CN103319475B - N'-benzothiazolyl-3-formamido-7-(N, N-diethyl)coumarin, and preparation method and applications thereof - Google Patents
N'-benzothiazolyl-3-formamido-7-(N, N-diethyl)coumarin, and preparation method and applications thereof Download PDFInfo
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- CN103319475B CN103319475B CN201310042509.8A CN201310042509A CN103319475B CN 103319475 B CN103319475 B CN 103319475B CN 201310042509 A CN201310042509 A CN 201310042509A CN 103319475 B CN103319475 B CN 103319475B
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- diethyl
- benzothiazolyl
- coumarin
- methane amide
- diethylin
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Abstract
The invention relates to a fluorescence reagent, specifically to a N'-benzothiazolyl-3-formamode-7-(N, N-diethyl)coumarin compound containing a heterocycle. The objective of the invention is to provide a N'-benzothiazolyl-3-formamode-7-(N, N-diethyl)coumarin compound with high fluorescence sensitivity and good selectivity. A specific preparation method is that: reacting 4-(diethylamino)salicylaldehyde with diethyl malonate in the presence of piperidine and acetic acid to generate ethyl 7-(diethylamino)coumarin-3- carboxylate allowing the product to be subjected to a hydrolysis reaction of ester under an alkaline condition, adjusting pH to obtain 7-(diethylamino)coumarin-3-carboxylic acid, then obtaining N'-benzothiazolyl-3-formamode-7-(N,N-diethyl)coumarin by an amidation reaction of 7-(diethylamino)coumarin-3-carboxylic acid and 2-aminobenzothiazole.
Description
Technical field
The present invention relates to a kind of fluorescent reagent, specifically relate to a kind of N '-(benzothiazolyl)-3-methane amide-7-N containing heterocycle, N-diethyl-coumarin compound, the invention still further relates to the preparation method and application of this compound.
Background technology
Coumarin kind compound is the important natural crossing cyclic cpds of a class that occurring in nature extensively exists, and has unique biological activity and excellent optical characteristics.The parent nucleus chromene of coumarin kind compound is the colorless substance not having fluorescence, but the coumarin derivatives after replacing, and particularly 7 is introduced electron-donating group, 3 or 4 upper introduce electron-withdrawing groups after, form push and pull component, just obtain hyperfluorescenceZeng Yongminggaoyingguang material.And benzothiazole group is as strong electron-withdrawing group group, can be used for constructing fluorescent organic molecule.
Summary of the invention
The object of this invention is to provide N '-(benzothiazolyl)-3-methane amide-7-N that a kind of fluorescence sensitivity is high, selectivity is good, N-diethyl-coumarin compound, the present invention also provides the preparation method and application of this compound.
N ' of the present invention-(benzothiazolyl)-3-methane amide-7-N, the molecular structure of N-diethyl-tonka bean camphor is as follows
Preparation method of the present invention is:
By 4-(diethylin)-salicylic aldehyde reacts with diethyl malonate and generates 7-(diethylin under the condition of piperidines, acetic acid)-Coumarin-3-carboxylic Acid Ethyl Ester, 7-(diethylin)-Coumarin-3-carboxylic Acid Ethyl Ester carries out ester hydrolysis reaction in the basic conditions, adjust ph obtains 7-(diethylin)-coumarin-3-carboxylic acid, again by 7-(diethylin)-coumarin-3-carboxylic acid and 2-aminobenzothiazole carry out acid amides and react and prepare N '-(benzothiazolyl)-3-methane amide-7-N, N-diethyl-tonka bean camphor.
Concrete preparation method is:
By 4-(diethylin)-salicylic aldehyde is at piperidines, with diethyl malonate stirring and refluxing 2.5 ~ 3h under the condition of acetic acid, reaction generates 7-(diethylin)-Coumarin-3-carboxylic Acid Ethyl Ester, this compound carries out ester hydrolysis reaction in the basic conditions, adjust ph is 2 ~ 3, obtain 7-(diethylin)-coumarin-3-carboxylic acid, again by 7-(diethylin)-coumarin-3-carboxylic acid and 2, 6-diamino-pyridine reacts 4 ~ 6h under the condition adding dicyclohexylcarbodiimide and 4-dimethylaminopyridine, prepare N '-(benzothiazolyl)-3-methane amide-7-N, N-diethyl-tonka bean camphor.
The N ' that the present invention prepares-(benzothiazolyl)-3-methane amide-7-N, N-diethyl-tonka bean camphor can be applied to the fluoroscopic examination of metal ion as fluorescent reagent.
