DE1619612B2 - NITRODYING MATERIALS, THEIR USE AND METHOD OF MANUFACTURING THEREOF - Google Patents

Description

in which R is CH ₃ or CH ₂ CH ₂ OH, R 'is hydrogen or CH ₃ and η is an integer between 1 and 4 inclusive.

2. 1 - (fi - hydroxyethyl - amino) - 2 - nitro-4 - (N - methyl - N - carboxymethylamino) - benzene monohydrochloride.

3. 1 - methyl - amino - 2 - nitro - 4 - (N - carboxymethylamino) benzene monohydrochloride.

4. Process for the preparation of the dyes according to claim 1, characterized in that one. by reacting l-amino-2-nitro-4-N-methylaminobenzene with a chloroacylamide of the formula C1 (CH ₂ ) "CONH ₂ , where η denotes the number 1 to 4, a carbamylalkyl radical is introduced into the secondary amino group in the 4-position , the l-amino-2-nitro-4- (N-methyl-N-carbamylalkylamino) -benzene obtained with / f-chloroethyl chloroformate to the ß-chloroethyl ester of the corresponding N-carbamylalkyl compound, then the amide group by hydrolysis with hydrochloric acid the compound obtained is subjected to alkaline hydrolysis for the purpose of converting the chloroethyl ester group into the / I-oxyethyl group and then converted into the monohydrochloride by acidification with hydrochloric acid or l-methylamino-2-nitro-4-aminobenzene with a chloroacylamide of the formula

C1 (CH ₂ ) "CONH ₂

in which η denotes the number 1 to 4, and in the N-carbamylalkyl compound thus obtained the acid amide group is split off by hydrolysis with hydrochloric acid or by reaction of 1 - Amino - 2 - nitro - 4 - (N - methyl - N - carbamylalkylamino) benzene, in which the alkyl radical is 1 to Contains 4 carbon atoms, with p-toluenesulfonyl chloride primary amino group blocked, then the free hydrogen of this amino group by action replaced by dimethyl sulfate in a basic medium for the methyl radical, then the one before introduced tosyl residue by the action of conc. Splits off sulfuric acid and finally by hydrolysis with conc. Hydrochloric acid splits off the acid amide group.

5. Use of the compounds of claims 1 to 3 for coloring hair.

NH-R

Λ-

NO,

R'-N - (CH ₂ ) "- COOH

in which R is CH ₃ or CH ₂ CH ₂ OH, R 'is hydrogen or CH ₃ and η is an integer between 1 and 4' inclusive, a process for their production and their use for dyeing hair. As representative representatives of the above-mentioned nitro dyes are z. B. named the following compounds:

l-methylamino-2-nitro-4- (N-carboxymethylamino) -benzene · HCl,

l-methylamino-2-nitro-4- (ß-carboxyethylamino) -

benzene · HCl,
l-methylamino-2-nitro-4- (N-methyl-N-carboxymethylamino) -benzene · HCl,

l - (/? - Hydroxyethylamino) -2-nitro-4- (N-methyl-N-carboxymethylamino) benzene · HCI.

The new dyes can be used to advantage wherever nitro dyes are used is common, so preferably for dyeing keratin-containing materials (see. DT-PS 16 17 693).

From the French patent specification 11 37 929, the DT-AS 11 70 583, the Swiss patent specification 3 51357 and British Patent 8 67 220 are already known nitro dyes that are part of one of the Amino groups of the nitro-p-phenylenediamine carry a carboxymethyl group. It is already known that these compounds are suitable for coloring keratin fibers. However, you have that Disadvantage that in the pH range in question for their application, there are hardly any darker nuances can be achieved and practically no shading effects due to pH changes from the acidic to the alkaline range can be achieved.

The new dyes avoid these disadvantages, with them even darker ones, tending towards blue Color nuances are achieved, they are in a wide pH range, preferably between pH 3 and pH 10, applicable, and when the pH value changes from an acidic pH to an alkaline pH, a occurs clear deepening of the color nuance.

