CN111187241B - 二苯并呋喃衍生物及其制备方法 - Google Patents
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明涉及有机合成领域,公开了一种二苯并呋喃衍生物及其制备方法,所述制备方法包括:(1)将苯酚衍生物、溴化铵盐、无机碱催化剂和溶剂混合反应;(2)经TLC跟踪反应和硅胶色谱柱分离得到二苯并呋喃衍生物。该制备方法具有原料易得、无毒无害、反应条件简单温和等优点。
Description
技术领域
本发明涉及有机合成领域,具体地,涉及一种二苯并呋喃衍生物及其制备方法。
背景技术
二苯并呋喃类化合物是一类非常有用的有机化合物,用于医药,消毒剂,防腐剂,染料,合成树脂及高温润滑剂等的原料且具有抗血管生成作用。由于二苯并呋喃化合物具有稳定的化学结构,热稳定性和抗生物降解能力强,此类含氧化合物在油藏地球化学研究中得到更加广泛的应用。二苯并呋喃类含氧化合物具有和咔唑类含氮化合物类似的结构,由于在多环芳烃结构母环中引入了杂原子氧,使含氧多环芳烃化合物具有了两个重要的化学性质:①不同位置烷基取代异构体的热稳定性不同,主要是因为电负性较强的氧原子的引入,导致芳环上电子云密度变化,从而导致不同位置取代基的异构体热稳定的差异;②氧原子上一对未成键孤对电子,该孤对电子对环上电子云产生诱导效应(-I),同时氧原子上的电子还与碳原子产生共轭效应(+C)。
传统合成二苯并呋喃的方法有以下几种:(1)邻芳基酚的环醚化,以特戊酸或醋酸作为添加剂,以DMF作为溶剂在高温140℃条件下反应24h,此反应需要在1atm的O2氛围中才能得到良好的收率,此方法操作比较繁琐且反应时间比较;(2)以1-溴-2-碘苯和苯酚为原料,2倍当量的叔丁醇钾作为催化剂,在二甲亚砜中反应3h,此反应过程需要通N2保护且要光照;(3)用1当量的邻碘苯酚类化合物与1.2当量的三氟甲磺酸甲硅烷基芳基酯和3.5当量的CsF反应,以乙腈作为溶剂在室温下反应10h,然后添加5mol%的Pd(OAc)2和10mol%的PCy3,并在100℃加热1d即可获得产物;(4)用2-(2'-氨基芳基)苯酚衍生物作为反应原料,加入1%的T(p-F)PPT光敏剂和2当量的亚硝酸叔丁酯于2,2,2-三氟乙醇(TFE)溶剂中,然后在室温下使用CFL(23W)获得可见光反应15h即可获得二苯并呋喃产物;(5)在150℃条件下以2-苯氧基苯甲酸苯酯为原料,加入10mol%的Pd(OAc)2,20mol%的dcype和1.5当量的K2CO3在甲苯溶剂中反应12h,反应完成后可分离得到纯产物。以上关于二苯并呋喃衍生物的合成方法中存在的缺陷主要有以下:(1)反应条件比较苛刻,操作繁琐,需要在通气的条件下反应且反应的温度相对较高;(2)反应时间较长;(3)有些需要光照反应。
因此,提供一种原料易得、无毒无害、反应条件简单温和的二苯并呋喃衍生物及其制备方法是本发明亟需解决的问题。
发明内容
本发明的目的是提供一种二苯并呋喃衍生物及其制备方法,该制备方法具有原料易得、无毒无害、反应条件简单温和等优点。
为了实现上述目的,本发明提供一种二苯并呋喃衍生物的制备方法,所述制备方法包括:
(1)将苯酚衍生物、溴化铵盐、无机碱催化剂和溶剂混合反应;
(2)经TLC跟踪反应和硅胶色谱柱分离得到二苯并呋喃衍生物。
本发明还提供了一种二苯并呋喃衍生物,所述二苯并呋喃衍生物由上述的制备方法制得。
