CN105295007B - One kind conjugation water-soluble polymer tracer material and preparation method thereof - Google Patents

One kind conjugation water-soluble polymer tracer material and preparation method thereof Download PDF

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CN105295007B
CN105295007B CN201510769760.3A CN201510769760A CN105295007B CN 105295007 B CN105295007 B CN 105295007B CN 201510769760 A CN201510769760 A CN 201510769760A CN 105295007 B CN105295007 B CN 105295007B
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范曲立
梁浩
李�杰
曾高山
卢晓梅
黄维
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Xi'an Alberta Zihuan Analysis And Testing Technology Co ltd
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Nanjing Post and Telecommunication University
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Abstract

The present invention relates to a kind of soluble conjugated polymer tracer molecule, the material has following molecular structural formula:

Description

One kind conjugation water-soluble polymer tracer material and preparation method thereof
Technical field
The invention belongs to soluble conjugated polymer bio-sensing field, and in particular to using main chain as polyfluorene structure, side chain The synthesis of water-soluble polymer with azo quasi-molecule and season ammonification group.
Background technology
Conductive conjugated polymer due to excellent light, electrical property and by organic electronics, biological electronics etc. lead Domain researcher earnestly pays close attention to.Soluble conjugated polymer can be used for chemistry/life as high sensitivity fluorescence probe and sensing material The fields such as thing sensing, biomedical imaging, medical diagnosis on disease and treatment.Soluble conjugated polymer is poly- as the special conjugation of a class Compound is primarily referred to as the conjugated polymer that side chain contains ionic functional group or non-ionic water-soluble functional group, and it is common by tradition The water soluble nature of the excellent photoelectric property of conjugated polymer and polyelectrolyte is combined, and it is advantageously applied to DNA, albumen The detection of the biomolecule such as matter.
The content of the invention
Technical problem:It is an object of the invention to a kind of soluble conjugated polymer tracer material and preparation method thereof.This Prepared material has the characteristic for absorbing main chain polyfluorene structure blue light, the spy in colon cancer tumours cell is run into invention Determine in the case of azo reductase, azo molecules fracture, blue light recovers, and reaches the purpose of detection cancer cell.
Technical scheme:The soluble conjugated polymer tracer material of the present invention has following molecular structure:
Wherein, n is the degree of polymerization, and n is 8-12;
The 5 of side chain are the degree of polymerization of azo quasi-molecule, represent that a side chain is connected to 5 azo molecules.
The main chain of the material is made up of polyfluorene.
The side chain of the material is the molecular structure of azo.
The preparation method of soluble conjugated polymer tracer material of the present invention is:
This method is comprised the following steps that:
Compound 1:2,7- dibromo fluorenes, the positive tetrabutyl are added in two mouthfuls of round-bottomed flasks with reflux condensing tube and magneton Ammonium bromide and 1,6- dibromo-hexanes;Finish and vacuumize the sealing of whole reaction system, be then charged with nitrogen, holding was entirely reacted Journey is carried out in nitrogen atmosphere;The KOH aqueous solution of addition 50%, 4-5h is reacted under 90 DEG C of environment, reactant mixture is cooled down To room temperature;Reactant mixture is neutralized to after neutrality with hydrochloric acid solution, extracted with dichloromethane, extract is dry with anhydrous sodium sulfate It is dry;Filtering, with Rotary Evaporators depressurize precipitation, excessive 1,6-dibromo-hexane is removed with vacuum distillation;Solid crude product is mixed Upper silica gel is using petroleum ether as cleaning solution, and residue is recrystallized to give white crystal with ethanol/methylene after decompression precipitation;
