CN103319475A - 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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- CN103319475A CN103319475A CN2013100425098A CN201310042509A CN103319475A CN 103319475 A CN103319475 A CN 103319475A CN 2013100425098 A CN2013100425098 A CN 2013100425098A CN 201310042509 A CN201310042509 A CN 201310042509A CN 103319475 A CN103319475 A CN 103319475A
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- benzothiazolyl
- coumarin
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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 that contains 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.The parent nucleus chromene of coumarin kind compound is the colorless substance that does not have fluorescence, but the coumarin derivatives after replacing, particularly go up and introduce electron-donating group for 7,3 or 4 go up introduce electron-withdrawing group after, form the push-and-pull electron system, just obtain the hyperfluorescence material.And the benzothiazole group can be used for constructing the fluorescence organic molecule as strong electron-withdrawing group group.
Summary of the invention
The purpose of this invention is to provide a kind of fluorescence sensitivity height, N '-(benzothiazolyl)-3-methane amide-7-N that 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:
With the 4-(diethylin)-salicylic aldehyde generates the 7-(diethylin with diethyl malonate reaction under the condition of piperidines, acetic acid)-the coumarin-3-carboxylic acid ethyl ester, the 7-(diethylin)-the coumarin-3-carboxylic acid ethyl ester carries out the hydrolysis reaction of ester under alkaline condition, regulate the pH value and obtain the 7-(diethylin)-coumarin-3-carboxylic acid, again with the 7-(diethylin)-coumarin-3-carboxylic acid and 2-aminobenzothiazole carry out the acid amides prepared in reaction and obtain N '-(benzothiazolyl)-3-methane amide-7-N, N-diethyl-tonka bean camphor.
Concrete preparation method is:
With the 4-(diethylin)-salicylic aldehyde is at piperidines, under the condition of acetic acid with diethyl malonate stirring and refluxing 2.5～3h, reaction generates the 7-(diethylin)-the coumarin-3-carboxylic acid ethyl ester, this compound carries out the hydrolysis reaction of ester under alkaline condition, regulating the pH value is 2～3, obtain the 7-(diethylin)-coumarin-3-carboxylic acid, again with the 7-(diethylin)-coumarin-3-carboxylic acid and 2, the 6-diamino-pyridine reacts 4～6h under the condition that adds 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 used as the fluoroscopic examination that fluorescent reagent is applied to metal ion.
Especially, the N ' that the present invention prepares-(benzothiazolyl)-3-methane amide-7-N, N-diethyl-tonka bean camphor can be used as fluorescent reagent, is applied to H
2(3/7, the v/v) fluoroscopic examination of Ag (I) in the medium is at H to O/DMF
2O/DMF (3/7, v/v) detect the highly sensitive of Ag (I) in tealeaves and the hair, the fluorescent reagent of highly selective in the medium.
The N ' that the present invention prepares-(benzothiazolyl)-3-methane amide-7-N, N-diethyl-tonka bean camphor has the following advantages:
(1), tonka bean camphor structure and the benzothiazole of diethylin combines in 7 replacements, forms the push-and-pull electron system, obtains a kind of compound with hyperfluorescence;
(2), N '-(benzothiazolyl)-3-methane amide-7-N, N-diethyl-tonka bean camphor has acid amides, and the benzothiazole structure is behind the nitrogen-atoms and metallic ion coordination on amide oxygen atom and the benzothiazole, its fluorescence quantum yield reduces, and is the novel fluorescence reagent of highly sensitive, highly selective;
(3), the preparation method is simple, with low cost, stable performance.
