For detecting H2Isolongifolane colorimetric probe of S and preparation method thereof
阅读说明：本技术 一种用于检测h2s的异长叶烷基比色型探针及其制备方法 (For detecting H2Isolongifolane colorimetric probe of S and preparation method thereof ) 是由 王石发 巩帅 高语 王忠龙 张燕 李明新 杨益琴 徐徐 于 2020-06-09 设计创作，主要内容包括：本发明公开了一种用于检测H<Sub>2</Sub>S的异长叶烷基比色型探针及其制备方法。本发明利用天然可再生资源长叶烯衍生物异长叶烷酮为原料,与4-硝基苯甲醛缩合生成7-(4′-硝基苯亚甲基)异长叶烷酮；7-(4′-硝基苯亚甲基)异长叶烷酮再与水合肼和二氯二氰基苯醌进行缩合环化得到5,5,9,9-四甲基-3-(4-硝基苯基)-2,4,5,6,7,8,9,9a-八氢-5a,8-桥亚甲基苯并[g]吲唑,该化合物能专一性与H<Sub>2</Sub>S作用,颜色由无色变为黄褐色,可作为检测H<Sub>2</Sub>S浓度比色型探针。(The invention discloses a method for detecting H 2 S isolongifolane colorimetric probe and a preparation method thereof. According to the invention, a natural renewable resource longifolene derivative isolongifolanone is used as a raw material, and is condensed with 4-nitrobenzaldehyde to generate 7- (4' -nitrobenzylidene) isolongifolanone; condensing 7- (4' -nitrobenzylidene) isolongifolanone with hydrazine hydrate and dichloro dicyano benzoquinone for cyclization to obtain 5, 5, 9, 9-tetramethyl-3- (4-nitrophenyl) -2, 4, 5, 6, 7, 8, 9, 9 a-octahydro-5 a, 8-methanobenzo [ g]Indazoles, which compounds are specific for H 2 S is acted, the color is changed from colorless to yellow brown, and the S can be used for detecting H 2 And (3) an S concentration colorimetric type probe.)
1. For detecting H2S isolongifolane colorimetric probe, characterized in that the compound is: 5, 5, 9, 9-tetramethyl-3- (4-nitrophenyl) -2, 4, 5, 6, 7, 8, 9, 9 a-octahydro-5 a, 8-methanobenzo [ g ]]Indazoles, of the formula:
2. a process for the preparation of 5, 5, 9, 9-tetramethyl-3- (4-nitrophenyl) -2, 4, 5, 6, 7, 8, 9, 9 a-octahydro-5 a, 8-methanobenzo [ g ] indazole according to claim 1, comprising the steps of:
1) subjecting isolongifolanone and 4-nitrobenzaldehyde to aldol condensation to obtain 7- (4' -nitrobenzylidene) isolongifolanone;
2) condensation reaction of 7- (4' -nitrobenzylidene) isolongifolanone with hydrazine hydrate and dichlorodicyanobenzoquinone gives 5, 5, 9, 9-tetramethyl-3- (4-nitrophenyl) -2, 4, 5, 6, 7, 8, 9, 9 a-octahydro-5 a, 8-methanobenzo [ g ] indazole.
3. The method of preparing 5, 5, 9, 9-tetramethyl-3- (4-nitrophenyl) -2, 4, 5, 6, 7, 8, 9, 9 a-octahydro-5 a, 8-methanobenzo [ g ] indazole according to claim 2, wherein in step 1) isolongifolanone is aldolized with 4-nitrobenzaldehyde to give 7- (4' -nitrobenzylidene) isofolanone, which is specifically prepared as follows:
(1) sequentially adding 0.8mol of isolongifolanone, 1.5-3L of tert-butyl alcohol, 0.5mol of potassium tert-butoxide and 0.8-1.0 mol of 4-nitrobenzaldehyde into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, and reacting at 80-90 ℃;
(2) extracting the reactant by using 4-4.5L ethyl acetate for 3 times, combining organic phases, and washing the organic phases for a plurality of times by using saturated saline solution until the reaction mixture is neutral; drying the organic phase by anhydrous sodium sulfate, filtering and concentrating to obtain a crude product of 7- (4' -nitrobenzylidene) isolongifolanone;
(3) recrystallizing the crude product of the 7- (4 '-nitrobenzylidene) isolongifolanone with ethanol to obtain a pure product of the 7- (4' -nitrobenzylidene) isolongifolanone.
