cas 75-34-3, 1,1-Dichloroethane | Articles data

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PROCESS FOR THE PRODUCTION OF VINYL CHLORIDE, HEAVIES, AND HYDROGEN CHLORIDE FROM ETHANE
A process is provided for the chlorination of ethane using chlorine as the chlorinating agent to produce hydrogen chloride (HCl) and vinyl chloride (VCM) and heavies.
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Page/Page column 5-6

(2016/06/06)

Active carbon-supported nickel-palladium catalysts for hydrodechlorination of 1,2-dichloroethane and 1,1,2-trichloroethene
Norit active carbon-supported Ni-Pd catalysts were prepared, by incipient wetness impregnation, from the metal chlorides NiCl2.6H2O and PdCl2. The catalysts were characterized by temperature-programmed reduction, X-ray diffraction, and scanning electron microscopy, and by temperature-programmed hydrogenation (TPH) of the catalysts after use. When the catalysts were used for gasphase hydrodechlorination (HDC) of 1,2-dichloroethane (1,2-DCA) and 1,1,2-trichloroethene (TCE), very high activity and stability at a relatively low reaction temperature (503 K) were observed. Hydrodechlorination of TCE led to formation of hydrocarbons as the main products. Use of Ni and Ni-Pd catalysts for hydrodechlorination of 1,2-DCA resulted in very high (~100 %) selectivity for ethene. TPH of the catalysts after use for HDC of 1,2-DCA and TCE revealed the presence of carbon and chlorine-containing deposits on the surfaces of the catalysts. Formation of the NiCx fcc phase and the Ni3C hcp carbide phase were detected for the monometallic nickel and Ni95Pd05 catalysts.
Kamińska,?r?bowata
p. 9267 - 9280
(2015/03/14)

A crystallographic and spectroscopic study on the reactions of WCl 6 with carbonyl compounds
WCl6, 1, reacted with two equivalents of HC(O)NR2 (R = Me, Et) in CH2Cl2 to afford the W(vi) oxo-derivatives WOCl4(OCHNR2) (R = Me, 2a; R = Et, 2b) as main products. The hexachlorotungstate(v) salts [{OC-N(Me)CH2CH2CH 2}2(μ-H)][WCl6], 3, and [PhNHC(Me)N(Ph)C(O) Me][WCl6], 4, were isolated in moderate yields from the 1:2 molar reactions of 1 with N-methyl-2-pyrrolidone (in CH2Cl2) and acetanilide (in CDCl3), respectively. The additions of two equivalents of ketones/aldehydes to 1/CH2Cl2 yielded the complexes WOCl4[OC(R)(R′)] (R = Me, R′ = Ph, 5a; R = R′ = Ph, 5b; R = R′ = Me, 5c; R = R′ = Et, 5d; R = H, R′ = 2-Me-C6H4, 5e) and equimolar amounts of C(R)(R′)Cl2. Analogously, WOCl3[κ2- {1,2-C6H4(O)(CHO)}], 5f, and 1,2-C6H 4(OH)(CHCl2) were obtained from 1 and salicylaldehyde. The 1:1 reaction of 1 with acetone in CH2Cl2 resulted in the clean formation of WOCl4 and 2,2-dichloropropane. Compounds 5a,b,f were isolated as crystalline solids, whereas 5c,d,e could be detected by solution NMR only. The interaction of 1/CH2Cl2 with isatin, in a 1:1 molar ratio, revealed to be a new, convenient route for the synthesis of 3,3-dichloro-2,3-dihydro-1H-indol-2-one, 6. The 1:1 reactions of 1 with R′OCH(R)CO2Me (R = H, R′ = Me; R = Me, R′ = H) in a chlorinated solvent afforded the tungsten(v) adducts WCl 4[κ2-OCH(R)CO2Me] (R = H, 7a; R = Me, 7b). 1/CH2Cl2 reacted sluggishly with equimolar quantities of trans-(CO2Et)CHCH(CO2Et) and CH2(CO 2Me)2 to give, respectively, the W(iv) derivatives WCl4[κ2-CH2(CO2Me) 2], 8a, and [WCl4-κ2-{trans-(CO 2Et)CHCH (CO2Et)}]n, 8b, in about 70% yields. The molecular structures of 2a, 3, 4, 5a, 5f, 7a and 7b were ascertained by X-ray diffraction studies.
Dolci, Sara,Marchetti, Fabio,Pampaloni, Guido,Zacchini, Stefano
p. 5635 - 5648
(2013/06/05)

