Synthesis,structure and chemical properties of hypervalent germanium compounds,derivatives of lactams with a fragment

The results of studies aimed at elaborating methods for synthesizing penta- and hexacoordinated organogermanium derivatives containing lactamo-N-methyl and related bidentate ligands and investigating their structure and reactivity are reviewed. In these compounds the germanium coordination units include one or two O(or S)-Ge-X or N-Ge-X (X — an electron-deficient group) hypervalent fragments.The review is based on the report at the conference Workshop on the Modern Problems of Heteroorganic Chemistry, Moscow, May 8–13, 1993.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 982–993, June, 1994.     

SNH Amidation of 5-Nitroisoquinoline: Access to Nitro- and Nitroso Derivatives of Amides and Ureas on the Basis of Isoquinoline

For the first time, amides and ureas based on both 5-nitroisoquinoline and 5-nitrosoisoquinoline were obtained by direct nucleophilic substitution of hydrogen in the 5-nitroisoquinoline molecule. In the case of urea and monosubstituted ureas, only 5-nitrosoisoquinoline-6-amine is formed under anhydrous conditions.     

Synthesis and metal complexation studies of [2n]thiacalix[m]arene[m]pyrazine

Novel [2_n]thiacalixarenepyrazine and [2_n]thiacalixarenetriazine systems were synthesised by one-pot S_NAr reactions. A screening of the metal-complexing ability of [2₆]hexathiacalix[3]arene[3]pyrazine revealed its affinity for Cu^I, Cu^II and Ag^I metal salts.     

Synthesis and chemical properties of silapiperazines and derivatives of 1,6-dioxa-3,8-diaza-5,10-disilacyclodecane-2,7-dione

The results of studies dealing with the synthesis of six- and ten-membered silicon-nitrogen-containing heterocyclic compounds are presented. The structures and reactivities of these compounds have been studied. High reactivities of 2,5-disilapiperazines and 1,6-dioxa-3,8-diaza-5,10-disilacyclodecane-2,7-dione derivatives have been noted. Possible schemes of the formation of these compounds are discussed.Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 10, pp. 2407–2414, October, 1996.     

Synthesis and structure of azido-and amino-substituted dibenzoxazepinones

1,3-Dinitro[b, f][1,4]dibenzoxazepin-11(10H)-one enters nucleophilic substitution reactions with N-nucleophiles, azide ion preferably replacing the nitro group in position 3, whereas amines the one in position 1. Structures of the substitution products were confirmed by X-ray diffraction and ¹H NMR NOE spectroscopy. The selectivity observed in the reaction with amines was supposed to be caused by the stabilization of the intermediate σ-complex with the NH…O intramolecular hydrogen bond. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2018–2022, October, 2007.     

Synthesis of polyfluorodibenz[b,f][1,4]oxazepines by the cyclization of 2-[(polyfluorobenzylidene)amino]phenols

Thermolysis of 2-[(polyfluorobenzylidene)amino]phenols in ethanol in the presence of triethylamine affords the corresponding fluorinated dibenz[b,f][1,4]oxazepines in moderate to high yields. The structures of 2-[(2,3,4,5,6-pentafluorobenzylidene)amino]phenol and 1,2,3,4-tetrafluorodibenzo[b,f][1,4]oxazepine have been determined by single-crystal X-ray diffraction.     

Effect of intramolecular cyclization on the enthalpies of solvation of tetramethylurea in water and alkanols at 298.15 K

The enthalpies of solution of N,N′-dimethylethyleneurea (1,3-dimethyl-2-imidazolidinone) in water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and t-butanol (2-methyl-2-propanol) were measured calorimetrically at 298.15 K. For comparison purposes, the previous data on enthalpic effects of 1,1,3,3-tetramethylurea dissolution (solvation) in the same solvents were analyzed. It has been concluded that the intramolecular cyclization of tetramethylurea, to form dimethylethyleneurea, results in strengthening of the solute solvation and this tendency is more pronounced in a non-aqueous (alcoholic) medium.     

