DE2538363A1 - COLORING AGENTS CONTAINING QUATERNAER AZO COLORS DERIVED FROM 2-AMINOPYRIDINE - Google Patents

Description

PATENT ADVOCATE

DR.-ING. WOLFRAM BUNTE DR. WERNER KINZEBACH

D-eOOO MUNICH 4O. BAUERSTRASSE 22 ■ FERNRUF (O89) 37 SS 83 · TELEX B21B2O8 ISAR D POSTAL ADDRESS: D-BOOO MUNICH 43. POST BOX

Munich, August 28, 1975 M / 16

L ¹ OREAL

14 Rue Royale F-75008 Paris

Colorants containing quaternary azo dyes, the are derived from 2-aminopyridine

Addition to P 22 27 214.6

In the parent application No. P 22 27 214.6 of the same applicant Colorants for hair have been described and claimed which are essentially characterized in that they are in solution a diazamerocyanine or a salt of diazamerocyanine the formula

A = N-N = B

contain, in which:

A for a nitrogen heterocycle with 5 or 6 chain links the formula

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R-N

or * 8

where R is a lower alkyl radical having 1 to 4 carbon atoms or an optionally substituted phenyl radical, X is an oxygen atom or sulfur atom, a radical NR ¹ , where R ^{1 is} a lower alkyl radical, a radical -CHp, which is optionally substituted by one or two is substituted lower alkyl radicals, an ethylenic radical or a radical -C = N-, where R "represents a hydrogen-R"

atom or a lower alkyl radical, Z stands for an ethylenic radical or a radical -NR " ¹ , in which R"'represents a lower alkyl radical, R _{7 represents} a hydrogen atom, a lower alkyl radical or a phenyl radical, Rg a hydrogen atom or a lower alkyl radical represents, or in which R ₇ and Rg together with the carbon atoms to which they are attached form a condensed benzene ring which is optionally substituted by one or more halogen atoms or alkyl, alkoxy or nitro radicals,

B among other things a nitrogen heterocycle with 5 or 6 chain links, which may also contain other heteroatoms that are not identical to the heterocycles represented by A are, or a ring of the formula

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can represent, in which Y stands for an oxygen atom or a radical = NC ^ "Z ~, in which R ₁ and R ₂ each mean a hydrogen atom, a lower alkyl radical or a phenyl radical and in which Z ~ represents an anion that differs from an organic or mineral acid, such as a halogen ion, for example an iodine, chlorine, bromine ion, a fluoroborate, I perchlorate, sulfate, bisulfate or acetate ion, R ^ and Rg each a hydrogen atom, a lower alkyl or alkoxy radical with 1 to 4 carbon atoms, Ro represents a hydrogen atom, a lower alkyl or alkoxy radical or a phenylcarbamyl radical, whereas Rr represents a hydrogen atom or an amino radical which is optionally alkylated or acylated, where Rg and Rg also together with the j carbon atoms to which they are bound can form a condensed benzene ring or its mesomeric form.

According to the invention it has now been found that by Introduction of dyes of the formula I.

A ¹ - N = A - B ¹ (I)

wherein A ^{1 is} a nitrogen heterocycle with 6 chain links of the formula

denotes in which R is a lower alkyl radical having 1 to 4 carbon atoms, X is an ethylenic radical and B ^{1 is} a ring of the formula

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means that by this

are characterized in that the ethylene radical of the formula

R ¹

- C

R '

ΐ 10 C -

corresponds in such a way that the dyes according to the invention of the general formula II

N - N

(II)

obey what:

R is a lower alkyl radical with 1 to 4 carbon atoms means,

R ', Q have a hydrogen atom or a lower alkyl group 1 to 4 carbon atoms, preferably methyl, represents R'g'a hydrogen atom, a lower alkyl group with 1 to Carbon atoms, preferably methyl, or a group -CN represents, j

R'g is a hydrogen atom or a halogen, such as preferably i a chlorine atom, a lower alkyl group with 1 to 4 carbons!

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Substance atoms, preferably a methyl group, R'y is a hydrogen atom, a lower alkyl group, preferably methyl, or a cyano group, R ¹ , a hydrogen atom, a lower alkyl group or a lower hydroxyalkyl group with 1 to 4 carbon atoms and preferably β-hydroxyethyl, R ' _{2 represents} a hydrogen atom, a lower alkyl group, a lower hydroxyalkyl group with 1 to 4 carbon atoms, and preferably β-hydroxyethyl, phenyl, R' ₃ and / or R ' _{g represents} a hydrogen atom, a lower alkyl group with 1 to 4 carbon atoms and preferably methyl, or a lower alkoxy group with 1 to 4 carbon atoms and preferably methoxy, R * 4 and / or RV represent a hydrogen atom, a halogen atom, such as preferably chlorine, a lower alkyl group with 1 to 4 carbon atoms and preferably methyl, a nitro group, an amino group or an acetylamino group, R'g and R'g also denote an unsaturated ring with 6K may form ettengliedern, the (representing in which case R'j, R _'2 "R' ₃ and R _'4, only one hydrogen atom), a with one of the nitrogen atoms of the azo bond before! atisierten substituents, and preferably hydroxyl carries Z ~ may be an anion derived from a mineral or organic acid such as halogen (iodine, chlorine, bromine), fluoroborate, perchlorate, sulfate, acetate and especially methyl sulfate;

or the mesomeric form thereof,

in cosmetic colorants due to the greater solubility these compounds can arrive at agents which have improved coloring properties.

The compounds defined in this way are quaternary azo dyes j and can be represented by the two mesomeric forms :!

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The dyes of the general formula II lead to dyes which have an increased affinity for keratin fibers and in particular for human hair.

The dyeings carried out with this type of dyestuff also have improved lightfastness.

With regard to the known dyes and, inter alia, with regard to the dyes described in the parent application, the compounds of the present application have the advantage greater solubility in the solvents commonly used in cosmetics, such as water, alcohols and their mixtures.

The compounds according to the definition of general formula II which can be used in the agents according to the invention are new or known compounds which, according to the application, are produced by a known method, with compounds of formula III

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(III)

O - R ¹

those described in French patent 73 22 158 are to be used.

Among the known compounds one can name the 4 ¹ -dialkylamino-I ¹ , 2-azobenzene-1-alkylpyridinium salts, the pyridine ring of which is unsubstituted in the 3 and 4 position, but which can optionally carry a methyl group in the 5 and 6 position, and especially the methyl sulfate salts of these compounds.

Other particularly interesting and known compounds are the 4'-dialkylamino-1 ¹ , 2-azobenzene-1-alkylpyridinium salts, their pyridinium ring in the 3 and / or 4 and optionally in the or'6 position through a methyl group, or a chlorine atom in 5 Position can be substituted. Among these compounds one can also mention the compounds substituted in the 5-position by a chlorine atom, the positions 3 and 4 of which in the pyridinium ring are not substituted.

The benzene ring of the above-mentioned compounds can be noted in the 2'-position by a chlorine atom, a methyl group, a Nitro group, an amino group or an acetyl amino group and be substituted in the 5'-position by a methyl or methoxy group.

