CN102276564A - 一种12-苯基-苯并[b]氧杂蒽三酮衍生物的合成方法 - Google Patents
一种12-苯基-苯并[b]氧杂蒽三酮衍生物的合成方法 Download PDFInfo
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Abstract
本发明涉及12-苯基-苯并[b]氧杂蒽三酮衍生物的合成,具体是涉及3,4-二氢-12-苯基-2H-苯并[b]氧杂蒽-1,6,11(12H)-三酮的合成,是以醛、2-羟基-1,4-萘醌和环状1,3-二羰基化合物为原料,经三组分一锅法一步反应生成。合成工艺路线简捷,条件温和,总收率达到80%以上。
Description
技术领域
本发明属于有机合成技术领域,涉及3,4-二氢-12-苯基-2H-苯并[b]氧杂蒽-1,6,11(12H)-三酮的有机合成方法。
背景技术
苯并[b]氧杂蒽是一类具有重要的生理和药理活性的杂环化合物。具有抗微生物、抗炎、抗菌等活性。这一类化合物可作为染料用于激光技术和pH敏感荧光物质用于生物分子的显色剂。因此苯并[b]氧杂蒽衍生物一直是化学工作者和药物科学工作者关注的一个热点。具有1,4-萘醌结构也是具有抗真菌、抗微生物和抗癌活性的天然产物中广泛存在的结构单元。但对于具有1,4-萘醌结构的苯并[b]氧杂蒽衍生物的合成报道很少。有文献报道以芳醛和2-羟基-1,4-萘醌为原料在对甲基苯磺酸(p-TSA)催化下合成具有1,4-萘醌结构的苯并[b]氧杂蒽衍生物(Tisseh,Z.N.eta1.Dyes Pigm,2009,83:258-261),或以芳醛和2-羟基-1,4-萘醌为原料在醋酸和乙二醇的混合溶剂中通过微波辐射合成该类化合物(Chen,Y et al.J.Heterocyc.Chem.2008,45:931-934)。上述合成方法需要使用催化剂催化反应或使用专门的反应装置,反应过程复杂。而在离子液体中通过醛、2-羟基-1,4-萘醌和环状1,3-二羰基化合物为原料一步合成3,4-二氢-12-苯基-2H-苯并[b]氧杂蒽-1,6,11(12H)-三酮衍生物还未见报道。
发明内容
本发明的目的在于提供一种合成3,4-二氢-12-苯基-2H-苯并[b]氧杂蒽-1,6,11(12H)-三酮的方法:醛、2-羟基-1,4-萘醌和环状1,3-二羰基化合物为原料,按摩尔比1∶1∶1在离子液体(IL)中经三组分一锅法一步生成(如图1所示)。本发明在合成过程中引入离子液体,提供一种温和高效环境友好、应用范围广,产率高且反应介质可重复使用。
本发明通过下述方法实现的:在5毫升离子液体中加入1毫摩尔的醛,1毫摩尔的2-羟基-1,4-萘醌和1毫摩尔的环状1,3-二羰基化合物,在90℃下反应8-10小时,即得到相应的3,4-二氢12-苯基-2H-苯并[b]氧杂蒽-1,6,11(12H)-三酮类衍生物。
所述的离子液体为[Bmim]Br或[Bmim]BF4。
所述的醛为芳香醛、脂肪醛或杂环醛。
所述的环状1,3-二羰基化合物为1,3-环己二酮或5,5-二甲基-1,3-环己二酮。
所述的离子液体制备参见文献(Park,S.J.Org.Chem.2001,66:8395-8401)。
与文献中已有方法相比,本发明具有以下优点:
本发明在合成苯并[b]氧杂蒽衍生物的过程中引入离子液体,是一种绿色合成方法。离子液体具有蒸汽压低,毒性小、热稳定性好、不燃烧和不爆炸、溶解性能独特,反应产物分离简单等优点。且离子液体可循环使用,大大降低了成本。
具体实施方式
下面结合附图1及实施例对本发明作进一步描述。
实施例1:
3,4-二氢-3,3-二甲基-12-(4-氯苯基)-2H-苯并[b]氧杂蒽-1,6,11(12H)-三酮的制备:在5毫升离子液体[Bmim]Br中加入1毫摩尔的4-氯苯甲醛(0.14g),1毫摩尔的2-羟基-1,4-萘醌(0.17g)和1毫摩尔的5,5-二甲基-1,3-环己二酮(0.14g),在90℃下反应9小时,TLC跟踪监测,反应结束后,直接过滤,产物用少量水洗涤,干燥后用DMF/H2O重结晶即得到相应的3,4-二氢12-苯基-2H-苯并[b]氧杂蒽-1,6,11(12H)-三酮类衍生物(0.36g,产率86%)。本品为土黄色粉末,mp:247~248℃。
实施例2:
3,4-二氢-3,3-二甲基-12-(2-溴苯基)-2H-苯并[b]氧杂蒽-1,6,11(12H)-三酮的制备:在5毫升离子液体[Bmim]Br中加入1毫摩尔的2-溴苯甲醛(0.19g),1毫摩尔的2-羟基-1,4-萘醌(0.17g)和1毫摩尔的5,5-二甲基-1,3-环己二酮(0.14g),在90℃下反应8小时,TLC跟踪监测,反应结束后,直接过滤,产物用少量水洗涤,干燥后用DMF/H2O重结晶即得到相应的3,4-二氢12-(2-溴苯基)-2H-苯并[b]氧杂蒽-1,6,11(12H)-三酮类衍生物(0.38g,产率82%)。本品为黄色粉末,mp:275~277℃。
实施例3:
3,4-二氢-12-(4-氯苯基)-2H-苯并[b]氧杂蒽-1,6,11(12H)-三酮的制备:在5毫升离子液体[Bmim]Br中加入1毫摩尔的4-氯苯甲醛(0.14g),1毫摩尔的2-羟基-1,4-萘醌(0.17g)和1毫摩尔的1,3-环己二酮(0.11g),在90℃下反应9小时,TLC跟踪监测,反应结束后,直接过滤,产物用少量水洗涤,干燥后用DMF/H2O重结晶即得到相应的3,4-二氢-12-苯基-2H-苯并[b]氧杂蒽-1,6,11(12H)-三酮类衍生物(0.35g,产率89%)。本品为棕色粉末,mp:210-212℃。
