FR2842521A1 - BENZOQUINONEMONOIMINES DERIVATIVES, SYNTHESIS METHOD, COLORING COMPOSITIONS CONTAINING THEM, AND USES THEREOF - Google Patents

Abstract

The present invention relates to the field of synthetic organic chemistry and relates to new derivatives of benzoquinonemonoimines, their chemical synthesis process, the coloring compositions containing them and their uses as dyes or dyes, in particular as hair dyes. general (I) in which R1 represents an alkyl or aryl group and in which R2 represents a linear C1 to C10 alkyl group.

Description

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 The present invention relates to the field of synthetic organic chemistry and relates to new benzoquinonemonoimine derivatives, their method of synthesis, the compositions containing them and their uses as dyes, in particular as hair dyes.

 At present, the development of a new dye requires significant research efforts, given the many compounds already existing as well as the diversity of practical technical problems to be solved.

 A particularly crucial problem in the field of dyes is that of the substantivity, that is to say the ability of a dye to be fixed on the fiber, for example textile or hair, without the intervention of a mordant. . For reasons, in particular, of convenience of use and of cost reduction, a good number of research works have focused on increasing the substantivity of existing molecules or even on the creation of new compounds having higher substantivities.

 It has thus been proposed to use cationic surfactants to facilitate the adsorption of dyes on the keratin fiber of the hair and thus increase the substantivity of certain known dyes.

 In particular, it has been discovered that the substantivity properties of a large number of acid dyes can be considerably modified by complexing said dyes with a cationic surfactant derivative. The anion-cation complex obtained, in which the positive charge and the negative charge are carried by the two different chemical entities forming the complex, then behaves like a dye whose substantivity can be much more marked than that of the starting acid dye, allowing to color the fiber in unison conditions that are encountered quite rarely.

 However, the existing anion-cation complexes have the major drawback of being generally insoluble in the solvents usually used, so that it is essential to disperse them or to solubilize them with a surfactant which will most often be nonionic.

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 As a result, the formulation of coloring compositions containing one or more anion-cation complexes is particularly delicate. In addition, the complex must be as close as possible to its equimolar composition to have maximum substantivity and perfectly redissolved in a non-polar solvent. If the latter is present in insufficient quantity, the anion-cation complex will tend to stick to the fiber, giving opaque colors, very irregular and not very resistant to friction.

 If the solvent is in excess, the affinity of the dye for the fiber is considerably reduced, the partition coefficient of the anionization dye playing in favor of the solution, at the expense of the hair.

 Furthermore, some of the known compositions intended for the permanent coloring of the hair require the use of a separate oxidant which is mixed with the precursor of the dye in order to obtain the dye mass proper. However, such compositions with separate oxidants are impractical to use, the mixing of the various components as well as the application of the dye mixture obtained having to be carried out under very precise conditions in order to be able to guarantee successful coloring.

 Added to this is the problem that the oxidants or other chemical reagents which are used in the aforementioned known compositions are often irritating and / or corrosive substances and therefore present a risk for the health of persons who are brought into direct contact or indirect with said substances. As a result, the risks of allergies or burns are far from negligible for this type of product.

 There is therefore a real need for a coloring composition which, with equivalent or better results, can dispense with the use of problematic chemical reagents, such as oxidants.

 The problem posed by the present invention therefore consists in overcoming at least some of the aforementioned drawbacks.

To this end it relates to compounds of general formula (I)

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 in which R represents an alkyl or aryl group and in which R2 represents a linear C1 to C10 alkyl group.

 The present invention also relates to a process for the chemical synthesis of the compounds of general formula (I) (hereinafter also designated as compound (s) (I)), the use of a compound (I) in accordance with invention as a dye, as a permanent or semi-permanent dye and in particular as a hair dye, in particular for dyeing the hair.

 It also relates to a composition comprising at least one compound (I) according to the invention as a coloring substance.

