CN105482127B - A kind of functional hyperbranched ferrocene of amphipathic glucosides and preparation method thereof - Google Patents
A kind of functional hyperbranched ferrocene of amphipathic glucosides and preparation method thereof Download PDFInfo
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- CN105482127B CN105482127B CN201511027446.4A CN201511027446A CN105482127B CN 105482127 B CN105482127 B CN 105482127B CN 201511027446 A CN201511027446 A CN 201511027446A CN 105482127 B CN105482127 B CN 105482127B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
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Abstract
The invention discloses a kind of amphipathic functional hyperbranched ferrocene of glucosides and preparation method thereof, are related to cyclopentadienyl metal-containing polymer field of material technology.The chemical structural formula of the amphipathic functional hyperbranched ferrocene of glucosides is as shown in Equation 3.The hyperbranched ferrocene of glucosides end group modification is constructed in the compounds of this invention, on the one hand the important shape feature of molecule and spatial character are assigned, increase structure diversity, on the other hand, its good hydrophily and biocompatibility can be assigned, the defects of prior art hydrophily is poor, biological responding is bad and cytotoxicity can be overcome, to develop the cyclopentadienyl metal-containing polymer material haveing excellent performance.
Description
Technical field
The present invention relates to cyclopentadienyl metal-containing polymer field of material technology.
Background technology
There is dissaving polymer three-dimensional globular stereochemical structure, unique physics to be made it have with chemical constitution low glutinous
Degree and can largely modify the properties such as functional end-group at good dissolubility.
Ferrocene and its derivative is with unique molecular structure and special electrochemistry, magnetic, catalysis and redox property
And as important one kind in novel metal organic compound, catalysis, magnetic material, optical material, liquid crystal material with
And biochemical medicine etc. is used widely.
Ferrocene is introduced into in highly branched polymer the functional hyperbranched ferrocene synthesized, ferrocene is unique
Oxidation-reduction quality, catalytic etc. combine with the three-dimensional structure performance of dissaving polymer, biosensor,
Antitumor, antibacterial etc. is applied.
However that there are hydrophilies in the molecule construction and performance study of functionalization ferrocenyl hyperbranched polymer is poor,
The problems such as overall molecule biological responding is bad and cytotoxicity, reduces its application potential in bio-medical material.
Invention content
The technical problem to be solved in the present invention is to provide a kind of functional hyperbranched ferrocene of amphipathic glucosides and its preparations
Method, the hyperbranched ferrocene of glucosides end group modification is constructed in the compound, on the one hand assign the important shape feature of molecule and
Spatial character, on the other hand its good hydrophily and biocompatibility can be assigned, can overcome by increasing structure diversity
There is the defects of technology hydrophily is poor, biological responding is bad and cytotoxicity, to develop the cyclopentadienyl metal haveing excellent performance
Polymer material.
In order to solve the above technical problems, the technical solution used in the present invention is：A kind of amphipathic glucosides functionalization over-expense
Change ferrocene, the chemical structural formula of the amphipathic functional hyperbranched ferrocene of glucosides is as shown in Equation 3：
The preparation method of the above-mentioned functional hyperbranched ferrocene of amphipathic glucosides, includes the following steps：
Step (1), by compound shown in the azido-methyl methyl ferrocenylcarboxylate of compound 1,1 '-shown in formula 1-4 and formula 2-1
G3-HPAE obtains the hyperbranched ferrocene of compound azido shown in formula 2 by ester exchange reaction, the step chemical equation
It is as follows：
Step (2), by compound propargyl β-D- shown in the hyperbranched ferrocene of compound azido shown in formula 2 and formula 3-1
Glucopyranoside is reacted by Click Chemistry, obtains the amphipathic glucosides functionalization of compound shown in final product formula 3
Hyperbranched ferrocene, the step chemical equation are as follows：
Preferably, in step (1)：By compound 1,1 '-azido-methyl methyl ferrocenylcarboxylate shown in formula 1-4 and formula 2-1
Shown compound G3-HPAE, first in N2Atmosphere, react under conditions of 75~85 DEG C of temperature, close nitrogen after completion of the reaction, then
1.5~3h is vacuumized, the hyperbranched ferrocene of compound azido shown in formula 2 is obtained.
It is further preferred that 1,1 '-azido-methyl methyl ferrocenylcarboxylate of compound and formula shown in step (1) Chinese style 1-4
The molar ratio of compound G3-HPAE shown in 2-1 is 0.34-0.54:1.
Preferably, in step (2)：By compound alkynes shown in the hyperbranched ferrocene of compound azido shown in formula 2 and formula 3-1
Propyl β-D- glucopyranosides are dissolved in anhydrous DMF, and under the action of catalyst, dark stirs 22-26h at room temperature；It filters,
Freeze-drying obtains the functional hyperbranched ferrocene of the amphipathic glucosides of compound shown in final product formula 3.
It is further preferred that catalyst described in step (2) is CuBr and PMDETA.
Still more preferably, the hyperbranched ferrocene of compound azido shown in step (2) Chinese style 2 and formula 3-1 shownization
The molar ratio for closing object propargyl β-D- glucopyranosides is 1.1-1.3:1；Compound propargyl β-D- shown in CuBr and formula 3-1
The molar ratio of glucopyranoside is 1-1.5:1；Compound propargyl β-D- glucopyranosides shown in PMDETA and formula 3-1
Molar ratio is 1-1.5:1.
Preferably, the preparation method of the azido-methyl methyl ferrocenylcarboxylate of compound 1,1 '-shown in formula 1-4 includes following step
Suddenly：
Step a, compound 1 shown in formula 1,1 '-ferrocene dicarboxylic acid and absolute methanol carry out esterification, obtain formula 1-1
1,1 '-ferrocene dicarboxylic acid dimethyl ester of shown compound, the step chemical equation are as follows：
Step b, compound 1 shown in formula 1-1,1 '-ferrocene dicarboxylic acid dimethyl ester and NaOH after completion of the reaction, are added acid and adjust
PH value is saved to 1, obtains the carboxyl methyl ferrocenylcarboxylate of compound 1,1 '-shown in formula 1-2, the step chemical equation is as follows：
Step c, compound 1 shown in formula 1-2,1 '-carboxyl methyl ferrocenylcarboxylate are reacted with sodium borohydride, obtain formula 1-3
1,1 '-methylol methyl ferrocenylcarboxylate of shown compound, the step chemical equation are as follows：
Step d, compound 1 shown in formula 1-3,1 '-methylol methyl ferrocenylcarboxylate and Sodium azide reaction, obtain formula 1-4
1,1 '-azido-methyl methyl ferrocenylcarboxylate of shown compound, the step chemical equation are as follows：
It is further preferred that the preparation method of the azido-methyl methyl ferrocenylcarboxylate of compound 1,1 '-shown in formula 1-4 includes
Following steps：
In 1 '-ferrocene dicarboxylic acid and absolute methanol, triethylamine, control temperature is added in step a, the compound 1 shown in formula 1
Degree is added thionyl chloride, continues to be stirred to react 1~1.5h at such a temperature between 0~5 DEG C；Reheating rises to 40~55 DEG C,
4~5h is reacted, reaction solution natural cooling is obtained into the ferrocene dicarboxylic acid two of compound 1,1 '-shown in formula 1-1 except solvent, drying
Methyl esters；
The ferrocene dicarboxylic acid dimethyl ester of compound 1,1 '-shown in formula 1-1 is dissolved into acetone, and is added to by step b
In the mixed liquor of CH3OH and NaOH, 8~11h is stirred at room temperature, and acid for adjusting pH value is added to 1, obtains compound shown in formula 1-2
1,1 '-carboxyl methyl ferrocenylcarboxylates；
Grass is added in the CH2Cl2 suspension of 1 '-carboxyl methyl ferrocenylcarboxylate for step c, the compound 1 shown in formula 1-2
Acyl chlorides stirs 1~1.5h at room temperature, removes solvent, and be dissolved in dichloromethane, adds sodium borohydride, then CH3OH is added dropwise, room temperature
Lower stirring 25-40min obtains the methylol methyl ferrocenylcarboxylate of compound 1,1 '-shown in formula 1-3；
The methylol methyl ferrocenylcarboxylate of compound 1,1 '-shown in formula 1-3 and Sodium azide are dissolved in acetic acid by step d,
45~55 DEG C of reactions are heated to, after completion of the reaction, obtain the azido-methyl methyl ferrocenylcarboxylate of compound 1,1 '-shown in formula 1-4.
