- PROCESS FOR THE PRODUCTION OF CHLORINATED METHANES
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The present invention provides processes for the production of chlorinated methanes via the direct chlorination of methane. The processes include a dehydrochlorination and/or chlorination step that converts up to 100% of the higher chlorinated alkanes in a process stream from the methane chlorination reaction into more highly chlorinated alkanes. These more highly chlorinated alkanes can be easily removed from the process stream. The use of a cost effective feedstream of crude methane is thus rendered possible, without additional capital expenditure for the sophisticated separation equipment required to separate ethane and other hydrocarbon components from the methane feed.
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Paragraph 0062; 0063
(2017/04/11)
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- Determination of the rate constant of the reaction of CCl2 with HCl
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The rate constant of the reaction between CCl2 radicals and HCl was experimentally determined. The CCl2 radicals were obtained by infrared multiphoton dissociation of CDCl3. The time dependence of the CCl2 radic
- Gomez, Nicolas D.,D'Accurso, Violeta,Manzano, Francisco A.,Codnia, Jorge,Azcarate, M. Laura
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p. 382 - 388
(2014/05/20)
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- Photocatalytic degradation of lindane by polyoxometalates: Intermediates and mechanistic aspects
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The photocatalytic degradation of lindane (γ-1,2,3,4,5,6-hexachlorocyclohexane) has been studied in the presence of the polyoxometalate PW12O403- in aqueous solutions. Lindane is fully decomposed to CO2, Cl- and H2O, while a great variety of intermediates has been detected using GC-MS, including aromatic compounds (dichlorophenol, trichlorophenols, tetrachlorophenol, hexachlorobenzene, di- and trichloro-benzenodiol), non-aromatic cyclic compounds (penta-, tetrachlorocyclohexene, heptachlorocyclohexane), aliphatic compounds (tetrachloroethane) and condensation products (polychlorinated biphenyls). The number and nature of the intermediates implies that the mechanism of decomposition of lindane is based on both oxidative and reductive processes. Common intermediates have been reported during photolysis of lindane in the presence of titanium dioxide. A similar overall mechanism of polyoxometalates and TiO2 photocatalysis through the formation of common reactive species is suggested.
- Antonaraki,Triantis,Papaconstantinou,Hiskia
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experimental part
p. 119 - 124
(2010/08/22)
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- ArF laser photolytic deposition and thermal modification of an ultrafine chlorohydrocarbon
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MW ArF laser irradiation of gaseous cis-dichloroethene results in fast decomposition of this compound and in deposition of solid ultrafine Cl- and H-containing carbonaceous powder which is of interest due to its sub-microscopic structure and possible reactive modification of the C-Cl bonds. The product was characterized by electron microscopy, and FTIR and Raman spectra and it was revealed that HCl, H2, and C/H fragments are lost and graphitic features are adopted upon heating to 700°C.
- Pola, Josef,Galikova, Anna,Subrt, Jan,Ouchi, Akihiko
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experimental part
p. 625 - 629
(2011/10/19)
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- Photocatalysis of chloroform decomposition by hexachloroosmate(IV)
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Hexachloroosmate(IV) effectively catalyzes the photodecomposition of chloroform in aerated solutions. The decomposition products are consistent with a mechanism in which excited state OsCl62- reduces chloroform, rather than one involving photodissociation of chlorine atoms. Trace amounts of ethanol or water in the chloroform lead to photosubstitution to form OsCl5(EtOH)- or OsCl5(H2O) -, neither of which is photocatalytically active.
- Pena, Laura A.,Hoggard, Patrick E.
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body text
p. 467 - 470
(2010/10/19)
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- Fluorodecarboxylation, rearrangement and cyclisation: the influence of structure and environment on the reactions of carboxylic acids with xenon difluoride
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The reactions of structurally diverse carboxylic acids with XeF2 in both CH2Cl2/Pyrex and CH2Cl2/PTFE have been studied. Pyrex appears to be a very effective heterogeneous catalyst for an electrophilic mode of reaction of polarised XeF2, leading to rearrangement, cyclisation and cationic products. In CH2Cl2/PTFE, fluorodecarboxylation is the main mode of reaction, in accordance with previous studies, and may occur via a SET reaction of unpolarised XeF2.
- Ramsden, Christopher A.,Shaw, Maxine M.
