2-甲基磺酰-4,6-二甲氧基嘧啶的合成及应用

以硫脲和丙二酸二乙酯为初始原料合成2甲基磺酰4,6二甲氧基嘧啶,总收率为62.3%(以硫脲为基准),其合成路线新颖、简便。2甲基磺酰4,6二甲氧基嘧啶是农药合成的重要中间体,特别在绿色农药新品种2嘧啶氧基N芳基苄胺衍生物的合成中。     

6-羟基-2-氟-N-取代芳基苄胺类化合物的合成

6-羟基-2-氟-N-取代芳基苄胺类化合物是合成含氟嘧啶氧苄胺类除草剂的关键中间体,本文以2,6-二氟苯醛为起始原料,合成6-羟基-2-氟苯甲醛,再与芳胺缩合成Schiff 碱,最后经硼氢化钠还原,合成了5个化合物,其结构经1HNMR和MS表征.     

5,7-二甲基-N-芳基-1,2,4-三唑[1,5-a]嘧啶-2-磺酰胺的合成

以5-氨基-3-巯基-1,2,4-三唑为原料,经氧氯化后分别与6个芳胺反应,得到5氨基-N-芳基1,2,4-三唑-3-磺酰胺,继而和乙酰丙酮于乙酸中环合,制得6个取代的1,2,4-三唑[1,5-a]嘧啶-2-磺酰胺衍生物,同时讨论了胺解反应和环合反应的影响因素。所有目标产物的结构均经IR和1HNMR谱验证。     

一类新型嘧啶苯氧（硫）醚的合成及生物活性

嘧啶杂环在农药研究与应用中占据重要的地位,多种商品化的杀虫剂、杀菌剂、除草剂中均含有嘧啶结构。例如具有杀虫活性的芳氧基嘧啶和嘧啶胺,以抗菌素Strobilurin为先得到的新型杀菌剂ICIA 5504、具杀菌活性的芳基嘧啶,具有除草活性     

2-甲基磺酰-4,6-二甲氧基嘧啶的合成

以硫脲和丙二酸二乙酯为初始原料合成2-甲基磺酰-4,6-二甲氧基嘧啶,其合成路线新颖、简便.2-甲基磺酰-4,6-二甲氧基嘧啶是农药合成的重要中间体,特别在绿色农药新品种2-(4,6-二甲氧基)嘧啶氧基-N-芳基苄胺衍生物的合成中.     

5-甲基-N-芳基-1，2，4-三唑[1，5-a]嘧啶-2-磺酰胺的合成

以4个N-芳基-5-氨基-1,2,4-三唑-3-磺酰胺为原料,分别与4,4-二甲氧基-2-丁酮在碱性水溶液中环合,制得4个5-甲基-N-芳基-1,2,4-三唑[1,5-a]嘧啶-2-磺酰胺衍生物,并比较了4,4-二甲氧基-2-丁酮的合成路线,所有目标产物的结构均经IR和1HNMR谱验证.     

N-双嘧啶取代芳胺的合成及其抗氧化损伤研究

报道了一种N-双嘧啶取代芳胺衍生物2-(3-氯苯基)-N-(2-(3-氯苯基)-6-甲基嘧啶-4-基)-N-(2-甲氧苯基)-6-甲基嘧啶-4-胺的合成、表征及其抗氧化生物活性,该N-双嘧啶取代芳胺衍生物是以3-氯苄腈为原料经4步反应合成而得到,其结构通过1HNMR、13CNMR、HR-MS进行了表征和确认。化合物的抗氧化作用与细胞毒作用分别通过是否进行双氧水处理的SH-SY5Y细胞与CCK-8试剂盒进行检测,通过荧光探针DCFH-DA标记检测细胞内ROS含量。结果表明,该化合物具有抗双氧水氧化损伤的可能,能够显著提高细胞存活率且没有明显的细胞毒性。     

药物中间体5-溴-2-氯-N-环戊胺嘧啶-4-胺的有关物质含量分析方法

建立了5-溴-2-氯-N-环戊胺嘧啶-4-胺高效液相色谱法测定有关物质含量的分析方法。以自身对照,按外标法加校正因子计算有关物质含量。使用Agilent HC-C₁₈色谱柱,流动相为0.1%磷酸和乙腈,梯度洗脱;检测波长240 nm。各杂质在0.025～1.000μg/mL浓度范围内线性关系良好,平均加样回收率在90%～110%,其RSD小于5%。该方法快速、准确,适用于5-溴-2-氯-N-环戊胺嘧啶-4-胺有关物质含量分析方法的检测。     

2-芳氧基-噻吩并[2,3-d]嘧啶-4（3H）-酮衍生物的合成

采用串联氮杂Wittig反应,合成了5种未见文献报道的2-芳氧基-噻吩并[2,3-d]嘧啶-4（3 H）-酮衍生物。首先由膦亚胺与芳基异氰酸酯反应得到碳二亚胺,再与取代酚在碳酸钾的催化下反应得到目标化合物,收率为62%～85%,并采用元素分析、IR、MS、1 HNMR等手段对目标化合物的结构进行了确证。     

