143788-52-7

Basic information

• Product Name: (2S)-2-methyl-1,3-benzodithiole 1-oxide
• CAS NO: 143788-52-7
• Molecular Formula: C₈H₈OS₂
• Molecular Weight: 184.2785
• Mol File: 143788-52-7.mol

Chemical Properties

• Boiling Point: 352.5°C at 760 mmHg
• Flash Point: 167°C
• Density: 1.42g/cm³
• Vapor Pressure: 7.77E-05mmHg at 25°C
• Refractive Index: 1.718
• CAS DataBase Reference: (2S)-2-methyl-1,3-benzodithiole 1-oxide(CAS DataBase Reference)
• NIST Chemistry Reference: (2S)-2-methyl-1,3-benzodithiole 1-oxide(143788-52-7)
• EPA Substance Registry System: (2S)-2-methyl-1,3-benzodithiole 1-oxide(143788-52-7)

Safety Data

• Hazardous Substances Data: 143788-52-7(Hazardous Substances Data)

Upstream product

• 142181-68-8 cis-2-methyl-1,3-benzodithiole 1-oxide 
• 68486-94-2 2-methylbenzo[d][1,3]dithiole 
• 17534-15-5 Benzene-1,2-dithiol 

Relevant articles and documents

Dioxygenase-catalysed sulfoxidation of bicyclic alkylaryl sulfides and chemoenzymatic synthesis of acyclic disulfoxides

Toluene- and naphthalene-dioxygenase-catalysed oxidation of six bicyclic disulfide substrates, using whole cells of Pseudomonas putida, gave the corresponding monosulfoxides with high ee values and enantiocomplementarity, in most cases. Two alcohol-sulfox

Stereoselective reductase-catalysed deoxygenation of sulfoxides in aerobic and anaerobic bacteria.

Direct and indirect evidence, of unexpected stereoselective reductase-catalysed deoxygenations of sulfoxides, was found. The deoxygenations proceeded simultaneously, with the expected dioxygenase-catalysed asymmetric sulfoxidation of sulfides, during some biotransformations with the aerobic bacterium Pseudomonas putida UV4. Stereoselective reductase-catalysed asymmetric deoxygenation of racemic alkylaryl, dialkyl and phenolic sulfoxides was observed, without evidence of the reverse sulfoxidation reaction, using anaerobic bacterial strains. A purified dimethyl sulfoxide reductase, obtained from the intact cells of the anaerobic bacterium Citrobacter braakii DMSO 11, yielded, from the corresponding racemates, enantiopure alkylaryl sulfoxide and thiosulfinate samples.

Sulfoxides of High Enantiopurity from Bacterial Dioxygenase-catalysed Oxidation

Selected strains of the bacterium Pseudomonas putida (previously shown to effect dioxygenase-catalysed asymmetric cis-dihydroxylation of alkenes) have been found to yield chiral sulfoxides from the corresponding sulfides with a strong preference for the (R)- or (S)-configurations but without evidence of sulfone formation; similar results obtained using an Escherichia coli clone (pKST11, containing the Tod C1 C2 B and A genes encoding toluene dioxygenase from P. putida NCIMB 11767) are again consistent with a stereoselective dioxygenase-catalysed sulfoxidation.

Stereoselectivity of enzymatic and chemical oxygenation of sulfur atoms in 2-methyl-1,3-benzodithiole

S-Monooxygenation of 2-methyl-1,3-benzodithiole, to yield cis- and trans-2-methyl-1,3-benzodithiole 1-oxide, has been studied as a new stereochemical probe using achiral and chiral chemical oxidants and enzymes from microbial and animal sources. Chemical oxidants showed a preference for trans S-oxide formation, and this preference was enhanced in the presence of a chiral matrix. The ability of pure enzymes to stereodifferentiate between geminal lone pairs on a prochiral sulfur atom, or geminal sulfur atoms on a prochiral carbon atom, has been observed. Thus, intact fungal and bacterial oxidations showed a marked selectivity (87-96%) for formation of the cis S-oxide isomers. In addition, highly purified hog liver and rabbit lung flavin-containing monooxygenases showed a marked preference for formation of the cis S-oxide and the pro-R sulfur atom. Other monooxygenase-catalyzed sulfoxidations of 2-methyl-1,3-benzodithiole, including cytochrome P-450 2B1 (P450PB-B), showed a markedly lower stereoselectivity.

Synthesis, Separation and Absolute Configuration Assignment to Enantiomers of 1,3-Benzodithiole 1-Oxide and 2-Alkyl-1,3-Benzodithiole 1-Oxides

1,3-Benzodithiole 1-oxide, 5, has been resolved into enantiomers using chiral stationary phase high performance liquid chromatography.Alkylation of an excess (25percent) of the late eluting (+)-(1R) enantiomer of the sulfoxide 5 under basic conditions yielded both cis and trans isomers of 2-methyl (6cis-1R,2S,6trans-1R,2R), 2-ethyl (7cis-1R,2S, 7trans-1R,2R) and 2-isopropyl (8cis-1R,2S, 8trans-1R,2R)-benzodithiole 1-oxide (25percent e.e.) and allowed a stereochemically correlation of absolute configuration between the suloxides 5 - 8. Treatment of racemic 1,3-benzodithiole 1-oxide (51S/51R) with potassium bis(trimethylsilyl)amide and (S)-(+)-1-iodo-2-methylbutane yielded four diastereoisomers of 2-(2'-methylbutyl)-1,3-benzodithiole 1-oxide (9cis-1R,2S,2'S, 9cis-1S,2R,2'S, 9trans-1S,2S,2'S, 9trans-1R,2R,2'S) which were separated by chiral stationary phase HPLC (CSP-HPLC).The most strongly retained diastereoisomer was analysed by X-ray crystallography and was assigned the (1S:1S:2'S) absolute configuration.Further alkylation of 9trans-1S,2S,2'S under similar conditions yielded 2-(2'S-methylbutyl)-2-(2"S-methylbutyl)-1,3-benzodithiole 1-oxide 10 of (1S,2'S,2"S) configuration exclusively.The same stereoisomer of the sulfoxide 10 was also obtained by dialkylation of the early eluting (-)-enantiomer of 1,3-benzodithiole 1-oxide (51S) using (+)-1-iodo-2-metrhylbutane, thus enabling the unequivocal establishment of the absolute configurations of the enantiomers of 1,3-benzodithiole 1-oxides listed in Table 1.A comparison of circular dichroism (CD) spectra for sulfoxides 5 - 9 indicates that this method may also be used to correlate absolute configurations of 2-alkyl substituted 1,3-benzodithiole 1-oxides.