1-Dibutylboryl-2-diphenylphosphinoethene and its derivatives

1-Butyl-1-dibutylboryl-2-diphenylphosphino-2-phenylethene, which exists in the form 1,1,2-tributyl-3,4,4-triphenyT-1-borata-4-phosphoniacyclobut-2-ene, reacts with sulfur, selenium, methyl iodide, and pyridine under mild conditions with ring cleavage. In (2-butyl-2-dibutylboryl-1-phenylethenyl) diphenylphosphine sulfide and selenide, there is a coordinate bond between the thio-or selenophosphoryl group and the boron atom.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2793–2796, December, 1989.     

Conformational Analysis of Four Stereoisomeric Methyl 3-Acetoxy-2-Butyl-1-Cyclohexanecarboxylates and Their Derivatives in Solution

The conformational analysis of six-membered ring compounds such as mono- and disubstituted cyclohexane is a well-documented subject, and hence prediction of the most stable conformation of a given compound can be in general achieved with reasonable accuracy either by use of thermodynamic data or by spectroscopic methods.¹⁾ When considering polysubstituted cyclohexane, the configurational and the conformationay possibilities become large. The conformational aspects of 1,2,3-trisubstituted cyclohexanes would be complex depending on the nature of substituents because so many parameters are involved.¹⁾     

Crystal and Molecular Structures of Phosphonolactone Derivatives of Chromone

The crystal structure of chromone hydrazonium salt (±)-1-hydroxy-1-oxo-3-phenyl-1,3-dihydro-1λ⁵-2,1-oxaphospholo[4,5-b]-4H-1-benzopyran-4-one (2) and its acid (±)-1-hydroxy-1-oxo-3-phenyl-1,3-dihydro-1λ⁵-2,1-oxaphospholo[4,5-b]-4H-1-benzopyran-4-one (3) have been solved. Condensed rings are almost planar, the P atom adopts nearly tetragonal geometry. The molecular packing is influenced by inter- and intramolecular contacts, which can be recognized as hydrogen bonds.     

Correlation of the Solubilizing Abilities of 1-Butyl-1-methylpiperidinium Bis(trifluoromethylsulfonyl)imide and 1-Butyl-1-methylpyrrolidinium Tetracyanoborate

Chromatographic retention data were measured for a wide range of organic solutes on 1-butyl-1-methylpyrrolidinium tetracyanoborate ([BMPyrr]⁺[B(CN)₄]^?) and 1-butyl-1-methyl-piperidinium bis(trifluoromethylsulfonyl)imide ([BMPip]⁺[Tf₂N]^?) stationary phases at 323 K and 353 K. The measured retention factors were combined with published infinite dilution activity coefficient and gas-to-water partition coefficient data to yield gas-to-anhydrous ionic liquid (IL) and water-to-anhydrous IL partition coefficients. Both sets of partition coefficients were analyzed using the Abraham model. The derived Abraham model correlations describe the observed gas-to-IL (log₁₀ K) and water-to-IL (log₁₀ P) partition coefficient data to within average standard deviations of about 0.10 and 0.15 log₁₀ units, respectively.     

Synthesis of 1-Butyl-3,6-diazahomoadamantane

Russian Journal of Organic Chemistry - 1-Butyl-3,6-diazahomoadamantan-9-one was synthesized by condensation of heptan-2-one with diethylenetetramethylenetetramine...     

Syntheses and Molecular Structures of Titanium Derivatives with Polymerizable Ligands. Toward Extended Arrays

The reactions between Ti(OR)₄ and allylacetatoacetate (HAAA) in 1:1 or 1:2 stoichiometry at rt gave Ti₂(OR)₆(AAA)₂ R = Et ( 1 ), iPr ( 2 ) and Ti(OR)₂(AAA)₂ R = Et ( 3 ), iPr ( 4 ) species. A monosubstituted derivative Ti₂(OiPr)₆(AMP)₂ ( 5 ) was isolated with allylmethylphenol (AMPH). 1 and 5 were characterized by single crystal X‐ray diffraction. Their molecular structures consist of dimers with the polymerizable ligands in terminal positions andbridging alkoxide ligands assembling five and six‐coordinated metal atoms, respectively. The Ti‐O bond lengths of 1 are in the range 1.76(1) to 2.11(1) Å with the variation Ti‐OEt < Ti‐μ‐OEt < Ti‐η²‐O (allylacetatoacetate). All compounds were characterized by FT‐IR and ¹H NMR. The possibility to accede to more extended arrays either by hydrolysis or by radical initiated homo‐ or co‐polymerization reactions was investigated for the allylacetato derivatives as well as for Ti(OiPr)₂(AAEMA)₂ AAEMA = [2‐(methacryloyloxy)ethylacetoacetato] for the latter reactions.     

