CN108997258A - Method for synthesizing the intermediate and its synthetic method and detection CN- of diazosulfide malononitrile - Google Patents
Method for synthesizing the intermediate and its synthetic method and detection CN- of diazosulfide malononitrile Download PDFInfo
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- CN108997258A CN108997258A CN201810721663.0A CN201810721663A CN108997258A CN 108997258 A CN108997258 A CN 108997258A CN 201810721663 A CN201810721663 A CN 201810721663A CN 108997258 A CN108997258 A CN 108997258A
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- btd
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- diazosulfide
- malononitrile
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- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 title claims abstract description 93
- OBISXEJSEGNNKL-UHFFFAOYSA-N dinitrogen-n-sulfide Chemical compound [N-]=[N+]=S OBISXEJSEGNNKL-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000010189 synthetic method Methods 0.000 title claims abstract description 21
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 15
- 238000001514 detection method Methods 0.000 title claims abstract description 13
- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000862 absorption spectrum Methods 0.000 claims abstract description 17
- 238000002189 fluorescence spectrum Methods 0.000 claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 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 38
- 238000006243 chemical reaction Methods 0.000 claims description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 238000004440 column chromatography Methods 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 27
- 238000000926 separation method Methods 0.000 claims description 26
- 239000012074 organic phase Substances 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 23
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 20
- 239000003208 petroleum Substances 0.000 claims description 20
- 238000010521 absorption reaction Methods 0.000 claims description 19
- 239000012141 concentrate Substances 0.000 claims description 19
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- 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 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000012153 distilled water Substances 0.000 claims description 15
- 239000003480 eluent 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
- 238000000605 extraction Methods 0.000 claims description 13
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 235000019270 ammonium chloride Nutrition 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000004458 analytical method Methods 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- 238000002390 rotary evaporation Methods 0.000 claims description 8
- 238000002371 ultraviolet--visible spectrum Methods 0.000 claims description 8
- -1 amido phenyl boric acid Chemical compound 0.000 claims description 7
- 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 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 239000000376 reactant Substances 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 4
- 239000004575 stone Substances 0.000 claims description 4
- ZSAIDYISADJCTG-UHFFFAOYSA-N CC(CCCCCCC)P(CCCCCCCC)CCCCCCCC Chemical compound CC(CCCCCCC)P(CCCCCCCC)CCCCCCCC ZSAIDYISADJCTG-UHFFFAOYSA-N 0.000 claims description 2
- QNEFNFIKZWUAEQ-UHFFFAOYSA-N carbonic acid;potassium Chemical compound [K].OC(O)=O QNEFNFIKZWUAEQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 239000002027 dichloromethane extract Substances 0.000 claims 1
- 238000012850 discrimination method Methods 0.000 claims 1
- 239000000284 extract Substances 0.000 claims 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 claims 1
- 230000003595 spectral effect Effects 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 4
- 150000001450 anions Chemical class 0.000 description 21
- 239000000126 substance Substances 0.000 description 19
- 239000000523 sample Substances 0.000 description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 7
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 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
- 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
- 230000000694 effects Effects 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 3
- 238000004566 IR spectroscopy Methods 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 150000003851 azoles Chemical class 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000002156 mixing 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
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 210000001508 eye Anatomy 0.000 description 2
- 238000001917 fluorescence detection Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 238000005935 nucleophilic addition reaction Methods 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
- 238000010992 reflux Methods 0.000 description 2
- 150000004867 thiadiazoles Chemical class 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
- 206010021143 Hypoxia Diseases 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
- 150000001335 aliphatic alkanes 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
- 238000012512 characterization method Methods 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
- 230000005611 electricity Effects 0.000 description 1
- 230000005274 electronic transitions Effects 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
- 238000000227 grinding Methods 0.000 description 1
- 230000000215 hyperchromic effect Effects 0.000 description 1
- 230000007954 hypoxia Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000003993 interaction Effects 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
- 238000005272 metallurgy Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 150000004893 oxazines Chemical class 0.000 description 1
- 150000004880 oxines Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 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
- 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
- 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
-
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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
-
- 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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
-
- 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
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N24/00—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects
- G01N24/08—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects by using nuclear magnetic resonance
- G01N24/088—Assessment or manipulation of a chemical or biochemical reaction, e.g. verification whether a chemical reaction occurred or whether a ligand binds to a receptor in drug screening or assessing reaction kinetics
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
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- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—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
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- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
Abstract
The present invention discloses intermediate for synthesizing diazosulfide malononitrile and its synthetic method and detection CN‑Method, for synthesizing shown in the intermediate such as formula (III) of diazosulfide malononitrile:The synthetic method of intermediate shown in formula (III) includes the following steps: the synthesis of (1) intermediate TPA-BTD-Br；(2) synthesis of intermediate TPA-BTD-CHO shown in formula (III).Detect CN‑Method include the following steps: (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‑.Intermediate shown in formula (III) can be used for constructing to CN‑Highly selective, the strong anti-interference ability of turn-on type fluorescent optical sensor.
