Organophosphorus Compounds; 129. Mesitylphosphaacetylene: Synthesis and Reactivity Studies of a New Phosphaalkyne
Organophosphorus Compounds; 129. Mesitylphosphaacetylene: Synthesis and Reactivity Studies of a New Phosphaalkyne
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有机磷化合物；
DOI：
10.1055/s-1998-6089
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发表时间：
1998
期刊：
影响因子：
--
通讯作者：
M. Regitz
中科院分区：
文献类型：
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作者：
Andreas Mack;E. Pierron;T. Allspach;U. Bergstraesser;M. Regitz
以磷酸烯2b为原料，用氯化铝引发消去双（三甲基硅基）醚，合成了甲酰基磷酸乙炔（1b）。该新型磷酸己炔与重氮化合物（→6a, b）、叠氮化合物（→8a-c）和腈氧化物（→10a, b）发生[3+2]环加成反应，得到五元杂环产物。介离子伙伴11和13分别在CO 2和COS的消除下与1b反应，生成1,3-氮杂和1,3-硫磷孔12和14。1b与丁-1,3-二烯反应生成二磷酸环烯18；结果表明，1-磷酸环己-1,4-二烯15（通过W(CO) 5配合物17的x射线结构分析表征）是多步反应的中间体。此外，1b还与环丁二烯19和氮杂环丁二烯21发生diols - alder反应，生成杜瓦烯20和杜瓦烯22。
Mesitylphosphaacetylene (1b) has been synthesized by AlCl 3 initiated elimination of bis(trimethylsilyl) ether from the phosphaalkene 2b . This new phosphaalkyne undergoes [3+2] cycloaddition reactions with diazo compounds ( → 6a , b ), azides ( → 8a–c ), and nitrile oxides ( → 10a , b ) to yield five-membered heterocyclic products. The mesoionic reaction partners 11 and 13 react with 1b under elimination of CO 2 and COS, respectively, to furnish the 1,3-azaand 1,3-thiaphospholes 12 and 14 . Reaction of 1b with buta-1,3-diene leads to the diphosphatricyclooctene 18 ; it has been shown that the 1-phosphacyclohexa-1,4-diene 15 (characterized by an X-ray structure analysis of its W(CO) 5 complex 17 ) is an intermediate in the multistep reaction. Moreover, 1b has been characterized by Diels–Alder reactions with the cyclobutadiene 19 and the azacyclobutadiene 21 to afford the Dewar hetarenes 20 and 22 .