1,3-二(炔丙基氧)苯与4,4'-二叠氮甲基联苯的聚合反应及聚合物性能的研究

研究了1,3-二(炔丙基氧)苯(BPOB)与4,4'-二叠氮甲基联苯(DAMBP)的本体聚合行为. 核磁共振氢谱(¹H NMR)表征了聚合物的结构, 通过傅立叶红外技术(FT-IR)观察了反应过程中的基团变化情况, 采用差示扫描量热技术(DSC)研究了聚合反应动力学, 在较低温度(80 ℃)下二元叠氮与二元炔发生了1,3-偶极环加成聚合反应, 生成了主链含三唑环的聚合物; 利用Kissinger法和Crane法处理得到了反应的动力学参数: 反应级数为0.92, 反应活化能E_a为79.8 kJ• mol^－1, 频率因子A为1.26×10¹⁰ min^－1. 利用凝胶渗透色谱(GPC)、动态热机械分析(DMA)和热重分析方法(TGA)研究了聚合产物的性能. 结果表明, 聚合物的数均分子量达4.22×10⁴, 聚合物有较高的玻璃化转变温度和良好的热稳定性, 玻璃化转变温度达到131 ℃, 热分解温度(T_d5)达355 ℃     

Quinone Diazides for Olefin Functionalization

The utility of quinone diazides in materials science is vast and well‐documented, yet this potentially useful motif has languished in the annals of organic synthesis. Herein we show that modern tools of catalysis can be employed with free or suitably masked quinone diazides to unleash the power of these classic diazo compounds in the context of both inter‐ and intramolecular olefin cyclopropanation.     

2-甲基重氮萘醌在环醚中光解产物的2D NMR研究

应用二维核磁共振对2-甲基重氮萘醌在四氢呋喃和二氧六环中光解反应的产物：2-甲基-4-螺(2′-四氢吡喃)萘-1-酮 (3)、2-甲基-4-(2′-四氢呋喃基)-1- 萘酚 (4)、2-甲基-4-螺［7′-(1′,4′-二氧杂环庚烷)萘-1-酮 (5)、2-甲基-4 -［2′-(1′,4′-二氧杂环己基)］-1-萘酚 (6)和二(2-甲基-萘 -22-冠-6) (7)的¹H和¹³C NMR谱进行了全归属.     

Photolysis of 1,2-anthraquinone diazide in aromatic hydrocarbons

It has been determined that the main products of photolysis of 1,2-anthraquinone diazide in benzene, toluene, anisole, nitrobenzene, and pyridine are the corresponding 1-hydroxy-2-arylanthraquinones that form as a mixture ofortho, meta, andpara isomers with significant content of themeta isomer (40–55%).Novosibirsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk 630090. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 1000–1003, April, 1992.     

Syntheses and structures of N-phenylmaleimidetriazoles and by-products

The syntheses, properties, and structures of N-phenylmaleimidetriazole derivatives are described. Intermediates and by-products are also discussed. 1b. a = 43.997(7) Å, 5.7610(9) Å, 8.245(1) Å, = 99.339(4), C₂/c; 2a. a = 13.646(4) Å, b = 7.744(2) Å, c = 10.612(3) Å, = 91.979(6), P2₁/c. 3a. a = 22.245(1) Å, b = 22.245(1) Å, 10.010(1) Å, P42/n. 3a. a = 11.727(2) Å, b = 14.075(3) Å, c = 16.080(3) Å, = 105.859(3), = 105.331(3), = 98.187(3), P-1. 3b. a = 8.561(3) Å, b = 14.755(5) Å, c = 22.771(7) Å, = 97.006(5), P2₁/c. 3c. a = 10.500(2) Å, b = 12.189(2) Å, c = 13.040(2) Å, = 109.091(3), = 106.089(3), = 101.022(3), P-1. 8a. a = 16.389(8) Å, b = 5.749(3) Å, c = 19.316(3) Å, = 97.467(9), P2₁/n. 8b. a = 5.822(2) Å, b = 10.114(3) Å, c = 16.705(4) Å, = 84.681(5), = 82.840(5), = 75.769(4), P-1. 9b. a = 11.251(1) Å, 13.335(3) Å, 13.376(3) Å, = 102.456(4), P2₁/n. 9c. a = 15.836(3) Å, b = 8.236(2) Å, c = 5.447(3) Å, = 92.551(3), P2₁/c. 10a. a = 13.177(2) Å, b = 14.597(2) Å, c = 5.5505(8) Å, = 110.979(2), Cc. 11a. a = 14.720(2) Å, b = 13.995(2) Å, c = 38.245(6) Å, = 94.430(3), P2₁/n. 12b. a = 15.067(5) Å, b = 20.378(6) Å, c = 8.669(5) Å, = 99.16(4), = 99.32(3), = 105.23(3), P-1. 13b. a = 8.2824(6) Å, b = 10.5245(7) Å, c = 15.518(1) Å, = 92.305(1), = 100.473(1), = 100.124(1), P-1. 15a. a = 15.357(3) Å, b = 7.778(2) Å, c = 22.957(2) Å, Pbca. 16b. a = 18.0384(4) Å, b = 12.474(3) Å, c = 20.078(5) Å, Pbca.     

含重氮萘醌化合物翻转成像体系的研究概述

本文对含重氮萘醌化合物的翻转成像体系作了详细的总结.所述翻转成像体系主要分为三类,其一主要是通过脱羧反应、酯化反应、酰胺化反应等化学反应生成碱难溶性化合物,使原本通过曝光、显影可获得的阳图图像翻转成负像;其二是以重氮萘醌化合物为产酸剂,通过酸的催化作用使交联剂与成膜树脂发生交联反应,或发生脱保护基的反应,实现翻转成像;还有一类是利用近紫外光和高能射线相结合实现翻转成像.第一类和第三类翻转成像体系在抗蚀剂方面可能有较大的应用价值,而第二类翻转成像体系可能在印刷版材方面有一定的应用前景.     

The Further Cross-Linking of Polydiallylamines with Dihalo Compounds

Highly swollen ion-exchange resins result from the polymerization of diallylamine in the presence of 2 mol% of a bis-diallyl-amino compound as the cross-linking reagent. It is shown that post cross-linking with a dihalo compound is an acceptable method for decreasing the swelling propensity of the resins. The secondary amino groups are then converted to tertiary types, although there is some formation of quaternary ammonium groups which is detrimental in ion-exchange resins which are to be regenerated thermally. The aromatic compound α,α-dichloro-p-xylene is more suitable than the less rapidly reacting aliphatic compound Br(CH₂)₄Br and the even slower reacting reagent Cl(CH₂)₄Cl. However, satisfactory products are obtained with the use of Br(CH₂)₆Br. The additional cross-linking of the poly-diallylamine results in a lowering of the basicity level by one to two orders of magnitude, with the electron-withdrawing aromatic product exhibiting the greatest effect. Better pH buffering properties are usually obtained when the product is subsequently treated with hot alkali, which transforms any quaternary ammonium groups present to tertiary amino types.     

Synthesis of Nitro‐Octaaza Derivatives of Reduced Anthracene

Nitro compounds of octaaza derivatives of reduced anthracene were synthesized for the first time by reaction of 2,3,4a,6,7,8a,9,10‐octaaza‐4,8‐dioxo‐3,4,4a,7,8,8a,9,9a,10,10a‐decahydroanthracene with nitric acid, mixed nitric acid/sulfuric acid, and nitric acid/acetic anhydride at between –20 and –30 °C. In addition, 1,2,4,5‐tetrazine azido derivatives were obtained by hydrolytic decomposition of the starting compound by nitrous acid. All the resultant compounds exhibit high thermal stability.     

2-Amino-1,2,3-triazole derivatives

The syntheses and structure of 2-triarylphosphoranimine-1,2,3-triazole derivatives from vicinal diazides have been investigated. Compounds derived from dichloronapththoquinone, 2,3-dichloro-5,6-dimethylbenzoquinone, and 2,3,5,6-tetrachlorobenzoquinone are included. X-ray structures, NMR, IR, UV, and cyclic voltammetry data are reported. Compound 2 crystallizes in space group with a = 12.31(1), b = 12.469(3), c = 10.088(3) Å, = 97.19(3), = 103.79(6), = 101.84(4)°, and D _calc = 1.466 g/cm for Z = 2. Compound 4 crystallizes in space group P2₁/c with a = 9.044(2), b = 10.882(2), c = 19.110(4) Å, = 99.06(2)°, and D _calc = 1.324 g/cm for Z = 2. Compound 6 crystallizes in space group P2₁/a with a = 8.85(1), b = 14.841(8), c = 11.372(8) Å, = 107.19(3)°, and D _calc = 1.397 g/cm for Z = 4. Compound 11 crystallizes in space group P2₁/n with a = 8.823(3), b = 16.501(6), c = 16.221(3) Å, = 103.58(2)°, and D _calc = 1.309 g/cm for Z = 4. Compound 12 crystallizes in space group with a = 11.606(8), b = 11.671(5), c = 10.734(3) Å, = 101.62(3), = 93.70(4), = 64.33(4)°, and D _calc = 1.438 g/cm for Z = 2. Compound 13 crystallizes in space group C2/c with a = 13.337(7), b = 9.217(6), c = 24.78(1) Å, = 102.85(5)°, and D _calc = 1.478 g/cm for Z = 8.