AU2007247213B2

AU2007247213B2 - Triazine derivatives

Info

Publication number: AU2007247213B2
Application number: AU2007247213A
Authority: AU
Inventors: Elek Borsos; Thomas Ehlis
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2006-05-08
Filing date: 2007-05-02
Publication date: 2012-11-22
Anticipated expiration: 2027-05-02

Description

Triazine derivatives

The present invention relates to specific triazine derivatives, preparation of these compounds, the preparation of micronized particles of the new tirazine derivatives and cosmetic compositions comprising these triazine derivatives.

The triazine derivatives correspond to formula

X₁ is a bivalent radical of formula (1a) -NRg-A-NRg-; (1 b) ; or

(1 c) *-O-A-O-* A and A' independently from each other are unsubstituted or substituted, straight-chain or branched Ci-Ci₂alkylene, which is optionally interrupted by C₅-Ci₂cycloalkylene, N, O or S; C₅-Ci₂cycloalkylene; biphenylene; C₆-Ci₀arylene; or C₅-Cioarylene-(Ci-Ci₂alkylene);

R₁ is a radical of formula (1d) _*^/ ; (1 e) *-S=O _; (if) _t_(/ ^■ o- R₅ O_χ R₅

(1fl) ^*^ _: or (1 h) 1 _Wi ;

R₆ R₂ and R₃ independently from each other are hydrogen; Ci-Ci₂alkyl; OR₇; NR₇R₈; C₆-Ci₀aryl;

X₂ is O, or NH;

W₁ is CrC₂₀alkyl; or a group Sp-SiI;

Sp is a straight-chain or branched saturated or single or multiple unsaturated C3-C₁₂ hydrocarbon; SiI is a silane; an oligosiloxane; or a polysiloxanes moiety; and

R₄, R5 Re, R7, Re and Rg independently from each other are hydrogen; d-C^alkyl; or

C₃-Ci₂cycloalkyl.

CrCi₂alkyl is for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2'-dimethylpropyl, cyclopentyl, cyclohexyl, n-hexyl, n-octyl, 1 ,1 ',3,3'-tetramethylbutyl or 2-ethylhexyl, nonyl, decyl, undecyl or dodecyl.

C6-Cioaryl is for example naphthyl or preferably phenyl.

Ci-Ci₂alkylene is for example methylene, ethylene, propylene, isopropylene, n-butylene, sec- butylene, tert-butylene, n-pentylene, 2-pentylene 3-pentylene, 2,2'-dimethylpropylene, cyclopentylene, cyclohexylene, n-hexylene, n-octylene, 1 ,1 ',3,3'-tetramethylbutylene, 2- ethylhexylene, nonylene, decylene or dodecylene.

Alkylene may be straight-chain, branched, or, from C₅alkyl upwards, monocyclic or polycyclic, and may be interrupted by hetero atoms, such as such as O, S, -CO-, N, NH, NR_x -OCO-, -CO(OR_x)-, -CONR_x-, -(R_x)NC(O)-; for example C_rCi_Oalkylene may be a bivalent radical such as: -CH₂CH₂-O-CH₂CH₂-O-CH₂CH₂- -CH₂CH₂-O-CH₂CH₂- -CH₂CH₂-O-CH₂-, -CH₂-O-CH₂-, -CH₂CH₂-CH₂CH₂-O-CH₂-CH₂-, -CH₂CH₂-CH(N(CH₃)₂)-CH₂-CH₂-,

CH₂-NH₂-CH₂-CH₂, -CH₂CH₂-NH-CH₂CH₂-, -CH₂CH₂-NCH₃-CH₂CH₂-, -CO-CH₂-, -CH₂CO-, -CH₂CH₂-NHCO-CH₂CH₂-, -CH₂CH₂-CONH-CH₃-CH₂CH₂-, -CH₂CH₂-NCH₃CO-CH₂CH₂-, -CH₂CH₂-CONCH₃-CH₃-CH₂CH₂-, -CH₂-NHCO-CH₂CH₂-, -CH₂CH₂-NHCO-CH₂-, -CH₂CH₂-CONH-CH₂- Or -CH₂-CONH-CH₂CH₂-. R_x is hydrogen or C_rCi₂alkyl.

C₅-Ciocycloalkylene is for example cyclopentylene, cyclohexylene, cycloheptylene or cyclooctylene.

