CN106831839A - One class fluorine boron near infrared fluorescent dye and the application in the non-protonic solvent in the detection of Trace Methanol - Google Patents

One class fluorine boron near infrared fluorescent dye and the application in the non-protonic solvent in the detection of Trace Methanol Download PDF

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CN106831839A
CN106831839A CN201710133738.9A CN201710133738A CN106831839A CN 106831839 A CN106831839 A CN 106831839A CN 201710133738 A CN201710133738 A CN 201710133738A CN 106831839 A CN106831839 A CN 106831839A
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fluorine boron
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fluorescent dye
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但飞君
鲁茜
刘瑶
张吉
刘璐璐
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China Three Gorges University CTGU
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    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms

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Abstract

One class fluorine boron near infrared fluorescent dye and the application in the non-protonic solvent in the detection of Trace Methanol, the present invention relates to a class fluorine boron complexing dye preparation and its apply the detection of the methanol content in non-protonic solvent.Fluoroboric dye of the invention reacts with methyl alcohol, is hydrolyzed into part.Dyestuff is compared with part, its fluorescence emission peak has larger red shift, and its glow color is significantly different, can be recognized with bore hole, the ratio of two absworption peaks and two emission peaks has preferable linear relationship with methanol content in aprotic solvent, is capable of achieving colorimetric and the fluoroscopic examination of Trace Methanol content.The dyestuff is fast to methyl alcohol response, sensitivity is high, detection limit is low, is expected to Trace Methanol detection and monitoring field in non-protonic solvent and obtains practical application.

Description

One class fluorine boron near infrared fluorescent dye and in non-protonic solvent Trace Methanol inspection Application in survey
Technical field
The present invention relates to organic synthesis and analysis detection field, BF is specifically related to2- 2- (aromatic ethylene base) -8- (2- benzos Imidazoles) quinolines synthesis and its they analysis detection purposes, be particularly applied to first in non-protonic solvent The detection of alcohol content.
Background technology
Methyl alcohol is widely used, is the Organic Chemicals and high-grade fuel on basis, and has severe toxicity.It is mainly used in and becomes more meticulous The fields such as work, plastics, for manufacturing various organic products such as formaldehyde, acetic acid, chloromethanes, first ammonia, sulphur dimethyl ester, be also agricultural chemicals, One of important source material of medicine.Methyl alcohol can also add gasoline to mix burning after deep processing as a kind of Novel clean-fuel.Therefore it is right The measure of methanol content is particularly important in organic solvent.
There are many analysis methods, technology at present for determining the content of methyl alcohol in organic solvent, such as it is colorimetric method, solid Surely change enzyme flow injection analysis, Enzyme Electrode, refraction process, the way of distillation, based on liquid chromatography, the chromatogram of gas chromatography Method, the spectroscopic methodology based on infra-red sepectrometry, ultravioletvisible spectroscopy and fluorescence method etc..Wherein based on fluorescence method spectroscopic methodology because It has easily and fast, high sensitivity and selectivity the features such as, the emerging of many researchers is also drawn in terms of methanol content measuring Interest.The fluorescence probe of Ratio-type is that fluorescence intensity (or absorbance) is determined under two different wave lengths, and using its ratio as survey Determine signal, therefore it can eliminate the interference of the factors such as environmental factor, light source stability, concentration and probe concentration by built-in correction, So that testing result does not receive the intensity of light source.Instrumental sensitivity, concentration and probe concentration, the influence of environmental factor, overcome conventional fluorescent Shortcoming existing for probe, therefore Ratiometric fluorescent probe molecule can obtain more accurate testing result, and then improve detection side The sensitivity of method and broader responding range, it is of increased attention.Additionally, based on the fluoroscopic examination than color base The in situ detection and monitor in real time of methanol content can be realized, has good application preceding in fields such as medicine, chemical industry, food, materials Scape.
The content of the invention
It is an object of the invention to provide a class be used for detect methanol content in aprotic organic solvent fluorescence probe and its Preparation method and application.
Fluorescence probe provided by the present invention, as fluorescence probe, is somebody's turn to do using to the sensitive fluorine boron complex of methanol content Fluorescence probe is made up of three parts, and wherein part A is the benzimidazole quinoline fluorine boron list of coordination units of electron deficient, and D parts are power supply (substitution) virtue (miscellaneous) ring element of son, A is connected with D by double bond (π) unit, forms push-and-pull electronics D- π-A systems：
R1~R9 is H- or F-, Cl-, CF3- substitution wherein in A units；D units are that five yuan of virtues of donor residues (substitution) are miscellaneous Ring or hexa-atomic aromatic rings.