Non-mercury catalytic acetylene hydrochlorination over bimetallic Au-Co(III)/SAC catalysts for vinyl chloride monomer production
Several gold-based catalysts including Au, Au-La(iii), Au-Co(ii), and Au-Co(iii) were prepared and assessed for acetylene hydrochlorination, combining with characterizations of low-temperature N2 adsorption/desorption, thermogravimetric analysis, X-ray diffraction, temperature-programmed reduction, inductively coupled plasma-atomic emission spectroscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy. The best catalytic performance was obtained over Au1Co(iii)3/SAC catalysts with an acetylene conversion of 92% and a selectivity to VCM of 99.9%. It is indicated that the additives of Co(iii), Co(ii) and La(iii) are preferential to stabilize the catalytic active Au+ species and inhibit the reduction of Au3+ to Au 0 in the preparation process of Au-based/SAC catalysts. The addition of these additives can greatly inhibit the occurrence of coke deposition on the catalyst surface, and also inhibit the catalyst sintering, thereby improving the activity and long-term stability of the Au-based catalysts.
Zhang, Haiyang,Dai, Bin,Wang, Xugen,Li, Wei,Han, You,Gu, Junjie,Zhang, Jinli
supporting information
p. 829 - 836
(2013/04/10)

RESIST COMPOSITION, METHOD OF FORMING RESIST PATTERN, NOVEL COMPOUND AND METHOD OF PRODUCING THE SAME, AND ACID GENERATOR
A compound represented by formula (I); and a compound represented by formula (b1-1): wherein X represents —O—, —S—, —O—R3— or —S—R4—, wherein each of R3 and R4 independently represents an alkylene group of 1 to 5 carbon atoms; R2 represents an alkyl group of 1 to 6 carbon atoms, an alkoxy group of 1 to 6 carbon atoms, a halogenated alkyl group of 1 to 6 carbon atoms, a halogen atom, a hydroxyalkyl group of 1 to 6 carbon atoms, a hydroxyl group or a cyano group; a represents an integer of 0 to 2; Q1 represents an alkylene group of 1 to 12 carbon atoms or a single bond; Y1 represents an alkylene group of 1 to 4 carbon atoms or a fluorinated alkylene group; M+ represents an alkali metal ion; and A+ represents an organic cation.
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(2009/04/24)

METHOD FOR PURIFICATION OF 1,1-DICHLOROETHANE AND PROCESS FOR PRODUCTION OF 1,1-DIFLUOROETHANE USING THIS METHOD
1,1-dichloroethane containing a compound having a nitro group and/or a hydroxyl group as a stabilizer is brought into contact with zeolite having an average pore size of 3.4 to 11A and/or a carbonaceous adsorbent having an average pore size of 3.4 to 11A in a liquid phase. A stabilizer contained in 1,1-dichloroethane is efficiently removed by a simple and convenient method and 1,1-difluoroethane can be economically produced.
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Page/Page column 11; 13

(2008/06/13)

Process for the preparation of 1-chloro-1-fluoroethane and/or 1,1-difluoroethane
The invention relates to a process for the preparation of chloro-1-fluoroethane and 1,1-difluoroethane by reaction of vinyl chloride with hydrogen fluoride, in organic solvent consisting of at least one saturated halogen-containing hydrocarbon.
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Page column 7-8; Table I

(2008/06/13)

Anti-inflammatory compounds
This invention relates to anti-inflammatory compounds, methods of making such compounds and methods of using such compounds having the following structure:
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(2008/06/13)

