CN115160283B - Preparation method of fluorescent reagent 5-aminofluorescein - Google Patents

Preparation method of fluorescent reagent 5-aminofluorescein Download PDF

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CN115160283B
CN115160283B CN202210860940.2A CN202210860940A CN115160283B CN 115160283 B CN115160283 B CN 115160283B CN 202210860940 A CN202210860940 A CN 202210860940A CN 115160283 B CN115160283 B CN 115160283B
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aminofluorescein
acid
fluorescent reagent
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filtering
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CN115160283A (en
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张胜海
陈思梦
邓佳旺
石亚林
路东胜
石德康
解昱辰
李润
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Ankang University
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    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
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    • C07D311/90—Xanthenes with hydrocarbon radicals, substituted by amino radicals, directly attached in position 9
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Abstract

The invention discloses a preparation method of fluorescent reagent 5-aminofluorescein, which comprises the following steps: (1) preparation of 4-aminophthalic acid: 4-Nitrophthalic acid, N 2 H 4 ·H 2 O, feOOH mixing, reflux reacting, filtering while the mixture is hot, adjusting the pH to 3-4, cooling to room temperature, refrigerating until no solid is separated out, filtering, washing a filter cake with water to be neutral, and drying to obtain 4-aminophthalic acid; (2) preparation of 5-aminofluorescein: sequentially adding resorcinol and methane sulfonic acid into 4-aminophthalic acid, reacting under the protection of inert gas, cooling the reaction liquid to room temperature, pouring into ice water, regulating the pH value of the system to 5-6, standing and refrigerating until no solid is separated out, filtering, washing the filter cake with water to be neutral, and drying. The method for preparing the 5-aminofluorescein by the method of reduction and condensation has the advantages of high yield, lower reaction temperature, mild reaction conditions and no use of controlled reagent acetic anhydride.