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The amino group in the 4 ¹ position can be substituted by alkyl groups, such as methyl or ethyl, or by a hydroxyalkyl group, such as β-hydroxyethyl.

The new compounds of the general formula II which can be used in the agents according to the invention correspond to general formula

R ¹ ~

R Z

R '

wherein R ¹ _1Q , R'g, R'- ,, R ¹

R ¹ 2, R and

Z "the

have the meanings given above in the definition of the general formula II and in which R ¹ ″ or R ′ _{7 represent} a cyano group, regardless of what the meanings of the abovementioned substituents may be.

Other new compounds used in the agents according to the invention are compounds which correspond to the general formula II, in which R ' _g and R' ₇ are different from a cyano group if R '(- and R' c form an unsaturated ring with 6 chain members, the carries a hydroxy substituent which is chelated in each case with a nitrogen atom of the azo bond, R'i, R ¹

represent, where R ¹

R ¹

Have 10 '"8' as previously stated.

R'o and R ' ₄ hydrogen R and Z "have the same meanings

The compounds corresponding to the general formula II are prepared by a process which consists in that one of compounds of the formula III

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O - R ¹ R 'R' 5 ο

(III)

as described in French patent specification 73 22 158 are going out. These compounds are subjected to the action of alkali to give a compound of the formula Obtaining IV according to a well known mechanism:

R ¹

OH

III-

R ¹ , - ¹

wherein the compounds IV finally with an alkylating agent RZ, in which R and Z have the meanings mentioned above, are treated to, according to the reaction, the compounds of the general formula II

RZ

where R ' _lt R ^ ₂ , R' ₃ , R ' ₄ , R' ₅ , R '_6>R' ₇

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R'g, R'iQ> Z and R have the meanings mentioned above.

The present invention also relates to colorants for kefatin fibers and in particular for human hair which are in the form of solutions are available.

The agents according to the invention are aqueous or aqueous-alcoholic solutions that can be easily obtained by dissolving one or several compounds of the formula II in water or in a water-alcohol mixture.

The concentration of dyestuffs of the formula II in the colorants according to the invention can vary within wide ranges, namely because of the great affinity of these compounds for the keratin fibers. This concentration is generally between 0.0005 and 5% by weight and preferably between 0.01 and 1.5 %.

The pH of the agents mentioned is generally between 3 and 12. One sets by adding an acid such as orthophosphoric acid, citric acid or acetic acid or a base such as Triäthanolamiη, monoethanolamine or ammonia to the desired value.

The agents according to the invention contain only the dyes Formula II; in this case, you can achieve reflective tints on the hair, ranging from orange to blue.

However, the agents can also contain other direct dyes, such as azo dyes or anthraquinone dyes, nitrated dyes from the benzene series, indoaniline, indo phenols or indamines.

They can also be different commonly used in cosmetics! contain adjuvants used, for example anionic,!

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RD9ft? N / 1 1 11

cationic, non-ionic, amphoteric or zwitterionic surfactants, oxidants,, synergists or Foam stabilizers, sequestrants, fatliquors, Thickeners, preservatives, swelling agents, Penetrants, plasticizers or perfumes. You can also be conditioned in aerosol containers.

The dyeing of human hair with the agents according to the invention is carried out in the usual way by applying the agent to 'the hair with which it is in contact for a period of time' which varies between 3 and 30 minutes, this application of rinsing and optionally washing and drying the Hair is followed.

The present invention also relates to water wave lotions for the hair, characterized in that it is in watery-alcoholic ' shear solution contain at least one cosmetic resin and at least one compound of the formula II, as defined above.

The Wasserwel1otionen according to the invention generally contain 20 to 70% by weight of a low molecular weight alcohol and 1 to 3% by weight of a cosmetic resin.

Among the cosmetic resins that are included in the composition of these water-waving lotions, one can mention: the film-forming ones Polymers such as polyvinylpyrrolidone, the copolymers made of polyvinylpyrrolidone / vinyl acetate, the copolymers made of Vinyl acetate and an unsaturated carboxylic acid, such as crotonic acid, resulting from the copolymerization of vinyl acetate, crotonic acid and a copolymer derived from acrylic or methacrylic ester, the copolymers resulting from the copolymerization of vinyl acetate and an alkyl vinyl ether which are produced by the;

Copolymerization of vinyl acetate, crotonic acid and a vinyl; ester of an acid with a short carbon chain or a Allyl or methyl ester of an acid with a long carbon

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chain-derived copolymers resulting from copolymerization an ester that is different from an unsaturated alcohol and an acid with a short carbon chain, an unsaturated one Short chain acid and at least one ester derived from a saturated short chain alcohol, and an unsaturated acid derived copolymers, which from the copolymerization of at least one unsaturated ester and at least one unsaturated acid derived copolymer.

The preferred resins include: polyvinylpyrrolidone with a molecular weight of 10,000 to 70,000, the copolymers of 10 % crotonic acid, 90 % vinyl acetate with a molecular weight of 10,000 to 70,000, the copolymers of polyvinylpyrrolidone (PVP) / vinyl acetate (AV) with a molecular weight of 30,000 to 200,000, the PVP: AV ratio between 30:70 and 70:30, the copolymers of maleic anhydride / methyl vinyl ether in a molar ratio of preferably 1: 1 with a specific viscosity that

is between 0.1 and 3.5 when it is at 25 ⁰ C and a Konzenfcra

3 tion of 1 g in 100 cm methyl ethyl ketone is measured, the Monoethyl ester, monoisopropyl ester or monobutyl ester of the copolymer of maleic anhydride and methyl vinyl ether, the copolymer of maleic anhydride and butyl vinyl ether, the molar ratio of male anhydride to butyl vinyl ether being 1: 1, the terpolymers of 15 to 25 % methyl methacrylate / 18 to 28 % stearyl methacrylate up to 62% dimethyl aminoethyl methacrylate, which are quaternized with dimethyl sulfate, the terpolymers from 75 to 85 % vinyl acetate / 10 to 20 % aluminum stearate / 3 to 10 % aluminum oxyacetic acid. These resins are used in a proportion of 1 to 3% by weight.

The low molecular weight alcohols used in making the water wave lotions of the present invention; are preferably ethanol and isopropanol.

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The pH of the water wave lotions according to the invention is generally between 3 and 8.

The water wave lotions according to the invention can contain dyes of the formula II on their own; in this case they form so-called tinting agents. However, you can also use other DirektH dyes such as the direct dyes mentioned above. They can also contain adjuvants such as the aforementioned adjuvants.

The water wave lotions according to the invention are customary Applied by applying it to damp, previously washed and rinsed hair, followed by wrapping and drying the hair.

The dyes of the formula II can also be used in the form of hair lacquers, characterized in that they contain at least contain at least one cosmetic resin and at least one compound of the formula II in alcoholic solution.

The alcohols used in the paints according to the invention are Low molecular weight alcohols such as ethanol or Isopropanol.

The cosmetic resins used can be the aforementioned resins. They are incorporated into the agent at 1 to 3% by weight.

The following examples serve to illustrate the invention without, however, restricting it.