Description
Technical field
The present invention relates to CN-Detection technique field.It is particularly used for the intermediate of synthesis diazosulfide malononitrile
And its synthetic method and detection CN-Method.
Background technique
Cyanide in the industrial production be widely used in life, can be used for being electroplated in the industrial production, plastics manufacture,
Metallurgy, 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 poisoning, causes to have difficulty in breathing, cell hypoxia is choked to death.Adult, which takes orally 150-250mg, can cause death.Therefore, it opens
It sends out one kind and fast and accurately detects 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 is higher, and 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, this project 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, Yi Jifu
Positive municipal government-Fuyang Teachers College's Horizontal Cooperation is great, under key project (XDHX201704, XDHX201701) subsidy, if
Meter synthesizes a kind of novel CN-Chemical sensor fluorescence probe.
Summary of the invention
For this purpose, a kind of for synthesizing in diazosulfide malononitrile technical problem to be solved by the present invention lies in providing
Mesosome and its synthetic method and detection CN-Method.
In order to solve the above technical problems, the invention provides the following technical scheme:
For synthesizing the intermediate of diazosulfide malononitrile, as shown in formula (III):
For synthesizing the synthetic method of the intermediate of diazosulfide malononitrile, include the following steps:
(1) synthesis of intermediate TPA-BTD-Br, shown in intermediate TPA-BTD-Br such as formula (II):
(2) by intermediate TPA-BTD-Br synthetic intermediate TPA-BTD-CHO, intermediate TPA-BTD-CHO such as formula (III)
It is shown:
The synthetic method of the above-mentioned intermediate for being used to synthesize diazosulfide malononitrile, in step (1), by 4- diphenylamines
Base phenyl boric acid, 4,7- bis- bromo- 2,1,3- diazosulfide, 4- (triphenylphosphine) palladium and potassium carbonate are placed in there-necked flask, to mixing
Tetrahydrofuran THF, toluene and distilled water H are added in object2O, then methyl tricapryl ammonium chloride is added dropwise；Magnetite is added to be sufficiently stirred,
It reacts under nitrogen atmosphere；After reaction, distilled water is added into reactant, organic phase is then extracted with dichloromethane to obtain, it will
The organic phase vacuum distillation being obtained by extraction, obtains concentrate, concentrate obtains intermediate through column chromatography for separation, concentration and drying
TPA-BTD-Br；The eluent of column chromatography for separation is the mixture of methylene chloride and petroleum ether.
The synthetic method of the above-mentioned intermediate for being used to synthesize diazosulfide malononitrile, in step (1), by 4- diphenylamines
Base phenyl boric acid 2.7568g, 4,7- bis- bromo- 2,1,3- diazosulfide 2.3576g, 4- (triphenylphosphine) palladium 0.1342g and carbonic acid
Potassium 1.7880g is placed in 250mL there-necked flask, and 60mL tetrahydrofuran THF, 45mL toluene and 22mL distilled water are added into mixture
H2O, then 0.1mL methyl tricapryl ammonium chloride is added dropwise；Magnetite is added to be sufficiently stirred, under nitrogen atmosphere back flow reaction 16h, reflux is anti-
The temperature answered is 85 DEG C；After reaction, 200mL distilled water is added into reactant, is then extracted with dichloromethane organic
The organic phase being obtained by extraction is evaporated under reduced pressure, obtains concentrate by phase, and concentrate is obtained through column chromatography for separation, concentration and drying
Mesosome TPA-BTD-Br；The eluent of column chromatography for separation is the mixture of methylene chloride and petroleum ether, the methylene chloride and stone
The volume ratio of oily ether is 1:3.5.