实施例1-21的反应原料,反应条件及产率见表1。
表1实施例1-21的反应原料,反应条件及产率
表1中,实施例1-14中反应的环状1,3-二羰基化合物为5,5-二甲基-1,3-环己二酮,实施例15-21反应的环状1,3-二羰基化合物为1,3-环己二酮。
表2为实施例1中离子液体的循环使用结果。
表2离子液体的循环使用
编号 | 循环次数 | 产率 |
1 | 1 | 86 |
2 | 2 | 85 |
3 | 3 | 83 |
4 | 4 | 83 |
由表1和表2可知,本发明的方法原料易得,操作简单安全,反应条件温和、收率高,后处理简单,原子经济性高,而且离子液体能够重复使用,环境污染小,因而具有极大的实施价值和潜在社会经济效益。
Claims (5)
1.本发明涉及3,4-二氢-12-苯基-2H-苯并[b]氧杂蒽-1,6,11(12H)-三酮的合成,是以醛、2-羟基-1,4-萘醌和环状1,3-二羰基化合物为原料,经三组分一锅法一步反应生成。
2.按照权利要求(1)所述的苯并[b]氧杂蒽衍生物的合成方法,其特征是合成的反应条件是醛、2-羟基-1,4-萘醌和1,3-二羰基化合物在离子液体中反应,适宜的条件是常压、90℃和反应8~10小时,原料的摩尔比为醛∶2-羟基-1,4-萘醌∶1,3-二羰基化合物=1∶1∶1。
3.按照权利要求(1)所述的苯并[b]氧杂蒽衍生物的合成方法,其特征在于所述的离子液体为[Bmim]Br或[Bmim]BF4。
4.按照权利要求(1)所述的苯并[b]氧杂蒽衍生物的合成方法,其特征在于所述的醛为芳香醛、脂肪醛或杂环醛。
5.按照权利要求(1)所述的苯并[b]氧杂蒽衍生物的合成方法,其特征在于所述的环状1,3-二羰基化合物为1,3-环己二酮或5,5-二甲基-1,3-环己二酮。
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CN102850314A (zh) * | 2012-07-12 | 2013-01-02 | 盐城师范学院 | 双功能碱性离子液体水相催化苯并氧杂蒽衍生物的合成 |
CN102911151A (zh) * | 2012-07-12 | 2013-02-06 | 盐城师范学院 | 一种水相合成苯并氧杂蒽衍生物的方法 |
EP2690094A1 (en) * | 2012-07-24 | 2014-01-29 | Centro Atlantico del Medicamento S.A (Ceamed, S.A) | Fused quinonic compounds |
CN103664858A (zh) * | 2013-11-08 | 2014-03-26 | 盐城师范学院 | 一种合成苯并氧杂蒽衍生物的方法 |
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Cited By (8)
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CN102850314A (zh) * | 2012-07-12 | 2013-01-02 | 盐城师范学院 | 双功能碱性离子液体水相催化苯并氧杂蒽衍生物的合成 |
CN102911151A (zh) * | 2012-07-12 | 2013-02-06 | 盐城师范学院 | 一种水相合成苯并氧杂蒽衍生物的方法 |
CN102850314B (zh) * | 2012-07-12 | 2014-08-13 | 盐城师范学院 | 双功能碱性离子液体水相催化苯并氧杂蒽衍生物的合成 |
CN102911151B (zh) * | 2012-07-12 | 2014-10-22 | 盐城师范学院 | 一种水相合成苯并氧杂蒽衍生物的方法 |
EP2690094A1 (en) * | 2012-07-24 | 2014-01-29 | Centro Atlantico del Medicamento S.A (Ceamed, S.A) | Fused quinonic compounds |
WO2014016314A1 (en) * | 2012-07-24 | 2014-01-30 | Centro Atlantico Del Medicamento S.A (Ceamed, S.A) | Fused quinonic compounds |
US20150175585A1 (en) * | 2012-07-24 | 2015-06-25 | Centro Atlantico Del Medicamento S.A (Ceamed S.A.) | Fused quinonic compounds |
CN103664858A (zh) * | 2013-11-08 | 2014-03-26 | 盐城师范学院 | 一种合成苯并氧杂蒽衍生物的方法 |
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