CN110483333A - A kind of preparation method for the polycarboxylic acid organic ligand that dicyanogen methyl isophorone replaces - Google Patents
A kind of preparation method for the polycarboxylic acid organic ligand that dicyanogen methyl isophorone replaces Download PDFInfo
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- CN110483333A CN110483333A CN201910809986.XA CN201910809986A CN110483333A CN 110483333 A CN110483333 A CN 110483333A CN 201910809986 A CN201910809986 A CN 201910809986A CN 110483333 A CN110483333 A CN 110483333A
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- dicarboxylic acid
- dimethyl ester
- biphenyl dicarboxylic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/14—Preparation of carboxylic acid nitriles by reaction of cyanides with halogen-containing compounds with replacement of halogen atoms by cyano groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- 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
Abstract
The invention belongs to organic chemical industry's synthesis technical fields, provide a kind of preparation method of polycarboxylic acid organic ligand that dicyanogen methyl isophorone replaces, the following steps are included: under dark conditions, using biphenyl dicarboxylic acid dimethyl ester as raw material, using the concentrated sulfuric acid as reaction dissolvent, it reacts to obtain crude product with elemental iodine, crude product is added in methanol, uses the concentrated sulfuric acid as catalyst, back flow reaction obtains 2, iodo- 4, the 4'- biphenyl dicarboxylic acid dimethyl ester of 2'- bis-；In an inert atmosphere, iodo- 4, the 4'- biphenyl dicarboxylic acid dimethyl ester of 2,2'- bis-, tetra-triphenylphosphine palladium, cuprous cyanide and anhydrous DMF are added in microwave reaction pipe, temperature reaction obtains 2,2'- dicyano -4,4'- biphenyl dicarboxylic acid dimethyl ester；The polycarboxylic acid organic ligand i.e. 2,2'- dicyano -4,4'- biphenyl dicarboxylic acid of dicyanogen methyl isophorone substitution is obtained by hydrolysis using 2,2'- dicyano -4,4'- biphenyl dicarboxylic acid dimethyl ester.The raw material and solvent that this method uses are cheap, readily available, only need three-step reaction just to obtain the target product of high-purity, and reaction yield is high.
Description
Technical field
The invention belongs to organic chemical industry's synthesis technical fields, and in particular to a kind of polycarboxylic acid organic ligand that dicyanogen methyl isophorone replaces
Preparation method.
Background technique
Metal-organic framework materials (MOFs) receive scientific research in the application of many aspects such as absorption, catalysis, separation, sensing
The concern of worker, thousands of kinds of MOFs materials are synthesized, and are greatly enriched the type of MOFs material.MOFs material
It is by organic ligand and metal salt by being self-assembly of, the type either metal salt of change organic ligand can be passed through
Type, to prepare a variety of different MOFs materials.By the direct modification to organic ligand, synthesize the organic of functionalization
Ligand, to prepare the MOFs material containing functional group, this is also the common method for preparing functionalization MOFs material.MOFs
The synthesis of material be unable to do without organic ligand, and the polycarboxylic acid organic ligand of dicyanogen methyl isophorone functionalization is seldom synthesized.It has been reported
Synthesize the route of the polycarboxylic acid organic ligand of dicyanogen methyl isophorone functionalization are as follows: first using biphenyl dicarboxylic acid as raw material, synthesize 2,2'- bis-
Iodo- 4,4'- biphenyl dicarboxylic acid dimethyl ester, obtained above-mentioned substance is in the environment of absolute anaerobic, with anhydrous N-methyl pyrrole
Pyrrolidone is solvent, reacts 6 hours under reflux state, which needs stringent anhydrous and oxygen-free to operate, slightly operation error
It is all unable to get final product, operability is very poor.Polycarboxylic acid organic ligand and the mantoquita complexing that the dicyanogen methyl isophorone being prepared replaces,
It is prepared for a kind of framework material.
Summary of the invention
The present invention is to carry out to solve the above-mentioned problems, and it is an object of the present invention to provide a kind of dicyanogen methyl isophorone easy to operate replaces
Polycarboxylic acid organic ligand preparation method.
The present invention provides a kind of preparation methods for the polycarboxylic acid organic ligand that dicyanogen methyl isophorone replaces, and have the feature that,
The following steps are included: step 1, under dark conditions, using biphenyl dicarboxylic acid dimethyl ester as raw material, using the concentrated sulfuric acid as reaction dissolvent,
It reacts to obtain crude product with elemental iodine, crude product is added in methanol, use the concentrated sulfuric acid as catalyst, back flow reaction obtains 2,
The iodo- 4,4'- biphenyl dicarboxylic acid dimethyl ester of 2'- bis-；Step 2, in an inert atmosphere, by iodo- 4, the 4'- biphenyl two of 2,2'- bis-
Formic acid dimethyl ester, tetra-triphenylphosphine palladium, cuprous cyanide and anhydrous DMF are added in microwave reaction pipe, and temperature reaction obtains 2,
2'- dicyano -4,4'- biphenyl dicarboxylic acid dimethyl ester；Step 3, it is passed through using 2,2'- dicyano -4,4'- biphenyl dicarboxylic acid dimethyl ester
It crosses hydrolysis and obtains the polycarboxylic acid organic ligand i.e. 2,2'- dicyano -4,4'- biphenyl dicarboxylic acid of dicyanogen methyl isophorone substitution.
