CN106496009A - 可见光促进重氮盐、炔烃和醇串联加成羰基化反应 - Google Patents

可见光促进重氮盐、炔烃和醇串联加成羰基化反应 Download PDF

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CN106496009A
CN106496009A CN201610899442.3A CN201610899442A CN106496009A CN 106496009 A CN106496009 A CN 106496009A CN 201610899442 A CN201610899442 A CN 201610899442A CN 106496009 A CN106496009 A CN 106496009A
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alkoxy base
compounds according
aryl ketones
alkynes
base aryl
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钮腾飞
姜丁允
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Jiangnan University
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Jiangnan University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings

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Abstract

本发明目的是一种在中性条件下，通过可见光促进下四氟硼酸重氮盐、炔和醇串联加成反应，氧化生成α‑烷氧基化芳基酮类化合物。

Description

可见光促进重氮盐、炔烃和醇串联加成羰基化反应
技术领域
本发明涉及化工、医药、天然产品等技术领域羰基类化合物的有机合成，尤其是可见光促进下氧气参与的炔烃氧化生成α-烷氧基化芳基酮类化合物。
背景技术
寻找高效、温和、绿色的反应条件，发展新颖的化学反应，一直是有机化学家们孜孜以求的目标。芳基酮类化合物是一种重要的中间体，在药物合成、生物制药、材料科学领域都有着广泛的应用。近几年来，芳基酮类化合物的合成往往反应体系中会加入一些强酸、有毒的氧化剂等，基于此，寻找一条可持续合成发展方向，是化学工业绿色化进程中一个挑战性课题。
有鉴于此，本项目将发展基于可见光促进的下氧气参与的炔烃双官能化多组分串联反应，合成α-烷氧基化芳基酮类化合物，该合成方法反应温和，操作简单，无酸、无有毒氧化剂等。同时，为制备一些高附加值的精细化工中间体提供一条简洁高效、清洁绿色的捷径。
发明内容
本发明目的是一种在中性条件下，通过可见光促进下四氟硼酸重氮盐、炔和醇串联加成反应，氧化生成α-烷氧基化芳基酮类化合物。
本发明所提供的炔烃氧化生成α-烷氧基化芳基酮类化合物合成方法是：在反应器中，加入作为引发剂的四氟硼酸芳基重氮盐，作为催化剂的钌的配合物、炔烃、有机溶剂和氧气，在室温、5w蓝色LED灯照射下搅拌8-12h。反应产物通过柱色谱法和薄层色谱法进行产物的的分离纯化。
在一个优选实施方案中，所述四氟硼酸芳基重氮盐、炔烃、催化剂摩尔比为0.5:0.6～1:0.01。
在一个优选实施方案中，所述催化剂是Ru(bpy)3Cl·6H2O。
在一个优选实施方案中，所述四氟硼酸重氮盐是选自对甲氧基四氟硼酸重氮盐、对氟四氟硼酸重氮盐中的一种。
在一个优选实施方案中,所述炔烃是选自苯乙炔、对甲基苯乙炔、邻甲基苯乙炔、邻氟苯乙炔、对氯苯乙炔中的一种。
在一个优选实施方案中，在反应之前，用氧气置换反应器中的空气。
在一个优选实施方案中，所述灯为5w蓝色LED灯，波长为450纳米。。
在一个优选实施方案中，所述有机溶剂为甲醇、异丙醇和乙腈中的一种或多种。
本发明的优点在于：反应条件温和、操作简单、无酸无碱的中性环境以及无有毒氧化物。
附图说明
图1实验的反应方程；图2为本发明的实验机理图。
具体实施方法
实例1
在25ml的Schlenk反应管中加入0.5mmol对甲氧基四氟硼酸芳基重氮盐，0.01mmol催化剂三联吡啶氯化钌(Ⅱ)六水合物，加转子,用氧气置换管内空气，加入1mmol苯乙炔，加入2ml甲醇溶液，在5瓦蓝色LED灯照射下用磁力搅拌器搅拌12h，结束反应。反应产物通过柱色谱法和薄层色谱法进行各种产物的的分离纯化，分离得到产品。经计算，转化率为65％。
实例2
在25ml的Schlenk反应管中加入0.5mmol对甲氧基四氟硼酸芳基重氮盐，0.01mmol催化剂三联吡啶氯化钌(Ⅱ)六水合物，加转子,用氧气置换管内空气，加入1mmol邻甲基苯乙炔，再加入2ml甲醇溶液，在5瓦蓝色LED灯照射下用磁力搅拌器搅拌12h，结束反应。反应产物通过柱色谱法和薄层色谱法进行各种产物的的分离纯化，分离得到产品。经计算，转化率为72％。
实例3
在25ml的Schlenk反应管中加入0.5mmol对氟四氟硼酸芳基重氮盐，0.01mmol催化剂三联吡啶氯化钌(Ⅱ)六水合物，加转子,用氧气置换管内空气，加入1mmol苯乙炔，加入2ml甲醇溶液，在5瓦蓝色LED灯照射下用磁力搅拌器搅拌12h，结束反应。反应产物通过柱色谱法和薄层色谱法进行各种产物的的分离纯化，分离得到产品。经计算，转化率为69％。

