MXPA97009075A - Cosmetic and pharmaceutical preparations containing photoestable filters against rays - Google Patents

Abstract

The use of compounds of the formula I: where the double bond C = C is in the E or Z configuration, the variables have the following meanings: R1 represents COOR5, COR5, CONR5R6, CN, O = S (-R5) = O, O = S (-OR5) = O, R7O-P (-OR8) = O; R2 represents COOR6, COR6, CONR5R6, CN, O = S (-R6) = O, O = S (-OR6) = O, R7O-P (-OR8) = O; Re represents hydrogen, an aliphatic, cycloaliphatic, araliphatic or aromatic radical optionally substituted with carbon atoms, R4 represents an aromatic or heteroaromatic radical optionally substituted with 5 to 12 atoms of R5 bis R8 independently represents hydrogen, a cycloaliphatic, araliphatic, aliphatic radical of open chain or branched or an aromatic radical optionally substituted with up to 18 carbon atoms, where the variables R3 to R8 between them, each time together with The carbon atoms, where they are attached, can together form a ring of 5 or 6 atoms that eventually may have additional rings, as filters against UV radiation in cosmetic and pharmaceutical preparations for the protection of human skin or human hair against solar radiation, alone or together with known pharmaceutical and cosmetic preparations, in compounds that absorb lightning within the range of radiation

Description

FR F? GT W "; G? ^ HFTIG?", V FAPMAGFHTT? A QHG rnr.?ttFMFfj FTI Tpnq F? TG.G GAG-Ü F? ONTP? PAYOS MV DF e, rp T P? Í OM DF TO TUVFNG I ON I "j),,. ,,, - (!, _? i (iVi'lli I ótl -;,! ••> t go "fi f.1 F f -> rf 1 - MO 1? ~" 1 d "- > • -''- •! i V "í? | nj 'it- * Hp'lllU IH L >.? tlH > fjl L | i > =? f? l' .H-rll go > _ fd 1 H l'ct i »-) UV ¡'ll μ G> JJÍ-I p-ji IO? PI • Ur-iim'-la •. =) - * yf A mac ^ uia ^ er 1 -t pro j rn d «-> Either human epi ermis or to protect roptM i-ayos UV hair, speci fi cally within the range of 1? C? O nm. •) - ' - agents I-1 protection against you? light that are used < ^ n ju IJ¡ »H > -u i une-; c u m ^ t i a -_ > and f • * r m ^ cen l x > . to s ie n the object of H) > '• !! or to itu-'oo-j i? - 'd'i > "i i. r. < H < -ii lo > 11. r] i? ^? ?? H5 harmful - > MI - 1 1 < •* 1"?; -, filí? io iv ¡Jμi? -1 h ana. A > !? - m - '? - > , t- ~) lo-. "i? j? -nte-1"? pi jón nntrp 1 -t 3 u GÍ I'V H l -t? i? h? (? to protect i ngi ed i ^ ut »• - &- - , additional cofactors or degradation caused by r and r = UV, In many cases, the damage to the UV fibers will be reduced, the solar line that will lead to the terrestrial surface it has nz μ-ir f- of UV-B 'd 280 to "^ 2 nn) and of UV-A C 0 nm), e -ae find directly ady-icente a] range of light visiblf. The influence on human 3-pif-1 is especially noticeable in the case of UV-B radiation through l - »sunburn. Correspondingly the industry offers a large number of substances that absorb UV-B radiation V r ~ J I I - < (t μ? • I ii ll l-> I> 'I f-'f I • i' 1 i • '' j '> f30 (i> > > * • > df-1 - >? > 1. A! L I -I vl J dll (4 l H "l 3 -« d'-1 I IH- "! 'L> 1 lJ ll "- ') - < II Í-ii • < I | l If-? I; l i \ i -! i J? ll 1 IV A μ F O Vi H. -? I, - > lllb I fl l! -t ñi l- I i, I '«> ll-? i, plv'l'ij I -I-i. ! 'P ] 3 i. i lf-'í J '? dan- * i '? | ir'i j ^ 1 »?? -» (d f- 3 • qi l, -iiati na ob \ > ~ 11 P'I -Í; tin «, Di- -I af ? n n? -? fi edu? fu 1 -i? i? l? g? r pa d ad-a 1 slow water df- water * 1 11 μn- »l, that is, The skin becomes soft and there is a propensity for wrinkling, a high frequency of third skin cancers in the areas where strong solar radiation shows that the solar UI also provokes li Genetic Identification: Genuinely Almena!, Go to: - Of the? a? &An. IV.-. All-, -r.li.:- ». >» no > h = f "Jf? i? i? u -ji- '-i uní μ-ij ii -11? l.?? ^^? e í - -ni-si, A p >. ia - > fi 1 t raid, * - * - »f-1 fici» rd ii ndi'd -1 t -oiij de? -n¡t =.? - ioiie-! GO «F-> - n? i n f-1 - ienle f-1 protection elements i ntra the lu, 'for cosmetic and clinical preparations that can erl l1 al to the mind as f 3 ro for radiation l! V ~ A and whose absorption maximums, therefore, are in the range of approximately 20 to 380 nm. In order to be able to achieve the effect of the same or the same amount as possible, such agents of protection against the environment must present a high specific extinction at the same time. In addition, the agents for protecting against UI for cosmetic preparations must also satisfy numerous conditions, for example, a good solubility in cosmetic oils, a high solubility in cosmetic preparations, and a high solubility in cosmetic oils. il -i i > )? i 1 • < (M i 'ii -i'l "> u -3 1 - * - >? H q I i i- < | ij -t d'1 HÍt'i ¡?' AI i i i ii ln.O i. ioi. ioii 1.? l |? n? oi 3 1 lili! -IIJI I-. , l! t | ,. i i ioil o j r'i i i < H I | l OII -t l ll o lif-'bf- t ¡íSei- 3 - "" i j I! I I i, i 1 l / i 1 Ol C H 1,. 