CN106008358A - Benzimidazolyl chemical sensor used for fluorescence quenching detection of nitroaromatic explosives, and preparation method of benzimidazolyl chemical sensor - Google Patents
Benzimidazolyl chemical sensor used for fluorescence quenching detection of nitroaromatic explosives, and preparation method of benzimidazolyl chemical sensor Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/18—Benzimidazoles; Hydrogenated benzimidazoles with aryl radicals directly attached in position 2
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
Abstract
The invention relates to a benzimidazolyl chemical sensor used for fluorescence quenching detection of nitroaromatic explosives, and a preparation method of the benzimidazolyl chemical sensor. Bi(benzimidazole)naphthalene and halohydrocarbon are taken as raw materials, and the benzimidazolyl chemical sensor mainly used for PA detection and having high selectivity and high sensitivity in explosive NAC detection is mainly prepared through a simple and feasible N-alkylate substitution reaction. The prepared benzimidazolyl chemical sensor can be used for PA detection under a UV lamp by utilizing the principle that fluorescence quenching solution neutralization is visible in a solid state, and gaseous PA detection can be realized. The invention provides a structure and a synthetic method of a bi(benzimidazole)naphthalene novel chemical sensor used for fluorescence quenching detection of nitroaromatic explosives, the preparation process is simple to operate, and the prepared bi(benzimidazole)naphthalene novel chemical sensor can detect nitroaromatic explosives, particularly picric acid, in various manners with high selectivity and high sensitivity.
Description
Technical field
The invention belongs to the detection technique field of nitro arene explosive substance, particularly relate to a kind of sudden for nitro-aromatic explosive fluorescence
Go out benzimidazole based chemical sensors of detection and preparation method thereof.
Background technology
Owing to explosive nitro arene compound (NAC) causes the worst impact to safety, environment and health, the most instead
Probably, nonmetallic mine detection, the demand such as environmental quality monitoring sharply increase, make micro-trace detection of NAC come into one's own, need exploitation badly
Low cost, high efficiency, simple and easy to do, selectivity are strong, the detection method of rapid sensitive.Wherein, high sensitivity and high selectivity fluorescence
Detection method receives much concern in recent years.But, relate at present based on organic molecule fluorescence high sensitivity and highly selective solid-state detection
The report of the chemical sensor of NAC, particularly picric acid (PA) is little.
It should be noted that the kind of these organic molecules is very limited, mainly the most nitrogenous heterocyclic benzo virtue hydrocarbons and their derivates
[Bhalla V,Gupta A,Kumar M,Rao D S,Prasad S K.ACS Appl.Mater.Inter.2013,5(3):672-679；Bhalla V,
Gupta A,Kumar M.Org.Lett.2012,14(12):3112-3115；Roy B,Bar AK,Gole B,Mukherjee P S.J.Org.
Chem.2013,78(3):1306-1310；Vij V,Bhalla V,Kumar M.ACS Appl.Mater.Inter.2013,5(11):5373-5380；
Bhalla V,Arora H,Singh H,Kumar M.Dalton Trans.2013,42(4),969-974]。
Moreover, these organic molecules, in terms of synthesis, more or less also exist synthesis material costliness, complex synthetic route, mesh
Mark compound productivity is low, and uses the deficiencies such as expensive Pd catalyst.
By contrast, it is easy to the benzimidazoles derivative of synthesis biological medicine, chemical sensor, supramolecular chemistry, photoelectric material,
The fields such as fire retardant have a wide range of applications, but utilize its fluorescence property to be applied to the chemical sensitisation of NAC context of detection based on benzimidazole
The report of device seldom [Xiong J F, Li J X, Mo G Z, Huo J P, Liu J Y, Chen X Y, Wang Z Y.J.Org.Chem.2014,
79(23):11619-11630]。
In consideration of it, the application is with two (benzimidazole) naphthalene, halogenated hydrocarbons etc. as raw material, by steps such as simple N-alkylation replacements,
Synthesize first for explosive nitroaromatic (particularly PA) high selectivity, two (benzimidazole) naphthalene of high sensitivity detection
Class novel fluorescence chemical sensor.
