Pd_2(dba)_3/BINAP催化合成1,4-双-(4′-苯胺基苯酰基)苯

以Pd2(dba)3/BINAP催化1,4-双-(4′-溴苯酰基)苯和苯胺反应,合成了1,4-双-(4′-苯胺基苯酰基)苯,其结构经UV,1HNMR,13CNMR和元素分析表征。     

1,4-双(4''''-溴苯酰基)苯的合成工艺改进

以对苯二甲酰氯和溴苯为原料,无水氯化铝粉末为催化剂,合成了1,4-双(4'-溴苯酰基)苯,其结构经1H NMR,IR和DSC表征.     

4-羟甲基-N-(4-乙氧基苯基)-N-(4'-硝基苯基)苯胺的合成

以碘化亚铜为催化剂,对硝基苯胺与对碘苯乙醚经取代反应制得4-乙氧基-N-(4-硝基苯)苯胺(1);1与对氟苯甲醛在碳酸钾作用下经取代反应制得4-(N-4-硝基苯-N-4-乙氧基苯)氨基苯甲醛(2);2经Na BH4还原合成了新化合物4-羟甲基-N-(4-乙氧基苯基)-N-(4'-硝基苯基)苯胺,其结构经1H NMR,13C NMR和IR表征。     

1,4-双(取代苯乙炔基)苯及反,反-1,4-双(β-取代苯乙烯基)苯的电子光谱的研究

测定了1,4-双(取代苯乙炔基)苯(Ⅰ)和反,反-1,4-双(β-取代苯乙烯基)苯(Ⅱ)的紫外光谱、荧光光谱.用CNDO/S-CI和HMO方法对苯乙炔、二苯乙炔和(Ⅰ)及苯乙烯、1,2-二苯乙烯和(Ⅱ)的激发能进行了计算和研究.讨论了化合物结构对光谱的影响.     

对甲苯磺酸催化下二乙酰苯与含有羟基的苯甲醛的Aldol缩合反应

以对甲苯磺酸(p-TsOH)作催化剂, 二乙酰苯与含有羟基的苯甲醛发生aldol缩合反应, 合成了3个1,3-双[3-(取代苯基)丙烯酰基]苯衍生物1～3, 3个1,4-双[3-(取代苯基)丙烯酰基]苯衍生物4～6和2个中间体7, 8, 中间体7, 8再与含有羟基的苯甲醛发生aldol反应合成了3个1-[3-(4-羟基苯基)丙烯酰基]-4-[3-(取代苯基)丙烯酰基]苯衍生物9～11, 反应均能在2～6 d内完成, 操作和后处理简便. 以上11个新化合物均未见报道, 其结构经1H NMR, IR, MS和HRMS加以确证.     

1,4-双(4′-溴苯酰基)苯的合成工艺改进

以对苯二甲酰氯和溴苯为原料,无水氯化铝粉末为催化剂,合成了1,4-双(4′-溴苯酰基)苯,其结构经1HNMR,IR和DSC表征。     

1,4-双(三氯甲基)苯的微量分析研究

本文报道在氯化锌存在下用二甲基替苯胺的丙酮溶液作为1,4-双(三氯甲基)苯的微量分析试剂.在1,4-双(三氯甲基)苯和二甲基替苯胺的反应混合物中加入氯化锌,在沸水浴中加热6分钟,生成一稳定的蓝绿色产物,用丙酮溶解后在624毫微米处进行分光光度测定.本法设备简单,操作快速、方便,灵敏度和再现性均较好.     

