IP Library Granted Patent US 8,889,908
Granted Patent B2
US 8,889,908 · App. 13/575,150 · Granted Nov 18, 2014

Silver-catalyzed synthesis of amides from amines and aldehydes

Inventors: Robert J. Madix (Lexington, MA); Ling Zhou (Cambridge, MA); Bingjun Xu (Cambridge, MA); Cynthia M. Friend (Lexington, MA); Cassandra G. Freyschlag (Colorado Springs, CO)
Assignee: President and Fellows of Harvard College
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Quick Facts
Patent No.
US 8,889,908
App. No.
13/575,150
Granted
Nov 18, 2014
Kind
B2
Abstract

The invention provides a method for producing amides via the reaction of aldehydes and amines with oxygen adsorbed on a metallic silver or silver alloy catalyst. An exemplary reaction is shown in Scheme 1: (I), (II), (III).

Claims (16)

1. A method for preparing an amide comprising reacting an aldehyde and a primary or secondary amine with oxygen adsorbed on a catalyst comprising silver metal or an alloy thereof to produce the amide.

2. The method of claim 1 , wherein the amide is of formula III, the aldehyde is of formula I and the primary or secondary amine is of formula II:

wherein R 1 is selected from the group consisting of H, C 1 -C 6 straight chain alkyl, C 3 -C 6 branched alkyl, and C 3 -C 8 cycloalkyl; and

wherein R 2 and R 3 are independently selected from the group consisting of H, C 1 -C 6 straight chain alkyl, C 3 -C 6 branched alkyl, and C 3 -C 8 cycloalkyl, or R 2 and R 3 , together with the nitrogen to which they are attached, form a 3- to 6-membered heterocyclic ring; or R 1 and R 2 together are C 1 -C 6 alkylene.

3. The method of claim 2 , wherein R 1 is selected from the group consisting of H, C 1 -C 4 straight chain alkyl, C 3 -C 4 branched alkyl, and C 3 -C 4 cycloalkyl; and

wherein R 2 and R 3 are independently selected from the group consisting of H, C 1 -C 4 straight chain alkyl, C 3 -C 4 branched alkyl, and C 3 -C 4 cycloalkyl, or R 2 and R 3 , together with the nitrogen to which they are attached, form a 3- to 6-membered heterocyclic ring.

4. The method of claim 2 , wherein R 2 and R 3 are methyl.

5. The method of claim 1 , wherein the aldehyde is formaldehyde.

6. The method of claim 1 , wherein the silver alloy is an alloy of silver and gold.

7. The method of claim 1 , wherein the source of the adsorbed oxygen is oxygen gas.

8. The method of claim 1 , wherein the amine is a primary amine.

9. The method of claim 1 , wherein the amine is a secondary amine.

10. The method of claim 1 , wherein the catalyst is promoted by a material selected from the group consisting of metal halides, carbonates, sulfites, sulfates, nitrites, and nitrates, transition metal oxoanions, lanthanides, and alkali and alkaline earth metals.

11. The method of claim 1 , wherein the temperatures is from 270 to 1000 K.

12. The method of claim 1 , wherein the pressure is from 0.1 atm to 5 atmospheres.

13. The method of claim 1 , wherein the catalyst is carried on an inert supporting material.

Assignments (2)
CONFIRMATORY LICENSE Recorded Dec 4, 2012
From: HARVARD UNIVERSITY
To: ENERGY, UNITED STATES DEPARTMENT OF
Reel/Frame 029435/0099 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Oct 10, 2012
From: FREYSCHLAG, CASSANDRA G.; FRIEND, CYNTHIA; MADIX, ROBERT J.; XU, BINGJUN; ZHOU, LING
To: PRESIDENT AND FELLOWS OF HARVARD COLLEGE
Reel/Frame 029108/0097 →
Continuity (2)
Provisional Application 61336673 · Jan 25, 2010
Related Publication 20130079556A1 · Mar 28, 2013