Novel diazamerocyanines and their use for dyeing keratinous fibers

Abstract

Novel diazamerocyanines and salts thereof useful for dyeing keratinous fibers, particularly human hair, are disclosed. Illustrative is 3-methyl 2,3-dihydro 2:4'-azino benzothiazole 3'-amino 6'-methyl 1'-oxo 1', 4'-dihydro benzene having the formula: ##SPC1## Hair setting lotions, hair dye compositions and hair lacquers containing the diazamerocyanines, preferably in alcoholic solutions, are also disclosed.

Description

Currently, one of the most frequently used processes in capillary dyeing includes using oxidation dyes or "bases" associated with dyeing modifiers or "couplers" which can be aromatic metadiamines or metaaminophenols, or pyrazolones or diketones. When using this process of capillary dyeing, an oxidizing agent as hydrogen peroxide is added to the mixture of bases and couplers selected which has been previously alkalized.

It is known to use heterocyclic hydrazones associated with couplers for dyeing hair, as described for example in French Pat. No. 1,599,968.

However, this process has the disadvantage of requiring the use of hydrogen peroxide in an alkaline medium, which has been found to cause degradation of the hair, which rapidly becomes porous and brittle. Further, the shades obtained are capable of reproduction only with great difficulty because of secondary reactions that occur along with the reaction of coupling hydrazone and coupler. An additional disadvantage is that the hydrazones are relatively aggressive compounds in regard to the skin, which often causes problems with their use.

The present invention makes it possible to avoid these drawbacks by using, not a mixture of hydrazone and couplers thereof, but their coupling products, which constitute direct dyes which can be used over a varied range of pHs and are capable of forming easily reproducible shades. One embodiment of the present invention has as its object novel dyeing compositions for human hair, characterized by the fact that they contain in solution at least a diazamerocyanine or a diazamerocyanine salt of the formula

A = N -- N = B (I)

wherein A is a nitrogen heterocycle of the formula ##SPC2##

Wherein R is selected from the group consisting of lower alkyl having 1-4 carbon atoms and phenyl; X is selected from the group consisting of oxygen, sulfur, --NR'--, wherein R' is lower alkyl having 1-4 carbon atoms, --CH= CH--, ##SPC3##

wherein R" is selected from the group consisting of hydrogen and lower alkyl having 1-4 carbon atoms, and --C(R")(R")--, wherein R" each independently have the meaning given above, Z is a member selected from the group consisting of --CH= CH-- and --NR"', wherein R"' is a lower alkyl having 1-4 carbon atoms; R.sub.7 is selected from the group consisting of hydrogen, lower alkyl having 1-4 carbon atoms and phenyl; R.sub.8 is selected from the group consisting of hydrogen and lower alkyl having 1-4 carbon atoms, or R.sub.7 and R.sub.8, taken together with the carbon atoms to which they are linked, form a benzene ring, a halogen-substituted benzene ring, a benzene ring substituted with lower alkyl having 1-4 carbon atoms, a benzene ring substituted with lower alkoxy having 1-4 carbon atoms or a nitro-substituted benzene ring; B is selected from the group consisting of (i) a nitrogen-containing heterocycle different from the nitrogen containing heterocycle of A; (ii) a cycle of the formula ##SPC4##

wherein Y is a member selected from the group consisting of oxygen and ##SPC5##

wherein R.sub.1 and R.sub.2 each independently represent a member selected from the group consisting of hydrogen, lower alkyl having 1-4 carbon atoms and phenyl; and Z.sup.- is an anion derived from a member selected from the group consisting of inorganic acids and organic acids, such as halide, fluoborate, perchlorate, sulfate, bisulfate and acetate; R.sub.3 , represents a member selected from the group consisting of hydrogen, lower alkyl, lower alkoxy and phenyl carbamyl; R.sub.4 and R.sub.6 each independently represent a member selected from the group consisting of hydrogen, lower alkyl having 1-4 carbon atoms and lower alkoxy having 1-4 carbon atoms, and R.sub.5 represents a member selected from the group consisting of hydrogen, amino, alkylated amino having 1-4 carbon atoms, acylated amino having 2-5 carbon atoms; R.sub.5 and R.sub.6 being able, together with the carbon atoms to which they are attached, to form a condensed benzene ring; (iii) a cycle having the formula ##SPC6##

wherein R.sub.1 and R.sub.9, together with the nitrogen and carbon atoms to which they are attached, form a compound selected from the group consisting of a saturated heterocycle having 5 ring atoms, an unsaturated heterocycle having 5 ring atoms, a saturated heterocycle having 6 ring atoms, an unsaturated heterocycle having 6 ring atoms, in which case R.sub.10 is hydrogen and R.sub.2 represents a member selected from the group consisting of hydrogen and lower alkyl having 1-4 carbon atoms; or wherein R.sub.2 and R.sub.10, when taken together with the nitrogen and carbon atoms to which they are attached, form a compound selected from the group consisting of a saturated heterocycle having 5 ring atoms, an unsaturated heterocycle having 5 ring atoms, a saturated heterocycle having 6 ring atoms and an unsaturated heterocycle having 6 ring atoms, in which case R.sub.9 is hydrogen and R.sub.1 is selected from the group consisting of hydrogen, lower alkyl having 1-4 carbon atoms and acyl having 2 to 5 carbon atoms; and a cycle having the formula ##SPC7##

wherein R.sub.1, R.sub.2, R.sub.9, R.sub.10 and R.sub.11 have the meaning given above and X.sup.- represents an anion derived from a member selected from the group consisting of inorganic acid and organic acid, such as halide, fluoborate, perchlorate, sulfate, bisulfate and acetate.

The organic or inorganic acid salts of the compounds of Formula I can be acetates, oxalates, hydrochlorides, hydrobromides, persulfates or perchlorates. Of course, other organic and inorganic salts may be found.