具有大的双光子吸收截面的A-A-A型双苯乙烯基苯类化合物的合成

合成了A-A-A型双苯乙烯基苯类化合物FR[2,5-二氰基-1,4-二(4'-氟苯乙烯基)苯],并采用核磁共振、红外光谱和元素分析等手段对其进行了表征.用飞秒脉冲诱导荧光光谱法分别研究了2个A-A-A型双苯乙烯基苯类化合物FR与CY[2,5-二氰基-1,4-二(4'-氰基苯乙烯基)苯]以及2个D-A-D型双苯乙烯基苯类化合物MO[2,5-二氰基-1,4-二(4'-甲氧基苯乙烯基)苯]和MA[2,5-二氰基-1,4-二(4'-二甲胺基苯乙烯基)苯]的单、双光子吸收与发射特性.实验结果表明,最大单光子吸收与发射波长随末端取代基供电子能力的增强而增大,末端强吸电子基化合物FR和CY具有相当高的荧光量子产率(分别为0.92与0.89)、较长的荧光寿命(分别为5.8与6.1 ns)及较大的双光子吸收系数(分别为19.1与20.5).末端带强吸电子基的化合物FR与CY的双光子吸收截面(δ,分别为6350 GM和6870 GM)比末端带供电子基的化合物MO和MA的δ(分别为270 GM与1790 GM)要大得多,表明A-A-A型双苯乙烯基苯类化合物具有异常大的δ.     

1,4—双（取代苯乙炔基）苯电子光谱的溶剂效应

1,4-双(取代苯乙炔基)苯是较好的荧光物质并有良好的激光转换效率。本文测定了1,4-双(苯乙炔基)苯1和1,4-双[(4-叔丁基苯基)乙炔基]苯2在14种溶剂中的紫外吸收光谱和荧光发射光谱,并用多元回归QSAR程序研究了它们的溶剂效应。 1 实验 UV谱用Beckman DU-8B紫外可见分光光度计测定。荧光光谱在MPF-4荧光仪上测得。     

3-碘-5-甲基-1,5-苯并硫氮杂(艹卓)-4(5H)-酮的合成

以2-甲基硫代苯胺为原料,通过酰化反应、碘环化反应合成了3-碘-5-甲基-1,5-苯并硫氮杂(艹卓)-4(5H)-酮,总收率86.3%,其结构经NMR,IR和MS表征.     

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.     

Mixed ligand titanium(IV) complexes. Chlorobis(dithiocarbamato)bis(methylsalicylato)titanium(IV) andbis(dithiocarbamato)bis(methylsalicylato)titanium(IV)

Summary Dichlorobis(methylsalicylato)titanium(IV) reacts with potassium or amine salts of dialkyl or diaryl dithiocarbamates in 11 and 12 molar ratios in anhydrous benzene (room temperature) or in boiling CH₂Cl₂ to yield mixed ligand complexes: (AcOC₆H₄O)₂ Ti(S₂CNR₂)Cl (1) and (AcOC₆H₄O)₂ Ti(S₂CNR₂)₂ (2), R=Et, n-Pr, n-Bu, cyclo-C₄H₈ and cyclo-C₅H₁₀. These compounds are moisture sensitive and highly soluble in polar solvents. Molecular weight measurement in conjunction with i.r.,¹H and¹³C n.m.r. spectral studies suggest coordination number 7 and 8 around titanium(IV) in (1) and (2) respectively.     

Bis(trifluoroacetyl) peroxide, CF(3)C(O)OOC(O)CF(3)

Pure, highly explosive CF(3)C(O)OOC(O)CF(3) is prepared for the first time by low-temperature reaction between CF(3)C(O)Cl and Na(2)O(2). At room temperature CF(3)C(O)OOC(O)CF(3) is stable for days in the liquid or gaseous state. The melting point is -37.5 degrees C, and the boiling point is extrapolated to 44 degrees C from the vapor pressure curve log p = -1875/T + 8.92 (p/mbar, T/K). Above room temperature the first-order unimolecular decay into C(2)F(6) + CO(2) occurs with an activation energy of 129 kJ mol(-1). CF(3)C(O)OOC(O)CF(3) is a clean source for CF(3) radicals as demonstrated by matrix-isolation experiments. The pure compound is characterized by NMR, vibrational, and UV spectroscopy. The geometric structure is determined by gas electron diffraction and quantum chemical calculations (HF, B3PW91, B3LYP, and MP2 with 6-31G basis sets). The molecule possesses syn-syn conformation (both C=O bonds synperiplanar to the O-O bond) with O-O = 1.426(10) A and dihedral angle phi(C-O-O-C) = 86.5(32) degrees. The density functional calculations reproduce the experimental structure very well.