1,2,4-triazole and imidazole derivatives,their preparation and their use as fungicides
Abstract
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11 claims: 1 independent, 10 dependent
- 1A compound of the formula:wherein q 2 is H or CH^;Y is CH or N;R. is C,,-C. o alkyl, C,-C cycloalkyl, napthyl, ם כי 10 2 1 R 2 and R 3 are independently C^Cg alkyl, ORg, or where R^ and R,. are independently -H;halogen;“θ^-^3׳ -OCF 3 ;-SCH 3 ;-SO 2 CH 3 ;phenyl;phenyl substituted with halogen and/or alkyl and/or -CF 3 ;phenoxy;phenoxy substituted with halogen and/or C^-C^ alkyl and/or -CF 3 ;-CF 3 ;0 4 ס-ן alkyl;or cyclohexyl;and Rg is H or C^-C^ alkyl;provided that a) both R 2 and R 3 may not be OH;and b) when Y is CH and two of R^, R 2 and R 3 represent alkyl or unsubstituted phenyl, then the remaining one of R^, R 2 and R 3 may not be alkyl, cycloalkyl or unsubstituted phenyl.
- 2The compound of Claim 1 which is (l,l'-biphenyl-4-yl)dimethyl(lH-l,2,4-triazol-l-ylmethyl)silane.
- 3The compound of Claim 1 which is bis(4chlorophenyl)methyl(lH-l,2,4-triazol-l-ylmethyl)silane.
- 4The compound of Claim 1 which is [bis(4fluorophenyl)]methyl(lH-l,2,4-triazol-l-ylmethyl)silane.
- 5The compound of Claim 1 which is 4-fluorophenyl(methyl)phenyl(lH-l,2,4-triazol-l-ylmethyl)silane.
- 6The compound of Claim 1 which is (2,4-dichlorophenyl)dimethyl(IH-imidazol-l-ylmethyl)silane.
- 8A method for controlling fungus disease which comprises applying to the locus to be protected an effective amount of a compound of Claim 1 through Claim ¢ , .
- 9A method for controlling fungus disease which comprises applying to the locus to be protected an effective amount of a compound of the formula I in Claim 1 wherein Y is CH.
- 10A process for preparing a compound of the ' formula I in Claim 1 in which Y is N;־ 167 which comprises reacting 1) an intermediate selected from the group ?3 ?2 CljSiCH 2 Cl, Cl 2 SiCH 2 Cl and Cl-Si-CH 2 C1 in a suitable solvent with R^M where M is Na, Li or MgX where X is Br, Cl, I, at a temperature of from -80° to 40°C to form a chloromethylsilane;and 2) reacting the chloromethylsilane with 1,2,4-triazole or its 3-methyl derivative, or their alkali metal salts in polar aprotic solvents, ethers or ketones at 0° to 150°C.
- 11A process for preparing a compound of Formula I as defined in Claim 1 in which Y is N which comprises 1) reacting Cl R 2 R,-SiCI־LCl and R.-Si-CH,C1 1 4 ן 1 4 ן Cl Cl with RgOH in a suitable solvent with a suitable base at a temperature of 0°-100°C to form an alkoxy or dialkoxy chloromethylsilane;and 2) reacting the chloromethylsilanes with 1,2,4-triazole or its 3-methyl derivative or their alkali ־ K metal salts in polar aprotic solvents, ethers or ketones at 0° to 150 3 C. \ - ץ /3. /?. A process for preparing a compound of Formula I in Claim 1 in which Y is CH, which comprises reacting 1) an intermediate selected from the group Cl 3 SiCH 2 Cl, Cl 2 SiCH 2 Cl and Cl-Si-CHjCl r 3 in a suitable solvent with R^M where M is Na, Li or MgX where X is Br, Cl, I, at a temperature of from -80° to 40°C to form a chloromethylsilane;and 2) reacting the chloromethylsilane with imidazole or its 4-methyl derivative, or their alkali metal salts in polar aprotic solvents, ethers or ketones at 0° to 150°C. • /3. //. A process for preparing a compound of Formula I in Claim 1 in which Y is CH;which comprises 1) reacting Cl r 2 R 1 -SiCH 2 Cl and RpSi-Cf^Cl, Cl Cl with RgOH in a suitable solvent with a suitable base at a temperature of 0° to 100°C to form an alkoxy or dialkoxy chloromethylsilane;and 2) reacting the chloromethylsilane with imidazole or its 4-methyl derivative, or their alkali metal salts in polar aprotic solvents, ethers or ketones at 0° to 150°C.
Independent claims11
1,881 paragraphs in 22 sections, as filed
The present invention relates to silylmethyltriazoles and imidazoles such as, for example, dimethyl(phenyl)(lH-l,2,4-triazol-l-ylmethyl)silane and (1,1.-biphenyl-4-yl)dimethyl(lH-imidazol-l-ylmethyl)silane, and to the use of these new compounds, in controlling fungus diseases, particularly diseases of living plants.
U.S. Patent 3,692,798 discloses compounds of the formula:
?1 R<sub>2</sub>-SiCH <sup>R</sup>3 wherein Rp R<sub>2</sub> and R-j can be lower alkyl and phenyl. It is stated that these compounds are useful as antimicrobial agents.
European Patent 29,993 discloses compounds of the formula:
<img file="IL66114A_D0001.tif" />
<img file="IL66114A_D0002.tif" />
wherein R can be C^-C^ alkyl and Y and Z can be H or SiR<sub>1</sub>R<sub>2</sub>R<sub>?</sub>, wherein Rp R<sub>2</sub>, and R^ can be alkyl, haloalkyl, alkenyl, alkynyl, or substituted phenyl. It is taught that the compounds are useful as agricultural fungicides.
U.S. Patents 3,256,308 and 3,337,598 disclose compounds of the formula:
1
CH<sub>3</sub> wherein can be methyl, ethyl, vinyl, or phenyl. Their use to control fungi is also taught.
Belgian Patent 785,127 discloses quaternary ammonium salts such as:
cn<sub>3</sub> 0 (CH,0),SiCH<sub>o</sub>CH״N-n-C<sub>1Q</sub>H,<sub>7</sub> כ כ £ c כ 10 — ן /
CH<sub>3</sub> and their use as fungicides.
Research Disclosure 17,652 discloses silyl ethers of the formula:
0SiR<sub>3</sub>
Ar-CH<sub>2</sub>-CH-CH-C(CH<sub>3</sub>)<sub>3</sub> wherein Ar can be substituted phenyl, X can be CH or N, and R can be alkyl. It is taught that the compounds are useful as agricultural fungicides.
West German Patent DE 3,000,140 discloses silyl ethers of the formula:
0SiR<sub>3</sub>
Ar-0-CH-CH-C(CH<sub>3</sub>)<sub>3</sub>
<img file="IL66114A_D0003.tif" />
wherein Ar can be substituted phenyl, X can be CH or N, and R can be phenyl or lower alkyl. It is taught that these compounds are useful as agricultural fungicides.
U.S. Patent 4,248,992 discloses a class of organosilicon compounds having in a molecule at least one monovalent guanidine group represented by the general formula:
<img file="IL66114A_D0004.tif" />
in which R is a hydrocarbon atom or a monovalent hydrocarbon group. These guanidine-containing organosilicon compounds are described as useful as antifungal agents for molded plastics and rubbers, particularly silicone rubbers.
U.S.S.R. Patent 346,306 discloses silylmethylazoles of the formula:
<sup>(R</sup>l<sup>)</sup>n<sup>(R</sup>2<sup>0)</sup>3-n<sup>SiCH</sup>2<sup>Az</sup> wherein and R<sub>2</sub> are alkyl groups, n is 0-3, and Az is a pyrazole, imidazole, or benzimidazole ring, optionally substituted.
U.S.S.R. Patent 271,552 discloses silylethylazoles of the formula:
(R.) (R0״), SiCH״CH״Az in z 3-n z z wherein R^, R<sub>2</sub>, n, and Az are as described in the previous reference.
Summary of the Invention
This invention relates to silylmethyltriazoles and silylmethylimidazoles of the following formula and to agriculturally useful compositions of these 5 compounds.
<img file="IL66114A_D0005.tif" />
wherein
Q<sub>2</sub> is H or CH<sub>3</sub>;
Y is CH or N;
R<sub>x</sub> is C<sub>2</sub>־C<sub>18</sub> alkyl, C<sub>3</sub>־C<sub>6</sub> cycloalkyl, napthyl, or
<img file="IL66114A_D0006.tif" />
R<sub>2</sub> and R<sub>3</sub> are independently C^C^ alkyl, OR^, or
<img file="IL66114A_D0007.tif" />
where
R^ and R$ are independently -H; halogen;
-OCH<sub>3</sub>; -OCF<sub>3</sub>; -SCH<sub>3</sub>; -SO<sub>2</sub>CH<sub>3</sub>; phenyl; phenyl substituted with halogen and/or C^-C^ alkyl and/or -CF<sub>3</sub>; phenoxy; phenoxy substituted with halogen and/or C^C^ alkyl and/or -CF<sub>3</sub>; -CF<sub>3</sub>; C^-C^ alkyl; or cyclohexyl; and
R, is H or C-C. alkyl;
1 4 <sup>J</sup> provided that
a) both R<sub>2</sub> and Rg may not be OH; and
b) when Y is CH and two of R^, R<sub>2</sub> and Rg represent alkyl or unsubstituted phenyl, then the remaining one of R^, R<sub>2 </sub>and Rg may not be alkyl, cycloalkyl or unsubstituted phenyl.
This invention also relates to a method for con-) trolling fungus diseases, particularly fungus diseases of living plants which comprises applying to the locus to be protected an effective amount of a triazole or imidazole compound of the invention.
The salts of the triazoles and imidazoles of the invention with protic acids and complexes with metal ions are also novel.
Preferred for their high activity and/or favorable ease of synthesis are compounds of the generic scope wherein
Q<sub>2</sub> = H.
More preferred for their higher activity and/or more favorable ease of synthesis are compounds of the preferred scope wherein
R^ is
R<sub>2</sub> is Cj-C^ alkyl or
R<sub>3</sub> is alkyl.
Most preferred for their highest activity and/or most favorable ease of synthesis are compounds of the more preferred scope wherein
R| is where
R<sub>4</sub> is at the para position of , and is H, F, Cl, Br, or phenyl, and
R<sub>5</sub> is H, F, Cl, or Br; and
R<sub>2</sub> is or Cj-C^ alkyl; and Rj is Cj-C<sub>4</sub> alkyl.
Specifically preferred for their excellent activity and/or most favorable ease of synthesis are the following triazole compounds:
(Dimethyl)phenyl(lH-l2,4<sub>׳</sub>-triazol-l-ylmethyDsilane;
Dimethyl(4-methyIphenyl)(1H-1,2,4-triazol-l-yImethyl)silane;
(4-Bromophenyl)dimethyl(1H-1,2,4-triazol-l-y!methyl)silane;
(l,r-Biphenyl-4-yl)dimethyl(lH-l, 2,4-triazol-l-y 1methyDsllane;
(4-Chlorophenyl)dimethyl(lH-l,2,4-triazol-l-ylmethyDsllane;
(2,4-Dichlorophenyl)dimethyl(1H-1,2,4-triazol-l-ylmethyDsllane;
Butyl(4-chlorophenyl)methyl(lH-l,2,4-triazol-l-ylmethyDsllane;
b is( 4-Chlorophenyl) methy H1H-1,2,4-triazol-l-ylmethyDsllane;
Methyl(diphenyl)(lH-l,2,4-triazol-l-ylmethyl)silane;
[bis(4-Fluorophenyl)]methyl(lH-l,2,4-triazol-l-ylmethyDsllane;
(4-FluorophenyDdimethyl(1H-I<sub>t</sub>2,4-triazol-l-yImethyl)silane;
Butyl(2,4-dichlorophenyl)methyl(lH-l,2,4-triazol-l-ylmethyDsllane;
[bis(2,4-Dichlorophenyl)]methyK1H-1,2,4-triazol-l-ylmethyDsllane;
2,4<-Di chlorophenyl( methy l)phenyl(lH-l ,2,4-triazol-l-ylmethyDsllane;
4-Chlorophenyl\inethyl)phenyl(lH-l, 2,4-triazol-l-ylmethyDsllane;
4-Fluorophenyl(methyl)phenyl(lH-l,2,4-triazol-l-ylmethyDsllane;
Buty 1( methy Dphenyl(lH-l, 2,4-triazol-l-y Imethyl) silane;
Butyl(4-fluorophenyl)methy1(1H-1,2,4-triazol-l-ylmethyDsllane;
[bis(l,l'-Biphenyl-4-yl)]methyl(lH-l,2,A-triazol-l-ylmethyl)silane;
(1,I'-Bipheny1-4-yl)butyl(methyl)(1H-1,2,4-triazol-lylmethyDsilane; and (1,1'-Biphenyl-4-y!)methyl(phenyl)(1H-1,2,4-trlazol-lylmethyDsilane.
Especially preferred compounds, methods, and compositions of imidazoles are those compounds wherein at least one group R^, R<sub>2</sub> or R^ is other than lower alkyl (^־C^) or phenyl. In particular, the following imidazole compounds are specifically preferred for their excellent activity and/or most favorable ease of synthesis:
(1,l’-Biphenyl-4-yl)dimethyl(IH-lmidazol-l-ylmethy1)silane;
(2,4-Dichlorophenyl)dimethyl(lH-lmidazol-l-ylmethyl)silane;
Butyl(2,4-dichlorophenyl)(lH-lmidazol-l-ylmethyl)methylsilane;
[bis(4-Fluorophenyl)](IH-lmidazol-l-ylmethyl)methylsilane;
[bis(2,4-Dichlorophenyl)](IH-lmidazol-l-ylmethy1)methylsilane;
(2,4-Dichlorophenyl)(IH-imidazol-l-ylmethyl)methyl(phenyl)silane;
(4-Chlorophenyl)(IH-imidazol-l-ylmethy!)methyl(phenyl)silane;
(4-Fluorophenyl)(IH-imidazol-l-ylmethyl)methyl(phenyl)silane;
(1,1״-Biphenyl-4-yl)butyl(IH-imidazol-l-y!methyl)methylsilane;
(1,I'-Bipheny1-4-yl)(IH-imidazol-l-ylmethyl)methyl(phenyl)silane;
[bis(l,l-Bipheny1-4-yl)](IH-imidazol-l-ylmethyl)methylsilane;
Butyl(A-chlorophenyl)(IH-lmidazol-l-ylmethy!)methylsilane;
(A-Chlorophenyl)dimethyl(lH-imidazol-l-y!methyl)silane;
Dimethyl(4-fluorophenyl)(lH-imidazol-l-ylmethyDsilane; and
Butyl(4-fluorophenyl)(lH-lmidazol-l-ylmethyl)methylsilane.
When Q<sub>2</sub> is H, the process for preparing the triazole derivatives will ordinarily produce a mixture of two triazole isomers:
Formula IA
Formula IB
Two isomers are possible when the triazole substituent is CHy.
CH
Formula IC
R
Formula ID
The mixture will contain predominately the isomers of
Formula IA or Formula IC; however, the isomers of
Formulas IB and ID also have fungicidal activity, and separation of the isomers is not required.
For the imidazole derivatives, isomers are also produced:
<img file="IL66114A_D0008.tif" />
and
Formula IIA
<img file="IL66114A_D0009.tif" />
Formula I1B
The isomers of Formula IIA will generally predominate; however» the isomer of Formula IIB also has fungitoxic activity and separation of the Isomers is not required.
Detailed Description of the Invention
The term azole will be used to refer to appropriately substituted 1,2,4-triazoles and imidazoles
<img file="IL66114A_D0010.tif" />
and
<img file="IL66114A_D0011.tif" />
where may be H or CH^. In drawing structural formulas, the part-structure
<img file="IL66114A_D0012.tif" />
where Y is N or CH will be used to denote both triazole and imidazole ring systems.
Synthesis
The compounds of this Invention can be prepared from chloromethylsilanes and 1,2,4-triazole or imldazole sodium salt or their methylated homologs:
־ל
Rj-Si-CHjCl
<img file="IL66114A_D0013.tif" />
<img file="IL66114A_D0014.tif" />
Lithium and potassium azole salts may also be used. Bromomethylsilanes, iodomethylsilanes, or arylsulfonyloxymethylsilanes may be used instead of chloromethyl־ silanes. Roughly equimolar amounts of the reagents are used (except when R<sub>?</sub> 0 ־R<sub>fi</sub>; see below), with the azole salt often taken in 5-10% excess of theory. In addition, 1,2,4-trlazole or imidazole themselves can be used if an acid acceptor is added. Suitable acceptors include excess azole, alkali metal alkoxides such as sodium methoxide or potassium tert-butoxide, inorganic bases such as potassium carbonate, or sodium hydride, and tertiary amines such as triethylamine, when the acid acceptor is a good nucleophile, such as sodium methoxide, an excess should be avoided to prevent undesired side reactions. Suitable solvents inelude polar aprotic solvents such as dimethylformamide, dimethyl sulfoxide, or acetonitrile; ethers such as tetrahydrofuran or 1,2-dimethoxyethane; and ketones such as 2-butanone. The reaction temperature can vary between 0° and 200°C, preferably between 25° and 100°C. The reaction can be conducted under elevated pressure, but it is generally preferable to operate at atmospheric pressure. The optimum temperature and reaction time will vary with the concentra tion and choice of reagents, and especially with the choice of solvent. For example, 1,2,4-triazole and sodium methoxide at roughly 2 molar concentration in dimethylformamide gives good conversion in approximately 2 hours at 80-90°C, whereas 1,2,4-triazolt and potassium carbonate at roughly 1 molar concentration in 2-butanone requires 8-12 hours at reflux. The imidazole reactions are generally more rapid. In general, reaction times of 1 to 24 hours are required.
Progress of the reaction can be followed by working up aliquots for nmr analysis and following the intensities of the starting material SiCH^Cl singlet near 2.9 and the product SiCHgN singlets, which are near 3.8 for compounds of Formula I and near 3.7 for compounds of Formula II.
With respect to the triazole derivatives, the 1H-1,2,4-triazol-l-y!methyl compound as prepared above is accompanied by a minor amount of the isomeric 4H-1,2,4-triazol-4-ylmethyl compound:
RpSi-CH R,
<img file="IL66114A_D0015.tif" />
The ratio of isomers varies with values of R and reaction conditions, with a !-substituted to 4-substituted ratio of roughly 10:1 often observed. The monomethyltriazoles give similar 4H-isomers as minor products:
CH, <sup>R</sup>2 D ׳q-h-cv J
When the unsubstituted silylmethyltriazole Is available, metalatlon-methylatlon provides an alter־ nate synthesis of the methylated homologs:
<img file="IL66114A_D0016.tif" />
1. c<sub>4</sub>h<sub>9</sub>h
2. CHjI
R.-SI-ChV ן
Rj <sup>N</sup>^CHj
With respect to the imidazole derivatives, isomers are also possible. Two isomers result:
<img file="IL66114A_D0017.tif" />
and
<img file="IL66114A_D0018.tif" />
Formula IIA
Formula IIB
The product of Formula IIA will generally predomi־ nate. If desired, the Isomers may be separated by standard techniques such as crystallization, distillation, or chromatography.
For the case where Rj * ORg In the triazole or Imidazole product, the chlorines of a chloro(chloromethyDsilane can be replaced in one of two ways. In one method, at least two equivalents of the azole sodium salt can be used. An intermediate containing a very reactive sllicon-azole bond forms, and reaction with water or an alcohol gives the desired oxygenated compounds:
*2 RpSi-CHjCl
Cl
<img file="IL66114A_D0019.tif" />
<img file="IL66114A_D0020.tif" />
R<sub>r</sub>0H o
<img file="IL66114A_D0021.tif" />
Suitable solvents and reaction conditions are the same as those outlined on pages 11, 12 and 13 for azole displacements. The temperature of alcoholysis is not critical, and warming to 50-100°C can be used to ensure complete reaction when = C^-C^ alkyl. For R<sub>fi</sub> = H, however, hydrolysis is best conducted near room temperature to minimize disiloxane formation, recognizing that silanol-disiloxane equilibrium is possible whenever ־ H:
<sup>R</sup>2 /5?
R.-Si-CH<sub>O</sub>N ן 1 . 2 \ A
OH <sup>Y x</sup>Q<sub>2</sub>
-h<sub>9</sub>0 j,—־ +H<sub>2</sub>0
<img file="IL66114A_D0022.tif" />
The position of equilibrium and the rate at which it is established will vary with the values of R^ and R<sub>2</sub>, solvent, temperature, end the presence or ebsence of acidic or basic catalysts.
In the second method, the slllcon-oxygen bond is formed first, followed by azole displacement as de* scribed earlier:
R<sub>1</sub>-Si-CH<sub>2</sub>C1 ------> RpSi-CHjCl
Cl OR, o
<img file="IL66114A_D0023.tif" />
Reaction of the chlorosilane with R^OH may be conducted in almost any non-hydroxylic solvent, with ethers such as diethyl ether, 1,2-dimethoxyethane, and tetrahydrofuran or dipolar aprotic solvents such as dimethylformamide and acetonitrile being preferred. Although an acid acceptor is not required, it is preferred to add a tertiary amine such as triethylamine or pyridine. The reaction temperature may vary from 0° to 100°C, and R<sub>fi</sub>0H is often taken in excess of theory. The combination of 2 equivalents of R^OK, 1.1 equivalents of triethylamine, and 0.1 equivalents of imidazole in dimethylformamide at 60° for two hours has been broadly applicable.
Extending these methods to (chloromethyl)dichlorosxlanes provides dioxygenated silanes:
Cl
RpSi-CHjCl
Cl
OR,
R.-Si-CH,N <sup>,</sup>ו
0r<sub>6</sub>
Glycol derivatives are formed similarly, using a diol instead of two molecules of R^OK.
An alternative synthesis for alkoxy(chloromethyDsilanes involves selective replacement of one alkoxy group of a dialkoxysilane with an organometallie reagent:
2ל 2?
(R<sub>6</sub>0)<sub>2</sub>Si-CH<sub>2</sub>Cl <sup>8</sup>!<sup>MgX></sup> x RpSi-CH^l <sup>R</sup>l<sup>Li</sup>’ ' OR.
or R^Na
Conditions for this displacement are as described in the next paragraph, with the added stipulation that the organometallic should be added to the dialkoxy15 silane.
The required chloromethylsilane starting materials are made from commercially available chloro(chloromethyl)dimethylsilane, chloromethyl(dichloro)methylsilane, or chloromethyltrichlorosilane:
<sup>20</sup> ?״,ch,
Cl-Si-CH״C1 , Cl-Si-CH«C1, <sup>1 2</sup> ׳<sup> z</sup>R
CH, Cl,2 <sup>צ</sup> R<sub>1</sub>-Si-CH<sub>2</sub>C1 or Cl,SiCH<sub>?</sub>Cl
The Si-Cl bonds in these compounds react with organolithium, organosodium, or Grignard reagents to introduce alkyl and/or aryl groups according to literature procedures, leaving the C-Cl bond intact. For the silanes containing two or three Si-Cl bonds, stepwise replacements are possible, giving considerable flexibility to the values of R^-R^. Bromosilanes, iodosilanes, or alkoxysilanes may be substituted for chlorosilanes in these reactions. Preferred solvents <sup>35</sup> for these reactions include ethers such as tetrahydro furan, 1,2-dimethoxyethane, and diethyl ether, or hydrocarbons such as hexane and toluene. The preferred temperature will vary between -80° and 40° depending on the nature of the organometallic reagent, how it was generated, and the solvent. For example, when aryllithium reagents are generated in tetrahydrofuran from aryl bromides using butyllithium, the mixture should be held below roughly -40° to avoid side reactions involving the bromobutane produced. If the organometallic solution is stable at higher temperatures, however, reactions may be run at -20° to 25° without competing reaction of the Ch^Cl group. The reaction is rapid at all temperatures, and only a short period, for example 30 to 60 minutes, is required after the reagents are combined to ensure complete reaction.
Reactions of ClSi(CH^)<sub>2</sub>CH<sub>2</sub>C1 with Grignard reagents are described by C. Eaborn and J. C. Jeffrey, J. Chem. Soc., 1954, 4266; and a recent review on synthesis of aryltrimethylsilanes from CISKCH^)^, which contains experimental procedures useful for CISKCHj)2CH<sub>2</sub>C1 reactions, is that of D. Habich and F. Effenberger, Synthesis, 1979, 841. Selective intraduction of one new alkyl group into Cl<sub>2</sub>Si(CH<sub>3</sub>)CH<sub>2</sub>01 is described by V. P. Kuznetsova and R. M. Sokolovaskaya, Zh. Obshch. Khim., 1969, 1977; Chem. Abstr., 72, 31897 p; and one aryl group may be introduced selectively as well:
ch<sub>3</sub> ch<sub>3</sub>
Cl<sub>2</sub>Si-CH<sub>2</sub>Cl + ArLi Cl-Si-CH<sub>2</sub>C1
Ar
In both cases the organometallic reagent should be added to the dichlorosilane at low temperature with good mixing for best yields.
Reactions of Cl<sub>3</sub>SiCH<sub>2</sub>Cl with Grignard reagents are described by A. A. Zhdanov, V. I. Pakhomov, and
T. Bazhanova, Zh. Obshch. Khim., 1973, 1280; Chem.
Abstr., 79, 66452 m. Adding organometallic reagents to the trichlorosilane is recommended even when three identical groups are being introduced, because adding Cl<sub>3</sub>SiCH<sub>2</sub>Cl to an organometallic reagent is not usually successful. A single aryl group may also be introduced:
<sup>10</sup> 01
Cl<sub>3</sub>SiCH<sub>2</sub>Cl + ArLi Ar-Si-CH<sub>2</sub>C1
Cl
A useful modification of literature procedures, applicable when R! or R'^ is an aryl group, has been developed in the present work. Instead of preforming an organolithium reagent and then combining it with a chlorosilane, it has been found that an aryl bromide and a chlorosilane such as ClSi(CH<sub>3</sub>)<sub>2</sub>CH<sub>2</sub>Cl וחay be combined in an inert solvent such as tetrahydrofuran and treated at -80 to -40° with butyllithium. Bromine-lithium exchange proceeds selectively, and the resulting aryllithium reacts with the Si-Cl bond as it is formed:
25Γ ch<sub>3</sub>0h
ArBr + Cl-Si-CH<sub>9</sub>C1 H־<sup>C</sup>4<sup>H</sup>9<sup>L1</sup> ArLi + Cl-Si-CH9C1 ־ * ן p 11 pw״״׳*f
CH<sub>3</sub> ־<sup>b</sup>4<sup>n</sup>9<sup>br</sup>CH <sup>30</sup>ch
Ar-Si-CH<sub>9</sub>C1
-LiClL
This reaction works equally well for aryl-substituted chlorosilanes such as ClSi(CH<sub>3</sub>)(CgH<sub>5</sub>)CH<sub>2</sub>Cl, and it can be used to introduce two aryl groups into C12Si(CH<sub>3</sub>)CH2Cl. In a further extension, an aryl and an £-butyl group may be introduced in one step:
CH, CH, ' ? 9η-Γ Uli <sup>כ</sup> י
ArBr + . C^Si-CH^l Ar-Si-CH<sub>2</sub>C1 n־C<sub>4</sub><sup>H</sup>9
Substitution of other alkyllithiums RLi for ri-butyllithium provides a general route to Ar(CH<sub>3</sub>)Si(R)CH2Cl.
In the following examples, temperatures are reported in degrees Celsius. Abbreviations for nuclear magnetic resonance (nmr) spectra are s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet; peak positions are reported as parts per million downfield from internal tetramethylsilane. Infrared (ir) peak positions are given in reciprocal centimeters (cm<sup>-</sup>^). Hexanes refers to the mixture of isomers boiling 68-69°, and ether refers to diethyl ether.
Example 1 Preparation of (1,1'-Biphenyl-4-yl)(chloromethyl)dimethylsilane
A solution of 9.9 g (0.042 mol) of 4-bromobiphenyl in 50 ml of dry tetrahydrofuran was cooled to -78° under nitrogen and stirred while 26.5 ml (0.042 mol) of 1.6 molar n-butyllithium in hexane was added dropwise over 15 minutes. A thick slurry formed, and 35 ml of tetrahydrofuran was added to facilitate stirring. With continued cooling, 5.9 ml (6.7 g, 0.046 mol) of chloro(chloromethyl)dimethylsilane was added over 10 minutes, giving a clear solution that was allowed to warm to room temperature. Addition of 300 ml of ether, filtration to remove precipitated lithium chloride, and evaporation Of the filtrate left 13.2 g of semisolid. Redissolution in ether, filtration, and evaporation of the filtrate left 11.0 g (100% crude) of the title compound as a colorless solid, m.p. 30-40°, suitable for further reaction. Trace impurities could be removed by sublimation at 30°/0.1 mm, leaving the title compound unsublimed in 83% re0 covery: m.p. 37-40°; ir (Nujol ) 1585, 1240, 1110, 830, 810, 750, 690 cm<sup>1</sup>־; nmr (COCl-j) 0.4 (6H, s),
2.9 (2H, s), 7.3-7.7 (9H, m).
Example 2 Preparation of (4-Bromophenyl)(chloromethyl)dimethylsilane.....................
4-Bromophenylmagnesium bromide was prepared from 5 11.8 g (0.050 mol) of 1,4-dibromobenzene and 1.2 g (0.050 g-atom) of magnesium turnings in 75 ml of ether according to G. P. Schiemenz, Org. Syn., Coll. Vol. 5, 496 (1973). The resulting mixture was chilled in ice under a nitrogen atmosphere while a solution of 6.6 ml 10 (7.2 g, 0.050 mol) of chloro(chloromethyl)dimethylsilane in 10 ml of ether was added dropwise. The reaction mixture was then stirred overnight at room temperature, quenched carefully with saturated aqueous ammonium chloride, and filtered. The ether phase of 15 the filtrate was washed with brine, dried over magnesium sulfate, and evaporated to leave 9.8 g of an oil. Distillation gave 3.8 g (29%) of the title compound as a colorless liquid: bp 97° (1 mm); ir (neat) 2950, 1575, 1475, 1370, 1250, 1065, 1010, 840, 20 805, 720 cm“<sup>1</sup>; nmr (CDClj) 0.4 (6H, s), 2.9 (2H, s), 7.3-7.7 (4H, m).
Example 3
Preparation of Chloromethyl(4-chlorophenyl)dimethylsilane.....................
A solution of 9.6 g (0.050 mol) of 4-bromochlorobenzene and 6.6 ml (7.2 g, 0.050 mol) of chloro(chloromethyl)dimethylsilane in 75 ml of tetrahydrofuran was stirred at -78° under nitrogen while 31 ml (0.050 mol) of 1.6 molar n-butyllithium in hexane was added dropwise. The resulting clear solution was allowed to warm to room temperature, diluted with ether until no more lithium chloride precipitated, and filtered. Evaporation of the filtrate left 10.6 g of a light yellow liquid, which was distilled to give 6.0 g (55%) of the title compound as a colorless liquid: bp 54-58°C (0.05 mm); ir (neat) 2910, 1560, 1470, 1370, 1250, 1080, 1010, 840, 805, 790, 740 cm<sup>1</sup>־; nmr (CDClj) 0.4 (6H, s), 2.9 (2H, s), 7.1-7.6 (4H, q).
The in situ aryllithium generation described in this example is also useful for preparing the product of Example 1. If the reaction is run at 0.5-0.7 molar in 4-bromobiphenyl and the temperature is held at -65 to -55°C during butyllithium addition, little or no solid precipitates.
Example 4
Preparation of Chloromethyl(2,4-dichlorophenyl)dimethylsilane.......
A solution of 17.0 g (0.075 mol) of 2,4-dichlorobromobenzene and 10.8 ml (11.8 g, 0.082 mol) of chloro(chloromethyl)dimethylsilane in 100 ml of dry tetrahydrofuran was chilled to -70° under nitrogen and stirred while 49 ml (0.079 mol) of 1.6 molar n-butyllithium in hexane was added dropwise at a rate that held the mixture below -70°. The resulting cloudy reaction mixture was allowed to warm to room temperature, poured into 400 ml of hexanes, filtered, and evaporated to leave 20.5 of yellow liquid. Distillation gave 12.6 g (66%) of the title compound as a colorless liquid: bp 83° (0.02 mm); ηθ<sup>4</sup> 1.5522; ir (neat) 1565, 1455, 1360, 1255, 1120, 1100, 1040, 825 cm<sup>1</sup>־; nmr (COClj) 0.5 (6H, s), 3.1 (2H, s), 7.0-7.5 (3H, m).
Example 5
Preparation of Chloromethyl(2,6-dimethoxyphenyl)dimethylsilane .....,
A solution of 25.0 g (0.181 mol) of 1,3-dimethoxybenzene in 250 ml of tetrahydrofuran was stirred at room temperature under nitrogen while 125 ml (0.200 mol) of 1.6 molar n-butyllithium in hexane was added dropwise over 30 minutes. The resulting mixture was refluxed 1.5 hour, giving an orange-brown solution that was cooled to 5° and stirred while 27 ml (29.4 g, 0.205 mol) of chloro(chloromethyl)dimethylsilane was added dropwise over 15 minutes. The resulting white suspension was allowed to warm to room temperature, stirred there 1 hour, diluted with ethyl acetate, poured into water, and extracted with ether. The organic layers were washed with brine, dried over magnesium sulfate, and distilled to give 37.0 g (84%) of the title compound as a colorless liquid: bp 98-110° (0.1 mm); nmr (CDCip 0.4 (6H, s), 3.1 (2H, s), 3.7 (6H, s), 6.3 (2H, d), 7.1 (IH, m).
By varying the organolithium or Grignard reagent, the procedures of Examples 1-5 can be used to prepare the compounds of Table I. Closely related procedures are also known in the literature, for example the use of arylmagnesium chlorides by C. Eaborn and J. C. Jeffrey, J. Chem. Soc., 1954, 4266. For compounds where is a phenyl ring bearing a
2-halo substituent, an alternative to the in situ procedure of Example 4 is the special arylmagnesium iodide method of C. Eaborn, K. L. Jaura, and 0. R. M. Walton, J. Chem. Soc., 1964, 1198.
