2362-50-7Relevant articles and documents
Alkaline hydrolysis of N-bromoiminothianthrene derivatives
Kawaguchi, Hiroyuki,Nakajima, Akitaka,Fujii, Takayoshi,Kim, Bung Ju,Hashimoto, Junko,Fujimoto, Akihiro,Yoshimura, Toshiaki,Morita, Hiroyuki
, p. 10907 - 10913 (2006)
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
Kim, Jongyup,Kim, Kab Sig,Kim, Kyongtae
, p. 617 - 622 (1999)
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
Fujita, Tomoyuki,Kamiyama, Hideo,Osawa, Yasushi,Kawaguchi, Hiroyuki,Kim, Bung Ju,Tatami, Atsushi,Kawashima, Wataru,Maeda, Tetsuo,Nakanishi, Atsushi,Morita, Hiroyuki
, p. 7708 - 7716 (2008/02/07)
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
Liu, Bo,Shine, Henry J.,Zhao, Wenyi
, p. 827 - 836 (2007/10/03)
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