4,4′-(双3,4-二氰基苯氧基)联苯树脂复合材料研究

以二苯砜二胺为固化剂,钼酸铵为催化剂合成了4,4′-(双3,4-二氰基苯氧基)联苯(BPH)的预聚物树脂,采用溶液浸渍法制备了玻璃纤维布预浸料,热压方式制备了玻纤增强4,4′-(双3,4-二氰基苯氧基)联苯树脂复合材料。通过示差扫描量热仪(DSC)、旋转流变仪(Rheometer)、傅里叶变换红外光谱(FTIR)、热重分析仪(TGA)和扫描电子显微镜(SEM)对树脂的固化反应,化学结构,复合材料的热稳定性和断面形貌进行了研究与表征。结果表明,钼酸铵可以显著的促进单体的预聚反应,聚合物玻璃化转变温度为380℃,复合材料具有优良的热稳定性,在氮气和空气中的5%分解温度分别为542℃和482℃,375℃处理20 h后弯曲强度保持率为97%,沸水中处理24 h后吸水率为1.4%。     

大孔磺酸树脂催化合成7-羟基-4-甲基香豆素

考察了DT-852大孔磺酸树脂催化合成7-羟基-4-甲基香豆素的工艺。结果表明,DT-852大孔磺酸树脂具有较好的催化活性;7-羟基-4-甲基香豆素较佳的合成工艺为:反应温度105℃,反应时间2.5h,催化剂用量1.0g,物料比n(乙酰乙酸乙酯)∶n(间苯二酚)=1∶1,产率为93.8%,w(7-羟基-4-甲基香豆素)=98.3%(HPLC),催化剂可重复使用多次。产物结构经FTIR验证。     

7-羟基-4-甲基香豆素的合成

研究了间苯二酚和乙酰乙酸乙酯合成7-羟基-4-甲基香豆素，考察了影响反应的主要因素。反应的最优条件：反应温度为75℃，对甲苯磺酸0．5g，间苯二酚0．1mol，a(间苯二酚)：n(乙酰乙酸乙酯)为1．0：1．0，反应时间为2h，在此条件下产率为91．8％。     

N-甲基-2-(4-苯氧基苯氧基)乙酰胺的合成

在无水碳酸钾存在下,N,N-二甲基甲酰胺(DMF)为溶剂,由N-甲基氯乙酰胺和4-苯氧基苯酚反应,制备了一种新的化合物N-甲基-2-(4-苯氧基苯氧基)乙酰胺,该化合物已取得中国发明专利ZL2004100.84390.1。考察了反应温度、反应时间、物料摩尔比对化合物收率的影响,确定了合成工艺条件为:反应温度75~85℃,反应时间4 h,n(N-甲基氯乙酰胺)∶n(4-苯氧基苯酚)=1.2∶1.0。在此条件下,N-甲基-2-(4-苯氧基苯氧基)乙酰胺的产率达85%以上。用N-甲基-2-(4-苯氧基苯氧基)乙酰胺与苯氧威分别对蔬菜蚜虫进行了防治实验,两化合物药效接近。化合物的结构经IR、MS1、HNMR和元素分析进行了表征。     

4-巯基-1,2-苯二甲腈的合成

以邻苯二甲酰亚胺为起始原料，经硝化，氨解、脱水、还原、重氮化等5步反应合成了4－巯基－1，2－苯二甲腈，用核磁共振谱和质谱确证了结构。     

香豆素肟酯类化合物的合成

以取代的3-乙酰基香豆素或3-丁酰基香豆素为原料,通过两步法合成了一系列香豆素肟酯类化合物(Ⅲa~k)。以3-乙酰基香豆素肟与乙酸酐的反应为模板反应,考察了溶剂的种类和反应温度对产物Ⅲa产率的影响,结果表明:以四氢呋喃为溶剂、反应温度为60℃时,产物Ⅲa的产率最高(88%)。在最优条件下,以67%~92%的收率得到11种含不同取代基的香豆素肟酯类化合物。对目标化合物的结构进行了红外、核磁、高分辨质谱确证,并对Ⅲa进行了X射线单晶衍射分析。     

