阅读说明：本技术 一种具有三个碳碳双键的有机胺连接剂及其制备方法 (Organic amine connecting agent with three carbon-carbon double bonds and preparation method thereof ) 是由 李伟 谭建华 张星 于 2021-09-02 设计创作，主要内容包括：本申请涉及烯烃类有机胺连接剂领域,具体公开了一种具有三个碳碳双键的有机胺连接剂及其制备方法。一种具有三个碳碳双键的有机胺连接剂的化学结构式为：,R-(1)和R-(2)中至少有一个为H；其制备方法包括以下步骤：S1、上保护基反应：取卤代乙胺作为原料1,进行上X基和/或Y基保护反应,得到化合物1；S2、醚化反应：取季戊四醇三烯丙基醚作为原料2,与化合物1进行醚化反应,得到化合物2；S3、脱保护基反应,得到目标产物。本申请的有机胺连接剂具有加成点位更多、应用范围更广的优点。(The application relates to the field of olefin organic amine connecting agents, and particularly discloses an organic amine connecting agent with three carbon-carbon double bonds and a preparation method thereof. An organic amine linking agent having three carbon-carbon double bonds has the chemical formula: ，R 1 and R 2 At least one of which is H; the preparation method comprises the following steps: s1, reaction of upper protecting group: taking halogenated ethylamine as a raw material 1, and carrying out protection reaction on an X group and/or a Y group to obtain a compound 1; s2, etherification reaction: taking pentaerythritol triallyl ether as a raw material 2, and carrying out etherification reaction with a compound 1 to obtain a compound 2; and S3, carrying out deprotection reaction to obtain the target product. The organic amine linking agent has the advantages of more addition points and wider application range.)

1. An organic amine linking agent having three carbon-carbon double bonds, characterized by the chemical formula:said R is₁And R₂At least one of which is H.

2. The organic amine linking agent having three carbon-carbon double bonds as claimed in claim 1, wherein the chemical formula of the organic amine linking agent is:。

3. a method of making an organic amine linking agent having three carbon-carbon double bonds as defined in claim 1, comprising the steps of:

s1, reaction of upper protecting group: taking halogenated ethylamine as a raw material 1, and carrying out an X-group and/or Y-group protection reaction by adopting an X-group protection reagent and/or a Y-group protection reagent to obtain a compound 1;

s2, etherification reaction: taking pentaerythritol triallyl ether as a raw material 2, and carrying out etherification reaction with a compound 1 to obtain a compound 2;

s3, deprotection reaction: and carrying out X-group and/or Y-group removing reaction on the compound 2 to obtain a target product.

4. The method of claim 3, wherein in S1, the haloethylamine is used as the raw material 1, the protection reaction of the upper X group is performed first, and then the protection reaction of the upper Y group is performed, and in S3, the reaction of removing the Y group is performed first, and then the reaction of removing the X group is performed.

5. The method for preparing an organic amine linking agent with three carbon-carbon double bonds as claimed in claim 3 or 4, wherein the X group is at least one of p-nitrobenzenesulfonyl, tert-butoxycarbonyl, and benzyloxycarbonyl.

6. The method for preparing an organic amine linking agent with three carbon-carbon double bonds as claimed in claim 3 or 4, wherein the Y group is at least one of p-nitrobenzenesulfonyl, tert-butoxycarbonyl, and benzyloxycarbonyl.

7. The method for preparing an organic amine linker with three carbon-carbon double bonds as claimed in claim 4, wherein the X group is p-nitrobenzenesulfonyl derived from p-nitrobenzenesulfonyl chloride, and the Y group is t-butoxycarbonyl derived from Boc anhydride.

8. The method for preparing an organic amine linking agent with three carbon-carbon double bonds as claimed in claim 7, wherein the raw material 1 is bromoethylamine derived from bromoethylamine hydrobromide.

9. The method for preparing an organic amine linking agent with three carbon-carbon double bonds according to claim 8, wherein the amount of bromoethylamine hydrobromide is 87-95 parts, the amount of p-nitrobenzenesulfonyl chloride is 82-91 parts, the amount of Boc anhydride is 100-110 parts, and the amount of pentaerythritol triallyl ether is 169-177 parts.

10. The method for preparing an organic amine linking agent having three carbon-carbon double bonds as claimed in claim 7, wherein the reaction temperature in S1 and S3 is 15-50 ℃.