It is further preferred that the molar ratio of 1,1 '-ferrocene dicarboxylic acid and thionyl chloride is 1 in step a:2~4；Step b
Middle CH3The molar ratio of OH and NaOH is 1:8.9-9.2；It is quenched with water when the reaction is finished in step c；In step d, reaction finishes
Afterwards, solvent is evaporated, solvent temperature≤55 DEG C is evaporated, obtains the azido-methyl ferrocenecarboxylic acid first of compound 1,1 '-shown in formula 1-4
Ester.
The Chinese of compound G3-HPAE shown in formula 2-1 is：Hyperbranched poly (amine) ester of the third generation；In PMDETA
Literary fame is known as：Pentamethyl-diethylenetriamine, the entitled Pentamethyldiethylenetriamine of English, molecular formula are
C9H23N3, molecular weight 173.299, CAS registration numbers are 3030-47-5.
It is using advantageous effect caused by above-mentioned technical proposal：
(1) present invention using the ease of solubility of saccharide compound, one's own object, with the affinity of body relationship and anti-swollen
The characteristics such as tumor, antiviral activity construct the hyperbranched ferrocene of glucosides end group modification, to overcome hyperbranched ferrocene hydrophilic
Poor, the undesirable defect of bioactivity of property.
(2) the hyperbranched ferrocene of glucosides end group modification is constructed in the present invention, and it is special on the one hand to assign the important shape of molecule
Seek peace spatial character, increase structure diversity, on the other hand, its good hydrophily and biocompatibility can be assigned, can gram
The defects of prior art hydrophily is poor, biological responding is bad and cytotoxicity is taken, to develop the cyclopentadienyl haveing excellent performance
Metal-containing polymer material.
(3) the functional hyperbranched ferrocene of glucosides that the present invention constructs has good aqueous solubility and biological responding, is
Its application in terms of the medical materials such as biosensor, anti-tumor agent provides experiment basis, also for the synthesis of new material and
Exploitation provides technical strategies.
(4) present invention is led to as raw material using click chemistry (Click chemistry) with 1,1 '-ferrocene dicarboxylic acid
Excessive step reaction, reaction condition is easy to implement, avoids the use of poisoned catalyst.Ferrocene is introduced into G3-HPAE,
And glucoside is introduced into hyperbranched ferrocene using the reaction of ferrocene side chain, prepare the over-expense of glucosides functionalization
Change ferrocene.The polymer can good amphipathic, electrochemistry and thermal stability.
(5) preparation method reaction condition of the present invention is easy to implement, and preparation condition is mild.
Specific implementation mode
Below in conjunction with specific embodiment, the present invention is further illustrated：
Embodiment 1
1,1 '-ferrocene dicarboxylic acid 1.5g (5.5mmol), absolute methanol 35ml are sequentially added 250mL tri- by step (1)
In mouth round-bottomed flask, triethylamine 2.8ml (20mmol) is added dropwise, solution colour is deepened, and reaction temperature, control are reduced using ice salt bath
Between 0~5 DEG C, thionyl chloride 1.5ml (20mmol) is slowly added dropwise by constant pressure funnel at this time, reaction is violent, has big
It measures white smoke to generate, after being added dropwise, continues to be stirred to react 1h at such a temperature.Remove ice salt bath, using oil bath heating, rises
To 50 DEG C, 4.5h is reacted, after reaction solution natural cooling, three-necked flask is taken out, reaction mixture is poured into 250mL single-necked flasks
In, it is installed on Rotary Evaporators.Control Rotary Evaporators temperature is gradually warming up to 45 DEG C from 25 DEG C, and rotary evaporation removes methanol
Dope is obtained, saturated nacl aqueous solution 40ml is then added thereto, is extracted with 90mL ethyl acetate, is poured into after merging organic phase
In separatory funnel, static layering takes upper layer.Then rotary evaporation remove ethyl acetate, control Rotary Evaporators temperature at 40 DEG C,
It is put into thermostatic drying chamber, 50 DEG C of set temperature, is dried to obtain 1,1 '-ferrocene dicarboxylic acid dimethyl ester (formula 1- of brown needles object
1), yield 91.1%.
At room temperature in CH3NaOH (2.9g, 72.5mmol) is added dropwise in OH (26mL, 642.5mmol), then by 1,1 '-
Ferrocene dicarboxylic acid dimethyl ester (20g, 66mmol) is dissolved into acetone (300ml) solution, and this solution is added to above-mentioned standard
The CH got ready3In OH, resulting slurry is placed in 250mL three-necked flasks 10h is stirred at room temperature after, orange is consolidated
Body residue is dissolved in water (500ml), is poured the mixture into 250mL single-necked flasks, is installed on Rotary Evaporators.Control
Rotary Evaporators temperature is gradually warming up to 45 DEG C from 25 DEG C, and rotary evaporation removes methanol and acetone obtains dope.Pour into small beaker
In, it is added at 0 DEG C in dense HCl solution and adjusts pH until 1, and collect sediment, be put into thermostatic drying chamber, set temperature 50
DEG C drying, obtains 1,1 '-carboxyl methyl ferrocenylcarboxylate (formula 1-2) of yellow solid, yield 91%.
1,1 '-carboxyl methyl ferrocenylcarboxylate (20g, 69mmol) and CH are respectively put into 250mL three-necked flasks2Cl2
Then the suspension of (200mL) solution is slowly added to oxalyl chloride (9.1ml, 104mmol) by constant pressure funnel, and will mix
It closes object and 1h is stirred at room temperature, solvent and excessive oxalyl chloride are removed in a vacuum, obtained residue.The remnants that will be obtained
Object is dissolved in dichloromethane (200mL), obtains red solution, and sodium borohydride (10.5g, 277mmol) is added in solution.Lead to again
Constant pressure funnel is crossed by CH3OH (100mL) is added dropwise wherein, and 30min is stirred at room temperature in mixture, is used after stirring
Water (300ml) is quenched, by organic layer separation.Water layer CH2Cl2(200ml) is extracted.Vacuum drying, obtains yellow solid residue
1,1 '-methylol methyl ferrocenylcarboxylate (formula 1-3), yield 94%.
1,1 '-methylol methyl ferrocenylcarboxylate (1.11g, 4.05mmol) and Sodium azide (1.58g, 1.58mmol) is molten
Solution is poured into acetic acid (30ml) in 250mL three-necked flasks, and 50 DEG C of reaction 18h are heated to.After completion of the reaction, three mouthfuls of burnings are removed
Bottle, liquid is poured into 250mL single-necked flasks, is installed on Rotary Evaporators.It is gradual from 25 DEG C to control Rotary Evaporators temperature
50 DEG C are warming up to, ethyl acetate is steamed, obtains grease, reaction mixture concentrates in a vacuum, and it is folded to obtain orange solids 1,1 '-
N-methyl methyl ferrocenylcarboxylate (formula 1-4), yield 81%.
