Thiophenes continued

Thiophenes continue to play a major role in commercial applications as well as basic research. In addition to its aromatic properties that make it a useful replacement for benzene in small molecule syntheses, thiophene is a key element in superconductors, photochemical switches and polymers. The presence of sulfur-containing components (especially thiophene and benzothiophene) in crude petroleum requires development of new catalysts to promote their removal (hydrodesulfurization, HDS) at refineries. Interspersed with these commercial applications, basic research on thiophene has continued to study its role in electrocyclic reactions, newer routes for its formation and substitution and new derivatives of therapeutic potential. New reports of selenophenes and tellurophenes continue to be modest in number. 

Fig. 6.30 Flow scheme of the rig for performing the bromination of thiophene continuously in a microstructured reactor. (Courtesy of the American Chemical Society [45].)...

Thiocyanogen has been used for thiocyanation of porphyrin (as its copper complex), and for the conversion of 2-bromothiophen into 5-bromo-2-thiocyanatothiophen in the presence of AICI3, a procedure which results in conversion of 2-(methylthio)thiophen into 3,5-di(thio-cyanato)-2-(methylthio)thiophen. Continuation of studies of the... 

This chapter is a continuation of the one on organometallic chemistry of furans and thiophenes [01AHC(78)1]. It starts with the trends of coordination of... 

A solution of 2 grams of A -19-norandrosten-3,17-dione and 0.4 gram of pyridine hydrochloride in 50 cc of benzene free of thiophene was made free of moisture by distilling a small portion 4 cc of absolute alcohol and 4 cc of ethyl orthoformate were added and the mixture was refluxed during 3 hours. 5 cc of the mixture were then distilled and after adding an additional 4 cc of ethyl orthoformate the refluxing was continued for 2 hours longer. The mixture was evaporated to dryness under vacuum and the residue was taken up in ether, washed, dried and evaporated to dryness. The residue was crystallized from... 

In addition to useful polymers, thiophene derivatives have a variety of other interesting properties. Novel benzodiazepine analogues such as 46 and related compound 47 continue to... 

The [2 + 2] photodimerization of a, j8-unsaturated sulfones is correctly viewed as a photoreaction of alkenes, rather than the sulfone group, and this aspect has been reviewed recently by Reid, as part of a wider survey of the photoreaction of O- and S-heterocycles. The topic continues to attract considerable interest and a few recent examples, as well as some synthetic applications, will be discussed here. Much of the photodimerization work has been carried out on the benzo[fc]thiophene (thianaphthene) 1,1-dioxide system. For example. Porter and coworkers have shown that both 3-carboxybenzo[i]thiophene 1,1-dioxide (65) and its methyl ester give only the head-to-head (hth), anti dimer (66) on irradiation in ethanol. In a rather unusual finding for such systems, the same dimer was obtained on thermal dimerization of 65. Similar findings for a much wider variety of 3-substituted benzo[fi]thiophene 1,1-dioxides have been reported more recently by Geneste and coworkers . In the 2-substituted analogs, the hth dimer is accompanied by some of the head-to-tail (htt), anti dimer. The formation of the major dimer appears to proceed by way of an excited triplet and the regiochemistry observed is in accord with frontier MO theory. 

Atlantic Richfield Company has reported strains of Pseudomonas sp. CB1 (ATCC 39381) [108] and Acinetobacter species CB2 [109] (ATCC 53515) to be effective for the removal of sulfur from organic molecules found in petroleum, coal, etc. In fact, the aerobic and heterotrophic soil microorganisms Pseudomonas CB1 and Acinetobacter CB2 were reported to convert thiophene sulfur into sulfate, using a bench-scale continuous bioreactor. The direct contact with Illinois 6 coal reduced the organic sulfur content in about 40% to 50%. As already mentioned, most of this work was carried out on coal. Further work was not pursued probably due to decrease in coal usage or due to the economics of the processes. 

The patent described a method for the removal of thiophenic compounds from fossil fuels, in which the reacting media might contain organic solvents. Additionally, the biocatalyst may be contacted with the fuel directly either as free enzyme or in its immobilized form. The process could, therefore, be performed either in a batch reactor or in a semi-continuous or continuous manner. Further, it may be performed either as a stand... 

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