CN107090191B - A kind of rhodamine fluorescent dyes and preparation method thereof - Google Patents
A kind of rhodamine fluorescent dyes and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of rhodamine fluorescent dyes and preparation method thereof, based on classical rhodamine synthetic method, pass through reasonable structural modification, the chemical group of different function is introduced on rhodamine parent, increase conjugation, change hyperchromic group, such as: hydroxyl, diethylin, the structures such as azabicyclo.Novel rhodamine dyestuff produced by the present invention has bigger launch wavelength and bigger quantum yield, also has more reaction sites, keeps subsequent reactions more convenient；And there is moderate Stokes shift, the interference for the excitation wavelength that can forgo in subsequent fluorescence detection keeps analysis result more accurate.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to a kind of rhodamine fluorescent dyes and preparation method thereof.
Background technique
Rhodamine compound is the alkaline xanthene dye using xanthene as parent, due to special structure and corresponding glimmering
Light characteristic becomes rhodamine fluorescent dye in chemistry and field of bioanalysis and studies relatively broad project.Related Luo Dan
The report of synthesis, ionization and the structure of bright fluorochrome, optical characteristics and analysis etc. is existing very much.It is commonly used with other
Fluorescent dye compare, rhodamine fluorescent dye has good light stability, wider wave-length coverage insensitive to pH and higher
Fluorescence quantum yield the advantages that, therefore be widely used in pharmacology, physiology, molecular biology, cell biology, molecule
Science of heredity, Environmental Chemistry, individual molecule detection, information science, fluorescent marker, laser dye etc., are analytical chemistry and life
Most common fluorescent dye in the field of biotechnology such as object medical science.
Rhodamine Derivatives are most widely used a class of dyes, rhodamine 6G and Luo Dan in small organic molecule probe field
Bright B have many advantages, such as that molar absorption coefficient is big, fluorescence quantum yield is high and the preferable object of photostability and rhodamine it is 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 variation, to realize the fluorescence detection to object, which is widely used to rhodamine small-molecule fluorescent probe
Design.Become the research hotspot of sensory field using principle building fluorescence probe.
General with will be used wider and wider, the research and development of rhodamine fluorescent dye is rapid and receives more weights
Report detection of the fluorescence probe based on rhodamine Spirocyclic derivatives for plurality of target object depending on, lot of documents, 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 valence
Value, design synthesis a series of new rhodamine fluorescent dye are necessary.
Summary of the invention
The object of the present invention is to provide a kind of novel rhodamine fluorescent dyes, with bigger quantum yield and fit
In Stokes shift, the present invention also provides the preparation methods of such rhodamine fluorescent dyes.
To achieve the goals above, the technical solution adopted by the present invention are as follows:
A kind of rhodamine fluorescent dyes, the fluorochrome are any one in dyestuff 1, dyestuff 2 and dyestuff 3, wherein
Dyestuff 1, dyestuff 2, the structural formula difference of dyestuff 3 are as follows:
The preparation method of above-mentioned rhodamine fluorescent dyes, comprising the following steps:
(1) resorcinol and phthalic anhydride obtain compound 1；3- hydroxy-n, N- diethylaniline and adjacent benzene
Dicarboxylic acid anhydride reacts to obtain compound 2；Meta-aminophenol reacts to obtain compound 3, compound 3 and adjacent benzene two with the bromo- 3- chloropropane of 1-
Formic acid anhydride reactant obtains compound 4；Compound 1, compound 2, the chemical formula of compound 3 and compound 4 are as follows:
It (2) is reaction dissolvent by catalyst, toluene of methanesulfonic acid, by acenaphthene phenol difference compound 1, compound 2 and compound 4
Reaction, obtains dyestuff 1, dyestuff 2 and dyestuff 3.
Preferably, in step (1) compound 1 preparation method specifically: resorcinol and phthalic anhydride are dissolved
In toluene, be stirred at reflux to generate solid, suction filtration take solid, with recrystallizing methanol to get；Wherein, resorcinol in toluene
Dosage be 2~3mol/L, the molar ratio of resorcinol and phthalic anhydride is 1:1.
