CN109651291B - 一种多取代萘并[1,2-d]噻唑及衍生物及其合成方法 - Google Patents
一种多取代萘并[1,2-d]噻唑及衍生物及其合成方法 Download PDFInfo
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Abstract
本发明涉及一种多取代萘并[1,2‑d]噻唑及衍生物及其合成方法。本发明首次采用在Cu催化下,在空气氛围中,将酮肟酯类化合物,甲醛类化合物和硫粉转化为多取代萘并[1,2‑d]噻唑及衍生物,制得分子结构稳定,化学性质优良。合成方法的反应原料廉价易得,且不需要经过预处理,反应的原子经济性高;反应只需要使用廉价的铜催化剂,减少环境污染,节约原材料,减少反应成本;整个反应体系简单,反应条件温和,反应设备较少,实验操作简便,用料来源广泛。
Description
技术领域
本发明涉及一种多取代萘并[1,2-d]噻唑及衍生物及其合成方法,属于有机化合物合成技术领域。
背景技术
萘并[1,2-d]噻唑及衍生物是一类重要的芳杂环化合物,而噻唑的多种衍生物又是重要的药物或生理活性的物质。在光电材料等多领域可能具有潜在的应用。
发明内容
本发明为了补充现有技术的缺陷,提供一种分子结构稳定、化学性质优良的多取代萘并[1,2-d]噻唑及衍生物
本发明还提供一种多取代萘并[1,2-d]噻唑及衍生物的合成方法。
本发明解决其技术问题所采用的技术方案是:本发明提供一种多取代萘并[1,2-d]噻唑及衍生物,其通式为式I或II:
其中
R1选自:
氢原子,卤素基,烷基,取代或非取代的C6-C10芳基,取代或未取代的含有氮、氧、硫原子的杂环基团;其中芳基或者杂环基团的取代基选自C1-C4的直链烷基、支链烷基,具有一个或多个卤素取代基的C1-C4的直链烷基、支链烷基,烷氧基,取代或非取代芳基;
R2选自:
取代或非取代的C6-C10芳基;取代或未取代的含有氮、氧、硫原子的C4-C10杂环基团;其中芳基或者杂环基团的取代基选自C1-C4的直链烷基、支链烷基,具有一个或多个卤素取代基的C1-C4的直链烷基、支链烷基,烷氧基,卤素基,氧烷基,取代或非取代芳基。
本发明还提供一种多取代萘并[1,2-d]噻唑及衍生物的方法,以铜类化合物作催化剂,包括以下步骤:
以铜类化合物作催化剂,包括以下步骤:
S1:将酮肟酯类化合物,甲醛类化合物,硫粉,催化剂与有机溶剂在反应容器内进行充分混合;
S2:空气氛围下,对反应物加热进行反应;
S3:纯化得到多取代萘并[1,2-d]噻唑及衍生物。
优选地,本发明的合成方法,所述酮肟酯类化合物,是选自C8-C20芳香类酮肟酯,其通式为式III:
其中
R1选自:
氢原子,卤素基,烷基,取代或非取代的C6-C10芳基,取代或非取代的与苯环并列的1个或多个C6-C10芳基,取代或未取代的含有氮、氧、硫原子的杂环基团;其中芳基或者杂环基团的取代基选自C1-C4的直链烷基、支链烷基,具有一个或多个卤素取代基的C1-C4的直链烷基、支链烷基,烷氧基,取代或非取代芳基;
优选地,本发明的合成方法,所述酮肟酯类化合物选自:四氢萘酮肟酯,5-甲氧基-3,4-二氢萘-1(2H)-酮肟酯,6-甲氧基-3,4-二氢萘-1(2H)-酮肟酯,7-甲氧基-3,4-二氢萘-1(2H)-酮肟酯,7-溴-3,4-二氢萘-1(2H)-酮肟酯,4-甲基-3,4-二氢萘-1(2H)-酮肟酯,4-(3,4-二氯苯基)-3,4-二氢萘-1(2H)-酮肟酯,6,7-二氢苯并呋喃-4(5H)-酮肟酯,6,7-二氢苯并[b]噻吩-4(5H)-酮肟酯,2,3-二氢-1H-咔唑-4(9H)-酮肟酯,9-甲基-2,3-二氢-1H-咔唑-4(9H)-酮肟酯,4″-甲基-1′,6′-二氢-[1,1′:3′,1“-三联苯]-5′(2′H)-酮肟酯,4″-甲氧基-1′,6′-二氢-[1,1′:3′,1“-三联苯]-5′(2′H)-酮酮肟酯,5-(萘-2-基)-1,6-二氢-[1,1′-联苯]-3(2H)-酮肟酯,3-甲基环己-2-烯酮肟酯,4,5-二氢-[1,1′-联苯基]-2(3H)-酮肟酯。