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experimental part
p. 3321 - 3324
(2009/08/09)
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- Polychloroethyltrifluoromethylsulfonamides from N,N-dichlorotrifluoromethylsulfonamide and dichloroethenes
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The interaction of trifluoromethylsulfonic acid N,N-dichloroamide with 1,1- and 1,2-dichloroethenes is a convenient way to N-(2,2,2-trichloroethyl)trifluoromethylsulfonamide, N-(2,2-dichloroethylidene)amide of trifluoromethylsulfonic acid and its derivatives.
- Kondrashov, Evgenii V.,Rozentsveig, Igor B.,Levkovskaya, Galina G.,Mirskova, Anna N.
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- Generation of radical species in surface reactions of chlorohydrocarbons and chlorocarbons with fluorinated gallium(III) oxide or indium(III) oxide
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The reactions of C1 and C2 chlorohydrocarbons and chlorocarbons have been studied with the Lewis acid catalysts fluorinated gallium(III) oxide and fluorinated indium(III) oxide, respectively. Product analysis shows chlorine-for-fluorine exchange reactions together with the formation of 2-methylpropane and its chlorinated analogues 2-chloromethyl-1,3-dichloropropane and 2-chloromethyl-1,2,3-trichloropropane. Reactivities of the chlorohydrocarbon probe molecules show fluorinated gallium(III) oxide to be a stronger Lewis acid than fluorinated indium(III) oxide. The formation of the symmetrical butyl compounds is consistent with the generation of surface radical species and is also consistent with a 1,2-migration mechanism operating within radical moieties at the Lewis acid surface.
- Thomson
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p. 1881 - 1885
(2007/10/03)
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- Role of copper species in chlorination and condensation reactions of acetylene
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We examined the thermally induced acetylene chlorination and condensation reactions on different types of copper salt impregnated surfaces. The System for Thermal Diagnostic Studies provided a powerful tool to study these reactions under defined reaction conditions, which were related to typical conditions in postcombustion incineration processes. Experiments were conducted with acetylene or acetylene/HCl mixtures in a quarts reactor filled with a borosilicate foam of known pore size at temperatures between 150 and 500 °C. Borosilicate was also used as the catalytic support for gas-solid reactions of acetylene and acetylene/HCl mixtures with CuCl2 and CuO. Reaction products were trapped in-line and analyzed by GC/MS. It was shown that borosilicate is not able to catalyze acetylene condensation reactions. CuCl2-impregnated borosilicate was a highly effective catalyst for acetylene chlorination/condensation reactions at temperatures above 150 °C. The same behavior was found for CuO- impregnated borosilicate in the presence of HCl. However, temperatures above 300 °C were required for this catalytic system. Mainly perchlorinated C-2 to C-8 hydrocarbons were trapped as reaction products in the gas phase. Maximum yields for acetylene chlorination/condensation reactions in each related catalytic system were found at temperatures between 300 and 400 °C. Results of the surface-catalyzed acetylene chlorination and condensation reactions were summarized in a global mechanism. A ligand transfer oxidative chlorination of acetylene with CuCl2 was proposed to be the initiation of acetylene with CuCl2 was proposed to be the initiating step. Chlorinated acetylene then condenses to higher molecular weight compounds, catalyzed by CuCl in metallacyclization reactions. We examined the thermally induced acetylene chlorination and condensation reactions on different types of copper salt impregnated surfaces. The System for Thermal Diagnostic Studies provided a powerful tool to study these reactions under defined reaction conditions, which were related to typical conditions in postcombustion incineration processes. Experiments were conducted with acetylene or acetylene/HCl mixtures in a quartz reactor filled with a borosilicate foam of known pore size at temperatures between 150 and 500 °C. Borosilicate was also used as the catalytic support for gas-solid reactions of acetylene and acetylene/HCl mixtures with CuCl2 and CuO. Reaction products were trapped in-line and analyzed by GC/MS. It was shown that borosilicate is not able to catalyze acetylene condensation reactions. CuCl2-impregnated borosilicate was a highly effective catalyst for acetylene chlorination/condensation reactions at temperatures above 150 °C. The same behavior was found for CuO-impregnated borosilicate in the presence of HCl. However, temperatures above 300 °C were required for this catalytic system. Mainly perchlorinated C-2 to C-8 hydrocarbons were trapped as reaction products in the gas phase. Maximum yields for acetylene chlorination/condensation reactions in each related catalytic system were found at temperatures between 300 and 400 °C. Results of the surface-catalyzed acetylene chlorination and condensation reactions were summarized in a global mechanism. A ligand transfer oxidative chlorination of acetylene with CuCl2 was proposed to be the initiating step. Chlorinated acetylene then condenses to higher molecular weight compounds, catalyzed by CuCl in metallacyclization reactions.