C₆-Ci₀arylene is for example naphthylene like , or preferably

phenylene. Preferred are compounds of formula (1 ) wherein

O

Ri is a radical of formula (1d) _* — Y /? ; or (1g) —4 \ ; wherein

\ N-R.

R₅ and R₆ independently from each other are hydrogen; or d-C₅alkyl; and more preferably, wherein R₅ is CrC₅alkyl; or hydrogen; and Re is hydrogen.

In formula (1 )

Xi is preferably a radical of formula (1 b), wherein A and A' are CrC₄alkylene; or wherein

Xi is preferably a radical of formula (1a), wherein A is Ci-C₅alkylene; or phenylene; and Rg is hydrogen.

Most preferably in formula (1 )

X₁ is selected from -NH-(CH₂)₂-NH-; — ; and

Most preferred are compounds of formula (1 ), wherein R₂, R3 and R₄ are hydrogen.

Preferred are also compounds of formula (1 ), wherein SiI is the group SiRi₀RnRi₂, wherein

R₁₀, Rn and Ri₂ each independently are Ci-Cβalkyl; Ci-Cβalkoxy; or phenyl; or an oligosiloxane of formula -SiMe_m(OSiMe₃)_n; or an oligosiloxane of the formulae -A-

Me Me Me Me Me Me I I I I I

(1i) Me — Si-O- -Si-O- -Si-* _; (_1k) Me- -Si-O- Si — 0 — Si-Me. _or

Me Me Me Me ' Me

Me Me

(11) 0- Si-O- -Si — O — Si-Me

Me ! Me

wherein Me is methyl; m is O; 1; or 2; n is 1; 2; or 3; m + n are 3; and u is 0 to 6.

Very most preferred are compounds of formula

o _t_ύ o

R₁ is a radical of formula (1d) _*—i/ ; (1g) \ ;or(1h) IJ o— R, 5 X.

X₁ is radical of formula (1a) -NR₉-A-NR₉-; (1c) *-O-A-O-* ; and — N N— ;

A, W₁, X₂ and R₉ are defined as in formula (1); and R₅ and R₆ independently from each other are hydrogen; or CrC₄alkyl.

Preferred are compounds of formula (2), wherein o

Ri is a radical of formula (1d) _* — i/ or (1g) Α N— FL o— R.

R_β

X₁ is selected from -NH-(CH₂)₂-NH-; -^Nw^N" and

* — N— (( \ — N — * ; and

H \ / H

R₅ and Re independently from each other are hydrogen; or Ci-C₄alkyl.

Examples of compounds of formula (1 ) are listed in the Table below:

Table 1 :

Compound Ri Xi of formula

(3) -CO(O)-C₂H₅

* — N N-*

(4) -CO(O)-C₂H₅ -NH-(CH₂)₂-NH-

(5) -CO(O)-C₂H₅ _*

H \ / H ^*

(6) -CO-NH₂

(7) -CO-NH₂ -NH-(CH₂)₂-NH-

(8) -CO(O)-C₂H₅

H

The compounds of formula (1 ) are prepared by methods known from the prior art, as disclosed for example in Journal of the Institution of Chemists (inida), 6(5), p. 197 (1984); or in Journal of the Institution of Chemists (inida), 57(6), p. 233 (1985); or in EP 818 450. The method generally comprises reacting 2 moles of a halogentriazine of formula (1 m), preferably chlorotriazine, with 1 mole of the compound of formula (1 n) to give the compound of formula (1 ) according to the follwing reaction scheme:

(1 m) (1 n) (1 ) wherein

Ri, R2, R3, R4 and Xi are defined as in formula (1 ).

The reaction is preferably carried out in dipolar aprotic solvents, like dimetylfomamide, di- methylsulfoxide, sulfolane, N-methyl-pyrrolidone; hydrocarbons like xylene or toluene, tetra- line, petroleum, mesytilene or benzene; hydrogenated halocarbons like chlorobenzene or dichlorobenzene; or without a solvent using an excess of a base like tetraalylamines; or without any solvent and a base in a "melt process".

The reaction temperature is preferably from 20 to 280, preferably 30 to 200, and most preferably from 40 to 150°C.

Preferred bases used in the present process are trialkylamines like triethylamine, ethyl-iso- propylamine, heterocyclic amines like DABCO or DBU, or inorganic bases like NH₂CO₃ or NaHCO₃.

