Arbuzov reactions of the fluorous primary iodides Rfn(CH2)mI [Rfn = CF3(CF2)n-1; n/m = 6/2, 8/2, 8/3, 10/2] and P(OEt)3 (excess, 160 °C) give the fluorous phosphonates Rfn(CH2)mP(O)(OEt)2 (56-59%), which are reduced with LiAlH4 to the title compounds Rfn(CH2)mPH2 (62-78%). Fluorophilicities (CF3C6F11/toluene partition coefficients) increase with the length of the Rfn moiety, decrease with the length of the (CH2)m moiety, and decrease in the functional group sequence Rfn(CH2)mNH2 > Rfn(CH2)mPH2 > Rfn(CH2)mP(O)(OEt)2.
Arbuzov反应中,
氟化的一级
碘化物Rfn(
CH2)mI [Rfn =
CF3(
CF2)n-1; n/m = 6/2, 8/2, 8/3, 10/2]与P(OEt)3(过量,160°C)反应生成
氟化
磷酸酯Rfn( )mP(O)(OEt)2(收率为56-59%),随后用LiAlH4还原为标题化合物Rfn( )mPH2(收率为62-78%)。
氟亲和性( C6F11/
甲苯分配系数)随着Rfn部分的长度增加而增加,随着( )m部分的长度增加而减小,并且在功能团序列中呈现递减趋势:Rfn( )mNH2 > Rfn( )mPH2 > Rfn( )mP(O)(OEt)2。