FR2497662A1 - TINCTORIAL COMPOSITION FOR KERATINIC FIBERS BASED ON NITRO-3 ORTHOPHENYLENEDIAMINES, NOVEL NITRO-3 ORTHOPHENYLENEDIAMINES USED AND METHODS FOR THEIR PREPARATION - Google Patents

Abstract

THE INVENTION RELATES TO TINCTORIAL COMPOSITIONS FOR KERATINIC FIBERS CHARACTERIZED BY THE FACT THAT THEY CONTAIN AT LEAST ONE DYE THAT MEETS THE FORMULA: (CF DRAWING IN BOPI) IN WHICH R AND R DESIGNATE INDEPENDENTLY ONE OF THE OTHER ONE HYDROGEN ATOM, AN ALKYL GROUP, A MONO- OR POLYHYDROXYL ALKYL GROUP, AN ALKYL GROUP SUBSTITUTED BY AN ALCOXY GROUP, AN AMINOALKYL GROUP OF WHICH THE AMINO GROUP MAY POSSIBLY BE MONO- OR A LITTLE ALKYL GROUP, ALSO RADTITUSLY DESIGNATION OF A PHENYL GROUP, OR PHENYL SUBSTITUTED BY AN ALKYL, HYDROXYL, OR AMINO GROUP, Z DESIGNATES AN ATOM OF HYDROGEN OR AN ALKYL GROUP OR THEIR COSMETICALLY ACCEPTABLE SALTS.

Description

Dyeing composition for keratin fibers - base

  nitro-3 orthophenylenediamines, new nitro-3 orthophenyl

  Nylenediamines used and processes for their preparation.

  As is well known, fiber is often

  keratinous and in particular to human hair a colora-

  direct or complementary reflections in the case of oxidation dyeing using nitro derivatives of

  benzene series. The plaintiff has discovered that in order

  keratin fibers of red shades could be used, contrary to what could be expected,

  nitro-ortho. This is particularly

  taking into consideration that nitro-4-orthophenylenediamine

  gives rise to yellow colorings.

  It found that the hair dyes thus obtained using this class of dyes

good light stability.

  These dyes also have the advantage of being little or not selective. Selectivity is, as is well known, an important practical problem in the field of

  hair dye due to the different sensitization

  rent of the hair from the root to the point. Indeed, the

  is usually in the presence of a hair whose

  sensitization is practically zero for the fresh root

  strongly developed, strong for the parties previously

  stained, discolored or

  manente and very strong for tips that have undergone several

  these treatments and which are exposed daily to the

  light and weather.

  The Applicant has discovered that the new class of nitro-3 orthophenylenediamines retained makes it possible to obtain coloration intensities substantially similar to that of the hair

are permed or not.

  It has also been found that the dyes used in accordance with the invention were particularly stable in oxidation dye supports and in particular in ammonia medium in the presence of reducing agents, which makes it possible to associate them with the so-called oxidation dyes in order to obtain oxidation dyes.

shades rich in reflections.

  The present invention therefore relates to dyeing compositions for keratinous fibers containing nitro-3 orthophenylenediamines. Another object of the invention is constituted by the

  new nitro-3 orthophenylenediamines used in accordance

  according to the invention and their methods of preparation.

  Other objects of the present invention will appear at

  reading the description and examples that follow.

  The dyeing compositions for keratinous fibers in accordance with the invention are essentially characterized by the fact that they contain, in a suitable solvent medium for dyeing the keratinous fibers, at least one dye corresponding to the NHR 2 formula

O2N NHR1

{I)

  wherein R1 and R2 independently designate one of

  the other a hydrogen atom, an alkyl group, a group

  monoalkyl or polyhydroxy alkyl group, an alkyl group substituted by an alkoxy group, an aminoalkyl group whose amino group may optionally be mono- or disubstituted with an alkyl group, the radical R2 may also designate a phenyl group, or phenyl substituted by a alkyl, hydroxyl, or amino group, Z denotes a

  hydrogen atom or an alkyl group.

  In the aforementioned formula, the alkyl radical preferably denotes a radical having from 1 to 4 carbon atoms and the

  alkoxy group is preferably methoxy or ethoxy.

  Among the more particularly preferred groups

  can be cited for R2 a hydrogen atom, a metal group

  thyl, ethyl, propyl, butyl, a 5-hydroxyethyl group,

  an β-hydroxypropyl group, a β-dihydroxy group;

  propyl, an N, N-diethylaminoethyl group, a hydroxyphenyl group, or a / -methoxyethyl group for R1 a

  hydrogen atom, a methyl, ethyl, A-hydroxy-

  ethyl and for Z a hydrogen atom and a methyl group.

  Compounds giving particularly advantageous results

  tageux in the context of the present invention meet the

  formula (I) in which Z obligatorily designates a group

  methylation. Other compounds giving particular results

  particularly appreciable are those for which R2 is different.

  of hydrogen and in particular designates methyl or t-hydroxy

  ethyl. These compounds have in particular a good safety.

  These compounds can also be used in the form of their cosmetically acceptable salts, such as in the form of

hydrochloride, sulfate, etc.

  The preferred compounds used according to the invention make it possible to obtain more or less rich coppery shades.

  in red ranging from 7.5 YR to 10 R according to the Munsell evaluation.

  The shade is denoted by H in the Munsell notation that a color is defined by the formula HV / C in which the three parameters denote respectively the shade or "hue" (H), the intensity or Wvalue "(V) and purity or "chromaticity" (C), the slash being a simple convention As far as Munsell's notation is concerned, reference may be made to the publication of "Official Digest" April 1964,

pages 373 to 377.

  Among the compounds used according to the invention, the compounds of formula (II): NHR '

O2N NHR'1

I (II)

Z '

2 2

  wherein R 'and R' independently denote one of i 2

  the other a hydrogen atom, an alkyl group, a group

  mono or polyhydroxy alkyl, a substituted alkyl group

  killed by an alkoxy group, an amino alkyl group

  the amino group can optionally be mono or di-substituted

  killed by an alkyl group, the radical R2 may also denote a phenyl or phenyl-substituted by a hydroxyl or amino alkyl group and Z 'denotes a hydrogen atom or an alkyl group provided that R'1, R'2 and Z 'can not designate hydrogen simultaneously, when R'2 denotes methyl or phenyl R'1 and Z' can not both designate hydrogen simultaneously, when Z 'denotes methyl

  at least one of the groups R'1 or R'2 is different from hydro-

  gene, when R'1 and R'2 denote methyl Z 'is different from hydrogen, and their cosmetically acceptable salts are new. The process for preparing these compounds, which constitutes another subject of the invention, consists, with regard to the compounds of formula (I) for which R 1 denotes hydrogen, to selectively reduce the compounds of formula

(III):

NHR 2

02N NO2

2o (III)

  selective reduction being carried out either with the aid of

  alkaline salt according to Mr. Kamel, Mr. Ali and Mr. M. Kamel,

  Tetrahedron 1966, vol. 22, page 3353 either by transfer of

  from cyclohexene to the compound of formula (III) in

  Palladium on carbon as a catalyst according to Ian D. Entwistle, Robert A. W Johnstone and T. Jeffery Povall, JCS

Perkin I 1975, page 1300.

  The compounds of formula (I) for which R1 denotes

  alkyl or substituted alkyl can be obtained by benzene-

  selectively sulphonating or paratoluenesulfonating the compounds of formula (I) for which R1 denotes hydrogen. The arylsulphonamides thus obtained are then reacted with a haloalkane of formula XR1, in which X denotes a halogen atom and R1 alkyl or substituted alkyl, and then

  substitution or hydrolysis sulfonamides.

  The reaction scheme can essentially be summarized as follows:

NHR2 NHR2

NH 2 2N

NHSO i R3 = H or NHR2

N - SO 3

  A number of the intermediate compounds of formula (III) used in accordance with the process of the invention are known per se. In general, these compounds of formula (III) can be obtained by the action of ammonia or amines of formula R 2 NH 2, in which R 2 has the same meaning as that indicated above, on the compounds

  dinitrated, chlorinated or methoxylated using the

  the chlorine atom or the methoxy group.

