CN111233725A - Methyl sulfur functionalized organic aromatic carboxylic acid ligand and preparation method and application thereof - Google Patents
Methyl sulfur functionalized organic aromatic carboxylic acid ligand and preparation method and application thereof Download PDFInfo
- Publication number
- CN111233725A CN111233725A CN202010080193.1A CN202010080193A CN111233725A CN 111233725 A CN111233725 A CN 111233725A CN 202010080193 A CN202010080193 A CN 202010080193A CN 111233725 A CN111233725 A CN 111233725A
- Authority
- CN
- China
- Prior art keywords
- carboxylic acid
- aromatic carboxylic
- acid ligand
- organic aromatic
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/62—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of organic synthesis, in particular to a methyl sulfide functionalized organic aromatic carboxylic acid ligand and a preparation method and application thereof. The invention discloses a methyl sulfide functionalized organic aromatic carboxylic acid ligand which has a structure shown in a formula (I), and is rich in methyl sulfide functionalized modification.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a methyl sulfide functionalized organic aromatic carboxylic acid ligand and a preparation method and application thereof.
Background
In recent 30 years, metal organic framework Materials (MOFs) have been rapidly developed, and 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 organic ligands containing elements or functional groups such as nitrogen, carboxylic acid, phosphoric acid and the like, among which organic aromatic carboxylic acid ligands have been most widely used. Since the sulfur element has abundant valence states, an organic aromatic carboxylic acid ligand which is partially functionalized by sulfide is synthesized (a compound with a structure shown in the specification, 4, 4' -dicarboxylic acid-tetrathiomethyl benzene) and is used for synthesizing a sulfide functionalized MOF material, so that the MOF material shows excellent performance.
The sulfur atoms of the existing thioether functionalized organic aromatic carboxylic acid ligand are not rich enough, and because only one aromatic ring is arranged between two carboxylic acids, the distance between the two carboxylic acids is short, the pore channel and the specific surface area of the synthesized MOF material are often small, and the application of the thioether functionalized MOF is limited to a great extent.
Disclosure of Invention
The invention provides a methyl sulfide functionalized organic aromatic carboxylic acid ligand, a preparation method and application thereof, and solves the problems of insufficient length and insufficient content of methyl sulfide functionalized modification in the conventional organic aromatic carboxylic acid ligand.
The specific technical scheme is as follows:
the invention provides a methyl sulfide functionalized organic aromatic carboxylic acid ligand which has a structure shown in a formula (I);
the invention also provides a preparation method of the methyl sulfide functionalized organic aromatic carboxylic acid ligand, which comprises the following steps:
step 1: carrying out nucleophilic substitution reaction on a compound with a structure shown in a formula (II) and thiolate to obtain a precursor;
step 2: hydrolyzing the precursor to obtain a methyl sulfide functionalized organic aromatic carboxylic acid ligand shown in a formula (I);
the structure of the precursor is shown as a formula (II);
wherein X is a halogen atom.
In the present invention, the compound having the structure represented by formula (II) and the thiolate are preferably introduced into a two-necked round-bottomed flask under an atmosphere of nitrogen or an inert gas, then the round-bottomed flask is preferably connected to a Schlenk line well known to those skilled in the art, and then a solvent is preferably added to the round-bottomed flask to perform a nucleophilic substitution reaction.
In the invention, the thiolate is NaSMe or KSMe. KSMe is relatively expensive and, in order to reduce the cost of preparing precursors of methyl sulfide functionalized organic aromatic carboxylic acid ligands, the mercaptide of the present invention is more preferably NaSMe.
The solvent preferably comprises one or more of water, methanol, tetrahydrofuran and N, N-dimethylformamide.
The mass-to-volume ratio of the compound of formula (II) to the solvent is (1.0g:5mL) - (1.0g:20 mL).
The molar ratio of the compound having the structure represented by the formula (II) to the thiolate is (1: 8) to (1: 24), and is preferably 24.1: 386.1 of the total weight of the steel; the time of the nucleophilic substitution reaction is 8-48 h, the temperature is 25-80 ℃, and the room temperature is more preferably 28 h.
