CN108689963A - Diazosulfide malononitrile and its synthetic method and the method for detecting CN- - Google Patents
Diazosulfide malononitrile and its synthetic method and the method for detecting CN- Download PDFInfo
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- CN108689963A CN108689963A CN201810721697.XA CN201810721697A CN108689963A CN 108689963 A CN108689963 A CN 108689963A CN 201810721697 A CN201810721697 A CN 201810721697A CN 108689963 A CN108689963 A CN 108689963A
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- btd
- diazosulfide
- tpa
- malononitrile
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- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 title claims abstract description 106
- OBISXEJSEGNNKL-UHFFFAOYSA-N dinitrogen-n-sulfide Chemical compound [N-]=[N+]=S OBISXEJSEGNNKL-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000010189 synthetic method Methods 0.000 title claims abstract description 21
- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000862 absorption spectrum Methods 0.000 claims abstract description 16
- 238000002189 fluorescence spectrum Methods 0.000 claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 12
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 111
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 48
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 238000004440 column chromatography Methods 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 29
- 238000000926 separation method Methods 0.000 claims description 29
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 25
- 239000003208 petroleum Substances 0.000 claims description 23
- 239000012074 organic phase Substances 0.000 claims description 22
- 238000010521 absorption reaction Methods 0.000 claims description 20
- 239000012141 concentrate Substances 0.000 claims description 20
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 20
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 20
- 239000012153 distilled water Substances 0.000 claims description 15
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000003480 eluent Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 238000000605 extraction Methods 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 10
- 238000002390 rotary evaporation Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 235000019270 ammonium chloride Nutrition 0.000 claims description 9
- 238000002371 ultraviolet--visible spectrum Methods 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- VXWBQOJISHAKKM-UHFFFAOYSA-N (4-formylphenyl)boronic acid Chemical compound OB(O)C1=CC=C(C=O)C=C1 VXWBQOJISHAKKM-UHFFFAOYSA-N 0.000 claims description 5
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 5
- 239000005695 Ammonium acetate Substances 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 229940043376 ammonium acetate Drugs 0.000 claims description 5
- 235000019257 ammonium acetate Nutrition 0.000 claims description 5
- 230000005284 excitation Effects 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 239000005416 organic matter Substances 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 3
- 210000001508 eye Anatomy 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 239000002027 dichloromethane extract Substances 0.000 claims 1
- 150000002240 furans Chemical class 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000002386 leaching Methods 0.000 claims 1
- 239000006210 lotion Substances 0.000 claims 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 8
- 230000003287 optical effect Effects 0.000 abstract description 4
- 150000001450 anions Chemical class 0.000 description 21
- 239000000523 sample Substances 0.000 description 20
- 239000000126 substance Substances 0.000 description 20
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 11
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 229910052805 deuterium Inorganic materials 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000284 extract Substances 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- -1 amido phenyl boric acid Chemical compound 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 150000003851 azoles Chemical class 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 230000000269 nucleophilic effect Effects 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- KZJRKRQSDZGHEC-UHFFFAOYSA-N 2,2,2-trifluoro-1-phenylethanone Chemical compound FC(F)(F)C(=O)C1=CC=CC=C1 KZJRKRQSDZGHEC-UHFFFAOYSA-N 0.000 description 1
- NIBFJPXGNVPNHK-UHFFFAOYSA-N 2,2-difluoro-1,3-benzodioxole-4-carbaldehyde Chemical group C1=CC(C=O)=C2OC(F)(F)OC2=C1 NIBFJPXGNVPNHK-UHFFFAOYSA-N 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 241001465805 Nymphalidae Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- 210000005252 bulbus oculi Anatomy 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000012850 discrimination method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005274 electronic transitions Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- KFIFDKLIFPYSAZ-UHFFFAOYSA-N formyloxy(phenyl)borinic acid Chemical compound O=COB(O)C1=CC=CC=C1 KFIFDKLIFPYSAZ-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000000215 hyperchromic effect Effects 0.000 description 1
- 230000007954 hypoxia Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 150000004893 oxazines Chemical class 0.000 description 1
- 150000004880 oxines Chemical class 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 230000000007 visual effect Effects 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
-
- 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
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Immunology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Molecular Biology (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The present invention discloses diazosulfide malononitrile and its synthetic method and detection CN-Method, diazosulfide malononitrile is shown below:The synthetic method of diazosulfide malononitrile, including step:(1) synthesis of intermediate TPA-BTD-Br;(2) synthesis of intermediate TPA-BTD-CHO;(3) synthesis of diazosulfide malononitrile TPA-BTD-BT.Diazosulfide malononitrile fluoroscopic examination CN-Method, (1) using tetrahydrofuran THF as solvent, be added diazosulfide malononitrile TPA-BTD-BT, be configured to the tetrahydrofuran THF solution of diazosulfide malononitrile TPA-BTD-BT;(2) sample to be tested is added to the tetrahydrofuran THF solution of diazosulfide malononitrile TPA-BTD-BT;(3) it observes by the naked eye, whether have CN in uv-visible absorption spectra or fluorescence spectrum identification sample to be tested-.The present invention is successfully constructed to CN-Turn-on types are highly selective, fluorescent optical sensor of strong anti-interference ability.
Description
Technical field
The present invention relates to CN-Detection technique field.Specifically diazosulfide malononitrile and its synthetic method and
Detect CN-Method.
Background technology
Cyanide in the industrial production be widely used in life, can be used for being electroplated in the industrial production, plastic manufacturing,
Metallurgical, gold extraction and process hides etc..But cyanide is a kind of extremely toxic substance, and it is very fast to be poisoned.They can be by being permitted
Multipath enters human body, such as skin absorbs, wound enters, the sucking of respiratory tract can make blood red in blood into after human body
Albumen is poisoned, and causes to have difficulty in breathing, cell hypoxia is choked to death.Adult, which takes orally 150-250mg, can cause death.Therefore, it opens
Hair one kind fast and accurately detecting CN-The method of ion is very significant, in the past few decades come, chemical sensor fluorescence probe because
It is to CN-The superior sensitivity of ion and selectivity are greatly paid close attention to so as to cause people.
Up to the present, scientists have developed many detection CN-Method, including with transition metal, boron derivative
With the formation of the cyanide complex of CdSe quantum dot, titration, chromatography, electrochemical process.But it is visited with chemical sensor fluorescence
Needle method is compared, and chemical sensor should be that selectivity is more preferable, and sensitivity higher, cost is lower, easy to operate simple.Chemistry passes
Sensor fluorescence probe is to CN-Mechanism include nucleophilic addition, interaction of hydrogen bond and sloughs proton at Supramolecular self assembly.
