Developments of New Organic Synthetic Reactions Using Inorganic Supports

利用无机载体的新型有机合成反应的进展

• 批准号: 62850148
• 负责人: HOJO Masaru
• 金额: $ 4.16万
• 依托单位: Faculty of Engineering, Kobe University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research
• 财政年份: 1987
• 资助国家: 日本
• 起止时间: 1987 至 1989
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-62850148/
• 关键词: Organic Synthesis Using Inorganic Supports; Substitution at Olefinic Carbons; Fluorine-Containing Heterocycles; Acylation of Aldehyde Hydrazones; Fluorine-Containing Oxadiazines; Fluorine-Containing Thiadiazines; Fluorine-Containing Naphthooxazines

In these ten years we have been engaged in the study of development of new synthetic organic reactions with the use of silica gel as a useful catalyst. Another important recent project in our laboratory is electrophilic and nucleophilic substitution reactions at olefinic carbon atoms. The present study was undertaken to combine the both projects and to develop new synthetic methods for the syntheses of various fluorine-containing heterocycles which are otherwise difficultly accessible. The results are as follows. (1) Ethyl vinyl ether was trifluoroacetylated at the beta-position and then converted to allyl beta-trifluoroacetylvinyl ethers by reaction with various allyl alcohols in the presence of silica gel. The products were submitted to Claisen rearrangement with the use of silica gel to yield 3-allyl-1,1,1-trifluoroacetylacetones, from which various fluorine-containing heterocycles were obtained. (2) Various aldehyde hydrazones were successfully trifluoro- acetylated at the azomethine carbons and then converted by novel cyclization to fluorine- containing oxadiazines in the presence of silica gel. From these oxadiazines various fluorine-containing heterocycles such as thiadiazines, imidazoles, pyrazoles, quinoxalines, pyrazines, thiophenes, furans and pyrroles were obtained. (3) 2,4-Bistrifluoroacetyl- 1-dimethylaminonaphthalene was successfully converted with the use of silica gel as catalyst into fluorine-containing [1,2-d][1,3]oxazine.

在这十年里，我们一直致力于利用硅胶作为有用的催化剂来开发新的合成有机反应。我们实验室最近的另一个重要项目是烯碳原子上的亲电和亲核取代反应。本研究旨在将这两个项目结合起来，并开发新的合成方法，用于合成本来难以获得的各种含氟杂环化合物。研究结果如下。(1)乙基乙烯基醚在硅胶存在下，通过与不同的烯丙醇反应，在β-位发生三氟乙酰化反应生成烯丙基-β-三氟乙酰基乙烯基醚。产物经硅胶Claisen重排得到3-烯丙基-1，1，1-三氟乙酰丙酮，得到各种含氟杂环。(2)在硅胶的存在下，不同的缩醛肼类化合物成功地在甲亚胺碳上进行了三氟乙酰化反应，然后通过新的环化反应转化为含氟的恶二氮类化合物。从这些恶二嗪中得到了各种含氟杂环，如噻二氮、咪唑、吡唑、喹恶啉、吡嗪、噻吩类、呋喃和吡咯等。(3)以硅胶为催化剂，成功地将2，4-二氟乙酰基-1-二甲氨基萘转化为含氟的[1，2-d][1，3]恶嗪。

项目成果

Y.Kamitori: "Electrophilic Subsitution at Azomethine Carbon Atoms. Reaction of Aromatic Aldehyde Hydeazone with Trifluoroacetic Anhydride" J.Org.Chem. 53. 129-134 (1988)

Y.Kamitori：“偶氮甲碱碳原子的亲电取代。芳香醛腙与三氟乙酸酐的反应”J.Org.Chem。

M.Hojo: "Aromatic Nucleophilic Nitrogen-Nitrogen Exchange Reaction of N,N-Dimethyl-2,4-bis(trifluoroacetyl)-1-naphthy with Amino Acid Derivatives:A Facile Syntheis of Fluorine-Containing 1H-Benzo〔g〕-indolines and 1H-Benzo〔g〕indoles" Synthesis. 550-552 (19

M.Hojo：“N,N-二甲基-2,4-双(三氟乙酰基)-1-萘基与氨基酸衍生物的芳香族亲核氮-氮交换反应：含氟1H-苯并[g]-的简便合成二氢吲哚和1H-苯并〔g〕吲哚”的合成。550-552 (19

Masaru Hojo.: Tetrahedron Lett.29. 4599-4602 (1988)

Masaru Hojo.：四面体 Lett.29。

M. Hojo: "A Facile Synthesis of 2,4-Dialkoxy-, 2-Alkoxy-4-Phenoxy-, and 2,4-Diphenoxy-6-trifluoromethyl-3,4-dihydro-2H-pyrans: Hetero-Diels-Alder Reactions of trans-beta-Trifluoroacetylvinyl Ethers with Various Vinyl Ethers" Synthesis p.215-p.217, 1989.

M. Hojo：“2,4-二烷氧基-、2-烷氧基-4-苯氧基-和2,4-二苯氧基-6-三氟甲基-3,4-二氢-2H-吡喃的简便合成：杂-二烯-

M.Hojo: "A Facile Synthesis of 2,4-Dialkoxy-,2-Alkoxy-4-Phenozy-,and2,4-Diphenoxy-6-trifouoromethy1-3,4-ditydro-2H-pyrans:Hetero-Diels-Alder Reactions of Trans-β-Trifluoroacetylvinyl Ethers with Various Vinyl Ethera" Synthesis. 215-217 (1989)

M.Hojo：“2,4-二烷氧基-,2-烷氧基-4-苯氧基-和2,4-二苯氧基-6-三氟甲基1-3,4-二苯并-2H-吡喃的简便合成：Hetero-Diels-Alder反式-β-三氟乙酰乙烯基醚与各种乙烯基醚的反应”合成。215-217 (1989)