Method for purification of 4-hydroxyacetophenone

Patent metadata

Field	Value
Publication number	US-10752571-B2
Application number	US-201716337467-A
Country	US
Kind code	B2
Filing date	Apr 21, 2017
Priority date	Oct 14, 2016
Publication date	Aug 25, 2020
Grant date	Aug 25, 2020

Abstract

Methods of purifying crude 4-hydroxyacetophenone using one or more solvents as well as products comprising or consisting of crystallized 4-hydroxyacetophenone and one, two or more solvent(s). The products may be obtained or obtainable from the methods for purifying crude 4-hydroxyacetophenone.

First claim

The invention claimed is:

1. A method of purifying crude 4-hydroxyacetophenone comprising:
(a) providing crude 4-hydroxyacetophenone,
(b) mixing the crude 4-hydroxyacetophenone of step (a) with one or more solvent(s) to obtain a mixture,
(c) optionally, heating the mixture obtained in step (b) to dissolve the 4-hydroxyacetophenone,
(d) optionally, adding an adsorbent to the mixture of step (b) or step (c), if present,
(e) optionally, cooling the mixture of step (b), step (c) or step (d), if present, to a temperature above the crystallization temperature of 4-hydroxyacetophenone,
(f) if step (d) is present, removing the adsorbent from the mixture of step (d) or step (e), if present,
(g) cooling of the mixture of step (b) or step (c), if present, or further cooling of the mixture obtained in step (e), if step (d) is not present, or step (f), if present, to a temperature below the crystallization temperature of 4-hydroxyacetophenone to induce crystallization of 4-hydroxyacetophenone and to obtain crystallized 4-hydroxyacetophenone,
(h) collecting the crystallized 4-hydroxyacetophenone,

optionally, carrying out steps (i) to (k) one or more times:
(i) dissolving the crystallized 4-hydroxyacetophenone of step (h) or step (k) in one or more solvent(s), optionally under heating, to produce a solution,
(j) cooling of the solution of step (i) to a temperature below the crystallization temperature of 4-hydroxyacetophenone to induce crystallization of 4-hydroxyacetophenone and to obtain crystallized 4-hydroxyacetophenone,
(k) collecting the crystallized 4-hydroxyacetophenone obtained in step (j),
(l) optionally, drying of the crystallized 4-hydroxyacetophenone of step (h) or step (k),
wherein at least one of the solvent(s) used in steps (b) and (i), if present, is independently selected from cyclohexane, ethyl acetate, butyl acetate, diethyl carbonate and dimethyl carbonate.

2. The method according to claim 1 , wherein the one or more solvent(s) used in steps (b) and (i), if present, independently comprise one of the following combinations:
ethanol/water,
ethyl acetate/cyclohexane,
dimethyl carbonate/cyclohexane,
butyl acetate/cyclohexane, or
diethyl carbonate/cyclohexane.

3. The method according to claim 1 , wherein in step(s) (b) and/or (i), if present, independently 0.5 to 70 wt. % of 4-hydroxyacetophenone, based on the total weight of the mixture obtained in step (b) or step (i), respectively, is combined with the one or more solvent(s).

4. The method according to claim 1 , wherein in step (c), the mixture obtained in step (b) is heated to reflux.

5. The method according to claim 1 , wherein in step (d), 0.1 to 25 wt. %, of the adsorbent, based on the total weight of the mixture of step (d), is added to the mixture of step (b) or step (c), if present.

6. The method according to claim 1 , wherein when step (c) and step (e) are present, in step (e) the mixture of step (c) or step (d), if present, is cooled to a temperature of 30 to 125° C.

7. The method according to claim 1 , wherein in step (g) the mixture of step (b) or step (c), if present, or the mixture of step (e), if step (d) is not present, or step (f), if present, or the solution obtained in step (i), if present, is cooled to a temperature of −10° C. to below room temperature.

8. The method according to claim 1 , wherein the drying of the crystallized 4-hydroxyacetophenone in step (1), if present, is carried out at reduced pressure, and at a temperature of 50 to 100° C., and wherein the drying time is between 1 and 48 hours.

9. A product consisting of crystallized 4-hydroxyacetophenone and one of the following:
a solvent selected from cyclohexane, ethyl acetate, butyl acetate, diethyl carbonate and dimethyl carbonate, or
two or more solvents each independently selected from ethanol, water, cyclohexane, ethyl acetate, butyl acetate, diethyl carbonate and dimethyl carbonate,
wherein the product is obtained by a method according to claim 1 .

10. A product according to claim 9 , wherein the total amount of the solvent(s) contained in the product is less than 10000 ppm.

11. A product according to claim 9 wherein the solvents contained in the product are chosen from:
(a) dimethyl carbonate, cyclohexane, water and ethanol, or
(b) dimethyl carbonate, cyclohexane and ethanol.

12. A product according to claim 10 , wherein the solvents contained in the product are chosen from:
(a) ethanol and water,
(b) dimethyl carbonate and cyclohexane,
(c) ethyl acetate and cyclohexane,
(d) butyl acetate and cyclohexane, and
(e) diethyl carbonate and cyclohexane.

13. The method of claim 1 , wherein the crystallized 4-hydroxyacetophenone obtained in step (h) or step (k) are dried until the total amount of the residual solvent(s) in the 4-hydroxyacetophenone is less than 10000 ppm.

14. The method of claim 13 , wherein the crystallized 4-hydroxyacetophenone is dried until the total amount of the residual solvent(s) in the 4-hydroxyacetophenone is less than 10000 ppm.

15. The method of claim 13 , wherein the crystallized 4-hydroxyacetophenone is dried until the total amount of the residual solvent(s) in the 4-hydroxyacetophenone is less than 5000 ppm.

16. The method of claim 13 , wherein the crystallized 4-hydroxyacetophenone is dried until the total amount of the residual solvent(s) in the 4-hydroxyacetophenone is less than 2500 ppm.

17. The method of claim 13 , wherein the crystallized 4-hydroxyacetophenone is dried until the total amount of the residual solvent(s) in the 4-hydroxyacetophenone is less than 1000 ppm.

18. The method of claim 1 , wherein when two or more solvents are used in steps (b) and (i), if present, each of the two or more solvents are independently selected from the group consisting of ethanol, water, cyclohexane, ethyl acetate, butyl acetate, diethyl carbonate and dimethyl carbonate.

19. The method of claim 1 , wherein 0.1 to 10 wt. % of the adsorbent, based on the total weight of the mixture obtained in step (d) is added to the mixture obtained in step (b) or step (c), if present.

20. The method of claim 7 , wherein in step (g) the mixture obtained in step (b) or step (c), if present, or the mixture obtained in step (e), if step (d) is not present, or step (f), if present, or the solution obtained in step (i), if present, is cooled to a temperature to a temperature of 0 to 20° C.

Assignees

• Symrise Ag
• Sino-High (China) Co Ltd

Inventors

• Pillai Ravikumar
• Siegel Sven
• Suess Ev
• Bolte Karolin
• Liuxin Yan

Classifications

• C07C49/825

  all hydroxy groups bound to the ring · CPC title

• C07C45/81 Primary

  by change in the physical state, e.g. crystallisation · CPC title

• C07C45/79 Primary

  by solid-liquid treatment; by chemisorption · CPC title

• C07C45/78 Primary

  Separation; Purification; Stabilisation; Use of additives · CPC title