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example

Preparation of 4'-dimethyl amino-1 ', 2-azobenzene-1-methylpyridinium methyl sulfate.

A) Preparation of 4'-dimethyl amino-1 ', 2-azobenzene-pyridine-N oxyds of the formula

N-N

^{A solution, cooled to 0} ° C., of 0.1 mol of N-oxy-2-pyridyl-diazo is slowly added, while the temperature is kept at +5 ° C. nium chloride, made according to Katritzky J.C.S. 1957, p

191, to a solution of 1.2.1 g of N, N-dimethyl ani 1 in in 12 cm Acetic acid too.

The mixture is stirred for 30 minutes and then 40 cm of sodium acetate in 40% aqueous solution is added twice. The precipitate obtained is filtered off, washed with water and dried. After recrystallization from 50% alcohol to obtain a product having a melting point of 188 ⁰ C.

J. J
calculated: C. 64 .45; H 5 .79; N 23 , 15 found: C. 64 , 25; H 6th , 11; N 22nd , 95

B) Preparation of 4'-dimethylamino-1 ', 2-azobenzene-1-methoxypyridinium methyl sulfate of the formula

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0.1 mol of the compound obtained in step A) is suspended in 100 cm of N-methyl-2-pyrrolidone. One adds drop by drop vigorous stirring 35 cm of dimethyl sulfate and stirred for 1 hour. It is then filtered and washed with 35 cm acetone and recrystallized from alcohol.

The product obtained has a melting point of 197 ^° C.

Analysis C, 5 ^H 20 N ₄ ° 5 ^S. H 5 .43 N ft .22 % calculated: C. 48 , 90- H 5 .62 N 15th .10 % found C. 49 , 08 15th

C) Preparation of 4 ¹ -dimethylamino-1 ', 2-azobenzolpyridine • of the formula

N-N

-CH.

0.1 mol of the compound obtained in stage B) is dissolved in

3 3

600 cm of 90% alcohol and 42 cm of concentrated ammonia.

The mixture is refluxed for 1 hour, then the solvent is distilled

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solvent under reduced pressure. The residue will

3 taken up again in 100 cm of water and filtered. After at kristal1 isation from cyclohexane to give a product with a melting point of 112 ⁰ C.

Analysis C ₁₃ H ₁₄ N ₄ O

Calculated: C 69.00 H 6.2 N 24.8 % found: C 69.03 H 5.93 N 25.06 %

D) Preparation of 4 ^1- dimethyl amino-1 ', 2-azobenzene-1-methylpyridinium methyl sulfate of the formula

^CH 3 ^SO 4

0.1 mol of the compound obtained in step C) is dissolved in 100 cm of N-methyl-2-pyrrhdone. One adds drop by drop vigorous stirring 19.5 cm of dimethyl sulfate. One stirs one Hour, then filtered and washed with 35 cm acetone and crystallized from alcohol.

The product obtained has a melting point of 210 ^° C. Analysis C ₁₅ H ₂₀ N ₄ O ₄ S

calculated: C 51.12 H 5.68 N 15.95 % found: C 51.12 H 5.77 N 16.04 %

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example

Preparation of 4'-diethylamino-1 ', 2-azobenzene-1-methyl pyridinium methyl sulfate of the formula

N = N

NC ₂ H ₅

^C 2 ^H 5

This compound is prepared according to the procedure described in Example 1, with the only exception that one in stage A) a solution of N, N-diethyl at "1 in used. Das

received Kroauk .Z KNOW . ei r ien O CIIII ie ι ζ.μ U HK , 73 Analysis C 17 ^H 24 ^N 4 ° 4 ^pp , 72 calculated: Xi C ^
C. 53 , 70 H 6th , 32 N 14th found: C. 53 , 34 H 6th , 49 N 14th : B e i s ρ i e 1 3

Production of 4'-dimethylamino-1 ', 2-azobenzene-1,3-dimethyl pyridinium methyl sulfate of the formula:

CH ₃ SO ₄

N CH.

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This compound is obtained according to the procedure described in Example 1, with the only exception that the diazotized amine is 2-amino-3-methylpyridine-N-oxide. The melting point of the product obtained is 210 ^° C.

Analysis C 1 6 ^H. 22 ^N. 4 ° 4 ^pp H 6th , 0 1 N 1 5 , 30 calculated: 1 D. C C
C. 52 * T
, 44 H 6th ,1 6th N 1 5 , 11 found: C. 52 , 47

Example 4:

Production of bis (ß-hydroxyethyl) -4'-amino-1 ', 2-azobenzene- | 1,4-dimethylpyridinium methyl sulfate of the formula: \

CH ₃ SO ₄ O

N CH ₂ CH ₂ OH

This compound is obtained according to the procedure described in Example 1, with the only exception that the in stage A) used Diazoniumsalζ from 2-amino-4-methylpyridine-N-oxide is derived and that the aniline derivative used is N, N- (ß-hydroxyethyl) aniline. According to Umkristallv a product with a melting point is obtained from alcohol

point of 16 5 ⁰ C. 4 ° 6 ^p H 2 6th , 10 1 1 N 1 13th , 13 Analysis C 18th H 26 ^N. 50 , 70 H 6th , 11 N 13th , 27 calculated: C. 50 , 73 - 18th found: C. 6098 0 /1

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example

/ f «

Preparation of 4'-dimethylamino-2'-methyl-1 '^ - azobenzene-S-chloro-1-methylpyridinium methyl sulfate of the formula

Cl-

CH_SO. 3 4

N CH.

This compound is obtained according to the procedure described in Example 1, with the only exception that 2-N-oxypyridyl-4-chloro-diazonium chloride and 3-methyl-N, N-dimethylani1 are used in stage A). The product melts at 242 ⁰ C.

example

Preparation of 4 ^1- amino-1 ¹ , 2-azobenzene-1-methylpyridinium methyl sulfate.

A) Preparation of the sodium salt of 1'-oxy-2 ¹ , 4-azopyridinaniline methylsulfonic acid of the formula:

NHCH ₂ SO ₃ Na

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0.11 mol of deso> salt of aniline are dissolved in 17 cm of water. Is added to 53 g of crystalline sodium acetate and cooled to +5 ^0C. A cold solution of 0.1 mol of 2-N-oxypyridyldiazonium chloride, prepared according to J Katritzki, JCS 1957, page 191, is slowly added. Then you give | 130 g of crystallized sodium acetate and allowed to react for 1 hour. It is suctioned off and dried over phosphoric anhydride. The recrystallized from water product having a melting point of 16O ⁰ C.

Analysis ^c i2 ^H ll ^N 4 ° 4 ^{S Na> 3 H} 2 °

Calculated: C 37.50 H 4.32 N 14.55 % found: C 37.99 H 3.46 N 14.26 %

B) Production of 4'-amino-1 ', 2-azobenzolpyridine-N-oxide of formula

Dissolve 0.1 mol of the compound obtained in Step A) in 200 cm of 10% ammonia and heated for 5 hours at 6O ⁰ C, allowed to cool, then filtered, washed with water and dried. The product recrystallized from methanol has a melting point of 300 ^° C. (decomposition).