In the present invention, after the nucleophilic substitution reaction is completed, the method further comprises: post-treatment; the post-treatment specifically 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 a crude precursor of the methyl sulfur functionalized organic aromatic carboxylic acid ligand.
Preferably, the extraction solvent is selected from ethyl acetate, dichloromethane or chloroform.
According to the invention, the crude product of the precursor of the methyl sulfur functionalized organic aromatic carboxylic acid ligand is preferably further purified by silica gel column chromatography to obtain a white solid product, namely the precursor of the methyl sulfur functionalized organic aromatic carboxylic acid ligand.
The compound of formula (I) provided by the invention contains abundant methyl sulfur, and can be used as a precursor of a methyl sulfur functionalized organic aromatic carboxylic acid ligand, and the thioether functionalized organic aromatic carboxylic acid ligand can be obtained by directly hydrolyzing the compound.
In step 2 of the present invention, the precursor is preferably hydrolyzed in an alcohol solvent under an alkaline condition in a nitrogen or inert gas atmosphere.
In the present invention, the alkaline agent providing the alkaline condition is preferably sodium hydroxide or potassium hydroxide; the alcohol solvent is preferably methanol.
The mass-to-volume ratio of the precursor to the alkaline reagent and the alcohol solvent is (1 g: 2.4 g: 18mL) - (1 g: 4.8 g: 18mL), preferably 1 g: 3.6 g: 18 mL.
The time of the reflux is preferably 12h to 36h, the temperature is preferably 90 ℃ to 110 ℃, more preferably 90 ℃ and 48 h.
In the present invention, before obtaining the methyl sulfide functionalized organic aromatic carboxylic acid ligand represented by formula (i) after the hydrolysis, the method further comprises: acidifying; the acidifying agent used for acidification is hydrochloric acid.
The acidifying agent used for acidification is hydrochloric acid with the mass fraction of 10-37%, and the preferred mass fraction is 10%; the acidification is specifically as follows: the acidifying agent is added slowly to the mixture with vigorous stirring until the pH is below 2.
Before the methyl sulfur functionalized organic aromatic carboxylic acid ligand is obtained, the method further comprises the following steps: and (4) carrying out suction filtration and washing on the acidified product to obtain a white solid, namely the ligand.
In the organic aromatic carboxylic acid ligand, the more the content of thioether functionalized modification is, the more excellent the performance of the synthesized MOF material is. Compared with the existing 4, 4' -dicarboxylic acid-tetrathiomethyl benzene, the ligand of the invention has higher sulfur content, and the rich thiomethyl ensures that the synthesized MOF material has better performance. The preparation method of the thioether functionalized modified organic aromatic carboxylic acid ligand is simple, few in preparation steps and easy to operate.
In the invention, the room temperature is 25 ℃ +/-5 ℃.
The invention also provides application of the methyl sulfide functionalized organic aromatic carboxylic acid ligand in a metal organic framework material. The metal organic framework material can be applied to heavy metal adsorption, heavy metal detection, catalysis and sensing.
According to the technical scheme, the invention has the following advantages:
the invention provides a methyl sulfide functionalized organic aromatic carboxylic acid ligand which has a structure shown in a formula (I). The organic aromatic carboxylic acid ligand is longer and contains more abundant methyl sulfur. The ligand is applied to the MOF material, so that the MOF material has more excellent 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 methyl sulfide functionalized organic aromatic carboxylic acid ligand prepared in example 1 of the present invention;
FIG. 2 is a nuclear magnetic carbon spectrum of a precursor of a methyl sulfide functionalized organic aromatic carboxylic acid ligand prepared in example 1 of the present invention;
FIG. 3 is a nuclear magnetic hydrogen spectrum of a methyl sulfide functionalized organic aromatic carboxylic acid ligand prepared in example 2 of the present invention;
FIG. 4 is a nuclear magnetic carbon spectrum of a methyl sulfide functionalized organic aromatic carboxylic acid ligand prepared in example 2 of the present invention.
