Of dibenzothiophenes

Example 15 Estimate solid heat capacity of dibenzothiophene, Ci2HsS. The required atomic element contributions from Table 2-393 are C = 10.89, H = 7.56, and S = 12.36. Substituting in Eq. (2-63) ... 

The rhodium and iridium complexes of dibenzothiophene (L) reveal an interesting case of linkage isomerism (91IC5046). Thus, the ti S) coordinated species [MCp LCb] on thermolysis with silver tetrafluoroborate afford the Ti -coordinated dicationic species. 

Omori T, L Monna, Y Saiki, T Kodama (1992) Desulfurization of dibenzothiophene by Corynebacterium sp. strain SYl. Appl Environ Microbiol 58 911-915. 

The enzyme in Rhodococcus sp. strain IGTS8 that brings about successive oxidation of dibenzothiophene to the sulfoxide and the sulfone is a flavin mononucleotide-dependent monooxygenase that carries out both reactions by sequential incorporation of a single atom of oxygen from Oj (Lei and Tu 1996). 

Monticello DJ, D Bakker, WR Finnerty (1985) Plasmid-mediated degradation of dibenzothiophene by Pseudomonas species. Appl Environ Microbiol 49 756-760. 

Benzothiophene is isoelectronic with naphthalene, dibenzothiophene with anthracene, and benzothiazole with quinoline, and this is reflected in their aerobic degradation that is initiated by dioxygenation. The diversity of pathways for the degradation of dibenzothiophene is illustrated by the following examples ... 

By analogy with anthracene, dioxygenation of dibenzothiophene produces 2-hydroxyben-zothiophene-3-carboxaldehyde, and this may be transformed into a number of products including benzothiophene-2,3-dione and further into disulfides and thioindigo (Bressler and Fedorak 2001a,b). 

Bressler DC, PM Fedorak (2001a) Purification, stability, and mineralization of 3-hydroxy-2-formylbenzothio-phene, a metabolite of dibenzothiophene. Appl Environ Microbiol 67 821-826. 

Rhee S-K, JH Chang, YK Chang, HN Chang (1998) Desulfurization of dibenzothiophene and diesel oils by a newly isolated Gordona strain CYKSl. Appl Environ Microbiol 64 2327-2331. 

Van Afferden M, S Schacht, J Klein, HG Triiper (1990) Degradation of dibenzothiophene by Brevibacterium sp. DO. Arch Microbiol 153 324-328. 

Wang P, AE Humphrey, S Krawiec (1996) Kinetic analysis of desulfurization of dibenzothiophene by Rhodo-coccus erythropolis in continuous cultures. Appl Environ Microbiol 62 3066-3068. 

In contrast with the relatively facile thermal rearrangement of sulfinates to sulfones discussed in the preceding section, the reverse process is relatively, rarely encountered and is usually observed only at elevated temperatures. One of the first thermal sulfone to sulfinate isomerizations has been invoked by Fields and Meyerson to occur during the pyrolysis of dibenzothiophene S, S-dioxide (26) to dibenzofuran, through elimination of sulfur monoxide from the sultine intermediate 27 (equation 27). More recently, the flash vapor-phase pyrolysis of various 2,5-dialkyl and diaryl thiophene-S, S-dioxides has also been shown to involve SO extrusion and formation of the corresponding furans in good yields . 

Although single-electron-transfer (SET) processes would be expected to be important in reactions that use metals as reagents, this type of process has also been recognized in the reduction of carbonyl groups that involve 1,4-dihydronicotinamide derivatives . Recent work by Oae and coworkers" has shown that an SET process is operative in the reduction of dibenzothiophene S-oxide by l-benzyl-l,4-dihydronicotinamide when the reaction is catalyzed by metalloporphins. The reaction is outlined in equation (18), but the study gave results of much more mechanistic than synthetic value. This type of study is relevant to understanding biochemical mechanisms since it is known that methionine sulphoxide is reduced to methionine by NADPH when the reaction is catalyzed by an enzyme isolated from certain yeasts . 

Figure 15. Relative removal of dibenzothiophenes and benzothiophenes from the middle-distillate cut of OB oil in the presence (left frame) and absence (right frame) of sulfate. Compounds are ranked in order of their relative depletion. Bars with solid and hatched lines represent the sum of the results for alkylated compounds with n pendant carbons, with CO indicating the unalkylated parent open bars in the left frame represent individual dibenzothiophenes. In the right frame, the bars represent sum of alkylated analogs for each carbon number. Figure reproduced from Ref. [86],...

Kargi, F., and Robinson, J. M., Microbial Oxidation of Dibenzothiophene by the Thermophilic Organism Sulfolobus Acidocaldarius. Biotechnology and Bioengineering, 1984. 26 p. 687. 

Kayser, K. J. Cleveland, L. Park, H. S., et al., Isolation and Characterization of a Moderate Thermophile, Mycobacterium Phlei GTIS10, Capable of Dibenzothiophene Desulfurization. Applied Microbiology and Biotechnology, 2002. 59(6) pp. 737-745. 

Furuya, T. Kirimura, K. Kino, K., and Usami, S., Thermophilic biodesulfurization of dibenzothiophene and its derivatives by Mycobacterium phlei WU-F1. Ferns Microbiology Letters, 2001. 204(1) pp. 129-133. 

Wang, P., and Krawiec, S., Kinetic analyses of desulfurization of dibenzothiophene by Rhodococcus erythropolis in batch and fed-batch cultures. Applied and Environmental Microbiology, 1996. 62(5) pp. 1670-1675. 

Ohshiro, T. Hirata, T. Hashimoto, I., and Izumi, Y., Characterization of Dibenzothiophene Desulfurization Reaction by Whole Cells of Rhodococcus Erythropolis H-2 in the Presence of Hydrocarbon. J. Ferm. Bioeng., 1996. 82 pp. 610-612. 

Castorena, G. Suarez, C. Valdez, I., et al., Sulfur-Selective Desulfurization of Dibenzothiophene and Diesel Oil by Newly Isolated Rhodococcus Sp Strains. Ferns Microbiology Letters, 2002. 215(1) pp. 157-161. 

Lee, M. Senius, J. D., and Grossman, M. J., Sulfur-specific microbial desulfurization of sterically hindered analogs of dibenzothiophene. Applied and Environmental Microbiology, 1995. 61(12) pp. 4362-4366. 

Maghsoudi, S. Kheirolomoom, A. Vossoughi, M., et al., Selective desulfurization of dibenzothiophene by newly isolated Corynebacterium sp strain P32C1. Biochemical Engineering Journal, 2000. 5(1) pp. 11-16. 

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