Analysis C ₁₁ H ₁₀ N ₄ O

Calculated: C 61.70 H 4.67 N 26.17% found: C 61.79 H 4.93 N 25.99 %

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C) Preparation of 4'-amino-1 ', 2-azobenzene-1-methoxypyridinium methyl sulfate of the formula

N-N

0.1 mol of the compound obtained in stage B) is dissolved in

3 3

100 cm N-methyl-2-pyrrolidone. One drops 12.5 cm Dimethyl sulfate and leaves in contact for 1 night. The dye is precipitated by adding ethyl acetate. One filters, washes with alcohol, later with ether and dries.

D) Preparation of 4 ^1- amino-1 ', 2-azobenzolpyridine of the formula 0.1 mol of the compound obtained in stage C) is dissolved in

3 3

600 cm of 90% alcohol and 42 cm of concentrated ammonia and refluxed for 1 hour. The solvent is distilled off under reduced pressure and the product becomes recrystallized from ethyl acetate.

E) Production of 4'-amino-l ', 2-azobenzene-l-methylpyridinium methyl sulfate of the formula:

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N-N

CH.SO.O 3 4

0.1 mol of the compound obtained in step D) is dissolved in

3

100 cm N-methyl-2-pyrrolidone. 12.5 cm are added with stirring Dimethyl sulfate and allowed to react for 1 hour 30 minutes. 400 cm of ethyl acetate are added, the oil obtained is decanted and crystallized from absolute ethanol. The product has a melting point of 193 C.

Analysis: C ₁ → H ₁₆ N ₄ O ₄ S Calculated: C 48.15 H 4.94 N 17.29 found: C 48.28 H 5.00 N 17.21

Example 7

Preparation of 4 ¹ -amino-1 ', 2-azobenzene-l-i3-dimethyl pyridinium methyl sulfate of the formula:

CH ₃ SO ₄

This compound is obtained according to the procedure described in Example 6, the diazotized amine being the 2-amino Is 3-methylpyridine-N-oxide. After recrystallization from absolute

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lutem alcohol has the product, a melting point of 183 ⁰ C.

Analysis C ₁₄ H ₁₈ N ₄ O ₄ S

Calculated: C 49.70 H 5.33 N 16.56 % found: C 49.54 H 5.35 N 16.35 %

Example 8

Preparation of 4 ¹ -amino-8 ¹ -hydroxy-1 ¹ , 2-azonaphthalene-1-methylpyridinium methyl sulfate

A) Preparation of 4 ¹ -amino-8 ¹ -hydroxy-1 ', 2-azonaphthalenpyridine-N-oxide of the formula:

N = N

HO:

A ^{solution, cooled to 0} ° C., of 0.1 mol of 2-N-oxypyridyldiazonium chloride, which according to Katritzki JCS 1957,

Page 191, is prepared, to a solution of the 5-acetoxy

l-naphthylamine monohydrochloride in 900 cm of 80% acetic acid, while keeping the temperature at +5 ⁰ C. The reaction f

mixture is brought to pH 4 by adding sodium acetate The mixture is stirred for 30 minutes and then 1.5 liters of water are added, the mixture is filtered and dried. The product obtained is dissolved in 450 cm 2-methoxyethanol. 150 cm of sodium hydroxide solution are added and the mixture is stirred

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30 minutes. It is poured into 3 liters of water, neutralized with acetic acid and dried. The product has a melting point of 28O ⁰ C (decomposition).

B) Preparation of 4'-amino-8 ^1- hydroxy-1 ', 2-azonaphthalene-1 methoxypyridinium methyl sulfate of the formula:

OCH.

N = N

CH.SO.ß 3 4

0.1 mol of the compound obtained in step A) is dissolved in

125 cm N-methyl-2-pyrrolidone and are dropwise under RUh-3

ren 15 cm of dimethyl sulfate. The mixture is stirred until the reaction has ended. The product becomes after the addition of ethyl acetate to Reaction mixture filtered.

C) Preparation of 4'-amino-8 ^1- hydroxy-1 ', 2-azonaphthalene pyridine of the formula:

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0.1 mol of the compound obtained in step B) is dissolved in 1 liter of 90% alcohol and 100 cm of concentrated ammonia The mixture is refluxed for 1 hour and evaporated to dryness. ι The product is triturated in water, filtered and dried !.

D) Preparation of 4'-amino-8 ^1- hydroxy-1 ', 2-azonaphthalene-1methylpyridinium methyl sulfate of the formula:

CH ₃ SO ₄

0.1 mol of the compound obtained in stage C) is dissolved in

125 cm N-methyl-2-pyrrolidone. One adds drop by drop

3
Stir in 15 cm of dimethyl sulfate and stir until the reaction has ended. The product is precipitated by adding ethyl acetate. The product has a melting point of 25O ⁰ C (decomposition).

example

Preparation of 4'-diinethylamino-1 ', 2-azobenzene-4-cyano-imethylpyridinium methyl sulfate.

A) Preparation of 4 ^1- dimethyl amino-1 ', 2-azobenzene-4-cyano pyridine of the formula:

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-CH.

0.1 mol of that obtained in Example 1 in stage B) is dissolved

3
Compound in 40 cm of water and add dropwise while stirring

3 Add 10 g of sodium cyanide in 50 cm of water. It is heated for 3 hours, to 8O ⁰ C and then allowed to cool and filtered. The product recrystallized from chloroform has a melting point of

19O ⁰ C.

analysis

^C 14 ^H 13 ^N 5

Calculated: C 66.95 H 5.18 N 27.87 % found: C 66.81 H 5.18 N 27.78 %

B) Preparation of 4 ¹ -Dimethylamino-1 '^ -azobenzene ^ -cyano-imethylpyridinium methyl sulfate of the formula:

CN

N = N

0.1 mol of the compound obtained in step A) is dissolved in

3 3

300 cm of N-methyl-2-pyrrolidone and gives dropwise 15 cm

Dimethyl sulfate too. The mixture is heated to 5O ⁰ C until the reaction begins

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ends is. The product is precipitated by the addition of ethyl acetate and purified by chromatography on a silica gel column. The product has a melting point of 208 ^° C.

example

10

Preparation of 2 ¹ -chloro-4 ¹ -dimethylamino-1 ', 2-azobenzene-1-methylpyridinium methyl sulfate

A) Preparation of 2 ¹ -chloro-4 ¹ -dimethylamino-1 ', 2-azobenzene pyridine-N-oxide of the formula:

Man "dissolved 5 g (0.032 mol) Metachlor-N, N-dimethylaniline in 6 CNT acetic acid and the solution is cooled to 5 ⁰ C. Then, gradually adding a solution of the according to Example 1, starting from 0.032 mol of 2-aminopyridine-N-oxide The resulting precipitate is suspended in water and a saturated sodium bicarbonate solution is added until it is neutral. It is filtered off with suction, dried and the dye obtained is crystallized from ethyl alcohol. It melts at 202 ^° C.

B) Preparation of 2'-chloro-4 ¹ -dimethylamino-1 ', 2-azobenzene-1-methoxypyridinium methyl sulfate:

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OCH

CH, S0.O
3 4

N CH.

