Oxidation hair dyes based upon tetraaminopyrimidine developers

Of great importance for the dyeing of hair are the so-called oxidation dyestuffs because of their intensive colors and very good fastness. These dyestuffs are formed by the oxidative coupling of a developer component with a coupling component. The developers customarily used are nitrogenous bases, such as p-phenylenediamine derivatives, diaminopyridines, 4-aminopyrazolone derivatives or heterocyclic hydrazones. Useful as so-called coupling components are m-phenylenediamine derivatives, phenols, naphthols, resorcinol derivatives and pyrazolones.

Good oxidation dyestuff components for hair dyeing must fulfill all of the following requirements.

They have to be able to develop a sufficient intensity of the desired color shades when oxidatively coupled with the respective developer component or coupling component. Furthermore, they have to possess a capacity for being absorbed by human hair, which capacity ranges from sufficient to very good; and in addition, they should be unobjectionable from toxicological and dermatological viewpoints.

As developers, it is customary to use the class of compounds consisting of substituted or unsubstituted p-phenylenediamines. However, this class of compounds has the disadvantage that sensitivity reactions and subsequently severe allergies are caused in numerous persons. The developers which have been recently proposed for avoiding these dermatological disadvantages are not always fully satisfactory with respect to their technical application.

An object of the invention is to provide usable oxidation hair dyes containing suitable components which optimally satisfy the above requirements.

Another object of the present invention is to provide an oxidation dyestuff combination of a coupling component and a developer component, which is based on tetraaminopyrimidines as the developer component.

These and further objects of the present invention will become apparent as the description thereof proceeds.

The present invention provides a composition and process for dyeing hair based upon an oxidation dyestuff combination of a coupling component and a developer component with tetraaminopyrimidines being the developer component, as well as novel tetraaminopyrimidines. It has now been found that the abovespecified requirements can be fulfilled to an especially significant extent by the use of hair coloring preparations that are based on oxidation dyestuff combinations containing tetraaminopyrimidines of the formula ##STR1## and their inorganic or organic water-soluble acid addition salts as developers, and containing the couplers customarily used in oxidation hair dyes, in which R 1 to R 6 are each selected from the group consisting of hydrogen, alkyl having 1 to 4 carbon atoms, aryl, substituted aryl and --(CH 2 ) n --X, in which n is an integer from 1 to 4, and X is selected from the group consisting of hydroxy, halogen and --NR 7 R 8 wherein R 7 and R 8 are selected from the group consisting of hydrogen and alkyl having 1 to 4 carbon atoms and can form with the nitrogen atom a heterocyclic ring which may contain one additional nitrogen atom or an oxygen atom. In the above formula, R 1 to R 6 likewise can designate an optionally substituted five-membered or six-membered heterocyclic ring containing one or two nitrogen atoms, or one nitrogen atom and one oxygen atom.

More particularly, the present invention is directed to an aqueous preparation for the dyeing of hair consisting essentially of (1) from 0.2% to 5% by weight of an oxidation dyestuff combination of a developer component, and a coupling component in substantially equimolar amounts, said developer component consisting essentially of (A) a tetraaminopyrimidine of the formula ##STR2## wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each selected from the group consisting of hydrogen, phenyl, alkyl having 1 to 4 carbon atoms, phenylalkyl having 7 to 10 atoms, phenylalkenyl having 7 to 10 carbon atoms,

X--(CH.sub.2).sub.n --

wherein n is an integer from 1 to 4, and X is selected from the group consisting of hydroxyl, halogen and NR 7 R 8 -- in which R 7 and R 8 are each hydrogen or alkyl having 1 to 4 carbon atoms, and together with the nitrogen atom R 7 and R 8 from a member selected from the group consisting of a 5 to 6 membered heterocyclic ring optionally containing an additional nitrogen atom or oxygen atom,

and wherein R 1 and R 2 , or R 3 and R 4 , or R 5 and R 6 , together with the nitrogen atom form a five to six membered heterocyclic ring optionally containing another nitrogen or oxygen atom in the ring and (B) a water-soluble acid addition salt of (A); (2) from 0% to 5% by weight of a direct dyestuff; (3) from 0% to 30% by weight of a surfactant; (4) from 0% to 25% by weight of thickeners; and (5) the balance up to 100% by weight of water.

A particularly preferred subgenus of the above-mentioned developer component is wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each selected from the group consisting of hydrogen, methyl, ethyl, isopropyl, n-propyl, butyl, phenyl, benzyl and benzylidene, or --(CH 2 ) n --X

wherein R 1 and R 2 , or R 3 and R 4 , or R 5 and R 6 , together with the nitrogen atom form a substituent selected from the group consisting of hydroxyl, halogen and --NR 7 R 8 in which R 7 and R 8 are each hydrogen or alkyl having 1 to 4 carbon atoms.

When the compounds according to the invention are used as developer components, they react with the known couplers generally used in oxidation hair dyestuffs to give very intensive, varying shades which previously heretofore could not be effected with these known couplers and these developers known so far. Thus, the compounds of the invention considerably increase the possibilities for utilizing oxidation hair dyes. Furthermore, the tetraaminopyrimidines according to the invention are distinguished by very good fastness of the dyeings effects with them, by good water-solubility, by good storage stability, and by excellent toxicological as well as dermatological unobjectionableness.

The tetraaminopyrimidines which are to be used as developer components according to the invention can be used either as such or in form of their water-soluble acid addition salts with non-toxic inorganic acids or organic acids, such as for example, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, propionic acid, lactic acid or citric acid.

The preparation of most tetraaminopyrimidines to be used as developer components according to the invention is already known in the literature and can be taken from the monograph by D. J. Brown, in the series "Heterocyclic Compounds", Interscience Publishers, 1962, Vols. I and II, "The Pyrimidines". Only a few of the compounds used are novel substances, the preparation of which is separately described below.

Specific examples of the novel tetraaminopyrimidines according to the invention are 5-amino-2,4,6-tris(methylamino)-pyrimidine, 2,4,5-triamino-6-(di-n-propylamino)-pyrimidine and 2,4,5-triamino-6-morpholino-pyrimidine, or a water-solution acid addition salt thereof.