1 (in emb ry with lo- 1? I _¡ tj > - »absorb UV-ray-to-gt; - tua3menl and isponsible can not be achieved by stability or is achieved only photoestabí 3 i dad i its In the e3 Patent document F? n &?, No. 2 40 933 is described 4- M, 3 -d i? »F? I 3 el, j 1) -4 '-»? l o, u J j ben.'o J 1 me • ¡* no • _ mo f i 3 I ro I ^. i i «v - I IV? * -)! - μ oμ or > oiiiiu II-JI e-ite i lt o l o tra, i, UV-A -? ?, f l, end i o fi t the > mu i OIVAHDA? b ..n_? l nomin or "P R ^.? L 1789" i n -, -i i ios f i 1 I, t > S or * i -i radiates »> ue =,! IV-5 B, μ r-t abso ber l i-- > I-i UV radiations that t i ne loiiy i iiiJes il onda between 280 and 380 nm. in ety sl, filter for UV-A radii, when used alone or in combi tion with fi les LIV-B n is n lently n b l for p ropo vr on a r protection or di ? - ad skin for a sunbath long as c¡uw want live from uiid repeated application to írdet vals ime "reyulares and short, if you want to" achieve uu < ip otecc effective ion skin against all I? S rsdiai i on -n UV P i 'in accordance with EP 0514491, the UV-A filter not sufficiently photo-stable must; I? ID1?? "- > > - > i? > -d? before the iK-is ei -? ? j? ~? r gone 2-ti -p 1-3, "di fef lpr r í 1 oo, that go an llo-? i itit s > ~ n-iiu filter deutio ijel ta o rad? < > .. io?) • • • • • UV-B In addition to complying with EP 251 398, it was proposed to join the UV-A absorption chromophore and the UV-B radiation by means of a link in a This has the disadvantage of not allowing on the one hand a free combination of filters for UV-A radiation and UV-B radiation in the cosmetic preparation and complicates ions in the chemical bond of the chromophore allows only certain combinations. object of the present invention is to propose light protection agents for cosmetic and pharmaceutical purposes that absorb with a higher extinction within the range of UV-A, photostable radiations, which have a limited own color, that is to say, that have a structure of acute band and, depending on the substituent, soluble in a This object is achieved in accordance with the present invention by the use of compounds of the formula I ond ul obl nl ^ .t-j C = C was eui | l? -i on 1 ^ with f irra IOM F n bi n 7, 3 -i - > *-to? ishles I. if > ? i.-f? 3o "> jnie! -, or ijnj f irados; pi, ^ pr í ..-, _..-, ^ COOP5, COP5, C? NRG» P ?,? N,? -SÍ-R5 > - = O, OR O ^ i- -n, F70-Pi-NP8) = - 0; R2 represents CHORA ,, C0R6, C0NR5R6, CN, 0-S-R6 t > = 0, 0 = 5 í- P3 It represents hydrogen, a radical to i phatic, cicloal Ifa ico, araliphatic or aromatic, optionally substituted with up to 18 carbon atoms; A represents an ai radical ornamental I ico or fteteroaromá t ico ßv ntija lly substituted 5 to 12 atom s of ring; R5 and bi * FR represents the re enl the hi :, drógenn, ra n ic ic loa lf i 1 i fat co, lifático, alifátu.o i adt-na open or branched or aromatic radical eventualmepte replaced with up to 18 carbon atoms, where the variables R3 to R8 between them, each time together with the carbon atoms where they are attached, can together form a ring of 5 or 6 atoms that can eventually have additional rings, as filters against UV radiation, especially filters with UV-A radiation, in cosmetic and pharmaceutical preparations for the protection of human skin or human hair against solar radiation, alone or together with pharmaceutical and cosmetic preparations (iil,!)! ol '< > . in 'otitμt ti- - I i > : -. ? .jne b i-Ot be. i ln; F a o- =? inside cJel ra I lijo 1 -s f d > (Oue =; IJV Re μce fi - f c omμ >.? E ^ >? 1, I - l Fót ula I wherein P3 = r ftr'e bidróijeno .enta, Pi represents CN, C00P5 and C0R5 and P2 represents CN, and CORA COOP¿ ,, where R5 and Re > independently of one another are aliphatic radicals of aromatic radicals straight or branched chain or optionally substituted with up to 8 carbon atoms employing compounds is particularly preferred. of Formula I in 3 which P3 represents hydrogen, R1 represents CN, C00P5 and C0P5 and P2 represents CN, C00R6 and C0R6, where R5 and PA >; Independently and pril r? they represent radic ls to the filarias de oadena abi-o ta or branched or else mátic "eventually substituted with up to 8 carbon atoms and R4 represents an aromatic radical to hetero hetero or optionally substituted with up to 10 carbon atoms in rings, especially a phenyl, thienyl, furyl, pyridyl, indolyl or substituted naphthyl radical, and a substituted phenyl or thienyl radical is especially preferred. All substituents include their lipophilic and hydrophilic components with, for example, up to 20 carbon atoms.