  The compositions in accordance with the invention may be used for the direct dyeing of keratinous fibers or for the oxidation dyeing of these fibers, in which case the O 2 N O 2 N O 2 N compounds of formula (I) confer complementary reflections on the basic coloration obtained by oxidative development of

  precursors of oxidation dyes. These compositions

  contain the compounds of formula (I) in proportions of between 0.001 and 5% by weight and preferably between

  0.01 and 3% by weight relative to the total weight of the composition

dyeing.

  They may contain anionic surfactants

  cationic, nonionic, amphoteric or

  diapers. These surfactants are present in the compositions of the invention in proportions of between 0.5 and 55% by weight and preferably between 4 and 40% by weight.

  weight relative to the total weight of the composition.

  The cosmetic vehicle is generally constituted by water and organic solvents can also be added to the compositions to solubilize compounds which are not sufficiently soluble in water. Among these solvents there may be mentioned lower alkanols such as ethanol and isopropanol, polyols such as glycerol, glycols or glycol ethers such as butoxy-2 ethanol, ethylene glycol, ethylene glycol monoethyl ether. , propylene glycol, diethylene glycol monoethyl ether and monomethyl ether as well as similar products and mixtures thereof. These solvents are preferably present in proportions ranging from 1 to 75% by weight and in particular from

  at 50% by weight relative to the total weight of the composition.

  The compositions can be thickened preferably with the compounds chosen from sodium alginate, gum

  arabic, cellulose derivatives such as methylcellulose

  lulose, hydroxyethylcellulose, hydroxypropylmethylcellulose

  lulose, carboxymethylcellulose and various polymers

  having the function of thickener such as more particularly

  acrylic acid derivatives. It is also possible

  sible to use mineral thickeners such as

  bentonite. These thickeners are preferably present

  in proportions of between 0.5 and 10% by weight and in particular between 0.5 and 3% by weight with respect to

total weight of the composition.

  The compositions according to the invention may also contain various adjuvants usually used in hair dye compositions and in particular penetrating agents, sequestering agents, film-forming agents, buffers, preservatives and perfumes.

  These compositions may be in various forms

  such as liquids, creams, gels or any other form suitable for dyeing hair. They can also be packaged in aerosol bottles in

presence of a propellant.

  The pH of these dyeing compositions can be between 3 and 11.5, preferably between 5 and 11.5. It is adjusted to the desired value using an alkalinizing agent such as

  ammonia, sodium carbonate, potassium carbonate or ammo-

  nium, sodium or potassium hydroxides, alkanol-

  amines such as mono, di- or triethanolamine, alkylamines such as ethylamine or triethylamine or

  using an acidifying agent such as phosphoric acid

  hydrochloric acid, tartaric acid, acetic acid, lactic acid or

cudgel.

  When the compositions are intended to be used in a direct hair dyeing process, they may contain, in addition to the compounds in accordance with the invention, other direct dyes such as azo dyes or

  anthraquinones, such as tetraminoanthraqui-

  none, nitro dyes of the benzene series different from the compounds of formula (I) and more particularly the following compounds: methyl 2-nitro-6-aniline, 3-nitro-4-aminophenol, 3-nitro-4-hydroxyethylamino phenol, 3-nitro-4-amino-6-methylphenol, 3-amino-4-nitro-phenol, 2-amino-3-nitro-phenol, 3-nitro, N-hydroxyethylamino-6-anisole, N-f, 3-dihydroxypropylamino-3-nitroanisole, (N-methylamino-3-nitro-4) phenoxyethanol,

  (N-methylamino-3-nitro-4) phenyl, f, r-dihydroxypropyl-

  ether, N, N '- (- (-hydroxyethyl) nitro paraphenylenediamine, nitro-3, N'-methylamino-4, N, N- (di- (-hydroxyethyl) aniline, 2-methyl-4-amino-nitro- N- (-hydroxyethylaniline), 2-methyl-4-amino-5-nitro-N-methylaminoethylaniline,

  2-methyl-4-amino-5-nitro-N-methylaniline. Concentrations

  These direct dyes other than the dyes of formula (I) may be between 0.001 and 5% by weight.

  relative to the total weight of the composition.

  These compositions are applied to keratin fibers

  during a laying time of 5 to 70 minutes, then the fibers are rinsed, possibly washed, rinsed again

and dried.

  These compositions may also be used in the form of a hair styling lotion designed both to give the hair a slight coloration and to improve the holding of the setting. In this case, they are in the form of aqueous, alcoholic or aqueous-alcoholic solutions containing at least one cosmetic resin and

  their application is carried out on wet hair previously

  washed and rinsed, which may be rolled up and then dried. The cosmetic resins used in lotions of

  in particular, the polyvinyl pyrrole

  pyrrolidone; crotonic acid-vinyl acetate copporters,

  vinylpyrrolidone-vinyl acetate, semi-esters of copoly-

  maleic anhydride-butylvinyl ether and maleic anhydride-methylvinyl ether as well as any other cationic, anionic, nonionic or amphoteric polymer usually used in this type of compositions. These cosmetic resins are used in the compositions of the invention in amounts of 1 to 3% by weight and preferably 1 to 2% by weight on the basis of

total weight of the composition.

  When the compositions constitute oxy dyes,

  The compounds of formula (I) according to the invention are essentially used in order to bring reflections to

the final dyeing.

  These compositions then contain, in combination with at least one nitro dye of formula (I), oxidation dye precursors.

  They may contain, for example, paraphenylene

  diamines such as: para-phenylenediamine, para-

  lylenediamine, 2,6-dimethyl paraphenylenediamine,

  2,6-dimethyl-3-methoxy-para-phenylenediamine, the N- (-methyl)

  thoxyethyl) paraphenylenediamine, N, N-di ((-hydroxy)

  ethyl) amino-4-aniline, N, N- (ethyl, carbamylmethyl) amino-4

aniline, as well as their salts.

  They may also contain para-aminophenols, for example: para-aminophenol, N-methyl-para-aminophenol, 2-chloro-4-aminophenol, 3-chloro-4-aminophenol,

  2-methyl-4-amino phenol, and their salts.

  They may also contain heterocyclic derivatives, for example: 2,5-diaminopyridine, N, N-diethylamino-5

  2-amino-pyridine, 7-amino-benzomorpholine, 2-amino-hydrochloride

xy-5 pyridine.

  The compositions according to the invention may contain, in combination with para-type oxidation dye precursors, couplers well known in the state of the art.

  As couplers, mention may be made in particular of:

  diphenols such as resorcinol, 2-methyl resorcinol, meta-aminophenols such as: metaminophenol, methyl-2

  5-amino-phenol, 2-methyl-N- (-hydroxyethyl) amino-5-phenol

  6-hydroxybenzomorpholine and their salts, metaphors

  nylenediamines such as: (2,4-diamino) phenoxyethanol,

  2,4-diaminophenyl-aminoethyl ether, 6-amino benzomor-

  pholine, N- (e-hydroxyethyl) amino-2-amino-47-phenoxyphenol

  ethanol, (2,4-diamino) phenyl e, β-dihydroxypropyl ether and their salts, metaacylaminophenols, metauridophenols,

  metacarbalcoxyaminophenols such as: 2-methyl acetyl

  5-amino-phenol, 2-methyl-5-ureido phenol, methyl-2

carbethoxyamino-5-phenol.

  Finally, we can mention as other couplers used

  in the compositions of the invention: α-naphthol, couplers having an active methylene group such as diketone compounds and pyrazolones and heterocyclic couplers such as 2,4-diaminopyridine, as well as

their salts.

