CN113264876A - Method for selectively catalyzing and hydrogenating aromatic heterocyclic compounds by non-hydrogen participation - Google Patents

Method for selectively catalyzing and hydrogenating aromatic heterocyclic compounds by non-hydrogen participation Download PDF

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CN113264876A
CN113264876A CN202110591481.8A CN202110591481A CN113264876A CN 113264876 A CN113264876 A CN 113264876A CN 202110591481 A CN202110591481 A CN 202110591481A CN 113264876 A CN113264876 A CN 113264876A
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tetrahydroquinoline
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韩波
张苗苗
张玉琦
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Yanan University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
    • C07D215/06—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/12—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/04—Ortho- or peri-condensed ring systems
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    • C07D471/00—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
    • C07D471/02—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 two hetero rings
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Abstract

The invention discloses a method for selectively catalyzing and hydrogenating heteroaromatic compounds by non-hydrogen, which takes 1, 5-cyclooctadiene iridium chloride dimer as a catalyst and phenyl silane as a hydrogen source, does not need to add a ligand, and is stirred and reacted under mild conditions to catalytically hydrogenate the heteroaromatic compounds to obtain hydrogenated products. The method has the advantages of low cost, mild reaction conditions, high selectivity and the like, and avoids the need of special equipment such as an autoclave and the like and high-temperature conditions due to the use of hydrogen.

Description

Method for selectively catalyzing and hydrogenating aromatic heterocyclic compounds by non-hydrogen participation
Technical Field
The invention belongs to the technical field of synthesis of aromatic heterocyclic compounds, and particularly relates to a high-selectivity hydrogenation method of aromatic heterocyclic compounds.
Background
Aromatic heterocyclic compounds exist in coal, petroleum and organisms in nature in a large amount, and particularly saturated or partially saturated heterocyclic compounds are common structural units and some drug intermediates in bioactive molecules or have certain physiological activity, play an important role in metabolism of organisms and exist in a plurality of alkaloids.
Research shows that the tetrahydroquinoline derivatives show better activity in the aspects of inhibiting viruses, fungi, cancers and the like. Therefore, the search for an efficient, cheap and green synthetic method to construct aromatic heterocyclic compounds represented by tetrahydroquinoline is of great scientific significance. The direct catalytic hydrogenation of heteroaromatic compounds using simple heteroaromatic substrates as raw materials is one of the most effective ways to construct partially saturated heterocyclic compounds with physiological activity. At present, the catalytic hydrogenation of aromatic heterocyclic compounds has certain difficulty, and the hydrogenation conditions are harsh. The reason is that: first, to overcome the stability of such compounds due to higher resonance energy; secondly, the presence of multiple heteroatoms which can coordinate with the transition metal in the substrate or hydrogenation product may lead, inter alia, to strong chelation, which leads to poisoning of the metal catalyst and loss of activity.
Polycyclic aromatic hydrocarbons are produced from coal tar, petroleum and organic compounds that are not fully combusted. Polycyclic aromatic hydrocarbons are recognized as major pollutants threatening the ecological environment due to their strong carcinogenic, mutagenic, and kawasaki properties, and their hydrophobic nature and low water solubility that enable them to rapidly deposit into the environment. On the contrary, the partially saturated polycyclic aromatic hydrocarbon obtained by the reduction method not only can greatly reduce the toxicity, but also has wide application in the fields of macromolecules, medicines, fuels and the like, thereby greatly improving the added value of the polycyclic aromatic hydrocarbon. At present, the reduction methods for polycyclic aromatic hydrocarbons mainly comprise: birch reduction, lithium aluminum hydride reduction, and transition metal-based catalytic hydrogenation. The transition metal catalyst comprises noble metals such as rhodium, ruthenium, palladium, platinum and the like.
TiO for Cao subject group in 20122The method is efficient, simple and convenient, and can be compatible with most of compoundsFunctional groups are easier to hydrogenate, including halogens, aldehydes ketones, and olefins. The catalytic system also successfully avoids the defect that quinoline compounds easily deactivate catalysts, and hydrogenates aromatic rings with high selectivity, wherein hetero atoms are positioned (J.Am.chem.Soc.2012,134, 17592-17598).
In 2013, a simple and efficient catalyst platinum nanowire is developed by the Gu subject group, and the aromatic heterocyclic compound can be subjected to reversible hydrogenation-oxidative dehydrogenation under mild conditions, so that the method can avoid severe conditions of high temperature and high pressure, and can be compatible with functional groups such as COOH, OH, OMe groups and the like (ChemCatchem,2013,5,2183-2186.) in the hydrogenation process.
Beller topic group report in 2015 by Co (OAc)2And phenanthroline as starting materials, preparing nitrogen-doped graphene layer modified cobalt oxide nanoparticles (Co) on alumina through a pyrolysis method3O4-Co/NGr@α-Al2O3) Is used as an active catalyst for the hydrogenation of various azaaromatics, including quinolines, acridines, benzo [ h ]]Quinolones, 1, 5-naphthyridines, and unprotected indoles. The unique structure of the novel heterogeneous catalyst can activate hydrogen molecules at lower temperature, and high selectivity and high activity are realized in the hydrogenation reaction process (J.Am.chem.Soc.2015,137, 11718-11724).
