# Patent

## Title
Triazine derivatives

## Abstract

Disclosed are triazine derivatives of formula




wherein

    X1 is a bivalent radical of formula






    A and A′ independently from each other are unsubstituted or substituted, straight-chain or branched C1-C12alkylene, which is optionally interrupted by C5-C12cycloalkylene, N, O or S; C5-C12cycloalkylene; biphenylene; C6-C10arylene; or C5-C10arylene-(C1-C12alkylene);
    R1 is a radical of formula






    R2 and R3 independently from each other are hydrogen; C1-C12alkyl; OR7; NR7R8; C6-C10aryl;
    X2 is O, or NH;
    W1 is C1-C20alkyl; or a group Sp-Sil;
    Sp is a straight-chain or branched saturated or single or multiple unsaturated C3-C12 hydrocarbon;
    Sil is a silane; an oligosiloxane; or a polysiloxane moiety; and
    R4, R5 R6, R7, R8 and R9 independently from each other are hydrogen; C1-C12alkyl; or C3-C12cycloalkyl.

## Background
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




wherein

    X1 is a bivalent radical of formula






    A and A′ independently from each other are unsubstituted or substituted, straight-chain or branched C1-C12alkylene, which is optionally interrupted by C5-C12cycloalkylene, N, O or S; C5-C12cycloalkylene; biphenylene; C6-C10arylene; or C5-C10arylene-(C1-C12alkylene);
    R1 is a radical of formula






    R2 and R3 independently from each other are hydrogen; C1-C12alkyl; OR7; NR7R8; C6-C10aryl;
    X2 is O, or NH;
    W1 is C1-C20alkyl; or a group Sp-Sil;
    Sp is a straight-chain or branched saturated or single or multiple unsaturated C3-C12 hydrocarbon;
    Sil is a silane; an oligosiloxane; or a polysiloxanes moiety;
    and
    R4, R5R6, R7, R8 and R9 independently from each other are hydrogen; C1-C12alkyl; or C3-C12cycloalkyl.


C1-C12alkyl 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-C10aryl is for example naphthyl or preferably phenyl.
C1-C12alkylene 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, NRx, —OCO—, —CO(ORx)—, —CONRx—, —(RX)NC(O)—; for example C1-C10alkylene 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—. Rx is hydrogen or C1-C12alkyl.
C5-C10cycloalkylene is for example cyclopentylene, cyclohexylene, cycloheptylene or cyclooctylene.
C6-C10arylene is for example naphthylene like




or preferably phenylene.

Preferred are compounds of formula (1) wherein

    R1 is a radical of formula






wherein

    R5 and R6 independently from each other are hydrogen; or C1-C5alkyl; and more preferably, wherein
    R5 is C1-C5alkyl; or hydrogen; and
    R6 is hydrogen.


In formula (1)

    X1 is preferably a radical of formula (1b), wherein
    A and A′ are C1-C4alkylene; or wherein
    X1 is preferably a radical of formula (1a), wherein
    A is C1-C5alkylene; or phenylene; and
    R9 is hydrogen.


Most preferably in formula (1)

    X1 is selected from






Most preferred are compounds of formula (1), wherein

    R2, R3 and R4 are hydrogen.


Preferred are also compounds of formula (1), wherein

    Sil is the group SiR10R11R12, wherein
    R10, R11 and R12 each independently are C1-C6alkyl; C1-C6alkoxy; or phenyl; or an oligosiloxane of formula —SiMem(OSiMe3)n; or an oligosiloxane of the formulae






    wherein
    Me is methyl;
    m is 0; 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




wherein

    R1 is a radical of formula






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






    A, W1, X2 and R9 are defined as in formula (1); and
    R5 and R6 independently from each other are hydrogen; or C1-C4alkyl.


Preferred are compounds of formula (2), wherein

    R1 is a radical of formula






    X1 is selected from






and

    R5 and R6 independently from each other are hydrogen; or C1-C4alkyl.


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








TABLE 1








T








 









Compound




of formula
R1
X1





(3)
—CO(O)—C2H5






 


(4)
—CO(O)—C2H5
—NH—(CH2)2—NH—


 


(5)
—CO(O)—C2H5






 


(6)
—CO—NH2






 


(7)
—CO—NH2
—NH—(CH2)2—NH—


 


(8)
—CO(O)—C2H5






 


(9)










 


(10)










 


(11)










 


(12)










 


(13)
—CO(O)—CH3






 


(14)










 


(15)










 


(16)










 


(17)










 


(18)










 


(19)










 


(20)










 


(21)










 


(22)










 


(23)










 


(24)










 


(25)










 


(26)










 


(27)










 


(28)










 


(29)










 


(30)










 


(31)










 


(32)










 


(33)










 


(34)










 


(35)










 


(36)










 


(37)










 


(38)










 


(39)










 


(40)










 


(41)










 


(42)










 


(43)










 


(44)










 


(45)










 


(46)










 


(47)










 


(48)










 


(49)










 


(50)










 


(51)










 


(52)










 


(53)










 


(54)










 


(55)
—CO(O)—CH3
—NH—(CH2)2—NH—


 


(56)










 


(57)










 


(58)










 


(59)










 


(60)

















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 (1m), preferably chlorotriazine, with 1 mole of the compound of formula (1n) to give the compound of formula (1) according to the following reaction scheme:




    wherein
    R1, R2, R3, R4 and X1 are defined as in formula (1).


