslinkable prepolymers are commercial products in many variants. By such is meant dispersions consisting of water and at least one prepolymer dispersed therein. The water concentration in these systems is, for example, between 2 and 80%, in particular between 30 and 60% by weight. The radiation-crosslinkable prepolymer or mixture of prepolymers is present, for example, in a concentration of 95 to 20%, especially 70 to 40% by weight. In these compositions, the sum of the percentages of the water and the prepolymers must be equal to 100, the auxiliaries and additives intervene in various amounts, depending on the intended purpose.

The film-forming, radiation-crosslinkable prepolymers, dispersed and often even dissolved in water, are unsaturated, mono- or polyfunctional prepolymers, initiable by free radicals, already known per se, having, for example, a content of 0.01 to 1.0 mol of polymerizable double bonds per 100 g of prepolymer and have an average molecular weight, for example, of at least 400, in particular 500 to 10,000. Depending on the field of application, other prepolymers with higher molecular weights are also taken into consideration.

For example, polyesters containing polymerizable CC double bonds, whose acid number is at most 10, polyethers containing polymerizable CC double bonds, reaction products that contain hydroxyl groups and result from the reaction of a polyepaoxide provided with less two epoxy groups per molecule with at least one α, β-unsaturated carboxylic acid, polyurethane- (meth) acrylates and acrylic copolymers bearing α, β-unsaturated acrylic moieties, described eg in EP-12339. Mixtures of these prepolymers can also be used. The polymerizable prepolymers described in EP-33896 are also taken into consideration, which are thioether adducts of polymerizable prepolymers whose average molecular weight is at least 600, their content of carboxyl groups is between 0.2 and 15% and their content is of polymerizable CC double bonds is between 0.01 and 0.8 moles per 100 9 of prepolymer. In EP-41125 other idoane aqueous dispersions are described, based on special polymers of alkyl (meth) acrylates; DE-2936039 describes water-dispersible, radioactively crosslinkable, urethane-acrylate prepolymers.

Other additives that may be included in these aqueous radiation-crosslinkable prepolymer dispersions are the complementary additives (d) described above, eg dispersions, emulsifiers, antioxidants, light stabilizers, colorants, pigments, fillers, etc. .ej. talc, gypsum, silicic acid, rutile, carbon black, zinc oxide, iron oxides, reaction accelerators, leveling agents, lubricants, humectants, thickeners, matting agents, defoamers and other common auxiliaries in paint technology. Suitable dispersion aids are high molecular weight, water-soluble organic compounds provided with polar groups, for example polyvinyl alcohol, polyvinylpyrrolidone or cellulose ethers. The emulsifiers used can be non-ionic or, if desired, ionic.

The photoinitiators of the phaormulas I, where R is

II

-CY_x or Z₁₍ According to the invention, they can also be dispersed in aqueous solutions and added in dispersed form to the mixtures to be crosslinked. Treated with non-ionic emulsifiers, or, if applicable, ionic, the compounds of formula I, where R is

OR

II

-C-Υι or Z_lz According to the invention they can be incorporated by mixing and fixed eg. ex. in water. This results in emulsions

ES 2 194 584 A1 which can be used as such as photoinitiators, especially in aqueous photocrosslinkable mixtures described above.

In certain cases, the use of mixtures of two or more photoinitiators of the invention may be advantageous. It is of course also possible to use mixtures with other known photoinitiators, eg. mixtures with camphorquinone, benzophenone, benzophenone derivatives, acetophenone, acetophenone derivatives, for example α-hydroxycycloalkylphenylketones or 2-hydroxy-2-methyl-1-phenylpropanone, dialkoxyacetophenones, α-hydroxy α-aminoacetophenones, for example 4-methyl-1-benzoylthio -methyl-1-morpholinoethane, 4-morpholinobenzoyl-1-benzyl-1-dimethylaminopropane, 4-aroyl-1,3-dioxolanes, benzoone-alkyl ethers and benzylketals, for example benzyldimethylketal, phenyl glyoxalates and derivatives thereof, dimer phenyl glyoxalates, peroesters, eg. benzophenone pertetracarboxylates, described for example in EP-126541, monoacylphosphine oxides, for example (2,4,6-trimethylbenzoyl) diphenylphosphine ooxide, bisacylphosphine oxides, for example bis (2,6-dimethoxy) benzoyl) - (2,4,4-trimethylpent-1-yl) phosphine, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide or bis (2,4,6-trimethylbenzoyl) - (2,4 -dipentoxyphenyl) phosphine ooxide , trisacylphosphine oxides, halo-methyltriazines, e.g. ex. 2- [2- (4-methoxyphenyl) vinyl] -4,6-bistrichloromethyl- [1,3,5] triazine, 2- (4-methoxyphenyl) -4,6-bis-trichloromethyl- [1,3, 5] triazine, 2 (3,4-dimethoxyphenyl) -4,6-bis-trichloromethyl- [1,3,5] triazine, 2-methyl-4,6-bis-trichloromethyl- [1,3,5] triazine , coinitiator / hexaarylbisimidazole systems, eg ortho-chlorohexaphenylbisimidazole combined with 2-mercaptobenzothiazole, ferrocene or titanocene compounds, eg dicyclo-pentadienylbis (2,6-difluoro-3-pyrrolophenyl) titanium. They can also be used in co-initiators of the borate type.

If the new photoinitiator systems are used in hybrid systems, in addition to the free radical crosslinkers of the invention, cationic photoinitiators, peroxide compounds, such as benzool peroxide are used (other suitable peroxides are described in document US-4950581 , column 19, lines 17-25), to aromatic sulfonium, phosphonium or iodonium salts, described eg. in US4950581, from column 18, row 60 to column 19, row 10; or to salts of cyclopentadienylarene-iron (II) complex, eg. hexafluorophosphate (η⁶-isopropylbenzene) (n⁵-cyclopentadienyl) iron (II).