Summary of the invention
Present invention aims in prior art based on organic molecule fluorescence high sensitivity and highly selective solid-state detection
The chemical sensor of NAC, particularly PA is difficult to defects such as preparing, kind is less, it is provided that a kind of for nitro arene explosive substance inspection
Two (benzimidazole) naphthalenes novel fluorescence chemical sensor surveyed and preparation method thereof, this preparation method is simple, and target compound structure changes
Various, effect is obvious, has preferable industrial applications prospect.
The present invention is achieved through the following technical solutions:
The preparation method of a kind of benzimidazole based chemical sensors for the detection of nitro-aromatic explosive fluorescent quenching, with two (benzimidazoles)
Naphthalene compounds and halogenated hydrocarbons are raw material, mainly by simple N-alkylation substitution reaction, prepare based on detection PA,
The benzimidazolyl fluorescence chemical sensor of the explosive NAC of high selectivity, high sensitivity detection, described benzimidazolyl fluorescence chemical passes
Sensor utilizes in fluorescent quenching solution and visual detection PA under solid-state under uviol lamp, and can realize the detection of gaseous state PA.
The preparation method of a kind of benzimidazole based chemical sensors for the detection of nitro-aromatic explosive fluorescent quenching, comprises the steps:
(1) after halogenated hydrocarbons and two (benzimidazole) naphthalene compounds being mixed in organic solvent, add alkali solid catalyst, control
Reaction temperature, carries out N-alkylation substitution reaction；
(2) after reaction terminates, with acetic acid ethyl dissolution, transfer, taking organic facies after washing, anhydrous magnesium sulfate is dried, and rotation boils off molten
Agent, thick product, through column chromatography for separation, obtains two (benzimidazole) naphthalenes new chemical sensor, i.e. described glimmering for nitro-aromatic explosive
The benzimidazole based chemical sensors of optical quenching detection.
Further, described halogenated hydrocarbons is propargyl bromide or saturated straight chain end halogenated hydrocarbons CnH2n+1X, wherein n=3-18, X be Cl,
Br or I.
Further, described two (benzimidazole) naphthalene compounds has following structural formula:
Wherein, left side benzimidazolyl may be alternatively located at 5,7,8 positions, and the benzimidazolyl on the right may be alternatively located at 1,3,4 positions,
Preferably there is symmetrical structure；R1For CH3、C2H5, Cl or Br, preferably CH3, C2H5.
Further, in step (1), described organic solvent is in acetonitrile, dimethyl sulfoxide, oxolane, ethyl acetate and toluene
One or both.
Further, in step (1), described alkali solid catalyst is in sodium hydroxide, sodium carbonate, potassium hydroxide and sodium hydride
One or both.
Further, in step (1), the mol ratio of described halogenated hydrocarbons and two (benzimidazole) naphthalene compounds is 1.8 1～5.0:1,
It is preferably 1.8 1～3.0:1.
Further, in step (1), the mol ratio of described alkali solid catalyst and two (benzimidazole) naphthalene compounds is 2 1～6:
1, preferably 3 1～5 1.
Further, in step (1), the reaction temperature of described N-alkylation substitution reaction is 0～100 DEG C, preferably 60～90
℃。
Further, in step (1), the response time of described N-alkylation substitution reaction is 1～20 hour, preferably 1～10
Hour.
Further, when in step (1), halogenated hydrocarbons is propargyl bromide, reaction obtain containing end alkynyl radical two (benzimidazole) naphthalenes chemical combination
Thing continues to carry out Click reaction under copper salt catalyst effect with alkyl azide, then is prepared for nitro by step (2)
The benzimidazole based chemical sensors of aromatic hydrocarbons explosive fluorescent quenching detection.
Further, when relating to Click reaction in step (1), the reaction temperature of described Click reaction is 0～100 DEG C, excellent
Elect as is 20～80 DEG C.
