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1.
1.  Oxidation of 5-R1-2R2-4H-imidazole 1,3-dioxides in methanol with lead dioxide leads to the formation of stable nitroxyl and nitronylnitroxyl radicals with methoxy groups at the -carbon atom of the radical center. The ratio between these radicals is determined by the electronic character of the substituents at the 2- and 5-positions of the heterocyclic ring.
2.  Oxidation of 4H-imidazole 1-oxides and 4H-imidazole 3-oxides in methanol with lead dioxide leads to the formation of iminonitroxyl radicals.
3.  Oxidation of 2-unsubstituted 4H-imidazole 1,3-dioxides and 4H-imidazole 3-oxides in alcohols by lead or manganese dioxides leads to 2,2-dialkoxy-substituted stable nitroxyl radicals, which are derivatives of 3-imidazoline 3-oxide and 3-imidazoline.
Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1624–1630, July, 1989.  相似文献   

2.
1.  1,2-Oxathiolan-5-one-2-oxides are readily cleaved by nucleophiles (H2O, ROH, HNR2) under mild conditions at the O-CO bond only, with the formation of the -(hydroxysulfinyl)-alkanoic acid derivatives.
2.  2,1-Benzoxathiol-3-one-1-oxide is cleaved by alcohols at both the O-CO and the O-SO bonds to give the unstable monoesters at the carboxyl and sulfinyl groups.
3.  Unlike 2,1-benzoxathiol-3-one-1-oxide, 1,2-oxathiolan-5-one-2-oxides on boiling with excess alcohols give -(hydroxysulfinyl)alkanoic acid bisesters.
For previous communication, see [1].  相似文献   

3.
1.  Ethylbenzene in acetonitrile is slowly oxidized by atmospheric oxygen to acetophenone in the presence of a catalytic amount of CrO3.
2.  Ethylbenzene is oxidized to acetophenone by iodosobenzene in acetonitrile in the air in the presence of catalytic amounts of CrO3 and -picolinic acid.
Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1185–1188, May, 1989.  相似文献   

4.
1.  The kinetics of formation of methyl 4-methyl-4-hydroxy-2-pentynoate from 3-methyl-1-butyl-3-ol and carbon monoxide in methanol in the presence of PdCl2-CuCl2-NaOAc system was studied by the method of regression analysis.
2.  Under the conditions used, the reaction was zero order with respect to CO, CuCl2, PdCl2, and NaOAc and first order with respect to the acetylenic alcohol; the energy of activation of the gross process is 68.0 kJ/mole.
Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1738–1742, August, 1988.  相似文献   

5.
1.  It was shown on the example of the reaction of 1-hydroxy-5-methyltetrazole with methyl vinyl ketone that N-hydroxytetrazoles attach to substances with activated multiple bonds. The addition products are solely the products of N(3 and 4)--oxoalkylation.
2.  Upon heating, 3- and 4--oxoalkylated 1-oxides of tetrazoles are in a tautomeric equilibrium.
Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1619–1623, July, 1989.  相似文献   

6.
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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7.
1.  2-Methyl-2-peroxytetrahydrofuran under the influence of FeSO4 or the FeSO4-CuSO4 system decomposes to give 3-acetoxypropyl radicals, which predominantly recombine to 1,6-hexanediol diacetate.
2.  When 2-methyl-2-peroxytetrahydrofuran is reduced with FeCl2, or with the FeSO4-FeCl3 system, the generated 3-acetoxypropyl radicals are oxidized to 3-acetoxypropyl chloride.
  相似文献   

8.
1.  Using seven independent methods it was found that the concentration of the active centers on the surface of-Al2O3, which are responsible for the dehydration, is (9±1)×1017 centers/m2. The catalytically active centers are identical with adsorption centers.
2.  A method of calculating the stochiometry, concentration, and thermodynamics of the surface association reactions has been developed.
3.  The first reaction step proceeds according to the associative bimolecular substitution mechanism, with the formation of an associative intermediate compound. The association enthalpy and entropy have been calculated.
  相似文献   

9.
1.  A series of C-functional derivatives of (3)-1,2-dicarbaundecaborate was synthesized and some of their properties were studied.
2.  Apparent ionization constants of acids of the (3)-1,2-dicarbaundecaborate series were measured and it was found that they are very weak carboxylic acids.
3.  Upon reaction with excess LiA1H4, under mild conditions the carbonyl, *20c \CH(OH) / \begin{array}{*{20}c} \backslash \\ {CH(OH)} \\ / \\ \end{array} , and CH2OH groups of dicarbaundecaborate ketones and alcohols are reduced to CH2 and CH3 groups, respectively.
4.  The effect of Grignard reagent on ketones and esters of the dicarbaundecarbprate series was studied and it was established that the composition of reaction products depends both on the steric hindrance of the carbonyl group and on the electron-donating effect of the (3)-1,2-dicarbaundecaborate substituent.
  相似文献   

