DE2359399A1 - Tetraaminopyrimidines as developers in oxidation hair dyes - esp. used with meta aminophenol couplers for blue shading dyes - Google Patents

Abstract

Oxidn. hair dyeing compsns. contain as developer tetraaminopyrimidines of formula (I) or their salts or mixts.; (where R1-R6 = H, 1-4 C alkyl or -(CH2)nX; n = 1-4; X = OH, halo, NH2, NHR1 or NR1R11; R1 and R11 = 1-4 C alkly or together complete a heterocycle opt. contg. a further O or N; opt. substd. aryl or opt. substd. 5 or 6 membered heterocycles contg. 1 or 2 N atoms or 1N plus 1 O). (I) give intense colours varying from blond to dark brown and from green to violet; they are highly sol. in water, storage stable, are non-toxic and do not irritate the skin or mucosa. Dyeings are stable to light, washing and abrasion, but may easily be removed with reducing agents.

Description

Düsseldorf, November 27, 1975. ■ Henkel & Cie GmbH

Henkelstrasse 67 ■ Patent department

:,: .. / V ■ -A-, Z / Br

Patent application

D 4774 "Hair dye"

The invention relates to agents for oxidative Hair coloring based on tetraaminopyrimidines as a developer component.

The so-called oxidation colors, which are produced by oxidative coupling, play a role in the coloring of hair Developer components with a coupler component are created because of their intense colors and very good colors Fastness properties .a preferred role. Nitrogen bases are usually used as developer substances, such as p-phenylenediamine derivatives, diaininopyridines ,. 4-Amino-pyrazolone derivatives, heterocyclic hydrazones used. As so-called coupler components m-phenylene diamine derivatives, phenols, naphthols, resorcinol derivatives and called pyrazolones. .

Good oxidative hair dye components need to be first Line meet the following requirements:

You must with the oxidative coupling with the respective Developer or coupler components develop the desired color nuances with sufficient intensity. she must also have sufficient to very good winding wealth on human hair and they should about it h: '. naus in toxicological and dermatological \ In terms of concern.

Those commonly used as developing substances Compound class of the substituted or unsubstituted

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Henkel & Cie GmbH

Patent department

p-Phenylenediamines has the disadvantage that they are at sensitized a number of people and caused severe allergies as a result. The for Avoidance of these dermatological disadvantages recently proposed developer substances can in do not always fully satisfy their application properties.

There was therefore a search for useful oxidation hair dyes the task of finding suitable components that meet the above requirements in meet in an optimal way.

It was found that hair dye based of oxidation dyes containing tetraaminopyriiridines the general formula

in which R, - Rg hydrogen, an alkyl radical with 1 - K carbon atoms,

the radical - (CH ₂ ) _n - X, in which η = 1 - K and X is a hydroxyl group, a halogen atom, an -NH ₂ -, -NHR ^! - and -NR ¹ 'R "groups, where R ¹ and R" can represent alkyl radicals with 1 - K carbon atoms or are closed with the nitrogen atom to form a heterocyclic ring which can contain a further nitrogen atom or oxygen atom,

an optionally substituted heterocyclic 5- or 6-membered ring with one or two nitrogen atoms or a nitrogen atom and an oxygen

509824/0371

Henkel & Cie GmbH

Patent department

display atom ^;; konhen; ^ «0w; 3Ce ^ eren. inorganic or organic '= salting ^: as'Botwifekrlorswbs-feanzen; and .den _; in:, _; . Oxidation oris'haarfarben = usual Küpplersutistanzien, the "... ν ........ provided" Aniörderuiigen in ^; especially, to a high degree, to be fair. ■ "-v- ¹ · ¹ ; ' ¹ < ni -'- 3V5 --'- 'rvv-i ■ ^: - ^<: ^ - ^; '"·'^:-" - ^ ■' - ·: '.. ■: ■ -; .-- ". ■, ': ~ -

