CN110078664B - Phosgene fluorescent probe and preparation method thereof - Google Patents

Phosgene fluorescent probe and preparation method thereof Download PDF

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CN110078664B
CN110078664B CN201910249828.3A CN201910249828A CN110078664B CN 110078664 B CN110078664 B CN 110078664B CN 201910249828 A CN201910249828 A CN 201910249828A CN 110078664 B CN110078664 B CN 110078664B
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phosgene
fluorescent probe
naphthalene anhydride
washing
diamino
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CN110078664A (en
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吴爱斌
周五
陈倩
胡艳雄
师春甜
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Yangtze University
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Abstract

The invention provides a phosgene fluorescent probe and a preparation method thereof, wherein the structural formula of the fluorescent probe is as follows:the fluorescent probe has good chemical stability, solubility and phosgene selectivity, high sensitivity and low detection limit, and is not interfered by other active acyl chloride and other substances. In the preparation process, 4, 5-binitro-1, 8-naphthalene anhydride is used as a raw material, C 2 H 5 OH/HCl as solvent, snCl 2 As a reducing agent, 4, 5-diamino-1, 8-naphthalene anhydride is obtained; then reacted with various amines in a solvent to obtain an orange-yellow probe product. The preparation method has the characteristics of stable reaction, high product yield and purity, low cost, simple process and easy industrialization.

Description

Phosgene fluorescent probe and preparation method thereof
Technical Field
The invention relates to the field of fine chemical engineering; in particular to a phosgene fluorescent probe and a preparation method thereof.
Background
Phosgene (Phosgene, COCl) 2 ) Is a kind of high chemical activityThe acyl chloride derivative is colorless and extremely toxic gas, and invades into human body through the way of permeation of respiratory tract and skin, so as to cause serious injury and asphyxia of lung. The mechanism of phosgene poisoning is currently still unclear and lacks effective treatment means, and has been used as a chemical weapon in the first and second world war. However, phosgene is an industrially extremely important starting material and plays a great role in the synthesis of agricultural chemicals, medicines and other products, so that a substitute triphosgene thereof is widely used. Since triphosgene is easy to obtain and is extremely easy to be converted into phosgene, accidental leakage in production and use can cause great disasters to environment, society and personal safety, and therefore the triphosgene has extremely important significance for real-time monitoring of extremely toxic substances such as the phosgene.
The traditional phosgene detection method mainly comprises Raman, GC-MS, enzymatic biosensing and the like, and although the results obtained by the detection methods are accurate and reliable, large-scale instruments and complex operation are needed in most cases, and the sample treatment is tedious and takes a long time. In contrast, the fluorescent probe technology has the advantages of real-time, convenience, high sensitivity, good selectivity, simple operation, low cost and the like, and is widely paid attention to.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a phosgene fluorescent probe and a preparation method thereof, wherein the obtained fluorescent probe has a brand new structure, and has the advantages of good selectivity, high sensitivity, low detection limit and the like, and the preparation method is simple and easy to obtain.
In order to achieve the above object, in a basic embodiment, the present invention provides a phosgene fluorescent probe having the following structural formula:
wherein r= -OCH 2 CH 3 ，-OCH 2 CH 2 OCH 2 CH 3 ，-N(CH 3 ) 2 ，-N(CH 3 )CH 2 CH 2 N(CH 3 ) 2 ，
The invention also provides a preparation method of the phosgene fluorescent probe, which comprises the following steps:
1) Adding 4, 5-dinitro-1, 8-naphthalene anhydride (III) and stannous chloride into C under the protection of nitrogen 2 H 5 Reflux reaction is carried out in OH/HCl for 2-4 h; cooling to room temperature, filtering, washing a filter cake, and vacuum drying to obtain a yellow product 4, 5-diamino-1, 8-naphthalene anhydride (II);
2) Under the protection of nitrogen, dissolving 4, 5-diamino-1, 8-naphthalene anhydride (II) in a solvent, adding primary amine, and reacting for 2-4 h at 70-90 ℃; pouring the obtained reaction liquid into a proper amount of ice water, filtering, washing, and purifying the crude product by column chromatography to obtain an orange-yellow product (I).
