Nitro-Paraphenylene-Diamines and their use as Hair Dyes

DESCRIPTIVE MEMORY filed in support of a request for the 1st Certificate of Addition to the PATENT OF INVENTION at 49,214 of 30.7.65 formed by the Société Anonyme known as t L * 0PEAL for

Basic nitro derivatives of ni. reparaphény '.ènediamine' Invcntours: Grégoire KALOPISSIS

Andrée DUGAÜT born OIE .sCEY.

i;?

I 'f

I '¥ · - · h;,:

W v:

ï fc û

fe • 'j':

fe • mîî

In the principle patent.

fe ment characterized by the fact that it consists of; 'ife aqueous solution of one or more dyes corresponding to. * the following formula t. t

R \

Don't

(I)

-f

- pi -'Xi '···

-NO, i

NOT

A \ M »

RR

<img file="LU50348A1_D0001.tif" />

, ·/* ·

- \ fe '' · '· ν ·' t?

X "fe: -Z?

• fe dun 3 which R, Π and R represent a hydrogen atom,

Pt v; r ..

!

"C, a lower alkyl radical or a lower Jhydroxyalkyl radical | and in which R is an optionally quatemi sablo radical on the nitrogen at the end of the chain when this nitrogen is · tertiary, radical which has the formula t · R.

- (CH) 2 π ^R2 where R, and R can be the same or different and represent X 2 a

fy'l.

A? * · "Li ·;

'By g

.fë ite

- R

r .. · /, feel a hydrogen atony, a lower alkyl radical or a lower hydroxyalkyl radical, R ^ and R ^ can also '/, form with the nitrogen atom on which they are fixed a · ÿg yi heterocycle, and where lo parameter n is an integer between ^ "B and k inclusive, the amino group located in position ortho ^ of the nitro group in formula (l) never denoting tertiary ejfjy" j¹'·'? · 'Β Λ, ·, the radicals S ot H not being able to representor simultaneously

4 'r \ *.

hydrogen when the nitro group is in the meta yz position with respect to the nitrogen atom carrying the amino chain represented:

Ml estéo by R.

î- vï Ιΐ-'Λ »

The main patent further describes, at. titref§® of a new industrial product, a dye having the formula ^

R^r R

XS \ BJ

R • NO, (II) 'S ·' · * fe;

- cfafe -; 'Λ · £ ζ · tô?; -:

tte (• '•• s • W tte î ···. ·. · .. · • ·· - 1 {in laquollo R, R, R ot R have the same definitions as above, the amino group located in the ortho position of the nitro group in the formula (il) never being tertiary ';.' ;. ·?

î W - ·; Λ_α and the radicals R and R cannot represent simultaneously ·;, ·; ' 'hydrogen"

Ο.^ιΛ ' ^nV· "* · Kit?

t ·

<img file="LU50348A1_D0002.tif" />

-^&lt;3

3.The present addition is intended to supplement * with additional examples! the illustration of the general formula which has already been given in the main patent (y ,; \

The present addition describes the new dyes. wishes corresponding to the formula genie alo I

Z ~ NZ.

X t

NHZ ·, in which Z represents a methyl, ethylol or araino-ftâ 1 · 'Î'.S ethyl group; in which Z „represents hydrogen or a group £ *. · '' 'X. î ·: · .B 'v^; · '> Îii

X- -V ·· · »«.

methyl; and in which Z „represents a methyl group,,

J \ yù-hydroxyethylaminopropyl, diethylaminoethyl or a group in which n takes the values ​​2, 4, 6 ..

The present addition also describes the use of the dyes of formula (III) in compositions \

hair cosmetics »It should be noted that the dyes of formula (ill) all correspond to certain cases. · Particulars of the general formula (l) of the dyes described

r. · '. ·>

f in the main patent. As a result, all of these dyes a,.:

have the particular properties indicated in the patent i '.

main, in particular from the point of view of the production of hair dyes.

To better understand the object of the invention, we will now describe, by way of illustration and without any limitation, a few examples of preparation and use of the compounds of formula (ill) * ·.

. '· ·' 7.,. y- '' X î X

X x

;; · λλ · / ..

<img file="LU50348A1_D0003.tif" />

. - j • V »V

- ·?, *., V ·. X7:

h * ·, y. X \ £ 0

EXAMPLE I

h.Preparation of dihydrochloride do N- (at -hydroxyethylamino-1.

nits'n-2 .Π'-methyl-N - h-diethylaminoethylamino-4 .benzene. · -./S? h

The preparation reaction can be schematized as follows // I

NIICIL

<img file="LU50348A1_D0004.tif" />

d / 01- (011, ^ (0 ^ ¾, H ci ^NOT° 2 '' '· ch₂-ch₂oh '7²⁵ “OH -CH -N '° Λ

<img file="LU50348A1_D0005.tif" />

, HC1

NH-CH -CH OH

A mixture composed of 0.237 of H-ß-hydroxyethylamino-l, 2-nitro, N-methyl-amino-4 "benzene 'pv η λ.'λ \ (that is to say 50 g) is brought to reflux. , do 200 cnr of water and 20 g of carbonate of lime * We introduce, little by little and with stirring, 0.355 meiy;

sSÎ · “';

do p-diethylaminoethylchloride hydrochloride (ie dircp

Q -ît'ôl g) in solution in 120 cnr of water, After having maintained the '7 i · \ © reflux for three hours, wring it out boiling' After having cooled the filtrate, it is made alkaline with soda and we extract> 7. · M .- {the product obtained with ethyl acetate. solvent under • -Λ-1 * '',

video * The oily residue (i.e. 65 g) is dissolved in 'hjn, Wi

500 cm of propanol. This saturated propa./Z solution then cooled with dry gaseous hydrochloric acid is saturated and 71.5 g of dichlorhydrato do N-ß> -hydroxy0thylaraino-l, nitro-2, (N'-methyljN'-β-diethylaminoethyl) are wrung out. ) -amino ^ 4, benzene which melts with decomposition between 118 and 123 * C.

