DE1768464A1 - Nitroparaphenylenediamine offshoots, processes for their production and their use in coloring agents and processes for coloring with them - Google Patents

Description

PATENT AGENCIES ^ 768464

PROF. DR. DR. J. REITSTÖTTER DR.-ING. WOLFRAM BUNTE

DR. KARL GEORG LÖSCH

D - 8OOO MUNICH 13, BAUERSTRASSE 22. FERNRUF (O811) 37 68 83

P 17 68 464.9
Pa.L ¹ OREAL, Paris

Munich, February 27, 1970 M / 9241

Nitroparaphenylenediamine derivatives, processes for their preparation and their use in dyes and methods of dyeing with them

The invention relates to a method for producing Compounds of the formula

(D

Documents (Art. Ί ι \ Abs,? No. ι uu - c ^ s Alteruriawet. V.4.

109833/2018

wherein R is hydrogen, a substituted or unsubstituted one lower alkyl radical, especially a substituted or unsubstituted hydroxyalkyl, Carooxyalkyl, carbamylalkyl or aminoalkyl radical, whose amino nitrogen atoms belong to a heterocycle can means? Z hydrogen, a radical

R ¹ or a radical OC-R "(in which R ^{1 is} hydrogen, a methyl group or an N0 ₂ group and R" is a lower alkyl group), at least one of the radicals Z and R being hydrogen; R, a lower alkyl, lower hydroxyalkyl, lower alkoxyalkyl radical or a chain - (CH ₃ ) - N * ²

(where η is an integer from 2 to 6 inclusive and R1 and R1, which are the same or different. are hydrogen, a lower alkyl or lower hydroxyalkyl radical, where the nitrogen atom which is adjacent to R2 and R- are with them can also form a heterocyclic radical, such as a morpholine or piperidine radical), the alkyl radical of R, R ", R _{1, R 3} and R ₃ having 1-6 carbon atoms, and their corresponding quaternary derivatives, according to which process an amine of the formula R ₁ -NH ₃ (in which R 1 has the meaning given above) with a compound of the formula (II)

(H)

109833/2018

(where R has the meaning given above, X is halogen, preferably chlorine, D is and Z ^{1 is} a group

R ¹ or a group OC-R ", wherein R ¹ and R"

have the meaning given above, represents) is reacted, whereupon, if you want to obtain a product in which Z is hydrogen, an acid hydrolysis of the product obtained Product is carried out.

Any quaternization of the compound of the formula ^w (I) takes place in a conventional manner by means of a quaternization agent such as methyl sulfate or an alkyl or aryl halide.

The invention also relates as a new product to the Compounds of general formula (I) in which

1) Z = H

.R ₂

R ₁ = - (CH ₃ ) -N ^ (where R ₀ and R-. The above

R have given meanings ³ )

and R = aminoalkyl, optionally its amine function

can be substituted

2) Z = H

R 1 = alkoxyalkyl
R = H or alkyl

3) R = H

1098 33/2018

"" TC "™

Z = SO

R ¹ (where R ^{1 has} the meaning given above)

R = - (CH ₀ )

(where R ₀ and R-, the above-

3 have given meanings)

and the corresponding quaternary derivatives when these compounds have a tertiary amine function.

The compounds defined above are for dyeing keratin fibers, especially of hair, particularly suitable dyes.

They have a good affinity for the fiber, good resistance to light and weathering and a great solubility in water.

The invention also relates to a colorant for keratin fibers, especially for hair, which is characterized in that it contains at least one colorant such as that in solution
is defined above.

The colorants according to the invention preferably exist
from simple aqueous solutions, the pH of which is generally between 4 and 10, preferably between 7 and 10.

These colorants can be various, usually, for
Ingredients used in hair coloring, such as organic solvents, thickeners, detergents, emollients, perfumes and varnishes, contain. The dyes according to the invention can also be used with one another
and with other dyes, such as nitrided dyes,

109833/2018

Azo, anthraquinone dyes !! or with each other Type of dyes commonly used for hair coloring.

