Method for producing lactam compound, and lactam compound produced thereby

Patent metadata

Field	Value
Publication number	US-11046661-B2
Application number	US-201916959863-A
Country	US
Kind code	B2
Filing date	Jan 2, 2019
Priority date	Jan 2, 2018
Publication date	Jun 29, 2021
Grant date	Jun 29, 2021

Abstract

The present invention relates to a method for producing a lactam compound from dioxazolone in the presence of a catalyst having a particular ligand, and to a lactam compound produced thereby, and can produce a lactam compound with excellent selectivity and an excellent yield by using the combination of a starting material having a particular functional group and a particular catalyst having a particular ligand.

First claim

The invention claimed is:

1. A method of preparing a lactam compound, the method comprising: amidating a 3-substituted dioxazol-one compound in the presence of a catalyst represented by the following Chemical Formula 1 and a base to prepare a lactam compound:

wherein
M is iridium, rhodium, ruthenium, or cobalt;
X is a halogen;
R1 to R5 are independently of one another hydrogen or (C1-C7)alkyl; and
R6 is a halogen, (C1-C20)alkyl, halo(C1-C20)alkyl, (C1-C20)alkoxy, (C6-C20)aryl, or (C3-C20)heteroaryl; and
n is an integer of 0 to 6.

2. The method of preparing a lactam compound of claim 1 , wherein amidating a 3-substituted dioxazol-one compound of the following Chemical Formula 2 in the presence of the catalyst represented by Chemical Formula 1 and the base to prepare a lactam compound of the following Chemical Formula 3 is included:

wherein
Ra1 and Ra2 are independently of each other hydrogen, (C1-C20)alkyl, (C6-C20)aryl, or (C3-C20)heterocyclalkyl;
Ra3 to Ra6 are independently of one another hydrogen, a halogen, (C1-C20)alkyl, halo(C1-C20)alkyl, (C2-C20)alkenyl, (C2-C20)alkynyl, (C1-C20)alkoxy, (C6-C20)aryl, or (C3-C20)heteroaryl, or may be connected to an adjacent substituent to form an aromatic ring or an alicyclic ring with or without a fused ring; and
q is an integer of 1 or 2.

3. The method of preparing a lactam compound of claim 1 , wherein amidating a 3-substituted dioxazol-one compound of the following Chemical Formula 4 in the presence of the catalyst represented by Chemical Formula 1 and the base to prepare a lactam compound of the following Chemical Formula 5 is included:

wherein
Ra1 and Ra2 are independently of each other hydrogen, (C1-C20)alkyl, (C6-C20)aryl, or (C3-C20)heterocyclalkyl;
Ra7 to Ra10) are independently of one another hydrogen, a halogen, (C1-C20)alkyl, halo(C1-C20)alkyl, (C2-C20)alkenyl, (C2-C20)alkynyl, (C1-C20)alkoxy, (C6-C20)aryl, or (C3-C20)heteroaryl, or may be connected to an adjacent substituent to form an aromatic ring or an alicyclic ring with or without a fused ring;
q is an integer of 1 or 2.

4. The method of preparing a lactam compound of claim 1 , wherein amidating a 3-substituted dioxazol-one compound of the following Chemical Formula 6 in the presence of the catalyst represented by Chemical Formula 1 and the base to prepare a lactam compound of the following Chemical Formula 7 is included:

wherein
Ra1 and Ra2 are independently of each other hydrogen, (C1-C20)alkyl, (C6-C20)aryl, or (C3-C20)heterocycloalkyl;
Ra7 to Ra11) are independently of one another hydrogen, a halogen, (C1-C20)alkyl, halo(C1-C20)alkyl, (C2-C20)alkenyl, (C2-C20)alkynyl, (C1-C20)alkoxy, (C6-C20)aryl, or (C3-C20)heteroaryl, or may be connected to an adjacent substituent to form an aromatic ring or an alicyclic ring with or without a fused ring; and
q is an integer of 1 or 2.

5. The method of preparing a lactam compound of claim 1 , wherein amidating a 3-substituted dioxazol-one compound of the following Chemical Formula 8 in the presence of the catalyst represented by Chemical Formula 1 and the base to prepare a lactam compound of the following Chemical Formula 9 is included:

wherein
Ra11 to Ra14 are independently of one another hydrogen or (C1-C20)alkyl;
Ra15 is a halogen, (C1-C20)alkyl, halo(C1-C20)alkyl, (C2-C20)alkenyl, (C2-C20)alkynyl, (C1-C20)alkoxy, (C6-C20)aryl, or (C3-C20)heteroaryl;
Ra16 is hydrogen or (C1-C20)alkyl; and
p is an integer of 0 to 4.

6. The method of preparing a lactam compound of claim 1 , wherein the catalyst is used at 0.01 to 0.1 mol with respect to 1 mol of the 3-substituted dioxazol-one compound.

7. The method of preparing a lactam compound of claim 1 , wherein the base is one or two or more selected from NaBArF4, AgSbF6, AgNTf2, AgBF4, AgPF6, AgOTf, and AgOAc.

8. The method of preparing a lactam compound of claim 1 , wherein the base is used at 0.01 to 0.1 mol with respect to 1 mol of the 3-substituted dioxazol-one compound.

9. The method of preparing a lactam compound of claim 1 , wherein the amidating is performed at 20 to 80° C.

10. The method of preparing a lactam compound of claim 1 , wherein in Chemical Formula 1, M is iridium, X is chloro, R1 to R5 are independently of one another (C1-C30)alkyl, R6 is a halogen, and n is an integer of 0 to 2.

11. The method of preparing a lactam compound of claim 2 , wherein
Ra1 and Ra2 are independently of each other hydrogen, (C6-C20)aryl, or phthalimido;
Ra3 to Ra6 are independently of one another hydrogen, a halogen, (C1-C20)alkyl, halo(C1-C20)alkyl, or (C1-C20)alkoxy, or may be connected to an adjacent substituent to form an aromatic ring with or without a fused ring; and
q is an integer of 1 or 2.

12. The method of preparing a lactam compound of claim 3 , wherein
Ra1 and Ra2 are independently of each other hydrogen or phthalimido;
Ra7 to Ra10 are independently of one another hydrogen, a halogen, (C1-C20)alkyl, or (C1-C20)alkoxy, or may be connected to an adjacent substituent to form an aromatic ring with or without a fused ring; and
q is an integer of 1 or 2.

13. The method of preparing a lactam compound of claim 5 , wherein
Ra11 to Ra14 are independently of one another hydrogen;
Ra15 is a halogen, (C1-C20)alkyl, or (C1-C20)alkoxy;
Ra16 is hydrogen or (C1-C20)alkyl; and
q is an integer of 0 or 1.

14. The method of preparing a lactam compound of claim 4 , wherein
Ra1 and Ra2 are independently of each other hydrogen or phthalimido;
Ra7 to Ra10) are independently of one another hydrogen, a halogen, (C1-C20)alkyl, or (C1-C20)alkoxy, or may be connected to an adjacent substituent to form an aromatic ring with or without a fused ring; and
q is an integer of 1 or 2.

Assignees

• Inst Basic Science
• Korea Advanced Inst Sci & Tech

Inventors

• Chang Sukbok
• Hong Seung Youn
• Park Yoon Su
• Hwang Yeongyu
• Kim Yeong Bum

Classifications

• C07D215/227

  only one oxygen atom which is attached in position 2 · CPC title

• C07F15/0046

  Ruthenium compounds · CPC title

• C07D205/12 Primary

  condensed with carbocyclic rings or ring systems · CPC title

• C07F15/0073

  Rhodium compounds · CPC title

• C07D273/01 Primary

  having one nitrogen atom · CPC title