Wherein D units include that five yuan of heteroaromatics include furans, pyrroles, thiophene, and hexatomic ring is (R- substitutions) benzene series fragrance Ring, five yuan of (substitution), hexa-atomic condensed hetero ring.
Wherein (replace) five yuan, it is hexa-atomic thick including 9- substituted carbazoles, 3- (7- substitutions) cumarin, 2- indole rings and 3- indoles Ring.
Wherein D units substituent R includes alkyl (methyl, ethyl, isopropyl, the tert-butyl group, preferably methyl and the tert-butyl group), hydroxyl Base, alkoxy (methoxyl group, ethyoxyl, preferably phenoxy group, methoxyl group), amino and substituted-amino (including N, N- dimethyl, N, N- Diethyl, N, N- diphenyl, piperidyl, piperazinyl, morpholinyl, nafoxidine base) etc..
The fluorine boron complex is more preferably compound in detail below：
A kind of advantage of the application process of Ratiometric fluorescent probe molecule of the present invention is：
The chemical reaction machine that the method for the Ratio-type fluorine boron fluorescent probe molecule detection methanol content that the present invention is provided is relied on Complex is decomposed at system, electron deficient boron center in nucleophilicity methanol molecules attack probe molecule, obtains part.Part and complex It is the D- π-A systems of push-and-pull electronics.Compared with part, after boron is complexed with benzimidazole quinoline, the electron attraction of fluorine boron The dipole effect of whole molecule is significantly increased, electro transfer of the electron-donating group in intramolecular is increased, so that its fluorescence Red shift of the emission spectra, absorption spectrum and fluorescence emission spectrum color occur substantially to change；Simultaneously benzimidazole and quinoline ring from It is restricted by rotation, reduces non-radiative energy loss, so that fluorescence intensity strengthens, can be with naked under natural light and uviol lamp The other methanol molecules of outlook.
The Ratio-type fluorine boron fluorescent probe molecule that the present invention is provided, in the presence of methanol molecules, its Fluorescence Fluorescence emission peak subtracts It is weak, there is the fluorescence emission peak of part and as the increase of methanol content gradually strengthens.By glimmering under two different wave lengths of detection Light emissive porwer, and realize quantifying for colorimetric and the twin-channel methanol content of fluorescence using its ratio as signal is determined respectively Detection, can be effectively prevented from the interference in itself, caused by the extraneous factor such as environment and concentration and probe concentration because of instrument.
The preparation of the Ratio-type fluorine boron fluorescent probe molecule that the present invention is provided is that benzimidazole quinoline provides active methyl With substitution aldehyde, the quinoline of the D- π-A structures for obtaining further is reacted with boron trifluoride ether solution after Knoevenagel reacts N in quinoline and benzimidazole forms the hexatomic ring boron compound of four-coordination.Part and probe molecule synthesis are respectively provided with synthesis technique Simply, high income, purity is high, with low cost, advantage easy to operate.
Methanol content in the Ratio-type fluorine boron fluorescent probe molecule detection non-protonic solvent that the present invention is provided, including alkane Hydrocarbon (chain hydrocarbon, cyclic hydrocarbon etc.), aromatic hydrocarbon (benzene, toluene etc.), halogenated hydrocarbons (dichloromethane, chloroform, 1,2- dichloroethanes etc.), ether Class solvent (ether, tetrahydrofuran, dioxane etc.), ketone (acetone, pentanone etc.), nitrile (acetonitrile), N, N- dimethyl formyls Amine, dimethyl sulfoxide etc., it is applied widely.
Relative to the assay method of Trace Methanol in traditional non-proton organic solvent, this law has following in practicality Prominent advantage：(1) synthetic method is simple, it is easy to produce, with low cost；(2) it is fast to methyl alcohol response, sensitivity is high, result is accurate Really；(3) detection mode is various, you can Fluorophotometry；Also can bore hole it is qualitative, and than rate quantify；Can be in natural light Under, can be observed under uviol lamp again；(4) simple to operate, sensing system can directly be formed in prepare liquid, without sample pre-treatments Process, is very beneficial in situ detection and on line real-time monitoring is used；(5) it is applied widely, both can be applied to different aprotics The measure of Trace Methanol in organic solvent, can be applied to the different systems to be measured containing quantity of methyl alcohol scope again.
