Mass spectra of some phenyl- and chloro-substituted thianaphthenes and their sulfones

The mass spectra of 2,3-dichlorothianaphthene, 2-phenylthianaphthene, 2,3-diphenylthianaphthene, 3-chlorothianaphthene 1,1-dioxide, 2,3-dichlorothianaphthene 1,1-dioxide, 2-phenylthianaphthene 1,1-dioxide, 3-phenylthianaphthene 1,1-dioxide, and 2,3-diphenylthianaphthene 1,1-dioxide were studied. The fundamental mechanisms of fragmentation of molecules of these compounds under the influence of electron impact are examined.Translated from Khimiya Geterotsilicheskikh Soedinenii, No. 3, pp. 326–332, March, 1971.     

Hydrolysis of carbamates and carbonates of 3-hydroxythiolane 1,1-dioxide

Alkylcarbamates of 3-hydroxy-thiolane 1,1-dioxide are hydrolyzed in the presence of bases to give alkyl(1,1-dioxo-3-thiolanyl) amines and 2-thiolene 1,1-dioxide (I). Aryl esters undergo hydrolysis to give sulfone I and 3-hydroxythiolane 1,1-dioxide (II). The corresponding alkyl- and arylcarbonates also form sulfone I and a very small amount of hydroxy derivative II under these conditions.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1482–1484, November, 1980.     

Selectivity in cycloadditions—X : Regiochemistry of cycloadditions of nitrile oxides to thiophene and benzothiophene 1,1-dioxides

Thiophene-1,1-dioxide undergoes regioselective cycloaddition to benzonitrile oxide. In the reaction with the less reactive mesitonitrile oxide the sulfur dioxide deriving from the dimerization of the dipolarophile causes a catalytic decomposition of the nitrile oxide, which competes with the cycloaddition. Benzothiophene-1,1-dioxide and the vinyl sulfone system of 2,3-dihydrothiophene-1,1-dioxide and nitrile oxides with lower regioselectivity. The directing effect of the sulfonyl group has been elucidated with the aid of CNDO/2 calculations.     

Synthesis and chemical properties of cyclic β-keto sulfones (review)

Published data on the synthesis and chemical properties of dihydrothiophen-3(2H)-one 1,1-dioxide, dihydro-2H-thiopyran-3(4H)-one 1,1-dioxide, 1-benzothiophen-3(2H)-one 1,1-dioxide, and 1H-isothio-chromen-4(3H)-one 2,2-dioxide are reviewed. The choice of subjects was based on the presence of identical structural fragments, carbonyl, active methylene, and sulfonyl groups.     

Adsorption of methane and ethane, 1. Studies of work function changes of Pt foil. Effect of pressure

Liquid-phase hydrogenation of 3-thiolene-1,1-dioxide to thiolane-1,1-dioxide on Pd catalysts has been studied. According to the kinetic and adsorption data, at 20°C and P_{H 2}=0.1–1.0 MPa the reaction proceedsvia the interaction of adsorbed 3-thiolene-1,1-dioxide with dissolved H₂. At P_{H 2}=2–7 MPa, the reaction between the adsorbed H₂ and dissolved 3-thiolene-1,1-dioxide is the limiting step of the process.     

Diels-alder reactions with cyclic sulfones: VIII. Organic catalysis in the synthesis of spiro[1-benzothiophene-4,5′-pyrimidine]-2′,4′,6′-trione 1,1-dioxides and 2′-thioxospiro[1-benzothiophene-4,5′-pyrimidine]-4′,6′-dione 1,1-dioxides

5-Isopropenyl-2,3-dihydrothiophene 1,1-dioxide reacted with 5-methylidenepyrimidine-2,4,6-triones and 5-methylidene-2-thioxopyrimidine-4,6-diones in the presence of chiral amines or amino acids with high regio- and stereoselectivity to give optically active derivatives of barbituric and thiobarbituric acids spirofused at the 5-position to 1-benzothiophene 1,1-dioxide fragment. The reaction of 5-isopropenyl-2,3-dihydrothiophene 1,1-dioxide with 5-(2-methoxybenzylidene)-2-thioxopyrimidine-4,6-dione (generated in situ from 2-methoxybenzaldehyde and thiobarbituric acid) in the presence of (?)-ephedrine or L-4-(tert-butyldimethylsiloxy) proline gave the corresponding 2-thioxospiro[1-benzothiophene-4,5′-pyrimidine]-4′,6′-dione 1,1-dioxide with an enantiomeric excess of 80%.     