The process for the preparation of the compounds according to the invention is characterized in that by reacting l-amino-2-nitro-4-methylaminobenzene with a chloroacylamide of the formula C1 (CH ₂ ) "CONH ₂ , where η denotes the number 1 to 4, introduces a carbamylalkyl radical into the secondary amino group in the 4-position, the 1-amino-2-nitro-4- (N-methyl-N-carbamylalkylamino) -benzene with / i-chloroethyl chloroformate to / f-chloroethyl ester of the corresponding N-carbamylalkyl compound reacted, then by hydro-

lysis with hydrochloric acid splits off the acid amide group, the compound obtained is subjected to alkaline hydrolysis for the purpose of converting the chloroethyl ester group into the // - oxyethyl group and then converted into the monohydrochloride by acidification with hydrochloric acid or 1-methylamino - ^ - nitro- ^ aminobenzene with a chloroacylamide of Formula C1 (CH ₂ ) "CONH ₂ , where η is the number 1 to 4, and the amide group is split off in the N-carbamylalkyl compound thus obtained by hydrolysis with hydrochloric acid or by reaction of 1 - amino - 2 - nitro - 4 - (N - methyl - N - carbamyl - alkylamino) benzene, in which the alkyl radical contains 1 to 4 carbon atoms, blocks the primary amino group with p-toluene sulfochloride, then the free hydrogen of this amino group by the action of dimethyl sulfate ίή basic medium against the Replaced methyl radical, then the previously introduced tosyl radical by the action of conc. Splitting off sulfuric acid and finally by hydrolysis with conc. Hydrochloric acid splits off the acid amide group.

The first-mentioned variant of the process described above, ie the reaction of l-amino-2-nitro-4-methylaminobenzene with a chloroacylamide of the formula C1 (CH ₂ ) "CONH ₂ and the subsequent reaction of the product obtained with / i-chloroethyl chloroformate and the work-up of the reaction product proceeds according to the following scheme:

HCl

II ... "■ ■ ....-; H CO-CH ₂ -CH ₂ -Cl

NO ₂

KOH

H ₃ C (CH ₂ ) "- COOH

H CH ₂ -CH ₂ OH

NO ₂

H ₃ C (CH ₂ ) ,, - COOH

NH,

NO ₂ It is advantageous to use ζ as the chloroacylamide. B. chloracetamide or // - chloropropionamide.

The second variant of the process described above, namely the conversion of 1-methylamino-2-nitro-4-aminobenzene runs with a chloroacylamide, e.g. chloroacetamide or / i-chloropropionamide according to the following reaction equation:

NH,

40

45

N

/ \
H ₃ C. (CH ₂ ) ,, -CONH ₂

Cl-CO-CH ₂ -CH ₂ -Cl / \ _N0

H ₃ C (CH ₂ ) "- CONH ₂

NH-CH,

Cl- (CH ₂ ) ,, - CO-NH ₂

55

H CO-CH ₂ -CH ₂ -Cl

N ■. .

HCl

65 NH ₂

NH-CH ₃
NO ₂

NH- (CH ₂ ) "- CONH ₂

NH-CH ₃

NO _{2 f HC1} NH- (CH ₂ ) - COOH

The last variant of the process described above can be found using the following reaction equation explain:

CH, - <O

SO ₂ Cl

SO ₄ (CH ₃ )

SO ₄ H ₂

HCl

NH,

-NO

H ₃ C (CH ₂ ) ,, -CONH ₂

H ₃ C (CH ₂ ) _n -CONH ₂

H ₃ C (CH ₂ ) ,, -CONH ₂

(CH ₂ ) _n -COOH

The compounds according to the invention are used for dyeing keratin fibers, in particular of human hair, an aqueous solution of at least one dye is applied to the hair of formula I applied, and after a period of about 15 to 40 minutes, the hair is rinsed, washed and dried. The compounds according to the invention are physiologically acceptable and have no harmful side effects on hair or skin.

