BE895697A - NOVEL COMPOUNDS FOR HAIR DYEING, PROCESS FOR THEIR PREPARATION, DYEING COMPOSITION CONTAINING THEM - Google Patents

Description

       

  : New compounds usable for hair dyeing, their preparation process, dyeing composition

  
containing them

NOVEL COMPOUNDS FOR HAIR DYEING, PROCESS FOR THEIR PREPARATION, DYE COMPOSITION CONTAINING THEM

  
The present invention relates to new (phenoxy-substituted) -1 amino-propanol-2 compounds, in which the extra-nuclear amine group may or may not be substituted, and to their process of preparation. The invention also relates to hair dye compositions comprising these new compounds and to a dyeing process using said compositions.

  
The intention is to propose a new class of compounds capable of being used in hair dyes to give powerful dyes, stable to light, and having good resistance to weathering and washing. The invention further aims to propose a new category of compounds having good safety and satisfactory characteristics from the point of view of mutagenesis.

  
The present invention relates to a new chemical compound of formula (I) (or a corresponding acid salt)
  <EMI ID = 1.1>
 formula in which: <EMI ID = 2.1>

  
Y representing two identical or different substituent groups lower alkyl or lower hydroxyalkyl having at most 4 carbon atoms, these two groups possibly forming with the nitrogen atom which carries them a morpholinic or piperidinic heterocycle, one or both substituents which make up Y which can also represent hydrogen

  
  <EMI ID = 3.1>

  
titrating lower alkyl having at most 4 carbon atoms and X representing an anion; <EMI ID = 4.1> hydrogen atom or a lower alkyl or hydroxyalkyl radical having at most 4 carbon atoms,

  
provided that, when A designates NY, 1 [deg.]) if Z is in posi-

  
  <EMI ID = 5.1>

  
one of the two substituents that make up Y does not represent an ethyl group when the other substituent represents a hydrogen atom, and the two substituents that make up Y do not form, with the nitrogen atom that carries them, a morpholinic or piperidinic heterocycle, and 2 [deg.]) when one of the two substituents which compose Y designates a hydrogen atom or an alkyl group and the other designates a group

  
  <EMI ID = 6.1>

  
a hydrogen atom or an alkyl group.

  
X can advantageously be a halogen, in particular chlorine.

  
The present invention also relates to a process for the preparation of a chemical compound of formula (I)
(or a corresponding acid salt), in.which.

  
  <EMI ID = 7.1>
- A denotes NY,

  
Y representing two identical or different substituent groups lower alkyl or lower hydroxyalkyl having at most 4 carbon atoms, these two groups possibly forming with the nitrogen atom which carries them a heter-

  
  <EMI ID = 8.1>

  
constituents which make up Y which may also represent hydrogen; <EMI ID = 9.1> that if Z is in position 4 on the benzene nucleus and if NR1 R2 is in position 2, one of the two substituents which compose Y does not represent an ethyl group when the other substituent represents a atom d Hydrogen and the two substituents which compose Y do not form, with the nitrogen atom which carries them, a morpholinic or piperidinqie cycle, this process being characterized by the fact that it comprises the following stages:
a) acting on the known compound of formula
(II)
  <EMI ID = 10.1>
  <EMI ID = 11.1>
  <EMI ID = 12.1>
 b) acting on the compound of formula (III) a <EMI ID = 13.1>

  
indicated, to obtain the compound of formula (IV)
  <EMI ID = 14.1>
 c) on the compound of formula (IV), a strong acid is made to act, such as hydrochloric acid, to obtain the compound of formula (V)
  <EMI ID = 15.1>
 d) and, optionally, to result in the compound of <EMI ID = 16.1>

  
reduction either, for example, by zinc powder in an alcoholic medium in the presence of ammonium chloride, or by catalytic hydrogenation, the palladium on carbon being able to serve as catalyst, which makes it possible to obtain the compound of formula (VI)

  

  <EMI ID = 17.1>


  
The present invention also relates to a process for the preparation of a chemical compound of formula (I)
(or a corresponding acid salt) in which: <EMI ID = 18.1>
- A denotes NY,

  
Y representing two identical or different substituent groups lower alkyl or lower hydroxyalkyl having at most 4 carbon atoms, these two groups optionally forming with the nitrogen atom which carries them a morpholinic heterocycle. or piperidinic, one or both of the substituents which make up Y can also represent hydrogen;
- Ri and R2 are identical or different and represent a hydrogen atom or an alkyl or hydroxyalkyl radical <EMI ID = 19.1>

  
R2 = H being excluded, process according to which the compound of formula (VII) is used as starting material

  

  <EMI ID = 20.1>


  
  <EMI ID = 21.1>

  
previously indicated, and the reactions provided for in steps a) and b) above are carried out successively in order to obtain a product of formula (VIII)

  

  <EMI ID = 22.1>


  
  <EMI ID = 23.1>

  
and when we want to obtain a compound of formula (I) (or

  
  <EMI ID = 24.1>

  
A designating NY, the compound of formula (VIII) is subjected to a reduction, as indicated for step d) mentioned above. As a variant, if none of the substituents which make up Y represents a hydrogen atom, it is possible to use a preparation process starting from a compound of formula (II), practicing steps a), b), c), d), then substitute one of the nuclear amine groups of the compound of formula (VI), for example, by substitution of the corresponding arylsulf-amide

  
  <EMI ID = 25.1>

  
The present invention also relates to a process for the preparation of a compound of formula (I), in which: <EMI ID = 26.1>

  
Y representing two identical or different substituent groups lower alkyl or lower hydroxyalkyl having at most 4 carbon atoms, these two groups possibly forming with the nitrogen atom which carries them a morpholinic or piperidinic heterocycle, Y 'representing a substituent group lower alkyl having at most 4 carbon atoms and X representing an anion; <EMI ID = 27.1> hydrogen atom or a lower alkyl or hydroxyalkyl radical having at most 4 carbon atoms,

  
characterized by the fact that the nuclear amine function (s) is (are) protected from the corresponding tertiary compound by acetylation, then a quaternizing agent is made to act. Subsequently, by the action of an acid, we des
-acetyl and, optionally, we can at the same time change the quaternization anion. ,

  
In the case where Z represents a nitro group, the compounds of formula (I) are direct dyes which can be used for dyeing keratin fibers and, in particular, hair. It has been found that these compounds have good solubility in the solvents generally used in hair dyeing, which makes it possible to use them at a concentration high enough to give the keratin fiber a powerful coloring with a good leveling.

  
The dye obtained has good light and weather stability. In addition, the use in hair dye of these compounds is characterized by good safety. The invention therefore also relates to a dye composition for keratin fibers and in particular for hair, characterized in that it comprises, in a support. suitable, at least one compound of formula (I) (or a corresponding acid salt), in which:
- Z represents a nitro group;

  
  <EMI ID = 28.1>

  
Y representing two identical or different substituent groups lower alkyl or lower hydroxyalkyl having at most 4 carbon atoms, these two groups possibly forming with the nitrogen atom which carries them a morpholinic or piperidinic heterocycle, one or both substituents which make up Y which may also represent hydrogen when A denotes NY only, Y 'representing a lower alkyl substituent group having at most 4 carbon atoms and X representing an anion; <EMI ID = 29.1> a hydrogen atom or a lower alkyl or hydroxyalkyl radical, having at most 4 carbon atoms. In a preferred embodiment, the dye composition according to the invention comprises from 0.001% to 4% by weight of at least one compound of formula (I).

  
  <EMI ID = 30.1>

  
compounds of formula (I) are either oxidation bases if they are para-or ortho-diamines, or couplers intended to be used in combination with oxidation bases, when it is acts of metadiamines.