4-硝基邻苯二甲腈的合成研究

以邻苯二甲酸酐为原料经亚酰胺化,硝化、氨解后得到4－硝基邻苯二甲酰胺,再在N,N－二甲胺存在下用三氯氧磷脱水制得4－硝基邻苯二甲腈,反应条件温和,产品纯度高,总产率达到36％。     

香豆素类荧光化合物的合成及表征

以取代苯甲醛分别与丙二酸及丙二腈反应制备了两种3-羧酸香豆素及两种3-氰基香豆素,用IR、1HNMR、质谱、元素分析对产物进行了结构表征。3-羧基香豆素最优环合反应时间是72 h。经解析发现,3-羧基-6-氟-7-羟基香豆素(Ⅱa1)的晶体结构属三斜晶系,P-1空间群,晶胞参数:a=0.686 9(3)nm,b=0.699 6(3)nm,c=1.431 5(6)nm,Z=2,F(000)=310。最终偏离因子R=0.111 4,wR=0.309 0。晶体结构中存在π-π堆积作用。     

1,2-二甲基-4-叔丁基苯的合成

以氧化铁为催化剂,叔丁基氯和邻二甲苯为原料合成了1,2-二甲基-4-叔丁基苯。反应过程不用添加溶剂,没有废液产生,对环境更为友好。探讨了反应温度、反应时间、叔丁基氯和邻二甲苯摩尔比、催化剂用量对反应的影响。结果表明:反应温度50℃,反应2.5 h,以氧化铁为催化剂,1,2-二甲基-4-叔丁基苯收率97.77%,选择性为99.48%。纯度为99.3%(GC),结构经核磁(1HNMR)表征。     

Reversible addition-fragmentation chain transfer polymerization of 7-(4-(acryloyloxy)butoxy)coumarin

The light sensitive vinyl monomer with coumarin unit, 7-(4-(acryloyloxy)butoxy)coumarin (7AC), was synthesized. The reversible addition-fragmentation chain transfer (RAFT) polymerization of 7AC, initiated by 2,2′-azobisisobutyronitrile (AIBN), was carried out using 2-cyanoprop-2-yl dithiobenzoate (CPDB) as a RAFT agent in N,N-dimethylformamide (DMF) solution. The kinetics exhibited first-order relationship with respect to the monomer concentration. The molecular weight of the polymer increased linearly with the monomer conversion. The chain extension of poly(7-(4-(acryloyloxy)butoxy)coumarin) (P7AC) using styrene (St) as the second monomer demonstrated that the obtained polymers were almost “living”. The fluorescence intensity of P7AC increased with the molecular weight of P7AC and was stronger than that of the monomer. The obtained polymer had strong ultraviolet (UV) absorption at 322 nm. The molecular weights of the polymer had no effect on its ultraviolet absorption intensity. The coumarin structure existing in P7AC underwent [2 + 2] cycloaddition reaction (photodimerization) under UV irradiation in tetrahydrofuran (THF) solution, which can be further used to prepare small particles from the single polymer.     

4-(水杨醛氧基)邻苯二甲腈的合成及其表征

以4-硝基邻苯二甲腈和水杨醛为原料,在无水碳酸钾的催化下合成了一种新的酞菁前驱体4-(水杨醛氧基)邻苯二甲腈。产物经IR、UV-Vis、^1HNMR及MS表征确认了其结构,同时对该物质的最佳合成条件进行了优化,产率达94．3％。     

