Conversion of alcohols to carboxylic acids using heterogeneous palladium-based catalysts

Patent metadata

Field	Value
Publication number	US-9957217-B2
Application number	US-201715420378-A
Country	US
Kind code	B2
Filing date	Jan 31, 2017
Priority date	May 1, 2014
Publication date	May 1, 2018
Grant date	May 1, 2018

Abstract

Disclosed are methods for synthesizing an ester or a carboxylic acid from an organic alcohol. To form the ester one reacts, in the presence of oxygen gas, the alcohol with methanol or ethanol. This reaction occurs in the presence of a catalyst comprising palladium and a co-catalyst comprising bismuth, tellurium, lead, cerium, titanium, zinc and/or niobium (most preferably at least bismuth and tellurium). Alternatively that catalyst can be used to generate an acid from that alcohol, when water is also added to the reaction mix.

First claim

We claim:

1. A method for synthesizing an acid from an alcohol, comprising:
exposing a compound of the formula R—CH 2 —OH to oxygen gas and methanol-water mixture so as to yield a compound of the formula RCOOH;
wherein said exposing is in the presence of a catalyst comprising palladium, bismuth and tellurium;
wherein R is an alkyl, cyclic, amine, or ether, with or without sulfur or halogen content.

2. The method of claim 1 , wherein the catalyst further comprises an elemental carbon support in the form of charcoal or activated carbon.

3. The method of claim 1 , wherein there is at least 0.1 mol percent palladium, at least 0.01 mol percent bismuth, and at least 0.01 mol percent tellurium in the catalyst.

4. The method of claim 1 , in which the bismuth is present in a salt form and the tellurium is present in a metal form.

5. The method of claim 4 , wherein the bismuth salt is Bi(NO 3 ) 3 .5H 2 O.

6. A method for synthesizing an acid from an alcohol, comprising:
exposing a compound of the formula R—CH 2 —OH to oxygen gas and water so as to yield a compound of the formula RCOOH;
wherein said exposing is in the presence of a catalyst comprising palladium and a co-catalyst comprising at least two of the following: bismuth, tellurium, lead, cerium, titanium, zinc and niobium;
wherein R is an alkyl, cyclic, amine, ether, or ester, with or without sulfur or halogen content.

Assignees

• Wisconsin Alumni Res Found

Inventors

• Stahl Shannon S
• Powell Adam B
• Root Thatcher W
• Mannel David S
• Ahmed Maaz S

Classifications

• B01J21/18

  Carbon · CPC title

• C07C51/235 Primary

  of —CHO groups or primary alcohol groups · CPC title

• C07D307/68

  Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen · CPC title

• B01J35/0006

  Operations & Transport · mapped topic

• B01J27/0576

  Tellurium; Compounds thereof · CPC title