铜胺络合物催化合成1-羟基-二苯并[α,kl]呫吨化合物

以CuCl·22H2O与乙醇胺形成的络合物模拟氧化还原酶的功能,对联萘酚类化合物1a～1b进行了仿生氧化反应,生成结构新颖的二苯并[a,kl]呫吨化合物2a～2b,产物的结构经核磁、红外光谱及质谱等方法进行确证。     

铜胺络合物催化合成1-羟基-二苯并呫吨化合物

以CuCl2·2H2O与乙醇胺形成的络合物模拟氧化还原酶的功能，对联萘酚类化合物1a-1b进行了仿生氧化反应．生成结构新颖的二苯并[α，kl]呫吨化合物2a-2b，产物的结构经核磁、红外光谱及质谱等方法进行确证。     

3,7-二氟-10,11-二氢-二苯并[b,f]-氮杂■的合成

以4-氟-2-硝基甲苯为原料,经聚合、还原、缩合得到标题化合物,总收率20.3%.该方法步骤少、操作简便、收率较高,具有工业应用价值.     

3,7-二氟-10,11-二氢-二苯并[b,f]-氮杂▌的合成

以4-氟-2-硝基甲苯为原料,经聚合、还原、缩合得到标题化合物,总收率20.3%。该方法步骤少、操作简便、收率较高,具有工业应用价值。     

2-羟基-4-(5,6-二硝基-1H-苯并[2,3-d]咪唑-2-基)苯甲酸甲酯的 合成探索

以4,5-二硝基邻苯二胺和2-羟基对苯二甲酸单甲酯为起始原料,设计并成功采用一锅法合成出2-羟 基-4-(5,6-二硝基-1H-苯并[2,3-d]咪唑-2-基)苯甲酸甲酯（MHDIB）。以50 mL二乙二醇二甲醚为溶剂,1.5 g的2-羟基对苯二甲酸单甲酯和2.5 g SOCl2在80 ℃反应2 h制2-羟基-4-氯羰基苯甲酸甲酯。室温下快速向反应体系中加入1.56 g 4,5-二硝基邻苯二胺,并于85 ℃反应1 h后加入3.52 g 多聚磷酸,回流反应1 h后水析出粗产品,经乙醇重结晶得到纯度为93.67%的黄色针状产物,产率为17.82%。产物经IR、MS、1H NMR的准确定性和表征,作为AB型新单体的前体可应用于羟基改性PBI纤维即聚2-羟基-1,4-亚苯基-2,6-苯并[2,3-d：5',6'-d']二咪唑（H-PBI）的创新研究。     

硝基-3-氧-3,4-二氢-2H-[1,4]苯并(口恶)嗪-6-羧酸的合成

以4-羟基-3-硝基苯甲酸为原料,经酯化、醚化、还原合环、硝化、水解等5步反应,合成了两个未见文献报导的化合物7-硝基-3-氧-3,4-二氢-2H-[1,4]苯并(口恶)嗪-6-羧酸和8-硝基-3-氧-3,4-二氢-2H-[1,4]苯并(口恶)嗪-6-羧酸,其结构经IR、LC/MS、1HNMR和元素分析确证.     

无溶剂一锅法三氟乙酸铁高效催化合成14-取代-14-氢-二苯并[a，j]氧杂蒽

通过发展一种高效合成14-芳基或烷基取代-14-氢-二苯并[a,j]氧杂蒽的方法,可高收率地合成一系列目标产物。此外,该法具有反应时间短（仅为1～1．5h）、便于操作、环境友好、使用的铁催化剂价廉易得等一系列优点。因而,为合成该类化合物提供了一种切实可行的方法。     

2，6-二（对氨基苯）苯并[1，2-d；5，4-d’]二噁唑的合成

以三氯苯为原料，依此经过硝化、水解和催化加氢制得4，6-二氨基间苯二酚盐酸盐。在多聚磷酸中，此盐酸盐和对氨基苯甲酸缩合成标题化合物。分别对中间体的重结晶、缩合反应温度、缩合反应体系组成等方面进行了改进，总产率为70％。     

