Method for synthesizing 1,2,3,4-tetrahydropyridine derivatives from chain 1,3-dicarbonyl compound in one-pot method

A technology of dicarbonyl compounds and tetrahydropyridines, applied in the field of synthesis of organic intermediates, achieving high yield, mild conditions, and scientific and reasonable synthesis methods

Inactive Publication Date: 2010-08-04
ZHENGZHOU UNIV
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Problems solved by technology

At present, there is no report on the synthesis of 1,2,3,4-tetrahydropyridine derivatives from chain-like 1,3-dicarbonyl compounds

Method used

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  • Method for synthesizing 1,2,3,4-tetrahydropyridine derivatives from chain 1,3-dicarbonyl compound in one-pot method
  • Method for synthesizing 1,2,3,4-tetrahydropyridine derivatives from chain 1,3-dicarbonyl compound in one-pot method
  • Method for synthesizing 1,2,3,4-tetrahydropyridine derivatives from chain 1,3-dicarbonyl compound in one-pot method

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] Example 1: Synthesis of N-n-propyl-2-methyl-3,5,5-triacetyl-1,2,3,4-tetrahydropyridine:

[0024] At room temperature, add 3 mmol (315 μl) of acetylacetone, 1 mmol (82 μl) of n-propylamine, 2 mmol of formaldehyde (157 μl of 37% aqueous formaldehyde solution) and 1 mL of ethanol as a solvent in a 5 ml small flask, and react with magnetic stirring for 6 hours at room temperature. After the reaction was completed, it was concentrated by a rotary evaporator, and the residue was separated by silica gel thin-layer chromatography using 1:1 petroleum ether / ethyl acetate as a developing solvent. Pure N-n-propyl-2-methyl-3,5,5-triacetyl-1,2,3,4-tetrahydropyridine (purity>98%, red viscous liquid) was obtained. The isolated yield was 74%. The nuclear magnetic analysis data of this compound are as follows:

[0025] 1 H NMR δ=0.74(t, 3H, CH 3 ), 1.44 (m, 2H, CH 2 ), 2.00(s, 6H, 2CH 3 ), 2.05(s, 3H, CH 3 ), 2.17 (s, 3H, CH 3 ), 2.72 (s, 2H, CH 2 ), 3.08(t, 2H, CH 2 ), 3.39 (s...

Embodiment 2

[0027] Example 2: Synthesis of N-isopropyl-2-methyl-3,5,5-triacetyl-1,2,3,4-tetrahydropyridine:

[0028] At room temperature, add 2mmol (210μl) acetylacetone, 1mmol (86μl) isopropylamine, 2mmol formaldehyde (157μl of 37% formaldehyde aqueous solution) to a 5ml small flask, and 2mL of DMF as a solvent, magnetic stirring reaction at room temperature for 4 hours, and 1 : 1 petroleum ether / ethyl acetate as developing solvent, separated by silica gel thin-layer chromatography to obtain pure product N-isopropyl-2-methyl-3,5,5-triacetyl-1,2,3,4 - Tetrahydropyridine (purity > 98%, red viscous liquid). Isolated yield 78%.

[0029] The NMR data of this compound are as follows.

[0030] 1 H NMR δ=1.04(s, 3H, 1CH 3 ), 1.06(s, 3H, 1CH 3 ), 2.03(s, 6H, 2CH 3 ), 2.08(s, 3H, 1CH 3 ), 2.22(s, 3H, 1CH 3 ), 2.75(s, 2H, 1CH 2 ), 3.28(s, 2H, 1CH 2 ), 4.06(m, 1H, 1CH)

[0031] 13 C NMR δ = 16.7, 19.8, 26.2, 30.1, 30.2, 43.8, 48.1, 64.0, 101.7, 155.4, 195.4, 204.2.

Embodiment 3

[0032] Example 3: Synthesis of N-n-propyl-2-methyl-5-acetyl-1,2,3,4-tetrahydropyridine-3,5-dioic acid diethyl ester:

[0033] At room temperature, add 3mmol (381μl) ethyl acetoacetate, 1mmol (82μl) n-propylamine, 2.5mmol formaldehyde (196μl of 37% formaldehyde aqueous solution) and 2mL of methanol as a solvent in a 5ml small flask, and magnetically stir the reaction for 7 hours at room temperature , using 5:1 petroleum ether / ethyl acetate as a developing solvent, separated by silica gel thin layer chromatography to obtain pure product N-n-propyl-2-methyl-5-acetyl-1,2,3,4-tetra Hydropyridine-3,5-dioic acid diethyl ester (purity>98%, yellow viscous liquid). Isolated yield 83%.

[0034] The NMR data of this compound are as follows:

[0035] 1 H NMR δ=0.89(t, 3H, 1CH 3 ), 1.265 (m, 6H, 2CH 3 ), 1.583 (m, 2H, 1CH 2 ,), 2.23(s, 3H, 1CH 3 ), 2.36(s, 3H, 1CH 3 ), 2.92 (m, 2H, 1CH 2 ), 3.21(t, 2H, 1CH 2 ), 3.44(t, 2H, 1CH 2 ), 4.18 (m, 4H, 2CH 2 )

[0036] 13 C NMR δ = 11...

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Abstract

The invention belongs to synthesis of organic intermediates, more particularly relates to a method for synthesizing 1,2,3,4-tetrahydropyridine derivatives from a chain 1,3-dicarbonyl compound in one-pot method. The method comprises the following steps of: adding the chain 1,3-dicarbonyl compound, primary amine and a formaldehyde water solution into a reaction vessel, then adding a solvent and reacting for 4 to 8h, concentrating and purifying after the reaction is finished to obtain the 1,2,3,4-tetrahydropyridine derivatives. The invention provides a synthesis method of the 1,2,3,4-tetrahydropyridine derivatives and has scientific and reasonable synthesis method, mild conditions, simple and easy operation and production yield of up to more than 80 percent.

Description

(1) Technical field [0001] The invention belongs to the synthesis of organic intermediates, in particular to a method for synthesizing 1,2,3,4-tetrahydropyridine derivatives in one pot from a chain 1,3-dicarbonyl compound. (2) Background technology [0002] 1,2,3,4-Tetrahydropyridine derivatives are important intermediates in pharmaceutical, pesticide, chemical and other industries. They can also be used to synthesize amides, carboxylic acids, carboxylic acid esters, imidazoles, etc. by changing ester groups and carbonyl groups. The field is very broad. At present, there is no report on the synthesis of 1,2,3,4-tetrahydropyridine derivatives from chain-like 1,3-dicarbonyl compounds. (3) Contents of the invention [0003] The object of the present invention is to provide a method for synthesizing 1,2,3,4-tetrahydropyridine derivatives from chain 1,3-dicarbonyl compounds in one pot, which has reasonable synthesis route, mild conditions and high yield. [0004] The technica...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D211/02C07D211/70C07D211/78
Inventor 段征赵伟宁杨付来
Owner ZHENGZHOU UNIV
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