Symmetrical triazine derivatives and the way they are received (options)

 

(57) Abstract:

Describes the symmetrical triazine derivatives of General formula I, where R1and R2- identical and denote hydrogen or C1-C5-alkyl; R3- C1-C12-alkoxy, and two ways of obtaining them. The connection I have protective properties against UV radiation. 3 S. and 1 C.p. f-crystals.

The invention relates to symmetrical triazine derivative, to obtain these compounds and to their use for the protection of organic materials from the harmful effects of ultraviolet radiation.

O-alkylated o-hydroxyphenyltriazine (GFT) containing at least one o-hydroxyl group or at least two alkoxyphenyl-Deputy, known, for example, from a European patent application 0743309 as cosmetic absorbers of ultraviolet radiation having good spectral properties and good properties for technical applications. However, obtaining such derivatives of triazine, which originate from the asymmetrical main patterns

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requires multi-step synthesis process.

In the above formula, each of Raand R

For symmetrical triazine derivative, which can be obtained from the symmetric primary structure

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you can easily gain access in a simple one-time process.

Such "basic structure of the triazine can be obtained, for example, by trimerization of the corresponding compounds of benzonitrile or starting from cyanuric chloride by the Grignard reaction or alkylation Friedel -. Subsequent esterification of free groups IT allows to obtain the desired derivatives of triazine in the process of two-step reactions.

In accordance with this present invention relates to symmetrical triazine derivative of the formula

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where R1and R2are the same and represent hydrogen or C1-C5-alkyl; R3- C1-C12-alkoxy.

C1-C12-alkyl or C1-C12-alkoxy denotes remotemachine or branched radical of alkyl, typically methyl, ethyl, n-propyl, isopropyl, sec-butyl, tert-butyl, amyl, isoamyl or tert-amyl, heptyl, octyl, isooctyl, nonyl, decyl, undecyl or dodecyl, or methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy or DoD is12-alkoxy, a R1and R2have the meanings given in the formula (1).

Derivatives of triazine in accordance with the present invention can be used as individual compounds or as mixtures of different individual connections with each other.

New symmetrical triazine derivatives of formula (1) may, in particular, also be used as mixtures with triazine compounds of the formula (4)

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where R10denotes hydrogen, C6-C12-alkyl or C2-C6alkenyl, and R11stands WITH1-C12-alkoxy.

WITH2-C6Alkenyl means, for example, allyl, methallyl, Isopropenyl, 2-butenyl, 3-butenyl, Isobutanol, n-Penta-2,4-dienyl or 3-methyl-but-2-enyl.

New triazine derivatives of formula (1) can be obtained in various ways. In the Grignard reaction, for example, 1 mol of cyanuric chloride is subjected to interaction with 3 moles of the corresponding connection fenermine bromide, which depending on the values of R1, R2and R3in the formula (1) may contain an alkyl radical and/or one or more free hydroxyl groups. Methods of obtaining this intermediate compounds are known and described the Ute by alkylation Friedel-of cyanuric chloride with the corresponding connection phenyl formula

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where R1and R2is hydrogen or C1-C5alkyl, in the presence of a Lewis acid, preferably aluminum chloride.

In accordance with the work of A. Ninagawa, M. Kawazoe, H. Matsuda, Makromol. Chem. 180 (1979), 2123, this intermediate compound is also obtained by cyclotrimerization connection benzonitrile formula

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where R1and R2is hydrogen or C1-C5alkyl.

The final products corresponding to the formula (1), get to the second stage reaction, the esterification of the free hydroxyl groups of the intermediate compounds obtained in the first stage reaction, an alkylating agent lR3where R3- C1-C12-alkoxy, in accordance with the traditional methods.

Another object of the present invention relates to methods of producing new derivatives of triazine.

Symmetrical triazine derivatives of formula (1) or a mixture of these compounds with compounds triazine of the formula (4), and also compounds of the formula (5)

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where AG denotes the radical of the formula

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R1denotes hydrogen, hydroxy, C1-C12-alkyl or C1-C12-alkoxy;

R2denotes hydroxy, C1-C12-alkoxy; or benzyloxy;1
-C12-alkoxy; or

R1and R2together with the phenyl radical denote heterocyclic five-membered ring, which is condensed with benzene, preferably a radical of the formula (5A),

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especially suitable as filters ultraviolet radiation, that is to protect sensitive to UV light organic materials, especially the skin and hair of humans and animals, from the harmful effects of ultraviolet radiation.