CN based on nucleophilic addition-Chemical sensor fluorescence probe possesses outstanding selectivity and sensitivity.Based on above-mentioned machine
A series of reason, in the past few years it has been reported that probes, such as oxazines, pyrans, square alkane, trifluoroacetyl benzene, acyl group triazine, a word used for translation
Pyridine, salicylide and carboxylic acid amides.Therefore, design synthesizes a kind of novel CN-Chemical sensor fluorescence probe becomes people's research
Hot spot.Natural Science Fund In The Light (1708085MB43) in Anhui Province, Anhui Department of Education of Shanxi Province major project (KJ2018ZD035), colleges and universities
Outstanding youth talent's support plan key project (gxyqZD2016192) and Fuyang municipal government-Fuyang Teachers College laterally close
Under the subsidy for making great, key project (XDHX201704, XDHX201701), applicant is to detecting CN-Method carried out depth
Enter research.
Invention content
For this purpose, a kind of for CN technical problem to be solved by the present invention lies in providing-The chemical sensor fluorescence of detection
Probe diazosulfide malononitrile and its synthetic method and detection CN-Method.
In order to solve the above technical problems, the present invention provides the following technical solutions:
Diazosulfide malononitrile, which is characterized in that as shown in formula (I):
The synthetic method of diazosulfide malononitrile, which is characterized in that include the following steps:
(1) synthesis of intermediate TPA-BTD-Br, shown in intermediate TPA-BTD-Br such as formulas (II):
(2) by intermediate TPA-BTD-Br synthetic intermediate TPA-BTD-CHO, intermediate TPA-BTD-CHO such as formulas (III)
It is shown:
(3) synthesis of diazosulfide malononitrile TPA-BTD-BT, diazosulfide malononitrile TPA-BTD-BT such as formulas (I)
It is shown:
The synthetic method of above-mentioned diazosulfide malononitrile, in step (1), by 4- hexichol amidos phenyl boric acid, 4,7- bis-
Bromo- 2,1,3- diazosulfide, 4- (triphenylphosphine) palladiums and potassium carbonate are placed in there-necked flask, and tetrahydrofuran is added into mixture
THF, toluene and distilled water H2O, then methyl tricapryl ammonium chloride is added dropwise;Magnetite is added to be sufficiently stirred, reacts under nitrogen atmosphere;Instead
After answering, distilled water is added into reactant, then extracts to obtain organic phase with dichloromethane, organic subtracts each other what is be obtained by extraction
Pressure distillation, obtains concentrate, concentrate obtains intermediate TPA-BTD-Br through column chromatography for separation, concentration and drying;Column chromatography point
From eluent be dichloromethane and petroleum ether mixture.
The synthetic method of above-mentioned diazosulfide malononitrile, in step (1), by 4- hexichol amido phenyl boric acids 2.7568g,
4,7- bis- bromo- 2,1,3- diazosulfide 2.3576g, 4- (triphenylphosphine) palladium 0.1342g and potassium carbonate 1.7880g is placed in
In 250mL there-necked flasks, 60mL tetrahydrofuran THFs, 45mL toluene and 22mL distilled water H are added into mixture2O, then be added dropwise
0.1mL methyl tricapryl ammonium chlorides;Magnetite is added to be sufficiently stirred, back flow reaction 16h, the temperature of back flow reaction are under nitrogen atmosphere
85℃;After reaction, 200mL distilled water is added into reactant, then extracts to obtain organic phase with dichloromethane, will extract
The organic phase vacuum distillation arrived, obtains concentrate, concentrate obtains intermediate TPA- through column chromatography for separation, concentration and drying
BTD-Br;The eluent of column chromatography for separation is the mixture of dichloromethane and petroleum ether, the body of the dichloromethane and petroleum ether
Product is than being 1:3.5.
The synthetic method of above-mentioned diazosulfide malononitrile, in step (2), by intermediate TPA-BTD-Br, 4- formyl
Base phenyl boric acid, 4- (triphenylphosphine) palladiums and potassium carbonate are placed in there-necked flask, then methyl tricapryl ammonium chloride is added dropwise, then to mixing
Tetrahydrofuran THF, toluene and distilled water H are added in object2O;Magnetite is added and is sufficiently stirred dissolving, under nitrogen atmosphere back flow reaction;
After reaction, organic phase is extracted to obtain with extractant dichloromethane, the organic phase rotary evaporation being obtained by extraction is obtained into drying solid;
By drying solid through column chromatography for separation, concentration and drying, intermediate TPA-BTD-CHO is obtained, the eluent of column chromatography for separation is
The mixture of dichloromethane and petroleum ether.
The synthetic method of above-mentioned diazosulfide malononitrile, in step (2), by intermediate TPA-BTD-Br2.2737g,
4- formylphenylboronic acids 1.1100g, 4- (triphenylphosphine) palladium 0.2588g and potassium carbonate 1.5525g are placed in 250mL there-necked flasks,
0.1mL methyl tricapryl ammonium chlorides are added dropwise again, 40mL tetrahydrofuran THFs, 60mL toluene and 25mL are then added into mixture
Distilled water H2O;Magnetite is added and is sufficiently stirred dissolving, under nitrogen atmosphere back flow reaction 16h, the temperature of back flow reaction is 85 DEG C;Instead
After answering, organic phase is extracted to obtain with extractant dichloromethane, the organic phase rotary evaporation being obtained by extraction is obtained into drying solid;It will
Drying solid obtains intermediate TPA-BTD-CHO, the eluent of column chromatography for separation is two through column chromatography for separation, concentration and drying
The volume ratio of the mixture of chloromethanes and petroleum ether, the dichloromethane and petroleum ether is 1:3.5.
The synthetic method of above-mentioned diazosulfide malononitrile, in step (3), by intermediate TPA-BTD-CHO, malononitrile
And ammonium acetate, it is placed in three-necked flask, and glacial acetic acid is added into mixture, adds magnetite and be sufficiently stirred, then in nitrogen
It is reacted under atmosphere;After reaction, organic phase is extracted to obtain with extractant dichloromethane, the organic phase rotary evaporation being obtained by extraction is obtained
Concentrate obtains diazosulfide malononitrile TPA-BTD-BT, column chromatography by concentrate through column chromatography for separation, concentration and drying
The eluent of separation is the mixture of dichloromethane and petroleum ether.
The synthetic method of above-mentioned diazosulfide malononitrile, in step (3), by intermediate TPA-BTD-
CHO1.5045g, malononitrile 2.5219g and ammonium acetate 4.7811g, are placed in 500mL three-necked flasks, and be added into mixture
200mL glacial acetic acid adds magnetite and is sufficiently stirred, and then reacts 8h under nitrogen atmosphere, and reaction temperature is 117 DEG C;Reaction terminates
Afterwards, upper layer organic matter is extracted with extractant dichloromethane, upper layer organic matter rotary evaporation is obtained into concentrate, by concentrate through column layer
Analysis separation, concentration and drying obtain diazosulfide malononitrile TPA-BTD-BT, and the eluent of column chromatography for separation is dichloromethane
With the mixture of petroleum ether, the volume ratio of the dichloromethane and petroleum ether is 1:1.
