CN109369543A

CN109369543A - A kind of tetraphenylethylene synthetic method that urea groups pyrimidone replaces

Info

Publication number: CN109369543A
Application number: CN201811508163.5A
Authority: CN
Inventors: 肖唐鑫; 夏晗; 甄子涵; 陶玉红; 吴月晗; 周玲
Original assignee: Changzhou University
Current assignee: Changzhou University
Priority date: 2018-12-11
Filing date: 2018-12-11
Publication date: 2019-02-22

Abstract

A kind of tetraphenylethylene synthetic method that urea groups pyrimidone replaces, it is directed to three kinds of compounds and its synthetic method, specific synthesis step is first to synthesize compound A by UPy precursor, compound B is synthesized by benzophenone and 4- aminobenzophenone again, the tetraphenylethylene of urea groups pyrimidone substitution is finally synthesized by compound A and compound B.The beneficial effects of the present invention are embodied in: urea groups pyrimidone is convieniently synthesized, it can occur from complementary dimerization, tetraphenylethylene molecular structure is simple, convenient for chemical modification and functionalization, AIE efficiency can be enhanced in the Supramolecular Functions material that dimeric forms are formed after urea groups pyrimidone combination tetraphenylethylene, provides foundation for supermolecule solid luminescent material.

Description

A kind of tetraphenylethylene synthetic method that urea groups pyrimidone replaces

Technical field

The invention belongs to supramolecular chemistry fluorescence sense field, in particular to a kind of tetraphenyl second of urea groups pyrimidone substitution Alkene synthetic method.

Background technique

Tetraphenylethylene (Tetraphenylethene, TPE) class compound has big conjugated system, 4 benzene of molecule Ring is connected in the same isolated double bond, and since the presence of steric hindrance distorts phenyl ring between each other, thus molecule is in Airfoil shape.It is such compound light-emitting function admirable, convieniently synthesized, it is a kind of excellent aggregation-induced emission (AIE) chemical combination Object is furtherd investigate in fields such as Organic Light Emitting Diode, liquid crystal device, Supramolecular Assembling, drug release, sensors. The urea groups pyrimidone unit (UPy) developed first by E.W.Meijer seminar is current most widely used Quadrupolar hydrogen bond module (Science 1997,278,1601.).Why UPy, which receives significant attention reason, three: first is that UPy is convenient for synthesis；Second is that The binding pattern of the Quadrupolar hydrogen bond of UPy is from complementation, and DDAA type therein, itself can be with dimerization, so being widely used.This The UPy module that invention will form Quadrupolar hydrogen bond is joined in TPE, develops a kind of oversubscription that can be combined by Hyarogen-bonding Sub- dimerization TPE material.

Summary of the invention

The tetraphenylethylene that urea groups pyrimidone provided by the invention replaces, is denoted as compound C, the following institute of molecular structural formula Show:

Its synthetic route is as follows:

A kind of specific preparation method for the tetraphenylethylene that urea groups pyrimidone replaces, carries out as steps described below:

Step 1 (synthesis of compound A): being added UPy precursor and CDI into reaction vessel, and under nitrogen protection, drying is added CHCl₃, after being stirred at room temperature more than two hours, stop reaction, water quenching added to go out, filter, liquid separation, take organic phase dry, changed Close object A.

The molar ratio of UPy precursor and CDI in step (1) is 1:3.5, and CDI mass fraction is 98%.

Step 2 (synthesis of compound B): further, 5.8g zinc powder is added into reaction vessel, is added under nitrogen protection TiCl is slowly added dropwise with constant pressure funnel under the conditions of ice-water bath in dry THF₄, 2h is then stirred at room temperature, then in ice bath Lower addition pyridine stirs 10min, is slow added into benzophenone and 4- aminobenzophenone and dry THF, is heated to reflux, Stop reaction, post-processing is cooled to room temperature, with 10% K₂CO₃Solution is quenched, diatomite filtering, and DCM extraction merges organic phase It is dry, compound B is obtained after revolving.

Wherein 4- aminobenzophenone in step (2): benzophenone: pyridine: TiCl₄: the molar ratio of Zn is 1:1.24:3: 5:10, the mass fraction of pyridine are 99.5%.

Step 3 (synthesis of compound C): it further, the synthesis of compound C: is added into reaction vessel and obtains step (1) The compound A arrived under nitrogen protection, is added the compound B that step (2) obtain, adds dry CHCl₃Solution, at room temperature Stirring is more than 2h, the post-processing HCl, the NaHCO of saturation of 1mol/L₃The washing of the NaCl solution of solution and saturation, merges organic With anhydrous MgSO after phase₄It is dry, compound C is obtained after revolving.

Wherein the molar ratio of compound B and compound A described in step (3) is 1:1.5, dry CHCl₃For 20mL, TLC DCM:MeOH=40:1.

The beneficial effects of the present invention are embodied in:

(1) for the present invention using tetraphenylethylene as luminophore, tetraphenylethylene molecular structure is simple, repairs convenient for chemistry Decorations and functionalization, the luminescent material of available very high solid fluorescence quantum efficiency.

(2) the hydrogen bond unit urea groups pyrimidone that the present invention utilizes is current most widely used Quadrupolar hydrogen bond module, it Synthesis is simple, can occur from complementary dimerization, for forming the supermolecule function of dimeric forms after combination tetraphenylethylene AIE efficiency can be enhanced in energy material.