- Wehrmeier, Andreas,Lenoir, Dieter,Sidhu, Sukh S.,Taylor, Philip H.,Rubey, Wayne A.,Kettrup, Antonious,Dellinger, Barry
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p. 2741 - 2748
(2007/10/03)
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- Decomposition of acenaphthylene by ultrasonic irradiation
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Polycyclic aromatic hydrocarbons were extracted from a soil sample using ultrasound and dichloromethane-, cyclohexane-, and toluene-water mixtures. It was found that when dichloromethane is used as an extractant, acenaphthylene reacts with the solvent Several chlorinated and oxygenated derivatives were identified. The results show that chlorinated solvents should be avoided because of their sonolytic decomposition. Particularly unsaturated nonaromatic compounds might react with intermediate decomposition radicals of the solvent
- Leonhardt,Stahl
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p. 1228 - 1230
(2007/10/03)
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- A tetrachloro guest in a molecular box
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The new lattice inclusion host exo-7,exo-15-dibromo-6,7,14,15-tetrahydro-6,14-methanocycloocta[1,2-b:5,6-b'] diquinoxaline (6) has been synthesized in three steps from bicyclo[3.3.1]nonane-2,6-dione and benzofurazan oxide. It preferentially forms crystalline inclusion compounds with small polyhaloalkane guest molecules, and the crystal structure of the 1,1,2,2-tetrachloroethane compound [(C21H14N4Br2)2· C2H2Cl4, Pbcn, a 11 · 663(2), b 13 · 195(3), c 27 · 444(5) A, Z 4, R 0 · 041] is described. The key characteristic of this compound is a series of molecular boxes in which the guest molecules reside. Construction of the six surrounding walls is achieved with the aromatic rings of just four host molecules, and the guest molecule occupies a fixed position within the box. The intermolecular forces resulting in formation of this novel inclusion structure are analysed in detail.
- Marjo, Christopher E.,Bishop, Roger,Craig, Donald C.,Scudder, Marcia L.
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p. 337 - 342
(2007/10/03)
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- Liquid-phase chlorination of C-chlorovinylsilanes
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Liquid-phase chlorination of a number of chloro(chlorovinyl)methylsilanes was investigated.A number of novel C-chlorosilanes were characterized by IR and 1H NMR spectra.Some regularities of these reactions were determined: correlations between the structure of chloro(chlorovinyl)methylsilanes and their reactivities were identified. - Key words: chloro(chlorovinyl)methylsilanes; chlorine; chlorination; chloroethylsilanes; C-chlorosilanes; IR spectra; 1H NMR spectra.
- Lakhtin, V. G.,Ryabkov, V. L.,Kisin, A. V.,Nosova, V. M.,Polyakova, M. V.,Chernyshev, E. A.
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p. 2163 - 2167
(2007/10/03)
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- FTIR Study of the Cl + C2H2 Reaction: Formation of cis- and trans-CHCl=CH Radicals
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FTIR spectroscopic studies of the photolysis (λ >/= 300 nm) of mixtures containing Cl2 and C2H2, cis-CHCl=CHCl, or trans-CHCl=CHCl were carried out in 700 Torr of N2 at 295 +/- 2 K.On the basis of the kinetic analysis of cis- and trans-CHCl=CHCl formed from C2H2, the branching ratio k1a/k1b has been determined to be 0.19 +/- 0.05.Cl + C2H2 (+M) -> cis=ClCH-CH (+M); Cl + C2H2 (+M) -> trans-ClCH=CH (+M).Implications of these results for our previously postulated mechanism of Cl atom initiated oxidation of C2H2 are discussed.
- Zhu, T.,Yarwood, G.,Chen, J.,Niki, H.
