Reaction of 3,6-di-tert-butylpyrocatechol with thionyl chloride in the presence of dimethylformamide

Conclusions An unusual type of reaction of 3,6-di-tert-butylpyrocatechol with thionyl chloride was discovered, which leads to the formation of elementary sulfur. A mechanism, including the formation of sulfuran, was proposed.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1635–1637, July, 1984.     

Reaction of cis- and trans-4-alkoxycarbonylamino-3-hydroxythiophans with thionyl chloride

The reaction of cis- and trans-4-alkoxycarbonylamino-3-hydroxythiophans with thionyl chloride gives chlorosulfites. trans-4-Alkoxycarbonylamino-3-chlorosulfito-thiophans are converted to cis-3a,4,6,6a-tetrahydrothieno[3,4-d]oxazolidone by heating or by treatment with pyridine. cis-4-Carboalkoxyamino-3-hydroxythiophans form 3-carboalkoxy-3a,4,6,6a-tetrahydrothieno[3,4-d]oxathiazolidones.     

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.     

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.     

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.     

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.     

Reaction of O,O-dialkyl alkylphosphonates with thionyl chloride. A remarkable effect of the O-(2-dialkylamino)ethyl substituent

Reaction of dialkyl alkylphosphonates with SOCl₂ in the presence of DMF, reported by Maier, can serve as a convenient route to simple monoalkyl alkylphosphonochloridates. However, when a substrate contains a (2-dialkylamino)ethyl group as one of the ester functions, the course of the reaction is determined by the nature of the N-alkyl groups. With the NMe₂ group present, reaction with SOCl₂ occurs at nitrogen, and no exchange of groups at phosphorus takes place. The NEt₂ group, on the other hand, directs the reaction to phosphorus, and the Maier reaction of the exchange of one ester group OR for Cl proceeds in high yields. © 1996 John Wiley & Sons, Inc.     

Nuclear quadrupole coupling constants of thionyl chloride

The nuclear quadrupole structure of some low J transitions with large splittings has been measured for thionyl chloride (SO³⁵Cl₂) and analysed in terms of a first order perturbation. The following nuclear quadrupole coupling constants were obtained: x_aa = ?25.01 ± 0.07 MHz, x_bb = ?0.03 ± 0.45 MHz and x_cc = 25.04 ± 0.45 MHz.     

Direct polycondensation of hydroxybenzoic acids with thionyl chloride in pyridine

The reaction promoted by thionyl chloride and pyridine could selectively activate carboxyl groups of hydroxybenzoic acids to give polyesters of high inherent viscosities up to 3.8. Favorable conditions were studied in terms of the temperatures for the initial reaction with the acids and subsequent aging at room temperature. Copolymers of several combinations of hydroxybenzoic acids with high molecular weights were obtained in quantitative yield by carrying out the polycondensation at 80°C for 3 h. The reaction could also produce high molecular polyesters in a simpler process without the initial activation of dicarboxylic acids by adding a mixture of these monomers to the condensing agent, and a tough film- and fiberforming polymer was obtained from 4,4′-dihydroxyphenylsulfone of low nucleophilicity whose polymer of high molecular weight is difficult to obtain. The process was also successfully applied to the direct copolycondensations of hydroxybenzoic acids, aromatic dicarboxylic acids, and bisphenols to produce polyesters of η_inh up to 5.6.     

Synthesis of hindered hydrazones and their reaction with thionyl chloride

Hydrazones 12a–c and ketazines 13a–c were prepared by the reaction of ketones 11a–c with hydrazine hydrate depending on the temperature and the reaction time. Some ketone (aryl)hydrazone derivatives 14a,c,e reacted with thionyl chloride to afford the chlorothiadiazoline derivatives 15a–c . Surprisingly, the chlorine atom in the latter compounds was found to undergo smooth nucleophilic substitution, and by boiling these compounds in absolute ethanol gave the corresponding ethoxythiadiazoline derivatives 16a–c . The structure of the ethoxythiadiazoline 16b was confirmed by single crystal X‐ray determination. © 2003 Wiley Periodicals, Inc. Heteroatom Chem 14:223–228, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10125     

Lithium-lithium tetrachloroaluminate reference electrode in thionyl chloride

Three in situ techniques for charging current compensation (c.c.c.) in d.c. polarography are described. These methods envisage the superposition of an a.c. ripple and analogue processing of the response to yield a quantity proportional to the d.c. charging current. The theory of these procedures outlined in this paper, enables one to approach c.c.c. without any reliance on trial and error. Details of the appropriate circuitry and supporting experimental verification of the theory are also presented.     

亚硫酰氯还原的电催化研究

利用碳粉微电极和显微Raman分子探针技术研究了SOCl~2阴极还原的电催化性能.在八硫杂氢化酞菁的催化作用下, SOCl~2还原过程中的产物硫将进一步还原.碳粉微电极表面沉积物形貌和Raman光谱分析表明硫是引起电极钝化的另一个重要因素,催化剂存在的条件下,硫进一步还原的结果是使碳表面有不同程度的活化,这对提高电池容量和电压有较大影响.     

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.