CN105777574B - Gelator, molecular gel and preparation method thereof - Google Patents
Gelator, molecular gel and preparation method thereof Download PDFInfo
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- CN105777574B CN105777574B CN201610154025.6A CN201610154025A CN105777574B CN 105777574 B CN105777574 B CN 105777574B CN 201610154025 A CN201610154025 A CN 201610154025A CN 105777574 B CN105777574 B CN 105777574B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0052—Preparation of gels
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0052—Preparation of gels
- B01J13/0065—Preparation of gels containing an organic phase
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/14—Preparation of carboxylic acid amides by formation of carboxamide groups together with reactions not involving the carboxamide groups
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Abstract
The present invention provides a kind of gelator and its gel of formation, and the molecular formula of the gelator is C40H61N5O14.The invention also discloses the preparation method of the gelator and its molecular gel of formation.Gelator provided by the invention can be under low concentration 0.8wt% 2wt%, by heating, cooling down or supersonic induced, either changing the external actions such as pH value makes water, benzene, toluene or ethyl acetate that gelation occur, and, the molecular gel formed after gelation can by the external action that heats, cool down between solution state and gel state reversible transition, catalysis, chemical sensitisation, drug delivery, separating chiral compound special efficacy color medium and with given shape nano material prepare etc., there is potential application value.
Description
Technical field
The invention belongs to supramolecular chemistry technical field, and in particular to can make water and solvent that gel occur under a kind of low concentration
Change forms gelator, molecular gel of gel and preparation method thereof.
Background technology
Some small molecular organic compounds (mass fraction is less than 2%) can make water and sol gel at very low concentrations
Change, the gel formed is referred to as molecular gel.This kind of organic compound is referred to as gelator.Molecular gel is divided into gel and water
Gel, gel are the gels using solvent as decentralized medium, and hydrogel is the gel using water as decentralized medium.Gelator is in solvent
Middle heating for dissolving, during being cooled to room temperature, pass through hydrogen bond between gelator.The non-covalent bonds such as pi-pi accumulation, Van der Waals force
Interaction is spontaneously assembled, is assembled into orderly fibre structure, and these fibers can further tangle into the three-dimensional network of complexity
Structure, so as to by small solvent molecule gelation.
Hydrogel has much a little：First, assembling of the hydrogelator for research molecule in aqueous provides ten
Divide convenient system；Second, hydrogelator typically all has accurate configuration and conformation, and this is the complicated water gel of structure
System and the nanostructured with biological function provide good platform；3rd, the water-base cement factor has good bio-compatible
Property and degradability；4th, hydrogelator provides a good platform for medicament slow release.
Molecular gel is in catalysis, chemical sensitisation, drug delivery, the special efficacy color medium of separating chiral compound and with specific
Nano material preparation of shape etc., has potential application value.
The content of the invention
As the result of various extensive and careful research and experiment, it has been found by the inventor that in phenyl ring two
End is the different hydrophobicity saturated alkane chain of length respectively, is that being used as the group containing amido link is solidifying in the other end of phenyl ring
The glue factor causes water, benzene, toluene or ethyl acetate that gelation occurs and forms molecular gel at low concentrations, in catalysis, chemistry
Sensing, drug delivery, the special efficacy color medium of separating chiral compound and nano material preparation with given shape etc., tool
There is potential application value.Based on this discovery, the present invention is completed.
It is an object of the invention to solve at least the above or defect, and provide the advantages of at least will be described later.
It is a still further object of the present invention to provide a kind of gelator, its can cause under low concentration water, benzene, toluene or
Ethyl acetate occurs gelation and forms molecular gel.
It is a still further object of the present invention to provide the synthetic method of gelator, and the gelator and solvent formation
Molecular gel and its preparation method.
