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本文研究了(+)-(R)-(R)-O-乙基苯基硫代膦酸O-乙基O-苯基硫代磷酸混合酐1的(1)碱性甲醇解反应;(2)酸性甲醇解反应;(3)碱性水解反应;(4)氨解反应;(5)与硫氢化钾反应以及(6)与五氯化磷反应的立体化学。发现所研究的反应均使P—O—P键断裂。在反应(1)—(4)中,亲核试剂的进攻发生在膦酰基磷原子上,得到构型翻转的产物;而未受亲核进攻的磷酰基磷原子构型保留。在反应(5)中,亲核试剂~-SH的进攻也发生在膦酰基磷原子上,但由于生成Ph(EtO)P(S)S~-而失去手性,使之消旋化;未受进攻的磷酰基磷原子仍为构型保留。在反应(6)中,膦酰基和磷酰基均被氯化,分别得到构型翻转的产物硫代膦酰氯14和硫代磷酰氯16,前者有明显的消旋化。本文还探讨了个别反应的反应机理。
In this paper, the basic methanolysis of (+) - (R) - (R) -O-ethylphenylphosphonothioic acid O-ethyl O-phenylphosphoric acid anhydride 1 was studied. 2) acidic methanolysis reaction; (3) alkaline hydrolysis reaction; (4) ammonolysis reaction; (5) reaction with potassium hydrogen sulfide and (6) stereochemistry of reaction with phosphorus pentachloride. It was found that all the reactions studied cleaved the P-O-P bond. In reactions (1) - (4), the attack of the nucleophile takes place on the phosphonophosphorus atom, resulting in a product with a reversed configuration; the phosphoryl phosphorus atom, which is not attacked by the nucleophile, remains in the configuration. In reaction (5), the attack of the nucleophile ~ -SH also takes place on the phosphonophosphorus phosphorus atom but it is racemized due to the formation of Ph (EtO) P (S) S ~ -; The phosphoryl Phosphorus atom attacked remains conformational. In reaction (6), the phosphono and phosphoryl are both chlorinated to give the tosylated thiophosphoryl chloride 14 and thiophosphoryl chloride 16, respectively, the former being clearly racemized. This article also explored the reaction mechanism of individual reactions.