Studies on organic reactions in which supercritical alcohols participate as reaction partners

超临界醇作为反应伙伴参与的有机反应的研究

基本信息

  • 批准号:
    11640602
  • 负责人:
  • 金额:
    $ 2.37万
  • 依托单位:
  • 依托单位国家:
    日本
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
  • 财政年份:
    1999
  • 资助国家:
    日本
  • 起止时间:
    1999 至 2001
  • 项目状态:
    已结题

项目摘要

In this study, we found some novel reactions, in which supercritical alcohols participate as the reaction partners.1. Alkenes and alkynes with conjugated aromatic rings reacted with supercritical alcohols to afford hydroxyalkylated derivatives and hydrogenated derivatives. Reaction rates of the hydroxyalkylation of alkenes decreased as follows: Ph_2CH = CH_2 > trans-PhCH = CEPh, PhCH = CH_2 > PhCH_2CH = CH_2, and (CH_3)_2CHOH > CH_3CH_2OH > CH_3OH. It can be posturated that the cleavage of the α-C-H bonds in supercritical alcohols is the rate determining step in the hydroxyalkylation of alkenes.2. Carboxylic acids reacted with supercritical primary alcohols to afford esters. The esterification yields 41 were less than 10 % in the reactions using 2-propanol. Benzoic and 2,4,6-trimethylbenzoic acids were esterified using supercritical ^<18>O-methanol. Based on the results of GC/MS of the resulting esters, the reaction mechanism was suggested to be susceptible to steric hindrance of the carboxylic acids. In the cases of carboxylic acids with no steric hindrance around the carboxylic groups, the esters will be formed via the carbonyl-oxygen bond cleavage in the carboxylic group. On the other hand, the esterification of carboxylic acids with steric hindrance will proceed via the carbon-oxygen bond cleavage in the supercritical alcohol.3. Pyrrole was converted to pyrrole-2-carboxylate in supercritical carbon dioxide using cells of Bacillus megaterium PYR 2910, and the yield of the carboxylation reaction in supercritical carbon dioxide was 12 times than under atmospheric pressure.
在本研究中,我们发现了一些以超临界醇为反应伙伴的新型反应.含共轭芳环的烯烃和炔烃与超临界醇反应,得到羟烷基化衍生物和氢化衍生物。烯烃羟烷基化反应速率依次为Ph_2CH = CH_2 > trans-PhCH = CEPh,PhCH = CH_2 > PhCH_2CH = CH_2,(CH_3)_2CHOH > CH_3CH_2OH > CH_3OH。超临界醇中α-C-H键的断裂是烯烃羟烷基化反应的速率控制步骤.羧酸与超临界伯醇反应生成酯。在使用2-丙醇的反应中,酯化产率41小于10%。苯甲酸和2,4,6-三甲基苯甲酸用超临界甲醇酯化<18>。基于所得酯的GC/MS结果,反应机理被认为是对羧酸的空间位阻敏感。在羧酸基团周围没有空间位阻的情况下,酯将通过羧酸基团中的羰基-氧键断裂形成。另一方面,具有空间位阻的羧酸的酯化反应将通过超临界醇中碳氧键的断裂进行.利用巨大芽孢杆菌PYR 2910细胞在超临界CO2中将吡咯转化为吡咯-2-羧酸酯,超临界CO2中的羧基化反应产率是常压下的12倍。

项目成果

期刊论文数量(10)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
T. Matsuda, R. Kanamaru, K. Watanabe, T. Harada, K. Nakamura: "Control on enantioselectivity with pressure for lipase catalyzed esterification in supercritical carbon dioxide"Tetrahedron Lett.. 42. 8319-8321 (2001)
T. Matsuda、R. Kanamaru、K. Watanabe、T. Harada、K. Nakamura:“用压力控制超临界二氧化碳中脂肪酶催化酯化的对映选择性”Tetrahedron Lett.. 42. 8319-8321 (2001)
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T.Matsuda, R.Kanamaru, K.Watanabe, T.Harada, K.Nakamura: "Control on enantioselectivity with pressure for lipase catalyzed esterification in supercritical carbon dioxide"Tetrahedron Lett.. 42. 8319-8321 (2001)
T.Matsuda、R.Kanamaru、K.Watanabe、T.Harada、K.Nakamura:“用压力控制超临界二氧化碳中脂肪酶催化酯化的对映选择性”Tetrahedron Lett.. 42. 8319-8321 (2001)
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T.Matsuda, R.Kanamaru, K.Watanabe, T.Harada, K.Nakamura: "Control on enantioselectivity with pressure for lipase catalyzed esterification in supercritical carbon dioxide"Tetrahedron Lett.. 42・47. 8319-8321 (2001)
T.Matsuda、R.Kanamaru、K.Watanabe、T.Harada、K.Nakamura:“通过压力控制超临界二氧化碳中脂肪酶催化酯化的对映选择性” Tetrahedron Lett.. 8319-8321 (2001)
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    0
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松田知子, 原田忠夫, 中村薫: "チチカビによる立体選択的酸化還元反応"有機合成化学協会誌. 59. 659-669 (2001)
Tomoko Matsuda、Tadao Harada、Kaoru Nakamura:“C. chinensis 的立体选择性氧化还原反应”合成有机化学学会杂志 59. 659-669 (2001)。
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T. Matsuda, T. Harada: "Enzymatic Reactions in Supercritical carbon dioxide (in Japanese)"BUNRIGIJUTSU. 32 (in press).
T. Matsuda、T. Harada:“超临界二氧化碳中的酶反应(日语)”BUNRIGIJUTSU。
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HARADA Tadao其他文献

HARADA Tadao的其他文献

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{{ truncateString('HARADA Tadao', 18)}}的其他基金

Solid-phase Hydrogenation of Organic Compounds over Metal Catalysts
金属催化剂上有机化合物的固相加氢
  • 批准号:
    03804038
  • 财政年份:
    1991
  • 资助金额:
    $ 2.37万
  • 项目类别:
    Grant-in-Aid for General Scientific Research (C)
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