2-芳基-3,4-二氮杂芴酮和2-芳基-3,4-二氮杂螺二芴衍生物的合成

水合茚三酮与芳甲基酮、水合肼缩合环化制得2-芳基-3,4-二氮杂芴酮(2); 2经还原得2-芳基-3,4-二氮杂芴(3).2与2-溴联苯格氏试剂反应得到中间体叔醇(4); 4在酸性条件下关环合成了2-芳基-3,4-二氮杂螺二芴,其结构经1H NMR,13C NMR和元素分析表征.     

4-(1-硫杂-2亚氨基-3,4-二氮杂-1,4-亚丁基)-4-脱氧阿维菌素B1a的合成

以阿维菌素B1a为原料经选择性C-5羟基保护、氧化合成5-O-烯丙氧羰基-5-氧代-5-脱氧阿维菌素B1a (3), 然后与N-取代氨基硫脲偶联, 缩合产物经MnO2氧化关环、脱保护得到10个未见文献报道的4-(1-硫杂-2-亚氨基- 3,4-二氮杂-1,4-亚丁基)-4-脱氧阿维菌素B1a (7a～7j). 目标化合物结构经1H NMR, 13C NMR和MS确证.     

6,7-二氧亚甲基-3-氮杂(硫杂)-1(2H,4H)吖啶酮及其衍生物的合成

氮杂吖啶酮;硫杂吖啶酮;杂环化合物;6;7-二氧亚甲基-3-氮杂(硫杂)-1(2H;4H)吖啶酮及其衍生物的合成     

(1R,3S,4S)-2-苄氧羰基-2-氮杂双环[2.2.1]庚烷-3-羧酸的合成

以(R)-(+)-α-甲基苄胺为原料,依次经缩合,Diels-Alder反应,还原,Cbz-保护和水解反应,合成了抗丙肝新药HCV NS3/4A蛋白酶拟肽类抑制剂的重要中间体——(1R,3S,4S)-2-苄氧羰基-2-氮杂双环[2.2.1]庚烷-3-羧酸,总收率66%,其结构经1H NMR和ESI-MS确证。     

3-氨基-1,3,4,5-四氢-2H-1-苯并氮杂-2-酮的合成

以3-溴-1,3,4,5-四氢-2H-1-苯并氮杂-2-酮为起始原料,与苄胺反应制得3-苄氨基-1,3,4,5-四氢-2H-1-苯并氮杂-2-酮(2);2经5%Pd/C催化加氢合成了3-氨基-1,3,4,5-四氢-2H-1-苯并氮杂-2-酮(3),总收率90%。最佳氢化反应条件为:以无水乙醇为溶剂,5%Pd/C用量为总用量的10%,于100℃/2.5 MPa条件下反应10 h,3的收率95.5%,纯度99.7%。5%Pd/C可套用7次,收率稳定在95%左右。     

3-氨基-1,3,4,5-四氢-2H-1-苯并氮杂革-2-酮的合成

以3-溴-1,3,4,5-四氢-2H-1-苯并氮杂--2-酮为起始原料,与苄胺反应制得3-苄氨基-1,3,4,5-四氢-2H-1-苯并氮杂(堇)-2-酮(2);2经5％ Pd/C催化加氢合成了3-氨基-1,3,4,5-四氢-2H-1-苯并氮杂——革)-2-酮(3),总收率90％.最佳氢化反应条件为:以无水乙醇为溶剂,5％ Pd/C用量为总用量的10％,于100℃/2.5 MPa条件下反应10 h,3的收率95.5％,纯度99.7％.5％ Pd/C可套用7次,收率稳定在95％左右.     

1-(3-氨基丙基)-2,8,9-三氧杂-5-氮杂-1-硅杂双环[3,3,3]十一烷衍生物的合成及其抗肿瘤活性研究

通过1-(3-氨基丙基)-2,8,9-三氧杂-5-氮杂-1-硅杂双环[3,3,3]十一烷与酸反应或1-(3-氯丙基)-2,8,9-三氧杂-5-氮杂-1-硅杂双环[3,3,3]十一烷与胺反应,合成了14种1-(3-氨基丙基)-2,8,9-三氧杂-5-氮杂-1-硅杂双环[3,3,3]十一烷衍生物.体外细胞培养试验结果表明,某些1-(3-氨基丙基)-2,8,9-三氧杂-5-氮杂-1-硅杂双环[3,3,3]十一烷衍生物对艾氏腹水癌细胞具有较好的杀伤活性.     

-羧基二硫缩烯酮的脱羧重氮化偶联反应研究：一种合成4，4-二烷硫基-1，2-二氮杂-1，3-丁二烯衍生物的新方法

报道了一种合成二烷硫基取代的1，2-二氮杂-1，3-丁二烯类化合物的新方法：在NaHCO₃水溶液中，a-羧基二硫缩烯酮和芳基重氮盐发生脱羧重氮化偶联反应，以较高的产率生成4，4-二烷硫基-1，2-二氮杂-1，3-丁二烯衍生物。     

[Hg(C5H4S5)I2]2的合成与晶体结构(C5H4S5 = 4,5-亚乙基二硫杂-1,3-二硫杂-2-硫酮)

用 HgI2 和 4,5-亚乙基二硫杂-1,3-二硫杂-2-硫酮 (C5H4S5)反应,合成一种二核汞配合物[Hg(C5H4S5)I2]2 1。X 射线衍射结果表明,晶体属于单斜晶系,C2/c 空间群,晶胞参数 a =21.6847(1),b = 8.5125(4),c = 15.6699(8),a=112.7850(1)°,V=2666.8(2) ?3。Mr = 1357.54,Z = 4,Dx = 3.381 g/cm3,ì = 16.913 cm–1,F(000) = 2400,R=0.0639,wR=0.1711,S=1.052。配合物 1 具有二聚体结构,2 个汞原子通过 2 个碘原子桥联,形成 1 个 Hg2I2菱形平面,汞原子周围的配位是四面体结构,通过分子间的硫…硫作用和碘…硫作用,形成准二维超分子网络。 S S S H g I I S S S S I I H g S     

3-杂环基硫取代-1,3,4,5-四氢-2-氧代-苯并氮杂衍生物的合成

以芳酰肼为原料,合成了一系列3-巯基-5-芳基-1,2,4-三唑、2-巯基-5-芳基-1,3,4-噁二唑和2-巯基-5-芳基-1,3,4-噻二唑,并通过硫原子对3-溴-2-氧代-苯并氮杂3-位上的亲核取代反应将杂环化合物引入了苯并氮杂的结构当中,合成了32个新的苯并氮杂杂环衍生物.为提高其在有机溶剂中的溶解性,在苯并氮杂的N原子上引入乙酸乙酯和乙酸叔丁酯基取代基,合成了36个新衍生物.所有化合物经质谱、核磁共振谱及元素分析确证了结构并初步测定了抗菌活性.     

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.