3.0 properties of phosgene
《蜂胶》国际标准的英文
《蜂胶》国际标准的英文International Standard for PropolisPropolis is a natural substance that has been used for centuries due to its wide range of beneficial properties. It is derived from the resinous substance collected by bees from various plants, mixed with beeswax, enzymes, and pollen. Propolis has been widely recognized for its antimicrobial, antioxidant, and anti-inflammatory effects, making it a valuable ingredient in food, cosmetics, and medicinal products. As the global demand for propolis grows, the establishment of an international standard for propolis becomes crucialto ensure its quality and safety. In this article, we will explore the importance of an international standard for propolis and its key components.I. Definition and ScopeThe international standard for propolis aims to provide a concise and comprehensive definition of propolis and its key components. It covers the types of propolis commonly found worldwide, including the resinous content, beeswax ratio, and pollen composition. The standard outlines the acceptable quality parameters for propolis, such as its color, odor, and purity. Additionally, it defines the specific tests and analytical methods to determine the propolis content accurately.II. Chemical Composition AnalysisTo establish an international standard for propolis, a thorough analysis of its chemical composition is essential. The standard should include detailed instructions on the identification and quantification of the major classes of compounds found in propolis, such as polyphenols, flavonoids, andterpenoids. Gas chromatography-mass spectrometry (GC-MS) and high-performance liquid chromatography (HPLC) are some of the advanced analytical techniques used to determine the chemical profile of propolis accurately.III. Quality Control and Safety AssessmentEnsuring the quality and safety of propolis is of utmost importance to protect consumers and promote international trade. The international standard should incorporate guidelines for quality control, including the establishment of maximum limits for contaminants, such as heavy metals, pesticides, and microbial impurities. Moreover, the standard should outline the safety assessment procedures, including acute and chronic toxicity tests, to determine the harmful effects of propolis consumption.IV. Labeling and Packaging RequirementsIn order to facilitate international trade and enhance consumer awareness, the international standard for propolis should also cover labeling and packaging requirements. This includes clear and accurate labeling of the propolis content, origin, and batch number. Additionally, the standard should specify the recommended storage conditions and shelf life to maintain the quality and efficacy of propolis products.V. International Harmonization and RecognitionTo ensure global acceptance and harmonization of the international standard for propolis, collaborations and mutual recognition agreements are essential. International organizations and regulatory bodies should work together to establish a unified standard that can be adopted by differentcountries. This will streamline the import-export procedures and facilitate the trade of propolis products while maintaining consistent quality and safety standards worldwide.ConclusionThe establishment of an international standard for propolis will play a crucial role in promoting the quality, safety, and trade of propolis products globally. With a comprehensive definition, accurate chemical composition analysis, robust quality control measures, and harmonization efforts, the international standard will serve as a benchmark for propolis producers, manufacturers, and consumers. By adhering to the standard, the industry can ensure the availability of high-quality propolis products that deliver the expected therapeutic benefits while building trust among consumers worldwide.。
非光气法聚碳酸酯与光气法聚碳酸酯性能差异研究
ｄｉｓｔｒｉｂｕｔｉｏｎ ｏｆ ｐｈｏｓｇｅｎｅ ＰＣ ｉｓ ｗｉｄｅ ａｎｄ ｉｔ ｈａｓ ｍｏｒｅ ｈｉｇｈ ｍｏｌｅｃｕｌａｒ ｗｅｉｇｈｔ ｍｏｌｅｃｕｌｅｓ. Ｔｈｅ ｎｏｔｃｈｅｄ ｉｍｐａｃｔ ｓｔｒｅｎｇｔｈ ｏｆ ｐｈｏｓｇｅｎｅ ＰＣ ｉｓ
ｂｅｔｔｅｒ ｔｈａｎ ｎｏｎ￣ｐｈｏｓｇｅｎｅ ＰＣ. Ｉｎ ａｄｄｉｔｉｏｎꎬ ｉｔ ｉｓ ｆｏｕｎｄ ｔｈａｔ ｎｏｎ￣ｐｈｏｓｇｅｎｅ ＰＣ ｉｓ ｅａｓｙ ｔｏ ｂｅ ｄｅｃｏｍｐｏｓｅｄ ｗｉｔｈ ｗｏｒｓｅ ｔｈｅｒｍａｌ ｓｔａｂｉｌｉｔｙ ｂｙ ｔｈｅ
Ｓｔｕｄｙ ｏｎ ｔｈｅ Ｐｅｒｆｏｒｍａｎｃｅ Ｄｉｆｆｅｒｅｎｃｅ ｂｅｔｗｅｅｎ Ｎｏｎ￣Ｐｈｏｓｇｅｎｅ
Ｐｏｌｙｃａｒｂｏｎａｔｅ ａｎｄ Ｐｈｏｓｇｅｎｅ Ｐｏｌｙｃａｒｂｏｎａｔｅ
ＦＵ Ｈｕｉ￣ｊｕａｎꎬ ＣＡＯ Ｈｕａｎ
( Ｒｅｓｅａｒｃｈ Ｉｎｓｔｉｔｕｔｅ ｏｆ ＳＩＮＯＰＥＣ Ｔｉａｎｊｉｎ Ｂｒａｎｃｈꎬ Ｔｉａｎｊｉｎ ３００２７１ꎬ Ｃｈｉｎａ)
Ａｂｓｔｒａｃｔ: Ｔｈｅ ｍｉｃｒｏｓｔｒｕｃｔｕｒｅ ａｎｄ ｍｅｃｈａｎｉｃａｌ ｐｒｏｐｅｒｔｉｅｓ ｏｆ ｎｏｎ￣ｐｈｏｓｇｅｎｅ ｐｏｌｙｃａｒｂｏｎａｔｅ ( ＰＣ) ａｎｄ ｐｈｏｓｇｅｎｅ ｐｏｌｙｃａｒｂｏｎａｔｅ ( ＰＣ)
ｗｅｒｅ ａｎａｌｙｚｅｄ. Ｔｈｅ ｄｉｆｆｅｒｅｎｃｅｓ ｉｎ ｍａｃｒｏｓｃｏｐｉｃ ｐｒｏｐｅｒｔｉｅｓ ｗｅｒｅ ｅｘｐｌａｉｎｅｄ ｆｒｏｍ ｔｈｅ ｄｉｆｆｅｒｅｎｔ ｍｉｃｒｏｓｔｒｕｃｔｕｒｅｓ. Ｔｈｅ ｄｉｆｆｅｒｅｎｃｅ ｏｆ ｔｗｏ ｋｉｎｄｓ
polycarbonate?engineeringplastic?phosgenation?nonphosgenation聚碳酸酯pc是一种综合性能优良的热塑性工程塑料?被广泛应用于电子电器家电建筑建材汽车制造医疗器械航空航天光学安全防护等领域1?目前?pc在五大通用工程塑料中增长速度最快?同时?随着改性技术的发展?改性pc在特殊外形设计超薄电子产品开发机器人新能源汽车3d打印等领域表现出优于传统材料的优势2?2018年国内聚碳酸酯消费量184万吨?2019年预测国内消费量192万吨?到2021年国内消费量预计207万吨?2019年国内产能150万吨a?实际产量预计有80100万吨a?到2021年预计国内新增产能174????5万吨a?国内总产能将达到324????5万吨a?20192021年?国内pc近200万吨a产能集中释放?市场竞争加剧?pc装置按生产工艺可分为光气法和非光气法?其中?光气法主要是界面缩聚光气法?非光气法又分为熔融酯交换法和非光气熔融酯交换法34?界面缩聚光气法最早实现工业化?工艺成熟?但因环境污染问题产能扩张受到了严格限制5?非光气熔融酯交换法由于不使用剧毒光气和二氯甲烷等有机溶剂?绿色环保?当前新建装置大多采用该种工艺6?sabic是非光气熔融酯交换法pc的龙头企业?pc生产技术先进?同时pc改性技术处于领先地位?pc及其改性产品占据高端市场份额7?目前?国内改性企业大都生产光气法pc改性产品?非光气法pc改性高端产品还处于探索阶段?预计随着非光气法pc产能的释放?非光气法pc改性技术会迎来广阔的发展空间?目前?国内虽然很多研究机构在进行pc改性研究?但鲜有对光气法pc和非光气法pc的系统对比?本文选取了同类型的典型非光气pc和光气法pc进行了微观分析和力学性能分析?从微观结构的不同解释了宏观性能的区别?从而从根本找出两种????62????作者简介
AirGas 压缩气体安全：理解气体类型与危险说明书
COMPRESSED GAS SAFETY: Understanding Gas Types & HazardsPART 1 OF THEAIRGAS EBOOK SERIESTable of Contents1 What you need to know before getting started2 Defining compressed gas3 Understanding hazard classifications and gas types4 Inert5 Flammable6 Oxidizer7 Pyrophoric8 Cryogenic9 Corrosive10 Asphyxiant11 Toxic or Poison12 Conclusion: Understanding gas types and hazards Please note:The information in this guide is general information and should not be used as specific informationfor a particular gas, or in lieu of an SDS for any specific gas product. Emergency response activities must only be undertaken by certified hazmat technicians, in accordance with OSHA 29 CFR §1910.120(q). Further, this information is not a substitutefor training nor is it to be used as a replacement reference for Federal and State laws and regulations. It simply presents brief highlights of someof the more common compressed gas categories, and associated compressed gas handling, storing and transporting procedures that are industry standards.!What you need to know before getting started While some gases have more dangerous properties than others, all compressed gases are considered hazardous materials. As such, they require specific training on federal and state regulations covering the safe storage, use and transportation before you can even touch a cylinder. Therefore, anyone handling compressed gas should be familiar with the potential hazards before using the gas by:•Educating personnel who handle compressed gases through discussion with a supervisor orknowledgeable coworker before beginning a new task. Use available resources and understand your local and State regulations•Outlining the actions necessary to complete any given job•Addressing potential emergencies and corresponding measures necessary to safely avoidsuch emergencies•Considering scenarios that could result in gas leaks or other emergencies in order to be fully prepared to react appropriatelyDefining compressed gasBefore understanding the properties and hazards of various gas types, it’s important to understand what a compressed gas is.Compressed gas is defined as any non-flammable material or mixture contained under pressure exceeding41 psia (3 bar) at 70°F (21°C), or any flammable or poisonous material that is a gas at 70°F (21°C), stored at a pressure of 14.7 psia (1 bar) or greater. Most compressed gases will not exceed 2,000-2,640 psig (138-182 bar), though some go up to 6,000 psig (414 bar).Liquefied compressed gas is any chemical or material that, under the charged pressure, is partially liquid at a temperature of 70°F (21°C).Non-liquefied compressed gas is any chemical or material (other than gas in solution) that, under the charged pressure, is entirely gaseous at a temperature of 70°F (21°C).Compressed gas in solution is a non-liquefied compressed gas that is dissolved in a solvent.Understanding hazard classifications and gas typesMany