CN113929642B - Dehydroabietylamine silver ion fluorescent probe and preparation method thereof - Google Patents
Dehydroabietylamine silver ion fluorescent probe and preparation method thereof Download PDFInfo
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Abstract
The invention discloses dehydroabietylamine silver ionThe dehydroabietic acid directly reacts with NBS to generate 12-bromo-dehydroabietic acid, the product is subjected to double nitration to synthesize 12-bromo-13, 14-dinitrodehydroabietic acid, the product reacts with 4-triphenylamine borate under the catalysis of tetratriphenylphosphine palladium to generate 12- (triphenylamine) -13, 14-dinitrodehydroabietic acid, the product is subjected to amide formation and N-aminopropylmorpholine reaction to generate 6-propylmorpholinyl-12- (triphenylamine) -13, 14-dinitrodehydroabietic amine, and finally the compound is generated under the reduction of iron powder/hydrochloric acid. The compound can selectively react with Ag + Forming complex, quenching blue fluorescence after complex formation, and using as Ag + Fluorescent probes for concentration detection.
Description
Technical Field
The invention belongs to the technical field of fine organic synthesis, and particularly relates to a dehydroabietylamine silver ion fluorescent probe and a preparation method thereof.
Background
Silver is one of noble metals having good thermal and electrical conductivity and a few natural antibacterial substances. Due to their special properties, silver ions and silver nanoparticles have recently attracted attention in many fields such as medical devices, biomedicine, and textiles.
However, the excessive silver is harmful to the environment and human body, and the aquatic organisms such as fish and the like are killed or concentrated in the aquatic organisms due to the excessive silver contained in the water. Repeated exposure of silver to the human body can lead to the functional changes of heart enlargement, growth retardation, liver and the like, so that the detection of the silver content is particularly important. At present, the conventional methods such as voltammetry and electrothermal atomic absorption spectrometry are commonly used. These methods are very good for quantitative or qualitative detection, but have many drawbacks, such as too long detection time, too high sample requirement and cumbersome processing, which make real-time monitoring of silver ions impossible.
Thus, highly selective and highly sensitive Ag can be developed + The detection method has important significance for environmental protection and human health. In recent years, many organic fluorescent probes are researched for detecting metal ions, such as rhodamine fluorescent probes for detecting silver ions and coumarin fluorescent probes for detecting silver ions, but no reports related to the synthesis of dehydroabietic acid-based fluorescent probes for detecting silver ions exist.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made keeping in mind the above and/or other problems occurring in the prior art.
Therefore, the invention aims to overcome the defects in the prior art and provide a 6-propylmorpholinyl-12- (triphenylamine) -13, 14-diamino dehydroabietylamine silver ion fluorescent probe.
In order to solve the technical problems, the invention provides the following technical scheme: a 6-propylmorpholinyl-12- (triphenylamine) -13, 14-diamino dehydroabietylamine silver ion fluorescent probe,
the compound name is: 7, 8-diamino-6- (4-triphenylaminyl) 1, 4 a-dimethyl-N- (3-morpholinopropyl) 1,2,3,4,4a,9,10 a-octahydro-3H-phenanthro-1-carboxamide, having the formula:
the invention further aims to overcome the defects in the prior art and provide a preparation method of the 6-propylmorpholinyl-12- (triphenylamine) -13, 14-diamino dehydroabietylamine silver ion fluorescent probe.
In order to solve the technical problems, the invention provides the following technical scheme: a preparation method of a 6-propylmorpholinyl-12- (triphenylamine) -13, 14-diamino dehydroabietylamine silver ion fluorescent probe comprises the following steps,
the dehydroabietic acid is subjected to bromination and double nitration to prepare 12-bromo-13, 14-dinitrodehydroabietic acid;
reacting 12-bromo-13, 14-dinitrodehydroabietic acid with 4-triphenylamine borate to generate 12- (triphenylamine) -13, 14-dinitrodehydroabietic acid;
amidating 12- (triphenylamine) -13, 14-dinitrodehydroabietic acid to obtain 6-propylmorpholinyl-12- (triphenylamine) -13, 14-dinitrodehydroabietic amine;
6-propylmorpholinyl-12- (triphenylamine) -13, 14-dinitrodehydroabietylamine is reacted under the reduction of iron powder hydrochloric acid to generate 7, 8-diamino-6- (4-triphenylamine) -1, 4 a-dimethyl-N- (3-morpholinopropyl) -1,2,3, 4a,9,10 a-octahydro-3H-phenanthro-1-formamide.