  These compositions contain, in addition to oxidation dye precursors, reducing agents such as, more particularly, sodium sulphite, thioglycolic acid,

  thiolactic acid, sodium bisulfite, ascorbic acid

  and hydroquinone. These reducing agents are present in proportions of between 0.05 and 1.5% by weight relative to the total weight of the composition. The precursors of

  oxidation dyes may be used in

  compositions of the invention at concentrations of between 0.001 and 5% by weight and preferably between 0.03 and 2% by weight.

  weight based on the total weight of the composition. The

  Tears may also be present in proportions of between 0.001 and 5% by weight, preferably between 0.015 and 2% by weight. Their pH is preferably between 7 and 11.5 and is adjusted using alkalinizing agents defined above. The Applicant has found that the compounds according to the invention were particularly stable in such

compositions.

  The process for dyeing keratinous fibers, in particular

  human hair, implementing the revelation

  by an oxidant, consists in applying to the hair the

  dyeing position comprising both a dye according to the invention and oxidation dye precursors and to develop the coloration with the aid of an oxidizing agent present in the dyeing composition or applied to the dyes;

hair in a second time.

  The oxidizing agent is preferably chosen from hydrogen peroxide, urea peroxide and persalts. We use

  particularly a solution of hydrogen peroxide at 20 volumes.

  Once the composition with the oxidizing agent has been applied to the keratinous fibers, the composition is allowed to stand for 10 to 50 minutes, preferably 15 to 30 minutes, after which the keratinous fibers are rinsed, washed optionally with

  5. Shampoo rinse again and dry.

  The following examples are intended to illustrate the

  vention without being limiting in nature.

249-7662

EXAMPLE 1

  The following dye composition is prepared: Amino-2-nitro-3-methyl-5-N-methylaniline ........ 0.9 g Butoxy-2 ethanol ............... ..............

  . 10 g Alfol C16 / 18 (50/50) ............................ 8 g Wax of lanette ...... ........................... 0,5 g Cemulsol B ................. ... DTD: ................. 1 g Oleic diethanolamide ........................ ..1, 5 g Triethanolamine ................................. 1 g Water ....... ..100 g E u .......... qsp .......................... 1OOg..DTD: This composition has a pH of 9.

  This mixture applied 25 minutes at 28 C on hair

  discolored gives them after rinsing and shampooing a colo-

  ration of 2.0 YR 5.5 / 8 according to Munsell.

  The compositions mentioned in Table 1 following the support being the same as that used in Example 1 are prepared in the same way as that indicated above.

  the basifying agent being specified as well as the pH. The conditions

  Dyestuffs such as temperature, rinsing and washing being similar to that shown in Example 1. A sufficient amount of water per 100 g of composition being

always added.

  By applying the composition of Example 2 to naturally white hair at 90% previously permed 2 and, in the same way, proceeding in the same way, a coloration of 7.5 YR 6/8 according to Munsell is observed identical to that observed on hair naturally occurring. 90% whites, dyed in

the same conditions.

TABLE I

  k COLORING COMPOSITIONS DYE EX ._____.___ ------------------- t -----------! ----- --____________ _ alkalizing% g I pH Natural Hair 4 I --I -----------------__-__________ _____ ____ - bleached white 90%: 1 amino-2-nitro-3 methyl-5,9-triethanolamine: 19: 25 min 2: YR 5.5 / 8: N-méthylanillne

*: *:::

  2-nitro-3-orthophenylene diamine-0.35: triethanolamine: 19 30: 7.5Y R6 / 8 3 :: * R 6 /: a: N .: 3: N-methylamino-2-nitro-3-aniline: ammonia 1

::::: :::

  220B i 10.6 7.5 'R 6/9: .4: 4 N-3-hydroxyethylamino-2-nitro-3 aniline ammonia 2: 22B 1 106 20: 5 YR 6/11: 2-amino-2-nitro- 3 N -ethylaniline.2: ammonia:::;:;:. 22 B 2 1: 25: 10 R 5/10: 1.5 YR 4/8 ç 2-amino-3-nitro, N-methylaniline.1 N-5-hydroxyethylamino-2-nitro-3-ammonia: 22 B 1:10, 5:25 :: YR4 / 7: aniline:

:::::

  tetraaminoanthraquinone: 0.25 N-methylamino2-nitro-3-aniline: 12.5: 25: 3 YR 4/3:: N, N'-hydroxyethyl-nitro-p - ::: 4: 3 7 phenylenediamine: 0.31 ::: ::: tetraaminoanthraquinone 0.4:

: * :::: ::::

:: 0, .2 5 <;: _

:::, ::

  8 * N-methylamino-2-nitro-3-methyl-5-aniline: 0.25: ammonia &: 0, 8: 10: 30: 6 YR 7/4 ::

:: 220B ::::

  : 7: n: 1: n: e, i: di (4'-hydroxyphenyl) amino-2-nitro-3-C-methyl-5-aniline 0.35 "ononthanolamine 110 30 6YR *

EXAMPLE JO0

  The following dye composition is prepared: Amino-2, nitro-3, methyl5, N-methylaniline ... 0.5 g Nitro-3, N'-methylamino-4, N- (aminoethylaniline) 100, 1 g (N-methylamino-3, nitro-4) phenoxyethanol .......

  0.28 g Ethanol 96 ..................................... 5 g Propylene glycol .. ................................. 5 g Coconut fatty acids diethanolamides ........ .... 2.2 g Lauric Acid ..................... DTD: ............... 0, 8 g Ethylene glycol monoethyl ether ................ 2 g Monoethanolamine ........................ .......... 1,1 g Water ............ DTD: .... sp ................ ........... 10 g pH 10.5..DTD: This mixture applied for 25 minutes at 30 C on hair

  colored to white gives them after rinsing and shampooing a

light red copper color.

EXAMPLE 11l

  The following dye composition is prepared: Amino-2, nitro-3, methyl5 aniline ................ 0.5 g Nitro-3, N- (4-hydroxyethylamino) phenol. .

  .... 0.15 g Tetraminoanthraquinone ............................ O, 10 g Butoxy-2 ethanol ..... ............................. 10 g Cemulsol NP4 ......... DTD: ...... ..................... 12 g Cemulsol NP9 ......................... ..... DTD: ....... 15 g Oleic alcohol oxyethylenated with 2 moles of ethylene oxide ....... DTD: ............. .................... 1.5 g Oleic alcohol oxyethylenated with 4 moles of ethylene oxide .............. .......................... 1.5 g Triethanolamine ................... ................ 2 g..DTD: Water ............

  at ......... qsp ............................. 1OO g pH 9. This mixture applied 35 minutes at 30 C on hair

  discolored straw-blonde confers them after rinsing and shampooing

  pooing a medium coppery brown coloring.

EXAMPLE 12

  The following dye composition is prepared: Nitro-3 orthophenylenediamine ..................... 0.3 g

  Nitro-3, N'-methylamino-4, N, N-di-A-hydroxyethyl-

  aniline ............................................. 0O, 11 g N, N'-hydroxyethyl nitroparaphenylene diamine ... 0.18 g Alcohol at 960 .............

....................... 10 g Carboxymethylcellulose ........................ DTD: .... 2 g Ammonium Lauryl Sulfate .......................... 5 g Monoethanolamine ......... ......................... 2 g Water ........... qs p ............................... 100 g..DTD: pH 10.5.

  This mixture applied 25 minutes to 30 on hair

  discolored straw-blonde confers them after rinsing and shampooing

  pooing a very coppery brown coloring.

EXAMPLE 13

  The following dye composition is prepared: N-butylamino-2-nitro-3-methyl-5-aniline 0.3 g

  Nitro-3, N'-methylamino-4, N, N-dihydroxyethyl-

* aniline ........................................... 0.05 g Butoxy -2 ethanol.

  ............................... 10 g Diethanolamides of copra fatty acids .... 2 ..... .2,2 g Lauric acid .................................... 0,8 g Monoethyl ether ethylene glycol ............... 2 g Monoethanolamine ............................. ..... 1 g Water ........... qs p ..................... 100 g pH 8.5 This mixture applied for 30 minutes at 28 C on white-bleached hair gives them after rinsing and shampooing. DTD: a light beige color with golden highlights.

EXAMPLE 14

  The following dye composition is prepared: N-diethylaminoethylamino-2-nitro-3-methyl-5-aniline .........................