The compounds of the formula (1 ) according to the present invention are particularly suitable as UV filters, i.e. for protecting ultraviolet-sensitive organic materials, in particular the skin and hair of humans and animals, from the harmful effects of UV radiation. These compounds are therefore suitable as sunscreens in cosmetic, pharmaceutical and veterinary medical preparations.

The UV absorbers of formula (1 ) according to the present invention, depending on the definition of Xi and Ri can be used either in the dissolved state (soluble organic filters, solubelized organic filters) or in the micronised state (nanoscalar organic filters, particulate organic filters, UV-absorber pigments). Any known process suitable for the preparation of microparticles can be used for the preparation of the micronised UV absorbers, for example wet-milling,wet-kneading, spray-drying from a suitable solvent, by the expansion according to the RESS process (Rapid Expansion of Supercritical Solutions) by reprecipitation from suitable solvents.

The micronised UV absorbers so obtained usually have an average particle size from 0.02 to 2, preferably from 0.03 to 1.5, and more especially from 0.05 to 1.0 micrometer.

The process for the preparation of the micronized compound of formula (1 ) is another object of the present invention.

A further object of the present invention is a UV absorber dispersion, comprising

(a) a micronised UV absorber of formula (1 ), each of them having a particle size from 0,02 to 2 μm, and (b) a suitable dispersing agent.

The cosmetic formulations or pharmaceutical compositions according to the present invention may additionally contain one or more than one further conventional UV filter.

The cosmetic or pharmaceutical preparations may be, for example, creams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick preparations, powders or ointments. In addition to the above-mentioned UV filters, the cosmetic or pharmaceutical preparations may contain further adjuvants as described below.

As water- and oil-containing emulsions (e.g. VWO, O/W, 0/W/O and W/O/W emulsions or mi- croemulsions) the preparations contain, for example, from 0.1 to 30 % by weight, preferably from 0.1 to 15 % by weight and especially from 0.5 to 10 % by weight, based on the total weight of the composition, of one or more UV absorbers, from 1 to 60 % by weight, especially from 5 to 50 % by weight and preferably from 10 to 35 % by weight, based on the total weight of the composition, of at least one oil component, from 0 to 30 % by weight, especially from 1 to 30 % by weight und preferably from 4 to 20 % by weight, based on the total weight of the composition, of at least one emulsifier, from 10 to 90 % by weight, especially from 30 to 90 % by weight, based on the total weight of the composition, of water, and from 0 to 88.9 % by weight, especially from 1 to 50 % by weight, of further cosmetically acceptable adjuvants.

The cosmetic or pharmaceutical preparations may be, for example, creams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick preparations, powders or ointments. In addition to the above mentioned UV filters, the cosmetic or pharmaceutical preparations may contain further adjuvants as described below.

As water- and oil-containing emulsions (e.g. W/O, O/W, 0/W/O and W/O/W emulsions or microemulsions) the preparations contain, for example, from 0.1 to 30 % by weight, preferably from 0.1 to 15 % by weight and especially from 0.5 to 10 % by weight, based on the total weight of the composition, of one or more UV absorbers, from 1 to 60 % by weight, especially from 5 to 50 % by weight and preferably from 10 to 35 % by weight, based on the total weight of the composition, of at least one oil component, from 0 to 30 % by weight, especially from 1 to 30 % by weight und preferably from 4 to 20 % by weight, based on the total weight of the composition, of at least one emulsifier, from 10 to 90 % by weight, especially from 30 to 90 % by weight, based on the total weight of the composition, of water, and from 0 to 88.9 % by weight, especially from 1 to 50 % by weight, of further cosmetically acceptable adjuvants.

The cosmetic or pharmaceutical compositions/preparations according to the invention may also contain one or one more additional compounds like fatty alcohols, esters of fatty acids, natural or synthetic triglycerides including glyceryl esters and derivatives, pearlescent waxes: hydrocarbon oils: silicones or siloxanes, organosubstituted super-fatting agents, surfactantsconsistency regulators/thickeners and rheology modifiers, polymers, biogenic active ingredients, deodorising active ingredients, anti-dandruff agents, antioxidants, hydrotropic agents, preservatives and bacteria-inhibiting agents, perfume oils, colourants, polymeric beads or hollow spheres as spf enhancers.

