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1.
1.  Nonsterically hindered primary arylamines react with hexafluoroacetone benzenesulfonyl- and trifluoroacetylimines to give stable gem-diamino compounds.
2.  The presence of substituents at the nitrogen of the arylamine destabilizes these gem-diamino compounds, with the formation of C2- and C4-alkylation products. With hexafluoroacetone trifluoroacetylimine, C2-alkylation is accompanied by heterocyclization to give 1-substituted 2,4,4-tris(trifluoroacetyl)-1,4-dihydroquinazolines.
3.  N,N-Dialkylanilines are regioselectively alkylated at C4.
For previous communication, see [1].  相似文献   

2.
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   

3.
1.  Nitroxyl biradicals of the triazine, N,N-bis(triazinyl)ethylenediamine, N,N-bis(triazinyl)piperazine, and s-nitropyrimidine series have been prepared.
2.  The ESR spectra of liquid and frozen solutions of these biradicals have been obtained and N. - O group separations calculated.
3.  Toluene solutions of (II), (V), (VI), and (X) biradicals contain at least four different conformations, each with its own value of the exchange integral.
4.  In one of the biradical (V) conformations, spin interaction exchange is through the chain of atoms linking the N.-O fragments.
  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 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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6.
1.  The alkylation of 2,2,4-trimethyl-1,2-dihydroquinoline and its derivatives by hexafluoroacetone occurs regioselectively and leads, depending on the conditions, to 6-(2-hydroxyhexafluoro-2-propyl)-2,2,4-trimethyl-1,2-dihydroquinolines or the 6,8-disubstituted products.
2.  The reaction of methyl trifluoropyruvate with 2,2,4-trimethyl-1,2-dihydroquinoline gave the product of C8-alkylation, accompanied by lactamization.
3.  The oxidation of 6-(2-hyhdroxyhexafluoro-2-propyl)-2,2,4-trimethyl-1,2-dihydroquinoline by hydrogen peroxide in the presence of sodium tungstenate gave a stable nitroxyl radical.
Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 472–475, February, 1989.  相似文献   

7.
1.  A comparison of the results of studying the products of thermal polymerization of phenylacetylene by mass spectrometry and13C NMR showed that tetra-substituted cyclohexadiene and/or benzene rings are the terminal groups in polyphenylacetylene macromolecules.
2.  The terminal cyclohexadiene rings are formed as a result of chain breaking by intramolecular cyclization of the propagating end.
Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 67–70, January, 1988.  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.  A procedure has been developed for carrying out the reaction between ozone and paraffins directly in an EPR resonator.
2.  EPR signals of the products of the reaction between ozone and paraffins in the liquid phase have been obtained.
  相似文献   

10.
1.  The13C NMR spectra of several 1-alkoxy(phenoxy)-2-phenoxycyclopropanes have been studied.
2.  The configurations of substituted cyclopropanediol ethers have been established with the aid of1H and13C NMR spectroscopy.
  相似文献   

11.
1.  Depending on the conditions, the reaction of methyl aryl ketones with phosphorus pentachloride leads to products from substitution of the carbonyl oxygen by chlorine, αβ-dichlorovinylarenes, or compounds with higher degrees of chlorination.
2.  By eliminating a molecule of hydrogen chloride under the influence of an equimolar amount of sodium amide in ammonia, substituted, α,β-dichloroethylenes give high yields of the respective 2-chloroacetylene.
3.  The synthesis of a series of ethynyl- and β-chloroethynylpyrazoles from methylpyrazolyl ketones was realized.
  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.
  相似文献   

13.
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   

14.
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.
  相似文献   

15.
1.  Replacing Na+ ions by Ca2+in zeolites leads to a significant shift of the region in which thermally stimulated polarographic [TSD] current peaks appear toward higher temperatures.
2.  Reducing the cation content in zeolites leads to a decrease in the intensity of TSD currents.
3.  The data obtained-can be explained by the differences in the distributions of the cations between different crystallographic positions in the zeolite lattices.
Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 1969–1972, September, 1988.  相似文献   

