2-hydroxyphenyl benzotriazoles as UV-A/B filters

Details 2-hydroxyphenyl benzotriazoles as UV-A/B filters 2-hydroxyphenyl benzotriazoles as UV-A/B filters

2001-01-18

2002-12-03

McKane, Joseph K. (Department: 1626)

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

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

Reexamination Certificate

active

06489486

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to a process for alkylating 2-hydroxyphenyl-benzotriazoles, which are effective in absorbing ultra violet radiation. In a further aspect, the present invention relates to novel alkylated 2-hydroxyphenyl-benzotriazoles, to novel cosmetic or dermatological sunscreen compositions containing alkylated 2-hydroxyphenyl-benzotriazoles, and to their use as UV screening agents.
BACKGROUND OF THE INVENTION
Winter et al., U.S. Pat. No. 4,587,346 discloses a process for alkylating 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazoles by reaction with alkene compound ions in the presence of a catalyst. The process produces random mixtures of isomers.
UV screening compositions containing 2-hydroxyphenyl-benzotriazoles are described in European Patent Publications EP 0711778 A (Herve et al., U.S. Pat. No. 5,569,451), EP 0392883 A (Gerard et al., U.S. Pat. No. 5,089,250), Ching, U.S. Pat. Nos. 4,316,033 and 4,349,602, and International Patent Application WO 94/06404 (Hansenne et al., U.S. Pat. No. 5,089,250).
It has been found that alkylated 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazoles can be obtained in substantially pure form. Further, it has been found that certain novel 2-hydroxyphenyl-benzotriazoles have improved solubility and extinction coefficients, and are more economical to prepare than those of the prior art quoted above.
SUMMARY OF THE INVENTION
The present invention is a process for the preparation of compounds of the formula:
wherein
R
1
is alkyl; R
2
, R
3
, R
4
, R
5
, and R
6
are, independently, hydrogen, alkyl or alkenyl; X is hydrogen, halogen, alkyl or alkoxy; and the dotted bond is an optional bond,
which includes the steps of
a) reacting a compound of the formula:
with a compound of the formula:
to obtain a compound of the formula:
b) heating the compound of formula II obtained in step a) to yield a compound of the formula
and if desired,
c) hydrogenating the double bond between R
2
and R
3
in the compound of formula I A to obtain a compound of formula I wherein the dotted bond is absent;
wherein in the above formulae IA, II, III and IV, R
1
, R
2
, R
3
, R
4
, R
5
, R
6
, X and the dotted line are as defined in formula I, and Y is a leaving group.
The following compounds are novel, and are also part of the present invention: compounds of formula I above, wherein X, R
1
, R
2
, R
3
, R
4
, R
5
, R
6
and the dotted bond are as defined in claim
1
, with the proviso that if the dotted bond is present, one of R
2
, R
4
, R
5
, and R
6
is alkenyl, and if the dotted bond is absent, one of R
2
and R
6
is alkenyl or branched alkyl. In addition, the following compounds are also novel:
2-(Benzotriazole-2-yl)-4-methyl-6-(1-octen-3-yl)-phenol,
2-(Benzotriazole-2-yl)-4-methyl-6-(3-octen-2-yl)-phenol
2-(Benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)-6-(1-hexen-3-yl)-phenol,
2-(Benzotriazole-2-yl)-4-methyl-6-(1-decen-3-yl)-phenol,
2-(Benzotriazole-2-yl)-4-methyl-6-(1-hexen-3-yl)-phenol,
2-(Benzotriazole-2-yl)-4-methyl-6-(1-dodecen-3-yl)-phenol,
2-(Benzotriazole-2-yl)-4-methyl-6- (1-hexadecen-3-yl)-phenol,
2-(Benzotriazole-2-yl)-4-methyl-6-(3-octyl)-phenol,
2-(Benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)-6-(3-hexyl)-phenol,
2-(Benzotriazole-2-yl)-4-methyl-6-(3-hexyl)-phenol,
2-(Benzotriazole-2-yl)-4-methyl-6-(3-decyl)-phenol,
2-(Benzotriazole-2-yl)-4-methyl-6-(3-dodecyl)-phenol,
2-(Benzotriazole-2-yl)-4-methyl-6-(3-hexadecyl)-phenol,
2-(Benzotriazole-2-yl)-4-methyl-6-(3,7-dimethyl-2-octenyl)-phenol,
2-(Benzotriazole-2-yl)-4-methyl-6-(3,7-dimethyl-3-octyl)-phenol,
2-(Benzotriazole-2-yl)-4-methyl-6-(3,7-dimethyl-1-octen-3-yl)-phenol,
2-(Benzotriazole-2-yl)-4-methyl-6-(3,7-dimethyl-3-octyl)-phenol,
2-(Benzotriazole-2-yl)-4-methyl-6-(3,7-dimethyl-3-octen-2-yl)-phenol, and
2-(Benzotriazole-2-yl)-4-methyl-6-(3,7-dimethyl-2-octyl)-phenol.
Further examples of novel compounds of the present invention are:
2-(Benzotriazole-2-yl)-4-methyl-6-(3,7-dimethyl-2,6-octadienyl)-phenol,
2-(Benzotriazole-2-yl)-4-methyl-6-(3,7-dimethyl- 1,6-octadienyl)-phenol, and
2-(Benzotriazole-2-yl)-4-methyl-6-(3,7-dimethyl-3,6-octadienyl)-phenol.
Another aspect of the invention relates to novel cosmetic or dermatological UV light screening compositions containing a 2-hydroxyphenyl-benzotriazole of formula I above, wherein X, R
1
, R
2
, R
3
, R
4
, R
5
, R
6
, and the dotted bond are as defined in claim 1, with the proviso that either R
4
or R
5
is an alkyl having at least 2 carbon atoms, or is alkenyl. In yet another aspect, the invention relates to novel UV light screening compositions containing a 2-hydroxyphenyl-benzotriazole of formula I above, wherein X, R
1
, R
2
, R
3
, R
4
, R
5
, R
6
, and the dotted bond, are as defined in claim 1, with the proviso that either R
4
or R
5
is an alkyl having at least 2 carbon atoms or is an alkenyl; and at least one additional UV-A and/or UV-B screening agent. Finally, the present invention relates to a method for protecting hair or skin from damage caused by UV-radiation comprising administering to the hair or skin prior to exposure to a UV-radiation source a composition comprising an UV-radiation blocking amount of the novel 2-hydroxyphenyl-benzotriazoles as defined earlier, as UV light screening agents.
Especially preferred compounds of formula I for use as UV light screening agents are:
2-(Benzotriazole-2-yl)-4-methyl-6-(1-octen-3-yl)-phenol,
2-(Benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)-6-(1-hexen-3-yl)-phenol,
2-(Benzotriazole-2-yl)-4-methyl-6-(3-octyl)-phenol, and
2-(Benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)-6-(3-hexyl)-phenol.
The most preferred compound is 2-(Benzotriazole-2-yl)-4-methyl-6-(1-octen-3-yl)-phenol.
As used herein the term “alkyl” denotes saturated straight or branched chain hydrocarbon groups containing 1 to 21, preferably 1 to 8 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, sec. butyl, isobutyl, pentyl, neopentyl, hexyl, 2-ethyl-hexyl, and octyl. Similarly, the term “alkoxy” denotes saturated straight or branched chain hydrocarbon groups which are bound through an oxygen atom and which contain 1 to 21, preferably 1 to 8 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec. butoxy, isobutoxy, pentyloxy, neopentyloxy, hexyloxy, 2-ethyl-hexyloxy and octyloxy. The term “alkenyl” denotes straight or branched chain hydrocarbon groups containing at least one double bond and 2 to 21, preferably 2 to 8, carbon atoms. Examples of such alkenyl groups are propen-2-yl, propen-3-yl, buten-3-yl, buten-4-yl, penten-4-yl, and penten-5-yl. The term “halogen” denotes fluoro, chloro, bromo and iodo.
A preferred group of compounds within formula I are those wherein the dotted bond is present. Also preferred are compounds of formula I wherein R
5
and R
6
are hydrogen. Further preferred are compounds wherein one of R
2
, R
3
, or R
4
is an alkyl having at least three carbon atoms, and the other two are hydrogen. The total number of carbon atoms in R
2
to R
6
is preferably 3 to 21, more particularly 3 to 9 carbon atoms, most preferably 3 to 5. Especially preferred are compounds of formula I wherein R
2
and R
3
are hydrogen and R
4
is an alkyl having 3 to 5 carbon atoms. R
1
is preferably methyl or 1,1,3,3-tetramethylbutyl. X is preferably hydrogen, methoxy or chloro, and most preferably hydrogen.


REFERENCES:
patent: 4316033 (1982-02-01), Ching et al.
patent: 4349602 (1982-09-01), Ching
patent: 4587346 (1986-05-01), Winter et al.
patent: 4812575 (1989-03-01), Vogl et al.
patent: 5164462 (1992-11-01), Yang et al.
patent: 5352753 (1994-10-01), Yang et al.
patent: 2 077 747 (1981-12-01), None
Chemical Abstracts, CAS Registry No. 139079-27-9.
Chemical Abstracts, CAS Registry No. 207738-75-8.
Chemical Abstracts, CAS Registry Nos. 2170-39-0 and 2170-39-8.
Chemical Abstracts, CAS Registry No. 218900-69-7.
Chemical Abstracts, CAS Registry No. 102116-80-3.
Tiffany, “Partial para-Migration in the Allylic Rearrangement of o-Acetamidophenyl Allyl Ether and of o-Aminophenyl Allyl Ether,”Journal of the American Chemical Society,vol. 70, pp. 592-594 (1948).

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