Dibenzo thiophene methylation

Allyl- and benzyl-thiophenes may be cyclized by a direct Bradsher reaction, using dichloromethyl methyl ether or related dichloroalkyl methyl ethers and tin(IV) chloride catalysis to give the corresponding benzo- or dibenzo-thiophenes in 55-60% yield (73JCS(P1)1099). Thus substituted thiophenes having a benzyl group at either the 2- or 3-position, e.g. (349), when treated with a 1,1-dichloroalkyl methyl ether and tin(IV)... 

Thiophene is obtained in 6% yield by passing butadiene into molten sulfur at 320-420°. The reaction is general and affords somewhat higher yields (31 40%) of methylated thiophenes from homologs of butadiene. The free-radical nature of the reaction has been discussed. Dibenzo-thiophene is conveniently prepared by heating biphenyl and melted sulfur with aluminum chloride at 120°. The yield is 47%... 

Unter gleichen Bedingungen gibt Bis-[4-methyl-phenyl -sulfid das 2,8-Bimethyl-(dibenzo-thiophen> (40% d.Th. F 1190)1 ... 

In a further work, Tang and Curtis26 have studied the influence of the tyre components by replacing coal with model compounds 4-(l-naphthylmethyl)-bibenzyl (NMBB), dibenzothiophene and 5-methyl-8-(l-methylethyl)dibenzo-thiophen-4-ol (MMDH). Carbon black was active for the NMBB hydrocracking, whereas little activity was found with SBR, waste tyres and waste tyre liquefaction residues. However, when the latter residues were previously heat treated to remove organic coatings and recover the carbon black component, significant NMBB conversions were observed. Moreover, both carbon black and heat-treated residues were active for the hydrodesulfurization of dibenzothiophene and MMDH, particularly when combined with Mo naphthenate and S. These results confirm the catalytic properties of carbon black in coal-tyre coliquefaction, provided that its surface area is accessible. 

When A.A-dimethylisoindolinium bromide is treated with phenyl-lithium, it gives V-methylisoindole via the ylid (54).2 59,60 An attempt to prepare benzo[c]thiophene via the analogous ylid (55) failed. Thus, when l,3-dihydrobenzo[c]thiophene methylsulfonium iodide was treated with phenyllithium, it gave a mixture of methyl phenyl sulfide, spiro[5.5]-l-methylthio-2,3-benzo-6-methylthio-methyleneundeca-7,9-diene (56), and 3,4-bis(methylthio)-l,2 5,6-dibenzo-l,5-cyclooctadiene (57).59,60 The formation of methyl phenyl sulfide may be explained by the formation and ring cleavage of compound 58, and compounds 56 and 57 arise by Diels-Alder dimerization of the o-quinodimethane (59) formed by ring cleavage of the ylid (55). 

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