Cosmetic or pharmaceutical preparations

Cosmetic or pharmaceutical formulations are contained in a wide variety of cosmetic preparations. There come into consideration, for example, especially the following preparations: skin-care preparations, e.g. skin-washing and cleansing preparations in the form of tablet-form or liquid soaps, soapless detergents or washing pastes, bath preparations, e.g. liquid (foam baths, milks, shower preparations) or solid bath preparations, e.g. bath cubes and bath salts; - skin-care preparations, e.g. skin emulsions, multi-emulsions or skin oils; cosmetic personal care preparations, e.g. facial make-up in the form of day creams or powder creams, face powder (loose or pressed), rouge or cream make-up, eye-care preparations, e.g. eyeshadow preparations, mascara, eyeliner, eye creams or eye-fix creams; lip-care preparations, e.g. lipsticks, lip gloss, lip contour pencils, nail-care preparations, such as nail varnish, nail varnish removers, nail hardeners or cuticle removers; foot-care preparations, e.g. foot baths, foot powders, foot creams or foot balsams, special deodorants and antiperspirants or callus-removing preparations; light-protective preparations, such as sun milks, lotions, creams or oils, sunblocks or tropicals, pre-tanning preparations or after-sun preparations; skin-tanning preparations, e.g. self-tanning creams; depigmenting preparations, e.g. preparations for bleaching the skin or skin-lightening preparations; insect-repellents, e.g. insect-repellent oils, lotions, sprays or sticks; - deodorants, such as deodorant sprays, pump-action sprays, deodorant gels, sticks or roll-ons; antiperspirants, e.g. antiperspirant sticks, creams or roll-ons; preparations for cleansing and caring for blemished skin, e.g. synthetic detergents (solid or liquid), peeling or scrub preparations or peeling masks; - hair-removal preparations in chemical form (depilation), e.g. hair-removing powders, liquid hair-removing preparations, cream- or paste-form hair-removing preparations, hair- removing preparations in gel form or aerosol foams; shaving preparations, e.g. shaving soap, foaming shaving creams, non-foaming shaving creams, foams and gels, preshave preparations for dry shaving, aftershaves or aftershave lotions; fragrance preparations, e.g. fragrances (eau de Cologne, eau de toilette, eau de parfum, parfum de toilette, perfume), perfume oils or perfume creams; cosmetic hair-treatment preparations, e.g. hair-washing preparations in the form of shampoos and conditioners, hair-care preparations, e.g. pretreatment preparations, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-structuring preparations, e.g. hair-waving preparations for permanent waves (hot wave, mild wave, cold wave), hair-straightening preparations, liquid hair- setting preparations, hair foams, hairsprays, bleaching preparations, e.g. hydrogen per- oxide solutions, lightening shampoos, bleaching creams, bleaching powders, bleaching pastes or oils, temporary, semi-permanent or permanent hair colourants, preparations containing self-oxidising dyes, or natural hair colourants, such as henna or camomile.

Presentation forms The final formulations listed may exist in a wide variety of presentation forms, for example:

in the form of liquid preparations as a VWO, O/W, 0/W/O, W/O/W or PIT emulsion and all kinds of microemulsions, in the form of a gel, - in the form of an oil, a cream, milk or lotion, in the form of a powder, a lacquer, a tablet or make-up, in the form of a stick, in the form of a spray (spray with propellent gas or pump-action spray) or an aerosol, in the form of a foam, or - in the form of a paste.

Of special importance as cosmetic preparations for the skin are light-protective preparations, such as sun milks, lotions, creams, oils, sunblocks or tropicals, pretanning preparations or after-sun preparations, also skin-tanning preparations, for example self-tanning creams. Of particular interest are sun protection creams, sun protection lotions, sun protection milk and sun protection preparations in the form of a spray.

Of special importance as cosmetic preparations for the hair are the above-mentioned preparations for hair treatment, especially hair-washing preparations in the form of shampoos, hair conditioners, hair-care preparations, e.g. pretreatment preparations, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair- straightening preparations, liquid hair-setting preparations, hair foams and hairsprays. Of special interest are hair-washing preparations in the form of shampoos. A shampoo has, for example, the following composition: from 0.01 to 5 % by weight of a UV absorber according to the invention, 12.0 % by weight of sodium laureth-2-sulfate, 4.0 % by weight of cocamidopropyl betaine, 3.0 % by weight of sodium chloride, and water ad 100%.

