Sulfoxidation catalysts and methods for their preparation and use

Patent metadata

Field	Value
Publication number	US-9982002-B2
Application number	US-201415029945-A
Country	US
Kind code	B2
Filing date	Sep 8, 2014
Priority date	Oct 15, 2013
Publication date	May 29, 2018
Grant date	May 29, 2018

Abstract

Methods and compositions of catalysts for sulfoxidation reaction processes are disclosed. The sulfoxidation reaction process can be performed in an aqueous medium, and the catalysts can be recycled for further use. In some embodiments, a method of making a catalyst may include contacting a transition metal compound with an oxidizing agent to form a first solution, contacting a carboxylic acid compound with a cationic surfactant to form a second solution, mixing the first solution and the second solution to form a precipitate, and isolating the precipitate.

First claim

We claim:

1. A method of making a catalyst of formula I:

wherein Z is alkylene, arylene, alkenylene, or alkynylene;
R 1 is alkyl, aryl, alkenyl, or alkynyl;
R 2 is alkyl, aryl, alkenyl, or alkynyl;
R 3 is alkyl, aryl, alkenyl, or alkynyl;
n is an integer from 1 to 20; and
X is Mo, V, or Cr, the method comprising:

contacting a transition metal compound with an oxidizing agent to form a first solution;
contacting a carboxylic acid compound with a cationic surfactant to form a second solution;
mixing the first solution and the second solution to form a precipitate; and
isolating the catalyst.

2. The method of claim 1 , wherein contacting the transition metal compound comprises contacting a molybdate compound, a vanadate compound, or a chromate compound.

3. The method of claim 1 , wherein contacting the carboxylic acid compound comprises contacting oxalic acid, malonic acid, benzoic acid, a pyridine carboxylic acid, lactic acid, maleic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, fumaric acid, or any combination thereof.

4. The method of claim 1 , wherein contacting the transition metal compound with the oxidizing agent comprises contacting with potassium persulfate, ammonium persulfate, hydrogen peroxide, benzoyl peroxide, di-tert-butyl peroxide, decanoyl peroxide, lauroyl peroxide, perbenzoic acid, peracetic acid, performic acid, monoperphthalic acid, or any combination thereof.

5. The method of claim 1 , wherein contacting the carboxylic acid compound with the cationic surfactant comprises contacting with dimethyl dioctadecyl ammonium chloride, alkyldimethylbenzyl ammonium chloride, cetyltrimethyl ammonium bromide, cetyltrimethyl ammonium chloride, benzethonium chloride, or any combination thereof.

6. The method of claim 1 , wherein contacting the transition metal compound with the oxidizing agent comprises contacting the transition metal compound with the oxidizing agent in a molar ratio of 1:10 to 1:20.

7. The method of claim 1 , wherein contacting the transition metal compound with the oxidizing agent comprises contacting the transition metal compound with the oxidizing agent to form a solution having a pH of 1 to 4.

8. The method of claim 1 , wherein contacting the carboxylic acid compound with the cationic surfactant comprises contacting the carboxylic acid compound with the cationic surfactant in a molar ratio of 1:1 to 1:3.

9. The method of claim 1 , further comprising maintaining acidity below a pH of 4 during mixing the first solution and the second solution.

10. A sulfoxidation process comprising:
contacting a sulfide with a catalyst of formula I

wherein Z is alkylene, arylene, alkenylene, or alkynylene;
R 1 is alkyl, aryl, alkenyl, or alkynyl;
R 2 is alkyl, aryl, alkenyl, or alkynyl;
R 3 is alkyl, aryl, alkenyl, or alkynyl;
n is an integer from 1 to 20; and
X is Mo, V, or Cr, to form a first reaction mixture;

contacting an oxidizing agent with the first reaction mixture to form a second reaction mixture; and
isolating a product from the second reaction mixture.

11. The method of claim 10 , wherein contacting the sulfide comprises contacting an alkyl sulfide, an aryl sulfide, a substituted aryl sulfide, a cyclic alkyl sulfide, or a combination thereof.

12. The method of claim 10 , wherein contacting the oxidizing agent comprises contacting potassium persulfate, ammonium persulfate, hydrogen peroxide, benzoyl peroxide, di-tert-butyl peroxide, decanoyl peroxide, lauroyl peroxide, perbenzoic acid, peracetic acid, performic acid, monoperphthalic acid, or any combination thereof.

13. The method of claim 10 , wherein contacting the oxidizing agent comprises contacting with the sulfide present in the second reaction mixture at a concentration of 30 mole percent to 60 mole percent.

14. The method of claim 10 , wherein contacting the oxidizing agent comprises contacting with the catalyst present in the second reaction mixture at a concentration of 1 mole percent to 10 mole percent.

15. The method of claim 10 , wherein the oxidizing agent is present in the second reaction mixture at a concentration of 40 mole percent to 60 mole percent.

16. The method of claim 10 , wherein isolating the product comprises adding at least one organic solvent to the second reaction mixture.

17. The method of claim 16 , wherein isolating the product further comprises removing the solvent from the second reaction mixture.

18. The method of claim 10 , wherein isolating the product comprises isolating at least one sulfoxide, at least one sulfone, or any combination thereof.

Assignees

• Indian Institute Of Tech Madras

Inventors

• Chand Dillip Kumar
• Chakravarthy Rajan Deepan

Classifications

• B01J37/031

  Precipitation · CPC title

• B01J37/12

  Oxidising · 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

• B01J31/2239

  Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands · CPC title

• B01J31/2295

  Cyclic compounds, e.g. cyclopentadienyls · CPC title