To synthesize the compounds to be used according to the invention, the starting material generally is a 2,4,6-aminopyrimidine, into which the 5-amino group is introduced by nitrosation and subsequent reduction. It is also possible to start from the correspondingly substituted triaminoalkylmercaptopyrimides and to replace the alkylmercapto group with an amino group. The latter method is especially suitable for the introduction of substituted amino groups into the 2-, 4-, or 6-positions of the pyrimidine ring. Suitable examples of developer components to be used according to the invention are, for example: 2,4,5,6-tetraamino-pyrimidine, 4,5-diamino-2,6-bis-(methylamino)-pyrimidine,

2,5-diamino-4,6-bis-(methylamino)-pyrimidine,

4,5-diamino-6-(butylamino)-2-(dimethylamino)-6-pyrimidine,

2,5-diamino-4-(diethylamino)-6-(methylamino)-pyrimidine,

4,5-diamino-6-(diethylamino)-(2-dimethylamino)-pyrimidine,

4,5-diamino-2-(diethylamino)-6-(methylamino)-pyrimidine,

4,5-diamino-2-(dimethylamino)-6-(ethylamino)-pyrimidine,

4,5-diamino-2-(dimethylamino)-6-(isopropylamino)-pyrimidine,

4,5-diamino-2-(dimethylamino)-6-(methylamino)-pyrimidine,

4,5-diamino-6-(dimethylamino)-2-(methylamino)-pyrimidine,

4,5-diamino-2-(dimethylamino)-6-(propylamino)-pyrimidine,

2,4,5-triamino-6-(dimethylamino)-pyrimidine,

4,5,6-triamino-2-(dimethylamino)-pyrimidine,

2,4,5-triamino-6-(methylamino)-pyrimidine,

4,5,6-triamino-2-(methylamino)-pyrimidine,

4,5-diamino-2-(dimethylamino)-6-piperidino-pyrimidine,

4,5-diamino-6-(methylamino)-2-piperidino-pyrimidine,

2,4,5-triamino-6-piperidino-pyrimidine,

2,4,5-triamino-6-anilino-pyrimidine,

2,4,5-triamino-6-(benzylamino)-pyrimidine,

2,4,5-triamino-6-(benzylideneamino)-pyrimidine,

4,5,6-triamino-2-piperidino-pyrimidine,

5-amino-2,4,6-tris-(methylamino)-pyrimidine,

2,4,5-triamino-6-(di-n-propylamino)-pyridine,

2,4,5-triamino-6-morpholino-pyrimidine,

2,.Badd..[.4.]..Baddend..Iadd.5.Iaddend.,6-triamino-4-(dimethylamino)-pyrimidine

4,5,6-triamino-2-morpholino-pyrimidine,

2,4,5-triamino-6-(β-hydroxyethyl-amino)-pyrimidine,

4,5,6-triamino-2-[(β-aminoethyl)amino]-pyrimidine,

2,5,6-triamino-4-[(β-methylamino)-ethylamino]pyrimidine,

2,5-diamino-4,6[bis-(γ-diethylamino)-propylamino]-pyrimidine,

4,5-diamino-6-[(.[.B.]..Iadd.β.Iaddend.-hydroxyethyl)-amino]-2-(methylamino)-pyrimidine,

5-amino-2,4,6-(triethylamino)-pyrimidine, and

5-amino-6-anilino-2,4-[bis-(β-hydroxyethyl)-amino]-pyrimidine.

Generally speaking, the coupling components include 1-phenyl-pyrazol-5-ones, aromatic amines, aromatic alcohols, preferably m-aminophenols, 1,3-diamino-4-nitrobenzenes, 1,4-diamino-2-nitrobenzenes and pyrazolidine-diones.

Examples of coupling components include 1-phenylpyrazol-5-one derivatives of the formula ##STR3## wherein D represents lower alkyl such as methyl, NH 2 --,--NH--CO--D 1 or --NH--CO--NH--D 1 or NH--CS--NH--D 1 and D 1 denotes a hydrocarbon radical with 1 to 12 carbon atoms or a heterocylic radical, and preferably D 1 is alkyl having 1 to 6 carbon atoms such as methyl, ethyl, isopropyl, n-propyl, n-butyl; phenyl; halopenyl such as p-chlorophenyl; alkylphenyl having from 7 to 12 carbon atoms such as p-methylphenyl, p-ethylphenyl, o-propylphenyl; alkoxyphenyl, having from 7 to 12 carbon atoms such as o-methoxyphenyl p-isopropoxyphenyl; dialkylaminophenyl having 1 to 4 carbon atoms in the alkyl such as p-dimethylaminophenyl; cyclohexyl; alkylcyclohexyl having from 7 to 12 carbon atoms such as methylcyclohexyl; pyridyl; and piperidyl.

Examples of readily available substituted 1-phenyl-3-aminopyrazol-5-ones are the following:

1-phenyl-3-amino-pyrazol-5-one,

1-phenyl-3-methyl-pyrazol-5-one,

1-phenyl-3-acetamido-pyrazol-5-one,

1-phenyl-3-benzamido-pyrazol-5-one,

1-phenyl-3-(3'-cyclohexylureido)-pyrazol-5-one,

1-phenyl-3-(3'-phenylureido)-pyrazol-5-one,

1-phenyl-3-(3'-p-chlorophenylureido)-pyrazol-5-one,

1-phenyl-3-(3'-ethyl-2'-thioureido)-pyrazol-5-one,

1-phenyl-3-(3'-n-butyl-2'-thioureido)-pyrazol-5-one,

1-phenyl-3-(3'-phenyl-2'-thioureido)-pyrazol-5-one,

1-phenyl-3-(3'methylureido)-pyrazol-5-one,

1-phenyl-3-(3'-ethylureido)-pyrazol-5-one,

1-phenyl-3-(3'-n-propylureido-pyrazole-5-one,

1-phenyl-3-(3'-isopropylureido)-pyrazol-5-one, and

1-phenyl-3-(3'-n-butylureido)-pyrazol-5-one.

Another coupling component for the hair dyes is based on aromatic amines and/or aromatic alcohols, preferably a compound having the formula

E--Ar--F

in which Ar represents an aromatic nucleus, preferably consisting of naphthylene, hydroxynaphthylene, aminonaphthylene, phenylene, aminophenylene, hydroxyphenylene, toluylene, alkoxyphenylene having from 7 to 10 carbon atoms and quinolylene; E represents hydrogen, hydroxyl, or amino, dialkylamino having from 1 to 4 carbon atoms in the alkyls; and F represents hydroxyl, amino or dialkylamino having from 1 to 4 carbon atoms in the alkyls.

Suitable coupling components include aromatic amines and diamines, phenols, naphthols and aminophenols. The metacompounds are preferably used in the case of the diamines, aminophenols and phenols. When diamines are used, those in which the hydrogen atoms of the amino groups are substituted by lower alkyl residues (C 1 -C 4 ) may also be used.