 The invention will be better understood from the description below, which relates to preferred embodiments, given by way of nonlimiting examples.

dans laquelle R1 représente un groupement alkyle ou aryle et dans laquelle R2 représente un groupement alkyle linéaire en Clà CIO. In a first aspect, the subject of the present invention is the compounds of general formula (I)

in which R1 represents an alkyl or aryl group and in which R2 represents a linear C1 to C10 alkyl group.

 Unless otherwise indicated, the following terms used in the present description and the present set of claims have the following meanings: - alkyl denotes a linear saturated monovalent hydrocarbon radical having from 1 to 10 carbon atoms or a branched saturated monovalent hydrocarbon radical having from 3 to 15 carbon atoms, for example, methyl, ethyl, propyl, 2-propyl, tert-butyl, etc.

 - aryl denotes an aromatic hydrocarbon radical of optionally substituted phenyl type, that is to say a phenyl group which is optionally independently substituted with one or more substituents chosen from the group formed by an alkyl group (as defined above), amino , hydroxy, halo, sulfonate, alkoxy obtained

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 from an alkyl group as defined above or aryloxy obtained from an aryl group as defined above.

 More preferably, the present invention relates to the compounds of general formula (I) in which R1 represents an alkyl group, preferably chosen from the group formed by methyl, ethyl, propyl, butyl or tert-butyl groups.

 In the case where R1 represents an alkyl group, the compounds (I) according to the invention have very high solubilities in water of the order of 40 g / 1.

 Even more preferably, R1 represents a tert-butyl group.

 In particular, the compound (I) according to the invention is characterized in that R1 preferably represents a tert-butyl group and R2 represents a methyl group or in that R1 preferably represents a tert-butyl group and R2 represents an ethyl group.

 According to another variant, the compound (I) is further characterized in that RI preferably represents a paratertiobutylphenyl group.

 Advantageously, R1 preferably represents a paratertiobutylphenyl group and R2 represents a methyl group. In these two cases, compounds are obtained which are insoluble in water but whose other properties (solubility in other solvents, substantivity, etc.) remain very advantageous for the applications envisaged in the context of the present invention.

 The introduction of a sulfonate functionality within the group R1 can, if necessary, overcome this lack of solubility while maintaining the various advantages provided by the nature of the second substituent R2 as defined above.

 Thanks to the structure of the new derivatives of general formula (I) proposed by the present invention, the cationic active part of the latter binds much more easily and more durably to the products to be colored, for example to the negatively charged keratin of the hair, without present the drawbacks of known conventional dyes.

 Indeed, the inventors have demonstrated in a surprising and unexpected way that by functionalizing compounds of the family of benzoquinonemonoimines, in particular by selective alkylation of a

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 oxygen atom, it was possible to obtain synthetic derivatives which, on the one hand, are perfectly soluble in the solvents commonly used in the field of coloring (in particular in water) and which, on the other hand , present a significant increase in the substantivity for the products or fibers to be colored, in particular for the keratin present in the hair.

 Without wishing to be bound by a very particular theory, the inventors believe that the unexpected and surprising new properties of the compounds according to the invention result mainly from the abovementioned alkylation.

 As shown in the general formula (I), the positive charge is delocalized on the lower part of said cycle between the nitrogen atoms while the negative charge is localized on the anion BF4-.

 In addition, the present invention describes various synthetic routes, which relate to preferred embodiments, given by way of nonlimiting examples.

 Another object of the invention is thus a process for the synthesis of a compound (I) according to the invention, characterized in that it essentially comprises the steps consisting in: a) reacting 2,4-diaminoresorcinol or a derivative of 2,4-diaminoresorcinol with R'COCl in an appropriate solvent, b) reducing the compound isolated in step a) using an appropriate reducing agent and isolating the reduced compound obtained, c) reacting the reduced product obtained from step b) with an alkylating reagent of formula (R2) 30BF4 until the gas evolution stops, then isolate and, if necessary, purify the final product obtained.

 The starting compounds can be obtained commercially or synthesized according to the usual methods. Advantageously, the inventors have found a particularly effective synthetic route and the present invention extends to this process allowing the preparation of the indicated compounds.

 The compounds of general formula (I) are prepared as indicated below. The actual synthesis is carried out in three main stages which are perfectly controlled and allow access to fully characterized compounds.

