CN110304982A - A kind of pyrenyl six substituted benzenes class compound and its synthetic method and application with aggregation-induced emission enhancement - Google Patents
A kind of pyrenyl six substituted benzenes class compound and its synthetic method and application with aggregation-induced emission enhancement Download PDFInfo
- Publication number
- CN110304982A CN110304982A CN201910203632.0A CN201910203632A CN110304982A CN 110304982 A CN110304982 A CN 110304982A CN 201910203632 A CN201910203632 A CN 201910203632A CN 110304982 A CN110304982 A CN 110304982A
- Authority
- CN
- China
- Prior art keywords
- pyrenyl
- aggregation
- substituted benzenes
- class compound
- induced emission
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/20—Polycyclic condensed hydrocarbons
- C07C15/38—Polycyclic condensed hydrocarbons containing four rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C22/00—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom
- C07C22/02—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings
- C07C22/04—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings containing six-membered aromatic rings
- C07C22/08—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings containing six-membered aromatic rings containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/50—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of non-condensed six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/205—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring the aromatic ring being a non-condensed ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
- C07C47/546—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings polycyclic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/40—Ortho- or ortho- and peri-condensed systems containing four condensed rings
- C07C2603/42—Ortho- or ortho- and peri-condensed systems containing four condensed rings containing only six-membered rings
- C07C2603/50—Pyrenes; Hydrogenated pyrenes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
Abstract
The pyrenyl six substituted benzenes class compound and its synthetic method and application that the invention discloses a kind of with aggregation-induced emission enhancement, R in the pyrenyl six substituted benzenes class compound is one of hydrogen atom, tert-butyl, methoxyl group, trifluoromethyl, cyano, aldehyde radical, which has potential application in luminescent material, chemical sensitisation, biological fluorescent labeling, bio-imaging and detection field；Each raw material is prepared fairly simple in the synthetic method, and performance is highly stable, does not need special preservation condition；Related reagent and solvent are all common commercial reagents, and cost is relatively low；Whole synthetic route is simple, and yield is high, of reduced contamination；The synthetic method includes three synthesis, extraction and purification steps, simplifies synthesis step compared with conventional aggregation induced luminous compound, this method is made to be easier to industrial applications popularization.
Description
Technical field
The invention belongs to luminescent material technical fields, and in particular to a kind of pyrenyl six with aggregation-induced emission enhancement takes
For benzene-like compounds and its synthetic method and application.
Background technique
Aggregation-induced emission (AIE) is Tang Benzhong professor in the unconventional optical physics phenomenon of one kind of discovery in 2001: one
Propeller-like molecules do not shine or shine in the solution and is faint a bit, and luminous intensity is remarkably reinforced in the collected state.In turn
Cause the interest of scientific research personnel in world wide.Currently, AIE system is also focused on based on four benzene second of tetraphenyl ethylene or class mostly
The derivative compound of alkene structure synthesizes the other kinds of structural system with AIE property and need to be explored.Especially synthesize pyrene
Base AIE system is even more rarer, although pyrene is play an important role in the research of photoelectric functional material, since its is biggish
Planar conjugate structure, easily formation pi-pi accumulation, make it that fluorescent quenching occur in coherent condition.
Summary of the invention
It is an object of the present invention to overcome defect existing in the prior art, provide a kind of with aggregation-induced emission increasing
Strong pyrenyl six substituted benzenes class compound, the series compound have larger in fields such as luminescent material, bio-imaging or detections
Application potential；The present invention is being heated using 7- tert-butyl -1- benzyne base pyrene compound and tetraphenylcyclopentadienone as raw material
Under the conditions of, by Diels-Alder reaction (D-A reaction), a series of pyrenyl six substituted benzenes class compounds are prepared, to synthesize pyrene
Base aggregation inducing fluorescence enhancement class compound provides new method.
In order to expand the classes of compounds of conventional aggregation induced luminescence system, it is proposed that there is one kind aggregation-induced emission to increase
The structural formula of strong pyrenyl six substituted benzenes class compound are as follows:
Wherein, R is one of hydrogen atom, tert-butyl, methoxyl group, trifluoromethyl, cyano, aldehyde radical.Pyrenyl six substituted benzenes class
The property that object has aggregation-induced emission enhancement is closed, there are the potentiality applied to fields such as luminescent material or bio-imaging and detections.
In order to preferably prepare the above-mentioned pyrenyl six substituted benzenes class compound with aggregation-induced emission enhancement, this hair
Bright technical solution proposes a kind of synthetic method of pyrenyl six substituted benzenes class compound with aggregation-induced emission enhancement, packet
Include following steps:
S1: 7- tert-butyl -1- benzyne base pyrene compound and tetraphenylcyclopentadienone are passed through diels-Alder by synthesis
It reacts (D-A reaction), prepares pyrenyl six substituted benzenes class compound, reaction equation are as follows:
S2: extraction, end of reaction are collected organic phase solution, will be collected with reaction product 2 ~ 3 times after cooling of good solvent extraction
Organic phase solution successively use saturated common salt water washing 2 ~ 3 times, anhydrous magnesium sulfate it is dry, obtain the mixed of reacting coarse product and good solvent
Close liquid；
S3: the mixed liquor of reacting coarse product and good solvent is successively chromatographed through distillation, column, obtains pure target product by purification.
