Title:
PROCESS FOR PRODUCING DIFLUOROCYCLOPROPANE COMPOUND
Document Type and Number:
WIPO Patent Application WO/2011/083612
Kind Code:
A1
Abstract:
Provided is a process for producing a difluorocyclopropane compound under milder reaction conditions and with high selectivity and high yield. The disclosed process for producing a difluorocyclopropane compound is characterized by using sodium bromodifluoroacetate as a difluorocyclopropanation agent. With the disclosed process, a difluorocyclopropane compound can be produced under milder reaction conditions and with a higher conversion rate and higher yield compared to conventional art. Also, by-products can be reduced significantly, thus allowing waste to be greatly reduced. Accordingly, the disclosed production process is easy to implement industrially (can be employed on an industrial scale) and is thus extremely practical and useful.
Inventors:
AMII HIDEKI (JP)
OSHIRO KOJUN (JP)
MORIMOTO YOSHIMICHI (JP)
MATSUURA MAKOTO (JP)
OSHIRO KOJUN (JP)
MORIMOTO YOSHIMICHI (JP)
MATSUURA MAKOTO (JP)
Application Number:
PCT/JP2010/068932
Publication Date:
July 14, 2011
Filing Date:
October 26, 2010
Export Citation:
Assignee:
CENTRAL GLASS CO LTD (JP)
AMII HIDEKI (JP)
OSHIRO KOJUN (JP)
MORIMOTO YOSHIMICHI (JP)
MATSUURA MAKOTO (JP)
AMII HIDEKI (JP)
OSHIRO KOJUN (JP)
MORIMOTO YOSHIMICHI (JP)
MATSUURA MAKOTO (JP)
International Classes:
C07C17/272; C07C23/04; C07C23/28; C07C67/293; C07C67/347; C07C69/157; C07C69/74; C07F5/04; C07F7/18
Foreign References:
| JP2004182671A | 2004-07-02 | |||
| JPS4948637A | 1974-05-11 | |||
| JPS50126642A | 1975-10-04 | |||
| JPH0578272A | 1993-03-30 | |||
| JPS56500296A | 1981-03-12 | |||
| JP2003524593A | 2003-08-19 | |||
| JP2001213830A | 2001-08-07 |
Other References:
KOJUN, OSHIRO. ET AL.: "Sodium Bromodifluoroacetate: A Difluorocarbene Source for the Synthesis of gem-Difluorocyclopropanes.", SYNTHESIS., 16 June 2010 (2010-06-16), pages 2080 - 2084
KOJUN OSHIRO ET AL.: "Shinki Carbene-gen o Mochiiru Difluorocyclopropane no Gosei", 90TH ANNUAL MEETING OF CHEMICAL SOCIETY OF JAPAN IN SPRING 2010 NEN KOEN YOKOSHU IV, 12 March 2010 (2010-03-12), pages 1346, XP008169685
YOSSI, ZAFRANI. ET AL.: "Diethyl bromodifluoromethylphosphonate:a highly efficient and environmentally benign difluorocarbene precursor.", TETRAHEDRON, vol. 65, no. 27, 4 July 2009 (2009-07-04), pages 5278 - 5283, XP026149872
YVES, BESSARD. ET AL.: "gem-DIFLUOROCYCLOPROPENES BY [1+2] CYCLOADDITION REACTIONS BETWEEN DIFLUOROCARBENE AND ACETYLENES HAVING TERMINAL OR INTERNAL TRIPLE BONDS.", TETRAHEDRON, vol. 47, no. 35, 26 August 1991 (1991-08-26), pages 7323 - 7328, XP022160204
YOSHIMICHI MORIMOTO ET AL.: "Kannoki o Yusuru Difluorocyclopropane no Gosei Kagakuteki Oyo", 87TH ANNUAL MEETING OF CHEMICAL SOCIETY OF JAPAN IN SPRING 2007 NEN KOEN YOKOSHU II, 12 March 2007 (2007-03-12), pages 904, XP008169720
See also references of EP 2522648A4
OJIMA, I.,: "Fluorine in Bioorganic and Medicinal Chemistry", 2009, WILEY-BLACKWELL: LONDON, pages: 313 - 334
"Modem Fluoroorganic Chemistry: Synthesis, Reactivity, Applications", 2004, WILEY-VCH: WEINHEIM, pages: 135 - 141
BIRCHALL, J. M.; CROSS, G. E.; HASZELDINE, R. N, PROC. CHEM. SOC., 1960, pages 81
WU, S.-H.; YU, Q., ACTA CHIM. SINICA, 1989, pages 253
TIAN, F.; KRUGER, V K.; BAUTISTA, 0.; DUAN, J.-X.; LI, A.-R.; DOLBIER, W. R., JR.; CHEN, Q.-Y, ORG. LETT., vol. 2, 2000, pages 563
XU, W.; CHEN, Q.-Y, J. ORG. CHEM., vol. 67, 2002, pages 9421
SEYFERTH, D.; DENTOUZOS, H.; ZUZLCI, R.; MUY, J. Y-P., J. ORG. CHEM., vol. 32, 1967, pages 2980
TISSOT, P.; WAEFLER, J. P., THERMOCHIM. ACTA, vol. 66, 1983, pages 315
"Protective Groups in Organic Synthesis,Third Edition,", 1999, JOHN WILEY & SONS, INC.