In a preferred embodiment, in said step 1), the molar ratio of said 4, 5-dinitro-1, 8-naphthalic anhydride (III) to stannous chloride is from 1:3 to 5.
In a preferred embodiment, in said step 1), said washing is an anhydrous diethyl ether and ethanol washing.
In a preferred embodiment, in the step 1), the reflux reaction is 3 hours.
In a preferred embodiment, in step 2), the solvent is DMF.
In a preferred embodiment, in step 2), the molar ratio of 4, 5-diamino-1, 8-naphthalene anhydride (II) to primary amine is from 1:1 to 1.2.
In a preferred embodiment, in said step 2), said primary amine is selected from the group consisting of 2-ethoxyethylamine, 2- (2-ethoxy) ethoxyethylamine, N-dimethylethylenediamine, N-methyl-N- (2-dimethylamino) ethylethylenediamine, 2-morpholinoethylamine, 2-thiomorpholinoethylamine, 2- (N-methylpiperazino) ethylamine, 2- (triphenylphosphine) ethylamine, and 3- (triphenylphosphine) propylamine.
In a preferred embodiment, in said step 2), the reaction is carried out at 80℃for 3h.
In a preferred embodiment, in said step 2), said column chromatography employs CH 2 Cl 2 /CH 3 OH is a developing agent.
Through the technical scheme, the optimal excitation wavelength of the fluorescent probe is 425nm, and the maximum emission wavelength is 480nm; the fluorescent probe is insensitive to the polarity of the solvent, has better chemical stability, good selectivity to the light and high sensitivity, and is not interfered by other active acyl chloride and other substances; the solubility and pH of the probe can be adjusted with various primary amines to be suitable for detecting phosgene in different environments, and the detection limit is in the range of 5-10 nmol. CH of fluorescent probe according to the invention 2 Cl 2 The solution is light green under the irradiation of a fluorescent lamp, and is yellow-green fluorescent under a 365nm ultraviolet lamp; phosgene (triphosgene/triethylamine as a substitute) was added to the solution and the solution became colorless and the fluorescence turned blue within tens of seconds. The fluorescent probe effectively realizes the real-time and high-sensitivity detection of phosgene, and the design principle is based on an intramolecular charge transfer mechanism.
In conclusion, the preparation method of the fluorescent probe has the characteristics of stable chemical reaction, high product yield and purity, low cost, simple process and easy industrialization.
Drawings
FIG. 1 is a graph showing the response of the fluorescent probe provided in example 1 of the present invention to phosgene.
Detailed Description
In order to better understand the technical solutions described above, the following detailed description of the technical solutions of the present application is provided by specific embodiments, and it should be understood that specific features of the embodiments and embodiments of the present application are detailed descriptions of the technical solutions of the present application, and not limiting the technical solutions of the present application, and the technical features of the embodiments and embodiments of the present application may be combined with each other without conflict. It is to be understood that the term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In order to overcome the defects in the prior art, the main idea of the embodiment of the invention is as follows:
the phosgene fluorescent probe comprises the following structural formula:
wherein r= -OCH 2 CH 3 ，-OCH 2 CH 2 OCH 2 CH 3 ，-N(CH 3 ) 2 ，-N(CH 3 )CH 2 CH 2 N(CH 3 ) 2 ，
The preparation method of the phosgene fluorescent probe comprises the following steps:
1) Adding 4, 5-dinitro-1, 8-naphthalene anhydride (III) and stannous chloride into C under the protection of nitrogen 2 H 5 Reflux reaction is carried out in OH/HCl for 2-4 h; cooling to room temperature, filtering, washing a filter cake, and vacuum drying to obtain a yellow product 4, 5-diamino-1, 8-naphthalene anhydride (II);
2) Under the protection of nitrogen, dissolving 4, 5-diamino-1, 8-naphthalene anhydride (II) in a solvent, adding primary amine, and reacting for 2-4 h at 70-90 ℃; pouring the obtained reaction liquid into a proper amount of ice water, filtering, washing, and purifying the crude product by column chromatography to obtain an orange-yellow product (I).