Especially, the N ' that the present invention prepares-(benzothiazolyl)-3-methane amide-7-N, N-diethyl-tonka bean camphor as fluorescent reagent, can be applied to H
2in O/DMF (3/7, v/v) medium, the fluoroscopic examination of Ag (I), is at H
2the highly sensitive of Ag (I) in tealeaves and hair, the fluorescent reagent of highly selective is detected in O/DMF (3/7, v/v) medium.
The N ' that the present invention prepares-(benzothiazolyl)-3-methane amide-7-N, N-diethyl-tonka bean camphor has the following advantages:
(1), 7 tonka bean camphor structures replacing upper diethylins and benzothiazole combine, and forms push and pull component, obtain a kind of compound with hyperfluorescenceZeng Yongminggaoyingguang;
(2), N '-(benzothiazolyl)-3-methane amide-7-N, N-diethyl-tonka bean camphor has acid amides, benzothiazole structure, after nitrogen-atoms on amide oxygen atom and benzothiazole and metallic ion coordination, its fluorescence quantum yield reduces, and is the novel fluorescence reagent of highly sensitive, highly selective;
(3), preparation method is simple, with low cost, stable performance.
Accompanying drawing explanation
Fig. 1 is 7-(diethylin) infrared spectrogram of-Coumarin-3-carboxylic Acid Ethyl Ester;
Fig. 2 is 7-(diethylin) nmr spectrum of-Coumarin-3-carboxylic Acid Ethyl Ester;
Fig. 3 is 7-(diethylin) infrared spectrogram of-coumarin-3-carboxylic acid;
Fig. 4 is 7-(diethylin) nmr spectrum of-coumarin-3-carboxylic acid;
Fig. 5 is N '-(benzothiazolyl)-3-methane amide-7-N, the infrared spectrogram of N-diethyl-tonka bean camphor;
Fig. 6 is N '-(benzothiazolyl)-3-methane amide-7-N, the nmr spectrum of N-diethyl-tonka bean camphor;
Fig. 7 is N '-(benzothiazolyl)-3-methane amide-7-N, and N-diethyl-tonka bean camphor detects the fluorescence spectrum figure of Ag (I) in the aqueous solution as fluorescent reagent;
Fig. 8 is N '-(benzothiazolyl)-3-methane amide-7-N, and N-diethyl-tonka bean camphor detects Ag (I) linear dependence figure in the aqueous solution as fluorescent reagent.
Embodiment
Embodiment 1
A kind of N '-(benzothiazolyl)-3-methane amide-7-N, N-diethyl-tonka bean camphor, its molecular structure is as follows:
Concrete preparation method comprises the following steps:
1), 7-(diethylin) preparation of-Coumarin-3-carboxylic Acid Ethyl Ester: by 4.8g4-(diethylin)-salicylic aldehyde is dissolved in 25mL ethanol, add 4.8mL diethyl malonate, 3 piperidines, 1 acetic acid, water-bath return stirring 3h, 25mL water is added after cooling, be cooled to 0 DEG C, suction filtration, with the ice ethanolic soln washing of 50%, obtains straight product 7-(diethylin with the ethanolic soln recrystallization of 50% after dry)-Coumarin-3-carboxylic Acid Ethyl Ester; Productive rate 43.4%
Through ultimate analysis, infrared spectra and nucleus magnetic resonance spectral test and target product 7-(diethylin)-Coumarin-3-carboxylic Acid Ethyl Ester coincide.Make a concrete analysis of as follows:
Ultimate analysis (C
16h
19nO
4) measured value (%; Theoretical value): C67.96 (66.42), N5.00 (4.84), H6.528 (6.62).
Infrared analysis: see Fig. 1, FT-IR (KBr compressing tablet) v/cm
-1: 3027 is the absorption peak of Ar-H, and 2975 is-CH
3absorption peak, 1755 is lactone C=O absorption peak, and 1701 is C=O absorption peak in-COEt, and 1615,1592,1513 is phenyl ring skeleton absorption peak, and 1422-C=CH-absorption peaks, 1222 have-C-O-absorption peak.