Brief description of the drawings
The structure of parts and fluorescence probe of the Fig. 1 prepared by embodiment 6.
Fig. 2 UV absorption figures in different solvents of the fluorescence probe prepared by embodiment 6.
Fig. 3 fluorescent emission figures in different solvents of the fluorescence probe prepared by embodiment 6.
The fluorescence emission spectrum of methanol content in fluorescence probe detection acetonitriles of the Fig. 4 prepared by embodiment 6.
Fluorescent emission ratio (the F of methanol content in fluorescence probe detection acetonitriles of the Fig. 5 prepared by embodiment 6570/F667) with Methanol content changes linear relationship chart.
Specific embodiment
The synthesis of the ligand 1 of embodiment 1 and fluorescence probe 1
(1) synthesis of ligand 1
To sequentially adding the benzimidazolyl quinoline (1.9mmol) of 0.51g 2- methyl -8, benzene containing 0.31g in 50mL two-mouth bottles Formaldehyde (2.9mmol), 10mL methyl alcohol, 0.57mL piperidines (4.8mmol), 0.33mL glacial acetic acids (4.8mmol), flow back 8h, cooling, There is yellow solid to separate out, suction filtration obtains solid, filter cake is washed with methyl alcohol 3 times, obtain yellow solid 0.58g, yield：78.4%, fusing point 179.3~179.5 DEG C.1HNMR(400MHz,CDCl3) δ 13.73 (s, 1H), 9.12 (dd, J=7.4,1.1Hz, 1H), 8.25 (d, J=8.6Hz, 1H), 7.89 (dd, J=11.0,7.5Hz, 2H), 7.78-7.63 (m, 6H), 7.52-7.45 (m, 3H), 7.42 (t, J=7.3Hz, 1H), 7.35-7.30 (m, 2H)；MS, m/z (%):347.7(M+, 100).
(2) synthesis of fluorescence probe 1
To sequentially adding 0.35g ligand 1s (1.0mmol), 10mL chloroforms, 1.47mL triethylamines, nitrogen in 50mL two-mouth bottles Under protection, 1.10mL BFEEs are slowly added dropwise at 0 DEG C, flow back 6h, there are a large amount of solids to separate out, suction filtration is washed with chloroform Wash filter cake 3 times, obtain solid 0.25g, yield：63.3%.
1HNMR(400MHz,CDCl3) δ 9.26 (d, J=7.6Hz, 1H), 8.65-8.54 (m, 2H), 8.24 (d, J= 8.6Hz, 1H), 8.00 (d, J=7.4Hz, 1H), 7.94 (d, J=6.3Hz, 1H), 7.91-7.83 (m, 2H), 7.78 (d, J= 7.2Hz, 2H), 7.69 (d, J=16.3Hz, 1H), 7.51 (d, J=7.3Hz, 3H), 7.35 (dd, J=5.5,2.8Hz, 2H)； MS, m/z (%):395.2(M+, 100).
The synthesis of the part 3 of embodiment 2 and fluorescence probe 3
(1) synthesis of part 3
To sequentially adding the benzimidazolyl quinoline (1.9mmol) of 0.51g 2- methyl -8, benzene containing 0.39g in 50mL two-mouth bottles Formaldehyde (2.9mmol), 10mL methyl alcohol, 0.57mL piperidines (4.8mmol), 0.33mL glacial acetic acids (4.8mmol), flow back 8h, cooling, There is yellow solid to separate out, suction filtration obtains solid, filter cake is washed with methyl alcohol 3 times, obtain yellow solid 0.48g, yield：65.7%, fusing point 187.2~187.6 DEG C.1H NMR(400MHz,CDCl3) δ 13.80 (s, 1H), 9.10 (dd, J=7.5,1.4Hz, 1H), 8.20 (d, J=8.6Hz, 1H), 7.88 (d, J=12.9Hz, 1H), 7.86-7.79 (m, 1H), 7.76-7.55 (m, 6H), 7.39- 7.29(m,3H),7.05–6.97(m,2H)；MS, m/z (%):377.6(M+, 100).