  
When the compound of formula (I) is an oxidation base, the invention also relates to a dye composition for keratin fibers, in particular for hair, characterized in that it contains, in an appropriate carrier, at least a compound of formula (I)
(or a corresponding acid salt), formula in which: <EMI ID = 31.1>

  
Y representing two identical or different substituent groups lower alkyl or lower hydroxyalkyl having at most 4 carbon atoms, these two groups possibly forming with the nitrogen atom which carries them a morpholinic or piperidinic heterocycle, one or both substituents which make up Y which can also represent hydrogen <EMI ID = 32.1>

  
substituent lower alkyl having at most 4 carbon atoms

  
  <EMI ID = 33.1> a hydrogen atom or a lower alkyl or hydroxyalkyl radical having at most 4 carbon atoms. In a preferred embodiment, the compound of formula (I) is used in a proportion of between 0.001% and 4% by weight relative to the total weight of the composition.

  
In the case where the compound of formula (I) is a metaphenylenediamine, the invention also relates to a dye composition for keratin fibers, and in particular for hair, containing, in an appropriate support, at least one oxidation base, characterized in that it also contains at least one compound of formula (I) (or a corresponding acid salt), formula in which: <EMI ID = 34.1> <EMI ID = 35.1>

  
Y representing two identical or different substituent groups lower alkyl or lower hydroxyalkyl having at most 4 carbon atoms, these two groups possibly forming with the nitrogen atom which carries them a morpholinic or piperidinic heterocycle, one or both substituents which make up Y which can also represent hydrogen when A denotes NY only, Y 'representing

  
a lower alkyl substituent group having at most 4 carbon atoms and X representing an anion; <EMI ID = 36.1> a hydrogen atom or a lower alkyl or hydroxyalkyl radical having at most 4 carbon atoms,

  
provided that when A designates NY if Z is in position

  
  <EMI ID = 37.1>

  
  <EMI ID = 38.1>

  
one of the two substituents which make up Y does not represent an ethyl group when the other substituent represents

  
a hydrogen atom and the two substituents which make up Y do not form, with the nitrogen atom which carries them, a morpholinic or piperidine heterocycle. The compound of formula (I) is preferably used in a proportion of between 0.001% and 2.5% by weight relative to the total weight of the composition.

  
The dye compositions according to the invention may comprise, in addition to the compounds of formula (I), oxidation bases consisting of:

  
A- Paraphenylenediamines of general formula
(IX)
  <EMI ID = 39.1>
 or the corresponding acid salts, formula in which

  
  <EMI ID = 40.1>

  
a hydrogen atom, an alkyl radical having from 1 to 4 carbon atoms, an alkoxy radical having 1 or 2 carbon atoms,

  
  <EMI ID = 41.1>

  
or different and represent a hydrogen atom, an alkyl, hydroxyalkyl or alkoxyalkyl radical, in which the alkoxy group contains 1 or 2 carbon atoms, carbamyl-

  
  <EMI ID = 42.1>

  
kyle, carbethoxyaminoalkyle, aminoalkyle, monoalkylaminoalkyle, dialkylaminoalkyle, pipéridinoalkyle, morpholinoalkyle,

  
  <EMI ID = 43.1>

  
  <EMI ID = 44.1>

  
nitrogen to which they are attached, .........................

  
................................. a piperidino group <EMI ID = 45.1>

  
  <EMI ID = 46.1>

  
hydrogen atom; or

  
B- The paraaminophenols of general formula (X)
  <EMI ID = 47.1>
 or the corresponding acid salts, formula in which R6 represents a hydrogen atom, an alkyl radical containing 1 to 4 carbon atoms or a halogen atom such as, for example, chlorine or bromine.

  
C - Heterocyclic bases such as 2,5-diamino pyridine, 3-methyl-7-amino benzomorpholine, 5-amino indole.

  
The dye compositions according to the invention may contain, in addition to the compounds of formula (I),

  
the following products, taken individually or in combination:

  
1) when the composition contains at least one oxidation base, at least one coupler taken from the group formed by resorcin, pyrocatechol, 2-methyl resorcin, 2-ethyl resorcin, metaaminophenol, 2-methyl

  
  <EMI ID = 48.1>

  
phenol, 6-hydroxy benzomorpholine, 2,6-dimethyl-3-acetylamino phenol, 2-methyl-5-carbethoxyamino-phenol, 2-methoxy-5-carbethoxyamino-phenol, 2-methyl-5-ureido phenol, diamino- 2,4 phenoxyethanol, 2,4-diamino anisole, 2,6-dimethyl metaphenylenediamine, (2-amino-methylmino-4) phenoxyethanol, (2,4-diamino) phenyl,--methoxyethyl ether, (2,4-diamino) phenyl,--mesylaminoethyl ether, N-carbamylmethylamino-2 amino-4 anisole, amino-3 <EMI ID = 49.1>

  
droxypropyl-ether;

  
2) orthophenylenediamines and orthoaminophenols optionally comprising substituents on the nucleus or on the amine functions or also ortho-diphenol, these products, by complex oxidation mechanisms, which can lead to new colored compounds, either by cy-

  
  <EMI ID = 50.1>

  
3) dye precursors of the benzene series comprising on the nucleus at least three substituents chosen from the group formed by hydroxy, methoxy or amino groups such as 2,6-diamino hydrochloride hydrochloride, diamino-2 hydrochloride, 6 N, N-bis- (ethyl) amino-4

  
phenol, 2,4-diamino dihydrochloride phenol, 1,2,4 trihydroxy benzene, 2,3,5 trihydroxy toluene or 4-methoxy-2-amino-N - (&#65533; -hydroxyethyl) aniline ;

  
4) quinone dyes such as 2-hydroxy naphthoquino-

  
  <EMI ID = 51.1>

  
N'-methylamino-4 benzene, N, N -...........................

  
(methyl,--hydroxyethyl) amino-l nitro-3 N '- (&#65533; -hydroxyethyl)

  
  <EMI ID = 52.1>

  
phenol, (3-nitro-amino 4) phenoxyethanol, (3-nitro N-methylamino-4) phenoxyethanol, N-methyl-amino-3 nitro-4

  
  <EMI ID = 53.1>

  
7) various usual adjuvants such as water, penetration agents, surface-active agents, thickening agents, antioxidant agents, alkalizing or acidifying agents, perfumes, agents

  
  <EMI ID = 54.1>

  
The pH of the dye compositions according to the invention is between 5 and 11.5. Among the alkalinizing agents which can be used, there may be mentioned ammonia, alkylamines such as ethylamine or triethylamine, alkanolamines such as mono,

  
di or trietha ol olamine, alkyl alkanolamines such as methyl diethanolamine, sodium or potassium hydroxides, sodium, potassium or ammonium carbonates. Among the acidifying agents which can be used, there may be mentioned lactic acid, acetic acid, tartaric acid and phosphoric acid.

  
It is also possible to add to the composition according to the invention water-soluble, anionic, cationic, non-ionic, amphoteric surfactants or a mixture thereof. Among the surfactants which can be particularly used, mention may be made of alkylbenzene sulfonates, alkylnaphthalene sulfonates, sulfates, ether sulfates and sulfonates of fatty alcohols, quaternary ammonium salts such as trimethylketyl ammonium bromide, cetyl pyridinium bromide, fatty acid diethanolamides, or polyoxyethylenated or polyglycerolated acids, alcohols or alkylphenols. Preferably, the surfactants are present in the composition according to the invention in a proportion of between 0.5 and 55% by weight and, advantageously, between 4 and 40% by weight relative to the total weight of the composition.

  
It is also possible to add to the composition according to the invention organic solvents among which mention may advantageously be made, for example, of ethanol, isopropanol, glycerin, glycols and their ethers such as 2-butoxyethanol, ethylene glycol, propylene glycol,

  
monoethyl ether and monomethyl ether of diethylene glycol and similar solvents. The solvents can advantageously be present in the composition in a proportion ranging from 1 to 40% by weight and, preferably, between 5 and 30% by weight relative to the total weight of the composition.

