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1.
M. O. Talismanova A. A. Sidorov G. G. Aleksandrov V. N. Charushin S. K. Kotovskaya V. P. Ananikov I. L. Eremenko I. I. Moiseeva 《Russian Chemical Bulletin》2008,57(1):47-55
The reactions of palladium(II) salts with 2-mercaptobenzimidazole (HL) and its 5,6-difluorinated derivative (HLF) were investigated. In the presence of hydrochloric acid, PdCl2 and K2PdCl4 react with HL and HLF in the ethanol—water and acetonitrile—water systems to form the mono-nuclear dicationic complexes [Pd(HL)4]Cl2 (1) and [Pd(LF)4]Cl2 (2). In the absence of HCl, the reactions afford the tetranuclear complex Pd4[(L)2(μ3-S,N-(L))2(μS,N-(L))4] (3). The reaction of triethylamine with an ethanolic solution of 3 leads to degradation of 3 and the formation of the lantern-type dinuclear complex Pd2[(μ2-(L)4] (4), in which the palladium atoms are in the nonequivalent coordination environment, PdN4 and PdS4. The reaction of K2PdCl4 with HL or HLF in the THF—water or acetonitrile—water systems (for the reaction with HLF) in the presence of Et3N produces the lantern-type dinuclear complexes Pd2[(μS,N′-(L3))4] and Pd2[(μ-S,N′-(LF))4] (5), in which the metal atoms are in the equivalent coordination environment (cis-PdN2S2).
Dedicated to Academician G. A. Tolstikov on the occasion of his 75th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 45–52, January, 2008. 相似文献
2.
L. A. Musina E. E. Shul’ts L. A. Krichevskii S. M. Adekenov M. M. Shakirov G. A. Tolstikova 《Russian Chemical Bulletin》2006,55(2):331-337
The oxidation of N-acetyl-and N-benzoylanabasine with the tert-butyl hydroperoxide (TBHP)— MoCl5 system or MCPBA proceeds selectively at the nitrogen atom of the pyridine ring. The oxidation of N-methylanabasine under similar conditions gives a mixture of stereo-isomeric N-oxides at the piperidine nitrogen atom, their ratio depending on the reagent used. The oxidation of anabasine by TBHP— MoCl5 or MCPBA is accompanied by dehydrogenation and results in anabaseine N-oxide. The reactions of anabasine and anabaseine pyridine N-oxides with acetic anhydride were investigated. The substituted 1H-3-pyridin-2-ones were prepared.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 322—328, February, 2006. 相似文献
3.
Kenjiro Onimura Yuan Zhang Michihiro Yagyu Tsutomu Oishi 《Journal of polymer science. Part A, Polymer chemistry》2004,42(18):4682-4692
Chiral (S)-(−)-N-1-cyclohexylethylmaleimide [(S)-CEMI] and (R)-(+)-N-1-cyclohexylethylmaleimide [(R)-CEMI] were synthesized successfully and then polymerized with chiral complexes of (−)-sparteine or (S,S)-(1-ethylpropylidene)bis(4-benzyl-2-oxazoline) [(S,S)-Bnbox] and organometal as initiators in toluene or tetrahydrofuran to obtain optically active polymers. The effects of the polymerization conditions on the optical activity and structure of poly(N-1-cyclohexylethylmaleimide)s were investigated with gel permeation chromatography, circular dichroism, specific rotation, and 13C NMR measurements. Poly[(R)-CEMI] obtained with dimethylzinc (Me2Zn)/(S,S)-Bnbox had the highest specific rotation ([α]435 = +323.7°). Complexes of Bnbox and diethylzinc or Me2Zn were used very effectively as chiral initiators for the asymmetric anionic polymerization of (S)-CEMI and (R)-CEMI. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4682–4692, 2004 相似文献
4.
