Organic compounds -- part of the class 532-570 series – Organic compounds – Silicon containing
Reexamination Certificate
1999-06-14
2002-07-30
Gerstl, Robert (Department: 1613)
Organic compounds -- part of the class 532-570 series
Organic compounds
Silicon containing
Reexamination Certificate
active
06426428
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Technical Field of the Invention
The present invention relates to novel topically applicable UV-photoprotective compositions containing at least one normally photolabile dibenzoylmethane UV-screening compound and, as a photostabilizer therefor, an effective amount of at least one particular benzalmalonate silane.
This invention also relates to certain novel processes for the synthesis of said particular benzalmalonate silanes.
2. Description of the Prior Art
It is known to this art that light radiation of wavelengths ranging from 280 nm to 400 nm promote tanning of the human epidermis, and that radiation of wavelengths more particularly ranging from 280 to 320 nm, i.e., UV-B irradiation, causes erythemas and skin burns which are detrimental to the development of natural bronzing and tanning. For these reasons, as well as for aesthetic reasons, there is a constant demand for means to control this natural bronzing and thus control the coloration of the skin; it is thus advisable to filter such UV-B radiation from the skin.
It is also known to this art that UV-A irradiation, of wavelengths of from 320 to 400 nm, which promotes tanning of the skin, also adversely affects it, especially in the case of a sensitive skin or of a skin which is continuously exposed to solar radiation. The UV-A rays, in particular, cause a loss in the elasticity of the skin and the appearance of wrinkles, resulting in premature cutaneous aging. UV-A radiation promotes triggering of the erythematous reaction or amplifies this reaction in certain individuals and can even be the source of phototoxic or photoallergic reactions. Thus, for aesthetic and cosmetic reasons such as the preservation of the natural elasticity of the skin, for example, more and more individuals seek to control the effect of UV-A rays on their skin. It is thus desirable to also filter out UV-A radiation.
In this respect, one class of UV-A filters of particular interest comprises the dibenzoylmethane compounds, and especially 4-tert-butyl-4′-methoxydibenzoylmethane, which indeed have a great capacity for intrinsic absorption. These dibenzoylmethane compounds, which are per se well known as active filters in the UV-A region, are described, in particular, in FR-A-2,326,405 and FR-2,440,933, as well as in EP-A-0,114,607; 4-tert-butyl-4′-methoxydibenzoylmethane is also commercially available under the trademark “PARSOL 1789” by GIVAUDAN.
Unfortunately, the dibenzoylmethane derivatives are compounds which are relatively sensitive to ultraviolet radiation (especially UV-A irradiation), namely, they have an unfortunate tendency to degrade to a more or less rapid extent under the action of such radiation. Thus, this substantial lack of photochemical stability of dibenzoylmethane compounds with regard to ultraviolet radiation which by their very nature they are intended to be subjected, does not permit constant protection to be guaranteed during prolonged exposure to the sun, such that, in a restrictive fashion, repeated applications at regular and close intervals of time must be carried out by the user to provide an efficacious protection of the skin against UV rays.
The photostabilization of dibenzoylmethane compounds with respect to UV radiation remains a problem which to date has not satisfactorily been resolved.
Thus, EP-A-0,709,080 describes combining dibenzoylmethane derivatives with very specific benzalmalonate derivatives, namely, benzalmalonate siloxanes, in order to decrease the photoinstability of said dibenzoylmethane compounds. In particular, this ′080 application mandates that the siloxane structure of these compounds is essential to provide satisfactory photostabilization (see page 10, line 22 of EP-A-0,709,080). However, these benzalmalonate siloxanes are molecules which are bulky and complex to synthesize.
SUMMARY OF THE INVENTION
It has now unexpectedly and surprisingly been determined that combining the dibenzoylmethane compounds indicated above with a photostabilizing effective amount, not of a benzalmalonate siloxane, but of a benzalmalonate silane, markedly enhances the photochemical stability (or photostability) of these same dibenzoylmethane compounds.
It has also been determined that certain novel processes for the preparation of various of these benzalmalonate silanes present the advantage of being much more easy to carry out than the hydrosilylation process described in the prior art, for example, in JP-07/330,779.
