CN107805228B - What a kind of near-infrared fluorescent region had reversible machine discoloration property is framework compound, preparation and its application based on diazosulfide - Google Patents
What a kind of near-infrared fluorescent region had reversible machine discoloration property is framework compound, preparation and its application based on diazosulfide Download PDFInfo
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- CN107805228B CN107805228B CN201711021584.0A CN201711021584A CN107805228B CN 107805228 B CN107805228 B CN 107805228B CN 201711021584 A CN201711021584 A CN 201711021584A CN 107805228 B CN107805228 B CN 107805228B
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 46
- 238000002845 discoloration Methods 0.000 title claims abstract description 24
- 230000002441 reversible effect Effects 0.000 title claims abstract description 17
- OBISXEJSEGNNKL-UHFFFAOYSA-N dinitrogen-n-sulfide Chemical compound [N-]=[N+]=S OBISXEJSEGNNKL-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 99
- 239000000463 material Substances 0.000 claims abstract description 20
- SAHIZENKTPRYSN-UHFFFAOYSA-N [2-[3-(phenoxymethyl)phenoxy]-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound O(C1=CC=CC=C1)CC=1C=C(OC2=NC(=CC(=C2)CN)C(F)(F)F)C=CC=1 SAHIZENKTPRYSN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 38
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 34
- 239000007787 solid Substances 0.000 claims description 31
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 25
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 18
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 17
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 16
- 238000012805 post-processing Methods 0.000 claims description 14
- 238000005859 coupling reaction Methods 0.000 claims description 12
- 229940125904 compound 1 Drugs 0.000 claims description 11
- -1 diazosulfide class compound Chemical class 0.000 claims description 10
- 229940126214 compound 3 Drugs 0.000 claims description 9
- GQWAOUOHRMHSHL-UHFFFAOYSA-N 4-ethenyl-n,n-dimethylaniline Chemical compound CN(C)C1=CC=C(C=C)C=C1 GQWAOUOHRMHSHL-UHFFFAOYSA-N 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 239000003444 phase transfer catalyst Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000004440 column chromatography Methods 0.000 claims description 7
- 229940125782 compound 2 Drugs 0.000 claims description 7
- 239000012044 organic layer Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 6
- 239000007832 Na2SO4 Substances 0.000 claims description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 6
- 238000010189 synthetic method Methods 0.000 claims description 6
- 230000002146 bilateral effect Effects 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims 1
- 238000000227 grinding Methods 0.000 abstract description 28
- 238000002189 fluorescence spectrum Methods 0.000 abstract description 11
- 238000002059 diagnostic imaging Methods 0.000 abstract description 3
- 238000000295 emission spectrum Methods 0.000 abstract description 2
- 230000005284 excitation Effects 0.000 description 15
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002451 electron ionisation mass spectrometry Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 241000021375 Xenogenes Species 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- FEOWHLLJXAECMU-UHFFFAOYSA-N 4,7-dibromo-2,1,3-benzothiadiazole Chemical class BrC1=CC=C(Br)C2=NSN=C12 FEOWHLLJXAECMU-UHFFFAOYSA-N 0.000 description 1
- XGOACEXUXLKAFR-UHFFFAOYSA-N 4-ethenyl-n-methylaniline Chemical compound CNC1=CC=C(C=C)C=C1 XGOACEXUXLKAFR-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKUSWAGOKUGEDX-UHFFFAOYSA-N C(CCC)Br(CCCC)(CCCC)CCCC Chemical compound C(CCC)Br(CCCC)(CCCC)CCCC OKUSWAGOKUGEDX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/01—Five-membered rings
- C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
- C07D285/14—Thiadiazoles; Hydrogenated thiadiazoles condensed with carbocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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- 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
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/286—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q involving mechanical work, e.g. chopping, disintegrating, compacting, homogenising
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/645—Specially adapted constructive features of fluorimeters
- G01N21/6456—Spatial resolved fluorescence measurements; Imaging
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- 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
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
- C09K2211/1051—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with sulfur
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/286—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q involving mechanical work, e.g. chopping, disintegrating, compacting, homogenising
- G01N2001/2866—Grinding or homogeneising
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Abstract
Have reversible machine discoloration property the present invention relates to a kind of novel near-infrared fluorescent region is framework compound based on diazosulfide, has structural formula described in following compound 1-4.The fluorescence emission spectrum of itself is close or reaches near infrared light region, after mechanical lapping, emission spectrum range occurs red shift and reaches near infrared light region, then handles the sample after grinding with dichloromethane solution, maximum fluorescence emission peak return to original state again under position.It is expected to the sensor material as novel near-infrared fluorescent zone machines stimuli responsive, to be applied to the research fields such as medical imaging, anti-counterfeiting ink.