The synthetic method of the above-mentioned intermediate for being used to synthesize diazosulfide malononitrile, in step (2), by intermediate
TPA-BTD-Br, 4- formylphenylboronic acid, 4- (triphenylphosphine) palladium and potassium carbonate are placed in there-necked flask, then methyl trioctylphosphine is added dropwise
Then tetrahydrofuran THF, toluene and distilled water H is added in ammonium chloride into mixture2O；Magnetite is added, dissolution is sufficiently stirred,
Back flow reaction under nitrogen atmosphere；After reaction, organic phase is extracted to obtain with extractant methylene chloride, the organic phase being obtained by extraction is revolved
Turn to evaporate to obtain drying solid；By drying solid through column chromatography for separation, concentration and drying, intermediate TPA-BTD-CHO, column layer are obtained
Analyse the mixture that isolated eluent is methylene chloride and petroleum ether.
The synthetic method of the above-mentioned intermediate for being used to synthesize diazosulfide malononitrile, in step (2), by intermediate
TPA-BTD-Br2.2737g, 4- formylphenylboronic acid 1.1100g, 4- (triphenylphosphine) palladium 0.2588g and potassium carbonate 1.5525g
It is placed in 250mL there-necked flask, then 0.1mL methyl tricapryl ammonium chloride is added dropwise, 40mL tetrahydrofuran is then added into mixture
THF, 60mL toluene and 25mL distilled water H2O；Magnetite is added, dissolution is sufficiently stirred, under nitrogen atmosphere back flow reaction 16h, reflux
The temperature of reaction is 85 DEG C；After reaction, organic phase is extracted to obtain with extractant methylene chloride, the organic phase that will be obtained by extraction
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 methylene chloride and petroleum ether, and the volume ratio of the methylene chloride and petroleum ether is 1:
3.5。
Detect 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；Shown in diazosulfide malononitrile TPA-BTD-BT such as following formula (I):
Diazosulfide malononitrile TPA-BTD-BT synthetic method shown in formula (I) is as follows: by intermediate TPA-BTD-CHO,
Malononitrile and ammonium acetate, are placed in three-necked flask, and glacial acetic acid is added into mixture, add magnetite and are sufficiently stirred, then
It reacts under nitrogen atmosphere；After reaction, organic phase is extracted to obtain with extractant methylene chloride, the organic phase being obtained by extraction is rotated
Concentrate is evaporated to obtain, by concentrate through column chromatography for separation, concentration and drying, obtains diazosulfide malononitrile TPA-BTD-BT,
The eluent of column chromatography for separation is the mixture of methylene chloride and petroleum ether.
(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 detection CN-Method, visually observe recognition methods are as follows: solution colour is turned yellow by orange, is illustrated to be measured
There is CN in sample-；Uv-visible absorption spectra recognition methods are as follows: UV-vis spectrum test, UV- are carried out at 200-660nm
Vis absorption spectrum absorption peak at 367nm declines or disappears, and the absorption peak at 465 nm declines and be blue shifted to 440nm, together
When at 430 and 407nm occur two isobestic points, illustrate there is CN in sample to be tested-；Fluorescence spectrum recognition methods are as follows: 465nm
Emission peak is generated under excitation, at 600 nm, illustrates there is CN in sample to be tested-, or under the ultraviolet light irradiation of 365nm, solution be in
Existing bright orange fluorescence illustrates there is CN in sample to be tested-。
Above-mentioned detection CN-Method, the specific synthetic method of diazosulfide malononitrile TPA-BTD-BT shown in formula (I) is such as
Under: by intermediate TPA-BTD-CHO1.5045g, malononitrile 2.5219g and ammonium acetate 4.7811g, it is placed in 500mL three-necked flask
In, and 200mL glacial acetic acid is added into mixture, it adds magnetite and is sufficiently stirred, then react 8h, reaction temperature under nitrogen atmosphere
Degree is 117 DEG C；After reaction, upper layer organic matter is extracted with extractant methylene chloride, upper layer organic matter rotary evaporation is obtained dense
Contracting object obtains diazosulfide malononitrile TPA-BTD-BT, column chromatography point by concentrate through column chromatography for separation, concentration and drying
From eluent be methylene chloride and petroleum ether mixture, the volume ratio of the methylene chloride and petroleum ether is 1:1.