The base isolated in the usual way from this dihydrochloride is an oil, the analysis of which gives the following results;

'm / s'; Sî

5 / ¾ .ΫχΑ * î'j'f '¹·

7/

- j;. · ''>

ί^;· 7 ”· / · ·: î-Λ 'k'Z. : ¾¾ '· M./V .i A --ig®

-,¾

<td>Analysis</td><td>Calculated</td><td>Find</td>

<td>he ii</td><td>^{for C}15^H/.ô^NOT4°3</td><td></td>

<td>II II 1 'p £ &lt; not ^u P II</td><td> 58,06</td><td> 58&gt;31 - 58, 14</td>

<td>ΐί H fi, II</td><td> 8,5?</td><td> 8,10 - 8, 25</td>

<td>I l N fi II II</td><td> 18,06</td><td> 18,27 - 18, 25</td>

.y-,

, V

EXAMPLE II

Preparation of N-methylamin.ol &amp; hydrochloride_tnitro-2_t

H^at -amlnobutylamino-4 »benzene

The preparation reactions can be schematized as follows: ':, v.

ΊΙ • W i? /

D *:

• ·. i û \ / K to n

<img file="LU50348A1_D0006.tif" />

^Br (^CHAT^Br

Nhoi ^

G "0

NK> \ C = 0 '

<img file="LU50348A1_D0007.tif" />

NHCH, ^S%^^CH2\ ~^NOT:

<img file="LU50348A1_D0008.tif" />

.. | Ç₇ t, ·> $ ^S%/^(CHHave

-¾¾

4.?.ç t ni fix

<img file="LU50348A1_D0009.tif" />

HCl

Λ no.

NHCKL ': / ¾ sjt &amp; Λ' &lt;î! &amp;

~ 1st Phase g Preparation of N-niüthylamino-l, nitro ~ 2, (N * ~ bnrrênesulfonylH^vs-bromobutyl) 4-amino »benzene.

Dissolve 0.4 mole of potassium salt of, N-methylamino-ljnitro- ^ jN'-benzonesulfonylaaiino-Ni, benzene (c'ost-à-diro'13θ g) in 350 cm^J of dimethylformamide "On

V-,%

h; '· rp \ ". &lt;Hv, * 'i £ », r .30

<img file="LU50348A1_D0010.tif" />

6.-- ;

add 0.8 mole of 1,4-dibromobutane (ie 95.5 cm 3) and the reaction mixture is maintained for 30 minutes at 90 ° C. Cool, pour into 2 500 liters of water and drain 190 gAf. · / Of a crude product which, after fractional crystallization suede lo benzene, provides i¹ ν * ζ Ά

Zï / 'ii (' b Ji .'f? -R.

- on the one hand, 145 G of N-methylaniino-1, nitro-2, (N'benzene- i- £ and “yf” suifonyl “îI'bromobutyl) -amino-4, benzene, which 'melts at 14O^eC / whose analysis results are as follows X

<td>II II II II II II II</td><td>Analysis</td><td>Calculated for ^VS17^H2O^NOT3°4^{S Br}</td><td></td><td>Find</td><td></td><td>lî II II 1 1 1</td>

<td>· K-- H</td><td></td><td></td><td> -</td><td></td><td></td><td> 1</td>

<td>II II II II</td><td>G fi</td><td> 46,15</td><td> 46,</td><td> 30 -</td><td> 46,</td><td>24 ίΐ</td>

<td>&lt;1 II II he</td><td>He fi</td><td> 4,52</td><td> 4,</td><td> 59 -</td><td> 4,</td><td> 41</td>

<td>II II II</td><td>H fi</td><td> 9,50</td><td> 9»</td><td> 53 -</td><td> 9,</td><td> 77</td>

<td>II He___</td><td></td><td></td><td></td><td></td><td></td><td></td>

'F'-L

- on the other hand, jO g of bifl ~ / ft® ~ (methylamino-4, nitro-3) -phenyJylf 'bonzenosulfemidobutano which melts at 245 ° C whose results; Analysis are as follows: yi

J. ;; Have;,/

I-t-

<td></td><td></td><td></td>

<td>Analysis</td><td>Calculated for \</td><td>Find</td>

<td></td><td>^VSAW₂</td><td></td>

<td> ~----—4— — — -</td><td> ----------_{-------------}</td><td></td>

<td>c fi</td><td> 53,88</td><td> 53,78 - 53,70</td>

<td>H fi</td><td> 4,79 ·</td><td> “ 4,97 - 4,93 ·</td>

<td>N fi</td><td> 12,27</td><td> 12,45 - 12,40</td>

7_v^z- \ kc-Hawai'i ¹ there j * y γ% ·

I i ”.-% * / · îH i &lt;; f L -tHskf.

ΐνΛ, · - '., ~ 2èmo Phase S Preparation of N-methylajiiino-l, nitro-2 "(N'-benzenesulfonyl), N^f ~ phthalimldobutyi) ainino-4.benzene "

0.25 mole of N ~ methylamino-l, nitro-2 is dissolved^;-, ÿ (K'-benzènosU ', lfonyl, N^?-bromobutyl) ainino-4 (i.e.

O 'WA

110.5 c) in_z500 cnr do dimethylformamido. 0.3 moles are added¹ do phthaliruide do potash (that is 55.5 g), then we

P '\ _k"VS· ,"".

heat the reaction mixture for one hour in a boiling water bath— giÿy ·· / - ··

7·- .

slow. Pour into 4 liters of water and wring 12é> g of *^: - -.- ΛλΛ crude product which, after recrystallization from the benzene-hexane mixture, melts at 14-1 ^ 0. Los analysis results of this.