Description
Technical field
The present invention relates to a kind of novel small organic molecule luminescent material and its applications, more particularly to a kind of novel near-infrared
What fluorescence area had reversible machine discoloration property is framework compound, preparation and its application based on diazosulfide.
Background technique
Off-color material typically refers to be pressed by the changed material of color energy, this kind of off-color material under the conditions of outside stimulus
According to the difference of environmental stimuli mode, it is generally divided into mechanical discoloration, electrochromism, photochromic, thermochromism, five kinds of steam discoloration
Type.So-called mechanical discoloration refers to material, and material color or fluorescence can under conditions of mechanical lapping, extruding perhaps rub
A kind of changed phenomenon.Under normal conditions, there are two types of modes for mechanical discoloration, and one is the spaces that outside stimulus leads to molecule
Pushing changes, and one is outside stimulus to cause molecular configuration that certain isomerization occurs, both processes often show
The variation of fluorescence spectrum out.In recent years, mechanical tenebrescent material is due in stress sensing, memory chip, data storage, information
The potential application in fields and the extensive concerns by chemist such as safety.
Near infrared light stimuli responsive material has superior application prospect in fields such as medical imaging, anti-counterfeiting inks, therefore,
Novel near-infrared fluorescent region is developed to be very important with the small organic molecule fluorescent material of reversible machine discoloration property.
However, the mechanical electrochromic compound being currently known, the fluorescence emission spectral limit overwhelming majority of machinery discoloration front and back is all concentrated
In visible light region.The small organic molecule machinery off-color material field of metallic element is especially free of, its is glimmering before and after machinery discoloration
The compound that optical emission spectroscopy reaches near-infrared fluorescent region is seldom reported.
Summary of the invention
It is a kind of novel close the technical problem to be solved by the present invention is to aiming at the above shortcomings existing in the prior art, provide
What IR fluorescence region had reversible machine discoloration property is framework compound, preparation and its application based on diazosulfide.
In order to solve the above technical problems, present invention provide the technical scheme that
What a kind of novel near-infrared fluorescent region of offer had reversible machine discoloration property is skeleton based on diazosulfide
Compound, with structure described in compound 1-4:
It is of the present invention near-infrared fluorescent region have reversible machine discoloration property based on diazosulfide be bone
The preparation method of frame compound, steps are as follows: the synthetic method of compound 1 and 2 are as follows: under an inert atmosphere, by diazosulfide
Class compound and N, N- dimethyl -4- vinyl aniline is using potassium carbonate as alkali, using palladium acetate as catalyst, with tetrabutyl bromine
Change ammonium as phase transfer catalyst and carry out bilateral Heck coupling reaction, post-processing obtains luminescent material after reaction；
The diazosulfide class compound is that the bis- fluoro- 2,1,3- diazosulfide of bromo- 5,6- bis- of 4,7- or 4,7- bis- are bromo-
2,1,3- diazosulfide.
The synthetic method of compound 3 are as follows: under an inert atmosphere, by 4,7- bis- bromo- 2,1,3- diazosulfide and N, N- bis-
Methyl -4- vinyl aniline makees alkali in potassium carbonate, palladium acetate as catalyst, tetrabutylammonium bromide as phase transfer catalyst,
Under conditions of unilateral Heck coupling reaction occurs, after reaction post-processing obtain target compound 3.