Preferably, in step (1) compound 2 preparation method specifically: by 3- hydroxy-n, N- diethylaniline and adjacent benzene
Dicarboxylic acid anhydride is dissolved in toluene, be stirred at reflux to generate solid, suction filtration take solid, with recrystallizing methanol to get；Wherein, first
3- hydroxy-n in benzene, the dosage of N- diethylaniline are 2~3mol/L, 3- hydroxy-n, N- diethylaniline and O-phthalic
The molar ratio of acid anhydrides is 1:1.
Preferably, in step (1) compound 3 preparation method specifically: into dimethylformamide be added meta-aminophenol,
Sodium bicarbonate and the bromo- 3- chloropropane of 1-, stir and evenly mix, and continue to stir in 65~75 DEG C, and thin-layer chromatography detection reaction has generated
Compound 3, then using column chromatography further separate to get；In dimethylformamide the dosage of meta-aminophenol be 1.5~
2.5mol/L, the molar ratio of meta-aminophenol, sodium bicarbonate and the bromo- 3- chloropropane of 1- are 1:3~3.5:2.5~3, pillar layer separation
When eluant, eluent use petroleum ether: ethyl acetate=20:1.
Preferably, in step (1) compound 4 preparation method specifically: compound 3 and phthalic anhydride are dissolved in
In toluene, be stirred at reflux to generate solid, suction filtration take solid, with recrystallizing methanol to get；Wherein, in toluene compound 3 throwing
Dosage is 2~3mol/L, and the molar ratio of compound 3 and phthalic anhydride is 1:1.
Preferably, in step (2) acenaphthene phenol preparation method the following steps are included:
(1) phosphorus oxychloride and n,N-Dimethylformamide are sequentially added into acenaphthene, and 90~95 DEG C are warming up to after stirring and evenly mixing,
Continue stirring 2.5~3.5 hours, obtains reaction solution；Reaction solution is added in mixture of ice and water, sticky solid is generated, through filtering
And vacuum drying, obtain 5- acenaphthene aldehyde crude product；Wherein, the molar ratio of acenaphthene, phosphorus oxychloride and n,N-Dimethylformamide be 1:2~
2.5:5~6；
(2) 5- acenaphthene aldehyde crude product obtained by step (1) is used into pillar layer separation, vacuum drying obtains 5- acenaphthene aldehyde sterling；Its
In, eluant, eluent is petroleum ether: ethyl acetate=38~42:1 when pillar layer separation；
(3) 5- acenaphthene aldehyde sterling, selenium dioxide, hydrogen peroxide and glacial acetic acid are added into methylene chloride, is stirred in 20~30 DEG C
It mixes 35~40 hours, after filtering to take filtrate, stratification, takes organic layer to evaporate solvent, and be dissolved in hydroxide 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 acidification is added, then is extracted with ethyl acetate,
Ethyl acetate extraction phase, drying are washed, acenaphthene phenol crude product is obtained；Wherein, in methylene chloride 5- acenaphthene aldehyde sterling dosage be 80~
100g/L, selenium dioxide dosage be 2~3g/L, the dosage of hydrogen peroxide is 1.6~2mol/L, the dosage of 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, be dried in vacuo to get acenaphthene phenol sterling；Wherein, it washes
De- agent is petroleum ether: ethyl acetate=28~32:1.
Preferably, in step (2) dyestuff 1 preparation method specifically: compound 1, acenaphthene phenol and methylsulphur are added into toluene
Acid continues stirring 25~35 minutes in 60~70 DEG C, reaction solution is extracted with ethyl acetate, then wash ethyl acetate extraction phase,
It is dry, obtain 1 crude product of dyestuff；1 crude product of dyestuff is further used into pillar layer separation, is dried in vacuo, obtains 1 sterling of dyestuff；Wherein,
The dosage of compound 1 is 0.09~1.0mol/L in toluene, the molar ratio of compound 1, acenaphthene phenol and methanesulfonic acid be 1:1:26~
27, eluant, eluent uses methylene chloride: methanol=48~52:1 when pillar layer separation.
Preferably, in step (2) dyestuff 2 preparation method specifically: compound 2, acenaphthene phenol and methylsulphur are added into toluene
Acid continues stirring 25~35 minutes in 60~70 DEG C, reaction solution is extracted with ethyl acetate, then wash ethyl acetate extraction phase,
It is dry, obtain 2 crude product of dyestuff；2 crude product of dyestuff is further used into pillar layer separation, is dried in vacuo, obtains 2 sterling of dyestuff；Wherein,
The dosage of compound 2 is 0.18~0.19mol/L in toluene, the molar ratio of compound 2, acenaphthene phenol and methanesulfonic acid be 1:1.0~
1.1:8~9, eluant, eluent uses methylene chloride: methanol=38~42:1 when pillar layer separation.
