Process for preparing 3-chloro-2-vinylphenylsulfonates

Patent metadata

Field	Value
Publication number	US-10618872-B2
Application number	US-201615554271-A
Country	US
Kind code	B2
Filing date	Feb 29, 2016
Priority date	Mar 5, 2015
Publication date	Apr 14, 2020
Grant date	Apr 14, 2020

Abstract

The present invention relates to a new process for preparing 3-chloro-2-vinylphenylsulfonate derivatives.

First claim

The invention claimed is:

1. A process for preparing one or more 3-chloro-2-vinylphenylsulfonate derivatives of formula (I),

wherein
R 1 represents C 1 -C 6 -alkyl, phenyl, 4-methylphenyl or benzyl,
comprising
(A) reacting 3-chloro-2-methylphenol of formula (II)

with a compound of formula (III),

wherein
Hal represents F or Cl and
R 2 represents F, Cl, F 3 C, F 2 HC, Cl 3 C, Cl 2 HC, ClH 2 C or Cl 3 CO,
or reacting the 3-chloro-2-methylphenol of formula (II)
with an acid derivative of formula (IV),

wherein
R 3 and R 4 independently from each other represent F 3 C, F 2 HC, Cl 3 C, Cl 2 HC, or ClH 2 C,
or reacting the 3-chloro-2-methylphenol of formula (II)
with triphosgene
in the presence of a base and a solvent
to form a compound of formula (V)

wherein
R 5 represents F, Cl, CCl 3 , CHCl 2 , CH 2 Cl, CF 3 , CHF 2 or 3-chloro-2-methylphenoxy;
(B) reacting one or more compounds of formula (V) with a chlorinating agent to produce one or more compounds of formula (VI)

wherein
R 6 represents F, Cl, CCl 3 , CHCl 2 , CH 2 Cl, CF 3 , CHF 2 or 3-chloro-2-(dichloromethyl)phenoxy;
(C) reacting the compound of formula (VI) under acidic conditions or at elevated temperature in water to produce 2-chloro-6-hydroxybenzaldehyde (VII)

(D) reacting the compound of formula (VII) or an alkaline or alkaline earth metal salt thereof in the presence of a solvent with a compound of formula (VIII)
Me-Q  (VIII),

wherein
Q represents Li, Na, K, MgCl, MgBr or, MgI
to produce 3-chloro-2-(1-hydroxyethyl)phenol (IX)

and
(E) forming 3-chloro-2-vinylphenylsulfonate derivatives of formula (I) by reacting the compound of formula (IX) in the presence of a base with a compound of formula (X)
R 1 —SO 2 —W  (X),

wherein
W represents F, Cl, Br or OSO 2 R 1 .

2. The process according to claim 1 , wherein
R 1 represents methyl, ethyl, n-propyl, i-propyl, n-butyl, phenyl, 4-methylphenyl or benzyl;
R 2 represents F, Cl, F 3 C, F 2 HC, Cl 3 C, Cl 2 HC, ClH 2 C or Cl 3 CO;
R 3 and R 4 independently from each other represent F 3 C, F 2 HC, Cl 3 C, Cl 2 HC or ClH 2 C;
R 5 represents F, Cl, CCl 3 , CHCl 2 , CH 2 Cl, CF 3 , CHF 2 or 3-chloro-2-methylphenoxy;
R 6 represents F, Cl, CCl 3 , CHCl 2 , CH 2 Cl, CF 3 , CHF 2 or 3-chloro-2-(dichloromethyl) phenoxy;
W represents F, Cl or OSO 2 R 1 ; and
Q represents Na, K, MgCl or MgBr.

3. The process according to claim 1 , wherein
R 1 represents methyl, ethyl, n-propyl, phenyl, or 4-methylphenyl;
R 2 represents F, Cl, F 3 C, F 2 HC, Cl 3 C, Cl 2 HC, ClH 2 C or Cl 3 CO;
R 3 and R 4 independently from each other represent F 3 C, Cl 3 C, Cl 2 HC, or ClH 2 C;
R 5 represents F, Cl, CCl 3 , CHCl 2 , CH 2 Cl, CF 3 , F 2 HC or 3-chloro-2-methylphenoxy;
R 6 represents F, Cl, CCl 3 , CHCl 2 , CH 2 Cl, CF 3 , F 2 HC or 3-chloro-2-(dichloro)methylphenoxy;
W represents F, Cl or OSO 2 R 1 ; and
Q represents Na, K, MgCl or MgBr.

4. The process according to claim 1 , wherein
R 1 represents methyl or 4-methylphenyl;
R 2 represents F, Cl, F 3 C or Cl 3 CO;
R 3 and R 4 independently from each other represent F 3 C or Cl 3 C;
R 5 represents F, Cl, CCl 3 , F 3 C or 3-chloro-2-methylphenoxy;
R 6 represents F, Cl, CCl 3 ,F 3 C or 3-chloro-2-(dichloro)methylphenoxy;
W represents F, Cl or OSO 2 R 1 ; and
Q represents MgCl or MgBr.

5. The process according to claim 1 , wherein in (A), 3-methylpyridine and 2-methyl-5-ethylpyridine are used as base and dichloromethane, toluene, chlorobenzene or dichloromethane as solvent.

6. The process according to claim 1 , wherein in (B), chlorine is used as chlorinating agent.

7. The process according to claim 1 , wherein in (C), HCOOH, CH 3 COOH, H 2 SO 4 , or HCl is used as acid.

8. The process according to claim 1 , wherein (C) is performed in water at temperatures between 80° C. and 140° C.

9. The process according to claim 1 , wherein in (D), MeMgCl or MeMgBr is used as organometallic reagent and THF, 2-Me-THF, toluene or xylene as solvent.

10. The process according to claim 1 wherein in (E), alkali metal carbonate or hydroxide, triethylamine or pyridine is used as base.

11. The process for preparing one or more 3-chloro-2-vinylphenylsulfonate derivatives of formula (I),

according to claim 1 further comprising
(F) transforming one or more compounds of formula (IX) into 3-chloro-2-vinylphenol of formula (XII)

in the presence of an acid and a solvent and
(G) transforming 3-chloro-2-vinylphenol of formula (XII) into a 3-chloro-2-vinylphenylsulfonate derivative of formula (I) in the presence of one or more compounds of formula (X) and a base.

12. The process according to claim 1 , comprising reacting the 3-chloro-2-methylphenol of formula (II) with the compound of formula (III).

13. The process according to claim 1 , comprising reacting the 3-chloro-2-methylphenol of formula (II) with the acid derivative of formula (IV).

14. The process according to claim 1 , comprising reacting the 3-chloro-2-methylphenol of formula (II) with triphosgene.

15. A compound of formula (V)

wherein
R 5 represents F, Cl, CCl 3 , CHCl 2 , CH 2 Cl, CF 3 , CHF 2 or 3-chloro-2-methylphenoxy.

Assignees

• Bayer Cropscience Ag

Inventors

• Brüchner Peter
• Himmler Thomas
• Pazenok Sergii
• Ford Mark James

Classifications

• C07C303/28 Primary

  by reaction of hydroxy compounds with sulfonic acids or derivatives thereof · CPC title

• C07C45/43 Primary

  of >CX2 groups, X being halogen · CPC title

• C07C69/63

  of saturated acids · CPC title

• C07C67/14 Primary

  from carboxylic acid halides · CPC title

• C07C67/287

  by introduction of halogen; by substitution of halogen atoms by other halogen atoms · CPC title