# US 4,399,309 A · Preparation of 1-aryloxy-methyl ketones

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- Number: US 4,399,309 A
- Document ID: US4399309A
- Status: Granted
- Kind: A
- Application number: 06/335,942
- Filed: 1981-12-30
- Granted: 1983-08-16
- Earliest claimed: 1981-01-16
- Assignees: Bayer Aktiengesellschaft
- Inventors: Manfred Jautelat; Jorg Stetter; Dieter Arlt
- Web page: https://patentgrep.com/patent/US4399309A

## CPC

- C07C 41/16: by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
- C07C 45/42: by hydrolysis
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

A process for the preparation of a 1-aryloxy-methyl ketone of the formula ##STR1## in which R.sup.1, R.sup.2 and R.sup.3 each independently is hydrogen, optionally substituted alkyl, alkenyl, alkynyl or optionally substituted aryl, or R.sup.1 and R.sup.2 together are an alkylene chain, R.sup.4 each independently is halogen, alkyl, alkoxy, optionally substituted aryl or nitro, and n is 0, 1, 2 or 3, comprising hydrolyzing a 1-halogeno-2-aryloxy-1-alkene of the formula ##STR2## in which Hal is chlorine or bromine, under acidic conditions at a temperature from about 20.degree. to 150.degree. C. until it is about 95 to 100% complete, adding a base, and then bringing the reaction to completion under weakly alkaline conditions at about 20.degree. to 150.degree. C. Advantageously all stages of the reaction are effected in a single vessel at a temperature from about 40.degree. to 100.degree. C. and in the presence of an inert organic solvent, optionally in admixture with water as a solution or as a two-phase system, about 1 mol of a monobasic acid and 2 mols of alkali metal carbonate being employed per mol of the 1-halogeno-2-aryloxy-1-alkene. The end products are known intermediates for fungicides.

## Claims

### Claim 1

A process for the preparation of a 1-aryloxy-methyl ketone of the formula ##STR10## in which R.sup.1 and R.sup.2 each independently is alkyl, alkenyl or alkynyl with up to 4 carbon atoms, or phenyl, the alkyl and phenyl groups optionally being substituted by halogen, nitro, phenyl, halogenophenyl, alkoxy with up to 3 carbon atoms, phenoxy or halogenophenoxy, or
R.sup.1 and R.sup.2 together form an alkylene chain with 2 to 7 carbon atoms,
R.sup.3 is alkyl with up to 10 carbon atoms or aryl with 6 to 10 carbon atoms, the alkyl or aryl radicals optionally being substituted by halogen, nitro, phenyl, halogenophenyl, alkoxy with up to 3 carbon atoms, phenoxy or halogenophenoxy,
R.sup.4 each independently is halogen, alkyl, alkoxy, nitro, alkyl or alkoxy with up to 3 carbon atoms, phenyl or halogenophenyl, and
n is 0, 1, 2 or 3,
comprising contacting a 1-halogeno-2-aryloxy-1-alkene of the formula ##STR11## in which Hal is chlorine or bromine, with acid at a temperature from about 20.degree. to 150.degree. C., until about 95 to 100% of the alkene reacts, adding a base, and then allowing the reaction to go to completion under weakly alkaline conditions by continuing contact of the reactants at about 20.degree. to 150.degree. C.

### Claim 2 (depends on 1)

A process according to claim 1, wherein all stages of the reaction are effected in a single vessel.

### Claim 3 (depends on 1)

A process according to claim 1, wherein the acid reaction and the subsequent alkaline reaction are each carried out in the temperature range of about 40.degree. to 100.degree. C.

### Claim 4 (depends on 1)

A process according to claim 1, wherein the acid reaction is effected in the presence of hydrochloric acid, sulphuric acid, formic acid, acetic acid, trifluoro-acetic acid, methanesulphonic acid or p-toluenesulphonic acid.

### Claim 5 (depends on 1)

A process according to claim 1, wherein the basic substance is an alkali metal carbonate, alkaline earth metal carbonate, alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal bicarbonate, alkaline earth metal oxide or amine.

### Claim 6 (depends on 1)

A process according to claim 1, wherein the acid reaction is effected in the presence of an inert organic solvent in admixture with water as a solution or as a two-phase system.

### Claim 7 (depends on 1)

A process according to claim 1, wherein about 1 mol of monobasic acid and 2 mols of alkali metal carbonate are employed per mol of the 1-halogeno-2-aryloxy-1-alkene.

### Claim 8 (depends on 1)

A process according to claim 1, in which
n is 0, 1 or 2.

### Claim 9 (depends on 1)

A process according to claim 1, in which Hal is chlorine.

### Claim 10 (depends on 9)

A process according to claim 9, wherein all stages of the reaction are effected in a single vessel at a temperature from about 40.degree. to 100.degree. C. and in the presence of an inert organic solvent, optionally in admixture with water as a solution or as a two-phase system, about 1 mol of a monobasic acid and 2 mols of alkali metal carbonate being employed per mol of the 1-halogeno-2-aryloxy-1-alkene.