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1.
T. N. Fedotova G. G. Aleksandrov G. N. Kuznetsova 《Russian Journal of Inorganic Chemistry》2011,56(5):698-706
Reactions of acetamide with platinum(II) diamines [Pt(N,N-DimeEn)Cl2], [Pt(Tm)Cl2], and [Pt(N,N-DimeTm)Cl2] (N,N-DimeEn = (CH3)2N(CH2)2NH2, Tm = NH2(CH2)3NH2, N,N-DimeTm = (CH3)2N(CH2)3NH2) with preliminary precipitation of chlorine ions by silver salts gave binuclear Pt(II) acetamidates [Pt2(CH3)2N(CH2)2NH2)2(μ-NHCOCH3)2](NO3)2 · H2O (I), [Pt2(NH2(CH2)3NH2)2)(μ-NHCOCH3)2](NO3)2 · H2O (II), and [Pt2(CH3)2N(CH2)3NH2)2(μ-NHCOCH3)2](HSO4)2 (III), whose crystal structures were determined. Crystals of I are monoclinic: a = 14.459(2) Å, b = 17.197(3) Å, c = 9.822(2) Å, β = 105.923(10)°, V = 3348.6(8) Å3, space group P2(1)/c, Z = 4, R hkl = 0.0419 for 6663 reflections. Complex I is a binuclear acetamidate with bridging (NHCOCH3)? ligands, one of which is bound to two Pt atoms through the N and O atoms, and the other ligand is bound only through the N atom. The Pt-Pt distance is 2.987(1) Å. Crystals of II are monoclinic: a = 10.213(7) Å, b = 13.373(9) Å, c = 16.533(11) Å, β = 97.971(9)°, V = 2236(3) Å3, space group P2(1)/n, Z = 4, R hkl = 0.557 for 6462 reflections. The Pt-Pt distance is 3.057(1) Å. Crystals of III are monoclinic: a = 10.557(12) Å, b = 18.531(2) Å, c = 14.4744(17) Å, β = 108.705(2)°, V = 2682(5) Å3, space group P2(1)/n, Z = 4, R hkl = 0.569 for 8506 reflections. The Pt-Pt distance is 3.202(1) Å. Complexes II and III are binuclear acetamidates, in which two chelating Pt(Tm) or Pt(N,N-DimeTm) moieties are coordinated through the N and O atoms of (NHCOCH3)? cis-bridges. 相似文献
2.
The rate of substitution of aqua ligands from three mononuclear platinum(II) complexes, namely [Pt{2-(pyrazol-1-ylmethyl)pyridine}(H2O)2](ClO4)2, [Pt(H 2 Py)]; [Pt{2-(3,5-dimethylpyrazol-1-ylmethyl)pyridine}(H2O)2](ClO4)2, [Pt(dCH 3 Py)] and [Pt{2-[(3,5-bis(trifluoromethyl)pyrazoly-1-ylmethyl]pyridine}(H2O)2](ClO4)2, [Pt(dCF 3 Py)] by thiourea, N,N-dimethylthiourea and N,N,N′,N′-tetramethylthiourea, was studied in aqueous perchloric acid medium of constant ionic strength. The substitution reactions were investigated under pseudo-first-order conditions as a function of nucleophile concentration and temperature using UV/Visible and stopped-flow spectrophotometries. The observed pseudo-first-order rate constants, \( k_{{{\text{obs }}\left( {1/2} \right)}} \), for the stepwise substitution of the first and second aqua ligands obeyed the rate law: \( k_{{{\text{obs}}\left( {1/2} \right)}} = k_{{2 \left( { 1 {\text{st/2nd}}} \right)}} \left[ {\text{Nu}} \right] \). The first substitution reaction takes place trans to the pyrazole ligand, while the second entering nucleophile is stabilised at the reaction site trans to the pyridine ligand. The rate of substitution of the first aqua ligand from the complexes followed the order: Pt(dCF 3 Py) > Pt(H 2 Py) > Pt(dCH 3 Py), while that of the second was Pt(H 2 Py) ≈ Pt(dCF 3 Py) > Pt(dCH 3 Py). Lower pK a values were found for the deprotonation of the aqua ligand cis to the pyrazole ring. Density functional theory calculations were performed to support the interpretation of the experimental results. 相似文献
3.