Preferably, in step (2) dyestuff 3 preparation method specifically: compound 4, acenaphthene phenol and methylsulphur are added into toluene
Acid continues stirring 25~35 minutes in 60~70 DEG C, reaction solution is extracted with dichloromethane, then wash methylene chloride extraction phase,
It is dry, obtain 3 crude product of dyestuff；3 crude product of dyestuff is further used into pillar layer separation, is dried in vacuo, obtains 3 sterling of dyestuff；Wherein,
The dosage of compound 4 is 0.035~0.045mol/L in toluene, the molar ratio of compound 4, acenaphthene phenol and methanesulfonic acid be 1:2~
3:64~66, eluant, eluent uses methylene chloride: methanol=78~82:1 when pillar layer separation.
Application of the above-mentioned rhodamine fluorescent dyes in fluorescence detection and pH probe.
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 disclosed in method or the prior art obtains.
The present invention has more excellent performance compared to classical rhodamine, above-mentioned three kinds of Novel rhodamine dyestuffs:
(1) more reaction sites keep subsequent reactions more convenient；(2) fluorescence emission wavelengths of bigger launch wavelength, dyestuff three exist
606nm belongs near infrared region, can be fabulous applied to active somatic cell dyeing, analysis；(3) bigger quantum yield is inherited
The feature high with rhodamine fluorescent dye quantum yield has been developed；(4) moderate Stokes shift, can be in subsequent fluorescence
The interference for excitation wavelength of forgoing in detection keeps analysis result more accurate.
Detailed description of the invention
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 color photo；
Figure 10 is the photo of color shown in dyestuff 1, the fluorescence spectrum of dyestuff 2 and dyestuff 3 and its 365nm ultraviolet lamp are lower；
Figure 11 is uv-vis spectra and fluorescence spectrum of the dyestuff 1 at different pH；
Figure 12 is uv-vis spectra and fluorescence spectrum of the dyestuff 2 at different pH；
Figure 13 is uv-vis spectra and fluorescence spectrum of the dyestuff 3 at different pH.
Specific 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 the three-necked flask of 100mL, then by 6.5mL phosphorus oxychloride (POCl3) use perseverance
Pressure funnel is slowly added in three-necked flask and (is added dropwise in 15 minutes), adds 13.5mL n,N-Dimethylformamide
(DMF), stirring is to slowly warm up to 90~95 DEG C after five minutes, continues stirring 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, filters and is dried in vacuo through decompression, obtains acenaphthene aldehyde crude product；Then
Using pillar layer separation, eluant, eluent is petroleum ether: ethyl acetate=40:1, and it is solid to obtain 2.759g pale yellow needles for vacuum drying
Body, i.e. 5- acenaphthene aldehyde sterling, yield 46.74%.
11mL methylene chloride and 1.0g 5- acenaphthene aldehyde are added into the round-bottomed flask of 50mL, adds 30mg selenium dioxide
(SeO2) and 30% hydrogen peroxide (H of 2mL2O2), 4 drops glacial acetic acid (about 0.2mL) are then added dropwise, it is small in 25 DEG C of stirring in water bath 38
When, after filtering to take filtrate, stratification, take organic layer to rotate solvent, and 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, be added 5mL mass fraction
It is acidified, then is extracted with ethyl acetate for 10% dilute hydrochloric acid, be washed with deionized ethyl acetate extraction phase 2 times, then with suitable
It is 30 minutes dry to measure anhydrous sodium sulfate, obtains 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 solid, i.e. acenaphthene phenol sterling, yield 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 flask, adds resorcinol 11.0g (0.1mol) and adjacent benzene
Dicarboxylic acid anhydride 14.8g (0.1mol), stirring and dissolving are stirred at reflux 5 hours, increasingly generate solid, suction filtration removes solid, with 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 flask
(0.29mol) acenaphthene phenol sterling and 0.5mL methanesulfonic acid (MeSO3H), in 65 DEG C of oil bath heatings, stir 30 minutes, by reaction solution second
Acetoacetic ester extraction, then wash ethyl acetate extraction phase 2 times, use anhydrous Na2SO4It is dry, obtain 1 crude product of dyestuff；By 1 crude product of dyestuff
Pillar layer separation is further used, eluant, eluent is methylene chloride: methanol (DCM:MeOH)=50:1 rotates out solvent, vacuum drying,
Obtain 85mg dark red solid (yield, 74%), i.e. 1 sterling of dyestuff.
