Biphenyl compounds substituted by camphor or hydantoin...

Details Biphenyl compounds substituted by camphor or hydantoin... Biphenyl compounds substituted by camphor or hydantoin...

2001-03-29

2002-05-07

Richter, Johann (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Oxygen containing

C568S318000, C568S326000, C568S330000, C568S333000, C568S339000, C548S301700, C548S312100, C424S059000, C424S060000

Reexamination Certificate

active

06384284

ABSTRACT:

The present invention relates to diphenyl compounds, to a process for their preparation and to their use as light stabilisers.
Benzylidene camphors and their use as sunscreens in cosmetics are known, for example, from EP-A-0,693,471 and EP-A-0,370,867.
Surprisingly, it has now been found that reaction products of diphenylbisaldehyde and camphor and hydantoin compounds have pronounced photostability.
Accordingly, this invention relates to diphenyl compounds of formula
wherein
R is a camphor or hydantoin derivative; and
R
1
is hydrogen; or C
1
-C
5
alkyl.
C
1
-C
5
Alkyl is straight-chain or branched alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl or tert-amyl.
Preferred diphenyl compounds are those of formula (1), wherein
R is a radical of formulae
In these formulae
Y
+
is hydrogen; alkali metal; alkaline earth metal, ½ Zn
2+
, {fraction (1/3 +L )} Al
3+
, {fraction (1/2 )} Ba
2+
,
 and
R
2
, R
3
and R
4
are each independently of one another hydrogen; C
1
-C
5
alkyl or hydroxy-C
1
-C
5
alkyl.
Particularly preferred compounds are those of formula
wherein
R
1
is hydrogen; or C
1
-C
5
alkyl; and
Y
+
has the meaning given in formula (1).
The compounds of formula (1) are obtained, for example, by reacting a diphenylbisaldehyde of formula
wherein
R
1
has the meaning given in formula (1), in the presence of a base or a Lewis acid with the corresponding camphor or hydantoin derivative.
The reaction is usually carried out in an inert diluent, preferably in a protic solvent, in particular an alcohol, such as methanol, ethanol, isopropanol or tert-butanol, or in an aprotic solvent, such as diethyl ether, toluene or cyclohexane, or in mixtures of the cited solvents.
The base is preferably an alkali alcoholate, such as sodium methylate, sodium ethylate or potassium tert-butylate.
The reaction can be carried out in the temperature range from 0° C. to the boiling point of the reaction mixture, the preferred reaction temperature being in the range from 25 to 60° C.
As a rule, about 0.8 to 1.2 mol of the camphor or hydantoin derivative, based on 1 mol of the compound of formula (1), is used.
The camphor or hydantoin derivatives used as starting compounds are known compounds which are commercially available.
The process for the preparation of the compounds of formula (1) is another subject matter of this invention.
The compounds of formula (1) are particularly suitable as UV filters, i.e. for protecting ultraviolet-sensitive organic materials, especially human and animal skin and hair, from the harmful effect of UV radiation. These compounds are therefore suitable as light stabilisers in cosmetic, pharmaceutical and veterinary formulations. The compounds can be used both in dissolved and in micronised state.
In another of its aspects, this invention relates to a cosmetic formulation comprising a compound of formula (1).
For cosmetic application, these light stabilisers—unless they are water-soluble—usually have an average particle size in the range from 0.02 to 2, preferably from 0.05 to 1.5, particularly preferably from 0.1 to 1.0 nm. The insoluble light stabilisers of this invention can be brought to the desired particle size by conventional methods, for example by grinding using e.g. a nozzle mill, ball mill, vibratory or hammer mill. Grinding is preferably carried out in the presence of 0.1 to 30, preferably of 0.5 to 15% by weight, based on the UV absorber, of a grinding aid, for example a vinyl pyrrolidone polymer, a vinyl pyrrolidone-vinyl acetate copolymer, an acylglutamate, an alkylpolyglucoside or, preferably, a phospholipid.