Meliha Burcu Gürdere Onur Gümüş Ayse Sahin Yaglioglu Yakup Budak Mustafa Ceylan 《Research on Chemical Intermediates》2017,43(3):1277-1289
Novel 1,4-phenylene-bis-N-acetyl- (3a–h) and bis-N-phenylpyrazoline derivatives (4a–h) were obtained by addition of hydrazine hydrate and phenylhydrazine to bis-chalcone derivatives (1a–h) in acetic acid and acetic acid/ethanol for 4 and 8 h in reflux conditions, respectively. The structures of the obtained bis-N-acetylpyrazoline and bis-N-phenylpyrazoline derivatives were characterized by nuclear magnetic resonance (NMR) and infrared (IR) spectroscopic methods and elemental analysis. Compounds 3a–h and 4a–h were investigated to evaluate their anticancer activities against C6 (rat brain tumor cells) and HeLa (human uterus carcinoma) in vitro using a dose-dependent assay from 5 to 100 μM with 5-fluorouracil (5-FU) as standard anticancer drug. Compound 3a showed higher cell-selective activity compared with 5-FU against HeLa cells. Compounds 3a–h (except 3d) were shown to have better activities than 5-FU against both cells, particularly at high concentration. Compound 4c showed higher cell-selective activity compared with 5-FU against C6 cells. Compound 3a may be particularly promising as an anticancer drug against HeLa cells. 相似文献
4.
Shotaro Iwata Hidenori Takahashi Asami Ihara Kumiko Hiramatsu Junya Adachi Soichiro Kawamorita Naruyoshi Komiya Takeshi Naota 《Transition Metal Chemistry》2018,43(2):115-125
The syntheses, structures, and solid-state emission characteristics of trans-bis(salicylaldiminato)Pt(II) complexes bearing N-aromatic functionalities are described herein. A series of Pt complexes bearing various N-phenyl (1) and N-(1-naphthyl) (2) groups on the salicylaldiminato ligands were prepared by reacting PtCl2(CH3CN)2 with the corresponding N-salicylidene aromatic amines, and the trans-coordination and crystal packing of these complexes were unequivocally established based on X-ray diffraction (XRD). Complexes with 2,6-dimethylphenyl (1c), 2,6-diisopropylphenyl (1d), 1-naphthyl (2a), and 1-(2-methylnaphthyl) (2b) groups on the N atoms exhibited intense phosphorescent emission at ambient temperature in the crystalline state, while those with phenyl (1a), 2,6-dibromophenyl (1b), and 2,6-bis(N,N-dimethylamino)phenyl (1e) functionalities were either less emissive or non-emissive under the same conditions. XRD analyses identified significant intramolecular interactions between Pt and H atoms of the N-aryl functionalities in the emissive crystals of 1c, 1d, and 2a. These interactions were evidently an important factor associated with intense emission at ambient temperature. 相似文献
5.
I. P. Pozdnyakov N. M. Storozhok N. P. Medyanik S. A. Krekov V. E. Borisenko A. P. Krysin V. F. Plyusnin V. P. Grivin 《Russian Chemical Bulletin》2015,64(6):1319-1326
The products of photolysis of N-substituted salicylic acid amides, viz., 2-hydroxy-3-tert-butyl-5-ethylbenzoic acid N-(4-hydroxy-3,5-di-tert-butylphenyl)amide (1) and 2-hydroxybenzoic acid N-[3-(4-hydroxy-3,5-di-tert-butylphenyl)prop-1-yl]amide (2), in heptane were studied by optical spectroscopy and stationary and nanosecond laser photolysis (Nd: YAG laser, 355 nm). It was shown by the method of partial deuteration of amides 1 and 2 that they exist in both the unbound state and as complexes with intraand intermolecular hydrogen bond. Amides 1 and 2 are subjected to photolysis, which results in the formation of a triplet state and phenoxyl radicals RO? presumably due to the absorption of the second photon by the excited singlet state. The formation of radical products due to N–H bond ionization was not observed. The main channel of decay of the triplet state and radicals RO? is triplet–triplet annihilation and recombination (k r ≈ 2.3?108 L mol–1 s–1), respectively. The UV irradiation of compounds 1 and 2 leads to the excitation of the amide groups, and no formation of radical products due to N–H bond ionization was observed. 相似文献
6.
