Sulfenyl Halides in the Synthesis of Heterocycles. 2. Cyclization in Reactions of Hetarenesulfenyl Chlorides with 3,3-Dimethyl-1-butene

Abstract

We have formulated and developed a route for the synthesis of sulfur-containing heterocycles based on the interaction of sulfenyl chlorides with unsaturated compounds which occurs by ring closure at the nucleophilic center of the sulfenyl unit [1-6].In the current work reactions of 3,3-dimethyl-1-butene (1) with the hetarenesulfenyl chlorides 2a-d which contain a potentially nucleophilic nitrogen atom in the hetaryl unit: 4,6-dimethylpyrimidine-2-(2a), 3-cyano-4,6-dimethylpyridine-2-(2b), quinoline-8-(2c), and 1,3-benzothiazole-2-sulfenyl chloride (2d). S-Het Cl N N Me Me N Me Me CN N S N t-Bu 1 + Het-SCl 2a-d t-Bu 2, 3 a Het = b Het = c Het = d Het = , , , 3a-dWith the help of 1 H NMR spectroscopy it was established that addition products at the double bond contrary to Markovnikov's rule -the corresponding β-chlorosulfides 3a-d -were obtained rapidly and with quantitative yield from compounds 2a-d and the alkene 1 at 20°C.

Synthesis of 2,3-dihydroselenazolo[3,2-a]pyridinium salts based on reactions of pyridine-2-selanyl chloride with alkenes and dienes

“…Assignment of the signals in the 1 H NMR spectra was carried out with consideration of the spectroscopic parameters for the previously obtained products of cycloaddition of hetarylsulfenyl chlorides to alkenes or dienes, the structures of which were proved by X-ray crystallographic analysis [12,[16][17][18].…”

A Novel Family of [1,4]Thiazino[2,3,4-ij]quinolin-4-ium Derivatives: Regioselective Synthesis Based on Unsaturated Heteroatom and Heterocyclic Compounds and Antibacterial Activity

“…The action of sulfuryl chloride on di(8-quinolinyl) disulfide (2) in methylene chloride or chloroform led to the generation of 8-quinolinesulfenyl chloride (3), which was used in situ without isolation in further reactions with unsaturated heteroatom compounds (Scheme 2). Despite some progress in the development of synthetic methods for the preparation of 2H,3H- [1,4]thiazino [2,3,4-ij]quinolin-4-ium derivatives [33][34][35][36][37][38][39][40][41], the annulation reactions of 8-quinolinesulfenyl halides with a number of vinylic heteroatom compounds (4-pentenoic acid, 5-hexenoic acid, allyl chloride and bromide, allyl cyanate, N-vinyl pyrrolidin-2-one, 1-vinylimidazole, ethyl and butyl vinyl ethers) have not been described in the literature. The synthesis of novel families of compounds with potential biological activity and evaluation of their antimicrobial properties represent urgent tasks.…”

“…Recently we described the annulation reactions of 8-pyridinesulfenyl halides with functionalized alkenes and cycloalkenes affording a series of 2Н,3Н- [1,4]thiazino [2,3,4-ij]quinolin-4-ium derivatives in high yields [33,34]. For example, the annulation reactions with divinyl and vinyl phenyl sulfides proceeded with the attachment of the sulfur atom of 8-pyridinesulfenyl halides at the β-position of the vinylsulfanyl group, while the addition of the sulfur atom occurred at the α-carbon atom of the vinylsilyl moiety in the case of tetravinyl silane with the formation of 2-(trivinylsilyl)-2Н,3Н- [1,4]thiazino [2,3,4- Despite some progress in the development of synthetic methods for the preparation of 2H,3H- [1,4]thiazino [2,3,4-ij]quinolin-4-ium derivatives [33][34][35][36][37][38][39][40][41], the annulation reactions of 8-quinolinesulfenyl halides with a number of vinylic heteroatom compounds (4-pentenoic acid, 5-hexenoic acid, allyl chloride and bromide, allyl cyanate, N-vinyl pyrrolidin-2-one, 1-vinylimidazole, ethyl and butyl vinyl ethers) have not been described in the literature. The synthesis of novel families of compounds with potential biological activity and evaluation of their antimicrobial properties represent urgent tasks.…”

Crystal structure of (E)-3-(1-iodoethylidene)-2,3-dihydro-[1,4]thiazino- [2,3,4-ij]quinolin-4-ium triiodide, C13H11I4NS

“…Anumber of syntheses for 8-thioquinoline compounds with fused N-1/C-8 centers [3][4][5] werereported. Represented crystal structure can be aconvenient model for studying cation×××triiodide anion interactions [6][7] as it illustrates I×××Inon-covalent interactions involving terminal triiodide atomsa sd onors of electrons and iodine atom in =C12-I1 group as electron acceptor.…”