Method for preparing carboxylic esters from aldehydes

• US 20180334423A1
• Filed: 04/30/2018
• Published: 11/22/2018
• Est. Priority Date: 05/17/2017
• Status: Active Grant

• Current Assignee: Evonik Operations GmbH (Rag-Stiftung)
• Original Assignee: Evonik Rã¶Hm GmbH (Rag-Stiftung)
• Inventors: Lygin, Alexander, Krill, Steffen, Gromping, Matthias, Tepperis, Andreas
• Granted Patent: US 10,640,448 B2
• Time in Patent Office: Days
• CPC Class Codes: B01J 21/04 Alumina
• CPC Class Codes: B01J 21/063 Titanium; Oxides or hydroxides thereof
• CPC Class Codes: B01J 21/066 Zirconium or hafnium; Oxides or hydroxides thereof
• CPC Class Codes: B01J 21/08 Silica
• CPC Class Codes: B01J 21/12 Silica and alumina
• CPC Class Codes: B01J 21/14 Silica and magnesia
• CPC Class Codes: B01J 23/04 Alkali metals
• CPC Class Codes: B01J 23/10 of rare earths
• CPC Class Codes: B01J 23/14 of germanium, tin or lead
• CPC Class Codes: B01J 23/18 Arsenic, antimony or bismuth
• CPC Class Codes: B01J 23/34 Manganese
• CPC Class Codes: B01J 23/72 Copper
• CPC Class Codes: B01J 2531/31 Aluminium
• CPC Class Codes: B01J 31/0212 Alkoxylates
• CPC Class Codes: C07C 2531/14 of aluminium or boron
• CPC Class Codes: C07C 67/44 by oxidation-reduction of aldehydes, e.g. Tishchenko reaction
• CPC Class Codes: C07C 69/54 Acrylic acid esters; Methacrylic acid esters

Abstract

A method can prepare a carboxylic ester. The method includes reacting an aldehyde in the presence of an aluminium alkoxide applied to a support material.

Claims

1. :

A method for preparing a carboxylic ester, the method comprising;

reacting an aldehyde in the presence of an aluminium alkoxide applied to a support material.

2. :

The method according to claim 1, wherein the aldehyde is a compound of formula (I);

R¹—

CHO 

 

(I),

wherein R¹ is a —

(C₁-C₁₂)-alkyl group or a —

(C₂-C₁₂)-alkenyl group and R¹ may optionally be substituted by one or more substituents selected from the group consisting of —

(C₁-C₁₂)-alkyl, —

(C₃-C₁₂)-cycloalkyl, —

(C₆-C₁₂)-heterocycloalkyl, —

(C₆-C₂₀)-alkyl, —

(C₄-C₂₀)-heteroaryl, —

O—

(C₁-C₁₂)-alkyl, —

O—

(C₃-C₁₂)-cycloalkyl, —

S—

(C₁-C₁₂)-alkyl, —

S—

(C₃-C₁₂)-cycloalkyl, —

COO—

(C₁-C₁₂)-alkyl, —

COO—

(C₃-C₁₂)-cycloalkyl, —

CONH—

(C₁-C₁₂)-alkyl, —

CONH—

(C₃-C₁₂)-cycloalkyl, —

N—

[(C₁-C₁₂)-alkyl]₂, —

OH, —

NH₂, and a halogen atom.

3. :

The method according to claim 1, wherein the aldehyde is at least one member selected from the group consisting of acrolein and methacrolein.

4. :

The method according to claim 1, wherein the aluminium alkoxide is a compound of formula (II);

Al(OR²)₃ 

 

(II),

wherein each R² radical is independently of one another a —

(C₁-C₁₂)-alkyl group or a —

(C₂-C₁₂)-alkenyl group and each R² radical may independently of one another optionally be substituted by one or more substituents selected from the group consisting of —

(C₁-C₁₂)-alkyl, —

(C₃-C₁₂)-cycloalkyl, —

(C₄-C₁₂)-heterocycloalkyl, —

(C₆-C₂₀)-aryl, —

(C₄-C₂₀)-heteroaryl, —

O—

(C₁-C₁₂)-alkyl, —

O—

(C₃-C₁₂)-cycloalkyl, —

S—

(C₁-C₁₂)-alkyl, —

S—

(C₃-C₁₂)-cycloalkyl, —

COO—

(C₁-C₁₂)-alkyl, —

COO—

(C₃-C₁₂)-cycloalkyl, —

CONH—

(C₁-C₁₂)-alkyl, —

CONH—

(C₃-C₁₂)-cycloalkyl, —

N—

[(C₁-C₁₂)-alkyl]₂, —

OH, —

NH₂, and a halogen atom.