Table I
CH<sub>3</sub>
X-Si-CH<sub>2</sub>C1
CH, j
X = «ן R־y —
n־<sup>c</sup>12<sup>H</sup>25 —”^18<sup>H</sup>37 cyclopropyl cyclopentyl cyclohexyl
1- naphthyl
2- naphthyl phenyl 4-fluorophenyl 4-methoxyphenyl 4-phenoxyphenyl
4-(4-chlorophenoxy)phenyl 4-(4-fluorophenoxy)phenyl bp 127-128° bp 172° ηθ<sup>3</sup> 1.4510 ηθ 1.4556 bp 120-130° (10 mm) bp 112° (0.08 mm) bp 85-86° (3 mm) bp 59-60° (0.1 mm) bp 80° (0.05 mm) bp 122° (0.03 mm) ηθ 1.5773
4-(4-trifluoromethyIphenoxy) phenyl
4-(4-methylphenoxy)phenyl
4-thiomethylphenyl
4-trifluoromethylphenyl
4-methylphenyl
4-i-propylphenyl
4-t-butylphenyl
4-methyIsulfonylphenyl
4-cyclohexylphenyl
4-trifluoromethoxyphenyl bp 92-93° (0.05 mm) ηθ 1.4686 bp 96° (7 mm) ηθ<sup>3</sup> 1.5056
m.p. 64-68° ηθ 1.5424 bp 55-57° (0.15 mm)
4-(4-chlorophenyl)phenyl
4-(4-bromophenyl)phenyl
Table I (continued)
4-(4-methylphenyl)phenyl
4-(4-tri fluoromethylphenyl)phenyl
4-(4-fluor□phenyl)phenyl
3-phenylphenyl
3-tri fluoromethylphenyl
3-chlorophenyl
2-trifluoromethylphenyl
2-phenylphenyl
2-chlorophenyl 2-methoxyphenyl
2,3-dimethylphenyl
2.3- dimethoxyphenyl
2.4- difluorophenyl
2-fluoro-4-chlorophenyl 2-chloro-4-phenylphenyl
2-fluoro-4-phenylphenyl
2- methyl-5-chlorophenyl
2,6-dimethylphenyl
3.4- dichlorophenyl
3- methy1-4-fluorophenyl
3,5-dichlorophenyl ηθ 1.5862 bp 59-62° (0.3 mm) bp 73° (0.15 mm)
Πρ 1.4826
Πρ° 1.5772 bp 78-80° (0.3 mm) np<sup>1</sup> 1.5164
Πρ 1.5254 bp 98° (0.6 mm) bp 94-95° (0.25 mm)
Example 6
Preparation of (l,l'-Biphenyl-4-yl)butyl(chloromethyl)methylsilane...... ׳ ־ ־ ......
The title compound can be prepared by the procedure of Example 1 by substituting (butyl)chloro(chloromethyDmethylsilane for chloro(chloromethyl)dimethylsilane.
Related compounds can be prepared by the procedures of Examples 1-5, using the appropriate organolithium or Grignard reagent and Cl(R<sub>2</sub>)Si(CH<sub>3</sub>)CH<sub>2</sub>Cl. The required chloromethylsilane starting materials are made from R<sub>2</sub>MgCl or R<sub>2</sub>Li and Cl<sub>2</sub>Si(CH-j)CH<sub>2</sub>Cl according to Examples 14 and 15, and literature procedures such as V. P. Kuznetsova and R. M. Sokolovaskaya, Zh. Obshch. Khim., 1969, 1997.
Alternatively, both the biphenyl and butyl groups can be introduced simultaneously as follows: A solution of 23.3 g (0.10 mol) of 4-bromobiphenyl and 12.7 ml (16.4 g, 0.10 mol) of chloromethyl(dichloro)methylsilane in 150 ml of dry tetrahydrofuran was chilled under nitrogen to -70° and stirred while 125 ml (0.20 mol) of 1.6 molar n-butyllithium in hexane was added at a rate that held the mixture below -60°C. The resulting thin slurry was allowed to warm to room temperature, treated cautiously with 10 ml of ethyl acetate, and poured into 300 ml of water. The organic layer was separated, the aqueous phase was washed with another 100 ml of hexanes, and the combined organic phases were washed three times with water, once with brine, dried over magnesium sulfate, and evaporated to leave 33.9 g of a viscous yellow oil. Distillation gave 9.5 g (31%) of the title compound: bp 135-158° (0.1 mm); n<sup>22</sup> 1.5743; ir (neat) 3060, 3015, 2960, 2920, 2870, 1600, 1485, 1390, 1380, 1250, 1120, 1075, 1005, 875, 810, 800, 760, 700 cm<sup>1</sup>; nmr (CDCl-j): 0.4 (3H, s), 0.6-1.8 (9H, m), 2.9 (2H, s) and 7.0-7.7 (9H, m).
Example 7
Preparation of Butyl(chloromethyl)(4-chlorophenyl)methylsilane .............
A solution of 14.4 g (0.075 mol) of 4-bromochlorobenzene and 9.5 ml (12.3 g, 0.075 mol) of chloromethyl(dichloro)methylsilane in 150 ml of tetrahydrofuran was cooled to -60° under nitrogen and stirred while 94 ml (0.15 mol) of 1.6 molar n-butyllithium in hexane was added dropwise at a rate that held the mixture between -65 and -55°. The resulting slurry was allowed to warm to room temperature, giving a solution that was diluted with hexanes until no more lithium chloride precipitated. Filtration, evaporation of the filtrate, dissolution of the residue in hexanes, refiltration, and evaporation left 19.8 g of a pale orange liquid. Distillation gave first 1.8 g (12%) of chloromethylCdibutyDmethylsilane, bp 45°C (0.05 mm),. followed by 6.8 g (35%) of the title compound as a colorless liquid: bp 90°C (0.05 mm); n^<sup>1</sup> 1.5246; ir (neat) 2925, 1580, 1380, 1260, 1090, 1015, 820, 740 cm<sup>1</sup>־; nmr (CDClg) 0.4 (3H, s), 0.6-1.5 (9H, m), 2.9 (2H, s), 7.0-7.4 (4H, q).
Example 8 Preparation of Chloromethyl(2,4-dichlorophenyl)methyl(phenyl)silane
A solution of 13.6 g (0.060 mol) of 2,4-dichloro5 bromobenzene and 12.3 g (0.060 mol) of chloro(chloromethyl)methyl(phenyl)silane (prepared as in Example 14) in 85 ml of dry tetrahydrofuran was chilled to -60° under nitrogen and stirred while 38 ml (0.060 mol) of 1.6 molar n-butyllithium in hexane was added 10 dropwise at a rate that held the mixture below -55°.
The resulting red solution was allowed to warm to room temperature, treated with 5 ml of ethyl acetate to quench any unreacted organolithium reagent, and poured into 170 ml of water. The organic layer was sepa15 rated, the aqueous phase was washed with 50 ml of hexanes, and the combined organic phases were washed three times with water and once with brine, dried over magnesium sulfate, and evaporated to leave 19.0 g of bright yellow oil. Distillation gave 8.6 g (45%) of 20 the title compound as a colorless liquid: b.p.
125-130° (0.05 mm); n^<sup>1</sup> 1.5978; ir (neat) 3080, 3060, 2960, 2930, 1570, 1540, 1460, 1430, 1365, 1260, 1120, 1100, 1040, 820, 745, 735, 705 cm<sup>1</sup>־; nmr (CDClj) 0.8 (3H, s), 3.4 (2H, s), 7.2-7.9 (8H, m).
Example 8A Preparation of (1,1'-Biphenyl-A-yDchlorbmethyKAfluorophenyDmethylsilane ______________________
A solution of 10.0 g (32.8 mmol) of (l,l'-biphenyl-4-yl)(chloromethyl)methyl(2-propoxy)silane and
3.6 ml (32.8 mmol) of 4-bromofluorbbenzene in 30 ml of dry tetrahydrofuran was cooled to -60° under nitrogen and stirred while 20.5 ml (32.8 mmol) of 1.6 molar n-butyllithium in hexane was added at a rate that held the mixture below 50°. After stirring at -70° for another 30 minutes, the solution was allowed to warm to room temperature and was worked up as in Example
8. The resulting crude product was subjected to distillation at 130-150° (0.2 mm) to remove unreacted starting material, leaving the title compound as an oil: ηθ<sup>3</sup> 1.5128; nmr (CDClj): 0.7 (3H, s), 3.1 (2H, s), 7.1 (2H, t), 7.2-7.8 (11H, m).
χ 30
Example 9 Preparation of Chloromethyl[bis(4-chlorophenyl)]methylsilane...................
A solution of 19.1 g (0.10 mol) of 4-chlorobromobenzene in 200 ml of dry tetrahydrofuran was chilled to -60° under nitrogen and stirred while 63 ml (0.10 mol) of 1.6 molar n-butyllithium in hexane was added dropwise at a rate that held the mixture below -55°. Stirring and cooling were continued while 6.3 ml (8.2 g, 0.05 mol) of chloromethyl(dichloro)methylsilane was added dropwise at a rate that held the mixture below -50°. The resulting orange solution was allowed to warm to room temperature, and workup as in Example 8 provided 16.5 g of a pale yellow oil. Kugelrohr distillation at 0.05 mm and an airbath ternperature of 130-150°C gave 9.5 g (60%) of the title 24 compound as a colorless liquid: n^ 1.5913; ir (neat) 3080, 3040, 3020, 2960, 2930, 1580, 1490, 1380, 1260, 1085, 1015, 805, 790, 775, 740 cm<sup>1</sup>־; nmr (C0Cl<sub>3</sub>) 0.7 (3H, s), 3.1 (2H, s), 7.2-7.7 (8H, וזו) ; analysis for C^H^C^Si (mw 315.70):
Calculated: C, 53.26; H, 4.15; Cl, 33.69.
Found: C, 53.4; H, 4.4; Cl, 34.2.
53.5; 4.4; 34.1.
Example 10
Preparation of (Chloromethyl)bis(4-fluorophenyl)methylsilane_____
A solution of 35 g (0.20 mol) of 4-fluorobromobenzene in 300 ml of dry tetrahydrofuran was chilled to -60° under nitrogen and stirred while 126 ml (0.20 mol) of 1.6 molar n-butyllithium in hexane was added dropwise at a rate that held the mixture below -55°. Stirring and cooling were continued while 12.6 ml (16.4 g, 0.10 mol) of chloromethyl(dichloro)methylsilane was added dropwise at a rate that held the mixture below -50°. The resulting solution was allowed to warm to room temperature, and workup as in Example 8 provided 26.4 g of a clear yellow liquid. Distillation gave 20.6 g (73%) of the title compound as a colorless liquid: bp 107-127° (0.1 mm); ηθ^ !.5481; nmr (CDCl^): 0.7 (3H, s), 3.2 (2H, s), 7.1 (4H, t, J = 9) and 7.6 (4H, d of d, J = 6 and 9).
Repeating this reaction using chloromethyKdiethbxy)methylsilane instead of the dichlorosilane gave the title compound In 58% yield after distillation:
ו?
bp 115-138° (0.2 mm); ηθ 1.5464; nmr as above.
A similar sample of the title compound was crystallized from ether-hexane at -78° to give a colorless solid, m.p. 39-40°.
Example 11 Preparation of Chloromethyl(2-chlorophenyl)(4-chlorophenyl)methylsilane
A solution of 6.3 ml (8.2 g, 0.05 mol) of chloromethyl(dichloro)methylsilane and 8.1 g (0.05 mol) of 2-bromochlorobenzene in 75 ml of dry tetrahydrofuran was chilled to -60° under and stirred while 31 ml (0.05 mol) of 1.6 molar n-butyllithiumhexane solution was added at a rate that held the mixture below -55°. With continued cooling and stirring,
8.1 g (0.05 mol) of 4-bromochlorobenzene was added as a solid, followed by another 31 ml portion of the 1.6 molar n-butyllithium solution at a rate that held the mixture below -55°C. The resulting thin slurry was allowed to warm to room temperature, treated cautiously with 10 ml of ethyl acetate, and worked up as in Example 8 to give 15.0 g of a clear yellow oil. Disfiliation provided 5.9 g (37%) of the title compound: bp 150-165° (0.7 mm); n{1.5916 °־; ir (neat) 3060, 3020, 2960, 2920, 2870, 1580, 1560, 1490, 1420, 1380, 1255, 1125, 1115, 1085, 1035, 1015, 805, 750 cm<sup>1</sup>־;
nmr (CDClj) 0.8 (3H, s), 3.3 (2H, s), 7.2-7.7 (8H, m).
The compounds of Table II are made by stepwise replacement of the Si-Cl bonds of Cl<sub>2</sub>Si(CH<sub>3</sub>)CH<sub>2</sub>Cl, according to the procedures of Examples 6-11.
Table Π “j X-Sl-CHjCl
<td> X « R<sub>x</sub></td><td></td><td></td>
<td></td><td></td><td></td>
<td><sup>C</sup>A</td><td><sub>C2</sub>h<sub>5</sub></td><td></td>
<td> a־<sup>c</sup>A</td><td></td><td> bp 45. (0.05 mm)</td>
<td> S־<sup>C</sup>1A7</td><td> 3-methylbutyl</td><td></td>
<td> cyclopropyl</td><td> *Vij</td><td></td>
<td> 1-naphthyl</td><td> -<sup>Κ</sup>Λ</td><td></td>
<td> 2-naphthyl</td><td></td><td></td>
<td> phenyl</td><td></td><td></td>
<td> phenyl</td><td> s־<sup>c</sup>A</td><td> bp 82-900.1)״ urn)</td>
<td> phenyl</td><td> 1,1-dimethyIpropy1</td><td></td>
<td> 4-phenylphenyl</td><td></td><td></td>
<td> 4-bromophenyl</td><td> 7^־1</td><td></td>
<td> 4-fluorophenyl</td><td></td><td> bp 90-920.1)״ mm)</td>
<td> 4-phenoxyphenyl</td><td> -<sup>0</sup>״Λ</td><td></td>
<td> 3-tri fluoromethyIpheny1</td><td></td><td></td>
<td> 3-chlorophenyl</td><td> n-<sup>c</sup>5<sup>H</sup>u</td><td></td>
<td> 2-phenylphenyl</td><td> -<sup>0</sup>Λ</td><td></td>
<td> 2,4-dichlorophenyl</td><td> h־c<sub>4</sub>h<sub>9</sub></td><td> bp 109-1120.1)״ mm)</td>
<td> 2,3-dimethy Ipheny1</td><td> n-CjH?</td><td></td>
<td> 2,5-dimethoxypheny1</td><td> 4-methylpentyl</td><td></td>
Table II (continued)
X « R<sub>x</sub>
2,6-dimethylphenyl
3,5-dichlorophenyl
ל
1-methylbutyl
<td> phenyl</td><td> phenyl</td><td> bp 104-110°(0.2 mm)</td>
<td> 4-fluorophenyl</td><td> phenyl</td><td> nj*<sup>2</sup> 1.5624</td>
<td> 4-chlorophenyl</td><td> phenyl</td><td> bp 140-148°(0.1 mm)</td>
<td> 4-bromophenyl</td><td> phenyl</td><td> bp 145-155°(0.1 mm)</td>
<td> 4-phenylphenyl</td><td> phenyl</td><td> bp 173-1780(0.1 mm)</td>
<td> 4-t-butylphenyl</td><td> phenyl</td><td></td>
<td> 4-thiomethylphenyl</td><td> phenyl</td><td></td>
<td> 4-phenoxyphenyl</td><td> phenyl</td><td></td>
<td> 4-tri fluoromethoxy phenyl</td><td> phenyl</td><td></td>
<td> 4-methylsulfonylphenyl</td><td> phenyl</td><td></td>
<td> 4-cyclohexylphenyl</td><td> phenyl</td><td></td>
<td> 4-(4-fluorophenyl)phenyl</td><td> phenyl</td><td></td>
<td> 3-tri fluoromethylphenyl</td><td> phenyl</td><td></td>
<td> 2-chlorophenyl</td><td> phenyl</td><td> bp 132-135°(0.1 nm)</td>
<td> 2-methaxyphenyl</td><td> phenyl</td><td></td>
<td> 2-chloro-4-phenylphenyl</td><td> phenyl</td><td></td>
<td> 2-fluoro-4-phenylphenyl</td><td> phenyl</td><td></td>
<td> 3,5-dichlorophenyl</td><td> phenyl</td><td></td>
<td> 2,5-dimethoxypheny1</td><td> phenyl</td><td></td>
<td> 2,6-dimethoxypheny1</td><td> phenyl</td><td></td>
<td> 4-bromophenyl</td><td> 4-bromophenyl</td><td> bp 160-170°(0.1 mm)</td>
<td> 4-phenylphenyl</td><td> 4-phenylphenyl</td><td> m.p. 115-117°</td>
<td> 4-methoxyphenyl</td><td> 4-methoxyphenyl</td><td> bp 166-171°(0.1 mm)</td>
<td> 3-trifluoromethylphenyl</td><td colspan="2"> 3-trifluoromethylphenyl</td>
<td> 2-methoxyphenyl</td><td> 2-methoxyphenyl</td><td></td>
<td> 2-chlorophenyl</td><td> 2-chlorophenyl</td><td> bp 135-1400.1)״ mm)</td>
<td> 2,4-dichlarophenyl</td><td> 2,4-dichloropheny1</td><td> n^<sup>-</sup> 1.5956</td>
<td> 3,5-dichlorophenyl</td><td> 3,5-dichlorophenyl</td><td></td>
Table ΙΓ (continued)
X =
2-chlorophenyl 4-phenylphenyl 4-phenylphenyl 4-phenylphenyl 4-fluorophenyl
4-chlorophenyl 1-naphthyl 4-phenoxyphenyl
4-methylphenyl
4-fluorophenyl
4-chlorophenyl
4-fluorophenyl
2.4- dichloropheny1
2.4- dichlorophenyl
2.4- dichlorophenyl
2,6-dime thoxypheny1
3.4- dichlorophenyl
4-methylphenyl b.p. 118-122 (0.1 mm)
Example 12
Preparation of (1-1<sup>1</sup>-Biphenyl-l-yl)(chloromethyl)diethylsilane .........
The title compound can be prepared by the procedure of Example 1, using chlorochloromethyldiethylsilane instead of chlorochloromethyldimethylsilane.
Similar compounds can be prepared by applying the procedures of Examples 1-5 to the appropriate organolithium or Grignard reagent and Cl(R<sub>2</sub>)Si(R<sub>3</sub>)CH<sub>2</sub>Cl. The required chlorochloromethyldialkylsilanes are made from Cl<sub>3</sub>SiCH<sub>2</sub>Cl, using two equivalents of R<sub>2</sub>MgCl or R<sub>2</sub>Li when R<sub>2</sub> = R^ (see, for example, A. A. Zhdanov, V. I. Pakhomov, and T. Bazhanova, Zh. Obshch. Khim., 1973, 1280), or using one equivalent of R<sub>2</sub>MgCl or R<sub>2</sub>Li followed by one equivalent of R^MgCl or R-jLi when R<sub>2</sub> is not equal to R-j.
Example
Preparation of (Chloromethyl)triphenylsilane A solution of 12.6 ml (18.4 g, 0.10 mol) of (chloromethyl)trichlorosilane in 150 ml □f dry ether 5 was stirred under nitrogen and chilled in ice while 162 ml (0.30 mol) of 1.85 molar phenyllithium in cyclohexane-ether 70:30 was added dropwise at a rate that held the mixture below 15°C. The resulting slurry was stirred overnight at room temperature, 10 treated carefully with 10 ml of ethyl acetate to quench any remaining phenyllithium, washed with water and brine, dried over magnesium sulfate, and evaporated to leave 33 g of sticky solid. Recrystallization from 30 ml of cyclohexane provided 15.8 g (51%) of the 15 title compound as an off white solid: m.p. 112-115°C;
ir (Nujol<sup>R</sup>) 1420, 1110, 735, 730, 705, 695 cm<sup>1</sup>־; nmr (CDCl-j) 3.5 (2H, s), 7.0-7.8 (15H, m).
37a
Example 13ft Preparation of Chloromethyl[tris(4-chlorophenyl)]silane
A solution of 24.5 g (0.128 mol) of 4-bromochlorobenzene in dry tetrahjdrofuran was cooled to . -60° under nitrogen and stirred while 80 ml (0.128 mol) of 1.6 molar n-bufyllithium in hexane was added at a rate that held the mixture below -50°. The resuiting solution was stirred another 10 minutes at -60 to -70°, and then a solution of 5.2 ml (0.041 mol) chloromethyltrichlorosilane in tetrahydrofuran was added dropwise over 30 minutes. The resulting solution was stirred at -70° for 1 hour, allowed to warm to room temperature, quenched with saturated aqueous ammonium chloride, and extracted with ether. Washing the ether extracts with brine, drying over magnesium sulfate, and evaporation left a viscous oil, which was chromatographed over silica gel (hexanes elution) to give 9.1 g (53%) of the title compound as a colorless oil that solidified oh standing: m.p. 89-93°; nmr (CDC1 ) 3.4 (2H, s), 7.5 (12H, broad s).
The compounds of Table III are made by stepwise replacement of the Si-Cl bonds of CljSiCH<sub>2</sub>Cl, according to the procedures of Examples 12-13A.
<td></td><td> 38 Table ΙΠ</td><td></td>
<td></td><td> 2ל X-Sl-CHjCl S</td><td></td>
<td> X . R,</td><td> ^2. <sup>C</sup>?5 ίΚΛ</td><td> ל ε<sub>Λ </sub>l-CjH, 2־ε<sub>Λ</sub></td>
<td> 37״8ף־ב</td><td> 15^־2</td><td> ^6*13</td>
<td> cyclopropyl</td><td> ε<sub>Λ</sub></td><td> s-C^Hp</td>
<td> cyclohexyl</td><td> 2-^7</td><td> 2*Λ</td>
<td> 1-naphthyl</td><td></td><td></td>
<td> 4-phenylphenyl 4-phenylphenyl</td><td> 2־<sup>ε</sup>Λί</td><td> 2*Λ 2^Λ5</td>
<td> 4-chlorophenyl</td><td> ,5»<sub>4</sub>ט-פ</td><td> 2-^<sup>1</sup>¼</td>
<td> 4-fluarophenyl</td><td> 7^־2</td><td> a-c^</td>
<td> 4-( 4-chlorophenoxy )phenyl</td><td> £!־ε<sub>4</sub>Η<sub>9</sub></td><td> 2-<sup>0</sup>^</td>
<td> 4-t-butylphenyl</td><td></td><td> Α־<sup>ε</sup>Λ</td>
<td> 3-methoxyphenyl</td><td><sup>C</sup>2H<sub>5</sub></td><td> . !.*Λ</td>
<td> 3-tri fluoromethyIphenyl</td><td> S־<sup>c</sup>4<sup>h</sup>9</td><td> ־־ε<sub>Λ</sub></td>
<td> 2-thiomethylphenyl</td><td> 7^־1</td><td> 3-methylbutyl</td>
<td> 2,4-dichlorophenyl</td><td> 2^Λ</td><td> ^־2</td>
<td> 2,6-dlmethylphenyl</td><td> «Λ</td><td><sup>0</sup>Λ־!</td>
<td> 3-methyl-4-chlorophenyl</td><td> —~^4^9</td><td></td>
Table III (continued)
<td></td><td> X =</td><td> R2</td><td> ב</td>
<td></td><td><sup>C</sup>2<sup>H</sup>5</td><td> phenyl</td><td> phenyl</td>
<td> 5</td><td> cyclohexyl</td><td> phenyl</td><td> phenyl</td>
<td></td><td> i/!8<sup>H</sup>37</td><td> phenyl</td><td> phenyl</td>
<td></td><td> ι1-0<sub>4</sub>η<sub>9</sub></td><td> 4-chlorophenyl</td><td> 4-chlorophenyl</td>
<td></td><td> ^־<sup>C</sup>12<sup>H</sup>25</td><td> 4-chlorophenyl</td><td> 4-chlorophenyl</td>
<td></td><td> 1-naphthyl</td><td> 4-fluorophenyl</td><td> 4-fluorophenyl</td>
<td> 10</td><td> cyclopropyl</td><td> phenyl</td><td> 4-t-butylphenyl</td>
<td></td><td> £L-C<sub>4</sub>H<sub>9</sub></td><td> phenyl</td><td> 4-phenylphenyl</td>
<td></td><td> t־C<sub>4</sub>H<sub>9</sub></td><td> phenyl'</td><td> 2,4-dichlorophenyl</td>
<td></td><td> n-CjH?</td><td> phenyl</td><td> 3-tr i fluoromethyIph eny1</td>
<td></td><td> i-W</td><td> phenyl</td><td> 3,5-dichlorophenyl</td>
<td> 15</td><td> cyclopentyl</td><td> phenyl</td><td> 2,6-dimethoxyphenyl</td>
<td></td><td> H־<sup>C</sup>14<sup>H</sup>29</td><td> 4-chlorophenyl</td><td> 2-fluorophenyl</td>
<td></td><td> n-c<sub>4</sub>H<sub>9</sub></td><td> 4-fluorophenyl</td><td> 4-phenylphenyl</td>
<td></td><td> 4-chlorophenyl</td><td> 4-chlorophenyl</td><td> 4-chlorophenyl</td>
<td></td><td> 4-fluorophenyl</td><td> 4-fluorophenyl</td><td> 4-fluorophenyl m.p. 57-60°</td>
<td> 20</td><td> 4-phenylphenyl</td><td> 4-phenylphenyl</td><td> 4-phenylphenyl</td>
<td></td><td> 2,4-dichlorophenyl</td><td> 2,4-dichlorophenyl</td><td> 2,4-dichlorophenyl</td>
<td></td><td> phenyl</td><td> 4-fluorophenyl</td><td> 4-fluorophenyl</td>
<td></td><td> phenyl</td><td> 4-chlorophenyl</td><td> 4-chlorophenyl</td>
<td></td><td> phenyl</td><td> 4-phenylphenyl</td><td> 4-phenylphenyl</td>
<td> 25</td><td> phenyl</td><td> 2,4-dichlorophenyl</td><td> 2,4-dichlorophenyl</td>
<td></td><td> 2-naphthyl</td><td> 4-methylthiophenyl</td><td> 4-methylthiophenyl</td>
<td></td><td> 4-chlorophenyl</td><td> 2-methoxyphenyl</td><td> 2-methoxyphenyl</td>
<td></td><td> 4-chlorophenyl</td><td> 3-chlorophenyl</td><td> 3-chlorophenyl</td>
<td></td><td> phenyl</td><td> 2-chlorophenyl</td><td> 4-fluorophenyl</td>
<td> 30</td><td> phenyl</td><td> 4-chlorophenyl</td><td> 4-phenylphenyl</td>
<td></td><td> 1-naphthyl</td><td> 4-bromophenyl</td><td> 3-methylphenyl</td>
<td></td><td> 4-phenoxyphenyl</td><td> 3,5-dimethylphenyl</td><td> 3,4-dichlorophenyl</td>
Example Preparation of Chloro(chloromethyl)methyl(phenyl)silane A solution of 12.7 ml (16.4 g, 0.10 mol) of chloromethyl(dichloro)methylsilane in 200 ml of ether 5 was chilled to -70° under nitrogen and stirred vigorously while a mixture of 55 ml (0.10 mol) of 1.8 molar phenyllithium in 30:70 ether-cyclohexane and 55 ml of ether was added dropwise at a rate that kept the mixture below -70°. The resulting slurry was stirred and 10 warmed to room temperature, then allowed to stand overnight. Filtration and evaporation of the filtrate left 20.4 g of a golden oil, which was distilled to give 14.6 g (71%) of the title compound as a colorless liquid: bp 71-74° (0.6 mm); n&<sup>3</sup> 1.5337; ir (neat) 15 3080, 3060, 2980, 2930, 1590, 1430, 1260, 1120, 820, 790, 740, 700 cm<sup>1</sup>־; nmr (CDCl^) 0.8 (3H, s), 3.1 (2H, s), 7.3-7.6 (3H, m), 7.6-7.8 (2H, m).
Example 14A Preparation of Chloro[bis(4-fluorophenyl)]methylsilane_______________
A suspension of 7.0 g (0.288 mol) of magnesium turnings in 50 ml of ether was stirred under nitrogen while a solution of 50.2 g (0.287 mol) of 4-bromofluorobenzene in 200 ml of ether was added dropwise at a rate that maintained gentle reflux. After another 2 hours at reflux, the mixture was chilled in ice and a solution of 12.0 ml (0.096 mol) of chloromethyltrichlorosilane in 30 ml of ether was added dropwise. The resulting mixture was refluxed for 4 hours, chilled in ice, treated with a solution of 7.5 ml of isopropanol in 20 ml of ether, stirred 5 minutes, and filtered. The filtrate was evaporated to leave a viscous oil that was stirred with hexanes to give a slurry. Filtration under nitrogen and evaporation of the filtrate left a mobile oil that was distilled to 'י give 17.6 g (61%) of the title compound: bp 100-140° (0.1 mm); nmr (CDCl^) 3.3 (2H, s), 7.1 (4H, t), 7.7 (4H, d of d).
40a
Example 15
Preparation of (l,l'-Biphenyl-4-yl)chloro(chloromethypmethylsilane
The title compound can be prepared by reaction □f equimolar quantities of 4-bromobiphenyl, chloromethyldichloro(methyl)silane, and jT-butyllithium according to the procedure of Example 3.
The compounds of Table IV can be prepared using the procedures of Examples 14 and 15.
<td> ξ.</td><td> י ־“ ־</td><td> י. *</td><td> ר£*ן*י,.’. *t.</td><td> י- י .*- '> יי ’’*V *״'*?ή .׳♦ 66114/2</td><td></td>
<td></td><td></td><td colspan="2"> 41 Table</td><td> 1ϊ</td><td></td>
<td></td><td></td><td></td><td> ?2 X-Si» Cl</td><td> CH<sub>2</sub>C1</td><td> 1 ן</td>
<td></td><td></td><td> X « R. 1 <sup>c</sup>25״ t־c4<sup>H</sup>, n-C4<sup>H</sup><sub>9 </sub>—“<sup>C</sup>12<sup>M</sup>25 -<sup>C</sup>18<sup>H</sup>S7 cyclopropyl cyclohexyl 1-naphthyl</td><td></td><td> !2 ch<sub>3 </sub>ch<sub>3 </sub>CHj c<sub>2</sub>H<sub>5 </sub>£־<sup>C</sup>6<sup>H</sup>15 CHj CHj W7</td><td> i r</td>
<td></td><td></td><td> phenyl 4-phenylphenyl 4-phenylphenyl 4-chlorophenyl 4-chlorophenyl 4-fluorophenyl</td><td></td><td> t‘C<sub>A</sub>H<sub>9 </sub>h-c<sub>4</sub>h<sub>9 </sub>n-C<sub>6</sub><sup>H</sup>13 B־<sup>C</sup>4<sup>H</sup>9 ch3 n-C<sub>6</sub><sup>H</sup><sub>i3</sub></td><td></td>
<td></td><td></td><td> 4-t-butylphenyl 4-trifluoromethoxyphenyl 4-(4-fluorophenyl)phenyl 3-trifluoromethylphenyl</td><td></td><td> n-C<sub>3</sub>H<sub>7 </sub>ch<sub>3 </sub><sup>CH</sup>3 t־C<sub>4</sub>H<sub>9</sub></td><td></td>
<td></td><td></td><td> 2,4-dichlorophenyl 2,4-dichlorophenyl 2-chloro-4-phenylphenyl</td><td></td><td> CH<sub>3 </sub>n-C<sub>4</sub>H<sub>9 </sub>ch<sub>3</sub></td><td></td>
<td></td><td></td><td> 2-methyl-5-fluorophenyl 2,6-dimethoxypheny1</td><td></td><td> -־<sup>C</sup>4<sup>H</sup>9 1,1-dimethylpropyl</td><td></td>
Table IV (continued)
<td> 5</td><td> x = <sub>R1</sub>^y 3-methy1-4-chlorophenyl 3,5-dichlorophenyl</td><td> 2! <sup>C</sup>2<sup>H</sup>5 <sup>C</sup>5<sup>H</sup>11־2</td>
<td></td><td> £־<sup>c</sup>12<sup>h</sup>25</td><td> 2,4-dichlorophenyl</td>
<td></td><td> H־<sup>C</sup>18<sup>H</sup>37</td><td> phenyl</td>
<td></td><td> 1-naphthyl</td><td> phenyl</td>
<td></td><td> phenyl</td><td> phenyl</td>
<td> 10</td><td> 4-fluorophenyl</td><td> phenyl</td>
<td></td><td> 4-chlorophenyl</td><td> phenyl</td>
<td></td><td> 4-phenylphenyl</td><td> phenyl</td>
<td></td><td> 4-t-butylphenyl</td><td> phenyl</td>
<td></td><td> 3-fluorophenyl</td><td> phenyl</td>
<td> 15</td><td> 2-methoxyphenyl</td><td> phenyl</td>
<td></td><td> 2-chlorophenyl</td><td> phenyl</td>
<td></td><td> 2,4-dichlorophenyl</td><td> phenyl</td>
<td></td><td> 3,5-dichlorophenyl</td><td> phenyl</td>
<td></td><td> 4-fluorophenyl</td><td> 4-fluorophenyl</td>
<td> 20</td><td> 4-chlorophenyl</td><td> 4-chlorophenyl b.p. 110-130 (0.1 mm)</td>
<td></td><td> 4-phenylphenyl</td><td> 4-phenylphenyl</td>
<td></td><td> 2,4-dichlorophenyl</td><td> 2,4-dichlorophenyl</td>
<td></td><td> 3-tri fluoromethylphenyl</td><td> 3-trifluromethylpheny1</td>
<td></td><td> 2-methoxyphenyl</td><td> 2-methoxyphenyl</td>
<td> 25.</td><td> 2-chlorophenyl</td><td> 4-fluorophenyl</td>
<td></td><td> 3-trifluoromethylphenyl</td><td> 4-t-butylphenyl</td>
<td></td><td> 2-fluoro-4-chlorophenyl</td><td> 4-bromophenyl</td>
<td></td><td> 2,3-dimethylphenyl</td><td> 4-methylthiophenyl</td>
<td rowspan="2"> 30</td><td> 2,6-dimethoxyphenyl</td><td> 4-methoxyphenyl</td>
<td> 3,4-dichlorophenyl</td><td> 4-methylphenyl</td>
Example 16
Preparation of Chloromethyl(methoxy)methyKphenyl)silane ___________;_______- _______________
A solution of 1.6 ml (1.3 g, 0.040 mol) of methanol and 3.0 ml (2.2 g, 0.022 mol) of triethylamine in 100 ml of ether was stirred while a solution of 4.1 g (0.020 mol) of chloro(chloromethyl)methyl(phenyl)silane in 10 ml of ether was added dropwise. The resulting slurry was refluxed for 2 hours, cooled, washed with water, 0.1 N aqueous HC1, saturated aqueous NaHCOj, water, and brine, dried over magnesium sulfate, and evaporated to leave 3.2 g of a pale yellow liquid. Distillation provided 1.7 g (42%) of the title compound as a colorless liquid: bp 46-49° (0.05 mm); ηθ<sup>2</sup> 1.5207; nmr (COCip: 0.5 (3H, s), 3.0 (2H, s), 3.5 (3H, s) and 7.3-7.8 (5H, m).