Iiophophilic radicals, is redials that increase the oil solubility of the compounds of the formula I are for example aliphatic or cycloaliphatic radicals. i a 3 ni f \ tf- 'r -i »I a 11- - a 3 qu i 1 o c uri 1 -í 18 ti tiio = > 11 > > .-i r b? id, 1 ad l? "" 1 e- to n, i, monkey? 3 q? i 1 a. ?? 1 'to go.), To Iqn 1 liiti i il'.l »le ni-ic -4 F'bi ini 3 o, onoa lqu J. lamí noc boro, di l i i noca rboni lo, a mua 1 qn lac-musul fon i lo alqui i ai nosi'3 f oni 1 o, adema- »substituents of cuno, nitro, bromo, chloro, iodo well fluorine. The hydrophilic radicals, ie radicals which increase the solubility in water of the compounds of the formula 7 are, for example, carboxy and sulfoky radicals and especially their salts with any physiologically acceptable cation, such as, for example, salts alkaline or slen of tr ia 3 qu i 3 an to, as p? ~ > ? example sa3e- »de tr i - fli id oM ln 11) ammonia or bien les d 2-m fc i i ni-o-o 3 o 3-diFionio, In addition we will consider radicals of a3 qu 3 -3 moni or with any physiologically acceptable anion. As alcohol radicals: < i are considered radicals with 1 to 12 carbon atoms, preferably with 1 to 8 carbon atoms. We can mention the following examples: meto isopropoxy-n-propo? I-1-meti lpropo? I-n-butoxin-pent ?! < i-2-ylprspoxy-3-methylobute? i-1, 1-di.methylpropo? i-2,2-imethylpropoxy-hexoxy-1-methyl-1-ylpropoxy-hepto < i - oc. ton i - 2-et i. lbe: < o¡ < i- Co or radicals of onoalqu i 3. ami. no or dialqui lamin * can be mentioned, for example, alkyl radicals containing from 1 to 8 carbon atoms, such as methyl, n-prqpils, n-butyl, 2-methylprspiol, 1,1- dimethyl lpro ilo, * t? e? i la, heptyl, 2-ethe lhe: < It is isopropyl, 1-methylpropyl, n-pentyl, 3-methyl Ibutiol, 2,2-di-ethylpropyl, 1-methyl, and 1-ethyl-1-propyl, and octyl These radicals are in the same proportion in the monoalkyl radicals laminoc rboni, di-lyalkylaminocarbonyl and sulfonyl, the alkoxycarbonyl radicals are, for example, esters containing the aforementioned alkoxy radicals or radicals of higher alcohols, for example with up to 20 carbon atoms, for example iso -alcshsl C15 The invention also relates to novel compounds of the formula II, in which the double bond C = C is in the E and Z configuration and where X represents a cyano or C0CH3 radical, R4 represents a phenyl radical which, when X = CN, may be substituted by one or several radicals ilo, aleo;, i, a 3 qu i 3 ami GIOL G < I pump it, to 3 icarbom 3 or, each I?.? Not with up to ^ or of bonus or either radi? Ales or bi n aí bu. i, as well as r "ti tiyente- that f ore in 3 a solubility in water, chosen-" within the group of radicals of carbonate, sulfonate or a3 qui the ouio, for example alkaline carboxylate or radicals carboni loxi-tri- (hydroethyl) amanium or ß-sulfonyl i-tri- (hydroxyethyl) ammonia, or, when X = C0CH3, it may be substituted by one or more alkoxy radicals with up to 20 carbon atoms or alkoxycarbonyl radicals with 4 to 20 carbon atoms, as well as by substituents that facilitate the solution in water, chosen from the group consisting of carbon and lato radicals, sulfonate or a3 qui onium, and P5, when X = CN, represents a radical C (CH3) 3 or, when X = C0CH3, an alkyl, alkoxy to alkoxyalkyl group of open, branched or cyclic chain each with up to 18 carbon atoms or an aryloxy group. In the following table, preferred compounds according to the present invention are indicated ion of formula II. Table I. * 3 1 or 10 ? » ? 8 7? -. « Z6 4? 4? 4 , The compounds of the. Formula I employed according to the present invention can be prepared in accordance with the following equation - 3 ROB R1-Cfl2- R2 + R «-NH2 + R3G40R).

R ß CB3, C3B5 by condensation, where R1 to R4 have the meanings mentioned above. By way of example, the reaction of 2,4-pentanedione with 2-ethylhexyl ester of anthranilic acid and triethylformamide provides compound 24 of Table 2. Cosmetic and pharmaceutical preparations containing light protection agents are they are generally found on a base of a vehicle that contains at least one oil phase. However, there are also preparations based only on water by using compounds with their hydrophilic components. Correspondingly, oils, oil-in-water and water-in-oil emulsions, creams and pastes, lipsticks or fat-free gels are considered. Such sun protection preparations can be correspondingly in liquid, pasty or solid form, preferably in the form of water-in-oil creams, oil-in-water creams and lotions, foaming creams, aerosol, gels, oils, pencils , dust, dew or ¡ji > j | liir? 1llf > 5 > ? ? * i i. i ?? "ít 1? l l > í < t a 1 • - ') h ?! V,? fji 13.

