Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Having -c- – wherein x is chalcogen – bonded directly to...
Reexamination Certificate
2000-09-01
2003-06-03
Ford, John M. (Department: 1624)
Drug, bio-affecting and body treating compositions
Designated organic active ingredient containing
Having -c-, wherein x is chalcogen, bonded directly to...
C544S306000, C556S009000, C252S589000, C424S059000, C424S060000, C424S400000, C424S401000
Reexamination Certificate
active
06573269
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to novel pyrimidine-2,4,6-trione compounds which are effective in absorbing ultra violet radiation and to light screening compositions containing such pyrimidine-2,4,6-trione compounds.
BACKGROUND OF THE INVENTION
Light screening compositions containing pyrimidine-2,4,6-trione compounds are described in WO 98/14423. This publication refers, inter alia, to compounds of the general formula:
wherein
R is alkyl, cyclic alkyl, aralkyl or aryl; and
R
a
and R
b
are each independently hydrogen, alkyl, cyclic alkyl, aralkyl and aryl.
This publication discloses that such compounds have an excellent ultraviolet absorbing ability. These compounds, however, are sensitive to hydrolytic decomposition.
SUMMARY OF THE INVENTION
It has now been found that compounds of the above formula in which the —COOR group is replaced by an ether group —OR or an ester group —OCOR surprisingly exhibit superior chemical stability.
Thus, one embodiment of the invention are compounds of the general formula I
wherein
R
1
and R
2
are each independently C
2
-C
18
alkyl, C
5
-C
7
cycloalkyl or C
2
-C
18
alkyl in which at least one methylene group is replaced by oxygen;
R
3
is hydrogen, C
1
-C
18
alkyl, C
2
-C
18
alkyl in which at least one methylene group is replaced by oxygen, C
1
-C
18
alkyl carbonyl, C
3
-C
18
alkenyl, C
3
-C
18
alkynyl, or a group YS;
R
4
is hydrogen, C
1
-C
8
alkyl or a group OR
3
;
Y is a linker group; and
S is a silane-, an oligosiloxane- or a polysiloxane moiety.
Another embodiment of the invention are light screening compositions containing a compound of formula I.
A further embodiment of the invention is a method for protecting a surface of a substrate from ultraviolet light. This method includes applying to a surface of a substrate a UV-blocking amount of a light screening composition containing a cosmetic base and a compound of formula I.
DETAILED DESCRIPTION OF THE INVENTION
In the compounds of formula I, R
1
and R
2
may be the same or different. Preferably, R
1
and R
2
have the same meaning and are ethyl, propyl, isopropyl, n-butyl, sec. butyl, tert. butyl, 2-ethyl hexyl or cyclohexyl. Particularly preferred is isopropyl.
The residue OR
3
is preferably in the para position. R
3
preferably is C
2
-C
8
alkyl or a group YS, more preferably 2-ethyl hexyl or a group YS.
The residue R
4
preferably is hydrogen or hydroxy.
In the present invention, the term “C
1
-C
18
alkyl” means straight chain or branched saturated hydrocarbon residues with 1 to 18 carbon atoms such as methyl, ethyl, propyl, isopropyl, thexyl, (1,1,2 trimethyl-1-propyl), n-butyl, sec. butyl, tert. butyl, pentyl, neopentyl, hexyl, 2-ethyl-hexyl, octyl and the like.
The term “C
5
-C
7
cycloalkyl” means saturated hydrocarbon rings with 5 to 7 carbon atoms, i.e. cyclopentyl, cyclohexyl, and cycloheptyl.
The term “C
2
-C
18
alkyl in which at least one methylene group is replaced by oxygen” means straight chain or branched saturated hydrocarbon residues with up to 17 carbon atoms which are bound via a carbon atom and have at least one group such as —(CH
2
—O)—, —(CH
2
—CH
2
—O)—, —(CH
2
—CH
2
—CH
2
—O)—, —(CH
2
—CH
2
—CH
2
—CH
2
—O)—, and the like.
In the term “C
1
-C
18
alkyl carbonyl,” the alkyl residue is as defined above.
The term “C
3
-C
18
alkenyl” means straight chain or branched unsaturated hydrocarbon residues with 3 to 18 carbon atoms containing at least one double bond such as propen-2-yl, propen-3-yl, buten-3-yl, buten-4-yl, penten-4-yl, penten-5-yl, and the like.
The term “C
3
-C
18
alkynyl” means straight chain or branched unsaturated hydrocarbon residues with 3 to 18 carbon atoms containing at least one triple bond. A preferred alkynyl residue is propargyl.