通过上述技术方案,本发明提供了一种二苯并呋喃衍生物及其制备方法,与现有合成方法相比,本发明以无机碱催化剂为碱,以苯酚衍生物和溴化铵盐为原料,在溶剂下反应即可高产率得到目标产物。该方法的改进较传统技术解决的关键技术有:(1)以廉价易得、无毒、对环境友好的无机碱催化剂为碱;(2)使用简单易得的化合物作为基本原料;(3)反应条件温和,反应过程中只需加入碱,在温和条件下可得到目标产物;(3)反应产物产率高,副反应少,反应后处理简单;(4)利用本方法可以高效合成得到一种二苯并呋喃类化合物,其结构更加复杂多样,易于进一步对产物结构进行修饰,在天然产物、活性药物合成等领域也具有十分重要的应用。
本发明的其它特征和优点将在随后的具体实施方式部分予以详细说明。
附图说明
附图是用来提供对本发明的进一步理解,并且构成说明书的一部分,与下面的具体实施方式一起用于解释本发明,但并不构成对本发明的限制。在附图中:
图1是化合物A1的核磁氢谱图;
图2是化合物A1的核磁碳谱图;
图3是化合物A2的核磁氢谱图;
图4是化合物A2的核磁碳谱图;
图5是化合物A5的核磁氢谱图;
图6是化合物A5的核磁碳谱图;
图7是化合物A7的核磁氢谱图;
图8是化合物A7的核磁碳谱图;
图9是化合物A8的核磁氢谱图;
图10是化合物A8的核磁碳谱图。
具体实施方式
以下对本发明的具体实施方式进行详细说明。应当理解的是,此处所描述的具体实施方式仅用于说明和解释本发明,并不用于限制本发明。
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值,这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说,各个范围的端点值之间、各个范围的端点值和单独的点值之间,以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围,这些数值范围应被视为在本文中具体公开。
本发明提供了一种二苯并呋喃衍生物的制备方法,所述制备方法包括:
(1)将苯酚衍生物、溴化铵盐、无机碱催化剂和溶剂混合反应;
(2)经TLC跟踪反应和硅胶色谱柱分离得到二苯并呋喃衍生物。
在本发明的一种优选的实施方式中,苯酚衍生物选自2-(3-(4-甲氧基苯基)-1-(吡咯烷基-1-基)丙-2-炔-1-基)苯酚、2,4-二叔丁基-6-(1-(吡咯烷-1-基)-3-(对甲苯基)丙-2-炔-1-基)苯酚、2-(3-(4-甲氧基苯基)-1-(吡咯烷基-1-基)丙-2-炔-1-基)-4-甲基苯酚、2-溴-4-氯-6-(3-(4-甲氧基苯基)-1-(吡咯烷基-1-基)丙-2-炔-1-基)苯酚、4-氯-2-(3-(4-氯苯基)-1-(吡咯烷-1-基)丙-2-炔-1-基)苯酚、2-(3-(4-甲氧基苯基)-1-(吡咯烷基-1-基)丙-2-炔-1-基)苯酚、4-溴-2-(1-(吡咯烷-1-基)-3-(噻吩-3-基)丙-2-炔-1-基)苯酚、2-(3-苯基-1-(吡咯烷基-1-基)丙-2-炔-1-基)苯酚、4-溴-2-(1-(吡咯烷-1-基)-3-(对甲苯基)丙-2-炔-1-基)苯酚或4-溴-2-(3-苯基-1-(吡咯烷基-1-基)丙-2-炔-1-基)苯酚中的一种。
在本发明的一种优选的实施方式中,溴化铵盐选自1-甲基-3-(2-氧代-2-苯基乙基)-1H-咪唑-3-溴化铵盐、3-(2-(4-溴苯基)-2-氧乙基)-1-甲基-1H-咪唑-3-溴化铵盐或1-甲基-3-(2-氧代-2-(间甲苯基)乙基)-1H-咪唑-3-溴化铵盐中的一种。
在本发明的一种优选的实施方式中,溶剂选自乙腈、N,N-二甲基甲酰胺或二甲亚砜。
在本发明的一种优选的实施方式中,相对于5mL的溶剂,苯酚衍生物的用量为0.4-0.6mmol,溴化铵盐的用量为0.8-1.2mmol,无机碱催化剂的用量为1.4-1.6mmol。
在本发明的一种优选的实施方式中,无机碱催化剂由叔丁醇钾和氢氧化钾组成;
优选地,相对于1mmol的氢氧化钾,叔丁醇钾的用量为0.4-0.6mmol。
在本发明的一种优选的实施方式中,在步骤(1)中,混合反应的条件包括:
温度为75-85℃;和/或
时间为2-4h。
在本发明的一种优选的实施方式中,在硅胶色谱柱分离中,展开剂由石油醚和乙酸乙酯组成。
在本发明的一种优选的实施方式中,石油醚和乙酸乙酯按照体积比为19~21:1进行混合。
本发明还提供了一种二苯并呋喃衍生物,所述二苯并呋喃衍生物由上述的制备方法制得。
以下将通过实施例对本发明进行详细描述。
实施例1
向50mL反应瓶中依次加入2-(3-(4-甲氧基苯基)-1-(吡咯烷基-1-基)丙-2-炔-1-基)苯酚(0.5mmol),1-甲基-3-(2-氧代-2-苯基乙基)-1H-咪唑-3-溴化铵盐(1mmol),叔丁醇钾(0.5mmol),氢氧化钾(1mmol),乙腈(5mL),80℃下反应3h,反应用薄层层析跟踪,反应结束后,减压蒸去溶剂,硅胶色谱柱分离(展开剂石油醚/乙酸乙酯v:v=20:1),即可以82%的产率得到纯的白色固体2-(4-甲氧基苯基)-4-苯基-5-苯甲酰基二苯并[b,d]呋喃(A1)。
目标产物的结构通过1H NMR和13C NMR来测定,测定结果如下:
1H NMR(400MHz,CDCl3)δ8.01–7.89(m,2H),7.80–7.70(m,2H),7.68–7.54(m,3H),7.50–7.25(m,6H),7.24–7.09(m,6H),3.91(s,3H).
13C NMR(400MHz,CDCl3)δ198.05,159.80,156.85,152.55,139.99,137.22,135.78,133.45,130.87,130.19,129.76,129.56,128.42,128.29,128.24,128.09,127.75,127.32,126.59,123.01,122.77,122.73,122.65,114.31,111.83,77.38,77.06,76.75,55.45。
实施例2
向50mL反应瓶中依次加入2,4-二叔丁基-6-(1-(吡咯烷-1-基)-3-(对甲苯基)丙-2-炔-1-基)苯酚(0.5mmol),1-甲基-3-(2-氧代-2-苯基乙基)-1H-咪唑-3-溴化铵盐(1mmol),叔丁醇钾(0.5mmol),氢氧化钾(1mmol),乙腈(5mL),80℃下反应3h,反应用薄层层析跟踪,反应结束后,减压蒸去溶剂,硅胶色谱柱分离(展开剂石油醚/乙酸乙酯v:v=20:1),即可以75%的产率得到纯的白色固体2-(4-甲基苯基)-4-苯基-5-苯甲酰基-6,8-二叔丁基二苯并[b,d]呋喃(A2)。
目标产物的结构通过1H NMR和13C NMR来测定,测定结果如下:
1H NMR(400MHz,CDCl3)δ7.97–7.92(m,2H),7.87–7.82(m,2H),7.69(s,1H),7.47–7.37(m,6H),7.36–7.26(m,4H),7.25–7.19(m,2H),2.48(s,3H),1.56(s,9H),1.20(s,9H).
13C NMR(400MHz,CDCl3)δ197.91,153.22,152.28,145.59,140.29,138.03,137.50,135.43,134.01,133.39,133.01,131.26,129.80,129.57,129.49,128.68,128.59,128.27,127.98,127.19,126.19,122.85,122.45,122.24,116.84,77.37,77.05,76.73,34.87,34.60,31.66,29.95,21.37。
实施例3
向50mL反应瓶中依次加入2-(3-(4-甲氧基苯基)-1-(吡咯烷基-1-基)丙-2-炔-1-基)-4-甲基苯酚(0.5mmol),1-甲基-3-(2-氧代-2-苯基乙基)-1H-咪唑-3-溴化铵盐(1mmol),叔丁醇钾(0.5mmol),氢氧化钾(1mmol),乙腈(5mL),80℃下反应3h,反应用薄层层析跟踪,反应结束后,减压蒸去溶剂,硅胶色谱柱分离(展开剂石油醚/乙酸乙酯v:v=20:1),即可以72%的产率得到纯的白色固体2-(4-甲氧基苯基)-4-苯基-5-苯甲酰基-8-甲基二苯并[b,d]呋喃(A3)。
目标产物的结构通过1H NMR和13C NMR来测定,测定结果如下:
1H NMR(400MHz,CDCl3)δ7.97–7.92(m,2H),7.75–7.71(m,2H),7.63(s,1H),7.50–7.35(m,5H),7.29–7.26(m,1H),7.25–7.09(m,7H),3.92(s,3H),2.35(s,3H).
13C NMR(400MHz,CDCl3)δ198.18,159.75,155.24,152.82,140.07,137.39,135.66,133.33,132.51,130.79,130.18,129.74,129.57,128.95,128.35,128.25,128.17,128.01,127.25,126.52,122.72,122.48,114.28,111.31,77.37,77.06,76.74,55.45,21.40.
实施例4
向50mL反应瓶中依次加入2-溴-4-氯-6-(3-(4-甲氧基苯基)-1-(吡咯烷基-1-基)丙-2-炔-1-基)苯酚(0.5mmol),1-甲基-3-(2-氧代-2-苯基乙基)-1H-咪唑-3-溴化铵盐(1mmol),叔丁醇钾(0.5mmol),氢氧化钾(1mmol),乙腈(5mL),80℃下反应3h,反应用薄层层析跟踪,反应结束后,减压蒸去溶剂,硅胶色谱柱分离(展开剂石油醚/乙酸乙酯v:v=20:1),即可以80%的产率得到纯的白色固体2-(4-甲氧基苯基)-4-苯基-5-苯甲酰基-8-氯-6-溴二苯并[b,d]呋喃(A4)。
目标产物的结构通过1H NMR和13C NMR来测定,测定结果如下:
1H NMR(400MHz,CDCl3)δ8.03–7.97(m,2H),7.75–7.67(m,3H),7.62–7.53(m,2H),7.43–7.39(m,1H),7.37–7.26(m,3H),7.25–7.09(m,6H),3.92(s,3H).
13C NMR(400MHz,CDCl3)δ197.35,160.04,152.93,152.66,139.54,136.95,136.86,133.65,131.06,130.31,130.11,129.71,129.51,129.23,128.96,128.45,128.39,127.59,127.24,127.14,124.99,122.17,121.52,114.44,104.90,77.37,77.06,76.74,55.46。
实施例5
向50mL反应瓶中依次加入4-氯-2-(3-(4-氯苯基)-1-(吡咯烷-1-基)丙-2-炔-1-基)苯酚(0.5mmol),1-甲基-3-(2-氧代-2-苯基乙基)-1H-咪唑-3-溴化铵盐(1mmol),叔丁醇钾(0.5mmol),氢氧化钾(1mmol),乙腈(5mL),80℃下反应3h,反应用薄层层析跟踪,反应结束后,减压蒸去溶剂,硅胶色谱柱分离(展开剂石油醚/乙酸乙酯v:v=20:1),即可以72%的产率得到纯的白色固体2-(4-氯苯基)-4-苯基-5-苯甲酰基-8-氯二苯并[b,d]呋喃(A5)。
目标产物的结构通过1H NMR和13C NMR来测定,测定结果如下:
1H NMR(400MHz,CDCl3)δ7.95–7.88(m,2H),7.74–7.66(m,3H),7.59–7.50(m,4H),7.45–7.39(m,2H),7.36–7.26(m,4H),7.25–7.17(m,3H).
13C NMR(400MHz,CDCl3)δ197.41,155.17,139.45,136.88,136.31,134.61,133.80,133.67,130.22,129.72,129.50,129.12,129.05,128.71,128.47,128.40,128.17,127.59,125.93,122.43,112.85,77.24,77.04,76.72.
实施例6
向50mL反应瓶中依次加入2-(3-(4-甲氧基苯基)-1-(吡咯烷基-1-基)丙-2-炔-1-基)苯酚(0.5mmol),3-(2-(4-溴苯基)-2-氧乙基)-1-甲基-1H-咪唑-3-溴化铵盐(1mmol),叔丁醇钾(0.5mmol),氢氧化钾(1mmol),乙腈(5mL),80℃下反应3h,反应用薄层层析跟踪,反应结束后,减压蒸去溶剂,硅胶色谱柱分离(展开剂石油醚/乙酸乙酯v:v=20:1),即可以69%的产率得到纯的白色固体2-(4-甲氧基苯基)-4-(4-溴苯基)-5-(4-溴苯甲酰基)二苯并[b,d]呋喃(A6)。
目标产物的结构通过1H NMR和13C NMR来测定,测定结果如下:
1H NMR(400MHz,CDCl3)δ7.96–7.91(m,2H),7.64–7.59(m,4H),7.54–7.42(m,4H),7.41–7.36(m,2H),7.25–7.16(m,3H),7.14–7.09(m,2H),3.92(s,3H).
13C NMR(400MHz,CDCl3)δ196.73,159.94,156.87,152.65,138.73,135.79,134.30,132.04,131.60,131.13,131.03,130.17,130.11,129.21,128.04,127.97,127.73,126.99,123.20,122.78,122.44,121.99,114.38,111.96,77.38,77.06,76.75,55.46,18.47。
实施例7
向50mL反应瓶中依次加入4-溴-2-(1-(吡咯烷-1-基)-3-(噻吩-3-基)丙-2-炔-1-基)苯酚(0.5mmol),1-甲基-3-(2-氧代-2-苯基乙基)-1H-咪唑-3-溴化铵盐(1mmol),叔丁醇钾(0.5mmol),氢氧化钾(1mmol),乙腈(5mL),80℃下反应3h,反应用薄层层析跟踪,反应结束后,减压蒸去溶剂,硅胶色谱柱分离(展开剂石油醚/乙酸乙酯v:v=20:1),即可以73%的产率得到纯的白色固体2-(噻吩-3-基)-4-苯基-5-苯甲酰基-8-溴二苯并[b,d]呋喃(A7)。
目标产物的结构通过1H NMR和13C NMR来测定,测定结果如下:
1H NMR(400MHz,CDCl3)δ8.22–8.14(m,1H),7.83–7.79(m,2H),7.74–7.66(m,3H),7.58–7.55(m,1H),7.54–7.50(m,2H),7.43–7.27(m,4H),7.25–7.15(m,4H).
13C NMR(400MHz,CDCl3)δ197.49,155.54,139.65,137.08,136.33,135.55,133.54,131.07,130.81,129.70,129.53,128.41,128.35,127.94,127.51,127.08,126.13,125.45,124.81,124.77,122.00,121.83,116.11,113.28,77.35,77.03,76.72。
实施例8
向50mL反应瓶中依次加入2-(3-苯基-1-(吡咯烷基-1-基)丙-2-炔-1-基)苯酚(0.5mmol),1-甲基-3-(2-氧代-2-(间甲苯基)乙基)-1H-咪唑-3-溴化铵盐(1mmol),叔丁醇钾(0.5mmol),氢氧化钾(1mmol),乙腈(5mL),80℃下反应3h,反应用薄层层析跟踪,反应结束后,减压蒸去溶剂,硅胶色谱柱分离(展开剂石油醚/乙酸乙酯v:v=20:1),即可以54%的产率得到纯的白色固体2-苯基-4-(3-甲基苯基)-5-(3-甲基苯甲酰基)二苯并[b,d]呋喃(A8)。
目标产物的结构通过1H NMR和13C NMR来测定,测定结果如下:
1H NMR(400MHz,CDCl3)δ8.04–7.96(m,2H),7.71(s,1H),7.65–7.52(m,6H),7.50–7.41(m,2H),7.25–7.05(m,6H),7.02–6.95(m,1H),2.28(s,3H),2.25(s,3H).
13C NMR(400MHz,CDCl3)δ198.07,156.87,152.61,139.90,138.13,137.83,137.20,135.86,134.24,131.68,130.34,130.06,129.01,128.83,128.69,128.31,128.28,128.13,128.01,127.73,127.18,126.74,126.63,123.01,122.80,122.75,122.71,111.80,77.37,77.05,21.33,21.20。
实施例9
向50mL反应瓶中依次加入4-溴-2-(1-(吡咯烷-1-基)-3-(对甲苯基)丙-2-炔-1-基)苯酚(0.5mmol),1-甲基-3-(2-氧代-2-苯基乙基)-1H-咪唑-3-溴化铵盐(1mmol),叔丁醇钾(0.5mmol),氢氧化钾(1mmol),乙腈(5mL),80℃下反应3h,反应用薄层层析跟踪,反应结束后,减压蒸去溶剂,硅胶色谱柱分离(展开剂石油醚/乙酸乙酯v:v=20:1),即可以68%的产率得到纯的白色固体2-(4-甲基苯基)-4-苯基-5-苯甲酰基-8-溴二苯并[b,d]呋喃(A9)。
目标产物的结构通过1H NMR和13C NMR来测定,测定结果如下:
1H NMR(400MHz,CDCl3)δ7.95–7.92(m,2H),7.74–7.72(m,3H),7.56–7.48(m,3H),7.44–7.26(m,6H),7.25–7.17(m,4H),2.35(s,3H).
13C NMR(400MHz,CDCl3)δ197.92,155.23,152.74,139.77,137.21,135.71,134.34,134.21,133.45,132.74,131.74,130.25,129.72,129.54,129.18,129.04,128.41,128.31,128.16,127.39,125.52,122.91,122.53,122.50,111.32,77.05,76.73,21.40。
实施例10
向50mL反应瓶中依次加入4-溴-2-(3-苯基-1-(吡咯烷基-1-基)丙-2-炔-1-基)苯酚(0.5mmol),1-甲基-3-(2-氧代-2-苯基乙基)-1H-咪唑-3-溴化铵盐(1mmol),叔丁醇钾(0.5mmol),氢氧化钾(1mmol),乙腈(5mL),80℃下反应3h,反应用薄层层析跟踪,反应结束后,减压蒸去溶剂,硅胶色谱柱分离(展开剂石油醚/乙酸乙酯v:v=20:1),即可以80%的产率得到纯的白色固体2,4-二苯基-5-苯甲酰基二苯并[b,d]呋喃(A10)。
目标产物的结构通过1H NMR和13C NMR来测定,测定结果如下:
1H NMR(400MHz,CDCl3)δ7.99–7.93(m,2H),7.75–7.68(m,4H),7.60–7.48(m,5H),7.42–7.35(m,3H),7.29–7.27(m,1H),7.25–7.11(m,4H).
