CN110615770B - CO useful for Click reactions2Responsive compounds and methods of making the same - Google Patents

Abstract

The CO provided by the invention can be used for Click reaction₂A responsive compound and a method of making the same comprising the steps of: (1) adding cyanuric chloride and deionized water into a reaction bottle, and stirring in an ice-water bath until the cyanuric chloride and the deionized water are uniformly dispersed; (2) dropwise adding N, N-dimethyl alkyl diamine into the mixed solution, heating to 58-65 ℃ after dropwise adding, and continuing to react for 4-8 h; (3) dropwise adding propargylamine into the reaction liquid, gradually heating to 80-95 ℃, and continuing to react for 4-8 hours; (4) adding a sodium hydroxide solution into the reaction solution, and continuing to react for 0.5-1 h; (5) removing the solvent in the reaction solution, and purifying the product. The compound can be introduced to the surface or special part of a material through a Click reaction to endow the material with CO₂Stimulus response performance.

Description

CO useful for Click reactions2Responsive compounds and methods of making the same

Technical Field

The invention belongs to the field of stimulus responsive materials, and particularly relates to CO for Click reaction₂A responsive compound.

Description of the background

In recent years, research on smart materials has gained widespread attention. The intelligent material is one of the highest targets of material research, is a hotspot of research of various branch subjects in the field of materials at present, and is considered as a core technology for solving key problems of sustainable development, human health and the like in the future. By smart materials are meant new materials with self-perception, recognition and response capabilities like life height. It is not a single material but a complex material system, the core of which is the recognition and response to external changes.

The environmental stimulus response material is the core for constructing a smart material system, and is a material of which certain physical or chemical properties change correspondingly under the stimulus of environmental factors. Such materials recognize and respond to one or more stimuli and typically contain functional groups that are very sensitive to environmental stimuli. When these stimuli change, the structure (shape, morphology, etc.) and properties (such as phase, surface energy, charge distribution, reaction rate, solubility, transparency or surface wettability, etc.) of the material itself change, and these changes can be further converted into signals such as optical, electrical, thermal and stress changes. By utilizing the special environment stimulus response function of the materials, a higher-grade intelligent material system can be constructed, and special functions which are not possessed by the traditional materials, such as drug delivery and controllable release, disease diagnosis, an intelligent optical system, an intelligent surface, intelligent fiber fabric, biomass separation, bionic performance, biochemical sensors and the like, can be developed.

At present, a great deal of research has been conducted on stimuli-responsive materials that are sensitive to light, temperature, pH, ions and ionic strength, electric fields, magnetic fields, stress, and some particular chemical substances. In recent years, CO₂Has gained a great deal of attention as a biocompatible gas stimulus, and has been successfully used for preparing materials such as 'switch' type solvents, solutions, fluids, self-assembled microstructures, smart surfaces and the like. Tertiary amines are typically CO₂Responsive groups, with CO in a humid environment₂The ammonium bicarbonate salt is generated by the reaction. When the temperature rises, the ammonium bicarbonate can be decomposed again to release CO₂Reverting to tertiary amine (Lin, S.; Theato, P., CO.)₂Reactive polymers Macromol Rapid Comm 2013,34, 1118-1133.). Before and after the reaction, the hydrophilicity, the charge property and the like of the groups can be obviously changed, and the change of the properties such as the shape, the strength, the volume and the like of the material can be further triggered, so that the material can be endowed with special stimulus response performance (Jessop, P.G.; Mercer, S.M.; Heldebrant, D.J., CO)₂-triggered switchable solvents,surfactants,and other materials.EnergEnviron Sci 2012,5,7240-7253)。

In the preparation of CO₂When responding to the material, the material is required to beSome special parts of the functional group are introduced with functional groups with response functions, which often needs fine design and synthesis, and has large workload, low efficiency and high cost. Click Chemistry (Click Chemistry) provides a new approach to solving this problem. Click chemistry is the splicing of small units to complete the chemical synthesis of various molecules quickly and reliably, and has the characteristics of simplicity, quickness and high efficiency. The Click reaction can be used for quickly and efficiently introducing functional groups with special properties into special positions of the material, particularly the surface of the material. Research into the preparation of tertiary amine compounds useful in the Click reaction, which will have CO₂The responsive tertiary amine group is quickly and efficiently introduced into a target material to endow the material with CO₂A response characteristic. CO thus usable for Click reaction₂The study of responsive compounds is of great significance.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide CO which can be used for Click reaction₂Responsive compounds and methods of making the same.

