DE2227214A1 - New colorants for keratin fibers and new diaza merocyanines for use in these compositions - Google Patents

Description

PATENT TO WX LT E PROF. DR. DR. J. REITSTÖTTER

DR.-ING. WOLFRAM BUNTE 222721

DR. KARL GEORG LÖSCH D - 8OOO MUNICH 13 BAUERSTRASSE 22 POST BOX 780, FERNRUF (OBII) 37 65 S3

Munich, M / 12029

L 'O RE AL
14, Rue Royale, Paris, France

New colorants for keratin fibers and new diaza-merocyanine. ; for use in these agents

One of the most common hair coloring methods is there in that one oxidizes dyes or "bases" together with Color modifiers or "couplers" used which aromatic m-diamines or m-aminophenols or pyrazolones or Can be diketones. When performing this procedure, one must have an oxidizing agent such as Hydrogen peroxide, to mix the chosen bases and Give couplers previously made alkaline.

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It is also known to use heterocyclic hydrazones together with couplers for coloring the hair. This is particular Subject of French patent 1,599,968.

However, this process has the disadvantage that hydrogen peroxide is used must use in alkaline medium, which brings a breakdown of the hair with it, which quickly become porous and brittle. In addition, the nuances obtained are due to the side reactions that take place in addition to the coupling reaction of the hydrazone occur with the coupler, rather difficult to reproduce. Added to this is the fact that the hydrazones are compounds which are relatively aggressive towards the skin, which is why they are used often makes problematic.

According to the invention, these disadvantages can be avoided by not using a mixture of hydrazone and couplers, but their coupling products used, which direct dyes which can be used at different pH values and produce easily reproducible nuances. The present invention accordingly relates to new colorants for human hair, which are characterized in that they have at least one diazamerocyanine or a diazamerocyanine salt of the formula in solution

A = NN = B
contain, in which

A is a nitrogen heterocycle with 5 or 6 ring members of the formula

■ - ^R 7 ^R 8.

R-N,

(II) or ** (III)

2 0 9 8 5 1/12 12

means in which R is a lower alkyl radical having 1 to 4 carbon atoms or an optionally substituted phenyl radical and X is an oxygen or sulfur atom, a radical NR ¹ , in which R ^{1 is} a lower alkyl radical, a radical -C ^ -, which is optionally with one or two Lower alkyl is substituted, an ethylene radical or a radical -C = N-

R "

wherein R "represents a hydrogen atom or a lower alkyl radical means to represent

Z is an ethylene radical or a radical -NR "', in which R" ^{1 is} a lower alkyl radical,

a hydrogen atom, a lower alkyl radical or a phenyl radical, R ₈ denotes a hydrogen atom or a lower alkyl radical, or Ry and Rg together with the carbon atoms to which they are bonded form a condensed benzene ring, optionally with one or more halogen atoms or alkyl, alkoxy - or nitro residues can be substituted,

B denotes a nitrogen heterocycle with 5 or 6 which may contain other heteroatoms and is not identical to the heterocycle according to definition A, or a ring of the formula (IV)

^R 4 ^R 3

VT

^R 5 ^R 6

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wherein Y is an oxygen atom or a radical

^R 2

means in which

R ₁ and R2 each denote a hydrogen atom, a lower alkyl group or a phenyl group, and Z " denotes an anion derived from an inorganic or organic acid such as a halide, fluoborate, perchlorate, sulfate, bisulfate or acetate, R ^ denotes a hydrogen atom, a Lower alkyl or lower alkoxy radical or a phenylcarbamyl radical, R ^ and Rg each mean a hydrogen atom or a lower alkyl or lower alkoxy radical having 1 to 4 carbon atoms, whereas R ^ means a hydrogen atom or an amino radical which can optionally be alkylated or acylated, and R = and Rg in addition, together with the carbon atoms to which they are attached, can form a condensed benzene ring,
or a ring of the formula. (V)

(V)

wherein either R ₁ and R ₉ or R ₂ and R ₁₀ , together with the carbon and nitrogen atoms to which they are attached, form a heterocycle with 5 or 6 ring members which can be saturated or unsaturated and can comprise other heteroatoms, wherein in the first case R ₁₀ denotes a hydrogen atom and R ₂ denotes a hydrogen atom or a lower alkyl group, and in the second case R ₉ denotes a hydrogen atom and R ₁ denotes a hydrogen atom, a lower alkyl group or an acyl group, and R ₁₁ denotes a hydrogen atom or a lower alkyl group,

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or a ring of the formula

V = <.X

^R 10

means in which R ₁ ', R ₂ , Rq »Rio ¹ ^ ^R n have ^the meanings given above and X""is an anion derived from an inorganic or organic acid, such as a halide, fluoborate, perchlorate, sulfate, bisulfate or acetate means, where the diazamerocyanines and the diazamerocyanine salts of the formula (I) can also be present in a mesomeric form of the formula (I).

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

The concentration of the dyestuffs of the formula I in the colorants according to the invention can be reduced due to their great affinity Connections for keratin fibers vary within wide limits. This concentration is generally between 0.001 and 0.5 wt%. .

The pH of the agents according to the invention is in general between 3 and 8. It is prepared by adding an acid such as orthophosphoric acid or acetic acid, or a base such as Triethanolamine or ammonia, to the desired value.

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The agents according to the invention can only contain dyes of the formula (I), in which case it is applied to the hair reflective nuances that range from yellow to blue across the entire light spectrum.

However, the agents according to the invention can also contain other direct dyes, for example azo or anthraquinone dyes, Contain nitro dyes of the benzene series, indoanilines, indophenols or indamines.

