DK144641B - DIPHENYLAMINE COMPOUNDS FOR USING DYE HAIR - Google Patents

Description

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É | (12) PUBLICATION MANUAL OR 11 * 4641 B

DIRECTORATE OF THE PATENT AND TRADEMARKET SYSTEM

(21) Application No. ^ 9 ^ 5/75 (51) Int.CI.3 C 09 B S1 / 00 (22) Filing Day 5 ^ · Oct · 1975 A 61 K 7/13 (24) Running Day 20 Dec. 1975 (41) Aim. available Oct. 50 1975 (44) Posted Apr 26 1982 (86) International Application No. - (86) International Filing Day - (85) Continuation Day - (62) Master Application No. 6975/75

(30) Priority Dec 26 1972 * 518295 * US

(71) Applicant BRISTOL-MYERS COMPANY, New York * US.

(72) Inventor Alexander Halasz * US: David Cohen, US.

(74) Clerk Th. Ostenfeld Patentbureau A / S.

(54) Dlphenylarain compounds for use in hair dyeing.

The present invention relates to certain novel diphenylamine compounds for use in hair dyeing.

For the preparation of hair dye preparations for human hair of the direct dyeing type, it is often necessary to mix colors having a yellow to orange or red tone with other colors to obtain a desired naturally-appearing tone. It has been common practice in this art to use certain nitro-p-phenylene diamines for this purpose since they are easily soluble or dispersible in water and readily diffuse into the hair. Typical of these compounds. [Alpha-2-nitro-p-phenylenediamine, Ν'-methyl-2-nitro-p-phenylenediamine, N '- (β-hydroxyethyl) -2-nitro-p-phenylenediamine These colors, however, are - Although these compounds have sufficient affinity for permanently wavy hair and give good staining, their wash fastness is initially poor even with a single hair wash.

Other yellow to orange or red colors which are of the azo and anthra-quinone color types are also known. However, these have too low water dispersibility or affinity for hair to be useful. This is thought to be due to the large molecular size of these colors, which prevents them from easily diffusing into the hair.

It has now been found that a certain group of nitrodiphenylamine dyes, defined further below, constitute a group of yellow to orange and red colors which possess the advantage of having good affinity for damaged hair, especially permanently wavy hair, and yet greater hair wash fastness than the known nitrophenylenediamine dyes previously used for this purpose.

Accordingly, it is an object of the invention to provide certain novel compounds which are useful as hair dyes and especially as direct dyeing hair colors.

The novel diphenylamine compounds of the invention are characterized in that they have the formula: HN-Q-R1 wherein R is OH, -NHtC1 (hydroxyalkyl) or -N (C1-6 hydroxyalkyl) 2r and the NO9 group are in the o-group. or p-position, provided that 5 ^ R is -N (C1-6 hydroxyalkyl) 2 ^ when the NO2 group is in the p-position.

In the above compounds, C ^gg hydroxyalkyl may in particular be hydroxyalkyl of 2-4 carbon atoms and 1-3 hydroxy groups, e.g. 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, tris- (hydroxymethyl) methyl, 1,3-dihydroxy-2-methyl-2-propyl, 2,3-dihydroxypropyl and 1,3-dihydroxy-2- propyl.

The invention thus encompasses compounds which can be defined by the formula 3 144641

-NO, IV

u 5 where R has the meaning given above. Of particular interest and utility are the compounds of formula IV wherein R represents -OH or -N (CH 2 CH 2 OH) 2. These are preferred compounds of the invention.

Further, among the novel compounds of the invention are those of the formula HN-N-N (C 1-6 hydroxy alkyl)

Of particular interest is the compound of formula V wherein the group -N (C 1-6 hydroxyalkyl) 2 is -N (CH 2 CH 2 OH) 2. This is also a preferred compound of the invention.

The advantage of the above dyes when used for dyeing hair lies in a combination of tone, affinity for hair and washability. The color generally varies from yellow to orange and red. They can therefore usually be used to apply all or part of the red component in toner which requires it. Although they only show a certain affinity for undamaged gray hair, the damaged hair ends color particularly well. This is especially true for hair ends that have previously been damaged by permanent waviness and to a lesser extent bleaching. Furthermore, they generally tolerate better hair washing than current reds. When used with the blue colors of the nitro-p-phenylenediamine group, the final effect is therefore that they provide coverage (uniformity, good compatibility) of dyes with permanently wavy ends, and the obtained tone remains opaque after at least one hair wash.

