Method for producing 3-alkylsulfanyl-2-chloro-N-(1-alkyl-1H-tetrazol-5-yl)-4-trifluoromethyl-benzamides

Patent metadata

Field	Value
Publication number	US-10457651-B2
Application number	US-201716342280-A
Country	US
Kind code	B2
Filing date	Oct 16, 2017
Priority date	Oct 20, 2016
Publication date	Oct 29, 2019
Grant date	Oct 29, 2019

Abstract

The substituents R1 and R2 therein are radicals such as alkyl and substituted phenyl.

First claim

The invention claimed is:

1. Method for preparing 3-alkylsulphanyl-2-chloro-N-(1-alkyl-1H-tetrazol-5-yl)-4-trifluoromethylbenzamides of the general formula (I), comprising reacting 2,3-dichlorobenzotrifluoride (II) with a thiolate (IV) to give a 2-alkysulphanyl-3-chlorobenzotrifluoride (III),
b) reacting the 2-alkysulphanyl-3-chlorobenzotrifluoride (III) with an organometallic reagent to give [2-chloro-3-(alkylsulphanyl)-4-(trifluoromethyl) phenyl] metal anion (V) and subsequently with a carboxylating reagent to give 3-alkylsulphanyl-2-chloro-4-trifluoromethylbenzoic acid (VI), and
c) effecting amidation with a 5-amino-1-alkyltetrazole (VII) with an activator in the presence of a base and an acyl transfer reagent to give 3-alkylsulphanyl-2-chloro-N-(1-alkyl-1H-tetrazol-5-yl)-4-trifluoromethylbenzamide (I):

and
d) where the substituents are as defined hereinbelow:
R 1 is C 1 -C 4 -alkyl or phenyl substituted by s radicals selected from the group consisting of chlorine, fluorine, methoxy and ethoxy,
R 2 is C 1 -C 4 -alkyl or phenyl substituted by s radicals selected from the group consisting of chlorine, fluorine, methoxy and ethoxy,
M 1 is lithium, sodium or potassium,
M 2 is Li, ZnX, MgX,
X is chlorine, bromine or iodine,
s is 0, 1, 2 or 3.

2. Method according to claim 1 , wherein the thiolate (IV) used is NaSMe or KSMe.

3. Method according to claim 1 , where R 1 is C 1 -C 4 -alkyl.

4. Method according to claim 1 , wherein R 1 is methyl.

5. Method according to any claim 1 , wherein M 1 is sodium.

6. Method according to claim 1 , wherein R 2 is methyl.

7. Method according to claim 1 , wherein the organometallic reagent used is an alkyllithium compound.

8. Method according to claim 1 , wherein the carboxylating reagent used is carbon dioxide.

9. Method according to claim 1 , wherein the activator used is thionyl chloride.

10. Method according claim 1 , wherein the acyl transfer reagent used is 1-methyl-1H-imidazole.

11. Compound of formula (III), in which

R 1 is C 1 -C 4 -alkyl or phenyl substituted by s radicals selected from the group consisting of chlorine, fluorine, methoxy and ethoxy, and
s is 0, 1, 2 or 3.

12. Compound of formula (III) according to claim 11 , where R 1 is methyl.

13. Compound of formula (VI) in which
R 1 is C 1 -C 4 -alkyl or phenyl substituted by s radicals from the group consisting of chlorine, fluorine, methoxy and ethoxy, and
s is 0, 1, 2 or 3

14. Compound of formula (VI) according to claim 13 , where R 1 is methyl.

Assignees

• Bayer Cropscience Ag

Inventors

• Gallenkamp Daniel
• Ford Mark James

Classifications

• C07C323/20

  with singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring · CPC title

• C07C319/14

  of sulfides · CPC title

• C07D257/06 Primary

  with nitrogen atoms directly attached to the ring carbon atom · CPC title

• C07C323/09

  having sulfur atoms of thio groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton · CPC title

• C07C323/62

  having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton · CPC title