新型多重氮杂杯[4]芳烃衍生物的合成

对叔丁基杯[4]芳烃-1,3-二醛基衍生物1与水杨酰肼、烟酰肼、异烟酰肼反应, 合成了具有开链结构新型杯[4]多重氮杂衍生物2a～2c, 产率分别为88%, 85%和90%. 化合物1与乙二酰肼、丙二酰肼、己二酰肼反应, 得到具有桥联结构的新型杯[4]多重氮杂衍生物3a～3c, 产率分别为86%, 89%和90%. 新化合物的结构经元素分析、质谱、核磁共振谱等表征证实, 杯[4]芳烃单元均为1,3-取代且采取锥式构象.     

气相色谱-质谱法测定浓缩苹果汁中丁酰肼残留量

采用在碱性条件下将样品中丁酰肼水解为不对称二甲基联氨,再用水杨醛与之发生衍生化反应的前处理方法,建立了浓缩苹果汁中丁酰肼残留量的气相色谱-质谱(GC-MS)测定方法。以丁酰肼浓度对峰面积作图得校正曲线,回归方程为y=100 211x-11 156(r=0.999 6),检出限(3S/N)为0.01 mg.kg-1,测定结果的相对标准偏差为1.60%~6.23%,回收率为92%~107%。     

缩胺硫脲的合成及其抗癌活性的研究

缩胺硫脲是一类结构新颖,具有多种生物活性的新化合物(Ⅰ_1-12)。首先用硫酸二甲酯代替文献中的碘甲烷,与肼、二硫化碳在氢氧化钾作用下生成肼基二硫代甲酸甲酯(Ⅱ),产率60%。Ⅱ与2-乙酰取代基或苯甲醛缩合反应生成3-(1-取代乙撑)肼基二硫代甲酸甲酯(Ⅲ),产率54.0-91.6%。Ⅲ与1-取代哌嗪反应生成Ⅰ_1-12,产率41.7-83.8%。     

1-吡唑酰基-2-烷氧基羰基肼类化合物的合成及其生物活性

4-取代-1-甲基-3-乙基-5-吡唑甲酰肼与氯甲酸酯缩合得到16个1-吡唑酰基-2-烷氧基羰基肼类化合物(2a~2h和3a~3h,其中14个是新化合物),其结构经1H NMR,IR,MS和元素分析表征。初步生物活性测试结果表明,当浓度为500μg.mL-1时,3a,3b和3 e对油菜菌核病菌抑制活性均达到90%,3d对小麦白粉病菌的抑制活性达到90%;2h对蚕豆蚜的抑制活性达到92.75%。当浓度为1 000μg.mL-1时,2h对粘虫的抑制活性达到100%。     

水合肼在多壁碳纳米管修饰电极上的电化学行为及测定

报道了水合肼在碳纳米管修饰电极上的电化学行为以及水合肼测定的新方法。与裸玻碳电极相比,多壁碳纳米管修饰玻碳电极使水合肼的氧化峰电流显著提高,同时氧化过电位降低,测定灵敏度大为提高。优化了底液、pH、修饰剂量等测定条件。在最佳条件下,该修饰电极测定水合肼的线性范围为2.9×10-8~9.8×10-4mol/L,线性相关系数为-0.9945,检出限为1.0×10-9mol/L。对1.0×10-4mol/L的水合肼平行测定10次的相对标准偏差为4.4%。此方法已用于模拟水样中水合肼的测定。     

3,6-二取代苯基-二-1,2,4-三唑并[3,4-b]-1,3,4-噻二唑衍生物的合成

以2,5-二巯基-1,3,4-噻二唑为原料, 与水合肼缩合, 生成2,5-二肼基-1,3,4-噻二唑. 2,5-二肼基-1,3,4-噻二唑与苯甲酰氯反应生成2,5-二酰肼基-1,3,4-噻二唑, 以POCl₃为环合剂环合酰肼基-1,3,4-噻二唑, 合成3,6-二取代苯基- 二-1,2,4-三唑并[3,4-b]-1,3,4-噻二唑衍生物, 合成的新化合物的结构通过元素分析、红外光谱、核磁共振氢谱和质谱予以证实, 并提出了环化反应机理.     

系列新型硫杂杯[4]芳烃氮杂衍生物的合成

在对叔丁基硫杂杯[4]芳烃的下缘1,3位引入芳醛基, 合成了硫杂杯[4]二醛基衍生物2. 化合物2与苯胺、水杨酰肼、烟酰肼、异烟酰肼等通过席夫碱缩合反应得到新型硫杂杯[4]氮杂衍生物3a～3d, 产率分别为83%, 80%, 77%和79%. 化合物2与邻苯二胺、乙二酰肼、丙二酰肼、己二酰肼等通过“1＋1”分子间缩合得到新型1,3-桥联硫杂杯[4]氮杂衍生物4a～4d, 产率53%, 51%, 59%和66%. 新化合物的结构经IR, ¹H NMR, MS和元素分析等证实.     

异菸酰肼的 N-氯乙酰衍生物及2,6-二氨基异菸酸衍生物的合成及其抗结核作用

1.合成了三种异烟酰肼的衍生物,即 sym-氯乙酰基-异烟醯基肼、sym-三氯乙酰基-异烟酰基肼及 sym-一氯乙酰基-异烟酰肼盐酸(?)菜碱。这三种衍生物对 B.sme-gmatis 的抗菌作用分别为1∶16,000;1∶8,000;1∶8,000。2.制备了八种2,6-二氨基异烟酸酯,即甲酯、乙酯、正丙酯、异丙酯、正丁酯、异丁酯、正戊酯、异戊酯。其中甲酯为已知物,馀为新化合物。其抗 B.smegmatis 的作用均为1∶2000。3.2,6-二氨基-异烟酰肼的抗 B.smegmatis为1∶2000;2,6-二氨基-异烟酰胺及2,6-二氨基-异烟酸均无抗 B.smegmatis 作用。     

高效液相色谱法测定粮食制品中甲醛残留量

研究建立了一种用HPLC测定粮食制品中甲醛残留量的分析方法。样品中甲醛经60℃水浴提取,与2,4 二硝基苯肼衍生后,生成的2,4 二硝基苯腙经石油醚萃取净化,用HPLC DAD分离测定,外标法定量。最小检出质量浓度为5×10-11g,对于5g样品,最低检出量为0.01mg kg,样品回收率>80%,相对标准偏差≤10%,能满足残留量分析的要求。     

1,1,1-三氯-2-取代肼基-3-硝基丙烷及其衍生物的合成

叙述了以1,1,1-三氯-2-乙酰氧基-3-硝基丙烷和1,1,1-三氯-2-肼基-3-硝基丙烷为原料,合成脂肪和芳香肼类、酰肼类、偶氮类以及腙类等四十三个新化合物的方法,将N-芳基-N'-[2-(1,1,1-三氯-3-硝基)丙基]肼用N-溴代丁二酰亚胺氧化成1,1-二氯-2-芳偶氮基-3-硝基丙烯后,不经分离直接加入过量的醇和定量的水继续反应,可方便地获得β-硝基丙酮酸酯腙类化合物,收率达60%以上。初步抑菌活性测定结果表明,大多数化合物呈现不同程度的抑菌活性,其中以肼类和偶氮类化合物的活性最高,丙酮酸酯腙类化合物次之。     

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.