The 2016 Gao group developed a highly regioselective catalytic hydrogenation of quinoline by manipulating the size of platinum nanoparticles, which depends on the structure of the d-band electrons, and the yield of 1,2,3, 4-tetrahydroquinoline from the product was nearly quantitative (Angew. chem. int. Ed,2016,55, 15656-.
The Beller topic group in 2017 develops a hydrogenation method for catalyzing quinoline and other nitrogen-containing heterocyclic compounds with high selectivity based on a homogeneous cobalt metal catalytic system. Using 3 mol% of cheap Co (BF) at a temperature between 60-100 deg.C and a hydrogen pressure of 10atm4)2·6H2O is used as a catalyst, 3mol percent of triphenylphosphine derivative is used as a ligand, the system can hydrogenate a series of heterocyclic compounds, 20 examples of conventional substrates are expanded, the yield range is 78-98 percent, particularly the substrate is 2, 2' -biquinoline, and high-selectivity addition with two reduced heterocycles can be obtained with the yield of 96 percentHydrogen production. In addition, 4 cases of aza polycyclic aromatic hydrocarbon are expanded, the conversion can be realized at a relatively harsh temperature, and the yield is higher than 80%. In terms of functional groups, F, Cl, Br, OH and NH can be compatible2Some sensitive groups such as CHO, COOH, COOMe and amido can even retain alkenyl and alkynyl groups in the substrate, have good regioselectivity, and exceed the catalytic efficiency of noble metals to some extent (Angew. chem. int. Ed,2017,56, 3216-3220).
In the present stage, the main synthesis method of the 1,2,3, 4-tetrahydroquinoline compound still adopts hydrogen as a reducing agent, so that special equipment and harsh conditions, such as an autoclave and higher reaction temperature, are necessarily used. Therefore, the development of an efficient green synthetic method has important research significance.
Disclosure of Invention
The invention aims to provide a method for efficiently and selectively catalyzing and hydrogenating heteroaromatic compounds in a non-hydrogen atmosphere by using 1, 5-cyclooctadiene iridium chloride dimer as a catalyst and phenyl silane as a hydrogen source.
Aiming at the purposes, the technical scheme adopted by the invention is as follows: adding 1, 5-cyclooctadiene iridium chloride dimer, phenyl silane and an aromatic heterocyclic compound shown in formula I, formula II or formula III into an organic solvent, stirring and reacting at 40-50 ℃ under a nitrogen atmosphere and a closed condition, separating and purifying a product after the reaction is finished, and correspondingly obtaining a hydrogenated product shown in formula I ', formula II ' or formula III '.
Figure BDA0003089739020000031
In the formula, R, R1、R2Each independent representative H, C1～C4Alkyl radical, C1～C3Any one of alkoxy, phenyl, hydroxyl, carboxyl, ester group, cyano, trifluoromethyl, halogen and nitro; x represents N, Y represents CH, or X represents CH, Y represents N, and M represents CH or N.
In the above structural formula, R preferably represents H, methyl, isopropyl, phenyl, hydroxy, ester group, cyano, trifluoromethyl,Any one of ethoxy, methoxy, fluorine, chlorine, bromine and nitro, R1、R2Each independently represents any one of H, methyl and phenyl.
In the above synthesis method, the molar ratio of the heteroaromatic compound to the 1, 5-cyclooctadiene iridium chloride dimer and the phenylsilane is preferably 1:2 to 3:35 to 50.
The organic solvent is preferably methanol or ethanol.
In the above synthesis method, the reaction is preferably carried out under stirring at 40 to 50 ℃ for 20 to 30 hours in a nitrogen atmosphere and under a sealed condition.
Compared with the prior art, the invention has the following beneficial effects:
(1) the synthesis method is simple and green, the raw materials are cheap and easy to obtain, and the reaction is carried out in a non-hydrogen atmosphere, so that the use of special equipment is avoided.
(2) The method has the advantages of mild reaction conditions, simple operation, high yield up to 96.3%, high selectivity and high yield.
(3) The 1, 5-cyclooctadiene iridium chloride dimer and the phenylsilane used in the present invention are commercially available reagents.
(4) The invention has good substrate universality, thereby being better and convenient to apply.
Detailed Description
The present invention will be described in further detail with reference to examples, but the scope of the present invention is not limited to these examples.
Example 1
Synthesizing 1,2,3, 4-tetrahydroquinoline with the structural formula
Figure BDA0003089739020000041
0.0067g (0.05mol) of [ Ir (cod) Cl]2Adding into a 25mL high pressure reaction tube, discharging with three-way tube, adding 24 μ L (0.02mmol) quinoline, 0.1mL (0.8mmol) phenylsilane, and 2.5mL methanol under nitrogen flow, sealing, stirring at 45 deg.C for 24 hr, adding 10mL saturated ammonium chloride water solution to quench reaction, extracting with ethyl acetate (10 mL each time)And 3 times), combining the extracts, adding anhydrous sodium sulfate, drying, taking a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 10:1 as a developing agent, and separating the product by column chromatography to obtain an oily product 1,2,3, 4-tetrahydroquinoline with the yield of 93.6%.
