Selective hydrolysis and alcoholysis of chlorinated benzenes

Patent metadata

Field	Value
Publication number	US-10093607-B2
Application number	US-201415026878-A
Country	US
Kind code	B2
Filing date	Oct 2, 2014
Priority date	Oct 4, 2013
Publication date	Oct 9, 2018
Grant date	Oct 9, 2018

Abstract

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

wherein R is hydrogen or R′, wherein R′ is —(C 1 -C 4 )alkyl, and 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 alkoxide of the formula XOR′, wherein X is an alkali metal, and R′ is defined as above.

First claim

The invention claimed is:

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

wherein R is hydrogen or R′, wherein R′ is (C 1 -C 4 )alkyl, and Hal is chloro,
the process comprising the step of:
reacting a compound of formula (II)

wherein Hal is defined as above,
with an alkali metal alkoxide of the formula XOR′, wherein X is an alkali metal, and R′ is defined as above,
wherein the alkali metal alkoxide of formula XOR′ is added to the reaction mixture in the form of an alcoholic solution in an alcohol of formula HOR′ having a concentration of 25 wt.-% to 67 wt.-%, based on the weight of the total weight of the alcohol HOR′ and the alkali metal alkoxide of the formula XOR′; and
wherein the step of reacting the compound of formula (II) with an alkali metal alkoxide of formula XOR′ is carried out at a temperature of at least 150° C.

2. The process according to claim 1 , wherein the process is carried out in a solvent, wherein the solvent is an alcohol of formula HOR′, wherein R′ is as defined in claim 1 .

3. The process according to claim 1 , wherein about one molar equivalent of the compound of formula (II) is reacted in the presence of 2 to 3 molar equivalents of the alkali metal alkoxide of formula XOR′ in 2 to 14 molar equivalents of a solvent of formula HOR′.

4. The process according to claim 3 , wherein about one molar equivalent of the compound of formula (II) is reacted in the presence of 2.2 to 2.6 molar equivalents of the alkali metal alkoxide of formula XOR′ in 11.5 to 12.5 molar equivalents of a solvent of formula HOR′.

5. The process according to claim 4 , wherein about one molar equivalent of the compound of formula (II) is reacted in the presence of about 2.4 molar equivalents of the alkali metal alkoxide of formula XOR′ in about 12 molar equivalents of a solvent of formula HOR′.

6. The process according to claim 1 , wherein the step of reacting the compound of formula (II) with an alkali metal alkoxide of formula XOR′ is carried out at 150° C. to 190° C.

7. The process according to claim 1 , wherein the step of reacting the compound of formula (II) with an alkali metal alkoxide of formula XOR′ is carried out within 30 to 180 minutes.

8. The process according to claim 7 , wherein the step of reacting the compound of formula (II) with an alkali metal alkoxide of formula XOR′ is carried out within 45 to 120 minutes.

9. The process according to claim 1 , wherein the compound of formula (I) is obtained in a 2,5-regioselectivity of at least 72.

10. The process according to claim 9 , wherein the compound of formula (I) is obtained in a 2,5-regioselectivity of at least 77%.

11. The process according to claim 1 , wherein the compound of formula (I), in which R is hydrogen or (C 1 -C 4 )alkyl, is obtained in a yield of at least 70%.

12. The process according to claim 11 , wherein the compound of formula (I), in which R is hydrogen or —(C 1 -C 4 )alkyl, is obtained in a yield of at least 74%.

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

wherein R 1 is an alkali metal.

14. The process according to claim 13 , 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.

15. The process according to claim 13 , 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 1′ is an alkali metal or is the same as R 2 .

16. The process according to claim 15 , 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 15 .

17. The process according to claim 1 , wherein
(b) R is selected from hydrogen and R′; and R′ is selected from methyl and ethyl; and/or
(c) X is sodium or potassium.

18. The process according to claim 17 , wherein
(f) R′ is methyl.

19. The process according to claim 17 , wherein
(g) X is sodium.

20. The process according to claim 15 , wherein
(a) R is selected from hydrogen and R′; and R′ is selected from methyl and ethyl; and/or
(b) X is 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 R 2 , and R 2 is selected from ethyl and methyl.

21. The process according to claim 16 , wherein the compound of formula (V) is

22. The process according to claim 20 , wherein
(h) R 1′ is R 2 , and R 2 is methyl.

Assignees

• Basf Se

Inventors

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

Classifications

• C07C41/16

  by reaction of esters of mineral or organic acids with hydroxy or O-metal groups · CPC title

• C07C51/377 Primary

  by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups {(C07C51/36 - C07C51/373 take precedence)} · CPC title

• C07F1/04

  Sodium compounds · CPC title

• C07F1/005

  without C-Metal linkages · CPC title

• C07C67/297

  by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups · CPC title