The method that diazosulfide malononitrile detects CN-, includes the following steps:(1) using tetrahydrofuran THF as solvent, add
Enter diazosulfide malononitrile TPA-BTD-BT, the tetrahydrofuran THF for being configured to diazosulfide malononitrile TPA-BTD-BT is molten
Liquid;Diazosulfide malononitrile TPA-BTD-BT is as follows:
(2) sample to be tested is added to the tetrahydrofuran THF solution of diazosulfide malononitrile TPA-BTD-BT;(3) pass through
It visually observes, whether have CN in uv-visible absorption spectra or fluorescence spectrum identification sample to be tested-。
Above-mentioned diazosulfide malononitrile fluoroscopic examination CN-Method, visually observing recognition methods is:Solution colour is by orange
Discoloration yellowly, illustrates there is CN in sample to be tested-;Uv-visible absorption spectra recognition methods is:It is carried out at 200-660nm
UV-vis spectrum tests, UV-vis absorption spectrums absorption peak at 367nm decline or disappear, and the absorption peak at 465nm declines simultaneously
It is blue shifted to 440nm, while occurring two isobestic points at 430 and 407nm, illustrates there is CN in sample to be tested-;Fluorescence light
Spectrum discrimination method is:Emission peak is generated under 465nm excitations, at 600nm, illustrates there is CN in sample to be tested-, or in 365nm purples
Under outer light irradiation, solution presentation bright orange fluorescence, illustrate there is CN in sample to be tested-。
Technical scheme of the present invention achieves following beneficial technique effect:
The present invention is in Anhui Province's Natural Science Fund In The Light (1708085MB43), Anhui Department of Education of Shanxi Province major project
(KJ2018ZD035), the outstanding youth talent's support plan key project (gxyqZD2016192) of colleges and universities and Fuyang municipal government-
Fuyang Teachers College's Horizontal Cooperation is great, under key project (XDHX201704, XDHX201701) subsidy, with 4- hexichol amidos
Phenyl boric acid, 4- formylphenylboronic acids, bis- bromo- 2,1,3- diazosulfides of 4,7-, malononitrile are Material synthesis subbase group containing short of electricity
Diazosulfide malononitrile molecule (TPA-BDT-BT).Synthesized intermediate and product using infrared spectrum (IR), it is ultraviolet-
Visible absorption spectra (UV-vis), fluorescence spectrum (FS), nuclear magnetic resonance spectroscopy (1HNMR) and carbon-13 nmr spectra (13CNMR) into
Characterization is gone.Diazosulfide malononitrile TPA-BTD-BT contains electron deficient group, has activated CN-The nucleophilic of dicyano is added
At the electron-withdrawing ability for breaking dicyano acts on, and hinders electric charge transfer.Using diazosulfide malononitrile TPA-BTD-BT as fluorescence
Probe is used for CN-Detection, the molecule only to CN-Selective recognition reaction, the Fluorescence Increasing factor obtain 16, it is other it is cloudy from
Son (F-,Cl-,Br-,I-,CH3COO-,NO2 -,NO3 -,H2PO4 -,HCO3 -,CO3 2-,SO4 2-) presence have no effect on the sensor pair
CN-Identification.Diazosulfide malononitrile TPA-BTD-BT is successfully constructed to CN-Turn-on types it is highly selective, strong anti-
The fluorescent optical sensor of interference performance.
Description of the drawings
The diazosulfide malononitrile TPA-BTD-BT synthetic route charts of Fig. 1 present invention;
The 4- hexichol amido phenyl boric acid TPA-BTD-B (OH) of Fig. 2 present invention2With the infrared spectrum of intermediate TPA-BTD-Br
Figure;
The infrared spectrogram of the intermediate TPA-BTD-Br and intermediate TPA-BTD-CHO of Fig. 3 present invention;
The infrared spectrogram of the intermediate TPA-BTD-CHO and diazosulfide malononitrile TPA-BTD-BT of Fig. 4 present invention.
The ultraviolet-ray visible absorbing light of the tetrahydrofuran solution of the diazosulfide malononitrile TPA-BTD-BT of Fig. 5 present invention
Spectrum, a concentration of the 2 × 10 of TPA-BTD-BT-5mol/L;
The fluorescence spectrum of the tetrahydrofuran solution of the diazosulfide malononitrile TPA-BTD-BT of Fig. 6 present invention, TPA-
A concentration of the 2 × 10 of BTD-BT-5mol/L;
The intermediate TPA-BTD-Br's of Fig. 7 present invention1HNMR (deuterium band chloroform CDCl3For solvent);
The intermediate TPA-BTD-Br's of Fig. 8 present invention13CNMR (deuterium band chloroform CDCl3For solvent);
The intermediate TPA-BTD-CHO's of Fig. 9 present invention1HNMR (deuterium band chloroform CDCl3For solvent);
The intermediate TPA-BTD-CHO's of Figure 10 present invention13CNMR (deuterium band chloroform CDCl3For solvent);Figure 11 present invention
Diazosulfide malononitrile TPA-BTD-BT1HNMR (deuterium band chloroform CDCl3For solvent);
The TPA-BTD-BT's of the diazosulfide malononitrile of Figure 12 present invention13CNMR (deuterium band chloroform CDCl3For solvent);
The nuclear-magnetism chemical shift analysis chart of the intermediate TPA-BTD-CHO of Figure 13 present invention;
The nuclear-magnetism chemical shift analysis chart of the diazosulfide malononitrile TPA-BTD-BT of Figure 14 present invention
THF solution (a concentration of the 2.0 of TPA-BTD-BT of the diazosulfide malononitrile TPA-BTD-BT of Figure 15 present invention
×10-5Mol/L CN is added in)-With the UV-visible absorption spectrum (CN of addition of other anion-With other anion
Concentration is 4.0 × 10-5mol/L);
THF solution (a concentration of the 2.0 of TPA-BTD-BT of the diazosulfide malononitrile TPA-BTD-BT of Figure 16 present invention
×10-5Mol/L CN is added in)-With the fluorescence spectra (CN of addition of other anion-Concentration with other anion is
4.0×10-5mol/L)
THF solution (a concentration of the 2.0 of TPA-BTD-BT of the diazosulfide malononitrile TPA-BTD-BT of Figure 17 present invention
×10-5Mol/L CN is added in)-With other anion, 365 nano-ultraviolet lights irradiation under color change, (from left to right according to
Secondary is Blank, CN-, F-,Cl-, Br-, I-,CH3COO-, NO2 -, NO3 -, H2PO4 -, HCO3 -, CO3 2-, SO4 2-);
THF solution (a concentration of the 2.0 of TPA-BTD-BT of the diazosulfide malononitrile TPA-BTD-BT of Figure 18 present invention
×10-5Mol/L in), the CN of various concentration is added-UV-visible absorption spectrum (CN-Concentration increases from 0 in the direction of the arrow
To 4.0 × 10-5mol/L);
THF solution (a concentration of the 2.0 of TPA-BTD-BT of the diazosulfide malononitrile TPA-BTD-BT of Figure 19 present invention
×10-5Mol/L in), the CN of various concentration is added-Fluorescence spectra (λex=465nm, slit 5,5;CN-Concentration is along arrow
Direction increases to 4.0 × 10 from 0-5mol/L);
THF solution (a concentration of the 2.0 of TPA-BTD-BT of the diazosulfide malononitrile TPA-BTD-BT of Figure 20 present invention
×10-5Mol/L it in), is added after various anion and CN-The UV-visible absorption spectrum (CN of addition-With other it is cloudy from
The concentration of son is 4.0 × 10-5mol/L);
THF solution (a concentration of the 2.0 of TPA-BTD-BT of the diazosulfide malononitrile TPA-BTD-BT of Figure 21 present invention
×10-5Mol/L it in), is added after various anion and CN-The Fluorescence Increasing factor block diagram (CN of addition-With other anion
Concentration be 4.0 × 10-5mol/L)。
Specific implementation mode
1. diazosulfide malononitrile, is shown below:
Diazosulfide (BTD) has good electronic carrier transfer performance, and it is total can to form D-A with the group of electron
Yoke structure.Diazosulfide is introduced into the delocalization range for the pi-electron that can increase molecule in molecule so that ultraviolet light wave occurs red
It moves, plays conjugation hyperchromic effect.Due to the introducing of diazosulfide in present patent application, can make containing the third two eyeball type molecules to CN-
Selectivity and sensitivity greatly improve.
