2-甲基-4-芳基噻唑的溴代反应研究

2-甲基-4芳基噻唑类化合物是重要的光电功能材料中间体,通过控制NBS溴代条件,选择性地得到了2-甲基-4芳基噻唑类在2位甲基和在5位碳上两种溴代产物并利用HNMR对产物结构进行了确定.最后对溴代机理及反应条件进行了分析.     

二卤海因参与的(取代苯基)-(吡啶-2-基)-甲酮类化合物的卤化反应

以(取代苯基)-(吡啶-2-基)-甲酮类化合物为原料，二溴海因和二氯海因为溴源和氯源，1,2-二氯乙烷为溶剂，通过醋酸钯催化的卤化反应，实现了该类化合物的邻位溴代和氯代，得到18种(卤代苯基)-(吡啶-2-基)-甲酮类化合物，并采用1HNMR、13CNMR对产物进行了结构鉴定。从底物普适性研究可知，对不同取代基的苯基-(吡啶-2-基)-甲酮类化合物进行邻位溴代或氯代，得到中等或良好的产率。研究发现，二溴海因的反应活性比二氯海因高。控制实验表明该反应为碳氢活化卤代反应，并提出了一种可能的反应机理。     

4-溴-2-(溴甲基)苯甲醛的合成研究

4-溴-2-(溴甲基)苯甲醛是合成1, 2-二氢酞嗪化合物的重要中间体。以4-溴-2-甲基苯腈为原料,通过溴代、还原得两步反应得到目标化合物4-溴-2-(溴甲基)苯甲醛。确定了溴代反应最佳条件:N-溴代丁二酰亚胺(24.0 mmol)、过氧苯甲酰(4.0 mmol),反应体系在CCl_4中回流反应8 h。还原反应最佳条件:二异丁基氢化铝(DIBAL-H)(12.0 mmol),反应溶剂二氯甲烷,室温反应3 h。两步反应总收率85.4%,产物及中间体结构通过~1H NMR、~(13)C NMR和电喷雾电离质谱(ESI-MS)进行了表征。     

达沙替尼的合成研究

以2-氯-6-甲基苯胺为起始原料,在吡啶的催化下,以99％的转化率得到酰化产物（E）-N-（2-氯-6-甲基苯基）-3-乙氧基丙烯酰胺（Ⅲ）;Ⅲ在以水为主的溶剂中与N-溴代丁二酰亚胺（NBS）、硫脲经“一锅法”连续反应得化合物2-氨基-N-（2-氯-6-甲基苯基）-5-噻唑甲酰胺（V）;V经纯化后与4,6-二氯-2-甲基嘧啶反应得化合物2-（6-氯-2-甲基嘧啶-4-氨基）-N-（2-氯-6-甲基苯基）-5-噻唑甲酰胺（Ⅵ）;Ⅵ与1-（2-羟乙基）哌嗪缩舍得达沙替尼（Ⅶ）,总收率为71％.该合成方法条件温和、反应步骤少、收率高.     

3,5-二甲基-4-溴碘苯和2,6-二甲基-4-溴碘苯的合成

二甲基对溴碘代苯是带有两种不同卤素基团的芳香族有机合成中间体。2,6-二甲基苯胺在过碳酸钠作用下,于45~50℃与碘反应1 h,得到2,6-二甲基-4-碘苯胺,收率42.5%。2,6-二甲基-4-碘苯胺在-5~0℃下进行重氮化,进一步与溴化亚铜发生Sandm eyer反应,得到3,5-二甲基-4-溴碘苯,收率31.5%。2,6-二甲基苯胺室温下与六亚甲基四胺溴络合物反应30 m in,得到2,6-二甲基-4-溴苯胺,收率62.0%。2,6-二甲基-4-溴苯胺在-5~0℃进行重氮化,与K I反应,得到2,6-二甲基-4-溴碘苯,收率33.1%。通过熔点、红外光谱和核磁共振氢谱对中间体2,6-二甲基-4-碘苯胺、2,6-二甲基-4-溴苯胺以及最终产物3,5-二甲基-4-溴碘苯和2,6-二甲基-4-溴碘苯进行了表征。     

1,4-二(溴甲基)-2-氟苯的合成工艺改进

以对二甲苯为原料,经硝化、还原、重氮化、溴代4步反应得到标题化合物。其中溴代反应中,1,4-二甲基-2-氟苯在偶氮二异丁腈(AIBN)引发下与N-溴代丁二酰亚胺(NBS)发生自由基反应。总收率达到30%,其结构经1HNMR和GC/MS确证。     

4-甲基-5-甲酰基噻唑的合成工艺研究

研究了头孢托仑匹酯关键中间体4-甲基-5-噻唑甲醛(1)的合成新工艺.以乙酰乙酸甲酯(2)为起始原料,首先进行α-溴代反应、与硫脲缩合反应,制得2-氨基-4-甲基-5-噻唑甲酸甲酯(3),收率高达96%;其次用廉价的次亚磷酸钠(1.5当量)替代次亚磷酸,进行氨基重氮化还原反应,制得4-甲基-5-噻唑甲酸甲酯(4),收率为75%;最后用硼氢化钾/氯化锂体系(1.5当量)在回流的无水乙醇中进行酯还原反应,所得粗产物不经分离提纯,直接用次氯酸钠(2.0当量)氧化得到目标化合物,收率为62%,反应总收率在44%以上.该过程条件温和,操作简便,后处理简单,具有工业化应用前景.     

高纯度2-(3-醛基-4-异丁氧基苯基)-4-甲基噻唑-5-甲酸乙酯的合成方法

<正>本发明提供了一种高纯度2-(3-醛基-4-异丁氧基苯基)-4-甲基噻唑-5-甲酸乙酯的合成方法,以对氰基苯酚、硫代乙酰胺为起始原料,经硫酰化反应得到4-羟基硫代苯甲酰胺(II),反应产物不分离直接进行噻唑化反应,分离得到2-(4-羟基苯基)-4-甲基-5-噻唑甲酸乙酯(III);将式(III)化合物经甲酰化反应得2-(3-甲醛基-4-羟基苯基)-4-甲     

α-溴-ω-（4-溴甲基苯氧基）烷烃的合成

通过对甲苯酚钠盐和过量α,ω-二溴代烷烃的亲核取代反应,合成得到α-溴-ω-(4-甲基苯氧基)烷烃,然后再与N-溴代丁二酰亚胺进行自由基取代反应,合成得到一系列的标题化合物,并通过元素分析、NMR、IR等方法对目标化合物的结构进行确定.     

6-溴甲基-3,4-二氢-2-甲基-4-氧代喹唑啉的合成

用对甲基苯胺与水合三氯乙醛、盐酸羟胺反应制得对甲基(N-肟基乙酰)苯胺,再与浓硫酸反应生成5-甲基靛红,后经碱性过氧化氢氧化,制得2-氨基-5-甲基苯甲酸。将2-氨基-5-甲基苯甲酸与硫代乙酰胺反应生成的3,4-二氢-2,6_二甲基4氧代喹唑啉,经N-溴代琥珀酰亚胺溴化得到标题化合物,其结构经IR,MS,^1HNMR和元素分析确证,5步反应总收率为23．1％。     

A Simulation Model for Heat Pump Dryer Plants for Fruits and Roots.

Dryer design requires food properties, drying rate and mass-heat transfer coefficients. These values change continuously during drying due to changes in food fractions, particularly the water fraction. The high energy demand and costs allied to inefficient devices, creates a great need for new processing equipment. Along these guide-lines, several heat pump drying research projects were established at the Norwegian University of Science and Technology. The heat pump dryer provides high quality final product as its drying conditions can be controlled. Its efficiency and non-polluting operation come from closed air-refrigerant circuits and from its ability to fully recover the latent heat of moist air as it exits the drying chamber. Most of the above features are quite the opposite of the conventional dryer characteristics. Several experiments were made on heat pump drying of fruits and roots at temperatures from -22.5 to 40°C to obtain data and correlations on thermophysical properties, specific enthalpy and rehydration. Also, tests were done on drying rate, moisture content, drying constant, effective mass diffusivity and heat and mass transfer equations. The next important phase is the development of a simulation model to predict the performance and characteristics of the heat pump dryer plant. The objectives of the present work are to develop and lo test a heat pump dryer simulation model. The simulation provides results on the characteristics of both plant and components which are integrated by heat and mass transfer equations. The program has menus with click-on icons, input and output pop-up dialogue boxes. The usual commands such as, file-open, file-save, edit-delete are available in this program simply called Hpdryer. The model contains moist air psychrometric. natural and conventional refrigerant property libraries. Ammonia is a time-tested, self-alarming and natural refrigerant. It has been used extensively in the past, and it has better thermodynamic and transport properties than halocarbons. Safety is easily attained by design and its restrictive standards have helped increase its use in several countries. There are 36 ammonia installations in Norway and in the United Kingdom, including a drying plant. Ammonia has zero Odp, zero Gwp and the recent R&D has led to viable small-sale heat pump plants. Ammonia and dichlarodifluoromethane refrigerants were used in the test cases simulated by Hpdryer madel.     

木质素/热塑性塑料复合材料界面增容的研究进展

将木质素作为一种有机颗粒填料添加到热塑性塑料中,可解决造纸黑液资源化利用、石油原料日渐紧张以及环境污染加剧等严峻问题。而木质素与热塑性塑料之间相容性直接影响木质素在塑料工业中的应用与发展。首先简要概述了木质素结构与性质和木质素/热塑性塑料复合材料的性能分析,然后系统地阐述国内外研究木质素/热塑性塑料复合材料界面增容方法及其原理;增容方法按添加相容剂、改性木质素和改性塑料进行归类,并对3种增容方法进行比较分析;接着综述了木质素复合材料中增容方法的交叉复合使用;最后对未来木质素/热塑性塑料复合材料界面增容的研究方向以及思路进行了展望。     

2,3,6-三甲基苯酚一步氧化制备2,3,5-三甲基-1,4-苯醌研究进展

2,3,6-三甲基苯酚一步氧化制备2,3,5-三甲基-1,4-苯醌相对于传统的磺化-氧化法具有产品收率高、过程简单、条件温和以及环境友好等特点。本文针对2,3,6-三甲基苯酚一步氧化制备2,3,5-三甲基-1,4-苯醌的均相催化氧化和非均相催化氧化工艺进行了综述,对两种工艺的发展过程及研究现状进行了评价及总结。详细讨论了不同方法和路线在催化活性、选择性以及产品分离和催化剂回收等方面的优缺点,简要分析并总结了2,3,6-三甲基苯酚一步氧化研究的发展规律和最新动态,展望了以非均相催化反应机制为重点的微观机理研究和以提高催化剂循环稳定性、降低制备成本为重点的工业化探索两个潜在的发展方向。     

Characterization of chlorophyll pigments present in canola seed,meal and oil

Chlorophyll pigments present in canola seed, meal and crude and degummed oils were analyzed by high-performance liquid chromatography (HPLC) with a fluorescence detector. Chlorophylls a and b, low levels of pheophytin a, and occasionally traces of pheophorbide and its methyl ester were present in canola seed. Meals and oils contained magnesium-deficient chlorophyll pigments such as pheophorbide a, methylpheophorbide a, pheophytins a and b, and pyropheophytins a and b but not chlorophyll a or b. The amounts of chlorophyll pigments were oil > seed >> meal. Both crude and degummed oils contained pheophytin a and pyropheophytin a as main components, but the ratio of pyropheophytin a to pheophytin a was markedly higher in degummed oils. No pheophorbides were detected in degummed oils. These results suggest that oil processing steps such as extraction and degumming affect the composition of chlorophyll pigments. Publication No. 678 Canadian Grain Commission.     

A Simulation Model for Heat Pump Dryer Plants for Fruits and Roots.

ABSTRACT

Dryer design requires food properties, drying rate and mass-heat transfer coefficients. These values change continuously during drying due to changes in food fractions, particularly the water fraction. The high energy demand and costs allied to inefficient devices, creates a great need for new processing equipment. Along these guide-lines, several heat pump drying research projects were established at the Norwegian University of Science and Technology. The heat pump dryer provides high quality final product as its drying conditions can be controlled. Its efficiency and non-polluting operation come from closed air-refrigerant circuits and from its ability to fully recover the latent heat of moist air as it exits the drying chamber. Most of the above features are quite the opposite of the conventional dryer characteristics. Several experiments were made on heat pump drying of fruits and roots at temperatures from -22.5 to 40°C to obtain data and correlations on thermophysical properties, specific enthalpy and rehydration. Also, tests were done on drying rate, moisture content, drying constant, effective mass diffusivity and heat and mass transfer equations. The next important phase is the development of a simulation model to predict the performance and characteristics of the heat pump dryer plant. The objectives of the present work are to develop and lo test a heat pump dryer simulation model. The simulation provides results on the characteristics of both plant and components which are integrated by heat and mass transfer equations. The program has menus with click-on icons, input and output pop-up dialogue boxes. The usual commands such as, file-open, file-save, edit-delete are available in this program simply called Hpdryer. The model contains moist air psychrometric. natural and conventional refrigerant property libraries. Ammonia is a time-tested, self-alarming and natural refrigerant. It has been used extensively in the past, and it has better thermodynamic and transport properties than halocarbons. Safety is easily attained by design and its restrictive standards have helped increase its use in several countries. There are 36 ammonia installations in Norway and in the United Kingdom, including a drying plant. Ammonia has zero Odp, zero Gwp and the recent R&D has led to viable small-sale heat pump plants. Ammonia and dichlarodifluoromethane refrigerants were used in the test cases simulated by Hpdryer madel.     

振动丝法测定常压和加压下液体的黏度和密度

介绍了自行研制的高温高压振动丝黏度密度仪的构造和测定原理,并以正戊烷作为实验流体对仪器的可靠性和准确性进行了测试.测定了环己烷在323.15～413.15 K温度范围内、正辛烷在313.15～393.15 K温度范围内、苯在303.15～445.15 K温度范围内压力分别为常压和6.10 MPa、正庚烷和异辛烷在298.15～403.15 K温度范围内压力分别为常压和5.10 MPa下的黏度与密度,并分别对不同压力下的黏度、密度数据进行了关联.     

Biosorption: critical review of scientific rationale,environmental importance and significance for pollution treatment

Biosorption may be simply defined as the removal of substances from solution by biological material. Such substances can be organic and inorganic, and in gaseous, soluble or insoluble forms. Biosorption is a physico‐chemical process and includes such mechanisms as absorption, adsorption, ion exchange, surface complexation and precipitation. Biosorption is a property of both living and dead organisms (and their components) and has been heralded as a promising biotechnology for pollutant removal from solution, and/or pollutant recovery, for a number of years, because of its efficiency, simplicity, analogous operation to conventional ion exchange technology, and availability of biomass. Most biosorption studies have carried out on microbial systems, chiefly bacteria, microalgae and fungi, and with toxic metals and radionuclides, including actinides like uranium and thorium. However, practically all biological material has an affinity for metal species and a considerable amount of other research exists with macroalgae (seaweeds) as well as plant and animal biomass, waste organic sludges, and many other wastes or derived bio‐products. While most biosorption research concerns metals and related substances, including radionuclides, the term is now applied to particulates and all manner of organic substances as well. However, despite continuing dramatic increases in published research on biosorption, there has been little or no exploitation in an industrial context. This article critically reviews aspects of biosorption research regarding the benefits, disadvantages, and future potential of biosorption as an industrial process, the rationale, scope and scientific value of biosorption research, and the significance of biosorption in other waste treatment processes and in the environment. Copyright © 2008 Society of Chemical Industry     

The Emerging Roles of Chromogranins and Derived Polypeptides in Atherosclerosis,Diabetes, and Coronary Heart Disease

Chromogranin A (CgA), B (CgB), and C (CgC), the family members of the granin glycoproteins, are associated with diabetes. These proteins are abundantly expressed in neurons, endocrine, and neuroendocrine cells. They are also present in other areas of the body. Patients with diabetic retinopathy have higher levels of CgA, CgB, and CgC in the vitreous humor. In addition, type 1 diabetic patients have high CgA and low CgB levels in the circulating blood. Plasma CgA levels are increased in patients with hypertension, coronary heart disease, and heart failure. CgA is the precursor to several functional peptides, including catestatin, vasostatin-1, vasostatin-2, pancreastatin, chromofungin, and many others. Catestatin, vasostain-1, and vasostatin-2 suppress the expression of vascular cell adhesion molecule-1 and intercellular adhesion molecule-1 in human vascular endothelial cells. Catestatin and vasostatin-1 suppress oxidized low-density lipoprotein-induced foam cell formation in human macrophages. Catestatin and vasostatin-2, but not vasostatin-1, suppress the proliferation and these three peptides suppress the migration in human vascular smooth muscles. Chronic infusion of catestatin, vasostatin-1, or vasostatin-2 suppresses the development of atherosclerosis of the aorta in apolipoprotein E-deficient mice. Catestatin, vasostatin-1, vasostatin-2, and chromofungin protect ischemia/reperfusion-induced myocardial dysfunction in rats. Since pancreastatin inhibits insulin secretion from pancreatic β-cells, and regulates glucose metabolism in liver and adipose tissues, pancreastatin inhibitor peptide-8 (PSTi8) improves insulin resistance and glucose homeostasis. Catestatin stimulates therapeutic angiogenesis in the mouse hind limb ischemia model. Gene therapy with secretoneurin, a CgC-derived peptide, stimulates postischemic neovascularization in apolipoprotein E-deficient mice and streptozotocin-induced diabetic mice, and improves diabetic neuropathy in db/db mice. Therefore, CgA is a biomarker for atherosclerosis, diabetes, hypertension, and coronary heart disease. CgA- and CgC--derived polypeptides provide the therapeutic target for atherosclerosis and ischemia-induced tissue damages. PSTi8 is useful in the treatment of diabetes.     

民用工业中复合材料桁架的应用和发展

本文叙述了复合材料桁架的构造、分类和计算方法,突出了复合材料桁架的优越性能和在民用工业中的应用前景;在分析大量文献资料的基础上阐述复合材料桁架杆件的多种加工工艺,并比较不同截面形式对杆件性能的影响;探讨复合材料杆件的破坏机理和分析方法,介绍节点的类型和各自的特点,提出节点及连接部位存在的关键问题;根据国内外复合材料桁架的研究和应用现状,阐述了复合材料桁架的性能和不同的设计方法,总结归纳影响复合材料桁架性能的关键因素和设计中存在的一些问题,并提出改进杆件设计、节点设计和优化复合材料桁架的建议。     

Social behavior and chemical communication in reindeer (Rangifer t. tarandus L.)

The social interactions of captive reindeer were observed for one year. The seasonal changes of agonistic behavior, the social rank order, social affinity during rest, social sniffing and licking, solitary sniffing and licking, hindleg-head contact, and other motor patterns involving head and antlers are described. Social sniffing and licking correlated more with sex than with social rank. Olfactory responses during encounters and tracking were investigated experimentally. Chemical communication is particularly important in sexual and maternal behavior and during encounters.