CN107857766B - Synthetic method and application of spiroindole compound based on phenylalanine and polycarbonyl cyclic ketone compound - Google Patents
Synthetic method and application of spiroindole compound based on phenylalanine and polycarbonyl cyclic ketone compound Download PDFInfo
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Abstract
The invention discloses a synthesis method of a spiral indole compound based on phenylalanine and a polycarbonyl cyclic ketone compound. Compared with the prior art, the synthesis method is simple and convenient, the original multi-step reaction is replaced by the single-pot synthesis method, the raw materials are easy to obtain, the reaction efficiency is high, and the method is suitable for various reaction substrates; meanwhile, the obtained spiral indole compound has pharmaceutical activity and can be used in drugs which can effectively treat tumors and cancers clinically.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a synthetic method and application of a spiral indole compound based on phenylalanine and a polycarbonyl cyclic ketone compound.
Background
The spirooxindole (spirooxindole) compound can be used as an inhibitor of P53-MDM2, and the small molecular compounds can be used as a drug for treating tumors and directly target tumor cells without influencing normal cells. Over the last few years, significant progress has been made in the synthesis of spiroindole derivatives, creating a means of chiral quaternary carbon centers. For example, overlaman reported an asymmetric intramolecular heck reaction with high selectivity for the synthesis of spiro-pyrrole-3, 3' -indole derivatives; (references V.Caprio, B.Guyen, Y.Opoku-Boahen, J.Mann, S.M.Gowan, L.M.Kelland, M.A.read and S.Neidle, Bio.Med.Chem.Lett.,2000,10,2063-
Xie and Wang reported a one-pot reaction of indole with amino acid esters and isatin. (references J.Liu, H.Sun, X.Liu, L.Ouyang, T.Kang, Y.Xie and X.Wang, Tetrahedron Lett.,2012,53,2336-
The method reported above requires modification on indole ring in advance, reaction sites are limited, and derivatization and modification of molecular skeleton can not be rapidly carried out in large quantities, which greatly limits the research on product diversity. At present, the method for rapidly preparing a fused ring framework by utilizing a multi-component synthesis method and a step-by-step synthesis method is widely adopted by pharmaceutical synthesis, the functionalization of the spiroindole compound can be rapidly realized by establishing the multi-component synthesis method of the spiroindole compound, the existing structure is modified, and the construction of a complex system is realized. However, the existing synthesis technology generally needs to pass through more complex synthesis steps, and has the problems of high price of reaction raw materials, certain difficulty in operation and the like. Therefore, it is necessary to provide a novel synthesis method of the spiral indole compound.
Disclosure of Invention
The invention aims to provide a method for synthesizing a spiral indole compound based on phenylalanine and a polycarbonyl cyclic ketone compound, which replaces the original multi-step reaction by using a single-pot synthesis method, and performs addition condensation reaction on a pyridine indole compound, the phenylalanine and the polycarbonyl cyclic ketone compound in an ethanol aqueous solution to obtain the spiral indole compound with high yield.
The invention also provides application of the spiral indole compound in the aspect of testing lung cancer or gastric cancer cell proliferation experiments.
In order to achieve the purpose, the invention adopts the technical scheme that: a synthetic method of a spiral indole compound based on phenylalanine and a polycarbonyl cyclic ketone compound comprises the following steps:
(1) putting a pyridine indole compound, phenylalanine and a polycarbonyl cyclic ketone compound into an ethanol water solution reaction solvent, and heating, stirring and refluxing for reaction; wherein the mol ratio of the pyridine indole compound, the phenylalanine and the polycarbonyl cyclic ketone compound is 1 (0.8-1) to 1-1.2;
(2) and after the reaction is finished, cooling to room temperature, and performing suction filtration, recrystallization, separation and purification on the product to obtain the spiral indole compound.
In the step (1), the volume ratio of the absolute ethyl alcohol to the distilled water in the ethyl alcohol water solution is 2 (1-1.2).
The reaction conditions of the step (1) are as follows: stirring and refluxing for reaction for 2-4h under the condition of heating in the air environment.
In the step (1), the dosage ratio of the pyridine indole compound to the reaction solvent is 1mmol (45-50) mL.
The step (2) comprises the following specific steps: after the reaction is finished, cooling the temperature to room temperature, carrying out suction filtration on the reaction product to obtain a solid crude product, and then using CH for the solid crude product3Recrystallizing the OH/DMF mixed solvent for 1-2 times to obtain the spiral indole compound; wherein, CH3CH in OH/DMF mixed solvent3The volume ratio of OH to DMF is 7: 3.
In the step (1), the structural formula of the pyridine indole compound is shown in the specification
Wherein R is-H, -CH3，-CH2CH3，-CHO，-COOCH2CH3，-OCH3，-CF3，-NO2，-NH2Any one of-Ph, -Cl, Br or-I.
In the step (1), the polycarbonyl cyclic ketone compound is selected from
Any one of the above; wherein R is1is-H, -CH3，-CH2CH3，-CHO，-COOCH2CH3，-OCH3，-CF3，-NO2，-NH2Any one of-Ph, -Cl, Br or-I.
The invention provides a spiral indole compound which is prepared by the method.
The invention also provides the application of the spiral indole compound in the aspect of testing lung cancer or gastric cancer cell proliferation experiments, namely, the product obtained by reaction is prepared into a solution with the concentration of 0, 1.5625, 3.125, 6.25, 12.5,25,50,100 micrograms/ml, and then the solution with the concentration gradient is used for respectively carrying out cell proliferation experiment tests and analysis on lung cancer and gastric cancer cells.
The reaction mechanism of the present invention: pyridyl indole firstly generates Michael addition reaction with polycarbonyl ketone, and then is condensed with phenylalanine to form spiro.
The invention has the beneficial effects that: compared with the prior art, the method adopts a single-pot synthesis method to replace the original multi-step reaction, and the pyridine indole compound, the phenylalanine and the polycarbonyl cyclic ketone compound are subjected to addition condensation reaction in an ethanol water solution to obtain the high-yield spiral indole compound.
Drawings
FIG. 1 is a NMR chart of example 1;
FIG. 2 is a NMR carbon spectrum of example 1;
FIG. 3 is a NMR chart of example 2;
FIG. 4 is a NMR carbon spectrum of example 2;
FIG. 5 is a NMR chart of example 3;
FIG. 6 is a NMR carbon spectrum of example 3;
FIG. 7 is a NMR chart of example 4;
FIG. 8 is a NMR carbon spectrum of example 4;
FIG. 9 is a graph of data of concentration gradients after formulation of products obtained in examples 1-4 on lung cancer or gastric cancer cell proliferation experiments;
wherein, IC50(BGC-823) is data obtained from gastric cancer cell proliferation experiment, and IC50(A549) is data obtained from lung cancer cell proliferation experiment;
FIG. 10 is a graph showing the effect of concentration gradients on lung cancer or gastric cancer cell activity after formulation of the products of examples 1-4;
wherein, the tumor chemotherapy medicament cisplatin (Cis-DDP) is a positive reference controller, DMSO is a negative reference controller, and P1-P4 respectively correspond to the concentration gradients of the prepared products of the examples 1-4;
FIG. 11 shows the reaction equation of the present invention.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the invention, are given by way of illustration and explanation only. In the examples, all the reaction raw materials, solvents and the like are Annage reagent products.
Example 1
A method for synthesizing a phenylalanine-based helix indole compound, which comprises the following steps:
(1) respectively weighing 1mmol of 2-vinylpyridinylindoline, 1mmol of phenylalanine and 1mmol of isatin, placing the materials in 50mL of ethanol water solution reaction solvent, and heating, stirring and refluxing for reaction for 3 hours in an air environment;
(2) after the reaction is finished, cooling the temperature to room temperature, carrying out suction filtration on the reaction product to obtain a solid crude product, and then using CH for the solid crude product3Recrystallizing the OH/DMF mixed solvent for 2 times to obtain an orange solid, namely the pyridino-indoline compound 1; (ii) a The yield was 50%, and the melting point was 120-124 ℃.
The structural formula of the obtained pyridino-indoline compound 1 is as follows:
nuclear magnetic resonance hydrogen spectrum data of the product:
1H NMR(400MHz,DMSO-d6)10.43(s,1H),10.26(s,1H),8.28-8.15(m,2H),7.91-7.78(m,1H),7.51(d,J＝7.0Hz,1H),7.24(dd,J＝5.1,3.3Hz,2H),7.19-7.13(m,3H),7.13-7.05(m,2H),6.89(dtd,J＝11.5,7.6,1.1Hz,2H),6.61-6.47(m,4H),4.97(s,1H),4.03(q,J＝7.1Hz,1H),3.83(d,J＝8.6Hz,1H),2.98(ddd,J＝18.9,13.8,6.7Hz,2H).
nuclear magnetic resonance carbon spectrum data of the product:
13C NMR(101MHz,DMSO-d6)180.67,177.27,150.95,147.56,142.55,142.37,139.15,136.74,134.10,129.48,128.98,128.03,127.19,126.05,125.91,125.41,124.91,122.83,121.47,120.65,109.11,108.98,75.69,65.07,64.05,59.77,57.96。
example 2
A method for synthesizing a phenylalanine-based helix indole compound, which comprises the following steps:
(1) respectively weighing 1mmol of 2-vinylpyridinylindoline, 1mmol of phenylalanine and 1mmol of 4-nitro-isatin, placing the materials in 50mL of ethanol aqueous solution reaction solvent, and heating, stirring and refluxing for reaction for 3 hours in an air environment;
(2) after the reaction is finished, cooling the temperature to room temperature, carrying out suction filtration on the reaction product to obtain a solid crude product, and then using CH for the solid crude product3Recrystallizing the OH/DMF mixed solvent for 2 times to obtain a white solid, namely the pyridinoindoline compound 2; (ii) a The yield was 35% and the melting point was 80-82 ℃.
The structural formula of the obtained pyridino-indoline compound 2 is as follows:
nuclear magnetic resonance hydrogen spectrum data of the product:
1H NMR(400MHz,DMSO-d6)10.89(s,1H),10.56(s,1H),8.42(dd,J＝6.0,2.3Hz,1H),8.31-8.20(m,2H),8.11(ddd,J＝8.6,4.2,1.8Hz,1H),7.78(d,J＝7.6Hz,1H),7.27(d,J＝7.0Hz,2H),7.24-7.14(m,3H),7.10(dd,J＝8.6,4.8Hz,1H),6.97-6.83(m,1H),6.81-6.68(m,1H),6.60(t,J＝6.2Hz,1H),6.57-6.42(m,2H),4.98(d,J＝2.6Hz,1H),3.93(dd,J＝35.4,8.6Hz,2H),2.99(ddd,J＝18.0,13.5,6.4Hz,2H).
nuclear magnetic resonance carbon spectrum data of the product:
13C NMR(101MHz,DMSO-d6)179.82,178.38,150.73,148.98,147.76,142.36,141.97,139.21,136.63,133.52,129.05,128.34,128.06,127.56,127.38,126.72,125.96,124.42,122.99,121.93,120.78,109.31,109.12,74.95,65.10,63.75,57.12。
example 3
A method for synthesizing a phenylalanine-based helix indole compound, which comprises the following steps:
(1) respectively weighing 1mmol of 2-vinylpyridinylindoline, 1mmol of phenylalanine and 1mmol of acenaphthenequinone, placing the materials in 50mL of ethanol water solution reaction solvent, and heating, stirring and refluxing for reaction for 2 hours in an air environment;
(2) after the reaction is finished, cooling the temperature to room temperature, carrying out suction filtration on the reaction product to obtain a solid crude product, and then using CH for the solid crude product3Recrystallizing the OH/DMF mixed solvent for 2 times to obtain an orange solid, namely the pyridino-indoline compound 3; the yield was 63% and the melting point was 86-87 ℃.
The structural formula of the obtained pyridino-indoline compound 3 is as follows:
nuclear magnetic resonance hydrogen spectrum data of the product:
1H NMR(400MHz,DMSO-d6)10.23(s,1H),8.18(d,J＝2.8Hz,2H),8.11-8.02(m,1H),7.87(d,J＝8.3Hz,1H),7.80(d,J＝7.0Hz,1H),7.73(d,J＝8.0Hz,1H),7.69-7.51(m,3H),7.23(d,J＝7.1Hz,2H),7.20-7.08(m,3H),7.05(t,J＝7.3Hz,1H),6.69(td,J＝7.7,1.1Hz,1H),6.54(d,J＝7.6Hz,1H),6.47-6.35(m,1H),6.30(d,J＝7.5Hz,1H),5.00(d,J＝1.2Hz,1H),3.98(d,J＝9.1Hz,1H),3.81(d,J＝8.1Hz,1H),3.01(ddd,J＝18.9,13.7,6.5Hz,2H).
nuclear magnetic resonance carbon spectrum data of the product:
13C NMR(101MHz,DMSO-d6)203.36,179.59,150.65,147.70,142.15,140.84,139.02,136.57,133.40,131.71,130.80,129.70,129.15,128.64,128.19,128.03,127.97,127.87,125.93,125.25,124.66,122.92,122.54,121.06,120.32,108.94,78.58,65.97,63.42,57.43。
example 4
A method for synthesizing a phenylalanine-based helix indole compound, which comprises the following steps:
(1) respectively weighing 1mmol of 2-vinylpyridinylindoline, 1mmol of phenylalanine and 1mmol of 4-bromo-isatin, placing in 48mL of ethanol aqueous solution reaction solvent, and heating, stirring and refluxing for reaction for 3 hours in an air environment;
(2) after the reaction is finished, cooling the temperature to room temperature, carrying out suction filtration on the reaction product to obtain a solid crude product, and then using CH for the solid crude product3Recrystallizing the OH/DMF mixed solvent for 2 times to obtain a white solid, namely the pyridino-indoline compound 4; the yield was 26% and the melting point was 87-89 ℃.
The structural formula of the obtained pyridino-indoline compound 4 is as follows:
nuclear magnetic resonance hydrogen spectrum data of the product:
1H NMR(400MHz,DMSO-d6)10.57(s,1H),10.36(s,1H),8.23(dd,J＝4.7,1.5Hz,2H),7.81(d,J＝8.0Hz,1H),7.66(d,J＝2.0Hz,1H),7.32(dd,J＝8.3,2.1Hz,1H),7.28-7.22(m,2H),7.22-7.14(m,3H),7.10(dd,J＝8.3,6.2Hz,1H),6.90(td,J＝7.6,1.1Hz,1H),6.62(d,J＝7.4Hz,1H),6.52(ddd,J＝8.5,5.5,2.0Hz,3H),4.95(dd,J＝8.7,5.1Hz,1H),3.83(d,J＝8.8Hz,1H),3.74(d,J＝9.8Hz,1H),3.03(dd,J＝13.7,8.3Hz,1H),2.90(dd,J＝13.7,4.8Hz,1H).
nuclear magnetic resonance carbon spectrum data of the product:
13C NMR(101MHz,DMSO-d6)180.78,177.76,151.35,148.17,142.95,142.23,139.75,137.21,134.34,132.64,129.56,129.25,129.18,128.64,128.53,127.88,126.44,125.21,123.43,121.23,113.69,111.50,109.54,75.98,65.63,64.57,58.16,56.56。
test examples
The products obtained in examples 1-4 were dissolved in DMSO to 100. mu.g/ml standard solutions, diluted in half to 0, 1.5625, 3.125, 6.25, 12.5,25, 50. mu.g/ml solutions, and then the solutions with this concentration gradient were used to perform cell proliferation assays on lung and stomach cancer cells, respectively, and the cell viability was measured by the ability of the cells to reduce CCK-8 to bluish purple compounds. The lung cancer cell strain A549 and the gastric cancer cell strain BGC-823 are respectively inoculated in a 96-well plate 24h in advance, and the cell density is 3 multiplied by 104. And (3) grouping and treating the cells for 36-48h by using the solution with the concentration gradient, adding 10 mu L of CCK-8 into each hole, continuously culturing for 2h, and detecting the absorbance of each hole at the wavelength of 450nm by using an enzyme-labeling instrument. From fig. 9 and 10, it can be derived that: by taking a tumor chemotherapeutic medicament cisplatin (Cis-DDP) as a positive reference controller and DMSO as a negative reference controller, the product obtained in the example 4 has the most obvious inhibition effect on an A549 lung cancer cell proliferation experiment test, and meanwhile, the product obtained in the example 4 has the most obvious inhibition effect on a BGC-823 stomach cancer cell proliferation experiment test.
Claims (2)
1. A process for preparing the spiral indole-type compound,
the compound has a structural formula as follows:
2. the use of the spiroindoles compound of claim 1 in the preparation of a medicament for treating gastric cancer.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6114540A (en) * | 1997-09-08 | 2000-09-05 | Arqule, Inc. | Spiro[pyrrolidine-2,3'-oxindole] compounds and methods of use |
| CN105585570A (en) * | 2015-12-15 | 2016-05-18 | 贵州大学 | Isoxazole and pyrrolidinyl spirooxindole spliced compound and preparation method and application thereof |
| CN106866686A (en) * | 2017-03-30 | 2017-06-20 | 贵州大学 | Isoxazole splices double volution Oxoindole compounds of 3,3 ' pyrroles and preparation method and application |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6114540A (en) * | 1997-09-08 | 2000-09-05 | Arqule, Inc. | Spiro[pyrrolidine-2,3'-oxindole] compounds and methods of use |
| CN105585570A (en) * | 2015-12-15 | 2016-05-18 | 贵州大学 | Isoxazole and pyrrolidinyl spirooxindole spliced compound and preparation method and application thereof |
| CN106866686A (en) * | 2017-03-30 | 2017-06-20 | 贵州大学 | Isoxazole splices double volution Oxoindole compounds of 3,3 ' pyrroles and preparation method and application |
Non-Patent Citations (6)
| Title |
|---|
| Direct construction of novel exo0-selective spiropyrrolidine bisoxindoles via a three-component 1,3-dipolar cycloaddition reaction;J. Liu et al.;《Tetrahedron Letters》;Tetrahedron Letters;20120303;第53卷(第18期);第2336-2340页 * |
| Facile one-pot synthesis of novel dispirooxindole-pyrrolidine derivatives and their antimicrobial and anticancer activity against A549 human lung adenocarcinoma cancer cell line;Y. Arun et al.;《Bioorganic & Medicinal Chemistry Letters》;Bioorganic & Medicinal Chemistry Letters;20130122;第23卷(第6期);第1839-1845页 * |
| One-Pot Synthesis of Dispiro[oxindole-3,3"-pyrrolidines] by Three-Component [3+2] Cycloadditions of in situ-generated Azomethine Yildes with 3-Benzylidene-2,3-dihydro-1H-indol-2-ones;F.M.Moghaddam;《Helvetica Chimica Acta》;Helvetica Chimica Acta;20131231;第96卷;第2103-2114页 * |
| Spirooxindoles: Promising scaffolds for anticancer agents;B.Yu et al.;《European Journal of Medicinal Chemistry》;European Journal of Medicinal Chemistry;20140627;第97卷(第32期);第673-698页 * |
| Synthesis and biological evaluation of new;S.Mathusalini et al.;《New Journal of Chemistry》;New Journal of Chemistry;20160331;第40卷(第6期);第5164-5169页 * |
| 基质金属蛋白酶抑制剂的研究进展;涂国刚等;《中国新药与临床杂志》;中国新药与临床杂志;20080331;第27卷(第3期);第219-226页 * |
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