CN102154003A - Novel carbazole-bridge-based fluorescent cyanine dye probe and preparation method thereof - Google Patents
Novel carbazole-bridge-based fluorescent cyanine dye probe and preparation method thereof Download PDFInfo
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- CN102154003A CN102154003A CN2011100366688A CN201110036668A CN102154003A CN 102154003 A CN102154003 A CN 102154003A CN 2011100366688 A CN2011100366688 A CN 2011100366688A CN 201110036668 A CN201110036668 A CN 201110036668A CN 102154003 A CN102154003 A CN 102154003A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000000975 dye Substances 0.000 claims abstract description 59
- ACOJCCLIDPZYJC-UHFFFAOYSA-M thiazole orange Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1.C1=CC=C2C(C=C3N(C4=CC=CC=C4S3)C)=CC=[N+](C)C2=C1 ACOJCCLIDPZYJC-UHFFFAOYSA-M 0.000 claims abstract description 29
- 238000006862 quantum yield reaction Methods 0.000 claims abstract description 9
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- 238000006243 chemical reaction Methods 0.000 claims description 17
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 15
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- 239000000126 substance Substances 0.000 claims description 5
- VKAPZVJTVQIWJN-UHFFFAOYSA-N 2-(9-benzylcarbazol-3-yl)-1,3-benzothiazole Chemical compound C(c1ccccc1)n1c2ccccc2c2cc(ccc12)-c1nc2ccccc2s1 VKAPZVJTVQIWJN-UHFFFAOYSA-N 0.000 claims description 3
- PVOYLRQNEBDJAD-UHFFFAOYSA-N 2-(9-benzylcarbazol-3-yl)-1,3-benzoxazole Chemical compound O1C(=NC2=C1C=CC=C2)C=2C=CC=1N(C3=CC=CC=C3C1C2)CC2=CC=CC=C2 PVOYLRQNEBDJAD-UHFFFAOYSA-N 0.000 claims description 3
- HGVWMQMVHVJTGC-UHFFFAOYSA-N 2-(9-ethylcarbazol-3-yl)-1,3-benzothiazole Chemical group C1=CC=C2SC(C=3C=C4C5=CC=CC=C5N(C4=CC=3)CC)=NC2=C1 HGVWMQMVHVJTGC-UHFFFAOYSA-N 0.000 claims description 3
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- 230000001186 cumulative effect Effects 0.000 claims description 2
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- 239000007850 fluorescent dye Substances 0.000 abstract description 14
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Images
Abstract
The invention provides a carbazole-bridge-based fluorescent cyanine dye probe. The structure of the cyanine dye probe comprises a cyanine dye probe which is formed by respectively bonding carbazole bridge bases between enzoxazol and 4-methyl quinoline salt of thiazole orange and thiazole yellow; one end of a 3-site side chain of a carbazole ring is connected with the 2-C of the enzoxazol, and the other end of the 6-formoxy is connected with 4-vinyl quinoline salt compound. The invention simultaneously provides a preparation method of the carbazole-bridge-based fluorescent cyanine dye probe. According to the invention, the preparation method of the fluorescent dye biological probe is simple, and a raw material is available; by the preparation method, the maximum emission wavelength of the newly synthesized fluorescent dye probe generates red shift, fluorescence strength is enlarged, Stocks displacement is enlarged, fluorescence quantum yield is improved, and light stability is enhanced. In the probe provided by the invention, the advantages of hiazole orange and thiazole yellow embedded fluorescent dye are maintained, thereby being beneficial to further improvement of sensitivity and reduction of dosage as well as improvement of stability. The probe provided by the invention has the characteristics of wide spectral range, large molar extinction coefficient, high capitalization rate, high sensitivity and the like.
Description
Technical field
The present invention relates to from chemical field and be applied to the fluorescence dye technology, particularly carbazole abutment novel fluorescence cyanine dyes probe and preparation method thereof of biological field.
