CN111875522B - Tetraphenyl vinyl dihexyl sulfonic acid sodium salt surfactant as well as preparation method and application thereof - Google Patents
Tetraphenyl vinyl dihexyl sulfonic acid sodium salt surfactant as well as preparation method and application thereof Download PDFInfo
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- CN111875522B CN111875522B CN202010426997.2A CN202010426997A CN111875522B CN 111875522 B CN111875522 B CN 111875522B CN 202010426997 A CN202010426997 A CN 202010426997A CN 111875522 B CN111875522 B CN 111875522B
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- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/07—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton
- C07C309/09—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing etherified hydroxy groups bound to the carbon skeleton
- C07C309/11—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing etherified hydroxy groups bound to the carbon skeleton with the oxygen atom of at least one of the etherified hydroxy groups further bound to a carbon atom of a six-membered aromatic ring
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- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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Abstract
The invention discloses a tetraphenyl vinyl dihexyl sulfonic acid sodium salt surfactant, and a preparation method and application thereof. The preparation method comprises the following steps: (1) Modifying 4-aminobenzophenone by using bromine-substituted long-chain alkane; (2) Reacting the product obtained in the step (1) with 4-hydroxybenzophenone to obtain amino-modified tetraphenylethylene with para positions respectively substituted by hydroxyl and a long alkyl chain; (3) Salifying the product obtained in the step (2) to obtain the sodium tetraphenylyl dihexyl sulfonate. The sodium tetraphenyl dihexyl sulfonate has surfactant property, can form microemulsion in solvents such as isooctane and the like, and can be applied to double-phase reaction, liquid extraction, biomolecule stabilization and synthesis of soft template nano materials. The microemulsion obtained by the method has large hydrophobic interface cage area and high efficiency of extracting the microemulsion, and opens up a new path for developing the microemulsion with the hydrophobic interface cage.
Description
Technical Field
The invention belongs to the technical field of microemulsion composition materials, and particularly relates to a tetraphenyl vinyl dihexyl sulfonic acid sodium salt surfactant and a preparation method thereof.
Background
Water-in-oil (w/o) microemulsions are optically clear solutions with monodisperse, nanoscale water pools in the oil phase. Pools in microemulsions have been widely used for biphasic reactions, liquid extraction, biomolecule stabilization and soft template nanomaterial synthesis. Some water molecules in the pool may penetrate to the hydrophobic interface region between the hydrophobic tails of the surfactant, resulting in partial hydration. However, since the confinement cavity of the hydrophobic interface region is small in current microemulsions, there are few applications of microemulsions based on hydrophobic interface regions. Therefore, there is an urgent need to expand the confined cavity of the hydrophobic interfacial region in microemulsion to expand its potential application in the field of microemulsion.
Cage molecules/assemblies with three-dimensional (3D) porous cavities of different sizes and shapes are one of the most important supramolecular hosts. Currently, various cage-type molecules/assemblies with large cavities can be fabricated by either directly using rigid non-coplanar units as building blocks or incorporating non-coplanar units into building blocks. Tetraphenylethylene (TPE) has an intrinsic propeller-like structure (4 highly symmetric and twisted benzene rings) and 4 symmetric reaction sites. The inherent properties of TPEs make them an excellent building block for the fabrication of various 3D cage-type molecules/assemblies. Currently, 3D cavities in TPE-based cage molecules/assemblies have been used to assemble various guest molecules for gas adsorption and separation, drug encapsulation and release, phase transfer catalysis, and optical applications. Therefore, the incorporation of propeller-like TPE into the double tail surfactant backbone is expected to construct a new microemulsion system as well as a cage-type hydrophobic interface region.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a tetraphenyl vinyl dihexyl sulfonic acid sodium salt surfactant, and a preparation method and application thereof. The microemulsion formed by the sodium tetraphenyl vinyl dihexyl sulfonate in solvents such as isooctane has large hydrophobic interface cage area and high microemulsion extraction efficiency, opens up a new path for developing the microemulsion with the hydrophobic interface cages and provides wide prospect for the application of the microemulsion.