Example 17
Preparation of Chloromethyl(l,l-dimethylethoxy)methyl(phenyl)silane_________________________________________
A mixture of 15.4 g (0.075 mol) of chloro(chloromethyl)methyl(phenyl)silane, 14 ml (11.1 g, 0.15 mol) of t-butanol, 11.5 ml (8.3 g, 0.082 g) of triethylamine, and 0.5 g (0.008 mol) of imidazole in 60 ml of dimethylformamide was stirred at 80° for 2 hours. The resulting slurry was cooled, poured into 200 ml of water, and extracted with ether. The ether extracts were washed three times with water, followed by 0.1 N aqueous HC1, saturated aqueous NaHCO^, and brine, dried over magnesium sulfate, and evaporated to leave 14.0 g of a pale orange oil. Distillation provided
11.9 g (65%) of the title compound: bp 78-82° (0.2 mm); n<sup>21</sup> 1.5010; ir (neat) 3080, 3060, 2990, 2940, 1600, 1435, 1395, 1370, 1260, 1245, 1195, 1125, 1060, 1030, 815, 790, 740, 725, 705, 650 cm<sup>1</sup>־; nmr (CDClj): 0.5 (3H, s), 1.3 (9H, s), 2.9 (2H, s) and 7.3-7.8 (5H, m).
43a
Exampls 17A
Preparation of (1,1'-Biphenyl-4-yl)cnloromethyl(־methyl) (2-propoxy )silane__________________________
A solution of 73.3 g (0.315 mol) of 4-bromobiphenyl in 300 ml of tetrahydrofuran was added dropwise to a stirred suspension of 7.64 g (0.315 mol) of magnesium in 100. ml of tetrahydrofuran at a rate that maintained gentle reflux. The resulting clear solution was stirred at room temperature for 1 hour and then cooled in ice, and a solution of 40 ml (0.315 mol) of chloromethyl(dichloro)methylsilane in 100 ml of tetrahydrofuran was added rapidly. The resulting solution was stirred at room temperature for 20 hours, treated with 50 ml of isopropanol, and cooled in ice again. A solution of 48 ml (0.344 mol) of triethylamine in tetrahydrofuran was then added at a rate that held the mixture below 25°. Stirring at room temperature for 90 minutes gave a slurry. Filtration, evaporation of the filtrate, trituration with hexanes, and a second filtration removed residual amine hydrochloride. Evaporation of the hexanes solution gave 92 g (96%) of the title compound as a pale yellow oil that solidified on standing: . m.p. 35-38°; nmr (CDClj) 0.5 (3H, s), 1.2 (6H, d), 3.0 (2H, s), 4.2 (1H, septet), 7.3-7.8 (9H, m).
43b
Example 17B
Preparation of Chloromethyl[bis(4-fluorophenyl)](2־propoxy)silane______________________________
A mixture of 23.2 g (0.955 mol) of magnesium and 50 mg of iodine in 200 ml of ether was stirred while a solution of 167 g (0.954 mol) of 4-bromofluorobenzene in 600 ml of ether was added at a rate that maintained gentle reflux. After another 2 hours at reflux, the solution was cooled in ice and stirred while a solution of 40 ml (0.32 mol) of chloiomethyltrichlorosilane in ether was added dropwise over 40 minutes. The resulting mixture was stirred at room temperature for 17 hours, chilled in ice, treated with 24 ml of isopropanol, stirred another 10 minutes, and filtered. The filtrate was concentrated to a gummy solid, hexanes was added, the resulting slurry was filtered, and the hexanes filtrate was evaporated to leave an oil. Analysis by nmr showed the presence of unreacted chlorosilane, so the oil was dissolved in hexanes containing 30 ml of isopropanol, and the solution was chilled in ice and treated with a solution of 42 ml (0.30 mol) of triethylamine in hexanes. The resulting slurry was stirred at room temperature for 3 hours and filtered, and the filtrate was evaporated to leave an oil. Distillation provided 44.8 g (43%) of the title compound as a. colorless liquid: bp 120-140° (0.1 mm); n<sup>22</sup> 1.5211; nmr (CDClj) 1.2 (6H, d),
3.2 (2H, s), 4.1 (1H, septet), 7.1 (4H, t), 7.7 (4H, d of d).
Example Preparation of Chloromethyl(ethoxy)methyl(phenyl)silane A solution of 18.2 ml (18.2 g, 0.10 mol) of chloromethyl(diethoxy)methylsilane in 200 ml of dry ether was stirred vigorously under N<sub>2</sub> and chilled while 56 ml (0.10 mol) of 1.8 molar phenyllithium in 70:30 cyclohexane-ether was added at a rate that held the mixture below -50°. The resulting slurry was allowed to warm to room temperature, treated cautiously with 10 ml of ethyl acetate, washed with water and brine, dried over magnesium sulfate, and evaporated to leave 16.8 g of a golden yellow liquid. Disfiliation provided 9.5 g (44%) of the title compound
חס as a colorless liquid: bp 80-84° (0.1 mm); ηθ 1.5144; nmr (CDCl-j) 0.5 (3H, s), 1.2 (3H, t, J = 7), 3.0 (2H, s), 3.8 (2H, q, J 5) 7.2-7.8 ,(7 ־H, m).
The compounds of Table V can be prepared using the procedures of Examples 16-18.
ללי ^^¾^¾¾[¾¾¾^^¾¾11¢<sup>1</sup> ' ’.'.*ftsiiLessia. ׳,^,-, ־ ־*
Table V
־״
X-S1-CH-C1
<td> X . R,</td><td> ב</td><td> צ!</td>
<td></td><td> %</td><td><sup>0</sup>s</td>
<td></td><td></td><td> £-°4<sup>Η</sup>9</td>
<td> ®*Λ</td><td> CH,</td><td><sup>C</sup>A</td>
<td> £¾¾5</td><td> *ft</td><td><sup>W</sup>3</td>
<td></td><td></td><td> 3</td>
<td> cycloprapyl</td><td> ״CHj -</td><td> »-C<sub>4</sub>H<sub>9</sub></td>
<td> cyclohexyl</td><td> %</td><td> °b</td>
<td> 1-naphthyl</td><td></td><td> A־^</td>
<td> phenyl</td><td> CH,</td><td> H</td>
<td> phenyl</td><td> °S</td><td> i-CjH? bp 72-76<sup>e</sup>(0.1 mm)</td>
<td> phenyl</td><td> —”^4^9</td><td> H</td>
<td> 4-phenylphenyl</td><td></td><td> CHj</td>
<td> 4-phenylphenyl</td><td> —</td><td> H</td>
<td> 4-phenylphenyl</td><td> c<sub>3</sub>״</td><td><sup>C</sup>2<sup>H</sup>5</td>
<td> 4-phenylphenyl</td><td><sup>01</sup>3</td><td> ί^Λ</td>
<td> 4-chlarophenyl</td><td> 2-C<sub>4</sub>H<sub>9</sub></td><td></td>
<td> 4-chlorophenyl</td><td> ch<sub>3</sub></td><td> 043</td>
<td> 4-chlorophenyl</td><td> ch<sub>3</sub></td><td><sup>C</sup>2<sup>H</sup>5</td>
<td> 4-fluarophenyl</td><td></td><td></td>
<td> 4-fluorophenyl</td><td> C<sub>3</sub>״</td><td> ^5 .</td>
<td> -</td><td></td><td></td>
<td> 4-t-butylphenyl</td><td> 7^־פ</td><td></td>
<td> 3-trifluoromethylphenyl</td><td> i־<sup>C</sup>4<sup>H</sup>9</td><td> H</td>
<td> 2,4-dichlorophenyl</td><td> CHj</td><td> ch<sub>3</sub></td>
<td> 2,4-dichlorophenyl</td><td> ch<sub>3</sub></td><td><sup>C</sup>2<sup>H</sup>5</td>
<td> 2,4-dichlorophenyl</td><td> ch<sub>3</sub></td><td> t-C<sub>4</sub>H<sub>9</sub></td>
־. . -?־ ‘ .,
Table V (continued) °Λ
7^־ב
Η °b <sup>c</sup>25״ Kft “3 <sup>C</sup>A ί-ε<sub>Λ </sub>“3 ׳!-CjH, <sup>C</sup>A **Λ —”^4^9 CjHj l־^ η-Ο^Ηγ t-C.Hq b.p. 110-111
5.1) <sup>4$</sup> ־ nan) <sup>c</sup>r5
CHj
CH, % «Λ
<td colspan="2"> ף ש X</td><td> ב</td>
<td> 5</td><td> 2,4-dichlorophenyl ’</td><td></td>
<td> 10 15 20 25 30 35</td><td> 2- methyl-5-fluorophenyl 2,6-dimethoxyphenyl 3- methyl-4-chlorophenyl 3,5-dichlorophenyl ^12”25 ^18”37 1- naphthyl phenyl 4- fluorophenyl 4-chlorophenyl 4-phenylphenyl 4-phenylphenyl 4-b-butylphenyl 3- fluarophenyl 2- eethoxyphenyl 2- chlorophenyl 2.4- dichlorophenyl 3.5- dichlorophenyl 4- fluorophenyl 4-fluorophenyl 4-chlorophenyl 4-chlorophenyl 4-phenylphenyl 2,4-dichlorophenyl 3- trifluoromethylphenyl 2-methoxyphenyl 2- chlorophenyl 3- tri fluoromethylphenyl 2-f luor0-4-chloropheny1 2,3-dimethyIphenyl</td><td> £־<sup>C</sup>4<sup>H</sup>9 1,1-dimethy!propyl <sup>C</sup>2<sup>H</sup>5 2־°Λ1 2,4-dichlorophenyl Uhenyl *phenyl phenyl phenyl . phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl 4-fluorophenyl 4-fluorophenyl 4-chlorophenyl 4-chlorophenyl 4-phenylphenyl 2,4-dichlorophenyl 3- trifluoromethylphenyl 2-methoxyphenyl 4- fluorophenyl 4-t-butyIphenyl 4-bromophenyl 4-methylthiophenyl</td>
<td> Table</td><td colspan="3"> 47 (continued)</td>
<td> *'*!/ή</td><td> 1</td><td> ל</td><td></td>
<td> 2,6-dimethoxyphenyl</td><td> 4-methoxyphenyl</td><td> H</td><td></td>
<td> 3,4-dichlorophenyl</td><td> 4-methylphenyl</td><td colspan="2"> 1־<sup>C</sup>A</td>
<td> 4-fluorophenyl</td><td><sup>CH</sup>3</td><td> i־<sup>c</sup>3<sup>H</sup><sub>7</sub></td><td> 22 n^ 1.4827</td>
<td> 4-chlorophenyl</td><td> 4-chlorophenyl</td><td> i־<sup>c</sup>3<sup>H</sup><sub>7</sub></td><td> 22 n^ 1.5650</td>
Example 19
Preparation of (l,l’-Biphenyl-4-yl)dimethyl(lH-l,2,4triazol-l-y!methyl)silane______
A mixture of 2.6 g (0.010 mol) of (1,1'-biphenyl-
4-yl)chloromethyldimethylsilane and 1.1 g (0.012 mol) of 1,2,4-triazole sodium salt in 5 ml of dimethylformamide was warmed to 80-90° for 2 hours, cooled, diluted with water, and extracted with ether. The ether solution was washed with water and brine, dried over magnesium sulfate, and evaporated to leave 2.3 g of colorless solid, m.p. 79-86°. Recrystallization from a mixture of 25 ml of hexanes and 2 ml of ethyl acetate gave 1.1 g (38%) of the title compound: m.p. 92-93°; ir (Nujol<sup>R</sup>) 1255, 1130, 1000, 825, 760, 695 cm<sup>1</sup>־; nmr (CDClj) 0.4 (6H, s), 3.9 (2H, s), 7.2-7.7 (9H, m), 7.8 (1H, s), 7.9 (1H, s); analysis for <sup>C</sup>17<sup>H</sup>19<sup>N</sup>3<sup>Si (mw 293</sup>.<sup>43):</sup>
Calculated C, 69.58; H, 6.53; N, 14.32; Found C, 70.0; H, 6.6; N, 13.9; 69.8; 6.7; 13.8.
An equimolar mixture of 1,2,4-triazole and sodium methoxide can be used instead of preformed triazole sodium salt. Note that these reagents must be combined before the silane is added, since chloromethylsilanes react very vigorously with sodium methoxide in dimethylformamide, giving undesired products.
Example 20
Isolation of (l,l'-Biphenyl-4-yl)dimethyl(4H-l,2,4triazol-4־ylmethyl)silane ______
A 5 g sample of once-crystallized 1,!'-(biphenyl4-y1)dimethy1(1H-1,2,4-triazol-l-ylmethyl)silane, prepared as in Example 14 using sodium methoxide-1,2,4triazole, was subjected to high pressure liquid chromatography (Waters Prep PAK-500 silica gel cartridge, 250 ml per minute flow rate). Elution with ethyl acetate-hexane 50:50 removed first some minor impurities and then provided the pure 1H-1,2,4-triazol-l-ylmethyl compound, m.p. 99-100°. Continued elution with ethyl acetate-acetonitrile 80:20 provided a small amount of the title compound as a colorless solid: m.p. 130-133°C; nmr (CDCl^) 0.4 (6H, s), 3.7 (2H, s),
7.2-7.7 (9H, m), 7.9 (2H, s).; microanalysis for <sup>C</sup>17<sup>H</sup>19<sup>N</sup>3<sup>Si (mw 293</sup>.<sup>43):</sup>
Calculated: C, 69.58; H, 6.53; N, 14.32.
Found: C, 69.0; H, 6.7; N, 13.9.
69.3; 6.7; 14.2.
Example 21
Preparation of Dimethyl(phenyl)(lH-l,2,4-triazol-l-ylmethyl) silane ...__..........
A mixture of 9.0 ml (9.2 g, 0.050 mol) of chloro5 methyldimethylphenylsilane and 5.5 g (0.060 mol) of
1,2,4-triazole sodium salt in 25 ml of dimethylformamide was stirred and warmed to 90-95°C for 2 hours, cooled, diluted with water, and extracted with ether. The ether solution was washed with water and brine, 10־ dried over magnesium sulfate, and evaporated to leave
8.1 g (75%) of a pale brown oil, ηθ<sup>2</sup> 1.5350, containing the title compound and minor impurities as judged by nmr. A purer sample was obtained by distillation: bp 99° (0.02 mm); ηθ° 1.5403; nmr (CDC1<sub>3</sub>)
0.4 (6H, s), 3.8 (2H, s), 7.2-7.7 (5H, m), 7.7 (IH, s), 7.8 (IH, s); analysis for <sup>C</sup>11<sup>H</sup>15<sup>N</sup><sub>3</sub>Si (mw 217.34):
Calculated C, 60.78; H, 6.96; N, 19.33;
Found C, 60.7; H, 7.0; N, 16.9;
60.2; H, 7.0; N, 16.8.
Example 22 Preparation of (4-Chlorophenyl)dimethyl(lH-l,2,4triazol-l-ylmethyDsilane.........
A mixture of 2.2 g (0.010 mol) of chloromethyl(4chlorophenyDdimethylsilane and 1.1 g (0.012 mol) of
1,2,4-triazole sodium salt in 5 ml of dimethylformamide was warmed to 80-90° for 2 hours, diluted with water, and extracted with ether. The ether solution was washed with water and brine, dried over magnesium sulfate, and evaporated to leave 2.1 g (83%) of the 21 title compound as a yellow liquid: n<sub>Q</sub> 1.5428; ir (neat). 1555, 1470, 1245, 1130, 1080, 1010, 835, 805, 795, 735 cm<sup>1</sup>־; nmr (CDClj) 0.4 (6H, 5), 3.8 (2H, s), 7.4 (4H, broad s), 7.8 (1H, s), 7.9 (1H, s) .
Example 23 Preparation of (2,4-0ichlorophenyl)dimethyl(lH-l,2,4triazol-l-ylmethyl)silane______________
A mixture of 5.1 g (0.020 mol) of chloromethyl(2,4-dichlorophenyl)dimethylsilane and 2.0 g (0.022 mol) of 1,2,4-triazole sodium salt in 10 ml of dry dimethylformamide was stirred at 80-90° for 2 hours. The resulting slurry was cooled, diluted with water, and washed with ether. The ether extracts were washed with several portions of water and once with brine, dried over magnesium sulfate, and evaporated to leave
4.6 g (81%) of the title compound as a pale yellow liquid: 1.5580; ir (neat) 1550, 1485, 1440,
1345, 1260, 1240, 1130, 1085, 1025, 1005, 835 cm<sup>1</sup>־; nmr (CDC1<sub>3</sub>) 0.5 (6H, s), 4.1 (2H, s), 7.2-7.5 (3H, m), 7.8 (1H, s), 7.9 (1H, s).
Example 24
Preparation of bis(4-Chlorophenyl)methyl(lH-l,2,4triazol-l-ylmethyl)silane .........
A mixture of 6.3 g (0.020 mol) of chloromethylbis(4-chlorophenyl)methylsilane and 2.0 g (0.022 mol) of 1,2,4-triazole sodium salt in 10 ml of dry dimethylformamide was stirred at 80°C for 4 hours. The resulting slurry was cooled, diluted with water, and washed with ether. The ether extracts were washed with several portions of water and once with brine, dried over magnesium sulfate, and evaporated to leave 5.4 g of yellow oil. Kugelrohr distillation at 120-150° (airbath)/0.05 mm gave 4.0 g (58%) of the title compound as a pale yellow oil: n<sub>D</sub> 1.5966; nmr (CDCl^) 0.7 (3H, s), 4.1 (2H, s), 7.2-7.5 (8H, m), 7.8 (1H, s), 7.9 (1H, s).
' In a similar experiment, evaporation of the ether extracts gave a gummy solid that was triturated with hexanes to give the title compound as a colorless solid, m.p. 76-80°.
Example 25
Preparation of bis(4-Fluorophenyl)methyl(lH-l,2,4triazol-l-ylmethypsilane .
A mixture of 4.2 g (0.015 mol) of (chloromethyl)bis(4-fluorophenyl)methylsilane and 1.4 g (0.015 mol) of 1,2,4-triazole sodium salt in 8 ml of dimethylformamide was stirred at 80° for 2 hours. The resulting slurry was cooled, diluted with water, and worked up as in Example 24 to give 4.0 g of a pale yellow oil. Impurities were removed by Kugelrohr distillation at 120-125° (0.05 mm), leaving behind 2.3 g (49%) of the title compound as a yellow oil: n^ 1.5538; ir (neat) 3065, 3030, 2960, 2925, 1590, 1500, 1270, 1235, 1165, 1110, 1010, 830, 790 cm<sup>1</sup>־; nmr (CDClj): 0.7 (3H, s),
4.2 (2H, s), 7.1 (4H, t, J = 9), 7.5 (4H, d of d, ΰ = 6 and 9), 7.8 (IH, s) and 7.9 (IH, s).
By applying the procedures of Examples 19 and 21-25 to appropriate chloromethylsilanes, the compounds of Table VI in which ^/q<sub>2</sub>=H can be prepared.
Table VI
<td> 5</td><td colspan="5"> ל</td>
<td></td><td></td><td><sup>R</sup>2</td><td></td><td></td><td></td>
<td></td><td></td><td></td><td></td><td></td><td></td>
<td></td><td></td><td> CH<sub>3</sub></td><td> CH<sub>3</sub></td><td> 22 ם<sup>ח</sup></td><td> 1.4713</td>
<td> 10</td><td> i־<sup>C</sup>3<sup>H</sup>7</td><td> ch<sub>3</sub></td><td> ch<sub>3</sub></td><td> 19</td><td></td>
<td></td><td></td><td> ch<sub>3</sub></td><td> ch<sub>3</sub></td><td><sup>n</sup>D</td><td> 1.4687</td>
<td></td><td> t־C4<sup>H</sup><sub>9</sub></td><td> CH<sub>3</sub></td><td> CH<sub>3</sub></td><td></td><td></td>
<td></td><td> !?<sup>C</sup>12<sup>H</sup>25</td><td> ch<sub>3</sub></td><td> ch<sub>3</sub></td><td> 23 <sup>n</sup>D</td><td> 1.4626</td>
<td></td><td> £־<sup>C</sup>14<sup>H</sup>29</td><td> ch<sub>3</sub></td><td> CH<sub>3</sub></td><td></td><td></td>
<td> 15</td><td> I?<sup>C</sup>18<sup>H</sup>37</td><td> ch<sub>3</sub></td><td> ch<sub>3</sub></td><td> 21״ <sup>n</sup>D</td><td> 1.4597</td>
<td></td><td> cyclopropyl</td><td> ch<sub>3</sub></td><td> ch<sub>3</sub></td><td></td><td></td>
<td></td><td> cyclobutyl</td><td> ch<sub>3</sub></td><td> ch<sub>3</sub></td><td></td><td></td>
<td></td><td> cyclopentyl</td><td> ch<sub>3</sub></td><td> ch<sub>3</sub></td><td></td><td></td>
<td> 20</td><td> cyclohexyl</td><td> ch<sub>3</sub></td><td> ch<sub>3</sub></td><td> 22 <sup>n</sup>D</td><td> 1.4906</td>
<td></td><td> 1-naphthyl</td><td> CH, ג</td><td> ch<sub>3</sub></td><td> 23 <sup>n</sup>D</td><td> 1.6051</td>
<td></td><td> 2-naphthyl</td><td> CH<sub>3</sub></td><td> CH, J</td><td></td><td></td>
<td></td><td> 4-bromophenyl</td><td> CH<sub>3</sub></td><td> CH<sub>3</sub></td><td> 20 <sup>n</sup>D</td><td> 1.5647</td>
<td></td><td> 4-fluorophenyl</td><td> ch<sub>3</sub></td><td> ch<sub>3</sub></td><td colspan="2"> bp 108° (0,2 mm)</td>
<td> 25</td><td> 4-methoxyphenyl</td><td> CH<sub>3</sub></td><td> ch<sub>3</sub></td><td> 26״ <sup>n</sup>D</td><td> 1.5401</td>
<td></td><td> 4-phenoxyphenyl</td><td> ch<sub>3</sub></td><td> ch<sub>3</sub></td><td> 22״ סי<sup>,</sup></td><td> 1.5754</td>
<td></td><td> 4-(4-chlorophenoxy)phenyl</td><td> ch<sub>3</sub></td><td> CH<sub>3</sub></td><td> 22״ <sup>n</sup>D</td><td> 1.5703</td>
<td></td><td> 4-(4-fluorophenoxy)phenyl</td><td> ch<sub>3</sub></td><td> ch<sub>3</sub></td><td></td><td></td>
<td> 30</td><td> 4-(4-tri fluoromethylphenoxy)ph eny1</td><td> ch<sub>3</sub></td><td> CH<sub>3</sub></td><td></td><td></td>
<td></td><td> 4-(4-methylphenoxy)phenyl</td><td> ch<sub>3</sub></td><td> CH<sub>3</sub></td><td></td><td></td>
<td></td><td> 4-thiomethylphenyl</td><td> ch, כ</td><td> CH<sub>3</sub></td><td> 23״ <sup>n</sup>D</td><td> 1.5790</td>
<td></td><td> 4-trifluoromethylphenyl</td><td> CH<sub>3</sub></td><td> CH<sub>3</sub></td><td> 22 <sup>n</sup>D</td><td> 1.4909</td>
<td> 35</td><td> 4-methylphenyl</td><td> cn<sub>3</sub></td><td> CH<sub>3</sub></td><td> 21״ <sup>n</sup>D</td><td> 1.5350</td>
Table VI (continued)
<td> .1</td><td> r<sub>2</sub></td><td><sup>R</sup>3</td>
<td></td><td></td><td></td>
<td><sub>5</sub> 4-methylsulfonylphenyl</td><td> CH<sub>3</sub></td><td> CH<sub>3</sub> n<sup>21</sup> 1.5538</td>
<td> 4-i-propyIpheny1</td><td> ch<sub>3</sub></td><td> ch<sub>3</sub></td>
<td> 4-t-butylphenyl</td><td> ch<sub>3</sub></td><td> CH<sub>3</sub> n<sup>23</sup> 1.5125</td>
<td> 4-cyclohexylphenyl</td><td> ch<sub>3</sub></td><td> CH<sub>3</sub> n^<sup>1</sup> 1.5235</td>
<td> 4-trifluoromethoxyphenyl</td><td> ch<sub>3</sub></td><td> CH<sub>3</sub> n<sup>22</sup> 1.4768</td>
<td> 4-(4-chloropheny1)phenyl</td><td> ch<sub>3</sub></td><td> ch<sub>3</sub></td>
<td> 4-(4-bromopheny1)phenyl</td><td> ch<sub>3</sub></td><td> CH<sub>3</sub> n<sup>22</sup> 1.5802</td>
<td> 4-(4-methyIpheny1)phenyl</td><td> ch<sub>3</sub></td><td> ch<sub>3</sub></td>
<td> 4-(4-tri fluoromethylphenyl)phenyl</td><td> ch<sub>3</sub></td><td> CH, כ</td>
<td> 15 4-(4-fluoropheny1)phenyl</td><td> ch<sub>3</sub></td><td> CH<sub>3</sub></td>
<td> 3-phenylphenyl</td><td> ch<sub>3</sub></td><td> CH<sub>3</sub> n<sup>21</sup> 1.5939</td>
<td> 3-tri fluorome thyIpheny1</td><td> ch<sub>3</sub></td><td> CH<sub>3</sub> n<sup>20</sup> 1.4845</td>
<td> 3-chlorophenyl</td><td> ch<sub>3</sub></td><td> CH<sub>3</sub> m.p. 37-43°</td>
<td> 20 2-trifluoromethylphenyl</td><td> ch<sub>3</sub></td><td> CH<sub>3</sub> n<sup>23</sup> 1.4964</td>
<td> 2-phenylphenyl</td><td> CH<sub>3</sub></td><td> 22 CH<sub>3</sub> n& 1.5900</td>
<td> 2-chlorophenyl</td><td> CH<sub>3</sub></td><td> CH<sub>3</sub> n<sup>22</sup> 1.5442</td>
<td> 2-methoxyphenyl</td><td> ch<sub>3</sub></td><td> ?1 CH<sub>3</sub> n& 1.5216</td>
<td> 25 2,3-dimethylphenyl</td><td> CH<sub>3</sub></td><td> ch<sub>3</sub></td>
<td> 2,3-dimethoxypheny1</td><td> ch<sub>3</sub></td><td> CH<sub>3</sub> n<sup>22</sup> 1.5322</td>
<td> 2,4-difluorophenyl</td><td> ch<sub>3</sub></td><td> ch<sub>3</sub></td>
<td> 2-fluoro-4-chlorophenyl</td><td> ch<sub>3</sub></td><td> ch<sub>3</sub></td>
<td> 2-chloro-4-fluorophenyl</td><td> ch<sub>3</sub></td><td> ch<sub>3</sub></td>
<td><sup>30</sup> 2-chloro-4-phenyIpheny1</td><td> ch<sub>3</sub></td><td> ch<sub>3</sub></td>
<td> 2-fluoro-4-phenyIpheny1</td><td> ch<sub>3</sub></td><td> ch<sub>3</sub></td>
<td> 2-methy1-5-chlorophenyl</td><td> ch<sub>3</sub></td><td> ch<sub>3</sub></td>
<td> 2,6-dimethoxyphenyl</td><td> ch<sub>3</sub></td><td> 23 CH<sub>3</sub> ng 1.5404</td>
<td><sub>35</sub> 2,6-dimethyIpheny1</td><td> ch<sub>3</sub></td><td> ch<sub>3</sub></td>
Table VI (continued)
<td> 1</td><td> !2</td><td> ב</td>
<td> 3,4-dichlorophenyl</td><td> CHj</td><td> 22 CH<sub>?</sub> rff 1.5602</td>
<td> 3-methy1-4-fluorophenyl</td><td> CHj</td><td> %</td>
<td> 3,5-dichlorophenyl</td><td> CHj</td><td> CH. m.p. 63-69°</td>
<td></td><td><sup>C</sup>2<sup>H</sup>5</td><td> 3״</td>
<td> 2־<sup>c</sup>a<sup>h</sup>9</td><td> s-c<sub>4</sub>h<sub>9</sub></td><td> ch, rff !.ten</td>
<td> 1H12׳<sup>H</sup>25</td><td> ^3*7</td><td><sup>W</sup>3</td>
<td> 1H14׳<sup>H</sup>29</td><td> ^7</td><td> 3״</td>
<td> 2־<sup>c</sup>18<sup>h</sup>37</td><td> 3-methylbutyl</td><td> CH,</td>
<td> cyclopropyl</td><td></td><td><sup>W</sup>3</td>
<td> 1-naphthyl</td><td> n־C<sub>4</sub><sup>H</sup><sub>9</sub></td><td><sup>0,</sup>3</td><td></td>
<td> 1-naphthyl</td><td> t-c<sub>4</sub>n<sub>9</sub></td><td> CT,</td><td></td>
<td> 2-naphthyl</td><td> ^5<sup>H</sup>11</td><td> 3״</td><td></td>
<td> phenyl</td><td></td><td> Of,</td><td></td>
<td> phenyl</td><td> D־c<sub>4</sub>h<sub>9</sub></td><td> “3</td><td> 21 nJ<sup>1</sup> 1.5297</td>
<td> phenyl</td><td> 1,1-dimethylpropyl</td><td> CHj</td><td></td>
<td> phenyl</td><td> £^13</td><td> CHj</td><td></td>
<td> 4-phenylphenyl</td><td></td><td> ch<sub>3</sub></td><td></td>
<td> 4-phenylphenyl</td><td> 2־<sup>C</sup>4<sup>H</sup>9</td><td><sup>0,</sup>3</td><td> 22 Πρ 1.5838</td>
<td> 4-bromophenyl</td><td> i-C^</td><td> Olj</td><td></td>
<td> 4-chlorophenyl</td><td><sup>0</sup>-״Λ</td><td> 3״)</td><td> 21 nJ<sup>1</sup> 1.5344</td>
<td> 4-fluorophenyl</td><td> ׳SA</td><td> CH,</td><td> 22 nj<sup>z</sup> 1.5120</td>
<td> 4-phenoxyphenyl</td><td></td><td> cnj</td><td></td>
<td> 4-t-butylphenyl</td><td> 1־<sup>c</sup>4<sup>h</sup>9</td><td> °<sup>,</sup>3</td><td></td>
<td> 3-phenylphenyl</td><td> 1־<sup>C</sup>4<sup>H</sup>9</td><td><sup>W</sup>3</td><td></td>
<td> 3-trifluoromethylphenyl</td><td></td><td> CH,</td><td></td>
Table VI (continued)
<td> 3-chlorophenyl 2-methoxyphenyl</td><td> !2 fr^ll t-c<sub>4</sub>H,</td><td> ל CHj</td>
<td> 2-phenylphenyl</td><td></td><td> %</td>
<td> 2,4-dichlorophenyl</td><td> S־<sup>c</sup>4<sup>h</sup>j</td><td> CHj η<sup>23</sup> 1.5411</td>
<td> 2,3-dimethylphenyl</td><td> ®*Λ</td><td></td>
<td> 2,5-dimethoxypheny 1</td><td> 4-methyIpentyl</td><td> CHj</td>
<td> 2,6-dimethyIphenyl</td><td> 1-methylbutyl</td><td></td>
<td> 3,4-dichiorophenyl</td><td></td><td> 3״</td>
<td> 3,5-dichlorophenyl</td><td> 2־<sup>C</sup>4<sup>H</sup>9</td><td> CHj</td>
<td> phenyl</td><td> phenyl</td><td> CHj ηξ<sup>2</sup> 1.5852</td>
<td> 4-fluorophenyl</td><td> phenyl</td><td> CHj np° 1.5718</td>
<td> 4-chlorophenyl</td><td> phenyl</td><td> CHj r£<sup>2</sup> 1.5926</td>
<td> 4-bromophenyl</td><td> phenyl</td><td> CHj n£ 1.6076</td>
<td> 4-phenyIphenyl</td><td> phenyl</td><td> CHj n?<sup>1</sup> 1.6328</td>
<td> 4-t-butylphenyl</td><td> phenyl</td><td> CHj</td>
<td> 4-thiomethylphenyl</td><td> phenyl</td><td> CHj</td>
<td> 4-phenoxyphenyl</td><td> phenyl</td><td> CH,</td>
<td> 4-tri fluoromethoxyphenyl</td><td> phenyl</td><td><sup>01</sup>3</td>
<td> 4-methylsulfonyIphenyl</td><td> phenyl</td><td> CH,</td>
<td> 4-cyclohexyIphenyl</td><td> phenyl</td><td> CH,</td>
<td> 4-(4-fluorophenyDphenyl</td><td> phenyl</td><td> CH,</td>
<td> 3-trifluorome thy Iphenyl</td><td> phenyl</td><td> CH,</td>
<td> 2-chlorophenyl</td><td> phenyl</td><td> CHj . n^° 1.5742</td>
<td> 2-methoxyphenyl</td><td> phenyl <sup>1</sup></td><td> CH,</td>
Table VI (continued)
<td> 21</td><td> ב</td><td> S</td>
<td><sub>5</sub> 2,4-dichlorophenyl</td><td> phenyl</td><td> CH<sub>3</sub> n<sup>23</sup> 1.5941</td>
<td> 2-chloro-4-phenyIpheny1</td><td> phenyl</td><td><sup>CH</sup>3</td>
<td> 2-fluor0-4-phenyIpheny1</td><td> phenyl</td><td> (Ή3</td>
<td> 3,5-dichlorophenyl '</td><td> phenyl</td><td> °<sup>1</sup>3</td>
<td> 2,5-dime thoxypheny1</td><td> phenyl</td><td><sup>04</sup>3</td>
<td> 1<sub>0</sub> 2,6-dimethoxyphenyl</td><td> phenyl</td><td> CK<sub>3</sub></td>
<td> 4-bromophenyl</td><td> 4-bromophenyl</td><td> CH<sub>3</sub> n^<sup>1</sup> 1.6245</td>
<td> 4-phenylphenyl</td><td> 4-phenylphenyl</td><td> CHj m.p. 42-46°</td>
<td> 4-methoxyphenyl</td><td> 4-methoxyphenyl</td><td> CH<sub>3</sub> n<sup>21</sup> 1.5890</td>
<td> 3-trifluoromethylphenyl</td><td> 3-tri fluoromethylphenyl</td><td> <*3</td>
<td><sup>15</sup> 2-chlorophenyl</td><td> 2-chlorophenyl</td><td> CH<sub>3</sub> n<sup>21</sup> 1.5965</td>
<td> 2-methoxyphenyl</td><td> 2-methoxyphenyl</td><td> cm<sub>3</sub></td>
<td> 2,4-dichlorophenyl</td><td> 2,4-dichloropheny1</td><td> CH<sub>3</sub> n^<sup>2</sup> 1.6009</td>
<td> 3,5-dichlorophenyl</td><td> 3,5-dichlorophenyl</td><td> *3</td>
<td> 20 2-chlorophenyl</td><td> 4-chlorophenyl</td><td> CH<sub>3</sub> r^° 1.5918</td>
<td> 2-chlorophenyl</td><td> 4-fluarophenyl</td><td> cm<sub>3</sub></td>
<td> 4-phenylphenyl</td><td> 4-chlorophenyl</td><td> CH,</td>
<td> 4-phenylphenyl</td><td> 4-fluorophenyl</td><td> > 22 CH, n“ 1.6151</td>
<td> 4-phenylphenyl</td><td> 2,4-dichlorophenyl</td><td> 3״</td>
<td> 25 4-fluorophenyl</td><td> 2,4-dichlorophenyl</td><td> CH,</td>
<td> 4-chlorophenyl</td><td> 2,4-dichloropheny1</td><td> CH</td>
<td> 1-naphthyl</td><td> 2,6-dimethoxyphenyl</td><td> CHj</td>
<td> 4-phenoxyphenyl</td><td> 3,4-dichlorophenyl</td><td><sup>W</sup>3</td>
<td></td><td></td><td></td>
<td> 30 i-CjH,</td><td> l־<sup>c</sup>^7</td><td> 7^־1</td>
<td> ^־<sup>C</sup>4<sup>H</sup>9</td><td> 2־<sup>c</sup>z,<sup>H</sup>9</td><td> ׳><sup>C</sup>A</td>
<td> ^18^7</td><td> 2־<sup>C</sup>6<sup>H</sup>13</td><td> ^Λ3</td>
<td> cyclopropyl</td><td><sup>C</sup>2<sup>H</sup>5</td><td><sup>0</sup>Λ־!</td>
Table VI (continued)
<td> 21</td><td> ב</td><td> ל</td>
<td> cyclohexyl</td><td> n-CjH,</td><td> *94</td>
<td> 1-naphthyl</td><td></td><td> 9״°4־ב</td>
<td> 4-phenylphenyl</td><td></td><td> ε<sub>Λ</sub></td>
<td> 4-phenylphenyl</td><td></td><td> £-C<sub>4</sub>H<sub>9</sub></td>
<td> 4-phenylphenyl</td><td></td><td></td>
<td> 4-chlorophenyl</td><td> 2־<sup>C</sup>A</td><td> ^ו<sub>4</sub>ם־יי</td>
<td> 4-fluorophenyl</td><td></td><td></td>
<td> 4-(4-chlorophenoxy)phenyl</td><td> 2־C<sub>4</sub>H<sub>?</sub></td><td></td>
<td> 4-t-butylphenyl</td><td> s-c<sub>4</sub>h<sub>?</sub></td><td> 1-^9</td>
<td> 3-methoxyphenyl</td><td> %</td><td> 9”4<sup>ש</sup>־1</td>
<td> 3-trifluoromethylphenyl</td><td><sup>0</sup>Λ־־</td><td> srC<sub>4</sub>^</td>
<td> 2-thiomethylphenyl</td><td> l-CjHy</td><td> 3-methylbutyl</td>
<td> 2,4-dichlorophenyl</td><td> H-C<sub>4</sub>h<sub>9</sub></td><td> 2־C<sub>4</sub>h<sub>9</sub></td>
<td> 2,6-dimethylphenyl</td><td> t־C<sub>4</sub>H<sub>9</sub></td><td> «Λ</td>
<td> 3-methyl-4-chlorophenyl</td><td></td><td> 57^4^9</td>
<td> 2-<nethyl-5-fluorophenyl</td><td> I^c<sub>4</sub>h<sub>9</sub></td><td> K4H9</td>
<td><sup>C</sup>25״</td><td> phenyl</td><td> phenyl</td>
<td> cyclohexyl</td><td> phenyl</td><td> phenyl</td>
<td> ^18^7</td><td> phenyl</td><td> phenyl</td>
<td></td><td> 4-chlorophenyl</td><td> 4-chlorophenyl</td>
<td> 5^2!<sup>ש</sup>־2</td><td> 4-chlorophenyl</td><td> 4-chlorophenyl</td>
<td> 1-naphthyl</td><td> 4-fluorophenyl</td><td> 4-fluorophenyl</td>
<td> cyclopropyl</td><td> phenyl</td><td> 4-t-butylphenyl</td>
<td> —<sup>-</sup>^4^9</td><td> phenyl</td><td> 4-phenylphenyl</td>
<td> —<sup>-</sup>^4^9</td><td> phenyl</td><td> 2,4-dichlorophenyl</td>
<td> n-CjH<sub>7</sub></td><td> phenyl</td><td> 3-trifluoromethylphenyl</td>
Table VI (continued)
<td></td><td><sup>r</sup>2</td><td><sup>R</sup>3 ־</td>
<td></td><td></td><td><sup>1</sup></td>
<td> i־<sup>c</sup>A</td><td> phenyl</td><td> 3,5-di chioroph eny1</td>
<td> 5 cyclopentyl</td><td> phenyl</td><td> 2,6-dimethoxyphenyl</td>
<td> 2־<sup>c</sup>!4<sup>h</sup>29</td><td> 4-chlorophenyl</td><td> 2-fluorophenyl</td>
<td> n־C<sub>4</sub>H<sub>9</sub></td><td> 4-fluorophenyl</td><td> 4-phenylphenyl</td>
<td> phenyl</td><td> phenyl</td><td> phenyl m.p. 118-121°</td>
<td> 4-chlorophenyl</td><td> 4-chlorophenyl</td><td> 4-chlorophenyl m.p. 136-138°</td>
<td><sup>1</sup>θ 4-fluorophenyl</td><td> 4-fluorophenyl</td><td> 4-fluorophenyl m.p. 84-85°</td>
<td> 4-phenylphenyl</td><td> 4-phenylphenyl</td><td> 4-phenylphenyl</td>
<td> 2,4-dichlorophenyl</td><td> 2,4-dichlorophenyl</td><td> 2,4-dichlorophenyl</td>
<td> phenyl</td><td> 4-fluorophenyl</td><td> 4-fluorophenyl</td>
<td> phenyl</td><td> 4-chlorophenyl</td><td> 4-chlorophenyl</td>
<td><sup>15</sup> phenyl</td><td> 4-phenylphenyl</td><td> 4-phenylphenyl</td>
<td> phenyl</td><td> 2,4-dichlorophenyl</td><td> 2,4-dichlorophenyl</td>
<td> 2-naphthyl</td><td> 4-methylthiopheny1</td><td> 4-methylthiophenyl</td>
<td> 4-chlorophenyl</td><td> 2-methoxyphenyl</td><td> 2-methoxyphenyl</td>
<td> 4-chlorophenyl</td><td> 3-chlorophenyl</td><td> 3-chlorophenyl</td>
<td><sup>20</sup> phenyl</td><td> 2-chlorophenyl</td><td> 4-fluorophenyl</td>
<td> phenyl</td><td> 4-chlorophenyl</td><td> 4-phenylphenyl</td>
<td> 1-naphthyl</td><td> 4-bromophenyl</td><td> 3-methyIphenyl</td>
<td> 4-phenoxyphenyl</td><td> 3,5-dimethylphenyl</td><td> 3,4-dichlorophenyl</td>
<td> 4-methylphenyl 25 > , ,</td><td> 4-methylphenyl</td><td> .CH<sub>q</sub> b.p. 169-173 3 (u. 1 mm)</td>
Example 26
Preparation of (1,1'-Blphenyl-4-yl)dlmethyl(3-methyl1H-1,2,4-triazol-l-y!methyl)silane_______
A solution of 5.9 g (0.020 mol) of (l,l’-biphenyl-4-y!)dimethyl(1H-1,2,4-triazol-l-ylmethyl)silane in 40 ml of dry tetrahydrofuran was chilled to -40° under N? and stirred while 12.5 ml (0.020 mol) of 1.6 molar n-butyllithium in hexane<sup>1</sup> was added dropwise. The resulting yellow solution was stirred another 15 minutes at -40°, treated with 1.9 ml (4.2 g, 0.030 mol) of methyl iodide, and allowed to warm to room temperature. The resulting solution was diluted with water and extracted with hexanes. Washing the organic extracts with water and brine, drying over magnesium sulfate, and evaporation gave 5.7 g of solid, which was purified by dry-column chromatography over silica gel (ethyl acetate elution) to give 1.1 g of crude product. Recrystallization from 12 ml of 3:1 hexanesethyl acetate then gave 0.97 g (16%) of the title comp pound as an off white solid: m.p. 95-98°; ir (Nujol ) 1590, 1270, 1250, 1180, 1120, 830, 765, 700 cm<sup>1</sup>־; nmr (CDClj) 0.5 (6H, s), 2.2 (3H, s), 3.7 (2H, s), 7.2-7.7 (9H, m), 7.8 (1H, s).
