CN107090191A - One class rhodamine fluorescent dyes and preparation method thereof - Google Patents
One class rhodamine fluorescent dyes and preparation method thereof Download PDFInfo
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Abstract
The invention discloses class rhodamine fluorescent dyes and preparation method thereof, based on classical rhodamine synthetic method, by rational structural modification, the chemical group of difference in functionality is introduced on rhodamine parent, increases conjugation, changes hyperchromic group, such as：Hydroxyl, diethylin, the structure such as azabicyclo.Novel rhodamine dyestuff produced by the present invention has bigger launch wavelength and bigger quantum yield, also with more reaction sites, subsequent reactions is more facilitated；And with moderate Stokes shift, the interference for the excitation wavelength that can be forgone in follow-up fluoroscopic examination makes analysis result more accurate.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to class rhodamine fluorescent dyes and preparation method thereof.
Background technology
Rhodamine compound is the alkaline xanthene dye by parent of xanthene, due to special structure and corresponding glimmering
Light characteristic, makes rhodamine fluorescent dye turn into chemistry and field of bioanalysis and studies relatively broad problem.Relevant Luo Dan
Report in terms of synthesis, ionization and the structure of bright fluorochrome, optical characteristics and analysis is a lot.Commonly used with other
Fluorescent dye compare, rhodamine fluorescent dye has good light stability, wave-length coverage insensitive to pH, wider and higher
Fluorescence quantum yield the advantages of, therefore be widely used in pharmacology, physiology, molecular biology, cell biology, molecule
It is analytical chemistry and life in terms of science of heredity, Environmental Chemistry, individual molecule detection, information science, fluorescence labeling, laser dye
The most frequently used fluorescent dye in the biological technical fields such as thing medical science.
Rhodamine Derivatives are most widely used dye, rhodamine 6G and Luo Dan in organic molecule probe field
Bright B has the advantages that big molar absorption coefficient, high fluorescence quantum yield and the preferable object of photostability and rhodamine are glimmering
The specific reaction or Non-covalent binding of light probe can induce the switch of rhodamine lactams loop coil, cause the off- of fluorescence signal
On changes, so as to realize the fluoroscopic examination to object, the mechanism is widely used to rhodamine small-molecule fluorescent probe
Design.Building fluorescence probe using the principle turns into the study hotspot of sensory field.
As application is more and more extensive, the research and development of rhodamine fluorescent dye is rapid and receives more weights
Reporting the fluorescence probe based on rhodamine Spirocyclic derivatives depending on, lot of documents is used for the detection of plurality of target thing, such as metal from
Son (Cu2+、Hg2+、Fe3+、Zn2+、Cr3+、Ag+、Au+、Pb2+And Pd2+), anion (OCl-、CN-And P2O7 4-), reactive oxygen species/work
Property nitrogen cluster, sulfur alcohol compound, pH value and temperature etc..Based on the wide research space of rhodamine fluorescent dyes and apply valency
Value, design synthesis a series of new rhodamine fluorescent dye is necessary.
The content of the invention
Object of the present invention is to provide the new rhodamine fluorescent dyes of a class, with bigger quantum yield and suitable
In Stokes shift, present invention also offers the preparation method of such rhodamine fluorescent dyes.
To achieve these goals, the technical solution adopted by the present invention is：
One class rhodamine fluorescent dyes, the fluorochrome is any one in dyestuff 1, dyestuff 2 and dyestuff 3, wherein
Dyestuff 1, dyestuff 2, the structural formula of dyestuff 3 distinguish as follows：
The preparation method of above-mentioned rhodamine fluorescent dyes, comprises the following steps：
(1) resorcinol obtains compound 1 with phthalic anhydride；3- hydroxy-ns, N- diethylanilines and adjacent benzene
Dicarboxylic acid anhydride reaction obtains compound 2；Meta-aminophenol reacts to obtain compound 3, compound 3 and adjacent benzene two with the bromo- 3- chloropropanes of 1-
Formic acid anhydride reactant obtains compound 4；Compound 1, compound 2, compound 3 and compound 4 chemical formula it is as follows：
(2) by catalyst of methanesulfonic acid, toluene be reaction dissolvent, compound 1, compound 2 and compound 4 are distinguished by acenaphthene phenol
Reaction, obtains dyestuff 1, dyestuff 2 and dyestuff 3.
