Process for hydrolyzing 1,2,4-trihalobenzene

Patent metadata

Field	Value
Publication number	US-9643909-B2
Application number	US-201415026715-A
Country	US
Kind code	B2
Filing date	Sep 25, 2014
Priority date	Oct 4, 2013
Publication date	May 9, 2017
Grant date	May 9, 2017

Abstract

The present invention relates to a process for providing a compound of formula (I):

wherein Hal is a halogen, the process comprising the step of: reacting a compound of formula (II)

wherein Hal is defined as above, with an alkali metal sulfite of the formula X 2 SO 3 and an alkali metal hydroxide of the formula YOH, wherein X and Y are independently selected from an alkali metal.

First claim

The invention claimed is:

1. A process for providing a compound of formula (I):

wherein Hal is a halogen,
the process comprising the step of:
reacting a compound of formula (II)

wherein Hal is defined as above,
with an alkali metal sulfite of the formula X 2 SO 3 and an alkali metal hydroxide of the formula YOH, wherein X and Y are independently selected from an alkali metal.

2. The process of claim 1 , wherein the process is carried out in the presence of water.

3. The process of claim 2 , wherein the process is carried out in the presence of a C 1 -C 4 alcohol.

4. The process of claim 3 , wherein the process is carried in the absence of organic solvents apart from the optional presence of a C 1 -C 4 alcohol.

5. The process of claim 1 , wherein the process is carried out in in the absence of organic solvents.

6. The process of claim 1 , wherein about one molar equivalent of the compound of formula (II) is reacted in the presence of
(a) about 1.0 to about 1.4 molar equivalents of an alkali metal sulfite of formula X 2 SO 3 , wherein X is as defined in claim 1 ; and/or
(b) about 0.5 to about 4.0 molar equivalents of an alkali metal hydroxide of formula YOH, wherein Y is as defined in claim 1 ; and/or
(c) about 20 to about 40 molar equivalents of water; and/or
(d) up to 3 molar equivalents of a C 1 -C 4 alcohol, wherein apart from the C 1 -C 4 alcohol no further organic solvent is present.

7. The process of claim 1 , wherein the step of reacting the compound of formula (II) is carried out at a
(a) temperature of at least about 250° C.; and/or
(b) pressure of about 2050 kPa to about 5600 kPa.

8. The process of claim 1 , further comprising the step of reacting the compound of formula (I) to obtain a compound of formula (III)

wherein Hal is as defined in claim 1 , and R 1 is an alkali metal.

9. The process of claim 8 , wherein the step of reacting the compound of formula (I) to obtain a compound of formula (III) is carried out in the presence of an alkali metal hydroxide and carbon dioxide.

10. The process of claim 8 , further comprising the step of reacting the compound of formula (III) to obtain a compound of formula (IV)

wherein R 2 is —(C 1 -C 4 )alkyl, R″ is an alkali metal or —(C 1 -C 4 )alkyl, and Hal is a halogen.

11. The process of claim 10 , further comprising the step of reacting the compound of formula (IV) to obtain a compound of formula (V)

wherein R 2 and Hal are as defined in claim 10 .

12. The process of claim 1 , wherein
(a) Hal is selected from the group consisting of F, Cl, Br and I; and/or
(b) X and Y are independently selected from sodium or potassium; and/or
(c) R 1 is selected from sodium and potassium; and/or
(d) R 1′ is selected from sodium and potassium, or R 1′ is selected from ethyl and methyl.

13. The process of claim 11 , wherein the compound of formula (V) is

14. The process of claim 13 , wherein the process is carried out in the presence of water.

15. The process of claim 14 , wherein the process is carried out in the presence of a C 1 -C 4 alcohol.

16. The process of claim 15 , wherein the process is carried in the absence of organic solvents apart from the optional presence of a C 1 -C 4 alcohol.

17. The process of claim 13 , wherein the process is carried out in in the absence of organic solvents.

18. The process of claim 7 , wherein the step of reacting the compound of formula (II) is carried out at a temperature of at least about 265° C.

19. The process of claim 7 , wherein the step of reacting the compound of formula (II) is carried out at a temperature of about 265° C. to about 290° C.

Assignees

• Basf Se

Inventors

• Schmelebeck Gerald
• Ji Junmin
• Klauber Eric George
• Rack Michael
• Zierke Thomas
• Holub Nicole
• CORTES David

Classifications

• C07C37/02 Primary

  by substitution of halogen · CPC title

• C07C51/367

  by introduction of functional groups containing oxygen only in singly bound form · CPC title

• C07C65/05

  o-Hydroxy carboxylic acids · CPC title

• A01N37/40

  having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same aromatic ring system · CPC title

• C07C67/00

  Preparation of carboxylic acid esters · CPC title