Technical solution of the present invention achieves following beneficial technical 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- diphenylamines
Base phenyl boric acid, 4- formylphenylboronic acid, the bromo- 2,1,3- diazosulfide of 4,7- bis-, malononitrile are Material synthesis subbase containing short of electricity
The diazosulfide malononitrile molecule (TPA-BDT-BT) of group.Synthesized intermediate and product is using infrared spectroscopy (IR), purple
Outside-visible absorption spectra (UV-vis), fluorescence spectrum (FS), nuclear magnetic resonance spectroscopy (1) and carbon-13 nmr spectra HNMR
(13CNMR it) is characterized.Diazosulfide malononitrile TPA-BTD-BT contains electron deficient group, has activated CN-To dicyano
Nucleophilic addition, break dicyano electron-withdrawing ability effect, hinder electric charge transfer.With diazosulfide malononitrile TPA-BTD-
BT is that fluorescence probe is used for CN-Detection, the molecule only to CN-Selective recognition reaction, the fluorescence enhancement factor obtain 16,
Other anion (F-, Cl-,Br-,I-,CH3COO-,NO2 -,NO3 -,H2PO4 -,HCO3 -,CO3 2-,SO4 2-) presence have no effect on
The sensor is to CN-Identification.Diazosulfide malononitrile TPA-BTD-BT is successfully constructed to CN-Turn-on type Gao Xuan
The fluorescent optical sensor of selecting property, strong anti-interference ability.
Detailed description of the invention
Diazosulfide malononitrile TPA-BTD-BT synthetic route chart in Fig. 1 present invention；
4- hexichol amido phenyl boric acid TPA-BTD-B (OH) in Fig. 2 present invention2It is infrared with intermediate TPA-BTD-Br
Spectrogram；
The infrared spectrogram of intermediate TPA-BTD-Br and intermediate TPA-BTD-CHO in Fig. 3 present invention；
The infrared spectroscopy of intermediate TPA-BTD-CHO and diazosulfide malononitrile TPA-BTD-BT in Fig. 4 present invention
Figure.
The ultraviolet-ray visible absorbing of the tetrahydrofuran solution of diazosulfide malononitrile TPA-BTD-BT in Fig. 5 present invention
Spectrum, the concentration of TPA-BTD-BT are 2 × 10-5mol/L；
The fluorescence spectrum of the tetrahydrofuran solution of diazosulfide malononitrile TPA-BTD-BT Fig. 6 of the invention, TPA-
The concentration of BTD-BT is 2 × 10-5mol/L；
Intermediate TPA-BTD-Br in Fig. 7 present invention1HNMR (deuterium band chloroform CDCl3For solvent)；
Intermediate TPA-BTD-Br in Fig. 8 present invention13CNMR (deuterium band chloroform CDCl3For solvent)；
Intermediate TPA-BTD-CHO in Fig. 9 present invention1HNMR (deuterium band chloroform CDCl3For solvent)；
Intermediate TPA-BTD-CHO in Figure 10 present invention13CNMR (deuterium band chloroform CDCl3For solvent)；
The TPA-BTD-BT's of diazosulfide malononitrile in Figure 11 present invention1HNMR (deuterium band chloroform CDCl3It is molten
Agent)；
The TPA-BTD-BT's of diazosulfide malononitrile in Figure 12 present invention13CNMR (deuterium band chloroform CDCl3It is molten
Agent)；
The nuclear-magnetism chemical shift analysis chart of intermediate TPA-BTD-CHO in Figure 13 present invention；
The nuclear-magnetism chemical shift analysis chart of diazosulfide malononitrile TPA-BTD-BT in Figure 14 present invention
(concentration of TPA-BTD-BT is the THF solution of diazosulfide malononitrile TPA-BTD-BT in Figure 15 present invention
2.0×10-5Mol/L CN is added in)-With ultraviolet-visible absorption spectra figure (CN of addition of other anion-With other yin from
The concentration of son is 4.0 × 10-5mol/L)；
(concentration of TPA-BTD-BT is the THF solution of diazosulfide malononitrile TPA-BTD-BT in Figure 16 present invention
2.0×10-5Mol/L CN is added in)-With the fluorescence spectra (CN of addition of other anion-It is equal with the concentration of other anion
It is 4.0 × 10-5mol/L)
(concentration of TPA-BTD-BT is the THF solution of diazosulfide malononitrile TPA-BTD-BT in Figure 17 present invention
2.0×10-5Mol/L CN is added in)-With other anion, 365 nano-ultraviolet lights irradiation under color change, (from a left side to
The right side is followed successively by Blank, CN-, F-,Cl-, Br-, I-,CH3COO-, NO2 -, NO3 -, H2PO4 -, HCO3 -, CO3 2-, SO4 2-)；
