CN108164458B - 一种柠嗪酸的合成方法 - Google Patents

一种柠嗪酸的合成方法 Download PDF

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CN108164458B
CN108164458B CN201810129627.5A CN201810129627A CN108164458B CN 108164458 B CN108164458 B CN 108164458B CN 201810129627 A CN201810129627 A CN 201810129627A CN 108164458 B CN108164458 B CN 108164458B
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acid
solution
citrazinic
urea
citrazinic acid
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CN108164458A (zh
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翁雪香
王嘉君
向雪琴
陈静茹
阮永明
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Zhejiang Normal University CJNU
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
    • C07D213/803—Processes of preparation

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明属于化合物制备技术领域，具体为一种柠嗪酸的合成方法。本发明采用柠檬酸和尿素的水热反应法，具体步骤包括:将柠檬酸和尿素溶于去离子水中，超声分散，充分混匀；然后反应釜内，在一定温度条件下进行水热反应；最后对反应液高速离心，除去上清液，将得到的黄色沉淀物烘干，即得色泽好，高产率，高纯度的柠嗪酸产物。本发明方法，反应条件温和，操作简单，只需一步硫酸水解，产物纯度高（>96%），产率高（70%‑85%）。

Description

一种柠嗪酸的合成方法
技术领域
本发明属于化合物制备技术领域，具体涉及柠嗪酸的合成方法。
背景技术
柠嗪酸(CitrazinicAcid,CA)是一种杂环化合物，含有羟基和吡啶环结构，可以作为合成了一系列吡啶、嘧啶和恶唑酮的原料。此外，柠嗪酸还可以通过重氮和偶联反应间接检测重金属离子，作为起始原料用于太阳能电池（DSC）上TiO2敏化剂的固定。柠嗪酸在摄影领域作为漂白剂、定影剂，在电镀行业可以作为抑制剂、助溶剂，其衍生物与氨节毒霉素结合具有一定抗菌作用。电化学中柠嗪酸可以作为电化学传感器检测生物小分子。
目前关于柠嗪酸合成的路线有：
1.柠檬酸酯化加压氨解法。先将柠檬酸与醇反应形成酯，酯在加压条件下进行氨解生成柠檬酸酰胺,再经环化脱氨生成柠嗪酸酰胺,得到最终产物。此法合成路线长,消耗大量的原材料。
2.柠檬酸、尿素高温水解法。将尿素与柠檬酸熔融,高温回流反应后，以酸处理，并加大量NaOH水解中和得到柠嗪酸。该方法中NaOH既是催化剂,亦是反应物。NaOH的浓度愈高,愈有利于水解。然而NaOH量过大,需耗较多的H2SO4中和。同时生成的Na2SO4在冷却时易结晶出来，不易制得纯度高的最终产物。
发明内容
本发明的目的在于提供一种反应条件温和,原材料消耗省，实验周期短，最终产物纯度高的柠嗪酸的合成方法。
本发明提供的柠嗪酸的合成方法，采用柠檬酸和尿素的水热反应法，具体步骤如下:
（1）取柠檬酸0.2438-1.2188 g和尿素0.6966-1.3932 g溶于60-80ml去离子水中，超声5-10 min，充分混匀；
（2）把混合液装入100 ml反应釜内，设置烘箱温度为160℃-200℃，水热条件下保温2-6 h；冷却至室温，获得墨绿色溶液；
