CN113336696B - 一种间位烯丙基芳香化合物的制备方法 - Google Patents

一种间位烯丙基芳香化合物的制备方法 Download PDF

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CN113336696B
CN113336696B CN202110634272.7A CN202110634272A CN113336696B CN 113336696 B CN113336696 B CN 113336696B CN 202110634272 A CN202110634272 A CN 202110634272A CN 113336696 B CN113336696 B CN 113336696B
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李刚
贾春起
吴妮妮
崔秀玲
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    • C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms

Abstract

一种间位烯丙基芳香化合物的制备方法，采用式芳香化合物和丙烯衍生物在钌催化剂氧化剂的作用下反应制备，所述的钌催化剂为三（三苯基膦）二氯化钌；所述氧化剂为过氧化二叔丁基醚，将芳香化合物、烯丙基化试剂、钌催化剂、氧化剂直接加入反应装置中，搅拌加热温度至120℃，在氮气保护下反应12小时，分离产物得到间位烯丙基芳香化合物。本制备方法便捷、安全、经济性好。

Description

一种间位烯丙基芳香化合物的制备方法
技术领域
本发明涉及芳香化合物的制备方法，特别涉及间位烯丙基芳香化合物的制备方法，属于化学技术领域。
背景技术
芳香化合物的选择性官能化反应是一类重要的有机合成反应，一直受到药物研发、材料科学和精细化工等领域的广泛关注。其中，芳烃的烯丙基化反应所制得的烯丙基芳香化合物可以作为天然产物和生物活性分子的结构骨架或者反应中间体，如黄樟素就是烯丙苯的衍生物。此外，烯丙基可以进一步发生多类化学反应，如氧化反应、复分解反应、偶联反应及亲电取代反应等。近几十年来，对芳烃进行烯丙基化的方法主要有三种：Friedel-Crafts烷基化反应、过渡金属催化的交叉偶联反应和芳环sp2碳-氢键活化反应。目前的各种制备方法反应步骤繁琐，效率低下。
发明内容
本发明的目的在于克服目前的间位烯丙基芳香化合物制备中存在的上述问题，提供一种间位烯丙基芳香化合物的制备方法。
为实现本发明的目的，采用了下述的技术方案：一种间位烯丙基芳香化合物的制备方法，所述的间位烯丙基芳香化合物为式Ⅲ所示的结构，所述的间位烯丙基芳香化合物采用式Ⅰ所示的芳香化合物和式Ⅱ所示的丙烯衍生物在钌催化剂和氧化剂的作用下反应制备， 反应式如下：
其中： R为氢或甲氧基或氯或溴；DG为2-吡啶基或2-嘧啶基或吡唑；所述的钌催化剂为三（三苯基膦）二氯化钌；所述氧化剂为过氧化二叔丁基醚，将芳香化合物、丙烯衍生物、钌催化剂、氧化剂直接加入反应装置中，搅拌加热温度至120℃，在氮气保护下反应12小时，分离产物得到间位烯丙基芳香化合物。
进一步的；所述的丙烯衍生物为芳香化合物摩尔数的15-25倍。
进一步的；所述的丙烯衍生物为环己烯或环戊烯或四甲基乙烯。
本发明的积极有益技术效果在于：本发明采用廉价易得的丙烯衍生物作为烯丙基化试剂，在钌催化作用下，直接与间位芳基C-H键C-H发生脱氢偶联反应，从而合成间位烯丙基芳香化合物，本制备方法便捷、安全、经济性好。
具体实施方式
为了更充分的解释本发明的实施，提供本发明的实施实例，这些实施实例仅仅是对本发明的阐述，不限制本发明的范围。本申请中的过氧化二叔丁基醚又称二叔丁基过氧化物。
实施例1：
在20mL耐压反应管中加入0.2mmol2-苯基吡啶， 4.0 mmol 环己烯， 0.02mmol 三(三苯基膦)二氯化钌， 0.4mmol过氧化二叔丁基醚，氮气条件下密封，加热到120℃反应，搅拌12小时，反应后，柱色谱分离，得目标产物27.3mg，产率为58%。
实施例2：
在20mL耐压反应管中加入0.2mmol2-对甲氧基苯基吡啶， 4.0 mmol 环己烯，0.02mmol三(三苯基膦)二氯化钌， 0.4mmol过氧化二叔丁基醚，氮气条件下密封，加热到120℃反应，搅拌12小时，反应后，柱色谱分离，得目标产物43.5mg，产率为82%。
实施例3：
在20mL耐压反应管中加入0.2mmol2-对甲氧基苯基吡唑， 4.0 mmol环己烯，0.02mmol)三(三苯基膦)二氯化钌， 0.4mmol过氧化二叔丁基醚，氮气条件下密封，加热到120℃反应，搅拌12小时，反应后，柱色谱分离，得目标产物39.1mg，产率为77%。
实施例4：
在20mL耐压反应管中加入0.2mmol)2-对氯苯基嘧啶， 4.0 mmol 环己烯，0.02mmol 三(三苯基膦)二氯化钌， 0.4mmol过氧化二叔丁基醚，氮气条件下密封，加热到120℃反应，搅拌12小时，反应后，柱色谱分离，得目标产物39.4mg，产率为73%。
实施例5：
在20mL耐压反应管中加入0.2mmol2-对溴苯基吡啶， 4.0 mmol 环戊烯，0.02mmol 三(三苯基膦)二氯化钌， 0.4mmol过氧化二叔丁基醚，氮气条件下密封，加热到120℃反应，搅拌12小时，反应后，柱色谱分离，得目标产物26.3mg，产率为44%。
实施例6：
在20mL耐压反应管中加入0.2mmol2-对甲氧基苯基吡唑， 4.0 mmol 四甲基乙烯，0.02mmol)三(三苯基膦)二氯化钌， 0.4mmol过氧化二叔丁基醚，氮气条件下密封，加热到120℃反应，搅拌12小时，反应后，柱色谱分离，得目标产物29.9mg，产率为56%。
以下表一为采用本发明的技术方案合成的产物及对应的收率：
表一
在详细说明本发明的实施方式之后，熟悉该项技术的人士可清楚地了解，在不脱离上述申请专利范围与精神下可进行各种变化与修改，凡依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰，均属于本发明技术方案的范围，且本发明亦不受限于说明书中所举实例的实施方式。

