微波作用下2-烃基-4-喹啉酮的简便合成法

在微波作用下5-(甲硫亚烃基)丙二酸亚异丙酯可与芳胺发生加成消除反应,首先生成5-(芳胺基亚烃基)丙二酸亚异丙酯,继而进一步闭环,提供了2-烃基-4-喹啉酮的快速合成法。     

四氢糠基丙二酸二乙酯的新法合成

四氢糠基丙二酸二乙酯的新法合成牛福水陈楠周智明＊（北京理工大学精细化工教研室１０００８１）四氢糠基丙二酸二乙酯是合成萘呋胺酯草酸盐的重要前体，而萘呋胺酯草酸盐做为一种新型周围血管扩张剂，对脑动脉硬化、脑血栓形成、脑栓塞、耳鸣、头颈损伤及其后遗症有良好...     

(1-萘甲基)四氢糠基丙二酸二乙酯的新法合成

（１－萘甲基）四氢糠基丙二酸二乙酯（Ⅴ）是合成萘呋胺酯草酸盐的重要前体,而萘呋胺酯草酸盐作为一种新型周围血管扩张剂,正受到越来越多的重视［１,２］．（１－萘甲基）四氢糠基丙二酸二乙酯（Ⅴ）的原有合成方法［３］产率低,且反应时间长．本文改进了（Ⅴ）的原...     

新型α-乙氧羰基-γ-芳氧甲基-γ-丁内酯的合成

3-芳氧基-1,2-环氧丙烷与丙二酸二乙酯在乙醇钠存在下反应,合成了6个新型α-乙氧羰基-γ-芳氧甲基-γ-丁内酯,收率47％～89％。其结构经^1H NMR,IR和MS表征。     

环化聚合的研究——4-取代1,6二烯类单体的聚合

合成了二丙烯基丙二酸二乙酯,二丙烯基丙二酸二甲酯,二丙烯基腈基醋酸乙酯,二丙烯基醋酸乙酯,α,α′二氯代丙烯基丙二酸二乙酯,二丙烯基二仲丁基硅烷及—丙烯基丙二酸二乙酯,并在游离基引发下进行了环化聚合。其中二丙烯基丙二酸二甲酯,α,α′二氯代丙烯基丙二酸二乙酯及二丙烯基二仲丁基硅烷三者为文献上未见报导的新单休。所得聚合体可溶在有机溶剂中。测定了聚合体的环化率、分子量、特征粘度等数据。     

(+)-2-甲基-4-戊烯酸的合成

丙二酸二乙酯与碘甲烷反应生成二乙基甲基丙二酸酯(1). 由(1)进行皂化和脱羧反应制备2-甲基-4-戊烯酸(4).用一种新的拆分剂葡辛胺拆分(4)得到(+)-2-甲基-4-戊烯酸.     

喹啉二酮类化合物的合成研究——形成双(二氢喹啉二酮基)甲烷的可能途径

我们曾用2-(3-甲基丁烯-2-基)丙二酸二乙酯与 N-取代芳胺在高温下环合,制备了一系列4-羟基-3-(3-甲基丁烯-2-基)二氢喹啉-2-酮类化合物.在此反应中除得到正常产物外,尚分离到若干副产物,最主要的副产物为3,3′-双(二氢喹啉-2,4-二酮基)甲烷.Young 等人曾对产生这类副产物的机理作过讨论,并提出如下途径:     

新型3-芳甲基-5-芳氧甲基丁内酯的合成及其抑制肺癌细胞生长活性评价

通过2-芳氧甲基环氧烷与α-芳甲基丙二酸二乙酯在乙醇钠条件下反应, 合成了8个新型3-芳甲基-5-芳氧甲基丁内酯, 收率为13%～81%. 由IR, ¹H NMR和MS波谱数据进行了结构表征. 所得化合物均具有抑制A549肺癌细胞生长的活性, 其抑制效果具有浓度依赖性.     

用草酸二乙酯合成正丙氧基丙二酸二乙酯

前言丙二酸二乙酯是重要的合成原料,不同取代的丙二酸酯可进一步合成多种不同取代的化合物。烷氧基取代丙二酸酯的合成,文献报导不多。用草酸酯作原料,以醇钠作缩合剂,对于合成脂肪族烷氧基取代的丙二酸酯尚未得到满意的结果。本文进行了正丙氧基丙二酸二乙酯之合成,全部合成过程以反应式表述如下:     

氟阴离子在有机合成中的应用 I: 无水氟化钾催化丙二酸二乙酯与苯甲醛的Knoevenagel缩合反应

研究了用无水氟化钾催化苯甲醛与丙二酸二乙酯的Knoevenagel反应的反应条件,发现在适宜条件下可进行这一反应, 并制得予其产物苯甲叉丙二酸二乙酯.     

Liquid-liquid equilibria of (water + butyric acid + diethyl succinate or diethyl glutarate or diethyl adipate) ternary systems

Liquid-liquid equilibrium (LLE) data of the solubility (binodal) curves and tie-line end compositions were examined for mixtures of {(water (1) + butyric acid (2) + diethyl succinate or diethyl glutarate or diethyl adipate (3)} at 298.2 K and 101.3 ± 0.7 kPa. The relative mutual solubility of butyric acid is higher in the diethyl succinate or diethyl glutarate or diethyl adipate layers than water layers. The consistency of the experimental tie-lines was determined through the Othmer-Tobias correlation equation. The LLE data were correlated with NRTL model, indicating the reliability of the NRTL equations for these ternary systems. The best results were achieved with the NRTL equation, using non-randomness parameter (α = 0.3) for the correlation. Distribution coefficients and separation factors were measured to evaluate the extracting capability of the solvents.     

