Production method for 2-alkenylamine compound

Patent metadata

Field	Value
Publication number	US-9346740-B2
Application number	US-201214237497-A
Country	US
Kind code	B2
Filing date	Aug 29, 2012
Priority date	Aug 31, 2011
Publication date	May 24, 2016
Grant date	May 24, 2016

Abstract

Provided is a method for producing a 2-alkenylamine compound efficiently and at low cost, using a primary or secondary amine compound and a 2-alkenyl compound as the starting materials therefor. The 2-alkenyleamine compound is produced by 2-alkenylating a primary or secondary amine compound, using a specified 2-alkenylating agent and in the presence of a catalyst comprising a complexing agent and a transition metal precursor stabilized by a monovalent anionic five-membered conjugated diene.

First claim

The invention claimed is:

1. A method for producing a 2-alkenylamine compound by reacting a primary or secondary amine compound with a 2-alkenyl compound of the following formula (1):

wherein R 1 , R 2 , R 3 , R 4 and R 5 are, independently from each other, a hydrogen atom, a C1 to C10 alkyl group, a C2 to C10 alkenyl group, a C1 to C10 alkoxy group, a C3 to C12 cycloalkyl group, a C3 to C12 cycloalkenyl group, an acetoxy group, or a C6 to C10 aryl group; and X is a substituent selected from the group consisting of —NO 2 , RO—, RS(O) 2 O—, RCOO—, and ROCOO— wherein R is a C1 to C30 organic group, in the presence of a catalyst,
wherein the catalyst is a transition metal complex which is a reaction product of a complexing agent having a nitrogen coordination site and an oxygen coordination site bidentate-coordinated to a transition metal atom in the molecule and a transition metal precursor having a monovalent anionic five-membered ring-conjugated diene as a ligand in the molecule,
wherein the monovalent anionic 5-membered ring-conjugated diene has a conjugatable monovalent anionic structure, wherein the anion is conjugated to the binding carbons of R 10 to R 30 , the structure of any of the following formulae (3-1), (3-2) and (3-3):

wherein R 10 to R 30 are a hydrogen atom.

2. The method for producing a 2-alkenylamine compound according to claim 1 , wherein the complexing agent is an α-imino acid type ligand compound of the following formula (2):

wherein R 6 to R 9 are, independently from each other, a hydrogen atom, a C1 to C10 alkyl group, a C3 to C12 cycloalkyl group, a C6 to C10 aryl group, an alkyl-substituted silyl group, said substituent having a total of 1 to 30 carbons, or an aryl-substituted silyl group, said substituent having a total of 6 to 30 carbons, or R 6 and R 7 , R 7 and R 8 , R 8 and R 9 , R 6 and R 8 , R 6 and R 9 , or R 7 and R 9 may bind to each other to form a saturated or unsaturated 4 to 8-membered ring.

3. The method for producing a 2-alkenylamine compound according to claim 1 , wherein the transition metal precursor comprises at least one of transition metal atoms selected from the group consisting of the transition metals belonging to Group 8 and Group 9 of the periodic table.

4. The method for producing a 2-alkenylamine compound according to claim 3 , wherein the transition metal atom is selected from the group consisting of ruthenium, rhodium, and iridium.

5. The method for producing a 2-alkenylamine compound according to claim 1 , wherein the monovalent anionic 5-membered ring-conjugated diene has a conjugatable monovalent anionic structure, wherein the anion is conjugated to the binding carbons of R 10 to R 14 , the structure of following formula (3-1):

wherein R 10 to R 14 are a hydrogen atom.

6. The method for producing a 2-alkenylamine compound according to claim 1 , wherein all of R 1 , R 2 , R 3 , R 4 and R 5 in formula (1) each are a hydrogen atom.

7. The method for producing a 2-alkenylamine compound according to claim 1 , wherein the primary or secondary amine compound is selected from the group consisting of a saturated C1 to C30 aliphatic amine having one or two amino group(s) in the molecule, a saturated C3 to C30 alicyclic amine having one or two amino group(s) in the molecule, a C6 to C30 arylamine compound having 1 to 10 amino group(s) in the molecule, and a nitrogen-containing C2 to C30 heterocyclic compound having a hydrogen atom on the nitrogen atom constituting the heterocyclic ring.

8. The method for producing a 2-alkenylamine compound according to claim 1 , wherein 0.000001 to 10 moles of the transition metal complex is used relative to one total mole of the primary or secondary amine compound and the 2-alkenyl compound (moles of the primary or secondary amine compound plus moles of the 2-alkenyl compound).

9. The method for producing a 2-alkenylamine compound according to claim 1 , comprising the steps of:
reacting a compound having a monovalent anionic 5-membered ring-conjugated diene backbone and a transition metal compound to produce the transition metal precursor having the monovalent anionic 5-membered ring-conjugated diene as a ligand in the molecule,
mixing the transition metal precursor and the complexing agent to produce the transition metal complex, and
mixing and reacting the transition metal complex, the primary or secondary amine compound, and the 2-alkenyl compound to produce a 2-alkenylamine compound.

10. The method for producing a 2-alkenylamine compound according to claim 2 , wherein the transition metal precursor comprises at least one of transition metal atoms selected from the group consisting of the transition metals belonging to Group 8 and Group 9 of the periodic table.

11. The method for producing a 2-alkenylamine compound according to claim 10 , wherein the transition metal atom is selected from the group consisting of ruthenium, rhodium, and iridium.

Assignees

• Ishibashi Yoshitaka
• Fukumoto Naoya
• Kitamura Masato
• Showa Denko Kk
• Univ Nagoya Nat Univ Corp

Inventors

• Ishibashi Yoshitaka
• Fukumoto Naoya
• Kitamura Masato

Classifications

• C07D295/03

  with the ring nitrogen atoms directly attached to acyclic carbon atoms · CPC title

• C07C209/22

  by substitution of other functional groups · CPC title

• C07C209/60 Primary

  by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes · CPC title

• C07C209/14 Primary

  by substitution of hydroxy groups or of etherified or esterified hydroxy groups · CPC title

• C07C211/21

  Monoamines · CPC title