DE1492274A1 - Cosmetic creams and lotions for topical use and processes for the preparation of new compounds that can be used as protective substances against ultraviolet rays - Google Patents

Description

Cosmetic creams and lotions for topical use and processes for the preparation of novel compounds useful as anti-ultraviolet ray anti-ultraviolet ray compounds

It is known that normal-skinned people are exposed to ultraviolet rays, which correspond to a wavelength of about 280 or 290 m / u to about 320 m / u, slightly in undesirable y / eiae are influenced. This relatively limited radiation area is responsible for that Damage that normal-fair-skinned people can suffer when their skin is exposed to strong or long-term exposure expose to sunlight. The ultraviolet rays with longer wavelengths up to about 400 or 420 m / rev, on the other hand, cause the tanning of the skin aesthetically desirable, while in contrast the reddish one caused by the first mentioned rays Discoloration is undesirable.

With this in mind, cosmetic preparations have already been made, which are usually in the form of creams and lotions and are used locally and whose purpose is to leave a film or precipitate on the surface of the skin after application, which contains a protective substance, through which at least the greater part of those rays are absorbed which have a wavelength of about 290-320 m Ai , while the protective material, on the other hand, should let through the essential part of the rays which have a wavelength above 320 m / u.

'Cosmic preparations of the kind mentioned for many years Individuals who are well suited to lead them at certain Personal circles do not lead to the desired success, v / eil the effect of sun rays on these persons runs abnormally. This is especially true for people who suffer from certain diseases, e.g. photophobia,

ORIGINAL BATH 909845/162 8

or both types of dermatitis. In these individuals often occur unwanted films not only in economic V / range of 290-320 m / u, but also upon irradiation with V / Ellen of more than 320 m .u up to 400 or even 420 m

u e.uf. The usual sunscreen ointments work for people of this type not to the desired success, since the previous preparations aimed at filtering out the lower The range of ultraviolet rays are limited.

One object of the present invention is to produce cosmetic preparations which also give adequate protection to those persons who are also sensitive to exposure to ultraviolet rays with a wavelength above 320 m / rev. A further object of the present invention is to produce new products which are suitable as all protective substances in the sense of the object.

The invention initially relates to cosmetic creams and lotions for topical use containing a dermatologically acceptable liquid or semi-liquid Carrier and dissolved or dispersed therein a dermatologically compatible iiehutzstoff of the general formula I

H.

X)

COY

-CH = C

wherein W is hydrogen or a COZ group; Y and Z, which can be the same or different, for an alkyl group, an OH ^ group, in which IU is hydrogen, denotes an alkyl or an alkoxy-alkyl group, or an OB group, in which B is a derinatologically compatible cationic group, stand; and

R.J unu Rg, which can be the same or different, for 7 / hydrogen, an alkyl or aralkyl group or together for an alkylene group with straight or

909845 / me

- 3 - ORIGINAL BATHROOM

branched, possibly by a hetero atom broken chain.

For example, R ₁ and / or H _{0 can} each stand for a benzyl group or together for a pyrrolidine, piperidine, urorpholine or piperazine group. H-, for example, can represent a methyl, ethyl, n-propyl or isobutyl group. Suitable alkoxyalkyl groups include, for example, the ethoxypropyl, ethoxyethyl, n-butoxyethyl and ethoxy-butyl groups. Suitable cationic groups of the alkali metals such as sodium or potassium, which are, for example Aminoniumgruppe UNU appropriately substituted Jeli.e ammonium üruppen as the 'j? Rishydroxyäthylammonium group.

According to a preferred embodiment, the preparation according to the invention should be dermatologically compatible Contain protective substance of the general formula II

-CH = CH-COOK ₄ II

where R ₁ and H «have the same meaning as in formula I and H- stands for an alkyl group with 1-4 C atoms.

The protective ointments that have a particularly good effect contain a protective agent of the general formula II, in the r-, ilp and ii. ötehen for alkyl groups with 1-4 carbon atoms. Examples of such groups are the methyl, ethyl, n-propyl and n-3utyl groups. The Diallerlaiaino Group is in place zv / eok in the p-position of the benzene ring.

