Carbacylamidophosphates, IR Data, X-Ray Data Dimorpholido-N-trichloroacetylphosphorylamide: CCl3C(0 )NHP(0 )[N(CH2CH2)2 0 ] 2 [HL] and its sodium [NaL] and morpholine [HN(CH2CH2 ) 2 0 HL] salts were synthesized for the first time. The compounds were studied by IR spectroscopy and assignments of the characteristic IR bands have been made. The structure of [HL] was determined by X-ray diffraction. Crystals are monoclinic, a = 11.412(2) A, b = 16.056(3) A, c = 9.622(2) Ä, ß = 108.55(3)°, space group P2i/c; Z = 4. The refinement of the structure converged at R = 0.066. The molecules are connected into centrosymmetric dimers via hydrogen bonds formed by the phosphorylic oxygen atoms and hydrogen atoms of amide groups.
IntroductionCarbacylamidophosphates of the general formula R 'C (0 )N H P (0 )(R 2)2 are interesting as potential new ligands for metal ions [1 -4]. On the other hand, many of these compounds show interesting biological properties, including anticancer activ ity [5,6]. The X-ray structures of three carbacy lamidophosphates: CCl3C (0)N H P (0)(0M e)2 (I), CCl3C (0)N H P(0)(N E t2)2 (II), and CCl3C (0)N H P(0)(N H Ph)2 (III) were studied ear lier [7 -9 ]. The results have shown that in the molec ular core unit, -C (0)N (H )P(0)=, the C = 0 and P = 0 oxygen atoms are in trans position to each other, and that the C -C (0)N -unit is virtually planar.This work reports the synthesis, the structure de termination and the properties of dimorpholido-Ntrichloroacetylphosphorylamide and its sodium and morpholine salts. Experimental The synthesis of the dimorpholido-N-trichloroacetylphosphorylamide was carried out according to the scheme: CC13C(0)NHP(0)C12 + 5HN(CH2CH2)20 -*• CC13C(0)NHP(0)[N(CH2CH2)20]2HN(CH2CH2)20 + 2 HN(CH2CH2)20 HC1 * Reprint requests to Dr. V. Amirkhanov. The dichloride of trichloroacetylamidophosphoric acid was obtained by the method described earlier [1 0 ].The solution of morpholine [35 g (0.4 mol)] in 100 ml of benzene was placed into a three-neck round-bottomed flask and cooled to 10°C. A solution of the dichloride [23 g (0.083 mol)] of trichloroacetylamidophosphoric acid in 400 ml of a toluene-dioxane mixture (10:1) was added slowly with stirring.(The temperature was not al lowed to rise above 10°C!). Stirring was continued for about 40 min. The resulting mixture, containing the HN(CH2CH2)2O HL (HL = dimorpholide-N-trichloroacetylphosphorylamide) and HN(CH2CH2) 2 0 HC1, was filtered from the precipitate and HN(CH2CH2 ) 2 0 HL was extracted by acetone. Then the extract was evaporated and the residue was dissolved in water. After the addition of HC1 to the aqueous solution the product precipitated as a white crystalline powder (80% yield).Single crystals for the structure investigations were obtained by recrystallization from methanol.The product, m.p. 205 °C with the decomposition, is soluble in methanol and acetone, less soluble in nonpolar aprotic solvents, and essentially insoluble in water.The sodium salt [NaL] was obtained from methanol solution with sodium methoxide. It is a white...