Oligomeric diarylbutadienes

Details Oligomeric diarylbutadienes Oligomeric diarylbutadienes

1999-12-06

2002-08-20

Dees, Jose′ G. (Department: 1616)

Drug, bio-affecting and body treating compositions

Topical sun or radiation screening, or tanning preparations

C424S401000, C558S308000, C560S001000

Reexamination Certificate

active

06436373

ABSTRACT:

The present invention relates to novel oligomeric 4,4-diarylbutadienecarboxylates and -carboxamides and their use as sunscreens and also to a process for their preparation.
The sunscreens employed in cosmetic and pharmaceutical preparations have the task of preventing, or at least diminishing the consequences of, harmful effects of sunlight on the human skin. However, these sunscreens also serve to protect other ingredients from decomposition or breakdown by UV radiation. In hair cosmetic formulations the aim is to reduce damage to the keratin fibers by UV rays.
The sunlight reaching the surface of the earth contains UV-B radiation (280 to 320 nm) and UV-A radiation (>320 nm), which are directly adjacent to the visible light region. The effect on the human skin is manifested, particularly in the case of UV-B radiation, by sunburn. Accordingly, the industry offers a relatively large number of substances which absorb UV-B radiation and thus prevent sunburn.
Dermatological investigations have now shown that UV-A radiation is also perfectly capable of causing skin damage and allergies by, for example, damaging the keratin or elastin. This reduces the elasticity and water storage capacity of the skin, i.e. the skin becomes less supple and tends to form wrinkles. The noticeably high incidence of skin cancer in regions where the sun's radiation is strong shows that damage to the genetic information in the cells is evidently also caused by sunlight, specifically by UV-A radiation. All these findings therefore make it appear necessary to develop efficient filter substances for the UV-A region.
There is a growing demand for sunscreens for cosmetic and pharmaceutical preparations which can be used in particular as UV-A filters and whose absorption maxima ought therefore to be in the range from about 320 to 380 nm. In order to achieve the required effect by using the minimum amount, sunscreens of this type ought additionally to have a highly specific absorbance. Sunscreens for cosmetic preparations must also meet a large number of other requirements, for example good solubility in cosmetic oils, high stability of the emulsions produced with them, toxicological acceptability, and slight intrinsic odor and slight intrinsic color.
Another requirement which sunscreens must meet is adequate photostability. However, this is only inadequately ensured, if at all, with the UV-A-absorbing sunscreens hitherto available.
French Patent No. 2 440 933 describes 4-(1,1-dimethylethyl)-4′-methoxydibenzoylmethane as a UV-A filter. It is proposed to combine this specific UV-A filter, which is sold by GIVAUDAN under the name “PARSOL 1789”, with various UV-B filters in order to absorb all UV rays having a wavelength from 280 to 380 nm.
However, this UV-A filter does not have sufficient photochemical stability, when used alone or in combination with UV-B filters, to ensure sustained protection of the skin during sunbathing for prolonged periods, which means that repeated applications at regular and frequent intervals are required if effective protection of the skin from all UV rays is desired.
For this reason, EP-A-0 514 491 discloses the stabilization of the insufficiently photostable UV-A filters by adding 2-cyano-3,3-diphenylacrylic esters which themselves act as filters in the UV-B region.
It has furthermore already been proposed in EP-A-0 251 398 to combine chromophores absorbing UV-A radiation and UV-B radiation into one molecule by using a linker. This has the disadvantage that, firstly a free combination of UV-A and UV-B filters in the cosmetic preparation is no longer possible, and that difficulties in the chemical linkage of the chromophores allow only certain combinations.