In order to realize according to object of the present invention and further advantage, there is provided a kind of gelator, the gel because
The structural formula of son is as follows：
The purpose of the present invention can also further be realized that the synthetic route of this method is such as by the preparation method of gelator
Under：
Methods described specific steps include：
Added Step 1: weighing the compound of formula 2 and catalyst in proportion in anhydrous solvent, react 8 under an atmosphere of hydrogen~
10 hours, after reaction terminates, suction filtration obtained the compound of formula 3；
Step 2: the compound of formula 3 that the step 1 is obtained, caproyl chloride and organic base are added in anhydrous solvent, in argon
Atmosphere encloses lower reaction 1~2 hour, after reaction terminates, is concentrated under reduced pressure, washs, column chromatography for separation obtains the compound of formula 4；
Step 3: the compound of formula 4 that the step 2 is obtained is added in solvent, sodium hydroxide solution is added, is heated back
Stream, react 1~2 hour, after reaction terminates, be concentrated under reduced pressure plus dilute acid for adjusting pH to acidity, washing obtains the compound of formula 5, its
In, the ratio of the amount of the material of the compound of formula 4 and sodium hydroxide is 1:1.5；
Step 4: the compound of formula 5, catalyst, condensing agent, the compound of formula 6 and the organic base that the step 3 obtains are added
Enter in anhydrous solvent, reacted 8~10 hours under argon atmosphere, after reaction terminates, be concentrated under reduced pressure, wash, be recrystallized to give formula 7
Compound；
Added Step 5: the step 4 is obtained into the compound of formula 7, catalyst, condensing agent, Boc- glycine and organic base
In anhydrous solvent, reacted 8~10 hours under argon atmosphere, after reaction terminates, add trifluoroacetic acid, react 1 hour, addition has
Machine alkali, regulation system to alkalescent, washing, column chromatography for separation obtain the compound gel factor of formula 1.
Preferably, wherein, in the step 1, the catalyst is palladium carbon, the compound of formula 2 and the catalyst
Mass ratio is 10:1.
Preferably, wherein, in the step 2, the ratio of the amount of the material of the compound of formula 3 and caproyl chloride is 1:
1, the organic base is triethylamine, and the eluant, eluent used in column chromatography for separation is petroleum ether and acetone, the body of petroleum ether and acetone
Product is than being 4:1.
Preferably, wherein, in the step 4, the amount of the material of the compound of formula 5 and the formula 6 compound
Than for 1:1, the catalyst is I-hydroxybenzotriazole, and the condensing agent is 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne
Diimine hydrochloric acid, the organic base are triethylamine, recrystallize the solvent used as ethyl acetate.
Preferably, wherein, in the step 5, the ratio of the amount of the material of the compound of formula 7 and Boc- glycine
For 1:1, the catalyst is I-hydroxybenzotriazole, and the condensing agent is 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne two
Imide hydrochloride, the organic base are triethylamine, and the eluant, eluent used in column chromatography for separation is dichloromethane and methanol, dichloromethane
Volume ratio with methanol is 20:1.
In order to realize according to object of the present invention and further advantage, a kind of molecular gel, the gel are additionally provided
The mixed system being made up of gelator and solvent；Wherein, the concentration of gelator is 0.8wt%-2wt%.
Preferably, wherein, the solvent is water, benzene, toluene or ethyl acetate.
The purpose of the present invention can also realize further by the preparation method of molecular gel, methods described using heating-
Cooling or ultrasonic method prepare gel：
(1) method of heating-cooling
The gelator that concentration is 0.8wt%-2wt% is dissolved in solvent under condition of water bath heating, then room temperature
Lower standing, cools down and produces molecular gel；
(2) ultrasonic method
After the gelator that concentration is 0.8wt%-2wt% is mixed with solvent, using ultrasonic cleaner to mixture
Supersonic induced 30s is carried out in the case where power is 200W, then stands at room temperature, produces molecular gel.
Preferably, wherein, the temperature of the heating water bath is not higher than the boiling point of the solvent.
The present invention comprises at least following beneficial effect：
1st, the molecular gel that gelator and aqueous solvent are formed is thermal reversion, be can dissolve after heating, with temperature
Reduce, gelation occurs for solvent, the molecular gel of formation is reheated, then cool down, can gelation again, can repeatedly weigh
It is multiple；
2nd, gelator concentration be 0.8wt%-2wt% and water form the fiber interweaving of certain length into three dimensional network
Shape structure, the fibre diameter are about 200~400nm, long about tens μm, have higher draw ratio, are formed with other solvents
The fibrous-network structure that is no longer ordered into of molecular gel pattern, but form the irregular laminated structure with hole,
It is different from the different solvents property for forming molecular gel.
