Process for forming a primary, a secondary or a tertiary amine via a direct amination reaction

Patent metadata

Field	Value
Publication number	US-9663446-B2
Application number	US-201315027727-A
Country	US
Kind code	B2
Filing date	Oct 15, 2013
Priority date	Oct 15, 2013
Publication date	May 30, 2017
Grant date	May 30, 2017

Abstract

Disclosed is a process for preparing a primary, a secondary or a tertiary amine via the direct amination of an alcohol in the presence of a catalyst. The catalyst is composed of palladium or a palladium compound and a cerium oxide supporter.

First claim

The invention claimed is:

1. A process to produce a primary, a secondary or a tertiary amine, the process comprising at least reacting:
1) a first reactant being a compound having at least one primary or secondary hydroxyl function, with
2) a second reactant being NH 3 or a compound having at least one primary or secondary amine function,
and at least in the presence of a catalyst composed of a cerium oxide support and comprising at least a palladium compound.

2. The process according to claim 1 wherein the cerium oxide provides a specific surface of at least 190 m 2 /g, measured after calcination at a temperature of 350° C. for 2 hours.

3. The process according to claim 1 wherein the palladium compound is selected from the group consisting of: palladium metal, PdO, PdO 2 , palladium nitrate, palladium chloride, palladium acetate, palladium acetylacetonate, and palladium hydroxide.

4. The process according to claim 1 wherein the catalyst is obtained by impregnation or co-precipitation.

5. The process according to of claim 1 wherein the weight ratio of the catalyst to the second reactant is between 0.05 and 2.

6. The process according to claim 1 wherein the first reactant is a compound of formula (I):
R 1 —(CH 2 —OH) x   (I)

wherein:
x is 1 or 2, and
R 1 is H or a straight, branched or cyclic hydrocarbon group.

7. The process according to claim 1 wherein the first reactant is selected from the group consisting of: furfuryl alcohol, 2,5 furandimethanol, 2,5-tetrahydrofuranedimethanol, benzyl alcohol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1-phenylethanol, 1,7-heptandiol, 1,3-propanediol, 1,4-butanediol, ethylene glycol, and isosorbide.

8. Process The process according to anyone of claim 1 wherein the second reactant is a compound of formula (II):
R 2 —NH 2   (II)

wherein R 2 is H or a straight, branched or cyclic hydrocarbon group.

9. The process according to claim 1 wherein the second reactant is a compound of formula (III):
R 3 —NH—R 4   (III)

wherein R 3 and R 4 represent, independently from each other, a straight, branched or cyclic hydrocarbon group, R 3 and R 4 may together form a cyclic group, which may optionally contain a heteroatom.

10. The process according to claim 1 wherein the second reactant is selected from the group consisting of: ammonia, phenylamine, n-heptylamine, aniline, methylamine, dimethylamine, dodecylamine, pyrrolidine, pyrrol, pyridine, imidazole, quinoleine tetrahydroquinoleine, aziridine, azirine, and piperidine.

11. The process according to claim 1 wherein the obtained primary or secondary amine is a compound of formula (IV):
R 1 (CH 2 —NHR 2 )x  (IV)

wherein:
x is 1 or 2,
R 1 is H or a straight, branched or cyclic hydrocarbon group, and
R 2 is H or a straight, branched or cyclic hydrocarbon group.

12. The process according to claim 1 wherein the obtained primary or secondary amine is selected from the group consisting of: N-phenylbenzylamine (N-benzylaniline), dibenzylamine, N-(1-phenylethyl)aniline, 1-benzyl-1,2,3,4-tetrahydroquinoline, N-(cyclohex-2-en-1-yl)benzenamine, (tetrahydrofuran-2,5-diyl) dimethanamine, (furan-2,5-diyl)dimethanamine, 1,6-hexamethylenediamine, 1,1′-(tetrahydrofuran-2,5-diyl)bis(N-methylethylamine), and 1,1′-(tetrahydrofuran-2,5-diyl)bis(N-heptaneaminomethane).

13. The process according to claim 1 wherein the reaction medium comprises at the start of the reaction, between 0.1 and 5 molar equivalent of the second reactant for 1 molar equivalent of the first reactant.

14. The process according to claim 1 wherein the reaction medium comprises an apolar solvent, a polar aprotic solvent or water.

Assignees

• Rhodia Operations
• Centre Nat Rech Scient

Inventors

• Yan Zhen
• Ousmane Mohamad
• Pera-Titus Marc
• Decampo Floryan

Classifications

• C07C209/18 Primary

  with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings · CPC title

• C07D307/52

  Radicals substituted by nitrogen atoms not forming part of a nitro radical · CPC title

• B01J23/63

  with rare earths or actinides · CPC title

• C07D307/14

  Radicals substituted by nitrogen atoms not forming part of a nitro radical · CPC title

• C07D215/06

  having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom · CPC title