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p. 5065 - 5067
(2007/10/02)
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- KINETICS OF SOME CHLOROMETHANES: SONOLYSIS IN AQUEOUS MEDIA
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The kinetics of Cl2 generation in mixed CH2Cl2/H2O, CHCl3/H2O, and CCl4/H2O systems under sonolysis at 25 deg C was studied. Both the reaction order and the dependence of the rate constant upon the incident ultrasonic power are consistent with a reaction mechanism involving H., OH. and chloromethyl radicals.
- Popa, Niculae,Ionescu, Savu Gheorghe
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p. 697 - 702
(2007/10/03)
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- Oxidation of Trichloroethene by NO2 at 445-485 K
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Trichloroethene oxidation by NO2 / Nitrogen dioxide oxidation of trichloroethene.Within the temperature range of 445-484 K, trichloroethene is oxidized by NO2 to CO and HCl, ClNO being the principal nitrogen containing product.NO, COCl2 and N2O were also produced and at 485 K the formation of 1,1,2,2-tetrachloroethane was also observed.In presence of stoichiometric excess of trichloroethene, the conversion of NO2 to ClNO was within 70-80percent.A reaction mechanism is proposed.
- Czarnowski, J.
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- Ultraviolet Absorption Spectra of the CH2Cl and CHCl2 Radicals and the Kinetics of their Self-recombination Reactions from 273 to 686 K
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The UV absorption spectra of the chloromethyl (CH2Cl) and dichloromethyl (CHCl2) radicals have been determined between 197.5 and 230 nm, together with the absolute rate constants for their association reactions: CH2Cl + CH2Cl -> products (1a), CHCl2 + CHCl2 -> products (1b) as a function of temperature from 273 to 686 K and between 29 and 760 Torr N2 total pressure.The transient decays of the radicals were monitored by time-resolved UV absorption following the flash photolysis of Cl2 mixed with the parent molecules (CH3Cl or CH2Cl2).At a resolution of 2 nm, no vibrational structure was detected in either spectrum which both appear as strong broad electronic bands with maxima around 200 nm (CH2Cl) and 215 nm (CHCl2).At these wavelengths the absolute absorption cross-sections were measured as (1.45 +/- 0.16) x 10-17 and (1.34 +/- 0.24) x 10-17 cm2 molecule-1, respectively, relative to that of CH3O2 at 240 nm (4.55 x 10-18 cm2 molecule-1).The experimental results, supported by RRKM calculations, demonstrate that the measured rate constants for removal of the radicals correspond to the high-pressure limiting rate constants for recombination, both of which exhibit a negative temperature dependence, represented by the following expressions: CH2Cl: k1a = (2.8 +/- 0.3) x 10-11 (T/298)-(0.85 +/- 0.14) cm3 molecule-1 s-1.CHCl2: k1b = (9.3 +/- 1.7) x 10-12 (T/298)-(0.74 +/- 0.10) cm3 molecule-1 s-1.Errors are 1?.The present results are compared to existing data on the self-recombination reactions of the CH3 and CCl3 radicals; the negative temperature dependence of the self-association rate constants for the series CH3, CH2Cl, CHCl2 and CCl3 are shown to be consistent within the framework of a recently developed variational transition-state theory method.
- Roussel, Pascal B.,Lightfoot, Philip D.,Caralp, Francoise,Catoire, Valery,Lesclaux, Robert,Forst, Wendell
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p. 2367 - 2377
(2007/10/02)
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- Photochemical Reactions of Primary Aromatic Amines with Chloromethanes in Solution. II. The Products and Mechanisms of Partial Reactions of Aniline in Tetrachloromethane, Chloroform and Dichloromethane
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Major products of photochemical reactions of aniline in tetrachloromethane, chloroform and dichloromethane have been isolated and identified.The mechanisms of partial reactions have been discussed. - Keywords: Photochemical Reactions, Primary Aromatic Amines, Chloromethanes
- Boszczyk, Wojciech,Latowski, Tadeusz
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p. 1589 - 1592
(2007/10/02)
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- Products and reaction pats in the liquid phase oxidation of trans-1,2-dichloroethene with oxygen
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Ultraviolet initiated liquid phase oxidation of neat trans-1,2-dichloroethene (1a) with oxigen at 30 deg C afforded ca. 45percent of the combined Cl-products CO, CO2, and phosgene as well as nine oxygenated and nine non-oxygenated chlorinated organic products.Major oxigenated products were cis- and trans-2,3-dichlorooxirane (6a, b) and 1,2,2-trichloroethyl formate (13); minor products were e.g., meso and rac bis(1,2,2-trichloroethyl)ether (11c, d) and dichloromethyl 1,2,2,-trichloroethyl ether (12).The mode of formation of all products is rationalized by a unified reaction scheme.