Background technology
As everyone knows, cancer has become first killer who threatens human health, and how controlling its generation effectively and developing has become the task of top priority.Most scholars think that in the control of tumour, tumour obtains secondary prevention, promptly early look into, early examine, early control and will be the direction that following solid tumor quite over a long time obtains to increase substantially curative effect.Because the molecular biosciences mark has advantages such as inexpensive, safe, accurate, more and more is being subjected to people's attention aspect the medical science early diagnosis.This technology is having application preferably aspect the identification of cancer and acquired immune deficiency syndrome (AIDS) at present.
Biological fluorescent labeling compare with traditional isotope detection in the related detecting method of biological field and technology have that speed is fast, good reproducibility, consumption reach characteristics such as radiationless less.The bioluminescence pigment probe that is used for cell marking at present mainly contains acridine, phenanthridines class, fluoresceins, two fluothane boron classes, diphenylethylene, naphthalimide, cyanine dyes class etc.Cyanine dyes has characteristics such as quick, sensitive and safety as the labeling dye of biomacromolecule, has become the biomolecules fluorescent marker dyes of a new generation.And thiazole orange (TO) is with oxazole Huang (YO) has become two important branch of cyanine dyes as embedded fluorescence dye, this unsymmetrical cyanine dye has big, the fluorescence quantum yield advantages of higher of molar absorptivity, and under unbound state, almost there is not fluorescence, but combine back fluorescence significantly strengthens with nucleic acid, thereby the fluorescence interference that when fluoroscopic examination, does not have dyestuff self, improve the sensitivity that detects, reduced the complex steps of removing free dye in the labeling process.But because thiazole orange (TO) He the fluorescence intensity of oxazole Huang (YO) itself a little less than, shortcoming such as maximum emission wavelength is little, the Stocks displacement is little has restricted this two kinds of fluorescence dye application in biomarker.
The fluorescence spy of fluorescence probe dye can be relevant with factors such as the coplanarity of the conjugated system size of probe, conjugation ∏ key system and degrees of rigidity, carbazole and derivative are electron rich systems, are easy to carry out structural modification and introduce advantages such as multiple functional group and be widely used in fields such as dyestuff, biology, medicine, photoelectric material owing to it has big conjugated system, strong intramolecularly electron transfer capacity, special rigid plane condensed ring structure, strong fluorescence and carbazole ring.Therefore this special stiffening ring of carbazole ring is bonded in thiazole orange (in the TO) Huo oxazole Huang (YO), the conjugated system and the plane rigid structure of original fluorescence dye have been increased, to help the maximum emission wavelength generation red shift of fluorescence dye, fluorescence intensity increases, the Stocks displacement increases, and improves fluorescence quantum yield.
Summary of the invention
The purpose of this invention is to provide carbazole abutment fluorescent cyanogen dye probe and preparation method thereof, with conjugated system and the plane rigid structure that increases original fluorescence probe dye, to help the maximum emission wavelength generation red shift of fluorescence dye, fluorescence intensity increases, the Stocks displacement increases, and improves fluorescence quantum yield and light stability.
For achieving the above object, the technical solution used in the present invention provides a kind of carbazole abutment fluorescent cyanogen dye probe, and wherein: this cyanine dyes probe structure includes the cyanine dyes probe that the carbazole abutment is bonded in respectively between thiazole orange (TO) is Ji the benzo thiophene (Evil of oxazole Huang (YO)) azoles and the 4-toluquinoline salt and form; 3 side chain one ends of described carbazole ring and benzo thiophene (Evil) 2 carbon of azoles link to each other, and 6 formyl radicals of the carbazole the other end link to each other with 4-vinylquinoline salt compound.
The present invention also provides a kind of preparation method of carbazole abutment fluorescent cyanogen dye probe simultaneously.
Effect of the present invention is:
1. fluorescent dye biological probe preparation method of the present invention is simple, and raw material is easy to get.
2. the introducing of carbazole abutment makes the maximum emission wavelength generation red shift of new synthetic fluorescence probe dye, and fluorescence intensity increases, and the Stocks displacement increases, and fluorescence quantum yield improves, and light stability strengthens.
