Preparation method of 4,4',4''-tritert-butyl-2,2':6',2''-terpyridine

A technology of tert-butyl pyridine and tributyl tin alkyl pyridine, which is applied in the field of organic synthesis, can solve the problems of low synthesis yield, difficult product separation and purification, use of high-risk reagents, etc., and achieves the effect of simple separation and purification

Inactive Publication Date: 2020-09-11
南京合巨药业有限公司
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Problems solved by technology

[0011] The purpose of the present invention is to provide a method for fast and efficient preparation of 4,4',4''-tri-tert-butyl-2,2':6',2''-terpyridine, which solves the problem of the synthetic yield of existing methods Low, difficult product separation and purification and use of high-risk reagents and other issues

Method used

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  • Preparation method of 4,4',4''-tritert-butyl-2,2':6',2''-terpyridine
  • Preparation method of 4,4',4''-tritert-butyl-2,2':6',2''-terpyridine
  • Preparation method of 4,4',4''-tritert-butyl-2,2':6',2''-terpyridine

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Experimental program
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Effect test

Embodiment 1

[0033] Synthesis of Compound IV:

[0034]

[0035] Under the protection of nitrogen, N,N-dimethylethanolamine (131.5 g, 1.48 mol, 2.0 equiv.) was added into 2.5 L of n-hexane, and the temperature was lowered to -20°C. Add n-butyllithium (2.5 M in hexanes, 1.18 L, 2.96 mol, 4.0 equiv.), react at -30°C for 30 minutes, and then add 4-tert-butylpyridine (100.0 g, 0.74 mol, 1.0 equiv. ), react at -20°C for 1 hour after the dropwise addition is completed. Cool the above reaction solution to -70°C, add tributyltin chloride (481.7 g, 1.48 mol, 2.0 equiv.) dropwise, react at -70°C for 2 hours after the dropwise addition, naturally rise to room temperature, and detect the reaction by TLC Finish. The reaction solution was added with 1.0 L of ice water, extracted with ethyl acetate (500 mL), washed with water, column chromatography, and quickly rinsed with petroleum ether to obtain 210.97 g of a colorless liquid, yield: 67.2%, purity 85%.

[0036] 1 H NMR (400 MHz, CDCl 3 ) δ (ppm...

Embodiment 2

[0039] Synthesis of Compound IV:

[0040]

[0041] Under nitrogen protection, N,N-dimethylethanolamine (44.57 g, 0.50 mol, 2.0 equiv.) was added to 1.0 L of n-heptane, and the temperature was lowered to -20°C. Add sec-butyllithium (1.3 M in hexanes, 0.77 L, 1.0 mol, 4.0 equiv.), react at -30°C for 30 minutes, and then add 4-tert-butylpyridine (33.80 g, 0.25 mol, 1.0 equiv. ), react at -20°C for 1 hour after the dropwise addition is completed. Cool the above reaction solution to -70°C, add tributyltin chloride (97.65 g, 0.30 mol, 1.2 equiv.) dropwise, react at -70°C for 2 hours after the dropwise addition, naturally rise to room temperature, and detect the reaction by TLC Finish. The reaction solution was added to 500 mL of ice water, extracted with ethyl acetate (500 mL), washed with water, column chromatography, and quickly eluted with petroleum ether to obtain 40.83 g of a colorless liquid, yield: 38.5 %.

Embodiment 3

[0043] Synthesis of compound I:

[0044]

[0045]Under nitrogen protection, 4-tert-butyl-2-tributylstannylpyridine (IV, 50.00 g, 0.118 mol, 2.0 equiv., theoretical) prepared in Example 1, 4-tert-butyl-2,6-di Chloropyridine (V, 13.24 g, 0.065 mol, 1.1 equiv.), Pd(dppf)Cl 2 (2.16 g, 3.0 mmol, 5 mol%) was added into 100 mL of toluene, heated to 100°C for 16 hours, and the TLC reaction was complete. The reaction solution was concentrated under reduced pressure, made into sand, and column chromatography (washed with DCM) to obtain 17.06 g of a white solid with a yield of 72.0% and a purity of 97%.

[0046] 1 H NMR (400 MHz, CDCl3) δ (ppm): 8.74 (d, J = 1.96 Hz, 2H), 8.63 (d, J = 5.2Hz, 2H), 8.48 (s, 2H), 7.34 (dd, J = 5.2, 2.0 Hz, 2H), 1.47 (s, 9H), 1.44 (s, 18H).

[0047] LC-MS (ESI+): m / z 423.95 (M+Na).

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Abstract

The invention relates to a preparation method of 4,4',4''-tritert-butyl-2,2':6',2''-terpyridine, which comprises the following steps: dissolving an additive in a solvent, and carrying out a reaction with 4-tert-butylpyridine and a tin reagent under strong alkali conditions to obtain 4-tert-butyl-2-tributyltin alkyl pyridine; then carrying out a coupling reaction with 4-tert-butyl-2,6-dichloropyridine under the effect of a catalyst to obtain 4,4',4''-tritert-butyl-2,2':6',2''-terpyridine. Beginning from the raw material 4-tert-butylpyridine, the product 4,4',4''-tritert-butyl-2,2':6',2''-terpyridine is prepared through two reaction steps. The method is simple in product separation and purification and is suitable for large-scale production.

Description

technical field [0001] The invention relates to a preparation method of 4,4',4''-tri-tert-butyl-2,2':6',2''-terpyridine, which belongs to the field of organic synthesis. Background technique [0002] 4,4',4''-tri-tert-butyl-2,2':6',2''-terpyridine (I) as a ligand, is widely used in the synthesis of a series of transition metal complexes, in catalytic chemistry , supramolecular chemistry, material chemistry, electrochemistry, anti-tumor drug development and other fields are widely used. For example, the document J.Am.Chem.Soc.2003,125,16202-16203 reported that the silver ion complex of I was used to catalyze the aziridine reaction; J.Am.Chem.Soc.2002,124,11215- 11222 reported the cobalt ion complex of I as an efficient electron transfer material in dye-sensitized solar cells; Polyhedron, 2018, 140, 99-108 reported the iron and cobalt ion complexes of I for redox flow batteries The galvanic couple material; WO2019241873A1 reported that the copper ion complex of I can induce ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D213/22
CPCC07D213/22
Inventor 柏钊潘国骏
Owner 南京合巨药业有限公司
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