Step (2) is separately added into 1,1 '-azido-methyl methyl ferrocenylcarboxylate (formula 1- of product in 250mL three-necked flasks
4), G3-HPAE (molar ratios：0.34:1), by three-necked flask as in thermostat water bath, reacting 6h, temperature in a nitrogen atmosphere
Control closes nitrogen, vacuumizes 2h and obtain the hyperbranched ferrocene (formula of milky white shape viscous fluid azido after completion of the reaction at 80 DEG C
2), the grafting rate of the step is 76%.
Step (3), N2Under protection, in 250mL three-necked flasks, by the hyperbranched ferrocene of product azido (formula 2) and alkynes
Propyl β-D- glucopyranosides (formula 3-1) are dissolved in anhydrous DMF (1mL is per 50mg propargyl β-D- glucopyranosides),
Then CuBr and PMDETA are added sequentially in the solution, the mixture of gained is stirred for 24 hours at room temperature in dark.It has reacted
Crude product is dissolved in acetone (the nearly half of anhydrous DMF) by Bi Hou, and the sediment of gained is filtered with Buchner funnel, by gained
Solid is dissolved in deionized water, takes be put into test tube on a small quantity respectively, freeze 16h in refrigerator, is then removed solvent with desivac, is obtained
The functional hyperbranched ferrocene of the amphipathic glucosides of product (formula 3), yield 64%.Wherein, the hyperbranched ferrocene of azido and alkynes third
The molar ratio of base β-D- glucopyranosides is 1.1:1；The molar ratio of CuBr and propargyl β-D- glucopyranosides is 1:1；
The molar ratio of PMDETA and propargyl β-D- glucopyranosides is 1:1.
Embodiment 2
1,1 '-ferrocene dicarboxylic acid 1.5g, absolute methanol 35ml are sequentially added 250mL three neck round bottom flask by step (1)
In, triethylamine 2.8ml is added dropwise, reduces reaction temperature, controls between 0~5 DEG C, thionyl chloride 1.5ml is slowly added dropwise, stirring is anti-
1h is answered, is warming up to 45 DEG C, reaction mixture is poured into reaction solution natural cooling in 250mL single-necked flasks by reaction 5h, is rotated
Methanol removed by evaporation obtains dope, and saturated nacl aqueous solution 40ml is then added thereto, is extracted with 90mL ethyl acetate, merges
It is poured into separatory funnel after organic phase, static layering takes upper layer.Then rotary evaporation removes ethyl acetate, is dried to obtain brown
1,1 '-ferrocene dicarboxylic acid dimethyl ester (formula 1-1) of spicule, yield 87%.
At room temperature in CH3NaOH (2.9g) is added dropwise in OH (26mL), then by 1,1 '-ferrocene dicarboxylic acid dimethyl ester
(20g) is dissolved into acetone (300ml) solution, and this solution is added to above-mentioned ready CH3In OH, resulting slurry
Shape object is placed in 250mL three-necked flasks 10h is stirred at room temperature after, orange solid residue is dissolved in water (500ml),
It pours the mixture into 250mL single-necked flasks, rotary evaporation removes methanol and acetone obtains dope.It is molten that dense HCl is added at 0 DEG C
PH is adjusted in liquid until 1, and collects sediment, is put into drying in thermostatic drying chamber, is obtained 1,1 '-carboxyl ferrocene of yellow solid
Methyl formate (formula 1-2), yield 91%.
1,1 '-carboxyl methyl ferrocenylcarboxylates (20g) and CH are respectively put into 250mL three-necked flasks2Cl2(200mL) is molten
The suspension of liquid is then slowly added into oxalyl chloride (9.1ml), 1h is stirred at room temperature, by solvent and excessive oxalyl chloride true
It is aerial to remove.Obtained residue is dissolved in dichloromethane (200mL), red solution is obtained, hydroboration is added in solution
Sodium (10.5g).Again by CH3OH (100mL) is added dropwise wherein, and 30min is stirred at room temperature in mixture, and water is used after stirring
(300ml) is quenched, by organic layer separation.Water layer CH2Cl2(200ml) is extracted.Vacuum drying, obtains yellow solid residue 1,
1 '-methylol methyl ferrocenylcarboxylate (formula 1-3), yield 94%.
1,1 '-methylol methyl ferrocenylcarboxylate (1.11g) and Sodium azide (1.58g) are dissolved in acetic acid (30ml),
It pours into 250mL three-necked flasks, is heated to 50 DEG C of reaction 18h.After completion of the reaction, three-necked flask is removed, liquid is poured into 250mL
In single-necked flask, it is installed on Rotary Evaporators.Control Rotary Evaporators temperature is gradually warming up to 50 DEG C from 25 DEG C, steams acetic acid
Ethyl ester obtains grease, and reaction mixture concentrates in a vacuum, obtains 1,1 '-azido-methyl ferrocenecarboxylic acid first of orange solids
Ester (formula 1-4), yield 81%.
Step (2) is separately added into 1,1 '-azido-methyl methyl ferrocenylcarboxylate (formula 1- of product in 250mL three-necked flasks
4), G3-HPAE (molar ratios：0.34:1), by three-necked flask as in thermostat water bath, reacting 6h, temperature in a nitrogen atmosphere
Control closes nitrogen, vacuumizes 2h and obtain the hyperbranched ferrocene (formula of milky white shape viscous fluid azido after completion of the reaction at 80 DEG C
2), the grafting rate of the step is 76%.
Step (3), N2Under protection, in 250mL three-necked flasks, by the hyperbranched ferrocene of product azido (formula 2) and alkynes
Propyl β-D- glucopyranosides (formula 3-1) are dissolved in anhydrous DMF (1mL is per 50mg propargyl β-D- glucopyranosides),
Then CuBr and PMDETA are added sequentially in the solution, the mixture of gained is stirred for 24 hours at room temperature in dark.It has reacted
Crude product is dissolved in acetone (the nearly half of anhydrous DMF) by Bi Hou, and the sediment of gained is filtered with Buchner funnel, by gained
Solid is dissolved in deionized water, takes be put into test tube on a small quantity respectively, freeze 16h in refrigerator, is then removed solvent with desivac, is obtained
The functional hyperbranched ferrocene of the amphipathic glucosides of product (formula 3), yield 64%.Wherein, the hyperbranched ferrocene of azido and alkynes third
The molar ratio of base β-D- glucopyranosides is 1.1:1；The molar ratio of CuBr and propargyl β-D- glucopyranosides is 1:1；
The molar ratio of PMDETA and propargyl β-D- glucopyranosides is 1:1.
Embodiment 3
1,1 '-ferrocene dicarboxylic acid 1.5g, absolute methanol 35ml are sequentially added 250mL three neck round bottom flask by step (1)
In, triethylamine 2.8ml is added dropwise, reduces reaction temperature, controls between 0~5 DEG C, thionyl chloride 1.5ml is slowly added dropwise, stirring is anti-
1h is answered, is warming up to 55 DEG C, reaction mixture is poured into reaction solution natural cooling in 250mL single-necked flasks by reaction 4h, is rotated
Methanol removed by evaporation obtains dope, and saturated nacl aqueous solution 40ml is then added thereto, is extracted with 90mL ethyl acetate, merges
It is poured into separatory funnel after organic phase, static layering takes upper layer.Then rotary evaporation removes ethyl acetate, is dried to obtain brown
1,1 '-ferrocene dicarboxylic acid dimethyl ester (formula 1-1) of spicule, yield 80.1%.