Although the indicated structure is preferred for steric reasons, the position of the methyl group on the triezole ring has not been proven, and it is possible that the product is (l,l’-blphenyl-4-yl)dimethyl(5-methyl-lH-l,2,4-triazol-l-ylmethyl)silane.
The procedure' of Example 26 may be used to prepare the compounds of Table VII.
Table VII *pSi-CHjN r<sub>3</sub>
<td> ב</td><td> 52</td><td> 22</td><td> 52</td>
<td> ¾¾7</td><td> CH,</td><td> CH,</td><td> %</td>
<td> phenyl</td><td> CHj</td><td> CH,</td><td><sup>01</sup>J</td>
<td> 4-phenylphenyl</td><td> 2־<sup>c</sup><sub>4</sub>H<sub>9</sub></td><td> CHj</td><td> CH,</td>
<td> phenyl</td><td> phenyl</td><td> %</td><td> CH,</td>
<td> 4-fluorophenyl</td><td> phenyl</td><td> CH,</td><td> CH</td>
<td> 4-chlorophenyl</td><td> phenyl</td><td> 3 CH,</td><td> 3 CH_</td>
4-fluorophenyl 4-fluorophenyl CH<sub>3</sub> CK
4-chlorophenyl 4-chlorophenyl CH^ch.
2-chlorophenyl 4-chlorophenyl CH^CH^
1-naphthyl n-C^n-C^ phenyl phenyl phenylCH^
Example 78
Preparation of the 1:1 complex of (l,l'-Biphenyl-4-yl)dimethyl(lH-l,2,4-triazol-l-ylmethyl)silane and Cuprous
Chloride....................
A mixture of 5.0 g (0.017 mol) of (1,1’-biphenyl4-yl)dimethyl(lH-l,2,4-triazol-l-ylmethyl)silane and
1.7 g (0.017 mol) of cuprous chloride in 170 ml of tetrahydrofuran was refluxed under N<sub>2</sub> for 30 minutes, and the resulting deep green solution was evaporated to leave the title compound as a dark greenish-brown solid: m.p. 85-90°; ir (Nujol<sup>R</sup>) 3110, 1590, 1280, 1250, 1120, 1010, 990, 840, 825, 760, 700 cm<sup>1</sup>־.
The following metal complexes of (l,l'-biphenyl4-yl)dimethyl(lH-l,2,4-triazol-4-y!methyl)silane were prepared similarly:
1:1 Complex with cupric chloride: m.p. 83-87°
2:1 Complex with cupric chloride: m.p. 85-92° 21
1:1 Complex with zinc chloride: n£ 1.5737
1:1 Complex with manganous sulfate: m.p. 244-250° (decomp.)
Example 27 Preparation of the 4-Dodecylbenzenesulfonate Salt of (1,1’-Biphenyl-4-yl)dimethyK1H-1,2,4-triazol-l-ylmethyDsilane
A solution of 1.0 g (0.0034 mol) of (l,l'-biphenyl-4-yl)dimethyl(lH-l,2,4-triazol-l-ylmethyl)silane in 10 ml of dichloromethane was combined with a solution of 1.1 g (0.0034 mol) of 4-dodecylbenzenesulfonic acid in 10 ml of dichloromethane. The resulting solution was evaporated to leave the title salt as a viscous yellow oil: ηθ 1,5645; ir (neat) 3110, 3050, 3020, 2960, 2920, 2850, 2570, 1920, 1600, 1545, 1485, 1455, 1405, 1250, 1225, 1165, 1120, 1030, 1010, 990, 845, 825, 755, 735, 700, 670, 635 cm<sup>1</sup>־.
Example 29
Preparation of the 2:1 complex of [bis(4-Fluorophenyl)]methyl(1H-1,2,4-triazol-l-ylmethyl)silane and Cupric Chloride______
A mixture of 1.0 g (0.0032 mol) of [bis(4-fluorophenyl)]muthyl(lH-l,2,4-triazol-l-ylmethyl)silane and 0.2 g (0.0016 mol) of cupric chloride in 30 ml of tetrahydrofuran was refluxed under N? for 30 minutes and evaporated to leave the title complex as a blue* p green glass: no distinct m.p.; ir (Nujol ) 1580, 1490, 1230, 1160, 1110, 830, 785 cm<sup>1</sup>־.
The 1:1 complex with cuprous chloride was pre* pared similarly to give a dark green glass: no dis* tinct m.p.; ir as above.
By applying the procedures of Examples 27-29, any of the compounds of Tables VI, VII, VIII, IX, XII and XIII can be converted to salts or metal complexes.
Example 30
Preparation of (l,l-’Biphenyl-4-yl)(lH-l,2,4-triazol1-ylmethyl)(methoxy)methylsilane
A mixture of (l,l’-biphenyl-4-yl)chlorochloromethylmethylsilane and two equivalents of 1,2,4-triazole sodium salt in dimethylformamide is warmed to 80-90°C for 2 hours. Ten equivalents of methanol is then added, and the mixture is held at 70°C for 1 hour, cooled, diluted with water, and quickly extracted with ether. Washing the ether solution with water and brine, drying over magnesium sulfate, and evaporation leaves the title compound.
Related compounds can be aiade in the same way, using the appropriate chlorosilane and alcohol; for Rg = OH, water is used instead of an alcohol, and hydrolysis is conducted at 20-25<sup>e</sup>C instead of 70°.
- 66114/2
Example 3? Preparation of (l,l-dimethylethoxy)methyl(phenyl)(1Hl,2,4־-triazol-l־ylmethyl)silane______׳
A mixture of 3.6 g (0.015 mol) of chloromethyl5 (l,l-dimethylethoxy)methyl(phenyl)silane and 1.3 g (0.015 mol) of 1,2,4-triazole sodium salt in 8 ml of dimethylformamide was stirred at 80° for 2 hours, cooled, and poured onto water. The resulting mixture was extracted with ether, and the ether extracts were 10 washed with water and brine, dried over magnesium sulfate, and evaporated to leave 2.7 g of a yellow oil. Chromatography on silica gel, eluting with 50:50 ethyl acetate-hexanes, provided 1.5 g (36%) of the title compound as a pale yellow oil: ηθ 1.5134; ir (neat) 15 3120, 3070, 3045, 2975, 2925, 1500, 1425, 1380, 1365, 1270, 1255, 1240, 1190, 1140, 1115, 1050, 1020, 1010, 830, 810, 790, 740, 700, 680 cm<sup></sup>; nmr (CDClj): 0.6 (3H, s), 1.3 (9H, s), 3.9 (2H, s), 7.3-7.7 (5H, m), 7.9 (1H, s) and 8.0 (1H, s).
- £/½ 31A Example ZZX Preparation of bis(4-Fluorcphenyl)hydroxy (1H-1,2,4triazol-l-ylmethyl)silane . A mixture of 10.0 g (30.6 mmol) of chlorcmethy1[bis(4-fluorophenyl)](2-prcpoxy)silane and 3.1 c (30.6 mmol) of 1,2,4-triazole <sup>,</sup>sodium salt in dimethyl formamide was stirred at 80-90° under nitrogen for 2 hours. Workup as in Example 32 gave a waxy solid that was washed with 1:1 ether-hexanes to leave 3.0 g (30%) of the title compound. Recrystallization from chlorobutane gave a purer sample: m.p. 130-131°; nmr (CDCl-j) 4.1 (2H, s) , 5.8 (1H, broad s) , 7.1 (4H, t),
7.7 (4H, d Of d), 7.8 (IH, s), 8.0 (IH, s).
31B . Example ZZZ.
Preparation of bis(4-Chlorophenyl)hydroxy(1H-1,2,4triazol-l-yImethyl) silane and bis (4-Chlorophenyl)hydr0xy(4H-l,2,4-triaZ01-4-ylmethyl)silane
The procedure of Example 32A was applied to chloromethy 1[bis(4-chlorophenyl)](2-propoxy)silane. Workup gave an oil, which was swirled with hexanes. The hexanes layer was then decanted, and the residual oil was crystallized from 9:1 hexanes-ethyl acetate to give the 1H isomer as a solid: m.p. 13C-131<sup>־</sup>; nmr (CDClj) 4.1 (2H, s), 6.3 (1H, broad s), 7.4 (4H, d) , 7.6 (4H, d), 7.8. (IH, s) , 8.0 (IH, s).
Chromatography of the mother liquors over silica gel, eluting first with hexanes and then with 9:1 dichloromethane-acetone, provided the 4H Isomer as a solid: m.p. 98-103°; nmr (CDCl^) 1.7 (1H, broad s) ,
4.2 (2H, s), 7.8 (8H, s), 7.8 (2H, s).
Example 312
Preparation of (l,l’-Biphenyl-4-yl)hydroxy(methyl)(1H-1,2,4-triazol-l-y!methyl)si lane
A mixture of 3.0 g (8.9 mmol) of (1,I'-biphenyl4-yl)methyl(2-propoxy)(1H-1,2,4-triaz01-1-yImethy 1)silane, 3 ml of concentrated hydrochloric acid, ID ml of water, and 10 ml of tetrahydrofuran was stirred at room temperature overnight. The resulting solution was diluted with ether, washed with saturated aqueous sodium bicarbonate, water, and brine, dried over magnesium sulfate, and evaporated to leave 2.3 g of viscous oil. Chromatography over silica gel, eluting with hexane followed by ether, provided 1.1 g (42%) of the title compound as a viscous oil that solidified on standing: m.p. 97-99°; nmr (CDCij) 0.5 (3H, s), 3.9 (2H, s), 5.2 (1H, broad 5), 7.3-7.8 (9H, m), 7.9 (1H, s), 8.0 (1H, s).
The compounds of Tables VIII and IX can be made using the procedures of Examples 30-31C.
- W ־
31D
Preparation of a disolxane is^jTlustrated by Example 3/P׳. Example //1/
Preparation of Oxybis[bis(4-fluoropneny1)(1H-1,2,4triazol-l-y!methyl)si lane]
A solution of 11.0 g (33.7 mmol) of chloromethyl[bis(4-fluorophenyl)](2-propoxy)silane and 10 ml of 49% aqueous hydrofluoric acid in ethanol was refluxed for 2 hours under nitrogen, cooled, and partitioned between water and ether. The organic layer was washed with water and brine, dried over magnesium sulfate, and evaporated to leave 9.7 g (100%) of chloromethyl(flupro)[bis(4-fluorophenyl)]silane as a mobile oil: n<sup>22</sup> 1.5337; nmr (COCip 3.2 (2H, d) , 7.2 (4H, t), 7.8 (4H, d of d).
A mixture of 4.5 g (16 mmol) of the fluorcsilane prepared above and 1.6 g (13 mmol) of 1,2,4-triazole sodium salt in dimethylformamide was stirred at 30-90° for 2 hours. The resulting slurry was diluted with ether, washed three times with water and once with brine, dried over magnesium sulfate, and evaporated to leave a viscous oil. Trituration with 1:1 etherhexanes gave 1.1 g (23%) of the title disiloxane as a colorless solid: m.p. 165-168°; nmr (0001^) 4.1 (2H, s), 7.0 (4H, t), 7.4 (4H, d of d), 7.3 (1H, s),
7.9 (1H, s) .
Table VIII ?2
<img file="IL66114A_D0024.tif" />
<td> 21</td><td> 22</td><td> 2«</td>
<td> ε<sub>Λ</sub></td><td> %</td><td> CHj</td>
<td> «A</td><td> ל°</td><td> W9</td>
<td> a^A</td><td> CH,</td><td></td>
<td></td><td> CjH<sub>5</sub></td><td> CM,</td>
<td> £¾8^7</td><td></td><td> “3</td>
<td> cyclopropyl</td><td> “j</td><td> ^4^</td>
<td> cyclohexyl</td><td> ch.</td><td> *3</td>
<td> 1-naphthyl</td><td> i^cyiy</td><td> l-c^</td>
<td> phenyl</td><td> ch<sub>3</sub></td><td> H</td>
<td> phenyl</td><td> CHj</td><td> CH,</td>
<td> phenyl</td><td> %</td><td></td>
<td> phenyl</td><td> ch,</td><td> i-C^ r^° 1.5367</td>
<td> phenyl</td><td> i־<sup>c</sup>A</td><td> H</td>
<td> 4-phenylphenyl</td><td> a9^4^־</td><td> ch<sub>3</sub></td>
<td> 4-phenylphenyl</td><td> t־C<sub>4</sub>H<sub>9</sub></td><td> H</td>
<td> 4-phenylphenyl</td><td> CH<sub>3</sub></td><td> 5”2<sup>ש</sup></td>
<td> 4-phenylphenyl</td><td> ch<sub>3</sub></td><td> n־C<sub>4</sub><sup>H</sup><sub>9</sub></td>
<td> 4-chlorophenyl</td><td> 4^9</td><td> a־c<sub>4</sub>H<sub>9</sub></td>
<td> 4-chlorophenyl</td><td> CHj</td><td> ^3</td>
<td> 4-chlorophenyl</td><td> ch<sub>3</sub></td><td> ^5</td>
<td> 4-fluorophenyl</td><td></td><td></td>
<td> 4-fluorophenyl</td><td> CH,</td><td> %</td>
<td> 4-t-butylphenyl</td><td> 2־<sup>C</sup>A</td><td></td>
<td> 3-trifluorome thyIpheny1</td><td> 1־<sup>C</sup>A</td><td> H</td>
־.י naij
66114/2 1
- ’
Table VIII (continued)
<td> ב</td><td></td><td> %</td>
<td> 2,4-dichlorophenyl</td><td></td><td> CH^</td>
<td> 2,4-dJchlaropheny1</td><td> CH, J</td><td></td>
<td> 2,4-dichlorophenyl</td><td> CHj</td><td></td>
<td> 2,4-dichlorophenyl 1</td><td></td><td> CjHj</td>
<td> 2-methyl-5-fluorophenyl</td><td> s־C<sub>4</sub>H<sub>9</sub></td><td></td>
<td> 2,6-dimethoxyphenyl</td><td> 1,1-dimethylpropyl</td><td> H !</td>
<td> 3-methyl-4-chlorophenyl</td><td> 'Λ</td><td> CH,</td>
<td> 3,5-dichlorophenyl</td><td></td><td><sup>c</sup>25״</td>
<td></td><td> 2,4-dichlorophenyl</td><td></td>
<td> 37”18<sup>ס</sup>־פ</td><td> phenyl</td><td></td>
<td> 1-naphthyl</td><td> phenyl</td><td> %</td>
<td> phenyl</td><td> phenyl</td><td></td>
<td> 4-fluorophenyl</td><td> phenyl</td><td> CH,</td>
<td> 4-chlorophenyl</td><td> phenyl</td><td></td>
<td> 4-phenylphenyl</td><td> phenyl</td><td> C^<sub>5</sub></td>
<td> 4-phenylphenyl</td><td> phenyl</td><td></td>
<td> 4-t-butylphenyl</td><td> phenyl</td><td> 27^4^9</td>
<td> 3-fluorophenyl</td><td> phenyl</td><td> ^5</td>
<td> 2-methoxyphenyl</td><td> phenyl</td><td> H</td>
<td> 2-chlorophenyl</td><td> phenyl</td><td></td>
<td> 2,4-dichlorophenyl</td><td> phenyl</td><td> A“<sup>C</sup>3<sup>H</sup>7</td>
<td> 3,5-dichlorophenyl</td><td> phenyl</td><td></td>
<td> 4-fluorophenyl</td><td> 4-fluorophenyl</td><td> 1־<sup>C</sup>4<sup>H</sup>9</td>
<td> 4-fluorophenyl</td><td> 4-fluorophenyl</td><td> C2H<sub>5</sub></td>
<td> 4-chlorophenyl</td><td> 4-chlorophenyl</td><td> CHj</td>
<td> 4-chlorophenyl</td><td> 4-chlorophenyl</td><td> ^5</td>
<td> 4-phenylphenyl</td><td> 4-phenylphenyl</td><td> CHj</td>
<td> 2,4-dichlorophenyl</td><td> 2,4-dichlorophenyl</td><td> %</td>
<td> 3-trifluoromethylphenyl</td><td> 3-tri fluoromethylphenyl</td><td> 1־C4<sup>H</sup>9</td>
<td> 2-methoxyphenyl</td><td> 2-methoxyphenyl</td><td> H</td>
<td> 2-chlorophenyl</td><td> 4-fluorophenyl</td><td> H</td>
׳79
Table VIII(continued)
3-trifluoromethylphenyl 4-t-butylphenyl n-C^H^ <sup>5</sup> 2-fluoro-4-chlorophenyl 4-bromophenyl -<sup></sup>ל’<sup>1</sup>{׳־
2.3- dimethylphenyl 4-methyl thiophenylC^
2,6-dimethoxyphenyl 4-methoxyphenylH
3.4- dichlorophenyl 4-methyIphenyl—“^9
Table IX
<img file="IL66114A_D0025.tif" />
<td> 21</td><td></td><td> צ</td>
<td> cyclohexyl</td><td></td><td><sup>0</sup>Λ־!</td>
<td> phenyl</td><td></td><td></td>
<td> phenyl</td><td></td><td></td>
<td> phenyl</td><td></td><td></td>
<td> 4-phenylphenyl</td><td> i־<sup>c</sup>A</td><td> «Λ</td>
<td> 4-phenylphenyl</td><td></td><td></td>
<td> 4-chlorophenyl</td><td> CHj</td><td></td>
<td> 4-fluorophenyl</td><td></td><td></td>
<td> 4-fluorophenyl</td><td> phenyl</td><td> i-cyb</td>
<td> 4-chlorophenyl</td><td> phenyl</td><td> l-'A</td>
<td> 4-fluorophenyl</td><td> 4-fluorophenyl</td><td> «Λ</td>
<td> 3-methylphenyl</td><td> 3-methylphenyl</td><td> —”^4^9</td>
7? 32
Example
Preparation of Chloromethyl(dichloro)phenylsilane
A solution of 25.1 ml (36.8 g, 0200־ mol) of chloromethyltrichlorosilane in 400 ml dry tetrahydrofuran was cooled to -78׳° under nitrogen and stirred vigorously while 48.0 ml (0.100 mol) of 2.1 molar phenyllithium was slowly dripped in over 1 hour. After stirring another 30 minutes at -78° the solution was allowed to warm to room temperature and evaporated to about 200 ml. Addition of 500 ml ether, filtration to remove precipitated lithium chloride, and evaporation of the filtrate left 25.0 g of liquid. Distillation gave 6.5 g (29%) of the title compound as a colorless liquid: bp 62-82° (0.15 mm); nmr (COClj): d*3.3 (s, 2) and 7.1-7.9 (m, 5).
Example Preparation of Chloromethyl(diethoxy)phenylsilane
A solution of 1.0 g (0.0044 mol) of chloromethyl(dichloro)phenylsilane in 8 ml of absolute ethanol was cooled to 0° under nitrogen and stirred while 0.61 ml (0.445 g, 0.0044 mol) of triethylamine was slowly added, giving a slurry that was allowed to warm to room temperature. Addition of 50 ml of ether, filtration to remove precipitated triethylamine/hydrochloride, and evaporation of the filtrate left a residue which was filtered through a short silica gel column (95% petroleum ether:ethyl acetate as the eluent) to give 0.80 (73%) of the title compound as a colorless oil: nmr (CDClj): 1.25 (t, 6, 3 6 ־Hz), 3.0 (s, 2),
3.9 (q, 4, 3 = 6Hz) and 7.2-7.9 (m, 5).
n 34 Example
Preparation of Chloromethy1(pheny1)bis(2-propoxy)silane A solution of 2.0 g (0.009 mol) of chloromethyl-־' (dichloro)phenylsilane and 5 ml of 2-propanol in 15 ml of dimethylformamide was stirred under N<sub>2</sub> while 2.5 ml (1.9 g, 0.018 mol) of triethylamine was added dropwise. The resulting slurry was warmed to 80° for 2 hours, cooled, diluted with water, and extracted with ether. The ether extracts were washed with water and brine, dried over magnesium sulfate, and evaporated to leave 2.2 g of liquid. Column chromatography over silica gel, eluting with petroleum ether, provided 1.4 g (58%) of the titlecompound as a colorless liquid: ηθ<sup>2</sup> 1.4741; nmr (CDClj) 1.2 (12H, d, J = 6), 3.0 (2H, s), 4.3 (2H, septet, 3 = 6), 7.3-7.8 (5H, m).
The compounds of Tables X and XI can be made using the procedures of Examples /3-35/ 32-34.
7?
Table X
<td> 5</td><td> R,-S1-CH<sub>2</sub>C1 °<sup>R</sup>6</td>
<td></td><td> 21 2« —“^4^9</td>
<td> 10</td><td> —*4^9 ^2^5 —^18<sup>H</sup>37 <sup>CH</sup>3 cyclohexyl n-CjH?</td>
<td></td><td> 1-naphthyl i<sup>-C</sup>4<sup>H</sup>9 phenyl CH^</td>
<td> 15</td><td> phenyl £“^j<sup>h</sup>7 phenyl t-C^H^ 4-phenylphenyl C<sub>2</sub>H<sub>5</sub> 4-phenylphenyl n-C^H^ 4-fluorophenyl CH^</td>
<td> 20</td><td> 4-fluorophenyl C<sub>2</sub>H<sub>5</sub> 4-chlorophenyl C<sub>2</sub>H<sub>5</sub> 4-chlorophenyl i־<sup>c</sup>3<sup>H</sup>7 3-trifluoromethylphenyl 1“^4<sup>H</sup>9 2-methoxyphenyl £־<sup>C</sup>3<sup>H</sup>7</td>
<td> 25</td><td> 2.3- dimethylphenyl i“<sup>c</sup>4<sup>H</sup>9 2.4- dichlorophenyl CH^ 2,4-dichlorophenyl C<sub>2</sub>H<sub>5</sub> 2-methoxy-5-fluorophenyl A־<sup>C</sup>3<sup>H</sup>7 2,6-dimethoxyphenyl CH^</td>
<td> 30</td><td> 3.4- dichlorophenyl ^2<sup>H</sup>5 3.5- dichlorophenyl £-C<sub>4</sub>H<sub>g</sub></td>
Example 35
Preparation of Phenylbis(2-propoxy)(1H-1,2,4-trlazoll-ylmethyl)silane
The title compound can be made by applying the procedure of Example 31 to chloromethyl(phenyl)bis(2-propoxy)silane: 1.4962; nmr (CDClj) 1.1 (12H, d, 3 = 6), 4.0 (2H, s), 4.3 (2H, septet, J * 6), 7.2-8.0 (7H, m)L
The compounds of Table XII can be made similarly.
Table XII
<img file="IL66114A_D0026.tif" />
<td></td><td> %</td><td></td>
<td><sup>C</sup>25״</td><td> t-c^</td><td> H</td>
<td> S־C<sub>4</sub><sup>h</sup>j</td><td> %</td><td> H</td>
<td> 2^1^37</td><td> °<sup>1</sup>3</td><td> H</td>
<td> cyclohexyl</td><td></td><td> H</td>
<td> 1-naphthyl</td><td></td><td> H</td>
<td> phenyl</td><td> **Λ</td><td><sup>0,</sup>3</td>
<td> phenyl</td><td> 9^־1</td><td> H</td>
<td> 4-phenylphenyl</td><td> ^<sub>4</sub>ס-<ז</td><td> H</td>
<td> 4-fluorophenyl</td><td> %</td><td> H</td>
<td> 4-fluarophenyl</td><td></td><td> H</td>
<td> 4-chlorophenyl</td><td></td><td> H</td>
<td> 4-chlorophenyl</td><td> A-C3H7</td><td> H</td>
<td> 2-methoxyphenyl</td><td></td><td> cn<sub>3</sub></td>
<td> 2,4-dichlorophenyl</td><td> %</td><td> H</td>
<td> 2,4-dichlorophenyl</td><td></td><td> H</td>
<td> 2-methoxy-5-fluorophenyl</td><td> 7^־1</td><td> H</td>
<td> 2,6-dimethoxy phenyl</td><td> CH,</td><td> H</td>
<td> 3,4-dichloropheny1</td><td><sup>C</sup>25״</td><td> H</td>
<td> 3,5-dichlorophenyl</td><td> 2־C<sub>4</sub>H<sub>9</sub></td><td> H</td>
MX Example 77 Preparation of (l,l’-Biphenyl-4-yl)dimethyl(lH-imidazol-l-ylmethypsilane................