- Griesbaum, Karl,Hayes, Michael P.,Werli, Vera
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p. 1366 - 1370
(2007/10/02)
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- Olefin complexes of gold(I) by CO displacement from AuCl(CO)
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The cis-cyclooctene and norbornene complexes of AuCl, AuCl(cis-C8H14) (1) and AuCl(C7H10) (2), respectively, have been prepared from the reaction of AuCl(CO) with the corresponding olefin at room temperature by a CO displacement reaction. Gas volumetric equilibrium data on the reaction between AuCl(CO) and norbornene show that the formation of the olefin complex is favored at atmospheric pressure of carbon monoxide. The constant of the equilibrium AuCl(CO) + norbornene ? AuCl(norbornene) + CO is K = 4 ± 1 at 21.5°C. No CO was found to be displaced from AuCl(CO) with cyanoolefins. The crystal structure of 1 has been solved by X-ray diffraction methods. For 2, only the crystal data and a structure with insufficient resolution were obtained. The crystal data at 190 K are as follows: 1, a = 23.115 (4) A?, b = 5.419 (3) A?, c = 7.356 (2) A?, Z = 4, orthorhombic, space group Pca21, R = 0.037; 2, a = 5.697 (2) A?, b = 20.24 (1) A?, c = 6.620 (2) A?, Z = 4, orthorhombic, space group Ama2, R = 0.085. The gold atom presents the expected linear geometry, considering the olefin as a monodentate ligand.
- Dell'Amico, Daniela Belli,Calderazzo, Fausto,Dantona, Robert,Str?hle, Joachim,Weiss, Herbert
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p. 1207 - 1210
(2008/10/08)
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- SYNTHESIS, STRUCTURE, AND REACTIVITY OF N-(2,2-DICHLOROETHYLIDENE)ARENESULFONAMIDES FROM 1,2-DICHLOROETHYLENE AND N,N-DICHLOROARENESULFONAMIDES
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The properties and reactivity of N-(2,2-dichloroethylidene)arenesulfonamides CHCl2CH=NSO2Ar, obtained from N,N-dichloroarenesulfoamides and 1,2-dichloroethylene, were studied.It was shown that the arylsulfonylimines of dichloroacetaldehyde are highly active in the nucleophilic addition of alcohols and amides at the azomethine bond.Intramolecular heterocyclization of the product from the addition of β-chloroethanol to 2,2-dichloroethylidenebenzenesulfonamide by the action of alkali leads to N-phenylsulfonyl-1-dichloromethyl-1,3-oxazolidine.The high electrophilicity of the azomethine bond of the imines ArSO2N=CHCHCl2 made it possible to realize the stereospecific C-amidoalkylation of aromatic compounds (furan, thiophene, anisole).
- Drozdova, T. I.,Mirskova, A. N.,Levkovskaya, G. G.,Kalikhman, I. D.,Voronkov, M. G.
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p. 1508 - 1512
(2007/10/02)
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- N,N-DICHLOROARENESULFONAMIDES IN REACTION WITH 1,2-DICHLOROETHYLENE
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The reaction of N,N-dichloroarenesulfonamides with cis- and trans-1,2-dichloroethylene under the conditions of free-radical initiation lead to the formation of the N-arylsulfonylimines of dichloroacetaldehyde and the products from their further transformation, i.e., 2,2-dichloro-1,1-di(arylsulfonylamino)ethanes.The arylsulfonylimines of chloral, arenesulfonamides, trichloroethylene, and the products from chlorination of 1,2-dichloroethylene are formed as side products.
- Mirskova, A. N.,Drozdova, T. I.,Levkovskaya, G. G.,Kalikhman, I. D.,Voronkov, M. G.