I had us! > ~ > s in l á «? b i tu eoniti l > : or p? For example, shave from parafipa, er-tearata eg 1 i • ".> - •> t, i, isoproyl, isoproyl, ii soprop 11 acl a, ceti lestear il ester de ar: io 2 -the physical, hydrated oil, petroleum jelly, caprylic acid / caprinic acid, microcrystalline waxes, lanolin and steric acid, common cosmetic auxiliaries, which can be considered as additional substances they are, for example, coef fi cients, fats and waxes, stabilizers, pads, biogemics, film formers, flavoring agents, cologrants, gas greases, preservatives, pigments, electrolytes (for example sulphate magnesium) and pH regulators Water-in-oil emulsions and also oil-in-water emulsions, such as polyglycerol ester, partially esterified sorbitan ester or glyceride, are preferably considered as co-emulsifiers. icéridosj as waxes are considered among other beeswax, paraffin wax or microcera eventually being in combination with hydrophilic waxes. Co-sensitizing agents may include metal salts of fatty acids such as magnesium, aluminum and / or zinc stearate. Suitable thickeners are, for example, acids? _f117 t - * 'i í 1 i f -os relicnlado-a and - »" - > IIPI col 3 -JÍ "- * GI dn, f -; f¡j ^ .. talm nt gum e MH IIO, ua r-iju r ¡^ g = «i --aya i, alg * naly o tilosa», ca i! > or. < iin fc i 1c ^ 1 * < 1 osa e nlf'n. j < i 1 *. e] ulnsa, ad m s alb s gra o, < -anoglycosides and fatty acids, pol i ar. r i] alcohol, polyvinyl alcohol and polyvinyl pyridone. Among the active substances "iogena" are, for example, plant extracts, albumin hydrolysates and itamine compounds. Film-forming substances are, for example, examples such as qui túsanos, q? Itosano mi ocr ist l ino or qui tosano cuaternario, pol i vini Ipira. i don, i.opo! i »« er i zados of vi nilpi crol idona-viitile acetate, polymers of the series of lo-? A i os a »: rí li os, deriva-; d «- = > c lulo a cua ern ia and similar compounds. Suitable preservatives are, for example, formaldehyde solution, p-hydroxybenzoate or sorbic acid. Suitable linting agents are, for example, esters of glycolistearic acid with, for example, ethylene glycol distearate, but also fatty acids and monoglycerol of fatty acids. As dye, they can use substances that are suitable and suitable for cosmetic purposes, such as those presented in the publication "osmet ische Fárbemittel" (Cosmetic dyes) of the Commission on Dyes of the German research community, published in Verlag Chemie, Weinhei, 1984. These dyes are used ha it "1 nte en? >; n > I'm facing US > ie f., O01 e ("'.TV * by weight, in! l' yes i I 'I l on I er = •» The tol el i ad of the.-. su -. > t arn- > a > au i li - "s and adn. j na] eu il < ect 1 to ROV., of p & rsnc of 6 =) 4 < See that and 1 - =) rí- no aqueos ("active substance j va") can represent from 20 to 80 * /., Preferably from 30 to 70 * /. by weight - in relation to the agent. The preparation of the agent can be carried out in a manner known per se, that is to say, for example, by hot, cold emulsion, hot / cold emulsion or PIT emulsion. This is a purely mechanical procedure, no chemical reaction is observed. Finally, their ancestors that absorb radiation within the range of UV-A rays can be used together, insofar as said radiations are stable within the overall system according to the present invention of the combination to be used of anti-UV filters. UV-B and UV-A radiations. The object of the present invention are cosmetic preparations containing 0.1 to 10 * 4 by weight, preferably 7% by weight, based on the total amount of cosmetic and pharmaceutical preparation, of one or more compounds of the formula I together with compounds that absorb radiation within the range of UV-B light as agents for light protection known for p.-ep r-ac: i os os? Pharmaceuticals, where the compounds of the formula I are generally employed in a lower amount than the absorption compounds of the UV-B r. Most of the. agent for protection against light in cosmetic and pharmaceutical preparations that serve to protect the human epidermis with compounds that absorb UV light within the range of UV-B radiation, that is, within the range of 280 to 320 nm. For example, the part of the UV-A radiation absorbers to be used according to the present invention reaches from 10 to 90 * /. by weight, preferably from 20 to 50 * by weight based on the total amount, of what substances? They absorb UV-B and UV-A radiation. As substances which filter UV-B radiation which are used in combination with the compounds of formula I according to the present invention, any substance which filters out UV-B radiation can be detected. By way of example, the following are mentioned: No. CAS-Nr substance (= acid) 1 4-aminobenzoic acid 150-13-0 2 aethylsulfat of 3- (4'-trimethylammonium) - 52793-97-2 benzyl 1 idenbornan-2-one 3 3,3,5-trimethyl-cyclohexyl salicylate 118-5A-9 (ho osalate) 4 2- hydrs: -: i -4-? r? etuxi -ben ..