The reaction is preferably carried out in dipolar aprotic solvents, like dimethylfomamide, 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 X1 and R1 can be used either in the dissolved state (soluble organic filters, solubilized 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. W/O, O/W, O/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 and 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, O/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 and 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, surfactants consistency 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 peroxide 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 W/O, O/W, O/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, antioxidants, 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.
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




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




in 50 ml dimethylformamide and stirred at 75° C. for 2 h.

The reaction solution is decanted on 100 ml 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: 2.0 g (44.6%) colorless crystals; 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




0.3 g ethylendiamine (0.005 mol) and 1.1 g triethylamine (0.011 mol) are added to a solution of 4.4 g (0.01 mol) of the monochlorotriazine of formula (101a) in 50 ml dimethylformamide and stirred for 2 h at 75° C.
The reaction solution concentrated with a rotary evaporator until drying, gathered in water and weakly acidified with hydrochloric acid (1N).
The raw product is filtered off and washed neutral.
After decocting in acetone a white product is obtained.
Yield: 2.7 g (62.0%); Fp=213-215° C.
13C NMR (90 MHz): 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 34.7 g (0.255 mol) 4-aminobenzamide in 100 ml methyl-2-pyrrolidone is added to a solution of 46.1 g cyanuric chloride (0.25 mol) in a 800 ml dioxan/water mixture (9:1) at 5° C. and a pH of 3.5.
Then a solution of 34.7 g 4-aminobenzamide (0.255 mol) in 100 ml methylpyrrolidone is added at 60-90° C. and pH of 8.5.
The suspension is diluted at 60° C., filtered off warm and washed with dioxan and water.
After decocting with in dimethylfomamide and acetone a white product of formula




is obtained.

0.432 g (0.005 mol) piperazine and 1.1 g triethylamine (0.01 mol) are added to a solution of 3.84 g (0.01 mol) of the monochlorotriazine of formula (103a) in dimethylfomamide.
The reaction mixture is stirred at 75° C. for 6 h 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: 1.95 g (49.9%)
Melting point: decomposition starting at 260° C.
Elemental analysis of the compound of formula (103:















C
H
N





















Calculated
58.45
4.65
28.70



Found
58.07
4.93
28.13










Example A4
Preparation of the Compound of Formula




0.30 g (0.005 mol) ethylenediamine and 1.1 g triethylamine (0.01 mol) are added to a solution of 3.84 g (0.01 mol) of the monochlorotriazine of formula (103a) in 50 ml dimethylformamide and stirred for 5.5 h at 75° C.
The clear solution is concentrated with a rotary evaporator 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: 0.8 g (21.2%)
NMR:
13C NMR (90 MHz): δ=31.14, 36.14, 119.26 (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




0.37 g (0.005 mol) propylenediamine and 1.1 g (0.01 mol) triethylamine are added to a solution of 4.4 g (0.01 mol) of the monochlorotriazine of formula (101a) in 50 ml dimethylformamide and stirred for 4 h 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: 2.3 g (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 (101a) 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 (101a) 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 (101a) 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 (101a) 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 (101a) 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 (101a) 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 (101a) 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 (101a) is replaced by




B. Application Examples


















A %
B %
C %
D %
E %
F %
G %


INCI-Name
w/w
w/w
w/w
w/w
w/w
w/w
w/w






















Example B1:









Ethylhexyl Methoxycinnnamate
9.8
9.8
9.8
9.8
9.8
9.8
9.8


Cyclomethicone
7.0
7.0
7.0
7.0
7.0
7.0
7.0


Octadecene/MA Copolymer (and) Methyl Acethyl

3.0


Ricinoleate (and) Di-methylhepthyl Adipate


C30-38 olefin/isopropyl maleate/MA copolymer


2.0


Hydrogenated Dimer Dilinoleyl/Dimethylcarbonate



3.0


Copolymer


Cyclopentasiloxane (and)




7.0


Acrylates/Polytrimethylsiloxymethacrylate


Copolymer


Isododecane (and)





8.0


Acrylates/Polytrimethylsiloxymethacrylate


Copolymer


Poly(Glycol Adipate)/Bis-Hydroxyethyoxypropyl






5.0


Dimethicone Copolymer


Ethylhexyl Palmitate
5.0
5.0
5.0
5.0
5.0
5.0
5.0


Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine
2.0
2.0
2.0
2.0
2.0
2.0
2.0


Pentaerythrityl Distearate

1.5




3.0


Glyceryl Dibehenate (and) Tribehenin (and)


2.0

4.0


Glyceryl Behenate


Glyceryl Stearate
1.5


1.5

1.5


C20-22 Alkyl Phosphate (and) C20-22 Alcohols

3.0



2.5


Candelilla/Jojoba/Rice Bran Polyglyceryl-3 esters


6.0



4.0


(and) glyceryl stearate (and) Cetearyl alcohol (and)


