CN-120247895-B - Thienyl group oxa Azohydrazide class Al3+Fluorescent probe and preparation method thereof

CN120247895BCN 120247895 BCN120247895 BCN 120247895BCN-120247895-B

Abstract

The invention relates to a thienyl oxazolyl formylhydrazine Al 3+ fluorescent probe and a preparation method thereof, wherein the preparation method comprises the steps of generating a cyclic compound through the reaction of thiophene-2-carbonyl chloride and isocyanoacetic acid ethyl ester to obtain an intermediate 1, carrying out acylation reaction on the intermediate 1 and hydrazine hydrate to obtain a compound SON, oxidizing 2, 6-bis (hydroxymethyl) -p-toluene phenol to obtain an intermediate 2, and carrying out amine aldehyde condensation reaction on the intermediate 2 and the compound SON to obtain the thienyl oxazolyl formylhydrazine Al 3+ fluorescent probe. The thienyl oxazolyl hydrazide Al 3+ fluorescent probe has high preparation yield, high sensitivity and strong specific recognition capability, is suitable for pH detection in natural environment and water body, generates strong blue fluorescence after being combined with metal Al 3+ , can realize naked eye recognition, can also be used for rapid monitoring of Al 3+ in natural environment and biological cell systems, and has important practical application and expansion value.

Inventors

HU BIN
CHEN HONG
YU MEIHUA
CHENG XIAOXIA
YANG YIHAN
WEN HANGYU

Assignees

南昌航空大学

Dates

Publication Date: 20260512
Application Date: 20250402

Claims (6)

1. A thienyl oxazolyl formylhydrazine Al 3+ fluorescent probe is characterized in that the chemical structural formula of the thienyl oxazolyl formylhydrazine Al 3+ fluorescent probe is as follows: 。
2. A preparation method of the thienyl oxazolyl formylhydrazine Al 3+ fluorescent probe according to claim 1 is characterized by comprising the steps of firstly reacting thiophene-2-carbonyl chloride with isocyanoacetic acid ethyl ester to generate a cyclic compound to obtain an intermediate 1, carrying out acylation reaction on the intermediate 1 and hydrazine hydrate to obtain a compound SON 5- (thiophene-2-yl) oxazole-4-formylhydrazine, oxidizing 2, 6-bis (hydroxymethyl) -p-cresol to obtain an intermediate 2:3- (hydroxymethyl) -5-methyl salicylaldehyde, and carrying out aldol condensation reaction on the intermediate 2 and the compound SON to obtain the thienyl oxazolyl formylhydrazine Al 3+ fluorescent probe; wherein, the structures of the intermediate 1, the compound SON and the intermediate 2 are as follows: ; The method comprises the following specific steps: Stirring thiophene-2-carbonyl chloride and ethyl isocyanoacetate in a mixed solution of triethylamine and tetrahydrofuran at room temperature overnight under the protection of argon, monitoring the reaction progress by thin layer chromatography, cooling the product to room temperature after the reaction is finished, performing column chromatography separation and elution, and removing an eluent by rotary evaporation to obtain an intermediate 1; Step 2, heating and refluxing the intermediate 1 and hydrazine hydrate in an absolute ethanol solution to 1-2 h, cooling the product to room temperature, separating and eluting by column chromatography, and removing an eluent by rotary evaporation to obtain a compound SON; Heating and refluxing 2, 6-bis (hydroxymethyl) -p-toluol and manganese dioxide in methylene dichloride solution under the protection of argon, monitoring the reaction progress by thin layer chromatography, cooling the product to room temperature, washing by ethanol, separating and eluting by column chromatography, and removing eluent by rotary evaporation to obtain an intermediate 2; And 4, heating and refluxing the intermediate 2 and the compound SON in an absolute ethanol solution for 4-6 h to separate out white solid, and filtering and washing the product by ethanol to obtain the thienyl oxazolyl hydrazide Al 3+ fluorescent probe.
3. The preparation method of the thienyl oxazolyl hydrazide Al 3+ fluorescent probe according to claim 2 is characterized in that in the step 1, the mol ratio of thiophene-2-carbonyl chloride to isocyanoacetic acid ethyl ester is 1:1, the volume ratio of triethylamine to tetrahydrofuran mixed solution is 1:3, and the eluent is acetic acid ethyl ester and petroleum ether with the volume ratio of 3:7.
4. The preparation method of the thienyl oxazolyl formylhydrazine Al 3+ fluorescent probe according to claim 2 is characterized in that in the step 2, the molar ratio of the intermediate 1 to hydrazine hydrate is 1:10, and the eluent is ethyl acetate and petroleum ether with the volume ratio of 6:4.
5. The method for preparing the thienyl oxazolyl formylhydrazine Al 3+ fluorescent probe according to claim 2, wherein in the step 3, the molar ratio of 2, 6-bis (hydroxymethyl) -p-cresol to manganese dioxide is 7:100, and the eluent is ethyl acetate and petroleum ether with the volume ratio of 2:8.
6. The method for preparing the thienyl oxazolyl hydrazide Al 3+ fluorescent probe according to claim 2, wherein in the step 4, the molar ratio of the intermediate 2 to the compound SON is 1:1.