Technical Field

The application relates to the field of olefin organic amine connecting agents, in particular to an organic amine connecting agent with three carbon-carbon double bonds and a preparation method thereof.

Background

The organic amine generally refers to an organic substance generated by a chemical reaction between an organic substance and ammonia, and the olefin organic amine linking agent can be used as a crosslinking agent and can be used for chemical synthesis and high-molecular polymerization reaction.

At present, most of the commercially available olefin organic amine connecting agents are compounds only containing one or two carbon-carbon double bonds, for example, diallyl amine contains two carbon-carbon double bonds in the structure, and the addition points are few, so that the wide application of the olefin organic amine connecting agents is limited.

Disclosure of Invention

In order to develop an organic amine connecting agent with more carbon-carbon double bond addition points and expand the application range of the olefin organic amine connecting agent, the application provides an organic amine connecting agent with three carbon-carbon double bonds and a preparation method thereof.

In a first aspect, the present application provides an organic amine linking agent having three carbon-carbon double bonds, using the following technical scheme:

an organic amine linking agent having three carbon-carbon double bonds, having the chemical formula:the R is₁And R₂At least one of which is H.

By adopting the technical scheme, the organic amine connecting agent has three carbon-carbon double bonds, can perform addition reaction at three point positions, has more addition point positions compared with a compound with only one or two carbon-carbon double bonds, and enlarges the application range of the olefin organic amine connecting agent.

Optionally, the organic amine linker has a chemical structural formula:

by adopting the technical scheme, the organic amine connecting agent not only contains three carbon-carbon double bonds and can perform addition reaction at three point positions, but also is primary amine type and has two active hydrogens, primary amine is exposed outside, and the primary amine and the carbon-carbon double bonds are equal in position from the central carbon atom of the compound, so that the steric hindrance is small, the reaction activity of the organic amine connecting agent is improved, and the effect of expanding the application range of the olefin organic amine connecting agent is further obtained.

In a second aspect, the present application provides a method for preparing an organic amine linking agent having three carbon-carbon double bonds, which adopts the following technical scheme:

a method of making an organic amine linker having three carbon-carbon double bonds comprising the steps of:

s1, reaction of upper protecting group: taking halogenated ethylamine as a raw material 1, and carrying out an X-group and/or Y-group protection reaction by adopting an X-group protection reagent and/or a Y-group protection reagent to obtain a compound 1;

s2, etherification reaction: taking pentaerythritol triallyl ether as a raw material 2, and carrying out etherification reaction with a compound 1 to obtain a compound 2;

s3, deprotection reaction: and carrying out X-group and/or Y-group removing reaction on the compound 2 to obtain a target product.

By adopting the technical scheme, the method adopts the halogenated ethylamine as the raw material 1 to provide amino, the amino is subjected to an upper protection reaction through an X-group protection reagent and/or a Y-group protection reagent, and the amino hydrogen is substituted by the X-group and/or the Y-group to obtain the compound 1. Pentaerythritol triallyl ether is adopted as a raw material 2, and is subjected to etherification reaction with a compound 1 to obtain a compound 2, the compound 2 has three double bonds, then the compound 2 is subjected to X group and/or Y group removal reaction, amino hydrogen is recovered, and a target product, namely an organic amine connecting agent with three carbon-carbon double bonds can be obtained, wherein R is₁And R₂At least one of which is H.

Optionally, in S1, the haloethylamine is taken as the raw material 1, the protection reaction of the upper X group is performed first, and then the protection reaction of the upper Y group is performed, and in S3, the reaction of removing the Y group is performed first, and then the reaction of removing the X group is performed.

By adopting the technical scheme, two amino hydrogens are respectively protected through an upper X group protection reaction and an upper Y group protection reaction, then the Y group removing reaction and the X group removing reaction are carried out, and the two amino hydrogens are recovered, so that the primary amine type organic amine linking agent can be obtained.

Optionally, the X group is at least one of p-nitrobenzenesulfonyl, tert-butyl dicarbonate, tert-butoxycarbonyl and benzyloxycarbonyl.

By adopting the technical scheme, the X group is adopted for carrying out the upper protection reaction, the amino group can be effectively protected, and the X group is easy to remove during the deprotection reaction.

Optionally, the Y group is at least one of p-nitrobenzenesulfonyl, tert-butyl dicarbonate, tert-butoxycarbonyl and benzyloxycarbonyl.

