Catalytic Decomposition of Chlorophenols Using Fiber-supported Cobalt Phthalocyanine
过氧化氢酶
过氧化氢酶科技名词定义中文名称：过氧化氢酶英文名称：catalase定义：编号：EC 1.11.1.6。
催化过氧化氢分解成氧和水的酶，存在于细胞的过氧化物体内。
应用学科：生物化学与分子生物学（一级学科）；酶（二级学科）以上内容由全国科学技术名词审定委员会审定公布求助编辑百科名片过氧化氢酶过氧化氢酶，是催化过氧化氢分解成氧和水的酶，存在于细胞的过氧化物体内。
过氧化氢酶是过氧化物酶体的标志酶, 约占过氧化物酶体酶总量的40%。
过氧化氢酶存在于所有已知的动物的各个组织中，特别在肝脏中以高浓度存在。
过氧化氢酶在食品工业中被用于除去用于制造奶酪的牛奶中的过氧化氢。
过氧化氢酶也被用于食品包装，防止食物被氧化。
过氧化氢酶存在于红细胞及某些组织内的过氧化体中，它的主要作用就是催化H2O2分解为H2O与O2，使得H2O2不至于与O2在铁螯合物作用下反应生成非常有害的-OH 过氧化氢酶的作用是使过氧化氢还原成水: 2H2O2 →O2 + 2H2O CAS号：9001-05-2[1]触酶过氧化氢酶（CAT）是一种酶类清除剂，又称为触酶，是以铁卟啉为辅基的结合酶。
它可促使H2O2分解为分子氧和水，清除体内的过氧化氢，从而使细胞免于遭受H2O2的毒害，是生物防御体系的关键酶之一。
CAT作用于过氧化氢的机理实质上是H2O2的歧化，必须有两个H2O2先后与CAT相遇且碰撞在活性中心上，才能发生反应。
H2O2浓度越高，分解速度越快。
来源几乎所有的生物机体都存在过氧化氢酶。
其普遍存在于能呼吸的生物体内，主要存在于植物的叶绿体、线粒体、内质网、动物的肝和红细胞中，其酶促活性为机体提供了抗氧化防御机理。
CAT是红血素酶，不同的来源有不同的结构。
在不同的组织中其活性水平高低不同。
过氧化氢在肝脏中分解速度比在脑或心脏等器官快，就是因为肝中的CAT含量水平高。
H2O2 分解酶这是一种稳定的过氧化氢分解酶, 能将过氧化氢分解成水和氧气, 而对纤维和染料没有影响, 因而漂白后染色前, 通过H2O2 分解酶去除漂白织物上和染缸中残留的过氧化氢, 以避免纤维的进一步氧化和染色时染料的氧化。
粮食中熏蒸剂硫酰氟残留量的顶空气相色谱测定
第19 卷第3 期2000 年5 月分析测试学报FENX I CESHI X UE BA O(Journal of I nstrumental Anal y si s)V ol . 19 N o . 3M a y 2000粮食中熏蒸剂硫酰氟残留量的顶空气相色谱测定瞿进文, 徐海聂, 张中亚(珠海出入境检验检疫局, 广东珠海519020)摘要: 报道了利用顶空气相色谱- 电子捕获检测法测定玉米、大米、黄豆、大麦等粮食中熏蒸剂硫酰氟残留量的方法。
该法回收率( 硫酰氟含量为2. 0 ×10 - 6 时) 为95. 7 %～101. 3 % , 相对标准偏差为1. 4 %～3. 5 % , 线性范围在1 ×10 - 1 ～1 ×10 - 7 g/ L , 粮食中硫酰氟检出限低于1. 0 ×10 - 8 。
该法操作简单, 分析时间短, 可用于粮食中残留硫酰氟含量的检测。
关键词: 硫酰氟; 熏蒸剂;气相色谱中图分类号: TS210. 753文献标识码: A文章编号: 1004 - 4957( 2000) 03 - 0076 - 03在粮食的储藏过程中, 为了防止虫害的发生, 通常需要使用熏蒸剂杀虫灭菌。
人们常用的熏蒸剂溴甲烷已被确定为Ⅰ级臭氧耗竭物质, 世界各国现已开始对其限量生产。
徐国淦等1 开发的新型熏蒸剂硫酰氟, 已证明对杀灭光肩星天牛、木蠹蛾、谷象等多种害虫有良好的效果, 其用量目前有较大的增长趋势。
而粮食中残留的熏蒸剂对人体有一定的毒害作用, 需对其含量进行控制。
对粮食中硫酰氟的测定, 通常使用碱液将其吸收转化为氟离子, 再利用氟离子选择电极法测定1 。
该法存在碱液吸收不够完全、检测限高、分析繁杂等弊端。
本文以顶空气相色谱法测定粮食中硫酰氟的残留量, 回收率高, 精密度好, 操作简单, 分析时间短。
1 实验部分1. 1 仪器与试剂HP - 5890 Ⅱ气相色谱仪, 63 Ni 电子捕获检测器, HP - 3365 化学工作站, Pora p ak Q 色谱柱( 183 cm ×0. 32 mm , 0. 175～0. 147 m m) , Ham ilton 气密性注射器( 0. 5 m L) 。
氯苯吩嗪
取本品，加三氯甲烷溶解并稀释制成每1ml中约含20mg的溶液，作为供试品溶液；精密量取适量，分别用三 氯甲烷定量稀释制成每1ml中约含0.10mg与0.16mg的溶液，作为对照溶液（1）和（2）。照薄层色谱法（2010年 版药典二部附录ⅤB）试验，吸取上述三种溶液各5μl，分别点于同一硅胶GF254薄层板上（该板先用3%氨溶液饱 和30分钟），以二氯甲烷－正丙醇（85：4）为展开剂，展开，晾干，再重新展开一次，晾干，置紫外光灯 （254nm）下检视后，喷以50%硫酸溶液再检视。供试品溶液如显杂质斑点，不得深于对照溶液（2）的主斑点， 且深于对照溶液（1）的主斑点不得多于2个。
（3）本品的红外光吸收图谱应与对照的图谱（《药品红外光谱集》671图）一致。
氯化物
取本品约0.40g，加冰醋酸5ml溶解，加水适量与硝酸1ml，再加水使成50ml，溶液如不澄清，滤过，将滤液 分为两等份，1份中加硝酸银试液1ml，放置15分钟，如显浑浊，滤过，至溶液澄清，加水使成约40ml，加标准氯 化钠溶液2.0ml与水适量使成50ml，摇匀，在暗处放置5分钟，作为对照液；另1份加水使成40ml，加硝酸银试液 1ml与水适量使成50ml，摇匀，在暗处放置5分钟，如发生浑浊，与上述对照液比较，不得更浓（0.01%）。
安全术语
S36Wear suitable protective clothing. 穿戴适当的防护服。
风险术语
R22Harmful if swallowed. 吞食有害。
药典标准
0 1
来源与含量
0 2
性状
0 3
鉴别
0 4
检查
0 6
药物分析
0 5
含量测定
来源（名称）、含量（效价）
迷迭香酸对过氧化氢处理下的皮肤黑色素瘤的抗氧化作用(原文翻译)
迷迭香酸（罗丹酚酸）对H2O2处理过的皮肤黑色素瘤细胞的抗氧化作用Sun Mi Yoo1 and Jeong Ran Kang2*1.韩国光州500-741号东冈大学美容系2.韩国首尔143-701号建国大学生物工程系2009.2.6收到 2009.4.17接收本学科旨在检测迷迭香酸对人工孵育的皮肤黑色素瘤细胞在ROS下的抗氧化作用。
通过XTT比色法，以细胞毒性和抗氧化作用来分析细胞粘附活性，DPPH自由基清除活性以及H2O2处理1-10h和未经处理的两种情况下乳酸脱氢酶的活性。
用20-110 μM 的H2O2处理皮肤黑色素瘤细胞5-7h后，细胞活性的降低呈剂量和时间依赖性。
通过XTT比色法测得H2O2的半抑制浓度（IC50 ）为90μM。
同时H2O2增强了LDH细胞的剂量依赖性。
用50-90μM的H2O2处理8h后测得LDH50为60 μM H2O2。
迷迭香酸能增强细胞活性和DPPH自由基清除活性，降低乳酸盐脱氢酶的活性。
细胞的H2O2处理证实了对人工孵育的皮肤黑色素瘤细胞的强抗氧化作用。
通过H2O2的处理，迷迭香酸能在细胞内能增强细胞活性和DPPH 自由基清除活性，降低乳酸盐脱氢酶的活性。
这被认为是迷迭香酸对ROS（ROS）如H2O2的抗氧化作用。
Key words：DPPH-radical scavenging, LDH, rosmarinic acid, XTT assay关键字：DPPH自由基清除活性，乳酸脱氢酶，迷迭香酸，XTT比色法据研究发现，ROS通过氧化应激对细胞的损伤和一些脑部疾病比如帕金森症或心脏疾病例如心肌梗塞之间有很大的关联[Difazio et al., 1992; Delanty and Dichter, 1998].尤其是研究人员认为ROS是皮肤老化的一个主要的因素后，一直试图从ROS方面研究衰老。
[Yokozawa et al., 1998].据研究表明，ROS的氧化应激会通过萎缩细胞引起各种疾病，例如超氧自由基、H2O2（H2O2）或羟基自由基的巯基蛋白反应中断酶的活性，破坏脱氧RMA（DNA）或RMA（RNA），诱导细胞膜脂质过氧化。
羟基自由基测定
Quantitation of hydroxyl radical during Fenton oxidationfollowing a single addition of iron and peroxideMichele E.Lindsey,Matthew A.Tarr*Department of Chemistry,University of New Orleans,New Orleans,LA 70148,USAReceived 2October 1998;accepted 15July 1999AbstractChemical probes were used to study the formation of hydroxyl radical in aqueous iron±hydrogen peroxide reaction.Hydroxyl radical formation rate and time dependent concentration were determined in pure water,in aqueous fulvic acid (FA)and humic acid (HA)solutions,and in natural surface waters.Indirect determinations of hydroxyl radical were made by quantitating hydroxyl radical reactions with probe compounds under controlled conditions.High probe concentrations were used to determine radical formation rates and low probe concentrations were used to determine time dependent radical concentration.Two independent probes were used for intercomparison:benzoic acid and 1-propanol.Good agreement between the two probes was observed.Natural water matrices resulted in lower radical formation rates and lower hydroxyl radical concentrations,with observed formation rate and yield in natural waters up to four times lower than in pure water.HA and FA also reduced hydroxyl radical formation under most conditions,although increased radical formation was observed with FA at certain pH values.Hydroxyl radical formation increased linearly with hydrogen peroxide concentration.