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.
In the examples of the present invention, 4, 4' -methyl-octafluorobiphenyl dicarboxylate was prepared by the method of Tuning Lewis Acidity of Metal-Organic Frameworks of Perfluorine of BridgingLigands, Spectroscopic, Theoretical, and Catalytic students, published by Pengfei Ji et al.
The synthetic route of the embodiment of the invention is as follows:
example 1
This example is the preparation of 4, 4' -methyl diformate-octathiomethyl biphenyl as the precursor of methyl sulfide functionalized organic aromatic carboxylic acid ligand
1) In N2Under protection, the starting materials 4, 4' -dimethyldicarboxylate-octafluorobiphenyl (10.0g, 24.1mmol) and NaSMe (27.2g, 386.1mmol) were weighed into a 250mL two-necked round-bottomed flask, which was then connected to a Schlenk line, and 90mL of degassed tetrahydrofuran and N, N-dimethylformamide solution were transferred to the round-bottomed flask and the reaction was stirred at room temperature (25 ℃) for 28 h.
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 product was obtained as a pale yellow solid. The residue was further purified by column chromatography (silica gel using petroleum ether and ethyl acetate as eluent) to give the product as a white solid, i.e., 4' -dimethyldicarboxylate-octathiomethylbiphenyl, as M2(M2 yield 9.3g, 60% yield).
And performing nuclear magnetic resonance hydrogen spectrum and carbon spectrum tests on the white solid product.
The NMR result is shown in FIG. 1, and shows two single peaks at a chemical shift of 2.3-2.5ppm, with an integral ratio of 12:12, which correspond to two methylsulfurs in compound M2. At the same time, there is a single peak at a chemical shift of about 4.0ppm, with an integral ratio of 6, which corresponds to the two methyl esters in compound M2. 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 result of nuclear magnetic resonance carbon spectrum is shown in FIG. 2, and has two single peaks around the chemical shift of 20.7ppm, which is the peak of methyl carbon in two methyl sulfides of compound M2; there is a single peak at a chemical shift of about 52ppm, which is the peak for the methyl carbon in the methyl ester in compound M2; four single peaks exist between the chemical shifts 138-154ppm, and the group of peaks are peaks of four carbons of a benzene ring in M2; there is a single peak at a chemical shift of 167ppm, which is the peak for carbon radicals in compound M2.
From the analysis of the hydrogen spectrum of FIG. 1 and the carbon spectrum of FIG. 2, it can be confirmed that the synthesis of 4, 4' -methyl diformate-octathiomethyl biphenyl of the present example is successful.
Example 2
This example is the preparation of the methyl sulfide functionalized organic aromatic carboxylic acid ligand 4, 4' -dicarboxylic acid octathiomethyl biphenyl
1) In N2M2(1.0g,1.6mmol) prepared in example 1 was weighed into a 100mL two-necked round bottom flask with protection. The round bottom flask was connected to a gas line conduit which was then evacuated and filled with N2, repeated three times. NaOH (3.6g, 90.0mmol)) was dissolved in methanol (18mL) and then bubbled with N2And (4) degassing. The methanol solution was transferred to a round bottom flask for hydrolysis reaction in N2Refluxing at 90 deg.C for 48h under protection.
2) After cooling the mixture obtained from the hydrolysis reaction of step 1) to room temperature, the mixture was poured into water (150 mL). HCl of 10% by mass was slowly added with vigorous stirring until the pH was below 2 and a large amount of yellow solid precipitated. The yellow solid was collected by suction filtration and the residue was washed thoroughly with a large amount of deionized water and air dried to give a yellow solid product, 4' -dimethyldicarboxylate-octathiomethylbiphenyl, designated as M1(M1 yield: 0.88g, 92% yield).
And performing nuclear magnetic resonance hydrogen spectrum and carbon spectrum tests on the yellow solid product.
