DE2201670A1 - New indamines that can be used for coloring keratin fibers, especially human hair - Google Patents

Description

PArENTANWXLTC

PROF. DR. DR. J. REITSTÖTTER

DR.-INQ. WOLFRAM BUNTE

DR. KARL GEORG LÖSCH

O - βΟΟΟ MUNICH la BAUtHSTRASSE 32 POST BOX 7βΟ. FEHNHUF (OBIL) 37 BB HS

Munich, M / 11745

JAN. 1972

L · OREAL
14, Rue Royale, Paris ^8e , France

New indamines that can be used for dyeing keratin fibers, especially human hair.

The present invention relates to new indamines of the general formula (i)

(D

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22CLIEZU

M / 11745

wherein R ^, R2 »R3 and R ^, which are the same or different can, a hydrogen atom or a halogen atom or a Lower alkyl or lower alkoxy radical with 1 to 4 carbon atoms ,, and Rc is a lower alkyl group, preferably with 1 to Carbon atoms, and the tautomeric forms of the compounds of the formula (i).

The compounds are prepared by condensing a p-phenylenediamine of formula (II),

(11)

where R ^, R £ »R * and R ^ have the meanings given above ! have a 6-hydroxy-4-alkyl-phenomorpholine of formula (III)

(III)

wherein R 1 - denotes a lower alkyl group. The used Starting materials can of course be the compounds (II)

ior (III) in the form of salts, such as hydrochlorides, sulates, ! Hydrobromides.

209830/1 132

M / 11745.

The condensation occurs in an aqueous, aqueous acetone or aqueous alcoholic medium at a pH equal to or above 8, in the presence of an oxidizing agent at temperatures »; carried out between 0 and 50 ° C.

'Hydrogen peroxide' is advantageously used as the oxidizing agent and the reaction medium is made alkaline by adding: sodium hydroxide solution or potassium hydroxide solution or, better still, ammonia, j

In the preparation of the indamines according to the invention, use-I bare p-phenylenediamines are in particular p-phenylenediamine, p-toluylenediamine, 2,5-diaminoanisole, 2,5-diaminochlorobenzene, 2-methoxy-5-methyl-p-phenylenediamine, 2, e-dimethyl-S-methoxyp-phenylenediamine or 1,4-diaminodurol.

\ The new compounds are dyes that are used to dye 'keratin fibers, especially human hair'.

The present invention accordingly also comprises a new colorant for keratinous fibers which comprises at least one compound ^; of formula (i).

The colorants according to the invention can only contain indamines of the above formula · (I) and in this case allow the ; Achieving colors that vary from green to blonde, are always rich in reflections and very often affect the hair Lend a shimmering mother-of-pearl appearance.

The concentration of the compounds (I) in the agents can vary from 0.002 to 1% by weight and preferably from 0.005 to 0.5% by weight .

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Μ / 11745 Η

The dyes according to the invention can be combined with other dyes commonly used for coloring hair, such as azo dyes, anthraquinone dyes ^ nitro derivatives Mix the benzene series, azines or oxazines. You can also use the dyes according to the invention with indoanilines or Combine indophenols or other indamines.

In general, the compounds according to the invention are in the form of aqueous or aqueous alcoholic solutions, which you can very easily by dissolving one or more compounds of the formula (I), optionally combined with other dyes. The solutions can also contain thickeners and are in the form of creams or Gels are present.

In addition, the agents according to the invention can contain various components commonly used in cosmetics,

! "for example wetting agents, dispersants» swelling- ' agents, penetrants, emollients or perfumes. j They can be conditioned in aerosol bombs.

·

The pH of the colorants according to the invention can vary considerably and is generally between 4 and 11, preferably between 7 and 11.

'The coloring of keratinous fibers, especially human ones ! Hair using the colorants according to the invention is done in the usual way by applying the agent to the hair ι coloring fibers with which it is left in contact for a period of 5 ι to 30 minutes, after which the fibers ι rinsed and, if necessary, washed and dried *

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The present invention also comprises a new hair lotion, which contains at least one cosmetic hair lotion and at least one compound of the formula (I) in an aqueous alcoholic solution.

