双（甲基二茂铁基）代烷羟的合成

二茂铁衍生物在复合固体火箭推进剂中用作燃速催化剂,但其挥发性和迁移性较大,直接影响储存或使用时导弹的弹导性能。本文报导三种新型燃速催化剂:双(甲基二茂铁基)甲烷,2,2-双(甲基二茂铁基)丙烷和2,2-双(甲基二茂铁基)丁烷的合成和表征。小型试验表明其催化活性、挥发性及迁移性能均优于国内目前使用的叔丁基二茂铁。     

烷基二茂铁的合成及性质

电化学性质;燃速催化性;烷基二茂铁的合成及性质     

二茂铁基环氧衍生物

二茂铁基环氧的分子结构中同时含有环氧和二茂铁,是一类兼具化学活性和多功能性的特殊材料。这类材料具有单体结构多样性和聚合物的多功能性,近年来对其制备方法和应用的研究受到广泛关注。研究者们已利用二茂铁醛、酮、烯、氯醇、双醇、乙酰氯等为中间体,制备出二十多种小分子化合物。采用二茂铁接枝环氧聚合物或含烯单体自由基聚合,分别得到多种结构的聚合物。本文在综述二茂铁基环氧制备方法的基础上,进一步讨论了这类材料的结构稳定性。研究发现,当二茂铁处于环氧的邻位时,极易形成卡宾结构,使得环氧开环并重排成醛。通过列举典型研究实例,阐明其在功能材料、传感介质、燃速催化、催化剂配体以及药物合成等方面的应用,并就其在材料表界面的发展趋势进行了展望。     

新型燃速催化剂—烷基二茂铁桥联双聚分子的电化学研究

液态烷基二茂铁桥联双聚分子是一类新型燃速催化剂,它不仅具有催化活性高的优良特性,而且挥发性及迁移性均有改善,适宜用于火箭燃料复合固体推进剂。本文合成9种含不同取代基的双核二茂铁化合物,其中6种为首次合成。该9种化合物的通式为:其结构通式、各化合物的编号、英文名缩写及所含取代基和桥联基表示如下:     

多二茂铁基二氮杂己烷及其过渡金属配合物的合成

乙二胺与二茂铁甲醛或双二茂铁甲基氟硼酸盐反应，合成了１，６－二（二茂铁基）－２，５－二氮杂己烷和１，１，６，６－四（二茂铁基）－２，５－二氮己烷，它们与过渡金属（Ｆｅ＾２＋，Ｃｏ＾２＋，Ｎｉ＾２＋，Ｃｕ＾２＋，Ｚｎ＾２＋）盐在乙醇或乙醇－二氯甲烷中反应，是１４种过渡金属配合物，对这些化合物进行了表征，二种配体及其铜配合物用作复合固体推进剂的燃速调节剂时，基本不迁移，而燃速催化效率均超过辛基二茂铁。     

二茂铁基β-二酮及其Cu(Ⅱ)、Ni(Ⅱ)配合物的燃速催化性质

合成了含有苯基的二茂铁β-二酮,并对其结构进行了表征.在核磁共振氢谱中,苯环上含有拉电子的硝基时,β-二酮烯醇式含量几乎是100%,而含有给电子的甲氧基时,其烯醇异构体含量下降到84%.当将其与Cu(II)或Ni(II)配位后,在紫外吸收光谱中,300 nm以下归属于Fe(d)-π*和芳基π-π*的跃迁向长波方向移动5~17 nm.热重-差示扫描量热法(TG-DSC)实验表明,添加二茂铁基β-二酮或它们的Cu(II)或Ni(II)配合物于高氯酸铵(AP)中,不仅在一定程度上抑制了AP高温热降解阶段的升华,而且可使AP的热降解温度提前,以Cu(II)配合物提前得更为显著,含有甲氧基的Cu(II)配合物可使AP的热降解温度提前87℃.因此相对于二茂铁β-二酮配体及Ni(II)配合物,Cu(II)配合物是更好的燃速催化剂.     

二茂铁甲酰基1,1'-二烷基二茂铁的合成与性质

在研制丁羟固体推进剂的高效不迁移燃速催化剂中 ,我们设计的目标物的结构为ＦｃＣＨ (ＯＨ)Ｆｃ′Ｒ2 (Ｆｃ =Ｃ5Ｈ5ＦｅＣ5Ｈ4 ,Ｆｃ′=Ｃ5Ｈ4 ＦｅＣ5Ｈ3,Ｒ为烷基 ) .该类化合物的特点是两个二茂铁核连在同一碳上 ,且含有羟基官能团 ,它们似应具有高效和不迁移的燃速催化性能[1].此类化合物的合成是由二茂铁甲酰基 1,1′ 二烷基二茂铁化合物的羰基还原为羟基实现的 .为此 ,我们较为详细地研究了 5种二烷基二茂铁在三氯化铝催化下的二茂铁甲酰化反应 .此项工作未见报道 .二烷基二茂铁的茂环有α(与烷基相邻 )和 β(与烷基相间 )两种Ｈ原…     

(二乙基二茂铁基)二茂铁基甲醇及其胺衍生物的合成与 性质

1,1'-二乙基-2-(和3)-二茂铁酰基二茂铁经LiAlH4还原得到两种相应的双二茂铁基甲醇。它们对酸的敏感性很高，与BF3在二氯甲烷中作用可形成稳定的二茂铁基甲基碳正离子，无需从溶液中分离出来，便可与胺RNH2[R=C2H5,n-C3H7,n-C4H9,HOCH2CH2,HOCH(CH3)CH2,HOCH2CH(C2H5)]作用得到产率颇高的二茂铁基胺，这种由α-二茂铁基醇制备α-二茂铁基胺的方法具有简单、快速和原料廉价的特点。     

N-烷基双二茂铁甲胺类化合物的合成研究

双二茂铁甲醇、2，1′二乙基双二藏铁甲醇和3，1′－二乙基双二茂铁甲醇与BF3在CH2C12中作用，形成相应的双二茂铁甲基碳正离子。无需从反应混合物中分离出来，该离子与乙胺、丙胺以及丁胺分别反应得到了9种标题化合物。研究了化合物的物性与其结构的关系；研究了反应物质的量比对反应的影响。通过元素分析、IR和^1HNMR确证了化合物的结构。     

几个新型二茂铁衍生物的合成

二茂铁及其衍生物作为油类消烟剂、燃速催化剂等已得到应用,在药物、合成材料等方面亦具有应用前景。文献曾报道含二茂铁基β-二酮的合成及以它为配体的金属配合物。此类配合物均含两个以上金属原子,它们在有机合成中具有独特的催化活性。 我们将二茂铁甲酰丙酮分别与水扬酰肼、异菸肼、乙二胺及硫代氨基脲在甲醇或甲醇-水介质中进行缩合反应,合成了4个新型二茂铁衍生物,它们含有三个或四个配位功能基团,可作为多齿配体用于金属有机配合物的合成。衍生物的合成路线如下:     

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%.     

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.     

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.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

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.