Ion radicals. XXXIV. Preparation of phenoxathiin cation radical perchlorate. Formation and reactions of S-iminophenoxathiin (phenoxathiin sulfilimine)

Mani, Serugudi R.; Shine, Henry J.

doi:10.1021/jo00907a011

Cited by 21 publications

(2 citation statements)

References 5 publications

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“…Thianthrene (Th •+ ) and phenoxathiin cation radical perchlorates (PO •+ ClO 4 - ) were prepared as described earlier. , The potential explosiveness of Th •+ ClO 4 - should be noted …”

Section: Methodsmentioning

confidence: 99%

Adducts of Phenoxathiin and Thianthrene Cation Radicals with Alkenes and Cycloalkenes

et al. 2003

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Phenoxathiin cation radical perchlorate (PO.+ClO4(-)) added stereospecifically to cyclopentene, cyclohexene, cycloheptene, and 1,5-cyclooctadiene to give 1,2-bis(5-phenoxathiiniumyl)cycloalkane diperchlorates (4-7) in good yield. The diaxial configuration of the PO+ groups was confirmed with X-ray crystallography. Unlike additions of thianthrene cation radical perchlorate (Th.+ClO4(-)) to these cycloalkenes, no evidence for formation of monoadducts was found in the reactions of PO.+ClO4(-). This difference is discussed. Addition of Th.+ClO4(-) to five trans alkenes (2-butene, 2-pentene, 4-methyl-2-pentene, 3-octene, 5-decene) and four cis alkenes (2-pentene, 2-hexene, 2-heptene, 5-decene) gave in each case a mixture of mono- and bisadducts in which the configuration of the alkene was retained. Thus, cis alkenes gave erythro monoadducts and threo bisadducts, whereas trans alkenes gave threo monoadducts and erythro bisadducts. In these additions to alkenes, cis alkenes gave predominantly bisadducts, while trans alkenes (except for trans-2-butene) gave predominantly monoadducts. This difference is explained. 1,2-Bis(5-phenoxathiiniumyl)cycloalkanes (4-7) and 1,2-bis(5-thianthreniumyl)cycloalkanes underwent fast elimination reactions on activated alumina forming, respectively, 1-(5-phenoxathiiniumyl)cycloalkenes (8-11) and 1-(5-thianthreniumyl)cycloalkenes (12-16). Among adducts of Th.+ClO4(-) and alkenes, monoadducts underwent fast ring opening on alumina to give (5-thianthreniumyl)alkenes, while bisadducts underwent fast eliminations of H+ and thianthrene (Th) to give (5-thianthreniumyl)alkenes also. Ring opening of monoadducts was a stereospecific reaction in which the configuration of the original alkene was retained. Thus, erythro monoadducts (from cis alkenes) gave (E)-(5-thianthreniumyl)alkenes and threo monoadducts (from trans alkenes) gave (Z)-(5-thianthreniumyl)alkenes. Among bisadducts, elimination of a proton and Th occurred and was more complex, giving both (E)- and (Z)-(5-thianthreniumyl)alkenes. These results are explained. Configurations of adducts and (5-thianthreniumyl)alkenes were deduced with the aid of X-ray crystallography and (1)H and (13)C NMR spectroscopy. In the NMR spectra of (E)- and (Z)-(5-thianthreniumyl)alkenes, the alkenyl proton of Z isomers always appeared at a lower field (0.8-1.0 ppm) than that of E isomers.

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Section: Methodsmentioning

confidence: 99%

Adducts of Phenoxathiin and Thianthrene Cation Radicals with Alkenes and Cycloalkenes

et al. 2003

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“…An analogous reaction of Th •+ 2 and of the phenoxathiin cation radical with ammonia was discovered about 20 years ago. That reaction is illustrated in Scheme with phenoxathiin cation radical, from which both the sulfiliminium perchlorate ( 1 ) and sulfilimine ( 2 ) were isolated 1 …”

Section: Introductionmentioning

confidence: 93%

Structure and Thermal Decomposition of Some 5-(Cyclohexyloxy)thianthreniumyl Perchlorates

1997

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Five sets of cis-and trans-substituted cyclohexanols were used for reaction with thianthrene cation radical perchlorate, namely, cis-and trans-cyclohexane-1, 2-diol, cis-and trans-2-methyl-, 3-methyl-, and 4-methylcyclohexanol, and cis,cis-and trans,trans-3,5-dimethylcyclohexanol. Reaction in CH 2 -Cl 2 solution and precipitation with ether gave the corresponding crystalline 5-(cyclohexyloxy)thianthreniumyl perchlorate salts. The configuration of each salt in CDCl 3 was shown by 1 H and 13 C NMR spectroscopy to correspond with the configuration of the cyclohexanol from which it was made. X-ray Ortep diagrams of four of the salts confirmed the structure deduced from NMR spectroscopy. In the NMR, inequivalence of the 1 H and 13 C signals from the thianthreniumyl 4and 6-, 1-and 9-, 2-and 8-, and 3-and 7-positions was found when the 1′-position of the cyclohexyl ring was stereogenic. In the four Ortep diagrams, the orientation of the S-O bond was psuedoaxial. Thermal decomposition of the salts made from the monosubstituted cyclohexanols at 100 °C in CH 3 CN solution gave products consistent with the assigned structures.

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Electron‐transfer Reactions of Heteroaromatic Compounds

Albini¹,

Fagnoni²

2001

Electron Transfer in Chemistry

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Ion radicals. XXXIV. Preparation of phenoxathiin cation radical perchlorate. Formation and reactions of S-iminophenoxathiin (phenoxathiin sulfilimine)

Cited by 21 publications

References 5 publications

Adducts of Phenoxathiin and Thianthrene Cation Radicals with Alkenes and Cycloalkenes

Adducts of Phenoxathiin and Thianthrene Cation Radicals with Alkenes and Cycloalkenes

Structure and Thermal Decomposition of Some 5-(Cyclohexyloxy)thianthreniumyl Perchlorates

Electron‐transfer Reactions of Heteroaromatic Compounds

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