6579-15-3

Upstream product

• 105084-58-0 (η5-cyclopentadienyl)(1,2-dimethoxycarbonyl-1,2-ethenedithiolato)rhodium(III) 
• 536-74-3 phenylacetylene 
• 941-69-5 N-phenyl-maleimide 
• 217084-64-5 3,4-bis(methoxycarbonyl)-1,2-dithiete 
• 762-42-5 dimethyl acetylenedicarboxylate 
• 162471-14-9 1,3-bis(1,3,4-oxathiazol-2-on-5-yl)-adamantane 
• 79068-53-4 4-(2,4,5-Trimethylphenyl)-1,3,2-oxathiazolylium-5-olat 
• 15185-51-0 3-oxo-3-phenyl-dithiopropionic acid 

Downstream Products

• 4506-94-9 thiophene-2,3,4,5-tetracarboxylic acid 

Relevant academic research and scientific papers

Rhodium-Catalyzed Isomerization and Alkyne Exchange Reactions of 1,4-Dithiins via the 1,2-Ethenedithiolato Rhodium Complex

Rhodium-catalyzed isomerization and alkyne exchange reactions of 1,4-dithiines occurred by cleavage of two C-S bonds. The 2,5- and 2,6-disubstituted 1,4-dithiins underwent isomerization reactions in toluene at 110 °C, providing equilibrium mixtures of isomers. At 150 °C, the reaction of 1,4-dithiins and dimethyl acetylenedicarboxylate gave unsymmetric 2,3-di(methoxycarbonyl)-1,4-dithiins and 2,3-di(methoxycarbonyl)thiophenes, the latter of which were formed by desulfurization of the 1,4-dithiins. A related reaction of the alkyne and a 1,2-dithiete gave a 2,3-di(methoxycarbonyl)thiophene. These reactions are considered to involve 1,2-ethenedithiolato rhodium intermediates.

Reaction of 1,2-Dithiete with Alkenes and Alkynes: Experimental and Theoretical Study

Reactions of 3,4-bis(methoxycarbonyl)-1,2-dithiete (1) with various alkenes or alkynes formed 2,3-dihydro-1,4-dithiins or thiophenes, respectively. The reactions with alkenes were stereospecific, which indicates the concerted reaction between 1,2-bis(methoxycarbonyl)ethane-1,2-dithione (13), the valence isomer of the 1,2-dithiete, and the dienophiles. Theoretical study confirmed the reactions of 13 with alkenes and alkynes are of reverse electron demand hetero Diels-Alder type. The MO calculations showed the 1,2-dithiete 1 was 5.8 kcal mol-1 more stable than the corresponding ethane-1,2-dithione 13, and the tautomerization energy between the 1,2-dithiete and the ethane-1,2-dithione was also calculated to be 28.5 kcal mol-1 from the 1,2-dithiete, which suggests the tautomerization from 1,2-dithiete 1 to ethane-1,2-dithione 13 is possible at least at high temperature. Reaction of 3,4,7,8-tetrakis(methoxycarbonyl)-1,2,5,6-tetrathiocin (2) or (Z,Z,Z,Z)-3,4,7,8,11,12,15,16-octakis-(methoxycarbonyl)-1,2,5,6,9,10,13,14- octathiacyclohexadeca-3,7,11,15-tetraene (3) with ethyl vinyl ether also formed the 2,3-dihydro-1,4-dithiin derivative, which is the same compound obtained by the reaction of 1,2-dithiete 1 with the ether. 1,2,5,6-Tetrathiocin 2 and 16-membered cyclic compound 3 also reacted with diphenylacetylene to give the thiophene derivative.

Adamantane-based nitrile sulfides: the generation of the synthetic equivalent of the first bis(nitrile sulfide)