Carrying out staining with these colorants does not require the addition of an oxidizing agent. The contact time with the hair can vary within wide limits, but is preferably 5 to 30 minutes. The application temperature of the colorants mentioned can also be varied, but they are preferably used at room temperature. The concentration of dyes according to the invention can also be varied remarkably, but this concentration is preferably 0.1 to 3 / o.

The invention finally relates to a method for dyeing hair, characterized in that one on the hair a dye, as defined above, applies for a time of 5 to 30 minutes, the Washes, rinses and dries hair.

In order to explain the invention, some will be given below Process for the preparation of compounds of formula (I) and the use of said compounds for coloring hair.

109833/2018

Example 1;

Production of l-HexvIamino-2-nitro-4-antinobenzene

0.1 mol of 2-nitro-4-acetylamino-chlorobenzene is dissolved
(21.5 g) in 2 moles of hexylamine (202 g). The mixture is refluxed for 8 hours; the excess of aliphatic amine is eliminated in vacuo. The oily residue obtained in this way is treated with 200 cm of an η hydrochloric acid solution which has ^{cooled to 0 °} C., and it is treated
centrifuged and washed with alcohol and 15 g of practically pure chlorohydrate of 1-hexylamino-2-nitro-4-aminobenzene are obtained. This product results from the deacetylation of a part of 1-hexylamino-2-nitro-4-acetylaminobenzene, which was formed after substitution with chlorine. After treatment with an ammoniacal solution, this chlorohydrate gives 12.8 g of 1-hexylamino-2-nitro-4-aminobenzene, which melts at 75 ° C. after recrystallization in toluene.

The analysis of the product obtained shows the following results.

analysis

C % K % N %

calculated for
^C 12 ^H 19 ^N 3 ° 2 found 60, 84 60.76 6O.95 - 8th, 19th 8.01 8.22 - 17th 71 17.72 17.69 -

109833/2018

Example 2;

Production of l-N-ß-diethylaminoethylamino ^ -nitro-4-acetylamino-benzene

0.065 mol (14 g) of 2-nitro-4-acetylamino-chlorobenzene (this derivative, which melts at 147 ° C, is obtained by heating 2-nitro-4-aiaino-clilobenzene in acetic anhydride) are in 1.04 mol Ν , Ν-diethylethylenediamine (12 g) dissolved. It is heated for three hours at 140 ° C and then the excess of aliphatic * diamine chased away in vacuo. The oily residue is ΜΛ

8 cm acetic anhydride treated to make the aromatic primary amine, which was partially deacetylated in the course of the reaction, to acetylate again. One pours Water that is adjusted to pH with the help of an i? Atrium solution of 12 was made alkaline, and the expected product was extracted using methyl isobutyl acetone. The solution of methyl isobutyl acetone is extracted using a 0.25 η hydrochloric acid solution. The aqueous hydrochloric acid phase is alkalinized to a pH of 12 and 10 g of 1-N-ß-diethylaminoäthylaiaino-2-nitro-4-acetylamino-benzene, that melts at 98 ° C are obtained.

Example 3;

Production of 1H-ß ~ diethylaminoethylamino-2-nitro-4-amino-benzene ,

The product prepared according to Example 2 becomes a hydrochloric acid Subject to ehydro Iy se. 1-N-ß-diethylaminoethylamino-2-nitro-4-aminobenzene is obtained, that melts at 65 C.