Compound 2:2,7- dibromos fluorenes and positive four fourth are added in two mouthfuls of round-bottomed flasks with reflux condensing tube and magneton Base ammonium bromide, finishes and vacuumizes the sealing of whole reaction system, be then charged with nitrogen, keeps whole course of reaction in nitrogen atmosphere It is middle to carry out;Solvent DMF is injected with syringe, fully after dissolving, sodium hydroxide solution, stirring are injected with syringe 30min;Place a device into and the bromo- 1- propyl alcohol of 3- is slowly added under 90 DEG C of environment, react 24 hours;Saturated common salt is used after completion of the reaction Water and dichloromethane are extracted three times, are merged organic layer, are then dried, mix solid crude product with anhydrous sodium sulfate after suction filtration Upper silica gel is with petroleum ether and ethyl acetate 4:1 is cleaning solution, is purified using silica gel chromatography, then organic layer is dried, It is concentrated to give white solid product;
Compound 3:Compound 1, connection boric acid pinacol ester and potassium acetate are added in two mouthfuls of round-bottomed flasks with magneton, And add catalyst 1, double (diphenylphosphine) ferrocene of 1'-] palladium chloride dichloromethane complex, finish whole reaction system Sealing lucifuge is simultaneously vacuumized, and is then charged with nitrogen, keeps whole course of reaction to be carried out in nitrogen atmosphere;Place a device into 90 DEG C Under environment, solvent DMF is injected with syringe, is reacted 24 hours;After completion of the reaction by crude product dichloromethane Dissolving, by alumina column, removes catalyst;Extracted three times with saturated aqueous common salt and dichloromethane, merge organic layer, Ran Houyong Anhydrous sodium sulfate is dried, and solid crude product is mixed into upper silica gel with petroleum ether and ethyl acetate 10 after suction filtration:1 is cleaning solution, Purified using silica gel chromatography, then organic layer is dried, white solid product is concentrated to give;
Compound 4:In the polymerization pipe with magneton, compound 2 and compound 3, positive TBAB are added, and urge Agent tetrakis triphenylphosphine palladium, finishes and whole reaction system is sealed into lucifuge and vacuumized, be then charged with nitrogen, keeps whole anti- Process is answered to be carried out in nitrogen atmosphere;By toluene solution, solution of potassium carbonate deoxygenation processing, after extract two kinds of solution with syringe and add In polymerization pipe, place a device under 90 DEG C of environment, react 4 days;Crude product tetrahydrofuran is dissolved after completion of the reaction, passes through oxygen Change aluminium post, remove catalyst;Settled after being spin-dried in petroleum ether, post-consumer polymer suction filtration, drying will be settled in beaker;
Compound 5:In the single necked round bottom flask with magneton, compound 4 is added, finishes and seals whole reaction system And vacuumize, nitrogen is then charged with, keeps whole course of reaction to be carried out in nitrogen atmosphere;Add anhydrous methylene chloride and three second Amine, after the bromo- 2- methyl propionyl bromides of 2- are added dropwise;Place a device under 0 DEG C of environment, react 2 hours;To slightly it produce after completion of the reaction Thing dichloromethane and water extraction;Merge organic layer, be then dried, be spin-dried for after suction filtration with anhydrous sodium sulfate, in beaker Settled with petroleum ether, by sedimentation post-consumer polymer drying;
Compound 6:In the polymerization pipe with magneton, compound 5 is added, methyl phenyl ethers anisole, CuBr, dry ice freezing is vacuumized, Logical nitrogen, ethanol thaws, such repetitive cycling three times;Add micro N, N, N, N, N- five methyl diethylentriamines, at 100 DEG C Reaction 24 hours, the crude product that reaction terminates removes catalyst by neutral alundum (Al2O3), concentrates, and is 4/1V/ in methanol/water Settled three times in V mixed liquors, the lower 40 DEG C of dryings of vacuum, you can obtain faint yellow solid;
Compound 7:In the single necked round bottom flask with magneton, compound 6 is added, tetrahydrofuran is added, at -78 DEG C Under, slowly instill after trimethylamine, 30min, solution temperature is warmed to room temperature, after 24h, steam solvent, obtain faint yellow solid.
Beneficial effect:The present invention synthesizes a kind of soluble conjugated polymer tracer molecule by a kind of efficient method.Will Material is dissolved in dichloromethane solution, before azo reductase is added, and no blue light is irradiated under 365nm laser, adds azo After reductase, blue light is had under the irradiation of 365nm laser, this property can effectively detect the colon with azo reductase Cancer cell, plays the applications well effect of cancer cell early detection.
Embodiment
A kind of soluble conjugated polymer tracer material structure of the present invention is as follows:
Wherein, n is the degree of polymerization, and n is 8-12;
The 5 of side chain are the degree of polymerization of azo quasi-molecule, represent that a side chain is connected to 5 azo molecules.