gases have flammable, toxic, corrosive, oxidizing, pyrophoric and other hazardous properties that can cause property damage, severe injuries or even death if proper safety precautions are not followed. In addition to the gas chemical hazards, the amount of energy resulting from the compression of the gas makes a compressed gas cylinder a potential rocket.The Global Harmonized System (GHS) has created classification criteria that determine the nature and relative hazard severity of a chemical substance or mixture. These GHS classification categories (listed here) enable workers to easily identify the type of gas they’re working with and its associated hazards.This way, anyone handling a compressed gas can quickly determine whether it’s toxic, explosive or a combination of properties, to ensure the safety of themselves and others in the workplace.GHS01 | ExplosivesGHS04 | Compressed GasesGHS07 | IrritantGHS03 | OxidizersGHS06 | Acute ToxicityGHS09 | EnvironmentGHS02 | FlammablesGHS05 | CorrosivesGHS08 | Health HazardInertInert gases do not react with other materials at ordinary temperatures and pressure. They are also colorless, odorless, non-toxic and non-flammable.While it might sound like inert gases are harmless, they can become life-threatening in a confined space and in large quantities. That’s because they displace the oxygen in the air required to sustain life, leading to asphyxiation over long periods. And due to their colorless, odorless nature, they can be difficult to detect until you begin experiencing the effects of oxygen deprivation.To minimize the danger of asphyxiation and ensure the safety of everyone, always use adequate ventilation and monitor the oxygen levels in confined places.Examples of inert gases include argon, helium, krypton and neon .HeHeGas DetectorPyrophoricPyrophoric gases are commonly used in the semiconductor industry and they are extremely dangerous to handle as they do not require a source of ignition to explode or erupt in flames.Pyrophoric gases are highly volatile and will ignite spontaneously in air at or below 130°F (54°C), though specific gases may not ignitein all circumstances or may explosively decompose. Under certain conditions, some pyrophoric gases can undergo polymerization, releasing large amounts of energy in the form of heat.Examples of pyrophoric gases include arsine, diborane, phosphineand silane.CryogenicCryogenic gases have a boiling point of -130°F (-90°C) at atmosphericpressure. While they can be non-flammable, flammable or oxidizing,they’re extremely cold and can easily cause intense burns if mishandled.At sub-freezing temperatures, system components can become brittleand crack, leading to damage and dangerous conditions.Cryogenic liquids can also build immense pressure, so it’s critical tonever block a filled line. Otherwise, the tremendous pressure could burstthe tube. It’s also why your system should be designed with safety reliefvalves and a vent line, depending on the gas.ArWhen handling cryogenic materials, always wear gauntlet gloves anda cryogenic apron to protect the body and exposed skin. To preventliquids from getting trapped inside your shoes, wear long pants thatcover your footwear. You should also wear safety glasses and a faceshield as cryogenic liquids tend to bounce when they are spilled.Examples of cryogenic gases include argon, helium, hydrogen, nitrogenand oxygen.CorrosiveCorrosive gases are those that corrode material or organic tissue on contact or in the presence of water. They are highly reactive and can also be toxic, flammable and/or an oxidizing agent. Most are hazardous in low concentrations over extended periods of time, so it’s essential that the equipment used for handling corrosive gases be constructed of proper materials. Where there is a possibility of water or other inorganic materials getting sucked back into the cylinder, use check valves and traps in your system.Due to the probability of irritation and damage to the lungs, mucous membranes and eye tissues from contact, you should rigidly observe the gas threshold limit values. Minimize exposure to corrosive materials by utilizing the proper protective clothing and equipment. Ensure that a full-body shower and eyewash station are available in caseof emergencies.Examples of corrosive gases include ammonia, hydrogen chloride, nitrogen dioxide and sulfur dioxide.NH3AsphyxiantAsphyxiants are gases that are either minimally or entirely non-toxic butcan dilute the oxygen in the surrounding air when released. This can leadto death by asphyxiation if inhaled for a long enough period of time.In large enough concentrations, toxic gases can also cause asphyxiationand lead to death by other mechanisms. This can include interactionswith the respiratory system where oxygen is outcompeted (such ascarbon monoxide poisoning) or direct damage caused by the gas (suchas phosgene).COBecause asphyxiant gases are relatively inert, their presence mightnot be recognized — even in large amounts — until you experience theeffects of low oxygen levels.Examples of asphyxiant gases include argon, carbon dioxide, carbonmonoxide, helium, methane, nitrogen and propane.Conclusion: Understanding gas types and hazardsUnderstanding the types of compressed gases and their individual safety requirements is vital to ensuring workplace safety and protecting yourself and other employees. Knowing how to safely store, handle and transport these gases can mean the difference between a successful project or ending up in the emergency room.That’s why it’s critical to complete training on any applicable Federal and State regulations along withreading and understanding the Safety Data Sheet (SDS) when using hazardous materials like compressed gases. More resources for your team are listed below.•Information on specific compressed gases is contained in SDS publications, which provide safety, technical and regulatory information on gas products. These are available from your point of product purchase or can be downloaded from /sds-search . •The Compressed Gas Association (CGA) offers publications on handling compressed gases such as pamphlet P-1, “Safe Handling of Compressed Gases in Containers,” and they also sell videos on compressed gas subject matter. •Additional information on compressed gases can be found at .At Airgas, we want you and your team to be safe — please don’t hesitate to contact your Airgas representative for more information on general compressed gas safety or specific products.To learn more about compressed gas safety, please continue reading all three parts of our ebook series!PART 1:Compressed Gas Basics PART 2:Storage & Handling PART 3:UsageCONTACT US855.625.5285|***************|MCM-028.1 | © 2022 Airgas, Inc.The information in this guide is general information and should not be used as specific information for a particular gas, or in lieu of an SDS for any specific gas product. Emergency response activities must only be undertaken by certified hazmat technicians, in accordance with OSHA 29 CFR §1910.120(q). Further, this information is not a substitute for training nor is it to be used as a replacement reference for Federal and State laws and regulations. It simply presents brief highlights of some of the more common compressed gas categories, and associated compressed gas handling, storing and transporting procedures that are industry standards. In the event of an emergency, please dial 911.。
奥托昆普超级奥氏体不锈钢资料
1.4404 316L
0.02 –
17 10 2.1 –
1.4439 S31726
0.02 0.14 18 13 4.1 –
1.4539 N08904
0.01 –
20 25 4.3 1.5 Cu
1.4547 S31254
0.01 0.20 20 18 6.1 Cu
1.4529 N08926/N08367 0.01 0.20 20 25 6.5 Cu
Characteristic properties • Very good resistance to uniform corrosion • Good to exceptionally good resistance to pitting and
crevice corrosion • Very good resistance to various types of stress
Chemical composition
Table 1
Outokumpu steel name
International steel No
EN ASTM
Chemical composition, % typical values
C
N Cr Ni Mo Others
4404 4439 904L 254 SMO® 4529 4565 654 SMO®
Mechanical properties at 20˚C
Mechanical properties The strength and elongation of 904L are similar to those for conventional austenitic stainless steels. The addition of nitrogen in 254 SMO®, 4529, 4565 and 654 SMO® gives higher proof strength and tensile strength, see tables 2 and 3. Despite the greater strength of these steels, the possibilities for cold as well as hot forming are very good.
