Method for preparing carboxylic esters from aldehydes

• US 10,640,448 B2
• Filed: 04/30/2018
• Issued: 05/05/2020
• Est. Priority Date: 05/17/2017
• Status: Expired due to Fees

• Current Assignee: Evonik Operations GmbH (Rag-Stiftung)
• Original Assignee: Evonik Operations GmbH (Rag-Stiftung)
• Inventors: Lygin, Alexander, Krill, Steffen, Gromping, Matthias, Tepperis, Andreas
• Primary Examiner(s): Parsa, Jafar F
• Assistant Examiner(s): Doletski, Blaine G
• Application Number:
  US15/967,463
• Publication Number:
  US 20180334423A1
• Time in Patent Office: 736 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 (meth)acrolein in the presence of an aluminum alkoxide applied to a support material comprising silicon dioxide.

2. The method according to claim 1, wherein the aluminum 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.

3. The method according to claim 1, wherein the aluminum alkoxide is a compound of formula (III)

Al(OCH₂R³)₃ 

 

(III),

wherein each of the R³ radicals corresponds to C₂ alkenyl or methyl substituted C₂ alkenyl.

4. The method according to claim 2, 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.

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

C.

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

7. The method according to claim 1, wherein said (meth)acrolein is reacted without addition of solvent.