Other typical ingredients in such formulations are preservatives, bactericides and bacteriostatic agents, perfumes, dyes, pigments, thickening agents, moisturizing agents, humectants, fats, oils, waxes or other typical ingredients of cosmetic and personal care formulations such as alcohols, poly-alcohols, polymers, electrolytes, organic solvents, silicon derivatives, emollients, emulsifiers or emulsifying surfactants, surfactants, dispersing agents, antioxi- dants, anti-irritants and anti-inflammatory agents etc.

The cosmetic preparation according to the invention is distinguished by excellent protection of human skin against the damaging effect of sunlight.

A. Preparation Examples

Example A1 : Preparation of the compound of formula

1.8g (0.021 mol) piperazine are added to a solution of 4.4g (0.01 mol) of the monochlorotriazine of formula

in 50ml dimethylformamide and stirred at 75°C for 2h. The reaction solution is decanted on 100ml water and stirred.

The raw product is filtered off, washed with water, stirred in aceton, filtered off and dried in vacuo at 80°C.

A white product is obtained.

Yield: 2.Og (44.6%) colorless cristals; Fp= 287-290°C NMR:

¹³C NMR (90 MHz): δ= 14.61 (CH₃), 60.63. (CH₂), 119.35 (CH), 122.99 (Cq), 130.35 (CH),

145.02 (Cq), 164.38 (Cq), 164.98 (Cq), 165.88 (Cq).

Example A2: Preparation of the compound of formula

0.3g ethylendiamine (O.OOδmol) and 1.1.g triethylamine (0.011 mol) are added to a solution of

4.4g (0.01 mol) of the monochlorotriazine of formula (101a) in 50ml dimethylformamide and stirred for 2h at 75°C.

The reaction solution concentrated with a rotary evapoarator until drying, gathered in water and weakly acidified with hydrochloric acid (1 N).

The raw product is filtered off and washed neutral.

After decocting in acetone a white product is obtained.

Yield: 2.7g (62.0%); Fp = 213-215°C.

¹³C NMR (90 MHz₁): δ= 14.55 (CH₃), 14.58 (CH₃), 60.52 (CH₂), 60.55 (CH₂), 119.20 (CH), 122.73 (CH ), 122.82 (CH), 130.15 (CH), 145.13 (Cq), 145.29 (Cq), 164.22 (Cq), 164.41 (Cq), 165.87 (Cq), 166.16 (Cq).

Example A3: Preparation of the compound of formula

A solution of 34.7g (0.255mol) 4-aminobenzamide in 100ml methyl-2-pyrrolidone is added to a solution of 46.1g cyanuric chloride (0.25mol) in a 800ml dioxan/water mixture (9:1 ) at 5°C and a pH of 3.5.

Then a solution of 34.7g 4-aminobenzamide (0.255mol) in 100ml methylpyrrolidone is added at 60-90°C and pH of 8.5. The suspension is diluted at 60°C, filterd off warm and washed with dioxan and water. After decocting with in dimethylfomamide and acetone a white product of formula

is obtained.

0.432g (O.OOδmol) piperazine and 1.1g triethylamine (0.01 mol) are added to a solution of

3.84g (0.01 mol) of the monochlorotriazine of formula (103a) in dimethylfomamide.

The reaction mixture is stirred at 75°C for 6h and then at 90°C for 1 h.

After concentrating with the rotary evaporator until drying the residue is gathered in water, weakly acidified with hydrochloric acid, filtered off and washed neutral with water.

After recrystallization from 1-methyl-2-pyrrolidone and decocting in methanol a white product is obtained.

Yield: 1.95g (49.9%)

Melting point: decomposition starting at 260°C Elemental anylysis of the compound of formula (103:

Example A4: Preparation of the compound of formula

0.3Og (O.OOδmol) ethylenediamine and 1.1g triethylamine (0.01 mol) are added to a solution of 3.84g (0.01 mol) of the monochlorotriazine of formula (103a) in 50ml dimethylformamide and stirred for 5.5h at 75°C.

The clear solution is concentrated with a rotary evapoarator until drying, gathered in water, weakly acidified with hydrochloric acid, filtered off and washed neutral with water.

After recrystallization from a dimethylformamide/water mixture (4:6) and decocting in acetone a white product is obtained.