Amino groups are compounds having the formula : ##SPC8##

where R.sub.a and R.sub.b are each independently hydrogen and lower alkyl having 1-4 carbon atoms.

The above-described hair dyeing compositions according to the present invention are aqueous solutions, to which most often have been added low molecular weight alcohols such as ethanol or isopropanol, or glycols such as propylene glycol or butylglycol, the alcohol or glycol facilitating the solution of the dye in the composition. These solutions are easily prepared by dissolving one or more compounds of Formula I in water or in a water-alcohol mixture. The proportion of alcohol used is generally between 20 and 70% by weight, while the proportion of glycol is generally between 1 and 6% by weight.

The concentration of the dye or dyes of Formula I in the dyeing compositions according to the present invention can vary in broad limits, because of the great affinity of these compounds for keratinous fibers. This concentration is generally between about 0.001 and about 0.5% by weight and preferably between about 0.002 and about 2% by weight.

The pH of the compositions according to the present invention is generally between about 2,5 and 10 and preferably between about 3 and 8. Preferably, however, the pH is adjusted to the desired value by addition of an acid such as orthophosphoric acid, lactic acid or acetic acid or a base such as mono-, di- or triethanolamine or ammonia.

The compositions according to the present invention can contain only one or more of the dyes of Formula I, in which case they make it possible to obtain on the hair shades rich in glints that go from yellow to blue, covering the light spectrum. The composition according to the invention can, however, contain other direct dyes, for example, azo or anthraquinone dyes, nitro dyes of the benzene series, indoanilines, indophenols or indamines.

The hair-dyeing compositions according to the present invention can also contain various adjuvants and ingredients customarily used in capillary cosmetics, for example, wetting agents, dispersing agents, swelling agents, penetrating agents, thickeners, softeners or perfumes. They can also be packaged under pressure in aerosol bombs or containers, together with a conventional aerosol propellant such as dichlorodifluoromethane, trichloromonofluoromethane and their mixtures. Of course, other conventional aerosol propellants can be used.

Dyeing of keratinous fibers, particularly human hair, with the dye compositions according to the invention, can be performed in the usual way, by application at ambient temperature of the composition to the fibers to be dyed, the composition being left in contact for a period varying from 3 to 30 minutes. Following this application, the fibers are rinsed and, if desired, washed. Thereafter the treated fibers are dryed.

In another embodiment of the present invention the compounds of Formula I can be employed in the production of capillary setting lotions. These lotions comprise an aqueous dilute alcohol solution, at least one cosmetic resin and at least a compound of Formula I or a salt thereof as defined above. The setting lotions according to the invention generally contain from 20 to 70% by weight of the total hairsetting lotion composition, of a low molecular weight alkanol such as ethanol or isopropanol and from 1 to 3% by weight of cosmetic resin.

Representative cosmetic resins that can be employed in the hair-setting lotions of the present invention include, for instance, polyvinyl pyrrolidone having a molecular weight of 40,000-400,000, copolymer of crotonic acid and vinyl acetate, said copolymer having a molecular weight ranging from about 10,000 to 70,000, copolymer vinyl pyrrolidone and vinyl acetate, wherein the ratio of PVP to VA ranges between 50-70: 50-30, said copolymer having a molecular weight ranging from about 30,000 to 200,000 and maleic anhydride-butylvinyl ether copolymers, a 1% solution of which is methylethyl ketone has a viscosity of 0.1-3.5 cps at 25.degree.C. These resins are used in a proportion of 1 to 3% by weight of the hair-setting lotion composition.

The pH of the hair setting lotions according to the invention is generally between 3 and 8. As stated above, it is possible to regulate the pH to the desired value by using mono- or di- or triethanolamine and an acidifying agents, acetic acid or lactic acid.

The setting lotions according to the invention can contain only the dyes of Formula I, in which case they constitute what is known as shading compositions. However, the hair-setting lotions of this invention can also contain other direct dyes such as anthraquinone dyes, nitro dyes of the benzene series and those mentioned above. The hair-setting lotions can also contain various ingredients usually used in capillary cosmetics, for example, wetting agents, dispersing agents, swelling agents, penetrating agents, thickeners, softeners or perfumes, as mentioned above. The hair-setting lotions disclosed herein are used in the customary manner by applying at ambient temperature to wet hair that has been previously washed and rinsed, followed by rolling the hair up on curlers and drying of the hair.

In another embodiment of the present invention, the dyes of Formula I can also be used in the production of hair lacquers. These lacquers contain in alcohol solution at least one cosmetic resin and at least a compound of Formula I.

The alcohols suitable for the preparation of the hair lacquers according to the invention are low molecular weight alcohols, such as ethanol or isopropanol. As resin there may be used one or more of polyvinyl pyrrolidone, copolymer of crotonic acid and vinyl acetate, copolymer of vinyl pyrrolidone and vinyl acetate, copolymer of maleic anhydride and butylvinyl ether, all as described above. The amount of dye of Formula I ranges from about 0.001 to about 0.5% by weight and the amount of cosmetic resin used is between about 1 and 3% by weight. Of course the hair lacquers of the present invention are conveniently packaged in pressurized containers or aerosol bombs of the type described above. The hair lacquers are conveniently applied directly to the hair, preferably in the form of a spray at ambient temperature.

Of the dyes of Formula I as described above, there are a certain number of novel compounds which are also part of and comprise another embodiment of the present invention.