In practice, however, the dyes of the invention will most often be used in conjunction with other red dyes which will supply most of the red component of the color mixture. However, for the yellower tones, the usual red component can be avoided.

Any of the above-described nitrodiphenylamine dyes or combinations thereof may be incorporated into a fluid hair dye carrier of the type suitable for application of direct dyeing dyes. Many such carriers are well known in the art. These can range from simple aqueous solutions and / or suspensions of the dye to very complicated aqueous preparations such as creams, lotions, pastes, gels, etc. containing mixtures of other dyes, nonionic and anionic detergents, solvents, thickeners, fragrances, etc. In these aqueous compositions, the carriers may be water or a combination of water and other solvents, e.g. ethanol. An aerosol system, e.g. an aerosol emulsion system wherein the dye is contained in an aqueous phase of the system.

The nitrodiphenylamine dyes of the invention can be used to prepare basic, neutral or acidic staining compositions.

Furthermore, they can also be added to hair dye preparations containing other direct dyeing dyes. From the dye technique, many direct dyeing dyes are known which are useful for this purpose.

They include nitro dyes, azo dyes, anthraquinone dyes, etc. For example, any of the nitro dyes disclosed in U.S.A. may be used in connection with the colors herein. U.S. Patent Nos. 2,750,326, 2,750,327, 3,088,877, 3,088,878 and 3,088,978.

The pH value of the staining compositions in question may vary from approx. 4 to approx. 12 and preferably from 7 to 11.5. Any preferred water-dispersible, compatible base (if desired to have compositions in the alkaline range) can be used to obtain the desired pH. The amount of base used can vary over a wide range depending on the color and the particular base used and the desired pH value. By way of example, the base amount may vary from less than ca. 0.05% to approx. And preferably from about 10%. 0.10% to approx.

5% by weight of the preparation.

Any one of many bases can be used to adjust the pH of the subject staining composition on the basic side. Ammonia water is an acceptable base due to its lack of toxicity over a wide range of concentrations and its easy accessibility. However, instead of or together with ammonia, any other compatible ammonia derivative such as an alkylamine, e.g. ethylamine, dipropylamine or triethylamine; an alkanediamine, e.g.

1,3-diaminopropane? an alkanolamine, e.g. monoethanolamine or diethanolamine, triethanolamine; a polyalkylene polyamine, e.g. diethylene triamine; or a heterocyclic amine such as morpholine.

5 U4641

The pH of the composition can be adjusted on the acid side with any inorganic or organic acid or acid salt which is compatible with the composition and does not introduce toxicity under the conditions of use, especially when acidic preparations are desired. Examples of acids or acidic salts include sulfuric, formic, acetic, lactic, citric or tartaric acids, or ammonium sulfate, sodium dihydrogen phosphate or potassium bisulfate.

Surfactants may also be used in the current dyeing compositions. These can be anionic, nonionic or cationic. The amount of surfactant may vary over a wide range, such as from ca. 0.05% to approx. And preferably from about 15%. 0.10% to approx.

5% by weight of the preparation.

A thickener may also be incorporated into the present dye composition, and one or more of those commonly used in hair dyeing may be used. The amount of this thickener may also vary over a wide range, such as from 0.1% to approx. 20%, and will usually range from approx. 0.5% to approx. 5% by weight of the preparation.

It is also useful to incorporate an antioxidant into the staining compositions. Many antioxidant agents are known in the art which can be used for this purpose. The amount of antioxidant may, when used, vary widely. However, it will usually be of the order of approx. 0.025 to approx. 1% by weight.

The nitrodiphenylamine dyes are incorporated into the compositions in effective staining amounts, i.e. in concentrations sufficient to color the hair. These amounts may vary over a wide range, but will usually range from about 0.001% to more than approx. 5%, e.g. 10% by weight of the preparation. Preferably, however, they will comprise from ca. 0.001% to approx. 2% by weight of the preparation. The main constituent of the composition used is usually water, and its contents may vary widely over a wide range depending on the amount of other additives. Thus, the water content may be as small as 10%, but will preferably comprise from ca. 70% to 99% by weight of the composition.

