CN110407718A - Using triphenylamine as the saccharin analog derivative of donor and its preparation and application - Google Patents
Using triphenylamine as the saccharin analog derivative of donor and its preparation and application Download PDFInfo
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- CN110407718A CN110407718A CN201910548735.0A CN201910548735A CN110407718A CN 110407718 A CN110407718 A CN 110407718A CN 201910548735 A CN201910548735 A CN 201910548735A CN 110407718 A CN110407718 A CN 110407718A
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- saccharin
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
- C07C251/28—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having nitrogen atoms of imino groups acylated
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- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
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Abstract
The present invention provides a kind of using triphenylamine as the saccharin analog derivative (I) of donor, and preparation method thereof and its preparation piezochromic material in application.Such novel saccharin analog derivative is as luminescent material, it can be obtained respectively by green by the grinding to its two kinds of crystal to photochromic transformation yellow and by indigo plant to Huang, its advantages are mainly reflected in: preparation method is simple, and material has excellent piezallochromy property.
Description
(1) technical field
The present invention relates to a kind of using triphenylamine as the saccharin analog derivative of donor, and preparation method thereof and its making
Application in standby piezochromic material.
(2) background technique
Organic stimuli responsive material refer to by outside environmental elements (such as temperature, pressure, solvent, PH) influence after, from
Body physical property (such as color shines) changed organic material.Wherein, piezochromic material has obtained extensively in recent years
In-depth study.The phenomenon that piezallochromy refers to material under external force, and fluorescence color can change.With pressure mutagens
The material of color property shows unprecedented application potential in multiple fields such as anti-counterfeit recognition, chemical sensitisations.Therefore, pressure is caused
The research and development of off-color material has important theoretical significance and practical application value.
Triphenylamine is often applied to constructing for light emitting molecule as a kind of stronger electron donating group.Saccharin class
Derivative due to oxygen, nitrogen-atoms presence, it is intermolecular to be easily formed the weak interaction such as hydrogen bond, lead to its changeable state of aggregation
Structure, and this is just conducive to it and obtains piezallochromy property.Derived using the novel saccharin class that triphenylamine is constructed as donor
Object is for pushing the development of piezallochromy luminescent material to have great significance.
(3) summary of the invention
The purpose of the present invention is to provide a kind of using triphenylamine as the novel saccharin analog derivative of donor, and its system
Preparation Method and its application in preparation piezochromic material.
The technical solution adopted by the present invention is that:
It is a kind of using triphenylamine as the saccharin analog derivative of donor, shown in structure such as formula (I):
The invention further relates to the methods for preparing the saccharin analog derivative, which comprises by formula (II) institute
Show that compound is dissolved in methylene chloride, for the ultraviolet light irradiation of 365nm after 5~7 days, reaction solution is isolated and purified to obtain the benzene first
Imide derivatives；The amount of methylene chloride at least will all dissolve reactant.
The isolation and purification method is as follows: reaction solution successively uses methylene chloride and deionized water to extract, and merges organic phase, adds
Enter MgSO4It is dry, it is concentrated under reduced pressure, column chromatography for separation purification obtains yellow solid target product, the as described saccharin class
Derivative；
When the column chromatography for separation, stationary phase is 300~400 mesh silica gel, and mobile phase is petroleum ether: ethyl acetate volume ratio
The mixed solvent of 3:1.
Formula (II) compound comprises the following steps: under nitrogen protection, by 4- fluoroaniline, benzil, hexichol amido benzene
Formaldehyde and Ammoniom-Acetate are dissolved in acetic acid solvent, and heating reflux reaction 10~18 hours, reaction solution was through isolating and purifying to obtain formula
(II) compound.
The isolation and purification method is as follows: deionized water is added after reaction solution is cooling, white solid, filtering, filter residue is precipitated
It is successively extracted with methylene chloride and deionized water, merges organic phase, MgSO is added4It is dry, it is concentrated under reduced pressure, column chromatography for separation mentions
It is pure, desired product as white solid is obtained, as described formula (II) compound.
The ratio between amount of the 4- fluoroaniline, benzil, diphenylamines benzaldehyde and Ammoniom-Acetate substance be 1~5:1:1~
1.2:1~4.To make the reactant just, all dissolution is advisable the additional amount of the acetic acid.
When the column chromatography for separation, stationary phase is 300~400 mesh silica gel, and mobile phase is ethyl acetate: methylene chloride volume
Mixed solvent than 1:200.
The invention further relates to application of the saccharin analog derivative in preparation piezochromic material.
Above-mentioned obtained compound (I) is dissolved in the in the mixed solvent of second alcohol and water under different proportion, it is slow to solvent
Slow vaporization grows crystal.Obtain the crystal of two kinds of colour light emittings of green and blue, respectively 1a and 1b.
1a and 1b, which is further carried out grinding with mortar, can change its luminous color, and 1a is turned yellow by green, 1b
It is turned yellow by blue.
The beneficial effects are mainly reflected as follows: the present invention provides a kind of new benzene that can be used as piezochromic material
Carboximide analog derivative, preparation method is simple, and material has excellent piezallochromy performance.
(4) Detailed description of the invention
Fig. 1 is the fluorescence emission spectrogram of compound of compound of the present invention (I).
Fig. 2 is crystal 1a of the present invention with the launching light spectrogram under different degrees of grinding.
Fig. 3 is crystal 1b of the present invention with the launching light spectrogram under different degrees of grinding.
(5) specific embodiment
The present invention is described further combined with specific embodiments below, but protection scope of the present invention is not limited in
This:
Embodiment 1: the synthesis of compound (II)
Under nitrogen protection, by 4- fluoroaniline (111mg, 10mmol), benzil (420mg, 2mmol), hexichol amido benzene
Formaldehyde (546.66mg, 2mmol), Ammoniom-Acetate (617mg, 8mmol) are dissolved in acetic acid (15mL) solvent, system back flow reaction 14
Hour.Deionized water is added after system is cooling, a large amount of white solids are precipitated, filters, the white solid dichloromethane that will be obtained
Alkane and deionized water extract, and merge organic phase, gained is organic to be added to anhydrous MgSO4After drying, it is concentrated under reduced pressure, then chromatographed with column
Separating-purifying, stationary phase are 300~400 mesh silica gel, and mobile phase is ethyl acetate: the mixing of methylene chloride=1:150~200 is molten
Agent finally obtains desired product as white solid (II) 500mg, yield 46%.
Compound (II)1H NMR data: (500MHz, DMSO) δ 7.50-7.46 (m, 2H), 7.36 (dt, J=9.0,
3.5Hz, 2H), 7.32 (dt, J=5.2,2.2Hz, 6H), 7.30-7.22 (m, 6H), 7.22-7.15 (m, 4H), 7.09 (t, J=
7.4Hz, 2H), 7.03 (dd, J=8.5,1.0Hz, 4H), 6.85-6.80 (m, 2H) .MS (ESI) theoretical value m/z:557.23 are real
Measured value: 559.1 (M+)。
Embodiment 2: the synthesis of compound (I)
1 gained compound (100mg, 0.18mmol) of embodiment is dissolved in methylene chloride (100mL) solvent, In
It is irradiated 7 days under the ultraviolet lamp of 365nm.It is extracted after reaction with methylene chloride and deionized water, merges organic phase, gained is organic
It is added to anhydrous MgSO4It after drying, is concentrated under reduced pressure, then use column chromatography purification, stationary phase is 300~400 mesh silica gel, flowing
Mutually be petroleum ether: ethyl acetate=3:1 mixed solvent finally obtains yellow solid target 42mg, yield 42%.
Compound (I)1H NMR data: (500MHz, Tol) δ 7.89 (d, J=3.5Hz, 1H), 7.79 (d, J=7.4Hz,
1H), 7.55 (dd, J=11.2,8.3Hz, 1H), 7.10 (s, 5H), 7.05-6.95 (m, 12H), 6.92 (dd, J=8.9,
5.6Hz, 3H), 6.89-6.82 (m, 3H), 6.73 (t, J=5.8Hz, 1H), 6.42 (t, J=8.5Hz, 1H) .MS (ESI) theory
Value m/z:589.22, measured value: 591.5 (M+)。
Embodiment 3: the crystal growth of crystal 1a, 1b
By the obtained compound in example 2 be dissolved separately in different proportion second alcohol and water (1:1,2:1,3:1,4:1,
It in mixed solution 5:1), slowly volatilizees to solvent at room temperature, there is the crystal of green and blue fluorescence to grow, respectively 1a,
1b。
Embodiment 4: the emission spectrum of crystal 1a, 1b and the piezallochromy spectrum of crystal
The crystal 1a and 1b that embodiment 3 is obtained carry out the fluorescence emission spectrum of solid, obtain its characteristic fluorescence transmitting light
Spectrogram, as shown in Figure 1, it was demonstrated that it has photoluminescent property.Substance 1a, 1b emission peak are respectively in 448nm, 497nm.
The fluorescence emission spectrum that crystal 1a and 1b that embodiment 3 obtains are carried out to different solids in mortar obtains its spy
Fluorescence emission spectrogram of compound is levied, as shown in Figure 2, it was demonstrated that its piezallochromy property.Substance 1a, 1b emission peak range is respectively in 495nm
~544nm, 451nm~547nm.
Claims (9)
1. it is a kind of using triphenylamine as the saccharin analog derivative of donor, shown in structure such as formula (I):
2. the method for preparing saccharin analog derivative as described in claim 1, which comprises
Compound shown in formula (II) is dissolved in methylene chloride, for the ultraviolet light irradiation of 365nm after 5~7 days, reaction solution is pure through separating
Change obtains the saccharin analog derivative；
3. method according to claim 2, it is characterised in that the isolation and purification method is as follows: reaction solution successively uses dichloromethane
Alkane and deionized water extract, and merge organic phase, and MgSO is added4It is dry, it is concentrated under reduced pressure, it is solid to obtain yellow for column chromatography for separation purification
Body target product, the as described saccharin analog derivative.
4. method as claimed in claim 3, it is characterised in that when the column chromatography for separation, stationary phase is 300~400 mesh silicon
Glue, mobile phase are petroleum ether: the mixed solvent of ethyl acetate volume ratio 3:1.
5. method according to claim 2, it is characterised in that formula (II) compound comprises the following steps: being protected in nitrogen
Under shield, 4- fluoroaniline, benzil, diphenylamines benzaldehyde and Ammoniom-Acetate are dissolved in acetic acid solvent, heating reflux reaction 10
~18 hours, reaction solution was isolated and purified to obtain formula (II) compound.
6. method as claimed in claim 5, it is characterised in that the isolation and purification method is as follows: being added and go after reaction solution is cooling
Ionized water, is precipitated white solid, filtering, and filter residue successively uses methylene chloride and deionized water to extract, merges organic phase, is added
MgSO4It is dry, it is concentrated under reduced pressure, column chromatography for separation purification obtains desired product as white solid, as described formula (II) compound.
7. method as claimed in claim 4, it is characterised in that the 4- fluoroaniline, benzil, diphenylamines benzaldehyde and vinegar
The ratio between amount of acid amide substance is 1~5:1:1~1.2:1~4.
8. method as claimed in claim 4, it is characterised in that when the column chromatography for separation, stationary phase is 300~400 mesh silicon
Glue, mobile phase are ethyl acetate: the mixed solvent of methylene chloride volume ratio 1:200.
9. application of the saccharin analog derivative described in claim 1 in preparation piezochromic material.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910548735.0A CN110407718B (en) | 2019-06-24 | 2019-06-24 | Benzoylimide derivative with triphenylamine as donor, and preparation and application thereof |
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| CN201910548735.0A CN110407718B (en) | 2019-06-24 | 2019-06-24 | Benzoylimide derivative with triphenylamine as donor, and preparation and application thereof |
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| CN110407718B CN110407718B (en) | 2022-07-26 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102079974A (en) * | 2009-11-26 | 2011-06-01 | 宁波大学 | Fluorinated triphenylamine derivative biological blue light materials and preparation method thereof |
| CN109761847A (en) * | 2018-12-26 | 2019-05-17 | 浙江工业大学 | A kind of saccharin derivative and the preparation method and application thereof |
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2019
- 2019-06-24 CN CN201910548735.0A patent/CN110407718B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102079974A (en) * | 2009-11-26 | 2011-06-01 | 宁波大学 | Fluorinated triphenylamine derivative biological blue light materials and preparation method thereof |
| CN109761847A (en) * | 2018-12-26 | 2019-05-17 | 浙江工业大学 | A kind of saccharin derivative and the preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| YU, YUE 等: "Highly efficient luminescent benzoylimino derivative and fluorescent probe from a photochemical reaction of imidazole as an oxygen sensor", 《 CHEMICAL COMMUNICATIONS 》 * |
| 吴锦霞 等: "三苯胺的压致变色机制研究", 《光谱学与光谱分析》 * |
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