Fluorination of terpenoid carbonyl compounds used in perfumery

香料中萜类羰基化合物的氟化

• 批准号: 06650977
• 负责人: WATANABE Shoji
• 金额: $ 1.47万
• 依托单位: Chiba University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-06650977/
• 关键词: Reformatsky reaction; Trifluromethylation; Olah reagent; Terpenic aldehyde; Swern oxidation; Trifluoroacetaldehyde; Antimicrobial test; ペンタフルオロエチル化; ジフルオロケトエステル; 不飽和フルオロカルボン酸; Grignard試薬; リパーゼMY

Reformatsky reaction of trifluoroacetaldehyde with lower bromoesters gave their corresponding adducts. The reaction of trifluoroacetaldehyde with methyl 2-(bromomethyl)acrylate gave gamma-trifluoromethyl-alpha-methylene-gamma-butyrolactone. Reformatsky reaction of terpenic aldehydes with difluoromonobromo acetate gave their corresponding adducts. The reaction of citronellal with difluoromonobromo acetate gave ethyl 2,2-difluoro-5,9-dimethyl-3-hydroxy-8-decenoate. Swern oxidation of these hydroxyesters gave their corresponding alpha, alpha-difluoro-beta-ketoesters.The reaction of trifluoromethyltrimethylsilane with a variety of terpenoid carbonyl compounds and other carbonyl compounds used in perfumery gave the corresponding trifluoromethylated derivatives. Pentafluoroethylated compounds were similarlly obtained from the reaction of pentafluoroethyltrimethylsilane with various substrate.(-)-2-Trifluoro-1-furyl ethanol has been obtained with high optical purity by enzymatic hydrolysis of 2-trifluoro-1-furyl ethyl acetate.We had expected that trifluoromethylated and pentafluoroethylated compounds derived from terpenoid compounds would have biological activity. However, our biological tests showed no antimicrobial activity agatint Gram positive and Gram negative bacteria, mycelial fungi and yeasts.

三氟乙醛与低级溴代酯的Reformatsky反应生成了相应的加合物。三氟乙醛与2-（溴甲基）丙烯酸甲酯反应得到γ-三氟甲基-α-亚甲基-γ-丁内酯。萜烯醛与二氟单溴乙酸酯的Reformatsky反应生成了相应的加合物。香茅醛与二氟单溴乙酸酯反应，得到2，2-二氟-5，9-二甲基-3-羟基-8-癸烯酸乙酯。这些羟基酯经Swern氧化得到相应的α，α-二氟-β-酮酯，三氟甲基三甲基硅烷与各种萜类羰基化合物及其它用于香料的羰基化合物反应得到相应的三氟甲基化衍生物。五氟乙基三甲基硅烷与不同底物反应，得到五氟乙基化产物。以2-三氟-1-呋喃基乙酸乙酯为原料，通过酶法水解得到了光学纯度较高的（-）-2-三氟-1-呋喃基乙醇，并期望从萜类化合物中得到具有生物活性的三氟甲基化和五氟乙基化化合物。然而，我们的生物学试验表明，对革兰氏阳性和革兰氏阴性细菌，菌丝真菌和酵母菌没有抗菌活性。

项目成果

S.Watanabe et al: "Trifluoromethylation and pentafluoroethylation of terpenoid carbonyl compounds used in perfumery" Journal of Fluorine Chemistry. 73. 21‐26 ((1995))

S. Watanabe 等人：“香料中使用的萜类羰基化合物的三氟甲基化和五氟乙基化”《氟化学杂志》73. 21-26 ((1995))

渡辺昭次 他: "Trifluoromethylation of Terpenoid Compounds" Journal of Fluorine Chemistry. (印刷中).

Shoji Watanabe 等人：“萜类化合物的三氟甲基化”，氟化学杂志（正在出版）。

S.Watanabe, et al.: "Trifluoromethylation and pentafluoroethylation of terpenoid carbonyl compounds used in perfumery" Journal of Fluorine Chemistry. 73. 21-26 ((1995))

S.Watanabe 等人：“香料中使用的萜类羰基化合物的三氟甲基化和五氟乙基化”《氟化学杂志》。

渡辺昭次 他: "Reaction of trifluoroaceta1dehyde with some bromoesters" Journal of Fluorine Chemistry. 68. 59-61 (1994)

Shoji Watanabe 等人：“三氟乙醛与一些溴代酯的反应”《氟化学杂志》68. 59-61 (1994)。

S.Watanabe, T.Fujita, M.Sakamoto, Y.Mino and T.Kitazume: "Trifluoromethylation and pontafluoroethylation of terpenoid carbonyl compounds used in perfumery" J.Fluorine Chemistry. Vol.73. 21-26 (1995)

S.Watanabe、T.Fujita、M.Sakamoto、Y.Mino 和 T.Kitazume：“香料中使用的萜类羰基化合物的三氟甲基化和五氟乙基化”J.Fluorine Chemistry。