Method for preparing corresponding pyridine compound with 1,4-dihydropyridine compound

A technology of dihydropyridine and compounds, which is applied in the field of preparation of pyridine compounds, can solve the problems of low atom utilization, low efficiency, large pollutants, etc., achieve high practical production significance and industrial application value, simple photosensitive oxidation operation, The effect of reducing environmental pollution

Inactive Publication Date: 2017-04-19
LANZHOU UNIVERSITY
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Problems solved by technology

These methods are generally inefficient and basically require heating
In addition, the equivalent amount of oxidant used in the reaction residue not only causes no change to the separation, but also causes a load on the environment.
Due to the cumbersome processing procedures of the reported schemes, the low utilization rate of atoms, and the large pollutants produced, they no longer meet the requirements of an economic model based on low energy consumption, low pollution, and low emissions. Therefore, the development of more efficient and greener photosensitive Oxidative aromatization methods are urgently needed

Method used

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  • Method for preparing corresponding pyridine compound with 1,4-dihydropyridine compound
  • Method for preparing corresponding pyridine compound with 1,4-dihydropyridine compound
  • Method for preparing corresponding pyridine compound with 1,4-dihydropyridine compound

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0019] Embodiment 1 Preparation of compound 1 as shown in formula 18

[0020]

[0021] Take a reaction test tube, add 34.6 mg Nifedipine (Nifedipine) 2,6-dimethyl-4-o-nitrophenyl-1,4-dihydropyridine-3,5-dicarbonate methyl ester, 1.13 mg of tetra-n-butylammonium salt TBA-eosinY of organic photosensitizer Eosin Y, 27.6 mg of potassium carbonate, 5.5 mL of mixed solvent of water and ethanol (ethanol and water are composed at a volume ratio of 10:1), at room temperature After reacting for 12 hours, spin-drying under vacuum, and passing through the column with petroleum ether and acetone, the yield of brownish-yellow oily liquid was 73.3%.

[0022] 1 H NMR: (400MHz, CDCl 3 )δ = 7.74-7.70 (m, 1H), 7.54-7.51 (m, 1H), 7.47-7.43 (m, 1H), 6.56 (d, J=8.0Hz, 1H), 3.39 (s, 6H), 2.68 (s, 6H) ppm. 13 C NMR: (400 MHz, CDCl 3 ):δ =167.3, 161.5, 156.2, 135.1, 130.9, 130.5, 129.0, 128.8,127.6, 65.6, 52.1, 29.7, 23.1, 19.2, 14.0 ppm. MS(70eV): m / z(%) : 3084.1( )[M + ], HRMS m / z (ESI) ca...

Embodiment 2

[0023] Embodiment 2 Preparation of compound 2 as shown in formula 19

[0024]

[0025] Take a reaction test tube, add 38.3 mg Felodipine (Felodipine) 4-(2,3-dichlorophenyl)-2,6-dimethyl-1,4-dihydropyridine-3-ethyl carbonate Ester-5-methyl carbonate, 1.13 mg of tetra-n-butylammonium salt TBA-eosinY of organic photosensitizer eosin Y, 27.6 mg of potassium carbonate, 5.5 mL of mixed solvent of water and ethanol (ethanol and water in a ratio of 10:1 volume ratio composition), reacted at room temperature for 12 hours, spin-dried in vacuum, and passed through the column with petroleum ether and acetone to obtain a light yellow oily liquid with a yield of 83.1%.

[0026] 1 H NMR: (400MHz, CDCl 3 ) δ =7.48 (dd, J = 6.8, 1.2Hz, 1H), 7.24-7.20 (t, J = 8.0Hz, 1H), 7.07 (dd, J = 6.0, 1.6Hz, 1H), 4.06-4.00 (m, 2H), 3.56 (s,3H), 2.66 (d, J = 5.6Hz, 6H), 0.97-0.93 (t, J = 7.2Hz, 3H) ppm. 13 C NMR: (400MHz, CDCl 3): δ =167.3, 166.7, 156.9, 156.7, 144.2, 137.7, 133.1, 131.5,130....