(2) synthesis of fluorescence probe 3
To sequentially adding 0.38g parts 3 (1.0mmol), 10mL chloroforms, 1.47mL triethylamines, nitrogen in 50mL two-mouth bottles Under protection, 1.10mL BFEEs are slowly added dropwise at 0 DEG C, flow back 6h, there are a large amount of solids to separate out, suction filtration is washed with chloroform Wash filter cake 3 times, obtain solid 0.19g, yield：42.2%.
1H NMR(400MHz,CDCl3) δ 9.26-9.11 (m, 1H), 8.65-8.37 (m, 2H), 8.19 (d, J=9.0Hz, 1H), 7.93 (d, J=7.9Hz, 2H), 7.90-7.77 (m, 2H), 7.69 (dd, J=25.9,12.4Hz, 3H), 7.43-7.30 (m, 2H), 7.01 (d, J=8.7Hz, 2H), 3.90 (s, 3H)；13C NMR(100MHz,DMSO)δ161.6,160.2,158.1, 157.3,148.8,144.2,144.2,137.8,136.1,135.1,131.6,131.1,130.1,129.1,128.6, 127.2,126.4,125.8,123.9,119.4,115.0,114.3,55.2；MS, m/z (%):426.1(M+, 100).
The synthesis of the part 5 of embodiment 3 and fluorescence probe 5
(1) synthesis of part 5
To sequentially adding the benzimidazolyl quinoline (1.9mmol) of 0.51g 2- methyl -8, benzene containing 0.43g in 50mL two-mouth bottles Formaldehyde (2.9mmol), 10mL methyl alcohol, 0.57mL piperidines (4.8mmol), 0.33mL glacial acetic acids (4.8mmol), flow back 8h, cooling, There is yellow solid to separate out, suction filtration obtains solid, filter cake is washed with methyl alcohol 3 times, obtain yellow solid 0.68g, yield：87.1%.1H NMR(400MHz,CDCl3) δ 13.93 (br, 1H), 9.07 (dd, J=7.5,1.5Hz, 1H), 8.14 (d, J=8.7Hz, 1H), 7.91-7.88 (m, 1H), 7.81 (dd, J=8.0,1.4Hz, 1H), 7.68-7.58 (m, 6H), 7.33-7.31 (m, 2H), 7.22 (s, 1H), 6.78 (d, J=8.8Hz, 2H), 3.06 (s, 6H)；MS, m/z (%):390.1(M+, 100).
(2) synthesis of fluorescence probe 5
To sequentially adding 0.39g parts 5 (1.0mmol), 10mL chloroforms, 1.47mL triethylamines, nitrogen in 50mL two-mouth bottles Under protection, 1.10mL BFEEs are slowly added dropwise at 0 DEG C, flow back 6h, there are a large amount of solids to separate out, suction filtration is washed with chloroform Wash filter cake 3 times, obtain solid 0.34g, yield：77.1%.
1H NMR(400MHz,CDCl3):δ9.15(s,1H),8.45–8.38(m,2H),8.18(d,1H),7.92–7.89 (m,2H),7.87–7.84(m,1H),7.78(t,1H),7.67-7.60(m,3H),7.36–7.30(m,6H),7.20–7.13 (m,6H),7.09(d,2H)；13C NMR(100MHz,CDCl3)δ152.5,144.6,141.6,137.2,131.6,130.9, 130.9,129.6,127.6,123.4,122.8,122.7,120.5,120.5,118.8,114.0,112.0,111.7；MS,m/ Z (%):438.1(M+, 100).
The synthesis of the part 6 of embodiment 4 and fluorescence probe 6
(1) synthesis of part 6
To sequentially adding the benzimidazolyl quinoline (1.9mmol) of 0.51g 2- methyl -8,0.79g in 50mL two-mouth bottles (2.9mmol) 4- formoxyl triphenylamines, 10mL n-butanols, 0.57mL (4.8mmol) piperidines, 0.33mL (4.8mmol) glacial acetic acid, Backflow 8h, cooling has yellow solid to separate out, and suction filtration obtains solid, filter cake is washed with ethanol 3 times, obtains yellow solid 0.83g, yield 82.1%.186.1~187.0 DEG C of fusing point.1H NMR(CDCl3, 400MHz), δ:13.85 (s, 1H), 9.11 (d, J=7.4Hz, 1H), 8.21 (d, J=8.6Hz, 1H), 7.85 (d, J=8.0Hz, 2H), 7.78-7.42 (m, 6H), 7.32 (ddd, J=7.6, 6.8,4.2Hz,7H),7.23–7.04(m,8H).MS, m/z (%):514.6(M+, 100).
