CN105152973B - stilbene derivative and preparation method and application thereof - Google Patents

Abstract

The invention provides a stilbene derivative (I) having a light stimulus response fluorescence conversion performance. The preparation method of the stilbene derivative comprises the following steps: firstly, p-bromobenzaldehyde (II) and 4-triphenylamine borate (III) are subjected to a Suzuki reaction to generate a triphenylamine intermediate (IV); the triphenylamine intermediate (IV) and 4-methoxyphenyl diethyl phosphate (V) are subjected to a Horner-Wadsworth-Emmons reaction to generate a target product; the light stimulus response fluorescence conversion performance of the stilbene derivative (I) has the characteristics of high contrast, recoverability, and flexible bending, and the synthesis method thereof is simple, and the stilbene derivative can be applied to the fields of fluorescent switches, sensors, storage, and display;

Description

A kind of stilbene derivative and its preparation method and application

(1) Technical field

The invention relates to a stilbene derivative, a preparation method thereof and an application as a reversible light-stimulated fluorescent conversion material, which is suitable for sensors, anti-counterfeiting, storage and displays.

(2) Background technology

The phenomenon that the fluorescent color changes when the material is stimulated by light is called photochromism, and substances with photochromism will have at least two molecular configuration changes. After being stimulated by light, the internal structure of the molecule changes, resulting in the cis-trans isomerization of the molecule, which makes the material change from a cis structure to another trans structure, and the photophysical properties of the material change accordingly. After being treated with heating and solvents, the molecular structure will return to its original state, realizing the reversibility of the fluorescent color change.

The photochromic pigment is added to the transparent resin to make a photochromic material, which can be used in sunglasses lenses, and has begun to be used in photochromic glasses in China. Linking photochromic pigments with high polymers can make materials with photochromic properties, which have great application prospects in photoelectric technology and light control devices. Photochromic materials can be used to make transparent plastic films, pasted or embedded on automobile glass or window glass, and the color will change immediately when exposed to sunlight, so that the sunlight will not be glare, protect eyesight, ensure safety, and can regulate the temperature of the room and the car. Function; It can also be dissolved or mixed into plastic film to be used as agricultural film for greenhouses to increase the output of agricultural products, vegetables, fruits, etc. Another important use is as a military concealment material, such as the clothing of military personnel and the outer cover of combat weapons.

In recent years, the use of photochromic materials in optical information storage, optical regulation, optical switches, optical device materials, optical information genetic materials, modified gene chip materials and other fields has attracted widespread attention worldwide. Chinese researchers have made new progress in the research of erasable high-density optical information storage using new thermally stable spirooxazine materials. They designed and synthesized a new spirooxazine molecular SOFC with good thermal stability of the ring-opening body. This new type of photochromic material shows good stability for information storage, and can be repeatedly written and erased, and can be applied to multi-layer three-dimensional high-density optical information storage based on two-photon technology, showing Strong application prospects.

(3) Contents of the invention

The first object of the present invention is to provide a stilbene derivative with reversible light-stimulus-responsive fluorescence transition properties, which has the characteristics of high contrast, recoverability, and flexibility.

A second object of the present invention is to provide a simple process for the preparation of said stilbene derivatives.

The third object of the present invention is to use the stilbene derivatives as reversible light-stimulated fluorescence conversion materials.

To achieve the above object, the present invention adopts the following technical solutions:

A stilbene derivative shown in a formula (I):

The stilbene derivatives show a reversible photo-stimuli-responsive fluorescence change phenomenon under the condition of light stimulation due to the change of fluorescence emission caused by molecular conformation transition, that is, the transition from one kind of fluorescence emission to multiple fluorescence emission states under external light stimulation , the material after photostimulation can be restored to the fluorescent state before being stimulated by certain means.

Specifically, after the stilbene derivative is exposed to natural light, it changes from blue fluorescence before light to yellow-green fluorescence under ultraviolet light, which has the characteristics of high contrast and many changes in fluorescent color.

The fluorescence conversion performance of the stilbene derivative (I) can be recovered by heating, for example, after the external natural light is applied, the stilbene derivative (I) is transformed from the light before the light under the ultraviolet light The blue fluorescence becomes yellow-green fluorescence after irradiation, and then the material is heat-treated, and the material will automatically recover to the original blue fluorescence before irradiation under the ultraviolet light.

In addition, the fluorescence conversion performance of the stilbene derivative (I) also has the characteristics of flexible bending: after being subjected to external force, it has flexible bending in the crystal state, and automatically returns to the original state when the external force is removed.