2,6-二[4-′(N,N-二苯基氨基)芪]苯并[1-2,4-5]二噁唑的合成与发光特性

通过对二苯氨基苯甲醛与2,6-二(4-氯甲基苯基)苯并[1-2,4-5]二唑之间的Wittig-Horner反应,设计并合成了一个2,6-二[4-′(N,N-二苯基氨基)芪]苯并[1-2,4-5]二唑新化合物,目的在于均二苯乙烯分子中同时引入空穴传输和电子传输结构单元,可望提高均二苯乙烯型发光材料的发光强度和光量子效率.采用UV-VisI、R1、HNMR和元素分析等分析方法对合成产物结构进行了确认,并考察了溶剂对其光致发光特性的影响.所合成化合物的相关分析数据表明:1)其分子中的两个均二苯乙烯基均为反式“芪”结构特征;2)随溶剂极性增高,其UV-Vis光谱和荧光光谱的λmax红移;3)可用作蓝色发光材料.     

2,6-二[4＇-（N,N-二苯基氨基）芪] 苯并[1-2,4-5]二唑的合成与发光特性

通过对二苯氨基苯甲醛与2,6-二（4-氯甲基苯基）苯并[1-2,4-5]二（口恶）唑之间的Wittig-Horner反应,设计并合成了一个2,6-二[4＇-（N,N-二苯基氨基）芪]苯并[1-2,4-5]二（口恶）唑新化合物,目的在于均二苯乙烯分子中同时引入空穴传输和电子传输结构单元,可望提高均二苯乙烯型发光材料的发光强度和光量子效率.采用UV-Vis、IR、1HNMR和元素分析等分析方法对合成产物结构进行了确认,并考察了溶剂对其光致发光特性的影响.所合成化合物的相关分析数据表明：1）其分子中的两个均二苯乙烯基均为反式＂芪＂结构特征;2）随溶剂极性增高,其UV-Vis光谱和荧光光谱的λmax红移;3）可用作蓝色发光材料.     

含环戊二烯络铁基团二苯并二噁英的合成

采用含环戊二烯络铁(FeCp)基团邻二氯苯和含羟基、巯基的二元酚类化合物合成含FeCp基团的二苯并二噁英.实验中,以N,N-二甲基甲酰胺(DMF)为溶剂,室温下,在K2CO3弱碱性介质中,产品收率高,副反应少,反应时间短.通过1H NMR和13C NMR对该类产品结构的研究表明产品纯度高;酚类的选择不同,H、C化学位移有一定差异.     

Synthesis of Condensed Benzo[N,N]-Heterocycles by Microwave-Assisted Solid Acid Catalysis

The synthesis of several types of condensed benzo[N,N]-heterocycles such as benzimidazoles, benzodiazepines, quinoxalinones by a microwave-assisted solvent-free solid acid catalyzed method is described. The commercially available, inexpensive K-10 montmorillonite is an excellent catalyst for the synthesis of the target compounds. Our approach is based on the reactions of a wide variety of o-phenylenediamines, with ketones, aldehydes and bifunctional reagents, respectively. The cyclization reactions were initiated by microwave irradiation. The products, in most cases, were obtained in very high yields (up to 98%) and excellent selectivities in very short reaction times. The effective combination of solid acid catalysis, solvent-free conditions and microwave irradiation provides an attractive and highly ecofriendly approach for the synthesis of these important heterocycles.     

相转移催化合成四乙酰氧基对叔丁基杯[4]芳烃

以聚乙二醇(PEG)600为相转移催化剂合成四乙酰氧基对叔丁基杯[4]芳烃。实验结果表明：当对叔丁基杯[4]芳烃1．0g,乙酸酐9mL,0．0224g浓98％H2SO4(质量分数)和0．4gPEG600,回流反应20min,产率达到75．1％。     