光气
3.0 Properties of PhosgeneTable of Contents3.1 Introduction3.2 Names3.3 Physical Properties3.4 Reactivity, Instability and Combustion Properties3.5 Commercial Chemistry3.6 Uses3.0 Properties of Phosgene3.1 IntroductionThe Phosgene Molecule:ClC = OClPhos gene (fasjen) n. [[so named (1812) by Sir Humphry DAVY< Gr phos,light+ -gene, born -GEN]] a colorless, volatile, highly poisonous liquid,COCl2, prepared by the reaction of carbon monoxide with chlorine in thepresence of activated charcoal or, originally, in sunlight; carbonyl chloride:used as a poison gas, in organic synthesis, in making dyes, etc.13.2 NamesChemical Name - PhosgeneChemical Abstract Registry Number - 0000 75-44-5Other Names:CARBON DICHLORIDE OXIDECARBONE (OXYCHLORURE DE) [FRENCH]CARBONIC DICHLORIDECARBONIO (OSSICLORURCI DI) [ITALIAN]CARBON OXYCHLORIDECARBONYLCHLORID [GERMAN]CARBONYL CHLORIDECARBONYL DICHLORIDECGCHLOROFORMYL CHLORIDEFOSGEEN (DUTCH)FOSGEN (POLISH)FOSGENE (ITALIAN)FOSGENO (SPANISH)HSDB 796KOOLSTOFOXYCHLORIDE (DUTCH)NCI-C60219PHOSGEN (GERMAN)PHOSGENERCRA WASTE NUMBER P095Formula:COCl2CCl2O3.3 PhysicalPropertiesGrade and Strength - Commercial 100%Properties & CharacteristicsColor and Physical State - At room temperature and pressure, phosgeneis a colorless, non-flammable, highly toxic gas. At sufficiently lowertemperatures or higher pressures or both, it is a highly toxic colorlessliquid.Note: Phosgene, in the presence of high humidity, water, fog or ammonia,may produce a white cloud.Property Value English Units Value Metric UnitsMolecular Weight 98.9158 lbm/lbmol 98.9158 g/mol Critical Temperature 359.33 F 181.85 C Critical Pressure 822.97462 psia 5.67E+07 dyne/cm² Critical Volume 3.04351 ft³/lbmol 190 cm³/mol Critical CompressibilityFactor0.285 0.285 Melting Point -198.004 F -127.78 CProperty Value English Units Value Metric UnitsTriple Point Temperature -198.004 F -127.78 CTriple Point Pressure 0.0001335 psia 9.20651 dyne/cm²Normal Boiling Point 45.608 F 7.56 CLiquid Molar Volume 1.12992 ft³/lbmol 70.5389 cm³/molIdeal Gas Heat of Formation -9.42E+04 BTU/lbmol -2.19E+12 erg/molIdeal Gas Gibbs ofFormation-8.81E+04 BTU/lbmol -2.05E+12 erg/molIdeal Gas Absolute Entropy 67.81556 BTU/lbmol·R 2.84E+09 erg/mol·KStandard Absolute Entropy 67.81556 BTU/lbmol·R 2.84E+09 erg/mol·KStandard Heat of Formation -9.42E+04 BTU/lbmol -2.19E+12 erg/molStandard Gibbs of Formation -8.81E+04 BTU/lbmol -2.05E+12 erg/molEnthalpy of Fusion at M.P. 2468.717 BTU/lbmol 5.74E+10 erg/molHeat of Combustion -7.51E+04 BTU/lbmol -1.75E+12 erg/molAcentric Factor 0.201309 0.201309Radius of Gyration 9.44E-10 ft 2.88E-08 cmSolubility Parameter 92.45383 (BTU/ft³)^½ 5.64E+04 (erg/cm³)^½Dipole Moment 1.17E-18 esu-cm 1.16919 Debye (D)Van der Waals Volume 0.5590444 ft³/lbmol 34.9 cm³/molVan der Waals Area 2.54E+09 ft²/lbmol 5.20E+09 cm²/molRefractive Index 1.35609 1.35609Flash Point Unknown R Unknown CUpper Flammability Limit Unknown vol% in air Unknown vol% in airLower Flammability Limit Unknown vol% in air Unknown vol% in airUpper FlammabilityTemperatureUnknown R Unknown CLower FlammabilityTemperatureUnknown R Unknown C Auto-ignition Temperature Unknown R Unknown COdor Threshold - 0. 12-5.7 ppm2. (Threshold varies with individuals and ishigher after prolonged exposure).Odor - Mildly sweet, not an unpleasant odor of musty hay in lowconcentrations, becoming more pungent in higher concentrations.Permissible Exposure Limit3 Threshold Limit Value4(by volume in air) - 0.1ppm.3.4 Reactivity, Instability and Combustion PropertiesPhosgene is a stable compound at normal ambient temperatures (21o C or70o F). At temperatures above 250o C (482o F), phosgene decomposes toform mixtures of carbon monoxide (CO), chlorine (CI2), carbon dioxide(CO2) and carbon tetrachloride (CCI4).Phosgene reacts slowly with water to form carbon dioxide and hydrochloric acid. Phosgene reacts readily with caustic solution and even more readily with ammonia and ammonia water.When fighting fires, one can minimize the reactivity hazards through precautionary measures such as those described in Section 5.Reactivity hazards exist when attempts are made to neutralize liquid spills because the heat of neutralization increases the rate of vaporization of liquid phosgene. Various techniques for minimizing the rate of vaporization from a liquid spill are listed in Section 6.1.4.Hazardous chemical reactions involving phosgene include the following: t-Butyl azidoformate - In the formation of tert-butyl-azidoformate (also known as tert-butyloxycarbonyl azide) by the addition of phosgene to alcohols followed by the addition of sodium nitride or hydrazoic acid in the presence of pyridine, reaction of phosgene with the azide can cause the formation of explosive carbazide. This reaction can be prevented by completely removing excess phosgene and passing nitrogen into the solution prior to addition of the azide.Aluminum - Powdered aluminum may burn in the vapor of phosgene.Alcohols - Phosgene may react with all alcohols; two examples follow: 2,4-Hexadiyne-1,6-diol - The reaction between 2,4-hexadiyne-1,6-diol and phosgene produces 2,4-hexadiyne-1,6-bischloroformate, which is a shock-sensitive compound.Isopropyl Alcohol - The reaction between isopropyl alcohol andphosgene generally forms isopropyl chloroformate and hydrogen chloride. At temperatures slightly above ambient isopropyl, chloroformate can decompose explosively in the presence of ironsalts.Secondary Amines - Phosgene may react with secondary amines to form hazardous products.Potassium - A mixture of potassium and phosgene may explode when subjected to shock.Sodium - Vapors of sodium and phosgene may react with luminescence at about 260o C.Chemistry3.5 CommercialPhosgene, COCl2, the acid chloride of carbonic acid, first was made by theaction of light on a mixture of carbon monoxide and chlorine (Gr. phoslight, genes born)1. In the current process, the mixed gasses are exposedto carbon catalyst. The reaction is exothermic, producing heat that mustbe removed from the reactor.The formula for the reaction to produce phosgene is:2ActivatedHeatCO + Cl22 +Carbon Monoxide Chlorine PhosgeneHydrogen and methane impurities in the carbon monoxide feed gas reactwith chlorine to produce hydrogen chloride and carbon tetrachloriderespectively. The formulas for these two impurity reactions are:Heat+H2 + Cl2HClCH4 + 4Cl24+ 4 HCl + HeatHydrogen and methane react with chlorine without catalyst, therefore thereaction can take place in the piping prior to the reactors. Normally, theseimpurities are at very low concentrations and the impurities formed are notsignificant. If a high concentration of either impurity exists, these reactionscan generate enough heat to melt the pipe. Since chlorine is an oxidizer,and methane, hydrogen and carbon monoxide are fuels, a fire can occurin the pipeline without oxygen. At temperatures above 250o F, chlorinecould start reacting with steel, weakening the piping and vessels. At483o F, chlorine could ignite iron and produce a fire. Detection of theseimpurity-generated reactions can be noticed by a rapid rise in thetemperature of the feed gas after the carbon monoxide and chlorinemixing point. The use of high mixing temperature automatic shut downcan help eliminate this type of failure.Carbon tetrachloride and carbon dioxide can also be formed at hightemperature by the reaction of two phosgene molecules. In the center ofthe reaction tubes temperatures are sufficiently hot to cause a smallamount of this impurity reaction. The formula for this reaction is:2 COCl+ CCI4 + CO23.6 UsesPhosgene is a widely used chemical intermediate, primarily manufacturedfor the synthesis of isocyanate-based polymers, carbonic acid esters andacid chlorides. It is also used in the manufacture of dyestuffs, someinsecticides and pharmaceuticals and in metallurgy(3,4,5). Phosgene consumption is summarized below:Toluene diisocyanate, 45 percent; MDI and polymeric isocyanates, 38 percent; polycarbonate resins, 12 percent; miscellaneous, including specialty isocyanates, chloroformates and agricultural chemicals, 5 percent6.Other uses in the miscellaneous category include certain dye intermediates and preparation of ethyl carbonate, a useful solvent.TDI Reaction:The overall reaction of toluene diamine with phosgene to form toluene diisocyanate (TDI) is shown below:CH3-C6H3(NH2)2+ 2 COCl2 ----- > CH3-C6H3(NCO)2 + 4 HCIToluene diamine Phosgene TDI HCIMDI Reaction: The overall reaction of Diaminodiphenyl methane with phosgene to form Methyldiphenyl diisocyanate (MDl) is shown below:2(C6H4)-CH2-2(NH2) + 2 COCl2 ----- > 2(C6H4)-CH2-2(NCO) + 4 HCI Diaminodiphenyl methane Phosgene MDI HClPolycarbonate Reaction:The reaction of Bisphenol-A with phosgene gives the very hard and strong polycarbonate plastics that can be molded and extruded.x(HO-C6H4-C(CH3)2-C6H4-OH) + x(COCl2) - > 2x HCI + [-OCO-O-C6H4-C(CH3)2-C6H4-]x Bisphenol-A Phosgene HCl PolycarbonateAlcohol Reaction: When phosgene reacts with alcohols, the alkyl chloroformate is formed first and further reaction gives the alkyl carbonate.COCl2 + C2H5OH --- > ClCOOC2H5 + HCIPhosgene Ethanol Ethyl chloroformateCICOOC2H5 + C2H5OH--- > OC(OC2H5)2+ HClEthyl carbonate EthanolCitations1. Excerpted from Compton's Interactive Encyclopedia, 1995Compton's NewMedia, Inc.2. Textbook of Organic Chemistry, C.R. Noller, W.B. SaundersCompany, 1966.3. U.S. Environmental Protection Agency. Health AssessmentDocument for Phosgene (External Review Draft).EPA/600/8-86/022A. Environmental Criteria and AssessmentOffice, Office of Health and Environmental Assessment, Office ofResearch and Development, Research Triangle Park, NC. 1986.4. M. Sittig. Handbook of Toxic and Hazardous Chemicals andCarcinogens. 