2. the synthetic method of diazosulfide malononitrile, synthetic route chart is as shown in Figure 1, include the following steps:
(1) synthesis of intermediate TPA-BTD-Br;
In step (1), by 4- hexichol amido phenyl boric acids 2.7568g, 4,7- bis- bromo- 2,1,3- diazosulfide
2.3576g, 4- (triphenylphosphine) palladium 0.1342g and potassium carbonate 1.7880g are placed in 250mL there-necked flasks, are added into mixture
60mL tetrahydrofuran THFs, 45mL toluene and 22mL distilled water H2O, then 0.1mL methyl tricapryl ammonium chlorides are added dropwise;Magnetite is added
It is sufficiently stirred, under nitrogen atmosphere back flow reaction 16h, the temperature of back flow reaction is 85 DEG C;After reaction, it is added into reactant
Then 200mL distilled water extracts to obtain organic phase with dichloromethane, the organic phase being obtained by extraction is evaporated under reduced pressure, concentrate is obtained,
Concentrate obtains intermediate TPA-BTD-Br through column chromatography for separation, concentration and drying;The eluent of column chromatography for separation is dichloromethane
The volume ratio of the mixture of alkane and petroleum ether, the dichloromethane and petroleum ether is 1:3.5.
The nuclear magnetic resonance spectroscopy of intermediate TPA-BTD-Br, as shown in Figure 7:1HNMR/ppm:7.82 (d, J=7.60Hz,
1H), 7.73 (d, J=8.76Hz, 2H), 7.49 (d, J=7.64Hz, 1H), 7.18-7.24 (m, 5H), 7.10-7.12 (m,
5H),6.98-7.02(m,2H).The carbon-13 nmr spectra of intermediate TPA-BTD-Br, as shown in Figure 8:13CNMR/ppm:
152.95.152.13,147.42,146.31,132.55,131.34,128.87,128.81,128.37,126.29,124.01,
122.49,121.59,111.16。
(2) synthesis of intermediate TPA-BTD-CHO;
In step (2), by intermediate TPA-BTD-Br2.2737g, 4- formylphenylboronic acid 1.1100g, 4- (triphenyl
Phosphine) palladium 0.2588g and potassium carbonate 1.5525g are placed in 250mL there-necked flasks, then 0.1mL methyl tricapryl ammonium chlorides are added dropwise, then
40mL tetrahydrofuran THFs, 60mL toluene and 25mL distilled water H are added into mixture2O;Magnetite is added and is sufficiently stirred dissolving,
The temperature of back flow reaction 16h under nitrogen atmosphere, back flow reaction are 85 DEG C;After reaction, it extracts to have with extractant dichloromethane
The organic phase rotary evaporation being obtained by extraction is obtained drying solid by machine phase;By drying solid through column chromatography for separation, concentration and drying,
Intermediate TPA-BTD-CHO is obtained, the eluent of column chromatography for separation is the mixture of dichloromethane and petroleum ether, the dichloromethane
The volume ratio of alkane and petroleum ether is 1:3.5.
The nuclear magnetic resonance spectroscopy of intermediate TPA-BTD-CHO, as shown in Figure 9:1HNMR/ppm:10.03(s,1H),7.92
(d, J=8.16Hz, 2H), 7.72 (d, J=8.12Hz, 2H), 7.52 (d, J=8.60Hz, 2H), 7.26-7.31 (m, 5H),
7.05-7.15(m,9H).Intermediate TPA-BTD-CHO carbon-13 nmr spectras, as shown in Figure 10:13CNMR/ppm:191.90,
148.45,147.36,146.65,134.70,132.80,130.35,129.42,128.04,126.91,124.90,123.50,
123.13。
(3) synthesis of diazosulfide malononitrile TPA-BTD-BT.
In step (3), by intermediate TPA-BTD-CHO1.5045g, malononitrile 2.5219g and ammonium acetate 4.7811g,
It is placed in 500mL three-necked flasks, and 200mL glacial acetic acid is added into mixture, add magnetite and be sufficiently stirred, then in nitrogen
8h is reacted under atmosphere, reaction temperature is 117 DEG C;After reaction, organic phase is extracted to obtain with extractant dichloromethane, will extracted
Obtained organic phase rotary evaporation obtains concentrate, by concentrate through column chromatography for separation, concentration and drying, obtains diazosulfide third
Dintrile TPA-BTD-BT, the eluent of column chromatography for separation are the mixture of dichloromethane and petroleum ether, the dichloromethane and stone
The volume ratio of oily ether is 1:1.
