克酮酸的合成研究

论文编号:HG024  字数:8603,页数:23

摘要：克酮酸是一种重要的化学中间体，用途十分广泛。现今克酮酸被用于生物分析领域，是与生物分子共价结合的近红外荧光染料。此外克酮酸染料是一类新型的近红外吸收染料，由于具有良好的光热稳定行和荧光发光性能，因而在光学记录与存储领域有着潜在的应用价值。研究了克酮酸的新合成路线,以四氯苯醌为原料,经甲氧基化,水解,氧化脱羧三步制得高纯度的克酮酸。和从乙二醛出发的传统制法相比,该路线原料易得,条件温和,总收率可达35%,高于传统法的收率约10%。反应以四氯苯醌为原料，合成高纯度的克酮酸（4,5-二羟基-4-环戊烯-1，2，3，-三酮）。整个反应通过六个步骤的研究，并得到了反应的最佳条件，具体如下：
 1) 四甲氧基苯醌过程中所用甲醇溶液必须为无水甲醇，在回流反应前溶液冷却后的温度15℃，然后进一步回流反应；
 2) 甲氧基苯醌水解反应过程中，当氢溴酸与醋酸摩尔比为1:1时，四羟基苯醌与2mol/L的盐酸溶液中重结晶产品收率最佳；
 3) 制备克酮酸的过程中加入浓硫酸的量为0.4ml时，产品收率最理想。
 经过优化的工艺条件比传统路线反应条件温和，收率高，为克酮酸的制备和工业化生产开辟了一条新的途径。
关键词：克酮酸；四氯苯醌；四甲氧基苯醌；四羟基苯醌；合成

Study on the New Synthetic Process of Croconic Acid
Abstract：The crocic acid is in the center a kind of important chemistry body, the use is very extensive.The crocic acid is used for living creature analysis realm, is the near red and outside fluorescence dyestuff that combines with the living creature member covalence at present.In addition the crocic acid dyestuff is a type of new near and red outside absorption dyestuff, in order to having, the good light heat stabilizes to go to give out light to go with fluorescence ability, as a result at optical record with saving the realm have latent of applied value.Studied a lately synthesizing of the crocic acid route, take tetrachlorobenzoquinone as raw material, Be turned by AN oxygen radicle, water solution, oxidize to take off Zui three step systems Gao Chun Du's crocic acid.The traditional method for making setting out with two Quans from B compares, the route's raw material easily get, the condition is moderate, always accepting a rate cans reach to 35%, is farer high than about 10% of traditional method.Respond to set out and synthesize Gao Chun Du's crocic acid from the tetrachlorobenzoquinone.((or4,5-dihydroxy-4-cyclopentene-1,2,3-trione)The whole reaction passes six researches of steps, and got the best condition of reaction, concretely as follows:
 1)The methyl alcohol aqua used in the etramethoxy process have to in order to have no water methyl alcohol, the aqua cools off the temperature of empress 15 ℃ before the reflux responds, then the further reflux responds;
 2)AN oxygen radicle benzene Mao water solution reaction process in, the hydrogen bromine is sour with acetic acid Mo Er compare for 1:be tetrahydroxy and 2 mols at 1:00|weigh to crystallize in the L hydrochloric acid aqua, the product accepts to lead superior turn;
 3)The product accepts to lead while making to join the measuring of oil of vitriol as 0.4 mls in the process of crocic acid the most ideal.
 After excellent craft condition for turning compare traditional route reaction the condition is moderate and accept to lead higher, developed a new path for a great deal of making and industrialization production of crocic acid.
Keywords：crocic acid；tetrachlorobenzoquinone； etramethoxy-1, 4-benzoquinone； tetrahydroxy-1, 4-benzoquinone；synthesis

目 录
引言…………………………………………………………………………………………1

第一章 克酮酸的合成综述……………………………………………………………2
  1.1克酮酸的简介………………………………………………………………………… 2
  1.2克酮酸的用途………………………………………………………………………2
  1.3克酮酸的合成方法……………………………………………………………………3
  1.3.1 乙二醛聚合、脱羧法………………………………………………………………3
  1.3.2四氯苯醌经甲基化、水解、氧化脱羧法………………………………………3
  1.4研究目的及其意义……………………………………………………………………4
第二章 实验部分………………………………………………………………5
  2.1实验原理………………………………………………………………………………5
  2.2 实验仪器、试剂………………………………………………………………5
  2.2.1实验仪器……………………………………………………………………………5
  2.2.2试剂…………………………………………………………………………………6
  2.3 实验步骤………………………………………………………………………………7
  2.3.1四甲氧基苯醌的合成………………………………………………………………7
  2.3.2 四羟基苯醌的合成…………………………………………………………………8
  2.3.3克酮酸的合成………………………………………………………………………8
第三章 结果与讨论 ……………………………………………………………………10
  3.1四氯苯醌甲氧基取代反应过程及影响因素…………………………………………10
  3.1.1反应中反应液中含水率对反应结果的影响………………………………10
 3.1.2 回流前反应冷却温度对结果的影响 ……………………………………………10
  3.2四甲氧基苯醌水解反应过程及其影响因素………………………………………11
  3.2.1氢溴酸和醋酸摩尔比对反应结果的影响…………………………………………11
  3.2.2 HCl浓度对实验结果的影响………………………………………………………12
  3.3四羟基苯醌反应制克酮酸过程及其影响因素………………………………13
 3.4 最佳实验条件的验证 ………………………………………………………………14
结论……………………………………………………………………………16
致谢……………………………………………………………………………17
参考文献………………………………………………………………………18