They can also be various commonly used in cosmetics auxiliaries used, such as wetting agents, dispersants, swelling agents, penetrants, emollients or Perfumes included. They can also be conditioned in aerosol containers.

The coloring human hair with the aid of the colorant according to the invention is carried out in the usual manner by applying the _v agent to the hair, with which one, leaves it for a period of time varying from 3 to 30 minutes in contact, after which the hair is rinsed and, optionally, washed and dries.

The present invention also relates to hair lotions, which are characterized in that they are divided into aqueous alcoholic: Solution containing at least one cosmetic resin and at least one compound of the formula (i) as defined above.

The Wasserwellotions invention generally contain 20 to 70 wt .-% alcohol with a low molecular weight, and 1 to 3 wt -.% Cosmetic resin.

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The cosmetic resins that are included in these water wave lotions include polyvinylpyrrolidone, the crotonic acid / Vinyl acetate copolymers, the vinyl pyrrolidone / vinyl acetate copolymers, maleic anhydride / butyl vinyl ether copolymers, etc. These resins are used in an amount of 1 to 3% by weight.

The low molecular weight alcohols suitable for making the water wave lotions of the invention are preferably ethanol and isopropanol.

■ r -

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 only contain dyes of the formula (I), in which case they represent what is traditionally referred to as nuanced agents. However, you can also use other direct dyes, such as contain the aforementioned. They can also contain aids such as those mentioned above.

The water wave lotions according to the invention are applied in the usual way to the moist, previously washed and rinsed hair, which is then rolled up and dried.

The dyes of the formula (I) can also be used in the form of hair lacquers} * which are characterized in that they contain at least one cosmetic resin in alcoholic solution and contain at least one compound of the formula (I).

The alcohols used in the paints of the invention are low molecular weight alcohols such as ethanol or isopropanol.

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The cosmetic resins used can be as mentioned above. They are used in an amount from 1 to 3 wt. 96 used.

Among the dyes of the formula (I) defined above are a certain number of new compounds which are also Are part of the present invention.

Consequently, the present invention also relates to the new Diazamerοcyanine and the Diazamerocyaninsalze of the formula (I ')

A = N-N = B '(I «)

wherein A is a nitrogen heterocycle as described above and B 'represents a radical corresponding to one of the following formulas

^R l

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11

R,

or

wherein

X "see an anion derived from an inorganic" öderj Örganischfeh Acid, such as a ^ halide, fluoborate, perchlorate, sulfate, bisulfa or acetate, R ^ e.in hydrogen atom. "or a lower alkyl radical, R-2 is a hydrogen atom, a lower alkyl radical, which is optionally is substituted by an amine or amide radical, or a group

- C - R «

Il

where X is an oxygen atom or a sulfur atom and R ' mean an amino group or a lower alkyl radical,

-9 -

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R ^ and R ^ each a hydrogen atom or a lower alkyl radical,
Y a remainder

= N - R't or = N

where R ^ and RV ₂ each represent a hydrogen atom or a lower alkyl radical and Z "an anion derived from an 'inorganic or organic see" acid, like a, halide, fluoborate, perchlorate, sulfate, bisulfate or acetate, Rfj is a hydrogen atom or group

- C - R ¹

II

where W is an oxygen or sulfur atom and R ^{1 is} an amino group or a lower alkyl radical,

Rg and Ry, which can be the same or different, denote a hydrogen atom, a lower alkyl radical or a methoxy group, where, however, Ry denotes a hydrogen atom when R ¹ - ^, R ' ₂ and R, - denote hydrogen atoms,

Rq and R ₁₀ together with the nitrogen and carbon atoms to which they are attached form a saturated or unsaturated heterocycle which may contain another _{hetero atom, in which case R n is} hydrogen and R _{11 is} hydrogen or a lower alkyl radical, or Rq and R ₁₁ together with the nitrogen and carbon atoms to which they are bonded form a saturated or unsaturated hetero cycle which may contain another heteroatom, in which case Rg is a hydrogen atom and R-, q is a hydrogen atom, a lower alkyl radical or an acyl group, it being possible for these new compounds to ^{exist in a mesomeric form of the formula (I 1} ).

- ¹⁰ - ■

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The new compounds according to the invention are made by processes known per se by condensation of a hydrazone. general formula (II ¹ )

.A = N-NH ₂

in which A has the meanings given above, with a coupler corresponding to one of the formulas below

EAR

• ^{8 R} io

^R 9

- 11 -

209851/1212

wherein Y ^{1 is} a residue

or - NH

■ ^ R

and the radicals R ₁ to R- ^ ₁ and R ¹ - ^, R ^f ₂ and Z have the meanings given above, in the presence of an oxidizing agent such as Hydrogenρeroxyd, an alkali persulfate, an alkali chlorite, potassium ferricyanide or iron III chloride at a temperature between 15 and 70 ⁰ C, either in an alkaline medium or in acidic medium, .if it is desired to obtain a compound having a quaternary ammonium group prepared. The acid used can be the acid corresponding to the desired salt or another acid, in which case, after the condensation reaction, a salt of the acid corresponding to the desired diazamerocyanine salt is added to the reaction medium, which is more water-soluble than the said diazamerocyanine salt, which is then isolated by filtration will.

The following examples are intended to further illustrate the invention, but not to limit it in any way. Temperatures are given in ^0C.

The terms lower alkyl and lower alkoxy used in describing the present invention denote radicals with 1 to 4 carbon atoms. Acyl groups mean aliphatic acyl groups with 2 to 5 carbon atoms. If at the Description of the invention by "alkylated" or "acylated" the When talking about it, it is also a matter of residues as defined above.