Preferably, the preparation method of compound 1 is specially in step (1)：Resorcinol and phthalic anhydride are dissolved
In toluene, it is stirred at reflux to generation solid, suction filtration takes solid, with recrystallizing methanol, produced；Wherein, resorcinol in toluene
Dosage be 2~3mol/L, the mol ratio of resorcinol and phthalic anhydride is 1：1.
Preferably, the preparation method of compound 2 is specially in step (1)：By 3- hydroxy-ns, N- diethylanilines and adjacent benzene
Dicarboxylic acid anhydride is dissolved in toluene, is stirred at reflux to generation solid, suction filtration takes solid, with recrystallizing methanol, produced；Wherein, first
3- hydroxy-ns in benzene, the dosage of N- diethylanilines is 2~3mol/L, 3- hydroxy-ns, N- diethylanilines and O-phthalic
The mol ratio of acid anhydrides is 1：1.
Preferably, the preparation method of compound 3 is specially in step (1)：Into dimethylformamide add meta-aminophenol,
Sodium acid carbonate and the bromo- 3- chloropropanes of 1-, are stirred and evenly mixed, and continue stirring in 65~75 DEG C, and thin-layer chromatography detection, which is reacted, have been generated
Compound 3, then further separated using column chromatography, produce；In dimethylformamide the dosage of meta-aminophenol be 1.5~
2.5mol/L, the mol ratio of meta-aminophenol, sodium acid carbonate and the bromo- 3- chloropropanes of 1- is 1：3~3.5：2.5~3, pillar layer separation
When eluant, eluent use petroleum ether：Ethyl acetate=20：1.
Preferably, the preparation method of compound 4 is specially in step (1)：Compound 3 and phthalic anhydride are dissolved in
In toluene, it is stirred at reflux to generation solid, suction filtration takes solid, with recrystallizing methanol, produced；Wherein, in toluene compound 3 throwing
Dosage is 2~3mol/L, and the mol ratio of compound 3 and phthalic anhydride is 1：1.
Preferably, the preparation method of acenaphthene phenol comprises the following steps in step (2)：
(1) POCl3 and DMF are sequentially added into acenaphthene, 90~95 DEG C are warming up to after stirring and evenly mixing,
Continue to stir 2.5~3.5 hours, obtain reaction solution；Reaction solution is added in mixture of ice and water, sticky solid is generated, through suction filtration
And vacuum drying, obtain 5- acenaphthene aldehyde crude products；Wherein, the mol ratio of acenaphthene, POCl3 and DMF is 1：2~
2.5：5~6；
(2) 5- acenaphthene aldehyde crude products obtained by step (1) are used into pillar layer separation, is dried in vacuo, obtains 5- acenaphthene aldehyde sterlings；Its
In, eluant, eluent is petroleum ether during pillar layer separation：Ethyl acetate=38~42：1；
(3) 5- acenaphthene aldehyde sterling, selenium dioxide, hydrogen peroxide and glacial acetic acid are added into dichloromethane, is stirred in 20~30 DEG C
Mix 35~40 hours, filter to take after filtrate, stratification, take organic layer to evaporate solvent, and hydroxide is dissolved in ice bath environment
In the methanol solution of potassium, then after being placed in and hydrolyzing 2.5~3.5 hours at room temperature, hydrochloric acid acidifying is added, then is extracted with ethyl acetate,
Ethyl acetate extraction phase, drying are washed, acenaphthene phenol crude product is obtained；Wherein, in dichloromethane the dosage of 5- acenaphthenes aldehyde sterling for 80~
The dosage that 100g/L, the dosage of selenium dioxide are 2~3g/L, the dosage of hydrogen peroxide is 1.6~2mol/L, glacial acetic acid
For 0.29~0.35mol/L, the concentration of potassium hydroxide is 0.13~0.16g/mL in the methanol solution of the potassium hydroxide；
(4) acenaphthene phenol crude product obtained by step (3) is used into pillar layer separation, is dried in vacuo, produces acenaphthene phenol sterling；Wherein, wash
De- agent is petroleum ether：Ethyl acetate=28~32：1.