Ó2000Elsevier Science Ltd.All rights reserved.Keywords:Fenton oxidation;Hydroxyl radical;Degradation;Iron;Hydrogen peroxide;Natural water1.IntroductionNumerous studies have investigated the use of Fen-ton chemistry for pollutant degradation or remediation (Graf et al.,1984;Puppo,1992;Yoshimura et al.,1992;Zepp et al.,1992).In these applications,hydrogen per-oxide is converted to hydroxyl radical in a catalytic cycle with cationic iron acting as catalyst.The high reactivity of hydroxyl radical is advantageous since it readily de-grades a wide array of pollutants (reaction with alkanes,k 107±109M À1s À1;reaction with alkenes and aro-matics,k 109±1010M À1s À1).Unfortunately this ad-vantage is also an important drawback since the hydroxyl radical often reacts with non-pollutant species present at higher concentration.Furthermore,the cata-lytic cycle is in¯uenced by pH,iron complexation,iron solubility,and iron redox cycling between the +2and +3states.In order to better understand the use of Fenton chemistry for pollutant degradation in waste streams or contaminated sites,a better understanding of matrix e ects is needed.This report focuses on the e ects of natural water matrices on hydroxyl radical formation and scavenging.Iron/peroxide systems have been used to degrade a number of contaminants,mostly in the aqueous phase.Degradation of the herbicides 2,4-D,2,4,5-T,and atr-azine in aqueous solution by Fe (II)/H 2O 2or Fe (III)/H 2O 2has been reported (Pignatello,1992).Reactions were pH sensitive,and acidic conditions were necessary for iron solubility.Vella and Munder (1993)used Fe (II)/H 2O 2for the degradation of phenolic compounds in water.Again,acidic conditions (pH 4)were used.Although complete elimination of the parent compound could be achieved for chlorinated and otherphenols,Chemosphere 41(2000)409±417*Corresponding author.Fax:+1-504-280-6860.E-mail address:mtarr@ (M.A.Tarr).0045-6535/00/$-see front matter Ó2000Elsevier Science Ltd.All rights reserved.PII:S 0045-6535(99)00296-9the presence of phosphate signi®cantly hindered degradation.To allow reaction at near neutral pH,researchers have utilized iron chelating agents(Sun and Pignatello, 1992,1993).Several iron chelates were found to be ac-tive in Fenton oxidation although the chelator was also degraded at a slower rate(Sun and Pignatello,1992). Naturally occurring compounds can act as metal che-lators.For example,inorganic salts,humic acids(HAs), fulvic acids(FAs),and organic colloids have been shown to exhibit signi®cant metal complexation(Pettersson et al.,1997;Ganguly et al.,1998;Klein and Niessner, 1998;Rose et al.,1998;Roux et al.,1998).Commercial applications of Fenton chemistry to remediation of contaminated soil are currently in use. These methods add both iron and peroxide to the sat-urated zone,and utilize iron chelators and peroxide stabilizers(Watts and Dilly,1996;Greenburg et al., 1997).Such applications have been successful in reme-diating the saturated zone after petroleum leakage from an underground storage tank.However,conditions for such remediation have typically been developed from empirical observations of degradation e ciency rather than from a fundamental understanding of the HOádynamics.Furthermore,a large excess of peroxide is often used.Fenton reagents have also been used for degradation of bio-recalcitrant perchloroethylene(PCE)and poly-chlorinated biphenyls(PCBs)adsorbed on sand(Sato et al.,1993).Treatment required adjustment of the pH to3with degradation severely limited at pH7.Even at optimum pH,PCB treatment still yielded chlorinated degradation products,indicating incomplete degrada-tion.Further studies on degradation of PCBs indicated that dissolved PCBs are much more readily degraded by hydroxyl radical than are PCBs sorbed to sand(Sedlak and Andren,1994).Some studies involving soil/water systems have re-lied on naturally occurring iron in soils to react with added H2O2(Croft et al.,1992;Watts et al.,1993). However,water insoluble pollutants adsorb to the surface of soil particles thus impeding degradation.Due to the di culty of oxidation across the liquid±solid boundary,high stoichiometric amounts of H2O2were required to achieve complete degradation of the pol-lutants in these environments(Watts et al.,1993). Again,a lack of understanding of the HOáand pollu-tant degradation dynamics was overcome in these sys-tems simply by using an excess of peroxide,rather than adjusting other parameters to optimize the degradation e ciency.The e ciency of hydroxyl radical production from peroxide is a ected by a number of factors,including pH,iron oxidation state,and iron chelation.Phosphate has been reported to inhibit hydroxyl radical production (Vella and Munder,1993),and additional reports indi-cate either inhibition(Croft et al.,1992)or acceleration (Puppo,1992)of HOáproduction in the presence of various ligands.Once formed,hydroxyl radicals may be lost through reaction with matrix mon matrices include FA and HA in natural freshwaters,as well as inorganic species in brackish waters.Due to the relatively high concentration of matrix species,generally only a small fraction of the radicals formed can react with the pol-lutant.This process is a major limitation of Fenton chemistry for degradation of pollutants in the presence of matrix constituents,and results in increased peroxide demand and higher costs.Although signi®cant research has focused on Fenton systems and quantitation of hydroxyl radical concen-tration,several important issues have not yet been ad-dressed.Some researches(Ravikumar and Gurol,1994; Lin and Gurol,1998)have measured loss of hydrogen peroxide as an indicator for hydroxyl radical formation. This approach is not entirely su cient because not all peroxide degraded is converted to hydroxyl radical,and hence measurement of peroxide loss does not allow di-rect determination of[HOá].Other researchers have measured hydroxyl radical concentration under steady state[HOá]conditions,primarily in photochemical sys-tems(Haag and Hoign e,1985;Zhou and Mopper, 1990).While this approach is applicable to photo-chemical systems,it is not representative of common Fenton systems in which peroxide is added in a single dose,resulting in non-steady state[HOá].Additional studies have attempted to quantitate hydroxyl radical under non-steady state conditions(Tomita et al.,1994; Mizuta et al.,1997);however,due to a number of fac-tors,these reports did not provide conclusive hydroxyl radical information.In this study,chemical probes were used to measure both hydroxyl radical formation rate and