CN107556259B - Organic small molecule with recognition effect on ammonia water, aliphatic amine and aromatic amine and recognition method thereof - Google Patents
Organic small molecule with recognition effect on ammonia water, aliphatic amine and aromatic amine and recognition method thereof Download PDFInfo
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- CN107556259B CN107556259B CN201710846475.6A CN201710846475A CN107556259B CN 107556259 B CN107556259 B CN 107556259B CN 201710846475 A CN201710846475 A CN 201710846475A CN 107556259 B CN107556259 B CN 107556259B
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Abstract
The invention discloses a compound with the functions of identifying ammonia water, aliphatic amine and aromatic amineThe other-acting organic small molecule, namely 5- (4-bromophenyl) isoxazole-3-carboxylic acid methyl ester has the following structure:
Description
Technical Field
The invention relates to the field of organic chemistry and supramolecules, in particular to a supramolecular system for chemical reaction regulation.
Background
The organic small molecules can usually change under certain chemical or physical conditions, and how to find and invent an organic molecule with a simple structure and identify and detect certain substances by utilizing the chemical changes and phenomena of the organic molecule is significant. The amine substance is a common organic substance widely existing in organisms, a chemical substance is searched and invented, ammonia water and a lower amine substance can be identified, and the visual identification by naked eyes through different changes of appearance phase states has certain biological and medical values. The invention patent with the application number of 201510120045.7 relates to an organic small molecule, and a methanol solution of the organic small molecule can show different appearance forms, namely solution, gel and crystallization, to lithium hydroxide, sodium hydroxide and potassium hydroxide, and the visible selective recognition of hydroxides of metal elements Li, Na and K in the first main group is realized. However, selective recognition of simple amino organic homologues is relatively few, and through intensive research, the application discloses a similar isoxazole molecule, and an alcoholic solution of the isooxazole molecule can rapidly detect ammonia water, aliphatic amine and aromatic amine, so that the isooxazole molecule is expected to provide valuable application in clinical medical detection.
Disclosure of Invention
The invention aims to solve the technical problem of providing small organic molecules for identifying ammonia water, aliphatic amine and aromatic amine, and realizing the rapid detection and identification of the ammonia water, the aliphatic amine and the aromatic amine through different appearance forms of alcoholic solutions of the small organic molecules for identifying the ammonia water, the aliphatic amine and the aromatic amine.
In order to solve the technical problems, the invention adopts the following technical scheme:
the organic small molecule is characterized in that the organic small molecule is 5- (4-bromophenyl) isoxazole-3-carboxylic acid methyl ester in Chinese name and methyl 5- (4-bromophenyl) isoxazole-3-carboxylate in English name, and the structural formula of the organic small molecule is as follows:
the method for identifying ammonia water, aliphatic amine and aromatic amine by the organic micromolecules comprises the following steps:
adding ammonia water into a methanol solution of 5- (4-bromophenyl) isoxazole-3-carboxylic acid methyl ester, standing for 1-5 minutes at room temperature to form a compact gel;
adding lower aliphatic amine (methylamine, ethylamine and propylamine) into a methanol solution of methyl 5- (4-bromophenyl) isoxazole-3-carboxylate, and standing at room temperature for 1-5 minutes to form crystals in the system;
adding aromatic amine (aniline, 1-naphthylamine and pyridine-2-amine) into a methanol solution of methyl 5- (4-bromophenyl) isoxazole-3-carboxylate, and standing at room temperature for 5 minutes to form a transparent solution.
The alcohol is methanol or ethanol.
The invention has the beneficial effects that: the organic micromolecules can realize different appearance recognition phase states for three types of amine substances, namely ammonia water, aliphatic amine and aromatic amine, so that the organic micromolecules can be applied to the aspects of molecular recognition, medical detection and the like. The synthesis method of the 5- (4-bromophenyl) isoxazole-3-carboxylic acid methyl ester is simple, has low cost, can be used for large-scale rapid preparation, and has an industrial production basis. The identifiability of the product is visible with naked eyes, and the operation is simple.