As used herein, the phrase “linker group” means a C
3
-C
12
divalent alkylene or alkylene chain which links the UV absorbing chromophoric residue to the silane, oligosiloxane or polysiloxane moiety.
The term “C
3
-C
12
divalent alkylene chain” means straight chain or branched saturated hydrocarbon residues such as 3-propylene, 2-propylene, 2-methyl-3-propylene, 3-butylene, 4-butylene, 4-pentylene, 5-pentylene, 6-hexylene, and the like.
The term “C
3
-C
12
divalent alkenylene chain” means unsaturated hydrocarbon residues containing at least one double bond, 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.
The divalent alkylene or alkenylene chains may be interrupted by one or several oxygen atoms. Examples of oxygen interrupted linker groups are e.g. 2-ethyloxy-eth-2-ylene, 4-butyloxy-eth-2-ylene or 3,6-dioxa-8-octylen. The linker groups of the present invention include 3-propylene, 4-butylene, 2-propen-2-ylene, 2-propen-3-ylene or 3-buten-4-ylene, preferably 2-propen-2-ylene or 2-propen-3-ylene.
The term “silane” means a group —SiR
5
R
6
R
7
, wherein R
5
, R
6
and R
7
are each independently C
1
-C
6
alkyl or phenyl. Preferred silane groups are e.g. trimethylsilane, triethylsilane, tripropylsilane, triisopropylsilane, dimethyl tert.butylsilane, dimethyl thexylsilane, triphenylsilane, dimethylphenylsilane and the like.
As used herein, the term “oligosiloxane” means groups of the general formula —SiR
8
m
(OSiR
8′
3
)
n
where m=0, 1 or 2; n=1, 2 or 3, m+n=3, and wherein R
8′
are each independently C
1
-C
6
alkyl or phenyl. Preferably R
8
and R
8′
have the same meaning. Preferably, the oligosiloxane is —SiMe(OSiMe
3
)
2
, wherein Me is methyl.
As used herein, the term “oligosiloxane” also includes groups of formulae IIa or IIb:
wherein R
9
is C
1
-C
6
alkyl or phenyl and r is an integer from 1 to 9, preferably 1 to 3. The residue R
9
is preferably C
1
-C
4
alkyl, such as for example, methyl.
As used herein, the term “polysiloxane” means groups of formulae IIIa or IIIb:
wherein
R
10
is C
1
-C
6
alkyl or phenyl;
s is an integer from 4 to 250;
t is an integer from 5 to 250; and
q is an integer from 1 to 30.
Preferably, “s” is an integer from 4 to 150. Preferably, “q” is an integer from 2 to 10, such as for example, it has statistical mean value of about 4. Preferably, “t” is an integer from 5 to 150, such as for example, it has statistical mean value of about 60. The residue R
10
is preferably C
1
-C
4
alkyl, such as for example, methyl.
The compounds of the general formula I may be prepared by methods known per se. For example, in compounds of the general formula I, wherein R
3
is C
1
-C
18
alkyl, C
2
-C
18
alkyl in which at least one methylene group is replaced by oxygen, C
3
-C
18
alkenyl or C
3
-C
18
alkynyl, and R
4
is hydrogen or C
1
-C
8
alkyl, the process starts by alkylation of a nitrophenol of the formula IVa:
wherein R
4′
is hydrogen or C
1
-C
8
alkyl; with an alkyl halide to provide a nitro phenolic ether IVb as set forth below:
The alkyl halide has the formula R
3′
Hal, wherein
R
3′
is C
1
-C
18
alkyl, C
2
-C
18
alkyl in which at least one methylene group is replaced by oxygen, C
3
-C
18
alkenyl or C
3
-C
18
alkynyl; and
Hal is chloro, bromo or iodo, preferably, chloro or bromo.
The starting nitrophenol is commercially available or may be readily prepared by known methods.
The reaction is run in a suitable reaction solvent. The choice of the solvent is not critical. Suitable solvents include toluene, pyridine or polar aprotic solvents, such as e.g., 1-methyl-2-pyrrolidone, dimethylformamide, dimethylsulfoxide, dioxane, tetrahydrofuran, acetonitrile, and the like. The reaction mixture includes an acid acceptor, such as a mild base, for example, sodium or potassium carbonate, which can absorb the acid-by-product of the alkylation. The reactants usually are present in about equal molar amounts and the reaction is run at an elevated temperature, e.g. at about 80° C.-150° C., preferably at about 100° C.
The nitro phenolic ether (IVb) obtained is then reduced either by conventional methods using reduction with tin or zinc and hydro
Bryan Cave LLP
Ford John M.
Roche Vitamins Inc.
Truong Tamthom N.
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