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 According to a first characteristic, the 2,4diaminoresorcinol derivative is preferably 2,4diaminoresorcinol dihydrochloride.

 More generally, the term 2,4diaminoresorcinol derivative is understood to mean any molecular precursor making it possible to release the organic reagent proper, namely 2,4-diaminoresorcinol.

 Advantageously, the solvent used in step a) is preferably acetonitrile. According to another characteristic, step a) is carried out under an inert atmosphere, preferably under a nitrogen atmosphere. Other common inert gases such as argon in particular may also be suitable.

 According to yet another characteristic, step a) is preferably carried out at room temperature, with stirring and for a reaction time of between approximately 6 and 12 hours.

 Advantageously, step b) is preferably carried out under a reflux of THF ,. with stirring and for a reaction time of between approximately 6 and 12 hours.

 Finally, the method according to the invention is further characterized in that the reducing agent used in step b) is preferably chosen from LiAIH4 and B2H6.

 As a global non-limiting example of synthesis of the process according to the present invention, 2,4-diaminoresorcinol dihydrochloride is placed in acetonitrile under an inert atmosphere in the presence of an excess of triethylamine. The corresponding necessary amount of R1COCl acid chloride is added slowly to the solution at room temperature. The solvent is then evaporated under reduced pressure.

The residue obtained is taken up in water and the insoluble product in suspension is then filtered through Büchner.

 The reduction of the compound previously obtained is then carried out in the presence of an excess of LiAIH4 after 4 to 6 hours of stirring under reflux with tetrahydrofuran (THF). The excess LiAlH4 is destroyed by adding an aqueous methanol solution.

 The aluminum salts obtained are then filtered through Büchner.

After evaporation of the filtrate, extraction with dichloromethane, drying over magnesium sulfate and evaporation of the solvent under reduced pressure, the intermediate product obtained is recrystallized from a mixture of dichloromethane and hexane.

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 Said intermediate product is then redissolved in a dichloromethane solution, then the alkylating reagent (R2) 3OBF4 is added. The compound of general formula (I) is then obtained in the form of a crystalline solid after evaporation to dryness under reduced pressure then recrystallization from a mixture of dichloromethane and hexane.

 The compounds (I) obtained showed perfect stability in air, in the solid state and in solution.

 Practical examples specifying the operating reaction conditions are described below.

Example 1: synthesis of a compound (I) where R1 is a t-butyl group (tBu) and R2a methyl group (Me)
Procedure: 1 g (4.7 mmol) of 2,4-diaminoresorcinol dihydrochloride is placed in acetonitrile (v = 200 ml) under an inert atmosphere and in the presence of an excess of triethylamine (v = 4 ml) . The tBu-C (O) Cl acid chloride (v = 2.34 ml, 18.8 mmol) is slowly added to the solution at room temperature and then stirred for 12 hours. The solvent is then evaporated under reduced pressure. The residue obtained is taken up in water and the insoluble product in suspension is then filtered through a Büchner allowing 2. 09 g (4.3 mmol) of the diester diamide intermediate to be isolated (92% yield).

The reduction of the compound previously obtained (2.09 g) is carried out in anhydrous tetrahydrofuran (v = 150 ml) in the presence of 1.63 g of LiAIH4 (43 mmol) after 12 hours of stirring under reflux. The excess LiAlH4 is destroyed using an aqueous methanol solution (2 ml of methanol and 4 ml of water). The product obtained (precursor of I) is then isolated with a yield of 70% (m = 0.84 g, 3.01 mmol) after purification by extraction (3 times 200 ml of dichloromethane).

This product is then placed in solution in dichloromethane (v = 100 ml) and then 0.45 g (3.01 mmol) of alkylating reagent (CH3) 30BF4 is added. The reaction is complete when there is no more evolution of Me-O-Me (gas). 1 is then obtained with a yield of 90% (m = 1.02 g, 2.70 mmol) after evaporation under reduced pressure of the solvent then recrystallization from a dichloromethane / hexane mixture.

