DIENE-DIENOPHILE METATHESIS : A NOVEL METHYLENE MIGRATION REACTION

二烯-亲二烯体复分解：一种新型的亚甲基迁移反应

• 批准号: 02804040
• 负责人: TOHDA Yasuo
• 金额: $ 1.22万
• 依托单位: Osaka Kyoiku 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: 1990
• 资助国家: 日本
• 起止时间: 1990 至 1992
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-02804040/
• 关键词: Diene-Dienophile Metathesis; Six-membered Cyclic Nitronate; Nitroalkene; alpha,beta-Unsaturated Oxime; Reverse Diels-Alder Decomposition; ジェン・ジェノフィル複分解; 逆電子要請Diels-Alder反応; 逆Diels-Alder分解; ジエンージエルフィル複分解; 逆電子要請DielsーAlder反応; ジエンージエノフィル複分解; ニトロオレ

A new reaction, "Diene-Dienophile Metathesis" was investigated which was defined as follow : The reaction is constructed by three consecutive elementary reactions. The first is either Diels-Alder or reverse electron-demand Diels-Alder addition of "diene" and "dienophile". The second is 1,3-prototrophy of the adduct. The third is Diels-Alder decomposition of the isomerized adduct to a rearranged "diene" and "dienophile".We found that nitroalkenes having an electron-withdrawing group such as p-nitrophenyl or sulfonyl groups were good "diene" to give alpha,beta-unsaturated oximes in which the beta-methylene carbon was migrated from the "dienophile". Vinyl ethers were found to be a good "dienophile", while vinyl sulfides derived from aldehydes could not act as "dienophile" because undesirable side reaction occurred.A key intermediate is a six-membered cyclic nitronate and formation and the decomposition of the compound was investigated. 3,5-Dinitro-2-pyridines was found to react with ethyl vinyl ethers to give the nitronate.

研究了一个新的反应--“双烯-亲双烯歧化反应”，其定义如下：该反应由三个连续的基元反应构成。第一种是Diels-Alder或反向电子需求Diels-Alder加成“双烯”和“双烯”。二是1，3-加合物的原生。第三种是异构化加合物的Diels-Alder分解为重排的“双烯”和“亲二烯”。我们发现，具有吸电子基团的硝基烯烃，如对-硝基苯基或磺酰基，是很好的“二烯”，可以生成α，β-不饱和肟类化合物，其中的β-亚甲基碳从“亲二烯基”迁移而来。乙烯基醚是一种很好的“双烯亲和剂”，而由醛衍生的乙烯基硫化物则不能起到“双烯亲和剂”的作用，因为会发生不良的副反应。一个关键中间体是六元环硝酸酯，并研究了该化合物的分解。3，5-二硝基-2-吡啶与乙基乙烯基醚反应生成硝酸酯。

项目成果

任田 康夫: "Novel A adition of 3,5-Dinitro-2-pyridone with Ethyl Vinyl Ether:Formation and Reaction of a Sixmembered Cyclic Nitronate" Bulletin of the Chemical Society of Japan. 66. (1993)

Yasuo Ninda：“新颖的 3,5-二硝基-2-吡啶酮与乙基乙烯基醚的加成：六元环状硝酸酯的形成和反应”日本化学学会公报 66。（1993）。

任田 康夫,有賀 正裕,谷 敬太,西脇 永敏: "ビニルエ-テルの3.5ージニトロー2ーピリドン類への付加反応:六員環環状ニトロン酸エステルの生成と新奇な分解" 日本化学会第63春季年会講演予稿集. 2315-2315 (1992)

Yasuo Nonda、Masahiro Ariga、Keita Tani、Nagatoshi Nishiwaki：“乙烯基醚与 3.5-二硝基-2-吡啶酮的加成反应：六元环状硝酸酯的形成和新型分解”第 63 届日本化学会春季年会讲座记录。2315-2315（1992）

任田 康夫: "Novel Addition of 3,5-Dinitro-2pyridone with Ethyl Vinyl Ether:Formation and Reactions of a Six-membered Cyclic Nitronate" Bulletin of Chemical Society of Japan. 66. 1222-1228 (1993)

Yasuo Ninda：“3,5-二硝基-2吡啶酮与乙基乙烯基醚的新加成：六元环状硝基化合物的形成和反应”日本化学学会公报 66. 1222-1228 (1993)。

Y. TOHDA: "Novel Addition of 3,5-Dinitro-2-pyridine with Ethyl Vinyl Ether : Formation and Reactions of a Six-membered Cyclic Nitronate" Bulletin of the Chemical Society of Japan. Vol.66. (1993)

Y. TOHDA：“3,5-二硝基-2-吡啶与乙基乙烯基醚的新加成：六元环状硝基化合物的形成和反应”日本化学会会刊。

任田 康夫: "3.5ージニトロー2ーピリドンとビニルエ-テルの新しい環化付加反応" Bulletin of the Chemical Society of Japan.

Yasuo Ninda：“3.5-二硝基-2-吡啶酮和乙烯基醚的新环加成反应”日本化学会会报。