CN109879858A - A kind of preparation method of the supermolecule polymer network based on tetraphenylethylene - Google Patents
A kind of preparation method of the supermolecule polymer network based on tetraphenylethylene Download PDFInfo
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- CN109879858A CN109879858A CN201910291796.3A CN201910291796A CN109879858A CN 109879858 A CN109879858 A CN 109879858A CN 201910291796 A CN201910291796 A CN 201910291796A CN 109879858 A CN109879858 A CN 109879858A
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Abstract
A kind of synthetic method of the tetraphenylethylene derivative replaced by urea groups pyrimidone, it is directed to the synthesis of wherein compound, specific synthetic reaction synthesizes compound B, Boron tribromide is used again, and it is by 4 that demethylation synthesis compound C, compound C and compound D, which synthesize chemical procedure, 4 '-dibromobenzo-phenones synthesize compound A, Suzuki E is passed through by compound A again, then synthesizes compound F with hydrazine hydrate reduction, final compound F synthesizes compound H with compound G.The beneficial effects of the present invention are embodied in: tetraphenylethylene is convenient for chemical modification and is easy to functionalization, and quaternary tetraphenylethylene class compound synthesis is simple, has apparent fluorescent characteristic, and the enhancing of AIE effect can be applied to supermolecule fluorescent material.
Description
Technical field
The present invention relates to AIE field of fluorescence, and in particular to quaternary tetraphenylethylene class compound and preparation method thereof
And application.
Background technique
Tetraphenylethylene is typical AIE type molecule, is had completely in conventional fluorescent molecule aggregation inducing fluorescent quenching (ACQ)
Opposite luminescence phenomenon: fluorescent chromophore Weak-luminescence under solution state does not shine even, and under solid or coherent condition
A kind of significantly luminous optical physics phenomenon.Wherein tetraphenylethylene have many advantages, such as to be easily-synthesized, easy functionalization, AIE effect it is obvious,
There are important researching value and wide application prospect in fields such as Organic Light Emitting Diode, fluoroscopies.
Fluorescent small molecule crosslinking can be gathered into super by the quaternary tetraphenylethylene derivative modified by urea groups pyrimidone
Molecular functional material, preparation process is simple, and yield is higher and is easy to purify, this AIE type supermolecule by hydrogen bond crosslinks
Polymer has higher luminous efficiency, forms high-intensitive supermolecule fluorescent material.
Summary of the invention
It is an object of the present invention to provide a kind of quaternary tetraphenylethylene class compound for being easily-synthesized, easily modifying and its systems
Preparation Method and application.
To achieve the goals above, the present invention provides a kind of quaternary tetraphenylethylene class compound, this is quaternary
The structure such as following formula of tetraphenylethylene class compound:
Its synthetic route is as follows:
A kind of specific preparation method of the tetraphenylethylene class compound of C4 cladodification carries out as steps described below:
Step 1 (synthesis of compound A): into reaction vessel, 4,4- benzophenone and zinc powder is added, inert gas is protected
Shield, is added dry THF, under ice bath, carbon tetrachloride 1h is added dropwise, addition is refluxed overnight, is cooled to room temperature, 10%K2CO3It is quenched,
Diatomite filtering, DCM extraction merge the drying of organic phase anhydrous magnesium sulfate, obtain compound A after purification.
Step 2 (synthesis of compound B): into reaction vessel, compound A, 4- methoxyphenylboronic acid, TBAB, carbon is added
Sour potassium solution, the toluene of tetra-triphenylphosphine palladium sum stir 16h at T=80 DEG C, are extracted with DCM, merge organic phase, with anhydrous sulphur
Sour magnesium is dry, and revolving obtains compound B after purification.
Step 3 (synthesis of compound C): into reaction vessel, compound B is added, inert gas shielding is added dry
DCM, catalyst are stirred overnight at room temperature, and water quenching is gone out, and compound C is obtained by filtration.
Step 4 (synthesis of compound D): into reaction vessel, phthalimide, K is added2CO3, two bromoalkanes and
Stir 2d at DMF, T=80 DEG C, diatomite filtering, washing, EA extraction, merge it is organic be concerned with dry, rotate to organic solvent-free, add
Enter EtOH ice bath 3h, compound D is obtained by filtration.
Step 5 (synthesis of compound E): into reaction vessel, compound C, compound D, K is added2CO3And DMF, T=80
Stir 2d at DEG C, diatomite filtering, washing, EA extraction, merge it is organic be concerned with dry, obtain compound E after purification.