优选地,本发明的合成方法,所述甲醛类化合物,其通式为式IV:
其中
R2选自:
取代或非取代的C6-C10芳基;取代或未取代的含有氮,氧,硫原子的C4-C10杂环基团;其中芳基或者杂环基团的取代基选自C1-C4的直链烷基、支链烷基,具有一个或多个卤素取代基的C1-C4的直链烷基、支链烷基,烷氧基,卤素基,氧烷基,取代或非取代芳基;
优选地,本发明的合成方法,所述甲醛类化合物选自:苯甲醛,4-甲基苯甲醛,4-苯基苯甲醛,4-叔丁基苯甲醛,4-甲氧基苯甲醛,4-氟苯甲醛,4-氯苯甲醛,4-溴苯甲醛,4-硝基苯甲醛,2-甲基苯甲醛,2-氟苯甲醛,2-氯苯甲醛,3-甲基苯甲醛,3-甲氧基苯甲醛,3-氟苯甲醛,3-氯苯甲醛,3-溴苯甲醛,4-三氟甲基苯甲醛,对苯基苯甲醛,2,4-二甲基苯甲醛,2,4-二氯苯甲醛,3,4-二甲氧基苯甲醛,3,4,5-三甲氧基苯甲醛,3,4-二氯苯甲醛,2-萘醛,2-噻吩甲醛,2-吡啶甲醛,4-吡啶甲醛,4-喹啉甲醛,糠醛,环丙基甲醛。
优选地,本发明的合成方法,所述铜类化合物选自:铜粉,氯化亚铜,溴化亚铜,碘化亚铜,氧化亚铜,无水硫酸铜,无水乙酰丙酮,无水乙酸铜,碱式碳酸铜,三氟甲基磺酸铜,氯化铜,溴化铜,氧化铜中的一种或多种。
优选地,本发明的合成方法,所述甲醛类化合物、酮肟酯类化合物、硫粉与催化剂的摩尔比为1.0∶1.1-4.0∶2.2-8.0∶0.1-0.3;反应温度为100℃-140℃,反应时长为8h-24h。
优选地,本发明的合成方法,所述有机溶剂为二甲基亚砜或N,N-二甲基甲酰胺。
本发明现有技术所产生的有益效果:
(I)本发明在铜类化合物的催化下,在空气氛围中,将酮肟酯类化合物,甲醛类化合物和硫粉转化为一种多取代萘并[1,2-d]噻唑及衍生物的技术方案,制得分子结构稳定;(II)反应原料廉价易得,不需要贵金属催化剂,只需要使用廉价的铜催化剂,减少环境污染,减少反应成本;(III)是科研道路上的又一新发现,为科研成果又添上完美的一笔;(IV)采用一锅法直接选择性的合成目标产物且收率高,节约了大量的研制时间与生产周期;(VI)它工艺科学、合理,操作容易,反应步骤少,所需设备少;(VII)它具有原料广泛,低投入、高产出,易于进一步大批量生产和普及推广;(VIII)它具有反应体系简单,反应条件温和,反应设备较少,实验操作简便,用料来源广泛等特点。
附图说明
为了证明本发明的产物,本发明提供部分实施例的核磁氢谱图和核磁碳谱图。
图1-1实施例1产物的核磁氢谱图。
图1-2实施例1产物的核磁碳谱图。
图2-1实施例2产物的核磁氢谱图。
图2-2实施例2产物的核磁碳谱图。
图3-1实施例3产物的核磁氢谱图。
图3-2实施例3产物的核磁碳谱图。
图4-1实施例4产物的核磁氢谱图。
图4-2实施例4产物的核磁碳谱图。
图5-1实施例5产物的核磁氢谱图。
图5-2实施例5产物的核磁碳谱图。
图6-1实施例6产物的核磁氢谱图。
图6-2实施例6产物的核磁碳谱图。
图7-1实施例7产物的核磁氢谱图。
图7-2实施例7产物的核磁碳谱图。
图8-1实施例8产物的核磁氢谱图。
图8-2实施例8产物的核磁碳谱图。
图9-1实施例9产物的核磁氢谱图。
图9-2实施例9产物的核磁碳谱图。
图10-1实施例10产物的核磁氢谱图。
图10-2实施例10产物的核磁碳谱图。
图11是本发明合成反应的反应方程式。
具体实施方式
现在结合附图对本发明作进一步详细的说明。这些附图均为简化的示意图,仅以示意方式说明本发明的基本结构,因此其仅显示与本发明有关的构成。
反应方程式为:
实施例1-45
多取代萘并[1,2-d]噻唑及衍生物的合成方法包括以下步骤:
步骤1:将酮肟酯类化合物(具体物质见表1)、甲醛类化合物(具体物质见表1)和硫粉和碱加入反应容器中,将铜催化剂(具体物质见表1)和有机溶剂(具体物质见表1)加入反应容器中混合均匀;