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p. 1129 - 1135
(2007/10/02)
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- Chlorine Atom/Benzene System. 1. The Role of the 6-Chlorocyclohexadienyl Radical
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The concept of radical reactivity mediated by solvation has rested mainly on the alteration of Cl. properties by aromatic solvents.For this reason, the full scope of the benzene/Cl. system has been reexamined to evaluate the discription of that system based largely on a ?-complex (solvation).At the present time, the ?-complex description rests narrowly on the assignment of a 490-nm absorption, which, even if correct, could not provide an unambiguous structure assignment.Results are presenteed which described the selectivities in alkane substitutions as a function of the concentrations of both benzene and the alkane.Selectivities increase with decreasing alkane concentrations, reaching a plateau below 0.1 M alkane.The change in selectivity is the result of variable contributions of both a low- and a high-selectivity intermediate, LSI and HSI, respectively.The observed selectivity at a given and is the consequence of a unique / ratio.A range of substrates and their effect of DMB selectivity were studied, and from these results details regarding the chemistry of the HSI were extracted.Several features of the LSI/HSI equilibrating system are realized. (1) Reaction of alkyl radicals with Cl2 in benzene produces the LSI, (2) the LSI does not exhibit the characteristics of free chlorine atom, and (3) at alkane concentrations and , added reagents (T) which react with CCH, such as maleic anhydride (MA) or Cl2, bring about an increase in the LSI/HSI ratio.Low-selectivity hydrogen abstractions (LSI function) are best ascribed to a mixture of chlorine atom and chlorine atom/benzene ?-complex.The chemistry of CCH is as follows: (1) loss of the ipso H to O2 yielding PhCl and HO2., (2) reactions of Cl2 or (3) maleic anhydride with the aromatic nucleus of CCH resulting in additions to the ring, (4) the transfer of Cl to alkenes, and (5) the highly selective retardation of rates of reaction with alkanes producing alkyl radicals, HCl, and benzene.The results of a kinetic analysis, accounting for the effect of , , and CCH trapping agents (T), are presented.For CCH, the following reactivity order is established: maleic anhydride (6) > trans-dichloroethene(5) > 2,3-dimethylbutane (2) > pentane (1) > Cl2 > neopentane ( 2 (27) > 1 .These properties can be rationalized with canonical structures for CCH wherein spin density at carbon, chlorine, and the ipso hydrogen makes contributions to the hybrid.
- Skell, Philip S.,Baxter, Harry N.,Tanko, James M.,Chebolu, Venkatasuryanarayana
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p. 6300 - 6311
(2007/10/02)
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- EFFECT OF STRUCTURAL FACTORS ON THE REACTIVITY OF C-H BONDS IN CHLOROALKANES IN REACTION WITH A CHLORINE ATOM AND WITH THE COMPLEX OF THE CHLORINE ATOM WITH o-DICHLOROBENZENE
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The competition reaction of dichloroethanes, 1,1,2-trichloroethane, and 1-chlorobutane in o-dichlorobenzene was investigated over a wide range of temperature (-20 to +80 deg C) and solvent concentrations (0-7 M).The selective action of the solvent is consistent with a mechanism involving attack on the C-H bonds of the chloroalkanes by free chlorine atoms and by ArH -> Cl ? complexes.Equations were obtained for the selectivity of the investigated processes on the basis of the proposed mechanism.The parameters of the obtained equations reflect the relative reactivityof the C-H bonds during chlorination by chlorine atoms and ArH -> Cl complexes and also the capacity of the solvent for the complex formation.It was shown that the reactivities of the C-H bonds during attack by chlorine atoms and ArH -> Cl complexes are described by a correlation equation including the inductive effect of the substituents on the reaction center and also stabilization of the obtained radicals through conjugation and hyperconjugation effects.
- Aver'yanov, V. A.,Zarytovskii, V. M.,Shvets, V. F.
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p. 1832 - 1839
(2007/10/02)
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- Direct Photolysis of 1-Halo-1-hexynes. Lack of Ionic Behavior
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Direct photolyses at >200 nm of 1-bromo- and 1-iodo-1-hexynes were performed in polar and nonpolar solvents.Only radical-derived products were obtained even in polar solvents, contrary to the previously reported ionic photochemical behavior of alkyl and vinyl halides.The results are discussed from an energy point of view; the ionization potential of the initially formed organic radical well accounts for the obvious difference in photobehavior between alkynyl and alkyl or vinyl halides.