4.45 g of the compound obtained in step A) are dissolved in

3
11.15 cm of N-methyl-pyrrolidone and is added dropwise

3
Stir in 1.70 cm of dimethyl sulfate. The mixture is stirred for a further 1 hour, the precipitate formed is filtered off and washed with acetone

C) Preparation of 2'-chloro-4 ¹ -dimethyl amino-1 ', 2-azobenzolpyridine:

To a solution of 4.75 g of the compound obtained in stage B)

3 3

Dung in 73 cm of 90% ethanol is given 5 cm of concentrated Ammonia. The mixture is then refluxed until the reaction has ended. The solution is then under reduced pressure concentrated to dryness and the reaction product is purified by chromatography on a column of silica gel, where-

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when using ethyl acetate as the eluant.

D) Preparation of 2'-chloro-4'-dimethylamino-l ^j , 2-azobenzene-1-methylpyridinium methyl sulfate:

- N

Cl-J

CH ₃ SO ₄

3 g of the compound obtained in stage C) are dissolved in 7 cm N-methylpyrrolidone and slowly gives with vigorous stirring

3
1.2 cm of dimethyl sulfate. After the addition has ended, the mixture is stirred for a further 1 hour and the precipitate obtained is filtered off with suction; this is then washed with ethyl acetate and dried. The dye is purified by crystallization from ethanol. It melts at 225 ⁰ C.

analysis

C ₁₅ H ₁₉ N ₄ O ₄ S Cl

calculated: N found: N

14.48 %

14.72 - 14.41%

example

11

Preparation of 2'-acetyl ami no-4'-dimethyl ami no-1 ', 2-azobenzene-1-methylpyridinium methyl sulfate of the formula

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NHCOCH,

CH,

This compound is obtained according to the procedure described in Example 1, with the only exception that in Stage A) a solution of metaacetylamino-N, N-dimethylani1 in used. The product obtained melts after recrystallization

from methanol at 222 ⁰ C.!

Analysis ^c i7 ^H ₂ 3 ^N 5 ° 5 ^S

calculated: C 49.89 found: C 49.66

H H

5.62 5.45

N N

17.11 % 17.31 %

example

Preparation of 2 ¹ -nitro-4 ¹ -dimethylamino-1 ', 2-azobenzene-lmethyl pyridini ummethyl sulfate of the formula:

NO.

CH

\ CH,

This compound is prepared according to the procedure described in Example 1, with the only exception that one in stage A) a solution of metanitro-N, N-dimethylanil in

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used. The product obtained melts after recrystallization from methanol at 254 ^° C.

Analysis C ₁₅ H ₁₉ N ₅ O ₅ S, 1/2 CH ₃ OH

calculated: found:

C 45.00 C 44.81

5.08
5.33

N 16.94 % N 17.08 %

example

13th

Preparation of 4 ^1- amino-3'-methoxy-1 ', 2-azobenzene-1-methyl pyridinium methyl sulfate of the formula:

This compound is obtained according to the procedure described in Example 1, with the only exception that a solution of orthoanisidine is used in step A). After recrystallization from alcohol, the melting point of the product obtained is 205 ^° C.

Analysis C ₁₄ H ₁₃ N ₄ O ₅ S

calculated: C 47.50 found: C 47.28

H 5.08 N 15.82 H 5.28 N 15.72

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example

14th

Preparation of 2 ', 4'-diamino-5 ¹ -methyl-1', 2-azobenzene-1,5-dimethylpyridinium methyl sulfate

A) Preparation of 2 ¹ , 4'-Diamino-5'-methyl-1 ', 2-azobenzene-5-methylpyridine-N-oxide of the formula:

A solution of 0.1 mol, cooled to OC, is slowly added B-methyl-2-N-oxypyridyldiazonium chloride, prepared according to

Katritzky, J. Chem. Soc. 1957, page 191, to a solution of

3 12.2 g of 2,4-diaminotoluene in 20 cm of acetic acid while one keeps the temperature at +5 ^{0 C.}

The mixture is stirred for 30 minutes and then 34 g of crystallized material are added Sodium acetate too. The precipitate obtained is filtered off, washes with water and dries.

B) Preparation of 2 ', 4'-diacetylamino-5'-methyl-1', 2-azobenzene-5-methylpyridine-N-oxide the formula:

CH.

NHCOCH.

NHCOCH.

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0.1 mol of the compound obtained in step A) is dissolved in

3 300 cm of acetic acid and gives drop by drop in the course of 2 hours | - add 88 g of acetic anhydride on a boiling water bath. It is allowed to cool and the reaction mass is poured onto 500 g of ice. the solution thus obtained is neutralized with sodium carbonate. The precipitate obtained is filtered off and washed with water and dries.

C) Preparation of V , 4'-Di acetylamino-5 ¹ -methyl-I ', 2-azobenzene-1-methoxy-5-methylpyridinium methyl sulfate of the formula

CH,

NHCOCH,

CH ₃ SO ₄ ^

OCH

NHCOCH.

0.1 mol of the compound obtained in stage B) is dissolved in 160 cm of N-methyl-2-pyrrolidone. One adds drop by drop vigorous stirring to 9 cm of dimethyl sulfate. One leaves one night in contact and then adds 2 cm of dimethyl sulfate. The precipitate obtained is filtered off, washed with acetone and dries.

D) Preparation of 2 ', 4'-diacetylamino-5 ¹ -methyl-1', 2-azobenzene-5-methylpyridine of the formula:

NHCCl

NHCOCH.

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0.1 mol of the compound obtained in stage C) is dissolved in 2300 cm of 90% alcohol. One gives 190 cm ^ concentrated Ammonia is added and the mixture is stirred for 45 minutes at ambient temperature. The solvent is distilled under reduced pressure

Pressure off. The residue is taken up again with 100 cm of water, filtered and dried.

E) Preparation of 2 ', 4'-diamino-5 ¹ -methyl-1', 2-azobenzene-5-methylpyridine of the formula:

NH _n

0.1 mol of the compound obtained in step D) is dissolved in 100 cm 5N hydrochloric acid and heated for 3 hours Reflux. The reaction mass is cooled and neutralized by adding sodium bicarbonate. One extracts with Chloroform and then the solvent is distilled off under reduced pressure. The product is determined by chromatography Purified on silica gel using dichloroethane as the eluant.

F) Preparation of V , 4'-diamino-5 ¹ -methyl-1 ', 2-azobenzene-1-, 5-dimethyl pyridinium methyl sulfate of the formula:

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NH.

0.1 mol of the compound obtained in step E) is dissolved in

3 3

7500 cm dichloroethane. 10 cm of dimethyl are added dropwise sulfate and stir for 30 minutes. It is filtered and the product obtained is recrystallized from alcohol. It melts at 252 ⁰ C.

