CN113416191A - Method for synthesizing tricyclic framework 2-pyridone/2-pyridine imine compound - Google Patents
Method for synthesizing tricyclic framework 2-pyridone/2-pyridine imine compound Download PDFInfo
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- C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
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Abstract
The invention discloses a method for synthesizing tricyclic framework 2-pyridone and 2-pyridine imine compounds, which belongs to the technical field of chemical synthesis, and is characterized in that one molecule of DBN (1, 5-diazabicyclo [4.3.0] non-5-ene) or DBU (1, 8-diazabicyclo [5.4.0] undec-7-ene) and one molecule of activated olefin, such as aryl methylene malononitrile and 2-cyano-3-aryl acrylate, are cyclized at room temperature or under heating condition to form new carbon-carbon and nitrogen-carbon bonds, and then are oxidized by another molecule of activated olefin to generate tricyclic framework 2-pyridone and 2-pyridine imine compounds, the operation is simple, the raw materials are easy to obtain, the conditions are mild, no catalyst is needed, the products are easy to separate and purify, the reaction yield is high, the synthesis method is a great breakthrough to the previous reaction and is expected to realize large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a method for synthesizing a tricyclic framework 2-pyridone or 2-pyridine imine compound.
Background
The 2-pyridone unit with a tricyclic framework has potential bioactivity, and a natural product containing the structural unit shows remarkable drug effect (chem.pharm.Bull.2005,53, 67-71), and related reports also show that the 2-pyridone with the tricyclic framework has excellent optical properties (Angew.chem., int.Ed.2015,54, 14492-.
However, the existing synthetic method for synthesizing the 2-pyridone structure of the tricyclic framework is relatively deficient, and the reported method has the limitations of long steps, complex raw materials, complicated operation, requirement of harsh conditions or necessity of using a catalyst and the like (J.org.chem.1998,63, 44-54; chem.Lett.2009,38, 1152-1153).
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for synthesizing a tricyclic framework 2-pyridone or 2-pyridine imine compound, which has the advantages of simple operation, mild reaction, easily obtained raw materials, no need of a catalyst and easy separation and purification of products.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a method for synthesizing tricyclic framework 2-pyridone or 2-pyridine imine compounds, which comprises the steps of cyclizing one equivalent of DBN or DBU and one equivalent of activated olefin at room temperature or under a heating condition to form new carbon-carbon and nitrogen-carbon bonds, and then carrying out hydrogen transfer redox reaction with the other equivalent of activated olefin to generate tricyclic framework 2-pyridone or 2-pyridine imine compounds; wherein:
the structural formula of the DBN or the DBU is as follows:
the activated olefin adopts 2-cyano-3-aryl acrylate or aryl methylene malononitrile;
the structural formula of the 2-cyano-3-aryl acrylate is as follows:
R1alkyl, haloAn aryl, amino, or alkoxy group;
the structural formula of the arylmethylenemalononitrile is as follows:
R2alkyl, halogen, aryl, amino or alkoxy.
The invention discloses a method for synthesizing a tricyclic framework 2-pyridone compound, which comprises the following steps:
1) under the protective atmosphere, dripping DBN or DBU into an organic solvent containing 2-cyano-3-aryl acrylate, and stirring and reacting for 3-5 h under the heating condition;
2) cooling, concentrating and separating the reaction product by column chromatography in sequence to obtain a tricyclic framework 2-pyridone or 2-pyridine imine compound;
the structural formula of the prepared tricyclic framework 2-pyridone compound is as follows:
R1alkyl, halogen, aryl, amino or alkoxy.
Preferably, the molar ratio of DBN or DBU to 2-cyano-3-aryl acrylate is 1 (2.0-2.2).
Preferably, in step 1), the organic solvent is acetonitrile, and the ratio of the DBN or DBU to the organic solvent is: 0.15 to 0.25mmol/1 mL.
Preferably, in the step 1), the protective atmosphere is a nitrogen atmosphere; the temperature adopted for heating is 100-140 ℃.
Preferably, in step 2), the column chromatography conditions are ethyl acetate: methanol-5: 1.
Further preferably, when R is1And (2) recrystallizing the mixed system of methanol and normal hexane to purify and separate.
The invention discloses a method for synthesizing a tricyclic framework 2-pyridine imine compound, which comprises the following steps:
1) under the protective atmosphere, adding DBN or DBU dropwise into an organic solvent containing aryl methylene malononitrile, and stirring and reacting for 5-8 h at room temperature;
2) filtering and recrystallizing the reaction product to obtain a tricyclic framework 2-pyridine imine compound;
the structural formula of the prepared tricyclic framework 2-pyridine imine compound is as follows:
wherein R is2Alkyl, halogen, aryl, amino or alkoxy.