In the preparation method for the polycarboxylic acid organic ligand that dicyanogen methyl isophorone provided by the invention replaces, can also have such
Feature: where in step 1, temperature when reacting with elemental iodine is 80 DEG C, and the reaction time is for 24 hours.
In the preparation method for the polycarboxylic acid organic ligand that dicyanogen methyl isophorone provided by the invention replaces, can also have such
Feature: where in step 1, the molar ratio of biphenyl dicarboxylic acid dimethyl ester and elemental iodine is 1:1.8~1:2.5.
In the preparation method for the polycarboxylic acid organic ligand that dicyanogen methyl isophorone provided by the invention replaces, can also have such
Feature: where in step 2,2,2'- bis- iodo- 4,4'- biphenyl dicarboxylic acid dimethyl esters, tetra-triphenylphosphine palladium, cuprous cyanide mole
Than for 50:150:1.
In the preparation method for the polycarboxylic acid organic ligand that dicyanogen methyl isophorone provided by the invention replaces, can also have such
Feature: where in step 2, be warming up to 120 DEG C of reaction 1h and obtain 2,2'- dicyano -4,4'- biphenyl dicarboxylic acid dimethyl ester.
The action and effect of invention
The preparation method for the polycarboxylic acid organic ligand that provided dicyanogen methyl isophorone replaces according to the present invention, first uses biphenyl dicarboxylic acid
Dimethyl ester is raw material, and in shading environment, iodination reaction occurs with elemental iodine；Then in inert gas environment, pass through microwave
Cyanogenation occurs for method and cuprous cyanide；The polycarboxylic acid organic ligand i.e. 2,2'- dicyan of dicyanogen methyl isophorone substitution is obtained using hydrolysis
Base -4,4'- biphenyl dicarboxylic acid.The simple organic reaction of three steps is only needed from raw material to target product, reaction is simple and generally fits
Synthetic route obtains the organic ligand that can synthesize metallic framework material by the introducing of dicyanogen methyl isophorone, so that later with the method
The type of synthesis metal-organic framework materials is enriched.
In addition, in step 1, it is rear again using the concentrated sulfuric acid as catalyst first using the concentrated sulfuric acid as solvent, reduce reaction system
The type of middle substance, and then reduce the impurity in reaction system, be conducive to the purification of product.
In addition, by nuclear-magnetism detection it is found that the reaction product purity of every step reaction is all very high, and reaction yield is all higher,
The prospect promoted with scale.
In addition, used raw material and solvent are cheap, it is readily available, and do not need any post-processing and can be used.
Detailed description of the invention
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of compound a in the embodiment of the present invention；
Fig. 2 is the nucleus magnetic hydrogen spectrum figure of compound b in the embodiment of the present invention；
Fig. 3 is the nucleus magnetic hydrogen spectrum figure of organic ligand L in the embodiment of the present invention；And
Fig. 4 is the nuclear-magnetism carbon spectrogram of organic ligand L in the embodiment of the present invention.
Specific embodiment
In order to be easy to understand the technical means, the creative features, the aims and the efficiencies achieved by the present invention, tie below
Examples and drawings are closed to be specifically addressed the preparation method for the polycarboxylic acid organic ligand that a kind of dicyanogen methyl isophorone of the present invention replaces.
Raw material employed in the embodiment of the present invention and solvent are that analysis is pure, can be with by the purchase of general commercial sources
It obtains.
Polycarboxylic acid organic ligand, that is, 2,2'- cyano -4,4'- biphenyl dicarboxylic acid conjunction that dicyanogen methyl isophorone provided by the invention replaces
It is as follows at route:
<embodiment>
The present embodiment is specifically described the synthesis process of 2,2'- cyano -4,4'- biphenyl dicarboxylic acid.
Step 1, under dark conditions, using biphenyl dicarboxylic acid dimethyl ester as raw material, using the concentrated sulfuric acid as reaction dissolvent, with iodine list
Qualitative response obtains crude product, and crude product is added in methanol, uses the concentrated sulfuric acid as catalyst, and back flow reaction obtains 2,2'- bis-
Iodo- 4,4'- biphenyl dicarboxylic acid dimethyl ester.Wherein, the molar ratio of biphenyl dicarboxylic acid dimethyl ester and elemental iodine is 1:1.8~1:2.5,
Temperature when reaction is 80 DEG C, and the reaction time is for 24 hours.