Further, when relating to Click reaction in step (1), the response time of described Click reaction is 28～65 hours,
It is preferably 38～60 hours.
Further, described alkyl azide is saturated straight chain end azide CnH2n+1N3, wherein n=4-12.
Further, described alkyl azide is 2 1～4:1 with the mol ratio containing end alkynyl radical two (benzimidazole) naphthalene compounds.
Further, the reaction dissolvent of described Click reaction is in acetonitrile, dimethyl sulfoxide, oxolane, ethyl acetate or toluene
One or both.
Further, described copper salt catalyst is cuprous salt catalyst or is mixed with, by cupric salt and reducing agent, the material obtained,
Wherein cuprous salt catalyst is CuI, CuCl or CuBr, and cupric salt is Schweinfurt green, copper sulfate or copper chloride, and reducing agent is copper powder.
The benzimidazole based chemical sensors prepared by any of the above-described preparation method.
The present invention compared with prior art, has the advantage that
1, the synthesis side for two (benzimidazole) naphthalenes new chemical sensor of nitro-aromatic explosive fluorescent quenching detection is proposed first
Method, and the character such as its fluorescent quenching are disclosed.
2, according to the difference of two (benzimidazole) naphthalenes novel fluorescence chemical sensor architecture, in conjunction with NAC (including PA) fluorescent quenching
Effect, filters out for different explosive NAC (particularly PA) high selectivitys, the benzimidazolyl chemical sensitisation of high sensitivity detection
Device.
3, relevant N-alkylation replaces, the raw material of middle use of Click reaction, catalyst, solvent are easy to get, easy temperature control, technique letter
Single, quickly, product is prone to purification in synthesis, is suitable for commercial production of magnifying.
4, synthesized two (benzimidazole) naphthalenes novel fluorescence chemical sensor, utilizes in fluorescent quenching solution and solid-state under uviol lamp
Lower visual detection NAC (particularly PA), it might even be possible to realize the detection of gaseous state PA, it is simple to application.
Accompanying drawing explanation
Fig. 1 is that prepared two (benzimidazole) the naphthalenes novel fluorescence chemical sensor of example 1 is in oxolane-aqueous solution (volume ratio 1 9)
Fluorescent quenching curve chart under excitation wavelength 335nm excites after middle dropping PA.
Fig. 2 is the design sketch that two (benzimidazole) naphthalenes novel fluorescence chemical sensor that example 1 prepares realizes gaseous state PA detection.
Fig. 3 is that prepared two (benzimidazole) the naphthalenes novel fluorescence chemical sensor of example 3 is in oxolane-aqueous solution (volume ratio 1 9)
Fluorescent quenching curve chart under excitation wavelength 335nm excites after middle dropping 2,4-DNT (DNT).
Detailed description of the invention
It is embodied as being described further to the present invention below in conjunction with example, but the enforcement of the present invention and protection domain are not limited to this.
Embodiment 1
(1) with 0.523 gram of 1-bromo-dodecane and 0.389 gram of 2,6-bis-(5-tolimidazole) naphthalene (the most aforementioned two (benzimidazole) naphthalenes
In structural formula of compound, benzimidazolyl is positioned at the 2 of naphthalene nucleus, 6-position, and R1=CH3) it is raw material, by the amount of material than n (1-bromine ten
Dioxane): n (2,6-bis-(5-tolimidazole) naphthalene)=2.1:1 mix homogeneously, is 80 DEG C, 0.160 gram of NaOH solid in temperature
Under conditions of being solvent for catalyst and 10 milliliters of acetonitriles, carry out N-alkylation substitution reaction 2 hours；
(2) after reaction terminates, with acetic acid ethyl dissolution, transfer, taking organic facies after washing 3 times, anhydrous magnesium sulfate is dried, and spins off molten
Agent, thick product, through column chromatography for separation, obtains white solid two (benzimidazole) naphthalenes novel fluorescence chemical sensor 0.600 gram, productivity
83%, fusing point 43.8-44.9 DEG C, the structure of product is through infrared spectrum, proton nmr spectra, carbon-13 nmr spectra, ultraviolet spectra, unit
The Organic substance characterizing methods such as element analysis, mass spectrum are confirmed.