Kinetics of the transformation of halogenated aliphatic compounds by iron sulfide
The transformation of nine halogenated aliphatic compounds, i.e., pentachloroethane (PCA), 1,1,2,2- and 1,1,1,2-tetrachloroethanes (1122-TeCA and 1112-TeCA), 1,1,1- and 1,1,2-trichloroethanes (111-TCA and 112-TCA), 1,1- and 1,2-dichloroethanes (11-DCA and 12-DCA), carbon tetrachloride (CT), and tribromomethane (TBM), by 10 g/L FeS at pH 8.3 was investigated in batch experiments. 11-DCA, 12-DCA, and 112-TCA showed no significant transformation by FeS over ~ 120 days, but the other compounds were transformed with half-lives of hours to days. PCA and 1122-TeCA underwent dehydrohalogenation faster than FeS-mediated reductive dehalogenation reactions. The remaining compounds for which considerable transformation was observed underwent FeS-mediated reactions more rapidly than hydrolysis or dehydrohalogenation. For 1112-TeCA, the dihaloelimination product, i.e., 1,1-dichlroethylene, was the only reaction product observed. For 111-TCA, CT, and TBM, hydrogenolysis products were the only products detected, even though their mass recoveries were significantly 100%. Two simple log-linear correlations between rate constants and either one-electron reduction potentials or homolytic bond dissociation enthalpies were developed, with determination coefficients of 0.48 and 0.82, respectively. These results were consistent with a rate-limiting step involving homolytic bond dissociation. However, neither correlation precisely characterized the reactivity of all the compounds, indicating distinctions among the mechanisms for reductive dehalogenation of the compounds by FeS or the influence of additional molecular or thermodynamic parameters on rate constants.
Hayes,Butler
p. 422 - 429
(2007/10/03)

Reactions of chlorinated vinylsilanes with hydrogen chloride
Catalytic hydrochlorination of a series of chloro(chlorovinyl)methylsilanes was studied. The course of the reaction depends on the number and position of the chlorine atoms in the initial monomers.
Lakhtin, V. G.,Ryabkov, V. L.,Kisin, A. V.,Nosova, V. M.,Chernyshev, E. A.
p. 375 - 378
(2007/10/03)

Reaction of 1,1,1-trichloroethane with zero-valent metals and bimetallic reductants
Information concerning the pathways and products of reaction of 1,1,1- trichloroethane (1,1,1-TCA) with zero-valent metals may be critical to the success of in situ treatment techniques. Many researchers assume that alkyl polyhalides undergo reduction via stepwise hydrogenolysis (replacement of halogen by hydrogen). Accordingly, 1,1,1-TCA should react to 1,1- dichloroethane (1,1-DCA), to chloroethane, and finally to ethane. Experiments conducted in laboratory-scale batch reactors indicate, however, that with zinc, iron, and two bimetallic reductants (nickel-plated iron and copper- plated iron) this simplistic stepwise scheme cannot explain observed results. 1,1,1-TCA was found to react rapidly with zinc to form ethane and 1,1-DCA. Independent experiments confirmed that 1,1-DCA reacts too slowly to represent an intermediate in the formation of ethane. In reactions with iron, nickel/iron, and copper/iron, cis-2-butene, ethylene, and 2-butene were also observed as minor products. Product ratios were dependent on the identity of the metal or bimetallic reductant, with zinc resulting in the lowest yield of chlorinated product. For reactions with iron and bimetallic reductants, a scheme involving successive one-electron reduction steps to form radicals and carbenoids can be invoked to explain the absence of observable intermediates, as well as the formation of products originating from radical or possibly from carbenoid coupling. Information concerning the pathways and products of reaction of 1,1,1-trichloroethane (1,1,1-TCA) with zero-valent metals may be critical to the success of in situ treatment techniques. Many researchers assume that alkyl polyhalides undergo reduction via stepwise hydrogenolysis (replacement of halogen by hydrogen). Accordingly, 1,1,1-TCA should react to 1,1-dichloroethane (1,1-DCA), to chloroethane, and finally to ethane. Experiments conducted in laboratory-scale batch reactors indicate, however, that with zinc, iron, and two bimetallic reductants (nickel-plated iron and copper-plated iron) this simplistic stepwise scheme cannot explain observed results. 1,1,1-TCA was found to react rapidly with zinc to form ethane and 1,1-DCA. Independent experiments confirmed that 1,1-DCA reacts too slowly to represent an intermediate in the formation of ethane. In reactions with iron, nickel/iron, and copper/iron, cis-2-butene, ethylene, and 2-butyne were also observed as minor products. Product ratios were dependent on the identity of the metal or bimetallic reductant, with zinc resulting in the lowest yield of chlorinated product. For reactions with iron and bimetallic reductants, a scheme involving successive one-electron reduction steps to form radicals and carbenoids can be invoked to explain the absence of observable intermediates, as well as the formation of products originating from radical or possibly from carbenoid coupling.
Fennelly, Jay P.,Roberts, A. Lynn
p. 1980 - 1988
(2007/10/03)