- O fen? na 131-57-7 Í Kiber'.ooio) 3 a «.. gone 2-f nilbenzi ida zo1-5-su1 phonic and 27503-81-7 its salts of potassium, sodium and triethanolamine 6, 3,3 '- (1,4-phenyndiimet in) -bis (7,7-90457-82-2 dimeti l-2-axob. icicla (2.2. i> heptan-lm «fucso-ufuonic and its s M < 7 polyether-ie ester of 4-bis acid (psl ieto) 113010-52-9 amino-benzoic 8 2-eti lhe; <; 4-dimethylamino acid 21245-02-3 benzoi acid or 9 2-ethylhexyl ester salicylic acid 118-60-5 2-isoamic acid ester inámico 7/6 / 7-10-2 11 2-eti lhe i. 4-Methoxyamic acid ester 5466-77-3 12 2-hydroxy-4-metho? i-benzofepor? -5-sulphone 4065-45-6 (sul-isobenzonium) and its sodium salt 13 3- ( 4'-sulfo) benzylidene-bornan-2-one and its 58030-58-6 s them 14 3- (4'-methyl) benzyliden-bornan-2-one 36861-47-9 15 3-benzyl idenbsrn n-2 -ana 16087-24-8 16 l- (4'-isopropyl-phenyl) -3-phenepropan-1-3- 63260-25-9 dione 17 4-isopropyl-1-benzyl salicylate 94134-93-7 18, 2,4,6-triamilin- (o-carb? -2'-ethylhe? Il-1'-88122-99-0 o, < i) -l, 3,5-triazine l 1? 3-i.midazole -4-i 1-a rl 1 ico acid and its 1 4-98-3 * esters of et i.1o 20 ethyl esters of 2-ci non-3,3-di f - 5232-99-5 ni 1acrl io 21 2'-e ilhe: < 2-ci ns-3,3-di-6197-30-4 phenylacrylamide i1-o-aminobenzoate acid ester: 134-09-8 5-methyl-2- (1-methylethyl) > -2-aminobenzoate 23 glyceryl p-aminobenzoate or: 136-44-7 1-glycometer 4-aminobenzoic acid 24'2'-dih id rax i-4-meta: < ibenzofensna 131- 53-3 (di. Ioi ibenzone) 25 2-h idrox i-4-meto? I- -met-i lbenzophenone 1641-17-4 (Mexonon) 26 triethanolamine salicylate 2174-16-5 27 Dimetoxy phenylalumonic acid or sodium salt of 3,4-dimethaxy-phenyl-1-glyoxalic acid 3- (4-sulphon) benzylidene-2-one-one and its 56039-58-8 salts Finally Micronized pigments such as titanium dioxide and zinc oxide should also be mentioned. For protection of human hair against UV radiation, the light protection agents according to the present invention of formula I can be integrated into shampoos, lotions, gels and emulsions in concentrations of 0.1 to 10 * 4 by weight , preferably from 1 to 7% by weight. The corresponding formulations can be used, for example, for washing, dyeing or curling the hair. The compounds to be used in accordance with the present invention show, in general terms, an especially high absorption capacity within the range of UV-A radiation with each acute band structure. They are also very soluble in cosmetic oils and are easily combined in cosmetic formulations. The emulsions prepared with the compounds of the formula I are characterized by high stability, the compounds I m are characterized by their high photo-stability, and the preparations made with the compounds I are characterized by being pleasant to the touch. The object of the present invention is also compounds of the formula I for use as a drug as well as a pharmaceutical medium for the preventive treatment of skin inflammations and allergies as well as for protection against specific types of skin cancers, said drugs contain a effective amount of a compound of formula I as the ati va substance. . The pharmaceutical agent according to the present invention can be administered orally or topically. In the case of an oral administration, the pharmaceutical agent is, for example, in the form of tablets, capsules,. ".] 3 i ina, drags, in the form of -i> 3I10-. -ol» tc in, eu sion • »well -ju-spension. 1 co s = => carried out, for example, by * means and ungín-nto, cream, gel, dew, solution not well l, ex emp I is: I. Preparation Example 1 General instructions (for the compound rto 3 of the Table 2) 0.1 mol of 2-ethylhexyl ester, 0.1 mol of pi to 1 oi of ketone tri lo and 0.1 mol of orthoformate d * triethyl in 100 ml of diethylene glycol were heated. 2 hours at a temperature of 12 ßC so that the ethanal was removed by des ilation. After cooling to a temperature of 80 ° C., it was mixed with water and filtered from the precipitate obtained, finally crystallized from petroleum ether Compound 1 of Table 2 was obtained in a yield of 80%. Two moles of anthranilic acid, 0.1 mole of 2,4-pentanedione and 0.1 mole of triethyl orthoformate in 100 ml of diethylene glycol were heated for 2 hours at a temperature of 120 ° C. Ethanol was removed by distillation, after cooling to a temperature of 80 ° C. it was mixed with water and filtered from the obtained precipitate, finally crystallized from petroleum ether Compound 24 of table 2 was obtained in a yield of 70 *. 