By adopting the technical scheme, the Y group is adopted for carrying out the upper protection reaction, the amino group can be effectively protected, and the Y group is easy to remove during the deprotection reaction.

Optionally, the X group is p-nitrobenzenesulfonyl derived from p-nitrobenzenesulfonyl chloride, and the Y group is tert-butoxycarbonyl derived from Boc anhydride.

By adopting the technical scheme, the Ns protective group protects the amino group through the NsCl protection reaction, the Ns protective group is easy to introduce, the Ns removal protection reaction is mild, and the operation is convenient. Through last Boc protection reaction, make Boc protective group protection amino, accomplish other subsequent reactions after, and Boc protective group easily acidolysis is got rid of, convenient operation can have certain stability again, and is little to the influence of product.

Optionally, the raw material 1 is bromoethylamine and is derived from bromoethylamine hydrobromide.

By adopting the technical scheme, the bromoethylamine is used as the raw material 1, and the yield after the reaction is finished is high.

Optionally, the amount of the bromoethylamine hydrobromide is 87-95 parts, the amount of the p-nitrobenzenesulfonyl chloride is 82-91 parts, the amount of the Boc anhydride is 100-110 parts, and the amount of the pentaerythritol triallyl ether is 169-177 parts.

By adopting the technical scheme, the yield of the obtained organic amine connecting agent is high in the proportion.

Optionally, the reaction temperature in S1 and S3 is 15-50 ℃.

By adopting the technical scheme, both the protecting group adding reaction and the protecting group removing reaction can be carried out at the reaction temperature, the reaction can be carried out at normal temperature, and the situation of complicated operation caused by special temperature regulation is reduced.

In summary, the present application has the following beneficial effects:

1. the organic amine connecting agent prepared by the method contains three carbon-carbon double bonds, and has many addition points and wide application range.

2. The organic amine connecting agent prepared by the method contains three carbon-carbon double bonds, can also be of a primary amine type, has small steric hindrance and high reaction activity because primary amine is exposed outside, and further expands the application range of the olefin organic amine connecting agent.

3. The method has the advantages of easily available raw materials, simple reaction steps, good process controllability and easy large-scale industrial mass production.

Drawings

FIG. 1 is a NMR chart of 1,1, 1-triallyl methyl ether-2-ethoxyamine prepared in the examples of the present application;

FIG. 2 is an electrospray ionization mass spectrum of 1,1, 1-triallyl methyl ether-2-ethoxyamine prepared in the examples of the present application.

Detailed Description

The present application will be described in further detail with reference to the following drawings and examples. The special description is as follows: the following examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer, and the starting materials used in the following examples were obtained from ordinary commercial sources unless otherwise specified.

TABLE 1 raw material specifications

In the following examples room temperature is 25 ℃.

Examples

Example 1

An organic amine linking agent having three carbon-carbon double bonds, having the chemical formula:R₁and R₂At least one of the organic amine linking agents is H, the organic amine linking agent has three carbon-carbon double bonds and multiple addition points, and the application range of the olefin organic amine linking agent is expanded.

When R is₁And R₂When all are H, the chemical structural formula isThe organic amine connecting agent is named as 1,1, 1-triallyl methyl ether-2-ethoxy amine, the organic amine connecting agent not only has three carbon-carbon double bonds, but also is a primary amine type compound, primary amine is exposed outside, the position of the primary amine is equal to the position of the three carbon-carbon double bonds away from the central carbon atom of the compound, the steric hindrance is small, the reaction activity of the organic amine connecting agent is improved, and the application range of the olefin organic amine connecting agent is further expanded.

A process for preparing 1,1, 1-triallyl methyl ether-2-ethoxyamine comprising the steps of:

s1, reaction of upper protecting group:

(1) and (3) protection reaction of the upper X group: bromoethylamine hydrobromide (17.84g, 87mmol) was taken as starting material 1 and dissolved in 200ml dichloromethane to give solution A, and sodium carbonate (19.36g, 182.8mmol) was taken and dissolved in 200ml water to give solution B. Take the X group protecting reagent, which is p-nitrobenzenesulfonyl in this example and is derived from p-nitrobenzenesulfonyl chloride, and dissolve the p-nitrobenzenesulfonyl chloride protecting reagent (18.12g, 82mmol) in 200ml dichloromethane to obtain solution C. Then, the solution A, the solution B and the solution C were mixed and stirred at room temperature for 1 hour. Thereafter, the organic phase dichloromethane was extracted, and the extracted organic phase dichloromethane was washed once with 400ml of water.