The spectral data of the product obtained are:1H NMR(400MHz,CDCl3):δ＝6.99-6.93(m,2H),6.61(td,J＝7.5,0.9Hz,1H),6.48(d,J＝7.8Hz,1H),3.30(t,J＝5.48,1H),2.77(t,J＝6.4Hz,1H),1.98-1.91(m,1H)；13C NMR(100MHz,CDCl3):δ＝144.9,129.7,126.9,121.6,117.1,114.3,42.1,27.1,22.3。
example 2
Synthesizing 1,2,3, 4-tetrahydroquinoxaline
Figure BDA0003089739020000051
In this example, the quinoline in example 1 was replaced with an equimolar amount of quinoxaline, and the other procedure was the same as in example 1 to obtain 1,2,3, 4-tetrahydroquinoxaline as a product with a yield of 59%.
The spectral data of the product obtained are:1H NMR(400MHz,CDCl3):δ＝6.62-6.56(m,2H),6.53-6.47(m,2H),3.42(bs,4H+2NH)；13C NMR(100MHz,CDCl3):δ＝133.3,118.4,114.4,40.9。
example 3
The synthetic structural formula of the compound is 1,2,3, 4-tetrahydro-1, 10-phenanthroline
Figure BDA0003089739020000052
In this example, quinoline in example 1 was replaced with 1, 10-phenanthroline in equimolar amount, and the other steps were the same as in example 1, to obtain 1,2,3, 4-tetrahydro-1, 10-phenanthroline as a product in 47.3% yield.
The spectral data of the product obtained are:1H NMR(400MHz,CDCl3):δ＝8.68(dd,J＝4.2,1.7Hz,1H),8.01(dd,J＝8.3,1.7Hz,1H),7.29(dd,J＝8.3,4.2Hz,1H),7.16(d,J＝8.2Hz,1H),6.98(d,J＝8.2Hz,1H),5.93(bs,NH),3.56-3.50(m,2H),2.92(t,J＝6.4Hz,2H),2.10-2.03(m,2H)；13C NMR(100MHz,CDCl3):δ＝147.1,140.8,137.6,136.0,127.5,120.7,116.7,113.2,41.4,27.2,21.9。
example 4
The synthetic structural formula of the compound is 5-bromo-1, 2,3, 4-tetrahydroquinoline
Figure BDA0003089739020000053
In this example, 5-bromo-1, 2,3, 4-tetrahydroquinoline was obtained in 85.4% yield by replacing quinoline with 5-bromo-quinoline in an equimolar amount and following the same procedure as in example 1.
The spectral data of the product obtained are:1H NMR(400MHz,CDCl3):δ＝6.87(dd,J＝7.9,1.3Hz,1H),6.81(t,J＝7.8Hz,1H),6.41(dd,J＝7.8,1.3Hz,1H),3.86(bs,NH),3.28-3.23(m,2H),2.77(t,J＝6.6Hz,2H),2.00-1.93(m,2H)；13C NMR(100MHz,CDCl3):δ＝146.3,127.4,125.8,120.5,112.9,41.3,27.4,21.9。
example 5
The synthetic structural formula of the compound is 6-cyano-1, 2,3, 4-tetrahydroquinoline
Figure BDA0003089739020000061
In this example, the quinoline in example 1 was replaced with equimolar 6-cyanoquinoline and the other procedure was the same as in example 1 to obtain 6-cyano-1, 2,3, 4-tetrahydroquinoline as a product in a yield of 71.8%.
The spectral data of the product obtained are:1H NMR(400MHz,CDCl3):δ＝7.18(dd,J＝10.4,2.1Hz,2H),6.38(d,J＝8.2Hz,1H),4.42(bs,NH),3.40-3.30(m,2H),2.72(t,J＝6.3Hz,2H),1.96-1.86(m,2H)；13C NMR(100MHz,CDCl3):δ＝148.0,132.9,131.0,120.7,112.9,97.3,41.3,26.5,20.7。
example 6
The synthetic structural formula of the compound is 1,2,3, 4-tetrahydro-1, 5-naphthyridine
Figure BDA0003089739020000062
In this example, the quinoline in example 1 was replaced with equimolar 1, 5-naphthyridine and the other procedure was the same as in example 1 to give the product 1,2,3, 4-tetrahydro-1, 5-naphthyridine in 48.5% yield.
