2974-09-6

Upstream product

• 3172-52-9 2,5-diclorothiophene 
• 108-98-5 thiophenol 
• 2873-18-9 5-bromo-2-chlorothiophene 
• 96-43-5 2-thienyl chloride 
• 882-33-7 diphenyldisulfane 
• 3141-27-3 2,5-dibromothiophen 

Downstream Products

• 796964-24-4 3,4-bis(chloromethyl)-2,5-bis(phenylthio)thiophene 
• 796964-25-5 5,7-bis(phenylthio)-1,4-dihydro-3λ⁴-thieno[3,4-d][1,2]oxathiin-3-oxide 

Relevant academic research and scientific papers

In situ generation and trapping of aryllithium and arylpotassium species by halogen, sulfur, and carbon electrophiles

(Chemical Equation Presented) A general method has been developed for in situ trapping of arylmetal intermediates by halogen, sulfur, ketone, and aldehyde electrophiles affording the functionalization of the most acidic position in arene. Pentafluorobenzene, benzothiazole, and benzoxazole can be functionalized by using K3PO4 base. For less acidic arenes, tBuOLi base is required. Arenes with DMSO pKa values of 35 or less are reactive. 2009 American Chemical Society.

Thermal and microwave assisted reactions of 2,5-disubstituted thienosultines with [60]fullerene: Non-Kekulé biradicals and self-sensitized oxygenation of the cycloadduct

Refluxing an o-dichlorobenzene solution of 2,5-disubstituted thienosultines 10a-f with [60]fullerene for 2-24 h gave both 1:1 and 2:1 cycloadducts in 37-79% isolated yields. The reaction was highly accelerated by microwave irradiation giving comparable yields of cycloadducts. Sultines 10a-f underwent cheletropic extrusion of SO2 to form the corresponding non-Kekulé biradical intermediates 11a-f, which were subsequently trapped by [60]fullerene to form corresponding cycloadducts. The activation energy barriers (ΔGc≠) determined for the boat-to-boat inversion of these 4′,5′,6′,7′-tetrahydrobenzo[c]thieno- [5′,6′:1,2][60]fullerene adducts 12a-f were found to be in the range of 13.5-14.8 kcal/mol. Unexpectedly, one of the monoadduct 12a was found to be labile when kept in air under ambient light. Two new products 15 (a sulfine-enone) and 16 (an endione) were isolated from the decomposed 12a and were found to derive from self-sensitized singlet oxygen reaction on the 2,5-dimethylthieno moiety of 12a.

Reactions of Halothiophenes with Arene- and Hetarenethiols

Reactions of halothiophenes with sulfanyl radicals generated from arene- and hetarenethiols at 140-200°C have been studied for the first time. The reactions result in replacement of halogen in 2-bromothiophene and 2,5-dichloro-, 2-bromo-5-chloro-, and 2,5-dibromothiophenes. The two halogen atoms in dihalothiophenes are replaced only by phenylthio radical generated from benzenethiol. 4-Methylbenzenethiol and naphthalene-1-thiol react with halothiophenes most selectively, yielding corresponding unsymmetrical sulfides. The reactions with 2-thiophenethiol are accompanied by self-condensation to give dithienyl sulfide. The reactions of arene- and hetarenethiols with halothiophenes provide a synthetic route to unsymmetrical sulfides of the thiophene series, which are difficult to obtain by other methods, and allow prediction of the behavior of other sulfanyl radicals in similar reactions.