Preferably, the preparation method of dyestuff 1 is specially in step (2)：Compound 1, acenaphthene phenol and first sulphur are added into toluene
Acid, in 60~70 DEG C continue stir 25~35 minutes, reaction solution is extracted with ethyl acetate, then wash ethyl acetate extraction phase,
Dry, obtain the crude product of dyestuff 1；The crude product of dyestuff 1 is further used into pillar layer separation, vacuum drying obtains the sterling of dyestuff 1；Wherein,
The dosage of compound 1 is 0.09~1.0mol/L in toluene, and the mol ratio of compound 1, acenaphthene phenol and methanesulfonic acid is 1：1：26~
27, eluant, eluent uses dichloromethane during pillar layer separation：Methanol=48~52：1.
Preferably, the preparation method of dyestuff 2 is specially in step (2)：Compound 2, acenaphthene phenol and first sulphur are added into toluene
Acid, in 60~70 DEG C continue stir 25~35 minutes, reaction solution is extracted with ethyl acetate, then wash ethyl acetate extraction phase,
Dry, obtain the crude product of dyestuff 2；The crude product of dyestuff 2 is further used into pillar layer separation, vacuum drying obtains the sterling of dyestuff 2；Wherein,
The dosage of compound 2 is 0.18~0.19mol/L in toluene, and the mol ratio of compound 2, acenaphthene phenol and methanesulfonic acid is 1：1.0~
1.1：8~9, eluant, eluent uses dichloromethane during pillar layer separation：Methanol=38~42：1.
Preferably, the preparation method of dyestuff 3 is specially in step (2)：Compound 4, acenaphthene phenol and first sulphur are added into toluene
Acid, in 60~70 DEG C continue stir 25~35 minutes, reaction solution is extracted with dichloromethane, then wash dichloromethane extraction phase,
Dry, obtain the crude product of dyestuff 3；The crude product of dyestuff 3 is further used into pillar layer separation, vacuum drying obtains the sterling of dyestuff 3；Wherein,
The dosage of compound 4 is 0.035~0.045mol/L in toluene, and the mol ratio of compound 4, acenaphthene phenol and methanesulfonic acid is 1：2~
3：64~66, eluant, eluent uses dichloromethane during pillar layer separation：Methanol=78~82：1.
Application of the above-mentioned rhodamine fluorescent dyes in fluoroscopic examination and pH probes.
The synthetic route of above-mentioned acenaphthene phenol is as follows：
The synthetic route of above-mentioned rhodamine fluorescent dye is as follows：
Various raw materials used in the present invention are ordinary commercial products, or by well known to a person skilled in the art
Method or in the prior art disclosed method acquisition.
The present invention has more excellent performance compared to classical rhodamine, above-mentioned three kinds of Novel rhodamine dyestuffs：
(1) more reaction sites, make subsequent reactions more facilitate；(2) bigger launch wavelength, the fluorescence emission wavelengths of dyestuff three exist
606nm, belongs near infrared region, can be fabulous applied to active somatic cell dyeing, analysis；(3) bigger quantum yield, is inherited
With developed the characteristics of rhodamine fluorescent dye quantum yield is high；(4) moderate Stokes shift, can be in follow-up fluorescence
The interference for excitation wavelength of being forgone in detection, makes analysis result more accurate.
Brief description of the drawings
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of dyestuff 1；
Fig. 2 is the nuclear-magnetism carbon spectrogram of dyestuff 1；
Fig. 3 is the mass spectrogram of dyestuff 1；
Fig. 4 is the nucleus magnetic hydrogen spectrum figure of dyestuff 2；
Fig. 5 is the nuclear-magnetism carbon spectrogram of dyestuff 2；
Fig. 6 is the mass spectrogram of dyestuff 2；
Fig. 7 is the nucleus magnetic hydrogen spectrum figure of dyestuff 3；
Fig. 8 is the mass spectrogram of dyestuff 3；
Fig. 9 be dyestuff 1, dyestuff 2 and dyestuff 3 uv-visible absorption spectra and its daylight under shown in color photo；
Figure 10 is the photo of the lower shown color of dyestuff 1, the fluorescence spectrum of dyestuff 2 and dyestuff 3 and its 365nm uviol lamps；
Figure 11 is uv-vis spectra and fluorescence spectrum of the dyestuff 1 under different pH；
Figure 12 is uv-vis spectra and fluorescence spectrum of the dyestuff 2 under different pH；
Figure 13 is uv-vis spectra and fluorescence spectrum of the dyestuff 3 under different pH.
Embodiment
Below by way of preferred embodiment, the present invention is described in more detail, but protection scope of the present invention is not limited to
This.