The following compounds are examples of the said coupling components:

m-cresol,

m-phenylenediamine,

o-cresol,

m-aminophenol,

anisidine,

2,4-diaminoanisole,

m-toluylenediamine,

resorcinol,

pyrogallol,

pyrocathechol,

resorcinol-monoethyl ether

resorcinol-monomethyl ether,

m-aminoresorcinol,

1,5-dihydroxynaphthalene,

1,6-dihydroxynaphthalene,

1,7-dihydroxynaphthalene,

2,7-dihydroxynaphthalene,

1,5-amino- or 1,8-amino-hydroxynaphthalene,

α-naphthol,

7-(dimethylamino)-4-hydroxy-1-methyl-2-quinoline,

8-hydroxyquinoline,

1,8-diaminonaphthalene,

2,6-dimethyl-phenol,

2,5-dimethyl-phenol,

3,4-dimethyl-phenol,

3,5-dimethyl-phenol,

5-amino-2-methyl-phenol,

hydroquinone,

4-aminophenol,

Other coupling compounds include

1,3-diamino-4-nitrobenzene derivatives of the formula ##STR4## and 1,4-diamino-2-nitrobenzene derivatives of the formula ##STR5## in which X is an electrophilic substituent and A 2 is a member selected from the group consisting of hydrogen, alkyl of 1 to 10 carbon atoms, hydroxyalkyl of 1 to 10 carbon atoms; N,N-dialkyl-aminoalkyl of 3 to 18 carbon atoms, alkanoyl of 2 to 10 carbon atoms, substituted alkanoyl of 2 to 10 carbon atoms with a substituent selected from the group consisting of nitro, phenyl, halo, cyano, carboxy and sulfo, acyl of aromatic hydrocarbon carboxylic acids having 7 to 15 carbon atoms, substituted acyl of aromatic hydrocarbon carboxylic acids having from 7 to 15 carbon atoms with a substituent selected from the group consisting of lower alkyl, nitro, halo, cyano, carboxyl and sulfo, and the activated methylene group --CO--CH 2 --X, in which X is an electrophilic substituent.

An electrophilic substituents X, the radicals containing a carbonyl, such as carboxyl, alkoxycarbonyl, and acyl, or a nitrile, or carbonyl containing radicals further substituted with halogen, the sulfo group and the nitro group, are considered. X is preferably a nitrile, acyl, or alkoxycarbonyl group.

Examples of X include carboxyl, cyano, alkanoyl of 2 to 10 carbon atoms, substituted alkanoyl of 2 to 10 carbon atoms with a substituent selected from the group consisting of nitro, phenyl, halo, cyano, carboxyl and sulfo, acyl of aromatic hydrocarbon carboxylic acids having 7 to 15 carbon atoms, substituted acyl of aromatic hydrocarbon carboxylic acids having from 7 to 15 carbon atoms with a substituent selected from the group consisting of lower alkyl, nitro, halo, cyano, carboxyl and sulfo, cycloalkylcarbonyl of 6 to 10 carbon atoms, alkoxylcarbonyl of 2 to 10 carbon atoms, cycloalkoxycarbonyl of 6 to 10 carbon atoms, phenylalkoxycarbonyl of 8 to 16 carbon atoms, furoyl, and thenoyl.

Suitable examples for compounds of the above described diamino-nitrobenzenes are as follows:

1-amino-3-cyanoacetylamino-4-nitrobenzene,

1-benzoylacetylamino-3-amino-4-nitrobenzene,

1-methylamino-3-cyanoacetylamino-4-nitrobenzene,

1,3-di(cyanoacetylamino)-4-nitrobenzene,

1,3-Di(ω-ethoxycarbonyl-acetylamino)-4-nitrobenzene,

1-Amino-3(ω-ethoxycarbonyl-acetylamino)-4-nitrobenzene,

1-Acetylamino-3-cyanoacetylamino-4-nitrobenzene,

1-Amino-3-acetoacetylamino-4-nitrobenzene,

1-(ρ-Nitro-benzylacetylamino)-3-amino-4-nitrobenzene,

1-Trifluoro-acetoacetylamino-3-amino-4-nitrobenzene,

1-(2-Hydroxy-ethylamino)-3-cyanoacetylamino-4-nitrobenzene,

1-Amino-2-nitro-4-ω-cyanoacetylamino-benzene,

1-Amino-2-nitro-4-ω-benzoyl-acetylamino-benzene,

1,4-Dicyanoacetylamino-2-nitrobenzene,

1-Amino-2-nitro-4-ω-ethoxycarbonyl-acetylamino-benzene,

1,4-Bis-(ω-ethoxycarbonyl-acetylamino)-2-nitrobenzene,

1-Amino-2-nitro-4ω-benzoxycarbonyl-acetylamino-benzene,

1-Amino-2-nitro-4-(ρ-nitrobenzoyl-acetylamino)-benzene,

1-Amino-2-nitro-4-acetoacetylamino-benzene,

1-Amino-2-nitro-4-nitroacetoacetylamino-benzene,

1-Amino-2-nitro-4-trifluoroacetoacetylamino-benzene,

1-Amino-2-nitro-4-ω-butyryl-acetylamino-benzene,

1-Amino-2-nitro-4-ω-(β-Naphthoylacetylamino)-benzene,

1-Amino-2-nitro-4-cyclohexylcarbonyl-acetylamino-benzene,

1-Amino-2-nitro-4-Furoylacetylamino-benzene,

1-Amino-2-nitro-4-Thenoylacetylamino-benzene,

1,4-Bis-(ω-butoxycarbonyl-acetylamino)-benzene,

1,4-Bis-(ω-cyclohexyloxycarbonyl-acetylamino)-benzene.

Further coupling components include pyrazolidinediones such as 1-phenyl-3,5-pyrazolidine dione.

Specific examples of preferred coupling components to be used for the hair dyes according to the invention are as follows:

α-naphthol,

o-cresol,

m-cresol,

2,6-dimethylphenol,

2,5-dimethylphenol

3,4-dimethylphenol,

3,5-dimethylphenol

pyrocatechol,

pyrogallol

1,5-dihydroxy-naphthalene,

1,7-dihydroxy-naphthalene,

5-amino-2-methylphenol,

hydroquinone,

2,4-diaminoanisole,

m-toluylenediamine

4-aminophenol,

resorcinol,

resorcinol monomethyl ether m-phenylenediamine,

3-methyl-1-phenyl-pyrazolone-5,

3-amino-1-phenyl-pyrazolone-5,

1-phenyl-3,5-dione-pyrazolidine,

7-(dimethylamino)-4-hydroxy-1-methyl-quinolone-2,

1-amino-3-(acetacetylamino)-4-nitrobenzene,

1-amino-3-(cyanoacetylamino)-4-nitrobenzene.

In order to obtain shades which are as strong as possible and which correspond to natural hair colors to a large extent, it is very important to use a superior blue dye as shade component. In the preparation of natural looking shades with the aid of coupler components for producing blue dyes, there are, however, difficulties encountered with the customary blue-couplers even when the otherwise very satisfactory tetraaminopyrimidines are used as developers.

It has now been found that this drawback can be corrected when, in combination with the tetraaminopyrimidines employed as developers, the following m-aminophenols are used as the coupling components. These m-aminophenols have the formula ##STR6## wherein Z and Y are each selected from the group consisting of hydrogen, halogen, hydroxyl, amino, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylamino having 1 to 4 carbon atoms, dialkylamino having 1 to 4 carbon atoms in each of the alkyls; R 9 is selected from the group consisting of alkyl having 1 to 10 carbon atoms, phenyl optionally substituted, benzyl, methylenecyanamido, propionamido, ureido, thioureido, oxalyl ester having 1 to 4 carbon atoms in the alcohol moiety, M--(CH 2 ) m --in which m is an integer from 1 to 4 and M is selected from the group consisting of hydroxyl, halogen, and--NR 11 R 12 in which R 11 and R 12 are each hydrogen or alkyl having 1 to 4 carbon atoms, and in which R 9 and R 10 can together with the nitrogen atom form an optionally substituted five- or six-membered heterocyclic ring which may contain an additional nitrogen atom or an oxygen atom, and R 10 is selected from the group consisting of hydrogen and R 9 .

