CN111233825A - Thiophene thiol functionalized organic aromatic carboxylic acid ligand and preparation method and application thereof - Google Patents
Thiophene thiol functionalized organic aromatic carboxylic acid ligand and preparation method and application thereof Download PDFInfo
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- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
The invention relates to the technical field of organic synthesis, in particular to a thiophene thiol functionalized organic aromatic carboxylic acid ligand and a preparation method and application thereof. The invention discloses a precursor of thiophene thiol functionalized organic aromatic carboxylic acid ligand, which has a structure shown in formula (I). The precursor can be directly hydrolyzed to obtain the thiophene thiol functionalized organic aromatic carboxylic acid ligand, and the ligand contains rich thiophene thiol functional groups, so that the thiophene thiol functionalized organic aromatic carboxylic acid ligand can be applied to a metal organic framework material and can endow the metal organic framework material with new functions.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a thiophene thiol functionalized organic aromatic carboxylic acid ligand and a preparation method and application thereof.
Background
Metal organic framework Materials (MOFs) have evolved rapidly over the last 30 years. As a part of the most diverse and flexible metal organic framework materials, a large number of organic ligands have been synthesized by researchers, including nitrogen-containing, carboxylic acid and phosphoric acid, among which organic aromatic carboxylic acid ligands are most widely used. Due to the abundant valence of elemental sulfur, some of the sulfur-containing organic aromatic carboxylic acid ligands have been synthesized and used to prepare sulfur-functionalized MOF materials, which exhibit superior properties. Thiophene thiol, the most common sulfide, has excellent conductivity and is widely used. However, few thiophene thiol functionalized organic aromatic carboxylic acid ligands have been reported.
Disclosure of Invention
In view of the above, the invention provides a thiophene thiol functionalized organic aromatic carboxylic acid ligand, and a preparation method and an application thereof, and the ligand contains abundant thiophene thiol functional groups, and can endow a metal organic framework material with a new function when being applied to the metal organic framework material.
The specific technical scheme is as follows:
the invention provides a thiophene mercaptan functionalized organic aromatic carboxylic acid precursor which has a structure shown in a formula (I);
the compound of formula (I) provided by the invention contains abundant thiophene thiol functional groups and can be used as a precursor of thiophene thiol functionalized organic aromatic carboxylic acid ligands.
The invention provides a preparation method of thiophene thiol functionalized organic aromatic carboxylic acid precursor, which comprises the following steps:
carrying out nucleophilic substitution reaction on a compound shown in a formula (II) and thiophenethiol in an alkaline reagent to obtain a thiophenethiol functionalized organic aromatic carboxylic acid precursor shown in a formula (I);
wherein X is a halogen atom.
In the preparation method of the thiophene thiol functionalized organic aromatic carboxylic acid precursor, the preparation is preferably carried out under the protection of nitrogen or inert gas; the compound of formula (ii) and thiophenethiol are then preferably added to a reaction flask, the basic reagent is added to the reaction flask, the reaction flask is connected to a Schlenk line well known to those skilled in the art, and the degassed solvent is preferably transferred to the reaction flask for nucleophilic substitution.
The solvent is an amide solvent, preferably N, N-dimethylformamide.
The mass-to-volume ratio of the compound of formula (II) to the solvent is (1.0g:10mL) to (1.0g:40 mL).
The alkaline agent is preferably potassium carbonate, sodium hydroxide or potassium hydroxide.
The mass ratio of the compound of formula (II) to the thiophenethiol and the alkaline reagent is (1: 4: 4) - (1: 16: 10), and preferably 1: 8: 5.
the time of the nucleophilic substitution reaction is 48-72 h, the temperature is 25-80 ℃, and the preferred time is 48h at room temperature.
In the invention, the room temperature is 25 ℃ +/-5 ℃.
In the invention, after the nucleophilic substitution reaction is finished, post-treatment is carried out, and the post-treatment comprises the following steps: pouring the mixture obtained by nucleophilic substitution reaction into water, preferably adding extraction solvent to make extraction, then preferably washing the extracted extraction solvent with water, anhydrous MgSO4Drying the extraction solvent, and preferably removing the extraction solvent by using a rotary evaporator to obtain a light yellow solid, namely the crude precursor.
Preferably, the extraction solvent is selected from ethyl acetate, dichloromethane or chloroform.
Preferably, the number of extraction with the extraction solvent is 3, and the number of washing with water is 3.
Preferably, the crude product is further purified by silica gel column chromatography to obtain a white solid product, namely a precursor of the thiophene thiol functionalized organic aromatic carboxylic acid ligand; the eluent used for the column chromatography is preferably petroleum ether and ethyl acetate.