At room temperature in CH3NaOH (2.9g) is added dropwise in OH (26mL), then by 1,1 '-ferrocene dicarboxylic acid dimethyl ester
(20g) is dissolved into acetone (300ml) solution, and this solution is added to above-mentioned ready CH3In OH, resulting slurry
Shape object is placed in 250mL three-necked flasks 10h is stirred at room temperature after, orange solid residue is dissolved in water (500ml),
It pours the mixture into 250mL single-necked flasks, rotary evaporation removes methanol and acetone obtains dope.It is molten that dense HCl is added at 0 DEG C
PH is adjusted in liquid until 1, and collects sediment, is put into drying in thermostatic drying chamber, is obtained 1,1 '-carboxyl ferrocene of yellow solid
Methyl formate (formula 1-2), yield 91%.
1,1 '-carboxyl methyl ferrocenylcarboxylates (20g) and CH are respectively put into 250mL three-necked flasks2Cl2(200mL) is molten
The suspension of liquid is then slowly added into oxalyl chloride (9.1ml), 1h is stirred at room temperature, by solvent and excessive oxalyl chloride true
It is aerial to remove.Obtained residue is dissolved in dichloromethane (200mL), red solution is obtained, hydroboration is added in solution
Sodium (10.5g).Again by CH3OH (100mL) is added dropwise wherein, and 30min is stirred at room temperature in mixture, and water is used after stirring
(300ml) is quenched, by organic layer separation.Water layer CH2Cl2(200ml) is extracted.Vacuum drying, obtains yellow solid residue 1,
1 '-methylol methyl ferrocenylcarboxylate (formula 1-3), yield 94%.
1,1 '-methylol methyl ferrocenylcarboxylate (1.11g) and Sodium azide (1.58g) are dissolved in acetic acid (30ml),
It pours into 250mL three-necked flasks, is heated to 50 DEG C of reaction 18h.After completion of the reaction, three-necked flask is removed, liquid is poured into 250mL
In single-necked flask, it is installed on Rotary Evaporators.Control Rotary Evaporators temperature is gradually warming up to 50 DEG C from 25 DEG C, steams acetic acid
Ethyl ester obtains grease, and reaction mixture concentrates in a vacuum, obtains 1,1 '-azido-methyl ferrocenecarboxylic acid first of orange solids
Ester (formula 1-4), yield 81%.
Step (2) is separately added into 1,1 '-azido-methyl methyl ferrocenylcarboxylate (formula 1- of product in 250mL three-necked flasks
4), G3-HPAE (molar ratios：0.34:1), by three-necked flask as in thermostat water bath, reacting 6h, temperature in a nitrogen atmosphere
Control closes nitrogen, vacuumizes 2h and obtain the hyperbranched ferrocene (formula of milky white shape viscous fluid azido after completion of the reaction at 80 DEG C
2), the grafting rate of the step is 76%.
Step (3), N2Under protection, in 250mL three-necked flasks, by the hyperbranched ferrocene of product azido (formula 2) and alkynes
Propyl β-D- glucopyranosides (formula 3-1) are dissolved in anhydrous DMF (1mL is per 50mg propargyl β-D- glucopyranosides),
Then CuBr and PMDETA are added sequentially in the solution, the mixture of gained is stirred for 24 hours at room temperature in dark.It has reacted
Crude product is dissolved in acetone (the nearly half of anhydrous DMF) by Bi Hou, and the sediment of gained is filtered with Buchner funnel, by gained
Solid is dissolved in deionized water, takes be put into test tube on a small quantity respectively, freeze 16h in refrigerator, is then removed solvent with desivac, is obtained
The functional hyperbranched ferrocene of the amphipathic glucosides of product (formula 3), yield 64%.Wherein, the hyperbranched ferrocene of azido and alkynes third
The molar ratio of base β-D- glucopyranosides is 1.1:1；The molar ratio of CuBr and propargyl β-D- glucopyranosides is 1:1；
The molar ratio of PMDETA and propargyl β-D- glucopyranosides is 1:1.
Embodiment 4
1,1 '-ferrocene dicarboxylic acid 1.5g, absolute methanol 35ml are sequentially added 250mL three neck round bottom flask by step (1)
In, triethylamine 2.8ml is added dropwise, reduces reaction temperature, controls between 0~5 DEG C, thionyl chloride 1.5ml is slowly added dropwise, stirring is anti-
1h is answered, is warming up to 50 DEG C, reaction mixture is poured into reaction solution natural cooling in 250mL single-necked flasks by reaction 4.5h, is revolved
Turn methanol removed by evaporation and obtain dope, saturated nacl aqueous solution 40ml is then added thereto, extracted with 90mL ethyl acetate, is closed
And poured into separatory funnel after organic phase, static layering takes upper layer.Then rotary evaporation removes ethyl acetate, is dried to obtain palm fibre
1,1 '-ferrocene dicarboxylic acid dimethyl ester (formula 1-1) of color spicule, yield 80.1%.
At room temperature in CH3NaOH (2.9g) is added dropwise in OH (26mL), then by 1,1 '-ferrocene dicarboxylic acid dimethyl ester
(20g) is dissolved into acetone (300ml) solution, and this solution is added to above-mentioned ready CH3In OH, resulting slurry
Shape object is placed in 250mL three-necked flasks 9h is stirred at room temperature after, orange solid residue is dissolved in water (500ml),
It pours the mixture into 250mL single-necked flasks, rotary evaporation removes methanol and acetone obtains dope.It is molten that dense HCl is added at 0 DEG C
PH is adjusted in liquid until 1, and collects sediment, is put into drying in thermostatic drying chamber, is obtained 1,1 '-carboxyl ferrocene of yellow solid
Methyl formate (formula 1-2), yield 86.3%.
1,1 '-carboxyl methyl ferrocenylcarboxylates (20g) and CH are respectively put into 250mL three-necked flasks2Cl2(200mL) is molten
The suspension of liquid is then slowly added into oxalyl chloride (9.1ml), 1h is stirred at room temperature, by solvent and excessive oxalyl chloride true
It is aerial to remove.Obtained residue is dissolved in dichloromethane (200mL), red solution is obtained, hydroboration is added in solution
Sodium (10.5g).Again by CH3OH (100mL) is added dropwise wherein, and 30min is stirred at room temperature in mixture, and water is used after stirring
(300ml) is quenched, by organic layer separation.Water layer CH2Cl2(200ml) is extracted.Vacuum drying, obtains yellow solid residue 1,
1 '-methylol methyl ferrocenylcarboxylate (formula 1-3), yield 94%.
1,1 '-methylol methyl ferrocenylcarboxylate (1.11g) and Sodium azide (1.58g) are dissolved in acetic acid (30ml),
It pours into 250mL three-necked flasks, is heated to 50 DEG C of reaction 18h.After completion of the reaction, three-necked flask is removed, liquid is poured into 250mL
In single-necked flask, it is installed on Rotary Evaporators.Control Rotary Evaporators temperature is gradually warming up to 50 DEG C from 25 DEG C, steams acetic acid
Ethyl ester obtains grease, and reaction mixture concentrates in a vacuum, obtains 1,1 '-azido-methyl ferrocenecarboxylic acid first of orange solids
Ester (formula 1-4), yield 81%.
Step (2) is separately added into 1,1 '-azido-methyl methyl ferrocenylcarboxylate (formula 1- of product in 250mL three-necked flasks
4), G3-HPAE (molar ratios：0.34:1), by three-necked flask as in thermostat water bath, reacting 6h, temperature in a nitrogen atmosphere
Control closes nitrogen, vacuumizes 2h and obtain the hyperbranched ferrocene (formula of milky white shape viscous fluid azido after completion of the reaction at 80 DEG C
2), the grafting rate of the step is 76%.