The object of the invention is the compositions in which the additional photoinitiators (c) are compounds of the formulas VIII, IX, X, XI or mixtures thereof,

<img file="ES2194584A1_D0075.tif" />

wherein R25 is hydrogenic, C1-C18 alkyl, C1-C18 alkoxy, -OCH2CH2- -OR29, morpholino, SCH3, a group

<img file="ES2194584A1_D0076.tif" />

n is a number from 2 to 10;

ES 2 194 584 A1

G1 and G2 independently of each other are terminal groups of a polymeric unit, especially hydrogen or CH3;

R26 is hydroxy, C1-C16 alkoxy, morpholino, dimethylamino or -O (CH2CH2O) m-C1-C16 alkyl;

R27 and R28 independently of each other are hydrogen, C1-C6 alkyl, phenyl, benzyl, C1-C16 alkoxy or O (CH2-CH2O) m-C1-C16 alkyl or R27 and R28 together with the carbon atom to which they are attached form a cyclohexyl ring ;

m is a number from 1 to 20;

provided that R26, R27 and R28 cannot all be C1-C16 alkoxy or O (CH2CH2O) m-C1-C16 alkyl at the same time and

R29 is hydrogen,

<img file="ES2194584A1_D0077.tif" />

R30 and R32 independently of one another are hydrogen or methyl;

R31 is hydrogen, methyl or phenylthio, the phenyl ring of the phenylthio moiety being unsubstituted or substituted by C1-C4 alkyl at position 4; 2; 2.4 or 2.4.6;

R33 and R34 independently of one another are C1-C20 alkyl, cyclohexyl, cyclopentyl, phenyl, naphthyl or biphenylyl, these moieties being unsubstituted or substituted by halogen, C1-C12 alkyl and / or C1-C12 alkoxy, or else

R₃₃ is a 5- and 6-membered heterocyclic ring containing S or N, or they are i '

R35 is cyclohexyl, cyclopentyl, phenyl, naphthyl or biphenyl, these moieties being unsubstituted or substituted by halogen, C1-C4 alkyl and / or C1-C4 alkoxy, or R35 is a 5- or 6-membered heterocyclic ring containing S or N;

R36 and R37 independently of one another are unsubstituted cyclopentadienyl or cyclopentadienyl substituted one, two or three times by C1-C18 alkyl, C1-C18 alkoxy, cyclopentyl, cyclohexyl or halogen; Y

R38 and R39 independently of each other are phenyl which is substituted on at least one of the ortho positions with respect to the carbon-titanium bond by fluorine or CF3 atoms and which may contain on the aromatic ring as additional unsubstituted pyrrolinyl substituents or substituted by one or two C1-C12 alkyl, di (C1-C12 alkyl) aminomethyl, morpholinomethyl, C2-C4 alkenyl, methoxymethyl, trimethylsilyl, formyl, methoxy, or phenyl; or polyoxaalkyl, or R38 and R39 are

<img file="ES2194584A1_D0078.tif" />

R40, R41 and R42 independently of one another are hydrogen, halogen, C2-C12 alkenyl, C1-C12 alkoxy, C2-C12 alkoxy interrupted by a number of one to four of atoms of O; cyclohexyloxy, cyclopentyloxy, phenoxy, benzyloxy, phenyl unsubstituted or substituted by C1-C4 alkoxy, halogen, phenylthio or C1-C4 alkylthio; or biphenyl,

ES 2 194 584 A1 but R40 and R42 cannot be hydrogen at the same time and in the rest

<img file="ES2194584A1_D0079.tif" />

at least one R40 or R42 residue is C1-C12 alkoxy, C2-C12 alkoxy interrupted by a one to four number of atoms of O; cyclohexyloxy, cyclopentyloxy, phenoxy, or benzyloxy;

E1 is O, S, or NR43; and

R43 is C1-C8 alkyl, phenyl, or cyclohexyl.

In its condition of C1-C18 alkyl, R25 can have the same meanings described for the compounds of formulas I, II or III. Also in R27 and R28, as C1-C6 alkyl, and R26, as C1-C4 alkyl, they can have the same meanings described above, taking into account the number of carbon atoms existing in each case.

C1-C18 alkoxy is for example linear or branched alkoxy, for example methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy, 2,4, 4-trimethylpent-1-yloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, dodecyloxy, or octadecyloxy.

C2 -C12 alkoxy has the meanings just described, but taking into account the number of carbon atoms existing in each case.

C1-C16 alkoxy has the same meanings just described, but taking into account the number of carbon atoms existing in each case, decyloxy, methoxy and ethoxy being preferred, especially methoxy and ethoxy.

The radical -O (CH2 CH2 O) m-C1-C16 alkyl means from 1 to 20 consecutive ethylene oxide units, the chain of which is terminated by a C1-C16 alkyl. m is preferably a 1-10 number, e.g. ex. 1 to 8, especially 1 to 6. The ethylene oxide unit chain is preferably terminated with a C1-C10 alkyl, eg C1-C8 alkyl, especially C1-C4 alkyl.

R31 is a substituted phenylthio ring, preferably p-tolylthio.

As C1-C20 alkyl, R33 and R34 are linear or branched and are for example C1 -C12 alkyl, C1-C8 alkyl, C1 -C6 alkyl or C1-C4 alkyl. Examples are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, octyl, nonyl, decyl , undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl or icosyl. As alkyl, R33 is preferably C1-C8 alkyl.

As substituted phenyls, R33, R34 and R35 were mono- to pentasubstituted, eg mono, gave trisubstituted, especially tri- or disubstituted on the phenyl ring. Substituted phenyl, naphthyl and biphenyl are substituted eg by a linear or branched C1-C4 alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl or by a linear or branched C1-C4 alkoxy, eg. methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, preferably methyl or methoxy.

If R33, R34 and R35 are a 5- or 6-membered heterocolic ring containing S or N, then for example they would be thienyl, pyrrolyl or pyridyl.

In the expression di (C1-C12 alkyl) aminomethyl, C1-C12 alkyl has the same meanings already defined above.

C2 -C12 alkenyl is straight or branched; it can be mono- or polyunsaturated and is eg allyl, methallyl, 1,1-dimethylallyl, 1-butenyl, 2-butenyl, 1,3-pentadienyl, 1-hexenyl or 1-octenyl, especially allyl.

ES 2 194 584 A1

C1-C4 alkylthio is linear or branched and is for example methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, s-butylthio or t-butylthio, preferably methylthio.

C2-C4 alkenyl is for example allyl, methallyl, 1-butenyl or 2-butenyl.

Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.

The term polyoxaalkyl includes C2-C20 alkyl interrupted by a nuomer of 1 to 9 of O atoms and means for example structural units of the type CH3-O-CH2-, CH3CH2-O-CH2CH2-, CH3O [CH2 CH2O] and-, where y is a nuomer of 1a9, - (CH2CH2 O) 7CH2CH3, -CH2-CH- (CH3) -O-CH2CH2CH3.

