Stereoselective total synthesis of (±)-α-vetispirene, (±)-hinesol, and (±)-β-vetivone based on a Claisen rearrangement

The stereoselective total syntheses of (±)-α-vetispirene, (±)-hinesol, and (±)-β-vetivone were accomplished based on a Claisen rearrangement in an alkenyl bicyclic dihydropyran system. The most striking feature of this approach is that the Claisen rearrangement of bicyclic dihydropyran proceeds stereoselectively to provide a multi-functionalized spiro[4.5]decane, which is an efficient precursor for the synthesis of the vetivane sesquiterpenes.     

Freezing temperatures and densities of solutions of some hydrocarbons and sodium oleate inN-methylacetamide. Evidence for a solvophobic interaction

The freezing temperatures and densities (at 31°C) of solutions of octane, nonane, decane, 3,3-diethylpentane, and sodium oleate inN-methylacetamide (NMA) have been measured. The molality of the freezing solution was calculated from the density. The solubilities of octane, nonane, and decane inN-methylacetamide are also reported. Apparent molal volumes calculated from the densities are close to the values in the pure hydrocarbons and are not strong functions of the concentration. This indicates the absence of any unusual packing effect. The calculated free energies of transfer of the hydrocarbons from pure hydrocarbon to NMA solution are much less negative than the corresponding values for water, showing that the bulk solvophobic interaction inN-methylacetamide is smaller than in water. This is consistent with the freezing temperatures of sodium oleate which show that micelles do not form below 0.1 mole-kg^–1. The osmotic coefficients of the hydrocarbons calculated from the freezing temperatures showed negative deviations from ideality that were larger for the hydrocarbons with the higher molecular weights. Two estimates of the pairwise solvophobic interaction inN-methylacetamide indicate that it is also smaller than in water. The solvophobic effect in this solvent does not include the large entropy and enthalpy effects found in aqueous solutions.     

Vibrational spectra and conformations of 2- and 3-methylbicyclo[4.4.0]decanes

The conformations and heats of formation of all trans(T)- and cis(C)-2- and 3-methyl-substituted T- and Cbicyclo[4.4.0]decanes (BD) were calculated by the MM2 method of molecular mechanics. It was shown that the conformationally mobile T-2-Me-CBD and T-3-Me-CBD can exist in normal conditions as an inseparable mixture of conformers with a different equatorial or axial orientation of the Me groups. The Raman scattering (RS) spectra of TBD and CBD were investigated. RS bands whose frequencies were sensitive to the type of ring linkage and orientation (but not the position) of the Me substituents were detected in the 700–300 cm^–1 region.A. V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 117912 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 9, pp. 2089–2097, September, 1992.     

Volume and heat capacity of model non-aqueous self-assembly systems

Blends of immiscible polymers are often stabilized by block copolymers which can form non-aqueous micelles and microemulsions in the liquid polymers. The phase diagrans, apparent volumes and apparent heat capacities of model non-aqueous binary and ternary systems were studied in order to investigate the conditions under which such self-assembly systems could form. 1,2-Hexanediol, which can cosolubilize hexane and ethyleneglycol, forms inverse micelles in hexane and weak microaggregates in ethyleneglycol. Genapol X-060, a commercial alcoholic surfactant containing on the average an aliphatic chain of 13 carbons and 6 oxyethylenes (C₁₃E₆), forms microaggregates in poly(ethyleneglycol) 400. These self-assembly systems are strengthen in the presence of a third component which has an affinity for the inner phase.Presented at the Symposium, 76^th CSC Congress, Sherbrooke, Quebec, May 30–June 3, 1993, honoring Professor Donald Patterson on the occasion of his 65^th birthday.     

Formation and structures of 2,5-di-<Emphasis Type="Italic">tert</Emphasis>-butylcyclopentadienone dimers

The structures of dimers formed from 2,5-di-tert-butylcyclopentadienone in the reaction with alkaline metals and in the Diels-Alder reaction were studied. A photochemical rearrangement with ring contraction was found for the second dimer. Spectral features of the dimers related to steric hindrance were studied by 1D and 2D NMR procedures.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2179–2183, October, 2004.     

Solubility of 1,3,5,7-tetra azatricyclo[3.3.1.1]decane (HMT) in water from 275.15 K to 313.15 K

The water solubility of 1,3,5,7-tetra azatricyclo[3.3.1.1^3,7]decane, hexamethylenetetramine (HMT) or urotropine was determined at temperatures between 275.15 K and 313.15 K. Van’t Hoff graphs of ln m_sat versus 1/T gave three different straight lines, suggesting the existence of three different forms of the substance in the temperature region studied.

Previous work reported both increasing and decreasing solubility with temperature. This work found the solubility does not have a simple behavior.     

聚(碳酸丁二醇酯-co-三环癸烷二甲醇碳酸酯)的制备与性能

采用熔融酯交换和缩聚两步法,合成了以1,4-丁二醇、4,8-三环[5.2.1.0(2,6)]癸烷二甲醇和碳酸二苯酯为原料的聚(碳酸丁二醇酯-co-三环癸烷二甲醇碳酸酯)(PBTCx, x为进料中TCD占二元醇总量的百分比)。用1H NMR和13C NMR对PBTCs的微观结构和组成进行了表征。采用GPC、 DSC、 XRD、 TG对PBTCs的分子量、玻璃化转变温度(Tg)、热稳定性等进行了研究。结果表明,PBTCs的Mw为10500~124800 g?mol-1, Mn为6300~73000 g?mol-1, PDI为1.59~1.73; PBTCs呈无定形态、Tg为-3.43 ℃~70.90 ℃, PBTCs表现出比PBC更高的热稳定性。薄膜拉伸试验结果表明,PBTC30(拉伸强度为33.54 MPa,断裂伸长率为275.69%)和PBTC40(拉伸强度为32.13 MPa,断裂伸长率为294.63%)具有较高的强度和韧性,在薄膜材料中具有一定的应用潜力。     

Synthesis and conformation of 6,8,10-trinitro-1,4-dioxaspiro[4.5]decane

cis, trans-6,8,10-Trinitro-1,4-dioxaspiro[4.5]decane was synthesized by reduction of the corresponding spirocyclic anionic δ-complex with potassium tetrahydroborate. The molecular structure and the conformation of the title compound were established by X-ray diffraction analysis and¹H NMR spectroscopy. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1713–1717, September, 1999.