2nd ed. Noyes Publications, Park Ridge, NJ. 1985.5. Information provided by Great Lakes Company.6. ChemExpo .Additional ResourcesPhosgene. Kirk-Othmer Encyclopedia of Chemical Technology. Third Edition. Volume 12. John Wiley and Sons, 1978.Davis, D. S., G. B. DeWolf, S. R. Penrod and J. D. Quass. Prevention Reference Manual: Chemical Specific, Vol. 14: Control of Accidental Releases of Phosgene, 1989.Phosgene. Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A 19, pp. 411 - 42.Section Title Page I. Properties 411 1.1. Physical Properties 4111.2. Chemical Properties 412 1.2. I. Reactions with OrganicCompounds 412 1.2.2. Reactions with Inorganic Compounds 4132. Production 4133. Storage and Transportation 4144. Qualityand Analysis 414 5. Waste-Gas Treatment and Monitoring 415 6.Safety Precautions 415 7. Uses 4l6 8. Economic Aspects 417 9.Toxicology and Occupational Health 417 10. References 419. Isocyanates, Organic. Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A 14, pp. 611 – 62.Section Title Page I. Physical Properties 611 2. ChemicalProperties 611 3. Production 616 3.I .Phosgenation of FreeAmines 617 3.2. Other Phosgenation Procedures 618 3.2. I.Phosgenation of Amine Hydrochlorides 618 3.2.2. Phosgenation ofCarbarnate Salts 618 3.2.3. Phosgenation of Ureas 619 3.3.Non-Phosgene Processes.。
黄酮类酚酸类
Chinese Journal of Natural Medicines 2010, 8(3): 0202 0207doi: 10.3724/SP.J.1009.2010.00202ChineseJournal ofNaturalMedicinesAnalysis of Flavonoids and Phenolic Acids in Iristectorum by HPLC-DAD-ESI-MS nSHU Pan 1,2, HONG Jun-Li 1,2, WU Gang 1,2, YU Bo-Yang3, QIN Min-Jian 1,2*1Department of Resources Science of Traditional Chinese Medicines, China Pharmaceutical University, Nanjing 210009;2Key Laboratory of Modern Traditional Chinese Medicines (Ministry of Education),China Pharmaceutical University, Nanjing 210009; 3Department of Complex Prescription of Traditional Chinese Medicines, China Pharmaceutical University, Nanjing 210009, ChinaAvailable online May 2010[ABSTRACT]AIM: To develop high performance liquid chromatography combined with photodiode-array detection and electrospray ionization multiple-stage mass spectrometry (HPLC-DAD-ESI-MS n) for the analysis and identification of flavonoids and phenolic acids in the rhizome of Iris tectorum Maxim.. METHOD: The structures of flavonoids and phenolic acids were identified by chroma-tographic retention times, UV spectra as well as ESI-MS n spectra. RESULTS: Ten isoflavones were identified as tectori-genin-7-O-ȕ-glucosyl-4'-O-ȕ-glucoside (3), tectoridin (5), iristectorin B (6), iristectorin A (7), iridin (8), genistein (11),tectorigenin (12), iristectorigenin A (14), iristectorigenin B (16), i and rigenin (17). Two flavanones, one flavonol and one flavanonol were tenta-tively identified as hesperetin (9), 5, 7, 3'-trihydroxy-6, 4'-dimethoxyflavanone (10), rhamnocitrin (13) and dihydrokaempferide (15), respectively. The three phenolic acids were tectoruside (1), androsin (2) and apocynin (4). CONCLUSION: The developed simple and rapid method is useful to rapidly identify the bioactive constituents in the rhizome of Iris tectorum. Two flavanones, hesperetin (9)and 5,7,3'-trihydroxy-6, 4'-dimethoxyflavanone (10) were identified from this species for the first time.[KEY WORDS]Iris tectorum Maxim.; HPLC-DAD-ESI-MS n; Flavonoids; Phenolic acids[CLC Number]R917 [Document code] A [Article ID] 1672-3651(2010)03-0202-061 IntroductionIris tectorum Maxim. (Iridaceae) is a perennial herbwidely distributed in China, called Yuan Wei in Chinese. It isalso known as Japanese Roof Iris in some literature, becauseit was first observed growing on roofs in Japan by the Rus-sian botanist, Carl Maximowicz (1827–1891) [1]. Its rhizomehas been used in traditional Japanese medicine as an emeticand laxative [2]. In traditional Chinese medicine, it was usedas a bitter medicine to treat disorders described as Zheng JiaJie Ju, which are similar to modern descriptions of tumors[3-4]. According to the latest edition of the Chinese Pharma-copoeia, the rhizome of I. tectorum is referred to as “ChuanShe Gan” (Rhizoma Iridis Tectori), which is used as a tradi-tional herbal medicine to treat sore throat, disperse phlegmand for heat-clearing as well as detoxifying [5]. Previous phy-[Received on] 18-Mar-2009[Research Funding] This project was supported by National NaturalScience Foundation of China (No. 30170103)[ Corresponding author] QIN Min-Jian: Prof., Tel: 86-025-********,Fax: 86-025-********, E-mail: minjianqin@Copyright © 2010, China Pharmaceutical University.Published by Elsevier B.V. All rights reserved.tochemical investigations resulted in the isolation of severalflavonoids [6-11], iridal-type triterpenoids [2, 12-14] and quinones[15]. Some isoflavones and phenolic acids were found to havehigh content in I. tectorum, and exhibit considerableanti-infective, antitussive, expectorant, antibacterial, cyto-toxic and hepatoprotective effects [3, 16-20]. Those compoundswere considered as the main active components of I. tectorum.However, in the Chinese Pharmacopoeia, only tectoridin hasbeen used as the chemical marker for the quality control ofthe rhizome of I. tectorum. Therefore, qualitative evaluationof these main components of I. tectorum is significant for thequality control of this medicinal herb.With the soft ionization source such as atmosphericpressure chemical ionization (APCI) and electrospray ioniza-tion (ESI), MS combined with chromatographic techniqueshas become a powerful approach in the identification, quanti-fication and structural confirmation of active components inmedicinal plants. Nowadays, HPLC with photodiode arraydetection–electrospray ionization multiple-stage mass spec-trometry (HPLC-DAD–ESI-MS n) has grown into one of themost powerful analytical techniques available for analyzingcomplex herbal extracts [21-23]. It can simultaneously provideUV and multiple-stage mass spectra, which can be applied toidentify known components by comparing on-line detected chromatograms and spectra with those of authentic com-pounds, and can elucidate unknown structures based on the tandem mass fragmentation pathways of known ones. Previ-ously, there were no reports on the qualitative research of the major components in the rhizome of I. tectorum by HPLC-DAD–ESI-MS n.In this study, a HPLC-DAD–ESI-MS n method was de-veloped and validated for the identification of ten known isoflavones, three phenolic acids, two flavanones, one fla-vonol and one flavanonol in the rhizome of I. tectorum.2 Experimental2.1 Instrumentation and reagentsLiquid chromatography separation was performed using an Agilent 1100 HPLC system (Agilent Technologies, Palo Alto, CA, USA) composed of a quaternary pump, an on-line degasser, a column temperature controller and a diode array detector (DAD). A KH5200DB ultrasonic cleaning instru-ment (Jiangsu Kscsb Ultrasonic Instrument Co., Jiangsu, China) was used for extraction. HPLC grade acetonitrile (TEDIA, Fair¿eld, OH, USA) was used. HPLC grade water was obtained from a water purifying system (Milli-pore, Bedford, MA, USA); analytical grade acetic acid (Nanjing Reagent, Jiangsu, China) and HPLC grade methanol (Han-bang, Jiangsu, China) were used for sample preparation. For HPLC-DAD–ESI-MS n analysis, the LC