Sodium stearoyl lactylate


Glyceryl oleate citrate (and) Caprylic/Capric



5.0


Triglycerides


Potassium Cetyl Phosphate
1.8



1.8


VP/Eicosene Copolymer
0.6



0.6


Aqua
Qs to 100
Qs to 100
Qs to 100
Qs to 100
Qs to 100
Qs to 100
Qs to 100


Methylene Bis-Benzotriazolyl
2.0
2.0
2.0
2.0
2.0
2.0
2.0


Tetramethylbutylphenol


PVP/dimethylconylacrylate/polycarbamyl/polyglycol


ester


Polyester-5


Acrylates/Palmeth-25 Acrylate Copolymer
0.3


Disteareth-75 IPDI

0.3
3.0


Disteareth-100 IPDI



0.3
3.0


Acrylates/Vinyl Neodecanoate Crosspolymer





1.5
5.0


Compound of formula (56) or (3) or (12) or (17) or
2.0
4.0
6.0
8.0
10.0
12.0
14.0


(18) or (19) or (20) or (24) or (30) or (31) or (32) or


(35) or (41) or (42) or (43) or (44) or (50) or (51) or


(53)


Micronized 2,4,6-Tris(p-biphenylyl)-s-triazine [CAS
5.0
9.0
3.0
1.0
7.0
2.0
15.0


No. 31274-51-8]


Glycerin
6.0
6.0
6.0
6.0
6.0
6.0
6.0


Disodium EDTA
0.2
0.2
0.2
0.2
0.2
0.2
0.2


Phenoxyethanol (and) Methylparaben (and)
0.7
0.7
0.7
0.7
0.7
0.7
0.7


Ethylparaben (and) Butylparaben (and)


Propylparaben (and) Isobutylparaben


Tocopheryl Acetate
0.3
0.3
0.3
0.3
0.3
0.3
0.3


Example B2


C12-15 Alkyl Benzoate
4.0
4.0
4.0
4.0
4.0
4.0
4.0


Butyl Methoxydibenzoylmethane
1.0
1.0
1.0
1.0
1.0
1.0
1.0


Octocrylene
7.5
7.5
7.5
7.5
7.5
7.5
7.5


Isohexadecane
3.0
3.0
3.0
3.0
3.0
3.0
3.0


Cyclopentasiloxane
4.0
4.0
4.0
4.0
4.0
4.0
4.0


Terephthalylidene Dicamphor Sulfonic Acid
0.3
0.3
0.3
0.3
0.3
0.3
0.3


Titanium Dioxide particles size 10 to 100 nm
1.7
1.7
1.7
1.7
1.7
1.7
1.7


TiO2 (and) isodeceth-6(and)Oleth-

1.5




1.0


10(and)Alumina(and) Simethicone


Alumina coated TiO2


2.0

4.0


TiO2(and)isolaureth-4 Phosphate(and)Vinylbuteth-
0.5
0.5
0.5
0.5
0.5
0.5
0.5


25/Sodium maleate copolymer


TiO2(and)Diethylhexylcarbonate(and)polyglyceryl-
0.8
0.8
0.8
0.8
0.8
0.8
0.8


6 polyhydroxystearate


TiO2(and)Aluminum hydroxide(and)Dimethiconol

3.0


methicone copolymer


TiO2(and)Aluminum hydroxide(and)Dimethiconol


2.0


methicone copolymer


Silica coated TiO2



3.0


TiO2(and)Aluminium hydroxide(and) Isostearic




7.0


acid


Maganese modified TiO2





8.0


ZnO particles size 10 to 100 nm
3.0
3.0
3.0
3.0
3.0
3.0
3.0


Pentaerythrityl Distearate

1.5




1.0


Glyceryl Dibehenate (and) Tribehenin (and)


2.0

4.0


Glyceryl Behenate


Stearic Acid
0.5
0.5
0.5
0.5
0.5
0.5
0.5


PEG-100 Stearate (and) Glyceryl Stearate
0.8
0.8
0.8
0.8
0.8
0.8
0.8


Octadecene/MA Copolymer (and) Methyl Acethyl

3.0


Ricinoleate (and) Di-methylhepthyl Adipate


C30-38 olefin/isopropyl maleate/MA copolymer


2.0


Hydrogenated Dimer Dilinoleyl/Dimethylcarbonate



3.0


Copolymer


Cyclopentasiloxane (and)




7.0


Acrylates/Polytrimethylsiloxymethacrylate


Copolymer


Isododecane (and)





8.0


Acrylates/Polytrimethylsiloxymethacrylate


Copolymer


Poly(Glycol Adipate)/Bis-Hydroxyethyoxypropyl






5.0


Dimethicone Copolymer


C20-22 Alkyl Phosphate (and) C20-22 Alcohols

2.5



3.0


Candelilla/Jojoba/Rice Bran Polyglyceryl-3 esters


5.0



6.0


(and) glyceryl stearate (and) Cetearyl alcohol (and)


