一种新的环状膦酸酐的合成与X射线晶体结构  

Synthesis and X-ray Crystal Structure of a Novel Cyclic Phosphonic Acid Anhydride

作　　者：安德烈[1] 张英俊[1] 彭志鸿[1] 

机构地区：[1]湖南大学化学化工学院,长沙410082

出　　处：《化学学报》2004年第12期1166-1170,MJ05,共6页Acta Chimica Sinica

基　　金：国家教育部留学人员科研启动基金 [教外司留 (1 998) 679]资助项目

摘　　要：2 ,4 二叔丁基 6 甲氧基苯膦二硫化物 [MoxP(S) 2 ,1]与H2 O/吡啶封管反应分别以 3 0 %和 2 2 %的收率得到一种新的环状膦酸酐的异构体 2a和 2b .通过3 1PNMR对反应过程的追踪探讨了 2的形成机制 .X射线晶体结构解析表明异构体 2b分子中有一个不规则的含磷六元杂环 .环内最大键角为 12 7.7° ,最小键角为 97.9° .六元杂环中 ,除CC具有双键性质外 ,其余的CP ,CO和PO键均具有典型的单键特征 .两个环外PS双键处于含磷杂环的同一侧 ,表明 2b分子是一个cis结构 .该晶体属单斜晶系 ,C2 /c空间群 ,a =2 .0 486( 3 )nm ,b =2 .2 3 66( 4 )nm ,c =1.63 3 4( 3 )nm ,β =112 .98( 1)° ,Z =8,V =6.890 ( 1)nm3 ,Dc=1.2 61g·cm-3 ,F( 0 0 0 ) =2 80 0 .0 0 ,μ(MoKα) =3 .40cm-1.最终偏差因子R =0 .0 63 ,Rw=0 .0 83 .最高和最低残余峰分别为 0 .82和 -0 .48× 10 3 e-/nm3 .The reaction of 2,4-di-t-butyl-6-methoxyphenyldithioxophosphorane [MoxP(=S)(2), 1] with H2O in the presence of pyridine afforded a novel cyclic phosphonic acid anhydride 2a and 2b in 30% and 22% yields, respectively. The mechanism for the formation of 2 was discussed by P-31 NMR monitoring. The results from X-ray crystallographic analysis for 2b indicated that it has a six membered phosphorus-containing hetero ring, which bears a 127.7degrees of the largest bond angle and a 97.9degrees of the smallest one. On the basis of bond length data, C-P, C-O and P-O bonds show typical single bond characters except C C double bond. The two P=S double bonds are located in the same side of hetero ring, indicating clearly that 2b is a cis isomer. Crystal data for 2b: monoclinic, space group C2/c, a = 2.0486(3) nm, b = 2.2366(4) nm, c = 1.6334(3) nm, beta = 112.98(1)degrees, Z = 8, V = 6.890(1) nm(3), D-c = 1.261 g (.) cm(-3), F(000) = 2800.00, mu(Mo Kalpha) = 3.40 cm(-1). The final deviation factor R = 0.063, R-w = 0.083. The maximum and minimum peaks on the final difference Fourier map correspond to 0. 82 and -0.48 x 10(3) e-/nm(3), respectively.

关 键 词：环状膦酸酐 合成 X射线晶体结构 反应机理 2 4-二叔丁基-6-甲氧基苯膦二硫化物 核磁共振磷谱 羰基反应 

分 类 号：O627.51[理学—有机化学]