Thus, the present invention in the composition of matter aspect thereof, includes novel diazamerocyanines and salts thereof of the formula

A = N -- N = B' (I')

wherein

A is a nitrogen heterocycle as defined above and B' is a residue corresponding to one of the following formulae: ##SPC9##

In the above formulae X.sup.- represents an anion derived from an inorganic or organic acid;

R.sub.1 is selected from the group consisting of hydrogen or lower alkyl having 1-4 carbon atoms;

R.sub.2 is hydrogen, lower alkyl having 1-4 carbon atoms, lower alkyl having 1-4 carbon atoms substituted by an amine, lower alkyl having 1-4 carbon atoms substituted by an amide, and ##SPC10##

wherein W is selected from the group consisting of oxygen and sulfur, and R' is selected from the group consisting of amino and lower alkyl of 1-4 carbon atoms,

R.sub.3 and R.sub.4 each independently represent a member selected from the group consisting of hydrogen and lower alkyl having 1-4 carbon atoms;

Y represents a member selected from the group consisting of ##SPC11##

wherein R.sub.1 ' and R.sub.2 ' each independently represent a member selected from the group consisting of hydrogen and lower alkyl having 1-4 carbon atoms, and Z.sup.- is an anion derived from an inorganic or organic acid, such as halide, perchlorate, fluoborate, acetate, bisulfate and sulfate;

R.sub.5 represents a member selected from the group consisting of hydrogen and ##SPC12##

wherein W represents a member selected from the group consisting of oxygen and sulfur, and R.sub.2 represents a member selected from the group consisting of amino and lower alkyl having 1-4 carbon atoms, R.sub.6 and R.sub.7 each independently represent a member selected from the group consisting of hydrogen, lower alkyl having 1-4 carbon atoms and methoxy, provided that R.sub.7 represents hydrogen when R'.sub.1, R'.sub.2 and R.sub.5 represent hydrogen, R.sub.8 and R.sub.10, together with the carbon and nitrogen atoms to which they are attached, represent a member selected from the group consisting of a saturated heterocycle containing 5 ring atoms, an unsaturated heterocycle containing 5 ring atoms, a saturated heterocycle containing 6 ring atoms, an unsaturated heterocycle containing 6 ring atoms, in which case R.sub.9 represents hydrogen and R.sub.11 represents a member selected from the group consisting of hydrogen and lower alkyl having 1-4 carbon atoms;

Or R.sub.9 and R.sub.11, together with the nitrogen atoms to which they are attached, represent a member selected from the group consisting of a saturated heterocycle containing 5 ring atoms, an unsaturated heterocycle containing 5 ring atoms, a saturated heterocycle containing 6 ring atoms, an unsaturated heterocycle containing 6 ring atoms, in which case R.sub.8 represents hydrogen and R.sub.10 represents a member selected from the group consisting of hydrogen, lower alkyl having 1-4 carbon atoms and acyl having 2 to 5 carbon atoms.

These novel compounds according to the present invention are obtained by known processes, including condensation of a hydrazone of the general formula

A = N -- NH.sub.2

wherein A has the signification indicated above, with a coupler corresponding to one of the following formulae: ##SPC13##

where Y' designates a residue --NHR'.sub.1 or ##SPC14##

and radicals R.sub.1 to R.sub.11 and R'.sub.1, R'.sub.2 and Z have the signification indicated above. This condensation being performed in the presence of an oxidizing agent which can be hydrogen peroxide, an alkaline persulfate, an alkaline chlorite, potassium ferricyanide or ferric chloride, at a temperature between 15 and 70.degree.C, either in an alkaline medium or an acid medium, in case it is desired to obtain a compound with a quaternary ammonium group. The acid used can be that corresponding to the desired salt, or a different acid, in which case the condensation is followed by an addition to the reaction medium of a salt of the acid corresponding to the desired diazamerocyanine salt that is more soluble in water than said diazamerocyanine salt, which is then isolated by filtering. This method of preparation has been generally described by S. Hunig in "Angewandte Chemie," International Edition, Volume 7, pages 335-344 (1968), the disclosure of which is hereby incorporated by reference.

The following examples are intended to illustrate various aspects of the present invention. Unless otherwise indicated, all parts and percentages are by weight and all temperatures used herein are expressed in degrees centigrade.

EXAMPLE 1

3-methyl 2,3-dihydro 2:4'-azino benzothiazole 3'-amino 6'-methyl 1'-oxo 1',4'-dihydro benzene having the formula as indicated below is prepared as follows: ##SPC15##

To a solution of 1.80 g of 3-methyl benzothiazolone hydrazone (0.01 mole) in 100 cc of 50% alcohol, a solution of 1.60 g of 3-amino 6-methyl phenol (0.01 mole) in 50 cc of 50% alcohol and 5 cc of ammonia at 22.degree.Be are added successively. The mixture is maintained at 30.degree.C with stirring, then there is introduced a solution of 2.28 g of ammonium persulfate in 20 cc of 50% alcohol. Stirring is continued for 30 minutes, then the precipitate obtained is drained, washed with water and dried on phosphoric anhydride.

The dye is in the form of a reddish brown solid with a melting point above 260.degree..

Molecular weight found by potentiometric determination in glacial acetic acid with HClO.sub.4 N/10 = 297, (the theoretical value is 298).

EXAMPLE 2

3-methyl 2,3-dihydro 2:4'-azino benzothiazole 2',6' -dimethyl 1'-oxo 1',4'-dihydro benzene having the formula below is prepared as follows: ##SPC16##

In a manner similar to that of Example 1, but using 2,6-dimethyl phenol for the 2-amino-6-methyl phenol, the above-indicated dye is obtained in form of a bright red solid with a melting point of 236.degree.. Molecular weight was calculated in a similar manner as Example 1 and found by potentiometric determination to be 300 (theory: 297).

EXAMPLE 3

Preparation of 3-methyl 2,3-dihydro 2:4'-azino benzothiazole 3'-acetamino 6'-methyl 1'-oxo 1',4' -dihydro benzene having the formula below is prepared as follows: ##SPC17##

In a manner identical to that of Example 1, but using 3-acetamino-6-methyl phenol a reddish orange product is obtained with a melting point above 260.degree.. Similarly, molecular weight was calculated by potentiometric determination and found to be 350 (theory: 340).