Sodium stearoyl lactylate


Glyceryl oleate citrate (and) Caprylic/Capric



4.0


Triglycerides


Potassium Cetyl Phosphate
1.3



1.3


PVP/Eicosene Copolymer
1.0


Aqua
Qs to 100
Qs to 100
Qs to 100
Qs to 100
Qs to 100
Qs to 100
Qs to 100


Glycerin
4.0
4.0
4.0
4.0
4.0
4.0
4.0


Compound of formula (56) or (3) or (12) or (17) or
2.0
4.0
6.0
8.0
10.0
12.0
14.0


(18) or (19) or (20) or (24) or (30) or (31) or (32) or


(35) or (41) or (42) or (43) or (44) or (50) or (51) or


(53)


Micronized 2,4,6-Tris(p-biphenylyl)-s-triazine [CAS
5.0
9.0
3.0
1.0
7.0
2.0
15.0


No. 31274-51-8]


Propylene Glycol
5.0
5.0
5.0
5.0
5.0
5.0
5.0


Xanthan Gum
0.2
0.2
0.2
0.2
0.2
0.2
0.2


PVP/dimethylconylacrylate/polycarbamyl/polyglycol


ester


Polyester-5


Disteareth-75 IPDI

0.3
3.0


Disteareth-100 IPDI



0.3
3.0


Acrylates/Vinyl Neodecanoate Crosspolymer





1.5
5.0


Acrylates/C10-30 Alkyl Acrylate Crosspolymer
0.2


Disodium EDTA
0.2
0.2
0.2
0.2
0.2
0.2
0.2


Triethanolamine
Qs
Qs
Qs
Qs
Qs
Qs
Qs


Dimethicone
0.4
0.4
0.4
0.4
0.4
0.4
0.4


Phenoxyethanol (and) Methylparaben (and)
0.7
0.7
0.7
0.7
0.7
0.7
0.7


Ethylparaben (and) Butylparaben (and)


Propylparaben (and) Isobutylparaben


Tocopheryl Acetate
0.9
0.9
0.9
0.9
0.9
0.9
0.9


Example B3


Synthetic Beeswax
0.5
0.5
0.5
0.5
0.5
0.5
0.5


Ethylhexyl Methoxycinnamate (stabilized by
9.8
9.8
9.8
9.8
9.8
9.8
9.8


incorporating into a polymer)


Isoamyl p-Methoxycinnamate
2.0
2.0
2.0
2.0
2.0
2.0
2.0


Ethylhexyl Salicylate
5.0
5.0
5.0
5.0
5.0
5.0
5.0


Butyl Methoxydibenzoylmethane (stabilized by
4.0
4.0
5.0
4.0
4.0
4.0
3.0


incorporating into a polymer)


4-Methylbenzylidene Camphor
4.0
4.0
4.0
4.0
4.0
4.0
4.0


Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine
2.0
3.0
2.0
1.0
1.0
1.0
1.0


Octadecene/MA Copolymer (and) Methyl Acethyl

3.0


Ricinoleate (and) Di-methylhepthyl Adipate


C30-38 olefin/isopropyl maleate/MA copolymer


2.0


Hydrogenated Dimer Dilinoleyl/Dimethylcarbonate



3.0


Copolymer


Cyclopentasiloxane (and) Acrylates/Polytrimethyl-




7.0


siloxymethacrylate Copolymer


Isododecane (and) Acrylates/Polytrimethylsiloxy-





8.0


methacrylate Copolymer


Poly(Glycol Adipate)/Bis-Hydroxyethyoxypropyl






5.0


Dimethicone Copolymer


Dimethicone
4.5
4.5
4.5
4.5
4.5
4.5
4.5


C20-22 Alkyl Phosphate (and) C20-22 Alcohols

3.0



3.0


Candelilla/Jojoba/Rice Bran Polyglyceryl-3 esters


4.0



4.0


(and) glyceryl stearate (and) Cetearyl alcohol (and)


Sodium stearoyl lactylate


Glyceryl oleate citrate (and) Caprylic/Capric



6.0


Triglycerides


Cetearyl Alcohol (and) Dicetyl Phosphate (and)
4.5



4.5


Ceteth-10 Phosphate


Cetyl Ricinoleate
3.0
3.0
3.0
3.0
3.0
3.0
3.0


Pentaerythrityl Distearate

1.5




3.0


Glyceryl Dibehenate (and) Tribehenin (and)


2.0

4.0


Glyceryl Behenate


Hydroxypropyl Dimethicone Behenate
2.2
1.0

2.2

2.2
0.5


Decyl Cocoate
1.0
1.0
1.0
1.0
1.0
1.0
1.0


Aqua
Qs to 100
Qs to 100
Qs to 100
Qs to 100
Qs to 100
Qs to 100
Qs to 100


Propylene Glycol
3.0
3.0
3.0
3.0
3.0
3.0
3.0


Compound of formula (56) or (3) or (12) or (17) or
3.0
3.0
3.0
3.0
3.0
3.0
3.0


(18) or (19) or (20) or (24) or (30) or (31) or (32) or


(35) or (41) or (42) or (43) or (44) or (50) or (51) or


(53)


1,1′-(1,4-piperazinediyl)bis[1-[2-[4-(diethylamino)-
2.0
3.0
1.0
8.0
4.0
3.0
1.0


2-hydroxybenzoyl]phenyl]-methanone (CAS No.


