Process for the preparation of amides from hindered anilines containing a perhaloalkyl group

Patent metadata

Field	Value
Publication number	US-9598369-B2
Application number	US-201414782033-A
Country	US
Kind code	B2
Filing date	Apr 1, 2014
Priority date	Apr 2, 2013
Publication date	Mar 21, 2017
Grant date	Mar 21, 2017

Abstract

The present invention provides a novel and improved process for the production of the production of hindered anilines containing perfluoroalky groups in good yield any by using close to stoichiometric amounts of acylating agent.

First claim

The invention claimed is:

1. A method for the preparation of

comprising reacting a compound of formula (I) with a compound of formula (II) in the presence of acid to obtain a compound of formula (III):

then
Step b)
reacting the compound of formula (III) with a compound of formula (IV) to obtain a compound of formula (V):

then
Step c)
reacting the compound of formula (V) with aqueous base to obtain a compound of formula (VI):

wherein
X 1 and X 2 each independently are halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkoxymethyl, C 1 -C 4 -alkylsulphonyl, C 1 -C 4 -haloalkylsulphonyl, C 1 -C 4 -alkylsulphinyl, C 1 -C 4 -haloalkylsulphinyl, C 1 -C 4 -alkylthio, C 1 -C 4 -haloalkylthio,
X 3 is heptafluoroprop-2-yl, 1-[chloro(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl, 1-[bromo(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl or nonafluorobut-2-yl;
X 4 is a leaving group selected from halogen, C 1 -C 6 -alkyl-C(O)O—, phenyl-C(O)O—, C 1 -C 6 -alkoxy-C(O)O—, phenoxy-C(O)O—, benzyloxy-C(O)O— and imidazol-1-yl;
R 1 is H, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl,
R 2 is C 1 -C 4 -alkyl
R 3 is H, fluorine, methoxy;
R 3a is H or CN,
Q 1 is 4-cyano-phenyl, 3-pyridyl or 4-pyridyl.

2. A method according to claim 1 wherein
X 1 and X 2 each independently are halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkoxymethyl,
X 3 is heptafluoroprop-2-yl, 1-[chloro(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl, 1-[bromo(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl or nonafluorobut-2-yl;
X 4 is a leaving group selected from halogen, C 1 -C 6 -alkyl-C(O)O—, phenyl-C(O)O—, C 1 -C 6 -alkoxy-C(O)O—;
R 1 is H, C 1 -C 4 alkyl,
R 2 is methyl or ethyl
Q 1 is 4-cyano-phenyl, 3-pyridyl or 4-pyridyl.

3. A method according to claim 1 wherein
X 1 and X 2 each independently are halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkoxymethyl,
X 3 is 1-[chloro(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl, 1-[bromo(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl;
X 4 is a leaving group selected from halogen, C 1 -C 6 -alkyl-C(O)O—, phenyl-C(O)O—, C 1 -C 6 -alkoxy-C(O)O—;
R 1 is H, C 1 -C 4 alkyl,
R 2 is methyl or ethyl
Q 1 is 3-pyridyl or 4-pyridyl.

4. A method according to claim 1 wherein
X 1 and X 2 each independently are halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy,
X 3 is heptafluoroprop-2-yl;
X 4 is a leaving group selected from halogen, C 1 -C 6 -alkyl-C(O)O—;
R 1 is H, methyl,
R 2 is ethyl
Q 1 is 4-pyridyl.

5. A method according to claim 1 wherein
X 1 and X 2 each independently are halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy,
X 3 is heptafluoroprop-2-yl;
X 4 is a leaving group selected from halogen, C 1 -C 6 -alkyl-C(O)O—;
R 1 is H, methyl,
R 2 is ethyl
Q 1 is 4-pyridyl.

6. A method according to claim 1 wherein
X 1 and X 2 each independently are halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy,
X 3 is 1-[chloro(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl;
X 4 is a leaving group selected from halogen, C 1 -C 6 -alkyl-C(O)O—;
R 1 is H, methyl,
R 2 is ethyl
Q 1 is 4-pyridyl.

7. A method according to claim 1 wherein
X 1 and X 2 each independently are halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy,
X 3 is 1-[bromo(difluoro)methyl]-1,2,2,2-tetrafluoro-ethyl;
X 4 is a leaving group selected from halogen, C 1 -C 6 -alkyl-C(O)O—;
R 1 is H, methyl,
R 2 is ethyl
Q 1 is 4-pyridyl.

8. A method according to claim 1 wherein
X 1 and X 2 each independently are halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy,
X 3 is nonafluorobut-2-yl;
X 4 is a leaving group selected from halogen, C 1 -C 6 -alkyl-C(O)O—;
R 1 is H, methyl,
R 2 is ethyl
Q 1 is 4-pyridyl.

9. A method according to claim 1 wherein
R 3 is methoxy and R 3a is H.

10. A method according to claim 1 wherein
R 3 is fluorine and R 3a is H.

11. A method according to claim 1 wherein
R 3 is H and R 3a is CN.

12. A method according to claim 1 wherein
R 3 is H and R 3a is H.

Assignees

• Syngenta Participations Ag

Inventors

• Smits Helmars
• Pitterna Thomas
• Hueter Ottmar Franz
• Edmunds Andrew
• Stoller Andre
• Jung Pierre Joseph Marcel

Classifications

• C07D213/82

  in position 3 · CPC title

• C07C255/57

  containing cyano groups and carboxyl groups, other than cyano groups, bound to the carbon skeleton · CPC title

• C07C253/30

  by reactions not involving the formation of cyano groups · CPC title

• C07C233/15

  with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring · CPC title

• C07D213/81 Primary

  Amides; Imides · CPC title