Further advantage, target and the feature of the present invention embodies part by following explanation, and part will also be by this
The research and practice of invention and be understood by the person skilled in the art.
Brief description of the drawings
Fig. 1 is that (multiplication factor 2000,1mm is 20 μ for the SEM photograph of the hydrogel that gelator and the water of the present invention is formed
m)；
Fig. 2 is the SEM photograph multiplication factor 2000 for the molecular gel that the gelator of the present invention is formed with ethyl acetate,
1mm is 20 μm)；
Fig. 3 is that (multiplication factor 2000,1mm is for the SEM photograph of the molecular gel that is formed with toluene of gelator of the present invention
20μm)；
Fig. 4 is that (multiplication factor 2000,1mm is 20 for the SEM photograph of the molecular gel that gelator and the benzene of the present invention is formed
μm)；
Fig. 5 is the ultra-violet absorption spectrum for the hydrogel that the gelator of the present invention is formed with water；
Fig. 6 is the fluorescence emission spectrum for the hydrogel that the gelator of the present invention is formed with water.
Embodiment
The present invention is described in further detail below in conjunction with the accompanying drawings, to make those skilled in the art with reference to specification text
Word can be implemented according to this.
It should be appreciated that such as " having ", "comprising" and " comprising " term used herein do not allot one or more
The presence or addition of individual other elements or its combination.
<Example 1>
A kind of gelator, the structural formula of the gelator are as follows：
The synthetic route of the preparation side of above-mentioned gelator is as follows：
The specific steps of the preparation method include：
Step 1: the compound of formula 2 (6.01g, 15.00mmol) and palladium-carbon catalyst (0.6g, 10wt%) are weighed in proportion,
Add anhydrous CH2Cl2Dissolving, connects H2Ball, take a breath 3~4 times, change the air ambient of system into H2Environment, in H2It is anti-under atmosphere
Answer 8~10 hours, after reaction terminates, suction filtration obtains the compound 5.56g (100%) of formula 3, is directly used in the next step；
Step 2: the compound of formula 3 (5.56g, 15.00mmol) that the step 1 is obtained, triethylamine (1.52g,
15.00mmol) it is dissolved in anhydrous CH2Cl2In, under ice-water bath, 10mL is contained into caproyl chloride (2.02g, 15.00mmol)
CH2Cl2Solution is instilled in reaction system, is reacted 1~2 hour under argon atmosphere, after reaction terminates, adds pH=1 hydrochloric acid solution
PH is adjusted to acidity, reaction solution is gone into separatory funnel, liquid separation, water layer CH2Cl2(100mL × 2) extract.Merge organic layer,
Use anhydrous Na2SO4Dry.Revolving removes organic solvent, crude by column chromatography (petroleum ether:Acetone=4:1) chemical combination of formula 4, is obtained
Thing 6.11g (87%)；
Step 3: the compound of formula 4 (4.68g, 10.00mmol) that the step 2 is obtained adds 50mLTHF dissolvings, stir
Mix down, add the aqueous solution containing NaOH (0.6g, 15.00mmol), be heated to reflux, react 1~2 hour, after reaction terminates, subtract
Pressure concentration plus pH=1 hydrochloric acid solution adjust pH to acidity, are gone to separatory funnel, use CH2Cl2(80mL × 3) extract.Close
And organic layer, use anhydrous Na2SO4Dry.Revolving removes organic solvent, obtains the compound 4.35g (96%) of formula 5；
Step 4: the compound of formula 5 (4.55g, 10.00mmol) that the step 3 obtains, I-hydroxybenzotriazole are urged
