Indanylidene compounds

Details Indanylidene compounds Indanylidene compounds

1999-11-11

2002-07-09

Dees, Jose′ G. (Department: 1616)

Drug, bio-affecting and body treating compositions

Topical sun or radiation screening, or tanning preparations

C424S401000

Reexamination Certificate

active

06416746

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to novel indanylidene compounds which effectively absorb ultra violet (UV) radiation and to light screening compositions containing these indanylidene compounds.
BACKGROUND OF THE INVENTION
Light screening compositions including indanylidene compounds are reportedly disclosed in EP 0823 418 A2. This publication emphasizes cyano-(2,3-dihydroxy-1H-inden-1-ylidene) acetic acid ester compounds. These compounds, however, do not have a sufficient solubility in the media typically employed in cosmetics, in particular in oil and fats. Furthermore, it is desirable that the active ingredient remain on the surface of the skin, rather than prior art compounds that penetrate into or through the skin.
SUMMARY OF THE INVENTION
It has now been found that compounds having an indanylidene residue grafted via a linker to a silane, an oligosiloxane- or a polysiloxane moiety overcome the problem of penetration and show improved solubility compared to prior art compounds.
Accordingly, the present invention provides compounds of the general formula I:
The invention also provides compositions containing these compounds, and methods of using the compounds and the compositions.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides compounds of the general formula I:
wherein
X is O or NH;
R
1
is C
1
-C
20
alkyl, C
2
-C
20
alkyl in which at least one methylene group is replaced by oxygen, C
3
-C
20
alkenyl, C
3
-C
20
alkynyl or a group YS;
R
2
is C
1
-C
20
alkyl, C
2
-C
20
alkyl in which at least one methylene group is replaced by oxygen, C
3
-C
20
alkenyl, C
3
-C
20
alkynyl or a group YS; or
R
1
and R
2
may combine on adjacent C-atoms to form a dioxomethylene ring;
R
3
is C
1
-C
20
alkyl, C
2
-C
20
alkyl in which at least one methylene group is replaced by oxygen, C
3
-C
20
alkenyl, C
3
-C
20
alkynyl or a group YS;
R
4
, R
5
, R
6
are each independently H or C
1
-C
20
alkyl;
n is 0, 1 or 2;
Y is a linker group;
S is a silane-, an oligosiloxane- or a polysiloxane-moiety;
with the proviso that at least one of the R
1
, R
2
or R
3
residues is YS.
As used herein, the phrase “C
1
-C
20
alkyl” refers to straight chain or branched saturated hydrocarbon residues with 1-20 carbon atoms, such as for example, methyl, ethyl, propyl, isopropyl, butyl, sec. butyl, isobutyl, pentyl, neopentyl, hexyl, 2-ethyl-hexyl, octyl, and the like.
As used herein, the phrase “C
2
-C
20
alkyl in which at least one methylene group is replaced by oxygen” refers to straight chain or branched saturated hydrocarbon residues with up to 19 carbon atoms having at least one group such as —(CH
2
—O)—,—(CH
2
—CH
2
—O)—, —(CH
2
—CH
2
—CH
2
—CH
2
—O) and the like.
In the present invention, the phrase “C
3
-C
20
alkenyl” refers to straight chain or branched unsaturated hydrocarbon residues with 3-20 carbon atoms containing a double bond, such as for example, propen-2-yl, propen-3-yl, buten-3-yl, buten-4-yl, penten-4-yl, penten-5-yl, and the like.
As used herein, the phrase “C
3
-C
20
alkynyl” refers to straight chain or branched unsaturated hydrocarbon residues with 3-20 carbon atoms containing a triple bond such as for example, propargyl and the like.
As used herein, the phrase “linker group” refers to a C
3
-C
12
divalent alkylene or alkenylene chain which links the silane, oligosiloxane or polysiloxane moiety to the UV absorbing chromophoric residue. In the present invention, “C
3
-C
12
divalent alkylene chain” includes straight chain or branched saturated hydrocarbon residues, such as for example, 3-propylene, 2-propylene, 2-methyl-3-propylene, 3-butylene, 4-butylene, 4-pentylene, 5-pentylene, 6-hexylene and the like. In the present invention, “C
3
-C
12
divalent alkenylene chain” includes unsaturated hydrocarbon residues containing one or multiple double bonds, such as for example, 2-propen-2-ylene, 2-propen-3-ylene, 3-buten-3-ylene 3-buten-4-ylene, 4-penten-4-ylene, 4-penten-5-ylene, (3-methyl)-penta-2,4-dien-4 or 5-ylene, 11-dodecen-11-ylene and the like. Such chains may be interrupted by one or several oxygen atomforming groups such as 2-ethyloxy-eth-2-ylene, 4-butyloxy-eth-2-ylene, 3,6-dioxa-8-octylene and the like. Preferred linker groups in the present invention are: 3-propylene , 4-butylene, 2-propen-2-ylene, 2-propen-3-ylene or 3-buten-4-ylene.
As used herein, the term “silane” refers to a group -SiR
7
R
8
R
9
wherein R
7
, R
8
and R
9
are each independently C
1
-C
6
alkyl, C
1
-C
6
alkoxy or phenyl. The “C
1
-C
6
alkyl” and “C-C
6
alkoxy” residues may be straight-chain or branched, such as for example, methyl, ethyl, propyl, isopropyl, n-butyl, tert. butyl, thexyl, (1,1,2 dimethylpropyl) and, respectively, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, tert. butoxy, and thexoxy for the C
1
-C
6
alkoxy. Preferred are alkyl-silane groups, such as for example, trimethylsilane, triethylsilane, tripropylsilane, triisopropylsilane, dimethyl tert. butylsilane, dimethyl thexylsilane, triphenylsilane, dimethylphenylsilane, and the like.
As used herein, “oligosiloxane” refers to groups of the general formula—SiR
10
m
(OSiR
10
3
)
n
wherein R
10
is defined below and m=0, 1 or 2; n=3, 2 or 1, and m+n=3; or groups of the general formula IIa or IIb
wherein
A is a bond to the linker Y;
R
10
is C
1
-C
6
alkyl or phenyl;
r is 1 to 9.
In the present invention, the term “polysiloxane” refers to groups of the general formulae IIIa or IIIb:
wherein
A is a bond to the linker Y;
R
11
is C
1
-C
6
alkyl or phenyl;
s is from 4 to 250;
t is from 5 to 250;
q is from 1 to 30.
In the present invention, the R
1
and R
2
residues are preferably C
1
-C
6
alkyl, more preferably C
1
-C
4
alkyl, such as for example, methyl, or a group YS. The R
3
residue is preferably C
1
-C
6
alkyl, more preferably C
1
-C
4
alkyl, such as for example, ethyl, or a group YS.
The R
4
and R
5
residues are preferably C
1
-C
6
alkyl, more preferably C
1
-C
4
alkyl, such as for example, methyl.
The R
6
residue is preferably C
1
-C
6
alkyl, more preferably C
1
-C
4
alkyl, such as for example, methyl or hydrogen.
The R
10
and R
11
residues are preferably C
1
-C
6
alkyl, more preferably C
1
-C
4
alkyl, such as for example, methyl.
In the present invention, the value of “n” is preferably 0 or 1, “r” is preferably 1 to 3, “s” is preferably 5 to 150, “q” is preferably 2 to 10, more preferably a statistical mean value of about 4, “t” is preferably 5 to 150, more preferably a statistical mean value of about 60.
In the present invention, each R
1
, R
2
or R
3
group may be YS. Thus, the silane-, oligosiloxane- or polysiloxane moiety may be linked via Y to the indane ring or to the carboxy or amide group. Preferably the silane-, oligosiloxane- or polysiloxane moiety is linked to the carboxy or amide group (e.g. R
3
is YS).
The compounds of formula I may be prepared as follows:
In a first step, compounds of formula Ia
wherein R
1
, R
2
, R
4
, R
5
, R
6
and n are as defined above are synthesized according to known reactions (see, e.g., F. Camps, Z. Naturforsch., B: Anorg. Chem., Org. Chem. (1984), 39B (12), 1801-5), and Tetrahedron Letters 27, 2941 (1973), which are hereby incorporated by reference as if recited in full herein.
In a second step, indanylidene compounds of the general formulae Ib, Ic and Id
wherein R
1
, R
2
, R
4
, R
5
, R
6
and n are as defined above and R
12
is a C
3
-C
12
divalent alkylene- or alkenylene chain are synthesized according to known reactions such as the Knoevenagel reaction. As stated above the C
3
-C
12
divalent alkylene- or alkenylene chain may be interrupted by one or several oxygen atoms.
An example synthesis of an indanylidene compound of formula Ib is set forth below for a compound wherein R
1
and R
2
are methyl, n is 1, R
4
and R
5
are methyl, R
6
is hydrogen and X is oxygen. The corresponding compounds wherein R
1
, R
2
, R
4
, R
5
, R
6
and n are as defined above may be prepared accordingly. The details are described in Example 1.
An example synthesis of an indanylidene compound of formula Ic is

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