含羟基自催化交联酞菁树脂固化行为的研究

利用4-硝基邻苯二甲腈的亲核取代反应合成含羟基的邻苯二甲腈衍生物4-(2-羟基苯氧基)邻苯二甲腈(2o),4-(3-羟基苯氧基)邻苯二甲腈(2m),4-(4-羟基苯氧基)邻苯二甲腈(2p)。傅立叶变换红外光谱(FT-IR)和核磁共振氢谱(1HNMR)的分析结果证明了所得化合物的化学结构;示差热分析(DSC)和热失重分析(TGA)分别对化合物的热固化行为进行了表征。     

7-(3,4-二氰基苯氧基)-4-甲基香豆素的合成

以间苯二酚和乙酰乙酸乙酯为原料,在浓硫酸的催化下合成7-羟基-4-甲基香豆素。以4-硝基邻苯二甲酰亚胺为原料,通过氨水催化开环,三氯氧磷脱水制得4-硝基邻苯二甲腈。得到的7-羟基-4-甲基香豆素和4-硝基邻苯二甲腈经过亲核取代反应得到7-(3,4-二氰基苯氧基)-4-甲基香豆素。考察了7-羟基-4-甲基香豆素和4-硝基邻苯二甲腈的投料比、缚酸剂用量、反应温度和反应时间对反应的影响,最优反应条件为:n(7-羟基-4-甲基香豆素)∶n(4-硝基邻苯二甲腈)∶n(无水碳酸钾)=1.4∶1.0∶1.5,反应温度30℃,反应时间14 h,收率为63.7%,并通过红外吸收光谱、核磁共振氢谱和高效液相色谱(色谱纯度为99.30%)对合成的化合物的结构进行了确证。在该条件下适当放大实验条件得到收率基本在83.1%,比文献报道收率68%要高。     

含咪唑的自加速固化邻苯二甲腈化合物的性能研究

通过三步反应合成了一种含咪唑的邻苯二甲腈的模型化合物(BIPN),同时合成了一种不含咪唑的邻苯二甲腈的模型化合物(Biphenyl-PN)用于对比。通过热重分析(TGA)、紫外光谱、热处理前后的红外光谱(FT-IR)、核磁共振氢谱(1H-NMR)对比研究了这两种化合物的结构和性能,并初步研究了BIPN的固化机理。结果表明:BIPN具有自催化作用,其固化过程中有酞菁环和三嗪环生成,且主要结构为三嗪环。     

具有优良热氧稳定性的可加工双邻苯二甲腈树脂

通过"一锅法"合成了含芳醚键的低聚双邻苯二甲腈单体,并以4,4'-双(4-氨基苯氧基)二苯砜(p-BAPS)为固化剂获得了具有较高稳定性和热氧稳定性的聚合物树脂。低聚邻苯二甲腈单体制备过程为过量间苯二酚与4'4-二氟二苯甲酮反应,以N,N-二甲基甲酰胺(DMF)/甲苯为溶剂,加入适量K2CO3,最后用4-硝基邻苯二甲腈进行封端。合成的低聚双邻苯二甲腈单体用IR及1H-NMR进行结构表征。该低聚物单体与4,4'-双(4-氨基苯氧基)二苯砜(p-BAPS)进行热交联形成一个密实的热固性材料。通过热重分析和差示扫描量热分析研究该聚合物树脂的固化性能及热氧稳定性,结果表明该聚合物固化温度在450℃左右,在氮气氛下开始分解的温度为330℃,因此该固化物具有优良的热稳定性和氧化稳定性。     

4-取代苯氧基苯甲酰胺衍生物的合成及其抗肿瘤活性研究

以4-羟基苯甲酸乙酯为原料,经烃化、水解、缩合反应,合成了6个酰胺类衍生物。其结构经核磁共振氢谱、碳谱和高分辨质谱进行了表征,并对人体肿瘤细胞株进行了初步体外抗肿瘤活性评价。结果表明化合物N-(4-氟苯基)-4-苯氧基苯甲酰胺具有良好的抗肿瘤活性。     

