Synthesis and Crystal Structure of 5,5-Dimethyl-2-(p-methylanilino)-2-oxo-1,3,2-diazaphosphorinane

Gholivand, Khodayar; Pourayoubi, Mehrdad; Farshadian, Sedigheh; Molani, Soheila; Shariatinia‬, Zahra

doi:10.2116/analscix.21.x55

Cited by 11 publications

(6 citation statements)

References 4 publications

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“…In diazaphosphorinane ring, the P=O bond is placed in an equatorial position, attributed to the endo anomeric effect which was previously observed by Bentrude for 1,3,2-oxazaphosphorinane [56]. Moreover, this configuration has been found for another derivative of diazaphosphorinane family reported by Gholivand et al [57]. This situation is observed for 1 probably via overlapping of the non-bonding orbital located on the endocyclic nitrogen atoms with the anti-bonding orbital of P-N(exocyclic) [56].…”

Section: Structural Descriptionsupporting

confidence: 58%

Different orientations of C=O versus P=O in P(O)NHC(O) skeleton: the first study on an aliphatic diazaphosphorinane with a gauche orientation

et al. 2010

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Different orientations of P(O) versus C(O) in P(O)NHC(O) skeleton have been discussed in two new phosphorus(V)-nitrogen compounds with formula XP(O)Y and XP(O)Z 2 where X = NHC(O)C 6 H 4 (4-F) and Y = NHCH 2 C(CH 3 ) 2 CH 2 NH (1), Z = NHC 6 H 4 (4-CH 3 ) (2). Compound 1 is the first example of an aliphatic diazaphosphorinane with a gauche orientation which has been studied by X-ray crystallography; the P=O bond is in the equatorial position of the ring. Both compounds show n J(F,C) and m J(F,H) coupling constants (n = 1, 2, 3 and 4; m = 3 and 4) and 3 J(P,C) [ 2 J(P,C). Quantum chemical calculations were performed with HF and Density Functional Theory (DFT) methods using 6-31?G(d,p) basis set. A tentative assignment of the observed vibrational bands for these molecules is discussed. Compound 1 shows a deshielded C atom of the carbonyl moiety (in 13 C NMR spectrum) relative to that of 2, which is supported by IR spectroscopy in which the considerably lower C=O frequency is observed for 1. Comparing the X-ray crystallography and IR spectra of 1 and 2 shows that the acyclic compound 2, containing P=O and C=O bonds in an anti position, are involving in a stronger N-HÁÁÁO=P hydrogen bond in crystal network. This leads to a weaker P=O and N C(O)NHP(O) -H bonds and stronger NÁÁÁO interaction. The N amide -H is involved in an intramolecular N-HÁÁÁO hydrogen bond.

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Section: Structural Descriptionsupporting

confidence: 58%

Different orientations of C=O versus P=O in P(O)NHC(O) skeleton: the first study on an aliphatic diazaphosphorinane with a gauche orientation

et al. 2010

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“…Nowadays, modification of cyclophosphamide (an oxazaphosphorinane compound) have led to the design and synthesis of numerous cyclic analogous compounds [4][5][6][7][8] to find an antitumor agent that has less side effects than drugs now present. The chemistry of 1,3,2-oxaza- [9,10] and dioxa-phosphorinanes [11,12], as well as the synthesis [13,14], stereochemistry [15], coordination chemistry [16,17] and, X-ray crystal structures [4,18] of 1,3,2-diazaphosphorinanes have frequently been studied. According to the stereochemical surveys, 1,3,2-diazaphosphorinanes prefer chair or flattened chair conformations, in contrast to 1,3,2-oxazaphosphorinanes which have diverse conformations [19].…”

Section: Introductionmentioning

confidence: 99%

The first naphthodiazaphosphorinane in the solid phase; syntheses, spectroscopic studies and X-ray crystallography of some new 1,3,2-diheterophosphorus compounds

et al. 2009

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New heterocyclic compounds of diazaphosphorinanes, diazaphospholes, and oxazaphospholes were synthesized and characterized by 1 H, 13 C, 31 P, NMR, IR spectroscopy, and CHN elemental analysis. The 3D structure of compound (5) was determined by X-ray crystallography. Since benzo-or naphthodiazaphospholes/diazaphosphorinanes containing aromatic rings are usually unstable in the solution state, their single crystal structures are rarely reported and, to the best of our knowledge, this structure is the first occasion of naphthodiazaphosphorinanes obtained here. It is noticeable that the P=O and C=O bonds are closer to syn than anti configuration and the P=O bond is placed in a pseudoequatorial position. This structure produced a 3D polymeric chain via strong hydrogen bonds and electrostatic short contacts. Due to the ring strain of five-membered rings, for all diazaphospholes great 2 J(PNH endocyclic ) coupling constants (about 18.0 Hz), as well as high 2,3 J(P,C) coupling constants for the aromatic carbon atoms connected to the five-membered ring (about 14.5, 13.5 Hz, respectively) were measured. Replacement of one NH group in a diazaphosphole ring by an oxygen atom caused exceedingly decreased ring strain and hence highly diminished 2 J(PNH endocyclic ) coupling constant.Furthermore, 31 P NMR spectra of oxazaphospholes, like the spectra of diazaphosphorinanes, indicated highly shielded phosphorus atoms relative to those of their diazaphospholes analogs.

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“…Hutchins et al studied the conformational analysis of 1,3-diazaphosphorinanes as well as their 1 H-and 31 P NMR spectroscopy [3]. Synthesis, conformational properties, and crystal structures [4,5] of several diazaphosphorinanes were reported [6][7][8][9]. Investigations on doubly connected phosphorus cations were made in some 1,3-diazaphosphorinanes [10].…”

Section: Introductionmentioning

confidence: 99%

Phosphorus heterocycles: synthesis, spectroscopic study and X-ray crystallography of some new diazaphosphorinanes

et al. 2007

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New diazaphosphorinanes with formula C 6 H 5 OP(O)[NHCH 2 C(CH 3 ) 2 CH 2 NH] (1), RP(O)[NH(CH 2 ) 3 NH], R=C 6 H 5 O (2), 4-CH 3 -C 6 H 4 NH (3), 4-NO 2 -C 6 H 4 NH (4), RP(O)[NHC 10 H 6 NH],R=Cl (5), 4-CH 3 -C 6 H 4 O (6), and C 6 H 5 NH (7) were synthesized and characterized by 1 H, 13 C, 31 P NMR and IR spectroscopy and elemental analysis. The crystal structures of compounds 1 and 4-CH 3 -C 6 H 4 OP(O)[NH(CH 2 ) 3 NH] (8) were determined using X-ray crystallography. In these structures, the P=O bond is placed in an equatorial position and the aliphatic six-membered rings show chair conformations. These compounds form two-dimensional polymeric chains via intermolecular P=O…H-N hydrogen bonds. 1 H NMR spectrum of compound 1 shows a ddd splitting pattern for the coupling of H equatorial proton with phosphorus atom, H axial atom, and NH proton with a highvalue 3 J(PNCH) coupling constant = 26.1 Hz. But, H axial indicates a dd splitting pattern because of the coupling with H equatorial and NH protons. 13 C NMR spectra of compounds 5-7, indicated high values for 3 J(P,C) aromatic = 11.9, 11.3 and 10.2 Hz due to the coupling of the aromatic carbon atom of naphthalene moiety with the phosphorus atom. 31 P NMR spectra indicate that the d( 31 P) of compounds 1-4 and 8 containing NH groups connected to the aliphatic carbon atoms appear downfield relative to those of compounds 5-7 that containing NH groups connected to the aromatic naphthalene group.Graphical abstract 4-CH 3 -C 6 H 4 OP(O)[NH(CH 2 ) 3 NH]

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Synthesis and Crystal Structure of 5,5-Dimethyl-2-(p-methylanilino)-2-oxo-1,3,2-diazaphosphorinane

Cited by 11 publications

References 4 publications

Different orientations of C=O versus P=O in P(O)NHC(O) skeleton: the first study on an aliphatic diazaphosphorinane with a gauche orientation

Different orientations of C=O versus P=O in P(O)NHC(O) skeleton: the first study on an aliphatic diazaphosphorinane with a gauche orientation

The first naphthodiazaphosphorinane in the solid phase; syntheses, spectroscopic studies and X-ray crystallography of some new 1,3,2-diheterophosphorus compounds

Phosphorus heterocycles: synthesis, spectroscopic study and X-ray crystallography of some new diazaphosphorinanes

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