  
The thickening products, which can be added to the composition according to the invention, can advantageously be taken from the group formed by sodium alginate, gum arabic, cellulose derivatives such as methylcellulose, hydroxyethylcellulose , hydroxypropylmethylcellulose, the sodium salt of carboxymethylcellulose and polymers of acrylic acid; mineral thickening agents such as bentonite can also be used. Preferably, the thickening agents are present in a proportion of between 0.5 and 5% by

  
weight relative to the total weight of the composition and, advantageously, between 0.5 and 3% by weight.

  
The antioxidant agents which can be added to the composition according to the invention can advantageously be taken from the group formed by sodium sulfite, thioglycolic acid, mercaptosuccinic acid, sodium bisulfite,

  
  <EMI ID = 55.1>

  
may be present in the composition in a proportion of between 0.05 and 1.5% by weight relative to the total weight of the composition.

  
The dye composition according to the invention, when it contains at least one oxidation base, contains, at the time of use, oxidizing agents such as hydrogen peroxide, urea peroxide or persalts such as ammonium persulfate.

  
The dye composition according to the invention may be in the form of a liquid, cream, gel, aerosol or in any other form suitable for dyeing keratin fibers.

  
The present invention also relates to a new hair dyeing process, characterized in that the above dye composition allowed to act on the hair for an exposure time varying between 10 and 45 min, which is rinsed, qu 'optionally wash and rinse again and dry the hair.

  
In the case where the dye composition used contains at least one oxidation base, the above-mentioned process comprises an initial phase in which a sufficient quantity of oxidizing agents is mixed with said composition, at the time of use.

  
To better understand the object of the invention, we will now describe, by way of purely illustrative and non-limiting examples, several modes of réali-sation.

Example 1:

  
  <EMI ID = 56.1>

  
N, N-diethylamino-3 propanoL-2

  

  <EMI ID = 57.1>


  
  <EMI ID = 58.1>

  
propane

  
To a solution of 0.376 mole (73.7 g) of 3-nitro-4-acetylamino phenol in 375 ml of 1.1 N sodium solution, 150 ml of epichlorohydrin are added at room temperature. The reaction medium is left at room temperature, with good stirring, for 48 hours, then the expected product is drained, which has precipitated. After drying under vacuum and recrystallization from benzene, this product melts

  
at 123 [deg.] C.

  
The product obtained corresponds to the following results:

  

  <EMI ID = 59.1>


  
Second step

  
  <EMI ID = 60.1>

  
146 g of diethylamine and 50 ml of absolute alcohol. Diethylamine and alcohol are removed in vacuo. The residual oil slowly crystallizes. After recrystallization from cyclohexane, 58 g of expected product are obtained, which melts

  
  <EMI ID = 61.1>

  
The product obtained corresponds to the following analysis results:

  

  <EMI ID = 62.1>


  
Third step

  
  <EMI ID = 63.1>

  
N, N-3-diethylamino-propanol-2

  
  <EMI ID = 64.1>

  
  <EMI ID = 65.1>

  
N, N-3-diethylaminô-propanol-2 in 100 ml of hydrochloric acid (d = 1.18). After addition of ammonia to the reaction medium, so as to have pH = 6, the monohydrochloride

  
  <EMI ID = 66.1>

  
nol-2 crystallizes. It is wrung, washed with a little alcohol at 80 [deg.], It is recrystallized from a hydroethanolic mixture

  
  <EMI ID = 67.1>

  
The product obtained corresponds to the following analysis results

  

  <EMI ID = 68.1>
 

Example 2:

  
  <EMI ID = 69.1>

  

  <EMI ID = 70.1>


  
  <EMI ID = 71.1>

  
3-amino-propanol-2

  
0.02 mole (5.0 g) of [(3-nitro acetyl-

  
  <EMI ID = 72.1> ......... then the mixture is heated for 3 hours at 45 [deg.] C. The reaction medium is then poured into 100 g of water <EMI ID = 73.1>

  
who rushed. After drying under vacuum and recrystallization from a benzene-ethyl acetate mixture, the product melts at 146 [deg.] C.

  
The product obtained corresponds to the following analysis results:

  

  <EMI ID = 74.1>


  
Second step

  
  <EMI ID = 75.1>

  
hydrochloric (d = 1.18). The cooled reaction mixture is supplemented with ammonia at 22 [deg.] Bé until a pH equal to 5. The monohydrochloride of the expected product precipitates. It is wrung, washed with a little alcohol at 80 [deg.], Then it is recrystallized in a hydroethanolic mixture. It melts at 224 [deg.] C.

  
The product obtained corresponds to the following analysis results:

  

  <EMI ID = 76.1>
 

Example 3:

  
  <EMI ID = 77.1>

  

  <EMI ID = 78.1>


  
First stage

  
  <EMI ID = 79.1>

  
2,3-propane epoxy (prepared according to the first step of Example 1) are introduced into 150 ml of absolute ethanol supplemented with 12 drops of pyridine. 0.24 mole is added
(23.7 g) succinimide. The mixture is heated to reflux

  
  <EMI ID = 80.1>

  
crystallizes. We wring it out, wash it with a little alcohol.

  
After recrystallization from alcohol and drying under vacuum, it melts at 154 [deg.] C.

  
The product obtained corresponds to the following analysis results

  

  <EMI ID = 81.1>


  
Second step :

  
  <EMI ID = 82.1>

  
50.9 g (0.145 mole) of the succinimido derivative obtained according to the first step are introduced into 100 ml of alcohol

  
to 96 [deg.] supplemented with 250 ml of hydrochloric acid (d = 1.18). After 14 hours of reflux, the cooled reaction medium is added with acetone. The expected product precipitates in the form of the hydrochloride. This hydrochloride is taken up in 70 ml of water. By alkalinization using a sodium solution

  
  <EMI ID = 83.1>

  
propanol-2 as an oil, which crystallizes quickly. After recrystallization from alcohol, the product melts at 124 [deg.] C.

  
The product obtained corresponds to the following analysis results:

  

  <EMI ID = 84.1>
 

Example 4:

  
  <EMI ID = 85.1>

  
propanol-2
  <EMI ID = 86.1>
 
  <EMI ID = 87.1>
 First floor _

  
  <EMI ID = 88.1>

  
propane

  
To a solution of 2 moles (392 g) of 2-acetylamino-4-nitro-phenol in two liters of 1.1N sodium solution, 1.6 liters of epichlorohydrin are added and the reaction medium is left for 96 hours at 20 [ deg.] C under agitation terminal. 282 g of the expected product are filtered off and washed with water, which

  
rushed. This product contains about 20% of a product

  
  <EMI ID = 89.1>

  
of an epichlorohydrin molecule on two moles of 2-acetylamino-4-nitro phenol. However, it will be used as is for the second synthesis stage, the secondary product being very easily eliminated at this stage. Second step

  
  <EMI ID = 90.1>

  
mido-3 propanol-2

  
100 g of crude product obtained during the previous step are introduced into 500 ml of ethanol at 95 [deg.]. 0.52 mol (51.5 g) of succinimide and 2.5 ml of pyridine are added and the mixture is brought to reflux, with stirring, during. two o'clock. The alcoholic solution is filtered boiling to isolate the expected product insoluble in

  
  <EMI ID = 91.1>

  
pure. This product, after recrystallization from alcohol,

  
background at 184 [deg.] C.

  
The product obtained corresponds to the following analysis results:

  

  <EMI ID = 92.1>


  
The mother liquors of the reaction medium contain

  
  <EMI ID = 93.1> .th stage are heated with stirring for 1 hour in a boiling water bath in 10 ml of hydrochloric acid <EMI ID = 94.1>

  
from the reaction medium, the expected product precipitates. It is drained, washed with water and recrystallized from ethanol. It melts at 200 [deg.] C.

