Preparation and chemistry of some cyclic phosphoranes
Preparation and chemistry of some cyclic phosphoranes
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一些环状正膦的制备和化学
DOI：
10.1021/ja00756a043
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发表时间：
1972
影响因子：
15
通讯作者：
K. L. Marsi
中科院分区：
文献类型：
--
作者：
D. B. Denney;D. Denney;C. Hall;K. L. Marsi
研究了膦1-8与过氧化二乙酯的反应。1和2的产物具有五取代磷化合物9和10的性质。4和5的产物由五取代磷化合物和烷氧磷烷氧化物的平衡混合物组成。7的产物经反环加成成异戊二烯和苯基膦酸二乙酯。8的乘积重新排列成7的乘积。在环戊烷中，膦与过氧化二乙酯的相对反应速率分别为1,3.8,6,2.0,4,1.3和3,1.0；在二氯甲烷中，相对速率分别为1,3.1,6,1.7,4,1.6和3,1.0。膦与碘化乙酯在乙腈中的相对反应速率分别为4、1.5、3、1.0、6、0.9和1.0.33。这两个反应的速率顺序是相反的。过氧化二乙酯反应的速率顺序支持这是一个亲疏置换过程的概念，其中磷原子在速率控制步骤的过渡态与两个氧成键。
The reactions of the phosphines 1-8 with diethyl peroxidehave been studied. The products from 1 and 2 havethe properties of pentasubstituted phosphorus compounds 9 and 10. The products from 4 and 5 consist of equilibrium mixtures of pentasubstituted phosphorus compounds and alkoxyphosphonium alkoxides. The prod-uct from 7 undergoes reverse cycloaddition to isoprene and diethyl phenylphosphonite. The product from 8 re-arranges to that from 7. The relative rates of reaction of the phosphines with diethyl peroxide in cyclopentane are1, 3.8, 6, 2.0, 4, 1.3, and 3, 1.0; in methylene chloride the relative rates are 1, 3.1, 6, 1.7, 4, 1.6, and 3, 1.0. The relative rates of reaction of the phosphines with ethyl iodide in acetonitrile are 4, 1.5, 3, 1.0, 6, 0.9, and 1, 0.33. The rate orders for these two reactions are the reverse of each other. The rate order for the diethyl peroxide re-action supports the concept of this being a biphilic displacement process in which the phosphorus atom is bonding to both oxygens in the transition state of the rate-controlling step.