(2) synthesis of fluorescence probe 6
To sequentially adding 0.52g (1.0mmol) part 6,10mL chloroforms, 1.35mL triethylamines, nitrogen in 50mL two-mouth bottles Under protection, 0.98mL BFEEs are slowly added dropwise at 0 DEG C, flow back 6h, cooling has solid to separate out, and suction filtration is washed with chloroform Wash 3 times, dry, obtain red solid 0.24g, yield 42.3%.
1H NMR(CDCl3, 400MHz), δ：9.11 (dd, J=7.5,1.4Hz, 1H), 8.43 (t, J=14.0Hz, 2H), 8.17 (d, J=9.0Hz, 1H), 7.91 (dt, J=5.0,2.5Hz, 2H), 7.85 (dd, J=6.3,2.7Hz, 1H), 7.77 (t, J=7.7Hz, 1H), 7.63 (dd, J=15.8,12.7Hz, 3H), 7.39-7.29 (m, 6H), 7.17 (dd, J=17.8, 7.5Hz, 6H), 7.09 (d, J=8.7Hz, 2H)；13C NMR(CDCl3, 100MHz), δ:158.6,150.7,146.5,146.4, 143.8,142.6,137.0,136.2,131.2,130.6,130.1,129.6,129.4,127.9,127.8,127.2, 125.8,125.2,124.6,123.8,123.6,123.4,122.1,120.9,120.8,120.0,119.9,118.0, 114.2.MS, m/z (%):562.5(M+, 100).
The synthesis of the part 7 of embodiment 5 and fluorescence probe 7
(1) synthesis of part 7
To sequentially adding the benzimidazolyl quinoline (1.9mmol) of 0.51g 2- methyl -8, benzene containing 0.54g in 50mL two-mouth bottles Formaldehyde (2.9mmol), 10mL methyl alcohol, 0.57mL piperidines (4.8mmol), 0.33mL glacial acetic acids (4.8mmol), flow back 8h, cooling, There is yellow solid to separate out, suction filtration obtains solid, filter cake is washed with methyl alcohol 3 times, obtain yellow solid 0.39g, yield：47.6%,1H NMR(400MHz,CDCl3) δ 13.63 (s, 1H), 9.12 (dd, J=7.4,1.5Hz, 2H), 8.57-8.49 (m, 4H), 8.15 (d, J=8.8Hz, 2H), 7.92 (tdd, J=5.8,3.8,1.9Hz, 6H), 7.84 (t, J=7.7Hz, 2H), 7.68-7.48 (m,11H),7.41–7.35(m,4H)；MS, m/z (%):426.3(M+, 100).
(2) synthesis of fluorescence probe 7
To sequentially adding 0.43g parts 7 (1.0mmol), 10mL chloroforms, 1.47mL triethylamines, nitrogen in 50mL two-mouth bottles Under protection, 1.10mL BFEEs are slowly added dropwise at 0 DEG C, flow back 6h, there are a large amount of solids to separate out, suction filtration is washed with chloroform Wash filter cake 3 times, obtain solid 0.18g, yield：40.1%.
1H NMR(400MHz,CDCl3) δ 9.18 (dd, J=7.4,1.5Hz, 2H), 8.57-8.49 (m, 4H), 8.15 (d, J =8.8Hz, 2H), 7.92 (tdd, J=5.8,3.8,1.9Hz, 6H), 7.84 (t, J=7.7Hz, 2H), 7.68-7.48 (m, 11H),7.41–7.35(m,4H)；MS, m/z (%):474.1(M+, 100).