Description

Preparation method of fluorescent reagent 5-aminofluorescein
Technical Field
The invention belongs to the technical field of fluorescent reagent preparation, and particularly relates to a preparation method of fluorescent reagent 5-amino fluorescein.
Background
5-aminofluorescein (5-amino-fluoroscein) has an excitation wavelength of 492nm and an emission wavelength of 515nm, and is one of commonly used fluorescent markers. The fluorescence of the fluorescent dye is weak, the fluorescence intensity of the fluorescent dye is only about 0.67 percent of that of fluorescein, and the derivatization reaction condition is quite harsh, so that the application range of the fluorescent dye is limited. By means of suitable condensing reagents, e.g. 3- (3-dimethylaminopropyl) -ethyl-carbodiimideThe (EDC), dicyclohexylcarbodiimide (DCC) and the like can be covalently bound with protein carboxyl, the fluorescence intensity of a binding product is obviously enhanced, and the fluorescent dye has been widely used in the fields of immunology research, protein tracing and the like. In order to overcome the defects of the 5-aminofluorescein and the severe derivatization reaction conditions, some researchers obtain derivatives with more excellent series fluorescence performance after the active amino isothiocyanate, hydrocarbylation, esterification, acylation, maleylation and azide of the 5-aminofluorescein, and the derivatives can be combined with-NH 2 The covalent bond is formed by the reaction of the-SH, -COOH and the like, so that the marker has higher selectivity, stability and sensitivity, and the application range of the 5-amino fluorescein in biological analysis is greatly expanded. However, the current price of 5-aminofluorescein derivatives is generally relatively expensive due to the limitation of high purity 5-aminofluorescein acquisition, making low cost bioassays difficult to achieve.
Pan Huiying et al 2006 (applied chemistry, 2006, 23, 193 _ 197. ) 4-nitrophthalic acid and resorcinol are used as raw materials, znCl 2 Is fused and condensed at high temperature by a catalyst, and then is subjected to Na 2 S/NaHS mixture reduction, 6% dilute hydrochloric acid recrystallization, respectively with 34% and 12.75% total yield to obtain high purity 5-amino fluorescein and 6-amino fluorescein. The synthesis process solves the problem of difficult separation of 5-position isomer and 6-position isomer by utilizing the difference of the solubility of 5-amino fluorescein and 6-amino fluorescein in 6% dilute hydrochloric acid and adopting a recrystallization method, but the high-temperature melting method is used for synthesizing the 5-amino fluorescein precursor, so that more byproducts and complex products are produced, and the yield of the 5-amino fluorescein is reduced besides bringing greater pressure to the subsequent separation. 2021, liu Jianwu et al (chemical agents, 2021, 43, 968 _ 972. ) Takes 4-nitrophthalic acid and resorcinol as raw materials, CH 3 -SO 3 H is used as a catalyst, and the key intermediate 5 (6) -nitrofluorescein is obtained by condensation reaction under the condition of lower temperature, and then is subjected to esterification separation and Na 2 S was reduced to give 5-aminofluorescein in a higher purity in a total yield of 51.6%. The synthesis process realizes the condensation of 4-nitrophthalic acid and resorcinol under the condition of lower temperature, and the yield of the key intermediate 5 (6) -nitrofluorescein is improvedThe overall yield of 5-aminofluorescein is now improved, but for the isolation of 5 (6) -nitrofluorescein, the acetic anhydride to be used in the esterification separation scheme is currently a tubular product, and the source of raw materials is difficult. Therefore, it is of great importance to develop a new process which can obtain high-purity 5-aminofluorescein at a lower temperature and at a lower cost.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of fluorescent reagent 5-amino fluorescein, which is simple and has high yield.
A preparation method of fluorescent reagent 5-aminofluorescein comprises the following steps:
(1) Preparation of 4-aminophthalic acid: 4-Nitrophthalic acid, N 2 H 4 ·H 2 O, feOOH, reflux reacting for 2-3 h at 90-110 ℃, filtering while the mixture is hot, adjusting the pH value to 3-4, cooling to room temperature, refrigerating until no solid is separated out, filtering, washing a filter cake with water to be neutral, and drying to obtain 4-aminophthalic acid;
(2) Preparation of 5-aminofluorescein: sequentially adding resorcinol and methane sulfonic acid into the 4-aminophthalic acid prepared in the step (1), reacting for 1-3 hours at 95-100 ℃ under the protection of inert gas, cooling the reaction liquid to room temperature, pouring into ice water, regulating the pH of the system to 5-6, standing and refrigerating until no solid is separated out, filtering, washing a filter cake with water to be neutral, and drying to obtain the 5-aminofluorescein.
Preferably, the 4-nitrophthalic acid, N 2 H 4 ·H 2 O, feOOH is 1mmol, 10-15 mmol and 0.5-0.8 mg.
Preferably, the ratio of the 4-aminophthalic acid, the resorcinol and the methane sulfonic acid is 6 mmol/12~13.2 mmol:8~12 mL.
Preferably, the volume of the ice water is 3-4 times that of the methane sulfonic acid.
Preferably, the drying is vacuum drying, and the temperature of the vacuum drying is 45-65 ℃.
Preferably, the refrigerating temperature is 2-8 ℃.
Preferably, in the step (1), the pH of the filtrate is adjusted to 3-4 by using concentrated hydrochloric acid.
Preferably, in the step (2), naOH solution is used for adjusting the pH of the system to 5-6.
Preferably, the concentration of the NaOH solution is 4-6mol.L -1 。
The ice water is ice water with the temperature of 0-5 ℃.
The reaction mechanism of the invention is as follows:
Figure 139538DEST_PATH_IMAGE001
。
the invention has the advantages that:
(1) The reaction is carried out in only two steps, the reaction temperature is relatively low, the reaction condition is mild, the use of controlled reagent acetic anhydride is avoided, and the experimental safety is good;
(2) The method for preparing the 5-aminofluorescein by the method of reduction and condensation is high in yield and suitable for industrial production.
Drawings
FIG. 1 5-mass spectrum of aminofluorescein;
FIG. 2 5-excitation and emission spectra of aminofluorescein.
Detailed Description
Example 1
A preparation method of fluorescent reagent 5-aminofluorescein comprises the following steps:
(1) Preparation of 4-aminophthalic acid: 10.0 mmol (2.1 g) of 4-nitrophthalic acid, 12.5mL, 40wt% of N were added in sequence in a three-necked flask 2 H 4 ·H 2 O aqueous solution (containing 100 mmol N) 2 H 4 ·H 2 O) and 5mg FeOOH, carrying out reflux reaction for 3h at 100 ℃, filtering while the mixture is hot to obtain clear solution, regulating the pH value to 3.5 by using concentrated hydrochloric acid, cooling to room temperature, refrigerating at 5 ℃ for 2. 2h, carrying out suction filtration, washing a filter cake with water to be neutral, and then carrying out vacuum drying at 50 ℃ to obtain 1.45g of light gray yellow solid which is 4-aminophthalic acid, wherein the melting point is 344.5 ℃ and the yield is 80%;
(2) Preparation of 5-aminofluorescein: 1.1g (6.0 mmol) of 4-aminophthalic acid prepared in the step (1) is added into a three-necked flask, 1.39 g (12.6 mmol) of resorcinol and 10mL of methanesulfonic acid are sequentially added, the mixture is reacted at 97 ℃ under the protection of argon, 3h is cooled to room temperature, the obtained reaction solution is poured into 30mL of ice water, the pH of the system is regulated to 6 by 5 mol/L of NaOH solution, reddish brown solid is separated out, the mixture is refrigerated at 5 ℃ for 2 hours, no solid is separated out, the mixture is filtered by suction, a filter cake is washed to be neutral by water, and the mixture is dried to be constant weight under vacuum at 50 ℃ to obtain 2.03g of the tan solid which is 5-aminofluorescein with the yield of 94.5%.
Example 2
A preparation method of fluorescent reagent 5-aminofluorescein comprises the following steps:
(1) Preparation of 4-aminophthalic acid: 10.0 mmol (2.1 g) of 4-nitrophthalic acid, 18.7mL, 40wt% N were added sequentially in a three-necked flask 2 H 4 ·H 2 O aqueous solution (containing 150 mmol N) 2 H 4 ·H 2 O) and 8mg FeOOH, carrying out reflux reaction for 2h at 110 ℃, filtering while the mixture is hot to obtain clear solution, regulating the pH value to 3 by using concentrated hydrochloric acid, cooling to room temperature, refrigerating at 2 ℃ for 1h, carrying out suction filtration, washing a filter cake with water to be neutral, and then carrying out vacuum drying at 45 ℃ to obtain 1.42g of light gray yellow solid which is 4-aminophthalic acid, wherein the melting point is 344.4 ℃ and the yield is 78.3%;
(2) Preparation of 5-aminofluorescein: 1.1g (6.0 mmol) of 4-aminophthalic acid prepared in the step (1) is added into a three-necked flask, then 1.32 g (12 mmol) of resorcinol and 8 mL of methanesulfonic acid are sequentially added, the mixture is reacted for 1h at 100 ℃ under the protection of argon, the mixture is cooled to room temperature, the obtained reaction solution is poured into 20mL of ice water, the pH of the system is regulated to 5 by 4 mol/L of NaOH solution, reddish brown solid is separated out, the mixture is refrigerated for 1h at 2 ℃, no solid is separated out, the mixture is filtered by suction, a filter cake is washed to be neutral by water, and the mixture is dried to be constant weight under vacuum at 45 ℃ to obtain 1.96g of 5-aminofluorescein as a tan solid, and the yield is 91.2%.
Example 3
A preparation method of fluorescent reagent 5-aminofluorescein comprises the following steps:
(1) Preparation of 4-aminophthalic acid: 10.0 mmol (2.1 g) of 4-nitrophthalic acid, 15mL, 40wt% N were added sequentially in a three-necked flask 2 H 4 ·H 2 O aqueous solution (containing 120 mmol N) 2 H 4 ·H 2 O) and 5mg FeOOH, carrying out reflux reaction for 3h at 90 ℃, filtering while the mixture is hot to obtain clear solution, regulating the pH value to 4 by using concentrated hydrochloric acid, cooling to room temperature, refrigerating at 8 ℃ for 3h, carrying out suction filtration, washing a filter cake with water to be neutral, and then carrying out vacuum drying at 65 ℃ to obtain 1.43g of light gray yellow solid which is 4-aminophthalic acid, wherein the melting point is 344.5 ℃ and the yield is 78.9%;
(2) Preparation of 5-aminofluorescein: 1.1g (6.0 mmol) of 4-aminophthalic acid prepared in the step (1) is added into a three-necked flask, then 1.45g (13.2 mmol) of resorcinol and 12mL of methanesulfonic acid are sequentially added, the mixture is reacted for 2 hours at 97 ℃ under the protection of argon, the mixture is cooled to room temperature, the obtained reaction solution is poured into 45mL of ice water, the pH of the system is regulated to 6 by 6 mol/L of NaOH solution, reddish brown solid is separated out, the mixture is refrigerated for 3 hours at 8 ℃, no solid is separated out, the mixture is filtered by suction, a filter cake is washed to be neutral by water, and the mixture is dried to be constant weight under vacuum at 65 ℃ to obtain 1.94g of 5-aminofluorescein as a tan solid, and the yield is 90.3%.
Mass spectrometry analysis
The tan solid prepared in example 1 was subjected to mass spectrometry and the results are shown in fig. 1.
As can be seen from FIG. 1, MS (ESI) + ) Theoretical value m/z [ C ] 20 H 14 NO 5 + ] + : 348.0866 [M+H] + Measured value m/z [ C 20 H 14 NO 5 + ] + : 348.0869 [M+H] + 。
Excitation and emission spectrogram analysis of di.5-aminofluorescein
The tan solid prepared in example 1 was formulated as 1.0X10 -6 The mol/L aqueous solution was scanned on an FL970 fluorescence spectrophotometer for excitation and emission spectra, respectively, with a maximum excitation wavelength of 492nm, maximum emission wavelength 517 nm, stokes shift 25 nm, consistent with excitation and emission spectra using 5-aminofluorescein of the prior art, e.g., pan Huiying (synthesis and characterization of aminofluorescein and its derivatives [ D ]]University of Tianjin, 2005.) study was consistent.
From the analysis, the preparation method provided by the invention can prepare 5-amino fluorescein.

Claims (9)

1. A preparation method of fluorescent reagent 5-aminofluorescein is characterized in that: the method comprises the following steps:
(1) Preparation of 4-aminophthalic acid: 4-Nitrophthalic acid, N 2 H 4 ·H 2 O, feOOH, reflux reacting for 2-3 h at 90-110 ℃, filtering while the mixture is hot, adjusting the pH value to 3-4, cooling to room temperature, refrigerating until no solid is separated out, filtering, washing a filter cake with water to be neutral, and drying to obtain 4-aminophthalic acid;
(2) Preparation of 5-aminofluorescein: sequentially adding resorcinol and methane sulfonic acid into the 4-aminophthalic acid prepared in the step (1), reacting for 1-3 hours at 95-100 ℃ under the protection of inert gas, cooling the reaction liquid to room temperature, pouring into ice water, regulating the pH of the system to 5-6, standing and refrigerating until no solid is separated out, filtering, washing a filter cake with water to be neutral, and drying to obtain the 5-aminofluorescein.
2. The method for preparing fluorescent reagent 5-aminofluorescein according to claim 1, wherein: the 4-nitrophthalic acid, N 2 H 4 ·H 2 O, feOOH is 1mmol, 10-15 mmol and 0.5-0.8 mg.
3. The method for preparing fluorescent reagent 5-aminofluorescein according to claim 2, which is characterized in that: the ratio of the 4-aminophthalic acid, the resorcinol and the methanesulfonic acid is 6 mmol/12~13.2 mmol:8~12 mL.
4. The method for producing a fluorescent reagent 5-aminofluorescein according to claim 3, wherein: the volume of the ice water is 3-4 times that of the methane sulfonic acid.
5. The method for preparing fluorescent reagent 5-aminofluorescein according to claim 1, wherein: the drying is vacuum drying, and the temperature of the vacuum drying is 45-65 ℃.
6. The method for preparing fluorescent reagent 5-aminofluorescein according to claim 1, wherein: the refrigerating temperature is 2-8 ℃.
7. The method for preparing fluorescent reagent 5-aminofluorescein according to claim 1, wherein: in the step (1), the pH of the filtrate is regulated to 3-4 by using concentrated hydrochloric acid.
8. The method for preparing fluorescent reagent 5-aminofluorescein according to claim 1, wherein: and (2) adjusting the pH of the system to 5-6 by using a NaOH solution.
9. The method for preparing fluorescent reagent 5-aminofluorescein according to claim 8, wherein: the concentration of the NaOH solution is 4-6mol.L -1 。
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2725666C1 (en) * 2019-12-17 2020-07-03 ФЕДЕРАЛЬНОЕ ГОСУДАРСТВЕННОЕ УНИТАРНОЕ ПРЕДПРИЯТИЕ "ИНСТИТУТ ХИМИЧЕСКИХ РЕАКТИВОВ И ОСОБО ЧИСТЫХ ХИМИЧЕСКИХ ВЕЩЕСТВ НАЦИОНАЛЬНОГО ИССЛЕДОВАТЕЛЬСКОГО ЦЕНТРА "КУРЧАТОВСКИЙ ИНСТИТУТ" (НИЦ "Курчатовский институт - ИРЕА) Method of producing 5-, 6-amino-fluoresceins
CN113444104A (en) * 2021-08-02 2021-09-28 苏州求索生物科技有限公司 Preparation process of 5-aminofluorescein

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RU2725666C1 (en) * 2019-12-17 2020-07-03 ФЕДЕРАЛЬНОЕ ГОСУДАРСТВЕННОЕ УНИТАРНОЕ ПРЕДПРИЯТИЕ "ИНСТИТУТ ХИМИЧЕСКИХ РЕАКТИВОВ И ОСОБО ЧИСТЫХ ХИМИЧЕСКИХ ВЕЩЕСТВ НАЦИОНАЛЬНОГО ИССЛЕДОВАТЕЛЬСКОГО ЦЕНТРА "КУРЧАТОВСКИЙ ИНСТИТУТ" (НИЦ "Курчатовский институт - ИРЕА) Method of producing 5-, 6-amino-fluoresceins
CN113444104A (en) * 2021-08-02 2021-09-28 苏州求索生物科技有限公司 Preparation process of 5-aminofluorescein

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氨基荧光素的合成、分离和表征;潘惠英，等;应用化学;第23卷;193-197 *

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