杂多酸催化7-羟基-4-甲基香豆素的无溶剂合成

报道了以杂多酸(H3PW12O40、H3PMo12O40、H8SiW12O42、H6P2W18O40、H4SiW12O40、H6PMo6W6O40)为催化剂,以乙酰乙酸乙酯和间苯二酚为原料,通过Pechmann反应合成标题化合物的方法。探讨了以H4SiW12O40为催化剂时反应温度、催化剂用量、反应时间、原料比诸因素对产品收率的影响。实验表明,H4SiW12O40是合成标题化合物的良好催化剂,在反应温度为130℃,反应时间为50min,n(间苯二酚)∶n(乙酰乙酸乙酯)=1∶1.3,催化剂用量为1.5%(与间苯二酚的物质的量比)时,产品收率75.9%。     

Synthesis,characterization and self-promoted cure behaviors of a new phthalonitrile derivative 4-(4-(3, 5-diaminobenzoyl) phenoxy) phthalonitrile

A new amino-containing phthalonitrile derivative 4-(4-(3, 5-diaminobenzoyl) phenoxy) phthalonitrile (DAPN) was successfully synthesized. Its structure was identified by FT-IR and ¹H-NMR. DAPN can be thermally polymerized by duration at 230 °C for various times under a nitrogen atmosphere, even in the absence of curing additives. The thermal properties of the cured products were characterized by TGA and DSC. The 5 and 10% weight loss temperatures ranged from 442 to 446 and 504 to 505 °C, respectively. Char yields (800 °C) were in the range of 72.7–72.9%. DSC data showed that the melting peak of the cured products disappeared due to their thermal polymerization. The insolubility in concentrated sulfuric acid and FT-IR of the cured products indicated the formation of cross-linked networks.     

四氯化锡催化合成 7-羟基-4-甲基香豆素

采用四氯化锡作催化剂,以间苯二酚和乙酰乙酸乙酯为原料,合成了7-羟基-4-甲基香豆素。通过实验条件找到了,以四氯化锡为催化剂合成目标化合物的适宜反应条件。     

2-(3,4-二氯苯基)-4-氟苯胺的合成工艺研究

以对氟苯胺为起始原料,经过乙酰化、溴化得到2-溴-4-氟乙酰苯胺,与3,4-二氯苯硼酸通过Suzuki偶联并脱去乙酰基得到2-(3,4-二氯苯基)-4-氟苯胺。并对反应条件进行了优化,目标总收率为66.3%,其结构经MS,1H NMR确证。     

7-羟甲基-3,4-二氢-2(1H)-喹啉酮的合成研究

以氢化肉桂酸和甲醇为原料,经过甲酯化、氯乙酰化、硝化、乙酯化、铁酸还原、环合以及硼氢化钠还原得到标题化合物。其中,改进了原参考文献中硝基还原关环及硼氢化钠还原等反应条件,提高了目标产物的总收率,各步产物经~1HNMR表征。     

Synthesis and in vitro Anticancer Activity of Zinc(II) Phthalocyanines Conjugated with Coumarin Derivatives for Dual Photodynamic and Chemotherapy

The combination of photodynamic therapy and chemotherapy is a promising strategy to overcome growing problems in contemporary medicine, such as low therapeutic efficacy and drug resistance. Four zinc(II) phthalocyanine–coumarin conjugates were synthesized and characterized. In these complexes, zinc(II) phthalocyanine was used as the photosensitizing unit, and a coumarin derivative was selected as the cytostatic moiety; the two components were linked via a tri(ethylene glycol) chain. These conjugates exhibit high photocytotoxicity against HepG2 human hepatocarcinoma cells, with low IC₅₀ values in the range of 0.014–0.044 μM . The high photodynamic activities of these conjugates are in accordance with their low aggregation tendency and high cellular uptake. One of these conjugates exhibits high photocytotoxicity and significantly higher chemocytotoxicity. The results clearly show that the two antitumor components in these conjugates work in a cooperative fashion. As shown by confocal microscopy, the conjugates can localize in the mitochondria and lysosomes, and one of the conjugates can also localize in the cell nuclei.