Analysis C _1c H _o1 N _c 0 _Ä S

calculated: C. 49 , 08 H 5 .72 N 19th .04 found: C. 48 , 78 H 5 , 88 N 19th .28

example

15th

Production of bis (ß-hydroxyethyl) -4'-amino-1 ', 2-azobenzene 6-cyano-1,4-dimethylpyridinium perchlorate of the formula:

CH

CH ₂ CH ₂ OH

ClO,

This compound is made according to that described in Example 9 Mode of operation, with the only exception that one is in

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Stage A) a solution of bis (ß-hydroxyethyl) -4'-amino-1 ', 2-azobenzene-1-methoxy-4-methylpyridinium methyl sulfate is used. The product is purified by dissolving it in water and adding an aqueous sodium perchlorate solution. It melts at 21O ⁰ C with decomposition.

example

16

Production of 4'-phenylamino-1 ', 2-azobenzene-l, 6-dimethyl pyridinium methyl sulfate of the formula:

This compound is prepared according to the procedure described in Example 1, with the only exception that 6-methyl-2-N-oxypyridyldiazonium chloride and diphenylamine are used in step A). The recrystallized from methanol the product melts at 22O ⁰ C to 222 ⁰ C.

Analysis ^c i7 ^H 23 ^N 5 ° 5 ^S

calculated: C 49.89 H 5.62 N 17.11 % found: C 49.66 H 5.45 N 17.31%

example

17th

Preparation of 4'-dimethylamino-1 ', 2-azobenzene-l, 5-dimethyl pyridinium methyl sulfate of the formula:

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CH ₃ SO ₄

CH.

This compound is obtained according to the procedure described in Example 1, with the only exception that in Step A) the 5-methyl-2-N-oxypyridyldiazonium chloride and the same N, N-Dimethylani1 used in.

The recrystallized from ethanol product melts at 168 ⁰ C

Analysis C 16 ^H 22 ^N 4 ° 4 ^pp H 6th , 01 N 1 5 , 30 calculated: C. 52 , 48 H 6th , 07 N 1 5 , 22 found: C. 52 , 18

The same connection made using traditional methods can also be used in the means described.

Examples of means Example I ^ Make the following dye:

2'-acetylamino-4 ¹ -dimethylamino-1 ', 2-azobenzene-

1-methylpyridinium methyl sulfate

2-amino-4-hydroxy-1, l'-azobenzene-4'-hydroxybenzene. Quaternary copolymer of vinyl pyrrolidone / dialkyl lower alkyl acrylate with a molecular weight of approximately 1,000,000 (under the trade designation GAFQUAT 755 sold)

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0.02 g 0.02 g

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- Water as much as required per 100 g

This agent is applied to natural gray hair with 95 % white hair that has previously been shampooed for 5 minutes. A gray-rose color is obtained.

Example II The following remedy is made:

- 4'-Phenylamino-l ', 2-azobenzene-1,6-dimethyl-pyridinium methyl sulfate 0.01 g

- (1-Anthraquinonylaminopropyl) trimethylammonium methyl sulfate 0.03 g

Quaternized cellulose, sold under the trade name JR 400 2 g

- Triethanolamine as much as necessary for pH 8

- Water as much as required per 100 g

This easily gelled agent is applied to previously washed and left bleached hair on for 10 minutes. Intense, pearly pink reflections are obtained.

Example III The following remedy is made:

4'-Amino-8'-hydroxy-1 ', 2-azonaphthalene-1-methyl pyridini ummethyl sul f at 0.03 g

- Bis- (ß-hydroxyethyl) -4'-amino-1 ', 2-azobenzene-1,4-dimethylpyridinium methyl sulfate 0.02 g

- Vinyl acetate / crotonic acid (90/10) copolymer 2 g

- 2-Amino-2-methyl-1-propanol as much as necessary for 100 % neutralization

- Ethyl alcohol as much as necessary to 100 ecm

- 38 -609820/1111

This alcoholic solution is mixed with a mixture of F.11 / F.12 conditioned in an aerosol container, where F.11 for Trichlorofluoromethane and F.12 denotes dichlorodifluoromethane, in a ratio of 60:40 to 30 g of solution and 70 grams of propellant.

When used on auburn tinted hair, this varnish gives the hair a pretty ash-colored reflex.

B e i s ρ i e 1 IV

Make the following solution:

- 4 ¹ -Dimethylamino-1 ', 2-azobenzene-1-methylpyridinium methyl sulfate 0.010 g

- Vinyl acetate / crotonic acid (90/10) copolymer 2 g

- 2-Amino-2-methyl-1-propanol as much as necessary for 100% neutralization

- Ethyl alcohol as much as necessary to 100 ecm

This alcoholic solution is mixed with a mixture of F.11 / F.12 conditioned in an aerosol container, where F.11 for Trichlorofluoromethane and F.12 means dichlorodifluoromethane, in a ratio of 60/40 to 30 g of solution and 70 g propellant.

When used on light auburn tinted hair, this varnish gives the hair a violet-blue reflex.

example

Make the following solution:

- Dye according to Example 10 0.050 g

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- Vinyl acetate / crotonic acid (90/10) copolymer 1.8 g

- Vinyl acetate / vinyl pyrrolidone copolymer

(40/60) 0.3 g

- Ethyl alcohol as much as necessary for 50 °

- Triethanolamine as much as required for pH 7

- Water as much as necessary to 100 ecm

When applied to chestnut-brown tinted hair, it gives this water wave lotion gives the hair a very luminous violet blue Reflexes.

Example VI

The following remedy is made:

- 2'-Nitro-4-dimethyl amino-1 ', 2-azobenzene-1-methylpyridinium methyl sulfate 0.5 g

- ethanol 40 g

- Copolymer of vinyl pyrrolidone / vinyl acetate

(30/70) 1.5 g

- Double chloride of zinc and N - ^ (NiN ¹ -Ethylacetylaminoethyl) -4'-aminophenylJ-2-aza-3-aminobenzoquinone diimine .... 0.1 g

- Triethanolamine as much as required for pH 7

- Water as much as required per 100 g

This agent is applied as a water wave lotion to naturally gray hair with 95 % white hair. A cardinal violet tint is obtained.

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Example VII The following remedy is made:

4'-Amino-3 ^1- methoxy-1 ', 2-azobenzene-1-methylpyridinium methyl sulfate 0.02 g

- ethanol 50 g

- Monobutyl ester of the copolymer of methyl vinyl ether / maleic anhydride (sold under the trade name GANTREZ ES 425) 2 g

- 1,4- (ß-morpholinoethyl) diaminoanthraquinone .... 0.2 g

- Triethanolamine as much as required for pH 8

- Water as much as required per 100 g

This remedy is used as a water wave lotion on bleached hair upset. A mauve tint is obtained.

Example VIII The following remedy is made:

- 2 ', 4'-Diamino-5'-methyl-r, 2-azobenzene-1 - _s 5-dimethylpyridinium methyl sulfate 0.04 g

- ethanol 70 g

- polyvinylpyrrolidone K / 30 3 g

- Methyl £ { 1-anthraquinonylamino propyl) trimethylammonium sulfate 0.5 g

- Triethanolamine as much as required for pH 6.5

- Water as much as required per 100 g

This agent, applied as a water wave lotion to 95% natural white hair, gives it a pink-1axe color.