Typical examples of compounds of the formula (5) are

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Accordingly these compounds are suitable as light stabilizers in cosmetic, pharmaceutical and veterinary preparations. They can be obtained in dissolved form or, if they are only sparingly soluble or insoluble, they can be entered into drugs in powdered form with an average particle size in the range from 0.02 to 2, preferably from 0.05 to 1.5, and most preferably from 0.1 to 1.0 μm.

In addition to the new ultraviolet light absorbers, the cosmetic compositions can also contain one or more than one of a number of other compounds that protect against ultraviolet islil 4-dimethylaminobenzoate;

2) salicylic acid derivatives, such as 2-ethylhexyl salicylate;

3) derivatives of benzophenone, usually 2-hydroxy-4-methoxybenzophenone and its derivatives 5-sulfonic acids;

4) derivative dibenzoylmethane, usually 1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)propane-1,3-dione;

5) diphenylacetate, usually 2-ethylhexyl-2-cyano-3,3-diphenylacetate and 3-(benzofuranyl)-2-cyanoacrylate;

6) 3-imidazol-4-yl-acrylic acid and 3-imidazol-4-yl-acrylate;

7) derivatives benzofuran, preferably derivatives of 2-(para-AMINOPHENYL)benzofuran disclosed in the application for the European patent 582189; U.S. patent 5338539; U.S. patent 5518713 and in the application for the European patent 613893;

8) polymeric ultraviolet light absorbers, such as derivatives of benzylidenemalonate described, among other things, the application for the European patent 709080;

9) derivatives of cinnamic acid, such as 2-ethylhexyl 4-methoxycinnamate or isoamyl or derivatives of cinnamic acid are disclosed, inter alia, in U.S. patent 5601811 and the patent application PCT WO 97/00851;

10) derivatives of camphor, usually 3-(4'-methyl)-benzylideneamino-2 he, 3-benzylideneamino-2-it, N-[2(and 4)-2-oxoborn-3'-ylidenemethyl) benzyl]acrylamide polymer, 3-(4'-ammonium)benzylideneamino-2-he shall, -(4'-sulfo)-benzylideneamino-2-he and its salts;

11) derivative trainline-second-triazine, 2,4,6-Tianjin-(para-Carbo-2'-ethyl-1'-oxy)-1,3,5-triazine, as well as ultraviolet light absorbers disclosed in U.S. patent 5332568, in the application for the European patent 517104, in the application for the European patent 507691, in the patent application PCT WO 93/17002 and in the application for the European patent 570838;

12) derivatives of 2-hydroxyphenylacetate;

13) 2-phenylbenzimidazol-5-acid and its salts;

14) of mental-ortho-aminobenzoate;

15) TiO2(c different coatings), ZnO and mica.

The ultraviolet light absorbers described in "Sunscreens", Eds. N. J. Lowe, N. A. Shaath, Marcel Dekker, Inc., New York and Basel, Cosmetics & Toiletries (107) 50 et seq. (1992), can also be used as an additional protective agents against UV radiation in the proposed structures.

The cosmetic compositions may also be used together with known antioxidants, such as vitamin E, carotenoids or spatial-employed amides, serve as light stabilizers for polymers.

New cosmetic formulations usually contain from 0.1 to 25, preferably from 0.5 to 10% by weight, based on the total weight of the composition, of the absorber ultraviol is also cosmetically compatible excipient.

Cosmetic compositions can be obtained by physical mixing of the absorber (absorbers) ultraviolet radiation with an auxiliary additive by conventional methods, for example by simple mixing of the individual components.

Cosmetic compositions can be prepared in the form of an emulsion of the type water-in-oil or oil-in-water, in the form of a lotion type of oil in alcohol, in the form of porous (porous) dispersion of ionic or nonionic amphiphilic lipid, as a gel, solid globular preparation or in the form of an aerosol composition.

As the emulsion of the type water-in-oil or oil-in-water cosmetically compatible excipient preferably contains from 5 to 50% oil phase, from 5 to 20% of an emulsifier and from 30 to 90% water. The oil phase may contain any oil suitable for cosmetic formulations, for example one or more hydrocarbon oils, paraffin wax, natural oil, silicone oil, ester of fatty acid or fatty alcohol. Preferred mono - or polyolene are ethanol, isopropanol, propylene glycol, hexyleneglycol, glycerin and sorbitol.