Description of drawings
Fig. 1 is the 7-(diethylin)-infrared spectrogram of coumarin-3-carboxylic acid ethyl ester;
Fig. 2 is the 7-(diethylin)-nmr spectrum of coumarin-3-carboxylic acid ethyl ester;
Fig. 3 is the 7-(diethylin)-infrared spectrogram of coumarin-3-carboxylic acid;
Fig. 4 is the 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
A kind of N '-(benzothiazolyl)-3-methane amide-7-N, N-diethyl-tonka bean camphor, its molecular structure is as follows:
Concrete preparation method may further comprise the steps:
1), 7-(diethylin)-preparation of coumarin-3-carboxylic acid ethyl ester: with the 4.8g4-(diethylin)-salicylic aldehyde is dissolved in 25mL ethanol, add 4.8mL diethyl malonate, 3 piperidines, 1 acetic acid, water-bath refluxes and stirs 3h, the cooling back adds 25mL water, be cooled to 0 ℃, suction filtration, with 50% ice ethanolic soln washing, dry back gets straight product 7-(diethylin with 50% ethanolic soln recrystallization)-the 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)-the coumarin-3-carboxylic acid ethyl ester is identical.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 are-CH
3Absorption peak, 1755 is lactone C=O absorption peak, 1701 be-COEt in the C=O absorption peak, 1615,1592,1513 is phenyl ring skeleton absorption peak, 1422-C=CH-absorption peak, 1222 have-the 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: with the 2.89g7-(diethylin)-the coumarin-3-carboxylic acid ethyl ester is dissolved in the 15mL ethanol, the NaOH solution that adds 15mL10%, water-bath refluxes and stirs 15min, the pH value of regulating mixed solution with concentrated hydrochloric acid is 2, cooling, suction filtration, the ice ethanolic soln washing with 50%, dry back gets straight product 7-(diethylin with 50% ethanolic soln recrystallization)-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 is identical.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 are-CH
3Absorption peak, 2924 are-the OH absorption peak, 1735 is lactone C=O absorption peak, 1667 be-COOH in the C=O absorption peak, 1620,1566,1511 is phenyl ring skeleton absorption peak, 1420-C=CH-absorption peak, 1357 have the C-N absorption peak, 1263 is the 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: with the 0.84g7-(diethylin)-coumarin-3-carboxylic acid is dissolved in the 25mL trichloromethane, add the 1.13g2-aminobenzothiazole, 12.5mg4-dimethyl aminopyridine, slowly add the 0.57g dicyclohexylcarbodiimide while stirring, sealing, stirring at room reaction 6h, reaction mixture is freezing, filter, mother liquor is used anhydrous sodium sulfate drying with 20mL water washing 3 times, is spin-dried for, be that methylene dichloride and the ethyl acetate mixed solution of 5:1 crossed post with volume ratio, behind the thick product drying ethanolic soln recrystallization with 50% get straight product N '-(benzothiazolyl)-3-methane amide-7-N, 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-the 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 the 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 the 10mL colorimetric cylinder, add a certain amount of aqueous solution that contains silver ions 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 the F-2500 of Hitachi type spectrophotofluorometer, Ag (I) aqueous solution that contains different concns is carried out fluorescence spectrometry, linear equation is F=2.37 * 10
3-2.36 * 10
7C, linearity range is 1.67 μ mol/L～83.3 μ mol/L, linearly dependent coefficient is R2=0.995 (n=6), specifically sees Fig. 7,8.
Embodiment 3:
Get tealeaves sample (Mount Huang Mao Feng) and wash after acetone soaks 50min again, in the oven dry down of 80 degree, accurately weighing 5.0g tealeaves adds 25ml HClO
4-HNO
3(volume ratio 1:8) mixed solution, heating stir evaporate to dryness after fully reacting, and collect powder as in the centrifuge tube, add 5ml H
2SO
4The aqueous solution (volume ratio 1:1) is put into whizzer behind the mixing, present the stillness of night with the centrifugal 4h of 2500r/s until the upper strata, gets 10 μ l supernatant liquors at every turn and measures, and in the 10mL colorimetric cylinder, adds quantity 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) is in λ
Ex/ λ
Em=447nm/492nm place with the F-2500 of Hitachi type fluorescent spectrophotometer assay, the results are shown in Table 1.