The invention also provides a thiophene thiol functionalized organic aromatic carboxylic acid ligand, which is prepared by the following method:
carrying out hydrolysis reaction on the precursor of the thiophene thiol functionalized organic aromatic carboxylic acid ligand or the precursor of the thiophene thiol functionalized organic aromatic carboxylic acid ligand prepared by the preparation method under alkaline conditions, and acidifying to obtain the precursor of the thiophene thiol functionalized organic aromatic carboxylic acid ligand;
the thiophene thiol functionalized organic aromatic carboxylic acid ligand has a structure shown in a formula (III);
the preparation method of the thiophene thiol functionalized organic aromatic carboxylic acid ligand provided by the invention specifically comprises the following steps: under alkaline condition, the precursor is added into a reaction eggplant bottle, then is preferably dissolved in alcohol solvent and water and then is added into the reaction eggplant bottle, and the hydrolysis reaction is carried out by oil bath reflux.
The hydrolysis reaction of the present invention is carried out under an atmosphere of nitrogen or an inert gas.
In the hydrolysis reaction, the alkali is preferably sodium hydroxide or potassium hydroxide; the alcohol solvent is preferably methanol; the mass volume ratio of the precursor to the alkaline reagent to the alcohol solvent is 1 g: (4-16) g: (2-8) mL, preferably 100g:800g:4 mL; the temperature of the hydrolysis reaction is 80-120 ℃, the time is 2-6 h, preferably 80 ℃, 2 h.
The acidifying agent used for the acidification is preferably hydrochloric acid; the mass concentration of the acidifying agent is 10-37%, and the acidifying agent is preferably 37%; the acidification is specifically as follows: the acidifying agent was slowly added to the reaction solution resulting from the oil bath reaction, with vigorous stirring, until the pH was below 2.
Before obtaining the ligand, the method further comprises the following steps: post-treatment; the post-treatment specifically comprises the following steps: and (3) carrying out suction filtration and washing on the acidified product to obtain a yellow solid, namely the thiophene thiol functionalized organic aromatic carboxylic acid ligand.
According to the technical scheme, the invention has the following advantages:
the invention provides a thiophene thiol functionalized organic aromatic carboxylic acid ligand precursor, which has a structure shown in a formula (I). The precursor can be directly subjected to ester hydrolysis to obtain the thiophene thiol functionalized organic aromatic carboxylic acid ligand, and the ligand contains rich thiophene thiol functional groups, so that the thiophene thiol functionalized organic aromatic carboxylic acid ligand can be applied to a metal organic framework material and can endow the metal organic framework material with new functions.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without inventive exercise.
FIG. 1 is a nuclear magnetic hydrogen spectrum of a precursor of a thiophene thiol functionalized organic aromatic carboxylic acid ligand prepared in example 1 of the present invention;
FIG. 2 is a nuclear magnetic fluorine spectrum of a precursor of thiophene thiol functionalized organic aromatic carboxylic acid ligand prepared in example 1 of the present invention;
FIG. 3 is a nuclear magnetic carbon spectrum of a precursor of thiophene thiol functionalized organic aromatic carboxylic acid ligand prepared in example 1 of the present invention;
FIG. 4 is a nuclear magnetic hydrogen spectrum of thiophene thiol functionalized organic aromatic carboxylic acid ligands prepared in example 2 of the present invention;
FIG. 5 is an infrared spectrum of a precursor of the thiophene thiol-functionalized organic aromatic carboxylic acid ligand prepared in example 1 and an infrared spectrum of the thiophene thiol-functionalized organic aromatic carboxylic acid ligand prepared in example 2.
Detailed Description
In order to make the objects, features and advantages of the present invention more obvious and understandable, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it should be apparent that the embodiments described below are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention discloses that the tetrafluoro-P-benzoic acid methyl ester is prepared by adopting a method in Trifluoro-3-hydroxy-1H-indole carboxylic Acids and Esters from Perfluorinated Benzenedicarboxylic Acids, which are published by Carlos Piez Medina and the like.
The synthetic route of the embodiment of the invention is as follows:
example 1
This example is the preparation of a precursor of a thiophenethiol functionalized organic aromatic carboxylic acid ligand
1) In N2Under protection, the raw materials of tetrafluoro-p-toluic acid methyl ester M1(1.0g) and thiophenethiol (8.0g) were weighed into a 25mL reaction flask, potassium carbonate (5g) was weighed into a 250mL reaction flask, the reaction flask was connected to a Schlenk line, 10mL of degassed DMF solution was transferred into the reaction flask, and the reaction was stirred at room temperature (25 ℃) for 72 hours.
