N-(11-羧基十一烷基)马来酰亚胺及其三聚体的合成

以顺丁烯二酸酐和12-氨基十二酸为原料,硫酸、三乙胺为脱水催化剂,经两步反应合成了N-(11-羧基十一烷基)马来酰亚胺.再在三苯基膦和苯酚作用下,N-(11-羧基十一烷基)马来酰亚胺进一步发生三聚反应合成了相应的马来酰亚胺三聚体.采用红外光谱和核磁共振谱对三聚体的结构进行了表征.     

酶促Michael-aldol串联反应合成四氢噻吩类化合物

在水介质和40℃条件下,碱性蛋白酶催化2,5-二羟基-1,4-二噻烷与N-苯基马来酰亚胺间的Michael-aldol反应,合成了四氢噻吩类化合物,反应取得了93%的产率及3∶1的非对映选择性。该方法具有反应条件温和、反应时间短、后处理简单等优点。     

聚[N-(4-二甲氨联苯基)马来酰亚胺]单体的合成及其聚合

N-取代的马来酰亚胺是缺电子的负性单体[1],它很容易进行自由基聚合或共聚合[2,3],特别是能够与负性单体如丙烯腈共聚合[4].如果在缺电子的N-取代马来酰亚胺单体中引入给电子生色基团,即给电子生色基团与受电子基团于一体,能够表现出较好的光化学性能[5].本文中报道了聚[N-(4-二甲氨联苯基)马来酰亚胺]及其单体的合成,聚合物的光化学性能将在另文报道.     

N-芳基马来海枞酸单甲酯二酰亚胺位阻异构化反应及其动力学特性

在合成松香基手性试剂(4a~4f)的过程中,首次发现N-(1-萘基)-马来海枞酸二酰亚胺(4f)的位阻异构现象,而与其结构类似的N-苯基-马来海枞酸二酰亚胺(4a)、N-(2-羧基苯基)-甲酯化马来海松酸二酰亚胺(4b)、N-(2-硝基苯基)-甲酯化马来海松酸二酰亚胺(4c)、N-(2-氯苯基)-甲酯化马来海松酸二酰亚胺(4d)和N-[1-(2-氨基)-苯基]-甲酯化马来海松酸二酰亚胺(4e)则没有该位阻异构现象.化合物4a~4f的结构通过核磁共振、质谱和红外光谱等方法进行了表征.采用变温条件下的1H NMR谱图研究了化合物4f的位阻异构化动力学特性.     

N-羟基马来酰亚胺-苯乙烯共聚物催化苯甲醇氧化的研究

本文合成了N-羟基马来酰亚胺与苯乙烯共聚物P(HOMI/St),并以P(HOMI/St)/Co(Ⅱ)催化分子氧氧化苯甲醇制备苯甲醛,考察了反应温度、P(HOMI/St)用量、氧气压力等因素对反应的影响。实验表明,在优化条件下,苯甲醛的产率可达26%。催化剂重复使用4次,仍保持良好的催化活性。     

通过1-磷杂富烯合成含磷多环化合物

1-磷杂富烯能够以2π、4π、6π体系参与环加成反应,并转化为多种磷杂多环化合物.报道了1-磷杂富烯和对苯醌以及N-苯基马来酰亚胺在加热条件下反应合成磷杂多环产物的新方法.研究结果表明对苯醌与1-磷杂富烯通过氧化加成反应产生一个易发生Diels-Alder反应的磷杂环戊烯中间体.该中间体与2分子N-苯基马来酰亚胺经过两次Diels-Alder反应形成磷杂多环化合物.研究还表明1-磷杂富烯环外双键对该反应的发生至关重要.     

红紫素-18酰亚胺衍生物的合成及其可见光谱的研究

选择脱镁叶绿酸 a甲酯为原料进行 3 位化学修饰和E环改造 .经 3 乙烯基的溴化氢加成和与联苯酚的亲核取代反应 ,完成了 3 位联苯氧基的引入 ;在碱性条件下 ,通过空气氧化将E环转变为环己二羧酸酐形成红紫素 18甲酯衍生物 ;所得氧化产物进而和盐酸羟胺反应 ,经胺解开环和再缩合成环构成N 羟基红紫素 18酰亚胺衍生物 ;对其羟基进行烷基化和酰基化 ,合成出N 取代红紫素 18酰亚胺衍生物 .同时讨论了化学结构变化对分子可见光谱的影响 .所合成新化合物的结构均经UV ,IR ,1 HNMR光谱和元素分析予以确认     

环己基马来酰亚胺的合成

用浓硫酸和三乙胺共催化环己基马来酰胺酸脱水关环合成环己基马来酰亚胺。探讨了催化剂、反应溶剂等对反应的影响。     

马来酰亚胺双键参与的官能化反应研究进展

马来酰亚胺是一类海洋天然生物碱、生物活性分子和功能材料的重要结构母核,并能转化为琥珀酰亚胺、四氢吡咯及2-吡咯酮等化合物,具有广泛的应用价值.以马来酰亚胺为合成子构建含有马来酰亚胺和琥珀酰亚胺结构单元的化合物已成为有机合成研究热点之一.对马来酰亚胺双键参与的官能化反应进行了综述,重点在马来酰亚胺的Michael加成、氧化偶联和环加成反应.     

两种耐高温紫外正型光刻胶成膜树脂的制备及性能

分别通过N-(p-羟基苯基)甲基丙烯酰胺与N-苯基马来酰亚胺、N-苯基甲基丙烯酰胺与N-(p-羟基苯基)马来酰亚胺的共聚合,制备了两种聚合物树脂聚N-(p-羟基苯基)甲基丙烯酰胺共N-苯基马来酰亚胺(poly(HPMA-co-PMI))和聚N-苯基甲基丙烯酰胺共N-(p-羟基苯基)马来酰亚胺(poly(MPA-co-HPMI)).结果表明,这两种聚合物都是按1∶1的摩尔比交替共聚的,它们都具有良好的溶解性、成膜性和亲水性,并且它们的玻璃化温度Tg都在280℃以上.将它们分别与感光剂2,1,5-磺酰氯的衍生物、助剂二苯甲酮等复配成两种紫外正型光刻胶,初步光刻实验表明,其最大分辨率都可以达到1μm,并且都可以耐270℃的高温.     

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.     

Syntheses and structures of the infinite chain compounds Cs(4)Ti(3)Se(13), Rb(4)Ti(3)S(14), Cs(4)Ti(3)S(14), Rb(4)Hf(3)S(14), Rb(4)Zr(3)Se(14), Cs(4)Zr(3)Se(14), and Cs(4)Hf(3)Se(14)

The alkali metal/group 4 metal/polychalcogenides Cs(4)Ti(3)Se(13), Rb(4)Ti(3)S(14), Cs(4)Ti(3)S(14), Rb(4)Hf(3)S(14), Rb(4)Zr(3)Se(14), Cs(4)Zr(3)Se(14), and Cs(4)Hf(3)Se(14) have been synthesized by means of the reactive flux method at 823 or 873 K. Cs(4)Ti(3)Se(13) crystallizes in a new structure type in space group C(2)(2)-P2(1) with eight formula units in a monoclinic cell at T = 153 K of dimensions a = 10.2524(6) A, b = 32.468(2) A, c = 14.6747(8) A, beta = 100.008(1) degrees. Cs(4)Ti(3)Se(13) is composed of four independent one-dimensional [Ti(3)Se(13)(4-)] chains separated by Cs(+) cations. These chains adopt hexagonal closest packing along the [100] direction. The [Ti(3)Se(13)(4-)] chains are built from the face- and edge-sharing of pentagonal pyramids and pentagonal bipyramids. Formal oxidation states cannot be assigned in Cs(4)Ti(3)Se(13). The compounds Rb(4)Ti(3)S(14), Cs(4)Ti(3)S(14), Rb(4)Hf(3)S(14), Rb(4)Zr(3)Se(14), Cs(4)Zr(3)Se(14), and Cs(4)Hf(3)Se(14) crystallize in the K(4)Ti(3)S(14) structure type with four formula units in space group C(2)(h)()(6)-C2/c of the monoclinic system at T = 153 K in cells of dimensions a = 21.085(1) A, b = 8.1169(5) A, c = 13.1992(8) A, beta = 112.835(1) degrees for Rb(4)Ti(3)S(14);a = 21.329(3) A, b = 8.415(1) A, c = 13.678(2) A, beta = 113.801(2) degrees for Cs(4)Ti(3)S(14); a = 21.643(2) A, b = 8.1848(8) A, c = 13.331(1) A, beta = 111.762(2) degrees for Rb(4)Hf(3)S(14); a = 22.605(7) A, b = 8.552(3) A, c = 13.880(4) A, beta = 110.919(9) degrees for Rb(4)Zr(3)Se(14); a = 22.826(5) A, b = 8.841(2) A, c = 14.278(3) A, beta = 111.456(4) degrees for Cs(4)Zr(3)Se(14); and a = 22.758(5) A, b = 8.844(2) A, c = 14.276(3) A, beta = 111.88(3) degrees for Cs(4)Hf(3)Se(14). These A(4)M(3)Q(14) compounds (A = alkali metal; M = group 4 metal; Q = chalcogen) contain hexagonally closest-packed [M(3)Q(14)(4-)] chains that run in the [101] direction and are separated by A(+) cations. Each [M(3)Q(14)(4-)] chain is built from a [M(3)Q(14)] unit that consists of two MQ(7) pentagonal bipyramids or one distorted MQ(8) bicapped octahedron bonded together by edge- or face-sharing. Each [M(3)Q(14)] unit contains six Q(2)(2-) dimers, with Q-Q distances in the normal single-bond range 2.0616(9)-2.095(2) A for S-S and 2.367(1)-2.391(2) A for Se-Se. The A(4)M(3)Q(14) compounds can be formulated as (A(+))(4)(M(4+))(3)(Q(2)(2-))(6)(Q(2-))(2).     

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.