919803-06-8)


Decyl Glucoside
0.5
0.5
0.5
0.5
0.5
0.5
0.5


Acrylates/Vinyl Neodecanoate Crosspolymer


Ammonium Acryloyldimethyltaurate/VP Copolymer
0.3
0.3
0.3
0.3
0.3
0.3
0.3


PVP/dimethylconylacrylate/polycarbamyl/polyglycol


ester


Polyester-5


Phenylbenzimidazole Sulfonic Acid
2.0
2.0
2.0
2.0
2.0
2.0
2.0


Disteareth-75 IPDI

0.3
3.0


Disteareth-100 IPDI



0.3
3.0


Acrylates/Vinyl Neodecanoate Crosspolymer





1.5
5.0


Acrylates/C10-30 Alkyl Acrylate Crosspolymer
0.2


Disodium EDTA
0.2
0.2
0.2
0.2
0.2
0.2
0.2


Methylene Bis-Benzotriazolyl
5.0
5.0
5.0
5.0
5.0
5.0
5.0


Tetramethylbutylphenol


Tromethamine
0.8
0.8
0.8
0.8
0.8
0.8
0.8


Cyclohexasiloxane (and) Cyclopentasiloxane
0.8
0.8
0.8
0.8
0.8
0.8
0.8


Phenoxyethanol (and) Methylparaben (and) Ethyl-
0.8
0.8
0.8
0.8
0.8
0.8
0.8


paraben (and) Butylparaben (and) Propylparaben


(and) Isobutylparaben


Tocopheryl Acetate
0.4
0.4
0.4
0.4
0.4
0.4
0.4


CAS-Regno. 88122-99-0, Ethylhexyl triazone
2.0
1.5
2.0

1.0


(Octyl triazone; Uvinul T 150)


CAS-Regno. 6197-30-4, Octocrylene
3.0
4.0
5.0


1.0
5.0


CAS-Regno. 180898-37-7, Disodium
3.0
4.0
5.0
3.0


phenyldibenzimidazoletetrasulfonate Neo Heliopan


AP or Neo-Heliopan APC


CAS-Regno. 302776-68-7, Uvinul A Plus
4.0

5.0


CAS-Regno. 444811-29-4, Propanedioic acid, [(4-
3.0

1.0


hydroxy-3,5-dimethoxyphenyl)methylene]-, bis(2-


ethylhexyl) ester (Oxynex ST)


CAS-Regno. 477844-93-2, Octofluorene

3.0
1.0


2-phenylethylbenzoate

1.0
1.0


CAS-Regno. 68890-66-4, Octopirox
2.0


3.0
1.0


Tinogard TT (INCI Tetradibutyl Pentaerithrityl
1.0

1.0
1.0
3.0


Hydroxy-hydrocinnamate)


Tinogard HS (INCI Sodium Benzotriazolyl

2.0
3.0


3.0


Butylphenol Sulfonate)


Tinogard TL (INCI Benzotriazolyl Dodecyl p-
2.0

1.0
1.0

1.0
3.0


Cresol)


Phenol, 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-

2.0


3.0


methyl-, branched and linear


Cibafast H Liquid (INCI Sodium Benzotriazolyl
1.0


Butylphenol Sulfonate, Buteth-3, Tributyl Citrate)


Tinogard AS (INCI Bumetrizole)
2.0

1.0


Tris(tetramethylhydroxypiperidinol) citrate
1.0

1.0


(Tinogard Q)


220410-74-2 4-Piperidinol, 1-hydroxy-2,2,6,6-


1.0



1.0


tetramethyl-, 2-hydroxy-1,2,3-


propanetricarboxylate (3:1) (salt)