E. B. Benetsky A. S. Safronov T. B. Grishina P. V. Petrovskii V. A. Davankov K. N. Gavrilov 《Russian Chemical Bulletin》2006,55(12):2187-2189
P,N-Bidentate oxazoline phosphite containing an acyclic phosphorus center with [(1S)-endo]-(−)-borneol fragments and its palladium chelate complex [Pd(η-C3H5)(η2-P,N)]BF4 were synthesized for the first time. The use of this new ligand in Pd-catalyzed asymmetric amination of 1,3-diphenylpropenyl
acetate with pyrrolidine afforded the product with 86% ee.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2106–2108, December, 2006. 相似文献
5.
Wai-Kwok Wong Tat-Wai Chik Kin-Ning Hui Ian Williams Xue Feng Thomas C.W. Mak Chi-Ming Che 《Polyhedron》1996,15(24):4447-4460
The interaction of optically pure 1R,2R-diammoniumyclohexane mono-(+)-tartrate and 1S,2S-diammoniumcyclohexane mono-(−)-tartrate with 2 equiv. of o-(diphenylphosphino)benzaldehyde in the presence of 2 equiv. of potassium carbonate in a refluxing ethanol/water mixture gave the optically pure condensation products N,N′-bis[o-(diphenylphosphino)benzylidene]-1R,2R-diiminocyclohexane[1R,2R-cyclohexyl-P2N2, (R,R)-I] and N,N′-bis[o-(diphenylphosphino)benzylidene]-1S,2S-diiminocyclohexane [1S,2S-cyclohexyl-P2N2, (S,S)-I], respectively, in good yield. Reduction of optically pure (R,R)-I and (S,S)-I with NaBH4 in ethanol gave the optically pure reduced products N,N′-bis[o-(diphenylphosphino)benzylidene]-1R,2R-diaminocyclohexane[1R,2R-cyclohexyl-P2N2H4, (R,R)-II] and N,N′-bis[o-diphenylphosphine)benzylidene]-1S,2S-diaminocyclohexane[1S,2S-cyclohexyl-P2N2H4, (S,S)-II], respectively, in good yield. The coordination behaviour of I and II toward salts of CuI and AgI have been examined. The interaction of [Cu(C)3CN)4][X] (X = ClO4−, PF6−) with 1 equiv. of optically pure L4 [L4 = (R,R)-I, (S,S)-I, (R,R)-II and (S,S)-II] gave the corresponding optically pure [CuL4][X] complexes, III–VI IIIa, L4 = (R,R)-I, X = PF6− IIIb, L4 = (R,R)-I, X = ClO4− IV, X = PF6−; Va, L4 = (R,R)-II, X = PF6−, Vb L4 = (R,R)-II, X= ClO4−, VI L4 = (S,S)-II, X = PF6−, in good yield. For the CuI complexes, the L4 ligand acted as a tetradentate ligand. However, a variable-temperature 31P[1H] NMR study of IIIb shows that at ambient temperature one of the imino groups of the tetradentate ligand undergoes rapid dissociation to form a tridentate ligand. The interaction of AgBF4 with 1 equiv. of otpically pure L4 [L4 = (R,R)-I, (S,S)-I, (R,R)-II and (S,S)-II gave the corresponding optically pure [AgL4][BF4] complexes, VII–X VII L4 = (R,R)-I; VIII, L4 = (S,S)-I; IX,L4 = (R,R)-II; X, L4 = (S,S)-II], in good yield. For the AgI complexes, the L4 ligand acted as a tetradentate ligand with the two amino groups coordinated unsymmetrically to the silver. A variable temperature 31P [1H] NMR study of VII suggests that at high temperature the complex exists as a tri-coordinated complex. The structurers of IV and IX were established by X-ray diffraction studies. 相似文献
6.
The cyclopropylcarbinyl rearrangement of (1R,1′ S,2S)-1-(3-diisopropylamino-3-oxo-propyl)-2-(1-hydroxyethyl)cyclopropane and the participation of the amide moiety in the intramolecular
process smoothly affords the (2′ E,5S)- N,N-diisopropyl-N-[5-(but-2′-enyl)tetra-hydrofuran-2-yridene ] ammonium salt. 相似文献
7.