The synthetic method of compound 4 are as follows: step 1): under an inert atmosphere, by 4,7- bis- bromo- 2,1,3- diazosulfide,
2- vinylpyridine makees alkali in potassium carbonate, and palladium acetate is as catalyst, under the conditions of tetrabutylammonium bromide is as phase transfer catalyst
Unilateral Heck coupling reaction occurs for control, and post-processing obtains greenish yellow solid after reaction；Step 2): under an inert atmosphere,
The greenish yellow solid and N that step 1) is obtained, N- dimethyl -4- vinyl aniline make alkali in potassium carbonate, and palladium acetate is as catalysis
Agent, tetrabutylammonium bromide post-process after reaction as unilateral Heck coupling reaction occurs under conditions of phase transfer catalyst
Obtain target compound 4.
According to the above scheme, the bilateral Heck coupling reaction condition are as follows: diazosulfide class compound and N in reactant,
N- dimethyl -4- vinyl benzene amine equivalent ratio is 1:10, in 110 DEG C of back flow reaction 48h.
According to the above scheme, unilateral Heck coupling reaction condition are as follows: diazosulfide class compound and N in reactant, N- bis-
Methyl -4- vinyl aniline or 2- vinylpyridine equivalent proportion are 1:1.2, in 110 DEG C of back flow reaction 40h.
According to the above scheme, reaction dissolvent is made with DMF in above-mentioned reaction.
According to the above scheme, the post-processing step are as follows: it is washed after being cooled to room temperature, organic layer is extracted with dichloromethane to obtain,
Then anhydrous Na is used2SO4Organic layer is dried, then rotates out dichloromethane solvent, then use column chromatography.
Specifically, bromo- 5, the 6- bis- fluoro- 2 of 4,7- bis-, 1,3- diazosulfide and N, N- bis- in the preparation of above compound 1
The molar ratio of methyl -4- vinyl aniline is 1:10, the reaction are as follows: under inertia oxygen free condition, by 4,7- bis- bromo- 5,
The fluoro- 2,1,3- diazosulfide of 6- bis-, N, N- dimethyl -4- vinyl aniline, potassium carbonate, palladium acetate, tetrabutylammonium bromide and
In pressure pipe after having been drained off the n,N-Dimethylformamide addition vacuum nitrogen gas of air, mixture is reacted at 110 DEG C
48h, after reaction, post-processing obtain brown solid compound 1.
The bromo- 2,1,3- diazosulfide of 4,7- bis- and N, N- dimethyl -4- vinyl aniline rubs in the preparation of compound 2
You are than being 1:10；The reaction are as follows: under inertia oxygen free condition, by 4,7- bis- bromo- 2,1,3- diazosulfide, N, N- diformazan
It base -4- vinyl aniline, potassium carbonate, palladium acetate, tetrabutylammonium bromide and has been drained off the N,N-dimethylformamide of air and adds
In pressure pipe after entering vacuum nitrogen gas, mixture is in 110 DEG C of reaction 48h, and after reaction, it is solid that post-processing obtains brownish red
Body compound 2.
The bromo- 2,1,3- diazosulfide of 4,7- bis- and N, N- dimethyl -4- vinyl aniline rubs in the preparation of compound 3
You are than being 1:1.2；The reaction are as follows: under inertia oxygen free condition, by 4,7- bis- bromo- 2,1,3- diazosulfide, N, N- bis-
Methyl -4- vinyl aniline, potassium carbonate, palladium acetate, tetrabutylammonium bromide and the N,N-dimethylformamide for having been drained off air
In pressure pipe after vacuum nitrogen gas is added, mixture is in 110 DEG C of reaction 40h, and after reaction, post-processing obtains kermesinus
Solid chemical compound 3.