EXAMPLE 4

Preparation of 3-methyl 2,3-dihydro 2:4'-azino benzothiazole 3'-amino 2',6'-dimethyl 1'-oxo 1',4'-dihydro benzene having the formula below is prepared as follows: ##SPC18##

In a manner identical to that of Example 1, but using 3-amino-2,6-dimethyl phenol a brown product is obtained with a melting point of 250.degree..

Molecular weight was determined by potentiometric determination and found to be 321 (theory: 312).

EXAMPLE 5

3-phenyl 4-methyl 2,3-dihydro 2:4'-azino thiazole 1',4'-dihydro 1'-oxo 2'-naphthanilide having the formula below ##SPC19##

was prepared as described by S. Huenig in "Liebigs Annalen der Chemie," Vol. 47, p. 77, the disclosure of which is hereby incorporated by reference.

A red product is obtained with a melting point of 238.degree..

EXAMPLE 6

3,4-diphenyl 2,3-dihydro 2:4'-azino thiazole 1',4'-dihydro 1'-oxo 2'-naphthanilide having the following formula: ##SPC20##

is prepared as described in Example 5, but using 3,4-diphenyl 2,3-dihydrothioazole.

A red product is obtained with a melting point of 240.degree..

EXAMPLE 7

2[(1-dimethylamino-phenyl (4) azo]-3 methyl benzothiazolium perchlorate having the following formula: ##SPC21##

is prepared by the method described by S. Huenig in "Liebigs Annalen der Chemie," Vol. 628, p. 88, the disclosure of which is hereby incorporated by reference.

A product with green glints is obtained with a melting point of 230.degree..

EXAMPLE 8

1,3-dimethyl-2[(1-dimethylamino phenyl (4)) azo]imidazolium perchloate having the following formula: ##SPC22##

is prepared by the method described by S. Huenig in "Liebigs Annalen der Chemie," Vol. 628, p. 90, the disclosure of which is hereby incorporated by reference.

A product with green glints is obtained with a melting point of 242.degree..

EXAMPLE 9

2[(1,3-diamino 6-methyl-phenyl (4)) azo]-3 methyl benzothiazolium iodide having the below formula, is prepared as follows: ##SPC23##

1.80 g of N-methyl benzothiazolone hydrazone are dissolved in 160 cc of normal hydrochloric acid containing 10 mg of ferrous sulfate. 1.22 g of meta-toluylene diamine are added and thereafter 2.5 cc of 30% hydrogen peroxide are added with stirring. The reaction mixture is stirred for a half hour at 30.degree.C, then 10 cc of formic acid are added. The reaction mixture is next heated to 70.degree.C, it is filtered and 2.2 g of potassium iodide are added to the filtrate. After cooling the precipitate is drained, washed with water and dried on phosphoric anhydride.

The dye is obtained in the form of a reddish violet solid with a melting point of 180.degree. (decomposition).

EXAMPLE 10

2[1,3-diamino 2,6-dimethyl phenyl (4)) azo]-3 methyl benzothiazolium iodide having the below formula ##SPC24##

is prepared in a manner identical with that of Example 9, except that 1,3-diamino 2,6-dimethyl phenol is employed.

The dye is isolated in the form of a reddish violet solid with a melting point of 170.degree. (decomposition).

EXAMPLE 11

3-methyl 2,3-dihydro 2:4'-azino benzothiazole 1'-phenyl 3'-methyl 4'-ylidene 5'-pyrazolone of the below formula is prepared as follows: ##SPC25##

1.80 g of N-methyl benzothiazolone hydrazone are dissolved in 200 cc of 50% methanol. A solution of 1.74 g of 1-phenyl-3-methyl-5-pyrazolone in 50 cc of 50% methanol are added and then a solution of 14.5 g of potassium ferricyanide in a mixture of 100 cc of 50% methanol and 10 cc of 25% ammonia are introduced with stirring. The reaction mixture is stirred for a half hour, then 300 cc of water are added. The precipitate that results is drained, washed with water and dried on phosphoric anhydride. The dye obtained is in the form of a reddish orange solid with a melting point of 262.degree..

EXAMPLE 12

1,3-dimethyl 2,3-dihydro 2:4'-azino benzimidazole 1'-phenyl 3"-methyl 4'-ylidene 5'-pyrazolone of the below formula: ##SPC26##

is prepared in a manner identical with that of Example 11, except that 1,3-dimethyl 2,3-dihydro benzimidazolone hydrazone is employed.

The dye is isolated in the form of a reddish orange product with a melting point of 268.degree..

EXAMPLE 13

1,2-dimethyl 2,3-dihydro 2:4'-azino indazole 1'-phenyl 3'-methyl 4'-pyrazolone of the below formula ##SPC27##

is prepared in a manner similar to that of Example 11.

The dye is obtained in the form of a brownish orange product with a melting point of 264.degree..

Molecular weight calculated by potentiometric determination was found to be 348 (theory: 346).

EXAMPLE 14

4-methyl 3-phenyl 2,3-dihydro 2:4'-azino thiazole 1'-phenyl 3'-methyl 4'-ylidene 5'-pyrazolone of the below formula ##SPC28##

is prepared in a manner similar to that described in Example 11.

An orange product is obtained with a melting point of 232.degree..

EXAMPLE 15

1-methyl 1,4-dihydro 4:4'-azino pyridine 1',4'-dihydro 1'-oxo benzene of the below formula: ##SPC29## is prepared in a manner as described by S. Huenig in "Liebigs Annalen der Chemie," Vol. 636, p. 27, the disclosure of which is hereby incorporated by reference.

A dye is obtained in the form of a deep violet solid with a melting point of 213.degree..

EXAMPLE 16

1-methyl 1,4-dihydro 4,4-azino pyridine 1',4'-dihydro 1'-oxo naphthalene of the below formula: ##SPC30##

is prepared by the process as described by S. Huenig in "Liebigs Annalen der Chemie," Vol. 636, p. 28, the disclosure of which is hereby incorporated by reference.