More particularly the coupling component is selected from the group consisting of (a) m-aminophenol of the formula ##STR7## wherein Z and Y are each selected from the group consisting of hydrogen, halogen, hydroxyl, amino, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylamino having 1 to 4 carbon atoms, dialkylamino having 1 to 4 carbon atoms in each of the alkyls;

Wherein R 9 is selected from the group consisting of alkyl having 1 to 10 carbon atoms, hydroxyalkyl having 1 to 10 carbon atoms, phenyl, anilino, hydroxyphenyl, benzyl, methylenecyanamido, propionamido, ureido, thioureido, oxalyl ester of an alcohol having 1 to 4 carbon atoms,

M--(CH.sub.2).sub.m --

wherein m is an integer from 1 to 4 and M is selected from the group consisting of hydroxyl, halogen, and --NR 11 R 12 , in which R 11 and R 12 are each hydrogen or alkyl having 1 to 4 carbon atoms and wherein R 10 is selected from the group consisting of hydrogen and R 9 ,

wherein R 9 and R 10 can together with the nitrogen atom form a member selected from the group consisting of a five- or six-membered heterocyclic ring optionally containing in the ring oxygen or nitrogen and

b. a water-soluble acid addition salt of (a).

A particularly preferred subgenus of said coupling component is

wherein Z and Y are each selected from the group consisting of hydrogen, methyl, methoxy, amino, chloro, and hydroxyl;

wherein R 9 is selected from the group consisting of methyl, ethyl, octyl, propyl, hydroxyethyl, phenyl, benzyl, anilino, hydroxyphenyl, ureido, thioureido, methylene-cyanamido, and diethylaminoethyl,

wherein R 10 is selected from the group consisting of hydrogen and R 9 ,

and wherein R 9 and R 10 together with the nitrogen atom form a member selected from the group consisting of pyrrolidino, morpholino, and piperidino.

The m-aminophenol derivatives to be employed as blue-coupling component can be used either as such or in form of their water-soluble acid addition salts with inorganic or organic acids, such as for example, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, propionic acid, lactic acid and citric acid.

Suitable examples of blue-coupling components to be employed according to the invention are as follows:

3-(dimethylamino)-phenol,

3-(diethylamino)-phenol,

3-(dioctylamino)-phenol,

3-(ethylmethylamino)-phenol,

3-(ethylpropylamino)-phenol,

3-(phenylethylamino)-phenol,

3-(phenyloctylamino)-phenol,

3-(benzylamino)-phenol,

3-(ethylbenzylamino)-phenol,

3-anilinophenol,

3-(methylamino)-phenol,

3-(ethylamino)-phenol,

3-(octylamino)-phenol,

3-(ethylureidoamino)-phenol,

3-ureidophenol,

3-(phenylureidoamino)-phenol,

3-(β-hydroxyethyl amino)-phenol,

3-(N-β-hydroxyethyl-N-methyl-amino)-phenol,

3-(thioureidoamino)-phenol,

N-ethyl-N-(3-hydroxyphenyl)-urea,

3-(methylenecyanamido)-phenol,

3-((2-diethylamino)-ethyl)-amino)-phenol,

3-N-(2-diethylaminoethyl)-N-methyl-aminophenol,

3-pyrrolidinophenol,

3-morpholinophenol,

3-piperidinophenol,

5-(ethylamino)-2-methylphenol,

5-(diethylamino)-2-methylphenol

3-ethylamino)-4-methoxyphenol,

3-diethylamino)-4-methoxyphenol,

2-chloro-5-(dimethylamino)-phenol

3,5-dihydroxy-N,N-dimethylaniline,

2-amino-5-(diethylamino)-phenol,

6-chloro-3-(diethylamino)-5-hydroxy-toluene,

3-anilino-6-chloro-5-hydroxy-toluene,

5-methyl-3-piperidino-phenol, and

4-chloro-3-pyrrolidino-phenol.

The preparation of the m-aminophenol derivatives to be used as blue-coupling components is already known from the literature. See the article of F. Effenberger et al in Chem. Ber. 103, 1456-62, (1970) and British Pat. No. 974,343. The preparation of several novel derivatives which were not found in the literature is separately described below.

Specific examples of novel m-aminophenols are as follows: 3-(diethylamino)-4-methoxy-phenol, 5-(ethylamino)-2-methyl-phenol and 5-(diethylamino)-2-methyl-phenol, as well as water-soluble acid addition salts thereof.

In the hair coloring preparations according to the invention, substantially equimolar quantities of the developer components are used based on the coupling components employed. Although an equimolar amount is preferred, it is possible to use more or less than molar amounts. Furthermore, the developer component and the coupling component may be used as pure ingredients or as mixtures. Not only can the developer component consist of mixtures of the tetraaminopyrimidines to be used according to the invention, but the coupling component can also consist of mixtures of the above-named coupling components.

In addition, the hair coloring preparations according to the invention can contain admixtures of other customary developing components and, if necessary, can also contain the customary direct dyestuffs in case the latter are needed for obtaining certain shades. From 0% to 5% direct dyestuffs may be employed. As in the case of other oxidation hair dyes, the oxidative coupling, i.e., the development of the dye can in principle be effected by atmospheric oxygen. Moreover, it is preferred to use chemical oxidizing agents. Suitable examples are especially hydrogen peroxide or its products of addition to urea, melamine and sodium borate, as well as mixtures of such hydrogen peroxide addition products with potassium peroxydisulfate.

When the tetraaminopyrimidines according to the invention are used as developer components, they have the advantage that the oxidative coupling with atmospheric oxygen readily produces highly satisfactory hair dyeing results. Thus, damage to the hair by the oxidizing agents, otherwise employed for oxidative coupling, can be prevented.

In the situation that a bleaching of the hair is simultaneously desired, then the concurrent use of chemical oxidizing agents is necessary.

For application, the hair dyes according to the invention are incorporated into suitable aqueous cosmetic preparations, such as creams, emulsions, gels or simple solutions and immediately before application to the hair, one of the above-named oxidizing agents is added. These hair dyeing preparations contain coupling and developing components in amounts of from 0.2% to 5% by weight, preferably from 1% to 3% by weight.

For the preparation of creams, emulsions or gels, the dye components are mixed with the additional ingredients customarily used in such preparations. Such additional ingredients are, for example, wetting agents or emulsifiers of the anionic or nonionic type, such as alkylbenzenesulfonates, higher fatty alcohol sulfates, higher alkylsulfonates, higher fatty acid alkanolamides, ethoxylated fatty alcohols; thickeners such as methyl cellulose, starch, higher fatty alcohols, paraffin oil and higher fatty acids. Furthermore, perfumes and hair-conditioning and grooming agents, such as panthothenic acid and cholesterol may be included.