Preferably, the molar ratio of DBN or DBU to arylmethylenemalononitrile is 1 (2.0-2.2).
Preferably, in step 1), the organic solvent is tetrahydrofuran, and the amount ratio of DBN or DBU to the organic solvent is: 0.9 to 1.1mmol/2 mL.
Preferably, in the step 2), a mixed system of chloroform and n-hexane or a mixed system of methanol and n-hexane is used for recrystallization.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a new method for synthesizing tricyclic framework 2-pyridone and 2-pyridine imine compounds, which generates cyclization to form new carbon-carbon and nitrogen-carbon bonds by one equivalent of DBN (1, 5-diazabicyclo [4.3.0] non-5-ene) or DBU (1, 8-diazabicyclo [5.4.0] undec-7-ene) and one equivalent of activated olefin, such as 2-cyano-3-aryl acrylate and aryl methylene malononitrile, at room temperature or under heating condition, and then generates tricyclic framework 2-pyridone and 2-pyridine imine compounds by the other equivalent of activated olefin, and has the advantages of simple operation, easily obtained raw materials, mild conditions, no need of catalysts, product separation and purification, high reaction yield, and the proposal of the synthesis method is a breakthrough of the prior easy reaction, is expected to be produced in large scale.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It is noted that the terms first, second and the like in the description and in the claims of the present invention are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The structure and spectroscopic parameters of the product obtained are as follows:
example 1: synthesis of tricyclic framework 2-pyridone compounds
Under the protection of nitrogen, adding DBN (0.2mmol) into acetonitrile solution (1mL) of ethyl 2-cyano-3-phenylacrylate (0.4mmol), stirring for 4h at 120 ℃, and cooling to room temperature after the reaction is finished; filtration and recrystallization from methanol and n-hexane (methanol: n-hexane ═ 1:5) gave 42.5mg of product in 77% yield as a yellow solid with melting point: over 289 ℃.
IR(ATR):3675,2973,2794,1700,1614,1557,1538,1495,1440,1392,1366, 1308,1273,1209,1180,1081,889,788,764,740,708,670cm-1.
1H NMR(400MHz,DMSO-d6):δ7.54–7.39(m,5H),3.83–3.75(m,2H),3.72 (t,J＝8.3Hz,2H),3.32–3.29(t,2H),2.76(t,J＝8.2Hz,2H),2.11–1.98(m,2H).
13C NMR(100MHz,DMSO-d6):δ161.2,154.9,150.2,136.4,129.4,129.0,128.3, 120.4,102.4,78.4,51.8,41.9,38.1,24.1,19.6.
HRMS(ESI):m/z:calcd for C17H16N3O+[M+H]+:278.1288；found:278.1284.
Example 2: synthesis of tricyclic framework 2-pyridone compounds
Under the protection of nitrogen, adding DBN (0.2mmol) into an acetonitrile solution (1mL) of ethyl 2-cyano-3- (4-methoxyphenyl) acrylate (0.4mmol), stirring at 120 ℃ for 4h, and cooling to room temperature after the reaction is finished; concentration and separation by column chromatography (ethyl acetate: methanol ═ 5:1) gave 54.4mg of product in 89% yield as a yellow solid with melting point 224-.
IR(ATR):3547,2913,2190,1711,1614,1535,1510,1459,1418,1392,1372, 1307,1278,1252,1175,1117,1025,973,891,842,771,755,725,700,655cm-1.
1H NMR(400MHz,CDCl3):δ7.38(d,J＝8.6Hz,2H),6.93(d,J＝8.6Hz,2H), 3.95–3.89(m,2H),3.83(s,3H),3.73(t,J＝8.4Hz,2H),3.33(t,J＝5.8Hz,2H),2.89 (t,J＝8.4Hz,2H),2.16–2.07(m,2H).
13C NMR(100MHz,CDCl3):δ161.5,160.2,154.2,151.6,129.6,127.9,119.8, 113.9,101.3,81.0,55.3,51.9,42.1,37.9,24.7,19.8.
HRMS(ESI):m/z:calcd for C18H18N3O2 +[M+H]+:308.1394；found:308.1389..