Step 6 (synthesis of compound F): into reaction vessel, compound E, hydrazine hydrate and EtOH is added, was heated to reflux
Night is cooled to room temperature, and a large amount of chloroform dissolutions are added, and washing merges organic phase, and anhydrous magnesium sulfate is dry, rotates to obtain compound F.
Step 7 (synthesis of compound H): into reaction vessel, compound F is added, inert gas shielding is added dry
Chloroform and compound G, are stirred overnight at room temperature, and it is molten that 1mol/L HCl solution, saturated sodium bicarbonate solution and saturated sodium-chloride is added
Liquid washing, dry with anhydrous magnesium sulfate, revolving, purifying obtains compound H.
Further, the ratio of 4,4- benzophenone, zinc powder and titanium tetrachloride is 1:2.4:1.8 in step 1.
Further, compound A, 4- methoxyphenylboronic acid, TBAB and solution of potassium carbonate in step 2, tetra-triphenylphosphine palladium
Ratio is 1:5:2:5:0.1.
Further, catalyst described in step 3 be Boron tribromide, boron chloride, iodate trimethyl silane, further it is excellent
Choosing, the catalyst are Boron tribromide.
Further, phthalimide described in step 4, K2CO3, two bromoalkanes ratio be 1:3:5.
Further, compound C, compound D and K in step 52CO3Ratio be 1:6:8.
Further, compound E in step 6, hydrazine hydrate ratio be 1:10.
Further, the ratio of compound F and compound G are 1:4.4~6 in step 7.
Further, the inert gas is high pure nitrogen, ordinary nitrogen or argon gas.
Beneficial effects of the present invention are as follows:
(1) the present invention provides the preparation methods of above-mentioned quaternary tetraphenylethylene derivative；
(2) a kind of tetraphenylethylene analog derivative of urea groups pyrimidone modification, is gathered into supermolecule function for fluorescent small molecule
Energy property material guarantees fluorescent small molecule in the effective compound of polymer, and the connection constraint of segment is conducive to aggregation-induced emission, from
And realize luminescence generated by light behavior；
(3) the quaternary tetraphenylethylene derivative synthesized directly has fluorescent characteristic, avoids adding fluorescent dye
It operates, the stabilization in guarantee system, it is convenient to operate.
Specific embodiment
The present invention is described in detail below by specific embodiment, but is not limited the scope of the invention.Unless otherwise specified, originally
Experimental method used by inventing is conventional method, and experiment equipment used, material, reagent etc. can chemically company be bought.
Embodiment 1
Step 1, in 100mL three-necked flask, 4,4 '-dibromobenzo-phenone of 3.00g and 2.88g zinc powder is added, nitrogen is protected
Shield is lower to be added the super dry solvent THF of 80mL, and 4mL TiCl is slowly added dropwise4, 1h is added dropwise, is added dropwise, is heated to reflux 12h, be cooled to
Room temperature is quenched with solution of potassium carbonate, and EA (80mL × 3) extraction is added in diatomite filtering, merges organic phase, and anhydrous magnesium sulfate is dry
It is dry, yellow solid is rotated to obtain, column layer PE:EA=10:1 → EA obtains compound A.
Under step 2, nitrogen protection, compound 1.00g compound A, 1.20g 4- methoxy are added in 100mL three-necked flask
Base phenyl boric acid, the 2mol/L solution of potassium carbonate of 0.5g TBAB, 6mL, the toluene of 1.00g tetra-triphenylphosphine palladium and 25mL, T=80
16h is stirred at DEG C, uses CH2Cl2(30mL × 3) extraction, merges organic phase, dry with anhydrous magnesium sulfate, revolving, column chromatography: PE:
EA=50:1 obtains compound B.
Step 3, the DCM that 0.8g compound B and 10mL is added in 50mL three-necked flask, are added 0.4mL in ice bath
BBr3, 1h is stirred, changes and is stirred overnight at room temperature, water quenching is added to go out, filter to obtain yellow solid, dried to obtain compound with vacuum oven
C。
4.12g phthalimide, 34.16g 1,6- dibromo-hexane, 11.6g is added in step 4 in 50mL single port bottle
2d is stirred at room temperature in the DMF of dried potassium carbonate and 20mL, and diatomite is filtered to remove potassium carbonate, and the EA and 30mL of 50m L is added
The saline solution of saturation, water phase are extracted with EA (70mL × 2), are merged organic phase, (30mL × 5) are washed with water, then use anhydrous magnesium sulfate
It is dry, it rotates to no EA, the ice ethyl alcohol that 300mL is added is put into refrigerator, until solid is precipitated completely, filters to obtain white solid, is put into
Vacuum oven drying, obtains compound D.