Compositions in which R25 is hydrogen, -OCH2CH2-OR29, morpholino, SCH3, a group are preferred.

<img file="ES2194584A1_D0080.tif" />

R₂₆ is hydroxyl, C alkoxy₁ -C₁₆, morpholino or dimethylamino;

R27 and R28 independently of one another are C1-C4 alkyl, phenyl, benzyl or C1-C16 alkoxy or R27 and R28 together with the carbon atom to which they are attached form a cyclohexyl ring;

R29 is hydrogenic or

<img file="ES2194584A1_D0081.tif" />

R30, R31 and R32 are hydrogen;

R33 is C1-C12 alkyl, unsubstituted phenyl or phenyl substituted by C1-C12 alkyl and / or C1-C12 alkoxy;

R34 is π; and ~^C~^ñ35

R35 is phenyl which is substituted by C1-C4 alkyl and / or C1-C4 alkoxy.

Preferred compounds of formulas VIII, IX, X and XI are α-hydroxycyclohexylphenylketone or 2-hydroxy-2-methyl-1-phenylpropanone, (4-methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) -1benzyl-1-dimethyl-aminopropane, benzoyldimethylketal, (2,4,6-trimethylbenzoyl) phenylphosphine ooxide, bis (2,6-dimethoxybenzoyl) - (2,4,4-trimethyl-pent-1-yl) oxide phosphine, bis- (2,4,6-trimethylbenzoyl) phenylphosphine ooxide or bis- (2,4,6-trimethylbenzoyl) - (2,4-dipentoxyphenyl) phosphine oxide and dicyclopentadienyl-bis (2,6-difluoro- 3pyrrolo) titanium.

Further preferred are compositions in which, in Formula VIII, R27 and R28 independently of each other are C1-C6 alkyl, or together with the carbon atom to which they are attached form a cyclohexyl ring, and R26 is hydroxyl.

The proportion between the compounds of formula I where R is

OR

C-Yj. or Z_lz

ES 2 194 584 A1 (photoinitiator component (b)) and the compounds of the formulas VIII, IX, X and / or XI (= photoinitiator component (c)) in the mixture was between 5 and 99%, p. eg between 20 and 80%, preferably between 25 and 75%.

Also important are compositions in which, in the compounds of formula VIII, R27 and R28 are identical and mean methyl and R26 is hydroxyl or isopropoxy.

Equally preferred are positions containing compounds of formula I, where R is or

C-Υα. OZ_lz and compounds of the formula X in which

R33 is unsubstituted phenyl or mono-, di- or tri-substituted by C1-C12 alkyl and / or C1-C12 alkoxy or is C1-C12 alkyl;

OR

R₃₄ it is a non-phenyl group; Y^C ~ ^R35

R35 is phenyl substituted one to three times by C1-C4 alkyl or C1-C4 alkoxy.

The compositions described above containing mixtures of photoinitiators of the formulas I, where R is

OR

II

C-Υι or Z_lz

VIII, IX, X and / or XI and are liquid at room temperature.

The preparation of the compounds of the formulas VIII, IX, X and XI is generally known to those skilled in the art and some of the compounds are commercial products. The preparation of the oligoomeric compounds of the formula VIII is described for example in EP 161463. A description of the production of the compounds of the formula IX is found for example in EP 209831. The preparation of the compounds of the formula X has been published for example in EP 7508, EP 184095 and GB 2259704. The preparation of the compounds of the formula XI is described for example in EP 318894, EP 318893 and EP 565488.

The photopolymerizable compositions contain 0.05 to 20%, preferably 0.05 to 15%, especially 0.1 to 5% by weight of photoinitiator, percentages based on the solid composition. The amount indicated is the sum of all the photoinitiators added, if mixtures thereof are used. Therefore, the amount indicated refers to the photoinitiator (b) or the photoinitiators (b) + (c).

The compounds of the invention in which Z1 or Z2 are siloxane-containing moieties are especially suitable as photoinitiators of surface coatings (paints), especially vehicle paints. These photoinitiators are not distributed in the most homogeneous way possible within the formulation to be crosslinked, but they are enriched (in higher concentration) specifically on the surface of the coating to be crosslinked, that is, a specific orientation of the initiator towards the surface takes place of the formulation.

The photopolymerizable compositions can be used for various purposes, for example as printing inks, for example screen printing inks, flexographic inks or offset printing inks, as clear varnishes, as colored paints, as white paint, eg on wood. or metal, like

ES 2 194 584 A1 powder paint, as a paint in general, intended among others for paper, wood, metal or plastic, as a crosslinking paint with daylight for marking buildings and roads, for photographic reproduction techniques, for holographic recording materials , for imaging techniques or to make printing plates that can be developed with organic solvents or aqueous alkalis; to manufacture screen printing screens; for dental filling compositions, for adhesives, for pressure sensitive adhesives; for laminatable resins; for etching reserve resins, welding reserve resins, galvanizing, or permanent reserve resins, both in liquid or solid film form; for photo-structuring dielectrics and for protection masks against the solder bath for electronic circuits; for reserve resins in the manufacture of color filters for any type of screen; to generate structures in processes of production of panels of plasma displays and electroluminescence displays, for the production of oaptic switches, optic grids (interference grids); to produce three-dimensional articles by mass crosslinking (UV crosslinking in transparent molds) or by the stereolithographic process, described eg. in US-4575330, to manufacture hybrid materials (composites) (eg styrene polyesters that may possibly contain glass fibers and / or other fibers and other auxiliaries) and other thick layer materials, for coating or sealing electronic components or as a coating of optic fibers. The compositions are also suitable for making oaptic lenses, eg. contact lenses or Fresnel lenses and for the manufacture of devices, ancillaries and implants for the medical sector.

The compositions of the invention can also be used to make gels with thermotropic properties. These gels are described eg in DE-19700064 and EP-678534.

The compositions can further be used in dry film paints, described for example in Paint &amp; Coatings Industry, April 1997, 72 or in Plastics World, volume 54, no. 7, page 48 (5).

The compounds of the invention can also be used as initiators of polymerizations in emulsion, in beads or in suspension or as initiators of a polymerization for fixing the ordering states of mono- and oligoamers of liquid crystal, or as initiators for fixing dyes on materials. organic.