In order to achieve the purpose, the invention comprises the following steps: will have a typical CO₂The tertiary amine group of the response characteristic is introduced into the compound of which the terminal group is alkynyl. The terminal alkyne can undergo a cyclization reaction with an azide group under the catalysis of Cu (I), namely a Huisgen1, 3-dipolar cycloaddition reaction catalyzed by Cu (I), which is a typical Click reaction. Thus, tertiary amine groups can be "grafted" directly onto the surface of other substances or materials by this Click reaction, giving them CO₂A stimulus response characteristic.

Based on the above concept, the present invention provides CO useful for Click reaction₂A method for the preparation of a responsive compound,

CO useful for Click reactions₂The response compound is characterized by having the following structural general formula,

wherein a is 1-5, b is 1-5, and a and b are integers.

The class of CO that can be used in the Click reaction₂A method of preparing a responsive compound comprising the steps of:

(1) adding cyanuric chloride and deionized water into a reaction vessel, and stirring in an ice-water bath until the cyanuric chloride and the deionized water are uniformly dispersed (for a plurality of minutes);

(2) dropwise adding N, N-dimethyl alkyl diamine into the reaction liquid obtained in the step (1), and after the dropwise adding is completed, heating to 58-65 ℃ to continue reacting for 4-8 hours;

(3) dropwise adding propargylamine into the reaction liquid obtained in the step (2), gradually heating to 80-95 ℃, and continuing to react for 4-8 hours;

(4) adding a sodium hydroxide solution into the reaction liquid obtained in the step (3), and continuously reacting for 0.5-1 h;

(5) and (4) removing the solvent from the reaction liquid obtained in the step (4) and purifying the product.

Further, the purification method in the step (5) is as follows: removing the solvent in the reaction solution, dissolving the product with dichloromethane, filtering to collect the solution (filtrate), adding anhydrous sodium sulfate into the solution, drying for 12-24 h, filtering, and removing the solvent to obtain a crude product; dissolving the obtained crude product in dichloromethane, adding petroleum ether, fully oscillating, standing for precipitation, collecting solids, dissolving the solids in dichloromethane again, repeating the operation for 2-3 times (repeating dichloromethane to dissolve the solids, adding petroleum ether, violently oscillating, standing for precipitation, filtering to collect the solids), and freeze-drying the collected solids for 12-24 hours to obtain the CO for Click reaction₂A responsive compound.

Further, the mass ratio of the cyanuric chloride to the deionized water in the step (1) is 1 (8-20).

Further, the N, N-dimethyl alkyl diamine added in the step (2) is one or two of the following structural formulas, and the adding amount is 2:1 in molar ratio to the cyanuric chloride in the step (1).

Wherein c is 1-5, and c is an integer.

Further, the molar ratio of the propargylamine added in the step (3) to the cyanuric chloride in the step (1) is (1.02-1.10): 1.

Further, the molar ratio of the sodium hydroxide added in the step (4) to the cyanuric chloride in the step (1) is 3:1, and the sodium hydroxide solution may be a saturated solution.

The invention provides CO prepared by the method₂Responsive compounds, which act as CO₂The stimulation response substance can be used for Click reaction to quickly and efficiently endow the material with CO₂And (4) responsiveness.

Compared with the prior art, the invention has the following beneficial effects:

(1) the invention has simple synthetic route and operation process. The invention adopts a one-pot boiling method, and the intermediate does not need to be purified and directly participates in the next reaction. After the reaction is finished, the solvent is removed through simple operations such as filtration, rotary evaporation and the like to obtain a purer crude product. The crude product is washed by petroleum ether and the like to obtain the final pure product. The whole process does not need column chromatography and other complex purification operations, and is suitable for large-scale industrial production.

(2) The compound of the invention contains two responsive tertiary amine groups, is far away from each other, does not interfere with each other, and therefore has high-efficiency CO₂The material has excellent response and can be endowed with excellent stimulus response performance.

