An effect of application of chiral aluminium alkoxides and amides as adducts to zirconium catalyzed carbo- and cycloalumination of olefins

This paper is dedicated to a study of properties of the following novel optically active organoaluminium compounds (OACs): (1S,2S)-l,7,7-trimethyl-2-[(dialkylalumina)oxy]-bicyclo[2.2.1]heptanes and (1S)-N-(dialkylalumina)-6,7-dimethoxy-1-methyl-1,2,3,4- tetrahydroisoquinolines. The synthesis of the chiral OACs was carried out in the reaction of either natural camphor or salsolidine with both AlEt₃ and i-Bu₂AlH. The main goal of the research was to investigate the stereodifferentiating activity of the chiral OACs in the olefin carbo- and cycloalumination reactions, catalyzed by Cp₂ZrCl₂.     

基于2,5-二(4′-甲酰基苯基)苯乙烯的螺旋链光学活性聚合物的合成与表征

通过2,5-二溴苯乙烯与对甲酰基苯硼酸的Suzuki偶联反应得到2,5-二(4′-甲酰基苯基)苯乙烯.在催化剂量的冰乙酸存在下,与光学纯的(S)-(-)-α-甲基苄胺或(R)-(+)-α-甲基苄胺发生缩和反应,得到了一对手性非外消旋单体,(+)-2,5-二{4-′[(N-(S)-α-甲基苄亚胺基)次甲基]苯基}苯乙烯和(-)-2,5-二{4′-[(N-(R)-α-甲基苄亚胺基)次甲基]苯基}苯乙烯.以偶氮二异丁腈(AIBN)或过氧化苯甲酰(BPO)为引发剂,经自由基溶液聚合得到光学活性聚合物.比旋光度、紫外-可见吸收光谱以及圆二色光谱研究表明,聚合物主链可能形成了某一方向占优的稳定螺旋构象,且该螺旋构象的旋光方向与单体的旋光方向相反.聚合条件对聚合物的光学活性有很大影响,在极性较大的芳香族溶剂和较高温度下得到的聚合物具有和单体相差更大的比旋光度.侧基的手性基团脱除后,聚合物仍具有一定的旋光性,说明聚合过程中形成的螺旋手性具有一定的记忆效应.     

The response of thermally and optically stimulated luminescence from Al2O3:C to high-energy heavy charged particles

The thermoluminescence (TL) and optically stimulated luminescence (OSL) response of Al₂O₃ dosimeters to high-energy heavy charged particles (HCP) has been studied using the heavy ion medical accelarator at Chiba, Japan. The samples were Al₂O₃ single-crystal chips, of the type usually known as TLD-500, and Luxel^TM dosimeters (Al₂O₃:C powder in plastic) from Landauer Inc. The samples were exposed to ⁴He (150 MeV/u), ¹²C (400 MeV/u), ²⁸Si (490 MeV/u) and ⁵⁶Fe (500 MeV/u) ions, with linear energy transfer values covering the range from 2.26 to 189 keV/μm in water and doses from 1 to 100 mGy (to water). A ⁹⁰Sr/⁹⁰Y beta source, calibrated against a ⁶⁰Co secondary standard, was used for calibration purposes. For OSL, we used both continuous-wave OSL measurements (CW-OSL, using green light stimulation at 525 nm) and pulsed OSL measurements (POSL, using 532 nm stimulation from a Nd:YAG Q-switched laser). The efficiencies (η_HCP,γ) of the different HCPs at producing OSL or TL were observed to depend not only upon the linear energy transfer (LET) of the HCP, but also upon the sample type (single crystal chip or Luxel^TM) and the luminescence method used to define the signal—i.e. TL, CW-OSL initial intensity, CW-OSL total area, or POSL. Observed changes in shape of the decay curve lead to potential methods for extracting LET information of unknown radiation fields. A discussion of the results is given, including the potential use of OSL from Al₂O₃ in the areas of space radiation dosimetry and radiation oncology.     

The energy exchange and the optimum length of the sample tube of opfirl

The energy exchange between the pumping laser and FIR signal in the optically pumped FIR laser (OPFIRL) system was studied. The iteration method has been used to calculate the power density of the pumping and FIR signals at any point along the optical axis of the sample tube. It was found that the power density of the FIR signal did not always increase along the length of the laser tube. There was a maximum FIR power density at the appropriate point in the sample tube. If the distance of maximum power point from the entrance of the OPFIRL tube was taken as the length of sample tube Z_opt, the maximum FIR laser output should be obtained. This was the optimum length of OPFIRL tube. The value of Z_opt was closely related to the parameter of OPFIRL such as the pumping power density, the pumping detuning and the frequency of the FIR laser. The energy-exchange and the maximum output of the fir laser were calculated under the ideal condition.     

