Pd2(dba)3/BINAP催化合成[4,4′-(4,4′-二苯亚胺基)二苯甲酰胺基]二苯醚

在三乙胺催化下,4-溴苯甲酰氯与4,4′-二氨基二苯醚反应制得[4,4 ′-(4,4′-二溴)-二苯甲酰胺基]二苯醚(1);1与苯胺在Pd2 (dba) 3/BINAP催化下合成了新化合物——[4,4′-(4,4′-二苯亚胺基)二苯甲酰胺基]二苯醚,其结构经1 H NMR和FT-IR表征.     

2,1,3-苯并硒二唑与联苯二胺类共轭共聚物的金属催化法合成与表征

利用金属催化法分别合成出了2,1,3-苯并硒二唑与N,N′-二氯联苯醌二亚胺、3,3′-二甲基-N,N′-二氯联苯醌二亚胺,3,3′-二甲氧基-N,N′-二氯联苯醌二亚胺的共轭交替共聚物:聚(N,N′-联苯醌二亚胺-2,1,3-苯并硒二唑),聚(3,3′-二甲基-N,N′-联苯醌二亚胺-2,1,3-苯并硒二唑),聚(3,3′-二甲氧基-N,N′-联苯醌二亚胺-2,1,3-苯并硒二唑)。利用凝胶色谱(GPC)、红外光谱、紫外可见光谱以及循环伏安(CV)等对这三种共聚物进行了表征和性能研究。紫外可见光谱分析结果表明,这三种共聚物分别在305nm、421nm,325nm、438nm和330nm、558nm处出现吸收峰,但由于受侧基的影响,聚(3,3′-二甲氧基-N,N′-联苯醌二亚胺-2,1,3-苯并硒二唑)相对于聚(N,N′-联苯醌二亚胺-2,1,3-苯并硒二唑)和聚(3,3′-二甲基-N,N′-联苯醌二亚胺-2,1,3-苯并硒二唑)的共轭程度要高,而且共聚物链上的侧基对其电化学性能也有一定的影响。     

3,3′-二氨基-2,2′,4,4′,6,6′-六硝基二苯胺钾的合成

由间二氯苯合成了热安定性炸药3,3′-二氨基-2,2′,4,4′,6,6′-六硝基二苯胺钾,目标化合物和部分中间体经元素分析,HNMR和MS表征,总收率58％。     

N,N’-二苯基-N,N’-二(9,9-二甲基芴-2-基)-9-己基-(4,4’-二胺基苯基)咔唑的合成方法及表征

以2,7-二溴咔唑为原料经过N-烷基化、Suzuki偶联反应、Buchwald-Hartwig偶联反应合成了有机发光二极管(OLED)空穴传输材料N,N’-二苯基-N,N’-二(9,9-二甲基芴-2-基)-9-己基-(4,4’-二胺基苯基)咔唑,利用NMR、IR和熔点等分析方法对产物结构进行了表征,并通过TG、UV-Vis及荧光光谱研究了物质的热稳定性和光学性能。     

5,5-二甲基-2-氧代-2-(N,N＇-对苯二胺基-二苄基)- 二-1,3,2-氧磷杂环己烷的合成及表征

以新戊二醇、三氯化磷和乙醇为原料制得中间体5,5-二甲基-1,3,2-二氧磷杂环己烷-2-氧(DPDO),用DPDO)与由芳醛和对苯二胺缩合制得的席夫碱SBⅠ～SBⅢ加成,合成了膨胀型阻燃剂5,5-二甲基-2-氧代-2-(N,N′-对苯二胺基-二苄基)-二-1,3,2-氧磷杂环己烷(DPPO Ⅰ～DPPOⅢ),通过元素分析,IR,NMR和MS对其结构进行表征,并对其在醇酸清漆中的应用进行了讨论.     

4-苯乙炔基苯胺封端聚酰亚胺树脂的合成与性能研究

使用4-苯乙炔基苯胺(4-PEA)作为反应性封端剂,和3,3′,4,4′-二苯醚四酸二酐(ODPA),3,3′,4,4′-联苯四酸二酐(BPDA),1,4-双(4′-氨基-2′-三氟甲基苯氧基)苯(BTPB)和3,4′-二氨基二苯醚(3,4-′ODA)反应合成了系列4-苯乙炔基苯基封端的聚酰亚胺低聚物,对低聚物的化学结构、热性能和熔体粘度以及固化后树脂的热性能等进行了研究.实验结果表明,低聚物均具有一定的结晶性,含有ODPA的聚酰亚胺低聚物较之含有BPDA的低聚物具有更低的熔体粘度,且出现最低熔体粘度的温度更低;固化后的树脂表现出良好的热性能,含有BPDA的树脂具有更高的玻璃化转变温度;系列低聚物中二胺单体的比例对于低聚物的熔体粘度和固化后树脂的热稳定性有一定影响.     

1-[2′,4′-二氟-(1,1′-联苯)-4-基苯基甲基]-咪唑的合成

以2,4-二氟联苯为起始原料,经酰化反应制得2′,4′-二氟-(1,1′-联苯)-4-基苯基甲酮(2);2经NaBH4还原得2′,4′-二氟-(1,1′-联苯)-4-基苯基甲醇(3);3经氯代得2′,4′-二氟-(1,1′-联苯)-4-基苯基氯甲烷(4);4与咪唑发生亲核取代反应合成了1-[2′,4′-二氟-(1,1′-联苯)-4-基苯基甲基]-咪唑(5). 2～5为新化合物,其结构经1H NMR, IR, MS和元素分析确证.     

原位一步法制备BTDA/4,4′-ODA/4,4′-SDA聚酰亚胺表面银化薄膜

采用原位一步自金属化的方法制备了具有反射性和导电性的表面银(Ag)化的聚酰亚胺(PI)薄膜,PI是由一种二酐(3,3′,4,4′-四羧基二苯酮酐,BTDA)和两种二胺(4,4′-二氨基二苯醚,4,4′-ODA与4,4′-二氨基二苯硫醚,4,4′-SDA)三元共聚而得,系统研究了4,4′-SDA的引入对薄膜性能及相态结构的影响.结果表明,4,4′-SDA的加入有助于银的还原和迁移,并利于薄膜导电性的提高,薄膜的反射率在两种二胺单体4,4′-ODA与4,4′-SDA的摩尔比为1比1时达到最佳.     

原位一步法制备BTDA/4,4′-ODA/4,4′-SDA 聚酰亚胺表面银化薄膜

采用原位一步自金属化的方法制备了具有反射性和导电性的表面银(Ag)化的聚酰亚胺(PI)薄膜,PI是由一种二酐(3,3′,4,4′-四羧基二苯酮酐,BTDA)和两种二胺(4,4′-二氨基二苯醚,4,4′-ODA与4,4′-二氨基二苯硫醚,4,4′-SDA)三元共聚而得,系统研究了4,4′-SDA的引入对薄膜性能及相态结构的影响.结果表明,4,4′-SDA的加入有助于银的还原和迁移,并利于薄膜导电性的提高,薄膜的反射率在两种二胺单体4,4′-ODA与4,4′-SDA的摩尔比为1比1时达到最佳.     

从中药佛手中分离鉴定两个柠檬油素二聚体

用 IR、NMR和X-射线晶体衍射分析了从佛手中分离出来的两个柠檬油素二聚体,证明它们的化学结构分别是顺式头-尾-3,3′,4,4′-柠檬油素二聚体(1)和顺式头-头-3,3′,4,4′-柠檬油素二聚体(2)。通过光反应从柠檬油素制备了1和反式头-头-3,3′,4,4′-柠檬油素二聚体(3)。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.