  ................ 1 g 2-Butoxyethanol ............................ ...... 5 g Laurel alcohol with 10.5 moles of ethylene oxide ... 5 g Ammonia at 22 B ... DTD: ............... ............... 1 g Water. ..... qsp .................... 100 g pH 9. This dye composition applied 25 minutes at 28 C..DTD: on discolored hair gives them after rinsing and shampooing

  6.5 YR 5/10 coloring according to Munsell.

EXAMPLE 15

  The following dye composition is prepared: N-3-hydroxypropylamino-2-nitro-3-methyl-5-aniline hydrochloride ........................... ..

  ... 0.5 g Propylene glycol .................................. 10 g Carboxymethylcellulose .... ........................ 10 g Monoethanolamine .... DTD: ................. ........... 5 g Water ............. qsp .................... DTD: ........ 100 g This mixture applied for 25 minutes at 30 C on white-bleached hair gives them after rinsing and shampooing. DTD: a 4 YR 7/7 coloring according to Munsell.

  EXAMPLE 16 The following dye composition is prepared: N-, 2-dihydroxypropylamino-2-nitro-3-methyl-5-aniline hydrochloride.

  ....................... 1.82 g Nitro-3, N- / -hydroxyethylamino-4-phenol .... DTD: ..... .0.3 g..DTD: Nitro-3, N'-methylamino-4, N, N-di-O -hydroxyethyl-

  aniline .................................................. 0.5 g Butoxy- 2 ethanol ..

  ............................... 10 g lauric acid monoethanolamide .... DTD: ...... ....... 1.5 g lauric acid .................................... 1 g Hydroxyethylcellulose ............................. 5 g Monoethanolamine ... DTD: ........... .................... 4 gEau ............ qsp ............... ... DTD: ........... 100 g..DTD: pH 10.

  This mixture applied for 25 minutes at 30 ° C. on 90% naturally white hair gives them a brown coloring.

clear red copper.

EXAMPLE 17

  The following dye composition is prepared: N-α-methoxyethylamino-2-nitro-3-methyl-5-aniline. 0.6 g 2-Butoxy ethanol ..........................

  ...... 10 g Carbopol 934 ...................................... 2 g Monoethanolamine .................................. 2 g Water ........... qs ..DTD: ... 100 ......................... OO g pH 8.8 This dye composition applied 30 minutes at 30 C .. DTD: on discolored hair confers them after rinsing and shampooing

  pooing a 7.5 YR 7/6 coloring according to Munsell.

EXAMPLE 18

  The following dye composition is prepared: N-A hydroxypropylamino-2-nitro-3-methyl-5-aniline hydrochloride .............................

  ... 1 g Paraphenylenediamine .............................. 0.25 g Paraaminophenol ......... .......................... 0.065 g Resorcinol ......... DTD: .......... ..................... 0.2 g Metaaminophenol ..................... DTD:. 0.08 g 2-methyl-N, 8-hydroxyethylamino-5-phenol ......... 0.05 g 2-Butoxyethanol .... .............................. 8 g Carboxymethylcellulose ................. ........... 2 g Ammonium lauryl sulphate .......................... 5 g Ammonium acetate. ................. DTD: ............. 1 g Propylene glycol. .................................. 8 g Masquol DTPA ............ .......................... 2 g Thioglycolic acid .................... ........ 0.4 g Ammonia at 22 B .......... DTD: ...................... .10 g Water ............. qsp ........................ DTD: .... 100 g ..DTD: pH 10.6.

  At the time of use, 100 g of hydrogen peroxide at 20 volumes are added. This mixture applied 30 minutes at 30 C on hair

  discolored straw-blonde confers them after rinsing and shampooing

  pooing a medium brown color with copper highlights.

EXAMPLE 19

  The following dye composition is prepared: Amino-2, 3-nitro-5-methylaniline ................. 0.8 g Para-phenylene diamine ......... ..............

  .... O, 18 g Paraaminophenol .................................... 0.05 g Resorcinol. ........................................ 0.12 g Metaaminophenol ... DTD: ................................ 0.115 g 2,4-Diamino phenoxyethanol dihydrochloride ...... 0, 03 g Cemulsol NP4 ..................................... DTD: .12 g Cemulsol NP 9. ..................................... 15 g Oleic alcohol with 2 moles of ethylene oxide ....... 1.5 g Oleic alcohol with 4 moles of ethylene oxide ....... 1.5 g Propylene glycol ............... .............. DTD: ..... 6 g Trilon B ......................... ................. 0.12 g Ammonia at 22 B ......................... ....... 11 g Thioglycolic acid .............................. 0.6 g Water .... ... qsp ......... DTD: ....................... 100 g..DTD: pH 10.5.

  At the time of use, 100 g of hydrogen peroxide are added

volumes.

  This mixture applied for 30 minutes at 30 ° C. on naturally white hair at 90% gives them, after rinsing and

  shampoo a medium coppery brown coloring.

EXAMPLE 20

  The following dye composition is prepared: N-diethylaminoethylamino-2-nitro-3-methyl-5-aniline .........................

  ............... 1 l, 5 g..DTD: Nitro-3, N'-methylamino-4, N, N-di-hydroxyethyl-

  aniline ............................................. 0.2 g Butoxy- 2 ethanol ..

.............................. 10 g Carboxymethylcellulose ................. DTD: ........... 10 g Monoethanolamine .................................. 5 g Water .......... qsp ............................... 100 g..DTD : pH 10.

  This mixture applied 30 minutes at 30 C on hair discolored to white, gives them after rinsing and shampooing

a beige beige color.

EXAMPLE 21

  The following dye composition is prepared: N-2-hydroxyethylamino-3-nitro-5-methyl-aniline .............................. ............. 1,2 g 2-Butoxyethanol ............................. ..... 10 g lauric acid monoethanolamide ................. 1.5 g lauric acid ............... ......

  ............. 1 g Hydroxyethylcellulose ............................. 5 g Monoethanolamine .. ................................ 2 g Water ........... qs p ............................... 100 g..DTD: pH 10.

  This mixture applied for 25 minutes at 28 C on white-bleached hair gives them after rinsing and shampooing

  staining 5 YR 8/6 according to Munsell.

EXAMPLE 22

  The following dye composition is prepared: N- <-hydroxyethylamino-2-nitro-3-methyl-5-aniline ............................. 1.21 g Paraphenylenediamine. ............................. 0.5 g Resorcinol ........

  ............................... O, 1 g Metaaminophenol .............. ..... DTD: ............... 0.21 g Orthoaminophenol ...................... ........... 0.17 g Carbopol 934 ...................................... 1,5 g Alcohol to 960 ..................................... 11 g Butoxy-2 ethanol ...... ....... DTD: ......................... 5 g Trimethyl cetyl ammonium bromide ......... DTD: ...... 1 g Trilon B ...................................... .... O, 1 g Ammonia at 22 B ................................. 10 g Thioglycolic acid. ................ 0, ........... 2 g Water ......... qsp.00 ...... DTD: .......... g..DTD: pH 10.5.

  At the time of use, 100 g of hydrogen peroxide at 20 volumes are added. This mixture applied for 25 minutes at 28 ° C. on naturally white hair at 90% gives them, after rinsing and

  shampoo a dark brown color with copper highlights.

EXAMPLE 23

  The following dye composition is prepared: Nitro-3 orthophenylenediamine .................... 0. 5 g 2-methyl-6-nitroaniline.

...................... 0.2 g Paraphenylenediamine ....................... ... DTD: .... 0.08 g Methyl-2 resorcinol .................... 0.045 g Metaaminophenol .......... ......................... 0.06 g Cemulsol NP4 ....... DTD: .......... ..................... 21 g Cemulsol NP9 ........................ 24 oleic acid ..................................... 4 g Butoxy-2 ethanol .... ............................... 3 g Ethanol at 96 .............. ... DTD: .................... 10 g Masquol DTPA ..................... ................ DTD: .2,5 g Sodium bisulphite solution at 35 B ............... 1 g Ammonia at 22B ... .............................. 10 g Water ......... qsp .... DTD:. ........................... 100 g..DTD: pH 11.

