107-05-1Relevant articles and documents
REDUCTION OF SOME POLYHALOGENATO- AND POLYACETOXYALLYLIC COMPOUNDS WITH TRIBUTYLTIN HYDRIDE IN THE PRESENCE OR ABSENCE OF A PALLADIUM CATALYST I. REDUCTION OF DICHLORO- AND DIACETOXY-PROPENES
Guibe, Francois,Zigna, Anne-Marie,Balavoine, G.
, p. 257 - 266 (1986)
Radical-promoted tributyltin hydride reduction of 3,3-dichloropropene, (Z)-1,3-dichloropropene, or (E)-1,3-dichloropropene yields a mixture of the three possible regio-stereoisomeric monochloropropenes.The palladium-catalyzed reduction yields regiospecifically the two stereoisomeric 1-chloropropenes with a Z/E ratio which remains constant whatever the starting dichloropropene but which is not the thermodynamic ratio.The results are against a radical mechanism and strongly support a polar ?-allyl mechanism for the catalytic reactions.
Collisional Energy Transfer in Thermal Decomposition Reaction of 1,2-Dichloropropane
Yun, Sun Jin,Jung, Kyung-Hoon,Kang, Wee-Kyeong
, p. 5842 - 5847 (1988)
The thermal decomposition reaction of 1,2-dichloropropane (1,2-DCP) was studied at temperatures from 663.2 to 703.2 K over the pressure range 0.04-10.0 Torr.The decomposition modes of 1,2-DCP were monitored via four reaction channels of unimolecular HCl eliminations and a negligible portion of a side radical chain reaction. 3-Chloropropene (3-CP), cis-1-chloropropene (cis-1-CP), trans-1-chloropropene (trans-1-CP), and 2-chloropropene (2-CP) were produced.Rate parameters for the thermal processes found in this study are k3(3-CP)/s-1=1013.61 +/- 0.30exp-1/RT>, kcis(cis-1-CP)/s-1=1012.90 +/- 0.70exp-1/RT>, ktrans(trans-1-CP)/s-1=1013.21 +/- 0.80exp-1/RT>, k2(2-CP)/s-1=1013.05 +/- 0.44exp-1/RT>, and ktot(total)/s-1=1013.70 +/- 0.50exp-1/RT>.The unimolecular thermal decomposition reactions of the four-channel 1,2-DCP system were carried out in the presence of a He bath gas to evaluate intermolecular-energy-transfer parameters.The average energies removed per collision from energized 1,2-DCP by bath gas are as follows: by the substrate, 1200 cm-1 for the stepladder model; by He, 250 cm-1 for the exponential model.The effects of active additives, CO2 and HCl, and the surface condition of the reaction vessel were also studied to ascertain the potential properties of the thermal decomposition reaction of 1,2-DCP.
INFRARED LASER MULTIPHOTON ABSORPTION AND REACTION OF ORGANIC COMPOUNDS: SYNTHETICALLY UNIQUE REACTION CONTROL
Danen, Wayne C.,Setser, D. W.,Nguyen, Hanh H.,Ibrahim, Md. Sani B.
, p. 173 - 180 (1987)
Several examples of synthetically unique reaction controll effect by pulsed infrared laser multiphoton irradiation are reviewed.The uniqueness derives from the ability of the pulsed laser to rapidly vibrationally heat molecules coupled with an extremely short reaction time of approximately 10 μs for the processes discussed herein.Three systems are discussed: a bifunctional reactant with competing reaction channels, a reactant with consecutive reaction channels, and the free radical chlorination of cyclopropane.
Pressure dependence of the reaction Cl + C3H6
Kaiser,Wallington
, p. 9788 - 9793 (1996)
The rate constant for the reaction Cl + C3H6 (k1) has been measured relative to that of Cl + C2H6 over the range 0.3-700 Torr in N2 at 298 K. UV irradiation was used to generate Cl atoms in mixtures of C3H6, C2H6, Cl2, and N2 in two different reactors using FTIR or GC analysis. The yields of the two major products, allyl chloride (3-C3H5Cl) and 1,2-dichloropropane were measured. k1 decreases by a factor of 5 between 700 and 1 Torr. Below 1 Torr, the rate constant becomes independent of pressure. The results indicate that k1 is a composite of three reaction channels, each having a different pressure dependence. Measurement of the yield of 1,2-dichloropropane, the final product formed from the addition of Cl to C3H6, at each pressure allows a determination of the rate constant (k1a) for the addition of Cl to C3H6. Assuming a typical center broadening factor (Fc = 0.6), the high- and low-pressure limiting constants are calculated to be k1a(∞) = (2.7 ± 0.4) × 10-10 cm3 molecule-1 s-1 and k1a(0) = (4.0 ± 0.4) × 10-28 cm6 molecule-2 s-1. The pressure dependence of the yield of 3-C3H5Cl indicates that the allyl radical is likely formed by both abstraction and addition-elimination channels. The rate constant of the abstraction reaction from the methyl radical in C3H6 is (2.3 ± 0.3) × 10-11 cm3 molecule-1 s-1. At pressures below 10 Torr, the rate constant for formation of the allyl radical increases by 50%, and this is ascribed to an addition-elimination process. Relative rate constant ratios were also measured for Cl atom reactions with allyl chloride (k6) and 1,2-dichloropropane (k7) relative to C3H6, C2H5Cl, or CH3Cl to correct the product yield experiments for secondary consumption. The observed values of k6/k1 are 0.75 for total pressures of 10-700 Torr, 0.44 at 1 Torr, and 0.33 at 0.4 Torr. On the basis of the relative rate measurements k7 = (3.9 ± 0.6) × 10-12 cm3 molecule-1 s-1 over the range 1-700 Torr.
