有机中间体合成中的新试剂、新反应、新技术、新工艺——Ⅲ 氟硝基苯系列产品

本文详细介绍了硝基氯苯在季铵盐和烷氧基聚氧乙烯醚存在下合成2,4-二氟硝基苯、2,3,4-三氟硝基苯、5-氯-2,4-二氟硝基苯、2,4,5-三氟硝基苯、5-氯-2-氟-4-(硝基甲基)硝基苯和5-氯-4-氟-2-(硝基甲基)硝基苯、2-氯-5-氟-4-硝基苯甲酸和4-氯-5-氟-2-硝基苯甲酸、2,4,5-三氟苯甲酸、2-氯-4,5-二氟苯甲酸的最新合成工艺。     

国外专利文献

2-(2-甲酰-6-甲氧基苯氧基)链烷酸的佩金环合反应新历程2-(2-甲酰-6-甲氧基苯氧基)链烷酸在传统的佩金反应条件下环合反应,生成2-烷基-7-甲氧基-5-硝基苯[b]呋喃Ⅰ(R1=Et,n-Pr,n-Bt),2-烷基-9-甲氧基-7-硝基-3-氧基-2,3-二氢-5H苯     

含哒嗪酮的吡唑醛腙类化合物的合成

以1,4,5,6-四氢-6-哒嗪酮-3-甲酰肼和1,6-二氢-6-哒嗪酮-3-甲酰肼与1-苯基-3-芳基-4-甲酰基吡唑反应,得到相应的新化合物1,4,5,6-四氢-6-哒嗪酮-3-羰基吡唑醛腙和1,6-二氢-6-哒嗪酮-3-羰基吡唑醛腙.所有化合物的结构均经IR,1HNMR和元素分析得以证实.     

1,3-二苯基-5-氯-吡唑-4-甲醛腙类化合物的合成

首先通过Vilismier反应得到的1,3-二苯基-5-氯-吡唑-4-甲醛与氨基硫脲反应制备了关键中间体1,3-二苯基-5-氯-吡唑-4-甲醛缩氨基硫脲.最后,经吡唑醛缩氨基硫脲中间体与7种不同的ω-溴代芳基乙酮反应合成了N-(1,3-二苯基-5-氯-吡唑-4-基)-N＇-(芳基-噻唑-2-基)-甲醛腙类衍生物.利用元...     

1-(3-氯-2-吡啶基)-3-三氟甲基-1H-吡唑-5-甲酸的合成

1-(3-氯-2-吡啶基)-3-三氟甲基-1H-吡唑-5-甲酸是鱼尼丁受体杀虫剂DP-23合成的关键中间体。以3-氯-2-吡啶肼及三氟乙酰基丙酮为原料合成1-(3-氯-2-吡啶基)-3-三氟甲基-5-甲基-1H-吡唑,再经溴代、水解和氧化得到1-(3-氯-2-吡啶基)-3-三氟甲基-1H-吡唑-5-甲酸,总收率达到37.4%。     

小蓬草鲜花和鲜果精油挥发性组分分析

利用气质联用仪(GC-MS)对水蒸气蒸馏提取小蓬草鲜花和鲜果精油的挥发性组分进行了分析,结果表明精油组分中匹配度96%以上的共5种化合物:烃类化合物2种,醇类化合物2种,酮类化合物1种。其中含有常用作香料的顺式-2-甲基-5-异丙烯基-2-环己烯-1-醇(顺式香芹醇)、反式-2-甲基-5-异丙烯基-2-环己烯-1-醇(反式香芹醇)和(s)-2-甲基-5-异丙烯基-2-环己烯-1-酮 (s-香芹酮),此外还含有2,6-二甲基-6-(4-甲基-3-戊烯基)双环庚-2-烯。萜类化合物、脂肪酮具有化感作用,小蓬草鲜花和鲜果精油具有开发为香料、除草剂的潜在价值。     

海南山苍子核仁油GC-MS分析

采用水蒸气蒸馏法提取海南山苍子核仁油,用气相色谱-质谱联用技术对其挥发油成分进行分析。GC-MS鉴定出54个化合物,占挥发油总量的70.02%。主要成分有6-甲基-5-庚烯-2-酮,D-苎烯,3,7-二甲基-1,6-辛二烯-3-醇,α,α-4-三甲基-3-环己烯-1-甲醇,3-甲基-2-丁烯醛,癸酸,1-甲基-4-(5-甲基-1-亚甲基-4-己烯基)-环己烯,2,6,6-三甲基-二环[3.1.1]庚烷-3-酮。     