The present invention also provides a preparation method of a stilbene derivative shown in formula (I), and the preparation method is carried out as follows:

(1) 4-boric acid triphenylamine shown in p-bromobenzaldehyde and formula (III) is produced triphenylamine intermediate shown in formula (IV) through Suzuki reaction by formula (II);

(2) The triphenylamine intermediate shown in the formula (IV) reacts with 4-methoxyphenyl diethyl phosphate shown in the formula (V) to generate stilbene shown in the formula (I) through the Horner-Wadsworth-Emmons reaction derivative.

Specifically, a preparation method of a stilbene derivative shown in formula (I), the preparation method is carried out as follows:

(1) p-bromobenzaldehyde shown in formula (II), 4-boric acid triphenylamine shown in formula (III), palladium acetate are dissolved in the mixed solvent of deionized water/isopropanol volume ratio 1:1.5～3, Add tripotassium phosphate again, react at room temperature for 10 to 15 minutes, then quench the reaction with saturated saline, and the reaction solution is post-treated to obtain the triphenylamine intermediate shown in formula (IV);

The ratio of the amount of p-bromobenzaldehyde shown in the formula (II) to the amount of triphenylamine borate, palladium acetate, and tripotassium phosphate shown in the formula (III) is 1:0.8～2:0.1～0.3:1.2 ~2;

(2) Under light-shielding conditions, the triphenylamine intermediate shown in formula (IV) obtained in step (1) and 4-methoxyphenyl diethyl phosphate shown in formula (V) are dissolved in tetrahydrofuran A, Cool down to -10-0°C, add potassium tert-butoxide and keep it warm for 10-20 minutes, then naturally return to room temperature and react for 8-16 hours, then quench the reaction with saturated saline, and the reaction solution is post-treated to obtain the formula (I) Show stilbene derivatives;

The ratio of the amount of the triphenylamine intermediate shown in the formula (IV) to the amount of 4-methoxyphenyl phosphate diethyl phosphate shown in the formula (V) is 1:0.5～2.0; the tert-butanol The mass ratio of potassium to the triphenylamine intermediate represented by formula (IV) is 1:5-20.

In step (1) of the preparation method, it is recommended that the volumetric dosage of the mixed solvent (calculated as isopropanol) is 20-35 mL/g based on the mass of p-bromobenzaldehyde represented by formula (II).

In step (1), the post-treatment method of the reaction solution is: after quenching the reaction with saturated brine, the reaction solution is extracted with ethyl acetate, the organic phase is collected, washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, The filtrate was concentrated under reduced pressure, and the residue was separated by silica gel column chromatography, eluted with a mixture of petroleum ether/ethyl acetate with a volume ratio of 30:1, and the eluate containing the target compound was collected, evaporated to remove the solvent, and then dried to obtain Triphenylamine intermediate shown in formula (IV).

In step (2), preferably, the volumetric amount of the tetrahydrofuran A is 15-30 mL/g based on the mass of the triphenylamine intermediate represented by formula (IV). The recommended feeding method of potassium tert-butoxide is: dissolving potassium tert-butoxide in tetrahydrofuran B to obtain a potassium tert-butoxide solution, and then adding it to the reaction system in the form of a solution; The mass of potassium alkoxide is 35-50 mL/g.

It should be noted that the terms "tetrahydrofuran A" and "tetrahydrofuran B" have no special meaning, and both refer to tetrahydrofuran in the usual sense, and the labels "A" and "B" are only used to distinguish tetrahydrofuran used in different operation steps.

In step (2), the post-treatment method of the reaction solution is: after quenching the reaction with saturated brine, the reaction solution is extracted with ethyl acetate, the organic phase is collected, washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, The filtrate was concentrated under reduced pressure, and the residue was separated by silica gel column chromatography, eluted with a mixture of petroleum ether/ethyl acetate with a volume ratio of 15:1, and the eluate containing the target compound was collected, evaporated to remove the solvent, and then dried to obtain A stilbene derivative represented by formula (I).

The present invention characterizes the stilbene derivative (I) through nuclear magnetic resonance (NMR), gas chromatography-mass spectrometry (GC-MS) and elemental analysis, and characterizes the crystal structure of the stilbene derivative (I) through single crystal X-ray diffraction , by differential scanning calorimetry (DSC) to test its structure change temperature transition point and crystallization properties, by scanning electron microscope (SEM) to observe the surface morphology of the material, by ultraviolet-visible light absorption spectrum and fluorescence spectrum to characterize the photophysical properties of the material.

