Process for producing 4,4′-dichlorodiphenyl sulfoxide

Patent metadata

Field	Value
Publication number	US-12168642-B2
Application number	US-202017429210-A
Country	US
Kind code	B2
Filing date	Feb 6, 2020
Priority date	Feb 8, 2019
Publication date	Dec 17, 2024
Grant date	Dec 17, 2024

Abstract

The invention relates to a process for producing 4,4′-dichlorodiphenyl sulfoxide comprising: (I) reacting thionyl chloride, chlorobenzene and aluminum chloride in a molar ratio of thionyl chloride:chlorobenzene:aluminum chloride of 1:(6 to 9):(1 to 1.5) at a temperature in the range from 0 to below 20° C., forming an intermediate reaction product and hydrogen chloride; (II) mixing aqueous hydrochloric acid and the intermediate reaction product at a temperature in the range from 70 to 110° C. to obtain an organic phase comprising 4,4′-dichlorodiphenyl sulfoxide and an aqueous phase; (III) cooling the organic phase comprising the 4,4′-dichlorodiphenyl sulfoxide to a temperature below the saturation point of 4,4′-dichlorodiphenyl sulfoxide to obtain a suspension comprising crystallized 4,4′-dichlorodiphenyl sulfoxide; (IV) solid-liquid-separation of the suspension to obtain a residual moisture containing solid 4,4′-dichlorodiphenyl sulfoxide comprising crystallized 4,4′-dichlorodiphenyl sulfoxide and mother liquor.

First claim

The invention claimed is:

1. A process for producing 4,4′-dichlorodiphenyl sulfoxide comprising:
(I) reacting thionyl chloride, chlorobenzene and aluminum chloride in a molar ratio of thionyl chloride:chlorobenzene:aluminum chloride of 1:(6 to 9):(1 to 1.5) at a temperature in the range from 0 to below 20° C., forming an intermediate reaction product and hydrogen chloride;
(II) mixing aqueous hydrochloric acid and the intermediate reaction product at a temperature in the range from 70 to 110° C. to obtain an organic phase comprising 4,4′-dichlorodiphenyl sulfoxide and an aqueous phase;
(III) cooling the organic phase comprising the 4,4′-dichlorodiphenyl sulfoxide to a temperature below the saturation point of 4,4′-dichlorodiphenyl sulfoxide to obtain a suspension comprising crystallized 4,4′-dichlorodiphenyl sulfoxide, wherein cooling of the organic phase is carried out in a gastight closed vessel by
(i) reducing the pressure in the gastight closed vessel;
(ii) evaporating chlorobenzene;
(iii) condensing the evaporated chlorobenzene by cooling;
(iv) returning the condensed chlorobenzene into the gastight closed vessel;
(IV) solid-liquid-separation of the suspension to obtain a residual moisture containing solid 4,4′-dichlorodiphenyl sulfoxide comprising crystallized 4,4′-dichlorodiphenyl sulfoxide and mother liquor.

2. The process according to claim 1 , wherein the organic phase obtained in (II) is separated off and washed with water at a temperature in the range from 70 to 110° C. before cooling in (III).

3. The process according to claim 1 , wherein the hydrogen chloride obtained in (I) is mixed with water to obtain the aqueous hydrochloric acid which is used in (II).

4. The process according to claim 2 , wherein the water which is used for washing the organic phase is separated off and mixed with the hydrogen chloride obtained in (I) to obtain the aqueous hydrochloric acid.

5. The process according to claim 1 , wherein in (I) aluminum chloride and chlorobenzene are first fed into a reactor and the thionyl chloride is added to the aluminum chloride and chlorobenzene.

6. The process according to claim 1 , wherein for initializing crystallization of the 4,4′-dichlorodiphenyl sulfoxide the following steps are carried out before setting the reduced pressure in step (i):
reducing the pressure in the vessel such that the boiling point of the organic phase is in the range from 80 to 95° C.;
evaporating chlorobenzene until an initial formation of solids takes place;
increasing the pressure in the vessel and heating the organic phase in the vessel to a temperature in the range from 85 to 100° C.

7. The process according to claim 1 , wherein the mother liquor obtained in (IV) is concentrated and at least a part of the concentrated mother liquor is recycled into the cooling of the organic phase.

8. The process according to claim 7 , wherein the mother liquor is concentrated by distillation or evaporation.

9. The process according to claim 7 , wherein the amount of concentrated mother liquor recycled into the cooling of the organic phase is in the range from 10 to 95 wt % based on the total amount of concentrated mother liquor.

10. The process according to claim 1 , wherein the residual moisture containing solid 4,4′-dichlorodiphenyl sulfoxide obtained in (IV) is washed with solvent.

11. The process according to claim 10 , wherein at least a part of the solvent is purified after being used for washing the residual moisture containing solid 4,4′-dichlorodiphenyl sulfoxide and recycled.

12. The process according to claim 11 , wherein at least a part of the purified solvent is recycled into step (I).

13. The process according to claim 12 , wherein at least a part of the purified solvent is reused for washing the residual moisture containing solid 4,4′-dichlorodiphenyl sulfoxide.

Assignees

• Basf Se

Inventors

• Gao Jun
• Thiel Indre
• Schuetz Christian
• Metzger Lukas
• Bey Oliver
• Blei Stefan

Classifications

• C07C315/06

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

• C07C315/02

  by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides · CPC title

• C07C317/14

  having sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings · CPC title

• C07C315/00 Primary

  Preparation of sulfones; Preparation of sulfoxides · CPC title

• C07C315/04 Primary

  by reactions not involving the formation of sulfone or sulfoxide groups · CPC title