In paints, mixtures of a prepolymer with polyunsaturated monoamers are often used, which mixtures can also contain a monounsaturated monoamer. The prepolymer is the one that largely decides the properties of the paint film, the expert can influence the properties of the crosslinked film by varying the prepolymer. The polyunsaturated monomer acts as a crosslinker that renders the paint film insoluble. The monounsaturated monomer acts as a reactive diluent that allows the viscosity to be reduced without the need to resort to a solvent.

Unsaturated polyester resins are often used in two-component systems together with a monounsaturated monomer, preferably styrene. For photoresist resins, specific one-component systems are usually used, for example polymaleimides, polyhalcones or polyimides, as described in DE-2308830.

The compositions of the invention can also be used to make radiation-crosslinkable powder paints. Powder paints can be based on solid resins and monoamers provided with reactive double bonds, eg maleates, vinyl ethers, acrylates, acrylamides and mixtures thereof. A radically UV crosslinkable powder paint can be formulated by mixing unsaturated polyester resins with saline acrylamides (e.g. methyl methacrylamidoglycolate) and with a radical photoinitiator of the invention, for example as described in the article "Radiation Curing of Powder Coating", Proceedings of the 1993 Radtech Europe conference, whose authors are M. Wittig and Th. Gohmann. They can also be formulated into radically UV crosslinkable powder paints by mixing unsaturated polyester resins with acrylates, methacrylates or solid vinyl ethers and with a photoinitiator (or mixture of photoinitiators). Powder paints can also contain binders, described for example in DE4228514 and EP-636669. UV-crosslinkable powder paints can contain white or colored pigments. For example, a titanium dioxide of the rutile type can preferably be used up to a concentration of 50% by weight, in order to achieve a crosslinked powder paint with good hiding power (good opacity). The procedure normally consists of the electrostatic or tribostatic projection of the powder material on the substrate, eg metal or wood, in the fusion of the powder by heating and, once a smooth film has been achieved, in the crosslinking of the coating by means of UV and / or visible light, eg with medium pressure mercury lamps, halogen lamps or xenoan lamps. A special advantage of radiation-crosslinkable powder paints over heat-crosslinkable ones is that the flow time after melting of the powder particles can be prolonged as desired, thereby ensuring the formation of a smooth and stable coating.

ES 2 194 584 A1 very bright. Unlike thermal crosslinking systems, radiation crosslinkable powder paints can be formulated without the annoying effect of reduced pot life, so that they melt at lower temperatures. For this reason they are also suitable for heat-sensitive substrates, eg wood or plastics.

In addition to photoinitiators, powder paint formulations can also contain UV absorbers. Examples of this have been listed above in items 1 to 8.

The photocrosslinkable compositions of the invention are suitable for example as coatings on substrates of all kinds, eg. wood, textiles, paper, ceramics, glass, plastic such as polyether, polyethylene terephthalate, polyolefins or cellulose acetate, especially in the form of films, as well as metals such as Al, Cu, Ni , Fe, Zn, Mg or Co and GaAs, Si or SiO2, on which it is intended to apply a protective layer or generate an image through exposure to a luminous figure or image.

The coating of the substrates can be effected by applying a liquid composition, a solution or a suspension on the substrate. The choice of solvent and concentration are primarily a function of the type of composition and the type of application procedure. The solvent must be inert, that is, it must not undergo any chemical reaction with the components and it must be possible to remove it again during drying after application. They are suitable solvents eg ketones, ethers, and esters, such as methyl ethyl ketone, isobutyl methyl ketone, cyclopentanone, cyclohexanone, N-methylpyrrolidone, dioxane, tetrahydrofuran, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol , 1,2-dimethoxyethane, ethyl acetate, n-butyl acetate, and ethyl 3-ethoxy-propionate.

The formulation in the form of a solution is applied uniformly to a substrate by known coating procedures, e.g. by centrifugation, immersion, squeegee coating, with a curtain machine, by brush, by spraying, especially by electrostatic spraying. and reverse motion roll coating as well as by electrophoretic deposition. It is also possible to apply the photosensitive layer on a flexible temporary support and then transfer said layer to the final substrate by lamination, eg to a circuit board laminated on copper.

The amount to be applied (layer thickness) and the type of substrate (layer support) depend on the desired field of application. The ideal layer thickness for the fields of application in question, eg. ex. in the photoreserves sector, the printing ink sector or the painting sector, it is already known to the technician in the field. Depending on the field of application, the layer thickness range was generally between 0.1 µm and more than 10 mm.

The new radiation sensitive compositions are also applied as negative reservoirs which have a high sensitivity to light and are capable of developing in alkaline aqueous medium without swelling. They are ideal as photoreserves for electroinics, for example galvanizing reserves, etching reserves, liquid and dry films, welding reserves, reserves to manufacture color filters in a wide variety of displays and electroluminescence displays, for production. from printing plates, for example offset plates and screen printing; to produce molds for relief printing, flat printing, gravure and screen printing; to produce raised copies, for example to produce Braille texts, for the production of stamps; for the etching of molds or for microreserves in the production of printed circuits. The compositions can also be used as a photo-moldable dielectric layer or coating, potting material, or insulating coating in the production of computer chips, printed circuits, and other electrical or electronic components. The possible supports of the layer and the conditions of process of the substrates of the coatings are very varied.

The compositions of the invention can also be applied to the production of mono- or multilayer materials for the recording or reproduction of images (copies, reprography), which can be mono- or polychromatic. On the other hand, the materials are ideal for stable color systems (color proofing). In this technology, microcapsules containing formulations can be applied and, with a view to producing the image, crosslinking by radiation is followed by a heat treatment. Such systems and technologies and their applications are published for example in US-5 376 459.

Substrates used to record photographic information include, for example, polyether films, cellulose acetate or polymer-coated papers; substrates for offset printing plates are made of specially treated aluminum; substrates for the manufacture of printed circuits are copper-clad laminates and the substrates for integrated circuits are silicon wafers. The layer thickness of photographic materials and offset printing plates was

ES 2 194 584 A1 in general between 0.5 µm and 10 µm, while in printed circuits it is between 1.0 µm and 100 µm.

After coating the substrates, the solvent is removed, usually by drying, leaving the photoresist on the substrate.

The term "image" exposure includes exposure through a mask that corresponds to a predetermined pattern, for example a reticle or a ruler, and also exposure to a laser or a light beam moving over the surface of the substrate. under the control, for example, of a computer, thereby generating an image, or the irradiation of electron beams controlled by a computer. Furthermore, liquid crystal masks that can be directed pixel by pixel can be used to generate digital images, such as those described for example by A. Bertsch, JY Jezequel, JC Andre in Journnal of Photochemistry and Photobiology, A: Chemistry, 1997, 107, pp. . 275-281 and by K.-P. Nicolay in Offset Printing 1997, 6, pp. 34-37.