The dissociation constants of 3-methyl-1-phenyl-{p-[N-(pyrimidin-2-yl)sulfamoyl]phenylazo}-2-pyrazolin-5-one and metal-ligand stability constants of its complexes with some transition
metal ions have been determined potentiometrically in 0.1 M-KCl and ethanol—water mixture (30 vol. %). The order of the stability
constants of the formed complexes increases in the sequence Mn2+, Co2+, Ni2+, Cu2+, La3+, Hf3+, UO
2
2+
, Zr4+. The effect of temperature was studied and the corresponding thermodynamic parameters (ΔG, ΔH, and ΔS) were derived and discussed. The dissociation process is nonspontaneous, endothermic, and entropically unfavourable. The
formation of the metal complexes was found to be spontaneous, exothermic, and entropically favourable.
Abstracted from his M.Sc. Thesis. 相似文献
8.
Prithwiraj Byabartta 《Transition Metal Chemistry》2005,30(8):978-986
The reaction of ctc-[Ru(RaaiR′)2Cl2] (3a–3i) [RaaiR′=1-alkyl-2-(arylazo)imidazole, p-R—C6H4—N=N— C3H2NN(1)—R′, R=H, OMe, NO2, R′=Me, Et, Bz] with KS2COR′′ (R′′=Me, Et, Pr, Bu or CH2Ph) in boiling dimethylformamide afforded [RuII{o-S—C6H4(p-R-)—N=N—C3H2NN(1)—R′}2] (4a–4i), where the ortho-carbon atom of the pendant phenyl ring of both ligands has been selectively and directedly thiolated. The newly formed tridentate
thiolate ligands are bound in a meridional fashion. The solution electronic spectra exhibit a strong MLCT band near 700 nm
and near 550 nm, respectively in DCM. The molecular geometry of the complexes in solution has been determined by H n.m.r.
spectroscopy. Cyclic voltammograms show a Ru(II)/Ru(III) couple near 0.4 V and an irreversible oxidation response near 1.0
V due to oxidation of the coordinated thiol group, along with two successive reversible ligand reductions in the range −0.80–0.87
V (one electron), −1.38–1.42 V (one electron). Coulometric oxidation of the complexes at 0.6 V versus SCE in CH2Cl2 produced an unstable Ru(III) congener. When R=Me the presence of trivalent ruthenium was proved by a rhombic e.p.r. spectrum
having g1=2.349, g2=2.310. 相似文献
9.
V. P. Kirin V. A. Maksakov A. V. Virovets P. A. Petukhov S. A. Popov A. V. Tkachev 《Russian Chemical Bulletin》2000,49(8):1440-1447
Reactions of the triosmium clusters Os3(CO)11(NCMe) (1) and Os3(CO)10(NCMe)2 (2) with terpene derivatives,viz., (1S,3S,4R,6R)-3-(N,N-dimethylamino)-4-amino-3,7,7-trimethylbicyclo [4.1.0]heptane (3). (3bR,4aR)-(3,4,4-trimethyl-3b,4,4a,5-tetrahydrocyclopropa [3,4]cyclopenta[1,2-c]pyrazol-1-yl)acetic acid (4a), and (3bR,4aR)-3-(3,4,4-trimethyl-3b, 4,4a,5-tetrahydrocyclopropa[3,4]cyclopenta[1,2-c]pyrazol-1-yl)propionic acid (4b), were studied. A complex with the terminally coordinated ligand is formed in the first step of the reaction of diamine3 with cluster1. Heating of the resulting complex is accompanied by activation of one of the methyl groups of the ligand to form diastereomers
with the bridging tricyclic dihydroimidazole ligand. One of these diastereomers was studied by X-ray diffraction analysis
and its absolute configuration was established. Pyrazolycarboxylic acids react with cluster2 as simple organic acids and are coordinated as a bridge at the Os—Os bond through the carboxyl group.
Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1447–1454, August, 2000. 相似文献
10.