The synthesis of the ligand 18 of embodiment 6 and fluorescence probe 18
(1) synthesis of ligand 18
To sequentially adding 0.6021g (2.4mmol) 3- aldehyde radical -7- diethyl amino coumarins in 50mL single port bottles, The benzimidazolyl quinoline of 0.5103g (1.9mmol) 2- methyl -8,10mL n-butanols, stirring adds 0.24mL piperidines, 0.13mL glacial acetic acid, plus fraction water device water-dividing, stir at 150 DEG C.There are a large amount of red precipitates to produce after 10h, stop reaction, cool down, Suction filtration obtains red solid, and gained solid is washed with ethanol.Suction filtration obtains product again, dries, weigh to obtain 0.3687g solids, yield 41%, 250~252 DEG C of fusing point.1H NMR(400MHz,CDCl3):δ 13.78 (s, 1H), 9.06 (d, J=7.5Hz, 1H), 8.29-7.99 (m, 1H), 7.97-7.50 (m, 7H), 7.42-7.28 (m, 3H), 6.59 (dd, J=8.8,2.3Hz, 1H), 6.47 (d, J=2.1Hz, 1H), 3.42 (d, J=7.1Hz, 4H), 1.24 (t, J=7.1Hz, 6H)
(2) synthesis of fluorescence probe 18
0.1034g (0.205mmol) ligand 18 is taken in two-mouth bottle, under nitrogen protection, 2mL chloroforms, 0.2mL is sequentially added Triethylamine, is heated to reflux, incomplete molten, adds 2mL chloroforms, continues to be heated to reflux, and solid all dissolves, and takes on a red color, and is slowly added to 0.2mLBF3·Et2O, has a large amount of white cigarettes to generate, and solution becomes purple, continues to be stirred at reflux, and TLC tracking still has raw material point after 3h, Add 0.2mLBF3·Et2O and 1mL chloroforms, continue to be stirred at reflux, suction filtration after 2h, obtain solid 0.06102g, yield 60%.
1HNMR (400MHz, DMSO) δ 9.09 (d, J=9.0Hz, 1H), 8.99 (d, J=7.5Hz, 1H), 8.89 (m, 3H), 8.75 (d, J=9.3Hz, 1H), 8.53 (d, J=7.8Hz, 1H), 8.32 (s, 1H), 8.12 (m, 2H), 8.00-7.85 (m, 1H), 7.64 (d, J=9.1Hz, 1H), 7.61-7.55 (m, 1H), 6.85 (d, J=11.3Hz, 1H), 6.68 (s, 1H), 3.19-2.92 (m, 4H), 1.18 (t, J=7.3Hz, 6H)
The preparation of the test solution of embodiment 7
(1) preparation of standard liquid
It is 10 to weigh a certain amount of fluorescence probe and be configured to concentration-3The acetonitrile solution of mol/L
(2) preparation of the different solution of aprotic containing quantity of methyl alcohol
10 are pipetted respectively-3The acetonitrile solution of mol/L is in some 25ml volumetric flasks and removes methyl alcohol, adds different amounts of Methyl alcohol addition is 0.01,0.02,0.05,0.10,0.20,0.50,1.00,2.00,5.00,10.00,15.00,20.00), Then with solvent constant volume to be measured.
The detection of methanol content in the non-protonic solvent of embodiment 8
The measure of fluorescent emission AAS spectrum is carried out on luminoscope, and solution to be measured is placed in into 1cm quartz cuvettes In ware, excitation wavelength 475nm,
The fluorescent probe molecule and ligand molecular fluorescence radiation intensity of probe under different methanol contents are determined respectively, calculate it Ratio, is mapped with methanol content in relative luminous intensity ratio-non-protonic solvent, draws standard curve, is calculated detection The test limit and the range of linearity of methanol content.Wherein, calculated according to minimum detectability formula (LOD=3 σ/b), in fluorescence spectrophotometer Photometry fluorescence probe is to the LOD of the detection of methanol content in non-protonic solvent：3.62%.

Claims (9)

1. a class fluorine boron near infrared fluorescent dye, it has formula one or the structure of formula two：
The structure part A is the benzimidazole quinoline fluorine boron list of coordination units of electron deficient, and D parts are the aromatic ring unit or virtue of supplied for electronic Heterocyclic units or substituted aromatic ring unit or aromatic ring unit heteroaromatic unit, A are connected with D by double bond (π), form push-and-pull electronics D- π-A systems.
2. the fluorine boron near infrared fluorescent dye described in claim 1, it is characterised in that in formula one, the R of A units1~R9For H-, F-、Cl-、CF3- in any one substitution base；D units are five yuan of heteroaromatics of donor residues or substituted five-membered heteroaromatic or hexa-atomic Aromatic rings；In formula two, the R of A units1~R9It is H-, F-, Cl-, CF3- in any one substitution base；D units are donor residues Five yuan of condensed hetero rings or substituted five-membered condensed hetero ring or hexa-atomic condensed hetero ring.