Kinetics and thermochemistry of the R + HBr ? RH + Br (R = CH2Cl, CHCl2, CH3CHCl or CH3CCl2) equilibrium
The kinetics of the reactions of CH2Cl, CHCl2, CH3CHCl and CH3CCl2 with HBr have been investigated in a heatable tubular reactor coupled to a photoionization mass spectrometer. The radicals, R, were produced homogeneously in the reactor by pulsed 248 nm exciplex laser photolysis. The decay of R was monitored as a function of HBr concentration under pseudo-first-order conditions to determine the rate constants as a function of temperature and pressure range. The reactions were studied separately over a wide temperature range and at these temperature ranges the rate constants determined were fitted to an Arrhenius expression (error limits stated are 1σ + Student's t values, units in cm3 molecule-1 s-1): k(CH2Cl) = (6.6 ± 1.7) × 10-13 exp[-(4.1 ± 0.2) kJ mol-1/RT], k(CHCl2) = (4.1 ± 1.0) × 10-13 exp[-(9.8 ± 1.0) kJ mol-1/RT], k(CH3CHCl) = (3.0 ± 0.9) × 10-13 exp[+(3.0 ± 0.2) kJ mol-1/RT] and k(CH3CCl2) = (4.4 ± 0.9) × 10-13 exp[-(5.9 ± 0.7) kJ mol-1/RT]. The kinetic information obtained was combined with the what is known of the recently measured rate constants of the reverse reactions to calculate the entropy and the heat of formation values of the radicals studied. The thermodynamic values were obtained at 298 K using a second law procedure. The results for entropy values are as follows (units in J K-1 mol-1): 271 ± 7 (CH2Cl), 280 ± 7 (CHCl2), 279 ± 6 (CH3CHCl) and 288 ± 5 (CH3CCl2). The results for ΔfH°298 are as follows (units in kJ mol-1): 117.3 ± 3.1 (CH2Cl), 89.0 ± 3.0 (CHCl2), 76.5 ± 1.6 (CH3CHCl) and 42.5 ± 1.7 (CH3CCl2). The C-H bond energy of analogous chlorinated hydrocarbons derived from the enthalpy of reaction values are as follows (units in kJ mol-1): 419.0 ± 2.3 (CH3Cl), 402.5 ± 2.7 (CH2Cl2), 406.6 ± 1.5 (α-C-H bond in CH3CH2Cl) and 390.6 ± 1.5 (α-C-H bond in CH3CHCl2). Improved heats of formation for the CH2ClO2 radical, ΔfH°298(CH2ClO2) = -(4 ± 11) kJ mol-1, and for the CHCl2O2 radical, ΔfH°298(CHCl2O2) = -(17 ± 7) kJ mol-1 are also calculated from the previously measured R′ + O2 ? R′O2 (R′ = CH2Cl or CHCl2) equilibriums.
Seetula, Jorma A.
p. 3069 - 3078
(2007/10/03)

Kinetics and Thermochemistry of the Reaction of 1-Chloroethyl Radical with Molecular Oxygen
The kinetics of the reaction CH3CHCl + O2 CH3CHClO2 -> products (1) has been studied at temperatures 296-839 K and He densities of (3-49)*1016 molecule cm-3 by laser photolysis/photoionization mass spectrometry.Rate constants were determined in time-resolved experiments as a function of temperature and bath gas density.At low temperatures (298-400 K) the rate constants are in the falloff region under the conditions of the experiments.Relaxation to equilibrium in the addition step of the reaction was monitored within the temperature range 520-590 K.Equilibrium constants were determined as a function of temperature and used to obtain the enthalpy and entropy of the addition step of the reaction (1).At hight temperatures (750-839 K) the reaction rate constant is independent of both pressure and temperature within the uncertainty of the experimental data and equal to (1.2 +/- 0.4)*10-14 cm3 molecule-1 s-1.Vinyl chloride (C2H3Cl) was detected as a major product of reaction 1 at T=800 K.The rate constant of the reaction CH3CHCl + Cl2 -> products (6) was determined at room temperature and He densities of (9-36)*1016 molecule cm-3 using the same technique.The value obtained is k6=(4.37 +/- 0.69)*10-12 cm3 molecule-1 s-1.An estimate of the high-pressure limit for reaction 1 was determined using this measured k6 and the k1/k6 ratio obtained by Kaiser et al.:1k1 (T=289K)=(1.04 +/- 0.22)*10-11 cm3 molecule-1 s-1.In a theoretical part of the study, structure, vibrational frequencies, and energies of nine conformations of CH3CHClO2 were calculated using ab initio UHF/6-31G* and MP2/6-31G** methods.The theoretical results are used to calculate the entropy change of the addition reaction ΔSo298=-152.3 +/- 3.3 J mol-1 K-1.This entropy change combined with the experimentally determined equilibrium constants resulted in a CH3CHCl-O2 bond energy ΔHo298=-131.2 +/- 1.8 kJ mol-1.The room-temperature entropy (So298=341.0 +/- 3.3 J mol-1 K-1) and the heat of formation (ΔHfo=-54.7 +/- 3.7 kJ mol-1) of the CH3CHClO2 adduct were obtained.
Knyazev, Vadim D.,Bencsura, Akos,Dubinsky, Ilia A.,Gutman, David,Melius, Carl F.,Senkan, Selim M.
p. 230 - 238
(2007/10/02)