4. The method of preparing 5, 5, 9, 9-tetramethyl-3- (4-nitrophenyl) -2, 4, 5, 6, 7, 8, 9, 9 a-octahydro-5 a, 8-methanobenzo [ g ] indazole according to claim 2, wherein the 7- (4' -nitrobenzylidene) isolongifolanone is reacted with hydrazine hydrate and dichlorodicyanobenzoquinone in step 2) to provide 5, 5, 9, 9-tetramethyl-3- (4-nitrophenyl) -2, 4, 5, 6, 7, 8, 9, 9 a-octahydro-5 a, 8-methanobenzo [ g ] indazole, the method comprising:
(1) sequentially adding 0.8mol of 7- (4' -nitrobenzylidene) isolongifolanone, 4-4.8 mol of hydrazine hydrate and 4.5-5.0L of ethanol into a three-neck flask with a stirrer, a thermometer and a reflux condenser, heating and carrying out reflux reaction for 10h, carrying out GC tracking detection, and stopping the reaction until the conversion rate reaches 95%;
(2) after the reaction mixture is cooled to room temperature, rotary evaporation is carried out to remove ethanol and excessive hydrazine hydrate, 4L of 1, 4-dioxane and 0.8-0.85 mol of dichloro dicyanobenzoquinone are added, heating reflux is carried out, 2L of potassium hydroxide solution and 5L of dichloromethane are added after 8h of reaction, dichloromethane is used for extraction for three times after stirring for 30 minutes at room temperature, the combined organic layers are washed to be neutral by deionized water, then anhydrous sodium sulfate is used for drying, filtration and concentration are carried out to obtain oily liquid, and 5, 5, 9, 9-tetramethyl-3- (4-nitrophenyl) -2, 4, 5, 6, 7, 8, 9, 9 a-octahydro-5 a, 8-methanobenzo [ g ] indazole is obtained through silica gel column chromatography (ethyl acetate/petroleum ether ═ 1/3) and recrystallization.
5. Use of the 5, 5, 9, 9-tetramethyl-3- (4-nitrophenyl) -2, 4, 5, 6, 7, 8, 9, 9 a-octahydro-5 a, 8-methanobenzo [ g ] indazole of claim 1, as a colorimetric-type probe for the detection of hydrogen sulfide.
6. Use of the 5, 5, 9, 9-tetramethyl-3- (4-nitrophenyl) -2, 4, 5, 6, 7, 8, 9, 9 a-octahydro-5 a, 8-methanobenzo [ g ] indazole of claim 1, for detecting hydrogen sulfide.
Technical Field
The invention belongs to the technical field of fine organic synthesis, and relates to H detection2S isolongifolane colorimetric probe and preparation method and application thereof.
Background
Hydrogen sulfide is a colorless, highly toxic acid gas, is highly corrosive and irritating, and can damage the respiratory system and central nervous system of human body. Recent studies have shown that: hydrogen sulfide is also an important endogenous gas signaling molecule in the human body, and has various physiological functions, including inhibition of insulin signaling, regulation of inflammation, tumor resistance, regulation of ion channels, protection of the cardiovascular system, oxidation resistance, relaxation of vascular smooth muscle and the like. At present, methods for detecting hydrogen sulfide mainly comprise high performance liquid chromatography, iodometry, gas chromatography, electrochemical analysis and the like. However, these conventional detection methods have the disadvantages of complicated pretreatment, expensive equipment, complex operation, time-consuming detection, etc., and are not suitable for real-time detection of field samples. The colorimetric probe has the advantages of simple operation, low cost, high sensitivity, fast response time and the like, and is gradually an important means for detecting hydrogen sulfide. Therefore, the development and design of colorimetric hydrogen sulfide probes are of great significance.
Disclosure of Invention
Aiming at the defects in the prior art, the technical problem to be solved by the invention is to provide a method for detecting H2S isolongifolane colorimetric probe, specificity and H2S acts to change the color of the compound from colorless to yellow brown, and can be used for treating H2And (5) detecting the concentration of S. Another technical problem to be solved by the present invention is to provide the above-mentioned detection method H2A preparation method of an isolongifolane colorimetric type probe of S. The invention also aims to provide the detection H2The application of the isolongifolane colorimetric probe of S.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
detection of H2The isolongifolane colorimetric probe of S is as follows: 5, 5, 9, 9-tetramethyl-3- (4-nitrophenyl) -2, 4, 5, 6, 7, 8, 9, 9 a-octahydro-5 a, 8-methanobenzo [ g ]]Indazoles, of the formula:
the preparation method of the 5, 5, 9, 9-tetramethyl-3- (4-nitrophenyl) -2, 4, 5, 6, 7, 8, 9, 9 a-octahydro-5 a, 8-methanobenzo [ g ] indazole comprises the following steps:
1) subjecting isolongifolanone and 4-nitrobenzaldehyde to aldol condensation to obtain 7- (4' -nitrobenzylidene) isolongifolanone;
2) condensation reaction of 7- (4' -nitrobenzylidene) isolongifolanone with hydrazine hydrate and dichlorodicyanobenzoquinone gives 5, 5, 9, 9-tetramethyl-3- (4-nitrophenyl) -2, 4, 5, 6, 7, 8, 9, 9 a-octahydro-5 a, 8-methanobenzo [ g ] indazole.
In the step 1), the isolongifolanone and 4-nitrobenzaldehyde are subjected to aldol condensation to obtain 7- (4' -nitrobenzylidene) isolongifolanone, and the specific preparation method is as follows:
(1) sequentially adding 0.8mol of isolongifolanone, 1.5-3L of tert-butyl alcohol, 0.5mol of potassium tert-butoxide and 0.8-1.0 mol of 4-nitrobenzaldehyde into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, and reacting at 80-90 ℃;
(2) extracting the reactant by using 4-4.5L ethyl acetate for 3 times, combining organic phases, and washing the organic phases for a plurality of times by using saturated saline solution until the reaction mixture is neutral; drying the organic phase by anhydrous sodium sulfate, filtering, concentrating and recovering a solvent 7- (4' -nitrobenzylidene) isolongifolanone crude product;
(3) recrystallizing the crude product of the 7- (4 '-nitrobenzylidene) isolongifolanone with ethanol to obtain a pure product of the 7- (4' -nitrobenzylidene) isolongifolanone.
In the step 2), 7- (4' -nitrobenzylidene) isolongifolanone reacts with hydrazine hydrate and dichlorodicyanoquinone to obtain 5, 5, 9, 9-tetramethyl-3- (4-nitrophenyl) -2, 4, 5, 6, 7, 8, 9, 9 a-octahydro-5 a, 8-methanobenzo [ g ] indazole, and the specific preparation method comprises the following steps:
(1) sequentially adding 0.8mol of 7- (4' -nitrobenzylidene) isolongifolanone, 4-4.8 mol of hydrazine hydrate and 4.5-5.0L of ethanol into a three-neck flask with a stirrer, a thermometer and a reflux condenser, heating and carrying out reflux reaction for 10h, carrying out GC tracking detection, and stopping the reaction until the conversion rate reaches 95%;
(2) after the reaction mixture is cooled to room temperature, removing ethanol by rotary evaporation, adding 4L of 1, 4-dioxane and 0.8-0.85 mol of dichloro dicyanobenzoquinone, heating and refluxing, reacting for 8h, adding 2L of potassium hydroxide solution and 5L of dichloromethane, stirring for 30 min at room temperature, extracting with dichloromethane for three times, washing the combined organic layers with deionized water to neutrality, drying with anhydrous sodium sulfate, filtering, concentrating to obtain an oily liquid, and performing silica gel column chromatography (ethyl acetate/petroleum ether ═ 1/3) and recrystallization to obtain 5, 5, 9, 9-tetramethyl-3- (4-nitrophenyl) -2, 4, 5, 6, 7, 8, 9, 9 a-octahydro-5 a, 8-methanobenzo [ g ] indazole.
The compound 5, 5, 9, 9-tetramethyl-3- (4-nitrophenyl) -2, 4, 5, 6, 7, 8, 9, 9 a-octahydro-5 a, 8-methanobenzo [ g ]]Indazole-specific and H2The color of the product changes from colorless to yellow brown under the action of S ions.
The 5, 5, 9, 9-tetramethyl-3- (4-nitrophenyl) -2, 4, 5, 6, 7, 8, 9, 9 a-octahydro-5 a, 8-methanobenzo [ g ] indazole is used as a colorimetric probe to detect hydrogen sulfide.
The 5, 5, 9, 9-tetramethyl-3- (4-nitrophenyl) -2, 4, 5, 6, 7, 8, 9, 9 a-octahydro-5 a, 8-methanobenzo [ g ] indazole is applied to detection of hydrogen sulfide.
Has the advantages that: compared with the existing research results, the invention utilizes the natural renewable resource longifolene derivative isolongifolanone as the raw material to prepare the 5, 5, 9, 9-tetramethyl-3- (4-nitrophenyl) -2, 4, 5, 6, 7, 8, 9, 9 a-octahydro-5 a, 8-methanobenzo [ g]Indazoles; can be specific with H2S doesCan be used as detection H2And (3) an S concentration colorimetric type probe.
Drawings
FIG. 1 is 5, 5, 9, 9-tetramethyl-3- (4-nitrophenyl) -2, 4, 5, 6, 7, 8, 9, 9 a-octahydro-5 a, 8-methanobenzo [ g ]]Indazole with varying concentrations of H2(ii) a graph of the ultraviolet absorption spectrum result of the S action;
FIG. 2 is a graph showing the results of ultraviolet absorption spectra of 5, 5, 9, 9-tetramethyl-3- (4-nitrophenyl) -2, 4, 5, 6, 7, 8, 9, 9 a-octahydro-5 a, 8-methanobenzo [ g ] indazole added with different ions.
Detailed Description
The present invention will be further described with reference to the following specific examples.