Each raw material used in the present invention prepares fairly simple, and performance is highly stable, does not need special preservation item
Part；Related reagent and solvent are all common commercial reagents, and cost is relatively low；Whole synthetic route is simple, and yield is high, pollution compared with
It is few.
In order to preferably prepare the pyrenyl six substituted benzenes class compound with aggregation-induced emission enhancement, preferred technical side
Case is that the molar ratio of 7- tert-butyl -1- benzyne base pyrene compound and tetraphenylcyclopentadienone is 1: 1 ~ 2 in step S1, molten
Agent is diphenyl ether, and reaction temperature is 200 ~ 260 DEG C, and the reaction time is 12 ~ 36h.
In order to improve the utilization rate and reaction efficiency of raw material, further preferred technical solution is uncle 7- in step S1
The molar ratio of butyl -1- benzyne base pyrene compound and tetraphenylcyclopentadienone is 1: 1.5, and solvent is diphenyl ether, reaction temperature
Degree is 260 DEG C, and the reaction time is for 24 hours.
In order to improve the extraction efficiency of reaction product, preferred technical solution is that the good solvent in the step S2 is two
Chloromethanes.
In order to improve purification efficiency, preferred technical solution is that step S3 center pillar chromatography stationary phase used is silicon
Glue, eluent are the mixed liquor of methylene chloride and n-hexane, and the volume ratio of methylene chloride and n-hexane is 1: 1.5 ~ 9.
In order to further increase the purification efficiency of product, further preferred technical solution is the step S3 center pillar layer
Analysis eluent used is the mixed liquor of methylene chloride and n-hexane, and the volume ratio of the two corresponds to different products and most preferably mixed
Composition and division in a proportion.
In order to which the pyrenyl six substituted benzenes class compound preferably by this with aggregation-induced emission enhancement promotes and applies, now mention
It is glimmering to be suitable for luminescent material, chemical sensitisation, biology for the pyrenyl six substituted benzenes class compound with aggregation-induced emission enhancement out
The application of light probe, bio-imaging and detection field.
The advantages and beneficial effects of the present invention are:
1, the invention proposes a kind of pyrenyl six substituted benzenes class compound with aggregation-induced emission enhancement has been expanded traditional poly-
Collect the type of induced luminescence system；The series compound luminescent material, chemical sensitisation, biological fluorescent labeling, bio-imaging with
And detection field has potential application value.
2, the present invention is being heated using 7- tert-butyl -1- benzyne base pyrene compound and tetraphenylcyclopentadienone as raw material
Under the conditions of, by Diels-Alder reaction (D-A reaction), a series of pyrenyl six substituted benzenes class compounds are prepared, to synthesize pyrene
Base aggregation inducing fluorescence enhancement class compound provides new method.
3, each raw material used in synthetic method of the present invention is prepared fairly simple, and performance is highly stable, does not need spy
Different preservation condition；Related reagent and solvent are all common commercial reagents, and cost is relatively low；Whole synthetic route is simple, produces
Rate is high, of reduced contamination；The synthetic method includes three synthesis, extraction and purification steps, compared with conventional aggregation induced luminous compound
Synthesis step is simplified, this method is made to be easier to industrial applications popularization.
Detailed description of the invention
Fig. 1 is a kind of structural formula of the pyrenyl six substituted benzenes class compound with aggregation-induced emission enhancement of the present invention；
Fig. 2 is the chemical equation for the pyrenyl six substituted benzenes class compound that present invention synthesis has aggregation-induced emission enhancement；
Fig. 3 is the chemical equation that embodiment 1 synthesizes five phenyl -6- of 1,2,3,4,5- (7'- tert-butyl -1'- pyrenyl) benzene (a)；
Fig. 4 is the mono-crystalline structures figure of the target product b of embodiment 8；
Fig. 5 is the mono-crystalline structures figure of the target product c of embodiment 9；
Fig. 6 is fluorescence emission spectrum of the target product a of embodiment 1 in different volumes proportion solution (water and tetrahydrofuran)
Figure；
Fig. 7 is that maximum fluorescence emission of the target product a of embodiment 1 in different volumes proportion solution (water and tetrahydrofuran) is strong
Spend crest value comparison diagram；
Fig. 8 is that maximum fluorescence emission of the target product b of embodiment 8 in different volumes proportion solution (water and tetrahydrofuran) is strong
Spend crest value comparison diagram；
Fig. 9 is that maximum fluorescence emission of the target product c of embodiment 9 in different volumes proportion solution (water and tetrahydrofuran) is strong
Spend crest value comparison diagram；
Figure 10 is maximum fluorescence emission of the target product d of embodiment 10 in different volumes proportion solution (water and tetrahydrofuran)
Intensity crest value comparison diagram；
Figure 11 is maximum fluorescence emission of the target product e of embodiment 11 in different volumes proportion solution (water and tetrahydrofuran)
Intensity crest value comparison diagram；
Figure 12 is maximum fluorescence emission of the target product f of embodiment 12 in different volumes proportion solution (water and tetrahydrofuran)
Intensity crest value comparison diagram.