The structure of product following (the digital labelling on structural formula is corresponding with the label in nuclear-magnetism test data):
Characterization of compound data: UV-vis (THF) λmax:408.0nm；1H NMR(CDCl3-TMS, 400MHz): δ=0.85 (6H, t,
J=8.0Hz, CH3-24,24′),1.09-1.35(36H,m,CH2-15,15′,16,16′,17,17′,18,18′,19,19′,20,20′,21,21′,22,22′,23,
23′),1.82-1.92(4H,m,CH2-14,14′),2.52(3H,s,ArCH3-12),2.55(3H,s,ArCH3-12′),4.26-4.34(4H,m,
NCH2-13,13 '), 7.13-7.18 (2H, m, ArH-7,7 '), 7.23 (1H, s, ArH-10), 7.34 (1H, d, J=8.0Hz, ArH-8), 7.65
(1H, s, ArH-10 '), 7.74 (1H, d, J=8.0Hz, ArH-8 '), 7.90 (2H, d, J=8.0Hz, ArH-4,4 '), 8.06 (2H, d, J=8.0
Hz,ArH-3,3′),8.28(2H,s,ArH-1,1′)；13C NMR(CDCl3-TMS, 100MHz): δ=14.1 (C-24,24 '), 21.6
(C-12),22.0(C-12′),22.7(C-23,23′),26.7(C-15,15′),29.0(C-16,16′),29.3(C-21,21′),29.4(C-17,17′),
29.5(C-18,18′),29.6(C-19,19′),29.8(C-20,20′),29.9(C-14,14′),31.9(C-22,22′),44.9(C-13),45.0
(C-13′),109.7(C-7),110.1(C-7′),119.5(C-10),119.7(C-10′),124.1(C-3),124.4(C-3′),127.1(C-1,1′),
129.0(C-8,8′),132.2(C-6,6′),132.9(C-4,4′),133.1(C-9,9′),133.8(C-25,25′),136.0(C-2,2′),141.2(C-11),
143.4(C-11′),152.7(C-5),153.1(C-5′)；IR(film),ν,cm-1: 3036.09 (aromatic rings unsaturation C-H stretching vibrations),
(2957.97,2928.07,2856.70 saturated C-H stretching vibration), 1655.00 (C=N stretching vibrations), 1607.74,1508.40,1460.18
(aromatic rings skeletal vibration), 1340.58 (C-N stretching vibrations), 878.61,807.24 (phenyl ring 1,2,4-tri-replacement)；ESI-MS, m/z (%):
Calcd for C50H69N4 +([M+H]+):725.55(100),Found:725.73(100)；Anal.Calcd for C50H68N4:C 82.82,H
9.45,N 7.73,Found:C 82.88,H 9.40,N 7.72.
Product fluorescent quenching in oxolane-aqueous solution (volume ratio 1 9) after dropping PA is have studied with fluorescence spectrum means of testing,
Exciting at 335nm, its fluorescence substantially completely quencher when PA addition arrives 5 equivalent, result is as shown in Figure 1.
Two (benzimidazole) naphthalenes novel fluorescence chemical sensor of synthesis can be used for the detection of NAC class explosive, and can realize gaseous state PA
Detection, Detection results figure is as shown in Figure 2.
Embodiment 2
(1) with 0.523 gram of 1-bromo-dodecane and 0.389 gram of 2,6-bis-(5-tolimidazole) naphthalene (the most aforementioned two (benzimidazole) naphthalenes
In structural formula of compound, benzimidazolyl is positioned at the 2 of naphthalene nucleus, 6-position, and R1=CH3) it is raw material, by the amount of material than n (1-bromine ten
Dioxane): n (2,6-bis-(5-tolimidazole) naphthalene)=2.1:1 mix homogeneously, is 80 DEG C, 0.080 gram of NaOH solid in temperature
Under conditions of being solvent for catalyst and 10 milliliters of acetonitriles, carry out N-alkylation substitution reaction 10 hours；
(2) after reaction terminates, with acetic acid ethyl dissolution, transfer, taking organic facies after washing 3 times, anhydrous magnesium sulfate is dried, and spins off molten
Agent, thick product, through column chromatography for separation, obtains white solid two (benzimidazole) naphthalenes novel fluorescence chemical sensor 0.464 gram, productivity
65%, fusing point 43.7-44.9 DEG C, the structure of product is through infrared spectrum, proton nmr spectra, carbon-13 nmr spectra, ultraviolet spectra, unit
The Organic substance characterizing methods such as element analysis, mass spectrum are confirmed, product dependency structure and data consistent with Example 1.
Product fluorescent quenching in oxolane-aqueous solution (volume ratio 1 9) after dropping PA is have studied with fluorescence spectrum means of testing,
Exciting at 335nm, its fluorescence substantially completely quencher when PA addition arrives 5 equivalent, result sees Fig. 1.
Two (benzimidazole) naphthalenes novel fluorescence chemical sensor of synthesis can be applicable to the detection of NAC class explosive, and can realize gaseous state
The detection of PA, Detection results figure is shown in Figure 2.
Embodiment 3
(1) with 1.247 grams of 1-bromo-dodecanes and 0.389 gram of 2,6-bis-(5-tolimidazole) naphthalene (the most aforementioned two (benzimidazole) naphthalenes
In structural formula of compound, benzimidazolyl is positioned at the 2 of naphthalene nucleus, 6-position, and R1=CH3) it is raw material, by the amount of material than n (1-bromine ten
Dioxane): n (2,6-bis-(5-tolimidazole) naphthalene)=5:1 mix homogeneously, temperature be 80 DEG C, 0.160 gram of NaOH solid be
Under conditions of catalyst and 10 milliliters of acetonitriles are solvent, carry out N-alkylation substitution reaction 2 hours；
(2) after reaction terminates, with acetic acid ethyl dissolution, transfer, taking organic facies after washing 3 times, anhydrous magnesium sulfate is dried, and spins off molten
Agent, thick product, through column chromatography for separation, obtains white solid two (benzimidazole) naphthalenes novel fluorescence chemical sensor 0.590 gram, productivity
81%, fusing point 43.8-45.0 DEG C, the structure of product is through infrared spectrum, proton nmr spectra, carbon-13 nmr spectra, ultraviolet spectra, unit
The Organic substance characterizing methods such as element analysis, mass spectrum are confirmed, product dependency structure and data consistent with Example 1.
Product dropping 2,4-DNT in oxolane-aqueous solution (volume ratio 1 9) is have studied with fluorescence spectrum means of testing
(DNT) fluorescent quenching after, excites at 335nm, its fluorescence substantially completely quencher when DNT addition arrives 30 equivalent, knot
Fruit is as shown in Figure 3.
Two (benzimidazole) naphthalenes novel fluorescence chemical sensor of synthesis can be applicable to the detection of NAC class explosive.
Embodiment 4
(1) with 0.214 gram of propargyl bromide and 0.389 gram of 1,5-bis-(5-tolimidazole) naphthalene (the most aforementioned two (benzimidazole) naphthalenes chemical combination
In thing structural formula, benzimidazolyl is positioned at the 1 of naphthalene nucleus, 5-position, and R1=CH3) it is raw material, by the amount of material than n (propargyl bromide):
N (1,5-bis-(5-tolimidazole) naphthalene)=1.8:1 mix homogeneously, temperature be 100 DEG C, 0.240 gram of NaOH solid be catalyst
Under conditions of being solvent with 10 milliliters of dimethyl sulfoxides, carry out N-alkylation substitution reaction 20 hours；
(2) after reaction terminates, with acetic acid ethyl dissolution, transfer, taking organic facies after washing 3 times, anhydrous magnesium sulfate is dried, and spins off molten
Agent, thick product, through column chromatography for separation, obtains thick white shape two (benzimidazole) naphthalenes novel fluorescence chemical sensor 0.225 gram, productivity
48%, the structure of product is organic through infrared spectrum, proton nmr spectra, carbon-13 nmr spectra, ultraviolet spectra, elementary analysis, mass spectrum etc.
