Method for preparing 3-substituted 2-vinylphenyl sulfonates

Patent metadata

Field	Value
Publication number	US-10647667-B2
Application number	US-201716466273-A
Country	US
Kind code	B2
Filing date	Nov 28, 2017
Priority date	Dec 5, 2016
Publication date	May 12, 2020
Grant date	May 12, 2020

Abstract

The present invention relates to a method for preparing 3-substituted 2-vinylphenyl sulfonates.

First claim

The invention claimed is:

1. Method for preparing a vinylphenyl sulfonate of formula (I):

in which R 1 is C 1 -C 6 -alkyl, phenyl, 4-methylphenyl or benzyl, and
R 2 is halogen or methyl,

comprising reacting
(a) a compound of formula (II)

with an activator in the presence of a base to give a compound of formula (III)

wherein one or more compounds are used as activators selected from the group consisting of thionyl chloride, phosgene, diphosgene, triphosgene, thiophosgene and chloroformic esters,
and reacting

(b) the compound of the formula (III) in the presence of a base with a compound of formula (IV)
R 1 —SO 2 —R 3   (IV),

where R 3 is F, Cl, Br or OSO 2 R 1 and R 1 is as defined in formula (I),
to give the vinylphenyl sulfonate of the formula (I).

2. Method according to claim 1 , wherein a) and b) are carried out in a one-pot process.

3. Method according to claim 1 , wherein one or more bases selected from the group consisting of trialkylamines, pyridyl bases, alkoxide bases and amidine bases is used in (a) and (b).

4. Method according to claim 3 , wherein the base used is tributylamine.

5. Method according to claim 1 , wherein one or more solvents are used in (a) and (b) selected from the group consisting of petroleum ether, n-hexane, n-heptane, cyclohexane, methylcyclohexane, toluene, o-xylene, m-xylene, p-xylene, decaline, chlorobenzene, 1,2-dichlorobenzene, dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, 1,4-dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, diglyme, anisole, acetonitrile, propionitrile, n-butyronitrile, isobutyronitrile, benzonitrile, ethyl acetate, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide.

6. Method according to claim 1 , wherein the solvent used is toluene or methyl tert-butyl ether.

7. Method according to claim 1 , wherein
R 1 is methyl, ethyl, n-propyl, isopropyl, n-butyl, phenyl, 4-methylphenyl or benzyl,
R 2 is Cl, F, Br, I or methyl, and
R 3 is F, Cl or OSO 2 R 1 .

8. Method according to claim 1 , wherein the compound of the formula (II) is obtained by reacting a compound of the formula (VI) or an alkali metal salt or alkaline earth metal salt of the compound of formula (VI)

with at least one compound of formula (VII)
Me-Q  (VII)

in the presence of a solvent, where Q is Li, Na, K, MgCl, MgBr or MgI.

9. Method according to claim 8 , wherein a deprotonating agent is first added to the compound of the formula (VI) before reacting with the compound of the formula (VII), wherein the deprotonating agent is not a compound of the formula (VII).

10. Method according to claim 9 , wherein an alkali metal alkoxide and/or alkali metal hydroxide is used as deprotonating agent.

11. Method according to claim 10 , wherein the deprotonating agent is selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium methoxide and potassium tert-butoxide.

12. Method according to claim 8 , wherein the compound of the formula (VI) is obtained by reacting a compound of formula (VIII)

where R 2 is methyl, I, Br or Cl,
with a hydroxide base.

13. Method according to claim 12 , wherein the hydroxide base used is an aqueous potassium hydroxide solution or an aqueous sodium hydroxide solution.

14. Method according to claim 12 , wherein the reaction of the compound of the formula (VIII) to the compound of the formula (VI) is carried out in the presence of an amide solvent, or a mixture of amide solvent or diglyme with ether solvent or aromatic solvent.

15. Compound of formula (V),

in which R 2 is halogen or methyl;
X is C or S, Y is S or O, and wherein X and Y cannot both be S.

Assignees

• Bayer Cropscience Ag

Inventors

• Gallenkamp Daniel
• Ford Mark James
• Brohm Dirk
• Erver Florian

Classifications

• C07C303/28 Primary

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

• C07D319/08

  condensed with carbocyclic rings or ring systems · CPC title

• C07C37/002

  by transformation of a functional group, e.g. oxo, carboxyl · CPC title

• C07C37/20 Primary

  using aldehydes or ketones · CPC title

• C07C309/66

  Methanesulfonates · CPC title