SYNTHETIC, N.M.R. SPECTROSCOPIC AND X-RAY CRYSTALLOGRAPHIC INVESTIGATIONS ON THE PRODUCTS OF THE REACTIONS OF PHENYL (METHYL) PHOSPHONOTHIOIC DICHLORIDE AND THIOPHOSPHORYL CHLORIDE AND PSCL<sub>3</sub>WITH PRIMARY AMINES

Hursthouse, Michael B.; Ibrahim, Emad; Parkes, Harold G.; Shaw, L. S.; Shaw, Robert A.; Watkins, David

doi:10.1080/03086648608072816

Cited by 7 publications

(5 citation statements)

References 2 publications

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“…A previous article mentioned the general procedure for the synthesis of P(S) [NHR] 3 phosphorothioic triamide and reported the 31 P NMR data for some derivatives, such as P(S)-[NHC 6 H 11 ] 3 (Hursthouse et al, 1986). Moreover, Mel'nikov & Zen'kevich (1955) reported a general method for the synthesis of some amides and hydrazides of dialkoxythiophosphoric acids, such as P(S)[OC 2 H 5 ] 2 [NHNHC 6 H 5 ], together with its melting point and the elemental analysis for the P atom.…”

Section: Synthesis and Crystallizationmentioning

confidence: 99%

“…In a more recent article (Riesel & Helbing, 1992), the phosphorous chemical shift of P(S)[OC 2 H 5 ] 2 [NHNHC 6 H 5 ] was found. The procedures reported here for the synthesis of (I) and (II) are similar to the literature methods but with a few modifications, for example, using an ice-bath temperature in this work instead of the reflux conditions used by Hursthouse et al (1986).…”

Section: Synthesis and Crystallizationmentioning

confidence: 99%

“…31 P NMR (162.0 MHz, DMSO-d 6 ): 57.25 (m); 1 H NMR (400.1 MHz, DMSO-d 6 ): 1.05 (m, 6H), 1.15 (m, 9H), 1.51 (br m, 3H), 1.64 (br m, 6H), 1.85 (br m, 6H), 2.95 (br m, 3H), 3.63 (pseudo-t, J = 9.2/9.6 Hz, 3H, NH); 13 C NMR (100.6 MHz, DMSO-d 6 ): 25.75 (d, J P,C = 4.7 Hz), 35.72 (d, J P,C = 4.9 Hz), 40.44 (s), 50.48 (s) {the 31 P chemical shift of P(S)[NHC 6 H 11 ] 3 in CDCl 3 was reported at 59.1 p.p.m. ; Hursthouse et al, 1986}. Compound (II) was synthesized from the reaction of C 6 H 5 NHNH 2 (20 mmol) and P(S)[OC 2 H 5 ] 2 Cl (10 mmol) in dry CH 3 CN [with a stirring time of 3 h and using the purification procedure mentioned for (I)]. Single crystals were obtained from a solution of the product in CH 3 C(O)CH 3 / CH 3 CN (1:1 v/v) after slow evaporation at room temperature.…”

Section: Synthesis and Crystallizationmentioning

confidence: 99%

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Two new thiophosphoramide structures:N,N′,N′′-tricyclohexylphosphorothioic triamide andO,O′-diethyl (2-phenylhydrazin-1-yl)thiophosphonate

et al. 2014

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The compound N,N',N''-tricyclohexylphosphorothioic triamide, C18H36N3PS or P(S)[NHC6H11]3, (I), crystallizes in the space group Pnma with the molecule lying across a mirror plane; one N atom lies on the mirror plane, whereas the bond-angle sum at the other N atom has a deviation of some 8° from the ideal value of 360° for a planar configuration. The orientation of the atoms attached to this nonplanar N atom corresponds to an anti orientation of the corresponding lone electron pair (LEP) with respect to the P=S group. The P=S bond length of 1.9785 (6) Å is within the expected range for compounds with a P(S)[N]3 skeleton; however, it is in the region of the longest bond lengths found for analogous structures. This may be due to the involvement of the P=S group in N-H···S=P hydrogen bonds. In O,O'-diethyl (2-phenylhydrazin-1-yl)thiophosphonate, C10H17N2O2PS or P(S)[OC2H5]2[NHNHC6H5], (II), the bond-angle sum at the N atom attached to the phenyl ring is 345.1°, whereas, for the N atom bonded to the P atom, a practically planar environment is observed, with a bond-angle sum of 359.1°. A Cambridge Structural Database [CSD; Allen (2002). Acta Cryst. B58, 380-388] analysis shows a shift of the maximum population of P=S bond lengths in compounds with a P(S)[O]2[N] skeleton to the shorter bond lengths relative to compounds with a P(S)[N]3 skeleton. The influence of this difference on the collective tendencies of N···S distances in N-H···S hydrogen bonds for structures with P(S)[N]3 and P(S)[O]2[N] segments were studied through a CSD analysis.

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Section: Synthesis and Crystallizationmentioning

confidence: 99%

Section: Synthesis and Crystallizationmentioning

confidence: 99%

Section: Synthesis and Crystallizationmentioning

confidence: 99%

See 1 more Smart Citation

Two new thiophosphoramide structures:N,N′,N′′-tricyclohexylphosphorothioic triamide andO,O′-diethyl (2-phenylhydrazin-1-yl)thiophosphonate

et al. 2014

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“…A previous article mentioned the general procedure for the synthesis of P(S) [NHR] 3 phosphorothioic triamide, and reported the 31 P NMR data for some derivatives, such as P(S)[NHCH 2 C 6 H 5 ] 3 (Hursthouse et al, 1986). The procedure reported here for the synthesis of (I) is similar to the literature method but with a few modifications, for example, using an ice-bath in this work instead of the reflux conditions reported earlier.…”

Section: Synthesis and Crystallizationmentioning

confidence: 99%

“…IR (KBr disc, , cm À1 ): 3377, 3199, 3024, 2917, 2862, 1952, 1874, 1809, 1661, 1601, 1494, 1453, 1396, 1306, 1207, 1076, 1046, 1000, 909, 860, 800, 744, 695, 643, 501; 31 Hursthouse et al (1986)}.…”

Section: Spectroscopic Analysismentioning

confidence: 99%

A new phosphorothioic triamide structure: P(S)[NHCH₂C₆H₅]₃

et al. 2015

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The structure of N,N',N''-tribenzylphosphorothioic triamide, C21H24N3PS, (I), and analysis of the bond-angle sums at the N atoms for this compound, and for 74 structures with a P(S)[N]3 skeleton and the N atom in a three-coordinate geometry found in the Cambridge Structural Database [CSD; Groom & Allen (2014). Angew. Chem. Int. Ed. 53, 662-671], are reported. For (I), the bond-angle sum at one of the N atoms [359 (1)°] shows a nearly planar configuration, while the other two show a nonplanar geometry with bond-angle sums of 342 (1) and 347 (1)°. The location of the atoms attached to the nonplanar N atoms suggests an anti orientation of the corresponding lone electron pairs (LEPs) on these N atoms with respect to the P=S group. For 74 structures with a P(S)[N]3 skeleton and with the N atom in a three-coordinate geometry, the bond-angle sums at the N atoms were found to be in the range 293-360°. Among 307 such three-coordinate N atoms, 39% (120 N atoms) have bond-angle sums in the range 359-360°, in accordance with sp(2) hybridization, and 45% (138 N atoms) have bond-angle sums in the range 352-359°, with hybridization close to sp(2). For the orientation of the LEP with respect to the P=S group, the anti orientation was found to be a general rule for N atoms, with the corresponding bond-angle sums deviating by more than 8° from the planar value of 360°. In the title structure, the S atom takes part in intermolecular (N-H···)(N-H···)S hydrogen bonds, connecting the molecules into extended chains parallel to the b axis. The co-operation of one N atom in an N-H···S hydrogen bond as an H-atom donor, and in an N-H···N hydrogen bond as an acceptor, is a novel feature of the crystal structure.

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The Synthesis and Reactions of Thio‐ and Seleno‐Phosphonic and ‐Phosphinic Acids

Edmundson¹

2009

Patai's Chemistry of Functional Groups

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Introduction The Synthesis of Monothio‐ and Monoseleno‐Phosphonic and ‐Phosphinic Acids and their Derivatives Interconversions of the Monothio(or Seleno) ‐Phosphonic and ‐Phosphinic Acids and Their Derivatives Syntheses and Reactions of Di‐ and Tri‐Thio(Seleno)‐Phosphonic Acids and Dithio(Seleno)Phosphinic Acids

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SYNTHETIC, N.M.R. SPECTROSCOPIC AND X-RAY CRYSTALLOGRAPHIC INVESTIGATIONS ON THE PRODUCTS OF THE REACTIONS OF PHENYL (METHYL) PHOSPHONOTHIOIC DICHLORIDE AND THIOPHOSPHORYL CHLORIDE AND PSCL₃WITH PRIMARY AMINES

Cited by 7 publications

References 2 publications

Two new thiophosphoramide structures:N,N′,N′′-tricyclohexylphosphorothioic triamide andO,O′-diethyl (2-phenylhydrazin-1-yl)thiophosphonate

Two new thiophosphoramide structures:N,N′,N′′-tricyclohexylphosphorothioic triamide andO,O′-diethyl (2-phenylhydrazin-1-yl)thiophosphonate

A new phosphorothioic triamide structure: P(S)[NHCH₂C₆H₅]₃

The Synthesis and Reactions of Thio‐ and Seleno‐Phosphonic and ‐Phosphinic Acids

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SYNTHETIC, N.M.R. SPECTROSCOPIC AND X-RAY CRYSTALLOGRAPHIC INVESTIGATIONS ON THE PRODUCTS OF THE REACTIONS OF PHENYL (METHYL) PHOSPHONOTHIOIC DICHLORIDE AND THIOPHOSPHORYL CHLORIDE AND PSCL3WITH PRIMARY AMINES

Cited by 7 publications

References 2 publications

Two new thiophosphoramide structures:N,N′,N′′-tricyclohexylphosphorothioic triamide andO,O′-diethyl (2-phenylhydrazin-1-yl)thiophosphonate

Two new thiophosphoramide structures:N,N′,N′′-tricyclohexylphosphorothioic triamide andO,O′-diethyl (2-phenylhydrazin-1-yl)thiophosphonate

A new phosphorothioic triamide structure: P(S)[NHCH2C6H5]3

The Synthesis and Reactions of Thio‐ and Seleno‐Phosphonic and ‐Phosphinic Acids

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SYNTHETIC, N.M.R. SPECTROSCOPIC AND X-RAY CRYSTALLOGRAPHIC INVESTIGATIONS ON THE PRODUCTS OF THE REACTIONS OF PHENYL (METHYL) PHOSPHONOTHIOIC DICHLORIDE AND THIOPHOSPHORYL CHLORIDE AND PSCL₃WITH PRIMARY AMINES

A new phosphorothioic triamide structure: P(S)[NHCH₂C₆H₅]₃