When used as developer components, the invention ^; 'V% rblndüngen ^ _m: ici; der3i';.... Generally ::, / for the "OxiolätiOnsllälir £ ärbüng- / Use part; Kvipplersub- / ■, punch the un ^ erfecMeäiiehsten: _very; .infcensiyein color - _: .., nuances that could not be achieved with these couplers with the previously known developers and thus represent an essential enrichment of oxidative hair coloring possibilities Teträaminopyriinidines according to the invention by · _; the dyeings obtained therewith have very good fastness properties, good solubility in water, good storage stability and toxicological and dermatological harmlessness. ^; ^ _:

The tetraaminopyrimidines to be used according to the invention as developer components can either be used as such or in the form of their salts with inorganic or organic see Acids, such as chlorides, SuI. fate, phosphates, ' Acetate, Propionate ;, Lac tate = ,; Citrate used; will.

The ^Vi making the most -, erf indungsgemäß "as the developer component _n ^ to ^^ _EEW; eηdenden Tejtraaminopyrimide is already literaturbekannt.- and ^ kanp which - monograph ,, D .. J. Brown." The pyrimidines · © "; invader- ^ eihe, He.teroeyelic .. Qompounds, Intersciöac ^: Pub.lishe ^ s _r X 19fe) _.; Volume χ, and * IJ /. are taken ^. Only / a few of the compounds used represent, naue ; Represent substances whose .production is described as' differently '' ., '.. "■ -''"" ^: '^;'-'"-^': - ■ ■■ ■■ - ■■ - ■ · ---" ■ - ■■ ^■:

5 D 9 824 / OBfI

Henkel & Cie GmbH

Patent department

The synthesis of the compounds to be used according to the invention is generally based on 2,4,6-triaminopyrimidines from, into which the 5-amino group is introduced by nitrosation and subsequent reduction. Man. but can also start from appropriately substituted triamino-alkyl mercaptopyrimidines and the Substitute alkyl mercapto groups with amines. The latter method is particularly suitable for introduction of amino groups or of substituted amino groups in the 2-, 4- or 6-position of the pyrimidine ring.

Developer components to be used according to the invention are, for example, 2,4,5,6-tetraamino-, 4,5-diamino-2,6-bismethylamino-, 2,5-diamino-4,6-bismethylanino- _> 4,5-diamino-6 -butylamino-2-dimethylamino-, 2,5-diamino-4-diethylamino-6-methylamino-, 4,5-diamino-6-diethylamino-2-dimethylamino-, 4,5-diamino-2-diethylamino-6- mefchylamino-, 4,5-diamiro-2-dimethylamino-6-ethylamino-, 4,5-diamino-2-dimethylamino-6-isopropylamino- _J 4 _i 5-diamino-2-dimethylamino-6-methylamino-, 4 _i 5-Dia-mino-6-dimethylamino-2-methylamino-, 4,5-diamino-2-dimethylamino-6-propylamino-, 2,4,5-triamino-6-dimethylamino- _ί 4 _J 5,6- Triamino-2-dimethylamino ^^^ Triaminoomethylamino ^^ iöTriarnino 2-methylamino-, 4,5-diamino-2-dimethylaraino-6-piperidino-, 4,5-diamino-6-methylamino-2-piperidino.- _ί 2, 4 _ί 5-triamino-6-piper idino-, 2,4,5-triamino-6-anilino-, 2,4,5-triamino-6-benzylamino-, 2,4,5-triamino- 6-benzy lidenamino-, 4,5 ^ 6-Tii ^ iidi ^^ oTithi 2,4,5-triamino-6-di-n-propy lamino-, 2,4,5-triamino-6-morpholino-, 2,5,6-triamine o-4-dimethylamino-, 4,5,6- _{triamino-2-morpholino- J} 2,4,5-triamino-6-β-hydroxyethylamino-, 4,5,6-triamino-2 - ^ - amino-ethy lamino-, 2,5,6-triamino-4-P-methylamino-ethylamino-, 2,5-diamino-4,6-bis-y'-diethylamino-propylamino-, 4 , 5-diamino-2-methylamino-6- / 3-hydroxy-

509824/0971

Henkel & Cie GmbH

Patent department

äthylamino-, S ^ iyii ^ hydroxyäthylamino-6ranilina ^ 5 ^ amino-pyrimidine to be mentioned.

