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Two bis-carbamoylmethylphosphine oxide compounds, namely {[(3-{[2-(diphenylphosphinoyl)ethanamido]methyl}benzyl)carbamoyl]methyl}diphenylphosphine oxide, C 36 H 34 N 2 O 4 P 2 , (I), and diethyl [({2-[2-(diethoxyphosphinoyl)ethanamido]ethyl}carbamoyl)methyl]phosphonate, C 14 H 30 N 2 O 8 P 2 , (II), were synthesized via nucleophilic acyl substitution reactions between an ester and a primary amine. Hydrogen-bonding interactions are present in both crystals, but these interactions are intramolecular in the case of compound (I) and intermolecular in compound (II). Intramolecular π–π stacking interactions are also present in the crystal of compound (I) with a centroid–centroid distance of 3.9479 (12) Å and a dihedral angle of 9.56 (12)°. Intermolecular C—H...π interactions [C...centroid distance of 3.622 (2) Å, C—H...centroid angle of 146°] give rise to supramolecular sheets that lie in the ab plane. Key geometric features for compound (I) involve a nearly planar, trans- amide group with a C—N—C—C torsion angle of 169.12 (17)°, and a torsion angle of −108.39 (15)° between the phosphine oxide phosphorus atom and the amide nitrogen atom. For compound (II), the electron density corresponding to the phosphoryl group was disordered, and was modeled as two parts with a 0.7387 (19):0.2613 (19) occupancy ratio. Compound (II) also boasts a trans -amide group that approaches planarity with a C—N—C—C torsion angle of −176.50 (16)°. The hydrogen bonds in this structure are intermolecular, with a D ... A distance of 2.883 (2) Å and a D —H... A angle of 175.0 (18)° between the amide hydrogen atom and the P=O oxygen atom. These non-covalent interactions create ribbons that run along the b -axis direction.
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Synthetic Routes to, Stabilities and Transformations of, and Characterization of (Carbamoyl)disulfanyl Chlorides and Related Compounds1,2
Previously unobserved (carbamoyl)disulfanyl chlorides were prepared by (i) addition of limiting aromatic secondary amine to (chlorocarbonyl)disulfanyl chloride; (ii) Harris reactions of sulfur dichloride with appropriate O-alkyl N-methyl-N-arylthiocarbamates; and (iii) regiospecific chlorolysis of bis(N-methyl-N-arylcarbamoyl)disulfanes. The newly synthesized unstable species were observed in situ by 1H NMR and were trapped with alkenes, thiocarbamates, and thiols using methods precedented by the chemistry of analogous (carbamoyl)sulfenyl chlorides. Furthermore, each of the trapped products was synthesized by an alternate route, reinforcing conclusions about their structures. While (N-methyl-N-phenylcarbamoyl)disulfanyl chloride was unstable and decomposed quickly or cyclized intramolecularly, introduction of the N,2,6-trimethylphenyl moiety led to significantly improved stability. As part of this study, an interesting, unexpectedly stable 1,2,4-dithiazinone was discovered and its structure was established by X-ray crystallography. The new heterocycle, with its twisted out-of-plane disulfide bond in a six-membered ring, readily donated a sulfur atom to triphenylphosphine; this reaction resulted in the formation of triphenylphosphine sulfide, along with the corresponding highly stable heterocycle in which the single sulfur that remains is part of a planar five-membered ring, fused to a co-planar aryl moiety.
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- Award ID(s):
- 2215973
- PAR ID:
- 10653935
- Publisher / Repository:
- Multidisciplinary Digital Publishing Institute
- Date Published:
- Journal Name:
- Molecules
- Volume:
- 30
- Issue:
- 19
- ISSN:
- 1420-3049
- Page Range / eLocation ID:
- 3892
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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