（3）将溶液置于20-80℃恒温水浴槽内，磁力搅拌，并向溶液中滴入20-98%硫酸至溶液pH为2-3，观察到大量黄色固体沉淀，以6000~12000 r/min速度离心5-10 min除去上清液，再用去离子水多次洗涤后抽干，将得到的黄色沉淀物于烘箱内烘干，即得高纯度的柠嗪酸产物。
为了进一步比较柠嗪酸水热反应生成最佳条件，我们比较了反映温度（160℃、185℃、200℃、210℃），反应时间（40 min、2 h、4 h、6 h）、柠檬酸和尿素的摩尔比(1:1、1:2、1:4、1：6、1:8)。我们得出结论反应温度160-200℃，反应时间2 h-6 h,尿素是柠檬酸的四倍以上时，此时生成柠嗪酸的产率高(以柠檬酸计产率70%-85%)。
本发明方法，反应条件温和，操作简单，只需一步硫酸水解，产物纯度高(>96%)，产率高(以柠檬酸计产率70%-85%)。
具体实施方式
下面通过具体实施例进一步描述本发明。
实施例1柠嗪酸制备
（1）取1.2188 g（0.0058 mol）柠檬酸和1.3932 g（0.0231mol）尿素溶于60 ml去离子水中，超声10 min，充分混匀；
（2）把混合液装入100 ml反应釜内，设置烘箱温度为185℃，水热条件下保温2 h；冷却至室温，获得墨绿色溶液；
（3）将溶液置于60℃恒温水浴槽内，磁力搅拌，并向溶液中滴入50%硫酸至溶液pH为2-3，观察到大量黄色固体沉淀，以12000 r/min速度离心5 min除去上清液，再用去离子水多次洗涤后抽干，将得到的黄色沉淀物于60℃烘箱内烘干，即得70.66%的柠嗪酸产物。
柠嗪酸的表征
1、紫外及荧光分析
该化合物有两个特征紫外吸收峰在~230 nm和~340 nm，荧光光谱中最佳激发峰和最佳发射峰分别在~340 nm和~440 nm；
2、红外分析
红外谱图在~3116cm-1和~2904 cm-1有两个谱带，这是属于N-H和C-H振动。在~1695cm-1和~1605 cm-1处观察到两个强的谱带,这属于VC=O和苯环上的VC=N的振动。同样，在~1310和~1250 cm-1处出现两个强烈的谱带分别属于VC-O和VC-N。在~1410 cm-1和~1530 cm-1两个位置谱带分别是-COOH的Vs和Vas振动模式。
实施例2柠嗪酸制备
（1）取1.2188 g（0.0058 mol）柠檬酸和2.0898 g（0.0348 mol）尿素溶于60 ml去离子水中，超声10 min，充分混匀；
（2）把混合液装入反应釜内，设置烘箱温度为185℃，水热条件下保温2 h；冷却至室温，获得墨绿色溶液；
（3）将溶液置于60℃恒温水浴槽内，磁力搅拌，并向溶液中滴入50%硫酸至溶液pH为2-3，观察到大量黄色固体沉淀，以12000 r/min速度离心10 min除去上清液，再用去离子水多次洗涤后抽干，将得到的黄色沉淀物于60℃烘箱内烘干，即得72.78%的柠嗪酸产物。
实施例3柠嗪酸制备
（1）取1.2188 g（0.0058 mol）柠檬酸和1.3932 g（0.0231 mol）尿素溶于60 ml去离子水中，超声10 min，充分混匀；
（2）把混合液装入反应釜内，设置烘箱温度为185℃，水热条件下保温2 h；冷却至室温，获得墨绿色溶液；
（3）将溶液置于60℃恒温水浴槽内，磁力搅拌，并向溶液中滴入98%硫酸至溶液pH为2-3，观察到大量黄色固体沉淀，以12000 r/min速度离心10 min除去上清液，再用去离子水多次洗涤后抽干，将得到的黄色沉淀物于60℃烘箱内烘干，即得85.18%的柠嗪酸产物。

Claims (1)

1.一种柠嗪酸的合成方法，其特征在于，具体步骤如下：
（1）取柠檬酸0.6094-1.2188 g和尿素0.6966-1.3932 g溶于60-80ml去离子水中，超声5-10 min，充分混匀；
（2）把混合液装入100 ml反应釜内，设置烘箱温度为160-200℃，水热条件下保温2-6h；冷却至室温，获得墨绿色溶液；
（3）将溶液置于20-80℃恒温水浴槽内，磁力搅拌，并向溶液中滴入20%-98%硫酸至溶液pH为2-3，观察到大量黄色固体沉淀，以6000-12000 r/min速度离心5-10 min除去上清液，再用去离子水多次洗涤后抽干，将得到的黄色沉淀物于烘箱内烘干，即得高产率、高纯度的柠嗪酸产物。
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