10983372018

Example 4;

Production of 2-methyl-ß- / N- (nitro-4-acetylamino) phanyl / -aminoethyl-methyl-diethylammonium sulfate

IN-ß-Diethylamino-2-nitro-4-acetylamino-j3enzene is obtained as described in Example 2. 0.017 mol (5 g) of this compound are dissolved in 50 cm chlorobenzene at 40 ⁰ C. Gradually, 0.019 mol of methyl sulfate (1.8 cm) are added with stirring and the reaction mixture is kept at 40 ° C. for four hours. After cooling, 6.36 g of the expected quaternary ammonium salt, which melts at 133 ° C., are obtained. After recrystallization in alcohol, the analysis of the product obtained shows the following results:

Analysis calculated for found

C / o H / o N / o

Example 5:

W. Production of l-N-ß-diethylaminoethylamino-2-nitro-4-N'-methylamino-benzo1

0.011 mol (5 g) of monochlorohydrate of lN-ß-dietnylaminoethylamino-2-nitro-4- (N'-mettiyl-N'-benzenesulfonyl) aminobenzene, the preparation of which is in Example 10 of the patent ... (on the same day as the present one Application filed by the same applicant) are gradually ^{added to 30 cm of sulfuric acid at 0} ° C. with stirring. After complete dissolution, the reaction mixture is heated for 6 hours at room

^C 16 ^H 28 ^N 4 ° 7 ^S. 45 .94 - 45 , 89 45, 71 6th .76 - 6th # 69 6, 67 13th , 11 - 13th , 10 13, 33

109833/2018

1768A64

left to stand at temperature, poured into 300 cm of ice water, alkalinized by means of a 5 η sodium solution and 3.1 g of l-N-ß-diethylaminoethylamino-2-nitro ^ -N'-methylaminobenzene are obtained, which melts at 74 ° C.

Example 6:

Preparation of 1-N-fl-Hydroxyethylamino-2- nitro-4-N'-methylaminobenzene

0.0288 mol (10.1 g) of INS-hydroxyethylamino ^ -nitro ^ - (N ^l -methyl-N ^I -benzenesulfonyl) -aminobenzene, the preparation of which is in Example 12 of the patent .... (on the same day as the present application deposited application of the same applicant), are dissolved in 20 cm previously heated to 95 ° C concentrated hydrochloric acid. It is heated for one hour in a boiling water bath, 20 cm of water are added, it is ^{cooled to -IQ 0} C and 5.5 g of practically pure monochlorohydrate of 1N-ß-hydroxyethylamino-2-nitro-4-N'- methylaminobenzene-. After treatment with a normal sodium solution, this chlorohydrate gives 4.5 g of 1-N-ß-hydroxyethylamino-2-nitro-4-N ^l -methylaminobenzene, which melts at 123.degree.

Example 7:

First process for the preparation of hydrochloride from 1-N- </ ^> -Methoxvpropvlamino-2-nitro-4-N'-methylaminobenzene

0.02 mol (7.58 g) of 1-Nf ^/ '-methoxypropylamino-2-nitro-4- (N'-methyl-N'-benzenesulfonylaminobenzene, the preparation of which is described in Example 13 of the patent .... (on the same

109833/2018

Days as the present application (filed application by the same applicant) has been described, are dissolved in 35 cm of sulfuric acid at ⁰ ° C. The reaction mixture is left to stand for 10 hours, it is poured onto 500 cm of ice water, made alkaline with 5 η sodium hydroxide and the desired product is extracted with the aid of methyl isobutyleetone. After washing with water and drying the methyl isobutyl acetone solution using sodium sulfate, the solvent is evaporated in vacuo. The oily residue is dissolved in 20 cm of propanol. After bubbling dry hydrochloric acid through the propanol ice solution, 5.10 g of hydrochloride of 1-N-j / '- methoxypropylamino-2-nitro-4-N'-methylaminobenzene, which melts at 115 ° to 120 ° C. with decomposition.

