10025-82-8 Purity
≥99%
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Specification
The synthesis of 4-substituted dibenzothiophenes (DBT) from dibenzothiophene-5-oxide (DBTO) can be achieved using a one-pot method. The method involves a sulfoxide-guided C-H metallation/boration/B2Pin2-mediated reduction/Suzuki coupling process. A variety of DBT-based heterobiaryl compounds were successfully prepared using DBTO as a model substrate.
Synthesis of DBT compounds from DBTO
· Optimal reaction conditions: DBTO (0.2 mmol), LiHMDS base (6.0 eq.), B2Pin2 (5.0 eq.), THF (1.2 mL), at 55 °C under Ar atmosphere for 13 h.
· Aryl halides with electron-withdrawing groups (including NO2, aldehydes, and ketones) at the ortho, meta, and para positions afforded the corresponding Suzuki coupling products in 35% to 76% yield.
· 1-tert-butyl-4-iodobenzene and 2-iodoanisole were also successfully converted into 4-aryl-substituted DBT products, with yields of 79% and 54%, respectively.
· The luminescent material PhImPOTD 39 was successfully synthesized through the reaction of DBTO and PhImPOI through a one-pot two-step method with a yield of 62%.
Dibenzothiophene-5-oxide (DBTO) cleanly generates dibenzothiophene (DBT) upon direct photolysis, but with very low quantum yields. A proposed mechanism involves the cleavage of the SO bond coupled to an intersystem crossing step to generate sulfide and O(3P) via a unimolecular pathway. To test this hypothesis, heavy atom-substituted DBTOs were prepared and subjected to photolysis. Iodine-, bromine-, and chlorine-substituted DBTOs showed higher deoxygenation quantum yields than the parent molecule, the order of which was consistent with heavy atom effects associated with intersystem crossing.
All solvents such as dibenzothiophene-5-oxide were spectroscopic grade or equivalent and were deoxygenated by bubbling with argon for 10 min prior to photolysis. Cyclohexene was refluxed over Na under an Ar atmosphere and distilled immediately before use. The initial concentrations of all photolysates ranged from 1.0 to 4.0 mM. Dodecane was used as an internal standard for all photoreactions. Quantum yield measurements were performed using pentobenzone as a photometer and the samples were illuminated in 1 cm square cells. Quantum yields were measured using a Xe arc lamp mounted on a grating set to 320 nm.
Rhodococcus strain lGTS8 is able to utilize dibenzothiophene (DBT) as a sole source of sulfur. The carbon skeleton of DBT is not metabolized and is preserved as 2-hydroxybiphenyl (HBP), which accumulates in the culture medium. Studies using radiolabeling showed that sulfur is released as inorganic sulfite. DBT is catalyzed to undergo a stepwise S oxidation, first to dibenzothiophene 5-oxide (DBTO), then to dibenzothiophene 5,5-dioxide (DBTO2), and finally to HBP and sulfite. The results are consistent with the role of DszC as a monooxygenase, the role of DUA as a distinct enzyme that catalyzes the reductive hydroxylation of DBTO2, resulting in cleavage of the thiophene ring, and the role of DszB as an aromatic sulfonic acid hydrolase.
Strain IGTS8 was grown in SRM with DMSO as the sole sulfur source. A volume of 100 ml of the cell suspension (approximately 9 g of dry cells) was diluted to 400 ml with 50 mM HEPPS buffer. The desired substrate was added to a final concentration of 200 pM and the suspension was incubated overnight in an orbital shaker (250 rpm, 30 "C). The cells were then removed by centrifugation and the supernatant was titrated to pH 1 with HCl. An equal volume of ethyl acetate was added and the mixture was stirred for 4 h. The ethyl acetate phase was recovered and dried by stirring over anhydrous MgSO4 for 1 h. The ethyl acetate was removed by rotary evaporation and the solid was redissolved in 3 ml of ethyl acetate. Uncharged compounds such as DBTO partition easily into the organic phase, and HBPSi- is transferred to BPSi after the first condensation.
Strain SYL was identified as the basis for the unique ability of Corynebacterium isolates to utilize dibenzothiophene (DBT) sulfur. Strain SYL can utilize a variety of organic and inorganic sulfur compounds, such as DBT sulfone, dimethyl sulfide, dimethyl sulfoxide, dimethyl sulfone, CS2, FeS2, and elemental sulfur. Strain SYL metabolizes DBT to dibenzothiophene-5-oxide, DBT sulfone, and 2-hydroxybiphenyl, which are subsequently nitrated during the culture to produce at least two different hydroxynitrobiphenyls. These metabolites were separated by silica gel column chromatography and identified by NMR, UV, and spectroscopic techniques.
Sulfate release was observed, but in small amounts, indicating that sulfate released from DBT was effectively utilized by SYL. 2HBP formation reached a maximum after 60 h and then decreased, indicating the formation of hydroxynitrobiphenyls. The amount of 2HBP formed was much less than the amount estimated by stoichiometry, compared with the amount of DBT reduced. It may be caused by the nitration and accumulation of dibenzothiophene-5-oxide and DBT sulfone.
Unique optical raw materials
The structure of dibenzothiophene-5-oxide enables it to obtain compounds with various optical properties through chemical modification.
C12H8OS
Dibenzothiophene-5-oxide should be stored in a dark, airtight and dry place at room temperature.
Dibenzothiophene-5-oxide is slightly soluble in chloroform and methanol
Dibenzothiophene is reacted by heating it in an oxygen atmosphere; common reaction conditions include high temperature and high pressure. By fully contacting dibenzothiophene with oxygen, an oxidation reaction can occur to form dibenzothiophene 5-oxide.
Dibenzothiophene 5-oxide can be used as a starting material or intermediate in organic synthesis to build complex organic molecules. And since dibenzothiophene 5-oxides and their derivatives may have potential pharmaceutical activities, they may also be used in pharmaceutical research and development to find new drug candidates for the treatment of various diseases. In addition dibenzothiophene 5-oxides have good electron transport properties and photophysical properties, which can be used in the construction of organic optoelectronic devices such as organic field-effect transistors (OFETs), organic light-emitting diodes (OLEDs) and organic solar cells (OPVs).
200.26
38.77
1.761
NGDPCAMPVQYGCW-UHFFFAOYSA-N
C1=CC=C2C(=C1)C3=CC=CC=C3S2=O
Reference: [1] Tetrahedron Letters, 2006, vol. 47, # 12, p. 2009 - 2012
Reference: [1] Synlett, 2015, vol. 26, # 18, p. 2547 - 2552
Reference: [1] Journal of the American Chemical Society, 1981, vol. 103, # 2, p. 289 - 295
Reference: [1]Bahrami
[Tetrahedron Letters, 2006, vol. 47, # 12, p. 2009 - 2012]
Reference: [1]Bresciani, Giulio; Ciancaleoni, Gianluca; Crucianelli, Marcello; Gemmiti, Mario; Marchetti, Fabio; Pampaloni, Guido
[Molecular catalysis, 2021, vol. 516]
Reference: [1]Fujiki, Kiyoko; Kurita, Shigehito; Yoshida, Eiji
[Synthetic Communications, 1996, vol. 26, # 19, p. 3619 - 3626]
* For details of the synthesis route, please refer to the original source to ensure accuracy.