The spectral data of the product obtained are:1H NMR(400MHz,CDCl3):δ＝7.85(dd,J＝4.6,1.2Hz,1H),6.87(dd,J＝8.0,4.7Hz,1H),6.71(dd,J＝8.0,1.4Hz,1H),3.82(bs,NH),3.31-3.26(m,2H),2.92(t,J＝6.5Hz,2H),2.06-1.98(m,2H)；13C NMR(101MHz,CDCl3):δ＝142.3,140.5,137.5,121.4,119.7,41.0,29.8,21.3。
example 7
The synthetic structural formula of the 2-methyl-1, 2, 34-tetrahydroquinoline is shown in the specification
Figure BDA0003089739020000063
In this example, the quinoline in example 1 was replaced with 2-methylquinoline in equimolar amount, and the other procedure was the same as in example 1 to obtain 2-methyl-1, 2,3, 4-tetrahydroquinoline as a product in a yield of 57.5%.
The spectral data of the product obtained are:1H NMR(400MHz,CDCl3):δ＝6.99-6.94(m,2H),6.61(td,J＝7.4,1.2Hz,1H),6.48(dd,J＝8.3,1.2Hz,1H),3.70(bs,NH),3.45-3.37(m,1H),2.90-2.80(m,1H),2.77-2.70(m,1H),1.97-1.90(m,1H),1.65-1.54(m,1H),1.22(d,J＝6.3Hz,3H)；13C NMR(101MHz,CDCl3):δ＝144.6,129.1,126.5,120.9,116.8,113.8,77.2,46.9,29.93,26.4,22.4。
example 8
The synthetic structural formula of the compound is 8-methyl-1, 2,3, 4-tetrahydroquinoline
Figure BDA0003089739020000071
In this example, the quinoline in example 1 was replaced by 8-methylquinoline in equimolar amount, and the other procedure was the same as in example 1 to obtain 8-methyl-1, 2,3, 4-tetrahydroquinoline as a product in 74.8% yield.
The spectral data of the product obtained are:1H NMR(400MHz,CDCl3):δ＝6.89(t,J＝9.0Hz,2H),6.61-6.55(m,1H),3.66(bs,NH),3.42-3.37(m,2H),2.81(t,J＝5.7Hz,2H),2.10(s,3H),2.00-1.92(m,2H)；13C NMR(101MHz,CDCl3):δ＝143.1,128.3,121.3,116.8,77.8,42.8,27.7,22.6,17.6。
example 9
The synthetic structural formula of the compound is 6-methoxy-1, 2,3, 4-tetrahydroquinoline
Figure BDA0003089739020000072
In this example, the quinoline in example 1 was replaced with equimolar 6-methoxyquinoline and the other procedures were the same as in example 1 to obtain 6-methoxy-1, 2,3, 4-tetrahydroquinoline as a product in a yield of 70.6%.
The spectral data of the product obtained are:1H NMR(400MHz,CDCl3):δ＝6.62-.55(m,2H),6.46(d,J＝8.5Hz,1H),3.73(s,3H),3.28-3.23(m,2H),2.76(t,J＝6.5Hz,2H),1.97-1.89(m,2H)；13C NMR(101MHz,CDCl3):δ＝151.6,138.7,122.9,115.4,114.6,112.7,77.2,55.6,42.1,26.9,22.2。
example 10
The synthetic structural formula of the compound is 6-fluoro-1, 2,3, 4-tetrahydroquinoline
Figure BDA0003089739020000081
In this example, the quinoline in example 1 was replaced with equimolar 6-fluoroquinoline and the other procedure was the same as in example 1 to obtain 6-fluoro-1, 2,3, 4-tetrahydroquinoline as a product in 52.0% yield.
The spectral data of the product obtained are:1H NMR(400MHz,CDCl3):δ＝6.71-6.64(m,2H),6.40(dd,J＝9.4,4.9Hz,1H),3.29-3.24(m,2H),2.74(t,J＝6.5Hz,2H),1.96-1.89(m,2H)；13C NMR(100MHz,CDCl3):δ＝155.3(d,J＝234.5Hz),140.7(d,J＝1Hz),122.6(d,J＝6.7Hz),115.4(d,J＝21.6Hz),114.7(d,J＝7.6Hz),113.0(d,J＝22.4Hz)。
example 11
The synthetic structural formula of the compound is 6-methyl-1, 2,3, 4-tetrahydroquinoline
Figure BDA0003089739020000082
In this example, the quinoline in example 1 was replaced with 6-methylquinoline in equimolar amount, and the other procedure was the same as in example 1 to obtain 6-methyl-1, 2,3, 4-tetrahydroquinoline as a product in a yield of 71.4%.
The spectral data of the product obtained are:1H NMR(400MHz,CDCl3):δ＝6.80(d,J＝5.7Hz,2H),6.44-6.41(m,1H),3.31-3.27(m,2H),2.75(t,J＝6.5Hz,2H),2.22(s,3H),1.98-1.91(m,2H)；13NMR(100MHz,CDCl3):δ＝142.2,129.9,127.0,126.1,121.4,114.3,41.9,26.7,22.2,20.2。
example 12
The synthetic structural formula of the 2-phenyl-1, 2,3, 4-tetrahydroquinoline is shown in the specification
Figure BDA0003089739020000083
In this example, the quinoline in example 1 was replaced with equimolar 2-phenylquinoline and the other procedure was the same as in example 1 to obtain 2-phenyl-1, 2,3, 4-tetrahydroquinoline as a product in 86.7% yield.