A. V. Timshina S. A. Rubtsova I. N. Alekseev P. A. Slepukhin A. V. Kuchin 《Russian Journal of Organic Chemistry》2010,46(3):363-367
(1R,1′R,2S,4R)-1,7,7-Trimethylspiro[bicyclo[2.2.1]heptane-2,2′-[1,3]dithiolane] 1′-oxide, (1R,2S,3′R,4R)-1,7,7-trimethylspiro[bicyclo[2.2.1]heptane-2,2′-[1,3]dithiolane] 1′,1′,3′-trioxide, and (1R,4R)-1,7,7-trimethylspiro[bicyclo[2.2.1]heptane-2,2′-[1,3]dithiolane] 1′,1′,3′,3′-tetraoxide were synthesized by oxidation of
camphor ethylene dithioacetal with m-chloroperoxybenzoic acid at different substrate-tooxidant ratios. The structure of the products was proved by IR and NMR
spectroscopy and X-ray analysis. 相似文献
11.
A. S. Sagiyan A. E. Avetisyan S. M. Djamgaryan L. R. Djilavyan E. A. Gyulumyan S. K. Grigoryan N. A. Kuz'mina S. A. Orlova N. S. Ikonnikov V. S. Larichev V. I. Tararov Yu. N. Belokon 《Russian Chemical Bulletin》1997,46(3):483-486
Asymmetric synthesis of β-N-substituted (S)-α,β-diamino acids was accomplished by Michael addition of amines to the NiII complex of the Schiff base derived from (S)-2-[N-(N′-benzylprolyl)amino]benzophenone (BPB) and dehydroalamine. Diastereoselectivity of the reaction is kinetically and thermodynamically
controlled. The chiral auxiliary reagent, BPB, can be recovered and reused.
Translated fromIzvestiya Akademii Nauk. Serya Khimicheskaya, No. 3, pp. 504–507, March, 1997. 相似文献
12.
Rakesh K. Rath G. A. Nagana Gowda Akhil R. Chakravarty 《Journal of Chemical Sciences》2002,114(5):461-472
2D NMR spectroscopy has been used to determine the metal configuration in solution of three complexes, viz. [(η6-p-cymene)Ru(L*)Cl] (1) and [(η6-p-cymene)Ru(L*)(L′)] (C1O4) (L′ = H2O,2; PPh3,3), where L* is the anion of (S)-(l-phenylethyl)salicylaldimine. The complexes exist in two diastereomeric forms in solution. Both the (RRu,Sc)- and (SRu,Sc)-diastereomers display the presence of attractive CH/π interaction involving the phenyl group attached to the chiral carbon
and the cymene ring hydrogens. This interaction restricts the rotation of the C*-N single bond and, as a result, two structural
types with either the hydrogen atom attached to the chiral carbon (C*) or the methyl group attached to C* in close proximity
of the cymene ring protons get stabilized. Using 2D NMR spectroscopy as a tool, the spatial interaction involving these protons
are studied in order to obtain the metal configuration(s) of the diastereomeric complexes in solution. This technique has
enabled us to determine the metal configuration as (R
Ru,S
c) for the major isomers of 1–3 in solution. 相似文献
13.
Takashi Yokoyama Kazuhiro Ikemoto Takatsugu Kihara Kouhei Teramura Keisuke Uryu Kohji Shimizu Motoki Bitoh Kohji Matsuzaki Michio Zenki 《Journal of solution chemistry》2006,35(5):639-657
Coordination equilibrium constants (K
NiS) of some donor solvent molecules to 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecanenickel(II) ([Ni(Me4[12]aneN4)]2+) were determined in nitrobenzene (a noncoordinating bulk solvent). The first (K
NiS1) and second stepwise coordination equilibrium constants (K
NiS2) for 1,4,7,10-tetraazacyclododecanenickel(II) ([Ni([12]aneN4)]2+), 1,4,8,11-tetraazac yclotetradecane- nickel(II) ([Ni([14] aneN4)]2+), 1,4,8,11-tetrathiacyclotetra-decanenickel(II) ([Ni([14]aneS4)]2+) were also reinvestigated. The K
NiS values for [Ni(Me4[12]aneN4)]2+ were compared to those of [Ni([12]aneN4)]2+, (1R,4S, 8R,11S)-1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecanenickel(II) (R,S,R,S-[Ni(Me4[14]aneN4)]2+), R,R,S,S-[Ni(Me4[14]aneN4)]2+, [Ni([14]aneN4)]2+, and [Ni([14]aneS4)]2+. Coordination of pyridine (Py), N,N,N′,N′-tetramethylurea (TMU), and N,N-dimethylacetamide (DMA) to [Ni(Me4[12]aneN4)]2+ was observed, although these donor solvent molecules did not coordinate to R,S,R,S-[Ni(Me4[14]aneN4)]2+. The K
NiS values for Py, TMU, and DMA are 7.9, 2.8, and 9.0 dm3⋅mol−1, respectively. Some hydrogen-bonding waters were coordinated to R,S,R,S-[Ni(Me4[14]aneN4)]2+, but such waters did not coordinate to [Ni(Me4[12] aneN4)]2+. Also, the K
NiS2 values were larger than the corresponding K
NiS1 values for [Ni([14]aneS4)]2+. Furthermore, the K
NiS1 values for [Ni([12]aneN4)]2+ were the largest among these nickel(II) complex cations. The K
NiS, K
NiS1, and K
NiS2 values are discussed in terms of properties of the donor solvents and steric strains of these nickel(II) complex cations. 相似文献
14.