Effective amounts of the above-named additives are those customarily employed for this purpose. Effective amounts of wetting agents range from 0.5% to 30% by weight, preferably from 1% to 15% by weight; and for thickeners, an effective amount ranges from 0.1% to 25% by weight, preferably from 1% to 15% by weight, based in each case on the total weight of the preparation. As a lower limit for the above additives, a zero percent lower limit is possible, if none of the additive is utilized.

The hair coloring preparations according to the invention can be applied in a weakly acid medium, a neutral medium or especially, in an alkaline medium, preferably at a pH of 8 to 10, regardless whether a solution, an emulsion, a cream, or a gel is employed.

These preparations are applied at a temperature which usually ranges from 15° C. to 40° C. and preferably is room temperature.

After the preparation has been allowed to react for about 30 minutes, the hair coloring preparation is removed from the hair to be dyed, by rinsing. Then the hair is washed with a mild shampoo, and finally is dried.

When different developer and coupling components are used, the shades obtainable by use of the hair coloring preparations according to the invention have the advantage of providing an extraordinary variations which extend from ash blond to dark brown and green to violet. The properties of the hair colors produced are excellent as far as fastness to light and washing are concerned, as well as good resistance to abrasion is concerned; and the hair dyes once fixed can be easily removed by means of reducing agents.

The following examples are merely illustrative of the present invention without being deemed limitative in any manner thereof.

First, there are examples for the preparation of some novel tetraminopyrimidines which are utilized according to the invention, but have not been previously described in the literature.

Preparation of

5-Amino-2,4,6-tris-(methylamino)-pyrimidine Sulfate,

C 7 H 14 N 6 ·H 2 SO 4 ·2H 2 O

2,4,6-tris(methylamino)-pyrimidine was prepared according to Winkelmann, J. Pract. Chem. 115, 292 (1927) and 5.5 gm of this compound were dissolved in 50 ml water. The solution was adjusted to a pH of 4 by means of sodium acetate and was then heated to 80° C.; and a solution of 1.4 gm of NaNO 2 in 5 ml of H 2 O was added to form a red solution. At 60° C., sodium dithionite was added until the solution became yellow. Dilute H 2 SO 4 was added to the yellow solution; and the precipitate was vacuum filtered. The yield was 55%; and the melting point was 215° C.

______________________________________

Elemental Analysis:

______________________________________

Found: 26.6 6.4 26.6

Calculated: 26.6 8.3 27.7

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Preparation of

2,4,5-Triamino-6-(di-n-propylamino)-pyrimidine

Dihydrochloride, C 10 H 20 H 6 ·2 HCl

2,4,5-Triamino-6-(di-n-propylamino)pyrimidine dihydrochloride was prepared stepwise as follows:

1. 2,4-Diamino-6-(di-n-propylamino)-pyrimidine

2,4-Diamino-6-chloropyrimidine was prepared according to Roth et al, J. Amer. Chem. Soc. 72, 1914 (1950). To 15 gm of this compound in 130 ml of ethanol, there was added 50 gm of di-n-propylamine, and the mixture was heated in an autoclave at 200° C. for three hours (at an initial gauge pressure of 10 atm. of N 2 ). After the autoclave had cooled and had been opened, the reaction mixture was cooled in an ice-salt bath to precipitate dipropylamine hydrochloride. After filtration, the mother liquor was considerably concentrated to give a residue of about 30 ml, whereby 18 gm or 82.9% of theory of crude raw product precipitated. This product was used as such for subsequent synthesis.

2. 2,4-Diamino-6-(di-n-propylamino)-5nitrosopyrimidine

18 gm of the crude product 2,4-diamino-6-(di-n-propylamino)-pyrimidine was suspended in 25 ml of water; and glacial acetic acid was added until a pH of 4 was reached. After heating to 50° C. had resulted in solution of the substance, 5.5 gm of sodium nitrite in 10 ml of water were slowly added. After a short time, a raspberry red precipitate was deposited, vacuum filtered, and dried under vacuum at room temperature. The remainder weighed 9.4 gm which was 46% theory; and had a melting point of 206°-208° C.

______________________________________

Elemental Analysis:

______________________________________

Found: 50.40 7.61 35.27

Calculated: 49.56 7.62 35.50

______________________________________

3. 2,4,5-Triamino-6-(di-n-propylamino)-pyrimidine Dihydrochloride

6.5 gm of 2,4-diamino-6-(di-n-propylamino)-5-nitrosopyrimidine in 150 ml of ethanol with 0.5 gm of catalyst (10% palladium-on-charcoal) were introduced into a pressure-tested hydrogenation vessel to be hydrogenated at room temperature in a catalytic apparatus of the shaker type. After H 2 -absorption had terminated, the catalyst was removed by filtration; the solution was acidified with hydrochloric acid, and concentrated. The residue was 5.6 gm which was 78.8% of theory of brown crystals; melting point (decomp.) was 105° C. The mass spectrum showed the molecular mass to be 224 (calcd.: 224).

Preparation of

2,4,5-Triamino-6-morpholino-pyrimidine Sulfate,

C 8 H 14 N 6 O·H 2 SO 4

2,4,5-Triamino-6-morpholino-pyrimidine sulfate was prepared stepwise from the following compounds:

1. 2,4-Diamino-6-morpholinopyrimidine

2,4-diamino-6-chloropyrimidine was prepared according to Roth et al, J. Amer. Chem. Soc. 72, 1914 (1950). To 10 gm of this compound, (0.07 mol), 30 gm of morpholine (30 ml, 0.34 mol) were added; and while stirring, the mixture was heated to 100° C. within one hour. The mixture was kept at this temperature for 21/2 hours. Then, 10 ml of ethanol were added; and the mixture was stored in a refrigerator until morpholine hydrochloride had precipitated. After removal of this salt, the filtrate was concentrated to produce the crude product which was half oily, half crystalline residue. There was 5.9 gm which constituted 43.7% of theory; and this crude product was utilized for subsequent synthesis.

2. 2,4-Diamino-6-morpholine-5-nitroso-pyrimidine

5.9 gm of the crude 2,4-diamino-6-morpholino-pyrimidine (0.03 mol), were dissolved by heating in 25 ml of water; and glacial acetic acid was added until a pH of 4 was reached. Then the solution was heated to 80° C., and a solution of 2 gm of sodium nitrite in 5 ml of water was slowly added. After a short time, the nitroso compound was obtained as a raspberry red precipitate. Concentration and cooling produced a total yield of a 4.1 gm which was 60.3% of theory. The melting point was 231°-233° C.

______________________________________

Elemental Analysis:

______________________________________

Found: 42.85 5.39 37.48

Calculated: 41.92 4.97 38.22

______________________________________

3. 2,4,5-Triamino-6-morpholino-pyrimidine Sulfate

2.5 gm of 2,4-diamino-6-morpholino-5-nitroso-pyrimidine was suspended in 15 ml of water, and 2 N HCl (5 ml) was added until the substance just dissolved. The mixture was heated to 50° C.; and sodium dithionite (Na 2 S 2 O 4 ) was added until the violet color solution took on a yellow color. Then, the solution was filtered, cooled, and adjusted to a pH 2 by means of sulfuric acid (1:1). After a short time, the pyrimidine derivative precipitated as pyrimidine sulfate; the yield was 2.6 gm which was 76.4% of theory.