A mixture of 2.6 g (0.010 mol) of (!,!<sup>,</sup>-biphenyl-
4-yl)chloromethyldimethylsilane and 1.1 g (0.012 mol) of imidazole sodium salt in 5 ml of dimethylformamide was warmed to 80-90° for 2 hours, cooled, diluted with water, and extracted with ether. The ether solution was washed with water and brine, dried over magnesium sulfate, and evaporated to leave 2.0 g of a viscous, pale yellow oil. Trituration of a small sample with hexanes gave a solid. The bulk of the crude product was then taken up in a hot mixture of 20 ml of hexanes and 3 ml of ethyl acetate, the solution was cooled slowly, and seed crystals were added when cloudiness was observed. The resulting crystals were collected and dried to give 0.84 g (29%) of the title compound
ם as colorless flakes: m.p. 51-53°; ir (Nujol ) 1235, 1215, 1105, 1065, 900, 830, 785, 750, 730, 685 cm<sup>1</sup>־; nmr (CDClj) 0.4 (6H, s), 3.7 (2H, s), 6.7 (1H, broad s), 7.0 (1H, broad s), 7.1-7.8 (10H, m); analysis for <sup>C</sup>18<sup>H</sup>20<sup>N</sup>2<sup>Si (mw 292</sup>.<sup>45</sup>)<sup>: </sup>Calculated C, 73.92; H, 6.89; N, 9.58; Found C, 73.4; H, 7.0; N, 9.4; 73.7; 7.0; 9.4.
Example 73
Preparation of (4-Chlorophenyl)dimethyl(lH-imidazol-l-ylmethyl)silane
A mixture of 2.2 g (0.010 mol) of chloromethyl(4chlorophenyDdimethylsilane and 1.1 g (0.012 mol) of imidazole sodium salt in 5 ml of dimethylformamide was stirred at 80-90° for 2 hours, cooled, diluted with water, and extracted with ether. The ether solution was washed with water and brine, dried over magnesium sulfate, and evaporated to leave 2.0 g (81%) of the 20 title compound as a yellow liquid: ηθ 1.5472; ir (neat) 1560, 1495, 1480, 1375, 1250, 1105, 1080, 905, 830, 810, 740 cm“<sup>1</sup>; nmr (CDCl-j) 0.3 (6H, s), 3.6 (2H, s), 6.6 (1H, broad s), 6.9 (1H, broad s), 7.1 (1H, broad s), 7.3 (4H, s).
Example M Preparation of (2,4-Dichlorophenyl)dimethyl(lHimidazol-l-ylmethyl)silane
A mixture of 5.1 g (0.020 mol) of chloromethyl(2,4-dichlorophenyl)dimethylsilane and 2.0 g (0.022 mol) of imidazole sodium salt in 10 ml of dry dimethylformamide was stirred at 80-90° for 2 hours and worked up as in Example 18 to give 3.9 g (69%) of the 23 title compound as a brown oil: n^ 1.5637; ir (neat) 1560, 1500, 1450, 1355, 1250, 1105, 1095, 1075, 1025, 840, 780, 735 cm“<sup>1</sup>; nmr (CDClj) 0.4 (6H, s),
3.9 (2H, s), 6.7 (1H, broad s), 7.0 (1H, broad s)
7.2-7.5 (4H, m).
Example #0
Preparation of Diphenyl(lH-imidazol-l-ylmethyl)methylsilane..................
A mixture of 4.9 g (0.020 mol) of chloromethyl(diphenyl)methylsilane and 2.0 g (0.022 mol) of imidazole sodium salt in 10 ml of dry dimethylformamide was stirred at 80°C for 3.5 hours and worked up as in Example 18 to give 4.8 g of a yellow oil. Kugelrohr distillation at 125°/0.05 mm removed volatile impurities, leaving behind 2.9 g (52%) of the title compound as an oil: ηθ 1.5995; ir (neat) 3375, 3250, 1500, 1430, 1255, 1230, 1110, 1075, 1025, 810, 790, 735, 700, 660 cm<sup>1</sup>־; nmr (CDClj) 0.6 (3H, s),
3.9 (2H, s), 6.6 (IH, broad s), 6.9 (IH, broad s),
7.2-7.5 (11H, m).
36-39
By applying the procedures of Example /7-4¢ to appropriate chloromethylsilanes, the compounds of Table XIV can be prepared.
Table XIV
<img file="IL66114A_D0027.tif" />
<td> 21</td><td> R2</td><td> 22</td>
<td> 1-naphthyl</td><td> ch<sub>3</sub></td><td> 23 CH<sub>3</sub> 1.6188</td>
<td> 2-naphthyl</td><td> ch<sub>3</sub></td><td> ch<sub>3</sub></td>
<td> 4-bromophenyl</td><td> CH<sub>3</sub></td><td> CH<sub>3</sub> n^° 1.5741</td>
<td> 4-fluorophenyl</td><td> ch<sub>3</sub></td><td> CH<sub>3</sub> n^<sup>3</sup> 1.5314</td>
<td> 4-methoxyphenyl</td><td> ch<sub>3</sub></td><td> 25 CH<sub>3</sub> rfr 1.5485</td>
<td> 4-phenoxy phenyl</td><td> CK<sub>3</sub></td><td> 77 CH<sub>3</sub> ηβ 1.5833</td>
<td> 4-(4-chlorophenoxy)phenyl</td><td> ch<sub>3</sub></td><td> CH<sub>3</sub> n<sup>22</sup> 1.5564</td>
<td> 4-(4-fluorophenoxy)phenyl</td><td> ch<sub>3</sub></td><td> ch<sub>3</sub></td>
<td> 4-(4-tri fluoromethylphenoxy)phenyl</td><td> ch<sub>3</sub></td><td> %</td>
<td> 4-(4-methyIphenoxy)phenyl</td><td> CH<sub>3</sub></td><td> CH<sub>3</sub></td>
<td colspan="2"> Table XIV (continued)</td><td></td><td></td>
<td><sup>R</sup>i</td><td> 2״</td><td><sup>R</sup>3</td><td></td>
<td> ' </td><td></td><td></td><td></td>
<td> 4-thiome thyIpheny1</td><td><sup>01</sup>3</td><td> CH<sub>3</sub></td><td> n^<sup>5</sup> 1.5855</td>
<td> 4-methylsulfonyIpheny1</td><td> CH<sub>3</sub></td><td> ch<sub>3</sub></td><td> 21 ηθ 1.5552</td>
<td> 4-trifluoromethylphenyl</td><td> CHj</td><td> ch<sub>3</sub></td><td> 77 ng 1.4867</td>
<td> 4-methylphenyl</td><td> CH<sub>3</sub></td><td> ch<sub>3</sub></td><td> n<sup>21</sup> 1.5482</td>
<td> 4-i-propylphenyl</td><td> ch<sub>3</sub></td><td> CH, j</td><td></td>
<td> 4-t-butyIpheny1</td><td> ch<sub>3</sub></td><td> CH<sub>3</sub></td><td> 23 ng 1.5229</td>
<td> 4-cyclohexylphenyl</td><td> CHj</td><td> ch<sub>3</sub></td><td> 22 ng 1.5085</td>
<td> 4-trifluoromethoxyphenyl</td><td> CHj</td><td> ch<sub>3</sub></td><td> 22 ng 1.4888</td>
<td> 4-(4-chlorophenyl)phenyl</td><td> ch<sub>3</sub></td><td> ch<sub>3</sub></td><td></td>
<td> 4-(4-methylphenyl)phenyl</td><td> ch<sub>3</sub></td><td> ch<sub>3</sub></td><td></td>
<td> 4-(4-tri fluoromethyIpheny1)phenyl</td><td> ch<sub>3</sub></td><td> ch<sub>3</sub></td><td></td>
<td> 4-(4-fluorophenyl)phenyl</td><td> ch<sub>3</sub></td><td> ch<sub>3</sub></td><td></td>
<td> 4-(4-bromophenyl)phenyl</td><td> ch<sub>3</sub></td><td> ch<sub>3</sub></td><td> n<sup>22</sup> 1.5745</td>
<td> 3-phenylphenyl</td><td> CHj</td><td> ch<sub>3</sub></td><td> 21 ng 1.6002</td>
<td> 3-trifluoromethylphenyl</td><td> CH<sub>3</sub></td><td> CH<sub>3</sub></td><td> ng° 1.4927</td>
<td> 3-chlorophenyl</td><td> CHj</td><td> ch<sub>3</sub></td><td> 22 ng 1.5560</td>
<td> 2-trifluoromethylphenyl</td><td> ch<sub>3</sub></td><td> ch<sub>3</sub></td><td> n<sup>23</sup> 1.5056</td>
<td> 2-phenylphenyl</td><td> ch<sub>3</sub></td><td> ch<sub>3</sub></td><td> 77 ng 1.5996</td>
<td> 2-chlorophenyl</td><td> ch<sub>3</sub></td><td> CH<sub>3</sub></td><td> 22 ng 1.5382</td>
<td> 2-methoxyphenyl</td><td> cn<sub>3</sub></td><td> CH, כ</td><td> n^<sup>2</sup> 1.5344</td>
<td> 2,3-dimethyIpheny1</td><td> CH<sub>3</sub></td><td> CH<sub>3</sub></td><td></td>
<td> 2,3-dimethoxyphenyl</td><td> CH<sub>3</sub></td><td> ch<sub>3</sub></td><td> ng<sup>2</sup> 1.5350</td>
<td> 2,4-di fluoropheny1</td><td> ch<sub>3</sub></td><td> ch<sub>3</sub></td><td></td>
<td> 2-fluoro-4-chloropheny1</td><td> ch<sub>3</sub></td><td> ch<sub>3</sub></td><td></td>
<td> 2-chloro-4-fluoropheny1</td><td> ch<sub>3</sub></td><td> ch<sub>3</sub></td><td></td>
<td> 2-chloro-4-phenylphenyl</td><td> ch<sub>3</sub></td><td> ch<sub>3</sub></td><td></td>
<td> 2-fluor 0-4-phenyIpheny1</td><td> ch<sub>3</sub></td><td> ch<sub>3</sub></td><td></td>
<td> 2-methy1-5-chloropheny1</td><td> CH<sub>3</sub></td><td> ch<sub>3</sub></td><td></td>
Table XIV (continued)
<td></td><td></td><td> י!</td>
<td> 2,6-oimethoxyphenyl</td><td> CH,</td><td> CH, «2’ 1.5J*8</td>
<td> 2,6-dimethyIpheny1</td><td> CH,</td><td> If ל°</td>
<td> 3,4-dichlorophenyl</td><td> CH,</td><td> CH, 1P 1.5CTJ</td>
<td> 3-methyl-4-fluorophenyl</td><td> CH,</td><td> w</td>
<td> 3,5-dichlorophenyl</td><td> %</td><td> CH, r^<sup>2</sup> 1.5481</td>
<td> 1-naphthyl</td><td></td><td> °S</td>
<td> 1-naphthyl</td><td> Wp</td><td></td>
<td> 2-naphthyl</td><td></td><td> °S</td>
<td> 4-phenylphenyl</td><td> ε<sub>Λ</sub></td><td> CH,</td>
<td> 4-phenylphenyl</td><td> *c<sub>4</sub>h,</td><td> CH, 12<sup>2</sup> 1.5880</td>
<td> 4-bromophenyl</td><td> ^־1</td><td></td>
<td> 4-chlorophenyl</td><td> *<sup>0</sup>Λ</td><td> CM, 1.5415</td>
<td> 4*fluorophenyl</td><td> *c<sub>4</sub>h,</td><td> CH, rff 1.5161</td>
<td> 4-phenoxyphenyl</td><td></td><td> ל°</td>
<td> 4-t-butylphenyl</td><td> «Λ</td><td> °b</td>
Table XIV (continued)
<td></td><td> 22</td><td></td>
<td> 3-phenylphenyl</td><td> l’<sup>c</sup>4«9</td><td> CHj</td>
<td> 3-trlfluoromethylphenyl</td><td> s־c<sub>4</sub>h<sub>9</sub></td><td> %</td>
<td> 3-chlorophenyl</td><td> £-^11</td><td> 3״</td>
<td> 2-methoxyphenyl (</td><td> t־C<sub>4</sub>H<sub>9</sub></td><td> *3</td>
<td> 2-phenylphenyl</td><td> 1S«9</td><td> CH,</td>
<td> 2,4-dichloropheny1</td><td> *S<sup>H</sup>9</td><td><sup>01</sup>3 $</td>
<td> 2,3-dimethyIpheny1</td><td></td><td> ch<sub>3</sub></td>
<td> 2,5-dimethoxyphenyl</td><td> 4-methylpentyl</td><td><sup>04</sup>3</td>
<td> 2,6-dimethyIpheny1</td><td> 1-methylbutyl</td><td> ch<sub>3</sub></td>
<td> 3,4-dichlorophenyl</td><td> ^Λ1</td><td> CH3</td>
<td> 3,5-dichlorophenyl</td><td></td><td> ch<sub>3</sub></td>
<td> 4-fluorophenyl</td><td> phenyl</td><td><sup>01</sup>3</td>
<td> 4-chlorophenyl</td><td> phenyl</td><td><sup>01</sup>3 H?</td>
<td> 4-bromophenyl</td><td> phenyl</td><td> %</td>
<td> 4-phenylphenyl</td><td> phenyl</td><td> ΠΗ n<sup>21</sup> °<sup>1</sup>3 %</td>
<td> 4-t-butyIpheny1</td><td> phenyl</td><td> CH,</td>
<td> 4-thiomethyIpheny1</td><td> phenyl</td><td></td>
<td> 4-phenoxyphenyl</td><td> phenyl</td><td> CH<sub>3</sub></td>
<td> 4-trifluoromethoxyphenyl</td><td> phenyl</td><td> CHj</td>
<td> 4-methylsulfonylphenyl</td><td> phenyl</td><td> %</td>
<td> 4-cyclohexylphenyl</td><td> phenyl</td><td> CH</td>
<td> 4-(4-fluorophenyl)phenyl</td><td> phenyl</td><td> *3</td>
<td> 3-trlfluoromethylphenyl</td><td> phenyl</td><td> CH<sub>3</sub></td>
<td> 2-chlorophenyl</td><td> phenyl</td><td> % ff</td>
<td> 2-methoxyphenyl</td><td> phenyl</td><td> CH<sub>3</sub></td>
1.5588
1.5810
1.6000
1.6115
1.6378
1.6058
־
Tible XIV (continued)
<td> 2.4- dichlorophenyl phenyl 2-chloro-4-phenylphenyl phenyl 2-fluoro-4-phenylphenyl phenyl 3.5- dichlorophenyl ׳ phenyl 2.5- dime thoxyphenyl phenyl 2.6- dimethoxyphenyl phenyl 4-fluorophenyl 4-fluorophenyl 4-chlorophenyl 4-chlorophenyl</td><td> 0<sup>2</sup>^ז <sub>ג</sub>י l.ttJO Oij גי° CHj ηξ<sup>2</sup> 1.5569 CHj 1.5820</td>
<td> 4-bromophenyl 4-bromophenyl 4-phenylphenyl 4-phenylphenyl</td><td> CHj 1.6305 CHj m.p. 44-53®</td>
4-methoxyphenyl 4-methoxyphenyl CH^ rff 1.5947 3-tri fluoromethylphenyl 3-trlfluoromethylphenyl CH^
2-chlorophenyl 2-chlorophenyl CH^ η^θ 1.5999
2-methaxyphenyl 2-methoxyphenylch_
2.4- dichlorophenyl 2,4-dichlorophenyl CH* n<sup>22</sup> 1.6019
3.5- dlchlorophenyl 3,5-dlchlorophenylCH*
2-chlorophenyl 4-chlorophenyl ־ ch<sub>3</sub> ng° 1.6044 2-chlorophenyl 4-fluorophenylCH
4-phenylphenyl 4-chlorophenylCH*
4-phenylphenyl 4-fluorophenyl CH* N<sup>22</sup> 1.6181
4-phenylphenyl 2,4-di chlorophenyl CH-j
4-fluorophenyl 2,4-dichlorophenylCH*
4-chlorophenyl 2,4-dichlorophenylCH*
1-naphthyl 2,6-dinethoxy phenylCH^
4-phenoxyphenyl 3,4-di chlorophenylCH
Table XIV (continued)
<td> ב</td><td></td><td> ל</td>
<td> 1-nephthyl</td><td> 2^/9</td><td></td>
<td> 4-phenylphenyl</td><td> CjHj</td><td> CjHj</td>
<td> 4-phenylphenyl</td><td></td><td></td>
<td> 4-phenylphenyl</td><td> 13^־פ</td><td> 2V15</td>
<td> 4-chlorophenyl</td><td></td><td></td>
<td> 4-fluorophenyl</td><td> fr'A</td><td></td>
<td> 4-(4-chlarophenoxy)phenyl</td><td></td><td></td>
<td> 4-t-butylphenyl</td><td> 57^4^9</td><td> 1-ε<sub>Λ</sub></td>
<td> 3-methoxyphenyl</td><td> <Α</td><td> 1-¾</td>
<td> 3-trifluoromethylphenyl</td><td></td><td> 8-04^</td>
<td> 2-thiomethylphenyl</td><td></td><td> 3-eethylbutyl</td>
<td> 2,4-dichlorophenyl</td><td></td><td> 2־<sup>ε</sup>Λ</td>
<td> 2,6-dimethyIpheny1</td><td> ΚΛ</td><td> t-C<sub>4</sub>H9</td>
<td> 3-methy 1-4-chlorophenyl</td><td></td><td> 2S*<sub>4</sub>^9</td>
<td> 2-®ethy1-5-fluorophenyl</td><td></td><td> -«6</td>
<td></td><td> 4-chlorophenyl</td><td> 4-chlorophenyl</td>
<td></td><td> 4-chlorophenyl</td><td> 4-chlorophenyl</td>
<td> 1-naphthyl</td><td> 4-fluorophenyl</td><td> 4-fluorophenyl</td>
<td> cyclopropyl</td><td> phenyl</td><td> 4-t-butylphenyl</td>
<td></td><td> phenyl</td><td> 4-phenylphenyl</td>
66114/3'
Table XIV (continued)
<td> ׳</td><td> A</td><td></td><td> «3</td>
<td></td><td> Ι1-ε<sub>Λ</sub></td><td> phenyl</td><td> 2,4-dichloropheny1</td>
<td> 1 λ ן</td><td></td><td> phenyl</td><td> 3-trif luoromethy Ipheny 1</td>
<td></td><td> JA״?</td><td> phenyl</td><td> 3,5-dichlorophenyl</td>
<td></td><td> • cyclopentyl</td><td> phenyl</td><td> 2,6-dimethoxyphenyl</td>
<td></td><td> B־<sup>c</sup>14<sup>H</sup>29</td><td> 4-chlorophenyl</td><td> 2-fluorophenyl</td>
<td></td><td> n-C<sub>4</sub>K<sub>9</sub></td><td> 4-fluorophenyl</td><td> 4-phenylphenyl</td>
<td></td><td> 4-chlorophenyl</td><td> 4-chlorophenyl</td><td> 4-chlorophenyl</td>
<td></td><td> 4-fluorophenyl</td><td> 4-fluorophenyl</td><td> 4-fluorophenyl</td>
<td></td><td> 4-phenyIphenyl</td><td> 4-phenylphenyl</td><td> 4-phenylphenyl m.p. 85-88</td>
<td></td><td> 2,4-dichlorophenyl</td><td> 2,4-dichlorophenyl</td><td> 2,4-dichlorophenyl</td>
<td></td><td> phenyl</td><td> 4-fluorophenyl</td><td> 4-fluorophenyl</td>
<td></td><td> phenyl</td><td> 4-chlorophenyl</td><td> 4-chlorophenyl</td>
<td></td><td> phenyl</td><td> 4-phenylphenyl</td><td> 4-phenylphenyl</td>
<td></td><td> phenyl</td><td> 2,4-dichlorophenyl</td><td> 2,4-dichlorophenyl</td>
<td></td><td> 2-naphthyl</td><td> 4-methylthiophenyl</td><td> 4-methylthiophenyl</td>
<td></td><td> 4-chlorophenyl</td><td> 2-methoxyphenyl</td><td> 2-methoxyphenyl</td>
<td></td><td> 4-chlorophenyl</td><td> 3-chlorophenyl</td><td> 3-chlorophenyl</td>
<td></td><td> phenyl</td><td> 2-chlorophenyl</td><td> 4-fluorophenyl</td>
<td></td><td> phenyl</td><td> 4-chlorophenyl</td><td> 4-phenylphenyl</td>
<td></td><td> 1-naphthyl</td><td> 4-bromophenyl</td><td> 3-methyIphenyl</td>
<td></td><td> 4-phenoxyphenyl</td><td> 3,5-dimethyIphenyl</td><td> 3,4-dichlorophenyl</td>
־ 89 Example 40
Preparation of (l,l’-Biphenyl-4-yl)dimethyl(2-methyliH-imidazol-l-ylmethyDsilane
The title compound is prepared by applying the procedure of Example 36 to (l,l'-biphenyl-4-yl)chloromethyldimethylsilane and the sodium salt of 4-methylimidazole.
« 41 Example $7 Preparation of the 1:1 complex of (l,l'-Biphenyl-4-yl)dimethyl(lH-imidazol-l-ylmethyl)silane and Cuprous Chloride...................
A mixture of 0.50 g (0.0017 mol) of (l,l’-biphenyl-4-yl)dimethyl(lH-imidazol-l-ylmethyl)silane and 0.22 g (0.0017 mol) of cuprous chloride in 15 ml of tetrahydrofuran was refluxed under N<sub>2</sub> for 15 minutes, and the resulting deep green solution was evaporated to leave the title complex as a dark green solid: m.p. 72-80° (decomp.); ir (Nujol<sup>R</sup>) 1590, 1515, 1250, 1110, 840, 820, 750, 695, 650 cm<sup>1</sup>־.
By applying the procedure of Example 24, .any of the compounds of Tables XIV, XV, XVI, XVII, XVIII or XIX can be converted to metal complexes or salts.
Example #7 Preparation of (l,l-'Biphenyl-4-yl)(IH-imidazol-
1-y!methyl)(methoxy)methylsilane
A mixture of (l,l'-biphenyl-4-yl)chloro(chloromethyDmethylsilane and two equivalents of imidazole sodium salt in dimethylformamide is warmed to 80-90°C for 2 hours. Ten equivalents of methanol is then added, and the mixture is held at 70° for 1 hour, cooled, diluted with water, and quickly extracted with ether. Washing the ether solution with water and brine, drying over magnesium sulfate, and evaporation leaves the title compound.
Related compounds can be made in the same way, using the appropriate chlorosilane and alcohol; for R, = OH, water is used instead of an alcohol, and □ hydrolysis is conducted at 20-25° instead of 70°.
־
Example 43
Preparation of l,l-(Dimethylethoxy)(lH-imldazol-l-ylmethyl)methyl(phenyl)silane______. _______
A mixture of 3.6 0 (0.015 mol) of chloromethyl(l,l-dlmethylethoxy)methyl(phenyl)silane and 1.3 g (0.015 mol) of imidazole sodium salt in 10 ml of dimethylformamid,e was stirred at 50° for 3 hours, allowed to stand at room temperature for 72 hours, poured into water, and extracted with ether. The ether extracts were washed three times with water and once with brine, dried over magnesium sulfate, and evaporated to leave 3.8 g of an oil. Impurities were removed by Kugelrohr distillation at 90° (airbath)/ 0.05 mm to leave 2.9 g (71%) of the title compound as a pale yellow oil: ηθ° 1.5291; ir (neat) 3105, 3070, 3045, 2970, 1590, 1500, 1425, 1360, 1250, 1235, 1185, 1110, 1055, 1020, 900, 805, 740, 700, 660 cm<sup>1</sup>; nmr (CDClj): 0.6 (3H, s), 1.3 (9H, s), 3.6 (2H, s), 6.8 (1H, s), 7.0 (1H, s) and 7.3-7.7 (6H, m).
Example 44
Preparation of [bis(4-chlorophenyl)]hydroxy(lHimidazol-l-yltnethyl)sllane
A mixture of 5.5 g (15.3 mmol) of chloromethyl[bis(4-chlorophenyl)](2-propoxy)silane and 1.5 g (17 mmol) of imidazole sodium salt in dimethyl formamide was warmed to 80 to 90° for 2 hours, cooled, diluted with ethyl acetate, washed three times with water and once with brine, dried over magnesium sulfate, and evaporated to leave a viscous oil. Trituration with ether gave 1.0 g (19%) of the title compound as a colorless solid: m.p. 131-133°; nmr (CDjSDCDj) 4.1 (2H, s), 6.8 (1H, s), 6.9 (1H, s), 7.4 (4H, d), 7.6 (5H, d).
The compounds of Tables XVI and XVII can be made using the procedures of Examples 42 and 43.
Table XVI
R
<img file="IL66114A_D0028.tif" />
<td> .1</td><td> .2</td><td> %</td>
<td><sup>C</sup>/5</td><td></td><td> CH,</td>
<td> «Λ</td><td> CH,</td><td> i־<sup>c</sup>A</td>
<td> *c<sub>4</sub>h,</td><td> CH,</td><td> %</td>
<td> 25״12^פ</td><td><sup>ε</sup>Λ</td><td> a,</td>
<td> 7ל*18^פ</td><td> ^13</td><td> “j</td>
<td> cyclopropyl</td><td> »3</td><td> 2־<sup>ε</sup>Λ</td>
<td> cyclohexyl</td><td><sup>01</sup>3</td><td> CH,</td>
<td> 1-naphthyl</td><td> ל9־1</td><td></td>
<td> phenyl</td><td> CH,</td><td> H</td>
<td> phenyl</td><td> CH,</td><td> CH,</td>
<td> phenyl</td><td> CH,</td><td><sup>C</sup>2*5 ,-</td>
<td> Phenyl</td><td> CH,</td><td> °ί׳ 7^־1</td>
<td> phenyl</td><td></td><td> H</td>
<td> 4-phenylphenyl</td><td> 2־C<sub>4</sub><sup>h</sup><sub>s</sub></td><td> CH,</td>
<td> 4-phenylphenyl</td><td> «Λ</td><td> H</td>
<td> 4-phenylphenyl</td><td> CH,</td><td><sup>0</sup>Λ</td>
<td> 4-phenylphenyl</td><td> CH,</td><td> ׳rtA</td>
<td> 4-chlorophenyl</td><td> 2-c<sub>4</sub>h<sub>9</sub></td><td></td>
<td> 4-chlorophenyl</td><td><sup>W</sup>3</td><td> ' °<sup>4</sup>3</td>
<td> 4-chlorophenyl</td><td> CH,</td><td> CjH,</td>
<td> 4-fluorophenyl</td><td></td><td> 7״3^פ</td>
<td> 4-fluorophenyl</td><td> “3</td><td></td>
<td> 4-t-butylphenyl</td><td></td><td></td>
<td> 3-trifluoromethylphenyl</td><td></td><td> H</td>
1.5352
Table XVI (continued)
<td> !i</td><td></td><td> צ</td>
<td> 2,4-dichlorophenyl</td><td></td><td> %</td>
<td> 2,4-dichlorophenyl</td><td> »J</td><td><sup>C</sup>2<sup>H</sup>5</td>
<td> 2,4-dichlorophenyl</td><td> CHj</td><td> ίτ'Λ</td>
<td> 2,4-dichlarophenyl ז</td><td></td><td> V5'</td>
<td> 2-<nethyl-5-fluorophenyl</td><td></td><td></td>
<td> 2,6-dimethoxyphenyl</td><td> 1,1-dimethylpropyl</td><td> Η</td>
<td> 3-methyl-4-chlorophenyl</td><td></td><td> %</td>
<td> 3,5-dichlorophenyl</td><td></td><td></td>
<td> ^12^5-</td><td> 2,4-dichlorophenyl</td><td> t-CjM,</td>
<td></td><td> phenyl</td><td></td>
<td> 1-naphthyl</td><td> phenyl</td><td><sup>C</sup>A</td>
<td> phenyl</td><td> phenyl</td><td></td>
<td> 4-fluorophenyl</td><td> phenyl</td><td> *3</td>
<td> 4-chlorophenyl</td><td> phenyl</td><td></td>
<td> 4-phenylphenyl</td><td> phenyl</td><td> %</td>
<td> 4-phenylphenyl</td><td> phenyl</td><td></td>
<td> 4-t-butylphenyl</td><td> phenyl</td><td> i־<sup>C</sup>4<sup>H</sup>9</td>
<td> 3-fluorophenyl</td><td> phenyl</td><td> C2H<sub>5</sub></td>
<td> 2-methoxyphenyl</td><td> phenyl</td><td> H</td>
<td> 2-chlorophenyl</td><td> phenyl</td><td> CHj</td>
<td> 2,4-dichlorophenyl</td><td> phenyl</td><td></td>
<td> 3,5-dichlorophenyl</td><td> phenyl</td><td></td>
<td> 4-fluorophenyl</td><td> 4-fluorophenyl</td><td> «Λ</td>
<td> 4-fluorophenyl</td><td> 4-fluorophenyl</td><td></td>
<td> 4-chlorophenyl</td><td> 4-chlorophenyl</td><td><sup>W</sup>3</td>
<td> 4-chlorophenyl</td><td> 4-chlorophenyl</td><td></td>
<td> 4-phenylphenyl</td><td> 4-phenylphenyl</td><td> CK<sub>3</sub></td>
<td> 2,4-dichlorophenyl</td><td> 2,4-dichlorophenyl</td><td></td>
<td> 3-trifluoromethylphenyl</td><td> 3-trifluoromethylphenyl</td><td></td>
<td> 2-methoxyphenyl</td><td> 2-methoxyphenyl</td><td> Η</td>
<td> 2-chlorophenyl</td><td> 4-fluorophenyl</td><td> Η</td>
Μ
Table XVI׳(continued)
R<
3- trifluoromethylphenyl
2-fluoro-4-chlorophenyl
2.3- dimethyIphenyl
2,6-dimethoxyphenyl
3.4- dichlorophenyl
4- fluorophenyl
4-t-butylphenyl 4-bromophenyl 4-methylthiophenyl 4-methoxyphenyl 4-methylphenyl
4-fluorophenyl n־C<sub>4</sub>H<sub>9</sub>
1-c<sub>3</sub>h<sub>7</sub> (¾
H
1־<sup>ε</sup>Λ
H m.p. 114-116°
66114/ 4'
Table XVII <sup>r</sup>2 Αγ<sup>2</sup>
6״ X <sup>R</sup>1 <sup>R</sup>2 % ί2 phenyl CHj t-C^ CHj
4-fluorophenyl CH^ CH^
66114/2 :
Example 44a
Preparation of (lH-Imldazol-l-ylmethyl)phenylbls(2- | propoxy)8ilane
The title compound can be made by applying the procedure of Example 26 to chloromethyl(phenyl)bls(2-propoxy)silane: n^<sup>2</sup> 1.4971; nmr (CDClj) 1.2 (12H, d, 2) 5.6 ,(6 » נH, s), 4.2 (2H, septet, J 6 ״), 6.8-7.6 (8H, m).
The compounds of Table XVIII can be made similarly.
־ 97 ־
Table XVIII ?% z<<sup>2</sup>
R.-Si-CH<sub>O</sub>N J. 1 ן * \ -ς’’
OR, 0
<td> 2!</td><td> %</td><td></td>
<td><sup>C</sup>2<sup>H</sup>5</td><td></td><td> H</td>
<td> H-C<sub>4</sub>H<sub>9</sub></td><td> C<sub>2</sub><sup>H</sup>j</td><td> H</td>
<td> £־<sup>C</sup>18<sup>H</sup>3.7_</td><td> CH,</td><td> H</td>
<td> cyclohexyl</td><td> n-CjH<sub>7</sub></td><td> H</td>
<td> 1-naphthyl</td><td> i-c?,</td><td> H</td>
<td> phenyl</td><td></td><td> H</td>
<td> 4-phenylphenyl</td><td> c<sub>2</sub>h<sub>5</sub></td><td> H</td>
<td> 4-fluorophenyl</td><td> c<sub>2</sub>h<sub>5</sub></td><td> H</td>
<td> 4-chlorophenyl</td><td> C<sub>2</sub><sup>h</sup><sub>5</sub></td><td> H</td>
<td> 4-chlorophenyl</td><td> 1־<sup>C</sup>3<sup>H</sup>7</td><td> H</td>
<td> 2,3-dimethylphenyl</td><td> 1-c<sub>4</sub>h,</td><td> H</td>
<td> 2,4-dichlorophenyl</td><td> CH,</td><td> H</td>
<td> 2,4-dichlorophenyl</td><td> c<sub>2</sub>h<sub>5</sub></td><td> H</td>
<td> 2-methoxy-5-fluorophenyl</td><td> 1־<sup>C</sup><sub>5</sub><sup>H</sup>7</td><td> H</td>
<td> 2,6-dimethoxyphenyl</td><td> CH,</td><td> H</td>
<td> 3,4-dichlorophenyl</td><td> c<sub>2</sub>h<sub>5</sub></td><td> H</td>
<td> 3,5-dichlorophenyl</td><td> £^4^9</td><td> H</td>
Ϊ04 Formulations
Useful formulations of the compounds within the scope of this invention can be prepared in conventional ways. They include dusts, granules, pellets, solutions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of these may be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from a few pints to several hundred gallons per acre. High strength compositions are primarily used as intermediates for further formulations. The formulations, broadly, contain about 1% to 99% by weight of active ingredient(s) and at least one of a) about 0.1% to 20% surfactant(s) and b) about 5% to 99% solid or liquid inert diluent(s). More specifically, they will contain these ingredients in the following approximate proportions:
Percent by Weight Active
Ingredient Diluent(s) Surfactant(s)
<td> Wettable Powders</td><td> 20-90</td><td> 0-74</td><td> 1-10</td>
<td colspan="2"> Oil Suspensions, 5-50 Emulsions, Solutions, (including Emulsifiable Concentrates)</td><td> 40-95</td><td> 0-15</td>
<td> Aqueous Suspensions</td><td> 10-50</td><td> 40-84</td><td> 1-20</td>
<td> Dusts</td><td> 1-25</td><td> 70-99</td><td> 0-5</td>
<td> Granules and Pellets</td><td> 1-95</td><td> 5-99</td><td> 0-15</td>
<td> High Strength Compositions</td><td> 90-99</td><td> 0-10</td><td> 0-2</td>
<td> Lower or higher</td><td> levels of</td><td> active</td><td> ingredient c</td>
<td> of course, be present</td><td> depending</td><td> on the</td><td> intended use</td>
and the physical properties of the compound. Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing.
ΪΜ
Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey. The more absorptive diluents are preferred for the wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0°C. McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood, New Jersey, as well as Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publishing Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth, etc.
The methods of making such compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, U.S. Patent 3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J. E. Browning, Agglomeration, Chemical Engineering, December 4, 1967, pg. 147ff. and Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pp. 8-59ff.