步骤2:将反应容器均匀加热(如油浴加热)至表1中所述的温度,酮肟酯类化合物、甲醛类化合物和硫粉在溶剂中进行反应,并持续表1中所述的时间;
步骤3:反应完成后进行提纯得到。
表1:实施例1-45中甲醛化合物、酮肟酯类化合物、硫粉和铜催化剂摩尔比、反应温度和反应时间
*为甲醛类化合物、酮肟酯类化合物、硫粉和铜催化剂的摩尔比
将步骤3后反应容器内的物质进行转化率检测并进行核磁共振,部分实施例的结果如下:
实施例1产物的核磁数据如下:
1H NMR(400MHz,CDCl3,ppm)δ8.96(d,J=8.2Hz,1H),8.21(dt,J=8.5,2.3Hz,2H),7.94(dd,J=15.9,8.4Hz,2H),7.81(d,J=8.7Hz,1H),7.73-7.68(m,1H),7.63-7.56(m,1H),7.55-7.47(m,3H);13C NMR(100MHz,CDCl3)δ167.0,150.4,134.0,132.1,131.7,130.6,129.0,128.8,128.1,127.3,126.9,126.1,125.9,124.0,119.0.
.实施例2产物的核磁数据如下:
1H NMR(400MHz,CDCl3,ppm)δ8.50(d,J=8.3Hz,1H),8.23(d,J=9.0Hz,1H),8.17(dd,J=7.8,1.7Hz,2H),7.85(d,J=9.0Hz,1H),7.58(t,J=8.0Hz,1H),7.51-7.44(m,3H),6.91(d,J=7.7Hz,1H),4.00(s,3H).13C NMR(100MHz,CDCl3)δ166.7,155.6,150.1,133.9,132.3,130.5,129.8,128.9,127.2,127.1,123.7,119.8,118.0,116.2,104.6,55.5.
实施例3产物的核磁数据如下:
1H NMR(400MHz,CDCl3,ppm)δ8.80(d,J=9.0Hz,1H),8.18-8.10(m,2H),7.82(d,J=8.7Hz,1H),7.66(d,J=8.7Hz,1H),7.51-7.43(m,3H),7.32(dd,J=9.0,2.5Hz,1H),7.23(d,J=2.4Hz,1H),3.93(s,3H).13C NMR(100MHz,CDCl3)δ167.1,157.8,150.5,134.0,133.4,130.5,129.5,128.9,127.2,125.6,125.0,123.9,119.5,118.7,106.9,55.3.
实施例4产物的核磁数据如下:
1H NMR(400MHz,CDCl3,ppm)δ8.23(d,J=2.6Hz,1H),8.19(dd,J=7.8,1.6Hz,2H),7.83(d,J=8.9Hz,1H),7.76-7.69(m,2H),7.53-7.47(m,3H),7.25-7.19(m,1H),4.06(s,3H).13C NMR(100MHz,CDCl3)δ166.5,158.6,149.7,133.9,132.2,130.5,130.0,129.7,129.0,127.3,127.2,125.7,118.4,116.4,102.7,55.6.
实施例5产物的核磁数据如下:
1H NMR(400MHz,CDCl3,ppm)δ9.02(s,1H),8.21-8.10(m,2H),7.86(d,J=8.7Hz,1H),7.75(d,J=8.7Hz,1H),7.69(d,J=8.7Hz,1H),7.65-7.57(m,1H),7.50(d,J=5.3Hz,3H).13C NMR(100MHz,CDCl3)δ167.5,149.4,133.7,132.5,130.8,130.4,129.7,129.6,129.4,129.0,127.3,126.5,125.4,121.1,119.4.
实施例6产物的核磁数据如下:
1H NMR(400MHz,CDCl3,ppm)δ8.95(d,J=7.5Hz,1H),8.16(dd,J=7.9,1.5Hz,2H),8.04(d,J=8.3Hz,1H),7.77-7.65(m,2H),7.64-7.54(m,1H),7.55-7.39(m,3H),2.74(s,3H).13C NMR(100MHz,CDCl3)δ165.8,149.4,134.0,132.5,131.4,131.3,130.3,129.0,128.6,127.2,126.6,126.0,124.5,124.5,119.0,20.0.
实施例7产物的核磁数据如下:
1H NMR(400MHz,CDCl3,ppm)δ8.98(d,J=8.1Hz,1H),8.22-8.07(m,2H),7.82(d,J=8.4Hz,1H),7.73(s,1H),7.67(t,J=7.5Hz,1H),7.60(d,J=2.0Hz,1H),7.56-7.45(m,5H),7.31(dd,J=8.2,2.0Hz,1H).13C NMR(100MHz,CDCl3)δ167.5,150.5,140.3,135.6,133.8,132.5,131.9,131.8,131.1,130.7,130.3,130.1,129.5,129.0,128.8,127.3,127.0,126.5,125.9,124.6,119.8.
实施例8产物的核磁数据如下:
1H NMR(400MHz,CDCl3,ppm)δ8.20-8.12(m,2H),7.82-7.75(m,2H),7.61(d,J=8.8Hz,1H),7.51(d,J=5.3Hz,3H),7.43-7.37(m,1H).13C NMR(100MHz,CDCl3)δ168.9,154.5,147.4,145.1,133.8,130.8,129.6,129.0,127.4,121.9,116.6,109.9,105.5.
.实施例9产物的核磁数据如下:
1H NMR(400MHz,CDCl3,ppm)δ8.14(dd,J=7.2,2.0Hz,2H),8.07(d,J=5.4Hz,1H),7.83(d,J=8.6Hz,1H),7.79(d,J=8.6Hz,1H),7.59(d,J=5.4Hz,1H),7.51-7.45(m,3H).13C NMR(100MHz,CDCl3)δ167.7,149.2,138.4,134.3,133.8,131.1,130.7,129.0,127.4,127.0,122.2,119.6,117.3.
实施例10产物的核磁数据如下:
1H NMR(400MHz,CDCl3,ppm)δ8.84(d,J=7.8Hz,1H),8.32-8.18(m,3H),7.86(d,J=8.5Hz,1H),7.55-7.45(m,6H),7.41-7.36(m,1H).13C NMR(100MHz,CDCl3)δ168.6,148.8,138.8,138.4,134.2,130.6,129.0,127.5,126.9,125.7,123.3,122.5,120.1,118.3,116.6,110.5,109.6.
实施例12产物的核磁数据如下:
1H NMR(400MHz,CDCl3,ppm)δ8.28(s,1H),8.15-8.08(m,2H),7.77(d,J=7.6Hz,2H),7.69(s,1H),7.64(d,J=7.7Hz,2H),7.57-7.45(m,6H),7.31(d,J=7.7Hz,2H),2.43(s,3H).13C NMR(100MHz,CDCl3)δ168.9,155.2,140.6,140.5,137.7,137.4,136.4,133.4,133.0,131.1,129.7,129.0,129.0,128.3,127.9,127.5,127.2,124.4,120.1,21.1.
实施例13产物的核磁数据如下:
1H NMR(400MHz,CDCl3,ppm)δ8.22(s,1H),8.13-8.05(m,2H),7.75(d,J=7.6Hz,2H),7.65(d,J=8.4Hz,3H),7.52(t,J=7.5Hz,2H),7.49-7.40(m,4H),7.01(d,J=8.3Hz,2H),3.85(s,3H).13C NMR(100MHz,CDCl3)δ168.8,159.4,155.4,140.6,140.1,136.3,133.5,133.1,132.8,131.0,129.0,128.9,128.4,128.2,127.8,127.4,124.1,119.9,114.4,55.3.
实施例14产物的核磁数据如下:
1H NMR(400MHz,CDCl3,ppm)δ8.39(s,1H),8.16(s,1H),8.14-8.04(m,2H),7.94(d,J=8.5Hz,1H),7.92-7.83(m,3H),7.83-7.74(m,3H),7.59-7.40(m,8H).13C NMR(100MHz,CDCl3)δ169.0,155.4,140.5,140.3,137.8,136.5,133.6,133.5,133.4,132.7,131.1,129.0,129.0,128.6,128.3,128.2,127.9,127.6,127.5,126.4,126.1,125.6,124.5,120.6.
实施例15产物的核磁数据如下:
1H NMR(400MHz,CDCl3,ppm)δ8.09(dd,J=6.6,2.9Hz,2H),7.89(s,1H),7.77(d,J=8.2Hz,1H),7.51-7.47(m,3H),7.22(d,J=8.0Hz,1H),2.52(s,3H).13C NMR(100MHz,CDCl3)δ168.2,154.3,136.5,133.6,131.9,130.9,129.0,127.5,126.9,123.2,121.1,21.5.
实施例16产物的核磁数据如下:
1H NMR(400MHz,CDCl3,ppm)δ8.06(dd,J=6.4,3.1Hz,2H),7.93(d,J=7.7Hz,2H),7.84(d,J=7.9Hz,1H),7.55(d,J=7.5Hz,1H),7.49(t,J=7.6Hz,2H),7.46-7.37(m,5H).13C NMR(100MHz,CDCl3)δ167.2,151.7,139.0,136.3,133.8,130.9,129.9,129.0,128.2,127.7,127.6,126.5,125.4,120.7.
实施例18产物的核磁数据如下:
1H NMR(400MHz,CDCl3,ppm)δ8.88(d,J=8.2Hz,1H),7.94(dd,J=12.0,8.4Hz,2H),7.86(d,J=7.3Hz,1H),7.81(d,J=8.7Hz,1H),7.71-7.64(m,1H),7.61-7.55(m,1H),7.40-7.29(m,3H),2.78(s,3H).13C NMR(100MHz,CDCl3)δ167.1,150.0,137.3,133.1,132.0,131.7,130.5,129.8,128.8,128.0,126.9,126.2,126.1,125.8,124.0,118.8,21.8.
实施例20产物的核磁数据如下:
1H NMR(400MHz,CDCl3,ppm)δ8.94(d,J=8.2Hz,1H),8.04(s,1H),8.01-7.89(m,3H),7.81(d,J=8.7Hz,1H),7.73-7.65(m,1H),7.63-7.55(m,1H),7.40(t,J=7.6Hz,1H),7.31(d,J=7.6Hz,1H),2.49(s,3H).13C NMR(100MHz,CDCl3)δ167.3,150.4,138.8,133.9,132.1,131.6,131.4,128.9,128.8,128.1,127.8.126.9,126.1,125.8,124.6,124.1,119.0,21.4.
实施例21产物的核磁数据如下:
1H NMR(400MHz,CDCl3,ppm)δ8.92(d,J=8.2Hz,1H),8.07(d,J=8.1Hz,2H),7.93(d,J=8.1Hz,1H),7.88(d,J=8.7Hz,1H),7.77(d,J=8.7Hz,1H),7.71-7.64(m,1H),7.57(td,J=7.6,7.0,1.2Hz,1H),7.30(d,J=7.9Hz,2H),2.42(s,3H).13C NMR(100MHz,CDCl3)δ167.3,150.3,141.0,132.0,131.4,131.3,129.7,128.7,128.0,127.2,126.8,126.0,125.7,124.0,118.9,21.5.
实施例22产物的核磁数据如下:
1H NMR(400MHz,CDCl3,ppm)δ8.87(d,J=8.2Hz,1H),8.14-8.01(m,2H),7.92(d,J=8.1Hz,1H),7.85(d,J=8.7Hz,1H),7.77(d,J=8.7Hz,1H),7.71-7.63(m,1H),7.61-7.52(m,1H),7.49-7.36(m,2H).13C NMR(100MHz,CDCl3)δ165.5,150.4,136.5,132.4,132.1,131.7,129.2,128.7,128.4,128.1,127.0,126.2,126.1,123.9,118.8.
实施例24产物的核磁数据如下:
1H NMR(400MHz,CDCl3,ppm)δ8.91(d,J=8.2Hz,1H),8.13(d,J=8.8Hz,2H),7.94(d,J=8.1Hz,1H),7.88(d,J=8.7Hz,1H),7.77(d,J=8.7Hz,1H),7.71-7.64(m,1H),7.61-7.53(m,1H),7.02(d,J=8.8Hz,2H),3.89(s,3H).13C NMR(100MHz,CDCl3)δ167.0,161.7,150.3,132.1,131.2,128.9,128.6,128.0,126.8,126.0,125.5,124.0,118.9,114.4,55.5.
实施例28产物的核磁数据如下:
1H NMR(400MHz,CDCl3,ppm)δ8.92(d,J=8.2Hz,1H),7.93(d,J=8.1Hz,1H),7.88(d,J=8.7Hz,1H),7.83-7.75(m,2H),7.75-7.63(m,2H),7.58(ddd,J=8.1,7.0,1.3Hz,1H),7.40(t,J=8.0Hz,1H),7.02(ddd,J=8.3,2.6,0.8Hz,1H),3.93(s,3H).13C NMR(100MHz,CDCl3)δ166.9,160.1,150.3,135.2,132.0,131.7,130.0,128.8,128.1,126.9,126.1,125.9,124.0,120.0,118.9,116.7,112.1,55.5.
实施例30产物的核磁数据如下:
1H NMR(400MHz,CDCl3,ppm)δ8.89(d,J=8.2Hz,1H),8.37-8.24(m,4H),7.94(dd,J=17.6,8.4Hz,2H),7.85(d,J=8.8Hz,1H),7.72(t,J=7.1Hz,1H),7.65-7.59(m,1H).13CNMR(100MHz,CDCl3)δ163.6,150.7,148.7,139.4,132.6,132.2,128.9,128.2,127.8,127.4,127.2,126.6,124.3,123.9,118.8.
实施例31产物的核磁数据如下:
1H NMR(400MHz,CDCl3,ppm)δ8.93(d,J=8.2Hz,1H),8.11(d,J=8.3Hz,2H),7.93(d,J=8.1Hz,1H),7.88(d,J=8.7Hz,1H),7.77(d,J=8.7Hz,1H),7.68(t,J=7.6Hz,1H),7.60-7.54(m,1H),7.52(d,J=8.4Hz,2H),1.37(s,9H).13C NMR(100MHz,CDCl3)δ167.2,154.1,150.4,132.0,131.5,131.2,128.7,128.0,127.1,126.9,126.0,126.0,125.7,124.1,119.0,35.0,31.2.
实施例32产物的核磁数据如下:
1H NMR(400MHz,CDCl3,ppm)δ8.94(d,J=8.2Hz,1H),8.67(d,J=8.8Hz,1H),7.90(dd,J=13.8,8.4Hz,2H),7.72(d,J=8.7Hz,1H),7.69-7.63(m,1H),7.60-7.48(m,1H),6.67(dd,J=8.8,2.4Hz,1H),6.53(d,J=2.3Hz,1H),3.99(s,3H),3.84(s,3H).13C NMR(100MHz,CDCl3)δ162.5,162.0,158.2,148.3,131.9,131.9,130.5,128.4,128.0,126.5,125.7,124.7,123.9,118.9,116.0,106.0,98.3,55.6,55.5.
实施例33产物的核磁数据如下:
1H NMR(400MHz,CDCl3,ppm)δ8.90(d,J=8.1Hz,1H),8.48(d,J=8.5Hz,1H),7.94(dd,J=14.4,8.4Hz,2H),7.83(d,J=8.7Hz,1H),7.70(t,J=7.4Hz,1H),7.60(t,J=7.4Hz,1H),7.56(s,1H),7.42(d,J=8.5Hz,1H).13C NMR(100MHz,CDCl3)δ161.5,148.7,136.2,133.0,132.4,132.1,131.0,130.5,128.7,128.2,127.6,127.1,126.5,126.3,123.9,118.6.
实施例34产物的核磁数据如下:
1H NMR(400MHz,CDCl3,ppm)δ8.92(d,J=8.2Hz,1H),7.97(s,1H),7.92(d,J=8.1Hz,1H),7.91-7.84(m,2H),7.76(d,J=8.7Hz,1H),7.71-7.63(m,1H),7.60-7.53(m,1H),7.27-7.21(m,1H),2.37(s,3H),2.32(s,3H).13C NMR(100MHz,CDCl3)δ167.5,150.4,139.7,137.3,132.0,131.6,131.4,130.2,128.7,128.3,128.0,126.8,126.0,125.6,124.8,124.1,118.9,19.8,19.8.
实施例35产物的核磁数据如下:
1H NMR(400MHz,CDCl3,ppm)δ8.75(d,J=8.2Hz,1H),7.90(d,J=8.1Hz,1H),7.79(d,J=8.7Hz,1H),7.72(d,J=8.7Hz,1H),7.65-7.60(m,1H),7.57-7.50(m,1H),2.57-2.46(m,1H),1.25(d,J=6.5Hz,4H).13C NMR(100MHz,CDCl3)δ173.6,149.3,131.9,130.2,128.2,127.9,126.6,125.8,124.9,123.9,118.8,15.4,11.8
实施例36产物的核磁数据如下:
1H NMR(400MHz,CDCl3,ppm)δ8.98(d,J=8.2Hz,1H),8.63(s,1H),8.32(d,J=8.5Hz,1H),8.01-7.84(m,5H),7.80(d,J=8.7Hz,1H),7.71(t,J=7.6Hz,1H),7.59(t,J=7.5Hz,1H),7.54(dd,J=6.1,3.2Hz,2H).13C NMR(100MHz,CDCl3)δ167.1,150.4,134.5,133.3,132.1,131.7,131.3,128.8,128.8,128.1,127.9,127.3,127.1,127.0,126.8,126.2,126.0,124.5,124.1,118.9.
实施例37产物的核磁数据如下:
1H NMR(400MHz,CDCl3,ppm)δ8.93(d,J=8.2Hz,1H),7.95(d,J=8.1Hz,1H),7.89(d,J=8.7Hz,1H),7.79(d,J=8.7Hz,1H),7.69(t,J=7.2Hz,1H),7.62-7.56(m,1H),7.42(s,2H),4.02(s,6H),3.94(s,3H).13C NMR(100MHz,CDCl3)δ166.8,153.6,150.3,140.4,132.1,131.6,129.4,128.6,128.1,126.9,126.1,125.8,124.0,118.9,104.6,61.0,56.3.
实施例38产物的核磁数据如下:
1H NMR(400MHz,CDCl3,ppm)δ8.91(d,J=8.2Hz,1H),8.68(d,J=7.9Hz,1H),8.52(d,J=7.9Hz,1H),7.96(d,J=8.8Hz,2H),7.87(td,J=7.8,1.7Hz,1H),7.83(d,J=8.7Hz,1H),7.73-7.67(m,1H),7.62-7.56(m,1H),7.41-7.33(m,1H).13C NMR(100MHz,CDCl3)δ168.0,151.7,150.6,149.5,137.1,133.2,132.0,128.9,128.1,127.0,126.5,126.2,124.9,123.7,120.6,119.3.
实施例39产物的核磁数据如下:
1H NMR(400MHz,CDCl3,ppm)δ8.86(d,J=8.2Hz,1H),7.91(d,J=8.1Hz,1H),7.83(d,J=8.7Hz,1H),7.76(d,J=8.7Hz,1H),7.70-7.62(m,2H),7.56(ddd,J=8.1,7.0,1.3Hz,1H),7.47(dd,J=5.0,1.1Hz,1H),7.12(dd,J=5.0,3.7Hz,1H).13C NMR(100MHz,CDCl3)δ160.4,150.0,137.8,132.0,131.2,128.7,128.4,128.0,127.8,126.9,126.1,125.9,124.1,118.7.
实施例41产物的核磁数据如下:
1H NMR(400MHz,CDCl3,ppm)δ8.88(d,J=8.2Hz,1H),7.94(d,J=8.1Hz,1H),7.88(d,J=8.7Hz,1H),7.79(d,J=8.7Hz,1H),7.70-7.64(m,1H),7.62-7.54(m,2H),7.28-7.23(m,1H),6.61(dd,J=3.5,1.8Hz,1H).13C NMR(100MHz,CDCl3)δ156.7,150.1,149.1,144.3,132.1,130.9,128.5,128.0,126.9,126.2,126.0,124.0,118.8,112.5,110.8.
实施例42产物的核磁数据如下:
1H NMR(400MHz,CDCl3,ppm)δ8.06(d,J=5.4Hz,1H),7.85(d,J=8.6Hz,1H),7.79(d,J=8.6Hz,1H),7.63-7.57(m,2H),7.23(d,J=3.4Hz,1H),6.62-6.57(m,1H).13C NMR(100MHz,CDCl3)δ157.2,148.9,148.9,144.5,138.6,134.1,130.3,127.1,122.2,119.7,117.2,112.5,111.2.
实施例43产物的核磁数据如下:
1H NMR(400MHz,CDCl3,ppm)δ9.42-9.18(m,1H),9.03(d,J=4.5Hz,1H),8.95(d,J=8.2Hz,1H),8.25(d,J=8.3Hz,1H),8.05-7.94(m,2H),7.90(d,J=8.8Hz,1H),7.88-7.79(m,2H),7.74(m,2H),7.68-7.61(m,1H).13C NMR(100MHz,CDCl3)δ163.6,150.7,149.5,148.9,138.5,132.4,132.1,130.1,129.7,128.9,128.2,127.4,127.2,126.6,126.4,125.0,124.0,121.9,118.6.
表 实施例1-46反应的转化率及产物图
以上述依据本发明的理想实施例为启示,通过上述的说明内容,相关工作人员完全可以在不偏离本项发明技术思想的范围内,进行多样的变更以及修改。本项发明的技术性范围并不局限于说明书上的内容,必须要根据权利要求范围来确定其技术性范围。
Claims (2)
1.一种多取代萘并[1,2-d]噻唑及衍生物的合成方法,其特征在于,以铜类化合物作催化剂,包括以下步骤:
S1:将酮肟酯类化合物,甲醛类化合物,硫粉,催化剂与有机溶剂在反应容器内进行充分混合;
S2:空气氛围下,对反应物加热进行反应;
S3:纯化得到多取代萘并[1,2-d]噻唑及衍生物;
所述酮肟酯类化合物选自:四氢萘酮肟酯,5-甲氧基-3,4-二氢萘-1(2H)-酮肟酯,6-甲氧基-3,4-二氢萘-1(2H)-酮肟酯,7-甲氧基-3,4-二氢萘-1(2H)-酮肟酯,7-溴-3,4-二氢萘-1(2H)-酮肟酯,4-甲基-3,4-二氢萘-1(2H)-酮肟酯,4-(3,4-二氯苯基)-3,4-二氢萘-1(2H)-酮肟酯,6,7-二氢苯并呋喃-4(5H)-酮肟酯,6,7-二氢苯并[b]噻吩-4(5H)-酮肟酯,2,3-二氢-1H-咔唑-4(9H)-酮肟酯,9-甲基-2,3-二氢-1H-咔唑-4(9H)-酮肟酯,4″-甲基-1′,6′-二氢-[1,1′:3′,1“-三联苯]-5′(2′H)-酮肟酯,4″-甲氧基-1′,6′-二氢-[1,1′:3′,1“-三联苯]-5′(2′H)-酮酮肟酯,5-(萘-2-基)-1,6-二氢-[1,1′-联苯]-3(2H)-酮肟酯,3-甲基环己-2-烯酮肟酯,4,5-二氢-[1,1′-联苯基]-2(3H)-酮肟酯;
所述甲醛类化合物选自:苯甲醛,4-甲基苯甲醛,4-苯基苯甲醛,4-叔丁基苯甲醛,4-甲氧基苯甲醛,4-氟苯甲醛,4-氯苯甲醛,4-溴苯甲醛,4-硝基苯甲醛,2-甲基苯甲醛,2-氟苯甲醛,2-氯苯甲醛,3-甲基苯甲醛,3-甲氧基苯甲醛,3-氟苯甲醛,3-氯苯甲醛,3-溴苯甲醛,4-三氟甲基苯甲醛,对苯基苯甲醛,2,4-二甲基苯甲醛,2,4-二氯苯甲醛,3,4-二甲氧基苯甲醛,3,4,5-三甲氧基苯甲醛,3,4-二氯苯甲醛,2-萘醛,2-噻吩甲醛,2-吡啶甲醛,4-吡啶甲醛,4-喹啉甲醛,糠醛,环丙基甲醛;
所述铜类化合物选自:铜粉,氯化亚铜,溴化亚铜,碘化亚铜,氧化亚铜,无水硫酸铜,无水乙酰丙酮,无水乙酸铜,磺化亚铜,碱式碳酸铜,氯化铜,溴化铜,氧化铜中的一种或多种;
所述甲醛类化合物、酮肟酯类化合物、硫粉与催化剂的摩尔比为1.0∶1.1-4.0∶2.2-8.0∶0.1-0.3;反应温度为100℃-140℃,反应时长为8h-24h;
得到的多取代萘并[1,2-d]噻唑及衍生物的结构式为:
2.根据权利要求1所述的合成方法,其特征在于,所述有机溶剂为二甲基亚砜或N,N-二甲基甲酰胺。
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