Have a particularly good effect in the context of the invention The substances of the general formula III

909845/1828 _

-CH = CH-COOiI ₄ III

where R ₁ , Rp and H ,, which can be the same or different, each represent an alkyl group with 1-4 C atoms. Those substances of the above formula in which R ₁ and R ₂ stand for methyl or ethyl and R for ethyl or butyl have the best effect.

An example of the compounds of the general formula III is isobutyl-p-methylamino-cinnamic acid ester.

If W in the general formula I stands for a COZ group, the preferred group corresponds to these compounds of the general formula V

where R ₁ and R ₂ , which can be the same or different, each represent an alkyl group with 1-4 and advantageously with 1-2 carbon atoms ^ and the two R ~, which can be identical or different, each represent an alkyl group with 1 -4 and expediently mean with 1-2 carbon atoms. A compound of this type is the diethyl ether of r-dimethyl-aminobenzalmalonic acid.

The substituted malonic acid esters according to the invention can be prepared by condensing a suitably substituted amxnobenzaldehyde with a suitable ester of alonic acid. This can for example be done by uie from _B angsprodukte v / as zv / eckmäßi ^ reflux and Jüinschaltung be heated, an apparatus for d ... a separator ces Re-

909845/162

BATH ORIGINAL

action water takes place.

The condensation is advantageously carried out in solution using a solvent which is effective for both substances and in the presence a condenation catalyst, for example piperidine, carried out. Jenn the desired end product an acid or is a salt, the initially formed ester can be hydrolyzed under alkaline conditions and careful work. The acid so obtained can be isolated as such or neutralized with the appropriate base to form a salt. Ueiin the desired end product ent a primary amino group holds (i.e. R. and Rp stand for hydrogen), this group must be protected during the condensation by introducing a protective group, e.g. an acetyl residue. The protective one Groups are removed again in a suitable manner at the end of the reaction will.

The substituted cinnamic acid esters used according to the invention v / he intended can be prepared by combining a suitable aminobenzaldehyde with a suitable ester of acetic acid is condensed. This is conveniently done using a mutual solvent such as a Excess of the ester can be used. Furthermore, the Use of a corrosion catalyst, for example sodium metal or sodium hydride, appropriate. If the desired end product is an acid, the ester initially obtained can hydrolyzed v / earth. Products of this type are technically grounded advantageously prepared by the corresponding alinobenzaldehyde with malonic acid in a mutual solvent is condensed in the presence of a condensation catalyst, for example piperidine. Λ / enn the desired end product is a salt, ks.nn the salt by neutralizing the acid using a suitable base. V / enn the desired End product containing a primary amino group, muli the group be protected during the condensation by introducing a protective agent, e.g. the acetyl group. This can be removed again in a suitable manner at the end of the reaction.

As far as is known so far, the substances to be used according to the invention (with the exception of 3 compounds) New. In view of this, the invention not only encompasses

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_ 6 «.BAD ORIGINAL

the use of the aforementioned substances as protective substances, but also the manufacture of the high-quality fabrics, insofar as these are still new, is another subject matter of the patent thus the process of dividing the new ones, as protective substances Compounds of the general formula VI which can be used against ultraviolet rays

VI

in which W stands for hydrogen or the group -COZ, Y and Z, which can be identical or different, for an alkyl group, for an OIU group, in which R, hydrogen, an alkyl group or an alkoxyalkyl group represents, or represents an OB group in which B represents a dermatologically acceptable cationic group; R ₁ and Rp, which can be identical or different, represent hydrogen, an alkylene group or an aralkyl group or together represent an alkylene group with a straight or branched chain, optionally interrupted by a hetero atom; and the values for V /, Y, Z, R ^ and Rp are chosen such that in cases in which the phenyl radical in the p-position is substituted by a dimethylamino group, Y is not a hydroxyl group if \ 7 for Is hydrogen, and Y is not an ethoxy group when M is hydrogen or a carbethoxy group,

which is characterized in that an _{aminobenzaldehyde substituted in the amino group by R 1} and H ₂ and optionally protected with respect to the subsequent condensation with a compound of the general formula VII

