论文部分内容阅读
O一乙基-O-苯基硫代磷酸(1)及其硫(醇)代酯(2)的绝对构型可由以下两步反应确定(见图1)。即,(-)-(2)的氯化和(-)-O-乙基-O-苯基磷酰氯(3)的酯化反应。由(-)-(2)→(-)-(3)氯化反应的立体化学过程已a.R′=CH_3b.R′=n-prc.R′=CH_2CH_2OC_2H_5经证明,不管是使用氯气还是使用SO_2Cl_2为氯化剂,均为磷原子构型保留,由(-)-(3)生成(-)-O-乙基-O-甲基O-苯基磷酸酯(4)的反应则使构型翻转。同时(-)-(4)构型已知为(R)-(+)-(4)、(S)-(-)-(4),所以(+)-(1)和(-)-(2)的绝对构型可确定为:(R)-(+)-(1)和(R)-(-)-(2)。这一结果与X-射线衍射法所得结果完全一致。
The absolute configuration of O-ethyl-O-phenyl phosphorothioate (1) and its thiol (2) can be determined by the following two-step reaction (see Figure 1). That is, esterification of (-) - (2) and (-) - O-ethyl-O-phenylphosphoryl chloride (3). The stereochemistry of the chlorination reaction has been confirmed by (-) - (2) → (-) - (3) aR ’= CH_3b.R’ = n-prc.R’ = CH_2CH_2OC_2H_5. It has been demonstrated that whether chlorine is used or SO_2Cl_2 Is a chlorinating agent, both of which remain in the phosphorus atom configuration. The reaction of (-) - O-ethyl-O-methyl O-phenylphosphate (4) from (-) - Flip. (+) - (1) and (-) - (4) are known as (R) - (+) - The absolute configuration of (2) can be determined as (R) - (+) - (1) and (R) - (-) - (2). This result is in good agreement with the results obtained by X-ray diffraction.