トリフルオロメチル基を有する合成ピレスロイドの新規合成法 : 亜鉛カルベノイド反応剤CF<SUB>3</SUB>CCl<SUB>2</SUB>ZnClの開発と応用
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Practical and stereocontrolled new methods for the synthesis of highly potent synthetic pyrethroids, 2, 2-dimethyl-3- (2-chloro- 3, 3, 3- trifluoro- 2- propenyl) cyclopropanecarboxylates are described. The key of the methods is the transformation of RCHO to RCH=C (Cl) CF<SUB>3</SUB>. This was achieved (1) by aldehyde addition of a zinc carbenoid CF<SUB>3</SUB>CCl<SUB>2</SUB>ZnCl prepared from CCl<SUB>3</SUB>CF<SUB>3</SUB> and Zn, followed by acetylation and reduction; (2) by one-pot procedure using CF<SUB>3</SUB>CCl<SUB>3</SUB>/Zn (> 2mol) /Ac<SUB>2</SUB>O (1mol); or (3) by conversion to RCH (OH) CX = CF<SUB>2</SUB> with CF<SUB>3</SUB>CCl<SUB>3</SUB>/Zn (> 2mol) /AlCl<SUB>3</SUB> (cat.) followed by regio- and stereoselective fluorination. Application of these to 3- formyl- 2, 2- dimethycyclopropanecarboxylates afforded the trans isomer of the target compounds. A series of transformation involving addition of CF<SUB>3</SUB>CCl<SUB>2</SUB>ZnCl to 3- methy- 2- butenal, conversion into Me<SUB>2</SUB>C = CHCH (COCHN<SUB>2</SUB>) CCl<SUB>2</SUB>CF<SUB>3</SUB>, intramolecular carbene addition, and reduction gave the cis acid of the aimed pyrethroids.
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