CH ₅ -CO-Y VII

where Y has the same meaning as in formula VI,

90Sft4S / 1Of

or uit a connection of the formula VIII

CH ₀ -CO-Y

I ^ά viii

CO -Z

where Y and Z have the same meaning as in formula VI,

condensed in the presence of a condensation agent and if necessary, the protective group is removed from the product obtained in this way and / or the starting groups ϊ and / or Z can optionally be converted into other groups Y and / or Z.

The cosmetic preparations for the purposes of the invention include cosmetic oils, alcoholic solutions, lotions, lipsticks, Jalben, creams and other emulsified products. in the general can be used for making the cosmetic Preparations Raw materials of the usual kind are used, but they must match the protective substances used in each case compatible i-a.

Depending on the desired protective effect and the additives used, satisfactory results can be obtained with the preparations that are free of use in an amount of about. 0.5 to 10 '/> (calculated aui the evicLt of the formulation) contained. Preferably all of the protective substances should run between 1 and 3; however, the use of larger hens is generally not acceptable. The optimal level of the protective substance used in EinEeli'all zi depends, among other things, on the nature of the protective coating remaining on the skin, since some recipes have a greater concentration of the .jchutΕ; = toffee per unit of the to be protected Allow area old; joidere. Influencing factors are, for example, the viscosity, the Ausbreitun _o ISVE: riüögen and the resistance per animal ^i. Eils formed bc: ot.

The organic preparations according to the rHnUUn ₁ ; are not for: - tiELate classes of cosmetic ingredients or

909845 / 162f -s-

BATH ORIGINAL

limited to certain recipes. In general, however, it is desirable to use the protective substances according to the invention to use with a larger amount of a dermatologically acceptable carrier. As such, e.g. Consider: corn oil, aqueous ethanol, isopropanol, sesame oil, Propylene glycol, benzyl alcohol, oleyl alcohol, isopropyl ester of fatty acids, e.g. myristic or palmitic acids, mineral oils and waxes. The carriers used should have such a viscosity and / or wetting power that the preparation, even if it is a 'Has an oily character, properly applied to the skin as a continuous film or coating can be.

The new preparations can be applied to the skin in the usual way. In general, the application should be carried out before the person using the preparation is exposed to the sun's rays.

According to a preferred embodiment of the present invention, in addition to the already developed protective substance of the general formula I, at least one other, dermatologically compatible, ultraviolet-resistant absorbent protective substance is added to the cosmetic preparations, which has an absorbent substance iet that it is able to supplement and / or strengthen the protection of the compound of the formula I. Expediently, the effect of the second protective substance should be complementary to the first protective substance, so that the range of the absorbed wavelength is increased and / or the strength of the absorption is increased. Preferably to the compound of For _"-r;. El I r their i / ^ le .uxim absorption Beiu ultraviolet light;. It exert a wavelength between 320 UNU 4CO m / U, while the second protective substances a maximum absorption at a wavelength of 290 - 320 m / rev.

The. Preparations according to this special embodiment Le? , Invention can cie two protective substances in such

909845/1621 -

Amounts contain that they together 0.5 - 10 # (bereohf ^. * Net on the Cfewioht of the preparation) and appropriate 0.9-5 'Ji. The molar ratio of the two 3ohuteetofie Äueinandar can be between 1s10 to 10 | 1, ^ί beforeBixgeweiee asohen 5: 1 to 1i5 and optimally at 2t 1 bi 1 * 2

;; It is necessary that the two protective substances and the ratio in which the two protective substances are used are selected in such a way that a 2.5% solution of the two compounds Ratio) in a solvent that is transparent to ultraviolet rays (for example in ethanol) "in a layer thickness of 1 cm should reduce the intensity of all rays with wavelengths between 290 and 40 Ω m. / Rev by at least 90 i" :

Examples of protective substances in the sense of the above * ' guides can be used as a second component, j are isobutyl dimethylaminobenzoate, menthyl salicylate, Ethoxyäthyl- and other lower alkoxyalkyl esters of p-methoxy-cinnamic acid, especially those that are at least 4 and preferably 4-6 G atoms in the alkoxyalkyl group have, e.g. 2-ethoxyethyl-p-methoxy-cinnamic acid ester. in the In general, the outer sole should shine the rays erythematogeni.Bclien area absorb and so the absorption of the Sohutgstoffee, which more in the tan « area lies, complement.