system was coupled to ion trap mass spectrometer (Agilent Corp., Santa Clara, CA, USA) equipped with an ESI source.2.2 MaterialsI. tectorum was collected from Beijing, China, in August 2008. The plant was identified by Prof. QIN Min-jian and a voucher specimen (SP-08-0810) was deposited at the Her-barium of Medicinal Plants of China Pharmaceutical Univer-sity. Eight authentic compounds: Androsin, tectoridin, iris-tectorin A, iristectorin B, iridin, tectorigenin, iristectorigenin A and irigenin were isolated in our laboratory from I. tecto-rum. Their structures were elucidated by spectral data (MS, 1H NMR and 13C NMR). The purity of each compound was determined to be higher than 95% by HPLC. The samples of the herb and chemicals for analysis were stored in the refrig-erator at 20 q C.2.3 Sample preparationThe rhizomes of I. tectorum were air-dried and ground into powder. An aliquot (0.5 g) of the powder was weighed into a conical flask and 25 mL methanol (HPLC grade) was added. Then the mixture was ultrasonically extracted at room temperature for 40 min. The solution was centrifuged at 2 500 r·min 1, at room temperature for 10 min, the supernatant was filtered through a syringe filter (0.45 ȝm) before HPLC analysis.2.4 HPLC proceduresChromatographic separation was carried out on an Agilent Eclipse Plus TM C18 column (150 mm × 3.0 mm, 3.5 ȝm) at 40°C. Elution was performed at a flow rate of 0.8 mL·min 1. Solvents used were acetonitrile (A) and 0.05% acetic acid in water (B). All solvents were filtered through a 0.45 ȝm nylon filter and then degassed by sonication in an ultrasonic bath prior to use. Gradient was as follows: 5% B at 0 min, 12% B at 3 min, 15% B at 8 min, 20% B at 20 min, 28% B at 24 min, 35% B at 28 min, 65% B at 32 min, 65% B at 35 min, 100% B at 50 min, and the injection volume of sample solution was 5 ȝL. The chromatograms were recorded at 270 nm.2.5 ESI-MS parameterAgilent 1100 HPLC-MSD Trap SL mass spectrometer (Agilent Technologies, Palo Alto, CA, USA) equipped with an electrospray ionization source was used in both positive and negative ion modes. The mass spectrometry detector (MSD) parameters were as follows: negative and positive ionization modes, scan range from m/z 100 to 1 000, desol-vent gas temperature 350 °C, capillary voltage 3.1 kV (posi-tive mode) and 3.5 kV (negative mode). Nitrogen was used as nebulizing gas at a pressure of 40 psi and the flow rate was adjusted to 9.0 lL/min. All the operations, data acquisition and analysis were controlled by Chemstation software (Agilent Technologies, Palo Alto, CA, USA).3 Results and discussion3.1 Optimization of HPLC–DAD–ESI-MS conditions and method validationPhotodiode array detector (DAD) was used in HPLC analysis and the optimum monitor wavelength at 270 nm was selected from the full range spectra. Several binary solvent gradients were compared with respect to separation efficiency of phenolic acids and flavonoids. Modifiers such as formic acid, acetic acid and phosphoric acid were added to the mo-bile phase to enhance peak resolution. After several trials, a gradient solvent system described in the experimental section with acetic acid as modifier was developed and a total of 17 flavonoids and phenolic acids were resolved within 30 min. Since a complicated gradient of elution was used, variation in retention time may happen. The repeatability was assessed by analyzing six independent extracts prepared from the same batch of herb, respectively. The RSDs of the retention time were lower than 0.15% (Table 1).The flavonoids and phenolic acids were analyzed in both positive and negative ionization mode. According to the lit-erature, the negative ion mode should be more selective and more sensitive than the positive ion mode in crude plant phytochemical analysis [25]. Although the pseudomolecular ion signals of all the components investigated were observed in negative ion mode, some of the diagnostic Retro-Diels-Alder (RDA) ions were only observed in the positive ion mode which is helpful for the structural determi-nation of the A- and B-ring substitution patterns. As a result, the combined application of negative and positive ion mode appeared to be necessary for the structural analysis of flavon-oids by mass spectrometry.3.2 Identification of flavonoids and phenolic acids in I. tectorum by HPLC–DAD– ESI-MS nThe dominant fragmentation pathways of authentic compounds were studied. All authentic compounds exhibited [M + H]+ ions in positive ion mode and [M – H]- in negative ion mode with sufficient abundances that could be subjected to MS2 and MS3 analysis. MS2 and MS3 data were obtained by collision-induced dissociation (CID), and utilized for the structural identification of compounds with similar fragmen-tation patterns. Comparing retention times and the MS n spec-tra with those of the authentic standards, eight peaks were unambiguously identified as androsin (2), tectoridin (5), iris-tectorin B (6), iristectorin A (7), iridin (8), tectorigenin (12), iristectorigenin A (14) and irigenin (17). Nine other peaks were tentatively identified as tectoruside (1), tectori-genin-7-O-ȕ-glucosyl-4'-O-ȕ-glucoside (3), apocynin (4), hesperetin (9), 5,7,3'-trihydroxy-6,4'-dimethoxyflavanone (10), genistein (11), rhamnocitrin (13), dihydrokaempferide (15) and iristectorigenin B (16) by comparing their MS data and UV spectra with those reported in the literature [10, 23-28].The total ion currents (TIC) together with HPLC chro-matograms of the samples are shown in Fig. 1, and the chemical structures of the compounds from 1 to 17 are shown in Fig. 2From the above results, isoflavonoids were identified as the major constituents in the rhizome of I. tectorum. Four isoflavone O-glycosides and five aglycones were identified. Peak 5 (tectoridin) was taken as an example to discuss the fragmentation pathways in detail. The molecule ion at m/z 463 in positive ion mode showed MS2 fragment ion at m/z 301, due to the loss of one glucose residue. In the following MS3 experiment, the loss of a methyl radical (15 Da) from [M + H – 162]+ was the predominant fragmentation, indicat-ing an methoxyl group linked at the aglycone. Furthermore, the ion at m/z 301 successively yielded the diagnostic ions of isoflavonoids at m/z 183, with the neutral loss of 118 Da produced by RDA fragmentation [26, 29], suggesting that the methoxyl group was attached to the A-ring. Therefore, peak 5 was identified as tectoridin by comparing its retention time and mass fragmentation pattern with those of the standards. The proposed fragmentation pathway in positive ion mode is given in Fig. 3. Similar fragmentation pathways were ob-served in the spectra of other isoflavonoids.Table 1 HPLC-DAD-ESI-MS n data of flavonoids and phenolic acids identified in the rhizome of Iris tectorum Maxim.Peak No. t R/minRSD oft R/%UV Ȝmax/nm[M+H]+(m/z)Fragment ions (+)[M–H]-(m/z)Fragment ions(-) Identi¿cation1 4.5 0.11 226, 270, 304 491 329, 167 489 373, 327, 165 tectoruside2 5.3 0.08 228, 270, 304 - - 327 283, 165, 150 androsin3 6.7 0.07 212(sh*),264,336(sh) - - 623 461,299tectori-genin-7-O-ȕ-glucosyl-4'-O-ȕ-glucoside4 9.4 0.13 232, 278, 304 - - 165 150, 122 apocynin5 13.2 0.13 214 (sh), 266,334(sh) 463 301, 286, 183 461 446, 428, 299, 284 tectoridin6 14.7 0.10 230(sh),266,340(sh) 493 331, 316, 298, 183, 168491 437, 331, 329, 314, 262 iristectorin B7 16.8 0.14 230(sh),266,340(sh) 493 331, 316, 299, 183, 168491 437, 331, 329, 314 iristectorin A8 17.5 0.14 238(sh), 268 523 361, 346 521 506,488,466,442,359,344 iridin9 25.7 0.03 214(sh), 294 - - 301 286,273,259,257,244,193,181, 179, 151, 124hesperetin10 26.6 0.03 212(sh), 266 - - 331 316, 313, 301, 274, 251,193, 1815,7,3'-trihydroxy-6,4'-dimethoxyflava-none11 26.7 0.02 271, 210 - - 269 212, 167, 152, 118 genistein12 27.3 0.05 214(sh),266,340(sh) 301 286, 229, 168, 159 299 284, 240, 212 tectorigenin13 27.9 0.04 218(sh), 282, 338 - - 299 284, 271, 255, 132, 120 rhamnocitrin14 28.1 0.03 216(sh), 268, 340(sh) 331 316, 301, 298, 242,186, 134329 314, 299, 271 iristectorigenin A15 28.5 0.05 220(sh), 292 - - 301 283, 273, 139 dihydrokaempferide16 28.9 0.04 224(sh), 268 331 316, 301, 298, 287,273, 243, 195329 314, 301, 289 iristectorigenin B17 29.2 0.04 234(sh), 268 361 346, 328, 310, 301,286, 271, 183 359 344,299 irigenin* shoulder peak - not observedreferred to as 5, 7, 3'-trihydroxy-6, 4'-dimethoxyflavanone likewise. According to the literature, the structures of known flavonol and flavanonol as well as three