CN107337626A - A kind of alkyl hydrosulfide functionalization aromatic carboxylic acids and preparation method thereof - Google Patents
A kind of alkyl hydrosulfide functionalization aromatic carboxylic acids and preparation method thereof Download PDFInfo
- Publication number
- CN107337626A CN107337626A CN201710660250.1A CN201710660250A CN107337626A CN 107337626 A CN107337626 A CN 107337626A CN 201710660250 A CN201710660250 A CN 201710660250A CN 107337626 A CN107337626 A CN 107337626A
- Authority
- CN
- China
- Prior art keywords
- tpa
- preparation
- terephthalic acid
- carboxylic acids
- methyl esters
- 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.)
- Granted
Links
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
- C07C323/51—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 atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/56—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 atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton containing six-membered aromatic rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
- C07C319/12—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by reactions not involving the formation of mercapto groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/307—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a kind of alkyl hydrosulfide functionalization aromatic carboxylic acids, its preparation method and its application, the compound has structure shown in formula I.There is sulfydryl in the compound of structure shown in formula I to be separated with phenyl ring with methylene for this, and solution releases sulfydryl so that sulfydryl can preferably play the effect of its functionalization, make it easier to modify, reactivity is higher；Heavy metal ion can be adsorbed；The flexibility of side chain benzyl mercaptan can be increased.Test result indicates that：The compound can adsorb Hg2+。
Description
Technical field
The present invention relates to compound synthesis technical field, more particularly to a kind of alkyl hydrosulfide functionalization aromatic carboxylic acids
And preparation method thereof.
Background technology
Metal-organic framework materials (Metal-Organic framework, MOF) obtain as emerging stephanoporate framework material
Fast development is arrived, the polyporous materials can be by the design to functional ligand, and then orients self assembly and go out to have default knot
The metal-organic framework material of structure and function.MOF has certain exploration in terms of pharmaceutical carrier, in MOF uio-66 series by
Proof has extraordinary biocompatibility and biological degradability, suitable for making pharmaceutical carrier.Research discovery based on early stage, mercapto
Base aromatic carboxylic acids have annexed soft or hard atom and have been integrated (hsab theory), and the O wherein on carboxyl is as hard base, sulfydryl
On S as soft base, make the advantage of this kind of compound very notable.When selection hard acid metalloid ion is as coordination center, in
Heart ion can select to form metal organic frame with carboxyl, and sulfydryl is not involved in being coordinated, free and modify framework material sulfydryl work(
Aryl carboxylic acid compound can be changed.Sulfydryl is incorporated into metal-organic framework materials, and its advantage major embodiment is as follows：
(1) mercapto functional group is advantageous to synthetic modification after MOF materials are carried out in the activity of organic aspect；
(2) can degrade functional group containing sulfydryl in organism.
At present, the research chemist such as Laurent Vial (J.Am.Chem.Soc.2006,128,10253~10257)
The compound of the structure as shown in formula II is synthesized：
But the compound is difficult to modify, its extensive use is limited.
The content of the invention
In view of this, it is an object of the invention to provide a kind of alkyl hydrosulfide functionalization aromatic carboxylic acids and its preparation
Method, the compound are easy to modify, and reactivity is higher.
The invention provides a kind of alkyl hydrosulfide functionalization aromatic carboxylic acids, have structure shown in formula I：
The invention provides a kind of preparation side of alkyl hydrosulfide functionalization aromatic carboxylic acids described in above-mentioned technical proposal
Method, comprise the following steps：
2- methylterephthalic acids methyl esters, N-bromosuccinimide and benzoyl peroxide are mixed, in nitrogen and
CCl4In the presence of back flow reaction, separate reaction product, obtain 2- bromomethyl terephthalic acid (TPA) methyl esters；
By 2- bromomethyls terephthalic acid (TPA) methyl esters, NaHS and the absolute methanol hybrid reaction, acidifying, alkyl is obtained
Thiol functionalised aromatic carboxylic acids.
Preferably, the 2- bromomethyls terephthalic acid (TPA) methyl esters, N-bromosuccinimide and benzoyl peroxide reaction
Temperature be 60~80 DEG C；Time is 2.5~3.5h.