Detailed Description
The invention provides an organic small molecule for detecting and identifying ammonia water, aliphatic amine and aromatic amine, wherein the organic small molecule is named as 5- (4-bromophenyl) isoxazole-3-carboxylic acid methyl ester in Chinese and named as methyl 5- (4-bromophenyl) isoxazole-3-carboxylate in English, and the structural formula of the organic small molecule is as follows:
the method for identifying ammonia water, aliphatic amine and aromatic amine by the organic micromolecules comprises the following steps:
dissolving 0.01-0.1mmol of the methyl 5- (4-bromophenyl) isoxazole-3-carboxylate in 1mL of alcohol to form an alcoholic solution of methyl 5- (4-bromophenyl) isoxazole-3-carboxylate;
adding ammonia water with equal molar quantity into 5- (4-bromophenyl) isoxazole-3-carboxylic acid methyl ester alcoholic solution, uniformly mixing, standing for 1-5 minutes at the temperature of 20-30 ℃, and forming a dense alcogel by a system;
adding equimolar amount of lower aliphatic amine (methylamine, ethylamine, propylamine) into 5- (4-bromophenyl) isoxazole-3-carboxylic acid methyl ester alcoholic solution, mixing uniformly, standing for 1-5 minutes at 20-30 ℃ to form crystals;
adding aromatic amine (aniline, 1-naphthylamine, pyridine-2-amine) with equal molar amount into 5- (4-bromophenyl) isoxazole-3-carboxylic acid methyl ester alcoholic solution, mixing well, standing at 20-30 deg.C for 1-5 min to form transparent solution.
The alcohol is methanol or ethanol.
The present invention will be further described with reference to the following examples. It is to be understood that the following examples are illustrative only and are not intended to limit the scope of the invention, which is to be given numerous insubstantial modifications and adaptations by those skilled in the art based on the teachings set forth above.
Example 1
Synthesis of methyl 5- (4-bromophenyl) isoxazole-3-carboxylate
In a 2000mL three-necked flask with reflux condenser, mechanical stirring was used. 1000mL of methanol was added to the three-necked flask. 12g of solid sodium metal are weighed into petroleum ether, carefully cut into sodium threads with scissors and then added in portions to the methanol solution. A large amount of heat is released in the adding process, cooling is not needed at the moment, and the methanol is kept in a slightly boiling state. After the sodium threads disappeared after the addition was complete, the mixture of 4-bromoacetophenone (100 g, 0.5 mol) and diethyl oxalate (73.06 g, 0.5 mol) was placed in a constant pressure funnel and slowly added to a solution of sodium methoxide in methanol. After the addition, the mixture was stirred at room temperature for 1 hour. Then 24.5g of concentrated sulfuric acid is weighed in a constant pressure funnel and slowly dropped. After the addition, 35.75g of solid hydroxylamine hydrochloride was added in one portion. After the addition, the temperature is raised to 100 ℃ by heating, and the reaction is carried out for 8 hours by mechanical stirring. The heating was turned off and the reaction flask was allowed to cool at room temperature and after half an hour white solid gradually precipitated. After the crystallization is finished, the mixture is filtered under reduced pressure to obtain 132.5g of white granular solid with the yield of 94 percent. .
LC-MS；λ=214nm,99.45%.λ=254nm,99.1%.MS:[M+H]+280.97，282.96；[M+Na]+225.9；
1H-NMR(500MHz,CDCl3)：δ=7.69-7.65(m,4H)，7.12(s,1H) ，3.99(s,3H);
13C-NMR (500MHz,CDCl3): 162.5 158.7 131.6 130.3 129.5 127.8101.9 55.8；
Anal.calcd for C11H8BrNO3: C, 46.84; H, 2.86; Br, 28.33; N, 4.97; O,17.02；found 46.62; H, 2.76; Br, 28.13; N, 5.02。
Example 2 identification of Ammonia
2.8mg (0.01 mmol) of methyl 5- (4-bromophenyl) isoxazole-3-carboxylate is weighed, dissolved in 1mL of methanol, 1.5mL of ammonia water is added into the prepared alcoholic solution, and after full dissolution, the solution stands for 5 minutes, and the system is solidified to form dense gel.
Example 3 identification of p-methylamine
Weighing 2.8mg (0.01 mmol) of 5- (4-bromophenyl) isoxazole-3-carboxylic acid methyl ester, dissolving in 1mL of methanol, weighing 1mL of methylamine, adding into the prepared alcoholic solution, fully dissolving, standing, and forming crystals after 5 minutes. .
Example 4 identification of para-anilines
2.8mg (0.01 mmol) of methyl 5- (4-bromophenyl) isoxazole-3-carboxylate is weighed out and dissolved in 1mL of methanol, 0.93mg of aniline (0.01 mmol) is weighed out and added into the prepared alcoholic solution, the mixture is fully dissolved and stands still, and after 5 minutes, the system is still a transparent solution.
Example 5 identification of Ammonia
14mg (0.05 mmol) of methyl 5- (4-bromophenyl) isoxazole-3-carboxylate is weighed out and dissolved in 5mL of methanol, 7.5mL of ammonia water is added to the prepared alcoholic solution, and after sufficient dissolution, the solution is left for 5 minutes, and the system is solidified to form a compact gel.