3. the present invention has kept thiazole orange (TO) will help further improving sensitivity, reduces consumption, improve stability with the advantage of the embedded fluorescence dye of oxazole Huang (YO).
4. have that spectral range is wide, characteristics such as molar extinction coefficient is big, two assets rate height and sensitivity height.
Description of drawings
Fig. 1 is a carbazole abutment fluorescent cyanogen dye probe design structure route map of the present invention;
Fig. 2 is a carbazole abutment fluorescent cyanogen dye probe experimental road line chart of the present invention.
Embodiment
Further carbazole abutment novel fluorescence cyanine dyes probe of the present invention and preparation method thereof is illustrated below in conjunction with drawings and Examples.
As shown in Figure 1, carbazole abutment novel fluorescence cyanine dyes probe of the present invention is based on carbazole and derivative is an electron rich system, has big conjugated system, strong intramolecularly electron transfer capacity, special rigid plane condensed ring structure, strong fluorescence and be easy to carry out structural modification to introduce advantages such as multiple functional group.Therefore this special stiffening ring of carbazole ring is bonded in thiazole orange (in TO) Huo oxazole Huang (YO) molecular structure, the conjugated system and the plane rigid structure of original two fluorochrome probes have been increased, to help the maximum emission wavelength generation red shift of fluorescence dye, fluorescence intensity increases, the Stocks displacement increases, and improves fluorescence quantum yield and light stability.
Carbazole abutment fluorescent cyanogen dye probe of the present invention, this cyanine dyes probe structure include the cyanine dyes probe that the carbazole abutment is bonded in respectively between thiazole orange (TO) is Ji the benzo thiophene (Evil of oxazole Huang (YO)) azoles and the 4-toluquinoline salt and form; 3 side chain one ends of described carbazole ring and benzo thiophene (Evil) 2 carbon of azoles link to each other, and 6 formyl radicals of the carbazole the other end link to each other with 4-vinylquinoline salt compound.
Described 4-toluquinoline salt is with Br
-Be anionic 4-toluquinoline salt, the group on the N position of 4-toluquinoline salt is respectively-CH
2CH
2COOH ,-CH
2CH
2CH
2CH
2CH
2COOH ,-CH
2CH
3,-CH
2CH
2CH
2Br,
The characteristic of described carbazole abutment fluorescent cyanogen dye probe:
Fluorescent emission wavelength: 630nm-660nm;
Fluorescence intensity: 30-55;
Stoke shift (Stocks): 130-151nm;
Fluorescence quantum yield: 0.02-0.6.
The preparation method of carbazole abutment fluorescent cyanogen dye probe of the present invention includes following steps:
1) preparation of 3-benzothiazolyl-6-formyl radical-N-ethyl carbazole, 3-benzoxazolyl-6-formyl radical-N-ethyl carbazole, 3-benzoxazolyl-6-formyl radical-N-benzyl carbazole, 3-benzothiazolyl-6-formyl radical-N-benzyl carbazole
In 4 100mL round-bottomed flasks, add the amount of substance ratio respectively and be 1: 1 N, dinethylformamide (DMF) and phosphorus oxychloride, drip and finish, after stirring at room to reaction system is blush, dripping amount of substance respectively is 3-benzothiazolyl-N-ethyl carbazole of 17 times of DMF, 3-benzoxazolyl-N-ethyl carbazole, 3-benzoxazolyl-N-benzyl carbazole, 1 of 3-benzothiazolyl-N-benzyl carbazole, the 2-dichloroethane solution, cumulative volume is at 40-70mL, backflow stirring reaction 6h-12h when temperature is 79-85 ℃, pour in the frozen water after being cooled to room temperature, use dichloromethane extraction, column chromatography for separation is purified, and obtains 3-benzothiazolyl-6-formyl radical-N-ethyl carbazole respectively, 3-benzoxazolyl-6-formyl radical-N-ethyl carbazole, 3-benzoxazolyl-6-formyl radical-N-benzyl carbazole, 3-benzothiazolyl-6-formyl radical-N-benzyl carbazole;
2) preparation of carbazole abutment fluorescent cyanogen dye probe
1 mole the 3-benzothiazolyl-6-formyl radical-N-ethyl carbazole that will draw through step 1 respectively; 3-benzoxazolyl-6-formyl radical-N-ethyl carbazole; 3-benzoxazolyl-6-formyl radical-N-benzyl carbazole; the 4-toluquinoline salt that has different substituents on the N position of 3-benzothiazolyl-6-formyl radical-N-benzyl carbazole and four parts 1.5 moles is dissolved in the ethanol; drip piperidines with 4-toluquinoline salt equivalent; backflow stirring reaction time 8-16h when temperature is 75-80 ℃; be cooled to room temperature; add ether again and separate out red solid; suction filtration; get filter cake through column chromatography for separation, obtain described carbazole abutment fluorescent cyanogen dye probe.