The light stabilisers can also be used dry in powder form. To this purpose, the light stabilisers are subjected to known grinding processes, such as vacuum atomisation, counter-current spray drying and the like. These powders have a particle size of 0.1 nm to 2 &mgr;m. In order to avoid agglomeration processes, the light stabilisers can be coated prior to the pulverisation process with a surfactant, for example with an anionic, nonionic or amphoteric surfactant, e.g. phospholipids or known polymers, such as PVP, acrylates etc.
Besides the novel UV absorber, the cosmetic formulation can also contain one or several UV protectives of the following substance classes.
1. p-Aminobenzoic acid derivatives, such as 4-dimethylaminobenzoic acid-2-ethylhexyl ester;
2. Salicylic acid derivatives, such as salicylic acid-2-ethylhexyl ester;
3. Benzophenone derivatives, such as 2-hydroxy-4-methoxybenzophenone and its 5-sulfonic acid derivative;
4. Dibenzoylmethane derivatives, such as 1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)-propane-1,3-dione;
5. Diphenylacrylates, such as 2-ethylhexyl-2-cyano-3,3-diphenylacrylate and 3-(benzofuranyl)-2-cyanoacrylate;
6. 3-imidazol-4-yl-acrylic acid and 3-imidazol-4-yl-acrylate;
7. Benzofuran derivatives, in particular 2-(p-aminophenyl)benzofuran derivatives, described in EP-A-582,189, U.S. Pat. Nos. 5,338,539, 5,518,713 and EP-A-613,893;
8. Polymeric UV absorbers, such as the benzylidenemalonate derivatives described, inter alia, in EP-A-709,080;
9. Cinnamic acid derivatives, such as the 4-methoxycinnamic acid-2-ethylhexyl ester or isoamyl esters or cinnamic acid derivatives disclosed, inter alia, in U.S. Pat. No. 5,601,811 and WO 97/00851;
10. Camphor derivatives, such as 3-(4′-methyl)benzylidenebornan-2-one, 3-benzylidenebornan-2-one, N-[2(and 4)-2-oxyborn-3-ylidenemethyl)benzyl]acrylamide polymer, 3-(4′-trimethyl ammonium)benzylidenebornan-2-one methylsulfate, 3,3′-(1,4-phenylenedime-thine)bis(7,7-dimethyl-2-oxo-bicyclo-[2.2.1]heptane-1-methanesulfonic acid) and its salts, 3-(4′-sulfo)benzylidenebornan-2-one and its salts;
11. Trianilino-s-triazine derivatives, such as 2,4,6-trianiline-(p-carbo-2′-ethyl-1′-oxi)-1,3,5-triazine and the UV absorbers disclosed in U.S. Pat. No. 5,332,568, EP-A-517,104, EP-A-507,691, WO 93/17002 and EP-A-570,838;
12. 2-Hydroxyphenylbenzotriazole derivatives;
13. 2-Phenylbenzimidazole-5-sulfonic acid and their salts;
14. Menthyl-o-aminobenzoate;
15. Inorganic micropigments, such as TiO
2
(differently coated);
16. N-substituted benzimidazoles, such as described in EP-A-0,843,995;
17. Hydroxyphenylbenzotriazoles and their derivatives, in particular siloxane derivatives;
18. Siloxanes of oxanilide derivatives, such as described in EP-A-0,712,856.
It is also possible to use the UV absorbers described in “Sunscreens”, Eds. N. J. Lowe, N. A. Shaath, Marcel Dekker, Inc., New York and Basel or in Cosmetics & Toiletries (107), 50ff (1992) as additional UV protectives in the formulation of this invention.
The novel cosmetic formulation can furthermore also be used together with known anti-oxidants, for example amino acids (e.g. glycerol, histidine, tyrosine, tryptophane) and their derivatives, peptides (e.g. carnosine) and their derivatives, vitamin E or vitamin A and their derivatives, derivatives of vitamin C, carotinoids, flavanoids and their derivatives and ubiquinones or HALS (=hindered amine light stabiliser) compounds.
The cosmetic formulations contain 0.1 to 15% by weight, preferably 0.5 to 10% by weight, based on the total weight of the formulation, of a light stabiliser of formula (1) or of a mixture of light stabilisers and a cosmetically compatible auxiliary.
The cosmetic formulations may be prepared by physically mixing the UV absorber(s) with the auxiliary by standard methods, for example by simply stirring the individual components together, preferably by exploiting the solubility characteristics of known cosmetic UV absorbers, such as OMC, isooctyl salicylate and others.
The cosmetic formulations can be formulated as water-in-oil or oil-in-water emulsion, as oil-in-alcohol lotion, as vesicular dispersion of a ionic or nonionic amphiphilic lipid, as gel, solid stick or as aerosol formulation.
As water-in-oil or oil-in-water emulsion, the cosmetically compatible auxiliary preferably comprises 5 to 50% of an oil phase, 5 to 20% of an emulsifie

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