CN107739333B - 一种绿色的喹啉化合物的制备方法 - Google Patents

一种绿色的喹啉化合物的制备方法 Download PDF

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CN107739333B
CN107739333B CN201711119462.5A CN201711119462A CN107739333B CN 107739333 B CN107739333 B CN 107739333B CN 201711119462 A CN201711119462 A CN 201711119462A CN 107739333 B CN107739333 B CN 107739333B
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quinoline
quinoline compound
phenyl
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CN107739333A (zh
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张胜
包明
艾哈迈德·瓦卡
于晓强
冯秀娟
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Dalian University of Technology
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    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract

本发明属于医药化工中间体及相关化学技术领域，提供了一种绿色的喹啉化合物的制备方法。以N‑取代苯胺衍生物为原料，在酸催化剂及氧化剂的存在、无溶剂条件下，与苯乙炔或苯乙烯衍生物在80℃～160℃下反应24小时，即可得到喹啉化合物。本发明的有益效果是操作简便、条件温和、环境友好、有实现工业化的可能性，并且以较高收率得到喹啉化合物；利用该方法所合成的喹啉化合物可以进一步官能化得到各类化合物，应用于天然产物、功能材料及精细化学品的开发与研究。

Description

一种绿色的喹啉化合物的制备方法
技术领域
本发明属于医药化工中间体及相关化学技术领域，涉及到一种绿色的喹啉化合物的制备方法。
背景技术
喹啉类化合物在有机化学中是一类极其重要的结构单元，其在医药、农药、染料、功能材料和香料等领域中都有着很重要的应用价值。自从1834年喹啉被 Runge从煤焦油中分离得到，如何用化学方法来合成喹啉类衍生物一直是有机合成化学家们研究的热点。
经典的有机合成喹啉类衍生物的化学方法包括Skraup–Doebner–von Miller 合成法，Combes–Conrad–Limpach合成法,合成法和Pfitzinger合成法等[Fallah-Mehrjardi M.,Mini-Rev.Org.Chem.,2017,14,187]，这些合成方法有很大的缺点就是通常是在高温、强酸体系下进行的，存在着工业生产中对设备要求高，环境污染压力大的缺点。近年来，过渡金属催化的偶联反应因其高效性逐渐受到人们的广泛关注，成为合成喹啉化合物的重要方法[Prajapati S.M.,Patel K. D.,Vekariya R.H.,Panchal S.N.,Patel H.D.,RSC Adv.,2014,4,24463]。虽然过渡金属催化合成方法避免了浓硫酸或浓盐酸等无机酸的使用，但是过渡金属催化剂在催化合成喹啉类衍生物的过程中依然存在着催化剂的分离和回收困难等不足。因此，研究绿色的喹啉化合物的合成方法具有重大的意义。作为重要的绿色合成法，无金属催化反应引起人们的关注。2015年报道了使用自由基阳离子盐作为催化剂，由N-苄基苯胺制备喹啉的方法，而催化剂的合成限制了该方法的发展[Liu J.,Liu F.,Zhu Y.,Ma X.,Jia X.,Org.Lett.,2015,17,1409]。
发明内容
本发明提供了一种喹啉化合物的新颖制备方法，该方法简便，无金属催化剂和溶剂参与，环境友好、条件温和、操作简便，并且收率较高。
本发明的技术方案：
一种绿色的喹啉化合物的制备方法，以N-取代苯胺衍生物为原料，在酸催化剂及氧化剂的存在、无溶剂条件下，与苯乙炔或苯乙烯衍生物在80℃～160℃下反应24小时，即可到喹啉化合物；合成路线如下：
R1选自氢、烷基、卤素；
R2选自氢、烷基、酯基、取代苯基、噻吩基；
R3选自氢、烷基、酯基、卤素、甲氧基、甲氧甲酰基；
N-取代苯胺衍生物与催化剂的摩尔比为1:0.05～1:0.2；
N-取代苯胺衍生物与苯乙炔或苯乙烯衍生物的摩尔比为1:1～1:20；
所述的催化剂包括醋酸、三氟乙酸、对甲苯磺酸和三氟甲磺酸；
所述的氧化剂包括空气、纯氧和过氧化物；
分离方法包括重结晶、柱层析等。
重结晶方法使用的溶剂包括苯、乙醇、石油醚、乙腈、四氢呋喃、氯仿、正己烷、丙酮、乙酸乙酯、二氯甲烷；
用柱层析方法进行产物分离时，可以使用硅胶或氧化铝作为固定相，展开剂一般为极性与非极性的混合溶剂，如乙酸乙酯-石油醚、乙酸乙酯-正己烷、二氯甲烷-石油醚、甲醇-石油醚。
本发明的有益效果是操作简便、条件温和、环境友好、有实现工业化的可能性，并且以较高收率得到喹啉化合物；利用该方法所合成的喹啉化合物可以进一步官能化得到各类化合物，应用于天然产物、功能材料及精细化学品的开发与研究。
附图说明
图1是实施例1中2,4-二苯基喹啉的1H核磁谱图。
图2是实施例1中2,4-二苯基喹啉的13C核磁谱图。
图3是实施例2中2-(5-溴噻吩基-2-)-6-甲基-4-苯基喹啉的1H核磁谱图。
图4是实施例2中2-(5-溴噻吩基-2-)-6-甲基-4-苯基喹啉的13C核磁谱图。
图5是实施例3中2-(3,4-二氯苯基)-6-甲基-4-苯基喹啉的1H核磁谱图。
图6是实施例3中2-(3,4-二氯苯基)-6-甲基-4-苯基喹啉的13C核磁谱图。
图7是实施例4中6-甲基-4-苯基喹啉-2-甲酸乙酯的1H核磁谱图。
图8是实施例4中6-甲基-4-苯基喹啉-2-甲酸乙酯的13C核磁谱图。
图9是实施例5中6-甲基-2-苯基-4-(2-甲苯基)喹啉的1H核磁谱图。
图10是实施例5中6-甲基-2-苯基-4-(2-甲苯基)喹啉的13C核磁谱图。
图11是实施例6中4-(4-氟苯基)-6-甲基-2-苯基喹啉的1H核磁谱图。
图12是实施例6中4-(4-氟苯基)-6-甲基-2-苯基喹啉的13C核磁谱图。图13是实施例7中4-(4-甲氧基苯基)-6-甲基-2-苯基喹啉的1H核磁谱图。
图14是实施例7中4-(4-甲氧基苯基)-6-甲基-2-苯基喹啉的13C核磁谱图。
图15是实施例8中乙酸4-(6-甲基-2-苯基喹啉4-)苯酯的1H核磁谱图。
图16是实施例8中乙酸4-(6-甲基-2-苯基喹啉4-)苯酯的13C核磁谱图。
具体实施方式
本发明所述的喹啉化合物的制备方法，具有原料价格低廉、反应步骤少、反应条件温和、环境友好、便于操作和反应收率高等优点。
下面结合具体实施例，进一步阐述本发明。这些实施例仅用于说明本发明而不用于限制本发明的范围。在本领域内的技术人员对本发明所做的简单替换或改进均属于本发明所保护的技术方案之内。
实施例1：2,4-二苯基喹啉的合成
在25mL反应器中，加入N-苄基苯胺(0.037g,0.2mmol)，苯乙炔(0.102 g,1.0mmol)，搅拌下加入三氟乙酸(0.003g,0.03mmol)，80℃、氧气球条件下搅拌24h。柱层析分离(硅胶，200-300目；展开剂，石油醚/二氯甲烷＝4/1) 得到2,4-二苯基喹啉0.047g，产率83％。
2,4-二苯基喹啉
黄色油状液体；1H NMR(400MHz,CDCl3):δ8.23(d,J＝8.4Hz,1H),8.19(d,J＝8.4Hz,2H),7.91(d,J＝8.3Hz,1H),7.82(s,1H),7.75–7.71(m,1H),7.57–7.46(m, 9H)；13CNMR(125MHz,CDCl3):δ156.8,149.1,148.8,139.6,138.4,130.1,129.5, 129.5,129.3,128.8,128.6,128.4,127.5,126.3,125.7,125.6,119.3.
实施例2：2-(5-溴噻吩基-2-)-6-甲基-4-苯基喹啉的合成
操作同实施例1，由N-[(5-溴噻吩基-2-)甲基]-4-甲基苯胺与苯乙炔反应得到 2-(5-溴噻吩基-2-)-6-甲基-4-苯基喹啉0.059g，产率78％。
2-(5-溴噻吩基-2-)-6-甲基-4-苯基喹啉
棕色固体；熔点181.1–182.0℃；1H NMR(400MHz,CDCl3):δ8.01(d,J＝8.6Hz, 1H),7.56–7.50(m,8H),7.42(d,J＝4.0Hz,1H),7.06(d,J＝4.0Hz,1H),2.43(s, 3H)；13C NMR(100MHz,CDCl3):δ149.8,148.9,146.6,138.0,136.5,132.2,131.0, 129.4,128.9,128.6,128.5,125.8,125.7,124.5,117.1,116.0,21.8；HRMS(ESI,m/z) calcd for C20H15NBrS+:380.0103[M+H]+；found:380.0109；IR(neat)3046,2959, 2825,1608,1563,1442,1021,850,790,732,574cm-1.
实施例3：2-(3,4-二氯苯基)-6-甲基-4-苯基喹啉的合成
操作同实施例1，由N-(3,4-二氯苄基)-4-甲基苯胺与苯乙炔反应得到2-(3,4- 二氯苯基)-6-甲基-4-苯基喹啉0.067g，产率92％。
2-(3,4-二氯苯基)-6-甲基-4-苯基喹啉
白色固体；熔点143.0–143.6℃；1H NMR(400MHz,CDCl3):δ8.11(d,J＝8.5Hz, 1H),7.71–7.68(m,2H),7.62(s,1H),7.58–7.48(m,7H),7.37(dd,J＝8.5,2.1Hz, 1H),2.47(s,3H)；13C NMR(125MHz,CDCl3):δ154.8,147.5,147.2,138.1,138.1, 137.0,135.0,133.1,132.6,131.8,129.8,129.7,129.5,128.5,128.3,127.4,125.6, 124.4,122.7,21.8.
实施例4：6-甲基-4-苯基喹啉-2-甲酸乙酯的合成
操作同实施例1，由N-(4-甲基苯基)甘氨酸乙酯与苯乙炔反应得到6-甲基-4-苯基喹啉-2-甲酸乙酯0.051g，产率87％。
6-甲基-4-苯基喹啉-2-甲酸乙酯
棕色固体；熔点115.4–116.1℃；1H NMR(400MHz,CDCl3):δ8.27(d,J＝8.7Hz, 1H),8.10(s,1H),7.70(s,1H),7.61(dd,J＝8.7,1.8Hz,1H),7.56–7.51(m,5H), 4.56(q,J＝7.1Hz,2H),2.49(s,3H),1.49(t,J＝7.1Hz,3H)；13C NMR(100MHz, CDCl3):δ165.5,148.9,146.8,146.7,138.9,137.7,132.3,130.8,129.5,128.6,128.5, 127.7,124.3,121.3,62.1,21.9,14.3.
实施例5：6-甲基-2-苯基-4-(2-甲苯基)喹啉的合成
在25mL反应器中，加入N-苄基-4-甲基苯胺(0.039g,0.2mmol)，2-甲基苯乙烯(0.236g,2.0mmol)，搅拌下加入对甲苯磺酸(0.003g,0.02mmol)，130℃、空气条件下搅拌24h。柱层析分离(硅胶，200-300目；展开剂，石油醚/二氯甲烷＝2:1)得到6-甲基-2-苯基-4-(2-甲苯基)喹啉0.048g，产率78％。
6-甲基-2-苯基-4-(2-甲苯基)喹啉
棕色固体；熔点122.1–123.0℃；1H NMR(400MHz,CDCl3):δ8.18–8.12(m,3H), 7.71(s,1H),7.53–7.22(m,9H),2.39(s,3H),2.07(s,3H)；13C NMR(125MHz, CDCl3):δ155.9,148.3,147.1,139.6,138.0,136.2,136.0,131.7,130.1,129.7,129.6, 129.1,128.7,128.2,127.4,126.1,125.7,124.4,119.3,21.6,20.0.
实施例6：4-(4-氟苯基)-6-甲基-2-苯基喹啉的合成
操作同实施例5，由N-苄基-4-甲基苯胺与4-氟苯乙烯反应得到4-(4-氟苯基)-6-甲基-2-苯基喹啉0.044g，产率71％。
4-(4-氟苯基)-6-甲基-2-苯基喹啉
黄色固体；熔点112.9–113.5℃；1H NMR(400MHz,CDCl3):δ8.17–8.12(m,3H), 7.72(s,1H),7.58–7.43(m,7H),7.25–7.20(m,2H),2.46(s,3H)；13C NMR(125 MHz,CDCl3):δ163.7(d,1JC-F＝248.0),154.8,148.6,147.3,138.5,136.3,135.9(d, 4JC-F＝3.0Hz),131.8,129.7,129.5,129.2(d,3JC-F＝8.4Hz),128.6,128.3,125.6, 124.4,119.0,115.7(d,2JC-F＝21.5Hz),113.0,21.8.
实施例7：4-(4-甲氧基苯基)-6-甲基-2-苯基喹啉的合成
在25mL反应器中，加入N-苄基-4-甲基苯胺(0.039g,0.2mmol)，4-甲氧基苯乙炔(0.198g,1.5mmol)，搅拌下加入三氟甲磺酸(0.005g,0.03mmol)， 110℃、氧气球条件下搅拌24h。柱层析分离(硅胶，200-300目；展开剂，石油醚/乙酸乙酯＝5:1)得到4-(4-甲氧基苯基)-6-甲基-2-苯基喹啉0.056g，产率 86％。
4-(4-甲氧基苯基)-6-甲基-2-苯基喹啉
黄色固体；熔点104.7–105.8℃；1H NMR(400MHz,CDCl3):δ8.17–8.11(m,3H), 7.73(s,1H),7.67(s,1H),7.54–7.41(m,6H),7.07–7.03(m,2H),3.86(s,3H),2.44(s, 3H)；13CNMR(125MHz,CDCl3):δ159.7,155.9,148.1,147.4,139.8,136.0,131.6, 130.8,130.7,129.8,129.0,128.7,127.4,125.8,124.4,119.3,114.0,55.3,21.8.
实施例8：乙酸[4-(6-甲基-2-苯基喹啉4-)]苯酯的合成
操作同实施例7，由N-苄基-4-甲基苯胺与乙酸(4-乙炔基)苯酯反应得到乙酸4-(6-甲基-2-苯基喹啉4-)苯酯0.048g，产率68％。
乙酸4-(6-甲基-2-苯基喹啉4-)苯酯
棕色固体；熔点126.5–127.3℃；1H NMR(400MHz,CDCl3):δ8.16–8.13(m,3H), 7.75(s,1H),7.64(s,1H),7.57–7.43(m,6H),7.27(d,J＝8.5Hz,2H),2.47(s,3H), 2.36(s,3H)；13C NMR(125MHz,CDCl3):δ169.4,156.0,150.7,147.5,147.3,139.6, 136.4,136.1,131.8,130.6,129.8,129.2,128.8,127.4,125.6,124.2,121.8,119.5, 21.8,21.2。

Claims (1)

1.一种绿色的喹啉化合物的制备方法，其特征在于，以N-取代苯胺衍生物为原料，在酸催化剂及氧化剂的存在、无溶剂条件下，与苯乙炔或苯乙烯衍生物在80℃～160℃下反应24小时，即可到喹啉化合物；合成路线如下：
R1选自氢、烷基、卤素；
R2选自氢、烷基、酯基、取代苯基、噻吩基；
R3选自氢、烷基、酯基、卤素、甲氧基、甲氧甲酰基；
N-取代苯胺衍生物与催化剂的摩尔比为1:0.05～1:0.2；
N-取代苯胺衍生物与苯乙炔或苯乙烯衍生物的摩尔比为1:1～1:20；
所述的催化剂为醋酸、三氟乙酸、对甲苯磺酸或三氟甲磺酸；
所述的氧化剂为空气或纯氧。
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CN108794394A (zh) * 2018-07-24 2018-11-13 南通大学 一种配体促进的廉价金属催化合成多取代喹啉的方法
CN110156681B (zh) * 2019-05-30 2022-11-11 安徽工程大学宣城产业技术研究院有限公司 一种2-酯基喹啉的合成方法
CN110423217B (zh) * 2019-08-30 2022-04-12 大连理工大学 一种共轭烯炔化合物的制备方法
CN110606829B (zh) * 2019-09-26 2023-04-28 上海城建职业学院 一种钯催化合成4-取代喹啉衍生物的方法
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CN113277978B (zh) * 2021-06-02 2022-06-03 河南师范大学 一种2，4-双取代喹啉类化合物的制备方法
CN113603627B (zh) * 2021-08-05 2023-08-18 江西省科学院应用化学研究所 一种吡咯酮螺环丙烷化合物的合成方法
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