Quinolinium in the carbazole abutment fluorescent cyanogen dye probe structure of the present invention is with Br
-Be anionic 4-toluquinoline salt, the group on the N position is respectively-CH
2CH
2COOH ,-CH
2CH
2CH
2CH
2CH
2COOH ,-CH
2CH
3,-CH
2CH
2CH
2Br,
The preparation method of carbazole abutment fluorescent cyanogen dye probe of the present invention further specifies by following examples, as shown in Figure 2, but is not limited to this.
Target compound a-e represents R
1Be ethyl, X is S, R
2Be respectively-CH
2CH
2COOH ,-CH2CH
2CH
2Br ,-CH
2CH
3,-CH
2CH
2CH
2CH
2CH
2The N-ethyl carbazole abutment thiazole orange cyanine dyes probe of different substituents such as COOH group; F-j represents R
1Be ethyl, X is O, R
2Be respectively-CH
2CH
2COOH ,-CH2CH
2CH
2Br ,-CH
2CH
3,-CH
2CH
2CH
2CH
2CH
2Different substituents such as COOH groups the yellow cyanine dyes probe of N-ethyl carbazole Qiao Ji oxazole; K-o represents R
1Be benzyl, X is S, R
2Be respectively-CH
2CH
2COOH ,-CH2CH
2CH
2Br ,-CH
2CH
3,-CH
2CH
2CH
2CH
2CH
2The N-benzyl carbazole abutment thiazole orange cyanine dyes probe of different substituents such as COOH group; P-t represents R
1Be benzyl, X is O, R
2Be respectively-CH
2CH
2COOH ,-CH2CH
2CH
2Br ,-CH
2CH
3,-CH
2CH
2CH
2CH
2CH
2Different substituents such as COOH groups the yellow cyanine dyes probe of N-benzyl carbazole bridge base oxazole, experiment route and target compound see Table 1:
Table 1 target compound a～t
The preparation of embodiment 1N-ethyl carbazole abutment thiazole orange cyanine dyes probe may further comprise the steps:
1.3-benzothiazolyl-6-formyl radical-N-ethyl carbazole
In the 100mL round-bottomed flask, add DMF 7.7mL (100mmol), ice-water bath drips phosphorus oxychloride 9.5mL (15.2g down, 100mmol), drip and finish, be blush in stirring at room to reaction system, slowly drip 1 of 3-benzothiazolyl-N-ethyl carbazole 2g (6mmol), the solution of 2-ethylene dichloride 30mL, drip and finish 83 ℃ of back flow reaction 6h.Pour in the frozen water after being cooled to room temperature, use dichloromethane extraction, column chromatography for separation gets 3-benzothiazolyl-6-formyl radical-N-ethyl carbazole.
