CN106588708B - The synthetic method of Gemini surface active agent - Google Patents

The synthetic method of Gemini surface active agent Download PDF

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CN106588708B
CN106588708B CN201611014078.4A CN201611014078A CN106588708B CN 106588708 B CN106588708 B CN 106588708B CN 201611014078 A CN201611014078 A CN 201611014078A CN 106588708 B CN106588708 B CN 106588708B
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active agent
surface active
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gemini surface
synthesis
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CN106588708A (en
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姜建辉
梁鹏举
赵俭波
朱晶晶
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Tarim University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
    • C07C303/16—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by oxidation of thiols, sulfides, hydropolysulfides, or polysulfides with formation of sulfo or halosulfonyl groups
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    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
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    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/58—Preparation of carboxylic acid halides
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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Abstract

The present invention discloses the synthetic method of Gemini surface active agent, comprises the following steps：(1) synthesis of bromotetradecane acid methyl esters or bromotetradecane acid methyl esters；(2) synthesis of potassium xanthate；(3) synthesis of intermediate I；(4) synthesis of intermediate II.The Gemini surface active agent that the method for the present invention is prepared, critical micelle concentration and surface tension are all smaller, there is good application prospect.

Description

The synthetic method of Gemini surface active agent
Technical field
The present invention relates to the preparation of surfactant.More particularly, to a kind of synthetic method of Gemini surface active agent.
Background technology
Surfactant caused self-organizing behavior and reduction aqueous solution surface tension due to molecule dissymmetrical structure Ability, making it, all tool has been widely used and important meaning in scientific research and production application.Reduce surfactant parent Electrostatic and hydrated sheath repulsion between head base, promote it to tend to more be closely spaced in self-organizing structures, will effectively carry Its high surface-active, such as：When surfactant is in loose arrangement in air liquid interface, due to the inclination of carbochain on interface Caused some methylene (rather than methyl of carbochain end group) occupy the area towards air side；If surface-active Agent mainly will be made up of in close upright arrangement in air liquid interface towards air side the methyl end groups of its carbochain, be put into practice Show that the latter reduces the surface tension of water to a greater extent.Because surfactant is in industrial and agricultural production and daily life Significant role is played, how to improve its surface-active turns into the problem that application study is paid close attention to all the time.Conventionally by physics Method (such as improves solution temperature to reduce the electrostatic between surfactant hydrophilic head base (such as addition inorganic salts) and hydrated sheath repulsion Degree), (such as positive/negative ionic surface active agent is answered for the interaction that is promoted using the attraction between surfactant head group between the two With).However, these physical methods are there is also limitation, such as compounding of positive/negative ionic surface active agent, although to a certain degree On improve the surface-active of solution, but being electrically neutralized due to 1: 1 positive/negative ionic surface active agent ion head base, destroy The aqueous stability of mixed composition and easily produce precipitation, which has limited their popularization and application.Find overcoming method One of trial is the embedded polyoxyethylene chain on positive/negative ionic surface active agent, is allowed to hydrophily enhancing, but this can not keep away again Bring the repulsion side effect of oxyethylene group group hydrated sheath into exempting from.
But change made above, do not made a breakthrough on molecular structure, thus exploration has high surface Novel surfactant be always heat subject.Live on the Gemini surfaces that surfactant of new generation is seriously described as by Rosen Property agent achieves breakthrough on molecular structure, and two ion head bases are connected by spacer group by chemical bond, are thereby resulted in Two surfactant monomer ions closely connect, and cause its hydrocarbon interchain to be more prone to strong interaction, that is, strengthen The hydrophobic binding power of hydrocarbon interchain, and the reprimand tendency between ion head base is limited by chemical bond force and is weakened severely, therefore Gemini surface active has higher surface-active than conventional surfactant.Meanwhile two chamical binding between head base Connect and do not destroy its hydrophily, so as to be provided the foundation for the extensive use of Gemini surface active.Exactly, due to Gemini tables Face activating agent has excellent property, and people just constantly explore and synthesized, research and development.
The content of the invention
It is an object of the present invention to provide a kind of synthetic method of Gemini surface active agent, obtained surface-active is more It is good.
To reach above-mentioned purpose, the present invention uses following technical proposals：
The synthetic method of Gemini surface active agent, comprises the following steps：
(1) synthesis of bromotetradecane acetoacetic ester or bromotetradecane acid methyl esters；
(2) synthesis of potassium xanthate；
(3) synthesis of intermediate I；
(4) synthesis of intermediate II；
(5) synthesis of Gemini surface active agent.