Example 3: synthesis of tricyclic framework 2-pyridone compounds
Under the protection of nitrogen, adding DBN (0.2mmol) into acetonitrile solution (1mL) of ethyl 2-cyano-3- (4-chlorophenyl) acrylate (0.4mmol), stirring at 120 ℃ for 4h, and cooling to room temperature after the reaction is finished; concentration and separation by column chromatography (ethyl acetate: methanol ═ 5:1) gave 35mg of product in 56% yield as a yellow solid with melting point 237-.
IR(ATR):3545,2912,2194,1617,1554,1534,1488,1406,1371,1307,1279, 1187,1151,1108,1089,1043,1009,977,891,833,768,754,700,651cm-1.
1H NMR(400MHz,CDCl3):δ7.42–7.32(m,4H),3.97–3.89(m,2H),3.75(t, J＝8.4Hz,2H),3.35(t,J＝5.8Hz,2H),2.86(t,J＝8.4Hz,2H),2.19–2.08(m,2H).
13C NMR(100MHz,CDCl3):δ161.2,154.3,150.7,135.3,134.1,129.5,128.8, 119.3,101.4,80.8,51.9,42.1,37.9,24.3,19.8.
HRMS(ESI):m/z:calcd for C17H15ClN3O+[M+H]+:312.0898；found:312.0885.
Example 4: synthesis of tricyclic framework 2-pyridone compounds
Under the protection of nitrogen, adding DBN (0.2mmol) into acetonitrile solution (1mL) of ethyl 2-cyano-3- (4-dimethylaminophenyl) acrylate (0.4mmol), stirring at 120 ℃ for 4h, and cooling to room temperature after the reaction is finished; concentration and separation by column chromatography (ethyl acetate: methanol ═ 5:1) gave 44.5mg of product in 69% yield as a green solid with melting point 287-289 ℃.
IR(ATR):2883,2189,1631,1604,1519,1444,1394,1355,1303,1272,1212, 1193,1163,1126,1100,1043,942,825,762,654cm-1.
1H NMR(400MHz,CDCl3):δ7.37(d,J＝8.9Hz,2H),6.74(d,J＝8.7Hz,2H), 3.95–3.89(m,2H),3.71(t,J＝8.4Hz,2H),3.31(t,J＝5.8Hz,2H),3.00(s,6H),2.93 (t,J＝8.4Hz,2H),2.14–2.07(m,2H).
13C NMR(100MHz,CDCl3):δ161.8,154.0,152.4,150.8,129.5(2C),120.1,111.7, 100.7,81.2,52.0,42.3,40.3,37.9,25.0,20.0.
HRMS(ESI):m/z:calcd for C19H20LiN4O+[M+Li]+:327.1792；found:327.1776.
Example 5: synthesis of tricyclic framework 2-pyridone compounds
Under the protection of nitrogen, adding DBN (0.2mmol) into acetonitrile solution (1mL) of ethyl 2-cyano-3- (3, 4-dimethylphenyl) acrylate (0.4mmol), stirring at 120 ℃ for 4h, and cooling to room temperature after the reaction is finished; concentration and separation by column chromatography (ethyl acetate: methanol ═ 5:1) gave 48.3mg of product in 79% yield as a yellow solid with melting point 229-.
IR(ATR):2910,2188,1620,1582,1539,1503,1451,1411,1366,1309,1276, 1242,1210,1196,1173,1151,1125,1106,1049,1027,1001,923,836,791,753, 662cm-1.
1H NMR(400MHz,CDCl3):δ7.19–7.11(m,3H),3.97–3.90(m,2H),3.77–3.69(m,2H),3.34(t,J＝5.8Hz,2H),2.87(t,J＝8.4Hz,2H),2.27(s,3H),2.26(s, 3H),2.18–2.09(m,2H).
13C NMR(100MHz,CDCl3):δ161.5,154.2,152.3,137.8,136.7,133.2,129.7, 129.1,125.5,119.6,101.2,81.2,51.9,42.1,37.9,24.6,19.9,19.8,19.7.
HRMS(ESI):m/z:calcd for C19H20N3O+[M+H]+:306.1601；found:306.1602.
Example 6: synthesis of tricyclic framework 2-pyridone compounds
Under the protection of nitrogen, adding DBU (0.2mmol) into acetonitrile solution (1mL) of ethyl 2-cyano-3-phenylacrylate (0.4mmol), stirring for 4h at 120 ℃, and cooling to room temperature after the reaction is finished; concentration and column chromatography (ethyl acetate: methanol ═ 5:1) gave 52mg of product in 85% yield as a yellow solid with melting point >289 ℃.