______________________________________

Elemental Analysis

(of the recrystallized compound):

______________________________________

Found: 31.17 5.23 27.2

Calculated: 29.81 4.98 27.8

Melting Point: the compound sintered at 230°

slow decomposition from 255° C. on.

______________________________________

Melting Point: the compound sintered at 230° slow decomposition from 255° C. on.

The other tetraaminopyrimidines which were used in the following Examples were reported in the literature and were prepared by the synthesis indicated in the monograph of D. J. Brown, "The Pyrimidines" in the series of Heterocyclic Compounds, Interscience Publishers, 1962, Vols. I and II.

Several m-aminophenol derivatives which were used as blue-coupling components in the hair coloring preparations according to the invention are novel and are not found in the literature. Hence, their preparation is described in the following examples.

3-(Diethylamino)-4-methoxyphenol Hydrochloride

8.3 gm ethyl bromide were added to a solution of 10.5 gm of 3-amino-4-methoxyphenol in 50 ml of ethanol. The reaction mixture was refluxed for 24 hours. After the solution had cooled, it was diluted with 800 ml of water; and the pH was adjusted to slight alkalinity by the addition of sodium carbonate. The solution was repeatedly extracted with ether, and the combined extracts were dried over anhydrous sodium sulfate. After the precipitate had been filtered off, the residue was concentrated; and the remaining residue as dissolved in 50 ml of ethanol. Then, after 8.7 gm of ethyl bromide had been added, the alkylation and treatment of the product were repeated as described above with the exception that this time, the dried ether extract was only concentrated to a volume of about 300 ml and dry HCl gas was passed into the solution while it was being cooled with ice. The precipitate was vacuum filtered; the residue was dried, dissolved in ethanol, and treated with active charcoal. Addition of ether to the ethanolic solution resulted in the precipitation of the pure product, which had a melting point of 197°-198° C.

______________________________________

Elemental Analysis:

% C % H % N C1

______________________________________

Found: 57.1 7.8 6.03 15.3

Calculated: 56.3 7.8 5.4 14.6

______________________________________

Mass Spectrum: 195 (calcd.: 195).

5-(Ethylamino)-2-methylphenol

88.6 gm of ethyl bromide were added to a solution of 50 gm of 5-amino-2-methylphenol in 250 ml of ethanol; and the mixture was refluxed for four hours. After the solution had cooled, it was diluted with 1.2 liters of water and was made weakly alkaline with sodium carbonate. After repeated extraction with ether, the ether extracts were dried and concentrated. The residue was recrystallized from ethanol, and had a melting point of 128° C. to 129° C.

______________________________________

Elemental Analysis:

______________________________________

Found: 71.5 8.6 9.3

Calculated: 70.79 8.51 9.5

______________________________________

Mass Spectrum: 151 (calcd.: 151)

5-(Diethylamino)-2-methylphenol Hydrochloride

5 gm of 5-(ethylamino)-2-methylphenol were dissolved in 50 ml of ethanol, then alkylated analogously to the procedure described in Example 4 with 5,2 gm ethyl bromide, and worked up. The hydrochloride had a melting point of 192° C.

______________________________________

Elemental Analysis:

% C % H % N % Cl

______________________________________

Found: 61.3 8.4 6.5 16.5

Calculated: 62.9 8.8 6.8 15.9

______________________________________

Mass Spectrum: 179 (calcd.: 179)

The hair dyes according to the invention were applied in form of an aqueous preparation such as an emulsified cream. The emulsion contained

10 parts by weight of fatty alcohols having 12 to 18 carbon atoms,

10 parts by weight of fatty alcohol sulfate (sodium salt) having 12 to 18 carbon atoms and

75 parts by weight of water.

Into each emulsion, there was incorporated 0.01 mol of the tetraaminopyrimidines and couplers which are listed in the following Table I. Then, the pH-value of the emulsion was adjusted to 9.5 with ammonia, and the emulsion was made up to 100 parts by weight with water. The oxidative coupling was effected by using as an oxidizing agent either atmospheric oxygen, or a 1% hydrogen peroxide solution with the proviso that 10 parts by weight of hydrogen peroxide solution were added to 100 parts by weight of the emulsion. The respective dyeing cream, with or without additional oxidizing agent, was applied to human hair that was 90% gray and that had not been pretreated in a special manner. After the cream had remained on the hair for 30 minutes to complete the dyeing process, the hair was washed with a customary shampoo and then dried. The shades thereby obtained are also listed in the following Table I.

