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CN118772036A - A method for synthesizing an organic compound containing an indole naphthoquinone skeleton - Google Patents

A method for synthesizing an organic compound containing an indole naphthoquinone skeleton Download PDF

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CN118772036A
CN118772036A CN202410769330.0A CN202410769330A CN118772036A CN 118772036 A CN118772036 A CN 118772036A CN 202410769330 A CN202410769330 A CN 202410769330A CN 118772036 A CN118772036 A CN 118772036A
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naphthoquinone
indolyl
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cdcl
nmr
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董宇
吴春梅
陈林
邓国伟
何冰
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Chengdu Normal University
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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
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
    • C07D209/18—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • 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
    • C07D209/94—[b, c]- or [b, d]-condensed containing carbocyclic rings other than six-membered

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Abstract

本发明提供了一种合成含有吲哚萘醌骨架的有机化合物的方法，涉及有机合成技术领域。本发明以吲哚萘醌衍生物和丙二酸二乙酯为原料，在催化剂的作用下于有机溶剂中进行合成反应，得到含有吲哚萘醌骨架的有机化合物。本发明通过调整催化剂以及反应物料，从而合成了一系列烷基化吲哚萘醌化合物和并环吲哚萘醌的化合物。本发明的合成工艺简单且难度低，能够便于工业化生成。The invention provides a method for synthesizing an organic compound containing an indole naphthoquinone skeleton, and relates to the technical field of organic synthesis. The invention uses an indole naphthoquinone derivative and diethyl malonate as raw materials, performs a synthesis reaction in an organic solvent under the action of a catalyst, and obtains an organic compound containing an indole naphthoquinone skeleton. The invention synthesizes a series of alkylated indole naphthoquinone compounds and cycloindole naphthoquinone compounds by adjusting the catalyst and the reaction materials. The synthesis process of the invention is simple and has low difficulty, and can be easily produced in industrialized form.

Description

一种合成含有吲哚萘醌骨架的有机化合物的方法A method for synthesizing an organic compound containing an indole naphthoquinone skeleton

技术领域Technical Field

本发明提供一种合成含有吲哚萘醌骨架的有机化合物的方法，属于有机合成技术领域。The invention provides a method for synthesizing an organic compound containing an indole naphthoquinone skeleton, belonging to the technical field of organic synthesis.

背景技术Background Art

基于醌类有机分子在全合成、药物化学、材料科学、农业化学和作为染料中发挥重要作用，由于其独特的视觉和醌的电子转移特性。其中值得注意的是醌类衍生物的烷基取代，如巴伐醌，已被批准用于治疗一种来自泰勒虫和疟疾的疾病。拉帕乔尔也通常显示出重要的生物活性。因此，开发合成方法将功能性烷基化纳入醌是非常重要的意义。此外，多环N-杂环化合物广泛存在于各种天然产物、药物和功能材料中，因而成为特殊的结构基序。醌类融合多环氮杂环蓟菌素A的代表性例子以剂量依赖的方式抑制人类寄生虫耐氯喹菌株恶性疟原虫的体外生长。在2017年，米妥妥林(FDA批准的药物)被批准用于治疗被诊断为急性骨髓性白血病的血癌患。因此，发展简明、直接的方法来合成这样的烷基化吲哚萘醌和并环吲哚萘醌化合物是非常可取的。Quinone-based organic molecules play an important role in total synthesis, medicinal chemistry, materials science, agricultural chemistry and as dyes due to their unique visual and electron transfer properties of quinones. Notable among them are alkyl substitutions of quinone derivatives, such as bavaquinone, which has been approved for the treatment of a disease from Theileria and malaria. Rapachoul also generally displays important biological activities. Therefore, the development of synthetic methods to incorporate functional alkylation into quinones is of great significance. In addition, polycyclic N-heterocyclic compounds are widely present in various natural products, drugs and functional materials, thus becoming special structural motifs. A representative example of quinone-fused polycyclic azacyclopentylin A inhibits the in vitro growth of chloroquine-resistant strains of the human parasite Plasmodium falciparum in a dose-dependent manner. In 2017, metoclopramide (an FDA-approved drug) was approved for the treatment of blood cancer patients diagnosed with acute myeloid leukemia. Therefore, the development of concise and direct methods to synthesize such alkylated indole naphthoquinone and para-indole naphthoquinone compounds is highly desirable.

目前，醌的C-H烷基化是构建烷基化醌的一种众所周知的有效方法(Ind.Eng.Chem.Res.,2019,58,13076-13084)。其他策略是通过弗里德尔·克拉夫特提出的反应，光烷基化有机锡，自由基反应，有机铵，铜酸盐，烷基硼烷，烷基锂和格氏反应。然而，大多数现有方法都受到危险和昂贵的金属催化、预功能化和相当有限的底物范围的要求。因此，开发一种可应用于醌衍生物的新型高效烷基化方法非常可取。此外，在2020年和2021年，开发了钴/铜催化的[4+1]吲哚萘醌和各种(杂)芳香胺的环胺反应，用于合成多环N-杂环(Journal of Fluorine Chemistry.,2021,250,109864；Org.Lett.,2020,22,528–532；J.Chem.Soc.,Perkin Trans.1986,2,1827–1831；J.Am.Chem.Soc.,2011,133,3292-3295；Synlett.,2021,32,1772-1776.)。综上所述目前吲哚萘醌与丙二酸二乙酯的直接烷基化和[4+1]环加成尚未报道。Currently, C-H alkylation of quinones is a well-known and efficient method for constructing alkylated quinones (Ind. Eng. Chem. Res., 2019, 58, 13076-13084). Other strategies are through the reaction proposed by Friedel Craft, photoalkylation of organotin, free radical reactions, organoammonium, cuprates, alkylboranes, alkyllithium and Grignard reactions. However, most existing methods are subject to the requirements of dangerous and expensive metal catalysis, prefunctionalization and a rather limited substrate range. Therefore, it is highly desirable to develop a new and efficient alkylation method that can be applied to quinone derivatives. In addition, in 2020 and 2021, cobalt/copper-catalyzed [4+1] cycloaddition reactions of indole naphthoquinone and various (hetero)aromatic amines were developed for the synthesis of polycyclic N-heterocycles (Journal of Fluorine Chemistry., 2021, 250, 109864; Org. Lett., 2020, 22, 528–532; J. Chem. Soc., Perkin Trans. 1986, 2, 1827–1831; J. Am. Chem. Soc., 2011, 133, 3292-3295; Synlett., 2021, 32, 1772-1776.). In summary, direct alkylation and [4+1] cycloaddition of indole naphthoquinone with diethyl malonate have not been reported.

发明内容Summary of the invention

有鉴于此，本发明的目的在于：提供一种合成含有吲哚萘醌骨架的有机化合物，具体是利用吲哚萘醌衍生物和丙二酸二乙酯为原料，在催化剂的作用下合成烷基化吲哚萘醌化合物或并环吲哚萘醌的化合物。In view of this, the purpose of the present invention is to provide a method for synthesizing an organic compound containing an indole naphthoquinone skeleton, specifically using an indole naphthoquinone derivative and diethyl malonate as raw materials to synthesize an alkylated indole naphthoquinone compound or a cycloindole naphthoquinone compound under the action of a catalyst.

本发明是采用以下技术方案实现的：The present invention is achieved by adopting the following technical solutions:

一种合成含有吲哚萘醌骨架的有机化合物的方法，具体是以吲哚萘醌衍生物和丙二酸二乙酯为原料，在催化剂的作用下于有机溶剂中进行合成反应，得到含有吲哚萘醌骨架的有机化合物；A method for synthesizing an organic compound containing an indole naphthoquinone skeleton, specifically using an indole naphthoquinone derivative and diethyl malonate as raw materials, carrying out a synthesis reaction in an organic solvent under the action of a catalyst, to obtain an organic compound containing an indole naphthoquinone skeleton;

所述含有吲哚萘醌骨架的有机化合物包括烷基化吲哚萘醌化合物或并环吲哚萘醌的化合物；The organic compound containing an indole naphthoquinone skeleton includes an alkylated indole naphthoquinone compound or a cycloindole naphthoquinone compound;

所述烷基化吲哚萘醌化合物的结构式如下：The structural formula of the alkylated indole naphthoquinone compound is as follows:

所述并环吲哚萘醌的化合物为下列结构式中的一种：The compound of the cycloindole naphthoquinone is one of the following structural formulas:

所述结构式(III)和结构式(IV)中，R1均选自C1-C3的烷基；R2均选自氢或甲基；R3均选自烷基、烷氧基、卤素基或氢；R4为苯基。In the structural formula (III) and the structural formula (IV), R 1 is selected from a C1-C3 alkyl group; R 2 is selected from hydrogen or methyl; R 3 is selected from an alkyl group, an alkoxy group, a halogen group or hydrogen; and R 4 is a phenyl group.

优选的，所述吲哚萘醌衍生物的结构式如下：Preferably, the structural formula of the indole naphthoquinone derivative is as follows:

所述结构式(I)中，R1均选自C1-C3的烷基；R2均选自氢或甲基；R3均选自烷基、烷氧基、卤素基或氢；R4为苯基。In the structural formula (I), R 1 is selected from C1-C3 alkyl; R 2 is selected from hydrogen or methyl; R 3 is selected from alkyl, alkoxy, halogen or hydrogen; R 4 is phenyl.

优选的，当合成烷基化吲哚萘醌化合物时，所采用的催化剂为氯化锌和叔丁醇钾；Preferably, when synthesizing the alkylated indole naphthoquinone compound, the catalysts used are zinc chloride and potassium tert-butoxide;

所述吲哚萘醌衍生物与丙二酸二乙酯的摩尔比为1:(1-3)；The molar ratio of the indole naphthoquinone derivative to diethyl malonate is 1:(1-3);

所述氯化锌占吲哚萘醌衍生物摩尔量的(20-50)％；The zinc chloride accounts for (20-50)% of the molar amount of the indole naphthoquinone derivative;

所述叔丁醇钾与吲哚萘醌衍生物的摩尔比(1-4):1。The molar ratio of the potassium tert-butoxide to the indole naphthoquinone derivative is (1-4):1.

优选的，当并环吲哚萘醌的化合物时，所采用的催化剂为碳酸钾和碘化亚铜；Preferably, when the compound is a cyclized indole naphthoquinone, the catalyst used is potassium carbonate and cuprous iodide;

所述吲哚萘醌衍生物与丙二酸二乙酯的摩尔比为1:(1-4)；The molar ratio of the indole naphthoquinone derivative to diethyl malonate is 1:(1-4);

所述碳酸钾与吲哚萘醌衍生物的摩尔比(1-2):1；The molar ratio of potassium carbonate to indole naphthoquinone derivative is (1-2): 1;

所述碘化亚铜占吲哚萘醌衍生物摩尔量的(10-40)％。The cuprous iodide accounts for (10-40)% of the molar amount of the indole naphthoquinone derivative.

优选的，所述有机溶剂为乙腈。Preferably, the organic solvent is acetonitrile.

优选的，所述合成反应时间为0.5h-2h，反应温度为80℃-120℃，反应条件为密闭条件。Preferably, the synthesis reaction time is 0.5h-2h, the reaction temperature is 80°C-120°C, and the reaction conditions are closed conditions.

与现有技术相比，本发明本发明的合成方法具有操作简单且成本低，同时还具有选择性高且产率高等优点，在制药、功能材料等领域具有应用前景。Compared with the prior art, the synthesis method of the present invention has the advantages of simple operation and low cost, as well as high selectivity and high yield, and has application prospects in the fields of pharmaceuticals, functional materials, etc.