2.N-the preparation of ethyl carbazole abutment thiazole orange cyanine dyes probe a
0.1g (0.28mmol) 3-benzothiazolyl-6-formyl radical-N-ethyl carbazole is dissolved in the 30mL ethanol; again 0.13g (0.42mmol) carboxyl quinoline salt is dissolved in the 20mL ethanol; the two mixing is placed flask; drip 0.04mL (0.42mmol) piperidines, 78 ℃ of back flow reaction 12h are cooled to room temperature; add ether and separate out red solid; suction filtration, the filter cake column chromatography for separation promptly gets red target product a.
Get respectively on the N position of 0.42mmol and have-CH
2CH
2CH
2CH
2CH
2COOH ,-CH
2CH
3,-CH
2CH
2CH
2Br,
Substituent quinolinium replaces above-mentioned 0.13g (0.42mmol) carboxyl quinoline salt, repeats the chemical reaction of above-mentioned steps 2, gets the target product b～e among the present invention.
The preparation of embodiment 2N-benzyl carbazole bridge thiazole orange cyanine dyes probe may further comprise the steps:
1.3-the preparation of benzothiazolyl-6-formyl radical-N-benzyl carbazole
In flask, add DMF 7.7mL (100mmol), ice-water bath drips phosphorus oxychloride 9.5mL (15.2g down, 100mmol), drip and finish, be blush in stirring at room to solution, slowly drip 1 of 3-benzothiazolyl-N-benzyl carbazole 2.34g (6mmol), the solution of 2-ethylene dichloride 30mL, drip and finish 83 ℃ of back flow reaction 16h.Pour in the frozen water after being cooled to room temperature, use dichloromethane extraction, column chromatography for separation gets 3-benzothiazolyl-6-formyl radical-N-benzyl carbazole.
2.N-the preparation of benzyl carbazole abutment thiazole orange cyanine dyes probe k
0.1g (0.28mmol) 3-benzothiazolyl-6-formyl radical-N-benzyl carbazole is dissolved in the 30mL ethanol; again 0.13g (0.42mmol) carboxyl quinoline salt is dissolved in the 20mL ethanol; the two mixing is placed flask; drip 0.04mL (0.42mmol) piperidines; 78 ℃ of back flow reaction 12h are cooled to room temperature, add ether and separate out red solid; suction filtration, filter cake column chromatography promptly get red target product k.
Get respectively on the N position of 0.42mmol and have-CH
2CH
2CH
2CH
2CH
2COOH ,-CH
2CH
3,-CH
2CH
2CH
2Br,
Substituent quinolinium replaces above-mentioned 0.13g (0.42mmol) carboxyl quinoline salt, repeats the chemical reaction of above-mentioned steps 2, gets the target product l～o among the present invention.
The preparation of the yellow cyanine dyes probe of embodiment 3N-ethyl Ka Zuo oxazole may further comprise the steps:
1.3-the preparation of benzoxazolyl-6 formyl radicals-N-ethyl carbazole
In flask, add DMF 7.7mL (100mmol), ice-water bath drips phosphorus oxychloride 9.5mL (15.2g down, 100mmol), drip and finish, be blush in stirring at room to solution, slowly drip 1 of 3-benzoxazolyl-N-ethyl carbazole 2.25g (6mmol), the solution of 2-ethylene dichloride 30mL, drip and finish 83 ℃ of back flow reaction 16h.Pour in the frozen water after being cooled to room temperature, use dichloromethane extraction, column chromatography for separation gets 3-benzoxazolyl-6-formyl radical-N-ethyl carbazole.
2.N-the preparation of the yellow cyanine dyes probe of ethyl Ka Zuo oxazole f
0.11g (0.28mmol) 3-benzoxazolyl-6-formyl radical-N-ethyl carbazole is dissolved in the 30mL ethanol; again 0.13g (0.42mmol) carboxyl quinoline salt is dissolved in the 20mL ethanol; the two mixing is placed flask; drip 0.04mL (0.42mmol) piperidines; 78 ℃ of back flow reaction 12h are cooled to room temperature, add ether and separate out red solid; suction filtration, filter cake column chromatography promptly get red target product f.