Yield: 0.8g (21.2%)

NMR:

13 ¹C NMR (90 MHz): δ= 31.14, 36.14, 1 19.26 (CH), 127.72 (Cq), 128.51 (CH), 128.69, 143.09 (Cq), 162.70 (Cq), 163.35 (CH), 163.90 (Cq), 165.13 (Cq), 168.03 (Cq).

Example A5: Preparation of the compound of formula

0.37g (O.OOδmol) propylenediamine and 1.1g (0.01 mol) triethylamine are added to a solution of 4.4g (0.01 mol) of the monochlorotriazine of formula (101a) in 50ml dimethylformamide and stirred for 4h at 75°C. After concentrating with the rotary evaporator until drying the residue is gathered in water and filtered off.

After dissolving in tert. butylmethylether the organic phase is shaken out with brine solution

(5%), dried over sodium sulfate and concentrated until drying.

A white product is obtained by column chromatographic purification. Yield: 2.3g (52%) NMR:

¹³C NMR (90 MHz): δ= 14.53 (CH₃), 14.58 (CH₃), 19.04 (CH₃), 46.03. (CH₂), 46.68.(CH), 60.54 (CH₂), 119.22 (CH), 122.73 (Cq), 122.85 (Cq), 130.13 (CH), 145.11 (Cq), 145.25 (Cq), 145.32 (Cq), 164.25 (Cq), 164.38 (Cq), 165.75 (Cq), 165.84 (Cq), 165.87 (Cq), 166.26 (Cq).

Example A6:

The compound of formula (5) (Table 1 ) is prepared according to the method as described in

Example 1. Piperazine is replaced by p-phenylene-diamine.

Example A7:

The compound of formula (18) (Table 1 ) is prepared according to the method as described in Example 1. Piperazine is replaced by isophoron-diamine (CAS No. 2855-13-2). The compound of formula (101 a) is replaced by

Example A8:

The compound of formula (19) (Table 1 ) is prepared according to the method as described in Example 1. Piperazine is replaced by 4,4'-diamino-3,3'-dimethyldicyclohexylmethane. The compound of formula (101 a) is replaced by

Example A9:

The compound of formula (20) (Table 1 ) is prepared according to the method as described in Example 1. Piperazine is replaced by dodecane-1 ,12-diamine. The compound of formula (101 a) is replaced by

Example A10:

The compound of formula (30) (Table 1 ) is prepared according to the method as described in Example 1. Piperazine is replaced by isophoron-diamine. The compound of formula (101 a) is replaced by

Example A11 : The compound of formula (32) (Table 1 ) is prepared according to the method as described in Example 1. Piperazine is replaced by dodecane-1 ,12-diamine. The compound of formula (101 a) is replaced by

Example A12:

The compound of formula (43) (Table 1 ) is prepared according to the method as described in Example 1. Piperazine is replaced by 4,4'-diamino-3,3'-dimethyldicyclohexylmethane The compound of formula (101 a) is replaced by

Example A13:

The compound of formula (31 ) (Table 1 ) is prepared according to the method as described in Example 1. Piperazine is replaced by 4,4'-Diamino-3,3'-dimethyldicyclohexylmethane. The compound of formula (101 a) is replaced by

Example A14:

The compound of formula (51 ) (Table 1 ) is prepared according to the method as described in Example 1. Piperazine is replaced by 1 ,6-hexandiol. The compound of formula (101a) is replaced by

Example A15:

The compound of formula (53) (Table 1 ) is prepared according to the method as described in Example 1. Piperazine is replaced by neopentylglycol (CAS No. 126-30-7). The compound of formula (101a) is replaced by

Example A16:

The compound of formula (57) (Table 1 ) is prepared according to the method as described in Example 1. Piperazine is replaced by neopentylglycol. The compound of formula (101a) is replaced by

Example A17:

The compound of formula (50) (Table 1 ) is prepared according to the method as described in Example 1. Piperazine is replaced by 1 ,6-hexandiol. The compound of formula (101a) is replaced by

Example A18:

The compound of formula (49) (Table 1 ) is prepared according to the method as described in Example 1. Piperazine is replaced by 1 ,6-hexandiol. The compound of formula (101 a) is replaced by

B. Application examples

Claims

1. Compounds of formula

(1 ) , wherein

Xi is a bivalent radical of formula (1 a) -NRg-A-NRg-; (1 b) or

(1 c) *-O-A-O-*

A and A' independently from each other are unsubstituted or substituted, straight-chain or branched CrC^alkylene, which is optionally interrupted by C₅-Ci₂cycloalkylene, N, O or S; C₅-Ci₂cycloalkylene; biphenylene; C₆-Ci₀arylene; or C₅-Cioarylene-(Ci-Ci₂alkylene);

R₁ is a radical of formula (1d) _*^/ ; (1 e) *-S=O _; (if) _t_(/ ^■

O,

^'R.