5. :

The method according to claim 2, wherein the aluminium alkoxide used is a compound of formula (III)

Al(OCH₂R³)₃ 

 

(III),

wherein each of the R³ radicals corresponds to the R¹ radical of the respective aldehyde according to formula (I).

6. :

The method according to claim 4, wherein each R² group is, independently, a group selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, allyl, and 2-methylallyl.

7. :

The method according to claim 1, wherein the support material comprises silicon dioxide.

8. :

The method according to claim 1, wherein the support material comprises 0-11% by weight of at least one oxide selected from the group consisting of an oxide of aluminium, an oxide of an alkali metal, an oxide of an alkaline earth metal, an oxide of a rare earth metal, an oxide of titanium, an oxide of zirconium, an oxide of copper, an oxide of manganese, an oxide of lead, an oxide of tin, and an oxide of bismuth.

9. :

The method according to claim 1, wherein the support material comprises

89-100% by weight silicon dioxide,

0-10% by weight of an aluminium oxide, and

0-3% by weight of at least one oxide selected from the group consisting of an oxide of an alkali metal, an oxide of an alkaline earth metal, an oxide of a rare earth metal, an oxide of titanium, an oxide of zirconium, an oxide of copper, an oxide of manganese, an oxide of lead, an oxide of tin, and an oxide of bismuth.

10. :

The method according to claim 1, wherein said reacting is carried out at a reaction temperature of 10 to 60°

C.

11. :

The method according to claim 1, wherein said reacting is carried out continuously.

12. :

A method for preparing a supported aluminium alkoxide, the method comprising;

reacting an aluminium alkoxide with a support material such that the aluminium alkoxide is adsorbed onto the support material.

13. :

The method according to claim 12, wherein the aluminium alkoxide is a compound of formula (II);

Al(OR²)₃ 

 

(II),

wherein each R² radical is independently of one another a —

(C₁-C₁₂)-alkyl group or a —

(C₂-C₁₂)-alkenyl group and each R² radical may independently of one another optionally be substituted by one or more substituents selected from —

(C₁-C₁₂)-alkyl, —

(C₃-C₁₂)-cycloalkyl, —

(C₄-C₁₂)-heterocycloalkyl, —

(C₆-C₁₂)-aryl, —

(C₄-C₁₂)-heteroaryl, —

O—

(C₁-C₁₂)-alkyl, —

O—

(C₃-C₁₂)-cycloalkyl, —

S—

(C₁-C₁₂)-alkyl, —

S—

(C₃-C₁₂)-cycloalkyl, —

COO—

(C₁-C₁₂)-alkyl, —

COO—

(C₃-C₁₂)-cycloalkyl, —

CONH—

(C₁-C₁₂)-alkyl, —

CONH—

(C₁-C₁₂)-cycloalkyl, —

N—

[(C₁-C₁₂)-alkyl]₂, —

OH, —

NH₂, and a halogen atom.

14. :

The method according to claim 13, wherein each R² group is, independently, a group selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, allyl, and 2-methylallyl.

15. :

The method according to claim 12, wherein the support material comprises

89-100% by weight SiO₂,

0-10% by weight Al₂O₃, and

0-3% by weight of at least one oxide selected from the group consisting of an oxide of an alkali metal, an oxide of an alkaline earth metal, an oxide of a rare earth metal, an oxide of titanium, an oxide of zirconium, an oxide of cooper, an oxide of manganese, an oxide of lead, an oxide of tin, and an oxide of bismuth.