Hereinafter, a high-sensitivity fluorescent probe for detecting phosgene based on 4, 5-diamino-1, 8-naphthalimide and a method for preparing the same according to the present invention will be described in detail with reference to the accompanying examples. The materials used in the examples are available through commercial sources.
Example 1
a. 2.5940g (9 mmol) of Compound III, 10.1543g (45 mmol) of SnCl are reacted under nitrogen 2 .2H 2 O is added to 50mL C 2 H 5 And (3) in an OH+21mL concentrated HCl solution, carrying out reflux reaction for 3h, and monitoring by TLC until the raw material point disappears to obtain a reaction end point. Cooling to room temperature, suction filtering, washing filter cakes with absolute ethyl ether and ethanol respectively, and vacuum drying to obtain a yellow product 4, 5-diamino-1, 8-naphthalene anhydride (II) with the yield of 95%. HRMS (ES+) calcd for C 12 H 9 N 2 O 3 ([M+H]) + 229.0613,found 219.0610. The purity of the target compound was 99.5% as determined by HPLC.
b. 0.3534g (1.55 mmol) of Compound II is dissolved in 2mL of DMF under the protection of nitrogen, 0.1658g (1.86 mmol) of 2-ethoxyethylamine is added, and after reaction is carried out for 3h at 80 ℃, TLC is monitored until the starting point disappears, thus obtaining the reaction end point. Pouring the reaction solution into a proper amount of ice water, filtering, washing, and obtaining a crude product by CH 2 Cl 2 /CH 3 OH (20:1) as developing solvent was purified by silica gel column chromatography to give orange-yellow product (I-1) in 91% yield. HRMS (ES+) calcd for C 16 H 18 N 3 O 3 ([M+H]) + 300.1348,found 300.1346. The purity of the target compound was 99.0% as determined by HPLC.
Example 2
In the step b, 2- (2-ethoxy) ethoxyethylamine was used in place of 2-ethoxyethylamine, and the other ingredients were the same as in example 1 to give an orange-yellow product (I-2) in 93% yield. HRMS (ES+) calcd for C 18 H 22 N 3 O 4 ([M+H]) + 344.1610,found 344.1608. The purity of the target compound was 99.2% as determined by HPLC.
Example 3
In the step b, N-dimethylethylenediamine was used instead of 2-ethoxyethylamine, and the other steps were carried out in the same manner as in example 1 to obtain an orange-yellow product (I-3) in a yield of 92%. HRMS (ES+) calcd for C 16 H 19 N 4 O 2 ([M+H]) + 299.1508,found 299.1508. The purity of the target compound was 99.5% as determined by HPLC.
Example 4
In the step b, N-methyl-N- (2-dimethylamino) ethyl ethylenediamine was used instead of 2-ethoxyethylamine, and the same procedure as in example 1 was followed to obtain an orange-yellow product (I-4) in a yield of 90%. HRMS (ES+) calcd for C 19 H 26 N 5 O 2 ([M+H]) + 356.2087,found 356.2089. The purity of the target compound was 99.3% as determined by HPLC.
Example 5
In the step b, 2-morpholinoethylamine was used in place of 2-ethoxyethylamine, and the other steps were the same as in example 1 to obtain an orange-yellow product (I-5) in 91% yield. HRMS (ES+) calcd for C 18 H 21 N 4 O 3 ([M+H]) + 341.1614, found341.1612. Via HPLC assay, the purity of the target compound was 99.2%.
Example 6
In the step b, 2-thiomorpholinoethylamine was used in place of 2-ethoxyethylamine, and the other steps were the same as in example 1 to obtain an orange-yellow product (I-6) in 92% yield. HRMS (ES+) calcd for C 18 H 21 N 4 O 2 S([M+H]) + 357.1385,
found 357.1385. The purity of the target compound was 99.5% as determined by HPLC.
Example 7
In the step b, 2- (N-methylpiperazinyl) ethylamine was used in place of 2-ethoxyethylamine, and the other ingredients were the same as in example 1 to give an orange-yellow product (I-7) in a yield of 90%. HRMS (ES+) calcd for C 19 H 24 N 5 O 2 ([M+H]) + 354.1930,found 354.1328. The purity of the target compound was 99.3% as determined by HPLC.
Example 8
In the step b, 2- (triphenylphosphine) ethylamine was used instead of 2-ethoxyethylamine, and the other steps were the same as in example 1 to obtain an orange-yellow product (I-8) in 92% yield. HRMS (ES+) calcd for C 32 H 28 N 5 O 2 P([M+H]) + 517.1919,found 517.1917. The purity of the target compound was 99.5% as determined by HPLC.
Example 9
In the step b, 3- (triphenylphosphine) propylamine was used in place of 2-ethoxyethylamine, and the other steps were the same as in example 1 to obtain an orange-yellow product (I-9) in 93% yield. HRMS (ES+) calcd for C 32 H 28 N 5 O 2 P([M+H]) + 531.2076,found 531.2075. The purity of the target compound was 99.2% as determined by HPLC.
Example 10
a. 2.5940g (9 mmol) of Compound III, 6.093g (27 mmol) of SnCl are reacted under nitrogen 2 .2H 2 O is added to 50mL C 2 H 5 And (3) in an OH+21mL concentrated HCl solution, carrying out reflux reaction for 4h, and monitoring by TLC until the raw material point disappears to obtain a reaction end point. Cooling to room temperature, suction filtering, washing filter cakes with absolute ethyl ether and ethanol respectively, and vacuum drying to obtain a yellow product 4, 5-diamino-1, 8-naphthalene anhydride (II) with the yield of 94.2%. HRMS (ES+) calcd for C 12 H 9 N 2 O 3 ([M+H]) + 229.0613,found 219.0610. The purity of the target compound was 99.4% as determined by HPLC.
b. 0.3534g (1.55 mmol) of Compound II is dissolved in 2mL of DMF under the protection of nitrogen, 0.152g (1.71 mmol) of 2-ethoxyethylamine is added, and after reaction is carried out for 4h at 90 ℃, TLC is monitored until the starting point disappears, thus obtaining the reaction end point. Pouring the reaction solution into a proper amount of ice water, filtering, washing, and obtaining a crude product by CH 2 Cl 2 /CH 3 OH (20:1) as developing solvent was purified by silica gel column chromatography to give orange-yellow product (I-1) in 91.2% yield. HRMS (ES+) calcd for C 16 H 18 N 3 O 3 ([M+H]) + 300.1348,found 300.1346. The purity of the target compound was 99.0% as determined by HPLC.
The fluorescent probe provided by the embodiment of the invention has the advantages of good selectivity: is not interfered by other active acyl chloride substances, such as CH 3 COCl，SOCl 2 ，SO 2 Cl 2 ，DCP，DCNP，POCl 3 TosCl, etc. That is, none of these substances interfere with the response of the fluorescent probe to phosgene, and the fluorescence of the probe does not change at all after the addition of these substances, but the fluorescence of the probe changes significantly after the addition of phosgene.
The fluorescent probe has high sensitivity: as shown in FIG. 1, with the addition of phosgene, the fluorescence of the probe changed significantly, the maximum emission wavelength was blue shifted, and the intensity was enhanced.
The detection limit of the embodiment of the invention is low: the detection limit is in the range of 5-10 nmol.
According to the preparation method of the high-sensitivity fluorescent probe for detecting phosgene based on 4, 5-diamino-1, 8-naphthalimide, provided by the embodiment of the invention, under the set reaction conditions, the product yield is more than or equal to 90%, and the purity is more than or equal to 99%. The preparation method has the characteristics of stable reaction, high product yield and purity, low cost, simple process and easy industrialization, and has obvious implementation value and economic benefit.

Claims (7)

1. A phosgene fluorescent probe, characterized by: comprises the following structural formula:
wherein r= -OCH 2 CH 3 ，-OCH 2 CH 2 OCH 2 CH 3 ，-N(CH 3 ) 2 ，-N(CH 3 )CH 2 CH 2 N(CH 3 ) 2
The preparation method of the phosgene fluorescent probe comprises the following steps:
1) Adding 4, 5-dinitro-1, 8-naphthalene anhydride (III) and stannous chloride into C under the protection of nitrogen 2 H 5 Reflux reaction in OH/HCl for 3h; cooling to room temperature, filtering, washing a filter cake, and vacuum drying to obtain a yellow product 4, 5-diamino-1, 8-naphthalene anhydride (II);
2) Under the protection of nitrogen, dissolving 4, 5-diamino-1, 8-naphthalene anhydride (II) in a solvent, adding primary amine, and reacting for 3 hours at 80 ℃; pouring the obtained reaction liquid into a proper amount of ice water, filtering, washing, and purifying the crude product by column chromatography to obtain an orange-yellow product (I);
the yield of the prepared product is larger than or equal to 99 percent, and the purity is larger than or equal to 99 percent;
in the step 1), the molar ratio of the 4, 5-dinitro-1, 8-naphthalene anhydride (III) to stannous chloride is 1:3-5;
in the step 1), the washing is washing by absolute ethyl ether and ethanol;
in the step 1), the reflux reaction time is 3h.
2. A method of preparing the phosgene fluorescent probe of claim 1, wherein: the method comprises the following steps:
1) Adding 4, 5-dinitro-1, 8-naphthalene anhydride (III) and stannous chloride into C under the protection of nitrogen 2 H 5 Reflux reaction is carried out in OH/HCl for 2-4 h; cooling to room temperature, filtering, washing a filter cake, and vacuum drying to obtain a yellow product 4, 5-diamino-1, 8-naphthalene anhydride (II);
2) Under the protection of nitrogen, dissolving 4, 5-diamino-1, 8-naphthalene anhydride (II) in a solvent, adding primary amine, and reacting for 2-4 h at 70-90 ℃; pouring the obtained reaction liquid into a proper amount of ice water, filtering, washing, and purifying the crude product by column chromatography to obtain an orange-yellow product (I).
3. The method for preparing a phosgene fluorescent probe according to claim 2, wherein: in the step 2), the solvent is DMF.
4. The method for preparing a phosgene fluorescent probe according to claim 2, wherein: in the step 2), the molar ratio of the 4, 5-diamino-1, 8-naphthalene anhydride (II) to the primary amine is 1:1-1.2.
5. The method for preparing a phosgene fluorescent probe according to claim 2, wherein: in the step 2), the primary amine is selected from the group consisting of 2-ethoxyethylamine, 2- (2-ethoxy) ethoxyethylamine, N-dimethylethylenediamine, N-methyl-N- (2-dimethylamino) ethylethylenediamine, 2-morpholinoethylamine, 2-thiomorpholinoethylamine, 2- (N-methylpiperazinoethylamine).
6. The method for preparing a phosgene fluorescent probe according to claim 2, wherein: in said step 2), the reaction is carried out at 80℃for 3h.
7. The method for preparing a phosgene fluorescent probe according to claim 2, wherein: in the step 2), the column chromatography developing agent is CH 2 Cl 2 /CH 3 OH。
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