The molar ratio of 4,7- bis- bromo- 2,1,3- diazosulfide and 2- vinylpyridine in step 1) prepared by compound 4
For 1:1.2, the reaction are as follows: under inertia oxygen free condition, under inertia oxygen free condition, by 4,7- bis- bromo- 2,1,3- benzo
Thiadiazoles, 2- vinylpyridine, potassium carbonate, palladium acetate, tetrabutylammonium bromide and the N for having been drained off air, N- dimethyl formyl
In pressure pipe after amine addition vacuum nitrogen gas, mixture is in 110 DEG C of reaction 40h, and after reaction, post-processing obtains yellowish green
Color solid.The greenish yellow solid 4a and N for obtaining step 1) in step 2), the molar ratio of N- dimethyl -4- vinyl aniline are
1:1.2, the reaction are as follows: under inertia oxygen free condition, greenish yellow solid 4a, N that step 1) is obtained, N- dimethyl -4-
Vinyl aniline, potassium carbonate, palladium acetate, tetrabutylammonium bromide and have been drained off air N,N-dimethylformamide be added take out it is true
In pressure pipe after empty inflated with nitrogen, mixture is in 110 DEG C of reaction 40h, and after reaction, post-processing obtains brown-red solid chemical combination
Object 4.
The invention also includes above-mentioned being passed based on diazosulfide for framework compound with reversible machine discoloration property
Application in terms of sensor material.
Reversible engine is had in near-infrared fluorescent region for framework compound based on diazosulfide the invention also includes above-mentioned
Application in terms of the sensor material of tool discoloration property.
The beneficial effects of the present invention are:
1, luminescent material provided by the invention is with D- π-A- π-D or A- π-D skeleton, with 2,1,3- diazosulfides work
For receptor, dimethylamino or pyridine are connected with the conjugated system of styrene as donor, have in near-infrared fluorescent region reversible
Machinery discoloration property.The fluorescence emission spectrum of this kind of compound itself is close or reaches near infrared light region, after mechanical lapping
Emission spectrum range occurs red shift and all reaches near infrared light region, shows good mechanical discoloration property, methylene chloride is added dropwise
Solution is on the sample after grinding, after dry, maximum fluorescence emission peak return to original state again under position, show machine
The invertibity of tool discoloration.
2, preparation method of the present invention is relatively simple, yield 28.6-48.3%.
3, luminescent material provided by the invention is expected to the sensor as novel near-infrared fluorescent zone machines stimuli responsive
Material, to be applied to the research fields such as medical imaging, anti-counterfeiting ink.
Detailed description of the invention
Fig. 1 be the embodiment of the present invention 1 prepared by compound 1 grind before, grinding after and grinding after use methylene chloride again
Fluorescence emission spectrogram of compound of the sample of solution processing under 470nm excitation wavelength；
Fig. 2 be embodiment 1 prepared by compound 1 grind before, grinding after and grinding after again at dichloromethane solution
Solid fluorescence picture of the sample of reason under 365nm UV illumination；
Fig. 3 is fluorescent emission intensity figure under 1 solid sample different conditions of compound prepared by embodiment 1 (in A
Fluorescence photo under Xenogen IVIS spectrum imaging system)；
Fig. 4 be embodiment 2 prepared by compound 2 grind before, grinding after and grinding after again at dichloromethane solution
Fluorescence emission spectrogram of compound of the sample of reason under 470nm excitation wavelength；
Fig. 5 be embodiment 3 prepared by compound 3 grind before, grinding after and grinding after again at dichloromethane solution
Fluorescence emission spectrogram of compound of the sample of reason under 470nm excitation wavelength；
Fig. 6 be embodiment 4 prepared by compound 4 grind before, grinding after and grinding after again at dichloromethane solution
Fluorescence emission spectrogram of compound of the sample of reason under 470nm excitation wavelength.
Specific embodiment
Technical solution in order to enable those skilled in the art to better understand the present invention, with reference to the accompanying drawing to the present invention make into
One step detailed description.
Embodiment 1
Compound 1 is synthesized, synthetic route is as follows:
DMF-N in reaction equation, dinethylformamide, Pd (OAC)2Palladium acetate, Bu4N+Br-Tetrabutylammonium bromide.
