超临界CO2+EtOH+CO+H2四元体系压力和温度变化规律及超临界性质的研究

在5～11MPa的范围内,利用恒容静态平衡法详细考察了CO2密度在0.542～0.590g/cm3范围的不同组成的超临界CO2+EtOH+CO+H2四元体系的压力和温度的变化规律,并测定了相应的临界温度和临界压力.模拟了超临界丙烯氢甲酰反应体系的相行为.结果发现,CO+H2加入量的增多可明显改变超临界CO2+EtOH+CO+H2四元体系的超临界性质,主要表现为该体系的临界温度随着CO和H2摩尔分数的增加而线性降低,临界压力随着CO和H2摩尔分数的增加而线性增加.在相同的CO和H2组成下,超临界四元体系的压力随着体系温度的增加而线性增加,并且p-T线的斜率基本相同.在相同温度下超临界四元体系的压力随着体系中CO和H2摩尔分数的增加线性增加,并且不同温度时的变化率基本相同.     

超临界流体色谱法分离生育酚同系物

用超临界流体色谱法进行了生育酚异构体的分离研究。在实验温度303．15K～343．15K和压力14～22MPa范围内，考察了ODS柱上温度、压力和密度与容量因子和选择性的关系，得到了生育酚在超临界色谱中的最佳分离条件：温度为343．15K，压力为20MPa，CO2流量750mL/min。     

分散红60在超临界CO2中的溶解度实验研究

有关分散染料与超临界CO2二元体系的相平衡数据(溶解度)实验测定及模型关联,对超临界流体染色工艺基础研究及工业化至关重要。本文建立了高压溶解度测试实验装置,在温度353～393K、压力15～30MPa条件下,对分散红60在超临界CO2中的溶解度进行了测定。并利用zcan经验公式对实验结果进行关联,关联结果和实验结果吻合较好,最大误差为9.3%。结果表明:体系的压力、温度和混合物密度是影响分散染料在超临界CO2中溶解度的重要因素;可利用zcan经验公式对染料等固体物质在超临界CO2中的溶解度进行关联计算。     

低温高活性熔铁催化剂上的超临界相费托合成反应

在固定床反应器中超临界相条件下研究了熔铁催化剂上的费托合成反应,发现在超临界介质中反应物和产物更容易扩散,较好地抑制了催化剂表面非活性碳的沉积,从而提高了费托合成反应中的CO转化率和烯烃选择性,增加了链增长因子,降低了甲烷选择性.同时,考察了超临界介质、反应温度、压力、H2/CO比和空速等条件对费托合成反应的影响.结果表明,C5-8正构烷烃在催化剂活性温度下都是适宜的超临界介质.当温度和压力都在介质的临界点以上时,介质表现出较好的传质与传热性能,可改善费托合成反应性能.     

超临界CO2-溶质二元系的密度及溶质的偏摩尔体积

在308．15和318．15K温度下，80－170bar压力范围内，测定了CO2-乙醇、CO2-丙酮和CO2-正庚烷混合物的密度，溶质的浓度范围是0－1．3mol·L－1．在此基础上，计算了溶质的偏摩尔体积，系统地研究了温度、压力和溶质浓度对二元混合物密度的影响，并从压力和溶质浓度对溶质偏摩尔体积影响的角度研究体系中的分子间相互作用．     

二氧化碳从它溶胀后的聚合物中的解吸

研究了经过40℃,8.0～14.0MPa的超临界二氧化碳溶胀后的6种聚合物LDPE、PP、PA6、EVA、PS和PU中的CO2解吸情况,模拟了聚合物中CO2的解吸规律,即以时间的自然指数递减规律,并根据Fick扩散定理从理论上推导出CO2在聚合物中的解吸方程,由解吸方程计算解吸扩散系数,结果表明CO2的解吸扩散系数数量级达10-7cm2/s,解吸扩散系数与CO2在聚合物中的浓度和温度以及解吸前聚合物在超临界二氧化碳中的压力有关。     

栀子花挥发油超临界CO2萃取工艺优选分析

采用超临界CO2萃取法,使用正交试验设计方案,以提取率为指标,对萃取温度、萃取压力、分离压力和分离温度等影响因素进行考察。结果表明,超临界CO2萃取法萃取栀子花挥发油成分的最佳工艺条件为：萃取压力15mPa,萃取温度35℃,分离压力15mPa,分离温度25℃。该方法简便、可靠、选择性高,适于工业化生产。     

超临界CO2+碳酸二乙酯二元体系高压气-液相平衡

在带有石英视窗的可变体积高压釜内,于333,353,373和393K等4个温度下,测定了3.0～15.0MPa范围内超临界CO2与碳酸二乙酯(DEC)二元体系的气-液平衡数据.结果表明,当温度恒定时,随着压力的增大,液相中超临界CO2的浓度急剧增大,气相中碳酸二乙酯的浓度缓慢增加.根据实验结果推测出了体系的pc,Tc,xc和Vc等临界性质.     

用微扰硬球链理论计算超临界CO-2-溶质二元系的密度

溶质在超临界流体中的溶解度与流体的密度密切相关。本文采用微扰硬球链理论对纯CO2及CO2-正戊烷、CO2-正庚烷、CO2-正癸烷体系在不同条件下的密度进行计算,计算值与文献给出的实验值符合很好。     

超临界CO2与叔丁醇二元系统高压相平衡研究

采用固定体积可视观察法测量装置测定了CO2与叔丁醇在323.2~353.2 K温度范围内于不同压力下的平衡数据, 并运用Peng-Robinson状态方程(PR)和Van der Waals-2混合规则建立了相平衡模型, 通过非线性最小二乘法优化计算得到了不同温度下的模型参数. 并得到了模型参数与温度的表达式, 分别为k12=-199.2066+1.8136T-0.00548T2+5.50×10-6T3; n12=-384.5626+3.4960T-0.01056T2+1.06×10-5T3.获得了此体系在不同组成下的临界压力、临界温度、临界摩尔体积、临界压缩因子和临界密度等临界性质. 研究结果表明, CO2与叔丁醇二元体系的临界温度、临界压力和临界压缩因子均随着临界CO2组成的增加而降低.     

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%.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

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.     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

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.     

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.     

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.