2) Stirring was stopped and the reaction mixture was then poured into water (150mL), the aqueous solution was extracted with ethyl acetate (3X 80mL) and the ethyl acetate solutions were combined. The extracted ethyl acetate was washed with water (3X 100mL) and then with anhydrous MgSO4The ethyl acetate was dried. The ethyl acetate was removed on a rotary evaporator. The crude product was obtained as a pale yellow solid. The crude product was further purified by column chromatography (silica gel using PE (petroleum ether) and EA (ethyl acetate) as eluent) to give the product as a white solid, i.e., the thiotetra-thioethylene terephthalate, as M2 (11.2 g yield M2, 46% yield).
The white solid product M2 was subjected to NMR hydrogen, fluorine and carbon spectra.
The NMR result is shown in FIG. 1, which has a single peak at a chemical shift of 3.84ppm and an integrated area of 6, and the peak corresponds to the hydrogen of the methyl ester in the compound M4; meanwhile, three groups of multiple peaks exist at chemical shifts of 6.95, 7.27 and 7.35ppm, the ratio of integrated areas is 4:4:4, and the three groups of multiple peaks correspond to three kinds of hydrogen in the side chain thiophene thiol of the compound M4 one by one. In the hydrogen spectrum, regardless of the peak position, the peak shape and the integral ratio, the characteristics of the product M2 were met.
The NMR spectrum showed no F peak in FIG. 2, indicating that all 4F groups in the starting material reacted.
The NMR spectrum showed a single peak at 52.88ppm, which is the peak of methyl carbon in compound M4, as shown in FIG. 2; four single peaks at chemical shifts 134.87, 131.96, 130.44, and 127.40ppm, corresponding to the four carbons in the side chain thiophenethiol of compound M4; there are two single peaks at chemical shifts 147.45 and 139.84ppm, which correspond to the two carbons of the benzene ring of compound M4; there is a single peak at a chemical shift of 166.05ppm, which corresponds to the carbon of the carbonyl of compound M4.
From the analysis of the hydrogen spectrum of fig. 1, the fluorine spectrum of fig. 2 and the carbon spectrum of fig. 3, it can be confirmed that the present example successfully synthesizes the tetrathiophenylthio methyl terephthalate which is the precursor of the thiophenethiol functionalized organic aromatic carboxylic acid ligand.
Example 2
This example is the preparation of a thiophenethiol functionalized organic aromatic carboxylic acid ligand tetrathiophenylthioterephthalic acid
1) In N2M2(100mg) prepared in example 1 was weighed into a 50mL reaction flask under protection. Sodium hydroxide (800mg) is weighed in a small beaker, water and methanol are added into the small beaker for 4mL respectively, ultrasonic dissolution is carried out, then the solution in the small beaker is added into a reaction eggplant bottle, and reflux reaction is carried out for 2 hours in an oil bath at the temperature of 80 ℃, so as to obtain clear and transparent reaction liquid.
2) And cooling the reaction liquid, stopping the reaction, adding a large amount of water, adding concentrated hydrochloric acid (37 wt%) for acidification until the pH value of the solution is less than 2, separating out a large amount of solids, filtering under reduced pressure, washing the filter residue with a large amount of water, airing, and drying in vacuum to obtain a yellow solid, namely the tetrahydrothiophene sulfenyl terephthalic acid, wherein the mark is M3, and the yield of M3 is 58 mg.
The yellow solids M2 and M3 were tested by infrared spectroscopy and M3 by hydrogen nuclear magnetic resonance spectroscopy.
The results of the infrared spectroscopy are shown in FIG. 5, where the single peak at chemical shift 3.84ppm disappeared compared to compound M2, indicating that the methyl ester in M2 was hydrolyzed; meanwhile, three groups of multiple peaks exist at chemical shifts of 6.92, 7.22 and 7.43ppm, the ratio of integrated areas is 4:4:4, and the three groups of multiple peaks correspond to three kinds of hydrogen in the side chain thiophene thiol of the compound M3 one by one. In the hydrogen spectrum, regardless of the peak position, the peak shape and the integral ratio, the characteristics of the product M3 were met.
The NMR spectrum is shown in FIG. 4, and the IR spectrum of M3 is significantly changed from that of M2. In M2, the vibration absorption peak of carbonyl group in methyl ester appeared at 1738cm-1The vibration absorption peak of carbonyl group in M3 appeared at 1711cm-1The methyl ester in M2 is reacted to generate formic acid; in the spectrum of M3, it is evident that at 2616 and 2540cm-1The broad absorption vibration peak is the characteristic absorption peak of carboxylic acid, and the methyl ester in M2 is shown to react to generate formic acid.
The analysis of the infrared spectrum of fig. 5 and the hydrogen spectrum of fig. 4 proves that the thiophene thiol functionalized organic aromatic carboxylic acid ligand tetrathiophene thio terephthalic acid M3 is successfully synthesized in the embodiment.