The reaction process is as follows:

(2) protection reaction of the Y group: taking a Y-based protective reagent, wherein Y is tert-butyloxycarbonyl in the example and is derived from Boc anhydride, adding Boc anhydride (21.8g and 100mmol) into the organic phase dichloromethane washed in the step (1) to form a system A, stirring the system A at room temperature for 2h, washing the system A with 400ml of water for three times, drying the system A with anhydrous magnesium sulfate for 12h to remove dichloromethane, filtering, collecting filtrate, and concentrating to obtain a light yellow solid compound 1.

The reaction process is as follows:

s2, etherification reaction: pentaerythritol triallyl ether was used as a starting material 2, and compound 1(34.5g, 84.5mmol) and pentaerythritol triallyl ether (43.26g, 169mmol) were dissolved in 400ml of N, N-dimethylformamide to form a system B, and potassium hydroxide powder (4.7g, 84.5mmol) was added to system B while stirring, and then the mixture was heated to 60 ℃ and stirred for 2 hours. The mixture was extracted with 600ml of dichloromethane and 600ml of water, and the extracted organic phase dichloromethane was dried over anhydrous magnesium sulfate for 12 hours, filtered, and the filtrate was collected and concentrated to give compound 2 as a pale yellow liquid.

The reaction process is as follows:

s3, deprotection reaction:

(1) and (3) removing Y group protection reaction: taking compound 2(54.75g, 82.46mmol) and dissolving in 1000ml dichloromethane to form system C, cooling to 0 ℃, dropwise adding 32ml trifluoroacetic acid into the system C while stirring, raising the temperature to room temperature, continuing stirring for 2h, and removing Y group, namely tert-butyloxycarbonyl group, to form system D.

The reaction process is as follows:

(2) and (3) removing X group protection reaction: and (3) dropwise adding 28ml of thioglycollic acid into the system D while stirring, continuing stirring for 2 hours after dropwise adding is finished, and removing the X group, namely the p-nitrobenzenesulfonyl. Extracting with 1500ml ethyl acetate and 1500ml sodium carbonate aqueous solution with mass concentration of 5%, adjusting pH to 10, washing the organic phase with 1000ml water for three times, drying the extracted organic phase ethyl acetate with anhydrous magnesium sulfate for 12h, filtering, collecting the filtrate, and concentrating to obtain light yellow liquid, namely the target product 1,1, 1-triallyl methyl ether-2-ethoxy amine.

The reaction process is as follows:

example 2 to example 3

The following examples differ from example 1 in the amounts of starting material 1, starting material 2, p-nitrobenzenesulfonyl chloride, Boc anhydride, compound 1 and potassium hydroxide powder and are detailed in table 2.

Example 4

This example differs from example 2 in that:

s3, deprotection reaction:

(1) and (3) removing X group protection reaction: dissolving compound 2(54.75g, 82.46mmol) in 1000ml dichloromethane to form system C, dropwise adding thioglycolic acid 28ml into system C while stirring, continuing stirring for 2h after dropwise adding is finished, and removing X group, namely p-nitrobenzenesulfonyl to form system D.

The reaction process is as follows:(2) and (3) removing Y group protection reaction: 32ml of trifluoroacetic acid was added dropwise to the system D while stirring, and after the temperature was raised to room temperature, stirring was continued for 2 hours to remove the Y group, i.e., t-butoxycarbonyl group. Extracting with 1500ml ethyl acetate and 1500ml sodium carbonate aqueous solution with mass concentration of 5%, adjusting pH to 10, washing the organic phase with 1000ml water for three times, drying the extracted organic phase ethyl acetate with anhydrous magnesium sulfate for 12h, filtering, collecting the filtrate, and concentrating to obtain light yellow liquid, namely the target product 1,1, 1-triallyl methyl ether-2-ethoxy amine.

The reaction process is as follows:

example 5

This example differs from example 4 in that: an organic amine linking agent having three carbon-carbon double bonds, having the chemical formula:R₁and R₂One of which is H.

