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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  • 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 wit

Method used

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

Examples

Experimental program
Comparison scheme
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Example Embodiment

[0034] Example 1-16 Optimization of reaction conditions

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

[0036] (Formula 2)

[0037] The operation of embodiment 1 is as follows:

[0038] Add a magnetic stir bar to a 25 mL SCHELNK sealed tube reaction tube, and add 0.3 mmol (about 70.8 mg) of substrate II-1, and then replace the air in the reaction tube with nitrogen. After 3-5 replacements, Add 2.0 equiv TBHP (tert-butanol peroxy, 5.0 M in decane) (approximately 0.15 mL) and 2.0 mL of tetrahydrofuran under a nitrogen atmosphere, cover the reaction tube, and place it in an oil bath at 110°C for 24 hours. After the reaction is complete, use a rotary evaporator to evaporate the solvent, and use a chromatographic column to separate and purify the product. The m...

Example Embodiment

[0051] Example 18

[0052] (Formula 3)

[0053] Add a magnetic stir bar to a 25 mL SCHELNK sealed tube reaction tube, and add 0.3 mmol substrate II-2, and then replace the air in the reaction tube with nitrogen. After replacing it for 3-5 times, add it under nitrogen flow 2.0 equiv TBHP (tert-butanol peroxy, 5.0 M in decane) (approximately 0.15 mL) and 2.0 mL tetrahydrofuran, cover the reaction tube lid, and place it in an oil bath at 110 degrees Celsius for 24 hours. After the reaction is complete, use a rotary evaporator to evaporate the solvent, and use a chromatographic column to separate and purify the product. The mobile phase is petroleum ether and ethyl acetate in a ratio of 30:1. The product I-2 can be obtained with a yield of about 70% ( 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)...

Example Embodiment

[0054] Example 19

[0055] (Formula 4)

[0056] Add a magnetic stir bar to a 25 mL SCHELNK sealed tube reaction tube, and add 0.3 mmol substrate II-3, and then replace the air in the reaction tube with nitrogen. After replacing it for 3-5 times, add it under nitrogen flow 2.0 equiv TBHP (tert-butanol peroxy, 5.0 M in decane) (approximately 0.15 mL) and 2.0 mL tetrahydrofuran, cover the reaction tube lid, and place it in an oil bath at 110 degrees Celsius for 24 hours. After the reaction is complete, use a rotary evaporator to evaporate the solvent, and use a chromatographic column to separate and purify the product. The mobile phase is petroleum ether and ethyl acetate in a ratio of 30:1. The product I-3 can be obtained with a yield of 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 ...

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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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