time depen-dent hydroxyl radical concentration under non-steady state conditions.Methods were developed that allow these determinations in pure water and natural waters, allowing assessment of the role of natural matrices on Fenton oxidations.2.ExperimentalMaterials.Puri®ed water was obtained by further puri®cation of distilled water with a NanopureUV (Barnstead)water treatment system.Natural water samples were collected from sites in Southeast Louisiana at Crawford Landing(CL)on the West Pearl River and from a small water body connecting Lake Pontchartrain and Lake Maurepas(LM).The LM water contained a higher concentration of dissolved organic carbon and inorganic species than the CL water.All natural water samples were®ltered using pre-combusted0.5l m glass410M.E.Lindsey,M.A.Tarr/Chemosphere41(2000)409±417®ber®lters(Machery±Nagel,Rund®lter MN,Alberta, Canada)and were stored in the dark at4°C.Natural water samples were used directly or were diluted with pure water.Suwannee River FA and HA standard ma-terials were purchased from the International Humic Substances Society.FA and HA concentrations are reported as mg FA lÀ1and mg HA lÀ1.The carbon content of these materials are52.44%and52.55%by weight,respectively.Hydrogen peroxide(EM science,$30%)was stan-dardized using iodometric titration(Christian,1994). Iron(II)perchlorate(99+%)was purchased from Alfa. Benzoic acid(BA)(99.5+%),p-hydroxybenzoic acid (99+%),and2,4-dinitrophenylhydrazine(DNPH)(70%) were purchased from Aldrich.Propionaldehyde(98%) was purchased from Fluka,and1-propanol(PrOH) (99+%)was purchased from Mallinkrodt.Dimethyl sulfoxide(certi®ed ACS)and acetonitrile(HPLC grade) were obtained from Fisher.All reagents were used as received.Hydroxyl radical trapping.Both benzoic acid and n-propanol were used as probes for hydroxyl radical. Benzoic acid has a known reaction rate constant of 4.2´109MÀ1sÀ1with hydroxyl radical in aqueous media(Buxton et al.,1988).This reaction produces p-hydroxybenzoic acid(p-HBA)as well as o-HBA, m-HBA,and other products.The fraction of p-HBA produced per reaction was taken from(Zhou and Mopper,1990),who reported5X87Æ0X18moles HOáreacted per mole p-HBA produced.1-Propanol reacts with hydroxyl radical in aqueous media at a rate of 2.8´109MÀ1sÀ1to form propionaldehyde in46%yield (Buxton et al.,1988).BA or PrOH solutions of various concentrations were prepared in pure and natural water.At time zero, a single dose of hydrogen peroxide and a single dose of Fe(II)were added with vigorous mixing.These additions resulted in time zero concentrations of 0.2±1.0mM H2O2and0.2±0.53mM Fe(II).Reactions were stirred,kept in the dark,and maintained at20°C. After a given time interval,reactions were quenched by addition of a su cient amount of a quencher that e ectively outcompeted the probe molecule for reaction with hydroxyl radical.For benzoic acid probe studies, 0.5ml of PrOH was added per10ml of reaction solution.For PrOH probe studies,4ml of dimethyl sulfoxide(DMSO)containing5mM DNPH were added per10ml of reaction solution.These amounts of added quencher had rates of reaction with hydroxyl radical of 50±5600times greater than the probe;therefore,it was assumed that upon addition of quencher,no signi®cant reaction of probe with hydroxyl radical occurred.The resulting products of probe-hydroxyl radical reaction were then analyzed as described below.Each of these experiments produced a single time point.Repetition of the experiment for di erent times then enabled recon-struction of time dependent data from the individual experiments.Quantitation of products.Reaction products were quantitated by high performance liquid chromatography using a Hewlett-Packard1090liquid chromatograph.A Spherisorb ODS-2column(5l m particle size,25cm length´4.6mm id)was used for all separations.Benzoic acid and hydroxybenzoic acids were sepa-rated using the following procedure(Zhou and Mopper, 1990).Samples were brought to pH2±3using HCl then loaded onto a1.5ml loop.After injection,the analytes were pre-concentrated on-column during the initial 3min,then were eluted by increasing the solvent strength.The elution gradient was:water at pH$2.5(A) and acetonitrile(B);0±3min15%B,3±13min linear to 75%B,13±15min linear to100%B.The¯ow rate was 1.0ml minÀ1.Analytes were detected by absorbance at 254nm.For natural water samples it was necessary to ®lter the samples before injection to remove particulates. This was accomplished by raising the pH to P8using NaOH then passing the sample through a0.2l m nylon ®lter(Cole Parmer).The pH adjustment eliminated loss of benzoic acid and hydroxybenzoic acids on the®lters by forming the more soluble ionized species.After®l-tration,the pH was re-adjusted to2±3using HCl and the sample was analyzed as above.Both benzoic acid and p-hydroxybenzoic acid were stable under these condi-tions over the time required for analysis.Propionaldehyde,the product of1-propanol reac-tion with hydroxyl radical,was quantitated following derivitization with DNPH(Coutrim et al.,1993).The derivitization was carried out by adding5mM DNPH in DMSO and allowing12h for the derivitization to occur.Extended time periods(up to48h)did not a ect the concentration of propionaldehyde detected. The derivitized product was injected using a50l l loop.The elution gradient was:water(A)and aceto-nitrile(B);0±2min50%B,2±16min linear to100% B.The analytes were detected by absorbance at 254nm.Hydrogen peroxide determination.Hydrogen peroxide was determined by titration(Christian,1994).In this method,excess IÀplus a catalyst was added to the hy-drogen peroxide solution to form IÀ3.The IÀ3was then titrated with thiosulfate.Hydrogen peroxide was quantitated at di erent times after addition of Fe2 ,and it was assumed that any further Fenton reaction was quenched upon the addition