The soluble conjugated polymer tracer material preparation method of the present invention is as follows:
Compound 1:2,7- dibromo fluorenes, the positive tetrabutyl are added in two mouthfuls of round-bottomed flasks with reflux condensing tube and magneton Ammonium bromide and 1,6- dibromo-hexanes;Finish and vacuumize the sealing of whole reaction system, be then charged with nitrogen, holding was entirely reacted Journey is carried out in nitrogen atmosphere;The KOH aqueous solution of addition 50%, 4-5h is reacted under 90 DEG C of environment, reactant mixture is cooled down To room temperature;Reactant mixture is neutralized to after neutrality with hydrochloric acid solution, extracted with dichloromethane, extract is dry with anhydrous sodium sulfate It is dry;Filtering, with Rotary Evaporators depressurize precipitation, excessive 1,6-dibromo-hexane is removed with vacuum distillation;Solid crude product is mixed Upper silica gel is using petroleum ether as cleaning solution, and residue is recrystallized to give white crystal with ethanol/methylene after decompression precipitation;
Compound 2:2,7- dibromos fluorenes and positive four fourth are added in two mouthfuls of round-bottomed flasks with reflux condensing tube and magneton Base ammonium bromide, finishes and vacuumizes the sealing of whole reaction system, be then charged with nitrogen, keeps whole course of reaction in nitrogen atmosphere It is middle to carry out;Solvent DMF is injected with syringe, fully after dissolving, sodium hydroxide solution, stirring are injected with syringe 30min;Place a device into and the bromo- 1- propyl alcohol of 3- is slowly added under 90 DEG C of environment, react 24 hours;Saturated common salt is used after completion of the reaction Water and dichloromethane are extracted three times, are merged organic layer, are then dried, mix solid crude product with anhydrous sodium sulfate after suction filtration Upper silica gel is with petroleum ether and ethyl acetate 4:1 is cleaning solution, is purified using silica gel chromatography, then organic layer is dried, It is concentrated to give white solid product;
Compound 3:Compound 1, connection boric acid pinacol ester and potassium acetate are added in two mouthfuls of round-bottomed flasks with magneton, And add catalyst 1, double (diphenylphosphine) ferrocene of 1'-] palladium chloride dichloromethane complex, finish whole reaction system Sealing lucifuge is simultaneously vacuumized, and is then charged with nitrogen, keeps whole course of reaction to be carried out in nitrogen atmosphere;Place a device into 90 DEG C Under environment, solvent DMF is injected with syringe, is reacted 24 hours;After completion of the reaction by crude product dichloromethane Dissolving, by alumina column, removes catalyst;Extracted three times with saturated aqueous common salt and dichloromethane, merge organic layer, Ran Houyong Anhydrous sodium sulfate is dried, and solid crude product is mixed into upper silica gel with petroleum ether and ethyl acetate 10 after suction filtration:1 is cleaning solution, Purified using silica gel chromatography, then organic layer is dried, white solid product is concentrated to give;
Compound 4:In the polymerization pipe with magneton, compound 2 and compound 3, positive TBAB are added, and urge Agent tetrakis triphenylphosphine palladium, finishes and whole reaction system is sealed into lucifuge and vacuumized, be then charged with nitrogen, keeps whole anti- Process is answered to be carried out in nitrogen atmosphere;By toluene solution, solution of potassium carbonate deoxygenation processing, after extract two kinds of solution with syringe and add In polymerization pipe, place a device under 90 DEG C of environment, react 4 days;Crude product tetrahydrofuran is dissolved after completion of the reaction, passes through oxygen Change aluminium post, remove catalyst;Settled after being spin-dried in petroleum ether, post-consumer polymer suction filtration, drying will be settled in beaker;
Compound 5:In the single necked round bottom flask with magneton, compound 4 is added, finishes and seals whole reaction system And vacuumize, nitrogen is then charged with, keeps whole course of reaction to be carried out in nitrogen atmosphere;Add anhydrous methylene chloride and three second Amine, after the bromo- 2- methyl propionyl bromides of 2- are added dropwise;Place a device under 0 DEG C of environment, react 2 hours;To slightly it produce after completion of the reaction Thing dichloromethane and water extraction;Merge organic layer, be then dried, be spin-dried for after suction filtration with anhydrous sodium sulfate, in beaker Settled with petroleum ether, by sedimentation post-consumer polymer drying;
Compound 6:In the polymerization pipe with magneton, compound 5 is added, methyl phenyl ethers anisole, CuBr, dry ice freezing is vacuumized, Logical nitrogen, ethanol thaws, such repetitive cycling three times;Add micro N, N, N, N, N- five methyl diethylentriamines, at 100 DEG C Reaction 24 hours, the crude product that reaction terminates removes catalyst by neutral alundum (Al2O3), concentrates, and is 4 in first alcohol and water:1 Settled three times in mixed liquor, the lower 40 DEG C of dryings of vacuum, you can obtain faint yellow solid;
Compound 7:In the single necked round bottom flask with magneton, compound 6 is added, tetrahydrofuran is added, at -78 DEG C Under, slowly instill after trimethylamine, 30min, solution temperature is warmed to room temperature, after 24h, steam solvent, obtain faint yellow solid.
For a better understanding of the present invention, the technical side of the present invention is further illustrated below by embodiment Case:
Compound 1:2,7- dibromo fluorenes 9.72g are added in two mouthfuls of round-bottomed flasks with reflux condensing tube and magneton, just TBAB 2g and 1,6- dibromo-hexane 12ml;Finish and vacuumize the sealing of whole reaction system, be then charged with nitrogen, protect Whole course of reaction is held to carry out in nitrogen atmosphere;Add 50% KOH aqueous solution 100ml, under 90 DEG C of environment react 4- 5h, room temperature is cooled to by reactant mixture;Reactant mixture is neutralized to after neutrality with hydrochloric acid solution, extracted with dichloromethane, Extract anhydrous sodium sulfate drying;Filtering, precipitation, excessive 1, the decompression steaming of 6-dibromo-hexane are depressurized with Rotary Evaporators Distillation is gone;Solid crude product is mixed into upper silica gel using petroleum ether as cleaning solution, residue methanol and dichloromethane after decompression precipitation It is recrystallized to give white crystal, i.e. compound 1, common 16.5g (yield 85%);
Compound 2:2,7- dibromo fluorenes 9.72g and just are added in two mouthfuls of round-bottomed flasks with reflux condensing tube and magneton TBAB 3g, finishes and vacuumizes the sealing of whole reaction system, be then charged with nitrogen, keeps whole course of reaction in nitrogen Atmosphere encloses middle progress;Solvent DMF is injected with syringe, fully after dissolving, 50% KOH water is injected with syringe Solution 100ml, stirs 30min;Place a device into and the bromo- 1- propyl alcohol 8ml of 3- are slowly added under 90 DEG C of environment, react 24 hours;Instead Extracted three times with saturated aqueous common salt and dichloromethane after should finishing, merge organic layer, be then dried, taken out with anhydrous sodium sulfate Solid crude product is mixed into upper silica gel with petroleum ether and ethyl acetate 4 after filter:1 is cleaning solution, is purified using silica gel chromatography, Then organic layer dried, be concentrated to give white solid product, i.e. compound 2, common 9.5g (yield 72%);
Compound 3:Compound 1 common 6.5g, connection boric acid pinacol ester 10g are added in two mouthfuls of round-bottomed flasks with magneton With potassium acetate 3g, and catalyst 1 is added, double (diphenylphosphine) ferrocene of 1'-] palladium chloride dichloromethane complex 150mg, plus Finish and whole reaction system is sealed into lucifuge and vacuumized, be then charged with nitrogen, keep whole course of reaction to enter in nitrogen atmosphere OK;Place a device under 90 DEG C of environment, solvent DMF 60ml is injected with syringe, react 24 hours;React Crude product dichloromethane is dissolved after finishing, by alumina column, catalyst is removed;Extracted with saturated aqueous common salt and dichloromethane Three times, merge organic layer, be then dried with anhydrous sodium sulfate, after suction filtration by solid crude product mix upper silica gel with petroleum ether and Ethyl acetate 10:1 is cleaning solution, is purified using silica gel chromatography, and then organic layer is dried, white solid is concentrated to give Product, i.e. compound 3, common 4.68g (yield 63%);
Compound 4:In the polymerization pipe with magneton, the common 0.88g of compound 2, the common 1.48g of compound 3, positive four fourth are added Base ammonium bromide 2g, and catalyst tetrakis triphenylphosphine palladium 150mg, finish and whole reaction system are sealed into lucifuge and vacuumized, so After be filled with nitrogen, keep whole course of reaction to be carried out in nitrogen atmosphere;By toluene solution, solution of potassium carbonate deoxygenation is handled, after Extracted with syringe in two kinds of solution each 10ml, 3ml addition polymerization pipes, place a device under 90 DEG C of environment, react 4 days;React Crude product tetrahydrofuran is dissolved after finishing, by alumina column, catalyst is removed;Settle, will be burnt in petroleum ether after being spin-dried for Post-consumer polymer suction filtration is settled in cup, drying obtains the common 1g (yield 62%) of compound 4;
Compound 5:In the single necked round bottom flask with magneton, the common 0.8g of compound 4 is added, is finished whole reactant System seals and vacuumized, and is then charged with nitrogen, keeps whole course of reaction to be carried out in nitrogen atmosphere;Add anhydrous methylene chloride 10ml, triethylamine 5ml, after the bromo- 2- methyl propionyl bromide 3ml of 2- are added dropwise;Place a device under 0 DEG C of environment, react 2 hours; Crude product dichloromethane and water are extracted after completion of the reaction;Merge organic layer, be then dried with anhydrous sodium sulfate, suction filtration After be spin-dried for, settled in beaker with petroleum ether, will sedimentation post-consumer polymer drying, obtain the common 0.6g (yield 54%) of compound 5;
Compound 6:In the polymerization pipe with magneton, compound 5 common 0.3g, methyl phenyl ethers anisole 3ml, CuBr30mg are added, is done Shaft ice frozen, is vacuumized, and leads to nitrogen, and ethanol thaws, such repetitive cycling three times;Add micro N, N, N, N, the sub- second of N- pentamethyls two Base triamine, reacts 24 hours at 100 DEG C, and the crude product that reaction terminates removes catalyst by neutral alundum (Al2O3), concentrates, First alcohol and water is 4:Settled three times in 1 mixed liquor, the lower 40 DEG C of dryings of vacuum, you can obtain faint yellow solid, yield is 67%;
Compound 7:In the single necked round bottom flask with magneton, compound 6 is added, tetrahydrofuran is added, at -78 DEG C Under, slowly instill after trimethylamine, 30min, solution temperature is warmed to room temperature, after 24h, steam solvent, obtain faint yellow solid, yield For 71%.

Claims (4)

1. one kind conjugation water-soluble polymer tracer material, it is characterised in that the material has following molecular structural formula:
Wherein, n is the degree of polymerization, and n is 8-12;
The 5 of side chain are the degree of polymerization of azo quasi-molecule, represent that a side chain is connected to 5 azo molecules.
2. conjugation water-soluble polymer tracer material according to claim 1, it is characterised in that the main chain of the material is by gathering Fluorenes is constituted.
3. conjugation water-soluble polymer tracer material according to claim 1, it is characterised in that the molecular side chain of the material For the molecular structure of azo.