Conjugated polyomers, for example polyanilines, can be converted from a semiconductor state to a conductive state by proton doping. The photoinitiators of the invention can also be used for image exposure of polymerizable compositions containing such polyomers in order to generate conductive structures (in the irradiated areas) that are occluded within the insulating material (unexposed areas). Such materials can be used for example as wiring or connector components for the manufacture of electrical or electronic components.

After exposing the material to the image and before development, a short-term thermal treatment may be advantageous. Only the exposed parts are thermally crosslinked. The temperatures are generally between 50 and 150 ° C, preferably between 80 and 130 ° C; the duration of the thoracic treatment is normally 0.25 to 10 minutes.

The photocrosslinkable composition can also be used in printing plate or photoresist manufacturing processes, as described for example in DE-4 013 358. In this process, the composition is exposed for a short time to visible light, the wavelength of which is greater than 400 nm, without mask, before, simultaneously or after irradiation with the image. After exposure and, if desired, thermal treatment, the unexposed areas of the photosensitive coating are removed with a developer by known methods.

As mentioned above, the compositions of the invention can be developed with aqueous alkalis. Particularly suitable aqueous alkaline developer solutions are aqueous solutions of tetraalkylammonium hydroxide or alkali metal silicates, phosphates, hydrooxides or carbonates. Small amounts of humectants and / or organic solvents can be added to these solutions, if desired. Typical examples of orgone solvents, which can be added in small amounts to developing liquids, are cyclohexanone, 2-ethoxyethanol, toluene, acetone and mixtures of these solvents.

Photoreticulation is very important in printing, since the drying time of the ink is a critical parameter of the production speed of graphic articles, which you have to adjust to values ​​of fractions of a second. UV crosslinkable inks are very important for screen printing, flexo printing and also for offset printing.

As mentioned before, the new mixtures are also very suitable for making printing plates. In such an application recourse is made, for example, to blends of soluble linear polyamides or of styrene / butadiene or styrene / isoprene rubber, polyacrylates or poly (methyl methacrylate) having carboxyl groups; poly (vinyl alcohol) or urethane acrylates with photopolymerizable monoomers, for example acrylamides or methacrylamides, or acrylates or methacrylates, and a photoinitiator. The films and plates of these systems (huomeric or dry) are exposed through a negative (or positive) of the original and the uncrosslinked parts are then removed by washing, using a suitable solvent or aqueous solutions.

Another field of application of photocrosslinking is the coating of metals, in which case metal plates or tubes, cans or bottle caps are coated, for example, and also in the photocrosslinking of polymer-based paints, for example synthetic flooring or PVC-based wallpapers. . Examples of photocrosslinking of paper coatings are colorless varnishes on labels, record covers, and book covers.

It is also interesting to use the compositions of the invention for the manufacture of molded parts from mixed materials. A mixed material (composite) consists of a self-porous material59

ES 2 194 584 A1, for example a fiberglass fabric, or also vegetable fibers [see K.-P. Mieck, T. Reussmann in Kunststoffe 85 (1995), 366-370] which is impregnated with a photocrosslinkable formulation. The molded parts obtained with the compositions of the present invention starting from mixed masses achieve great stability and mechanical resistance. The compositions of the invention can also be used in molding, impregnating and coating compositions, described for example in EP-7086. Such compositions are, for example, thin-film resins, which must meet high requirements in terms of crosslinking activity and resistance to yellowing, fiberglass-reinforced molding resins, eg flat, longitudinally or transversely corrugated skylights. The process for the manufacture of these molding materials, eg. by manual application, by fiber spraying, by centrifugation or by rolling, is described eg in PH Selden, "Glasfaserverstarkte Kunststoffe" (= Plastics reinforced with fiberglass), page 610, Springer publishing house, Berlm-Heidelberg-New York, 1967. Consumables that can be manufactured by this process are, for example, boats, chipboards or carpenter's boards covered on both sides with fiberglass-reinforced plastic, pipes, sports equipment, roof coatings, tanks, etc. Other examples of molding, impregnating and coating compositions are thin layers of unsaturated polyester resin for glass fiber reinforced (GFP) parts, eg corrugated sheets and paper laminates. Paper laminates can be based on urea or melamine resins. The thin layer is applied on a support (eg a sheet) before the laminate is manufactured. The photocrosslinkable compositions of the invention can also be used for casting resins or for the inclusion of objects, eg electronic components, etc. They can also be used for lining cavities and pipes. Medium pressure mercury lamps, common in UV crosslinking, are used for crosslinking. However, lamps of lower intensity are of special interest, eg those of the type TL 40W / 03 or TL 40W / 05. The intensity of these lamps is roughly equal to that of sunlight. It can also be used for crosslinking in direct sunlight. It is also advantageous that the mixed material can be removed from the light source in a semi-cured, still plastic state, and can be subjected to shaping. The final crosslinking is then carried out.

The compositions of the present invention can also be used for the production of optic waveguides and oaptic inverters, in which case the difference in refractive indices between the irradiated and non-irradiated areas is exploited.

The use of photocrosslinkable compositions is also important for image-based techniques and for the optical production of informational media. In these applications, as mentioned before, the layer (wet or dry) applied on the support is irradiated with the image, that is, it is irradiated through a photomask with UV or visible light and the unexposed areas are eliminated. by action of a solvent (= developer). The application of photocrosslinkable layers on metal can be carried out by electrodeposition. The exposed areas polymerize by crosslinking and, in this way, become insoluble, remaining fixed on the support. Proper coloration produces visible images. When the support is a metallized layer, then the metal, after exposure and development, can be etched away from the unexposed areas or reinforced by electrodeposition. In this way printed electronic circuits and photoreserves can be manufactured.