The reaction of 1,3-adamantanedicarbonamide with chlorocarbonylsulfenyl chloride in hot toluene gives two new oxathiazolone derivatives that have had their structures confirmed crystallographically: 1,3-bis(1,3,4-oxathiazol-2-on-5-yl)-adamantane and 1-cyano-3-(1,3,4-oxathiazol-2-on-5-yl)-adamantane. (Crystal data: C10H14(COC(O)SN)2: P21/m, a = 10.447(2), b = 7.119(3), c = 10.684(2) Angstroem, β = 112.98(1) deg, V = 731.5(3) Angstroem3, z = 2, Dc = 1.536 g cm-3, R = 0.034, Rw = 0.029; (NC)C10H14(COC(O)SN): P21/c, a = 9.153(2), b = 19.134(2), c = 7.130(3) Angstroem, β = 105.38(2) deg, V = 1204(1) Angstroem3, z = 4, Dc = 1.447 g cm-3, R = 0.038, Rw = 0.035).The reaction of the precursor with dimethyl acetylenedicarboxylate (DMAD) in refluxing chlorobenzene gave a mixture that was resolved into pure compounds by Kugelrohr sublimation; these were shown to be sulfur, tetramethyl thiophenetetracarboxylate, 1,3-adamantanedinitrile, 1,3-bis(4,5-bis(methoxycarbonyl)-isothiazol-3-yl)-adamantane, and 1-cyano-3-(4,5-bis(methoxycarbonyl)-isothiazol-3-yl)-adamantane.The structures of the two new isothiazole derivatives were confirmed crystallographically. (Crystal data: C10H14(CNS*DMAD)2: Pca21, a = 15.857(4), b = 11.562(4), c = 13.602(4) Angstroem, V = 2494(2) Angstroem3, z = 4, Dc = 1.424 g cm-3, R = 0.057, Rw = 0.038; C10H14(CN)(CNS*DMAD): P21/c, a = 19.683(2), b = 11.566(3), c = 7.727(3) Angstroem, β = 93.30(2) deg, V = 1756(1) Angstroem3, z = 4, Dc = 1.363 g cm-3, R = 0.079, Rw = 0.076).The pattern of reactivity indicates that the synthetic equivalent of the bis(nitrile sulfide) may be present in solution but has a very short lifetime and failed to react at all with 1,3-adamantanedinitrile.Key words: oxathiazolone, nitrile sulfide, cycloaddition, isothiazole.

REACTION OF 2-BENZOYL- AND 2-NITROETHENE-1,1-DITHIOLATES WITH DIMETHYL ACETYLENEDICARBOXYLATE

The reaction of dimethyl acetylenedicarboxylate with 2-benzoyl- and 2-nitroethene-1,1-dithiolates leads to 2-alkylidene-4,5-dimethoxycarbonyl-1,3-dithiolanes (in the form of an equilibrium mixture of the trans and cis isomers).A series of side products are also formed under the reaction conditions. 2,3,4,5-Tetramethoxycarbonylthiophene and 3,5-di(benzoylmethylene)-1,2,4-trithiolane were identified among them.

REACTIONS OF ELEMENTAL SULFUR AND SELENIUM WITH SOME ACETYLENIC COMPOUNDS. FORMATION OF THIOPHENES AND SELENOPHENES

The reaction of 3-butyn-2-one with elemental sulfur at 205-215 deg C in benzene in a stainless autoclave afforded 2,4- and 2,5-diacetylthiophenes in 43percent and 22percent yields, respectively. Under similar conditions, the reaction with elemental selenium gave 2,4- and 2,5-diacetylselenophenes in 32percent and 29percent yields, respectively. Diphenylacetylene reacted with sulfur and selenium to produce tetraphenylthiophene (78percent) and tetraphenylselenophene (38percent), respectively. The reaction of di(2-thienyl)acetylene with sulfur provided tetra(2-thienyl)thiophene in 57percent yield. The reactionof dimethyl acetylenedicarboxylate with sulfur in the presence of diphenylacetylene afforded 2,3-bis(methoxycarbonyl)-4,5-diphenylthiophene (29percent) and tetrakis(methoxycarbonyl)thiophene (15percent). On the basis of these results, the mechanism for the formation of thiophenes and selenophenes is discussed.

Synthesis, Thermal and Photochemical Reactions of New Mesoionic 1,3,2-Oxathiazolones

The synthesis and spectroscopic data of the new mesoionic 1,3,2-oxathiazolones 3b, c, e are described.As cyclic thiocarbonyl imine, 3e reacts with dimethyl acetylenedicarboxylate at 80 deg C with evolution of carbon dioxide to produce the 5-arylisothiazole derivative 6e (80percent).On the other hand, the visible light-induced fragmentation of 3e leads to a nitrile sulfide intermediate of type 10 which suffers unimolecular decay with formation of sulfur and the arylnitrile 11e or which can be partially trapped with dimethyl acethylenedicarboxylate to form the iosmeric 3-arylisothiazole derivative 13e (29-21percent).The analogous photochemical decay of 3c in the presence of dimethyl acetylenedicarboxylate proceeds with formation of the isothiazole derivative 13c besides sulfur and the nitrile 11c, whereas the nitrile sulfide 10b - photochemically generated from 3b - does not more react with formation of an isothiazole derivative.