; For example

Preparation of l-methyl-amino-2-nitro-4-carboxymethylaminobenzene monochlorohydrate

A mixture of 0.2 mol (33.4 g) of 1-methylamino-2-nitro-4-aminobenzene, 450 cm ^{3 of} water and 10 g of calcium carbonate is heated to the boil under reflux cooling. Gradually, with stirring, 0.214 mol (20 g) of chloroacetamide are added and refluxing is continued for one hour. After cooling, 1-methylamino-2-nitro-4-carbamylmethylaminobenzene is separated off in an amount of 40 g; after recrystallization from acetic acid and dioxane, the product melts at 167 ° C.

Analysis for C ₉ H ₁₂ O ₃ N ₄ :

Calculated:

C 48.21, H 5.35, N 25.00%;

found:
C 48.14-47.99, H 5.35-5.30, N 25.19-25.00%.

0.085 mol (19 g) of the 1-methylamino-2-nitro-4-carbamylmethylaminobenzene thus obtained are concentrated in 150 cm ³ with stirring and heating under reflux cooling. Hydrochloric acid entered. After an additional 30 minutes heating to reflux is cooled and the monohydrochloride of 1-methylamino - 2 - nitro -A- carboxy - methylaminobenzols separated g in an amount of from 16th After recrystallization from conc. Hydrochloric acid melts the product with decomposition between 163 and 166 ° C.

Analysis door C ₉ H ₁₂ O ₄ N ₃ Cl:
Calculated:

C 41.30, H 4.58, N 16.06%; found:

C 41.48-41.51, H 4.90-4.88, N 16.12-16.10%.

Example 2

Production of 1-methylamino-2-nitro-4 - (/? - carboxyäthylamino) benzene monochlorohydrate

A mixture of 0.4 mol (64 g) of 1-methylamino-2-nitro-4-aminobenzene, 900 cm ^{3 of} water and 21 g of calcium carbonate are heated to the boil under reflux cooling. Gradually 0.4 mol (43 g) / Ϊ-chloropropionamide are added with stirring. The heating under reflux is maintained for 2 hours, then the reaction mixture is filtered boiling. After the filtrate has cooled, 65 g of the crude product obtained are separated off, which, after washing with boiling toluene to remove the unreacted 1-methylamino ^ -nitro ^ -aminobenzene, melts at 157 ° C. after recrystallization from dioxane.

Analysis for C ₁₀ H ₁₄ O ₃ N ₄ :

Calculated ... C 50.41, H 5.88%; found .... C 50.24-50.48, H 5.99-5.82%.

With stirring, 0.021 mol (5 g) of the product obtained are then concentrated ^{in 25 cm 3.} Hydrochloric acid, which was ^{diluted with 13 cm 3 of} water, entered. The mixture is then refluxed for _1/2 hour, and the reaction mixture is then cooled

and g in an amount of 4.5 deposited monohydrochloride of l-methylamino-2-nitro-4 - (/ J-carboxyäthylamino) benzene separated, which melts after recrystallization from dilute hydrochloric acid with decomposition at 170 ⁰ C.

Analysis for Cj ₀ Hi ₄ O ₄ N ₃ Cl.
Calculated:

C 43.53, H 5.08, N 15.24%;

found:

. C 43.58-43.64, H 5.0 ^ -5.08, N 15.53-15.48%.

Example 3

Preparation of l-methylamino-2-nitro-4- (N-methyl-N-carboxymethylamino) benzene

'5

20th

To a solution of 0.866 mole (194 g) of 1-amino-2-nitro-4-carbamylmethyl-aminobenzene in 700 cm ³ of pyridine at 45 ⁰ C under stirring gradually 0.953 mole (181 g) of p-toluenesulfonyl chloride added. The reaction mixture is kept at 45 ° C. for 4 hours and then poured into ice water with stirring, the 525 cm ^{3 of} conc. Contains hydrochloric acid. The crude product is separated off, dissolved in n / 2 sodium hydroxide solution and the alkaline solution is filtered to remove unconverted starting product. After acidifying the filtrate with hydrochloric acid, the l- (p-toluenesulfonylamino) -2-nitro-4- (N-methyl-N-carbamylmethylamino) benzene is separated off in an amount of 229 g. After recrystallization from alcohol, the product melts at 181 ^° C.