Preferably, the temperature of the 2- bromomethyls terephthalic acid (TPA) methyl esters, NaHS and absolute methanol reaction for 75~
85℃；Time is 22~26h.
Preferably, the acidifying specifically includes：
The product and water that 2- bromomethyls terephthalic acid (TPA) methyl esters, NaHS and the absolute methanol hybrid reaction are obtained
Mixing, add the hydrochloric acid that mass fraction is 10% and be acidified.
The invention provides alkyl hydrosulfide functionalization aromatic carboxylic acids described in a kind of above-mentioned technical proposal or above-mentioned skill
Alkyl hydrosulfide functionalization aromatic carboxylic acids prepared by preparation method described in art scheme answering in heavy metal absorbent preparation
With.
The invention provides a kind of alkyl hydrosulfide functionalization aromatic carboxylic acids, have structure shown in formula I.There should be the knot of formula I
Sulfydryl is separated with phenyl ring with methylene in the compound of structure, and solution releases sulfydryl so that sulfydryl can preferably play its function and be turned into
With making it easier to modify, reactivity is higher；Heavy metal ion can be adsorbed；The flexibility of side chain benzyl mercaptan can be increased.It is real
Result is tested to show：The compound can adsorb Hg2+。
Brief description of the drawings
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of 2- bromomethyl terephthalic acid (TPA) methyl esters in the embodiment of the present invention 1；
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of 2- sulfydryl methylene terephthalic acid (TPA)s in the embodiment of the present invention 1；
Fig. 3 is the nuclear-magnetism carbon spectrogram of 2- sulfydryl methylene terephthalic acid (TPA)s in the embodiment of the present invention 1；
Fig. 4 is the ion mass spectrum figure of 2- sulfydryl methylene terephthalic acid (TPA)s in the embodiment of the present invention 1；
Fig. 5 is 2- sulfydryl methylene terephthalic acid (TPA) heavy metal IONS OF Hs g in the embodiment of the present invention 12+Fluorescence after absorption
Spectrogram.
Embodiment
The invention provides a kind of alkyl hydrosulfide functionalization aromatic carboxylic acids, have structure shown in formula I：
There is sulfydryl in the compound of structure shown in formula I to be separated with phenyl ring with methylene for this, and solution releases sulfydryl so that sulfydryl can be more
The effect of its functionalization is played well, makes it easier to modify, reactivity is higher；Heavy metal ion can be adsorbed.In addition, this method
Products collection efficiency is higher.Test result indicates that：The compound can adsorb Hg2+；The yield of compound with structure shown in formula I reaches
88%, high purity 97%.
The invention provides a kind of preparation side of alkyl hydrosulfide functionalization aromatic carboxylic acids described in above-mentioned technical proposal
Method, comprise the following steps：
2- methylterephthalic acids methyl esters, N-bromosuccinimide and benzoyl peroxide are mixed, in nitrogen and
CCl4In the presence of back flow reaction, separate reaction product, obtain 2- bromomethyl terephthalic acid (TPA) methyl esters；
By 2- bromomethyls terephthalic acid (TPA) methyl esters, NaHS and the absolute methanol hybrid reaction, acidifying, alkyl is obtained
Thiol functionalised aromatic carboxylic acids.
The synthetic route of above-mentioned preparation method is shown in reaction scheme 1：
Reaction scheme 1；
The present invention is by 2- methylterephthalic acids methyl esters, N-bromosuccinimide (NBS) and benzoyl peroxide (BPO)
Mixing, in nitrogen and CCl4In the presence of back flow reaction, separate reaction product, obtain 2- bromomethyl terephthalic acid (TPA) methyl esters, i.e.,
Compound 2 in reaction scheme 1.
In the present invention, the 2- methylterephthalic acids methyl esters is preferably made in accordance with the following methods：
2- methylterephthalic acids, methanol are mixed with the concentrated sulfuric acid, reacts, obtains 2- methylterephthalic acid's methyl esters.
In the present invention, the temperature of the 2- methylterephthalic acids, methanol and strong sulfuric acid response is preferably 50 DEG C~100
DEG C, the time of the 2- methylterephthalic acids, methanol and strong sulfuric acid response are preferably 24~28h.Preferred pair reaction of the present invention
Product is cooled to after 10~35 DEG C to be mixed with water again, there is white solid precipitation, and decompression filters, and obtains white plates crystal product,
Compound 1 in as 2- methylterephthalic acids methyl esters, i.e. reaction scheme.