KOJUN OSHIRO ET AL.: "Shinki Carbene-gen o Mochiiru Difluorocyclopropane no Gosei", 90TH ANNUAL MEETING OF CHEMICAL SOCIETY OF JAPAN IN SPRING 2010 NEN KOEN YOKOSHU IV, 12 March 2010 (2010-03-12), pages 1346, XP008169685
YOSSI, ZAFRANI. ET AL.: "Diethyl bromodifluoromethylphosphonate:a highly efficient and environmentally benign difluorocarbene precursor.", TETRAHEDRON, vol. 65, no. 27, 4 July 2009 (2009-07-04), pages 5278 - 5283, XP026149872
YVES, BESSARD. ET AL.: "gem-DIFLUOROCYCLOPROPENES BY [1+2] CYCLOADDITION REACTIONS BETWEEN DIFLUOROCARBENE AND ACETYLENES HAVING TERMINAL OR INTERNAL TRIPLE BONDS.", TETRAHEDRON, vol. 47, no. 35, 26 August 1991 (1991-08-26), pages 7323 - 7328, XP022160204
YOSHIMICHI MORIMOTO ET AL.: "Kannoki o Yusuru Difluorocyclopropane no Gosei Kagakuteki Oyo", 87TH ANNUAL MEETING OF CHEMICAL SOCIETY OF JAPAN IN SPRING 2007 NEN KOEN YOKOSHU II, 12 March 2007 (2007-03-12), pages 904, XP008169720
See also references of EP 2522648A4
OJIMA, I.,: "Fluorine in Bioorganic and Medicinal Chemistry", 2009, WILEY-BLACKWELL: LONDON, pages: 313 - 334
"Modem Fluoroorganic Chemistry: Synthesis, Reactivity, Applications", 2004, WILEY-VCH: WEINHEIM, pages: 135 - 141
BIRCHALL, J. M.; CROSS, G. E.; HASZELDINE, R. N, PROC. CHEM. SOC., 1960, pages 81
WU, S.-H.; YU, Q., ACTA CHIM. SINICA, 1989, pages 253
TIAN, F.; KRUGER, V K.; BAUTISTA, 0.; DUAN, J.-X.; LI, A.-R.; DOLBIER, W. R., JR.; CHEN, Q.-Y, ORG. LETT., vol. 2, 2000, pages 563
XU, W.; CHEN, Q.-Y, J. ORG. CHEM., vol. 67, 2002, pages 9421
SEYFERTH, D.; DENTOUZOS, H.; ZUZLCI, R.; MUY, J. Y-P., J. ORG. CHEM., vol. 32, 1967, pages 2980
TISSOT, P.; WAEFLER, J. P., THERMOCHIM. ACTA, vol. 66, 1983, pages 315
"Protective Groups in Organic Synthesis,Third Edition,", 1999, JOHN WILEY & SONS, INC.
Attorney, Agent or Firm:
KOBAYASHI Hiroshi et al. (JP)
Kobayashi 浩 (JP)
Kobayashi 浩 (JP)
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