FI68070C - NYA BIS-AMINOPYRIDINER FRAMSTAELLNING OCH ANVAENDNING DAERAV SOM COMPONENTER I OXIDATIONSHAORFAERGER SAMT DESSA INNEHAOLLANDE HAORFAERGAEMNEN - Google Patents

Description

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C (45) Γ ^ ϋ .: '. . Ι .ό '' (51) Kv.ik. * / Int.ci. * C 09 B 57/00, C 07 D 213/74, A 61 K 7/13 (21) Patent application - Patentinsökning 792244 (22) Application date - Ansökningsdag 17.07.79 ^) (23) Start date - Giltighetsdag 17.07.79 (41) Has become public - Blivit offentlig gg Q2 gg

National Board of Patents and Registration Date of display and publication--

Patent- och registerstyrelsen '' Ansökan utlagd och utl.skriften publiccrad 29 .03.85 (32) (33) (31) Requested privilege - Begärd priority 07.08.78

Federal Republic of Germany Förbundsrepubli ken Tyskland (DE) P 2834605.6 (71) Henkel Kommanditgesel1schaft auf Aktien, Henkelstrasse 67, 4000 Diissel-Dorf 1, Federal Republic of Germany-Förbundsrepubliken Tyskland (DE) (72) David Rose, H, , Edgar Lieske, Dusseldorf, Federal Republic of Germany-Förbundsrepubliken Tyskland (DE) (74) Oy Heinänen Ab (54) New bis-aminopyridines, their preparation and use as components in hair oxidation dyes and hair dyes containing them -Nya bis-aminopyridiner, framstä11 Ning The present invention relates to bis-aminopyridines which are suitable for use as components of hair oxidation dyes and which have the general formula v-jol R foV'-v

N N

wherein R is -HN-CH 2 -NH-, or -HN-CH-CH 2 -NH-.

2 68070

Other objects of the invention are a process for the preparation of said bis-aminopyridines, the use of said bis-aminopyridines as such or their salts with inorganic or organic acids as coupling and / or developer components in hair oxidation dyes and hair dyes containing said bis-aminopyridines salts.

The so-called oxidative dyes, which are formed in the oxidative coupling reaction of the developer component with the coupling component, are of great importance in hair coloring due to their intense color tones and very good authenticity properties. Nitrogen bases such as p-phenylenediamine derivatives, diaminopyridines, 4-aminopyrazole derivatives and heterocyclic hydrazones are usually used as developing agents. Among the so-called coupling components, mention may be made of m-phenylenediamine derivatives, phenols, naphthols, resorcinol derivatives and pyrazolone.

Above all, the oxidative dye components of good hair must meet the following requirements:

They must form the desired color tones with a sufficiently high color intensity as a result of the oxidative coupling reaction with the developer or coupling component used in each case. In addition, they must have a sufficiently high or even very good adhesion to human hair, in addition to which they must be products which are harmless in toxicological and dermatological terms.

As a result, there is a need to find suitable components for hair oxidation dyes that meet the above requirements in the best possible way.

It has now been observed that hair oxidation dyes which meet their requirements very well can be prepared by using bis-aminopyridines of the general formula 3 68070 h / '~ f 0] RI Or “2 · N ^ as developing components and / or coupling agents. (v wherein R represents -HN-CH 2 -NH- or -HN-CH 2 -CF 2 -NH-, and their inorganic or organic salts.

Dyes based on oxidizing dyes with a certain amount of bis-aminopyridines of the general formula H * N ~ f Oi r | OVNH2 'k N> - ^ N - where R may represent the group -HN-CHg-NH- or -HN -CH 2 -CF 2 -NH-, or their inorganic or organic salts as developer components and / or coupling agents and optionally also coupling agents or developer components commonly used in hair oxidation dyes, thus form particularly useful hair oxidation dye compositions.

When the bis-aminopyridines according to the invention are used as developer components and / or coupling agents, either alone or in combination with coupling agents or developer components commonly used in hair oxidation dyeing, a wide variety of high-intensity shades are obtained, in particular brown The dyes obtained with the bis-aminopyridine according to the invention have very good authenticity properties, in addition to which they are very soluble in water, have good storage properties and are harmless in toxicological as well as dermatological proportions.

