Efficient synthesis of N-oxysulfonyl formamidines through thionyl chloride-promoted reaction of sulfamates with formamides

N-Oxysulfonyl formamidine derivatives have been efficiently synthesized under mild conditions through direct condensation of various sulfamates and formamides in the presence of thionyl chloride. The scope of this reaction was investigated, and a plausible mechanism was proposed. The resulting N-oxysulfonyl formamidines can be converted to sulfamates through appropriate deprotection.     

Sulfenylation reactions activated by thionyl and sulfuryl chlorides

Reactions ofN-(4-nitrophenylthio)morpholine,N,N′-thiobismorpholine, andN,N′-dithiobismorpholine with thionyl chloride or sulfuryl chloride at −40°C afford electrophilic chlorosulfenylating reagents, which add to the C=C bond of norbornene in high yields. Semiempirical quantum-chemical calculations and comparison of the relative reactivity of the sulfenylating complexes formed upon activation of arenesulfenamides by sulfur and phosphorus oxohalides were performed. The mechanism of the reactions is discussed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2516–2518, December, 1998.     

Zirconyl chloride promoted highly efficient solid phase synthesis of amide derivatives

An efficient solid phase route for the synthesis of amide derivatives by the reaction of carboxylic acids with urea in the presence of catalytic amount of zirconyl chloride under microwave irradiation conditions was described.In this way,a range of interesting amide derivatives was obtained in good to excellent yields.The catalyst was recycled with fresh reactants and it gave almost similar results without significant loss of activity up to the third run.     

Efficient synthesis of pyrimidinone derivatives by ytterbium chloride catalyzed Biginelli-type reaction under solvent-free conditions

An efficient and clean method was developed for the one-pot synthesis of pyrimidinones by ytterbium chloride catalyzed Biginelli-type reaction of aromatic aldehyde, cyclopentanone, and urea or thiourea under solvent-free conditions.     

Preparation and characterization of new thermally stable and optically active poly(ester‐imide)s by direct polycondensation with thionyl chloride in pyridine

4,4′‐hexafluoroisopropylidene‐2,2‐bis‐(phthalic acid anhydride) (1) was reacted with L ‐methionine (2) in acetic acid and the resulting N,N′–(4,4′‐hexafluoroisopropylidenediphthaloyl)‐bis‐L ‐methionine (4) was obtained in high yield. The direct polycondensation reaction of this diacid with several aromatic diols such as bisphenol A (5a), phenolphthalein (5b), 1,4‐dihydroxybenzene (5c), 4,4′‐dihydroxydiphenyl sulfide (5d), 4,6‐dihydroxypyrimidine (5e), 4,4′‐dihydroxydiphenyl sulfone (5f) and 2,4′‐dihydroxyacetophenone (5g) was carried out in a system of thionyl chloride and pyridine. Expecting that the reaction with thionyl chloride in pyridine might involve alternative intermediates different from an acyl chloride, the polycondensation at a higher temperature favorable for the reaction of the expected intermediate with nucleophiles was attempted, and a highly thermally stable poly(ester‐imide) was obtained by carrying out the reaction at 80°C. All of the above polymers were fully characterized by ¹H‐NMR, ¹⁹F‐NMR FT‐IR spectroscopy, elemental analysis and specific rotation. Some structural characterization and physical properties of these optically active poly(ester‐ imide)s are reported. Copyright © 2006 John Wiley & Sons, Ltd.     

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.     

Facile synthesis of 2,2,2-trifluoroacetimidoyl chloride derivatives

Several 2,2,2-trifluoroacetimidoyl chlorides have been prepared in a one-pot stage from primary aromatic amines and trifluoroacetic acid. The reactions were carried out with different primary aromatic amines which they contain additional functional groups and good yield were obtained.     

Iodine catalyzed efficient synthesis of symmetrical diaryl sulfoxides from arenes and thionyl chloride under solvent-free conditions

Synthesis of symmetrical diaryl sulfoxides from arenes and thionyl chloride in the presence of a catalytic amount of iodine at room temperature under solvent-free conditions is described.Mild reaction conditions,easy workup,high yield,and easily available catalyst are important features of this method.     

Synthesis of pyrimidine derivatives via multicomponent reaction catalyzed by ferric chloride

An eco-friendly and practical approach was developed for the synthesis of pyrimidine derivatives via a one-pot, three-component coupling reaction of commercially available aldehydes, alkynes, and indazole3/triazole catalyzed by ferric chloride with good to excellent yields. The advantages of this method include environmentally friendly catalyst, easily available materials, and ease of product isolation.     

Wet cyanuric chloride promoted efficient synthesis of amidoalkyl naphthols under solvent-free conditions

An efficient and direct procedure has been developed for the preparation of amidoalkyl naphthols by a one-pot condensation of aryl aldehydes.2-naphthol and area or amides,in the presence of wet-cyanuric chloride(wet-TCT)as a catalyst.The reactions were carried out under solvent.flee media.The present methodology offers several advantages such as excellent yields,simple procedure and eco-friendly reaction condition.     