The present invention is preferably by 2- methylterephthalic acids methyl esters, N-bromosuccinimide and benzoyl peroxide in ability
Mixed in eggplant type bottle known to field technique personnel, add magnetic stick, vacuum nitrogen gas repeats repeatedly.The present invention will be anti-
Answer solvent C Cl4Middle bulging nitrogen, then be transferred in eggplant type bottle and reacted with vacuum tube.In the present invention, the 2- methyl is to benzene
The temperature of dicarboxylic acid methyl ester, N-bromosuccinimide and benzoyl peroxide reaction is preferably 60~80 DEG C；Time is preferably
2.5~3.5h.
The present invention is preferably by the reaction of 2- methylterephthalic acids methyl esters, N-bromosuccinimide and benzoyl peroxide
Product at reduced pressure filters, and the material obtained after suction filtration obtains 2- bromomethyls to benzene two by the method separating-purifying of silica gel column chromatography
Methyl formate.
It is of the invention by the 2- bromomethyls terephthalic acid (TPA) methyl esters, sulphur hydrogen after obtaining 2- bromomethyl terephthalic acid (TPA) methyl esters
Change sodium and absolute methanol hybrid reaction, acidifying, obtain 2- sulfydryl methylene terephthalic acid (TPA)s.
The present invention carries out 2- bromomethyls pair preferably in the reactor well known to those skilled in the art with reflux condenser
The hybrid reaction of phthalic acid methyl ester, NaHS and absolute methanol.The 2- bromomethyls terephthalic acid (TPA) methyl esters, NaHS
Temperature with absolute methanol reaction is preferably 75~85 DEG C；Time is preferably 22~26h, more preferably 24h.
In the present invention, the acidifying preferably specifically includes：
The product and water that 2- bromomethyls terephthalic acid (TPA) methyl esters, NaHS and the absolute methanol hybrid reaction are obtained
Mixing, add the hydrochloric acid that mass fraction is 10% and be acidified.
Present invention preferably employs the hydrochloric acid that mass fraction is 10% to be acidified to precipitation solid, and decompression filters, and natural air drying obtains
To 2- sulfydryl methylene terephthalic acid (TPA)s, i.e. L compounds in reaction scheme 1.
The invention provides alkyl hydrosulfide functionalization aromatic carboxylic acids described in a kind of above-mentioned technical proposal or above-mentioned skill
Alkyl hydrosulfide functionalization aromatic carboxylic acids prepared by preparation method described in art scheme answering in heavy metal absorbent preparation
With.
The alkyl hydrosulfide functionalization aromatic carboxylic acids methylene separates phenyl ring and sulfydryl, liberates sulfydryl,
So that sulfydryl plays optimum response performance, and easily modification, beneficial to the application in being prepared in pharmaceutical carrier or heavy metal absorbent.
The invention provides a kind of alkyl hydrosulfide functionalization aromatic carboxylic acids, have structure shown in formula I.There should be the knot of formula I
Sulfydryl is separated with phenyl ring with methylene in the compound of structure, and solution releases sulfydryl so that sulfydryl can preferably play its function and be turned into
With making it easier to modify, reactivity is higher；Heavy metal ion can be adsorbed；The flexibility of side chain benzyl mercaptan can be increased.It is real
Result is tested to show：The compound can adsorb Hg2+。
In order to further illustrate the present invention, with reference to embodiment to a kind of alkyl hydrosulfide functionalization virtue provided by the invention
Fragrant carboxylic acid compound and preparation method thereof is described in detail, but they can not be interpreted as to the limit to the scope of the present invention
It is fixed.
Embodiment 1
First, the synthesis step of 2- methylterephthalic acids methyl esters (intermediate 1)：
(1) raw material 2- methylterephthalic acids (1801.6mg, 10mmol) are weighed and add the single neck round bottom burning that 100mL is dried
In bottle and add magnetic stick；
(2) absolute methanol 20mL is measured with graduated cylinder to be added in single necked round bottom flask；
(3) stir at room temperature and the concentrated sulfuric acid (0.5mL) is slowly added dropwise, be subsequently placed in oil bath the 48h that flows back.Question response is complete
Afterwards, room temperature is cooled to, substantial amounts of distilled water is added into mixture, there are a large amount of solids to separate out, decompression filters, and obtains white solid
Product (i.e. intermediate 1) 1873mg, yield 90%, purity 99%.
