Tetrahydrothiophenes, aromatization

Does the fact that thiophene reacts similarly to benzene mean that it is aromatic One way to tell is to calculate first and second hydrogenation energies of thiophene, leading to dihydrothiophene and tetrahydrothiophene, respectively. (The energy of hydrogen is provided at right.)... 

Dichlorothiophene has become easily available through chlorination and dehydrochlorination of tetrahydrothiophened Another example of the aromatization of tetrahydrothiophene derivatives is the preparation of 3-substituted thiophenes by the reaction of 3-ketotetrahydrothiophene with Grignard reagents followed by the aromatization of the intermediate dihydrothiophene. Recent gas chromatographic analysis showed, however, that 2,3-dichlorothio-phene is the main product from the dehydrochlorination of tetra-chlorotetrahydrothiophene. 

The potential of MIL-47 and MIL-53(A1) for adsorption of other types of aromatic adsorbates has also been explored, for instance, of dichlorobenzene, cresol, or alkylnaphthalene isomers [17, 98]. The removal of sulfur-containing aromatics from fuels via physisorption on MOFs has been investigated on several instances in literature, for instance, via the selective removal of thiophene from a stream of methane gas by MIL-47 [99], the removal of tetrahydrothiophene from methane by... 

The thienothienoimidazolium salts 29 were prepared by the reaction of thiophanes 362 with HX (X = halogen) and crystallization from solvents selected from ketones, aromatic hydrocarbons, and halohydrocarbons. l-(—)-3,4-(l, 3 -dibenzyl-2 -ketoimidazolido)-2-(u -ethoxypropyl)tetrahydrothiophene 362 was reacted with HBr at 99-103 °G for 2h and crystallized from methyl-Tro-butyl ketone to give l-(—)-3,4-(T,3 -dibenzyl-2 -ketoimidazolido)-l,2-trimethyle-nethiophanium bromide 29 (95%, 98.7% purity) (Scheme 75) <2001JAK100477>. 

Sulfolane A process for removing aromatic hydrocarbons from petroleum fractions by liquid-liquid extraction using sulfolane (tetramethylene sulfone tetrahydrothiophene-1,1-dioxide) at approximately 190°C. Developed by Shell Development Company in 1959 and first commercialized in 1962 now licensed through UOP. It replaced the Udex process. Sulfolane is used for another purpose in the Sulfinol process. 

This technique has been applied to the determination of aromatic hydrocarbons, alcohols, aldehydes, ketones, chloroaliphatic compounds, haloaromatic compounds, acrylonitrile, acetonitrile, mixtures of organic compounds and tetrahydrothiophene in soils, chloroaliphatic and haloaromatic compounds and organotin compounds in non-saline sediments, and organotin compounds in saline sediments. 

The resulting tetrahydropyrroles and tetrahydrothiophenes could be easily aromatized under basic conditions (Scheme 36), thus allowing a convenient access to a new class of pyrrole and thiophene derivatives, which have found application in the preparation of new organic materials [304-308]. 

Thiophenes and Tetrahydrothiophenes. Thiophenes (thioles) are subject to aromatic hydroxylation tetrahydrothiophenes (thiolanes) undergo oxidation of the sulfur to give sulfoxides or sulfones. 

Sulfides with a hydrogen atoms like dimethyl sulfide, dimethyl disulfide, and tetrahydrothiophene form diols under UV irradiation (795). In the tetrahydrothiophene-2HFA2 adduct the hydroxyhexafluoropropyl groups are in trans positions and the trifluoromethyl groups show nonequivalence (795). Aromatic thio compounds like thiophenols (77), diaryl sulfides (779, 180, 207), and thiophene (95) add HFA in an ortho position, as does furan (95). 

The fact that the lone pair on sulfur contributes to the aromaticity is seen in the lower dipole moment of thiophene as compared to its saturated analogue tetrahydrothiophene (0.52 D vs. 1.90 D) <1972JA8854>. In thiophene, the dipole is directed from the ring toward the heteroatom. 

Hence the currently most favoured mechanism of thiophen hds is that thiophen adsorbs parallel to the catalyst surface through the rr-system of the ring, and then undergoes aromatic-type hydrogenation to tetrahydrothiophen prior to S-elimination. 

Aromatic thiophenes play no part in animal metabolism, however aromatic thiophenes do occur in some plants, in association with polyacetylenes with which they are biogenetically linked. Biotin (vitamin H), is a tetrahydrothiophene. 

Removal of Aromatic Compounds. Because of the demand for high-purity aromatic compounds for petrochemical feedstocks, several processes have been developed for BTX (benzene, toluene, and xylenes) recovery from distillate streams. In these processes, aromatic compounds are separated from nonaromatic compounds by liquid—liquid extraction using polar solvents. The three major processes in use are the UOP—Dow UDEX process (di- or triethylene glycol solvent), the UOP sulfolane process (tetrahydrothiophene 1,1-dioxide), and the Union Carbide TETRA process (tetraethylene glycol). 

The role of heteroatoms in ground- and excited-state electronic distribution in saturated and aromatic heterocyclic compounds is easily demonstrated by a comparison of a number of heteroaromatic systems with their perhydro counterparts. In Jt-excessive heteroaromatic systems, because of their resonance structures, their dipole moments are less in the direction of the heteroatom than in the corresponding saturated heterocycles furan (1, 0.71 D) vs. tetrahydrofliran (2, 1.68 D), thiophene (3, 0.52 D) vs. tetrahydrothiophene (4, 1.87 D), and selenophene (5, 0.40 D) vs. tetrahydroselenophene (6, 1.97 D). In the case of pyrrole (7, 1.80 D), the dipole moment is reversed and is actually higher than that of pyrrolidine (8, 1.57 D) due to the acidic nature of the pyrrole ring (the N-H bond) In contrast, the dipole moment of n-deficient pyridine (9, 2.22 D) is higher than that of piperidine (10, 1.17 D). In all these compounds, with the exception of pyrrole (7), the direction of the dipole moment is from the ring towards the heteroatom [32-34]. 

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