CN106588695A - 一种一锅法合成取代丙烯腈的方法 - Google Patents

一种一锅法合成取代丙烯腈的方法 Download PDF

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CN106588695A
CN106588695A CN201611106002.4A CN201611106002A CN106588695A CN 106588695 A CN106588695 A CN 106588695A CN 201611106002 A CN201611106002 A CN 201611106002A CN 106588695 A CN106588695 A CN 106588695A
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acrylonitrile
pot process
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alkali
oxygen atmosphere
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毛武涛
鲍克燕
刘光印
陈宝宽
王炜博
李亭
张旭
李娜
谢海泉
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Nanyang Normal University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/16—Preparation of carboxylic acid nitriles by reaction of cyanides with lactones or compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • 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
    • C07D213/24—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 substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/57—Nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals

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Abstract

本发明提出了一种一锅法合成取代丙烯腈的方法，其是以0.01mol‑1.0mol的芳基取代甲醇或杂环取代甲醇为原料，以浓度为0.2‑2.0 mol/L的乙腈为溶剂，在碱的作用下得到β‑芳基取代的丙烯腈。本发明在氧气氛下，加入半导体光催化剂，光照辅助反应，能大幅提高反应速率和收率；本发明的反应原料易得、简便，产物具有重要的应用价值。