The spectral data of the product obtained are:1H NMR(400MHz,CDCl3):δ＝7.46-7.29(m,5H),7.05(t,J＝7.4Hz,2H),6.69(td,J＝7.4,1.0Hz,1H),6.57(d,J＝7.6Hz,1H),4.47(dd,J＝9.3,3.3Hz,1H),4.07(bs,NH),3.02-2.90(m,1H),2.77(dt,J＝16.3,4.8Hz,1H),2.08-2.98(m,1H)；13C NMR(100MHz,CDCl3):δ＝144.6,144.5,129.1,128.4,127.2,126.7,126.4,120.7,116.9,113.8,77.2,56.0,30.8,26.2。
example 13
Synthesizing 1,2,3, 4-tetrahydrobenzo [ h ] quinoline
Figure BDA0003089739020000091
In this example, the quinoline in example 1 was replaced with equimolar benzo [ h ] quinoline and the other procedure was the same as in example 1 to obtain 1,2,3, 4-tetrahydrobenzo [ h ] quinoline as a product in 83.4% yield.
The spectral data of the product obtained are:1H NMR(400MHz,CDCl3):δ＝7.80-7.75(m,1H),7.73-7.68(m,1H),7.43(dd,J＝8.5,1.3Hz,2H),7.23-7.14(m,2H),4.25(bs,NH),3.50(t,J＝5.4,Hz,2H),2.95(t,J＝6.4Hz,2H),2.06(dt,J＝11.9,6.4Hz,2H)；13C NMR(100MHz,CDCl3):δ＝139.4,133.4,129.0,128.9,125.4,125.2,123.6,119.9,117.3,116.2,42.8,27.9,22.5。
example 14
The synthetic structural formula of the compound is 5-methyl-1, 2,3, 4-tetrahydroquinoline
Figure BDA0003089739020000092
In this example, 5-methyl-1, 2,3, 4-tetrahydroquinoline was obtained in 70.0% yield by replacing quinoline with 5-methylquinoline in an equimolar amount and following the same procedure as in example 1.
The spectral data of the product obtained are:1H NMR(400MHz,CDCl3):δ＝6.90(t,J＝7.7Hz,1H),6.54(d,J＝7.4Hz,1H),6.39(d,J＝8.0Hz,1H),3.29-3.25(m,2H),2.66(t,J＝6.6Hz,2H),2.19(s,3H),2.04-1.97(m,2H)；13C NMR(100MHz,CDCl3):δ＝144.8,137.1,125.9,120.0,118.7,112.3,41.4,23.9,22.3,19.2。
example 15
The synthetic structural formula of the compound is shown as the following 7-chloro-2-methyl-1, 2,3, 4-tetrahydroquinoline
Figure BDA0003089739020000093
In this example, the quinoline in example 1 was replaced with equimolar 7-chloro-2-methylquinoline and the other procedure was the same as in example 1 to give 7-chloro-2-methyl-1, 2,3, 4-tetrahydroquinoline as a product in 69.7% yield.
The spectral data of the product obtained are:1H NMR(400MHz,CDCl3):δ＝6.85(d,J＝8.0Hz,1H),6.55(dd,J＝8.0,2.1Hz,1H),6.44(d,J＝2.1Hz,1H),3.75(bs,NH),3.46-3.32(m,1H),2.84-2.62(m,2H),1.99-1.86(m,1H),1.60-1.50(m,1H),1.21(d,J＝6.3Hz,3H)；13C NMR(100MHz,CDCl3):δ＝145.8,132.0,130.3,119.4,116.7,113.4,47.1,29.9,26.2,22.6。
example 16
Synthesis of methyl 1,2,3, 4-tetrahydroquinoline-6-carboxylate
Figure BDA0003089739020000101
In this example, the same procedures as in example 1 were repeated except for using equimolar 6-quinolinecarboxylic acid methyl ester instead of quinoline in example 1 to give the product 1,2,3, 4-tetrahydroquinoline-6-carboxylic acid methyl ester in a yield of 68.6%.
The spectral data of the product obtained are:1H NMR(400MHz,CDCl3):δ＝7.68-7.59(m,2H),6.38(d,J＝8.9Hz,1H),4.36(bs,NH),3.83(s,2H),3.39-3.30(m,3H),2.76(t,J＝6.3Hz,2H),1.95-1.88(m,2H)；13C NMR(100MHz,CDCl3):δ＝167.4,148.6,131.1,128.9,119.7,117.1,112.4,51.3,41.5,26.7,21.2。
example 17
Synthesizing 7-trifluoro-1, 2,3, 4-tetrahydroquinoline with the structural formula
Figure BDA0003089739020000102
In this example, the quinoline in example 1 was replaced with equimolar 7-trifluoroquinoline and the other procedure was the same as in example 1 to obtain 7-trifluoro-1, 2,3, 4-tetrahydroquinoline as a product in a yield of 71.2%.