Analysis for Ci ₆ H ₁₈ N ₄ O ₅ S:
Calculated:

C 50.79, H 4.76, N 14.81%;

found:

C 50.89-50.88, H 4.83-4.86, N 14.97-14.86%.

To a solution of 0.424 mole (160 g) of the product so obtained in 1250 ^cm-3 n / 2-sodium hydroxide solution are between 35 and 40 ° C gradually 0.945 mol (90 cm ³⁾ of dimethyl sulfate and at the same 800 cm ³ of n / 2 Sodium hydroxide solution added to maintain a sufficiently alkaline environment. After cooling, the resulting 1- [N'-methyl-N '- (p-toluenesulfonyl) -amino] -2-nitro-4- (N-methyl-N-carbamylmethylamino) -benzene in an amount of 162 g separated, which melts at 184 ° C after recrystallization from acetic acid.

Analysis for C ₁₇ H ₂₀ N ₄ O ₅ S:
Calculated:

C 52.04, H 5.10, N 14.29%;
found:

C 52.02-52.17, H 5.25-5.20, N 14.41-14.39%.

55

60

Gradually, 0.294 mol (115 g) of the product thus obtained in 230 cm ^{3 of} conc. Entered sulfuric acid, the temperature between 0 and 5 ° C is maintained. After this reaction mixture has been kept at the same temperature for 4 hours, it is poured onto 2 kg of crushed ice. It is then neutralized with ammonia and the l-methylamino-2-nitro-4- (N-methyl-N-carbamylmethylamino) benzene, which melts at 184 ° C., is separated off in an amount of 68 g.

Analysis for C ₁₀ H ₁₄ N ₄ O ₃ :
Calculated:

C 50.41, H 5.88, N 23.53%; found:

C 50.62-50.45, H 6.20-6.16, N 23.75-23.54%.

0.286 mol (68 g) of this methylamino derivative are concentrated ^{in 250 cm 3.} Dissolved hydrochloric acid and then refluxed for 45 minutes. After cooling, 72.5 g of 1-methylamino

2 - nitro - 4 - (N - methyl - N - carboxymethyl - amino) benzene monochlorohydrate, which ^{begins to melt with decomposition at 150 °} C., is separated off.

Analysis for C ₁₀ H ₁₄ N ₃ O ₄ Cl:

Calculated:

C 43.55, H 5.08, N 15.24%; found:

C 43.53-r43.24, H 5.11-5.18, N 15.38-15.41%.

B e i s ρ i e 1 4

Production of l - (/? - Hydroxyethyl-amino) -2-nitro-4- (N-methyl-N-carboxymethylamino) -benzene-

Monochlorohydrate

A mixture of 0.4 mol (66.8 g) of 1-amino-2-nitro-4-methylaminobenzene, 800 cm ^{3 of} water and 80 g of calcium carbonate are refluxed. With stirring, 1.2 moles (112.5 g) of chloroacetamide are gradually added. When the addition is complete, refluxing is maintained for an additional hour; the reaction mixture is then cooled and acidified to pH 3 with hydrochloric acid. The precipitated 1-amino-2-nitro-4- (N-methyl-N-carbamylmethylamino) -benzene is separated off; Yield: 86 g. After recrystallization from acetic acid, the compound thus obtained melts at 238 ° C.

Analysis for C ₉ H ₁₂ O ₃ N ₄ :
Calculated:

C 48.21, H 5.35, N 25.00%; found:

C 48.58-48.29, H 5.45-5.50, N 24.86-24.90%.

1.45 mol (325 g) of the product thus obtained are dissolved in 2 l of dioxane. After adding 105 g Calcium carbonate are gradually refluxed with stirring 1.7 mol (244 g) / S-chloroethyl chloroformate added. Then it will be

Further heated under reflux for 3 hours. The reaction mixture is then added to remove the mineral salts Filtered boiling and the filtrate left to stand in the refrigerator for 1 night. The one in a crowd of 120 g precipitated jS-chloroethyl ester of 2-nitro-4- (N-methyl-N-carbamyl-methylamino) -phenyl- carbamic acid is separated off. After recrystallization from alcohol, the ester melts 145 ° C.