The dyeing compositions containing the diphenylamine compounds of the invention are preferably aqueous compositions. The term aqueous composition is used herein in its usual generic sense, by which is meant any aqueous preparation which may be used for the purpose. It thus comprises true solutions of the color in an aqueous medium either alone or in association with other materials which are also dissolved or dispersed in the aqueous medium. The term aqueous composition 6 further includes any mixture of color with the aqueous medium, either alone or together with other ingredients. The color may be colloidly dispersed in the medium or may simply be intimately mixed therein. Furthermore, the aqueous medium may comprise water or water together with an additional or additional solvent. The latter can be used as a common solvent to increase the solubility of the dye or any other organic material. Other auxiliary solvents which may be used for this purpose include ethanol, carbitol, isopropanol, propylene glycol, ethylene glycol, glycation, etc.

Typical staining compositions of the simple aqueous alkaline species described above are listed below:

Aqueous alkaline preparations

Generally Preferred range interval

Nitrodiphenylamine color 0.001 - 5% 0.001 - 2%

Surfactants 0.05 - 15% 0.10 - 5%

Base 0.05 - 10% 0.10 - 5%

Thickener 0.1 - 20% 0.5 - 5%

Water q.s. to 100% q.s. to 100% pH (acid added if necessary) 7.0 -11.5 7.5 -10.5

The nitrodiphenylamine dye and any of the surfactants, thickeners and combinations thereof listed above can be used in the proportions specified in the table just given. The base of these compositions will be one or more of the bases described above.

The simple aqueous alkaline dye composition can be prepared by conventional methods of the hair dye technique. Thus, they can be prepared by dissolving or suspending the dye in water at the desired concentrations. Organic solvents which are miscible with water, e.g. ethanol, can be used to facilitate the dissolution of the dye. In this case, the dye can first be dissolved in solvents and then diluted with water. The dispersion of the various components can also be facilitated by heating the composition to temperatures varying from 40 ° C to 110 ° C either before dilution with water or later.

These compositions can be applied to hair by the methods conventionally used for this purpose. For illustration thereof, mention may be made of application to live hair on the human head, wherein the compositions may be applied to the hair by means of a brush, sponge or other contact agent, such as by pouring the composition directly onto the hair until saturation. The reaction time or contact time of the dye preparation with the hair is not critical and can vary over a wide range as used in the hair dye technique, such as periods of from 5 minutes to approx. 2 hours. Preferably, a period of from about 1 5 minutes to approx. 60 minutes, and most often a period of 10-30 minutes. The staining temperature can vary between wide limits, as is conventional in this technique. Thus, the staining temperature may vary from ca. room temperature, e.g. 20 ° C to approx. And preferably from about 60 ° C. 20 ° C to approx. 45 ° C.

As previously mentioned, the present invention may also apply to aerosol systems containing an aqueous phase in which the nitrodiphenylamine dyes are incorporated. In this aspect of the invention, an aqueous alkaline composition is prepared as described above, and it serves as an aqueous concentrate incorporated into the aerosol system.

To prepare a direct staining aerosol staining composition, the above-described alkaline concentrate (97-90% by weight) is mixed with an expelling agent (3-10% by weight). In a preferred embodiment, the expelling agent is approx. 5% by weight of the total aerosol composition and the concentrate constitutes the remainder.

The invention is further illustrated in the following examples.

Example 1

Preparation of 41-hydroxy-2-nitrodiphenylamine

F NH2 OH

^ Λ ^^ Ν02 Sodium Acetate || + [f I "methylcellosolve" ^ ([^ v v OH Ψ N ° 2 u

Starting material: A. 141 g (1M) ortho-fluoronitrobenzene B. 109 g (1M) para-aminophenol C. 136 g (1M) sodium acetate .3H20 D. 350 ml of "methyl cellosolve" (2-methoxyethanol) 8

Procedure: Place A, B, C and D in a 2 liter 3-neck flask fitted with a stirrer and reflux condenser. The reaction mixture is heated by means of a heating jacket with stirring to reflux (about 115 ° C) for 23 hours. The reaction mixture is allowed to cool to room temperature and the resulting mixture is filtered. The solid obtained is a salt residue that is discarded. The solvent is removed from the filtrate by evaporation on a rotary evaporator. The resulting solid is recrystallized from aqueous ethanol (50/50). Weight of pure product obtained = 189 g. Melting point = 144-145.5 ° C. Yield = 82.2%.

