Br(o)nsted酸性离子液体催化合成阿司匹林

用Brcnsted酸性离子液体[Hmim]BF4、[bmim]HSO4和[bmim]H2PO4代替浓H2SO4为催化剂催化乙酸酐对水杨酸的乙酰化，合成阿司匹林。考察了反应温度、反应时间、催化剂用量、酐／醇摩尔比对水杨酸酰化反应产率的影响和离子液体的重复使用性能。选择了最佳反应条件，以[bmim]H2PO4作为催化剂，催化剂用量为0．28g（1．18×10^-3mol），水杨酸2．762g（0．02mol），乙酸酐4．083g（0．04mol），n（酐）：n（醇）=2：1，反应时间30min，反应温度70℃，产率最高达63．43％，并且[bmim]H2PO4溶于水后通过过滤和旋蒸脱水，重复使用3次，产率无明显变化。     

高聚合度Ⅱ-型聚磷酸铵的合成

用聚合反应-热处理两段工艺合成了高聚合度的聚磷酸铵（APP）阻燃材料,其结构经XRD,粒度及平均聚合度表征。优化反应条件为：磷酸氢二铵1mol,n（磷酸氢二铵）：n（五氧化二磷）：n（脲）：1．0：1．0：0．3．干燥氨气氛下于290℃反应30min,再经250℃-280℃后处理100min-110min。APP的平均聚合度大于150,粒度小于50μm。     

松香基琥珀酸双酯磺酸钠的合成及性质

以松香性产品歧化松香醇聚氧乙烯醚（RP）为原料合成了非离子表面活性剂歧化松香醇聚氧乙烯醚琥珀酸双酯磺酸钠（RPS）,研究了影响RP与马来酸酐（MA）的酯化反应及酯与NaHSO,磺化反应的各种因素,得出比较适宜的反应条件：酯化反应以对-甲苯磺酸作催化剂,其用量为RP质量用量的0．3％,反应温度130-140℃,n（RP）n（MA）=2：1,反应时间4h;磺化反应温度120-130℃,n（NaHSO3）：n（双酯）=1．1：1,反应时间4h。研究了合成产物的表面物理化学性质,结果表明：随着环氧乙烷（EO）聚合度（n）的增加,表面张力、钙皂分散力、乳化力先逐渐提高,临界胶束浓度和润湿力先逐渐减小,然后趋于平衡;RPS和RP相比,乳化力,泡沫性能及润湿力均有明显提高。     

纳米固体超强酸SO4^2-／Fe2O3催化合成尼泊金酸乙酯

以纳米固体超强酸SO4^2-／Fe2O3,催化尼泊金酸与乙醇的酯化反应合成了尼泊金酸乙酯。较适宜的反应条件为：尼泊金酸25mmol,n（尼泊金酸）：n（乙醇）=1：4,w（催化剂）=3．73％,甲苯15mL,于84℃～86℃反应3h,产率达到93．3％。     

配合物RuCl2（bdpx）（NH2CH2CH2NH2）的合成及其催化活性

合成了一种新的双膦-钌-二胺配合物——Rucl2（bdpx）（N心CH2CH2NH2）[bdpx=邻-二（二苯基膦）二甲苯]（1）,并研究了1催化苯乙酮（2）的加氢反应。在10．032mmol,n（2）：n（Me3COK）：n（1）=10000：120：1,氢气压力为3MPa的条件下,于70℃反应4h,2的转化率达100％。     

壳聚糖-（4-叔丁基邻苯二酚）的酪氨酸酶催化接枝初探

以自制马铃薯酪氨酸酶催化氧化4-叔丁基邻苯二酚成活性邻醌,后与壳聚糖接枝反应,并着重探讨了反应条件对接枝率的影响。通过红外光谱对该反应产物进行结构的初步表征,结果表明酶催化接枝反应的适宜条件为：4-叔丁基邻苯二酚浓度3．0mmol／L、酶活力20U／mL、反应时间30min、壳聚糖溶液百分含量0．5％;用线性电位滴定法测定其接枝率为37％～64％。     