Pavle Mocilac Mark Farrell Alan J. Lough Christian Jelsch John F. Gallagher 《Structural chemistry》2018,29(4):1153-1164
Crystal structures of 4-chloro-N-(4-chlorobenzoyl)-N-(2-pyridyl)benzamide (I) Clpod, 3-chloro-N-(3-chlorobenzoyl)-N-(2-pyridyl)benzamide (II) Clmod and 2-chloro-N-(2-chlorobenzoyl)-N-(2-pyridyl)benzamide (III) Clood together with three methylated analogues, Mpod, Mmod and Mood, are presented herein. The Clxod acyclic imides are produced from reacting the 4-/3-/2-chlorobenzoyl chlorides (Clx) with 2-aminopyridine (o), respectively, together with their benzamide analogues Clxo; the Mxod/Mxo triad are produced similarly and in good yield. The five Clxod, Mpod and Mmod structures adopt the open transoid conformations as expected, but Mood crystallises with cisoid oriented benzoyl groups, and this conformation was unexpected, though not unknown. Halogen bonding contacts and weak hydrogen bonding C-H···N/O/π contacts are noted in the structures lacking strong hydrogen bonding donor atoms/groups but possessing a variety of strong and weaker acceptor atoms/groups. For Clxod, contact studies show that both hydrogen and carbon account for a high percentage of elements (70–75%) on the molecular surface and being the most abundant have C···H forming 26–30% of the contacts. Contact enrichment ratios are an indicator of the likelihood of chemical species to form intermolecular interactions with themselves and other species. The C-H···N and C-H···O are the most enriched (with EHN?>?2.15), indicating that these weak hydrogen bonds are the driving force in the Clxod crystal packing formation. For Mxod, the C···H contact type at 40–52% is the most abundant contact type and C-H···O and C-H···N weak hydrogen bonds dominate with enrichment values in the 1.48–1.78 range. In Mxod, N/O···N/O contacts are effectively absent, except for Mpod (0.2%, N···N contacts) and both H···H and C···C non-polar contacts are moderately impoverished while the C···H interactions are slightly enriched (E?=?1.1–1.21). 相似文献
7.
Jan Zitko Barbora Servusová-Vaňásková Pavla Paterová Lucie Navrátilová František Trejtnar Jiří Kuneš Martin Doležal 《Chemical Papers》2016,70(5):649-657
N-Phenylpyrazine-2-carboxamides (anilides of pyrazinoic acids with simple substituents in various positions) were previously shown to possess significant biological activities in vitro, markedly anti-mycobacterial and photosynthesis-inhibiting activity. Based on structure-activity relationships (SAR) extracted from previously published series, 25 new anilides of non-substituted pyrazinoic acid (POA), 5-CH3-POA, 6-Cl-POA, 5-tert-butyl-POA and 5-tert-butyl-6-Cl-POA were designed and synthesised. The phenyl part was substituted with simple hydrophobic substituents chosen from methyl and halogens. 5-tert-Butyl-N-(5-fluoro-2-methylphenyl)pyrazine-2-carboxamide (9), N-(3-chloro-4-methylphenyl)-5-methylpyrazine-2-carboxamide (12), 6-chloro-N-(3-chloro-4-methylphenyl)pyrazine-2-carboxamide (13) and 6-chloro-N-(5-iodo-2-methylphenyl)pyrazine-2-carboxamide (18) possessed whole cell anti-mycobacterial activity in vitro against Mycobacterium tuberculosis H37Rv with minimum inhibitory concentration (MIC) of around 10 μM. Importantly, no cytotoxicity in the HepG2 model was detected in vitro at the concentrations tested and the estimated IC50 values were in hundreds of μM, indicating promising selectivity. N-(3-Chloro-4-methylphenyl)pyrazine-2-carboxamide (11) and N-(4-chloro-2-iodophenyl)pyrazine-2-carboxamide (21) exerted significant activity against Mycobacterium kansasii with MIC 12.6 μM and 8.7 μM, respectively. No activity was detected against Mycobacterium avium. SAR were in accordance with those observed for the derivatives previously published. 相似文献
8.