  At the time of use, 80 g of hydrogen peroxide are added

volumes.

  -This mixture applied for 25 minutes at 30 ° C on 90% naturally white hair gives them after rinsing and

  shampoo a dark golden color very golden.

  The following examples are intended to illustrate the

  processes for the preparation of new compounds used in

according to the invention.

PREPARATION EXAMPLE 1

  Preparation of N-Butylamino-2, Nitro-3, Methyl-5-aniline

NH-CH 2 -CH 2 -CH 3

2 days NH2

0 2N NH2

CH3 and NH- (CH2) 3

02N - N02 02N 2

+ H2N- (CH2) 3CH3

CH3 CH3

NH-CH2 CH2 CH 2 -CH3

H2N N 2

  CH 3 a) Preparation of 2,6-dinitro-4-methyl-N-butylaniline 0.05 mol (10.8 g) of 2,6-dinitrophenyl-4-chlorobenzene are added slowly with stirring over 10 minutes. in ml of butylamine cooling, if necessary, the reaction medium so as not to exceed 50 C. The addition is complete,

  maintain the stirring for 5 minutes and then pour the reaction medium

  in 100 ml of ice water. The expected product

  peel, wring it out, wash it with water and recrystallise it

  ethanol. After drying under vacuum it melts at 52 C.

  Analysis Calculated for Found CllH15N304

C, 52.17, 52.13

H% 5.93 6.04

N% 16.60 16.59

0% 25.30 25.34

  b) Preparation of N-butylamino-2, nitro-3, methyl-5 aniline. 0.041 mole (10.4 g) of 2,6-dinitrobromyl-N-butylaniline is added to 50 ml of ethanol to which are added 10.8 g of cyclohexene and 2.8 g of 10% Pd / C. The reaction medium is refluxed for one hour and then filtered hot to remove the catalyst. The filtrate is cooled to -15 C. The expected product crystallizes. It is drained, washed with a little iced alcohol and dried under vacuum. He created

68oC.

  Analysis Calculated for Found CllH17N32

C% 59.19 59.33

H% 7.62 7.75

N% 18.83 18.98

0% 14.35 14.44

EXAMPLE OF PREPARATION 2

  Preparation of N-methoxyethylamino-2-nitro-3-methyl-5-aniline

NH-CH2-CH2-OCH3

O2N // H

2 2

CH3 Cl O2N

NH-CH2-CH2-OCH

2 2 3

NO2 O2

H2N-CH2CH 20CH3

NH-CH2CH2OCH3

  H2N a) Preparation of 2,6-dinitro-4-methyl-N-C-methoxyethylaniline. 0.05 mol (10.8 g) of 2,6-dinitrobromylchlorobenzene in 25 ml of methoxyethylamine are added gradually with stirring over 10 minutes, cooling the reaction medium if necessary in order not to exceed 50.degree. The addition ended on

  maintain the stirring for 5 minutes and then pour the reaction medium

  in 100 ml of ice water. The expected product

  mite. It is wrung, washed with water and recrystallized in

  ethanol. After drying under vacuum it melts at 75 C.

  Analysis Calculated for Found CloH 13N305

C% 47.06 47.08

H% 5.13 4.99

0% 31.34 31.07

N% 16.47 16.50

  b) Preparation of N-methoxyethylamino-2, nitro-3,

5-methylaniline.

  0.03 moles (7.65 g) of 2,6-dinitrophenyl, methyl-4-methoxyethylaniline are dissolved in 38 ml of absolute alcohol containing 12.3 g of cyclohexene and 3.8 g of Pd / C. 10%. The alcoholic solution is then refluxed for 15 minutes. The hot reaction medium is filtered to remove the catalyst and, after

  After cooling down, 15 ml of alcohol saturated with

  water. The expected product precipitates in the form of

  hydrate. The hydrochloride is filtered off and washed with a little alcohol, and then it is put back into solution in water. This aqueous solution is alkalinized with ammonia to precipitate the expected product which is drained, washed with water and

  recrystallized from ethanol, it melts at 71 ° C.

  Analysis Calculated for Found Clo0H15N303

C% 53.33 53.46

H% 6.67 6.70

N% 18.67 18.55

0% 21.33 21.27

EXAMPLE OF PREPARATION 3

  Preparation of Nitro-2, 4-methyl-6-amino-4-hydroxy-4-diphenylamine l

H3 NH H

NH2 Cl OH NO2 2 t N 2 X3

H3 H2 N2

NO2

-.} H3 I C NH- H

  NH 2 a) Preparation of 2,6-dinitro-4-methyl-4'-hydroxy-diphenylamine. Refluxed for 2 hours, 0.1 mole (10.9 g) of para-aminophenol and 0.05 mole (10.83 g) of 2,6-dinitrile are heated under reflux for 2 hours.

  4-methylchlorobenzene in 60 ml of alcohol. After cooling

  reaction medium, the mixture is filtered off and washed with alcohol

  2,6-dinitrophenyl-4-hydroxy-4'-diphenylamine insoluble.

  After recrystallization from alcohol and drying under vacuum, the

product background ê 192 C.

  b) Preparation of Nitro-2, methyl-4, 6-amino-4-hydroxy-diphenylamine. After adding 0.038 mole (11 g) of 2,6-dinitro,

  methyl-4-hydroxy-4'-diphenylamine to 200 ml of additional alcohol

  20 ml of ammonia at 22 B is bubbled hydrogen sulfide for 30 minutes in this solution. The reaction medium is then refluxed for 2 hours. The alcoholic solution is filtered after cooling and then evaporated to dryness under vacuum. The residue is taken up in 150 ml of 2N hydrochloric solution. It is filtered to remove the insoluble

  then the filtrate is alkalinized with ammonia. The pro-

  Expected desire precipitates. It is drained, washed with water and then

  recrystallized from ethanol, it melts at 163 C.

Calculated Analysis for Found

13 13 3 3

C% 60.23 60.03

H% 5.02 5.11

N% 16.22 16.25

0% 18.53 18.55

EXAMPLE OF PREPARATION 4

  Preparation of N-hydroxyethylamino-2, nitro-3,

5-methylaniline.

2CH2OH

O2N C1

02 NO2

H3

[CH2CH2OH

H 2N-CH 2 CH 20H

0N 'CH3

NH-CH2CH20H

0 2N NH2

H3 y

  a) Preparation of 2,6-dinitro-4-methyl-N, -hydroxy--

  ethylaniline. 0.35 moles (76 g) of 2,6-dinitropropyl-4-chlorobenzene are slowly added in the course of 10 minutes to 150 ml of ethanolamine, cooling the reaction medium, if necessary.

  to avoid exceeding 75 C. The addition is completed

  hold the stirring for 5 minutes then pour the reaction medium

  in 600 g of ice water. The expected product precipitates. We

  the wring, wash with water, then recrystallize it in the étha-

  nol. After drying under vacuum it melts at 131 C.

  Calculated Analysis for Found C9H11N305

C% 44.81 44.93

H% 4.56 4.49

N% 17.43 17.32

0% 33.20 33.00

  b) Preparation of N-α-hydroxyethylamino-2, nitro-3,

5-methylaniline.

  After adding 0.4 mole (96.4 g) of 2,6-dinitrobromyl-N-hydroxyethylaniline to 1500 ml of absolute alcohol added with 160 ml of 22 B ammonia, hydrogen sulphide is bubbled through. for 30 minutes in this alcoholic solution. The temperature goes up to 50 C then goes down again. We then stop bubbling and then bring the reaction medium

  for an hour at reflux. After concentration of the solu-

  alcoholic solution to 300 ml, the mineral salts are filtered. The filtrate is then evaporated to dryness. The residue obtained in the form of a red oil is redissolved in 80 ml of 96% ethanol. After addition of 170 ml of hydrochloric ethanol (at 7

  moles of hydrochloric acid per liter of alcohol) and

  at 0 ° C., the expected product which has precipitated in the form of hydrochloride is filtered off with suction. After washing with alcohol, this hydrochloride is dissolved in 300 ml of water. By neutralization of this solution with ammonia, N-3-hydroxyethylamino-2-nitro-3-methyl-5-aniline is precipitated. We drain

  this product, wash it with water and then recrystallise it in

  cool to 96. After drying under vacuum, it melts at 96 C.