Application of Time-Resolved Infrared Spectroscopy to the Determination of Absolute Rate Constants for Cl + C2H6 and Cl + C2H5Cl
Time-resolved infrared spectroscopy (TRISP) has been used to determine at 700 Torr and 298 K the absolute rate constants of reactions (1) Cl + C2H6 = C2H5 + HCl 1 = 7.05 (+/-1.4)*10-11 cm3/molecule s> and (2) Cl + C2H5Cl = C2H4Cl + HCl 2 = 6.8 (+/-1.4)*10-12 cm3/molecule s>.Pulsed UV laser photolysis of Cl2 in flowing mixtures of Cl2, C2H6 (or C2H5Cl), and air initiated the reaction.Absolute rate constants were measured by observing the rate of HCl production using this pulsed, broad-band IR technique for time delays from 50 ns to 10 μs after the photolysis laser pulse.Because chain propagation occurs via reactions (4) C2H5 + Cl2 = C2H5Cl + Cl or (6) C2H4Cl + Cl2 = C2H4Cl2 + Cl, corrections for these reactions were included in the absolute rate calculations.A determination of the rate constant of reaction 6 relative to reaction 5, C2H4Cl + O2 = C2H4ClO2, was required to calculate k2.The ratio k6/k5 was measured at 700 Torr by continuous UV photolysis of Cl2, O2, and C2H5Cl mixtures in a static reactor using the relative rate technique.Values of k6/k5 = 0.42 (+/-0.06) and 0.63 (+/-0.15) were obtained for 1-chloroethyl and 2-chloroethyl radicals, respectively.The measured value of k1 agrees with previous low-pressure (10 Torr) determinations verifying that reaction 1 is pressure independent.
Kaiser, E. W.,Rimai, L.,Schwab, E.,Lim, E. C.
p. 303 - 306
(2007/10/02)

Biphenyl derivative composition for nerve cell degeneration repairing or protective agent and process for preparing a phenyl derivative contained in the composition
There is disclosed a biphenyl derivative of the formula (B): STR1 wherein R1, R3, R4, R5 and Rc are as defined or its salt, a composition for nerve cell degeneration repairing or protecting agent containing a phenyl derivative selected from compounds (1) to (4) and (B) as defined, and a process for preparing a phenyl derivative contained in the composition.
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(2008/06/13)

Kinetic Isotope Effects for Proton Abstraction from Methanol by Polyhalogenomethyl Carbanions. Cleavage of Me3SiCHX2 and Me3SiCX3 by Base in Methanol.
The carbanions XxH(3-x)C- (X=Cl or Br; x=2 or 3) generated by base cleavage of Me3SiCH(3-x)Xx (or some related compounds) in MeOH, show a kinetic isotope kH/kD of ca. 1.1 in proton abstraction from methanol, as given by the product ratio XxH(3-x)CH/XxH(3-x)CD observed for reaction in MeOH-MeOD (1:1) at ca. 21 deg C.The low value of the isotope effect is attributed to the fact that the free electron pair in the carbanion is localized on the carbon centre; carbanions derived from acids of acidities comparable with those of X3CH and X2CH2 but in which the electron pair is conjugatively delocalized, show much larger isotope effects.
Eaborn, Colin,Stanczyk, Wlodzimierz A.
p. 471 - 473
(2007/10/02)