IR(ATR):2932,2200,1630,1543,1476,1453,1402,1375,1310,1283,1257, 1216,1187,1156,1131,1104,1079,1042,1023,991,959,934,802,774,755,727, 667cm-1.
1H NMR(400MHz,DMSO-d6):δ7.53–7.40(m,3H),7.32–7.24(m,2H),3.98 –3.90(m,2H),3.64–3.56(m,2H),3.38(d,J＝6.3Hz,2H),2.25–2.17(m,2H),2.06 –1.97(m,2H),1.91–1.81(m,2H),1.62–1.53(m,2H).
13C NMR(100MHz,DMSO-d6):δ159.1,157.51,157.49,153.7,137.3,128.5, 128.4,127.8,118.5,102.2,84.1,51.7,49.0,27.0,23.7,23.5,21.1.
HRMS(ESI):m/z:calcd for C19H19N3NaO+[M+Na]+:328.1420；found: 328.1400.
Example 7: synthesis of tricyclic framework 2-pyridone compounds
Under the protection of nitrogen, adding DBU (0.2mmol) into acetonitrile (1mL) of ethyl 2-cyano-3- (4-methylphenyl) acrylate (0.4mmol), stirring at 120 ℃ for 4h, and cooling to room temperature after the reaction is finished; concentration and column chromatography (ethyl acetate: methanol ═ 5:1) gave 50mg, 78% yield, pale yellow solid, m.p. 231-.
IR(ATR):2930,2200,1740,1634,1543,1479,1403,1378,1314,1285,1257, 1219,1175,1156,1108,1083,1041,993,959,939,908,878,827,786,768,669cm-1.
1H NMR(400MHz,CDCl3):δ7.24(d,J＝7.9Hz,2H),7.15(d,J＝8.1Hz,2H), 4.16–4.08(m,2H),3.64–3.55(m,2H),3.38(t,J＝6.5Hz,2H),2.37(s,3H),2.32(dd, J＝11.8,5.6Hz,2H),2.14–2.05(m,2H),1.99–1.87(m,2H),1.67(dt,J＝12.8,6.6 Hz,2H).
13C NMR(100MHz,CDCl3):δ159.9,159.8,153.3,138.8,134.2,129.3,128.0, 118.1,102.9,88.1,52.6,49.6,39.8,27.7,24.4,24.3,22.4,21.4.
HRMS(ESI):m/z:calcd for C20H21N3NaO+[M+Na]+:342.1577；found: 342.1559.
Example 8: synthesis of tricyclic framework 2-pyridone compounds
Under the protection of nitrogen, adding DBU (0.2mmol) into acetonitrile solution (1mL) of 2-cyano-3- (4-bromophenyl) ethyl acrylate (0.4mmol), stirring at 120 ℃ for 4h, and cooling to room temperature after the reaction is finished; concentration and separation by column chromatography (ethyl acetate: methanol ═ 5:1) gave 59.7mg of product in 78% yield as a pale yellow solid with melting point 258-.
IR(ATR):2936,2860,2202,1628,1551,1504,1476,1450,1407,1379,1363, 1337,1311,1213,1173,1148,1100,1069,1028,1007,972,910,882,844,826,793, 768,754,728,671cm-1.
1H NMR(400MHz,CDCl3):δ7.61–7.51(m,2H),7.21–7.10(m,2H),4.17– 4.03(m,2H),3.65–3.55(m,2H),3.39(t,J＝6.4Hz,2H),2.36–2.24(m,2H),2.13– 2.04(m,2H),1.99–1.90(m,2H),1.66(dt,J＝12.9,6.6Hz,2H).
13C NMR(100MHz,CDCl3):δ159.8,158.0,153.7,136.1,131.8,129.9,123.2, 118.0,102.8,87.1,52.6,49.7,39.9,27.6,24.3,24.2,22.2.
HRMS(ESI):m/z:calcd for C19H18BrLiN3O+[M+Li]+:390.0788；found: 390.0768.
Example 9: synthesis of tricyclic framework 2-pyridone compounds
Under the protection of nitrogen, adding DBU (0.2mmol) into acetonitrile solution (1mL) of ethyl 2-cyano-3-naphthyl acrylate (0.4mmol), stirring for 4h at 120 ℃, and cooling to room temperature after the reaction is finished; concentration and separation by column chromatography (ethyl acetate: methanol ═ 5:1) gave 59.7mg of product in 84% yield as a pale yellow solid with melting point 254-.