(concentration of TPA-BTD-BT is the THF solution of diazosulfide malononitrile TPA-BTD-BT in Figure 18 present invention
2.0×10-5Mol/L in), the CN of various concentration is added-Ultraviolet-visible absorption spectra figure (CN-Concentration is in the direction of the arrow from 0
Increase to 4.0 × 10-5mol/L)；
(concentration of TPA-BTD-BT is the THF solution of diazosulfide malononitrile TPA-BTD-BT in Figure 19 present invention
2.0×10-5Mol/L in), the CN of various concentration is added-Fluorescence spectra (λex=465nm, slit 5,5；CN-Concentration edge
Arrow direction increases to 4.0 × 10 from 0-5mol/L))；
(concentration of TPA-BTD-BT is the THF solution of diazosulfide malononitrile TPA-BTD-BT in Figure 20 present invention
2.0×10-5Mol/L it in), is added after various anion and CN-The UV-visible absorption spectrum (CN of addition-With other yin
The concentration of ion is 4.0 × 10-5mol/L)；
(concentration of TPA-BTD-BT is the THF solution of diazosulfide malononitrile TPA-BTD-BT in Figure 21 present invention
2.0×10-5Mol/L it in), is added after various anion and CN-The fluorescence enhancement factor histogram (CN of addition-With other yin
The concentration of ion is 4.0 × 10-5mol/L)。
Specific embodiment
1. the intermediate for synthesizing diazosulfide malononitrile, as shown in formula (III):
2. the synthetic method of intermediate and diazosulfide malononitrile for synthesizing diazosulfide malononitrile, synthesis
Route map is as shown in Figure 1, include the following steps:
(1) synthesis of intermediate TPA-BTD-Br；
By 4- hexichol amido phenyl boric acid 2.7568g, 4,7- bis- bromo- 2,1,3- diazosulfide 2.3576g, 4- (triphenyl
Phosphine) palladium 0.1342g and potassium carbonate 1.7880g be placed in 250mL there-necked flask, be added into mixture 60mL tetrahydrofuran THF,
45mL toluene and 22mL distilled water H2O, then 0.1mL methyl tricapryl ammonium chloride is added dropwise；Magnetite is added to be sufficiently stirred, in nitrogen atmosphere
Lower back flow reaction 16h, the temperature of back flow reaction are 85 DEG C；After reaction, 200mL distilled water is added into reactant, then
Organic phase is extracted with dichloromethane to obtain, the organic phase being obtained by extraction is evaporated under reduced pressure, obtains concentrate, concentrate is through column chromatography point
From, concentration and dry, intermediate TPA-BTD-Br is obtained；The eluent of column chromatography for separation is the mixing of methylene chloride and petroleum ether
The volume ratio of object, the methylene chloride 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- (triphen
Base phosphine) palladium 0.2588g and potassium carbonate 1.5525g are placed in 250mL there-necked flask, then 0.1mL methyl tricapryl ammonium chloride is added dropwise, so
40mL tetrahydrofuran THF, 60mL toluene and 25mL distilled water H is added in backward mixture2O；Addition magnetite is sufficiently stirred molten
Solution, back flow reaction 16h, the temperature of back flow reaction are 85 DEG C under nitrogen atmosphere；After reaction, it is extracted with extractant methylene chloride
Organic phase is obtained, the organic phase rotary evaporation being obtained by extraction is obtained into drying solid；Drying solid through column chromatography for separation, concentration and is done
It is dry, obtain intermediate TPA-BTD-CHO, the eluent of column chromatography for separation is the mixture of methylene chloride and petroleum ether, described two
The volume ratio of chloromethanes 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 spectra, 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 flask, 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 methylene chloride, 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 methylene chloride and petroleum ether, the methylene chloride 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。
The synthesized diazosulfide malononitrile come out 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 molecule the delocalization range that can increase the pi-electron of molecule, so that ultraviolet light wave generation is 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.
3. the characterization of compound
3.1 infrared spectrum
Take grinding in suitable dry potassium bromide and sample to be tested and agate mortar uniform, tabletting is surveyed infrared.4- hexichol
Amido phenyl boric acid TPA-BTD-B (OH)2, intermediate TPA-BTD-Br, intermediate TPA-BTD-CHO and diazosulfide the third two
The infrared spectrum of nitrile 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-1
And 1500cm-1Nearby there is strong absorption peak, in 900-600cm-1Also there is strong absworption peak in range.Because of the C=of monokaryon aromatic hydrocarbons
The stretching vibration of C double bond is in 1600cm-1And 1500cm-1There is absorption peak, c h bond out-of-plane bending vibration is in 900-690cm-1Area
Domain.It is known that TPA-BTD-Br contains phenyl ring.The stretching vibration of C=N double bond is in 1600-1690cm-1Between, by Fig. 2 institute
Show, throughout peak intensity is enhanced intermediate TPA-BTD-Br；This is because the force constant of the key of diazosulfide compared with
Greatly, thus everywhere peak intensity enhances.4- hexichol amido phenyl boric acid TPA-B (OH) known to analysis2With the bromo- 2,1,3- benzene of 4,7- bis-
And thiadiazoles 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 of the flexible vibration of the C=C double bond of monokaryon aromatic hydrocarbons
It moves in 1600cm-1And 1500cm-1There is absorption peak, c h bond out-of-plane bending vibration is in 900-690cm-1Region.It is known that TPA-
BTD-CHO contains phenyl ring.The stretching vibration of aldehyde radical is in 1750-1680cm-1Region, intermediate TPA-BTD-CHO exists as shown in Figure 3
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.
It is known that diazosulfide malononitrile TPA-BTD-BT contains phenyl ring.The stretching vibration of aldehyde radical is in 1750-1680cm-1Region,
TPA-BTD-BT is in this area without absorption peak as shown in Figure 3, illustrate diazosulfide malononitrile TPA-BTD-BT without-CHO,
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 institute
Show, carries out two main absorption bands occur at 200-400nm, bands of a spectrum are respectively 317 and 367nm.Visual field is in 465nm
There is a 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 excitation, the THF solution of TPA-BTD-BT generates transmitting at 600nm
Peak shows biggish stokes displacement.
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 greater 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 have the chemical shift of a hydrogen 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. the method for fluorescence detection CN-, includes 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 observation recognition methods are as follows: solution colour is turned yellow by orange, illustrates there is CN in sample to be tested-；Uv-visible absorption spectra
Recognition methods are as follows: UV-vis spectrum test is carried out at 200-660nm, UV-vis absorption spectrum 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 are as follows: under 465nm excitation, emission peak, explanation are generated at 600nm
There is CN in sample to be tested-, or under the ultraviolet light irradiation of 365nm, solution present bright orange fluorescence, illustrate have in sample to be tested
CN-。
Diazosulfide malononitrile TPA-BTD-BT is dissolved in tetrahydrofuran THF, then in diazosulfide malononitrile TPA-
CN is separately added into 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-
The concentration of BT is 2 × 10-5Mol/L, the CN of the addition-Concentration with other anion is 4 × 10-5mol/L；It is described its
His 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 in THF solution with 2equiv-And its
He is anion (F-,Cl-,Br-,I-,CH3COO-,NO2 -,NO3 -,H2PO4 -,HCO3 -,CO3 2-, SO4 2-) carried out at 200-660nm
UV-vis spectrum test figure, CN-It is added in the THF solution of TPA-BTD-BT, UV-vis absorption spectrum absorbs at 367nm
Until disappearing, the absorption peak at 465nm declines and is blue shifted to 440nm for peak decline, illustrates the conjugated degree of TPA-BTD-BT
Weaken, 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 excitation, diazosulfide third
The THF solution of dintrile TPA-BTD-BT generates emission peak at 600nm, shows biggish stokes displacement.When with 2equiv
Other anion (F-,Cl-,Br-,I-,CH3COO-, NO2 -,NO3 -,H2PO4 -,HCO3 -,CO3 2-,SO4 2-) carry out the inspection of FS fluorescence
When survey, 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 ultraviolet light irradiation (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 (0-4.0 × 10-5Mol/L), UV-vis absorption spectrum
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 turns 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 enhancement factor
It is 16.Illustrate CN-It is acted on TPA-BTD-BT, forms novel substance.This is also that CN is added under ultraviolet light irradiation-Afterwards
The reason of fluorescence of solution is remarkably reinforced.The above results sufficiently 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 fluorescence detection 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
CN is separately added into 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-It is ultraviolet-can
See Absorption and fluorescence spectrum；The concentration of the diazosulfide malononitrile TPA-BTD-BT is 2 × 10-5Mol/L, it is described to add
The concentration of other anion entered is 4 × 10-5mol/L；The CN of the addition-Concentration be 4 × 10-5mol/L；It is described its
His anion 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 is not changed 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 obvious
Enhancing.