The dye is obtained in the form of a solid with green glints with a melting point of 225.degree..

EXAMPLE 17

1,2-dimethyl 2,3-dihydro 3:7'-azino indazole 6'-oxo 6',7'-dihydro benzomorpholine of the below formula, is prepared as follows: ##SPC31##

2.12 g of 1,2-dimethyl 3-indazolone hydrazone hydrochloride are dissolved in 80 cc of water. At ambient temperature a solution of 1.51 g of 6-hydroxy benzomorpholine in 80 cc of water is added, then, with stirring, in 15 minutes a solution of 4.56 g of ammonium persulfate and 12 cc of ammonia at 22.degree.Be is added. Stirring is continued for 30 minutes, followed by filtering, washing with cold water and drying of the precipitate thus obtained on phosphoric anhydride. The product obtained is a brownish red dye with a melting point of 230.degree..

EXAMPLE 18

1,3-dimethyl 1,2-dihydro 2:7'-azino benzimidazole 6'-oxo 6',7'-dihydro benzomorpholine of the below formula: ##SPC32##

is prepared in a manner identical with that described in Example 17. The dye is obtained in the form of a brown solid with green glints having a melting point of 184.degree..

Molecular weight found: 324.

Molecular weight calculated (theoretical): 323.

EXAMPLE 19

3-methyl 2,3-dihydro 2:7'-aminobenzothiazole 6'-oxo 6',7'-dihydro benzomorpholine of the below formula: ##SPC33##

is prepared in a manner identical with that described in Example 17. The dye is obtained in the form of a brown solid with a melting point of 195.degree..

EXAMPLE 20

7'-(6'-hydroxy benzomorpholine) 2-ozo 3-methyl benzothiazolium chloride of the below formula, is prepared as follows: ##SPC34##

2.52 g (0.01 mole) of N-methylbenzothiazolone hydrazone dihydrochloride and 1.51 g (0.01 mole) of 6-hydroxy benzomorpholine are dissolved in 200 cc of 1 N HCl, then, over a period of 45 minutes, 26 cc of 28% FeCl.sub.3 dissolved in 24 cc of water is added. The mixture takes on a violet shade and a precipitate appears. The reaction mixture is allowed to react for 15 minutes, then filtered and the product dried under vacuum on phosphoric anhydride. The chloride thus obtained is purified by dissolving in dimethylformamide and reprecipitation with water. Melting point: 225.degree.C (decomposition).

______________________________________ Analysis: C%: 48.66 - 48.66 (49.3 theoretical) H%: 3.87 - 3.99 (4.62 theoretical) N%: 14.35 - 15.51 (14.12 theoretical) ______________________________________

EXAMPLE 21

7'-(6'-hydroxy benzomorpholine) 2-ozo 3-methyl benzothiazolium perchlorate is obtained by dissolving of the chloride prepared in Example 20 in a suitable quantity of acetic acid and reprecipitation by sodium perchlorate.

______________________________________ Analysis: C%: 42.69 - 42.46 (42.40 theoretical) H%: 3.62 - 3.68 (3.97 theoretical) N%: 12.43 - 12.55 (12.37 theoretical) ______________________________________

The melting point was found to be 240.degree.C (decomposition).

EXAMPLE 22

7'-(6'-hydroxy benzomorpholine 2-ozo 4-methyl 3-methyl thiazolium perchlorate of the below formula, is prepared as follows: ##SPC35##

3.45 g (0.01 mole) of 4-methyl 3-phenyl thiazolone benzene sulfonylhydrazone and 1.51 g (0.01 mole) of 6-hydroxy benzomorpholine are dissolved in 100 cc of crystallizable acetic acid. Thereafter, in 15 minutes about 2.28 g (0.01 mole) of ammonium persulfate in 10 cc of water is added and the solution takes on a violet tint. The reaction mixture is stirred for 30 minutes, then 5 cc of sodium perchlorate dissolved in 20 cc of water are added. The reaction mixture is again stirred for 1 hour, then filtered and dried under vacuum on phosphoric anhydride.

The product is purified by dissolving in a suitable quantity of dichlorethane, filtering of the insoluble material and reprecipitation by carbon tetrahydrochloride. A powder with green glints is obtained with a melting point of 230.degree..

______________________________________ Analysis: C%: 45.18 - 44.70 (54.04 theoretical) H%: 4.07 - 3.94 (4.17 theoretical) N%: 11.69 - 11.84 (11.68 theoretical) ______________________________________

EXAMPLE 23

7'-(6'-hydroxy benzomorpholine) 2-azo 3,4-diphenyl thiazolium perchlorate of the below formula, is prepared as follows: ##SPC36##

1.33 g (0.005 mole) of 3.4-diphenyl thiazolone hydrazone and 0.75 g (0.005 mole) of 6-hydroxy benzomorpholine are dissolved in 50 cc of crystallizable acetic acid. 2.28 g (0.001 mole) of ammonium persulfate dissolved in 10 cc of water are added in 30 minutes and an intense violet coloring appears. After stirring the reaction mixture for 30 minutes, 2 g of sodium perchlorate dissolved in 10 cc of water are added. The reaction mixture is filtered, washed with water and dried under a vacuum on phosphoric anhydride.

The product is purified by dissolving in a sufficient quantity of dichlorethane and precipitation by carbon tetrachloride, there being obtained crystals with green glints with a melting point of 170.degree.C.

