4-正戊基环己酮的合成

以骨架镍催化4－正戊基苯酚加氢得到4－正戊基环己醇，再经氧化作用合成了4－正戊基环己酮，并探讨了催化加氢反应中的溶剂化作用。     

4-（4′-丙基环己基）环己醇的合成

钌／碳催化剂应用于4-(4′-丙基环己基)苯酚(3PCO)的加氢反应，合成了4-(4′-丙基环己基)环己醇。以环己烷为溶剂，在98℃／2MPa，3PCO的转化率为100．0％，催化剂可以重复使用两次。     

4-硝基二苯胺和4-亚硝基二苯胺钠催化加氢制4-氨基二苯胺 Ⅰ.溶剂对加氢反应的影响

用Pd—M/C催化剂(M为非贵金属),对工业原料4-硝基二苯胺及4-亚硝基二苯胺钠催化加氢制4-氨基二苯胺,其活性和选择性都较好。本文报导了在常压加氢中添加各种溶剂对反应的影响,并建议采用苯胺溶剂较适宜。     

超声条件下合成4—戊基（4‘—丙基）双环己基联苯

在超声辐射下,用相转移催化剂十六烷基三甲基溴化铵作助催化剂,室温下通过氯化钯催化４－（４’－丙基）环己基苯基硼酸与４－（４’－戊基）环己基溴苯偶联反应２０ｍｉｎ,合成了４－戊基（４’－丙基）双环己基联苯,反应转化率９７％,反式产物选择性６２％。     

TS-1分子筛催化苯的羟基化性能

研究了在温和反应条件下自制的ＴＳ－１分子筛催化苯羟基化的反应规律．着重考察了酸介质的影响和溶剂的作用，发现在水相和有机相中苯的羟基化和苯酚的进一步羟基化具有不同的规律，有机相中苯的羟基化是主要反应，水相中的主要反应是中间产物苯酚的进一步羟基化，溶剂的作用则是使苯和双氧水分子在ＴＳ－１分子筛表面上充分接触并发生反应．发现以丙酮为溶剂，采用乙酸或乙酸酐作介质，较之硫酸介质能更有效地提高苯的转化率；同中性介质相比，苯转化率提高了３２％；同硫酸相比，苯转化率提高了１５％，苯酚选择性提高了４５％．此外，还考察了反应温度、反应时间等其它因素对苯羟基化反应的影响，并在实验基础上推测了ＴＳ－１分子筛催化苯羟基化的反应机理．     

在Pt/HZSM-5双功能催化剂上FCC汽油加氢异构化反应机理及动力学研究

在活性趋于稳定的Pt/HZSM-5双功能催化剂上，利用连续流动微反一色谱装置，进行了催化裂化汽油加氢异构化反应机理和动力学的研究．在250-330℃，1．0-3．0MPa反应条件下，考察了催化汽油加氢异构化反应产物分布，按单分子反应机理，建立了催化裂化汽油中烯烃加氢异构化反应网络和动力学模型，计算了反应网络中各步的反应速率常数和活化能．结果表明：Pt／HZSM-5双功能催化剂具有较好的加氢和异构活性，在保证辛烷值不下降的条件下，可使催化裂化汽油中烯烃加氢饱和，达到降低汽油烯烃和提高安定性的目的．     

4-戊基(4′-丙基环己基)三联苯液晶的合成

在相转移催化剂十六烷基三甲基溴化铵的助催化作用下,用PdCl2催化芳基硼酸与溴代芳烃偶联反应合成了液晶化合物4－戊基（4′－丙基环己基）三联苯,反应转化率达到93％,反式产物选择性86％。结构经IR,^1H NMR和MS确证,并用DSC测定了此液晶的相变数据。考察了加料顺序和相转移催化剂对偶联反应的影响。提出了相转移条件下可能的催化循环机理,认为芳基硼酸是以ArB(OH)3^-离子形式参与偶联反应的。     

磷酸铈对磷化镍催化苯酚转移加氢的促进作用

通过氢气原位程序升温还原法制备了一系列不同Ce/Ni摩尔比的CePO₄-Ni₃P及Ni₃P催化剂,考察了其在苯酚催化转移加氢反应的催化性能.研究了Ce/Ni摩尔比、供氢溶剂、反应温度和反应时间对催化剂性能的影响,并初步考察了苯酚转移加氢的反应动力学.研究结果表明,CePO₄的加入能显著提升体相Ni₃P催化苯酚转移加氢的转化率,且Ce/Ni摩尔比为0. 2时促进作用最显著;在所考察的供氢溶剂中异丙醇展现出最好的性能;使用Ce PO₄(0. 2)-Ni3P作为反应催化剂,异丙醇作为供氢溶剂,220℃下反应6 h,苯酚转化率和环己醇选择性分别可达93. 1%和92. 0%.     

NaBH4/I2催化加氢还原碱木质素的研究

从麦草碱法制浆黑液中提取木质素,精制后,以苯乙酮为木质素的模型化合物,对催化剂组成及溶剂进行了考察.在此基础上,以NaBH4/I2为催化剂,无水乙醇为溶剂,对木质素进行加氢还原裂解反应研究.考察了温度和时间对木质素催化加氢效果的影响,采用红外光谱(FTIR)、元素分析及凝胶渗透色谱分析(GPC),表征木质素反应前后结构的变化.凝胶渗透色谱分析表明,加氢还原后木质素的分子量明显降低.采用自动电位滴定法测定反应前后木质素中总羟基含量,反应后木质素中总羟基含量为10.19%.得到了NaBH4/I2催化木质素加氢还原反应的最优条件:以1,2-二氯乙烷和乙醇(2∶1,v/v)作溶剂,m(NaBH4)∶m(I2)=1∶1,温度175℃,反应时间15 h.     

Hydrogenolysis of Lignin Catalyzed by NaBH4/I2

从麦草碱法制浆黑液中提取木质素,精制后,以苯乙酮为木质素的模型化合物,对催化剂组成及溶剂进行了考察.在此基础上,以NaBH4/I2为催化剂,无水乙醇为溶剂,对木质素进行加氢还原裂解反应研究.考察了温度和时间对木质素催化加氢效果的影响,采用红外光谱（FTIR）、元素分析及凝胶渗透色谱分析（GPC）,表征木质素反应前后结构的变化.凝胶渗透色谱分析表明,加氢还原后木质素的分子量明显降低.采用自动电位滴定法测定反应前后木质素中总羟基含量,反应后木质素中总羟基含量为10.19%.得到了NaBH4/I2催化木质素加氢还原反应的最优条件：以1,2-二氯乙烷和乙醇（2∶1,v/v）作溶剂,m（NaBH4）∶m（I2）=1∶1,温度175℃,反应时间15 h.     

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.     

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.     

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.     

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.