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1.
I. V. Kostyuchenko G. P. Okonnishnikova E. V. Shulishov Yu. V. Tomilov 《Russian Chemical Bulletin》2004,53(10):2257-2261
3-Cyano- and 3-(alkoxycarbonyl)spiro[2-pyrazoline-5,1’-cyclopropane] and 5-phenylspiro[1-pyrazoline-3,1’-cyclopropane] undergo unusual transformations into 3(5)-substituted 5(3)-(2-hydroperoxyethyl)pyrazoles in the presence of atmospheric oxygen. The conditions for the formation of hydroperoxides (e.g., in oxygen-saturated solutions of spiro[2-pyrazoline-5,1’-cyclopropanes] in CHCl3) and their conversion into (2-hydroxyethyl)pyrazoles or the corresponding nitrates under the action of nitrosating reagents were considered.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2160–2164, October, 2004. 相似文献
2.
Yu. V. Tomilov I. V. Kostyuchenko E. V. Shulishov B. B. Averkiev M. Yu. Antipin 《Russian Chemical Bulletin》2000,49(11):1919-1922
The addition of the phthalimidonitrene fragment, resulting from oxidation ofN-aminophthalimide by lead tetraacetate at −20 to −30°C, to the N=N-bond of 5-bromospirol[l-pyrazolinio-3,1′-cyclopropane]
(1) affords, apart from the stable 5-bromo-N {spiro[l-pyrazolinio-3,1′-cyclopropane]}-N-phthalimidoamide (azimine2), regioisomeric azimine3, which is completely transformed into 3-acetoxy-N-{spiro[l-pyrazolinio-5,1′-cyclopropane]}-N-phthalimidoamide (4) under the reaction conditions. The acetoxy group in this product easily undergoes nuclcophilic substitution on treatment
with McOH, NaN3, or the starting bromopyrazoline1. The structures of azimines obtained were established using NMR spectra, and the structure of the product of reaction of4 with1 was additionally proved by X-ray difraction data.
Published inIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 1949–1953, November, 2000. 相似文献
3.
Yu. V. Tomilov I. V. Kostyuchenko E. V. Shulishov O. M. Nefedov 《Russian Chemical Bulletin》1997,46(3):511-518
The reaction of diazocyclopropane generatedin situ with acrylonitrile or methyl acrylate to give 1∶1, 1∶2, and 2∶1 cycloadducts was carried out. The products resulting from
1,3-dipolar cycloaddition and subsequent isomeriation,viz., 3-cyano- and 3-methoxycarbonylspiro(2-pyrazoline-5,1′-cyclopropanes), isolated in the first step in ∼70% yield, react in
an alkaline solution with the above acrylates or diazocyclopropane as C(3)-nucleophiles to give the corresponding 3-(2′-cyanoethyl)-,
3-(2′-methoxycarbonylethyl)-, or 3-(cyclopropylazo)-1-pyrazolines. The thermal deazotization of these pyrazolines to spiropentane
derivatives was investigated.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 532–539, March, 1997. 相似文献
4.
Yu. V. Tomilov I. V. Kostyuchenko E. V. Shulishov O. M. Nefedov 《Russian Chemical Bulletin》1998,47(4):666-668
The reaction of diazocyclopropane generatedin situ with vinyl bromide occurs as regioselective 1,3-dipolar cycloaddition to give 5-bromospiro(1-pyrazoline-3,1′-cyclopropane)
in ∼60% yield. Reactions of the latter with nucleophilic reagents, which can occur both with retention and opening of the
cyclopropane ring, were studied.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 688–690, April 1998. 相似文献
5.
Yu. V. Tomilov I. V. Kostyuchenko E. V. Shulishov B. B. Averkiev M. Yu. Antipin O. M. Nefedov 《Russian Chemical Bulletin》1999,48(7):1316-1322
Oxidation ofN-aminophthalimide with lead tetraacetate in the presence of spiro(1-pyrazolinecyclopropanes) at temperature from −20°C to
−30°C resulted in the formal generation of phthalimidonitrene followed by its addition at the N=N bond of the pyrazoline ring
to form 5(3)-substitutedN-{spiro[1-pyrazolinio-3(5),1′-cyclopropane]}-N-phthalimidoamides (azimines), whose regioisomeric compositions were determined to a large extent by the nature of the substituents
in the pyrazoline ring. The structures of phthalimidoazimines were established based on the NMR spectra and X-ray diffraction
data. Thermal conversions of the resulting adducts, which proceeded either with retention or with opening of the spiro-fused
cyclopropane ring, were studied.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1328–1333, July, 1999. 相似文献
6.