W 45
Example
Wettable Powder (l,l-Biphenyl-4-yl)dimethyl(lH-l,2,4-triazol-l-ylmethyDsilane 40% dioctyl sodium sulfosuccinate 1.5% sodium ligninsulfonate 3% low viscosity methyl cellulose 1.5% attapulgite 54%
The ingredients are thoroughly blended, passed through an air mill, to produce an average particle size under 15 microns, reblended, and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) before packaging.
All compounds of the invention may be formulated in the same manner. <sub>46</sub>
Example
Wettable Powder (4-Bromophenyl)dimethyl(1H-1,2,4-triazol-l-ylmethyl)silane 20% sodium alkylnaphthalenesulfonate 2% low viscosity methyl cellulose 2% diatomaceous earth 76%
The ingredients are blended, coarsely hammermilled and then air milled to produce particles of active essentially all below 10 microns in diameter. The product is reblended before packaging. Example High Strength Concentrate (4-Chlorophenyl)dimethyl(lH-l,2,4-triazol-l-ylmethyDsilane 98.5% silica aerogel , 0.5% synthetic amorphous fine silica 1.0%
The ingredients are blended and ground in a hammer-mill to produce a high strength concentrate essentially all passing a U.S.S. No. 50 sieve (0.3 mm openings). This material may then be formulated in a variety of ways.
W 48
Example
Dust high strength concentrate from
Example «825.4% ׳ pyrophyllite, powdered 74.6%
The ingredients are thoroughly blended and packaged for use. <sub>4g</sub>
Example
Aqueous Suspension (1,I’-Bipheny1-4-yl)dimethyl(1H-1,2,4-triazol-l-ylmethyl)silane 50.0% polyacrylic acid thickener 0.3% dodecylphenyl polyethylene glycol ether 0.5% disodium phosphate 1.0% monosodium phosphate 0.5% polyvinyl alcohol 1.0% pentachlorophenyl 0.4% water 46.3%
The ingredients are ground together in a sand mill to produce particles substantially all under five microns in size.
Example
Emulsifiable Concentrate
Dimethyl(phenyl)(1H-1,2,4-triazol-l-ylmethyl)silane 20% chlorobenzene 74% sorbitan monostearate and polyoxyethylene condensates thereof 6%
The ingredients are combined and stirred to produce a solution which can be emulsified in water for application.
102 100 51 Example Emulsifiable Concentrate
Dimethy1(4-methylphenyl)(1H-1,2,4-triazol-l-ylmethyl) silane 30% blend of oil soluble sulfonates and polyoxyethylene ethers 4% xylene 66%
The ingredients are combined and stirred with gentle warming to speed solution. A fine screen filter is included in packaging operation to insure the absence of any extraneous undissolved material in the product. <sub>52</sub>
Example 5/3/
Granule <sub>45</sub> wettable powder of example A6 15% gypsum 69% potassium sulfate 16%
The ingredients are blended in a rotating mixer and water sprayed on to accomplish granulation. When most of the material has reached the desired range of 1.0 to 0.42'mm. (U.S.S. # 18 to 40 sieves), the granules are removed, dried, and screened. Oversize material is crushed to produce additional material in the desired range. These granules contain active ingredient. 53
Example
Emulsifiable Concentrate (2,4-Dichlorophenyl)dimethyl(lH-l,2,4-triazol-l-ylmethyDsilane 30% blend of oil soluble sulfonates and polyoxyethylene ethers 4% xylene 66%
The ingredients are combined and stirred with gentle warming to speed solution. A fine screen filter is included in packaging operation to insure the absence of any extraneous undissolved material in the product.
wz <sub>54</sub>
Example
Emulsifiable Concentrate
Butyl(4-chlorophenyl)methyl(lH-l,2,4-triazol-l-yl(nethyl)silane 30% blend of oil soluble sulfonates and polyoxyethylene ethers 4% xylene 66%
The ingredients are combined and stirred with gentle warming to speed solution. A fine screen filter is included in packaging operation to insure the absence of any extraneous undissolved material in the product. <sub>55</sub>
Example
Emulsifiable Concentrate bis(4-Chlorophenyl)methyl(lH-l,2,4-triazol-l-ylmethyl)silane 30% blend of oil soluble sulfonates and polyoxyethylene ethers 4% xylene 66%
The ingredients are combined and stirred with gentle warming to speed solution. A fine screen filter is included in packaging operation to insure the absence of any extraneous undissolved material in the product.
Example
Emulsifiable Concentrate bis(4-Fluorophenyl)methyl(1H-1,2,4-triazol-l-ylmethyl)silane 20% chlorobenzene 74% sorbitan monostearate and polyoxyethylene condensates thereof 6%
The ingredients are combined and stirred to produce a solution which can be emulsified in water for application.
104 Π0 <sub>57 </sub>Example Emulsifiable Concentrate
4-Fluorophenyl(methyl)phenyl(1H-1,2,4-triazol-l-yl- methyDsilane 30% blend of oil soluble sulfonates and polyoxyethylene ethers 4% xylene 66%
The ingredients are combined and stirred with gentle warming to speed solution. A fine screen filter is included in packaging operation to insure the absence of any extraneous undissolved material in the product. <sub>58</sub>
Example
Wettable Powder (1,l'-Bipheny1-4-yl)dimethyl(IH-imidazol-l-y!methyl)silane 50% sodium alkylnaphthalenesulfonate 2% low viscosity methyl cellulose 2% diatomaceous earth 46%
The ingredients are blended, coarsely hammermilled and then air milled to produce particles of active essentially all below 10 microns in diameter.
The product is reblended before packaging.
Example 00
Wettable Powder (1,1-Bipheny1-4-yl)dimethyl(lH-imidazol-l-y!methyl)silane 40% dioctyl sodium sulfosuccinate 1.5% sodium ligninsulfonate 3% low viscosity methyl cellulose 1.5% attapulgite 54%
The ingredients are thoroughly blended, passed through an air mill, to produce an average particle size under 15 microns, reblended, and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) before packaging.
All compounds of the invention may be formulated in the same manner.
I <sup>m</sup> 60 Example Emulsifiable Concentrate (1,1'-Biphenyl-4-yl)dimethyl(IH-imidazo1-1-y!methyl)silane 30% blend of oil soluble sulfonates and polyoxyethylene ethers 4% xylene 66%
The ingredients are combined and stirred with gentle warming to speed solution. A fine screen filter is included in packaging operation to insure the absence of any extraneous undissolved material in the product. <sub>gl</sub>
Example
Emulsifiable Concentrate (1,1.-Bipheny1-4-yl)dimethyl(IH-imidazol-l-ylmethyl)silane 20% chlorobenzene 74% sorbitan monostearate and polyoxyethylene condensates thereof , 6%
The ingredients are combined and stirred to produce a solution which can be emulsified in water for application.
v 4
Example
Aqueous Suspension (1,1'-Bipheny1-4-yl)dimethyl(IH-imidazo1-1-ylmethyl)silane 25% hydrated attapulgite 3% crude calcium ligninsulfonate 10% sodium dihydrogen phosphate/ 0.5% water 61.5%
The ingredients are ground together in a ball or roller mill until the solid particles have been reduced to diameters under 10 microns.
m 63
Example
High Strength Concentrate (l,l’-Biphenyl-4-yl)dimethyl(lH-imidazol-l-y!methyl)silane 98.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0%
The ingredients are blended and ground in a hammer-mill to produce a high strength concentrate essentially all passing a U.S.S. No. 50 sieve (0.3 mm openings). This material may then be formulated in a variety of ways.
Example 00
Granule 5g wettable powder of example 00 15% gypsum 69% potassium sulfate 16%
The ingredients are blended in a rotating mixer and water sprayed on to accomplish granulation. When most of the material has reached the desired range of 1.0 to 0.42 mm. (U.S.S. #18 to 40 sieves), the gran ules are removed, dried, and screened. Oversize material is crushed to produce additional material in the desired range. These granules contain active ingredient.
Example
Dust high strength concentrate from
Example 64 25.4% pyrophyllite, powdered 74.6%
The ingredients are thoroughly blended and packaged for use.
107 W 66 Example
Emulsifiable Concentrate
4-Chlorophenyl(methyl)phenyl(lH-imidazol-l-ylmethyDsilane 20% chlorobenzene 74% sorbitan monostearate and polyoxyethylene condensates thereof 6%
The ingredients are combined and stirred to produce a solution which can be emulsified in water for application.
108 1W
Utility
The compounds of this invention are useful as plant disease control agents. They are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental, vegetable, field, cereal and fruit crops, such as, Puccinia recondita, Erysiphe cichoracearum, Erysiphe graminis, Venturia inaequalis, Helminthosporium maydis, Cercospora arachidicola, Uromyces phaseoli and Monilinia fructicola, Rhizoctonia solani, Pyricularia oryzae, Phytophthora infestans and other Phytophthora species. They also control seed pathogens such as Pythium aphanadermatum.
Disease control is ordinarily accomplished by applying an effective amount of the compound either pre- or post-infection to the portion of the plant to be protected, such as the roots, stems, foliage, fruit, seeds, tubers or bulbs, or to the media (soil or sand) in which the plants to be protected are growing. The compound may also be applied to the seed from which the plants to be protected are to be grown.
Rates of application for these compounds can be influenced by many factors of the environment and should be determined under actual use conditions. Foliage can normally be protected when treated at a rate of from less than 1 to 500 ppm of active ingredient. Plants growing in soil treated at a concentration from 0.1 to about 20 kg/ha can be protected from disease. Seed and seedlings can normally be protected when seed is treated at a rate of from 0.06 to about 3 grams per kilogram of seed.
W
The compounds of this invention can be mixed with fungicides, bactericides, acaricides, nematicides, insecticides, or other biologically active compounds in order to achieve desired results with a minimum expenditure of time, effort and material. Amounts of these biologically active materials added for each part by weight of the composition of this invention may vary from 0.05 to 25 parts by weight. Suitable agents of this type are well-known to those skilled in the art. Some are listed below: Fungicides: methyl 2-benzimidazolecarbamate (carbendazim) tetramethylthiuram disulfide (thiuram) n-dodecylguanidine acetate (dodine) manganese ethylenebisdithiocarbamate (maneb)
1,4-dichlor0-2,5-dimethoxybenzene (chloroneb) methyl 1-( butylcarbamoyl)-2-benzimidazolecarbamate (benomyl)
2-cyano-N-ethyIcarbarney1-2-methoxyiminoacetamide (cymoxanil)
N-trichloromethy1thiotetrahydrophthalimide (captan) N-trichloromethylthiophthalimide (folpet) dimethyl 4,4'-(o-phenylene)bis(3-thioallophanate) Cthiophanate-methyl)
2- (thiazol-4-yl)benzimidazole (thiabendazole) aluminum tris(O-ethyl phosphonate) (Aliette) tetrachloroisophthalonitrile (chlorothalonil)
2,6-dichloro-4-nitroaniline (dichloran)
N-(2,6-dimethylphenyl)-N-(methoxyacetyl)alanine methyl ester (metalaxyl) cis-N-[(l,1,2,2-tetrachloroethyl)thio]cyclohex-4-ene-
1,2-dicarbioximide (captafol)
3- (3,5-dichlorophenyl)-N-(l-methylethyl)-2,4-dioxo-limidazolidine carboxamide (iprodione)
3-(3,5-dichlorophenyl)-5-ethenyl-5-methyl-2,4-oxazolidinedione (vinclozolin) kasugamycin
CI-ethyl-S,S-diphenylphosphorodithioate (edifenphos)
Bactericides:
tribasic copper sulfate streptomycin sulfate oxytetracycline
Acaricides senecioic acid, ester with 2-sec-butyl-4,6-dinitrophenol (binapacryl)
6-methyl-l,3-dithiolo[2,3-B]quinonolin-2-one (oxythioquinox)
2,2,2-trichloro-l,1-bis(4-chlorophenyl)ethanol (dicofol) bis(pentachloro-2,4-cyclopentadien-l-yl) (dienochlor) tricyclohexyltin hydroxide (cyhexatin) hexakis(2-methyl-2-phenylpropyl)distannoxane (fenbutin oxide)
Nematicides:
2- [diethoxyphosphinylimino]-1,3-dithietane (fosthietan)
S-methy1-1-(dimethylcarbamoyl)-N-(methylcarbamoyloxy)thioformimidate (oxamyl)
S-methyl-l-carbamoyl-N-(methylcarbamoyloxy)thioformimidate
N-isopropylphosphoramidic acid, 0-ethyl-0'-[4-(methylthio)-m-tolyl]diester (fenamiphos)
Insecticides:
3- hydroxy-N-methylcrotonamide(dimethylphosphate)ester (monocrotophos) methylcarbamic acid, ester with 2,3-dihydro-2,2-dimethyl-7-benzofuranol (carbofuran)
0-[2,4,5-trichloro-a-(chloromethyl)benzyl]phosphoric acid, 0',O'-dimethyl ester (tetrachlorvinphos)
2-mercaptosuccinic acid, diethyl ester, S-ester with thionophosphoric acid, dimethyl ester (malathion) phosphorothioic acid, 0,0-dimethyl, 0-£-nitrophenyl ester (methyl parathion) methylcarbamic acid, ester with a-naphthol (carbaryl) methyl N-[[(methylamina)carbonyl]oxy]ethanimidothioate (methomyl)
N'-(4-chloro-o-tolyl)-N,N-dimethyIformamidine (chlordimeform)
0,0-die thy 1-0-( 2-isopropy l-4-methyl-6-p yr imidyDphosphorothioate (diazinon) octachlorocamphene (toxaphene)
O-ethyl O-£-nitrophenyl phenylphosphonothioate (EPN) cyano(3-phenoxyphenyl)-methyl 4-chloro-a-(l-methylethyl)benzeneacetate (fenvalerate) (3-phenoxyphenyl)methyl (+)-cis,trans-3-(2,2-dichloroethenyl)-2,2-dimethyIcyclopropanecarboxylate (permethrin) dimethyl N,N*-[thiobis](N-methylimino)carbonyloxy]]bis[ethanimidothioate] (thiodicarb) phosphorothiolothionic acid, 0-ethyl-0-[4-(methylthio)phenyl]-S-n-propyl ester (sulprofos) a-cyano-3-phenoxybenzyl 3-(2,2-dichlorovinyl)-2,2dimethylcyclopropane carboxylate (cypermethrin) cyano(3-phenoxyphenyl)methyl 4-(difluoromethoxy)-a(methylethyl)benzeneacetate (Payoff”)
0,0-diethyl-0-(3,5,6-trichloro-2-pyridyl)phosphorothioate (chlorpyrifos)
0,0-dimethyl-S-[(4-oxo-l,2,3-benzotriazin-3-(4H)-yl)methy!]phosphorodithioate (azinphos-methyl)
5,6-dimethyl-2-dimethylamino-4-pyrimidinyl dimethyl carbamate (Pirimor”)
S-(N-formyl-N-methylcarbamoylmethyl)-0,O-dimethyl phosphorodithioate (formothion)
S-2-(ethylthioethyl)-0,O-dimethyl phosphiorothioate (demeton-S-methyl) a-cyano-3-phenoxybenzyl cis-3-(2,2-dibromovinyl)-2,2dimethylcyclopropane carboxylate (deltamethrin) cyano(3-phenoxyphenyl)methyl ester of N-(2-chloro-4trifluoromethylphenyl)alanine (Mavrik)
112 /U0 This invention is further illustrated by the following examples.
Example 68
Compounds of this invention were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of the surfactant TREM 014 (polyhydric alcohol esters). These suspensions were sprayed to the point of run-off on wheat seedlings. The following day, the plants were inoculated with a spore suspension of Puccinia recondita var. tritici, causal agent of wheat leaf rust, and incubated in a saturated humidity chamber at 20° for 24 hours and then in a growth room for an additional 7 days, when .disease ratings were made. Percent disease control is shown in the following table. Treated plants had few or no rust pustules while the untreated plants had numerous rust pustules on each leaf.
Table 1
<td> Compound %</td><td> Control Wheat Rust</td>
<td> (Dimethyl)phenyl(1,2,4-triazo1-1ylmethyDsilane</td><td> 90</td>
<td> (4-Bromophenyl)dimethyl(1H-1,2,4triazol-l-y!methyl)silane</td><td> 80</td>
<td> (1,1'-Biphenyl-4-yl)dimethyl(lH- 1,2,4-triazol-l-y!methyl)silane</td><td> 100 .</td>
<td> (4-Chlorophenyl)dimethyl(lH-l,2,4triazol-l-yImethyl)silane</td><td> 100</td>
<td> Butyl(4-chlorophenyl)methyl(lH1,2,4-triazol-l-yImethyl)silane</td><td> 80</td>
<td> (3,4-Dichlorophenyl)dimethy1(1H- 1,2,4-triazol-l-yImethyl)silane</td><td> 60</td>
m
Table 1 (continued)
Compound % Control Wheat Rust (2,4-0ichlorophenyl)dimethyl(lH-
1,2,4-triazol-l-ylmethyl)silane90 bis(4-Chlorophenyl)(methyl)(1H-
1.2.4- triazol-l-ylmethyl)silane90
Dimethy1(4-fluorophenyl)(1H-1,2,4triazol-l-ylmethyl)silane100
[4-(l,l-Dimethylethyl)phenyl]dimethyl(lH-l,2,4-triazol-l-ylmethyDsilane80
Buty 1(2,4-dichlorophenyl )me thy K1H-
1.2.4- triazol-l-y!methyl)silane100 bis(2,4-0ichlorophenyl)(methyl)(1H-
1.2.4- triazol-l-ylmethyl)silane100 (2,4-Dichlorophenyl)methyl(phenyl)(1H-1,2,4-triazol-l-y!methyl)silane100 (4-Chlorophenyl)methyl(phenyl)(1H-
1.2.4- triazol-l-y!methyl)silane100 (4-Fluorophenyl)methyl(phenyl)(1H-
1.2.4- triazol-l-ylmethyl)silane90
Dodecyl(dimethyl)(lH-l,2,4-triazol- l-ylmethyl)silane100
[4-(4-Chlorophenoxy)phenyl]dimethyl(1H-1,2,4-triazol-l-y!methyl)silane90 (3,5-Dichlorophenyl)dimethyl(lH-
1,2,4-triazol-l-ylmethyl)silane80 (1,1'-Bipheny1-4-yl)buty!(methyl)(1H-1,2,4-triazol-l-ylmethyl)silane90 bis(1,1'-Bipheny1-4-yl)(methyl)(1H-
1,2,4-triazol-l-ylmethyl)silane80 (1,1.-Bipheny1-4-yl)methyl(phenyl)(1H-1,2,4-triazol-l-ylmethyl)silane100 (1,1 ’-Bipheny 1-3-y 1) dime thy K1H-1,2,4triazol-1-ylmethyl)silane m
Table 1 (continued)
Compound ׳ % Control Wheat Rust
2-Chlorophenyl(methyl)phenyl(lH-l,2,4triazol-l-ylmethyl)silane80 (bis(2-Chlorophenyl)]methyl(1H-1,2,4triazol-l-ylmethyl)silane100 (1,1'-Biphenyl-4-yl)dimethyl(1H-1,2,4triazol-l-ylmethyl)silane, 4-dodecylbenzenesulfonic acid salt100 (1,1'-Biphenyl-4-yl)dimethyl(lH-l,2,4triazol-l-ylmethyl)silane, 1:1 complex with zinc (II) chloride100 (1,1' -Bipheny 1-4-yl )dime thy K1H-1,2,4triazol-l-ylmethyl)silane, 1:1 complex with manganous sulfate90
2-Chlorophenyl(4-chlorophenyl)methyl(1H-1,2,4-triazol-l-ylmethyl)silane100
[bis(2-Fluorophenyl)]methyl(1H-
1,2,4-triazol-l-ylmethyl)silane, 1:1 complex with cuprous chloride90
[bis(2-Fluorophenyl)]methyl(lH-
1,2,4-triazol-l-ylmethyl)silane,
2:1 complex with cupric chloride100 (1,1'-Bipheny1-4-yl)dimethyl(1Himidazol-l-ylmethyl)silane100 (4-Chlorophenyl)(lH-imidazol-lylmethyl)dimethylsilane50
Butyl(4-chlorophenyl)(IH-imidazol- l-ylmethyl)methylsilane90 (IH-Imidazol-l-y!methyl)dimethyl(4-phenoxyphenyl)silane60
Dimethyl(lH-imidazol-l-y!methyl)(4-methoxyphenyl)silane60 (2,4-Dichlorophenyl)dimethyl(1Himidazol-l-ylmethyl)silane90 m
Table 1 (continued)
Compound % Control Wheat Rust bis(4-Fluorophenyl)(IH-imidazol-lylmethyDmethylsilane100
Dimethyl(4-fluorophenyl)(IH-imidazol-l-ylmethyl)silane80
Dimethyl(IH-imidazol-l-y!methyl)(4-trifluoromethylphenyl)silane100
Butyl(2,4-dichlorophenyl)(IH-imidazol-l-y ImethyDmethylsilane100 bis(2,4-Dichlorophenyl)(IH-imidazol!-ylmethyDmethylsilane100
2,4-Dichlorophenyl(IH-imidazol-lylmethyl)methyl(phenyl)silane90
4-Chlorophenyl(lH-imidazol-l-ylmethyl)methyl(phenyl)silane100
Dodecyl(dimethyl)(IH-imidazol-lylmethyDsilane80
[4-(4-Chlorophenoxy)phenyl]dimethyl(IH-imidazol-l-y!methyl)silane90
Butyl(IH-imidazol-l-y!methyl)methyl(phenyl)silane90 (1,1'-Bipheny1-4-yl)butyl(lH-imidazol-l-ylmethyl)methylsilane100 (1,1'-Biphenyl-4-yl)(IH-imidazol-
1-ylmethyl)methyl(phenyl)silane100 (1,1'-Biphenyl-3-yl)dimethyl(lHimidazol-l-y ImethyDsilane90 (4-Bromophenyl)(IH-imidazol-1-ylmethyl)methyl(phenyl)silane90 (1,1'-Bipheny1-4-yl)dimethyl(1Himidazol-l-ylmethyl)silane, 1:1 complex with cuprous chloride100 (2-Chlorophenyl)(4-chlorophenyl)(1Himidazol-1-ylmethyl)methylsilane100 m
Table 1 (continued)
Compound % Control Wheat Rust (2-Chlorophenyl)(dimethyl)(IH-imidazol-l-ylmethyl)silane80 tris(4-F)uorophenyl)(lH-imidazo)-<sup>f</sup> l־-y)methy) )si 1 ane80 bis(4-F)uoropheny))hydroxy(lH-imidazol- l-y)methy)) s i)ane100 bis(4-Ch)oropheny)) hydroxy(1H-imidazo)- l-y)methy))si)ane80 (3-Ch)oropheny) )dimethyl (IH-im-idazo)- l-y)methy))si lane80 (1,1<sup>1</sup>-Bi phenyl-4-y)) (4-f)uoropheny))(IH-imidazo)-l-y)methyl)methy)si)ane80
Dimethyl(lH-imidazo)-l-y)methy))(4trif)uoromethoxyphenyl)si)ane100 (4 '-Bromo-1,1'-bipheny)-4-y))dimethyl(lH-imidazo)-l-y)methy))$i)ane100
TABLE 1 (continued)
Compound % Control Wheat Rust bis(4-Chlorophenyl)hydroxy(lH-l,2,4friazol-l-ylmethyl)silane90 . bis(4-Fluoropheny1) hydroxy(1H-l,2,4triazdl-l-ylmethyl)silane90 ,־ tris(4-Chlorophenyl)(1H-l,2,4-tri azol1-ylmethyl)si 1ane40 tris(4-Fluorophenyl)(1H-1,2,4-triazol־ 1-ylmethyl)silane90 bis(4-Chlorophenyl)hydroxy(4H-l,2,4triazol-4-ylmethyl)si lane90 (1-1'-Bi phenyl-4-yl)methyl(2-propoxy) (lH-l,2,4-triazol-l-yImethyl)silane100 (1,1'-Biphenyl-4-yl)hydroxy(methyl)(1H-1,2,4-triazol-l-ylmethyl)silane90 (1,1'-Biphenyl-4-yl)(4-fluorophenyl)methyl(lH-l,2,4-tr ו azol-1-ylmethyl)silane100
Dimethyl(4-trifluoromethoxyphenyl)(1H-l,2,4-triaz01-1-ylmethyl)silane100 (4 '-Bromo-1,1'-biphenyl-4-yl)dimethyl(1H-l,2,4-triazol-l-y1methyl)silane100 (1,1 '-Bi phenyl-4-yl)dimethyl(5-methyllH-l,2,4-triazol-l-yImethyl)silane100 (1,1'-Bi phenyl-4-yl)dimethyl(1H-l,2,4triazol-l־ylmethyl)silane, 1:1 complex with cupric chloride100 (1,1 <sup>,</sup>-Biphenyl-4-yl)dimethyl(1H-1,2,4triazol-l-ylmethyl)silane, 2:1 complex with cupric chloride100
A Compound applied at a concentration of 200 ppm.
118 68 ׳׳«
Example
Compounds of this invention were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of the surfactant TREM 014 (polyhydric alcohol esters). These suspensions were sprayed to the point of run-off on cucumber seedlings. The following day, the plants were inoculated with a spore suspension of the fungus Erysiphe cichoracearum, causal agent of cucumber powdery mildew, and incubated in a growth room for 7 days. Disease ratings were then made. Percent disease control is shown in the following table. Treated plants had little or no powdery mildew in contrast to untreated plants which were covered with powdery mildew. Phytotoxicity in the form of growth reduction or hormonal effects was observed on some of the plants in association with disease control.
Table 2 % Control Cucumber Compound Powdery Mildew (Dimethyl)phenyl(l,2,4-triazol-lylmethyl)silane100
Ethyldimethyl(lH-l,2,4-triazol-lylmethyl)silane100
Butyldimethyl(lH-l,2,4-triazol-lylmethyDsilane100
Dimethyl(4-methyIphenyl)(1H-1,2,4triazol-l-y!methyl)silane100G (4-Bromopheny !)dime thy K1H-1,2,4triazol-l-ylmethyl)silane100G
HA
Table 2 (continued) % Control Cucumber
Compound Powdery Mildew (1,1'-Biphenyl-4-yl)dimethyl(1H-
1.2.4- triazol-l-y!methyl)silane100 (4-Chlorophenyl)dimethyl(lH-l,2,4triazol-l-ylmethyl)silane100
Butyl(4-chlorophenyl)methyl(lH-
1.2.4- triazol-l-ylmethyl)silane100G
Dimethyl(l-naphthalenyl)(1H-1,2,4triazol-l-ylmethyl)silane100 (3,4-Dichlorophenyl)dimethyl(lH-
1.2.4- triazol-l-ylmethyl)silane100
Dimethyl(4-phenoxyphenyl)(1H-1,2,4triazol-l-ylmethyl)silane70
Dimethyl(4-methoxyphenyl)(1H-1,2,4triazol-l-ylmethyl)silane100 (2,4-Dichlorophenyl)dimethyl(1H-
1.2.4- triazol-l-ylmethyl)silane100H bis(4-Chlorophenyl)(methyl)(1H-
1.2.4- triazol-l-ylmethyl)silane100 (1H-1,2,4-Triazol-l-ylmethyl)triphenylsilane100
Methyldiphenyl(IK-1,2,4-triazo1-1ylmethyDsilane100G (1,1'-Biphenyl-4-yl)dimethyl(4H-
1.2.4- triazol-4-y!methyl)silane90 bis(4-Fluorophenyl)(methyl)(1H-
1.2.4- triazol-l-ylmethyl)silane100G
Dimethyl(4-fluorophenyl)(1H-1,2,4triazol-l-y ImethyDsilane100G
Dimethyl(4-methylthiophenyl)(1H-
1.2.4- triazol-l-y ImethyDsilane100
Table2 (continued)
<td></td><td colspan="2"> % Control Cucumber Compound Powdery Mildew</td>
<td> 5</td><td> Dimethyl(lH-l,2,4-triazol-l-yl- methyl)(4-trifluoromethylphenyl)silane</td><td> 1OOG</td>
<td></td><td> Dimethyl(lH-l,2,4-triazol-l-ylmethyl)(3-trifluQromethylphenyl)silane</td><td> 100</td>
<td> 10</td><td> Dimethyl(lH-l,2,4-triazol-l-ylmethyl)(2-trifluoromethylphenyl)silane</td><td> 100</td>
<td></td><td> (2-Methoxyphenyl)dimethyl(lH-l,2,4triazol-l-ylmethyl)silane</td><td> 100G</td>
<td> 15</td><td> Buty 1 (2,4-di chlorophenyl )methylQH1,2,4-triazol-l-y!methyl)silane</td><td> 100G</td>
<td></td><td> bis(2,4-Dichlorophenyl)(methyl)(1H1,2,4-triazol-l-ylmethyl)silane</td><td> 100G</td>
<td> 20</td><td> (2,4-Dichlorophenyl)methyl(phenyl)(1H-1,2,4-triazol-l-ylmethyl)si lane</td><td> 100G</td>
<td></td><td> (4-Chlorophenyl)methyl(phenyl)(1H1,2,4-triazol-l-y!methyl)silane</td><td> 100G</td>
<td></td><td> (4-Fluorophenyl)methyl(phenyl)(1H1,2,4-triazol-l-ylmethyl)silane</td><td> 100</td>
<td> 25</td><td> Butyl(methyl)phenyl(1H-1,2,4-triazoll-ylmethyl)silane</td><td> 100</td>
<td></td><td> (2,3-Dimethoxyphenyl)dimethy1(1H1,2,4-triazol-l-ylmethyl)silane</td><td> 100G</td>
<td> 30</td><td> (2,6-Dimethoxyphenyl)dimethyl(1H1,2,4-triazol-l-ylmethyl)silane</td><td> 100G</td>
<td></td><td> Dodecyl(dimethyl)(1H-1,2,4-triazoll-ylmethyl)silane</td><td> 60<sup>c</sup></td>
<td></td><td> (2-Chlorophenyl)dimethyl(lH-l,2,4triazol-l-ylmethyl)silane</td><td> 100G</td>
<td> 35</td><td> [4-(4-Chlorophenoxy)phenyl]dimethyl- (1H-1,2,4-triazol-l-ylmethyl)silane</td><td> 80</td>
m
Table.2 (continued) % Control Cucumber
Compound Powdery Mildew (1,1' -Bipheny1-4-yl)butyl(methyl)(1H-1,2,4-triazol-l-y!methyl)silane100
Butyl(4-fluorophenyl)methyl(lH-l,2,4'triazol-l-ylmethyDsilane100 bis(1,1<sup>,</sup>-Bipheny1-4-yl)(methyl)(1H-
1,2,4-trlazol-l-y!methyl)silane100 (1,1'-Bipheny1-4-yl)methyl(phenyl)(1H-1,2,4-triazol-l-y!methyl)silane100 (1,!-Dimethylethoxy)methyl(phenyl)(1H-1,2,4-triazol-l-ylmethyDsilane100
Methyl(phenyl)(2-propoxy)(1H-1,2,4triazol-l-ylmethyDsilane100 (1,1'-Bipheny1-2-yl)dimethyl(lH-l,2,4triazol-l-ylmethyDsilane90
2-Chlorophenyl(methyl)phenyl(lH-l,2,4triazol-l-ylmethyl)silane100
4-Bromophenyl(methyl)phenyl(lH-l,2,4triazol-l-ylmethyDsilane100
[bis(2-Chlorophenyl)]methyl(lH-l,2,4triazol-l-ylmethyDsilane100
Cyclohexyl(dimethyl)(1H-1,2,4-triazol- l-ylmethyl)silane100G
[bis(4-Bromophenyl)]methyl(lH-l,2,4triazol-l-ylmethyDsilane80G (l,l<sup>,</sup>-Biphenyl-4-yl)dimethyl(lH-l,2,4triazol-l-yImethy1)silane, 4-dodecylbenzenesulfonic acid salt100 (1,1' -Bipheny l-4-yl)dimethy K1H-1,2,4triazol-l-ylmethyDsilane, 1:1 complex with cuprous chloride100 (1,1' -Biphenyl-4-yl)dimethyl(lH-l,2,4triazol-l-ylmethyDsilane, 1:1 complex with zinc (II) chloride80
Table 2 (continued) % Control Cucumber
Compound Powdery Mildew (l,l'-Blphenyl-4-yl)dimethyl(!H-l,2,4triazol-l-ylmethyl)silane, 1:1 complex with manganous sulfate90
2-Chlorophenyl(4-chlorophenyl)methyl(1H-1,2,4-triazol-l-ylmethyl)silane100
Phenyl[bis(2-propoxy)](1H-1,2,4triazol-l-ylmethyl)silane100
[bis(2-Fluorophenyl)]methyl(lH1,2,4-triazol-l-ylmethyl)silane, 1:1 complex with cuprous chloride 100
[bis(2-Fluorophenyl)]methylClH1,2,4-triazol-l-ylmethyl)silane, 2:1 complex with cupric chloride 100 (IH-Imidazol-l-ylmethyl)dimethyl(4-methylphenyl)silane 100G<sup>A</sup> (4-Bromophenyl)(IH-imidazol-l-ylmethyDdimethylsilane100 (1,1’-Biphenyl-4-yl)dimethyl(lHimidazol-l-ylmethyl)silane100 (4-Chloropheny1)(IH-imidazol-lylmethyDdimethylsilane!00
Butyl(4-chlorophenyl)(IH-imidazoll-ylmethyl)methylsilane100G (IH-Imidazol-l-ylmethyl)dimethyl(l-naphthalenyl)silane100
Table 2 (continued) % Control Cucumber Compound Powdery Mildew (3,4-Dichlorophenyl)(lH-imidazoll-ylmethyl)dimethylsilane100 *
(IH-Imidazol-l-y!methyl)dimethyl(4-phenoxyphenyl)silane100
Dimethyl(IH-imidazol-l-y!methyl)(4-methoxyphenyl)silane100 (2,4-Dichlorophenyl)dimethyl(lHimidazol-l-ylmethyl)silaneΙΟΟΗθ bis(4-Chlorophenyl)(IH-imidazol-lylmethyDmethylsilane100 bis(4-Fluorophenyl)(IH-imidazol-lylmethyDmethylsilane!00
Dimethyl(4-fluorophenyl)(IH-imidazol-l-ylmethyl)silane100G
Dimethyl(lH-imidazol-l-ylmethyl)(4-methylthiophenyl)silane100
Dimethyl(IH-imidazol-l-ylmethyl)(4-trifluoromethylphenyl)silane100
Dimethyl(IH-imidazol-l-y!methyl)(3-trifluoromethylphenyl)silane80
[4-(1,1-Dimethylethyl)phenyl](1Himidazol-l-ylmethyl)dimethylsilane80 (IH-Imidazol-l-ylmethyl)dimethyl(2-trifluoromethylphenyl)silane100G
Butyl(2,4-dichlorophenyl)(IH-imidazol-l-y ImethyDmethylsilane100G “66114/2
124 Table 2 (continued)
X Control Cucumber
Compound Powdery Mildew bis(2,4-Dichlorophenyl)(IH-imidazoll-ylmethyl)methylsilane100 (2,4-Dichlorophenyl)(lH-imidazol-lylmethyl)methyl(phenyl)silane100 (4-Chlorophenyl)(IH-imidazol-l-ylmethyl)methyl(phenyl)silane100 (4-Fluorophenyl)(IH-imidazol-l-ylmethyl)methyl(phenyl)silane100 (IH-Imidazol-l-yImethyl)(2-methoxyphenyDdimethylsilane100G (2,3-Dimethoxyphenyl)(IH-imidazoll-ylmethyl)dimethylsilane100 (2-Chlorophenyl)(IH-imidazol-l-ylmethyl)dimethylsilane
[4-(4-Chlorophenoxy)phenyl]dimethyl(IH-imidazol-l-ylmethyl)silane100 (1,1'-Bipheny1-4-yl)butyl(lH-imidazol-l-ylmethyl)methylsilane100
Butyl(4-fluorpphenyl)(IH-imidazoll-ylmethyl)methylsilane100 (1,1 <sup>,</sup>-Biphenyl-4-yl)(IH-imidazoll-ylmethyl)methyl(phenyl)silane100 (l,l-Dimethylethoxy)(lH-imidazol-lylmethyl)methyl(phenyl)silane100
66114/ 3
Table 2 (continued) % Control Cucumber (lH-Imidazol-1-y!methyl)methyl(phenyl)(2-propoxy)silane90 (IH-Imidazol-l-y!methyl)[bis(4methoxyphenyl)]methylsilane50 (1,1'-Biphenyl-2-yl )dlmethyKlHimidazol-l-ylmethyl)silane50 (2-Chlorophenyl)(lH-imidazol-l-ylmethyl)methyl(phenyl)silane100 (4-Bromophenyl)(IH-imidazol-l-ylmethyl)methyl(phenyl)silane100
[bis(2-Chlorophenyl)](lH-lmidazoll-ylmethyl)methylsilane100
[bis(A-Bromophenyl)](IH-imidazol-lylmethyl)methylsilane100 (1,1<sup>,</sup>-Bipheny1-4-yl)dimethyl(1Himidazol-l-ylmethyl)silane, 1:1 complex with cuprous chloride100 (2-Chlorophenyl)(4-chlorophenyl)(1Himidazol-l-y!methyl)methylsilane100 (2-Chlorophenyl)(dimethyl)(IH-imidazol-l-y ImethyDsilane80
W
TABLE 2 (Continued)
Compound tris(4-Ch)oropheny))(lH-imidazo)-
I-y)methy))silane tris(4-F)uoropheny))(lH-imidazo)-
1-y)methyl)silane bis(4-F)uoropheny))hydroxy(lH-imidazo)- l-y)methy))si)ane bis(4-Ch)oropheny))hydroxy(lH-imidazo)-
1-ylmethy))si lane (3-Ch)oropheny))dimethyl(IH-imida20)-
1-ylmethyl)si)ane (1,I'-Bipheny)-4-y1)(4-f)uoropheny))(1H-imidazo)-1-y)methyl)methy)si)ane
Dimethyl(IH-imidazol-l-ylmethy))(4trifluoromethoxypheny) )silane (4'-Bromo-1 ,l'-bipheny)-4-y) )dimethy).(IH-imidazol-l-ylmethy))si)ane (3,5-Dich)oropheny))dimethyl(1Hו mid azo)-1-y)methy))si)ane % Control Cucumber
Powdery Mildew
100
100G
100G
7»
TABLE 2 (continued)
Compound _ b i s(4-Chlorophenyl)hydroxy (1H-1,2,4tri azo1-1-y)methyl)si1ane bis(4-Fluorophenyl)hydroxy(lH-l,2,4triazol-l-y!methyl)silane trוs(4-Chlorophenyl)(1H-1,2,4-triazol-
1-ylmethyl)silane bis(4-Chlorophenyl)hydroxy(4H-l,2,4triazol-4-ylmethyljsilane
Oxybi s[bi s(4-f1uoropheny!)(1H-1,2,4tri az 01-1-ylmethyl)silane] (1-1'-Biphenyl-4-yl)methyl(2-propoxy) (lH-1,2,4-triazol-l-y!methyl.)si lane (1,1'-Biphenyl-4-yl)hydroxy(methyl)(lH-l,2,4-triazol-l-ylmethyl)silane (1,1<sup>,</sup>-Biphenyl-4-yl)(4-fluorophenyl)methyl(1H-1,2,4-triazo 1-1-yl methyl )silane
Dimethyl(4-trif 1uoromethoxyphenyl)(1H-I,2,4־triazol-l-y!methyl)silane (4 '-Brom.o-1,1 '-biphenyl-4-yl )dimethyl(1H-1,2,4-triazol-l-y!methyl)silane (1,1'-Biphenyl-4-yl)dimethyl(5-methyllH-l,2,4-triazol-l-ylmethyl)silane (1,1'-Biphenyl-4-yl)dimethyl(1H-1,2,4tri azol-1-ylmethyl)si1ane, 1:1 complex with cupric chloride.