Description

一种一锅法合成取代丙烯腈的方法
技术领域
本发明涉及丙烯腈，具体涉及一种一锅法合成取代丙烯腈的方法，是指一种制备β-取代丙烯腈的方法。
背景技术
β-取代的丙烯腈是一类重要的化工原料和医药中间体(PCT专利，WO2004058253；US20140275179)，可以用来制备α,β-二羟基取代的腈类化合物，制备环氧衍生物，制备私单做类衍生物等。还是β-取代的丙烯腈特别是β-芳基取代的丙烯腈通常由以下几种方法合成：一、以碘苯或苯硼酸和丙烯腈为主要原料通过偶联反应制备，二、首先利用偶联反应制备β-芳基取代的丙烯醛，进一步制备对应的羟肟酸，最后通过脱水制备β-芳基取代的丙烯醛，三、以β-芳基取代的丙烯酰胺为原料，利用脱水剂脱水制备对用的产物，四、以苯甲醛为主要原料，通过和魏悌锡试剂反应制备对应的产物。以上反应要么步骤多路线长、工艺繁杂，要么试剂复杂，副产物多。
说明内容
本发明所要解决的技术问题是提供一种原料易得、简便、收率高的一锅合成β-取代丙烯腈的方法，其具有重要的应用价值。
为解决上述技术问题，本发明所采取的技术方案是：一种一锅法合成取代丙烯腈的方法，是以0.01mol-1.0mol的芳基取代甲醇或杂环取代甲醇为原料，以浓度为0.2-2.0mol/L的乙腈为溶剂，在碱的作用下得到β-芳基取代的丙烯腈，碱的用量为底物量的2.0-5.0倍；在氧气氛下，加入半导体光催化剂，光照辅助反应，能大幅提高反应速率和收率；反应式为：
进一步地，在氧气氛下室温搅拌15小时，过滤除去固体，减压浓缩，粗产品经制备薄层色谱纯化，展开剂为石油醚：乙酸乙酯＝20:1的混合物，得到淡黄色油状物。
所述的芳基为各种取代的苯基或萘基，所述的杂环为各种取代的吡啶、呋喃、噻吩、吡咯、喹啉或吲哚，所述碱为氢氧化钠、氢氧化钾、乙醇钠或碳酸钾，所述半导体催化剂为氧化钨或二氧化钛。
本发明采用上述技术方案所设计的一种一锅法合成取代丙烯腈的方法，反应原料易得、简便，反应收率高，产物具有重要的应用价值。
具体实施方式
本发明一种一锅法合成取代丙烯腈的方法，是以芳基取代甲醇或杂环取代甲醇为主要原料，乙腈为溶剂，在适量碱的作用下既可以得到β-芳基取代的丙烯腈。在氧气氛下，加入半导体光催化剂，光照辅助反应，可以大幅提高反应速率和收率。
所述的芳基为各种取代的苯基、萘基等，所述的杂环为各种取代的吡啶、呋喃、噻吩、吡咯、喹啉、吲哚等，所述的碱为氢氧化钠、氢氧化钾、乙醇钠、碳酸钾等，所述的半导体催化剂为氧化钨、二氧化钛等。
实施例1
向25毫升圆底烧瓶中加入苯甲醇108毫克，乙腈4毫升，氢氧化钠80毫克，氧气氛下室温搅拌15小时，过滤除去固体，减压浓缩，粗产品经制备薄层色谱纯化，展开剂为石油醚：乙酸乙酯＝20:1的混合物，得到淡黄色油状物，收率46％，产品经1H NMR、13C NMR、HR-MS表征，1H NMR(400MHz,CDCl3)δ7.43(m,5H),7.40(d,J＝9.0Hz,1H),5.88(d,J＝16.7Hz,1H).13C NMR(100MHz,CDCl3)δ150.59,133.56,131.21,129.13,127.36,118.11,96.38.HR-MS,Calcd for C9H7N[M+H]+130.0651,found 130.0648。
实施例2
向25毫升圆底烧瓶中加入1毫摩尔苯甲醇108毫克，乙腈4毫升，氢氧化钠120毫克，氧气氛下室温搅拌15小时，过滤除去固体，减压浓缩，粗产品经制备薄层色谱纯化，展开剂为石油醚：乙酸乙酯＝20:1的混合物，得到淡黄色油状物，收率72％，产品经1H NMR、13CNMR、HR-MS表征，1H NMR(400MHz,CDCl3)δ7.43(m,5H),7.40(d,J＝9.0Hz,1H),5.88(d,J＝16.7Hz,1H).13C NMR(100MHz,CDCl3)δ150.59,133.56,131.21,129.13,127.36,118.11,96.38.HR-MS,Calcd for C9H7N[M+H]+130.0651,found 130.0648。
实施例3
向25毫升圆底烧瓶中加入1毫摩尔苯甲醇108毫克，乙腈5毫升，氢氧化钠160毫克，氧气氛下50摄氏度搅拌15小时，过滤除去固体，减压浓缩，粗产品经制备薄层色谱纯化，展开剂为石油醚：乙酸乙酯＝20:1的混合物，得到淡黄色油状物，收率90％，产品经1H NMR、13CNMR、HR-MS表征，1H NMR(400MHz,CDCl3)δ7.43(m,5H),7.40(d,J＝9.0Hz,1H),5.88(d,J＝16.7Hz,1H).13C NMR(100MHz,CDCl3)δ150.59,133.56,131.21,129.13,127.36,118.11,96.38.HR-MS,Calcd for C9H7N[M+H]+130.0651,found 130.0648。
实施例4
向25毫升圆底烧瓶中加入1毫摩尔苯甲醇108毫克，乙腈5毫升，氢氧化钠200毫克，氧气氛下50摄氏度搅拌15小时，过滤除去固体，减压浓缩，粗产品经制备薄层色谱纯化，展开剂为石油醚：乙酸乙酯＝20:1的混合物，得到淡黄色油状物，收率92％，产品经1H NMR、13CNMR、HR-MS表征，1H NMR(400MHz,CDCl3)δ7.43(m,5H),7.40(d,J＝9.0Hz,1H),5.88(d,J＝16.7Hz,1H).13C NMR(100MHz,CDCl3)δ150.59,133.56,131.21,129.13,127.36,118.11,96.38.HR-MS,Calcd for C9H7N[M+H]+130.0651,found 130.0648。
实施例5
向25毫升圆底烧瓶中加入1毫摩尔苯甲醇108毫克，乙腈5毫升，氢氧化钠100毫克，蓝灰色氧化钨纳米片(自制)，光照(12W LED灯)室温搅拌15小时，过滤除去固体，减压浓缩，粗产品经制备薄层色谱纯化，展开剂为石油醚：乙酸乙酯＝20:1的混合物，得到淡黄色油状物，收率85％，产品经1H NMR、13C NMR、HR-MS表征，1H NMR(400MHz,CDCl3)δ7.43(m,5H),7.40(d,J＝9.0Hz,1H),5.88(d,J＝16.7Hz,1H).13C NMR(100MHz,CDCl3)δ150.59,133.56,131.21,129.13,127.36,118.11,96.38.HR-MS,Calcd for C9H7N[M+H]+130.0651,found130.0648。
实施例6
向25毫升圆底烧瓶中加入1毫摩尔苯甲醇108毫克，乙腈5毫升，氢氧化钾4毫摩尔，氧气氛下50摄氏度搅拌15小时，过滤除去固体，减压浓缩，粗产品经制备薄层色谱纯化，展开剂为石油醚：乙酸乙酯＝20:1的混合物，得到淡黄色油状物，收率91％。
实施例7
向25毫升圆底烧瓶中加入1毫摩尔苯甲醇108毫克，乙腈5毫升，乙醇钠4毫摩尔，氧气氛下50摄氏度搅拌15小时，过滤除去固体，减压浓缩，粗产品经制备薄层色谱纯化，展开剂为石油醚：乙酸乙酯＝20:1的混合物，得到淡黄色油状物，收率63％。
实施例8
向25毫升圆底烧瓶中加入1毫摩尔苯甲醇108毫克，乙腈5毫升，乙醇钠4毫摩尔，氧气氛下50摄氏度搅拌15小时，过滤除去固体，减压浓缩，粗产品经制备薄层色谱纯化，展开剂为石油醚：乙酸乙酯＝20:1的混合物，得到淡黄色油状物，收率7％。
实施例8
以实施例4类似的条件，拓展应用范围，具体的结果见表1所示。
表1：方法普适性拓展