4. a kind of preparation method of conjugation water-soluble polymer tracer material as claimed in claim 1, it is characterised in that the party Method comprises the following steps:
Compound 1:2,7- dibromo fluorenes, positive tetrabutyl phosphonium bromide are added in two mouthfuls of round-bottomed flasks with reflux condensing tube and magneton Ammonium and 1,6- dibromo-hexanes;Finish and vacuumize the sealing of whole reaction system, be then charged with nitrogen, keep whole course of reaction to exist Carried out in nitrogen atmosphere;The KOH aqueous solution of addition 50%, 4-5h is reacted under 90 DEG C of environment, reactant mixture is cooled into room Temperature;Reactant mixture is neutralized to after neutrality with hydrochloric acid solution, extracted with dichloromethane, extract anhydrous sodium sulfate drying; Filtering, with Rotary Evaporators depressurize precipitation, excessive 1,6-dibromo-hexane is removed with vacuum distillation;Solid crude product is mixed Silica gel is using petroleum ether as cleaning solution, and residue is recrystallized to give white crystal with ethanol/methylene after decompression precipitation;
Compound 2:Compound 1, connection boric acid pinacol ester and potassium acetate are added in two mouthfuls of round-bottomed flasks with magneton, and is added Enter catalyst [1,1'- double (diphenylphosphine) ferrocene] palladium chloride dichloromethane complex, finish whole reaction system is close Envelope lucifuge is simultaneously vacuumized, and is then charged with nitrogen, keeps whole course of reaction to be carried out in nitrogen atmosphere;Place a device into 90 DEG C of rings Under border, solvent DMF is injected with syringe, is reacted 24 hours;It is after completion of the reaction that crude product is molten with dichloromethane Solution, by alumina column, removes catalyst;Extracted three times with saturated aqueous common salt and dichloromethane, merge organic layer, then with nothing Aqueous sodium persulfate is dried, and solid crude product is mixed into upper silica gel with petroleum ether and ethyl acetate 10 after suction filtration:1 is cleaning solution, profit Purified with silica gel chromatography, then organic layer is dried, white solid product is concentrated to give;
Compound 3:2,7- dibromos fluorenes and positive tetrabutyl bromine are added in two mouthfuls of round-bottomed flasks with reflux condensing tube and magneton Change ammonium, finish and vacuumize the sealing of whole reaction system, be then charged with nitrogen, keep whole course of reaction to enter in nitrogen atmosphere OK;Solvent DMF is injected with syringe, fully after dissolving, sodium hydroxide solution, stirring are injected with syringe 30min;Place a device into and the bromo- 1- propyl alcohol of 3- is slowly added under 90 DEG C of environment, react 24 hours;Saturated common salt is used after completion of the reaction Water and dichloromethane are extracted three times, are merged organic layer, are then dried, mix solid crude product with anhydrous sodium sulfate after suction filtration Upper silica gel is with petroleum ether and ethyl acetate 4:1 is cleaning solution, is purified using silica gel chromatography, then organic layer is dried, It is concentrated to give white solid product;
Compound 4:In the polymerization pipe with magneton, compound 2 and compound 3, positive TBAB, and catalyst are added Tetrakis triphenylphosphine palladium, is finished and whole reaction system is sealed into lucifuge and vacuumized, and is then charged with nitrogen, and holding was entirely reacted Journey is carried out in nitrogen atmosphere;By toluene solution, solution of potassium carbonate deoxygenation processing, after extracted two kinds of solution with syringe and added and polymerize Guan Zhong, is placed a device under 90 DEG C of environment, is reacted 4 days;Crude product tetrahydrofuran is dissolved after completion of the reaction, passes through aluminum oxide Post, removes catalyst;Settled after being spin-dried in petroleum ether, post-consumer polymer suction filtration, drying will be settled in beaker;
Compound 5:In the single necked round bottom flask with magneton, compound 4 is added, finishes and whole reaction system is sealed and taken out Vacuum, is then charged with nitrogen, keeps whole course of reaction to be carried out in nitrogen atmosphere;Anhydrous methylene chloride and triethylamine are added, After the bromo- 2- methyl propionyl bromides of 2- are added dropwise;Place a device under 0 DEG C of environment, react 2 hours;After completion of the reaction by crude product Extracted with dichloromethane and water;Merge organic layer, be then dried, be spin-dried for after suction filtration with anhydrous sodium sulfate, used in beaker Petroleum ether is settled, by sedimentation post-consumer polymer drying;
Compound 6:In the polymerization pipe with magneton, compound 5, methyl phenyl ethers anisole, 4- methacryls amido -2 ', 3- bis- are added Methyl- benzene, CuBr, dry ice freezing is vacuumized, and leads to nitrogen, and ethanol thaws, such repetitive cycling three times;Micro N, N are added, N, N, N- five methyl diethylentriamine, react 24 hours at 100 DEG C, and the crude product that reaction terminates is by neutral alundum (Al2O3) Catalyst is removed, is concentrated, is settled three times in methanol/water is 4/1V/V mixed liquors, the lower 40 DEG C of dryings of vacuum, you can obtain yellowish Color solid;
Compound 7:In the single necked round bottom flask with magneton, compound 6 is added, tetrahydrofuran is added, at -78 DEG C, slowly Slow to instill after trimethylamine, 30min, solution temperature is warmed to room temperature, after 24h, steams solvent, obtains faint yellow solid.
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