The nuclear magnetic resonance spectroscopy of diazosulfide malononitrile TPA-BTD-BT, as shown in figure 11:1HNMR/ppm:8.20(d,
J=8.40Hz, 2H), 8.07 (d, J=8.48Hz, 2H), 7.86-7.90 (m, 3H), 7.78-7.82 (m, 2H), 7.28-7.32
(m,4H),7.18-7.22(m,6H),7.06-7.12(m,2H),0.87-0.90(m,3H).Diazosulfide malononitrile TPA-
The carbon-13 nmr spectra of BTD-BT, as shown in figure 12:13CNMR/ppm:176.81,159.06,158.07,154.09,153.74,
148.58,147.32,143.64,134.68,131.51,131.09,130.41,130.11,129.98,129.46,129.20,
128.28,126.93,125.93,125.15,123.63,122.50,113.91,112.79。
3. the characterization of compound
3.1 infrared spectrum
It takes suitable dry potassium bromide and sample to be tested and grinds uniform, tabletting in agate mortar, survey is infrared.4- diphenylamines
Base phenyl boric acid TPA-BTD-B (OH)2, intermediate TPA-BTD-Br, intermediate TPA-BTD-CHO and diazosulfide malononitrile
The infrared spectrum of TPA-BTD-BT is as shown in Figure 2, Figure 3 and Figure 4.
As shown in Figure 2,4- hexichol amido phenyl boric acid TPA-BTD-B (OH)2With intermediate TPA-BTD-Br in 1600cm-1With
1500cm-1Nearby there is strong absorption peak, in 900-600cm-1Also there is strong absworption peak in range.Because of the C=C of monokaryon aromatic hydrocarbons
The stretching vibration of double bond is in 1600cm-1And 1500cm-1There is absorption peak, c h bond out-of-plane bending vibration is in 900-690cm-1Region.
So understanding that TPA-BTD-Br contains phenyl ring.The stretching vibration of C=N double bonds is in 1600-1690cm-1Between, as shown in Figure 2, in
Throughout peak intensity is enhanced mesosome TPA-BTD-Br;This is because the force constant of the key of diazosulfide is larger, thus
Peak intensity enhances everywhere.4- hexichol amido phenyl boric acid TPA-B (OH) known to analysis2With bis- bromo- 2,1,3- diazosulfides of 4,7-
Reaction generates intermediate TPA-BTD-Br.
From the figure 3, it may be seen that intermediate TPA-BTD-Br and intermediate TPA-BTD-CHO are in 1600cm-1And 1500cm-1Near
There is strong absorption peak, in 900-600cm-1Also there is strong absworption peak in range.Because the flexible of C=C double bonds of monokaryon aromatic hydrocarbons shakes
It moves in 1600cm-1And 1500cm-1There is absorption peak, c h bond out-of-plane bending vibration is in 900-690cm-1Region.So understanding TPA-
BTD-CHO contains phenyl ring.The stretching vibration of aldehyde radical is in 1750-1680cm-1Region, as shown in Figure 3 intermediate TPA-BTD-CHO exist
1695cm-1There is an absorption peak, then intermediate TPA-BTD-CHO contains-CHO.By analysis it is found that intermediate TPA-BTD-Br with it is right
Formylphenylboronic acid reaction generates intermediate TPA-BTD-CHO.
As shown in Figure 4, intermediate TPA-BTD-CHO and diazosulfide malononitrile TPA-BTD-BT are in 1600cm-1With
1500cm-1Nearby there is strong absorption peak, in 900-600cm-1Also there is strong absworption peak in range.Because of the C=C of monokaryon aromatic hydrocarbons
The stretching vibration of double bond is in 1600cm-1And 1500cm-1There is absorption peak, c h bond out-of-plane bending vibration is in 900-690cm-1Region.
So understanding that diazosulfide malononitrile TPA-BTD-BT contains phenyl ring.The stretching vibration of aldehyde radical is in 1750-1680cm-1Region,
TPA-BTD-BT illustrates that diazosulfide malononitrile TPA-BTD-BT without-CHO, divides in this area without absorption peak as shown in Figure 3
TPA-BTD-CHO known to analysis is reacted with malononitrile generates diazosulfide malononitrile TPA-BTD-BT.
3.2 ultraviolet-ray visible absorbings and fluorescence spectrum
The uv-visible absorption spectra of the tetrahydrofuran solution of diazosulfide malononitrile TPA-BTD-BT, such as Fig. 5 institutes
Show, carries out two main absorption bands occur at 200-400nm, bands of a spectrum are respectively 317 and 367nm.Visual field goes out in 465nm
An existing wide absorption band.
The fluorescence spectrum of the tetrahydrofuran solution of diazosulfide malononitrile TPA-BTD-BT, as shown in fig. 6, incident narrow
In the case that seam and exit slit are 5, under 465nm excitations, the THF solution of TPA-BTD-BT generates emission peak at 600nm,
Show larger stokes displacements.
3.3 nmr spectrum
Fig. 7 and Fig. 8 is the hydrogen nuclear magnetic resonance spectrogram and carbon-13 nmr spectra figure of intermediate TPA-BTD-Br;
Fig. 9 and Figure 10 is the hydrogen nuclear magnetic resonance spectrogram and carbon-13 nmr spectra figure of intermediate TPA-BTD-CHO;
Figure 11 and Figure 12 is the hydrogen nuclear magnetic resonance spectrogram and carbon-13 nmr spectra of diazosulfide malononitrile TPA-BTD-BT
Figure.
The chemical shift of aldehyde radical hydrogen is 10.03 (s, 1H) as shown in Figure 9, since the electron attraction of aldehyde radical is more than benzo
The electron attraction of thiadiazoles:
So as shown in figure 11:2, the chemical shift of hydrogen is 7.92 (d, J=8.16Hz, 2H) on No. 4 carbon, on 3, No. 5 carbon
The chemical shift of hydrogen is 7.52 (d, J=8.60Hz, 2H);6, the chemical shift of hydrogen is 7.72 (d, J=8.12Hz, 2H) on 7 carbon;
8, on 10,13,15,17, No. 19 carbon hydrogen chemical shift be 7.26-7.31 (m, 6H), 9,11,12,14,16,18,19, No. 20
The chemical shift of hydrogen is 7.05-7.15 (m, 8H) on carbon.
Because the chemical shift of aldehyde radical shown in Figure 11 and Figure 12 disappears, intermediate TPA-BTD- can determine whether out
CHO is reacted with malononitrile, generates diazosulfide malononitrile TPA-BTD-BT.As shown in figure 14, hydrogen on No. 22 carbon
Chemical shift should 8.2 or so, and because Figure 11 in diazosulfide malononitrile TPA-BTD-BT nuclear magnetic resonance spectroscopy
In there are one hydrogen chemical shift in 8.20 (d, J=8.40Hz, 2H), so can to sum up obtain intermediate TPA-BTD-CHO and third
Dintrile has occurred reaction and generates diazosulfide malononitrile TPA-BTD-BT.