. > »Product are as follows i. '' j®

<td> 5</td><td>ii II II II II</td><td>Analysis</td><td>Calculated for ^VS25^H24^NOT4°6^S</td><td>Find</td>

<td></td><td>1! " he II II II</td><td>• c $</td><td> 59, 05 ·</td><td> 59,16 - 58,99</td>

<td></td><td>II II II II</td><td>$ II</td><td> 4» 72</td><td> 4,89 - 4,90</td>

<td> 10</td><td>II II II</td><td>NOT</td><td> 11, 02</td><td> 10,99 - 11,09</td>

<td></td><td>II HE.</td><td></td><td></td><td></td>

B ¹ L;

i · "·. ft ,. . &lt;

R

- 3rd Phase: Preparation of N-methylamino-l, nitro-2. i / · (N'-benzonesulfonyl, N'-aminobutyl) -amino-4 "benzene. '

To a solution of 0 ^ 02 mole of phthalimide subs- y /

O \>., · Tituéo (ie 10, 16 g) in 80 cnr of propanol, we ', / ··. · Add 0.04 mole of hydrazine hydrate, then heat

Λ ', ο minutes in a boiling water bath.' · By filtration of the hot reaction mixture, the major part of the phthaly is removed;

drazide formed. After cooling, an orange-colored oil is isolated by decantation, which is dissolved in ethyl acetate, iS '. This ethyl aoiate solution is extracted with '.' · Ÿ- / a semi-normal hydrochloric solution. We alkalize it. ...

t, - * -p, hydrochloric aqueous phase and 4.5 g of N'methylaminf S are drained; - (% ¾

-1, 2-nitro, (N'benzenesuif onyl, N '-aminobut'ÿl) 4-amino benzene,' '· /? / Which after recrystallization from ethyl acetate. '' 'B

135^dC <> The results of the analysis for this product are as follows:?

<td>Γ 1 I analyse 1 1</td><td>Calculated for ^VS17^H22°4^NOT4^S</td><td>\. \ Found 1 \ '“* F 11 „X .....- It</td>

<td>1 ic £ 1 1 wd i H. J NOT</td><td> 53,96 5,82 14,82</td><td>\ i 54, lï - 53.95 1 5.76% 5.91, 14.93 7 14.80 '___________ λ __________</td>

λ · /// \ * / ♦ · ^f-'h.% ·

vs.

- .ÿ / t * L-λ

8i0n caturci of acid hydrochloric gaseous dry the mother liquids propnnoliqu £ cooled and still isolated by spin 2 g do jiro. has been used as hydrochloride · · ·; - 4? · Ιηο Phase S Pr-f a aal; ! nn of the hydrochloride of N-nr '· thylamino-2-nitro'. ? P-amlnobutylr-mino-'f .benzene ·

0.013 mole of N-methylamino-1, nitro-2, (K '-benzenosulfonyl, N' -aliinobutyl) amino-4, benzene o are heated!

(i.e. 5 g) in 15 cm^J concentrated hydrochloric acid, p!

at reflux during gentle stroke <> Add to the solution, the hydrochloric acid cooled its volume of alcohol and drain 3.2 g

I do dichlorhydrato of N-methylamino-2-nitro-2, N * -aminobutylamino-4, benzene which, after recrystallization from acid. . · »&lt;· Concentrated hydrochloric acid, gives the results &lt;êx;

Next S 8!

11.

<td>Analyso</td><td>V Calculated for ^VSli^not20°2^NOT4^C12</td><td>i found The -. .</td>

<td>C $ H $ N $</td><td> 42,44 6,43 18,00</td><td>i 1 • '42, 49 - 42.38 \ \ 6.4l - 6.25 l \ / - 18., 05 - 18.10 \</td>

/ '-' ï fi y

• / • y '- • »u

J'N

'..' Yi

VT rVÎ «('λ

J; fë »2 • rrf-w ^fc 'W. • i “': ςη.,.

$ ♦ '' λ * hd 'i *' *

<img file="LU50348A1_D0011.tif" />

Λ · 7 ^;· •7/· ·

EXAMPLE III

Filo'- loi preparation ·· '¹ vd rate of N-methylamino-1 &lt;nitro-2,; ''

7 '- Y- (jn-hy.Î rc -r'é tliyl, ré thyl) 7-aminopropyl-aniino-4 .benzene

- ^;7 · '. J

7® as follows î

The preparation reactions can be schematized from the 's; 7 i ·, · 77 ΐ &lt;E / “SO, CII -CH -CH„ Br

2\ / 2

<img file="LU50348A1_D0012.tif" />

NHCH,

·./%

NH,

7gh „-ch, oh r

A · y

• · ·;

·'

CH,

S0₂-r^CK2-^CH2-^CH2-^NOT \/^CII2-^Cn2-^CH2-^NOT'

NOT

<img file="LU50348A1_D0013.tif" />

NO, 2 HCl

NHCH,

CH 'CH -CH -OH i' CH ^ -CHgOH

HCl \ · '. ·. - · &amp;

7:

.your:

S

J

7; î. '7 \ j .- ·' fy

u 1st Phaso i Preparation of N-methylamino-l, nitro-2, (î7-benzene.sulfonyl, N⁸- fi -Iihydroxyé thyl, mé thyl) 7 amino-/l propyl) nmino-4, benzone a • ·. ··, ·; ·

0.0466 mol of N-methylamino-1, / 7- = 7 is heated:

V ni tro -2, (N »-benzene sulfonyl, N ® - 'ïf -bromopropyl) araino-4 Ibeaz one;

(that is to say 20 g) in 0.373 mol of methyl, -hydroxyethyl ^ / amine (that is to say 28 g) for 7 hours at 120 ° C., The excess methyl is removed, [ 5-hydroxyethylamine under vacuum "The residue li ί '' is taken up in twice-normal hydrochloric acid, / ίβ

The expected product is then drained, meaning the hydrochloride form; /; We say all this hydrochloride in hot water and make

B '··' alkaline with the aido solution of soda. After cooling, 10 g of N-methyloinino-1 are drained; nitro-2, (N'-benzenesul-T / A '7

7’

10. ~ f onyl, N '- 7 - / Π - (7 -hydroiiyé thyl, raé thylJ / + - aminopropyl) amino-4,' ¹ : ·. · Benzene which, after recriatallization in methanol, melts. . 5; $ ·:

• - '. VA at 85 ° C. The analysis results for this product are as follows

ΙΟ

<img file="LU50348A1_D0014.tif" />

Calculated for ^ö19^lW5^S

Find

5li, 02 6, lô i 27

54 * 33 6.23 i

13,43 \

54,18

6,30

13,57

Î5XW f * '0. · ·' \

Λ

- 2nd Fhaso 3 Preparation of the dichlorhydrato of N-rtiethylamino nltro-2, (iP- 7 - / P ”(V> -3i-hydroxyethyl, methyl) 7-aminopropyl) amino-kv · .benzene”