The sensitivity to light of the compositions of the invention is generally between 200 nm and 600 nm (UV region). Suitable radiation is, for example, that of sunlight or light generated by an artificial spotlight. Therefore, a large number of very diverse types are used as light sources. They can be point bulbs and also surface bulbs (carpets of light). Examples of this are carbon arc lamps, xenoan arc lamps, medium, high or low pressure mercury lamps, possibly equipped with metal halides (halogen lamps), metal vapor lamps, "excimer" lamps, fluorescent tubes. super-practical, fluorescent lamps, argon incandescent lamps, flash lamps, photographic flood lamps, light-emitting diodes (LEDs), electronic rays, and X-rays. The distance between the lamp and the substrate of the invention that must be exposed to light can vary depending on the intended purpose and the type and intensity of the lamp, eg between 2 cm and 150 cm. Laser light sources, eg excimer lasers, such as cryptan-F lasers, are particularly suitable for light emission of 248 nm. Lasers in the visible region can also be used. By this method, they can be produced, for example, lithographic offset printing plates or relief printing plates or even photographic image recording materials.

Another object of the invention is a photopolymerization process of monomeric, oligomeric or polymeric compounds, provided with at least one unsaturated double bond, characterized in that the composition described above is subjected to light in the range of 200 to 600 nm. It is also the object of the invention to use the compounds of formula I, where R is

ES 2 194 584 A1 or

II

C-Υι or Zi, as photoinitiators for the photopolymerization of non-volatile monomer, oligoomer or polymer compounds, which are provided with at least one unsaturated double bond, by exposure to light in the spectral region between 200 and 600 nm.

The invention also refers to the use of the composition described above or a process for obtaining pigmented or non-pigmented paints and varnishes, from printing inks, for example screen printing inks, offset printing inks, flexographic inks, powder paints, of impression plates, adhesives, dental masses, waveguides, optical inverters, stable color systems, hybrid materials (composites), fiber optic cable coatings, patterns (screens) of silk-screen printing, of reserve materials, color filters, the use of a composition to encapsulate electrical or electronic components, to produce magnetic recording materials, to manufacture three-dimensional items by stereolithography, for photographic reproduction, for materials of image recording, especially holographic recording; bleaching materials, e.g. for imaging materials, including those based on microcapsules.

The invention also provides a substrate coated on at least one side with a composition as described above, and describes a process for the photographic obtaining of relief images, in which the coated substrate is subjected to exposure to the image and thereafter unexposed areas are removed with developer. Exposure to the image can be done by irradiation through a mask or by laoser rays. In this context, exposure to laoser rays is particularly advantageous.

The following examples illustrate the invention in more detail. Data in parts or percentages refer to weight, as in the remaining description and in the claims, unless otherwise indicated. When we speak of alkyl moieties of more than three carbon atoms without specifying their isomeric form, then it is assumed that these moieties are straight-chain isomers.

Example 1

Obtaining lithium (2,4,6-trimethylbenzoyl) -isobutylphosphine

To 4.5 g (0.025 mol) of isobutylphenylphosphine (50% solution in toluene) in 30 ml of tetrahydrofuran are slowly added dropwise between 0 and 10 ° C 34.4 ml (0.055 mol, +10%) of butyl- 1.6 M lithium. Without varying the temperature, 4.6 g (0.025 mol) of 2,4,6-trimethylbenzoyl chloride are then added dropwise. Warming to room temperature to give the title compound as an orange suspension. The δ-shift signal of the P-NMR spectrum³¹ it appears at 50 ppm, measured against CDCl3 that is taken as a reference.

Example 2

Obtaining lithium (2,4,6-trimethylbenzoyl) - (2,4,4-trimethylpentyl) phosphine

This compound is obtained in a similar way to the procedure described in Example 1 starting from 2,4,6-trimethylbenzoyl chloride and 2,4,4-trimethylpentylphosphine. The δ-shift signal of the p-NMR spectrum³¹ it appears at 49.2 ppm, measured against CDCl3 that is taken as a reference.

Example 3

Obtaining 2,4,6-trimethylbenzoylisobutylphosphine

The suspension obtained in the manner described in Example 1 is added dropwise onto a mixture of toluene / water and acetic acid. The orgaonic phase is separated, dried over magnesium sulfate and concentrated by evaporation in a rotary evaporator (rotary evaporator) in argon atmosphere. The residue is distilled in a bulb tube furnace at 110^°C and 0.1 torr. 6 g of the title compound are obtained as a pale yellow oil. The δ [ppm] shift signal of the p31-NMR spectrum appears at -37.5.

ES 2 194 584 A1

Shift signals δ [ppm] of the H-NMR spectrum¹ : 1.01 (dd.); 1.85 (m); 1.98 (m); 2.23 (s); 2.28 (s); 3.91 (t); 4.66 (t, 1H of the P); 6.83 (s); measured in C6D6).

Example 4

Obtained from 2,4,6-trimethylbenzoylisobutylbenzylphosphine oxide

To the suspension obtained by the method described in Example 1, 4.30 g (0.025 mol) of benzyl bromide are slowly added dropwise at room temperature. Stir at room temperature for 1 hour and concentrate the orange reaction suspension on a rotary evaporator ("rotary evaporator"). The residue is taken up in 50 ml of toluene and 4.2 g (0.0375 mol) of 30% hydrogen peroxide are added. Stirred at 20-30^°C for 2 hours, finishing the reaction. The reaction emulsion was poured into water and washed with a saturated aqueous sodium hydrogen carbonate solution, then dried over magnesium sulfate and filtered. The filtered liquid is concentrated on the rotary evaporator. The residue is purified through solid gel and dried under high vacuum. 6.0 g of the title compound are obtained as a viscous yellow oil.

The δ-shift signal of the p-NMR spectrum³¹ it appears at 39.6 ppm, measured against CDCl3 that is taken as a reference.

The corresponding signals of the H-NMR spectrum¹ (ppm), measured in CDCl3, are as follows: 7.17.2 (m), 6.7 (s), 3.1-3.4 (m), 2.15 (s), 2.0 ( s), 1.6-1.9 (m) and 0.87-0.93 (q).

Examples 5-14

In a similar way, the compounds of Examples 5-14 are prepared according to the method described in Example 4 and using the corresponding starting materials. The structures and analytical data are shown in Table 1.