含侧烃基的特种低分子脂肪族二元醇

对部分已工业化生产的含侧烃基的脂肪族二元醇(包括新戊二醇、2-甲基-1,3-丙二醇、1,3-丁二醇、3-甲基-1,5-戊二醇、2,4-二乙基-1,5-戊二醇、2,2,4-三甲基-1,3-戊二醇、2-丁基-2-乙基-1,3-丙二醇、2-乙基-1,3-己二醇、2-甲基-1,8-辛二醇、二聚体二醇、羟基新戊酸羟基新戊醇酯、一缩二丙二醇等)进行了简要介绍。介绍了它们的性能特点和用途,特别是在高分子合成材料中的应用。     

吲哒帕胺的合成研究

以4-氯-3-磺胺基苯甲酸和2,3-二氢-2-甲基-1H-吲哚为主要原料,经3步反应合成了降压药吲哒帕胺.4-氯-3-磺胺基苯甲酸与氯化亚砜反应得4-氯-3-磺胺基苯甲酰氯(Ⅰ),产率98.0%;2,3-二氢-2-甲基-1H-吲哚与亚硝酸反应得到N-亚硝基-2,3-二氢-2-甲基-1H-吲哚(Ⅱ),不用分离出Ⅱ,直接用钯/碳催化剂催化氢化得到N-氨基-2,3-二氢-2-甲基-1H-吲哚(Ⅲ),再进一步制成N-氨基-2,3-二氢-2-甲基-1H-吲哚盐酸盐(Ⅳ),产率92.0%;Ⅰ和Ⅳ反应得到目标产物吲哒帕胺(Ⅴ),产率92.5%,所得产品符合药典标准.     

Amorfrutin B的关键中间体的关环合成

以米氏酸和香叶醇为原料,采用钯催化的一锅串联反应为关键步骤,通过5步反应,高效率地合成了Amorfrutin B的关键中间体——(E)-7-羟基-2,2-二甲基-8-(3,7-二甲基-2,6-辛二烯-1-基)-5-苯乙基-4H-苯并[d][1,3]二噁英-4-酮(Ⅹ)。各中间体和产物的结构通过FTIR和1HNMR得以确认。中间体（E)-3-(3,7-二甲基-2,6-辛二烯-1-氧基)-3-丙二酸酯(Ⅲ)、(E)-3,7-二甲基-2,6-辛二烯-1-基-4-(2,2-二甲基-4-氧代-4H-1,3-二氧六环-6-基)-3-氧代丁酸(Ⅵ)的反应条件得以优化,提高了产率,降低了成本,使合成路线更加经济合理。对关键串联反应的机理进行了解释,即中间体(E)-3,7-二甲基-2,6-辛二烯-1-基-4-(2-(2,2-二甲基-4-氧代-4H-1,3-二氧六环-6-基）乙酰基)-3-氧代-5-苯基戊酯(Ⅸ)通过两次卡罗尔重排、脱羧后分子内Aldol缩合及脱水后芳构化等一系列转变形成了具有苯酚结构的关键中间体Ⅹ。Ⅹ的成功合成为Amorfrutin B的完全合成奠定了重要基础。     

Drying characteristics of porous material immersed in a bed of hygroscopic porous particles fluidized under reduced pressure

A relatively large wet material was immersed in a fluidized bed of hygroscopic porous particle (silica gel beads) under reduced pressure. And then the drying characteristics were compared with those in the case of inert particle (glass beads). The comparison of drying characteristics is performed experimentally and theoretically. In calculation, the water transfer from the sample to the fluidized bed was considered. The calculation results are in good agreement with the experimental data. The effects of the operational conditions (the pressure in the drying chamber and the temperature of the drying gas) on the drying characteristics were also examined in both fluidizing particles.The drying finishes earlier in the case of hygroscopic porous particle than in the case of inert particle regardless of pressure in the drying chamber, since the water transfer from the sample facilitates the drying in the case of hygroscopic porous particles. The temperature decrement in drying appears in the case of inert particle. This phenomenon is also observed in the case of hygroscopic porous particle, but the decrement degree of the temperature is much smaller than that in the case of inert particle. The difference of the minimum temperature in the sample in drying between the cases of hygroscopic porous particle and inert particle is very slight for different pressures in the drying chamber.     

