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1.
1.  Study has been made of the kinetics of the-elimination of alcohol from 3-carbethoxy-4-ethoxy-2-pentanone in benzene and under the catalytic action of acetic acid.
2.  This reaction involves formation of a complex between substrate and acetic acid.
3.  The equilibrium constant for the reaction of forming the complex between substrate and acetic acid, and the rate constant for complex formation, have both been determined.
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2.
1.  Dimethyl, diphenyl, and tetramethylene sulfoxide hydrochlorides react with methylheptenyl, citronellyl, and geranyl acetates to give predominantly the allylic chlorination products.
2.  These findings are preferably to be regarded as involving AdE reactions between the weakly electrophlic hydroxy and (or) chlorosulfonium cation and the trisubstituted C=C bond in these olefins at the key stage.
3.  The addition of lithium perchlorate has been found to accelerate this reaction.
4.  Sulfoxide hydrobromides are highly selective brominating agents for the terminal grouping in isopropenoid oligoolefins.
Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1797–1803, August, 1988.  相似文献   

3.
1.  The kinetics of the Cannizzaro reaction of benzaldehyde in aqueous KOH solution have been studied spectrophotometrically, working at 25°C and at concentrations ranging from 19.1 to 37.9%.
2.  Reaction proceeds through the formation of an activated complex consisting of the doubly ionized and the un-ionized forms of benzaldehyde and the hydroxide cation.
3.  The spectrophotometric data and the kinetic data have been combined to give an estimate of the benzaldehyde ionization constant in aqueous KOH solution at 25°C.
4.  Analysis of the kinetic data for benzaldehyde reduction by formaldehyde has shown the activated complex for this reaction to be composed of an un-ionized benzaldehyde molecule and a doubly ionized formaldehyde molecule, with or without participation of the hydroxide cation.
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4.
1.  The molecular-sieve properties of a number of synthetic and natural chabazites have been investigated.
2.  Characteristic differences have been revealed in the molecular-sieve properties, thermal stability, and x-ray characteristics between the two groups of the zeolites studied.
3.  A reversal of the molecular-sieve effect on passing from the calcium to the sodium-calcium forms of certain synthetic and natural chabazites has been observed.
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5.
1.  In NaA zeolite a homocharge is formed by charges deposited on the surface of the zeolite from the gas gap between the electrode and the specimen.
2.  The existence of thermoelectret effects has been found in the systems NaA-zeolite -air, NaA-helium, NaA-nitrogen, and NaA-oxygen.
3.  The thermoelectret effects are caused by both the accumulation of charges in the specimen and the adsorption of molecules in the electric field.
4.  A low mobility has been noted for adsorbed molecules in the electret state of the system.
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6.
1.  The reaction of 6-nitro-2,9-dioxa-1-azabicyclo[4.3.0]nonane derivatives with alcohols and alcoholates leads to remplacement of the nitro group by the corresponding alkoxy group.
2.  The reaction proceeds with either a complete (for the case of the alcoholates) or predominant (for the case of alcohols) inversion of the configuration at the substitution center.
3.  The reaction proceeds via the intermediately formed bicyclic immonium cation.
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7.
1.  An intermediate alkoxyphosphorane with two pentacoordinated phosphorus atoms was isolated and characterized during the reaction of 2,5-bis(diethylaminomethyl)hydroquinone with trialkyl phosphites.
2.  A method has been developed for the synthesis of phosphorylated dihydric phenols.
3.  The triethylether of 3-ethoxy-6-hydroxy-1,4-xylyenediphosphonic acid was prepared by the interaction of 2,5-bis(diethylaminomethyl)hydroquinone with diethylphosphorous acid in the presence of triethyl phosphite.
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8.
1.  The intramolecular Khand-Pauson reaction is substantially accelerated when it is carried out on the surface of a Chromatographic adsorbent in the absence of a solvent.
2.  A method has been developed for the preparation of substituted 3-oxabicyclo[3.3.0]-oct-5-en-7-ones, by cyclization of the dicobalt hexacarbonyl complexes of allyl propargyl ethers.
3.  A novel cyclization reaction of dicobalt hexacarbonyl complexes has been found, which provides a convenient synthetic route to 4-hydroxymethylcyclopent-2-en-1-ones.
Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2802–2812, December, 1988.  相似文献   

9.
1.  The kinetics of reactions of alkali metal salts of 9-carbomethoxy- and 9-cyanofluorene with para-nitrofluorobenzene and of Me3SnM with pentafluoropyridine have been studied.
2.  In the case of carbanions the free anions are more reactive, while in the case of Me3SnM the corresponding tight (contact) ion pairs are more reactive.
3.  The effect of the leaving group (on reactivity) was investigated using the reactions of pentafluorochlorobenzene with the K salts of 9-carbomethoxyfluorene and cyclopentadienylirondicarbonyl anions as examples.
4.  The reaction mechanism has been shown to depend on the nature of the nucleophile.
Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2826–2832, December, 1988.  相似文献   

10.
1.  An efficient method of aziridine dimer synthesis is presented involving reaction of aziridine with esters of strong organic acids followed by alkaline hydrolysis of the resultant N-acyl derivatives.
2.  New N-acyl and carbamoyl derivatives of aziridine dimer and trimer were synthesized.
3.  Linear and branched isomers of aziridine tetramer and also diastereomers of 2-methylaziridine dimer were isolated and characterized.
4.  An efficient regiospecific synthesis of 2,2-dimethylaziridine dimer and trimer was developed.
Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2566–2575, November, 1988.  相似文献   