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,
30.84,29.62.1 sterling of dyestuff is analyzed by mass spectrometry, as a result as shown in figure 3, illustrating to have synthesized dyestuff 1.
(4) preparation of compound 2
40mL toluene is added into 150mL round-bottomed flask, adds 3- hydroxy-n, N- diethylaniline 16.5g
(0.1mol), phthalic anhydride 14.8g (0.1mol), stirring and dissolving are stirred at reflux 5 hours, increasingly generate solid, and suction filtration is gone
Solid obtains orange solids with recrystallizing methanol.
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 flask
(2.0mol) acenaphthene phenol sterling and 1.0mL methanesulfonic acid stir 30 minutes in 65 DEG C of oil bath heatings, reaction solution ethyl acetate are extracted
It takes, then washes ethyl acetate extraction phase 2 times, uses anhydrous Na2SO4It is dry, obtain 2 crude product of dyestuff；2 crude product of dyestuff is further used
Pillar layer separation, eluant, eluent: DCM:MeOH=40:1 rotates out solvent, and vacuum drying obtains dark red solid 305.7mg
(yield, 37%), i.e. 2 sterling of dyestuff.
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 2 sterling of dyestuff
Spectrum analysis, as a result as shown in fig. 6, illustrating to have synthesized dyestuff 2.
(6) preparation of compound 3
6mL dimethylformamide is added into 100mL round-bottomed flask, adds 1.3g meta-aminophenol, 3.2g sodium bicarbonate
And the bromo- 3- chloropropane of 3.4mL 1-, it stirring and evenly mixing, and stirred in 70 DEG C, thin-layer chromatography detection reaction has generated compound 3, then
It is further separated using column chromatography, eluant, eluent uses petroleum ether: ethyl acetate=20:1 obtains compound 3.
Synthetic route is as follows:
(7) preparation of compound 4
40mL toluene is added into 150mL round-bottomed flask, adds 18.9g (0.1mol) compound 3, phthalic anhydride
14.8g (0.1mol), stirring and dissolving are stirred at reflux 5 hours, increasingly generate solid, and 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 flask
(0.29mol) acenaphthene phenol sterling and 0.5mL methanesulfonic acid stir 30 minutes in 65 DEG C of oil bath heatings, reaction solution ethyl acetate are extracted
It takes, then washes ethyl acetate extraction phase 2 times, uses anhydrous Na2SO4It is dry, obtain 3 crude product of dyestuff；3 crude product of dyestuff is further used
Pillar layer separation, eluant, eluent: DCM:MeOH=80:1 rotates out solvent, and vacuum drying obtains dark red solid 50mg
(yield, 89.3%), i.e. 3 sterling of dyestuff.
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 are analyzed by mass spectrometry, and the results are 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. 1 sample solution (1.00 × 10 of dyestuff-3mol·L-1) preparation: take 0.0039g (M=392) dyestuff 1 to be dissolved in
In 10mL ethyl alcohol, being made into concentration is 1.00 × 10-3mol·L-1Solution.
B. 2 sample solution (1.00 × 10 of dyestuff-3mol·L-1) preparation: take 0.0045g (M=448) dyestuff 2 to be dissolved in
In 10mL ethyl alcohol, being made into concentration is 1.00 × 10-3mol·L-1Solution.
C. 3 sample solution (1.00 × 10 of dyestuff-3mol·L-1) preparation: take 0.0047g (M=472) dyestuff 3 to be dissolved in
10mL ethyl alcohol, being made into concentration is 1.00 × 10-3mol·L-1Solution.
D. the solution of pH=1 is prepared with 37% hydrochloric acid, determines pH value with pH test paper；PH is made into sodium hydroxide solution
=14 solution determines pH value with pH test paper；It is mutually matched in two solution and obtains pH by 1 to 14 13 kinds of different soda acids
The solution for spending gradient, determines pH value with pH test paper.
2) it tests and analyzes
30 μ L dyestuff, 1 sample solution, 3 sample solution of 2 sample solution of dyestuff and dyestuff 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 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 displacement is the difference of maximum emission wavelength and maximum absorption wavelength).
The physical property of 1 dyestuff 1 of table, dyestuff 2 and dyestuff 3
The solution of 3mL pH=1 is taken, 30 μ L dyestuff, 1 sample solution is added, is put into ultraviolet-visible spectrometer and detects dyestuff
1 absorbance change under the conditions of this pH, same detection method obtain dyestuff 1 in the absorbance change of pH=2~14.
The solution of 3mL pH=1 is taken, 30 μ L dyestuff, 1 sample solution is added, is put into Fluorescence Spectrometer and detects dyestuff 1 herein
Absorbance change under the conditions of pH, same detection method obtain dyestuff 1 in the fluorescence intensity change of pH=2~14.
It as a result is ((a) is uv-vis spectra, (b) is fluorescence spectrum) shown in Figure 11, in the range of pH=4~14, dye
The absorbance and fluorescence intensity of material 1 are gradually lower with the increase of pH.
The solution of 3mL pH=1 is taken, 30 μ L dyestuff, 2 sample solution is added, is put into ultraviolet-visible spectrometer and detects dyestuff
2 absorbance change under the conditions of this pH, same detection method obtain dyestuff 2 in the absorbance change of pH=2~14.
The solution of 3mL pH=1 is taken, 30 μ L dyestuff, 2 sample solution is added, is put into Fluorescence Spectrometer and detects dyestuff 2 herein
Absorbance change under the conditions of pH, same detection method obtain dyestuff 2 in the fluorescence intensity change of pH=2~14.
It as a result is ((a) is uv-vis spectra, (b) is fluorescence spectrum) shown in Figure 12, in the range of pH=2~14, dye
The absorbance and fluorescence intensity of material 2 are gradually lower with the increase of pH.
The solution of 3mL pH=1 is taken, 30 μ L dyestuff, 3 sample solution is added, is put into ultraviolet-visible spectrometer and detects dyestuff
3 absorbance change under the conditions of this pH, same detection method obtain dyestuff 3 in the absorbance change of pH=2~14.
The solution of 3mL pH=1 is taken, 30 μ L dyestuff, 3 sample solution is added, is put into Fluorescence Spectrometer and detects dyestuff 3 herein
Absorbance change under the conditions of pH, same detection method obtain dyestuff 3 in the fluorescence intensity change of pH=2~14.
As a result it is ((a) is uv-vis spectra, (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 dyestuff 3 is gradually lower with the increase of pH；It can be seen that from fluorescence spectrum
In the range of pH=1~7, the fluorescence intensity of dyestuff 3 is gradually got higher with the increase of pH, in the range of pH=8~14, dyestuff
Fluorescence intensity is gradually lower with the increase of pH.
Claims (9)
1. a kind of rhodamine fluorescent dyes, which is characterized in that the fluorochrome is any one in dyestuff 1 and dyestuff 3,
Middle dyestuff 1, the structural formula difference of dyestuff 3 are as follows:
2. the preparation method of rhodamine fluorescent dyes described in claim 1, which comprises the following steps:
(1) resorcinol and phthalic anhydride obtain compound 1；Meta-aminophenol reacts to change with the bromo- 3- chloropropane of 1-
Object 3 is closed, compound 3 and phthalic anhydride obtain compound 4；The chemical formula of compound 1, compound 3 and compound 4 is such as
Under:
(2) it is reaction dissolvent by catalyst, toluene of methanesulfonic acid, is reacted, obtained with compound 1 and compound 4 respectively by acenaphthene phenol
Dyestuff 1 and dyestuff 3.
3. the preparation method of rhodamine fluorescent dyes according to claim 2, which is characterized in that compound 1 in step (1)
Preparation method specifically: resorcinol and phthalic anhydride are dissolved in toluene, are stirred at reflux to solid is generated, suction filtration takes
Solid, with recrystallizing methanol to get；Wherein, the molar ratio of resorcinol and phthalic anhydride is 1:1.
4. the preparation method of rhodamine fluorescent dyes according to claim 2, which is characterized in that compound 3 in step (1)
Preparation method specifically: meta-aminophenol, sodium bicarbonate and the bromo- 3- chloropropane of 1- are added into dimethylformamide, stirs and evenly mixs,
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 molar ratio of meta-aminophenol, sodium bicarbonate and the bromo- 3- chloropropane of 1- is 1:3~3.5:2.5~3.
5. the preparation method of rhodamine fluorescent dyes according to claim 2, which is characterized in that compound 4 in step (1)
Preparation method specifically: compound 3 and phthalic anhydride are dissolved in toluene, are stirred at reflux to solid is generated, suction filtration takes
Solid, with recrystallizing methanol to get；Wherein, the molar ratio of compound 3 and phthalic anhydride is 1:1.
6. the preparation method of rhodamine fluorescent dyes according to claim 2, which is characterized in that the system of acenaphthene phenol in step (2)
Preparation Method the following steps are included:
(1) phosphorus oxychloride and n,N-Dimethylformamide are sequentially added into acenaphthene, 90~95 DEG C are warming up to after stirring and evenly mixing, and are continued
Stirring 2.5~3.5 hours, obtains reaction solution；Reaction solution is added in mixture of ice and water, sticky solid is generated, is filtered and true
Sky is dry, obtains 5- acenaphthene aldehyde crude product；Wherein, the molar ratio of acenaphthene, phosphorus oxychloride and n,N-Dimethylformamide is 1:2~2.5:5
~6；
(2) 5- acenaphthene aldehyde crude product obtained by step (1) is used into pillar layer separation, vacuum drying obtains 5- acenaphthene aldehyde sterling；
(3) 5- acenaphthene aldehyde sterling, selenium dioxide, hydrogen peroxide and glacial acetic acid are added into methylene chloride, stirs 35 in 20~30 DEG C
~40 hours, after filtering to take filtrate, stratification, organic layer is taken to evaporate solvent, and be dissolved in potassium hydroxide in ice bath environment
In methanol solution, then after being placed in and hydrolyzing 2.5~3.5 hours at room temperature, hydrochloric acid acidification is added, then is extracted with ethyl acetate, washes
Ethyl acetate extraction phase, drying obtain acenaphthene phenol crude product；Wherein, the dosage of 5- acenaphthene aldehyde sterling is 80~100g/ in methylene chloride
L, the dosage of selenium dioxide is 2~3g/L, the dosage of hydrogen peroxide is 1.6~2mol/L, the dosage of glacial acetic acid is
0.29~0.35mol/L；
(4) acenaphthene phenol crude product obtained by step (3) is used into pillar layer separation, be dried in vacuo to get acenaphthene phenol sterling.
7. the preparation method of rhodamine fluorescent dyes according to claim 2, which is characterized in that the system of dyestuff 1 in step (2)
Preparation Method specifically: compound 1 is added into toluene, adds acenaphthene phenol and methanesulfonic acid, is stirred 25~35 minutes in 60~70 DEG C,
Reaction solution is extracted with ethyl acetate, then washes ethyl acetate extraction phase, drying, obtains 1 crude product of dyestuff；By 1 crude product of dyestuff into
One step pillar layer separation, vacuum drying, obtains 1 sterling of dyestuff；Wherein, the molar ratio of compound 1, acenaphthene phenol and methanesulfonic acid is 1:
1:26~27.
8. the preparation method of rhodamine fluorescent dyes according to claim 2, which is characterized in that the system of dyestuff 3 in step (2)
Preparation Method specifically: 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 methylene chloride extraction phase, drying, obtains 3 crude product of dyestuff；3 crude product of dyestuff is further used
Pillar layer separation, vacuum drying, obtains 3 sterling of dyestuff；Wherein, the molar ratio of compound 4, acenaphthene phenol and methanesulfonic acid is 1:2~3:
64~66.
9. application of the rhodamine fluorescent dyes described in claim 1 in fluorescence detection and pH probe.
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| CN103079598A (en) * | 2010-04-02 | 2013-05-01 | 药物影像股份有限公司 | Single isomeric conjugates of rhodamine dyes |
| CN102337041A (en) * | 2011-07-19 | 2012-02-01 | 华东理工大学 | Method for preparing rhodamine fluorescent dyes |
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