Streptozotocin-Induced Diabetes Causes Changes in Serotonin-Positive Neurons in the Small Intestine in Pig Model

Serotonin (5-hydroxytryptamine or 5-HT) is an important neurotransmitter of the central and peripheral nervous systems, predominantly secreted in the gastrointestinal tract, especially in the gut. 5-HT is a crucial enteric signaling molecule and is well known for playing a key role in sensory-motor and secretory functions in the gut. Gastroenteropathy is one of the most clinical problems in diabetic patients with frequent episodes of hyperglycemia. Changes in 5-HT expression may mediate gastrointestinal tract disturbances seen in diabetes, such as nausea and diarrhea. Based on the double immunohistochemical staining, this study determined the variability in the population of 5-HT-positive neurons in the porcine small intestinal enteric neurons in the course of streptozotocin-induced diabetes. The results show changes in the number of 5-HT-positive neurons in the examined intestinal sections. The greatest changes were observed in the jejunum, particularly within the myenteric plexus. In the ileum, both de novo 5-HT synthesis in the inner submucosal plexus neurons and an increase in the number of neurons in the outer submucosal plexus were noted. The changes observed in the duodenum were also increasing in nature. The results of the current study confirm the previous observations concerning the involvement of 5-HT in inflammatory processes, and an increase in the number of 5-HT -positive neurons may also be a result of increased concentration of the 5-HT in the gastrointestinal tract wall and affects the motor and secretory processes, which are particularly intense in the small intestines.     

污泥生物炭中氮硫行为及环境效应研究进展

污泥生物炭中氮硫元素含量高,其氮硫行为和环境效应对全球气候变化的影响不容忽视。以往的研究中,研究者往往以富碳生物炭作为主要研究对象,关注碳对全球气候变化的行为和功效,而对氮硫元素的作用关注不够。本文从原始污泥基本性质到其热解过程,再到生物炭的老化,逐步对污泥生物炭整个生命周期内氮硫的行为及其环境效应研究进行综述,并对未来应注重开展的研究方向进行展望,为生物炭中氮硫元素固定、释放及与之关联的环境效应和温室气体排放控制研究提供理论基础。分析表明,污泥中氮元素含量普遍高于硫元素,且热解过程中氮比硫更容易转移至气相产物。氮硫元素随热解温度的增加,在三相产物中的分配都是炭中持续减少,油中先增后减,气中一直增加。高温（＞800℃）条件下,气相中的氮含量高于固相,而硫元素则仍然主要存在于固相中。污泥生物炭老化及其环境效应研究表明,污泥生物炭氮硫元素与土壤的相互作用及其温室效应问题在今后的研究中应引起重视。     

Evaluation of surfactant-aided degumming of vegetable oils by membrane technology

The first step in the process of vegetable oil refining is degumming, in which phospholipids and mucilaginous gums are removed that otherwise result in a low-grade oil. A membrane process is remarkably simple yet potentially offers many advantages in degumming. Studies were conducted on surfactant-aided membrane degumming with soybean and rapeseed oils in a magnetically stirred flat membrane batch cell with different types of microfiltration membranes. The reduction of phospholipids in soybean oil was in the range of 85.8–92.8% during the membrane process. The phosphorus content of membrane permeates of soybean oil was in the range of 20–58 mg/kg. Crude rapeseed oil contained higher amount of nonhydratable phospholipids and hence resulted in lower reduction in phospholipids, in the range of 66.4–83.2%. Addition of hydratable phospholipids could improve the efficiency of degumming in the membrane process without using any electrolyte, resulting in improvement of quality as well as quantity of the phospholipids.     

Possible Role of Crystal-Bearing Cells in Tomato Fertility and Formation of Seedless Fruits

Crystal-bearing cells or idioblasts, which deposit calcium oxalate, are located in various tissues and organs of many plant species. The functional significance of their formation is currently unclear. Idioblasts in the leaf parenchyma and the development of crystal-bearing cells in the anther tissues of transgenic tomato plants (Solanum lycopersicon L.), expressing the heterologous FeSOD gene and which showed a decrease in fertility, were studied by transmission and scanning electron microscopy. The amount of calcium oxalate crystals was found to increase significantly in the transgenic plants compared to the wild type (WT) ones in idioblasts and crystal-bearing cells of the upper part of the anther. At the same time, changes in the size and shape of the crystals and their location in anther organs were noted. It seems that the interruption in the break of the anther stomium in transgenic plants was associated with the formation and cell death regulation of a specialized group of crystal-bearing cells. This disturbance caused an increase in the pool of these cells and their localization in the upper part of the anther, where rupture is initiated. Perturbations were also noted in the lower part of the anther in transgenic plants, where the amount of calcium oxalate crystals in crystal-bearing cells was reduced that was accompanied by disturbances in the morphology of pollen grains. Thus, the induction of the formation of crystal-bearing cells and calcium oxalate crystals can have multidirectional effects, contributing to the regulation of oxalate metabolism in the generative and vegetative organs and preventing fertility when the ROS balance changes, in particular, during oxidative stresses accompanying most abiotic and biotic environmental factors.     

