107-20-0Relevant articles and documents
The reactions of atomic chlorine with acrolein, methacrolein and methyl vinyl ketone
Wayne,Canosa-Mas,Cotter,Duffy,Thompson
, p. 3075 - 3084 (2001)
The rate constants and the products of the reactions between atomic chlorine and acrolein, methachlorine, and methyl vinyl ketone were determined. Rate coefficients for the reactions of chlorine with acrolein and with methyl vinyl ketone were slightly dependent at 1.6 and 760 torr, although the rate coefficients at 1.6 torr were a factor of only ～ 2 smaller than the values obtained at 1 atm. The reaction between Cl atoms and methacrolein in synthetic air and 1 atm yielded chloroacetone, formaldehyde, CO, and HCl. Between Cl atoms and acrolein, the products of reaction were HCl, chloroacetaldehyde, formaldehyde, and CO. For the reaction between Cl atoms and methyl vinyl ketone, the products were chloroacetaldehyde, formaldehyde, and CO. Branching ratios for abstraction (the fraction of reactions occurring by abstraction relative to the sum of addition and abstraction processes) were 0.22 for acrolein, 0.18 for methacrolein, and 0.03 for methyl vinyl ketone. Vast quantities of isoprene were converted to methacrolein in the atmosphere, and several channels of oxidation following attack by chlorine on methacrolein led to CO formation, with an overall yield of ～ 0.75.
Oxidation mechanisms for ethyl chloride and ethyl bromide under atmospheric conditions
Orlando,Tyndall
, p. 312 - 319 (2002)
Partially chlorinated and/or brominated alkanes are present in the earth's atmosphere as the result of natural and anthropogenic activities, and their oxidation mechanisms under atmospheric conditions have been the subject of a number of recent studies. The Cl-atom initiated oxidation of ethyl chloride and ethyl bromide was studied as a function of temperature (220-298 K) in an environmental chamber equipped with an FTIR spectrometer. Products resulting from abstraction at the -CH2Cl group included CH3C(O)Cl, CO2, CH3C(O)OOH, CH3C(O)OH, CH2O, CO, HCOOH, and CH3OH. The HCl-elimination reaction possessed an energy barrier of about 6 kcal/mole. As a result of this modest barrier, chemical activation played an important role in the chemistry of internally excited CH3CHClO radicals generated from the exothermic reaction of the CH3CHClO2 radical with NO. BrCH2CH2 radicals, generated via Cl-atom abstraction at the -CH3 group, reacted via Br-atom elimination to form ethylene or via addition of O2 to form a peroxy radical. The generation of an alkene is likely to be general a occurrence in the tropospheric chemistry of alkyl bromides.
Photooxidation of exhaust pollutants: III. Photooxidation of the chloroethenes: Degradation efficiencies, quantum yields and products
Guertler,Moeller,Sommer,Mueller,Kleinermanns
, p. 1671 - 1682 (1994)
The photochemical decomposition and oxidation of the chloroethenes C2H4-XClX (x=1-4) was investigated in the gas phase by irradiation with a low pressure mercury lamp in an oxygen atmosphere. Degradation efficiencies directly depend on the number of chlorine atoms both at 185 and 254 nm. The quantum yields for degradation increase from 2-3 for vinyl chloride to > 100 for tri- and tetrachloroethene at 185 nm in the 10-3 bar concentration range. At 254 nm we measured nearly time independent quantum yields of around 10 for tri- and 40 for tetrachloroethene. The photooxidation products and their mechanism of formation are discussed in detail.
Atmospheric chemistry and environmental assessment of inhalational fluroxene
Bravo, Ivan,Rodriguez, Ana,Rodriguez, Diana,Diaz-De-Mera, Yolanda,Notario, Alberto,Aranda, Alfonso
, p. 3834 - 3842 (2013)
Smog chamber/gas chromatography techniques are used to investigate the atmospheric degradation of fluroxene, an anesthetic, through oxidation with OH and Cl radicals at 298 K and under atmospheric pressure of N2 or air. The measured rate consta
One-pot Preparation of 2-Chloromethyldioxolanes and 2-Aminothiazoles from Chloromethyltrioxanes
Wakasugi, Takashi,Miyakawa, Tadashi,Suzuki, Fukuichi,Itsuno, Shinichi,Ito, Koichi
, p. 2039 - 2042 (1994)
Thermal degradation of chloromethyltrioxanes in the presence of catalytic amount of montmorillonite clay generated α-chloroaldehydes with high purity, which were treated in situ with ethylene glycol or thiourea to afford 2-chloromethyldioxolanes and 2-aminothiazoles, respectively.The clay catalysts used were removed by filtration.
Kinetics and mechanism of the oxidative regeneration of carbonyl compounds from oximes by pyridinium bromochromate
Sharma, Pradeep K.