Step (3), N2Under protection, in 250mL three-necked flasks, by the hyperbranched ferrocene of product azido (formula 2) and alkynes
Propyl β-D- glucopyranosides (formula 3-1) are dissolved in anhydrous DMF (1mL is per 50mg propargyl β-D- glucopyranosides),
Then CuBr and PMDETA are added sequentially in the solution, the mixture of gained is stirred for 24 hours at room temperature in dark.It has reacted
Crude product is dissolved in acetone (the nearly half of anhydrous DMF) by Bi Hou, and the sediment of gained is filtered with Buchner funnel, by gained
Solid is dissolved in deionized water, takes be put into test tube on a small quantity respectively, freeze 16h in refrigerator, is then removed solvent with desivac, is obtained
The functional hyperbranched ferrocene of the amphipathic glucosides of product (formula 3), yield 64%.Wherein, the hyperbranched ferrocene of azido and alkynes third
The molar ratio of base β-D- glucopyranosides is 1.1:1；The molar ratio of CuBr and propargyl β-D- glucopyranosides is 1:1；
The molar ratio of PMDETA and propargyl β-D- glucopyranosides is 1:1.
Embodiment 5
1,1 '-ferrocene dicarboxylic acid 1.5g (5.5mmol), absolute methanol 35ml are sequentially added 250mL tri- by step (1)
In mouth round-bottomed flask, triethylamine 2.8ml is added dropwise, reduces reaction temperature, controls between 0~5 DEG C, thionyl chloride is slowly added dropwise
1.6ml (22mmol), is stirred to react 1h, is warming up to 40 DEG C, reaction mixture is poured into reaction solution natural cooling by reaction 5h
In 250mL single-necked flasks, rotary evaporation removes methanol and obtains dope, and saturated nacl aqueous solution 40ml is then added thereto, uses
90mL ethyl acetate extracts, and is poured into separatory funnel after merging organic phase, static layering takes upper layer.Then rotary evaporation removes
Ethyl acetate is dried to obtain 1,1 '-ferrocene dicarboxylic acid dimethyl ester (formula 1-1) of brown needles object, yield 83.5%.
At room temperature in CH3NaOH (2.9g) is added dropwise in OH (26mL), then by 1,1 '-ferrocene dicarboxylic acid dimethyl ester
(20g) is dissolved into acetone (300ml) solution, and this solution is added to above-mentioned ready CH3In OH, resulting slurry
Shape object is placed in 250mL three-necked flasks 11h is stirred at room temperature after, orange solid residue is dissolved in water (500ml),
It pours the mixture into 250mL single-necked flasks, rotary evaporation removes methanol and acetone obtains dope.It is molten that dense HCl is added at 0 DEG C
PH is adjusted in liquid until 1, and collects sediment, is put into drying in thermostatic drying chamber, is obtained 1,1 '-carboxyl ferrocene of yellow solid
Methyl formate (formula 1-2), yield 88.6%.
1,1 '-carboxyl methyl ferrocenylcarboxylates (20g) and CH are respectively put into 250mL three-necked flasks2Cl2(200mL) is molten
The suspension of liquid is then slowly added into oxalyl chloride (9.1ml), 1.5h is stirred at room temperature, solvent and excessive oxalyl chloride are existed
It is removed in vacuum.Obtained residue is dissolved in dichloromethane (200mL), red solution is obtained, boron hydrogen is added in solution
Change sodium (10.5g).Again by CH3OH (100mL) is added dropwise wherein, and 25min is stirred at room temperature in mixture, is used after stirring
Water (300ml) is quenched, by organic layer separation.Water layer CH2Cl2(200ml) is extracted.Vacuum drying, obtains yellow solid residue
1,1 '-methylol methyl ferrocenylcarboxylate (formula 1-3), yield 94%.
1,1 '-methylol methyl ferrocenylcarboxylate (1.11g) and Sodium azide (1.58g) are dissolved in acetic acid (30ml),
It pours into 250mL three-necked flasks, is heated to 50 DEG C of reaction 18h.After completion of the reaction, three-necked flask is removed, liquid is poured into 250mL
In single-necked flask, it is installed on Rotary Evaporators.Control Rotary Evaporators temperature is gradually warming up to 50 DEG C from 25 DEG C, steams acetic acid
Ethyl ester obtains grease, and reaction mixture concentrates in a vacuum, obtains 1,1 '-azido-methyl ferrocenecarboxylic acid first of orange solids
Ester (formula 1-4), yield 81%.
Step (2) is separately added into 1,1 '-azido-methyl methyl ferrocenylcarboxylate (formula 1- of product in 250mL three-necked flasks
4), G3-HPAE (molar ratios：0.34:1), by three-necked flask as in thermostat water bath, reacting 6h, temperature in a nitrogen atmosphere
Control closes nitrogen, vacuumizes 2h and obtain the hyperbranched ferrocene (formula of milky white shape viscous fluid azido after completion of the reaction at 80 DEG C
2), the grafting rate of the step is 76%.
Step (3), N2Under protection, in 250mL three-necked flasks, by the hyperbranched ferrocene of product azido (formula 2) and alkynes
Propyl β-D- glucopyranosides (formula 3-1) are dissolved in anhydrous DMF (1mL is per 50mg propargyl β-D- glucopyranosides),
Then CuBr and PMDETA are added sequentially in the solution, the mixture of gained is stirred for 24 hours at room temperature in dark.It has reacted
Crude product is dissolved in acetone (the nearly half of anhydrous DMF) by Bi Hou, and the sediment of gained is filtered with Buchner funnel, by gained
Solid is dissolved in deionized water, takes be put into test tube on a small quantity respectively, freeze 16h in refrigerator, is then removed solvent with desivac, is obtained
The functional hyperbranched ferrocene of the amphipathic glucosides of product (formula 3), yield 64%.Wherein, the hyperbranched ferrocene of azido and alkynes third
The molar ratio of base β-D- glucopyranosides is 1.1:1；The molar ratio of CuBr and propargyl β-D- glucopyranosides is 1:1；
The molar ratio of PMDETA and propargyl β-D- glucopyranosides is 1:1.
Embodiment 6
1,1 '-ferrocene dicarboxylic acid 1.5g (5.5mmol), absolute methanol 35ml are sequentially added 250mL tri- by step (1)
In mouth round-bottomed flask, triethylamine 2.8ml is added dropwise, reduces reaction temperature, controls between 0~5 DEG C, thionyl chloride is slowly added dropwise
0.8ml (11mmol), is stirred to react 1h, is warming up to 50 DEG C, reaction mixture is fallen reaction solution natural cooling by reaction 4.5h
Entering in 250mL single-necked flasks, rotary evaporation removes methanol and obtains dope, and saturated nacl aqueous solution 40ml is then added thereto,
It is extracted, is poured into separatory funnel after merging organic phase, static layering takes upper layer with 90mL ethyl acetate.Then rotary evaporation removes
Ethyl acetate is removed, 1,1 '-ferrocene dicarboxylic acid dimethyl ester (formula 1-1) of brown needles object, yield 80% are dried to obtain.
At room temperature in CH3NaOH (2.9g) is added dropwise in OH (26mL), then by 1,1 '-ferrocene dicarboxylic acid dimethyl ester
(20g) is dissolved into acetone (300ml) solution, and this solution is added to above-mentioned ready CH3In OH, resulting slurry
Shape object is placed in 250mL three-necked flasks 8h is stirred at room temperature after, orange solid residue is dissolved in water (500ml),
It pours the mixture into 250mL single-necked flasks, rotary evaporation removes methanol and acetone obtains dope.It is molten that dense HCl is added at 0 DEG C
PH is adjusted in liquid until 1, and collects sediment, is put into drying in thermostatic drying chamber, is obtained 1,1 '-carboxyl ferrocene of yellow solid
Methyl formate (formula 1-2), yield 90.2%.
