一锅法制备1-吡啶基-3-哌啶-4-甲酸的合成研究

N杂环类分子是一类重要的医药切块分子,多用作多肽类医药分子的合成原料中间体。报道了一种N杂环类分子1-吡啶基-3-哌啶-4-甲酸新的合成方法。高压反应釜依次加入3-溴吡啶、4-哌啶甲酸乙酯、碳酸钾、N-甲基吡咯烷酮,反应釜密封好,升温至180℃,压力保持0.5MPa,液质监测反应,反应72h,原料反应完毕。将反应体系冷却至室温后抽滤,滤饼用甲醇打浆后再次抽滤,将滤液浓缩后再甲醇重结晶得黄色粉末,产率最高可达46%。该合成方法,碱性高压条件,一锅法得到目标化合物,极大地降低了工业成本,且后处理方法简单且收率高,具有工业化生产前景。

Al_(2)(SO_(4))_(3)催化热解油转化生产酯类燃料

酸类、糖类等不稳定组分的存在是制约热解油直接用作生物燃料的主要因素。为了解决此问题,提出采用Al_(2)(SO_(4))_(3)催化剂将这些不稳定成分酯化为燃料类化合物的途径。首先,分别以单模型化合物左旋葡萄糖或乙酸为原料,考察各种金属硫酸盐催化其转化制备乙酰丙酸乙酯或乙酸乙酯的能力,筛选出催化性能最好的催化剂;其次,以左旋葡萄糖和乙酸的模型混合物为原料,探究Al_(2)(SO_(4))_(3)催化同时转化制备酯类的最佳反应条件;最后,以真实热解油为原料,验证Al_(2)(SO_(4))_(3)在最佳反应条件下催化酯化的可行性。结果表明,酯化后热解油中大部分酸、糖、醛消失,同时产生大量的酯和缩醛,酯类和缩醛类占改性热解油总色谱面积的39.5%。Al_(2)(SO_(4))_(3)能有效将热解油中的酸类、糖类等不稳定组分酯化为燃料类化合物,可为热解油转化制备生物燃料提供借鉴。

Synthesis and Antitumor Activity of 3-[2-(4-Hydroxy-Phenyl)-Ethyl]-Benzo[d] Isoxazole-4,6-Diol

A new phloretin derivative 1 3-[2-(4-hydroxy-phenyl)-ethyl]-benzo[d] isoxazole-4,6-diol (yield 63%) was synthesized from phloretin by carbonyl nucleophilic addition condensation reaction. Its structure was characterized by 1H NMR, 13C NMR and HR-MS. The phloretin, compound 1, resveratrol and acetylated resveratrol were determined by comparing them with paclitaxel. Anti-tumor activity of alcohol on SPC-A1, EC109, A549, MCF-7 and MDA-MB-231 cell lines. Compound 1 showed better antitumor activity than docetaxel against A549 tumor cells.

4-氯乙酰乙酸乙酯的连续合成工艺

文章采用微通道反应器进行连续氯化反应来提高4-氯乙酰乙酸乙酯的收率。将双乙烯酮和氯气分别溶解于二氯甲烷,再通过计量泵按比例泵入微通道反应器中,在正压条件下以一定反应温度、时间进行反应。其结果表明,在双乙烯酮含量为20%、氯气含量为10%、氯气与双乙烯酮摩尔比为1.05∶1.00、反应温度为-10℃、流速为60 mL/min、停留时间为1 min的反应条件下制备的4-氯乙酰乙酸乙酯产品,其产品收率达到96.7%,产品提纯后含量达到98%以上。