Calculated Analysis for

C9H13N303

Find

C% 51.18 51.09

H% 6.16 6.21

N% 19.91 20.06

- 0% 22.75 22.79

PREPARATION EXAMPLE 5

  Preparation of amino-2, 3-nitro, 5-methyl-N-e-hydroxy

ethyl aniline.

O2N

NH-CH2CH2OH

  H2 02N NH Tosyl i> N-Tosyl 6H2CH2On NH

02N NH-CH2-CH2OH

CIso CH

  a) Preparation of amino-2, 3-nitro, 5-methyl-N-hydroxy-

ethyl, N-tosyl aniline.

  0.087 moles (28 g) of 2-amino-3-nitro-methyl-5-N-tosylaniline are dissolved in 85 ml of DMF preheated on a boiling water bath. 9.7 g of quicklime are then added and then, over 30 minutes, the mixture is introduced little by little and with stirring.

  0.174 moles (21.75 g) of glycol bromhydrin, while maintaining

  heating in boiling water bath. After 1½ hours, the hot reaction medium is filtered and the filtrate is then poured into 250 ml of ice water. The expected product precipitates. We

  spin, wash with water and dry under vacuum. After recreating

  in acetic acid and dried under vacuum

at 201 C.

Calculated Analysis for Found

C16H19N305S

C% 52.60 52.47

H% 5.21 5.14

o10N% 11.51 11.41

0% 21.92 21.81

S% 8.77 8.68

  b) Preparation of amino-2, 3-nitro, 5-methyl-N-A-hydroxy-

ethylaniline.

  0.0458 mol (16.7 g) of amine are introduced with stirring.

  no-2, 3-nitro, 5-methyl, N-hydroxyethyl, N-tosyl aniline in 167 ml of concentrated sulfuric acid with 48 ml of water. The mixture is heated for 1 hour in a boiling water bath and then poured over 850 g of crushed ice. The sulfuric solution is neutralized with ammonia. The expected product precipitates. After spinning, washing with water, drying under vacuum

  and recrystallization from ethanol melts at 166 ° C.

Calculated Analysis for Found

C9H1303N3

C% 51.18 50.93

H% 6.16 6.20

N% 19.91 19.85

0% 22.75 22.68

EXAMPLE OF PREPARATION 6

  Preparation of amino-2, nitro-3, methyl-5, N-methylaniline

NH2 NH2

NH Tosyl

02N -

CH3

NH2 NH2

02N - N-Tosyl -> 02N NHCH3 CH3

CH3 3

  a) Preparation of 2-amino-3-nitro-methyl-5, N-tosyl-

  aniline. 0.15 moles (25.05 g) of 2-amino-3-nitro-5-methyl-aniline are dissolved in 75 ml of pyridine, and 0.165 mole is then gradually added, with stirring, between 40 and 45.degree. (31.4 g) para-toluenesulfochloride. The addition is complete, stirring is maintained for 1 hour at 45 ° C., then the reaction medium is poured into 450 ml of ice water and the pyridine is neutralized with hydrochloric acid. The desired product is wrung out and precipitated, washed with water and then recrystallized using

  of acetic acid. After drying under vacuum it melts at 184 C.

Calculated Analysis for Found

C14H15N304S

C% 52.34 52.33

H% 4.67 4.69

N% 13.08 12.89

0% 19.94 19.86

S% 9.97 10.12

  b) Preparation of 2-amino, 3-nitro, 5-methyl-N, methyl,

N-tosyl aniline.

  0.246 moles (79 g) of 2-amino-3-nitro-5-methyl are dissolved

  N-Tosylaniline in 260 ml of normal sodium solution at 40 C.

  0.286 moles (30 ml) of sulphoxide are added slowly over 3 hours.

  After the end of the addition of the methyl sulfate, maintaining the temperature of the alkaline reaction medium is maintained by simultaneously adding 20 ml of normal sodium solution. After cooling to about 10 ° C., the expected product which has precipitated is filtered off. It is washed with a normal sodium solution

  then to water and recrystallized with acetic acid.

* After drying under vacuum it melts at 208 C.

Calculated Analysis for Found

C15H17N304S

C% 53.73 53.81

H% 5.07 5.11

N% 12.54 12.39

0% 19.10 19.01

S% 9.55 9.41

  c) Preparation of 2-amino-3-nitro, 5-methyl-N-methyl aniline. In 354 ml of concentrated sulfuric acid added with 60 ml of water and preheated to 90 ° C., 0.1785 moles (59.8 g) of 2-amino are added slowly with stirring over 1 hour. Nitro-3, N-methyl, N-tosyl aniline. We maintain the

  heating for another 15 minutes and then the reaction medium

  in 1.5 kg of ice water. The expected product precipitates as sulphate. It is wrung, washed with a little ice water. The sulphate is suspended in water and, by the addition of ammonia with stirring, the amino-2-nitro-3-methyl-5-N-methylaniline is released, which after spinning, washing

  with water and vacuum drying at 113 C.

  Calculated Analysis for Found C8H11N302

C% 53.04 53.12

H% 6.08 6.13

N% 23.20 23.14

0% 17.68 17.54

EXAMPLE OF PREPARATION 7

  Preparation of amino-2, nitro-3, N-methylaniline

NH2 NH2

02N NE2 -> 02N- $ NHSO2 XO

NH NH2

  ## STR2 ## a) Preparation of amino-2, nitro-3, Ntosylaniline

  0.1 mole (15.3 g) of 3-nitro orthophenylene

  diamine in 50 ml of pyridine and then gradually added, under

  stirring, between 40 and 45 C, 0.11 mol (21 g) of paratoluenesulphonate

  fochlorure. Once the addition is complete, stirring is maintained for 15 minutes and then the reaction medium is poured into 250 ml of ice water. The expected product precipitates. It is wrung, washed with water and recrystallized with acetic acid. It melts at C. b) Preparation of amino-2, nitro3, N-methyl N-tosylaniline 0.093 mol (28.5 g) of 2-amino-3-nitro is dissolved

  N-Tosylaniline in 112 ml of normal sodium solution at 30 C.

  0.122 moles (15.45 g) of methyl sulfate are added slowly with stirring over 1.5 hours. The temperature is maintained between 35 and 40 C. At the end of the addition of the methyl sulphate, 3 ml of solution are added simultaneously.

  1N sodium to maintain the alkaline pH.

  The reaction medium is cooled and then the expected product which has precipitated is filtered off. It is washed with a solution

  normal sodium then water and alcohol. After recreating

  in acetic acid and vacuum drying it melts at

183 C.

  c) Preparation of 2-amino-3-nitro-N-methylaniline In 230 ml of concentrated sulfuric acid added with 23 ml of water and preheated to 90 ° C., little is added to

  little, in 10 minutes, with stirring 0.0716 mol (23 g) of amine

  no-2, nitro-3, N-methyl, N-tosylaniline. The addition is complete the reaction medium is maintained for 5 minutes at 90 C and then poured on crushed ice. The acidic aqueous solution obtained is alkalinized with ammonia to precipitate the

  expected product. It is wrung, washed with water and recreated

  tallise in 40 ml of alcohol. After drying under vacuum it melts at 93 C. Calculated Analysis for Found

C7H9N30 2

C% 50.30 50.51

H% 5.39 5.31

N% 25.15 25.04

0% 19.16 19.02

EXAMPLE OF PREPARATION 8

  Preparation of N-A-hydroxypropylamino-2-nitro-3-methyl-5-aniline hydrochloride

NH-CH3-CH2CHOH

2N NH2

, HCl H3

OCH3 NH-CH2-CHOH-CH3

ON NO2> 02N - NO

02 NNH2-CH2-CHOH-CH3

CH3 CH3

3

NH-CH2-CHOH-CH3

02N NH2

  IQ, HCl H3 a) Preparation of 2,6-dinitro-methyl-N- (γ-hydroxypropylaniline 0.05 mol (10.6) are introduced gradually with stirring.

  g) 2,6-dinitro-4-methylanisole in 30 ml of 1-aminopropane

  nol-2. The reaction medium is heated for 30 minutes at 60 ° C. and then

  it is poured into 120 g of ice water. The expected product

  mite. It is wrung, washed with water and then recrystallized with a hydroalcoholic mixture. After drying under vacuum

it melts at 80 C.