Process for making halogenated phosphonophosphoric acid-esters and their use
Halogenated phosphonophosphoric acid esters of the general formula STR1 in which X stands for a halogen R' stands for an alkylene having from 1 to 4 carbon atoms A stands for STR2 R'" stands for identical or different alkyl groups having from 1 to 4 carbon atoms, a halogen or hydrogen, and RIV stands for a halogen or hydrogen, are made. To this end, phosphorus (III) chloride is reacted in a first step with an alkylene oxide in the presence of a catalyst; the resulting reaction product consisting substantially of phosphorous acid trialkylesters is freed from alkylene oxide in excess and reacted in a second step with a suitable halogenoacyl halide in a molar ratio of 2:1-1.5; the resulting phosphonophosphoric acid ester is repeatedly scrubbed with water and/or an aqueous solution of ammonia and then either separated or halogenated in a third step under ultraviolet light, repeatedly scrubbed with water and/or an aqueous ammonia solution, and separated.
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(2008/06/13)

Process for the preparation of 2-chloroethanephosphonic dichloride
The invention relates to a process for the preparation of 2-chloroethanephosphonic dichloride through reaction of a 2-chloroethanephosphonate of the formula STR1 or a mixture of the two esters, with thionyl chloride at a temperature of 60° to 160° C. In this reaction, tertiary phosphines, quaternary ammonium or phosphonium salts or alkali metal or alkaline-earth metal halides are employed as catalysts. The thionyl chloride is introduced into the initially introduced ester.
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(2008/06/13)

Process for making 1,2-dichloroethane
The disclosure relates to a process for making 1,2-dichloroethane by reacting ethylene with chlorine in a solvent in the presence of a catalyst, at a temperature of about 20° to 200° C. at atmospheric or elevated pressure, and distillatively separating the 1,2-dichloroethane from the chlorination mixture. The disclosure provides more particularly for the catalyst used to be an anhydrous tetrachloroferrate(1-) or a substance capable of forming a tetrachloroferrate(1-) in the reaction mixture.
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(2008/06/13)

Ethene Chlorination and Oxidative Coupling over Supported Mono- and Bi-metallic Chloride Catalysts
Temperature-programmed reduction of metal chlorides upon silica, alumina, and titania supports using ethene produces chloroethene and 1,2-dichloroethane, together with rather unexpectedly, 1,1-dichloroethane and benzene in yields which differ from one metal chloride to another; results suggest the involvement of novel ..H/Cl.. exchange and oxidative-coupling reactions and also suggest that this technique of ethene titration may be of value in characterising the active sites in chloride catalysts and catalytic precursors.
Rollins, Keith,Sermon, Paul A.
p. 1171 - 1173
(2007/10/02)

Gas-Phase Reactions of Atomic Chlorine with Vinyl Chloride
The reactions of chlorine atoms with CH2=CHCl have been investigated over the pressure range from 70 to 4000 torr by using radioactive (38)Cl atoms formed by neutron irradiation of CClF3.The only observed product when CH2=CHCl is the sole substrate is CH2=CH(38)Cl in yields varying from 1.35percent at 4000 torr to 44.2percent at 71-torr total pressure.With HI present as a second substrate, CH2ClCH2(38)Cl is observed as a major product with a yield as high as 78percent at 4000-torr total pressure, and CH3CHCl(38)Cl is also found in yields of 2percent or less.A 1,2-chlorine atom migration is required in the overall mechanism, and two quite different kinetic schemes fit the observed yields of CH2=CH(38)Cl and CH2ClCH2(38)Cl very satisfactorily.The favored mechanism involves little initial preference for addition to the CH2 or CHCl ends of CH2=CHCl.The yields of CH2ClCH2(38)Cl at high pressures are proceded by a 1,2-chlorine atom migration from collisionally stabilized CH2CHCl(38)Cl radicals to form CH2(38)ClCHCl or CH2ClCH(38)Cl prior to abstraction of H from HI to form CH2ClCH2(38)Cl.The absolute reaction rate for (38)Cl with CH2=CHCl has been estimated from its relative rate vs. reaction with HI to be about 1.5 X 10E-10 cm3 molecule-1s-1.The energy barriers for chlorine atom addition to either end of CH2=CHCl are no larger than a few hundred cal/mol, and the loss of chlorine atoms from excited CH2(38)ClCHCl* or CH2CHCl(38)Cl* radicals must also have barriers in the exit channels no larger than a few hundred cal/mol.
Iyer, R. Subramonia,Rowland, F. S.
p. 3730 - 3737
(2007/10/02)