According to the invention, the bis-aminopyridines to be used as component and / or to be used can be used either as such or in the form of their salts with inorganic or organic acids, such as, for example, chlorides, sulphates, phosphates, acetates, as propionates, lactates and sitates.

The bis-aminopyridines used according to the invention are prepared analogously to methods known from organic chemistry by reacting 2-halonitropyridines, in particular 2-chloronitropyridine, with the corresponding divalent diaamines and carrying out the catalytic reduction of the reaction product to the corresponding bis-aminopyride.

Among the developer components and / or coupling agents to be added according to the invention, mention may be made, for example, of N, N'-bis- [5-aminopyridyl- (2)] -ethylenediamine dihydrochloride, N, N'-bis - [? 3-aminopyridyl- (2-ethylenediamine tetrahydrochloride). and N, N'-bis-η 5 -aminopyridyl- (2) 3-diaminomethane tetrahydrochloride.

Examples of hair dye coupling agents to be added according to the invention are -naphthol, o-cresol, m-cresol, 2,6-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, brentscatechin, pyrogallol, 1,5- or alternatively 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, hydroquinone, 2,4-diaminoanisole, m-toluenediamine, 4-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, l- Phenyl-3-methyl-pyrazolone-5,1-phenyl-3-aminopyrazolone-5,1-phenyl-3,5-diketo-pyrazolidine, 1-methyl-7-dimethylamino-4-hydroxy-quinolone-2 , 1-amino-3-acetacetylamino-4-nitrobenzene or 1-amino-3-cyanoacetylamino-4-nitrobenzene.

Examples of developer components to be added to hair dyes according to the invention include primary aromatic amines which additionally have functional groups in the p-position, such as p-toluenediamine, monochloro-p-phenylenediamine, p-dimethylaminoaniline, p-aminophenol, p-aminophenol, compounds which are similar, which may additionally have one or more functional groups such as OH group, NH 4 group, NHR groups, NR 4 groups, wherein R is an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms, and in addition diaminopyridine derivatives, heterocyclic hydrazone derivatives, 4-aminopyrazolone derivatives such as 4-amino-1-phenyl-3-carbamoylpyrazolone-5, tetraaminopyrimidines 68070 such as 2,4,5,6-tetraamino-, 2-dimethylamino- 4,5,6-Triamino-, 6-morpholino-2,4,5-triamino-, 2,4,5-triamino-6-β-hydroxyethylaminopyrimidine, N, N-bis- (β-hydroxyethyl) p-phenylenediamine: ni.

As stated above, the bis-aminopyridines according to the invention can also be used as the exclusive dye components of hair dyes, since these can be subjected to an oxidative coupling reaction with one another.

According to the invention, developer components are generally added to hair dyes in approximately molar proportions based on the amounts of coupling agents used. However, if a molar mixing ratio of the substances proves to be appropriate, it is not a disadvantage, even if the developer component is used in the mixture in a certain amount in excess or in excess.

Furthermore, it is not necessary that the developer component and also the coupling agent be homogeneous products, but rather the developer components as well as the coupling agents may be mixtures formed from the above-mentioned corresponding compounds.

In addition, the hair dyes according to the invention may also contain other known and conventionally used developer components or coupling agents, and possibly also other direct coloring dyes in admixture, if this is necessary to obtain certain color shades.

The oxidative coupling reaction, i.e. the development of coloring, can in principle be carried out in the same manner as when other hair oxidation dyes are used, in which case the oxidant is oxygen in the air. However, chemically active oxidizing agents are preferably added. These are, in particular, hydrogen peroxide or its coupling products with urea, melamine and sodium borate, as well as mixtures of such hydrogen peroxide coupling products with potassium peroxide sulphate.