In the method for preparing the organic amine connecting agent with three carbon-carbon double bonds, Y-removing protection reaction is not carried out, 1500ml of ethyl acetate and 1500ml of sodium carbonate aqueous solution with the mass concentration of 5% are used for extracting a system D, the pH value is adjusted to 10, an organic phase is washed with 1000ml of water for three times, the extracted organic phase ethyl acetate is dried for 12 hours by anhydrous magnesium sulfate, the filtration is carried out, the filtrate is collected and concentrated, and the target product, namely the target product, is obtainedThe amount of the objective product was 17.2 g.

Example 6

This example differs from example 2 in that: an organic amine linking agent having three carbon-carbon double bonds, having the chemical formula:R₁and R₂One of which is H.

In the method for preparing the organic amine connecting agent with three carbon-carbon double bonds, no X-removing protection reaction is carried out, 1500ml of ethyl acetate and 1500ml of sodium carbonate aqueous solution with the mass concentration of 5% are used for extracting a system D, the pH value is adjusted to 10, an organic phase is washed with 1000ml of water for three times, the extracted organic phase ethyl acetate is dried for 12 hours by anhydrous magnesium sulfate, the filtration is carried out, the filtrate is collected and concentrated, and the target product, namely the target product, is obtainedThe amount of the objective product was 15.7 g.

Example 7

This example differs from example 2 in that: the starting material 1 was chloroethylamine hydrochloride, the amount of which is specified in table 2.

Example 8

This example differs from example 2 in that: the room temperature in the steps S1 and S3 was replaced with 15 ℃.

Example 9

This example differs from example 2 in that: the room temperature in the steps S1 and S3 was replaced with 50 ℃.

Example 10

This example differs from example 2 in that:

a process for preparing 1,1, 1-triallyl methyl ether-2-ethoxyamine comprising the steps of:

s1, reaction of upper protecting group:

bromoethylamine hydrobromide (18.74g, 91.4mmol) was taken as starting material 1 and dissolved in 200ml dichloromethane to give solution A, and sodium carbonate (19.36g, 182.8mmol) was taken and dissolved in 200ml water to give solution B. Take p-nitrobenzenesulfonyl protecting reagent, in this example p-nitrobenzenesulfonyl is derived from p-nitrobenzenesulfonyl chloride, and dissolve p-nitrobenzenesulfonyl chloride (19.23g, 87mmol) in 200ml dichloromethane to obtain solution C. Then, the solution A, the solution B and the solution C were mixed and stirred at room temperature for 1 hour. Thereafter, the organic phase dichloromethane was extracted, and the extracted organic phase dichloromethane was washed three times with 400ml of water. Drying over anhydrous magnesium sulfate for 12h to remove dichloromethane, filtering, collecting the filtrate, and concentrating to obtain compound 1.

The reaction process is as follows:

s2, etherification reaction: pentaerythritol triallyl ether was taken as a raw material 2, 86.8mmol of the compound 1 and pentaerythritol triallyl ether (44.44g, 173.6mmol) were dissolved in 400ml of N, N-dimethylformamide to form a system B, potassium hydroxide powder (4.86g, 86.8mmol) was added to the system B while stirring, and then the temperature was raised to 60 ℃ and stirring was continued for 2 hours. The mixture was extracted with 600ml of dichloromethane and 600ml of water, and the extracted organic phase dichloromethane was dried over anhydrous magnesium sulfate for 12 hours, filtered, and the filtrate was collected and concentrated to obtain compound 2.

The reaction process is as follows:

s3, deprotection reaction:

82.46mmol of compound 2 is dissolved in 1000ml of dichloromethane to form a system C, 28ml of thioglycolic acid is dropwise added into the system C while stirring, stirring is continued for 2 hours after the dropwise addition is finished, and the p-nitrobenzenesulfonyl is removed. Extracting with 1500ml ethyl acetate and 1500ml sodium carbonate aqueous solution with mass concentration of 5%, adjusting pH to 10, washing the organic phase with 1000ml water for three times, drying the extracted organic phase ethyl acetate with anhydrous magnesium sulfate for 12h, filtering, collecting the filtrate, and concentrating to obtain light yellow liquid, namely the target product 1,1, 1-triallyl methyl ether-2-ethoxy amine.