2nd, the synthesis step of 2- bromomethyls terephthalic acid (TPA) methyl esters (intermediate 2)：
(1) weighing the 1st intermediate (1666mg, 8mmol) obtained above, N-bromosuccinimide (1780mg,
10mmol), benzoyl peroxide (194mg, 0.8mmol) is added in the reaction eggplant bottle of 25mL dryings, is opened stirring, is vacuumized
Inflated with nitrogen repeats repeatedly.
(2) carbon tetrachloride 20ml is measured with graduated cylinder, under a nitrogen bubbling 10min；
(3) carbon tetrachloride solvent is transferred in 50ml reaction eggplant bottles with vacuum tube, reaction eggplant bottle is placed in 70 DEG C of oil baths
Middle backflow 5h；
(4) after reaction terminates, product is filtered to obtain organic phase, the purification of by silica gel chromatography post separation, obtains white solid production
Thing (i.e. the 2nd intermediate) 1633mg, yield 71%, purity 98%.
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of 2- bromomethyl terephthalic acid (TPA) methyl esters in the embodiment of the present invention 1；As shown in Figure 1：
Chemical shift is that 2.51 peak represents the peak of deuterated dimethyl sulfoxide, and chemical shift is that the peak at 3.32 is represented in deuterated dimethyl sulfoxide
Water peak, chemical shift is that the peak at 3.91 represents the peaks of 6 hydrogen atoms of methyl in two ester groups, and chemical shift is 5.08
Peak represents the peak of 2 hydrogen atoms of methylene, and the peak at chemical shift 8.00,8.01,8.18 represents 3 hydrogen originals on phenyl ring respectively
The peak of son.
3rd, the synthesis step of 2- sulfydryls methylene terephthalic acid (TPA)：
The 2nd intermediate (1580mg, 5.5mmol) is added in the methanol solution of 25mL NaHSs, is placed in 85 DEG C of oil
Flow back 48h in bath.Reaction is finished, and is cooled to room temperature, and substantial amounts of distilled water is added into mixed solution and adds excessive dense salt
Acid, it is in highly acid to make solution.There are a large amount of faint yellow solids to separate out, decompression filters, and obtains pale yellow powder product 1025mg, yield
88%, purity 97%.
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of 2- sulfydryl methylene terephthalic acid (TPA)s in the embodiment of the present invention 1；As shown in Figure 2：
The peak that chemical shift is 2.50 represents the peak of deuterated dimethyl sulfoxide, and chemical shift is that the peak at 2.87 represents in part hydrogen in sulfydryl
The peak of atom, chemical shift are that the peak at 3.32 represents water peak in deuterated dimethyl sulfoxide, and chemical shift is the peak generation at 4.09
The peak of hydrogen atom on table methylene, the peak at chemical shift 7.87,7.90,8.01 represent on phenyl ring 3 hydrogen atoms respectively
Peak, last chemical shift are that the peak at 13.32 represents the peak of hydrogen atom on carboxyl.
Fig. 3 is the nuclear-magnetism carbon spectrogram of 2- sulfydryl methylene terephthalic acid (TPA)s in the embodiment of the present invention 1；As shown in Figure 3：Carbon is former
The number of son is consistent with the product synthesized.
Fig. 4 is the ion mass spectrum figure of 2- sulfydryl methylene terephthalic acid (TPA)s in the embodiment of the present invention 1.As shown in Figure 4：Survey
Test result is consistent with the molecular weight of 2- sulfydryl methylene terephthalic acid (TPA)s.
Fig. 1~Fig. 4 proves that the present embodiment successfully synthesizes 2- sulfydryl methylene terephthalic acid (TPA)s.Sulfydryl in the compound
Being separated with phenyl ring with methylene, solution releases sulfydryl so that sulfydryl can preferably play the effect of its functionalization, make it easier to modify,
Reactivity is higher, can adsorb heavy metal ion；The flexibility of side chain benzyl mercaptan can be increased.