A. S. Antsyshkina G. G. Sadikov I. A. Solonina M. N. Rodnikova 《Russian Journal of Inorganic Chemistry》2007,52(10):1561-1566
Two ethylenediamine derivatives—N-(2-ammoniumethyl)carbamate HN(COO?)CH2CH2N+H3 (I) and tetraacetylethylenediamine (H3CC(O))2NCH2CH2N(C(O)CH3)2 (II) (synthesized for the first time)—have been synthesized and characterized by X-ray crystallography. Compounds I and II are isolated as minor admixtures upon an attempt to synthesize ethylenediamine complexes of lanthanum and neodymium nitrates, respectively. The crystals of I and II are monoclinic: a = 7.778 Å, b = 8.060 Å, c = 7.568 Å, β = 95.73°, Z = 4, space group P21/c (I); a = 5.946, b = 10.255, c = 9.343 Å, β = 95.72°, Z = 2, space group P21/c (II). The bond lengths and bond angles lie within the corresponding standard values. Compounds I and II have different conformations of the N-C-C-N ethylenediamine moiety: gauche in I and trans in II, and the corresponding torsion angles are equal to 66.6° and 180°, respectively. 相似文献
9.
Vad. V. Negrebetsky E. P. Kramarova D. E. Arkhipov A. A. Korlyukov A. G. Shipov Yu. I. Baukov 《Russian Chemical Bulletin》2015,64(8):1808-1813
Bis[(2,2-dimethyl-4-oxo-2H-benzo[e][1,3]oxazin-3(4H)-yl)methyl]dichlorosilane (1) and -germane (2) were synthesized by the reaction of 2,2-dimethyl-3-(trimethylsilyl)-2H-benzo[e][1,3]oxazin-3(4H)-one with bis(chloromethyl)dichlorosilane and -germane, respectively, taken in a ratio of 2 : 1. The structures of these compounds were determined and their stereodynamic behavior in solution was studied by multinuclear (1H, 13C, and 29Si) and twodimensional (1H, 13C COSY, HETCOR) NMR spectroscopy. The 29Si NMR spectroscopic study of a solution of complex 1 provides evidence that the silicon atom in this complex is pentacoordinate. The X-ray diffraction study showed that the germanium atom in complex 2 in the solid state is hexacoordinate. The permutation isomerization in the coordination units of complexes 1 and 2 was found and investigated by dynamic 1H NMR spectroscopy. Different mechanisms of stereodynamic transformations are suggested and discussed. 相似文献
10.
A 3 × 3 isomer grid of nine Methylphenyl-N-pyridinylcarbamates (CxxM) is reported with seven CxxM crystal structures at 294 K (xx = pp, pm, po, mp, op, om, oo; x = para-, meta-, ortho), where Cx = pyridinyl ring (as C5NH4NH-) and xM is representative of –C(=O)OC6H4CH3. All seven carbamate crystal structures aggregate via N–H…N intermolecular interactions with the three CpxM carbamates having C(6) zigzag chains, CmpM with C(5) zigzag chains and three ortho-pyridine CoxM structures as hydrogen-bonded dimers with graph set \(R_{2}^{2}\) (8) and augmented by flanking C–H…O contacts. The CpoM crystal structure crystallises with 0.25 CHCl3 per carbamate molecule and solvent channels aligning along the a-axis direction. Conformational analyses of the nine minimised CxxM structures in gas phase are detailed for comparisons with the solid-state structures and demonstrate similarities between both structural methods. The modelling results also demonstrate the problems associated with pendant ortho-groups sterically clashing in the CmoM and CooM structures and methods to find a reasonable estimate of the CxxM conformational landscape. 相似文献
11.
V. V. Sharutin O. K. Sharutina K. A. Khnykina 《Russian Journal of Inorganic Chemistry》2016,61(2):180-182
Tetraphenylantimony N-benzoylglycinate (I) has been synthesized by the reaction between pentaphenylantimony and N-benzoylglycine in toluene. According to X-ray diffraction data, the antimony atom in a molecule of complex I has a trigonal bipyramidal coordination to the oxygen atom in axial position. The Sb?Ceq, Sb?Cax, and Sb?O bond lengths are 2.116(6)?2.138(6), 2.183(6), and 2.200(4) Å, respectively. The intramolecular Sb?O=C distance between the carbonyl oxygen atom and the central antimony atom is 3.35(2) Å. 相似文献
12.
