Process for the preparation of alpha, beta unsaturated aldehydes by oxidation of alcohols in the presence of a liquid phase

Patent metadata

Field	Value
Publication number	US-11111197-B2
Application number	US-201816956972-A
Country	US
Kind code	B2
Filing date	Dec 5, 2018
Priority date	Dec 21, 2017
Publication date	Sep 7, 2021
Grant date	Sep 7, 2021

Abstract

Process for the preparation of alpha, beta unsaturated aldehydes by oxidation of alcohols in the presence of a liquid phase.

First claim

The invention claimed is:

1. A process for the preparation of alpha, beta unsaturated aldehydes of general formula (I)

wherein R 1 , R 2 and R 3 , independently of one another, are selected from
hydrogen; C 1 -C 6 -alkyl, which optionally carry 1, 2, 3, or 4 identical or different substituents which are selected from NO 2 , CN, halogen, C 1 -C 6 alkoxy, (C 1 -C 6 -alkoxy)carbonyl, C 1 -C 6 acyl, C 1 -C 6 acyloxy and aryl; and C 2 -C 6 -alkenyl, which optionally carry 1, 2, 3, or 4 identical or different substituents which are selected from NO 2 , CN, halogen, C 1 -C 6 alkoxy, (C 1 -C 6 -alkoxy)carbonyl, C 1 -C 6 acyl, C 1 -C 6 acyloxy and aryl;
by oxidation of alcohols of general formula (II)

wherein R 1 , R 2 and R 3 have the meaning as given above
in the presence of a catalyst and in the presence of a liquid phase,
wherein the liquid phase contains at least 25 weight-% water based on the total weight of the liquid phase, determined at a temperature of 20° C. and a pressure of 1 bar and
wherein the oxidant is oxygen, and
wherein the catalyst comprises a catalytically active metal on a support and the catalytically active metal is located mainly in the outer shell of the catalyst, wherein the outer shell of the catalyst is the space from the outer surface of the catalyst to a depth of X from the outer surface of the catalyst, wherein X is 15 % of the distance from the outer surface of the catalyst to the center of the catalyst.

2. A process for the preparation of alpha, beta unsaturated aldehydes of general formula (I)

wherein R 1 , R 2 and R 3 , independently of one another, are selected from
hydrogen; C 1 -C 6 -alkyl, which optionally carry 1, 2, 3, or 4 identical or different substituents which are selected from NO 2 , CN, halogen, C 1 -C 6 alkoxy, (C 1 -C 6 -alkoxy)carbonyl, C 1 -C 6 acyl, C 1 -C 6 acyloxy and aryl; and C 2 -C 6 -alkenyl, which optionally carry 1, 2, 3, or 4 identical or different substituents which are selected from NO 2 , CN, halogen, C 1 -C 6 alkoxy, (C 1 -C 6 -alkoxy)carbonyl, C 1 -C 6 acyl, C 1 -C 6 acyloxy and aryl;
by oxidation of alcohols of general formula (II)

wherein R 1 , R 2 and R 3 have the meaning as given above
in the presence of a catalyst and in the presence of a liquid phase,
wherein the liquid phase contains at least 25 weight-% water based on the total weight of the liquid phase, determined at a temperature of 20° C. and a pressure of 1 bar and
wherein the oxidant is oxygen, and
wherein a catalyst is used which is obtainable by
a) providing a support
b) providing a metal compound
c) depositing the metal compound on the support
d) optionally calcinating the so obtained catalyst precursor
e) reducing the catalyst precursor, by treatment of the catalyst precursor with a solution of a reducing agent
f) optionally recovering the catalyst.

3. The process according to claim 1 , wherein an alcohol according to formula (II) is used, wherein R 1 , R 2 or R 3 , independently of one another, are selected from H and CH 3 .

4. The process according to claim 1 , wherein an alcohol according to formula (II) is used, wherein R 3 is H and R 2 and R 1 are CH 3 .

5. The process according to claim 1 , wherein the liquid phase contains at least 50 weight-%, water based on the total weight of the liquid phase.

6. The process according to claim 1 , wherein the oxidation is carried out at a temperature of 20° C. to 100° C.

7. The process according to claim 1 , wherein the oxidation is carried out under a partial pressure of oxygen between 0.2 and 8 bar.

8. The process according to claim 1 , wherein the catalytically active metal is selected from elements selected from the group consisting of platinum, palladium and gold.

9. The process according to claim 1 , wherein the support is selected from the group consisting of carbonaceous materials and oxidic materials.

10. The process according to claim 1 , wherein the support is selected from the group consisting of alpha aluminium oxide (α-Al 2 O 3 ), beta aluminium oxide (ß-Al 2 O 3 ) and gamma aluminium oxide (γ-Al 2 O 3 ).

11. The process according to claim 2 , wherein an alcohol according to formula (II) is used, wherein R 1 , R 2 or R 3 , independently of one another, are selected from H and CH 3 .

12. The process according to claim 2 , wherein an alcohol according to formula (II) is used, wherein R 3 is H and R 2 and R 1 are CH 3 .

13. The process according to claim 2 , wherein the liquid phase contains at least 50 weight-% water based on the total weight of the liquid phase.

14. The process according to claim 2 , wherein the oxidation is carried out at a temperature of 20° C. to 100° C.

15. The process according to claim 2 , wherein the oxidation is carried out under a partial pressure of oxygen between 0.2 and 8 bar.

16. The process according to claim 2 , wherein the catalytically active metal is selected from elements selected from the group consisting of platinum, palladium and gold.

17. The process according to claim 2 , wherein the support is selected from the group consisting of carbonaceous materials and oxidic materials.

18. The process according to claim 2 , wherein the support is selected from the group consisting of alpha aluminium oxide (α-Al 2 O 3 ), beta aluminium oxide (ß-Al 2 O 3 ) and gamma aluminium oxide (γ-Al 2 O 3 ).

19. The process according to claim 1 , wherein the liquid phase contains at least 70 weight-% water based on the total weight of the liquid phase and the oxidation is carried out at a temperature of 20° C. to 70° C.

20. The process according to claim 2 , wherein the liquid phase contains at least 70 weight-% water based on the total weight of the liquid phase and the oxidation is carried out at a temperature of 20° C. to 70° C.

21. The process according to claim 1 , wherein the outer shell of the catalyst is the space from the outer surface of the catalyst to a depth of X from the outer surface of the catalyst, wherein X is 30 % of the distance from the outer surface of the catalyst to the center of the catalyst.

22. The process according to claim 2 , wherein the liquid phase contains at least 95 weight-% water based on the total weight of the liquid phase.

23. The process according to claim 2 , wherein the catalyst comprises Pt and Bi.

Assignees

• Basf Se

Inventors

• Fenyn Michaela
• Zakzeski Joseph John
• Vautravers Nicolas
• Teles Joaquim Henrique

Classifications

• B01J23/52

  Gold · CPC title

• B01J23/44

  Palladium · CPC title

• B01J23/42

  Platinum · CPC title

• C07C45/38 Primary

  being a primary hydroxyl group · CPC title

• C07C47/21

  with only carbon-to-carbon double bonds as unsaturation · CPC title