Specific embodiment
With reference to the accompanying drawings and examples, further description of the specific embodiments of the present invention.Following embodiment is only
For clearly illustrating technical solution of the present invention, and not intended to limit the protection scope of the present invention.Implement this hair
Bright process, condition, reagent, test method, test method etc. are in addition to what is specifically mentioned below this field
Universal knowledege and common knowledge, there are no special restrictions to content by the present invention.Data given by following embodiment include concrete operations
With reaction condition and product.Product purity passes through nuclear-magnetism, high resolution mass spectrum analyzes and identifies, and part of compounds passes through X-ray list
Brilliant diffractometer obtains Precise structural information.
A kind of pyrenyl six substituted benzenes class compound with aggregation-induced emission enhancement, structural formula are as follows:
Wherein, R is one of hydrogen atom, tert-butyl, methoxyl group, trifluoromethyl, cyano, aldehyde radical.
The synthetic method of the above-mentioned pyrenyl six substituted benzenes class compound with aggregation-induced emission enhancement, including walk as follows
It is rapid:
S1: 7- tert-butyl -1- benzyne base pyrene compound and tetraphenylcyclopentadienone are passed through diels-Alder by synthesis
It reacts (D-A reaction), prepares pyrenyl six substituted benzenes class compound, reaction equation is as follows:
S2: extraction, end of reaction are collected organic phase solution, will be collected with reaction product 2 ~ 3 times after cooling of good solvent extraction
Organic phase solution successively use saturated common salt water washing 2 ~ 3 times, anhydrous magnesium sulfate it is dry, obtain the mixed of reacting coarse product and good solvent
Close liquid；
S3: the mixed liquor of reacting coarse product and good solvent is successively chromatographed through distillation, column, obtains pure target product by purification.
In order to preferably prepare the pyrenyl six substituted benzenes class compound with aggregation-induced emission enhancement, preferred technical side
Case is that the molar ratio of 7- tert-butyl -1- benzyne base pyrene compound and tetraphenylcyclopentadienone is 1: 1 ~ 2 in step S1, molten
Agent is diphenyl ether, and reaction temperature is 200 ~ 260 DEG C, and the reaction time is 12 ~ 36h.
In order to improve the utilization rate and reaction efficiency of raw material, further preferred technical solution is uncle 7- in step S1
The molar ratio of butyl -1- benzyne base pyrene compound and tetraphenylcyclopentadienone is 1: 1.5, and solvent is diphenyl ether, reaction temperature
Degree is 260 DEG C, and the reaction time is for 24 hours.
In order to improve the extraction efficiency of reaction product, preferred technical solution is that the good solvent in the step S2 is two
Chloromethanes.
In order to improve purification efficiency, preferred technical solution is that step S3 center pillar chromatography stationary phase used is silicon
Glue, eluent are the mixed liquor of methylene chloride and n-hexane, and the volume ratio of methylene chloride and n-hexane is 1: 1.5 ~ 9.
In order to further increase the purification efficiency of product, further preferred technical solution is the step S3 center pillar layer
Analysis eluent used is the mixed liquor of methylene chloride and n-hexane, and the volume ratio of the two corresponds to different products and most preferably mixed
Composition and division in a proportion.
In order to which the pyrenyl six substituted benzenes class compound preferably by this with aggregation-induced emission enhancement promotes and applies, now mention
It is glimmering to be suitable for luminescent material, chemical sensitisation, biology for the pyrenyl six substituted benzenes class compound with aggregation-induced emission enhancement out
The application of light probe, bio-imaging and detection field.
Embodiment 1
By taking the synthesis of 1,2,3,4,5- five phenyl -6- (7'- tert-butyl -1'- pyrenyl) benzene as an example, chemical equation is as follows.