浓香型白酒发酵过程中4-甲/乙基愈创木酚的代谢规律分析

4-甲/乙基愈创木酚是浓香型白酒中重要的风味和健康成分,是影响白酒烟熏、丁香风味及抗氧化、抗炎等健康特性的重要因素,但其在浓香型白酒发酵过程中的代谢规律不清晰。因此,该文首先采用真空辅助吸附萃取分析法(vacuum assisted adsorption extraction,VASE)结合GC-MS分析揭示浓香型白酒发酵过程中4-甲/乙基愈创木酚及其前体物质的变化规律。研究发现:(1)4-甲/乙基愈创木酚的前体物质(阿魏酸、4-乙烯基愈创木酚)是由原料提供的,其中对阿魏酸的贡献粮食约为65.13%、大曲20.69%、稻壳14.18%;对于4-乙烯基愈创木酚的贡献稻壳最大,约为98.29%、大曲0.28%、粮食1.33%;(2)发酵过程中,4-甲/乙基愈创木酚主要在窖池发酵阶段产生,尤其是于窖池发酵后期产生,4-甲基愈创木酚由53.63μg/kg增长到93.78μg/kg,生成率达74.86%,4-乙基愈创木酚的含量由13.14μg/kg达到53.98μg/kg,生成率超过300%。该研究系统揭示了浓香型白酒发酵过程中4-甲/乙基愈创木酚及其前体物质的变化规律,为调控4-甲/乙基愈创木酚代谢提高浓香型白酒风味健康品质具有重要意义。

Synthesis and Crystal Structure of a Novel Ethyl 5-(4-(2-Phenylacetamido)phenyl)-1H-pyrazole-3-carboxylate as an Acrosin Inhibitor

The title compound （ethyl5-（4-（2-phenylacetamido）phenyl）-lH-pyrazole-3-carboxylate, C20H19N3O3） was synthesized by the reaction of Claisen condensation, cyclization, reduction and acylation. The structure was characterized by X-ray diffraction, MS, NMR and IR. It belongs to the monoclinic system, space group C2/c with a = 22.723（9）, b = 9.324（4）, c = 18.890（8） A, β = 114.259（6）°, V = 3649（3） A^3, Dc = 1.272 Mg·m^3, Z = 8, Mr = 349.38, p = 0.087 mm^-1, F（000） = 1472, the final R = 0.0615 and wR = 0.1643. The biological test shows that the title compound has a moderate acrosin inhibition activity.

Synthesis and Crystal Structure of Ethyl 3-(4-Chlorophenyl)-3,4-dihydro-6-methyl-4-oxo-2-(pyrrolidin-1-yl)furo[2,3-d]pyrimidine-5-carboxylate

The crystal structure of the title compound ethyl 3-（4-chlorophenyl）-3,4-dihydro-6- methyl-4-oxo-2-（pyrrolidin-1-yl）furo[2,3-d]pyrimidine-5-carboxylate （C20H20ClN3O4, Mr= 401.84） has been prepared and determined by single-crystal X-ray diffraction. The crystal is of monoclinic, space group P21/n with a = 20.6215（9）, b = 8.5311（4）, c = 21.6886（9） A^°, β = 91.607（1）°, V = 3814.0（3）A^°^3, Z = 8, Dc = 1.400 g/cm^3, F（000） = 1680, μ = 0.233 mm^-1, R = 0.0718 and wR = 0.1545 for 6717 observed reflections with I 〉 2σ（I）. X-ray diffraction analysis reveals two crystallographically independent molecules in the asymmetric unit.

Enantioselective Hydrogenation of Ethyl 2-Oxo-4-phenylbutyrate on Cinchona-Platinum Catalysts

到 10,11-dihydrocinchonidine 修改的 Pt/gamma-Al_2O_3 上的乙醇(R)-2-hydroxy-4-phenyl-丁酸盐的乙醇 2-oxo-4-phenylbutyrate 的 Enantioselective 加氢被在一个搅动的压热器和液体速度的效果在变换和 enantiometric 过量上调查修饰词，反应物的起始浓度，压力和温度的数量的影响学习，气体速度，在一个涓涓细流床反应堆的修饰词集中和各种各样的催化的床。最大的光收益在反应堆的二种类型是大约50%和60%， respectively.It 被假定全部的加氢率在铂上在未修改、修改的活性部位上包括了反应速率表面和一个运动模型，在压热器适合试验数据很好， obtained.A 简化了塞子流动模型被建议描述涓涓细流床的床一般水准效率反应堆。

