Preparation method of para-diimide derivative

A technology for secondary diimides and derivatives, which is applied in the field of preparation of secondary diimide derivatives, can solve the problems of reducing the reactivity of nitrogen-hydrogen bonds on amides, large steric hindrance, etc., and achieve saving of reaction steps and operation The effect of simplicity and mild reaction conditions

Inactive Publication Date: 2013-09-25
ZHEJIANG UNIV
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Problems solved by technology

However, the preparation of secondary imides by the intermolecular reaction between aldehydes and open-chain secondary amides has not been reported; this may be due to the greater steric hindrance of the nitrogen on the secondary amide than that of the primary amide, thereby reducing the nitrogen-hydrogen concentration on the amide. bond reactivity

Method used

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  • Preparation method of para-diimide derivative
  • Preparation method of para-diimide derivative
  • Preparation method of para-diimide derivative

Examples

Experimental program
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Effect test

Embodiment 1

[0038] In this example, N-propyl-N-(4-chlorobenzoyl)pyridinecarboxamide 3a was prepared by the carbon-hydrogen functionalization reaction of N-propylpicolinamide and 4-chlorobenzaldehyde.

[0039] A solution of N-propylpicolinamide (0.25mmol), 4-chlorobenzaldehyde (0.5mmol) and bis(triphenylphosphine)palladium acetate (0.025mmol, 10mol%) in acetonitrile (1.0mL) was added at room temperature After stirring for 2 minutes, a decane solution (5.5 M) of tert-butanol peroxide (4.0 mmol) was added dropwise. The reaction mixture was stirred at 120° C. for 24 hours to complete the reaction. Concentrate the mixed solution, use petroleum ether / ethyl acetate=4 / 1 (v / v) mixed solvent as eluent, and through silica gel column chromatography, the desired N-propyl-N-(4-chloro Benzoyl)pyridinecarboxamide 3a in 80% yield.

[0040] The NMR data are as follows: 1 H NMR (300MHz, CDCl 3 ) δ (ppm): 8.30 (d, J = 4.5Hz, 1H), 7.72 (d, J = 7.8Hz, 1H), 7.61 (td, J = 7.5, 1.2Hz, 1H), 7.45 (d, J = 8.7Hz...

Embodiment 2

[0044] This example prepares N-(4-chlorobenzyl)-N-(4-chlorobenzoyl) through the carbon-hydrogen functionalization reaction of N-(4-chlorobenzyl)pyridinecarboxamide and 4-chlorobenzaldehyde Pyridinecarboxamide 3b:

[0045] Toluene (1.0mL ) solution was stirred at room temperature for 2 minutes, and a decane solution (5.5M) of tert-butanol peroxide (4.0 mmol) was added dropwise. The reaction mixture was stirred at 120°C for 19 hours to complete the reaction. Concentrate the mixed solution, use petroleum ether / ethyl acetate=8 / 1 (v / v) mixed solvent as eluent, and use silica gel column chromatography to obtain the desired N-(4-chlorobenzyl)-N -(4-Chlorobenzoyl)picolinamide 3b, 74% yield.

[0046] The NMR data are as follows: 1 H NMR (300MHz, CDCl 3 )δ (ppm): 8.30 (d, J = 4.8Hz, 1H), 7.72 (d, J = 7.8Hz, 1H), 7.59 (td, J = 7.5, 1.2Hz, 1H), 7.48 (d, J = 8.1Hz, 2H), 7.39-7.35(m, 2H), 7.28-7.26(m, 2H), 7.15-7.07(m, 3H), 5.19(s, 2H).

[0047] The mass spectrometry data is as follo...

Embodiment 3

[0050] This example prepares N-(3-methoxypropyl)-N-(4-chloro Benzoyl) pyridinecarboxamide 3c:

[0051] N-(3-methoxypropyl)pyridinecarboxamide (0.50mmol)), 4-chlorobenzaldehyde (1.0mmol) and bis(triphenylphosphine)palladium chloride (0.05mmol, 10mol%) in acetonitrile (2.0 mL) was stirred at room temperature for 2 minutes, and a decane solution (5.5 M) of tert-butanol peroxide (8.0 mmol) was added dropwise. The reaction mixture was stirred at 120° C. for 27 hours to complete the reaction. Concentrate the mixed solution, use petroleum ether / ethyl acetate=3 / 1 (v / v) mixed solvent as eluent, and use silica gel column chromatography to obtain the desired N-(3-methoxypropyl) -N-(4-Chlorobenzoyl)pyridinecarboxamide 3c, yield 78%.

[0052] The NMR data are as follows: 1 H NMR (300MHz, CDCl 3 )δ (ppm): 8.30 (d, J = 4.8Hz, 1H), 7.73 (d, J = 7.8Hz, 1H), 7.62 (td, J = 7.8, 1.5Hz, 1H), 7.47 (d, J = 8.4Hz, 2H), 7.18-7.12(m, 3H), 4.13(t, J=7.2Hz, 2H), 3.51(t, J=6.0Hz, 2H), 3.26(s, 3H), 2...

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Abstract

The invention discloses a preparation method of a para-diimide derivative. N-substituted-2-nicotinamide, aromatic aldehyde, and a palladium catalyst are dissolved in a solvent; tert-butyl hydroperoxide is dropped into the reaction system under a temperature of 10-30 DEG C; the temperature is increased to 110-130 DEG C; the mixture is stirred for 1-100h; and when a reaction is sufficiently carried out, the reaction product is subjected to separation and purification, such that the para-diimide derivative is obtained. The reaction condition of the para-diimide derivative preparation method is neutral, and the method has wide functional group tolerance scope. The operation is simple, and the method has certain potential to be applied in industrialized productions.

Description

technical field [0001] The invention belongs to the field of organic synthesis, in particular to a preparation method of secondary diimide derivatives. Background technique [0002] Secondary imides are a class of imides with substituents attached to the nitrogen. Secondary imide structures widely exist in natural products, and many secondary imide derivatives have important physiological activities (Pacher, T,; Raninger, A.; Lorbeer, E.; Brecker, L.; But, P.P. -H.; Greger, H.J.Nat.Prod.2010, 73, 1389. and Nakamura, H.; Iitaka, Y.; Sakakibara, H.; Umezawa, H.J.Antibiot.1974, 27, 894.); Imides are also important intermediates in organic synthesis, and are widely used in the fields of pesticides, medicines, and materials. However, there are only sporadic reports on the synthesis methods of secondary imides. It has been reported that an open-chain secondary imide derivative can be prepared by reacting a secondary amide with an acid chloride (Sharma, R.N.; Sharma, K.P.; Dikshi...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D213/81
Inventor 黄志真边永军
Owner ZHEJIANG UNIV
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