Specific synthesis step is as follows:
By compound 4, bromo- 5, the 6- bis- fluoro- 2 of 7- bis-, 1,3- diazosulfide (0.80g, 2.42mmol), palladium acetate
(22.45mg, 0.10mmol), potassium carbonate (0.87g, 6.29mmol) and tetrabutylammonium bromide (1.64g, 5.08mmol) are set
In pressure pipe, anhydrous DMF (30mL) is added in a nitrogen atmosphere, N, N- dimethyl -4- aminobenzene second is added under stirring condition
Alkene (3.57 g, 24.25mmol), mixture reacts 48h under 110 DEG C of counterflow conditions, is cooled to room temperature after reaction, washing
Three times, it is extracted with dichloromethane, obtained organic layer anhydrous Na2SO4It is dry, dichloromethane solvent is screwed out, column chromatography for separation obtains
To brown solid 320mg, yield 28.6%.1H NMR(400MHz,CDCl3): δ (ppm)=8.23 (d, J=16Hz, 2H),
7.57 (d, J=8Hz, 4H), 7.41 (d, J=20Hz, 2H), 6.74 (d, J=8Hz, 4H), 3.03 (s, 12H) .EI-MS:m/z
=462.09 [M]+；Calculated exact mass=462.17.
The solid fluorescence emission spectrum (excitation wavelength 470nm) of the present embodiment products obtained therefrom is as shown in Figure 1, solid line in figure
For the fluorescent emission spectrogram before the grinding of 1 sample of compound, pecked line is the fluorescent emission spectrogram after the grinding of 1 sample of compound,
The processed fluorescent emission spectrogram of sample dichloromethane solution after line is grinding.Fig. 2 is change prepared by the present embodiment
Solid fluorescence picture of the object 1 under 365nm UV illumination is closed, wherein (a) is the solid fluorescence picture before sample grinding, (b)
It (c) is to use the processed sample solid fluorescence figure of dichloromethane solution again after grinding for the solid fluorescence picture after sample grinding
Piece.It can be seen from fig. 1 and fig. 2 that have an emission peak when 1 original state of compound at 695nm, under mechanical external force effect,
Apparent red shift occurs for the fluorescence spectrum of compound 1, occurs new fluorescence emission peak at 740nm.It is shone in 365nm ultraviolet lamp
It penetrates down, the fluorescence color of compound 1 is also accordingly by near-infrared red fluorescence to near-infrared fluorescent.And at dichloromethane solution
Reason grinding after sample, maximum fluorescence emission peak return to original state again under position, product is in the ultraviolet light irradiation of 365nm
Under fluorescence color also return to initial red.
Fig. 3 is fluorescence photo of the sample manufactured in the present embodiment under A Xenogen IVIS spectrum imaging system, in figure
(a) emissive porwer for primary sample under the excitation wavelength excitation of 470nm at 640nm, it is (b) ground for primary sample
Emissive porwer of the solid afterwards under the excitation wavelength of 470nm at 640nm uses methylene chloride after (c) grinding for primary sample
Emissive porwer of the processed solid of solution under the excitation wavelength of 470nm at 640nm is (d) primary sample 470nm's
Emissive porwer under excitation wavelength at 745nm is (e) the polished solid of primary sample under the excitation wavelength of 470nm
Emissive porwer at 745nm (f) uses the processed solid of dichloromethane solution in the excitation of 470nm after primary sample grinding
Emissive porwer under wavelength at 745nm.From figure 3, it can be seen that compound 1 is in A Xenogen IVIS spectrum imaging system
Under, there is strong fluorescence in when original state at 640nm, and fluorescence is weaker at 745nm.Under mechanical external force effect, compound 1 exists
Fluorescence intensity weakens at 640nm, and fluorescence intensity increases at 745nm.And the sample after being ground with dichloromethane solution is processed
Product, fluorescence intensity enhances at 640nm, and fluorescence intensity weakens at 745nm.Thus obtain compound 1 in near-infrared fluorescent
Region shows good reversible machine discoloration property.