Nuclear magnetic resonance spectrum: see Fig. 2,
1h NMR (400MHz, CDCl
3): δ 8.41 (s, 1H ,-C=CH), 7.34 (m, 1H, ArH), 6.59 (d, J=8.9Hz, 1H, ArH), 6.44 (d, J=2.1Hz, 1H, ArH), 4.35 (d, J=7.1Hz, 2H ,-CH
2-), 3.43 (q, J=7.1Hz, 4H ,-CH
2-), 1.37 (t, J=7.1Hz, 3H ,-CH
3), 1.21 (t, J=7.1Hz, 6H ,-CH
3);
2), 7-(diethylin) preparation of-coumarin-3-carboxylic acid: by 2.89g7-(diethylin)-Coumarin-3-carboxylic Acid Ethyl Ester is dissolved in 15mL ethanol, add the NaOH solution of 15mL10%, water-bath return stirring 15min, the pH value regulating mixed solution with concentrated hydrochloric acid is 2, cooling, suction filtration, with the ice ethanolic soln washing of 50%, straight product 7-(diethylin is obtained with the ethanolic soln recrystallization of 50% after dry)-coumarin-3-carboxylic acid, productive rate 71.2%
Through ultimate analysis, infrared spectra and nucleus magnetic resonance spectral test and target product 7-(diethylin)-coumarin-3-carboxylic acid coincide.Make a concrete analysis of as follows:
Ultimate analysis (C
14h
15nO
4) measured value (%; Theoretical value): C64.92 (64.35), N5.44 (5.36), H5.876 (5.78);
Infrared analysis: see Fig. 3, FT-IR (KBr compressing tablet) v/cm
-1: 3110 is the absorption peak of Ar-H, and 2986 is-CH
3absorption peak, 2924 is-OH absorption peak, and 1735 is lactone C=O absorption peak, and 1667 is C=O absorption peak in-COOH, and 1620,1566,1511 is phenyl ring skeleton absorption peak, 1420-C=CH-absorption peaks, and 1357 have C-N absorption peak, and 1263 is C-O absorption peak;
Nuclear magnetic resonance spectrum: see Fig. 4,
1h NMR (400MHz, CDCl
3): δ 12.52 (s, 1H ,-OH), 8.57 (s, 1H ,-C=CH), 7.62 (d, J=9.0Hz, 1H, ArH), 6.78 (d, J=8.9Hz, 1H, ArH), 6.55 (s, 1H, Ar-H), 3.46 (q, J=6.81Hz, 4H ,-CH
2-), 1.11 (q, J=6.9Hz, 6H ,-CH
3);
3), N '-(benzothiazolyl)-3-methane amide-7-N, the preparation of N-diethyl-tonka bean camphor: by 0.84g7-(diethylin)-coumarin-3-carboxylic acid is dissolved in 25mL trichloromethane, add 1.13g2-aminobenzothiazole, 12.5mg4-dimethyl aminopyridine, slowly add 0.57g dicyclohexylcarbodiimide while stirring, sealing, stirring at room temperature reaction 6h, reaction mixture is freezing, filter, mother liquor 20mL water washing 3 times, with anhydrous sodium sulfate drying, be spin-dried for, be that the methylene dichloride of 5:1 and ethyl acetate mixtures cross post by volume ratio, straight product N '-(benzothiazolyl)-3-methane amide-7-N is obtained with the ethanolic soln recrystallization of 50% after obtaining thick product drying, N-diethyl-tonka bean camphor, productive rate 43.9%.
Through ultimate analysis, infrared spectra and nucleus magnetic resonance spectral test and target product N '-(benzothiazolyl)-3-methane amide-7-N, N-diethyl-tonka bean camphor coincide.Make a concrete analysis of as follows:
Ultimate analysis (C
21h
19n
3o
3s) measured value (%; Theoretical value): C65.34 (64.10), N10.81 (10.67), S7.63 (8.15), H5.255 (4.87);
Infrared analysis: see Fig. 5, FT-IR (KBr compressing tablet) v/cm
-1: 3201 places are-NH-absorption peak, and 3060 is the absorption peak of Ar-H, and 1705 is lactone C=O absorption peak, and 1660 is C=O absorption peak in acid amides, and 1620,1579,1504 is phenyl ring skeleton absorption peak;
Nuclear magnetic resonance spectrum: see Fig. 6,
1h NMR (400MHz, DMSO-d
6) δ 12.11 (s, 1H ,-C=CH), 8.86 (s, 1H ,-NH), 8.01 (s, 1H, ArH), 7.78 (d, J=8.3Hz, 2H, ArH), 7.46 (t, J=7.4Hz, 1H, ArH), 7.34 (t, J=7.3Hz, 1H, ArH), 6.90 (d, J=7.5Hz, 1H, ArH), 6.70 (s, 1H, ArH), 3.54 (d, J=6.8Hz, 4H ,-CH
2), 1.18 (t, J=6.6Hz, 6H ,-CH
3).
Embodiment 2:
In 10mL colorimetric cylinder, add the aqueous solution of a certain amount of silver ion successively, 1.0 × 10
-6the N ' of mol/L-(benzothiazolyl)-3-methane amide-7-N, N-diethyl-tonka bean camphor solution 3mL; Then with the solution constant volume of H2O/DMF=3/7 (V:V).In λ ex/ λ em=447nm/492nm place, survey its fluorescence intensity with Hitachi F-2500 type spectrophotofluorometer, carry out fluorescence spectrometry to Ag (I) aqueous solution containing different concns, linear equation is F=2.37 × 10
3-2.36 × 10
7c, linearity range is 1.67 μm of ol/L ~ 83.3 μm ol/L, and linearly dependent coefficient is R2=0.995 (n=6), specifically sees Fig. 7,8.