4. diazosulfide malononitrile fluoroscopic examination CN-Method, include the following steps:
(1) using tetrahydrofuran THF as solvent, diazosulfide malononitrile TPA-BTD-BT is added, is configured to benzo thiophene two
The tetrahydrofuran THF solution of azoles malononitrile TPA-BTD-BT;Diazosulfide malononitrile TPA-BTD-BT is as follows:
(2) sample to be tested is added to the tetrahydrofuran THF solution of diazosulfide malononitrile TPA-BTD-BT;
(3) it observes by the naked eye, whether have CN in uv-visible absorption spectra or fluorescence spectrum identification sample to be tested-;Meat
Eye observes recognition methods:Solution colour is turned yellow by orange, illustrates there is CN in sample to be tested-;Uv-visible absorption spectra
Recognition methods is:UV-vis spectrum tests are carried out at 200-660nm, UV-vis absorption spectrums absorption peak at 367nm declines
Or disappear, the absorption peak at 465nm declines and is blue shifted to 440nm, while occurring two etc. at 430 and 407nm and absorbing
Point, illustrates there is CN in sample to be tested-;Fluorescence spectrum recognition methods is:Under 465nm excitations, emission peak, explanation are generated at 600nm
There is CN in sample to be tested-, or under 365nm ultra violet lamps, solution is presented bright orange fluorescence, illustrates have in sample to be tested
CN-。
Diazosulfide malononitrile TPA-BTD-BT is dissolved in tetrahydrofuran THF, then in diazosulfide malononitrile TPA-
It is separately added into CN in the tetrahydrofuran THF solution of BTD-BT-With other anion, CN is then measured respectively-Diazosulfide is added
The tetrahydrofuran THF solution of malononitrile TPA-BTD-BT neutralizes other anion and diazosulfide malononitrile TPA-BTD-BT is added
Tetrahydrofuran THF solution in uv-visible absorption spectra and fluorescence spectrum;The diazosulfide malononitrile TPA-BTD-
A concentration of the 2 × 10 of BT-5Mol/L, the CN of the addition-Concentration with other anion is 4 × 10-5mol/L;It is described other
Anion includes Cl-,SO4 2-,F-,Br-,I-,H2PO4 -,NO2 -,NO3 -,CO3 2-,HCO3 -And CH3COO-。
As shown in Figure 15, diazosulfide malononitrile TPA-BTD-BT is the CN with 2equiv in THF solution-And other
Anion (F-,Cl-,Br-,I-,CH3COO-,NO2 -,NO3 -,H2PO4 -,HCO3 -,CO3 2-,SO4 2-) UV- is carried out at 200-660nm
Vis spectrum test figures, CN-It is added in the THF solution of TPA-BTD-BT, UV-vis absorption spectrums are under absorption peak at 367nm
For drop until disappearing, the absorption peak at 465nm declines and is blue shifted to 440nm, illustrates that the conjugated degree of TPA-BTD-BT weakens,
System electronic transition energy increases so as to cause blue shift.Solution colour is turned yellow by orange.
As shown in figure 16, in the case where entrance slit and exit slit are 5, under 465nm excitations, diazosulfide third
The THF solution of dintrile TPA-BTD-BT generates emission peak at 600nm, shows larger stokes displacements.When with 2equiv
Other anion (F-,Cl-,Br-,I-,CH3COO-,NO2 -,NO3 -,H2PO4 -,HCO3 -,CO3 2-,SO4 2-) carry out FS fluoroscopic examinations
When, TPA-BTD-BT does not change significantly the response of other anion, and to CN-It has a greater change, illustrates TPA-
BTD-BT is to CN-Selectivity it is preferable.With CN-Ion is added, and fluorescence intensity is remarkably reinforced, i.e., this compound is very potential
As detection CN-Chemical sensor.Under ultra violet lamp (365nm), solution colour, such as Figure 17 can be significantly observed
It is shown, CN is added-Bright orange fluorescence is presented in solution afterwards, and after other ions are added, fluorescence color is constant, this also absolutely proves TPA-
BTD-BT is to CN-There is preferable selectivity.
As shown in Figure 18, with CN-Ion concentration gradually increases (0-4 × 10-5Mol/L), UV-vis absorption spectrums exist
Absorption peak is gradually reduced until disappearing at 367nm, and the absorption peak at 465nm is gradually reduced and blue shift occurs (blue shift arrives
440nm), while at 430nm and 407nm there are two isobestic points, illustrate CN-Having an effect with TPA-BTD-BT, there have to be new
Substance generates.Meanwhile solution colour is turned yellow (as shown in figure 18) by orange.
As seen from Figure 19, with CN-Be continuously added, the generation peak intensity of 600nm is remarkably reinforced, the Fluorescence Increasing factor
It is 16.Illustrate CN-It is acted on TPA-BTD-BT, forms novel substance.This is also that CN is added under ultra violet lamp-Afterwards
The reason of fluorescence of solution is remarkably reinforced.The above results fully show TPA-BTD-BT to CN-Identification be one well
" turn-on " type fluorescent optical sensor.
(2) other anion are to diazosulfide malononitrile TPA-BTD-BT fluoroscopic examinations CN-Interference effect.
In method (2), diazosulfide malononitrile TPA-BTD-BT is dissolved in tetrahydrofuran THF, then to benzo thiophene two
It is separately added into other anion in the tetrahydrofuran THF solution of azoles malononitrile TPA-BTD-BT, then to other anion are added
It is separately added into CN in the tetrahydrofuran THF solution of diazosulfide malononitrile TPA-BTD-BT-, after mixing, then survey respectively
Determine that other anion and CN is added in the tetrahydrofuran THF solution of diazosulfide malononitrile TPA-BTD-BT-Ultraviolet-visible
Absorption and fluorescence spectrum;A concentration of the 2 × 10 of the diazosulfide malononitrile TPA-BTD-BT-5Mol/L, the addition
The concentration of other anion be 4 × 10-5mol/L;The CN of the addition-A concentration of 4 × 10-5mol/L;Other described the moon
Ion includes Cl-,SO4 2-,F-,Br-,I-,H2PO4 -,NO2 -,NO3 -,CO3 2-,HCO3 -And CH3COO-。
As shown in Figure 20,4 × 10 are added-5When other anion of mol/L, absorption spectrum does not change significantly, when again
It is added 4 × 10-5The CN of mol/L-When, the variation of absorption spectrum and only an addition CN-Spectrum variation it is similar.This explanation, TPA-
BTD-BT is in the presence of other ions to CN-Still there is superior recognition reaction.
As shown in Figure 21, in no CN-In the presence of, it is added 4 × 10-5When other anion of mol/L, fluorescence intensity does not have
Apparent variation, when continuously adding 4 × 10 in the solution containing other anion-5The CN of mol/L-When, fluorescence intensity is apparent
Enhancing.
