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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:
相似文献
| – | - 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. |
2.
S. G. Smirnov A. N. Rodionov K. L. Rogozhin O. P. Syutkina E. M. Panov D. N. Shigorin K. A. Kocheshkov 《Russian Chemical Bulletin》1976,25(2):316-318
| 1. | A trap method has been used to identify and quantitatively determine radical products formed in a primary photochemical act. |
| 2. | In the photolysis of solutions of compounds with the general formula Ph3M at 300°K the quantum yield of the radical products increases substantially with increasing atomic number of the element. |
3.
| 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%. |
4.
K. L. Rogozhin A. N. Rodionov S. G. Smirnov D. N. Shigorin O. P. Syutkina V. I. Lodochnikova K. A. Kocheshkov 《Russian Chemical Bulletin》1976,25(2):319-322
| 1. | There is a regular increase in the energy of the lowest singlet and triplet excited levels in the aromatic derivatives of the elements C, Si, Ge, Sn and N, P, As, Sb, Bi, which is consistent with the quantum-mechanical model of the mixing of the electronic states of the aromatic system with states involving p and s orbitals of the heteroatom with different energies and symmetries. |
| 2. | The yields of the radiative electronic transitions regularly decrease, and the probabilities of nonradiative intramolecular electronic transitions increase. |
| 3. | The temperature effects inthe 300–77°K range in the electronic absorption spectra have been found and are associated with a postulated change in the spatial configuration of the compounds investigated. |
5.
Kozachenko A. G. Uryupin A. B. Spivak L. L. Grigor'eva A. A. Matrosov E. I. Kabachnik M. I. Mastryukova T. A. 《Russian Chemical Bulletin》1976,25(7):1561-1563
| 1. | The method of potentiometric titration in transfer circuits was used to determine the dissociation constants of phosphorus monothioacids ABPSOH in abs. ethanol and nitromethane at 25°. In these solvents the thione-thiol equilibrium is shifted toward the thione forms. |
| 2. | The differentiating effect of nitromethane on the strength of the studied phosphorus monothioacids was established. |
6.
| 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. |
7.
G. A. Artamkina A. Yu. Mil'chenko I. P. Beletskaya O. A. Reutov 《Russian Chemical Bulletin》1988,37(12):2550-2556
| 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. |
8.
| 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. |
9.
B. K. Nefedov N. S. Sergeeva T. V. Zueva E. M. Shutkina Ya. T. Eidus 《Russian Chemical Bulletin》1976,25(3):565-569
| 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. |
10.
B. A. Arbuzov S. G. Vul'fson G. G. Butenko O. A. Samarina A. B. Teitel'baum A. N. Vereshchagin 《Russian Chemical Bulletin》1976,25(1):75-81
| 1. | The ellipsoids of polarizability of dimethylsulfone, sulfuryl chloride, and methanesulfonyl chloride were determined, and the nonadditivity of the parameters of the bonds in the sulfonyl chloride group was demonstrated. |
| 2. | Substituted methane sulfonyl chloride exist in gauche conformations. |
| 3. | In benzenesulfonyl chloride and a series of its para-substituted derivatives, the aryls are situated in the C-S-Cl plane; the para-nitro group induces a 35° rotation. |
11.
| 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. |
12.
G. Grossman G. Komber G. Kroshvitts P. A. Kirpichnikov N. A. Mukmeneva D. G. Pobedimskii 《Russian Chemical Bulletin》1989,38(1):26-32
| 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. |
13.
R. G. Kostyanovskii V. P. Leshchinskaya R. K. Alekperov G. K. Kadorkina L. L. Shustova Yu. I. Él'natanov G. L. Gromova A. É. Aliev I. I. Chervin 《Russian Chemical Bulletin》1988,37(11):2315-2323
| 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. |
14.
Yu. V. Kuznetsov L. G. Stolyarova V. P. Lezina L. D. Smirnov 《Russian Chemical Bulletin》1989,38(7):1494-1500
| 1. | New halogen derivatives of 1-ethyl-2-methyl-, 2-methyl- and 5-hydroxybenzimidazole were obtained. |
| 2. | A method for the chlorination of aromatic compounds by an alcoholic solution of hydrogen chloride in the presence of hydrogen peroxide was proposed, which enables carrying out the reaction with a high yield. |
| 3. | The reactivity of the series of 5(6)-hydroxybenzimidazole derivatives during the electrophilic substitution (halogenation) was shown to be as follows: 1-ethyl-2-methyl-5-hydroxybenzimidazole >5(6)-hydroxybenzimidazole 2-methyl-5-hydroxybenzimidazole. |
15.
Zh. L. Dykh L. I. Lafer V. I. Yakerson A. M. Rubinshtein A. M. Taber I. V. Kalechits S. S. Zhukovskii V. É. Vasserberg 《Russian Chemical Bulletin》1976,25(2):282-286
| 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. |
16.
| 1. | 3,6-Di-tert-butyl-o-quinone (I) forms both hydrogen-bonded and donor-acceptor complexes with 3,6-di-tert-butylpyrocatechol (II) and 3,5-di-tert-butylpyrocatechol (III) in CCl4, and n-hexane solutions. The concentrations of these two types of complexes are approximately equal. |
| 2. | Photoreduction of quinone (I) at 77 K occurs in both the H-bonded and donor-acceptor complexes. |
| 3. | A new mechanism has been proposed to account for radical formation and stabilization in mixed complexes with both H-bonding and donor-acceptor interactions. |
17.
L. D. Belyakova G. A. Gerasimova L. T. Zhuravlev G. V. Kudryavtsev G. V. Lisichkin N. S. Ovchinnikova N. P. Platonova T. I. Shevchenko 《Russian Chemical Bulletin》1989,38(5):885-891
| 1. | When silicas are modified with amines, not all surface silanol groups participate in the chemical reaction. |
| 2. | When amine-modified silica gels are heated, water is produced; the maximum rate of the formation of gas occurs at 625 and 750 K. Destruction of the modifying layer begins with the liberation of ammonia at T > 640 K. |
| 3. | Adsorption of SO2 and CO2 on aminated silicas is determined by the surface concentration of amino groups, by their nature, and by their mutual position. |
18.
A. Teies Gonsalo A. I. Donskikh V. N. Kulagin Yu. V. Moiseev G. M. Tseitlin 《Russian Chemical Bulletin》1976,25(5):1156-1158
| 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. |
19.
F. M. Stoyanovich G. B. Chermanova Ya. L. Gol'dfarb R. G. Karpenko 《Russian Chemical Bulletin》1976,25(7):1503-1508
| 1. | p-Bis(tert-butylsulfonyl)benzene (I) and 2,5-bis(tert-butylsulfonyl)thiophene (II) when treated with n-BuLi are capable of replacing one of the sulfonyl groups by the n-butyl group. |
| 2. | The conditions were found where sulfone (II) is metalated in the position of the thiophene ring. |
| 3. | Lithium 2-thienyimercaptide is metalated in the free position. |
20.
| 1. | Hexafluorides may have a positive second electron affinity, i.e., their doubly-charged anions may be stable toward the loss of an electron. |
| 2. | Species with maximum possible second and higher electron affinity should be sought among polynuclear MnkXnk+1 compounds, where k is the maximal formal valence of atom M and X is a monovalent electronegative ligand. |