Synthesis of 3S-methylundec-1-ylbromide, a key synthon in the synthesis of (S,S,S)-diprionylacetate, from L-(-)-menthol

Three new approaches to the synthesis of 1-bromo-3S-methylundecane, a key synthon in the synthesis of (S,S,S)-diprionylacetate, a sex pheromone of pine sawflies of the genera Diprion and Neodiprion, were proposed based on chemo-and stereoselective transformations of L-(-)-menthol derivatives. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 73–76, January–February, 2006.     

Synthesis and studies of organic nitrates of the heterofunctional series

N-Nicotinoyltris(hydroxymethy)aminomethane trinitrate hydronitrate, an analog ofN-nicotinoylethanolamine nitrate (the active principle of the antianginal drug nicorandil), was prepared byO-nitration of the corresponding triol with concentrated HNO₃. The structure of the reaction product was established by X-ray structural analysis. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2224–2227, December, 1997.     

卤素离子与卤代苯气相SNAr反应理论研究

采用B3LYP/6-311+G**和MP2/6-311+G**方法,研究了卤素离子与卤代苯气相SNAr反应(Ar Y+X-=Ar X+Y-,X,Y=F,Cl,Br和I)。结果显示,气相里除了X=Y=F反应为分步路径外,其余反应通道都是协同SNAr机理;F离子进攻卤苯SNAr反应无论从动力学(总能垒ΔGb=9.0~17.3 k J/mol)还是热力学上来说都很容易进行,然而Cl、Br和I离子进攻的反应,其MP2吉布斯自由能垒(ΔGb)高达91.3~202.5 k J/mol,因此在气相里很难发生;另外,标题反应的反应性可以通过卤素离子质子亲和能(PA)、最高占据轨道能(EHOMO)、Mulliken电负性(χ)以及Wiberg键级(BO)与NPA电荷(Q)来分析,其中,过渡态里C─Y键的断裂是引起反应能垒升高的主要因素,亲核试剂的亲核能力主要由EHOMO控制,而卤素离子的离去能力由其PA或χ决定。     

A study of influence of temperature and <Emphasis Type="Italic">N</Emphasis>, <Emphasis Type="Italic">N</Emphasis>-acyl protected keto ylides structure on their predominant transformations

The effect of temperature and keto ylides structure on preference of their intramolecular cyclization leading to N-containing heterocyclic compounds or linear products formation has been investigated at the B3LYP/6-31G(d,p) level of theory. It has been determined that the thermodynamic advantage of the cyclization reactions of ylides increases with temperature, while Gibbs free energies of linear products formation reactions depend insignificantly on temperature. The Wittig and the Corey–Chaykovsky reactions are least probable in the case of the sulfonium and ammonium ylides considered. However, for phosphonium ylides the Wittig reaction must be considerably preferable in comparison with other routes, while behavior of the arsonium ylides is predicted to be more complex. Research of S-ylides transformations shows that formation of methylthio-substituted heterocycles with five-, six- or seven- membered rings is possible from a thermodynamic standpoint, while conversion of the corresponding ylide to a four-membered heterocycle is disadvantageous. Presence of a methyl substituent and its position in the ylide carbon chain depends ambiguously on the behavior of sulfur keto ylides.     