CAS-Regno. 1750-49-8, N-(2-Hydroxypropyl)urea

5.0



10.0


CAS-Regno. 2078-71-9, N-(2-Hydroxyethyl)urea


10.0

10.0


mixture of n-butylphthalimide and
0.5


5.0


isopropylphthalimide


CAS-Regno. 872424-70-9
2.0



1.0


CAS-Regno. 872424-71-0

2.0



1.0


CAS-Regno. 872424-72-1


2.0



1.0


CAS-Regno. 872424-73-2



2.0


mixture of glycosylglycerides or 2-O-beta-
3.0



2.0


glucopyranosyl-sn-glycerin


diaminobenzimidazole
0.1


dihydroxyacetone

2.0
4.0
2.0


2.0


carnitine
3.0

1.0


1.0


Tropolone
0.3



0.2


CAS-Regno. 130603-71-3, alpha-Glucosylrutin
0.5
0.1

1.0


CAS-Regno. 425371-14-8


CAS-Regno. 425371-15-9


CAS-Regno. 261356-13-2






2.0


CAS-Regno. 425371-03-5





2.0


CAS-Regno. 425371-04-6




2.0


CAS-Regno. 25371-05-7



2.0


CAS-Regno. 425371-06-8




2.0


CAS-Regno. 425371-07-9






2.0


CAS-Regno. 425371-08-0


CAS-Regno. 425371-09-1


CAS-Regno. 425371-10-4


CAS-Regno. 425371-11-5





2.0


CAS-Regno. 494198-67-3


CAS-Regno. 803699-05-0


CAS-Regno. 803699-07-2






2.0


CAS-Regno. 803699-09-4





2.0


CAS-Regno. 803699-11-8




2.0


CAS-Regno. 803699-14-1



2.0


CAS-Regno. 803699-15-2




2.0


CAS-Regno. 803699-17-4






2.0


CAS-Regno. 803699-18-5


CAS-Regno. 88137-31-9




3.0


CAS-Regno. 101220-33-1





2.0


CAS-Regno. 875878-17-4


CAS-Regno. 875878-18-5


CAS-Regno. 916463-32-6






2.0


CAS-Regno. 880761-99-9




2.0


CAS-Regno. 880761-95-5



2.0


Example B4


C12-15 Alkyl Benzoate
1.0
1.0
1.0
1.0
1.0
1.0
1.0


Butyl Methoxydibenzoylmethane
1.0
1.0
1.0
1.0
1.0
1.0
1.0


Octocrylene
7.5
7.5
7.5
7.5
7.5
7.5
7.5


Neopentyl Glycol Diheptanoate
6.0

5.0


Propylene Glycol Dibenzoate
4.0


Polyester-7 and Neopenthyl Glycol




8.0


Diheptanoate


Diethylhexyl Syringylidenemalonate

6.0


Polyester 8


4.0


Diethylhexyl Malate



7.0


PPG-3 Myristyl Ether Neoheptanoate





6.0


Phenethyl Benzoate






8.0


Isopropyl PPG-2 Isodeceth-7


Carboxylate


Isopropyl C12-15-Pareth-9 Carboxylate


Cetyl PPG-2 Isodeceth-7 Carboxylate


Isohexadecane
1.5
1.5
1.5
1.5
1.5
1.5
1.5


Cyclopentasiloxane
2.0
2.0
2.0
2.0
2.0
2.0
2.0


Terephthalylidene Dicamphor Sulfonic
0.3
0.3
0.3
0.3
0.3
0.3
0.3


Acid


Titanium Dioxide particles size 10 to
1.7
1.7
1.7
1.7
1.7
1.7
1.7


100 nm


Stearic Acid
0.5
0.5
0.5
0.5
0.5
0.5
0.5


PEG-100 Stearate (and) Glyceryl
0.8
0.8
0.8
0.8
0.8
0.8
0.8


Stearate


Potassium Cetyl Phosphate
1.3
1.3
1.3
1.3
1.3
1.3
1.3


PVP/Eicosene Copolymer
1.0
1.0
1.0
1.0
1.0
1.0
1.0


Aqua
Qs to 100
Qs to 100
Qs to 100
Qs to 100
Qs to 100
Qs to 100
Qs to 100


Glycerin
4.0
4.0
4.0
4.0
4.0
4.0
4.0


Compound of formula (56) or (3) or (12)
4.0
4.0
4.0
4.0
4.0
4.0
4.0


or (17) or (18) or (19) or (20) or (24) or


(30) or (31) or (32) or (35) or (41) or


(42) or (43) or (44) or (50) or (51) or


(53)


1,1′-(1,4-piperazinediyl)bis[1-[2-[4-
2.0
4.0
3.0
4.0
2.0
1.0
4.0


(diethylamino)-2-


hydroxybenzoyl]phenyl]-methanone


(CAS No. 919803-06-8)


Micronized 2,4,6-Tris(p-biphenylyl)-s-
5.0
9.0
3.0
1.0
7.0
2.0
15.0


triazine [CAS No. 31274-51-8]


Propylene Glycol
5.0
5.0
5.0
5.0
5.0
5.0
5.0


Xanthan Gum
0.2
0.2
0.2
0.2
0.2
0.2
0.2


Acrylates/C10-30 Alkyl Acrylate
0.2
0.2
0.2
0.2
0.2
0.2
0.2


Crosspolymer


Disodium EDTA
0.2
0.2
0.2
0.2
0.2
0.2
0.2


Triethanolamine
Qs
Qs
Qs
Qs
Qs
Qs
Qs


Dimethicone
0.4
0.4
0.4
0.4
0.4
0.4
0.4


Phenoxyethanol (and) Methylparaben
0.7
0.7
0.7
0.7
0.7
0.7
0.7


(and) Ethylparaben (and) Butylparaben


(and) Propylparaben (and)


