阅读说明：本技术 固体超强酸催化剂催化烯烃环丙烷化反应的方法 (Method for catalyzing cyclopropanation reaction of olefin by solid super acidic catalyst ) 是由 邹吉军 史成香 潘伦 张香文 于 2021-09-06 设计创作，主要内容包括：本发明公开了一种固体超强酸催化烯烃环丙烷化的方法,包括如下步骤：①在-30℃～10℃和氮气氛围下,将固体超强酸催化剂与锌类卡宾体混合；②向步骤①的体系中加入原料烯烃进行反应；③分离提纯步骤②的反应产物即得到环丙烷化产物。本发明采用固体超强酸作为烯烃环丙烷化反应的非均相催化剂具有容易与反应物分离、可重复使用等优点；烯烃的转化率和产物收率高。(The invention discloses a method for cyclopropanizing olefin by solid super acid catalysis, which comprises the following steps: firstly, mixing a solid super acidic catalyst with a zinc carbene compound at a temperature of between 30 ℃ below zero and 10 ℃ in a nitrogen atmosphere; secondly, adding olefin serving as a raw material into the system obtained in the step I for reaction; and thirdly, separating and purifying the reaction product obtained in the second step to obtain a cyclopropanation product. The method adopts the solid super acid as the heterogeneous catalyst for the cyclopropanation reaction of the olefin, and has the advantages of easy separation from reactants, reusability and the like; the conversion rate of olefin and the yield of products are high.)

1. A method for cyclopropanizing olefin by solid super acid catalysis is characterized by comprising the following steps:

firstly, mixing a solid super acidic catalyst with a zinc carbene compound at a temperature of between 30 ℃ below zero and 10 ℃ in a nitrogen atmosphere; secondly, adding olefin serving as a raw material into the system obtained in the step I for reaction; and thirdly, separating and purifying the reaction product obtained in the second step to obtain a cyclopropanation product.

2. The method of claim 1, wherein the solid super acidic catalyst is phosphotungstic acid, silicotungstic acid, sulfonic acid type resin Amberlyst-15, perfluorosulfonic acid type resin Nafion-212, SO^4-/ZrO₂、SO^4-/TiO₂Or SO^4-/Fe₂O₃One or more of them.

3. The method according to claim 1 or 2, wherein the amount of the solid super acid catalyst is 10 to 50 wt% of the raw material olefin.

4. The method of claim 1, wherein the zinc-based carbene is EtZnCH₂I。

5. The method according to claim 1 or 4, wherein the mass ratio of the raw material olefin to the zinc-based carbene is 1 (1-6).

6. The method according to claim 1, wherein the olefin is one or more of myrcene, alpha-pinene, beta-pinene, dicyclopentadiene, norbornene, norbornadiene.

Technical Field

The invention relates to the technical field of organic chemistry, in particular to a method for catalyzing cyclopropanation reaction of olefin by a solid super acidic catalyst.

Background

The cyclopropane is used as a basic structural unit with larger tensile energy, and the introduction of the cyclopropane into fuel molecules can remarkably improve the energy density and the specific impulse of the fuel, thereby increasing the range and the payload of the aerospace craft. Simmons-SmithThe reaction is a simple and efficient cyclopropanation method, and zinc carbine-IZNCH is generated in situ by zinc powder and diiodomethane₂I cyclopropanation of an alkene.

With the continuous innovation of research, the structure of the zinc carbene is continuously optimized, and the reactivity and the stability are continuously improved. For example, adding organic compounds to the reaction systemAcids such as CF₃COOH，CCl₃COOH, etc., or Lewis acids such as TiCl₄、AlCl₃、ZnCl₂And the like, can improve the reactivity of the carbene and promote cyclopropanation reaction. However, it is not limited toThe Acid or Lewis Acid has some inevitable disadvantages, such as, during use,acid is volatile and has pungent odor; lewis Acid is fuming in the air to generate hydrochloric Acid droplets, and the hydrochloric Acid droplets are corrosive; in addition to this, the present invention is,the Acid and the Lewis Acid are continuously consumed in the reaction and cannot be recycled, thereby causing waste.