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example 1

Preparation of 3-methyl-2,3-dihydro-2: 4'-azino-benzothiazole-3'-amino-6 * -methyl-1'-oxo-1 ', 4'-dihydro-benzene

To a solution of 1.80 g of 3-methyl benzothiazolone hydrazone (0.01 mol) in 100 cnr ⁵ 50% alcohol is added successively a solution of 1.60 g (0.01 mol) of 3-amino- 6-methyl.-phenol in 50 ens? 50% alcohol and 5 cnr ⁵ with ammonia 22 ⁰ B. and keeping the mixture at 30 unter_Rühren ⁰ C, were then added to a solution of 2.28 g ammonium persulfate in 20 cm 50% alcohol. The mixture is stirred for a further 30 minutes, then the precipitate obtained is filtered off with suction, washed with water and dried over phosphoric anhydride.

The dye is in the form of a red-brown solid with a melting point above 260 ° b.

Molecular weight, determined by potentiometric titration 297 (theory 298).

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Example 2

222721A

Preparation of 3-methyl-2,3-dihydro-2: 4'-azino-benzothiazole-2 ', 6'-dimethyl-1'-oxo-1 ', 4'-dihydro-benzene

CH.

CH

The procedure is identical to that described in Example 1. The dye is obtained in the form of a bright red solid with a melting point of 236 ^° C.

Molecular weight determined by potentiometric titration 300 (theory 297).

Example 3

Preparation of 3-methyl-2,3-dihydro-2: 4 ^f -azino-benzo ^ thiazole-3'-acetamino-6'-methyl-1'-oxo-1 ', 4'-dihydro-benzene

CH. ·

»A. _N J N =

NHCOCH,

- 14 -

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The procedure is identical to that described in Example 1. An orange-red product with a melting point above 260 ° is obtained.

Molecular weight determined by potentiometric titration 350 (theory 340).

Example 4

Preparation of 3-methyl-2,3-dihydro-2: 4'-azino-benzothiazole-3'-amino-2 ·, 6 · -dimethyl-I'-oxo-1 ', 4'-dihydro-benzene

NH ₂ CH ₃ .

The procedure is identical to that described in Example 1. A brown product is obtained with an F = 250 °.

Molecular weight determined by potentiometric titration: 321 (theory: 312).

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Example 5

Preparation of 3-phenyl-4-methyl-2,3-d.ihyd.ro-2: 4 -azino-thiazof 1 ', 4'-dihydro-1'-oxo-2 "-naphthanilide

CONHC H l 6

The method of operation is identical to that described by S. Hünig in "Liebigs Annalen der Chemie" Volume 647, page 77 ».

A red product is obtained. F = 238 °.

Example 6

Preparation of 3,4-diphenyl-2,3-dihydro-2: 4'-azino-thiazol-1 ^f, 4'-dihydro-1'-oxo-2'-naphthanilide

CONHC.H ο

The procedure is identical to that of Example 5. A red product is obtained. F = 240 °.

- 16 -

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Example 7

22272U

Production of 2 - [(l-dimethylaminophenyl (4)) azo] -3 methyl benzothiazolium perchlorate.

CH,

ClO, -

The method of operation is identical to that described by S. Hünig in "Liebigs Annalen der Chemie", volume 628, page 88

A green shimmering product is obtained. F = 230 °.

Example 8

Preparation of 1,3-dimethyl-2 [(l-dimethylaminophenyl- (4)) azo] imidazolium perchlorate

CH.

CH,

ClO ₄ -

The method of operation is identical to that of S. ^ Hünig in "Liebigs Annalen der Chemie", Volume 628, page 90, described

A green shimmering product is obtained. F = 242 °.

- 17 -

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Example 9

Preparation of 2 - [(1,3-diamino-6-methyl-phenyl- (4)) azo] -3 methyl benzothiazolium iodide

CH,

I / γ

■ NH "J ^c

NH ₂

1.80 g of N-methylbenzothiazolone hydrazone are dissolved in 160 liters of hydrochloric acid, to which 10 mg of iron (II) sulfate are added. 1.22 g of m-toluenediamine are added, followed by 2.5 cm ^{-3 of} 30% strength hydrogen peroxide with stirring. The mixture is stirred for half an hour at 30 ⁰ C, then outputs it to 10 cnr formic acid. The mixture is heated to 70 ^° C. It is filtered off. 2.2 g of potassium iodide are added to the filtrate. It is allowed to cool, the precipitate is filtered off with suction, washed with water and dried over phosphoric anhydride.

The dye is obtained in the form of a red-violet solid. F = 180 ° (decomp.).

Example 10

Preparation of 2 - [(1,3-diamino-2,6-dimethyl-phenyl- (4)) azo] -3-methyl-benzothiazolium iodide

- 18 -

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f ^ x ~ -

N = N ^ \ NH ₂ ?

CH

The procedure is identical to that described in Example 9

The dye is isolated in the form of a red-violet solid. F = 170 ° (dec).

Example 11

Preparation of 3-methyl-2,3-dihydro-2: 4 ^l -azino-benzothiazole-1'-phenyl-3'-methyl-4-ylidene-5'-pyrazolone

1.80 g of N-methyl-benzothiazolone-hydrazon'in 200 cnr are dissolved 50% methanol. A solution of 1.74 g of 1-phenyl-3-methyl-5-pyrazolone is added in 50 cnr 50% methanol and gives

- 19 -

2 0 9 8 Γ, 1/1 2 1 2

^{M / 12029} \ 22272H

then with stirring a solution of 14.5 g of potassium ferricyanide in a mixture of 100 cnr 50% methanol and 10 cnr 25 % ammonia. The mixture is stirred for 1/2 hour, then 300 cnr of water are added. The precipitate is filtered off with suction, washed with water and dried over phosphoric anhydride. The dye is obtained in the form of an orange-red solid. F = 262 °.