Colors hair cute.

Example 1A

Preparation of 4'-hydroxy-2-nitrodiphenylamine

F NH9 OH

You ° * Λ Λ + sodium acetate S / "me thylcellosolve" ^

OH

CP

Starting material: A. 28.2 g (0.2M) of ortho-fluoronitrobenzene B. 21.8 g (0.2M) of p-aminophenol C. 27.2 g (0.2M) of sodium acetate. "methylcellosolve"

Procedure: A, B, C and D are mixed in a small autoclave and heated to 170-180 ° C for 28 hours. Then, the reaction mixture is cooled and filtered. The solvent is removed from the filtrate by evaporation on a "roto-vac" and the resulting solid is recrystallized from a mixture of ethanol and water (50/50). 33.3 g (75% yield) of a reddish brown crystalline material having a melting point in the range 140-141 ° C were obtained.

9 144641

Example 2

Preparation of 41 - (N, N-bis-3-hydroxyethylaminoV-2-nitrodiphenylmarinine Reaction: ^ ch2ch2oh, ch2ch2oh

F N W

2 CH2 CH2 OH (\ CH2CH2OH

J + I ^ sodium acetate_ ^

"methylcellosolve" I

T T

NHo.S0 „NH

2 4 A NO0 (j

Starting material: A. 14.1 g (0.1M) o-fluoro-nitrobenzene B. 28.8 g (0.1M) N, N- (bis-hydroxyethyl) -p-phenylenediamine sulfate C. 40.8 g (0.3M) sodium acetate . D. 70 ml of "methylcellosolve" (2-methoxyethanol)

Procedure: Mix A, B, C and D in a 500 ml 3-neck flask equipped with a stirrer and reflux condenser. The reaction mixture is warmed by stirring under reflux (about 108 ° C for 22 hours. The reaction mixture is cooled to room temperature and filtered. The solvent is removed from the filtrate by evaporation on a rotary evaporator. The sticky mass is recrystallized from aqueous ethanol (50 50). A sticky solid forms which solidifies upon cooling in ice bath and scraping. Thin layer chromatogram shows a violet impurity which is B. The solid is dissolved in ethyl acetate and extracted with water. The B impurity is soluble in the water layer. Charcoal is filtered and the filtrate is evaporated, and the resulting sticky product is dried on a porous plate followed by desiccator drying.

Weight of product = 21.4 g. Melting point (fast) = 100-105 ° C. Colors hair orange-brown.

144641 ίο

Example 3

Preparation of 4'-bishydroxyethylamino-2-nitrodiphenylamine Reaction: F N (CH ~ CHoOH) n N (CHoCH-OH) -. in III in 2. Δ λ

JL no2 JL

sodium acetate.3H 2 O isopropanol HH 2 -H 2 SO 4 J? .NO, σ

Starting material: A. 70.5 g (0.5M) o-fluoro-nitrobenzene B. 144.0 g (0.5M N, N- (bis-hydroxyethyl) -p-phenylenediamine sulfate C. 204.0 g (1.5M) sodium acetate. 3H20 D. 375 ml of isopropanol

Procedure: A, B, C and D are placed in a 1 liter 3-neck flask and heated to reflux stirring for 4 hours. The reaction mixture is then cooled and filtered to remove salt. The resulting filtrate is vapor distilled to remove all traces of o-fluoronitrobenzene. The hot contents of the flask are then transferred to a beaker and cooled with stirring. The solid that forms is filtered and then this solid is treated with distilled water, filtered and washed out. This water-leaching purifying procedure is repeated twice. The product is dried in an oven at 50 ° C overnight. Weight of product = 88.1 g. Melting point 102-105 ° C. Yield = 55.6%. Colors hair orange-brown.

