E-、Z-2-(1-咪唑基)-O-（α-甲基对卤苄基）-2′，4′-二氯苯乙 酮肟硝酸盐的合成与结构表征

首先以2,4-二氯氯代苯乙酮、咪唑、羟胺和对卤苯乙酮为原料,分别合成E-、Z-2-（1-咪唑基）-2′,4′-二氯苯乙酮肟(ⅠE、ⅠZ)和对卤-α-氯乙苯（ⅡA和ⅡB）,ⅠE和ⅠZ分别与ⅡA和ⅡB反应,生成E-、Z-2-（1-咪唑基）-O-（α-甲基对卤苄基）-2′,4′-二氯苯乙酮肟硝酸盐四个新化合物,产率为52.0%～60.0%,并经元素分析、IR和1HNMR进行了表征。     

α—（α′—甲基—卤代苄氧基）—β—（1—咪唑基）—2，4—二氯乙苯硝酸盐的合成与结构表征

先以间二氯苯,氯乙酰氯和咪唑为原料合成β－（1－咪唑基）－2,4－二氯－α－苯乙醇（I）,再以二卤苯为原料合成α－氯－卤代乙苯（Ⅱa-Ⅱd),然后, Ⅰ分别与Ⅱa-Ⅱd反应,生成α－α′－甲基－卤代苄氧基）β－（1－咪唑基）－2,4－二氯乙苯硝酸盐4个新化事物,产率分别为66．8％,78．5％,76．8％和81．2％,新化合物的结构经元素分析,IR和1H NMR表征。     

E-、Z-2’-(1-咪唑基)-O-(α-甲基-二氯苄基)-2,4-二氯苯乙酮肟硝酸盐的合成与抑菌活性

以间二氯苯、氯乙酰氯和咪唑为原料 ,利用成肟和引入咪唑基顺序不同 ,首先合成了 E-,Z-2 -(1 -咪唑基 ) -2 ,4 -二氯苯乙酮肟 ( E、IZ) ,从二氯苯合成了 α-氯 -二氯取代乙苯 ( A、 B和 C) ,咪唑基 -二氯苯乙酮肟顺反异构体 ( Z、 E)分别与 α-氯 -二氯乙苯反应 ,生成 E-、Z-2 -(1 -咪唑基 ) -O-(α-甲基 -二氯苄基 ) -2 ,4 -二氯苯乙酮肟硝酸盐共 6种新化合物 ,产率为 5 7.5 %～ 64 .5 %,新化合物结构经元素分析、IR和 1H NMR表征 .初步实验表明 ,各化合物对水稻苗腐根有不同程度抑制活性 .     

2-(1H-唑基)-1-(2,3,4-三甲氧基)苯乙酮衍生物的合成与结构表征

首先以2－溴－1－（2，3，4－三甲氧基）苯乙酮，四丁基铵－1H－1，2，4－三唑或咪唑为原料，分别合成了2－（1H－1，2，4－三唑－1－基）－1－（2，3，4－三甲氧基）苯乙酮（Ia)和2－（1H－咪唑0－1－基）－1－（2，3，4－三甲氧基）苯乙酮（Ib)与盐酸羟胺反应生成2－（1H－1，2，4－三唑－1－基）－1－（2，3，4－三甲氧基）苯乙酮肟和1－（1H－咪唑－1－基）－1－（2，3，4三甲氧基）苯乙酮肟，产率为63％－72％，并经元素分析，IR和1H NMR进行了表征。     

E-、Z-2＇-(1-咪唑基)-O-(α-甲基-二氯苄基)-2,4-二氯苯乙酮肟硝酸盐的合成与抑菌活性

E-、Z-2＇-(1-咪唑基)-O-(α-甲基-二氯苄基)-2;4-二氯苯乙酮肟硝酸盐的合成与抑菌活性     

E，E—1，4—二[2′,2^〃—（苯并恶唑基乙烯基）]苯及衍生物的合成和光性能

合成了E，E－1，4－二[2′,2^〃-（苯并恶唑基乙烯基）]苯及衍生物共14种，测定了它们的熔点、红外光谱、核磁共振氢谱、紫外吸收光谱和荧光发射光谱、荧光量子产率及激光性能。     

A Practical Synthesis of （S）—（＋）—2—（6′—methoxyl—2—naphthyl） propionic Acid

A simplified procedure for enantioselective synthesis of (S)-( )-2-(6′-methoxyl-2-naphthyl)propionic acid ((S)-( )-naproxen), starting from (6-methoxy-α-naphthyl)-1-propanone,with D-mannitol as auxiliary catalyzed by SmCl3 in one-pot is described. The yield is 87.5%(ee value 99%).     

