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Process for producing nitrogenous 5-membered cyclic compound

Foreign code F110003811
File No. E07609WO
Posted date Jul 5, 2011
Country United States of America
Application number 59213905
Gazette No. 20070191614
Gazette No. 7705161
Date of filing Feb 21, 2005
Gazette Date Aug 16, 2007
Gazette Date Apr 27, 2010
International application number JP2005003236
International publication number WO2005085204
Date of international filing Feb 21, 2005
Date of international publication Sep 15, 2005
Priority data
  • P2004-066434 (Mar 9, 2004) JP
  • 2005WO-JP03236 (Feb 21, 2005) WO
Title Process for producing nitrogenous 5-membered cyclic compound
Abstract (US7705161)
A method of the intramolecular and intermolecular cyclization of an N-acylhydrazone for obtaining a pyrazoline skeleton or pyrazolidine skeleton under ordinary conditions with high stereoselectivity and in high yield.
An N-acylhydrazone represented by the following formula (I): (wherein R1 and R2 are the same or different and each represents hydrogen or a hydrocarbon group and Ar represents an optionally substituted aromatic hydrocarbon group) is converted to an N-acylpyrazoline derivative with high stereoselectivity in the presence of a Lewis acid catalyst or asymmetric Lewis acid catalyst.
Scope of claims [claim1]
1. A process for intramolecular cyclization of an N-acylhydrazone which comprises reacting an N-acylhydrazone represented by the following formula (I)

wherein R1 and R2 are the same or different and each represents a hydrogen atom or a hydrocarbon group, and Ar represents an optionally substituted aromatic hydrocarbon group, with a Lewis acid catalyst to obtain an N-acylpyrazoline derivative represented by the following formula (II)

wherein R1, R2 and Ar have the same meanings as indicated above.
[claim2]
2. A process according to claim 1 wherein the Lewis acid catalyst is scandium triflate.
[claim3]
3. A process for asymmetric intramolecular cyclization of an N-acylhydrazone which comprises reacting an N-acylhydrazone represented by the following formula (I)

wherein R1 and R2 are the same or different and each represents a hydrogen atom or a hydrocarbon group, and Ar represents an optionally substituted aromatic hydrocarbon group, with an asymmetric Lewis acid catalyst, which can be obtained by mixing a zirconium alkoxide or zirconium dialkoxide dihalide represented by the following formula (III)
ZrP2Q2 (III)
wherein P represents an alkoxy group, and Q represents an alkoxy group or a halogen atom, and a binaphthol derivative represented by the following formula (IV)

wherein X represents a hydrogen atom, a halogen atom, a hydrocarbon group or a perfluoroalkyl group; Y represents a hydrogen atom, a halogen atom, a hydrocarbon group or a perfluoroalkyl group; and X and Y may be the same, to obtain an optically active N-acylpyrazoline derivative represented by the following formula (II')

wherein R1, R2 and Ar have the same meanings as indicated above.
[claim4]
4. A process for asymmetric intermolecular cyclization of an N-acylhydrazone which comprises reacting an N-acylhydrazone represented by the following formula (V)

wherein R3 represents an optionally substituted hydrocarbon group and Ar represents an optionally substituted aromatic hydrocarbon group, with an olefinic compound represented by the following formula (VI)

wherein R4 and R5 are the same or different and each represents a hydrogen atom or a substituent selected from the group consisting of hydrocarbon group, alkoxy group and alkylthio group and at least one of R4 and R5 is other than a hydrogen atom, in the presence of an asymmetric Lewis acid catalyst, obtained by mixing a zirconium alkoxide or zirconium dialkoxide dihalide represented by the following formula (III)
ZrP2Q2 (III)
wherein P represents an alkoxy group and Q represents an alkoxy group or a halogen atom, and a binaphthol derivative represented by the following formula (IV)

wherein X represents a hydrogen atom, a halogen atom, a hydrocarbon group or a perfluoroalkyl group, and Y represents a hydrogen atom, a halogen atom, a hydrocarbon group or a perfluoroalkyl group and X and Y may be the same, to obtain an optically active N-acylpyrazolidine derivative represented by the following formula (VII)

wherein R3 to R5 and Ar have the same meanings as indicated above.
  • Inventor, and Inventor/Applicant
  • KOBAYASHI SHU
  • YAMASHITA YASUHIRO
  • JAPAN SCIENCE AND TECHNOLOGY AGENCY
IPC(International Patent Classification)
Reference ( R and D project ) ERATO KOBAYASHI Highly Functionalized Reaction Environments AREA
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