The synthetic method of above-mentioned Gemini surface active agent, in step (1)：0.1mol is added into three-necked bottle 【22.837g】Tetradecanoic acid, the agitation and dropping 0.125mol at 60 DEG C【14.71g】Thionyl chloride, 2h is added dropwise, is added dropwise After continue react 1h, heating boil off excessive thionyl chloride；Add 1.2mmol【0.305g】Iodine, stirred at 85~90 DEG C 0.12mol is added dropwise【19.176g】Bromine simple substance, continue after dripping off react 1h, then at 55 DEG C be added dropwise 0.27mol anhydrous second Alcohol or absolute methanol, continue to stir, flowed back 1h, and 32mL water and 2.9mmol are added after being cooled to room temperature【0.458g】Na2S2O3, Organic layer is washed, then uses anhydrous Na2SO4It is evaporated under reduced pressure after drying, pillar layer separation, eluant, eluent is petroleum ether and ethyl acetate, stone The volume ratio of oily ether and ethyl acetate is 30:1, obtain colourless liquid, as bromotetradecane acetoacetic ester or bromotetradecane acid Methyl esters.
The synthetic method of above-mentioned Gemini surface active agent, in step (2)：Add 6mL's into 150mL round-bottomed flask CS2With the ethanol that 50mL mass fractions are 95wt%, it is water-soluble to add the KOH that 20mL concentration is 5mol/L while stirring in ice bath Liquid, continue to stir 1.5h after adding, be spin-dried for solvent, potassium xanthate is recrystallized to obtain with absolute ethyl alcohol.
The synthetic method of above-mentioned Gemini surface active agent, in step (3)：40mL is added in 100mL round-bottomed flask Acetone, 10mmol bromotetradecane acetoacetic ester or bromotetradecane acid methyl esters are added, round-bottomed flask is placed in ice bath, point Criticize and add potassium xanthate 11mmol altogether, 4h is stirred at room temperature after adding, is spin-dried for, add water and dichloromethane, liquid separation, collect organic phase, Aqueous phase is extracted with dichloromethane, merges organic phase, washing, saturated common salt washing, magnesium sulfate drying, pillar layer separation；Eluant, eluent For petroleum ether and ethyl acetate, the volume ratio of petroleum ether and ethyl acetate is 10:1, obtain pale yellowish oil liquid.
The synthetic method of above-mentioned Gemini surface active agent, in step (4)：In 50mL three-necked bottle plus among 8mmol Body I, vacuum nitrogen gas, 4mL 1,2- dichloroethanes is injected into, reinjects 16mmol 1- decene, oil bath heating, at 85 DEG C After lower backflow 10min；60mg lauroyl peroxides are first added, nitrogen protection reaction, TLC detection reactions, were added every 1 hour 60mg lauroyl peroxide, reaction in six hours terminate, and are spin-dried for solvent, pillar layer separation；Eluant, eluent is petroleum ether and acetic acid second The volume ratio of ester, petroleum ether and ethyl acetate is 200:1, obtain pale yellowish oil liquid.
The synthetic method of above-mentioned Gemini surface active agent, add five oxidations two simultaneously when adding lauroyl peroxide every time Vanadium, the addition of vanadic anhydride are 1-1.5 times of the amount of lauroyl peroxide material.
The synthetic method of above-mentioned Gemini surface active agent, in step (5)：15mL mass is added in 100mL flask Fraction is 98wt% formic acid, and it is 30wt%H that 10mL mass fractions, which are added dropwise,2O2, 1h is stirred at room temperature, is then slowly added dropwise in 3mmol Mesosome II, 2h is reacted at room temperature, then 65 DEG C of reactions overnight, remove solvent under reduced pressure at 65 DEG C and obtained corresponding to Gemini surface active agent Acid, the amount ratio of acid and the material of sodium hydroxide as corresponding to Gemini surface active agent is 1:2 addition sodium hydroxides make acid be changed into salt, Produce Gemini surface active agent.
Beneficial effects of the present invention are as follows：The Gemini surface active agent that the method for the present invention is prepared, critical micell are dense Degree and surface tension are all smaller, there is good application prospect.