4. EXAMPLE 3 0.1 mol of m-toluidine, 0.1 mol of pivaloi lacetoni tri lo and 0.1 mol of triethyl orthoformate and 1 g of zinc chloride in 100 ml of diethyltin were heated for 2 hours at a temperature of 120 * C, so the et was removed anol by distillation. After cooling to a temperature of 80 * C it was mixed with water and removed by filtering the precipitate obtained. Finally, it was crystallized from petroleum ether. Compound 2 of Table 2 was obtained with a yield of 70 *. Table 2 shows other compounds prepared in this way. Table 2 1 > C8H17 = 2-ethylhexyl General riu ions for the repair of r-a p muli? - op i t > '> s c o s e I ', i o =; All in re i n is soluble in oil and heated in a container with agi ation. a temperature of 85 * C. When all the ingredients are melted, or they are in a fluid phase, the aqueous phase is integrated with homogenization. Under stirring, the water is cooled to a temperature of about 40 ° C, and said juice is perfumed, homogenized and then cooled constantly at a temperature of 25 ° C. P reparae: ions Example 4 Formulate ion for lip care up to 100 Fuce inum anhydricum 10.00 glycerin 10.00 titanium dioxide 0.5-10 compound no. 1 of table 2 8.00 octyl methoxylate 5.00 zinc oxide 4.00 kidney oil 4.00 pentaerythi trityl stearate / caprate / caprylate adipate 3.00 glyceryl stearate SE 2.00 beeswax 2.00 microcrystal wax ina 7..00 bib? ntonite Q? > a fcerni um-18 1,50 npol (mere FF8-45 / dodec i. lgl icol Example 5 Formulation for the care of the lips up to 100 Eucerin? ma bycl icum 10.00 glycerin 10.00 titanium dioxide "* 0.5-10 compound no 24 of Table 2 8.00 Oceana Methoxymate 5.00 Zinc Oxide 4.00 Castor Oil 4.00 Pentaeryl Stearate / Cap / Cap Adiplate 3.00 is glyceryl time SE 2.00 Wax », Bee 2.00 microcrystalline wax 2.00 bentonite Quaternium-18 1.50 copolymer PEG-45 / dodecylglol Example 6 Formulation for solar charger with microplates up to 100 Water 10.00 et octyl inaseate 6.00 PEG-7 hydrogenated castor oil .00 titanium dioxide 0.5- 10 compound no.1 of table 2 5.00 ace i. Ie i nera.1 5.00? -mefc! -: isoamallo ic to 5. 0 prop i 1eng1 ico1 3.00 a • ::: ei te d ojoba 3.00 camphor of 4-met ilben i 1 iderto 2.00 copolymer PEG-45 / dodeci lgl icol 1. 00 di met icona 0.50 PEG-40 hydrogenated castor oil 0. 50 tocopheryl acetate 0.50 phenoxyethanol 0.20 EDTA Example 7 Formula for sunscreen with microp oments up to 100 Water 10.00 octyl methoxine 6.00 PEG-7 hydrogenated castor oil 6. 00 titanium dioxide 0.5-10 compound no. 24 of table 2 5.00 mineral oil 5.00 isoamyl p-methoxycinnamate 5.00 propylene glycol 3.00 jojoba oil 3.00 camphor of 4-me i lbenci 1 ideno 2.00 copolymer PEG-45 / dodec: i lgl icol 1.00 dimethicone, PEG- 4 ac: ei. I give you r i. c i no i i id rogeciacl >;:: > 0.50 acet to ta oferi lo 0.50 f oxy nol 0.20 EDTA Example 8 Fat-free gel up to 100 Agufc 8.00 octyl metho-cypamate 7.00 titanium dioxide 0.5-10 compound No. 1 of table 2 5.00 glycerin 5.00 PEG-25 PABA 1.00 camphor of 4-met i Ibep i 1 idena 0.40 cross polymer of alkyl acrylate CÍO-C30 acril to 0.30 imidazole idini lurea 0.25 hydro, butylcellulose 0.25 methylparaben sodium 0.20 EDTA disodium 0.15 fragrance 0.15 propylparaben sodium 0.10 sodium hydroxide Example 9 Tel fat-free up to 100 Water 8.00 methox i > :::. i nama t.o de t t .1 or 7. OO d i ó: < i. of t i Un i. 0.5-10 Item No. 24 of * table? 5.00 l i er i na 5 5.00 PEG-25 PA8A 1.00 camphor of 4-met i Iben i 1 ideno 0.40,; cross polymer of alkyl acrylate CÍO-C30 acrylate 0.30 imidazole id i ni lurea 10 0.25 hydroxyethylcellulose 0.25 methylparathaene sodium 0.20 EDTA disodium 0.15 f ag n ia 0.15 propylp rabeno sodium 15 0.10 sodium hydroxide Example 10 Sunscreen (LSF 20) up to 100 Water 8.00 meta octylamine i!? 0 8.00 titanium dioxide 6.00 PEG-7 - hydrogenated castor oil t 0.5-10 compound No. I of Table 2 6.00 mineral oil 5.00 or zinc gone 25 5.00 isopropyl palmitate 5.00 J midi "r> > i] d my lu t -" • > =? 3.00 = "" * -_. te de jo joba 2.00 copol Imero e PEG - 45 / dode i lg 1 i col 1. 00 camphor of 4-met i 1 be._ > ~ i 1 i deno 0.60 gnesium stearate 0.50 tocopheryl acetate 0.25 methylparaben 0.20 disodium EDTA 0.15 propylparaben Example 11 Sun cream r U.SF 20) ha a 100 Water 8.00 me go breast to octila 8. 0 dio :, gone from itanio 6.00 PEG-7 - hydrogenated castor oil 0. 5-10 compound No. 24 of Table 2 6. 00 mineral oil 5.00 zinc oxide 5.00 isopropyl palmitate 5.00 imidazole idinylurea 3.00 jojoba oil 2.00 copolymer of PEG-45 / dodeci lgl icol 1. 