Research on the production of new type of cyclic carbonates by using organomaignroup metal-compounds as high active catalysts

以有机金属化合物为高活性催化剂生产新型环状碳酸酯的研究

• 批准号: 61850152
• 负责人: MATSUDA Haruo
• 金额: $ 2.56万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research
• 财政年份: 1986
• 资助国家: 日本
• 起止时间: 1986 至 1987
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-61850152/
• 关键词: carbonate; carbon dioxide; oxirance; stereo-specificity; organotin halide complexes; 有機スズ錯体触煤

This project aims the production of various carbonates from oxiranes and carbon dioxide at industrially practical reaction-rate. For this aim, we have developed novel organomaingrroup-metallic catalyst; R_3 SnI-Lewis bases, R_2 SnI_2 -onium iodides, PH_4 SBI, so on. These catalytic cystems have some advanitages as follows.(1) High catalystic activity; the cycloaddition of carbon dioxide and oxiranes proceeds under very mild conditions such as room temperature and lower pressure of carbon dioxide. Less reactive oxiranes such as 2,3-dimethyloxirance readily react with carbon dioxide to give carbonates in high yield.(2) Neutrality; these catalysts are so nearly neutral that wide range of oxiranes area appliciable. Particularyly, it is noteworthy that the acidity of the tin complexes is considerably lower than one of non-complexed organotin halides.(3) Stereospecificity; cis oxiranes gave cis carbonates in high selectivity, although the isomerization of oxiranes to corresponding ketones are accompanied. This isomerization could not be depressed completely even by our novel catgalyst.

该项目的目标是以工业实用的反应速率从环氧乙烷和二氧化碳生产各种碳酸酯。为此，我们开发了新型有机基团金属催化剂； R_3 SnI-Lewis碱、R_2 SnI_2-碘化鎓、PH_4 SBI等。这些催化体系具有以下优点：（1）催化活性高；二氧化碳和环氧乙烷的环加成在非常温和的条件下进行，例如室温和较低的二氧化碳压力。反应性较低的环氧乙烷，如2,3-二甲基环氧乙烷，很容易与二氧化碳反应，高产率地生成碳酸酯。(2)中性；这些催化剂几乎是中性的，因此环氧乙烷的适用范围很广。特别值得注意的是，锡络合物的酸度远低于非络合的有机锡卤化物。(3)立体定向性；顺式环氧乙烷以高选择性生成顺式碳酸酯，尽管伴随着环氧乙烷异构化为相应的酮。即使我们的新型催化剂也不能完全抑制这种异构化。

项目成果

Carbonate Formation from Oxiranes and Carbon Dioxide Catalyzed by Organotin Halide-Tetraalkylphosphonium Halide Complexes: Bull. Chem. Soc. Jpn.60. 1552-1554 (1987)

有机锡卤化物-四烷基鏻卤化物配合物催化环氧乙烷和二氧化碳形成碳酸盐：Bull。

A.Baba: Bull.Chem.Soc.Jpn.

A.Baba：Bull.Chem.Soc.Jpn。

A. Baba: "Cyclic Carbonate Formation from carbon Dioxide and Oxiranes in the Presence of Organotin Halide-Complexed Catalysts" Nippon Kagaku Kaishi. 1987. 1189-1193 (1987)

A. Baba：“在有机锡卤化物络合催化剂存在下，由二氧化碳和环氧乙烷形成环状碳酸盐”，Nippon Kagaku Kaishi。

A.Baba: Bull. Chem. Soc. Jpn.60. 1552-1554 (1987)

阿巴巴：公牛。

馬場 章夫: 日本化学会誌. 1987. 1189-1193 (1987)

马场明夫：日本化学会杂志 1987 年。1189-1193 (1987)