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Preparation method of cyclopropane compounds

A cyclopropanation and compound technology, which is applied in the field of preparation of cyclopropane compounds, can solve problems such as being not suitable for acid-sensitive compounds, and achieve the effects of large industrialization potential, high yield and wide application range

Inactive Publication Date: 2013-07-10
INST OF CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

In addition, the use of a large amount of acid makes the system more acidic, making this method less suitable for acid-sensitive compounds

Method used

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  • Preparation method of cyclopropane compounds
  • Preparation method of cyclopropane compounds
  • Preparation method of cyclopropane compounds

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] Example 1. Synthesis of trans 1-methyl-2-phenylcyclopropane (see structural formula Ⅰ-a)

[0023]

[0024] Under nitrogen at room temperature, freshly distilled dichloromethane (2.0 mL) was added to the schlenk tube, followed by diethylzinc solution (2.0 mL, 2.0 mmol) (1.0 M in hexane). After cooling at -40°C for 5 min, a solution of diiodomethane (1.080 g, 4.0 mmol) in dichloromethane (1.0 mL) was added dropwise to the schlenk tube. After reacting at -40°C for 1h, a solution of trichloroacetic acid (0.0326g, 0.20mmol) and DME (0.090g, 1.0mmol) in dichloromethane (1.0mL) was added to the reaction solution, and the reaction temperature rose to -15°C and stirred at this temperature for 1 h. At -15°C, a solution of olefin (formula II-a) (0.121 g, 1.0 mmol) in dichloromethane (1.0 mL) was added dropwise to the reaction solution. The schlenk tube was then transferred to an oil bath at 25°C for 18h, quenched with 0.1N HCl (10mL), diluted with water (10mL), CH 2 Cl 2 (1...

Embodiment 2

[0026] Example 2. Synthesis of trans (2-phenylcyclopropanyl)-methanol (Formula Ⅰ-b)

[0027]

[0028] Under nitrogen at room temperature, freshly distilled dichloromethane (1.0 mL) was added to the schlenk tube, followed by diethylzinc solution (1.0 mL, 1.0 mmol) (1.0 M in hexane). After cooling at -40°C for 5 min, a solution of diiodomethane (0.540 g, 2.0 mmol) in dichloromethane (0.5 mL) was added dropwise to the schlenk tube. After reacting at -40°C for 1h, a solution of trichloroacetic acid (0.0163g, 0.10mmol) and DME (0.045g, 0.5mmol) in dichloromethane (0.5mL) was added to the reaction solution, and the reaction temperature rose to -15°C and stirred at this temperature for 1 h. At -15°C, a solution of alkene (Formula II-b) (0.069g, 0.5mmol) in dichloromethane (0.5mL) was added dropwise to the reaction solution. Then the schlenk tube was transferred to an oil bath at 25°C for 2 h, and saturated NaHCO 3 solution (5mL) to quench the reaction, stirred at room temperatu...

Embodiment 3

[0030] Example 3. Synthesis of trans 1-[(tert-butyldimethylsilyloxy)methyl]-2-phenylcyclopropane (Formula I-c)

[0031]

[0032]Under nitrogen at room temperature, freshly distilled dichloromethane (1.0 mL) was added to the schlenk tube, followed by diethylzinc solution (1.0 mL, 1.0 mmol) (1.0 M in hexane). After cooling at -40°C for 5 min, a solution of diiodomethane (0.540 g, 2.0 mmol) in dichloromethane (0.5 mL) was added dropwise to the schlenk tube. After reacting at -40°C for 1h, a solution of trichloroacetic acid (0.0163g, 0.10mmol) and DME (0.045g, 0.5mmol) in dichloromethane (0.5mL) was added to the reaction solution, and the reaction temperature rose to -15°C and stirred at this temperature for 1 h. At -15°C, a solution of alkene (Formula II-c) (0.124 g, 0.5 mmol) in dichloromethane (0.5 mL) was added dropwise to the reaction solution. Then the schlenk tube was transferred to an oil bath at 25°C for 18 h, saturated with NH 4 Cl (10 mL) quenched the reaction, CH...

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Abstract

The invention discloses a preparation method of cyclopropane compounds. The structural formula of the cyclopropane compounds is shown in a formula I. According to the preparation method, olefins shown as a formula II have cyclopropanation reaction under the actions of a methylene transfer agent and an additive to generate cyclopropane compounds shown as the formula I, wherein the methylene transfer agent is a mixture of diethylzinc and diiodomethane, and the additive is a mixture of acid and ether. According to the preparation method provided by the invention, olefins with different structures are taken as substrates, and the mixture of diethylzinc solution and diiodomethane is taken as the methylene agent, so that the cyclopropane compounds are finally obtained with high yield under the synergistic effect of catalytic amount of trichloroacetic acid and equivalent amount of 1, 2-dimethoxyethane. The preparation method is mild and safe in reaction conditions, easy for large-scale operation, wide in the using range of the substrates and high in yield and has great industrialization potential.

Description

technical field [0001] The invention relates to a preparation method of cyclopropane compounds. Background technique [0002] Due to the special physical and chemical properties of cyclopropane compounds, cyclopropane compounds have important application value in the fields of medicine and agriculture. Many active pharmaceutical molecules are cyclopropane compounds or derived from cyclopropane compounds. In organic chemistry, cyclopropane compounds can be used as important intermediates. [0003] At present, the methods for preparing cyclopropane compounds in organic synthesis mainly include metal-catalyzed cycloaddition, intramolecular substitution reaction, rearrangement reaction and Simmons-Smith cyclopropanation reaction. Among them, the Simmons-Smith cyclopropanation reaction is a very effective method for olefin cyclopropanation, and the efficiency of the cyclopropanation reaction can be greatly improved by adding an acid or alcohol, such as trifluoroacetic acid, into...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C13/28C07C2/86
Inventor 史一安程东浩黄德顺
Owner INST OF CHEM CHINESE ACAD OF SCI
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