I. V. Kostyuchenko E. V. Shulishov R. R. Rafikov Yu. V. Tomilov 《Russian Chemical Bulletin》2008,57(8):1712-1717
1-Pyrazolines, obtained by 1,3-dipolar cycloaddition of diazocyclopropane to N-phenyl- and N-cyclohexylmaleimides, undergo complete dediazoniation at 175 °C for 10–16 h with the formation of spiro[3-azabicyclo[3.1.0]hexane-6,1′-cyclopropane]-2,4-diones
3 (80–89%) and isomeric 3-cyclopropyl-1H-pyrrole-2,5-diones 4. On the example of 3-cyclopropyl-1-phenyl-1H-pyrrole-2,5-dione, it was shown that compounds 4 are able again to enter into 1,3-dipolar cycloaddition with diazomethane or diazocyclopropane with the reaction in the case
of diazocyclopropane being nonselective and leading to two regioisomeric pyrazolines in the ratio ∼1.7: 1, thermolysis of
which, conversely, proceeds with high selectivity and exclusively affords a spiropentane derivative. An action of the aqueous
methanol solution of sodium hydroxide on the spiropentanes fused with succinimide fragment and subsequent acidification of
the salts obtained lead to stable cis-amidoacids of spiropentane series.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1680–1685, August, 2008. 相似文献
7.
The hydrolysis of SbCl3 in hydrochloric acid solution (2.0 mol dm-3 HCl) at 0 °C yields an amor-phous product consisting of uniform spherical particles (d∼0.5 μm), which on continuous aging at the same temperature transform to larger crystals, indicated by XRD to be Sb4O5Cl2. In contrast, in the same solution kept at 25 °C crystalline particles of the same composition form directly after an induction
period and then grow with time. The final products, obtained at 0 °C and 25 °C consist of aggregated subunits. These powders
on calcination in nitrogen are converted to Sb2O3 and in air to Sb2O4.
Received: 23 June 1997 Accepted: 1 July 1997 相似文献
8.
R. R. Gataullin I. S. Afon'kin I. V. Pavlova I. B. Abdrakhmanov G. A. Tolstikov 《Russian Chemical Bulletin》1999,48(2):396-397
N-Acetyl-6-(cyclopent-1-enyl)-2-methylaniline underwent intramolecular cyclization in the presence of HCl in CH2Cl2 at 20°C to form 2,8-dimethylspiro[cyclopentane-1,4′-4′H-3,1-benzooxazine] in quantitative yield.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 398–400, February, 1999. 相似文献
9.
A. V. Varlamov D. G. Grudinin A. A. Eganov A. I. Chernyshev A. N. Levov 《Chemistry of Heterocyclic Compounds》2005,41(7):872-876
Substitution of the nitrile group by hydroxylamine and hydrazine has been effected in 1-cyanodihydrospiro[benzo-2-azepine-3,1′-cyclohexane].
From the 1-cyano and 1-hydrazino derivatives tetrahydrospiro{1,2,3- and 1,2,4-triazolo[5,1-a]benzoazepine-5,1′-cyclohexanes}
have been obtained. It was established that 1-carbamoyldihydrospiro[benzo-2-azepine-3,1′-cyclohexanes] are converted under
the conditions of the Hoffmann reaction into spiro{diaziridino[3,1-a]benzo-2-azepine-3,1′-cyclohexane{, and is reduced by
sodium borohydride to the tetrahydro derivative.
__________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 1033–1037, July, 2005. 相似文献
10.
V. R. Akhmetova E. B. Rakhimova A. B. Minnebaev R. V. Kunakova N. F. Galimzyanova 《Russian Journal of Organic Chemistry》2012,48(2):202-208
Cyclothiomethylation was performed of heterochain (O, S-S, NH) α,ω-diamines with formaldehyde and H2S in aqueous medium at 20–60°C to obtain new α,ω-bis(1,3,5-dithiazinanes). The cyclocondensation of N-(3-aminopropyl)butane-1,4-diamine
(spermidine), formaldehyde, and H2S proceeds efficiently in the medium of BuOH-H2O at 0°C and leads to the formation of previously unknown O,S-containing macroheterocycle, 1,7-dioxa-3,5,9,11-tetrathiacyclododecane.
