Alkyl chloride substitution method for participation of CH2Cl2 in C-H bond activation
By using the method of participating in CH2CL2 at room temperature, combined with the reaction system for the reaction system of glycol potassium and dichloromethane and dichlori, the selective activation and alkyl chloride replacement reaction of the C-H key can be achieved. The problem of selective transformation realizes the reaction of alkyl chloride replacement under high efficiency, selective and mild conditions.
Patent Information
- Application Number
- CN202411942317.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-27
- Publication Date
- 2025-01-28
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
The stability and similarity of the C-H bond makes its activation and selective conversion a difficult point in organic chemistry, especially when achieving an alkyl chloride substitution reaction under efficient, selective and mild conditions.
By using CH2CL2 to participate at room temperature, combine the reaction system of glycol potassium and dichloromethane and dichlorolytic ash, to achieve the selective activation of the C-H key and alkyl chloride replacement reactions.
This method can efficiently and selectively transform the C (SP3) -H bonds with different structures with different structures as the corresponding C-alkyl chloride replacement product. The operation is easy to promote.
Smart Images
Figure CN119371281A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of organic chemistry, and in particular to a method for substitution of alkyl chlorides by CH2Cl2 with CH bond activation. Background Art
[0002] C-H bond activation is a key step in achieving efficient, highly selective and mild transformations between organic compounds, and is also an important part of green chemistry. The production of high value-added chemicals such as alcohols, alkenes, alkynes, and carboxylic acids through C-H bond activation is of great significance to the modern chemical industry. However, C-H bonds have high bond energy, and the electronegativity of carbon atoms and hydrogen atoms is similar, so C-H bonds are stable and strong with low polarity, and chemical reactions are usually difficult to occur without functional group activation. In addition, most organic molecules contain multiple C-H bonds with similar chemical properties, and how to selectively activate one or several C-H bonds is a core issue. Therefore, the activation of C-H bonds requires not only improving the reaction activity, but also improving the selectivity of the reaction.
[0003] Chlorinated alkanes are important intermediates for many chemicals and drugs. With the development of transition metal catalysis and photocatalysis technology, the research on alkyl chloride substitution reaction has also made significant progress. Scientists have improved the activity and selectivity of alkyl chloride substitution reaction by designing new catalytic systems and optimizing reaction conditions. Alkyl chloride substitution reaction is an important organic synthesis reaction that can be achieved by CH bond activation. Summary of the invention
[0004] The purpose of the present invention is to provide a method for alkyl chloride substitution with CH2Cl2 participating in CH bond activation, which is also effective for the later alkyl chloride substitution reaction of pharmaceutical-related molecules and is easy to promote.
[0005] The technical solution of the present invention is achieved in this way: The present invention provides a method for protecting an alkyl chloride substitution in which CH2Cl2 participates in CH bond activation, and has the following reaction equation:
[0006] The molar ratio of the raw material 1 to potassium tert-butoxide is 1:1.5-2.5; The reaction condition is stirring at room temperature for 20-40 seconds.
[0007] As a further improvement of the present invention, raw material 1 is added to a reaction tube, and potassium tert-butoxide is added, dichloromethane and dimethyl sulfoxide are added in the air, the reaction mixture is stirred at room temperature, the mixture is filtered, and then concentrated in vacuo, and the residue is purified by silica gel column chromatography to obtain the desired product 2.
[0008] As a further improvement of the present invention, the volume ratio of dichloromethane to dimethyl sulfoxide is 1:2.5-3.5.
[0009] The present invention has the following beneficial effects: the present invention develops an efficient method (short reaction time and simple operation) for selective C-alkyl chloride substitution reaction of CH bonds using dichloromethane. Under mild conditions, various C (sp 3 )-H bonds can be efficiently and selectively converted into the corresponding C-alkyl chloride substitution products. This method is also very effective for the later alkyl chloride substitution reaction of pharmaceutical-related molecules and is easy to promote. BRIEF DESCRIPTION OF THE DRAWINGS
[0010] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative labor.
[0011] Figure 1 is the hydrogen spectrum of the product obtained in Example 1; Figure 2 The carbon spectrum of the product obtained in Example 1; Figure 3 This is a single crystal structure diagram of the product obtained in Example 2. DETAILED DESCRIPTION
[0012] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0013] Example
[0014] This embodiment provides a method for replacing alkyl chloride with CH2Cl2 in CH bond activation. Raw material 1 is added to a reaction tube, and potassium tert-butoxide is added. Dichloromethane and dimethyl sulfoxide are added in the air. After the reaction mixture is stirred at room temperature, the mixture is filtered and then concentrated in vacuo. The residue is purified by silica gel column chromatography to obtain the desired product 2.
[0015] The raw materials and products and their proportions are as follows:
[0016] Figure 1 and Figure 2 The hydrogen spectrum and carbon spectrum of the product obtained in Example 1 are shown in FIG. Figure 3 This is a single crystal structure diagram of the product obtained in Example 2. It can be seen from the figure that the structure of the compound is consistent with the predicted structure.
[0017] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims
1. A method for substitution of alkyl chlorides with CH2Cl2 for CH bond activation, characterized in that: Has the following reaction equation: ， The molar ratio of the raw material 1 to potassium tert-butoxide is 1:1.5-2.5; The reaction condition is stirring at room temperature for 20-40 seconds.
2. The method for alkyl chloride substitution with CH2Cl2 participating in CH bond activation according to claim 1, characterized in that: Add raw material 1 into a reaction tube, add potassium tert-butoxide, add dichloromethane and dimethyl sulfoxide in the air, stir the reaction mixture at room temperature, filter the mixture, and then concentrate in vacuo. Purify the residue by silica gel column chromatography to obtain the desired product 2.
3. The method for alkyl chloride substitution with CH2Cl2 participating in CH bond activation according to claim 2, characterized in that: The volume ratio of the dichloromethane to dimethyl sulfoxide is 1:2.5-3.5.
Citation Information
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