The present invention tests the absorption property of 2- sulfydryl methylene terephthalic acid (TPA) heavy metal mercury ions using following methods：
1. test ligand L (2- sulfydryl methylene terephthalic acid (TPA)) solid fluorescence；
2. prepare the HgCl of mass fraction 0.3%2Solution；
Weigh 9mg HgCl2In 2991 μ L water, stir and ultrasound makes it fully dissolve；
3. the L (0.024mmol) for weighing 5mg is soaked in above-mentioned HgCl2In solution, 8h is soaked；
4. being centrifuged off supernatant, after repeatedly being washed with deionized water, ligand L is collected, vacuum drying, carries out solid again
The test of fluorescence.
Absorption test result is shown in that Fig. 5, Fig. 5 are 2- sulfydryl methylene terephthalic acid (TPA) heavy metals in the embodiment of the present invention 1
IONS OF H g2+Fluorescence spectra after absorption；Curve A is the solid state fluorescence curve of 2- sulfydryl methylene terephthalic acid (TPA)s in Fig. 5, bent
Line B is 2- sulfydryl methylene terephthalic acid (TPA) absorption heavy metal Hg2+Fluorescence curve afterwards.As seen from Figure 5：2- sulfydryl methylenes
Base terephthalic acid (TPA) has adsorbed Hg2+Afterwards, its nattier blue fluorescence disappears substantially.
Embodiment 2
First, the synthesis of 2- methylterephthalic acids methyl esters
1g 2- methylterephthalic acids are weighed, add 9mL methanol, the 40 dense H of drop are added dropwise2SO4(2mol/L) makees catalyst, in
60~75 DEG C of oil baths backflow 24h.Increasing amount deionized water separates out white solid, and the white solid filtered is dissolved in into acetic acid second
Ester, add anhydrous MgSO4Water removal, filters to obtain liquid, ethyl acetate is removed in vacuum and obtains white solid 2- methylterephthalic acid's first
Ester.
2nd, the synthesis of 2- bromomethyls terephthalic acid (TPA) methyl esters
300mg 2- methylterephthalic acids methyl esters (1.46mmol) is weighed, anhydrous and oxygen-free operation adds 277.5mg
The NBS, the BPO of 0.09~0.11 times of mole, 8mLCCl of (1.533mmol, 1.05~1.2 times of moles)4Solvent, 75~85
6~8h of oil bath backflow at DEG C.Insoluble solids are washed with ether, filter vacuum is removed into solvent, obtain white solid 2- bromomethyls pair
Phthalic acid methyl ester.
3rd, the synthesis of 2- sulfydryls methylene terephthalic acid (TPA)
202mg (0.704mmol) 2- bromomethyl dimethyl terephthalate (DMT)s are weighed, 41.4mg is added under the conditions of anhydrous and oxygen-free
NaSH (0.739mmol, 1.05~1.2 times of moles), add solvent absolute ethyl alcohol (or anhydrous propanone) 6mL, 75~85 DEG C of oil
Bath backflow 6h.Solvent is removed in vacuum, dries faint yellow solid.
84.48mg NaOH (2.112mmol, more than 2.5 times moles) are dissolved in 6mL deionized waters, will be above-mentioned yellowish
Color solid is added in NaOH solution, 100~110 DEG C of oil baths backflow 4h.After solution cooling, dense HCl is added dropwise under condition of ice bath extremely
PH value=2, obtain a large amount of white solids.Solvent is removed, vacuum drying white solid obtains product 2- sulfydryls methylene to benzene two
Formic acid.
Sulfydryl is separated with phenyl ring with methylene in the compound that embodiment 2 is prepared, and solution releases sulfydryl so that sulfydryl energy
The effect of its functionalization is preferably played, makes it easier to modify, reactivity is higher, can adsorb heavy metal ion；It can increase
The flexibility of side chain benzyl mercaptan.
The 2- sulfydryl methylene terephthalic acid (TPA) heavy metal IONS OF Hs g that the present embodiment 2 provides2+Adsorption effect and implementation
Example 1 is similar.
