A kind of preparation method of 2,3,4,6-tetrasubstituted pyridine compounds

A ketone compound and compound technology are applied in the field of preparation of 2,3,4,6-tetra-substituted pyridine compounds, which can solve the problems of poor applicability of functional groups of substrates, achieve diverse structures, good application value, and avoid heavy metal pollution. Effect

Active Publication Date: 2022-04-26
TAIZHOU UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0012] The above four types of methods all have the shortcomings of being highly dependent on metal catalysts and poor applicability of substrate functional groups.

Method used

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  • A kind of preparation method of 2,3,4,6-tetrasubstituted pyridine compounds
  • A kind of preparation method of 2,3,4,6-tetrasubstituted pyridine compounds
  • A kind of preparation method of 2,3,4,6-tetrasubstituted pyridine compounds

Examples

Experimental program
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Effect test

Embodiment 1

[0052] Embodiment 1: the preparation of 2,3,4,6-tetraphenylpyridine (Ia)

[0053]

[0054] Acetophenone (1.2g, 10mmol), benzaldehyde (1.06g, 10mmol), diacetophenone (1.96g, 10mmol), ammonium acetate (2.31g, 30mmol) were stirred and reacted at 100°C for 20 hours. After the reaction, add water (15mL) to quench, extract with ethyl acetate (3×8mL), combine the organic phases and dry with anhydrous sodium sulfate, filter and spin the filtrate to dry the solvent under reduced pressure, and quickly separate by silica gel column chromatography The desired 2,3,4,6-tetraphenylpyridine (Ia) was obtained as 3.3 g of white solid, and the yield was 87% based on acetophenone.

[0055] 1 H NMR (400MHz, CDCl 3 )δ8.18-8.15(m,2H),7.78(s,1H),7.49(t,J=7.2Hz,2H),7.44-7.37(m,3H),7.24-7.19(m,6H),7.14 -7.12(m,2H),7.09-7.04(m3H),6.93-6.91(m,2H). 13 C NMR (101MHz, CDCl 3 )δ157.99,154.61,150.64,140.99,139.85,139.10,137.87,132.88,131.44,130.20,129.34,129.01,128.71,127.94,127.72,127.53,127.38,127.3...

Embodiment 2

[0056] Embodiment 2: Preparation of 6-(2-bromophenyl)-2,3,4-triphenylpyridine (Ib)

[0057]

[0058] 2-Bromoacetophenone (1.99g, 10mmol), benzaldehyde (1.06g, 10mmol), diacetophenone (1.96g, 10mmol), ammonium acetate (2.31g, 30mmol) were stirred at 120°C for 19 hours . After the reaction, add water (15mL) to quench, extract with ethyl acetate (3×8mL), combine the organic phases and dry with anhydrous sodium sulfate, filter and spin the filtrate to dry the solvent under reduced pressure, and quickly separate by silica gel column chromatography The desired 6-(2-bromophenyl)-2,3,4-triphenylpyridine (Ib) was obtained as 3.7 g of white solid, and the yield was 81% based on acetophenone.

[0059] 1 H NMR (400MHz, CDCl 3 )δ7.77(dd,J=7.6,1.7Hz,1H),7.73–7.68(m,2H),7.46–7.41(m,1H),7.37–7.31(m,2H),7.28(d,J= 1.7Hz,1H),7.24–7.16(m,6H),7.16–7.12(m,2H),7.12–7.05(m,3H),6.98–6.92(m,2H). 13 C NMR (101MHz, CDCl 3 )δ158.03,156.61,156.58,149.64,140.97,140.70,139.43,137.61,133.45,133.04,13...

Embodiment 3

[0060] Example 3: Preparation of 6-(2-chlorophenyl)-2,3,4-triphenylpyridine (Ic)

[0061]

[0062] 2-Chloroacetophenone (1.54g, 10mmol), benzaldehyde (1.06g, 10mmol), diacetophenone (1.96g, 10mmol), ammonium acetate (2.31g, 30mmol) were stirred and reacted at 110°C for 18 hours . After the reaction, add water (15mL) to quench, extract with ethyl acetate (3×8mL), combine the organic phases and dry with anhydrous sodium sulfate, filter and spin the filtrate to dry the solvent under reduced pressure, and quickly separate by silica gel column chromatography The desired 6-(2-chlorophenyl)-2,3,4-triphenylpyridine (Ic) was obtained as 3.5 g of white solid, and the yield was 83% based on acetophenone.

[0063] 1 H NMR (400MHz, CDCl 3 )δ7.82(dd, J=7.6,1.8Hz,1H),7.74(s,1H),7.50(dd,J=7.8,1.4Hz,1H),7.39(td,J=7.5,1.5Hz,1H ),7.36-7.32(m,3H),7.23–7.16(m,6H),7.15–7.05(m,5H),6.96–6.92(m,2H). 13 C NMR (101MHz, CDCl 3)δ158.15,155.16,149.67,140.72,139.44,138.99,137.61,133.04,132.38,131.9...

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Abstract

The invention discloses a preparation method of a 2,3,4,6-tetrasubstituted pyridine compound, comprising the following steps: making a diaryl ketone compound as shown in formula (II) and a compound as shown in formula (III) Aromatic aldehyde compounds, ketone compounds as shown in formula (IV) and amine source are mixed, carry out multi-component reaction, one-pot method is prepared as shown in formula (I) 2,3,4,6-tetrasubstituted Pyridine compounds; the amine source is ammonium salt, ammonia water, primary amine or hydroxylamine hydrochloride; R 1 and R 2 Both are aryl groups, and the aryl groups are optionally substituted by 1 to 5 substituents; R 3 is aryl or heteroaryl, and said aryl or heteroaryl is optionally substituted by 1 to 5 substituents; R 4 is an aryl group, a heteroaryl group or an aliphatic group, and the aryl group, a heteroaryl group or an aliphatic group is optionally substituted by 1 to 5 substituents. The raw materials of the preparation method provided by the invention are cheap and easy to obtain; the use of metal catalysts is eliminated, and heavy metal pollution in pharmaceutical chemicals is avoided from the source; the substrate has wide applicability and has good application value and potential social and economic benefits.

Description

technical field [0001] The invention belongs to the technical field of synthesis of pharmaceutical and chemical intermediates, and in particular relates to a preparation method of 2,3,4,6-tetrasubstituted pyridine compounds. Background technique [0002] Multi-substituted pyridine compounds are an important class of heterocyclic compounds. In many natural products, functional materials, electrochemistry, pesticides, drugs, organic catalysis and various valuable ligands, the pyridine skeleton often appears as the core structure. Such as rosiglitazone for the treatment of diabetes, the commonly used antihistamine chlorpheniramine, and omeprazole for the treatment of gastric ulcer. Therefore, in modern heterocyclic chemistry, the construction of this framework has been extensively studied, and a large number of highly efficient regioselective syntheses of such compounds have been established, especially transition metal-catalyzed C–H functionalization and cyclization reactions....

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D213/16C07D213/26C07D213/30C07D213/22C07D409/04
CPCC07D213/16C07D213/26C07D213/30C07D213/22C07D409/04
Inventor 马永敏丁雨昕
Owner TAIZHOU UNIV
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