Meglumine promoted one-pot,four-component synthesis of pyranopyrazole derivatives

Meglumine, a bio-based chemical, was demonstrated to be a highly efficient and reusable catalyst for the synthesis of a series of pyranopyrazole derivatives via a one-pot, four-component reaction of carbonyl compound or isatin, hydrazine hydrate, malononitrile, and β-keto ester in EtOH–H₂O. The catalyst was found to work extremely for aldehydes, ketones or isatins at room temperature to give the corresponding dihydropyrano[2,3-c]pyrazole or spiro[indoline-3,4′-pyrano[2,3-c]pyrazole] derivatives in high yields. The salient features of this new methodology are broad substrate scope, room temperature reaction conditions, short reaction times, high yields, easy work-up process, reusability of catalyst, and the absence of hazardous organic solvents.     

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.     

Ammonium Chloride Promoted Palladium-Catalyzed UIImann Coupling of Aryl Bromide

In water, ammonium chloride was found to promote palladium-catalyzed Ullmann coupling reactions of aryl bromides. In the presence of Pd/C, zinc, NH4Cl, and water, coupling of various aryl bromides was carried out smoothly to afford the corresponding homocoupling products in moderate yields.     

High-molecular-weight poly(p-phenyleneterephthalamide) by CaCl2 promoted direct polycondensation with thionyl chloride in N-methylpyrrolidone

The direct polycondensation of terephthalic acid and p-phenylenediamine hydrochloride (PPD.2HCl) with thionyl chloride was found to be significantly promoted in N-methylpyrrolidone (NMP) by dissolved CaCl₂ and tertiary amines. The inherent viscosity of the polymer obtained varied with the amount of CaCl₂ and tertiary amines added. The reaction, when effectively promoted by CaCl₂, proceeded homogeneously in the early state of polycondensation, and then resulted in a highly swollen gel. CaCl₂ had to be present in the PPD.2HCl/tertiary amines/NMP solution as well as in the TPA/SOCl₂/NMP mixture for the polycondensation to proceed to high molecular weight. Complexes of CaCl₂, PPD.2HCl, and tertiary amines in NMP similar to the well known complex, CaCl₂ · nNH₃ (n = 2, 4, 8) was proposed to facilitate the polycondensation.     

Impedance diagnostics of lithium—thionyl chloride power sources

The problem associated with the use of an impedance spectroscopy method for the determination of the state (in the first place, depth of discharge) of primary power sources in the system thionyl chloride-lithium is considered. The conclusion is made on the basis of an analysis of literature data concerning the problem under consideration and the results of comprehensive investigations of lithium-thionyl chloride cells about the impossibility of performing sufficiently correct diagnostics of the latter by the impedance method. Information, which is provided by this method, is of a semiquantitative character. It may be utilized solely for carrying out rough estimates of the state of the cells, for example, for sorting out the power sources that exhausted practically completely (by more than 80%) their resource.     

On the mechanism of conversion of 4-carboxy-3,4-dihydro-3-phenyl-1(2H)-isoquinolones to indeno[1,2-c]isoquinolines by thionyl chloride

It has been known for a long time that thionyl chloride can effectively mediate the transformation of 4-carboxy-3,4-dihydro-3-phenyl-1(2H)-isoquinolones to indeno[1,2-c]isoquinolines. The mechanism of this unique transformation, however, remains to be established. Evidence is presented to demonstrate that (1) the two-electron dehydrogenation precedes Friedel-Crafts cyclization and (2) the two-electron dehydrogenation occurs via H-4 deprotonation and subsequent O-sulfinylation of the lactam moiety instead of C-sulfinylation of the carbon α to the carboxyl group.     

Ferric chloride/tetraethyl orthosilicate as an efficient system for synthesis of dihydropyrimidinones by Biginelli reaction

An efficient method for the Biginelli reaction of aldehydes, acetoacetate esters and urea employing tetraethyl orthosilicate in the presence of ferric chloride is described. These improved reaction conditions allow the preparation of a wide variety of substituted dihydropyrimidinones (including sterically encumbered ones) in high yields and purity under mild reaction conditions.     

Synthesis of substituted 1,3,4-oxadiazole derivatives

Monosubstituted oxadiazoles were synthesized by the reaction of hydrazides with triethyl orthoformate. Their reactions with benzoyl chloride gave benzoylcarbohydrazides, which under the action of thionyl chloride were cyclized to the respective 2,5-disubstituted oxadiazoles. 1-Aryl-4-(5-thioxo-4,5-dihydro-1,3,4-oxadiazol-2-yl)-pyrrolidin-2-ones were synthesized from acid hydrazides using carbon disulfide under basic conditions. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 269-272, February, 2009.