The reaction process is as follows:

example 11

This example differs from example 2 in that:

a process for preparing 1,1, 1-triallyl methyl ether-2-ethoxyamine comprising the steps of:

s1, reaction of upper protecting group:

bromoethylamine hydrobromide (18.74g, 91.4mmol) was taken as the starting material 1 and dissolved in 200ml dichloromethane to give a solution A. A tert-butyloxycarbonyl protecting reagent, which in this example was derived from Boc anhydride (22.8g, 104.4mmol), was taken and dissolved in 200ml dichloromethane to give solution B. And mixing the solution A and the solution B to form a system A, stirring the system A at room temperature for 2 hours, washing the system A with 400ml of water for three times, drying the system A with anhydrous magnesium sulfate for 12 hours to remove dichloromethane, filtering, collecting filtrate, and concentrating to obtain the compound 1.

The reaction process is as follows:

s2, etherification reaction: pentaerythritol triallyl ether was taken as a raw material 2, 86.8mmol of the compound 1 and pentaerythritol triallyl ether (44.44g, 173.6mmol) were dissolved in 400ml of N, N-dimethylformamide to form a system B, potassium hydroxide powder (4.86g, 86.8mmol) was added to the system B while stirring, and then the temperature was raised to 60 ℃ and stirring was continued for 2 hours. The mixture was extracted with 600ml of dichloromethane and 600ml of water, and the extracted organic phase dichloromethane was dried over anhydrous magnesium sulfate for 12 hours, filtered, and the filtrate was collected and concentrated to obtain compound 2.

The reaction process is as follows:

s3, deprotection reaction:

82.46mmol of compound 2 is dissolved in 1000ml of dichloromethane to form a system C, the system C is cooled to 0 ℃, 32ml of trifluoroacetic acid is dripped into the system C while stirring, the temperature is raised to room temperature, and then the stirring is continued for 2h, thus the tert-butyloxycarbonyl group can be removed. Extracting with 1500ml ethyl acetate and 1500ml sodium carbonate aqueous solution with mass concentration of 5%, adjusting pH to 10, washing the organic phase with 1000ml water for three times, drying the extracted organic phase ethyl acetate with anhydrous magnesium sulfate for 12h, filtering, collecting the filtrate, and concentrating to obtain light yellow liquid, namely the target product 1,1, 1-triallyl methyl ether-2-ethoxy amine.

The reaction process is as follows:

example 12

This embodiment differs from embodiment 11 in that: the protecting group in this example is benzyloxycarbonyl, derived from benzyl chloroformate.

A process for preparing 1,1, 1-triallyl methyl ether-2-ethoxyamine comprising the steps of:

s1, reaction of upper protecting group:

bromoethylamine hydrobromide (18.74g, 91.4mmol) was taken as the starting material 1 and dissolved in 200ml dichloromethane to give a solution A. The benzyloxycarbonyl protecting reagent, in this example the benzyloxycarbonyl group was derived from benzyl chloroformate, i.e., benzyl chloroformate (15.59g, 91.4mmol) was dissolved in 200ml of dichloromethane to give solution B. Mixing the solution A and the solution B to form a system A, and continuously dropwise adding 2mol/L sodium hydroxide solution into the system A at 0 ℃ to maintain the pH at 9. Then, the mixture was heated to room temperature, the system a was stirred at room temperature for 2 hours, the system a was washed three times with 400ml of water, dried over anhydrous magnesium sulfate for 12 hours to remove methylene chloride, filtered, and the filtrate was collected and concentrated to obtain compound 1.

The reaction process is as follows:

s2, etherification reaction: pentaerythritol triallyl ether was taken as a raw material 2, 86.8mmol of the compound 1 and pentaerythritol triallyl ether (44.44g, 173.6mmol) were dissolved in 400ml of N, N-dimethylformamide to form a system B, potassium hydroxide powder (4.86g, 86.8mmol) was added to the system B while stirring, and then the temperature was raised to 60 ℃ and stirring was continued for 2 hours. The mixture was extracted with 600ml of dichloromethane and 600ml of water, and the extracted organic phase dichloromethane was dried over anhydrous magnesium sulfate for 12 hours, filtered, and the filtrate was collected and concentrated to obtain compound 2.

The reaction process is as follows:

s3, deprotection reaction:

82.46mmol of compound 2 was dissolved in 1000ml of dichloromethane to form a system C, 32ml of trifluoroacetic acid was added dropwise to the system C while stirring at room temperature, and the mixture was further stirred for 2 hours to remove benzyloxycarbonyl. Extracting with 1500ml ethyl acetate and 1500ml sodium carbonate aqueous solution with mass concentration of 5%, adjusting pH to 10, washing the organic phase with 1000ml water for three times, drying the extracted organic phase ethyl acetate with anhydrous magnesium sulfate for 12h, filtering, collecting the filtrate, and concentrating to obtain light yellow liquid, namely the target product 1,1, 1-triallyl methyl ether-2-ethoxy amine.

