2-imino-2,3-dihydro-1H-indole derivatives for dyeing keratin...

Details 2-imino-2,3-dihydro-1H-indole derivatives for dyeing keratin... 2-imino-2,3-dihydro-1H-indole derivatives for dyeing keratin...

1997-08-22

2001-01-30

Liott, Caroline D. (Department: 1751)

Bleaching and dyeing; fluid treatment and chemical modification

Dyeing involving animal-derived natural fiber material ,...

Hair dyeing

C008S406000, C008S574000, C008S618000, C548S483000

Reexamination Certificate

active

06179883

ABSTRACT:

The present invention relates to novel 2-imino-2,3-dihydro-1H-indole derivatives, to a process for their preparation, to their use in dyeing keratin fibres such as the hair and to dyeing processes using them.
It has already been proposed in the past to dye the hair using, as couplers, certain monohydroxy-indoles or monoaminoindolines, in particular in French patent FR-A-2 008 797. U.S. Pat. No. 4,013,404 describes the use of mono- or diaminoindolines or monohydroxy-indolines as oxidation bases or as couplers in the oxidation dyeing of the hair.
Dyes of the indole family, in particular 5,6-dihydroxyindole, and their use for dyeing keratin fibres such as human hair are moreover known, in particular from French patents FR-A-1,133,594 and FR-A-1,166,172.
The inventors have discovered novel monoalkoxy, mono- or dihydroxy 2-imino-2,3-dihydro-1H-indole derivatives which can have noteworthy dyeing properties towards keratin fibres such as the hair. These compounds are readily oxidized in alkaline medium and may be used in hair dyeing possibly without using an oxidizing agent, which makes it possible to obtain a varied range of more or less intense shades.
The subject of the invention is novel 2-imino-2,3-dihydro-1H-indole derivatives as well as the addition salts thereof with an acid, of formula (I) or (II) which will be defined below.
Another subject of the invention is the use of these compounds in the dyeing of keratin fibres.
The subject of the invention is dye compositions intended for dyeing keratin fibres, and in particular human hair, containing at least one 2-imino-2,3-dihydro-1H-indole derivative of formula (I) or (II) defined below.
The subject of the invention is also dyeing processes using these compounds.
Other subjects of the invention will become apparent on reading the description and the examples which follow.
The 2-imino-2,3-dihydro-1H-indole derivatives in accordance with the invention correspond to formula (I) or (II) below:
in which:
R, R
2
and R
3
, which may be identical or different, denote a hydrogen atom or a C
1
-C
4
alkyl, carboxyl, alkoxy(C
1
-C
4
)carbonyl, C
1
-C
4
monohydroxyalkyl, C
2
-C
4
polyhydroxyalkyl, (C
1
-C
4
)alkoxy(C
1
C
4
)alkyl, mono(C
1
-C
4
)alkylamino(C
1
-C
4
)alkyl or di(C
1
-C
4
)alkyl-amino(C
1
-C
4
)alkyl radical;
R′
3
and R
4
, which may be identical or different, denote a C
1
-C
4
alkyl, carboxyl, (C
1
-C
4
)alkoxycarbonyl, C
1
-C
4
monohydroxyalkyl, C
2
-C
4
polyhydroxyalkyl, (C
1
-C
4
)alkoxy(C
1
-C
4
)alkyl, mono(C
1
-C
4
)alkylamino(C
1
-C
4
)alkyl or di(C
1
-C
4
)alkylamino(C
1
-C
4
)alkyl radical;
R
5
denotes a hydrogen atom or a C
1
-C
4
alkyl, C
1
-C
4
monohydroxyalkyl, C
2
-C
4
polyhydroxyalkyl, (C
1
-C
4
)alkoxy(C
1
-C
4
)alkyl, mono(C
1
-C
4
)alkylamino(C
1
-C
4
)alkyl or di(C
1
-C
4
)alkylamino(C
1
-C
4
)alkyl radical;
it being possible for the said alkyl or alkoxy radicals to be linear or branched.
The addition salts with an acid of the compounds of formula (I) or (II) also constitute a subject of the invention, and may be chosen in particular from the hydrochlorides, hydrobromides, sulphates, tartrates, lactates and acetates.
Each of the formulae (I) or (II) defined above may give rise to several forms, in which the preponderance and/or stability of each form will depend on the nature of the various substituents R
1
, R
2
, R
3
, R′
3
and R
4
.
Formula (I) may give rise to the 3 forms below:
Formula (II) may give rise to the two forms below:
For the sake of clarity, all the 2-imino-2,3-dihydro-1H-indole derivatives will be defined hereinbelow by formulae (I) or (II) below:
in which R
1
, R
2
, R
3
, R′
3
, R
4
and R
5
have the same meanings as those indicated above in the definitions of formulae (I) and (II).