00 camphor of 4-methylbenzene 1 ideno 0.60 magnesium stearate 0.50 tocaferyl acetate .25 met i Ipa rataene .20 EDT disdi ca. 15 prop i 1pa ra.taeno Ejem 1o 12 Sunscreen water resistant to 100 Water 8.00 meto icinama or octilo 5.00 PEG-7 - hydrogenated castor oil . 00 propi lepgl icol 4.00 isopropyl palmitate 4.00 caprylic / capric triglyceride 0. 5-10 compound No. 5 of table 2 4.00 glycerin 3. 0 c ite d jo mba 2.00 camphor of 4-me i Ibep i 1 ideno 2.00 titanium dioxide 1.50 copolymer PEG-45 / dode i lgl icol 1. 50 dimethicone 0.70 magnesium sulfate 0.50 magnesium stearate 0.15 fragrance Example 13 Water-resistant solar cream up to 100 Water 8.00 octyl metho-icine 5. OO GFR- - 5"OO μ n > p i \ P? U 1 t c ol 4.00 palmitate d ^ i = - p rop i 1 > J 4. OO 1, F i g 1 ic ér i d > ) cap r 11 i o / r A r j c o 0.5- 1 compound No. 24 of table 2 4.00 glycerin 3.00 jojoba oil 2.00 camphor of 4-met i lbepci 1 ideno 2. 00 titanium dioxide 1.50 PEG-45 / dodecylglycol copolymer 1. 50 dime icone 0.70 magnesium sulfate 0.50 agniosium stearate 0.15 f ag nc i Example 14 Solar milk (LSF 6) up to 100 Water 10.00 mineral oil 6.00 PE6-7 - hydrogenated castor oil 5.00 isopropyl palmitate 3.50 meto? I inamata de 0.5-10 actyl compound No. 1 of table 2 3.00 caprilic / capric triglycerides 3.00 jojoba oil 2.00 copolymer PEG-45 / dope ilgl icol "7 í.? (1 fat 'iem ^> j (i- •> i?.? O,, -', 0 is fa -ito d ^ =?> Jn sio 0.50 ai the ti.i de fo fucil 5 0.25 me i 1 paraben 0.15 propilp abeno 0.05 tocopherol Example 15 Solar milk (LSF 6) io up to 100 Water 10.00 oil and mineral 6. 0 PET-7 - hydrogenated hydric acid . 00 isopropyl palmitate 3.50 meto :, octylamine icinama 15 0.5-10 compound No. 24 of table 2 3.00 caprylic / capric triglyceride 3.00 jojoba oil 2.00 copoll ero PEG-45 / dodecylglol 0.70 magnesium sulfate? O 0.60 magnesium stearate 0.50 tocopheryl acetate 0.30 glycerin 0.25 methylparaben 0.15 pro ilparaben! 5 0.05 tocopherol E jem lo 1 st solar resistance resistant to water up to 100 Agu 8.00 methox ic ina tio de oc t i.1o 5.00 PEC3-7 - castor oil hydrogenated . 00 propyl ngli ol 4.00 isopropyl palmitate 4.00 triglyceride capr í 1 ica / eaprico 0. 5-10 compound No. 17 of Table 2 05-10 Compound No. 24 of Table 2 4. 00 gl. iceriña 3.00 jojoba oil 2.00 camphor de 4-met i Ibenc: i 1 idena 2. 00 Iodium dioxide 1.50 copolymer PEG-45 / clodec and Igl icol 1. 50 dimethicone 0.70 magnesium sulfate 0.50 magnesium stearate 0.15 fragrance Example 17 Solar milk up to 100 Water 10.00 mineral oil 6.00 PE6-7 - hydrogenated castor oil 5.00 isopropyl palmitate -, r < Methodology of Oc: 1 or -10 Response No. 17 of Table 2 O Tri 1 i C ovi e C h io r / Y o p e r o p e r o p e e tio n o P a ectio n PEG-45 / dodec Igl. icol 0 magnesium sulfate 0 magnesium stearate 0 tocopheryl acetate 0 gl icer ina 5 me i Iparaben 5 p opi 1p abeno 5 tocopherol

Claims (13)

1. CLAIMS 1. The use of compounds of the same type I where the double bond C = C is in the E or Z configuration, the variables have the following meanings, Rl represents C00R5, C0R5, C0NR5R6, CN, 0 = S (-R5) = 0, 0 = 8 (. -OR5) = 0, R70-P < -0R8) = 0f R2 represents C00R6, C0R6, C0NR5R6, CN, 0 = S (-R6) = 0, 0 = 8 < -0R6 > = 0, R70-P (-OR8) = 0 | R3 represents hydrogen, an aliphatic, cycloaliphatic, araliphatic or aromatic radical optionally substituted with up to 18 carbon atoms; R 4 represents an aromatic or heteroaromatic radical optionally substituted by 5 to 12 ring atoms; R 5 bis R 8 independently represents hydrogen, a cyclic, ifatic, araliphatic, open-chain or branched aliphatic radical or an aromatic radical optionally substituted with up to 18 carbon atoms, where the variables R ^ to P.8 include, each Once together with the carbon atoms where they are attached, they can together form a ring of 5 or 6 atoms that can eventually have additional rings, i-uii fiii.ro-, i-nu rri > 1 i -ic i ions UV in f "? - '(? - HI ions (>? -. Mé LJ i as and fa rm =» cient ira - > for the protection of human skin or hair human against colloidal radiations, either alone or together with prepared pharmaceutical and cosmetic products, in compounds that absorb the keys within the range of UV radiation 2. The use of compounds of the formula I of according to the rei indication 1 co or filters against UV-A 3. The use of compounds of the formula I according to claim 1, wherein R3 represents hydrogen, R1 represents CN, C00R5 and CGP5 and R2 represents CN, C00R6 and C0R6, where R5 and R? I depend between them refer to straight chain or branched aliphatic compounds or optionally substituted aromatic radicals with up to 8 carbon atoms. Formula I according to claim 1, wherein P4 optionally represents phenyl substituted by hydrafyl substituents lieos or 1 ipof í 1 icos. 5. The use of compounds of the formula I according to claim 1 wherein R4 represents an alkoxyphenyl or alkoxycarbsil phenyl radical. 