Step 5, in 250mL three-necked flask, the dried carbonic acid of 0.5g compound C, 0.97g compound D, 0.43g is added
The DMF of potassium and 15mL is stirred at room temperature 2 days.Be dissolved in water potassium carbonate, filters water washing collection, and the dissolution of 120mL chloroform is added, anhydrous
Magnesium sulfate is dry, revolving, and column chromatography: EA:PE=1:5 → EA obtains compound E.
Step 6, in 100mL three-necked flask, be added 0.8g compound E, 1.0g hydrazine hydrate and 40mL ethyl alcohol, heat back
Night is flowed through, is cooled to room temperature, the dissolution of 300mL chloroform is added, washes (80mL × 3), collects organic phase anhydrous magnesium sulfate drying,
Revolving obtains compound F.
Step 7, N2Under protection, 0.4g compound F, 0.5g compound G and 15mL are added in 50mL three-necked flask
CHCl3, it is stirred at room temperature for 24 hours, fully reacting is cooled to room temperature, and uses 1M HCl, the NaHCO of saturation respectively3, the NaCl solution of saturation
Washing, merge it is organic be concerned with dry, be spin-dried for, column chromatographs DCM:MeOH=400:1, obtains compound G, yield 80%.
Embodiment 2
Step 1, in 100mL three-necked flask, 4,4 '-dibromobenzo-phenone of 5.00g and 4.80g zinc powder is added, nitrogen is protected
Shield is lower to be added the super dry solvent THF of 120mL, and 2.4mL TiCl is slowly added dropwise4, 1h is added dropwise, is added dropwise, is heated to reflux 12h, it is cooling
It to room temperature, is quenched with solution of potassium carbonate, diatomite filtering is added EA (100mL × 3) extraction, merges organic phase, anhydrous magnesium sulfate
It is dry, yellow solid is rotated to obtain, column layer PE:EA=10:1 → EA obtains compound A.
Under step 2, nitrogen protection, compound 0.60g compound A, 0.72g 4- methoxy are added in 100mL three-necked flask
Base phenyl boric acid, the 2mol/L solution of potassium carbonate of 0.60g TBAB, 3.6mL, the toluene of 0.60g tetra-triphenylphosphine palladium and 25mL, T=
16h is stirred at 80 DEG C, uses CH2Cl2(40mL × 3) extraction, merges organic phase, dry with anhydrous magnesium sulfate, revolving, column chromatography:
PE:EA=50:1 obtains compound B.
Step 3, the DCM that 0.5g compound B and 10mL is added in 50mL three-necked flask, are added 0.3mL in ice bath
BBr3, 1h is stirred, changes and is stirred overnight at room temperature, water quenching is added to go out, filter to obtain yellow solid, dried to obtain compound with vacuum oven
C。
4.12g phthalimide, 34.16g 1,6- dibromo-hexane, 11.6g is added in step 4 in 50mL single port bottle
2d is stirred at room temperature in the DMF of dried potassium carbonate and 20mL, and diatomite is filtered to remove potassium carbonate, and the EA and 30mL of 50m L is added
The saline solution of saturation, water phase are extracted with EA (70mL × 2), are merged organic phase, (30mL × 5) are washed with water, then use anhydrous magnesium sulfate
It is dry, it rotates to no EA, the ice ethyl alcohol that 300mL is added is put into refrigerator, until solid is precipitated completely, filters to obtain white solid, is put into
Vacuum oven drying, obtains compound D.
Step 5, in 250mL three-necked flask, the dried carbonic acid of 0.4g compound C, 0.87g compound D, 0.34g is added
The DMF of potassium and 15mL is stirred at room temperature 2 days.Be dissolved in water potassium carbonate, filters water washing collection, and the dissolution of 150mL chloroform is added, anhydrous
Magnesium sulfate is dry, revolving, and column chromatography: EA:PE=1:5 → EA obtains compound E.
Step 6, in 100mL three-necked flask, be added 0.6g compound E, 0.75g hydrazine hydrate and 30mL ethyl alcohol, heating
It is refluxed overnight, is cooled to room temperature, the dissolution of 400mL chloroform is added, washes (80mL × 3), it is dry with anhydrous magnesium sulfate to collect organic phase
Dry, revolving obtains compound F.