The effect of the valent state of the heteroatom on the spectrochemical evidence of conjugation in allyl compounds of sulfur and phosphorus

The effect of valency of the heteroatom on the spectrochemical evidence of the conjugation in allyl derivatives of S^II,VI and P^III,IV was studied by quantum chemical methods. The geometric and electronic structures of thetrans- andgauche-conformers, including those for allyl compounds of P^V with equatorial or axial P-C bonds, were calculated. According to the calculations, inversion of the higher occupied molecular orbitals (MO) and the convergence of their energies resulting from the replacement of weak n,-conjugation by strong ,-conjugation should occur on going from S^II and P^III to S^VI and P^V. Increasing the interaction between the higher occupied MO of the fragments in the non-planar conformation of the molecule causes strengthening of the spectral evidence of conjugation: a decrease in the first ionization potential and a bathochromic shift of the long-wavelength absorption band in the electronic spectrum. The increased relative stability of thegauche-conformers of allyl compounds of hypervalent elements was explained by the through-space interaction between the vacant d-orbitals of the S^VI and P^V atoms and the -orbital of the C=C bond. Charge transfer between the molecular fragments makes the major contribution to the energy of conjugation.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 43–47, January, 1995.The work was carried out with the financial support of the Russian Foundation for Basic Research (Project No. 93-03-5566).     

Synthesis and Characterization of an α-Fe2O3-Decorated g-C3N4 Heterostructure for the Photocatalytic Removal of MO

This study describes the preparation of graphitic carbon nitride (g-C₃N₄), hematite (α-Fe₂O₃), and their g-C₃N₄/α-Fe₂O₃ heterostructure for the photocatalytic removal of methyl orange (MO) under visible light illumination. The facile hydrothermal approach was utilized for the preparation of the nanomaterials. Powder X-ray diffraction (XRD), Scanning electron microscopy (SEM), Energy dispersive X-ray (EDX), and Brunauer–Emmett–Teller (BET) were carried out to study the physiochemical and optoelectronic properties of all the synthesized photocatalysts. Based on the X-ray photoelectron spectroscopy (XPS) and UV-visible diffuse reflectance (DRS) results, an energy level diagram vs. SHE was established. The acquired results indicated that the nanocomposite exhibited a type-II heterojunction and degraded the MO dye by 97%. The degradation ability of the nanocomposite was higher than that of pristine g-C₃N₄ (41%) and α-Fe₂O₃ (30%) photocatalysts under 300 min of light irradiation. The formation of a type-II heterostructure with desirable band alignment and band edge positions for efficient interfacial charge carrier separation along with a larger specific surface area was collectively responsible for the higher photocatalytic efficiency of the g-C₃N₄/α-Fe₂O₃ nanocomposite. The mechanism of the nanocomposite was also studied through results obtained from UV-vis and XPS analyses. A reactive species trapping experiment confirmed the involvement of the superoxide radical anion (O₂^•−) as the key reactive oxygen species for MO removal. The degradation kinetics were also monitored, and the reaction was observed to be pseudo-first order. Moreover, the sustainability of the photocatalyst was also investigated.     

亚硝胺在小微孔沸石上的“嵌入式”吸附探讨

通过结构计算分析了大体积的六亚甲基亚硝胺（NHMI）和N’-亚硝基去甲烟碱（NNN）在小微孔沸石上各种可能的吸附方式,结合实验事实推断出它们以－N－N=O官能团嵌入沸石孔道进行吸附的几率最大.这种“嵌入式”吸附方式是小微孔沸石得以吸附、分离那些体积远远大于其孔径的毒物分子的重要原因,可用以拓宽沸石在生态环境保护中的应用.     

Solvent effect on catalytic properties of the HCI-DMF-1,1,2,2-tetrachloroethane system

Ionization of 2- and 3-nitroanilines was studied in HCl-DMF-1,1,2,2-tetrachloro-ethane (TCE) solutions at 25 °C. The ionization capability of the medium and basicity constants pK _i of indicators change depending on the ratio of the components. The numerical values of pK _i are found to depend on the analytical composition of the DMF-TCE solvent. The solvent effect on pK _i is associated with a change in the solvation of the nonionized form of the indicators.Translanted fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1446–1449, June, 1996.     