(1,1 <sup>,</sup>-Biphenyl-4-yl)dimethyl (1H-1,2,4triazol-l-ylmethyl)si 1ane, 2:1 complex with cupric chloride (4-F1uoropheny!)methyl(2-propoxy)lH-
1,2,4-triazol-l-yImethy!)silane (l,l-Dimethyllethoxy)[bis(4-fluoro-phenyl)](lH-l,2,4-triazol-l-ylmethyl)silane
A_ = growth reduction; and
B - hormonal, effects.
H
Control Cucumber
Powdery Mildew
100H
100H
100G
128 <sup>m</sup> 69 Example 7,0
Compounds of this invention were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of the surfactant TREM 014 (polyhydric alcohol esters). These suspensions were sprayed to the point of run-off on barley seedlings. The following day, the plants were inoculated with a spore suspension of the fungus Erysiphe qraminis, causal agent of barley powdery mildew, and incubated in a growth room for 7 days. Disease ratings were then made. Percent disease control is shown in the following table. Treated plants had little or no powdery mildew in contrast to untreated plants which were covered with powdery mildew.
Table 3 % Control Barley
Compound .Powdery Mildew
Butyl(4-chlorophenyl)methyl(lH-
1,2,4-triazol-l-ylmethyl)silane90 (3,4-Dichlorophenyl)dimethyl(lH-
1,2,4-triazol-l-ylmethyl)silane100
Dimethyl(4-methoxyphenyl)(1H-1,2,4triazol-l-ylmethyl)silane100 (2,4-Dichlorophenyl)dimethyl(lH-
1.2.4- triazol-l-ylmethyl)silane100 bis(4-Chlorophenyl)(methyl)(IH-
1.2.4- triazol-l-ylmethyl)silane100 (lH-l,2,4-Triazol-l-ylmethyl)triphenylsilane100
Methyldiphenyl(1H-1,2,4-triazol-1ylmethyDsilane100
Dimethyl(lH-l,2,4-triazol-l-ylmethyl)(2-trifluoromethylphenyl)silane100
Table 3 (continued)
<td> Compound</td><td> X Control Barley Powdery Mildew</td>
<td> Dodecyl(dimethyl)(lH-l,2,4-triazoll-ylmethyl)silane</td><td> 100<sup>A</sup></td>
<td> Butyl(4-chlorophenyl)(IH-imidazol1-y!methyl)methylsilane</td><td> 100</td>
<td> (3,4-Dichlorophenyl)(IH-imidazol1-y!methyl)dimethylsilane</td><td> 80</td>
<td> Dimethyl(lH-imidazol-l-y!methyl)(4-methoxyphenyl)silane</td><td> 100</td>
<td> (2,4-Dichlorophenyl)dimethyl(lHimidazol-l-ylmethyl)silane</td><td> 100</td>
<td> bis(4-Chlorophenyl)(IH-imidazol-lylmethyDmethylsilane</td><td> 100</td>
<td> Dimethyl(IH-imidazol-l-y!methyl)(4-trifluoromethylphenyl)silane</td><td> 100</td>
<sup>A</sup> Compound applied at a concentration of 200 ppm.
130 m סל Example 77 Compounds of this invention were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of the surfactant TREM 014 (polyhydric alcohol esters). These suspensions were sprayed to the point of run-off on apple seedlings. The following day, the plants were inoculated with a spore suspension of the fungus Venturia inaequalis, causal agent of apple scab, and incubated in a saturated humidity chamber at 20° for 24 hours and then in a growth room for an additional 10-12 days. Disease ratings were then made and recorded as shown in the following table. Treated plants had fewer apple scab lesions when compared to untreated plants which were covered with scab lesions. Phytotoxicity expressed as growth reduction was observed on some of the plants in association with disease control.
Table 4
<td> Compound %</td><td> Control Apple Scab</td>
<td> Dimethyl(4-methylphenyl)(1H-1,2,4triazol-1-ylmethyl)silane</td><td> 50G<sup>a</sup></td>
<td> (4-Bromophenyl)dimethyl(1H-1,2,4triazol-1-ylmethyl)silane</td><td> 90G</td>
<td> (l,l'-Biphenyl-4-yl)dimethyl(lH- 1,2,4-triazol-l-yImethyl)silane</td><td> 100</td>
<td> (4-Chlorophenyl)dimethyl(lH-l,2,4triazol-l-ylmethyl)silane</td><td> 100</td>
<td> Butyl( 4-chlorophenyl )me thy K1H1,2,4-triazol-l-yImethyl)silane</td><td> 1000</td>
<td> Dimethyl(1-naphthalenyl)(1H-1,2,4triazol-l-ylmethyl)silane</td><td> 50</td>
/00
Table 4 % Control Apple Scab
Compound
<td> (3,4-Dichlorophenyl)dimethyl(1H- 1,2,4 <sup>כ</sup>-triazol-l-ylmethyl)silane</td><td> 80</td>
<td> Dimethyl(4-phenoxyphenyl)(1H-1,2,4triazol-l-ylmethyl)silane</td><td> 100</td>
<td> Dimethyl(4-methoxyphenyl)(1H-1,2,4triazol-l-ylmethyl)silane</td><td> 100</td>
<td> 10 (2,4-Dichlorophenyl)dimethyl(lH1,2,4-triazol-l-ylmethyl)silane</td><td> 100</td>
<td> bis(4-Chlorophenyl)(methyl)(1H1,2,4-triazol-l-ylmethyl)silane</td><td> 100</td>
<td> Methy!diphenyl(1H-1,2,4-triazol-1- <sup>15</sup> ylmethyDsilane</td><td> 100</td>
<td> (1,1'-Biphenyl-4-yl)dimethyl(4H1,2,4-triazol-4-ylmethyl)silane</td><td> 80</td>
<td> bis(4-Fluorophenyl)(methyl)(1H1,2,4-triazol-l-ylmethyl)silane</td><td> 100</td>
<td> 20 Dimethyl(4-fluorophenyl)(1H-1,2,4triazol-l-ylmethyl)silane</td><td> 80C<sup>b</sup></td>
<td> Dimethyl(4-methy1thiophenyl)(1H1,2,4-triazol-l-ylmethyl)silane</td><td> 60</td>
<td> _ Dimethyl(1H-1,2,4-triazol-l-ylmethyl)- <sup>25</sup> (2-trifluoromethylphenyl)silane</td><td> 65G<sup>A</sup>»<sup>C</sup></td>
<td> (2-Methoxyphenyl)dimethyl(lH-l,2,4triazol-l-ylmethyl)silane</td><td> 80</td>
<td> Buty1(2,4-dichlorophenyl)methy1(1H1,2,4-triazol-l-ylmethyl)silane</td><td> 100G</td>
<td> 30 bis(2,4-Dichlorophenyl)(methyl)(1H1,2,4-triazol-l-ylmethyl)silane</td><td> 100</td>
<td> (2,4-Dichiorophenyl)methyl(phenyl)(1H-1,2,4-triazol-l-ylmethyl)silane</td><td> 100G</td>
<td> (4-Chlorophenyl)methyl(phenyl)(1H- <sup>35</sup> 1,2,4-triazol-l-ylmethyl)silane</td><td> 100</td>
Table 4 (continued)
Compound % Control Apple Scab (4-Fluorophenyl)methyl(phenyl)(1H-
1,2,4-triazol-l-yImethyl)silane100
Butyl(methyl)phenyl(lH-l., 2,4-triazol- l-ylmethyl)silane80
Dodecyl(dimethyl)(lH-l,2,4-triazol- l-ylmethyl)silane 40B<sup>c</sup>»<sup>D</sup> (2-Chlorophenyl)dimethyl(lH-l,2,4triazol-l-ylmethyl)silane100
[4-(4-Chlorophenoxy)phenyl]dimethyl(1H-1,2,4-triazol-l-yImethyl)silane100 (1,1'-8iphenyl-4-yl)butyl(methyl)(lH-l,2,4-triazol-l-ylmethyl)silane80
Buty !(4-fluorophenyl )me thy K1H-1,2,4triazol-l-ylmethyl)silane100 (1,1<sup>,</sup>-Biphenyl-4-yl)methyl(phenyl)(1H-1,2,4-triazol-l-yImethyl)silane100 (l,l'-Biphenyl-2-yl)dimethyl(lH-l,2,4triazol-l-ylmethyl)silane60 (1,1'-Bipheny1-3-yl)dimethyl(1H-1,2,4triazol-l-ylmethyl)silane50
2-Chlorophenyl(methyl)phenyl(lH-l,2,4triazol-l-ylmethyDsilane90
4-Bromophenyl(methyl) phenyl(1H-1,2,4triazol-l-ylmethyl)silane100
[ b is (2-Chlor □phenyl) ]me thy K1H-1,2,4triazol-l-y ImethyDsilane40
[bis(4-Bromophenyl)]methyl(1H-1,2,4triazol-l-y ImethyDsilane80 (1,1' -Bipheny 1-4-yl )dimethyK1H-1,2,4triazol-l-yImethyDsilane, 4-dodecylbenzenesulfonic acid salt100 ־ 133 Table 4 (continued)
Compound X Control Apple Scab (l,l'-Biphenyl-4-yl)dimethyl(lH-l,2,4triazol-l-y ImethyDsilane, 1:1 complex with cuprous chloride!00 (l,D־Biphenyl-4-yl)dimethyl(lH-l,2.4triazol-l-ylmethyl)silane, 1:1 complex with zinc (II) chloride100 (l,l'-Biphenyl-4-yl)dimethyl(lH-l,2,4triazol-l-y ImethyDsilane, 1:1 complex with manganous sulfate100
2-Chlorophenyl(4-chlorophenyl)methyl(1H-1,2,4-triazol-l-y ImethyDsilane90
2-Chlorophenyl(dimethyl)(1H-1,2,4triazol-l-y ImethyDsilane¢0 (1,l’-Biphenyl-4-yl)dimethyl(1Himidazol-l-ylmethyl)silane00
Butyl(4-chiorophenyl)(lH-imidazol1-ylmethyDmethylsilane90 (IH-Imidazol-l-ylmethyl)dimethyl(l-naphthalenyl)silane40 (3,4-Dichlorophenyl)(IH-imidazol1-ylmethyDdimethylsilane30 (1H-Imidazol-1-ylmethy!)dimethyl(4-phenoxyphenyDsilane100 (2,4-Dichlorophenyl)dimethyl(lHimidazol-l-ylmethyDsilaneiqq bis(4-Fluorophenyl)(IH-imidazol-lylmethyDmethylsilane100
Dimethyl(IH-imidazo1-1-ylmethyl)(4-trifluoromethyIphenyl)silane6O
[4-(1,l-0imethylethyl)phenylJ(1Himidazol-l-y!methyl)dimethylsilane 50
Table 4 (continued)
Compound X Control Apple Scab
Butyl(2,4-dichlprophenyl)(lH-imidazpl-l-ylmethyl)methylsilane100B bis(2,4-Dichlorophenyl)(IH-imidazoll-ylmethyl)methylsllane40 (2,4-Dichlorophenyl)(IH-imidazol-lylmethyl)methyl(phenyl)silane80 (4-Chlorophenyl)(IH-imidazol-l-ylmethyl)methyl(phenyl)silane100 (4-Fluorophenyl)(IH-imidazol-l-ylmethyl)methyl(phenyl)silane100 (IH-Imidazol-l-ylmethyl)(2-methoxyphenyDdimethylsilane .60 (2-Chlorophenyl)(IH-imidazol-l-ylmethyDdimethylsilane90 (1,1'-Biphenyl-4-yl)butyl(lH-imidazol-l-ylmethyl)methylsilane100
Butyl(4-fluorophenyl)(IH-imidazoll-ylmethyl)methylsilane80 bis(1,1'-Bipheny1-4-yl)(IH-imidazol-l-ylmethyl)methylsilane50 (lH-Imidazol-l-ylmethyl)[bis(4methoxyphenyl)]methylsilane50 (1,1'-Bipheny1-2-yl)dimethy1(1Himidazol-l-ylmethyl)silane90 (1,1'-Bipheny1-3-yl)dimethyl(lHimidazol-l-ylmethyl)silane90 (2-Chlorophenyl)(IH-imidazol-l-ylmethyl)methyl(phenyl)silane 100
Table A (continued)
Compound X Control Apple Scab (4-Bromophenyl)(lH-imidazol-l-ylmethyl)methyl(phenyl)silane30
[bis(2-Chlorophenyl)](IH-imidazoll-ylmethyl)methylsilane60
Dimethyl(IH-imidazol-l-ylmethyl)(4-methylsulfonyIphenyl)silane80
[bis(4-Bromophenyl)](lH-imidazol-lylmethyDmethylsilane50 (1,1’-Biphenyl-A-yl)dimethyl(1Himidazol-l-ylmethyl)silane, 1:1 complex with cuprous chloride100 (2-Chlorophenyl)(4-chlorophenyl)(1Himidazol-l-y!methyl)methylsilane80 (IH-Imidazol-l-ylmethyl)phenyl[bis(2-propoxy)]silane70 (2-Chlorophenyl)(dimethyl)(IH-imidazol-l-ylmethyl)silane60 (3-Chlorophenyl)dimethyl(lH-imidazol1-ylmethyl)si 1ane 60 ׳ (1,1'-Biphenyl-4-yl )(4-fluorophenyl)(IH-imidaz01-1-yl methyl)methyl si lane50
Dimethyl(IH-imidazol-1-yl methyl)(4.tr if 1 uor ome th oxy phenyl )silane50 (4<sup>,</sup>-Bromo-1,1'-bipheny1-4-yl)dimethyl(IH-imidazol-1-ylmethyl)silane50 (3,5-Dichlorophenyl)dimethyl(1Himidazol-l-ylmethyl )silane 50
TABLE 4 (continued)
Compound % Control Apple Scab bis(4-Chlorophenyl)hydroxy(lH-l,2,4triazol-l-ylmethyl)silane100 bi s (^F1 uoropheny 1 )hydroxy(lH-l ,2,4־ triazol-l-ylmethyl)si 1ane100 tris(4-Fluorophenyl)(1H-1,2,4-triazol1-ylmethyl)si 1ane .60 bi$(4-Chlorophenyl)hydroxy(4H-1,2,4triazol-4-ylmethyl)si 1ane100 (l-l'-Biphenyl4־-yl)methyl(2-propoxy) (1H-1,2,4-triazol-l-ylmethyl)silane100 (1,1'-Biphenyl-4-yl)hydroxy(methyl)(1H-1,2,4-triazol-l-ylmethyl)silane100 (1,1<sup>,</sup>-Biphenyl-4-yl)(4-fluorophenyl)methyl(lH-l,2,4-triazol-l-ylmethyl)silane100
Dimethyl(4-trifluoromethoxyphenyl)(lH-l,2,4-triazol-l-ylmethyl)silane90 (4'-Bromo-1,1'-biphenyl-4-yl)dimethyl(1H-1,2,4-triazol-l-ylmethyl)silane100 (1,1'-Bi phenyl-4-yl)dimethyl(5-methyl1H-1,2,4-triazol-l-ylmethyl)silane100 (1,1'-Biphenyl-4-yl )dimethyl(1H-1,2,4triazol-l-ylmethyl)silane, 1:1 complex with cupric chloride100 (1 ,l'-Biphenyl-4-yl )dimethyl(1H-1,2,4triazol-l-ylmethyl)silane, 2:1 complex with cupric chloride100 (3-Chlorophenyl)dimethyl(1H-1,2,4triazol-l-ylmethyl)silane60
Dimethyl(octadecyl)(lH-l,2,4-triazol-l־ylmethyl)si 1ane60 <sup>a</sup>G = growth reduction.
<sup>B</sup>C = chlorosis.
^compound applied at a concentration of 400 ppm. <sup>d</sup>B ־ burn.
Example 77
Compounds of this invention were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of the surfactant TREM 014 (polyhydric alcohol esters). These suspensions were sprayed to the point of run-off on corn seedlings. The following day, the plants were inoculated with a spore suspension of Helminthosporium maydis, causal agent of southern corn leaf blight, and incubated in a saturated humidity chamber at 20° for 24 hours and then in a growth room for an additional 7 days, when disease ratings were made. Percent disease control is shown in the following table. Treated plants had few or no lesions while the untreated plants had numerous lesions on each leaf. Phytotoxicity expressed as growth reduction was observed on some of the plants in association with disease control.
Table 5
<td> % Compound _</td><td> Control of Southern Corn Leaf Blight</td>
<td> (4-Bromopheny!)dimethyl(1H-1,2,4triazol-l-ylmethyl)silane</td><td> 90</td>
<td> (1,1*-Biphenyl-4-yl)dimethyl(1H1,2,4-triazol-l-ylmethyl)silane</td><td> 90</td>
<td> (3,4-Dichlorophenyl)dimethyl(lH1,2,4-triazol-l-ylmethyl)silane</td><td> 90</td>
<td> Dimethyl(4-methoxyphenyl)(1H-1,2,4triazol-l-ylmethyl)silane</td><td> 90</td>
<td> (2,4-Dichloropheny!)dimethyl(1H1,2,4-triazol-1-ylmethyl)silane</td><td> 90</td>
<td> bis(4-Chloropheny1)(methyl)(1H1,2,4-triazol-l-yImethyl)silane</td><td> 80</td>
ΛΑΟ
Table 5 (continued)
Compound % Control of Southern Corn Leaf Blight
Methyldiphenyl(lH-l,2,4-triazol-lylmethyDsilane80 (1,1'-Biphenyl-4-yl)dimethyl(4H-
1.2.4- triazol-4-ylmethy!)silane100 bis(4-Fluorophenyl)(methyl)(1H-
1.2.4- triazol-l-ylmethyl)silane100
Dimethyl(4-fluoropheny1)(1H-1,2,4triazol-l-ylmethyl)silane90
Di methyl(4-methylthiophenyl)(1H-
1.2.4- triazol-l-ylmethyl)silane80
Di me thy K1H-1,2,4-triazol-l-ylmethyl)(4-trifluoromethylphenyl)silane50
[4-(1,1-Dimethylethyl)phenyl]dimethyl(lH-l,2,4-triazol-l-ylmethyDsilane60 (2-Methoxyphenyl)dimethyl(lH-l,2,4triazol-l-ylmethyl)silane70
Butyl(2,4-dichlorophenyl)methyl(lH-
1.2.4- triazol-l-ylmethyl)silane100 bis(2,4-Dichlor□phenyl)(methyl)(1H-
1.2.4- triazol-l-y ImethyDsilane80 (4-Chlorophenyl)methyl(phenyl)(1H-
1.2.4- triazol-l-ylmethyl)silane90 (4-Fluorophenyl)methyl(phenyl)(1H-
1,2,4-triazol-l-ylmethyl)silane90 (2-Chloropheny1)dimethyl(1H-1,2,4triazol-l-ylmethyl)silane100
[4-(4-Chlorophenoxy)phenyl]dimethyl(1H-1,2,4-triazol-l-y!methyl)silane50 (3,5-Dichlorophenyl)dimethyl(lH-
1,2,4-triazol-l-ylmethyl)silane40 m׳
Table 5 (continued) % Control of Southern
Compound Corn Leaf Blight
<td> 5</td><td> (1,1' -Biphenyl-4-״yl)butyl(methyl)- (1H-1,2,4-triazol-1-ylmethyl)silane</td><td> 50</td>
<td></td><td> (1,l'-Biphenyl-4-yl)methyl(phenyl)(1H-1,2,4-triazol-1-ylmethyl)silane</td><td> 90</td>
<td> 10</td><td> [bis(4-Methoxyphenyl)]methyl(lH-l,2,4triazol-l-ylmethyl)silane</td><td> 90</td>
<td></td><td> (1,1'-Biphenyl-2-yl)dimethyl(lH-l,2,4triazol-l-ylmethyl)silane</td><td> 90</td>
<td></td><td> (1,1 '-Biphenyl-3-y!)dimethyl(1H-1,2,4triazol-l-ylmethyl)silane</td><td> 100</td>
<td> 15</td><td> 2-Chlorophenyl(methyl)phenyl(lH-l,2,4- triazol-l-ylmethyl)silane</td><td> 100</td>
<td></td><td> 4-Bromophenyl(methyl)phenyl(lH-l,2,4triazol-l-ylmethyl)silane</td><td> 80</td>
<td> 20</td><td> [bis(2-Chlorophenyl)]methyl(lH-l,2,4triazol-l-ylmethyl)silane</td><td> 60</td>
<td></td><td> Cyclohexyl(dimethyl)(1H-1,2,4-triazol1-ylmethyl)silane</td><td> 50</td>
<td> 25</td><td> (1,1' -Biphenyl-4-yl)dimethyl(1H-1,2,4triazol-l-ylmethyl)silane, 4-dodecylbenzenesulfonic acid salt</td><td> 100</td>
<td></td><td> (1,1' -Biphenyl-4-yl )dime thy K1H-1,2,4triazol-l-ylmethyl)silane, 1:1 complex with cuprous chloride</td><td> 100</td>
<td> 30</td><td> (1,1'-Biphenyl-4-yl)dimethyl(1H-1,2,4triazol-l-ylmethyl)silane, 1:1 complex with zinc (II) chloride</td><td> 90</td>
<td></td><td> (1,1'-Biphenyl-4-yl)dimethyl(1H-1,2,4triazol-l-ylmethyl)silane, 1:1 complex with manganous sulfate</td><td> 100</td>
<td> 35</td><td> 2-Chlorophenyl(4-chlorophenyl)methyl(1H-1,2,4-triazol-1-ylmethyl)silane</td><td> 60</td>
Table 5 (continued) % Control of Southern Compound Corn Leaf Blight (1,!<sup>,</sup>-Biphenyl-4-y!)dimethyl(1Hlmidazol-l-ylmethyl)silane90
Butyl(4-chlorophenyl)(IH-imidazoll-ylmethyl)methyl5ilane50 (3,4-Dichlorophenyl)(IH-imidazoll-ylmethyl)dimethylsilane70 (2,4-Dichlorophenyl)dimethyl(lHimidazol-l-ylmethyDsilane70 bis(4-Chlorophenyl)(IH-imidazol-lylmethyDmethylsilane60 bis(4-Fluorophenyl)(IH-imidazol-lylmethyDmethylsilane60
[4-(1,1-Dimethylethyl)phenyl](1Himidazo 1-1-ylmethyDdimethylsilane70 (IH-Imidazol-l-ylmethyl)dimethyl(2-trifluoromethylphenyDsilane90
Butyl(2,4-dichlorophenyl)(IH-imidazol-l-ylmethyl)methylsilane80 bis(2,4-Dichlorophenyl)(IH-imidazol1-ylmethyDmsthylsilane80 (4-Fluorophenyl)(IH-imidazol-l-ylmethyl)methyl(phenyl)silane80 (2,6-Dimethoxyphenyl)(dimethyl)(1Himidazol-l-ylmethyDsilane50
Table 5 (continued) % Control of Southern
Compound Corn Leaf Blight (1,J'-Biphenyl-4-yl)(IH-imidazol1-ylmethyl)methyl(phenyl)silane80 (1,1’-Bipheny1-3-yl)dimethyl(1Himidazol-l-ylmethyl)sllane90
[bis(2-Chlorophenyl)]( IH-imidazoll-ylmethyl)methylsilane90 bis(4-Chlorophenyl)hydroxy(1H-1,2,4triazol-l-ylmethyl)silane90 . bis(4-Fluorophenyl )hydroxy(!H-l,2,4triazol-l-ylmethyl)silaneΙθθ bis(4-Chlorophenyl) hydroxy(4H-l,2,4triazol-4-ylmethyl)silane80 (1-1'-Biphenyl-4-yl)methyl(2-propoxy) (1H-l,2,4-tri azol-1-y!methyl)silane90 (1,1<sup>,</sup>-Bi phenyl-4-yl)(4-fluorophenyl)methyl(1H-l,2,4-triazol-l-ylmethyl)silane80
Dimethyl(4-trifluoromethoxyphenyl)(1H-l,2,4-tri azo1-1-yl methyl)silane80 (4<sup>1</sup>-Bromo-1,1<sup>,</sup>-biphenyl-4-yl)dimethyl(lH-l,2,4-triazol-l-ylmethyl)silane70 (1,1<sup>,</sup>-Bi phenyl-4-yl)dimethyl(5-methyl1H-l,2,4-triazol-l-ylmethyl)silane80 (1,1'-Bipheny1-4-yl )dimethyl(1H-1,2,4triazol-l-ylmethyl )silane, 1:1 complex with cupric chloride80 (l,l'-Biphenyl-4-yl)dimethyl(lH-l,2,4triazol-l-ylmethyl)silane, 2:1 complex with cupric chloride
Μ 72 Example 7?
Compounds of this invention were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of the surfactant TREM 014 (polyhydric alcohol esters). These suspensions were sprayed to the point of run-off on peanut seedlings. The following day, the plants were inoculated with a spore suspension of Cercospora arachidicola, causal agent of peanut early leafspot, and incubated in a saturated humidity chamber at 27° for 24 hours and then in a growth room for an additional 14 days, when disease ratings were made. The results are shown in the following table. Treated plants had few or no leafspots while the untreated plants had numerous leafspots. Phytotoxicity expressed as burn was observed in association with disease control for some treated plants.
Table 6 % Control Peanut Compound Early Leafspot bis(4-Chlorophenyl)(methyl)(1H-
1,2,4-triazol-l-ylmethyl)silane100
Methyldiphenyl(1H-1,2,4-triazol-1ylmethyl)silane100 (1,1<sup>,</sup>-Bipheny1-4-yl)dimethyl(1H-
1,2,4-triazol-l-ylmethyl)silane100 (4-Chlorophenyl)dimethyl(1H-1,2,4triazol-l-ylmethyl)silane90
Dimethyl(l-naphthalenyl)(1H-1,2,4triazol-l-ylmethyl)silane90 (2,4-Dichlorophenyl)dimethyl(lH-
1,2,4-triazol-l-ylmethyl)silane100 m
Table 6 (continued)
Compound % Control Peanut Early Leafspot bis(4-Fluorophenyl)(methyl)(1H-
1.2.4- triazol-l-yImethyl)silane100
Dimethyl(4-fluorophenyl)(1H-1,2,4triazol-l-ylmethyl)silane50
[4-(1,1-Dimethylethyl)phenyl]dime thy K1H-1,2,4-triazol-l-y 1methyDsilane35
Dimethyl(lH-l,2,4-triazol-l-y1methyl)(2-trifluoromethylphenyl)silane25
Butyl( 2,4-di chlorophenyl )methylQH-
1.2.4- triazol-l-y!methyl)silane100 bis(2,4-Dichlorophenyl)(methyl)(1H-
1.2.4- triazol-l-yImethyl)silane100 (2,4-Dichlorophenyl)methyl(phenyl)(1H-1,2,4-triazol-l-yImethyl) silane100 (4-Chlorophenyl)methyl(phenyl)(1H-
1,2,4-triazol-l-yImethyl)silane100 (4-Fluorophenyl)methyl(phenyl)(1H-
1,2,4-triazol-l-yImethyl)silane100 (2-Chlorophenyl)dimethy1(1H-1,2,4triazol-l-y !methyDsilane30 (1,1'-Biphenyl-4-yl)butyl(methyl)(lH-l,2,4-triazol-l-ylmethyl)silane100 bis(1,1<sup>,</sup>-Bipheny1-4-yl)(methyl)(1H-
1,2,4-triazol-l-yImethyl)silane80 (1,1'-Bipheny1-4-yl)methyl(phenyl)(lH-l,2,4-triazol-l-ylmethyl)silane100
[bis(4-Methoxyphenyl)]methyl(1H-1,2,4triazol-l-ylmethyl)silane30 (1,1<sup>1</sup>-Bipheny1-2-yl)dimethy1(1H-1,2,4triazol-l-y !methyDsilane100 m
Table 6 (continued) % Control Peanut
Compound Early ׳Leafspot (1,1'-Biphenyl-3-yl)dimethyl(lH-l,2,4triazol-l-ylmethyl)silane90
2-Chlorophenyl(methyl)phenyl(lH-l,2,4triazol-l-ylmethyl)silane100
4-Bromophenyl(methyl)phenyl(lH-l,2,4triazol-l-ylmethyl)silane100
[bis(2-Chlorophenyl)]methyl(1H-1,2,4triazol-l-ylmethyl)silane100
[bis(4-Bromophenyl)]methyl(lH-l,2,4triazol-l-ylmethyl)silane100 (1,1<sup>,</sup>-Biphenyl-4-yl)dimethyl(lH-l,2,4triazol-l-ylmethyl)silane, 4-dodecylbenzenesulfonic acid salt100 (1,1'-Bipheny1-4-yl) dimethyl(1H-1,2,4triazol-l-ylmethyDsilane, 1:1 complex with cuprous chloride100 (1,1*-Biphenyl-4-y!)dimethyl(1H-1,2,4triazol-l-ylmethyl)silane, 1:1 complex with zinc (II) chloride100 (1,1'-Bipheny1-4-yl)dimethy1(1H-1,2,4triazol-l-y ImethyDsilane, 1:1 complex with manganous sulfate100
2-Chlorophenyl(4-chlorophenyl)methyl- (1H-1,2,4-triazol-l-y ImethyDsilane 90
[bis(2-Fluorophenyl)]methyl(IH-
1.2.4- triazol-l-y ImethyDsilane,
1.:1 complex with cuprous chloride 10.0
[bis(2-Fluorophenyl)]methyl (IH-
1.2.4- triazol-l-ylmethyl)silane,
2:1 complex with cupric chloride 100 (1,l’-Biphenyl-4-yl)dimethyl(IHimidazbl-l-ylmethyDsilane 100
Ml
Table 6 (continued)
Compound % Control Peanut
Early Leafspot (2,4-D1 chlor opheny DdimethyHlHimidazol-l-ylmethyl)silane
Diphenyl(lH-imidazol-l-yImethyl)methylsilane bis(4-Fluoropheny1)(IH-imidazol-l<sup>10</sup> ylmethyDmethylsilane
Dimethyl(4-fluorophenyl)(IH-imidazol-l-yImethyl)silane
Dimethyl(lH-imidazol-l-yImethyl)(4-trifluoromethylphenyl)silane
Dimethyl(IH-imidazol-l-yImethyl)(3-trifluoromethylphenyl)silane
Butyl(2,4-dichlorophenyl)(IH-imidazol-l-ylmethyl)methylsilane .
bis(2,4-Dichlorophenyl)(IH-imidazol<sup>20</sup> !-ylmethyDmethylsilane (2,4-Dichloropheny1)(IH-imidazol-lyImethyl)methyl(phenyl)si lane (4-Chlorophenyl)(IH-imidazo1-1-ylmethy!)methyl(phenyl)silane (4-Fluorophenyl)(IH-imidazo1-1-ylmethy!)methyl(phenyl)silane (2-Chlorophenyl)(IH-imidazol-l-ylmethyl)dimethyl silane (1,1'-Biphenyl-4-yl)butyl(IH-imida׳<sup>51</sup>־ zol-l-ylmethyl)methylsilane bis(1,1'-Biphenyl-4-yl)(IH-imidazo1-1-ylmethy!)methylsilane (l,l'-8iphenyl-4-yl)(IH-imidazol-l-yImethyl)methyl(phenyl)35 silane
60B<sup>a</sup>
36B
Table 6 (continued) % Control Peanut
Compound
Early Leafspot (1,1'-Bipheny1-2-yl)dimethyl(1Himidazol-l-ylmethyl)silane (1,1'-Bipheny1-3-y!)dimethyl(1Himidazol-l-ylmethyl)silane (2-Chlor□phenyl)(IH-imidazol-l-y1methyl)methyl(phenyl)silane (4-Bromophenyl)(IH-imidazol-l-ylme'thyl)methyl (phenyl)silane
[bis(2-Chlorophenyl)](IH-imidazol- l-ylmethyl)methylsilane
[bis(4-Bromophenyl)](IH-imidazol-1ylmethyl)methylsilane (1,1'-Biphenyl-4-y!)dimethyl(1Himidazol-l-ylmethyl)silane, 1:1 complex with cuprous chloride (2-Chlorophenyl)(4-chlorophenyl)(1Himidazol-l-ylmethyl)methylsilane bis(4-F1uoropheny))hydroxy(IH-imidazol-
I-ylmethyl)si1ane bi s(4-Chlorophenyl) hydroxy(IH-imidazol-
1-ylmethyl)si 1ane (1,1'-Bipheny1-4-yl) (4-f1uorophenyl)(IH-imidazol-1-ylmethyl)methylsi lane
Dimethyl (IH-imidazol-1-ylmethyl)(4trifluoromethoxyphenyl ).silane (4'-Bromo-1,1<sup>1</sup>-bipheny1-4-yl)dimethyl(IH-imidazol-l-ylmethyl )silane
100 .