The analysis of the product obtained shows the following results:

analysis calculated for
^C 11 ^H 17 ° 3 ^N 3 ' ^HC1 found 48.09 C % 47.91 47.99 - 6.70 H % 6.53 6.56 - 15.12 N % 15.25 15.08 - Example 8:

Second process for the preparation of hydrochloride of 1- (A-methoxypropylamino-2-nitro-4-N ^t -methylaminobenzene

0.0071 mol (2 g) 1- \ A-methoxypropylamino-2-nitro-4- (N-

109833/2018

- ii -

methyl-N-acetyl) aminobenzene, the production of which is described in Example 14 of the patent .... (application filed on the same day as the present application of same applicant), are concentrated for 1 1/2 hours in a water bath in 20 cm Hydrochloric acid, to which 40 cm of water was added, heated. After cooling, the reaction mixture becomes diluted, made alkaline by means of a 5 η sodium solution and 1.61 g of 1-O ^ -Methoxypropylamino-2-nitro-4-N-methylaminobenzene are obtained, which melts at 52 ° C after recrystallization in benzene. After solving this The product in propanol and bubbling with dry hydrochloric acid gives the corresponding chlorohydrate.

Example 9: -

Production of l-N-ß-D: Läthylaminoäthylamino-2-nitro-4- (N'-ß-diethylaminoethyl) -aminobenzene

0.0387 mol (19 g) 1-N- (ß-diethylaminoethyl) -amino-2-nitro-4- (N'-ß-diethylaminoethyl-N'-benzenesulfonyl) -aminobenzene are dissolved in 76 cm of concentrated sulfuric acid, the temperature being kept at 40 ° C. That Reaction mixture is for 4 hours at this temperature

3 door held, then it is in 600 cm of ice water poured, it is alkalinized with 5 η sodium hydroxide and the expected product extracted using methyl isobutyl acetone. After the methyl isobutyl acetone solution washed and dried over sodium sulfate, the solvent is evaporated in vacuo and 12 g practically pure 1-N- (ß-diethylaminoethyl) amino-2-nitro-4-N * - (ßdiethylaminoethyl) aminobenzene are called this way

109833/2018

17884S4

separated a purple oil.

Analysis of the product obtained shows the following results;

analysis calculated for
^C 18 ^H 33 ^N 5 ° 2 found 49 C / o 61.53 61.54 - 61, 25th H % 9.40 9.42 - 9, 15th N % 19.94 20.10 - 20 Example 10: of 1-N-ß-aminoethylaraino- Production of monochlorohydrate 2-nitro-4-benzenesulfonyl benzene

0.1 mol (31.2 g) of 2-nitro-4-benzenesulfonylaminochlorobenzene in 2 mol of ethylenediamine (120 g) in the presence of 50 cm of water dissolved. It is refluxed for 22 hours worked, the excess of ethylenediamine in a vacuum

hunted, the oily residue dissolved in 200 cm of a 2 η hydrochloric acid solution at 50 ° C, ^{cooled to 0} ° C for 24 hours and there are 25.7 g of monochlorohydrate of 1-N-ß-aminoethylamino-2-nitro-4-benzenesulfonylaminobenzene obtained which, after recrystallization in a normal hydrochloric acid solution, melts at 237 ° C. with decomposition.

Analysis of the product obtained shows the following Results:

109833/2018

analysis

calculated for ^G 14 ^H 16 ° A ^S 1 ^HC1

found

N / ο
Cl %

15.03

8.59

15.08-15.13 8.72-8.78

Example 11:

Preparation of the dichlorohydrate of 1-N-ß-aminoethylamino-2-nitro-4-aminobenzene

0.1 mol of monochlorohydrate of l-N-ß-aminoethylamino-2-nitro-4-benzenesulfonylaminobenzene (37.2 g), which was produced in Example 10 of the present application, are placed in a boiling water bath at 500 cm "for three hours. concentrated hydrochloric acid. After cooling, 26 g of dichlorohydrate of 1-N-ß-aminoethylamino-2-nitro-4-aminobenzene are added obtain.