11.
1.  Using DMSO and MeSOPh it has been shown for the first time that O-trifluoroacetylated sulfoxides react with unactivated trisubstituted olefins to give allylsulfonium salts.
2.  LiClO4 has been found to accelerate this ene-type reaction.
3.  It has been found for the first time in the aliphatic series that the competition between [3, 2]-rearrangement and the Stevens rearrangement of the S-ylid generated from the allylsulfonium salt is governed by the type of counterion present, and this observation has been rationalized.
Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 365–372, February, 1989.  相似文献   

12.
1.  A general method of synthesis of azomethine compounds of boron has been proposed from imines and esters of thioboric acids. The reaction between ketimines and diesters of thioboroorganic acids led to the formation of diiminoboranes. Triiminoboranes were obtained on interacting ketimines and thioborates.
2.  Diiminoboranes and triiminoboranes obtained from alkylarylketimines exist as mixtures of imines and enamines.
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13.
1.  Following the CNDO/2 approximation to the SCF MO LCAO method, electronic parameters have been calculated for the molecules and ions of various nitro compounds.
2.  Calculated values of the dipole moment and enthalpy of atomization proved to be in satisfactory agreement with the experimentally determined values, the maximum deviation between them amounting to 1.4% for the aromatic systems.
3.  The nitro compound parameters most sensitive to change in the intramolecular interaction are the C-N bond energy and the charges on the carbon and halide atoms.
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14.
1.  The first stable compound with an O-Hg-Ge grouping was obtained by the reaction of 4,6-ditert-butyl-1,2-benzoquinone with bis(triisopropylgermyl)mercury.
2.  A study was made of the photodecomposition of 1-triisopropylgermyloxy-2-triisopropylgermyl-mercuroxy-3,5-di-tert-butylbenzene, and also of its reaction with hydrochloric acid and ethylmercury chloride.
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15.
1.  Vinyl- and isopropenyl-o-carborane are hydrogenated under the reaction conditions for the hydroformylation and carboxylation of olefins in the presence of cobalt or rhodium carbonyls.
2.  A mechanism was proposed for the hydrogenation of olefin-o-carboranes in alcohol solutions under CO pressure.
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16.
1.  A new method of analysis of autocatalytic reactions was developed which permits determining the rate constants of noncatalytic and catalytic reaction pathways with the data from one kinetic curve.
2.  The reverse reaction of acylation has an autocatalytic character.
3.  In comparison to CHCl3, in CH3CN, all of the rate constants increase by 2–4 times, and the noncatalytic reaction pathways are more sensitive to the nature of the solvent.
Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 1978–1984, September, 1988.  相似文献   

17.
1.  Methanol, containing 10–20 mole % of CH3I, is carbonylated to methyl acetate in the presence of impregnated Eh-zeolite NaX catalyst at 230–250° and atmospheric pressure.
2.  The specific (per gram of Rh) rate of methyl acetate formation is antibatic to the Rh content in the catalyst, it increases with increase in the methanol contact time, and shows little change in the range 230–250°.
3.  The rate of forming the sole secondary product, namely dimethyl ether, decreases with increase in the amount of Rh and the methanol contact time.
4.  CH2I is an astoichiometric component of the reaction.
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18.
1.  The reaction between 1-chloro-1,3,5,7-tetramethyl-2,4,6,8-tetrathioprotoadamantane and mercapto-compounds or weakly basic amines produces sulfides and amine derivatives with the protostructure. When (II) reacts with strongly basic amines, dehydrochloridation takes place.
2.  The reaction between 9-bromo-1,3,5,7-tetramethyl-2,4,6,8-tetrathioadamantane and thioacetic acid in ethanol in presence of alkali proceeds by regrouping, with the formation of the thiolacetate of 2,4,6,8-tetra-thioprotoadamantane.
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19.
1.  Potentiometric titration in nitromethane at 25°C has been used to determine dissociation constants for 16 mono-substituted benzoic acids.
2.  Brönsted and Hammett equations have been set up for the compound series under study here.
3.  The data of the literature have been used to evaluate the nitromethane autoprotolysis constant, pKS24.
4.  The relative differentiating action of nitromethane with respect to other solvents has been evaluated from the slopes of the Brönsted and Hammett plots and the values of the autoprotolysis constant. The differentiating action of nitromethane with respect to acids is greater than that of acids with respect to alcohols and acetone, but less than that of DMSO, acetonitrile, and DMF.
5.  Study has been made of the dissociation of the aminobenzoic acids in nitromethane. Solutions of p-aminobenzoic acid are free of zwitterions, while solutions of the m-aminobenzoic acid contain these ions to the extent of 50%.
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20.
1.  The principal reaction path for flash photolysis of fluorotrinitromethane (FTNM) in alcoholic solvents is that leading to the formation of fluorodinitromethane anions through an ionic mechanism.
2.  Study has been made of the kinetics of FDNM anion formation in FTNM photolysis in abs. methanol containing CH3ONa. It was found that the reaction is first order with respect to the FTNM.
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