As a preferable scheme of the preparation method of the 6-propylmorpholinyl-12- (triphenylamine) -13, 14-diamino dehydroabietylamine silver ion fluorescent probe, the method comprises the following steps: a process for producing 12-bromo-13, 14-dinitrodehydroabietic acid, which comprises,
adding NBS into the dehydroabietic acid dichloromethane solution for reaction, after the reaction is finished, drying, adding methanol for dissolution and crystallization to obtain 12-bromodehydroabietic acid; the concentration of the dehydroabietic acid dichloromethane solution is 0.15-0.2 g/mL, the molar ratio of dehydroabietic acid to NBS is 1.1-1.2, the reaction temperature of the dehydroabietic acid to thionyl chloride is room temperature, and the reaction time is 20-24 h;
adding 12-bromo dehydroabietic acid into fuming nitric acid and concentrated sulfuric acid to carry out double nitration reaction, pouring into ice water after the reaction is finished, washing with dichloromethane three times and three times, washing with saturated sodium bicarbonate aqueous solution once, washing with saturated salt once, drying with anhydrous sodium sulfate to remove water, and adding petroleum ether: ethyl acetate =200, 1-10, column purification to give 12-bromo-13, 14-dinitrodehydroabietic acid as a pale yellow color;
the dosage ratio of the 12-bromo dehydroabietic acid to fuming nitric acid is 1g to 6-7 mL, the dosage ratio of the 12-bromo dehydroabietic acid to concentrated sulfuric acid is 1-3g to 1mL, and the nitration reaction is carried out for 0.5-1.5 h under the ice-bath condition.
As a preferred scheme of the preparation method of the 6-propylmorpholinyl-12- (triphenylamine) -13, 14-diamine dehydroabietylamine silver ion fluorescent probe, the method comprises the following steps: a process for producing 12- (triphenylamine) -13, 14-dinitrodehydroabietic acid, which comprises,
dissolving 12-bromine-13, 14-dinitrodehydroabietic acid in toluene and ethanol, and adding 4-triphenylamine borate and K 2 CO 3 Solution, pd (pph) 3 ) 4 Refluxing for 12h at 80-100 ℃ under the protection of nitrogen; after the reaction is finished, extracting with ethyl acetate for three times, washing with water for three times, washing with saturated sodium bicarbonate aqueous solution for one time, washing with saturated salt water for one time, drying with anhydrous sodium sulfate for dewatering, and removing water by petroleum ether: ethyl acetate =20:1-5, purifying by passing through a column to obtain 12- (triphenylamine) -13, 14-dinitrodehydroabietic acid as a yellow solid;
the dosage ratio of the 12-bromo-13, 14-dinitrodehydroabietic acid to the toluene is 1g;
the dosage ratio of the 12-bromo-13, 14-dinitrodehydroabietic acid to the triphenylamine boric acid is 1.2-1;
the 12-bromo-13, 14-dinitrodehydroabietic acid was reacted with pd (pph) 3 ) 4 The dosage ratio is 1.
As a preferred scheme of the preparation method of the 6-propylmorpholinyl-12- (triphenylamine) -13, 14-diamine dehydroabietylamine silver ion fluorescent probe, the method comprises the following steps: the preparation method of 6-propylmorpholinyl-12- (triphenylamine) -13, 14-dinitrodehydroabietylamine comprises the following steps,
dissolving 12- (triphenylamine) -13, 14-dinitrodehydroabietic acid in toluene, then adding thionyl chloride for acyl chlorination reaction, after the reaction is finished, decompressing and rotary steaming to obtain a crude product 6-propylmorpholinyl-12- (triphenylamine) -13, 14-dinitrodehydroabietic acid acyl chloride, dissolving the crude product with diethyl ether, adding triethylamine and N-propylmorpholine for amidation reaction under the ice bath condition, after the reaction is finished, extracting with dichloromethane for three times, washing with water for three times, washing with saturated sodium bicarbonate aqueous solution once, washing with saturated salt water once, drying with anhydrous sodium sulfate to remove water, and removing water with dichloromethane: methanol =400, 1-100;
the dosage ratio of the 12- (triphenylamine) -13, 14-dinitrodehydroabietic acid to the toluene is 1g;
the molar ratio of the 12- (triphenylamine) -13, 14-dinitrodehydroabietic acid to the thionyl chloride is 1.5-1;
the dosage ratio of the 6-propylmorpholinyl-12- (triphenylamine) -13, 14-dinitrodehydroabietic acid acyl chloride to the ether is 1g;
the molar ratio of the 6-propylmorpholinyl-12- (triphenylamine) -13, 14-dinitrodehydroabietic acid acyl chloride to the N-propylmorpholine is 1.1-1;
the molar ratio of the 6-propylmorpholinyl-12- (triphenylamine) -13, 14-dinitrodehydroabietic acid acyl chloride to triethylamine is 1.5-1.
As a preferable scheme of the preparation method of the 6-propylmorpholinyl-12- (triphenylamine) -13, 14-diamino dehydroabietylamine silver ion fluorescent probe, the method comprises the following steps: dissolving 6-propylmorpholinyl-12- (triphenylamine) -13, 14-dinitrodehydroabietylamine in HFIP, then adding iron powder, distilled water and hydrochloric acid for reduction reaction, extracting with ethyl acetate for three times after the reaction is finished, washing with water for three times, washing with saturated sodium bicarbonate aqueous solution for one time, washing with saturated salt water for one time, drying with anhydrous sodium sulfate to remove water, and spin-drying; with dichloromethane: methanol =500, 1-200, column purification to give pure 7, 8-diamino-6- (4-triphenylamino) 1, 4 a-dimethyl-N- (3-morpholinopropyl) 1,2,3,4,4a,9,10 a-octahydro-3H-phenanthro-1-carboxamide;
the dosage ratio of the 6-propylmorpholinyl-12- (triphenylamine) -13, 14-dinitrodehydroabietylamine to the HFIP is 1g;
the molar ratio of the 6-propylmorpholinyl-12- (triphenylamine) -13, 14-dinitrodehydroabietylamine to the iron powder is 1;
the dosage ratio of the 6-propylmorpholinyl-12- (triphenylamine) -13, 14-dinitrodehydroabietylamine to the hydrochloric acid solution is 0.1-0.12g;
the reduction temperature of the Fe/HCl is 40-50 ℃, and the reaction time is 2-3 h.
The invention also aims to overcome the defects in the prior art and provide the application of the 6-propylmorpholinyl-12- (triphenylamine) -13, 14-diamino dehydroabietylamine silver ion fluorescent probe in the detection of silver ions.
As a preferable aspect of the application of the present invention, wherein: the concentration of silver ion is 0-60 μ M.
The invention has the beneficial effects that:
compared with the prior dehydroabietic acid, the 7, 8-diamino-6- (4-triphenylamine) -1, 4 a-dimethyl-N- (3-morpholinopropyl) 1,2,3, 4a,9,10 a-octahydro-3H-phenanthro-1-formamide prepared by taking dehydroabietic acid extracted from natural renewable resource disproportionated rosin as a raw material can effectively improve the water solubility of the compound by carrying out amidation modification on carboxyl, and can selectively react with Ag + Complexation and blue fluorescence quenching, and the compound can be used as a fluorescent probe for detecting Ag + Ions.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 is a graph showing the results of complexing 12- [4- (dianilino) phenyl ] -13, 14-diamino-N- [3- (4-morpholinyl) propyl ] -deisopropyldehydroabietylamide with silver ions under sunlight and 365nm ultraviolet light in accordance with the present invention;
FIG. 2 is a graph showing the effect of the ultraviolet absorption spectrum of the complexation of 12- [4- (dianilino) phenyl ] -13, 14-diamino-N- [3- (4-morpholinyl) propyl ] -deisopropyldehydroabietylamide with silver ions;
FIG. 3 is a graph showing the effect of fluorescence emission spectra of 12- [4- (dianilino) phenyl ] -13, 14-diamino-N- [3- (4-morpholinyl) propyl ] -deisopropyldehydroabietylamide on the action of different metal ions.
FIG. 4 is a graph showing a fluorescence emission spectrum of 12- [4- (dianilino) phenyl ] -13, 14-diamino-N- [3- (4-morpholinyl) propyl ] -deisopropyldehydroabietylamide upon addition of silver ions;
FIG. 5 shows the fluorescence emission spectrum of 12- [4- (diphenylamino) phenyl ] -13, 14-diamino-N- [3- (4-morpholinyl) propyl ] -deisopropyldehydroabietylamide with the addition of other metal ions.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, embodiments accompanying the present invention are described in detail below with reference to examples.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. In the present invention, the raw materials are not specifically described, and are all generally commercially available.
Example 1
The synthesis method of the dehydroabietic acid-based 2, 4-diaryl benzimidazole compound comprises the following steps:
the method comprises the following specific steps:
1) Preparation of 12-bromo-13, 14-dinitrodehydroabietic acid: the dehydroabietic acid is prepared by bromination and double nitration, and the specific process is as follows:
weighing 5g of dehydroabietic acid, dissolving in 30mL of dichloromethane, adding 4g of NBS, reacting at room temperature in a dark place for 24h, after the reaction is finished, carrying out rotary evaporation with 30mL of dichloromethane for three times, carrying out vacuum rotary drying, adding methanol for dissolving, and crystallizing at room temperature to obtain a white solid compound, namely 12-bromo dehydroabietic acid, wherein the yield is 80%.
Accurately weighing 6g of 12-bromo dehydroabietic acid, dissolving in 38mL of fuming nitric acid and 3mL of concentrated sulfuric acid, reacting for 1h under an ice bath condition, pouring into ice water after the reaction is finished, extracting with dichloromethane for three times, washing with water for three times, washing with saturated sodium bicarbonate aqueous solution for one time, washing with saturated salt water for one time, drying with anhydrous sodium sulfate to remove water, and reacting with petroleum ether: ethyl acetate =200, and 1-50 gradient column purification yielded light yellow 12-bromo-13, 14-dinitrodehydroabietic acid with a yield of 60.7%.
2) Preparation of 12- (triphenylamino) -13, 14-dinitrodehydroabietic acid
0.852g of 12-bromo-13, 14-dinitrodehydroabietic acid is accurately weighed and dissolved in 30mL of toluene and 15mL of ethanol, 0.72g of 4-triphenylamine borate, 12mL of a 2mol/L K2CO3 solution, 0.115g of pd (pph 3), and refluxed at 90 ℃ for 12 hours under the protection of nitrogen. After the reaction is finished, extracting with ethyl acetate for three times, washing with water for three times, washing with saturated sodium bicarbonate aqueous solution for one time, washing with saturated salt water for one time, drying with anhydrous sodium sulfate to remove water, and performing reaction by using petroleum ether: ethyl acetate =100, and the ratio of 1 to 1 was purified by column chromatography to obtain 12- (triphenylamine) -13, 14-dinitrodehydroabietic acid as a yellowish red solid in a yield of 82.1%.
3) Preparation of 6-propylmorpholinyl-12- (triphenylamine) -13, 14-dinitrodehydroabietylamine
Accurately weighing 0.59g of 12- (triphenylamine) -13, 14-dinitrodehydroabietic acid, dissolving in 20mL of toluene, adding SOCl2750 mu L of toluene and toluene 20mL of toluene, stirring at 80 ℃ for reacting for 6 hours, distilling under reduced pressure after the reaction is finished, dissolving a crude product by using diethyl ether, slowly adding 300 mu L of N-propyl morpholine amide and 280 mu L of triethylamine under the ice bath condition, and reacting at room temperature overnight. After the reaction was completed, the reaction mixture was concentrated under reduced pressure and extracted with dichloromethane: methanol =400, 1-100, to obtain yellow pure 6-propylmorpholinyl-12- (triphenylamino) -13, 14-dinitrodehydroabietylamine, with a yield of 84.2%.
4) Preparation of 7, 8-diamino-6- (4-triphenylamino) 1, 4 a-dimethyl-N- (3-morpholinopropyl) 1,2,3,4,4a,9,10 a-octahydro-3H-phenanthro-1-carboxamide
Accurately weighing 0.72g of 6-propylmorpholinyl-12- (triphenylamine) -13, 14-dinitrodehydroabietylamine obtained in the previous step, dissolving in 2.5mL of HFIP, adding 0.56g of iron powder and 30mL of 2M hydrochloric acid solution, and reacting at 45 ℃ for 2.5h; after the reaction is finished, evaporating to dryness, extracting for three times by using dichloromethane, washing for three times by using water, extracting for one time by using a saturated sodium carbonate solution, extracting for one time by using saturated saline, drying and dehydrating by using anhydrous sodium sulfate, and purifying by using dichloromethane: methanol =400:1-50, and purifying by passing through a column to obtain light yellow pure 7, 8-diamino-6- (4-triphenylamine) 1, 4 a-dimethyl-N- (3-morpholinopropyl) 1,2,3,4,4a,9,10 a-octahydro-3H-phenanthro-1-formamide with the yield of 84.5%.
Product characterization data were: m.p is 120.2-121.9 ℃;1H NMR (600mhz, dmso-d 6) δ 1.14 (s, 6H), 1.41 (dd, J =18.0,10.2hz, 3H), 1.71-1.53 (m, 6H), 1.99 (d, J =12.5hz, 1h), 2.18 (d, J =12.4hz, 1h), 2.27 (s, 2H), 2.39-2.30 (m, 4H), 2.57-2.51 (m, 2H), 3.18-3.03 (m, 2H), 3.94 (s, 2H), 3.56 (s, 4H), 4.18 (s, 2H), 6.35 (s, 1H), 7.05 (dd, J =14.0,7.1hz, 8h), 7.27 (d, J =8.4hz, 2h), 7.31 (t, J =7.9hz, 4h), 7.62 (t, J =5.2hz, 1h), 13C NMR (150mhz, dmso-d 6) δ 177.97,147.73,145.91,140.37,136.02,132.52,130.33,129.96,124.91,124.25,124.19,123.30,118.72,114.29,66.58,60.22,56.73,55.37,53.83,46.79,44.93,38.62,38.19,36.95,36.64,26.29,25.77,21.23,20.77,19.06,16.90,14.56; HRMS calcd for C42H52N5O2658.4121, found [ M + H + ]658.4119.
Example 2
69mg7, 8-diamino-6- (4-triphenylamine) 1, 4 a-dimethyl-N- (3-morpholinopropyl) 1,2,3, 4a,9,10 a-octahydro-3H-phenanthro-1-formamide are accurately weighed and dissolved in 10mL of absolute ethyl alcohol to prepare 1 × 10 -3 M, 200. Mu.M stock solution was diluted with an ethanol PBS solution (ethanol: PBS = 3) -5 M, adding 100 mu L of Ag + (1×10 -2 M) with Ag + The added solution became yellow.
Observed under a 365nm ultraviolet lamp, as shown in fig. 1,1 (a): addition of Ag to compounds under sunlight + Photos before and after the ion; 1 (b): adding Ag into the compound under 365nm ultraviolet lamp + Photo before and after ion, adding Ag + Blue fluorescence quenching of solutions of ions indicating that the compound reacts with Ag + Complexing and then adding Ag + And then quenching blue fluorescence under 365nm ultraviolet light, and detecting silver ions.
And by adding an equimolar amount of K + ，Na + ，Ag + ，Mg 2+ ，Ca 2+ ，Co 2+ ，Ni 2+ ，Mn 2+ ，Cu 2+ ，Cd 2+ ，Cs + ，Zn 2+ ，Fe 2+ ，Sn 2+ ，Hg 2+ ，Al 3+ ，Cr 3+ ，La 3+ ，Fe 3+ ，Ce 4+ ，Pb 2+ ，In 3+ ，Ga 3+ Plasma metal ions, which do not cause quenching of the fluorescence of the compound. The compound can be used as effective Ag + Fluorescent probes for ions.
Example 3
7, 8-diamino-6- (4-triphenylaminyl) 1, 4 a-dimethyl-N- (3-morpholinopropyl) 1,2,3,4,4a,9,10 a-octahydro-3H-phenanthro-1-carboxamide was dissolved in ethanol \ PBS buffer (ethanol: PBS =3, ph =7.4,10 mm) (2 × 10 -5 M), separately adding K + ，Na + ，Ag + ，Mg 2+ ，Ca 2+ ，Co 2+ ，Ni 2+ ，Mn 2+ ，Cu 2+ ，Cd 2+ ，Cs + ，Zn 2+ ，Fe 2+ ，Sn 2+ ，Hg 2 + ，Al 3+ ，Cr 3+ ，La 3+ ，Fe 3+ ，Ce 4+ ，Pb 2+ ，In 3+ ，Ga 3+ And (3) recording the ultraviolet absorption spectrum and the fluorescence spectrum of the solution by using the metal ions, and adding different interference ions to obtain the ultraviolet absorption spectrum of the compound as shown in figure 2. The compound mainly has an absorption peak at 320nm, and when other metal ions are added, the absorption peak of the ultraviolet absorption spectrum of the compound is not changed, and only the absorption intensity is slightly changed, butWhen adding Ag + When the ultraviolet absorption spectrum of the compound is changed, an absorption peak is newly generated at 440nm, and the absorption intensity at 320nm is obviously enhanced. Indicating that the compound may react with Ag + Ions are bonded to identify Ag + Ions. FIG. 3 shows the fluorescence spectra of compounds after addition of different interfering ions. The fluorescence intensity of the compound does not change greatly when other metal ions are added, but the fluorescence intensity is reduced sharply when Ag + is added, and the solution shows a very obvious fluorescence quenching phenomenon after the Ag + ions are added. The compound is proved to have excellent selectivity as a fluorescence quenching type probe for detecting Ag + ions.
Example 4
7, 8-diamino-6- (4-triphenylamine) 1, 4 a-dimethyl-N- (3-morpholinopropyl) 1,2,3, 4a,9,10 a-octahydro-3H-phenanthro-1-carboxamide was dissolved in ethanol \ PBS solution (ethanol: PBS = 3) (2X 10-5M), and the fluorescence emission spectra of different concentrations of Ag + versus 7, 8-diamino-6- (4-triphenylamine) 1, 4 a-dimethyl-N- (3-morpholinopropyl) 1,2,3, 4a,9,10 a-octahydro-3H-phenanthro-1-carboxamide were measured by adding (0-35) X10-5M of Ag +, and the fluorescence emission spectra of silver ions were added as shown in FIG. 4, and the fluorescence emission spectra of the compound was significantly diminished until the compound was able to complex with Ag +.
Example 5
In the case of compound 7, 8-diamino-6- (4-triphenylamino) 1, 4 a-dimethyl-N- (3-morpholinopropyl) 1,2,3,4,4a,9,10 a-octahydro-3H-phenanthro-1-carboxamide (2X 10) -5 M) and Ag + (1×10 -4 M), adding other metal ions in equimolar amount: k is + ，Na + ，Ag + ，Mg 2+ ，Ca 2+ ，Co 2+ ，Ni 2+ ，Mn 2+ ，Cu 2+ ，Cd 2+ ，Cs + ，Zn 2+ ，Fe 2+ ，Sn 2+ ，Hg 2+ ，Al 3+ ，Cr 3+ ，La 3+ ，Fe 3+ ，Ce 4+ ，Pb 2+ ，In 3+ ，Ga 3+ Metal ion interference experiments were performed.
The change in fluorescence intensity was recorded with a fluorescence spectrophotometer.
As shown in FIG. 5, since the fluorescence intensity of the above-mentioned fluorescent system does not change much after addition of another metal ion, and is still in a quenched state, this compound was used for detecting Ag + When the ion is generated, the metal ion interference resistance is good. The compound is a detection Ag + Highly specific fluorescent probes for ions.
Example 6
Optimization of the preparation method of 6-propylmorpholinyl-12- (triphenylamine) -13, 14-dinitrodehydroabietylamine:
test 1: 0.59g of 12- (triphenylamine) -13, 14-dinitrodehydroabietic acid was accurately weighed and dissolved in 2mL of methylene chloride, and 0.018g of HOBt and 0.024g of DCC were added, and after stirring at room temperature for 30 minutes, 300. Mu.L of propyl morpholinamide was added, and the mixture was reacted at room temperature overnight. After the reaction, filtering DCU, dissolving the filtrate in acetonitrile after vacuum concentration, stirring overnight, further filtering DCU, carrying out vacuum concentration to remove the solvent, and reacting with dichloromethane: methanol =400, 1-100, to obtain yellow pure 6-propylmorpholinyl-12- (triphenylamine) -13, 14-dinitrodehydroabietylamine, with a yield of 56.3%.
Test 2: accurately weighed 0.59g of 12- (triphenylaminyl) -13, 14-dinitrodehydroabietic acid was dissolved in 3mL of DCM, 64mg of oxalyl chloride, 90. Mu.L of triethylamine and 2mg of DMF were added, stirred at room temperature for 6 hours, the solvent was removed under reduced pressure, then 60mL of anhydrous tetrahydrofuran was added and re-evaporated, the residue was immediately dissolved in 10mL of DCM, 280. Mu.L of triethylamine, 2mg of DMAP and 300. Mu.L of N-propylmorpholinamide were added under ice-bath conditions, after stirring for 30 minutes, the solvent was removed, the residue was re-dissolved with 5mL of methanol, precipitated with 20mL of water, filtered and dried with dichloromethane: methanol =400, 1-100, to obtain yellow pure 6-propylmorpholinyl-12- (triphenylamino) -13, 14-dinitrodehydroabietylamine, with a yield of 61.2%.
Test 3: 0.59g of 12- (triphenylamino) -13, 14-dinitrodehydroabietic acid was accurately weighed and dissolved in 20mL of toluene, and SOCl was added 2 Stirring and reacting at 750 mu L and toluene 20mL at 80 ℃ for 6 hours, decompressing and distilling after the reaction is finished, dissolving a crude product by using diethyl ether, and slowly adding 300 mu L of N-propyl under the ice bath conditionMorpholine amide and 280. Mu.L triethylamine were reacted overnight at room temperature. After the reaction was completed, the reaction mixture was concentrated under reduced pressure, and extracted with dichloromethane: methanol =400, 1-100, to obtain yellow pure 6-propylmorpholinyl-12- (triphenylamino) -13, 14-dinitrodehydroabietylamine, with a yield of 84.2%.
Table 1 shows the yields of 6-propylmorpholinyl-12- (triphenylaminyl) -13, 14-dinitrodehydroabietylamine under different conditions.
TABLE 1
As can be seen from Table 1, the conditions of run 3 are the highest yield relative to the other reaction conditions, and therefore the reaction is run using this condition-toluene as solvent, SOCl 2 The yield of 6-propylmorpholinyl-12- (triphenylaminyl) -13, 14-dinitrodehydroabietylamine obtained as the acylating agent was the highest.
The invention provides a 6-propylmorpholinyl-12- (triphenylamine) -13, 14-diamino dehydroabietylamine silver ion fluorescent probe and Ag + Complexing and quenching blue light under the irradiation of an ultraviolet lamp with the wavelength of 365nm for detecting Ag + And (4) concentration. The invention provides a preparation method of the 6-propylmorpholinyl-12- (triphenylamine) -13, 14-diamine dehydroabietylamine silver ion fluorescent probe, dehydroabietic acid extracted from natural renewable resource disproportionated rosin is used as a raw material, and the probe is prepared through a series of chemical reactions, has wide raw material sources, and lays a foundation for mass production. The compound can be selectively complexed with Ag < + > and quenched in blue fluorescence, and can be used as a fluorescent probe for detecting Ag + Ions.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (8)
1. A dehydroabietylamine silver ion fluorescent probe is characterized in that:
the name of the compound is: 12- [4- (dianilino) phenyl ] -13, 14-diamino-N- [3- (4-morpholinyl) propyl ] -deisopropyl dehydroabietylamide, and the structural formula is as follows:
2. the method for preparing the dehydroabietylamine silver ion fluorescent probe of claim 1, which is characterized by comprising the following steps of: comprises the steps of (a) preparing a substrate,
carrying out bromination and double nitration on the dehydroabietic acid to prepare 12-bromo-13, 14-dinitro de-isopropyl dehydroabietic acid;
12-bromine-13, 14-dinitro isopropyl dehydroabietic acid reacts with 4-triphenylamine borate to generate 12- [4- (diphenylamine group) phenyl ] -13, 14-dinitro isopropyl dehydroabietic acid;
amidating 12- [4- (diphenylamine) phenyl ] -13, 14-dinitro isopropyl-removed dehydroabietic acid to prepare 12- [4- (diphenylamine) phenyl ] -13, 14-dinitro-N- [3- (4-morpholinyl) propyl ] -isopropyl-removed dehydroabietic amide;
the 12- [4- (diphenylamine) phenyl ] -13, 14-dinitro-N- [3- (4-morpholinyl) propyl ] -deisopropyl dehydroabietylamide reacts under the reduction of iron powder hydrochloric acid to generate 12- [4- (diphenylamine) phenyl ] -13, 14-diamino-N- [3- (4-morpholinyl) propyl ] -deisopropyl dehydroabietylamide.
3. The method for preparing the dehydroabietylamine silver ion fluorescent probe according to claim 2, which is characterized in that: a preparation method of 12-bromo-13, 14-dinitrodeisopropyldehydroabietic acid comprises the steps of,
adding NBS into the dehydroabietic acid dichloromethane solution for reaction, after the reaction is finished, drying, adding methanol for dissolution and crystallization to obtain 12-bromine dehydroabietic acid; the concentration of the dehydroabietic acid dichloromethane solution is 0.15-0.2 g/mL, the molar ratio of dehydroabietic acid to NBS is 1.1-1.2, the reaction temperature of the dehydroabietic acid to thionyl chloride is room temperature, and the reaction time is 20-24 h;
adding 12-bromo dehydroabietic acid into fuming nitric acid and concentrated sulfuric acid to carry out double nitration reaction, pouring into ice water after the reaction is finished, washing with dichloromethane three times and water three times, washing with saturated sodium bicarbonate water solution once, washing with saturated salt once, drying with anhydrous sodium sulfate to remove water, and removing water with petroleum ether: ethyl acetate =200, 1-10, and the obtained product is purified by column chromatography to obtain light yellow 12-bromo-13, 14-dinitrodeisopropyl dehydroabietic acid;
the dosage ratio of the 12-bromo dehydroabietic acid to fuming nitric acid is 1g to 6-7 mL, the dosage ratio of the 12-bromo dehydroabietic acid to concentrated sulfuric acid is 1-3g to 1mL, and the nitration reaction is carried out for 0.5-1.5 h under the ice-bath condition.
4. The method for preparing the dehydroabietylamine silver ion fluorescent probe according to claim 2, which is characterized in that: a process for producing 12- [4- (dianilino) phenyl ] -13, 14-dinitrodeisopropyldehydroabietic acid which comprises,
dissolving 12-bromine-13, 14-dinitro isopropyl dehydroabietic acid in toluene and ethanol, and adding 4-triphenylamine borate and K 2 CO 3 Solution, pd (PPh) 3 ) 4 Refluxing for 12h at 80-100 ℃ under the protection of nitrogen; after the reaction is finished, extracting with ethyl acetate for three times, washing with water for three times, washing with saturated sodium bicarbonate aqueous solution for one time, washing with saturated salt water for one time, drying with anhydrous sodium sulfate to remove water, and performing reaction by using petroleum ether: ethyl acetate =20:1-5, purifying by passing through a column to obtain 12- [4- (diphenylamine) phenyl ] yellow solid]-13, 14-dinitrodeisopropyldehydroabietic acid;
the dosage ratio of the 12-bromo-13, 14-dinitro de-isopropyl dehydroabietic acid to toluene is 1g;
the dosage ratio of the 12-bromo-13, 14-dinitrodeisopropyldehydroabietic acid to the triphenylamine boric acid is 1.2-1;
said 12Bromo-13, 14 dinitrodeisopropyldehydroabietic acid with Pd (PPh) 3 ) 4 The dosage ratio is 1.
5. The method for preparing the dehydroabietylamine silver ion fluorescent probe according to claim 2, which is characterized in that: a process for the preparation of 12- [4- (dianilino) phenyl ] -13, 14-dinitro-N- [3- (4-morpholinyl) propyl ] -deisopropyl dehydroabietylamide which comprises,
dissolving 12- [4- (diphenylamine) phenyl ] -13, 14-dinitro isopropyl dehydroabietic acid in toluene, then adding thionyl chloride for acyl chlorination, after the reaction is finished, carrying out reduced pressure rotary evaporation to obtain a crude product, namely 12- [4- (diphenylamine) phenyl ] -13, 14-dinitro isopropyl dehydroabietic acid chloride, dissolving the crude product in diethyl ether, adding triethylamine and 3-morpholinylpropylamine for amidation reaction under the condition of ice bath, extracting the crude product with dichloromethane for three times, washing the crude product with water for three times, washing the crude product with saturated sodium bicarbonate aqueous solution once, washing the crude product with saturated common salt water once, drying anhydrous sodium sulfate to remove water, and carrying out amidation reaction with dichloromethane: methanol =400, 1-100;
the dosage ratio of the 12- [4- (diphenylamine) phenyl ] -13, 14-dinitro de-isopropyl dehydroabietic acid to the toluene is 1g;
the molar ratio of the 12- [4- (diphenylamine) phenyl ] -13, 14-dinitro de-isopropyl dehydroabietic acid to the thionyl chloride is 1.5-1;
the dosage ratio of 12- [4- (diphenylamine group) phenyl ] -13, 14-dinitro deisopropyl dehydroabietyl chloride to the ether is 1g;
the molar ratio of the 12- [4- (diphenylamine) phenyl ] -13, 14-dinitro de-isopropyl dehydroabietylchloride to the 3-morpholinyl propylamine is 1.1-1.2;
the molar ratio of the 12- [4- (diphenylamine) phenyl ] -13, 14-dinitrodeisopropyldehydroabietylchloride to the triethylamine is 1.5-1.2.
6. The method for preparing the dehydroabietylamine silver ion fluorescent probe according to claim 2, which is characterized in that:
dissolving 12- [4- (diphenylamine) phenyl ] -13, 14-dinitro-N- [3- (4-morpholinyl) propyl ] -deisopropyl dehydroabietylamide in Hexafluoroisopropanol (HFIP), then adding iron powder, distilled water and hydrochloric acid to perform a reduction reaction, extracting with ethyl acetate for three times after the reaction is finished, washing with water for three times, washing with saturated sodium bicarbonate aqueous solution once, washing with saturated salt water once, drying with anhydrous sodium sulfate to remove water, and spin-drying; with dichloromethane: methanol =500, 1-200, column purified to give pure 12- [4- (dianilino) phenyl ] -13, 14-diamino-N- [3- (4-morpholinyl) propyl ] -deisopropyldehydroabietylamide;
the dosage ratio of the 12- [4- (diphenylamine) phenyl ] -13, 14-dinitro-N- [3- (4-morpholinyl) propyl ] -deisopropyl dehydroabietylamide to HFIP is 1 g;
the molar ratio of the 12- [4- (diphenylamine) phenyl ] -13, 14-dinitro-N- [3- (4-morpholinyl) propyl ] -deisopropyl dehydroabietylamide to the iron powder is 1;
the dosage ratio of the 12- [4- (diphenylamine) phenyl ] -13, 14-dinitro-N- [3- (4-morpholinyl) propyl ] -deisopropyl dehydroabietylamide to the hydrochloric acid solution is 0.1-0.12g;
the reduction temperature of iron powder hydrochloric acid is 40-50 ℃, and the reaction time is 2-3 h.
7. The use of the dehydroabietylamine silver ion fluorescent probe according to claim 1 for detecting silver ions.
8. The use of claim 7, wherein: the concentration of silver ion is 0-60 μ M.
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