Photoelectrochemical behavior of coupled SnO2|CdSe nanocrystalline semiconductor films

A photoelectrochemical cell with a coupled SnO₂|CdSe nanocrystalline semiconductor electrode has been prepared by sequential deposition of SnO₂ and CdSe films onto an optically transparent electrode (OTE), and its photoelectrochemical behavior has been studied. The results show that the coupling of CdSe with SnO₂ leads to an improvement in the performance of OTE|SnO₂|CdSe over OTE|CdSe cells in terms of increased incident photon-to-current conversion efficiency, increased stability and smaller reversal of current. The favorable positioning of the energy bands of SnO₂ and CdSe is responsible for the above observations. Various photoelectrochemical parameters of the OTE|SnO₂|CdSe cell obtained for an incident light power of 0.31 mW cm⁻² at 470nm, are as follows: I_sc ≈ 25–30 μA cm⁻², V_oc ≈ 0.5–0.6 V, ƒƒ = 0.47 and a power conversion efficiency of about 2.25%.     

Nucleophilic aromatic substitution reactions of fluorobenzenechromium complexes with P-chiral secondary phosphine-boranes: synthesis of optically pure P-chiral (dialkyl)arylphosphine-boranes

Optically pure P-chiral (dialkyl)arylphosphine-boranes having high structural diversity were prepared by two- or three-component coupling of fluorobenzenechromium complexes, P-chiral secondary phosphine-boranes, and other nucleophiles. The stereochemical integrity at the P-stereogenic center was completely retained during the S_NAr process when the reaction was carried out in THF at low temperature.     

含金鸡纳碱的光活性聚合物──Ⅰ．金鸡纳碱／丙烯酰胺共聚物的合成与表征

研究了金鸡纳碱与丙烯酰胺的自由基共聚反应。发现在氯仿／乙醇混合溶剂中采用硫酸奎宁作为金鸡纳碱共聚单体可以合成收率和金鸡纳碱含量均较高的新型水溶性共聚物。对共聚物用元素分析、核磁共振、粘度和旋光度测定等方法进行表征，发现在假定丙烯酰胺链节为非光活性的条件下共聚物中金鸡纳碱链节的比旋光度随聚合配方中金鸡纳碱含量的增加而增加。     

A novel method for asymmetric synthesis of both enantiomers of α-substituted carboxylic acid derivatives from optically active 1-chlorovinyl p-tolyl sulfoxides and lithium ester enolates with 1,4-chiral induction from the sulfur chiral center

Treatment of optically active 1-chlorovinyl p-tolyl sulfoxides, which were synthesized from symmetrical ketones and (R)-(−)-chloromethyl p-tolyl sulfoxide in three steps, with lithium enolate of carboxylic acid tert-butyl esters gave optically active adducts having a substituent at the α-position with high 1,4-chiral induction from the sulfur chiral center in high yields. The adducts were converted to optically active esters and carboxylic acids having a chiral center at the α-position. When this addition reaction was carried out with the ester enolate generated from excess carboxylic acid tert-butyl ester with LDA in the presence of HMPA, the diastereomer of the adduct was obtained. By using the two reaction conditions for the generation of the ester enolates, a new method for asymmetric synthesis of both enantiomers of carboxylic acid derivatives having a substituent at the α-position from the one chiral source, (R)-(−)-chloromethyl p-tolyl sulfoxide, was realized.     

Diisocyanate route as a convenient method for the preparation of novel optically active poly(amide-imide)s based on N-trimellitylimido-S-valine

A new class of optically active poly(amide-imide)s based on an α-amino acid was synthesized via direct polycondensation reaction of different diisocyanates with a chiral diacid monomer. The step-growth polymerization reactions of N-trimellitylimido-S-valine (TISV) (1) with 4,4′-methylene-bis(4-phenylisocyanate) (MDI) (2) was performed under microwave irradiation, as well as solution polymerization under graduate heating and reflux conditions. The optimized polymerization conditions for each method were performed with tolylene-2,4-diisocyanate (TDI) (3), hexamethylene diisocyanate (HDI) (4), and isophorone diisocyanate (IPDI) (5) to produce optically active poly(amide-imide)s via diisocyanate route. The resulting polymers have inherent viscosities in the range of 0.02-1.10 dL/g. Decomposition temperatures for 5% weight loss (T₅) occurred above 300 °C (by TGA) in nitrogen atmospheres. These polymers are optically active, thermally stable and soluble in amide-type solvents. Some structural characterization and physical properties of this new optically active poly(amide-imide)s are reported.     

Preparation and Characterization of New Optically Active Poly(amide-imide)s from N,N′-(bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetra carboxylic)-bis-L-isoleucine and Aromatic Diamines

Five new optically active aromatic poly(amide-imide)s (PAIs) 5a–e were prepared from a direct polycondensation reaction of a new diacid of N,N′-(bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetra carboxylic)-bis-L-isoleucine 3 with various aromatic diamines 4a–e in a medium consisting of triphenyl phosphite (TPP), calcium chloride (CaCl₂), pyridine (Py) and N-methyl-2-pyrrolidone (NMP). The polycondensation reaction produced a series of novel poly(amid-imide)s 5a–e in quantitative yields with inherent viscosities of 0.39–0.51 dL/g. The resulting polymers were fully characterized by means of ¹H-NMR, FT-IR spectroscopy, elemental analyses, inherent viscosity, solubility test, specific rotation and thermal properties of them were investigated using TGA/DTG and differential scanning calorimeter (DSC). The diacid 4 was synthesized by the condensation reaction of bicyclo[2,2,2]oct-7-ene-2,3,5,6- tetracarboxylic dianhydride 1 with L-isoleucine 2 in acetic acid solution.