Method for producing 2-(4-N,N-dialkylamino-2-hydroxybenzoyl) benzoates

Patent metadata

Field	Value
Publication number	US-9682920-B2
Application number	US-201414901170-A
Country	US
Kind code	B2
Filing date	Jun 25, 2014
Priority date	Jun 27, 2013
Publication date	Jun 20, 2017
Grant date	Jun 20, 2017

Abstract

The present invention relates to a novel method for producing 2-(4-N,N-dialkylamino-2-hydroxybenzoyl) benzoates.

First claim

The invention claimed is:

1. A method for producing a benzoate compound of formula (I);

wherein
R 1 and R 2 are C 1 -C 6 -alkyl, propargyl or allyl; or
R 1 and R 2 together with the nitrogen atom are attached to form a ring with 2-9 carbon atoms; and
R 3 is C 1 -C 12 -alkyl or C 3 -C 10 -cycloalkyl, wherein
the method comprises the consecutive steps of:
(i) conducting esterification of a benzoic acid compound of formula (II) by means of a C 1 -C 12 alcohol or a cyclic C 3 -C 10 alcohol in the presence of an acidic catalyst to obtain a reaction mixture comprising the benzoate compound of formula (I):

(ii) forming a diluted reaction mixture by diluting the reaction mixture obtained in step (i) with an organic solvent and optionally with water,
(iii) neutralizing the diluted reaction mixture obtained in step (ii) with an aqueous base to form a diluted neutralized reaction mixture comprising an aqueous phase and an organic solvent phase,
(iv) conducting phase separation of the aqueous phase and the organic solvent phase,
(v) extracting the organic solvent phase separated according to step (iv) with an aqueous base until an amount of the benzoic acid compound according to formula (II) in the organic solvent phase is below 0.1%, and
(vi) filtering the organic solvent phase through an adsorbent.

2. The method according to claim 1 , wherein R 1 and R 2 are linear C 1 -C 3 -alkyl radicals.

3. The method according to claim 1 , wherein R 3 is a linear C 1 -C 6 -alkyl radical.

4. The method according to claim 1 wherein R 1 and R 2 are ethyl and R 3 is methyl.

5. The method according to claim 1 , wherein the organic solvent is toluene.

6. The method according to claim 5 , wherein the extraction of step (v) is carried out at a temperature which is in a range of 30-70° C.

7. The method according to claim 1 , wherein the aqueous base in step (v) is an aqueous NaOH solution.

8. The method according to claim 1 , wherein, between the phase separation step (iv) and the filtration step (vi), the process further comprises a step of drying the organic solvent phase with a drying agent.

9. The method according to claim 8 , wherein the absorbent is silica gel.

10. The method according to claim 8 , wherein the benzoate compound of formula (I) in the organic solvent phase during filtering according to step (vi) is present in a concentration within a range of 50-500 g/l.

11. The method according to claim 8 , wherein the adsorbent is present in an amount in a range from 0.1 to 1 g, based on 1 g of the benzoate compound of formula (I).

12. The method according to claim 1 , after the filtration step (vi), the process comprises a precipitation step (vii) which comprises precipitating the benzoate compound of formula (I) from the organic solvent phase with a precipitation aid.

13. The method according to claim 12 , wherein a ratio (v/v) of the organic solvent phase to the precipitation aid is in a range of 5:1 to 1:5.

14. The method according to claim 13 , wherein the precipitation aid is methyl t butylether.

15. The method according to claim 10 , wherein the concentration of the benzoate compound of formula (I) in the organic solvent phase during filtering according to step (vi) is the range of 100-350 g/l.

16. The method according to claim 10 , wherein the concentration of the benzoate compound of formula (I) in the organic solvent phase during filtering according to step (vi) is in the range of 200-300 g/l.

17. The method according to claim 11 , wherein the adsorbent is present in an amount in the range from 0.25 to 0.75 g, based on 1 g of the benzoate compound of formula (I).

18. The method according to claim 13 , wherein the ratio (v/v) of the organic solvent phase to the precipitation aid is in the range of 1:1 to 1:3.

19. The method according to claim 13 , wherein the ratio (v/v) of the organic solvent phase to the precipitation aid is in the range of 1:1.5 to 1:2.5.

20. A method for producing methyl 2-(4-N,N-diethylamino-2-hydroxybenzoyl) benzoate, wherein the method comprises the consecutive steps of:
(i) conducting esterification of 2-(4-N,N-diethylamino-2-hydroxybenzol) benzoic acid by means of methanol in the presence of sulfuric acid to obtain a reaction mixture comprising methyl 2-(4 N,N-diethylamino-2-hydroxybenzoyl) benzoate,
(ii) forming a diluted reaction mixture by diluting the reaction mixture obtained according to step (i) with toluene and optionally with water,
(iii) neutralizing the diluted reaction mixture with an aqueous ammonia solution to form a neutralized diluted reaction mixture having an aqueous phase and a toluene phase,
(iv) conducting phase separation of the aqueous phase and the toluene phase,
(v) extracting of the toluene phase at a temperature of 40-60° C. with an aqueous solution of NaOH until an amount of 2-(4-diethylamino-2-hydroxybenzoyl) benzoic acid in the organic solvent phase is below 0.1%,
(vi) filtering the toluene phase through silica gel, and
(vii) isolating the methyl 2-(4-N,N-diethylamino-2-hydroxybenzol) benzoate by causing precipitation with methyl t-butylether.

21. The method according to claim 20 , wherein after the extracting step (v) and before the filtering step (vi) the method further comprises drying and concentrating the toluene phase.

Assignees

• Dsm Ip Assets Bv

Inventors

• Zhang ji-yong
• Xu xu-feng

Classifications

• C07C227/18 Primary

  by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters · CPC title

• C07D295/033

  with the ring nitrogen atoms directly attached to carbocyclic rings · CPC title

• C07C227/40

  Separation; Purification · CPC title

• C07D209/02

  condensed with one carbocyclic ring · CPC title

• C07C229/52

  having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton · CPC title