Embodiment 2
Compound 2 is synthesized, synthetic route is as follows:
DMF-N in reaction equation, dinethylformamide, Pd (OAC)2Palladium acetate, Bu4N+Br-Tetrabutylammonium bromide.
Specific synthesis step is as follows:
By compound 4,7- bis- bromo- 2,1,3- diazosulfide (0.80g, 2.72mmol), palladium acetate (24.69mg, 0.11
Mmol), potassium carbonate (0.98g, 7.07mmol) and tetrabutylammonium bromide (1.84g, 5.71mmol) are placed in pressure pipe,
Anhydrous DMF (30mL) is added under condition of nitrogen gas, is added N under stirring condition, N- dimethyl -4- aminostyryl (4.00g,
27.21mmol), mixture reacts 48h in 110 DEG C of stirred at reflux condition, is cooled to room temperature after reaction, washes three times,
It is extracted with dichloromethane, obtained organic layer anhydrous Na2SO4It is dry, dichloromethane solvent is screwed out, column chromatography for separation obtains palm fibre
Red solid 400mg, yield 34.5%.1H NMR(400MHz,CDCl3): δ (ppm)=7.87 (d, J=16Hz, 2H), 7.63
(s, 2H), 7.55 (d, J=8Hz, 4H), 7.49 (d, J=16Hz, 2H), 6.75 (d, J=8Hz, 4H), 3.02 (s, 12H)
.EI-MS:m/z=426.19 [M]+；Calculated exact mass=426.19.
The solid fluorescence emission spectrum (excitation wavelength 470nm) of product 2 manufactured in the present embodiment is as shown in figure 4, in figure
Solid line is the fluorescent emission spectrogram before the grinding of 2 sample of compound, and pecked line is the fluorescent emission spectrogram after sample grinding, septal line
For the processed fluorescent emission spectrogram of sample dichloromethane solution after grinding.2 original state of compound as can be seen from Figure 4
When have an emission peak at 685nm, under mechanical external force effect, apparent red shift occurs for the fluorescence spectrum of compound 2,
Occurs new fluorescence emission peak at 715nm.And the sample after being ground with dichloromethane solution is processed, maximum fluorescence emission peak is again
Position under returning to original state, to show good reversible machine discoloration property in near-infrared fluorescent region.
Embodiment 3
Compound 3 is synthesized, synthetic route is as follows:
DMF-N in reaction equation, dinethylformamide, Pd (OAC)2Palladium acetate, Bu4N+Br-Tetrabutylammonium bromide.
Specific synthesis step is as follows:
By compound 4,7- bis- bromo- 2,1,3- diazosulfide (0.80g, 2.72mmol), palladium acetate (11.22mg, 0.05
Mmol), potassium carbonate (0.49g, 3.54mmol) and tetrabutylammonium bromide (0.92g, 2.86mmol) are placed in pressure pipe,
Anhydrous DMF (30mL) is added under condition of nitrogen gas, is added N under stirring condition, N- dimethyl -4- aminostyryl (0.48g,
3.26mmol), 40h is reacted under 110 DEG C of counterflow conditions.It is cooled to room temperature after reaction, washing three times, is extracted with methylene chloride
It takes, obtained organic layer anhydrous Na2SO4It is dry, dichloromethane solvent is screwed out, column chromatography for separation obtains dark red solid
420mg, yield 42.8%.1H NMR(400MHz,CDCl3): δ (ppm)=7.86 (d, J=20Hz, 1H), 7.80 (d, J=
8Hz, 1H), 7.54 (d, J=8Hz, 2H), 7.50 (d, J=8Hz, 1H), 7.41 (d, J=16Hz, 1H), 6.74 (d, J=
8Hz, 2H), 3.02 (s, 6H) .EI-MS:m/z=359.03 [M]+；Calculated exact mass=359.01.
The solid fluorescence emission spectrum (excitation wavelength 470nm) of the product 3 of the embodiment is as shown in figure 5, solid line in figure
For the fluorescent emission spectrogram before the grinding of 3 sample of compound, pecked line is the fluorescent emission spectrogram after sample grinding, and septal line is to grind
The processed fluorescent emission spectrogram of sample dichloromethane solution after mill.As can be seen from Figure 53 original state of compound when
There is an emission peak at 640nm, under mechanical external force effect, apparent red shift occurs for the fluorescence spectrum of compound 3, at 665nm
There is new fluorescence emission peak.And the sample after being ground with dichloromethane solution is processed, maximum fluorescence emission peak is restored to again
Position under original state, to show good reversible machine discoloration property in near-infrared fluorescent region.
Embodiment 4
Compound 4 is synthesized, synthetic route is as follows:
DMF-N in reaction equation, dinethylformamide, Pd (OAC)2Palladium acetate, Bu4N+Br-Tetrabutylammonium bromide.
Specific synthesis step is as follows:
1, by compound 4,7- bis- bromo- 2,1,3- diazosulfide (0.80g, 2.72mmol), palladium acetate (11.22mg,
0.05 mmol), potassium carbonate (0.49g, 3.54mmol) and tetrabutylammonium bromide (0.92g, 2.86mmol) are placed in pressure pipe
In, anhydrous DMF (30mL) is added under a nitrogen atmosphere, 2- vinylpyridine (0.34g, 3.26mmol) is added under stirring condition,
40h is reacted under 110 DEG C of counterflow conditions.It is cooled to room temperature after reaction, washing three times, is extracted with dichloromethane, what is obtained has
Machine layer anhydrous Na2SO4It is dry, dichloromethane solvent is screwed out, column chromatography for separation obtains greenish yellow solid 380mg, yield
43.9%.1H NMR(400MHz,CDCl3): δ (ppm)=8.66 (d, J=4Hz, 1H), 8.18 (d, J=16Hz, 1H), 8.03
(d, J=16Hz, 1H), 7.86 (d, J=8Hz, 1H), 7.72 (t, J=8Hz, 1H), 7.60 (d, J=8Hz, 1H), 7.51 (d,
J=8Hz, 1H), 7.26-7.18 (m, 1H) .EI-MS:m/z=315.98 [M]+；Calculated exact mass=
316.96。
2, the greenish yellow solid (0.80g, 2.52mmol) obtained step 1, palladium acetate (11.22mg, 0.05mmol), carbon
Sour potassium (0.45g, 3.28mmol) and tetrabutylammonium bromide (0.85g, 2.65mmol) are placed in pressure pipe, in condition of nitrogen gas
Lower addition anhydrous DMF (30mL), is added N under stirring condition, N- dimethyl -4- aminostyryl (0.45g, 3.02 mmol),
40h is reacted under 110 DEG C of counterflow conditions.It is cooled to room temperature after reaction, washing three times, is extracted with dichloromethane, what is obtained has
Machine layer anhydrous Na2SO4It is dry, dichloromethane solvent is screwed out, column chromatography for separation obtains 360 mg of brown-red solid, yield
37.2%.1H NMR(600MHz,CDCl3): δ (ppm)=8.68 (s, 1H), 8.21 (d, J=18Hz, 1H), 8.11 (d, J=
18Hz, 1H), 7.93 (d, J=18Hz, 1H), 7.73 (dd, J=6,6Hz, 2H), 7.69 (d, J=6Hz, 1H), 7.59 (d, J
=12Hz, 2H), 7.56-7.51 (m, 2H), 7.20 (d, J=6Hz, 1H), 6.77 (d, J=6Hz, 2H), 3.05 (s, 6H)
.EI-MS:m/z=384.25 [M]+；Calculated exact mass=384.14.