It is heated &amp; reflux for two hours. 0.048 mo / ft · /; $ Γ '„do N-niethylamino-l, nitro-2, N'benzènesulfonyl,. (. N' * - / N^rt- (ft- 55.¾ ¹ 'xx hydroxyé thyl, ni é t hyljy ^ -aininopropyl) amino-4, b enz en (that is to say XX ο, ννλ.'7 say 2.04 g) donations 6 cnr of concentrated hydrochloric acid. AprèiV *; dilution, alkalinize with sodium hydroxide and extract the solution 7¾ '' ί '·' '' X¹· 'Sodiquo to. using methylisobutyicetone. After chasing Ti.'y:

under .methylisobutyicetone, the .B residue is redissolved;

oily in normal propyl alcohol and we saturate this V [6 ^

K alcoholic solution well cooled with hydrochloric acid.

quo gaseous soc. 1.4 g of dichlorhydrato are wrung out

N-mothylamino-l_snitro-2, (N * - 7ft -hydroxyethyl, methyl I, auiinopropyl) aniino-4, benzene, which melts with deposition at 100 * 0 "The results of analysis of this product are as follows

<img file="LU50348A1_D0015.tif" />

« */· ·

ÿ.Sïi 'f' / r »f ς»> 1.

'Λ, r,₄. j ..., ..

II 11 *

II

HE-

<td>Analysis</td><td>Calculated for^Ο13^ΪΣ2Λ^Ο12^Ο3</td><td>Find · !</td>

<td>r. &lt;o,.&gt; H &lt;$</td><td> 4.3,94 6,76 ' 15,77</td><td>• 7 43, '88 - 43.94 6.72 '- 6.52 15.86 \ - 15.79 'J \ 1 _________L____________¹</td>

EXAMPLE IV

Ircporntlnji of N- —ethylarolno-l 'dichlorhyclrate, 2-nitro, sm5.ro -': - bor nzoro "fei:

'· -' • '-S ri --Λ w

• EV> '«-if jy.

• t -Ä ί • R 'Ris, ϊΛ'

- Ö; -P '- ^¹·

- wire '' ÎS '' $ &amp;

The preparation reactions can be schematized from the '' 'fl ·.

next way J

<img file="LU50348A1_D0016.tif" />

Br

<img file="LU50348A1_D0017.tif" />

v / ,,;

£·&amp;:

Μ^ν'ί> * V 7 -, .-- 1 "A. · n- (eH₂)_at-_K-so / 2> -OH₃ g

H COCIL · \ / ³

<img file="LU50348A1_D0018.tif" />

HCl ·>

* Λ- '· r⁴'? l · • ”“ H' * ”'“ i ·.

<img file="LU50348A1_D0019.tif" />

'· - Ίτ /' · / ^SRWI>

• s? • -A ^ ''. AT··' ,¹W

- ,. yZ:

• Γ, '“Γ- · Χ -. .. -. f "*;

i J · β &amp; κ ' ^; B. ί '“&lt;Ά' - ^;

· > »/- ·. .··£&*

<img file="LU50348A1_D0020.tif" />

·'···.;·.

12,• .· ·'.

'fe / ·

'?. ·. ·· fe; ·;

i

<img file="LU50348A1_D0021.tif" />

n ï; · "

- Phnso s Prepa ^! on du (Np-toluènesulfonyl, N-ft-phtaljf;% r Idoétbyl) -nmÎT) o-Iuiiltro-2, N^i!~ Acetylamino-4 bcnzèno. ?

Oxi dissolved 0.01 mol% of (Np-toluenesulfonyl, $>?

· '·' 'J ·:., Îf- p> -brouioethyl) -œino-1, nitro-2,11' -acetylamino-4, benzene '3 V (i.e. 4 »5ég) in lé cm ^ do diméthylformamide, On r t '.' ·., '

ΙΟ fe adds 0.012 mol of potassium phthalimide and the reaction mixture is heated for one hour in a boiling water bath. On - yd / P i · ''.

hot filter, pour into 200 cnr of water and spin 5 g • "fe; · do raw product yes" after recrystallization from the 3''ï acetone-water mixture melts at 205 ° C. The analysis of the product obtained gives yd the following results 2 - &lt;.% «SaasacssssaszssxsssssässsssssssSsssasss

Analysis

VS

M

N £

Calculated for ^VS25^H22°7^NOT4^S

57, 4

4, 21'

10,'72 \

Find

57,61 - 57,63

4,37 - 4,31

10.93. - 10.79 \ -'S?

- aè'po Phase j Preparation of (N-p4toluenesulfonyl, N- ß-aminc'Ufe ethyl) -amino-l, nitro-2 „N'-acetyloniino-4.benzene. · '>' 'W

0.215 mol of (Np-toluenesulfonyl, "-ÿÿ? N-fo-phthalimidoethyl) -amino-l, 2-nitro, 4-acetylamino are dissolved._ibenzene · fefe (i.e. 112.2 g) in 6θθ cnr of propanol. Add to .ffe) '';; Sâ · this solution 0.43 mole of hydrazine hydrate (i.e.

g) and it is heated for 20 minutes in a boiling water bath. By .'fe # i "- 'filtration of the hot reaction mixture, 34 g of' · · are isolated.

phtalâydrazide. The propanolic mother liquors are cooled to \, '' ,,,,

-5 ° 0. It then separates a red oil which is removed \ '' Q; 'i by decantation, then .on saturate the alcoholic solution of acid &amp; fe \. / fe dry hydrochloric gas and the product 10 is filtered under \ r:

form of hydrochloride. We release the base in the usual way * '.' · · Ϊ́ ': · ·>. ;

<img file="LU50348A1_D0022.tif" />

&lt;· I

13.- lo. This gives 66 g of (N - ^> - toluenesulfonyl, N- -amino- h; etkyl) -amino-l, nit: .O-2, K '^t-acetylainino-4, benzene which, after rcrristallisatien in pyridine, melts at 223®C. Analysis'? $; of the product obtained gives the following results J · fÿ '

ΙΟ

<td>II II II he II II</td><td>analyzed</td><td>Calculated for ^VSl₇^H20V 5</td><td></td><td>. Find</td>