The bis-aminopyridines used according to the invention also have the advantage that already during the oxidative coupling reaction with air without oxygen they form satisfactory coloring oxides, minrii damage to the hair due to the addition of hnpe t usa i ne i dc n to cause an otherwise oxidative coupling reaction. effect. '! 5 68070 can be avoided. However, if it is desired to achieve a hair bleaching effect at the same time as coloring, oxidizing agents must also be used in the mixture.

The hair dyes according to the invention are added to suitable cosmetic preparations such as creams, emulsions, gels or also to ordinary solutions by mixing the substances together and immediately before their application to the hair by mixing one of the above-mentioned oxidizing agents. Such coloring preparations contain from 0.2 to 5% by weight, preferably from 1 to 3% by weight, of coupling and developing agents. For the preparation of creams, emulsions or gels, the dye components are mixed with other ingredients commonly used in such preparations. Such other ingredients include, for example, wetting or emulsifying agents of the anionic or nonionic type, such as alkylbenzenesulfonates, fatty alcohol sulfates, alkyl sulfonates, fatty acid alkanolamides, reaction products of ethylene oxide with fatty alcohols, thickeners such as thickeners such as thickeners. alcohols, paraffin oil and fatty acids. Also to be mentioned are perfume oils and hair conditioners such as pantothenic acid and cholesterol. Said additives are then used for this purpose in conventional amounts, for example wetting and emulsifying agents are used in concentrations of 0.5 to 30% by weight and thickeners in concentrations of 0.5 to 25% by weight, these amounts being calculated on the total amount of the preparation.

The use of the hair dyes according to the invention can take place, whether in the form of a solution, emulsion, cream or gel, in a weakly acidic, neutral or even alkaline environment, in which case its pH can be in the range from 8 to 10. The operating temperatures are then in the range 15-40 ° C. After an exposure time of about 30 minutes, the hair dye is removed from the colored hair by rinsing. The hair is then washed with a mildly active shampoo, after which the hair is dried.

The hair dyes according to the invention have the possibility of providing a very wide range of variations by adding various developer and coupling components, whereby the color shades can vary from light brown to dark brown and reddish brown, which Iisak: - ·! can also be a i k n a n s n n d n Khuk i -v liic · j ä and t u m m .a line h 1 'c a li 7 68070 color tone. The dyes obtained have good color, washing and abrasion-resistant properties, in addition to which they can be easily removed by using reducing agents.

The following examples further illustrate the invention without limiting the scope of this invention in any way.

E _s i_m_e_r_k_k_e j__a

First, a process for the preparation of some novel bis-aminopyrimidines of the invention will be described.

product A

N, N 1 - Bis- [5-aminopyridyl] - (2β-ethylene diamine hydrochloride) To a solution of 15.9 g of 2-chloro-5-nitropyridine in ethanol was added dropwise 3 g of ethylenediamine. The reaction mixture was refluxed for one hour under cooling and after cooling the mixture gave a yellow reaction product, N, N'-bi s- [5-aminopyridyl - (2) -3-ethylenediamine, which was removed by suction filtration. ° C.

5 g of the obtained intermediate in 50 ml of ethanol were reduced from catalytic (10% palladium on carbon). After uptake of hydrogen, the catalyst was removed by filtration and the solution was acidified using dilute hydrochloric acid. After evaporation to dryness, 5 g of N, N'-bis- [5-aminopyridyl] - (2) -J-ethylene diamine hydrochloride were obtained as a brown powder. The mass spectrum showed that its molecular weight was 268 (calc. 268).

Example_2 product B

ϋχΝ'-bis-β-aminopyridyl 11- (2) -ethylenediamine hydrochloride As described in Example 1, 15.9 g of 2-chloro-3-nitropyridine was reacted in ethanolic solution with 2.4 g of ethylenediamine to give N, N '-bi s-β-nitropyridium with 1 - (2) -ethylenediamine. This gave 10.3 g of a yellow powder with a melting point of 125 ° G.

8 68070

In the same manner as in Example 1, 5 g of the obtained color product was catalytically reduced in ethanol solution, after which the mixture was acidified. 4.5 g of N, N'-bis-β-aminopyridyl- (2) -N-ethylenediamine hydrochloride were obtained as a brown powder.