(3) The invention provides a novel CO which can be used for Click reaction₂Responsive compound, the compound CO₂The modified polycarbonate has excellent response performance and good solubility, can be dissolved in common organic solvents such as water, ethanol, tetrahydrofuran, dichloromethane, chloroform, DMF (dimethyl formamide), dimethyl sulfoxide and the like, can be widely used for modification reaction of various materials, and can be particularly used for preparing CO in click chemistry₂A responsive material. Rapid and efficient direct "grafting" of tertiary amine groups to the surface of other substances or materials using Click reactions to impart CO thereto₂The stimulation response characteristic avoids the need of introducing CO in the initial stage of material preparation₂A complex process of responsive functional groups. The invention provides a new method for modifying the prepared material.

Drawings

FIG. 1 is an IR spectrum of 2- (propargylamino) -4, 6-bis (N, N-dimethyl-1, 3-propanediamyl) -1,3, 5-triazine of example 1.

FIG. 2 shows the NMR spectrum of 2- (propargylamino) -4, 6-bis (N, N-dimethyl-1, 3-propanediamino) -1,3, 5-triazine in deuterated chloroform in example 1.

FIG. 3 is the NMR carbon spectrum of 2- (propargylamino) -4, 6-bis (N, N-dimethyl-1, 3-propanediamido) -1,3, 5-triazine in example 1 (solvent DMSO-d 6);

FIG. 4 is a mass spectrum of 2- (propargylamino) -4, 6-bis (N, N-dimethyl-1, 3-propanediamine) -1,3, 5-triazine in example 1.

FIG. 5 is a scanning electron micrograph of a honeycomb porous film in an application example.

Fig. 6 shows the change in contact angle of a water drop of the honeycomb porous membrane in the application example.

DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION

The following description of the present invention will be made in conjunction with the examples and the accompanying drawings, which illustrate CO that can be used in the Click reaction₂Responsive compounds and methods for their preparation are further described. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.

All materials in the following examples were commercially available.

Example 1

Preparation of 2- (propargylamino) -4, 6-bis (N, N-dimethyl-1, 3-propanediamido) -1,3, 5-triazine

(1) Adding 7.38g of cyanuric chloride and 80mL of deionized water into a 250mL reaction vessel, and fully stirring in an ice-water bath;

(2) dropwise adding 8.17g of 3-dimethylamino-1-propylamine into the flask by using a constant-pressure dropping funnel, and heating to 60 ℃ after the dropwise adding is finished to continue reacting for 5 hours; (3) dropwise adding 2.31g of propargylamine into the reaction solution, gradually heating to 85 ℃, and continuing to react for 5 hours;

(4) adding a saturated solution containing 4.80g of sodium hydroxide into the reaction solution, and continuing to react for 1 hour;

(5) stopping the reaction, removing the solvent, adding 50mL of dichloromethane to dissolve the product, filtering, collecting the solution, adding anhydrous sodium sulfate into the solution, drying for 24h, filtering, and removing the solvent to obtain a crude product;

(6) dissolving the crude product in dichloromethane, adding a proper amount of petroleum ether, violently shaking, standing for precipitation, filtering, collecting a solid, dissolving the solid in dichloromethane again, repeating the operation twice, and freeze-drying the collected solid for 24 hours to obtain the product.

In the infrared spectrum (fig. 1): 3430cm^-1Belonging to N-H stretching vibration; 2945cm^-1And 2865cm^-1Due to alkane C-H stretching vibration; 2120cm^-1C ≡ C stretching vibration; 1580cm^-1Ascribed to N-H bending vibration; 1400cm^-1And 1350cm^-1Ascribed to C-H bending vibration; 1250cm-1, attributed to C-N stretching vibration and C-C stretching vibration. The infrared spectrum shows that the substance contains N-H, C ≡ C, C-N, C-C or C-H groups.

¹H NMR: the peak at 1.67ppm was assigned to (CH)₃)₂NCH₂CH₂CH₂-; the peak at 2.16ppm is assigned to (CH)₃)₂N-; the peak at 2.28ppm is assigned to (CH)₃)₂NCH₂CH₂CH₂-; the peak at 2.82ppm was assigned to-C.ident.CH, and the peak at 3.0ppm was assigned to HC.ident.C-CH₂-; the peak at 2.33ppm is assigned to (CH)₃)₂NCH₂CH₂CH₂-。

Carbon spectrum (fig. 3): the peak at 166ppm is attributed to C on the triazine ring, the peak at 77.6ppm is attributed to C ≡ C, and C in the rest groups is distributed at 20-60 ppm.