  
. The product obtained corresponds to the following analysis results:

  

  <EMI ID = 95.1>


  
Step four

  
  <EMI ID = 96.1>

  
3-amino-propanol-2

  
7.9 g (0.0256 mole) of the succinimido derivative prepared during the previous step are heated for 8 hours with stirring in 40 ml of hydrochloric acid (d = 1.18) at reflux. After cooling the reaction medium, the expected product is drained, which has crystallized in the form of dihydrochloride. This dihydrochloride is dissolved in 175 ml of water and, using a sodium solution, the pH is brought to

  
9. The expected product which has precipitated is filtered off. After washing with water and recrystallization from alcohol, the product melts at 159 [deg.] C.

  
The product obtained corresponds to the following analysis results:

  

  <EMI ID = 97.1>
 

Example 5:

  
  <EMI ID = 98.1>

  
panol-2

  

  <EMI ID = 99.1>


  
First stage

  
  <EMI ID = 100.1>

  
2.3 propane 0.376 mol (73.7 g) of acetylamino-2 is dissolved

  
  <EMI ID = 101.1>

  
add 300 ml of epichlorohydrin. The reaction medium is left for 96 hours at 20 [deg.] C with good stirring, then filtered and the expected product, which has precipitated, is washed with water. After recrystallization from ethanol and drying under vacuum, it melts at 164 [deg.] C.

  
The product obtained corresponds to the following analysis results:

  

  <EMI ID = 102.1>


  
  <EMI ID = 103.1>

  
absolute supplemented with 6 drops of pyridine. 0.087 mole (8.6 g) of succinimide is added, then the mixture is brought to reflux for 5 hours. After cooling, add
150 ml of water and the alcohol is removed under vacuum. The expected product, obtained first in the form of an oil insoluble in water, crystallizes slowly. We wring it out and recrystallize it

  
  <EMI ID = 104.1>

  
The product obtained corresponds to the following analysis results:

  

  <EMI ID = 105.1>


  
Third step

  
Preparation of L (2-amino-5-nitro) phenoxy -1 amino-3-propanol-2

  
7.0 g (0.02 mole) of the succinimido derivative obtained during the second stage are heated for 14 hours at

  
  <EMI ID = 106.1>

  
hydrochloric (d = 1.18 & The reaction medium is then cooled and added with acetone to precipitate the expected product in the form of the hydrochloride. This hydrochloride is drained and then dissolved in 12 ml of water. Using an ION sodium solution, we pre-

  
  <EMI ID = 107.1>

  
in the form of an oil, which crystallizes quickly. The product is drained, washed with water and recrystallized from ethanol. It melts at 141 [deg.] C.

  
The product obtained corresponds to the following analysis results:

  

  <EMI ID = 108.1>
 

Example 6:

  
  <EMI ID = 109.1>

  
thylamino-3 propanol-2

  

  <EMI ID = 110.1>


  
First stage <EMI ID = 111.1>

  
2,3 propane epoxy prepared according to the first phase of Example 5 are dissolved, by heating in a boiling water bath, in 36.6 g of monoethanolamine and 10 ml of absolute alcohol. After 1.5 hours of heating in a boiling water bath, the reaction medium is poured into 300 g of ice water. The expected partially deacetylated product precipitates. It is drained, washed with water and dried under vacuum. It will be used as is for the second phase of the synthesis.

  
Second step :

  
  <EMI ID = 112.1>

  
3-ethylamino-propanol-2

  
8.7 g of the crude product obtained during the first synthesis phase are heated for 30 min in a water bath

  
  <EMI ID = 113.1>

  
The reaction mixture is cooled and ammonia added to a pH of 6. The expected product precipitates as monohydrochloride. This monohydrochloride is drained, recrystallized from an ethanol / water mixture and dried under vacuum. He created
156 [deg.] C.

  
The monohydrochloride is dissolved in 20 ml of water. Basified with 20% ammonia. The

  
  <EMI ID = 114.1>

  
panol-2 precipitates. The product is drained, washed with water, recrystallized from water and dried under vacuum. He created

  
  <EMI ID = 115.1>

  
The product obtained corresponds to the following results:

  

  <EMI ID = 116.1>
 

Example 7: _

  
  <EMI ID = 117.1>

  
3-amino-propanol-2

  

  <EMI ID = 118.1>


  
7.5 g of zinc powder and 0.3 g of ammonium chloride dissolved in 1.5 ml of water are added to 15 ml of 96% alcohol. The mixture is brought to reflux with stirring, then, little by little, added so as to maintain the reflux without external heating, 0.015 mole (3.4 g) of

  
  <EMI ID = 119.1>

  
according to Example 5. When the addition is complete, the reflux is maintained for 5 min, then the boiling reaction medium is filtered through 4.6 ml of ice-cold hydrochloric acid (d = 1.18).

  
The expected product crystallizes in the form of hydrochloride. The product is drained, washed with alcohol and dried under vacuum. It melts with decomposition at 216-218 [deg.] C.

  
The product obtained corresponds to the following analysis results:

  

  <EMI ID = 120.1>
 

Example 8:

  
  <EMI ID = 121.1>

  
3-amino-propanol-2

  

  <EMI ID = 122.1>


  
0.02 mole (5.3 g) of monohydrochloride is introduced

  
  <EMI ID = 123.1>

  
according to Example 4 with 50 ml of 96% alcohol and 0.2 g of 10% palladium / carbon. The mixture is brought to 85 [deg.] C for one hour under 35 bars of hydrogen. After cooling, it is filtered to remove the catalyst, collecting the filtrate on 20 ml of ice-cold ethanol saturated with hydrochloric gas. The expected product precipitates in the form of hydrochloride. After recrystallization of this hydrochloride from an ethanol / water mixture, it melts with decomposition at 236-238 [deg.] C.

  
The product obtained corresponds to the following analysis results:

  

  <EMI ID = 124.1>
 

  
It has been found that this compound, which constitutes a coupler, surprisingly gives, by coupling with paraaminophenol, much redder hues than its counterpart, which does not contain an OH group on the side catne; it has also been found that, surprisingly, the red tints obtained were much more stable than with the non-hydroxylated counterpart.

Example 9:

  
Preparation of (methylamino-3 nitro-4) hydrochloride

  
  <EMI ID = 125.1>
  <EMI ID = 126.1>
 First stage :

  
  <EMI ID = 127.1>

  
propyl ether (product described in Example 2 of French patent application 80-17 617) in 150 ml of pyridine. To this pyridine solution, maintained at -5 [deg.] C, 0.22 mol is added dropwise, with stirring, in 10 minutes
(25.2 g) of methanesulfochloride. When the addition is complete, the temperature of the reaction medium is allowed to rise to
20 [deg.] C then, after having left the reaction medium for 45 minutes at room temperature, it is added to <EMI ID = 128.1> sodium methylate 27.8%. When the addition is complete, the mixture is stirred for two hours at room temperature, then the methylene chloride is washed with water, with an IN hydrochloric solution, then with a saturated solution of sodium bicarbonate. The methylene chloride is removed in vacuo.

   The expected product, consisting of the residual oil, crystallizes very quickly. - ,, - by recrystallization from ethyl acetate

  
  <EMI ID = 129.1>

  
The product obtained corresponds to the following analysis results:

  

  <EMI ID = 130.1>


  
Second step :

  
  <EMI ID = 131.1>

  
cinimido-3 propanol-2 <EMI ID = 132.1>

  
absolute supplemented with 6 drops of pyridine. 0.10 mole (10.1 g) of succinimide is added, then the mixture is brought to reflux for 4 hours. The boiling reaction mixture is filtered. By cooling the filtrate, the expected product crystallizes. After recrystallization from alcohol and drying under vacuum, it melts at 152 [deg.] C.