R₂ and R3 independently from each other are hydrogen; Ci-Ci₂alkyl; OR₇; NR₇R₈; C6-Cioaryl;

X₂ is O, or NH;

W₁ is CrC₂₀alkyl; or a group Sp-SiI;

Sp is a straight-chain or branched saturated or single or multiple unsaturated C₃-C₁₂ hydrocarbon;

SiI is a silane; an oligosiloxane; or a polysiloxane moiety; and

R₄, R₅, R₆, R₇, Rs and Rg independently from each other are hydrogen; CrC₁₂alkyl; or C₃-C₁₂cycloalkyl.

2. Compounds according to claim 1 wherein O O //

R₁ is a radical of formula (1d) _* — </ ; or (1g) \ ; wherein

\ N — R_c

O— R. ^V5

R_κ

R₅ and Re independently from each other are hydrogen; or CrC₅alkyl.

3. Compounds according to claim 2, wherein R₅ is CrC₅alkyl; or hydrogen; and

Re is hydrogen.

4. Compounds according to any of claims 1 to 3, wherein Xi is a radical of formula (1 b), wherein A₁ and A₂ are CrC₄alkylene.

5. Compounds according to any of claims 1 to 3, wherein Xi is a radical of formula (1a), wherein

A₁ is CrC₅alkylene; or phenylene; and R₉ is hydrogen;

6. Compounds according to any of claims 1 to 5, wherein

X₁ is selected from -NH-(CH₂)₂-NH-; — ; and

7. Compounds according to any of claims 1 to 6, wherein R₂, R₃ and R₄ are hydrogen.

8. Compounds according to any of claims 1 to 7, wherein SiI is the group SiR₁₀R₁₁R₁₂, wherein

R₁₀, R₁₁ and R₁₂ each independently are Ci-Cβalkyl; CrCβalkoxy; or phenyl; or an oligosiloxane of formula -SiMe_m(OSiMe₃)_n; or an oligosiloxane of the formulae Me Me Me Me Me Me I I I I I

(1i) Me — Si-O- -Si-O- -Si-* _; (_1k) Me- -Si-O- Si — O — Si-Me. _or

Me Me Me Me ' Me

Me Me

(11) O- Si-O- -Si — O — Si-Me

Me ! Me

9. Compounds according to any of claims 1 to 8, which conform to formula

O _t_ύ o

R₁ is a radical of formula (1d) _*—i/ ; (1g) \ ;or(1h) IJ o— R, 5 X.

10. Compounds according to claim 9, wherein o

Ri is a radical of formula (1d) _* — i/ or (1g) Α N— R_c o— R.

R_β

X₁ is selected from -NH-(CH₂)₂-NH-; — N N— . _and

R₅ and Re independently from each other are hydrogen; or Ci-C₄alkyl.

1 1. Process for the preparation of the compounds of formula (1 ) which comprises reacting 2 moles of the chlorotriazine of formula (1 m) with 1 mole of the compound of formula (1 n) according to the follwing reaction scheme:

(1 m) (1 n) (1 ) wherein

R-i, R2, R3, R4 and Xi are defined as in claim 1.

12. Process for the preparation of the micronized compound of formula (1 ) comprising wet- milling.wet-kneading, spray-drying from a suitable solvent, by the expansion according to the RESS process or by reprecipitation from suitable solvents of the compounds of formula (1 ) to obtain microparticles having a mean particle size from 0,02 to 2 μm.

13. Cosmetic composition comprising at least one compound of formula (1 ) according to claim 1 together with cosmetically tolerable carriers or adjuvants.

14. Cosmetic composition according to claim 13 wherein the compound of formula (1 ) is present in the composition in the micronized state.

15. UV absorber dispersion, comprising

(a) at least one micronised UV absorber of formula (1 ), having a particle size from 0.02 to 2 μm, and

(b) a suitable dispersing agent.