The structural formula of the tetraphenyl vinyl dihexyl sulfonic acid sodium salt surfactant is as follows:
the preparation method of the tetraphenyl vinyl dihexyl sulfonic acid sodium salt surfactant comprises the following steps: (1) Modifying 4-aminobenzophenone by using bromine-substituted long-chain alkane; (2) Reacting the product obtained in the step (1) with 4-hydroxybenzophenone to obtain amino-modified tetraphenylethylene with para positions respectively substituted by hydroxyl and a long alkyl chain; (3) Salifying the product obtained in the step (2) to obtain tetraphenyl vinyl dihexyl sulfonic acid sodium salt.
The specific operation steps of the step (1) are as follows: vacuumizing a reaction device, introducing nitrogen for protection, firstly adding 4-aminobenzophenone and anhydrous tetrahydrofuran, then adding NaH at low temperature, heating the system to room temperature, then adding bromine-substituted long-chain alkane, reacting at room temperature for 12-36h, then adding ice water to react to remove redundant NaH, finally extracting with dichloromethane and water, removing water from an organic phase extraction liquid, removing the solvent by using a rotary evaporation method, and purifying the obtained crude product by using a silica gel column chromatography.
The molar ratio of the 4-aminobenzophenone to NaH is 1:3, and the molar ratio of the 4-aminobenzophenone to the bromine-substituted long-chain alkane is 1:6.
The specific operation steps of the step (2) are as follows: vacuumizing a reaction device, introducing nitrogen for protection, adding 4-hydroxybenzophenone and zinc powder, adding a product obtained in the step (1) dissolved in anhydrous tetrahydrofuran, and dropwise adding TiCl at low temperature 4 After the dropwise addition is finished, the temperature of the system is raised to room temperature, the reaction is continued for 10 to 20 hours after the temperature is slowly raised to 70 to 80 ℃ after the reaction is carried out for 0.5 to 1 hour, and after the reaction is finished, K is added 2 CO 3 Quenching the reaction solution, extracting with dichloromethane and water, removing water from the organic phase extract, removing the solvent by rotary evaporation, and purifying the crude product by silica gel column chromatography.
The molar ratio of the 4-hydroxybenzophenone to the zinc powder is 1 4 Is 1:2.
The specific operation steps of the step (3) are as follows: after the reaction device is vacuumized and nitrogen is introduced for protection, the product obtained in the step (2) and (CH) are added 3 ) 3 CONa, injecting solvent absolute ethyl alcohol, stirring at room temperature for 2-5h, then dropwise adding 1,4-butyl sultone, slowly raising the temperature to 70-80 ℃, reacting for 40-60h, and quenching the reaction by water after the reaction is finishedThe solvent was removed by rotary evaporation and the crude product was purified by silica gel column chromatography.
The product obtained in the step (2) is mixed with (CH) 3 ) 3 The molar ratio of CONa is 1:4, and the molar ratio of the product obtained in step (2) to 1,4-butanesultone is 1.2.
The eluent of the silica gel column chromatography in the steps (1) and (2) is a mixed solution of petroleum ether and ethyl acetate, wherein the volume ratio of the petroleum ether to the ethyl acetate is 10.
The eluent of the silica gel column chromatography in the step (3) is mixed solution of dichloromethane and methanol, wherein the volume ratio of the dichloromethane to the methanol is 8:1.
The microemulsion is prepared by the following steps: adding the tetraphenyl vinyl dihexyl sulfonic acid sodium salt surfactant prepared in the above way into an organic solvent, adding water and stirring to obtain the product. The organic solvent is isooctane.
The extracting agent is prepared by adding the prepared tetraphenyl vinyl dihexyl sulfonic acid sodium salt surfactant into an organic solvent, adding water and stirring to form a microemulsion.
Compared with the prior art, the invention has the following beneficial effects:
1. the tetraphenyl vinyl dihexyl sulfonic acid sodium salt surfactant is formed by covalently connecting tetraphenyl ethylene groups, two hexyl chains and an anionic sulfonate head group through a methoxybutyl spacer, and the molecule is not reported in the prior art.
2. The sodium tetraphenyl dihexyl sulfonate surfactant has the surfactant property, can form water-in-oil type microemulsion in solvents such as isooctane and the like, has a larger 3D cavity in a hydrophobic interface region, and can be applied to double-phase reaction, liquid extraction, biomolecule stabilization and synthesis of soft template nano materials.
Drawings
FIG. 1 shows the NMR spectrum of TPE-di-C6SS.
FIG. 2 is a MS plot of TPE-di-C6SS.
FIG. 3 is a size distribution plot of TPE-di-C6SS microemulsion.
FIG. 4 is a graph showing the effect of extraction of TPE-di-C6SS microemulsion.
FIG. 5 is an extraction efficiency-time curve for TPE-di-C6SS microemulsion.
Detailed Description
For a further understanding of the invention, reference will now be made to the following descriptions taken in conjunction with the accompanying drawings and specific examples. The embodiments of the present invention are not limited thereto.
Example 1: preparation of TPE-di-C6SS (sodium tetraphenylbehexylsulfonate)
(1) 1.225g (6.25 mmol) of 4-aminobenzophenone were weighed into a 100mL two-necked round bottom flask equipped with a stirring magneton, a rubber stopper was fitted to one of the flask openings, a double row pipe was connected to the other flask opening, a vacuum operation was started, and nitrogen was introduced, and these two operations were repeated 3 times. After addition of 37.5mL of anhydrous tetrahydrofuran solution, a cold environment was created by mixing ethyl acetate with liquid nitrogen, maintaining the temperature at-10 deg.C, adding 0.45g (18.75 mmol) of NaH, removing the ice bath unit and allowing the temperature to rise to room temperature, and adding 6.5g (37.5 mmol) of C dropwise 6 H 13 Br, stirred at room temperature for 24h. After the reaction is finished, adding ice water to react to remove excessive NaH, extracting with dichloromethane and a water system, collecting extract liquor in an organic phase, and using saturated NaCl solution and anhydrous MgSO 4 Removing water, and performing rotary evaporation to obtain crude product. The resulting crude product was purified by silica gel column chromatography eluting with petroleum ether/ethyl acetate (v/v = 10. 2.26g (5.38 mmol) of intermediate of formula (IV) are obtained as a yellow solid with a yield of 86%. By using 1 The intermediate of formula (IV) was characterized by H NMR and the specific data results are as follows:
1 H NMR(400MHz,CDCl 3 ,δ)：0.87-0.90(t,6H),1.25-1.33(m,12H),1.60-1.62(m,4H),3.31-3.34(t,4H),6.60-6.61(m,2H),7.42-7.44(m,2H),7.49-7.51(m,1H),7.71-7.72(m,2H),7.76-7.78(m,2H)。
(2)0.5g (2.5 mmol) of 4-hydroxybenzophenone and 1.64g (25 mmol) of zinc powder were weighed into a 100mL two-necked round-bottomed flask equipped with a stirring magneton, a rubber stopper was attached to one neck of the flask, a double row tube was attached to the other neck of the flask, a vacuum operation was started, and nitrogen was introduced, and these two operations were repeated 3 times. 1.05g (2.5 mmol) of the intermediate of formula (IV) are dissolved in 37.5mL of anhydrous tetrahydrofuran and introduced into a two-necked round-bottomed flask, a low temperature environment is created by mixing ethyl acetate with liquid nitrogen, the temperature is maintained at-10 ℃ and 2.36g (12.5 mmol) of TiCl are added dropwise 4 The ice bath device was removed and the temperature was allowed to rise to room temperature, after 0.5h reaction at room temperature, the temperature was slowly raised to 75 ℃ for 12h. After the reaction is complete, add 10% of K 2 CO 3 Quenching the solution, extracting with dichloromethane/water system, collecting the extract in organic phase, adding saturated NaCl solution and anhydrous MgSO 4 Removing water, and performing rotary evaporation to obtain crude product. The resulting crude product was purified by column chromatography on silica gel eluting with petroleum ether/ethyl acetate (v/v = 10. This gave 0.475g (1.8 mmol) of intermediate of formula (VI) as a yellow solid in 32% yield. By using 1 H NMR characterizes the intermediate of formula (VI) with the following data:
1 H NMR(400MHz,CDCl 3 ,δ)：0.87-0.90(t,6H),1.23-1.31(m,12H),1.48-1.55(m,4H),3.12-3.21(m,4H),6.30-6.37(m,2H),6.49-6.62(m,2H),6.74-6.96(m,4H),6.97-7.14(m,10H)。
(3) 0.725g (1.25 mmol) of the intermediate of formula (VI) and 0.475g (5 mmol) of (CH) are weighed out 3 ) 3 CONa, which was added to a 100mL two-necked round-bottomed flask equipped with a stirring magneton, was fitted with a rubber stopper at one bottle mouth and a double row pipe at the other bottle mouth, and vacuum operation was started and nitrogen gas was introduced, and these two operations were repeated three times. 18.75mL of absolute ethanol was added, the reaction was carried out at room temperature for 2 hours, 203.75mg (1.5 mmol) of 1,4-butanesultone was added dropwise, the temperature was slowly raised to 75 ℃ and the reaction was carried out under reflux for 48 hours. After the reaction is finishedAfter completion, the reaction was quenched with water and the crude product was obtained by rotary evaporation. The resulting crude product was purified by column chromatography on silica gel eluting with dichloromethane/methanol (v/v = 8:1). This gave 0.4g of the product of formula (I) as a yellow solid in 53% yield, designated TPE-di-C6SS. By using 1 The product of formula (I) was characterized by H NMR and the specific data results are as follows, as shown in figure 1:
1 H NMR(400MHz,DMSO-d 6 ,δ)：0.81-0.89(t,6H),1.19-1.27(m,12H),1.37-1.47(m,4H),1.64-1.76(m,4H),2.41(m,2H),3.06-3.21(m,4H),3.79-3.89(m,2H),6.28-6.39(m,2H),6.59-6.73(m,4H),6.75-7.17(m,12H)。
MS is shown in fig. 2: m/z =666.3621 ([ M-Na)] - Molecular formula C 42 H 52 NO 4 S, theoretical value 666.3623).
Application example 1 particle size distribution test of TPE-di-C6SS microemulsion
37.6mg of TPE-di-C6SS was dissolved in 10mL of isooctane to form a yellow cloudy solution. Addition of 18 μ L of water and stirring at room temperature for 8h produced an ω =20 TPE-di-C6SS pale yellow transparent microemulsion with an average diameter of droplets of about 8.4nm, as shown in figure 3.
Application example 2
And extracting 30 mu M of rhodamine B aqueous solution by using the TPE-di-C6SS microemulsion prepared in the application example 1. With the increase of time, the color of the lower layer of rhodamine B aqueous solution gradually becomes lighter, the color of the upper layer of microemulsion gradually becomes red, and the lower layer of rhodamine B is extracted into the microemulsion, as shown in fig. 4. The rule of the extraction efficiency of the TPE-di-C6SS microemulsion on rhodamine B along with the change of the extraction time is shown in figure 5.
Claims (1)
1. A method for extracting rhodamine B is characterized by comprising the following specific operations:
dissolving a tetraphenyl vinyl dihexyl sulfonic acid sodium salt surfactant of 37.6mg in isooctane of 10mL to form a yellow turbid solution; adding 18 mu L of water and stirring at room temperature for 8h to prepare omega =20 tetraphenyl vinyl dihexyl sulfonic acid sodium salt surfactant light yellow transparent microemulsion, wherein the average diameter of droplets of the microemulsion is 8.4 nm; extracting a 30 mu M rhodamine B aqueous solution by using the microemulsion, wherein the color of the lower rhodamine B aqueous solution gradually becomes lighter and the color of the upper microemulsion gradually becomes red along with the increase of time, which shows that the lower rhodamine B is extracted into the microemulsion;
the structural formula of the tetraphenyl vinyl dihexyl sulfonic acid sodium salt surfactant is as follows:
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