Embodiment 1
(1) preparation of acenaphthene phenol
5.0g (32mmol) acenaphthene is added into 100mL three-necked flask, then by 6.5mL POCl3s (POCl3) use permanent
Pressure funnel is slowly added in three-necked flask (completion of dropping in 15 minutes), adds 13.5mL DMFs
(DMF) 90~95 DEG C are to slowly warm up to after, stirring 5 minutes, continues to stir 3 hours, obtains reaction solution；Reaction solution is added
In 270mL mixture of ice and water, there are a large amount of sticky solids in stirring, through depressurizing suction filtration and vacuum drying, obtains acenaphthene aldehyde crude product；Then
Using pillar layer separation, eluant, eluent is petroleum ether：Ethyl acetate=40：1, vacuum drying obtains 2.759g pale yellow needles and consolidated
Body, i.e. 5- acenaphthenes aldehyde sterling, yield is 46.74%.
11mL dichloromethane and 1.0g 5- acenaphthene aldehyde are added into 50mL round-bottomed flask, 30mg selenium dioxide is added
(SeO2) and the hydrogen peroxide (H of 2mL 30%2O2), then it is added dropwise 4 and drips glacial acetic acid (about 0.2mL), it is small in 25 DEG C of stirring in water bath 38
When, filter to take after filtrate, stratification, take organic layer to rotate solvent, and it is molten in the methanol that ice bath environment is dissolved in potassium hydroxide
In liquid (being dissolved in 6mL methanol by 0.85g potassium hydroxide to be made), then be placed at room temperature hydrolyze 3 hours after, add 5mL mass fractions
It is acidified, then is extracted with ethyl acetate for 10% watery hydrochloric acid, ethyl acetate extraction phase is washed with deionized 2 times, then with suitable
Measure anhydrous sodium sulfate drying 30 minutes, obtain acenaphthene phenol crude product；Acenaphthene phenol crude product is used into pillar layer separation, eluant, eluent is petroleum ether：
Ethyl acetate=30：1, vacuum drying obtains 573mg pale yellow needles solids, i.e. acenaphthene phenol sterling, yield is 61.3%.1H
NMR(400MHz,CDCl3) δ 7.72 (d, J=8.3Hz, 1H), 7.46-7.40 (m, 1H), 7.28 (d, J=6.8Hz, 1H),
7.08 (d, J=7.3Hz, 1H), 6.79 (d, J=7.3Hz, 1H), 5.08 (s, 1H), 3.43-3.38 (m, 2H), 3.31 (dd, J
=8.2,5.0Hz, 2H).
Synthetic route is as follows：
(2) preparation of compound 1
40mL toluene (PhMe) is added into 150mL round-bottomed flasks, resorcinol 11.0g (0.1mol) and adjacent benzene is added
Dicarboxylic acid anhydride 14.8g (0.1mol), stirring and dissolving is stirred at reflux 5 hours, increasingly generates solid, suction filtration removes solid, uses methanol weight
Crystallization, obtains orange solids.
Synthetic route is as follows：
(3) preparation of dyestuff 1
3mL toluene, then middle addition 75mg (0.29mol) compound 1,50mg are added into 50mL round-bottomed flasks
(0.29mol) acenaphthene phenol sterling and 0.5mL methanesulfonic acids (MeSO3H), in 65 DEG C of oil bath heatings, stir 30 minutes, by reaction solution second
Acetoacetic ester is extracted, then is washed ethyl acetate extraction phase 2 times, used anhydrous Na2SO4Dry, obtain the crude product of dyestuff 1；By the crude product of dyestuff 1
Pillar layer separation is further used, eluant, eluent is dichloromethane：Methanol (DCM：MeOH)=50：1, solvent is rotated out, is dried in vacuo,
Obtain 85mg dark red solids (yield, 74%), the i.e. sterling of dyestuff 1.