The reaction process is as follows:

TABLE 2

Comparative example

Comparative example 1

Diallyl amine purchased from Shandong Luyue chemical group, Inc., with CAS number of 124-02-7, and chemical structural formula:

performance test

Detection method

1. 1,1, 1-triallyl methyl ether-2-ethoxyamine obtained in each example except for example 5 and example 6 was analyzed by nuclear magnetic resonance carbon spectrometry and electrospray mass spectrometry to obtain 1,1, 1-triallyl methyl ether-2-ethoxyamine of which nuclear magnetic resonance carbon spectrum and electrospray ionization mass spectrum are respectively shown in FIG. 1 and FIG. 2.

It can be seen that the chemical structure of the 1,1, 1-triallyl methyl ether-2-ethoxyamine contains three carbon-carbon double bonds, and compared with the conventional compound only containing one or two carbon-carbon double bonds, the compound has more addition points, and the application range of the olefin organic amine linking agent is expanded.

The 1,1, 1-triallyl methyl ether-2-ethoxy amine is primary amine type, primary amine is exposed outside, and the positions of the primary amine and a carbon-carbon double bond which are far away from the central carbon atom of the compound are equivalent, so that the compound has higher reaction activity.

The diallylamine of comparative example 1 has only two carbon-carbon double bonds, is a secondary amine type, has only one active hydrogen, and has few addition points and low reactivity.

In addition, the target products prepared in the examples 5 and 6 are secondary amine type, only have one active hydrogen and have low reaction activity, and the 1,1, 1-triallyl methyl ether-2-ethoxyamine is primary amine type, has two active hydrogens and has higher reaction activity, thereby further expanding the application range of the olefin organic amine linking agent.

2. The yields of 1,1, 1-triallyl methyl ether-2-ethoxyamine from the various examples are shown in Table 3:

TABLE 3

Examples	Target product amount/g
		Example 1	21.3g
Example 2	23.9g
		Example 3	21.8g
Example 4	13.7g
		Example 7	20.4g
Example 8	22.1g
		Example 9	23.4g
Example 10	17.1g
		Example 11	17.6g
Example 12	16.2g

As can be seen from Table 3, the yield of 1,1, 1-triallyl methyl ether-2-ethoxyamine produced by the preparation method of example 2 is the highest, and the following specific analysis is made:

example 4 differs from example 2 in the order of deprotection, and in example 4, p-nitrobenzenesulfonyl and then tert-butoxycarbonyl are removed to finally obtain 1,1, 1-triallyl methyl ether-2-ethoxyamine, but the yield is reduced by 42.7% compared with the yield of 1,1, 1-triallyl methyl ether-2-ethoxyamine obtained in example 2. The method embodies that the last protecting group is removed in the preparation method, and the two amino hydrogens can be recovered better, so that the yield can be improved to a greater extent.

Example 7 differs from example 2 in that instead of using 1 as starting material, bromoethylamine was used in example 2 and chloroethylamine was used in example 7, and 1,1, 1-triallyl methyl ether-2-ethoxyamine was produced despite the fact that haloethylamine was used in all cases, but the yield of 1,1, 1-triallyl methyl ether-2-ethoxyamine produced in example 7 was reduced by 23% compared to the yield of 1,1, 1-triallyl methyl ether-2-ethoxyamine produced in example 2. The method embodies that the finished product rate of the finally prepared target product is higher when the bromoethylamine is used as a raw material.

The difference between the example 8 and the example 9 and the example 2 is that the reaction temperature is different, the reaction can be normally carried out at the reaction temperature of 15-50 ℃, and the yield of the target product is high, but the example 2 is a normal-temperature reaction, the temperature regulation is not required, the operation is simple, and the yield of the target product is the highest.

In comparison with example 2, 1, 1-triallyl methyl ether-2-ethoxyamine was also obtained in the end of the reactions in examples 10, 11 and 12, which all used a protecting group, but the yields were lower than those of 1,1, 1-triallyl methyl ether-2-ethoxyamine obtained in example 2. The method has the effect of high yield when the target product is prepared by the twice protecting group reactions and twice protecting group removing reactions in the preparation method.

The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.