Description

Thienyl oxazolyl formylhydrazine Al 3+ fluorescent probe and preparation method thereof Technical Field The invention relates to a thienyl oxazolyl formylhydrazine Al 3+ fluorescent probe and a preparation method thereof, and particularly belongs to the technical field of organic chemistry. Background Aluminum is a silvery light metal, is abundant in crust, and is next to oxygen and silicon, the most abundant metal element in crust. Aluminum is used as an active metal, has softer texture, has good electrical conductivity, thermal conductivity, heat resistance and nuclear radiation resistance, and can form a layer of compact oxide film in humid air to prevent further corrosion of the metal, and aluminum alloys occupy important positions in aviation, construction, automobile industry, household utensils, electronic products and the like. Although aluminum and its alloys are very widely used in industry and daily life, their potential hazards are not negligible. Excessive intake of aluminum metal can cause various hazards to the human body, mainly including nervous system effects, osteoporosis, skin problems, endocrine disruptors, and the like. Prolonged exposure to aluminum or accumulation of aluminum in the body may lead to decreased memory, increased risk of developing Alzheimer's disease, and also may cause skin irritation and inflammation. Aluminum is considered an endocrine disruptor and may affect hormone balance and even the reproductive system. Therefore, development of the method can specifically identify, has high sensitivity and is important to realizing trace monitoring of Al 3+ in industrial and water and soil environments. With the rapid development of science and technology, researchers have developed a number of fluorescence chemical sensors for the detection of Al 3+ in environmental and biological systems. However, most of the Al 3+ fluorescence sensors have the defects of complicated synthesis steps, low selectivity and solubility, poor recycling performance, narrow application range of pH, long response time and the like, and are limited in application fields. The TianL.M and the like synthesize a novel double-probe aluminum ion fluorescent probe, but the synthesis steps are complex and the yield is low. The aluminum ion fluorescent probe synthesized by Tian Z.N and the like has poor solubility, and the fluorescent performance is shifted and enhanced obviously. Li Na and the like, and the detection of aluminum ions can be interfered by other ions. The response time of the Zhang C.L and other designed and synthesized fluorescent probes to aluminum ions reaches 10min, and the response time is too long. Gao Huan and the like are designed and synthesized, the fluorescent probe has response to aluminum ions within the pH range of 5-6, the applicable pH range is narrower, and the anti-interference capability of the probe is poor. The compound containing the thiophene ring unit has certain electronic adjustability, the salicylaldehyde and the salicylaldehyde derivative have better solubility, the salicylaldehyde derivative is used for expanding the thienyl oxazolyl formylhydrazine compound to realize compound energy level matching, multi-site recognition of target metal ions is provided, the compound has good chemical properties, the compound is less interfered by environmental factors, the pH application range is wide, and the compound can be used for real-time detection and on-site recognition. Therefore, the design and development of the Al 3+ fluorescent probe with rapid detection and specific recognition have important practical application value. Disclosure of Invention The invention aims to provide a thienyl oxazolyl formylhydrazine Al 3+ fluorescent probe and a preparation method thereof. The fluorescent probe can be used for detecting Al 3+ in biological and water environments, and has the characteristics of good solubility, specific recognition, high synthesis yield, strong anti-interference capability and the like. The chemical structural formula of the thienyl oxazolyl formylhydrazine Al 3+ fluorescent probe is as follows: ; The preparation method of the thienyl oxazolyl formylhydrazine Al 3+ fluorescent probe comprises the steps of reacting thiophene-2-carbonyl chloride with isocyanoacetic acid ethyl ester to generate a cyclic compound to obtain an intermediate 1, carrying out acylation reaction on the intermediate 1 and hydrazine hydrate to obtain a compound SON, oxidizing 2, 6-bis (hydroxymethyl) -p-toluene phenol to obtain an intermediate 2, carrying out amine aldehyde condensation reaction on the intermediate 2 and the compound SON to obtain the thienyl oxazolyl formylhydrazine Al 3+ fluorescent probe; The method comprises the following specific steps: Stirring thiophene-2-carbonyl chloride and ethyl isocyanoacetate in a mixed solution of triethylamine and tetrahydrofuran at room temperature overnight under the protection of argon, monitoring the reaction progress by Thin Layer C