Into 5mL eggplant type bottle be added benzyne base pyrene (100 mg, 0.279 mmol), tetraphenylcyclopentadienone (161 mg,
0.419 mmol), solvent diphenyl ether (1.0 mL) then is added.It is reacted by electric jacket heating, temperature is controlled 260
DEG C, reaction reflux 24 hours.After completion of the reaction, it is extracted twice with 20 mL methylene chloride, with 20 mL saturated common salt water washings two
It is secondary, it is then dry with appropriate anhydrous magnesium sulfate.Above-mentioned solution is distilled to remaining a small amount of liquid, by column chromatography, with two
Chloromethanes/n-hexane mixed liquor (1: 9, volume ratio) does eluent, and the yield of isolated desired product as white solid a is
95.7 mg(target product theoretical yields are the g/mol=199.2 of 0.279 mmol × 714 mg), yield 48%.The mesh measured
The fusing point for marking product a is 318-320 DEG C；
1H NMR (400 MHz, CDCl3): δH = 1.55 (s, 9H, tBu), 6.38 (t, J = 7.5 Hz, 2H,
Ph-H), 6.48 (t, J = 7.4 Hz, 2H, Ph-H), 6.63 (t, J = 7.4 Hz, 2H, Ph-H), 6.70
(d, J = 7.5 Hz, 2H, Ph-H), 6.83–6.98 (m, 17H, Ph-H), 7.64 (d, J = 7.9 Hz, 1H,
pyrene-H), 7.73 (d, J = 7.9 Hz, 1H, pyrene-H), 7.79 (d, J = 9.0 Hz, 1H,
pyrene-H), 7.86 (d, J = 9.0 Hz, 1H, pyrene-H), 7.91 (d, J = 9.3 Hz, 1H,
pyrene-H), 8.06 (d, J = 9.2 Hz, 1H, pyrene-H), 8.10 (s, 1H, pyrene-H), 8.11
ppm (s, 1H, pyrene-H);
13C NMR (100 MHz, CDCl3): δC = 31.93, 35.14, 121.74, 121.90, 122.81,
123.24, 123.93, 125.12, 125.19, 125.23, 126.04, 126.35, 126.53, 126.57,
126.63, 127.39, 129.28, 129.38, 129.54, 130.34, 130.70, 130.91, 131.03,
131.45, 131.51, 131.56, 136.27, 138.78, 140.27, 140.42, 140.60, 140.73,
141.52, 148.56 ppm;
FAB-MS: m/z calcd for C56H42 714.3287 [M+]; found 714.3266 [M+]。
Embodiment 2
The difference of embodiment 2 and embodiment 1 is that benzyne base pyrene feeds intake as (100 mg, 0.279 mmol), tetraphenyl ring penta 2
Ketenes feeds intake as (107 mg, 0.279 mmol), and the yield of isolated desired product as white solid a is 61.8 mg, yield
It is 31%, test data is the same as embodiment 1.
Embodiment 3
The difference of embodiment 3 and embodiment 1 is that benzyne base pyrene feeds intake as (100 mg, 0.279 mmol), tetraphenyl ring penta 2
Ketenes feeds intake as (214 mg, 0.558 mmol), and the yield of isolated desired product as white solid a is 97.7 mg, yield
It is 49%, test data is the same as embodiment 1.
Embodiment 4
The difference of embodiment 4 and embodiment 1 is that benzyne base pyrene feeds intake as (100 mg, 0.279 mmol), tetraphenyl ring penta 2
Ketenes feeds intake as (161 mg, 0.419 mmol), and reaction temperature is 200 DEG C, the production of isolated desired product as white solid a
Amount is 83.7 mg, and yield 42%, test data is the same as embodiment 1.
Embodiment 5
The difference of embodiment 5 and embodiment 1 is that benzyne base pyrene feeds intake as (100 mg, 0.279 mmol), tetraphenyl ring penta 2
Ketenes feeds intake as (161 mg, 0.419 mmol), and reaction temperature is 240 DEG C, the production of isolated desired product as white solid a
Amount is 89.7 mg, and yield 45%, test data is the same as embodiment 1.
Embodiment 6
The difference of embodiment 5 and embodiment 1 is that benzyne base pyrene feeds intake as (100 mg, 0.279 mmol), tetraphenyl ring penta 2
Ketenes feeds intake as (161 mg, 0.419 mmol), reaction time 12h, the yield of isolated desired product as white solid a
For 59.8 mg, yield 30%, test data is the same as embodiment 1.
Embodiment 7
The difference of embodiment 7 and embodiment 1 is that benzyne base pyrene feeds intake as (100 mg, 0.279 mmol), tetraphenyl ring penta 2
Ketenes feeds intake as (161 mg, 0.419 mmol), reaction time 36h, the yield of isolated desired product as white solid a
For 97.7 mg, yield 49%, test data is the same as embodiment 1.
The reaction condition and experimental result of 1 embodiment 1 ~ 7 of table
The results showed that the target product yield of embodiment 1 and embodiment 3 is above embodiment 2 and embodiment 4 ~ 7, wherein
The raw material input amount of embodiment 3 is more, it is thus determined that the reaction condition of embodiment 1 is optimal, i.e. benzyne base pyrene and tetraphenyl ring
Pentadienone molar ratio be 1: 1.5, reaction temperature be 260 DEG C, the reaction time be for 24 hours.
