四磺化酞菁钴在微乳液、醇-水体系中的二聚现象研究

采用分光光度法研究了四磺化酞菁钴（ＣｏＴＳＰｃ），在微乳液（ＴｒｉｔｏｎＸ－１００－壬烷－正戊醇－水）、醇－水（甲醇、乙醇、丙醇）体系中的二聚现象，计算了ＣｏＴＳＰｃ的二聚常数ＫＤ。结果表明，ＣｏＴＳＰｃ的二聚常数ＫＤ值随着微乳液中表面活性的浓度及醇－水溶液的介电常数的增加而减小。     

Catalytic activity of tetracoordinated stereochemically flexible Ni(II) bis(5-thiopyrazol-4-aldiminates) in the dimerization of propylene

The catalytic activity of Ni(II) bis-(5-thiopyrazol-4-aldiminates) was found to be related to the stereochemical flexibility of these compounds in the dimerization of propylene. The propylene conversion decreases with decreasing stereochemical flexibility of the complexes resulting from an increase in the bulk of the substituent at the coordinated nitrogen atom of the NiN₂S₂ chelate ring.Institute of Inorganic and Physical Chemistry, Academy of Sciences of Azerbaidjan, 370143 Baku. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 2667–2670, November, 1992.     

离子液体体系中1－丁烯二聚反应的研究

 研究了在强酸性AlCl3／Et2AlCl／［BMIM］Cl型离子液体体系中过渡金属化合物对1－丁烯二聚反应的催化作用．结果表明，［BMIM］Cl对强酸性AlCl3／Et2AlCl催化剂催化1－丁烯高聚反应有明显的阻聚作用，并显著提高了1－丁烯二聚的选择性．在过渡金属化合物中，含镍化合物对1－丁烯二聚反应有最好的催化效果．在最佳反应条件下，1－丁烯的转化率可达95．1％，二聚产物C8烯的选择性为85．8％．同时，对1－丁烯二聚反应的机理进行了初步探讨．     

Dimerization and Coordination Properties of Zinc(II)tetra-4-alkoxybenzoyloxiphthalocyanine in Relation to DABCO in <Emphasis Type="Italic">o</Emphasis>-Xylene and Chloroform

For the first time the interactions between zinc(II)tetra-4-alkoxybenzoyloxiphthalocyanine (Zn(4—O—CO—C₆H₄—OC₁₁H₂₃)Pc) and 1,4-diazabicyclo[2.2.2]octane (DABCO) in o-xylene and chloroform have been studied by calorimetric titration and NMR and electron absorption spectroscopic methods. It has been found that in o-xylene at concentrations of Zn(4—O—CO—C₆H₄—OC₁₁H₂₃)Pc higher than 6×10⁻⁴ mol⋅L⁻¹ π–π dimers species are formed (λ _max= 685 nm). Additions of DABCO to the solution up to mole ratio 1 : 8 (Zn(4—O—CO—C₆H₄—OC₁₁H₂₃)Pc : DABCO) lead to a shift of the aggregation equilibrium towards monomer species due to formation of monoligand axial complexes. Further increasing the DABCO concentration results in formation of Zn(4—O—CO—C₆H₄—OC₁₁H₂₃)Pc—DABCO—Zn(4—O—CO—C₆H₄—OC₁₁H₂₃)Pc sandwich dimers (λ _max= 675 nm).     

二茂铁亚胺环钯化合物－－一种新型芳基氯化汞偶联催化剂

发现在催化量二茂铁亚胺环钯化合物催化下，芳基氯化汞可在湿和条件下偶联 ，以中等或高的收率生成联芳烃。对于铑盐不能催化偶联的邻位取代苯基氯化汞和 α－基氯化汞，在此体系中亦可发生偶联。以HMPA为溶剂，在x = 0.025（摩尔分 数）化合物1或2催化下与2.0当量氯化锂存在时，得到最好的催化效果。     

Structure-NMR chemical shift relationships for novel functionalized derivatives of quinoxalines

(1)H, (13)C and (15)N NMR chemical shifts for a variety of novel quinoxalines were determined by different 2D methods and were calculated using the GIAO DFT approach. Comparison with experimental data shows good correlations in the case of (1)H, (13)C and (15)N chemical shifts. Different combinations of basis sets were tested. In non-polar solvents quinoxalines exist as dimers owing to strong hydrogen bonding. Calculations for dimers improve the correlation between experiment and theory. Additive empirical methods for estimating chemical shifts have drawbacks and have to be used with a great care for this type of compound.     