Zorica D. Petrović Jelena Đorović Dušica Simijonović Snežana Trifunović Vladimir P. Petrović 《Chemical Papers》2018,72(9):2171-2180
N-Salicylidene and N-vanillidene anil Schiff bases SB-1–5 were evaluated for their iron-coordinating properties. For this purpose, reactions with Fe(III) chloride were performed. The obtained results showed that salicylaldehyde bases SB-1 and SB-2 are the best coordinating ligands among the investigated SBs. The corresponding complexes are obtained in good yield and investigated using UV–Vis spectrophotometry and IR spectroscopy. The inhibitory potential of SB-1–5 against iron-containing enzyme lipoxygenase (LOX) was also tested. Salicylidene bases exerted better activity then vanilliden. The cytotoxic in vitro activities against human breast carcinoma MDA-MB-231 and human colon carcinoma HCT-116 cell lines were determined. Based on these results, SB-1 and SB-2 can be considered as interesting compounds for further in vivo investigations. 相似文献
13.
O. G. Strukov V. B. Kondrat’ev Z. V. Vlasova V. A. Petrunin 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2017,91(1):100-105
Conformers of the biologically active compounds CH3P(O)(OR)(SCH2CH2NR 2 ′ ), where (I) R = i-C4H9, R′ = C2H5 and (II) R = C2H5, R′ = i-C3H7, are calculated within the AM1 level of theory. The elongated and twisted forms with maximum and minimum distances between a nitrogen atom and those of a phosphorus tetrahedron, respectively, and bearing a syn and anti oriented alkoxy group relative to a phosphoryl oxygen, are studied. It is found that the differences between the energy, electronic, and geometric parameters of these forms are apparent in differences between their properties, e.g., the ability to participate in complexation and protonation, reactions that to some extent simulate the interaction between a substance and a biological object. 相似文献
14.
Cyclocondensation reaction of 3-hydrazinyl-2-naphthoic acid with diphenyl-N-cyanoimidocarbonate furnished the target 2-phenoxy-benzo[g][1,2,4]triazolo[1,5-a]quinazolin-5(4H)-one (1) in high yield. Alkylation, thionation and chlorination of the lactam group in the compound 1 produced a variety of derivatives 2–17. Their structures were characterized by NMR and HREI-MS analyses. 相似文献
15.
V. O. Gel’mboldt L. Kh. Minacheva E. V. Ganin V. S. Sergienko M. M. Botoshanskii 《Russian Journal of Inorganic Chemistry》2009,54(12):1891-1894
The complex [(CH3)2NC(NH2)NHC(NH2)NH2]SiF6 (I) was synthesized and its structure was determined by X-ray crystallography. The crystals are monoclinic: a = 7.4346(10) Å, b = 12.7628(10) Å, c = 11.0828(10) Å, β 104.080(10)°, V = 1020.01(18) Å3, ρcalc = 1.780 g/cm3, μ(MoK α) = 0.302 mm?1, Z = 4, space group P21/c. The crystals of I are composed of SiF 6 2? anions (Si-F, 1.657(2)–1.699(2) Å) and N,N-dimethylbiguanidinium (H2L2+) cations combined in a framework by interionic H-bonds NH···F. In the cations, protonation sites are the terminal imide groups. 相似文献
16.
Yanmei Chen Bin Hu Bin Xu Suyun Zhang Fengying Zhou Yahong Li 《Russian Journal of Inorganic Chemistry》2012,57(3):386-389
Two new square planar complexes with the formula Co(L)2 · CH3OH (1) and Ni(L)2 · CH3OH (2) (HL = HN{C(Me)=NH}2 = N-acetimidoylacetamidine) have been synthesized by solvothermal reactions in methanol/acetonitrile. N-acetimidoylacetamidine ligand was derived from the self-condensation reaction of acetonitrile, and the reaction was promoted by the cooperation of M(II) (M = Co in 1 and M = Ni in 2) with diphenylcarbazide. 1 and 2 are characterized by single crystal X-ray diffraction, elemental analysis and infrared spectrum. Both complexes crystallize in the monoclinic space group P21/c with a = 9.329(6) Å, b = 11.494(7) Å, c = 13.040(8) Å, β = 92.945(11)°, V = 1396.3(16) Å3 and Z = 4 for 1, and a = 9.323(4)Å, b = 11.512(5) Å, c = 13.020(6)Å, β = 92.819(7)°, V = 1395.7(10)Å3 and Z = 4 for 2. 相似文献
17.
