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Method for carrying out reaction on methylenecyclopropane derivative and ether compound C(sp<3>)-H bond

A technology of methylene cyclopropane and ether compounds, which is applied in the field of C-H bond reaction between methylene cyclopropane derivatives and ether compounds, achieving the effect of high atom economy, high yield, high efficiency and environmental protection of the reaction system

Inactive Publication Date: 2017-07-14
HUNAN INSTITUTE OF SCIENCE AND TECHNOLOGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Though also have many reaction ether compounds as reactant, because ether C (sp3)-H bond is a stable inert bond, therefore, participate in the report of reaction with ether C (sp3)-H bond seldom, according to the inventor As known, there is no prior art report of methylcyclopropane derivatives and ether C(sp 3 )-H bond reaction

Method used

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  • Method for carrying out reaction on methylenecyclopropane derivative and ether compound C(sp&lt;3&gt;)-H bond

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Experimental program
Comparison scheme
Effect test

Embodiment 1-16

[0034] Embodiment 1-16 Reaction condition optimization

[0035] Using the compound shown in Formula II-1 and tetrahydrofuran as the reaction raw materials, the influence of various conditions on the reaction (Formula 2) was explored, and representative examples 1-17 were selected. The results are shown in Table 1. Show:

[0036] (Formula 2)

[0037] Wherein the operation of embodiment 1 is as follows:

[0038] Add a magnetic stirrer bar into a 25 mL SCHELNK sealed reaction tube, and add 0.3 mmol (about 70.8 mg) of substrate II-1, then replace the air in the reaction tube with nitrogen for 3-5 times, after Add 2.0 equiv TBHP (tert-butanol peroxide, 5.0 M in decane) (about 0.15 mL) and 2.0 mL tetrahydrofuran under a nitrogen gas flow environment, cover the reaction tube, and place it in an oil bath at 110°C for 24 hours to react. After the reaction was complete, the solvent was evaporated to dryness with a rotary evaporator, and the product was separated and purified with a...

Embodiment 18

[0052] (Formula 3)

[0053] Add a magnetic stirring bar to a 25 mL SCHELNK sealed reaction tube, and put in 0.3 mmol of substrate II-2, then replace the air in the reaction tube with nitrogen, replace it 3-5 times, and then add 2.0 equiv TBHP (tert-butanol peroxide, 5.0 M in decane) (about 0.15 mL) and 2.0 mL tetrahydrofuran, cap the reaction tube, and place it in an oil bath at 110 degrees Celsius to heat for 24 hours. After the reaction was complete, the solvent was evaporated to dryness with a rotary evaporator, and the product was separated and purified with a chromatographic column. The mobile phase was petroleum ether and ethyl acetate, and the ratio was 30:1. Can obtain product 1-2, about 70% of productive rate ( 1 HNMR (400 MHz, CDCl 3 ): 7.42-7.33 (m, 3H), 7.23-7.07 (m, 4H), 7.01 (t, J = 7.2Hz, 1H), 6.57 (d, J = 7.6 Hz, 1H), 4.34 (t, J = 8.0 Hz, 1H), 3.94-3.89 (m,1H), 3.75-3.70 (m, 1H), 2.99-2.81 (m, 2H), 2.61-2.54 (m, 1H), 2.37-2.29 (m,1H ), 1.94-1.64 (m, ...

Embodiment 19

[0055] (Formula 4)

[0056]Add a magnetic stirrer bar into a 25 mL SCHELNK sealed reaction tube, and put in 0.3 mmol of substrate II-3, then replace the air in the reaction tube with nitrogen, replace it 3-5 times, and then add 2.0 equiv TBHP (tert-butanol peroxide, 5.0 M in decane) (about 0.15 mL) and 2.0 mL tetrahydrofuran, cap the reaction tube, and place it in an oil bath at 110 degrees Celsius to heat for 24 hours. After the reaction was complete, the solvent was evaporated to dryness with a rotary evaporator, and the product was separated and purified with a chromatographic column. The mobile phase was petroleum ether and ethyl acetate, and the ratio was 30:1. Product I-3 can be obtained, and the yield is about 68% ( 1 HNMR (400 MHz, CDCl 3 ): 6.84 (s, 1H), 6.72 (s, 1H), 5.94 (s, 2H), 4.46 (t, J =7.2 Hz, 1H), 4.02-3.96 (m, 1H), 3.90-3.84 (m, 1H), 2.77-2.71 (m, 2H), 2.28-2.16 (m, 2H), 2.12-2.05 (m, 1H ), 1.99-1.94 (m, 2H), 1.76-1.70 (m, 1H); 13 C NMR (100 MHz, CDC...

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Abstract

The present invention belongs to the technical field of organic synthesis, and particularly relates to a method for carrying out a reaction on a methylenecyclopropane derivative and an ether compound C(sp<3>)-H bond. According to the present invention, a methylenecyclopropane derivative represented by a formula II and an ether compound represented by a formula III are subjected to a reaction in the presence of a free radical initiator to obtain a 1,2-dihydronaphthalene derivative represented by a formula I, wherein the free radical initiator is the mixture comprising one or a plurality of materials selected from TBHP (tert-butyl hydroperoxide), CHP (Cumyl hydroperoxide), and THAP (tert-amyl hydroperoxide). The formulas I, II and III are defined in the specification.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a methylenylcyclopropane derivative and an ether compound C(sp 3 )-H bond reaction method. Background technique [0002] Methylenecyclopropanes (MCPs) are a three-membered carbocyclic molecular structure with a large angular tension. Its reactivity is very high, so it is often used to synthesize many important ring skeletons in organic synthesis. In recent years, there have been a lot of researches on methylenecyclopropane. Generally, transition metals are used to catalyze ring opening, and most of them focus on the reaction with heteroatoms. [0003] Xian Huang's group has reported a kind of methylene cyclopropane derivatives in Mn(OAc) 3 Or under the promotion of AIBN respectively with ethylene glycol malonate (Prior Art Document 1: J. Org. Chem., 2004, 69, 5471-5472.), methyl-substituted dicarbonyl compounds (Prior Art Document 2: Journal of Organometa...

Claims

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Application Information

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IPC IPC(8): C07D307/12C07D307/06C07D407/04C07C41/30C07C43/168
CPCC07C41/30C07D307/06C07D307/12C07D407/04C07C43/168
Inventor 刘宇
Owner HUNAN INSTITUTE OF SCIENCE AND TECHNOLOGY
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