Claims (3)

1.一种一锅法合成取代丙烯腈的方法，其特征是以0.01mol-1.0mol的芳基取代甲醇或杂环取代甲醇为原料，以浓度为0.2-2.0mol/L的乙腈为溶剂，在碱的作用下得到β-芳基取代的丙烯腈，碱的用量为底物量的2.0-5.0倍；在氧气氛下，加入半导体光催化剂，光照辅助反应，能大幅提高反应速率和收率；反应式为：
2.根据权利要求1所述的一种一锅法合成取代丙烯腈的方法，其特征是在氧气氛下室温搅拌15小时，过滤除去固体，减压浓缩，粗产品经制备薄层色谱纯化，展开剂为石油醚：乙酸乙酯＝20:1的混合物，得到淡黄色油状物。
3.根据权利要求1或2所述的一种一锅法合成取代丙烯腈的方法，其特征是所述的芳基为各种取代的苯基或萘基，所述的杂环为各种取代的吡啶、呋喃、噻吩、吡咯、喹啉或吲哚，所述碱为氢氧化钠、氢氧化钾、乙醇钠或碳酸钾，所述半导体催化剂为氧化钨或二氧化钛。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115215762A (zh) * 2022-08-08 2022-10-21 陕西师范大学 一种由醇合成脂肪腈的方法

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CN105498748A (zh) * 2015-11-25 2016-04-20 南阳师范学院 一种钨氧化物纳米片及其制备方法和催化应用

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WO2003053344A2 (en) * 2001-12-10 2003-07-03 Bristol-Myers Squibb Company Substituted 2-methyl-benzimidazole respiratory syncytial virus antiviral agents
CN101531575A (zh) * 2009-04-24 2009-09-16 中国科学院化学研究所 利用光催化选择性氧化一级醇或二级醇制备醛或酮的方法
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* Cited by examiner, † Cited by third party
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CN115215762A (zh) * 2022-08-08 2022-10-21 陕西师范大学 一种由醇合成脂肪腈的方法
CN115215762B (zh) * 2022-08-08 2024-02-02 陕西师范大学 一种由醇合成脂肪腈的方法

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