Benzylic oxidation and catalyst therefor

• US 5,280,001 A
• Filed: 10/05/1992
• Issued: 01/18/1994
• Est. Priority Date: 02/10/1992
• Status: Expired due to Fees

• Current Assignee: Phillips Petroleum Company (ConocoPhillips)
• Original Assignee: Phillips Petroleum Company (ConocoPhillips)
• Inventors: Tso, Chung C., Wynn, Robert L.
• Primary Examiner(s): GARVIN, PATRICK
• Application Number:
  US07/956,925
• Time in Patent Office: 470 Days
• Field of Search: 502/169, 502/170
• US Class Current: 502/170
• CPC Class Codes: C07C 67/00 Preparation of carboxylic acid esters

Abstract

Oxidation of alkylaromatics having a benzylic hydrogen atom is catalyzed by a catalyst comprising a palladium salt, a metal persulfate, a third metal salt, and a tin salt in a carboxylic acid for a period of time sufficient to convert the alkylaromatics to their corresponding oxidized derivatives. The catalyst is prepared by preheating the palladium salt and the metal persulfate at a temperature sufficient to provide the desired catalytic activity followed by addition of the third metal salt and the tin salt.

Claims

1. A catalyst comprising a palladium salt, a metal persulfate, a third metal salt and a tin salt, in a carboxylic acid;

wherein said third metal salt has a general formula of MX wherein M is a metal selected from the group consisting of alkali metals and alkaline earth metals and X is an anion selected from the group consisting of carboxylate, sulfate, nitrate, phosphate, halide, and mixtures thereof; and

said metal persulfate is selected from the group consisting of an alkali metal persulfate, an alkaline earth metal persulfate, and mixtures thereof.

2. A catalyst according to claim 1, wherein said palladium salt is selected from the group consisting of palladium acrylate, palladium acetate, palladium propionate, palladium butyrate, palladium hexanoate, palladium cyclohexanoate, palladium chloride, and palladium nitrate.

3. A catalyst according to claim 2 wherein said palladium salt is palladium acetate.

4. A catalyst according to claim 1 wherein said metal persulfate is selected from the group consisting of lithium persulfate, sodium persulfate, potassium persulfate, magnesium persulfate, and calcium persulfate.

5. A catalyst according to claim 4 wherein said metal persulfate is potassium persulfate.

6. A catalyst according to claim 1 wherein said third metal salt is selected from the group consisting of lithium acetate, sodium acetate, potassium acetate, potassium acrylate, potassium propionate, potassium butyrate, potassium sulfate, potassium phosphate, and potassium chloride.

7. A catalyst according to claim 6 wherein said third metal salt is potassium acetate.

8. A catalyst according to claim 1 wherein said tin salt is selected from the group consisting of stannous acetate, stannous propionate, stannous butyrate, stannous laurate, stannous oleate, stannous benzoate, stannous gluconate, stannous naphthenate, stannous chloride, and stannous nitrate.

9. A catalyst according to claim 8 wherein said tin salt is stannous acetate.

10. A catalyst according to claim 1 wherein said carboxylic acid is selected the group consisting of aromatic and saturated aliphatic carboxylic acids having 1 to 18 carbon atoms.

11. A catalyst according to claim 10 wherein said carboxylic acid is saturated aliphatic carboxylic acid selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, octanoic acid, lauric acid, stearic acid, and chloroacetic acid.

12. A catalyst according to claim 11 wherein said carboxylic acid is acetic acid.

13. A catalyst according to claim 1 wherein:

said palladium salt is selected from the group consisting of palladium acrylate, palladium acetate, palladium propionate, palladium butyrate, palladium hexonoate, palladium cyclohexanoate, palladium chloride, and palladium nitrate;

said metal persulfate is selected from the group consisting of lithium persulfate, sodium persulfate, potassium persulfate, magnesium persulfate, and calcium persulfate;

said third metal salt is selected from the group consisting of lithium acetate, sodium acetate, potassium acetate, potassium propionate, potassium butyrate, potassium acrylate, potassium sulfate, potassium phosphate and potassium chloride;

said tin salt is selected from the group consisting of stannous acetate, stannous propionate, stannous butyrate, stannous laurate, stannous oleate, stannous benzoate, stannous gluconate, stannous naphthenate, stannous chloride, and stannous nitrate; and

said carboxylic acid is selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, octanoic acid, lauric acid, stearic acid, and chloroacetic acid.

14. A catalyst according to claim 13 wherein said palladium salt is palladium acetate, said metal persulfate is potassium persulfate, said third metal salt is potassium acetate and said carboxylic acid is acetic acid.

15. A catalyst according to claim 1 wherein said catalyst is prepared by the steps comprising:

(a) mixing a palladium salt, a metal persulfate and a third metal salt wherein said third metal salt has a general formula of MX wherein M is a metal selected from the group consisting of alkali metals and alkaline earth metals and X is an anion selected from the group consisting of carboxylate, sulfate, nitrate, phosphate, halide, and mixtures thereof, in a carboxylic acid, to form a suspension;

(b) heating said suspension to form a heated suspension; and

(c) adding an additional amount of said third metal salt and a tin salt to said heated suspension.

16. A catalyst according to claim 15 wherein:

said palladium salt is selected from the group consisting of palladium acrylate, palladium acetate, palladium propionate, palladium butyrate, palladium hexanoate, palladium cyclohexanoate, palladium chloride, and palladium nitrate;

said metal persulfate is selected from the group consisting of lithium persulfate, sodium persulfate, potassium persulfate, magnesium persulfate, and calcium persulfate;

said third metal salt is selected from the group consisting of lithium acetate, sodium acetate, potassium acetate, potassium propionate, potassium butyrate, potassium acrylate, potassium sulfate, potassium phosphate and potassium chloride;

said tin salt is selected from the group consisting of stannous acetate, stannous propionate, stannous butyrate, stannous laurate, stannous oleate, stannous benzoate, stannous gluconate, stannous naphthenate, stannous chloride, and stannous nitrate; and

said carboxylic acid is a saturated aliphatic carboxylic acid selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, octanoic acid, lauric acid, stearic acid, and chloroacetic acid;

said temperature is about 60°

C. to about 150°

C.; and

said period of time is about 5 minutes to about 3 hours.

17. A catalyst according to claim 16 wherein said palladium salt is palladium acetate, said metal persulfate is potassium persulfate, said third metal salt is potassium acetate said tin salt is stannous acetate, said carboxylic acid is acetic acid, said temperature is 90°

C. to 120°

C., and said period of time is 20 minutes to 1 hour.

18. A catalyst according to claim 1 further comprising an antiagglomerant selected from the group consisting of charcoal, alumina, silicate, silica, and mixtures thereof.

19. A catalyst comprising palladium acetate, potassium persulfate, potassium acetate and stannous acetate, in acetic acid wherein said catalyst is prepared by the process comprising:

(1) mixing said palladium acetate, said potassium persulfate, and said potassium acetate to form a suspension;

(2) heating said suspension at 90°

C. to 120°

C. for 20 minutes to 1 hour to form a heated suspension; and

(3) adding said potassium acetate and said stannous acetate to said heated suspension.