The spectral data of the product obtained are:1H NMR(400MHz,CDCl3):δ＝7.05-6.97(m,1H),6.85-6.77(m,1H),6.67(s,1H),4.01(bs,NH),3.37-3.28(m,2H),2.78(t,J＝6.4Hz,2H),1.98-1.91(m,2H)；13C NMR(100MHz,CDCl3):δ＝144.9,129.8,129.2(q,J＝32.0Hz),124.9,124.5(q,J＝271.0Hz),113.1,110.3,41.8,27.1,21.6。
example 18
The synthetic structural formula of the compound is 6-chloro-1, 2,3, 4-tetrahydroquinoline
Figure BDA0003089739020000111
In this example, the quinoline in example 1 was replaced with 6-chloroquinoline in equimolar amount, and the other procedure was the same as in example 1 to obtain 6-chloro-1, 2,3, 4-tetrahydroquinoline as a product in a yield of 71.5%.
The spectral data of the product obtained are:1H NMR(400MHz,CDCl3):δ＝6.95-6.85(m,2H),6.38(d,J＝8.3Hz,1H),3.80(bs,NH),3.33-3.24(m,2H),2.72(t,J＝6.4Hz,2H),1.95-1.87(m,2H)；13C NMR(100MHz,CDCl3):δ＝143.4,129.2,126.6,122.9,121.3,115.2,77.2,41.9,26.9,21.9。
example 19
The synthetic structural formula of the compound is as follows, namely 6-ethoxy-2-methyl-1, 2,3, 4-tetrahydroquinoline
Figure BDA0003089739020000112
In this example, the quinoline in example 1 was replaced with equimolar 6-ethoxy-2-methylquinoline and the other procedure was the same as in example 1 to obtain 6-ethoxy-2-methyl-1, 2,3, 4-tetrahydroquinoline as a product in a yield of 96.3%.
The spectral data of the product obtained are:1H NMR(400MHz,CDCl3):δ＝6.64-6.55(m,2H),6.44(d,J＝8.1Hz,1H),3.94(q,J＝7.0Hz,2H),3.40-3.26(m,1H),2.92-2.77(m,1H),2.70(ddd,J＝16.6,5.4,3.1Hz,1H),1.98-1.85(m,1H),1.63-1.52(m,1H),1.37(t,J＝7.0Hz,3H),1.20(d,J＝6.3Hz,3H)；13C NMR(100MHz,CDCl3):δ＝150.9,138.7,122.3,115.4,115.1,113.4,63.9,47.3,30.1,26.7,22.4,14.9。
example 20
The synthetic structural formula of the 2, 6-dimethyl-1, 2,3, 4-tetrahydroquinoline is shown in the specification
Figure BDA0003089739020000113
In this example, the quinoline in example 1 was replaced with 2, 6-dimethylquinoline in equimolar amount, and the other procedure was the same as in example 1 to obtain 2, 6-dimethyl-1, 2,3, 4-tetrahydroquinoline as a product in 89.2% yield.
The spectral data of the product obtained are:1H NMR(400MHz,CDCl3):δ＝6.80(d,J＝7.4Hz,2H),6.43(d,J＝8.2Hz,1H),3.43-3.33(m,1H),2.92-2.77(m,1H),2.71(ddd,J＝16.4,5.4,3.3Hz,1H),2.23(s,3H),1.98-1.89(m,1H),1.65-1.54(m,1H),1.22(d,J＝6.3Hz,3H)；13C NMR(100MHz,CDCl3):δ＝142.6,129.9,127.3,126.4,121.4,114.4,47.4,30.5,26.7,22.7,20.5。
example 21
The synthetic structural formula of the compound is as follows, namely 6-methoxy-2-methyl-1, 2,3, 4-tetrahydroquinoline
Figure BDA0003089739020000121
In this example, the quinoline in example 1 was replaced with equimolar 6-methoxy-2-methylquinoline and the other procedure was the same as in example 1 to obtain 6-methoxy-2-methyl-1, 2,3, 4-tetrahydroquinoline as a product with a yield of 84.5%.
The spectral data of the product obtained are:1H NMR(400MHz,CDCl3):δ＝6.65-6.55(m,2H),6.46(d,J＝8.3Hz,1H),3.73(s,3H),3.39-3.28(m,1H),2.93-2.78(m,1H),2.78-2.65(m,1H),1.98-1.86(m,1H),1.61-1.55(m,1H),1.21(d,J＝6.3Hz,3H)；13C NMR(100MHz,CDCl3):δ＝151.9,139.0,122.6,115.4,114.7,112.9,55.9,47.6,30.4,27.0,22.7。
example 22
The synthetic structural formula of the compound is 5-hydroxy-1, 2,3, 4-tetrahydroquinoline
Figure BDA0003089739020000122
In this example, 5-hydroxy-1, 2,3, 4-tetrahydroquinoline was obtained in 83.6% yield by replacing quinoline with 5-hydroxyquinoline in an equimolar amount and following the same procedure as in example 1.