2—（芳磺酰基）—1—（2—噻吩基）乙酮的合成

２－（芳磺酰基）－１－（２－噻吩基）乙酮的合成丁言斌樊爱龙张正＊（南京大学化学系南京２１００９３）关键词氯噻吩基乙酮，芳磺酰基噻吩基乙酮，合成，相转移催化１９９６－０８－１２收稿，１９９７－０１－１３修回砜类化合物不仅是有机合成的有用中间体［１］，而...     

罗非昔布类似物4—[4—（甲磺酰基）苯基]—3—环己基—2（5H）呋喃酮的合成

对环氧合物－2选择性抑制剂罗非昔布（Rofecoxib)进行了结构修饰,以对甲磺酰基苯乙酮为原料,经过溴化得到溴酮,然后与环己基乙酸钠在室温下反应,得到环己基乙基乙酸酯,后者在避光,碱存在下环合得到了新合物4－[4－（甲磺酰基）苯基]－3－环己基－2（5H）呋喃酮。目标产物结构经IR和^1H NMR验证。     

4-酰基-双(1,3-二苯基-5-吡唑啉酮)铽(Ⅲ)配合物的和成及荧光性质

合成了3种4－酰基－双（1，3－二苯基－5－吡唑啉酮），1，5－双（1′，3′－二苯基－5′－吡唑啉酮－4′－基）－1，5－戊二酮；1，6－双（1′，3′－二苯基－5′－吡唑啉酮－4′－基）－1，6－己二酮和1，10－双（1′，3′－二苯基－5′－吡唑啉酮－4′－基）－1，10－癸二酮，通过元素分析，红外光谱和核磁共振氢谱对产物组成进行了表征，合成了它们的Tb(Ⅲ）二元和三元[1,10-二氮杂菲（Phen)或2，2′－联吡啶（Dipy)]配合物，测定了配合物的荧光光谱，对其荧光性质进行了研究，结果表明，配合物发射Tb(Ⅲ）的特征荧光，4－酰基0双（1，3－二苯基－5－吡唑啉酮）配体的三重态能级与Tb(Ⅲ）的最低激发态（5D4）能级匹配较好，配合物荧光强度随4－酰基－双（1，3－二苯基－5－吡唑啉酮）配体2个吡唑环间碳链的增长而减弱，第2配体Phen和Dipy具有荧光增强作用，且前者优于后者。′     

OH(3) (-) and O(2)H(5) (-) double Rydberg anions: predictions and comparisons with NH(4) (-) and N(2)H(7) (-)

A low barrier in the reaction pathway between the double Rydberg isomer of OH(3) (-) and a hydride-water complex indicates that the former species is more difficult to isolate and characterize through anion photoelectron spectroscopy than the well known double Rydberg anion (DRA), tetrahedral NH(4) (-). Electron propagator calculations of vertical electron detachment energies (VEDEs) and isosurface plots of the electron localization function disclose that the transition state's electronic structure more closely resembles that of the DRA than that of the hydride-water complex. Possible stabilization of the OH(3) (-) DRA through hydrogen bonding or ion-dipole interactions is examined through calculations on O(2)H(5) (-) species. Three O(2)H(5) (-) minima with H(-)(H(2)O)(2), hydrogen-bridged, and DRA-molecule structures resemble previously discovered N(2)H(7) (-) species and have well separated VEDEs that may be observable in anion photoelectron spectra.     

Monohydrazido(2-)-complexes of molybdenum and tungsten (IV), (V) and (VI)

Summary Reaction of MoCl₅ or WCl₆ with 1-methyl-1-phenylhydrazine or 1, 1-diphenylhydrazine hydrochloride results in the formation of M^VI species [MCl₄(NNRR)]. These react with tertiary phosphines PR₃ to form M^V species [MCl₃(NNRR)(PR₃) _n ] (n=1 or 2).[MoCl₃(NNMePh)(PMe₃)₂] can be reduced in the presence of PMe₃ to the Mo^IV speciescis-mer-[MoCl₂(NNMePh)(PMe₃)₃].     