phenolic acids were also tentatively identified. Results of all the HPLC-DAD and MS n analyses are listed in Table 1.4 ConclusionIn this study, fourteen known flavonoids and three phe-nolic acids were identified in the rhizome of I. tectorum by using HPLC-DAD-ESI-MS n in both positive and negative ion modes. Isoflavones seem to be the major constituents ac-cording to our study. Two flavanones were identified from this species for the first time.This newly established method was successfully applied to simultaneously identify the major constituents in the rhi-zome of I. tectorum. The results were consistent to other phytochemical analyses, but it’s timesaving and simple com-pared with the traditional phytochemical method [2, 6-15]. Moreover, with the high sensitivity of the mass spectrum detector (MSD), some components with trace amounts were also identified, and thus a full-scale chemical profile could be obtained. Those phenols identified in I. tectorum could be considered as chemical markers of this species which might be the major bioactive constituents of I. tectorum. Further quantitative analysis method of those components should be developed for the quality control of this medicinal herb. References[1] Klingaman G. Plant of the week: Japanese roof iris, Latin:Iris tectorum, Division of Agriculture, University of Arkan-sas, Little Rock, Arkansas, USA [EB/OL]. 2005. Availablefrom: /plantoftheweek/ articles/iris_ japanese_roof_3-4-05.htm,[2] Seki K, Tomihari T, Haga K, et al. Iristectorene B, a mono-cyclic triterpene ester from Iris tectorum [J].Phytochemistry,1994, 36(2): 433-438.[3] Fang R, Houghton PJ, Hylands PJ. Cytotoxic effects ofcompounds from Iris tectorum on human cancer cell lines [J].J of Ethnopharmacology, 2008, 118(2): 257-263.[4] Fang R, Houghton PJ, Luo C, et al. Isolation and structuredetermination of triterpenes from Iris tectorum [J]. Phyto-chemistry, 2007, 68(9): 1242-1247.[5] The State Pharmacopoeia Committee of the People's Repub-lic of China. Pharmacopoeia of the People’s Republic of China[Z]. Beijing: Chemical Industry Press, 2000: 28-29. [6] Shibata B. Constituents of Iris tectorum Maxim. [J]. Yaku-gaku Zasshi,1927, 543: 380-385.[7] Morita N, Shimokoriyama M, Shimizu M, et al. Studies onthe Medicinal Resources. XXXII. The Components of Rhi-zome of Iris tectorum Maximowicz (Iridaceae) [J]. ChemPharm Bull, 1972, 20 (4): 730-733.[8] Morita N, Shimokoriyama M, Shimizu M, et al. Studies onmedicinal resources. XXXċ. The Components of rhizome of Iris tectorum (Iridaceae) [J]. Yakugaku Zasshi, 1972, 92(8): 1052-1054.[9] Xu YL, Ma YB, Jiang X. Isoflavonoidsof Iris tectorum [J].Acta Bot Yunnan, 1999, 21 (1): 125-130.[10] Shan HQ, Qin MJ, Wu JR. Constituents of Rhizomes of Iristectorum [J]. Chin J Nat Med, 2007, 5 (4): 312-314.[11] Yuan CJ, Wang J, Chen S, et al. Study on the chemical con-stituents of Iris tectorum Maxim. [J]. Nat Prod Res Dev,2008, 20 (3): 444-446.[12] Seki K, Tomihari T, Haga K, et al. Iristectorenes A and C-G,monocyclic triterpene esters from Iris tectorum [J]. Phyto-chemistry, 1994, 36(2): 425-431.[13] Takahashi K, Hano Y, Suganuma M, et al.28-Deacetylbelamcandal, a tumor-promoting triterpenoidfrom Iris tectorum [J]. J Nat Prod, 1999, 62(2): 291-293. [14] Takahashi K, Hoshino Y, Suzuki S, et al. Iridals from Iristectorum and Belamcanda chinensis [J]. Phytochemistry,2000, 53(8): 925-929.[15] Seki K, Tomihari T, Haga K, et al. Iristectorones A-H, spiro-triterpene-quinone adducts from Iris tectorum [J]. Phyto-chemistry, 1994, 37(3): 807-815.[16] Kim YP, Yamada M, Lim SS, et al. Inhibition by tectorigeninand tectoridin of prostaglandin E2 production and cyclooxygenase-2 induction in rat peritoneal macrophages[J]. Biochim Biophys Acta-Mol Cell Biol Lipids, 1999,1438(3): 399-407.[17] Qin MJ, Ji WL, Liu J, et al. Scavenging effects on radicals ofisoflavones from rhizome of Belamcandae chinensis [J].Chin Tradit Herb Drugs, 2003, 34(7): 640-641.[18] Kang KA, Lee KH, Chae S, et al. Cytoprotective effect oftectorigenin, a metabolite formed by transformation of tec-toridin by intestinal microflora, on oxidative stress inducedby hydrogen peroxide [J]. Eur J Pharmacol, 2005, 519(1-2):16-23.[19] Thelen P, Scharf JG, Burfeind P, et al. Tectorigenin and otherphytochemicals extracted from leopard lily Belamcandachinensis affect new and established targets for therapies inprostate cancer[J]. Carcinogenesis, 2005, 26(8): 1360-1367.[20] Lee HU, Bae EA, Kim DH. Hepatoprotective effect of tec-toridin and tectorigenin on tert-butyl hyperoxide-inducedliver injury [J]. J Pharmacol Sci, 2005, 97(4): 541-544. [21] Sun JM, Zhang H, Yang JS. Analysis of Secoiridoid Gluco-sides in Jasminum lanceolarium Roxb. by HPLC-MS [J].Chin J Nat Med, 2009, 7 (6): 436-439.[22] Zhuoma D,Yan Z, Yang B, et al. Development of anHPLC-DAD–ESI-MS n method for quantitative analysis ofSaussurea tridactyla [J]. J Pharmaceut Biomed, 2008, 48 (4): 1076-1081.[23] Li J, Li WZM, Huang W, et al. Quality evaluation of Rhi-zoma Belamcandae (Belamcanda chinensis (L.) DC.) by us-ing high-performance liquid chromatography coupled withdiode array detector and mass spectrometry [J]. J Chroma-togr A, 2009, 1216(11): 2071-2078.[24] Abad-Garcia B, Garmon-Lobato S, Berrueta LA, et al. Afragmentation study of dihydroquercetin using triple quad-rupole mass spectrometry and its application for identifica-tion of dihydroflavonols in Citrus juices [J]. Rapid CommunMass Spectrom, 2009; 23(17): 2785-2792.[25] Fabre N, Rustan I, Hoffmann E, et al. Determination of fla-vone, flavonol, and flavanone aglycones by negative ion liq-uid chromatography electrospray ion trap mass spectrometry[J]. J Am Soc Mass Spectrom, 2001, 12(6): 707-715[26] Ma YL, Li QM, Heuvel HV, et al. Characterization of fla-vone and flavonol aglycones by collision-induced dissocia-tion tandem mass spectrometry [J]. Rapid Commun MassSpectrom, 1997, 11(12): 1357-1364.[27] Zhou DY, Xu Q, Xue XY, et al. Rapid qualitative and quan-titative analyses of flavanone aglycones in Fructus aurantiiby HPLC ion-trap MS [J]. J Sep Sci, 2007, 30(6): 858-867. [28] McNaba H, Ferreira ESB, Hulme AN, et al. Negative ionESI-MS analysis of natural yellow dye flavonoids-an iso-topic labelling study [J]. Int J Mass Spectrom,2009,284(1-3): 57-65.[29] Zhang X, Xiao HB, Xue XY, et al. Simultaneous characteri-zation of isoflavonoids and astragalosides in two Astragalusspecies by high-performance liquid chromatography coupledwith atmospheric pressure chemical ionization tandem massspectrometry [J]. J Sep Sci,2007, 30(13): 2059-2069.。
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反应实例（3）：手性离子液体
By combining the advantages of organocatalysts and ionic liquids,a functionalized chiral ionic liquid such as 1 can act as a highly efficient and reusable organocatalyst for the asymmetric Michael addition reaction of ketones and aldehydes with nitroalkenes
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Facts About Phosgene
February 7, 2005 Page 1 of 3FACT SHEETFacts About PhosgeneWhat phosgene is·Phosgene is a major industrial chemical used to make plastics and pesticides. ·At room temperature (70°F), phosgene is a poisonous gas. · With cooling and pressure, phosgene gas can be converted into a liquid so that it can be shippedand stored. When liquid phosgene is released, it quickly turns into a gas that stays close to theground and spreads rapidly.· Phosgene gas may appear colorless or as a white to pale yellow cloud. At low concentrations, it has a pleasant odor of newly mown hay or green corn, but its odor may not be noticed by all peopleexposed. At high concentrations, the odor may be strong and unpleasant.· Phosgene itself is nonflammable (not easily ignited and burned).·Phosgene is also known by its military designation, “CG.” Where phosgene is found and how it is used·Phosgene was used extensively during World War I as a choking (pulmonary) agent. Among the chemicals used in the war, phosgene was responsible for the large majority of deaths. ·Phosgene is not found naturally in the environment. ·Phosgene is used in industry to produce many other chemicals such as pesticides. · Phosgene can be formed when chlorinated hydrocarbon compounds are exposed to hightemperatures. Chlorinated hydrocarbon compounds are substances sometimes used or created in industry that contain the elements chlorine, hydrogen, and carbon.