R. A. Novikov R. R. Rafikov E. V. Shulishov Yu. V. Tomilov 《Russian Chemical Bulletin》2010,59(10):1930-1936
A new method for the synthesis of (1R,4S,5S)-4-hydroxymethyl-3-oxabicyclo[3.1.0]hexan2-one, the cyclopropane analog of (S)-5-hydroxypent-2-en-4-olide, has been suggested based on oxidation of (1S,2S,4R,6R)-7,9-dioxatricyclo[4.2.1.02,4]nonan-5-one. Oxidation of cyclobutanones, spirojoined with the fragments of 6,8-dioxabicyclo[3.2.1]oct-2-ene, 6,8-dioxabicyclo[3.2.1]octane
(at position 4), or 7,9-dioxatricyclo[4.2.1.02,4]nonane (at position 5), upon the action of m-chloroperoxybenzoic acid or the KMnO4-H2SO4-H2O system leads to the corresponding spirojoined butanolides in 73–85% yields. The same cyclobutanones easily undergo the four-membered
ring opening upon the action of dilute H2SO4 at 50–90 °C to form 6,8-dioxabicyclo[3.2.1]octane-4- or 7,9-dioxatricyclo[4.2.1.02,4]nonane-5-propionic acid. 相似文献
15.
A new chromone-substituted dihydrotriflavonol, (2S,3S)[6-{(3S) 3″,5″-dihydroxy-6″-methoxydihydrochromone}5,3′,4′,5′-tetrahydroxy-7-methoxy-3-O-8-dihydroflavone]2 3-O-8[6-{(3S) 3″,5″-dihydroxy-6″methoxydihydrochromone}3,5,3′,4′,5′-pentahydroxy-7-methoxydihydroflavonol] was isolated from the leaves
of Anogeissus pendula. The structure was determined by UV, 1H NMR, 13C NMR, HMBC, and CD data. 相似文献
16.
Masoud Salavati-Niasari 《Transition Metal Chemistry》2008,33(4):443-452
Mn(II) complexes of 12-membered macrocyclic ligands with three different donating atom sets (N2O2, N2S2 and N4) in the macrocyclic ring have been encapsulated in the nanopores of zeolite-Y by the Flexible-Ligand Method (FLM). The complexes
were entrapped in the nanocavity of zeolite-Y by a two-step process in the liquid phase: (i) adsorption of 1,2-di(o-aminophenyl-, amino, oxo, thio)ethane in the supercages of the zeolite and (ii) in situ condensation of the Mn(II) precursor
complex ([Mn(N2X2)]2+) with glyoxal or biacetyl. The new host–guest nanocatalysts, [Mn([R]2–N2X2)]2+–NaY (R = H, CH3; X = NH, O, S), have been characterized by various physico-chemical methods. These complexes, both in their free states and
as host–guest nanocatalysts, were used for oxidation of cyclohexene with tert-butylhydroperoxide (TBHP) oxidant in different solvents. Di-2-cyclohexenylether was identified as the main product. 2-Cyclohexene-1-one,
2-cyclohexene-1-ol and 1-(tert-butylperoxy)-2-cyclohexene were obtained as minor products. [Mn([H]2–N4)]2+–NaY was found to give the best reactivity and selectivity. 相似文献
17.