1,1 '-carboxyl methyl ferrocenylcarboxylates (20g) and CH are respectively put into 250mL three-necked flasks2Cl2(200mL) is molten
The suspension of liquid is then slowly added into oxalyl chloride (9.1ml), 1.2h is stirred at room temperature, solvent and excessive oxalyl chloride are existed
It is removed in vacuum.Obtained residue is dissolved in dichloromethane (200mL), red solution is obtained, boron hydrogen is added in solution
Change sodium (10.5g).Again by CH3OH (100mL) is added dropwise wherein, and 40min is stirred at room temperature in mixture, is used after stirring
Water (300ml) is quenched, by organic layer separation.Water layer CH2Cl2(200ml) is extracted.Vacuum drying, obtains yellow solid residue
1,1 '-methylol methyl ferrocenylcarboxylate (formula 1-3), yield 94%.
1,1 '-methylol methyl ferrocenylcarboxylate (1.11g) and Sodium azide (1.58g) are dissolved in acetic acid (30ml),
It pours into 250mL three-necked flasks, is heated to 45 DEG C of reaction 18h.After completion of the reaction, three-necked flask is removed, liquid is poured into 250mL
In single-necked flask, it is installed on Rotary Evaporators.Control Rotary Evaporators temperature is gradually warming up to 55 DEG C from 25 DEG C, steams acetic acid
Ethyl ester obtains grease, and reaction mixture concentrates in a vacuum, obtains 1,1 '-azido-methyl ferrocenecarboxylic acid first of orange solids
Ester (formula 1-4), yield 77.8%.
Step (2) is separately added into 1,1 '-azido-methyl methyl ferrocenylcarboxylate (formula 1- of product in 250mL three-necked flasks
4), G3-HPAE (molar ratios：0.54:1), by three-necked flask as in thermostat water bath, reacting 6h, temperature in a nitrogen atmosphere
Control closes nitrogen, vacuumizes 1.5h and obtain the hyperbranched ferrocene (formula of milky white shape viscous fluid azido after completion of the reaction at 80 DEG C
2), the grafting rate of the step is 74%.
Step (3), N2Under protection, in 250mL three-necked flasks, by the hyperbranched ferrocene of product azido (formula 2) and alkynes
Propyl β-D- glucopyranosides (formula 3-1) are dissolved in anhydrous DMF (1mL is per 50mg propargyl β-D- glucopyranosides),
Then CuBr and PMDETA are added sequentially in the solution, the mixture of gained is stirred into 22h at room temperature in dark.It has reacted
Crude product is dissolved in acetone (the nearly half of anhydrous DMF) by Bi Hou, and the sediment of gained is filtered with Buchner funnel, by gained
Solid is dissolved in deionized water, takes be put into test tube on a small quantity respectively, freeze 16h in refrigerator, is then removed solvent with desivac, is obtained
The functional hyperbranched ferrocene of the amphipathic glucosides of product (formula 3), yield 63%.Wherein, the hyperbranched ferrocene of azido and alkynes third
The molar ratio of base β-D- glucopyranosides is 1.2:1；The molar ratio of CuBr and propargyl β-D- glucopyranosides is 1.1:
1；The molar ratio of PMDETA and propargyl β-D- glucopyranosides is 1.1:1.
Embodiment 7
1,1 '-ferrocene dicarboxylic acid 1.5g, absolute methanol 35ml are sequentially added 250mL three neck round bottom flask by step (1)
In, triethylamine 2.8ml is added dropwise, reduces reaction temperature, controls between 0~5 DEG C, thionyl chloride 1.5ml is slowly added dropwise, stirring is anti-
1h is answered, is warming up to 50 DEG C, reaction mixture is poured into reaction solution natural cooling in 250mL single-necked flasks by reaction 4.5h, is revolved
Turn methanol removed by evaporation and obtain dope, saturated nacl aqueous solution 40ml is then added thereto, extracted with 90mL ethyl acetate, is closed
And poured into separatory funnel after organic phase, static layering takes upper layer.Then rotary evaporation removes ethyl acetate, is dried to obtain palm fibre
1,1 '-ferrocene dicarboxylic acid dimethyl ester (formula 1-1) of color spicule, yield 80.1%.
At room temperature in CH3NaOH (2.79g, 69.8mmol) is added dropwise in OH (26mL, 642.5mmol), then by 1,1 '-
Ferrocene dicarboxylic acid dimethyl ester (20g) is dissolved into acetone (300ml) solution, and this solution is added to above-mentioned ready
CH3In OH, resulting slurry is placed in 250mL three-necked flasks 10h is stirred at room temperature after, by orange solid residue
Object is dissolved in water (500ml), is poured the mixture into 250mL single-necked flasks, rotary evaporation remove methanol and acetone obtain it is sticky
Object.It is added at 0 DEG C in dense HCl solution and adjusts pH until 1, and collect sediment, be put into drying in thermostatic drying chamber, obtain Huang
1,1 '-carboxyl methyl ferrocenylcarboxylate (formula 1-2) of color solid, yield 88.5%.
1,1 '-carboxyl methyl ferrocenylcarboxylates (20g) and CH are respectively put into 250mL three-necked flasks2Cl2(200mL) is molten
The suspension of liquid is then slowly added into oxalyl chloride (9.1ml), 1h is stirred at room temperature, by solvent and excessive oxalyl chloride true
It is aerial to remove.Obtained residue is dissolved in dichloromethane (200mL), red solution is obtained, hydroboration is added in solution
Sodium (10.5g).Again by CH3OH (100mL) is added dropwise wherein, and 30min is stirred at room temperature in mixture, and water is used after stirring
(300ml) is quenched, by organic layer separation.Water layer CH2Cl2(200ml) is extracted.Vacuum drying, obtains yellow solid residue 1,
1 '-methylol methyl ferrocenylcarboxylate (formula 1-3), yield 94%.
1,1 '-methylol methyl ferrocenylcarboxylate (1.11g) and Sodium azide (1.58g) are dissolved in acetic acid (30ml),
It pours into 250mL three-necked flasks, is heated to 55 DEG C of reaction 18h.After completion of the reaction, three-necked flask is removed, liquid is poured into 250mL
In single-necked flask, it is installed on Rotary Evaporators.Control Rotary Evaporators temperature is gradually warming up to 55 DEG C from 25 DEG C, steams acetic acid
Ethyl ester obtains grease, and reaction mixture concentrates in a vacuum, obtains 1,1 '-azido-methyl ferrocenecarboxylic acid first of orange solids
Ester (formula 1-4), yield 81%.
Step (2) is separately added into 1,1 '-azido-methyl methyl ferrocenylcarboxylate (formula 1- of product in 250mL three-necked flasks
4), G3-HPAE (molar ratios：0.44:1), by three-necked flask as in thermostat water bath, reacting 6h, temperature in a nitrogen atmosphere
Control closes nitrogen, vacuumizes 3h and obtain the hyperbranched ferrocene (formula of milky white shape viscous fluid azido after completion of the reaction at 75 DEG C
2), the grafting rate of the step is 70.4%.