Synthesis and spectral properties of new complexes between glycine and titanium(III), vanadium(III), chromium(III), iron(III), cobalt(II), nickel(II) and copper(II)

Summary Complexes of formula [MCl₃(glyH)₃] (M=Ti, V and Fe) [CrCl₃(glyH)₂H₂O], [MCl₂(glyH)₂(H₂O)₂] (M=Co and Cu) and [NiCl₂(glyH)₃H₂O] have been prepared and characterized by potentiometric curves, chemical analysis, magnetic properties, i.r. and electronic spectral data.     

Tetrachloro- and Tetrabromostibonium(V) Cations: Raman and (19)F, (121)Sb, and (123)Sb NMR Spectroscopic Characterization and X-ray Crystal Structures of SbCl(4)(+)Sb(OTeF(5))(6)(-) and SbBr(4)(+)Sb(OTeF(5))(6)(-)

The stable salts, SbCl(4)(+)Sb(OTeF(5))(6)(-) and SbBr(4)(+)Sb(OTeF(5))(6)(-), have been prepared by oxidation of Sb(OTeF(5))(3) with Cl(2) and Br(2), respectively. The SbBr(4)(+) cation is reported for the first time and is only the second example of a tetrahalostibonium(V) cation. The SbCl(4)(+) cation had been previously characterized as the Sb(2)F(11)(-), Sb(2)Cl(2)F(9)(-), and Sb(2)Cl(0.5)F(10.5)(-) salts. Both Sb(OTeF(5))(6)(-) salts have been characterized in the solid state by low-temperature Raman spectroscopy and X-ray crystallography. Owing to the weakly coordinating nature of the Sb(OTeF(5))(6)(-) anion, both salts are readily soluble in SO(2)ClF and have been characterized in solution by (121)Sb, (123)Sb, and (19)F NMR spectroscopy. The tetrahedral environments around the Sb atoms of the cations result in low electric field gradients at the quadrupolar (121)Sb and (123)Sb nuclei and correspondingly long relaxation times, allowing the first solution NMR characterization of a tetrahalocation of the heavy pnicogens. The following crystal structures are reported: SbCl(4)(+)Sb(OTeF(5))(6)(-), trigonal system, space group P&thremacr;, a = 10.022(1) ?, c = 18.995(4) ?, V = 1652.3(6) ?(3), D(calc) = 3.652 g cm(-)(3), Z = 2, R(1) = 0.0461; SbBr(4)(+)Sb(OTeF(5))(6)(-), trigonal system, space group P&thremacr;, a = 10.206(1) ?, c = 19.297(3) ?, V = 1740.9(5) ?(3), D(calc) = 3.806 g cm(-)(3), Z = 2, R(1) = 0.0425. The crystal structures of both Sb(OTeF(5))(6)(-) salts are similar and reveal considerably weaker interactions between anion and cation than in previously known SbCl(4)(+) salts. Both cations are undistorted tetrahedra with bond lengths of 2.221(3) ? for SbCl(4)(+) and 2.385(2) ? for SbBr(4)(+). The Raman spectra are consistent with undistorted SbX(4)(+) tetrahedra and have been assigned under T(d)() point symmetry. Trends within groups 15 and 17 are noted among the general valence force constants of the PI(4)(+), AsF(4)(+), AsBr(4)(+), AsI(4)(+), SbCl(4)(+) and SbBr(4)(+) cations, which have been calculated for the first time, and the previously determined force constants for NF(4)(+), NCl(4)(+), PF(4)(+), PCl(4)(+), PBr(4)(+), and AsCl(4)(+), which have been recalculated for the P and As cations in the present study. The SbCl(4)(+) salt is stable in SO(2)ClF solution, whereas the SbBr(4)(+) salt decomposes slowly in SO(2)ClF at room temperature and rapidly in the presence of Br(-) ion and in CH(3)CN solution at low temperatures. The major products of the decompositions are SbBr(2)(+)Sb(OTeF(5))(6)(-), as an adduct with CH(3)CN in CH(3)CN solvent, and Br(2).     

Bis(tetramethylammonium), bis(tetrabutylammonium), and bis(tetraphenylarsonium) dihydrohexaoxoxenonates(VIII)

Bis(tetramethylammonium), bis(tetrabutylammonium), and bis(tetraphenylarsonium) dihydrohexaoxoxenonates(VIII) were obtained in an aqueous solution and in acetonitriie. The rate constants of their decomposition were determined.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 184–185, January, 1995.This work was carried out with financial support from the International Scientific Foundation (Grant REI 000).