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Example IX

The following remedy is made:

- 4'-Dimethyl amino-1 ', 2-azobenzene-1,5-dimethyl pyridinium methyl sulfate 0.3 g

-Ethanol 60 g

- Polyvinylpyrrolidone / vinyl acetate copolymer (30/70) 2.5 g

- 2-Ami no-4-hydroxyl, 1 '-azobenzene -4' -hydroxy-

benzene O, 4g

- Triethanolamine as much as required for pH 6

- Water as much as required per 100 g

This Wasserwel1otion as applied to gray hair means giving them a _{copper-t-pearly} tint.

Example X

Make the following dye:

- Dyestuff according to Example 1 0.050 g

- Vinyl acetate / crotonic acid (90/10) copolymer 1.8 g

- Vinyl acetate / vinyl pyrrolidone copolymer

(40/60) 0.3 g

- Ethyl alcohol as much as necessary for 50 °

- Triäthanolami η as much as necessary for pH 9

- Water as much as necessary to 100 ecm

When used on naturally auburn hair, this water wave lotion gives the hair a pretty, very luminous violet-blue reflex.

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Example XI Make the following dye:

- Dyestuff according to Example 2 0.050 g

- Vinyl acetate / crotonic acid (90/10) copolymer 1.8 g

- Vinyl acetate / vinyl pyrrolidone copolymer

(40/60) 0.3 g

- Ethyl alcohol as much as necessary for 50 °

- Triethanolamine as much as required for pH 7

- Water as much as necessary to 100 ecm

When used on auburn-tinted hair, this water wave lotion gives the hair a violet-auburn color Tint.

Example XII Make the following dye:

- Dyestuff according to Example 6 0.050 g

- Vinyl acetate / crotonic acid (90/10) copolymer 1.8 g

- Vinyl acetate / vinyl pyrrolidone copolymer

(40/60) 0.3 g

- Ethyl alcohol as much as necessary for 50 °

- Citric acid as much as required for pH 5

- water as much as necessary to 100 cc »

When used on naturally dark auburn hair j this water wave lotion gives the hair a particularly aesthetic ; tables mahogany-colored reflex.

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Example XIII Make the following dye:

- Dyestuff according to Example 8 0.050 g

- Vinyl acetate / crotonic acid (90/10) copolymer 1.8 g

- Vinyl acetate / vinyl pyrrolidone copolymer

(40 / 6O) 0.3 g

- Ethyl alcohol as much as necessary for 50 °

- Citric acid as much as required for pH 5

- Water as much as necessary to 100 ecm

When applied to dark blonde colored hair, it gives this water wave lotion gives the hair a particularly aesthetic ash-colored reflex.

Example XIV

Make the following dye:

- Dyestuff according to Example 3 0.050 g

- Vinyl acetate / crotonic acid (90/10) copolymer 1.8 g

- Copolymer of vinyl acetate / vinyl pyrrolidone

(40/60) 0.3 g

- Ethyl alcohol as much as necessary for 50 °

- Triethanolamine as much as required for pH 7

- Water as much as required per 100 g

When used on blonde dyed hair, this gives it Wasserwel lotion gives the hair a particularly bright blond-rose tint.

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609820/1111

Example XV Make the following dye:

- Dyestuff according to Example 7 0.050 g

- Vinyl acetate / crotonic acid (90/10) copolymer 1.8 g

- Vinyl acetate / vinyl pyrrolidone copolymer

(40/60) 0.3 g

- Ethyl alcohol as much as necessary for 50 °

- Citric acid as much as required for pH 5

- Water as much as necessary to 100 ecm

When used on naturally auburn hair, this water wave lotion gives the hair magnificent red-orange reflections.

Example XVI

Make the following dye:

- Dyestuff according to Example 4 0.050 g

- Vinyl acetate / crotonic acid (90/10) copolymer 1.8 g

- Vinyl acetate / vinyl pyrrolidone copolymer

j (40/60) 0.3 g

! - Ethyl alcohol as much as necessary for 50 °

- Triethanolamine as much as required for pH 7

- Water as much as necessary to 100 ecm

When used on naturally auburn hair j this water wave lotion gives the hair very beautiful purple reflections.

Example XVII Make the following dye:

- Dyestuff according to Example 9 0.050 g

- Vinyl acetate / crotonic acid (90/10) copolymer 1.8 g

- Vinyl acetate / vinyl pyrrolidone copolymer

(40/60) 0.3 g

- Ethyl alcohol as much as necessary for 50 °

- Triethanolamine as much as required for pH 9

- Water as much as necessary to 100 ecm

When used on dark chestnut tinted hair this water wel1otion gives the hair a splendid, iri emanating ash-colored reflex.

Example XIX Make the following dye:

- Dye according to Example 5 0.050 g

- Vinyl acetate / crotonic acid (90/10) copolymer 1.8 g

- Vinyl acetate / vinyl pyrrolidone copolymer

(40/60) 0.3 g

- Ethyl alcohol as much as necessary for 50 °

- Citric acid as much as required for pH 5

- Water as much as necessary to 100 ecm

When used on naturally dark auburn hair, this water wave lotion gives the hair a particularly luminous look ash-mauve reflections.

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Example XX Make the following dye:

- Dye according to Example 8 0.0312 g

- Dye according to Example 4 0.0187 g

- Vinyl acetate / crotonic acid (90/10) copolymer 1.8 g

- Vinyl acetate / vinyl pyrrolidone copolymer

(40/60) 0.3 g

- Ethyl alcohol as much as necessary for 50 °

- Triethanolamine as much as necessary for pH 7

- Water as much as necessary to 100 ecm

When applied to maroon tinted, this water wave lotion gave the hair a pretty look brown tint.

Hair gives ash-chestnut

Example XXI Make the following dye:

- Dyestuff according to Example 7 0.020 g

- Dyestuff according to Example 9 0.025 g

- Vinyl acetate / crotonic acid (90/10) copolymer 1.8 g

- Ethyl alcohol as much as required for 55 °

- hydrogen peroxide to 200 volumes 5 ecm

- Orthophosphoric acid as much as necessary for pH 3

- Water as much as necessary to 100 ecm

When used on naturally dark blonde hair, this water wave lotion lightly brightens and gives the hair a very bright purple reflex.

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Example XXII Make the following dye:

- Dye according to Example 4 0.300 g

- Hydroxyethylpropylellulose, under the trade name Methocel 65 Hg from Dow Chemical expelled 0.7 g

- Monoethanolami η as much as necessary for pH 11.4

- Water as much as required per 100 g

This solution, applied to naturally dark auburn hair and rinsed after 15 minutes, gives the hair a lot glowing purple reflections.

Example XXIII Make the following dye:

- Dye according to Example 5 0.400 g

Hydroxyethyl propyl cellulose, under the trade name Methocel 65 Hg 4000 from Dow Chemical expelled 0.7 g

- Monoethanolamine as much as required for pH 11.6

- Water as much as required per 100 g

This solution, applied to natural brown hair and rinsed after 15 minutes, gives the hair violet-blue reflections,

Example XXIV Make the following dye:

- Dye according to Example 7 1.0 g

- Butyl cellosolve 8 g

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- propylene glycol - 8 g

- Alkylphenolpolyäthoxyäther, under the trade name "Remcopal 334" from the company Gerland expelled 22 g

- Alkylphenolpolyäthoxyäther, under the trade name "Remcopal 349" from the company Gerland expelled 22 g

- Ammonia of 22 ° Baume 10 ecm

- Water as much as required per 100 g

20 g of hydrogen peroxide are added in 20 volumes to 20 g of the solution thus prepared.

