The structure of an unusual disulfide, formed from reaction between a sulfene–amine zwitterion and thionyl chloride

Grossert, J. Stuart; Bharadwaj, Madan M.; Faught, J. Brian; Terzis, Aris

doi:10.1139/v80-172

Cited by 6 publications

(4 citation statements)

References 12 publications

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“…6-9 (21) withdrawing chlorine, which also causes the C,-cp bond to be longer in 2 than in 1 (1.525(5), 1; 1.553(6) A , 2). The S-C, bond in 4 should be shorter than that of 2, since 4 lacks the benzoyl group, but it should be jonger than the S-C bond in dimethyl sulfone (20) 1.765(9) A) are equivalent and similar to a previously reported compound (34), yet possibly significan!ly shorter than those angles are listed in Table 4 and presented graphically in Fig. 5.…”

Section: Molecular Geotnetriessupporting

confidence: 77%

“…Two a-bromosulfones have been reported as having a bromine gauche to both sulfonyl oxygens (25). However, sulfones with a polar group at C, usually adopt a conformation in the crystalline state in which the polar group is gauche to only one of the sulfonyl oxygens (23,27,28,34). Dipole moment evidence by Exner and Engberts suggests that this same conformation is predominant in solution (the gallche effect) although in such molecules the causes of this phenomenon are obviously more complex than in simple molecules like 1,2-dihaloethanes or dialkyl disulfides (23).…”

Section: Along S-ca Bondmentioning

confidence: 99%

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The preparation, spectral properties, structures, and base-induced cleavage reactions of some α-halo-β-ketosulfones

Grossert¹,

Dubey²,

Gill³

et al. 1984

Can. J. Chem.

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The halogenation of β-ketosulfones such as α-methylsulfonylacetophenone (1) and benzenesulfonylacetone (10) can be effected with sulfuryl chloride or pyridinium bromide perbromide. Regiochemical control can be achieved by control of stoichiometry and/or the reaction conditions. Detailed 1H and 13C nmr, and mass spectra are recorded for a series of halogenated β-ketosulfones, together with structures by X-ray crystallography for 1, 2-chloro-2-methylsulfonyl-1-phenylethanone (2), chloromethyl methyl sulfone (4), and α-chloroacetophenone (21). Results from these studies are used to suggest a reason for the difficulty associated with substitution reactions of α-halosulfones.

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Section: Molecular Geotnetriessupporting

confidence: 77%

Section: Along S-ca Bondmentioning

confidence: 99%

The preparation, spectral properties, structures, and base-induced cleavage reactions of some α-halo-β-ketosulfones

Grossert¹,

Dubey²,

Gill³

et al. 1984

Can. J. Chem.

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“…These data and analogous 13C NMR results for the adamantanethione (17) and thiofenchone (18) reactions with sulfur dichloride are summarized in Table II and effectively confirm the presence of the expected products 21 and 22, respectively. In the case of thiofenchone, the addition of sulfur dichloride not unexpectedly produces a mixture of diastereomers (22a,b).…”

supporting

confidence: 70%

“…Reactions of Other Thiones (1,(16)(17)(18)(19) with Sulfur Dichloride. The general procedure followed that used in the reaction of xanthione with sulfur dichloride in CS2.…”

Section: Methodsmentioning

confidence: 99%

Synthesis of .alpha.-chlorothiosulfenyl chlorides. A new class of reactive organosulfur compounds

Still¹,

Kutney²,

McLean³

1982

J. Org. Chem.

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acid in 20 mL of methylene chloride. To the reaction mixture, which was allowed to warm to 20 °C over a period of 40 min, was then added 0.5 g of dimethyl sulfide followed (after 5 min) by a solution of 0.3 g (2.4 mmol) of p-anisidine in 10 mL of methylene chloride. The mixture was stirred at room temperature for 12 h, filtered, and the filtrate was concentrated and passed over basic alumina (elution with chloroform) to give 0.136 g (32%) of 6d as a brown solid: mp 108-109 °C; NMR 3.94 (s, 3 H, OCH3), 7.05 (d, 2 H), 7.35 (t, 1 ), 8.18 (d, 2 H), 8.96 (d, 2 H).

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Force field and self‐consistent field calculations on a trans coplanar disulfide: Bis(2‐pyrimidyl)disulfide

Boyd¹,

Lipkowitz²

1981

J Comput Chem

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Two diary1 disulfides, bis(2-pyrimidy1)disulfide and diphenyldisulfide, have been characterized by molecular mechanics and molecular orbital calculations. When complexed with Cu(I), the pyrimidyl disulfide is known to have a unique 180' C-S-S-C dihedral angle and to be coplanar. Our analysis of the conformational energies of the rotamers suggests that copper-ring interactions are primarily responsible for altering the molecular and electronic structure of the disulfide such that the trans barrier to rotation about the S-S bond is effectively overcome. In contrast, the phenyl and uncomplexed pyrimidyl disulfides prefer the usual C-S-S-C torsional angle near 8 5 O and have trans barriers greater than 7 kcal/mol. The barrier to rotation about S-Cspz bonds (2-3 kcal/mol) is low and consistent with ab initio calculations and experiments on other molecules. The force field calculations were done using M M P~. A serious problem was encountered in the use of the M M P l computer program on molecules with N,,a-type atoms that contribute only one electron to the a-electron system. A solution is to modify the variable electronegativity self-consistent field (VESCF) part of the M M P l calculation to use another set of parameters in the program that pertain to a type of nitrogen with one x electron. CND0/2 was used for most of the MO calculations, although INDO and extended Hiickel were also used.

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The structure of an unusual disulfide, formed from reaction between a sulfene–amine zwitterion and thionyl chloride

Cited by 6 publications

References 12 publications

The preparation, spectral properties, structures, and base-induced cleavage reactions of some α-halo-β-ketosulfones

The preparation, spectral properties, structures, and base-induced cleavage reactions of some α-halo-β-ketosulfones

Synthesis of .alpha.-chlorothiosulfenyl chlorides. A new class of reactive organosulfur compounds

Force field and self‐consistent field calculations on a trans coplanar disulfide: Bis(2‐pyrimidyl)disulfide

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