Although from Figure 21 by emission band other anion it can be seen from fluorescence enhancement factor histogram 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 type 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
It changes among still in present patent application scope of protection of the claims.
Claims (9)
1. the intermediate for synthesizing diazosulfide malononitrile, which is characterized in that as shown in formula (III):
2. the synthetic method for the intermediate for synthesizing diazosulfide malononitrile, which comprises the steps of:
(1) synthesis of intermediate TPA-BTD-Br, shown in intermediate TPA-BTD-Br such as formula (II):
(2) by shown in intermediate TPA-BTD-Br synthetic intermediate TPA-BTD-CHO, intermediate TPA-BTD-CHO such as formula (III):
3. according to claim 2 for synthesizing the synthetic method of the intermediate of diazosulfide malononitrile, which is characterized in that
In step (1), by 4- hexichol amido phenyl boric acid, 4,7- bis- bromo- 2,1,3- diazosulfide, 4- (triphenylphosphine) palladium and carbonic acid
Potassium is placed in there-necked flask, and tetrahydrofuran THF, toluene and distilled water H are added into mixture2O, then methyl trioctylphosphine chlorination is added dropwise
Ammonium；Magnetite is added to be sufficiently stirred, reacts under nitrogen atmosphere；After reaction, 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 methylene chloride and petroleum ether.
4. according to claim 3 for synthesizing the synthetic method of the intermediate of diazosulfide malononitrile, which is characterized in that
In step (1), by 4- hexichol amido phenyl boric acid 2.7568g, 4,7- bis- bromo- 2,1,3- diazosulfide 2.3576g, 4- (three
Phenylphosphine) palladium 0.1342g and potassium carbonate 1.7880g be placed in 250mL there-necked flask, 60mL tetrahydrofuran is added into mixture
THF, 45mL toluene and 22mL distilled water H2O, then 0.1mL methyl tricapryl ammonium chloride is added dropwise；Magnetite is added to be sufficiently stirred, in nitrogen
Back flow reaction 16h under atmosphere, the temperature of back flow reaction are 85 DEG C；After reaction, 200mL distilled water is added into reactant,
Then organic phase is extracted with dichloromethane to obtain, the organic phase being obtained by extraction is evaporated under reduced pressure, obtains concentrate, concentrate is through column layer
Analysis separation, concentration and drying, obtain intermediate TPA-BTD-Br；The eluent of column chromatography for separation is methylene chloride and petroleum ether
The volume ratio of mixture, the methylene chloride and petroleum ether is 1:3.5.
5. according to claim 2 for synthesizing the synthetic method of the intermediate of diazosulfide malononitrile, which is characterized in that
In step (2), intermediate TPA-BTD-Br, 4- formylphenylboronic acid, 4- (triphenylphosphine) palladium and potassium carbonate are placed in three mouthfuls
In bottle, then methyl tricapryl ammonium chloride is added dropwise, tetrahydrofuran THF, toluene and distilled water H are then added into mixture2O；Add
Enter magnetite and dissolution is sufficiently stirred, under nitrogen atmosphere back flow reaction；After reaction, extract organic with extractant methylene chloride
The organic phase rotary evaporation being obtained by extraction is obtained drying solid by phase；By drying solid through column chromatography for separation, concentration and drying, obtain
To intermediate TPA-BTD-CHO, the eluent of column chromatography for separation is the mixture of methylene chloride and petroleum ether.