Isobutylparaben


Tocopheryl Acetate
0.9
0.9
0.9
0.9
0.9
0.9
0.9


Example B5


Synthetic Beeswax
0.5
0.5
0.5
0.5
0.5
0.5
0.5


Ethylhexyl Methoxycinnamate
9.8
9.8
9.8
9.8
9.8
9.8
9.8


Isoamyl p-Methoxycinnamate
2.0
2.0
2.0
2.0
2.0
2.0
2.0


Ethylhexyl Salicylate
5.0
5.0
5.0
5.0
5.0
5.0
5.0


Butyl Methoxydibenzoylmethane
2.8
2.8
2.8
2.8
2.8
2.8
2.8


4-Methylbenzylidene Camphor
4.0
4.0
4.0
4.0
4.0
4.0
4.0


Bis-Ethylhexyloxyphenol
1.0
1.0
1.0
1.0
1.0
1.0
1.0


Methoxyphenyl Triazine


Dimethicone
4.5
4.5
4.5
4.5
4.5
4.5
4.5


Cetearyl Alcohol (and) Dicetyl Phos-
4.5
4.5
4.5
4.5
4.5
4.5
4.5


phate (and) Ceteth-10 Phosphate


Cetyl Ricinoleate
3.0
3.0
3.0
3.0
3.0
3.0
3.0


Butylene Glycol Cocoate
4.0
6.0
4.0
3.0
2.0
1.0
2.5


Hydroxypropyl Dimethicone
2.2
2.2
2.2
2.2
2.2
2.2
2.2


Behenate


Decyl Cocoate
1.0
1.0
1.0
1.0
1.0
1.0
1.0


Aqua
Qs to 100
Qs to 100
Qs to 100
Qs to 100
Qs to 100
Qs to 100
Qs to 100


Propylene Glycol
3.0
3.0
3.0
3.0
3.0
3.0
3.0


Micronized 2,4,6-Tris(p-biphenylyl)-s-
1.0
3.0
2.0
2.0
1.0
0.5
1.0


triazine [CAS No. 31274-51-8]


Micronized 1,1′-(1,4-piperazinediyl)-
3.0
1.0
1.0
4.0
2.0
1.0
3.0


bis[1-[2-[4-(diethylamino)-2-hydroxy-


benzoyl]phenyl]-methanone (CAS


No. 919803-06-8)


Compound of formula (56) or (3) or
4.0
3.0
2.0
1.0
3.0
5.0
3.0


(12) or (17) or (18) or (19) or (20) or


(24) or (30) or (31) or (32) or (35) or


(41) or (42) or (43) or (44) or (50) or


(51) or (53)


Octocrylene
2.0
4.0
6.0
8.0
10.0
10.0
8.0


Decyl Glucoside
0.5
0.5
0.5
0.5
0.5
0.5
0.5


Ammonium Acryloyldimethyltaurate/-
0.3
0.3
0.3
0.3
0.3
0.3
0.3


VP Copolymer


Phenylbenzimidazole Sulfonic Acid
2.0
2.0
2.0
2.0
2.0
2.0
2.0


Acrylates/C10-30 Alkyl Acrylate
0.2
0.2
0.2
0.2
0.2
0.2
0.2


Crosspolymer


Disodium EDTA
0.2
0.2
0.2
0.2
0.2
0.2
0.2


Methylene Bis-Benzotriazolyl Tetra-
5.0
5.0
5.0
5.0
5.0
5.0
5.0


methylbutylphenol


Tromethamine
0.8
0.8
0.8
0.8
0.8
0.8
0.8


Styrene/Acrylates Copolymer
5.0




3.0


PEG-6 Isostearate (and) Hesperetin

3.0



1.0
4.0


Laurate


Polyacrylate-15 (and) Polyacrylate-17


4.0


Carthamus Tinctorius (Safflower)



5.0


Oleosomes


PTFE




4.0


Cyclohexasiloxane (and) Cyclopenta-
0.8
0.8
0.8
0.8
0.8
0.8
0.8


siloxane


Phenoxyethanol (and) Methylparaben
0.8
0.8
0.8
0.8
0.8
0.8
0.8


(and) Ethylparaben (and) Butylparaben


(and) Propylparaben (and)


Isobutylparaben


Tocopheryl Acetate
0.4
0.4
0.4
0.4
0.4
0.4
0.4

## Claims

1. A Cosmetic composition comprising
a) at least one compound of formula (1)




wherein
X1 is a bivalent radical of formula




A in (1a) and (1c) is independently unsubstituted or substituted, straight-chain or branched C1-C12alkylene, which is optionally interrupted by C5-C12cycloalkylene, N, O or S; C5-C12cycloalkylene; biphenylene; C6-C10arylene; or C5-C10arylene-(C1-C12alkylene);
A and A′ in (1b) independently from each other are unsubstituted or substituted, straight-chain or branched C1-C12alkylene;
R1 is a radical of formula




R2 and R3 independently from each other are hydrogen; C1-C12alkyl; OR7; NR7R8; or C6-C10aryl;
X2 is O, or NH;
W1 is C1-C20alkyl; or a group Sp-Sil;
Sp is a straight-chain or branched saturated or single or multiple unsaturated C3-C12 hydrocarbon;
Sil is a silane; an oligosiloxane; or a polysiloxane moiety; and
R4, R5, R6, R7, R8 and R9 independently from each other are hydrogen; C1-C12alkyl; or C3-C12cycloalkyl; and
b)cosmetically tolerable carriers or adjuvants.

2. The composition according to claim 1 wherein
R1 is a radical of formula




 wherein
R5 and R6 independently from each other are hydrogen; or C1-C5alkyl.

