以二苯甲酮为端基的第一代树状取代酞菁锌的合成

4-甲基二苯甲酮经N-溴代丁二酰亚胺溴代制得4-溴甲基二苯甲酮(1);1与3,5-二羟基苯甲醇反应合成了外围带有二苯甲酮取代基的第一代树枝状分子3,5-二(二苯甲酮-4-甲氧基)苯甲醇(2);2与4-硝基邻苯二甲腈缩合制得外围带有二苯甲酮取代基的第一代树枝状分子4-[3,5-二(二苯甲酮-4-甲氧基)苯甲氧基]邻苯二甲腈(3);3经"液相法"环合生成外围带有二苯甲酮取代基的第一代树枝状分子取代的酞菁锌配合物——四[3,5-二(二苯甲酮-4-甲氧基)苯甲氧基]锌酞菁[ZnPc(C35H27O5)4],其结构经UV,1HNMR,IR和MS表征。     

新型不对称酞菁锌的合成和表征

以4-硝基邻苯二甲腈为主要原料,合成了2(3),9(10),16(17),23(24)-四-(正庚酰胺基)-酞菁锌、2(3),9(10),16(17),23(24)-四-(甲氧基)-酞菁锌、2(3),9(10),16(17),23(24)-四-(对叔丁基苯氧基)-酞菁锌和2(3),9(10),16(17),23(24)-四-(苯氧基)-酞菁锌等4种对称型酞菁.在此基础上,选取4-对叔丁基苯氧基邻苯二甲腈为前驱体,采用概率法合成了含有氨基、羧基的2种不对称酞菁锌(A3B).     

4-磺酸钾基邻苯二甲腈的合成

以4-硝基邻苯二甲腈为起始原料,经还原、重氮化、酰氯化、水解加碱中和得到酞菁水溶性前驱体4-磺酸钾基邻苯二甲腈,总收率22%,其结构由1H NMR,IR,MS和元素分析表征。     

4-(甲氧基噻吩基)-3-(取代苯甲酰基)-吡咯类化合物的合成与抗肿瘤活性研究

分别以2-甲氧基噻吩、3-甲氧基噻吩、3,4-二溴噻吩和取代苯乙酮为原料,经过溴甲氧基取代反应、VilsmeierHack反应、羟醛缩合和Van Leusen吡咯合成法,设计并合成了33个未见文献报道的4-取代噻吩基吡咯类化合物.其结构均经~1H NMR,~(13)C NMR及HRMS确认,同时采用噻唑蓝(MTT)法测试了目标化合物对CHO、HCT-116、MGC80-3、SGC-7901以及HUVEC细胞增殖抑制活性.结果显示,部分化合对MGC80-3细胞有较强(IC_(50)≤20μml/L)或中等(20μmol/LIC_(50)≤50μmol/L)增殖抑制作用,其中[4-(3,4-二甲氧基噻吩-2-基)-1H-吡咯-3-基](4-苯基苯基)甲酮(4a-2)和[4-(3,4-二甲氧基噻吩-2-基)-1H-吡咯-3-基](3-溴苯基)甲酮(4a-7)的IC_(50)值分别为8.6和8.5μmol/L;化合物4a-7对HCT-116细胞有中等抑制活性;化合物4a-2和4a-7对SGC-7901细胞有中等增殖抑制活性;并且几乎所有化合物对正常人体细胞HUVEC无明显抑制作用.     

3-硝基邻苯二甲腈的合成

以邻苯二甲酸酐为原料,经过硝化、脱水、亚胺化、氨解、脱水5步反应,高产率地合成了3-硝基邻苯二甲腈,研究了邻苯二甲酸酐的硝化反应、3-硝基邻苯二甲酰胺的脱水条件对产率的影响。目标化合物的结构用元素分析,IR和^1H NMR表征。     

负载芳基苄醚树枝形酞菁锌聚合物纳米粒子的合成及其离体光动力活性

首先将对氰基溴化苄与3,5-二羟基苯甲醇通过Frétchet反应合成芳基苄醚树枝分子3,5[二-(4'-氰基苯甲氧基)]苯甲醇(1),1与4-硝基邻苯二甲腈合成前驱物4-{3',5'-[二-(4"-氰基苯甲氧基)]}苯甲氧基邻苯二甲腈(3),然后3在乙酸锌,1,8-二氮杂二环(5,4,0)-7-十一烯(DBU)和正戊醇...     

新型手性双功能有机催化剂的合成及其催化不对称Henry反应合成(R)-aegeline

以(S)-2-氨甲基-1-乙基吡咯烷为原料,合成了新型手性双功能有机催化剂(S)-1-[3,5-二(三氟甲基)苯基]-3-(1-乙基吡咯烷基-2-甲基)硫脲(2,产率82.2%).用2催化对甲氧基苯甲醛与硝基甲烷的不对称Henry反应,制得(R)-1-(4-甲氧基苯基)-2-硝基乙醇(3, 84%ee);3经Pd/C催化氢化得到(R)-2-氨基-1-(4-甲氧基苯基)乙醇(4);4与反式肉桂酰氯反应合成了(R)-aegeline,总产率37.6%(以对甲氧基苯甲醛计).化合物的结构经1H NMR, 13C NMR和MS表征.     

2-氰基-3,4-二氢喹唑啉衍生物的合成

邻硝基苯甲醛与取代苯胺(1)或取代苄胺(2)进行还原氨化反应得N-(2-硝基苄基)取代苯胺(3)或N-(2-硝基苄基)取代苄胺(4);将3或4的硝基还原为氨基生成关键中间体N-(2-氨基苄基)取代苯胺(5)或N-(2-氨基苄基)取代苄胺(6);5或6分别与4,5-二氯-1,2,3-二噻唑氯化物进行缩合反应,合成了一系列新的2-氰基-3,4-二氢喹唑啉类衍生物,收率36%~72%,其结构经1H NMR和HR-MS确证。     

氯霉素相似化合物的合成——Ⅳ.3-(邻羥基-对硝基苯基)-2-二氯乙酰氨基-丙醇

本文叙述自邻乙酰氧基-对硝基溴化苄(Ⅶ)或邻甲氧基-对硝基溴化苄开始合成氯霉素的相似化合物——3-(邻羟基-对硝基苯基)-2-二氯乙酰氨基-丙醇(V)及其有关化合物。化合物V对金色葡萄球菌及大肠杆菌均无明显的抑制作用。     

二-吡啶氧基-轴向取代-四-α-(3-戊氧基)锡(IV)酞菁的合成与表征

以3-硝基邻苯二甲腈为起始原料,与正戊醇反应合成3-戊氧基邻苯二甲腈(1),然后在高温溶剂1-氯萘中经缩聚反应合成二氯-轴向取代-四-α-(3-戊氧基)锡酞菁(2),2进一步与2-羟基吡啶在N,N-二甲基甲酰胺中合成二-吡啶氧基-轴向取代-四-α-(3-戊氧基)锡酞菁配合物3,同时对相关化合物分别进行了元素分析,IR,1HNMR,UV/Vis,荧光和质谱表征.     

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.