______________________________________ Analysis: C%: 52.57 - 52.60 (52.75 theoretical) H%: 4.38 - 4.10 (3.82 theoretical) N%: 10.05 - 10.29 (10.7 theoretical) ______________________________________

Determination by water (Karl Fisher): 1.5%

EXAMPLE 24

7'-(6'-hydroxy benzomorpholine) 2-azo 1,3-dimethyl benzimidazolium perchlorate of the below formula, is prepared as follows: ##SPC37##

10 g (0.04 mole) of N,N'-dimethyl benzimidazolone hydrazone dihydrochloride and 6.04 g (0.04 mole) of 6-hydroxy benzomorpholine are dissolved in 250 cc of acetic acid. 30 g of sodium acetate dissolved in 100 cc of acetic acid are added and then, in about 30 minutes, 18.24 g (0.08 mole) of ammonium persulfate dissolved in 100 cc of water are added. The mixture is allowed to react for 30 minutes, then the inorganic salts are separated by filtering and the product is precipitated by addition of 20 g of sodium perchlorate dissolved in 300 cc of water. 9 g of the product are collected, corresponding to a yield of 70%, which is purified by extraction with methanol and concentration. The melting point was found to be 240.degree.C.

______________________________________ Analysis: C.sub.17 H.sub.18 N.sub.5 O.sub.2 . ClO.sub.4 C%: 48.6 (48.2 theoretical) H%: 4.6 (4.2 theoretical) ______________________________________

The following examples relate to another embodiment of the present invention wherein the dyes produced in the preceding examples are used in hair-setting lotions as hereinbefore described.

EXAMPLE 25

The following hair-setting lotion is prepared

Dye of Example 8 0.100 g Vinyl pyrrolidone-vinyl acetate copolymer (Vinyl pyrrolidone - 70 %, vinyl acetate - 30 %, molecular weight 35,000 - 45,000) 3 g Ethyl alcohol, 96.degree. titer 50 cc Triethanolamine, q.s.p. pH 5 Water, q.s.p. 100 cc

This hair-setting lotion when applied to hair dyed brown, imparts thereto a purplish brown shade.

EXAMPLE 26

The following hair-setting lotion is prepared:

Dye of Example 7 0.1 g Vinyl acetate-crotonic acid copolymer (vinyl acetate-90% crotonic acid- 10 %, molecular weight 45,000 - 50,000) 2 g Ethyl alcohol, 96.degree. titer 50 cc Benzylidene camphor 0.2 g Triethanolamine, q.s.p. pH 7 Water, q.s.p. 100 cc

This hair-setting lotion when applied to hair dyed deep blond, imparts thereto a luminous ash glint.

EXAMPLE 27

The following dyeing composition is prepared:

Dye of Example 7 0.0012 g Vinyl pyrrolidone-vinyl acetate copolymer (vinyl pyrrolidone - 70 %, vinyl acetate - 30 %, molecular weight - 35,000 - 45,000) 2 g Ethyl alcohol, 96.degree. titer 50 cc 200 volume hydrogen peroxide 5 g Orthophosphoric acid, q.s.p. pH 3 Water, q.s.p. 100 cc

This hair-setting lotion is applied at ambient temperature to naturally light brown hair. After setting and drying, the hair is lightly brightened and imparts thereto a pearly glint.

EXAMPLE 28

The following composition is prepared:

Dye of Example 7 0.0015 g Ethyl alcohol, 96.degree. titer 50 cc 200 volume hydrogen peroxide 5 g Orthophosphoric acid, q.s.p. pH 3 Water, q.s.p. 100 cc

This composition is applied to naturally dark blond hair. After setting and drying the hair is lightly brightened up and the lotion imparts thereto an ash rose glint.

EXAMPLE 29

The following dyeing composition is prepared

Dye of Example 1 0.0006 g Dye of Example 8 0.0006 g Vinyl acetate-crotonic acid copolymer (vinyl acetate - 90 %, crotonic acid - 10 %, molecular weight 45,000 - 50,000) 2 g Ethyl alcohol, 96.degree. titer 55 cc 200 volume hydrogen peroxide 5 g Orthophosphoric acid, q.s.p. pH 3 Water, q.s.p. 100 cc

This lotion is applied to natural blond hair. After setting and drying, the hair is brightened and presents an ash pearly blond shade.

EXAMPLE 30

The following dyeing composition suitable for packaging in an aerosol container is prepared:

Dye of Example 4 0.03 g Dye of Example 1 0.1 g Vinyl pyrrolidone-vinyl acetate copolymer (vinyl pyrrolidone - 60 %, vinyl acetate- 40 %, molecular weight 45,000 - 60,000) 3 g Ethyl alcohol, 96.degree. titer, q.s.p. 100 cc

This composition, packaged in an aerosol container with dichlorodifluoromethane as the propellant and sprayed in the form of a lacquer gives natural blond hair luminous golden glints.

EXAMPLE 31

The following hair-setting lotion is prepared:

Dye of Example 11 0.005 g Dye of Example 1 0.01 g Dye of Example 8 0.001 g Vinyl pyrrolidone-vinyl acetate copolymer (Vinyl pyrrolidone - 60 %, vinyl acetate - 40 %, molecular weight - 45,000 - 60,000) 2 g Ethyl alcohol, 96.degree. titer 50 cc Triethanolamine, q.s.p. pH 7 Water, q.s.p. 100 cc

This hair-setting lotion when applied to freshly bleached hair, imparts thereto a light silvery shade.

EXAMPLE 32

The following dyeing composition is prepared:

Dye of Example 17 0.096 g Butylcellosolve 8 g Propylene glycol 8 g Alkyl phenol polyethoxyether sold under the name "Remcopal 334" by the Gerland company 22 g Alkylphenol polyethoxyether sold under the name "Remcopal 349" by the Gerland company 22 g Ammonia at 22.degree.Be 8 g Water, q.s.p. 100 g

20 g of 20 volume hydrogen peroxide is added to 20 g of the solution thus prepared and the gel thus obtained which, applied to ambient temperatures to bleached hair for 10 minutes, imparts to the hair a beige pearly shade.