Syntheses and Molecular Structures of 2-(1-Methyliminoethyl)phenolato Zinc Complexes

2-(1-Methyliminoethyl)phenol ( 1 a ) reacts with diethyl zinc to give bis[2-(1-methyliminoethyl)phenolato]zinc ( 3 ) via [2-(1-methyliminoethyl)phenolato]ethylzinc ( 2 ) as an intermediate. The complex 3 is also formed in the reaction of bis(trimethylsilyl)amide zinc with 1 a . The compounds were characterized by microanalysis, NMR (¹H, ¹³C) and IR spectroscopy. X-ray structure analysis of the compounds 2 and 3 revealed that both compounds form in the solid state dimeric species where the monomeric units are bridged via two oxygen atoms forming a planar Zn₂O₂ ring with tetrahedral [ZnO₂NC] and trigonal-bipyramidal [ZnO₃N₂] coordination of the zinc atom, respectively.     

Theoretical Study of the Molecular and Electronic Structures of CPDT-TCNQ and Its Difluoro and Dimethyl Derivatives

1 INTRODUCTION Since the discovery of one-dimensional metallic behavior of tetrathiafulvalene (TTF) with tetracyano- quinodimethane (TCNQ)[1], organic charge-transfer (CT) complexes and CT salts have been intensively studied in search of electrically conducting and superconducting properties[2 ～ 6] which are most unusual for an organic material. The most intriguing property is that it is excellent metal with conducti- vity similar to that of metals at room temperature[7, 8]. In these…     

Synthesis,Structures, and Molecular Docking of Some Bioactive Benzamide Derivatives as Ionic Solids

Russian Journal of General Chemistry - Five new substituted benzamide derivatives as ionic solids are prepared and characterized by FT-IR, 1H, and 13C NMR spectroscopy. The crystal structure for...     

Acylation and Carbamoylation of 2-Hydrazinothiazole Derivatives. Identification of Isomeric Structures

Acylation and carbamoylation of 2-(arylmethylidenehydrazino)- and 2-(aroylhydrazino)thiazoles was performed, and structure of the products was established.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 4, 2005, pp. 594–600.Original Russian Text Copyright © 2005 by Denisova, Bakulev, Dehaen, Toppet, Van Meervelt, Kodess.     

苯酚和苯胺类衍生物的结构与薄层色谱保留值关系的研究

以不同比例的己烷－乙酸乙酯二元体系作为展开剂,在硅胶板上测定了２４种苯酚和苯胺类衍生物的比移值Ｒｆ。用斜交因子分析方法将这２４种化合物分为具有不同特征的两大类：第一类的苯环上均不含甲基,而第二类的苯环上均含甲基。第一类化合物的比移值均比第二类要小;苯环上取代基团使Ｒｆ值增大的顺序为ＣＨ３＞ＯＨ＞ＮＨ２;邻位取代的化合物,由于分子内形成氢键,极性减弱,因而比移值增大。分别对两类化合物的保留值与其拓扑指数进行多元回归分析的结果表明,它们的色谱保留行为与其分子结构之间存在着较好的相关性。     

Formation of 1-Butyl-3-methylimidazolium Bis(2-ethyl-1-hexyl)sulfosuccinate Stabilized Water-in-1-Butyl-3-methylimidazolium Bis(trifluoromethanesulfonyl)imide Microemulsion and the Effects of Additives

A new strategy is proposed here to formulate a bis(2-ethyl-1-hexyl)sulfosuccinate (AOT^?) stabilized water-in-ionic liquid microemulsion without any additives. Replacing the inorganic counter ion Na⁺ by the organic 1-butyl-3-methylimidazolium ([Bmim]⁺) ion greatly improves the solubility of AOT^? in hydrophobic 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([Bmim]Tf₂N) (IL) and favors the formation of water-in-IL (W/IL) microdroplets. The existence of the W/IL microdroplets has been confirmed by dynamic light scattering, Fourier transform infrared absorption spectroscopy and ultraviolet–visible absorption spectroscopy. Also, presented for the first time are the effects of salts and alcohols on the microstructure and water solubilization capacity of the ternary H₂O/[Bmim]AOT/[Bmim]Tf₂N system. For inorganic salts, larger concentrations of the salt and higher charge density of the cation result in smaller microdroplet size and weak water solubilization capacity. For 1-hexanol, a high concentration of this alcohol results in small microdroplet size but high water solubilization capacity. Analyses indicate that the salts compress the electric double layers of W/IL microemulsions, decrease the size of the microdroplets and consequently reduce the water solubilization capacity; the alcohol, however, facilitates the aggregation of AOT^?, increases the number of W/IL microdroplets, and therefore improves the water solubilization capacity of the system.     