Claims (9)

1.可见光促进的下氧气参与的炔烃双官能化多组分串联反应，氧化生成α-烷氧基芳基酮类化合物合成方法：在反应器中，加入作为引发剂的四氟硼酸芳基重氮盐，作为催化剂的钌的配合物、有机溶剂和氧气，在室温、5w蓝色LED灯照射下搅拌8-12h。其中所述催化剂为三联吡啶氯化钌(Ⅱ)六水合物，有机溶剂为甲醇或异丙醇。
2.根据权利1所述制备α-烷氧基化芳基酮类化合物的方法，其特征在于：以四氟硼酸重氮盐为引发剂。
3.根据权利1所述制备α-烷氧基化芳基酮类化合物的方法，其特征在于：以三联吡啶氯化钌(Ⅱ)六水合物为催化剂。
4.根据权利1所述制备α-烷氧基化芳基酮类化合物的方法，其特征在于：可见光为5瓦蓝色LED灯。
5.根据权利1所述制备α-烷氧基化芳基酮类化合物的方法，其特征在于：按摩尔比，催化剂：引发剂：炔烃＝0.01:0.5:1。
6.根据权利1所述制备α-烷氧基化芳基酮类化合物的方法，其特征在于：所述四氟硼酸重氮盐是选自对甲氧基四氟硼酸重氮盐、对氟四氟硼酸重氮盐中的一种。
7.根据权利1所述制备α-烷氧基化芳基酮类化合物的方法，其特征在于：所述炔烃是选自苯乙炔、对甲基苯乙炔、邻甲基苯乙炔、邻氟苯乙炔、对氯苯乙炔中的一种。
8.根据权利1所述制备α-烷氧基化芳基酮类化合物的方法，其特征在于：有机溶剂为甲醇、异丙醇和乙腈中的一种或多种。
9.根据权利1所述制备α-烷氧基化芳基酮类化合物的方法，其特征在于：反应前，用氧气置换管内的空气。
CN201610899442.3A 2016-10-14 2016-10-14 可见光促进重氮盐、炔烃和醇串联加成羰基化反应 Pending CN106496009A (zh)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108671961A (zh) * 2018-05-10 2018-10-19 三峡大学 一种钌配合物光催化剂，制备方法及其应用
CN109111541A (zh) * 2018-08-20 2019-01-01 江南大学 一种含叠氮基高分子聚合物的制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105753668A (zh) * 2016-03-11 2016-07-13 江南大学 可见光促进下氧气参与的炔烃绿色氧化羰基化反应

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105753668A (zh) * 2016-03-11 2016-07-13 江南大学 可见光促进下氧气参与的炔烃绿色氧化羰基化反应

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Title
TENG-FEI NIU等: "A visible-light-induced chemoselective radical/oxidative addition domino process to access α-chloro and α-alkoxy aryl ketones", 《CHEM. COMMUN.》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108671961A (zh) * 2018-05-10 2018-10-19 三峡大学 一种钌配合物光催化剂，制备方法及其应用
CN108671961B (zh) * 2018-05-10 2021-01-26 三峡大学 一种钌配合物光催化剂，制备方法及其应用
CN109111541A (zh) * 2018-08-20 2019-01-01 江南大学 一种含叠氮基高分子聚合物的制备方法

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