KI催化酯交换合成碳酸二正辛酯的研究

研究了碳酸二甲酯与正辛醇酯交换合成碳酸二正辛酯（DOC）的反应，比较了卤化钾与系列碳酸钾复合催化剂的性能，考察了物料配比、反应温度、反应时间诸因素对该反应的影响，得出了该反应的最佳工艺条件．结果表明，KI具有较好的催化活性和选择性；在最佳反应条件（常压、反应温度140℃、反应时间为4h、n（DMC）：n（n-OctOH）=1：4、催化剂用量为总重1．25％。）下，DMC的转化率为83．7％，DOC的收率为70．0％，DOC的选择性为83．7％，甲基辛基碳酸酯（MOC）的收率为13．7％．     

一种聚氧乙烯醚链三头季铵盐表面活性剂的合成

以五甲基二乙烯三胺（PMDETA）、脂肪醇聚氧乙烯醚（FAPOE）和环氧氯丙烷（ECP）为原料,分两步合成了一种含聚氧乙烯醚链三头季铵盐的表面活性剂。对反应影响因素、产物结构与部分性能进行了分析与表征。结果表明：第一步反应n（ECP）：n（FAPOE）为2．5～3：1,溶剂为正己烷,四丁基溴化铵作相转移催化剂,无水K2CO3作缚酸剂,时间6～8h。第二步反应n（中间体）：n（PMDETA）为3．5—4．0：1,溶剂为正丁醇,时间40-45h;溶剂与时间是主要影响因素。定性表征符合产物结构：定量表征n（Cl^-）：n（阳离子部分）为3．4：1,略高于理论值。产物的表面活性高,1．0×10^-4mol／L水溶液的表面张力可降至6．65mN／m。     

高效抗菌Cu2+-壳聚糖季铵盐/丙烯酸复合物的制备

以过硫酸铵为引发剂,在壳聚糖季铵盐（HACC）上接枝丙烯酸（AAc）并络合Cu²⁺,制备了具有高效抗菌性能的HACC-g-PAAc-Cu²⁺复合物.采用红外光谱（FTIR）和核磁共振波谱（¹H NMR）表征了壳聚糖季铵盐接枝改性前后的化学结构变化;利用紫外-可见吸收光谱（UV-Vis）、Cu²⁺选择电极和热失重分析（TGA）表征了壳聚糖季铵盐接枝前后负载Cu²⁺的能力;测定了HACC-Cu²⁺和HACC-g-PAAc-Cu²⁺对金黄色葡萄球菌及大肠杆菌的最小抑菌浓度,并对小鼠经口摄入毒性和兔皮肤敷涂刺激性进行了考察.研究结果表明,在壳聚糖季铵盐上负载Cu²⁺能够有效提高其抗菌性;接枝丙烯酸能提高HACC负载Cu²⁺的能力和抗菌性,Cu/HACC结构单元的摩尔比由接枝前的3：7提高到接枝后的1：1;对金黄色葡萄球菌的最小抑菌浓度由60 mg/L下降到9.2 mg/L,对大肠杆菌的最小抑菌浓度由37 mg/L下降到6.3 mg/L,无摄入毒性和皮肤刺激性.     

C02（CO）8催化苯乙烯氢酯基化制α-苯基丙酸酯研究

以Co2（CO）8为催化剂,对苯乙烯与CO及甲醇氢酯基化反应制α-苯基丙酸甲酯的反应进行了研究,并根据实验结果提出了可能的催化反应机理．考察了催化剂用量、配体、溶剂、CO压力及反应温度等因素对氢酯基化反应的影响．结果表明：以甲苯为溶剂,在n（Co2（CO）8）／n（苯乙烯）=0．06,吡啶为配体且n（吡啶）／n（Co）=2,CO压力6．0MPa、反应温度95℃的较佳条件下反应12h,苯乙烯的转化率接近100％,α-苯基丙酸甲酯的收率达到89．07％,异正比24．35．     

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.