泰乐菌素在提取工艺中溶液中的稳定性研究

为探讨泰乐菌素在提取工艺中溶液中的稳定性,取提取工艺中不同环节的泰乐菌素溶液,采用高效液相色谱法测定在一定时间内检测泰乐菌素的含量,观察不同环节的泰乐菌素溶液的降解情况。结果显示,在提取工艺中不同环节的泰乐菌素溶液,均较稳定,结果证明,提取工艺中不同环节的泰乐菌素溶液稳定,基本上不降解。     

The stability of sodium hypochlorite in the presence of surfactants

Studies were made on the stability of NaOCl at 40°C in the presence of sodium alkanesulfonate or alkylarenesulfonate anionic surfactants, and in the presence of a nonionic surfactant,N-octylpyrrolidinone. The results were compared with NaOCl stability in the absence of additives and in the presence of nonsurfactant short-chain sodium alkylbenzenesulfonates. The data indicated that the rate of NaOCl loss is greatly dependent upon the pH of the solution, even at alkaline pHs. At initial pHs below 11, in the absence of additive, there is significant disproportionation of OCl⁻ to ClO ₃ ⁻ , accompanied by decrease in the pH of the solution, within a period of several days. Even at an initial pH of 11.3, in the presence of the surfactants investigated, there is significant disproportionation of OCl⁻ and decrease in the pH of the solution in the first several days. When the initial pH of the solution is 13.5, there is no significant decrease in pH of the solution for at least two months in the presence of the surfactants studied. NaOCl stability in the presence of surfactant decreases in the order: sodium linear alkanesulfonate > sodium linear alkyldiphenylethersulfonate > sodium linear alkylbenzenesulfonate >>N-octylpyrrolidinone. Stability was greater in the presence of linear alkylarenesulfonates than in the presence of branched alkylarenesulfonates. It is suggested that the differences in stability observed are due to the greater ease of oxidation of tertiary carbon atoms compared to primary or secondary atoms.     

Stress and strain state of concrete during freezing and thawing cycles

The objective of this work is to calculate the pressures, stresses, and strains induced into moist concrete during freezing and thawing. The applied theory is based on thermodynamics and the linear theory of elasticity. If no additional salts are dissolved in the pore water the inputs needed in the theory are relative humidity and temperature measured in the sample chamber and inside concrete and evaporable water amount in the pore structure. Theoretical results were compared with the test results made with two concretes cured under water or at 96% relative humidity. One of the concretes was air entrained and in the comparison concrete no air-entraining agents were used. In the test cylinders cured under water the largest tensional stresses in freezing occurred on the surface of the test cylinders both in the axial and tangential direction. The largest tensional stress was 2.2 MPa, both in air-entrained and in non air-entrained concretes. The largest tensional stresses in the warming phase took place at the end of the thawing period when the chamber temperature was around +5 °C. Then the maximum tension occurred in the middle of the concrete cylinder in the axial direction of the cylinder. This maximum tensional stress was over 2.5 MPa in the air-entrained concrete cured in the relative humidity of 96%. The thermodynamic pumping effect at the end of the thawing phase in every cycle can increase the pore water amount remarkably if free water or moisture is available on the surface of the structure or in the environment vapor. The thermodynamic pumping effect seems to be remarkably greater and more dangerous in air-entrained concretes.     

Oxygen Fugacity Control in Nonflowing Atmospheres: I, Experimental Observations in CO/CO2 and O2/N2 Mixtures

The performance of a stabilized zirconia sensor and electrochemical oxygen pump combination in the isothermal control of oxygen fugacity in a nonflowing atmosphere was studied in a closed furnace system in the temperature range of 800° to 1100°C. Under certain conditions, large differences in oxygen pressure were found between sensors at the same constant temperature in close proximity to each other. This result reflected the existence of a stable steplike oxygen fugacity "front" in the furnace, separating regions which differed by several orders of magnitude in oxygen fugacity. This oxygen pressure profile in the furnace resulted from the steady-state transport of oxygen from oxygen leakage sources to the pump. The existence, magnitude, and position of the oxygen fugacity front were found to depend on the gas-phase composition, the relative locations of the leakage sources and the pump, the oxygen fugacity of the reference electrode, and the magnitude of the oxygen flux in the gas phase.     

循环流化床提升管T形弯头动态压力的小波分析

针对循环流化床提升管出口T形弯头,以FCC催化剂颗粒为物料,采用动态压力传感器,对T形弯头内的气固两相流的动态压力进行了实验测量,以此分析T形弯头内动态压力的特性。实验结果表明,由于在T形弯头盲管处颗粒折返造成的冲击,形成了一个压力脉动源。小波分析表明T形弯头处的压力脉动主频来自盲管内,而次频能量所占比例随着颗粒质量流率增加而加大。T形弯头内的动态压力的标准偏差与颗粒质量流率呈线性关系,可以用于表征循环流化床内的颗粒质量流率。