Pressure-Induced Solidification of 1-Butyl-3-methylimidazolium Tetrafluoroborate

We have used Raman spectroscopy to investigate the high-pressure phase behavior of 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF₄]), a representative ionic liquid, at pressures up to ~7.5 GPa. We have also studied how increasing pressure leads to conformational changes in the [bmim]⁺ cation. We have found that liquid [bmim][BF₄] undergoes pressure-induced solidification (freezing) into a superpressed (metastable) state at 2.5 GPa; another structural change probably occurs at ~6 GPa. Remarkably, conformational changes in the [bmim]⁺ cation between trans and gauche conformers are concordant with the metastable structural changes of [bmim][BF₄]. As the pressure is increased from ambient, the fraction of gauche conformers increases, but the gauche fraction decreases above the solidification pressure (2.5 GPa), and slope of the gauche/trans ratio changes again above 6 GPa. We interpret these results in terms of the fragility of the ionic liquid.     

COX抑制剂——氟比洛芬衍生物的作用方式及选择性研究

用DOCK4.0程序搜索氟比洛芬衍生物与环氧合酶结合的构象。用Cscore综合评 分体系确定最佳构象，复合物经分子力学优化后，发现衍生物在COX-1中的取向和 位置与X射线衍射测犁晶体复合物中氟比洛芬作用方式相同；衍生物在COX-2中也有 与氟比洛芬类似的结合方式。衍生物对COX-2/COX-1 的选择掏性与衍生物作用于两 种酶的结合自由能之差有较好的相关性。相关系数     

Crystal,Molecular, and Electronic Structure of 1-Acetyl-indoline and Derivatives

The crystal and molecular structures of the following molecules have been determined: 1-acetyl-indoline, 1-acetyl-5-nitro-indoline, l-acetyl-5-nitro-7-bromo-indoline, 1-acetyl-5-bromo-7-nitroindoline, and l-acetyl-5-bromo-7-nitro-indol. Molecular orbital calculations are performed for these compounds and two related species.     

Molecular Structures and Thermodynamic Stabilities of Cycloalkadienes and Their Methoxy Derivatives: An Ab Initio and DFT Study

The geometry-optimized molecular structures and total energies of 4- to 6-membered cycloalkadienes, and of a number of their monoand dimethoxy derivatives, have been calculated by ab initio (HF/6-31G^*, MP2/6-31G^*//HF/6-31G^*) and DFT (B3LYP/6-31G^*) methods. By comparison with available experimental data, the reliability of these computational methods for an estimation of the relative stabilities (enthalpies) of the isomeric forms of the title compounds was tested. The experimental enthalpies of isomerization proved to agree best with the respective theoretical data based on the mean of the HF/6-31G^* and B3LYP/6-31G^* energies. The theoretical calculations were then extended to several isomeric methoxy-substituted cycloalkadienes, for which no previous thermodynamic data exist. Some structural features of the title dienes were also discussed.     

1,3,2—氧氮磷杂环戊烷衍生物晶体结构研究

用X射线衍射方法测定了两个1,3,2-氧氮磷杂环戊烷衍生物的晶体结构:2-二乙氨基-3-(4′-甲基苯甲酰基)-2-硫代-1,3,2-氧氮磷杂环戊烷,C_(14)H_(21)N_2O_2PS(1),空间群为P_(bco),α=0.9057(5)nm,b=1.3974(6)nm,c=2.5130(7)nm,Z=8,R=0.051;2-二乙氨基-3-(2′,4′-二氯苯甲酰基)-2-硫代-1,3,2-氧氮磷杂环戊烷,C_(13)H_(17)N_2O_2PSCl_2(2),空间群P2_1/c,α=0.7375(1)nm,b=1.4370(3)nm,c=1.6015(7)nm,β=93.70(2)°,Z=4,R=0.054。结构均由直接法解出。两个化合物中氧氮磷杂五元环均为半椅式构象。其中P—N键长环内分别为0.1712(2)nm和0.1723(0)nn;环外为0.1620(3)nm和0.1620(0)nm,由于成环作用所致环内P—N键长大于环外的。