The results of NMR are shown in FIG. 3, and similar to the NMR spectrum of M2, two single peaks were observed at chemical shifts of 2.3 to 2.5ppm, and the integral ratio was 12:12, which is the peak of hydrogen in two methyl sulfides in compound M1. Meanwhile, compared with the compound M2, a single peak disappears at a chemical shift of 4.0ppm, which indicates that methyl ester is hydrolyzed to generate formic acid during the reaction. In the hydrogen spectrum, regardless of the peak position, the peak shape and the integral ratio, the characteristics of the product M1 were met.
The NMR result is shown in FIG. 4, and has two single peaks around the chemical shift of 20ppm, which is the peak of methyl carbon in two methyl sulfides in compound M1; meanwhile, compared with the compound M2, the compound has a disappearance of a single peak near a chemical shift of 52ppm, which corresponds to the disappearance of a single peak at a chemical shift of 4.0ppm in the figure IV, which shows that methyl ester is hydrolyzed to generate formic acid during the reaction; four single peaks exist between the chemical shifts 136-152ppm, and the group of peaks are peaks of four carbons of a benzene ring in M1; similarly, there is a single peak at a chemical shift of 167ppm, which is the peak for carbon radicals in compound M1.
The successful synthesis of compound M1 was demonstrated by analysis of the hydrogen spectrum of fig. 3 and the carbon spectrum of fig. 4.
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 methyl sulfur functionalized organic aromatic carboxylic acid ligand has a structure shown in a formula (I);
2. the preparation method of the methyl sulfide functionalized organic aromatic carboxylic acid ligand is characterized by comprising the following steps:
step 1: carrying out nucleophilic substitution reaction on a compound with a structure shown in a formula (II) and thiolate to obtain a precursor;
step 2: hydrolyzing the precursor to obtain a methyl sulfide functionalized organic aromatic carboxylic acid ligand with a structure shown in a formula (I);
the structure of the precursor is shown as a formula (III);
wherein X is a halogen atom.
3. The process according to claim 2, wherein the molar ratio of the compound having a structure represented by the formula (II) to the thiolate is (1: 8) to (1: 24).
4. The process according to claim 2, wherein the thiolate is NaSMe or KSMe.
5. The production method according to claim 2, characterized in that the nucleophilic substitution reaction is carried out under an atmosphere of nitrogen or an inert gas;
the time of the nucleophilic substitution reaction is 8-48 h, and the temperature is 25-80 ℃.
6. The method according to claim 2, wherein the solvent for the nucleophilic substitution reaction comprises one or more of water, methanol, tetrahydrofuran, and N, N-dimethylformamide;
the mass-to-volume ratio of the compound of formula (II) to the solvent is (1.0g:5mL) - (1.0g:20 mL).
7. The method of claim 2, wherein the hydrolysis is performed under alkaline conditions;
the alkaline reagent for providing the alkaline condition is potassium hydroxide or sodium hydroxide;
the hydrolysis time is 12-36 h, and the temperature is 90-110 ℃.
8. The production method according to claim 7, wherein the mass ratio of the precursor to the alkali agent in step 2 is (1: 2.4) to (1: 4.8).
9. The method of claim 2, wherein after the hydrolyzing, before obtaining the methyl sulfide functionalized organic aromatic carboxylic acid ligand represented by formula (I), further comprises: acidifying;
the acidifying agent used for acidification is hydrochloric acid.
