高效液相色谱法同时测定间二甲胺基苯甲酸、间氨基苯甲酸和间硝基苯甲酸

1　引　　言间二甲胺基苯甲酸是重要的染料、医药、农药和有机试剂的中间体 ,尤其是压敏和热敏染料结晶紫内酯的重要中间体之一。随着对结晶紫内酯的需求不断增长 ,国内近几年正在研究开发该产品。本文是伴随以间硝基苯甲酸为原料 ,加氢还原为间氨基苯甲酸 ,再以甲醛甲基化合成间二甲胺基苯甲酸的研究过程的分析测试研究。本方法适用于间二甲胺基苯甲酸产品检测及含有各种中间产物的过程检测。2　实验部分2 .1　仪器和试剂　Ｗａｔｅｒｓ高效液相色谱仪 (包括 5 15泵 ;772 5Ｉ手动进样器 ,2 0 μＬ定量管 ;4 86紫外检测器 ) ,Ａｎａｓｔａｒ…     

间羟基苯甲醛制备新方法研究

间羟基苯甲醛是一种重要的精细化工原料，主要用于药物合成，香料生产及电镀工业等领域。目前工业生产间羟基苯甲醛大都采用苯甲醛的硝化反应、还原反应、重氮化水解和间甲酚的乙酰化反应、氯化反应及水解反应两种方法。由于这两种化学方法反应步骤多，伴生的付产物量多，...     

环氧化丁基橡胶的合成与表征

以正己烷为溶剂、间氯过氧苯甲酸(mCPBA)为环氧化试剂对丁基橡胶(IIR)进行环氧化改性研究,考察了原料配比、反应温度、胶液浓度等反应条件对环氧化反应的影响,并对反应过程中发生的副反应进行了探究.采用核磁共振氢谱(1H-NMR)对合成的环氧化丁基橡胶(EIIR)的结构进行了表征,并对环氧化度进行了定量计算.确定了最优...     

三光气法合成间苯二亚甲基二异氰酸酯研究

采用无毒的三光气代替光气与间苯二甲胺反应,合成了间苯二亚甲基二异氰酸酯。考察了原料的摩尔比、反应温度、反应时间和氮气气速的影响。结果表明,间苯二甲胺和三光气的摩尔比为1.25∶1.0,用10m L·min-1的氮气连续通入反应体系,反应温度为130℃,反应时间为6.0 h,间苯二亚甲基二异氰酸酯的产率为80.65%。     

汉黄芩素的方便合成

汉黄芩素(Wogonin)是一种重要的黄酮类化合物,具有广泛的药理活性,其研究越来越受到重视.汉黄芩素的大量获得是对其深入研究的基础,但目前存在从天然产物中提取困难、全合成原料不易获得、反应条件苛刻、贵重及有毒试剂的使用、分离纯化困难或收率低等问题.以间苯三酚为原料,经七步反应得到汉黄芩素,总收率达到58%.具有原料及试剂便宜易得、反应条件温和、操作简便及无需柱层析纯化等优点,为汉黄芩素的规模化制备及深入研究奠定了基础.     

间磺酸基偶氮氯磷与镧显色反应的研究及应用

间磺酸基偶氮氯膦(CPAmS)是测定钍优良试剂,本文研究了在β-环糊精及溴化十六烷基三甲基铵存在下,该试剂与La(Ⅲ)的显色反应,并用于钛酸镧烧结物中游离氧化镧的测定,结果满意.1试验部分1.1试剂与仪器La(Ⅲ)标准溶液:按常法配成1.omg·ml~(-1)贮备液,用时稀释为10μg·ml~(-1)工作溶液     

新显色剂间羧基偶氮苦胺酸光度法测定铌的研究——钢铁中微量铌的测定

本文研究了间羧基偶氮苦胺酸与铌的显色反应,在硝酸介质中,试剂与铌形成1∶1的蓝色配合物,在639nm波长处具有最大吸收,对比度为70nm,摩尔吸光系数为3.74×10~4,铌量在0～40μg/25mL范围内符合比尔定律。试剂用于钢铁中微量铌的测定,结果令人满意。     