The difficulty which often arises in the manufacture of preparations containing koimetic substances results from the fact that those in question are concerned Protective substances in the dermatologically compatible carrier substances are often only slightly soluble, while on the other hand A minimum requirement is required for the protective material is to achieve a sufficient protective effect. If in the context of the present invention, two different

'1 ·! · - 10 -BAD

? Γ

- 10 - *

Protective substances are used », verr ingerfc. § £ # $ Difficulty, since every Sohutaotof ^ »fine ft cold in the carrier cloth be »it» - $ and die Fabrics to cook with a <Jeia »itkon» «ntra $ ion $ let, the generally lower of those Jton »entr» tio » which lies with an eimei «·« Sohutaetoff # ** «iiffe1) er l * i, You can use swei chute materials So does niohi only lead to the fact that a denunciation g the length of the absorbed skin, but also an increase in the intensity of the absorption.

Preview of the brewers according to the invention, di not contain a few two agreements illustrated in the accompanying drawing which graphically shows the ultraviolet absorption of three highly absorbing iotlons. The ones shown in the drawing Spectra were made of smears of lung heaptures containing protective substances on silica plates without drying. The Kuirve 1 was obtained from a lotion that thißlt ϊ, 5 öew.Ji dee known Schutj2etofies 2-Äthoxyäthyl- |) -methoxy-ZiBitBäüreeßter. The curve

2 was made from a lotion containing 1 * 5 Gen. ^ one. new protective substance according to the invention, namely the isobutyl-p-dimethylajaino-cinnamon acidic acid ester. Curve

3 was made from a lotion, each 1.5 wt. £

an a-ethoxyethyl-p-eethoiy-ZlmtBaureeBter and ieobutyl-pdiiaethy?, amino-ÄlJit # ^ would be kept free. The. Curves were so hergeetelXt that the variations in the thickness of the three Spreads Reohjcm & g was worn.

The preparation of the aforementioned lotion used was as follows

Oetylalkohüi; Stearic acid] Lanolin _'s Petroleum j bactericide triethanolamine

Me ^ ge & 0.5 ε 3.0 G 0.5 G 5.0 S. 0.2 G 3.0

- 11 "

- 11 - 3 , 0 G 1492274 83 , 3 G Glycerin \ 7asser Distilled

The preparations according to the invention can be advantageous can also be used by people who love the ',' 'ung, not to tan despite exposure to the sun. In dieeem Sense k; in which the invention can be used in such cases, in which the extent of the clothing changes from time to time and the w'unscii konstx, ικ-ch on the outside not to show the extent to which the Body on an earlier occasion under tanning conditions clothed ooier was undressed.

The invention also includes concentrated substance mixtures which at least 2 ultraviolet absorbing compounds im For the purposes of the invention and which can be used in the manufacture of cosmetic preparations, in which they in a suitable amount of a dermctoloeich compatible, liquid or semi-liquid carriers be incorporated. These concentrates can only benefit from the protective substances as such, if they are used are mutually compatible, or they can additionally Contain diluents that are: η a part of the cosmetic Form the final preparation or can be separated before further processing. For example, can liquid diluents are evaporated.

The expression "dermatologically tolerable" is intended to indicate in the sense of the present invention that the substance in question is not only useful in dermatological terms in the narrower sense, but that it also corresponds to other physiological aspects if, for example, de: * comes under consideration diirch .e fabric skin aoyorbiert and v.ird introduced into the bloodstream, he is in!, learn, and on the way to de- ^1, he absorciert v / ill not be toxic.