Photochlorination of Chloroethane and Chloroethane-d5
The hydrogen/deuterium abstraction from C2H5Cl and C2D5Cl by ground-state chlorine atoms has been investigated between 8 and 94 deg C.Results from the internal competition in chloroethane and chloroethane-d5 combined with the results of external competition with CH4 as the reference reaction have yielded rate constant data for the following reactions: CH3CH2Cl + Cl -> CH3CHCl + HCl, k2s; CH3CH2Cl + Cl -> CH2CH2Cl + HCl, k2p; CD3CD2Cl + Cl -> CD3CDCl + DCl, k2s,D; CD3CDCl + Cl -> CD2CD2Cl + DCl, k2p,D.The temperature dependence of the rate constants (cm3s-1) is given by k2s = (1.43 +/- 0.29) X 1E-11 exp, k2p = (1.35 +/- 0.28) X 1E-11 exp, k2s,D = (0.72 +/- 0.14) X 1E-11 exp , and k2p,D = (0.60 +/- 0.12) X 1E-11 exp.The results confirm the general trend of chlorine atom attack being faster at the substituted carbon atom.Kinetic isotope effects for the abstraction of primary and secondary hydrogen are kH/kD = 5.8 and 2.0 at 298 K, respectively.The magnitude of these relatively weak isotope effects agrees with expectations based on other exothermic chlorination reactions and suggests that in the temperature range of the investigation tunneling does not play an important role.
Tschuikow-Roux, E.,Yano, T.,Niedzielski, J.
p. 1408 - 1414
(2007/10/02)

Process for producing phloroglucin
A process for producing phloroglucin important as an intermediate compound of medicine, sensitizer and the like which comprises reacting an oxidation product containing at least one carbinol compound of carbinol dihydroperoxide, dicarbinol hydroperoxide and tricarbinol obtained by oxidation of 1,3,5-triisopropylbenzene, with hydrogen peroxide in a heterogeneous system in the presence of an acid catalyst and an organic solvent inert to the hydrogen peroxide and capable of dissolving the oxidation product, and decomposing the reaction product with an acid.
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(2008/06/13)

REDUCTION OF 1,1,1-TRICHLOROETHANE AND ITS ADDITION TO 1-HEPTENE INITIATED BY tert-BUTYL PEROXIDE OR Fe(CO)5 IN THE PRESENCE OF TRIETHYLSILANE
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Kruglova, N. V.,Freidlina, R. Kh.
p. 346 - 350
(2007/10/02)

Kinetics of Cl(2PJ) Reactions with the Chloroethanes CH3CH2Cl, CH3CHCl2, CH2ClCH2Cl and CH2ClCHCl2
The kinetics of the reactions Cl(2PJ) + RHCl -> RCl + HCl were investigated over the temperature range 257-426 K for RHCl = CH3CH2Cl (k2), CH3CHCl2 (k3), CH2ClCH2Cl (k4), and CH2ClCHCl2 (k5).Cl(2PJ) was produced by 355 nm pulsed laser photolysis of Cl2 and monitored by time-resolved resonance fluorescence spectroscopy.The data are adequately described by the following Arrhenius expressions (units are cm3 molecule-1 s-1, errors are 2? and refer to precision only): k2=(2.34+/-0.42)E-11exp, k3=(8.19+/-1.84)E-12exp,k4=(2.21+/-0.51)E-11exp, and k5=(4.88+/-1.41)E-12exp.Under some experimental conditions evidence for Cl(2PJ) regeneration via a secondary reaction was observed.At 258+/-1 K, deviations of Cl(2PJ) temporal profiles from first-order behavior were attributable to the reactions RCl + Cl2 -> RCl2 + Cl(2PJ)(kj).By modeling the observed C(2PJ) temporal profiles, we found the rate constant kj to lie in the range (5-12)E-14 cm3 molecule-1 s-1 for all RCl investigated.The reactivity trends observed in reactions of Cl2PJ) with C2HXCl(6-x), x=3-6, are discussed.
Wine, P. H.,Semmes, D. H.
p. 3572 - 3578
(2007/10/02)