Calculated Analysis for Found

13 3 5

C% 47.06 47.05

H% 5.13 5.10

0% 31.34 31.44

N% 16.47 16.36

  b) Preparation of N-e-hydroxypropylamino hydrochloride

2-nitro-3, methyl-5 aniline.

  0.02 moles (5.10 g) of 2,6-dinitro-methyl-4 are dissolved

  N- (-hydroxypropyl aniline in 40 ml of absolute alcohol containing

  0.1 mole (8.6 g) of cyclohexene. 2.5 g of 10% Pd / C are added and then the alcohol solution is brought to reflux for 10 minutes. After cooling, the reaction medium is filtered to remove the catalyst. Approximately 20 ml of alcohol is

  under vacuum and then 7 ml of ethanol saturated with chlorinated

  drique. After cooling to -10 C the expected product crystallizes. It is drained, washed with a little alcohol and then recrystallized with absolute alcohol. After drying under vacuum the expected hydrochloride melts with decomposition between 145

and 150 C.

  Analysis C% H% N% 0% C1% Calculated for C 1015N 3031HCl, 89 6.12 16.06 18.36 13.58 Found, 96 6.14 16.19 18.43 13.76

EXAMPLE OF PREPARATION 9

  Preparation of N-, r-dihydroxypropylamino-2 hydrochloride,

nitro-3, methyl-5 aniline.

NH-CH2-CHOH-CH 20H

2N NH2

HC1 H3

OCH3 NH-CH2CHOH-CH2 OH

3 2 2

O2N 2 2N NO2

'<NH2CH2CHOHCH20H

H3 H3

NH-CH2CHOH-CH20H

02N NH2

  ## STR1 ## a) Preparation of 2,6-dinitro-4-methyl-1-dihydroxy

propylaniline.

  0.05 moles (10.6 g) of 2,6-dinitrobenzylanisole are dissolved in 50 ml of absolute alcohol. To this solution we add

  with stirring, 0.1 mol (9.1 g) of 1-amino propane-

  diol-2,3. The solution is refluxed for 3 hours 30 minutes.

  The alcohol is removed under vacuum and 40 ml of ice-cold water are added to the residual red oil. The expected product crystallizes. It is wrung and washed with water. After recrystallization using a hydroalcoholic mixture and drying under vacuum it melts at

118 C.

Calculated Analysis for Found

C10H13N306

C% 44.28 44.33

H% 4.80 4.80

N% 15.50 15.72

0% 35.42 35.80

  b) Preparation of N-, -dihydroxypropyl-2-amino-3-nitro-5-methyl-aniline hydrochloride 0.03 moles (8,13 g) of 2,6-dinitro-4-methyl-N (Y) are dissolved -dihydroxypropylaniline in 60 ml of absolute alcohol

  containing 12.3 g of cyclohexene. 4 g of 10% Pd / C are added.

  The alcoholic solution is brought to reflux for 10 minutes. After cooling, the reaction medium is filtered to remove the catalyst. About 30 ml of alcohol are removed under vacuum and then 8 ml of ethanol saturated with hydrochloric gas are added. After cooling to -100C the expected product precipitates. The hydrochloride is filtered off, washed with a little ethyl ether and dried under vacuum. After two recrystallizations in absolute alcohol the expected product melts with decomposition

between 130-134 ° C.

  Analysis Calculated for Found CloH15N3O4, HCl

0% 43.24 43.18

H% 5.77 5.82

N% 15.14 15.30

0% 23.06 23.10

C1% 12.79 12.88

EXAMPLE OF PREPARATION 10

  Preparation of N-methylamino-2, nitro-3, methyl-5 aniline NHCH3 O2N Cl O2N NH2 NHCH3

NHCH 3

l NHCH3

NH2CH3

_.3 -3 -3

  a) Preparation of 2,6-dinitro-methyl-N-methylaniline To 40 ml of a 33% solution of methylamine in ethanol,

  gradually added, with stirring, 0.05 mole (18 g) of

  2,6-trichloro-4-chlorobenzene. The temperature rises to 50 ° C. and the expected derivative precipitates immediately.The addition is complete and stirring is maintained for 5 minutes, then the mixture is drained and washed with water.

  2,6-dinitro-4-methyl-N-methylaniline which, after recrystallization

  alcoholization and vacuum drying at 1320C.

Calculated Analysis for Found

C8H9N304

C% 45.50 45.40

H% 4.27 4.38

N% 19.91 19.94

0% 30.33 30.26

  b) Preparation of N-methylamino-2, nitro-3, methyl-5 aniline. 0.0407 moles (8.6 g) of 2,6-dinitrobromyl-N-methylaniline are dissolved in 45 ml of alcohol containing 0.203 moles (16.7 g) of cyclohexene. 4.3 g of 10% Pd / C are added. Wear it

  The mixture is refluxed for 20 minutes and then the reaction medium is filtered off.

  boiling point to remove the catalyst. By cooling

  The expected product crystallizes out of the filtrate. We wring it out,

  wash it with a little alcohol and recrystallise it in the étha-

  nol. After drying under vacuum it melts at 131 C.

  Calculated Analysis for Found C8H11N302

C% 53.04 53.07

H% 6.08 6.06

N% 23.20 23.26

0% 17.68 17.57

EXAMPLE OF PREPARATION 11

  Preparation of N- (-diethylaminoethylamino-2, nitro-3,.

5-methylaniline.

  ## STR5 ## wherein R 2 is O 2 N 2 CH 2 -CO 2 N 02 C2H5

/ C2H5

NH-CH2CH2-N H

I 2H5

- NO

i 2 N cyclohexene Pd / C 10% O2N

/ C 2H5

NH-CH2-CH 2 -N H

1 - 225

  a) Preparation of 2,6-dinitro-methyl-4, N, N-diethylamine

amino ethylaniline.

  0.05 mol (10.8 g) of 2,6-dinitrobutyl-chlorobenzene in 25 ml of N, N-diethylaminoethylamine are added slowly with stirring over 10 minutes, cooling the reaction medium so as not to exceed 50 C. The addition is complete

  maintain the stirring for 5 minutes and then pour the reaction medium

  in 150 ml of ice water. The expected product

  mite. It is wrung, washed with water and recrystallized in

  ethanol. After drying under vacuum it melts at 72 C.

Calculated Analysis for Found

C13H 20N404

C% 52.70 52.59

H% 6.76 6.79

N% 18.92 18.99

0% 21.62 21.50

  a) Preparation of N-P-diethylaminoethyl amino-2,

nitro-3, methyl-5 aniline.

  0.03 moles (8.52 g) of 2,6-dinitro-methyl, N, N-diethylaminoethylaniline are dissolved in 42 ml of ethanol containing 0.15 mole (12.3 g) of cyclohexene and 4.3 g of Pd / C at 10%. The reaction mixture was refluxed for 30 minutes and then boiled off to remove the catalyst. After

  30 ml of chlorinated ethanol are added to the filtrate.

  hydric (containing 7 moles of hydrochloric gas per liter).

  The expected product precipitates as hydrochloride. The hydrochloride is filtered off, washed with a little acetone and then dissolved in 30 ml of water. By neutralization of this aqueous solution with ammonia, N-12-diethylaminoethylamino-2-nitro-3-methyl-5-aniline is precipitated. This product is filtered off, washed with water and then recrystallized from

  alcohol at 95. After drying under vacuum it melts at 45 C.