Step (3), N2Under protection, in 250mL three-necked flasks, by the hyperbranched ferrocene of product azido (formula 2) and alkynes
Propyl β-D- glucopyranosides (formula 3-1) are dissolved in anhydrous DMF (1mL is per 50mg propargyl β-D- glucopyranosides),
Then CuBr and PMDETA are added sequentially in the solution, the mixture of gained is stirred into 26h at room temperature in dark.It has reacted
Crude product is dissolved in acetone (the nearly half of anhydrous DMF) by Bi Hou, and the sediment of gained is filtered with Buchner funnel, by gained
Solid is dissolved in deionized water, takes be put into test tube on a small quantity respectively, freeze 16h in refrigerator, is then removed solvent with desivac, is obtained
The functional hyperbranched ferrocene of the amphipathic glucosides of product (formula 3), yield 63%.Wherein, the hyperbranched ferrocene of azido and alkynes third
The molar ratio of base β-D- glucopyranosides is 1.3:1；The molar ratio of CuBr and propargyl β-D- glucopyranosides is 1.5:
1；The molar ratio of PMDETA and propargyl β-D- glucopyranosides is 1.5:1.
Embodiment 8
1,1 '-ferrocene dicarboxylic acid 1.5g, absolute methanol 35ml are sequentially added 250mL three neck round bottom flask by step (1)
In, triethylamine 2.8ml is added dropwise, reduces reaction temperature, controls between 0~5 DEG C, thionyl chloride 1.5ml is slowly added dropwise, stirring is anti-
1h is answered, is warming up to 50 DEG C, reaction mixture is poured into reaction solution natural cooling in 250mL single-necked flasks by reaction 4.5h, is revolved
Turn methanol removed by evaporation and obtain dope, saturated nacl aqueous solution 40ml is then added thereto, extracted with 90mL ethyl acetate, is closed
And poured into separatory funnel after organic phase, static layering takes upper layer.Then rotary evaporation removes ethyl acetate, is dried to obtain palm fibre
1,1 '-ferrocene dicarboxylic acid dimethyl ester (formula 1-1) of color spicule, yield 80.1%.
At room temperature in CH3NaOH (2.86g, 71.5mmol) is added dropwise in OH (26mL, 642.5mmol), then by 1,1 '-
Ferrocene dicarboxylic acid dimethyl ester (20g) is dissolved into acetone (300ml) solution, and this solution is added to above-mentioned ready
CH3In OH, resulting slurry is placed in 250mL three-necked flasks 10h is stirred at room temperature after, by orange solid residue
Object is dissolved in water (500ml), is poured the mixture into 250mL single-necked flasks, rotary evaporation remove methanol and acetone obtain it is sticky
Object.It is added at 0 DEG C in dense HCl solution and adjusts pH until 1, and collect sediment, be put into drying in thermostatic drying chamber, obtain Huang
1,1 '-carboxyl methyl ferrocenylcarboxylate (formula 1-2) of color solid, yield 90.2%.
1,1 '-carboxyl methyl ferrocenylcarboxylates (20g) and CH are respectively put into 250mL three-necked flasks2Cl2(200mL) is molten
The suspension of liquid is then slowly added into oxalyl chloride (9.1ml), 1h is stirred at room temperature, by solvent and excessive oxalyl chloride true
It is aerial to remove.Obtained residue is dissolved in dichloromethane (200mL), red solution is obtained, hydroboration is added in solution
Sodium (10.5g).Again by CH3OH (100mL) is added dropwise wherein, and 30min is stirred at room temperature in mixture, and water is used after stirring
(300ml) is quenched, by organic layer separation.Water layer CH2Cl2(200ml) is extracted.Vacuum drying, obtains yellow solid residue 1,
1 '-methylol methyl ferrocenylcarboxylate (formula 1-3), yield 94%.
1,1 '-methylol methyl ferrocenylcarboxylate (1.11g) and Sodium azide (1.58g) are dissolved in acetic acid (30ml),
It pours into 250mL three-necked flasks, is heated to 50 DEG C of reaction 18h.After completion of the reaction, three-necked flask is removed, liquid is poured into 250mL
In single-necked flask, it is installed on Rotary Evaporators.Control Rotary Evaporators temperature is gradually warming up to 50 DEG C from 25 DEG C, steams acetic acid
Ethyl ester obtains grease, and reaction mixture concentrates in a vacuum, obtains 1,1 '-azido-methyl ferrocenecarboxylic acid first of orange solids
Ester (formula 1-4), yield 81%.
Step (2) is separately added into 1,1 '-azido-methyl methyl ferrocenylcarboxylate (formula 1- of product in 250mL three-necked flasks
4), G3-HPAE (molar ratios：0.34:1), by three-necked flask as in thermostat water bath, reacting 6h, temperature in a nitrogen atmosphere
Control closes nitrogen, vacuumizes 2h and obtain the hyperbranched ferrocene (formula of milky white shape viscous fluid azido after completion of the reaction at 85 DEG C
2), the grafting rate of the step is 72.3%.
Step (3), N2Under protection, in 250mL three-necked flasks, by the hyperbranched ferrocene of product azido (formula 2) and alkynes
Propyl β-D- glucopyranosides (formula 3-1) are dissolved in anhydrous DMF (1mL is per 50mg propargyl β-D- glucopyranosides),
Then CuBr and PMDETA are added sequentially in the solution, the mixture of gained is stirred into 25h at room temperature in dark.It has reacted
Crude product is dissolved in acetone (the nearly half of anhydrous DMF) by Bi Hou, and the sediment of gained is filtered with Buchner funnel, by gained
Solid is dissolved in deionized water, takes be put into test tube on a small quantity respectively, freeze 16h in refrigerator, is then removed solvent with desivac, is obtained
The functional hyperbranched ferrocene of the amphipathic glucosides of product (formula 3), yield 65%.Wherein, the hyperbranched ferrocene of azido and alkynes third
The molar ratio of base β-D- glucopyranosides is 1.25:1；The molar ratio of CuBr and propargyl β-D- glucopyranosides is 1.3:
1；The molar ratio of PMDETA and propargyl β-D- glucopyranosides is 1.3:1.
The present invention is passed through as raw material using click chemistry (Click chemistry) with 1,1 '-ferrocene dicarboxylic acid
Multi-step reacts, and reaction condition is easy to implement, avoids the use of poisoned catalyst.Ferrocene is introduced into HPAE, and profit
Glucoside is introduced into hyperbranched ferrocene with the reaction of ferrocene side chain, has prepared amphipathic glucosides functionalization over-expense
Change ferrocene.The polymer can good amphipathic, electrochemistry and thermal stability.
Although specific embodiments of the present invention have been described above, those familiar with the art should manage
Solution, we are merely exemplary described specific embodiment, rather than for the restriction to the scope of the present invention, it is familiar with this
The technical staff in field modification and variation equivalent made by the spirit according to the present invention, should all cover the present invention's
In scope of the claimed protection.
Claims (10)
1. a kind of functional hyperbranched ferrocene of amphipathic glucosides, it is characterised in that：The amphipathic glucosides is functional hyperbranched
The chemical structural formula of ferrocene is as shown in Equation 3：
2. a kind of preparation method of the amphipathic functional hyperbranched ferrocene of glucosides as described in claim 1, which is characterized in that
Include the following steps：
Step (1), by compound G3- shown in the azido-methyl methyl ferrocenylcarboxylate of compound 1,1 '-shown in formula 1-4 and formula 2-1
HPAE obtains the hyperbranched ferrocene of compound azido shown in formula 2 by ester exchange reaction, and the step chemical equation is such as
Under：
Step (2), by compound propargyl β-D- pyrans shown in the hyperbranched ferrocene of compound azido shown in formula 2 and formula 3-1
Glucoside is reacted by Click Chemistry, obtains the amphipathic glucosides functionalization over-expense of compound shown in final product formula 3
Change ferrocene, the step chemical equation is as follows：
3. a kind of preparation method of amphipathic functional hyperbranched ferrocene of glucosides according to claim 2, feature exist
In in step (1)：By compound G3- shown in compound 1,1 '-azido-methyl methyl ferrocenylcarboxylate shown in formula 1-4 and formula 2-1
HPAE, first in N2Atmosphere, react under conditions of 75~85 DEG C of temperature, close N after completion of the reaction2, then 1.5~3h is vacuumized, it obtains
To the hyperbranched ferrocene of compound azido shown in formula 2.
