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Photochemical synthesis method of 1, 4-dicarbonyl compound derivative

A technology of dicarbonyl compound and synthesis method, which is applied in the field of organic synthetic chemistry, can solve problems such as atom economy and environmental pollution, and achieve the effects of simple operation, high reactivity and mild conditions

Pending Publication Date: 2022-01-18
NANJING UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0015] These methods usually require an equivalent or excess amount of base, which leads to atomic economy problems, and produces a large amount of metal salt waste, which seriously pollutes the environment.

Method used

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  • Photochemical synthesis method of 1, 4-dicarbonyl compound derivative
  • Photochemical synthesis method of 1, 4-dicarbonyl compound derivative
  • Photochemical synthesis method of 1, 4-dicarbonyl compound derivative

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0038] Example 1: Benzyl 4-oxoheptanoate

[0039]

[0040] Benzyl acrylate (64.8mg, 0.4mmol), di-n-butylamine (12.9mg, 0.1mmol), 2,4,5,6 tetrakis(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.2mg , 2mol%), and toluene:water=3:1 (4mL) were sequentially added to a 25mL reaction tube, the reaction tube was sealed, and under blue light irradiation, reacted at 80°C for 12h, cooled to room temperature, and diluted with 20mL ethyl acetate, After extraction, the obtained organic phase was dried with anhydrous magnesium sulfate, and the solvent was removed by a rotary evaporator to obtain a crude product; the target compound was separated and purified by silica gel column chromatography to obtain 17.8 mg of a yellow liquid with a yield of 76%.

[0041] 1 H NMR (500MHz, CDCl 3 )δ7.35(qd, J=7.0,2.4Hz,5H),5.12(s,2H),2.73(t,J=6.2Hz,2H),2.65(t,J=6.2Hz,2H),2.42( t, J=7.4Hz, 2H), 1.62(h, J=7.4Hz, 2H), 0.91(t, J=7.4Hz, 3H).

[0042] 13 C NMR (126MHz, CDCl 3 )δ209.0, 172.7, 135.9, 128.6,...

Embodiment 2

[0043] Example 2: 4-Methylbenzyl 4-oxoheptanoate

[0044]

[0045] Benzyl p-methacrylate (70.5 mg, 0.4 mmol), di-n-butylamine (12.9 mg, 0.1 mmol), 2,4,5,6 tetrakis(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.2mg, 2mol%), and toluene: water = 3:1 (4mL) were sequentially added to a 25mL reaction tube, the reaction tube was sealed, and reacted at 80°C for 12h under blue light irradiation, cooled to room temperature, and 20mL of ethyl acetate was added Ester was diluted and extracted, and the obtained organic phase was dried with anhydrous magnesium sulfate, and the solvent was removed by a rotary evaporator to obtain a crude product; the target compound was separated and purified by silica gel column chromatography to obtain 16.6 mg of a yellow liquid with a yield of 67%.

[0046] 1 H NMR (500MHz, CDCl 3 )δ7.33–7.27(m,2H),7.22(d,J=7.8Hz,2H),5.12(s,2H),2.77(t,J=6.5Hz,2H),2.68(t,J=6.4 Hz, 2H), 2.47(t, J=7.4Hz, 2H), 2.40(s, 3H), 1.66(dt, J=14.7, 7.4Hz, 2H), 0.96(t, J=7.4Hz, 3H...

Embodiment 3

[0048] Example 3: 4-Methoxybenzyl 4-oxoheptanoate

[0049]

[0050]Benzyl p-methoxyacrylate (64.8mg, 0.4mmol), di-n-butylamine (12.9mg, 0.1mmol), 2,4,5,6 tetrakis(9-carbazolyl)-isophthalonitrile (4CzIPN ) (3.2mg, 2mol%), and toluene: water = 3:1 (4mL) were sequentially added to a 25mL reaction tube, the reaction tube was sealed, and reacted at 80°C for 12h under blue light irradiation, cooled to room temperature, and 20mL of acetic acid was added Diluted with ethyl ester, extracted, dried the obtained organic phase with anhydrous magnesium sulfate, and removed the solvent with a rotary evaporator to obtain a crude product; separated and purified by silica gel column chromatography to obtain 18.4 mg of the target compound as a yellow liquid, with a yield of 68%.

[0051] 1 H NMR (500MHz, CDCl 3 )δ7.33–7.27(m,2H),7.22(d,J=7.8Hz,2H),5.12(s,2H),2.77(t,J=6.5Hz,2H),2.68(t,J=6.4 Hz, 2H), 2.47(t, J=7.4Hz, 2H), 2.40(s, 3H), 1.66(dt, J=14.7, 7.4Hz, 2H), 0.96(t, J=7.4Hz, 3H).

[0...

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Abstract

The invention belongs to the field of organic synthesis, and discloses a photochemical synthesis method of a 1, 4-dicarbonyl compound derivative. The method comprises the following steps: taking an acrylate compound and an amine compound as raw materials, taking 2, 4, 5, 6-tetra (9-carbazolyl)-isophthalonitrile (4CzIPN) as a catalyst, reacting at 80 DEG C under the irradiation of blue light, and taking air as an oxidant to synthesize the 1, 4-dicarbonyl compound derivative. According to the invention, cheap and easily available acrylic ester and amine compounds are used as raw materials, air is used as an oxidant, the reaction is carried out under the photocatalytic condition, the reaction condition is mild, the product selectivity and yield are high, and the method has a wide development prospect.

Description

technical field [0001] The invention relates to a photochemical synthesis method of 1,4-dicarbonyl compound derivatives, belonging to the technical field of organic synthesis chemistry. Background technique [0002] 1,4-dicarbonyl compounds are common intermediates in organic synthesis, and are often used to prepare five-membered heterocyclic furans, thiophenes, pyrroles and cyclopentenones. These structural units are widely found in natural products and drug molecules. For example, Herquline A and Amphidinolide F, among them, Herquline A is a metabolite of fungus, it can inhibit the aggregation of platelets, and has antiviral effect; while Amphidinolide F is isolated from marine organisms, it has the effect of reducing cytotoxicity effect. In addition, Bevirimat is a class of anti-HIV drugs that have shown good clinical activity. [0003] [0004] Synthetic 1,4-dicarbonyl compounds so far mainly include: [0005] 1. Stetter reaction synthesis of aldehydes and α, β-uns...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C67/347C07C67/313C07C69/716C07C231/12C07C235/74C07C69/738
CPCC07C67/347C07C67/313C07C231/12C07C69/716C07C69/738C07C235/74
Inventor 李斌栋张谦侯静詹乐武黄燕征明
Owner NANJING UNIV OF SCI & TECH