Example 12:

Production of 1-NC ^A -Hydroxypropvlamino-2-nitro-4-N'-methylaminobenzene ■

0.0075 mol (2 g) 1-N- ^ -hydroxypropylamino-2-nitro-4- (N-methyl-N-acetyl) aminobenzene, its preparation in example 16 of the patent .... (application filed on the same day as the present application of the same Applicant) has been described, are concentrated for one hour in a boiling water bath in 20 cm Hydrochloric acid mixed with 40 cm of water is heated. It is cooled using a 5 η sodium solution

109833/2018

alkalinized and 1.6 g of 1-NJ / '- hydroxypropylamino-2-nitro-4-N ^l -methylaminobenzene are obtained, which melts at 107.5 ° C. after recrystallization in toluene.

The analysis of the product obtained shows the following results:

analysis calculated for
^C lo ^H 15 ° 3 ^N 3 found 53 , 23 C % 53.33 53.37 - 6th , 74 H ^J / o 6.67 6.65 - 18th , 87 N % 18.67 18.72 - Example 13:

Preparation of the dichlorohydrate of 1-N-ß-diethylaminoethylamino ^ -nitro ^ -N'-ß-hydroxväthylantinopenzene

0.0106 mol (5 g) monochlorohydrate of 1-N-ß-diethylaminoethylamino-2-nitro-4- (N'-ß-hydroxyethyl-N'-benzenesulfonyl) aminobenzene, the preparation of which is described in Example 17 of the patent .... (on the same day as the present application deposited application of the same applicant) are heated for one hour in a boiling water bath in 10 cm of concentrated hydrochloric acid.

3 The reaction mixture is poured into 100 cm of ice water, alkalized using a 5 η sodium solution and the desired product is extracted using methyl isobutyleetone. After washing with water and drying over sodium sulfate, the methyl isobutyl acetone solution becomes the solvent evaporated in a vacuum. The oily residue will

109833/2018

brought into solution in 20cm propanol »After blowing through 3.5 g of dichlorohydrate of 1-N-ß-diethylaminoethylamino-2-nitro-4-N-ß-hydroxyethylaminobenzene are obtained from dry hydrochloric acid through the propanol ice solution, after recrystallization in a mixture (propylene alcohol, concentrated hydrochloric acid) with decomposition Melts at 178 ° to 183 ° C.

The analysis of the product obtained shows the following results:

analysis calculated
^C 14 ^H 2A ° for
3 ^C1 22 - found 45 , 69 C% 45.52 45.64 - 7th , 25 H % 7.04 7.11 - 15th , 23 N % 15.17 15.38 -

Example 14s

The following remedy is made;

- Trichlorohydrate of 1- (N-ß-diethylaminoethyl) -amino-2-nitro-4- (N ^l -ß-diethyl-

aminoethyl) aminobenzene 0.4 g

- Isooctylphenylpolyethoxyethanol 1.5 g

- NH ^ OH up to a pH value of 9

- fill up with water to 100 g

This agent is applied to natural "light brown" hair; it is allowed to act for 10 minutes and a greyish purple-red coloration is obtained.

109833/2018

1768484

Example 15;

The following means are made:

- 1-N- i "-Methoxypropylamino-2-nitro-4-N ^l methylaminobenzene 1.2 g

- Isooctylphenylpolyethoxyethanol 1.3 g

- Sodium carbonate up to a pH value of ..... 9

- fill up with water to 100 g

This agent is applied to natural "light brown" hair; it is left to act for 10 minutes, rinsed and washed with a shampoo. A greyish-tinged purple color is obtained.