As seen from the above embodiment, the invention provides a kind of alkyl hydrosulfide functionalization aromatic carboxylic acids, there is formula I
Structure.There is sulfydryl in the compound of structure shown in formula I to be separated with phenyl ring with methylene for this, and solution releases sulfydryl so that sulfydryl can be more preferable
Ground plays the effect of its functionalization, makes it easier to modify, reactivity is higher；Heavy metal ion can be adsorbed；Side chain can be increased
The flexibility of benzyl mercaptan.Test result indicates that：The compound can adsorb Hg2+。
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (6)
1. a kind of alkyl hydrosulfide functionalization aromatic carboxylic acids, there is structure shown in formula I：
2. the preparation method of alkyl hydrosulfide functionalization aromatic carboxylic acids, comprises the following steps described in a kind of claim 1：
2- methylterephthalic acids methyl esters, N-bromosuccinimide and benzoyl peroxide are mixed, in nitrogen and CCl4Deposit
In lower back flow reaction, reaction product is separated, obtains 2- bromomethyl terephthalic acid (TPA) methyl esters；
By 2- bromomethyls terephthalic acid (TPA) methyl esters, NaHS and the absolute methanol hybrid reaction, acidifying, alkyl hydrosulfide is obtained
Functionalization aromatic carboxylic acids.
3. preparation method according to claim 2, it is characterised in that the 2- bromomethyls terephthalic acid (TPA) methyl esters, N- bromines
The temperature reacted for succinimide and benzoyl peroxide is 60~80 DEG C；Time is 2.5~3.5h.
4. preparation method according to claim 2, it is characterised in that the 2- bromomethyls terephthalic acid (TPA) methyl esters, sulphur hydrogen
The temperature for changing sodium and absolute methanol reaction is 75~85 DEG C；Time is 22~26h.
5. preparation method according to claim 2, it is characterised in that the acidifying specifically includes：
The product and water that 2- bromomethyls terephthalic acid (TPA) methyl esters, NaHS and the absolute methanol hybrid reaction are obtained mix
Close, add the hydrochloric acid that mass fraction is 10% and be acidified.
6. described in alkyl hydrosulfide functionalization aromatic carboxylic acids described in a kind of claim 1 or claim 2~5 any one
The application of alkyl hydrosulfide functionalization aromatic carboxylic acids prepared by preparation method in heavy metal absorbent preparation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710660250.1A CN107337626B (en) | 2017-08-04 | 2017-08-04 | A kind of alkyl hydrosulfide functionalization aromatic carboxylic acids and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710660250.1A CN107337626B (en) | 2017-08-04 | 2017-08-04 | A kind of alkyl hydrosulfide functionalization aromatic carboxylic acids and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107337626A true CN107337626A (en) | 2017-11-10 |
| CN107337626B CN107337626B (en) | 2019-04-12 |
Family
ID=60217648
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710660250.1A Active CN107337626B (en) | 2017-08-04 | 2017-08-04 | A kind of alkyl hydrosulfide functionalization aromatic carboxylic acids and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107337626B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110845470A (en) * | 2019-11-29 | 2020-02-28 | 广东工业大学 | Thiophene thiol functionalized organic carboxylic acid precursor, thiophene thiol functionalized organic carboxylic acid ligand, preparation method of thiophene thiol functionalized organic carboxylic acid precursor and ligand, and preparation method of metal organic framework material |
| CN111233825A (en) * | 2020-01-22 | 2020-06-05 | 广东工业大学 | Thiophene thiol functionalized organic aromatic carboxylic acid ligand and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999038924A1 (en) * | 1998-01-29 | 1999-08-05 | Sola International Holdings Ltd. | Coating composition |
| JP2005037439A (en) * | 2003-07-15 | 2005-02-10 | Konica Minolta Medical & Graphic Inc | Silver salt photothermographic dry imaging material and image forming method |
| CN101801922A (en) * | 2007-09-20 | 2010-08-11 | 昭和电工株式会社 | Method of producing beta-mercaptocarboxylic acids |
| CN104447452A (en) * | 2014-11-06 | 2015-03-25 | 广东工业大学 | Synthetic method of mercapto functionalized polyaryl carboxylic acid compound |
-
2017