The spectral data of the product obtained are:1H NMR(400MHz,CDCl3):δ＝6.84(t,J＝8.0Hz,1H),6.12(d,J＝8.0Hz,2H),4.39(bs,NH),3.29-3.24(m,2H),2.66(t,J＝6.6Hz,2H),2.01-1.93(m,2H)；13C NMR(100MHz,CDCl3):δ＝154.1,146.3,127.1,108.3,107.4,103.9,41.6,21.9,20.5。
example 22
The synthetic structural formula of the compound is 3-methyl-1, 2,3, 4-tetrahydroquinoline
Figure BDA0003089739020000131
In this example, the quinoline in example 1 was replaced by equimolar 3-methylquinoline, and the other steps were the same as in example 1 to obtain 3-methyl-1, 2,3, 4-tetrahydroquinoline as a product in a yield of 95.2%.
The spectral data of the product obtained are:1H NMR(400MHz,CDCl3):δ＝7.03-6.92(m,2H),6.62(td,J＝7.4,1.0Hz,1H),6.50(d,J＝7.9Hz,1H),3.28(ddd,J＝11.0,3.7,2.0Hz,1H),2.91(dd,J＝10.8,9.9Hz,1H),2.79(ddd,J＝16.0,4.8,1.7Hz,1H),2.45(dd,J＝16.0,10.3Hz,1H),2.13-1.98(m,1H),1.06(d,J＝6.6Hz,3H)；13C NMR(100MHz,CDCl3):δ＝144.4,129.7,126.8,121.3,117.1,113.9,48.9,35.6,29.9,27.3,19.2。
example 23
The synthetic structural formula is shown as the following 1,1 ', 2,2 ', 3,3 ', 4,4 ' -decahydro-2, 2 ' -biquinoline
Figure BDA0003089739020000132
In this example, the quinoline in example 1 was replaced with 2, 2-biquinoline in equimolar amount, and the other procedure was the same as in example 1 to obtain 1,1 ', 2,2 ', 3,3 ', 4,4 ' -decahydro-2, 2 ' -biquinoline (racemate) in 50.8% yield.
The obtained racemate spectrum data are as follows:1H NMR(400MHz,CDCl3):δ＝7.01(t,J＝7.8Hz,4H),6.66(t,J＝7.8Hz,2H),6.54(d,J＝7.8Hz,2H),4.00(bs,2H),3.49-3.39(m,2H),2.98-2.75(m,4H),2.00-1.89(m,4H)；13C NMR(100MHz,CDCl3):δ＝144.8,129.3,127.0,121.6,117.4,114.364,77.2,55.4,26.7,23.1。
in addition, 1 ', 2,2 ', 3,3 ', 4,4 ' -decahydro-2, 2 ' -biquinoline meso form having the following structural formula was obtained in this example with a yield of 25.2%.
Figure BDA0003089739020000133
The spectral data of the resulting mesomer are:1H NMR(400MHz,CDCl3):δ＝7.06-6.94(m,4H),6.65(td,J＝7.4,1.2Hz,12H),6.57(dd,J＝8.0,1.2Hz,2H),4.10(bs,2NH),3.34-3.27(m,2H),2.90-2.70(m,4H),2.03-1.80(m,4H).13C NMR(100MHz,CDCl3):δ＝144.2,129.4,127.1,121.7,117.6,114.9,77.2,54.9,25.9,24.3。
example 24
The synthetic structural formula of the compound is shown as the following 2, 9-dimethyl-1, 2,3, 4-tetrahydro-1, 10-phenanthroline
Figure BDA0003089739020000141
In this example, quinoline in example 1 was replaced with 2, 9-dimethyl-1, 10-phenanthroline in equimolar amount, and the other procedure was the same as in example 1 to obtain 2, 9-dimethyl-1, 2,3, 4-tetrahydro-1, 10-phenanthroline as a product in 47.5% yield.
The spectral data of the product obtained are:1H NMR(400MHz,CDCl3):δ＝7.89(d,J＝8.4Hz,1H),7.17(d,J＝8.4Hz,1H),7.10(d,J＝8.2Hz,1H),6.95(d,J＝8.2Hz,1H),5.85(bs,1NH),3.66-3.53(m,1H),3.00(ddd,J＝16.7,11.0,5.8Hz,1H),2.87(ddd,J＝16.7,5.5,3.9Hz,1H),2.69(s,3H),2.05(dddd,J＝12.7,6.1,3.2,1.2Hz,1H),1.73(dddd,J＝12.8,11.0,9.6,5.4Hz,1H),1.38(d,J＝6.3Hz,3H)；13C NMR(100MHz,CDCl3):δ＝155.9,140.2,136.9,136.1,127.9,125.4,121.4,116.7,113.4,77.5,46.7,30.2,26.8,25.3,22.6。
example 25
The synthetic structural formula of the compound is 6-isopropyl-1, 2,3, 4-tetrahydroquinoline
Figure BDA0003089739020000142
In this example, the quinoline in example 1 was replaced with equimolar 6-isopropylquinoline and the other procedure was the same as in example 1 to obtain 2, 6-isopropyl-1, 2,3, 4-tetrahydroquinoline as a product in 73.8% yield.
