2362-50-7

Basic information

• Product Name: thianthrene 5-oxide
• Synonyms: thianthrene 5-oxide;Thianthrene 10-oxide;Benzothianthrene Oxide
• CAS NO: 2362-50-7
• Molecular Formula: C₁₂H₈OS₂
• Molecular Weight: 232.3213
• Mol File: 2362-50-7.mol
• Article Data: 19

Chemical Properties

• Melting Point: 143-143.5 °C
• Boiling Point: 423.2 °C at 760 mmHg
• Flash Point: 209.7 °C
• Appearance: /
• Density: 1.49 g/cm³
• Vapor Pressure: 5.61E-07mmHg at 25°C
• Refractive Index: 1.797
• Storage Temp.: 2-8°C
• CAS DataBase Reference: thianthrene 5-oxide(CAS DataBase Reference)
• NIST Chemistry Reference: thianthrene 5-oxide(2362-50-7)
• EPA Substance Registry System: thianthrene 5-oxide(2362-50-7)

Safety Data

• Hazardous Substances Data: 2362-50-7(Hazardous Substances Data)

Usage

Uses

Thianthrene S-oxide is a sulfoxide-based thianthrene reagent for late-stage C-H functionalization. Developed by the Ritter Lab, C-H functionalization by thianthrenation proceeds with >99% selectivity and furnishes functionalized arenes serving as synthetic linchpins for further participation in diverse transformations. Nonfluorinated thianthrene S-oxide is best used for all arenes more electron-rich than anisole. For other arenes, the fluorinated TFT S-oxide (903981) was demonstrated as the thanthrenation reagent.

Synthesis Reference(s)

Journal of the American Chemical Society, 78, p. 2163, 1956 DOI: 10.1021/ja01591a037Synthetic Communications, 22, p. 1799, 1992 DOI: 10.1080/00397919208020500

InChI:InChI=1/C12H8OS2/c13-15-11-7-3-1-5-9(11)14-10-6-2-4-8-12(10)15/h1-8H

Upstream product

• 576-26-1 2.6-dimethylphenol 
• 35787-71-4 thianthrene cation radical perchlorate 
• 5775-76-8 valeraldoxime 
• 35787-71-4 thianthrene cation radical perchlorate 
• 6033-61-0 hexanal oxime 
• 98-54-4 para-tert-butylphenol 
• 2078-54-8 2,6-diisopropylphenol 
• 150-13-0 4-amino-benzoic acid 
• 587-85-9 diphenylmercury(II) 
• 1745-81-9 o-Allylphenol 
• 108-95-2 phenol 
• 19615-38-4 5-(N-p-Toluenesulfonyl)iminothianthrene 
• 13269-52-8 trans-3-Hexene 
• 593-74-8 dimethylmercury 

Downstream Products

• 92-85-3 Thianthrene 
• 92-85-3 thianthrene cation radical 
• 132-65-0 dibenzothiophene 

Relevant articles and documents

Alkaline hydrolysis of N-bromoiminothianthrene derivatives

5-(N-Bromo)iminothianthrene (2) and 5-(N-bromo)iminothianthrene 10-oxide (5) and 10,10-dioxide (8) were prepared and their alkaline hydrolyses were studied. The compound 2 and cis-5-(N-bromo)iminothianthrene 10-oxide (cis-5) afforded the corresponding sulfoximine exclusively. While, unexpectedly, both trans-5-(N-bromo)iminothianthrene 10-oxide (trans-5) and 8 afforded mainly de-brominated products, trans-5-iminothianthrene 10-oxide (trans-4) and 5-iminothianthrene 10,10-dioxide (7), respectively. In these cases, 5-iminothianthrene 5,10-dioxide (6) (Z- and E-mixture) and 5-iminothianthrene 5,10,10-trioxide (9) and further de-iminated products were also formed respectively as minor products. The stereochemical considerations on the SN reactions are described in view of the steric effect and 'flip-flap' motion of the thianthrene framework.

Complete regioselective formation of 2-(arylsulfinyl)diphenyl sulfides from 5-arylthianthreniumyl perchlorates

Treatment of 5-arylthianthreniumyl perchlorates with potassium tert- butoxide in dimethyl sulfoxide at room temperature gave 2- (arylsulfinyl)diphenyl sulfides (29-79% yields), which are the first examples for complete regioselective formation of S-monoxides from unsymmetrical arylthiodiphenyl sulfides.

Photo SN-bond cleavage and related reactions of thianthrene sulfilimine derivatives

Several 1- and 2-substituted thianthrene sulfilimine derivatives were prepared and the selectivity toward oxidation and N-tosylimination under several conditions was studied. In the photolysis of trans-5-(N-p-tosyl)iminothianthrene 10-oxide (trans-10), photo isomerization to cis-10 was observed. Further, photoimino-transfer reaction of sulfilimines and their 10-mono- and -dioxide derivatives to sulfides was intensively studied to make clear the ability as nitrene precursors.

Reactions of nucleophiles with 5-(alkoxy)thianthrenium ions

Reactions of 5-(alkoxy)thianthrenium perchlorates (1) with weakly basic nucleophiles Br-, I- and PhS- (X-) in MeCN and DMSO led to SN2 substitution, E2C elimination, and reaction at sulfornium sulfur to extents depending on the structure of the alkoxy group (RO) in 1 and the nucleophile. Three types of reaction occurred with R = cyclopentyl (1a), cyclohexyl (1b), cis- (1c) and trans- 4-methylcyclohexyl (1d) and cycloheptyl (1e), and X- = Br and I-. That is, SN2 reaction gave RX and thianithrene 5-oxide (ThO), E2C reaction gave cycloalkene and ThO and reaction at sulfonium sulfur gave X2, thianthrene (Th) and cycloalkanol (ROH). Earlier work with R = Me (1f) and Et (1g) and X- = I-. Br- had shown that only SN2 reaction occurred. In contrast with reactions of halide ions, reactions of PhS- with 1b-g occurred only at sulfonium sulfur, giving Th, ROH and PhSSPh (DPDS). For comparison with 1, reactions of Ph2S+OMe (2) with I- and PhS- were carried out. Reaction with I- gave only Ph2S=O and Mel (SN2), Reaction with PhS- gave very little PhSMe (SN2) but mainly Ph2S, MeOH, and DPDS from reaction at sulfonium sulfur. The differences in nucleophilic pathways (PhS- vs Br- and I-) in reactions with 1 and 2 are attributed to differences in thiophilicities of the nucleophiles. The thiophilicity of PhS- dominates its reactions with 1 and 2. The direction toward products (Th, ROH and DPDS) in these reactions is compounded by the ease of displacement of alkoxide from 1 and 2 by PhS-, and the ease with which, subsequently, thiophilic PhS- attacks sulfenyl sulfur in the resulting phenylthiosulfonium ion. Copyright