6. according to claim 5 for synthesizing the synthetic method of the intermediate of diazosulfide malononitrile, which is characterized in that
In step (2), by intermediate TPA-BTD-Br2.2737g, 4- formylphenylboronic acid 1.1100g, 4- (triphenylphosphine) palladium
0.2588g and potassium carbonate 1.5525g are placed in 250mL there-necked flask, then 0.1mL methyl tricapryl ammonium chloride is added dropwise, then to mixed
It closes and 40mL tetrahydrofuran THF, 60mL toluene and 25mL distilled water H is added in object2O；Magnetite is added, dissolution is sufficiently stirred, in nitrogen
Back flow reaction 16h under atmosphere, the temperature of back flow reaction are 85 DEG C；After reaction, organic phase is extracted to obtain with extractant methylene chloride,
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, obtain
Mesosome TPA-BTD-CHO, the eluent of column chromatography for separation are the mixture of methylene chloride and petroleum ether, the methylene chloride and stone
The volume ratio of oily ether is 1:3.5.
7. detecting CN-Method, which comprises the steps of:
(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；Shown in diazosulfide malononitrile TPA-BTD-BT such as following formula (I):
Diazosulfide malononitrile TPA-BTD-BT synthetic method shown in formula (I) is as follows: by intermediate TPA-BTD-CHO, the third two
Nitrile and ammonium acetate, are placed in three-necked flask, and glacial acetic acid is added into mixture, add magnetite and are sufficiently stirred, then in nitrogen
It is reacted under atmosphere；After reaction, organic phase is extracted to obtain with extractant methylene chloride, the organic phase rotary evaporation that will be obtained by extraction
It obtains concentrate and obtains diazosulfide malononitrile TPA-BTD-BT, column layer by concentrate through column chromatography for separation, concentration and drying
Analyse the mixture that isolated eluent is methylene chloride and petroleum ether；
(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-。
8. detection CN according to claim 7-Method, which is characterized in that visually observe recognition methods are as follows: solution colour
It is turned yellow by orange, illustrates there is CN in sample to be tested-；Uv-visible absorption spectra recognition methods are as follows: at 200-660nm
UV-vis spectrum test is carried out, UV-vis absorption spectrum absorption peak at 367nm declines or disappears, under the absorption peak at 465nm
440nm is dropped and be blue shifted to, while occurring two isobestic points at 430 and 407nm, illustrates there is CN in sample to be tested-；It is glimmering
Light spectral discrimination method are as follows: generate emission peak under 465nm excitation, at 600nm, illustrate there is CN in sample to be tested-, Huo Zhe
Under the ultraviolet light irradiation of 365nm, solution presentation bright orange fluorescence, illustrate there is CN in sample to be tested-。
9. detection CN according to claim 7-Method, which is characterized in that diazosulfide malononitrile shown in formula (I)
The specific synthetic method of TPA-BTD-BT is as follows: by intermediate TPA-BTD-CHO1.5045g, malononitrile 2.5219g and ammonium acetate
4.7811g is placed in 500mL three-necked flask, and 200mL glacial acetic acid is added into mixture, is added magnetite and is sufficiently stirred, so
React 8h under nitrogen atmosphere afterwards, reaction temperature is 117 DEG C；After reaction, upper layer organic matter is extracted with extractant methylene chloride,
Upper layer organic matter rotary evaporation is obtained into 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 methylene chloride and petroleum ether, the methylene chloride and stone
The volume ratio of oily ether is 1:1.
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| CN111471043A (en) * | 2020-04-21 | 2020-07-31 | 浙江工业大学 | Organic light-emitting material containing benzo [ c ] [1,2,5] thiadiazole derivative receptor structural unit and application thereof |
| CN114085195A (en) * | 2021-11-30 | 2022-02-25 | 浙江播下环保科技有限公司 | Biodegradable film material with light conversion function, preparation method thereof and film doping material 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 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111471043A (en) * | 2020-04-21 | 2020-07-31 | 浙江工业大学 | Organic light-emitting material containing benzo [ c ] [1,2,5] thiadiazole derivative receptor structural unit and application thereof |
| CN111471043B (en) * | 2020-04-21 | 2022-07-26 | 浙江工业大学 | Organic luminescent material containing benzo [ c ] [1,2,5] thiadiazole derivative receptor structural unit and application thereof |
| CN114085195A (en) * | 2021-11-30 | 2022-02-25 | 浙江播下环保科技有限公司 | Biodegradable film material with light conversion function, preparation method thereof and film doping material thereof |
| CN114085195B (en) * | 2021-11-30 | 2022-06-14 | 浙江播下环保科技有限公司 | Biodegradable film material with light conversion function, preparation method thereof and film doping material 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 |
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