The concentration of the compounds (I) in these water-wave lotions may 0.002 to 1 part by weight 96, and preferably from 0.005 to 0.5 wt -.% Vary. ,

; The Wasserwellotion can be used as cosmetic resins, such as polyvinyl pyrrolidone, crotonic acid / vinyl acetate copolymers, vinyl pyrrolidone / vinyl acetate copolymers, maleic anhydride / butyl vinyl ether-Mischpolyraerisate etc. containing these resins in an amount of 1 to 3 wt -%!. be used.

The for the production of the water wave lotions according to the invention I suitable alcohols are the alcohols with low molecular weight, and preferably ethanol or isopropanol. They make up a proportion of 20 to 50% by weight of the lotions.

ί ■ ··

! . '■ ■

; The water wave lotions according to the invention are in the usual j way applied by applying to damp, previously washed and rinsed hair, after which the hair is rolled up ; and dried ».

The following examples illustrate the various features of the present invention without limiting it. ₍ The temperatures given in the examples are measured in ⁰ C.

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example 1 ₍

Preparation of the monohydrate of N- [V ».- (6LrHydroxyr-4 ^l -methyl-l». Oxa-4'-aza-l ·, 2 »* 3 *, 4'-tetrahydro) -naphthyl] -3-methoxy - .J 6-methyl-benzoquinonediimine.

OCH,

OH I ³ A

»<4 1> = NH

H ₂ O

To a solution of 1.70 g (0.0075 mol dihydrochloride of 2-methyl-5-methoxy-p-phenylenediamine in 5 cm ⁵ water, 7 cm ³ are ammonia at 22 ° and 45 cm * B acetone a solution of 0.825 g (0.005 mol) of 6-hydroxy-4-methyl-phenomorpholine and then, with stirring, 35 cm · "hydrogen peroxide in 20 volumes. The reaction mixture is left to stand for 1 hour at ambient temperature. After cooling to ⁰ ° C., it is suctioned off, washed with water and dried in vacuo, 1.20 g of crystallized indamine which ^{melts at 166 °} C. being obtained.

Molecular weight calculated for

Molecular weight 325 found by potentiometric determination in acetic acid using perchloric acid

analysis

calculated: found:

C. , 63 H 34 N , 69 61 , 64 6, 36 12th , 49 61 , 74 6, 46 12th , 53 61 6, 12th

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example

Preparation of the monohydrate of N- [17 · - (6'-Hydroxy-4 ^f -methyl-1 ⁽ · oxa-4'-aza-1 ', 2 *, 3 *, 4'-tetrahydro) -naphthyl] -3 -methoxy- * _ 'benzoquinonediimine

OCH,

To a solution of 2.11 g (0.01 mol) of dihydrochloride of

Methoxy-p-phenylenediamine in 10 cm ° of water to which 7 cm ^{5 of} ammonia at 22 ° B have been added is a solution of €, 825 g (0.005 mol) of 6-hydroxy-4-methyl-phenomorpholine in 10 cm of acetone and then, with stirring, 26 cnr hydrogen peroxide in 20 volumes. Letting the reaction mixture stand for 20 minutes at ambient temperature, then filtered off with suction, washed with water and dried in vacuo to give 0.9 g of crystalline indamine obtained, which after recrystallization from a dimethylformamide / water mixture at 174 ⁰ C melts.

Analyee ^c i6 ^H 17 ^N 3 ° 3 * ^H 2 °

calculated: found:

C. 55 H , 03 N , 24 60, 60 6th , 96 13th , 02 60, 42 5 , 15 13th 60, 6th 13th

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Example 3

Preparation of the monohydrate of N- [7 ^l - (ö'-Hydrpxy-4 ^l -methyl ^L l ^l oxa-4'-aza-l ', 2', 3 * # 4'-tetrahydro) -naphthyl] -benzoquinone- _ ...... diimin.

OH

N = ^ f YES «NH, H ₂ O

To a solution of 3.62 g (0.02 mol) of dihydrochloride of p-phenylene diamine in 20 cnr water, which is mixed with 7.5 cm with ammonia 22 ⁰ B, is added a solution of 1.65 g (0, 01 mol) 6-hydroxy-4-methyl-phenomorpholine in 10 cnr acetone, then 20 cm hydrogen peroxide with 20 volumes with stirring. The reaction mixture is left to stand at ambient temperature for 30 minutes and then at ⁰ ° C. for 1 hour. It is suctioned off, washed with water and dried in vacuo to give 1.4 g indamine, melting after recrystallization from a dimethylformamide / water mixture at 160 ⁰ C. The product is ^ chromatographically pure.