Agent (1.35g, 10.00mmol), 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimine hydrochloric acid condensing agent (1.92g,
10.00mmol) with triethylamine (2.53g, 25.00mmol), dichloromethane solvent 50mL dissolvings are added, are activated under nitrogen atmosphere
30min.The compound of formula 6 (2.98g, 10.00mmol) is dissolved in 30mL dichloromethane.By the solution containing the compound of formula 5
It is slowly dropped into the solution of the compound of formula 6, reacts 8~10 hours.After reaction stops, reaction solution is gone into separatory funnel, successively
With water (50mL × 3), saturated aqueous common salt (50mL × 1) washing, organic layer anhydrous Na2SO4Dry.Revolving removes organic solvent,
Obtain yellow-brown solid.Re-crystallizing in ethyl acetate, obtain the compound 4.18g (57%) of formula 7；
Step 5: weigh Boc- glycine (0.63g, 3.00mmol), I-hydroxybenzotriazole catalyst (0.40g,
3.0mmol), 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimine hydrochloric acid condensing agent (0.58g, 3.0mmol) and triethylamine
(0.76g, 7.50mmol), dichloromethane solvent 30mL dissolvings are added, activate 30min under nitrogen atmosphere.By the compound of formula 7
(1.47g, 2.00mmol) is dissolved in 20mL dichloromethane.Solution containing the compound of formula 7 is slowly dropped into Boc- glycine
Solution in, reacted 8~10 hours under argon atmosphere, reaction terminate after, add trifluoroacetic acid (2mL), react 1 hour, add
Enter triethylamine, the weakly alkaline environment of regulation system to pH=8, reaction solution is gone into separatory funnel, successively with water (50mL × 3),
Saturated aqueous common salt (50mL × 1) washs, organic layer anhydrous Na2SO4Dry.It is spin-dried for organic solvent, column chromatography (CH2Cl2﹕ CH3OH
=20:1) the isolated compound gel factor of formula 1.
The structural formula of the compound of formula 4, nuclear-magnetism (1H-NMR,13C NMR) it is characterized as below：
Nuclear-magnetism1H NMR(400MHz,CDCl3) δ 8.76 (s, 1H), 8.21 (dd, J=8.9,2.8Hz, 1H), 7.80 (s,
1H), 7.54 (s, 1H), 6.94 (d, J=9.0Hz, 1H), 4.28-4.24 (m, 4H), 3.94 (m, 2H), 3.76 (s, 3H), 3.71
(m, 2H), 3.65-3.60 (m, 4H), 3.52 (m, 2H), 3.35 (s, 3H), 2.35 (t, J=7.6Hz, 2H), 1.71 (m, 2H),
1.36-1.32 (m, 4H), 0.90 (t, J=7.0Hz, 3H) nuclear-magnetisms13C NMR(101MHz,CDCl3)δ171.94,170.42,
165.20,153.19,132.73,125.37,123.18,121.16,113.67,71.87,70.63,70.57,70.53,
69.16,68.73,58.96,52.17,41.83,37.34,31.46,25.33,22.48,13.95.
The structural formula of the compound of formula 5, nuclear-magnetism (1H-NMR,13C NMR) it is characterized as below：
Nuclear-magnetism1H NMR(400MHz,CDCl3) δ 9.96 (s, 1H), 8.61 (dd, J=8.9,2.8Hz, 1H), 8.02 (s,
1H), 7.81 (s, 1H), 7.14 (d, J=9.0Hz, 1H), 4.24 (m, 2H), 4.01 (m, 2H), 3.82 (m, 2H), 3.60 (m,
2H),3.53-3.48(m,4H),3.41(m,2H),3.22(s,3H),2.02(s,3H).
Nuclear-magnetism13C NMR(101MHz,CDCl3)δ171.10,167.98,164.20,152.29,133.05,123.53,
121.66,121.41,114.29,71.17,69.78,69.72,69.50,68.73,68.48,57.96,41.36,23.73.
The structural formula of the compound of formula 7, nuclear-magnetism (1H-NMR,13C NMR) it is characterized as below：
Nuclear-magnetism1H NMR(400MHz,CDCl3) δ 9.76 (s, 1H), 9.23 (s, 1H), 8.81 (s, 1H), 8.24 (d, J=
Hz, 1H), 7.86 (s, 3H), 7.80 (s, 1H), 7.40 (s, 1H), 7.04 (s, 1H), 6.86 (d, J=Hz, 1H), 4.48 (m,
2H),4.45(m,2H),4.22(m,2H),4.02(m,2H),3.82-3.47(m,18H),3.36(s,3H),3.31(s,3H),
2.42 (t, J=Hz, 2H), 1.71 (m, 2H), 1.32 (m, 4H), 0.89 (t, J=Hz, 3H)；
Nuclear-magnetism13C NMR(101MHz,CDCl3)δ172.16,167.00,166.87,164.70,153.38,147.74,
139.72,132.51,130.67,125.21,122.64,120.32,112.86,111.04,110.52,110.31,71.87,
71.80,70.71,70.56,70.43,70.36,69.21,69.04,68.88,64.53,58.95,58.85,45.30,
37.13,31.52,25.22,22.51,13.96.