109833/2018

Claims (1)

where R is hydrogen »a substituted or unsubstituted lower alkyl radical» especially a substituted or unsubstituted hydroxyalkyl- * carbamylalkyl- · »carbamylalkyl or alinoalkyl radical, the amino nitrogen atom of which can belong to a heterocycle» means? % Hate substance * a radical or a radical QC-R "(in which R ^{1 is} hydrogen» an ethyl group or an NO ₂ group and R ¹ 'is a lower alkyl group) »where at least one of the radicals Z and R is hydrogen; R _{1 is} a lower alkyl group. »Lower hydroxyalkyl, lower alkoxyalkyl radical or a Chain - < (where η is an integer of · *% ^{L par} · ^a * ■ "18 - 2 to 6 inclusive _{and R 2 are} ^{un (} ^ ^ 3 * ^ i @ are identical or different i hydrogen «denote a lower © AJ, kylqder lower hydroxyalkyl radical, the nitrogen atom *! the su R" and R_ denichb ^ rfc i§t _# them also Rait a heterologous ^ ylclischtg radical such as a morpholine or Piperidinradikäl "bildenktenn) difsteli wherein the alkyl group VQN B _f R '% R _1, R ₂ and U ~ l-§ carbon atoms, characterized in _{# n} NCT ^ (where R ₁ , n, R ^ and R ₃ 3 the ob, © »i interpretations Traben ) and R == Aminoalkyl, whose anti-hydrogen he material if can be substituted, mean" 2, New chemical compounds of the general formula (I), in which ZS-H R, = alkoxyalkyl - R = H or alkyl mean. 3, New chemical compounds of the general formula (I) ₄ , in which R * (where R has the meaning given above) 109833/2018 ^R i = (CH ₂ ) _n - n: .R, "R- (where R ,, n, R ₂ and R, have the meaning given above) mean, and the corresponding quaternary derivatives, when these compounds have a tertiary amine function. 4. Process for the preparation of compounds of the formula (I) (D NHR _n wherein R is hydrogen, a substituted or unsubstituted lower alkyl radical, especially a substituted or unsubstituted hydroxyalkyl, carboxyalkyl, carbaraylalkyl or aminoalkyl radical, its amino nitrogen atom to a heterocycle can belong to; Z hydrogen, a radical R ¹ or a radical OC-R "(in which R ^{1 is} hydrogen, a methyl group or an N0 ₂ group and R" is a lower alkyl group), where at least one of the radicals Z and R is hydrogen; R, a lower alkyl, lower hydroxyalkyl, lower alkoxyalkyl radical or a 109833/2018 Chain - (CH ₉ ) - N. £> ΓΙ .R. R. (where η is an integer of and R ₃ the same is 2 to 6 inclusive and
or are different, are hydrogen, a lower alkyl or lower hydroxyalkyl _{radical, where the nitrogen atom which is adjacent to R 9} and R ~ can also form a heterocyclic radical, such as a morpholine or piperidine radical, with them, where the Alkyl radical of R, R ", R ,, R ₉ and R _{3 has} 1-6 carbon atoms, and their corresponding quaternary derivatives, characterized in that an amine of the formula R ₁ -NH ₉ (in which R 1 has the meaning given above ) with a compound of the formula (II) (in which R is as defined above, X is halogen, preferably chlorine, and Z ^{1 is} a group ■ R ¹ or a group OC-R ", wherein R 'and R "have the meaning given above, represents) is implemented, whereupon, if you have a product in which Z is hydrogen is to obtain, an acid hydrolysis of the reaction product is carried out and the product obtained is optionally quaternized if a quaternary derivative is desired. 109833/2018 ORfGiNAL INSPECTED " ²¹ " 17684B4 5. Colorants for keratin fibers, especially for hair, characterized in that it is at least in solution a compound according to claims 2, 3 and 4 contains. 6. coloring agent according to claim 5, characterized in that that, among other things, it is commonly used for hair coloring used dyes, such as nitrated dyes, azo or anthrachxnone dyes. * 4 | 7. Colorant according to claim 5, characterized in that its pH is 4 to 10, preferably 7 to 10, is. 8. coloring agent according to claim 5, characterized in that that, among other things, thickeners, detergents, Contains emollients, perfumes and varnishes. 9. A method for coloring hair, characterized in that that a dye according to the claims can be applied to the hair 5 to 8 for a period of 5 to 30 minutes applies, washes, rinses and dries hair. ™ 212 / V. 109 8 3SJiZJM *