909845/1621

The following examples 1-6 show the production of protective substances which can be used according to the invention; Examples 7-10 ^ ei _o en producing vcn leonine tables preparations according to the invention.

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Example 1; Diethyl p-dimethylamino-benzalmalonate

A solution of p-dimethylaminobenzaldehyde (10.5 g), piperidine (1 ml), benzoic acid (0.3 g) and ethyl malonate (9.4 ml) in dry benzene (20 ml) was ^{heated under reflux at 130 140 0} C until from the Distillate no more water could be separated. A Dean & Starke phase separation apparatus connected to the reflux column was used for this. After the reaction mixture has cooled, the desired end product crystallizes out. The yield after recrystallization from aqueous ethanol was 14 g. The product forms pale yellow crystals. Έ = 111-112 ⁰ C, solubility in water (2O ⁰ C) ^ 0.1 $, max 370 m, u, molecular dissolution coefficient = 33,000.

Example 2t

p-dimethylamino-cinnamic acid

p-Dimethylaminobenzaldehyde (50 g) and malonic acid (35 g) were heated in pyridine (250 ml) and piperidine (20 ml) on the steam bath for 12 hours. The reaction mixture was then poured into a mixture of crushed ice (1 kg) and glacial acetic acid (500 ml) with stirring. The unusual one Product was separated, washed with dilute acetic acid and with water. After drying, it was recrystallized from ethanol and thereby obtain the desired end product. Yield 39 g of a yellow solid. P = 227-232 ° C (with decomposition).

Example 3? Ethyl-p-dimethylamino-cinnamic acid ester

Sodium hydride (7 g of a 50% dispersion in 01) was In portions with stirring in a cooled mixture of dimethylaminobenzaldehyde (16.7 g) and ethyl acetate (200 ml registered. The mixture was left to stand overnight.

-14-

909845/1621

Glacial acetic acid was then added and excess ethyl acetate was distilled off in vacuo. The residue was kneaded with water, filtered off, dried and recrystallized from ligroin. The final product was obtained as a yellow crystalline solid. P = 70-72 ⁰ C. Yield 12 g.

Example 4: Isobutyl-p-dimethylamino-cinnamon acid ester

Sodium hydride (33 g of a 50% dispersion in oil) was added in portions to a cooled mixture of dimethylaminobenzaldehyde (18 g) and isobutyl acetate (400 ml) with stirring! The mixture stayed overnight. Glacial acetic acid (42 g) was then added, and excess isobutyl acetate was distilled off in vacuo. The residue was kneaded with water, filtered off, dried and recrystallized from ligroin. The desired end product forms pale yellow crystals. F = 60-63 ⁰ C yield 63 g.

Found: C, 72.8 $; H, 8.6%; N, 5.6 #

C ₁₅ H ₂₁ O ₂ N calcd: C, 72.8%; H, 8.4%; N, 5.7%

Example 5:

Triethanolamine-p ^ dimethylamino-cinnamic acid ester p-Dimethylamino-cinnamic acid ester (3 «ö g) and triethanolamine (3 g) were heated together on a water bath until a uniform melt was obtained. Then the mixture is cooled. The solidified melt is recrystallized from ethyl acetate. The desired end product forms a yellow, waxy solid.
F = 129-134 ⁰ C.

Example 6: Di-isobutyl-p-dimethylamino-benzalmalonate

A solution of p-dietethylaminobenzaldehyde (10.5 g) »pyridine (1 ml), benzoic acid (0.3 g) and di-isobutyl malonate (9 x 4 g) in dry benzene (50 ml) was refluxed

909845/16 2 - ¹⁵ ^ eAD original

heated at 130-14O ⁰ C until no more water can be separated from the distillate. A Dean & Starke phase separation apparatus connected to the reflux column was used for this. The desired end product crystallizes out on cooling.
Yield (after recrystallization from ethanol) 14.8 g

Crystals.
P = 99-100 ⁰ C.

Found: C, 69.2 #; H, 8.4 #; N, 4.3%.