Synthetic route is as follows：
The hydrogen nuclear magnetic resonance spectrogram of dyestuff 1 as shown in figure 1,1H NMRδH(400MHz,CDCl3)8.11(1H,d,J 8.2),
8.07(1H,dd,J 6.3,1.8),7.68–7.62(2H,m),7.62–7.56(1H,m),7.41(1H,d,J 6.8),7.14
(1H,dd,J 6.2,1.5),6.92(1H,d,J 2.5),6.73(1H,d,J 8.6),6.58(1H,dd,J 8.6,2.5),
6.51(1H,s),3.38(2H,dd,J 11.7,5.3),3.24–3.17(2H,m)；Carbon-13 nmr spectra figure such as Fig. 2 of dyestuff 1
It is shown, δC(101MHz,CDCl3)169.79,157.27,154.22,152.10,145.66,140.92,135.10,129.65,
128.46,126.48,125.04,124.02,121.60,117.89,116.49,113.98,112.31,111.36,103.14,
30.84,29.62.Mass spectral analysis is carried out to the sterling of dyestuff 1, as a result as shown in figure 3, explanation has synthesized dyestuff 1.
(4) preparation of compound 2
40mL toluene is added into 150mL round-bottomed flasks, 3- hydroxy-ns, N- diethylanilines 16.5g is added
(0.1mol), phthalic anhydride 14.8g (0.1mol), stirring and dissolving is stirred at reflux 5 hours, increasingly generates solid, suction filtration is gone
Solid, with recrystallizing methanol, obtains orange solids.
Synthetic route is as follows：
(5) preparation of dyestuff 2
10mL toluene, then middle addition 580mg (1.85mol) compound 2,341mg are added into 50mL round-bottomed flasks
(2.0mol) acenaphthene phenol sterling and 1.0mL methanesulfonic acids, in 65 DEG C of oil bath heatings, stir 30 minutes, reaction solution are extracted with ethyl acetate
Take, then wash ethyl acetate extraction phase 2 times, use anhydrous Na2SO4Dry, obtain the crude product of dyestuff 2；The crude product of dyestuff 2 is further used
Pillar layer separation, eluant, eluent：DCM：MeOH=40：1, solvent is rotated out, is dried in vacuo, obtains dark red solid 305.7mg
(yield, 37%), the i.e. sterling of dyestuff 2.
Synthetic route is as follows：
The hydrogen nuclear magnetic resonance spectrogram of dyestuff 2 as shown in figure 4,1H NMR(400MHz,CDCl3) δ 8.17 (d, J=8.2Hz,
1H), 8.05 (dd, J=6.5,1.4Hz, 1H), 7.62 (tdd, J=19.1,10.1,4.8Hz, 3H), 7.39 (d, J=6.8Hz,
1H), 7.19-7.15 (m, 1H), 6.63 (dd, J=8.1,5.7Hz, 2H), 6.51 (s, 1H), 6.41 (dd, J=8.9,2.6Hz,
1H), 5.30 (s, 2H), 3.47-3.28 (m, 6H), 3.24-3.11 (m, 2H), 1.21 (t, J=7.1Hz, 6H)；The core of dyestuff 2
Magnetic resonance carbon spectrogram as shown in figure 5,13C NMR(101MHz,CDCl3)δ169.55,164.04,154.11,151.75,
151.45,145.67,144.42,141.24,140.38,135.20,133.26,129.81,129.21,128.59,127.59,
126.16,125.12,124.11,121.85,121.70,117.84,117.47,116.39,116.31,113.84,110.38,
83.42,77.34,77.23,77.02,76.70,30.84,29.64,22.70,14.85,14.21.Matter is carried out to the sterling of dyestuff 2
Analysis of spectrum, as a result as shown in fig. 6, explanation has synthesized dyestuff 2.
(6) preparation of compound 3
6mL dimethylformamides are added into 100mL round-bottomed flasks, 1.3g meta-aminophenols, 3.2g sodium acid carbonates is added
And the bromo- 3- chloropropanes of 3.4mL 1-, stir and evenly mix, and in 70 DEG C of stirrings, thin-layer chromatography detection reaction has generated compound 3, then
Further separated using column chromatography, eluant, eluent uses petroleum ether：Ethyl acetate=20：1, obtain compound 3.
Synthetic route is as follows：
(7) preparation of compound 4
40mL toluene is added into 150mL round-bottomed flasks, 18.9g (0.1mol) compound 3, phthalic anhydride is added
14.8g (0.1mol), stirring and dissolving is stirred at reflux 5 hours, increasingly generates solid, suction filtration removes solid, with recrystallizing methanol, obtains
Dark red solid.
