# US 10,118,882 B2 · Process for the preparation of substituted phenyl ketones

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- Number: US 10,118,882 B2
- Document ID: US10118882B2
- Status: Granted
- Kind: B2
- Application number: 15/736,974
- Filed: 2016-06-14
- Published: 2018-06-21
- Granted: 2018-11-06
- Earliest claimed: 2015-06-17
- Assignees: BASF Agro B.V.
- Applicants: BASF Agro B.V.
- Inventors: Joachim Gebhardt; Daniel Saelinger; Manfred Ehresmann; Roland Goetz
- Web page: https://patentgrep.com/patent/US10118882B2

## CPC

- C07C 45/004: {by reaction with organometalhalides}
- C07C 45/64: by introduction of functional groups containing oxygen only in singly bound form
- C07C 49/80: containing halogen
- C07C 49/84: containing ether groups, [IMAGE cpc-sch-C07C-0958.gif] groups,[IMAGE cpc-sch-C07C-0959.gif] groups, or[IMAGE cpc-sch-C07C-0960.gif] groups
- C07D 249/08: 1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D 301/02: Synthesis of the oxirane ring
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)

## Abstract

The present invention relates to a process for providing substituted phenyl ketones. Furthermore, the invention relates to the use of substituted phenoxyphenyl ketones obtained by the inventive process for the preparation of triazoles.

## Claims

### Claim 1

A process for the preparation of the ketone compounds of formula (II)
wherein
X is F or Cl and
R1 is C1-C6-alkyl or C3-C8-cycloalkyl;
comprising the following step:
(i) reacting a compound of the formula (III)
with R′—Mg-Hal (IV) or Mg, and R1C(═O)Cl (V),
wherein the Grignard reagent is added as solution in a solvent selected from tetrahydrofurane (THF), 1,4-dioxane, diethylether and 2-methyl-tetrahydrofurane,
wherein the temperature during the reaction with (V) is kept in the range of −20° C. to 10° C.,
wherein
R1 is C1-C4-alkyl or C3-C6-cycloalkyl and
Hal is halogen.

### Claim 2 (depends on 1)

The process of claim 1, wherein a Cu(I)-catalyst is added in step (i).

### Claim 3 (depends on 2)

The process of claim 2, wherein the Cu(I)-catalyst is Cu(I)Cl.

### Claim 4 (depends on 1)

The process of claim 1, wherein R′ is iso-propyl.

### Claim 5 (depends on 1)

The process of claim 1, wherein Hal is Br or Cl, in particular Br.

### Claim 6 (depends on 1)

The process of claim 1, wherein X is F.

### Claim 7 (depends on 1)

The process of claim 1, wherein R1 is selected from CH3, CH(CH3)2 and cyclopropyl.

### Claim 8 (depends on 1)

The process of claim 1, wherein the temperature during the reaction with (V) is kept in the range of −15° C. to 5° C.

### Claim 9 (depends on 1)

The process of claim 1, wherein the temperature during the reaction with (V) is kept in the range of −10° C. to −5° C.

### Claim 10

A process for the preparation of triazole compounds of the formula (IC)
wherein R1 is C1-C6-alkyl or C3-C8-cycloalkyl; and
R2 is hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-C1-C6-alkyl, phenyl, phenyl-C1-C4-alkyl, phenyl-C2-C4-alkenyl or phenyl-C2-C4-alkynyl;
wherein the aliphatic moieties of R2 are not further substituted or do carry one, two, three or up to the maximum possible number of identical or different groups
R12a which independently are selected from:
R12a halogen, OH, CN, nitro, C1-C4-alkoxy, C3-C8-cycloalkyl, C3-C8-halocycloalkyl and C1-C4-halogenalkoxy;
wherein the cycloalkyl and/or phenyl moieties of R2 are not further substituted or do carry one, two, three, four, five or up to the maximum number of identical or different groups R12b which independently are selected from:
R12b halogen, OH, CN, nitro, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-halogenalkyl, C3-C8-cycloalkyl, C3-C8-halocycloalkyl and C1-C4-halogenalkoxy; and
R4 is F or Cl
comprising the following steps:
(i) preparing a compound of formula (II)
by reacting a compound of the formula (III)
with R′—Mg-Hal (IV) or Mg, and R1C(═O)Cl (V),
wherein the Grignard reagent is added as solution in a solvent selected from tetrahydrofurane (THF), 1,4-dioxane, diethylether and 2-methyl-tetrahydrofurane,
wherein the temperature during the reaction with (V) is kept in the range of −20° C. to 10° C.,
wherein
R′ is C1-C4-alkyl or C3-C6-cycloalkyl and
Hal is halogen;
(ii) reacting compound (II) as defined in step (i) with a phenol derivative of formula (VI)
wherein
R″ is hydrogen or an alkali metal kation;
in the presence of a base if R″ is hydrogen to result in a ketone of formula (IA)
(iii) reacting the ketone of the formula (IA) as defined in step (ii) to oxiranes (IB);
and
(iv) reacting the oxirane (IB) as defined in step (iii) with 1H-1,2,4-triazole in the presence of a base to obtain compounds (IC), wherein R2 is hydrogen (compounds IC-1);
and, for obtaining compounds wherein R2 is different from hydrogen (compounds IC-2);
(v) derivatizing the compound of formula (IC-1) as defined in step (iv) under basic conditions with R2-LG, wherein LG is a nucleophilically replaceable leaving group; to result in compounds (IC-2).

### Claim 11 (depends on 10)

The process of claim 10, wherein the reaction to the oxirane (IB) is carried out with a trimethylsulf(ox)onium halide ((CH3)3S+ (O)Hal−) (VII), wherein Hal is halogen, or trimethylsulfonium methylsulfate of the formula (VIII) (CH3)3S+ CH3SO4−.

### Claim 12 (depends on 10)

The process of claim 10, wherein R4 is Cl.