水杨醛－L－甲硫氨酸希夫碱钴（Ⅱ）配合物的热分解动力学

本文合成了一种新的希夫碱配合物，水杨醛－Ｌ－甲硫氨酸—水合钴（Ⅱ），Ｃｏ（ｓａｌｍｅｔ）·Ｈ２Ｏ，并用非等温热重法研究了它的热分解反应动力学。ＴＧ及ＤＴＧ曲线表明配合物按两步分解：Ｃｏ（ｓａｌｍｅｔ）·Ｈ２Ｏ１４２－１７５℃（１）→Ｃｏ（ｓａｌｍｅｔ）１７５－８２０℃（２）→ＣｏＯ用Ａｒｃｈａｒ微分法和Ｃｏａｔｓ－Ｒｅｄｆｅｒｎ积分法联合求出两步骤的动力学。步骤（１）、（２）的动力学方程分别表示如下：ｄα／ｄｔ＝Ａ·ｅ－Ｅ／ＲＴ（１－α）［－ｌｎ（１－α）］ｄα／ｄｔ＝Ａ·ｅ－Ｅ／ＲＴ（１－α）２［（１－α）－１－１］     

高效液相色谱法测定2-氨基萘-6-磺酰甲胺及其杂质

研究了一种同时测定２－氨基萘－６－磺酰甲胺及其杂质（２－氨基萘,２－乙酰氨基萘－６磺酸,２－氨基萘－６－磺酸和２－乙酰氨基萘－６－磺酰甲胺）含量的高效液相色谱法。采用ＨｙｐｅｒｓｉｌＢＤＳ Ｃ１８色谱柱,０．２％四丁基铵高氯酸盐（ＴＢＡＰＣ）／乙腈／３６％乙酸（６０：３８：２,Ｖ／Ｖ／Ｖ）为流动相,柱温３０℃,在流速为１ｍＬ／ｍｉｎ时,上述５种物质在２０ｍｉｎ内实现了基线分离。本方法快速、准确,适     

α-磷酸锆的制备及热分解非等温动力学研究

采用改进的直接沉淀氟配位法,在常温常压下制备出了α－磷酸锆（α－ＺｒＰ）,ＸＲＤ结果表明它的层间距为０．７６５ｎｍ,结晶度较好,并以热重分析法（ＴＧ）为手段,对α－ＺｒＰ的热分解过程和非等温热分解动力学机理进行了研究。结果显示,在线性升温速率为１０℃／ｍｉｎ时,α－ＺｒＰ在１３１℃开始脱结晶水;脱去结晶水后形成的Ｚｒ（ＨＰＯ４）２在４５３℃进行磷羟基缩合,至７２０℃完全分解为ＺｒＰ２Ｏ７。脱结晶水和分解过程的失重分别为６．２４％和５．６４％,与理论值基本相符。动力学研究确定了Ｚｒ（ＨＰＯ４）２分解反应属于Ａｖｒａｍｉ－Ｅｒｏｆｅｅｖ的成核和核成长为控制步骤的Ａｌ机理,热分解反应表观活化能为１６５．６ｋＪ／ｍｏｌ,频率因子为３．５０×１０７ｓ－１。     

磷酸三丁酯萃淋树脂富集水中痕量酚类化合物的研究

本文对磷酸三丁酯（ＴＢＰ）萃淋树脂为柱填料，研究了富集水中酚类化合物及其洗脱条件。结果表明，以ＴＢＰ萃淋树脂为富集剂，水样ｐＨ值为１－７，以３０ｍｌ／ｍｉｎ的流速通过吸附柱，用８ｍｌ０．１ｍｏｌ／Ｌ的ＮａＯＨ洗脱，多种酚类化合物回收率在９７％－１０３％。此外还试验了地面水中常见干扰物的影响，该方法富集倍数达１２５倍，最低检测限０．５μｇ／Ｌ。对实际样品１－１００μｇ／Ｌ范围内的测定相对标准偏差４．     

激光光散射研究聚(N-异丙基丙烯酰胺)单链及其智能凝胶微球在水中的相变(下)

（接上期）２聚（Ｎ－异丙基丙烯酰胺）微凝胶在水中的体积相变２．１理论部分凝胶体积相变热力学：聚合物凝胶的溶胀和蜷缩可以用膨胀因子α＝（Ｖ／Ｖ０）１／３＝（ΦＴ／ΦΘ）１／３来表征，其中ΦΘ的ΦＴ分别是温度Θ和Ｔ下凝胶网络的体积分数。在平均场理论中，中...     