application examples

Table I

Ingredients Ex. A weight% Ex. B wt% 4'-hydroxy-2-nitrodiphenylamine 0.25 4 '- (N, N-bis-p-hydroxyethylamino) -2-nitrodiphenylamine - 0.25

Diethanolamine 2,000 2,000 u 144641

Table I (continued)

Ingredients Ex. A weight% Ex. B wt%

Diethylene glycol monoalkyl ether 4,000 4,000

Laurindiethanolamide 3,000 3,000

Triethanolamine linear alkylate sulfonate 0.500 0.500

Polyoxyethylene hydrogenated fatty amide 1,900 1,900

Sodium carboxymethyl cellulose 2,400 2,400

Oleic acid 1,000 1,000

Scent 0.125 0.125

Water q.s. 100,000 100,000 pH 9.5 9.5

The compositions of Examples A and B were applied to samples of undamaged gray hair and permanent wavy hair at 38 ° C, remaining there for 20 minutes, then rinsing with lukewarm water.

Table II

Preparation Hair Tone Affinity ___ Gray Hair Permanent-wavy hair

Example A Orange Reasonably Good

Example B Matte Orange Rings Affordable

The colors are reasonably resistant to hair washing.

Table III

Weight Percent

Ex. C Ex. D Ex. E Ex. Eg. G

4'-hydroxy-2-nitro-diphenylamine - 0.1 0.05 4 '- (N, N-bis-3-hydroxyethylamino) -2-nitrodiphenylamine 0.05 - 0.16 0.25

Diethanolamine 2.00 2.00 2.00 2.00

Diethylene glycol monoalkyl ether 4.00 4.00 4.00 4.00 4.00

Laurindiethanolamide 1.50 1.50 1.50 1.50 1.50

Triethanolamine salt of p-dodecylbenzenesulfonate 0.50 0.50 0.50 0.50 0.50 CH3 (CH2) 7CH = CH (CH2) 7 CON [(CH2CH2O) 25H12 1.90 1.90 1.90 1.90 1 , 90

Methyl cellulose x) 2.40 2.40 2.40 2.40 2.40

Oleic Acid 1.00 1.00 1.00 1.00 1.00

Scent 0.125 0.125 0.125 0.125 0.125

Water q.s. 100,00 100.00 100.00 100.00 100.00 pH value is adjusted to 9.6 9.6 9.6 9.6 9.6 12 U4641 si) The methylcellulose mentioned in this example and elsewhere as follows: methoxy content 27.5 to 31.5%; viscosity of 2% aqueous solution about 20 ° C at cps 1500; average molecular weight 63,000.

If desired, the fragrance may be omitted from any of the compositions of Examples C through G.

The following examples further illustrate the use of a gel base and a cream base which serve as a carrier for the nitrodiphenylamine dye. The dyes used in these examples are of the type prepared according to Examples 1 to 4 above.

Table IV

Weight Percent

Ingredients Example H Example I

Dye 0.030 0.040

Diethanolamine - 0.800

Triethanolamine 2,750

Diethylene glycol monoalkyl ether 5,000 3,500

Laurindiethanolamide 3,000 1,800

Polyoxyethylene hydrogenated fatty amide 1,800 1,800

Sodium Carboxymethyl Cellulose 4,200 2,800

Oleic acid 1,500 2,000

Scent 0,100 0.125

Water q.s. 100,000 100,000 pH value is adjusted to 9.0 9.0

Table V

Weight Percent

Ingredients Ex.J Ex.K Ex.L Ex.M Ex.N Ex.O Ex-P Ex.Q

4'-hydroxy-2-nitro-diphenylamine 0.1 - 0.1 0.1 - 0.1 0.1 41-bis- (β-hydroxyethylamino) -2-nitrodiphenylamine - 0.2 - - 0.2 - 0.2

Ethyl alcohol 5.0 5.0 5.0 - - -

Diethylene glycol monoethyl lether - - - 5.0 5.0 5.0 5.0 5.0

Hexadecyltrimethylammonium chloride 2.0 - 1.0 2.0 - 1.0

Octadecenyl trimethyl ammonium chloride - 1.8 0.9 - 1.4 0.9 1/5 1.5

Octadecadienyltrimethylammonium chloride - - - - - · * · '^