阅读说明：本技术 有机叠氮类离子型化合物及其制备方法 (Organic azide ionic compound and preparation method thereof ) 是由 王桂春 张海燕 骆浩 于 2019-10-15 设计创作，主要内容包括：本发明提供一种有机叠氮类离子型化合物及其制备方法,其中,制备方法包括如下步骤：步骤1,将氯代离子型化合物溶解在乙腈中,得到氯代离子型化合物的乙腈溶液,其中,所述氯代离子型化合物具有氯取代烷结构或氯取代磷结构；步骤2,在所述氯代离子型化合物的乙腈溶液中加入叠氮化钠进行反应,生成所述有机叠氮类离子型化合物。根据本发明的实施例的有机叠氮类离子型化合物的制备方法,反应转化率高,且三废较少,减轻环保压力。且该操作简便易行,得到的产品纯度高,产品安全性好,易于储存及应用。(The invention provides an organic azide ionic compound and a preparation method thereof, wherein the preparation method comprises the following steps: step 1, dissolving a chloride ion type compound in acetonitrile to obtain an acetonitrile solution of the chloride ion type compound, wherein the chloride ion type compound has a chloride substituted alkane structure or a chloride substituted phosphorus structure; and 2, adding sodium azide into the acetonitrile solution of the chloride ion type compound for reaction to generate the organic azide ion type compound. According to the preparation method of the organic azide ionic compound provided by the embodiment of the invention, the reaction conversion rate is high, the three wastes are less, and the environmental protection pressure is reduced. The operation is simple and easy to implement, and the obtained product has high purity, good safety and easy storage and application.)

1. The preparation method of the organic azide ionic compound is characterized by comprising the following steps:

step 1, dissolving a chloride ion type compound in acetonitrile to obtain an acetonitrile solution of the chloride ion type compound, wherein the chloride ion type compound has a chloride substituted alkane structure or a chloride substituted phosphorus structure;

and 2, adding sodium azide into the acetonitrile solution of the chloride ion type compound for reaction to generate the organic azide ion type compound.

2. The method according to claim 1, wherein the structural formula of the chloro-substituted alkane is represented by the following formula (1),

the structural formula of the chlorine-substituted phosphorus structure is shown as the following formula (2),

wherein R1 represents an amine group, and R2 represents an amine group^-And represents hexafluorophosphate or tetrafluoroborate.

3. The method of claim 2, wherein the amine group is dipyrrole and its derivatives, tripyrrole and its derivatives, tetrahydropyridine, dimethylamine, or diisopropylamine.

4. The preparation method according to claim 1, wherein in the step 2, the molar ratio of the chloride ionic compound to the sodium azide is 1 (1.2-1.5).

5. The preparation method according to claim 1, wherein in the step 2, the reaction temperature is 10-15 ℃ and the reaction time is 3-5 h.

6. The method of claim 1, further comprising the steps of:

step 3, carrying out suction filtration on the product obtained in the step 2 to obtain a filtrate;

and 4, concentrating and drying the filtrate to obtain the organic azide ionic compound.

7. The method according to claim 6, wherein the step 3 further comprises:

the filter cake was rinsed with acetonitrile and the rinse was combined into the filtrate.

8. The method of claim 6 or 7, further comprising the steps of:

and 5, recrystallizing the organic azide ionic compound obtained by concentration in the step 4 to obtain the refined organic azide ionic compound.

9. The production method according to claim 8, wherein the recrystallization is performed using methanol.

10. An organoazide ionic compound produced by the production method according to any one of claims 1 to 9.

Technical Field

The invention relates to the technical field of chemical synthesis, in particular to an organic azide ionic compound and a preparation method thereof.

Background

At present, sodium azide is mainly used as an azide protective agent, has poor solubility in an organic solvent, slow reaction and high risk, cannot contact metal ions in the operation process, and has high toxicity and high explosiveness during the post-treatment acid adjustment. Therefore, there is a high necessity to solve this problem.

On the other hand, the organic azide ionic compound is a relatively stable organic azide protective agent and is a very important intermediate in organic synthesis. The compound is organic and can be well dissolved in an organic solvent, so that the compound can participate in the reaction more quickly. The amino group of the compound has variability, and the compound presents diversity. However, the conventional production methods are poor in versatility and complicated in post-treatment.

Disclosure of Invention

In view of the above, the invention provides a preparation method of an organic azide ionic compound, which has good solubility, easy post-treatment, simple operation and strong versatility.

The invention also provides an organic azide ionic compound.