Molecular weight calculated for C ₁₅ H ₁₅ N ₃ O ₂ · H ₂ O

Molecular weight, 'found by potentiometric determination in dimethylformamide using a 0.1 η Solution of tetra-n-butylammonium hydroxide in Isopropanol-methanol. '"....'

2 0 9 8 3 0/1132

j Μ / 11745

Example 4

^! Preparation of the monohydrate of N- [7 '- (6 ^l -hydr'oxy-4'-ethylt · l'-oxa ^' - aza-1 ·, 2 ·, 3 ', 4'-tetrahydro) -naphthyl] _r 3-methoxy- J "". ! 6-methyl-benzoquinonediimine:

To a solution of 3.4 g (0.015 mol) dihydrochloride of 2-methyl-5-methoxy-p-phenylendiainin in 10 cnr water, 90 cnr, are acetone and 14 cm ⁵ ammonia at 22 ° B was 2.60 g ( 0.01 mol) δ-hydroxy-ethyl-phenomorpholine hydrobromide in 5 cnr water, 10 cnr acetone and 3 cnr ammonia at 22 ° B. Then 70 cnr hydrogen peroxide in 20 volumes are added to the mixture and the reaction mixture is left to stand for 2 hours at ambient temperature. 20 cnr of water are then added and, after cooling to ⁰ ° C., 1.70 g of the expected indamine are filtered off with suction, washed with water and dried in vacuo. After recrystallization from a dimethylformamide / water mixture, the product is chromatographically pure and melts at 136 ^° C.

Molecular weight 'calculated for C ₁₈ H ₂₁ N ₃ O,' H ₂ O

Molecular weight, found by potentiometric determination in dimethylformamide using a 0.1 η Solution of tetra-n-butylammonium hydroxide in Isopropanol-methanol

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; M / 11745 * 1Q

: Example 5

'You create the following solution:

Dyestuff according to Example 2 0.05 g

Vinyl acetate / crotonic acid Mi schpolvraeri sat
(90 % vinyl acetate, 10%! Crotonic acid, ₂

Molecular weight 45,000 to 50,000) ^s

Alcohol with 96 "50 g

Water as much as necessary for 100 g

Triethanolamine as much as needed for pH

If this solution is applied to bleached hair as a water wave lotion, it gives it a pale green shade Shimmer of gold.

Example 6

The following solution is created:

Dye according to Example 2 0.2 g

I alcohol at 96 ° 35 g

Water as much as necessary for 100 g

Ammonia with 22 ⁰ B as much as necessary for pH 7

Apply this solution to bleached hair for 20 minutes

It gives it after rinsing and shampooing

; a golden blonde shade with a green shimmer.

- 10 -

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B ei ^ η i, e 1 7 ι

You create the following solution: '

Dye according to Example 1 0.3 g

Alcohol with 96 ° · 50 g

Water as much as necessary for 100 g

Ammonia at 22 ° B as much as required for pH 10.5 ''

Apply this solution for 20 minutes. 95 % naturally white hair, it gives it a pale green shade with a silver shimmer after rinsing and shampooing.

ft , ei β ρ ie 1 B

The following solution is created:

Dye according to Example 1 0.1 g

Vinyl acetate / crotonic acid copolymer 2 g

(90 ^ vinyl acetate, 10 % crotonic acid. Molecular weight 45,000 to 50,000) Alcohol with 96 ° as much as necessary for 50 ° water as much as necessary for 100 g

Triethanolamine. as much as necessary for pH 7

If you apply this solution to bleached hair as a water wave lotion, it gives it an almond green shade.

- 11 -

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B e 1 s ρ 1 e 1 9 ,

You create the following solution: '

Dyestuff according to Example 1 0.4 g

Alcohol at 96 ° as much as necessary for '50 °

Water as much as necessary for 100 g

10 % lactic acid as much as required for pH 4

If this solution is applied to 95 % naturally white hair for 15 minutes, it gives it a pearly appearance with pale green, very luminous reflections.