IR(ATR):2930,2197,1625,1543,1492,1465,1407,1378,1313,1284,1227, 1175,1077,963,935,903,860,831,791,762,743,674cm-1.
1H NMR(400MHz,CDCl3):δ7.90(d,J＝8.5Hz,1H),7.86(d,J＝6.8Hz,2H), 7.76(s,1H),7.55–7.48(m,2H),7.36(dd,J＝8.4,1.5Hz,1H),4.21–4.05(m,2H), 3.64–3.55(m,2H),3.37(t,J＝6.4Hz,2H),2.36–2.27(m,2H),2.09(dd,J＝11.7, 6.0Hz,2H),1.99–1.88(m,2H),1.71–1.58(m,2H).
13C NMR(100MHz,CDCl3):δ159.9,159.4,153.5,134.7,133.2,133.0,128.40, 128.38,127.8,127.5,126.7,126.5,125.8,118.1,103.1,87.9,52.6,49.6,39.9,27.7,24.4, 24.3,22.3.
HRMS(ESI):m/z:calcd for C23H22N3O+[M+H]+:356.1757；found:356.1754.
Example 10: synthesis of tricyclic framework 2-pyridine imine compound
Under the protection of nitrogen, adding DBN (0.5mmol) into a tetrahydrofuran solution (1mL) of 4-chlorobenzylidenemalononitrile (1.0mmol), stirring for 6h at 30 ℃, and cooling to room temperature after the reaction is finished; filtration and recrystallization from methanol and n-hexane (methanol: n-hexane: 1:5) gave 84.1mg of product in 54% yield as a yellow solid with melting point of 223-.
IR(ATR):3305,2863,2175,1616,1583,1554,1519,1488,1419,1377,1333, 1310,1280,1256,1200,1181,1147,1106,1088,1041,1010,976,959,922,893,831, 756,709,661cm-1.
1H NMR(400MHz,CDCl3):δ7.42(d,J＝8.6Hz,2H),7.36(d,J＝8.6Hz,2H), 4.07–3.94(m,2H),3.76–3.63(m,2H),3.35(t,J＝5.8Hz,2H),2.83–2.70(m,2H), 2.27–2.15(m,2H).
13C NMR(100MHz,CDCl3):δ158.2,154.1,149.7,135.1,134.7,129.3,128.9, 120.7,97.0,79.3,51.9,42.1,39.3,24.2,20.3.
HRMS(ESI):m/z:calcd for C17H16ClN4 +[M+H]+:311.1058；found:311.1053.
Example 11: synthesis of tricyclic framework 2-pyridine imine compound
Under the protection of nitrogen, adding DBN (0.5mmol) into a tetrahydrofuran solution (1mL) of (2-methoxybenzene) malononitrile (1.0mmol), stirring for 6h at 30 ℃, and cooling to room temperature after the reaction is finished; filtration and recrystallization from chloroform and n-hexane (chloroform: n-hexane: 1) gave 137.9mg, 90% yield, as a yellow solid with melting point 242 and 243 ℃.
IR(ATR):3301,2927,2867,2173,1616,1591,1548,1520,1487,1455,1432, 1408,1373,1335,1307,1281,1196,1156,1050,1024,957,918,793,743,714,667, cm-1.
1H NMR(400MHz,CDCl3):δ7.41–7.32(m,1H),7.23(dd,J＝7.5,1.6Hz,1H), 7.02(d,J＝7.5Hz,1H),7.00–6.96(m,1H),3.96(td,J＝5.8,1.8Hz,2H),3.85(s,3H), 3.70–3.58(m,2H),3.31(t,J＝5.8Hz,2H),2.77–2.53(m,2H),2.24–2.11(m,2H).
13C NMR(100MHz,CDCl3):δ158.4,155.9,153.7,148.4,130.4,129.6,125.0, 120.8,120.8,111.4,98.7,80.4,55.7,51.9,42.0,39.2,24.1,20.3.
HRMS(ESI):m/z:calcd for C18H19N4O+[M+H]+:307.1553；found:307.1545.
Example 12: synthesis of tricyclic framework 2-pyridine imine compound
Under the protection of nitrogen, adding DBN (0.5mmol) into a tetrahydrofuran solution (1mL) of 2-naphthyl methylene malononitrile (1.0mmol), stirring for 6h at 30 ℃, and cooling to room temperature after the reaction is finished; filtration and recrystallization from methanol and n-hexane (methanol: n-hexane: 1:10) gave 76mg of product in 47% yield as a yellow solid with melting point 220-.