Synthetic route is as follows：
(8) preparation of dyestuff 3
3mL toluene, then middle addition 40mg (0.119mol) compound 4,50mg are added into 50mL round-bottomed flasks
(0.29mol) acenaphthene phenol sterling and 0.5mL methanesulfonic acids, in 65 DEG C of oil bath heatings, stir 30 minutes, reaction solution are extracted with ethyl acetate
Take, then wash ethyl acetate extraction phase 2 times, use anhydrous Na2SO4Dry, obtain the crude product of dyestuff 3；The crude product of dyestuff 3 is further used
Pillar layer separation, eluant, eluent：DCM：MeOH=80:1, solvent is rotated out, is dried in vacuo, obtains dark red solid 50mg
(yield, 89.3%), the i.e. sterling of dyestuff 3.
Synthetic route is as follows：
The carbon-13 nmr spectra figure of dyestuff 3 as shown in fig. 7,1H NMR(400MHz,CDCl3)δ8.23–8.19(m,1H),
8.15 (d, J=8.2Hz, 1H), 7.71-7.63 (m, 2H), 7.63-7.58 (m, 1H), 7.47 (d, J=6.9Hz, 1H), 7.21-
7.15 (m, 1H), 6.64 (s, 1H), 6.49 (s, 1H), 3.46-3.30 (m, 6H), 3.27-3.18 (m, 2H), 3.14 (t, J=
6.4Hz, 2H), 2.69-2.56 (m, 3H), 2.17-2.06 (m, 2H), 1.93 (dd, J=11.9,5.9Hz, 2H).It is pure to dyestuff 3
Product carry out mass spectral analysis, as a result as shown in Figure 10, illustrate to have synthesized dyestuff 3.
Physical property is probed into
(9) application test
1) configuration of stand-by storage liquid is detected
A. the sample solution (1.00 × 10 of dyestuff 1-3mol·L-1) preparation：0.0039g (M=392) dyestuff 1 is taken to be dissolved in
In 10mL ethanol, it is 1.00 × 10 to be made into concentration-3mol·L-1Solution.
B. the sample solution (1.00 × 10 of dyestuff 2-3mol·L-1) preparation：0.0045g (M=448) dyestuff 2 is taken to be dissolved in
In 10mL ethanol, it is 1.00 × 10 to be made into concentration-3mol·L-1Solution.
C. the sample solution (1.00 × 10 of dyestuff 3-3mol·L-1) preparation：0.0047g (M=472) dyestuff 3 is taken to be dissolved in
10mL ethanol, it is 1.00 × 10 to be made into concentration-3mol·L-1Solution.
D. pH=1 solution is prepared with 37% hydrochloric acid, acid-base value is determined with pH test paper；PH is made into sodium hydroxide solution
=14 solution, acid-base value is determined with pH test paper；Mutually matched in two solutions and obtain pH by 1 to 14 13 kinds of different soda acids
The solution of gradient is spent, acid-base value is determined with pH test paper.
2) test and analyze
The sample solution of 30 μ L dyestuffs 1, the sample solution of dyestuff 2 and the sample solution of dyestuff 3 are taken respectively, are added and are extremely gone equipped with 3mL
In the cuvette of ionized water, spectrophotometry test and fluorescence spectrophotometry test are then carried out to it, is as a result divided
Not as shown in FIG. 9 and 10.
As can be seen that the physical property of dyestuff 1, dyestuff 2 and dyestuff 3 is as shown in table 1 (wherein, from Fig. 9 and Figure 10
Stokes displacements are the differences of maximum emission wavelength and maximum absorption wavelength).
The physical property of the dyestuff 1 of table 1, dyestuff 2 and dyestuff 3
3mL pH=1 solution is taken, the sample solution of 30 μ L dyestuffs 1 is added, is put into ultraviolet-visible spectrometer and detects dyestuff
1 absorbance change under the conditions of this pH, same detection method obtains dyestuff 1 in the absorbance change of pH=2~14.
3mL pH=1 solution is taken, the sample solution of 30 μ L dyestuffs 1 is added, is put into XRF and detects dyestuff 1 herein
Absorbance change under the conditions of pH, same detection method obtains dyestuff 1 in the fluorescence intensity change of pH=2~14.
As a result it is ((a) is uv-vis spectra, and (b) is fluorescence spectrum) shown in Figure 11, in the range of pH=4~14, dye
The absorbance and fluorescence intensity of material 1 gradually step-down with pH increase.
