Glonek T, Kleps R A, Van Wazer J R, Myers T C
Bioinorg Chem. 1976;5(4):283-310. doi: 10.1016/s0006-3061(00)80290-2.
Detailed analysis of appropriate 31P nuclear-magnetic-resonance spectra shows that under the usual laboratory conditions, carbodiimide-induced condensation of orthophosphoric acid in a number of solvents leads to condensation only slightly beyond the metaphosphate composition in the presence of strong tertiary amines; whereas in the absence of amine, the condensation proceeds into the ultraphosphate region about halfway between the metaphosphate and phosphoric anhydride compositions. With amine, the principal product consists of the cyclic trimetaphosphate anion, with one of the nonbridging oxygen atoms substituted by the urea resulting from hydration of the carboiimide, i.e., (O2-) P-O-P(O2-) -O-P(O) [N[CH(CH3)2] see article [C(O)NHCH(CH3)2]] for the condensation with diisopropylcarbodiimide. Without amine, the major product is the 1,5-mu-oxotetrametaphosphate anion see article. The well-known carbodiimide-mediated phosphorylation of alcohols with orthophosphoric acid is shown to be directly attributable to the high reactivity of the phosphate branch groups of the carbodiimide-generated ultraphosphates.
对合适的³¹P核磁共振谱的详细分析表明，在通常的实验室条件下，在多种溶剂中，碳二亚胺诱导的正磷酸缩合反应，在存在强叔胺的情况下，缩合仅略微超过偏磷酸盐组成；而在没有胺的情况下，缩合反应会进行到偏磷酸盐和磷酸酐组成之间大约一半位置的超磷酸盐区域。有胺存在时，主要产物由环状三聚偏磷酸根阴离子组成，其中一个非桥连氧原子被碳二亚胺水合产生的脲取代，即与二异丙基碳二亚胺缩合时为(O₂⁻)P - O - P(O₂⁻) - O - P(O)[N[CH(CH₃)₂]见文章[C(O)NHCH(CH₃)₂]]。没有胺时，主要产物是1,5-μ-氧代四聚偏磷酸根阴离子见文章。众所周知的碳二亚胺介导的正磷酸与醇的磷酸化反应被证明直接归因于碳二亚胺生成的超磷酸盐的磷酸分支基团的高反应活性。