Claims (2)

1. 一种间位烯丙基芳香化合物的制备方法，所述的间位烯丙基芳香化合物为式Ⅲ所示的结构，其特征在于：所述的间位烯丙基芳香化合物采用式Ⅰ所示的芳香化合物和式Ⅱ所示的丙烯衍生物在钌催化剂和氧化剂的作用下反应制备， 反应式如下：
其中： R为氢或甲氧基或氯或溴；DG为2-吡啶基或2-嘧啶基或吡唑；所述的钌催化剂为三（三苯基膦）二氯化钌；所述氧化剂为过氧化二叔丁基醚，所述的丙烯衍生物为环己烯或环戊烯或四甲基乙烯，将芳香化合物、丙烯衍生物、钌催化剂、氧化剂直接加入反应装置中，搅拌加热温度至120℃，在氮气保护下反应12小时，分离产物得到间位烯丙基芳香化合物。
2.根据权利要求1所述的一种间位烯丙基芳香化合物的制备方法，其特征在于：式Ⅱ所示丙烯衍生物为式Ⅰ所示的芳香化合物摩尔数的15-25倍。
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JPH05286932A (ja) * 1991-03-27 1993-11-02 Kawaken Fine Chem Co Ltd インドール類の製造方法
CN110818620A (zh) * 2019-11-17 2020-02-21 安阳师范学院 一种间位芳香醛的制备方法

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Li B等.Ru-Catalyzed Meta-C-H Benzylation of Arenes with Toluene Derivatives.《ORGANIC LETTERS》.2017,第19卷(第15期),第3950-3953页. *
Li GB等.Ligand-Enabled Regioselectivity in the Oxidative Cross-coupling of Arenes with Toluenes and Cycloalkanes Using Ruthenium Catalysts: Tuning the Site-Selectivity from the ortho to meta Positions.《ACS CATALYSIS》.2017,第7卷(第6期),第4138-4143页. *
田万发等.配体促进的过渡金属催化芳香远程meta-C-H键官能化反应研究进展.《有机化学》.2019,第40卷第625-644页. *

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