3mL pH=1 solution is taken, the sample solution of 30 μ L dyestuffs 2 is added, is put into ultraviolet-visible spectrometer and detects dyestuff
2 absorbance change under the conditions of this pH, same detection method obtains dyestuff 2 in the absorbance change of pH=2~14.
3mL pH=1 solution is taken, the sample solution of 30 μ L dyestuffs 2 is added, is put into XRF and detects dyestuff 2 herein
Absorbance change under the conditions of pH, same detection method obtains dyestuff 2 in the fluorescence intensity change of pH=2~14.
As a result it is ((a) is uv-vis spectra, and (b) is fluorescence spectrum) shown in Figure 12, in the range of pH=2~14, dye
The absorbance and fluorescence intensity of material 2 gradually step-down with pH increase.
3mL pH=1 solution is taken, the sample solution of 30 μ L dyestuffs 3 is added, is put into ultraviolet-visible spectrometer and detects dyestuff
3 absorbance change under the conditions of this pH, same detection method obtains dyestuff 3 in the absorbance change of pH=2~14.
3mL pH=1 solution is taken, the sample solution of 30 μ L dyestuffs 3 is added, is put into XRF and detects dyestuff 3 herein
Absorbance change under the conditions of pH, same detection method obtains dyestuff 3 in the fluorescence intensity change of pH=2~14.
As a result it is ((a) is uv-vis spectra, and (b) is fluorescence spectrum) shown in Figure 13, can be seen that from ultraviolet spectra
In the range of pH=1~14, the absorbance of the dyestuff 3 gradually step-down with pH increase；It can be seen that from fluorescence spectrum
In the range of pH=1~7, the fluorescence intensity of dyestuff 3 is gradually uprised with pH increase, in the range of pH=8~14, dyestuff
Fluorescence intensity gradually step-down with pH increase.
Claims (10)
1. a class rhodamine fluorescent dyes, it is characterised in that the fluorochrome is any in dyestuff 1, dyestuff 2 and dyestuff 3
One kind, wherein dyestuff 1, dyestuff 2, the structural formula of dyestuff 3 distinguish as follows：
2. the preparation method of rhodamine fluorescent dyes described in claim 1, it is characterised in that comprise the following steps：
(1) resorcinol obtains compound 1 with phthalic anhydride；3- hydroxy-ns, N- diethylanilines and O-phthalic
Anhydride reaction obtains compound 2；Meta-aminophenol reacts to obtain compound 3, compound 3 and phthalic acid with the bromo- 3- chloropropanes of 1-
Anhydride reactant obtains compound 4；Compound 1, compound 2, compound 3 and compound 4 chemical formula it is as follows：
(2) by catalyst of methanesulfonic acid, toluene be reaction dissolvent, by acenaphthene phenol distinguish compound 1, compound 2 and compound 4 it is anti-
Should, obtain dyestuff 1, dyestuff 2 and dyestuff 3.
3. the preparation method of rhodamine fluorescent dyes according to claim 2, it is characterised in that compound 1 in step (1)
Preparation method is specially：Resorcinol and phthalic anhydride are dissolved in toluene, are stirred at reflux to generation solid, suction filtration takes
Solid, with recrystallizing methanol, is produced；Wherein, the mol ratio of resorcinol and phthalic anhydride is 1：1.
4. the preparation method of rhodamine fluorescent dyes according to claim 2, it is characterised in that compound 2 in step (1)
Preparation method is specially：By 3- hydroxy-ns, N- diethylanilines and phthalic anhydride are dissolved in toluene, are stirred at reflux to life
Into solid, suction filtration takes solid, with recrystallizing methanol, produces；Wherein, 3- hydroxy-ns, N- diethylanilines and phthalic anhydride
Mol ratio be 1：1.
5. the preparation method of rhodamine fluorescent dyes according to claim 2, it is characterised in that compound 3 in step (1)
Preparation method is specially：Meta-aminophenol, sodium acid carbonate and the bromo- 3- chloropropanes of 1- are added into dimethylformamide, is stirred and evenly mixed,
And continue to stir in 65~75 DEG C, thin-layer chromatography detection reaction has generated compound 3, then is further separated using column chromatography, i.e.,
；Wherein, the mol ratio of meta-aminophenol, sodium acid carbonate and the bromo- 3- chloropropanes of 1- is 1：3~3.5：2.5~3.