Get respectively on the N position of 0.42mmol and have-CH
2CH
2CH
2CH
2CH
2COOH ,-CH
2CH
3,-CH
2CH
2CH
2Br,
Substituent quinolinium replaces above-mentioned 0.13g (0.42mmol) carboxyl quinoline salt, repeats the chemical reaction of above-mentioned steps 2, gets the target product g～j among the present invention.
The yellow cyanine dyes probe of embodiment 4N-benzyl carbazole Qiao Ji oxazole may further comprise the steps:
1.3-the preparation of benzoxazolyl-6 formyl radicals-N-benzyl carbazole
In flask, add DMF 7.7mL (100mmol), ice-water bath drips phosphorus oxychloride 9.5mL (15.2g down, 100mmol), drip and finish, be blush in stirring at room to solution, slowly drip 1 of 3-benzoxazolyl-N-benzyl carbazole 1.71g (6mmol), the solution of 2-ethylene dichloride 30mL, drip and finish 83 ℃ of back flow reaction 16h.Pour in the frozen water after being cooled to room temperature, use dichloromethane extraction, column chromatography for separation gets 3-benzoxazolyl-6-formyl radical-N-benzyl carbazole.
2.N-the preparation of the yellow cyanine dyes probe of benzyl carbazole Qiao Ji oxazole p
0.11g (0.28mmol) 3-benzoxazolyl-6-formyl radical-N-benzyl carbazole is dissolved in the 30mL ethanol; again 0.13g (0.42mmol) carboxyl quinoline salt is dissolved in the 20mL ethanol; the two mixing is placed flask; drip 0.04mL (0.42mmol) piperidines; 78 ℃ of back flow reaction 12h are cooled to room temperature, add ether and separate out red solid; suction filtration, filter cake column chromatography promptly get red target product p.
Get respectively on the N position of 0.42mmol and have-CH
2CH
2CH
2CH
2CH
2COOH ,-CH
2CH
3,-CH
2CH
2CH
2Br,
Substituent quinolinium replaces above-mentioned 0.13g (0.42mmol) carboxyl quinoline salt, repeats the chemical reaction of above-mentioned steps 2, gets the target product q～t among the present invention.
The performance that carbazole abutment fluorescent cyanogen dye probe of the present invention is shown is fluorescent emission wavelength: 630nm-660nm; 547nm compares with the TO emission wavelength, red shift 80nm-110nm; Fluorescence intensity: 30-55; Compare with 0.77 of TO and to have increased 39-71 doubly, so fluorescence intensity significantly strengthens; Stoke shift (Stocks): 130-151mm, TO is 67, displacement increases 2-3, fluorescence quantum yield: 0.02-0.6, compare increase 2-5 with TO doubly, light stability increases 1-6 doubly, the big planar molecule structure that has kept conjugated system simultaneously, (TO) particularly can embed the methylene radical quinoline structure of NDA or RNA with the constitutional features of the embedded fluorescence dye of oxazole Huang (YO), therefore has the advantage of embedded cyanine dyes to have kept thiazole orange, a little less than fluorescence background own, combine back fluorescence with DNA or RNA and strengthen greatly, nontoxic, advantages such as sensitivity height.
Claims (4)
1. carbazole abutment fluorescent cyanogen dye probe is characterized in that: this cyanine dyes probe structure includes that the carbazole abutment is bonded in respectively between benzo thiophene (Evil) azoles of thiazole orange (TO) and oxazole Huang (YO) and the 4-toluquinoline salt and the cyanine dyes probe that forms; 3 side chain one ends of described carbazole ring and benzo thiophene (Evil) 2 carbon of azoles link to each other, and 6 formyl radicals of the carbazole the other end link to each other with 4-vinylquinoline salt compound.