3. the fluorine boron near infrared fluorescent dye described in claim 2, it is characterised in that D units in formula one, five yuan of heteroaromatics include Furans, pyrroles, thiophene, hexa-atomic aromatic rings are the benzene series aromatic rings that benzene series aromatic rings or R- replace.
4. the fluorine boron near infrared fluorescent dye described in claim 3, it is characterised in that D units substituent R in formula one, including alkane Base, alkoxy or amino and substituted-amino；Wherein, alkyl is specially methyl, ethyl, isopropyl, the tert-butyl group or hydroxyl, preferably first Base and the tert-butyl group；Alkoxy is specially methoxyl group, ethyoxyl or phenoxy group, preferably methoxyl group；Amino and substituted-amino are specially Including N, N- dimethyl, N, N- diethyl, N, N- diphenyl, piperidyl, piperazinyl, morpholinyl, nafoxidine base.
5. the fluorine boron near infrared fluorescent dye described in claim 2, it is characterised in that characterized in that, D units include in formula two Five yuan of condensed hetero rings, five yuan of condensed hetero rings are 2- indoles, 3- indoles and 3- (9- substitutions) carbazole；9- substitutions base in 3- (9- substitutions) carbazole It is C1-C10Alkyl, specially methyl, ethyl or benzyl.
6. the fluorine boron near infrared fluorescent dye described in claim 2, it is characterised in that D units include hexa-atomic condensed hetero ring in formula two, Hexa-atomic condensed hetero ring is 3- (7- substitutions) coumarin ring；3- (7- substitutions) coumarin ring, substitution base includes hydroxyl, alkoxy or amino And substituted-amino；Wherein, alkoxy includes methoxyl group, ethyoxyl or phenoxy group, preferably methoxyl group；Amino and substituted-amino include N, N- dimethyl or N, N- diethyl.
7. the fluorine boron near infrared fluorescent dye described in claim 5, D units include condensed hetero ring in formula two, it is characterised in that five yuan Condensed hetero ring is 2- indole rings and 3- indole rings.
8. the detection of the fluorine boron near infrared fluorescent dye Trace Methanol in non-protonic solvent described in any one of claim 1-7 On application.
9. applied described in claim 8, it is characterised in that non-protonic solvent, including alkane, aromatic hydrocarbon, halogenated hydrocarbons, ethers are molten One or more in agent, ketone, nitrile, N,N-dimethylformamide, dimethyl sulfoxide；Wherein, alkane includes chain hydrocarbon, cyclic hydrocarbon； Aromatic hydrocarbon includes benzene or toluene；Halogenated hydrocarbons includes dichloromethane, chloroform or 1,2- dichloroethanes；Ether solvent includes second Ether, tetrahydrofuran or dioxane；Ketone includes acetone or pentanone；Nitrile is acetonitrile.
CN201710133738.9A 2017-03-08 2017-03-08 One class fluorine boron near infrared fluorescent dye and the application in the non-protonic solvent in the detection of Trace Methanol Pending CN106831839A (en)

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CN110105381A (en) * 2019-06-11 2019-08-09 青岛科技大学 A kind of cumarin is the preparation and application of the beta-diketon boron fluoride fluorescent dye of skeleton
CN110143977A (en) * 2019-06-12 2019-08-20 青岛科技大学 A kind of miscellaneous boron difluoride complex compound fluorochrome of cumarin and its application
CN110183478A (en) * 2019-07-11 2019-08-30 青岛科技大学 A kind of synthesis and its application of cyanines, cumarin, dicarbapentaborane boron fluoride hybrid fluorescent dyestuff

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108507901A (en) * 2018-06-21 2018-09-07 河南省煤气(集团)有限责任公司义马气化厂 The analysis method of trace carbinol in a kind of purified gas
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CN110105381B (en) * 2019-06-11 2021-10-29 青岛科技大学 Preparation and application of beta-diketone boron fluoride fluorescent dye with coumarin as skeleton
CN110143977A (en) * 2019-06-12 2019-08-20 青岛科技大学 A kind of miscellaneous boron difluoride complex compound fluorochrome of cumarin and its application
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CN110183478A (en) * 2019-07-11 2019-08-30 青岛科技大学 A kind of synthesis and its application of cyanines, cumarin, dicarbapentaborane boron fluoride hybrid fluorescent dyestuff
CN110183478B (en) * 2019-07-11 2021-07-23 青岛科技大学 Synthesis and application of cyanine, coumarin and dicarbonyl boron fluoride hybrid fluorescent dye

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