The Organic Reactions and Synthesis based on the Utilization of Carbon Monoxide

基于一氧化碳利用的有机反应与合成

• 批准号: 02650615
• 负责人: HAMANAKA Sawako
• 金额: $ 1.28万
• 依托单位: KASAI 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-02650615/
• 关键词: Carbon Monoxide; Hydrogen Selenide; Dibromination; Diorganylselenides; Selenocarboxylates; Aluminum Halide; Phenylalkylcarbocations; Adamantanecarboxaldehyde; フェニル置換α,βージケトン; アダマンタン; アダマンタンカルボキシルアルデヒド; ジアルキルセレニド; ジアルキルジセレニド; セレノカルボキシレ-ト; アダマ

1. Synthesis utilization reducing ability of carbon monoxide, - Using CO/H_2O/Se reaction system-(1) In the reductive dibromination of vic-dibromoalkanes with CO and H_2O in the presence of a catalytic amount of Se, vic-dibromoalkanes were converted to the corresponding alkanes in good yields and stereospecific.(2) The selective generation of tertiary amine salts of hydrogen selenide and diselenide has been achived by controlling the reaction conditions. Diorganylselenides and diorganyldiselenides were synthesized in good yields with perfect selectivity.(3) Phenyl substituted alpha- and beta-diketones were reduced to corresponding aromatic ketones in moderate to good yields.2. Utilization of carbon monoxide as a useful agentas for introducing carbonyl functions into organic molecules.(1) Treatment of 1, 1- or 1, 2-diphenylalkanes in benzene with AlCl_3-HCl formed the red-oil involving a phenylalkylcarbocations. When carbon monoxide was introduced to the red-oil, the phenylalkylcarbocations reacted with carbon monoxide to give 2-disubstituted-1-indanones via cyclization of the resulting acylcation.(2) 1-adamantanecarboxaldehyde was synthesized by the AlI_3-catalyzed reaction of adamantane with CO in CH_2Cl_2 at < 25ﾟC

1.利用CO/H_2O/Se反应体系，（1）在催化量Se存在下，用CO和H_2O还原二溴代邻二溴代烷烃，使其转化为相应的烷烃，产率高，立体定向性好。(2)通过控制反应条件，实现了硒化氢和二硒化氢叔胺盐的选择性生成。合成了二有机硒醚和二有机二硒醚，产率高，选择性好。(3)苯基取代的α-和β-二酮以中等至良好的产率被还原为相应的芳香酮。一氧化碳作为有机分子中引入羰基官能团的有效试剂的应用。(1)1，1-或1，2-二苯烷烃在苯中用AlCl_3-HCl处理形成含有苯烷基碳正离子的红色油。当红油中引入一氧化碳时，苯烷基碳正离子与一氧化碳反应，生成的酰基阳离子经环化反应生成2-二取代-1-茚满酮。(2)在AlI_3催化下，金刚烷与CO在CH_2Cl_2中于< 25 ℃反应合成了1-金刚烷甲醛

项目成果

西山 豊,浜中 佐和子 他6名: "Synthesis Utilizing Reducing Ability of Carbon Monoxide:A New Method for Selective Synthesis of Diorganyl Selenides and Diselenides Using a SeleniumーCarbon MonoxideーWater Reaction System" J.Org.Chem.56. 3776 (1991)

Yutaka Nishiyama、Sawako Hamanaka 等 6 人：“利用一氧化碳还原能力的合成：利用硒－一氧化碳－水反应系统选择性合成二有机基硒化物和二硒化物的新方法”J.Org.Chem.56（ 1991)

岡田 隆志: "塩化アルミニウムによるジフェニルアルカンと一酸化炭素との反応" Chemistry Express. 5. 293-296 (1990)

Takashi Okada：“使用氯化铝进行二苯基烷烃与一氧化碳的反应”Chemistry Express 5. 293-296 (1990)。

Yutaka Nishiyama: "Selenium-Assisted Reduction of alpha- and beta-Diketones with Carbon Monoxide and Water" Tetrahedoron Letters. 33-42. 6347-6350 (1992)

Yutaka Nishiyama：“硒辅助一氧化碳和水还原 α- 和 β-二酮”四面体字母。

Yutaka NISHIYAMA: "Selebium-Assisted Reduction of α-and β-Diketones with Carbon Monoxide and Water" Tetrahedoron Letters. 33. 6347-6350 (1992)

Yutaka NISHIYAMA：“一氧化碳和水的硒辅助还原 α-和 β-二酮”四面体快报 33. 6347-6350 (1992)

Yutaka Nishiyama: "Selenium-Catalyzed Debromination of vic-Dibromoalkanes and alpha-Bromo Ketones with Carbon Monoxide and Water" Heteroatom Chemistry. 1-6. 467-473 (1990)

Yutaka Nishiyama：“硒催化脱溴二溴烷烃和α-溴酮与一氧化碳和水”杂原子化学。