Thione-Thiol Rearrangement of Xanthates catalyzed by Pyridine N-Oxides. Remarkably Enhanced Reactivity of 4-Dialkylaminopyridine N-Oxides

Pyridine N-oxides bearing electron-donating substituents (III) are efficient catalysts for rearrangement of O-alkyl S-methyl dithiocarbonates (xanthates) (I) to the corresponding S-alkyl S-methyl dithiocarbonates (dithiolcarbonates) (II). Of the catalysts tested, 4-piperidinopyridine N-oxide (IIIh)...

Full description

Saved in:
Bibliographic Details
Published inChemical & pharmaceutical bulletin Vol. 40; no. 7; pp. 1675 - 1682
Main Authors HARANO, Kazunobu, NAKAGAWA, Hidetoshi, KAMEI, Kumiko, KIYONAGA, Hideo, HISANO, Takuzo
Format Journal Article
LanguageEnglish
Published TOKYO The Pharmaceutical Society of Japan 1992
Pharmaceutical Soc Japan
Maruzen
Japan Science and Technology Agency
Subjects
4-dialkylaminopyridine N-oxide
Aliphatic compounds
catalytic rearrangement
charge transfer
Chemistry
Chemistry, Medicinal
Chemistry, Multidisciplinary
Exact sciences and technology
Life Sciences & Biomedicine
MNDO
O, S-dialkyl dithiocarbonate
Organic chemistry
Pharmacology & Pharmacy
Physical Sciences
Preparations and properties
S, S-dialkyl dithiiocarbonate
Science & Technology
thione-thiol rearrangement
xanthate
O,S-DIALKYL DITHIOCARBONATE
MNDO
CHARGE TRANSFER
THIONE THIOL REARRANGEMENT
CATALYTIC REARRANGEMENT
DIPOLAROPHILES
4-DIALKYLAMINOPYRIDINE N-OXIDE
S,S-DIALKYL DITHIOCARBONATE
XANTHATE
O,S-DIALKYL DITHIOCARBONATES
S,S-DIALKYL DITHIOCARBONATES
Thione thiol tautomerism
Catalytic reaction
MNDO method
Frontier orbital
Aliphatic compound
Nitrone
Theoretical study
Reaction mechanism
Kinetics
Online AccessGet full text

Cover

More Information
Summary:Pyridine N-oxides bearing electron-donating substituents (III) are efficient catalysts for rearrangement of O-alkyl S-methyl dithiocarbonates (xanthates) (I) to the corresponding S-alkyl S-methyl dithiocarbonates (dithiolcarbonates) (II). Of the catalysts tested, 4-piperidinopyridine N-oxide (IIIh) is the best from the viewpoints of catalytic activity and solubility in I. Heating of I in the presence of catalytic amounts (0.02-0.05 molar eq) of IIIh gave II together with the symmetric S, S-dialkyl and S, S-dimethyl dithiocarbonates in good yields. The catalytic behavior of donor-substituted pyridine N-oxides is discussed on the basis of kinetic and molecular orbital calculation data. The complete calculation of the perturbation equation on the initial stage of the reaction was consistent with the experimentally observed activity of the catalysts.
ISSN:0009-2363
1347-5223
DOI:10.1248/cpb.40.1675