TS-1分子筛催化双氧水氧化环己烷(英文)

系统地研究了ＴＳ－１分子筛催化双氧水氧化环己烷的反应。制备了三种ＴＳ－１分子筛,它们具有窄的粒径分布,在６０℃表现出高的活性和选择性。考察了溶剂、催化剂、反应温度、反应时间、ＴＳ－１中Ｔｉ含量及Ｈ２Ｏ７用量对氧化反应的影响。对具有完好晶型的ＴＳ－１分子筛役有必要进行预处理。最佳反应温度为８０～１１０℃,丙酮为最佳溶剂。环己酮的选择性与ＴＳ－１粒子大小有关,而Ｈ２Ｏ２选择性与ＴＳ－１用量无关。实验结果显示．溶剂在反应中间体的形成中起重要作用,Ｔｉ与丙酮配体的过氧配合物具有活化环己烷的活性。关键词 ＴＳ－１ 环己烷 催化氧化 Ｈ２Ｏ２     

高效液相色谱法测定小鼠脑组织单胺递质及其相关化合物

采用苯基柱等度洗脱分离,自然荧光检测法,直接测定小鼠脑组织匀浆中单胺递质及其相关化合物。优化出了最佳色谱条件,流动相为２０ｍｍｏｌ／Ｌ柠檬酸三钠（ｐＨ４．５０）－甲醇（９５：５,Ｖ／Ｖ）;柱温为３５℃。该方法能同时检测８种化合物。最低检测限为１．０－２．５μｇ／Ｌ,回收率均在９３５以上;线性范围为１．０μｇ／Ｌ－１．０ｍｇ／Ｌ。     

1,4-双(1′-苯基-3′-甲基-5′-氧代吡唑-4′-基)丁二酮-(1,4)双缩邻氨基苯甲酸合双锌配合物的合成及性质

本文报导１，４－双（１′－苯基－３′－甲基－５′－氧代吡唑－４′－基）丁二酮（１，４）双缩邻氨基苯甲酸合双锌配合物的合成、表征、热分解反应动力学及电化学性质。运用Ａｃｈａｒ法与Ｃｏａｔｓ－Ｒｅｄｆｅｒｎ法对非等温动力学数据进行分析，推断第三步非等温热分解过程动力学方程为：ｄα／ｄｔ＝３／２Ａｅ－Ｅ／ＲＴ·（１－α）４／３［（１／（１－α）１／３－１］－１。第四步非等温热分解过程为一维扩散机理。其动力学方程为：ｄα／ｄｔ＝Ａｅ－Ｅ／ＲＴ·１／２α，运用粉末微电极技术测试了配合物的电化学性质，推断配合物为双电子一步的不可逆过程。     

对硝基苯磺酰基乙酸酯与α，β－不饱和酸酯类化合物在固液相转移条件下的反应

在固液相转移催化（Ｋ_２ＣＯ_３／ＤＭＦ／ＴＥＢＡ）条件下，对硝基苯磺酰基乙酸酯与α，β－不饱和酸酯反应意外地生成加成重排产物［如生成２－甲基－２－（对硝基苯基）戊二酸－１－甲酯－５－乙酯］。其反应机理可能是砜酯首先与α，β－不饱和酯起Ｍｉｃｈａｅｌ反应，随后加成物发生分子内芳环上的亲核性取代，酸化后脱去ＳＯ２得最终产物。     

4—（6—甲基—2—苯并噻唑偶氮）间苯三酚反相高效液相色谱分离测定钒钴镍铬

作以新研制的４－（６－甲基－２－苯并噻唑偶氮）间苯三酚为柱前衍生试剂，用含１０ｍｍｏｌ／Ｌ的ｐＨ６．８０的ＨＡｃ－ＮａＡｃ缓冲溶液，１０ｍｍｏｌ／Ｌ ＴＢＡ．Ｂｒ和１×１０＾－４ｍｏｌ／ＬＥＤＴＡ的甲醇－水溶液（７８：２２，Ｖ／Ｖ）作流动相，在Ｃ１８柱上，１１ｍｉｎ内反相ＨＰＬＣ分离测定了Ｃｒ（Ⅵ），Ｖ（Ⅴ），Ｃｏ（Ⅱ），Ｎｉ（Ⅱ）。当Ｓ／Ｎ＝３时，其检出限分别是Ｖ（Ⅴ）５．４５ｎｇ，Ｃｏ（Ⅱ）     

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%.     

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.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

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.