对异丙基苯甲醛的合成研究

以对异丙基苯甲酸为原料经酯化、还原、氧化反应合成了对异丙基苯甲醛。其中催化剂DMF加快了酯化反应速率,质子缓释剂乙醇的加入使得还原产率提高了34.5%,当以浓硫酸为质子缓释剂时,对异丙基苯甲酸可被直接还原为醇,氧化剂KMnO_4-CuSO_4·5H_2O以KMnO_4含量为50%最佳。合成方法相对安全环保,产品纯度达到了98.6%,总产率达到了73.8%(以对异丙基苯甲酸计)。目标化合物和中间产物通过~1H NMR表征。     

ZSM-5催化乙醇制低碳烯烃*

生物乙醇近年来得到蓬勃发展,由乙醇制备低碳烯烃得到广泛关注。本文综述了近年来在乙醇制低碳烯烃领域ZSM-5催化剂的研究进展,介绍了经过金属或磷改性后的催化剂能够改善催化剂的性能,表现为降低催化剂表面酸量,调节酸强度,抑制芳构化和氢转移反应的发生。与未改性分子筛催化剂相比,改性后的催化剂能够显著提高催化剂的活性和乙醇转化产物中低碳烯烃的选择性,同时延长了催化剂的使用寿命。讨论了影响反应的一些因素和该反应的可能机理;展望了催化剂在乙醇制低碳烯烃中的发展方向,指出由乙醇制低碳烯烃是传统石脑油裂解的一条可替代途径。     

起泡剂/稳泡剂/SiO2复合泡沫缓速酸液体系协同增效性能

为了有效控制液相中H⁺向岩石表面的扩散,降低酸-岩反应速率,进而达到深度酸化刻蚀的目的,通过对纳米颗粒、稳泡剂与表面活性剂协同增效作用的研究,制备了一种泡沫稳定、耐温性能及缓速性能优异的泡沫缓速酸。室内通过对比不同纳米材料在酸液中的分散性能及纳米颗粒粒径对泡沫缓速酸性能的影响,优选出d=25 nm的亲水型Si O₂纳米材料。采用自制的两性表面活性剂(MAC)作为起泡剂,并加入自制的酸液稠化剂(SY-1)作为稳泡剂以达到稳泡作用。当w(Si O₂)=1.5%、w(MAC)=1.0%、w(SY-1)=0.08%时,所形成的泡沫也更加致密,液膜厚度增强,泡沫稳定性提高,半衰期延长,从7 min增长到69 min;并且SY-1的加入提高了泡沫的耐高温性能,使体系在90℃时半衰期仍然能达到29 min。通过测定不同条件下酸岩反应速率并进行比较,结果表明,20%HCl基液的平均酸岩反应速率为1.148×10^-3 mg/(cm²·s),而实验室自制泡沫缓速酸液体系的平均酸-岩反应速率降至7....     

固定化脂肪酶催化高酸废油脂酯交换生产生物柴油

 探讨了固定化脂肪酶Novozym 435催化高酸废油脂与乙酸甲酯酯交换生产生物柴油. Novozym 435能催化高酸废油脂与乙酸甲酯的酯交换反应,反应24 h后甲酯产率为77.5%,但该值大大低于以精制玉米油为原料时的甲酯产率(86.2%). 系统研究了反应体系中的水、游离脂肪酸和乙酸对反应的影响. 当反应体系中的水含量低于0.05%时,水对酶反应速率和甲酯产率影响甚小,而水含量高于0.05%时,酶反应速率和甲酯产率随着水含量的增加而降低. 游离脂肪酸对反应有较大影响,甲酯产率随着游离脂肪酸含量的增加而急剧下降. 乙酸甲酯与游离脂肪酸反应产生的副产物乙酸是导致甲酯产率显著下降的原因. 在反应体系中添加适量(油重的10%)的有机碱三羟甲基氨基甲烷或三乙胺可有效提高酶促高酸废油脂的酯交换反应速率和甲酯产率,使反应12 h后的甲酯产率分别达到85.9%和80.8%; 碱的加入还提高了酶的操作稳定性,添加有机碱三羟甲基氨基甲烷或三乙胺可使反应10批次后Novozym 435的相对酶活力分别由对照值86%提高到97%和93%.     

用微反断流催化色谱研究催化剂中毒后乙醇脱水表观反应速率常数的变化

用微反断流催化色谱技术研究了HZSM-5催化剂上乙醇脱水生成乙烯的反应,发现表现反应速率常数k与反应是在催化剂表面强酸中心或弱酸中心上进行有关。当加入少量正丁胺时,乙烯生成率增加,这与酸中心中毒后使积炭量减少有关。当正丁胺加入量增至一定值时,乙烯生成率逐渐下降。在不同反应温度(185,198,208℃)下测定了加入正丁胺后k值的变化,得到了各温度下被中毒活性中心数(N)和反应速率常数(K)之间的关系,并用正弦曲线方程进行了拟合,说明了催化剂表面活性的非均一性。用吡啶中毒也得到了相似的结果。同时,也得到了表现活化能随中毒中心数的变化曲线,并观察到补偿效应的存在。     

高硅铝比高峰土超声强化酸浸反应动力学研究

用XRD谱图对比了煤系高岭土与高硅铝比高岭土煅烧酸浸前后的结晶分布特征，发现两者的煅烧活化过程完全相同，只有其中的高岭石经煅烧成为偏高岭石后才能进行酸反应，后者含有大量的硅铝化合物伴生矿使得最大浸取率很低，超声场的加入使颗粒细化，表面更新加快，导致浸出速率明显提高，但并未改变伴生矿结构与反应途径。故仍保持原有的最大浸取率，动力学分析表明，用液固缩芯反应模型能很好地模拟实验数据。与无超声下酸浸动力学相比，在较低的温度下，因超声空化效应造成颗粒细化与表面更新，加快了反应速率，使灰层扩散成为控制步骤。     

用热天平法研究煤的催化气化 Ⅱ.各种气化条件对转化率的影响与数学关联

本文对影响活性炭与水蒸汽催化气化速率和转化率的各种条件进行了探讨,并用数学表达式进行了关联,得出转化率与气化条件关系的数学模型,其平均拟合误差为7.9%。求出了催化剂的最佳选择量W(?)和最大速率点时间t_0的各自表达式,对如何选择气化时间、气化温度以及催化剂载量以达到最佳气化效果进行了讨论,为寻找最佳反应条件提供了依据。     

胡椒酸己二胺的合成

以胡椒碱为起始原料,与KOH反应生成胡椒酸钾盐,经酸化后制得胡椒酸(2); 2与乙醇经酯化反应制得胡椒酸乙酯(3); 3与己二胺在金属钠催化下经氨解反应合成了胡椒酸己二胺(4),其结构经¹H NMR, ¹³C NMR和IR确证。合成4的最佳反应条件为：催化剂用量2 wt%, n(3):n(己二胺)=0.6, m(乙醇):m(3)=2.5,于65～75 ℃反应48 h,收率83.5%。该工艺在微型实验基础上放大十倍,收率大于79%。     

酸法合成α-FeO(OH)反应动力学研究

本文对酸法合成α-FeO(OH)反应的动力学过程进行了研究, 考察了初始浓度、反应温度、pH值、氧分压、空气流量及搅拌强度对Fe(OH)_2悬浮液氧化速率的影响, 确定对Fe(Ⅱ)在晶核生成阶段为零级反应, 在晶体生长阶段近似为0.5级反应, 对氧分压均呈一级反应, 并分别求出反应活化能.提出了在晶核生成阶段存在溶解-氧化的动态平衡过程, 以解释零级反应及pH-时间曲线的平稳区。物理扩散为该多相反应的控制步骤. α-FeO(OH)生成动力学的研究将为工业反应器的研制、工程放大及过程优化控制提供基本依据。     

L-苯丙氨酸脲类化合物的合成工艺改进

以L-苯丙氨酸为原料,经甲酯化反应制得中间体丙谷胺酸甲酯盐酸盐(1);以三乙胺为缚酸剂,1经固体光气活化制得苯丙氨酸异氰酸酯后,再分别与伯胺反应合成了4个苯丙氨酸脲类化合物(3a~3d),收率90.7%~94.2%,其结构经1H NMR,MS和X-衍射确证。     

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.     

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.     

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.     

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.     

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.     

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.     

Microwave-assisted copper-catalyzed stereoselective ring expansion of three-membered heterocycles with α-diazo-β-dicarbonyl compounds

Microwave-assisted copper-catalyzed ring expansions of three-membered heterocycles with α-diazo-β-dicarbonyl compounds were investigated. Thiiranes generated 3-acyl-5,6-dihydro-1,4-oxathiines in the presence of copper sulfate and trans-3-acyl-5,6-dihydro-1,4-oxathiines as stereospecific products for 1,2-disubstituted cis-thiiranes through an intramolecular S_N2 process. Oxiranes gave rise to 2-acyl-5,6-dihydro-1,4-dioxines under the catalysis of copper hexafluoroacetylacetonate and cis-3-acyl-5,6-dihydro-1,4-dioxines as stereospecific products for 1,2-disubstituted cis-oxiranes via an intimate ion-pair mechanism. The current method provides a direct and simple strategy in efficient preparation of 3-acyl-5,6-dihydro-1,4-oxathiines and 2-acyl-5,6-dihydro-1,4-dioxines, important agents in medicinal and agricultural chemistry, from readily available thiiranes and oxiranes, respectively.     

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.