Analysis for C ₁₂ H ₁₅ O ₅ N ₄ Cl:
Calculated:

C 43.57, H 4.54, N 16.94%; found:

C 44.48 ^ 14.25, H 4.52-1.67, N 17.31-17.34%.

0.1 mol of this ester are stirred and heated under reflux in 450 cm ^{3 of} 5 n-salt

609512/444

IO

acid entered. When the product is completely dissolved, refluxing becomes ¹ Z ₄ . Maintain hour; then this reaction mixture is ^{poured into 500 cm 3 of} ice water. The separated ß-chloroethyl ester of 2-nitro-4- (N-methyl - N - carboxymethylamino) - phenyl - carbamic acid - 19 g - melts after recrystallization from dilute acetic acid at 147 ° C.

Analysis for Ci ₂ H ₁₄ O ₆ N ₃ Cl:
•Calculated:

C 43.43, H 4.22, N 12.67%;
found:

G 44.05-44.14, H 4.34-4.25, N 13.02-13.10%.

0.034 mol (11.2 g) of the ester obtained in this way are dissolved in 58.5 cm ^{3 of} 3 η-sodium hydroxide solution, then the mixture is refluxed for 1 hour. After cooling, 17 cm ^{3 of} conc. Hydrochloric acid acidified and the deposited monochlorohydrate of 1 - {ß - Hydroxyäthylamino) - 2 - nitro - 4 - (N - methyl-N-carboxymethylamino) -benzene separated, which after recrystallization from 2 η-hydrochloric acid with decomposition at 135 ° C begins to melt.

Analysis for C ₁₁ H ₁₆ N ₃ O ₅ Cl:

Calculated:

C 43.20, H 5.24, N 13.75, Cl 11.62%;

found:

C 43.48-43.37, H 5.39-5.35, N 13.58-13.64

Cl 11.61-11.78%.

Application example 1

An aqueous solution of 1-methylamino-2-nitro-4- (N-methyl-N-carboxymethylamino) benzene chlorohydrate is prepared 0.3 g, lauryl alcohol oxyethylenated with 10 moles of ethylene oxide, 5 g, sodium carbonate until a pH value of 3 is reached and make up to 100 g with water.

This coloring solution is applied to golden yellow bleached hair. After 20 minutes. Exposure time the hair is washed and rinsed. An ash blonde with a mother-of-pearl effect is obtained.

Application example 2

An aqueous solution of 1-methylamino - 2 - nitro - 4 - (N - methyl - N - carboxymethylamino) benzene chlorohydrate is prepared 0.6 g, laurylammonium sulfate (20%) 5 g, sodium carbonate until achieved a pH value of 5 and make up to 100 g with water. ,.

This staining solution will turn to .light auburn Hair applied. After an exposure time of 40 minutes, the hair is washed and: washes. A chestnut brown with golden beetle-colored reflections is obtained.

Application example 3

An aqueous solution of 1 - (/ S-hydroxyethyl-amino) -2-nitro-4- (N-methyl-N-carboxy- methylaminoj-benzene chlorohydrate 0.6 g, 1-hydroxy-2-amino-5-nitrobenzene 0.01 g, with 10 moles of ethylene oxide oxyäthylenierter Lauryl alcohol. 5 g, sodium carbonate until a pH value of 9 is reached and fill up with water. 100 g. .

This coloring solution is applied to auburn hair that is up to 50% white. After an exposure time of 20 minutes, the hair is washed and rinsed. A chestnut brown with a violet-colored effect is obtained. .. ■■ .-. ■.

Application example 4

An aqueous solution of \ - (ß-Hy droxyäthylamino) - 2 - nitro - 4 - (N - methyl-N - carboxymethylamino) - benzene - chlorohydrate 0.5 g, laurylammonium sulfate (20%) 5 g, sodium carbonate is prepared to achieve a pH value of 8 and make up to 100 g with water. .

This solution is applied to light, natural brown hair. After an exposure time of 35 minutes, the hair is washed and rinsed. An ash-colored light maroon brown is obtained.

Application example 5

An aqueous solution of 1-methylamino is prepared - 2 - nitro - 4 - (N - carboxymethylamino) - benzene chlorohydrate 0.8 g, sodium carbonate until achieved a pH of 9.5, lauryl ammonium sulfate (20%) 5 g and make up to 100 g with water.

This solution is applied to dark blonde hair. After an exposure time of 30 minutes, the hair is washed and rinsed. A light chestnut brown with a dark purple effect is obtained.

Application example 6

An aqueous solution of 1-methylamino is prepared - 2 - nitro - 4 - (N - carboxymethylamino) - benzene chlorohydrate 0.8 g, oxyäthylenated with 10 moles of ethylene oxide Lauryl alcohol 5 g, sodium carbonate until a pH value of 3 is reached and fills with water to 100 g. .

This solution is applied to blonde hair. After an exposure time of 40 minutes the hair washed and rinsed. A dark blonde with a mother-of-pearl-like effect is obtained.

Application example 7

An aqueous solution of 1-methylamino-2-nitro-4- (N-methyl-N-carboxymethylamino) benzene chlorohydrate is prepared 0.14 g, 4-nitro-l, 3-diaminobenzene 0.02 g, ammonia (20%) until one is reached pH value of 3 and make up to 100 g with water.

This solution is applied to straw blonde bleached hair. After an exposure time of 15 minutes the hair is rinsed, washed, rinsed again and dried. You get a beige with strong ash-colored pearlescent reflections.

Application example 8

An aqueous solution of 1 - (/ J-Hydroxyäthy lamino) - 2 - nitro - 4 - (N - methyl - N - carboxymethylamino) is prepared - benzene - chlorohydrate 0.15 g, 4 - nitro-1,3-diaminobenzene 0.02 g, ammonia (20%) until a pH value of 3 is reached and fills with Water up to 100 g.

This solution is applied to hair that has been bleached from platinum yellow. After an exposure time of 15 minutes the hair is rinsed, washed, rinsed again and dried. You get a warm beige gold color.

Application example 9

■: An aqueous solution of 1 - (/ S-hydroxyethylamino) is prepared - 2-nitro-4- (N-methyl-N-carboxy-

methylamino) benzene chlorohydrate 0.24 g, 4 - nitro-1,3-diaminobenzene 0.08 g, ammonia (20%) until a pH value of 3 is reached and make up to 100 g with water.

This mixture is applied to 100% white hair. After an exposure time of 25 minutes, the hair is rinsed, washed, and again rinsed and dried - an ash-blonde coloration with a violet-colored effect is obtained.

Application example 10

An aqueous solution of 1-methylamino-2-nitro-4- (carboxymethylamino) benzene chlorohydrate is prepared 0.1 g, 4-nitro-1,3-diaminobenzene 0.004 g, Acetoquinone violet Lumiere N 0.03 g, acetochinone yellow Lumiere RZ 0.03 g, ammonia (20%) up to Achieve a pH value of 3 and make up to 100 g with water.

This solution is applied to hair that is 100% white. After an exposure time of 20 minutes the hair is rinsed, washed and dried. It will be a very light blonde with one slight pearlescent reflex preserved.

Application example 11

An aqueous solution of 1-methylamino ^ -nitro ^ - ^ - carboxyäthylaminoJ-benzene chlorohydrate is prepared 1 g, sodium carbonate until a pH value of 9 is reached, lauryl ammonium sulfate (20%) 5 g and make up to 100 g with water.

This solution is applied to blonde hair. After an exposure time of 15 minutes the hair washed and rinsed. A beige-pink color is obtained.

Claims (1)

Patent claims:
1. p-phenylenediamine nitro dyes of the formula MR The invention relates to new nitro dyes of the general formula (CH ₂ ) ,, - COOH