Cosmetic compositions for the hair can be

in the form of shampoo, loses, before or after a process of permanent or straightening;

- in the form of a lotion, foam or gel for styling or hair treatment;

- in the form of a lotion or gel for hair or perming hair;

as hairspray;

- in the form of a composition for permanent or straightening, dyeing or removal of dye.

As for the hair, it is possible to use, for example, the following cosmetic ingredients:

a1) spontaneously emulsifying original compositions comprising an absorber of ultraviolet radiation, eskaleut sorbitan and10-oxopent PEG-6, which is loaded with water and any connection Quaternary ammonium compounds, such as 4% minamimorimachi-2-hydroxyethyl ammonium chloride or Quaternium 80;

a2) spontaneously emulsifying original compositions comprising an absorber of ultraviolet radiation, tributyl citrate and monooleate sorbitan PEG-20, which is loaded with water and any connection Quaternary ammonium compounds, such as 4% minamimorimachi-2-hydroxyethyl ammonium chloride or Quaternium 80;

b) quaternion-doped solutions absorber of ultraviolet radiation in the butyl triglycol and tributyl citrate;

c) dispersion of ground to micron of raw or mixtures of solutions, chopping) with an average diameter of 0.05 to 1.0 μm (for example, Plantaren), and the Quaternary compound (for example, minamimorimachi-2-hydroxyethyl ammonium chloride) in an aqueous formula;

d) a mixture of solutions absorber of ultraviolet radiation with n-alkylpyridinium.

Compositions for cosmetic use, used in accordance with the present invention for protecting the skin or hair, may also contain other ingredients, such as emollients, emulsion stabilizers, skin moisturizers, tanning accelerators, thickeners, such as xanthan gum, means to retain moisture, such as glycerol, preservatives, aromatics and dyes.

New cosmetic compositions for the skin or hair an excellent protection of the human skin and hair from the harmful effects of sunlight.

The following not limiting the scope of invention Examples illustrate the invention in more detail. The percentages are given by weight.

Example 1: Getting 2,4,6-Tris(4-2-ethylhexyloxyphenol) -(1,3,5)-triazine

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The basic structure formula

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produced by cyclotrimerization p-hydroxybenzonitrile. For this purpose, 5.0 g (42 mmol) of p-hydroxybenzonitrile added slowly to the keys of ice water, filtered off, washed with hot water and recrystallized from aqueous methanol. Output connections (101A) of 62%.

are 5.36 g of compound of formula (101A) are dissolved in 50 ml of dimethylformamide (DMF) and then adding to the mixture 6,53 g of finely ground potassium carbonate at a temperature of 100-105oC. This mixture is stirred for 30 minutes, after which 8,23 g of 3-(chloromethyl)heptane, dissolved in 10 ml of DMF, is added dropwise within 30 minutes at a temperature of 100-105oC. the Temperature of the mixture is slowly increased to 135oC for 6 hours. After cooling to a temperature of 100oWith add 50 ml of toluene and precipitated salts are removed by filtration. The filtrate is concentrated to dryness by evaporation and the residue is taken up with 50 ml of toluene and 100 ml of water, acidified and shaken out. The dried organic phase is concentrated by evaporation. The crude product (about 7 g) purified column chromatography (silica gel, cyclohexane/toluene 7:3). Yield: 4.8 g of colorless oil (46% of theoretical), characterized by13With NMR (90 MHz, Dl3): = 11,54; 14,50; 23,47; 24,27; 29,52; 30,93; 39,77; 71,11; 114,79; 129,11; 131,13; 163,43; 171,02.

Example 2: Obtain 2,4,6-Tris(3,5-dimethyl-4-(2 - ethylhexyloxyphenol)- (1,3,5)-triazine

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Basic Strokach 700 g of tetrachloroethylene, stirred for 40 min at room temperature. 73 g of 2,6-dimethylphenol add to this mixture (molar ratio of cyanuric chloride for 2,6-dimethylphenol 1:3). The reaction proceeds under stirring at room temperature over the next 93 hours. Dense reaction product is separated by filtration and washed with 100 g of 2 N HCl. This product is purified by recrystallization from 100 g of hot dimethylformamide. The recrystallized product has a melting point 311-315oC.

