ORGANIC SULFUR COMPOUNDS .15. CATIONIC ADDITION OF O,O'-DIETHYLTHIOPHOSPHORIC ACID TO OLEFINS
ORGANIC SULFUR COMPOUNDS .15. CATIONIC ADDITION OF O,O'-DIETHYLTHIOPHOSPHORIC ACID TO OLEFINS
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DOI：
10.1021/jo01344a051
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发表时间：
1966-01-01
影响因子：
3.6
通讯作者：
OSWALD, AA
中科院分区：
文献类型：
--
作者：
MUELLER, WH;OSWALD, AA
通过阳离子机理将1，2 ′-二乙基硫代磷酸（硫代磷酸0，0 ′-二乙酯）加成到异丁烯、异戊二烯、苯乙烯、茚、环戊烯和异戊二烯中。观察到主要形成O，O '-二乙基-S-烷基硫代磷酸盐。根据Markovnikov规则，高选择性地形成S-异丁基-、Sa-苯乙基-、S-1-茚满基-和S-环戊基硫代磷酸酯。由异戊二烯以4：1的比例得到S-（3-甲基-2-丁烯基）-和S-2-（2-甲基-3-丁烯基）硫代磷酸酯。用异戊烯，观察到O-和S-烷基化以2：3的特别高的比率进行。结果表明，加成反应只发生在有张力的环烯烃或在质子化时形成相对稳定的碳正离子的烯烃上.在我们研究，'-二烷基硫代磷酸（硫代磷酸O，O'-二烷基酯）与不饱和化合物的自由基加成反应过程中，我们开始关注在这类体系中同时发生阳离子加成的可能性. O，O ′-二烷基二硫代磷酸对烯烃的阳离子加成反应是一个研究得很好的反应，有关文献表明它具有相当普遍的适用性，即与烯烃的结构无关。1然而，类似的添加，'-二烷基硫代磷酸似乎几乎没有研究过。只有少数离子
,'-Diethylthiophosphoric acid (phosphorothioic acid 0, 0'-diethyl ester) was added to isobutylene, isoprene, styrene, indene, cyclopentene, and norborneneby a cationic mechanism. The predominant formation of O, O'-diethyl-S-alkylthiophosphates was observed. In accordance with the Markovnikov rule, S-í-butyl-, Sa-phenylethyl-, S-1-indanyl-, and S-cyclopentylthiophosphates were formed with highselectivities. From isoprene theS-(3-methyl-2-butenyl)-and S-2-(2-methyl-3-butenyl) thiophosphates were obtained in a 4: 1 ratio. With norbornene O-and S-alkylation was observed in an exceptionally high ratio of 2: 3. It was shown that addition occurs only to strained cyclic olefins or to olefins which form on protonation relatively stable carbonium ions.During the course of our investigation of thefreeradical addition of,'-dialkylthiophosphoric acid (phosphorothioic acidO, 0'-dialkylesters) to unsaturates, we became concerned with the possibility of concurrent cationic additions in such systems. Thecationic addi-tion of O, O'-dialkyldithiophosphoric acids to olefins is a well-studied reaction, and the relevant literature indi-cates that it is rather generally applicable, ie, independent from thestructure of the olefin. 1 Similar additions of,'-dialkylthiophosphoric acids, however, appear to be hardly investigated. Only a few ionic