Synthesis and Crystal Structure of Tri(4-(3-hydroxy2-ethyl-4-pyridinone-1-yl)-aniline Condensation Salicylaldehydato) Monohydratotricopper(II)Dimethylformamide Monohydrate Solvate

The title complex [Cu3L3(H2O)]DMFH2O (H2L = 4-(3-hydroxy-2-ethyl-4- pyridinone-1-yl)-aniline condensation salicylaldehyde) was obtained. The single-crystal X-ray study shows that it is a trinuclear compound [Cu3(C20H15N2O3)3(H2O)]DMFH2O. The coordi- nation sphere about each copper ion in the complex consists of two oxygen atoms from hydroxylpyridinone moiety of one ligand and one oxygen and one nitrogen atoms from salicyladehyde Schiff-base moiety of another ligand arranged in a slightly distorted square planar geometry. Among the three copper ions, one (Cu(2)) is coordinated by the other oxygen atom of water molecule on the fifth coordinate position to form a distorted square pyramid geometry. The crystal is of monoclinic, space group P21/c with a = 12.9202(5), b = 27.197(1), c = 17.0116(7) ? b = 100.588(1), V = 5875.9(4) 3, Z = 4, C63H57N7O12Cu3, Mr = 1294.78, Dc = 1.464 g/cm3, m = 1.146 mm-1, F(000) = 2668, R = 0.0784 and wR = 0.1546 for 6926 observed reflections with I > 2s(I). The differences of coordinate bond lengths are observed between anhydrous and hydrous units: in the former unit, the average bond lengths are 1.978 ?for CuN (azomethine), 1.883 ?for CuO (phenolic) in Schiff-base moiety, 1.959 ?for CuO (keto), and 1.919 ?for CuO (hydroxy) in hydroxypyridinone moiety; while those in the latter are longer with the following corresponding values: 1.985(5), 1.908(5), 1.993(5) and 1.919(4) ? respectively. The Cu(2)O (water) bond length is 2.375(6) ?

Extraction Separation of Scandium，Iron and Lutetium with Isopropyl Phosphonic Acid Mono（1－hexyl－4－ethyl）OctylEster

The extraction and stripping of scandium from its sulfate solutions by isopropyl phosphonic acid mono (1-hexyl-4-ethyl) octyl ester (PT-2, HL) diluted with n-hexane are reported. A high efficiency of separation between scandium, iron and lutetium can be achieved by controlling aqueous acidity. Different mechanisms of Sc3+ with PT-2 in various acid range have been proposed.At lower aqueous acidity, it is a cation exchange reaction, while at higher acidity. a solvation reaction was ascertained. Its IR and NMR spectra have been discussed. The effect of temperature on extraction of Sc3+ was observed and thermodynamic functions were calculated.

Synthesis and Crystal Structure of Ethyl 2-(6-(1,3-Dioxo-4,5,6,7-tetrahydro-1H-isoindol-2(3H)-yl)-7-fluoro-3-oxo-2H-benzo[b][1,4]oxazin-4(3H)-yl) Butanoate

The title compound ethyl 2-（6-（1,3-dioxo-4,5,6,7-tetrahydro-lH-isoindol-2（3H）- yl）-7-fluoro-3-oxo-2H-benzo[b][1,4]oxazin-4（3H）-yl） butanoate 3 was synthesized by the reaction of ethyl 2-（6-amino-7-fluoro-3-oxo-2H-benzo[b][1,4]oxazin-4（3H）-yl） butanoate with 4,5,6,7- tetraydrophthalic anhydride, and its structure was determined by X-ray single-crystal diffraction. The crystal belongs to the monoclinic system, space group P2 1/n with a = 9.3469（2）, b = 16.7715（5）, c = 13.7153（4） A, β= 104.9680（10）°, μ = 0.107 mm^-1, Mr = 430.42, V= 2077.08（10） ,A3, Z= 4, Dc = 1.376 g/cm3, F（000） = 904, T= 296（2） K, R = 0.0508 and wR = 0.1478.

Synthesis and Crystal Structure of 4-(4,6-Dimethoxylpyrimidin-2-yl)-3-thiourea Carboxylic Acid Ethyl Ester

4-（4,6-Dimethoxyl-pyrimidin-2-yl）-3-thiourea carboxylic acid ethyl ester was synthesized by the reaction of 2-amino-4,6-dimethoxyl pyrimidine, potassium thiocyanate and methyl chloroformate in ethyl acetate. Single crystals suitable for X-ray measurement were obtained by recrystallization with the solvent of dimethyl formamide at room temperature. The crystal structure was determined by X-ray diffraction analysis. Crystallographic data： C10H14N4O4S, M, = 286.31, monoclinic, space group C2/c with a = 2.5309（3）, b = 0.67682（6）, c = 1.74237（19） nm, β = 114.744（3）°, V= 2.7106（5） nm3, Dc = 1.403 g/cm3, p = 0.225 mm-1, F（000） = 1200, Z= 8, R= 0.0514 and wR= 0.1529.

Synthesis, Spectroscopic and Crystal Structure Studies on Ethyl 5,7-Dimethyl Coumarin-4-Acetate

Ethyl ester of 5,7-dimethyl coumarin-4-acetic acid has been synthesized from 3,5-Xylenol in a two step sequence of reaction involving Pechmann cyclisation and acid catalyzed esterification. The title compound 2 crystallizes in Monoclinic form, space group P 1 21/c 1, with a = 8.6248(4) ?, b = 18.9103(8) , c = 8.4204(4)?, β = 101.241(2)?, V = 1347.00(11) ?, D cal = 1.283 Mg/cm3, Z = 4. The molecule is stabilized by intermolecular C-H … O bonds.

产4-乙基愈创木酚菌株的筛选、鉴定及其在酱油酿造中的应用

该研究采用传统培养分离方法结合耐盐性及4-乙基愈创木酚(4-EG)生产能力测定,从广式高盐稀态酱油发酵酱醪中分离筛选能转化阿魏酸(FA)生成4-EG的细菌,通过形态观察及分子生物学技术对分离菌株进行鉴定,同时对其生长特性进行研究,并将其应用于酱油酿造。结果表明,分离筛选得到一株高产4-EG的菌株JLB30-2,被鉴定为枯草芽孢杆菌(Bacillus subtilis),该菌株在45℃、160 r/min、20%盐含量环境下,能将发酵液中的FA转化为4-EG。菌株JLB30-2在盐含量为20%的酱醪中培养60 d,4-EG含量最高达29.75 mg/L,是对照组(6.85 mg/L)的3.34倍,同时增加了酱油中氨基酸、酮类化合物的含量,强化了酱油醇香和酱香,提高了酱油的感官品质,对改善提升酱油品质具有重要实用价值。

Synthesis and Crystal Structure of (Z)-Ethyl-4-(4-methoxy)benzylidene-2-(3,5-dimethoxypheny-tetrahydrofuran-3,3-dicarboxylate

The title compound （Z）-ethyl-4-（4-methoxy）benzylidene-2-（3,5-dimethoxyphenyl）- tetrahydrofuran-3,3-dicarboxylate has been synthesized, and its crystal structure was characterized by X-ray single-crystal diffraction. The crystal belongs to triclinic, space group P1, with a = 8.140（3）, b = 11.966（4）, c = 13.771（5）Aα= 67.366（4）, β= 85.165（5）, γ= 75.806（4）°, V = 1200.1（7） A3, Z = 2, C26H3008, Mr = 470.50, Dc = 1.302 g/cm^3, F（000） = 500,λ（MoKa） = 0.71073 A, μ= 0.096 mm^-1, R = 0.0659 and wR = 0.1841 for 3080 observed reflections （I 〉 2σ（I））. As a key intermediate of HIV-1 integrase inhibitor, the synthesis and structure confirmation of the title compound are important for further studies.

Preparation of Ethyl 4-Nitrobenzoate Using Ultradispersed Natural Zeolite Catalysts, Ultrasound and Microwave Irradiation

The new possibilities of preparing the ethyl 4-nitrobenzoate by esterification of 4-nitrobenzoic acid (4-NBA) with ethanol under argon at 80°C are shown;particularly, over catalysts: on micrometric (4.8 - 7.0 μm) or ultradispersed crystallites (290 - 480 nm) of hydrogen forms of nanoporous natural zeolites H-CL, H-MOR, H-HEU-M, H-PHI and under irradiation of the reaction mixture with ultrasound (US, 37 kHz, 330 W, 2 h) or microwaves (MW, 2450 MHz, 300 W, 2 h). Ultradispersed crystallites of zeolite catalysts were prepared from hydrogen forms of parent natural zeolites by their treatment with US or MW. In the esterification, the synergism of the actions of catalysts and MW or US was revealed;wherein on the ultradispersed best catalysts H-HEU-M and H-MOR conversion of 4-NBA and yield of ethyl 4-nitrobenzoate reached up to 70% and 67%, respectively. GC/MS, FTIR, NMR methods were used in the study.

Synthesis and Crystal Structure of cis-Bis(3-hydroxy2-ethyl-4-pyranonato)dioxomolybdenum(Ⅵ)

The complex MoO2(C7H7O3)2 has been prepared by the reaction of 3-hydroxy- 2-ethyl-4-pyranone with (NH4)6Mo7O244H2O. The single-crystal X-ray study shows that the coordination sphere about the molybdenum atom in the complex consists of six oxygen atoms arranged in a distorted octahedral geometry with the dioxo ligands in cis positions. The crystal is of monoclinic, space group P21/c with a = 8.3968(2), b = 12.7534(4), c = 14.5443(4) ? b = 96.277(1), V = 1548.18(7) ?, Z = 4, C14H14O8Mo, Mr = 406.19, Dc = 1.743g/cm3, m = 0.886mm-1, F(000) = 816, R = 0.0444 and wR = 0.1091 for 2336 observed reflections with I>2s(I). The average Mo=O bond length is 1.695(4) ? The two ketonic oxygen atoms of the pyranone moieties are trans to the oxo ligands and the hydroxy oxygen atoms are trans to each other. The average MoO bond lengths are 2.248(4) ?for the ketone oxygens and 2.005(3) ?for the hydroxy oxygens. The average ligand bite angle of OMoO is 75.2(2) and the bond angle between two Mo=O is 105.1(2). The dihedral angle is 79.16(2)?between two chelate ring planes.

Swelling Properties of New Hydrogels Based on the Dimethyl Amino Ethyl Acrylate Methyl Chloride Quaternary Salt with Acrylic Acid and 2-Methylene Butane-1,4-Dioic Acid Monomers in Aqueous Solutions

Hydrogels of dimethylaminoethyl acrylate methyl chloride quaternary salt (Q9) have been synthesized with different monomer ratio by copolymerization of this poorly studied monomer either with acrylic acid or with 2-methylene bu-tane-1,4-dioic acid. Hydrogel swelling was measured as a function of the composition of the hydrogel and of the crosslinking agent ratio. High values of swelling have been obtained at very high crosslinking values (【14 wt %) and the equilibrium swelling was reached at very low time (less than 15 minutes). The swelling isotherms consisted of a steep initial portion and then levelled off as asymptotically to the equilibrium swelling limit. The experimental data suggest clearly that the swelling process obeys second-order kinetics. According to this, the kinetics rate constant and the equilibrium water content were determined at different comonomer composition and crosslinker concentration. The calculated kinetic constants ranged from 0.48 to 3.76 ×10-2 min-1 for poly (acrylic acid-co-Q9) hydrogels and from 0.68 to 4.0 ×10-2 min-1 for poly (2-methylene butane-1,4-dioic acid-co-Q9) hydrogels depending on the hydrogels composition. The diffusion process was evaluated for each hydrogel showing a non-Fickian type diffusion. In all cases was observed a considerable increase in diffusion coefficient as Q9 content increases.