of excess IÀ.3.Results and DiscussionHydroxyl radical quantitation.In a system with both sources and sinks for hydroxyl radical,the change in [HOá]with respect to time is described by Zhou and Mopper(1990):M.E.Lindsey,M.A.Tarr/Chemosphere41(2000)409±417411d HO áa d t F Àk p HO áP Àk S i HO á S iÀk HO HO á 21where F is the formation rate of hydroxyl radical,and the remaining negative terms are loss due to reaction with probe (P),with scavengers (S),and self reaction,respectively.This equation does not represent steady state conditions,but rather the rate of change in hy-droxyl radical concentration with respect to time.Therefore,this equation is applicable under non-steady state conditions.As [P]increases,the term Àk p HO á P will dominate the loss terms.Under these conditions,the total moles of P reacted will be stoichiometrically related to the total moles of HO áformed (Blough,1988),provided that the reaction product does not react signi®cantly with hy-droxyl radical.Since in this study product concentration was always considerably lower than the probe concen-tration,we assumed no signi®cant loss of product due to hydroxyl radical reaction.In the case of low probe concentrations,if [P]is small enough so that k p HO á P ( S i HO áS i k HO HO á 2,then d HO á a d t will be relatively una ected by the probe.In such cases,the concentration of hydroxyl radical in the absence of the probe can be calculated from the second order rate law R p k p HO á P 2 HO á R p a f k p P g 3 HO á avg R p a f k p P avg g4where R p is the rate of probe reaction,k p is the second order rate constant,and avg indicates time averaged values.Over short time intervals,the value for R p was calculated from the linear change in the concentration of the product resulting from probe-HO áreaction.This approach is valid when [HO á]and [P]do not change signi®cantly in the time interval.Validation of experimental approach .In order to con®rm that the approach used here is valid,several experiments were undertaken.The ®rst set of experi-ments involved measurement of product yield as a function of probe concentration.These experiments al-lowed de®nition of high probe concentrations (useful for determination of total HO áformation)and low probe concentration (useful for determination of HO ácon-centration with minimal perturbation by the probe).Product formation was quantitated as a function of re-action time for several probe concentrations.Data for benzoic acid experiments in several matrices are pre-sented in Fig.1.In all matrices,as the benzoic acid concentration increased,the amount of product in-creased,indicating that higher concentrations of benzoic acid were better able to outcomplete the naturalscavengers for reaction with HO á.At su ciently high benzoic acid concentrations,further increases in con-centration resulted in little increase in product yield,as seen by a plateau in the curves in Fig.1at higher [BA].Such behavior has been observed previously (Tomita et al.,1994).These data indicate that no additional trapping of HO ácould be achieved by increasing [BA],and therefore at these concentrations the benzoic acid must be trapping essentially all of the HO á.Under these conditions,the total moles of product obtained is directly proportional to the total moles HO áproduced (for benzoic acid,the proportionality factor is 5.9(Zhou and Mopper,1990)).Increased content of LM water resulted in a lower total amount of HO átrapped in the plateau region (above 5mM BA).This result is most likely due to a decrease in the e ciency of radical production in the presence of the natural water matrix.This result was also evident in time dependent measurements of total HO áproduced,as will be discussed below.As the benzoic acid concentration was lowered,the yield of product decreased.In order to determine hy-droxyl radical concentration in the absence of the added probe,it was necessary that the probe had a negligible e ect on hydroxyl radical concentration.We used the ratio of product yield at low [BA]to product yield at the high [BA]plateau to determine the extent of perturba-tion caused by the addition of benzoic acid.For exam-ple,in a 50/50mixture of pure water with LM water,0.5mM BA has a product yield of only 4%of the yield for P 5mM BA.In contrast,the product yield for 0.5mM BA in pure water was 40%of the yield at 5mM BA.Based on these results,we selected benzoic acid concentrations for use in further experiments to deter-mine HO áproduction and HO áconcentration.For HO áproduction,we used benzoic acid concentrations intheFig.1.Moles of hydroxyl radical trapped as a function of probe concentration (benzoic acid)in pure water and several dilutions of LM water.All data were acquired 10min after the addition of iron (II)perchlorate and H 2O 2at time zero concentrations of 0.2and 0.5mM,respectively.412M.E.Lindsey,M.A.Tarr /Chemosphere 41(2000)409±417plateau region(typically9mM),and for[HOá]mea-surements we used benzoic acid concentrations that had product yields of less than10%of the maximum yield on the plateau(typically0.2mM).Also illustrated in Fig.1is the e ect of increased matrix components on HOáscavenging.As the per-centage of natural water increased,higher concentra-tions of benzoic acid were required to reach the plateau region.These results indicate the higher level of scav-engers in the natural water,therefore requiring a higher benzoic acid concentration to trap all of the hydroxyl radical formed.The presence of these scavengers also minimized the perturbation at low benzoic acid concentrations.Similar studies using propanol as probe were also conducted,and the results are presented in Fig.2.For pure water,complete trapping could be achieved above 100mM PrOH.In contrast to the benzoic acid probe, propanol did not signi®cantly perturb the[HOá]with propanol concentrations below$2mM.For LM water, the PrOH product yield did not plateau as was observed for benzoic acid.Even with propanol concentrations as high as1M,the product yield did not plateau.Therefore PrOH was not used to determine formation rate of HOáin natural waters.However,measurement of[HOá]in natural water was deemed feasible at propanol concen-trations below$10mM.The use of higher concentra-tions of PrOH as compared to benzoic acid is likely a result of the lower rate constant for propanol reaction with hydroxyl radical.Propanol and benzoic acid are distinct probes with di erent mechanisms of reaction with hydroxyl radical. We used such distinct probes to eliminate any possible bias of a single parison of the BA and PrOH results under the same conditions showed good agree-ment.These results can be seen in Fig.3,and are dis-cussed further below.The strong agreement between data from these distinct probes indicate that the probes introduced little or no bias into these measurements.For example,complexation of iron by benzoic acid was de-termined to be insigni®cant,as any such interaction would have resulted in divergent results for the two probes.Measurement of HOáProduction.Hydroxyl radical production was measured in pure water,CL water,LM water,and aqueous solutions of Suwannee River HA and FA.For these experiments,benzoic acid was used as probe at a concentration of9mM(pH$3).The total moles of HOáproduced was measured as a function of time after a single addition of Fe(II)and H2O2.A comparison of moles HOáproduced as a function of time for pure water and the two natural waters is pre-sented in Fig.4.The CL water matrix showed slightly lower HOáproduction than pure water,and the LM water matrix showed dramatically lower production than pure water.After20min,the reaction in pure water had produced$3X5Â10À6mol of HOá,while in CL water only$3Â10À6mol HOáwere produced,and in LM water only$0X8Â10À6moles HOáwere produced. These data indicate that the natural water matrices used here resulted in a lower e ciency of hydroxyl radical formation compared to pure water.Observed rates of formation of hydroxyl radical were also lower in the natural waters than in pure water.We measured the initial rates of hydroxyl radical formation from the ini-tial slopes of the curves in Fig.4,and the resulting values are presented in Table1.Suwannee River HA and FA also showed decreased hydroxyl radical formation.Fig.5illustrates the for-mation of HOávs time for various concentrations of HA and FA.HA caused a more dramatic decrease inradicalFig.2.Moles of hydroxyl radical trapped as a function ofprobe concentration(PrOH)in pure water and dilutions of LMwater.All data were acquired10min after the addition of iron(II)perchlorate and H2O2at time zero concentrations of0.2and0.5mM,respectively.The x-axis is presented with a loga-rithmic scale due to the large range of propanol concentrationsused.Fig.3.Measured time dependent hydroxyl radical concentra-tion(symbols)based on reaction with benzoic acid(0.2mM,pH 4.3)or PrOH(1mM,pH 6).Curves are polynomial®tsto the data points.Matrix is CL water.M.E.Lindsey,M.A.Tarr/Chemosphere41(2000)409±417413production than FA.The initial rate of hydroxyl radical production was decreased by 11%in the presence of 30mg l À1FA and by 27%in the presence of 30mg l À1HA.For HA,the initial hydroxyl radical production rate showed a linear decrease over the range of HA concentrations studied,as illustrated in Fig.6.Since the FA and HA solutions (with 9mM BA)were very close in pH to pure water (with 9mM BA),and since no additional inorganic species were present,these data indicate that dissolved natural organic matter can have a dramatic e ect on hydroxyl radical formation as well as scavenging.Hydroxyl radical formation was assessed as a func-tion of pH with and without added FA.The total moles of HO áformed was measured at 20and 300s after mixing Fe 2 and peroxide.Fig.7represents total moles of HO áformed in a 300s time interval as a function of pH and FA content.The highest yield of hydroxyl radical was observed at pH 3.1,which is in good agreement with previous studies (Pignatello,1992).At this pH,addition of FA resulted in a slight decrease in radical production.However,as the pH was increased,the FA had the opposite e ect,with increased radical production at increased [FA].Furthermore,the e ect of pH was minimized at the highest FA concentration.The data for a 20s time interval showed similar results.The distribution of Fe 2 and Fe 3 is sensitive to pH,with the Fe 2 state becoming less stable with increasing pH,and the formation of oxides and hydroxides also increases with increasing pH.It is therefore reasonable to expect,as has been previously observed (Pignatello,1992),that Fenton production of hydroxylradicalFig.6.Initial rate of hydroxyl radical formation as a function of HA concentration.Benzoic acid used as probe at 9mM,(pH $3).Fig.5.Total moles of HO áformed as a function of time for aqueous FA (a)and HA (b)solutions.Benzoic acid used as probe at 9mM (pH $3).Fig.4.Total moles of HO áformed as a function of time for pure water (pH 3.1),CL water (pH 3.3),and LM water (pH 3.6).Benzoic acid used as probe at 9mM.Table 1Observed initial rate for hydroxyl radical formation in pure water and natural waters Water Initial rate (M s À1)DOC a (mg C l À1)Puri®ed 1.2´10À6<0.003CL 1.0´10À629.9LM0.3´10À6123aDissolved organic carbon.414M.E.Lindsey,M.A.Tarr /Chemosphere 41(2000)409±417becomes less e cient at higher pH.Also previously observed is that iron chelation minimizes these pH ef-fects by stabilizing the chelated Fe 2 ion (Sun and Pig-natello,1993).Our results provide evidence that iron chelation by FA results in stabilization of Fe 2 with respect to pH.At low pH,Fe 2 stability is high,and any