(See Table 1 on the following pages)

ES 2 194 584 A1

TABLE 1 ru

<img file="ES2194584A1_D0082.tif" />

CH₃

<td>Ex '.</td><td>Re</td><td> 2,</td><td>Starting materials</td><td>NMR data⁵in YPm]</td>

<td> 5</td><td>2,4,4-trimethyl- pentyl</td><td>benzyl</td><td>Lithium (2,4,6-trimethylbenzoyl) -2,4,4-trimethylpentylphosphine + benzyl bromide</td><td>Y: 39.25? H: 0.97-0.85 (d); 1.01-1.05 (q); 1,191.24 (t); 1.42-1.97 (m); 1.97 (s); 1,992.22 (m); 3.19-3.50 (m), 4.03-5.53 (q); 6.78 (s); 7.14-7.36 (m)</td>

<td> 6</td><td>2,4,4-trimethyl- pentyl</td><td>allyl</td><td>Lithium (2,4,6-trimethylbenzoyl) -2,4,4,4-trimethylpentylphosphine + allyl bromide</td><td>Y: 39.06 H: 1.11 (d); 1,131.70 (t); 1.76-1.39₃(m); 1.72-2.14 (m); 2.28 -2.31 (d); 2.76-2.88 (m); 5.20-5.27 (m); 5.77-5.90 (m); 6.86 :</td>

<td> 7</td><td>2,4,4-trimethylpentyl</td><td>isobutyl</td><td>Lithium (2,4,6-trimethylbenzoyl) -2,4,4-trimethylpentylphosphine + isot bromide</td><td>Y: 42.0 ' H: 0.95 (d); 1,071.37 (m); 1.72-2.15 (mi; 2.28 (s); 2.33 TO; §.86 (s)</td>

ES 2 194 584 A1

<td>Ex.</td><td>Re</td><td>z,</td><td>starting materials</td><td>^ NMR data in δ [ppm]</td>

<td> 8</td><td>2,4,4-trimethyl- pentyl</td><td>2-ethylhexyl</td><td>Lithium / 2,4,6-trimethyloenzoyl) -2,4,4-trimethylpentylphosphine + 2-ethylhexyl bromide</td><td>^ P: 40.77 lH: 0.92-0.95 (m); 1.19-1.28 (m); 1.46-1.59 (m); 1.73-2.28 (m); 2.46 (s); 6.69 (s)</td>

<td> 9</td><td>isobutyl</td><td>n-butyl „¡</td><td>Lithium (2,4,6-trimethylbenzoyl) -isobutyl phosphine + n-butyl bromide</td><td>Y: 42.5 Y 1.03 (d); 1.08 (d); 1.55-1.80 (m); 2.25 (m); 2.28 (s); 2.31 (s); 6.86 (s)</td>

<td> 10</td><td>isobutyl</td><td>allyl</td><td>(2,4,6-trimethyl- lithium benzoyl) -isobutylphosphine + allyl bromide</td><td>Y: 39.2 H: 1.04 (d); 1.07 (d); 1.83 (m); 2.19 (m); 2.28 (s); 2.31 (s); 2.84 (m); 5.21 (m); 5.27 (d); 5.83 (m); 6.86 (s)</td>

<td> 11</td><td>isobutyl</td><td>-CH₂(CO) OCH₃</td><td>(2,4,6-trimethyl- lithium benzoyl) -isobutylphosphine + methyl brcmate</td><td>Y: 36.0 H: 1.07 (d); 1.09 (d); 2.02 (m); 2.22 (m): 2.29 (s); 2.34 (s); 3.21 (m); 3.72 (s); 6.88 (s)</td>

<td> 12</td><td>isobutyl</td><td>-CH₂YES (CH₃)₂Yes (CH3) 3</td><td>Lithium (2,4,6-trimethylbenzoyl) -isobutylphosphine + chloromethyl pentamethyldisiloxane.</td><td>ÜP: 41.9 H: 0.10 (s); 0.22 (s); 0.32 (s); 1.02^Lfd); 1-07 (d); 1,201.42 (m); 1.86 (m); 1.96-2.04 (m); 2.28 (s); 2.31 (s); 6.86 (?) ........</td>

<td> 13</td><td>isobutyl</td><td>2-ethylhexyl</td><td>Lithium (2,4,6-trimethylbenzoyl) -isobutylphosphine + 2-ethylhexyl bromide</td><td>Y: 42.8 H: 0.87 (m); 1.06 (d); 1.09 (d); 1.26 (m); 1.45 (m); 1.74 (m); 1.90 (m); 2.17 (m); 2.28 (s); 2.33 (s); 6.86 (s)</td>

ES 2 194 584 A1

<td> 14</td><td>isobutyl</td><td>-CH (CH₃) (CO) OC₈Hi₇</td><td>Lithium (2,4,6-triinethylbenzoyl) -isobutllphosphine + octyl 2-bromopropionate. (mix of isomers)</td><td>A: 34.9 H: 0.81-0.88 (m); 1.07 (dd); 1,151.34 (m); 1.40 (d); 1.49 (m); 1.75 (m); 2.05-2.40 (m); 2.28 (s); 2.28 (s); 2.29 (s); 2.33 (s); 3.63 (m); 4.01 (m); 6.35 (s)</td>

Example 15

Obtained from 2,4,6-trimethylbenzoylisobutyl- (2-hydroxycyclohexyl) phosphine oxide

To a suspension prepared according to the method described in Example 1, 2.30 g (0.02 mol) of cyclohexene oxide are slowly added dropwise at room temperature. Heat to 55-55 ° C and stir for 1 hour at this temperature, the reaction mixture is treated with acetic acid and concentrated by rotary evaporation. The residue is taken up in 50 ml of toluene and treated with 3.4 g (0.03 mol) of hydrogen peroxide (30%). It is stirred for 2 hours between 20 and 30 ° C, the reaction being considered finished. The reaction emulsion was poured into water and washed with saturated aqueous sodium hydrogen carbonate solution, then dried over magnesium sulfate and filtered. Concentrate the filtered liquid on the rotary evaporator. The residue is purified through solid gel and dried under high vacuum. The title compound is obtained as a white solid.

The shift signal δ [ppm] of the P-NMR spectrum³¹ appears at 48.0. The δ [ppm] shift signals of the H-NMR spectrum¹, measured in CDCl₃, are the following: 1.08 (d); 1.09 (d); 1.28 (m), 1.42 (m), 1.78-1.94 (m), 2.16 (m), 2.29 (s), 2.34 (s), 3.93 ( m), 6.88 (s).

Example 16-17

The compounds of Examples 16 and 17 are prepared in a similar way to that described in Example 15, using the corresponding starting materials. The structures and analytical data are collected in Table 2.