Although from Figure 21 by emission band other anion it can be seen from Fluorescence Increasing factor block diagram at the 596nm
In the presence of on the slightly influence of its enhancement factor, but the presence of other ions has no effect on TPA-BTD-BT to CN-" turn-on "
Type fluorescence identifying.It can thus be seen that we successfully construct " TPA-BTD-BT " to CN-Turn-on types it is highly selective, strong
Anti-interference ability fluorescent optical sensor.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
Among changing still in present patent application scope of the claims.
Claims (10)
1. diazosulfide malononitrile, which is characterized in that as shown in formula (I):
2. the synthetic method of diazosulfide malononitrile, which is characterized in that include the following steps:
(1) synthesis of intermediate TPA-BTD-Br, shown in intermediate TPA-BTD-Br such as formulas (II):
(2) by shown in intermediate TPA-BTD-Br synthetic intermediate TPA-BTD-CHO, intermediate TPA-BTD-CHO such as formulas (III):
(3) synthesis of diazosulfide malononitrile TPA-BTD-BT, diazosulfide malononitrile TPA-BTD-BT such as formula (I) institutes
Show:
3. the synthetic method of diazosulfide malononitrile according to claim 2, which is characterized in that, will in step (1)
4- hexichol amidos phenyl boric acid, 4,7- bis- bromo- 2,1,3- diazosulfide, 4- (triphenylphosphine) palladiums and potassium carbonate are placed in there-necked flask
In, tetrahydrofuran THF, toluene and distilled water H are added into mixture2O, then methyl tricapryl ammonium chloride is added dropwise;Magnetite is added
It is sufficiently stirred, reacts under nitrogen atmosphere;After reaction, distilled water is added into reactant, is then extracted with dichloromethane
The organic phase being obtained by extraction is evaporated under reduced pressure, obtains concentrate, concentrate is obtained through column chromatography for separation, concentration and drying by organic phase
To intermediate TPA-BTD-Br;The eluent of column chromatography for separation is the mixture of dichloromethane and petroleum ether.
4. the synthetic method of diazosulfide malononitrile according to claim 3, which is characterized in that, will in step (1)
4- hexichol amido phenyl boric acids 2.7568g, 4,7- bis- bromo- 2,1,3- diazosulfide 2.3576g, 4- (triphenylphosphine) palladium
0.1342g and potassium carbonate 1.7880g are placed in 250mL there-necked flasks, and 60mL tetrahydrofuran THFs, 45mL first are added into mixture
Benzene and 22mL distilled water H2O, then 0.1mL methyl tricapryl ammonium chlorides are added dropwise;Magnetite is added to be sufficiently stirred, flows back under nitrogen atmosphere
16h is reacted, the temperature of back flow reaction is 85 DEG C;After reaction, 200mL distilled water is added into reactant, then uses dichloro
Methane extracts to obtain organic phase, and the organic phase being obtained by extraction is evaporated under reduced pressure, obtains concentrate, and concentrate is through column chromatography for separation, dense
Contracting and drying, obtain intermediate TPA-BTD-Br;The eluent of column chromatography for separation is the mixture of dichloromethane and petroleum ether, institute
The volume ratio for stating dichloromethane and petroleum ether is 1:3.5.
5. the synthetic method of diazosulfide malononitrile according to claim 2, which is characterized in that, will in step (2)
Intermediate TPA-BTD-Br, 4- formylphenylboronic acid, 4- (triphenylphosphine) palladiums and potassium carbonate are placed in there-necked flask, then methyl is added dropwise
Then tetrahydrofuran THF, toluene and distilled water H is added in trioctylmethylammonium chloride into mixture2O;Addition magnetite is sufficiently stirred molten
It solves, under nitrogen atmosphere back flow reaction;After reaction, organic phase is extracted to obtain with extractant dichloromethane, had what is be obtained by extraction
Machine phase rotary evaporation obtains drying solid;By drying solid through column chromatography for separation, concentration and drying, intermediate TPA-BTD- is obtained
CHO, the eluent of column chromatography for separation are the mixture of dichloromethane and petroleum ether.
6. the synthetic method of diazosulfide malononitrile according to claim 5, which is characterized in that, will in step (2)
Intermediate TPA-BTD-Br2.2737g, 4- formylphenylboronic acid 1.1100g, 4- (triphenylphosphine) palladium 0.2588g and potassium carbonate
1.5525g is placed in 250mL there-necked flasks, then 0.1mL methyl tricapryl ammonium chlorides are added dropwise, and 40mL tetra- is then added into mixture
Hydrogen furans THF, 60mL toluene and 25mL distilled water H2O;Magnetite is added and is sufficiently stirred dissolving, under nitrogen atmosphere back flow reaction 16h,
The temperature of back flow reaction is 85 DEG C;After reaction, organic phase is extracted to obtain with extractant dichloromethane, it is organic by what is be obtained by extraction
Phase rotary evaporation obtains drying solid;By drying solid through column chromatography for separation, concentration and drying, intermediate TPA-BTD-CHO is obtained,
The eluent of column chromatography for separation is the mixture of dichloromethane and petroleum ether, and the volume ratio of the dichloromethane and petroleum ether is 1:
3.5。
7. the synthetic method of diazosulfide malononitrile according to claim 2, which is characterized in that, will in step (3)
Intermediate TPA-BTD-CHO, malononitrile and ammonium acetate, are placed in three-necked flask, and glacial acetic acid is added into mixture, add
Magnetite is sufficiently stirred, and is then reacted under nitrogen atmosphere;After reaction, organic phase is extracted to obtain with extractant dichloromethane, will extracted
The organic phase rotary evaporation obtained obtains concentrate, by concentrate through column chromatography for separation, concentration and drying, obtains diazosulfide
Malononitrile TPA-BTD-BT, the eluent of column chromatography for separation are the mixture of dichloromethane and petroleum ether.
8. the synthetic method of diazosulfide malononitrile according to claim 7, which is characterized in that, will in step (3)
Intermediate TPA-BTD-CHO1.5045g, malononitrile 2.5219g and ammonium acetate 4.7811g, are placed in 500mL three-necked flasks, and
200mL glacial acetic acid is added into mixture, adds magnetite and is sufficiently stirred, then react 8h under nitrogen atmosphere, reaction temperature is
117℃;After reaction, upper layer organic matter is extracted with extractant dichloromethane, upper layer organic matter rotary evaporation is obtained into concentrate,
By concentrate through column chromatography for separation, concentration and drying, diazosulfide malononitrile TPA-BTD-BT, the leaching of column chromatography for separation are obtained
Lotion is the mixture of dichloromethane and petroleum ether, and the volume ratio of the dichloromethane and petroleum ether is 1:1.