Synthesis of the [Ga]-MFI under atmospheric pressure

The crystallization of the [Ga]-MFI was investigated as a function of synthesis time under atmospheric pressure. The molar composition of the reactants was 100SiO₂-Ga₂O₃-llNa₂O-llTPABr-3500H₂O. The crystallinity of the [Ga]-MFT was examined by using several analytical instruments, such as XRD, XPS, XRF, FT-IR, solid-statemas-NMR, DTG/DTA, and SEM. The [Ga]-MFI was successfully synthesized under atmospheric pressure at 97 ‡C in 72 h. It was found that the nucleation of the [Ga]-MFI took a quite long time, but the crystallization took place very fast. It is supposed that nucleation is the rate-controlling step in the [Ga]-MFI synthesis under atmospheric pressure. Consequently, if the induction period of the nucleation can be shortened, it would be possible to synthesize the [Ga]-MFI commercially under atmospheric pressure.     

酶催化技术在手性化合物合成中的应用

介绍了有机介质中酶催化的原理、酶催化反应的特点以及与化学反应相比较具有的优点,酶催化在合成手性化合物方面的相关应用,并且展望了酶催化技术的应用前景。     

[BMIM]BF4离子液体催化合成甲基丙烯酸异冰片酯

制备了离子液体[BMIM]BF4,并用于催化合成甲基丙烯酸异冰片酯,研究α-蒎烯与甲基丙烯酸的反应特性。最佳工艺条件为：反应物料配比n（α-蒎烯）：n（甲基丙烯酸）=1．0：0．8,反应温度40℃,反应时间6h,离子液体的用量为α-蒎烯质量的5％。在此条件下,甲基丙烯酸异冰片酯收率达74％以上,纯度达99％。其离子液体可重复利用,经5次利用后酯收率仍在70％以上。     

Synthesis of Aminopyridazines from Aminocyclopropenylium Salts and Diazomethyl Compounds [1]

Amino-substituted cyclopropenylium salts ( 11a,b ) react with diazomethyl compounds ( 12a-i ) in dichloromethane or acetonitrile in the presence of a base (ethyldiisopropylamine, 1,5-diazabicyclo[4.3.0] non-5-ene) to form 4-aminopyridazines ( 13a-i ) specifically. The reaction is interpreted in terms of an initial electrophilic diazoalkane substitution to give diazomethylcyclopropenes ( 11 + 12 → 14 ) which undergo a [1.5]-cyclisation to form the betaines 16 which, in turn, isomerise with opening of the bridging bond to give the aminopyridazines 13 . In a similar manner, the tris[amino] cyclopropenylium salts 8a,b and 10a-c are converted to the 3,4,5-tris[amino]-pyridazines ( 21a-k ) by treatment with diazomethyl compounds ( 12a, c-f ).     

Oxidative Gold Catalysis Meets Photochemistry – Synthesis of Benzo[a]fluorenones from Diynes

Diynes bearing one terminal and one triarylmethyl‐substituted alkyne were converted into complex benzofluorenone derivatives via a one‐pot process involving a gold‐catalyzed step followed by a photocyclization/oxidation. In the first step an N‐oxide was used to position‐selectively generate an α‐oxo carbenoid at the terminal alkyne which after a regioselective 1,6‐carbene transfer along the tethered tritylalkyne and a subsequent aryl 1,2‐shift furnished tetraphenylethylene‐like derivatives. These intermediates were successfully transformed to fluorenones via oxidative photocyclization.

     

Synthesis of 2-Hydroxybenzo[a]pyrene,a Tumorigenic Phenol Derivative of Benzo[a]pyrene

An efficient synthesis of 2-hydroxybenzo[a]pyrene (1a) from 4,5,9,10-tetrahydropyrene via 2-methoxy-4,5,9,10-tetrahydropyrene (2e) is described. Friedel–Crafts acetylation of tetrahydropyrene affords the 2-acetyl derivative which is transformed to the 2-methoxy derivative 2e via Baeyer–Villager oxidation, hydrolysis, and treatment with dimethyl sulfate. Friedel–Crafts succinoylation of 2e with succinic anhydride and AlCl₃ takes place regiospecifically in the 7-position. The product is transformed to 1a via Clemmensen reduction, HF cyclization, Wolff–Kishner reduction, catalytic dehydrogenation, and demethylation with HBr.