^C 20 ^H 29 ⁰ 4 ^{H calculated! c} » ⁶ 9.1 # i H, 8.4? t; N, $ 4.0.

Example 7:

Lotion ait strong Absorptionswirkunp for Radiation isopropyl ayristat (98 g) and diethyl-p-dimethylaminobenzalmalonat (0.5 g) were heated at 50 ⁰ C, is released to the malonate in myristate. Then 2-ethoxyethyl-pmethoxy-cinnamic acid ester (0.5 g) is added and the resulting mixture is cooled to room temperature.

Example 8:

Lotion with a strong protective effect material lot G Cetyl alcohol 0.5 G 1. Stearic acid 3.0 G 2. lanolin 5.0 G 3. mineral oil 5.0 G 4th Bactericidal agent 0.2 G 5. 2-ethoxyethyl-p-methoxy-cinnamon
acid ester. 2.0 G 6th Diethy1-p-dimethyIamino-
benzalmalonate 2.0 G 7th Triethanolamine 3.0 G 8th. Glycerin 3.0 G 9. Distilled water 83.3 10.

Substances 1-7 were mixed together and heated to y5 °. This temperature was maintained until the mixture was homogeneous. The mixture was then cooled to 70 ⁰ C.

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The substances 8-10 were heated to 7O ⁰ C and then added with stirring to the mixture of substances 1 - added. 7 Ee is stirred, is cooled until the mixture to 55 ⁰ C. The resulting mixture is left to stand overnight, the desired lotion then being formed.

Example 9: Cream with a stronger protective effect S> toff amount

1. Mineral oil 5.0 g

2. Lanolin 0.5 g

3. Polyoxyethylene lanolin derivative (Solulan 98) 3.0 g

4. Glyceryl monostearate SE
(self-emulsifying) 5.0 g

5. Stearic acid 15.0 g

6. Bactericidal agent 0.2 g

Y. 2-ethoxyethyl-p-methoxy-

Cinnamon ester 2.0 g

8. Diethyl p-dimethylaminobenzalmalonate 2.0 g

9. Propylene glycol 5.0 g 10. Distilled water 62.2 g .The materials 1-8 were homogenized with 80 ^0C. The substances 9 and 10 were heated to 80 ⁰ C and added to the mixture of the substances 1-8 at 80 ⁰ C. Here, was stirred mechanically and the mixture was then cooled to 35 ⁰ C. The product obtained was immediately packed in suitable containers.

Example 10:

Detergent with a strong protective effect material

1. Cetyl alcohol 0.5 g

2. Stearic acid 3.0 g

3. Lanolin 0.5 g

4. Mineral oil 5.0 g

5. Bactericidal agent 0.2

909845/162 * " ^1? "

.17 _ U92274

Fabric amount

6th 2-ethoxyethyl-p-methoxy-
Cinnamic acid ester 1.5 S. 7th Isobutyl-p-dimethylamino ».
Cinnamic acid ester 1.5 G 8th. Triethanolamine 3.0 G 9. - glycerin 3.0 G 10. Distilled water 81.8 ff

100.0 g

The materials 1-8 were homogenized with 80 ^0C. The 'materials 9 and 10 were heated to 80 ⁰ C and zugefügst at this temperature to the mixture of the substances 1-8. Here, was mechanically stirred and the total mixture is then cooled to 35 ⁰ C. The cream obtained was immediately filled into vessels.

In the preceding Examples 7-10, the one used in each case primary protective substance can be replaced in each case by a different compound according to the invention, wherein the replacement product has a comparable ultraviolet absorption spectrum in order to achieve a similar protective effect should have. The 2-ethoxyethyl-p-methoxy-cinnamic acid ester can be replaced in a similar way by comparable previously known protective agents.

The terms "strong protective solution or cream" used in some examples are intended to refer to it hint. that the absorption of the rays in these cases takes place not only in the area of the ultraviolet rays of the spectrum causing the burn, but also in the area that is generally considered to be the tanning area in normal fair-skinned individuals will. Otherwise, the lotions and creams described in the examples are only illustrations of the many forms in which the invention can find expression.

