Phosphoric carboxylic imides. I. Preparation and fragmentation behavior of dialkylphosphoryl (and phosphinyl) acetyl (and benzoyl) imides and related systems

Mizrahi, Valerie; Modro, Tomasz A.

doi:10.1021/jo00139a030

Cited by 27 publications

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“…The distance between these atoms (3.02 A) is slightly below than the sum of the Van-der-Waals radii of phosphorus and oxygen atoms (3.3 A). A similar contact was found in C6H5C(0 )NHP(0 )(0 CH3)2 studied earlier [14].…”

Section: Resultssupporting

confidence: 86%

Carbacylamidophosphates: Synthesis, Properties, and Structure of Dimorfolido-N-trichloroacetylphosphorylamide

Оvchynnikov

Amirkhanov

Timoshenko

et al. 1998

Zeitschrift Für Naturforschung B

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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...

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Section: Resultssupporting

confidence: 86%

Carbacylamidophosphates: Synthesis, Properties, and Structure of Dimorfolido-N-trichloroacetylphosphorylamide

Оvchynnikov

Amirkhanov

Timoshenko

et al. 1998

Zeitschrift Für Naturforschung B

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“…The second noted peak is a result of a McLafferty rearrangement. A similar mechanism was reported previously for compounds with a (H -CH 2 CH 2 O)P(O) segment, through migration of a -H atom to the phosphoryl group, followed by elimination of ethylene (Mizrahi & Modro, 1982). The signal related to the base peak at m/z = 133 is assigned to the C 6 H 2 (CH 3 ) 3 N cation.…”

Section: Nmr Spectroscopy and Mass Spectrometrysupporting

confidence: 75%

Evaluation of N—H...S and N—H...π interactions inO,O′-diethylN-(2,4,6-trimethylphenyl)thiophosphate: a combination of X-ray crystallographic and theoretical studies

et al. 2018

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In the crystal structure of O,O'-diethyl N-(2,4,6-trimethylphenyl)thiophosphate, CHNOPS, two symmetrically independent thiophosphoramide molecules are linked through N-H...S and N-H...π hydrogen bonds to form a noncentrosymmetric dimer, with Z' = 2. The strengths of the hydrogen bonds were evaluated using density functional theory (DFT) at the M06-2X level within the 6-311++G(d,p) basis set, and by considering the quantum theory of atoms in molecules (QTAIM). It was found that the N-H...S hydrogen bond is slightly stronger than the N-H...π hydrogen bond. This is reflected in differences between the calculated N-H stretching frequencies of the isolated molecules and the frequencies of the same N-H units involved in the different hydrogen bonds of the hydrogen-bonded dimer. For these hydrogen bonds, the corresponding charge transfers, i.e. lp (or π)→σ*, were studied, according to the second-order perturbation theory in natural bond orbital (NBO) methodology. Hirshfeld surface analysis was applied for a detailed investigation of all the contacts participating in the crystal packing.

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“…phosphoramides by the removing of the esters of phosphoric acid (Mizrahi and Modro 1982). The observation of this fragment indicates that the parent radical-cation rapidly undergoes a migration of phosphorous from nitrogen to oxygen.…”

Section: Mass Spectrometric Analysismentioning

confidence: 95%

Different molecular assemblies in two new phosphoric triamides with the same C(O)NHP(O)(NH)2 skeleton: crystallographic study and Hirshfeld surface analysis

et al. 2017

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Different molecular assemblies were compared in two new structures [4-CH 3 -C 6 H 4 C(O)NH]P(O) [NH] 2 (-CH 2 ) 3 , 1, and [4-CH 3 -C 6 H 4 C(O)NH]P(O) [NHC 6 H 3 (3, ) 2 ] 2 , 2, belonging to the families of "cyclic phosphoric triamide" and "phosphoric triamide", respectively. The differences in the hydrogen bond motifs were discussed (by single crystal X-ray diffraction) as a result of three factors: (1) action of two N atoms with a non-planar environment in 1 as an H-bond acceptor, (2) different orientations of three N-H bond vectors in two molecules and (3) different conformations of C=O and P=O groups. These differences lead to more complicated hydrogen bond pattern of 1, with respect to that of 2, as structure 1 may be considered as a model of four-acceptor-three-donor versus a two-acceptorthree-donor system in 2. The main discrepancies of 1 and 2, monitored by the Hirshfeld surface analysis, are related to the contribution portions of O···H/H···O contacts, in which compound 1 not only involves the greater existence of classical hydrogen bonds but also contains the further C-H···O weak interactions in its crystal packing with respect to compound 2. Instead, in 2, the shortage of O···H/H···O contacts has been partially compensated by the C···H/H···C interactions, due to the presence of more unsaturated carbon acceptors. The differences in assemblies are also reflected in the solid-state IR spectra, especially for the N-H vibration frequencies. The new compounds were further studied by 1D NMR experiments ( 1 H, 13 C, 31 P), 2D NMR techniques [HMQC and HMBC (H-C correlation), HSQC (N-H correlation)], high-resolution ESI-MS, EI-MS spectrometry and IR spectroscopy.

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Phosphoric carboxylic imides. I. Preparation and fragmentation behavior of dialkylphosphoryl (and phosphinyl) acetyl (and benzoyl) imides and related systems

Cited by 27 publications

References 0 publications

Carbacylamidophosphates: Synthesis, Properties, and Structure of Dimorfolido-N-trichloroacetylphosphorylamide

Carbacylamidophosphates: Synthesis, Properties, and Structure of Dimorfolido-N-trichloroacetylphosphorylamide

Evaluation of N—H...S and N—H...π interactions inO,O′-diethylN-(2,4,6-trimethylphenyl)thiophosphate: a combination of X-ray crystallographic and theoretical studies

Different molecular assemblies in two new phosphoric triamides with the same C(O)NHP(O)(NH)2 skeleton: crystallographic study and Hirshfeld surface analysis

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