CN106977445B - 一种苯并[a]咔唑衍生物的合成方法 - Google Patents
一种苯并[a]咔唑衍生物的合成方法 Download PDFInfo
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- MYKQKWIPLZEVOW-UHFFFAOYSA-N 11h-benzo[a]carbazole Chemical class C1=CC2=CC=CC=C2C2=C1C1=CC=CC=C1N2 MYKQKWIPLZEVOW-UHFFFAOYSA-N 0.000 title claims description 26
- 238000010189 synthetic method Methods 0.000 title description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 27
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 14
- -1 transition metal salt Chemical class 0.000 claims abstract description 12
- SIKJAQJRHWYJAI-UHFFFAOYSA-N benzopyrrole Natural products C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims abstract description 11
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims abstract description 11
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000008049 diazo compounds Chemical class 0.000 claims abstract description 10
- 125000005605 benzo group Chemical group 0.000 claims abstract description 9
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 8
- 230000000996 additive effect Effects 0.000 claims abstract description 8
- 239000002585 base Substances 0.000 claims abstract description 6
- 150000001879 copper Chemical class 0.000 claims abstract description 6
- 238000001308 synthesis method Methods 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 36
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 15
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- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 claims description 2
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- BWPGCNBJSRYYLD-UHFFFAOYSA-N 2-diazonio-1,4-dimethoxy-3-oxobut-1-en-1-olate Chemical compound COCC(=O)C(=[N+]=[N-])C(=O)OC BWPGCNBJSRYYLD-UHFFFAOYSA-N 0.000 description 1
- JPFTUUXPCFNLIX-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-indole Chemical compound C=1C2=CC(C)=CC=C2NC=1C1=CC=CC=C1 JPFTUUXPCFNLIX-UHFFFAOYSA-N 0.000 description 1
- RBWNDBNSJFCLBZ-UHFFFAOYSA-N 7-methyl-5,6,7,8-tetrahydro-3h-[1]benzothiolo[2,3-d]pyrimidine-4-thione Chemical compound N1=CNC(=S)C2=C1SC1=C2CCC(C)C1 RBWNDBNSJFCLBZ-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
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Abstract
本发明公开了一种苯并[a]咔唑衍生物的合成方法,该方法包括以下步骤:将2‑芳基吲哚、重氮化合物、过渡金属盐、添加剂、碱和铜盐溶解于有机溶剂中,再在N2保护下,80‑100℃下反应8‑12h,生成苯并[a]咔唑衍生物。本发明采用2‑芳基吲哚与重氮化合物为原料,反应条件温和,2‑芳基吲哚与重氮化合物可选种类多。同时现有合成方法都需要严格无水,反应步骤长,反应操作复杂,反应需要在低温下进行,制冷成本高。而本发明不需无水,同时可以一锅法构建苯并[a]咔唑醋酸乙酯类衍生物。
Description
技术领域
本发明属于有机合成领域,具体涉及一种苯并[a]咔唑衍生物的合成方法。
背景技术
苯并[a]咔唑是很多天然产物、药物以及药物中间体、功能材料的重要骨架结构。苯并[a]咔唑以及衍生物在有机发光半导体领域有重要的用途,同时它还是可以治疗肿瘤、心脑血管疾病、艾滋病、肥胖、免疫力下降等疾病中,此外苯并[a]咔唑还是许多化合物的合成前体。因此苯并[a]咔唑衍生物的合成方法一直得到广泛的重视。
苯并[a]咔唑衍生物的合成方法主要有两种策略。一种就是过渡金属作为催化剂来催化整个反应。2004年,Mamane和Fürstner等人[Mamane,V.;Hannen,P.;Fürstner,Chem.Eur.J.,2004,10,4556-4575.]在Chemistry-A European Journal报道了用PtCl2做催化剂,甲苯做溶剂的条件下,通过1-甲基-2-(2-(丙-1-炔-1-基)苯基)-1H-吲哚在80℃合成6,11-二甲基-11H-苯并[a]咔唑。2012年,Xie和Fu等人[Xie,R.;Ling,Y.;Fu,H.Chem.Commun.,2012,48,12210-12212.]在Chemical Communications上报道了用CuBr为催化剂,0.1当量的L-脯氨酸为配体,1.5当量的Cs2CO3为碱,二甲基亚砜为溶剂的条件下,通过2-(2-溴)-苯基吲哚和苯乙酮在80℃N2的保护下生成苯并[a]咔唑衍生物。这些反应虽然都以较好的收率得到产物,但还是存在着很多问题:例如,底物的合成较为复杂且普适性不强,反应的后处理比较繁琐,不符合绿色化学与原子经济学发展的趋势。另一种,是通过氧化剂、碱、光照来催化反应。在2004年,Snieckus等人[Cai,X.;Snieckus,V.Org.Lett.,2004,6,2293-2295.]在Organic Letters上报道了以N-甲基2-芳基吲哚类化合物作为原料,经过2.5当量的LED作为碱,THF作为溶剂的条件下,合成苯并[a]咔唑类衍生物。在2014年,Yu等人[Yang,J.;Zhang,Q.;Zhang,W.;Yu,W.RSC Adv.,2014,4,13704-13707.]在RSCAdvances上报道了光催化下2-苯基-3甲酰重氮吲哚类化合物合成6-羟基-11H-苯并[a]咔唑-5-甲腈类衍生物。在2016年,Pelkey等人在[Truax,N.J.;Banales Mejia,F.;Kwansare,D.O.;Lafferty,M.M.;Kean,M.H.;Pelkey,E.T.J.Org.Chem.,2016,81,6808-6815.]TheJournal of Organic Chemistry报道了以3-吡咯啉-2-酮类化合物原料,1.1当量的二(三氟乙酸基)苯基碘为氧化剂,1.2当量BF3.OEt2为添加剂,二氯甲烷为溶剂的条件下,在-40℃的环境中,反应得到苯并[a]咔唑衍生物。
该类虽然也能得到不错的收率,但同样也存在着很多问题。首先就是反应不是一步得到目标产物,反应的步骤长;其次,该类反应的条件比较苛刻,一般很难应用于实际工业生产中;第三,就是该类反应的原子经济性差。
发明内容
为了克服现有技术的缺点与不足,本发明的目的在于提供一种简便、高效的苯并[a]咔唑衍生物的合成方法,该方法所用到的原料廉价易得且无毒,整个操作过程简单易行。
本发明的目的通过下述技术方案实现。
一种苯并[a]咔唑衍生物的合成方法,包括以下步骤:
先将2-芳基吲哚、重氮化合物、过渡金属盐、添加剂、碱和铜盐溶解于有机溶剂中,再在N2保护下,80-100℃下反应,生成苯并[a]咔唑衍生物。
优选的,所述2-芳基吲哚的结构如式A所示,重氮化合物的结构如式B所示,苯并[a]咔唑衍生物的结构如式C所示:
在式A和式C中,R1为5-CH3、5-CN、5-CO2Et、5-F、5-Cl、5-OCH3、6-CH3、6-Br和6-CF3中的一种;R2为4-CH3、4-CN、4-NO2、4-F、4-Cl、4-Br、4-i-Bu、4-OCH3、3-Cl、3-F、3-OCH3和2-CH3中的一种;
在式B和C中,R3为CH3CO、CH3CH2CO、PhCH2CH2CO和CH3OCH2CO中的一种;R4为CO2Et或COCH3中的一种。
所述2-芳基吲哚A的制备方法已有文献报道(Wei,Y.;Deb,I.;Yoshikai,N.J.Am.Chem.Soc.,2012,134,9098-9101.);所述重氮化合物B的制备方法已有文献报道(Pasceri,R.;Bartrum,H.E.;Hayes,C.J.;Moody,C.J.Chem.Commun.,2012,48,12077-12079.)。
优选的,所述2-芳基吲哚与重氮化合物的摩尔比为1:1~1:3,最优选1:2。
优选的,所述的碱为Cs2CO3、KHCO3、LiOMe、Li2CO3、Na2CO3、NaOEt、K2CO3、NaHCO3和KOEt中的一种,优选Na2CO3,其产率较高。
优选的,所述2-芳基吲哚与碱的摩尔比为1:1~1:2,最优选1:2。
优选的,所述的铜盐为醋酸铜、氯化铜、溴化铜、三氟甲磺酸铜、氯化亚铜、溴化亚铜、碘化亚铜、氰化亚铜和高氯酸铜中的一种,优选氯化亚铜,其产率较高。
优选的,所述2-芳基吲哚与铜盐的摩尔比为1:0.5~1:1,最优选1:0.5。
优选的,所述的添加剂为六氟锑酸银、醋酸银、双三氟甲烷磺酰亚胺银、高氯酸银、醋酸铯、醋酸钾和醋酸钠中的一种,优选醋酸钠,其产率较高。
优选的,所述2-芳基吲哚与添加剂的摩尔比为1:0.2~1:0.3,最优选1:0.3。
优选的,所述的过渡金属盐为二氯(五甲基环戊二烯基)合铱(III)二聚体、醋酸钯、二氯(对甲基异丙基苯基)钌(II)二聚体、1,5-环辛二烯氯铑(I)二聚体、醋酸铜、碘化铜、三氯化铑和二氯(五甲基环戊二烯基)合铑(III)二聚体中的一种。
进一步优选的,所述的过渡金属盐为二氯(五甲基环戊二烯基)合铑(III)二聚体,其产率较高。
优选的,所述2-芳基吲哚与过渡金属盐的摩尔比为1:0.025~1:0.05,最优选1:0.05。
优选的,所述的有机溶剂为乙腈。
优选的,所述反应的温度为80℃。
优选的,所述反应的时间为8-12h。
优选的,反应结束后,采用柱层析将产物分离纯化;所述柱层析的洗脱液为石油醚和乙酸乙酯的混合溶剂。
优选的,上述过程中发生的化学反应如下所示:
本发明相对于现有技术具有如下的优点及效果:
1、本发明的方法简便、高效,所用到的原料简单易得且无毒,本制备方法原子经济性高。由于反应除了生成产物外,只有水和氮气产生,对环境无污染,符合绿色化学发展的观点。另外整个操作过程简单易行,步骤简便,产物易纯化。
2、本发明采用2-芳基吲哚与重氮为原料,反应条件温和,2-芳基吲哚与重氮可选种类多。同时现有合成方法都需要严格无水,反应步骤长,反应操作复杂,反应需要在低温下进行,制冷成本高。而本发明不需无水,同时反应可以一锅法构建苯并[a]咔唑醋酸乙酯类衍生物。
附图说明
图1为本发明实施例1的化合物1的1HNMR图谱。
图2为本发明实施例1的化合物1的13CNMR图谱。
图3为本发明实施例7的化合物2的1HNMR图谱。
图4为本发明实施例7的化合物2的13CNMR图谱。
图5为本发明实施例8的化合物3的1HNMR图谱。
图6为本发明实施例8的化合物3的13CNMR图谱。
图7为本发明实施例9的化合物4的1HNMR图谱。
图8为本发明实施例9的化合物4的13CNMR图谱。
图9为本发明实施例10的化合物5的1HNMR图谱。
图10为本发明实施例10的化合物5的13CNMR图谱。
具体实施方式
下面结合实施例及附图对本发明作进一步详细的描述,但本发明的实施方式不限于此。
实施例1
苯并[a]咔唑衍生物的合成方法,包括以下步骤:
(1)在密封管中,加入2-苯基吲哚(19.3mg,0.1mmol),乙酰乙酸乙酯重氮(15.6mg,0.1mmol),无水碳酸钠(21.2mg,0.2mmol),无水醋酸钠(2.52mg,0.02mmol),氯化亚铜(5.12mg,0.05mmol),二氯(五甲基环戊二烯基)合铑(III)二聚体(1.5mg,0.0025mmol),乙腈(2mL),混合液在80℃搅拌反应8h。反应完毕后,待反应体系冷却到室温后,过滤,旋干,采用柱层析进一步分离纯化,得到产品20.6mg,产率为:68%。
本实施例所得产品的结构表征数据如下:
1HNMR(400MHz,CDCl3)δ9.02(s,1H),8.16(d,J=8.0Hz,1H),8.02–7.94(m,1H),7.93–7.83(m,1H),7.52(d,J=8.1Hz,1H),7.48–7.37(m,3H),7.28(t,J=7.5Hz,1H),4.59(q,J=7.1Hz,2H),2.90(s,3H),1.49(t,J=7.1Hz,3H).氢谱图见图1。
13CNMR(100MHz,CDCl3)δ170.8,138.7,135.3,130.6,128.9,126.1,125.4,124.9,124.6,124.6,123.2,122.2,120.5,120.23,119.3,117.1,111.1,61.3,18.6,14.4.碳谱图见图2。
High Resolution MS:计算值C20H17NO2[M+H]+:304.1332,发现:304.1339。
根据以上数据推断所得产品的结构如下所示:
实施例2
苯并[a]咔唑衍生物的合成方法,包括以下步骤:
(1)在密封管中,加入2-苯基吲哚(19.3mg,0.1mmol),乙酰乙酸乙酯重氮(31.2mg,0.2mmol),无水碳酸钠(26.5mg,0.25mmol),无水醋酸钠(2.1mg,0.025mmol),氯化亚铜(7.42mg,0.075mmol),二氯(五甲基环戊二烯基)合铑(III)二聚体(2.25mg,0.00375mmol),乙腈(2mL),混合液在90℃搅拌反应8h。反应完毕后,待反应体系冷却到室温后,过滤,旋干,采用柱层析进一步分离纯化,得到产品19.6mg,产率为:65%。
本实施例所得产品的结构表征数据如下:
1HNMR(400MHz,CDCl3)δ9.02(s,1H),8.16(d,J=8.0Hz,1H),8.02–7.94(m,1H),7.93–7.83(m,1H),7.52(d,J=8.1Hz,1H),7.48–7.37(m,3H),7.28(t,J=7.5Hz,1H),4.59(q,J=7.1Hz,2H),2.90(s,3H),1.49(t,J=7.1Hz,3H).氢谱图见图1。
13CNMR(100MHz,CDCl3)δ170.8,138.7,135.3,130.6,128.9,126.1,125.4,124.9,124.6,124.6,123.2,122.2,120.5,120.23,119.3,117.1,111.1,61.3,18.6,14.4.碳谱图见图2。
High Resolution MS:计算值C20H17NO2[M+H]+:304.1332,发现:304.1339。
根据以上数据推断所得产品的结构如下所示:
实施例3
苯并[a]咔唑衍生物的合成方法,包括以下步骤:
(1)在密封管中,加入2-苯基吲哚(19.3mg,0.1mmol),乙酰乙酸乙酯重氮(31.2mg,0.2mmol),无水碳酸钠(21.2mg,0.2mmol),无水醋酸钠(2.52mg,0.03mmol),氯化亚铜(5.12mg,0.05mmol),二氯(五甲基环戊二烯基)合铑(III)二聚体(3mg,0.005mmol),乙腈(2mL),混合液在100℃搅拌反应8h。反应完毕后,待反应体系冷却到室温后,过滤,旋干,采用柱层析进一步分离纯化,得到产品21.5mg,产率为:71%。
本实施例所得产品的结构表征数据如下:
1HNMR(400MHz,CDCl3)δ9.02(s,1H),8.16(d,J=8.0Hz,1H),8.02–7.94(m,1H),7.93–7.83(m,1H),7.52(d,J=8.1Hz,1H),7.48–7.37(m,3H),7.28(t,J=7.5Hz,1H),4.59(q,J=7.1Hz,2H),2.90(s,3H),1.49(t,J=7.1Hz,3H).氢谱图见图1。
13CNMR(100MHz,CDCl3)δ170.8,138.7,135.3,130.6,128.9,126.1,125.4,124.9,124.6,124.6,123.2,122.2,120.5,120.23,119.3,117.1,111.1,61.3,18.6,14.4.碳谱图见图2。
High Resolution MS:计算值C20H17NO2[M+H]+:304.1332,发现:304.1339。
根据以上数据推断所得产品的结构如下所示:
实施例4
苯并[a]咔唑衍生物的合成方法,包括以下步骤:
(1)在密封管中,加入2-苯基吲哚(19.3mg,0.1mmol),乙酰乙酸乙酯重氮(46.8mg,0.3mmol),无水碳酸钠(31.8mg,0.3mmol),无水醋酸钠(2.52mg,0.03mmol),氯化亚铜(9.98mg,0.1mmol),二氯(五甲基环戊二烯基)合铑(III)二聚体(3mg,0.005mmol),乙腈(2mL),混合液在100℃搅拌反应12h。反应完毕后,待反应体系冷却到室温后,过滤,旋干,采用柱层析进一步分离纯化,得到产品23.0mg,产率为:76%。
本实施例所得产品的结构表征数据如下:
1HNMR(400MHz,CDCl3)δ9.02(s,1H),8.16(d,J=8.0Hz,1H),8.02–7.94(m,1H),7.93–7.83(m,1H),7.52(d,J=8.1Hz,1H),7.48–7.37(m,3H),7.28(t,J=7.5Hz,1H),4.59(q,J=7.1Hz,2H),2.90(s,3H),1.49(t,J=7.1Hz,3H).氢谱图见图1。
13CNMR(100MHz,CDCl3)δ170.8,138.7,135.3,130.6,128.9,126.1,125.4,124.9,124.6,124.6,123.2,122.2,120.5,120.23,119.3,117.1,111.1,61.3,18.6,14.4.碳谱图见图2。
High Resolution MS:计算值C20H17NO2[M+H]+:304.1332,发现:304.1339。
根据以上数据推断所得产品的结构如下所示:
实施例5
苯并[a]咔唑衍生物的合成方法,包括以下步骤:
(1)在密封管中,加入2-苯基吲哚(19.3mg,0.1mmol),乙酰乙酸乙酯重氮(31.2mg,0.2mmol),无水碳酸钠(21.2mg,0.2mmol),无水醋酸钠(2.52mg,0.03mmol),氯化亚铜(9.98mg,0.10mmol),二氯(五甲基环戊二烯基)合铑(III)二聚体(3mg,0.005mmol),乙腈(2mL),混合液在100℃搅拌反应10h。反应完毕后,待反应体系冷却到室温后,过滤,旋干,采用柱层析进一步分离纯化,得到产品22.4mg,产率为:74%。
本实施例所得产品的结构表征数据如下:
1HNMR(400MHz,CDCl3)δ9.02(s,1H),8.16(d,J=8.0Hz,1H),8.02–7.94(m,1H),7.93–7.83(m,1H),7.52(d,J=8.1Hz,1H),7.48–7.37(m,3H),7.28(t,J=7.5Hz,1H),4.59(q,J=7.1Hz,2H),2.90(s,3H),1.49(t,J=7.1Hz,3H).氢谱图见图1。
13CNMR(100MHz,CDCl3)δ170.8,138.7,135.3,130.6,128.9,126.1,125.4,124.9,124.6,124.6,123.2,122.2,120.5,120.23,119.3,117.1,111.1,61.3,18.6,14.4.碳谱图见图2。
High Resolution MS:计算值C20H17NO2[M+H]+:304.1332,发现:304.1339。
根据以上数据推断所得产品的结构如下所示:
实施例6
苯并[a]咔唑衍生物的合成方法,包括以下步骤:
(1)在密封管中,加入2-苯基吲哚(19.3mg,0.1mmol),乙酰乙酸乙酯重氮(31.2mg,0.2mmol),无水碳酸钠(21.2mg,0.2mmol),无水醋酸钠(2.52mg,0.03mmol),氯化亚铜(5.12mg,0.05mmol),二氯(五甲基环戊二烯基)合铑(III)二聚体(3mg,0.005mmol),乙腈(2mL),混合液在80℃搅拌反应8h。反应完毕后,待反应体系冷却到室温后,过滤,旋干,采用柱层析进一步分离纯化,得到产品25.4mg,产率为:84%。
本实施例所得产品的结构表征数据如下:
1HNMR(400MHz,CDCl3)δ9.02(s,1H),8.16(d,J=8.0Hz,1H),8.02–7.94(m,1H),7.93–7.83(m,1H),7.52(d,J=8.1Hz,1H),7.48–7.37(m,3H),7.28(t,J=7.5Hz,1H),4.59(q,J=7.1Hz,2H),2.90(s,3H),1.49(t,J=7.1Hz,3H).氢谱图见图1。
13CNMR(100MHz,CDCl3)δ170.8,138.7,135.3,130.6,128.9,126.1,125.4,124.9,124.6,124.6,123.2,122.2,120.5,120.23,119.3,117.1,111.1,61.3,18.6,14.4.碳谱图见图2。
High Resolution MS:计算值C20H17NO2[M+H]+:304.1332,发现:304.1339。
根据以上数据推断所得产品的结构如下所示:
实施例7
苯并[a]咔唑衍生物的合成方法,包括以下步骤:
(1)在密封管中,加入5-甲基2-苯基吲哚(20.7mg,0.1mmol),乙酰乙酸乙酯重氮(31.2mg,0.2mmol),无水碳酸钠(21.2mg,0.2mmol),无水醋酸钠(2.52mg,0.03mmol),氯化亚铜(5.12mg,0.05mmol),二氯(五甲基环戊二烯基)合铑(III)二聚体(3mg,0.005mmol),乙腈(2mL),混合液在80℃搅拌反应8h。反应完毕后,待反应体系冷却到室温后,过滤,旋干,采用柱层析进一步分离纯化,得到产品26.4mg,产率为:82%。
本实施例所得产品的结构表征数据如下:
1H NMR(400MHz,CDCl3)δ8.89(s,1H),8.03–7.84(m,3H),7.51–7.37(m,3H),7.25–7.20(m,1H),4.59(q,J=7.1Hz,2H),2.91(s,3H),2.55(s,3H),1.49(t,J=7.1Hz,3H).氢谱图见图3。
13C NMR(100MHz,CDCl3)δ170.9,137.0,135.6,130.8,129.4,128.8,126.0,126.0,125.3,124.8,124.8,122.9,122.0,120.5,119.3,116.8,110.7,61.3,21.7,18.7,14.4.碳谱图见图4。
High Resolution MS:计算值C21H20NO2[M+H]+:318.1489,发现:318.1491。
根据以上数据推断所得产品的结构如下所示:
实施例8
苯并[a]咔唑衍生物的合成方法,包括以下步骤:
(1)在密封管中,加入2-(4-甲氧基苯基)吲哚(22.3mg,0.1mmol),乙酰乙酸乙酯重氮(31.2mg,0.2mmol),无水碳酸钠(21.2mg,0.2mmol),无水醋酸钠(2.52mg,0.03mmol),氯化亚铜(5.12mg,0.05mmol),二氯(五甲基环戊二烯基)合铑(III)二聚体(3mg,0.005mmol),乙腈(2mL),混合液在80℃搅拌反应8h。反应完毕后,待反应体系冷却到室温后,过滤,旋干,采用柱层析进一步分离纯化,得到产品24.7mg,产率为:75%。
本实施例所得产品的结构表征数据如下:
1H NMR(400MHz,CDCl3)δ8.95(s,1H),8.10(d,J=7.9Hz,1H),7.84–7.74(m,1H),7.47(d,J=8.0Hz,1H),7.36(t,J=7.6Hz,1H),7.25(dd,J=10.2,4.8Hz,1H),7.07–6.93(m,1H),4.58(q,J=7.1Hz,2H),3.79(s,3H),2.86(s,3H),1.50(t,J=7.1Hz,3H).氢谱图见图5。
13C NMR(100MHz,CDCl3)δ171.1,157.8,138.7,135.8,131.5,130.3,124.7,124.1,122.1,122.0,121.8,120.0,116.2,115.6,114.1,111.0,104.9,61.3,55.1,18.7,14.5.碳谱图见图6。
High Resolution MS:计算值C21H20NO3[M+H]+:334.1438,发现:334.1443。
根据以上数据推断所得产品的结构如下所示:
实施例9
苯并[a]咔唑衍生物的合成方法,包括以下步骤:
(1)在密封管中,加入2-(2-氯苯基)吲哚(22.7mg,0.1mmol),乙酰乙酸乙酯重氮(31.2mg,0.2mmol),无水碳酸钠(21.2mg,0.2mmol),无水醋酸钠(2.52mg,0.03mmol),氯化亚铜(5.12mg,0.05mmol),二氯(五甲基环戊二烯基)合铑(III)二聚体(3mg,0.005mmol),乙腈(2mL),混合液在80℃搅拌反应8h。反应完毕后,待反应体系冷却到室温后,过滤,旋干,采用柱层析进一步分离纯化,得到产品23.3mg,产率为:67%。
本实施例所得产品的结构表征数据如下:
1H NMR(400MHz,DMSO-d6)δ12.53(s,1H),8.70(d,J=2.0Hz,1H),8.25(d,J=8.0Hz,1H),7.89(d,J=9.0Hz,1H),7.71(d,J=8.1Hz,1H),7.61(dd,J=9.0,2.1Hz,1H),7.49(t,J=7.5Hz,1H),7.30(t,J=7.5Hz,1H),4.51(q,J=7.1Hz,2H),2.90(s,3H),1.41(t,J=7.1Hz,3H).氢谱图见图7。
13C NMR(100MHz,DMSO-d6)δ169.1,139.1,134.6,130.6,129.7,127.1,126.5,126.4,124.9,123.2,122.1,121.9,121.1,120.2,119.8,116.7,111.6,61.0,18.2,14.1.碳谱图见图8。
High Resolution MS:计算值C20H17ClNO2[M+H]+:338.0942,发现:338.0943。
根据以上数据推断所得产品的结构如下所示:
实施例10
苯并[a]咔唑衍生物的合成方法,包括以下步骤:
(1)在密封管中,加入2-苯基吲哚(19.8mg,0.1mmol),2-重氮基-4-甲氧基-3-氧代丁酸甲酯(34.5mg,0.2mmol),无水碳酸钠(21.2mg,0.2mmol),无水醋酸钠(2.52mg,0.03mmol),氯化亚铜(5.12mg,0.05mmol),二氯(五甲基环戊二烯基)合铑(III)二聚体(3mg,0.005mmol),乙腈(2mL),混合液在80℃搅拌反应8h。反应完毕后,待反应体系冷却到室温后,过滤,旋干,采用柱层析进一步分离纯化,得到产品25.2mg,产率为:79%。
本实施例所得产品的结构表征数据如下:
1H NMR(400MHz,CDCl3)δ9.22(d,J=3.3Hz,1H),8.12(d,J=8.0Hz,1H),7.88(dd,J=22.0,8.2Hz,2H),7.42(dd,J=17.3,8.3Hz,2H),7.36(t,J=7.3Hz,2H),7.25(t,J=8.2Hz,1H),5.03(s,2H),4.08(s,3H),3.42(s,3H).氢谱图见图9。
13C NMR(100MHz,CDCl3)δ171.0,138.9,136.0,129.5,128.4,126.2,125.8,124.9,123.8,123.5,122.8,120.7,120.4,120.3,116.2,111.1,70.5,58.0,52.4.碳谱图见图10。
High Resolution MS:计算值C20H18NO3[M+H]+:320.1286,发现:320.1290。
根据以上数据推断所得产品的结构如下所示:
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (5)
1.一种苯并[a]咔唑衍生物的合成方法,其特征在于,包括以下步骤:
先将2-芳基吲哚、重氮化合物、过渡金属盐、添加剂、碱和铜盐溶解于有机溶剂中,再在N2保护下,80下反应8h,生成苯并[a]咔唑衍生物;
所述2-芳基吲哚的结构如式A所示,重氮化合物的结构如式B所示,苯并[a]咔唑衍生物的结构如式C所示:
在式A和式C中,R1为5-CH3、5-CN、5-CO2Et、5-F、5-Cl、5-OCH3、6-CH3、6-Br和6-CF3中的一种;R2为4-CH3、4-CN、4-NO2、4-F、4-Cl、4-Br、4-i-Bu、4-OCH3、3-Cl、3-F、3- OCH3和2-CH3中的一种;
在式B和C中,R3为CH3;R4为CO2Et;
所述的添加剂为醋酸钠;
所述的铜盐为氯化亚铜;
所述的过渡金属盐为二氯(五甲基环戊二烯基)合铑(III)二聚体。
2.根据权利要求1所述的合成方法,其特征在于,所述2-芳基吲哚与重氮化合物的摩尔比为1:1~1:3。
3.根据权利要求1所述的合成方法,其特征在于,所述的碱为Cs2CO3、KHCO3、 LiOMe、Li2CO3、Na2CO3、NaOEt、 K2CO3、NaHCO3和KOEt中的一种。
4.根据权利要求1所述的合成方法,其特征在于,所述的有机溶剂为乙腈。
5.根据权利要求1所述的合成方法,其特征在于,所述2-芳基吲哚与碱的摩尔比为1:1~1:3;所述2-芳基吲哚与铜盐的摩尔比为1:0.5~1:1;所述2-芳基吲哚与添加剂的摩尔比为1:0.2~1:0.3;所述2-芳基吲哚与过渡金属盐的摩尔比为1:0.025~1:0.05。
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