 The compound obtained in this example was characterized as follows:

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Mass spectrometry (El, 70 eV): m / z: 293 [M +]
NMR: 'H NMR (300 MHz, CDC13): 8 (ppm) = 1.06 (s, 9H, CH3), 1.07 (s, 9H, CH3), 3.27 (d, 2H, CH2), 3.53 (d, 2H, CH2), 4.07 (s, 3H, OCH3), 5.81 (s, 1H, C = CH), 5.89 (s, 1H, C = CH), 7, 41 (sb, 1H, NH), 8.99 (sb, 1H, NH).

 15N NMR (400 MHz, CDC13): 8 (ppm) = -245 (s, 1N, N-H), -255 (s, IN, N-H).

 Crystallographic data: C36H62N4O4B2Cl4F8, M = 930.32, monoclinic, space group C2 / c; a = 32.358 (2), = 13.502 (2), = 24.127 (2), a = 90,000 (10), p = 116.35 (5), y = 90,000 (10), V = 9445.8 (17) A3, Z = 8, u (Mo-Ka) = 0.71070 mm-1, T = 173 (2) 3663 data with I> 3 # (I), final R = 0.1278, Rw = 0.2809, GOF = 0.933.

Example 2: of a compound (I) where R1 is a t-butyl group (tBu) and R2 is an ethyl group (Et):
Procedure: 1 g (4.7 mmol) of 2,4-diaminoresorcinol dihydrochloride is placed in acetonitrile (v = 200 ml) under an inert atmosphere and in the presence of an excess of triethylamine (v = 4 ml) . The tBu-C (O) Cl acid chloride (v = 2.34 ml, 18.8 mmol) is slowly added to the solution at room temperature and then stirred for 12 hours. The solvent is then evaporated under reduced pressure. The residue obtained is taken up in water and the insoluble product in suspension is then filtered on a Büchner allowing 2.09 g (4.3 mmol) of the diester diamide intermediate to be isolated (92% yield).

The reduction of the compound obtained (2.09 g) is carried out in anhydrous tetrahydrofuran (v = 150 ml) in the presence of 1.63 g of LiAIH4 (43 mmol) after 12 hours of stirring under reflux. The excess LiAIH4 is destroyed using an aqueous methanol solution (2 ml of methanol and 4 ml of water). The product obtained (precursor of I) is then isolated with a yield of 70% (m = 0.84 g, 3.01 mmol) after purification by extraction (3 times 200 ml of dichloromethane).

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 This product is placed in solution in dichloromethane (v = 100 ml) and then 0.60 g (3.01 mmol) of alkylating reagent (Et) 30BF4 is added. The reaction is complete when there is no more evolution of Me-O-Me (gas). 1 is then obtained with a yield of 90% (m = 1.07 g, 2.70 mmol) after evaporation under reduced pressure of the solvent and then recrystallization from a dichloromethane / hexane mixture.

The compound obtained in this example was characterized as follows:
1H NMR (300 MHz, CDC13): 8 (ppm) = 1.06 (s, 9H, CH3), 1.07 (s, 9H, CH3), 1.60 (t, 3H, CH3), 3.30 (d, 2H, CH2), 3.57 (d, 2H, CH2), 4.27 (q, 2H, OCH2), 5.85 (s, 1H, C = CH), 5.88 (s, 1H , C = CH), 7.38 (sb, 1H, NH), 8.90 (sb, 1H, NH).

Example 3: synthesis of a compound (I) where R1 is a para-t-butyl-phenyl group (tBu-Ph) and R2 a methyl group (Me):
Procedure: 1 g (4.7 mmol) of 2,4-diaminoresorcinol dihydrochloride is placed in acetonitrile (v = 200 ml) under an inert atmosphere and in the presence of an excess of triethylamine (v = 4 ml) . R1C (O) Cl acid chloride (v = 3.4 ml, 18.8 mmol) is slowly added to the solution at room temperature and then stirred for 12 hours. The solvent is then evaporated under reduced pressure. The residue obtained is taken up in water and the insoluble product in suspension is then filtered through a Buchner allowing 2.38 g (3.055 mmol) of the diester diamide intermediate to be isolated (yield of 65%).