· The vapors of chlorinated solvents exposed to high temperatures have been known to producephosgene. Chlorinated solvents are chlorinecontaining chemicals that are typically used inindustrial processes to dissolve or clean other materials, such as in paint stripping, metal cleaning, and dry cleaning.·Phosgene gas is heavier than air, so it would be more likely found in lowlying areas. How people are exposed to phosgene·People’s risk for exposure depends on how close they are to the place where the phosgene was released. ·If phosgene gas is released into the air, people may be exposed through skin contact or eye contact. They may also be exposed by breathing air that contains phosgene. ·If phosgene liquid is released into water, people may be exposed by touching or drinking water that contains phosgene. · If phosgene liquid comes into contact with food, people may be exposed by eating thecontaminated food.How phosgene works· Poisoning caused by phosgene depends on the amount of phosgene to which a person is exposed,the route of exposure, and the length of time that a person is exposed.· Phosgene gas and liquid are irritants that can damage the skin, eyes, nose, throat, and lungs. Immediate signs and symptoms of phosgene exposure· During or immediately after exposure to dangerous concentrations of phosgene, the following signs and symptoms may develop:o Coughingo Burning sensation in the throat and eyeso Watery eyeso Blurred visiono Difficulty breathing or shortness of breatho Nausea and vomitingo Skin contact can result in lesions similar to those from frostbite or burnso Following exposure to high concentrations of phosgene, a person may develop fluid in the lungs (pulmonary edema) within 2 to 6 hours.· Exposure to phosgene may cause delayed effects that may not be apparent for up to 48 hours after exposure, even if the person feels better or appears well following removal from exposure.Therefore, people who have been exposed to phosgene should be monitored for 48 hoursafterward. Delayed effects that can appear for up to 48 hours include the following: o Difficulty breathingo Coughing up white to pinktinged fluid (a sign of pulmonary edema)o Low blood pressureo Heart failure· Showing these signs or symptoms does not necessarily mean that a person has been exposed to phosgene.What the longterm health effects are· Most people who recover after an exposure to phosgene make a complete recovery. However, chronic bronchitis and emphysema have been reported as a result of phosgene exposure.How people can protect themselves and what they should do if they are exposed to phosgene · Leave the area where the phosgene was released and get to fresh air. Quickly moving to an area where fresh air is available is highly effective in reducing the possibility of death from exposure to phosgene.o If the phosgene release was outdoors, move away from the area where the phosgene was released. Go to the highest ground possible, because phosgene is heavier than air and willsink to lowlying areas.o If the phosgene release was indoors, get out of the building.· If you think you may have been exposed, remove your clothing, rapidly wash your entire body with soap and water, and get medical care as quickly as possible.· Removing and disposing of clothing:o Quickly take off clothing that has liquid phosgene on it. Any clothing that has to be pulled over the head should be cut off the body instead of pulled over the head. If possible, sealthe clothing in a plastic bag. Then seal the first plastic bag in a second plastic bag.Removing and sealing the clothing in this way will help protect you and other people fromany chemicals that might be on your clothes.o If you placed your clothes in plastic bags, inform either the local or state health department or emergency personnel upon their arrival. Do not handle the plastic bags.February 7, 2005 Page 2 of 3o If you are helping other people remove their clothing, try to avoid touching anycontaminated areas, and remove the clothing as quickly as possible.· Washing the body:o As quickly as possible, wash your entire body with large amounts of soap and water.Washing with soap and water will help protect people from any chemicals on their bodies.o If your eyes are burning or your vision is blurred, rinse your eyes with plain water for 10 to15 minutes. If you wear contacts, remove them and place them in the bags with thecontaminated clothing. Do not put the contacts back in your eyes. If you wear eyeglasses,wash them with soap and water. You can put the eyeglasses back on after you wash them.· If you have ingested (swallowed) phosgene, do not induce vomiting or drink fluids.· Seek medical attention right away. Dial 911 and explain what has happened.How phosgene exposure is treatedTreatment for phosgene exposure consists of removing phosgene from the body as soon as possible and providing supportive medical care in a hospital setting. No antidote exists for phosgene. Exposed people should be observed for up to 48 hours, because it may take that long for symptoms to develop or reoccur.How people can get more information about phosgenePeople can contact one of the following:· Regional poison control center (18002221222)· Centers for Disease Control and Preventiono Public Response Hotline (CDC)§ (800) 2324636 (English and Spanish)§ TTY (888) 2326358o Emergency Preparedness and Response Web site (/)o Email inquiries: cdcinfo@Centers for Disease Control and Prevention (CDC), National Institute for Occupational Safety and Health (NIOSH), Pocket Guide to Chemical Hazards (/niosh/npg/npgd0504.html)For more information, visit /chemical, or call CDC at800CDCINFO (English and Spanish) or 8882326348 (TTY).February 7, 2005 Page 3 of 3。
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3.0 Properties of PhosgeneTable of Contents3.1 Introduction3.2 Names3.3 Physical Properties3.4 Reactivity, Instability and Combustion Properties3.5 Commercial Chemistry3.6 Uses3. Properties of Phosgene3.1. IntroductionThe Phosgene Molecule:ClC = OClPhos gene (fasjen) n. [[so named (1812) by Sir Humphry DAVY<Gr phos, light+ -gene, born -GEN]] a colorless, volatile, highlypoisonous liquid, COC12, prepared by the reaction of carbonmonoxide with chlorine in the presence of activated charcoal or,originally, in sunlight; carbonyl chloride: used as a poison gas, inorganic synthesis, in making dyes, etc.13.2. NamesChemical Name - PhosgeneChemical Abstract Registry Number - 0000 75-44-5Last Revised 2002Check for Potential UpdatesOther Names:CARBON DICHLORIDE OXIDECARBONE (OXYCHLORURE DE) [FRENCH]CARBONIC DICHLORIDECARBONIO (OSSICLORURCI DI) [ITALIAN]CARBON OXYCHLORIDECARBON OXYCHLORIDECARBONYLCHLORID [GERMAN]CARBONYL CHLORIDECARBONYL DIC"LORIDECGCHLOROFORMYL CHLORIDE1 Excerpted from Compton's Interactive Encyclopedia. Copyright (c) 1994, 1995Compton'sNewMedia, Inc. All Rights Reserved.FOSGEEN (DUTCH)FOSGEN (POLISH)FOSGENE (ITALIAN)FOSGENO (SPANISH)HSDB 796KOOLSTOFOXYCHLORIDE (DUTCH)NCI-C60219PHOSGEN (GERMAN)PHOSGENERCRA WASTE NUMBER P095Formula:COCl2CCl2O3.3. Physical PropertiesGrade and Strength - Commercial 100%Properties & CharacteristicsColor and Physical State - At room temperature and pressure,phosgene is a colorless, non-flammable, highly toxic gas. Atsufficiently lower temperatures or higher pressures or both, it is ahighly toxic colorless liquid.Note: Phosgene, in the presence of high humidity, water, fog orammonia, may produce a white cloud.Last Revised 2002Check for Potential UpdatesLast Revised 2002Check for Potential UpdatesPropertyValue English Units Value Metric Units Molecular Weight 98.9158 lbm/lbmol 98.9158 g/mol Critical Temperature 359.33 F 181.85 CCritical Pressure 822.97462 psia 5.67E+07 dyne/cm² Critical Volume3.04351 ft³/lbmol 190 cm³/mol Critical Compressibility Factor0.2850.285Melting Point-198.004 F -127.78 CTriple Point Temperature -198.004 F -127.78 C Triple Point Pressure 0.0001335 psia 9.20651 dyne/cm² Normal Boiling Point 45.608 F 7.56 C Liquid Molar Volume1.12992 ft³/lbmol 70.5389 cm³/mol Ideal Gas Heat of Formation -9.42E+04 BTU/lbmol -2.19E+12 erg/mol Ideal Gas Gibbs of Formation-8.81E+04 BTU/lbmol -2.05E+12 erg/mol Ideal Gas Absolute Entropy 67.81556 BTU/lbmol·R 2.84E+09 erg/mol·K Standard Absolute Entropy 67.81556 BTU/lbmol·R 2.84E+09 erg/mol·K Standard Heat of Formation -9.42E+04 BTU/lbmol -2.19E+12 erg/mol Standard Gibbs of Formation -8.81E+04 BTU/lbmol -2.05E+12 erg/mol Enthalpy of Fusion at M.P. 2468.717 BTU/lbmol 5.74E+10 erg/mol Heat of Combustion -7.51E+04 BTU/lbmol -1.75E+12 erg/mol Acentric Factor 0.201309 0.201309 Radius of Gyration 9.44E-10 ft 2.88E-08 cmSolubility Parameter 92.45383 (BTU/ft³)^½ 5.64E+04 (erg/cm³)^½Dipole Moment1.17E-18 esu-cm 1.16919 Debye (D) Van der Waals Volume 0.5590444 ft³/lbmol 34.9 cm³/mol Van der Waals Area2.54E+09 ft²/lbmol 5.20E+09 cm²/mol Refractive Index 1.35609 1.35609 Flash PointUnknown R Unknown C Upper Flammability Limit Unknown vol% in air Unknown vol% in air Lower Flammability Limit Unknown vol% in air Unknown vol% in air Upper Flammability TemperatureUnknown R Unknown C Lower Flammability TemperatureUnknown R Unknown C Auto-ignition TemperatureUnknownRUnknownCOdor Threshold - 0. 