A fungicidal activity was found in 5,5′-(3,6-dioxaoctane-1,8-diyl)bis-1,3,5-dithiazinane with respect to microscopic fungi
affecting agriculture. 相似文献
11.
Matthew J. Bernett Adrianne K. Tipton Michael T. Huggins Jonathan H. Reeder David A. Lightner 《Monatshefte für Chemie / Chemical Monthly》2000,131(3):239-249
Summary. A crystal structure determination of 2,2′-bipyrroyl (1; 2,2′-dipyrryl-diketone, bis (2-pyrrolyl)ethanedione) and its spectroscopic properties in solution are reported. In the crystal, 1 self-assembles via hydrogen bonding into supramolecular ribbons that extend indefinitely through the crystal lattice. The observed molecular
conformation is one where each pyrrole ring and adjacent carbonyl group are co-planar (torsion angle ∼ 0.9°), with the N-H
pointing in the same direction as the C=O. The two carbonyls have a transoid but not co-planar geometry with a torsion angle
of ∼128°. Adjacent molecules in the crystal are linked by pairs of intermolecular hydrogen bonds, pyrrole NH to carbonyl oxygen,
to form a matrix of polymeric chains that lie like neatly stacked, parallel streams of ribbons. Molecular mechanics calculations
on the monomer indicate an intra-molecularly hydrogen bonded planar conformation (sp, ap, sp) at the global energy minimum. In CHCl3, 1 is monomeric according to vapor pressure osmometry (MW
obs=179±10 vsċMW
calc=188). In THF, the measured molecular weight is 340±15, which corresponds best to one molecule of 1 solvated by two THF molecules (MW=322 for C10H8N2O4ċ2 C4H8O) rather than to a dimer.
Received October 21, 1999. Accepted November 2, 1999 相似文献
12.
Morphology of micron-sized monodispersed poly(butyl methacrylate)/polystyrene composite particles produced by seeded dispersion polymerization 总被引:1,自引:0,他引:1
In order to develop the seeded dispersion polymerization technique for the production of micron-sized monodispersed core/shell
composite polymer particles the effect of polymerization temperature on the core/shell morphology was examined. Micron-sized
monodispersed composite particles were produced by seeded dispersion polymerizations of styrene with about 1.4-μm-sized monodispersed
poly(n-butyl methacrylate) (Pn-BMA) and poly(i-butyl methacrylate) (Pi-BMA) particles in a methanol/water (4/1, w/w) medium in the temperature range from 20 to 90 °C. The composite particles,
PBMA/polystyrene (PS) (2/1, w/w), consisting of a PBMA core and a PS shell were produced with 2,2′-azobis(4-methoxy-2,4-dimethyl
valeronitrile) initiator at 30 °C for Pn-BMA seed and with 2,2′-azobis(isobutyronitrile) initiator at 60 °C for Pi-BMA seed. The polymerization temperatures were a little above the glass-transition temperatures (T
g) of both Pn-BMA (20 °C) and Pi-BMA (40 °C). On the other hand, when the seeded dispersion polymerizations were carried out at much higher temperatures than
the T
g of the seed polymers, composite particles having a polymeric oil-in-oil structure were produced.
Received: 14 October 1998 Accepted in revised form: 2 June 1999 相似文献
13.
Matthew J. Bernett Adrianne K. Tipton Michael T. Huggins Jonathan H. Reeder David A. Lightner 《Monatshefte für Chemie / Chemical Monthly》2000,40(12):239-249
A crystal structure determination of 2,2′-bipyrroyl (1; 2,2′-dipyrryl-diketone, bis (2-pyrrolyl)ethanedione) and its spectroscopic properties in solution are reported. In the crystal, 1 self-assembles via hydrogen bonding into supramolecular ribbons that extend indefinitely through the crystal lattice. The observed molecular conformation is one where each pyrrole ring and adjacent carbonyl group are co-planar (torsion angle ∼ 0.9°), with the N-H pointing in the same direction as the C=O. The two carbonyls have a transoid but not co-planar geometry with a torsion angle of ∼128°. Adjacent molecules in the crystal are linked by pairs of intermolecular hydrogen bonds, pyrrole NH to carbonyl oxygen, to form a matrix of polymeric chains that lie like neatly stacked, parallel streams of ribbons. Molecular mechanics calculations on the monomer indicate an intra-molecularly hydrogen bonded planar conformation (sp, ap, sp) at the global energy minimum. In CHCl3, 1 is monomeric according to vapor pressure osmometry (MW obs=179±10 vsċMW calc=188). In THF, the measured molecular weight is 340±15, which corresponds best to one molecule of 1 solvated by two THF molecules (MW=322 for C10H8N2O4ċ2 C4H8O) rather than to a dimer. 相似文献
14.