An efficient and general route to the synthesis of diethyl α,α-bromofluorophosphonates

An efficient and general two-step halogenation procedure to prepare diethyl α,α-bromofluorophosphonates was described, which included bromination by PPh₃, 2,3-dichloro-5,6-dicyanobenzquinone (DDQ) and n-Bu₄NBr, and electrophilic fluorination by N-fluorobisbenzenesulfonimide (NFSI). Both aromatic and aliphatic α,α-bromofluorophosphonates could be prepared by this method.     

Surface tension of diethyl carbonate, 1,2-dimethoxyethane and diethyl adipate

The surface tension was investigated with a differential capillary rise method in the temperature range from 273 to 373 K for diethyl carbonate, 278 to 373 K for 1,2-dimethoxyethane, and 293 to 373 K for diethyl adipate, respectively. The uncertainties of the temperature and surface tension were estimated to be within ±10 mK and ±0.2 mN m⁻¹, respectively. A surface tension correlation was developed as a function of temperature with the experimental data, and the average absolute deviations were 0.04, 0.07 and 0.09 mN m⁻¹ for diethyl carbonate, 1,2-dimethoxyethane and diethyl adipate, respectively.     

Diethyl bromodifluoromethylphosphonate: a highly efficient and environmentally benign difluorocarbene precursor

A convenient method for the difluoromethylation of phenols and thiophenols, using diethyl bromodifluoromethylphosphonate (1) as a difluorocarbene precursor, is described. This commercially available phosphonate was found to undergo an extremely facile P-C bond cleavage on basic hydrolysis (−78 °C to rt), presumably leading to the bromodifluoromethyl anion, which subsequently converts to a difluorocarbene intermediate. The latter is trapped by phenolates 2 or thiophenolates 3 to give the corresponding difluoromethyl ethers and thioethers in good to excellent yield. The resulting eco-friendly side product, diethyl phosphate ion, is easily separated from the reaction mixture due to its excellent solubility in water. Due to the mild conditions applied to this reaction, phenolate ions bearing carbonyl or enolate functions are selectively difluoromethylated.     

A catalyst-free novel synthesis of diethyl carbonate from ethyl carbamate in supercritical ethanol

Diethyl carbonate has been synthesized via the alcoholysis of ethyl carbamate in supercritical ethanol under catalyst-free conditions.The influences of various parameters such as reaction temperature,reaction time,reaction pressure,ethanol/ethyl molar ratios and reaction loading volume on the yield of DEC were studied systematically.The experimental results indicated that the alcoholysis of ethyl carbamate was greatly improved in supercritical ethanol.The optimal reaction conditions were as follows：a reaction temperature of 573 K,a reaction time of 30 min,a reaction pressure of 13.2 MPa,an ethanol/ethyl carbamate molar ratio of 10 and a reactor loading volume of 285 μL respectively.The optimal yield of DEC was 22.9%.     

超高效液相色谱法测定化妆品中马来酸二乙酯

采用超高效液相色谱法测定化妆品中马来酸二乙酯含量。样品经乙腈超声提取,Waters ACQUITY UPLC HSS T3色谱柱(100mm×2.1mm,1.8μm)分离,乙腈和水为流动相梯度淋洗,在220 nm波长处用二极管阵列检测器检测。马来酸二乙酯的质量浓度在0.50～20 mg·L~(-1)范围内与其峰面积呈线性关系,方法的测定下限(10S/N)为0.5 mg·kg~(-1)。应用此法测定化妆品中两种浓度水平马来酸二乙酯的回收量,方法的平均回收率分别为90.4%和105%,相对标准偏差(n=7)分别为1.5%和3.2%。     

Synthesis of Arylhydrazines by Reaction of Arylbromides with DEAD via Sonochemical Barbier Reaction

A series of arylhydrazines was synthesized from the reaction mixture of Mg powder, 1,2‐dibromoethane, aryl bromide and DEAD (diethyl azodicarboxylate) in THF under ultrasound. This sonochemical Barbier reaction provides an efficient and inexpensive preparation method for synthesis of arylhydrazines.     

Reaction between triphenylphosphine and aromatic amines in the presence of diethyl azodicarboxylate: an efficient synthesis of aryliminophosphoranes under neutral and mild conditions

An efficient synthesis of aryliminophosphoranes is described. A mixture of an aromatic amine, diethyl azodicarboxylate and triphenylphosphine undergo a Mitsonobu type reaction at ambient temperature in dry dichloromethane to afford aryliminophosphoranes in excellent yields.     

A Concise Synthesis of the Pyrroloquinoline Nucleus of the Makaluvamine Alkaloids

A concise five step synthesis of the pyrroloquinoline related to makaluvamine, and discorhabdine from 1,2-dimethoxy-3,5-dinitrobenzene is developed.     

Novel Bis-β-diketone-type Ligand and Its Copper and Zinc Complexes for Two-photon Biological Imaging

A curcumin derivative ligand, 1,7-bis(3-methoxyl-4-oxyethylacetate)phenyl-1,6-heptadiene-3,5-diketone (diethyl acetatecurcumin, abbreviated as HL), and its Cu(II) and Zn(II) complexes have been synthesized and characterized by elemental analyses, infrared(IR), ¹H NMR and molar conductivity. The experimental results show that the resulting complexes bear strong two-photon excited fluorescence(TPEF) in N,N-dimethyformamide solvent, which has been proven to be potentially useful for two-photon microscopy imaging in living cells. In addition, cytotoxicity tests show that the low-micromolar concentrations of metal-ligand complex(ML₂) did not cause significant reduction in cell viability over a period of, at least, 24 h and should be safe for further biological studies.