含氰基二元芳胺固化的酞菁预聚物的合成及表征

以亲核取代反应合成了3种酞菁单体(2,2′-二[4-(3,4-二氰基苯氧基)]丙烷(BAPh)、4,4′-二(3,4-二氰基苯氧基)联苯(BPh)、4,4′-二(3,4-二氰基苯氧基)甲烷(BFPh))和1种含有氰基的高熔点二元芳胺2,6-二(4-氨基苯氧基)苯甲腈(APBN)。通过核磁共振氢谱(1H-NMR)、傅里叶变换红外光谱(FT-IR)、示差扫描量热仪(DSC)和热重分析(TGA)对合成的化合物的化学结构,芳胺和酞菁单体的热聚合行为,不同固化时间预聚物的热性能进行了研究。结果表明,BAPh/APBN和BFPh/APBN体系分别具有宽达101℃与107℃的加工窗口。BFPh型预聚物(固化1 h)比其他2种预聚物具有更高的初始分解温度(390℃下失重5%)、高温残炭率(800℃下61.7%)和固化效率。     

含氟双氨基邻苯二甲腈树脂合成及性能研究

采用2,2-双（3-氨基-4-羟基苯基）六氟丙烷和4-硝基邻苯二甲腈为原料，通过亲核取代反应制备了一种含氟元素的双氨基邻苯二甲腈树脂（FPN-p）。通过傅里叶红外光谱（FT-IR）和核磁氢谱（1H-NMR）对其化学结构进行表征，通过差示扫描量热法（DSC）和FT-IR考察了树脂的固化行为，并研究了树脂的热稳定性、热机械性能以及耐湿热性能。研究结果表明：FPN-p树脂在不加促进剂的情况下可实现自催化聚合，产物结构以三嗪环和酞菁环为主；树脂的玻璃化转变温度和质量分数5%热分解温度均超过400℃，耐温等级较高；树脂的耐湿热性能良好，高温水煮168 h后吸水率小于1%。该树脂有望用于耐高温涂层、树脂基复合材料以及高性能胶粘剂等领域。     

(S)-4-苄氧基取代苯丙胺醇衍生物的制备

采用以L-N-Boc酪氨酸甲酯为原料，经苄基保护4位酚羟基、LiAlH4还原甲酯、脱苄基保护、醚化反应、脱Boc保护基等反应，合成了中间体3和(S)-4-苄氧基取代苯丙胺醇衍生物3个。实验过程中得到的中间体3和(S)-4-苄氧基取代苯丙胺醇衍生物分别为(S)-3-(4-羟基苯基)-2-叔丁氧甲酰氨基-1-丙醇、(S)-3-(4-苄氧苯基)-2-氨基-1-丙醇、(S)-3-[4-(3,4-二氟苄氧苯基)]-2-氨基-1-丙醇和(S)-3-[4-(2,6-二氟苄氧苯基)]-2-氨基-1-丙醇，所得化合物的化学结构经质谱和核磁共振氢谱确证。本合成路线具有操作简单、收率高的特点，其中中间体3可用于氨基醇类衍生物的合成，而(S)-4-苄氧基取代苯丙胺醇衍生物的合成提供了基础化合物和合成方法参考，以发现和研制新的活性药物。     

固化工艺对双酚AF型邻苯二甲腈树脂性能的影响

采用六氟双酚A(BPF)和4-硝基邻苯二甲腈为原料,通过亲核取代反应制备了一种双酚AF型邻苯二甲腈树脂(AFPN)。通过傅里叶红外光谱(FT-IR)、核磁氢谱(1H-NMR)、时间飞行质谱(TOF-MS)对其化学结构进行表征。考察了不同固化工艺对AFPN热稳定性、热机械性能和粘接性能的影响。研究结果表明：AFPN的熔点为230℃,1,3-双(3-氨基苯氧基)苯(TPE-M)可以加速其聚合过程;当固化温度为375℃时,AFPN聚合物质量分数为5%时的热分解温度(T_5%)为501℃,T_10%为522℃,玻璃化转变温度(T_g)为327℃;AFPN树脂具有较好的阻燃性能和高温粘接性能以及潜在的应用前景。     