4. a kind of preparation method of amphipathic functional hyperbranched ferrocene of glucosides according to claim 2 or 3, feature
It is, 1,1 '-azido-methyl methyl ferrocenylcarboxylate of compound shown in step (1) Chinese style 1-4 and compound G3- shown in formula 2-1
The molar ratio of HPAE is 0.34-0.54:1.
5. a kind of preparation method of amphipathic functional hyperbranched ferrocene of glucosides according to claim 2, feature exist
In in step (2)：By compound propargyl β-D- pyrans shown in the hyperbranched ferrocene of compound azido shown in formula 2 and formula 3-1
Glucoside is dissolved in anhydrous DMF, and under the action of catalyst, dark stirs 22-26h at room temperature；It filters, freeze-drying obtains
The functional hyperbranched ferrocene of the amphipathic glucosides of compound shown in final product formula 3.
6. a kind of preparation method of amphipathic functional hyperbranched ferrocene of glucosides according to claim 5, feature exist
In catalyst described in step (2) is CuBr and PMDETA.
7. a kind of preparation method of amphipathic functional hyperbranched ferrocene of glucosides according to claim 6, feature exist
In the hyperbranched ferrocene of compound azido shown in step (2) Chinese style 2 and compound propargyl β-D- pyrans Portugal shown in formula 3-1
The molar ratio of polyglycoside is 1.1-1.3:1；The molar ratio of compound propargyl β-D- glucopyranosides shown in CuBr and formula 3-1
For 1-1.5:1；The molar ratio of compound propargyl β-D- glucopyranosides shown in PMDETA and formula 3-1 is 1-1.5:1.
8. a kind of preparation method of amphipathic functional hyperbranched ferrocene of glucosides according to claim 2, feature exist
In the preparation method of compound 1 shown in formula 1-4,1 '-azido-methyl methyl ferrocenylcarboxylate includes the following steps：
Step a, compound 1 shown in formula 1,1 '-ferrocene dicarboxylic acid and absolute methanol carry out esterification, obtain shown in formula 1-1
1,1 '-ferrocene dicarboxylic acid dimethyl ester of compound, the step chemical equation are as follows：
After completion of the reaction, acid for adjusting pH is added in step b, compound 1 shown in formula 1-1,1 '-ferrocene dicarboxylic acid dimethyl ester and NaOH
It is worth 1, obtains the carboxyl methyl ferrocenylcarboxylate of compound 1,1 '-shown in formula 1-2, the step chemical equation is as follows：
Step c, compound 1 shown in formula 1-2,1 '-carboxyl methyl ferrocenylcarboxylate are reacted with sodium borohydride, are obtained shown in formula 1-3
1,1 '-methylol methyl ferrocenylcarboxylate of compound, the step chemical equation are as follows：
Step d, compound 1 shown in formula 1-3,1 '-methylol methyl ferrocenylcarboxylate and Sodium azide reaction, obtain shown in formula 1-4
1,1 '-azido-methyl methyl ferrocenylcarboxylate of compound, the step chemical equation are as follows：
9. a kind of preparation method of amphipathic functional hyperbranched ferrocene of glucosides according to claim 8, feature exist
In the preparation method of compound 1 shown in formula 1-4,1 '-azido-methyl methyl ferrocenylcarboxylate includes the following steps：
In 1 '-ferrocene dicarboxylic acid and absolute methanol, triethylamine is added, control temperature is 0 in step a, the compound 1 shown in formula 1
Between~5 DEG C, thionyl chloride is added, continues to be stirred to react 1~1.5h at such a temperature；Reheating rises to 40~55 DEG C, reaction 4
Reaction solution natural cooling is obtained the ferrocene dicarboxylic acid dimethyl ester of compound 1,1 '-shown in formula 1-1 by~5h except solvent, drying；
The ferrocene dicarboxylic acid dimethyl ester of compound 1,1 '-shown in formula 1-1 is dissolved into acetone, and is added to CH by step b3OH and
In the mixed liquor of NaOH, 8~11h is stirred at room temperature, and acid for adjusting pH value is added to 1, obtains the carboxylic of compound 1,1 '-shown in formula 1-2
Base methyl ferrocenylcarboxylate；
Step c, the compound 1 shown in formula 1-2, the CH of 1 '-carboxyl methyl ferrocenylcarboxylate2Cl2Oxalyl chloride is added in suspension,
1~1.5h is stirred at room temperature, is removed solvent, and be dissolved in dichloromethane, is added sodium borohydride, then CH is added dropwise3OH is stirred at room temperature
25-40min obtains the methylol methyl ferrocenylcarboxylate of compound 1,1 '-shown in formula 1-3；
The methylol methyl ferrocenylcarboxylate of compound 1,1 '-shown in formula 1-3 and Sodium azide are dissolved in acetic acid by step d, heating
It is reacted to 45~55 DEG C, after completion of the reaction, obtains the azido-methyl methyl ferrocenylcarboxylate of compound 1,1 '-shown in formula 1-4.
10. a kind of preparation method of amphipathic functional hyperbranched ferrocene of glucosides according to claim 9, feature exist
In the molar ratio of 1,1 '-ferrocene dicarboxylic acid and thionyl chloride is 1 in step a:2~4；CH in step b3OH's and NaOH rubs
You are than being 1:8.9-9.2；It is quenched with water when the reaction is finished in step c；In step d, after completion of the reaction, solvent, evaporation are evaporated
Solvent temperature≤55 DEG C obtain the azido-methyl methyl ferrocenylcarboxylate of compound 1,1 '-shown in formula 1-4.
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| CN101338024A (en) * | 2008-08-12 | 2009-01-07 | 浙江大学 | Method for preparing ferrocenyl hyperbranched polymer sensing material and applications |
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| Investigation of the Redox Property, Migration and Catalytic Performance of Ferrocene-Modified Hyperbranched Poly(amine) Ester;Fengjuan Xiao，等;《Journal of Inorganic and organometallic Polymers and Materials》;20121017;第23卷(第2期);第315-324页，尤其是第318页 * |
| Novel redox active bifunctional crosslinkers from unsymmetrical 1,10-disubstituted ferrocenes;Paul A. Bertin，等;《Tetrahedron Letters》;20090716;第50卷(第38期);第5409-5412页 * |
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| Spectroscopic Investigation on the Interaction of Ferrocene Containing Hyperbranched Poly(amine) Ester with Model Plasma Protein;Fengjuan Xiao，等;《Journal of Inorganic and organometallic Polymers and Materials》;20130918;第24卷(第2期);第360-370页，尤其是第362页 * |
| Spectroscopic investigation on the interaction of hyperbranched poly (amine) ester with model plasma protein: Effect on the structural and conformational changes;Fengjuan Xiao，等;《Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy》;20131008;第118卷;第1106-1112页 * |
| Synthesis of Ferrocene-Based Hyperbranched Polyether and Its Catalytic Performance for Thermal Decomposition of Ammonium Perchlorate;Ruoli Sun，等;《Journal of Inorganic and organometallic Polymers and Materials》;20140919;第24卷(第6期);第1063-1069页 * |
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