嘧啶氧苄胺类除草剂的合成研究

嘧啶氧苄胺类化合物作为新型ALS抑制剂类除草剂,具有广谱、高效、低毒、低残留、高选择性和与环境良好的兼容性等特点.本文分别对以6-卤代硝基苯为起始原料、以6-烷基水杨醛为起始原料和以水杨醛为起始原料的3条路线进行介绍,并对合成这3种类型化合物的重要中间体4,6-二甲氧基-2-甲磺酰嘧啶的合成方法作了初步的探讨.     

脱氢枞胺改性硅橡胶复合材料的制备及性能研究

以脱氢枞酸为原料采用衍生化反应合成了脱氢枞胺（DA）并通过FT-IR、MS和¹H NMR等手段对产物结构进行表征,分析表明确定合成了脱氢枞胺。以聚硅氧烷、白炭黑和脱氢枞胺等为原料,采用缩合反应合成了脱氢枞胺改性硅橡胶,并研究了脱氢枞胺添加量对硅橡胶性能的影响。研究发现随着脱氢枞胺添加量的增加改性硅橡胶的形貌越来越粗糙,密度、硬度相应提升,表干时间加快。此外,改性硅橡胶的力学性能和热稳定性随着脱氢枞胺添加量增加先升高后降低,当脱氢枞胺添加量为5%时,改性硅橡胶拉伸强度、断裂伸长率、失重10%所对应的温度和最大失重速率温度分别为0.57MPa、170%、373 ℃、583 ℃。     

An Unexpected Pressure Effect in the Catalytic Hydrogenolysis of a Complex Benzyl Amine

The selective hydrogenolysis of a complex benzylamine containing a pyridone ring and aryl fluorides was investigated. The aim of the research was to find a catalyst and reaction conditions under which the complete hydrogenolysis of the benzylamine could be accomplished with no aryl fluoride cleavage nor pyridone hydrogenation observed. This objective was accomplished by use of a specific 10 % Pd/C catalyst in a THF/EtOH solvent at 40 °C. It was found that as the H₂ pressure decreased the amount of debenzylated amine increased because of the decrease in pyridone hydrogenation. Unexpectedly, though, the rate of hydrogenolysis also increased with decreasing H₂ pressure. A rationale for this observation is presented.

     

Reaction of β-aminoamides with aromatic aldehydes

The American Oil Chemists’ Society official methods TF 1b-64 and TF 2b-64, “Quantitative Determination of Amines,” fail to correctly analyze fatty diethylenetriamine (DETA)-diamides and diamides of 3,3′’-iminobispropylamine (DPTA). Primary amine determination through the formation of Schiff base adducts using salicylaldehyde will, in the case of secondary amines that bear amide carbonyl at either the β or γ position, undergo reactions that consume salicyladehyde despite the absence of primary amine groups. The product of this reaction has been investigated, and a cyclic (2-arylimidazolidine) structure is advanced as the principal adduct of the reaction of aryl aldehydes with DETA-diamides.     

An Unexpected Pressure Effect in the Catalytic Hydrogenolysis of a Complex Benzyl Amine

The selective hydrogenolysis of a complex benzylamine containing a pyridone ring and aryl fluorides was investigated. The aim of the research was to find a catalyst and reaction conditions under which the complete hydrogenolysis of the benzylamine could be accomplished with no aryl fluoride cleavage nor pyridone hydrogenation observed. This objective was accomplished by use of a specific 10 % Pd/C catalyst in a THF/EtOH solvent at 40 °C. It was found that as the H₂ pressure decreased the amount of debenzylated amine increased because of the decrease in pyridone hydrogenation. Unexpectedly, though, the rate of hydrogenolysis also increased with decreasing H₂ pressure. A rationale for this observation is presented.     

N，N-双（2-（1,3-二氧异吲哚-2-基）乙基）丙烯酰胺的合成与表征

以邻苯二甲酸酐(PA)、二乙烯三胺(DETA)为原料,经亲电加成-消除反应合成有机中间体双(2-邻苯二甲酰亚胺)胺(DETA-2PA),其再与丙烯酰氯(AC)发生酰胺化反应合成有机中间体N,N-双[2-(1,3-二氧异吲哚-2-基)乙基]丙烯酰胺(AC-DETA-2PA)。通过FTIR、1HNMR、元素分析、HRMS、HPLC对产物结构进行了确证,并用TGA、荧光光谱对产物的性能进行了测试。考察了反应温度、反应时间、n(AC)∶n(DETA-2PA)及催化剂用量4个因素对合成AC-DETA-2PA胺值的影响。通过响应面设计对AC-DETA-2PA的合成工艺进行了优化,确定其较佳合成工艺条件为:n(AC)∶n(DEETA-2PA)=1.6∶1.0,反应温度为25℃,催化剂氢化钠用量占反应物(AC和DETA-2PA)总质量的8.46%,反应时间4h。在该条件下,AC-DETA-2PA的胺值可达2.96 mg KOH/g。     