A. A. Fedorov Sh. E. Duisenbaev V. V. Razin M. A. Kuznetsov E. Linden 《Russian Journal of Organic Chemistry》2007,43(2):231-240
Reaction of diphenyldiazomethane with methyl phenylpropiolate in diethyl ether alongside the expected methyl triphenyl-3H-pyrazole-4-and-5-carboxylates (I and II) (38 and 24%) gave rise also to 8% of methyl 3,5-diphenyl-1-(1-ethoxyethyl)-1H-pyrazole-4-carboxylate. The main thermolysis product obtained from 4-methoxy-carbonyl derivative I was methyl 1,3,5-triphenyl-1H-pyrazole-4-carboxylate, whereas from regioisomer II formed predominantly methyl 4,4,5-triphenyl-4H-pyrazole-3-carboxylate and 1-methoxycarbonyl-2,3,3-triphenylcyclopropene that was a minor product of 3H-pyrazole I thermolysis. Addition of concn. H2SO4 to the solutions of methyl triphenyl-3H-pyrazole-4-and-5-carboxylates in AcOH resulted in fast regioselective isomerization of the 3H-pyrazole derivatives into the corresponding 4H-pyrazoles. 相似文献
18.
A. E. Amr N. A. A. Hafez K. A. Ali M. A. Al-Omar H. A. Ghabbour 《Russian Journal of General Chemistry》2016,86(8):1944-1947
2-Dimethylamino methylenechromanone 1 reacted with 4H-1,2,4-triazol-3-amine in acetic acid to give only one isolated product which was identified by X-ray study as 6H-chromeno[3,4-e][1,3,4]triazolo[2,3-a]-pyrimidine. The molecular structure of 3, C12H8N4O, was determined to be monoclinic, P21/c, a = 16.3875(5), b = 8.8378(3), c = 13.8392(5) Å, β = 101.190(1)°, V = 1966.22(11) Å3, Z = 8. 相似文献
19.
A new class of piperazine-based 2-benzothiazolylimino-4-thiazolidinones has been efficiently prepared via highly accelerated N-formylation of N-isopropylpiperazine by the use of a mild heterogeneous catalyst, sulfated tungstate. Heterocyclization of N-(benzo[d]thiazol-2-yl)-2-chloroacetamides (3a–j) by use of NH4SCN in ethanol under reflux efficiently furnished the intermediates 2-benzothiazolyliminothiazolidin-4-ones (4a–j). These were treated with 4-isopropylpiperazine-1-carbaldehyde (2) to prepare the final products 5a–j. The structures of the new derivatives were confirmed by elemental analysis and use of spectroscopic data (FTIR and 1H NMR). Their pharmacological potential as promising antimicrobial agents was determined in vitro against bacteria and a fungus; the lowest minimum inhibitory concentrations (MIC) observed were in the range 4–8 µg/mL. 相似文献
20.
(μ2-Oxo)-bis[dichloro(Z-2-chloro-1-trimethylsilylethenyl)tellurium(IV)] (III) was prepared by electrophilic addition of TeCl4 to trimethylethynylsilane in CHCl3 at room temperature. The reaction is the first example of the anti-Markownikoff type addition of TeCl4 to terminal acetylenes affording as an intermediate the 1:1 adduct [Z-1-(trimethylsilyl)-2-chlorovinyl]tellurium trichloride (II). The latter is converted into III by a sequence of successive reactions of hydrolysis and dehydration. The structure of compound III was proved by the of multinuclear (1H, 13C, 29Si, 125Te) NMR spectroscopy and XRD analysis. Compound III is the first example of structurally characterized C-TeCl2-O fragment. 相似文献