用KOH／Al2O3合成N—烷基咪唑

N-烷基化咪唑类化合物的合成常以咪唑为原料,在强碱的作用下,经烷基化反应而获得。方法有醇钠或氨基钠与咪唑反应,生成咪唑负氮离子,然后再与烷基化试剂反应以及在相转移催化下咪唑与烷基化试剂的反应。近年来,应用无机载体试剂进行各种有机合成反应已引起人们的广泛兴趣。我们以KOH/Al_2O_3为载体试剂合成了10种N-烷基咪唑衍生物,收率一般在80%以上。其中某些反应室温下即可完成,操作十分简便。且载体经再生后使用活性不变。     

添加碳元素合成化学计量比LiNiO2

本文采用添加碳元素、葡萄糖及使用多种试剂为原料的合成方法,合成了具有化学计量比的LiNiO2.分析了这些方法在合成反应中的作用,同时给出了合成LiNiO2的最佳反应条件.     

载溴树脂作为活泼芳香族化合物的溴化剂

用载溴树脂作为间甲基茴香醚、间甲酚等活泼芳香化合物的溴化剂，得到一溴代产物，产率为75～85%。该试剂反应条件温和，选择性好，是一种有效的活泼芳环的溴化剂。离子交换树脂可回收使用。     

Development of the chemistry of phosphorus-containing macroheterocycles derived from dibenzylidenedipentaerythritol

Synthesis of 10-membered phosphorus-containing macroheterocycles derived from 1,3;1′,3′-dibenzylidene derivatives of dipentaerythritol and trivalent phosphorus compounds, ethyl phosphorodichloridite and ethyl tetraethylphosphorodiamidite, was studied. It was established that the synthesis is controlled by reaction temperature, along with reactant molar ratio.     

高铝MAP沸石的非自发结晶动力学研究

在强碱性水溶液体系中,以水玻璃为硅源,以铝酸钠为铝源,在类质同晶高硅P沸石晶种导向作用下,反应物中自发生成的A型沸石可转晶为纯相高铝MAP沸石。升高反应温度有利于提高产物的结晶度。由不同温度下的晶化曲线计算出MAP沸石表观生长活化能为59.6kJ.mol^-^1。不用晶种时,同一反应物体系结晶产物为单一的A型沸石。在该反应物体系中,A型沸石的成核活化能与生长活化能分别为40.3和50.7kJ.mol^-^1。MAP高的生长活化能以及A型沸石相对低的成核与生长活化能揭示合成MAP沸石时使用晶种的原因。     

Concise Synthesis of 2‐Arylpropanoic Acids and Study of Unprecedented Reduction of 3‐Hydroxy‐2‐arylpropenoic Acid Ethyl Ester to 2‐Arylpropenoic Acid Ethyl Ester by BH3⋅THF

We have developed a concise method of synthesizing racemic arylpropanoic acids, which have been widely used as nonsteroidal anti‐inflammatory drugs (NSAIDs). The synthesis involves only four steps from commercially available benzaldehyde. The synthesis incorporates an unprecedented reduction reaction, conversion of 3‐hydroxy‐2‐arylpropenoic acid ethyl ester to 2‐arylpropenoic acid ethyl ester by BH₃?THF. The reduction reaction has been investigated and optimized.     

高硫合成气法合成甲硫醇研究进展

甲硫醇是生产农药,医药,石油化工产品与合成材料的重要原料,其最主要的应用为合成动物饲料蛋氨酸.硫化氢合成气一步法制备甲硫醇具有原料易得,工艺简单等优点,因此该方法成为合成甲硫醇工艺的研究热点.我们综述了硫化氢合成气合成甲硫醇反应中钼基、钨基和钒基催化剂的研究进展,特别是钼基催化剂体系下载体和助剂对催化剂性能的影响,探索了该工艺的反应路径和反应机理,并对高硫合成气制备甲硫醇工艺的应用前景进行了展望.     

抗革兰氏阴性菌耐格霉素的形式合成

耐格霉素是具有抗革兰氏阴性菌活性的天然产物.以廉价易得的3-羰基-4-氯丁酸乙酯为原料,以八步29%的总收率实现了耐格霉素的形式合成.该工作改进了文献的合成路线,利用生物催化不对称还原高立体选择性引入C-5位的手性羟基,并将危险的叠氮引入反应放在合成后期,降低合成路线的操作风险.分子中C-3位的仲碳胺基手性中心通过Ellamn试剂介导的不对称Mannich反应构建.该路线易于放大,有望为构建耐格霉素类似物分子库以及高通量药物筛选奠定基础.     