Example_3 product C

N, N '- b i s- [5-aminopyridyl- (2) -diaminomethane tetrahydrochloride 5 g of Ν, Ν'-bis 5-aminopyridyl- (2) -diaminomethane prepared as described in A.E. Tschitschibabin & J.L. Kunjanz, Chem.Ber. 62 (1929) 3052, was catalytically reduced in 100 ml of ethanol using 1 g of palladium precipitated on carbon as a catalyst. After completion of the hydrogen coupling reaction, the mixture was filtered into 150 ml of dilute hydrochloric acid and evaporated to dryness. 2.5 g of an orange powder with a melting point of 240-244 ° C were obtained while the product decomposed.

The hair dyes according to the invention were converted into a cream emulsion. In this case, a mixture of 10 parts by weight of fatty alcohols having a carbon chain length of 011 C12 to C18 of 10 parts by weight of fatty alcohol sulfate (sodium salt) was prepared with a carbon chain length of C10 to C10 of 10 to 75 parts by weight of water. always mixed with 0.01 moles of the developer components and coupling agents shown in the following table. The pH of the emulsion was then adjusted to 9.5 with ammonia and made into 100 parts by weight by adding water to the emulsion. The oxidative coupling took place using either atmospheric oxygen or a 1% hydrogen peroxide solution as the oxidizing agent, with 10 parts by weight of the hydrogen peroxide solution being added to 100 parts by weight of the emulsion.

The respective coloring cream, with or without the addition of an oxidizing agent, was applied to 90% grayed and not specially pretreated human hair, with an exposure time of 30 minutes. At the end of the dyeing process

II

9,68070 The hair was washed with a conventional hair detergent and then dried. The staining results obtained are shown in Table 1 below.

In combination with the bis-aminopyridines used according to the invention, the following compounds were then added to the mixture as additional colorant components: the product 1 «--naphthol" 2 resorcinol "3 p-toluenediamine" 4 2,4,5,6-tetraaminopyrimidine , 4-diaminoananoyl 6 resorcinomethyl ether

Table_l ----------- r ----—-------------------------------- ------------------ _______________ oxidation using air _E erkk Kehitinänne Ky kkinine using 1 ^% M2 —2 4 product B product 4 amber brown j 5 "" 3 amber amber ji 6 "" 1 light green turkey j 7 j "" 5 light green dark green · 8 "" 2 brown brown jj 9 product A ”4 dark brown dark brown i 10" "3 brown dark brown 11" "6 red brown j red brown i 12" "5 green 1 dark green j

i 13 "4" C brown! brown I

I I! I 14 "3" C amber i dark brown 15 ί "C" 1 I khaki amber ill; 16! "C" 2 in khaki amber __________ i ___________ j __________ L _______________, __________________

Claims (6)

1. Bis-aminopyridines suitable for use as oxidizing dye components herein are characterized in that their all-enamelled forinel is h2n-To] IOnh2 · ^ N ^ N ^ where R represents the group -HN-CH2 -NH - or -HN-CH 2 -CH 2 -NH-. 2. Bis-aminopyridine according to Claim 1, characterized in that N, N'-bis-11L-5-aminopyridyl- (2) 3-ethylenediaraine, N, N * -bisTs-aminopyridyl- (2) 3-ethylenediamine, or N, N'-bis [α] -aminopyridyl- (2) 3-diaminomethane. Process for the preparation of bisaminopyridines according to claim 1 or 2, characterized in that the corresponding 2-halo-nitropyridine, especially 2-chloro-nitropyridine, is reacted with the corresponding dihydric diamine and the resulting reaction product is catalytically reduced . Use of bis-aminopyridines according to claim 1 or 2 and of salts formed therefrom and inorganic or organic acids as development components and / or coupling agents in oxidation dyes here. Dyeing agents here based on oxidation dyes, characterized in that they include a certain amount of bisaminopyridines according to claim 1 or 2 or salts formed from them and inorganic or organic acids such as developing agents and / or coupling agents and possibly Mven seeds. developer components or coupling agents normally used in oxidizing dyes