Embodiment 8
Embodiment 8 the difference from embodiment 1 is that, in 7- tert-butyl -1- benzyne base pyrene compound R substituent be tert-butyl,
It is carried out according to the reaction condition of embodiment 1, the yield of isolated desired product as white solid b is 88%, target product b structure
As shown in Figure 4.The fusing point of the target product measured is 327-329 DEG C;
1H NMR (400 MHz, CDCl3): δH = 1.55 (s, 9H, tBu), 6.40 (t, J = 7.5 Hz, 2H,
Ph-H), 6.48 (t, J = 7.4 Hz, 2H, Ph-H), 6.59 (t, J = 7.4 Hz, 2H, Ph-H), 6.72
(d, J = 7.5 Hz, 2H, Ph-H), 6.85–6.93 (m, 16H, Ph-H), 7.62 (d, J = 7.9 Hz, 1H,
pyrene-H), 7.72 (d, J = 7.9 Hz, 1H, pyrene-H), 7.81 (d, J = 9.0 Hz, 1H,
pyrene-H), 7.85 (d, J = 9.0 Hz, 1H, pyrene-H), 7.91 (d, J = 9.3 Hz, 1H,
pyrene-H), 8.05 (d, J = 9.2 Hz, 1H, pyrene-H), 8.08 (s, 1H, pyrene-H), 8.10
ppm (s, 1H, pyrene-H);
13C NMR (100 MHz, CDCl3): δC = 33.80, 35.13, 121.62, 121.72, 122.79
123.22, 123.95, 124.95, 125.05, 125.11, 125.16, 125.96, 126.30, 126.43,
126.53, 126.58, 126.66, 127.34, 129.29, 129.32, 129.60, 129.98, 130.50,
130.71, 130.94, 131.47, 131.58, 136.51, 137.14, 138.88, 140.15, 140.34,
140.54, 140.60, 140.70, 140.84, 141.37, 141.70, 147.58, 148.47 ppm;
FAB-MS: m/z calcd for C60H50 770.3913 [M+]; found 770.3946 [M+]。
Embodiment 9
Embodiment 9 the difference from embodiment 1 is that, in 7- tert-butyl -1- benzyne base pyrene compound R substituent be methoxyl group,
It is carried out according to the reaction condition of embodiment 1, the yield of isolated desired product as white solid c is 72%, target product c structure
Figure is as figure 5 illustrates.The fusing point of the target product measured is 281-283 DEG C；
1H NMR (400 MHz, CDCl3): δH = 1.55 (s, 9H, tBu), 3.34 (s, 3H, OMe), 5.93
(dd, J = 8.4 Hz, 2H, Ph-H), 6.18 (dd, J = 8.5 Hz, 2H, Ph-H), 6.37 (t, 2H, Ph-H), 6.48 (t, 2H, Ph-H), 6.66 (t, J = 7.4 Hz, 2H, Ph-H), 6.75 (d, J = 7.5 Hz,
2H, Ph-H), 6.84–6.89 (m, 16H, Ph-H), 7.65 (d, J = 7.9 Hz, 1H, pyrene-H), 7.74
(d, J = 7.9 Hz, 1H, pyrene-H), 7.83 (d, J = 9.0 Hz, 1H, pyrene-H), 7.89 (d, J
= 9.0 Hz, 1H, pyrene-H), 7.92 (d, J = 9.3 Hz, 1H, pyrene-H), 8.05 (d, J = 9.2
Hz, 1H, pyrene-H), 8.12 ppm (s, 2H, pyrene-H);
13C NMR (100 MHz, CDCl3): δC =31.93, 35.14, 54.53, 111.74, 121.68, 121.84,
122.84, 123.31, 123.95, 125.08, 125.12, 125.16, 126.00, 126.30, 126.53,
126.61, 127.41, 129.22, 129.30, 129.51, 130.29, 130.70, 130.86, 131.02,
131.35, 131.42, 131.53, 131.86, 132.67, 136.45, 139.00, 140.20, 140.31,
140.63, 140.78, 141.09, 141.49, 148.52, 156.67 ppm;
FAB-MS: m/z calcd for C57H44O 744.3392 [M+]; found 744.3386 [M+]。
Embodiment 10
Embodiment 10 the difference from embodiment 1 is that, in 7- tert-butyl -1- benzyne base pyrene compound R substituent be fluoroform
Base is carried out according to the reaction condition of embodiment 1, and the yield of isolated desired product as white solid d is 69%.The target measured
The fusing point of product d is 348-349 DEG C；
1H NMR (400 MHz, CDCl3): δH = 1.55 (s, 9H, tBu), 6.39 (t, J = 7.3 Hz, 2H,
Ph-H), 6.49 (t, J = 7.3 Hz, 2H, Ph-H), 6.63 (t, J = 7.6 Hz, 2H, Ph-H), 6.70
(d, J = 7.5 Hz, 2H, Ph-H), 6.78–6.93 (m, 16H, Ph-H), 7.62 (d, J = 7.7 Hz, 1H,
pyrene-H), 7.74 (d, J = 7.6 Hz, 1H, pyrene-H), 7.81 (d, J = 8.7 Hz, 1H,