chelation of iron by FA has only a small e ect on HO áformation.At higher pH,chelation by FA likely results in increased Fe 2 stability,resulting in a marked increase in Fenton reaction yield upon addition of FA.Previous reports have indicated pseudo ®rst order loss of H 2O 2in the presence of Fe (II)(Walling,1975),Fe (III)+light (Pignatello,1992),and iron oxides (Lin and Gurol,1998).Our peroxide data also indicate ®rst order behavior,although the kinetic behavior did not stabilize until 30±60s after the addition of peroxide.An illustration of this behavior is given in Fig.8.Previous studies did not monitor kinetics at such short times.Our observations were consistent over a wide range of per-oxide concentrations (5±100mM).A possible explana-tion is that initially all of the iron is present as Fe 2 ,which can react with H 2O 2to form HO á.As this reaction proceeds,the concentration of Fe 2 declines,and con-sequently the rate of H 2O 2consumption and HO áfor-mation decline.The loss of Fe 2 is eventually balanced by formation of Fe 2 through reduction of Fe 3 by re-action with peroxide or hydroperoxyl radical,and a steady state Fe 2 concentration is reached.At this point (>60s),pseudo ®rst order loss of H 2O 2is observed.This explanation is also supported by evidence that the HO áformation rate is signi®cantly higher in the ®rst 60s.The in¯uence of hydrogen peroxide concentration on hydroxyl radical production was also assessed.The moles of HO áformed increased linearly with increasing [H 2O 2].The hydroxyl radical formation was measured at20s and 300s intervals after mixing Fe 2 and H 2O 2.The data are presented in Fig.9.The slope of the line was greater at 300s than at 20s,indicating that increasing H 2O 2concentration will result in more signi®cant in-creases in hydroxyl radical over longer time periods.The above observations could be used in evaluating the e ciency of Fenton oxidation in a given matrix.Three possible explanations exist for the observed dif-ferences in the natural water matrices:(1)the rate of peroxide reaction with iron may be altered by iron complexation (Croft et al.,1992;Puppo,1992)with matrix components,(2)Fe (II)/Fe (III)redox cycling may be altered by complexation (Croft et al.,1992)or by the presence of oxidants /reductants in the matrix,or (3)peroxide may be consumed by reaction with matrix components.This method provides a basic understand-ing of the time dependent radical formation rate and allows direct assessment of matrix e ects onradicalFig.8.Plot of ln[H 2O 2]vs time after addition of peroxide to solution of 0.5mM Fe 2 (aq).Line is linear regression to the data points for t P 60s.Fig.9.Total moles of HO áformed as a function of hydrogen peroxide concentration.Benzoic acid used as probe at 9mM (pH 3.1).Measurements made 20and 300s after mixing Fe 2 and H 2O 2in purewater.Fig.7.Total moles of HO áformed as a function of pH for pure water and aqueous FA.Benzoic acid used as probe at 9mM.Lower pH was achieved by addition of perchloric acid,and higher pH was achieved by addition of NaOH.Measurements made 300s after mixing Fe 2 and H 2O 2.M.E.Lindsey,M.A.Tarr /Chemosphere 41(2000)409±417415。
羟基化研究——精选推荐
四川大学博士学位论文苯在催化剂作用下直接氨基化/羟基化研究姓名：***申请学位级别：博士专业：物理化学指导教师：***20030401四川大学博士学位论文苯在催化剂作用下直接氨基化／羟基化研究物理化学专业博士研究生：陈彤指导教师：田安民教授摘要通过活化芳环的Ｃ．Ｈ键，将所需官能团直接引入芳环，实现芳烃的直接功能化，是目前极具挑战性的课题之一，也是当今合成化学的研究热点。
苯胺和苯酚都是重要的有机化工原料，本论文设计了一组镍基催化剂，用之于直接将氨基／羟基引入苯环合成苯胺／苯酚的反应，将传统的多步骤合成反应变为一步反应，成功实现了苯胺Ｉ苯酚的绿色合成。
应用热分析方法和等离子体原子发射光谱分析，对设计的Ｎｉ基催化剂的制备过程、制备规律进行了研究，发现样品中载体与负载组分及负载组分间，在热分解前就存在相互作用，这种相互作用对其热分解过程有很大的影响。
负载一种组分时，载体与负载组分的作用削弱了硝酸盐与结晶水的作用，增强了硝酸根与金属离子的结合，使负载金属盐失去结晶水的温度降低，而最终分解温度升高；负载多种组分时，负载组分与载体之间以及负载组分之间的相互作用，削弱了金属与硝酸根的结合力，使负载的各金属盐的最终分解温度降低。
样品上的负载组分、浸渍顺序、热分解过程等制备方法，对样品中载体与负载组分及负载组分之间的相互作用均有很大的影响，使得样品的热分解机理的不同，造成其热分解动力学模型的差异；锆物种与载体的相互作用强于铈物种，锆、铈合浸过程中，锆与载体优先发生作用。
相同控制含量条件下，制备方法对催化剂样品中实际负载组分的含量有很大影响。
用Ｘ．射线衍射、Ｘ．射线光电子能谱、程序升温还原、氢吸附和氧吸附测试等对催化剂进行了表征。
由于催化剂组成不同、制备方法不同，载体与负载组分及负载组分间产生的相互作用就不同，因而负载的金属组分的分散状态和分散程度也就不同。
本文所研究的催化剂体系中，锆物种的分散效果最好。
这些分散状态和分散程度的差异，使得催化剂上镍氧化物品相生成情况、铈锆固溶体生成情况、催化剂的还原情况（尤其是低温还原情况）、催化剂对氢和氧的吸附能力有很大差异。
植物保护剂[发明专利]
![植物保护剂[发明专利]](https://img.taocdn.com/s3/m/96059aefe87101f69f31952d.png)
专利名称：植物保护剂
专利类型：发明专利
发明人：安德列斯·柴可,拉兹劳·帕波,拉约斯·耐奇,埃瓦·索姆菲,基约奇·朱塞尼,伊斯特万·柴克里,阿尼考·代阿克,
阿哥尼斯·哈杰迪斯
申请号：CN89102068.3
申请日：19890407
公开号：CN1037821A
公开日：
19891213
专利内容由知识产权出版社提供
摘要：本发明是关于ULV植物保护杀节肢动物制剂， 其中除了含有溶解在脂肪烃和向日葵油混合物中的 添加剂外还含有烷芳基聚乙二醇醚。
本发明制剂对植 物表面的初接触角大于13°，20分钟后大于6°， 120分钟后至少仍为2°。
申请人：奇诺英药物化学工厂有限公司
地址：匈牙利布达佩斯
国籍：HU
代理机构：中国国际贸易促进委员会专利代理部
代理人：张元忠
更多信息请下载全文后查看。
金的等离子共振等综述
a b s t r a c t
This review describes the fundamental aspects of laser–gold nanoparticle (Au NP) interaction that leads to nanoscale energy deposition to the surroundings through light amplification and heat generation. Besides the importance of the primary process in physics and chemistry, application of the light–NP interaction has attracted significant interest from various areas ranging from analytical chemistry to material chemistry and biomedicine. Here we consider both mechanistic and application aspects. Our attention is focused on pulsed-laser-induced fast processes that revealed the heating–cooling dynamics of electrons, lattice (particle), and particle’s environment. On the application side, we focus on material fabrication and processing that beat diffraction-limited resolution. Together, we will shed a light on the essence of research activities carried out in the past 10 years. In addition to an abundance of latest information obtained from currently available literature, this review includes figures obtained by our own calculations to provide readers with a better understanding of the basics of the optical properties and energy and heat-transfer processes of Au NPs, which are not familiar to photochemists. © 2012 Elsevier B.V. All rights reserved.