The stilbene derivative (I) of the present invention has reversible light-stimulated fluorescence conversion properties, so it can be used as a reversible light-stimulated fluorescence conversion material, and can be used to prepare reversible light-stimulated response fluorescence conversion devices, for example: the The crystalline solid or powder solid of stilbene derivative (I) can be coated with a thin film on the substrate or by doping it in polymers such as polymethyl methacrylate by existing film-forming technology. A fluorescent conversion device with light-stimuli-responsive properties was prepared by this method.

Compared with the prior art, the beneficial effect of the present invention is that: the present invention provides a kind of organic small molecule stilbene derivative (I) having light-stimulus-responsive fluorescence conversion performance, and the stilbene derivative (I) The photo-stimulus-responsive fluorescence transition performance has the characteristics of high contrast, recoverability, and flexibility, and its synthesis method is simple. It is convenient to prepare devices as a reversible light-stimulated fluorescence transition material, and can be applied to the fields of fluorescent switches, sensors, storage and display.

(4) Description of drawings

Fig. 1 is the photo of stilbene derivative (I) under ultraviolet light before and after light stimulation-heat treatment in the embodiment of the present invention 5,6;

Fig. 2 is the fluorescent photo of the stilbene derivative (I) before (straight), during (bending) and after (recovery) flexible bending in Example 7 of the present invention;

Fig. 3 is a scanning electron micrograph of the stilbene derivative (I) after flexible bending (recovery) in Example 7 of the present invention.

(5) Specific implementation methods

The technical solutions of the present invention will be further described below with specific examples, but the protection scope of the present invention is not limited thereto.

In the embodiment of the present invention, the stilbene derivative (I) and the fluorescence converter are subjected to light with a wavelength of about 190-400 nm.

Example 1

Dissolve 0.92g (5mmol) of p-bromobenzaldehyde (II), 1.88g (6.5mmol) of triphenylamine (III) 4-boronate, and 0.11g (0.5mmol) of palladium acetate in a mixed solvent of 10mL of deionized water/25mL of isopropanol 1.27 g (6 mmol) of tripotassium phosphate was added. React for 10 min at room temperature in air environment. After the reaction was quenched with saturated brine, it was extracted with ethyl acetate (50 mL×3 times), and the organic phases were combined, washed with saturated brine, and dried over anhydrous magnesium sulfate. Filtration, the filtrate was concentrated under reduced pressure, and the residue was separated by silica gel column chromatography, eluted with a mixed solvent with a volume ratio of petroleum ether/ethyl acetate of 30:1, and the eluate containing the target compound was collected, and the solvent was evaporated After drying, 1.56 g of a yellow powder product triphenylamine intermediate (IV) was obtained, with a yield of 90%. The structure confirmation of the substance is characterized as follows: ¹ H NMR (500MHz, DMSO) δ10.03(s, 1H), 7.97(d, J=8.4Hz, 2H), 7.88(d, J=8.3Hz, 2H), 7.75– 7.69(m,2H), 7.40–7.33(m,4H), 7.15–7.07(m,6H), 7.06–7.02(m,2H). MSm/z: 349.2.

Example 2

Dissolve 0.92g (5mmol) of p-bromobenzaldehyde (II), 1.56g (4mmol) of triphenylamine (III) 4-boronate, and 0.11g (0.5mmol) of palladium acetate in a mixed solvent of 10mL of deionized water/25mL of isopropanol , 1.27 g (6 mmol) of tripotassium phosphate was added. React for 10 min at room temperature in air environment. After the reaction was quenched with saturated brine, it was extracted with ethyl acetate (50 mL×3 times), and the organic phases were combined, washed with saturated brine, and dried over anhydrous magnesium sulfate. Filtration, the filtrate was concentrated under reduced pressure, and the residue was separated by silica gel column chromatography, eluted with a mixed solvent with a volume ratio of petroleum ether/ethyl acetate of 30:1, and the eluate containing the target compound was collected, and the solvent was evaporated Dry to obtain 1.27 g of a yellow powder product triphenylamine intermediate (IV), with a yield of 68%.