In this way you get a gel that you apply to auburn hair. Wash your hair after 30 minutes. After drying, the hair is lightened and has a chestnut-mahogany tint.

Example XXV

Make the following dye:

- Dyestuff according to Example 9 0.035 g

- Nitropharaphenylenediamine dye 0.012 g

- Vinyl acetate / crotonic acid (90/10) copolymer 1.8 g

- Vinyl acetate / vinyl pyrrolidone copolymer

(40/60) 0.3 g

- Ethyl alcohol as much as necessary for 50 °

- Triethanolamine as much as necessary for pH 7

- Water as much as necessary to 100 ecm

When used on naturally light auburn hair, this water wave lotion gives the hair a very luminous veil blue reflections.

- 49 τ 609820/1111

Claims (19)

Claims Coloring agent for human hair according to claim 1 of parent application P 22 27 214.6, which is in aqueous or aqueous alcoholic solution at a pH between 3 and 12 an amount of 0.0005 to 5 wt .-% of at least one quaternary Azo dye of the formula I A '-N = N-B (I) contains, characterized in that the connection of the Formula I of the general formula wherein: R is a lower alkyl group of 1 to 4 carbon atoms represents; R ¹ J ₀ denotes a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms, in particular methyl; R'g a hydrogen atom, a lower alkyl group with Represents 1 to 4 carbon atoms, in particular methyl, or a group -CN; R ¹ O is a hydrogen atom or a halogen atom, in particular - 50 - 609820/1111 M / 16 196 a chlorine atom, a lower alkyl group with 1 to 4 carbon atoms, especially a methyl group; R ^l j denotes a hydrogen atom, a lower alkyl group, especially methyl, or a cyano group; R'j is a hydrogen atom, a lower alkyl group or represents a lower hydroxyalkyl group with 1 to 4 carbon atoms, in particular β-hydroxyethyl; R'p is a hydrogen atom, a lower alkyl group, a represents a lower hydroxyalkyl group with 1 to 4 carbon atoms, in particular β-hydroxyethyl, phenyl; R ' ₃ and / or R' _g a hydrogen atom, a lower alkyl group with 1 to 4 carbon atoms, in particular methyl ^ j or a lower alkoxy group with 1 to 4 carbon [ atoms, especially methoxy, mean; j R ¹ . and / or RV represent a hydrogen atom, a halogen atom, in particular chlorine, a lower alkyl group with 1 to 4 carbon atoms, in particular methyl, a nitro, amino or acetylamino group; whereby R ' ₅ and R'g can also form an unsaturated ring with 6 chain links which carries a substituent chelated with one of the nitrogen atoms of the azo bond, in particular hydroxyl (in which case R'j »R'o» R'g> R * 4 only represent hydrogen); Z ~ can represent an anion derived from a mineral or organic acid, in particular halogen (iodine, chlorine, bromine), fluoroborate, perchlorate, sulfate, acetate, in particular methyl sulfate; or corresponds to its mesomeric form. 2. Agent according to claim 1, characterized in that the quaternary nitrogen compound is present in amounts between 0.01 and 1.5% by weight. - 51 - 609820/1111 3. Composition according to claims 1 or 2, characterized in that it is a low molecular weight alcohol, ins- ' special ethanol or isopropanol. : 4. Means according to claims 1 or 2, characterized in that that there are other direct dyes, especially azo dyes, anthraquinone dyes, nitrated dyes the benzene series, indoanilines, indophenols or indamines. 5. Means according to claims 1 or 2 in the form of a water wave; Lotion for hair, characterized in that it contains at least one cosmetic resin ent-j holds. j 6. Means according to claim 5, characterized in that it Contains 20 to 70 percent by weight of a low molecular weight alcohol. 7. Agent according to claim 6, characterized in that the low molecular weight alcohol is ethanol or isopropanol. 8. Agent according to one of claims 5 to 7, characterized in that it contains 1 to 3% by weight of a cosmetic resin contains. 9. Agent according to one of claims 5 to 8, characterized in that the cosmetic resin is polyvinylpyrrolidone, is a copolymer of crotonic acid / vinyl acetate, vinylpyrrolidone / vinyl acetate or male anhydride / butyl vinyl ether. 10. means in the form of a hair lacquer, characterized in that there is at least one cosmetic in alcoholic solution 'cal resin and at least one quaternary azo compound according to claims 1 or 2 contains. - 52 -609820/1111 M / 16 196 11. Composition according to claim 10, characterized in that it contains 0.0005 to 5% by weight of a quaternary azo compound contains. 12. Means according to claim 11, characterized in that the quaternary azo compound is present in amounts ranging between 0.01 and 1.5% by weight. 13. Agent according to one of claims 10 to 12, characterized in that the alcohol contained therein is an alcohol with a low molecular weight. 14. Composition according to claim 10, characterized in that the alcohol is ethanol or isopropanol. 15. Agent according to one of claims 10 to 14, characterized in that it contains 1 to 3% by weight of cosmetic resin contains. 16. Agent according to one of claims 10 to 15, characterized in that the cosmetic resin is polyvinylpyrrolidone, a copolymer of crotonic acid / vinyl acetate, vinylpyrrolidone / vinyl acetate or maleic anhydride / butyl vinyl ether. 17. Compounds of the general formula: A ¹ - N = N - B ¹ characterized in that they have the general formula: - 53 - 609820/1111 M / 16 196 ^r ' ⁸ tV where: R ' _1O ' ^R * 8 ' ^Κ 3' ^R 4 ' ^R 5' ^R 6 * ^R 'l * R'2 »R and Z have the meanings given in the definition of general formula II and in which either R'g or R '^ represent a cyano group, independently of which the meanings of the above-mentioned nouns; are doing. 18. Compounds of the general formula: A '- N = N - B ¹ characterized in that they have the formula: correspond, in which R'g and R ' ₇ are different from -CN and R' ₅ and R ' _{g form} an unsaturated ring with 6 chain members, which carries a hydroxy substituent, which in each case with a nitrogen atom of the azo bond is chelated, R ¹ j, R ' ₂ , R' ₃ and R ¹ represent substance and in which R - 54 - ₁₀ , R ' ₈ , R and , Water same 609820/1111 Si Have meanings as in claim 1. 19. Colorant according to any one of claims 1 to 15, characterized characterized that there is also at least one in cosmetics commonly used adjuvants, in particular anionic, cationic, non-ionic, amphoteric or zwitter-t ionic surface-active agents, oxidizing agents,
Synergists or stabilizers for foam, sequestering agents, fatliquoring agents, thickening agents, preservatives, dispersants, swelling agents, penetrants, plasticizers or perfumes. 21 / V. - 55 - 609820/1111