Step 7, N2Under protection, 0.35g compound F, 0.43g compound G and 15mL are added in 50mL three-necked flask
CHCl3, it is stirred at room temperature for 24 hours, fully reacting is cooled to room temperature, and uses 1M HCl, the NaHCO of saturation respectively3, the NaCl solution of saturation
Washing, merge it is organic be concerned with dry, be spin-dried for, column chromatographs DCM:MeOH=400:1, obtains compound G, yield 85%.
Embodiment 3
Step 1, in 100mL three-necked flask, 4,4 '-dibromobenzo-phenone of 8.00g and 9.60g zinc powder is added, nitrogen is protected
Shield is lower to be added the super dry solvent THF of 120mL, and 4.8mL TiCl is slowly added dropwise4, 1h is added dropwise, is added dropwise, is heated to reflux 12h, it is cooling
It to room temperature, is quenched with solution of potassium carbonate, diatomite filtering is added EA (120mL × 3) extraction, merges organic phase, anhydrous magnesium sulfate
It is dry, yellow solid is rotated to obtain, column layer PE:EA=10:1 → EA obtains compound A.
Under step 2, nitrogen protection, compound 1.20g compound A, 1.44g 4- methoxy are added in 100mL three-necked flask
Base phenyl boric acid, the 2mol/L solution of potassium carbonate of 1.20g TBAB, 7.2mL, the toluene of 1.20g tetra-triphenylphosphine palladium and 50mL, T=
16h is stirred at 80 DEG C, uses CH2Cl2(60mL × 3) extraction, merges organic phase, dry with anhydrous magnesium sulfate, revolving, column chromatography:
PE:EA=50:1 obtains compound B.
Step 3, the DCM that 1.00g compound B and 15mL is added in 50mL three-necked flask, are added 0.6mL in ice bath
BBr3, 1h is stirred, changes and is stirred overnight at room temperature, water quenching is added to go out, filter to obtain yellow solid, dried to obtain compound with vacuum oven
C。
8.24g phthalimide, 64.32g 1,6- dibromo-hexane, 23.2g is added in step 4 in 50mL single port bottle
The DMF of dried potassium carbonate and 40mL, is stirred at room temperature 2d, and diatomite is filtered to remove potassium carbonate, and the EA and 50mL of 80mL is added
The saline solution of saturation, water phase are extracted with EA (100mL × 2), are merged organic phase, (40mL × 5) are washed with water, then use anhydrous magnesium sulfate
It is dry, it rotates to no EA, the ice ethyl alcohol that 400mL is added is put into refrigerator, until solid is precipitated completely, filters to obtain white solid, is put into
Vacuum oven drying, obtains compound D.
Step 5, in 250mL three-necked flask, the dried carbonic acid of 0.8g compound C, 1.74g compound D, 0.68g is added
The DMF of potassium and 20mL is stirred at room temperature 2 days.Be dissolved in water potassium carbonate, filters water washing collection, and the dissolution of 200mL chloroform is added, anhydrous
Magnesium sulfate is dry, revolving, and column chromatography: EA:PE=1:5 → EA obtains compound E.
Step 6, in 100mL three-necked flask, be added 1.2g compound E, 1.50g hydrazine hydrate and 60mL ethyl alcohol, heating
It is refluxed overnight, is cooled to room temperature, the dissolution of 400mL chloroform is added, washes (100mL × 3), it is dry with anhydrous magnesium sulfate to collect organic phase
Dry, revolving obtains compound F.
Step 7, N2Under protection, 0.70g compound F, 0.86g compound G and 15mL are added in 50mL three-necked flask
CHCl3, it is stirred at room temperature for 24 hours, fully reacting is cooled to room temperature, and uses 1M HCl, the NaHCO of saturation respectively3, the NaCl solution of saturation
Washing, merge it is organic be concerned with dry, be spin-dried for, column chromatographs DCM:MeOH=400:1, obtains compound G, yield 82%.
