CN1300124C - Double heterocyclic tri azene compound and its preparing method and use - Google Patents
Double heterocyclic tri azene compound and its preparing method and use Download PDFInfo
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- CN1300124C CN1300124C CNB2005100126532A CN200510012653A CN1300124C CN 1300124 C CN1300124 C CN 1300124C CN B2005100126532 A CNB2005100126532 A CN B2005100126532A CN 200510012653 A CN200510012653 A CN 200510012653A CN 1300124 C CN1300124 C CN 1300124C
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Abstract
The present invention discloses a double-heterocyclic triazene compound 1, 3-double(2-benzothiazolyl diazo amino) benzene(BBTAB), a preparation method and application thereof. The preparation method comprises: after azotized in a double mode, lentine is coupled with 2-benzothiazolyl diazo amino. In an alkaline medium under the existence of beta-CD, after the double-heterocyclic triazene structure of a reagent is matched with copper ions, BBTAB rigidity is increased. Consequently, the fluorescence of the reagent is obviously increased. On the basis that a novel fluorescence analysis method for measuring Cu(II) by BBTAB is established. Different water samples containing copper ions are tested, and a result is satisfactory. The BBTAB can also be used as a coloring agent.
Description
Technical field
The present invention relates to a kind of pair of tri azene compound, particularly contain compound of double heterocyclic tri azene structure and preparation method thereof, and its application.
Background technology
Easy and transition metal ion cooperation is good coordinating group (J.Barker, N.D.Cameron, M.Kilner, et al, J.Chem.Soc.Dalton Trans., 12 (1991) 3435.) after the deprotonation of triazene structure.Triazene reagent is the good developer of metal ions such as cadmium, mercury, copper, nickel, silver, because of it has highly sensitive, advantage such as easily synthetic, just constantly be subjected to people's attention, but it is bigger that its coexisting ion disturbs, selectivity awaits to improve, and usually only is used for photometric analysis as developer, seldom is used for the fluoroscopic examination of metal ion as the coordination structure of fluorescent reagent.Two triazene structure reagent are than general triazene reagent sensitivity higher (Z.G.Chen, W.Wen, F.Y.Lei, etal, Chinese J.Anal.Chem., 31 (2003) 1279).Therefore, two triazene structures and the reagent with fluorescent characteristic are combined, formation has the double heterocyclic tri azene structure reagent of special big conjugated system, is good developer thereby be expected synthetic, is again fluorescent reagent highly sensitive, that selectivity is good.
Summary of the invention
The purpose of this invention is to provide a kind of be good developer be again the double heterocyclic tri azene compound of highly sensitive, that selectivity is good fluorescent reagent, and preparation method thereof, and its application.
The present invention combines two triazene structures and the benzothiazoles reagent with fluorescent characteristic, formed the double heterocyclic tri azene structure of semi-circular big conjugated system, and the double heterocyclic tri azene structure of benzothiazole makes ligating atom be nitrogen-atoms, thereby its selectivity improves greatly, thus synthesized a kind of be good developer be again fluorescent reagent highly sensitive, that selectivity is good.In the alkaline medium in the presence of β-CD, the double heterocyclic tri azene structure cooperates with cupric ion, its rigidity is increased, thereby its fluorescence significantly strengthens, and based on this, has set up it and has measured the new fluorescence analysis method of Cu (II).
A kind of double heterocyclic tri azene compound provided by the invention is 1, two (2-[4-morpholinodithio diazoamino) benzene (BBTAB) of 3-, and its molecular structural formula:
The preparation method of BBTAB of the present invention comprises the following steps:
(1) in flask, adds the 3.0mL concentrated hydrochloric acid, under-15 ℃ of stirrings, slowly add the aqueous solution 10.0mL that is dissolved with 0.7 gram Sodium Nitrite, drip the suspension that is made into by 0.54g mphenylenediamine and 5.0mL concentrated hydrochloric acid then, and quicken to stir, reacted 30 minutes, make diazotization complete, get the diazonium saline solution;
(2) 1.5g 2-aminobenzothiazole is dissolved in the 10mL ethanol, adds down slowly above-mentioned diazonium saline solution in-15 ℃ of stirrings, during to regulate pH with saturated sodium carbonate solution be 7～8, reacted standing over night, suction filtration, successively water and washing with alcohol 2 hours.Dried thick product N, dinethylformamide: 2: 3 by volume twice recrystallization of ethanol gets red-brown 1, the two pure product of (2-[4-morpholinodithio diazoamino) benzene of 3-.
Coincide through ultimate analysis, infrared spectra and nucleus magnetic resonance spectral test and target product.
This reagent is highly sensitive, the fluorescent reagent that selectivity is good that detects Cu (II) in the alkaline medium in the presence of β-CD.This reagent also can be used as developer.
Advantage of the present invention and positively effect: on (1)-N=N-NH-coupling base nitrogen-atoms to the avidity of metal ion-nitrogen-atoms on the N=N-base is big to the avidity of metal ion, is better coordinating group; (2) BBTAB has semi-circular double heterocyclic tri azene structure, and after metallic ion coordination, its rigidity increases, thereby its fluorescence quantum yield is increased, and is the novel fluorescence reagent highly sensitive, that selectivity is good; (3) BBTAB still is good developer.
Preparation method of the present invention is simple, and is with low cost, and it is good to be used to detect selectivity, highly sensitive, and stable performance can be used for the fluoroscopic examination of Cu (II) in the alkaline medium under β-CD existence.Also can be used as developer.
Embodiment
Embodiment 1:
(1) in flask, adds the 3.0mL concentrated hydrochloric acid, under-15 ℃ of stirrings, slowly add the aqueous solution 10.0mL that is dissolved with 0.7 gram Sodium Nitrite, drip the suspension that is made into by 0.54g mphenylenediamine and 5.0mL concentrated hydrochloric acid then, and quicken to stir, reacted 30 minutes, make diazotization complete, get the diazonium saline solution;
(2) 1.5g 2-aminobenzothiazole is dissolved in the 10mL ethanol, adds down slowly above-mentioned diazonium saline solution in-15 ℃ of stirrings, during to regulate pH with saturated sodium carbonate solution be 7～8, reacted standing over night, suction filtration, successively water and washing with alcohol 2 hours.Dried thick product N, dinethylformamide: twice recrystallization of ethanol (2: 3) gets reddish brown colour purity product BBTAB.
Coincide through ultimate analysis, infrared spectra and nucleus magnetic resonance spectral test and target product.
Embodiment 2:
The fluorescent reagent 1 that contains the double heterocyclic tri azene structure, two (2-[4-morpholinodithio diazoamino) benzene (BBTAB) of 3-in the alkaline medium in the presence of β-CD to fluoroscopic examination and the application thereof of Cu (II).
In the 25mL colorimetric cylinder, add the water sample of the copper ions of certain volume successively, 1.0 * 10
-5The BBTAB ethanolic soln 2.5mL of mol/L, the pH value is boric acid-sodium hydroxide buffer solution 3.0mL of 8.4,1.6 * 10
-4Mol/L β-CD aqueous solution 2.0mL, then with the water constant volume, with LS-55 type fluorescent/phosphorescent/luminescence spectrophotometer (U.S. Perkin Elmer company) in λ
Cx/ λ
Cm=386nm/492nm place surveys its fluorescence intensity.To the cupric ion in the different water samples measurement result see Table 1.
Cupric ion in the different water samples of table 1 measurement result
aRSD：relative standard deviation(n＝5)
| Sample | Spiked (μg/L) | Found(μg/L) | Recovery(％) | RSD a(％) | |||
| This method | FAAS | This method | FAAS | This method | FAAS | ||
| Double distilled water | 0 20 | ＜LOD b 20.1 | ＜LOD 20.1 | - | - | 3.8 4.0 | 4.3 4.5 |
| Tap water | 0 20 | 2.1 21.9 | 2.0 22.1 | 99.1 | 100.4 | 3.5 3.4 | 3.7 3.5 |
| River water | 0 20 | 106.7 126.9 | 106.3 126.8 | 100.2 | 100.3 | 4.1 4.3 | 4.6 4.7 |
bLOD：limit of detection
Claims (3)
1, a kind of double heterocyclic tri azene compound is 1, two (2-[4-morpholinodithio diazoamino) benzene of 3-, and its molecular structural formula:
2, according to the preparation method of the described a kind of double heterocyclic tri azene compound of claim 1, comprise the following steps:
(1) in flask, adds the 3.0mL concentrated hydrochloric acid, under-15 ℃ of stirrings, slowly add the aqueous solution 10.0mL that is dissolved with 0.7 gram Sodium Nitrite, drip the suspension that is made into by 0.54g mphenylenediamine and 5.0mL concentrated hydrochloric acid then, and quicken to stir, reacted 30 minutes, make diazotization complete, get the diazonium saline solution;
(2) 1.5g 2-aminobenzothiazole is dissolved in the 10mL ethanol, slowly add above-mentioned diazonium saline solution down in-15 ℃ of stirrings, regulating pH with saturated sodium carbonate solution during this time is 7～8, reacted 2 hours, standing over night, suction filtration, successively water and washing with alcohol. dried thick product N, dinethylformamide: 2: 3 by volume twice recrystallization of ethanol gets red-brown 1, the two pure product of (2-[4-morpholinodithio diazoamino) benzene of 3-.
3, according to the purposes of the described a kind of double heterocyclic tri azene compound of claim 1, as the application of fluorescent reagent and developer.
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| CN101270085B (en) * | 2008-05-16 | 2010-08-11 | 山西大同大学 | Bis(8-quinoline diazo amido)-biphenyl, preparation method and application thereof |
| CN102311404B (en) * | 2011-10-03 | 2013-10-30 | 山西大同大学 | 2,2'-bis(2-hydroxy-4-sulfonic-1-naphthylamine azoxyl)-5,5'-dimethyl-4,4'-bithiazole and preparation method thereof |
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| CN1478731A (en) * | 2003-06-30 | 2004-03-03 | 雁北师范学院 | Preparation method of triazene polymer chelant and its application |
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