D. L. Lipilin A. Yu. Tyurin O. Yu. Smirnov A. M. Churakov Yu. A. Strelenko V. A. Tartakovsky 《Russian Chemical Bulletin》2006,55(7):1239-1242
Treatment of 2-(tert-butyl)-1,2,3,4-benzotetrazinium tetrafluoroborates with sodium thiocyanate afforded 2-(tert-butylazo)phenyl isothiocyanates 3, which exist in equilibrium with 2-(tert-butyl)-1,2,4-benzotriazine-3(2H)-thiones 3′. The equilibrium depends on the substituents R in the benzene ring: the percentage of the open isomer 3 is about 20% for R = H or Me; for R = Cl or Br, the equilibrium is completely shifted to cyclic isomer 3′. The equilibrium is slow on the time scale of the 1H and 13C NMR experiments. For compounds 3a/3′a (R = H), the spectra at 24 °C show two sets of signals, while those at 0 °C contain only signals for isomer 3′a.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1192–1195, July, 2006. 相似文献
15.
Matthew L. Milling Jermaine Cooley Dmitriy V. Liskin Edward J. Valente 《Structural chemistry》2009,20(6):969-973
Abstract
Oxidation of 1,4-bis(4′-oxo-2′,2′-dimethylpent-2-yl)benzene with hypochlorite produces 1,4-bis(3′-carboxy-2′-methylbut-2-yl)benzene and 3-(4′-carboxyphenyl)-3,3-dimethylpropanoic acid. Cyclization of this mixture forms 3,3,7,7-tetramethyl-1,2,3,5,6,7-hexahydro-s-indacen-1,5-dione, 3,3,7,7-tetramethyl-1,2,3,5,6,7-hexahydro-as-indacen-1,5-dione (5) and 6-carboxy-3,3-dimethyl-1-indanone (6). Ketoacid (6) is converted to the arylpyran pseudoacid 7-carboxy-3-hydroxy-4,4-dimethylisobenzopyran-1-one (7). In the crystal structure of (7), carboxylic acid and the pseudoacid groups each form complementary dimer hydrogen bonds linking the molecules in chains. Contact O···O distances reflect their differing energetics, with pseudoacyl O···O at 2.78(1)Å and carboxylic O···O at 2.62(1)Å. 相似文献16.
O. V. Masloboishchikova E. G. Khelkovskaya-Sergeeva V. I. Bogdan T. V. Vasina L. M. Kustov 《Russian Chemical Bulletin》2006,55(4):656-660
The bimetallic Ru-Pt/Al2O3 catalysts with an overall metal content of 1 wt. % and Pt: Ru weight ratios from 1: 3 to 3: 1 were studied. The catalytic
activity for cyclohexane and benzene transformations, including hydrogenation, hydrogenolysis, and skeletal isomerization
of the initial substrates and products of intermediate transformations, was studied at temperatures 180–350 °C and H2 pressures from 1.0 to 5.0 MPa. The maximum yield of n-hexane from cyclohexane and benzene was obtained on the catalysts with a ruthenium content of 0.75–1.0%, being ∼29–30 wt.%
at 40% selectivity. The selectivity to form n-hexane decreases with an increase in the cyclohexane conversion and is almost independent of the composition of the Ru-Pt
system. On the catalysts under study, benzene is converted to the same products but at temperatures by 60 °C lower as compared
to cyclohexane conversion.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 633–637, April, 2006. 相似文献
17.
T. N. Komarova A. S. Nakhmanovich T. E. Glotova T. E. Glotova V. N. Elokhina A. L. Albanov V. A. Lopyrev 《Russian Chemical Bulletin》1997,46(1):195-196
Substituted thioureas react with 1-bromo-2-benzoylacetylene in various solvents at 20°C to give the correspondingN-substituted 4-benzoyl-2-(R-imino)-3-R′-thiazolium bromides.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 199–200, January, 1997. 相似文献
18.
The complexes M[La(C2O4)3]⋅xH2O (x=10 for M=Cr(III) and x=7 forM=Co(III)) have been synthesized and their thermal stability was investigated. The complexes were characterized by elemental
analysis, IR, reflectance and powder X-ray diffraction (XRD) studies. Thermal investigations using TG, DTG and DTA techniques
in air of chromium(III)tris(oxalato)lanthanum(III)decahydrate, Cr[La(C2O4)3]⋅10H2O showed the complex decomposition pattern in air. The compound released all the ten molecules of water within ∼170°C, followed
by decomposition to a mixture of oxides and carbides of chromium and lanthanum, i.e. CrO2, Cr2O3, Cr3O4, Cr3C2, La2O3, La2C3, LaCO, LaCrOx (2<x<3) and C at ∼1000°C through the intermediate formation of several compounds of chromium and lanthanum at ∼374, ∼430 and ∼550°C.
Thecobalt(III)tris(oxalato)lanthanum(III)heptahydrate, Co[La(C2O4)3]⋅7H2O becomes anhydrous around 225°C, followed by decomposition to Co3O4, La2(CO3)3 and C at ∼340°C and several other mixture species of cobalt and lanthanum at∼485°C. The end products were identified to be
LaCoO3, Co3O4, La2O3, La2C3, Co3C, LaCO and C at ∼ 2>1000°C. DSC studies in nitrogen of both the compounds showed several distinct steps of decomposition
along with ΔH and ΔSvalues. IR and powder XRD studies have identified some of the intermediate species. The tentative mechanisms for the decomposition
in air are proposed.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
19.
Krishna C. Majumdar Subhojit Ghosh 《Monatshefte für Chemie / Chemical Monthly》2002,133(10):1317-1323
Summary. Regioselective heterocyclization of 3-(cyclohex-2′-enyl)-4-hydroxy-6-methyl pyran-2-one with various reagents afforded different
heterocycles. With N-iodosuccinimide in acetonitrile at 0–5°C it gave 6-methyl-9′-iodo-2′-oxabicyclo[3.3.1]nonano[3,2-c]pyran-2-one, with C5H5NHBr3 or C6H12N4HBr3 in CHCl3 at 0–5°C it furnished 6-methyl-9′-bromo-2′-oxabicyclo[3.3.1]nonano[3,2-c]pyran-2-one. Cold concentrated H2SO4 lead to 6-methyl-2′-oxabicyclo[3.3.1]nonano[3,2-c]pyran-2-one, whereas PdCl2(PhCN)2 in C6H6 at 80°C afforded 9-methyl benzofuro[3,2-c]pyran-2-one.
Corresponding author. E-mail: kcm@klyuniv.ernet.in
Received December 27, 2001. Accepted (revised) March 1, 2002 相似文献
20.
Sushanta Saha Prodyut Kumar Sarkar Ambikesh Mahapatra 《Transition Metal Chemistry》2006,31(3):389-395
The reaction between Pd(N,N′)Cl2 [N,N′ ≡ 1-alkyl-2-(arylazo)imidazole (N,N′) and picolinic acid (picH) have been studied spectrophotometrically at λ = 463 nm in MeCN at 298 K. The product is [Pd(pic)2] which has been verified by the synthesis of the pure compound from Na2[PdCl4] and picH. The kinetics of the nucleophilic substitution reaction have been studied under pseudo-first-order conditions.
The reaction proceeds in a two-step-consecutive manner (A → B → C); each step follows first order kinetics with respect to
each complex and picH where the rate equations are: Rate 1 = {k′0 + k′2[picH]0} × [Pd(N,N′)Cl2] and Rate 2 = {k′′0 + k′′2[picH]0}[Pd(N,O)(monodentate N,N′)Cl2] such that the first step second order rate constant (k′2) is greater than the second step second order rate constant (k′′2). External addition of Cl− (as LiCl) suppresses the rate. Increase in π-acidity of the N,N′ ligand, increases the rate. The reaction has been studied
at different temperatures and the activation parameters (Δ‡H° and Δ‡S°) were calculated from the Eyring plot. 相似文献