__________________________________________________________________________

Shade obtained

With

Atmos- with

Developer Coupler pheric O.sub.2

1% H.sub.2 O.sub.2

__________________________________________________________________________

7 2,4,5,6-Tetra-amino-

m-Phenylenediamine

olive olive

pyrimidine

8 2,4,5,6-Tetra-amino-

2,4-Diaminoanisole

dark green

dark green

pyrimidine

9 2,4,5,6-Tetra-amino-

m-diamino toluene

yellowish

yellowish

pyrimidine

brown brown

10 2,4,5,6-Tetra-amino-

m-aminophenol violet violet

pyrimidine brown brown

11 2,4,5,6-Tetra-amino-

Resorcinol strawberry

grayish

pyrimidine red red

12 2,4,5,6-Tetra-amino-

3-Amino-1-phenyl-

brownish

brownish

pyrimidine pyrazolone-5 orange orange

13 2,4,5,6-Tetra-amino-

3-Methyl-1-phenyl-

brownish

brownish

pyrimidine pyrazolone-5 red orange

14 2,4,5,6-Tetra-amino-

Resorcinol golden golden

pyrimidine monomethyl ether

brown brown

15 2,4,5,6-Tetra-amino-

Naphthol yellowish

yellowish

pyrimidine brown brown

16 2,4,5,6-Tetra-amino-

1,5-Dihydroxy-

havanna

havanna

pyrimidine Naphthalene brown brown

17 2,4,5,6-Tetra-amino-

1,7-Dihydroxy-

olive olive

pyrimidine Naphthalene brown brown

18 4-Dimethylamino-

m-Phenylenediamine

yellowish

yellowish

2,5,6-Triamino- brown brown

pyrimidine

19 4-Dimethylamino-

2,4-Diaminoanisole

olive olive

2,5,6-Triamino- yellow yellow

pyrimidine

20 4-Dimethylamino-

m-Diaminotoluene

yellowish

yellowish

2,5,6-Triamino- brown brown

pyrimidine

21 4-Dimethylamino-

m-Aminophenol burgundy

burgundy

2,5,6-Triamino- red red

pyrimidine

22 4-Dimethylamino-

Resorcinol brownish

brownish

2,5,6-Triamino- red red

pyrimidine

23 4-Dimethylamino-

3-Amino-1-Phenyl-

raspberry

raspberry

2,5,6-Triamino-

pyrazolone-5 red red

pyrimidine

24 4-Dimethylamino-

m-Phenylenediamine

olive olive

2,5,6-Triamino- brown brown

pyrimidine

25 2-Dimethylamino-

m-Phenylenediamine

dark dark

4,5,6-triamino- green green

pyrimidine

26 2-Dimethylamino-

2,4-Diaminoanisole

dark dark

4,5,6-triamino- green green

pyrimidine

27 2-Dimethylamino-

m-Diaminotoluene

olive- olive-

4,5,6-triamino- tinged tinged

pyrimidine yellow yellow

28 2-Dimethylamino-

m-Aminophenol grayish

dark

4,5,6-triamino- violet violet

pyrimidine

29 2-Dimethylamino-

Resorcinol reddish

reddish

4,5,6-triamino- violet violet

pyrimidine

30 2-Dimethylamino-

3-Amino-1-phenyl-

brick red

brick red

4,5,6-triamino-

pyrazolone-5

pyrimidine

31 2-Dimethylamino-

3-Methyl-1-phenyl-

lake red

grayish

4,5,6-triamino-

pyrazolone-5 orange

pyrimidine

32 2-Dimethylamino-

Naphthol hair olive

4,5,6-triamino- brown brown

pyrimidine

33 2-Dimethylamino-

3-acetoacetylamino-

yellowish

brass

4,5,6-triaminio-

1-amino-4-nitroben-

brown yellow

pyrimidine zene

34 2-Dimethylamino-

1-Phenyl-3,5-pyra-

brownish

gray red

4,5,6-triamino-

zolidine-dione

orange

pyrimidine

35 2-Dimethylamino-

o-Cresol brownish

ivory

4,5,6-triamino- orange

pyrimidine

36 2-Dimethylamino-

m-Cresol brownish

ivory

4,5,6-triamino- orange

pyrimidine

37 2-Dimethylamino-

2,5-Dimethylphenol

brownish

grayish

4,5,6-triamino- red green

pyrimidine

38 2-Dimethylamino-

3,4-Dimethylphenol

brownish

grayish

4,5,6-triamino- orange green

pyrimidine

39 2-Dimethylamino-

3,5-Dimethylphenol

brownish

grayish

4,5,6-triamino- orange orange

pyrimidine

40 2-Dimethylamino-

1,5-Dihydroxy-

brown brown

4,5,6-triamino-

Naphthalene

pyrimidine

41 2-Dimethylamino-

Pyrogallol chocolate

zinc

4,5,6-triamino- brown gray

pyrimidine

42 2-Dimethylamino-

Pyrocatechol reddish

fallow

4,5,6-triamino- brown

pyrimidine

43 2-Dimethylamino-

7-(Dimethylamino)-4-

grayish

golden

4,5,6-triamino-

hydroxy-1-methyl-2-

orange blond

pyrimidine quinolone

44 2-Dimethylamino-

5-Amino-2-methyl-

brown brown

4,5,6-triamino-

phenol

pyrimidine

45 2-Dimethylamino-

Hydroquinone brownish

golden

4,5,6-triamino- red blond

pyrimidine

46 2-Piperidino-

m-Phenylenediamine

dark dark

4,5,6-triamino- green green

pyrimidine

47 2-Piperidino-

m-Aminophenol dark dark

4,5,6-triamino- violet violet

pyrimidine

48 2-Piperidino-

Resorcinol grayish

grayish

4,5,6-triamino- ruby ruby

pyrimidine

49 2-Piperidino-

2,4-Diaminoanisole

dark dark

4,5,6-triamino- green green

pyrimidine

50 2-Piperidino-

m-Diaminotoluene

brownish

brownish

4,5,6-triamino- orange orange

pyrimidine

51 2-Piperidino-

3-Amino-1-phenyl-

tomato tomato

4,5,6-triamino-

pyrazolone-5- red red

pyrimidine

52 2-Morpholino-

m-Phenylenediamine

olive olive

4,5,6-triamino

pyrimidine

53 2-Morpholino-

m-Aminophenol dark dark

4,5,6-triamino- violet violet

pyrimidine

54 2-Morpholino-

Resorcinol grayish

grayish

4,5,6-triamino- ruby ruby

pyrimidine

55 2-Morpholino-

2,4-Diaminoanisole

dark dark

4,5,6-triamino- green green

pyrimidine

56 2-Morpholino-

m-Diaminotoluene

olive olive

4,5,6-triamino- brown brown

pyrimidine

57 2-Morpholino-

3-Amino-1-phenyl-

brownish

brownish

4,5,6-triamino-

pyrazolone-(5)

