Patent
Method for producing difluorocyclopropane compound
| العنوان: | Method for producing difluorocyclopropane compound |
|---|---|
| Patent Number: | 8,729,320 |
| تاريخ النشر: | May 20, 2014 |
| Appl. No: | 13/520691 |
| Application Filed: | October 26, 2010 |
| مستخلص: | Provided is a method for producing a difluorocyclopropane compound under milder reaction conditions and with high selectivity and high yield. The method for producing a difluorocyclopropane compound of the present invention is characterized by using sodium bromodifluoroacetate as a difluorocyclopropanation agent. With the disclosed method, a difluorocyclopropane compound can be produced under milder reaction conditions and with a higher conversion rate and a higher yield compared to conventional art. Further, by-products can be reduced significantly, thus allowing waste to be greatly reduced. Accordingly, the production method of the present invention is easy to implement industrially (can be employed on an industrial scale) and is thus extremely practical and useful. |
| Inventors: | Amii, Hideki (Kobe, JP); Oshiro, Kojun (Kobe, JP); Morimoto, Yoshimichi (Kobe, JP); Matsuura, Makoto (Kawagoe, JP) |
| Assignees: | Central Glass Company, Limited (Ube-Shi, JP) |
| Claim: | 1. A method for producing a difluorocyclopropane compound by reacting a compound having a chain or cyclic ethylene skeleton with a difluorocyclopropanation agent, wherein bromodifluoroacetate is used as the difluorocyclopropanation agent. |
| Claim: | 2. The method according to claim 1 , wherein the compound having the ethylene skeleton is a compound having the following general formula (1): [chemical expression included] wherein in the general formula (1): R 1 to R 4 each independently represent a hydrogen atom, or a C 1-10 linear or branched aliphatic hydrocarbon group, aromatic ring group, alkoxy group, alkoxycarbonyl group, trialkylsilyl group or boryl group, which may be substituted with any group; and R 2 and R 4 may mutually constitute a portion of the same aliphatic ring or aliphatic heterocycle, or may mutually form a single bond, and wherein the difluorocyclopropane compound is a compound having the following general formula (2): [chemical expression included] wherein in the general formula (2), R 1 to R 4 are the same as above. |
| Claim: | 3. The method according to claim 1 or 2 , wherein the bromodifluoroacetate is represented by the following formula: BrCF 2 CO 2 R 5 wherein R 5 represents an alkali metal atom or an alkali earth metal atom. |
| Claim: | 4. The method according to claim 3 , wherein the alkali metal is sodium, lithium or potassium and the alkali earth metal is magnesium. |
| Claim: | 5. The method according to claim 1 , wherein a reaction temperature of the reaction is 100 to 200° C. |
| Claim: | 6. The method according to claim 1 , wherein a reaction time of the reaction is 5 to 60 minutes. |
| Current U.S. Class: | 570/133 |
| Patent References Cited: | 3825606 July 1974 O'Neill et al. 3903181 September 1975 O'Neill et al. 3906111 September 1975 Billings et al. 3928468 December 1975 Billings et al. 4201881 May 1980 DeLuca et al. 5089662 February 1992 Wegner et al. 6051539 April 2000 Kodali et al. 2009/0318408 December 2009 Cai et al. 1 026 154 August 2000 49-48637 May 1974 50-126642 October 1975 56-500296 March 1981 5-78272 March 1993 2001-213830 August 2001 2001-213830 August 2001 2003-524593 August 2003 2003-524593 August 2003 2004-182671 July 2004 2004-182671 July 2004 |
| Other References: | Bessard et al., “gem-Difluorocyclopropenes by [1+2] Cycloaddition Reactions Between Difluorocarbene and Acetylenes Having Terminal or Internal Triple Bonds”, Tetrahedron, Aug. 26, 1991, vol. 47, No. 35, pp. 7323-7328. cited by applicant Birchall et al., “Difluorocarbene”, Proc. Chem. Soc., Feb. 1960, p. 81. cited by applicant International Search Report issued in PCT/JP2010/068932 dated Jan. 18, 2011. cited by applicant Kirsch, “Modern Fluoroorganic Chemistry: Synthesis, Reactivity, Applications”, Wiley-VCH: 2004, Weinheim, Germany, pp. 135-141. cited by applicant Kojun et al., “Sodium Bromodifluoroacetate: A Difluorocarbene Source for the Synthesis of gem-Difluorocyclopropanes”, Synthesis, Jun. 16, 2010, No. 12, pp. 2080-2084. cited by applicant Kojun et al., “Synthesis of Difluorocyclopropane Using a New Difluorocyclopropane source”, 90th Annual Meeting of Chemical Society of Japan in Spring 2010 Nen Koen Yokoshu IV, Mar. 12, 2010, p. 1346. cited by applicant Morimoto et al., “Synthesic Applications of Functionalyzed Difluorocyclopropanes” 87th Annual Meeting of Chemical Society of Japan in Spring 2007 Nen Koen Yokoshu II, Mar. 12, 2007, p. 904. cited by applicant Ojima (Ed.), “Fluorine in Medicinal Chemistry and Chemical Biology”, Wiley-Blackwell, 2009, London, UK, pp. 313-334. cited by applicant Seyferth et al., “Halomethyl Metal Compounds. XIII. The Preparation of gem-Difluorocyclopropanes by Iodide Ion Induced CF2 Transfer from Trimethyl(trifluoromethyl)tin”, J. Org. Chem., 1967, vol. 32, pp. 2980-2984. cited by applicant Tian et al., “A Novel and Highly Efficient Synthesis of gem-Difluorocyclopropanes”, Organic Letters, 2000, vol. 2, No. 4, pp. 563-564. cited by applicant Tissot et al., “Thermal Decomposition of the Alkaline Salts of Difluorochloro-and Difluorobromoacetic Acids”, Thermochimica Acta, 1983, 66, pp. 315-321. cited by applicant Wu et al., “Application of carbene reactive intermediates in organic synthesis”, ACTA Chimica Sinica English Edition, 1989, No. 3, pp. 253-257. cited by applicant Xu et al., “3,3-Difluoro-1-iodocyclopropenes: A Simple Synthesis and Their Reactions”, J. Org. Chem., 2002, 67, pp. 9421-9427. cited by applicant Zafrani et al., “Diethyl bromodifluoromethylphosphonate: a highly efficient and environmentally benign difluorocarbene precursor”, Tetrahedron, Jul. 4, 2009, vol. 65, No. 27, pp. 5278-5283. cited by applicant Boyer et al., “Chemoselective and stereoselective synthesis of gem-difluoro-β-aminoesters or gem-difluoro-β-lactams from ethylbromodifluoroscetate and imines during Reformatsky reaction,” Tetrahedrom (2007), vol. 63, pp. 12352-12366. cited by applicant Extended European Search Report issued Apr. 25, 2013, in European Patent Application No. 10842127.2. cited by applicant |
| Assistant Examiner: | Bakshi, Pancham |
| Primary Examiner: | Sajjadi, Fereydoun G |
| Attorney, Agent or Firm: | Birch, Stewart, Kolasch & Birch, LLP |
| رقم الانضمام: | edspgr.08729320 |
| قاعدة البيانات: | USPTO Patent Grants |
| الوصف غير متاح. |