13C NMR(400MHz,CDCl3)δ197.56,155.62,153.12,139.63,137.01,136.30,135.39,133.59,130.78,129.74,129.54,129.41,128.99,128.90,128.54,128.45,128.36,127.50,127.21,125.39,124.75,121.87,116.01,113.33,77.36,77.04,76.72。
综上,本发明提供了一种二苯并呋喃衍生物及其制备方法,(1)采用价廉易得、无毒环保的无机碱作为催化剂,有望实现工业化生产;(2)反应条件温和,反应温度控制在80℃左右即可;反应时间短,反应过程TLC跟踪发现,反应在3h之间即可完成;(3)产物产率高,目标产物的产率中等至良好(60%-85%);(4)原料安全性高,原料自然放置不会产生有害有毒物质。
以上详细描述了本发明的优选实施方式,但是,本发明并不限于上述实施方式中的具体细节,在本发明的技术构思范围内,可以对本发明的技术方案进行多种简单变型,这些简单变型均属于本发明的保护范围。
另外需要说明的是,在上述具体实施方式中所描述的各个具体技术特征,在不矛盾的情况下,可以通过任何合适的方式进行组合。
此外,本发明的各种不同的实施方式之间也可以进行任意组合,只要其不违背本发明的思想,其同样应当视为本发明所公开的内容。
Claims (5)
1.一种二苯并呋喃衍生物的制备方法,其特征在于,所述制备方法包括:
(1)将苯酚衍生物、溴化铵盐、无机碱催化剂和溶剂混合反应;
(2)经TLC跟踪反应和硅胶色谱柱分离得到二苯并呋喃衍生物;
其中,苯酚衍生物选自2-(3-(4-甲氧基苯基)-1-(吡咯烷基-1-基)丙-2-炔-1-基)苯酚、2,4-二叔丁基-6-(1-(吡咯烷-1-基)-3-(对甲苯基)丙-2-炔-1-基)苯酚、2-(3-(4-甲氧基苯基)-1-(吡咯烷基-1-基)丙-2-炔-1-基)-4-甲基苯酚、2-溴-4-氯-6-(3-(4-甲氧基苯基)-1-(吡咯烷基-1-基)丙-2-炔-1-基)苯酚、4-氯-2-(3-(4-氯苯基)-1-(吡咯烷-1-基)丙-2-炔-1-基)苯酚、2-(3-(4-甲氧基苯基)-1-(吡咯烷基-1-基)丙-2-炔-1-基)苯酚、4-溴-2-(1-(吡咯烷-1-基)-3-(噻吩-3-基)丙-2-炔-1-基)苯酚、2-(3-苯基-1-(吡咯烷基-1-基)丙-2-炔-1-基)苯酚、4-溴-2-(1-(吡咯烷-1-基)-3-(对甲苯基)丙-2-炔-1-基)苯酚或4-溴-2-(3-苯基-1-(吡咯烷基-1-基)丙-2-炔-1-基)苯酚中的一种;
溴化铵盐选自1-甲基-3-(2-氧代-2-苯基乙基)-1H-咪唑-3-溴化铵盐、3-(2-(4-溴苯基)-2-氧乙基)-1-甲基-1H-咪唑-3-溴化铵盐或1-甲基-3-(2-氧代-2-(间甲苯基)乙基)-1H-咪唑-3-溴化铵盐中的一种;
相对于5 mL的溶剂,苯酚衍生物的用量为0.4-0.6 mmol,溴化铵盐的用量为0.8-1.2mmol,无机碱催化剂的用量为1.4-1.6mmol;
无机碱催化剂由叔丁醇钾和氢氧化钾组成;
在步骤(1)中,混合反应的条件包括:温度为75-85℃,时间为2-4h。
2.根据权利要求1所述的制备方法,其中,溶剂选自乙腈、N,N-二甲基甲酰胺或二甲亚砜。
3.根据权利要求1或2所述的制备方法,其中,相对于1 mmol的氢氧化钾,叔丁醇钾的用量为0.4-0.6 mmol。
4.根据权利要求1所述的制备方法,其中,在硅胶色谱柱分离中,展开剂由石油醚和乙酸乙酯组成。
5.根据权利要求4所述的制备方法,其中,石油醚和乙酸乙酯按照体积比为19~21:1进行混合。
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1077086A (en) * | 1963-11-20 | 1967-07-26 | Ibm | Novel dibenzofuran derivatives, processes for their preparation and polymers formed therefrom |
CN103113337A (zh) * | 2013-03-08 | 2013-05-22 | 宿迁德威化工有限公司 | 一种二苯并呋喃衍生物的制备方法 |
WO2015049616A1 (en) * | 2013-10-04 | 2015-04-09 | Pfizer Inc. | Novel bicyclic pyridinones as gamma-secretase modulators |
CN108358877A (zh) * | 2018-04-24 | 2018-08-03 | 沅江华龙催化科技有限公司 | 一种呋喃基邻二酮衍生物及其制备方法 |
CN108440467A (zh) * | 2018-03-20 | 2018-08-24 | 安徽师范大学 | 多取代呋喃衍生物及其制备方法 |
CN108467376A (zh) * | 2018-04-12 | 2018-08-31 | 常州大学 | 一种二苯并呋喃衍生物的合成方法 |
CN109020935A (zh) * | 2018-10-11 | 2018-12-18 | 西安近代化学研究所 | 一种二苯并呋喃衍生物及其制备方法 |
CN109206302A (zh) * | 2017-07-06 | 2019-01-15 | Dic株式会社 | 苯基苯酚衍生物和使用其的二苯并呋喃衍生物的制造方法 |
-
2020
- 2020-03-03 CN CN202010141681.9A patent/CN111187241B/zh active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1077086A (en) * | 1963-11-20 | 1967-07-26 | Ibm | Novel dibenzofuran derivatives, processes for their preparation and polymers formed therefrom |
CN103113337A (zh) * | 2013-03-08 | 2013-05-22 | 宿迁德威化工有限公司 | 一种二苯并呋喃衍生物的制备方法 |
WO2015049616A1 (en) * | 2013-10-04 | 2015-04-09 | Pfizer Inc. | Novel bicyclic pyridinones as gamma-secretase modulators |
CN109206302A (zh) * | 2017-07-06 | 2019-01-15 | Dic株式会社 | 苯基苯酚衍生物和使用其的二苯并呋喃衍生物的制造方法 |
CN108440467A (zh) * | 2018-03-20 | 2018-08-24 | 安徽师范大学 | 多取代呋喃衍生物及其制备方法 |
CN108467376A (zh) * | 2018-04-12 | 2018-08-31 | 常州大学 | 一种二苯并呋喃衍生物的合成方法 |
CN108358877A (zh) * | 2018-04-24 | 2018-08-03 | 沅江华龙催化科技有限公司 | 一种呋喃基邻二酮衍生物及其制备方法 |
CN109020935A (zh) * | 2018-10-11 | 2018-12-18 | 西安近代化学研究所 | 一种二苯并呋喃衍生物及其制备方法 |
Non-Patent Citations (3)
Title |
---|
Catalyst-Free Synthesis of 2,3-Dihydrobenzofurans via a Formal [4+1] Annulation of Propargylamines with Sulfur Ylides;Xinwei He 等;《J. Org. Chem.》;20190821;第84卷;11623-11638 * |
DMAP催化的有机串联反应——非有机溶剂条件下一锅法合成苯并呋喃衍生物;王翠娥 等;《中国化学会第27届学术年会第06分会场摘要集》;20100620;182 * |
Substituent-Guided Palladium-Ene Reaction for the Synthesis of Carbazoles and Cyclopenta[b]indoles;Sonu Yadav 等;《Org. Lett.》;20190415;第21卷;2983-2987 * |
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