专利号:EP-2644590-A1 优先权日:2012-03-30 标 题:Synthesis of 2-(3,4-difluorophenyl)cyclopropanamine derivatives and salts 权利人:LEK PHARMACEUTICALS 摘要:The present invention relates to the field of organic synthesis and describes the synthesis of specific intermediates suitable for the preparation of triazolopyrimidine compounds such as ticagrelor.
专利号:US-6025492-A 优先权日:1996-08-30 标 题 :Synthesis of a hydrazone β-keto ester by the reaction with a diazo ester 发明人:SHAH AJIT S; CLARK JERRY D; MA YINONG; PETERSON JAMES C; PATELIS LEFTERIS 权利人:MONSANTO CO 摘要:The present invention relates to the synthesis of a hydrazone β-keto ester by the reaction of an alkyl diazoester with a hydrazone aldehyde in the presence of a Lewis acid In a preferred embodiment, the hydrazone β-keto ester is then converted into a pyridazinone compound by the reaction with an alkyl acid chloride in the presence of a base, followed by acidification. A process for the production of a hydrazone aldehyde, which comprises contacting a hydrazine and glyoxal, is also described.
专利号:US-6258960-B1 优先权日:2000-03-17 标题:Catalytic asymmetric synthesis of chiral aziridines 发明人:ANTILLA JON; WULFF WILLIAM D 权利人:ARCH DEV CORP 摘要:The present invention relates to the synthesis of chiral cis-aziridines (IIIa and IIIb) by reacting an imine (I) with a diazo compound (II) in the presence of a chiral vaulted biary-Lewis Acid complex as shown below:
专利号:US-4284582-A 优先权日:1978-04-28 标 题 :Process for the preparation of cyclopropane derivatives, intermediates in the synthesis of pyrethroid insecticides 发明人:KAYE ALBERT E; TUCKER ALAN C 权利人:ICI LTD 摘要:Compounds of formula: wherein both groups X are chlorine, bromine or trifluoromethyl, or one X is chlorine or bromine and the other is trifluoromethyl, and Y is -CN or -COOR in which R is an alkyl group, are obtained by (A) reacting a compound of the formula: wherein X1 is chlorine or bromine, with a compound of the formula: X2C=CH-CH=C(CH3)2 in the presence of metallic copper or at least one copper salt and a base, or (B) reacting a compound of the formula: Y-CH2-CN with a compound of the formula: X2C=CH-CH=C(CH3)2 and chlorine or bromine, in the presence of at least one reducible copper salt and a base, or (C) reacting a compound of formula: X-CH2-CN with a compound of the formula: wherein X1 is chlorine or bromine, in the presence of at least one copper salt. The compounds are intermediates in the synthesis of pyrethroid insecticides.
专利号:WO-0056708-A1 优先权日:1999-03-19 标题 :Catalytic asymmetric synthesis of chiral aziridines 发明人:WULFF WILLIAM D; ANTILLA JON 权利人:ARCH DEV CORP 摘要:The present invention relates to the synthesis of chiral cis-aziridines (IIIa and IIIb) by reacting an imine (I) with a diazo compound (II) in the presence of a chiral vaulted biaryl-Lewis Acid complex as shown.
专利号:US-3699146-A 优先权日:1970-03-31 标题:Synthesis of methyl malvalate and methyl 5,6-methano-5-undecenoate 发明人:GENSLER WALTER J 权利人:US AGRICULTURE 摘要:This invention relates to the preparation of methyl malvalate, methyl 5,6-methano-5-undecenoate and the preparation of some new intermediates. Malvalic acid, the major cyclopropene component in cottonseed oil, has been synthesized. When 1-chloro-7-hexadecyne reacts with diazoacetic ester in the presence of copper bronze, the ester of 1-chloro-7,8-carboxymethano-7-hexadecene is formed. Treating the corresponding acid chloride with zinc chloride causes loss of carbon monoxide. Either sodium borohydride or lithium aluminum hydride reduces the resulting cyclopropenium compound to 1-chloro-7,8-methano-7-hexadecene. Replacing the chloro group with cyano yields malvalonitrile, which can be converted to methyl malvalate. An analogous sequence of steps has been applied to 1-chloro-4-decyne to produce methyl 5,6-methano5-undecenoate. An alternate synthesis of methyl malvalate starts by using 1-chloro-7-hexadecyne as the precursor for methyl 8heptadecynoate. This acetylenic ester is converted to 8,9carboxymethano-8-heptadecenoic acid, the diacid chloride of which decarbonylates selectively in the presence of metallic chlorides to form the cyclopropenium-acid chloride. After esterification the resulting cyclopropenium-ester is reduced with borohydride to methyl malvalate.
1: Delville MM, van Hest JC, Rutjes FP. Ethyl diazoacetate synthesis in flow. Beilstein J Org Chem. 2013 Sep 5;9:1813-8. doi: 10.3762/bjoc.9.211. eCollection 2013. 2: Ma C, Xing D, Zhai C, Che J, Liu S, Wang J, Hu W. Iron porphyrin-catalyzed three-component reaction of ethyl diazoacetate with aliphatic amines and β,γ-unsaturated α-keto esters. Org Lett. 2013 Dec 20;15(24):6140-3. doi: 10.1021/ol403011r. Epub 2013 Nov 19. doi: 10.3762/bjoc.11.245. eCollection 2015. 4: Li J, Qin G, Huang H. Silver-catalyzed nucleophilic substitution of aminals with ethyl diazoacetate: a new pathway to β-amino-α-diazoesters. Org Biomol Chem. 2016 Dec 7;14(45):10572-10575. Epub 2016 Oct 26. doi: 10.1021/ja206995s. Epub 2012 Jan 18.
合成参考文献
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