Thing characterizing method is confirmed.
The fluorescent quenching after product drips PA in four furanones (THF) solution is have studied, at 317nm with fluorescence spectrum means of testing
Excite, its fluorescence substantially completely quencher when PA addition arrives 125 equivalent.
Two (benzimidazole) naphthalenes novel fluorescence chemical sensor of synthesis can be applicable to the detection of NAC class explosive.
Embodiment 5
(1) with 0.357 gram of propargyl bromide and 0.389 gram of 1,5-bis-(5-tolimidazole) naphthalene (the most aforementioned two (benzimidazole) naphthalenes chemical combination
In thing structural formula, benzimidazolyl is positioned at the 1 of naphthalene nucleus, 5-position, and R1=CH3) it is raw material, by the amount of material than n (propargyl bromide):
N (1,5-bis-(5-tolimidazole) naphthalene)=3:1 mix homogeneously, temperature be 0 DEG C, 0.240 gram of NaOH solid be catalyst and 10
Under conditions of milliliter oxolane is solvent, carry out N-alkylation substitution reaction 20 hours；
(2) after reaction terminates, with acetic acid ethyl dissolution, transfer, taking organic facies after washing 3 times, anhydrous magnesium sulfate is dried, and spins off molten
Agent, thick product, through column chromatography for separation, obtains thick white shape two (benzimidazole) naphthalenes novel fluorescence chemical sensor 0.122 gram, productivity
26%, the structure of product is organic through infrared spectrum, proton nmr spectra, carbon-13 nmr spectra, ultraviolet spectra, elementary analysis, mass spectrum etc.
Thing characterizing method is confirmed.
The fluorescent quenching after product drips PA in four furanones (THF) solution is have studied, at 317nm with fluorescence spectrum means of testing
Excite, its fluorescence substantially completely quencher when PA addition arrives 125 equivalent.
Two (benzimidazole) naphthalenes novel fluorescence chemical sensor of synthesis can be applicable to the detection of NAC class explosive.
Embodiment 6
(1) with the products therefrom in 0.466 gram of 1-azido octane and 0.464 gram of embodiment 4 as raw material, by the amount of material than n (1-
Azido octane): n (products therefrom in embodiment 4)=3:1 mix homogeneously, is 50 DEG C, 0.032 gram of copper sulfate and 0.006 in temperature
Gram copper powder is catalyst and under conditions of 5 milliliters of dimethyl sulfoxides are solvent, carries out Click and reacts 48 hours；
(2) after reaction terminates, with acetic acid ethyl dissolution, transfer, taking organic facies after washing 3 times, anhydrous magnesium sulfate is dried, and spins off molten
Agent, thick product, through column chromatography for separation, obtains faint yellow thick two (benzimidazole) naphthalenes novel fluorescence chemical sensor 0.681 gram, produces
Rate 88%, the structure of product is through infrared spectrum, proton nmr spectra, carbon-13 nmr spectra, ultraviolet spectra, elementary analysis, mass spectrum etc.
Organic substance characterizing method is confirmed.
The fluorescent quenching after it drips 2，4，6-trinitrotoluene (TNT) in THF solution is have studied with fluorescence spectrum means of testing,
Excite at 320nm, its fluorescence substantially completely quencher when TNT addition arrives 8 equivalent.
Two (benzimidazole) naphthalenes novel fluorescence chemical sensor of synthesis can be applicable to the detection of NAC class explosive.
Embodiment 7
(1) with the products therefrom in 0.621 gram of 1-azido octane and 0.464 gram of embodiment 4 as raw material, by the amount of material than n (1-
Azido octane): n (products therefrom in embodiment 4)=4:1 mix homogeneously, is 0 DEG C, 0.032 gram of copper sulfate and 0.006 in temperature
Gram copper powder is catalyst and under conditions of 5 milliliters of oxolanes are solvent, carries out Click and reacts 65 hours；
(2) after reaction terminates, with acetic acid ethyl dissolution, transfer, taking organic facies after washing 3 times, anhydrous magnesium sulfate is dried, and spins off molten
Agent, thick product, through column chromatography for separation, obtains faint yellow thick two (benzimidazole) naphthalenes novel fluorescence chemical sensor 0.217 gram, produces
Rate 28%, the structure of product is through infrared spectrum, proton nmr spectra, carbon-13 nmr spectra, ultraviolet spectra, elementary analysis, mass spectrum etc.
Organic substance characterizing method is confirmed.
The fluorescent quenching after it drips 2，4，6-trinitrotoluene (TNT) in THF solution is have studied with fluorescence spectrum means of testing,
Excite at 320nm, its fluorescence substantially completely quencher when TNT addition arrives 8 equivalent.
Two (benzimidazole) naphthalenes novel fluorescence chemical sensor of synthesis can be applicable to the detection of NAC class explosive.
Embodiment 8
(1) with the products therefrom in 0.311 gram of 1-azido octane and 0.464 gram of embodiment 4 as raw material, by the amount of material than n (1-
Azido octane): n (products therefrom in embodiment 4)=2:1 mix homogeneously, temperature be 100 DEG C, 0.032 gram of copper sulfate and
0.006 gram of copper powder is catalyst and under conditions of 5 milliliters of dimethyl sulfoxides are solvent, carries out Click and reacts 28 hours；
(2) after reaction terminates, with acetic acid ethyl dissolution, transfer, taking organic facies after washing 3 times, anhydrous magnesium sulfate is dried, and spins off molten
Agent, thick product, through column chromatography for separation, obtains faint yellow thick two (benzimidazole) naphthalenes novel fluorescence chemical sensor 0.441 gram, produces
Rate 57%, the structure of product is through infrared spectrum, proton nmr spectra, carbon-13 nmr spectra, ultraviolet spectra, elementary analysis, mass spectrum etc.
Organic substance characterizing method is confirmed.
The fluorescent quenching after it drips 2，4，6-trinitrotoluene (TNT) in THF solution is have studied with fluorescence spectrum means of testing,
Excite at 320nm, its fluorescence substantially completely quencher when TNT addition arrives 8 equivalent.
Two (benzimidazole) naphthalenes novel fluorescence chemical sensor of synthesis can be applicable to the detection of NAC class explosive.
Claims (10)
1. the preparation method for the benzimidazole based chemical sensors of nitro-aromatic explosive fluorescent quenching detection, it is characterised in that
With two (benzimidazole) naphthalene compounds and halogenated hydrocarbons as raw material, main by N-alkylation substitution reaction, prepare and with detection picric acid be
Main, two (benzimidazole) naphthalenes novel fluorescence chemical sensor of the explosive nitroaromatic of detection, i.e. described benzimidazolyl
Chemical sensor.
A kind of benzimidazole based chemical sensors for the detection of nitro-aromatic explosive fluorescent quenching the most according to claim 1
Preparation method, it is characterised in that comprise the steps:
(1) after halogenated hydrocarbons and two (benzimidazole) naphthalene compounds being mixed in organic solvent, add alkali solid catalyst, control
Reaction temperature, carries out N-alkylation substitution reaction；
(2) after reaction terminates, with acetic acid ethyl dissolution, transfer, taking organic facies after washing, anhydrous magnesium sulfate is dried, and rotation boils off molten
Agent, thick product, through column chromatography for separation, obtains two (benzimidazole) naphthalenes novel fluorescence chemical sensor, i.e. described for nitro-aromatic blast
The benzimidazole based chemical sensors of thing fluorescent quenching detection.