<td>i 1 1 1</td><td>1 Ω IA</td><td> 52,04</td><td></td><td> 51,82 - 51,90</td>

<td> 1 1 1</td><td>I! £</td><td> 5,10</td><td></td><td> ’ 5,05 - 5,11</td>

<td>II</td><td></td><td></td><td></td><td>t</td>

<td>II II</td><td>II</td><td> 14,28</td><td></td><td> ; 14,21 - 14,08</td>

<td> 1</td><td></td><td></td><td></td><td></td>

<td>L .___</td><td></td><td></td><td></td><td></td>

The oil eliminated during the preparation ÿ · '; easily crystallized from methanol. We; obtains a product. '? / rougo with a melting point of zca ^ XsrwdAXacrsxxtcsx 175 ° C' '

- 3àt · Phase t Preparation of dlchlorhydrato do N-jè-amino- '? éthy.lpmlno-l_fnitro-2, ninlno-4, benzone "'

We heat one hour in a boiling water bath

0.102 mole do M (p-toluenesulfonyl, N- j5 -aminoethyl) ~ amino-l,.

nitro-2, N'-acetylamino-4, benzene (i.e. 40 g) in 200001--.

hydrochloric acid seven times normal. Cooled and - / 5 wrung 20.7 C of dlchlorhydrato Np> -aininoothylamino-l, '/ \? £ ·;

nitro-2-amino-4_sbenzene, which, after recrystallizing in,? '·?

If concentrated hydrochloric acid gives the following results to the analysis ï h · ..

<td> 25</td><td>XC = = II</td><td></td><td></td><td></td><td> 1</td>

<td></td><td>II II II II II II HE</td><td>Analysis</td><td>Calculated for</td><td>Find</td><td>J 1 1 1 1 1</td>

<td></td><td>11 II</td><td></td><td></td><td></td><td>II</td>

<td></td><td>II II he</td><td>C $ S</td><td> 35,09</td><td> 35,50 - 35,60</td><td>II II II</td>

<td></td><td>II II</td><td>'H%</td><td> 5,20</td><td> 5,01 « 5,10</td><td>II II</td>

<td> 30</td><td>II II II</td><td>-T. &lt;/ . 4.Ί /&gt;</td><td> 20,82</td><td> 21,00 - 20,82</td><td>¹ \ ¹¹\ !!</td>

<td></td><td>II</td><td></td><td></td><td></td><td></td>

<td></td><td>HE _</td><td></td><td></td><td></td><td> 21</td>

• « / · »

<img file="LU50348A1_D0023.tif" />

σ> · ί; 5 ο dί Η- {.> · 2Σ '' vé'nv '. •^r\ Ino-l_{! l}nltro-2, K^Î-β —djethyl— / It '. ·· '· υ; J1 ry .- /) '

L -. 'V rûr.Cv / next

Z .... of preparation can be schematically illustrated

HH! 2 'V

C "H"

Cl CI: 7-CIÎ „~ 2k ~ ⁹ HCl ' ^xvs₂^not5 ^°2^H5

H CH -CH-N ^Z >

v ²

C "H.

- "AO

NO, '2 5, HCl îï ^Z Αΐ -CH -OH 2 2 • A. H^z CH₂-CH -OH

The mixture of 0.17 mol of -yethylardno-l, 2-nitro, 4-amino, benzene (c ¹ that is to say · _

V "t

;)., 250 enk of water and 12 g of carbonate of lime "On iaîrvdit Le peu. à pou, et ..out: ag.i i-ation, 0.19 molo do hydrochloride do diethylaminoethyiohloride (it that is to say 32.7 s) in solution in 100 cm of water, The addition finished, the reflux is maintained for another hour, the mixture is boiled, and the cooled filtrate is extracted with methyl isobutylated. tone for î '\ possibly eliminating an initial product do not have /. _ acted. On alkaline round with sodium hydroxide, the aqueous phase. \ which centiont the expected product as monohydrochloride,¹It is extracted with the aido of methyl isobutyl ketone. After removing the solvent under vacuum, 46 g of oil are obtained.

¹ ti: · ...

violet, which crystallizes fairly quickly. After rocrystalll-, ·?. · Sation in the cyclohexano-bonzone mixture, the product melts 7. to 73^atVS_o Its analysis gives the following results t.

inalys g

Calculated for

56, 7&amp; 8,11

10,92

Find

56,67 - 56,76

7,98 _SSB> i> :; ·! r, ki Kin rpy H: ·· '··

8,17

II dj

It λ n ·;

He ·.

18,95 - 19,02

11 '· · IP; ·

-Ji

B-rENPI.K \ FL '·> <: ion du dl · -' -> rls-,.-Irato do N-méthyiamino-l, nltro-2,

- '· 6-A ^ u'!. No; io? R '\'¹P^,'Dr, cⁱ~ 'ï "bonzène"

The preparation reactions can be schematized as follows

<img file="LU50348A1_D0024.tif" />

Br (Cil 1 Br ZO

<img file="LU50348A1_D0025.tif" />

-ft / W so ^ yœ) .- &lt;% o ^ ^X

->

'NO.

NLICIL

II ·

-ft

HCl

NO.

I

NIICÏI, ft i

/, · L6o &lt;- “·^1ί'^{, ΓΡ} Phnsn * Preparation of N-methylamino-l, nitro-2; (NOT^t-benzèn '.' Y '.- Y- - -' • i. - - ru ifonyl, N'-ùJ- bromobexvl) -amino-4 „benzene” '. 0.05 mol of potassium salt of Y '/, · / / - -4- W "3j ^: r-metbylatnino-l, nitro-2, N'-benzenosulfonylarnino-4 , benzene · - -Y'ï jL? . .vMawv;

-S

- fe (that is to say 17.25 g) in 40 cnr-of dimethylforraamide · 0.1 mole of © 1,6-dibromoh.exane (i.e. 24.4 g) is added and rX '' ··· · -. , ·; ““> <: · <<_x ·· · ► 'x «· the reaction mixture is kept 30 minutes at 80^eC ”We are cool, pour into 3 °° cnr of water and wring 23.3 g.

f \ I ** '* ?:

dhm gross product which, after fractional crystallization · £ &lt;? ;;

'·'· ^v&lt;^;;: ':; pÿ $ / '• · - ίχ - on the one hand, 17 g of N-metliylamino-l, n ± tro-2, (li'benzènesulf onyYX in absolute alcohol, provides ï

N * -W-bromolioxyl) -amino-4, benzene which melts at 101 ° C and whose 4 $ ^ analysis results are as follows S 1

O Analysis

Calculated for ^VS19^H24^NOT3^{Br S}°4

<img file="LU50348A1_D0026.tif" />

Λ ''

Found YY b'Y fY ". ?