6. The use of compounds of the formula I according to claim 1 wherein R4 represents a phenyl radical carrying substituents that facilitate the solution in water, chosen from the group consisting of rad i a 1 * -. carbo ilato, su.1. fona to bien amoni. 7. Cosmetic and pharmacological treatments that protect against light, protect human and human hair against UV light within a range of 280 to 400 nm, characterized in that they contain in a suitable cosmetic and pharmaceutical vehicle, alone or together with cosmetic and pharmaceutical preparations known per se in UV absorbing compounds, effective amounts of compounds of the formula I or photostable UV filters, wherein the variables have the meaning indicated in the rei indication 1. 8. Light protection agent according to claim 7 which contains co or filters against UV-A compounds of the formula I wherein R3 represents hydrogen, R1 represents CN, C00R5 and C0R5 and R2 represents CN, C00R6 and C0R6, where R5 and R6 mean aliphatic or aromatic radicals optionally substituted with up to 8 carbon atoms. 9. Light protection agent according to claim 7, which contains as a filter against UV-A compounds of the formula I, wherein R4 represents phenyl 7: su-tHuido by sust i tuyerd es -v 'ua 1 mente h i dro f i 1 i > : Obin 1 i pof í 1 js "10. Protection agent against the nr according to claim 7, which has as a UV-A filter compounds of the formula I, where R 3 represents hydrogen, R 1 represents CN , C00R5 and COR5 and R2 represent CN, C00R6 and C0R6, and where R4 represents a phenyl radical, which may be substituted by means of alkyl, alkoxy, alkylaminocarboni or, alkoxycarboni radicals, each with up to 20 carbon atoms, either with cyano or carboxy radicals, as well as with substitutes that facilitate the solution in water, chosen from the group consisting of carboxylate, sulfonate or alkylammonium radicals. 11. Novel compounds of formula II, wherein the CC double bond is in the E or 7 configuration and where X represents a Ciapo or C0CH3 radical, P4 represents a phenyl radical, which, when X = CN, may be replaced by one or more alkyl radicals, alco; < i, alkylaminocarboni, alkoxycarbonyl, each having up to 20 carbon atoms, either cyano or carboxy radicals, as well as substituents that facilitate the solution in water, chosen from the y γup that > on j-ite > him nJi. l carboxylate, »ul fonato a hien a 1 n .1 - < a? or, or tan-n, ua or - C0CH3, can stat 5- = > inked by one or v? o = > lcoxi taclicales with up to 20 arbono or in ional branches alca, < i arbom lo > ~ of? 4 to 20 carbon atoms, as well as substituents that facilitate the solution in water, chosen from the group consisting of carboxylate, sulfonate or alkylammonium radicals, and R5, when X = CN, represents a CCH3 radical ) 3 or, when X = C0CH3, represents an alkyl, alkoxy, or alkoxyalkyl group branched or open chain, each with up to 18 carbon atoms to an aryloxy group. 12. Compounds of formula T for use as a drug. 13. PHARMACEUTICAL PREPARATION CHARACTERIZED IN THAT it contains an effective amount of at least one of the compounds of formula I in accordance with claim 1. SUMMARY OF THE INVENTION The comlesue spirit of the formula I where the double bond C = C is found in the E or Z configuration, the variables have the following meanings: P.l represents C00R5, C0R. , C0NP5R6, CN, 0 = S < -R5) = G, 0 = S < -OR5) = 0, R70 ~ Pí-0RB > = 0; R2 represents C00R6, C0R6, C0NR5R6, CN, 0 = S (-R6) = 0, 0 = S < -ORó) = 0, R70 ~ P < -0R8) = 0; R3 represents hydrogen, an aliphatic, cyclic, ifatic, araliphatic or aromatic radical optionally substituted with up to 18 carbon atoms; R4 represents an aromatic or heteroarytic radical optionally substituted with 5 a. 12 ring atoms; R 5 bis R 8 independently represents hydrogen, a cycloaliphatic radical, aral phallic radical, aliphatic radical having an open or branched chain, or a radical. aromatic optionally substituted with up to 18 carbon atoms, where the variables R3 to R8 between them, each time together with the carbon atoms where they are attached, can together form a ring of 5 or 6 atoms that can eventually have rings additional, such as rad filters > UV ions in pre aran i o < < • - »= - r? - > r. i is and f r acéu ica-;, for the olei ion of 1 JipiH skin or of the human against solar radiation, alone or together with pre arciones f =? \ macéu 1 •. a - .. and ethics • unoi t a-n, a compound that absorbs I n? -n within the range d *.? UV radiation.