The structure of the molecular complex between the chiral selector (+)1-(3-allylpropyl)-(5R,8S,10R)-N,N-diethyl-N′-[6-methyl ergolin-8-yl]urea, C23H33N4O, (allyl-terguride) and the HPLC more retained (S)-enantiomer of dansyl-tryptophan, C23H23N3O4S, has been determined. It is a part of the study on the chiral recognition mechanism of ergot alkaloids, when used in chiral
stationary phases (CSPs) for the separation of racemic mixture of organic acids by liquid chromatographic methods. At the
pH of crystallization conditions, which mimic those corresponding to the best enantiodiscriminative activity, each molecule
of (S)-dansyl-tryptophan is locked to a molecule of allyl-terguride by hydrogen bonds and by C–H···π edge-to-face interactions. 相似文献
18.
F. A. Gimalova G. M. Khalikova S. A. Torosyan D. Z. Akhmetshina M. S. Miftakhov 《Russian Journal of Organic Chemistry》2012,48(2):180-183
The oxidation with SeO2 of a methyl group linked to an sp2-hybridized carbon in the product of the intramolecular iodoetherification of cis-carveol afforded (1R,5R,7S)-7-iodomethyl-7-methyl-6-oxabicyclo[3.2.1]-oct-3-en-4-carbaldehyde and [(1R,5R,7S)-7-iodomethyl-7-methyl-6-oxabicyclo[3.2.1]oct-3-en-4-yl]methanol that were oxidized to methyl (1R,5R,7S)-7-iodomethyl-7-methyl-6-oxabicyclo[3.2.1]oct-3-en-4-carboxylate. The latter by the Zn-promoted opening of the γ-oxide ring
was converted into the target chiral block, methyl (4R,6R)-6-hydroxy-4-(prop-1-en-2-yl)cyclohex-1-encarboxylate. 相似文献
19.
K. I. Kuchkova A. N. Aryku A. N. Barba P. F. Vlad Ya. Lipkovskii Yu. A. Simonov V. Kh. Kravtsov 《Chemistry of Natural Compounds》2011,47(2):223-228
Products from the reaction of 11-dihomodriman-8α-ol-12-one with several reagents such as MeSO3SiMe3, CF3SO3SiMe3, Sc(CF3SO3)3, conc. H2SO4 in EtOH (30% solution), and Amberlist-15 ion-exchange resin were studied. 11-Dihomodrim-8(9)-en-12-one and its oxime were
synthesized. The reaction of its oxime with H3PO4 (86%) or CF3CO2H produced (1S,2S,4aS,8aS)-2,5,5,8a-tetramethyldecahydro-1H-naphtho [1,2-e]-3-methyl-4,5-dihydro-[1,2,6]-oxazine; with p-TsCl in Py, (1S,2S,4aS,8aS)-2,5,5,8a-tetramethyldecahydro-1H-naphtho[1,2-d]-2-methylpyrroline-N-oxide; and with PCl5 in Et2O, 11-acetylaminodrim-8(9)-ene and 11-methylaminooxodrim-8(9)-ene. 相似文献
20.
Yu. N. Belokon' V. I. Maleev T. F. Savel'eva M. A. Moskalenko D. A. Pripadchev V. N. Khrustalev E. V. Vorontsov A. S. Sagiyan E. P. Babayan 《Russian Chemical Bulletin》2005,54(4):981-987
Diastereoselective synthesis of new NiII complexes of Schiff bases of (S)-2-[N-(N-benzylprolyl)amino]benzophenone with (2S,4R)-4-bromoglutamic, (1S,2R)- and (1S,2S)-1-aminocyclopropane-1,2-dicarboxylic acid monoesters was performed.
Dedicated to Corresponding Member of the Russian Academy of Sciences E. P. Serebryakov on the occasion of his 70th birthday.
__________
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 958–963, April, 2005. 相似文献