Mass spectrometry conditions (fig. 4): ESI electrospray ionization mode, positive mode detection. 335.10 in the spectrum is M + H of 2- (propargylamino) -4, 6-bis (N, N-dimethyl-1, 3-propanediamido) -1,3, 5-triazine⁺。

The analysis of infrared spectrum (figure 1), nuclear magnetic resonance hydrogen spectrum (figure 2) and mass spectrum (figure 3) shows that the 2- (propargylamine) -4, 6-bis (N, N-dimethyl-1, 3-propane diamine) -1,3, 5-triazine is successfully prepared.

Example 2

Preparation of 2- (propargylamino) -4, 6-bis (N, N-dimethylethylenediamino) -1,3, 5-triazine

(1) Adding 7.38g of cyanuric chloride and 80mL of deionized water into a 250mL reaction vessel, and fully stirring in an ice-water bath;

(2) dropwise adding 7.06g of N, N-dimethylethylenediamine into the flask by using a constant-pressure dropping funnel, heating to 60 ℃ after the dropwise adding is finished, and continuing to react for 6 hours;

(3) dropwise adding 2.31g of propargylamine into the reaction solution, gradually heating to 90 ℃, and continuing to react for 6 hours;

(4) adding a solution containing 4.80g of sodium hydroxide into the reaction solution, and continuing to react for 0.5 h;

(5) stopping the reaction, removing the solvent, adding 50mL of dichloromethane to dissolve the product, filtering, collecting the solution, adding anhydrous sodium sulfate into the solution, drying for 12h, filtering, and removing the solvent to obtain a crude product;

(6) dissolving the crude product in dichloromethane, adding a proper amount of petroleum ether, violently shaking, standing for precipitation, filtering, collecting a solid, dissolving the solid in dichloromethane again, repeating the operation twice, and freeze-drying the collected solid for 24 hours to obtain the product.

The following illustrates that the compounds prepared according to the invention can be used in the Click reaction and impart CO to the material₂Response characteristic application example

The product 2- (propargylamino) -4, 6-bis (N, N-dimethyl-1, 3-propanediamine) -1,3, 5-triazine in example 1 and appropriate amount of cuprous chloride, sodium ascorbate and pentamethyldiethylenetriamine were dissolved in ethanol to obtain a solution, and then a honeycomb porous membrane (FIG. 4) having azide groups on the surface was immersed in the solution, stirred for 12 hours, taken out of the porous membrane, washed with deionized water and dried naturally.

The contact angle test of water drops shows that the contact angle of the honeycomb porous membrane before reaction is 130 degrees and is hydrophobic, and the contact angle is reduced to 108 degrees and is reduced after reaction, which shows that 2- (propargylamino) -4, 6-bis (N, N-dimethyl-1, 3-propanediamido) -1,3, 5-triazine with certain hydrophilicity is introduced to the surface of the porous membrane through Click reaction.

Subsequently, saturated CO₂And (3) dripping the aqueous solution onto the surface of the modified porous membrane, and naturally drying the modified porous membrane to reduce the contact angle of the porous membrane to 80 degrees, so that the modified porous membrane is changed into a hydrophilic surface. This is because of CO₂The tertiary amine at the surface of the porous membrane is protonated in the wet environment, resulting in a more hydrophilic ammonium bicarbonate salt. Thereafter, the porous membrane was placed in an oven at 60 ℃ for 3h, and after cooling, the test showed that its contact angle increased to 107 ° and returned to hydrophobicity (fig. 5). This is because ammonium bicarbonate is unstable and easily decomposed in a high-temperature environment, and CO is released₂And reverts to a tertiary amine.

The above results show that the compounds prepared by the process of the present invention can be used in Click reactions and impart CO to materials₂A response characteristic.

Claims (1)

1. CO useful for Click reactions₂The response compound is characterized by having the following structural general formula,

wherein a is 1-5, b is 1-5, and a and b are integers.

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