Ene-type reaction of trisubstituted monoterpene alkenes with methyl sulfite and thionyl chloride

Trisubstituted methylalkenes react with methyl sulfite at 25°C in the presence of BF₃ · Et₂O in the ene-type fashion to give the corresponding methallyl sulfinates. Such compounds can also be prepared under considerably milder conditions by the Et₂AlCl-catalyzed reaction of thionyl chloride with mono- and dienes followed by methanolysis of intermediate alkyl sulfinyl chlorides. These reactions represent a new method for terminal functionalization of linear isoprenoids.Deceased Nov.1, 1992.Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 105–107, January, 1993.     

A novel reaction of thionyl chloride with 3-aryl-2,1-benzisoxazoles

Novel reductive chlorination of 3-aryl-2,1-benzisoxazoles with thionyl chloride is described. The chlorinated aminobenzophenones have been characterised.     

An oxidation with thionyl chloride

The reaction of the 2-methylquinoline-3-carboxylic acid 1b with thionyl chloride gave the dichlorothiolactone 2 , the structure of which was confirmed by chemical transformations.     

Kinetics and mechanism of reaction between polyfluorinated alcohols and thionyl chloride

Complexing of polyfluorinated alcohols with triethylamine was studied by means of microcalorimetry, IR and NMR spectroscopy. The reaction kinetics of these polar complexes with thionyl chloride was investigated using calorimetry of heat fluxes applying mathematical simulation procedure. The second order of nucleophilic substitution reaction of chlorine by polyfluoroalkoxy group was established.Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 11, 2004, pp. 1628–1631.Original Russian Text Copyright © 2004 by Rakhimov, Popov, Vostrikova, Vostrikova, Zauer.     

Reactions of salicylamides with thionyl chloride

A series of compounds having the 1,2,3-benzoxathiazin-4 (3H) one 2-oxide structure have been synthesized by the interaction of thionyl chloride with the appropriate salicylamide. Some properties of these compounds as well as some by-products are described.     

Antioxidant activity of hydrazones with sterically hindered phenol fragments

Kinetic parameters of the antiradical activity of derivatives of hydrazones of 4-hydroxy-3,5-di-tert-butyl-benzaldehyde are determined photocolorimetrically in their reactions with a stable diphenylpicrylhydrazyl radical, and by chemiluminescence from the capture of peroxide radicals upon the initiated oxidation of ethylbenzene. It is found that during inhibited oxidation, the reactive centers (N-H and O-H) in hetaryl- and acylhydrazone molecules operate in parallel. Regularities of the compounds?? inhibiting effect are studied in heterogeneous systems upon the initiated oxidation of ethylbenzene in emulsion, and in a water-lipid model of the oxidation of phosphatidylcholine dispersion. It is established that hydrazone derivatives are antioxidants of combined action in heterophase processes of the oxidation of unsaturated substrates, displaying properties of hydroperoxide deactivators in addition to their antiradical activity.     

Reaction of 2-thiobenzazoles with thionyl chloride

A new reaction in the benzimidazole series, viz., replacement of the mercapto group by chlorine by the action of thionyl chloride on 2-thiobenzimidazoles, was discovered. Benzoxazolone is formed by treatment of 2-thiobenzoxazole with thionyl chloride, and 2,2-dithiobis(2-benzothiazole) is formed from 2-thiobenzothiazole.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1047–1050, August, 1985.     

Study of the reaction of cis- and trans-4-acylamino-3-hydroxythiophans with thionyl chloride

The reaction of cis- and trans-4-acylamino-3-hydroxythiophans with thionyl chloride was studied. It was found that chlorosulfites are initially formed with retention of the configuration of the starting compound. 2-Substituted 3a,4,6,6a-tetrahydrothieno[3,4-d]oxazoline is formed from trans-4-acylamino-3-chlorosulfitothiophans by thermal reaction or in the presence of pyridine, whereas trans-4-acylamino-3-chlorothiophans are obtained from cis-4-acylamino-3-chlorosulfitothiophans; both reactions proceed with inversion of configuration.     

Direct polyamidation with thionyl chloride in N-methyl-pyrrolidone

Mechanistic features of the reaction promoted by thionyl chloride and amides such as N-methylpyrrolidone (NMP) were studied. The reaction was effective in the amidation of carboxylic acids, but not effective in the esterification. The amidation was affected by the kind and the amount of amides used, most favorably by two equivalents of NMP with respect to the acid. These amides were assumed to be involved in the intermediate formation, and the reaction was proposed to proceed via Vilsmeier adducts derived from thionyl chloride and the amides, and through activation of a carboxylic acid different from an acyl chloride. The reaction was successfully applied to the direct polycondensation of aromatic dicarboxylic acids and diamines in NMP at 70°C to produce polyamides with high molecular weights. Initial reaction of dicarboxylic acids with the adducts, additive effect of tertiary amines, and polycondensation temperatures were studied in terms of the inherent viscosity of the polymers produced.     

Synthesis of hydrazones containing sterically hindered phenol groups and tetrathiacalix[4]arene fragment

1,3-Alternate and cone stereoisomers of tetrathiacalix[4]arene and 4-tert-butyltetrathiacalix[4]arene functionalized by carbohydrazide groups reacted with 3,5-di-tert-butyl-4-hydroxybenzaldehyde to give the corresponding hydrazones having sterically hindered phenol fragments.     

Polymerization of N-vinylcarbazole by thionyl chloride

The polymerization of N-vinylcarbazole (NVC) initiated by SOCl₂ in benzene and nitrobenzene solvents was studied at 32°C. R_p is first order with respect to SOCl₂ concentration and also to NVC concentration up to a certain NVC concentration, after which it falls. Rate and the molecular weight increase with increasing dielectric constant of the medium. The rate and molecular weight are depressed by the addition of amines, thiophene, and water. The degree of polymerization is independent of SOCl₂ and NVC concentration. A conventional cationic mechanism has been suggested, and a suitable kinetic scheme has been proposed in conformity with the findings.     

A facile entree to α-oxo sulfines by reaction of thionyl chloride with silyl enol ethers

Silyl enol ethers derived from 1-indanone, 2-indanone, α-tetralone and 4-chromanone react with thionyl chloride to give α-oxo sulfines (3) which can be either isolated or trapped by a cycloaddition reaction with a diene.     

N,N-二(2-羟乙基)对甲苯磺酰胺与氯化亚砜的反应

N,N-二(2-羟乙基)对甲苯磺酰胺(1)与SOCl_2反应,通常得化合物2. 文献报道采用过量SOCl_2作溶剂在130～140℃进行反应,但后处理较麻烦,且SOCl_2用量也较大.我们改用二甲苯作溶剂,并减少SOCl_2的用量及采用分次加入的方法,收到了较好的效果.在此反应过程中,意外地获得了一无色针状结晶,根据IR,~1H NMR,MS及元素分析证明此化合物为3.上述反应如控制反应条件可使1全部转化得3.