SELECTIVE EFFECTS OF CHLOROBENZENES ON THE FREE-RADICAL CHLORINATION OF ETHYL CHLORIDE
The effects have been examined of three aromatic solvents (chlorobenzene, o-dichlorobenzene, and 1,2,4-trichlorobenzene) on the selectivity of the free-radical chlorination of ethyl chloride.It has been shown that the yield of 1,1-dichloroethane increases as the solvent concentration is increased and the temperature reduced.Mathematical models have been obtained for selectivity in aromatic media, in accordance with a previously-proposed mechanism for the selective effects of solvents.It has been shown that the parameters of the selectivity models, which describe the ability of the solvents to form complexes and the relative reactivities of the C-H bonds towards attack by ?-complexes, vary directly with the electronic properties of the solvents.
Aver'yanov, V. A.,Kirichenko, S. E.,Shvets, V. F.
p. 1089 - 1092
(2007/10/02)

Process for resolving DL-S-benzoyl-β-mercaptoisobutyric acid, and products obtained
Resolution of DL-S-benzoyl-β-mercaptoisobutyric acid into its optical antipodes is effected by treating the DL-acid in solution with D-(+)-N-benzyl-α-phenethylamine. The D(-)-S-benzoyl-β-mercaptoisobutyric acid itself as well as its salts, esters or derivatives can be obtained advantageously by this process.
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(2008/06/13)

Benzodiazepine derivatives
This invention provides benzodiazepine derivatives of the general formula STR1 wherein R1 represents a lower alkyl group, R2 represents a hydrogen atom or a lower alkyl group, R3 represents a halogen atom and R4 represents a hydrogen or halogen atom and either R5 represents a hydrogen atom or a lower alkyl group and R6 represents a lower alkyl, lower hydroxyalkyl or lower acyloxyalkyl group or R5 represents a hydrogen atom and R6 represents an aryl or lower aralkyl group or R5 and R6 together with the nitrogen atom to which they are attached represent a 3-membered to 7-membered heterocycle which, when it is at least 5-membered, can contain as a ring member an oxygen or sulphur atom or a group of the formula >N-R7 in which R7 represents a hydrogen atom or a lower alkyl group, and pharmaceutically acceptable acid addition salts thereof, which possess aldosterone-antagonistic properties and are accordingly suitable for the control or prevention of heart failure, of hepatic ascites, of primary aldosteronism and of idiopathic hypertension. Some of these compounds and salts also inhibit the intestinal resorption of cholesterol and are according suitable for the prevention or control of atherosclerosis. Also provided are a process for the manufacture of the above end products and novel intermediates therefor.
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(2008/06/13)

Thermocatalytic Reactions of 1,1-Bromochloroethane
The thermocatalytic reactions of 1,1-bromochloroethane have been investigated and the thermodynamic characteristics (ΔH0T and ΔS0T) of the disproportionation and dehydrohalogenation reactions have been obtained.The thermodynamic functions (ΔH0f and S0) of 1,1-bromochloroethane have been estimated and the deviation of the enthalpy of formation from additivity owing to the Cl-Br mutual influence in the gem-positions has been determined.
Bushneva, L. I.,Levanova, S. V.,Rodova, R. M.,Rozhnov, A. M.
p. 1403 - 1404
(2007/10/02)

Substituted sulfamic acid halides
New sulfamic acid halides and a process for the manufacture of sulfamic acid halides by reacting sulfamic acids with formaldehyde and acid halides. The products are starting materials for the manufacture of crop protection agents, dyes and pharmaceuticals.
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(2008/06/13)

Oxychlorination of hydrocarbons in the presence of non-halide copper containing catalysts
Copper chloride has been employed as a reagent for oxychlorination of hydrocarbons. It has now been found that a non-halide copper compound in combination with a rare earth compound is an excellent oxychlorination catalyst, e.g. a CuCO3 - CeO2 catalyst calcined at 900° C. for 1 hour converted 99 mole % of ethylene fed at a selectivity of 100% to chlorinated products, principally vinyl chloride, ethyl chloride and dichloroethane.
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(2008/06/13)