2. according to the described carbazole abutment of claim 1 fluorescent cyanogen dye probe, it is characterized in that: described 4-toluquinoline salt is with Br
-Be anionic 4-toluquinoline salt, the group on the N position of 4-toluquinoline salt is respectively-CH
2CH
2COOH ,-CH
2CH
2CH
2CH
2CH
2COOH ,-CH
2CH
3,-CH
2CH
2CH
2Br,
3. carbazole abutment fluorescent cyanogen dye probe according to claim 1 is characterized in that: the characteristic of described carbazole abutment fluorescent cyanogen dye probe:
Fluorescent emission wavelength: 630nm-660nm;
Fluorescence intensity: 30-55;
Stoke shift (Stocks): 130-151nm;
Fluorescence quantum yield: 0.02-0.6.
4. according to the preparation method of the described carbazole abutment of claim 1 fluorescent cyanogen dye probe, this preparation method includes following steps:
1) preparation of 3-benzothiazolyl-6-formyl radical-N-ethyl carbazole, 3-benzoxazolyl-6-formyl radical-N-ethyl carbazole, 3-benzoxazolyl-6-formyl radical-N-benzyl carbazole, 3-benzothiazolyl-6-formyl radical-N-benzyl carbazole
In 4 100mL round-bottomed flasks, add the amount of substance ratio respectively and be 1: 1 N, dinethylformamide (DMF) and phosphorus oxychloride, drip and finish, after stirring at room to reaction system is blush, dripping amount of substance respectively is 3-benzothiazolyl-N-ethyl carbazole of 17 times of DMF, 3-benzoxazolyl-N-ethyl carbazole, 3-benzoxazolyl-N-benzyl carbazole, 1 of 3-benzothiazolyl-N-benzyl carbazole, the 2-dichloroethane solution, cumulative volume is at 40-70mL, backflow stirring reaction 6h-12h when temperature is 79-80 ℃, pour in the frozen water after being cooled to room temperature, use dichloromethane extraction, column chromatography for separation is purified, and obtains 3-benzothiazolyl-6-formyl radical-N-ethyl carbazole respectively, 3-benzoxazolyl-6-formyl radical-N-ethyl carbazole, 3-benzoxazolyl-6-formyl radical-N-benzyl carbazole, 3-benzothiazolyl-6-formyl radical-N-benzyl carbazole;
2) preparation of carbazole abutment fluorescent cyanogen dye probe
1 mole the 3-benzothiazolyl-6-formyl radical-N-ethyl carbazole that will draw through step 1 respectively; 3-benzoxazolyl-6-formyl radical-N-ethyl carbazole; 3-benzoxazolyl-6-formyl radical-N-benzyl carbazole; the 4-toluquinoline salt that has different substituents on the N position of 3-benzothiazolyl-6-formyl radical-N-benzyl carbazole and four parts 1.5 moles is dissolved in the ethanol; drip piperidines with 4-toluquinoline salt equivalent; backflow stirring reaction time 8-16h when temperature is 75-80 ℃; be cooled to room temperature; add ether again and separate out red solid; suction filtration; filter cake obtains described carbazole abutment fluorescent cyanogen dye probe through column chromatography for separation.
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| CN105968098A (en) * | 2016-05-12 | 2016-09-28 | 三峡大学 | Carbazole-contained benzimidazole-substituted quinoline derivative, preparation method and application thereof |
| CN105968098B (en) * | 2016-05-12 | 2018-03-02 | 三峡大学 | A kind of quinoline substituted containing carbazole, benzimidazole and its preparation method and application |
| CN106543169A (en) * | 2016-10-28 | 2017-03-29 | 安徽大学 | One kind is than colour pattern chemical sensor and its production and use |
| CN106543169B (en) * | 2016-10-28 | 2019-07-26 | 安徽大学 | It is a kind of than colour pattern chemical sensor and its preparation method and application |
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| CN113454067A (en) * | 2019-02-12 | 2021-09-28 | 香港科技大学 | Fluorescent probe for singlet oxygen generation and cancer ablation |
| CN113454067B (en) * | 2019-02-12 | 2023-02-21 | 香港科技大学 | Fluorescent probe for singlet oxygen generation and cancer ablation |
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| CN114835681A (en) * | 2022-04-27 | 2022-08-02 | 南通大学 | Carbazole quinoline heterozygote, preparation method and application |
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