CN107253894B - 卤代芳香化合物的羟基化方法 - Google Patents

卤代芳香化合物的羟基化方法 Download PDF

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CN107253894B
CN107253894B CN201710317238.0A CN201710317238A CN107253894B CN 107253894 B CN107253894 B CN 107253894B CN 201710317238 A CN201710317238 A CN 201710317238A CN 107253894 B CN107253894 B CN 107253894B
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王德平
许志锋
张复兴
李薇
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Hengyang Normal University
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Abstract

本发明涉及一种卤代芳香化合物的羟基化方法，该方法以2‑吡啶酮化合物为配体添加剂，以CuI作为催化剂，在相转移催化剂和溶剂的存在下，即可实现MOH与卤代芳香化合物的羟基化反应在温和条件下进行，且反应产率高，底物适用范围广。与文献中报道的同类型反应相比，本发明的方法反应条件温和，产率很高，有很好的应用前景。碘代芳香化合物的羟基化反应在水溶液中90℃就能进行且获得高产率的羟基化产物，反应的温度相比文献中的报道平均可以降低约30℃；溴代芳香化合物在水溶液中羟基化反应在120℃就能进行，反应温度相比文献中的报道平均可以降低约20℃。

Description

卤代芳香化合物的羟基化方法
技术领域
本发明涉及化学合成技术领域，特别是涉及一种卤代芳香化合物的羟基化方法。
背景技术
乌尔曼反应(Ullmann,F.ber Dtsch.Chem.Ges.1903,36,2382.)经过很长时间的发展，已经实现了工业化生产(Lindley,J.Tetrahedron 1984,40,1433)。但传统的乌尔曼偶联反应在高温、高极性溶剂条件下进行，而且需要当量或过量的铜试剂，因此，乌尔曼反应的应用受到了很大的限制(Lindley,J.Tetrahedron 1984, 40,1433)。近年来使用钯催化剂((a)Yang,B.H.；Buchwald,S.L.J. Organomet.Chem.1999,576(1-2),125-146.(b)Hartwig,J.F.Angew.Chem.,Int. Ed.Engl.1998,37,2046-2067)，使该反应得以在较温和的条件下进行。
但是，使用钯催化剂仍然存在着很多限制，比如含有某些特定官能团的底物很难反应，钯试剂及其共催化的配体价格昂贵，同时，钯催化该反应需要在相对昂贵的有机溶剂中进行。
发明内容
基于此，本发明提供了一种卤代芳香化合物的羟基化方法，该方法的反应条件温和，产率高，底物适用范围广。
具体技术方案如下：
一种卤代芳香化合物的羟基化方法，包括以下步骤：在碘化亚铜、配体、相转移催化剂PTS和溶剂的存在下，卤代芳香化合物Ar-X与碱MOH反应，即得羟基化产物Ar-OH，反应通式I如下:
Figure BDA0001286425560000011
其中，Ar为芳香环，X为卤素；
所述配体为2-吡啶酮类化合物，具有式II所示结构：
Figure BDA0001286425560000021
其中，R2选自：C1-C6烷基，芳基，或者与R3形成五～七元环状烷烃；
R3选自：H，C1-C6烷基，或者与R2形成五～七元环状烷烃。
在其中一些实施例中，所述2-吡啶酮类化合物为6,7-二氢喹啉-8(5H)-酮，甲基-2-吡啶基酮，苯基-2-吡啶基酮或皮考啉醛。
在其中一些实施例中，Ar为被一个或多个R1取代的芳香环，R1选自：H, -NO2，-COOH，乙酰基，甲醛基，卤素，C1-C6烷基，羟基取代的C1-C6烷基， C1-C6烷氧基，或芳基。
在其中一些实施例中，Ar为2-位R1取代的、3-位R1取代的、4-位R1取代的、2,5-位R1二取代的、或2,6-位R1二取代的芳香环，所述芳香环为苯、萘或者含氮原子的五～六元芳香杂环。
在其中一些实施例中，MOH选自：氢氧化钠，氢氧化钾，氢氧化铜，氢氧化铯，四丁基氢氧化铵，四甲基氢氧化铵，四乙基氢氧化铵。
在其中一些实施例中，MOH选自氢氧化钠，氢氧化钾，氢氧化铯，四丁基氢氧化铵，四乙基氢氧化铵。
在其中一些实施例中，所述溶剂为水，二甲基亚砜，N’N-二甲基甲酰胺， N’N-二甲基乙酰胺，或者二甲基亚砜与水的混合溶液。
在其中一些实施例中，所述溶剂为水。
在其中一些实施例中，X为碘或者溴。
在其中一些实施例中，所述相转移催化剂PTS为四丁基卤化铵。
在其中一些实施例中，所述四丁基卤化铵为四丁基溴化铵，四丁基氯化铵，或者四丁基氟化铵。
在其中一些实施例中，所述反应的温度为50-150℃。
在其中一些实施例中，碘代芳香化合物与碱MOH反应的温度为60～100℃，溴代芳香化合物与碱MOH反应的温度为90～145℃。
在其中一些实施例中，碘代芳香化合物与碱MOH反应的温度为70～95℃，溴代芳香化合物与碱MOH反应的温度为110～140℃
在其中一些实施例中，所述碘化亚铜与卤代芳香化合物Ar-X的摩尔比为 0.01～0.25:1；所述配体与碘化亚铜的摩尔比为1～4:1；所述碱MOH与卤代芳香化合物Ar-X的摩尔比为1.2～30:1；所述相转移催化剂PTS与卤代芳香化合物Ar-X的摩尔比为0.1～0.5:1。
在其中一些实施例中，所述碘化亚铜与卤代芳香化合物Ar-X的摩尔比为 0.03～0.2:1；所述配体与碘化亚铜的摩尔比为1～3:1；所述碱MOH与卤代芳香化合物Ar-X的摩尔比为1.5～20:1；所述相转移催化剂PTS与卤代芳香化合物 Ar-X的摩尔比为0.1～0.3:1。
在其中一些实施例中，所述碘化亚铜与卤代芳香化合物Ar-X的摩尔比为 0.04～0.06:1；所述配体与碘化亚铜的摩尔比为1.5～2.5:1；所述碱MOH与卤代芳香化合物Ar-X的摩尔比为4～6:1；所述相转移催化剂PTS与卤代芳香化合物 Ar-X的摩尔比为0.15～0.25:1。
本发明的卤代芳香化合物的羟基化方法具有以下优点和有益效果：
本发明的卤代芳香化合物的羟基化方法，以2-吡啶酮类化合物为配体添加剂，以CuI作为催化剂，能很好地促进卤代芳香化合物的羟基化反应，使MOH 与卤代芳香化合物的羟基化反应得以在温和条件下进行，特别是以水为溶剂的条件下具有很好的反应效果，能获得高产率的羟基化产物。
与文献中报道的同类型反应相比，本发明的方法反应条件温和，产率很高，有很好的应用前景。碘代芳香化合物的羟基化反应在水溶液中90℃就能进行且获得高产率的羟基化产物，反应的温度相比文献中的报道平均可以降低约30℃；溴代芳香化合物在水溶液中羟基化反应在120℃就能进行，反应温度相比文献中的报道平均可以降低约20℃，反应条件非常温和。
本发明的方法以该2-吡啶酮类化合物作为配体，可以促使许多含有各种官能团的卤代芳香化合物发生该类乌尔曼类羟基化反应，反应底物的适用范围很广。
本发明的羟基化反应所使用的催化剂为CuI，该催化剂价格便宜，易得；所使用的配体2-吡啶酮类化合物在空气中稳定，且廉价易得。
具体实施方式
以下结合具体实施例对本发明的卤代芳香化合物的羟基化方法做进一步详细的阐述。
实施例1 4-甲氧基苯酚的制备
Figure BDA0001286425560000041
在一个一端密封的反应管内，加入234mg对甲氧基碘苯(MW＝234,1.0 mmol)，然后依次加入280mg KOH(MW＝56,5mmol),14.7mg 6,7-二氢喹啉-8(5H)-酮(MW＝147,0.1mmol)，9.5mg CuI(MW＝190,0.05mmol)，64mg四丁基溴化铵(TBAB)(MW＝320,0.2mmol)和1mL水，在氩气或氮气保护下，于90℃搅拌反应24h，待反应液冷却后，加入5毫升30％的盐酸，接着用30mL乙酸乙酯分三次萃取反应混合液，合并萃取液，干燥，减压蒸馏，过硅胶柱分离(淋洗液为石油醚:乙酸乙酯＝3:1)，得到115mg产物4-甲氧基苯酚，产率93％。
Figure BDA0001286425560000042
1H NMR(CDCl3)δ6.79(m,4H),5.88(br,1H),3.77(s,3H)；13C NMR(CDCl3) δ153.5,149.5,116.1,114.9,55.9.
实施例2 4-甲氧基苯酚的制备
Figure BDA0001286425560000043
按照实施例1所述的方法，不同在于所用碱为NaOH，用NaOH200mg与 4-甲氧基碘苯(234mg,1.0mmol)搅拌反应24h。粗产物经柱层析(石油醚:乙酸乙酯＝3:1)提纯，产率：81％；
1H NMR(CDCl3)δ6.79(m,4H),5.88(br,1H),3.77(s,3H)；13C NMR(CDCl3) δ153.5,149.5,116.1,114.9,55.9.
实施例3 4-甲氧基苯酚的制备
Figure BDA0001286425560000051
按照实施例1所述的方法，不同在于所用碱为CsOH，用CsOH600mg与 4-甲氧基碘苯(234mg,1.0mmol)搅拌反应24h。粗产物经柱层析(石油醚:乙酸乙酯＝3:1)提纯，产率：96％；
1H NMR(CDCl3)δ6.79(m,4H),5.88(br,1H),3.77(s,3H)；13C NMR(CDCl3) δ153.5,149.5,116.1,114.9,55.9.
实施例4 4-甲氧基苯酚的制备
Figure BDA0001286425560000052
按照实施例1所述的方法，不同在于所用碱为nBu4NOH，用nBu4NOH 1.29g 与4-甲氧基碘苯(234mg,1.0mmol)搅拌反应24h。粗产物经柱层析(石油醚: 乙酸乙酯＝3:1)提纯，产率：95％；
1H NMR(CDCl3)δ6.79(m,4H),5.88(br,1H),3.77(s,3H)；13C NMR(CDCl3) δ153.5,149.5,116.1,114.9,55.9.
实施例5 4-甲氧基苯酚的制备
Figure BDA0001286425560000061
按照实施例1所述的方法，不同在于所用碱为nEt4NOH，用nEt4NOH735mg 与4-甲氧基碘苯(234mg,1.0mmol)搅拌反应24h。粗产物经柱层析(石油醚: 乙酸乙酯＝3:1)提纯，产率：90％；
1H NMR(CDCl3)δ6.79(m,4H),5.88(br,1H),3.77(s,3H)；13C NMR(CDCl3) δ153.5,149.5,116.1,114.9,55.9.
实施例64-甲氧基苯酚的制备
Figure BDA0001286425560000062
按照实施例1所述的方法，不同在于用DMSO做反应溶剂，KOH280mg 与4-甲氧基碘苯(234mg,1.0mmol)搅拌反应24h。粗产物经柱层析(石油醚: 乙酸乙酯＝3:1)提纯，产率：41％；
1H NMR(CDCl3)δ6.79(m,4H),5.88(br,1H),3.77(s,3H)；13C NMR(CDCl3) δ153.5,149.5,116.1,114.9,55.9.
实施例7 4-甲氧基苯酚的制备
Figure BDA0001286425560000063
按照实施例1所述的方法，不同在于用DMSO/H2O＝0.8/0.2做反应溶剂， KOH280mg与4-甲氧基碘苯(234mg,1.0mmol)搅拌反应24h。粗产物经柱层析(石油醚:乙酸乙酯＝3:1)提纯，产率：61％；
1H NMR(CDCl3)δ6.79(m,4H),5.88(br,1H),3.77(s,3H)；13C NMR(CDCl3) δ153.5,149.5,116.1,114.9,55.9.
实施例8 4-甲氧基苯酚的制备
Figure BDA0001286425560000071
按照实施例1所述的方法，不同在于用DMSO/H2O＝0.5/0.5做反应溶剂， KOH280mg与4-甲氧基碘苯(234mg,1.0mmol)搅拌反应24h。粗产物经柱层析(石油醚:乙酸乙酯＝3:1)提纯，产率：81％；
1H NMR(CDCl3)δ6.79(m,4H),5.88(br,1H),3.77(s,3H)；13C NMR(CDCl3) δ153.5,149.5,116.1,114.9,55.9.
实施例9 4-甲氧基苯酚的制备
Figure BDA0001286425560000072
按照实施例1所述的方法，不同在于用DMSO/H2O＝0.2/0.8做反应溶剂， KOH280mg与4-甲氧基碘苯(234mg,1.0mmol)搅拌反应24h。粗产物经柱层析(石油醚:乙酸乙酯＝3:1)提纯，产率：89％；
1H NMR(CDCl3)δ6.79(m,4H),5.88(br,1H),3.77(s,3H)；13C NMR(CDCl3) δ153.5,149.5,116.1,114.9,55.9.
实施例10 4-甲氧基苯酚的制备
Figure BDA0001286425560000073
按照实施例1所述的方法，不同在于用甲基-2-吡啶基酮12.1mg做配体， KOH280mg与4-甲氧基碘苯(234mg,1.0mmol)搅拌反应24h。粗产物经柱层析(石油醚:乙酸乙酯＝3:1)提纯，产率：70％；
1H NMR(CDCl3)δ6.79(m,4H),5.88(br,1H),3.77(s,3H)；13C NMR(CDCl3) δ153.5,149.5,116.1,114.9,55.9.
实施例11 4-甲氧基苯酚的制备
Figure BDA0001286425560000081
按照实施例1所述的方法，不同在于用苯基-2-吡啶基酮18.3mg做配体， KOH280mg与4-甲氧基碘苯(234mg,1.0mmol)搅拌反应24h。粗产物经柱层析(石油醚:乙酸乙酯＝3:1)提纯，产率：60％；
1H NMR(CDCl3)δ6.79(m,4H),5.88(br,1H),3.77(s,3H)；13C NMR(CDCl3) δ153.5,149.5,116.1,114.9,55.9.
实施例12 4-甲氧基苯酚的制备
Figure BDA0001286425560000082
按照实施例1所述的方法，不同在于用皮考啉醛10.7mg做配体，KOH 280mg与4-甲氧基碘苯(234mg,1.0mmol)搅拌反应24h。粗产物经柱层析(石油醚:乙酸乙酯＝3:1)提纯，产率：21％；
1H NMR(CDCl3)δ6.79(m,4H),5.88(br,1H),3.77(s,3H)；13C NMR(CDCl3) δ153.5,149.5,116.1,114.9,55.9.
实施例13苯酚的制备
Figure BDA0001286425560000083
按照实施例1所述的方法，不同在于卤代芳香化合物为碘苯(204mg,1.0 mmol)。粗产物经柱层析(石油醚:乙酸乙酯＝4:1)提纯，产率：90％；
1H NMR(CDCl3)δ7.32(t,J＝7.2Hz,2H),7.02(t,J＝7.2Hz,1H),6.91(d,J＝7.2Hz,2H)；13C NMR(CDCl3)δ155.2,129.7,120.8,115.3.
实施例14 1-萘酚的制备
Figure BDA0001286425560000091
按照实施例1所述的方法，不同在于卤代芳香化合物为1-碘萘(254mg,1.0 mmol)。粗产物经柱层析(石油醚:乙酸乙酯＝4:1)提纯，产率：89％；
1H NMR(CDCl3)δ8.23(m,1H),7.86(m,1H),7.54(m,3H),7.35(t,J＝7.6Hz, 1H),6.83(q,J＝7.6,0.8Hz,1H),5.39(br,1H)；13C NMR(CDCl3)δ151.3,134.7, 127.7,126.4,125.8,125.3,124.3,121.5,120.7,108.6.
实施例15 4-氟苯酚的制备
Figure BDA0001286425560000092
按照实施例1所述的方法，不同在于卤代芳香化合物为4-氟碘苯(222mg,1.0mmol)。粗产物经柱层析(石油醚:乙酸乙酯＝5:1)提纯，产率：91％；
1H NMR(CDCl3)δ6.95(m,2H),6.80(m,2H),6.10(br,1H)；13C NMR (CDCl3)δ158.3,156.4,151.0,116.3.
实施例16对羟基苯甲醛的制备
Figure BDA0001286425560000093
按照实施例1所述的方法，不同在于卤代芳香化合物为4-碘苯甲醛(232mg,1.0mmol)。粗产物经柱层析(石油醚:乙酸乙酯＝2:1)提纯，产率：78％；
1H NMR(CDCl3)δ10.59(s,1H),9.78(s,1H),7.77(d,J＝8.8Hz,2H),6.94(d, J＝8.8Hz,2H)；13C NMR(CDCl3)δ191.0,163.4,132.2,128.5,115.9.
实施例17间溴苯酚的制备
Figure BDA0001286425560000101
按照实施例1所述的方法，不同在于卤代芳香化合物为间溴碘苯(283mg,1.0mmol)。粗产物经柱层析(石油醚:乙酸乙酯＝2:1)提纯，产率：93％；
1H NMR(CDCl3)δ7.11(m,2H),7.03(d,J＝2.0Hz,1H),6.79(m,1H),5.66(br, 1H)；13C NMR(CDCl3)δ156.0,130.8,124.1,122.8,118.8,114.3.
实施例18邻甲基苯酚的制备
Figure BDA0001286425560000102
按照实施例1所述的方法，不同在于卤代芳香化合物为邻甲基碘苯(218 mg,1.0mmol)。粗产物经柱层析(石油醚:乙酸乙酯＝5:1)提纯，产率：83％；
1H NMR(CDCl3)δ7.19(m,2H),6.93(m,1H),6.83(d,J＝8.0Hz,1H),5.23(br, 1H),2.31(s,3H)；13C NMR(CDCl3)δ153.6,131.0,127.1,123.9,120.8,114.9,15.7.
实施例19 2,6-二甲基苯酚的制备
Figure BDA0001286425560000103
按照实施例1所述的方法，不同在于卤代芳香化合物为2,6-二甲基碘苯 (232mg,1.0mmol)。粗产物经柱层析(石油醚:乙酸乙酯＝5:1)提纯，产率：73％；
1H NMR(CDCl3)δ7.03(d,J＝7.2Hz,2H),6.82(m,1H),4.68(d,J＝3.6Hz,1H), 2.29(s,6H)；13C NMR(CDCl3)δ152.1,128.6,122.9,120.2,15.8.
实施例20间甲氧基苯酚的制备
Figure BDA0001286425560000111
按照实施例1所述的方法，不同在于卤代芳香化合物为间甲氧基碘苯(234 mg,1.0mmol)。粗产物经柱层析(石油醚:乙酸乙酯＝4:1)提纯，产率：92％；
1H NMR(CDCl3)δ7.16(t,J＝8.0Hz,1H),6.53(m,3H),6.26(br,1H),3.77(s, 3H)；13C NMR(CDCl3)δ160.7,156.6,130.2,108.0,106.4,101.6,55.2.
实施例21 4-苯基苯酚的制备
Figure BDA0001286425560000112
按照实施例1所述的方法，不同在于卤代芳香化合物为4-苯基碘苯(280mg,1.0mmol)。粗产物经柱层析(石油醚:乙酸乙酯＝5:1)提纯，产率：81％；
1H NMR(CDCl3)δ7.51(m,2H),7.46(m,2H),7.44(m,2H),7.33(t,J＝7.6Hz, 1H),6.93(m,2H),4.89(s,1H)；13C NMR(CDCl3)δ155.0,140.7,134.1,128.7,128.4, 126.7,115.6.
实施例22对甲基苯酚的制备
Figure BDA0001286425560000113
按照实施例1所述的方法，不同在于卤代芳香化合物为对甲基碘苯(218 mg,1.0mmol)。粗产物经柱层析(石油醚:乙酸乙酯＝5:1)提纯，产率：88％；
1H NMR(CDCl3)δ7.07(d,J＝8.0Hz,2H),6.78(d,J＝8.0Hz,2H),5.47(br,1H),2.30(s,3H)；13C NMR(CDCl3)δ153.0,130.0,115.1.
实施例23 4-乙酰基苯酚的制备
Figure BDA0001286425560000121
按照实施例1所述的方法，不同在于卤代芳香化合物为对乙酰基碘苯 (246mg,1.0mmol)。粗产物经柱层析(石油醚:乙酸乙酯＝5:1)提纯，产率：80％；
1H NMR(DMSO-d6)δ9.60(s,1H),7.99(m,1H),7.04(m,2H),2.33(s,3H)；13C NMR(DMSO-d6)δ151.4,147.8,136.8,123.3,122.6,22.9.
实施例24间乙酰基碘苯的制备
Figure BDA0001286425560000122
按照实施例1所述的方法，不同在于卤代芳香化合物为间乙酰基碘苯 (246mg,1.0mmol)。粗产物经柱层析(石油醚:乙酸乙酯＝5:1)提纯，产率：83％；
1H NMR(CDCl3)δ7.56(m,1H),7.52(d,J＝7.6Hz,1H),7.35(t,J＝8.0Hz, 1H),7.14(m,2H),2.61(s,3H)；13C NMR(CDCl3)δ199.4,156.4,138.3,129.9,121.0, 114.7,26.7.
实施例25 4-硝基苯酚的制备
Figure BDA0001286425560000123
按照实施例1所述的方法，不同在于卤代芳香化合物为4-硝基碘苯(249mg,1.0mmol)。粗产物经柱层析(石油醚:乙酸乙酯＝5:1)提纯，产率：85％；
1H NMR(DMSO-d6)δ11.03(s,1H),8.11(d,J＝9.2Hz,2H),6.93(d,J＝9.2Hz, 2H)；13C NMR(DMSO-d6)δ163.9,139.6,126.1,115.8.
实施例26邻乙酰基苯酚的制备
Figure BDA0001286425560000131
按照实施例1所述的方法，不同在于卤代芳香化合物为邻乙酰基碘苯(246 mg,1.0mmol)。粗产物经柱层析(石油醚:乙酸乙酯＝5:1)提纯，产率：75％；
1H NMR(CDCl3)δ12.26(s,1H),7.71(m,1H),7.46(m,1H),7.52(d,J＝8.4 Hz,1H),6.89(m,1H),2.59(s,3H)；13C NMR(CDCl3)δ204.4,162.2,136.3,130.6, 119.6,118.8,118.2,26.4.
实施例27对羧基苯酚的制备
Figure BDA0001286425560000132
按照实施例1所述的方法，不同在于卤代芳香化合物为对羧基碘苯(248mg,1.0mmol)。粗产物经柱层析(石油醚:乙酸乙酯＝1:1)提纯，产率：80％；
1H NMR(CDCl3)δ12.42(br,1H),10.21(br,1H),7.81(d,J＝8.8Hz,2H),6.83 (d,J＝8.8Hz,2H)；13C NMR(CDCl3)δ167.2,161.6,131.6,121.4,115.2.
实施例28 4-羟甲基苯酚的制备
Figure BDA0001286425560000133
按照实施例1所述的方法，不同在于卤代芳香化合物为对羟甲基碘苯(234 mg,1.0mmol)。粗产物经柱层析(石油醚:乙酸乙酯＝2:1)提纯，产率：87％；
1H NMR(CDCl3)δ7.24(m,2H),6.84(d,J＝8.4Hz,2H),4.78(s,1H),4.62(d, J＝5.6Hz,2H)；13C NMR(DMSO-d6)δ156.2,132.8,128.1,114.8,62.9.
实施例29 2-萘酚的制备
Figure BDA0001286425560000141
按照实施例1所述的方法，不同在于卤代芳香化合物为2-碘萘(254mg,1.0 mmol)。粗产物经柱层析(石油醚:乙酸乙酯＝4:1)提纯，产率：88％；
1H NMR(DMSO-d6)δ9.72(s,1H),7.77(m,2H),7.68(d,J＝8.0Hz,1H),7.39 (m,1H),7.27(m,1H)7.12(m,2H)；13C NMR(DMSO-d6)δ155.3,134.6,129.2, 127.7,127.5,126.1,125.9,122.6,118.6,108.6.
实施例30 2-甲基-5-羟基吡啶的制备
Figure BDA0001286425560000142
按照实施例1所述的方法，不同在于卤代芳香化合物为2-甲基-5碘吡啶(254mg,1.0mmol)。粗产物经柱层析(石油醚:乙酸乙酯＝3:1)提纯，产率：89％；
1H NMR(DMSO-d6)δ9.60(s,1H),7.99(m,1H),7.04(m,2H),2.33(s,3H)；13C NMR(DMSO-d6)δ151.4,147.8,136.8,123.3,122.6,22.9.
实施例31 2,5-二甲基苯酚的制备
Figure BDA0001286425560000143
按照实施例1所述的方法，不同在于卤代芳香化合物为2,5-二甲基碘苯 (232mg,1.0mmol)。粗产物经柱层析(石油醚:乙酸乙酯＝5:1)提纯，产率：83％；
1H NMR(CDCl3)δ7.05(d,J＝7.2Hz,1H),6.72(d,J＝7.6Hz,1H),6.62(s, 1H),4.85(br,1H),2.31(s,3H),2.25(s,3H)；13C NMR(CDCl3)δ153.5,137.0,130.7, 121.4,120.5,115.7,20.9,15.2.
实施例32 2-萘酚的制备
Figure BDA0001286425560000151
按照实施例1所述的方法，不同在于卤代芳香化合物为2-溴萘(207mg,1.0 mmol)，反应温度为120℃。粗产物经柱层析(石油醚:乙酸乙酯＝4:1)提纯，产率：85％；
1H NMR(DMSO-d6)δ9.72(s,1H),7.77(m,2H),7.68(d,J＝8.0Hz,1H),7.39 (m,1H),7.27(m,1H)7.12(m,2H)；13C NMR(DMSO-d6)δ155.3,134.6,129.2, 127.7,127.5,126.1,125.9,122.6,118.6,108.6.
实施例33对甲基苯酚的制备
Figure BDA0001286425560000152
按照实施例1所述的方法，不同在于卤代芳香化合物为对甲基溴苯(171 mg,1.0mmol)，反应温度为120℃。粗产物经柱层析(石油醚:乙酸乙酯＝5:1) 提纯，产率：83％；
1H NMR(CDCl3)δ7.07(d,J＝8.0Hz,2H),6.78(d,J＝8.0Hz,2H),5.47(br, 1H),2.30(s,3H)；13C NMR(CDCl3)δ153.0,130.0,115.1.
实施例34间甲氧基苯酚的制备
Figure BDA0001286425560000161
按照实施例1所述的方法，不同在于卤代芳香化合物为间甲氧基溴苯(187 mg,1.0mmol)，反应温度为120℃。粗产物经柱层析(石油醚:乙酸乙酯＝4:1) 提纯，产率：89％；
1H NMR(CDCl3)δ7.16(t,J＝8.0Hz,1H),6.53(m,3H),6.26(br,1H),3.77(s, 3H)；13C NMR(CDCl3)δ160.7,156.6,130.2,108.0,106.4,101.6,55.2.
实施例35对甲氧基苯酚的制备
Figure BDA0001286425560000162
按照实施例1所述的方法，不同在于卤代芳香化合物为对甲氧基溴苯(187 mg,1.0mmol)，反应温度为120℃。粗产物经柱层析(石油醚:乙酸乙酯＝4:1) 提纯，产率：89％；
1H NMR(CDCl3)δ6.79(m,4H),5.88(br,1H),3.77(s,3H)；13C NMR(CDCl3) δ153.5,149.5,116.1,114.9,55.9.
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (10)

1.一种卤代芳香化合物的羟基化方法，其特征在于，包括以下步骤：在碘化亚铜、配体、相转移催化剂和溶剂的存在下，卤代芳香化合物Ar-X与碱MOH反应，即得羟基化产物Ar-OH，反应通式I如下:
Figure 179913DEST_PATH_IMAGE001
；
I
其中，Ar为2-位R1取代的、3-位R1取代的、4-位R1取代的、2,5-位R1二取代的、或2,6-位R1二取代的芳香环；所述芳香环为苯、萘或者含氮原子的五～六元芳香杂环；R1选自：H,-NO2，-COOH，乙酰基，甲醛基，卤素，C1-C6烷基，羟基取代的C1-C6烷基，C1-C6烷氧基，或芳基；
X为卤素；
所述配体为2-吡啶酮类化合物，所述2-吡啶酮类化合物为6,7-二氢喹啉-8(5H)-酮，甲基-2-吡啶基酮或苯基-2-吡啶基酮；
所述溶剂为水，二甲基甲酰胺，二甲基乙酰胺，体积比为0.2:0.8的二甲基亚砜和水的混合液，或者体积比为0.5:0.5的二甲基亚砜和水的混合液；
所述反应的温度为90℃~120℃。
2.根据权利要求1所述的卤代芳香化合物的羟基化方法，其特征在于，所述2-吡啶酮类化合物为6,7-二氢喹啉-8(5H)-酮。
3.根据权利要求1所述的卤代芳香化合物的羟基化方法，其特征在于，所述溶剂为水。
4.根据权利要求3所述的卤代芳香化合物的羟基化方法，其特征在于，所述溶剂为体积比为0.2:0.8的二甲基亚砜和水的混合液。
5.根据权利要求1-4任一项所述的卤代芳香化合物的羟基化方法，其特征在于，所述碱选自氢氧化钠，氢氧化钾，氢氧化铜，氢氧化铯，四丁基氢氧化铵，四甲基氢氧化铵或四乙基氢氧化铵。
6.根据权利要求1-4任一项所述的卤代芳香化合物的羟基化方法，其特征在于，X为碘或者溴。
7.根据权利要求6所述的卤代芳香化合物的羟基化方法，其特征在于，当X为碘时，所述反应的温度为90℃。
8.根据权利要求1-4任一项所述的卤代芳香化合物的羟基化方法，其特征在于，所述相转移催化剂为四丁基卤化铵。
9.根据权利要求1-4任一项所述的卤代芳香化合物的羟基化方法，其特征在于，所述碱为CsOH。
10.根据权利要求1-4任一项所述的卤代芳香化合物的羟基化方法，其特征在于，所述碘化亚铜与卤代芳香化合物Ar-X的摩尔比为0.01～0.25 :1；所述配体与碘化亚铜的摩尔比为1～4:1；所述碱MOH与卤代芳香化合物Ar-X的摩尔比为1.2～30: 1；所述相转移催化剂与卤代芳香化合物Ar-X的摩尔比为0.1～0.5:1。
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