O-烃基-S-烃基二硫代磷酸的质谱初探

Preliminary Study on Mass Spectra of Derivatives of Dithiophosphonic Acid

摘要: 测定并解析了四个O-烃基-S-烃基二硫代磷酸衍生物(R_1O)(R_2S)P=O(SH)的EI谱。这些衍生物是(Ⅰ)R_1=R_2=n—C_3H_7;(Ⅱ)R_1=—CH_3,R_2=—CH(CH_3)_2;(Ⅲ)R_1=—CH_3,R_2=—C_2H_5;(Ⅳ)R_2=n—C_3H_7;R_2=—CH_3。探讨了对于P=O双键的多种α开裂。比较了R_1不同时α开裂碎片R_1O~((?)+)的Z值(Z=R_1O~((?)+)丰度/M~+丰度)。结果表明,R_1O~((?)+)的Z值为R_1的异构化所降低而为非异构化的直链R_1烷基所增加;在R_2S~((?)+)的情况下,R_2S~((?)+)的Z值(Z=R_2S~((?)+)丰度/M~+丰度)为较小的烷基R_2所增加,为较大的烷基R_2基团所减小。

Abstract: Four derivatives (R_1O)(R_2S)P=O(SH) of dithiophonic acid were determinated and interpretated. They are (Ⅰ) R_1=R_2=n-C_3H_7; (Ⅱ): R_1=-CH_3, R_2=-CH(CH_3)_2; (Ⅲ): R_1=-CH_3, R_2=-C_2H_5; (Ⅳ): R_1=n-C_3H_7, R_2=-CH_3.A variety of α cleavages to P=O double bond have been studied. The quantity Z(Z=R_1O~+ abundance/M~- abundance) of fragments R_1O~+ for different R_1 produced by α cleavages is compared with each other. The results indicate that the quantity Z of R_1O~+ is decreased by the isomerization of R_1 and increased by the nonbranching of R_1; In the case of R_2S~+ , the quantity Z (Z=R_2S~+ abundance/M~+ abundance) of R_2S~- is increased by smallar R_2 and decreased by bigger R_2.