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1.
Presently, a large variety of layered materials are synthesized that are able to intercalate neutral guest molecules or to exchange inorganic and organic ions for interlayer ions. Several of these materials are also found as minerals.The intracrystalline reactivity of a few selected compounds will be described and compared to clay minerals:
–  - intercalation into crystalline silicic acids;
–  - reactions of phosphates, arsenates, and sulfates;
–  - reactions of titanates, niobates, and molybdates with long chain alkylammonium ions, and
–  - anion exchange properties of double hydroxides.
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2.
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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3.
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   

4.
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   

5.
1.  The hydrolysis rate of N-benzoylanthranilic acid was studied at a KOH concentration of 2.2–44.6% and a temperature of 25–95°.
2.  The limiting step of the process is the reaction of the singly ionized form of the reagent with a molecule of water.
3.  The equilibrium constant for the addition of hydroxyl ion to the carbonyl atom of the amido group of N-benzoylanthranilic acid is 267, and the true rate constant for the reaction of the ionized form with a molecule of H2O at 25° is 0.13 min–1.
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6.
1.  The adsorption properties with respect to benzene vapors and the pore structure of carbon adsorbents with almost maximum development of the microporosity were studied.
2.  The position of the micropore volume distribution curves whose maxima correspond to a size (halfwidth) of 1.2–1.4 nm and micropore volumes 1.5 cm3/g is a characteristic feature of the adsorbents studied. The difference between ordinary active carbons and the active carbons investigated is only quantitative in the values of the parameters of the Dubinin-Stockley adsorption equation.
3.  The adsorption isotherms are described by the adsorption equation from the theory of volume filling of micropores in a wide range of equilibrium relative pressures and temperatures of 293–353 K with totally satisfactory precision.
4.  The question of the upper limit of the micropores of carbon adsorbents is discussed.
Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 977–983, May, 1988.  相似文献   

7.
1.  The planar alkoxydiazinoxide fragments are shown to have the Z-configuration and be orthogonal to each other by an x-ray structure study of a series of alkoxydiazinoxides.
2.  In the oxydiazinoxide fragments, p- conjugation occurs.
3.  The molecules of the compounds in the crystals studied are joined by hydrogen bonds.
Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 297–301, February, 1989.  相似文献   

8.
1.  New cationic o-tolyl and o-fluorophenyl complexes of Ni containing Ph3P, MeCN, or THF ligands have been synthesized.
2.  Reaction of these compounds with potassium carboxylates gave the novel o-tolyl and o-fluorophenylbis(triphenylphosphinyl)nickel carboxylates.
3.  According to19F NMR data o-tolylbis(triphenylphosphinyl)nickel p-fluorobetizoate contained a highly polarized Ni-O bond.
Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 166–170, January, 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.  Dithiophosphoric acids are either not catalysts or only act as moderate catalysts as a function of the structure in reactions of decomposition of CHP.
2.  The real catalyst of decomposition of CHP in the presence of dithiophosphoric acids is the sulfuric acid formed during the oxidation of the dithiophosphoric acids, or the combination of the sulfuric acid with phosphours-containing acids.
3.  Slow and fast stages of kinetic decomposition of CHP were detected, and the kinetic parameters of the fast stage were determined.
Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 34–41, January, 1989.  相似文献   

11.
1.  The (Cp2TiCl)2-LiAlH4 system with Al/Ti from 0.25 to 1.5 catalyzes both the homogeneous hydrogenation and isomerization of allylbenzene.
2.  In an argon atmosphere, allylbenzene is isomerized to trans-propenylbenzene with 90–92% selectivity when Al/Ti=1–1.5.
3.  The possibility was demonstrated for reactivation of this catalytic system by its retreatment with LiAlH4.
Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 729–731, March, 1989.  相似文献   

12.
1.  The dipole moments of the two kinds of C-O bonds in acetals and their analogs are not identical.
2.  In formal molecules and the dimethylketal of acetone the C-O-C-O -C chains have gauche-gauche conformation, with the methyl groups lying on different sides of the O-C-O plane.
3.  The dimethylketal of tetrachlorocyclopentadienone is represented by a mixture of trans-gauche and gauche-gauche conformers.
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13.
1.  The authors have studied the formation of electron and hole paramagnetic centers in gamma-irradiated magnesium hydroxide and oxide with various degrees of dehydration.
2.  Rise in the temperature of preliminary heat treatment of the magnesium oxide causes an increase in the radiation-chemical yield of FS + centers and a decrease in that of V su centers.
3.  The thermal stability of paramagnetic centers in magnesium oxide increases as the hydroxyl group content decreases.
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14.
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   

15.
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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16.
Prehistoric metal findings from Liguria are numerous, however, even though there were many metalliferous mines, the metal-working sites have not yet been ascertained.This work discusses results on some metal objects from different archaeological sites in Liguria.The objects examined were: 1) two melting drops 2) an axe, and 3) a knife. The physico-chemical investigation techniques employed were:
–  X-ray diffraction,
–  radiography,
–  microdrawing method, followed by optical and electron scanning microscopy observations,
–  differential thermal and thermogravimetric analyses to characterize the clay core found inside a socketed knife.
This work was supported by the Italian C. N. R., Comitato Nazionale per la Scienza e la Tecnologia dei Beni Culturali, Progetto Strategico Beni Culturali.Thanks are due to the Directress of the Calvet Museum, Mrs. Jadwiga Krzepowska, for kind permission to observe and study the fusion mould.The authors thank Mr. Claudio Uliana for the measurements carried out on the S.E.M. apparatus.  相似文献   

17.
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   

18.
1.  At 20–220° on aluminum oxide and NaX, NaY, CeNaY, and HY zeolites, aliene isomerizes to methylacetylene; zeolites whose IR spectra are characterized by the presence of absorption bands of the hydroxyl groups (CeNaY, HY) are more active in this reaction.
2.  The thermal dimerization of aliene at 450° proceeds with the formation of 1,2-dimethylenecyclobutane.
3.  The oligomerization of aliene on -allylnickel bromide, applied on aluminum oxide, at 20–180° gives chiefly 1,3-dimethylenecyclobutane, the formation of which evidently proceeds through a four-membered active complex.
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19.
1.  The strong bathochromic shift of the absorption bands of aminoazo compounds in acid medium is due to the formation of a cation of quinoid structure.
2.  Aminoazo compounds are weak NH acids in aprotic polar solvents, and they form the corresponding mesomeric anions in the presence of alkalis.
3.  The synthesized aminoazo compounds are very weak NH acids, and electron-donor substituents weaken the acid properties of the amino group, while electron-acceptor substituents intensify them.
Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1513–1518, July, 1989.  相似文献   

20.
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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