Method for efficiently synthesizing alpha, beta-unsaturated aldehyde without synthesis gas

A synthetic method, unsaturated technology

Active Publication Date: 2020-10-27
SICHUAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Despite the fruitful results in related fields, two important factors seriously hinder the further application of hydroformylation reactions: First, although syngas (CO:H 2 =1:1) It is cheap and abundant, but it is highly toxic, flammable and explosive, and the reaction process requires relatively high-pressure synthesis gas, so special equipment is required to accommodate high-pressure synthesis gas; in addition, compared to the hydroformylation of olefins reaction, the hydroformylation reaction of alkynes is more challenging, the regioselectivity of the reaction is difficult to control, and the side reaction products, such as the hydrogenation products of al

Method used

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  • Method for efficiently synthesizing alpha, beta-unsaturated aldehyde without synthesis gas
  • Method for efficiently synthesizing alpha, beta-unsaturated aldehyde without synthesis gas
  • Method for efficiently synthesizing alpha, beta-unsaturated aldehyde without synthesis gas

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032] Embodiment 1: the synthesis of (E)-2-heptyldec-2-enal

[0033] (1) Under nitrogen protection, hexadecane-8-yne (0.4mmol, 88.8mg), n-butyraldehyde (0.2mmol, 18μL), cyclopentadienemethoxyrhodium dimer (4μmol, 1.9mg ), 4,5-bisdiphenylphosphine-9,9-dimethylxanthene (8 μmol, 4.6 mg) and 4-nitrobenzoic acid (8 μmol, 1.3 mg) were added to the reaction equipped with a magnetic stir bar In the tube, tetrahydrofuran (100 μL) was added under nitrogen, and reacted at 80°C for 24 hours.

[0034] (2) After the reaction is completed, the reaction tube is cooled to room temperature, dichloromethane is added to dilute the reaction system, then filtered through diatomaceous earth, and washed with dichloromethane, the filtrates are combined, the solvent is removed under reduced pressure, and the residue is purified by silica gel column layer Analysis (petroleum ether / ethyl acetate=200:1, v / v) gave yellow oily liquid (E)-2-heptyldec-2-enal with a mass of 43 mg and a yield of 86%. 1 H NMR...

Embodiment 2

[0035] Embodiment 2: the synthesis of (E)-2-hexyl non-2-enal

[0036] (1) Under nitrogen protection, tetradecane-7-yne (0.4mmol, 77.6mg), n-butyraldehyde (0.2mmol, 18μL), cyclopentadiene methoxyrhodium dimer (4μmol, 1.9mg ), 4,5-bisdiphenylphosphine-9,9-dimethylxanthene (8 μmol, 4.6 mg) and 4-nitrobenzoic acid (8 μmol, 1.3 mg) were added to the reaction equipped with a magnetic stir bar In the tube, tetrahydrofuran (100 μL) was added under nitrogen, and reacted at 80°C for 24 hours.

[0037] (2) After the reaction is completed, the reaction tube is cooled to room temperature, dichloromethane is added to dilute the reaction system, then filtered through diatomaceous earth, and washed with dichloromethane, the filtrates are combined, the solvent is removed under reduced pressure, and the residue is purified by silica gel column layer Analysis (petroleum ether / ethyl acetate=200:1, v / v) gave yellow oily liquid (E)-2-hexylnon-2-enal with a mass of 40 mg and a yield of 90%. 1 H NM...

Embodiment 3

[0038] Embodiment 3: the synthesis of (E)-2-butyl hept-2-enal

[0039] (1) Under nitrogen protection, hept-2-yne (0.4mmol, 55.4mg), n-butyraldehyde (0.2mmol, 18μL), cyclopentadienemethoxyrhodium dimer (4μmol, 1.9mg), 4,5-bisdiphenylphosphine-9,9-dimethylxanthene (8 μmol, 4.6 mg) and 4-nitrobenzoic acid (8 μmol, 1.3 mg) were added to a reaction tube equipped with a magnetic stir bar , THF (100 μL) was added under nitrogen, and reacted at 80° C. for 24 hours.

[0040] (2) After the reaction is completed, the reaction tube is cooled to room temperature, dichloromethane is added to dilute the reaction system, then filtered through diatomaceous earth, and washed with dichloromethane, the filtrates are combined, the solvent is removed under reduced pressure, and the residue is purified by silica gel column layer Analysis (petroleum ether / ethyl acetate=200:1, v / v) gave yellow oily liquid (E)-2-butylhept-2-enal with a mass of 29 mg and a yield of 86%. 1 H NMR (400MHz, CDCl 3 ):δ=0....

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Abstract

The invention relates to a method for efficiently synthesizing alpha, beta-unsaturated aldehyde. A series of alkynes can be efficiently and rapidly converted into alpha, beta-unsaturated aldehydes through a hydroformyl transfer reaction between simple alkyl aldehydes and alkynes by using cheap and easily available n-butyraldehyde as a donor of hydroformyl. Compared with a traditional hydroformylation reaction system, the method does not need to use flammable and combustible synthesis gas, does not need to use a special device to contain the synthesis gas, adopts commercially available catalysts and ligands, is simple and convenient to operate, mild in condition and low in cost, and thoroughly inhibits side reaction products such as saturated aldehyde and alkyne hydrogenation products; andthe compound has specific chemoselectivity and excellent regioselectivity and stereoselectivity, and has huge application potential.

Description

technical field [0001] The invention relates to a method for efficiently synthesizing α, β-unsaturated aldehydes without synthesis gas. Background technique [0002] α,β-unsaturated aldehydes are an important class of synthetic intermediates in the field of organic synthesis, often used in the synthesis of pesticides, pharmaceuticals, bioactive molecules and fine chemicals [see: (a) E.F.Glorius in Science of Synthesis, Vol. 25 (Ed.: R. Bruckner), Georg Thieme, Stuttgart, 2007, p.733; (b) D. J. Rowe, Perfum. Flavor. 2000, 25, 1.]. [0003] Among the many methods for synthesizing α,β-unsaturated aldehydes, the hydroformylation reaction of alkynes is considered to be one of the most efficient and rapid synthetic strategies for the construction of unsaturated aldehydes, and has received great attention from synthetic chemists. In the past few decades, a series of catalytic systems for the synthesis of α,β-unsaturated aldehydes by alkyne hydroformylation have been reported, amon...

Claims

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Application Information

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IPC IPC(8): C07C45/69C07C47/21
CPCC07B2200/09C07C45/69C07C47/21
Inventor 游劲松谭光映吴祎民师洋兰静波高戈杨宇东
Owner SICHUAN UNIV
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