Example 10

The following solution is created:

Dye according to Example 1 0.1 g

benzoquinone imine 0.05 g

Alcohol at 96 ° 50 g

Water as much as necessary for 100 g of triethanolamine as much as necessary for pH 7

If you apply this solution to bleached hair for 20 minutes, it gives it one after rinsing and shampooing very light, iridescent golden brown shade,

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Example 11

The following solution is created:

Dye according to Example 3 0.1 g

Vinyl acetate / crotonic acid copolymer 2 g (90 % vinyl acetate, 10 % crotonic acid, molecular weight 45,000 to 50,000) alcohol with 96 ° as much as necessary for 50 ° water as much as necessary for 100 g

Triethanolamine as much as required for pH 7

If this solution is applied to bleached hair as a water wave lotion, it gives it a gold nuance with pale green reflections.

Example 12

The following solution is created:

Dye according to Example 3

Butyl glycol

Lauryl alcohol, 'oxyethylene with 10.5 moles of ethylene oxide

Water as much as necessary for the pH of the solution is 7.

If you apply this solution to 95 % naturally white hair for 20 minutes, it gives it a light bronze shade after rinsing and shampooing.

- 13 209830/1 132

O, 4 g 5 G 5 G 100 G

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Example 13 ,

The following solution is created:

Dyestuff according to Example 1 0.2 g i

N - [(4'-hydroxy) phenyl] -2,6-dimethyl-

benzoquinone imine 0.05 g '

Alcohol at 96 ° 25 g

Water as much as necessary for 100 g

Ammonia with 22 ⁰ B as much as necessary for pH 10

If this solution is applied to 95 % naturally white colors for 20 minutes, it gives them a beige shade with a rosewood shimmer after rinsing and shampooing.

Example 14

The following solution is created:

Dyestuff according to Example 3 0.15 g

N - [(4'-Amino) phenyl] -3-amino-6-methylbenzoquinone imine 0.05 g

Alcohol with 96 ° as much as necessary for 35 ° water as much as necessary for 100 g

Ammonia with 22 ⁰ B as much as required for pH 8.

You bring this. The solution is applied to bleached hair for 20 minutes, and after rinsing and shampooing it results in a very _: shiny mother-of-pearl blonde. j

I - 14 -!

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■ B e J. S ρ i el 15 Prepare the following solution:

Dyestuff according to Example 3 0.10 g

Ν · [(4t "Amino-2'-methoxy-5 ¹ -methyl) -phenyl] - · i

3-amino-6rniethyl-benzoquinonediimine acetate 0.025 g ^!

Safranin 0.0125 g,

Alcohol at 96 ° 25 g

Water as much as necessary for 100 g

Ammonia with 22 ⁰ B as much as necessary for pH 7

If this solution is applied to 95 % naturally white hair for 10 minutes, after rinsing and shampooing, it gives it a shimmering shade of pure silver.

IJJ . §Ρj. e 1 "16

The following solution is created:

Dyestuff according to Example 3 0.15 g

lwMethyl "ß" * arainoäthylamino-3-nitro-4-methylamino-benzpl-'hydrochloride vinyl acetate ^ crotonic acid copolymer (90 % vinyl acetate, 10 % crotonic acid, molecular weight 45,000 to 50,000) alcohol with 96 ⁹ '

Water as much as needed for

Triethanolamine as much as required for pH 7

If you bring this solution as a water wave lotion on decolorized Hair, it gives it a light brown, purple shade with a mother-of-pearl shimmer.

- 15 2098 30/1132

0, 15 g 2 G 50 G 100 G

M / 11745 * 46

Example 17

The following solution is created:

Dyestuff according to Example 2 0.04 g

Double chloride of zinc and N - [* 7 '- (6 ^f -hydroxy-4'-methyl-1'-oxa-4 · -aza-1 ·, 2', 3 ', 4'-tetrahydro) -naphthyl] - N ', N'-ethyl- ß-acetylaminoethylbenzoquinone iminium 0.01 g nitro-p-phenylenediamine 0.03 g

Alcohol with 96 ° as much as necessary for 50 ° water as much as necessary for 100 g

Triethanolamine as much as required for pH 7

If you apply this solution as a water wave lotion to bleached hair, it gives it a light brown ashy color Nuance with a pearly appearance.

Example 18

The following solution is created:

Dyestuff according to Example 4 0.05 g

Vinyl acetate / crotonic acid copolymer 2 g (90 % vinyl acetate. 10 % crotonic acid, molecular weight 45,000 to 50,000) alcohol with 96 ° as much as necessary for, 50 ° water as much as necessary for 100 g

Triethanolamine as much as required for pH 7

If you apply this solution to bleached hair as a water wave lotion, it gives it an almond green shade Mother-of-pearl shimmer.