The structural formula of the compound of formula 1, nuclear-magnetism (1H-NMR,13C NMR) it is characterized as below：
Nuclear-magnetism1H NMR(400MHz,CDCl3) δ 10.73 (s, 1H), 10.45 (s, 1H), 9.93 (s, 1H), 8.74 (d, J=
Hz, 1H), 8.25 (s, 1H), 8.16 (s, 3H), 8.10 (s, 1H), 8.00 (s, 1H), 7.97 (s, 1H), 7.79 (d, J=Hz,
1H), 7.17 (d, J=Hz, 1H), 4.46 (m, 2H), 4.27 (m, 2H), 4.19 (m, 2H), 3.85-3.73 (m, 6H), 3.56-
3.35 (m, 20H), 3.20 (s, 3H), 3.17 (s, 3H), 2.28 (t, J=Hz, 2H), 1.60 (m, 2H), 1.29 (m, 4H), 0.87
(t, J=6.8Hz, 3H)；
Nuclear-magnetism13C NMR(101MHz,CDCl3)δ172.37,170.98,167.71,165.43,164.31,152.33,
139.49,139.45,133.06,130.41,123.56,121.79,121.55,114.68,114.56,114.24,114.00,
71.18,71.13,69.84,69.71,69.55,69.44,68.82,68.56,68.32,64.14,57.92,45.57,
43.43,36.20,30.84,24.78,21.84,13.78.
<Example 2>
The method that hydrogel is prepared by gelator in embodiment 1 and water generation gelation：
The gelator (6.30mg, 7.96mmol) and water (1mL) are placed in high 5cm, diameter 1.5cm osculum screw thread
In bottle.By screw thread bottle closure, mixture in thread bottle is heated to compound using water-bath and is completely dissolved, is so stood at room temperature,
Hydrogel can be formed after cooling, the thread bottle equipped with hydrogel is inverted, no liquid flow phenomenon, is as shown in Figure 1 formation
Hydrogel SEM photograph (multiplication factor 2000,1mm be 20 μm), as shown in figure 1, gelator and aqueous solvent form by
The fiber interweaving of certain length into tridimensional network, the fibre diameter is about 200~400nm, long about tens μm, is had
Higher draw ratio, SEM photograph are explained when fibre structure grows into sufficient length and tangles, and solvent will be by " lock
It is fixed " in three-dimensional net structure, gelation occurs.
<Example 3>
The method that molecular gel is prepared by gelator in embodiment 1 and ethyl acetate generation gelation：
The gelator (15mg, 18.94mmol) and ethyl acetate (1mL) are placed in high 5cm, diameter 1.5cm's is small
In mouth thread bottle.By screw thread bottle closure, mixture is carried out in the case where power is 200W using ultrasonic cleaner supersonic induced
30s, then stand at room temperature, produce molecular gel, the thread bottle equipped with molecular gel is inverted, no liquid flow phenomenon, such as
Fig. 2 show the SEM photograph (multiplication factor 2000,1mm be 20 μm) for the molecular gel to be formed, as shown in Fig. 2 gelator with
The fibrous-network structure that the pattern for the molecular gel that solvent ethyl acetate is formed no longer is ordered into, but form irregular band
There is the laminated structure in hole.
<Example 4>
The method that molecular gel is prepared by gelator in embodiment 1 and toluene generation gelation：
The gelator (15mg, 18.94mmol) and toluene (1mL) are placed in high 5cm, diameter 1.5cm osculum spiral shell
In line bottle.By screw thread bottle closure, in the case where power is 200W supersonic induced 30s is carried out to mixture using ultrasonic cleaner, so
Stand at room temperature afterwards, produce molecular gel, the thread bottle equipped with gel is inverted, no liquid flow phenomenon, is illustrated in figure 3 shape
Into molecular gel SEM photograph (multiplication factor 2000,1mm be 20 μm), as shown in figure 3, gelator and solvent toluene shape
Into molecular gel the fibrous-network structure that is no longer ordered into of pattern, but form the irregular sheet knot with hole
Structure.
<Example 5>
The method that molecular gel is prepared by gelator in embodiment 1 and benzene generation gelation：
The gelator (10.3mg, 13.00mmol) and benzene (1mL) are placed in high 5cm, diameter 1.5cm osculum spiral shell
In line bottle.By screw thread bottle closure, in the case where power is 200W supersonic induced 30s is carried out to mixture using ultrasonic cleaner, so
Stand at room temperature afterwards, produce molecular gel, the thread bottle equipped with molecular gel is inverted, no liquid flow phenomenon, as shown in Figure 4
For the SEM photograph (multiplication factor 2000,1mm be 20 μm) of the molecular gel of formation, as shown in figure 4, gelator and solvent benzol
The fibrous-network structure that the pattern of the molecular gel of formation is no longer ordered into, but form the irregular sheet with hole
Structure.
<Example 6>
The gelatinization performance of gelator and different solvents is as shown in the table in embodiment 1：
Table 1 lists in embodiment 1 gelator to the gelatinization performance of different solvents
| Solvent | Gel-forming situation |
| Water | G |
| Ethyl acetate | G |
| N-hexane | I |
| Hexamethylene | I |
| Benzene | G |
| Toluene | G |
Note：Gelator concentration is 0.8wt%-2wt%；G：Expression can form stable gel；S：Represent that compound is complete
Dissolving；I：Represent insoluble.
As shown in table 1, gelator causes water, ethyl acetate, benzene or toluene to occur to coagulate at low concentrations in embodiment 1
Gel forms molecular gel, also, the hydrogel of formation is reheated, then cold true, can gelation again.This process can be with
It is repeated several times, it is thermal reversion to show formed hydrogel.
<Example 7>
The gelation of gelator and water forms the performance test of hydrogel in embodiment 1：
Ultraluminescence spectrum experiment
UV absorption is very sensitive to the distance and orientation of intermolecular chromophore, can reflect intermolecular interaction
Situation, it is widely used in the sign of Supramolecular self assembly system.
As shown in figure 5, it can be found that gelator has 243 and 306nm, two absorption bands under solution state, formation is coagulated
After glue, there occurs obvious red shift for absorption spectrum.
Fluorescence emission spectrum is tested
Fluorescence spectrum is very sensitive to the distance and orientation of intermolecular chromophore, can reflect intermolecular interaction
Situation, it is widely used in the sign of Supramolecular self assembly system.
As shown in fig. 6, it can be found that gelator is in solution state (1 × 10-4M fluorescence emission maximum value is 392nm under),
And (12mgmL under gel state-1) fluorescence emission maximum value be 373nm, blue shift 19nm.
Soda acid response experiment
Accordingly tested by different pH soda acids, it is found that under conditions of pH is more than 3, gelator can be with shape with water
Into hydrogel.Moreover, hydrogel reversible transition between solution state and gel state can be made by adjusting pH.
In summary, gelator provided by the invention can make solvent that gelation occur under low concentration, and it is synthesized
Method is simple, ripe, can be obtained by the gelator water, ethyl acetate, benzene or toluene shape by the method for being easy to control
Into molecular gel, by the method for heating-cooling and water gelation occurs for gelator, also, by the hydrogel weight of formation
New heating, then it is cold true, can gelation again.This process can be repeated several times, and it is thermal reversion to show formed hydrogel.
In addition, under conditions of supersonic induced, the gelator can make benzene, toluene and ethyl acetate form molecular gel, molecule
Gel catalysis, chemical sensitisation, drug delivery, separating chiral compound special efficacy color medium and with given shape nanometer material
Material preparation etc., has potential application value.
Although embodiment of the present invention is disclosed as above, it is not restricted in specification and embodiment listed
With.It can be applied to various suitable the field of the invention completely., can be easily for those skilled in the art
Realize other modification.Therefore it is of the invention and unlimited under the universal limited without departing substantially from claim and equivalency range
In specific details and shown here as the legend with description.