6,62 g of compound of formula (102A) is dissolved in 70 ml of dimethylformamide (DMF) and then adding to the mixture 6,53 g of finely ground potassium carbonate at a temperature of 100-105oC. This mixture is stirred for 30 minutes, after which 11,65 g of 3-(chloromethyl)heptane, dissolved in 10 ml of DMF, is added dropwise within 60 minutes at a temperature of 100-105oC. the Temperature of the mixture is maintained at the level 100-105oC for 3 hours. After cooling to a temperature of 100oWith add 50 ml of toluene and precipitated salts are removed by filtration. The filtrate is concentrated to dryness by evaporation and the residue was added 100 ml of toluene and 100 ml of water, acidified and shaken out. The organic phase is washed with water to neutrality, separated, schogetten/toluene 65:35). Yield: 4.7 g of colorless crystals, melting point 83-84o(40% of theoretical).

Example 3:

The compounds of formula

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receive by analogy with the method of example 1.

Examples of the application

Example 4: Obtaining an emulsion of the type oil-in-water

Composition (individual components are named in accordance with the recommendations of the Association of manufacturers of cosmetic, fragrance and toiletry products):

(a1) ceteareth 6 (and) stearyl alcohol - 2,0%

(a2) ceteareth 25 - 2,0%

(a3) Cetearyl alcohol - 5,0%

(a4) Caprylic/capric triglyceride - 5,0%

(a5) Cetearyl octant - 10,0%

(a6) vaseline - 5,0%

(a7) compound of formula (101) - 4,0%

(b1) propylene glycol - 3,0%

(b2) carbopol 934 - 0,2%

(b3) H2O - 63,53%

(C) triethanolamine - 0,27%

Components (a1)-(a7) (=phase a) and (b1)-(b3) (=phase) is heated to a temperature of 75-80oC. Then phase b is added to the phase a and homogenize. Then add the component (s) (=phase) and again homogenized.

The coefficients protection from sunlight is determined in accordance with the method described by Diffey and Robson, J. Soc. Cosmet. Chem. 40, 127-133 is lsia type oil-in-water has a coefficient of protection from sunlight, equal to 4.

Example 5: get the cream from sunburn

Composition (individual components are named in accordance with the recommendations of the Association of manufacturers of cosmetic, fragrance and toiletry products):

Phase A:

(a1) Dimethicone - 2,0%

(a2) isopropyl myristate - 9,0%

(a3) stearyl alcohol - 10,0%

(a4) stearic acid - 4,0%

(a5) compound of the formula (102) - 4,0%

(a6) ground to micron size 2,4-bis(phenyl)-6-(2-hydroxy-4-methoxyphenyl)-(1,3,5-triazine) (0.25 μm) to 3.2%

(b1) triethanolamine 1.2 per cent

(b2) carbomer 934 (1%) to 5.0%

(b3) H2O - 61,6%

Components (a1)-(a6) (= phase A) homogenized separately and very carefully, after which, as the components (b1)-(b3) (= phase) are heated separately to a temperature of 75-80oC. Then phase b is added to the phase a with vigorous stirring. Stirring, the mixture is cooled.

The factor of protection from sunlight this cream is 11.

1. Symmetrical triazine derivatives of General formula I

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where R1and R2- identical and denote hydrogen or C1-C5alkyl,

R3-C1-C12is burglared with 3 moles of the compound phenyl formula

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where R1and R2have listed in paragraph 1 values

the reaction conditions for the alkylation Friedel-in the presence of a Lewis acid followed by esterification of the free hydroxyl groups of the alkylating agent lR3where R3has specified in paragraph 1.

3. The method of obtaining compounds of formula (1) under item 1, in which cyclotrimerization connection benzonitrile formula

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where R1and R2have listed in paragraph 1 values

followed by etherification of the free hydroxyl groups of the alkylating agent lR3where R3has specified in paragraph 1.

4. Symmetrical triazine derivatives of formula (1) under item 1, with protective properties against UV radiation.

 

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indicates the asymmetric carbon atom in R - or S-configuration, and, if1= R2= R; C1= S, WITH2= S and1= R2= S; m1= 2 and the product of the joining may be in the form of a free base, acid, acid salt or Quaternary ammonium salt; the way they are received by the interaction diaminetetraacetic acid with thionyl chloride and an alcohol; the product of annexation determine formula (2)

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