Example 6 identification of p-methylamine
Weighing 14mg (0.05 mmol) of 5- (4-bromophenyl) isoxazole-3-carboxylic acid methyl ester, dissolving in 5mL of methanol, weighing 5mL of methylamine, adding into the prepared alcoholic solution, fully dissolving, standing, and crystallizing after 5 minutes.
Example 7 identification of para-anilines
14mg (0.05 mmol) of methyl 5- (4-bromophenyl) isoxazole-3-carboxylate is weighed out and dissolved in 5mL of methanol, 4.65mg of aniline (0.05 mmol) is weighed out and added into the prepared alcoholic solution, the mixture is fully dissolved and stands still, and after 5 minutes, the system is still a transparent solution.
Example 8 identification of Ammonia
28mg (0.1 mmol) of methyl 5- (4-bromophenyl) isoxazole-3-carboxylate is weighed, dissolved in 10mL of methanol, 15mL of ammonia water is added into the prepared alcoholic solution, and after full dissolution, the solution stands for 5 minutes, and the system is solidified to form a compact gel.
Example 9 identification of p-methylamine
Weighing 28mg (0.1 mmol) of 5- (4-bromophenyl) isoxazole-3-carboxylic acid methyl ester, dissolving in 10mL of methanol, weighing 10mL of methylamine, adding into the prepared alcohol solution, fully dissolving, standing, and forming crystals after 5 minutes.
Example 10 identification of para-anilines
28mg (0.1 mmol) of methyl 5- (4-bromophenyl) isoxazole-3-carboxylate is weighed out and dissolved in 10mL of methanol, 9.3mg of aniline (0.1 mmol) is weighed out and added into the prepared alcoholic solution, the mixture is fully dissolved and stands still, and after 5 minutes, the system is still a transparent solution.
Example 11 identification of ethylamine
14mg (0.05 mmol) of methyl 5- (4-bromophenyl) isoxazole-3-carboxylate are weighed out and dissolved in 5mL of methanol, 3.3mL of ethylamine are added to the prepared alcoholic solution, and after sufficient dissolution, the system is allowed to stand for 5 minutes, and then crystals are formed.
Example 12 identification of propylamines
14mg (0.05 mmol) of methyl 5- (4-bromophenyl) isoxazole-3-carboxylate was weighed out and dissolved in 5mL of methanol, 2.9mg of propylamine was added to the above alcohol solution which had been prepared, and after sufficient dissolution, the system was allowed to stand for 5 minutes, whereupon crystals formed.
Example 13 identification of 1-naphthylamine
14mg (0.05 mmol) of methyl 5- (4-bromophenyl) isoxazole-3-carboxylate is weighed out and dissolved in 5mL of methanol, 7.15mg of ethylamine is added to the prepared alcoholic solution, and after sufficient dissolution, the solution is kept stand for 5 minutes, and the system is still a transparent solution.
Example 14 identification of pyridin-2-Amines
14mg (0.05 mmol) of methyl 5- (4-bromophenyl) isoxazole-3-carboxylate is weighed out and dissolved in 5mL of methanol, 4.7mg of ethylamine is added to the prepared alcoholic solution, and after sufficient dissolution, the solution is kept stand for 5 minutes, and the system is still a transparent solution.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (2)
1. The application of the organic micromolecules in recognition of ammonia water, aliphatic amine and aromatic amine is characterized in that: the chemical name of the organic micromolecule is 5- (4-bromophenyl) isoxazole-3-carboxylic acid methyl ester, and the structural formula is as follows:
dissolving 0.01-0.1mmol of the methyl 5- (4-bromophenyl) isoxazole-3-carboxylate in 1-10 mL of alcohol to form an alcoholic solution of methyl 5- (4-bromophenyl) isoxazole-3-carboxylate;
adding ammonia water with equal molar quantity into 5- (4-bromophenyl) isoxazole-3-carboxylic acid methyl ester alcoholic solution, uniformly mixing, standing for 1-5 minutes at the temperature of 20-30 ℃, and forming a dense alcogel by a system;
adding equimolar amount of fatty amine into 5- (4-bromophenyl) isoxazole-3-carboxylic acid methyl ester alcoholic solution, mixing uniformly, and standing for 1-5 minutes at 20-30 ℃ to form crystals; the aliphatic amine is methylamine, ethylamine and propylamine;
adding aromatic amine with equal molar amount into 5- (4-bromophenyl) isoxazole-3-carboxylic acid methyl ester alcoholic solution, mixing uniformly, and standing for 1-5 minutes at 20-30 ℃ to form transparent solution; the aromatic amine is aniline.
2. The use of claim 1, wherein: the alcohol is methanol or ethanol.
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