Examples of coupler components to be used in the hair colorants according to the invention are

cC-naphthol, o-cresol, m-cresol, 2,6-dimethylphenol, 2,5-dimethylphenol, 5,4-dimethylphenol, 5/5-dimethylphenol, Catechol, pyrogallol, 1,5- or Ii7 * -dihydroxynaphthalene, "5-Amlno - 2-.methylph.enol, hydroquinone, 2,4-diamino-anisole, m-toluylenediamine, 4-aminophenpl / Resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-J-methyl-pyrazolon-Si 1 -P.'ienyl-j5-amino pyrazolon-5j l-phenyl- ^ iS-aiketo-pyrazolldin, 1-methyl-7-dimethyl-amino - ^ - hydroxy-quinolone-2, l-Amino-5-acet-: acetylamino - ^ - nitro-benzene or l-Amino-5-cyanoacetylamino - ^ - nitro-benzene to cite.

In the hair dyes according to the invention, the Developer components generally roughly molar Amounts, based on the coupler substances used, used. If so, molar use is also useful proves, however, it is not disadvantageous if the developer component is in a certain excess or a shortfall is used. .

It is also not required that the developer component and the coupling substance constitute uniform products, but the developer component mixtures according to the invention to be used Tetraaminö- ''■> pyrimidine and the Küppiersubstanz mixtures of the above intermediates may pose. ι

In addition, the hair according to the invention can be colored - ^; means other known and common developer components, '

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Henkel & Cie GmbH

Patent department

and also, if appropriate, customary direct-removing dyes included in the mixture if this is necessary to achieve certain color nuances.

The oxidative coupling, i.e. the development of the color, can in principle be carried out in the same way as with other oxidized hair dyes also, done by atmospheric oxygen. However, chemical oxidizing agents are expediently used. Hydrogen peroxide or its addition products with urea, melamine, in particular, are used as such and sodium borate, as well as mixtures of. such hydrogen peroxide addition compounds with potassium peroxide disulphate.

The developer components according to the invention have Tetraaminopyrimidines have the advantage that they are already full in the event of oxidative coupling by atmospheric oxygen Provide satisfactory coloring results and thus damage to the hair due to what is otherwise responsible for the oxidative coupling used oxidizing agents can be avoided. However, at the same time, in addition to the coloring, there is a lightening effect If desired on the hair, the use of oxidizing agents is necessary.

The Haarf arbenemit eel according to the invention are for the Use in corresponding cosmetic preparations such as creams, emulsions, gels or even simple solutions incorporated and treated with one of the oxidizing agents mentioned immediately before use on the hair. The concentration of coupler-developer combinations in such dyeing preparations is 0.2 to 5 Weight percent, preferably 1-3> weight percent. For the production of creams, emulsions or gels, the dye components are mixed with those for such preparations usual other ingredients mixed. as

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HenkelSt Cie GmbH

Patent department

such additional components are e.g. network or. Emulsifiers of the anionic or non-ionogenic type, such as alkylbenzenesulfonates, fatty alcoholsulfates .; · Alkyl sulfonates, ... fatty acid alkanolamides, addition products of ethylene oxide with fatty alcohols, thickeners, like methy! cellulose- ,. Starch, higher fatty alcohols, Paraffin oil, fatty acids, also perfume oils and hair care products such as pantothenic acid and cholesterol should be mentioned. The additives mentioned are used in the amounts customary for these purposes »such as network. and emulsifiers in concentrations of 0.5-30 percent by weight and thickeners in concentrations from 0.1 to 25 percent by weight, each based on the entire preparation. .

The application of the hair dye according to the invention can, regardless of whether it is a solution, a Emulsion, cream or gel, im weak acidic, neutral or especially alkaline environment at a pH of 8-10. The application temperatures are in the range from 15 to 4o C. After an exposure time of about 1½ minutes the hair dye is applied to the hair to be colored Rinse away. Then the hair is washed with a mild shampoo and dried.