12-5.7 ppm 1. (Threshold varies with individuals and is higher after prolonged exposure).Odor - Mildly sweet, not an unpleasant odor of musty hay in low concentrations, becoming more pungent in higher concentrations.Permissible Exposure Limit 2 Threshold Limit Value 3 (by volume in air) - 0.1 ppm.3.4. Reactivity, Instability and Combustion PropertiesPhosgene is a stable compound at normal ambient temperatures(21o C or 70o F). At temperatures above 250o C (482o F), phosgenedecomposes to form mixtures of carbon monoxide (CO), chlorine(CI2) carbon dioxide (CO2) and carbon tetrachloride (CCI4).Phosgene reacts slowly with water to form carbon dioxide andhydrochloric acid. Phosgene reacts readily with caustic solutionand even more readily with ammonia and ammonia water.When fighting fires, minimize the reactivity hazards throughprecautionary measures such as those described in Section 5.Reactivity hazards exist when attempts are made to neutralizeliquid spills because the heat of neutralization increases the rate ofvaporization of liquid phosgene. Various techniques for minimizingthe rate of vaporization from a liquid spill are listed in Section 6.1.4.Hazardous chemical reactions involving phosgene include thefollowing:t-Butyl azidoformate - In the formation of tert-butylazidoformate by the addition of phosgene to alcohols followedby the addition of sodium nitride or hydrazoic acid in thepresence of pyridine, reaction of phosgene with the azide cancause the formation of explosive carbazide. To prevent thisreaction, completely remove excess phosgene; pass nitrogeninto the solution prior to addition of the azide.Aluminum - Powdered aluminum burns in the vapor ofphosgene.Alcohols - Phosgene reacts with all alcohols; two examplesfollow:2,4-Hexadiyne-1,6-diol - The reaction between 2,4-hexadiyne-1,6-diol and phosgene produces 2,4-hexadiyne-1,6-bischloroformate which is a shock-sensitive compound.Isopropyl Alcohol - The reaction between isopropyl alcoholand phosgene forms isopropyl chloroformate and hydrogenchloride. At temperatures slightly above ambient isopropyl,chloroformate can decompose explosively in the presence ofiron salts.Last Revised 2002Check for Potential UpdatesLast Revised 2002Check for Potential UpdatesSecondary Amines - Phosgene may react with secondary amines to form hazardous products.Potassium - A mixture of potassium and phosgene explodes when subjected to shock.Sodium - Vapors of sodium and phosgene react with luminescence at about 260o C.3.5. Commercial ChemistryPhosgene, COCl 2, the acid chloride of carbonic acid, first was made by the action of light on a mixture of carbon monoxide and chlorine (Gr. phos light, genes bom)1. In the current process, the mixed gasses are exposed to carbon catalyst. The reaction is exothermic, producing heat that must be removed from the reactor.The formula for the reaction to produce phosgene is:ActivatedCO + Cl 2 COCl 2 + HeatCarbon MonoxideChlorineCarbonPhosgeneTextbook of Organic Chemistry, C.R. Noller, W.B. Saunders Company,1966.Hydrogen and methane impurities in the carbon monoxide feed gas react with chlorine to produce hydrogen chloride and carbon tetrachloride respectively. The formulas for these two impurity reactions are:H 2 + Cl 2 2 HCl + HeatCH 4 + 4Cl 2 CCl 4 + 4 HCl +HeatHydrogen and methane react with chlorine without catalyst, therefore the reaction can take place in the piping prior to the reactors. Normally, these impurities are at very low concentrations and the impurities formed are not significant. If a high concentration of either impurity exists, these reactions can generate enough heat to melt the pipe. Since chlorine is an oxidizer, and methane, hydrogen and carbon monoxide are fuels, a fire can occur in the pipeline without oxygen. At temperatures above 250o F, chlorine will start reacting with steel, weakening the piping andvessels. At 483o F, chlorine will ignite iron and produce a fire.Detection of these impurity generated reactions can be noticed by arapid rise in the temperature of the feed gas after the carbonmonoxide and chlorine mixing point. The use of high mixingtemperature automatic shut down is a useful method to helpeliminate this type of failure.Carbon tetrachloride and carbon dioxide can also be formed at hightemperature by the reaction of two phosgene molecules. In thecenter of the reaction tubes temperatures are sufficiently hot tocause a small amount of this impurity reaction. The formula for thisreaction is:2 COCl2 + Heat CCI4 + CO23.6. UsesPhosgene is a widely used chemical intermediate, primarilymanufactured for the synthesis of isocyanate-based polymers,carbonic acid esters and acid chlorides. It is also used in themanufacture of dyestuffs, some insecticides and pharmaceuticalsand in metallurgy. (1,2,3)1. Great Lakes2. U.S. Environmental Protection Agency. Health AssessmentDocument for Phosgene (External Review Draft).EPA/600/8-86/022A. Environmental Criteria and AssessmentOffice, Office of Health and Environmental Assessment, Office ofResearch and Development, Research Triangle Park, NC. 1986.3. M. Sittig. Handbook of Toxic and Hazardous Chemicals andCarcinogens. 2nd ed. Noyes Publications, Park Ridge, NJ.1985.Phosgene consumption is summarized below:Toluene diisocyanate, 45 percent; MDI and polymericisocyanates, 38 percent; polycarbonate resins, 12 percent;miscellaneous, including specialty isocyanates, chloroformatesand agricultural chemicals, 5 percent. (ChemExpo)Other uses in the miscellaneous category include certain dyeintermediates and preparation of ethyl carbonate, a useful solvent.TDI Reaction:The overall reaction of toluene diamine withphosgene to form toluene diisocyanate (TDI) is shown below:CH3-C6H3(NH2)2+ 2 COCl2 ----- > CH3-C6H3(NCO)2 + 4 HCIToluene diamine Phosgene TDI HCI Last Revised 2002Check for Potential UpdatesLast Revised 2002Check for Potential UpdatesMDI Reaction: The overall reaction of Diaminodiphenyl methane with phosgene to form Methyldiphenyl diisocyanate (MDl) is shown below:2(C 6H 4)-CH 2-2(NH 2) + 2 COCl 2 ----- > 2(C 6H 4)-CH 2-2(NCO) + 4 HCIDiaminodiphenyl methane Phosgene MDIHClPolycarbonate Reaction: The reaction of Bisphenol-A with phosgene gives the very hard and strong polycarbonate plastics that can be molded and extruded.x (HO-C 6H 4-C(CH 3)2-C 6H 4-OH) + x (COCl 2) - > 2x HCI + [-OCO-O-C 6H 4-C(CH 3)2-C 6H 4-]xBisphenol-A Phosgene HCl PolycarbonateWhen phosgene reacts with alcohols, the alkyl chloroformate is formed first and further reaction gives the alkyl carbonate.COCl 2 + C 2H 5OH --- > ClCOOC 2H 5 + HCIPhosgene Ethyl chloroformateCICOOC 2H 5 + C 2H 5OH--- > OC(OC 2H 5)2 + HClEthyl carbonateAdditional ResourcesPhosgene. Kirk-Othmer Encyclopedia of Chemical Technology. Third Edition. Volume 12. John Wiley and Sons, 1978.Davis, D. S., G. B. DeWolf, S. R. Penrod and J. D. Quass. Prevention Reference Manual: Chemical Specific, Vol. 14: Control of Accidental Releases of Phosgene, 1989.Phosgene. Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A 19, pp. 411 - 42.Section Title Page I. Properties 411 1.1. Physical Properties 411 1.2. Chemical Properties 412 1.2. I. Reactions with Organic Compounds 412 1.2.2. Reactions with Inorganic Compounds 413 2. Production 413 3. Storage and Transportation 414 4. Quality and Analysis 414 5. Waste-Gas Treatment and Monitoring 415 6. Safety Precautions 415 7. Uses 4l6 8. Economic Aspects 417 9. Toxicology and Occupational Health 417 10. References 419.Isocyanates, Organic. Ullmann's Encyclopedia of Industrial Chemistry, 5thEdition, Vol. A 14, pp. 611 – 62.Section Title Page I. Physical Properties 611 2. Chemical Properties611 3. Production 616 3.I .Phosgenation of Free Amines 617 3.2.Other Phosgenation Procedures 618 3.2. I. Phosgenation of AmineHydrochlorides 618 3.2.2. Phosgenation of Carbarnate Salts 618 3.2.3.Phosgenation of Ureas 619 3.3. Non-Phosgene Processes.Last Revised 2002Check for Potential Updates。