  
The product obtained corresponds to the following analysis results:

  

  <EMI ID = 133.1>


  
Third step :

  
Preparation of (methylamino-3-nitro-4) monohydrochloride

  
  <EMI ID = 134.1>

  
10.5 g (0.0324 mole) of the succimido derivative obtained according to the second step are heated for 7 hours at reflux in 20 ml of 96% alcohol and 60 ml of 36% hydrochloric acid. The reaction medium is cooled to O [deg.] C. The expected product crystallizes. It is drained, washed with acetone, recrystallized from a hydroalcoholic mixture. After drying under vacuum, it melts with decomposition between 258 and 260 [deg.] C.

  
  <EMI ID = 135.1>

  
following:

  

  <EMI ID = 136.1>

Example 10:

  
Preparation of trichlorhydrate, monohydrate

  
  <EMI ID = 137.1>

  

  <EMI ID = 138.1>


  
First stage :

  
  <EMI ID = 139.1> propanol-2.

  
  <EMI ID = 140.1>

  
  <EMI ID = 141.1> ............. in 100 ml of 40% aqueous dimethylamine solution and the reaction mixture is stirred for 30 min at room temperature. After dilution by adding 225 ml of ice water and then neutralizing with acetic acid, it is evaporated to dryness under vacuum. The dry residue is taken up in
150 ml of ethyl acetate. The insoluble ethyl acetate, after washing with acetone, consists of 28.5 g <EMI ID = 142.1>

  
Christmas-2. This acetylated derivative is brought to reflux for two hours in 220 ml of ethanol saturated with hydrochloric gas. After cooling the reaction medium, the expected product is drained in the form of the hydrochloride. After dissolving this hydrochloride in water and alkalinizing the aqueous solution using a sodium solution, precipitate

  
  <EMI ID = 143.1>

  
in crystallized form.

  
The product is drained, washed with water and dried under vacuum. It melts at 123 [deg.] C.

  
The elementary analysis gives the following results:

  

  <EMI ID = 144.1>


  
  <EMI ID = 145.1>

  
Is subjected to a catalytic hydrogenation at 80 [deg.] C, under a pressure of 40 bars of hydrogen, 0.12 mol (30.6 g)

  
  <EMI ID = 146.1>

  
dissolved in 92 ml of absolute alcohol and in the presence of 4.5 g of 10% palladium on carbon. The catalyst is removed by filtration, receiving the alcoholic filtrate

  
on 143 ml of ice-cold ethanol saturated with hydrochloric gas.

  
The expected product precipitates in the form of hydrochloride. This trihydrochloride is drained and recrystallized from a hydroalcoholic hydrochloric solution. After drying under vacuum, it melts with decomposition between 205 and 206 [deg.] C.

  
The elementary analysis gives the following results:

  

  <EMI ID = 147.1>


  
  <EMI ID = 148.1>

  
me thy lammon ium
  <EMI ID = 149.1>
 
  <EMI ID = 150.1>
  <EMI ID = 151.1>

  
According to the conditions described in the second step of Example 10, a catalytic hydrogenation is carried out.

  
  <EMI ID = 152.1>

  
in alcoholic solution. The catalyst is removed by filtration, the solvent is removed in vacuo, and the oily residue is taken up in 200 ml of ethyl acetate which is gradually added to 17 ml of acetic anhydride. The expected diacetylated derivative precipitates in crystallized form. It is wrung, washed with acetone and dried under vacuum.

  
  <EMI ID = 153.1>

  
Second step: Preparation of iodide, monohydrate

  
  <EMI ID = 154.1>

  
methylammonium

  
0.03 mole (9.3 g) of the diacetylated derivative is dissolved. obtained during the first step. in 30 ml of acetone added with 3 ml of water. The solution is brought to 50 ° C. and then 0.06 mol (3.75 ml) of methyl iodide is added, with stirring. The reaction medium is maintained for 30 min at 50 [deg.] C. The expected quaternary derivative precipitates. It is wrung, washed with acetone and dried. It melts with decomposition between 159 and 160 [deg.] C.

  
The elementary analysis gives the following results:

  

  <EMI ID = 155.1>


  
Third step: Preparation of the dihydrochloride, semihy-

  
  <EMI ID = 156.1>

  
propyltrimethylammonium

  
0.0137 mol (6.2 g) of the quaternary salt obtained in the second step is heated for three hours at reflux in 30 ml of ethanol saturated with hydrochloric gas. The expected product precipitates. It is wrung, washed with absolute alcohol and dried under vacuum. It melts with decomposition between 258 and 260 [deg.] C.

  
Elementary analysis gives the following results

  

  <EMI ID = 157.1>

Example 12:

  
The following dye composition is prepared:

  

  <EMI ID = 158.1>


  
The pH of the composition is equal to 8.4.

  
This mixture, applied for 20 min at 30 [deg.] C on bleached hair, gives them, after rinsing and shampooing, a coloring 7 YR 7/14 (determined by reading with standards

  
  <EMI ID = 159.1>

Example 13:

  
The following dye composition is prepared:

  

  <EMI ID = 160.1>


  
Polymer of acrylic acid having a molecular weight of 2 to 3 million sold under the name "CARBOPOL 934" by the company
  <EMI ID = 161.1>
 The pH of the composition is 6.7.

  
This mixture, applied for 35 min at 30 [deg.] C on bleached hair, gives them, after rinsing and shampooing, a coloration 3.75 Y 8.5 / 9.5 (determined by reading with "Munsell" standards) .

Example 14:

  
The following dye composition is prepared:
Hydrochloride

  
  <EMI ID = 162.1>

  

  <EMI ID = 163.1>


  
The pH of the composition is 7.8.

  
This mixture, applied for 25 min at 30 [deg.] C on bleached hair, gives them, after rinsing and shampooing, a coloration 7.5 YR 7/16 (determined by reading with "Munsell" standards).

Example 15:

  
The following dye composition is prepared:

  

  <EMI ID = 164.1>


  
The pH of the composition is equal to 10.

  
This mixture, applied for 25 min at 25 [deg.] C on bleached hair, gives them, after rinsing and shampooing, a coloration 6.25 Y 8.5 / 12 (determined by reading with "Munsell" standards).

Example 16:

  
The following dye composition is prepared:

  
  <EMI ID = 165.1>

  
  <EMI ID = 166.1>

  

  <EMI ID = 167.1>


  
Cetylstearyl alcohol sold under the name "ALFOL C16 / 18" by the company

  

  <EMI ID = 168.1>


  
Cetylstearyl sodium sulfate sold under the name "CI RE DE LANETTE E" by the

  

  <EMI ID = 169.1>


  
Ethoxylated castor oil sold under the name

  
  <EMI ID = 170.1>

  

  <EMI ID = 171.1>


  
  <EMI ID = 172.1>

  
This mixture, applied for 35 min at 28 [deg.] C on bleached hair, gives them, after rinsing and shampooing, a color 7 YR 7/16 (determined by reading with "Munsell" standards).

  
  <EMI ID = 173.1>

  

  <EMI ID = 174.1>


  
Cetylstearyl alcohol sold under the name "ALFOL C16 / 18" by the company

  

  <EMI ID = 175.1>


  
Cetylstearyl sodium sulfate sold under the name "CIRE DE LANETTE E" by

  

  <EMI ID = 176.1>


  
Ethoxylated castor oil sold under the name "CEMULSOL B" by the company

  

  <EMI ID = 177.1>


  
The pH of the composition is equal to 8.7.

  
This mixture, applied for 30 min at 28 [deg.] C on bleached hair, gives them, after rinsing and shampooing, a color 7.5 Y 8.5 / 11 (determined by reading with "Munsell" standards).