In order to solve the technical problems, the invention adopts the following technical scheme:

the preparation method of the organic azide ionic compound according to the embodiment of the first aspect of the present invention comprises the following steps:

step 1, dissolving a chloride ion type compound in acetonitrile to obtain an acetonitrile solution of the chloride ion type compound, wherein the chloride ion type compound has a chloride substituted alkane structure or a chloride substituted phosphorus structure,

and 2, adding sodium azide into the acetonitrile solution of the chloride ion type compound for reaction to generate the organic azide ion type compound.

Preferably, the structural formula of the chloro-substituted alkane structure is shown as the following formula (1):

the structural formula of the chlorine-substituted phosphorus structure is shown as the following formula (2):

wherein R1 represents an amine group, and R2 represents an amine group^-And represents hexafluorophosphate or tetrafluoroborate.

Preferably, the amine group is dipyrrole and its derivatives, tripyrrole and its derivatives, tetrahydropyridine, dimethylamine, or diisopropylamine.

Preferably, in the step 2, the molar ratio of the chloride ionic compound to the sodium azide is 1 (1.2-1.5).

Preferably, in the step 2, the reaction temperature is 10-15 ℃ and the reaction time is 3-5 h.

Preferably, the preparation method further comprises the following steps:

step 3, carrying out suction filtration on the product obtained in the step 2 to obtain a filtrate;

and 4, concentrating and drying the filtrate to obtain the organic azide ionic compound.

Further, the step 3 further includes:

the filter cake was rinsed with acetonitrile and the rinse was combined into the filtrate.

Further, the preparation method also comprises the following steps:

and 5, recrystallizing the organic azide ionic compound obtained by concentration in the step 4 to obtain the refined organic azide ionic compound.

Preferably, the recrystallization is carried out using methanol.

The organic azide type ionic compound according to the embodiment of the second aspect of the present invention is prepared by the preparation method described in any one of the above.

The technical scheme of the invention at least has one of the following beneficial effects:

(1) the reaction conversion rate is high, the three wastes are less, and the environmental protection pressure is reduced;

(2) the operation is simple and easy, and the obtained product has high purity;

(3) the product has good safety and is easy to store and apply.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention are clearly and completely described below. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention, are within the scope of the invention.

The preparation method of the organic azide ionic compound provided by the embodiment of the invention comprises the following steps:

step 1, dissolving a chloride ion type compound in acetonitrile to obtain an acetonitrile solution of the chloride ion type compound, wherein the chloride ion type compound has a chloride substituted alkane structure or a chloride substituted phosphorus structure.

Wherein, the structural formula of the chloro-substituted alkane structure can be shown as the following formula (1):

the structural formula of the chlorine-substituted phosphorus structure is shown as the following formula (2):

wherein R1 represents an amine group, and R2 represents an amine group^-And represents hexafluorophosphate or tetrafluoroborate.

Wherein, the amino group can be any one of dipyrrole and derivatives thereof, tetrahydropyridine, dimethylamine or diisopropylamine.

And 2, adding sodium azide into the acetonitrile solution of the chloride ion type compound for reaction to generate the organic azide ion type compound.

When a chloro-substituted alkane structure is used as the chloro-ionic compound, the reaction with sodium azide is represented by the following formula (3):

when a chlorine-substituted phosphorus structure is used as the chloride ion type compound, the reaction with sodium azide is shown in the following formula (4):

wherein the molar ratio of the chloride ion type compound to the sodium azide can be 1 (1.2-1.5).

In addition, the reaction temperature can be 10-15 ℃, and the reaction time can be 3-5 h.

Further, the preparation method of the organic azide ionic compound according to the embodiment of the invention further comprises the following steps:

and 3, carrying out suction filtration on the product obtained in the step 2 to obtain a filtrate.

Further, the filter cake after suction filtration may be washed with acetonitrile, and the washing solution may be added to the filtrate.

And 4, concentrating and drying the filtrate to obtain the organic azide ionic compound.

The concentration may be carried out by, for example, concentration under reduced pressure, and the precipitated solid phase is an organic azide-based ionic compound.

And 5, recrystallizing the organic azide ionic compound obtained by concentration in the step 4 to obtain the refined organic azide ionic compound.

The recrystallization may be carried out using methanol, for example, and the specific method and procedure for recrystallization may be a method commonly used in the field of organic synthesis, and a detailed description thereof will be omitted.

According to the preparation method of the organic azide ionic compound provided by the embodiment of the invention, the reaction conversion rate is high, the three wastes are less, and the environmental protection pressure is reduced. The operation is simple and easy to implement, and the obtained product has high purity, good safety and easy storage and application.

In order to make the technical solution of the present invention better understood by those skilled in the art, the present invention is further described in detail with reference to the following examples.