pyrene-H), 7.91 (dd, J = 16.5 Hz, 2H, pyrene-H), 8.04 (d, J = 9.2 Hz, 1H,
pyrene-H), 8.13 ppm (s, 2H, pyrene-H);
13C NMR (100 MHz, CDCl3): δC = 31.92, 35.16, 110.03, 121.89, 122.15,
122.75, 123.07, 123.36, 123.94, 125.31, 126.39, 126.63, 126.69, 126.81,
126.93, 127.32, 129.26, 129.58, 130.26, 130.43, 130.60, 130.81, 131.03,
131.12, 131.27, 131.33, 131.38, 135.46, 138.56, 139.91, 140.01, 140.11,
140.32, 140.37, 140.94, 141.04, 141.76, 144.28 ppm;
FAB-MS: m/z calcd for C57H41F3 782.3160 [M+]; found 782.3147 [M+]。
Embodiment 11
Embodiment 11 the difference from embodiment 1 is that, in 7- tert-butyl -1- benzyne base pyrene compound R substituent be cyano, press
It is carried out according to the reaction condition of embodiment 1, the yield of isolated desired product as white solid e is 68%.The target product e measured
Fusing point be 186-187 DEG C；
1H NMR (400 MHz, CDCl3): δH = 1.59 (s, 9H, tBu), 6.44 (t, J = 7.4 Hz, 1H,
Ph-H), 6.55 (t, J = 7.4 Hz, 1H, Ph-H), 6.68–6.77 (m, 3H, Ph-H), 6.82–7.04 (m,
19H, Ph-H), 7.64 (d, J = 7.8 Hz, 1H, pyrene-H), 7.78 (d, J = 7.9 Hz, 1H,
pyrene-H), 7.84 (d, J = 8.9 Hz, 1H, pyrene-H), 7.91–7.99 (m, 2H, pyrene-H),
8.04 (d, J = 9.1 Hz, 1H, pyrene-H), 8.18 ppm (d, J = 2.7 Hz, 2H, pyrene-H);
13C NMR (100 MHz, CDCl3): δC = 30.88, 34.13, 107.79, 117.80, 120.97,
121.32, 121.63, 122.34, 122.87, 124.37, 124.45, 124.70, 124.74, 125.18,
125.46, 125.64, 125.72, 125.91, 126.04, 126.11, 126.20, 128.08, 128.61,
128.91, 129.10, 129.19, 129.47, 129.73, 129.94, 130.18, 130.28, 130.40,
134.05, 137.40, 138.74, 138.95, 139.10, 140.00, 140.35, 140.80, 144.64,
147.83 ppm;
FAB-MS: m/z calcd for C57H41O 739.3239 [M+]; found 739.3235 [M+]。
Embodiment 12
Embodiment 12 the difference from embodiment 1 is that, in 7- tert-butyl -1- benzyne base pyrene compound R substituent be aldehyde radical, press
It is carried out according to the reaction condition of embodiment 1, the yield of isolated desired product as white solid f is 67%.The target product f measured
Fusing point be 170-171 DEG C；
1H NMR (400 MHz, CDCl3): δH = 1.55 (s, 9H, tBu), 6.38–6.43 (m, 1H, Ph-H),
6.49–6.54 (m, 1H, Ph-H), 6.68 (d, J = 12.1 Hz, 3H, Ph-H), 6.80–6.98 (m, 19H,
Ph-H), 7.63 (d, J = 7.8 Hz, 1H, pyrene-H), 7.73 (d, J = 7.7 Hz, 1H, pyrene-H), 7.79 (d, J = 8.9 Hz, 1H, pyrene-H), 7.88 (d, J = 8.9 Hz, 1H, pyrene-H),
7.93 (d, J = 9.2 Hz, 1H, pyrene-H), 8.04 (d, J = 11.2 Hz, 1H, pyrene-H), 8.12
(s, 2H, pyrene-H), 9.43 ppm (s, 1H, CHO-H);
13C NMR (100 MHz, CDCl3): δC = 31.89, 35.14, 121.91, 122.16, 122.67,
123.33, 123.87, 125.29, 126.63, 126.70, 126.82, 126.90, 127.27, 128.93,
130.97, 131.24, 131.29, 131.35, 131.42, 133.00, 135.36, 138.42, 139.87,
139.93, 139.99, 140.24, 140.92, 141.13, 141.73, 147.33, 148.74, 192.02 ppm;
FAB-MS: m/z calcd for C57H42O 742.3236 [M+]; found 742.3260 [M+]。
The reaction condition and experimental result of 2 embodiment 8 ~ 12 of table
The results showed that using the synthesis of the pyrenyl six substituted benzenes class compound with aggregation-induced emission enhancement of the invention
Method, can successfully synthesize substituent group be respectively tert-butyl, methoxyl group, trifluoromethyl, cyano, aldehyde radical have aggregation inducing
The pyrenyl six substituted benzenes class compound of luminescence enhancement.