Embodiment
Embodiment 1
The synthetic method of Gemini surface active agent, comprises the following steps：
(1) synthesis of bromotetradecane acetoacetic ester；
0.1mol tetradecanoic acid is added into three-necked bottle, the agitation and dropping 0.125mol thionyl chlorides at 60 DEG C, is added dropwise 2h, continue to react 1h, heating boils off excessive thionyl chloride；Add 1.2mmol iodine, the agitation and dropping at 85~90 DEG C 0.12mol bromine simple substance, continue to react 1h after dripping off, 0.27mol absolute ethyl alcohol be then added dropwise at 55 DEG C, continues to stir, Flowed back 1h, and 32mL water and 2.9mmol Na are added after being cooled to room temperature2S2O3, organic layer washing, then use anhydrous Na2SO4After drying It is evaporated under reduced pressure, pillar layer separation, chromatographic column is silicagel column, and eluant, eluent is petroleum ether and ethyl acetate, petroleum ether and ethyl acetate Volume ratio be 30:1 (target product purity can be caused to reach more than 98%), obtain colourless liquid, as bromotetradecane Acetoacetic ester, yield 87.3%.
(2) compound shown in formula 1 --- the synthesis of potassium xanthate；
6mL CS is added into 150mL round-bottomed flask2Ethanol with 50mL mass fractions for 95wt%, in ice bath The KOH aqueous solution that 20mL concentration is 5mol/L is added while stirring, is continued to stir 1.5h after adding, solvent is spin-dried for, with anhydrous second Alcohol recrystallizes to obtain compound --- potassium xanthate shown in formula 1, yield 90%.
(3) compound shown in formula 2 --- the synthesis of intermediate I；
40mL acetone is added in 100mL round-bottomed flask, 10mmol bromotetradecane acetoacetic ester is added, by round bottom Flask is placed in ice bath, adds potassium xanthate 11mmol altogether in batches, 4h is stirred at room temperature after adding, is spin-dried for, add water and dichloromethane, Liquid separation, organic phase is collected, aqueous phase is extracted with dichloromethane, merges organic phase, washing, saturated common salt washing, magnesium sulfate drying, post Chromatographic isolation；Chromatographic column is silicagel column, and eluant, eluent is petroleum ether and ethyl acetate, and the volume ratio of petroleum ether and ethyl acetate is 10:1 (target product purity can be caused to reach more than 98%), obtain pale yellowish oil liquid, yield 84.3%.
(4) compound shown in formula 3 --- the synthesis of intermediate II；
In 50mL three-necked bottle plus 8mmol intermediate Is, vacuum nitrogen gas, 4mL 1,2- dichloroethanes is injected into, Reinject 16mmol 1- decene, oil bath heating, at 85 DEG C after backflow 10min；First add 60mg lauroyl peroxide ( Whole vanadic anhydride raw materials are added when adding lauroyl peroxide for the first time simultaneously, the addition of vanadic anhydride in the present embodiment Measure the amount of the lauroyl peroxide total material for addition 1.5 times), nitrogen protection reaction, TLC detection reactions, every 1 hour again 60mg lauroyl peroxide is added, reaction in six hours terminates, and is spin-dried for solvent, pillar layer separation；Chromatographic column is silicagel column, elution Agent is petroleum ether and ethyl acetate, and the volume ratio of petroleum ether and ethyl acetate is 200:1 (can cause target product purity to reach More than 98%) pale yellowish oil liquid, yield 86.4%, are obtained.
(5) compound shown in formula 4 --- the synthesis of acid and Gemini surface active agent corresponding to Gemini surface active agent；
The formic acid that 15mL mass fractions are 98wt% is added in 100mL flask, 10mLH is added dropwise2O2Mass fraction is 30wt% hydrogen peroxide, is stirred at room temperature 1h, and 3mmol intermediate IIs are then slowly added dropwise, and reacts at room temperature 2h, then 65 DEG C were reacted At night, remove solvent under reduced pressure at 65 DEG C and obtain sour corresponding to Gemini surface active agent, yield 75%；It is corresponding by Gemini surface active agent Acid and the amount ratio of the material of sodium hydroxide be 1:2 addition sodium hydroxides make acid be changed into salt, produce Gemini surface active agent.