The solid fluorescence emission spectrum (excitation wavelength 470nm) of the product 4 of the embodiment is as shown in fig. 6, solid line in figure
For the fluorescent emission spectrogram before the grinding of 4 sample of compound, pecked line is the fluorescent emission spectrogram after sample grinding, and septal line is to grind
The processed fluorescent emission spectrogram of sample dichloromethane solution after mill.As can be seen from Figure 64 original state of compound when
There is an emission peak at 675nm, under mechanical external force effect, apparent red shift occurs for the fluorescence spectrum of compound 4, at 715nm
There is new fluorescence emission peak.And the sample after being ground with dichloromethane solution is processed, maximum fluorescence emission peak is restored to again
Position under original state, to show good reversible machine discoloration property in near-infrared fluorescent region.
Claims (7)
1. what a kind of near-infrared fluorescent region had reversible machine discoloration property is framework compound based on diazosulfide, special
Sign is: there is structure described in compound 1-4:
2. it is described in claim 1 based on diazosulfide be framework compound preparation method, steps are as follows:
The synthetic method of compound 1 and 2 are as follows: under an inert atmosphere, by diazosulfide class compound and N, N- dimethyl -4- second
Alkenyl aniline is using potassium carbonate as alkali, using palladium acetate as catalyst, is carried out using tetrabutylammonium bromide as phase transfer catalyst
Bilateral Heck coupling reaction, post-processing obtains luminescent material after reaction；The diazosulfide class compound is 4,7- bis-
The fluoro- 2,1,3- diazosulfide of bromo- 5,6- bis- or the bromo- 2,1,3- diazosulfide of 4,7- bis-；
The synthetic method of compound 3 are as follows: under an inert atmosphere, by 4,7- bis- bromo- 2,1,3- diazosulfide and N, N- dimethyl-
4- vinyl aniline makees alkali in potassium carbonate, palladium acetate as catalyst, tetrabutylammonium bromide as phase transfer catalyst, condition
Lower that unilateral Heck coupling reaction occurs, post-processing obtains target compound 3 after reaction；
The synthetic method of compound 4 are as follows: step 1): under an inert atmosphere, by 4,7- bis- bromo- 2,1,3- diazosulfide, 2- second
Alkenyl pyridine makees alkali in potassium carbonate, and palladium acetate is as catalyst, and tetrabutylammonium bromide under the conditions of phase transfer catalyst as controlling
Unilateral Heck coupling reaction occurs, post-processing obtains greenish yellow solid after reaction；Step 2: under an inert atmosphere, by step
1) greenish yellow solid and N obtained, N- dimethyl -4- vinyl aniline make alkali in potassium carbonate, and palladium acetate is as catalyst, four fourths
Base ammonium bromide is as occurring unilateral Heck coupling reaction under conditions of phase transfer catalyst, post-processing obtains target after reaction
Compound 4.
3. it is according to claim 2 based on diazosulfide be framework compound preparation method, it is characterised in that: institute
State bilateral Heck coupling reaction condition are as follows: diazosulfide class compound and N in reactant, N- dimethyl -4- vinyl aniline
Equivalent proportion is 1:10, in 110 DEG C of back flow reaction 48h；The unilateral Heck coupling reaction condition are as follows: diazosulfide in reactant
Class compound and N, N- dimethyl -4- vinyl aniline or 2- vinylpyridine equivalent proportion are 1:1.2, in 110 DEG C of back flow reactions
40h。
4. according to claim 2 is the preparation method of framework compound based on diazosulfide, it is characterised in that: anti-
Reaction dissolvent is made with DMF in answering.
5. it is according to claim 2 based on diazosulfide be framework compound preparation method, it is characterised in that: institute
State post-processing step are as follows: wash after being cooled to room temperature, organic layer is extracted with dichloromethane to obtain, then uses anhydrous Na2SO4To organic
Layer is dried, and then rotates out dichloromethane solvent, then use column chromatography.
6. it is described in claim 1 based on diazosulfide be application of the framework compound in terms of sensor material.
7. described in claim 1 become in near-infrared fluorescent region with reversible machine based on diazosulfide for framework compound
Application in terms of the sensor material of color property.
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