# US 5,326,900 A · Aromatic keto compounds, the preparation thereof, and drugs and cosmetics containing these

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- Number: US 5,326,900 A
- Document ID: US5326900A
- Status: Granted
- Kind: A
- Application number: 07/985,927
- Filed: 1992-12-04
- Granted: 1994-07-05
- Earliest claimed: 1989-02-10
- Assignees: BASF SE
- Inventors: Hans-Heiner Wuest; Bernd Janssen
- Web page: https://patentgrep.com/patent/US5326900A

## CPC

- C07C 65/36: containing rings other than six-membered aromatic rings
- C07C 65/40: containing singly bound oxygen-containing groups
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

Compounds of the general formula I ##STR1## and drugs and cosmetics prepared therefrom are described.

## Claims

### Claim 1

A compound of the formula I ##STR16## where A is ethylene or methylene which can be substituted by methyl, hydroxyl or oxo,
L is one of the following ##STR17## R.sup.1 and R.sup.2 are hydrogen or methyl, R.sup.3 is hydrogen, hydroxyl or C.sub.1 -C.sub.6 -alkoxy,
R.sup.4 is hydrogen, C.sub.1 -C.sub.4 -alkyl, halogen or methoxy,
R.sup.5 is hydrogen, or methoxy, and
R.sup.6 is ##STR18## or CHR.sup.7 --OH where
R.sup.7 is hydrogen or C.sub.1 -C.sub.4 -alkyl,
R.sup.11 is hydrogen, C.sub.1 -C.sub.4 -alkyl, or --OR.sup.13 or --NR.sup.14 R.sup.15 where R.sup.13 is hydrogen, C.sub.1 -C.sub.8 -alkyl, which can be substituted by 1 or 2 hydroxyls, or aryls or aralkyl, each of which can be substituted in the aryl moiety by a substituent selected from the group consisting of methyl, methoxy, cyano, and halogen, and where R.sup.14 and R.sup.15 are hydrogen, or aralkyl or aryl which can be substituted by a substituent selected from the group consisting of methyl, methoxy, cyano, and halogen, or R.sup.14 and R.sup.15 form, together with the nitrogen to which they are bonded, a 5- or 6-membered saturated heterocyclic radical, or a 5- or 6- membered saturated heterocyclic radical which has an oxygen in addition to the nitrogen, and R.sup.12 is C.sub.1 -C.sub.4 -alkyl, and the physiologically tolerated salts thereof.

### Claim 2

1-(4-Carbomethoxyphenyl)-3-(5,6,7, 8-tetrahydro-5,5,8,8,-tetramethyl-2-naphthyl)-1,3-propanedione.

### Claim 3

1-(4-Carboxyphenyl)-3-(5,6,7, 8-tetrahydro-5,5,8,8,-tetramethyl-2-naphthyl)-1,3-propanedione.

### Claim 4 (depends on 1)

A process for the preparation of a deoxybenzoin of the formula I as claimed in claim 1, wherein L=--CH.sub.2 --CO-- or --CO--CH.sub.2 --, which comprises reacting a phosphonic ester of the formula II ##STR19## where A and R.sup.1 --R.sup.5 have the meanings specified in claim 1, and X is --OR.sup.16 or --NR.sup.16 R.sup.17 where R.sup.16, R.sup.17 and R.sup.18 are each C.sub.1 -C.sub.4 -alkyl, with an aldehyde of the formula III ##STR20## where R.sup.6 has the meanings specified in claim 1, in the presence of a base, at a temperature in the range of -78.degree. to +60.degree. C., in a Wittig-Horner reaction, and subjecting the resulting enamine, wherein X=NR.sup.16 R.sup.17, or enol ether, wherein X=OR.sup.16, to acid hydrolysis

### Claim 5 (depends on 1)

A process for the preparation of a 1,3-diketo compound of the formula I as claimed in claim 1, wherein L=--C(O)CH.sub.2 C(O)--, or of the enol tautomer thereof, which comprises
reacting a ketone of the formula VIII ##STR21## where A and R.sup.1 --R.sup.5 have the meanings specified in claim 1, with a terephthalic ester of the formula IX ##STR22## where R.sup.18 is C.sub.1 -C.sub.4 -alkyl, at a temperature in the range of 20.degree. to 140.degree. C., in the presence of a base

### Claim 6 (depends on 1)

A process for the preparation of a 1,4-diketo compound of the formula I as claimed in claim 1, wherein L=--C(O)CH.sub.2 CH.sub.2 C(O)--, which comprises reacting a chloroethyl ketone of the formula XI ##STR23## where A and R.sup.1 to R.sup.5 have the meanings specified in claim 1, with a base to give a vinyl ketone of the formula XII ##STR24## where A and R.sup.1 have the meanings specified in claim 1, and then coupling the latter with a benzaldehyde of the formula XIII ##STR25## where R.sup.6 has the meaning specified in claim 1, in an umpolung reaction catalyzed by cyanide ions or thiazolium salts.

### Claim 7 (depends on 1)

A process for the preparation of a deoxybenzoin of the formula I as claimed in claim 1, wherein L=--CH.sub.2 --CO-- or --CO--CH.sub.2 --, which comprises
reacting a carbonyl chloride selected from the group consisting of formula IV and V ##STR26## where A and R.sup.1 --R.sup.6 have the meanings specified in claim 1, with a benzyl halide selected from the group consisting of formula VI and VII
where A and R.sup.1 --R.sup.6 have the meanings specified in claim 1, and Y is chlorine or bromine, at a temperature in the range of 0.degree. to 60.degree. C., in the presence of a suitable metal, with or without the addition of catalytic amounts of a transition metal catalyst, the reaction being between either IV and VII or V and VI.

### Claim 8 (depends on 1)

A process for the preparation of a 1,3-deketo compound of the formula I as claimed in claim 1, wherein L=--C(O)CH.sub.2 C(O)--, or of the enol tautomer thereof, which comprises
subjecting a chalcone of formula X ##STR27## where A and R.sup.1 --R.sup.6 have the meanings specified in claim 1, to addition of bromine, then eliminating hydrogen bromide with a suitable base, and finally carrying out acid hydrolysis.

### Claim 9 (depends on 1)

A pharmaceutical composition effective for the treatment of a dermatological disorder associated with pathological keratinization, precancerose, carcinoma, corneopathy, rheumatic disorder or arthritic disorder, comprising an effective amount of said compound according to claim 1 and a pharmaceutically acceptable auxiliary.

### Claim 10 (depends on 13)

A method of treating a dermatological disorder associated with pathological keratinization, precancerose, carcinoma, corneopathy, rheumatic disorder or arthritic disorder, comprising topically administering said composition according to claim 13 to a patient in need thereof.

### Claim 11 (depends on 13)

A method of treating a dermatological disorder associated with pathological keratinization, precancerose, carcinoma, corneopathy, rheumatic disorder or arthritic disorder, comprising systematically administering said composition according to claim 13 to a patient in need thereof.