48.,52 5,32 \ ·

9,18

48,30 '5,26 . 9,20 .

- on the other hand, 4 g of bis-N'-_{j (}^ i-métb.ylam ± no-4, nitro-3, ph, en z ^ -Sï benzenosulfomidohcxane, which melts at 200 * 0 and whose analysis results are as follows:

<td>analyzed</td><td>Calculated for</td><td>Find \</td>

<td></td><td>^VS32^H36^NOT6^S2°8</td><td> \</td>

<td>b "- Q î he</td><td> 55, 17</td><td> 1 55,33 - 55,12</td>

<td>¹¹ J [IH</td><td> 5, 17</td><td> 5,13 - 5,12</td>

<td> !( ^NOT</td><td>Ï2, 06</td><td> 12,17 - 12,01</td>

IJ.

>. A, 'p, li î: · î / .jj'>

'Y'; IX bA! Y i

I

U it ·. ·: - u; "&lt;'· -';

-NOT A WORD ·.

· "(.VYY • .ί ?. '·" "/ *". ¹⁷’*·

-, 2èmo - Phase »Pvhv.ro t ion of N-methylamino ~ l, nltro-2.v _; ..

(yo -bor-zèno suif on ^ l π · ~⁹-h ^;-phthalimidohGxyl.) - nmino-4, benzene. /.

0.0268 mol of N-methylamino-l, Λ nitro-2, (N'-benzonosulfonyl, N * - OJ — bromohexyl) —amino-4, benzene, are dissolved. : (that is to say 12.6 g) dan3 50 cm ^ dl dimethylformamido * We add 0.0322 molo of phthalimide, potash (ie. · ·

5.96 g) and the reaction mixture is heated for one hour,

. '3' i'- '·:

at ba ± n-ma ~ ie boiling. Pour into 400 cnr of water and add 13.8 S of crude product which, after recrystallization from ethyl acetate, melts at 149^eÇ »'Product analysis ·.

\. i · -i ·, '·. ï ·· 'obtained gives the following results t \ *':

y '' '- ^;

<td>i! He analyses 11 II</td><td>Calculated for '^vs27^H28V⁰6</td><td>· L Found 1 ^: . • 1. -. t</td>

<td>------------ ™ ίί G $ 1 ' !&gt; H # he he HN Co he ^AT 7 II</td><td>60.44 ί 5.22 10.44 '</td><td>60.50 - 60, '32 ï ¹ - 5.50 - 5.48 ' 10.4.8 - 10.47 7 A 't ··.'</td>

Ιί

JL

- 3rd phase? Preparation of N-met ^ lamino-lini'tro-2, (N * -

--- -.-V · I - L '- I · - I. Γ f II T—. . - - f Λ. ' t · - · Vi *.

bonzoncsulf onyl, N * -ûy-3ininalicxyl) -amino-4 .benzene.

\ ·' ''

To a solution of 0.0193 mole of V. phthalimide 'substituted (ie 10.37 g) in 80 cm', of propanol, on • V “· Λ · -.

add 2 g of hydrazine hydrate, then heat JO-, minutes in a boiling water bath. By filtration of the reaction mixture, ·, hot, most of the phthalhydrazide formed is eliminated.

After cooling, an orange oil is isolated by decantation which is dissolved in acetate; ethyl. This ethyl acetate solution is extr acted with semi-normal hydrochloric acid.

<img file="LU50348A1_D0027.tif" />

18, te ·.

ι. · Z.

After alkalinization of the hydrochloric phase _ry, v à la soudo ^ on essoro 3,5 {î do N-raothylamino "l, nitro-2>.

ΐ'ύ * 'λ ·; · Λ 'Λ'Λ (N'-ben • .ènosulf cnyl ,? P -éü-araino hexyl) -amino-4, benzene which melts at i30 ° c,' ·· 'Γι' "

Propanolic mother liquors, after saturation .tel with dry hydrochloric acid, provide another 2 g of _:product soughtj isolated as hydrochloride.

- 4th phase î Preparation of N-methylamino-l-ÿÿ nitro-2 dihydrochloride, (iT'-Oj-otnlnohexyjJ-àmii ^ -A "benzene", - 0.008 mol of N is heated^#-methylamino-1, nitro-2_î(NOT^î-éD-aminohexyl) -amino-4, benzene (ie 3.2 g) -;% ··; / solution in 10 cites of concentrated hydrochloric acid for te'J minutes in a water bath boiling. After cooling and φ ·· ''

Q î *; ' . ·, ** '' · addition of 10 hp^j absolute alcohol, 2 g of dichlorhy- 'te are wrung;

j drato do N-methylamino-l, nitro-2 / N * -6J-aininohexyl) -amino-A ·, · ·· - j ··,; · ;? ¹ benzene After recrystallization from concentrated hydrochloric acid added to its volume of alcohol, the product gives the analysis the following results. . ·.

<img file="LU50348A1_D0028.tif" />

-, ! ..

y ·· '.;.'. · · * Λ “tvî,;? ·; &amp;

*>? A

1$:

.'Λ% ·^:

<img file="LU50348A1_D0029.tif" />

19.g

: lg

K '·

-XT ..... · LIVE ^ΎΑ '·, · ΐ. ^ ~ · Process da>, -όρ; N'-methylamino-l> nitro-2, ί '· _., - »» · »! Ί '.) ·' '>> - 1 r-' · -h .1 · ·· <: .'_ rc,

Loc x-éac blanc do pr; \. Arabicn can be schematized in the following way, following J \ g!

·? · :: &lt;'&lt;· "te · i',

V j. · / ·. · --Te: Ί; ·

SO, CH -Cïï Br 2 ^, / 2 2

· JL.

<img file="LU50348A1_D0030.tif" />

' /^G

KN.

0^'

<img file="LU50348A1_D0031.tif" />

&lt;You.

head *? v?

SO_AT / η₂-οη₂. II¹ /° ^K^ And,

0*

<img file="LU50348A1_D0032.tif" />

KO

Nile - NIL. HO te / \

H CIL

-CJ _2XZvs_H2._VSh₂.nh₂

<img file="LU50348A1_D0033.tif" />

^SO4^H2

<img file="LU50348A1_D0034.tif" />

: Lfi • · V ". '

Ία;

<img file="LU50348A1_D0035.tif" />

- / 'J'j î Préu^not ·?. ^!: ί · - · ι of ÎI-methylamxno-1, nitro-2,. ; &lt;/. · '* ". · - J (-benzene mJ.fcnvl .î^rf- [-P-nhtalimidoethyl) -amino-4, benzene ·.

' -AT.

. • · I · * - " '

Z'étiiode n): \ / P \ '/

Cn dissolved 0.122 mole of 2-methylamino-2-nitro-2_r &lt;R *. . î o "(li'-bonzènesulf onyl, ±: '- jè-bronioethyl) -am i.no-4, bonzèno (that is to say - ÿ \ ° nL;

say 5βί »5 S) in 150 cm^-* of dimethylformamide, 5/1 "is added *

0.102 mole of potassium phthalimide (that is to say 30 g) and one i »i Z;

heat the reaction mixture for one hour in a water / boiling water bath. ”It is poured back into two liters of water and wrung out 57.5 g.

, 1 J, da K-methylaraino-1, nitro-2, (N * -benzenesuifonyl, N'- ïè-phtalimido- · / gthyl) -amino-4, benzene, which, after recrystallization in the ^;; ej toluene, background at 2l8^eC, Analysis of the product obtained gives the following results:

<td>II 15 dd Analysis H i;</td><td>Calculated for i ^VS23^H20°6^NOT4^S</td><td>Find</td>

<td>fl 1 ' He r J It c / he H i | H% he Ί i; .i $ 1 q / · * II --------------------</td><td> 57,53 4,17 11,66</td><td> 57,28 - 57,10 3,98 - 4,20 11,67 - 11,66</td>

B il é /. · '

H

It

II / 7 --ί! Μ '•^:A f "/".

, J1 'P' ^ tboé-é b). î

0.05 months of potassium salt of N-methylamino-l, nitro-2, N'-benzenesuifonyl-amino-4, benzene are dissolved

Λ (that is to say 17.25 g) dan3 50 cm of dimethylformamide * 13.97 g tlo | i-bromoétliyli5litaliinide are added and the mixture is heated for one hour at 14 ° C. After cooling, the ictionnol mixture is poured into a liter of water and a gummy product is wrung which, after three crystallizations from toluene, provides 12 g of N-methylamino-l, 2-nitro, (tallow benzene onyl, N'- pntaliaidoethyl) -amino-4, benzene which melts at 2l8^eVS, ' .

y> -j * '' • 'I · .- *' ^:'X <

'i i.ï îï'Wr iu⁴· &lt; /.

21 "" ".Λϊ · i, ι? '·'; i i. '.' .. c orect &lt;d .-- nî: r.

The::. ... t is less than that obtained by or f 'is II-m thylamin ο -1, nor tro-2, (N' -b enz ene. 1^:

Ί 'i! No-è “benzene“

I I. '.' i 'jt: .y I f ·· ::

! ί '··' ·· ''! d? ·

Cn dissolved 0.119 mole do N-methylaiaino-l, nitro-2,^h (n -bcnzenoculf onyi-ϊΓ '- -phthalimidoethyl) -amino-4 "benzene <>

(ie 57 g) hard ..; ' 350 eta^-1 do propanol. 0.238 mole of hydrazine hydrato (that is to say 11.9 g) ii; &lt;is added to this solution and the mixture is heated for one hour in a boiling water bath. After the reaction mixture has cooled to room temperature, the phthalhydrazide formed is removed by filtration.

The propanolic solution is then concentrated 1 00 c ../ approximately. By cooling, 30 g of the product are obtained. ii. tse ^ üu s ... is. form of an oil that slowly crystallizes. After rocriotallisa tion in an ethanol-water mixture, the product melts · at I1C^VS'Û3 The following results are obtained on analysis' î ey,

N ÿ,

<img file="LU50348A1_D0036.tif" />

Found = Bi | 11 11 U II

Kl lS · t * yh

16.

of

51,41 - ' 51,37

5.19 "5.28 l6.0i - 16.02 '" It

II

II

II

II

I!

II

II

II g

- Pènso 8 Preparation of N-niethylaniino ~ l, nitro-2, y '~ fi i reé Uiyir-pilno-4.benzène ₀ ’ \

0.0074 nolu of A is dissolved at room temperature^T-methyIamino-l, nitro-2, (ïi^f-benzene tallow onyl, N'- p) -aminoethyl) -amino-4_Pbenzcne (i.e. 2 „6 g) in 15 cm³ of sulfuric acid "The reaction mixture is left for 4 hours at 15 ^ 0 and then lo verso dan.3 150 cm '' - * ice cold. We make /

alkali. with soda. After a night in the cooler, we^{Z /}

AT

Have

22 »« · &lt;.... ore 1,5 £ do N-métl ·; '!: · .d bonzèno which, after r- -ris benzene, melts at I-IO' - 'C. The following r'-ùlLata:

in.o-1, nitro-2, N¹ -pV-amino-thylamino-4, À .isation in the cyclohexane mixture -. &lt;·;

ià / _x i. the light obtained gives the analysis the

<img file="LU50348A1_D0037.tif" />

tntuignn nr process ipmtion of N '~ methylamtro-l, nitro-2,

ΪΓ '- f5— "m * Hiyj n" i j.no-è. - b ^ nzènO'Ô

The preparation reaction can be schematized as follows:

<img file="LU50348A1_D0038.tif" />

NO

AT

H CIL

<img file="LU50348A1_D0039.tif" />

bound

t. , 7 Î.

•

;. · Ï.

. î / r

B

'.; w • $ * &lt;·' LL

The mixture of 0.30 mole of

N-méthylaniino ~ ljniti'o-2, 4-atnino_rbenzene (i.e. 50 g), £ * ·;

ί / do 250 cm of water and do 17 g of lime carbonate. We introduce ίΐ-,

K.1! .Ï 'little by little, ot with stirring, 0.330 molo hydrobromide; / àb!

jli-bromo ethylamino (that is to say 67.6 g) in solution in 150 cm3 of acue The addition finished, the y · 'is again heated for one hour at reflux and it is wrung dry. The filtrate is cooled to 0 * CO ot 60 g of the product are wrung in the form of a monohydrobromide. · / / '' Ά. Α'77_r;

<img file="LU50348A1_D0040.tif" />

23....