Claims;

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Claims (12)

Patent claims: R ₁ -N
¹ I. wherein W is hydrogen or an OOZ group; Y and Z, which can be the same or different, represent an alkyl group, an OR, group, in which R, Hydrogen, an alkyl or an alkoxy-alkyl group means, or an OB group in which B is a dermatologically acceptable cationic group means to stand; and R ₁ and R ₂ », which can be identical or different, represent hydrogen, an alkyl or aralkyl group or together represent an alkylene group with a straight or branched chain, optionally interrupted by a hetero atom. 2. Preparations according to claim 1 containing a dermatologically acceptable protective substance of the general formula II R, -N -CH = CH-COOR. II ¹ L -19-909845 / 182 « wherein R ₁ and R _{2 have} the same meaning as in formula I and R. is an alkyl group with 1-4 carbon atoms. 3. Preparations according to claim 2 containing a protective substance of the general formula II, in which R ₁ , R ₂ and R. are alkyl groups with 1-4 carbon atoms. 4. Preparations according to claim 3 containing a protective substance of the general formula II, in which R ₁ , R ₂ and R ^ are alkyl groups with 1-4 carbon atoms and the dialkylamino group in the p-position to the group -CH = CH -COOR. stands· 5. Preparations according to claim 4 containing isobutyl or ethyl-p-dimethylamino-cinnamic acid ester as protective substance. 6. Preparations according to claims 1-5 containing about 0.5-10, preferably 1-3 percent by weight of protective substances. 7 · Preparations according to claims 1-6, characterized in that, in addition to the first protective substance, they also contain at least contain a second protective substance whose ultraviolet absorbing properties are such that both Protective materials together result in an increased absorption effect. 8. Preparations according to claim 7, characterized in that the first protective substance has a maximum absorption with respect to the ultraviolet light at a wavelength of 320-400 mn and the second protective substance such at 290-320 m / u. 9. Preparations according to claims 7 and 8, characterized in that the protective substances together 0.5-10 #, calculated -20-909845 / 1620 to the total weight of the preparation. 10. Preparations according to claims 7-9 »characterized in that * that the two types of protective substances in a molar ratio from 1:10 to 10: 1 are available. 11. Preparations according to claims 7-10, characterized in that the two types of protective substances and their quantitative ratio be chosen so that a 0.5 $ solution of the protective substances in the chosen ratio in one for Ultraviolet rays in transparent solvent a layer thickness of 1 cm, the intensity of all introduced rays with wavelengths of 290-400 m / rev ψ reduced at least $ 90. 12. Process for the preparation of the new compounds which can be used as protective substances against ultraviolet rays of the general formula VI -CH = C-COY VI where W stands for hydrogen or the group -COZ, Y and Z _f ctie can be the same or different, for an alkyl group, for an OR ^ group, in which R is hydrogen, an alkyl group or an alkoxyalkyl group , or represent an OB group in which B is a dermatologically compatible cationic group; R ₁ and R ₂ , which can be identical or different, represent hydrogen, an alkyl or an aralkyl group or together represent an alkylene group with a straight or branched chain, optionally interrupted by a hetero atom; and the values 909845/162 -21- for W, Y, Z, R ₁ and R ₂ are chosen such that in cases in which the phenyl radical in the p-position is substituted by a dimethylamino group, Y is not a hydroxyl group when W is hydrogen, and Y does not mean an ethoxy group - if W stands for hydrogen or a carbethoxy group, characterized in that one in the amino group substituted by R and R «and optionally with respect to the subsequent condensation of protected aminobenzaldehyde with a compound of the general Formula VII CH ₅ -CO-Y VII where Y has the same meaning as in formula VI,
or with a compound of the formula VIII CH ₂ -CO-Y CO -Z ^Vni where Y and Z have the same meaning as in formula VI, condensed in the presence of a condensing agent and optionally the product obtained in this way protective group removed and / or the starting groups Y and / or Z optionally in other groups Y and / or Z are transferred » 909845/1621 Blank page