Reactions of Allenylphosphonates with Trioxatridecanediamine

摘要

Intensive development of aminophosphoryl compounds chemistry observed in the last few years is connected with the wide possibilities of their practical use [1]. In this report some results of studying allenylphosphonate reactions with 4,7,10-trioxa-1,13-tridecanediamine I are given. A thick oily adduct was obtained on mixing twofold excess of diethyl 3-methyl-l,2-butadienylphosphonate with diamine I, the reaction proceeds with gentle warming-up. This adduct was purified by repeated precipitation from CH2Cl2 with hexane to the constant value of refractive index. Yield 73%, n_D~(20) 1.4950. In the IR spectrum of adduct the stretching vibration band of allene triad (1955 cm~(-1) ) disappeared, and intensive bands at 1210 (P=O), 1583 (C=C) and 3296 cm~(-1) (NH) appeared. ~1H NMR spectrum (DMSO-d6), 5, ppm: 1.13 d [12H, (CH3)2· CHC=, ~1J_(hh) 7.0 Hz], 1.27 t (12H, CH3CH2OP, ~1J_(HH) 7.1 Hz), 1.82 q (4H, NHCH2CH2CH2O, ~1J_(HH) 6.4 Hz), 3.03 q (4H, NHCH2CH2CH2O, ~3J_(hh) 6.4 Hz ), 3.4-3.7 m [16H, (CH3)2CH-, CH2-O-CH2CH2O-, PCH=], 3.92 q(8H, CH3CH2OP, ~3J_(HH) 7.1 Hz,~3J_(PH)7.1 Hz), 6.19 m (2H, NH).~(31)P NMR spectrum (DMSO), δ_P, ppm: 28.06. Found, %: C 54.98; H 9.11; C_(28)H_(58)N2O9P2. Calculated, %: C 53.50; H 9.23.