Spin-adducts of radicals ·P(O)(OPri)2 and ·CMe3 with pyrrolidino[60]fullerenes studied by ESR spectroscopy

The addition of the ^·Bu^t (R¹) and ^·P(O)(OPrⁱ)₂ (R²) radicals to pyrrolidino[60]fullerenes C₆₀CH₂NMeCHX (X = C₆H₄N(CH₂CH₂Cl)₂, 2,6-(Bu^t)₂C₆H₂OH, PhC₆H₄, and indol-3-yl) was studied by ESR spectroscopy. The rate constants of R¹ radical addition to these compounds and dimerization of spin-adducts of the R¹ radicals with pyrrolidino[60]fullerenes were determined. Pyrrolidino[60]fullerenes manifest considerably higher reactivity toward the R¹ radicals than fullerene C₆₀ and methanofullerenes C₆₀CX¹X² (X¹ = X² = CO₂Et; X¹ = CO₂Me, X² = OP(OMe)₂, X¹ = X² = OP(OEt)₂).     

Oxidation of isomeric η6- and η5-fluorenylchromiumtricarbonyl anions

The oxidation of the carbon-centered [(⁶-C₁₃H₉)Cr(CO)₃]^– anion (1 ^–) results in formation of (-⁶:⁶-9,9-bifluorenyl)bis-chromiumtricarbonyl (3) due to coupling of the intermediate carbon-centered radical (1^.). The oxidation of the metal-centered anion [(⁵-C₁₃H₉)Cr(CO)₃]^– (2 ^–), which is isomeric to the 1^– anion, gives an equilibrium mixture of the chromium-centered radical {(⁵-C₁₃H₉)Cr(CO)₃}^. (2 ^.) and its dimer [(⁵-C₁₃H₉)Cr(CO)₃]₂ (6). Radical2 ^. readily reacts with MeI and the solvent (THF); the resulting derivatives, (⁵-C₁₃H₉)Cr(CO)₃R (R=Me (10); R=H (7)), undergo fast ricochet inter-ring ⁵⁶ rearrangements into (⁶-9R-C₁₃H₉)Cr(CO)₃ (R=CH₃ (9); R=H (4)).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1354–1358, July, 1995.The authors are grateful to D. V. Zagorevskii who recorded the mass spectra. This study was financially supported by the Russian Foundation for Basic Research (Grant No. 94-03-05209) and the International Science Foundation (Grant Nos. MQ 4000 and REV 000).     

Synthesis and photochemistry of beta,beta'-di(2-furyl)-substituted o-divinylbenzenes: intra- and/or intermolecular cycloaddition as an effect of annelation

New heteroaryl-substituted o-divinylbenzenes, 2,2'-(1,2-phenylenedivinylene)difuran (9), 2,2'-(1,2-phenylenedivinylene)bisbenzo[b]furan (10), and 2,2'-(1,2-phenylenedivinylene)bisnaphtho[2,1-b]furan (11), were prepared and irradiated at various concentrations; intramolecular photocycloaddition and intermolecular [2+2] twofold photoaddition reactions took place to give bicyclo[3.2.1]octadiene derivatives 12-14 and cyclophane derivatives 15-17, respectively. Compound 11 was the most selective of these o-divinylbenzenes, which, owing to pi-pi intra- or intermolecular complexation, gave only the exo-bicyclo[3.2.1]octadiene derivative 14 at low concentrations, and only the cyclophane derivative 17 at high concentrations.     

Synthesis and oxidation of 1-hydroxy-3(2)-imidazoline-derived enaminones

Interaction of 1-hydroxy-3-imidazoline and 3-imidazoline 3-oxide derivatives with esters in the presence of LDA gives enaminones, derivatives of imidazolidine. Oxidation of these compounds with MnO₂ leads to4H-imidazoleN-oxides, oxidative dirnerization products, or stable nitroxyl radicals, depending on the structure of the initial compound.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1789–1795, July, 1996.