EXAMPLE 33

The following dyeing composition is prepared:

Dye of Example 17 0.2 g Butylcellosolve 8 g Propylene glycol 8 g Alkylphenol polyethoxyether sold under the name "Remcopal 334" by the Gerland company 22 g Alkylphenol polyethoxyether sold under the name "Remcopal 349" by the Gerland company 22 g Ammonia at 22.degree.Be 10 g Water, q.s.p. 100 g

20 g of water are added to 20 g of the solution thus prepared. A gel is obtained which, applied to brown hair at ambient temperature for 15 minutes, imparts to the hair, after rinsing, a dark auburn brown shade.

EXAMPLE 34

The following dyeing composition is prepared:

Dye of Example 8 0.050 g Butylcellosolve 8 g Propylene glycol 8 g Alkylphenol polyethoxyether sold under the name "Remcopal 334" by the Gerland company 22 g Alkylphenol polyethoxyether sold under the name "Remcopal 349" by the Gerland company 22 g Water, q.s.p. 100 g

20 g of water are added to 20 g of the solution thus prepared. A gel is obtained which, applied at ambient temperature for 10 minutes to previously bleached hair, imparts to the hair an iridescent blond shade.

EXAMPLE 35

The following hair-setting lotion is prepared:

Dye of Example 20 0.010 g Vinyl pyrrolidone-vinyl acetate copolymer (vinyl pyrrolidone - 60 %, vinyl acetate - 40 %, molecular weight - 45,000-60,000) 2.0 g Ethyl alcohol, 96.degree. titer 50 cc Triethanolamine, q.s.p. pH 7 Water, q.s.p. 100 cc

This hair-setting lotion when applied to hair dyed blond, imparts thereto a golden glint.

EXAMPLE 36

The following hair-setting composition is prepared:

Dye of Example 22 0.012 g Vinyl pyrrolidone-vinyl acetate copolymer (vinyl pyrrolidone - 60 %, vinyl acetate - 40 %, molecular weight, 45,000 - 60,000) 2.0 g Ethyl alcohol, 96.degree. titer 50 cc Triethanolamine, q.s.p. pH 7 Water, q.s.p. 100 g

This hair-setting lotion when applied to bleached hair, imparts thereto a particularly luminous golden pink blond shade.

EXAMPLE 37

The following hair-setting lotion is prepared:

Dye of Example 24 0.010 g Vinyl pyrrolidone-vinyl acetate copolymer (vinyl pyrrolidone - 70 %, vinyl acetate 30 %, molecular weight 35,000 - 45,000) 2.0 g Ethyl alcohol, 96.degree. titer 50 cc Triethanolamine, q.s.p. pH 7 Water, q.s.p. 100 cc

This hair-setting lotion when applied to hair dyed golden blond, imparts thereto a luminous and aesthetic pearl glint.

EXAMPLE 38

The following hair-setting lotion is prepared:

Dye of Example 23 0.015 g Vinyl pyrrolidone-vinyl acetate copolymer (vinyl pyrrolidone - 70 %, vinyl acetate - 30 %, molecular weight 35,000 - 45,000) 2.0 g Ethyl alcohol, 96.degree. titer 50 cc Triethanolamine, q.s.p. pH 8 Water, q.s.p. 100 cc

This hair-setting lotion when applied to bleached hair, imparts thereto a very luminous light pink blond shade.

EXAMPLE 39

The following hair-setting lotion is prepared:

Dye of Example 7 0.70 g Vinyl acetate-crotonic acid copolymer (vinyl acetate - 90 %, crotonic acid - 10 %, molecular weight, 45,000 - 50,000) 2.0 g Ethyl alcohol, 96.degree. titer 50 cc Benzylidene camphor 0.2 g Triethanolamine, q.s.p. pH 7

This hair-setting lotion when applied to hair dyed dark blond, imparts thereto a luminous pearl ash glint.

EXAMPLE 40

The following hair-setting lotion is prepared:

Dye of Example 22 0.010 g Vinyl pyrrolidone-vinyl acetate copolymer (vinyl pyrrolidone - 70 %, vinyl acetate - 30 %, molecular weight 35,000 - 45,000) 2.0 g Ethyl alcohol, 96.degree. titer 50 cc Triethanolamine, q.s.p. pH 7 N-[(4'-amino 2'-methoxy 3',5'-dimethyl) phenyl] 2,5-dimethyl benzoquinoneimine 0.010 g Water, q.s.p 100 cc

This hair-setting lotion, when applied to light blond hair, imparts thereto a pearl ash shade.

EXAMPLE 41

The following dyeing composition is prepared:

Dye of Example 24 0.012 g N-[(4'-hydroxy)phenyl] 3-aamino 6-methyl benzoquinoneimine 0.010 g N-[(4'-amino 2'-methoxy 3',5'-dimethyl) phenyl] 2,6-dimethyl benzoquinoneimine 0.002 g Ethyl alcohol, 96.degree. titer 50 cc Water, q.s.p. 100 cc

This dye composition when applied to strongly bleached hair for 20 minutes at ambient temperature, imparts thereto after rinsing and shampooing, a golden apricot shade.

EXAMPLE 42

The following hair-setting composition is prepared:

Dye of Example 20 0.005 g Dye of Example 24 0.005 g N-[(4'-hydroxy)phenyl]3-amino 6-methyl benzoquinoneimine 0.0025 g N-[(4'-amino 2'-methoxy 3',5'-dimethyl) phenyl]2,5-dimethyl benzoquinoacimine 0.001 g Vinyl pyrrolidone-vinyl acetate copolymer (vinyl pyrrolidone 70 %, vinyl acetate- 30 %, molecular weight 35,000 - 45,000) 2.0 g Triethanolamine, q.s.p. pH 7 Water, q.s.p. 100 cc

This hair-setting lotion when applied to blond hair imparts thereto a pearly glint.