Example 12

Production of 1,3-dimethyl-2,3-dihydro-2: 4 ^! -azino-benzimidazole 1'-phenyl-3J-methy1-4'-yliden-5'-pyrazolone

The procedure is identical to that described in Example 11.

The dye is isolated in the form of an orange-red product. F = 268 °.

- 20 -

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Example 13 .

Preparation of 1,2-dimethyl-2,3-dihydro-2: 4 ^f -azino-indazol-1 · -phenyl-3'-methyl-4'-yliden-5 ^! -pyrazolone

/ ^CH 3

ν / Ν; η.

^C 6 ^H 5

The procedure is the same as that described in Example 11 " identical.

The dye is obtained in the form of a brown-orange-colored product. F = 264 °.

Molecular weight, determined by potentiometric titration: 348 (theory 346).

Example 14

Preparation of 4-methyl-3-phenyl-2,3-dihydro-2: 4'-azino-thiazo 1'-phenyl-3'-methyl-4'-yliden-5'-pyrazolone

- 21 -

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• M / 12029 _Ä 22272H 15th Dye in the form of a dark purple solid
O
• The procedure is the same as that described in Example 11
identical. An orange-colored product is obtained. F = 232 °. 1-methyl-1,4-dihydro-4: 4 -azino-pyridine-
'-oxo-benzene 16 example - N "N = N -N = VV ^ ₀ 1-methyl-1,4-dihydro-4: 4'-azino-pyridine
^1- oxo-naphthalene Production of
1 », 4'-dihydro-l The working method is the same as that of S. Hünig in "Liebigs Annalen
der Chemie ", Volume 636, page 27, described identically. CH - NV = NN - = / YO
\ · ■ '■ > /. \ / CH ₃ - You get the
Fabric. F = 213 - 22 - example Production of
l ', 4'-dihydro-l -

209851/1212

The procedure is the same as that of S. Hünig in "Liebigs Annalen der Chemie ", Volume 636, page 28, described identically.

The dye is obtained in the form of a green shimmering solid. F = 225 °. '

Example 17

Preparation of l, 2-dimethyl-2,3-dihydro-3: 7 ^l -azino-indazole-6'-oxo-6 ', 7'-dihydro-benzomorpholine'

N-N- / Λ N - H

2.12 g of 2-dimethyl-2-indazolone hydrazone hydrochloride are dissolved in 80 cm ^{5 of} water. At ordinary temperature, a solution of 1.51 g of 6-hydroxy-benzomorpholine in 80 Priority cn? Of water, were then added over 15 minutes with stirring a solution of 4.56 g ammonium persulfate and 12 cnr with ammonia 22 ⁰ B to. Man. . stir for a further 30 minutes, filter, wash with cold water and dry the resulting precipitate over phosphoric anhydride. The product obtained is a brown-red dye. F = 230 °.

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Example 18

22272H

Preparation of 1,3-dimethyl-1,2-dihydro-2: 7-azino-benzimidazo-6'-oxo-6 ', 7'-dihydro-benzomorpholine

describe

The procedure is identical to that in Example. The dye is obtained in the form of a brown solid with green shimmer. F = 184 °.

Molecular weight found:

Molecular weight, calculated:

Example 19

Preparation of 3-methyl-2,3-dihydro-2: 7'-azino-benzothiazole-6 ^f -oxo-6 ^! , 7'-dihydro-benzomorpholine

■ Λν -

CH,

The procedure is identical to that described in Example 17. The dye is obtained in the form of a brown Solids, mp = 195 °.

- 24 -

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Example 20

Preparation of 7 '- (6'-Hydroxy-benzomorpholine) -2-aza-3-methylbenzothiazolium chloride

N -N

Cl ", 1.5

2.52 g (0.01 mol) of N-methylbenzothiazolonhydrazone dihydrochloride and 1.51 g (0.01 mol) of 6-hydroxy-benzomorpholine are dissolved in 200 cnr in HCl, then 26 cnr 28% FeCl are added over 45 minutes -z dissolved in 24 enr water, too. The mixture turns purple and a precipitate forms. After a reaction time of 15 minutes, it is filtered off and dried in vacuo over phosphoric anhydride. The chloride thus obtained is purified by dissolving it in dimethylformamide and reprecipitating it with water. F = 225 ⁰ C (dec.)

Analysis: C. H N calculated: 49.3, 4.62 14.12 % found: 48.66 3.87 14.35 % 48.66 3.99 14.51 %

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Example 21

22272H

Preparation of 7 ^I - (6-hydroxy-benzomorpholine) -2-aza-3-methylbenzothiazolium perchlorate

This compound is obtained by dissolving the chloride prepared in Example 1 in acetic acid and reprecipitating with sodium perchlorate.
F = 240 ⁰ C (dec.)

Analysis: • .. c. H N calculated: 42.40 3.97 12.37 found: 42.69 3.62 12.43 42.46 3.68 12.55

Example 22

Preparation of 7 '- (6'-Hydroxy-benzomorpholine) -2-aza-4-methyl-3-phenyl-thiazolium perchlorate

N = N

, 1.5

3.45 g (0.01 mol) of 4-methyl-3-phenyl-thiazolonobenzenesulfonylhydrazone are dissolved and 1.51 g (0.01 mol) of 6-hydroxy-benzomorpholine in 100 cnr of crystallizable acetic acid, then added Approximately 2.28 g (0.01 mol) of ammonium persulfate dissolved for 15 minutes

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in 10 cm of water. The solution takes on a purple color

at. The mixture is stirred for 30 minutes, then 5 g of sodium perchlorate are added, dissolved in 20 cnr water. The mixture is stirred for 1 hour, then filtered off and dried in vacuo over phosphoric anhydride.