Embodiment 3

[0027] Preparation of compound 3 as shown in formula 20 in embodiment 3

[0028]

[0029] Take a reaction test tube, add 8 mg Nimodipine (Nimodipine) 2,6-dimethyl-4-m-nitrophenyl-1,4-dihydropyridine-3-isopropyl carbonate-5- 2-methoxyethyl carbonate, 0.2 mg tetra-n-butylammonium salt TBA-eosinY of organic photosensitizer eosin Y, 15.7 μL of 1,8-diazabicycloundec-7-ene, 2 mL of benzotrifluoride was reacted at room temperature for 12 hours, spin-dried in vacuo, and passed through the column with petroleum ether and acetone to obtain a colorless liquid with a yield of 78.4%.

[0030] 1 H NMR: (400MHz, CDCl 3 ) δ = 8.28-8.25 (m, 1H), 8.20-8.19(t, J = 1.6Hz,1H), 7.64-7.56 (m, 2H), 5.00-4.90 (m, 1H), 4.13 (s, 2H), 3.35 (s, 2H), 3.24(s, 3H), 2.65(d, J = 6.4Hz, 6H), 1.02(d, J = 6.4Hz, 6H) ppm. 13 C NMR: (400MHz, CDCl 3 ): δ=167.0, 166.5, 156.0, 155.9, 147.9, 137.9, 134.4, 129.2, 127.1, 123.5, 123.4, 69.8, 69.7, 64.4, 58.7, 22.9, 22.8, 21:3 ppm (MS) %): 416.1(584) [M + ], ...

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Abstract

The invention discloses a method for preparing a corresponding pyridine compound from a 1,4-dihydropyridine compound. The method comprises the following steps: adding a 1,4-dihydropyridine compound, tetra-n-butyl ammonium salt of eosin Y and potassium carbonate into an organic solvent-water mixed solvent, evenly mixing, and introducing air to react under the irradiation of visible light; and after the reaction finishes, adding ethyl acetate, washing respectively with water and saturated ammonium chloride, removing the inorganic alkali, regulating the system to a slightly acidic state, adding a small amount of activated carbon into the organic phase to remove the pigment, drying with anhydrous sodium sulfate, carrying out centrifugal drying, and recrystallizing to obtain the corresponding pyridine compound. Compared with the prior art, the method disclosed by the method uses oxygen in air, which is cheap, convenient and accessible, as the oxidizer. By using sunlight as the energy, the method is more beneficial to industrial production. By using the catalytic amount of non-metal photocatalyst, the method lowers the synthesis cost and prevents the noble metals from accumulation in drug synthesis.

Description

technical field [0001] The invention relates to a preparation method of a pyridine compound, specifically, the invention relates to a method of preparing a corresponding pyridine compound from a 1,4-dihydropyridine compound. Background technique [0002] 1,4-Dihydropyridine is a class of calcium channel blockers (Calcium Antagonists), commonly known as "dipine" drugs, is a very important class of compounds in the treatment of hypertension, the mechanism of action is by blocking the myocardial and vascular smooth muscle cell membrane It inhibits the influx of extracellular calcium ions, reduces the level of intracellular calcium ions and causes functional changes in cardiovascular and other tissues and organs. It was first researched in the 1960s and developed into a new type of drug in the 1970s. Its therapeutic range includes hypertension, cardiovascular disease, cerebrovascular disease, and peripheral vascular disease. Endocrine diseases, etc. In organisms, the aromatiza...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D211/90C07D401/12C07D413/12C07D311/82
CPCC07D213/80C07D213/803C07D401/12C07D413/12
Inventor 刘强王遴杜少甫
Owner LANZHOU UNIVERSITY
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