1468-37-7Relevant academic research and scientific papers
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.
Synthesis and Characterization of (Methoxy(thiocarbonyl))sulfenyl Chloride
Schroll, Alayne L.,Eastep, Steven J.,Barany, George
, p. 1475 - 1479 (2007/10/02)
(Methoxy(thiocarbonyl))sulfenyl chloride (1), a previously elusive compound, has now been generated by cleavage of methoxy(thiocarbonyl) N-methyl-N-phenylamino sulfide (7) with gaseous hydrogen chloride.The sulfenyl chloride 1 had limited stability and was characterized by trapping with O,O'-dimethyl thiocarbonate or with methanethiol to yield (methoxycarbonyl)(methoxy(thiocarbonyl))disulfane (8) or (methoxy(thiocarbonyl))methyldisulfane (9), respectively.Chlorination of acetyl methoxy(thiocarbonyl) sulfide (6) could be arrested at 1 plus acetyl chloride, and further chlorination of 1 provided (methoxydichloromethyl)disulfanyl chloride (5).
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.
Novel Symmetrical and Mixed Carbamoyl and Amino Polysulfanes by Reactions of (Alkoxydichloromethyl)polysulfanyl Substrates with N-Methylaniline
Schroll, Alayne L.,Barany, George
, p. 1866 - 1881 (2007/10/02)
Reactions of (alkoxydichloromethyl)polysulfanes with N-methylaniline can be rationalized by a "carbamoyl" route where the alkoxydichloromethyl group behaves via loss of alkyl chloride as a "masked" acid chloride or by a "sulfenyl" route which reflects fragmentation of the (alkoxydichloromethyl)polysulfanyl functionality into the corresponding alkoxy(thiocarbonyl) and sulfenyl components (cf.Scheme I).Application of this and related chemistry to bifunctional substrates arising from partial or complete chlorination of 2Sm, R = Me, Et, i-Pr, and m = 1-4, has led to Ph(Me)N(C=O)Sn(C=O)N(Me)Ph, n = 2-12; Ph(Me)N(C=O)SnN(Me)Ph, n = 1-6; Ph(Me)NSnN(Me)Ph, n = 1-10; RO(C=S)Sn(C=O)N(Me)Ph, n = 2, 3; and RO(C=S)SnN(Me)Ph, n = 1-5.These families allowed a test of reversed-phase high-pressure liquid chromatography for evaluating homologies in polysulfane series.Treatment of bis sulfide (27c) with sulfuryl chloride in the presence of calcium carbonate conveniently gave distillable bis(chlorocarbonyl)trisulfane (14), whereas the same procedure with SO2Cl2 alone gave directly (chlorocarbonyl)disulfanyl chloride (12) (see Scheme VII).Higher Cl(C=O)SmCl, m = 3-5, were indicated but could not be isolated in the course of studies generalizing results on 14 to the preparation of higher Cl(C=O)Sn(C=O)Cl, n = 4-6.The new bis(carbamoyl) monosulfide 61 was obtained by the relatively slow triphenylphosphine or cyanide promoted desulfurization of bis(methylphenylcarbamoyl)disulfane (4) (eq. 1 and 4); cyanide treatment of the higher polysulfanes Ph(Me)N(C=O)Sn(C=O)N(Me)Ph for n > 3 rapidly gave disulfane directly (eq 5).
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.
1,2,3-Thiadiazole-3-in-5-ylidene-urea derivatives, process for making the same and compositions containing the same having growth regulating activity for plants
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, (2008/06/13)
1,2,3-Thiadiazole-3-in-5-ylidene-urea derivative of the formula STR1 in which R1 is hydrogen or alkyl which may be substituted in one or several places by oxygen or sulfur and wherein R2 and R3 have the meaning as given in the attached specification and wherein X is oxygen or sulfur. The compounds have properties suited for controlling the natural growth and natural development of plants and in addition have a superior defoliating property without accompanying unpleasant odors.
1,2,3-Thiadiazole-2-id derivatives, process for making the same and composition containing the same having a growth regulating activity for plants
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, (2008/06/13)
1,2,3-Thiadiazole-2-id-derivative of the formula STR1 in which R1 is hydrogen or alkyl which may be substituted in one or several places by oxygen or sulfur and wherein R1 has the meaning as given in the attached specification and wherein X is oxygen or sulfur and B is a univalent metal atom. The compounds have properties suited for controlling the natural growth and natural development of plants and in addition have a superior defoliating property.