Example 18:

  
The following dye composition is prepared: Hydrochloride

  
  <EMI ID = 178.1>

  

  <EMI ID = 179.1>


  
Nitro-3 N'-methylamino-4 dihydrochloride

  

  <EMI ID = 180.1>


  
Hydroxyethylcellulose sold under the name "CELLOSIZE WP03" by the company

  

  <EMI ID = 181.1>


  
The pH of the composition is 8.5.

  
This mixture, applied for 25 min at 28 [deg.] C on naturally white hair at 90%, gives them, after rinsing and shampooing, a light coppery brown coloring.

Example 19:

  
The following dye composition is prepared:

  
  <EMI ID = 182.1>

  

  <EMI ID = 183.1>

The pH of the composition is equal to 8.4.

  
This mixture, applied for 20 min at 28 [deg.] C on naturally white hair at 90%, gives them, after rinsing and shampooing, a pinkish beige coloring.

Example 20:

  
The following dye composition is prepared:

  
  <EMI ID = 184.1>
  <EMI ID = 185.1>
 
  <EMI ID = 186.1>
 The pH of the composition is equal to 7.

  
This mixture, applied for 20 min at 30 [deg.] C on bleached hair, gives them, after rinsing and shampooing, a coppery blond coloring.

Example 21:

The following dye composition is prepared:

  
  <EMI ID = 187.1>

  

  <EMI ID = 188.1>


  
The pH of the composition is equal to 7.

  
This mixture, applied for 25 min at 30 [deg.] C on bleached hair, gives them, after rinsing and shampooing, a golden sand coloring.

Example n [deg.] 22:

  
The following dye composition is prepared:

  
  <EMI ID = 189.1>

  

  <EMI ID = 190.1>


  
Cetylstearyl alcohol sold under the name "ALFOL C16 / 18" by the company

  

  <EMI ID = 191.1>


  
The pH of the composition is equal to 9.

  
  <EMI ID = 192.1>

  
hair naturally white at 90%, gives them, after rinsing and shampooing, a golden blonde coloring.

  
  <EMI ID = 193.1>

  
The following dye composition is prepared:

  

  <EMI ID = 194.1>
 

  

  <EMI ID = 195.1>


  
Hydroxyethylcellulose sold under the name

  
  <EMI ID = 196.1>

  

  <EMI ID = 197.1>


  
  <EMI ID = 198.1>

  
hair discolored with straw yellow, gives them, after rinsing and shampooing, a very coppery brown color.

  
  <EMI ID = 199.1>

  
The following dye composition is prepared:

  

  <EMI ID = 200.1>


  
The pH of the composition is equal to 9.

  
  <EMI ID = 201.1>

  
bleached hair, gives them, after rinsing and shampooing, a red copper coloring.

Example 25:

  
The following dye composition is prepared:

  
  <EMI ID = 202.1>

  

  <EMI ID = 203.1>

The pH of the composition is equal to 10.1.

  
At the time of use, 100 g of hydrogen peroxide are added to 20 volumes.

  
This mixture, applied for 30 min at 30 [deg.] C on hair bleached with straw yellow, gives them, after rinsing and shampooing, a brown-black coloration.

Example 26:

  
The following dye composition is prepared:

  

  <EMI ID = 204.1>

The pH of the composition is equal to 10.5.

  
At the time of use, 75 g of hydrogen peroxide are added to 20 volumes.

  
This mixture, applied for 25 min at 30 [deg.] C on naturally white hair at 90%, gives them, after rinsing and shampooing, an ash brown color.

Example 27:

  
The following dye composition is prepared:

  
  <EMI ID = 205.1>

  

  <EMI ID = 206.1>

The pH of the composition is equal to 10.5.

  
At the time of use, 100 g of oxy water, obstructed at 20 volumes, are added.

  
. This mixture, applied for 25 minutes at 30 [deg.] C on naturally white hair at 90%, gives them, after rinsing and shampooing, a gray-blue coloring.

Example 2 8:

  
The following dye composition is prepared:
Trichlorhydrate
  <EMI ID = 207.1>
 -Pi <EMI ID = 208.1>

  
Polymer of acrylic acid having a molecular weight of 2 to 3 million sold under the name "CARBOPOL 934" by the company

  

  <EMI ID = 209.1>


  
The pH of the composition is equal to 10.

  
At the time of use, 100 g of hydrogen peroxide are added to 20 volumes.

  
This mixture, applied for 25 min at 30 [deg.] C on hair bleached with straw yellow, gives them, after rinsing and shampooing, a brown color.

Example 2 9:

  
The following dye composition is prepared:

  
  <EMI ID = 210.1>

  

  <EMI ID = 211.1>


  
Nonylphenol oxyethylenated with 4 moles of ethylene oxide

  
  <EMI ID = 212.1>

  

  <EMI ID = 213.1>


  
Nonylphenol oxyethylenated to 9 moles of oxide

  
) ethylene sold under the name "CEMULSOL
  <EMI ID = 214.1>
 Two mole oxyethylene oleic alcohol

  

  <EMI ID = 215.1>


  

  <EMI ID = 216.1>

The pH of the composition is equal to 9.9.

  
At the time of use, 100 g of hydrogen peroxide are added to 20 volumes.

  
This mixture, applied for 30 min at 28 [deg.] C on naturally white hair at 90%, gives them, after rinsing and shampooing, a clear blue coloring.

Example 30:

  
The following dye composition is prepared:

  
  <EMI ID = 217.1>

  

  <EMI ID = 218.1>


  
Oxyethylenated oleic amine containing 12 moles of ethylene oxide sold under the name

  
  <EMI ID = 219.1>
  <EMI ID = 220.1>
 
  <EMI ID = 221.1>
 Pentasodium salt of diethylene-triaminepentaacetic acid sold under the name

  

  <EMI ID = 222.1>

The pH of the composition is equal to 10.3.

  
At the time of use, 85 g of hydrogen peroxide are added to 20 volumes.

  
This mixture, applied for 25 min at 30 [deg.] C on naturally white hair at 90%, gives them, after rinsing and shampooing, a midnight blue coloring.

  
  <EMI ID = 223.1>

  
The following dye composition is prepared:

  
  <EMI ID = 224.1>

  

  <EMI ID = 225.1>


  
Cetylstearyl alcohol containing 15 moles of ethylene oxide sold under the name
  <EMI ID = 226.1>
 
  <EMI ID = 227.1>
 The pH of the composition is equal to 10.

  
At the time of use, 75 g of hydrogen peroxide are added to 20 volumes.

  
This mixture, applied for 20 min at 28 [deg.] C on bleached hair, gives them, after rinsing and shampooing, a pink Champagne coloration.

Example 32:

  
The following dye composition is prepared:

  
  <EMI ID = 228.1>

  

  <EMI ID = 229.1>


  
Polymer of acrylic acid with a molecular weight of 2 to 3 million sold under

  
the name "CARBOPOL 934" by the company

  

  <EMI ID = 230.1>


  
Ethylene-diamine-tetraacetic acid sold
  <EMI ID = 231.1>
 The pH of the composition is equal to 10.3.

  
At the time of use, 100 g of hydrogen peroxide are added to 20 volumes.

  
This mixture, applied for 30 min at 28 [deg.] C on hair bleached with straw yellow, gives them, after rinsing and shampooing, a medium brown red copper coloring.

Example 33:

  
The following dye composition is prepared:
Monohydrochloride

  
  <EMI ID = 232.1>

  

  <EMI ID = 233.1>


  
The pH of the composition is equal to 7.

  
This mixture, applied for 20 minutes at 30 [deg.] C on bleached hair, gives them, after rinsing and shampooing, a clear copper coloring.

Example 34:

  
The following dye composition is prepared: [(3-methylamino-nitro-4 ') hydrochloride

  

  <EMI ID = 234.1>


  
The pH of the composition is 7.5.

  
This mixture, applied for 30 min at 28 [deg.] C on bleached hair, gives them, after rinsing and shampooing, a coloration 4.5 Y 8.5 / 13 (determined by reading with "Munsell" standards).

Example 35:

  
The following dye composition is prepared:

  

  <EMI ID = 235.1>
 

  

  <EMI ID = 236.1>


  
The pH of the composition is equal to 10.2.

  
At the time of use, 120 g of hydrogen peroxide are added to 20 volumes.

  
  <EMI ID = 237.1>

  
naturally white hair at 90%, gives them, after rinsing and shampooing, a midnight blue coloring.

  
Example 36:

  
We prepare the following dye composition
- Hydrochloride, hydrochloride semihydrate &#65533; <EMI ID = 238.1>
  <EMI ID = 239.1>
- Nonylphenol oxyethylenated with 9 moles of ethylene oxide sold under the name
  <EMI ID = 240.1>
 
  <EMI ID = 241.1>
 The pH of the composition is equal to 10.

  
At the time of use, 100 g of hydrogen peroxide are added to 20 volumes.

  
This mixture, applied for 20 minutes at 30 [deg.] C on naturally white hair at 90%, gives them, after rinsing and shampooing, a blue-gray coloration.

Example 37:

  
The following dye composition is prepared:
- Trichlorhydrate, Rdiamino-2 'monohydrate, 4')

  

  <EMI ID = 242.1>

The pH of the composition is 9.8.

  
At the time of use, 100 g of hydrogen peroxide are added to 20 volumes.

  
This mixture, applied for 25 min at 28 [deg.] C on hair bleached with white, gives them, after rinsing and shampooing, a pink shade with golden reflections.

Example 38:

  
The following dye composition is prepared: <EMI ID = 243.1>

  

  <EMI ID = 244.1>

The pH of the composition is equal to 10.

  
At the time of use, 120 g of hydrogen peroxide are added to 20 volumes.

  
  <EMI ID = 245.1>

  
hair naturally white at 90%, gives them, after rinsing and shampooing, a hazelnut color.

Example 39:

  
The following dye composition is prepared: <EMI ID = 246.1>

  

  <EMI ID = 247.1>

The pH of the composition is equal to 10.1.

  
At the time of use, 120 g of hydrogen peroxide are added to 20 volumes.

  
This mixture, applied for 15 min at 30 [deg.] C on hair bleached with straw yellow, gives them, after rinsing and shampooing, a coppery brown coloring.

Example 40:

  
The following dye composition is prepared: <EMI ID = 248.1>

  

  <EMI ID = 249.1>


  
The pH of, the composition is equal to 9.3.

  
  <EMI ID = 250.1> <EMI ID = 251.1>

  
At the time of use, add 100 g of water

  
oxygenated to 20 volumes.

  
This mixture, applied for 25 min at 25 [deg.] C on naturally white hair at 90%, gives them, after rinsing and shampooing, a dark brown coloring with copper highlights.

Example 41:

The following dye composition is prepared:

  

  <EMI ID = 252.1>


  
The pH of the composition is equal to 9.9.

  
At the time of use, 100 g of hydrogen peroxide are added to 20 volumes.

  
  <EMI ID = 253.1>

  
hair naturally white at 90%, gives them, after rinsing and shampooing, a hazelnut color.

  
It is understood that the embodiments described above are in no way limiting and may give rise to any desirable modifications, without departing from the scope of the invention.


    

Claims (27)

1. New chemical compound of formula  <EMI ID = 254.1> or a corresponding acid salt, formula in which: <EMI ID = 255.1> Y representing two identical or different substituent groups lower alkyl or lower hydroxyalkyl having at most 4 carbon atoms, these two groups possibly forming, with the nitrogen atom which carries them, a morpholinic or piperidinic heterocycle, one or both of the substituents which make up Y can also represent hydrogen when A denotes NY only, Y 'representing a lower alkyl substituent group having at most 4 carbon atoms and X representing an anion; <EMI ID = 256.1> hydrogen atom, or a lower alkyl or hydroxyalkyl radical having at most 4 carbon atoms, provided that, when A designates NY, 1) if Z is in posi- <EMI ID = 257.1> R1 and R2 both representing a hydrogen atom, one of the two substituents which compose Y does not represent an ethyl group when the other substituent represents a hydrogen atom, and the two substituents that make up Y do not form, with the nitrogen atom which carries them, a morpholinic or piperidinic heterocycle, and 2) when one of the two substituents which compose Y designates a hydrogen atom or an alkyl group and the other designates a group alkyl,  <EMI ID = 258.1>  <EMI ID = 259.1> hydrogen or an alkyl group. 2. Process for the preparation of a chemical compound of formula CE) (or a corresponding acid salt), formula in which: <EMI ID = 260.1> - A denotes NY, Y representing two identical or different substituent groups lower alkyl or lower hydroxyalkyl having at most 4 carbon atoms, these two groups possibly forming with the nitrogen atom which carries them a morpholinic or piperidinic heterocycle, one or both substituents which make up Y which can also represent hydrogen; <EMI ID = 261.1> provided that if Z is in position 4 on the benzene nucleus  <EMI ID = 262.1> killers which compose Y does not represent an ethyl group when the other substituent represents a hydrogen atom, and the two substituents which compose Y do not form, with the nitrogen atom which carries them, a morpholinic or piperidinic cycle, characterized by the fact that it comprises the following succession of stages: a) acting on the known compound of formula (II)  <EMI ID = 263.1>  epichlorohydrin to obtain the compound of formula (III)  <EMI ID = 264.1>  b) an amine of formula HNY, where Y has the meaning indicated above, is made to act on the compound of formula (III) to obtain the compound of formula (IV)  <EMI ID = 265.1>  c) on the compound of formula (IV), a strong acid is made to act, such as hydrochloric acid, to obtain the compound of formula (V)  <EMI ID = 266.1> Y having the meaning specified above. 3. Process for the preparation of a compound of formula (I) (or a corresponding acid salt), formula in which: - Z represents NH2; - A denotes NY, Y representing two identical or different substituent groups lower alkyl or lower hydroxyalkyl having at most 4 carbon atoms, these two groups possibly forming with the nitrogen atom which carries them a morpholinic or piperidinic heterocycle, one or both substituents which make up Y which can also represent hydrogen, <EMI ID = 267.1> provided that if Z is in position 4 on the benzene nucleus  <EMI ID = 268.1> killers which compose Y does not represent an ethyl group when the other substituent represents a hydrogen atom, and the two substituents which compose Y do not form, with the nitrogen atom which carries them, a morpholinic or piperidinic cycle, characterized in that the process according to claim 2 is carried out and that the product obtained is subjected to a reduction of nitro group in order to obtain the compound of formula (VI)  <EMI ID = 269.1> Y having the meaning specified above. 4. Process for the preparation of a compound of formula (I) (or a corresponding acid salt), formula in which; <EMI ID = 270.1> - A represents NY, Y representing two identical or different substituent groups lower alkyl or lower hydroxyalkyl having at most 4 carbon atoms, these two groups possibly forming with the nitrogen atom which carries them a morpholinic or piperidinic heterocycle, one or both substituents which make up Y which can also represent hydrogen; <EMI ID = 271.1> hydrogen atom or a lower alkyl or hydroxyalkyl radical having at most 4 carbon atoms, the case where R1 = R2 = H being excluded, characterized by the fact that the compound of formula (VII) is acted on  <EMI ID = 272.1>  epichlorohydrin and acting on the compound obtained an amine of formula HNY, where Y has the meaning given above, to obtain the compound of formula (VIII)  <EMI ID = 273.1> 5. Process for the preparation of a compound of formula (I) (or a corresponding acid salt), formula in which: - Z represents an NI group; - A denotes NY, Y representing two identical or different substituent groups lower alkyl or lower hydroxyalkyl having at most 4 carbon atoms, these two groups possibly forming with the nitrogen atom which carries them a morpholinic or piperidinic heterocycle, one or both substituents which make up Y which can also represent hydrogen, <EMI ID = 274.1> hydrogen atom or a lower alkyl or hydroxyalkyl radical  <EMI ID = 275.1> being excluded, characterized in that the compound obtained by the process according to claim 4 is subjected to a reduction of the nitro group. 6. Method according to one of claims 3 or 5, characterized in that the reduction of the nitro group is carried out either by zinc powder in an alcoholic medium in the presence of ammonium chloride, or by catalytic hydrogenation. 7. Process for the preparation of a compound of formula (I) (or a corresponding acid salt), formula in which: <EMI ID = 276.1> - A denotes NY, Y representing two identical or different substituent groups lower alkyl or lower hydroxyalkyl having at most 4 carbon atoms, these two groups optionally forming with the nitrogen atom which carries them a morpholinic or piperidinic heterocycle; - R1 and R2 are identical or different and represent a hydrogen atom or a lower alkyl or hydroxyalkyl radical having at most 4 carbon atoms, the case where  <EMI ID = 277.1> characterized by the fact that the process according to claim 3 is carried out and that, on the product of formula (VI) obtained, a group is substituted  <EMI ID = 278.1> substituted. 8. Process for the preparation of a quaternary compound of formula (I), in which: <EMI ID = 279.1>  <EMI ID = 280.1> Y representing those identical or different substituent groups lower alkyl or lower hydroxyalkyl having at most 4 carbon atoms, these two groups optionally forming with the nitrogen atom which carries them a morpholinic or piperidinic heterocycle-, Y 'representing an alkyl substituent group lower having at most 4 carbon atoms and X representing an anion; <EMI ID = 281.1> hydrogen atom or a lower alkyl or hydroxyalkyl radical having at most 4 carbon atoms, characterized in that the nuclear amine (s) are acetylated from the corresponding tertiary compound; that a quaternization agent is then made to act; and finally deacetylated by the action of an acid. 9. Method according to claim 8, characterized in that one uses as quaternizing agent methyl iodide. 10. Dye composition for keratin fibers, and in particular for hair, characterized in that it comprises, in an appropriate support, at least one compound of formula (I) (or a corresponding acid salt), in which: - Z represents a nitro group; <EMI ID = 282.1> Y representing two identical or different substituent groups. lower alkyl or lower hydroxyalkyl having at most 4 carbon atoms, these two groups optionally forming, with the nitrogen atom which carries them, a morpholinic or piperidinic heterocycle, one or both of the substituents which make up Y can also represent the hydrogen when A denotes NY only, Y 'representing a lower alkyl substituent having at most 4 carbon atoms and X representing an anion; <EMI ID = 283.1> hydrogen atom or a lower alkyl or hydroxyalkyl radical having at most 4 carbon atoms. 11. Dye composition for keratin fibers, and in particular for hair, characterized in that it comprises, in an appropriate support, at least one compound of formula (I) (or a corresponding acid salt), formula in which: <EMI ID = 284.1>  <EMI ID = 285.1> dication 10. 12. Composition according to one of claims 10 or 11, characterized in that the compound of formula (I) is present in the composition at a concentration of between 0.001 and 4% by weight relative to the total weight of the composition. 13. Dye composition for keratin fibers, and in particular for hair, containing, in an appropriate support, at least one oxidation base, characterized in that it also contains at least one compound of formula (I) (or a corresponding acid salt) formula in which: <EMI ID = 286.1>  <EMI ID = 287.1> Y representing two identical or different substituent groups lower alkyl or lower hydroxyalkyl having at most 4 carbon atoms, these two groups possibly forming with the nitrogen atom which carries them a morpholinic or piperidinic heterocycle, one or both substituents which make up Y which may also represent hydrogen when A denotes NY only, Y ′ representing a lower alkyl substituent group having at most 4 carbon atoms and Y representing an anion; <EMI ID = 288.1> hydrogen atom or a lower alkyl or hydroxyalkyl radical, having at most 4 carbon atoms, provided that when A denotes NY, if Z is in position 4 on the benzene nucleus and if NR1R2 is in position 2,  <EMI ID = 289.1> of the two substituents that make up Y does not represent an ethyl group when the other substituent represents a hydrogen atom, and the two substituents which make up Y do not form, with the nitrogen atom which carries them, an orpholinic or piperidinic heterocycle. 14. Composition according to claim 13, characterized in that the compound of formula (I) is present in the composition at a concentration of between 0.001 and 2.5% by weight relative to the total weight of the composition. 15. Composition according to one of claims 10 to 14, characterized in that it contains at least one oxidation base taken from paraphenylenediamines, paraaminophenols or heterocyclic bases. 16. Composition according to one of claims 10 to 15, characterized in that it contains at least one coupler taken from the group formed by the. resorcin, pyrocatechol, 2-methyl resorcin, 2-ethyl resorcin,  <EMI ID = 290.1> N - (&#65533; -hydroxyethyl) 5-amino phenol, 6-hydroxy benzomorpholine, 2,6-dimethyl-3-acetylamino phenol, 2-methyl-5-arbethoxyamino phenol, 2-methoxy-5-carbethoxyamino phenol , 2-methyl-5-ureido phenol, 2,4-diamino phenoxyethanol, 2,4-diamino anisole, 2,6-dimethyl metaphenylenediamine, (2-amino-4-methylaminoamino) phenoxyethanol,  <EMI ID = 291.1> (2,4-diamino) phenyl.. mesylaminoethyl ether, N-carbamylmethylamino-2 amino-4 anisole, 3-amino-4-methoxyphenol,  <EMI ID = 292.1> xy-2,6 pyridine, 1-phenyl-3-methyl-pyrazolone-5, (2-amino, N - hyd -hydroxyethylamino-4) phenyl &#65533; -hydroxypropyl ether. 17. Composition according to one of claims 10 to 16, characterized in that it contains orthophenylenediamines and orthoaminophenols, optionally substituted on the nucleus or on the amine functions, or alternatively orthodiphenol. 18. Composition according to one of claims 10 to 17, characterized in that it contains dye precursors of the benzene series comprising, on the nucleus, at least three substituents chosen from the group formed by hydroxy, methoxy or amino groups. 19. Composition according to one of claims 10 to 18, characterized in that it contains quinone dyes. 20. Composition according to one of claims 10 to 19, characterized in that it comprises indoanilines, indophenols, indamines or their leuco-derivatives. 21. Composition according to one of claims 10 to 20, characterized in that it contains dyes  <EMI ID = 293.1> nitrates of the benzene series. 22. Composition according to one of claims 10 to 21, characterized in that its pH is between 5 and 11.5. 23. Composition according to one of claims 10 to 22, characterized in that it comprises at least one  <EMI ID = 294.1> tion, surface-active agents, thickening agents, antioxidants, alkalinizing or acidifying agents, perfumes, sequestering agents, film-forming products, treatment agents, solvents and anti- oxidants. 24. Composition according to one of claims 11 to 23, characterized in that it contains, at the time of use, an oxidizing agent ...... 25. Composition according to one of claims 10 to 24, characterized by the fact that it is in the form of a liquid, cream, gel or aerosol. 26. A hair dyeing method, characterized in that a composition according to one of claims 10, 24 or 25 is left to act on the hair for an exposure time varying between 10 and 45 minutes, which is rinsed, that eventually we wash and rinse again, and dry. 27. The method of claim 26, wherein the dye composition used contains at least one oxidation base, characterized in that at the time of  <EMI ID = 295.1>