Claims (4)
1. a kind of preparation method of the supermolecule polymer network based on tetraphenylethylene, which is characterized in that should be quaternary
Tetraphenylethylene class compound, is denoted as compound H, and chemical structural formula is as follows:
。
2. a kind of preparation method of the tetraphenylethylene class compound of C4 cladodification described in claim 1, this method comprises:
(1) under nitrogen protection, 4,4- benzophenone and zinc powder are dissolved in dry organic solvent, under ice bath, are added dropwise slow four
Chlorination carbon, addition are refluxed overnight, and are cooled to room temperature, and are quenched, and are filtered, extraction, merge it is organic be concerned with dry, obtain compound after purification
A
(2) under nitrogen protection, compound A, 4- methoxyphenylboronic acid, TBAB, the toluene of solution of potassium carbonate sum, addition catalysis is added
Agent carry out suzuki reaction, stir 16h, extracted with DCM, merge it is organic be concerned with it is dry, revolving, obtain compound B after purification
(3) into reaction vessel, compound B is added, dry DCM is added in inert gas shielding, and catalyst was stirred at room temperature
Night, water quenching are gone out, and compound C is obtained by filtration
(4) into reaction vessel, phthalimide, K is added2CO3, two bromoalkanes and DMF, stir 2d, filter, wash, extraction
It takes, merges organic dry, revolving to organic solvent-free that is concerned with, compound D is obtained by filtration, and above-mentioned has in addition organic solvent ice bath
Solvent includes methanol and ethyl alcohol
(5) into reaction vessel, compound C, compound D, K is added2CO3And DMF, lower stirring 2d, it filters, washing, EA extraction,
Merge it is organic be concerned with dry, obtain compound E after purification
(6) into reaction vessel, compound E, hydrazine hydrate and EtOH, heated overnight at reflux is added and is cooled to room temperature, be added a large amount of
Organic solvent dissolution, washing, merge it is organic be concerned with it is dry, revolving, obtain compound F, above-mentioned organic solvent includes chloroform and two
Chloromethanes
(7) into reaction vessel, compound F is added, inert gas shielding is added dry chloroform and compound G, is stirred at room temperature
Overnight, be added hydrochloric acid, saturated sodium bicarbonate and saturated sodium-chloride washing, merge it is organic be concerned with it is dry, revolving, purifying obtain compound
H, above-mentioned concentration of hydrochloric acid are 1mol/L.
3. tetraphenylethylene class compound according to claim 4, which is characterized in that suzuki reaction condition are as follows: catalyst
For tetra-triphenylphosphine palladium, reaction temperature is 80~100 DEG C, and the reaction time is 5~30h.
4. quaternary tetraphenylethylene class compound according to claim 1 is as blue light material application, feature exists
In as fluorescence supramolecular materials.
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| CN110628039A (en) * | 2019-09-27 | 2019-12-31 | 西北师范大学 | Supramolecular polymer hydrogel based on bipod gelator and application thereof |
| CN111269173A (en) * | 2020-02-16 | 2020-06-12 | 常州大学 | Preparation and application of solid fluorescent test paper material |
| CN112830992A (en) * | 2021-01-07 | 2021-05-25 | 浙江理工大学 | Cross-linked AIE polymer nano-particle, preparation thereof and application thereof in detection of aqueous phase nitroaromatic compound |
| CN115160912A (en) * | 2021-04-02 | 2022-10-11 | 南京工业大学 | Fluorescent temperature-sensitive coating material based on conjugated polymer and preparation method and application thereof |
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| CN109134384A (en) * | 2018-09-29 | 2019-01-04 | 常州大学 | A kind of preparation method of aggregation-induced emission hydrogen-bonded polymer network |
| CN109369543A (en) * | 2018-12-11 | 2019-02-22 | 常州大学 | A kind of tetraphenylethylene synthetic method that urea groups pyrimidone replaces |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109134384A (en) * | 2018-09-29 | 2019-01-04 | 常州大学 | A kind of preparation method of aggregation-induced emission hydrogen-bonded polymer network |
| CN109369543A (en) * | 2018-12-11 | 2019-02-22 | 常州大学 | A kind of tetraphenylethylene synthetic method that urea groups pyrimidone replaces |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110628039A (en) * | 2019-09-27 | 2019-12-31 | 西北师范大学 | Supramolecular polymer hydrogel based on bipod gelator and application thereof |
| CN110628039B (en) * | 2019-09-27 | 2021-06-08 | 西北师范大学 | Supramolecular polymer hydrogel based on bipod gelator and application thereof |
| CN111269173A (en) * | 2020-02-16 | 2020-06-12 | 常州大学 | Preparation and application of solid fluorescent test paper material |
| CN112830992A (en) * | 2021-01-07 | 2021-05-25 | 浙江理工大学 | Cross-linked AIE polymer nano-particle, preparation thereof and application thereof in detection of aqueous phase nitroaromatic compound |
| CN112830992B (en) * | 2021-01-07 | 2022-07-26 | 浙江理工大学 | Cross-linked AIE polymer nano particle, preparation thereof and application thereof in detection of aqueous phase nitroaromatic compound |
| CN115160912A (en) * | 2021-04-02 | 2022-10-11 | 南京工业大学 | Fluorescent temperature-sensitive coating material based on conjugated polymer and preparation method and application thereof |
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