Among the preferred compounds of formula (I) or (II) and the addition salts thereof with an acid, mention may be made more particularly of 5,6-dihydroxy-1,3-dihydroindol-2-ylideneamine and the addition salts thereof with an acid.
The specific compounds of formula (IA) or (IIA) below or the other forms thereof:
the radicals R
3
, R′
3
, R
4
and R
5
have the same meanings as those indicated above in the definitions of the formulae (I) and (II), may be obtained according to the process described in the RG Glushkov patent USSR Patent 179 320 (1965) and in the document Chem. Abstr 65, 2225(1966) and corresponding to schemes A and A′ below:
In Schemes A and A′ defined above, the meanings of the radicals R
3
, R′
3
, R
4
and R
5
in formulae (1), (1′), (2) and (2′) are identical to those indicated above in the formula (I) or (II).
This is a two-step process beginning with the starting compounds of formula (1) or (1′) which have the structure of orthonitrophenylacetonitriles whose method of synthesis is as in the literature (M. Makosza, J. Winiarski, Acc. Chem. Res., 87, 1987, 282; M. Makosza, W. Danikiewicz, K. Wojciechowski; Liebigs Ann. Chem. 1988, 203).
The first step is preferably either a chemical reduction in the presence of an organic solvent using metals such as zinc or tin, or a selective hydrogenation using a catalyst such as palladium or platinum. The solvents used are preferably ethers and more particularly tetrahydrofuran (THF). The reaction temperature ranges preferably from 25° C. to the reflux temperature of the solvent and more particularly from 25 to 40° C.
The second step is preferably a cyclization reaction in acidic medium in the presence of an organic solvent. Acetic acid is preferably used. The reaction temperature is that of reflux of the solvent. The final product of formula (IA) or (IIA) is preferably isolated in the form of an addition salt with an acid. It is obtained by precipitation of the reaction medium in acidic medium. For example, in order to obtain a hydrochloride, a stream of HCI gas is passed through at the end of the reaction.
Specific compounds of formula (IB) or (IIB) corresponding respectively to formula (I) and to formula (II), in which R
1
is a hydrogen atom, and the specific compounds of formula (IC) or (IIC) corresponding respectively to formula (I) and to formula (II), in which R
1
and R
2
are both other than a hydrogen atom, may be obtained according to a preparation process, with reference to the literature, and corresponding to Schemes B and B′ below:
Compound (1) or (1′) may be treated under cyclizing reduction conditions according to known methods such as, for example, that described by Makosza M. et al., in Liebigs Ann. Chem., 203, (1988) in order to lead respectively to the indole (3) or (3′). The indole (3) or (3′) may be alkylated to lead respectively to the indole (4) or (4′) according to standard methods as described, for example, in “Heterocyclic Compounds: Indoles” part 11 pp. 72-73, edited by N. J. Houlian, Wiley-lnterscience.
Compounds (3) or (3′) and (4) or (4′) may react with an azide of structure (5) to lead respectively to the 2-iminoindolines of formula (IB) or (IIB) and (IC) or (IIC) according to a method which has already been described [Harmon R. E., et al., J. Org. Chem. 38(1), 11, (1973)].
The compounds of structures (IB) or (IIB) and (IC) or (IIC) may also be obtained by reaction of an amine R
2
NH
2
respectively with a 2-indolinethione derivative of structure (6) or (6′) and (7) or (7′) as described by Hino T. et al. in Tetrahedron 27, 775, (1971) and represented in Schemes C and C′ below:
The 2-imino-2,3-dihydro-1H-indole derivatives of formula (I) or (II) defined above are generally used with the aid of compositions which constitute another subject of the invention.
The dye compositions intended to be used for dyeing keratin fibres, and in particular human keratin fibres such as the hair, in accordance with the invention are characterized in that they contain, preferably in a medium which is suitable for dyeing, at least one compound corresponding to formula (I) or (II) defined above.
The amount of compound of formula (I) or (II) used in the composition is generally present in proporti

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