2,6-二氨基吡嗪-1-氧化物的合成优化

以亚胺基二乙腈为起始原料,经过亚硝化、环化两步反应得到2,6-二氨基吡嗪-1-氧化物(DAPO),总产率为66.6%。采用1 H NMR、IR、MS对其结构进行了表征。研究了环化反应的催化剂、氢氧化钠用量、反应起始温度等因素对DAPO总收率的影响。将传统合成方法中的催化剂三乙胺用氢氧化钠代替,确定了环化反应制备DAPO的最佳工艺条件为:N-亚硝基亚氨基二乙腈、盐酸羟胺、氢氧化钠质量比为1.0∶0.6∶1.0,初始温度5~10℃,反应时间30min,随后反应温度20℃,反应时间2h。结果表明,与传统三乙胺作催化剂的合成方法相比,以氢氧化钠作环化反应催化剂合成DAPO的收率由57.0%提高至78.7%。结合DAPO的合成过程,提出了2,6-二氨基吡嗪-1-氧化物(DAPO)的成环机理为:羟胺亲核加成N-亚硝基亚氨基二乙腈的氰基,生成N-亚硝基亚氨基二乙腈单缩合产物,在碱作用下与羟胺缩合成环,得到最终产物DAPO。     

An Amine‐, Copper‐ and Phosphine‐Free Sonogashira Coupling Reaction Catalyzed by Immobilization of Palladium in Organic–Inorganic Hybrid Materials

An immobilization of palladium in organic‐inorganic hybrid materials‐catalyzed Sonogashira coupling reaction has been described. Terminal alkynes reacted with aryl iodides and aryl bromides only in the presence of a 3‐(2‐aminoethylamino)propyl‐functionalized, silica gel‐immobilized palladium catalyst under amine‐, copper‐ and phosphine‐free reaction conditions. The reaction generates the corresponding cross‐coupling products in excellent yields. Furthermore, the silica‐supported palladium can be recovered and recycled by a simple filtration of the reaction solution and used for 30 consecutive trials without any decreases in activity.     

Reaction kinetics of 2‐((2‐aminoethyl) amino) ethanol in aqueous and non‐aqueous solutions using the stopped‐flow technique

Observed pseudo‐first‐order rate constants (k_o) for the reaction between CO₂ and 2‐((2‐aminoethyl) amino) ethanol (AEEA) were measured using the stopped‐flow technique in an aqueous system at 298, 303, 308 and 313 K, and in non‐aqueous systems of methanol and ethanol at 293, 298, 303 and 308 K. Alkanolamine concentrations ranged from 9.93 to 80.29 mol m^?3 for the aqueous system, 29.99–88.3 mol m^?3 for methanol and 44.17–99.28 mol m^?3 for ethanol. Experimentally obtained rate constants were correlated with two mechanisms. For both the aqueous‐ and non‐aqueous‐AEEA systems, the zwitterion mechanism with a fast deprotonation step correlated the data well as assessed by the reported statistical analysis. As expected, the reaction rate of CO₂ in the aqueous‐AEEA system was found to be much faster than in methanol or ethanol. Compared to other promising amines and diamines studied using the stopped‐flow apparatus, the pseudo‐first‐order reaction rate constants were found to obey the following order: PZ (cyclic‐diamine) > EDA (diamine) > AEEA (diamine) > 3‐AP (primary amine) > MEA (primary amine) > EEA (primary amine) > MO (cyclic‐amine). The reaction rate constant of CO₂ in aqueous‐AEEA was double that in aqueous‐MEA, and the difference increased with an increase in concentration. All reaction orders were practically unity. With a higher capacity for carbon dioxide and a higher reaction rate, AEEA could have been a good substitute to MEA if not for its high thermal degradation. AEEA kinetic behaviour is still of interest as a degradation product of MEA. © 2012 Canadian Society for Chemical Engineering     

常压法制备3，3，3－三氟丙酮酸乙酯

常压制备法具有反应温度易于控制、副反应少、得率高的优点。     

混合醇胺溶液吸收烟气中CO2

研究了温度、CO2含量与吸收液浓度对醇胺溶液吸收CO2性能的影响,并比较了不同复配体系对二异丙醇胺(MDEA)的活化效果。结果表明,醇胺溶液对CO2的吸收速率随反应时间的增加而降低,随吸收温度的升高而增强,以40℃为宜;吸收反应速率均随气、液相反应物含量增大而增强;混合体系对MDEA的活化效果为二乙烯二胺最好,乙醇胺最差。