Structural factors influencing the reaction rates of 4-aryloxy-7-nitrobenzofurazans with amino acids

An interesting observation was made when studying the S _N Ar reaction between several 4-aryloxy-7-nitrobenzofurazans (2) and several amino acids leading to the apparition of detectable fluorescence from the substitution products3. Acidic amino acids reacted very slowly=while basic amino acids react fastest with2 having an unsubstituted phenyl or a 4-formyl-phenyl Ar group. Amongst neutral amino acids, proline reacts fastest at room temperature after 100 min. With2 having a methoxy-subtituted Ar group.     

Synthesis,structures and properties ofN-(trihalogermylmethyl)-substituted amides,lactams and imides,the derivatives of the five-coordinate germanium

The formation of trichlorogermyl-substituted amides, lactams, and imides occurs when 2Et₂O·HGeCl₃ is condensed with compounds possessing the -NCH₂Cl fragment and equally well when HGeCl₃ interacts with compounds containing -NCH₂OH and-NCH₂OSiMe₃ groups. In some cases, the use of the latter is more advantageous from the preparative point of view. In compounds thus obtained, the germanium is five-coordinate due to the coordination . Deceased August 13, 1993. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1793–1799, October, 1993.     

四(对氯苄基)锡的合成、结构和量子化学研究

The tetra(p-chlorobenzyl)tin has been synthesized via reaction of p-chlorobenzyl chloride with Sn and struc-turally determined by X-ray diffraction method. The crystal belongs to orthorhombic space group Fdd2 with a=2.1243(6), b=2.2136(6), c=1.1242(3)nm,V=5.286(2)nm³, Z=8, D_x=1.560Mg·m^-3, μ(MoKα)=13.86cm^-1,F(000)=2480,find R=0.0331 for 2191 unique reflection [I >2σ(I)]. The bond lengths of Sn-C is 0.2167,0.2183nm,respectively.The tin atom has a distorted tetrahedral geometry. The study on title compound has been performed,with ab initio calculation by means of G98W package and taking Lanl2dz basis set.The sta-bilities of the compound,some frontier molecular orbital energies,the populations of the atomic net charges in compound and composition characteristics of some frontier molecular orbitals have been investigated. CCDC:180868.     

5-氨基双四唑富氮配位化合物的合成、结构及其对高氯酸铵的热分解影响

水热条件下合成了两个5-氨基双四唑配位化合物Cu(bta)(bpy)(H2O)(1)和Pb2(bta)2(en)2.4H2O(2)(H2bta=5-氨基双四唑,bpy=2,2′-联吡啶,en=乙二胺),并借助单晶X-射线衍射技术对其结构进行了表征。在配合物1中,5-氨基双四唑配体以双齿螯合模式与铜离子配位形成离散的分子,并通过H键作用进一步形成了三维的超分子结构。在配合物2中,强的R22(8)氢键环作用将双核的Pb2(bta)2(en)2单元连接成一维的链,这些链通过与水分子氢键作用被进一步组装成三维的超分子结构。另外,通过DSC技术探究了它们作为添加剂对高氯酸铵的热分解催化影响。研究发现,铅基化合物2的催化效果较铜基化合物1要好。     

Discrete contributions to static dipole polarizabilities of excited bound states of non-relativistic hydrogen-like atoms

The static dipole polarizability α _{d, i} for an arbitrary bound state i of the non-relativistic hydrogen-like atom has been known for a long time from, e.g; the second-order perturbation theory treatment of the Stark effect. A reliable result for the ground state requires both summation over the discrete spectrum and inclusion of the continuum contribution. This continuum contribution is known to decrease for excited states, but a systematic study of this decrease has not been available so far. We present here representative results from a systematic study of α _{d, i} , which was performed as a first test of a new algorithm for the radial integrals involved. Partial sum approximations of the discrete contribution yield the total α _{d, i} with a relative error of less than 1% for all states i with principal quantum number n≥5. Corresponding results for the relativistic case, for which the radial integral algorithm was developed, will be presented elsewhere. Dedicated to Professor Hermann Stoll on the occasion of his 60th birthday An erratum to this article is available at .