- 2017-08-04 CN CN201710660250.1A patent/CN107337626B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999038924A1 (en) * | 1998-01-29 | 1999-08-05 | Sola International Holdings Ltd. | Coating composition |
| JP2005037439A (en) * | 2003-07-15 | 2005-02-10 | Konica Minolta Medical & Graphic Inc | Silver salt photothermographic dry imaging material and image forming method |
| CN101801922A (en) * | 2007-09-20 | 2010-08-11 | 昭和电工株式会社 | Method of producing beta-mercaptocarboxylic acids |
| CN104447452A (en) * | 2014-11-06 | 2015-03-25 | 广东工业大学 | Synthetic method of mercapto functionalized polyaryl carboxylic acid compound |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110845470A (en) * | 2019-11-29 | 2020-02-28 | 广东工业大学 | Thiophene thiol functionalized organic carboxylic acid precursor, thiophene thiol functionalized organic carboxylic acid ligand, preparation method of thiophene thiol functionalized organic carboxylic acid precursor and ligand, and preparation method of metal organic framework material |
| CN111233825A (en) * | 2020-01-22 | 2020-06-05 | 广东工业大学 | Thiophene thiol functionalized organic aromatic carboxylic acid ligand and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107337626B (en) | 2019-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Self-assembly of a novel 2D network polymer: Syntheses, characterization, crystal structure and properties of a four-tin-nuclear 36-membered diorganotin (IV) macrocyclic carboxylate | |
| JP2013056859A (en) | π-CONJUGATED ORGANIC BORON COMPOUND AND METHOD OF PRODUCING THE SAME | |
| CN107337626B (en) | A kind of alkyl hydrosulfide functionalization aromatic carboxylic acids and preparation method thereof | |
| Ma et al. | Two 3D metal− organic frameworks as multi-functional materials to detect Fe3+ ions and nitroaromatic explosives and to encapsulate Ln3+ ions for white-light emission | |
| Ohta et al. | Synthesis and characterization of heteroleptic iron (II) thiolate complexes with weak iron–arene interactions | |
| CN108456188A (en) | A kind of 7- lignocaines -4- methytal coumarins derivative, preparation method and the application as nanometer fragrance precursor | |
| Avila-Sorrosa et al. | Buchwald–Hartwig C–N cross coupling reactions catalyzed by a pseudo-pincer Pd (II) compound | |
| Klein et al. | Convenient synthesis of functionalized 4, 4′-disubstituted-2, 2′-bipyridine with extended π-system for dye-sensitized solar cell applications | |
| An et al. | Syntheses and crystal structures of the metal complexes based on pyrazolecarboxylic acid ligands | |
| Langer et al. | A new set of nickelacyclic carboxylates (“nickelalactones”) containing pyridine as supporting ligand: synthesis, structures and application in C–C–and C–S–linkage reactions | |
| JP5923823B2 (en) | Intermediate for acene dichalcogenophene derivative and synthesis method thereof | |
| Fan et al. | Salen-type nickel (II), palladium (II) and copper (II) complexes having chiral and racemic camphoric diamine components | |
| CN111233724A (en) | Sulfydryl functionalized organic aromatic carboxylic acid ligand and preparation method and application thereof | |
| CN107383079B (en) | Metal organic framework material based on alkyl mercaptan modification and synthetic method thereof | |
| Yamamoto et al. | Luminescent rhenium (I)–gold (I) hetero organometallics linked by ethynylphenanthrolines | |
| CN106496080B (en) | A kind of preparation method of mercapto-functionalized aryl carboxylic acid | |
| Sivaramakrishna et al. | Novel reactivity aspects of cis-bis (1-alkenyl) platinum (II) compounds of the type Pt (CH2 (CH2) nCHCH2) 2L2 (where L2= dppp, dppe, dppm and n= 1, 2) | |
| CN110272337B (en) | 6-gingerol derivative and preparation and application thereof | |
| CN109232586A (en) | A kind of synthetic method of the more imidazole salts cage compounds of three-dimensional | |
| CN109111392B (en) | Synthetic method of cyclobutane derivative | |
| JP2012236777A (en) | Indolocarbazole-containing imide compound, and intermediate for synthesizing the same, method for producing them, organic semiconductor composition, and organic solar cell element | |
| TWI486353B (en) | Production methods of sanshool | |
| JP2010235453A (en) | Method for producing platinum complex | |
| Liu et al. | Syntheses, crystal structures and properties of four iron and cobalt complexes bearing 1, 3, 5-triazapentadienyl ligands | |
| JP5407332B2 (en) | Method for producing quarterpyridine derivative and its intermediate |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |