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.

Epoxide Hydrolase-catalyzed Resolution of Ethyl 3-Phenylglycidate

Epoxide hydrolase-catalyzed resolution of ethyl 3-phenylglydidate was investigated using resting cells of Pseudomonas sp. BZS21. Under the present conditions 26.2 % of (2R, 3S)- ethyl 3-phenylglycidate with ee value of 94.6 % was obtained from the racemic mixture.

Synthesis of Ethyl 3-Fluoroalkyl-3-Halo Acrylate With CH_2N_2

When ethyl 3-fluoroalkyl-3-haloacrylate was treated with excess CH2N2,1-methyl-3-ethoxycarbonyl-4-fluoroalkylpyr azoles(3)and 1-methyl-5-ethoxycarbonyl-4-fluoroalkylpyrazoles(4)were obtained with a ratio of 90-95:10-5 in good yield.

(Z)-ETHYL 3-BROMO-4,4,4-TRIFLUORO-2-BUTENOATE AS A NOVEL CF_3-CONTAINING BUILDING BLOCK: Its Preparation and Pd-Catalysed Reaction with Alkynes and Organozinc Reagents

A novel CF_3-containing building block, (Z)-ethyl 3-bromo-4,4,4-trifluoro-2-butenoate, was easily prepared from CF_3CBr_3, the former reacted with alkynes Or organozinc reagents in the presence of Pd complexes to afford useful CF_3-containing intermediates in good yield.

Synthesis and Crystal Structure of Methyl 3-(5-Bromo-1-ethyl-1H-indole-3-carbonyl)aminopropionate

Methyl 3-（5-bromo-l-ethyl-lH-indole-3-carbonyl）aminopropionate has been synthesized by the acylation of 5-bromo-3-trichloroacetylindole with β-alanine methyl ester, followed by alkylation with ethyl iodide, in 82.6% yield. Its crystal structure was gotten and determined by X-ray diffraction method. The crystal is of monoclinic, space group P2/c with a = 11.7927（8）, b = 14.9342（8）, c = 9.0060（5） A, β = 101.558（6）°, V = 1553.93（16） A3, Z = 4, Dc= 1.510 g/cm3, 2 = 0.71073 A,μ（MoKa） = 2.656 mm-1, Mr = 353.22 and F（000） = 720. The structure was refined to R = 0.0401 and wR = 0.0825 for 1704 observed reflections with I 〉 2σ（I）. In the crystal structure, intermolecular N（2）-H（2）...O（1） hydrogen bond and weak intermolecular bonds （C（1）-H（1）...O（1） and C（10）-H（10B）-O（2）） are formed, and π-π stacking also exists.

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。

Facile One-pot Synthesis of Ethyl 3-Alkyl-4-hydroxy-2-thioxothiazolidine-4-carboxylates

Ethyl 3-alkyl-4-hydroxy-2-thioxothiazolidine-4-carboxylates were prepared in excellent yields from the reaction of corresponding primary amines with carbon disulfide and ethyl 3-bromo-2-oxopropanoate in the presence of anhydrous potassium phosphate in DMF at room temperature within 1 h. The structures of the highly functionalized products were corroborated spectroscopically （IR, ^1H NMR, ^13C NMR, EI-MS） and by elemental analyses. A plausible mechanism for such type of cyclization was proposed.

稀土修饰对Cu/Al_(2)O_(3)催化乙酰丙酸乙酯加氢性能的影响

生物质催化转化制大宗化学品符合低碳战略的重要研究方向,将纤维素衍生物乙酰丙酸乙酯转化为1,4-戊二醇是最具前景的技术路线之一。非贵金属铜基催化剂在该反应中表现出较好的活性,Cu/Al_(2)O_(3)在160℃、4 MPa H_(2)条件下催化乙酰丙酸乙酯氢解制1,4-戊二醇收率为50.8%,经稀土改性后催化剂的活性和选择性显著提升,其中CuNd0.25/Al_(2)O_(3)催化剂上获得1,4-戊二醇的收率高达92.7%。通过对催化剂性能以及X射线衍射(XRD)、透射电子显微镜(TEM)、氢气程序升温还原(H_(2)-TPR)、氢气程序升温脱附(NH3-TPD)和CO红外吸附(CO-DRIFT)等表征结果的分析发现,稀土元素的存在不仅改变了Cu活性中心的还原性质、分散度和电子结构,还改变了催化剂表面酸、碱性位点的分布。稀土元素的修饰既促进了催化剂表面反应物的吸附与活化,又抑制了目标产物1,4-戊二醇的脱水副反应,从而提高了活性和选择性。

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.

小红参乙酸乙酯提取物调控PI3K/AKT/GSK3-β通路对心肌缺血再灌注损伤大鼠雌激素的影响

目的研究小红参乙酸乙酯提取物通过调控磷脂酰肌醇3-激酶(phosphatidylinositol-3-OH kinase,PI3K)/蛋白激酶B(protein kinase B,Akt)/糖原合成酶激酶3-β(glycogen synthase kinase 3-β,GSK3-β)通路对心肌缺血再灌注损伤大鼠雌激素的影响。方法选取SPF级SD雌性大鼠50只,空白组10只,建模中死亡10只,随机分为模型组、低剂量组、高剂量组,每组10只。对照组不做任何处理,模型组、低剂量组、高剂量组进行心肌缺血再灌注损伤模型建模,建模成功后模型组不做任何处理,低剂量组、高剂量组分别给予小红参乙酸乙酯提取物灌胃,其剂量分别为56.7 mg/kg、280 mg/kg。观察大鼠心肌损伤[肌钙蛋白I(CTnI)、肌酸激酶同工酶(CK-MB)]、氧化应激[丙二醛(MDA)、超氧化物歧化酶(SOD)、谷胱甘肽过氧化物酶(GSH-PX)]、一氧化氮(NO)、内皮-氧化氮合酶(eNOS)含量、性激素、PI3K/AKT/GSK3-β信号通路表达量情况。结果与空白组比较,模型组、低剂量组、高剂量组cTnI、CK-MB、MDA、E2水平均升高(P<0.05),SOD、GSH-Px、NO、eNOS水平、PI3K、AKT、GSK3-β表达均降低(P<0.05);与模型组比较,低剂量组、高剂量组cTnI、CK-MB、MDA、E2水平均降低(P<0.05),SOD、GSH-PxNO、eNOS水平、PI3K、AKT、GSK3-β表达均升高(P<0.05);与低剂量组比较,高剂量组cTnI、CK-MBE2水平均降低(P<0.05),SOD、GSH-PxNO、eNOS水平、PI3K、AKT、GSK3-β表达均升高(P<0.05)。结论小红参乙酸乙酯提取物能对心肌缺血再灌注损伤大鼠能心肌损伤情况进行改善,抑制氧化应激状态,恢复雌激素水平,通过调节PI3K/AKT/GSK3-β通路能够反映出对心肌缺血再灌注损伤的干预效果。

Synthesis and in vitro-Anti-hepatitis B Virus Activities of Several Ethyl 5-Hydroxy-1H-indole-3-carboxylates

A series of ethyl 5-hydroxyindole-3-earboxylates 6a-10r was designed and synthesized. The structures of all the compounds were confirmed by IR, ^1H NMR, and MS and their anti-hepatitis B virus （HBV） activities were evaluated in 2.2.15 cells. Among them, compound 7g { ethyl 5-hydroxy-2- [ （ 3-methoxyphenylsulfinyl ） methyl ] -1-methyl-4- [ （4-methylpiperazin-1-yl） methyl ]-1H-indole-3-carboxylate} displays a significant anti-HBV activity, which is more potent than the positive control lamivudine.

Scale-up of biomass conversion using 1-ethyl-3-methylimidazolium acetate as the solvent

This scale-up study demonstrated the feasibility of an ionic liquid(IL)pretreatment process at 40 kg scale,using the IL 1-ethyl-3-methylimidazolium acetate([C2C1Im][OAc])as the solvent.The pretreatment was followed by enzymatic hydrolysis through which the process efficiency for biomass conversion to monomeric sugars was determined.The results show that 43 wt%of switchgrass was dissolved in IL after 2 h of pretreatment at 160℃ with 15 wt%solid loading.A 120 h enzymatic hydrolysis of the pretreated switchgrass results in 96%glucan and 98%xylan conversion.[C2C1Im][OAc]pretreatment has been successfully scaled up to 40 kg with improved sugar titers and yields relative to bench scale(6 kg).The mass flow of the overall process was established and the major scale-up challenges of the process were identified.

Synthesis and biological evaluation of ethyl 6-alkoxy-7-phenyl-4-hydroxy-3-quinolinecarboxylates against Eimeria tenella

A series of ethyl 6-alkoxy-7-phenyl-4-hydroxy-3-quinolinecarboxylates were designed and synthesized.Their structures were confirmed by ~1H NMR,^(13)C NMR,IR and HRMS.The biological activities were primarily evaluated against Eimeria tenella according to Anticoccidial Index(ACI) method in vivo.The results showed that compounds 5e,5f and 5i exhibited anticoccidial activities against E.tenella at 27 mg kg^(-1).

Ab Initio Calculation of Room Temperature Ionic Liquid 1-Ethyl-3-Methyl-Imidazolium Chlorocuprate (Ⅰ)

The Hartree-Fock method has been employed to investigate the electronic structures of EMIM^＋（1-ethyl-3-methyl-imidazolium^＋）, CuCl2^-, Cu2Cl3^-, CuCl3^2-, EMIM＋^-CuCl2^-, EMIM^＋-Cu2Cl3^-, and EMIM^＋-CuCl3^2- pairs. Full optimization and frequency analyses of EMIM^＋, CuCl2^-, Cu2Cl3^-, CuC13^-, eight initial EMIM^＋-CuCl2^-, six EMIM^＋-Cu2Cl3^-, and four EMIM^＋-CuCl3^2- geometries have been carried out using Gaussian-94 soft-package at 6-31＋G（d,p） basis set level for hydrogen, carbon, nitrogen, chlorine atoms and Hay-Wadt effective core potential for copper atom. The electronic structures of lowest energy of EMIM^＋-CuCl2^-, EMIM＋-Cu2Cl3^-, EMIM^＋-CuCl3^2-, single EMIM^＋, CuCl2^-, Cu2Cl3^-, and CuCl3^2- have been comparatively studied. The calculated results showed that EMIM^＋-CuCl2^- pair conformer of lowest energy was five ring parallel to Cl-Cu-Cl with 3.2A distance, EMIM^＋-CuCl3^2- pair conformer of lowest energy was five ring parallel to CuCl3^2-plane with 3.4A distance, and the optimized EMIM^＋-Cu2Cl3^- pair conformer of lowest energy was five ring perpendicular to Cl-Cu-Cl-Cu-Cl plane with 3.0A distance between the terminal Cl atoms and the 5-ring of EMIM^＋. The cohesion between cations and anions is brought about by C-H. C1 hydrogen bonds that are reinforced by charge assistance. The frequency analyses suggested that all stationary points are minimum because of no appearing of imaginary frequency. The assigned frequencies were in agreement with the experimental report. The low energy of interaction because of the bulkyasymmetry of EMIM＋ and the charge dispersion of cation and anion leads to the low melting point of the ionic liquids, EMIM^＋-CuCl2^-, EMIM^＋-Cu2Cl3^-, and EMIM^＋-CuCl3^2-. The interaction energy of EMIM^＋-CuCl2^-, EMIM^＋-Cu2Cl3^-, and EMIM^＋-CuCl3^2- is 309.0 kJ/mol, 316.8 kJ/mol, and 320.2 kJ/mol, respectively. The relationship of interaction energy via distance between cations and anions was also investigated by single point energy scan.

DFT Study on the Structure of Ionic Liquid 1-Ethyl-3-methylimidazolium Hexafluorophosphate

This paper reports the ab initio and Density Functional Theory (DFT) studies on the structure of the ionic liquid 1-ethyl-3-methylimidazolium hexafluorophosphate ([EMIM]+[PF6]-). Hartree-Fock (HF) and DFT(B3LYP) methods are respectively used to obtain the stable structure of the gas phase ion pair at the 6-311++G(d, p) basis set level. The theoretical IR spectra of [EMIM]+[PF6]- were obtained from the calculated vibrational frequencies and intensities. The changes of atomic charge population have been investigated using Natural Bond Orbital (NBO) analysis. The computational results show that there may exist hydrogen bonds between the cation and the anion. After ZPE and BSSE corrections, the interaction energy between the cation and the anion is –314.44 kJ?mol-1.

N-乙基咔唑-3-甲醛席夫碱荧光探针的合成及其检测Cu^(2+)性质

以咔唑为原料,经过两步反应制备得到N-乙基咔唑-3-甲醛,其结构经X射线单晶衍射测定属于单斜晶系,空间群为P2_(1)/n。再以N-乙基咔唑-3-甲醛与1,3-二氨-2-丙醇为原料,设计、合成了一种新型双席夫碱荧光探针分子CMP。借助荧光光谱在体积比为6∶4的DMSO/H_(2)O缓冲溶液(Tris-HCl,pH=7.0)中研究了探针CMP对Cu^(2+)的选择性识别。研究结果表明,探针CMP与Cu^(2+)以1∶2的比例配位,结合常数为1.52×10^(5) L·mol^(-1),检出限为0.205μmol·L^(-1)。回收实验表明,探针分子CMP可应用于环境水样中Cu^(2+)的检测。

Synthesis, Crystal Structure and Antitumor Activities of N-(2-(1H-indol-3-yl)ethyl)-2-nitroaniline

The title compound, N-(2-(1H-indol-3-yl)ethyl)-2-nitroaniline(C16H15N3O2, Mr = 281.31), has been synthesized by the multicomponent reaction of milder Ullmann, and its structure was characterized by 1H NMR, 13 C NMR, IR, H RMS(ESI) and single-crystal X-ray diffraction. It crystallizes in monoclinic, space group I2/c with a = 15.0212(10), b = 9.4911(6), c = 20.3075(13) A, β = 100.776(7)o, V = 2844.1(3)A3, Z = 8, Dc = 1.314 g/cm3, F(000) = 1184.0, μ = 0.089 mm-1, the final R = 0.0574 and w R = 0.1688 for 1701 observed reflections(I 】 2σ(I)). X-ray analysis indicates three major N(2)–H(2)···O(2), C(13)–H(13)···O(2), N(2)–H(2)···N(3) hydrogen bonds and π-π stacking interactions in the crystal structure. The preliminary biological test shows that the title compound has a good antitumor activity against A549 in vitro with the IC50 value of 35 μmol/L.

Long-term and combined effects of N-[2-(nitrooxy)ethyl]-3-pyridinecarboxamide and fumaric acid on methane production,rumen fermentation, and lactation performance in dairy goats

Background:In recent years,nitrooxy compounds have been identified as promising inhibitors of methanogenesis in ruminants.However,when animals receive a nitrooxy compound,a high portion of the spared hydrogen is eructated as gas,which partly offsets the energy savings of CH4mitigation.The objective of the present study was to evaluate the long-term and combined effects of supplementation with N-[2-(nitrooxy)ethyl]-3-pyridinecarboxamide(NPD),a methanogenesis inhibitor,and fumaric acid(FUM),a hydrogen sink,on enteric CH4production,rumen fermentation,bacterial populations,apparent nutrient digestibility,and lactation performance of dairy goats.Results:Twenty-four primiparous dairy goats were used in a randomized complete block design with a 2×2factorial arrangement of treatments:supplementation without or with FUM(32 g/d)or NPD(0.5 g/d).All samples were collected every 3 weeks during a 12-week feeding experiment.Both FUM and NPD supplementation persistently inhibited CH4yield(L/kg DMI,by 18.8%and 18.1%,respectively)without negative influence on DMI or apparent nutrient digestibility.When supplemented in combination,no additive CH4suppression was observed.FUM showed greater responses in increasing the molar proportion of propionate when supplemented with NPD than supplemented alone(by 10.2%vs.4.4%).The rumen microbiota structure in the animals receiving FUM was different from that of the other animals,particularly changed the structure of phylum Firmicutes.Daily milk production and serum total antioxidant capacity were improved by NPD,but the contents of milk fat and protein were decreased,probably due to the bioactivity of absorbed NPD on body metabolism.Conclusions:Supplementing NPD and FUM in combination is a promising way to persistently inhibit CH4emissions with a higher rumen propionate proportion.However,the side effects of this nitrooxy compound on animals and its residues in animal products need further evaluation before it can be used as an animal feed additive.

Synthesis, Bioactivity, and Crystal Structure Analysis of 2-(3-Oxobenzo[d]isothiazol-2(3H)-yl)ethyl Benzoates

Fifteen novel 2-（3-oxobenzo[d]isothiazol-2（3H）-yl）ethyl benzoates were synthesi- zed by the condensation of 2-（2-hydroxyethyl）benzo[d]isothiazol-3（2H）-one with substituted benzoic acids in dichloromethane. All the compounds were characterized by elemental analysis, IR, ESI-MS and 1H NMR. The crystal structures for 2-（2-hydroxyethyl）benzo[d]isothiazol-3（2H）-one （2） and 2-（3-oxobenzo[d]isothiazol-2（3H）-yl）ethyl 2-methoxybenzoate （30） have been determined by X-ray crystal structure analysis. Compound 2 （C9H9NO2S） crystallizes in the monoclinic system, space group Pn with a = 10.552（3）, b = 7.849（2）, c = 10.765（4） A, β = 103.128（4）°, V= 868.3（5） A3, Mr = 195.24, Dc = 1.493 Mg.m-3, μ = 0.33 mm-1, F（000） = 408, Z = 4, R= 0.0314 and wR= 0.0628. Compound 30 （C17H15NO4S） crystallizes in the triclinic system, space group P1 with a = 8.028（2）, b = 9.300（2）, c = 10.430（3）A, V= 752.1（3）A3, Mr = 329.36, D,= 1.454 Mg.m-3, p = 0.24 mm-1, F（000） = 344, Z = 2, R = 0.0377 and wR = 0.0904. The preliminary biological test indicated that the title compounds show better growth inhibitory activity against the gram-positive bacteria than the gram-negative bacteria.