The product is purified by dissolving it in dichloroethane, filtering off the insoluble materials and reprecipitating it with carbon tetrachloride. A powder with a green sheen is obtained in this way. P = 230 ⁰ C.

Analysis: • .. Ρ H N calculated: 45.04 4.17 11.68 found: 45.18 4.07 11.69 44.70 3.94 11.84

Example 23

Production of 7 ^t - (6 ^t -hydroxy-benzomorpholine) -2 ~ azo-3,4-diphenyl-thiazolium perchlorate

N = N

■ HO

ClO ₄ , 0.5

1.33 g (0.005 mol) of 3,4-diphenyl-thiazolone hydrazone are dissolved and 0.75 g (0.005 mol) of 6-hydroxy-benzomorpholih in 50 cm ^ crystallizable acetic acid. 2.28 g (0.01 mol) of ammonium persulfate, dissolved in 10 cm ^ of water, are added over a period of 30 minutes.

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to. An intense purple color appears. The mixture is stirred for 30 minutes, then 2 g of sodium perchlorate, dissolved in 10 cnr of water, too. It is filtered off, washed with water and dried in vacuo over phosphoric anhydride.

The product is purified by dissolving it in dichloroethane and precipitating it with carbon tetrachloride, and thus crystals with a green sheen are obtained. F = 170 ⁰ C.

Analysis: C. 75 H 82_J N 7 % calculated: "- 52, 57 3, 38 10, 05 % found: • 52, 60 4, 10 10, 29 % 52, 4, 10,

Water determination according to Karl Fischer, 1.5 %.

Example 24

Preparation of 7 '- (6'-Hydroxy-benzomorpholine) -2-azo-1,3-dimethyl-benzimidazolium perchlorate

.ch "

N-N

ClO,

10 g (0.04 mol) of N, N'-dimethyl-benzimidazolone-hydrazone-i are dissolved dihydrochloride and 6.04 g (0.04 mol) 6-hydroxy-benzomorpholine

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in 250 cm ^{5 of} acetic acid. Give 30 g. Sodium acetate dissolved in 100 cubic centimeters of acetic acid, then about 18.24 g (0.08 mol) of ammonium persulfate dissolved in 100 cubic centimeters of water over 30 minutes. After a reaction time of 30 minutes, the inorganic salts are separated off by filtering off and the product is precipitated by adding 20 g of sodium perchlorate, dissolved in 300 ml of water. 9 g of product are obtained, which corresponds to a yield of 70 % , which is purified by extraction with methanol and concentration. F = 24O ⁰ C.

Analysis of C-IyH-IgNcO ₂ -T

C H

calculated: 48.2 4.2

found: 48.6 4.6

Example 25

The following dye is made:

Vinylpyrrolidone-vinyl acetate copolymer 3 g

Ethyl alcohol 50 cm ³ triethanolamine as much as necessary for pH 5 dye according to Example 8 0.100 g

Water as much as necessary for 100 cnr

If you bring this water wave lotion to medium brown colored Hair on, so it gives it a particularly beautiful brown-red shade.

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3D

Example 26 The following colorant is prepared:

Vinyl acetate-crotonic acid copolymer 2 g

Ethyl alcohol 50 cnr ⁵

Benzylidene camphor 0.2 g

Triethanolamine, as much as necessary for pH 7

Dyestuff according to Example 7 0.1 g

Water as much as necessary for 100 cnr

If you apply this water wave lotion to dark blonde colored hair, it gives it a very shiny appearance As chs chimmer.

Example 27

The following dye is made:

Vinyl pyrrolidone-vinyl acetate copolymer

Ethyl alcohol

200 volumes of hydrogen peroxide

Orthophosphoric acid as much as needed for

Dye according to Example 7

Water as much as needed for

This lotion is applied to naturally light brown hair. After the water wave and drying, the hair is light brightened and have a particularly beautiful mother-of-pearl shimmer,

- 30 -

2 G 3 50 cnr 0012 g 5 G cm pH .0, 100

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Example 28_ '''^;' ^:

The following dye is made:

Ethyl alcohol 50 cm ³

Hydrogen peroxide with 200 volumes of 5 g

Orthophosphoric acid as much as necessary for pH 3

Dyestuff according to Example 7 0.0015 g

■ z.

Water as much as necessary for 100 cnr

This lotion is applied to naturally dark blonde hair. After the water wave and drying, the hair is light lightened and have a very nice pink ash shimmer.

Example 29

The following dye is made:

Vinyl acetate-crotonic acid copolymer 2 g

Ethyl alcohol

200 volumes of hydrogen peroxide

Orthophosphoric acid as much as needed for

Dye according to Example 1 Dye according to Example 8 Water as much as needed for

This lotion is applied to naturally blonde hair. After the water wave and drying, the hair is lightened and have a particularly beautiful shade of ash blonde with a mother-of-pearl shimmer.

- 31 -

55 cm 3 G 5 G 0006 G pH 0006 O, cm O, 100

? 0 9 H ', 1/1 2 1 2

M / 12029 222721A 2 g - 32 - i with silver Example 30 50 cm ³ The following dye is made: pH 7 Vinyl pyrrolidone-vinyl acetate copolymer 3 g 0.005 g Dye according to Example 4 0.03 g 0.01 g Dye according to Example 1 0.1 g 0.001 g Alcohol at 96 ° as much as required for 100 cm ³ 100 cm ³ If you spray this solution as a varnish, it gives you i
If you apply this lotion to freshly bleached hair, so naturally blonde hair has a very shimmering gold sheen. it gives them a very light blonde shade Example 31 Shine. The following dye is made: Vinyl pyrrolidone-vinyl acetate copolymer Ethyl alcohol Triethanolamine as much as needed for Dye according to Example 11 Dye according to Example 1 Dye according to Example 8 Water as much as needed for

2098 5 1/1212

Example 32.