:, tense "Or discor \ &lt;m · abromhydrato in the amount of acxite water, one would celution using methyl-isobutÿlacétono lice 'to eliminate a louse of the initial product, which did not react" On reri alkali: the aqueous phase with sodium hydroxide ot 40 g of X are filtered - ::. é J./la:..J...c~l,nitro-2,N^e- -aminoeth.ylamino-4, benzene which splits to 110^SVS_U

E7?. 'FPIÆ IX

We prj_?are the following dye composition: ethylnniino-1, nirro-2, N'— jS -aminoethylamino-4, benzene / monob rc:.: h yd race ..0..0..00..0.0. .. · “· .... ·. · *” ”.“ ”· * · .. 0.73 g

/...cool lauric oxyethylenated to 10.5 moles of oxide

vs. * e txiyleno 00.000..0..00 ... 0 ........ 0.0.0., 000000 .., 5.00 g

GO, ÿïa .. in solution 2 uq_oSop. .................... pH 8 mU q OS. po .... ...... ... .. uo. 00. 000000040000. 100 g * This composition is applied to z ... turol3 light brown hair, left to act for 10 minutes, rinsed and washed with shampoo.

We get a tointuro violino foncoo "

EXAMPLE X

The following dye composition is prepared t 'j / ~ X- / A-hydroxyethylamir oi, 2-nitro-diethylaminoethylamino4, benzene / dihydrochloride ...................... ... o 0.2 ^ 6 g

K- ß-ominoé thylamino-1, nitro-2, methyl-4, amino-5, benzene

.........................'........................ 0.042 g

Lavriquo oxyethylenated alcohol with 10.5 moles of oxide t *. “C. ûlij / IcflO 0 · Ο“ Ο ··· β4 * 4 · ΟΟ0 “40 · * 464Ο ***** 4 ** 4 **** 4 2 on gentle solution ηοΐΊπαΙ q“ s_#p. ·· “· * ·“ pH 9 J q © s ”p · ööo“ eoe ”* 4 *“ ** e ”* fcoo <> oe ··············· 100 g

This composition was applied to natural hair $ 100 white ”, left to act for 10 minutes, rinsed and washed with shampoo.

We get a reddish blonde_o \ / '' / / 4 4/4 4 i .'s ♦ linked · '· V^s {· ”· F- ·;

i · · «r:

r &lt;..

24,

p ..... ü ___ ZS

We prop;: · '- 1 :. following dye composition ί hydroxyethyi-- P r.-l, nitro - ?, Η'-méthyi, Β'- P enclliylaüiinoail / i '... ./.0-4,bonzene7dichlorhyd_ te .... 0.304 g noeth / 1: ..slue ... ..itrw-2, methyl-4, amino-J, cor ...... j · * .ο .. · .. ···. ·, · .., ^ .. ·. · * 0.042 g .lier ;! lauri ". uo oxyétZ.ylé.;. é to 10.5 moles of ethylene oxide. .......... .............................. 2 g

CO "Zta_z. in mild solution once normal qs ..... · .. · "pH 7 ··

1-zû.Ll Q o C po Ο ο “* 0ΛΛ“ Λβ ^ ”οα · οβ4 ** · 0 ···· Ο * ά ··· &lt;β4 ···· ό“ · 100 g

This composition is applied to heavily discolored hair, left to act for 10 minutes, rinsed and washed with shampoo * A dark copper-colored mahogany is obtained.

Pii

Gn prepares the following dye composition I £ ~ H-born tlrylnmino-l, n ± tro-2, N '-aminobutylamino-4, benzene / dihydrochloride .................. ....... 0.233 g p-aminoethylamino-1, nitro-2, methyl-4, amino-5, benzene ........... J ............ ..... ............ 0.052 g

Lauro-oxyethylenated alcohol with 10.5 moles of oxide d ¹ ethylene ........................................ 2. g

CO „ITa in solution twice normal qs ........ pH 9

2

Water qs ....................................... 100 g

This composition is applied to natural lûûÿj white hair, left to act for 10 minutes, rinsed and washed with shampoo, a pearly dark blonde is obtained,

ΒΡΡΡΡϊ.Β XXTX \ '

Or prepare the following dye composition S

/.V ominoé thylamino-1, nltro-2, amino-4, benzene *? hydrochloride .................................. 1.2 g

Laurylo-oxyethylenated alcohol containing 10.5 moles of ethylene oxide · ".". "" * *. ·· .. · ". ·. *. * ·." · 2 g

GO Ha on solution twice normal qs "...", pH 8 3 2, ·

Bau qs ...................................... 100 g /

!

• */· · &amp;

Ί> / <

!

I

25.Cr. apply · this composition to nat'U hair - .Is lOOp blans ... c; the.;. . this act 10 minutes, rinse and 'in wash with ohampoo. On targeting a red dye

„. Slightly purple background .C / O χτν

The following dye composition is prepared 1 / h -:> tétliylainiuo-l, γ.Λ ùrc-2, aminohexylamino-yA, benzene / dihydrochloride .................... ............... 1.5 g

Oxyéfchyléné Iauric alcohol with 10,5 moles of ethylene oxide .................................... ..... 5.0 g

C0_oKa_Q we solve twice normal qs_e ........ pH ß h at tp s «p. ........... .........-000. 100g

This composition is applied to natural IOO / white hair, left to act for 10 minutes, rinsed and washed with shampoo. "A very powerful violet dye is obtained.

₍ EXAMPLE XV • The following dye solution is prepared:

/~Z,m?tl'yl.mino-l,niLro-2jh^TI- // - (methyl, ß -hydroxyethyl) c.miuopropylamino-4, bonzèn27dichlorhydrate ............ 0.50 g

Oxyethylenated auric alcohol containing 10.5 moles of eahylene oxide ................................... ......... 5.00 g

C0 "Na_o in solution twice normal q "sp <> ............ pH 9

Ll Q 4 3 0 JD 4 100 Q

We apply this composition on. light brown hair, leave to act for 20 minutes, rinse and wash or shampoo. We get a deep purple color,