(See Table2 in next page)

ES 2 194 584 A1

TABLE 2

<img file="ES2194584A1_D0083.tif" />

ch₃

<td>E j</td><td>Re</td><td>z,</td><td>I materials of departure</td><td>δ [ppm]</td>

<td> 16</td><td></td><td>-5Ό</td><td>Lithium (2,2,6-trimethylbenzoyl) -isobutylphosphine + styrene oxide</td><td>X: 43.8 JH: 1.08 (d); 1.82 (m); 2.18 (m); 2.27 (m): 2.32 (s); 2.36 (s); 4.55 (s); 5.11 (dd); 6.92 (s); 7.29-7.37 (m)</td>

<td> 17</td><td></td><td>Hee-p</td><td>(2,4,6-trimethyl- benzoyl) -isobutylphosphine lithium + chlorobenzaldehyde</td><td>fP: 37.7; 38.3 H: 0.82 (d); 0.87 (d); 1.71-1.85 (m); 2.22 (s); 2.29 (s); 5.33 (d); 6.85 (s); 7.32 (d); 7.41 (d) (contains the second A diastereomer. |</td>

Example 18

Obtaining 2,4,6-trimethylbenzoyl- (2,6-dimethoxybenzoyl) -isobutylphosphine oxide

To a suspension prepared according to the method described in Example 1, 5.30 g (0.026 mol) of 2,6-dimethoxybenzool chloride are slowly added dropwise at room temperature. The mixture was stirred for 1 hour at room temperature and the orange reaction suspension was concentrated by rotary evaporation. The residue is taken up in 50 ml of toluene and treated with 3.4 g (0.03 mol) of hydrogen peroxide (30%). It is stirred for 2 hours between 20 and 30 ° C, when the reaction is finished. The reaction emulsion was poured into water and washed with saturated aqueous sodium hydrogencarbonate solution, then dried over magnesium sulfate and filtered. Concentrate the filtered liquid on the rotary evaporator. The residue is purified through solid gel and dried under high vacuum. 3.8 g of the title compound are obtained as a slightly yellow solid, the mp of which is 105-106 ° C.

The shift signal δ [ppm] of the P-NMR spectrum³¹ appears at 27.7. The δ [ppm] shift signals of the H-NMR spectrum¹, measured in CDCl3, are as follows: 1.05 (dd); 2.12-2.37 (m); 2.26 (2s); 3.56 (s); 6.54 (d); 6.85, 7.35 (t).

Examples 19-21

The compounds of examples 19-21 are obtained in a similar way to that described in example 18, using the corresponding starting materials. Table 3 shows the structures and analytical data.

ES 2 194 584 A1

TABLE 3 /^CH3 = Λ OOO

Λ II Ί η X^c-pc \ R.

CHa

<td>Ex.</td><td>Re</td><td>Y,</td><td>starting materials</td><td>NMR data in δ [ppm]</td>

<td> 19</td><td>2,4,4-trimethyl- pentyl</td><td>2,6-dimethoxy- phenyl</td><td>(2,4,6-trimeyl- lithium benzoyl) -trimethylpentylphosphine + 2,6-dimethoxybenzoyl chloride</td><td>! lP: 27.6 í [: 0.7 (d); 0.87_OR1.22 (m); 1.83-2.43 (m); 3.34 (s); 6.32 (d); 6.66 (s); 7.16 (t)</td>

<td> 20</td><td>isobutyl</td><td>ethoxy</td><td>Lithium (2,4,6-trimethylbenzoyl) -isobutylphosphine + ethyl chloroformate</td><td>ÜP: 24.1 H: 1.07 (d); 1.11 (d); 1.29 (t); 2,152.27 (m); 2.29 (s); 2.31 (s); 4.32 (m); 6.88 (s)</td>

<td> 21</td><td>isobutyl</td><td>diethylamino</td><td>Lithium (2,4,6-trimethylbenzoyl) -isobutyl osphine i- diethycarbamoyl chloride</td><td>X 29.5 ] H: 1.02 (d); 1.03 pÜ); 1.09 (d); 1.15 (t); 2.10-2.33 (m); 2.28 (s); 2.29 (s); 3.35 (m); 3.93 (m); 6.85 (s)</td>

Example 22

A white, UV-crosslinkable paint is prepared by mixing

67.5 parts of oligoomeric polyester-acrylate (^RTM EBECRYL 830, UCB, Belgium)

5.0 parts hexanediol diacrylate

2.5 parts trimethylolpropane triacrylate

25.0 parts of rutile titanium dioxide (^RTM R-TC2, Tioxide, France)

2.0 parts of the photoinitiator from Example 19.

The paint is applied on an aluminum sheet, provided with a “coil-coat” (sheet in the form of a tape that is painted continuously), by means of a 100 µm clearance scraper and is reticulated. Crosslinking was carried out by passing the sample twice on a conveyor belt advancing at a speed of 10 m / min under a mercury lamp of medium pressure and 80 W / cm (Hanovia, USA). Pendulum hardness is determined according to Konig (DIN 53157) in [s]. Pendulum hardness is an indicator of the degree of crosslinking in depth of the composition. The higher the values, the higher

ES 2 194 584 A1 more effective is the crosslinking carried out. A value of 163 s is achieved. After the first hardness evaluation, the sample is re-exposed to low-pressure mercury lamps of the TL 40W / 03 type (Philips; maximum emission at 430 nm), and after 15 minutes the hardness is determined again. pendulum. After this exposure a value of 183 s is achieved. The yellowness onyx determined according to ASTM-D 1925-88 is 4.23.

Examples 23-25

Instead of the photoinitiator compound from Example 19, 2 parts of the compound from Example 5, 20 or 21 are added to the photocrosslinkable formulation described in Example 22 and applied to an aluminum sheet coated with coil-coating, as described. in Example 22. Crosslinking was carried out by passing the samples repeatedly on a conveyor belt advancing with a speed of 10 m / min under a mercury lamp of medium pressure and 80 W / cm (Hanovia, USA). USA). The sample is re-exposed to low-pressure mercury lamps of the type TL 40W / 03 (Philips; maximum emission at 430 nm), and after 15 minutes the hardness of the pendule is determined again according to Konig (DIN 53157) in [s] and the yellowness index is determined according to ASTM-D 1925-88. The results are shown in Table 4.

TABLE 4

<td>Ex.</td><td>Composed of ex.</td><td>Number of passes</td><td>Póiidilio hardness [s]</td><td>yellowness index</td>

<td> 24</td><td> 5</td><td> 4</td><td> 104</td><td> 1,43</td>

<td> 25</td><td> 20</td><td> 3</td><td> 112</td><td> 1,51</td>

<td> 26</td><td> 21</td><td> 3</td><td> 137</td><td> 1,93</td>