The spectral data of the product obtained are:1H NMR(400MHz,CDCl3):δ＝6.91-6.81(m,2H),6.46(d,J＝8.0Hz,1H),3.34-3.25(m,2H),2.78(td,J＝6.7,2.3Hz,2H),2.04-1.89(m,2H),1.22(d,J＝7.0Hz,6H)；13C NMR(100MHz,CDCl3):δ＝142.9,137.8,127.6,124.7,121.5,114.6,42.3,33.3,29.8,27.2,24.4,22.5。
example 26
The synthetic structural formula of the compound is 6-hydroxy-1, 2,3, 4-tetrahydroquinoline
Figure BDA0003089739020000143
In this example, the quinoline in example 1 was replaced with 6-hydroxyquinoline in equimolar amount, and the other procedure was the same as in example 1 to obtain 6-hydroxy-1, 2,3, 4-tetrahydroquinoline as a product in a yield of 46.7%.
The spectral data of the product obtained are:1H NMR(400MHz,DMSO-d6)δ＝8.22(s,1H),6.34-6.23(m,2H),6.27-6.19(m,1H),4.92(s,1H),3.08-3.00(m,2H),2.55(t,J＝6.5Hz,2H),1.76-1.67(m,2H)；13C NMR(100MHz,DMSO-d6)δ＝147.9,138.2,121.3,115.6,114.9,113.6,41.4,26.8,22.1。
example 27
The synthetic structural formula is shown as the following 1,2,3, 4-tetrahydroquinoline-6-formic acid
Figure BDA0003089739020000151
In this example, the quinoline in example 1 was replaced with an equimolar amount of quinoline-6-carboxylic acid, and the other procedure was the same as in example 1 to obtain 1,2,3, 4-tetrahydroquinoline-6-carboxylic acid as a product in a yield of 72.1%.
The spectral data of the product obtained are:1H NMR(400MHz,CDCl3):δ＝7.71(d,J＝7.5Hz,2H),6.40(d,J＝8.7Hz,1H),3.41-3.32(m,2H),2.78(t,J＝6.3Hz,2H),1.97-1.90(m,2H)；13C NMR(100MHz,CDCl3):δ＝149.58,132.2,130.1,120.0,116.5,112.8,41.9,26.9,21.4。
example 28
The synthetic structural formula of the compound is 6-nitro-1, 2,3, 4-tetrahydroquinoline
Figure BDA0003089739020000152
In this example, the quinoline in example 1 was replaced with 6-nitroquinoline in equimolar amount, and the other procedure was the same as in example 1 to obtain 6-nitro-1, 2,3, 4-tetrahydroquinoline as a product in 89% yield.
The spectral data of the product obtained are:1H NMR (400MHz,CDCl3)δ＝7.87(t,J＝3.4Hz,2H),6.36(d,J＝9.6Hz,1H),4.80(s,1H),3.41(m,2H),2.84-2.73(m,2H),1.94(m,2H)；13C NMR(100MHz,CDCl3):δ＝150.6,137.2,126.0,124.2,119.9,112.2,41.8,41.9,26.9,20.9。

Claims (5)

1. a method for selectively catalyzing and hydrogenating aromatic heterocyclic compounds by non-hydrogen is characterized in that: adding 1, 5-cyclooctadiene iridium chloride dimer, phenyl silane and an aromatic heterocyclic compound shown in formula I, formula II or formula III into an organic solvent, stirring and reacting at 40-50 ℃ under a nitrogen atmosphere and a closed condition, separating and purifying a product after the reaction is finished, and correspondingly obtaining a hydrogenated product shown in formula I ', formula II ' or formula III ';
Figure FDA0003089739010000011
in the formula, R, R1、R2Each independent representative H, C1～C4Alkyl radical, C1～C3Any one of alkoxy, phenyl, hydroxyl, carboxyl, ester group, cyano, trifluoromethyl, halogen and nitro; x represents N, Y represents CH, or X represents CH, Y represents N, and M represents CH or N.
2. A process according to claim 1 for the non-hydrogen participation in the selective catalytic hydrogenation of heteroaromatic compounds, characterized in that: r represents any one of H, methyl, isopropyl, phenyl, hydroxyl, ester group, cyano, trifluoromethyl, ethoxy, methoxy, fluorine, chlorine, bromine and nitro, and R represents any one of1、R2Each independently represents any one of H, methyl and phenyl.
3. A process according to claim 1 for the non-hydrogen participation in the selective catalytic hydrogenation of heteroaromatic compounds, characterized in that: the molar ratio of the heteroaromatic compound to the 1, 5-cyclooctadiene iridium chloride dimer and the phenyl silane is 1: 2-3: 35-50.
4. A process according to claim 1 for the non-hydrogen participation in the selective catalytic hydrogenation of heteroaromatic compounds, characterized in that: the organic solvent is methanol or ethanol.
5. A process according to claim 1 for the non-hydrogen participation in the selective catalytic hydrogenation of heteroaromatic compounds, characterized in that: stirring and reacting for 20-30 hours at 40-50 ℃ under the condition of nitrogen atmosphere and sealing.
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