The reduction of the compound thus obtained (2.38 g) is carried out in anhydrous tetrahydrofuran (v = 150 ml) in the presence of 1.16 g of LiAIH4 (30.55 mmol) after 12 hours of stirring under reflux. The excess LiAIH4 is destroyed using an aqueous methanol solution (2 ml of methanol and 4 ml of water). The product obtained (precursor of I) is then isolated with a yield of 80% (m = 1.05 g, 2.44 mmol) after purification by extraction (3 times 200 ml of dichloromethane).

This product is placed in solution in dichloromethane (v = 100 ml) and then 0.36 g (2.44 mmol) of alkylating reagent (CH3) 30BF4 is added. The reaction is complete when there is no more evolution of Me-O-Me (gas). 1 is then obtained with a yield of 90% (m = 1.17 g, 2.20 mmol) after

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 evaporation under reduced pressure of the solvent then recrystallization from a dichloromethane / hexane mixture.

 The compound obtained in this example was characterized as follows: 'H NMR (300 MHz, CDCl3): 8 (ppm) = 1.33 (s, 9H, CH3), 1.36 (s, 9H, CH3) , 4.01 (s, 3H, OCH3), 4.53 (d, 2H, CH2), 4.82 (d, 2H, CH2), 5.80 (s, 1H, C = CH), 5.85 (s, 1H, C = CH), 7.30 (m, 8H, aromatic CH), 7.52 (sb, 1H, NH), 9.60 (sb, 1H, NH).

 In a second aspect, the subject of the present invention is the use of a compound (I) as a dye, in particular as a permanent or semi-permanent dye, and more particularly for the manufacture of a hair dye, in particular for dyeing. hair.

 The inventors have found that the compounds (I) as defined above are particularly suitable for the manufacture of a permanent dye.

 The semi-permanent adjective means that the color resists 4 or 5 washes, fading very slowly and very regularly.

 The permanent adjective means that the coloring is fixed for a period of several weeks or even several months with regard to the hair or more for other products.

 Unlike certain dyes known from the state of the art which are in reality only dye precursors and which require physical and / or chemical transformation before they can be used as coloring substances proper, the compounds (I) according to l The invention directly possesses all the properties and qualities of a dye and can be used as such when they are present in a suitable solvent or on a support.

 In addition, the new active principles of formula (I) for dyeing or dyeing fibers, in particular hair fibers, are both very soluble in water, in ethanol and also soluble in most polar solvents or nonpolar, protic or aprotic.

 In addition, they have a high substantivity for said fibers or products to be colored.

 For the reasons indicated above, the compounds (I) of the present invention are particularly advantageous with regard to

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 their use as hair dyes or cosmetic products intended for coloring or recolouring hair.

 The present invention therefore also relates to the use of a compound (I) according to the invention as a hair dye.

 Furthermore, the compounds (I) of the present invention are also advantageous with regard to their use for dyeing or recoloring all kinds of other fibers, and in particular, without this being a limitation here. any, synthetic or natural textile fibers, cellulose fibers (handkerchiefs, paper, cardboard ...) or other products such as leathers, furs ...

 The present invention also provides coloring compositions characterized in that they comprise at least one compound of general formula (I) as a coloring substance.

 Thanks to the presence of the compounds (I), these compositions do not require any additional problematic chemical additive and in particular no problematic solvent to form the dye and are therefore easier and safer to use.

 In particular, the compositions in accordance with the present invention can dispense with poorly tolerated substances, such as corrosive or irritant substances (for example certain oxidants), allergenic agents, desiccants, etc.

 The coloring or cosmetic compositions according to the invention are formulated in the usual way and may contain, in addition to the colored compounds (I), all the ingredients, excipients or vehicles commonly used (solvents, surfactants, emulsifiers, stabilizers, preservatives, dyes, perfumes ...) in this area, in all possible proportions and insofar as the added substances remain cosmetically acceptable if the coloring composition is intended for cosmetic use.