1,2,4-benzothiadiazine 1,1-dioxides 3. Reactions of 2-aminobenzenesulfonamide with chloroalkyl isocyanates

Reactions of 2-aminobenzenesulfonamide ( 1 ) with allyl, methyl, 2-chloroethyl aor 3-chloropropyl isocyanates gave 2-(methylureido)-, 2-(allylureido)-, 2-(2′-chloroethylureido)- and 2-(3′-chloropropylureido)-benzene sulfonamides 3a,b and 7a,b in excellent yields. Treatment of 3a,b at refluxing temperature of DMF afforded 2H-1,2,4-benzothiadiazin-3(4H)-one 1,1-dioxide ( 4 ) in good yield. However, when compounds 7a,b were refluxed in 2-propanol, 3-(2′-aminoethoxy)-2H-1,2,4-benzothiadiazine 1,1-dioxide ( 11a ) and 3-(3′-aminopropoxy)-2H-1,2,4-benzothiadiazine 1,1-dioxide ( 11b ) were obtained in a form of the hydrochloride salts 10a,b in 87% and 78% yields respectively. Heating 11b in ethanol gave a dimeric form of 2H-1,2,4-benzothiadiazin-3(4H)-one 1,1-dioxide and 3-(3′-aminopropoxy)-2H-1,2,4-benzothiadiazine 1,1-dioxide ( 12 ) in 55% yield. Treating of 7a,b or 11a,b with triethylamine at the refluxing temperature of 2-propanol afforded 3-(2′-hydroxyethylamino)-2H-1,2,4-benzothiadiazine 1,1-dioxide ( 2a ) and 3-(3′-hydroxypropylamine)-2H-1,2,4-benzothiadiazine 1,1-dioxide ( 2b ) via a Smiles rearrangement.     

Synthesis of purine-like ring systems derived from 1,2,6-thiadiazine 1,1-dioxide

7-Amino-1H,4H-imidazo[2,3-c][1,2,6]thiadiazine 5,5-dioxide was prepared by a multi-step reaction sequence form 3,5-diamino-4H-1,2,6-thiadiazine 1,1-dioxide. 7-Amino-4H-furazano-[3,4-c][1,2,6]thiadiazine 5,5-dioxide was obtained by lead tetraacetate oxidation of 3,5-diamino-4-hydroxyimino-4H-1,2,6-thiadiazine 1,1-dioxide.     

Synthesis and Structure of Dinitrosulfodienes of the Thiolene 1,1-Dioxide Series

A synthesis of previously unknown rigidly fixed heterocyclic structures, dinitrosulfodienes of the thiolene 1,1-dioxide series, was developed, and their structure was studied. The geometry and structural parameters of 3-methyl-4-nitro-2-[nitro(phenyl)methylene]-3-thiolene 1,1-dioxide were determined by X-ray diffraction.     

Chemistry of thienopyridines. XXXVIII. Diels-Alder reactions of thienopyridine sulfones. Part 2

Thieno[3,2-b]pyridine 1,1-dioxide ( 2 ) undergoes Diels-Alder condensation with the dienophiles cyclopentadiene, anthracene, and naphthacene in a manner analogous to its isomer thieno[2,3-b]pyridine 1,1-dioxide ( 1 ). Compound 2 dimerizes in refluxing xylene with the loss of sulfur dioxide plus either the loss or transfer of hydrogen to give a small yield (ca. 2%) of pyrido[2′,3′:4,5]thieno[3,2-f]quinoline 7,7-dioxide ( 7 ) and its 5,6-dihydro derivative 12 . Formation of 7 and 12 are compared and contrasted with products reported from dimerization of 1 and of benzo[b]thiophene 1,1-dioxide and its derivatives.     

Syntheses of pyrimidine and purine analogs derived from 1,2,6-thiadiazine 1,1-dioxide

5-Amino-3-oxo-2H, 4H-1,2,6-thiadiazine 1,1-dioxide and the monopotassium salt of 3,5-dioxo-2H, 4H,6H-1,2,6-thiadiazine 1,1-dioxide was obtained by condensation of sulfamide and ethyl cyanacetate and diethyl malonate, respectively. 7-Oxo-1H,4H,6H-imidazo[2,3-c]-1,2,6-thia-diazine 5,5-dioxide was prepared by a multi-step reaction sequence from 5-amino-3-oxo-2H, 4H-1,2,6-thiadiazine 1,1-dioxide.     

Thiirano-3,4-thiolane 1,1-dioxide and a method for its preparation

Thiirano-3,4-thiolane 1,1-dioxide was obtained by the action of triphenylphosphine sulfide on oxirano-3,4-thiolane 1,1-dioxide in the presence of an excess of trifluoroacetic acid.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1630–1632, December, 1983.     

Synthesis of 3,4-di(methylene)tetrahydrothiophene-1,1-dioxide and its use in organic synthesis

A convenient reaction scheme has been developed for obtaining 3,4-di(methylene)tetrahydrothiophene-1,2-dioxide from the readily available 3,4-dimethyl-2,4-dihydrothiophene-1,1-dioxide through 3,4-di(bromomethyl)-2,5-dihydrothiophene-1,1-dioxide. A feasibility study has been made of the use of the butadiene fragment of the heterocycle in a Dieb—Alder reaction with maleic acid derivatives, and the corresponding adducts have been obtained.DeceasedTranslated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 173–175, February, 1992.     