Monitoring of chemical reactions within microreactors using an inverted Raman microscopic spectrometer

An inverted Raman microscope spectrometer has been used to profile the spatial evolution of reactant and product concentrations for a chemical reaction within a microreactor operating under hydrodynamic flow control. The Raman spectrometer was equipped with a laser source at wavelength of 780 nm, confocal optics, a holographic transmission grating, and a charge-coupled device (CCD) detector. The microreactor consisted of a T-shaped channel network etched within a 0.5 mm thick glass bottom plate that was thermally bonded to a 0.5 mm thick glass top plate. The ends of the channel network were connected to reagent reservoirs that were linked to a syringe pump for driving the solutions by hydrodynamic pumping within the channels. The microchannels were 221 micro m wide and 73 micro m deep. The synthesis of ethyl acetate from ethanol and acetic acid was investigated as a model system within the microreactor as Raman scattering bands for each reactant and product species were clearly resolved. Raman spectral intensities of each band were proportional to concentration for each species and hence all concentrations could be quantitatively measured after calibration. By scanning specific Raman bands within a selected area in the microchannel network at given steps in the X-Y plane, spatially resolved concentration profiles were obtained under steady-state flow conditions. Under the flow conditions used, different positions within the concentration profile correspond to different times after contact and mixing of the reagents, thereby enabling one to observe the time dependence of the product formation. Raman microscopy provides a useful complementary technique to UV/VIS absorbance and fluorescence methods for the in situ monitoring and analysis of chemical reaction species having their lowest S(0)-S(1) absorption bands too far in the UV to be of use, due to their probable overlap with the bands from other reactant, product and solvent molecules.     

消炎镇痛药联苯乙酸乙酯的合成新工艺

以苯乙腈为超始原料，经5步反应合成了消炎镇痛药联苯乙酸乙酯，优化了反应条件，5步反应总收率为23.8%。     

大环二萜类化合物的研究(Ⅰ)——合成Sarcophytol-B关键中间体的新途径

本文报道了由香叶醇为起始原料合成Sarcophytol-B(1)关键中间体--(Z,E,E)-2-异丙基-5,9,13-三甲基十四碳-2,4,8,12-四烯酸乙酯(2)的新途径。其中关键步骤是溴化法呢基三苯基鏻(8)和2-氧代-3-甲基丁酸乙酯(3)的Wittig反应。     

Total synthesis of (±)-streptonigrin: de novo construction of a pentasubstituted pyridine using ring-closing metathesis

The synthesis of the potent antitumor agent (±)-streptonigrin has been achieved in 14 linear steps and 11% overall yield from ethyl glyoxalate. The synthesis features a challenging ring-closing metathesis reaction, followed by elimination and aromatization, to furnish a key pentasubstituted pyridine fragment.     

A concise synthesis of a very late antigen-4 antagonist trans-4-[1-[[2,5-dichloro-4-(1-methyl-3-indolylcarboxyamide)phenyl]acetyl]-(4S)-methoxy-(2S)-pyrrolidinylmethoxy]cyclohexanecarboxylic acid via reductive etherification

This contribution describes a concise synthesis to ethyl trans-[(4S)-methoxy-(2S)-pyrrolidinylmethoxy]cyclohexanecarboxylate (2b) as a key intermediate of very late antigen-4 (VLA-4) antagonist trans-4-[1-[[2,5-dichloro-4-(1-methyl-3-indolylcarboxyamide)phenyl]acetyl]-(4S)-methoxy-(2S)-pyrrolidinylmethoxy]cyclohexanecarboxylic acid (1). The synthesis employs a reductive etherification as a key reaction using (2S,4S)-1-benzyloxycarbonyl-4-methoxypyrrolidine-2-carboxyaldehyde (12) and trans-4-triethylsilyloxycyclohexanecarboxilic acid ethyl ester (13b). This synthesis provides 2b in 6 steps with 38% overall yield from commercially available starting material.