1468-37-7Relevant articles and documents
X-ray snapshot observation of palladium-mediated aromatic bromination in a porous complex
Ikemoto, Koki,Inokuma, Yasuhide,Rissanen, Kari,Fujita, Makoto
, p. 6892 - 6895 (2014)
Pd-mediated aromatic bromination is intriguing to synthetic and organometallic chemists due to both its synthetic utility and, more importantly, a proposed mechanism involving an uncommon Pd(IV)/Pd(II) catalytic cycle. Here, we report an X-ray snapshot observation of a Pd reaction center during a Pd-mediated aromatic bromination in a single crystal of a porous coordination network crystalline scaffold. Upon treatment of a single crystal with N-bromosuccinimide, sequential X-ray snapshots revealed that the aryl-Pd(II)-L species embedded in the network pores was converted to the brominated aryl product through a transient aryl-Pd(II)-Br species, which is normally unobservable because of its rapid dimerization into insoluble Pd 2(μ-Br)2 species. Though the reaction pathway may be biased by the crystalline state, the new X-ray snapshot method relies on crystalline flasks to provide important mechanistic insight.
DIORGANOTELLURBIS(ALKYLXANTHOGENATE), TEIL II
Wieber, Markus,Schmidt, Elmar
, p. 223 - 228 (2007/10/02)
Diphenyltelluriumbis(alkylxanthates) as well as telluracyclopentane-1,1-bis(alkylxanthates) of the general formula R2Te(S2COR')2 and C4H8Te(S2COR')2 (R = C6H5 and R' = CH3, C2H5, i-C3H7) are obtained by reaction of diphenyltellurium-dichloride or telluracyclopentane-1,1-diiodide with sodiumxanthates.The insertion of CS2 into the corresponding organotelluriumbis-alkoxydes is only successful in the case of the cyclic compound.Diphenyltelluriumbis-alkoxydes react with decomposition.This decomposition in substance and in solution is investigated.
A General Strategy for Elaboration of the Dithiocarbonyl Functionality, -(C=O)SS-: Application to the Synthesis of Bis(chlorocarbonyl)disulfane and Related Derivatives of Thiocarbonic Acids
Barany, George,Schroll, Alayne L.,Mott, Andrew W.,Halsrud, David A.
, p. 4750 - 4761 (2007/10/02)
A variety of sulfenyl chlorides have been reacted with a variety of alkoxythiocarbonyl compounds to give adducts which then lose (spontaneously, or upon thermolysis, or in the presence of Lewis acid catalyst) the alkyl chloride to provide an assortment of dithiocarbonyl compounds in good to excellent yields.The preparations of bis(chlorocarbonyl)disulfane (1), ((trichloromethyl)dithio)carbonyl chloride (2), ((alkoxycarbonyl)dithio)carbonyl chlorides (3 and 4), and (((alkylthio)carbonyl)dithio)carbonyl chlorides (5 and 6) by this methodology were optimized; some of the (alkoxydichloromethyl)disulfanyl adducts, e.g., ROCCl2SS(C=O)Cl (10) and ROCCl2SS(C=O)OR'(54), were reasonable stable and could be isolated.All new compounds were characterized by analytical data, 1H and 13C NMR, IR, UV, and mass spectrometry, and high-yield derivatizations with alcohols or N-methylaniline.The reaction with N-methylaniline was also adapted to a rapid, convenient, and precise analytical-scale assay of mixtures of compounds containing acid chloride and/or sulfenyl chloride functionalities.The kinetics, mechanism, and stereochemistry of the dithiocarbonyl synthesis are discussed.