The following dye is made:

Butyl cellosolve. 8g

Propylene glycol -8g

■ Alkylphenolpolyäthoxyäther, from the company

GERLAND under the trade name

"REMCOPAL 334" sold 22 g

Alkylphenolpolyäthoxyäther, from the company "

GERLAND under the trade name

"REMCOPAL 349" sold 22 g

Ammonia with 22 ⁰ B 8g

Compound according to Example 17 0.096 g

Water as much as necessary for 100 g

20 g of hydrogen are added to 20 g of the solution thus prepared peroxide with 20 volumes. A gel is obtained which after 10 minutes of action on bleached hair, this one very gives a luminous beige shade with a mother-of-pearl shimmer.

Example 33

The following dye is made:

Butyl cellosolve 8 g

Propylene glycol 8 g

Alkylphenol polyethoxyether from Finna GERLAND

sold under the trade name "REMCOPAL 334" 22 g Alkylphenolpolyäthoxyäther, from GERLAND

under the trade name "REMCOPAL 349" - sold 22 g

Ammonia with 22 ⁰ B 10 g

Compound according to Example 17 0.2g

Water as much as necessary for 100 g

- 33 2 0 9 8 5 1/1212

M / 12029 * 2227214 8 g 2.0 g It is added to 20 g of the solution thus prepared 20 g water .. 8 g 50 cm- ⁵ A gel is obtained that lasts for 15 minutes medium brown 22 g pH 7 Hair applied, this a mahogany colored after rinsing 22 g 0.010 g Gives nuance. 0.050 g 100 cnr ⁵ Example 34 100 g Mari makes the following dye: 20 g of water. Butylcellosolve .. previously discolored Propylene glycο1 Hair applied, this an iridescent shade of blonde ver Alkylphenol polyethoxyether, from the company
GERLAND under the trade name
"REMCOPAL 334" sold borrows. Alkylphenol polyethoxyether, from the company
GERLAND under the trade name
"REMCOPAL 349" sold Example 35 Compound according to Example 8 The following water wave lotion is produced: Water as much as needed for Vinyl pyrrolidone-vinyl acetate copolymer It is added to 20 g of the solution thus prepared Ethyl alcohol A gel is obtained that lasts for 10 minutes Triethanolamine, as much as needed for Dye according to Example 20 Water as much as needed for - 34 -

209851/1212

M / 12029. 22272 TA

Applied to blonde dyed hair, this lotion gives it a golden shimmer with a particularly beautiful effect.

Example 36

The following dye is made:

Viny! Pyrrolidone-vinyl acetate copolymer 2.0 g Ethyl alcohol 50 cm ^

Triethanolamine as much as necessary for pH 7 dye according to Example 22. 0.012 g

Water as much as necessary for 100 g

If you apply this water wave lotion to bleached hair, it gives it a particularly shiny rose gold blonde Nuance.

Example 57

The following water wave lotion is produced:

Vinylpyrrolidone-vinyl acetate copolymer 2.0 g Ethyl alcohol 50 cnr

Triethanolamine as much as required for pH 7 dye according to Example 24 0.010 g

Water as much as necessary for 100 cnr

Applied to hair dyed golden blonde, this lotion gives the hair a particularly shiny and beautiful look Mother-of-pearl shimmer.

- 35 -

2098 ^ 1/1212

M / 12029 2 2 2 7 21A

Example 38 ■ _;

The following dye is made:

Vinylpyrrolidone-vinyl acetate copolymer 2.0 g

Ethyl alcohol 50 cm ^ triethanolamine as much as necessary for pH 8

Dyestuff according to Example 23: 0.015 g

Water as much as necessary for 100 cnr

Applied to bleached hair, this lotion gives a very luminous light blonde shade with a pink shimmer.

Example 39

The following water wave lotion is produced:

Vinyl acetate-crotonic acid copolymer 2.0 g

Ethyl alcohol. _γ , 50 cnr

Benzylidene camphor 0.2 g

Triethanolamine as much as required for pH 7

Dyestuff according to Example 7 0.70 g

Dye according to Example 22 0.01 g

If you apply this lotion to dark blonde colored hair, it gives it a very bright ash-colored mother-of-pearl shimmer.

209851/1212

M / 12029 2227214 50 cm ³ 0.012 g. Example 40 •
The following dye is made: 0.010 g • Vinyl pyrrolidone-vinyl acetate copolymer 2.0 g Ethyl alcohol 50 cm ³ 0.002 g Triethanolamine as much as needed for pH 7 100 cm ³ Dye according to example 22 ' 0.010 g If you bring this agent to severely discolored ones for 20 minutes N - [(4 ^I -amino-2'-methoxy-3 ', 5'-dimethyl) -phenyl] - Hair on, so it gives them a particularly beautiful one 2,5-dimethyl-benzoquinoneimine 0.010 g
• -j gold-apricot-colored shade. Water as much as needed for 100 cm ^ - 37 - If you apply this water wave lotion to light blonde hair, so she gives them a particularly beautiful shimmering mother-of-pearlc Asnuance. Example 41 The following dye is made: Ethyl alcohol Dye according to Example 24 N - [(4'-hydroxy) phenyl] -3-amino-6-methyl- b enzo quinonimine N - [(4 ^l -amino-2 ^l -methoxy-3 ^l , 5'-dimethyl) -phenyl] - 2,6-dimethyl-benzoquinoneimine Water as much as needed for

2 0 9 8 51/1212

M / 12029 22272H 2.0 g 50 cm ³ Example 42 pH 7 The following dye is made: 0.2 g Vinyl pyrrolidone-vinyl acetate copolymer 2.0 g 0.006 g Ethyl alcohol 50 cnr 0.004 g Triethanolamine as much as needed for pH 7 Dye according to Example 20 0.005 g 0.001 g Dye according to Example 24 0.005 g N - [(4'-Hydroxy) phenyl] ^ - amino-e-methyl- 0.005 g benzoquinone imine 0.0025 g 100 approx? N - [(4 ^l -amino-2'-methoxy-3 ^l , 5'-dimethyl) -phenyl] - 2,5-dimethyl-benzoquinoneimine 0.001 g Water as much as needed for 100 cm ³ If you apply this water wave lotion to blonde hair, so it gives them a particularly beautiful mother-of-pearl shimmer. Example 43 The following water wave lotion is produced: Vinyl pyrrolidone-vinyl acetate copolymer Ethyl alcohol Triethanolamine as much as needed for Benzylidene camphor Dye according to Example 24 Dye according to Example 22 N - [(4'-hydroxy) phenyl] -3-amino-6-methyl- b enzo quinonimine N - [(4'-Amino-2'-methoxy-5'-methyl) -phenyl] - 3-acetylamino-6-methyl-benzoquinone imine Water as much as needed for - 38 -

209851 / ^ 212

M / 12029 & 22272H

Applied to naturally very light blonde hair, this lotion gives it a very luminous ash-mother-of-pearl shimmer. Example 44 ...... '

The following water wave lotion is produced:

Vinylpyrrolidone-vinyl acetate copolymer 2.0 g

Ethyl alcohol 50 cnr

Triethanolamine as much as required for pH 6

Dye according to Example 23 0.007 g of N- (4'-amino-2'-methoxy-3 ', 5'-dimethyl) -phenyl-

2,5-dimethyl-benzoquinoneimine 0.003 g of N- (4-hydroxy) -phenyl-2,6-dimethyl-benzoquinoneimine - 0.003 g

• 7.

Water as much as necessary for 100 cnr

If you apply this water wave lotion to light blonde colored hair, it gives it a very beautiful ash and mother-of-pearl shimmer.

Example 45

The following dye is made:

Vinylpyrrolidone-vinyl acetate copolymer 2.0 g

Ethyl alcohol

Triethanolamine as much as necessary for the dye according to Example 22. _% - ·

Nitrο-p-phenylenediamine

Water as much as needed for ~

If you apply this water wave lotion to light brown colored hair, it gives it a particularly beautiful gold copper shimmer.

- 39 -

60 cm , 010 G pH 9 , 010 G O ₁ cnr 0, 100

209851/1212

M / 12029 22272U Example 46 The following dye is made: 2.0 g Crotonic acid / vinyl acetate copolymer 70/30 50 cm ³ Ethyl alcohol pH 6 Triethanolamine as much as needed for 0.010 g Dye according to Example 22 0.010 g Dye according to Example 23 4-methyl-8-di-ß-hydroxyethylamino [2,3-b] -. 0.010 g morpholino-phenoxazonium bromide 100 cm ³ Water as much as needed for discolored If you apply this agent as a water wave lotion them this and dark brown dyed hair on, so gives a very luminous ash-blue shimmer. 1.
- 40 -

209851/1212

Claims (2)

M / 12029 22272H claims 1. Colorant for human hair, characterized in that it is in aqueous or aqueous-alcoholic solution, which has a pH between 3 and 8, 0.001 to 0.5% by weight at least one diazamerocyanine or a diazamerocyanine salt the formula A = NN = B
contains - ■ wherein A is a nitrogen-containing heterocycle with 5 or 6 ring members of the formula or (II) (III) denotes where R is a lower alkyl group having 1 to 4 carbon atoms or an optionally substituted phenyl group, and X is an oxygen or sulfur atom, a group NR ^f , where R ^{1 is} a lower alkyl group, a group -CH ₂ -, which is optionally with one or two lower alkyl radicals is substituted, an ethylene radical or a radical -C = N-, R " wherein R "represents a hydrogen atom or a lower alkyl radical, - 41 - 209851/1212 Z is an ethylene radical or a radical -NR " ¹ , in which R ¹ " is a lower alkyl radical, Ry denotes a hydrogen atom, a lower alkyl group or a phenyl group, Rg denotes a hydrogen atom or a lower alkyl group, or Ry and R _Q together with the carbon atoms to which they are bonded form a condensed benzene ring, which may optionally be substituted with one or more halogen atoms or alkyl, Substituted alkoxy or nitro radicals B denotes a nitrogen-containing heterocycle with 5 or 6 ring members, which optionally contains other heteroatoms and "_ is not identical to the heterocycle according to definition A, or a ring of the formula (IV) (IV) wherein Y is an oxygen atom or a radical = N t R ₂ means in which - 42 - 209851/1212 M / 12029 R _{1 and} R ₂ each represent a hydrogen atom, a lower alkyl radical or a phenyl radical and Z "denotes an anion derived from an inorganic or" organic acid, R ^, R ^ and Rg each represent a hydrogen atom, a lower alkyl or lower alkoxy radical 1 to 4 carbon atoms, whereas R ^ denotes a hydrogen atom or an amino radical which is optionally alkylated or acylated, _H ■ or a ring of the formula (V) (V) wherein R ₁ and Rq, together with the nitrogen and carbon atoms to which they are attached, form a heterocycle with 5 or 6 ring members, which may be saturated or unsaturated and may comprise another heteroatom, in which case R _{10 is} a hydrogen atom and R ₂ denotes a hydrogen atom or a lower alkyl radical, or R ₂ and R ₁₀ , together with the nitrogen and carbon atoms to which they are bonded, form a heterocycle with 5 or 6 ring members, which can be saturated or unsaturated and contain a further heteroatom, in which case Rg represents a hydrogen atom and R-, * represents a hydrogen atom, a lower alkyl radical or an acyl radical, and R _{11 represents} a hydrogen atom or a lower alkyl radical, - 43 - 209 8-1 / 1212 M / 12029 or a ring of the formula EAR denotes in which R ₁ , R ₂ , Rq, R ₁₀ ¹ ^ ^R u have ^the meanings given above and and X "denotes an anion derived from an inorganic or organic acid, these compounds being in a mesomeric form of the formula (I. ) may exist. 2. Composition according to claim 1, characterized in that it is a low molecular weight alcohol such as ethanol or isopropanol. 3. Agent according to claim 1, characterized in that there are other direct dyes, such as azo dyes, anthraquinone dyes, Contains nitro dyes of the benzene series, indoanilines, indophenols or indamines. 4. A method for dyeing human hair, characterized in that a dye is applied to the hair to be dyed according to one of claims 1 to 3, the agent is allowed to act for a period of time between 3 and 30 minutes, and then rinses the hair, washes it if necessary, and dries it. - 44 - 2 0 9 8 5 1/12 12 5. Composition according to claim 1, which is a hair tonic wave lotion represents, characterized in that it is divided into aqueous alcoholic | r Solution contains at least one cosmetic resin. 6. .Means according to claim 5, characterized in that it contains 20 to 70% by weight of a low molecular weight alcohol. 7. Means according to. Claim 6, characterized in that the low molecular weight alcohol or ethanol Is isopropanol. 8. Agent according to one of claims 3 to 7, characterized in that that it contains 1 to 3% by weight of cosmetic resin. 9. Agent according to one of claims 3 to 8, characterized in that that the cosmetic resin polyvinylpyrrolidone, a crotonic acid-vinyl acetate copolymer, a vinylpyrrolidone-vinyl acetate copolymer or maleic anhydride-butyl vinyl ether copolymer is. .10. Agent for hair lacquers, characterized in that it in alcoholic solution at least one cosmetic resin and at least one diazamerocyanine or one diazamerocyanine salt, as defined in claim 1. - 45 - 209851/1212 M / 12029 2 2 2 7 21 A 11. Means according to claim 10, characterized in that it 0.001 to 0.5 wt .-% diazamerocyanine or Diazamerocyaninsalζ contains. 12. Agent according to one of claims 10 and 11, characterized in that the alcohol it contains is an alcohol is of low molecular weight. 13. Agent according to claim 12, characterized in that the alcohol is ethanol or isopropanol. 14, means that it contains any one of claims 10 to 13, characterized in that 1 to 3 ^'G e \ t .-% cosmetic resin. 15. Agent according to one of claims 10 to 14, characterized in that the cosmetic resin is polyvinylpyrrolidone, a crotonic acid-vinyl acetate copolymer, a vinylpyrrolideqn Vinyl acetate copolymer or maleic anhydride-butyl vinyl ether copolymer is. 16. .New compounds of the general "formula (I ¹ ) A = NN = B ¹ (I ») - 46 - 209851/1212 M / 12029 . 22272U B ^{1 is} a remainder corresponding to a S. 0 ^L 7 wherein A is a nitrogen-containing heterocycle 'as in claim' represents 9 1 defines, means and ^R 2 -. ^R 4 EAR
V = NX
^R 9 of the formulas below NHR
I ⁵ - 47 - ■ ■. ^R i
N Q "■ I.
R ₅ E * or - = ^ 2098 F, 1/1212 M / 12029 * 222721A X "is an anion derived from an inorganic or organic one Acid, Rj is a hydrogen atom or a lower alkyl radical, R £ is a hydrogen atom, a lower alkyl radical, which optionally is substituted with an amine or amide radical, or a group - C - R ' t! in which X is an oxygen atom or a sulfur atom and R ^{1 is} an amino group or a lower alkyl radical, Rx and R ^ are each a hydrogen atom or a lower alkyl radical,
Y a remainder ₊ / ^Rt i = N - R'j or = N Z ~ " R «2 where R '- ^ and R * £ each represent a hydrogen atom or a Lower alkyl radical and Z "an anion derived from 'an"' inorganic or "organic acid", mean Rc is a hydrogen atom or a group -C-R 'W where W is an oxygen or sulfur atom and R 'is Mean amino group or a lower alkyl radical, 48 - 2 0 9 BB 1/1 2 1 2 «43 Rg and Rj, which can be the same or different Mean hydrogen atom, a lower alkyl radical or a methoxy group, where, however, Ry must mean a hydrogen atom if R ^, R ^f ₂ and R ^ mean hydrogen atoms, Rg and R ₁₀ together with the nitrogen and carbon atoms to which they are attached form a saturated or unsaturated heterocycle with 5 or 6 ring members, which may contain another heteroatom, in which case Rg is a hydrogen atom and R _{11 is} a hydrogen atom or a Lower alkyl radicals, or Rg and R ₁₁ together with the nitrogen and carbon atoms to which they are bonded represent a heterocycle with 5 or 6 ring members, which can be saturated or unsaturated and another. Heteroatom , "form Ϊ _in_ wela case Rg is a hydrogen atom and R ₁ Q is a hydrogen atom, a lower alkyl radical or an acyl group, these new compounds can also be in a mesomeric form of the formula (I ¹ ). 209851/1212