Embodiment 13
The aggregation-induced emission performance of target compound a ~ f in testing example 1 and embodiment 8 ~ 12:
Step 1: it is 5 × 10 that target compound a ~ f in embodiment 1 and embodiment 8 ~ 12, which is respectively configured as concentration,-7
11 parts of solution of mol/L, solvent are the mixture of water (poor solvent) and tetrahydrofuran (good solvent), wherein water and tetrahydrofuran
Volume ratio be respectively 100: 0,90: 10,80: 20,70: 30,60: 40,50: 50,40: 60,30: 70,20: 80,10: 90,1:
99；
Step 2: carrying out fluorometric investigation to 11 parts of solution of target compound a ~ f respectively using fluorescence spectrum analyzer.
The results showed that as shown in fig. 6, the maximum fluorescence emission intensity crest value of target compound a is in solvent
It after the increase of moisture volume content first gradually rises and gradually decreases, wherein occurring maximum fluorescence hair when moisture content is 60%
Penetrate maximum intensity crest value；As shown in Fig. 7 ~ 12, target compound a ~ f with water volume content in solvent increase maximum fluorescence
Emissive porwer crest value gradually increases, and occurs the maximum crest value of maximum fluorescence emission intensity when moisture content is 60%, then
Increase maximum fluorescence emission intensity crest value with moisture volume content in solvent gradually weakens, that is, illustrates synthesis side of the invention
Target compound a ~ f made from method all has aggregation-induced emission enhancement effect.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, several improvements and modifications can also be made, these improvements and modifications
Also it should be regarded as protection scope of the present invention.
Claims (7)
1. a kind of pyrenyl six substituted benzenes class compound with aggregation-induced emission enhancement, which is characterized in that structural formula are as follows:
Wherein, R is one of hydrogen atom, tert-butyl, methoxyl group, trifluoromethyl, cyano, aldehyde radical.
2. a kind of synthetic method of the pyrenyl six substituted benzenes class compound with aggregation-induced emission enhancement, which is characterized in that packet
Include following steps:
S1: 7- tert-butyl -1- benzyne base pyrene compound and tetraphenylcyclopentadienone are passed through diels-Alder by synthesis
It reacts (D-A reaction), prepares pyrenyl six substituted benzenes class compound, reaction equation are as follows:
S2: extraction, end of reaction are collected organic phase solution, will be collected with reaction product 2 ~ 3 times after cooling of good solvent extraction
Organic phase solution successively use saturated common salt water washing 2 ~ 3 times, anhydrous magnesium sulfate it is dry, obtain the mixed of reacting coarse product and good solvent
Close liquid；
S3: the mixed liquor of reacting coarse product and good solvent is successively chromatographed through distillation, column, obtains pure target product by purification.
3. the synthetic method of the pyrenyl six substituted benzenes class compound with aggregation-induced emission enhancement as claimed in claim 2,
It is characterized in that, the molar ratio of 7- tert-butyl -1- benzyne base pyrene compound and tetraphenylcyclopentadienone is 1: 1 in step S1
~ 2, solvent is diphenyl ether, and reaction temperature is 200 ~ 260 DEG C, and the reaction time is 12 ~ 36h.
4. the synthetic method of the pyrenyl six substituted benzenes class compound with aggregation-induced emission enhancement as claimed in claim 3,
It is characterized in that, the molar ratio of 7- tert-butyl -1- benzyne base pyrene compound and tetraphenylcyclopentadienone is 1 in step S1:
1.5, solvent is diphenyl ether, and reaction temperature is 260 DEG C, when the reaction time is for 24 hours, reaction efficiency highest.
5. the synthetic method of the pyrenyl six substituted benzenes class compound with aggregation-induced emission enhancement as claimed in claim 4,
It is characterized in that, the good solvent in the step S2 is methylene chloride.
6. the synthetic method of the pyrenyl six substituted benzenes class compound with aggregation-induced emission enhancement as claimed in claim 5,
It is characterized in that, step S3 center pillar chromatography stationary phase used is silica gel, eluent is the mixed of methylene chloride and n-hexane
The volume ratio of conjunction liquid, methylene chloride and n-hexane is 1: 1.5 ~ 9.