U.S. Pat. No. 4,950,467 describes the use of 2,4-pentadienoic acid derivatives as UV absorbers in cosmetic preparations. The monoaryl-substituted compounds specified as being preferred in this patent also have the disadvantage that they have inadequate photostability.
It is an object of the present invention to propose sunscreens for cosmetic and pharmaceutical purposes which absorb in the UV-A region with high absorbance, are photostable, have a low intrinsic coloration, i.e. a sharp band structure, and, depending on the substituents, are soluble in oil or water.
The object was essentially achieved in the previously unpublished DE-A 19755649 (O.Z. 48641) with monomeric 4,4-diarylbutadienes which are functionalized in the 1-position, with the limitation that the object still existed to find sunscreens which, in addition to said properties, have low skin penetration.
We have found that this object is achieved according to the invention with novel oligomeric 4,4-diarylbutadienecarboxylates or -carboxamides of the formula I
in which
R
1
and R
2
independently of one another are hydrogen, an aliphatic, cycloaliphatic, aromatic, araliphatic or heterocyclic radical or substituents which confer solubility in water, chosen from the group consisting of carboxylate, sulfonate or ammonium radicals;
R
3
is an aliphatic, cycloaliphatic, aromatic, araliphatic or heterocyclic radical or a radical which is bonded by a carbonyl, sulfonyl or a phosphonyl group, or is a carboxylate or a cyano group;
Y is the group
in which
R
4
is hydrogen, an aliphatic, cycloaliphatic, aromatic, araliphatic or heterocyclic radical and
m is from 2 to 10,
n is from 1 to 3, and
x is the m-valent radical of a polyol having from 2 to 10 hydroxyl groups.
In particular, the variables are defined as follows:
R
1
and R
2
are hydrogen, C
1
-C
20
-alkyl, C
2
-C
10
-alkenyl, C
3
-C
10
-cycloalkyl, C
3
-C
10
-cycloalkenyl, C
1
-C
12
-alkoxy, C
1
-C
20
-alkoxycarbonyl, C
1
-C
12
-alkylamino, C
1
-C
12
-dialkylamino, aryl, heteroaryl, optionally substituted, substituents which confer solubility in water, chosen from the group consisting of carboxylate, sulfonate or ammonium radicals;
R
3
is hydrogen, COOR
5
, COR
5
, CONR
5
R
6
, CN, O═S(—R
5
)═O, O═S(—OR
5
)═O, R
7
O—P(—OR
8
)═O, C
1
-C
20
-alkyl, C
2
-C
10
-alkenyl, C
3
-C
10
-cycloalkyl, C
7
-C
10
-bicycloalkyl, C
3
-C
10
-cycloalkenyl, C
7
-C
10
-bicycloalkenyl, aryl, heteroaryl, optionally substituted;
R
4
to R
8
are hydrogen, C
1
-C
20
-alkyl, C
2
-C
10
-alkenyl, C
3
-C
10
-cycloalkyl, C
7
-C
10
-bicycloalkyl, C
3
-C
10
-cycloalkenyl, C
7
-C
10
-bicycloalkenyl, aryl, heteroaryl, each optionally substituted;
it being possible for the variables R
5
to R
8
to form with each other, in each case together with the atoms to which they are bonded, a common 5- or 6-membered ring.
Alkyl radicals R
1
to R
8
which may be mentioned are branched or unbranched C
1
-C
20
-alkyl chains, preferably methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl or n-eicosyl.
Alkenyl radicals R
1
to R
8
which may be mentioned are branched or unbranched C
2
-C
10
-alkenyl chains, preferably vinyl, propenyl, isopropenyl, 1-butenyl, 2-butenyl, 1-pentenyl, 2-pentenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 3-methyl-1-butenyl, 1-hexenyl, 2-hexenyl, 1-heptenyl, 2-heptenyl, 1-octenyl or 2-octenyl.
Cycloalkyl radicals which may be mentioned for R
1
to R
8
are preferably branched or unbranched C
3
-C
10
-cycloalkyl chains, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, 1-methylcyclopropyl, 1-ethylcyclopropyl, 1-propylcyclopropyl, 1-butylcyclopropyl, 1-pentylcyclopropyl, 1-methyl-l-butylcyclopropyl, 1,2-dimethylcyclopropyl, 1-methyl-2-ethylcyclopropyl, cyclooct

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