 The term “cosmetically acceptable excipient” denotes a substance which is useful in the preparation of a cosmetic composition which is sufficiently stable and which does not present a biological or other risk for the user, both in humans and in animals.

 Thanks to the compounds (I) and to the compositions of the present invention, it also becomes possible to obtain various colored products the coloring of which is at least as good on an aesthetic level.

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 (uniformity and appearance of coloring, variety and reproducibility in the choice of shade) than on the physico-chemical level (fixation, stability over time, resistance to external aggressions such as friction, washing, rain, solar radiation ...) than that obtained with known products.

 It has in particular been found that the compounds (I) according to the present invention are mainly red, which is very advantageous insofar as there is currently a real need for this shade, the products currently available notably lacking resistance to washing.

 Furthermore, the inventors have also found that the compounds (I) in accordance with the present invention have the additional advantage of not exhibiting significant differences in the shades of red as a function of R2.

 Of course, the invention is not limited to the embodiments described. Modifications remain possible, in particular from the point of view of the constitution of the various elements or by substitution of technical equivalents, without thereby departing from the scope of protection of the invention.

Claims (19)

 in which R1 represents an alkyl or aryl group and in which R2 represents a linear C1 to C10 alkyl group.

 CLAIMS 1. Compounds of general formula (I)  2. Compound according to claim 1, characterized in that RI preferably represents an alkyl group, preferably chosen from the group formed by methyl, ethyl, propyl, butyl or tert-butyl groups.  3. Compound according to claim 1 or 2, characterized in that R1 more preferably represents a tert-butyl group.  4. Compound according to any one of claims 1 to 3, characterized in that RI preferably represents a tert-butyl group and R2 represents a methyl group.  5. Compound according to any one of claims 1 to 3, characterized in that R1 preferably represents a tert-butyl group and R2 represents an ethyl group.  6. Compound according to claim 1, characterized in that R1 preferably represents a paratertiobutylphenyl group.  7. Compound according to claim 1 or 6, characterized in that RI preferably represents a paratertiobutylphenyl group and R2 represents a methyl group.  8. Use of a compound (I) according to any one of claims 1 to 7 as a dye.  9. Use according to claim 8 of a compound (I) according to any one of claims 1 to 7 as a permanent dye.  10. Use according to claim 8 of a compound (I) according to any one of claims 1 to 7 as a semi-permanent dye. <Desc / Clms Page number 14>  11. Use according to any one of claims 8 to 10 of a compound (I) according to any one of claims 1 to 7 as a hair dye.  12. A coloring composition characterized in that it comprises at least one compound of general formula (I) according to any one of claims 1 to 7 as a coloring substance.  13. Process for the synthesis of a compound of general formula (I) according to any one of claims 1 to 7, characterized in that it essentially comprises the steps consisting in: a) reacting 2,4-diaminoresorcinol or a 2,4-diaminoresorcinol derivative with R'COCl in an appropriate solvent, b) reducing the compound isolated in step a) using an appropriate reducing agent and isolating the reduced compound obtained, c) reacting the reduced product from step b) with an alkylating reagent of formula (R2) 30BF4 until gas evolution stops, then isolate and, if necessary, purify the final product obtained.  14. Method according to claim 13, characterized in that the solvent used in step a) is preferably acetonitrile.  15. The method of claim 13 or 14, characterized in that step a) is carried out under an inert atmosphere, preferably under a nitrogen atmosphere.  16. Method according to any one of claims 13 to 15, characterized in that step a) is preferably carried out at room temperature, with stirring and for a reaction time of between approximately 6 and 12 hours.  17. Method according to any one of claims 13 to 16, characterized in that step b) is preferably carried out under a reflux of THF, with stirring and for a reaction time of between approximately 6 and 12 hours.  18. Method according to any one of claims 13 to 17, characterized in that the reducing agent used in step b) is preferably chosen from LiAlH4 and B2H6.  19. Method according to any one of claims 13 to 18, characterized in that the 2,4-diaminoresorcinol derivative is preferably 2,4-diaminoresorcinol dihydrochloride.