IR(ATR):2925,2171,1609,1581,1548,1527,1467,1409,1378,1303,1274, 1251,1199,1143,1032,959,890,855,813,772,758,746,669cm-1.
1H NMR(400MHz,CDCl3):δ7.93–7.83(m,4H),7.57–7.45(m,3H),4.06– 3.98(m,2H),3.67(t,J＝8.4Hz,2H),3.34(t,J＝5.8Hz,2H),2.81(t,J＝8.3Hz,2H), 2.25–2.16(m,2H).
13C NMR(100MHz,CDCl3):δ158.4,154.0,151.0,133.7,133.4,133.0,128.4, 127.8,127.4,126.8,126.5,125.3,120.8,100.0,97.6,79.8,52.0,42.1,39.5,24.4,20.3.
HRMS(ESI)calcd for C21H22N5 +[M+NH4]+:344.1870；found:344.1873.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. A method for synthesizing 2-pyridone or 2-pyridine imine compounds with tricyclic frameworks is characterized in that one equivalent of DBN or DBU and one equivalent of activated olefin are cyclized at room temperature or under a heating condition to form new carbon-carbon and nitrogen-carbon bonds, and then the new carbon-carbon and nitrogen-carbon bonds and the other equivalent of activated olefin are subjected to hydrogen transfer redox reaction to generate the 2-pyridone or 2-pyridine imine compounds with tricyclic frameworks; wherein:
the structural formula of the DBN or the DBU is as follows:
the activated olefin adopts 2-cyano-3-aryl acrylate or aryl methylene malononitrile;
the structural formula of the 2-cyano-3-aryl acrylate is as follows:
R1alkyl, halo, aryl, amino or alkoxy;
the structural formula of the arylmethylenemalononitrile is as follows:
R2alkyl, halogen, aryl, amino or alkoxy.
2. A method for synthesizing a tricyclic framework 2-pyridone compound is characterized by comprising the following steps:
1) under the protective atmosphere, dripping DBN or DBU into an organic solvent containing 2-cyano-3-aryl acrylate, and stirring and reacting for 3-5 h under the heating condition;
2) cooling, concentrating and separating the reaction product by column chromatography in sequence to obtain a tricyclic framework 2-pyridone or 2-pyridine imine compound;
the structural formula of the prepared tricyclic framework 2-pyridone compound is as follows:
R1alkyl, halogen, aryl, amino or alkoxy.
3. The method for synthesizing tricyclic framework 2-pyridone compounds according to claim 2, wherein the molar ratio of DBN or DBU to 2-cyano-3-aryl acrylate is 1 (2.0 to 2.2).
4. The method for synthesizing tricyclic framework 2-pyridone compounds according to claim 2, wherein in step 1), the organic solvent is acetonitrile, and the amount ratio of DBN or DBU to the organic solvent is: 0.15 to 0.25mmol/1 mL.
5. The method for synthesizing tricyclic framework 2-pyridone compounds according to claim 2, wherein in step 1), the protective atmosphere is a nitrogen atmosphere; the heating temperature is 100-140 ℃.
6. The method for synthesizing tricyclic framework 2-pyridone compounds according to claim 2, wherein in step 2), the column chromatography conditions are ethyl acetate: methanol-5: 1.
7. A method for synthesizing a tricyclic framework 2-pyridine imine compound is characterized by comprising the following steps:
1) under the protective atmosphere, adding DBN or DBU dropwise into an organic solvent containing aryl methylene malononitrile, and stirring and reacting for 5-8 h at room temperature;
2) filtering and recrystallizing the reaction product to obtain a tricyclic framework 2-pyridine imine compound;
the structural formula of the prepared tricyclic framework 2-pyridine imine compound is as follows:
wherein R is2Alkyl, halogen, aryl, amino or alkoxy.
8. The method for synthesizing tricyclic framework 2-pyridineimine compounds according to claim 7, wherein the molar ratio of DBN or DBU to arylmethylenemalononitrile is 1 (2.0-2.2).
9. The method for synthesizing tricyclic framework 2-pyridineimine compounds according to claim 7, wherein in step 1), the organic solvent is tetrahydrofuran, and the amount ratio of DBN or DBU to the organic solvent is: 0.9 to 1.1mmol/2 mL.
10. The method for synthesizing tricyclic framework 2-pyridinylimine compounds according to claim 7, wherein in the step 2), a mixed system of chloroform and n-hexane or a mixed system of methanol and n-hexane is used for recrystallization.
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