Claims (9)
1. a kind of gelator, the structural formula of the gelator is as follows：
2. a kind of method for preparing the gelator described in claim 1, its synthetic route are as follows：
Methods described specific steps include：
Step 1: weighing in proportion in the compound of formula 2 and catalyst addition anhydrous solvent, it is small that 8~10 are reacted under an atmosphere of hydrogen
When, after reaction terminates, suction filtration obtains the compound of formula 3；
Step 2: the compound of formula 3 that the step 1 is obtained, caproyl chloride and organic base are added in anhydrous solvent, in argon atmospher
Lower reaction 1~2 hour is enclosed, after reaction terminates, is concentrated under reduced pressure, washs, column chromatography for separation obtains the compound of formula 4；
Step 3: the compound of formula 4 that the step 2 is obtained is added in solvent, sodium hydroxide solution is added, is heated to reflux, instead
Answer 1~2 hour, after reaction terminates, be concentrated under reduced pressure plus dilute acid for adjusting pH to acidity, washing obtains the compound of formula 5, wherein, it is described
The ratio of the amount of the material of the compound of formula 4 and sodium hydroxide is 1:1.5；
Step 4: the compound of formula 5 that the step 3 is obtained, catalyst, condensing agent, the compound of formula 6 and organic base add nothing
In aqueous solvent, reacted 8~10 hours under argon atmosphere, after reaction terminates, be concentrated under reduced pressure, wash, be recrystallized to give the chemical combination of formula 7
Thing；
Step 5: it is anhydrous that the step 4 is obtained into the compound of formula 7, catalyst, condensing agent, Boc- glycine and organic base addition
In solvent, reacted 8~10 hours under argon atmosphere, after reaction terminates, add trifluoroacetic acid, react 1 hour, add organic
Alkali, regulation system to alkalescent, washing, column chromatography for separation obtain the compound gel factor of formula 1.
3. method as claimed in claim 2, wherein, in the step 1, the catalyst is palladium carbon, the compound of formula 2 with
The mass ratio of the catalyst is 10:1.
4. method as claimed in claim 2, wherein, in the step 2, the material of the compound of formula 3 and caproyl chloride
The ratio of amount is 1:1, the organic base is triethylamine, and the eluant, eluent used in column chromatography for separation is petroleum ether and acetone, petroleum ether
Volume ratio with acetone is 4:1.
5. method as claimed in claim 2, wherein, in the step 4, the compound of formula 5 and the formula 6 compound
Material amount ratio be 1:1, the catalyst is I-hydroxybenzotriazole, and the condensing agent is 1- ethyls-(3- dimethylaminos
Base propyl group) phosphinylidyne diimine hydrochloric acid, the organic base is triethylamine, recrystallizes the solvent used as ethyl acetate.
6. method as claimed in claim 2, wherein, in the step 5, the thing of the compound of formula 7 and Boc- glycine
The ratio of the amount of matter is 1:1, the catalyst is I-hydroxybenzotriazole, and the condensing agent is 1- ethyls-(3- dimethylaminos third
Base) phosphinylidyne diimine hydrochloric acid, the organic base is triethylamine, and the eluant, eluent used in column chromatography for separation is dichloromethane and first
The volume ratio of alcohol, dichloromethane and methanol is 20:1.
7. a kind of molecular gel, the mixed system being made up of the gelator described in claim 1 and solvent；Wherein, gel because
The concentration of son is 0.8wt%-2wt%, and the solvent is water, benzene, toluene or ethyl acetate.
8. a kind of method for preparing the molecular gel described in claim 7, methods described uses heating-cooling or ultrasonic method
Prepare molecular gel：
(1) method of heating-cooling
The gelator that concentration is 0.8wt%-2wt% is dissolved in solvent under condition of water bath heating, it is then quiet at room temperature
Put, cool down and produce molecular gel；
(2) ultrasonic method
After the gelator that concentration is 0.8wt%-2wt% is mixed with solvent, using ultrasonic cleaner to mixture in work(
Rate is to carry out supersonic induced 30s under 200W, then stands at room temperature, produces molecular gel.
9. the method described in claim 8, wherein, the temperature of the heating water bath is not higher than the boiling point of the solvent.
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