Isolongifolanone-based fluorescent probe for detecting hydrazine as well as preparation method and application of isolongifolanone-based fluorescent probe

Abstract

The invention discloses an isolongifolanone-based fluorescent probe for detecting hydrazine as well as a preparation method and application of the isolongifolanone-based fluorescent probe. Isolongifolanone is used as a raw material and is subjected to condensation with 2-amino-4 '-bromobenzophenone, the condensation product and 4-hydroxyphenylboronic acid are subjected to Suzuki coupling, the coupling product and urotropine are subjected to formylation, the formylation product and 1-bromobutane are etherified, and the isolongifolanone derivative is obtained. The preparation method comprises the following steps: reacting 2-(2-(4-butoxy-4 '-(1, 1, 5, 5-tetramethyl-1, 3, 4, 5, 6, 12b-hexahydro-2H-2, 4a-arbor methyl benzacridine-7-yl)-[1, 1'-biphenyl]-3-yl) vinyl)-3-ethyl-benzothiazole-3-onium (abbreviated as ABP-BBT) by using 2-(2-(4-butoxy-4 '-(1, 1, 5, 5-tetramethyl-1, 3, 4, 5, 6, 12b-hexahydro-2H-2, 4a-arbor methyl benzacridine-7-yl)-1, 1'-biphenyl)-1, 2, 4, 5-tetramethyl-1, 3, 4, 5 The compound ABP-BBT can specifically recognize hydrazine, the detection limit of hydrazine reaches 7.5 nM, and the compound ABP-BBT has a good application prospect.

Description

Technical Field

[0001] The present invention belongs to the technical field of fine organic synthesis, and relates to an isolongifolanyl ketone-based fluorescent probe for detecting hydrazine, a preparation method thereof, and an application thereof. Background Art

[0002] Hydrazine is an important chemical in laboratory and industrial environments and is widely used as a preservative, antioxidant, and insecticide, as well as in the synthesis of dyes and drugs. Its high combustion enthalpy further makes it a key component of missile and rocket propulsion systems. However, hydrazine is a highly toxic substance, and its widespread use poses a serious environmental pollution risk during storage, transportation, application, and wastewater treatment. Human exposure through skin contact, eye absorption, or inhalation can cause serious health effects, including shortness of breath, headache, hepatotoxicity, neurotoxicity, and teratogenicity. Therefore, the US Environmental Protection Agency (EPA) has classified hydrazine as a potential human carcinogen and has set a strict threshold limit of 10 ppb. Given these hazards, it is of great significance to develop a convenient, highly selective, and sensitive method for detecting hydrazine in environmental and biological systems.

[0003] Compared with traditional analytical detection methods, the fluorescent probe technology converts the chemical recognition process into observable fluorescence signal changes, and has the advantages of fast detection speed, high sensitivity, good selectivity, low cost, and simple operation. Summary of the Invention

[0004] Aiming at the deficiencies in the prior art, the technical problems to be solved by the present invention are to provide an isolongifolanyl ketone-based fluorescent probe for detecting hydrazine, which can meet the use requirements. Another technical problem to be solved by the present invention is to provide a preparation method of compound ABP-BBT. The technical problem to be solved by the present invention is also to provide an application of the above compound ABP-BBT.

[0005] To solve the above technical problems, the technical solution adopted by the present invention is as follows:

[0006] The isolongifolanyl ketone-based fluorescent probe is ABP-BBT, and its structural formula is:

[0007]

[0008] The preparation method of the isolongifolanyl ketone-based fluorescent probe for detecting hydrazine includes the following steps:

[0009] 1) Isolongifolanyl ketone reacts with 2-amino-4'-bromobenzophenone by condensation reaction to obtain compound AB-Br.

[0010] 2) Compound AB-Br undergoes Suzuki coupling reaction with 4-hydroxybenzeneboronic acid to obtain compound ABP-OH.

[0011] 3) The compound ABP-OH undergoes a formylation reaction with hexamethylenetetramine to obtain the compound ABP-HC.

[0012] 4) The compound ABP-HC undergoes an etherification reaction with n-butyl bromide to obtain ABP-BC.

[0013] 5) The compound ABP-BC undergoes a condensation reaction with 2-methyl-3-ethylbenzothiazol-3-ium salt to obtain the compound ABP-BBT.

[0014] In step 1), isolongifolanone undergoes a condensation reaction with 2-amino-4'-bromobenzophenone to obtain the compound AB-Br. The specific preparation steps are as follows:

[0015] (1) 11 mmol of 2-amino-4'-bromobenzophenone, 8 - 12 mmol of isolongifolanone, and 10 - 15 mmol of sulfamic acid are successively added to a sealed U-shaped tube equipped with a stirrer, and the reaction is carried out at 85 °C for 46 - 48 h;

[0016] (2) After the reaction mixture is extracted, washed, and the solvent is recovered by distillation, a crude product of AB-Br is obtained;

[0017] (3) The crude product of AB-Br is chromatographed on a silica gel column (petroleum ether) to obtain white powder AB-Br.

[0018] In step 2), AB-Br reacts with 4-hydroxyphenylboronic acid to obtain the compound ABP-OH. The specific preparation steps are as follows:

[0019] (1) 2 mmol of AB-Br, 4 - 6 mmol of 4-hydroxyphenylboronic acid, an aqueous solution of 1 M potassium carbonate, and 40 - 60 mL of 1,4-dioxane are successively added to a three-necked flask equipped with a stirrer. Under nitrogen protection, 0.1 mmol of tetrakis(triphenylphosphine)palladium is added and the reaction is carried out at 90 °C for 12 - 15 h;

[0020] (2) After the reaction solution is distilled to recover the solvent, a crude product of ABP-OH is obtained;

[0021] (3) The crude product of ABP-OH is purified by a silica gel column (petroleum ether:ethyl acetate = 100:1, v / v) to obtain white solid ABP-OH.

[0022] In step 3), ABP-OH reacts with hexamethylenetetramine to obtain ABP-HC. The specific preparation steps are as follows:

[0023] (1) 1 mmol of ABP-OH, 3 - 5 mmol of hexamethylenetetramine, and 10 - 12 mL of trifluoroacetic acid are successively added to a single-necked flask equipped with a stirrer, and the reaction is refluxed at 90 °C for 12 - 15 h;

[0024] (2) After the reaction solution is extracted, the pH is adjusted, and the solvent is recovered by distillation, the crude product of ABP-HC is obtained;

[0025] (3) After the crude product of ABP-HC is purified by a silica gel chromatographic column (dichloromethane), white solid ABP-HC is obtained.

[0026] In step 4), ABP-HC reacts with n-butyl bromide to obtain ABP-BC. The specific preparation steps are as follows:

[0027] (1) 1 mmol of ABP-HC, 1 - 3 mmol of n-butyl bromide, 2 - 3 mmol of anhydrous potassium carbonate, and 10 - 15 mL of N,N-dimethylformamide are successively added to a single-necked flask equipped with a stirrer, and the mixture is refluxed at 85 °C for 1 - 2 h;

[0028] (2) After the reaction solution is extracted and the solvent is recovered by distillation, the crude product of ABP-BC is obtained;

[0029] (3) After the crude product of ABP-BC is purified by a silica gel chromatographic column (petroleum ether:ethyl acetate = 80:1, v / v), white solid ABP-BC is obtained.

[0030] In step 5), ABP-BC undergoes a condensation reaction with 2-methyl-3-ethylbenzothiazol-3-ium salt to obtain ABP-BBT. The specific preparation steps are as follows:

[0031] (1) 1 mmol of ABP-BC, 1 - 2 mmol of 2-methyl-3-ethylbenzothiazol-3-ium salt, 1 - 2 mL of pyridine, and 10 - 15 mL of dichloromethane are successively added to a single-necked flask equipped with a stirrer, and the mixture is refluxed at room temperature for 4 - 5 h;

[0032] (2) After the reaction solution is extracted and the solvent is recovered by distillation, the crude product of ABP-BBT is obtained;

[0033] (3) After the crude product of ABP-BBT is purified by a silica gel chromatographic column (dichloromethane:methanol = 50:1, v / v), orange solid ABP-BBT is obtained.

[0034] The application of the described ABP-BBT in detecting hydrazine.

[0035] The application of the described ABP-BBT in preparing a fluorescent probe for detecting hydrazine.

[0036] Beneficial effects: Compared with the prior art, the present invention uses isolongifolanone as a raw material to prepare the compound ABP-BBT, which can specifically recognize hydrazine. As a fluorescent probe for detecting hydrazine, it has many advantages such as convenient synthesis, rapid response (20 minutes), high sensitivity (7.5 nM), and good selectivity, and has good application value. Description of the Drawings

[0037] Figure 1 It is the fluorescence spectrogram of the fluorescent probe ABP-BBT interacting with hydrazine at different concentrations;

[0038] Figure 2 It is the fluorescence spectrogram of the fluorescent probe ABP-BBT interacting with different amines and hydrazine derivatives. Detailed Embodiments

[0039] The present invention will be further described below in conjunction with specific embodiments.

[0040] Example 1

[0041] Preparation of the compound ABP-BBT, the reaction formula is as follows:

[0042]

[0043] The specific steps are as follows:

[0044] 1) Preparation of the compound AB-Br:

[0045] 11 mmol of 2-amino-4'-bromobenzophenone, 10 mmol of isolongifolanone, and 10 mmol of amidosulfonic acid were successively added to a sealed U-tube equipped with a stirrer, and reacted at 85 °C for 48 h. After the reaction mixture was extracted, washed, and the solvent was recovered by distillation, a crude product of the compound AB-Br was obtained. After purification by a silica gel chromatography column (using petroleum ether as the eluent), a white powder AB-Br was obtained, and the yield was 40%. 11H NMR (600 MHz, CDCl3), δ (ppm): 8.03 (s, 1H), 7.66 (ddt, J = 6.9, 4.8, 2.1 Hz, 2H), 7.60 (t, J = 7.3 Hz, 1H), 7.30 (tt, J = 8.4, 5.0 Hz, 2H), 7.17 (dd, J = 8.3, 2.2 Hz, 1H), 7.09 (dd, J = 8.3, 2.2 Hz, 1H), 2.84 (s, 1H), 2.71 (d, J = 16.4 Hz, 1H), 2.18 (d, J = 16.5 Hz, 1H), 2.00 (ddt, J = 12.6, 9.5, 3.2 Hz, 1H), 1.78 (dd, J = 10.3, 2.9 Hz, 2H), 1.71 (td, J = 12.1, 4.0 Hz, 1H), 1.58 (dt, J = 12.9, 4.7 Hz, 1H), 1.55 (s, 3H), 1.27 (dd, J = 11.7, 3.6 Hz, 2H), 0.98 (s, 3H), 0.72 (s, 3H), 0.64 (s, 3H). 13 13C NMR (151 MHz, CDCl3), δ (ppm): 161.52, 131.97, 131.94, 131.66, 131.20, 129.21, 128.19, 127.51, 125.92, 125.60, 125.44, 122.07, 58.98, 55.63, 48.26, 45.68, 41.43, 37.58, 32.68, 30.78, 28.60, 26.23, 25.60, 25.02, 23.44. MS (m / z): [M+H] + calcd. for C 28 H 30 BrN+H + , 460.1640; found, 460.1644.

[0046] 2) Preparation of compound ABP-OH:

[0047] 2 mmol of AB-Br, 4 mmol of 4-hydroxybenzeneboronic acid, an aqueous solution of 1 M potassium carbonate, and 40 mL of 1,4-dioxane were successively added to a three-necked flask equipped with a stirrer. Under nitrogen protection, 0.1 mmol of tetrakis(triphenylphosphine)palladium was added and the reaction was carried out at 90 °C for 12 h. After the reaction solution was distilled to recover the solvent, the crude product of ABP-OH was obtained. After chromatography on a silica gel column (petroleum ether:ethyl acetate = 100:1, v / v), white solid ABP-OH was obtained with a yield of 38%. 11H NMR (600 MHz, DMSO-d6), δ (ppm): 9.61 (s, 1H), 7.92 (dd, J = 8.5, 1.2 Hz, 1H), 7.80 - 7.75 (m, 2H), 7.65 - 7.60 (m, 3H), 7.41 - 7.35 (m, 2H), 7.32 (dd, J = 8.4, 1.4 Hz, 1H), 7.25 (dd, J = 7.8, 2.0 Hz, 1H), 6.92 - 6.87 (m, 2H), 2.81 (d, J = 16.4 Hz, 1H), 2.73 (d, J = 1.7 Hz, 1H), 2.20 (d, J = 16.4 Hz, 1H), 1.91 (dt, J = 9.1, 6.3 Hz, 1H), 1.85 - 1.80 (m, 1H), 1.76 (d, J = 4.3 Hz, 1H), 1.68 (td, J = 12.0, 3.9 Hz, 1H), 1.54 (tt, J = 12.3, 4.4 Hz, 1H), 1.47 (s, 3H), 1.22 (d, J = 9.6 Hz, 2H), 0.94 (s, 3H), 0.68 (s, 3H), 0.62 (s, 3H). 13 13C NMR (151 MHz, DMSO-d6), δ (ppm): 160.57, 157.35, 145.71, 145.14, 139.55, 134.44, 130.26, 130.20, 129.55, 128.59, 128.10, 127.79, 126.95, 126.06, 125.98, 125.48, 125.38, 125.35, 115.83, 58.19, 54.90, 47.48, 44.88, 40.88, 40.05, 36.97, 32.07, 30.14, 28.32, 25.93, 25.25, 24.47, 23.12. MS (m / z): [M+H] + calcd. for C 34 H 35 NO+H + , 474.2797; found, 474.2802.

[0048] 3) Preparation of compound ABP-HC:

[0049] 1 mmol of ABP-OH, 3 mmol of hexamethylenetetramine, and 10 mL of trifluoroacetic acid were successively added to a single-necked flask equipped with a stirrer, and the mixture was refluxed at 90 °C for 12 h. After the reaction solution was extracted, the pH was adjusted, and the solvent was recovered by distillation, a crude product of compound ABP-HC was obtained. After chromatography on a silica gel column (dichloromethane), white solid ABP-HC was obtained with a yield of 49%. 11H NMR (600 MHz, DMSO-d6), δ (ppm): 10.91 (s, 1H), 10.36 (s, 1H), 8.07 (d, J = 2.5 Hz, 1H), 8.00 (dd, J = 8.6, 2.5 Hz, 1H), 7.93 (d, J = 8.4 Hz, 1H), 7.87 - 7.81 (m, 2H), 7.66 - 7.61 (m, 1H), 7.44 (dd, J = 7.7, 2.1 Hz, 1H), 7.41 - 7.36 (m, 1H), 7.33 - 7.27 (m, 2H), 7.16 (d, J = 8.6 Hz, 1H), 2.82 (d, J = 16.4 Hz, 1H), 2.73 (s, 1H), 2.19 (d, J = 16.4 Hz, 1H), 1.91 (dt, J = 12.2, 6.3 Hz, 1H), 1.85 - 1.80 (m, 1H), 1.76 (d, J = 4.4 Hz, 1H), 1.68 (td, J = 12.0, 3.9 Hz, 1H), 1.54 (tt, J = 12.5, 4.5 Hz, 1H), 1.47 (s, 3H), 1.23 (d, J = 9.6 Hz, 2H), 0.94 (s, 3H), 0.68 (s, 3H), 0.62 (s, 3H). 13 13C NMR (151 MHz, DMSO-d6), δ (ppm): 191.67, 160.71, 160.55, 138.45, 135.39, 134.70, 130.98, 130.58, 129.88, 128.72, 128.31, 127.22, 127.11, 126.43, 126.37, 125.56, 125.48, 122.68, 118.21, 58.30, 55.05, 47.63, 45.04, 41.01, 40.20, 37.12, 32.22, 30.27, 28.45, 26.07, 25.38, 24.61, 23.27. MS (m / z): [M + H] + calcd. for C 35 H 35 NO2 + H + , 502.2746; found, 502.2745.

[0050] 4) Preparation of compound ABP-BC:

[0051] 1 mmol of ABP-HC, 1 mmol of n-butyl bromide, 2 mmol of anhydrous potassium carbonate, and 10 mL of N,N-dimethylformamide were successively added to a single-necked flask equipped with a stirrer, and the mixture was refluxed at 85 °C for 1 h. After the reaction solution was extracted and the solvent was recovered by distillation, the crude product of compound ABP-BC was obtained; after purification by a silica gel column chromatography (petroleum ether:ethyl acetate = 80:1, v / v), white solid ABP-BC was obtained with a yield of 99%. 1 1H NMR (600 MHz, CDCl3), δ (ppm): 10.60 (s, 1H), 8.20 (d, J = 2.5 Hz, 1H), 8.03 (d, J = 8.4 Hz, 1H), 7.90 (dd, J = 8.6, 2.5 Hz, 1H), 7.74 (ddt, J = 6.5, 4.5, 1.9 Hz, 2H), 7.59 (ddd, J = 8.4, 6.6, 1.5 Hz, 1H), 7.40 (dd, J = 8.5, 1.4 Hz, 1H), 7.35 (dd, J = 8.2, 1.9 Hz, 1H), 7.32 (ddd, J = 8.2, 6.7, 1.2 Hz, 1H), 7.30 - 7.27 (m, 1H), 7.12 (d, J = 8.6 Hz, 1H), 4.18 (t, J = 6.4 Hz, 2H), 2.85 (s, 1H), 2.76 (d, J = 16.5 Hz, 1H), 2.27 (d, J = 16.5 Hz, 1H), 2.00 (ddt, J = 12.5, 9.2, 2.8 Hz, 1H), 1.89 (dq, J = 8.4, 6.4 Hz, 2H), 1.84 - 1.79 (m, 2H), 1.71 (td, J = 12.1, 4.0 Hz, 1H), 1.62 - 1.57 (m, 3H), 1.56 (s, 3H), 1.28 - 1.24 (m, 2H), 1.03 (t, J = 7.4 Hz, 3H), 0.98 (s, 3H), 0.75 (s, 3H), 0.67 (s, 3H). 13 13C NMR (151 MHz, CDCl3), δ (ppm): 189.94, 161.30, 139.01, 134.36, 133.15, 130.49, 130.03, 126.89, 126.86, 126.73, 126.22, 125.91, 125.21, 113.25, 68.67, 55.68, 48.27, 45.68, 41.44, 37.59, 32.69, 31.30, 30.78, 28.62, 26.24, 25.60, 25.04, 23.42, 19.44, 13.98. MS (m / z): [M+H] + calcd. for C 39 H 43NO2 + H + , 558.3372; found, 558.3815.

[0052] 5) Preparation of compound ABP - BBT:

[0053] 1 mmol of ABP - BC, 1 mmol of 2 - methyl - 3 - ethylbenzothiazol - 3 - ylium salt, 1 mL of pyridine, and 10 mL of dichloromethane were successively added to a single - necked flask equipped with a stirrer, and the mixture was refluxed at room temperature for 4 h. After the reaction solution was extracted and the solvent was recovered by distillation, a crude product of compound ABP - BBT was obtained. After purification by a silica gel column chromatography (dichloromethane:methanol = 50:1, v / v), an orange solid ABP - BBT was obtained, and the yield was 62%. 1 1H NMR (600 MHz, DMSO - d6)), δ (ppm): 8.55 (d, J = 2.4 Hz, 1H), 8.47 (d, J = 8.1 Hz, 1H), 8.41 (d, J = 15.9 Hz, 1H), 8.34 (d, J = 8.5 Hz, 1H), 8.21 (d, J = 15.9 Hz, 1H), 8.03 (dd, J = 8.7, 2.2 Hz, 1H), 7.99 - 7.93 (m, 3H), 7.90 (t, J = 7.8 Hz, 1H), 7.82 (t, J = 7.7 Hz, 1H), 7.65 (t, J = 7.7 Hz, 1H), 7.52 (d, J = 7.8 Hz, 1H), 7.44 - 7.36 (m, 3H), 7.33 (d, J = 8.4 Hz, 1H), 4.98 (q, J = 7.3 Hz, 2H), 4.28 (t, J = 6.4 Hz, 2H), 2.85 (d, J = 16.3 Hz, 1H), 2.75 (s, 1H), 2.22 (d, J = 16.4 Hz, 1H), 1.90 (h, J = 6.6 Hz, 3H), 1.85 (d, J = 9.6 Hz, 1H), 1.78 (d, J = 4.3 Hz, 1H), 1.70 (td, J = 12.0, 3.7 Hz, 1H), 1.58 (p, J = 7.7 Hz, 3H), 1.52 (t, J = 7.3 Hz, 3H), 1.49 (s, 3H), 1.23 (d, J = 9.6 Hz, 2H), 1.03 (t, J = 7.4 Hz, 3H), 0.96 (s, 3H), 0.70 (s, 3H), 0.64 (s, 3H). 1313C NMR (151 MHz, DMSO-d6)), δ (ppm): 172.07, 160.59, 158.02, 143.27, 141.07, 138.31, 132.79, 132.53, 130.41, 129.71, 129.61, 128.47, 128.28, 128.23, 126.82, 126.75, 125.45, 125.28, 124.58, 122.56, 116.69, 113.85, 113.69, 68.53, 58.17, 54.91, 47.49, 44.92, 44.60, 40.95, 36.99, 32.10, 30.68, 30.13, 28.32, 25.97, 25.32, 24.47, 23.19, 18.89, 14.14, 13.77. MS (m / z): [M+H] + calcd. for C 49 H 53 N2OS + +H + , 718.3951; found, 718.3907.

[0054] Example 2

[0055] The compound ABP-BBT was formulated into a 1×10 -5 M PBS buffer solution. Hydrazine was dissolved in the PBS buffer to prepare solutions with concentrations of 0, 1.0×10 -5 , 2.0×10 -5 , 3.0×10 -5 , 4.0×10 -5 , 5.0×10 -5 , 6.0×10 -5 , 7.0×10 -5 , 8.0×10 -5 M. The fluorescence emission spectra of the compound ABP-BBT in the presence of hydrazine at different concentrations were measured on a fluorescence spectrophotometer using fluorescence spectral titration, as shown in Figure 1 . The results showed that as the concentration of hydrazine in the solution gradually increased, the fluorescence emission intensity of the probe at 598 nm gradually decreased. Thus, it was indicated that this compound could be used as a fluorescent probe for sensitively detecting the hydrazine content in the solution.

[0056] Example 3

[0057] The compound ABP-BBT was formulated into a 1×10 -5 M PBS buffer solution. At the same time, different amines and hydrazine derivatives were dissolved in ultrapure water to prepare solutions with a concentration of 1.0×10 -4Solution of M. The fluorescence emission spectra of compound ABP-BBT in the presence of different amine and hydrazine derivatives were measured on a fluorescence spectrophotometer using fluorescence spectral titration method, as Figure 2 shown. The results show that the addition of hydrazine will significantly reduce the fluorescence emission intensity of the probe at 598 nm. By adding different amine and hydrazine derivatives (leucine, valine, threonine, glycine, tryptophan, ammonium carbonate, hydroxylamine, benzylamine, triethylamine, ammonium tetrahydroborate, ammonium acetate, thiosemicarbazide, 2-hydroxyethylhydrazine, acetylhydrazine, isoniazid, benzoylhydrazine, 2-pyridinecarboxylic hydrazide, cetylamine, 2,4-dinitrophenylhydrazine, benzenesulfonylhydrazide) and observing by reference and comparison, the fluorescence spectrum of the probe did not change significantly. This shows that this compound can be used as a fluorescence probe for specific detection of hydrazine.

Claims

1. An isopulegol-based fluorescent probe for detecting hydrazine, characterized in that, The probe is 2-(2-(4-butoxy-4′-(1,1,5,5-tetramethyl-1,3,4,5,6,12b-hexahydro-2H-2,4a-chromeno[2,3-b]quinolin-7-yl)-[1,1′-biphenyl]-3-yl)vinyl)-3-ethyl-benzothiazol-3-ium salt (hereinafter referred to as ABP-BBT), and its structural formula is:

2. The preparation method of the isolongifolanyl fluorescent probe for detecting hydrazine according to claim 1, characterized in that, It includes the following steps: 1) Isolongifolione reacts with 2-amino-4′-bromobenzophenone through a condensation reaction to obtain 7-(4-bromophenyl)-1,1,5,5-tetramethyl-1,3,4,5,6,12b-hexahydro-2H-2,4a-chromeno[2,3-b]quinoline (hereinafter referred to as AB-Br); 2) Compound AB-Br undergoes a Suzuki coupling reaction with 4-hydroxyphenylboronic acid to obtain 4′-(1,1,5,5-tetramethyl-1,3,4,5,6,12b-hexahydro-2H-2,4a-chromeno[2,3-b]quinolin-7-yl)-[1,1′-biphenyl]-4-ol (hereinafter referred to as ABP-OH); 3) Compound ABP-OH undergoes a formylation reaction with hexamethylenetetramine to obtain 4-hydroxy-4′-(1,1,5,5-tetramethyl-1,3,4,5,6,12b-hexahydro-2H-2,4a-chromeno[2,3-b]quinolin-7-yl)-[1,1′-biphenyl]-3-carbaldehyde (hereinafter referred to as ABP-HC); 4) Compound ABP-HC further undergoes an etherification reaction with 1-bromobutane to obtain 4-butoxy-4′-(1,1,5,5-tetramethyl-1,3,4,5,6,12b-hexahydro-2H-2,4a-chromeno[2,3-b]quinolin-7-yl)-[1,1′-biphenyl]-3-carbaldehyde (hereinafter referred to as ABP-BC); 5) Compound ABP-BC undergoes a condensation reaction with 2-methyl-3-ethylbenzothiazol-3-ium salt to obtain 2-(2-(4-butoxy-4′-(1,1,5,5-tetramethyl-1,3,4,5,6,12b-hexahydro-2H-2,4a-chromeno[2,3-b]quinolin-7-yl)-[1,1′-biphenyl]-3-yl)vinyl)-3-ethyl-benzothiazol-3-ium (hereinafter referred to as ABP-BBT).

3. The preparation method of the isopimarenone-based fluorescent probe for detecting hydrazine according to claim 2, characterized in that, In step 1), under the catalysis of sulfamic acid, isolongifolione reacts with 2-amino-4′-bromobenzophenone to obtain compound AB-Br. The specific preparation method includes: (1) Add 11 mmol of 2-amino-4'-bromobenzophenone, 8-12 mmol of isolongifolione, and 10-15 mmol of sulfamic acid into a closed U-tube equipped with a stirrer, and react at 85 °C for 46-48 h; (2) After the reaction mixture is extracted, washed, and the solvent is recovered by distillation, a crude product of AB-Br is obtained; (3) The crude product of AB-Br is chromatographed on a silica gel column (petroleum ether) to obtain white powder AB-Br.

4. The preparation method of the isopimarenone-based fluorescent probe for detecting hydrazine according to claim 2, characterized in that, In step 2), under a nitrogen atmosphere, compound AB-Br reacts with 4-hydroxyphenylboronic acid to obtain compound ABP-OH. The specific preparation method includes: (1) 2 mmol of AB-Br, 4 - 6 mmol of 4-hydroxybenzeneboronic acid, an aqueous solution of 1 M potassium carbonate, and 40 - 60 mL of 1,4-dioxane were successively added to a three-necked flask equipped with a stirrer. Under nitrogen protection, 0.1 mmol of tetrakis(triphenylphosphine)palladium was added and the reaction was carried out at 90 °C for 12 - 15 h; (2) After the reaction solution was distilled to recover the solvent, a crude product of ABP-OH was obtained; (3) The crude product of ABP-OH was purified by a silica gel chromatography column (petroleum ether:ethyl acetate = 100:1) to obtain white solid ABP-OH.

5. The preparation method of the isopimaranyl fluorescent probe for detecting hydrazine according to claim 2, characterized in that, In step 3), compound ABP-OH reacts with hexamethylenetetramine to obtain compound ABP-HC. The specific preparation method includes: (1) 1 mmol of ABP-OH, 3 - 5 mmol of hexamethylenetetramine, and 10 - 12 mL of trifluoroacetic acid were successively added to a single-necked flask equipped with a stirrer. The reaction was refluxed at 90 °C for 12 - 15 h; (2) After the reaction solution was extracted, the pH was adjusted, and the solvent was distilled off to obtain a crude product of ABP-HC; (3) The crude product of ABP-HC was chromatographed on a silica gel column (dichloromethane) to obtain white solid ABP-HC.

6. The preparation method of the isolongifolanyl fluorescent probe for detecting hydrazine according to claim 2, characterized in that, In step 4), under the action of potassium carbonate, ABP-HC reacts with 1-bromobutane to obtain compound ABP-BC. The specific preparation method includes: (1) 1 mmol of ABP-HC, 1 - 3 mmol of 1-bromobutane, 2 - 3 mmol of anhydrous potassium carbonate, and 10 - 15 mL of N,N-dimethylformamide were successively added to a single-necked flask equipped with a stirrer. The reaction was refluxed at 85 °C for 1 - 2 h; (2) After the reaction solution was extracted and the solvent was distilled off, a crude product of ABP-BC was obtained; (3) The crude product of ABP-BC was purified by a silica gel chromatography column (petroleum ether:ethyl acetate = 80:1, v / v) to obtain white solid ABP-BC.

7. The preparation method of the isolongifolanyl fluorescence probe for detecting hydrazine according to claim 2, characterized in that In step 5), compound ABP-BC undergoes a condensation reaction with 2-methyl-3-ethylbenzothiazol-3-ium salt to obtain compound ABP-BBT. The specific preparation method includes: (1) 1 mmol of ABP-BC, 1 - 2 mmol of 2-methyl-3-ethylbenzothiazol-3-ium salt, 1 - 2 mL of pyridine, and 10 - 15 mL of dichloromethane were successively added to a single-necked flask equipped with a stirrer. The reaction was refluxed at room temperature for 4 - 5 h; (2) After the reaction solution was extracted and the solvent was distilled off, a crude product of ABP-BBT was obtained; (3) The crude product of ABP-BBT was purified by a silica gel chromatography column (dichloromethane:methanol = 50:1, v / v) to obtain orange solid ABP-BBT.

8. The application of ABP-BBT as claimed in claim 1 in the detection of hydrazine.

9. The application of ABP-BBT as claimed in claim 1 in the preparation of a fluorescent probe for the detection of hydrazine.

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