Novel generation of benzonitrile-N-sulfide

Grunwell, John R.; DYE, S. L.

doi:10.1016/s0040-4039(00)72247-7

Cited by 14 publications

(2 citation statements)

References 5 publications

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“…Experimentally, SF 4 is widely used in fluorination of alcohols, aldehydes, ketones, and carboxylic acids. , SF 4 is reacted with primary amines to yield sulfur difluoro imide and sulfur diimides. Although alternative methods for the synthesis of these compounds exist, the most common one is the reaction − of compounds containing the primary amino group (NH 2 ) with SF 4 . This tetravalent S is allowed to interact with a series of electron donor amines, covering a range of both alkylamines and N-containing heteroaromatic rings.…”

Section: Introductionmentioning

confidence: 99%

Chalcogen Bonding between Tetravalent SF₄ and Amines

Nziko

Scheiner

2014

J. Phys. Chem. A

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The N···S chalcogen bond between SF4 and a series of alkyl and arylamines is examined via ab initio calculations. This bond is a strong one, with a binding energy that varies from a minimum of 7 kcal/mol for NH3 to 14 kcal/mol for trimethylamine. Its strength derives in large measure from charge transfer from the N lone pair into the σ*(SF) antibonding orbitals involving the two equatorial F atoms, one of which is disposed directly opposite the N atom. Decomposition of the total interaction energy reveals that the induction energy constitutes more than half of the total attraction. The positive region of the molecular electrostatic potential of SF4 that lies directly opposite the equatorial F atoms is attracted to the N lone pair, but the magnitude of this negative region on each amine is a poor predictor of the binding energy. The shortness and strength of the N···S bond in the dimethylamine···SF4 complex suggest it may better be described as a weak covalent bond.

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Section: Introductionmentioning

confidence: 99%

Chalcogen Bonding between Tetravalent SF₄ and Amines

Nziko

Scheiner

2014

J. Phys. Chem. A

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“…Nitrile sulfides are known to undergo 1,3-dipolar cycloaddition reactions with alkenes 17,[23][24][25][26][27][28] and with ketones, 29,30 provided that the dipolarophiles are activated by electron-withdrawing substituents. For example, benzonitrile sulfide reacts with maleic anhydride 23 and with hexachloroacetone 29 to afford isothiazoline 7 and 1,3,4-oxathiazole 8, respectively (Scheme 2). In the present work we have explored the potential of nitrile sulfide chemistry for the preparation of novel isothiazole-fused quinones, and also examined the site selectivity of nitrile sulfide cycloadditions to the alkene and carbonyl dipolarophile units in NQ and BQ.…”

Section: Methodsmentioning

confidence: 99%

Nitrile sulfides Part 16. Synthesis of 1,2-benzisothiazoles via nitrile sulfide cycloaddition reactions

Ross¹,

Delipala²,

Watson³

et al. 2013

Arkivoc

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The cycloaddition reactions of nitrile sulfides have been used to prepare benzisothiazole quinones and 1,2-benzisothiazole-5,6-dicarboxylates. The nitrile sulfides, generated by thermal decarboxylation of 1,3,4-oxathiazol-2-ones, reacted with 1,4-naphthoquinone to afford 3-substituted naphtho [2,3-d]isothiazole-4,9-diones (17), together with nitriles as by-products. The corresponding reactions with 1,4-benzoquinone yielded regioisomeric mixtures of 2:1 adducts. The 1,2-benzisothiazole-5,6-dicarboxylates were synthesised by a sequence involving both nitrile sulfide and Diels-Alder cycloaddition reactions. Dimethyl 3-phenylisothiazole-4,5-dicarboxylate (34), prepared from benzonitrile sulfide and dimethyl acetylenedicarboxylate (DMAD), was converted into the 4,5-bis(dibromomethyl) analogue 37 via the bis(dihydroxymethyl) compound 35. Treatment of 37 with sodium iodide in the presence of DMAD afforded dimethyl 3-phenyl-1,2-benzisothiazole-5,6-dicarboxylate (30) via the isothiazole o-quinodimethane 32.

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