10.
1.  N-Ethyl and N-isopropyl-3-piperidones were synthesized and the stereochemistry of their reduction was studied.
2.  The dependenceof stereochemistryof a series of reactions at the carbonyl center on bulk of the substituent on nitrogen was established.
3.  Pure a- and e-epimers of N-ethyl- and N-isopropyl-3-piperidols were separated.
  相似文献   

11.
1.  The results of calculations of the first ionization potentials of the anions of the dihydrides of 3d metals by the discrete variation X method are in good agreement with the available experimental values.
2.  The electron affinities of the MH2 molecules are close to the first ionization potentials of the corresponding anions on account of the small values of the adiabatic corrections, and vary noniaonotonically on passing along the series of 3d metals.
3.  The electron affinity of the dihydrides of the 3d metals always exceeds the electron affinity of the central atom, but varies in parallel with the latter quantity along the series.
Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 81–87, January, 1989.  相似文献   

12.
1.  It has been shown that 2-bromo-l,3,2-dioxaarsenanes exist in chair conformation with axially oriented As-Br bonds.
2.  Polarity and polarizability parameters have been found for the As-O and As-Br bonds in 2-bromo-l,3,2-dioxaarsenanes.
3.  The so-called -effect is stronger in the O2AsBr group than in the O2AsCl group.
  相似文献   

13.
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.
  相似文献   

14.
To mitigate CO2 discharged from thermal power plants, studies on CO2 fixation by the photosynthesis of microalgae using actual exhaust gas have been carried out. The results are as follows.
1.  A method is proposed for evaluating the maximum photosynthesis rate in the raceway cultivator using only the algal physical properties;
2.  Outdoor cultivation tests taking actual flue gas were performed with no trouble or break throughout 1 yr using the strain collected in the test;
3.  The produced microalgae is effective as solid fuel; and
4.  The feasibility studies of this system were performed. The system required large land area, but the area is smaller than that required for other biomass systems, such as tree farms.
  相似文献   

15.
1.  Some new -oxides were synthesized, which contain a lactam ring in the substituent and have the general structure: where R = H, CH3; OC OC2H5, and Z = CH2, CH2OCH2, (CH2)2OCH2.
2.  It was shown on the example of the synthesized glycidyl ethers that they are capable of forming polymeric products under the influence of nucleophilic agents, and also of adding water, ammonia, and diethylamine under mild conditions.
  相似文献   

16.
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   

17.
1.  A method has been developed for the intercalation of solid substances from solutions in organic solvents into graphite fluoride C2Fx.
2.  Molecules of inserted paramagnetic copper complexes and nitroxyl radicals assume oriented positions between the structural layers in graphite fluoride.
3.  The planes of molecules of bis-chelate Cu(II) complexes with acetylacetone, o-hydroxyquinoline, and phenylsalicylaldimine were determined to lie parallel to the C2Fx planes.
4.  A method has also been suggested for the preparation of samples from C2Fx·yA compounds with a higher degree of texturizing (more nearly complete orientation) than can be achieved by pelletizing.
Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 272–276, February, 1988.  相似文献   

18.
1.  Indium atoms have been obtained in aqueous solutions of univalent indium by pulse radiolysis.
2.  In0 reacts with In+ to form the dimer In 2 + .
3.  The optical characteristics of these particles, the rate constants for their formation and loss, as well as the oxidation-reduction potentials have been determined.
We thank A. G. Egorova for providing the InBr salt.  相似文献   

19.
1.  Selective hydrogenation of piperylene into n-amylenes (300C) on applied nickel sulfide was studied in the pulsed mode. It was found that NiS/SiO2 is more selective than NiS/Al2O3.
2.  Treatment of applied NiS with air at 300–500C oxidizes a significant portion of NiS into NiSO4, which gives the catalyst hydroisomerizing properties and permits obtaining up to 44% isoamylenes from piperylene. In contrast to oxidized NiS/SiO2, oxidized NiS/Al2O3 retains hydroisomerizing activity for a much longer time, which is due to the higher resistance of NiSO4 to reduction on Al2O3 than on SiO2.
3.  The data obtained indicate that reduced nickel atoms are the active sites of selective hydrogenation, while sulfur, sulfide or sulfate, is the surface modifier.
Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1477–1482, July, 1989.  相似文献   

20.
1.  Complexes of the REE, Y, and Sc with hydroxyethylethylenediaminetriacetic acid have been isolated in solid form. The hydrate compositions of the complexes have been determined.
2.  The La and Pr complexes form hydrates of different compositions. The LnL hydrates form slightly nonisostructural groups in the series La-Lu.
3.  According to thermographic analysis data, the hydrate water in the LnL·nH2O complexes of different hydrate compositions is not bonded with the same firmness.
  相似文献   

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