含松香骨架的新型手性季铵盐相转移催化剂的合成及其在不对称环氧化反应中的应用

以天然松香为原料合成了4个新型手性季铵盐类相转移催化剂, 并用于催化不对称查尔酮环氧化反应, 发现这类手性相转移催化剂可以有效地催化查尔酮的不对称环氧化, 环氧化产物ee最高达20%.     

ON A SUFFICIENT CONDITION FOR THE METRIC COEFFICIENTS TO BE CONFORMALLY TIME-INDEPENDENT

The statement in Rindler's book "Essential Relativity" [(Springer-Verlag, New York, 1977), p. 119] claiming that "the metric coefficients are time-independent if light signals tracing out the same path always take the same coordinate time" has two problems, the first one has been pointed out by us in a recent paper "relation between choosing ‘good' coordinates and the behavior of light signals" [Acta Physica Sinica (Overseas Edition), 3(1994), 881], while the second is the main focus of the present article.     

A Novel Proton Sensor with Luminescence and Color Signaling Based on Platinum(II) Terpyridyl Acetylide Complex

Molecular switches that are controllable, reversible and readable at molecular level are an essential compo-nent of molecular electronics1 and chemical sensors.2-6 Of particular interest are the molecules which show dramatic and reversible changes in color and/or lumi-nescence in visible spectral region upon exposure to specific substrates. A number of chromophore- spacer-receptor systems that can selectively recognize specific guest molecules at their receptor site and pro-duce measurable col…     

Versatile photosensitization system for 1O2-mediated oxidation of alkenes based on nafion-supported platinum(II) terpyridyl acetylide complex

[structure: see text] Platinum(II) terpyridyl acetylide complex (1) was incorporated into Nafion membranes as a photosensitizer, and the Nafion was immersed in an aqueous or organic solution of 7-dehydrocholesterol, alpha-pinene, or cyclopentadiene. This photosensitizer system can generate singlet oxygen ((1)O(2)) in high quantum yield to oxidize the alkenes in the solution outside the Nafion and can be easily removed from the reaction vessel at the end of the photooxidation.     

Synthesis and Luminescent Properties of an Acetylide-Bridged Dinuclear Platinum(II) Terpyridyl Complex

Introduction Luminescent coordinatively unsaturated platinum(II) complexes are appealing from photochemical and pho-tophysical perspective.1,2 In particular, platinum(II) ter-pyridyl complexes have attracted considerable attention due to their rich spectroscopic2a-d and biological proper-ties.2a,e-g However, the development of the photochem-istry of these complexes is limited by their short-lived MLCT excited state in solution at room temperature. The lack of emission originates from low-l…     

Confined space-controlled hydroperoxidation of trisubstituted alkenes adsorbed on pentasil zeolites

Photosensitized oxidation of trialkylalkenes 2-methyl-2-pentene (1), 1-methylcyclohexene (2), trans-3-methyl-2-pentene (3), cis-3-methyl-2-pentene (4), and 2-methyl-2-butene (5) included in the internal framework of Na-ZSM-5 zeolites was investigated. The zeolite samples having adsorbed the alkenes were suspended in isooctane, and the sensitizer, tetraphenylporphyrin (TPP), was dissolved in the solution. Singlet oxygen produced in the solution diffused into the internal framework of the zeolites and reacted with alkenes. For all the substrates studied, the ene-type allylic hydroperoxides were obtained in a highly regioselective manner. The regiochemistry for 1-4 in favor of the allylic hydrogen abstraction from the largest substituents is in contrast to their photooxidation within the dye-supported zeolite Na-Y, where the secondary hydroperoxides are preferentially produced. The tight confinement of the alkenes within the narrow channels of the ZSM-5 zeolites is likely to be responsible for this selectivity.     

Yb(C~6Me~6) (AlCl~4)~3·MeC~6H~5 的合成及其晶体结构

合成了一种新的芳烃络合物Yb(C~6Me~6)(AlCl~4)~3·MeC~6H~5 , 并确定了其晶体结构.     

合成重要中间体1,4位官能化化合物的简便方法

5,6-取代环烯醚2在乙腈的单重态氧反应有效的生成一系列1,4位官能化化合物3。1,4位官能化化合物为合成上重要的中间体。环烯醚2可以通过β-二酰基化合物1和1,3-二溴丙烷在稀碱(碳酸钾/丙酮)条件下缩合生成。     

超分子化合物[M(4,4''''-bipy)2(H2O)4]·(4,4''''-bipy)2·(3,5-diaba)2·8H2O](M=Co,Ni,Cd)的合成及晶体结构

合成了3个超分子化合物[M(4,4'-bipy)2(H2O)4]·(4,4'-bipy)2·(3,5-diaba)2·8H2O(M=Co(1),Ni(2),Cd(3);4,4'-bipy=4,4'-联吡啶;3,5-diaba=3,5-二氨基苯甲酸阴离子),用红外光谱、元素分析及X-射线单晶衍射进行了表征。3个化合物的晶体都属于单斜晶系,空间群为P2/c。晶体学参数:化合物1:a=0.9389(2)nm,b=0.7751(1)nm,c=3.9284(6)nm,β=90.14(2)°,V=2.85880(69)nm3,Z=4,Dc=1.397g·cm-3,F(000)=1266,μ=0.380mm-1,R1=0.0349,wR2=0.0829;化合物2:a=0.9383(2)nm,b=0.7753(1)nm,c=3.9218(6)nm,β=90.09(1)°,V=2.85280(68)nm3,Z=2,Dc=1.399g·cm-3,F(000)=1268,μ=0.420mm-1,R1=0.0366,wR2=0.0805;化合物3:a=0.94091(13)nm,b=0.77885(11)nm,c=3.9712(5)nm,β=90.10°,V=2.9102(7)nm3,Z=2,Dc=1.433g·cm-3,F(000)=1308,μ=0.454mm-1,R1=0.0468,wR2=0.0964。3,5-diaba未参与配位,在配位阳离子[M(4,4'-bipy)2(H2O)4]2 中,金属离子M髤与来自2个4,4'-bipy的2个氮原子和4个水分子的氧原子配位,呈八面体的几何构型。分子中还存在未配位的4,4'-bipy。通过配位阳离子、游离4,4'-bipy及未配位的3,5-diaba间的丰富氢键,构建成具有三维结构的超分子化合物。     

对甲苯磺酰谷氨酸桥联的一维双链锰配合物的合成、表征与晶体结构

A one-dimensional double-chain coordination polymer [Mn(phen)(tsgluo)] was synthesized in a mixed solution and its crystal structure was determined by X-ray diffraction method. It crystallizes in orthorhombic system with space group P2₁2₁2₁. The crystal data are: a=0.530 78(17) nm, b=1.723 9(5) nm, c=2.456 9(8) nm, Z=4, μ=0.729 mm^-1, D_c=1.579 g·cm^-3, V=2.248 1(12) nm³, R₁=0.033 1, ωR₂=0.078 9. In the title complex, each Mn(Ⅱ) ion presents a octahedral geometry with the coordination of two nitrogen atoms from 1,10-phenanthroline and four oxygen atoms from three different tsgluo^2- ligands. The γ-carboxyl coordinates to Mn(Ⅱ) in the mode of bidentate chelate, while the α-carboxyl coordinates in a bidentate bridging mode. CCDC: 253910.