双邻苯二甲腈改性氰酸酯的性能研究

氰酸酯树脂是有较大应用潜力和发展前景的一种热固性树脂,但脆性较大,韧性不高,所以有很大的改性必要性。本文采用4-硝基邻苯二甲腈和双酚A溶于DMA,制备双邻苯二甲腈单体,利用核磁共振氢谱(~1H-NMR)对双邻苯二甲腈的结构进行表征,采用示热失重分析仪(TGA)对聚合物的固化行为和耐热性能进行了测试分析。采用加热熔融共混树脂,探究多种比例共混树脂的性能。探究双邻苯二甲腈单体的合成工艺并进行改进,得到合成双邻苯二甲腈单体的最佳条件,通过TGA测试得到双邻苯二甲腈改性氰酸酯的TGA图谱并进行分析,改善了氰酸酯树脂的耐热性。     

Reactions of Metal Ion Complexes with Lignin Model Compounds,Part II. Fe(TSPC) Catalyzed Formation of Oxidized Products in the Absence of Oxygen

The water soluble phthalocyanine complex trisodium tetra-4-sulfonatophthalocyanineiron(III) (Fe(TSPc)) was found to be an effective catalyst for the cleavage of the β-ether bonds in the phenolic lignin model compounds guaiacylglycol β-guaiacyl ether (1) and guaiacylglycerol β-guaiacyl ether (11). The products of these reactions were very different from those formed in the corresponding reactions catalyzed by anthraquinone (AQ) or Co(SPP).^1–4 In particular, they gave large quantities of oxidized products, even though the reactions were performed in the absence of oxygen or other added oxidant. Mechanisms have been proposed for the oxidation reactions involving 1 and 11. In both cases the first step involves one electron oxidation of the lignin model compound by the catalyst. The radical derived from 1 then undergoes further one electron oxidation and deprotonation to give 4′-hydroxy-3′-methoxy-l-(2″-methoxyphenoxy)acetophenone (8) whereas that derived from 11 undergoes Cα-Cβ bond cleavage to give vanillin (4). Reactions of the reduced form of the catalyst with 8 and the quinone methides produced from the phenolic models are important routes for guaiacol formation and regeneration of the oxidized form of the catalyst. The feasibility of these proposed reaction pathways was investigated by studying the reactions of the intermediate compounds with the catalyst.     

Synthesis and antibacterial activity of certain quinoline and quinazoline derivatives containing sulfide and sulfone moieties

Some aryl and/or heterocyclic mercaptans were allowed to react with 8-quinolyl chloroacetate (II), 8-quinolinoxyacetyl chloride (IV) and 3-(2′-chloroethyl)-2-methyl-3,4-dihydroquinazolin-4-one (X) in dry benzene and/or sodium hydroxide in absolute ethanol to give corresponding 8-quinolyl-α-mercaptoacetate (V), 8-quinolinoxythioacetate (VI) and 3-(2′-arylmercaptoethyl)-2-methyl-4-(3H)quinazolin-4-ones or 3-(2′-heterocyclicmercaptoethyl)-2-methyl-4(3H)-quinazolin-4-ones (XIa-h). The mercaptans V and XI were subjected to oxidation with hydrogen peroxide/acetic acid mixture (1:2) to afford the corresponding sulfones VII and XII. The structures of the synthesized compounds were elucidated by spectroscopic (IR and ¹H-NMR) and elemental analyses. Some of these compounds were tested for their antimicrobial activities in comparison with tetracycline as a reference compound.     