甲基氢化肉桂酰氧基
甲基氢化肉桂酰氧基一、甲基氢化肉桂酰氧基的合成方法甲基氢化肉桂酰氧基的合成方法多种多样，常见的有以下几种：1. 从对甲氧基苯乙酮与分子筛阳离子作用下，经过氢化反应得到。
2. 由氯烷基肉桂酸与试剂反应得到。
3. 由甲基苯丙酮加入无水过氧化氢下，得到。
以上合成方法具有不同的优点和局限性，研究者可以根据需要选择适合的方法。
二、甲基氢化肉桂酰氧基的结构特点甲基氢化肉桂酰氧基是一种香料类化合物，其分子结构如下：分子式：C11H14O2分子量：178.23甲基氢化肉桂酰氧基具有芳香族环和羟基等基团，这些基团赋予其独特的香气和化学性质。
它可以通过酯化反应、还原反应等反应发生不同的化学变化。
三、甲基氢化肉桂酰氧基的应用领域1. 医药领域：甲基氢化肉桂酰氧基具有抗菌、抗病毒、抗炎等药理活性，在医药领域有广泛应用。
2. 香料领域：甲基氢化肉桂酰氧基作为一种天然香料，广泛用于食品、化妆品等行业。
3. 润滑剂领域：甲基氢化肉桂酰氧基具有良好的润滑性能，可用于润滑油、油漆等领域。
以上只是甲基氢化肉桂酰氧基在应用领域中的一部分，未来还有更多潜在的应用价值等待挖掘。
四、甲基氢化肉桂酰氧基的未来发展方向1. 绿色合成：未来可以致力于绿色合成方法的研究，减少废弃物的产生。
2. 结构改性：通过改变甲基氢化肉桂酰氧基的分子结构，进一步优化其性能。
3. 多功能化应用：拓展甲基氢化肉桂酰氧基的应用领域，实现多功能化应用。
总的来说，甲基氢化肉桂酰氧基作为一种重要的有机合成化合物，在医药、香料、润滑剂等领域有着广泛的应用前景。
希望未来能够进一步深入研究，发挥其更大的潜力。
中枢解胆碱能抗晕动病新药盐酸苯环壬酯
中枢解胆碱能抗晕动病新药盐酸苯环壬酯刘传缋;恽榴红【期刊名称】《中国药理学与毒理学杂志》【年(卷),期】2005(19)4【摘要】At present scopolamine is the most powerful single anti-motion sickness drug, but with prominent unwanted side effects. Many attempts had been made to decrease the unwanted side effects, but no any approach was considered to be successful. Based on our working hypothesis that central cholinolytic activity of anticholinergics may not be parallel completely to their side effects, a series of alicyclic amino alcohol esters were designed, synthesized and evaluated. One of the best compounds, phencynonate HCl, was obtained by transesteration of methyl α-phenyl-α-cyclopentyl-α-hydroxy acetate with N-methyl-3-azabicyclo(3,3,1)nonan-9α-ol. In animal models it was demonstrated that at equivalent anti-motion sickness dose the side effects of phencynonate were milder than those of two other central anticholinergic anti-motion sickness drugs scopolamine HBr and difenidol HCl. In clinical trials the overall effectiveness rates for prevention of seasickness and carsickness of phencynonate (oral 2-4 mg/person) was very significantly higher than that of placebo, and also significantly higher than that of difenidol (oral 25-50 mg/person). In self controlled rotatory chair experiments in hospital laboratory, the preventive effects of phencynonate and difenidol inreducing the changes in electronystagmus and electrogastrogram were statistically significant. In another self controlled rotation experiment, phencynonate (2-4 mg/person) and scopolamine (0.3-0.6 mg/person) showed significant anti-motion sickness effects in reducing the gastric electric cycles of electrogastrogram and the Graybiel scores of acute motion sickness and significant inhibitory effects on visual-vestibular interaction dose-dependently. The anti-motion sickness effects of phencynonate 2 and 4 mg were correspondent with those of scopolamine 0.3 and 0.6 mg, respectively. Student pilots with high susceptibility to airsickness were stimulated by Coriolis acceleration. The course of desensitization and habituation to airsickness training in phencynonate group (3 mg/person) was significantly shorter than that of placebo. There was no rebounding in sensitivity to Coriolis stimulation after discontinuing phencynonate, which was reported in case of scopolamine. The side effects of phencynonate HCl were mild dry mouth (9.7%) and drowsiness (9.97%). The incidence of drowsiness is significantly lower than that of difenidol. The side effect of drowsiness was only appeared in aboard ship and bus expe riments, but not in PhaseⅠ trial in hospital or in laboratory rotation tests. The incidence of drowsiness of phencynonate was also lower than that of dramamine in aboard tank experiment. Phencynonate could effectively control the acute attack of vertigo, e specially Meniere′s disease and positional vertigo. In animal models of Parkinson′s disease and parkinsonism, phencynonate showed morepotent antagonistic effects than clinical common used trihexyphendyl. In summary, phencynonate is a newcentral anticholinergic anti-motion sickness drug with higher efficacy and lower central inhibitory side effect than difenidol and scopolamine in prevention of motion sickness. Phencynonate HCl was approved on Dec 25,1993 by State Food and Drug Administration of China as a Class Ⅰ new drug for the prevention and treatment of motion sickness in the market in China.%东莨菪碱是当前抗晕动病最强的单药,但有明显的不良反应.根据"抗胆碱药的中枢解胆碱能活性大小并不与其不良反应相平行"的假设,作者设计、合成了一系列氮杂双环醇的羧酸酯类化合物.