The advantages attainable with the inventive hair dye shades show using different developer "and intermediates an extraordinary possibility of variation which to dark brown and green ranges from blond to purple, the colors obtained ^have-good;. Light, washing and Reibechtheitseigenschaften and can be easily Remove reducing agents again.

The following examples are intended to illustrate the subject matter of the invention explain in more detail without, however, restricting it to this.

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Henkel & Cie GmbH

Patent department

Examples

First, the production of some in. The invention Hair dyes to be used tetraaminopyrimidines described, which are not previously known from the literature are.

Preparation of 2,4,6-trimethylamino-5-aminopyrimidine sulfate _{, C 7} H _{1 ^ Ng.H 2} SO ^ .2 H ₉ O

5.5 g of 2,4,6-trismethylaminopyrimidine were dissolved in 50 ml of water and brought to pH 4 with sodium acetate. The solution was heated to 80 ° C and added a solution of 1.4 g NanOp in 5 ^m l HPO. A red solution resulted. Sodium dithionite was added at 60 ° C. until the solution turned yellow. Dilute H ₂ SOh was added to the yellow solution and the precipitate was filtered off with suction. Yield 55 $

Pp 215 ° calculated: ■ % C 6th % H Jg N 6th Analysis: found: 26, 6th 6th , 4 26, 7th 26, 8th 27

x) According to Winkelmann, J. Prakt. Chem., 115> , 292, (1927).

Preparation of 2,4,5-triamino-6-di-n-propylaminopyrimidine dihydrochloride ^c iq ^H 20 ^N 6 * ^{2 HC1}

2,4,5-triamino-6-di-n-propylamino-pyrimidine sulfate shown in stages as follows :.

509824/0971

Henkel & Cie GmbH

Patent department

2,4-diamino-6-di-n-propy! Amino-pyrimidine

50 g of di-n-propylamine were added to 15 g of 2,4-diamino-6-chloropyrimidine ^x 'in 1 ^ 0 ml of ethanol and the mixture was ^{kept at 200 °} C. in the autoclave for 3 hours (initial pressure 10 atmospheric pressure). After cooling down and. Open """the reaction mixture in an ice-Kochsalzbad- was' cooled to di-propylaminhydrochlörid precipitate was filtered off and the mother liquor is largely concentrated (ca. ^ O radical ml) to yield 18 g = 82.9% precipitated crude product. this was processed as such,

2,4-digmino-5'-nitroso-6-di-n -prcpylanaino-pyrimidine

l8 g of 2,4-diamino-6-di-n-propylaiT.ino-pyrimidine (crude product) was slurried in 25 ml of water and with sufficient glacial acetic acid to pH \ was reached; it was then heated to 50 °, the substance being dissolved, and 5.5 g of sodium nitrite in 10 ml of water were slowly added; after a short time a raspberry-red precipitate fell out; sucked off and dried under vacuum at room temperature -

9.4 g = · ■ 46 $>. :. '. ·. · ■■ "Melting point : 206 - 208 ° C: ^; : Analysis:

calculated: found:

2 ', 4 ^ 5-triamino-6-di-n - pr'opylamino ^ pygimldindihydrochloride

6.5 g of 2-, 4-diamino-5 ^ nitro.so-6i-di-n-propyläminO-'pyrifflidin were hydrogenated in 150 ml of ethanol with 0.5 g of catalyst (Io % Pd on charcoal) in a shaking duck at room temperature . After the BU uptake was complete, the catalyst was filtered off, acidified with hydrochloric acid and concentrated. '

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SO 9824/0971

% C 40 7, H JB-N 27 50, 56 T, 61 35, 50 49, 62 35,

Henkel & Cie GmbH

Patent department

Residue: 5.6 g = 78.8 %, brown crystals, decomp. Point 105 ° C. The mass spectrum shows the. Molecular mass 224 (Ber. 224)

x) According to Roth, B., Smith, J.M., and Hultqüist, E.M., J..Am.Chem.Soc, 72, 1914 (1950).