具体实施方式DETAILED DESCRIPTION

为使本发明的目的、技术方案和优点更加清楚，下面结合实施例对本发明优选实施方案进行进一步地详细描述。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。In order to make the purpose, technical scheme and advantages of the present invention clearer, the preferred embodiments of the present invention are further described in detail in conjunction with the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

实施例1Example 1

按照上述合成路线，将吲哚萘醌1a(0.15mmol)和ZnCl2(0.06mmol，40mmol/％)，t-BuOK(0.3mmol，2eq)置于1ml CH3CN中，然后加入丙二酸二乙酯2a(0.3mmol)。将反应混合物在100℃下在密封管下搅拌1小时。反应完成后(通过TLC监测)。用饱和盐水(6mL)猝灭反应，并用EtOAc(3×3ml)萃取混合物。有机提取物用盐水洗涤，用Na2SO4干燥，过滤，真空除去溶剂。粗产物通过硅胶柱色谱法纯化，得到化合物3a。红色固体(50mg，产率89％)；mp 225-227℃；在硅胶柱上纯化(石油醚/乙酸乙酯＝5：1)。According to the above synthetic route, indole naphthoquinone 1a (0.15mmol) and ZnCl 2 (0.06mmol, 40mmol/%), t-BuOK (0.3mmol, 2eq) were placed in 1ml CH 3 CN, and then diethyl malonate 2a (0.3mmol) was added. The reaction mixture was stirred at 100°C under a sealed tube for 1 hour. After the reaction was completed (monitored by TLC). The reaction was quenched with saturated brine (6mL), and the mixture was extracted with EtOAc (3×3ml). The organic extract was washed with brine, dried over Na 2 SO 4 , filtered, and the solvent was removed in vacuo. The crude product was purified by silica gel column chromatography to obtain compound 3a. Red solid (50mg, yield 89%); mp 225-227°C; purified on a silica gel column (petroleum ether/ethyl acetate=5:1).

对化合物3a进行表征，具体如下：Compound 3a was characterized as follows:

表征特征：1H NMR(400MHz,CDCl3)δ8.14(s,2H),7.74(s,2H),7.42–7.23(m,5H),7.16(t,J＝7.2Hz,1H),4.13(dd,J＝13.6,6.7Hz,2H),3.87(s,3H),3.68(s,2H),1.24–1.20(m,3H).13C NMR(101MHz,CDCl3)δ184.95,184.34,170.85,142.11,139.20,136.94,133.67,133.57,132.39,132.05,131.78,127.22,126.82,126.28,122.30,120.65,120.26,109.83,106.47,61.04,35.46,33.29,14.13.HRMS(ESI)m/z calcd for C23H19NO4Na+(M+Na)+396.1211,found 396.1212.Characterization characteristics: 1 H NMR (400MHz, CDCl 3 )δ8.14(s,2H),7.74(s,2H),7.42–7.23(m,5H),7.16(t,J＝7.2Hz,1H),4.13(dd,J＝13.6,6.7Hz,2H),3.87(s,3H),3.68(s,2H),1.24–1.20(m,3H). 13 C NMR (101MHz,CDCl 3 )δ184.95,184.34,170.85,142.11,139.20,136.94,133.67,133.57,132.39,132.05,131.78,127.22,126.82,126.28,122.30,120.65,120.26,1 09.83,106.47,61.04,35.46,33.29,14.13.HRMS(ESI)m/z calcd for C 23 H 19 NO 4 Na + (M+Na) + 396.1211, found 396.1212.

实施例2Example 2

按照上述合成路线以及按照实施例1的方法，得到红色固体化合物3b(49mg，产率85％)；mp198-200℃；通过硅胶柱纯化(石油醚/乙酸乙酯＝5：1)。According to the above synthetic route and the method of Example 1, a red solid compound 3b (49 mg, yield 85%) was obtained; mp 198-200° C.; purified by silica gel column (petroleum ether/ethyl acetate=5:1).

对化合物3b进行表征，具体如下：Compound 3b was characterized as follows:

表征特征：1H NMR(400MHz,CDCl3)δ8.15(d,J＝6.5Hz,2H),7.75(dd,J＝8.6,5.2Hz,2H),7.40(d,J＝9.5Hz,3H),7.26(dd,J＝8.8,6.3Hz,1H),7.16(t,J＝7.5Hz,1H),4.29–4.23(m,2H),4.19–4.12(m,2H),3.70(s,2H),1.55(t,J＝7.3Hz,3H),1.22(d,J＝7.1Hz,3H).13C NMR(101MHz,CDCl3)δ184.89,184.35,170.90,142.07,139.15,135.82,133.61,133.53,132.53,132.17,130.16,127.43,126.77,126.27,122.14,120.59,120.43,109.88,106.62,60.99,41.41,35.48,15.30,14.12.HRMS(ESI)m/z calcd for C24H21NO4Na+(M+Na)+410.1371,found 410.1368.Characterization characteristics: 1 H NMR (400MHz, CDCl 3 )δ8.15 (d, J＝6.5Hz, 2H), 7.75 (dd, J＝8.6, 5.2Hz, 2H), 7.40 (d, J＝9.5Hz, 3H), 7.26 (dd, J＝8.8, 6.3Hz, 1H), 7.16 (t, J＝7.5Hz, 1H), 4.29–4.23 (m, 2H), 4.19–4.12 (m, 2H), 3.70 (s, 2H), 1.55 (t, J＝7.3Hz, 3H), 1.22 (d, J＝7.1Hz, 3H). 13 C NMR (101MHz, CDCl 3 )δ184.89,184.35,170.90,142.07,139.15,135.82,133.61,133.53,132.53,132.17,130.16,127.43,126.77,126.27,122.14,120.59,120.43,1 09.88,106.62,60.99,41.41,35.48,15.30,14.12.HRMS(ESI)m/z calcd for C 24 H 21 NO 4 Na + (M+Na) + 410.1371, found 410.1368.

实施例3Example 3

按照上述合成路线以及按照实施例1的方法，得到红色固体化合物3c(34mg，产率56％)；mp178-180℃；通过硅胶柱纯化(石油醚/乙酸乙酯＝5：1)。According to the above synthetic route and the method of Example 1, a red solid compound 3c (34 mg, yield 56%) was obtained; mp 178-180° C.; purified by silica gel column (petroleum ether/ethyl acetate=5:1).

对化合物3c进行表征，具体如下：Compound 3c was characterized as follows:

表征特征：1H NMR(400MHz,CDCl3)δ8.15(d,J＝4.3Hz,2H),7.78–7.72(m,2H),7.42–7.35(m,3H),7.31–7.20(m,2H),7.16(t,J＝7.5Hz,1H),6.11–6.02(m,1H),5.30–5.19(m,2H),4.80(d,J＝4.4Hz,2H),4.13(q,J＝7.1Hz,2H),3.69(s,2H),1.22(d,J＝7.1Hz,3H).13C NMR(101MHz,CDCl3)δ184.77,184.21,170.83,141.91,139.40,136.13,133.63,133.56,132.71,132.38,132.08,130.72,127.44,126.78,126.30,122.31,120.73,120.37,118.17,110.17,106.7,61.01,49.20,35.41,14.11.HRMS(ESI)m/z calcd for C25H22NO4 +(M+H)+400.1544,found400.1549.Characterization characteristics: 1 H NMR (400MHz, CDCl 3 )δ8.15(d, J＝4.3Hz,2H),7.78–7.72(m,2H),7.42–7.35(m,3H),7.31–7.20(m,2H),7.16(t, J＝7.5Hz,1H),6.11–6.02(m,1H),5.30–5.19(m,2H),4.80(d, J＝4.4Hz,2H),4.13(q, J＝7.1Hz,2H),3.69(s,2H),1.22(d, J＝7.1Hz,3H). 13 C NMR (101MHz,CDCl 3 )δ184.77,184.21,170.83,141.91,139.40,136.13,133.63,133.56,132.71,132.38,132.08,130.72,127.44,126.78,126.30,122.31,120.73,1 20.37,118.17,110.17,106.7,61.01,49.20,35.41,14.11.HRMS(ESI)m/z calcd for C 25 H 22 NO 4 + (M+H) + 400.1544,found400.1549.

实施例4Example 4

按照上述合成路线以及按照实施例1的方法，得到紫红色固体化合物3d(39mg，产率63％)；mp178-180℃；通过硅胶柱纯化(石油醚/乙酸乙酯＝5：1)。According to the above synthetic route and the method of Example 1, a purple solid compound 3d (39 mg, yield 63%) was obtained; mp 178-180° C.; purified by silica gel column (petroleum ether/ethyl acetate=5:1).

对化合物3d进行表征，具体如下：Compound 3d was characterized as follows:

表征特征：1H NMR(400MHz,CDCl3)δ8.16(t,J＝8.1Hz,2H),7.79–7.72(m,2H),7.34–7.17(m,3H),7.09(t,J＝7.4Hz,1H),4.10–4.01(m,2H),3.74(s,3H),3.66–3.51(m,2H),2.30(s,3H),1.16(t,J＝7.1Hz,3H).Characterization characteristics: 1 H NMR (400 MHz, CDCl 3 ) δ8.16 (t, J=8.1 Hz, 2H), 7.79–7.72 (m, 2H), 7.34–7.17 (m, 3H), 7.09 (t, J=7.4 Hz, 1H), 4.10–4.01 (m, 2H), 3.74 (s, 3H), 3.66–3.51 (m, 2H), 2.30 (s, 3H), 1.16 (t, J=7.1 Hz, 3H).

13C NMR(101MHz,CDCl3)δ184.82,183.96,170.18,143.08,142.27,136.91,133.64,132.54,132.18,126.93,126.89,126.39,121.35,120.26,118.70,109.19,104.8,60.87,34.95,29.83,14.05,12.08.HRMS(ESI)m/z calcd for C24H21NO4Na+(M+Na)+410.1371,found 410.1368. 13 C NMR (101MHz, CDCl 3 ) δ184.82,183.96,170.18,143.08,142.27,136.91,133.64,132.54,132.18,126.93,126.89,126.39,121.35,120.26,118.7 0,109.19,104.8,60.87,34.95,29.83,14.05 ,12.08.HRMS(ESI)m/z calcd for C 24 H 21 NO 4 Na + (M+Na) + 410.1371, found 410.1368.

实施例5Example 5

按照上述合成路线以及按照实施例1的方法，得到紫红色固体化合物3e(39mg，产率64％)；mp170-172℃；通过硅胶柱纯化(石油醚/乙酸乙酯＝5：1)。According to the above synthetic route and the method of Example 1, a purple solid compound 3e (39 mg, yield 64%) was obtained; mp 170-172° C.; purified by silica gel column (petroleum ether/ethyl acetate=5:1).

对化合物3e进行表征，具体如下：Compound 3e was characterized as follows:

表征特征：1H NMR(400MHz,CDCl3)δ8.17(dd,J＝4.2,1.6Hz,2H),7.82–7.73(m,2H),7.25–7.16(m,2H),7.07(s,1H),6.91(d,J＝6.6Hz,1H),4.17–4.06(m,2H),3.80(s,3H),2.30(s,3H),1.22(t,J＝7.1Hz,3H).Characterization characteristics: 1 H NMR (400 MHz, CDCl 3 ) δ8.17 (dd, J=4.2, 1.6 Hz, 2H), 7.82–7.73 (m, 2H), 7.25–7.16 (m, 2H), 7.07 (s, 1H), 6.91 (d, J=6.6 Hz, 1H), 4.17–4.06 (m, 2H), 3.80 (s, 3H), 2.30 (s, 3H), 1.22 (t, J=7.1 Hz, 3H).

13C NMR(101MHz,CDCl3)δ185.47,184.73,170.50,145.25,141.06,137.35,133.75,133.71,132.34,132.10,130.69,128.75,126.86,126.80,126.40,122.58,121.77,107.55,107.4,61.07,34.87,33.18,19.85,14.13.HRMS(ESI)m/z calcd for C24H21NO4Na+(M+Na)+410.1375,found 410.1368. 13 C NMR (101MHz, CDCl 3 ) δ185.47,184.73,170.50,145.25,141.06,137.35,133.75,133.71,132.34,132.10,130.69,128.75,126.86,126.80,126.4 0,122.58,121.77,107.55,107.4,61.07,34.87 ,33.18,19.85,14.13.HRMS(ESI)m/z calcd for C 24 H 21 NO 4 Na + (M+Na) + 410.1375, found 410.1368.

实施例6Example 6

按照上述合成路线以及按照实施例1的方法，得到红色固体化合物3f(41mg，产率67％)；mp192-194℃；通过硅胶柱纯化(石油醚/乙酸乙酯＝5：1)。According to the above synthetic route and the method of Example 1, a red solid compound 3f (41 mg, yield 67%) was obtained; mp 192-194° C.; and purified by silica gel column (petroleum ether/ethyl acetate=5:1).

对化合物3f进行表征，具体如下：Compound 3f was characterized as follows:

表征特征：1H NMR(400MHz,CDCl3)δ8.14(d,J＝4.5Hz,2H),7.77–7.72(m,2H),7.35(s,1H),7.28(dd,J＝8.8,4.2Hz,1H),7.03(dd,J＝20.4,9.5Hz,2H),4.15(q,J＝7.1Hz,2H),3.86(s,3H),3.66(s,2H),1.26–1.24(m,3H).13C NMR(101MHz,CDCl3)δ184.70,184.37,170.70,159.66,157.31,141.59,139.48,133.73,133.63,133.45,133.01,132.35,132.10,127.71,127.61,126.82,126.33,110.97,110.70,110.63,110.53,105.49,105.25,61.15,35.39,33.52,14.09.19F NMR(376MHz,CDCl3)δ-123.00.HRMS(ESI)m/z calcd forC23H18NO4FNa+(M+Na)+414.1114,found 414.1118.Characterization characteristics: 1 H NMR (400MHz, CDCl 3 )δ8.14 (d, J＝4.5Hz, 2H), 7.77–7.72 (m, 2H), 7.35 (s, 1H), 7.28 (dd, J＝8.8, 4.2Hz, 1H), 7.03 (dd, J＝20.4, 9.5Hz, 2H), 4.15 (q, J＝7.1Hz, 2H), 3.86 (s, 3H), 3.66 (s, 2H), 1.26–1.24 (m, 3H). 13 C NMR (101MHz, CDCl 3 )δ184.70,184.37,170.70,159.66,157.31,141.59,139.48,133.73,133.63,133.45,133.01,132.35,132.10,127.71,127.61,126.82,126.33,1 10.97,110.70,110.63,110.53,105.49,105.25,61.15,35.39,33.52,14.09. 19 F NMR (376MHz, CDCl 3 )δ-123.00.HRMS (ESI) m/z calcd forC 23 H 18 NO 4 FNa + (M+Na) + 414.1114,found 414.1118.

实施例7Example 7

按照上述合成路线以及按照实施例1的方法，得到橙红色固体化合物3g(42mg，产率65％)；mp167-169℃；通过硅胶柱纯化(石油醚/乙酸乙酯＝5：1)。According to the above synthetic route and the method of Example 1, 3 g (42 mg, yield 65%) of orange-red solid compound was obtained; mp 167-169° C.; purified by silica gel column (petroleum ether/ethyl acetate=5:1).

对化合物3g进行表征，具体如下：Compound 3g was characterized as follows:

表征特征：1H NMR(400MHz,CDCl3)δ8.17–8.10(m,2H),7.78–7.71(m,2H),7.39–7.18(m,4H),4.16(q,J＝7.1Hz,2H),3.85(s,3H),3.65(s,2H),1.24(s,3H).13C NMR(101MHz,CDCl3)δ184.86,184.32,170.68,141.43,139.77,135.21,133.80,133.69,132.62,132.27,132.05,128.22,126.86,126.60,126.36,122.71,119.66,110.89,106.18,61.25,35.40,33.47,14.13.HRMS(ESI)m/z calcd for C23H18NO4NaCl+(M+Na)+430.0828,found 430.0822.Characterization characteristics: 1 H NMR (400MHz, CDCl 3 )δ8.17–8.10 (m, 2H), 7.78–7.71 (m, 2H), 7.39–7.18 (m, 4H), 4.16 (q, J＝7.1Hz, 2H), 3.85 (s, 3H), 3.65 (s, 2H), 1.24 (s, 3H). 13 C NMR (101MHz, CDCl 3 )δ184.86,184.32,170.68,141.43,139.77,135.21,133.80,133.69,132.62,132.27,132.05,128.22,126.86,126.60,126.36,122.71,119.66,1 10.89,106.18,61.25,35.40,33.47,14.13.HRMS(ESI)m/z calcd for C 23 H 18 NO 4 NaCl + (M+Na) + 430.0828, found 430.0822.

实施例8Example 8

按照上述合成路线以及按照实施例1的方法，得到橙红色固体化合物3h(51mg，产率72％)；mp166-168℃；通过硅胶柱纯化(石油醚/乙酸乙酯＝5：1)。According to the above synthetic route and the method of Example 1, an orange-red solid compound 3h (51 mg, yield 72%) was obtained; mp 166-168° C.; purified by silica gel column (petroleum ether/ethyl acetate=5:1).

对化合物3h进行表征，具体如下：Compound 3h was characterized as follows:

表征特征：1H NMR(400MHz,CDCl3)δ8.16–8.09(m,2H),7.73(dd,J＝4.5,2.0Hz,2H),7.52(s,1H),7.31(d,J＝12.0Hz,2H),7.22(d,J＝8.7Hz,1H),4.16(q,J＝7.0Hz,2H),3.82(s,3H),3.64(s,2H),1.23(d,J＝7.1Hz,3H).13C NMR(101MHz,CDCl3)δ184.65,184.26,170.67,141.39,139.80,135.47,133.80,133.69,132.50,132.24,132.03,128.82,126.84,126.33,125.22,122.70,114.13,111.34,106.08,61.26,35.41,33.43,14.16.HRMS(ESI)m/z calcd for C23H18NO4NaBr+(M+Na)+474.0324,found 474.0317.Characterization characteristics: 1 H NMR (400MHz, CDCl 3 )δ8.16–8.09 (m, 2H), 7.73 (dd, J＝4.5, 2.0 Hz, 2H), 7.52 (s, 1H), 7.31 (d, J＝12.0 Hz, 2H), 7.22 (d, J＝8.7 Hz, 1H), 4.16 (q, J＝7.0 Hz, 2H), 3.82 (s, 3H), 3.64 (s, 2H), 1.23 (d, J＝7.1 Hz, 3H). 13 C NMR (101MHz, CDCl 3 )δ184.65,184.26,170.67,141.39,139.80,135.47,133.80,133.69,132.50,132.24,132.03,128.82,126.84,126.33,125.22,122.70,114.13,1 11.34,106.08,61.26,35.41,33.43,14.16.HRMS(ESI)m/z calcd for C 23 H 18 NO 4 NaBr + (M+Na) + 474.0324, found 474.0317.

实施例9Example 9

按照上述合成路线以及按照实施例1的方法，得到紫红色固体化合物3i(46mg，产率74％)；mp170-172℃；通过硅胶柱纯化(石油醚/乙酸乙酯＝5：1)。According to the above synthetic route and the method of Example 1, a purple solid compound 3i (46 mg, yield 74%) was obtained; mp 170-172° C.; and purified by silica gel column (petroleum ether/ethyl acetate=5:1).

对化合物3i进行表征，具体如下：Compound 3i was characterized as follows:

表征特征：1H NMR(400MHz,CDCl3)δ8.14(dd,J＝5.0,2.9Hz,2H),7.76–7.70(m,2H),7.28(s,2H),7.17(s,1H),7.01(d,J＝8.1Hz,1H),4.15(q,J＝7.1Hz,2H),3.83(s,3H),3.70(s,2H),2.50(s,3H),1.23(t,J＝7.1Hz,3H).13C NMR(101MHz,CDCl3)δ184.87,184.51,170.90,142.11,138.89,137.20,133.61,133.51,132.46,132.25,132.16,131.37,126.79,126.23,125.13,122.42,119.98,109.79,106.41,61.00,35.48,33.17,21.80,14.15.HRMS(ESI)m/z calcd for C24H21NO4Na+(M+Na)+410.1374,found 410.1368.Characterization characteristics: 1 H NMR (400MHz, CDCl 3 )δ8.14 (dd, J＝5.0,2.9Hz,2H),7.76–7.70 (m,2H),7.28 (s,2H),7.17 (s,1H),7.01 (d, J＝8.1Hz,1H),4.15 (q, J＝7.1Hz,2H),3.83 (s,3H),3.70 (s,2H),2.50 (s,3H),1.23 (t, J＝7.1Hz,3H). 13 C NMR (101MHz,CDCl 3 )δ184.87,184.51,170.90,142.11,138.89,137.20,133.61,133.51,132.46,132.25,132.16,131.37,126.79,126.23,125.13,122.42,119.98,1 09.79,106.41,61.00,35.48,33.17,21.80,14.15.HRMS(ESI)m/z calcd for C 24 H 21 NO 4 Na + (M+Na) + 410.1374, found 410.1368.

实施例10Example 10

按照上述合成路线以及按照实施例1的方法，得到红色固体化合物3j(44mg，产率71％)；mp182-184℃；通过硅胶柱纯化(石油醚/乙酸乙酯＝5：1)。According to the above synthetic route and the method of Example 1, a red solid compound 3j (44 mg, yield 71%) was obtained; mp 182-184° C.; purified by silica gel column (petroleum ether/ethyl acetate=5:1).

对化合物3j进行表征，具体如下：Compound 3j was characterized as follows:

表征特征：1H NMR(400MHz,CDCl3)δ8.13(s,2H),7.77–7.70(m,2H),7.35–7.27(m,2H),7.04(d,J＝9.3Hz,1H),6.92(t,J＝9.0Hz,1H),4.14(q,J＝7.1Hz,2H),3.81(s,3H),3.66(s,2H),1.25(s,3H).13C NMR(101MHz,CDCl3)δ184.71,184.35,170.71,141.77,139.71,133.72,133.64,132.35,132.08,131.74,131.71,126.82,126.33,123.77,121.29,121.19,109.47,109.23,96.35,96.0,61.10,35.34,33.34,14.12.19F NMR(376MHz,CDCl3)δ-119.93.HRMS(ESI)m/z calcd for C23H18NO4FNa+(M+Na)+414.1123,found 414.1118.Characterization characteristics: 1 H NMR (400MHz, CDCl 3 )δ8.13(s,2H),7.77–7.70(m,2H),7.35–7.27(m,2H),7.04(d,J＝9.3Hz,1H),6.92(t,J＝9.0Hz,1H),4.14(q,J＝7.1Hz,2H),3.81(s,3H),3.66(s,2H),1.25(s,3H). 13 C NMR (101MHz,CDCl 3 )δ184.71,184.35,170.71,141.77,139.71,133.72,133.64,132.35,132.08,131.74,131.71,126.82,126.33,123.77,121.29,121.19,109.47,1 09.23,96.35,96.0,61.10,35.34,33.34,14.12. 19 F NMR(376MHz,CDCl 3 )δ-119.93.HRMS(ESI)m/z calcd for C 23 H 18 NO 4 FNa + (M+Na) + 414.1123, found 414.1118.

实施例11Embodiment 11

按照上述合成路线以及按照实施例1的方法，红色固体化合物3k(52mg，产率71％)；mp131-133℃；通过硅胶柱纯化(石油醚/乙酸乙酯＝5：1)。According to the above synthetic route and the method of Example 1, red solid compound 3k (52 mg, yield 71%); mp 131-133° C.; purified by silica gel column (petroleum ether/ethyl acetate=5:1).

对化合物3k进行表征，具体如下：Compound 3k was characterized as follows:

表征特征：1H NMR(400MHz,CDCl3)δ8.12(s,2H),7.74(s,2H),7.33(d,J＝24.5Hz,3H),7.11(d,J＝8.4Hz,1H),4.18–4.09(m,2H),3.82(s,3H),3.64(s,2H),1.23(t,J＝6.5Hz,3H).13C NMR(101MHz,CDCl3)δ184.70,184.32,170.73,141.54,139.71,137.22,133.78,133.69,132.28,132.10,132.03,128.37,126.84,126.35,125.81,121.28,121.21,109.89,106.8,61.15,35.35,33.36,14.14.HRMS(ESI)m/z calcd for C23H18NO4NaCl+(M+Na)+430.0828,found 430.0822.Characterization characteristics: 1 H NMR (400MHz, CDCl 3 )δ8.12(s,2H),7.74(s,2H),7.33(d,J＝24.5Hz,3H),7.11(d,J＝8.4Hz,1H),4.18–4.09(m,2H),3.82(s,3H),3.64(s,2H),1.23(t,J＝6.5Hz,3H). 13 C NMR (101MHz,CDCl 3 )δ184.70,184.32,170.73,141.54,139.71,137.22,133.78,133.69,132.28,132.10,132.03,128.37,126.84,126.35,125.81,121.28,121.21,1 09.89,106.8,61.15,35.35,33.36,14.14.HRMS(ESI)m/z calcd for C 23 H 18 NO 4 NaCl + (M+Na) + 430.0828, found 430.0822.

实施例12Example 12

按照上述合成路线以及按照实施例1的方法，红色固体化合物3l(49mg，产率69％)；mp59-61℃；通过硅胶柱纯化(石油醚/乙酸乙酯＝5：1)。According to the above synthetic route and the method of Example 1, red solid compound 31 (49 mg, yield 69%); mp 59-61° C.; purified by silica gel column (petroleum ether/ethyl acetate=5:1).

对化合物3l进行表征，具体如下：Compound 31 was characterized as follows:

表征特征：1H NMR(400MHz,CDCl3)δ8.14(d,J＝4.5Hz,2H),7.77–7.74(m,2H),7.54(s,1H),7.27(d,J＝13.8Hz,3H),4.17–4.11(m,2H),3.84(s,3H),3.64(s,2H),1.25(s,3H).13C NMR(101MHz,CDCl3)δ184.85,184.07,170.54,141.68,139.52,137.49,133.76,133.66,132.32,132.04,131.97,126.83,126.35,123.86,121.54,115.98,112.89,106.59,61.13,35.32,33.33,14.11.HRMS(ESI)m/z calcd for C23H18NO4NaBr+(M+Na)+474.0323,found 474.0317.Characterization characteristics: 1 H NMR (400MHz, CDCl 3 )δ8.14 (d, J＝4.5Hz, 2H), 7.77–7.74 (m, 2H), 7.54 (s, 1H), 7.27 (d, J＝13.8Hz, 3H), 4.17–4.11 (m, 2H), 3.84 (s, 3H), 3.64 (s, 2H), 1.25 (s, 3H). 13 C NMR (101MHz, CDCl 3 )δ184.85,184.07,170.54,141.68,139.52,137.49,133.76,133.66,132.32,132.04,131.97,126.83,126.35,123.86,121.54,115.98,112.89,1 06.59,61.13,35.32,33.33,14.11.HRMS(ESI)m/z calcd for C 23 H 18 NO 4 NaBr + (M+Na) + 474.0323, found 474.0317.

实施例13Embodiment 13

按照上述合成路线以及按照实施例1的方法，红色固体化合物3m(41mg，产率67％)；mp169-171℃；通过硅胶柱纯化(石油醚/乙酸乙酯＝5：1)。According to the above synthetic route and the method of Example 1, red solid compound 3m (41 mg, yield 67%); mp 169-171° C.; purified by silica gel column (petroleum ether/ethyl acetate=5:1).

对化合物3m进行表征，具体如下：Compound 3m was characterized as follows:

表征特征：1H NMR(400MHz,CDCl3)δ8.18(dd,J＝3.9,2.8Hz,2H),7.81–7.74(m,2H),7.26–7.15(m,2H),7.06–6.95(m,2H),4.22–4.09(m,5H),3.69(s,2H),2.82(s,3H),1.27(d,J＝7.4Hz,3H).13C NMR(101MHz,CDCl3)δ184.82,184.27,170.88,142.22,139.52,135.29,133.60,133.52,133.06,132.17,128.28,126.80,126.27,124.95,121.79,120.78,118.30,106.05,60.97,37.32,35.43,19.68,14.11.HRMS(ESI)m/z calcd for C24H21NO4Na+(M+Na)+410.1372,found 410.1368.Characterization characteristics: 1 H NMR (400MHz, CDCl 3 )δ8.18 (dd, J＝3.9,2.8Hz,2H),7.81–7.74 (m,2H),7.26–7.15 (m,2H),7.06–6.95 (m,2H),4.22–4.09 (m,5H),3.69 (s,2H),2.82 (s,3H),1.27 (d, J＝7.4Hz,3H). 13 C NMR (101MHz,CDCl 3 )δ184.82,184.27,170.88,142.22,139.52,135.29,133.60,133.52,133.06,132.17,128.28,126.80,126.27,124.95,121.79,120.78,118.30,1 06.05,60.97,37.32,35.43,19.68,14.11.HRMS(ESI)m/z calcd for C 24 H 21 NO 4 Na + (M+Na) + 410.1372, found 410.1368.

实施例14Embodiment 14

按照上述合成路线以及按照实施例1的方法，紫红色固体化合物3n(42mg，产率65％)；mp165-167℃；通过硅胶柱纯化(石油醚/乙酸乙酯＝5：1)。According to the above synthetic route and the method of Example 1, purple solid compound 3n (42 mg, yield 65%); mp 165-167° C.; purified by silica gel column (petroleum ether/ethyl acetate=5:1).

对化合物3n进行表征，具体如下：Compound 3n was characterized as follows:

表征特征：1H NMR(400MHz,CDCl3)δ8.13(d,J＝2.8Hz,2H),7.73(s,2H),7.18(s,1H),7.02(t,J＝7.8Hz,1H),6.91(d,J＝7.9Hz,1H),6.64(d,J＝7.4Hz,1H),4.12(d,J＝9.5Hz,5H),3.93(s,3H),3.66(s,2H),1.22(s,3H).13C NMR(101MHz,CDCl3)δ184.91,184.18,170.65,148.15,141.85,138.93,133.61,133.53,132.61,132.41,132.12,129.43,126.80,126.52,126.26,121.18,112.86,106.10,102.90,60.99,55.48,37.18,35.44,14.13.HRMS(ESI)m/z calcd for C24H21NO5Na+(M+Na)+426.1319,found 426.1317.Characterization characteristics: 1 H NMR (400MHz, CDCl 3 )δ8.13(d, J＝2.8Hz,2H),7.73(s,2H),7.18(s,1H),7.02(t, J＝7.8Hz,1H),6.91(d, J＝7.9Hz,1H),6.64(d, J＝7.4Hz,1H),4.12(d, J＝9.5Hz,5H),3.93(s,3H),3.66(s,2H),1.22(s,3H). 13 C NMR (101MHz,CDCl 3 )δ184.91,184.18,170.65,148.15,141.85,138.93,133.61,133.53,132.61,132.41,132.12,129.43,126.80,126.52,126.26,121.18,112.86,1 06.10,102.90,60.99,55.48,37.18,35.44,14.13.HRMS(ESI)m/z calcd for C 24 H 21 NO 5 Na + (M+Na) + 426.1319, found 426.1317.

实施例15Embodiment 15

按照上述合成路线以及按照实施例1的方法，得到橙红色固体化合物3o(40mg，产率62％)；mp171-173℃；通过硅胶柱纯化(石油醚/乙酸乙酯＝5：1)。According to the above synthetic route and the method of Example 1, an orange-red solid compound 3o (40 mg, yield 62%) was obtained; mp 171-173° C.; and purified by silica gel column (petroleum ether/ethyl acetate=5:1).

对化合物3o进行表征，具体如下：Compound 3o was characterized as follows:

表征特征：1H NMR(400MHz,CDCl3)δ8.15(d,J＝5.3Hz,2H),7.78–7.73(m,2H),7.23(dd,J＝15.0,8.4Hz,3H),7.01(t,J＝7.8Hz,1H),4.22(s,3H),4.13(q,J＝7.1Hz,2H),3.62(s,2H),1.23(s,3H).13C NMR(101MHz,CDCl3)δ184.65,184.04,170.41,141.64,139.92,133.72,132.28,132.01,130.15,126.84,126.37,123.84,121.25,118.96,117.20,106.3,61.10,37.31,35.30,14.10.HRMS(ESI)m/z calcd for C23H18NO4NaCl+(M+Na)+430.0826,found 430.0822.Characterization characteristics: 1 H NMR (400MHz, CDCl 3 )δ8.15(d, J＝5.3Hz,2H),7.78–7.73(m,2H),7.23(dd, J＝15.0,8.4Hz,3H),7.01(t, J＝7.8Hz,1H),4.22(s,3H),4.13(q, J＝7.1Hz,2H),3.62(s,2H),1.23(s,3H). 13 C NMR (101MHz,CDCl 3 )δ184.65,184.04,170.41,141.64,139.92,133.72,132.28,132.01,130.15,126.84,126.37,123.84,121.25,118.96,117.20,106.3,61.10,37. 31,35.30,14.10.HRMS(ESI)m/z calcd for C 23 H 18 NO 4 NaCl + (M+Na) + 430.0826, found 430.0822.

实施例16Example 16

按照上述合成路线以及按照实施例1的方法，得到红色固体化合物3p(52mg，产率73％)；mp186-188℃；通过硅胶柱纯化(石油醚/乙酸乙酯＝5：1)。According to the above synthetic route and the method of Example 1, a red solid compound 3p (52 mg, yield 73%) was obtained; mp 186-188° C.; purified by silica gel column (petroleum ether/ethyl acetate=5:1).

对化合物3p进行表征，具体如下：Compound 3p was characterized as follows:

表征特征：1H NMR(400MHz,CDCl3)δ8.18–8.10(m,2H),7.78–7.72(m,2H),7.39(d,J＝7.6Hz,1H),7.26(dd,J＝13.9,8.0Hz,2H),6.95(t,J＝7.8Hz,1H),4.23(s,3H),4.13(q,J＝7.1Hz,2H),3.62(s,2H),1.22(d,J＝7.1Hz,3H).13C NMR(101MHz,CDCl3)δ184.66,184.13,170.53,141.48,140.32,133.94,133.75,133.68,133.24,132.32,132.07,130.21,127.37,126.84,126.38,121.61,119.56,106.37,104.3,61.10,37.45,35.30,14.11.HRMS(ESI)m/z calcd for C23H18NO4NaBr+(M+Na)+474.0322,found 474.0317.Characterization characteristics: 1 H NMR (400MHz, CDCl 3 )δ8.18–8.10 (m, 2H), 7.78–7.72 (m, 2H), 7.39 (d, J＝7.6Hz, 1H), 7.26 (dd, J＝13.9, 8.0Hz, 2H), 6.95 (t, J＝7.8Hz, 1H), 4.23 (s, 3H), 4.13 (q, J＝7.1Hz, 2H), 3.62 (s, 2H), 1.22 (d, J＝7.1Hz, 3H). 13 C NMR (101MHz, CDCl 3 )δ184.66,184.13,170.53,141.48,140.32,133.94,133.75,133.68,133.24,132.32,132.07,130.21,127.37,126.84,126.38,121.61,119.56,1 06.37,104.3,61.10,37.45,35.30,14.11.HRMS(ESI)m/z calcd for C 23 H 18 NO 4 NaBr + (M+Na) + 474.0322, found 474.0317.

实施例17Embodiment 17

按照上述合成路线以及按照实施例1的方法，得到红色固体化合物3q(48mg，产率72％)；mp164-166℃；通过硅胶柱纯化(石油醚/乙酸乙酯＝5：1)。According to the above synthetic route and the method of Example 1, a red solid compound 3q (48 mg, yield 72%) was obtained; mp 164-166° C.; purified by silica gel column (petroleum ether/ethyl acetate=5:1).

对化合物3q进行表征，具体如下：Compound 3q was characterized as follows:

表征特征：1H NMR(400MHz,CDCl3)δ8.68(s,2H),8.06(d,J＝4.9Hz,2H),7.69–7.65(m,2H),7.41(dd,J＝15.1,6.4Hz,3H),7.28(dd,J＝14.2,6.4Hz,1H),7.18(t,J＝7.5Hz,1H),4.15(q,J＝7.1Hz,2H),3.89(s,3H),3.74(s,2H),1.24(s,3H).13C NMR(101MHz,CDCl3)δ184.59,184.03,170.72,143.28,140.89,136.98,134.83,131.81,130.11,130.09,129.29,129.24,129.12,129.02,128.68,128.50,127.24,122.29,120.64,120.37,112.46,109.82,106.86,61.01,35.77,33.28,14.14.HRMS(ESI)m/z calcd for C27H21NO4Na+(M+Na)+446.1375,found 446.1368.Characterization characteristics: 1 H NMR (400MHz, CDCl 3 )δ8.68(s,2H),8.06(d,J＝4.9Hz,2H),7.69–7.65(m,2H),7.41(dd,J＝15.1,6.4Hz,3H),7.28(dd,J＝14.2,6.4Hz,1H),7.18(t,J＝7.5Hz,1H),4.15(q,J＝7.1Hz,2H),3.89(s,3H),3.74(s,2H),1.24(s,3H). 13 C NMR (101MHz,CDCl 3 )δ184.59,184.03,170.72,143.28,140.89,136.98,134.83,131.81,130.11,130.09,129.29,129.24,129.12,129.02,128.68,128.50,127.24,1 22.29,120.64,120.37,112.46,109.82,106.86,61.01,35.77,33.28,14.14.HRMS(ESI)m/z calcd for C 27 H 21 NO 4 Na + (M+Na) + 446.1375,found 446.1368.

实施例18Embodiment 18

按照上述合成路线，向吲哚萘醌1a(0.15mmol)和K2CO3(0.225mmol，1.5eq)、CuI(0.03mmol，20mmol％)在CH3CN(1mL)中的溶液中加入丙二酸二乙酯2a(0.3mmol，2eq)。将反应混合物在100℃下在密封管下搅拌1小时。反应完成后(通过TLC监测)。用饱和盐水(6mL)猝灭反应，并用EtOAc(3×3mL)萃取混合物。有机提取物用盐水洗涤，用Na2SO4干燥，过滤，真空除去溶剂。粗产物通过硅胶柱色谱法纯化，得到化合物4a。紫色固体(57mg，产率82％)；mp204-206℃；通过硅胶柱纯化(石油醚/乙酸乙酯＝5：1)。According to the above synthetic route, diethyl malonate 2a (0.3 mmol, 2 eq) was added to a solution of indole naphthoquinone 1a (0.15 mmol) and K 2 CO 3 (0.225 mmol, 1.5 eq), CuI (0.03 mmol, 20 mmol%) in CH 3 CN (1 mL). The reaction mixture was stirred at 100°C under a sealed tube for 1 hour. After the reaction was completed (monitored by TLC). The reaction was quenched with saturated brine (6 mL), and the mixture was extracted with EtOAc (3×3 mL). The organic extract was washed with brine, dried over Na 2 SO 4 , filtered, and the solvent was removed in vacuo. The crude product was purified by silica gel column chromatography to give compound 4a. Purple solid (57 mg, yield 82%); mp 204-206°C; purified by silica gel column (petroleum ether/ethyl acetate=5:1).

对化合物4a进行表征，具体如下：Compound 4a was characterized as follows:

表征特征：1H NMR(400MHz,CDCl3)δ8.41(d,J＝7.6Hz,1H),8.22–8.15(m,2H),7.78–7.70(m,2H),7.43–7.35(m,3H),4.25(tt,J＝10.7,5.5Hz,4H),3.99(s,3H),1.23(t,J＝7.1Hz,6H).13C NMR(101MHz,CDCl3)δ183.09,178.15,164.79,149.19,148.33,142.69,134.02,132.54,132.31,126.40,126.21,123.70,122.68,122.43,121.61,118.21,110.7,63.21,32.23,13.93.HRMS(ESI)m/z calcd for C26H21NO6Na+(M+Na)+466.1268,found466.1267.Characterization characteristics: 1 H NMR (400MHz, CDCl 3 )δ8.41(d, J＝7.6Hz,1H),8.22–8.15(m,2H),7.78–7.70(m,2H),7.43–7.35(m,3H),4.25(tt, J＝10.7,5.5Hz,4H),3.99(s,3H),1.23(t, J＝7.1Hz,6H). 13 C NMR (101MHz,CDCl 3 )δ183.09,178.15,164.79,149.19,148.33,142.69,134.02,132.54,132.31,126.40,126.21,123.70,122.68,122.43,121.61,118.21,110.7,63 .21,32.23,13.93.HRMS(ESI)m/z calcd for C 26 H 21 NO 6 Na + (M+Na) + 466.1268,found466.1267.

实施例19Embodiment 19

按照上述合成路线以及实施例18的方法，得到蓝紫色固体化合物4b(58mg，产率80％)；mp204-206℃；通过硅胶柱纯化(石油醚/乙酸乙酯＝5：1)。According to the above synthetic route and the method of Example 18, a blue-purple solid compound 4b (58 mg, yield 80%) was obtained; mp 204-206° C.; and purified by silica gel column (petroleum ether/ethyl acetate=5:1).

对化合物4b进行表征，具体如下：Compound 4b was characterized as follows:

表征特征：1H NMR(400MHz,CDCl3)δ8.45–8.40(m,1H),8.19(dd,J＝13.0,7.4Hz,2H),7.78–7.71(m,2H),7.47–7.44(m,1H),7.38–7.34(m,2H),4.56–4.51(m,2H),4.31–4.20(m,4H),1.44(t,J＝7.2Hz,1H),1.22(dd,J＝14.5,7.4Hz,8H).13C NMR(101MHz,CDCl3)δ183.12,178.50,164.96,148.53,148.29,141.55,138.93,133.99,132.52,132.38,126.36,126.22,123.63,122.85,122.32,122.04,118.28,112.36,111.2,64.12,63.17,40.91,29.68,14.70,13.88.HRMS(ESI)m/z calcd for C27H23NO6Na+(M+Na)+480.1433,found480.1423.Characterization characteristics: 1 H NMR (400MHz, CDCl 3 )δ8.45–8.40 (m, 1H), 8.19 (dd, J＝13.0, 7.4 Hz, 2H), 7.78–7.71 (m, 2H), 7.47–7.44 (m, 1H), 7.38–7.34 (m, 2H), 4.56–4.51 (m, 2H), 4.31–4.20 (m, 4H), 1.44 (t, J＝7.2 Hz, 1H), 1.22 (dd, J＝14.5, 7.4 Hz, 8H). 13 C NMR (101MHz, CDCl 3 )δ183.12,178.50,164.96,148.53,148.29,141.55,138.93,133.99,132.52,132.38,126.36,126.22,123.63,122.85,122.32,122.04,118.28,1 12.36,111.2,64.12,63.17,40.91,29.68,14.70,13.88.HRMS(ESI)m/z calcd for C 27 H 23 NO 6 Na + (M+Na) + 480.1433,found480.1423.

实施例20Embodiment 20

按照上述合成路线以及实施例18的方法，得到紫色固体化合物4c(52mg，产率71％)；mp196-198℃；通过硅胶柱纯化(石油醚/乙酸乙酯＝5：1)。According to the above synthetic route and the method of Example 18, a purple solid compound 4c (52 mg, yield 71%) was obtained; mp 196-198° C.; and purified by silica gel column (petroleum ether/ethyl acetate=5:1).

对化合物4c进行表征，具体如下：Compound 4c was characterized as follows:

表征特征：1H NMR(400MHz,CDCl3)δ8.45–8.39(m,1H),8.18(dd,J＝14.3,7.4Hz,2H),7.75(dd,J＝17.4,7.8Hz,2H),7.36(dt,J＝7.4,6.1Hz,3H),5.99–5.91(m,1H),5.15(dd,J＝24.0,7.6Hz,3H),5.00(d,J＝17.1Hz,1H),4.29–4.15(m,4H),1.21(d,J＝7.1Hz,7H).13C NMR(101MHz,CDCl3)δ182.95,178.37,164.75,148.55,148.19,142.09,139.46,134.01,132.58,132.37,132.14,129.94,129.70,126.38,126.24,123.73,122.71,122.44,121.85,118.65,117.21,111.72,63.18,48.21,29.68,22.67,13.85.HRMS(ESI)m/z calcdfor C28H23NO6Na+(M+Na)+492.1419,found 492.1423.Characterization characteristics: 1 H NMR (400MHz, CDCl 3 )δ8.45–8.39 (m, 1H), 8.18 (dd, J=14.3, 7.4 Hz, 2H), 7.75 (dd, J=17.4, 7.8 Hz, 2H), 7.36 (dt, J=7.4, 6.1 Hz, 3H), 5.99–5.91 (m, 1H), 5.15 (dd, J=24.0, 7.6 Hz, 3H), 5.00 (d, J=17.1 Hz, 1H), 4.29–4.15 (m, 4H), 1.21 (d, J=7.1 Hz, 7H). 13 C NMR (101MHz, CDCl 3 )δ182.95,178.37,164.75,148.55,148.19,142.09,139.46,134.01,132.58,132.37,132.14,129.94,129.70,126.38,126.24,123.73,122.71,1 22.44,121.85,118.65,117.21,111.72,63.18,48.21,29.68,22.67,13.85.HRMS(ESI)m/z calcdfor C 28 H 23 NO 6 Na + (M+Na) + 492.1419,found 492.1423.

实施例21Embodiment 21

按照上述合成路线以及实施例18的方法，得到紫红色固体化合物4d(50mg，产率69％)；mp186-198℃；通过硅胶柱纯化(石油醚/乙酸乙酯＝5：1)。According to the above synthetic route and the method of Example 18, a purple solid compound 4d (50 mg, yield 69%) was obtained; mp 186-198° C.; purified by silica gel column (petroleum ether/ethyl acetate=5:1).

对化合物4d进行表征，具体如下：Compound 4d was characterized as follows:

表征特征：1H NMR(400MHz,CDCl3)δ8.20(d,J＝6.8Hz,1H),8.14(d,J＝7.0Hz,1H),7.81–7.73(m,2H),7.29(dd,J＝15.5,8.1Hz,2H),7.19(t,J＝7.5Hz,1H),7.05(t,J＝7.4Hz,1H),4.57(s,1H),4.27–4.06(m,4H),3.73(s,3H),2.27(s,3H),1.19(q,J＝6.8Hz,6H).13C NMR(101MHz,CDCl3)δ183.84,183.57,166.86,166.71,144.25,142.90,136.97,136.63,133.85,133.74,132.31,132.14,126.93,126.88,126.69,121.51,120.26,118.36,109.93,109.25,104.08,61.73,52.65,29.83,13.96,13.92,11.72.HRMS(ESI)m/z calcdfor C27H25NO6Na+(M+Na)+482.1587,found 482.1580.Characterization characteristics: 1 H NMR (400MHz, CDCl 3 )δ8.20(d, J＝6.8Hz,1H),8.14(d, J＝7.0Hz,1H),7.81–7.73(m,2H),7.29(dd, J＝15.5,8.1Hz,2H),7.19(t, J＝7.5Hz,1H),7.05(t, J＝7.4Hz,1H),4.57(s,1H),4.27–4.06(m,4H),3.73(s,3H),2.27(s,3H),1.19(q, J＝6.8Hz,6H). 13 C NMR (101MHz,CDCl 3 )δ183.84,183.57,166.86,166.71,144.25,142.90,136.97,136.63,133.85,133.74,132.31,132.14,126.93,126.88,126.69,121.51,120.26,1 18.36,109.93,109.25,104.08,61.73,52.65,29.83,13.96,13.92,11.72.HRMS(ESI)m/z calcdfor C 27 H 25 NO 6 Na + (M+Na) + 482.1587,found 482.1580.

实施例22Embodiment 22

按照上述合成路线以及实施例18的方法，得到红色固体化合物4e(47mg，产率57％)；mp155-157℃；通过硅胶柱纯化(石油醚/乙酸乙酯＝5：1)。According to the above synthetic route and the method of Example 18, a red solid compound 4e (47 mg, yield 57%) was obtained; mp 155-157° C.; and purified by silica gel column (petroleum ether/ethyl acetate=5:1).

对化合物4e进行表征，具体如下：Compound 4e was characterized as follows:

表征特征：1H NMR(400MHz,CDCl3)δ7.86(d,J＝7.5Hz,1H),7.64(d,J＝7.5Hz,1H),7.40(dt,J＝23.7,7.2Hz,2H),7.15–6.97(m,8H),6.83(t,J＝7.5Hz,1H),4.39(s,1H),3.99–3.79(m,4H),3.48(s,3H),0.90(dd,J＝14.1,7.1Hz,6H).13C NMR(101MHz,CDCl3)δ183.52,183.03,166.76,166.52,144.45,142.90,140.80,137.55,133.60,133.53,132.16,132.01,131.19,130.02,128.45,128.38,127.06,126.74,126.57,122.54,120.77,118.88,110.13,105.3,61.76,52.84,31.33,29.69,13.93.HRMS(ESI)m/z calcd for C32H27NO6Na+(M+Na)+544.1740,found544.1736.Characterization characteristics: 1 H NMR (400MHz, CDCl 3 )δ7.86(d, J＝7.5Hz,1H),7.64(d, J＝7.5Hz,1H),7.40(dt, J＝23.7,7.2Hz,2H),7.15–6.97(m,8H),6.83(t, J＝7.5Hz,1H),4.39(s,1H),3.99–3.79(m,4H),3.48(s,3H),0.90(dd, J＝14.1,7.1Hz,6H). 13 C NMR (101MHz,CDCl 3 )δ183.52,183.03,166.76,166.52,144.45,142.90,140.80,137.55,133.60,133.53,132.16,132.01,131.19,130.02,128.45,128.38,127.06,1 26.74,126.57,122.54,120.77,118.88,110.13,105.3,61.76,52.84,31.33,29.69,13.93.HRMS(ESI)m/z calcd for C 32 H 27 NO 6 Na + (M+Na) + 544.1740, found 544.1736.

实施例23Embodiment 23

按照上述合成路线以及实施例18的方法，得到蓝色固体化合物4f(58mg，产率81％)；mp223-2225℃；通过硅胶柱纯化(石油醚/乙酸乙酯＝5：1)。According to the above synthetic route and the method of Example 18, a blue solid compound 4f (58 mg, yield 81%) was obtained; mp 223-2225° C.; purified by silica gel column (petroleum ether/ethyl acetate=5:1).

对化合物4f进行表征，具体如下：Compound 4f was characterized as follows:

表征特征：1H NMR(400MHz,CDCl3)δ8.21–8.14(m,3H),7.78–7.69(m,2H),7.30(d,J＝8.4Hz,1H),7.19(d,J＝8.4Hz,1H),4.31–4.21(m,4H),3.96(s,3H),2.54(s,3H),1.23(t,J＝7.1Hz,6H).13C NMR(101MHz,CDCl3)δ183.18,178.12,164.85,149.15,148.37,141.22,138.47,134.09,134.02,132.48,132.35,132.18,126.37,126.14,125.22,122.34,121.84,117.75,110.3,64.79,63.15,32.22,29.68,21.51,13.92.HRMS(ESI)m/z calcd forC27H23NO6Na+(M+Na)+480.1430,found 480.1423.Characterization characteristics: 1 H NMR (400MHz, CDCl 3 )δ8.21–8.14 (m, 3H), 7.78–7.69 (m, 2H), 7.30 (d, J＝8.4Hz, 1H), 7.19 (d, J＝8.4Hz, 1H), 4.31–4.21 (m, 4H), 3.96 (s, 3H), 2.54 (s, 3H), 1.23 (t, J＝7.1Hz, 6H). 13 C NMR (101MHz, CDCl 3 )δ183.18,178.12,164.85,149.15,148.37,141.22,138.47,134.09,134.02,132.48,132.35,132.18,126.37,126.14,125.22,122.34,121.84,1 17.75,110.3,64.79,63.15,32.22,29.68,21.51,13.92.HRMS(ESI)m/z calcd forC 27 H 23 NO 6 Na + (M+Na) + 480.1430,found 480.1423.

实施例24Embodiment 24

按照上述合成路线以及实施例18的方法，得到蓝紫色固体化合物4g(50mg，产率67％)；mp215-2175℃；通过硅胶柱纯化(石油醚/乙酸乙酯＝5：1)。According to the above synthetic route and the method of Example 18, 4 g (50 mg, yield 67%) of a blue-purple solid compound was obtained; mp 215-2175° C.; purified by silica gel column (petroleum ether/ethyl acetate=5:1).

对化合物4g进行表征，具体如下：Compound 4g was characterized as follows:

表征特征：1H NMR(400MHz,CDCl3)δ8.18(t,J＝7.3Hz,2H),7.89(d,J＝2.0Hz,1H),7.76–7.68(m,2H),7.30(d,J＝9.0Hz,1H),7.00(dd,J＝9.0,2.5Hz,1H),4.26(dd,J＝9.7,7.2Hz,3H),3.97(d,J＝11.2Hz,6H),1.27–1.16(m,9H).13C NMR(101MHz,CDCl3)δ183.17,177.93,164.85,156.18,148.96,148.40,138.39,137.78,134.10,134.05,132.46,132.25,126.41,126.12,122.29,117.87,114.02,111.53,109.63,103.9,64.69,63.16,55.92,32.31,29.68,13.92.HRMS(ESI)m/z calcd for C27H23NO7Na+(M+Na)+496.1373,found496.1372.Characterization characteristics: 1 H NMR (400MHz, CDCl 3 )δ8.18(t, J＝7.3Hz,2H),7.89(d, J＝2.0Hz,1H),7.76–7.68(m,2H),7.30(d, J＝9.0Hz,1H),7.00(dd, J＝9.0,2.5Hz,1H),4.26(dd, J＝9.7,7.2Hz,3H),3.97(d, J＝11.2Hz,6H),1.27–1.16(m,9H). 13 C NMR (101MHz,CDCl 3 )δ183.17,177.93,164.85,156.18,148.96,148.40,138.39,137.78,134.10,134.05,132.46,132.25,126.41,126.12,122.29,117.87,114.02,1 11.53,109.63,103.9,64.69,63.16,55.92,32.31,29.68,13.92.HRMS(ESI)m/z calcd for C 27 H 23 NO 7 Na + (M+Na) + 496.1373,found496.1372.

实施例25Embodiment 25

按照上述合成路线以及实施例18的方法，得到紫色固体化合物4h(52mg，产率72％)；mp194-196℃；通过硅胶柱纯化(石油醚/乙酸乙酯＝5：1)。According to the above synthetic route and the method of Example 18, a purple solid compound 4h (52 mg, yield 72%) was obtained; mp 194-196° C.; and purified by silica gel column (petroleum ether/ethyl acetate=5:1).

对化合物4h进行表征，具体如下：Compound 4h was characterized as follows:

表征特征：1H NMR(400MHz,CDCl3)δ8.17(t,J＝7.6Hz,2H),8.06(dd,J＝9.2,2.1Hz,1H),7.74(dt,J＝15.1,6.9Hz,2H),7.33(dd,J＝8.9,3.9Hz,1H),7.10(td,J＝9.0,2.2Hz,1H),4.34–4.21(m,4H),3.98(s,3H),1.26–1.23(m,6H).13C NMR(101MHz,CDCl3)δ182.86,178.30,164.63,160.48,158.20,149.98,148.05,139.27,138.68,134.09,133.94,132.64,132.25,126.44,126.23,112.09,111.83,111.56,111.46,108.09,107.84,63.31,32.44,29.68,13.91.19F NMR(376MHz,CDCl3)δ-121.19.HRMS(ESI)m/z calcd forC26H20NO6NaF+(M+Na)+484.1175,found 484.1172.Characterization characteristics: 1 H NMR (400MHz, CDCl 3 )δ8.17 (t, J＝7.6Hz, 2H), 8.06 (dd, J＝9.2, 2.1Hz, 1H), 7.74 (dt, J＝15.1, 6.9Hz, 2H), 7.33 (dd, J＝8.9, 3.9Hz, 1H), 7.10 (td, J＝9.0, 2.2Hz, 1H), 4.34–4.21 (m, 4H), 3.98 (s, 3H), 1.26–1.23 (m, 6H). 13 C NMR (101MHz, CDCl 3 )δ182.86,178.30,164.63,160.48,158.20,149.98,148.05,139.27,138.68,134.09,133.94,132.64,132.25,126.44,126.23,112.09,111.83,1 11.56,111.46,108.09,107.84,63.31,32.44,29.68,13.91. 19 F NMR(376MHz,CDCl 3 )δ-121.19.HRMS(ESI)m/z calcd forC 26 H 20 NO 6 NaF + (M+Na) + 484.1175, found 484.1172.

实施例26Embodiment 26

按照上述合成路线以及实施例18的方法，得到紫色固体化合物4i(55mg，产率73％)；mp226-228℃；通过硅胶柱纯化(石油醚/乙酸乙酯＝5：1)。According to the above synthetic route and the method of Example 18, a purple solid compound 4i (55 mg, yield 73%) was obtained; mp 226-228° C.; purified by silica gel column (petroleum ether/ethyl acetate=5:1).

对化合物4i进行表征，具体如下：Compound 4i was characterized as follows:

表征特征：1H NMR(400MHz,CDCl3)δ8.38(s,1H),8.18(t,J＝8.6Hz,2H),7.80–7.71(m,2H),7.32(s,2H),4.26(td,J＝17.6,10.6Hz,4H),3.97(s,3H),1.22(d,J＝7.2Hz,6H).13C NMR(101MHz,CDCl3)δ182.78,178.24,164.43,147.90,141.03,139.10,134.13,133.80,132.72,132.15,128.24,126.47,126.24,125.55,123.96,122.47,122.12,111.71,63.35,32.41,13.91.HRMS(ESI)m/z calcd for C26H20NO6NaCl+(M+Na)+500.0883,found500.0877.Characterization characteristics: 1 H NMR (400MHz, CDCl 3 )δ8.38(s,1H),8.18(t,J＝8.6Hz,2H),7.80–7.71(m,2H),7.32(s,2H),4.26(td,J＝17.6,10.6Hz,4H),3.97(s,3H),1.22(d,J＝7.2Hz,6H). 13 C NMR (101MHz,CDCl 3 )δ182.78,178.24,164.43,147.90,141.03,139.10,134.13,133.80,132.72,132.15,128.24,126.47,126.24,125.55,123.96,122.47,122.12,1 11.71,63.35,32.41,13.91.HRMS(ESI)m/z calcd for C 26 H 20 NO 6 NaCl + (M+Na) + 500.0883,found500.0877.

实施例27Embodiment 27

按照上述合成路线以及实施例18的方法，得到紫色固体化合物4j(55mg，产率68％)；mp230-232℃；通过硅胶柱纯化(石油醚/乙酸乙酯＝5：1)。According to the above synthetic route and the method of Example 18, a purple solid compound 4j (55 mg, yield 68%) was obtained; mp 230-232° C.; purified by silica gel column (petroleum ether/ethyl acetate=5:1).

对化合物4j进行表征，具体如下：Compound 4j was characterized as follows:

表征特征：1H NMR(400MHz,CDCl3)δ8.54(s,1H),8.18(t,J＝8.4Hz,2H),7.80–7.70(m,2H),7.45(d,J＝8.7Hz,1H),7.32–7.25(m,2H),4.34–4.20(m,4H),3.97(s,3H),1.23(t,J＝7.0Hz,6H).13C NMR(101MHz,CDCl3)δ178.38,164.52,149.43,147.72,145.05,141.38,139.10,134.14,133.90,132.73,132.23,126.57,126.48,126.24,125.16,123.02,117.47,115.92,112.11,63.36,32.39,13.91.HRMS(ESI)m/z calcd for C26H20NO6NaBr+(M+Na)+544.0377,found 544.0372.Characterization characteristics: 1 H NMR (400MHz, CDCl 3 )δ8.54(s,1H),8.18(t,J＝8.4Hz,2H),7.80–7.70(m,2H),7.45(d,J＝8.7Hz,1H),7.32–7.25(m,2H),4.34–4.20(m,4H),3.97(s,3H),1.23(t,J＝7.0Hz,6H). 13 C NMR (101MHz,CDCl 3 )δ178.38,164.52,149.43,147.72,145.05,141.38,139.10,134.14,133.90,132.73,132.23,126.57,126.48,126.24,125.16,123.02,117.47,1 15.92,112.11,63.36,32.39,13.91.HRMS(ESI)m/z calcd for C 26 H 20 NO 6 NaBr + (M+Na) + 544.0377, found 544.0372.

实施例28Embodiment 28

按照上述合成路线以及实施例18的方法，得到紫色固体化合物4k(55mg，产率76％)；mp207-209℃；通过硅胶柱纯化(石油醚/乙酸乙酯＝5：1)。According to the above synthetic route and the method of Example 18, a purple solid compound 4k (55 mg, yield 76%) was obtained; mp 207-209° C.; purified by silica gel column (petroleum ether/ethyl acetate=5:1).

对化合物4k进行表征，具体如下：Compound 4k was characterized as follows:

表征特征：1H NMR(400MHz,CDCl3)δ8.26(d,J＝8.1Hz,1H),8.18(t,J＝8.1Hz,2H),7.78–7.69(m,2H),7.24–7.16(m,2H),4.32–4.17(m,4H),3.95(s,3H),2.54(s,3H),1.22(s,6H).13C NMR(101MHz,CDCl3)δ183.02,178.12,164.87,148.74,148.27,143.07,138.51,134.11,133.98,133.92,132.44,132.35,126.37,126.16,124.07,122.28,119.37,118.21,111.73,110.75,63.12,32.13,29.68,22.66,21.99,13.91.HRMS(ESI)m/z calcd forC27H23NO6Na+(M+Na)+480.1429,found 480.1423.Characterization characteristics: 1 H NMR (400MHz, CDCl 3 )δ8.26(d,J＝8.1Hz,1H),8.18(t,J＝8.1Hz,2H),7.78–7.69(m,2H),7.24–7.16(m,2H),4.32–4.17(m,4H),3.95(s,3H),2.54(s,3H),1.22(s,6H). 13 C NMR (101MHz,CDCl 3 )δ183.02,178.12,164.87,148.74,148.27,143.07,138.51,134.11,133.98,133.92,132.44,132.35,126.37,126.16,124.07,122.28,119.37,1 18.21,111.73,110.75,63.12,32.13,29.68,22.66,21.99,13.91.HRMS(ESI)m/z calcd forC 27 H 23 NO 6 Na + (M+Na) + 480.1429,found 480.1423.

实施例29Embodiment 29

按照上述合成路线以及实施例18的方法，得到紫色固体化合物4l(57mg，产率78％)；mp203-205℃；通过硅胶柱纯化(石油醚/乙酸乙酯＝5：1)。According to the above synthetic route and the method of Example 18, a purple solid compound 41 (57 mg, yield 78%) was obtained; mp 203-205° C.; and purified by silica gel column (petroleum ether/ethyl acetate=5:1).

对化合物4l进行表征，具体如下：Compound 41 was characterized as follows:

表征特征：1H NMR(400MHz,CDCl3)δ8.32(dd,J＝9.3,5.4Hz,1H),8.17(dd,J＝6.7,2.7Hz,2H),7.79–7.69(m,2H),7.09(dd,J＝11.0,3.7Hz,2H),4.27(tdd,J＝10.7,7.2,3.7Hz,4H),3.94(s,3H),1.25(d,J＝6.9Hz,6H).13C NMR(101MHz,CDCl3)δ182.90,178.34,164.66,161.74,159.27,148.02,142.98,142.82,139.07,134.10,133.97,132.62,132.25,126.45,126.20,123.74,123.64,118.31,118.12,111.01,110.77,97.71,97.44,63.30,32.40,29.69,13.92.19F NMR(376MHz,CDCl3)δ-117.48.HRMS(ESI)m/z calcd forC26H20NO6FNa+(M+Na)+484.1176,found 484.1172.Characterization characteristics: 1 H NMR (400MHz, CDCl 3 )δ8.32 (dd, J＝9.3,5.4Hz,1H),8.17 (dd, J＝6.7,2.7Hz,2H),7.79–7.69 (m,2H),7.09 (dd, J＝11.0,3.7Hz,2H),4.27 (tdd, J＝10.7,7.2,3.7Hz,4H),3.94 (s,3H),1.25 (d, J＝6.9Hz,6H). 13 C NMR (101MHz,CDCl 3 )δ182.90,178.34,164.66,161.74,159.27,148.02,142.98,142.82,139.07,134.10,133.97,132.62,132.25,126.45,126.20,123.74,123.64,1 18.31,118.12,111.01,110.77,97.71,97.44,63.30,32.40,29.69,13.92. 19 F NMR(376MHz,CDCl 3 )δ-117.48.HRMS(ESI)m/z calcd forC 26 H 20 NO 6 FNa + (M+Na) + 484.1176, found 484.1172.

实施例30Embodiment 30

按照上述合成路线以及实施例18的方法，得到紫色固体化合物4m(56mg，产率75％)；mp220-222℃；通过硅胶柱纯化(石油醚/乙酸乙酯＝5：1)。According to the above synthetic route and the method of Example 18, a purple solid compound 4m (56 mg, yield 75%) was obtained; mp 220-222° C.; purified by silica gel column (petroleum ether/ethyl acetate=5:1).

对化合物4m进行表征，具体如下：Compound 4m was characterized as follows:

表征特征：1H NMR(400MHz,CDCl3)δ8.28(d,J＝8.4Hz,1H),8.16(d,J＝7.2Hz,2H),7.78–7.69(m,2H),7.40(s,1H),7.29(d,J＝8.4Hz,1H),4.27(dd,J＝11.0,7.1Hz,4H),3.95(s,3H),1.24(s,6H).13C NMR(101MHz,CDCl3)δ182.90,178.44,164.55,149.28,147.74,142.77,139.20,134.11,133.91,132.67,132.15,129.68,126.46,126.21,123.48,122.96,120.10,118.23,110.90,63.34,32.37,29.68,13.91.HRMS(ESI)m/z calcd forC26H20NO6ClNa+(M+Na)+500.0872,found500.0877.Characterization characteristics: 1 H NMR (400MHz, CDCl 3 )δ8.28(d, J＝8.4Hz,1H),8.16(d, J＝7.2Hz,2H),7.78–7.69(m,2H),7.40(s,1H),7.29(d, J＝8.4Hz,1H),4.27(dd, J＝11.0,7.1Hz,4H),3.95(s,3H),1.24(s,6H). 13 C NMR (101MHz,CDCl 3 )δ182.90,178.44,164.55,149.28,147.74,142.77,139.20,134.11,133.91,132.67,132.15,129.68,126.46,126.21,123.48,122.96,120.10,1 18.23,110.90,63.34,32.37,29.68,13.91.HRMS(ESI)m/z calcd forC 26 H 20 NO 6 ClNa + (M+Na) + 500.0872,found500.0877.

实施例31Embodiment 31

按照上述合成路线以及实施例18的方法，得到紫色固体化合物4n(58mg，产率71％)；mp240-242℃；通过硅胶柱纯化(石油醚/乙酸乙酯＝5：1)。According to the above synthetic route and the method of Example 18, a purple solid compound 4n (58 mg, yield 71%) was obtained; mp 240-242° C.; purified by silica gel column (petroleum ether/ethyl acetate=5:1).

对化合物4n进行表征，具体如下：Compound 4n was characterized as follows:

表征特征：1H NMR(400MHz,CDCl3)δ8.24(d,J＝8.5Hz,1H),8.17(d,J＝7.4Hz,2H),7.79–7.70(m,2H),7.57(s,1H),7.44(dd,J＝8.4,1.4Hz,1H),4.27(dddd,J＝17.9,10.8,7.1,3.7Hz,4H),3.96(s,3H),1.23(t,J＝5.8Hz,7H).13C NMR(101MHz,CDCl3)δ182.83,178.32,164.51,149.25,148.07,143.38,139.08,134.11,133.92,132.67,132.22,126.47,126.22,125.58,123.80,120.43,118.25,117.25,113.89,63.34,32.36,29.68,13.91.HRMS(ESI)m/z calcd for C26H20NO6NaBr+(M+Na)+544.0379,found 544.0372.Characterization characteristics: 1 H NMR (400MHz, CDCl 3 )δ8.24 (d, J＝8.5Hz, 1H), 8.17 (d, J＝7.4Hz, 2H), 7.79–7.70 (m, 2H), 7.57 (s, 1H), 7.44 (dd, J＝8.4, 1.4Hz, 1H), 4.27 (dddd, J＝17.9, 10.8, 7.1, 3.7Hz, 4H), 3.96 (s, 3H), 1.23 (t, J＝5.8Hz, 7H). 13 C NMR (101MHz, CDCl 3 )δ182.83,178.32,164.51,149.25,148.07,143.38,139.08,134.11,133.92,132.67,132.22,126.47,126.22,125.58,123.80,120.43,118.25,1 17.25,113.89,63.34,32.36,29.68,13.91.HRMS(ESI)m/z calcd for C 26 H 20 NO 6 NaBr + (M+Na) + 544.0379, found 544.0372.

实施例32Embodiment 32

按照上述合成路线以及实施例18的方法，得到蓝色固体化合物4o(55mg，产率76％)；mp239-241℃；通过硅胶柱纯化(石油醚/乙酸乙酯＝5：1)。According to the above synthetic route and the method of Example 18, a blue solid compound 4o (55 mg, yield 76%) was obtained; mp 239-241° C.; purified by silica gel column (petroleum ether/ethyl acetate=5:1).

对化合物4o进行表征，具体如下：Compound 4o was characterized as follows:

表征特征：1H NMR(400MHz,CDCl3)δ8.30(d,J＝7.9Hz,1H),8.17(dd,J＝11.9,7.5Hz,2H),7.73(dt,J＝19.2,7.3Hz,2H),7.20(t,J＝7.6Hz,1H),7.05(d,J＝7.2Hz,1H),4.42–4.06(m,7H),2.81(s,3H),1.21(d,J＝7.1Hz,6H).13C NMR(101MHz,CDCl3)δ183.17,177.93,164.85,156.18,148.96,148.40,138.39,137.78,134.10,134.05,132.46,132.25,126.41,126.12,122.29,117.87,114.02,111.53,109.63,103.99,64.69,63.16,55.92,32.31,29.68,13.92.HRMS(ESI)m/z calcd for C27H23NO6Na+(M+Na)+480.1430,found480.1423.Characterization characteristics: 1 H NMR (400MHz, CDCl 3 )δ8.30(d, J＝7.9Hz,1H),8.17(dd, J＝11.9,7.5Hz,2H),7.73(dt, J＝19.2,7.3Hz,2H),7.20(t, J＝7.6Hz,1H),7.05(d, J＝7.2Hz,1H),4.42–4.06(m,7H),2.81(s,3H),1.21(d, J＝7.1Hz,6H). 13 C NMR (101MHz,CDCl 3 )δ183.17,177.93,164.85,156.18,148.96,148.40,138.39,137.78,134.10,134.05,132.46,132.25,126.41,126.12,122.29,117.87,114.02,1 11.53,109.63,103.99,64.69,63.16,55.92,32.31,29.68,13.92.HRMS(ESI)m/z calcd for C 27 H 23 NO 6 Na + (M+Na) + 480.1430,found480.1423.

实施例33Embodiment 33

按照上述合成路线以及实施例18的方法，得到蓝色固体化合物4p(55mg，产率74％)；mp204-206℃；通过硅胶柱纯化(石油醚/乙酸乙酯＝5：1)。According to the above synthetic route and the method of Example 18, a blue solid compound 4p (55 mg, yield 74%) was obtained; mp 204-206° C.; and purified by silica gel column (petroleum ether/ethyl acetate=5:1).

对化合物4p进行表征，具体如下：Compound 4p was characterized as follows:

表征特征：1H NMR(400MHz,CDCl3)δ8.21–8.14(m,2H),8.01(d,J＝8.0Hz,1H),7.77–7.68(m,2H),7.23(dd,J＝15.2,7.3Hz,2H),6.77(d,J＝7.9Hz,1H),4.30–4.20(m,7H),3.95(s,3H),1.21(d,J＝6.9Hz,7H).13C NMR(101MHz,CDCl3)δ182.93,177.97,164.79,148.29,134.00,133.95,132.47,132.38,126.34,126.19,123.68,122.96,115.27,104.97,63.08,55.53,36.20,29.68,13.92.HRMS(ESI)m/z calcd for C27H23NO7Na+(M+Na)+496.1378,found 496.1372.Characterization characteristics: 1 H NMR (400MHz, CDCl 3 )δ8.21–8.14 (m, 2H), 8.01 (d, J＝8.0Hz, 1H), 7.77–7.68 (m, 2H), 7.23 (dd, J＝15.2, 7.3Hz, 2H), 6.77 (d, J＝7.9Hz, 1H), 4.30–4.20 (m, 7H), 3.95 (s, 3H), 1.21 (d, J＝6.9Hz, 7H). 13 C NMR (101MHz, CDCl 3 )δ182.93,177.97,164.79,148.29,134.00,133.95,132.47,132.38,126.34,126.19,123.68,122.96,115.27,104.97,63.08,55.53,36.20,29.6 8,13.92.HRMS(ESI)m/z calcd for C 27 H 23 NO 7 Na + (M+Na) + 496.1378,found 496.1372.

实施例34Embodiment 34

按照上述合成路线以及实施例18的方法，得到紫色固体化合物4q(44mg，产率63％)；mp223-225℃；通过硅胶柱纯化(石油醚/乙酸乙酯＝5：1)。According to the above synthetic route and the method of Example 18, a purple solid compound 4q (44 mg, yield 63%) was obtained; mp 223-225° C.; purified by silica gel column (petroleum ether/ethyl acetate=5:1).

对化合物4q进行表征，具体如下：Compound 4q was characterized as follows:

表征特征：1H NMR(400MHz,CDCl3)δ8.17(t,J＝7.8Hz,3H),7.81–7.67(m,2H),7.21(td,J＝8.0,4.5Hz,1H),7.01(dd,J＝12.8,8.0Hz,1H),4.37–4.19(m,4H),4.18(s,3H),1.25(t,J＝7.1Hz,6H).13C NMR(101MHz,CDCl3)δ182.61,177.92,164.49,151.64,149.67,149.17,147.91,134.09,133.85,132.68,132.27,130.19,126.45,126.25,124.98,122.72,122.65,118.50,118.46,109.74,109.56,63.33,35.39,35.32,29.68,13.91.19F NMR(376MHz,CDCl3)δ-85.39,-135.07.HRMS(ESI)m/z calcd for C26H20NO6FNa+(M+Na)+484.1153,found 484.1162.Characterization characteristics: 1 H NMR (400MHz, CDCl 3 )δ8.17 (t, J＝7.8Hz, 3H), 7.81–7.67 (m, 2H), 7.21 (td, J＝8.0, 4.5Hz, 1H), 7.01 (dd, J＝12.8, 8.0Hz, 1H), 4.37–4.19 (m, 4H), 4.18 (s, 3H), 1.25 (t, J＝7.1Hz, 6H). 13 C NMR (101MHz, CDCl 3 )δ182.61,177.92,164.49,151.64,149.67,149.17,147.91,134.09,133.85,132.68,132.27,130.19,126.45,126.25,124.98,122.72,122.65,1 18.50,118.46,109.74,109.56,63.33,35.39,35.32,29.68,13.91. 19 F NMR(376MHz, CDCl 3 )δ-85.39,-135.07.HRMS(ESI)m/z calcd for C 26 H 20 NO 6 FNa + (M+Na) + 484.1153, found 484.1162.

实施例35Embodiment 35

按照上述合成路线以及实施例18的方法，得到紫色固体化合物4r(53mg，产率65％)；mp215-217℃；通过硅胶柱纯化(石油醚/乙酸乙酯＝5：1)。According to the above synthetic route and the method of Example 18, a purple solid compound 4r (53 mg, yield 65%) was obtained; mp 215-217° C.; purified by silica gel column (petroleum ether/ethyl acetate=5:1).

对化合物4r进行表征，具体如下：Compound 4r was characterized as follows:

表征特征：1H NMR(400MHz,CDCl3)δ8.41(d,J＝7.9Hz,1H),8.17(t,J＝7.7Hz,2H),7.84–7.61(m,3H),7.48(d,J＝7.6Hz,1H),7.14(t,J＝7.7Hz,1H),4.34(s,3H),4.31–4.22(m,4H),1.24(t,J＝6.8Hz,6H).13C NMR(101MHz,CDCl3)δ182.63,178.42,164.49,150.26,147.91,139.69,138.49,134.10,133.78,132.72,132.28,129.11,126.43,126.28,124.67,123.35,122.17,118.18,104.8,63.34,36.57,29.68,13.92.HRMS(ESI)m/z calcd forC26H20NO6NaBr+(M+Na)+544.0378,found 544.0372.Characterization characteristics: 1 H NMR (400MHz, CDCl 3 )δ8.41(d, J＝7.9Hz,1H),8.17(t, J＝7.7Hz,2H),7.84–7.61(m,3H),7.48(d, J＝7.6Hz,1H),7.14(t, J＝7.7Hz,1H),4.34(s,3H),4.31–4.22(m,4H),1.24(t, J＝6.8Hz,6H). 13 C NMR (101MHz,CDCl 3 )δ182.63,178.42,164.49,150.26,147.91,139.69,138.49,134.10,133.78,132.72,132.28,129.11,126.43,126.28,124.67,123.35,122.17,1 18.18,104.8,63.34,36.57,29.68,13.92.HRMS(ESI)m/z calcd forC 26 H 20 NO 6 NaBr + (M+Na) + 544.0378, found 544.0372.

实施例36Embodiment 36

按照上述合成路线以及实施例18的方法，得到紫红色固体化合物4s(57mg，产率74％)；mp213-215℃；通过硅胶柱纯化(石油醚/乙酸乙酯＝5：1)。According to the above synthetic route and the method of Example 18, a purple solid compound 4s (57 mg, yield 74%) was obtained; mp 213-215° C.; purified by silica gel column (petroleum ether/ethyl acetate=5:1).

对化合物4s进行表征，具体如下：Compound 4s was characterized as follows:

表征特征：1H NMR(400MHz,CDCl3)δ8.69(d,J＝21.7Hz,2H),8.45(s,1H),8.07(t,J＝9.1Hz,2H),7.71–7.63(m,2H),7.40(d,J＝12.9Hz,3H),4.28(dd,J＝12.9,6.9Hz,4H),4.01(s,3H),1.25(d,J＝3.6Hz,9H).13C NMR(101MHz,CDCl3)δ182.35,177.93,164.84,149.70,149.04,142.81,140.60,135.17,134.25,130.58,130.21,129.99,129.56,129.41,128.92,128.74,128.25,123.69,122.79,122.44,121.80,118.38,110.69,63.20,32.24,29.68,13.94.HRMS(ESI)m/z calcd for C30H23NO6Na+(M+Na)+516.1430,found 516.1423.Characterization characteristics: 1 H NMR (400MHz, CDCl 3 )δ8.69(d, J＝21.7Hz,2H),8.45(s,1H),8.07(t, J＝9.1Hz,2H),7.71–7.63(m,2H),7.40(d, J＝12.9Hz,3H),4.28(dd, J＝12.9,6.9Hz,4H),4.01(s,3H),1.25(d, J＝3.6Hz,9H). 13 C NMR (101MHz,CDCl 3 )δ182.35,177.93,164.84,149.70,149.04,142.81,140.60,135.17,134.25,130.58,130.21,129.99,129.56,129.41,128.92,128.74,128.25,1 23.69,122.79,122.44,121.80,118.38,110.69,63.20,32.24,29.68,13.94.HRMS(ESI)m/z calcd for C 30 H 23 NO 6 Na + (M+Na) + 516.1430,found 516.1423.

以上所描述的实施例是本发明一部分实施例，而不是全部的实施例。本发明的实施例的详细描述并非旨在限制要求保护的本发明的范围，而是仅仅表示本发明的选定实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The embodiments described above are part of the embodiments of the present invention, rather than all of the embodiments. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention claimed for protection, but merely represents selected embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

Claims (6)

1. A method for synthesizing an organic compound containing an indolyl naphthoquinone skeleton is characterized in that indolyl naphthoquinone derivatives and diethyl malonate are used as raw materials, and a synthesis reaction is carried out in an organic solvent under the action of a catalyst to obtain the organic compound containing the indolyl naphthoquinone skeleton;
The organic compound containing an indolyl naphthoquinone skeleton comprises an alkylated indolyl naphthoquinone compound or a compound of a benzocycloindolyl naphthoquinone;
The structural formula of the alkylated indolyl naphthoquinone compound is as follows:
The compound of the acenoindole naphthoquinone is one of the following structural formulas:
In the structural formula (III) and the structural formula (IV), R 1 is selected from C1-C3 alkyl; r 2 is selected from hydrogen or methyl; r 3 is selected from alkyl, alkoxy, halo, or hydrogen; r 4 is phenyl.
2. The method for synthesizing an organic compound having an indolaphthoquinone skeleton according to claim 1, wherein the indolaphthoquinone derivative has the structural formula:
In the structural formula (I), R 1 is selected from C1-C3 alkyl; r 2 is selected from hydrogen or methyl; r 3 is selected from alkyl, alkoxy, halo, or hydrogen; r 4 is phenyl.
3. The method for synthesizing an organic compound having an indolyl naphthoquinone skeleton according to claim 1, wherein when synthesizing an alkylated indolyl naphthoquinone compound, the catalyst used is zinc chloride and potassium t-butoxide;
the molar ratio of the indolyl naphthoquinone derivative to diethyl malonate is 1 (1-3);
The zinc chloride accounts for (20-50)% of the mole amount of the indolyl naphthoquinone derivative;
the molar ratio of the potassium tert-butoxide to the indolyl naphthoquinone derivative (1-4) is 1.
4. The method for synthesizing an organic compound having an indolyl naphthoquinone skeleton according to claim 1, wherein when the indolyl naphthoquinone compound is fused, the catalyst used is potassium carbonate and cuprous iodide;
The molar ratio of the indolyl naphthoquinone derivative to diethyl malonate is 1 (1-4);
the molar ratio of the potassium carbonate to the indolyl naphthoquinone derivative (1-2) is 1;
the cuprous iodide accounts for (10-40)% of the mole amount of the indolyl naphthoquinone derivative.
5. The method for synthesizing an organic compound having an indolaphthoquinone skeleton according to claim 1, wherein the organic solvent is acetonitrile.
6. The method for synthesizing an organic compound containing an indolyl naphthoquinone skeleton according to claim 1, wherein the synthesis reaction time is 0.5h-2h, the reaction temperature is 80-120 ℃, and the reaction conditions are closed conditions.
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