Thus, the present invention features improving the photostability of at least one photolabile dibenzoylmethane compound with respect to UV-radiation, by intimately combining said dibenzoylmethane compounds with an effective amount of at least one benzalmalonate silane having the following structural formula (I):
in which R
1
, R
2
and R
3
, which may be identical or different, are each an optionally halogenated C
1
-C
10
alkyl radical or a phenyl radical; R
4
and R
5
, which may be identical or different, are each a hydrogen atom, a hydroxyl radical, a C
1
-C
6
alkyl radical, a C
1
-C
6
alkoxy radical, or a trimethylsilyloxy radical; R
6
and R
7
, which may be identical or different, are each a C
1
-C
8
alkyl radical; a is equal to 0 or 1; and Y is a divalent radical having one of the following formulae (1) to (4):
wherein R
8
is a hydrogen atom or a C
1
-C
5
alkyl radical, and p is an integer ranging from 1 to 10, inclusive, with the proviso that the group —Y—(O)
a
— and the two groups R
4
and R
5
are variously bonded to the aromatic ring member in the para-position and in the two meta-positions with respect to the radical —CH═C—[(CO
2
R
6
)](CO
2
R
7
).
REFERENCES:
patent: 5536732 (1996-07-01), Lesur
patent: 7-330779 (1995-12-01), None
Benkeser, R.A., M.L. Burraus, L.E. Noise and J.V. Schisler, “The Stereochemistry of the Addition of Silicochloroform to Acetylenes. A Comparison of Catalyst Systems”, J. Am. Chem. Soc. 83, p. 4385-4380 (1961).
Furuya, N. and T. Sukawa, “The Condensation Reaction of Trichlorosilane with Allylic Chlorides Catalyzed by copper Salts in the Presence of a Tertiary Amine”, J. Organometallic Chem. 96, C1-C3 (1975).
Hosomi, A.,M. Saito and H. Sakurai, “2-Trimethylsilymethyl-1,3-butadiene As a Novel Reagent for Isoprenylation. New Access to Ipsenol and Ipsdienol, Pheromones of Lps Paraconfususl”, Tetrahedron Letters, p. 429-432 (1979).
Hosomi, A.,M. Saito and H. Sakurai, “Synthesis of alpha,alpha-Dimethylallylsilanes, A Reagent of Regiospecific Prenylation of Acetals and Carbonyl compounds”, Tetrahedron Letters, p. 2589-2592 (1978).
Lefort, M. Simmonet, C., M. Birot, G. Deleris, J. Dunoues and R. Calas, “One-step Synthesis of Allylic Silanes-Extension to Benzylsilanes”, Tetrahedron Letters, p. 1857-1860 (1980).
Pillot, J., J. Douglas and R. Calas, “Synthese Originals Et Pratique De L'Artemisia Cetone”, Tetrahedron Letters, p. 1871-1872 (1976).
Sommer, L.H., L.J. Tyler and C. Whitmore, “Reactions of Allyltrimethylsilane”, J. Am. Chem. Soc. 70, p. 2872-2874 (1948).
Sommer, L.H., R.E. Van Strien and C. Whitmmore, “Gamma-Eliminations Involving Silicon. A New Synthesis of the Cyclopropane Ring”, J. Am. Chem. Soc. 71, p. 3056-060 (1949).
Weber, P.W., “Silicon Reagnets for Organic Synthesis” (Springer Verlag Berlin Hidelberg, Berlin) p. 430, (1983).
Yatagi, H. Y. Yamamoto and K. Maruyama, A New Procedure For The Stereoselective Synthesis of (Z)-2-alkenylsilanes And-Tins and Their Application to Erythro-selective Synthesis of Beta-alkyl Alcohol Derivatives, J. Am. Chem. Soc. 102, p. 4548-4549 (1980).
Gotteland Synthetic Comm 26(15), 2925-34, 1996.
Allard Delphine
Candau Didier
Forestier Serge
Richard Herve
Burns Doane Swecker & Mathis L.L.P.
Gerstl Robert
Societe L′Oreal
LandOfFree
UV-photoprotective dibenzoylmethane compositions comprising... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with UV-photoprotective dibenzoylmethane compositions comprising..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and UV-photoprotective dibenzoylmethane compositions comprising... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-2899323