Embodiment 2
The synthetic method of Gemini surface active agent, comprises the following steps：
(1) synthesis of bromotetradecane acetoacetic ester；
0.1mol tetradecanoic acid is added into three-necked bottle, the agitation and dropping 0.125mol thionyl chlorides at 60 DEG C, is added dropwise 2h, continue to react 1h, heating boils off excessive thionyl chloride；Add 1.2mmol iodine, the agitation and dropping at 85~90 DEG C 0.12mol bromine simple substance, continue to react 1h after dripping off, 0.27mol absolute ethyl alcohol be then added dropwise at 55 DEG C, continues to stir, Flowed back 1h, and 32mL water and 2.9mmol Na are added after being cooled to room temperature2S2O3, organic layer washing, then use anhydrous Na2SO4After drying It is evaporated under reduced pressure, pillar layer separation, chromatographic column is silicagel column, and eluant, eluent is petroleum ether and ethyl acetate, petroleum ether and ethyl acetate Volume ratio be 30:1 (target product purity can be caused to reach more than 98%), obtain colourless liquid, as bromotetradecane Acetoacetic ester, yield 87.3%.
(2) compound shown in formula 1 --- the synthesis of potassium xanthate；
6mL CS is added into 150mL round-bottomed flask2Ethanol with 50mL mass fractions for 95wt%, in ice bath The KOH aqueous solution that 20mL concentration is 5mol/L is added while stirring, is continued to stir 1.5h after adding, solvent is spin-dried for, with anhydrous second Alcohol recrystallizes to obtain compound --- potassium xanthate shown in formula 1, yield 90%.
(3) compound shown in formula 2 --- the synthesis of intermediate I；
40mL acetone is added in 100mL round-bottomed flask, 10mmol bromotetradecane acetoacetic ester is added, by round bottom Flask is placed in ice bath, adds potassium xanthate 11mmol altogether in batches, 4h is stirred at room temperature after adding, is spin-dried for, add water and dichloromethane, Liquid separation, organic phase is collected, aqueous phase is extracted with dichloromethane, merges organic phase, washing, saturated common salt washing, magnesium sulfate drying, post Chromatographic isolation；Chromatographic column is silicagel column, and eluant, eluent is petroleum ether and ethyl acetate, and the volume ratio of petroleum ether and ethyl acetate is 10:1 (target product purity can be caused to reach more than 98%), obtain pale yellowish oil liquid, yield 84.3%.
(4) compound shown in formula 3 --- the synthesis of intermediate II；
In 50mL three-necked bottle plus 8mmol intermediate Is, vacuum nitrogen gas, 4mL 1,2- dichloroethanes is injected into, Reinject 16mmol 1- decene, oil bath heating, at 85 DEG C after backflow 10min；First add 60mg lauroyl peroxide ( Vanadic anhydride is added when adding lauroyl peroxide every time simultaneously, and the addition of vanadic anhydride is every every time in the present embodiment 1.2 times of the amount of the lauroyl peroxide material of secondary addition), nitrogen protection reaction, TLC detection reactions, added every 1 hour 60mg lauroyl peroxide, reaction in six hours terminate, and are spin-dried for solvent, pillar layer separation；Chromatographic column is silicagel column, and eluant, eluent is The volume ratio of petroleum ether and ethyl acetate, petroleum ether and ethyl acetate is 200:1 (can cause target product purity to reach 98% More than), obtain pale yellowish oil liquid, yield 94.7%.
(5) compound shown in formula 4 --- the synthesis of acid and Gemini surface active agent corresponding to Gemini surface active agent；
The formic acid that 15mL mass fractions are 98wt% is added in 100mL flask, 10mL H are added dropwise2O2Mass fraction is 30wt% hydrogen peroxide, is stirred at room temperature 1h, and 3mmol intermediate IIs are then slowly added dropwise, and reacts at room temperature 2h, then 65 DEG C were reacted At night, remove solvent under reduced pressure at 65 DEG C and obtain sour corresponding to Gemini surface active agent, yield 75%；It is corresponding by Gemini surface active agent Acid and the amount ratio of the material of sodium hydroxide be 1:2 addition sodium hydroxides make acid be changed into salt, produce Gemini surface active agent.
Embodiment 3
The synthetic method of Gemini surface active agent, comprises the following steps：
(1) synthesis of bromotetradecane acetoacetic ester；
0.1mol tetradecanoic acid is added into three-necked bottle, the agitation and dropping 0.125mol thionyl chlorides at 60 DEG C, is added dropwise 2h, continue to react 1h, heating boils off excessive thionyl chloride；Add 1.2mmol iodine, the agitation and dropping at 85~90 DEG C 0.12mol bromine simple substance, continue to react 1h after dripping off, 0.27mol absolute ethyl alcohol be then added dropwise at 55 DEG C, continues to stir, Flowed back 1h, and 32mL water and 2.9mmol Na are added after being cooled to room temperature2S2O3, organic layer washing, then use anhydrous Na2SO4After drying It is evaporated under reduced pressure, pillar layer separation, chromatographic column is silicagel column, and eluant, eluent is petroleum ether and ethyl acetate, petroleum ether and ethyl acetate Volume ratio be 30:1 (target product purity can be caused to reach more than 98%), obtain colourless liquid, as bromotetradecane Acetoacetic ester, yield 87.3%.
(2) compound shown in formula 1 --- the synthesis of potassium xanthate；
6mL CS is added into 150mL round-bottomed flask2Ethanol with 50mL mass fractions for 95wt%, in ice bath The KOH aqueous solution that 20mL concentration is 5mol/L is added while stirring, is continued to stir 1.5h after adding, solvent is spin-dried for, with anhydrous second Alcohol recrystallizes to obtain compound --- potassium xanthate shown in formula 1, yield 90%.
(3) compound shown in formula 2 --- the synthesis of intermediate I；
40mL acetone is added in 100mL round-bottomed flask, 10mmol bromotetradecane acetoacetic ester is added, by round bottom Flask is placed in ice bath, adds potassium xanthate 11mmol altogether in batches, 4h is stirred at room temperature after adding, is spin-dried for, add water and dichloromethane, Liquid separation, organic phase is collected, aqueous phase is extracted with dichloromethane, merges organic phase, washing, saturated common salt washing, magnesium sulfate drying, post Chromatographic isolation；Chromatographic column is silicagel column, and eluant, eluent is petroleum ether and ethyl acetate, and the volume ratio of petroleum ether and ethyl acetate is 10:1 (target product purity can be caused to reach more than 98%), obtain pale yellowish oil liquid, yield 84.3%.
(4) compound shown in formula 3 --- the synthesis of intermediate II；
In 50mL three-necked bottle plus 8mmol intermediate Is, vacuum nitrogen gas, 4mL 1,2- dichloroethanes is injected into, Reinject 16mmol 1- decene, oil bath heating, at 85 DEG C after backflow 10min；First add 60mg lauroyl peroxide, nitrogen Gas shielded reacts, and TLC detection reactions, every the lauroyl peroxide that 1 hour adds 60mg, reaction in six hours terminates, is spin-dried for Solvent, pillar layer separation；Chromatographic column is silicagel column, and eluant, eluent is the body of petroleum ether and ethyl acetate, petroleum ether and ethyl acetate Product is than being 200:1 (target product purity can be caused to reach more than 98%), obtain pale yellowish oil liquid, yield 78.3%.
(5) compound shown in formula 4 --- the synthesis of acid and Gemini surface active agent corresponding to Gemini surface active agent；
The formic acid that 15mL mass fractions are 98wt% is added in 100mL flask, 10mLH is added dropwise2O2Mass fraction is 30wt% hydrogen peroxide, is stirred at room temperature 1h, and 3mmol intermediate IIs are then slowly added dropwise, and reacts at room temperature 2h, then 65 DEG C were reacted At night, remove solvent under reduced pressure at 65 DEG C and obtain sour corresponding to Gemini surface active agent, yield 75%；It is corresponding by Gemini surface active agent Acid and the amount ratio of the material of sodium hydroxide be 1:2 addition sodium hydroxides make acid be changed into salt, produce Gemini surface active agent.
The critical micelle concentration of Gemini surface active agent in embodiment 1-3 is determined using electrical conductivity method.Implementation is taken respectively Gemini surface active agent in example 1-3, each 100mL of solution of various concentrations gradient is prepared with conductivity water, uses conductivity meter respectively Determine the electrical conductivity of each solution of preparation respectively from dilute to dense, the electrical conductivity of water used in measure, draw the pass of electrical conductivity and concentration System's figure, finds out the critical micelle concentration of each nonionic Gemini surface active agent, and the Gemini surface active agent in embodiment 1-3 faces Boundary's micellar concentration is as shown in table 1 below：
The surface tension of Gemini surface active agent in embodiment 1-3 will be prepared using the around-France measure of electricity in embodiment 1-3 Obtained Gemini surface active agent is configured to the solution of same concentrations, suspension ring is slowly immersed inside solution, and suspension ring are slowly past Above carry, liquid level relative drop, make suspension ring that one section of fluid column be formed below, and finally separated with suspension ring, obtain the surface of a solution Power, the surface tension of Gemini surface active agent prepared by embodiment 1-3 are as shown in table 2 below：
Embodiment 1 Embodiment 2 Embodiment 3
Surface tension 12.6mN/m 12.4mN/m 13.2mN/m
Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not pair The restriction of embodiments of the present invention, for those of ordinary skill in the field, may be used also on the basis of the above description To make other changes in different forms, all embodiments can not be exhaustive here, it is every to belong to this hair Row of the obvious changes or variations that bright technical scheme is extended out still in protection scope of the present invention.

Claims (1)

1. the synthetic method of Gemini surface active agent, comprises the following steps：
(1) synthesis of bromotetradecane acetoacetic ester；
0.1mol tetradecanoic acid is added into three-necked bottle, the agitation and dropping 0.125mol thionyl chlorides at 60 DEG C, 2h is added dropwise, after Continuous reaction 1h, heating boil off excessive thionyl chloride；Add 1.2mmol iodine, the agitation and dropping 0.12mol at 85~90 DEG C Bromine simple substance, continue to react 1h after dripping off, 0.27mol absolute ethyl alcohol is then added dropwise at 55 DEG C, continues to stir, flow back 1h, cold But to addition 32mL water and 2.9mmol Na after room temperature2S2O3, organic layer washing, then use anhydrous Na2SO4It is evaporated under reduced pressure after drying, Pillar layer separation, chromatographic column are silicagel column, and eluant, eluent is petroleum ether and ethyl acetate, and the volume ratio of petroleum ether and ethyl acetate is 30:1, obtain colourless liquid, as bromotetradecane acetoacetic ester；
(2) compound shown in formula 1 --- the synthesis of potassium xanthate；
6mL CS is added into 150mL round-bottomed flask2With the ethanol that 50mL mass fractions are 95wt%, side is stirred in ice bath Side adds the KOH aqueous solution that 20mL concentration is 5mol/L, continues to stir 1.5h after adding, is spin-dried for solvent, is tied again with absolute ethyl alcohol It is brilliant to obtain compound --- potassium xanthate shown in formula 1；
(3) compound shown in formula 2 --- the synthesis of intermediate I；
40mL acetone is added in 100mL round-bottomed flask, 10mmol bromotetradecane acetoacetic ester is added, by round-bottomed flask It is placed in ice bath, adds potassium xanthate 11mmol altogether in batches, 4h is stirred at room temperature after adding, is spin-dried for, adds water and dichloromethane, divides Liquid, organic phase is collected, aqueous phase is extracted with dichloromethane, merges organic phase, washing, saturated common salt washing, magnesium sulfate drying, post color Spectrum separation；Chromatographic column is silicagel column, and eluant, eluent is petroleum ether and ethyl acetate, and the volume ratio of petroleum ether and ethyl acetate is 10: 1, obtain pale yellowish oil liquid；
(4) compound shown in formula 3 --- the synthesis of intermediate II；
Add 8mmol intermediate Is in 50mL three-necked bottle, vacuum nitrogen gas is injected into 4mL 1,2- dichloroethanes, then notes Enter 16mmol 1- decene, oil bath heating, at 85 DEG C after backflow 10min；60mg lauroyl peroxide is first added, nitrogen is protected Shield reaction, TLC detection reactions, every the lauroyl peroxide that 1 hour adds 60mg, reaction in six hours terminates, and is spin-dried for solvent, Pillar layer separation；Chromatographic column is silicagel column, and eluant, eluent is petroleum ether and ethyl acetate, and the volume ratio of petroleum ether and ethyl acetate is 200:1, obtain pale yellowish oil liquid；
(5) compound shown in formula 4 --- the synthesis of acid and Gemini surface active agent corresponding to Gemini surface active agent；
The formic acid that 15mL mass fractions are 98wt% is added in 100mL flask, 10mLH is added dropwise2O2Mass fraction is 30wt% Hydrogen peroxide, 1h is stirred at room temperature, is then slowly added dropwise 3mmol intermediate IIs, reacts at room temperature 2h, then 65 DEG C of reactions overnight, 65 DEG C remove solvent under reduced pressure and obtain acid corresponding to Gemini surface active agent；Acid and sodium hydroxide as corresponding to Gemini surface active agent Material amount ratio be 1:2 addition sodium hydroxides make acid be changed into salt, produce Gemini surface active agent.
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