16.
1.  The N-chloro-N-nitroamides of arylsulfonic acids react with olefins to give a mixture of the N- and O--chloroalkylation products of the nitroamides.
2.  When arylsulfonic acid N-chloro-N-nitroamides react with monosubstituted ethylene derivatives the nitroamide group adds to the least hydrogenated carbon atom of the multiple bond.
  相似文献   

17.
The energy metabolism of a mammalian cell line grown in vitro was analyzed by substrate consumption rates and metabolic flux measurements. The data allowed the determination of the relative importance of the pathways of glucose and glutamine metabolism to the energy requirements of the cell. Changes in the substrate concentrations during culture contributed to the changing catalytic activities of key enzymes, which were determined.
1.  A murine B-lymphocyte hybridoma (PQXB1/2) was grown in batch culture to a maximum cell density of 1–2×106 cells/mL in 3–4 d. The intracellular protein content showed a maximum value during the exponential growth phase of 0.55 mg/106 cells. Glutamine was completely depleted, but glucose only partially depleted to 50% of its original concentration when the cells reached a stationary phase following exponential growth.
2.  The specific rates of glutamine and glucose utilization varied during culture and showed maximal values at the midexponential phase of 2.4-nmol/min/106 cells and 4.3 nmol/min/106 cells, respectively.
3.  A high proportion of glucose (96%) was metabolized by glycolysis, but only limited amounts by the pentose phosphate pathway (3.3%) and TCA cycle (0.21%).
4.  The maximum catalytic activity of hexolinase approximates to the measured flux of glycolysis and is suggested as a rate-limiting step. In the stationary phase, the hexokinase activity reduced to 11% of its original value and may explain the reduced glucose utilization at this stage.
5.  The maximal activities of two TCA cycle enzymes were well above the measured metabolic flux and are unlikely to pose regulatory barriers. However, the activity of pyruvate dehydrogenase was undetectable by spectrophotometric assay and explains the low level of flux of glycolytic metabolites into the TCA cycle.
6.  A significant proportion of the glutamine (36%) utilized by the cells was completely oxidized to CO2.
7.  The measured rate of glutamine transport into the cells approximated to the metabolic flux and is suggested as a rate-limiting step.
8.  Glutamine metabolism is likely to occur via glutaminase and amino transaminase, which have significantly higher activities than glutamate dehydrogenase.
9.  The calculated potential ATP production suggests that, overall, glutamine is the major contributor of cellular energy. However, at the midexponential phase, the energy contribution from the catabolism of the two substrates was finely balanced—glutamine (55%) and glucose (45%).
  相似文献   

18.
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   

19.
1.  n-Nitro-p-toluenesulfonic acid N-nitroamide adds to olefin oxides to give N--hydroxyalkylation products. The direction of the addition to monosubstituted oxides is such that the nitroamide anion adds to the most sterically available carbon atom.
2.  m-Nitro-p-toluenesulfonic acid N-nitroamide reacts with unsubstituted ethylenimine to give the ethylenimine salt of the nitrosulfonamide.
3.  m-Nitro-p-toluenesulfonic acid N-nitroamide reacts with an N-acylated ethylenimine or trimethylenimine with ring opening and the respective formation of N-- or N--amidoalkylation products.
  相似文献   

20.
1.  The condensation of 1,2-hydroxylamino oximes with biacetyl leads to 1-hydroxy-2-acetyl-2,4,5,5-tetrasubstituted 3-imidazoline 3-oxides.
2.  When 1-hydroxy-2-acetyl-2,5,5-trimethyl-4-phenyl-3-imidazoline 3-oxide is oxidized the CH3CO group is cleaved to give the 5H-imidazole 1,3-dioxide.
3.  Stable nitroxyl radicals were obtained when the 1-hydroxy-2-oximiaoethyl-2,4,5,5-tetrasubstituted 3-imidazoline 3-oxides are oxidized.
  相似文献   

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