A kind of benzimidazolyl chemical sensitisation for the detection of nitro-aromatic explosive fluorescent quenching the most according to claim 1 and 2
The preparation method of device, it is characterised in that
Described halogenated hydrocarbons is propargyl bromide or saturated straight chain end halogenated hydrocarbons CnH2n+1X, wherein n=3-18, X is Cl, Br or I；
Described two (benzimidazole) naphthalene compounds has following structural formula:
Wherein, left side benzimidazolyl may be alternatively located at 5,7,8 positions, and the benzimidazolyl on the right may be alternatively located at 1,3,4 positions,
R1For CH3、C2H5, Cl or Br.
A kind of benzimidazole based chemical sensors for the detection of nitro-aromatic explosive fluorescent quenching the most according to claim 2
Preparation method, it is characterised in that in step (1), described alkali solid catalyst be sodium hydroxide, sodium carbonate, potassium hydroxide and
One or both in sodium hydride, described organic solvent is the one in acetonitrile, dimethyl sulfoxide, oxolane, ethyl acetate and toluene
Or two kinds；The mol ratio of described halogenated hydrocarbons and two (benzimidazole) naphthalene compounds is 1.8 1～5.0:1；Described alkali solid catalyst with
The mol ratio of two (benzimidazole) naphthalene compounds is 2 1～6:1.
A kind of benzimidazole based chemical sensors for the detection of nitro-aromatic explosive fluorescent quenching the most according to claim 2
Preparation method, it is characterised in that in step (1), the reaction temperature of described N-alkylation substitution reaction is 0～100 DEG C, during reaction
Between be 1～20 hour.
A kind of benzimidazole based chemical sensors for the detection of nitro-aromatic explosive fluorescent quenching the most according to claim 2
Preparation method, it is characterised in that when halogenated hydrocarbons is propargyl bromide in step (1), reaction obtain containing end alkynyl radical two (benzimidazole)
Naphthalene compounds continues to carry out Click reaction under copper salt catalyst effect with alkyl azide, then is prepared by step (2)
Benzimidazole based chemical sensors for the detection of nitro-aromatic explosive fluorescent quenching.
A kind of benzimidazole based chemical sensors for the detection of nitro-aromatic explosive fluorescent quenching the most according to claim 6
Preparation method, it is characterised in that the reaction temperature of described Click reaction is 0～100 DEG C, and the response time is 28～65 hours.
A kind of benzimidazole based chemical sensors for the detection of nitro-aromatic explosive fluorescent quenching the most according to claim 6
Preparation method, it is characterised in that described alkyl azide and mol ratio containing end alkynyl radical two (benzimidazole) naphthalene compounds be 2 1～
4:1；The reaction dissolvent of described Click reaction is one or both in acetonitrile, dimethyl sulfoxide, oxolane, ethyl acetate or toluene；
Described copper salt catalyst is cuprous salt catalyst or is mixed with, by cupric salt and reducing agent, the material obtained, and wherein cuprous salt is urged
Agent is CuI, CuCl or CuBr, and cupric salt is Schweinfurt green, copper sulfate or copper chloride, and reducing agent is copper powder.
A kind of benzimidazole based chemical sensors for the detection of nitro-aromatic explosive fluorescent quenching the most according to claim 6
Preparation method, it is characterised in that described alkyl azide is saturated straight chain end azide CnH2n+1N3, wherein n=4-12.
10. the benzimidazole for the detection of nitro-aromatic explosive fluorescent quenching prepared by preparation method described in any one of claim 1-9
Based chemical sensors.
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| CN113512038A (en) * | 2021-07-20 | 2021-10-19 | 华南师范大学 | Benzo [4,5] imidazo [1,2-a ] pyridine derivative and preparation method and application thereof |
| CN113801067A (en) * | 2021-08-11 | 2021-12-17 | 华南师范大学 | Benzimidazole derivative and application thereof in detection of nitro aromatic explosives |
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| CN110358106A (en) * | 2019-08-02 | 2019-10-22 | 湖北师范大学 | A kind of anion frame metal-organic framework material and its preparation method and application of pair of nitro-aromatic explosive sensing |
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| CN113801067B (en) * | 2021-08-11 | 2023-02-03 | 华南师范大学 | Benzimidazole derivative and application thereof in detection of nitro aromatic explosives |
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