Preparation of 2,4,5-triamino-6-morpholino-pyrimidine sulfate CgH ₁ ^ N ₆ O. HgSO ^

2,4,5-triamino-6-morpholinopyrimidine sulfate was gradually added made from the following compounds:

1. 50 g of morpholine (50 ml (0.54 mol) were added to 10 g of 2,4-diamino-6-chloropyrimidine ^{: x:) (0.07 mol) and the mixture was heated to 100 °} C. over the course of one hour while stirring ; at this temperature the mixture became

Held for 2 1/2 hours; then 10 ml of ethanol were added and left to stand in the refrigerator until morpholine hydrochloride had precipitated wax *, which was separated off. The filtrate was concentrated in order to obtain the crude product as a semi-oily semi-crystalline residue (5 * 9 = 45 * 7 %) '> processed further as a crude product.

2. 2,4-Diamino-6-morpholino-5-n-itroso-pyrimidine

5 * 9 g of 2 _{liters of} 4-diamino-6-morpholino-pyrimidine (0.05 mol) (crude product) were dissolved in 25 ml of water while warming, and acetic acid was added until pH 4 was reached. The solution was then heated to 80.degree and slowly add a sodium nitrite solution of 2 g in 5 ml of water; after a short time the nitroso compound precipitated out as a raspberry-red precipitate; concentration and cooling gave a total of 4.1 g = 60.3 % yield.

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509824/0971

2 »° bV :. ' H <yy tr Henkel & Cie GmbH 2,4,5-triamino-6-morpholinopyrimidine sulfate 5.39 Patent department _ calculated: % C 4y97 2359395 M.p .: 231 - found: 42.85 Analysis: 41.92 ^ N 37.48 38.22

2.5 s of 2,4-diamino-6-morpholino-5-nitroso-pyrimidine were suspended in 15 ml of water and treated with 2 η HCl (5 ml) until the substance was just dissolved; the substance mixture was then to 50; Sufficient sodium dithionite (Na ₂ SpO ^) was added slowly until the violet ring turned yellow. It was then filtered, cooled and adjusted to pH 2 with sulfuric acid (III). After a short time the pyrimidine precipitated as sulfate; 2, - 6 g = 76.4 % were obtained.

_Analysis:; (recrystallized): #C ^ H ^ N

calculated:. 31.17 5.23 '27.25 found: 29.8L 4.98, 27.86

Mp: sinters at 230 ° j slow decomp, from 255 ⁰ C

x) According to Roth, B., Smith, J.M. "and Hultquist, E.M., J. Am. Chem. Sog., 72, 1914 (1950).

The other tetraaminopyrimidines used in the examples below are known from the literature and are prepared in the manner shown in the monograph by DJ Brown "The Pyrimidines" in Heterocyclic Compounds, Intercsience Publishers, 1962 Volumes I and II. '

The hair dyes according to the invention were in the form of a Cream emulsion used. They were in an emulsion

the end . '■■ "-

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SO 9824/097 1

Henkel & Cie GmbH

Patent department

10 parts by weight of fatty alcohols with a key length of C, p-C, 6 10 parts by weight of fatty alcohol sulfate (sodium salt)

Chain length ^c io ~ ^C l8 75 parts by weight volume / water

0.01 mol each of the tetraaminopyrimidines and coupler substances listed in the table below incorporated. The pH of the emulsion was then adjusted to 9 * 5 by means of ammonia, and the emulsion made up to 100 parts by weight with water. The oxidative coupling was carried out either with atmospheric oxygen or with 1 $ iger Wf, .hydrogen peroxide solution as an oxidizing agent carried out, taking 100 pounds by weight; dividing the emulsion 10 parts by weight of hydrogen peroxide solution were given. The respective coloring cream with or without additional Oxidizer turned gray to 90 / £, Apply a not specially pretreated human larynx and leave it there for JO minutes. After the During the dyeing process, the hair was washed out with a conventional shampoo and then dried. The colorations obtained are shown in Table 1 below.

509824/0 9 71

Tabel

Henkel & Cie GmbH

Patent department

2359398

at developer Coupler game 1 2,4,5,6 -Tetraamino - m - Pheηy 1 ead.ia mi η pyrimidine 2 « 2,4-diaminoanisole 3 m-toluene diamine. 4th η m-aminophenol 5 ti Resorcinol 6th dd 1-Phenvl-3-amino ■

Preserved shade of air with

oxidation

^H 2 ° 2

-Dimethylamino 2,5,6-triamino pyrimidine

2-dimethylamine · 4,5,6 -triaminopyrimidine

py.razolone

1-phenyl -3 - me thy 1 ρ yr a ζ ο Io η

Res or a mono me thy 1-ether '

-Naphthol

1,5-dihydroxynaphthalene

1,7-dihydroxynaphthalene

m-phenylenediamine

2: 4 diaminoanisole m-tolylenediamine m-amino phenol Resorcinol

r-phenyl-3-amino pyrazolone

m - P hen y 1en d i am i η m-phenylenediamine olive

dark green-yellow-brown violet-brown strawberry red brown orange

brown red go ld br a u

olive

'' dark green yellow-brown violet-brown gray-red brown orange

brown orange golden brown

yellow-brown 'yellow-brown havanna-brown u η havana-brown

olive brown yellow brown

olive yellow yellow brown burgundy red brown-red raspberry-red

olive brown dark green

olive brown yellow brown

olive yellow

yellow-brown

burgundy red

brownish red

raspberry red

olive brown dark green

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9 82 4/09

game

Coupler Henkel & Cie GmbH
Patent department dark green 2: 4-x jiaminoanisole 23E olive-tinged -
yellow developer m-tolylenediamine > 9399 dark purple 2-dimethylamine) -
4, .5, 6-triamino-
pyrimidine m-aminophenol Preserved shade
for air with 1 ⁰ Jo HO
oxidation red-violet Resorcinol dark green brick red l-phenyl-3-amino-
pyrazolone (5) olive-tinged
yellow gray orange η 1-phenyl-3-methy 1-
pyrazolone (5) gray-violet olivbcaun η -Naphthol red-violet brass yellow η 3-acetylacetamino
1-amino-4-nitrobenzal brick red grey Red « l-phenyl-3,5-diketo-
pyrazolone lacquer red ivory π
Γ ο-cresol hair brown ivory - M m-cresol .yellow brown gray-green If 2, 5 -Di me thy Ip hen oil brown orange gray-green η 3, 4-dimethylphenol brown orange gray orange M. 3,5-dimethylphenol brown orange Brown η 1,5-dihydroxy
naphthalene brownish red metal gray η Pyrogallol brown or ange pale η Catechol brown orange golden blonde ft 1-methyl-4-hydroxy
7 -dimethylamino -
quinolone-2 Brown Brown η 5-amino-2-methyl-
phenol chocolate -
Brown ti red-brown M. gray orange Brown

509824/0971

Example developer

AS

Coupler

Henkel & Cie GmbH

Patent department

Color obtained with air oxidation

with 1 ⁰ Io H 2

2-Di me thy la min ο 4,5,6 -triaminopyrimidine

2-piperidino -4,5,6 'triaminopyrimidine

2-morpholines-4,5,6 triaminopyrimidine

2-methylamino-4,5,6 · triaminopyrimidine

6 -Morpholino -2, 4, 5-triami & opyrimidine

Hydroquinone

m-phenylenediamine

m-A minophenol

Resorcinol

2: 4 -D i am in ο a η i s oil

m-toluenediamine

1-phenyl-3 -amino pyrazolone (5)

m-phenylenediamine

m-A minophenol resorcinol

2: 4-diaminoanisole m-tolylenediamine

1 -P h eny1-3 -a mi no pyrazolone (5)

m-phenylenediamine

m ~ - amino ρ hen oil

Resorcinol

2: 4-Di a min pan is oil

m-tolylenediamine

1-phenyi-3 -anino pyrazolone (5)

m -Phenylendia ^ miri 2, 4-diamino an is oil

brownish red

dark green

golden blonde

dark green

dark purple dark purple

gray ruby. gray ruby

dark green dark green '

brown orange brown orange

tomato red. tomale red

olive

olive

dark purple dark purple

gray ruby gray ruby

dark green dark green

olive brown olive brown

brown-red brown-red

olive ■

dark purple

grey Red

dark green

yellow

brownish red

olive brown
gray-green

olive

dark purple

brown purple

dark green

yellow

brownish red

olive brown

olive

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Example developer

Coupler

Henkel & Cie GmbH

Patent department

2359393

Color obtained with air oxidation

with 1 "} o H 2

6-morpholino-2,4,5 · triaminopyrimidine

6-piperidino-2,4,5 · triaminopyrimidine

6-Di-n-propylamine »■ 2,4,5-triaminopyrimidine

m-tolylenediamine

m-aminophenol resorcinol

l-phenyl-3-aynino-pyrazolone-5

m-phenylenediamine

2,4-Di amino anisole m-aminophenol Resorcinol m-tolylenediamine

1-phenyl-3-aminopyrazolone-5

m-phenylenediamine

golden yellow

gray ruby brownish red

dull red

olive brown olive brown

gray-red gray-yellow gems-yellow

honey yellow

pyrazolone-5

509824/0971

brass yellow

gray-red brown-red

dull red

bamboo yellow gray yellow

olive

bamb us yellow

ivory

olive brown

straw yellow

olive

71 M. 2,4-diaminoanisole olive green olive 72 11 m-tolylenediamine honey yellow honey yellow 73 H m-aminophenol gray ruby dreadful 74 η Resorcinol brownish red brownish red 75 dd l-phenyl-3-amino- red-brown red-brown pyrazolone-5 76 2, 4, 6-trismethyl m-phenylenediamine oak brown olive amino-5-amino- pyrimidine 77 tf 2,4-diaminoanisole olive beaver brown 78 η m-tolylenediamine brass yellow olive 79 η m-aminophenol dark ruby Brown 80 η Resorcinol grey Red frosted! ot 81 H l-phenyl-3-ainino- red-brown light brown

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Henkel & Cie GmbH

Patent department

To check the toxicological and dernsato logical For properties of tetraaminopyrimidines, the investigations described below were carried out. The test substance used was 2-dimethyl'-4,5 * 6-triaminopyrimidine sulphate / which is set in comparison to p-phenylenediamine and p-toluenediamine sulfate; became. Included the following results were obtained; ..

1. Acute toxicity ■

The general tolerance tests were carried out on male white mice of the CFAi €> 8 strain. The average weight; the test animals was 22 g. The test substances were administered once in increasing doses with the gavage. 10 mice were used per dose. The application volume was a constant 0.2 ccm / 10 g body weight. After the 8-day observation period and after calculating the test results according to the method of Litchfield-Wilcoxori (J. Pharm. Exptl. Ther., 96 99-108 (1949)), the following LD ₁ - ^ values were found. ■ ·;

2-dimethylamino-4 _> 5j6 - triaminopyrimidine

sulfate. . 555 mg / kg.

p-phenylenediamine ■ 87 mg / kg "

p-Tolylenediamine sulfate x 110 mg / kg

Aqua de st "was used as the solvent,

2. Skin compatibility tests on hairless mice ·;

Groups of 5 animals per preparation were the; Test substances in 5% aqueous solutions once

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Hang! & Cie GmbH

Patent department

applied daily in small amounts to the skin of the back for 14 days. During the application time and at the end of the experiment all animals showed no reaction.

3. Mucosal compatibility tests on rabbit eyes

These local compatibility tests were done so that small amounts of the $ .igen aqueous test substances groups of albino rabbits once instilled into the conjunctival sac of one eye. The reactions of the mucous membranes were according to a point scheme by Draize (Appraisal of the safety of chemicals in foods, drugs and domestics. Ass. Of Pood and Drug Officials of the U.S., pp. 49-52 (1959)) 2, 6, 24 and 48 hours after application evaluated. It was found that · p-phenylenediamine led to a slight reddening and Exudation of the conjunctiva leads, which is no longer detectable 24 hours after instillation. The two other test substances were tolerated without reaction.

4. Skin (tissue) compatibility tests on white mice after a single intracutaneous application of various concentrations of egg test preparations

This test of the local compatibility according to Barail (J. Soc. Cosmet. Chemists JLL, 241 (1960)) is based on the intracutaneous application of small amounts of the test substance in increasing concentrations in the White mouse abdominal skin. After 2% hours, the test animals are sacrificed, the treated areas of the skin cut out and dried. The assessment of skin damage is based on a point scheme, taking into account blood flow and other damage to the treated skin. Since pro

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Henkel & Cie GmbH

Patent department

Preparation and per test concentration. If a larger group of animals of 10 mice was used, finer differences in terms of local tolerance can be determined using the above test method: The test results are shown in Table 2 below
refer to. ■

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Table 2

Skin (tissue) compatibility test on white mice after intracutaneous application (test according to

Barail)

Average values after assessing 10 test animals per preparation or per concentration

2-dimethylamino-4 > 5,6-triaminopyrimidine sulfate

Points or degree of skin damage

2 1

p-phenylenediamine

p-toluenediamine sulfate

1 O ₁ ? ο, 9 2.7

ο, 5 ο, 9

ο, 9 2.7 concentrations of the
Erüfsubstanzen in %

cn to co

CD

co

3 σ DC

Henkel & Cie GmbH

Patent department

The test results listed above are applicable infer that 2-dimethylamino-4-, 5/6-triaminO-v pyrimidine sulfate in terms of a general and local Compatibility among the tested developer substances behaves best. Besides these good ones toxicological and dermatological 'properties bring the tetraaminopyrimidines to be used in the hair colorant according to the invention the further advantages with it that the development of the color is already with Oxygen in the air can take place and. Leads to an extraordinary range of color shades that good light, wash and rub fastness properties g. mark and again with reduction labels are easily removable.

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9024/0971

Claims (7)

Henkel & Cie GmbH patent department patent claims 1). Hair dyes based on oxidation dyes, characterized by a content of tetraaminopyrimidines of the general formula ^H K J in which R - R ^ hydrogen, an alkyl radical with . 1-4 carbon atoms, the radical - (CH ₂ ) _n - X, in which η = 1 - 4 and X can be a hydroxyl group, a halogen atom, an -NRp-, -NHR ¹ - and -NR'R "group, where R ¹ and R "can denote alkyl radicals with 1-4 carbon atoms or are closed with the nitrogen atom to form a heterocyclic ring which can contain a further nitrogen atom or oxygen atom, an optionally substituted aryl radical, an optionally substituted heterocyclic 5- or 6-membered ring with one or two nitrogen atoms or one nitrogen atom and one Can represent oxygen atom, as well as their inorganic or organic salts as developer substances and those commonly used in oxidation hair colors Coupler substances. 2) Hair dye according to claim 1, characterized by a content of a mixture of Tefcraaminopyrimidines - 23 - SO9S24 / 0971 Hang! & Cie GmbH Patent department as a developer component with those in oxidation hair colors usual. Kupple.rsubs dance. . 3) Hair colorant according to claim / i and 2, characterized '" by a content of other conventional developers --- <' substances, and optionally conventional substantive dyes. 4) Hair dye according to claim i - '3l · characterized by a content of developer-coupler combinations of tetraaminopyrimidines and in the hair color common coupler substances from 0.2 to 5 percent by weight, preferably from 1 to 3 percent by weight. 5) 2,4,6-trismethylamino-5-aminopyrimidine. 6) 2,4,5- ^ iamino-6-di-n-propylaminopyriniidine. . 7) 2,4,5-triamino-6-morpholino-pyrimidiii. 824 / 097'f