- 16 209830/1132

Claims (23)

M / 11745 if Claims New compounds of formula (i) wherein R ₁ , R ₂ , R, and R ^, which may be the same or different, represent a hydrogen atom or a halogen atom or a lower alkyl or lower alkoxy radical having 1 to 4 carbon atoms, and Rc a lower alkyl group, as well as the tautomeric forms of the compounds of Formula (i). 2. Compounds according to claim 1, characterized in that the lower alkyl group is a methyl group. 3. Compounds according to claim 1, characterized in that the lower alkyl group is an ethyl group. 4. Process for the preparation of compounds according to claim 1, characterized in that one p-phenylenediamine of the formula (II) - 17 - 209830/1132 M / 11745 (II) wherein R ^, R2, R- * and R ^ have the values given in claim 1 have interpretations with a 6-hydroxy-4-alkyl-phenomorpholine of formula (III) (III) where R ^ is a lower alkyl group, in aqueous, aqueous-acetone or aqueous-alcoholic medium, the pH of which is equal to or greater than 8, in the presence of a Oxidizing agent and condensed at a temperature between 0 and 50 ° C. 5. The method according to claim 4, characterized in that the compounds of formulas (II) and (III) in the form of Salts such as hydrochlorides, hydrobromides, sulfates can be used. - 18 - 209830/1 1 32 M / 11745 13 6. The method according to any one of claims 4 or 5, characterized in that the 6-hydroxy-4-alkyl-phenomorpholine used which is 6-hydroxy-4-methyl-phenomorpholine. 7. The method according to any one of claims 4 or 5> thereby characterized in that the 6-hydroxy-4-alkyl-phenomorpholine, that is used is 6-hydroxy-4-ethyl-phenomorpholine. 8. The method according to any one of claims 4 to 7, characterized in that the oxidizing agent used is hydrogen peroxide is. 9. Colorants for keratin fibers, especially for human hair, characterized in that there is at least one Compound according to any one of claims 1 to 3. 10. Composition according to claim 9 »characterized in that its pH is between 4 and 11, preferably between 7 and 11 lies. 1: 1. Agent according to one of Claims 9 and 10, characterized in that it is 0.002 to 1% by weight and preferably 0.005 to 0.5% by weight of at least one compound according to one of Claims 1 to 3. 12. Agent according to one of claims 9 to 11, characterized in that there are also other hair dyes, for example Azo dyes, anthraquinone dyes, nitro derivatives of Contains denenzene series, azines or oxazines. - 19 2 0 9830/1132 M / 11745 13 * Agent according to one of claims 9 to 11, characterized in that it also contains other dyes, such as indoanilines, indophenols or other indamines. ' J 14. Agent according to one of claims 9 to 3, characterized 'characterized as being wetting agents, dispersing agents, penetrating agents or any other, usually in the Contains ingredient used in hair cosmetics. ! 18. Means according to claim 17, characterized in that the alcohol it contains is a low molecular weight alcohol, and preferably ethanol or isopropanol is. - 20 - 209830/1132 15. ■ 'means according to one of claims 9 to 14, characterized \ in that aqueous-aqueous or in the form! alcoholic solution, cream or gel. 16. Agent according to one of claims 9 to 14, characterized in that it is conditioned in aerosol bombs. 17. Means according to claim 9, in the form of a colored ', Hair water wave lotion, characterized in that; it in aqueous alcoholic solution at least 1 cosmetic ^! Contains resin. i M / 11745 19. Agent according to one of claims 17 and 18, characterized characterized in that it contains 20 to 50% by weight alcohol. ι 20. Agent according to one of claims 17 to 19 »characterized in that it is 1 to 3 wt .-% cosmetic resin! contains. ß.1. Agent according to one of Claims 17 to 20, characterized in that it contains 0.002 to 1% by weight and preferably 0.005 to 0.5% by weight of at least one compound according to one of Claims 1 to 3. 22. A method for dyeing keratin fibers, in particular human hair, characterized in that one impregnates the fibers to be dyed with an agent according to claims 9 to 16, this agent for a period of time that from 5 to 30 minutes varies with the fibers in contact and then rinses the fibers and if necessary shampooes and dries. 23. Process for the creation of water waves by human Hair, characterized in that an agent in the form of a water wave lotion according to one of the claims 17 to 20 is applied to previously washed and rinsed hair, untwisted and dried. - 21 - 209830/1132