Calculated Analysis for Found

C13H22N402

C% 58.65 58.75

H% 8.27 8.29

N% 21.05 21.03

0% 12.03 11.92

EXAMPLE OF PREPARATION 12

  Preparation of N-9-hydroxyethylamino-2, 3-nitroaniline

NH-CH2-CH2OH

O2N NH2

 2 <NH2

C1 NH-CH CH OH

2 2

02N_ N02> NO2

U H 2N-CH 2 CH 2 OH

NH-CH2CH 20H

I 2 2

02N NH2

  a) Preparation of dinitro 2,6-N-f-hydroxyethylaniline 0.05 moles (10.125 g) of 2,6-dinitro-chlorobenzene in 25 ml of ethanolamine are slowly added with stirring while cooling the reaction medium so that the temperature does not exceed 50 C. The reaction medium is poured into 100 ml of ice water. The expected product precipitates. It is wrung, washed with water and recrystallized from ethanol. After drying

under vacuum it melts at 160 ° C.

  Analysis Calculated for Found C8sH9N305

C 42.29 42.36

H% 3.96 4.05

N% 18.50 18.44

0% 35.24 35.30

  b) Preparation of N-hydroxy-2-hydroxyamino-2, 3-nitroaniline. After adding 0.04 moles (9.1 g) of 2,6-dinitro, N- [b-hydroxyethylaniline to 160 ml of absolute ethanol added with 16 ml of 22 B ammonia, hydrogen is bubbled through. sulphurated for 30 minutes in this alcoholic solution. The bubbling is stopped and then the reaction medium is brought to reflux for 2 hours. The boiling alcoholic solution is filtered to remove the inorganic salts and then the filtrate is evaporated to dryness. The red residue obtained is redissut hot

  in alcohol. By cooling the expected product crystal-

  read. It is drained, washed with a little cold alcohol and

dry under vacuum. It melts at 78 C.

  Analysis Calculated for Found C8H11N303

C% 48.73 48.88

H% 5.58 5.61

N% 21.32 21.46

0% 24.37 24.49

  The various trade names used in the foregoing examples are explained in more detail below: CARBOPOL 934: Polymer acrylic acid MW 2 to 3 million sold by

Goodrich Chemical Company.

  CEMULSOL NP4: Nonylphenol with 4 moles of oxide

  ethylene sold by Rhône Poulenc.

  CEMULSOL NP9: Nonylphenol with 9 moles of oxide

  ethylene sold by Rhône Poulenc.

  ALFOL C16 / 18 Cetylstearyl alcohol sold by

(50/50): the Condéa Company.

  Lanette wax E: Partial cetylstearyl alcohol

sulphate sold by Henkel.

  CEMULSOL B: Ethoxylated castor oil sold

by Rhône Poulenc.

  MASQUOL DTPA: Sodium salt of diethyl acid

pentacetic triamine.

  TRILON B: Sodium salt of ethylene-

diamine tetracetic.

Claims (17)

  1. Dyeing composition for keratin fibers which are   characterized in that it contains at least one dye corresponding to formula (I): NHR 2 O2N-- NHR1   in which R1 and R2 independently designate one of   the other a hydrogen atom, an alkyl group, a group   monoalkyl or polyhydroxy alkyl group, an alkyl group substituted by an alkoxy group, an aminoalkyl group whose amino group may optionally be mono- or disubstituted with an alkyl group, the radical R2 may also designate a phenyl group, or phenyl substituted by a alkyl, hydroxyl, or amino group, Z denotes a   hydrogen atom or an alkyl group or their cosmetic salts. acceptable.   2. Dye composition for keratin fibers according to claim 1, characterized in that it contains at least one dye of formula (I) in which Z denotes hydrogen or methyl, R2 denotes hydrogen, methyl, ethyl, propyl, butyl, hydroxyethyl, (hydroxypropyl,   / -dihydroxypropyl, (-methoxyethyl, N, N-diethylamino)   ethyl, p-hydroxyphenyl, R1 denotes hydrogen, methyl, ethyl or β-hydroxyethyl.   3. Composition according to Claim 1, characterized in that the dye corresponds to the formula (I) in which Z   denotes methyl or in which R2 is different from hy-   drogen. 4. Dye composition according to any one of   Claims 1 to 3, for dyeing hair   characterized by the fact that it contains in a   cosmetically acceptable medium at least one compound of   mule (I) in proportions of 0.001 to 5% by weight.   5. Dye composition according to any one of   claims 1 to 4, characterized in that it   holds a solvent selected from water, lower alkanols,   polyols, glycols or glycol ethers or their diapers.   6. Composition according to any one of the claims   1 to 3, characterized in that it additionally contains cosmetic adjuvants chosen from surfactants,   thickeners, penetrating agents, sequestrants   trants, film-forming agents, buffers, perfumes, agents alkalinizing or acidifying agents.   7. Composition according to any one of the claims   1 to 6, characterized in that it has a pH of between   3 and 11.5 and preferably between 5 and 11.5.   8. Composition according to any one of the claims   1 to 4, intended to be used for the direct dyeing of the hair, characterized in that it contains in addition   other direct dyes chosen from azol   anthraquinone derivatives, the nitro derivatives of the ben-   zenics other than those of formula (I).   9. Composition according to any one of the claims   1 to 4, intended to be used as a setting lotion, characterized in that it is in the form of an aqueous solution, alcoholic or hydroalcoholic, containing 2.5 less a cosmetic resin.   10. Composition according to any one of the claims   1 to 4, intended to be used for the oxidation dyeing, characterized in that it also contains at least   oxidation dye precursors.   11. Composition according to claim 10, characterized in that it has a pH of between 7 and 11.5 and that it   additionally contains a reducing agent.   12. Method for dyeing keratinous fibers,   the fact that a composition is applied to the fibers   as defined in any of the claims   tions 1 to 11, leave for 5 to 70 minutes,   rinse, wash if necessary rinsed again and dried.   13. Procedure for dyeing keratinous fibers,   terized by the fact that it is applied to the washed fibers and   rinsed a composition as defined in the claim   9, which may be rolled up and dried.   14. A process for dyeing keratinous fibers, characterized in that the fibers are applied to   composition as defined in claims 10 or   11, optionally supplemented with an oxidizing agent that is left   ask for 10 to 50 minutes, rinse, wash if necessary   shampoo, rinse again and dry.   15. Derivatives of nitro-orthophenylenediamine,   rised by the fact that they meet the formula: NHR ' 02N X NHR'1   (II) in which R'1 and R'2 independently designate one of   the other a hydrogen atom, an alkyl group, a group   mono or polyhydroxy alkyl, a substituted alkyl group   killed by an alkoxy group, an amino alkyl group   the amino group can optionally be mono or di-substituted   killed by an alkyl group, the radical R2 may also denote a phenyl or phenyl-substituted by a hydroxyl or amino alkyl group and Z 'denotes a hydrogen atom or an alkyl group provided that R'l, R'2 and Z 'can not designate hydrogen simultaneously, when R'2 3 denotes methyl or phenyl R'1 and Z' can not both designate hydrogen simultaneously, when Z 'denotes methyl   at least one of the groups R'1 or R'2 is different from hy-   when R'1 and R'2 denote methyl Z 'is different   hydrogen, and their cosmetically acceptable salts.   16. Process for the preparation of compounds as defined in claim 15, characterized in that when R '1 denotes hydrogen, the compounds are reduced   of formula (III ') using an alkaline sulphite or by trans-   hydrogen from cyclohexene to the compound of formula (III ') NHR'2 02N 2NO2 (III ') Z '   17. A process for the preparation of the compounds of the   15, in which R '1 denotes alkyl or substituted alkyl,   characterized in that sulphonyl benzene is carried out   selective paratoluene or sulfonation of the compositions of claim 15, wherein R'1 is H which is   reacts on the arylsulfonamides obtained a halogeno   cane of formula XR'1 in which X denotes halogen and R'1 has the meaning indicated above and that the hydrolysis of sulfonamides after substitution.