Example 3:

Weigh 1.74g (5mmol) of the above-synthesized triphenylamine intermediate (IV), 2.58g (10mmol) of diethyl 4-methoxyphenyl phosphate (V) and dissolve it in 45mL of tetrahydrofuran to obtain a mixed solution. Dissolve 0.11 g (1 mmol) of potassium tert-butoxide in 5 mL of tetrahydrofuran, and slowly add the obtained tetrahydrofuran solution of potassium tert-butoxide to the above mixed solution at 0°C, keep stirring for 15 minutes, then gradually return the temperature to room temperature, and The reaction was stirred at room temperature for 8 h, and saturated brine was added to terminate the reaction. Then it was extracted with ethyl acetate (45mL×3), the organic phases were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, the filtrate was concentrated under reduced pressure, and the residue was separated by silica gel column chromatography, and separated by petroleum ether/acetic acid The volume ratio of ethyl ester was 15:1 mixed solvent elution, collected the eluate containing the target compound, evaporated the solvent and dried to obtain 1.35g of light yellow powder product stilbene derivative (I), the yield was 60 %. The reaction and post-processing were protected from light during the whole process. The structure confirmation of the substance is characterized as follows: ¹ H NMR (500MHz, DMSO) δ7.64 (d, J = 4.6Hz, 4H), 7.56 (t, J = 5.8Hz, 2H), 7.38–7.34 (m, 2H), 7.33(dd, J=10.1,2.7Hz,4H),7.23(t,J=13.3Hz,2H),7.10(dd,J=6.3,0.9Hz,2H),7.08–7.06(m,6H),6.96 (d, J=8.8Hz, 2H), 3.78 (d, J=7.5Hz, 3H). MS m/z: 453.2.

Example 4

Weigh 2.80 g (8 mmol) of the above-synthesized triphenylamine intermediate (IV) and 1.29 g (5 mmol) of diethyl 4-methoxyphenyl phosphate (V) and dissolve it in 50 mL of tetrahydrofuran to obtain a mixed solution. Dissolve 0.14 (1.2 mmol) of potassium tert-butoxide in 5 mL of tetrahydrofuran, and slowly add the obtained tetrahydrofuran solution of potassium tert-butoxide to the above mixed solution at 0°C, heat and stir the reaction for 15 minutes, then gradually return the temperature to room temperature, and The reaction was stirred at room temperature for 8 h, and saturated brine was added to terminate the reaction. Then it was extracted with ethyl acetate (45mL×3 times), the organic phases were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, the filtrate was concentrated under reduced pressure, and the residue was separated by silica gel column chromatography and purified with petroleum ether/ The volume ratio of ethyl acetate is 15: 1 mixed solvent elution, collects the eluate containing target compound, evaporates and dries after removing solvent, obtains light yellow powder product stilbene derivative (I) 0.89g, yield is 40%.

Example 5

The stilbene derivative solid powder (I) of the present invention emits blue fluorescence under ultraviolet light, and when the blue fluorescent powder is exposed to light, the recrystallized fluorescent color changes from original blue fluorescence to yellow-green fluorescence.

Example 6

The stilbene derivative solid powder (I) of the present invention emits blue fluorescence under an ultraviolet lamp, and the fluorescent color changes to yellow-green after being illuminated, and is then placed in an oven at 80°C for heat treatment. It is found that the sample obtained after heat treatment is Under the ultraviolet light, the fluorescence color returns to the original blue fluorescence.

Example 7

The stilbene derivative solid powder (I) of the present invention is recrystallized, and the fluorescent color is yellow-green after being illuminated. Afterwards, one of its crystals is picked out independently, and it is found that it can be flexibly bent, and recovers to a straight shape after removing the external force, showing Crystals can be flexibly illuminated.

Claims (10)

1. diphenyl ethylene derivatives shown in a kind of formula (I)：

2. the preparation method of diphenyl ethylene derivatives shown in a kind of formula as claimed in claim 1 (I), it is characterised in that described Preparation method carry out as follows：

(1) p-bromobenzaldehyde and the reactions of 4- boric acid triphenylamine Jing Suzuki shown in formula (III) generate formula (IV) by shown in formula (II) Shown triphenylamine class intermediate；

(2) triphenylamine class intermediate shown in formula (IV) again with 4- methoxyphenyls diethyl phosphate Jing Horner- shown in formula (V) Wadsworth-Emmons reaction generates diphenyl ethylene derivatives shown in formula (I)；

3. the preparation method of diphenyl ethylene derivatives shown in formula (I) as claimed in claim 2, it is characterised in that described system Preparation Method is carried out as follows：

(1) p-bromobenzaldehyde shown in formula (II), 4- boric acid triphenylamines, palladium shown in formula (III) are dissolved in into deionized water/different Propanol volume ratio 1：In 1.5～3 mixed solvent, tripotassium phosphate is added, 10～15min of room temperature reaction is eaten afterwards with saturation Saline is quenched reaction, and reactant liquor is post-treated to obtain triphenylamine class intermediate shown in formula (IV)；

The thing that feeds intake of p-bromobenzaldehyde shown in the formula (II) and 4- boric acid triphenylamines, palladium, tripotassium phosphate shown in formula (III) The ratio of the amount of matter is 1：0.8～2：0.1～0.3：1.2～2；

(2) under the conditions of lucifuge, triphenylamine class intermediate shown in the formula (IV) that step (1) is obtained and 4- methoxyl groups shown in formula (V) Phosphenylic acid diethylester is dissolved in tetrahydrofuran A, is cooled to -10～0 DEG C, adds potassium tert-butoxide and 10～20min of insulation reaction, Then clear-cutting forestland is quenched reaction with saturated aqueous common salt afterwards to 8～16h of room temperature reaction, and reactant liquor is post-treated to obtain formula (I) Shown diphenyl ethylene derivatives；

Triphenylamine class intermediate shown in the formula (IV) and the material that feeds intake of 4- methoxyphenyl diethyl phosphates shown in formula (V) The ratio of amount is 1：0.5～2.0；The potassium tert-butoxide feeds intake mass ratio for 1 with triphenylamine class intermediate shown in formula (IV)：5～ 20。

4. the preparation method of diphenyl ethylene derivatives shown in formula (I) as claimed in claim 3, it is characterised in that step (1) In, the volumetric usage of isopropanol is calculated as 20～35mL/g with the quality of p-bromobenzaldehyde shown in formula (II) in the mixed solvent.

5. the preparation method of diphenyl ethylene derivatives shown in formula (I) as claimed in claim 3, it is characterised in that step (1) In, the method for the reactant liquor post processing is：Saturated aqueous common salt is quenched after reaction, and reactant liquor is extracted with ethyl acetate, and collection has Machine phase, uses saturated common salt water washing, anhydrous magnesium sulfate to be dried, and filters, and takes filtrate reduced in volume, and residue carries out silica gel column chromatography Separate, with petrol ether/ethyl acetate volume ratio 30：1 mixed liquor eluting, collects the eluent containing target compound, is evaporated off molten It is dried after agent, obtains final product triphenylamine class intermediate shown in formula (IV).

6. the preparation method of diphenyl ethylene derivatives shown in formula (I) as claimed in claim 3, it is characterised in that step (2) In, the volumetric usage of the tetrahydrofuran A is calculated as 15～30mL/g with the quality of triphenylamine class intermediate shown in formula (IV).

7. the preparation method of diphenyl ethylene derivatives shown in formula (I) as claimed in claim 3, it is characterised in that the tertiary fourth The feeding mode of potassium alcoholate is：Potassium tert-butoxide is dissolved in tetrahydrofuran B and obtains potassium tert-butoxide solution, then added as a solution In reaction system；The volumetric usage of the tetrahydrofuran B is calculated as 35～50mL/g with the quality of potassium tert-butoxide.

8. the preparation method of diphenyl ethylene derivatives shown in formula (I) as claimed in claim 3, it is characterised in that step (2) In, the method for the reactant liquor post processing is：Saturated aqueous common salt is quenched after reaction, and reactant liquor is extracted with ethyl acetate, and collection has Machine phase, uses saturated common salt water washing, anhydrous magnesium sulfate to be dried, and filters, and takes filtrate reduced in volume, and residue carries out silica gel column chromatography Separate, with petrol ether/ethyl acetate volume ratio 15：1 mixed liquor eluting, collects the eluent containing target compound, is evaporated off molten It is dried after agent, obtains final product diphenyl ethylene derivatives shown in formula (I).

9. application of the diphenyl ethylene derivatives (I) as claimed in claim 1 as reversible photostimulation fluorescence transition material.

10. diphenyl ethylene derivatives (I) as claimed in claim 1 as reversible photostimulation fluorescence transition material prepare it is reversible Photostimulation response fluorescence changes the application in device, and the method for the application is：Stilbene described in claim 1 is derived The crystalline solid or powder solid of thing (I), by way of existing film technique is with the coated film in substrate or passes through The mode being doped in polymethyl methacrylate is obtained the transformation device of the fluorescence with photostimulation response performance.