10. Use of the methyl sulfide functionalized organic aromatic carboxylic acid ligand of claim 1 or the methyl sulfide functionalized organic aromatic carboxylic acid ligand prepared by the preparation method of any one of claims 2 to 9 in the preparation of metal organic framework materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010080193.1A CN111233725A (en) | 2020-01-22 | 2020-01-22 | Methyl sulfur functionalized organic aromatic carboxylic acid ligand and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010080193.1A CN111233725A (en) | 2020-01-22 | 2020-01-22 | Methyl sulfur functionalized organic aromatic carboxylic acid ligand and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111233725A true CN111233725A (en) | 2020-06-05 |
Family
ID=70866975
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010080193.1A Pending CN111233725A (en) | 2020-01-22 | 2020-01-22 | Methyl sulfur functionalized organic aromatic carboxylic acid ligand and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111233725A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102933591A (en) * | 2010-04-30 | 2013-02-13 | 联邦科学与工业研究组织 | Crystallisation facilitators for the synthesis of metal organic frameworks |
-
2020
- 2020-01-22 CN CN202010080193.1A patent/CN111233725A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102933591A (en) * | 2010-04-30 | 2013-02-13 | 联邦科学与工业研究组织 | Crystallisation facilitators for the synthesis of metal organic frameworks |
Non-Patent Citations (3)
| Title |
|---|
| YAN-LUNG WONG ET AL.: "A Thiol-Functionalized UiO-67-Type Porous Single Crystal: Filling in the Synthetic Gap", 《INORG. CHEM.》 * |
| 刘丽艳 等: "《医用化学》", 31 January 2018 * |
| 夏瑞庆 主编: "《学生辞海 职高 中专卷》", 30 September 1992 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110627841B (en) | Iron complex containing m-carborane triazole ligand and preparation and application thereof | |
| CN111233724A (en) | Sulfydryl functionalized organic aromatic carboxylic acid ligand and preparation method and application thereof | |
| CN111233725A (en) | Methyl sulfur functionalized organic aromatic carboxylic acid ligand and preparation method and application thereof | |
| CN111170912A (en) | Thioether functionalized organic aromatic carboxylic acid ligand and preparation method and application thereof | |
| CN110683926B (en) | Preparation method of carboxylic acid aryl ester compound | |
| CN101321721B (en) | Method for producing polymerizable hydroxydiamantyl ester compound | |
| CN110668983A (en) | Synthesis method of novel pentaerythritol tetra (3-mercaptopropionate) | |
| CN101029125A (en) | Production of polyester polyhydric alcohol | |
| CN113105301B (en) | Method for preparing conjugated diyne compound by using copper complex | |
| CN110734354B (en) | Method for preparing biaryl compound from alcohol compound | |
| CN110078922B (en) | Method for synthesizing polysulfone by using palladium-catalyzed homogeneous allyl substitution reaction | |
| CN110078921B (en) | Method for synthesizing polysulfone through palladium-catalyzed heterogeneous allyl polymerization reaction | |
| CN107827913B (en) | 1, 10-phenanthroline-containing N-heterocyclic carbene copper (I) complex and application thereof | |
| CN100526275C (en) | Synthetic method of 1-chlorine-3-methoxy propane | |
| JP4822410B2 (en) | Phosphine-encapsulated amphiphilic dendrimer, process for producing the same, phosphine ligand and palladium-containing complex catalyst having a coordination structure thereof | |
| CN111233825A (en) | Thiophene thiol functionalized organic aromatic carboxylic acid ligand and preparation method and application thereof | |
| CN112079801B (en) | Preparation method of 2,5-furandicarboxylic acid dimethyl ester | |
| KR101341888B1 (en) | A process to synthesize 11-aminoundecanoic acid or the ester derivative thereof | |
| CN115433149B (en) | Preparation method of 3,3', 4' -biphenyl tetracarboxylic dianhydride | |
| CN115448942B (en) | Method for synthesizing silanol by catalytic hydrosilane oxidation | |
| CN112625257B (en) | Preparation method of MOF-Cu and application of MOF-Cu in synthesis of diaryl sulfone compounds | |
| CN115304465B (en) | Green method for converting 1, 3-dithiane derivative into carbonyl compound | |
| CN113387890B (en) | Ionic liquid, polyionic liquid and preparation method and application thereof | |
| US20230348413A1 (en) | Method for preparing 2-iodoheterocyclic aryl ether at room temperature | |
| CN1067979C (en) | Method for producing dimethyl carbonate by direct synthesizing carbon dioxide and methanol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200605 |