1-烷基-1''-乙酰基二茂铁的合成

用新方法合成了1-烷基-1'-乙酰基二茂铁,该法与传统方法相比易于得到单一产物.通过7种1-烷基二茂铁甲酸与三氯化磷作用形成酰氯,再与乙酰乙酸乙酯的钠盐进行反应,皂化脱羧得到1-烷基-1'-乙酰基二茂铁化合物,用元素分析、红外光谱、核磁共振氢谱确定了化合物的结构.     

1-烷基-1'-乙酰基二茂铁的合成

用新方法合成了1-烷基-1'-乙酰基二茂铁, 该法与传统方法相比易于得到单一产物. 通过7种1-烷基二茂铁甲酸与三氯化磷作用形成酰氯, 再与乙酰乙酸乙酯的钠盐进行反应, 皂化脱羧得到1-烷基-1'-乙酰基二茂铁化合物, 用元素分析、红外光谱、核磁共振氢谱确定了化合物的结构.     

由2-烷基蒽醌一步法制备2-烷基蒽

本文报道了以2-烷基蒽醌为原料,结晶硫酸铜为催化剂,锌粉为还原剂于浓氨水(25%～28%)中一步法制备2-烷基蒽.产物通过硅胶柱层析,收率范围:55%～90%.文中从取代基的电子效应和空间位阻角度分析了产率的变化规律.同时考察了其它几种无机盐用作催化剂的催化作用.     

1-三氯锡烷基-2,3-丁二烯和2-三氯锡烷基-1,3-丁二烯与甲醛反应的B3LYP研究

用密度泛函方法在B3LYP/6-31G^**水平上研究了1-三氯锡烷基-2,3-丁二烯和2-三氯锡烷基-1,3-丁二烯与甲醛的反应.优化得到各驻点的几何构型,通过振动分析和内禀反应坐标对过渡态进行了确认,解析了反应路径.并用SCRF(PCM)方法在同一水平上对在CH₂Cl₂溶液中的两反应进行了研究.计算了两反应在气相和CH₂Cl₂溶液中的活化能垒、自由能和平衡常数.结果表明,反应具有很强的选择性,主要得到1-三氯锡烷基-2,3-丁二烯与甲醛反应的产物.该结果与实验事实一致.     

3-烷氧基-3-烷基异吲哚啉-1-酮的合成

为探索3-亚烷基异吲哚啉-1-酮在有机合成中的应用潜力，构建新型的异吲哚啉-1-酮类化合物，本文以3-亚烷基异吲哚啉-1-酮和醇为原料，在三氯硅烷与路易斯碱催化剂作用下发生加成反应，得到一系列3-烷氧基-3-烷基异吲哚啉-1-酮类化合物，并初步尝试了以手性路易斯碱催化该反应。综上，本文建立了一种新型异吲哚啉-1-酮类化合物的合成方法，该方法条件具有温和、操作便捷、底物适用范围广和收率普遍较高的特点。     

新型N-取代苯基-9-烷基-3-咔唑磺酰脲类化合物的合成及其抗肿瘤活性

以9-烷基咔唑为原料,经磺化、氯化和氨化反应制得9-烷基咔唑-3-磺酰胺(4a和4o);取代苯胺与三光气反应制得取代苯基异氰酸酯(6a~6n,6s,6Ⅳ);4分别与6经缩合反应合成了30个新型的N-取代苯基-9-烷基-3-咔唑磺酰脲类化合物(7a~7Ⅳ),其结构经1H NMR,IR和ESI-MS表征。对7进行了Cdc25B抑制活性筛选。结果表明,在用药浓度为20μg·m L-1时,其中12个化合物对Cdc25B具有良好的抑制活性,抑制率大于90%。     

?-3-O-酰基-2-O-苄基-甘油二烷基磷酸酯的合成和结构表征

?-3-O-酰基-2-O-苄基-甘油二烷基磷酸酯的合成和结构表征; ?-O-酰基-O-苄基-甘油二烷基磷酸酯;磷脂类似物;生物活性物质     

氢氧化铯作用下α-烷基(或α,α-二烷基)丙二酸二乙酯的合成

以DMF为溶剂,卤代烃(RX)与丙二酸二乙酯(1)在氢氧化铯(CsOH)催化下合成了α-烷基丙二酸二乙酯(2)和α,α-二烷基丙二酸二乙酯(3). 当r[n(RX) ∶ n(CsOH) ∶ n(1)]=1.0 ∶ 1.0 ∶ 1.0时,2为主要产物;当r=2.2 ∶ 2.0 ∶ 1.0时,3为主要产物.化合物的结构经1H NMR和MS表征.     

3-(1-亚胺基氟烷基)-1H-喹啉-2-酮类化合物的合成研究

用2-氟烷基乙酸为初始原料, 用氯化亚砜或五氯化磷将其转化为相应的酰氯, 后者在室温与邻胺基苯甲醛缩合, 通入氨气回流反应得到3-(1-亚胺基氟烷基)-1H-喹啉-2-酮类化合物, 产率中等.     

2-烷基-6-甲氧基-1,4-苯醌的全合成

3,5-二甲氧基苯甲醛经格氏、氧化反应制到3,5-二甲氧基苯基烷基酮, 然后在微波辐射下经黄鸣龙还原和选择性脱甲基化、Teuber氧化反应制得目标化合物, 产率均在50%以上. 产物结构经IR, 1H NMR, 元素分析等进行了表征.     

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.