Method for producing oxime

Patent metadata

Field	Value
Publication number	US-9656950-B2
Application number	US-201414779737-A
Country	US
Kind code	B2
Filing date	Mar 17, 2014
Priority date	Mar 27, 2013
Publication date	May 23, 2017
Grant date	May 23, 2017

Abstract

Provided is a method for efficiently producing an oxime, which is a method for producing an oxime by oxidizing, an amine, the method comprising a first contact step and a second contact step, wherein the second contact step is performed by bringing an additional amine into contact with oxygen in the presence of at least a part of an oxidation product obtained in the first contact step.

First claim

The invention claimed is:

1. A method for producing an oxime having formula (II) provided below, the method comprising the following first contact step and second contact step:
a first contact step: in a first reactor, bringing an amine having formula (I):

wherein R 1 and R 2 are each independently a hydrogen atom, an optionally substituted hydrocarbon group, or an optionally substituted heterocyclic group, provided that R 1 and R 2 are not simultaneously hydrogen atoms, or
R 1 and R 2 , together with the carbon atom to which R 1 and R 2 are attached, form an optionally substituted alicyclic hydrocarbon group having 3 to 12 carbon atoms, into contact with an oxidizing agent in the presence of a first oxidation catalyst comprising a layered silicate to obtain an oxidation product: and
a second contact step: in a second reactor, bringing an additional quantity of the amine having formula (I) into contact with an oxidizing agent in the presence of at least a part of the oxidation product obtained in the first contact step to obtain an oxime having formula (II):

wherein R 1 and R 2 are as defined above.

2. The method according to claim 1 , wherein the first contact step is performed in a batch manner or a semibatch manner, and the second contact step is performed in a semibatch manner or a continuous manner.

3. The method according to claim 1 , wherein the second contact step is performed in the presence of at least one catalyst selected from the group consisting of a second oxidation catalyst and a first oxidation catalyst recovered after the first contact step.

4. The method according to claim 1 , wherein the layered silicate is smectite.

5. The method according to claim 1 , wherein the layered silicate contains at least one selected from the group consisting of hydrogen ions, ammonium ions, quaternary ammonium ions, cations of Group 4 metal elements, cations of Group 5 metal elements, cations of Group 6 metal elements, germanium ions, positively charged oxides of Group 4 metal elements, positively charged oxides of Group 5 metal elements, positively charged oxides of Group 6 metal elements, and positively charged germanium oxides.

6. The method according to any one of claim 1 , wherein the oxidation product in the first contact step comprises an oxime having formula (II) and a product, and the second contact step is a step of further bringing at least a part of a by-product obtained in the first contact step, the amine having formula (I), and oxygen into contact with each other to obtain an oxime having formula (II).

7. A method for producing an amide having formula (III):

wherein R 1 and R 2 are each independently a hydrogen atom, an optionally substituted hydrocarbon group, or an optionally substituted heterocyclic group, provided that R 1 and R 2 are not simultaneously hydrogen atoms, or
R 1 and R 2 , together with the nitrogen atom to which R 1 is attached and the carbon atom to which R 2 is attached, form an optionally substituted aliphatic heterocyclic group having 3 to 12 carbon atoms,
the method comprising subjecting an oxime represented by the formula (II) produced by the method according to claim 1 to a Beckmann rearrangement reaction.

Assignees

• Sumitomo Chemical Co

Inventors

• Hoshino Masahiro
• Kikuchi Yuta

Classifications

• C07C249/04 Primary

  of oximes · CPC title

• C07D223/10

  attached in position 2 · CPC title

• Y02P20/582

  Recycling of unreacted starting or intermediate materials · CPC title

• C07C2601/14

  The ring being saturated · CPC title

• C07C251/44

  with the carbon atom of at least one of the oxyimino groups being part of a ring other than a six-membered aromatic ring · CPC title