3. The composition according to claim 2, wherein
R5 is C1-C5alkyl; or hydrogen; and
R6 is hydrogen.

4. The composition according to claim 1, wherein
X1 is a radical of formula (1b), wherein
A and A′ are C1-C4alkylene.

5. The composition according to claim 1, wherein
X1 is a radical of formula (1a), wherein
A is C1-C5alkylene; or phenylene; and
R9 is hydrogen.

6. The composition according to claim 1, wherein
X1 is selected from

7. The composition according to claim 1, wherein
R2, R3 and R4 are hydrogen.

8. The composition according to claim 1, wherein
Sil is the group SiR10R11R12, wherein
R10, R11 and R12 each independently are C1-C6alkyl; C1-C6alkoxy; or phenyl; or an oligosiloxane of formula —SiMem(OSiMe3)n; or an oligosiloxane of the formulae




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

9. The composition according to claim 1, which conform to formula (2)



wherein
R1 is a radical of formula




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




 and
R5 and R6 independently from each other are hydrogen; or C1-C4alkyl.

10. The composition according to claim 9, wherein
R1 is a radical of formula




X1 is selected from




 and
R5 and R6 independently from each other are hydrogen; or C1-C4alkyl.

11. A process for the preparation of a compound of formula (1),



wherein
X1 is a bivalent radical of formula




A in (1a) and (1c) is independently unsubstituted or substituted, straight-chain or branched C1-C12alkylene, which is optionally interrupted by C5-C12cycloalkylene, N, O or S; C5-C12cycloalkylene; biphenylene; C6-C10arylene-(C1-C12alkylene);
A and A′ in (1b) independently from each other are unsubstituted or substituted, straight-chain or branched C1-C12alkylene;
R1 is a radical of formula




R2 and R3 independently from each other are hydrogen; C1-C12alkyl; OR7; NR7R8; or C6-C10aryl;
X2 is O, or NH;
W1 is C1-C20alkyl; or a group Sp-Sil;
Sp is a straight-chain or branched saturated or single or multiple unsaturated C3-C12 hydrocarbon;
Sil is a silane; an oliqosiloxane; or a polysiloxane moiety; and
R4, R5, R6, R7, R8 and R9 independently from each other are hydrogen; C1-C12alkyl; or C3-C12cycloalkyl;
which process comprises reacting 2 moles of a chlorotriazine of formula (1m) with 1 mole of a compound of formula (1n) according to the following reaction scheme:

12. A process for the preparation of a micronized compound of formula (1)



wherein
X1 is a bivalent radical of formula




A in (1a) and (1c) is independently unsubstituted or substituted, straight-chain or branched C1-C12alkylene, which is optionally interrupted by C5-C12cycloalkylene, N, O or S; C5-C12cycloalkylene; biphenylene; C6-C10arylene; or C5-C10arylene-(C1-C12alkylene);
A and A′ in (1b) independently from each other are unsubstituted or substituted, straight-chain or branched C1-C12alkylene;
R1 is a radical of formula




R2 and R3 independently from each other are hydrogen; C1-C12alkyl; OR7; NR7R8; or C6-C10aryl;
X2 is O, or NH;
W1 is C1-C20alkyl; or a group Sp-Sil;
Sp is a straight-chain or branched saturated or single or multiple unsaturated C3-C12 hydrocarbon;
Sil is a silane; an oligosiloxane; or a polysiloxane moiety; and
R4, R5, R6, R7, R8 and R9 independently from each other and hydrogen; C1-C12alkyl; or C3-C12cycloalkyl;
comprising wet-milling, wet-kneading, spray-drying from a suitable solvent, by expansion according to the RESS process or by reprecipitation from suitable solvents of the compound of formula (1) to obtain microparticles having a mean particle size from 0.02 to 2 μm.

13. The cosmetic composition according to claim 1 wherein at least one compound of formula (1) is present in the composition in a micronized state.

14. A UV absorber dispersion, comprising
(a) at least one micronised UV absorber of formula (1)




wherein
X1 is a bivalent radical of formula




A in (1a) and (1c) is independently unsubstituted or substituted, straight-chain or branched C1-C12alkylene, which is optionally interrupted by C5-C12cycloalkylene, N, O or S; C5-C12cycloalkylene; biphenylene; C6-C10arylene; or C5-C10arylene-(C1-C12alkylene);
A and A′ in (1b) independently from each other are unsubstituted or substituted, straight-chain or branched C1-C12alkylene;
R1 is a radical of formula




R2 and R3 independently from each other are hydrogen; C1-C12alkyl; OR7; NR7R8; or C6-C10aryl;
X2 is O, or NH;
W1 is C1-C20alkyl; or a group Sp-Sil;
Sp is a straight-chain or branched saturated or single or multiple unsaturated C3-C12 hydrocarbon;
Sil is a silane; an oligosiloxane; or a polysiloxane moiety; and
R4, R5, R6, R7, R8 and R9 independently from each other are hydrogen; C1-C12alkyl; or C3-C12cycloalkyl;
having a particle size from 0.02 to 2 μm, and
(b) a suitable dispersing agent.