Get middle-aged people's hair, adopt method similarly to Example 2 to handle, in the 10mL colorimetric cylinder, add quantity 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) is in λ
Ex/ λ
Em=447nm/492nm place with the F-2500 of Hitachi type fluorescent spectrophotometer assay, the results are shown in Table 1.
The detected result of silver ions in table 1 tealeaves and the 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, the molecular structure of N-diethyl-tonka bean camphor is as follows:
2. the described N ' of claim 1-(benzothiazolyl)-3-methane amide-7-N, the preparation method of N-diethyl-tonka bean camphor: it is characterized in that: with the 4-(diethylin)-salicylic aldehyde is at piperidines, generate the 7-(diethylin with the diethyl malonate reaction under the condition of acetic acid)-the coumarin-3-carboxylic acid ethyl ester, the 7-(diethylin)-the coumarin-3-carboxylic acid ethyl ester carries out the hydrolysis reaction of ester under alkaline condition, regulate the pH value and obtain the 7-(diethylin)-coumarin-3-carboxylic acid, again with the 7-(diethylin)-coumarin-3-carboxylic acid and 2-aminobenzothiazole carry out the acid amides prepared in reaction and obtain N '-(benzothiazolyl)-3-methane amide-7-N, N-diethyl-tonka bean camphor.
3. the described N ' of claim 1-(benzothiazolyl)-3-methane amide-7-N, the application of N-diethyl-tonka bean camphor is characterized in that: be applied to the fluoroscopic examination of 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
2O/DMF (3/7, v/v) detect Ag (I) in the 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
2O/DMF (3/7, v/v) detect Ag (I) in tealeaves and the hair in the medium.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105461675A (en) * | 2015-11-24 | 2016-04-06 | 山西大同大学 | 7-N,N-diethylamino-coumarin-3-carboxylic acid-7-benzopyrone and preparation method and application thereof |
| 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 |
| CN108844931A (en) * | 2018-05-23 | 2018-11-20 | 郑州大学 | LZQ fluorescence probe detects SO at the same time2With the application in HSA |
| CN112625033A (en) * | 2020-12-21 | 2021-04-09 | 青岛科技大学 | Fluorescent probe for detecting amine compound gas |
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| US4146712A (en) * | 1976-03-11 | 1979-03-27 | Ciba-Geigy Corporation | Process for the manufacture of coumarin dyes |
| JPH04134446A (en) * | 1990-09-27 | 1992-05-08 | Konica Corp | Silver halide photographic sensitive material |
| 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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2013
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Patent Citations (3)
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|---|---|---|---|---|
| US4146712A (en) * | 1976-03-11 | 1979-03-27 | Ciba-Geigy Corporation | Process for the manufacture of coumarin dyes |
| JPH04134446A (en) * | 1990-09-27 | 1992-05-08 | Konica Corp | Silver halide photographic sensitive material |
| 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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|---|
| MAO XIANG WANG，等: "Novel fluorescent chemosensor for Ag+ based on coumarin fluorophore", 《CHINESE CHEMICAL LETTERS》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105461675A (en) * | 2015-11-24 | 2016-04-06 | 山西大同大学 | 7-N,N-diethylamino-coumarin-3-carboxylic acid-7-benzopyrone and preparation method and application thereof |
| 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 |
| CN108844931A (en) * | 2018-05-23 | 2018-11-20 | 郑州大学 | LZQ fluorescence probe detects SO at the same time2With the application in HSA |
| CN108844931B (en) * | 2018-05-23 | 2020-09-11 | 郑州大学 | Simultaneous detection of SO with LZQ fluorescent probe2Derivatives and use in HSA |
| CN112625033A (en) * | 2020-12-21 | 2021-04-09 | 青岛科技大学 | Fluorescent probe for detecting amine compound gas |
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