Embodiment 3:
Get Tea Samples (Mount Huang Mao Feng) to wash after acetone immersion 50min, in 80 degree of lower oven dry, precise 5.0g tealeaves, adds 25ml HClO again
4-HNO
3(volume ratio 1:8) mixed solution, after heating is fully reacted, stirs evaporate to dryness, collects powder as in centrifuge tube, adds 5ml H
2sO
4the aqueous solution (volume ratio 1:1), puts into whizzer after mixing, with the centrifugal 4h of 2500r/s until upper strata presents the stillness of night, gets 10 μ l supernatant liquors at every turn and measures, in 10mL colorimetric cylinder, add a certain amount of sample solution successively, 1.0 × 10
-6the N ' of mol/L-(benzothiazolyl)-3-methane amide-7-N, N-diethyl-tonka bean camphor solution 3mL; Then with H
2the solution constant volume of O/DMF=3/7 (V:V), in λ
ex/ λ
em=447nm/492nm place, with Hitachi F-2500 type fluorescent spectrophotometer assay, the results are shown in Table 1.
Embodiment 4
Get middle-aged people's hair, adopt method process similarly to Example 2, in 10mL colorimetric cylinder, add a certain amount of sample solution successively, 1.0 × 10
-6the N ' of mol/L-(benzothiazolyl)-3-methane amide-7-N, N-diethyl-tonka bean camphor solution 3mL; Then with H
2the solution constant volume of O/DMF=3/7 (V:V), in λ
ex/ λ
em=447nm/492nm place, with Hitachi F-2500 type fluorescent spectrophotometer assay, the results are shown in Table 1.
The detected result of silver ions in table 1 tealeaves and hair
Claims (5)
1. N '-(benzothiazolyl)-3-methane amide-7-N, N-diethyl-tonka bean camphor, is characterized in that: N '-(benzothiazolyl)-3-methane amide-7-N, and the molecular structure of N-diethyl-tonka bean camphor is as follows:
2. N ' according to claim 1-(benzothiazolyl)-3-methane amide-7-N, the preparation method of N-diethyl-tonka bean camphor: it is characterized in that: by 4-(diethylin)-salicylic aldehyde at piperidines, react with diethyl malonate under the condition of acetic acid and generate 7-(diethylin)-Coumarin-3-carboxylic Acid Ethyl Ester, 7-(diethylin)-Coumarin-3-carboxylic Acid Ethyl Ester carries out ester hydrolysis reaction in the basic conditions, adjust ph obtains 7-(diethylin)-coumarin-3-carboxylic acid, again 7-(diethylin)-coumarin-3-carboxylic acid and 2-aminobenzothiazole are carried out acid amides to react and prepare N '-(benzothiazolyl)-3-methane amide-7-N, N-diethyl-tonka bean camphor.
3. N ' according to claim 1-(benzothiazolyl)-3-methane amide-7-N, the application of N-diethyl-tonka bean camphor, is characterized in that: the fluoroscopic examination being applied to metal ion as fluorescent reagent.
4. N ' according to claim 3-(benzothiazolyl)-3-methane amide-7-N, the application of N-diethyl-tonka bean camphor, is characterized in that: at H
2the volume ratio of O/DMF is detect Ag (I) in 3/7 medium.
5. N ' according to claim 3-(benzothiazolyl)-3-methane amide-7-N, the application of N-diethyl-tonka bean camphor, is characterized in that: at H
2the volume ratio of O/DMF is detect Ag (I) in tealeaves and hair in 3/7 medium.
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CN105461675B (en) * | 2015-11-24 | 2017-08-25 | 山西大同大学 | 7 N of one kind, the benzopyrone of 3 carboxylic acid of N diethylaminocoumarins 7 and preparation method and application |
CN105777729A (en) * | 2016-05-31 | 2016-07-20 | 浙江工业大学 | Coumarin amides compound as well as preparation method and application of coumarin amides compound |
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CN102516235A (en) * | 2011-11-08 | 2012-06-27 | 华南师范大学 | Dibenzothiophene chalcone containing coumarin skeleton and synthesis method and application thereof |
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JPH04134446A (en) * | 1990-09-27 | 1992-05-08 | Konica Corp | Silver halide photographic sensitive material |
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US4146712A (en) * | 1976-03-11 | 1979-03-27 | Ciba-Geigy Corporation | Process for the manufacture of coumarin dyes |
CN102516235A (en) * | 2011-11-08 | 2012-06-27 | 华南师范大学 | Dibenzothiophene chalcone containing coumarin skeleton and synthesis method and application thereof |
Non-Patent Citations (1)
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