7. a kind of application of the pyrenyl six substituted benzenes class compound with aggregation-induced emission enhancement, which is characterized in that such as right
It is required that the pyrenyl six substituted benzenes class compound described in 1 with aggregation-induced emission enhancement is in luminescent material, chemical sensitisation, biology
The application of fluorescence probe, bio-imaging and detection field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910203632.0A CN110304982B (en) | 2019-03-18 | 2019-03-18 | Pyrenyl hexa-substituted benzene compound with aggregation-induced emission enhancement function and synthesis method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910203632.0A CN110304982B (en) | 2019-03-18 | 2019-03-18 | Pyrenyl hexa-substituted benzene compound with aggregation-induced emission enhancement function and synthesis method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110304982A true CN110304982A (en) | 2019-10-08 |
| CN110304982B CN110304982B (en) | 2022-04-12 |
Family
ID=68074358
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910203632.0A Active CN110304982B (en) | 2019-03-18 | 2019-03-18 | Pyrenyl hexa-substituted benzene compound with aggregation-induced emission enhancement function and synthesis method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110304982B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113402422A (en) * | 2021-06-18 | 2021-09-17 | 山东理工大学 | Synthetic method and application of alpha-cyanoethylene aggregation induced luminophor |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1527871A (en) * | 2001-07-11 | 2004-09-08 | ��ʿ��Ƭ��ʽ���� | Light-emitting device and aromatic compound |
| EP1475361A2 (en) * | 2001-04-26 | 2004-11-10 | Fuji Photo Film Co., Ltd. | Aromatic condensed-ring compound, light emitting device material and light emitting device using the same |
| JP2005063938A (en) * | 2003-05-09 | 2005-03-10 | Fuji Photo Film Co Ltd | Organic electroluminescent element |
| JP2007221113A (en) * | 2006-01-23 | 2007-08-30 | Fujifilm Corp | Organic electroluminescent element |
-
2019
- 2019-03-18 CN CN201910203632.0A patent/CN110304982B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1475361A2 (en) * | 2001-04-26 | 2004-11-10 | Fuji Photo Film Co., Ltd. | Aromatic condensed-ring compound, light emitting device material and light emitting device using the same |
| CN1527871A (en) * | 2001-07-11 | 2004-09-08 | ��ʿ��Ƭ��ʽ���� | Light-emitting device and aromatic compound |
| JP2005063938A (en) * | 2003-05-09 | 2005-03-10 | Fuji Photo Film Co Ltd | Organic electroluminescent element |
| JP2007221113A (en) * | 2006-01-23 | 2007-08-30 | Fujifilm Corp | Organic electroluminescent element |
Non-Patent Citations (2)
| Title |
|---|
| WANG, CZ ET AL: "Multiple Photoluminescence from Pyrene-Fused Hexaarylbenzenes with Aggregation-Enhanced Emission Features", 《ASIAN JOURNAL OF ORGANIC CHEMISTRY》 * |
| 李思 等: "新型六芳基苯类衍生物的合成及其光物理性能研究", 《化学试剂》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113402422A (en) * | 2021-06-18 | 2021-09-17 | 山东理工大学 | Synthetic method and application of alpha-cyanoethylene aggregation induced luminophor |
| CN113402422B (en) * | 2021-06-18 | 2022-10-11 | 山东理工大学 | Synthetic method and application of alpha-cyanoethylene aggregation induced luminophor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110304982B (en) | 2022-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110818743B (en) | Preparation method and application of cyclometalated platinum complex with aggregation-induced emission property | |
| CN108546255B (en) | Tetraphenyl vinyl thiazole solvent water fluorescent probe and preparation method thereof | |
| CN105504860B (en) | The synthesis and its application of a kind of pyranoquinoline fluorochrome | |
| CN110256218A (en) | A kind of aggregation-induced emission dye molecule and its synthetic method | |
| CN110304982A (en) | A kind of pyrenyl six substituted benzenes class compound and its synthetic method and application with aggregation-induced emission enhancement | |
| CN103937487A (en) | Phosphorescent fluorinion probe, preparation and applications thereof | |
| CN110511191B (en) | Fluorescent probe for detecting water content in organic solvent and preparation method and application thereof | |
| CN111349109B (en) | Synthetic method of seven-element boron dipyrromethene fluorescent dye | |
| CN110407708B (en) | Chiral tetraphenylethylenetetramine for chiral carboxylic acid enantiomer recognition and purity analysis | |
| CN111793095A (en) | Preparation method and application of cyclometalated platinum complex | |
| CN114853656B (en) | Carbazole derivative with AEE characteristic, preparation method and application | |
| CN112480025B (en) | Compound with aggregation-induced emission function and preparation method and application thereof | |
| CN102702074B (en) | Preparation method of sulfonyl chloride compound taking carbazole as fluorogen | |
| CN111362795B (en) | Preparation method of substituted butyrate derivatives | |
| CN111393869B (en) | Fluorescent dye containing phenylethynyl naphthalene, preparation method and application thereof | |
| CN106632266A (en) | Switching mode thiol fluorescent labeling reagent as well as synthetic method and application thereof | |
| CN101318954B (en) | Cyanuric chloride derivant, preparation method and application thereof | |
| CN108409634A (en) | Carbazoles fluorescence amine compound label reagent, synthesis and application | |
| CN108191880A (en) | A kind of fluorescent dye preparation method and application with carbazole-rhodamine hybrid structure | |
| Zheng et al. | Enantiomer analysis of chiral carboxylic acids by AIE molecules bearing optically pure aminol groups | |
| CN107129512A (en) | A kind of fluorescence probe containing selenium atom and preparation method and application | |
| CN114773381B (en) | Pyridine ring-containing aromatic acrylonitrile carbazole reaction type fluoride ion fluorescent probe and preparation method and application thereof | |
| CN109894103A (en) | The method adsorbed carbon dioxide using conjugated polymer and boron nitride composite and monitor its slow release | |
| CN111233616A (en) | Pyrenyl [4] helicene and synthesis method and application thereof | |
| CN113402422B (en) | Synthetic method and application of alpha-cyanoethylene aggregation induced luminophor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |