53439-64-8Relevant articles and documents
Kinetics and mechanism of diallyl sulfoxide pyrolysis; A combined theoretical and experimental study in the gas phase
Izadyar,Gholami
, p. 62809 - 62816 (2015/02/19)
A combined experimental and computational study was carried out on the gas phase pyrolysis reaction of diallylsulfoxide. Allyl alcohol and thioacrolein were detected as the major products during a unimolecular reaction. Experimental kinetic studies were carried out via a static system under the pressure of 21-55 torr and temperature of 435.2-475.1 K. Based on the experiments, the reaction is homogeneous and proceeds through a zwitterionic intermediate. Computational studies at the DFT (B3LYP) and QCISD(T) levels with 6-311++G(d,p) basis set indicated a two-step concerted pathway as the possible route. Comparison between the experimental and theoretical activation parameters for the most probable path confirmed a good agreement.
Flash vacuum thermolysis - Synthesis and characterization of unstabilized cycloalkenethiones
Briard, Emmanuelle,Levillain, Jocelyne,Ripoll, Jean-Louis,Dat, Yves,Marcual, Albert,Lange, Catherine
, p. 869 - 874 (2007/10/03)
The flash vacuum thermolysis (FVT) of cydoalkenyl allyl (or propargyl) sulfides 8, 9, 12, and 13 led, as the main thermal pathway, to the conjugated cycloalkenethiones 1, 3, and 5, resulting from a retro-ene reaction. These reactive thioketones, thus obtained in ca. 70% yield, have been characterized in the gas phase by mass spectrometry, and at low temperature by IR, UV/Vis and NMR spectroscopy. The polymerization of 1, 3, and 5 upon warming is generally more rapid than the other attempted reactions and only the [2 + 3] dipolar cycloaddition with diazomethane led in low yield, besides polymeric materials, to isomeric 1,3-dithiolanes 20 from cyclopentenethione 1. The obtention of the nonconjugated cycloalkenethiones 2 and 4, expected in the FVT of sulfides 10 and 11, has been confirmed only by UV/Vis spectroscopy at -196 °C, due to their rapid enethiolization. In the case of the large-ring sulfide 14, the (E) geometry of the double bond favoured the competitive retro-ene reaction yielding cyclododecene and propynethial; on the other hand, the FVT of the tricyclic gem-dithiol 15, a possible precursor of cyclobutenethione (7), led to vinyl thioketene (18), obtained by thermal ring opening of 7.
GAS-PHASE THERMOLYSIS OF SULFUR COMPOUNDS. PART VI. ALLYL PROPARGYL AND ISOPROPYL PROPARGYL SULFIDES
Martin, Gonzalo,Lugo, Nery,Ropero, Marcos,Martinez, Henry
, p. 47 - 56 (2007/10/02)
Allyl propargyl and isopropyl propargyl sulfides were pyrolyzed in a stirred-flow system at temperatures in the range 312-402 deg C and pressures between2 and 14 torr.The allyl propargyl sulfide yielded as products a mixture of propene and allene and the corresponding propynethial and propenethial.The thioaldehydes react at room temperature to form polymers and the Diels-Alder adduct 1,3-dithia-2-ethynyl-cyclohex-5-ene.The reaction products from isopropyl propargyl sulfide were allene and thioacetone.The reaction showed first order kinetics, with the rate coefficients following the Arrhenius equations Allyl Propargyl Sulfide:k(sec-1) = 1011.22+/-0.28exp(-139 +/- 3 kJ/mol RT), Isopropyl Propargyl Sulfide: k(sec-1) = 1011.51+/-0.14exp(-155 +/- 2 kJ/mol RT).The kinetic deuterium isotope effect of 4-thia-5-deutero-5-methyl-hex-1-yne pyrolysis was studied over the temperature range 370-402 deg C.