red red

pyrimidine

58 2-Methylamino-

m-Phenylenediamine

olive olive

4,5,6-triamino-

pyrimidine

59 2-Methylamino-

m-Aminophenol dark dark

4,5,6-triamino- purple violet

pyrimidine

60 2-Methylamino-

Resorcinol grayish

brownish

4,5,6-triamino- red violet

pyrimidine

61 2-Methylamino-

2,4-Diaminoanisole

dark dark

4,5,6-triamino- green green

pyrimidine

62 2-Methylamino-

m-Diaminotoluene

yellow yellow

4,5,6-triamino-

pyrimidine

63 2-Methylamino-

3-Amino-1-phenyl-

brownish

brownish

4,5,6-triamino-

pyrazolone-5 red red

pyrimidine

64 6-Morpholino-

m-Phenylenediamine

olive olive

2,4,5-triamino- brown brown

pyrimidine

65 6-Morpholino-

2,4-Diaminoanisole

grayish

olive

2,4,5-triamino- green

pyrimidine

66 6-Morpholino-

m-Diaminotoluene

golden brass

2,4,5-triamino- yellow yellow

pyrimidine

67 6-Morpholino-

m-Aminophenol grayish

grayish

2,4,5-triamino- ruby red

pyrimidine

68 6-Morpholino-

Resorcinol brownish

brownish

2,4,5-triamino- red red

pyrimidine

69 6-Morpholino-

3-Amino-1-phenyl-

2,4,5-triamino-

pyrazolone-5 dull red

dull red

pyrimidine

70 6-Piperidino-

m-Phenylenediamine

bamboo grayish

2,4,5-Triamino- yellow yellow

pyrimidine

71 6-Piperidino-

2,4-Diaminoanisole

olive olive

2,4,5-Triamino- brown

pyrimidine

72 6-Piperidino-

m-Aminophenol olive bamboo

2,4,5-Triamino- brown yellow

pyrimidine

73 6-Piperidino-

Resorcinol grayish

ivory

2,4,5-Triamino- red

pyrimidine

74 6-Piperidino-

m-Diaminotoluene

grayish

olive

2,4,5-Triamino- yellow brown

pyrimidine

75 6-Piperidino-

3-Amino-1-phenyl-

chamois

straw

2,4,6-Triamino-

pyrazolone-5 yellow yellow

pyrimidine

76 6-(Di-n-propylamino)-

m-Phenylenediamine

honey olive

2,4,5-triamino- yellow

pyrimidine

77 6-(Di-n-propylamino)-

2,4-Diaminoanisole

olive olive

2,4,5-triamino- green

pyrimidine

78 6-(Di-n-propylamino)-

m-Diaminotoluene

honey honey

2,4,5-triamino- yellow yellow

pyrimidine

79 6-(Di-n-propylamino)-

m-Aminophenol grayish

grayish

2,4,5-triamino- ruby ruby

pyrimidine

80 6-(Di-n-propylamino)-

Resorcinol brownish

brownish

2,4,5-triamino- red red

pyrimidine

81 6-(Di-n-propylamino)-

3-Amino-1-phenyl-

reddish

reddish

2,4,5-triamino-

pyrazolone-5- brown brown

pyrimidine

82 5-Amino-2,4,6-

m-Phenylenediamine

oak brown

olive

tris-(methylamino)-

pyrimidine

83 5-Amino-2,4,6-

2,4-Diaminoanisole

olive beaver

tris-(methylamino)- brown

pyrimidine

84 5-Amino-2,4,6-

m-diaminotoluene

brass olive

tris-(methylamino)- yellow

pyrimidine

85 5-Amino-2,4,6-

m-Aminophenol dark brown

tris-(methylamino)- ruby

pyrimidine

86 5-Amino-2,4,6-

Resorcinol grayish

dull

tris-(methylamino)- red red

pyrimidine

87 5-Amino-2,4,6-

3-Amino-1-phenyl

reddish

light

tris-(methylamino)-

pyrazolone-5 brown brown

pyrimidine

88 2-Dimethylamino-

3-(Diethylamino)-

blue blue

4,5,6-Triamino-

phenol black black

pyrimidine

89 2-Dimethylamino-

3-[(β-Hydroxyethyl)-

blue blue

4,5,6-Triamino-

amino]-phenol black black

pyrimidine

90 2-Dimethylamino-

3-[2-(Diethylamino)-

blue blue

4,5,6-Triamino-

ethyl-amino]-phenol

black black

pyrimidine

91 2-Dimethylamino-

3-Morpholino-phenol

dark dark

4,5,6-Triamino- violet violet

pyrimidine

92 2-Dimethylamino-

3-(Ethylpropylamino)

blue blue

4,5,6-Triamino-

phenol black black

pyrimidine

93 2-Dimethylamino-

3-(Butylamino)-phenol

blue blue

4,5,6-Triamino- black black

pyrimidine

94 2-Dimethylamino-

3-(Ethylamino)-phenol

blue blue

4,5,6-Triamino- black black

pyrimidine

95 2-Dimethylamino-

3-(Octylamino)-phenol

dark dark

4,5,6-Triamino- violet violet

pyrimidine

96 2-Dimethylamino-

3-Pyrrolidino-phenol

blue blue

4,5,6-Triamino- black black

pyrimidine

97 2-Dimethylamino-

3-Piperidino-phenol

dark dark

4,5,6-Triamino- blue blue

pyrimidine

98 2-Dimethylamino-

3-(Dimethylamino)-

dark dark

4,5,6-Triamino-

phenol blue blue

pyrimidine

99 2-Dimethylamino-

5-(Ethylamino)-2-

bluish bluish

4,5,6-Triamino-

methyl-phenol gray gray

pyrimidine

100 2-Dimethylamino-

2-Chloro-5-(dimethyl-

dark dark

amino)-phenol

amion)-phenol violet violet

pyrimidine

101 2-Dimethylamino-

3-Hydroxydiphenyl-

dark dark

4,5,6-Triamino-

amine blue blue

pyrimidine

102 2-Dimethylamino-

3-(Methylenecyana-

dark dark

4,5,6-Triamino-

mido)-phenol violet violet

pyrimidine

103 2-Dimethylamino-

2-bromo-5-(methylene-

blue blue

4,5,6-Triamino-

cyanamido)-phenol

black black

pyrimidine

104 2-Dimethylamino-

3-Tihoureido-phenol

brownish

dull

4,5,6-Triamino- gray violet

pyrimidine

105 2-Dimethylamino-

3-(Diethylamino)-4-

dark dark

4,5,6-Triamino-

methoxy-phenol

blue blue

pyrimidine

106 2-Dimethylamino-

5-(Diethylamino)-2-

dark dark

4,5,6-Triamino-

methyl-phenol blue blue

pyrimidine

107 2-Morpholino-

m-Dimethylamino-

dark dark

4,5,6-triamino-

phenol blue blue

pyrimidine

108 2-Morpholino-

3-Hydroxydiphenyl-

dark dark

4,5,6-triamino-

amine blue blue

pyrimidine

109 2-Morpholino-

3-(Octylamino)-

dark violet

4,5,6-triamino-

phenol violet blue

pyrimidine

110 2-Piperidino-

m-(Dimethylamino)-

dark dark

4,5,6-triamino-

phenol blue blue

pyrimidine

111 2-Piperidino-

m-(Octylamino)-

blue blue

4,5,6-triamino-

phenol violet violet

pyrimidine

112 2-Piperidino-

3-Hydroxydiphenyl-

dark dark

4,5,6-triamino-

amine blue blue

pyrimidine

113 2-Methylamino-

3-Hydroxydiphenyl-

violet blue

4,5,6-triamino-

amine blue violet

pyrimidine

114 2-Methylamino-

3-(Octylamino)-

deep deep

4,5,6-triamino-

phenol violet violet

pyrimidine

115 2-Methylamino-

m-(Dimethylamino)-

deep violet

4,5,6-triamino-

phenol violet blue

pyrimidine

116 2,4,5,6-Tetraamino-

m-(Dimethylamino)-

dark dark

pyrimidine phenol violet violet

117 2,4,5,6-Tetraamino-

m-(Diethylamino)-

dark dark

pyrimidine phenol violet violet

118 2,4,5,6-Tetraamino-

m-(Ethylamino)-

indigo indigo

pyrimidine phenol blue blue

119 2,4,5,6-Tetraamino-

m-(Ethylpropylamino)-

dark dark

pyrimidine phenol violet violet

120 2,4,5,6-Tetraamino-

m-[(β-Hydroxyethyl)-

dark dark

pyrimidine amino]-phenol violet violet

121 2,4,5,6-Tetraamino-

m-Piperidino-phenol

light light

pyrimidine violet violet

122 2,4,5,6-Tetraamino-

m-Pyrrolidino-

violet violet

pyrimidine phenol

123 2,4,5,6-Tetraamino-

3-Hydroxydiphenyl-

indigo indigo

pyrimidine amine blue blue

__________________________________________________________________________

The following tests were conducted to determine the toxicological and dermatological properties of tetraaminopyrimidines. The test compound used was 2-dimethylamino-4,5,6-triamino-pyrimidine sulfate which was compared with known compounds, p-phenylenediamine and p-toluylenediamine sulfate. The following results were obtained.