6. the preparation method of rhodamine fluorescent dyes according to claim 2, it is characterised in that compound 4 in step (1)
Preparation method is specially：Compound 3 and phthalic anhydride are dissolved in toluene, are stirred at reflux to generation solid, suction filtration takes
Solid, with recrystallizing methanol, is produced；Wherein, compound 3 and the mol ratio of phthalic anhydride are 1：1.
7. the preparation method of rhodamine fluorescent dyes according to claim 2, it is characterised in that the system of acenaphthene phenol in step (2)
Preparation Method comprises the following steps：
(1) POCl3 and DMF are sequentially added into acenaphthene, 90~95 DEG C, continuation are warming up to after stirring and evenly mixing
Stirring 2.5~3.5 hours, obtains reaction solution；Reaction solution is added in mixture of ice and water, sticky solid is generated, through suction filtration and very
Sky is dried, and obtains 5- acenaphthene aldehyde crude products；Wherein, the mol ratio of acenaphthene, POCl3 and DMF is 1：2~2.5：5
~6；
(2) 5- acenaphthene aldehyde crude products obtained by step (1) are used into pillar layer separation, is dried in vacuo, obtains 5- acenaphthene aldehyde sterlings；
(3) 5- acenaphthene aldehyde sterling, selenium dioxide, hydrogen peroxide and glacial acetic acid are added into dichloromethane, 35 are stirred in 20~30 DEG C
~40 hours, filter to take after filtrate, stratification, take organic layer to evaporate solvent, and potassium hydroxide is dissolved in ice bath environment
In methanol solution, then after being placed in and hydrolyzing 2.5~3.5 hours at room temperature, hydrochloric acid acidifying is added, then is extracted with ethyl acetate, is washed
Ethyl acetate extraction phase, drying, obtain acenaphthene phenol crude product；Wherein, the dosage of 5- acenaphthenes aldehyde sterling is 80~100g/ in dichloromethane
L, the dosage of selenium dioxide are that 2~3g/L, the dosage of hydrogen peroxide are that 1.6~2mol/L, the dosage of glacial acetic acid are
0.29~0.35mol/L；
(4) acenaphthene phenol crude product obtained by step (3) is used into pillar layer separation, is dried in vacuo, produces acenaphthene phenol sterling.
8. the preparation method of rhodamine fluorescent dyes according to claim 2, it is characterised in that dyestuff 1, dye in step (2)
Material 2 preparation method be specially：Compound 1 or compound 2 are added into toluene, acenaphthene phenol and methanesulfonic acid are added, in 60~70
DEG C stirring 25~35 minutes, reaction solution is extracted with ethyl acetate, then wash ethyl acetate extraction phase, drying, respectively obtains dye
Expect 1 crude product or the crude product of dyestuff 2；The crude product of dyestuff 1 or the crude product of dyestuff 2 are further used into pillar layer separation, vacuum drying obtains dyestuff
1 sterling or the sterling of dyestuff 2；Wherein, the mol ratio of compound 1, acenaphthene phenol and methanesulfonic acid is 1：1：26~27, compound 2, acenaphthene phenol and
The mol ratio of methanesulfonic acid is 1：1.0~1.1：8~9.
9. the preparation method of rhodamine fluorescent dyes according to claim 2, it is characterised in that the system of dyestuff 3 in step (2)
Preparation Method is specially：Compound 4, acenaphthene phenol and methanesulfonic acid are added into toluene, stirs 25~35 minutes, will react in 60~70 DEG C
Liquid is extracted with dichloromethane, then washes dichloromethane extraction phase, drying, obtains the crude product of dyestuff 3；The crude product of dyestuff 3 is further used
Pillar layer separation, vacuum drying, obtains the sterling of dyestuff 3；Wherein, the mol ratio of compound 4, acenaphthene phenol and methanesulfonic acid is 1：2~3：
64~66.
10. application of the rhodamine fluorescent dyes in fluoroscopic examination and pH probes described in claim 1.
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| CN108191880A (en) * | 2018-01-19 | 2018-06-22 | 天津理工大学 | A kind of fluorescent dye preparation method and application with carbazole-rhodamine hybrid structure |
| CN110006870A (en) * | 2019-04-29 | 2019-07-12 | 陕西科技大学 | A kind of fluorescent optical sensor and its preparation method and application of efficient detection diethylamine |
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