CN107915700A - 7‑甲氧基香豆素的一种合成方法 - Google Patents

7‑甲氧基香豆素的一种合成方法 Download PDF

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Publication number
CN107915700A
CN107915700A CN201610882227.2A CN201610882227A CN107915700A CN 107915700 A CN107915700 A CN 107915700A CN 201610882227 A CN201610882227 A CN 201610882227A CN 107915700 A CN107915700 A CN 107915700A
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synthetic method
acid
ayapanin
phosphotungstic acid
methoxy
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杨绍祥
田红玉
刘永国
孙宝国
郝颜峰
王嘉琳
王皓
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Beijing Technology and Business University
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Beijing Technology and Business University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
    • C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
    • C07D311/16—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 7

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明公开了一种7‑甲氧基香豆素的一种合成方法，以间甲氧基苯酚和3，3‑二乙氧基丙酸乙酯为原料，在磷钨酸催化下，一步反应合成7‑甲氧基香豆素。本发明与现有的方法相比，合成步骤少、环境污染小。

Description

7-甲氧基香豆素的一种合成方法
技术领域
本发明涉及7-甲氧基香豆素的一种合成方法，具体是以间甲氧基苯酚和3，3-二乙氧基丙酸乙酯为原料，在磷钨酸催化下，一步反应合成7-甲氧基香豆素。
背景技术
7-甲氧基香豆素是一种重要的香豆素类化合物，具有一定的生物活性，可用于农药、医药等领域，可作为合成其他高活性香豆素类化合物的重要中间体，如蛇床子素、6，7-二甲氧基香豆素。
7-甲氧基香豆素的合成方法主要有：(1)以间苯二酚为起始原料，经甲酰化得2，4-二羟基苯甲醛、然后甲基化得2-羟基-4-甲氧基苯甲醛、最后环化得7-甲氧基香豆素；(2)以间苯二酚为起始原料，经甲酰化2，4-二羟基苯甲醛、然后环化得7-羟基香豆素、最后甲基化得7-甲氧基香豆素。反应中甲酰化主要采用Vilsmeier-Haack反应、Reimer-Tiemann反应、Gattermann反应；甲基化主要以碳酸二甲酯或硫酸二甲酯作为甲基化试剂；环化主要采用Perkin反应、Pechmann反应、Wittig反应、Knoevenagal反应。
两条主要的合成路线均需要经过三步反应才能制得7-甲氧基香豆素。为了使反应路线更加简捷，反应条件更加绿色化，广大的研究人员将研究的重点转移到采用新型的催化剂进行催化反应，使7-甲氧基香豆素的合成更加符合当今社会发展对环境友好化的要求。
发明内容
本发明目的是克服上述7-甲氧基香豆素合成方法的缺点，提供一种工艺步骤少、无环境污染的新合成方法。
为实现上述的目的，本发明采用的技术方案是，以间甲氧基苯酚和3，3-二乙氧基丙酸乙酯为原料，在磷钨酸催化下，采用无溶剂化反应，加热一步反应合成7-甲氧基香豆素，合成路线如下式所示。
本发明中所述磷钨酸为Wells-Dawson型磷钨酸、Keggin型磷钨酸、杂多酸H3PW12O40、杂多酸H2P6W18O42、磷钨盐Ag3PW12O40。所述反应温度为40℃-150℃。所述催化剂磷钨酸用量为10％-0.1％。所述反应时间为1小时-10小时。
本发明与现有的方法相比，工艺步骤少、反应时间短、无环境污染。
具体实施方式
实施例1：
在25mL圆底烧瓶中分别加入1.24g(10mmol)间甲氧基苯酚，催化剂Wells-Dawson型磷钨酸0.24g(0.1mmol)，1.90g(10mmol)甲酰乙酸乙酯，混匀后90℃加热3小时，甲苯萃取。旋蒸，除去溶剂，柱层析分离提纯，得0.88g白色固体，产率50.1％。
实施例2：
在25mL圆底烧瓶中分别加入1.24g(10mmol)间甲氧基苯酚，催化剂Keggin型磷钨酸0.24g(0.1mmol)，1.90g(10mmol)甲酰乙酸乙酯，混匀后90℃加热3小时，甲苯萃取。旋蒸，除去溶剂，柱层析分离提纯，得0.81g白色固体，产率46.0％。
本专业领域的普通技术人员可以根据本发明方法，参照上述实施例，对催化剂磷钨酸的选择及其用量、反应温度、反应时间在本发明的范围内任意选取，给出一种或多种具体的合成方法，均在本发明的保护范围内。
产物经过核磁氢谱表征。
1H NMR(300MHz，CDCl3)δ：3.87(3H，s，-OCH3)，6.26(1H，d，J＝9.3Hz，-CH＝C)，6.82-6.87(2H，m，Ar-H)，7.37(1H，d，J＝8.4Hz，Ar-H)，7.65(1H，d，J＝9.6Hz，-C＝CH)。

Claims (5)

1.一种7-甲氧基香豆素的合成方法，其特征是：以间甲氧基苯酚和3,3-二乙氧基丙酸乙酯为原料，在磷钨酸催化下，一步反应合成7-甲氧基香豆素。
2.根据权利要求1所述的合成方法，其特征是：所述磷钨酸为Wells-Dawson型磷钨酸、Keggin型磷钨酸、杂多酸H3PW12O40、杂多酸H2P6W18O42、磷钨盐Ag3PW12O40。
3.根据权利要求1所述的合成方法，其特征是：所述反应温度为40℃-150℃。
4.根据权利要求1所述的合成方法，其特征是：所述催化剂磷钨酸用量为10％-0.1％。
5.根据权利要求1所述的合成方法，其特征是：所述反应时间为1小时-10小时。
CN201610882227.2A 2016-10-10 2016-10-10 7‑甲氧基香豆素的一种合成方法 Pending CN107915700A (zh)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111436438A (zh) * 2020-04-24 2020-07-24 中国科学院兰州化学物理研究所 一种对植物病原真菌具有抑制活性的香豆素化合物的应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104356103A (zh) * 2014-11-26 2015-02-18 深圳波顿香料有限公司 一种6,7-二甲氧基香豆素的合成方法
CN105481813A (zh) * 2015-11-27 2016-04-13 北京工商大学 6-甲基香豆素的一种合成方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104356103A (zh) * 2014-11-26 2015-02-18 深圳波顿香料有限公司 一种6,7-二甲氧基香豆素的合成方法
CN105481813A (zh) * 2015-11-27 2016-04-13 北京工商大学 6-甲基香豆素的一种合成方法

Non-Patent Citations (1)

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MORINA ADFA ET AL.: "Antitermite Activities of Coumarin Derivatives and Scopoletin from Protium javanicum Burm. f.", 《J CHEM ECOL》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111436438A (zh) * 2020-04-24 2020-07-24 中国科学院兰州化学物理研究所 一种对植物病原真菌具有抑制活性的香豆素化合物的应用

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