3-(p-Nitrobenzolsulfonamido)-und 3-Sulfanilamidobenzisothiazol-1,1-dioxid

Zusammenfassung Kupplung von 3-Chlorbenzisothiazol-1,1-dioxid mit p-Nitrobenzolsulfonamid Führt zum 3-(p-Nitrobenzolsulfonamido)-benzisothiazol-1,1-dioxid, und zwar entweder unter Einsatz des freien Sulfonamids in Chlorbenzol in Gegenwart von Kupferbronze oder unter Einsatz des Natriumsalzes inDMF oder Schmelze. Katalytische Reduktion der Nitrogruppe führt zu 3-Sulfanilamidobenzisothiazol-1,1-dioxid, das direkt durch Kupplungsreaktionen nicht darstellbar ist.

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3-(p-Nitrobenzenesulfonamido)- and 3-sulfanilamidobenzoisoxazole-1.1-dioxide (new sulfonamides, XVI.)

3-(p-Nitrobenzenesulfonamido)-benzisothiazole-1,1-dioxide can be obtained from 3-chlorobenzisothiazole-1,1-dioxide by coupling with p-nitrobenzenesulfonamide in two ways: from the free sulfonamide in chlorobenzene solution in the presence of copper bronze, or from the sodium salt of the sulfonamide in dimethylformamide or in a melt. 3-sulfanilamidobenzisothiazole-1,1-dioxide, not directly available by coupling, was prepared by catalytic reduction of the nitro group.

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15. Mitt.:H. Bretschneider, W. Richter undW. Klötzer, Mh. Chem.96, 1661 (1965).     

Investigation of substituted 2- and 3-thiolene 1,1-dioxides by PMR spectroscopy with the aid of a lanthanide shift reagent

The reaction of lanthanide shift reagent Eu(FOD)₃ with 3-phenyl- and 3- and 4-chloro-2-thiolene 1,1-dioxides and with 3-phenyl-3-thiolene 1,1-dioxide was investigated by PMR spectroscopy. The geometrical structure of the adduct of the lanthanide shift reagent with 4-chloro-2-thiolene 1,1-dioxide was found.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 314–317, March, 1984.     

Reactions of 2,5-diphenyl-1,4 dithin sulfones with sodium azide

A number of unanticipated transformations were observed when various 2,5-diphenyl-1,4-dithiin sulfones were treated with sodium azide. These include a fragmentation to give 1,2-dicyano-1,2-diphenylethen, the formation of 2,5-dipehnyl-1,4-thiazine-1,1-dioxide, and the rearrangement of 3-bromo-2,5-diphenyl-1,4-dithiin-1,1-dioxide to its 2-bromo- isomer. Possible mechanism for these unusual reactions are discussed.     

1,3-Dipolar cycloaddition reactions of benzo[b]thiophene 1,1-dioxide with azomethine ylides

New pyrrolo derivatives of benzo[b]thiophene 1,1-dioxide have been synthesised via 1,3-dipolar cycloaddition reactions. Reaction of benzo[b]thiophene 1,1-dioxide with stabilised azomethine ylides gave products in low yield but high stereoselectivity whereas reaction with non-stabilised azomethine ylides gave high overall yields but low stereoselectivity.     

Beiträge zur Chemie schwefelhaltiger Heterocyclen, 2. Mitt.

Zusammenfassung 6-Nitro-benzo[b]thiophen-1,1-dioxid wurde unter verschiedenen Bedingungen hydriert. Das durchSkraupsche Synthese aus 2,3-Dihydro-6-amino-benzo[b]thiophen-1,1-dioxid gewonnene Produkt konnte auf Grund des NMR-Spektrums als 2,3-Dihydrothieno[2,3-f]chinolin-1,1-dioxid identifiziert werden.

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6-Nitro-benzo[b]thiophene-1,1-dioxide was hydrogenated under various conditions. The product prepared from 2,3-dihydro-6-amino-benzo[b]thiophene-1,1-dioxide by theSkraup synthesis was identified by nmr as 2,3-dihydro-thieno[2,3-f]quinoline-1,1-dioxide.

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1. Mitt.:F. Sauter, Mh. Chem.99, 1507 (1968).     

Synthesis and configuration of 4-alkyl-2-methyl-3,4-diphenyl-1,2-thiazetidine 1,1-dioxide

4-Alkyl-2-methyl-3,4-diphenyl-1,2-thiazetidine 1,1-dioxide 5, 6 and 7 were obtained from 2-methyl-3,4-diphenyl-1,2-thiazetidine 1,1-dioxide 1 by reaction of its anion 4 with alkyl halides. cis- and trans-Configuration of the 4-alkylated products were determined by ¹H-nmr and NOE difference spectro-scopy studies.     

The Study of Alcoholysis of 1,2-Thiazetidine-l,l-dioxide with Quantum Chemical Method

The alcoholysis mechanism of 1,2-thiazetidine-1,1-dioxide with methanol, in which the relatively stable product is sulfonate ester, has been investigated by quantum chemical method. Our calculations indicate the reaction for alcoholysis of 1,2-thiazetidine-1,1-dioxide proceeds via two possible mechanisms: concerted and stepwise. In the stepwise mechanism, two possible reaction pathways can be followed while only one possible reaction pathway can be followed in the concerted mechanism.