Kinetics of the Reactions of Unsaturated Hydrocarbon Free Radicals (Vinyl, Allyl, and Propargyl) with Molecular Chlorine
Timonen, Raimo S.,Russell, John J.,Sarzynski, Dariusz,Gutman, David
, p. 1873 - 1877 (1987)
The kinetics of the reactions of three unsaturated free radicals (vinyl, allyl, and propargyl) with molecular chlorine have been studied by using a tubular reactor coupled to a photoionization mass spectrometer.The radicals were homogeneously generated by the pulsed photolysis of precursor molecules at 193 nm.The subsequent decays of the radical concentrations were monitored in real-time experiments as a function of Cl2 concentration to obtain the rate constants of these Cl atom metathesis reactions.Rate constants were measured as a function of temperature to obtain Arrhenius parameters.The following rate constant expressions were obtained (units of the preexponential factor are cm3 molecule-1 s-1, and activation energies are in kJ mol-1; the temperature range covered in each study is also indicated): C2H3 + Cl2; C3H3 + Cl2 ; C3H5 + Cl2 .The factors governing the reactivity of polyatomic free radicals in these and other Cl atom transfer reactions with molecular chlorine are reviewed.
KrF Excimer Laser-induced Dehydrochlorination of 1,2-Dichloropropane
Ouchi, Akihiko,Niino, Hiroyuki,Yabe, Akira,Kawakami, Haruhiko
, p. 917 - 920 (1988)
Dehydrochlorination of 1,2-dichloropropane was conducted with and without irradiation of KrF excimer laser (248 nm).It afforded four products, cis-1-, trans-1-, 2-, and 3-chloropropene.The reaction was remarkably accelerated with irradiation of laser especially at the low temperatures.
Homolytic fragmentation of allyloxychlorocarbene
Moss, Robert A.,Ma, Yan,Fu, Xiaolin,Sauers, Ronald R.
, p. 2055 - 2058 (2005)
(Chemical Equation Presented) The decomposition of allyloxychlorocarbene in hydrocarbon solvents leads via homolysis to allyl and COCl radicals, which recombine to 3-butenoyl chloride or (after scission of ?COCl to CO and ?Cl) to all
Preperation and Properties of Inclusion Compounds of η3-Allylpalladium Complexes with Cyclodextrins
Harada, Akira,Takeuchi, Mizutomo,Takahashi, Shigetoshi
, p. 4367 - 4370 (1988)
Inclusion compounds of di-μ-chloro-bis(η-allyl)dipalladium and its analogues with cyclodextrins (CDs; α-CD, β-CD, and γ-CD) were prepared.One-to-one inclusion compounds were obtained in high yields by the treatment of β- and γ-cyclodextrin with di-μ-chlor
Silphos [PCl3-n(SiO2)n]: A heterogeneous phosphine reagent for the conversion of epoxides to β-bromoformates or alkenes
Iranpoor, Nasser,Firouzabadi, Habib,Jamalian, Arezu
, p. 1823 - 1827 (2006)
Silphos [PCl3-n(SiO2)n] as a heterogeneous phosphine reagent is efficiently applied for the transformation of epoxides to β-bromoformates in the presence of bromine or N-bromosuccinimide in dimethyl formamide at 0 °C. The combination of Silphos and iodine was also found suitable for the room temperature preparation of alkenes. The use of Silphos provides the advantage of easy separation of the phosphine oxide by-product from the reaction mixture.
The Coupling of Vinyl and μ-Methylene Ligands: A New View of the Mechanism of the Fischer-Tropsch Polymerisation Reaction
Martinez, Jesus M.,Adams, Harry,Bailey, Neil A.,Maitlis, Peter M.
, p. 286 - 287 (1989)
The ready decomposition of the vinyl-di-μ-methylene-dirhodium complex, >, to give C3 (propene or η3-allylic ligands) by linking of the vinyl and methylene ligands, prompts the proposal of a new mechanism for the polymerisation step in the Fischer-Tropsch reaction in which the polymer chain carriers are surface alkenyls rather than alkyls.