其中由α-苯基-α-环戊基-α-羟基乙酸甲酯与N-甲基-3-氮杂双环(3,3,1)壬-9α-醇的酯交换反应制得的盐酸苯环壬酯在动物模型上,等效抗晕剂量时,其不良反应较中枢解胆碱能抗晕动病药东莨菪碱和地芬尼多为轻.临床试验表明,志愿者口服该药(每人2～4 mg)后,其预防晕车晕船的总有效率显著高于安慰剂对照组和阳性对照药地芬尼多组(口服每人25～50 mg).在转椅致晕动症的志愿者自身对照试验中,苯环壬酯和地芬尼多都能显著减少旋转引起的眼电震图和胃电图异常改变.在另一组自身对照的旋转致晕动症人体试验中,苯环壬酯和东莨菪碱都能明显减少旋转引起的胃电活动异常,减少急性晕动病的Graybiel得分和抑制视-前庭-内耳反应.苯环壬酯每人2和4 mg的效用相当于东莨菪碱每人0.3和0.6 mg的效用.在易感空晕病的飞行学员中,苯环壬酯(每人3 mg)明显缩短习服空晕病所需的时间,并且在停药后其习服水平没有明显下降.苯环壬酯的不良反应主要是轻度口干(发生率9.7%)和轻度思睡(9.97%,仅发生于晕车晕船试验中).苯环壬酯是一个中枢解胆碱能抗晕动病新药,较地芬尼多和东莨菪碱抗晕效果更好,中枢不良反应更低.【总页数】10页(P311-320)【作者】刘传缋;恽榴红【作者单位】军事医学科学院毒物药物研究所,北京,100850;军事医学科学院毒物药物研究所,北京,100850【正文语种】中文【中图分类】R971.92【相关文献】1.Box-Behnken设计-响应面法优化盐酸苯环壬酯透皮贴剂的处方 [J], 廖诗琴;刘辉;赵静;王彦辰;郭真君2.盐酸苯环壬酯片预防晕动病的疗效研究 [J], 邓运龙;张咏梅3.左旋盐酸去甲基苯环壬酯对MPTP诱导的SH-SY5Y细胞损伤的保护作用 [J], 周琥;杨培;石京山;王丽韫4.盐酸苯环壬酯及其异构体抗NMDA神经毒性保护作用的比较 [J], 任振宇;彭双清;仲伯华;刘河;刘克良5.盐酸苯环壬酯及其衍生物抗胆碱作用比较研究 [J], 王赟;王丽韫;郑建全;仲伯华;刘河;刘克良因版权原因，仅展示原文概要，查看原文内容请购买。
3—氯—4—氟苯胺的合成
3—氯—4—氟苯胺的合成第21卷第3期2001年8月山西化工SHAXICHEMICALINDU盯RYV o1.2]No.3Aug.200l3一氯一4一氟苯胺的合成韩晓红(太化桌固有限司化工厂.太原030021)摘要:以邻二瓤苯为原料.经过硝化制得3.4-二氯硝基荤.再经过氟化反应得到3一氧一4一氟硝基苯,最后使用氢气加氧还原得到产品3一氧一4一氟苯胺.碱压蒸馏后可获得纯度98以上的产品.通过试验考察了各种影响因素.如反应时问,温度,压力,配比,得副最佳工艺路线.实验表明,该工艺使用原料筒单易得,反应条件温和t成本低.总收率56,工业生产可行关t.词:3一氯一4一氟苯胺{}邻二氯苯;台成引言3一氯4一氟苯胺系诺氟沙星(氟哌酸)抗菌素药物的起始原料.目前,文献报道的合成路线有五条:一是以邻二氯苯为原料,经硝化,氟置换,催化加氢还原合成3一氯4一氟苯胺,该路线原料易得,价格便宜,收率高,所需设备比较简单,操作易控制,只是氟代时易产生副产物;二是以对氯硝基苯为原料经氯化,氟取代和加氢还原生成3氧一4一氟苯胺,该路线使用氯气氯化,毒性大,而且对设备的密封性要求高,反应条件也不易控制;三是以氟苯为原料经硝化,氯化和加氢还原生成3?氯4一氟苯胺,该路线氟苯来源少且价格比较高,使产品成本太大提高;四是以对硝基苯为原料经氟取代,氯化和加氢还原生成3一氯一4一氟苯胺,该工艺路线复杂,对设备要求高,且成本高,其工业价值不太;五是以邻氯苯胺为原料,经氟取代,硝化和加氢还原生成3氯一4一氟苯胺,该路线原料成本高,经济教益低.通过对以上各种合成路线的分析,从其原料来源,操作条件及收率纯度来看,我们确定采用以邻二氯苯为原料合成3一氯4一氟苯胺1实验部分1.13,4-:氯硝基苹的告成在一装有温度计,搅拌器及回流管的500mL三口烧瓶中,加人98的浓硫酸374g.浓硝酸264g,开动搅拌,待混酸温度降到60℃以下时(水浴加热),用分液漏斗加130g邻二氯苯.在滴加过程中,控制反应温度在6OC以下,滴加完后,于60℃反应2h,然后降温,结晶,水洗,干燥,得到黄色结晶物,用色谱分析纯度.】,23一氯一4一氟硝基苯的合成在一装有温度计,搅拌器及回流管的250mI三口烧瓶中,加人合成的3,4二氯硝基苯及氟化钾和二甲基亚砜,在油浴上回流反应,水蒸气蒸馏得淡黄色结晶,分析纯度.1-33氯一4一氟苯胺的合成在lI的高压釜中加人如g3氯一4一氟硝基苯,20g雷尼镍及400ml无水乙醇,用氢气置换空气两次后,将氢气通至所需压力后,开启搅拌,加热至釜内温度与所需温度相差20℃时,停止加热,待高压釜内压力不再变化时,冷却高压釜至室温,排空残余气,将反应液滤去催化剂,回收溶剂后,减压蒸馏,收集】】6C～l20C/21.33kPa馏分,冷却结晶,分析纯度2结果与讨论2.1温度和时间时反应的影响收稿日期:30ol一06—2O作者简介:韩晓红.女,l969年出生.1991年毕业于沈阳化工学院精细化工奇业.学士学位.工程师一现任太化集团有限公司化工厂11分厂工艺员.第21卷第3斯韩晓芝.3一蒙一’一氟苯胺的台成?7?当反应温度低于l80lc时,反应不完全,而且易生成一些低沸点的副产物,影响其产率;当反应温度高于l9o℃时,使氟取代更复杂.也易发生二氟取代,使产品纯度大为降低.故温度应控制在180C～l90C,最好为l8OC～185C.在反应时间上,随着反应时间的变化,产品含量也变化较大.当反应时间小于lh时,原料转化率低;而反应时间过长时,会生成大量剐产物因此反应时问在lh～1.2h内原料转化完全.且3氯d一氟硝基苯纯度较高.2.2溶荆和配比时反应的影响根据文献报道,3,4二氯硝基苯的氟代可以用DMSO和环丁砜作溶剂.当用DMSO作溶剂时,反应温度相对低.而且原料转化为3氯一4一氟硝基苯的量比较大;而用环丁砜作溶剂时,需加入催化剂CsF.由于CsF价格昂贵,故我们采用DMSO作反应溶剂.本反应为固液反应,KF需要过量反应才可以顺利进行当KF与3,4-二氯硝基苯的配比过小时,由于KF的不溶性使一部分原料不能反应而降低收率;配比过大,则会造成KF的浪赞.我们通过实验比较,选定KF与3,4-二氯硝基苯配比为2:l.2.3水分对反应的影响由于水分的存在,使KF以KF?2H.O的形式存在,增大了释放F一的困难程度,使原料转化率降低,同时由于水分存在,使水与其中某一组分形成共沸,而使温度上升缓慢,间接延长了反应时问,故在反应前应对原料进行脱水处理.对3,4一二氨硝基苯和DMS0可通过水与苯共沸,使水分脱除.对于KF,先用蒸发器烘炒.除去其中大部分水分,然后在真空,150℃下干燥3h,除去剩余水分.本合成方法简单易操作,三废较少,收率为j6左右.参考文献1石川延南.氟化物的合成.工业化学杂志,1969,69:1484.2郭惠元.氟碾酸的合成与研究.中国医药工业杂志,1989,2O}3.Synthesisof3-Chlorine——4——FluoroanilineHanXiaohong(TheChemicalPlantofTaiyuanChemicalIndustryGroupCo.Ltd.,Taiyuan030021)Abstract:TheproductispreparatIOnr0mO-dichlorohenz~ene,3,,1-dicb]oronitrobenzenejsproduceb ynitrideOfdichloroben?zene.thenbyflourattongetthe3-chloro?4一flourottitrobenzone.1ast.wemadeuseofcatalystlnghydrogenoratlongeneratethe3-ch]oro一4一flouroaniline.Thepurityproductismadebyfdteration,thecontentofproductis98.Westudytotheallkindso ffactthatincludingreactingtemperature—reactingtime.additiverateofkindsofratarmaterial,andthesel ectat[onofcatalyst—wegeneratethebestexperimentsresultItturtsOutthroughexperimentsthattherawmaterialsiseasytoget ,theprocessarevtoeontrOIandthecostcallhecoweredwithafinn】outputrateof56Itisnlor~fitforindustria】izedmanu~acturing.Keywords:3-ch】orine一4一f】uoroaniline{O.dich】or0ben猢e;synthesis(上接第5页)StudyonSynthesisofHinderPhenolAntioxygenKY--586WangY ongmei(ShanxiProvincialInstituteofChemicalTechnology—Taiyuan030021)Abstract:Non.symmetcicalhinderphenolantioxLdantKY586wassynthesizedfrom0一cresol,isobutylene,propenoicacidmethylesterandtriglyo].Byalkylation.additionandes[erexchangereaction.Theprocessingconditions wereresearchedandthestructureofproductwascharacterizedinthisarticle.Keywords:antioxygen~KY?586~synthesis。