, p. 364 - 368 (2006)
The oxidative deoximination of several aldo- and keto-oximes by pyridinium bromochromate (PBC), in dimethylsulfoxide, exhibited a first-order dependence on both the reductant (oxime) and the oxidant (PBC). The oxidation of ketoximes is slower than that of aldoximes. The rates of oxidation of aldoximes correlated well in terms of the Pavelich-Taft dual substituent-parameter equation. The low positive value of polar reaction constant indicated a nucleophilic attack by a chromate-oxygen on the carbon. The reaction is subject to steric hindrance by the alkyl groups. The reaction of acetaldoxime has been studied in 19 different organic solvents. The solvent effect has been analyzed by Taft's and Swain's multiparametric equations. A mechanism involving the formation of a cyclic intermediate, in the rate-determining step, has been proposed.
Oxidative regeneration of carbonyl compounds from oximes by pyridinium fluorochromate: A kinetic and mechanistic study
Sharma, Ajay,Vyas, Neha,Choudhary,Prasadrao, Ptsrk,Sharma, Vinita
, p. 2792 - 2796 (2013)
The oxidative deoximination of several aldoximes and ketoximes by pyridinium fluorochromate, in dimethyl sulphoxide, exhibited a first order dependence on pyridinium fluorochromate. A Michaelis-Menten type kinetics was observed with respect to oximes. The oxidation of ketoximes is slower than that of aldoximes. The rates of oxidation of aldoximes correlated well in terms of Pavelich-Taft dual substituentparameter equation. The low positive value of polar reaction constant indicated a nucleophilic attack by a chromate-oxygen on the carbon. The reaction is subjected to steric hindrance by the alkyl groups. The reaction of acetaldoxime has been studied in 19 different organic solvents. The solvent effect has been analyzed by multiparametric equations. A mechanism involving the formation of a cyclic intermediate, in the rate-determining step is suggested.
Preparation of Chloroacetaldehyde Cyclic Trimer and Its Depolymerization
Wakasugi, Takashi,Tonouchi, Naka,Miyakawa, Tadashi,Ishizuka, Makoto,Yamauchi, Takashi,et al.
, p. 171 - 172 (1992)
Chlorination of paraldehyde gave chloroacetaldehydes which were treated with concd sulfuric acid to afford cyclic trimer (3) of chloroacetaldehyde (CA).Depolymerization of 3 yielded pure CA satisfactory.
Synthesis, characterisation and theoretical calculations of 2,6-diaminopurine etheno derivatives
Virta, Piritta,Koch, Andreas,Roslund, Mattias U.,Mattjus, Peter,Kleinpeter, Erich,Kronberg, Leif,Sjoeholm, Rainer,Klika, Karel D.
, p. 2924 - 2929 (2005)
Four derivatives of 2,6-diaminopurine (1) were synthesised and characterised. When 1 was reacted with chloroacetaldehyde, 5-aminoimidazo[2,1-i] purine (2), 9-aminoimidazo[2,1-b]purine (3), 9-aminoimidazo[1,2-a]purine (4) and diimidazo[2,1-&:2′,1′-i]purine (5) were formed. The purified products (3-5) were fully characterised by MS, complete NMR assignments as well as fluorescence and UV spectroscopy. The purified, isolated yields of these products (3-5) varied from 2.5 to 30%. The relative stability of different tautomers was investigated by theoretical calculations. Fluorescence characteristics are also discussed and compared to the starting material 1 and a reference molecule 2-aminopurine. The Royal Society of Chemistry 2005.
New nucleoside analogs from 2-amino-9-(β-d-ribofuranosyl)purine
Virta, Piritta,Holmstroem, Toni,Roslund, Mattias U.,Mattjus, Peter,Kronberg, Leif,Sjoeholm, Rainer
, p. 821 - 827 (2004)
Four novel derivatives of 2-amino-9-(β-D-ribofuranosyl)purine (1) were synthesised and fully characterised. When 1 was reacted with chloroacetaldehyde (a), 2-chloropropanal (b), bromomalonaldehyde (c) and a mixture of chloroacetaldehyde + malonaldehyde (d), 3-(β-D-ribofuranosyl)-imidazo-[1, 2a]purine (2), 3-(β-D-ribofuranosyl)-5-methylimidazo-[1,2a]purine (3), 3-(β-D-ribofuranosyl)-5-formylimidazo-[1,2a]purine (4) and 9-(β-D-ribofuranosyl) 2-(3,5-diformyl-4-methyl-1,4-dihydro-1-pyridyl)purine (5) were formed, respectively. The products were isolated, purified by chromatography and characterised by MS, complete NMR assignment as well as fluorescence and UV spectroscopy. The yields of these reactions were moderate (14-20%). The fluorescence properties differed from those of the starting compound and the quantum yields were considerably lower.