9. diazosulfide malononitrile fluoroscopic examination CN-Method, which is characterized in that include the following steps:
(1) using tetrahydrofuran THF as solvent, diazosulfide malononitrile TPA-BTD-BT is added, is configured to diazosulfide third
The tetrahydrofuran THF solution of dintrile TPA-BTD-BT;Diazosulfide malononitrile TPA-BTD-BT is as follows:
(2) sample to be tested is added to the tetrahydrofuran THF solution of diazosulfide malononitrile TPA-BTD-BT;(3) pass through naked eyes
Whether there is CN in observation, uv-visible absorption spectra or fluorescence spectrum identification sample to be tested-。
10. diazosulfide malononitrile according to claim 9 detects CN-Method, which is characterized in that visually observe knowledge
Other method is:Solution colour is turned yellow by orange, illustrates there is CN in sample to be tested-;Uv-visible absorption spectra recognition methods
For:UV-vis spectrum tests are carried out at 200-660nm, UV-vis absorption spectrums absorption peak at 367nm declines or disappears,
Absorption peak at 465nm declines and is blue shifted to 440nm, while occurring two isobestic points, explanation at 430 and 407nm
There is CN in sample to be tested-;Fluorescence spectrum recognition methods is:Emission peak is generated under 465nm excitations, at 600nm, illustrates sample to be tested
In have CN-, or under 365nm ultra violet lamps, solution is presented bright orange fluorescence, illustrates there is CN in sample to be tested-。
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109655436A (en) * | 2018-12-07 | 2019-04-19 | 武汉工程大学 | Cryanide ion fluorescence detection test of a kind of column aromatic hydrocarbons modification and preparation method thereof, detection method |
| CN113234071A (en) * | 2021-05-17 | 2021-08-10 | 阜阳师范大学 | Triphenylamine methyl pyridine salt, synthetic method thereof, and application of triphenylamine methyl pyridine salt in CN-recognition and biological imaging |
| CN114621159A (en) * | 2022-04-06 | 2022-06-14 | 电子科技大学 | Diazosulfide-based fluorescent material, fluorescent polymer, fluorescent nanoparticles, and preparation method and application thereof |
| CN115627082A (en) * | 2022-10-20 | 2023-01-20 | 浙江工业大学 | D-A-pi-A type benzothiadiazole functional dye and preparation method and application thereof |
| CN115745988A (en) * | 2022-11-14 | 2023-03-07 | 广州天赐高新材料股份有限公司 | D-A-A type deep red fluorescent compound and synthetic method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080254501A1 (en) * | 2005-03-01 | 2008-10-16 | Invitrogen Corporation | Chemical probe compounds that become fluorescent upon reduction, and methods for their use |
| CN106189343A (en) * | 2016-07-20 | 2016-12-07 | 南方医科大学 | A kind of benzothiazole 2 acetonitrile class dyestuff and application thereof |
| CN106748954A (en) * | 2016-09-22 | 2017-05-31 | 北京理工大学 | A kind of fluorescent chemicals, preparation method and application for detecting micro cryanide ion |
| CN107523088A (en) * | 2017-09-08 | 2017-12-29 | 常州大学 | A kind of asymmetric side's acid cyanines probe based on cyano group and its preparation method and application |
| CN108299293A (en) * | 2018-02-09 | 2018-07-20 | 中国科学技术大学 | Colorimetric-fluorescent probe compounds of cyanide/hydrogen cyanide and preparation method thereof |
-
2018
- 2018-07-04 CN CN201810721697.XA patent/CN108689963B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080254501A1 (en) * | 2005-03-01 | 2008-10-16 | Invitrogen Corporation | Chemical probe compounds that become fluorescent upon reduction, and methods for their use |
| CN106189343A (en) * | 2016-07-20 | 2016-12-07 | 南方医科大学 | A kind of benzothiazole 2 acetonitrile class dyestuff and application thereof |
| CN106748954A (en) * | 2016-09-22 | 2017-05-31 | 北京理工大学 | A kind of fluorescent chemicals, preparation method and application for detecting micro cryanide ion |
| CN107523088A (en) * | 2017-09-08 | 2017-12-29 | 常州大学 | A kind of asymmetric side's acid cyanines probe based on cyano group and its preparation method and application |
| CN108299293A (en) * | 2018-02-09 | 2018-07-20 | 中国科学技术大学 | Colorimetric-fluorescent probe compounds of cyanide/hydrogen cyanide and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| QISONG ZHANG，等: "A novel colorimetric and fluorescent sensor for cyanide anions detection based on triphenylamine and benzothiadiazole", 《TETRAHEDRON》 * |
| 林奇，等: "氰根离子比色、荧光传感器研究新进展", 《化学进展》 * |
| 蔡毅: "氰根离子反应型传感器分子的合成及性能研究", 《西北师范大学硕士学位论文》 * |
| 邱达立: "新型七甲川吲哚菁类荧光探针的设计合成及CN-检测性能研究", 《湘潭大学硕士学位论文》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109655436A (en) * | 2018-12-07 | 2019-04-19 | 武汉工程大学 | Cryanide ion fluorescence detection test of a kind of column aromatic hydrocarbons modification and preparation method thereof, detection method |
| CN109655436B (en) * | 2018-12-07 | 2021-03-30 | 武汉工程大学 | Column aromatic modified cyanide ion fluorescence detection test paper, and preparation method and detection method thereof |
| CN113234071A (en) * | 2021-05-17 | 2021-08-10 | 阜阳师范大学 | Triphenylamine methyl pyridine salt, synthetic method thereof, and application of triphenylamine methyl pyridine salt in CN-recognition and biological imaging |
| CN113234071B (en) * | 2021-05-17 | 2023-08-01 | 阜阳师范大学 | Triphenylamine methyl pyridine salt, synthesis method and application thereof in CN & lt- & gt identification and biological imaging |
| CN114621159A (en) * | 2022-04-06 | 2022-06-14 | 电子科技大学 | Diazosulfide-based fluorescent material, fluorescent polymer, fluorescent nanoparticles, and preparation method and application thereof |
| CN114621159B (en) * | 2022-04-06 | 2023-04-18 | 电子科技大学 | Diazosulfide-based fluorescent material, fluorescent polymer, fluorescent nanoparticles, and preparation method and application thereof |
| CN115627082A (en) * | 2022-10-20 | 2023-01-20 | 浙江工业大学 | D-A-pi-A type benzothiadiazole functional dye and preparation method and application thereof |
| CN115627082B (en) * | 2022-10-20 | 2024-02-02 | 浙江工业大学 | D-A-pi-A type benzothiadiazole functional dye and preparation method and application thereof |
| CN115745988A (en) * | 2022-11-14 | 2023-03-07 | 广州天赐高新材料股份有限公司 | D-A-A type deep red fluorescent compound and synthetic method and application thereof |
| CN115745988B (en) * | 2022-11-14 | 2024-05-24 | 广州天赐高新材料股份有限公司 | D-A-A type deep red fluorescent compound and synthetic method and application thereof |
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