The above-mentioned embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A precursor of thiophene thiol functionalized organic aromatic carboxylic acid ligand has a structure shown in formula (I):
2. a preparation method of a precursor of thiophene thiol functionalized organic aromatic carboxylic acid ligand is characterized by comprising the following steps:
carrying out nucleophilic substitution reaction on a compound shown as a formula (II) and thiophenethiol in the presence of an alkaline reagent to obtain a precursor of the thiophenethiol functionalized organic aromatic carboxylic acid ligand shown as a formula (I);
wherein X is a halogen atom.
3. The process according to claim 2, wherein the mass ratio of the compound represented by the formula (II) to the thiophenethiol and the basic agent is (1: 4: 4) to (1: 16: 10).
4. The method according to claim 2, wherein the alkaline agent is sodium bicarbonate, sodium hydroxide, or potassium hydroxide.
5. The preparation method according to claim 2, wherein the nucleophilic substitution reaction is carried out for 48 to 72 hours at a temperature of 25 to 80 ℃.
6. A thiophene thiol functionalized organic aromatic carboxylic acid ligand, which is prepared by the following method:
hydrolyzing the precursor of claim 1 or the precursor prepared by any one of the preparation methods of claims 2 to 4 under alkaline conditions, and then acidifying to obtain a thiophene thiol functionalized organic aromatic carboxylic acid ligand shown as a formula (III);
7. the thiophenethiol functionalized organic aromatic carboxylic acid ligand of claim 6, wherein said basic condition is sodium hydroxide or potassium hydroxide.
8. The thiophene thiol functionalized organic aromatic carboxylic acid ligand according to claim 6, wherein the hydrolysis reaction is carried out at a temperature of 80-120 ℃ for 2-6 h.
9. The thiophenethiol functionalized organic aromatic carboxylic acid ligand of claim 6, wherein the acidifying agent used for the acidification is hydrochloric acid;
the mass concentration of the acidifier is 10-37%.
10. Use of the thiophenethiol functionalized organic aromatic carboxylic acid ligand of any one of claims 6 to 9 in a metal organic framework material.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104311583A (en) * | 2014-11-22 | 2015-01-28 | 刘国政 | Zinc compound based on flexible double ligands containing nitrogen and carboxylic acid and preparation method thereof |
| CN104945422A (en) * | 2015-06-16 | 2015-09-30 | 广东工业大学 | Thioether-functionalized metal carboxylate molecular cage and synthetic method thereof |
| CN105175295A (en) * | 2015-09-24 | 2015-12-23 | 南昌航空大学 | Preparation for thiol-functionalization MOFs material and application thereof in adsorption and removal of heavy metal ions in water |
| CN107337626A (en) * | 2017-08-04 | 2017-11-10 | 广东工业大学 | A kind of alkyl hydrosulfide functionalization aromatic carboxylic acids and preparation method thereof |
-
2020
- 2020-01-22 CN CN202010075137.9A patent/CN111233825A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104311583A (en) * | 2014-11-22 | 2015-01-28 | 刘国政 | Zinc compound based on flexible double ligands containing nitrogen and carboxylic acid and preparation method thereof |
| CN104945422A (en) * | 2015-06-16 | 2015-09-30 | 广东工业大学 | Thioether-functionalized metal carboxylate molecular cage and synthetic method thereof |
| CN105175295A (en) * | 2015-09-24 | 2015-12-23 | 南昌航空大学 | Preparation for thiol-functionalization MOFs material and application thereof in adsorption and removal of heavy metal ions in water |
| CN107337626A (en) * | 2017-08-04 | 2017-11-10 | 广东工业大学 | A kind of alkyl hydrosulfide functionalization aromatic carboxylic acids and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| CARLOS PÉREZ MEDINA等: "Trifluoro-3-hydroxy-1H-indazolecarboxylic Acids and Esters from Perfluorinated Benzenedicarboxylic Acids", 《EUR. J. ORG. CHEM.》 * |
| STEPHEN D. PASTOR等: "SUBSTITUTION OF ARYL HALIDES BY THIOLATE ANIONS", 《PHOSPHORUS AND SULFUR》 * |
| XIAO-PING ZHOU等: "Coordination Networks from a Bifunctional Molecule Containing Carboxyl and Thioether Groups", 《INORG. CHEM.》 * |
| XIAO-PING ZHOU等: "Reversible uptake of HgCl2 in a porous coordination polymer based on the dual functions of carboxylate and thioether", 《CHEM. COMMUN.》 * |
| 黄一涛: "含硫金属-有机框架的设计合成与光电性能研究", 《万方学位论文数据库》 * |
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