# US 5,352,793 A · Sunscreen compounds

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- Number: US 5,352,793 A
- Document ID: US5352793A
- Status: Granted
- Kind: A
- Application number: 07/618,610
- Filed: 1990-11-27
- Granted: 1994-10-04
- Earliest claimed: 1986-09-26
- Assignees: ICI Australia Operations Proprietary Limited
- Inventors: Graham Bird; Neil Fitzmaurice; Walter C. Dunlap; Bruce E. Chalker; Wickramasinghe M. Bandaranayake
- Web page: https://patentgrep.com/patent/US5352793A

## CPC

- C07D 221/20: Spiro-condensed ring systems
- A61K 8/4926: {having six membered rings}
- A61Q 17/04: Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
- C07D 211/70: with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D 215/20: Oxygen atoms
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- A61K: PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES (devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms A61J3/00; chemical aspects of, or use of materials for deodorisation of air, for disinfection or sterilisation, or for bandages, dressings, absorbent pads or surgical articles A61L; soap compositions C11D)
- A61Q: SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS

## Abstract

The invention relates to sunscreen compounds of formula I ##STR1## wherein R.sup.1 is selected from alkyl, alkenyl, alkynyl substituted alkyl, substituted alkenyl, phenyl, substituted phenyl, substituted benzyl, cycloalkyl, cycloalkenyl, substituted cycloalkyl, substituted cycloalkenyl; R.sup.2 is selected from hydrogen, alkyl and alkoxy; R.sup.3 is selected from alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, phenyl, benzoyl, substituted phenyl, substituted benzyl, substituted benzoyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, alkanyoyl, substituted alkanoyl, the group OROROR.sup.9 wherein R is a bivalent hydrocarbon radical and R.sup.9 is alkyl, alkenyl, phenyl benzyl, substituted phenyl, substituted benzyl; R.sup.4 is alkyl or alkoxy; n is an integer from 0 to 4; and R.sup.5 and R.sup.6 are independently selected from alkyl, alkoxy, alkanoyl, alkanoyl substituted by hydroxyl or alkoxycarbonyl.

## Claims

### Claim 1

A compound of formula I ##STR44## wherein: R.sup.1 is selected from the group consisting of C.sub.1 to C.sub.18 alkyl; C.sub.1 to C.sub.9 alkyl substituted with a substituent selected from the group consisting of hydroxy, amino, C.sub.1 to C.sub.9 alkoxy, C.sub.2 to C.sub.9 alkenyloxy, C.sub.1 to C.sub.9 alkanoyl, (C.sub.1 to C.sub.9 alkoxy) carbonyl, carbamoyl, (C.sub.1 to C.sub.6 alkyl)carbamoyl and phenyl; C.sub.2 to C.sub.18 alkenyl; C.sub.2 to C.sub.9 alkenyl substituted with a substituent selected from the group consisting of hydroxy, amino, C.sub.1 to C.sub.9 alkoxy, C.sub.2 to C.sub.9 alkenyloxy, C.sub.1 to C.sub.9 alkanoyl, carbamoyl, (C.sub.1 to C.sub.6 alkyl)carbamoyl, and phenyl; C.sub.2 to C.sub.18 alkynyl; phenyl; benzyl; the groups phenyl and benzyl substituted on the benzene ring with a substituent selected from the group of C.sub.1 to C.sub.12 alkyl, C.sub.1 to C.sub.12 alkoxy, C.sub.2 -C.sub.9 alkylene, C.sub.2 to C.sub.12 alkenyloxy, C.sub.1 to C.sub.12 alkylamino N,N-di(C.sub.1 to C.sub.6 alkyl)amino, (C.sub.1 to C.sub.12 alkoxy)carbonyl and C.sub.1 to C.sub.12 alkanoyl; C.sub.5 to C.sub.7 cycloalkyl; C.sub.5 to C.sub.7 cycloalkenyl; the groups substituted C.sub.5 to C.sub.7 cycloalkyl and substituted C.sub.5 to C.sub.7 cycloalkenyl wherein the substituent is selected from the group consisting of hydroxy, amino, C.sub.1 to C.sub.9 alkyl, C.sub.1 to C.sub.9 alkoxy, and C.sub.1 to C.sub.9 alkenyloxy;
R.sup.3 is selected from the group consisting of C.sub.2 to C.sub.18 alkyl; C.sub.1 to C.sub.9 alkyl substituted with a substituent selected from the group consisting of hydroxy, amino, C.sub.1 to C.sub.9 alkoxy, C.sub.2 to C.sub.9 alkenyloxy, C.sub.1 to C.sub.9 alkanoyl, (C.sub.1 to C.sub.9 alkoxy)carbonyl, carbamoyl, (C.sub.1 to C.sub.6 alkyl)carbamoyl and phenyl; C.sub.2 to C.sub.18 alkenyl; C.sub.2 to C.sub.9 alkenyl substituted with a substituent selected from the group consisting of hydroxy, amino C.sub.1 to C.sub.9 alkoxy, C.sub.2 to C.sub.9 alkenyloxy, C.sub.1 to C.sub.9 alkanoyl, (C.sub.1 to C.sub.9 alkoxy)carbonyl, carbamoyl, (C.sub.1 to C.sub.9 alkyl) carbamoyl and phenyl; C.sub.2 to C.sub.18 alkynyl; phenyl; benzyl; benzoyl; the groups phenyl, benzyl and benzoyl optionally substituted on the benzene ring with a substituent selected from the group consisting of hydroxy, amino, C.sub.1 to C.sub.12 alkyl, C.sub.2 to C.sub.12 alkenyl, C.sub.1 to C.sub.12 alkoxy, C.sub.2 to C.sub.12 alkenyloxy, C.sub.1 to C.sub.12 alkylamino, N,N-di(C.sub.1 to C.sub.6 alkyl)amino, (C.sub.1 to C.sub.12 alkoxy)carbonyl, and C.sub.1 to C.sub.12 alkanoyl; C.sub.5 to C.sub.7 cycloalkyl; C.sub.5 to C.sub.7 cycloalkenyl; the groups substituted C.sub.5 to C.sub.7 cycloalkyl and substituted C.sub.5 to C.sub.7 cycloalkenyl wherein the substituent is selected from the group consisting of hydroxy, amino, C.sub.1 to C.sub.9 alkyl, C.sub.1 to C.sub.9 alkoxy, and C.sub.1 to C.sub.9 alkenyloxy; C.sub.1 to C.sub.18 alkanoyl; C.sub.2 to C.sub.9 alkanoyl substituted with a substituent selected from the group consisting of hydroxy, amino, C.sub.1 to C.sub.9 alkoxy, C.sub.2 to C.sub.9 alkenyloxy, C.sub.1 to C.sub.9 alkanoyl, carbamoyl, C.sub.1 to C.sub.6 alkyl)carbamoyl, (C.sub.1 to C.sub.9 alkoxy)carbonyl and phenyl; and the group --OROROR.sup.9 wherein R which may be the same or different are bivalent hydrocarbon radicals of 2 to 6 carbon atoms and R.sup.9 is a hydrocarbon radical selected from C.sub.1 to C.sub.6 alkyl, C.sub.2 to C.sub.6 alkenyl phenyl, benzyl, (C.sub.1 to C.sub.6 alkyl) phenyl and (C.sub.1 to C.sub.6 alkyl)benzyl;
R.sup.2 is selected from the group consisting of hydrogen, C.sub.1 to C.sub.6 alkyl, C.sub.1 to C.sub.6 alkoxy;
R.sup.4 is selected from the group consisting of C.sub.1 to C.sub.6 alkyl and C.sub.1 to C.sub.6 alkoxy;
n is an integer selected from 0 to 4 inclusive;
R.sup.5 and R.sup.6 which may be the same or different are selected from hydrogen, C.sub.1 to C.sub.6 alkyl, C.sub.1 to C.sub.6 alkoxy, C.sub.1 to C.sub.10 alkanoyl, C.sub.1 to C.sub.10 alkanoyl substituted by carboxyl or (C.sub.1 to C.sub.6 alkoxy) carbonyl;
with the proviso that when R.sup.1 is methyl then R.sup.3 is not selected from the group of hydroxyethyl, methoxymethyl and benzyl and when R.sup.1 is phenol, R.sup.3 is not acetyl or alkyl substituted with phenyl.

### Claim 2 (depends on 1)

A compound according to claim 1 wherein: R.sup.1 is selected from C.sub.1 to C.sub.18 alkyl; C.sub.1 to C.sub.9 alkyl substituted with a substituent selected from the group consisting of hydroxy, amino, C.sub.1 to C.sub.9 alkoxy, C.sub.1 to C.sub.9 alkanoyl and (C.sub.1 to C.sub.9 alkoxy)carbonyl; C.sub.1 to C.sub.18 alkenyl; cyclohexyl; phenyl; benzyl; the groups phenyl and benzyl said groups being substituted in the benzene ring with a substituent selected from the group of C.sub.1, to C.sub.9 alkyl, C.sub.2 to C.sub.9 alkenyl, C.sub.1 to C.sub.9 alkoxy, C.sub.1 to C.sub.9 alkanoyl and (C.sub.1 to C.sub.9 alkoxy) carbonyl;
R.sup.3 is selected from C.sub.2 to C.sub.18 alkyl; C.sub.1 to C.sub.9 alkyl substituted with a substituent selected from the group consisting of hydroxy, amino, C.sub.1 to C.sub.9 alkoxy and C.sub.1 to C.sub.9 alkanoyl; C.sub.2 to C.sub.18 alkenyl; cyclohexyl; phenyl; benzyl; benzoyl; the groups phenyl, benzyl and benzoyl said groups being substituted on the benzene ring with a substituent selected from the group of C.sub.1 to C.sub.9 alkyl, C.sub.2 to C.sub.9 alkenyl, C.sub.1 to C.sub.9 alkoxy, C.sub.1 to C.sub.9 alkanoyl and (C.sub.1 to C.sub.9 alkoxy)carbonyl; C.sub.3 to C.sub.18 alkanoyl; and C.sub.2 to C.sub.9 alkanoyl substituted with phenyl;
R.sup.2 is hydrogen or C.sub.1 or C.sub.6 alkyl;
R.sup.4 is C.sub.1 to C.sub.6 alkyl;
n is from 0 to 4;
R.sup.5 and R.sup.6 are independently selected from hydrogen;
C.sub.1 to C.sub.6 alkyl; the substituted alkanoyl group of formula III ##STR45## wherein R.sup.10, R.sup.11 and R.sup.12 are independently selected from C.sub.1 to C.sub.4 alkyl and hydrogen.

### Claim 3 (depends on 2)

A compound according to claim 2 wherein:
R.sup.1 is selected from the group consisting of C.sub.1 to C.sub.18 alkyl; C.sub.1 to C.sub.6 alkyl substituted with a substituent selected from C.sub.1 to C.sub.6 alkanoyl and (C.sub.1 to C.sub.6 alkoxy) carboxyl; C.sub.1 to C.sub.18 alkenyl; phenyl, and benzyl;
R.sup.2 is hydrogen or C.sub.1 to C.sub.4 alkyl;
R.sup.3 is selected from the group consisting of C.sub.2 to C.sub.18 alkyl; C.sub.1 to C.sub.9 alkyl substituted with a substituent selected from the group consisting of hydroxy and C.sub.1 to C.sub.9 alkoxy; C.sub.1 to C.sub.18 alkenyl; benzoyl; benzyl; benzoyl substituted with a substituent selected from C.sub.1 to C.sub.6 alkyl and C.sub.1 to C.sub.6 alkoxy; and C.sub.3 to C.sub.9 alkanoyl; R.sup.4 is C.sub.1 to C.sub.4 alkyl; and n is an integer from 0 to 3;
R.sup.5 and R.sup.6 are selected from the group consisting of: (i) R.sup.5 and R.sup.6 are independently selected from hydrogen and C.sub.1 to C.sub.4 alkyl and (ii) one of R.sup.5 and R.sup.6 is hydrogen and the other is a group of formula III. ##STR46## wherein R.sup.10, R.sup.11 and R.sup.12 are independently selected from the group consisting of hydrogen and C.sub.1 to C.sub.4 alkyl.

### Claim 4 (depends on 3)

A compound according to claim 3 wherein:
R.sup.1 is C.sub.1 to C.sub.9 alkyl;
R.sup.2 is selected from hydrogen and C.sub.1 to C.sub.4 alkyl;
R.sup.3 is selected from C.sub.2 to C.sub.9 alkyl; C.sub.2 to C.sub.9 alkenyl; C.sub.1 to C.sub.9 alkyl substituted with a substituent selected from hydroxy, phenyl and C.sub.1 to C.sub.6 alkoxy; benzoyl; benzoyl substituted with a substituent selected from the group consisting of C.sub.1 to C.sub.6 alkyl and C.sub.1 to C.sub.6 alkoxy; and C.sub.3 to C.sub.9 alkanoyl;
R.sup.4 is C.sub.1 to C.sub.4 alkyl;
n is from 0 to 3;
R.sup.5 and R.sup.6 are consisting of
(i) R.sup.5 and R.sup.6 are independently selected from hydrogen and C.sub.1 to C.sub.4 alkyl; and
(ii) one of R.sup.5 and R.sup.6 is hydrogen and the other is a group of formula III ##STR47## wherein R.sup.10 and R.sup.11 are methyl and R.sup.12 is hydrogen or C.sub.1 to C.sub.6 alkyl and wherein when one of R.sup.5 and R.sup.6 is not hydrogen or C.sub.1 to C.sub.4 alkyl, then n is zero.

### Claim 5 (depends on 3)

A compound according to claim 3 wherein:
R.sup.1 is C.sub.1 to C.sub.9 alkyl;
R.sup.2 is hydrogen;
R.sup.3 is selected from the group consisting of C.sub.1 to C.sub.9 alkyl; 2-phenylethyl and cyclohexyl;
R.sup.4 is methyl
n is chosen from 0 to 3;
R.sup.5 and R.sup.6 are selected from the group consisting of (i) R.sup.5 and R.sup.6 are independently selected from hydrogen and methyl; and (ii) one of R.sup.5 and R.sup.6 is hydrogen and the other is a group of formula III ##STR48## wherein R.sup.10 and R.sup.11 are methyl and R.sup.12 is ethyl; and wherein when at least one of R.sup.5 and R.sup.6 is not hydrogen or methyl, then n is zero.

### Claim 6 (depends on 1)

A compound of formula ##STR49## where R.sup.5 and R.sup.6 are independently selected from the group consisting of hydrogen, C.sub.1 to C.sub.6 alkyl and C.sub.1 to C.sub.6 alkoxy and R.sup.1, R.sup.2, R.sup.3, R.sup.4 and n are as defined according to claim 1.

### Claim 7 (depends on 6)

A compound according to claim 6 wherein R.sup.5 and R.sup.6 are independently selected from hydrogen and C.sub.1 to C.sub.6 alkyl.

### Claim 8 (depends on 7)

A compound according to claim 7 wherein R.sup.5 and R.sup.8 are hydrogen.

### Claim 9 (depends on 3)

A compound according to claim 3 wherein:
R.sup.1 is C.sub.1 to C.sub.18 alkyl;
R.sup.2 is hydrogen;
R.sup.3 is selected from the group consisting of C.sub.2 to C.sub.18 alkyl and C.sub.2 to C.sub.18 alkenyl;
n is O;
R.sup.5 and R.sup.6 are hydrogen.

### Claim 10 (depends on 6)

A compound according to claim 6 wherein:
R.sup.1 is selected from the group consisting of methyl, ethyl, propyl, 3-methylbutyl;
R.sup.2 is hydrogen;
R.sup.3 is selected from the group consisting of propyl, 1-methylethyl, butyl, 3-methylbutyl, 2-ethylhexyl, and 3-methyl-2-butenyl;
n is 0; and
R.sup.5 and R.sup.6 are hydrogen.

### Claim 11

A compound selected from the group consisting of
methyl 1-(3-methylbutyl)-1,4,5,6-tetrahydro-3-pyridyl ketone;
methyl 1-(3-methyl-2-butenyl)-1,4,5-6-tetrahydro-3-pyridyl ketone;
ethyl 1-butyl-1,4,5,6-tetrahydro-3-pyridyl ketone;
ethyl 1-(3-methylbutyl)-1,4,5,6-tetrahydro-3-pyridyl ketone;
propyl 1-propyl-1,4,5,6-tetrahydro-3-pyridyl ketone;
propyl 1-butyl-1,4,5,6-tetrahydro-3-pyridyl ketone;
propyl-1-(3-methylbutyl)-1,4,5,6-tetrahydro-3-pyridyl ketone;
4-methylpentyl 1-propyl-1,4,5,6-tetrahydro-3-pyridyl ketone;
phenyl 1-propyl-1,4,5,6-tetrahydro-3-pyridyl ketone; and
methyl 1-butyl-4,4,6 trimethyl-1,4,5,6-tetrahydro-3-pyridyl ketone.