The present invention has been made to solve the above problems.

Disclosure of Invention

The invention provides a method for catalyzing cyclopropanation reaction of olefin by solid super acidic catalyst.

The technical scheme of the invention is as follows:

a process for cyclopropanation of an alkene catalyzed by a solid super acid comprising the steps of: firstly, uniformly mixing a solid super acidic catalyst and a zinc carbene compound at-30-10 ℃ in a nitrogen atmosphere, and reacting for a certain time; secondly, adding olefin serving as a raw material into the system in the step I, and continuously reacting for a certain time; and thirdly, separating and purifying the reaction product obtained in the second step to obtain a cyclopropanation product.

Preferably, the solid super acidic catalyst is phosphotungstic acid, silicotungstic acid, sulfonic acid type resin Amberlyst-15, perfluorosulfonic acid type resin Nafion-212, SO^4-/ZrO₂、SO^4-/TiO₂Or SO^4-/Fe₂O₃One or more of them.

Preferably, the amount of the solid super acidic catalyst is 10-50 wt% of the raw material olefin.

Preferably, the zinc carbene is EtZnCH₂I。

Preferably, the mass ratio of the raw material olefin to the zinc-based carbene is 1 (1-6).

Preferably, the olefin is one or more of myrcene, alpha-pinene, beta-pinene, dicyclopentadiene, norbornene and norbornadiene.

The invention has the beneficial effects that:

1. the method of the invention adopts solid super acid as a heterogeneous catalyst for cyclopropanation of olefin for the first time. The acidity and acid content of the solid super acid are stronger than those of the common super acidThe Acid and the Lewis Acid have the advantages of easy separation from reactants, repeated use, no corrosion to a reactor, no environmental pollution and the like.

2. The catalyst of solid super acid has high activity, and the olefin converting rate and the product yield are higher than those of organic catalystAcid or Lewis Acid.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available by purchase.

Example 1, a process for cyclopropanation of an alkene catalyzed by a solid super acid comprising the steps of:

(1) at-20 ℃ and N₂In the atmosphere, 45mL of diethyl zinc solution and 45mL of dichloromethane solvent are added into a three-neck jacketed flask;

(2) weighing 0.612g of phosphotungstic acid, adding the phosphotungstic acid into the solution under mechanical stirring, then slowly dropwise adding 22.5mL of dichloromethane solvent into the solution, and reacting for 20 minutes;

(3) measuring 22.5mL of dichloromethane solvent, and adding 3.705mL of diiodomethane reagent into the dichloromethane solvent; then dropwise adding the mixture into the reaction solution obtained in the step (2) to react for 20 minutes;

(4) 22.5mL of a methylene chloride solvent was measured, 2.55mL of a myrcene reagent was added thereto, and the mixture was slowly added dropwise to the reaction solution of the step (3) and reacted at 25 ℃ for 2 hours.

(5) Slowly adding saturated NH into the reaction liquid in the step (4)₄Continuing stirring the Cl solution for 5 minutes; the organic phase was then separated from the aqueous phase, which was washed successively with deionized water, saturated NaCl solution and the product components were analyzed by gas chromatography. The yield of the cyclopropane compound was 85.2% by weight.

Examples 2 to 8

Examples 2-8 the reaction steps were the same as in example 1 except for the reaction raw materials, catalysts or reaction conditions, as shown in table 1.

Table 1 examples 2-8

The solid superacids used in examples 1 to 8 can be separated and reused.

As can be seen from Table 1, the solid super acid is used as the heterogeneous catalyst for the cyclopropanation reaction of the olefin, and the activity of the catalyst is high; the yield of the product is high and is over 85 percent.

While specific embodiments of, and examples for, the invention are described herein for illustrative purposes, various changes in detail will be apparent to those skilled in the art without departing from the invention.