EXAMPLE 43

The following setting lotion is prepared:

Dye of Example 24 0.006 g Dye of Example 22 0.004 g N-[(4'-hydroxy)phenyl] 3-amino 6-methyl benzequinoneimine 0.001 g N-[(4'-amino 2'-methoxy 5'-methyl)phenyl] 3-acetylamino 6-methyl benzoquinoneimine 0.005 g Vinylpyrrolidone-vinyl acetate copolymer (vinyl pyrrolidone - 60 %, vinyl acetate - 40 %, molecular weight - 45,000 - 60,000) 2.0 g Ethyl alcohol, 96.degree. titer 50 cc Triethanolamine, q.s.p. pH 7 Benzylidene camphor 0.2 g Water, q.s.p. 100 cc

This hair-setting lotion when applied to very light natural blond hair, imparts thereto a luminous ash pearl glint.

EXAMPLE 44

The following hair-setting lotion is prepared:

Dye of Example 23 0.007 g N-(4'-amino 2'-methoxy 3',5'-dimethyl) phenyl 2,5-dimethyl benzoquinoneimine 0.003 g N-(4'-hydroxy)phenyl 2,6-dimethyl benzoquinoneimine 0.003 g Vinyl pyrrolidone-vinyl acetate copolymer (vinyl pyrrolidone - 60 %, vinyl acetate - 40 %, molecular weight 45,000 - 60,000) 2.0 g Ethyl alcohol, 96.degree. titer 50 cc Triethanolamine, q.s.p. pH 6 Water, q.s.p. 100 cc

This hair-setting lotion when applied to hair dyed light blond, imparts thereto ash pearl glints.

EXAMPLE 45

The following hair-setting lotion is prepared:

Dye of Example 22 0.010 g Nitroparaphenylenediamine 0.010 g Vinyl pyrrolidone-vinyl acetate copolymer (vinyl pyrrolidone - 60 %, vinyl acetate - 40 %, molecular weight 45,000 - 60,000) 2.0 g Ethyl alcohol, 96.degree. titer 60 cc Triethanolamine, q.s.p. pH 9 Water, q.s.p. 100 cc

This hair-setting lotion when applied to hair dyed light brown, imparts thereto golden copper glints.

EXAMPLE 46

The following dyeing composition is prepared:

Dye of Example 22 0.010 g Dye of Example 23 0.010 g 4-methyl di-.beta.-hydroxymethylamino-8(2,3-b) morpholino phenoxazonium bromide 0.010 g Crotonic acid-vinyl acetate copolymer (crotonic acid - 10 %, vinyl acetate - 90 %, molecular weight 45,000 - 50,000) 2.0 g Ethyl alcohol, 96.degree. titer 50 cc Triethanolamine, q.s.p. pH 6 Water, q.s.p. 100 cc

This hair-setting lotion when applied to hair bleached and dyed dark brown imparts thereto a luminous bluish ash glint.

As used in the preceding examples, "Remcopal 334" is a nonylphenol polyethoxyether obtained by condensation of 4 moles of ethylene-oxide with 1 mole of nonylphenol, and "Remcopal 349" is a nonylphenol polyethoxyether obtained by condensation of 9 moles of ethylene-oxide with 1 mole of nonylphenol. Both are commercially available from the Gerland company.

Claims

1. A diazamerocyanine, including the mesomorphic form thereof, having the formula

A = N -- N = B'

wherein A is a nitrogen heterocycle selected from the group consisting of ##SPC38##

wherein:

R is lower alkyl having 1-4 carbon atoms or phenyl;

X is a member selected from the group consisting of oxygen, sulfur, --NR'--, where R' is lower alkyl having 1-4 carbon atoms; --CH= CH--; ##SPC39##

where R" is hydrogen or lower alkyl having 1-4 carbon atoms; or --C(R")(R")--, where R" each independently have the meaning above;

Z is --CH= CH-- or --NR"', where R"' is lower alkyl having 1-4 carbon atoms

R.sub.7 is hydrogen, lower alkyl having 1-4 carbon atoms, or phenyl;

R.sub.8 is hydrogen or lower alkyl having 1-4 carbon atoms, or R.sub.7 and R.sub.8, when taken together with the carbon atoms to which they are attached form a benzene ring, a halogen-substituted benzene ring, a benzene ring substituted with lower alkyl having 1-4 carbon atoms, a benzene ring substituted with lower alkoxy having 1-4 carbon atoms, or a nitro-substituted benzene ring; and B' is a member selected from the group consisting of ##SPC40##

where R.sub.8.sub.' and R.sub.10, together with the carbon and nitrogen atoms to which they are attached, form a morpholine group and R.sub.9 is hydrogen and R.sub.11 is hydrogen or lower alkyl having 1-4 carbon atoms, or R.sub.9 and R.sub.11, together with the carbon and nitrogen atoms to which they are attached, form a morpholine group, and R.sub.8.sub.' is hydrogen and R.sub.10 is hydrogen, lower alkyl having 1-4 carbon atoms and alkanoyl having 2 to 5 carbon atoms; and X.sup.- is a halide,

2. The compound of claim 1 which is selected from the group consisting of:

1,2-dimethyl 2,3-dihydro 3:7'-azino indazole 6'-oxo 6',7'-dihydro benzomorpholine,

1,3-dimethyl 1,2-dihydro 2:7'-azino benzimidazole 6'-oxo 6',7'-dihydro benzomorpholine,

3-methyl 2,3-dihydro 2:7'-aminobenzothiazole 6'-oxo 6',7'-dihydro benzomorpholine,

7'-(6'-hydroxy benzomorpholine) 2-azo 3-methyl benzothiazolium chloride,

7'-(6'-hydroxy benzomorpholine)2-azo 3-methyl benzothiazolium perchlorate,

7-(6'-hydroxy benzomorpholine) 2-azo 4-methyl 3-phenyl thiazolium perchlorate,

7-(6'-hydroxy benzomorpholine) 2-azo 3,4-diphenyl thiazolium perchlorate, and

7-(6'-hydroxy benzomorpholine) 2-azo 1,3-dimethyl benzimidazolium perchlorate.