100'
Α<sub>β</sub> = Phytotoxic burn.
נץ
Compound applied at a concentration of 400 ppm.
W?
TABLE 6 (continued) % Control Peanut
Compound Early Leafspot bis(4-Chlorophenyl)hydroxy(lH-l,2,4t'riazol-1-y 1 methyl)si 1 ane100 bis(4-F1 uoropheny! )hydroxy(1H-1,2-,4triazol-l-ylmethyl)si1ane100 tris(4-Fluoropheny1)(1H-l,2,4-triazol-
1-ylmethyl)si 1ane90 bis(4-Chlorophenyl)hydroxy(4H-l,2,4triazol-4-ylmethyl)si 1ane100
Oxybis[bis(4-f!uoropheny1)(1H-1,2,4triazol-l-ylmethyl)si 1ane]93^ (l-l’-Biphenyl-4-yl)methyl(2-propoxy) (1H-1,2,4-trוazol-l-ylmethyl)si1ane100 (l,l'-Biphenyl-4-yl)hydroxy(methyl)(1H-1»2,4-tri,azol-1-ylmethyl )silane100 (1,1<sup>1</sup>-Biphenyl-4-yl)(4-fluorophenyl)methyl(lH-l,2,4-triazol-1-yl methyl)silane100
Dimethyl(4-trif 1uoromethoxyphenyl)(1H-l,2,4-triazol-l-ylmethyl)silane50 (4 ' - Bromo-1,1<sup>1</sup>-b i phenyl-4-y1)dimethyl(1H-1,2,4-tri azol-l-ylmethy1)s i1ane100 (1,1<sup>1</sup>-Bi phenyl-4-yl)dimethyl(5-methyl1H-1,2,4-triazol-l-ylmethyl)si 1ane100 (1,1'-Bi phenyl-4-yl)dimethyl (1H-1,2,4triazol-l-ylmethyl)si 1ane , 1:1 complex with cupric chloride100 (1,1<sup>1</sup>-Bi phenyl-4-yl)dimethyl(1H-1,2,4triazol-l-ylmethyl )silane, 2:1 complex with cupric chloride100 & Compound applied at a concentration of 20 ppm.
148 W 73 Example W Compounds of this invention were dissolved in acetone in an amount equal to 6% of the final volume* and then suspended at a concentration of 80 ppm in purified water containing 250 ppm of the surfactant TREM 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on bean seedlings. The following day, the plants were inoculated with a spore suspension of the fungus Uromyces phaseoli, causal agent of bean rust, and incubated in a saturated humidity chamber at 20° for 24 hours and then in a greenhouse for 7 days. Disease ratings were then made. Percent disease control is shown in the following table. Treated plants had few or no rust pustules in contrast to untreated plants which were covered with rust pustules. Phytotoxicity in the form of growth reduction was observed in association with disease control for some treated plants.
Table 7 % Control
<td> Compound</td><td> Bean Rust</td>
<td> (1,1' -Bipheny1-4-yl)dimethyl(1H1,2,4-triazol-l-ylmethyl)silane</td><td> 100</td>
<td> (2,4-Dichlorophenyl)dimethyl(lH- 1,2,4-triazol-l-ylmethyl)silane</td><td> 30G<sup>a</sup></td>
<td> bis(4-Chlorophenyl)(methyl)(1H1,2,4-triazol-l-y!methyl)silane</td><td> 100G</td>
<td> (4-Chlorophenyl)methyl(phenyl)(1H1,2,4-triazol-l-ylmethyl)silane</td><td> 98<sup>B</sup></td>
<td> (4-Fluorophenyl)methyl(phenyl)(1H1,2,4-triazol-l-ylmethyl)silane</td><td> 100<sup>B</sup></td>
<td> bis(4-Fluorophenyl)(methyl)(1H1,2,4-triazol-l-yImethy!)silane</td><td> 98<sup>b</sup></td>
<td> (1,1'-Bipheny1-4-yl)dimethy1(1Himidazol-l-y!methyl)silane</td><td> 100</td>
/#
Table 7 (continued) % Control
Compound Bean Rust (2,4-0ich!orophenyl) dimethyl(lHimidazol-l-ylmethyl)silane 83 <sup>a</sup>G = growth reduction.
<sup>0</sup>compound applied at a concentration of 16 ppm.
W 74 Example 73
Compounds of this invention were dissolved in acetone in an amount equal to 5% of the final volume and then suspended at a concentration of 100 ppm in purified water containing 700 ppm of the surfactant TREM 014 (polyhydric alcohol esters). Canned peach halves were dipped in this suspension for three minutes and then placed to air dry in sterile containers. Upon drying, the peach halves were inoculated with two pieces of Monilinia fructicola mycelium, causal agent of stone fruit brown rot, and incubated in the sterile containers for five days. At that time the radii of the colonies' growth were measured on each peach. Colonies on treated peaches did not grow or grew only a few milliliters in diameter while those growing on untreated peaches covered the entire surface of the peach. Percent disease contol (percent growth inhibition of colonies on treated peaches as compared to that of colonies on untreated peaches) is expressed in the table below.
Table 8 % Control
Compound Brown Rot (Dimethyl)phenyl(l,2,4-triazol-lylmethyl)silane89 (Butyl)dimethyl(lH-l,2,4-triazol-lylmethyl)silane95 (1,1'-Bipheny1-4-yl)dimethy1(1H-
1,2,4-triazol-l-ylmethyl)silane100
Butyl(4-chlorophenyl)methyl(lH-
1,2,4-triazol-l-ylmethyl)silane98
Dimethyl(4-methoxyphenyl)(1H-1,2,4triazol-l-ylmethyl)silane97
<img file="IL66114A_D0029.tif" />
Table 8 (continued)
X Control
Compound Brown Rot (2,4-Dichlorophenyl)dimethyl(1H-
1,2,4-triazol-l-ylmethyl)silane 100 bIs(4-Chlorophenyl)(methyl)(1H-
1.2.4- triazol-l-ylmethyl)silane95 (1,1 ’-Bipheny1-4-yl)dimethyl(4H-
1.2.4- triazol-4-y!methyl)silane96 bis(4-Fluorophenyl)(methyl)(1H-
1.2.4- triazol-l-ylmethyl)silane100
Butyl(2,4-dichlorophenyl)methyl(1H-
1.2.4- triazol-l-ylmethyl)silane98 (4-Chlorophenyl)methyl(phenyl)(lH-
1.2.4- triazol-l-ylmethyl)silane70 (4-Fluorophenyl)methyl(phenyl)(lH-
1,2,4-triazol-l-ylmethyl)silane90
Butyl(4-fluorophenyl)methyl(lH-l,2,4triazol-l-ylmethyl)silane!00
Dibutyl(methyl)(1H-1,2,4-triazol-lylmethyDsilane0!
(l,l'-Biphenyl-4-yl)dlmethyl(lHimidazol-l-ylmethyl)silane83
Butyl(A-chlorophenyl)(IH-imidazol!-ylmethyDmethylsilane45 (IH-Imidazol-l-ylmethyl)dimethyl(4-phenoxyphenyl)silane80 (2,4-Dichlorophenyl)dimethyl(lHlmidazol-l-ylmethyl)silane100 (4-Chlorophenyl)(IH-imidazol-l-y1methyl)methyl(phenyl)silane45 (4-Fluorophenyl)(IH-imidazol-l-ylmethyl)methyl(phenyl)silane65
W <sub>75 </sub>Example 7¢ Compounds of this invention were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of the surfactant TREM 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on rice seedlings. The following day, the plants were inoculated with a mixture of bran and the mycelium of Rhizoctonia solani, causal agent of sheath blight of rice, and incubated in a growth room for 7 days. Disease ratings were then made. Percent disease control is shown in the following table. Treated plants had little sheath blight in contrast to untreated plants which were covered with sheath blight.
Table 9 % Control of Compound Rice Sheath Blight (1,1'-Biphenyl-4-y!)dimethyl(1H-1,2,4-triazol-l-y!methyl)silane40 (3,4-0ichlorophenyl)dimethyl(lH-
1.2.4- triazol-1-y!methyl)silane80 bis(4-Fluorophenyl)(methyl)(1H-
1.2.4- triazol-l-y!methyl)silane80
[4-(1,1-Dimethylethy1)phenyl]dimethyl(1H-1,2,4-triazol-l-y1methyl)silane90 >
Butyl(2,4-dichlorophenyl)methyl(lH-
1.2.4- triazol-l-y!methyl)silane50 (4-Chlorophenyl)methyl(phenyl)(1H-
1.2.4- triazol-l-ylmethyDsilane90 (4-Fluorophenyl)methyl(phenyl)(1H-
1.2.4- triazol-l-y!methyl)silane80
Μ
Table 9 (continued) % Control of
Compound Rice Sheath Blight
<td> 5</td><td> Butyl(methyl)phenyl(lH-l,2,4-triazoll-ylmethyl)silane</td><td> 90</td>
<td></td><td> (1,1'-Bipheny1-4-yl)butyl(methyl)(1H-1,2,4-triazol-l-ylmethyl)silane</td><td> 80</td>
<td> 10</td><td> Butyl(4-fluorophenyl)methyl(lH-l,2,4triazol-l-ylmethyl)silane</td><td> 80</td>
<td></td><td> bis(1,1'-Bipheny1-4-yl)(methyl)(1H1,2,4-triazol-l-yImethyl)silane</td><td> 90</td>
<td> 15</td><td> [bls(4-Methoxyphenyl)]methyl(lH-l,2,4triazol-l-ylmethyl)silane 2-Chlorophenyl(methyl)phenyl(lH-l,2,4triazol-l-ylmethyl)silane</td><td> 80 90</td>
<td></td><td> 4-Bromophenyl(methyl)phenyl(lH-l,2,4triazol-l-ylmethyl)silane</td><td> 90</td>
<td> 20</td><td> [bis(2-Chlorophenyl)]methyl(lH-l,2,4triazol-l-ylmethyl)silane</td><td> 60</td>
<td></td><td> (1,1'-Biphenyl-4-y!)dimethyl(1H-1,2,4triazol-l-ylmethyl)silane, 1:1 complex with cuprous chloride</td><td> 90</td>
<td> 25</td><td> (1,1'-Bipheny1-4-yl)dimethy1(1H-1,2,4triazol-l-ylmethyl)silane, 1:1 complex with zinc (II) chloride</td><td> 90</td>
<td></td><td> 2-Chlor□phenyl(4-chlorophenyl)methyl(1H-1,2,4-triazol-l-yImethyl)silane</td><td> 70</td>
<td> 30</td><td> [bis(2-Fluorophenyl) ]methyHlH1,2,4-triazol-l-yImethyl)silane, 1:1 complex with cuprous chloride</td><td> 90</td>
<td></td><td> (1H-Imidazol-1-ylmethyl)dimethyl(4-phenoxyphenyl)silane</td><td> 70</td>
<td></td><td> bis(4-Fluor□phenyl)(IH-imidazol-lylmethyl)methyls!lane</td><td> 90</td>
Table 9 (continued) % Control of Compound Rice Sheath Blight (IH-Imidazol-l-ylmethyl)dimethyl(2-trifluoromethylphenyl)silane 80
Butyl(2,4-dichlorophenyl)(IH-imidazol-l-ylmethyl)methylsilane90 bis(2,4-Dichlorophenyl)(IH-imidazoll-ylmethyl)methylsilane80 (4-Fluorophenyl)(IH-imldazol-l-ylmethyl)methyl(phenyl)silane90 (IH-Imidazol-l-ylmethyl)(2-methoxyphenyDdimethylsilane90
[4-(4-Chlorophenoxy)phenyl]dimethyl(IH-imidazol-l-ylmethyl)silane70 (1,1’-Biphenyl-4-yl)butyl(lH-imidazol-l-ylmethyl)methylsilane90
Butyl(4-fluorophenyl)(IH-imidazoll-ylmethyl)methylsilane80 (1,1<sup>,</sup>-Bipheny1-2-yl)dimethyl(1Himidazol-l-ylmethyl)silane90 (l,l'-Biphenyl-3-yl)dimethyl(lHimidazol-l-ylmethyl)silane90
[bis(2-Chlorophenyl)](IH-imidazoll-ylmethyl)methylsilane40 (1,1'-Bipheny1-4-yl)dimethyl(1Himidazol-l-ylmethyl)silane, 1:1 complex with cuprous chloride50 (2-Chlorophenyl)(dimethyl)(IH-imidazol-l-ylmethyl)silane 90
TABLE 9 (Continued)
<td> Compound .</td><td> % Control of Rice Sheath Blight</td>
<td> bis(4-Fluorophenyl)hydroxy(IH-imidazol1-ylmethyl)silane</td><td> 90</td>
<td> (3-Chlorophenyl)dimethyl(IH-imidazol1-ylmethyl)silane</td><td> 90</td>
<td> (4<sup>,</sup>-Bromo-1,1'-bi phenyl-4-yl)dimethyl- (IH-imidazol-l-ylmethyl)si lane</td><td> 90</td>
<td> (3,5-Dו ch!orophenyl)dimethyl(1H-’ imidaz01-1-yl methyl)silane</td><td> 90</td>
<td> (4<sup>,</sup>-Bromo-1,1<sup>,</sup>-biphenyl-4-yl)dimethyl(1H-1,2,4-tri azol-l-y!methyl)silane</td><td> 90</td>
<td> (1,1<sup>,</sup>-Biphenyl-4-yl)dimethyl(1H-1,2,4triazol-l-ylmethyl)si 1ane, 2:1 complex with cupric chloride</td><td> 80</td>
<td> Methyl[bis(4-methylphenyl)](1H-1,2,4triazol-l-ylmethyl)silane</td><td> 30</td>
<sup>156</sup> 76 Example 77 Compounds of this invention were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of 100 ppm in 5 purified water containing 250 ppm of the surfactant TREM 014 (polyhydric alcohol esters). These suspensions were sprayed to the point of run-off on rice seedlings. The following day, the plants were inoculated with a spore suspension of Pyricularia oryzae, 10 causal agent of rice blast, and incubated in a saturated humidity chamber at 28°C for 24 hours and then in a growth room for an additional 7 days, when disease ratings were made. Percent disease control is shown in the following table. Treated plants had no or few 15 lesions while the untreated plants had numerous lesions on each leaf.
Table 10 % Control of
Compound Rice Blast
Dimethyl(1-naphthalenyl)(1H-1,2,4triazol-l-ylmethyl)silane70 bis(4-Chloropheny1)(methyl)(1H<sup>25</sup> l,2,4-triazol-l-ylmethyl)silane90 bis(4-Fluorophenyl)<methyl)(1H-
1,2,4-triazol-l-yImethyl)silane100
[4-(1,1-Dimethylethyl)phenyl]dime thy H1H-1,2,4-triazol-l-yl30 methyDsllane90 (4-Chlorophenyl)methyl(phenyl)(1H-
1,2,4-triazol-l-yImethyl)silane100
Butyl(methyl)phenyl(lH-l,2,4-triazol- l-ylmethyl)silane90 <sup>5</sup> (2-Chl or opheny !)dime thy K1H-1,2,4triazol-l-ylmethyl)silane100
Table 10 (continued) % Control of
Compound ׳Rice Blast (1,1'-Biphenyl-4-yl)butyl(methyl)(1H-1,2,4-triazol-l-ylmethyl)silane100
Butyl(4-fluorophenyl)methyl(1H-1,2,4triazol-l-ylmethyl)silane100
Dibutyl(methyl)(1H-1,2,4-triazol-lylmethyl)silane80 bis(l,1'-Biphenyl-4-yl)(methyl)(IH-
1.2.4- triazol-l-ylmethyl)silane100 (1,1'-Biphenyl-2-yl)dimethyl(1H-1,2,4triazol-l-ylmethyl)silane90
2-Chlorophenyl(methyl)phenyl(lH-l,2,4triazol-l-ylmethyl)silane100
4-Bromophenyl(methyl)phenyl(lH-l,2,4triazol-l-ylmethyl)silane80
[bis(2-Chlorophenyl)]methyl(lH-l,2,4triazol-l-ylmethyl)silane90
Dimethyl(4-methylsulfanyIphenyl)(IH-
1.2.4- triazol-l-ylmethyl)silane70 (bis(4-Bromophenyl)]methyl(lH-l,2,4triazol-l-ylmethyl) silane90 (1,1'-Bipheny1-4-yl)dimethyl(1H-1,2,4triazol-l-ylmethyl)silane, 4-dodecylbenzenesulfonic acid salt80 (l,l'-Biphenyl-4-yl)dimethyl(lH-l,2,4triazol-l-ylmethyl)silane, 1:1 com.plex with cuprous chloride100 (1,1'-Bipheny1-4-yl)dimethyl(1H-1,2,4triazol-l-ylmethyl)silane, 1:1 complex with zinc (II) chloride100
[bis(2-Fluorophenyl)]methyl(IH-
1.2.4- triazol-l-ylmethyl)silane,
1:1 complex with cuprous chloride 90
Table 10 (continued) \
X Control of
Compound Rice Blast
[bis(2-F!uorophenyl)]methyl(lH-
2,4-triazol-l-ylmethyl )silane, 2:1 complex with cupric chloride 100 (IH-Imidazol-l-ylmethyl)dimethyl(4-phenoxyphenyl)silane70
[4-(1,l-Dimethylethyl)phenyl](lHimidazol-l-y!methyl)dimethylsilane80 (4-Fluorophenyl)(IH-imidazol-l-ylmethyl)methyl(phenyl)silane100
[4-(4-Chlorophenoxy)phenyl]dimethyl(ΙΉ-imidazol-l-y!methyl)silane100 (1,1*-Bipheny1-4-yl)butyl(IH-imidazol-l-ylmethyl)methylsilane90
Butyl(4-fluorophenyl)(IH-imidazoll-ylmethyl)methylsilane100 (1,1 י-Bipheny1-2-yl)dimethyl(1Himidazol-l-y ImethyDsilane90 (1,1'-Bipheny1-3-yl) dimethyl(1Himidazol-l-ylmethyl)silane80
[bis(2-Chlorophenyl)](IH-imidazol1-ylmethyDmethylsilane90
Dimethyl(lH-imidazol-l-ylmethyl)(4-methylsulfonylphenyl)silane100
[bis(4-Bromophenyl)](IH-imidazol-lylmethyDmethylsilane80 a TABLE 10 (Continued)
Compound bis(4-Fluorophenyl) hydroxy(IH-imidazol I-ylmethyl )si 1ane
Dimethyl(1H-ו mid azol-1-yl methyl)(4- . trifluoromethoxyphenyl)silane (4<sup>,</sup>-Bromo-1»1<sup>,</sup>-biphenyl-4-yl)dimethyl(IH-imidazol-1-yl methyl)silane (4'-Bromo-1,1'-bi phenyl-4-yl)dimethyl(1H-1,2,4-triazol-l-y!methyl)silane (1,1'-Bipheny1-4-yl)dimethyl(1H-1,2,4triazol-l-ylmethyl)si lane, 1:1 complex with cupric chloride
Methyl[bis(4-methylphenyl)](1H-1,2,4triazol-l-ylmethyl)silane % Control of Rice Blast <sup>159</sup> 77 Example 79 Compounds of this invention were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of the surfactant TREM 014 (polyhydric alcohol esters). These suspensions were sprayed to the point of run-off on tomato seedlings. The following day, the plants were inoculated with a spore suspension of Phytophthora infestans, causal agent of tomato late blight, and incubated in a saturated humidity chamber at 20°C for 24 hours and then in a growth room for an additional 7 days, when disease ratings were made. Percent disease control is shown in the following table. Treated plants had no or few lesions while the untreated plants had numerous lesions on each leaf.
Table 11 % Control of Compound Tomato Late Blight
Dimethyl(4-phenoxyphenyl)(1H-1,2,4triazol-l-ylmethyl)silane50
[4-(4-Chlorophenoxy)phenyl]dimethyl(1H-1,2,4-triazol-l-yImethyl)silane50 (l,l'-Biphenyl-2-yl)dimethyl(lH-l,2,4triazol-l-ylmethyl)silane50 (1,1'-Bipheny1-4-yl)dimethyl(lH-l,2,4triazol-l-ylmethyl)silane, 4-dodecylbenzenesulfonic acid salt60 (1,1'-Bipheny1-4-yl)dimethyl(1H-1,2,4triazol-l-ylmethyl)silane, 1:1 complex with cuprous chloride100 (1,1'-Bipheny1-4-yl)dimethyl(1H-1,2,4triazol-l-ylmethyl) silane, 1:1 complex with zinc (II) chloride90
Table 11 (continued) % Control of
[bis(2-Fluorophenyl)]methyl(1H-
1,2,4-triazol-l-ylmethyl)silane, 2:1 complex with cupric chloride40 ’(4-Bromophenyl)(IH-imidazol-l-ylmethyDdimethylsilane30 <sup>1</sup>θ (l,l'-Biphenyl-4-yl)dimethyl(lHimidazol-l-y ImethyDsilane50 (IH-Imidazol-l-y!methyl)dimethyl(4-phenoxyphenyl)silane80
Dimethyl(IH-imidazol-l-ylmethyl)15 (3-trifluoromethylphenyl)silane70 (2,6-Dimethoxyphenyl)(dimethyl)(1Himidazol-l-ylmethyl)silane50
[bis(2-Chlorophenyl)](IH-imidazol- l-ylmethyl)methylsilane60 (4'-Bromo-1,1'-bi phenyl-4-yl)dimethyl(1H-1,2,4-triazol-l-ylmethyl)silane30 (l,l'-Biphenyl-4-yl)dimethyl(5-methyl1H-1,2,4-tri azol-1-ylmethyl)silane80 (1,1'-Biphenyl-4-yl )dimethyl (,1 H-l,2,4triazol-l-ylmethyl)silane, 1:1 complex with cupric chloride90 ־-.־׳ י./rr - ..־י־ ־ ...־ .־' ־ ץ־:’^ךז,ץ י-׳ ׳ '
66114/2 ' 'ii
- . . > - 161 I
I
Example 78'
Compounds of this invention were incorporated' into 45<sup>e</sup>C standard strength V-8 agar at a concentration of 200.0 ppm. The amended media were then dis־ 5 pensed into petri dishes and allowed to solidify. 9
Plugs approximately 4 mm from agar cultures of 5
Phytophthora species: Phytophthora cinnamomi, P. cactorum, P. infestans, P. palmivora, and P. parasitica‘ var. nicotianae were placed on the media and incubated' at 22°C for 6 days. Colonies whose radial growth ex-| tended 1 mm or less were considered to be controlledן by a compound when compared to colonies whose radialί growth extended 15 mm or more when growing on unamended media. The number of Phytophthora species 15 controlled by certain compounds of this invention are listed in the table below.!
i Table 12 # of 5 Phytophthora species
Compound _____controlled in vitro i !
i (Butyl)dimethyl(lH-l,2,4-triazol-lylmethyDsilane 1ן (3,4־Dichlorophenyl)dimethyl(lH-!
l,2,4-triazol-l-ylmethyl)silane 2j (l,l'־Biphenyl-4־yl)dimethyl(lH-!
imidazol-l-ylmethyDsilane3 (IH-Imidazol-l-ylmethyl)dimethyl30 (4-phenoxyphenyDsilane4 (2,4-Di chlorophenyl )dimethyHIHimidazol-l-ylmethyl)silane (4-Fluorophenyl)(IH-imidazol-l-ylmethyl)methyl(phenyl)silane
Example 80
Compounds of this invention were incorporated into a proprietary formulation and used to coat cotton seeds at a rate of 2 gm/kg seed. After being thor5 oughly coated, the seeds were allowed to air dry at room temperature. The cotton seeds were then planted into soil amended with the fungus Pythium aphanadermatum, sand, and corn meal at a rate sufficient to kill most untreated seeds. The seeds were held at 10 room temperature for 1 week, after which time disease ratings were made. Percent disease control is shown in the following table. Most or all seeds from treatments germinated and produced vigorous seedlings in contrast to untreated seeds which either did not 15 germinate or produced damped off or weak seedlings.
Table 13 % Control of Compound Pythium on Cotton
Et hy !dime thy K1H-1,2,4-triazol-lylmethyl)silane48 (1,1'-Biphenyl-4-yl)dimethyl(lH-
1,2,4-triazol-l-y!methyl)silane12 (4-Chlorophenyl)dimethyl(lH-l,2,4triazol-l-ylmethyDsilane53
Dimethyl(4-phenoxyphenyl)(1H-1,2,4triazol-l-ylmethyDsilane18 (1,1'-Bipheny1-4-yl)dimethy1(1H<sup>30</sup> imidazol-l-ylmethyl)silane18 (4-Chlorophenyl)(IH-imidazol-lylmethyDdimethylsilane18 (3,4-Dichlorophenyl)(IH-imidazol- l-ylmethyDdimethylsilane15 ^control at a rate of 0.5 gm/kg seed.
Example 80
Compounds of this invention were incorporated into a proprietary formulation and used to coat corn seeds at a rate of 2 gm/kg seed. After being thor5 oughly coated, the seeds were allowed to air dry at room temperature. The seeds were then planted into soil amended with a mixture of the fungus Pythium aphanadermatum, sand, and corn meal at a rate sufficient to kill most untreated seeds. The seeds were 10 held at 49°F for 2 weeks and then at 70°F for 1 additional week. After this time disease ratings were made. Percent disease control is shown in the following table. Most or all seeds from treatments germinated and produced vigorous seedlings in contrast 13 to untreated seeds which either did not germinate or produced damped off or weak seedlings.
Table 14 % Control of
Compound Pythium on Corn
Ethyldimethyl(lH-l,2,4-triazol-lylmethyDsilane13 __ (l,l'-Biphenyl-4-yl)dimethyl(lH-
1.2.4- triazol-l-ylmethyl)silane 30 (4-Chlorophenyl)dimethyl(lH-l,2,4- triazol-l-ylmethyl)silane8
Dimethyl(l-naphthalenyl)(1H-1,2,4triazol-l-ylmethyl)silane30 (3,4-Dichlorophenyl)dimethyl(1H-
1.2.4- triazol-1-ylmethyl)silane43 (IH-Imidazol-l-ylmethyl)dimethyl(4-methylphenyl)silane 3°
Table 14 (continued)
Compound % Control of Pythium on Corn (1,1 '-Bipheny 1-4-yl )dime thy K1Himidazol-l-ylmethyl)silane32 (4-Chlorophenyl)(IH-imidazol-lylmethyDdimethylsilane25 (IH-Imidazol-l-ylmethyl)dimethyl(l-naphthalenyl)silane27
Γ (3,4-0ichlorophenyl)(ΙΗ-imidazolΙ-ylmethyDdimethylsilane30 (IH-Imidazol-l-yImethy!)dimethyl(4-phenoxyphenyl)silane5
Dimethyl(4-fluoropheny1)(IH-imidazol-l-ylmethyl)silane15
Contents22
32 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6 Sheet 7 Sheet 8 Sheet 9 Sheet 10 Sheet 11 Sheet 12 Sheet 13 Sheet 14 Sheet 15 Sheet 16 Sheet 17 Sheet 18 Sheet 19 Sheet 20 Sheet 21 Sheet 22 Sheet 23 Sheet 24 Sheet 25 Sheet 26 Sheet 27 Sheet 28 Sheet 29 Sheet 30 Sheet 31 Sheet 32
41 members in 20 offices
Priority claims24
| Document | Office | Kind | Date |
|---|---|---|---|
| 27698681 | United States of America | A | |
| 27698681 | United States of America | A | |
| 27698781 | United States of America | A | |
| 27698781 | United States of America | A | |
| 34926182 | United States of America | A | |
| 34926182 | United States of America | A | |
| 34926282 | United States of America | A | |
| 34926282 | United States of America | A | |
| 37712182 | United States of America | A | |
| 37712182 | United States of America | A | |
| 37712282 | United States of America | A | |
| 37712282 | United States of America | A | |
| 276986 | – | – | – |
| 276987 | – | – | – |
| 349261 | – | – | – |
| 349262 | – | – | – |
| 377121 | – | – | – |
| 377122 | – | – | – |
| US19810276986 | – | – | – |
| US19810276987 | – | – | – |
| US19820349261 | – | – | – |
| US19820349262 | – | – | – |
| US19820377121 | – | – | – |
| US19820377122 | – | – | – |
Members41
| Document | Office | Kind | |
|---|---|---|---|
| IL66114A0 | Israel | A0 | |
| IL66114D0 | Israel | D0 | |
| DK282782A | Denmark | A | |
| EP0068813A2 | European Patent Office (EPO) | A2 | |
| AU8509982A | Australia | A | |
| JPS584791A | Japan | A | |
| EP0068813A3 | European Patent Office (EPO) | A3 | |
| BR8203631A | Brazil | A | |
| ES8307829A1 | Spain | A1 | |
| JPS58144393A | Japan | A | |
| PL237088A1 | Poland | A1 | |
| KR840000570A | Republic of Korea | A | |
| ZA824460B | South Africa | B | |
| ES8404367A1 | Spain | A1 | |
| ES8404368A1 | Spain | A1 | |
| ES8404369A1 | Spain | A1 | |
| GR76497B | Greece | B | |
| CA1176258A | Canada | A | |
| US4496551A | United States of America | A | |
| NZ201061A | New Zealand | A | |
| PH18112A | Philippines | A | |
| PH18132A | Philippines | A | |
| US4510136A | United States of America | A | |
| PL133929B1 | Poland | B1 | |
| EP0068813B1 | European Patent Office (EPO) | B1 | |
| AT15804T | Austria | T | |
| ATE15804T1 | Austria | T1 | |
| DE3266532D1 | Germany | D1 | |
| CS238626B2 | Czechoslovakia (until 1993) | B2 | |
| HU189152B | Hungary | B | |
| AU553808B2 | Australia | B2 | |
| SU1324573A3 | Soviet Union (until 1991) | A3 | |
| JPS6253515B2 | Japan | B2 | |
| IL66114AThis record | Israel | A | |
| KR880002604B1 | Republic of Korea | B1 | |
| DK126490A | Denmark | A | |
| DK126490D0 | Denmark | D0 | |
| DK126790A | Denmark | A | |
| DK126790D0 | Denmark | D0 | |
| DK160364B | Denmark | B | |
| DK160364C | Denmark | C |
1 legal event, as the office reported them to INPADOC
Events
| Event | Code | |
|---|---|---|
| Patent renewedKB | KB |
Numbers
- Publication, DOCDB
- 66114
- Publication, EPODOC
- IL66114
- Application
- 66114
- Application, DOCDB
- 6611482
- Application, EPODOC
- IL19820066114
Titles
- English
- 1,2,4-TRIAZOLE AND IMIDAZOLE DERIVATIVES,THEIR PREPARATION AND THEIR USE AS FUNGICIDES
Classification
- CPC, 5
- C07F7/0812
- C07F7/08
- A01N55/00
- C07F7/0838
- C07F7/1804
- IPC, 3
- A01N55 00
- C07F7 08
- C07F7 18