氮苷1-(2,′3,′4,′6′-O-四乙酰基-β-D-吡喃葡萄糖基)-咪唑的制备

以D-葡萄糖(Ⅰ)、醋酸酐为原料,在无水吡啶中制得中间体1,2,3,4,6-O-五乙酰基-D-葡萄糖(Ⅱ),收率为87.5%。在HB r/CH3COOH条件下对Ⅱ异头碳上的乙酰基进行溴代,制得1-溴-2,3,4,6-O-四乙酰基-D-葡萄糖(Ⅲ),不经分离,在相转移催化剂TEBA催化下,Ⅲ直接与2,4-二硝基苯酚反应得到酚苷1-O-(2,′4′-二硝基苯)-2,3,4,6-O-四乙酰基-β-D-葡萄糖苷(Ⅳ),最后Ⅳ与1-三甲基硅基-咪唑在无水四氯化锡的催化下,室温反应52 h制得氮苷1-(2,′3,′4,′6′-O-四乙酰基-β-D-吡喃葡萄糖基)-咪唑(Ⅴ),此步反应收率为90%。     

Studies on the Vilsmeier-haack reaction. Part XIII: Novel heterocyclo-substituted 4,4′-bi-pyrazolyl dithiocarbamate derivatives

5-Imino-3-methyl-l-phenyl-2-pyrazoline-4-dithiocarbamic acid (I) underwent simultaneous formylation and dimerization reactions with the Vilsmeier reagent giving 4-[5′-imino-3-(1″-formyl-2″-dimethylaminoethenyl)-3′-methyl-1′-phenyl-1′H-pyrazolo-4′-dithiocarbamyl-2,4-dihydro-3-imino-5-methyl-2-phenyl-1-pyrazoline]dithiocarbamate (II) which hydrolysed with sodium hydroxide to give 4-[3′-(1″-formyl-2″-hydroxyethenyl)-3′-methyl-1-phenyl-1′-H-pyrazolo-4′-dithiocarbamyl-1′-pyrazoline]dithiocarbamate-5,5′-dione (IV). Treatment of II and/or IV with morpholine, piperidine, piperazine, hydroxylamine, hydrazine hydrate or phenylhydrazine afforded the corresponding dipyrazolo-4,4′-dithiocarbamate derivatives with different heterocyclic systems at the 3-position. The structures of these compounds were confirmed by microanalysis data, IR and ¹H-NMR spectrometry. All synthesized compounds have been screened in vitro against Gram-positive and Gram-negative bacteria, and fungi.     

4-[2′-(反式-4″-戊基环己基)乙基]环己酮的合成

以反式 4 戊基环己烷甲酸为原料 ,通过氢化铝锂还原、溴代、格氏反应、醇脱水、催化氢化、脱甲基、高压催化氢化和重铬酸钠氧化等 8步反应合成了 4 [2′ (反式 4″ 戊基环己基 )乙基 ]环己酮 ,熔点 40 9℃ ,气相色谱测定其质量分数为 99 1%。通过红外光谱、核磁共振氢谱和质谱的分析 ,确定了目标化合物的结构。此种化合物可以作为制备乙烷类多环体系液晶的重要中间体     

Nitriles in heterocyclic synthesis. Part III: New sulpha drugs related to cyanopyridine derivatives

4-Hydroxyacetophenone (1) was reacted with cinnamonitrile derivatives (2–6) to give 3-cyano-4-(substituted phenyl)-6-(p-hydroxyphenyl)-pyridines (7–11). Interaction of compounds 7–9 with 4-substituted heterocyclo-benzenesulphonyl diazoniura chloride gave the corresponding 3-cyano-4-(sub-stituted phenyl)-6-(3′-azobenzene sulphonamido-4′-hydroxyphenyl) pyridines (12–29). The corresponding iron (III) copper (II) and mercury (II) chelates were also prepared in a 1:2 metal-to-ligand ratio. All the synthesized compounds were characterized on the basis of microanalysis, IR and ¹H-NMR spectrometry.     

Synthesis and solution properties of phthalocyanines substituted with four crown ethers

Metal-free and metal phthalocyanines (M = Ni, Zn, Co) substituted with four benzo-15-crown-5 units through oxy-bridges have been synthesized from a new phthalonitrile derivative, 1-{[(benzo-15-crown-5)-4′-yl]oxy}phthalonitrile (3). The newly prepared compounds have been characterized by elemental analyses, IR, ¹H NMR, MS and UV–Vis spectroscopy. Alkali metal interactions of the crown ethers on the zinc phthalocyaninato (6) are shown to form intermolecular adduct. The electrochemical properties of ZnPc were investigated by using cyclic voltammetry and controlled potential coulometry.