- Inoue, Yoshihisa,Fukunaga, Takao,Hakushi, Tadao
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p. 1732 - 1737
(2007/10/02)
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- Pyrolysis of N,N-Dihalo Derivatives of Amides and Sulfonamides
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Pyrolysis of N,N-dichlorobenzenesulfonamide produced benzene (41percent) and chlorobenzene (40percent); the dibromo compound gave benzene (19percent) and bromobenzene (20percent).Toluene (46percent), chlorotoluene (27percent), and dichlorotoluene (10percent) were generated from the N,N-dichloro-p-tolyl derivative.From each aryl substrate, 1,1,2,2-tetrachloroethane was also produced from reactions involving CH2Cl2 solvent. 3-Chloro-N,N-dichloroadamantane-1-sulfonamide decomposed to 1,3-dichloroadamantane (52percent) and 1,3,5-trichloroadamantane (15percent).N,N-Dihalobenzamides produced phenyl isocyanate; N,N-dichloro and N-bromo derivatives gave isocyanate in 16-23percent and 21-28percent yields, respectively.N,N-Dichloroadamantane-1-carboxamide produced 1-adamantyl isocyanate (20-50percent) and 1-chloroadamantane (12-46percent).The mechanistic features of the various reactions are discussed.
- Roberts, John T.,Rittberg, Barry R.,Kovacic, Peter
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p. 3988 - 3991
(2007/10/02)
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- EFFECT OF o-DICHLOROBENZENE ON THE SELECTIVITY OF PHOTOCHLORINATION OF 1,1,2-TRICHLOROETHANE
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The selective action of o-dichlorobenzene on the photochlorination of 1,1,2-trichloroethane at 20 deg C was investigated.It was shown that the selectivity of the process is determined exclusively by the / ratio.The obtained data confirm the scheme for the selective action of aromatic solvents which presupposes the formation of ArH Cl ? complexes.The latter act together with the chlorine atoms as attacking particles during radical chlorination of the C-H bonds, and their concentration is determined by the steady state and not by the complexing equilibrium.
- Aver'yanov, V. A.,Zarytovskii, V. M.,Shvets, V. F.,Treger, Yu. A.
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p. 2229 - 2231
(2007/10/02)
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- TRANSFORMATIONS OF DI(CYCLOHEXYLOXY)METHANE IN CHLOROFORM, INITIATED BY FREE RADICALS
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Cyclohexyl formate, cyclohexane, cyclohexyl chloride, cyclohexanone and (chloromethoxy)cyclohexane are formed from di(cyclohexyloxy)methane by the action of tert-butoxyl radicals in chloroform.A scheme is proposed for the formation of the above-mentioned products through di(cyclohexyloxy)methyl and alkoxycyclohexyl radicals arising from di(cyclohexyloxy)methane.
- Rol'nik, L.Z.,,Kalashnikov, S.M.,Pastushenko, E.V.,Zlotskii, S.S.,Imashev, U.B.,,Rakhmankulov, D.L.
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p. 457 - 459
(2007/10/02)
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- Free-radical transformations of di-tert-alkoxymethanes in the absence of solvent and in chloroform
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In chloroform in the presence of tert-butyl peroxide di-tert-alkoxymethanes from the corresponding tert-alkyl formates, tert-alkyl chlorides, and alkanes; here the chloroform is converted into methylene chloride and 1,1,2,2-tetrachloroethane.The relationships between the accumulation rate of the reaction products and the concentration of acetal, chloroform, and initiator were determined.An unbranched radical-chain mechanism was established for the fragmentation of the acetals with quadratic termination at the tert-alkyl and dichloromethyl radicals.
- Rol'nik, L. Z.,Kalashnikov, S. M.,Pastushenko, E. V.,Zlotskii, S. S.,Rakhmankulov, D. L.
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p. 614 - 618
(2007/10/02)
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- KINETICS OF THE GAS-PHASE PHOTOCHLORINATION OF DICHLOROMETHANE IN A TUBULAR PHOTOREACTOR.
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The kinetics were studied with due consideration taken of the radial variation in light intensity across the reactor and with the proper selection of kinetic equations, including the recombination of dichloromethyl radicals as the dominant termination step. The dependence of the absorbed radiant energy on the chlorine concentration was well simulated by the use of the radial-light and line-source model. The predominance of the observed production rate of hydrogen chloride over that of chloroform was also reproduced well by the appropriately selected kinetic expressions, without any use of the long-chain approximation. This work is pertinent to photochemical reactor design.
- Sugawara,Suzuki,Ohashi
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p. 854 - 859
(2007/10/02)
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