(3) the present invention is based on the functional materials of oversubscription subbase, and supermolecule monomer structure is simple, ingenious in design, synthesis letter Just, foundation is provided for the supermolecule solid luminescent material in future.

Detailed description of the invention

Fig. 1 is compound C in CDCl₃In hydrogen nuclear magnetic resonance (¹H NMR) spectrogram, wherein abscissa is chemical shift (ppm)。

Fig. 2 is compound C in CDCl₃In nuclear magnetic resonance carbon (¹³C NMR) spectrogram, wherein abscissa is chemical shift (ppm)。

Specific embodiment

In order to better understand the present invention, below by specific embodiment, the invention will be further described.

Embodiment 1

The synthesis of step 1, compound A: in the three-necked flask of 500mL, 0.14g UPy precursor and 0.38g are separately added into CDI, vacuumizes for continuous 2~4 times, inflated with nitrogen circulation, and 10mL is added in the oxygen and moisture in exclusion system under nitrogen protection 98% dry CHCl₃, solution is stirred at room temperature more than 2h, stops reaction, water quenching is added to go out, filter, and liquid separation takes organic phase nothing Water MgSO₄It is dry, obtain compound A.

The synthesis of step 2, compound B: 5.8g zinc powder is added in 250mL three-necked flask, is vacuumized for continuous 2~4 times, 60mL THF is added under nitrogen protection in inflated with nitrogen circulation, oxygen and moisture in exclusion system, under the conditions of ice salt bath, with perseverance 5mLTiCl is slowly added dropwise in pressure dropping funel₄, 2.5h is stirred at room temperature, then be changed to ice salt bath, the stirring of 1.53mL pyridine is added 10min is slow added into the dry THF solution of 2g benzophenone, 1.75g4- aminobenzophenone and 40mL, was heated to reflux At night, stop reaction, post-processing is cooled to room temperature, uses 10%K₂CO₃Solution is quenched, diatomite filtering, DCM extraction (100mL × 3), merge organic dry revolving that is concerned with, obtain yellow solid, yield 82.3%.

The synthesis of step 3, compound C: 1g compound B is added in the three-necked flask of 500mL, and continuous 2~4 pumpings are true Sky, inflated with nitrogen recycle, the oxygen and moisture in exclusion system, and the compound A and 20mL that 1.31g is added under nitrogen protection are dry CHCl₃Solution stirs at room temperature, and the post-processing HCl of 1mol/L is saturated NaHCO₃The NaCl solution washing of solution, saturation, Merge the anhydrous MgSO of organic phase₄Compound C, yield 83.6% are obtained after dry revolving.

The step of 2~5 reference implementation example 1 of embodiment, only changing the step the molar ratio of compound B and compound A in three is 1:1,1:2,1:2.5,1:3.

Examples 1 to 5 yield list

As can be seen from the table when the molar ratio of compound B and compound A is less than 1:1.5, yield is with compound A institute The increase of accounting weight and become larger, when the molar ratio of compound B and compound A are more than 1:1.5, the yield of compound C is not bright It is aobvious to increase, so as to obtain under experimental conditions, when the molar ratio of compound B and compound A are 1:1.5 under the experiment condition Optimal.

Claims

1. the tetraphenylethylene synthetic method that a kind of urea groups pyrimidone (UPy) replaces, comprising the following steps:

A. it weighs a certain amount of UPy precursor and CDI is added to dry CHCl₃It is stirred at room temperature in solution, water quenching is added after fully reacting It goes out, then filtering, liquid separation, take organic phase to be dried to obtain compound A, and UPy precursor is 0.1~0.2g in the step, and the amount of CDI is 2.0~2.5g, mixing time are 2~4h.

B. it takes a certain amount of zinc powder in flask, tetrahydrofuran is added, under the conditions of ice-water bath, TiCl is added dropwise in constant pressure funnel₄, It stirs at room temperature, then pyridine stirring is added under ice-water bath, be eventually adding benzophenone, 4- aminobenzophenone and THF, heat Reflux, uses K after fully reacting₂CO₃It is quenched, diatomite filtering, DCM extraction, is dried to obtain compound B.Then into compound B The product A and dry CHCl of step a preparation is added₃Solution stirs at room temperature, with 1mol/L hydrochloric acid, saturation after fully reacting NaHCO₃The washing of the NaCl solution of solution and saturation obtains product urea groups pyrimidine after merging organic phase anhydrous magnesium sulfate drying The tetraphenylethylene that ketone replaces.

2. the tetraphenylethylene synthetic method that a kind of urea groups pyrimidone according to claim 1 replaces, which is characterized in that step It is 2~4h that the time is stirred at room temperature in rapid b, and mixing time is 10~15min under ice bath.

3. the tetraphenylethylene synthetic method that a kind of urea groups pyrimidone according to claim 1 replaces, which is characterized in that step The molar ratio of UPy precursor described in rapid a and CDI are 1:3.5, and CDI mass fraction used is 98%.Hexichol first described in step b The molar ratio of ketone and 4- aminobenzophenone is that the molar ratio of 1:1.24, compound B and compound A are 1:1.5.