Concrete operations are as follows: weigh 4,4'- biphenyl dicarboxylic acid (10.00g, 41.3mmol), silver sulfate (28.00g,
It 89.7mmol) is added in 500mL bottle with two necks, the 250mL concentrated sulfuric acid is then added and stirs at room temperature, then weigh iodine list
Matter (23.00g, 90.5mmol) is added in bottle with two necks, and carries out shading treatment with masking foil package bottle with two necks, under room temperature instead
1 hour is answered, then raises temperature to 80 DEG C, continues to be stirred to react 24 hours.It is cooled to room temperature after reaction, it will be in bottle with two necks
Reaction solution pours into 500mL ice water, generates a large amount of yellow mercury oxides, crude product is obtained by filtration.Above-mentioned crude product is added to 500mL
In single port bottle, and 300mL methanol is added, the 5mL concentrated sulfuric acid is slowly added dropwise after stirring, is warming up to 100 DEG C, back flow reaction 12 is small
When, it is cooled to room temperature, vacuum distillation removes organic solvent, adds 200mL saturated salt solution, then extracted with 500mL methylene chloride
It takes three times, organic phase is dry with anhydrous magnesium sulfate, and vacuum distillation removes organic solvent, utilizes thin layer chromatography column purification, expansion
Agent is methylene chloride, obtains white powder 2, iodo- 4, the 4'- biphenyl dicarboxylic acid dimethyl ester 18.35g of 2'- bis-, i.e. compound a, yield
For 85.1% (in terms of biphenyl dicarboxylic acid dimethyl ester).
Nuclear-magnetism detection is carried out to obtained white powder, testing result is shown in Fig. 1.
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of compound a in the embodiment of the present invention.
As shown in Figure 1,1H NMR(600MHz,CDCl3), δ 8.54 (s, 2H), 8.02 (d, J=7.8Hz 2H), 7.17 (d,
J=7.8Hz, 2H), 3.88 (s, 6H).
Because of the high symmetry of the structure of compound a, the upper peak for four kinds of hydrogen environment only occur of hydrogen spectrum, but H
Total number is consistent with the total number for the H for being theoretically synthesized ligand, is all for 12 H.Wherein, 8.54ppm (2H) it is unimodal,
8.02ppm's (2H) is bimodal, 7.17ppm (2H) bimodal, is respectively belonging to the hydrogen signal of 6 positions on phenyl ring；3.88ppm
The unimodal hydrogen signal for being respectively belonging to methyl position on two ester groups of (6H).It follows that obtained white powder is to change
Close the iodo- 4,4'- biphenyl dicarboxylic acid dimethyl ester of object a 2,2'- bis-.
Step 2, in an inert atmosphere, by iodo- 4, the 4'- biphenyl dicarboxylic acid dimethyl ester of 2,2'- bis-, four triphenylphosphines
Palladium, cuprous cyanide and anhydrous DMF are added in microwave reaction pipe, and temperature reaction obtains 2,2'- dicyano -4,4'- biphenyl two
Formic acid dimethyl ester.Wherein, the molar ratio of iodo- 4, the 4'- biphenyl dicarboxylic acid dimethyl ester of 2,2'- bis-, tetra-triphenylphosphine palladium, cuprous cyanide
For 50:150:1, it is warming up to 120 DEG C of reaction 1h and obtains 2,2'- dicyano -4,4'- biphenyl dicarboxylic acid dimethyl ester.
Concrete operations are as follows: iodo- 4, the 4'- biphenyl dicarboxylic acid dimethyl ester of Weigh Compound a 2,2'- bis- (1.04g,
2.0mmol), cuprous cyanide (0.54g, 6.0mmol), tetra-triphenylphosphine palladium (46.0mg, 0.04mmol) is in microwave tube, and stirring is simultaneously
It vacuumizes displacement Ar gas three times, absolute DMF 15mL is added, is stirred at room temperature 10 minutes, is put into microwave reactor, 5 minutes
120 DEG C are warming up to, and the reaction was continued 1 hour, are cooled to room temperature, obtained reaction solution is poured into 10% ammonia spirit of 100mL
In be stirred at room temperature 30 minutes, the solid was filtered crude product, and with thin layer chromatography column purification, solvent is methylene chloride, is obtained white
Color powder 0.35g, i.e. compound b, yield be 54.7% (with compound a 2, iodo- 4, the 4'- biphenyl dicarboxylic acid dimethyl ester of 2'- bis-
Meter).
Nuclear-magnetism detection is carried out to obtained white powder, testing result is shown in Fig. 2.
Fig. 2 is the nucleus magnetic hydrogen spectrum figure of compound b in the embodiment of the present invention.
As shown in Fig. 2,1H NMR(600MHz,CDCl3), δ 8.50 (s, 2H), 8.38 (d, J=12.0Hz, 2H), 7.69
(s, J=12.0Hz, 2H), 4.00 (s, 6H).
Because of the high symmetry of the structure of compound b, it only will appear the peaks of four kinds of hydrogen environment in hydrogen spectrum, but H
Total number it is consistent with the total number for the H for being theoretically synthesized ligand, be all for 12 H.Wherein, 8.50ppm (2H) it is unimodal,
8.38ppm's (2H) is bimodal, 7.69ppm (2H) bimodal, is respectively belonging to the hydrogen signal of 6 positions on phenyl ring；4.00ppm
The unimodal hydrogen signal for being respectively belonging to methyl position on two ester groups of (6H).It follows that the white powder is compound b
2,2'- dicyano -4,4'- biphenyl dicarboxylic acid dimethyl ester.
Step 3, dicyanogen methyl isophorone is obtained by hydrolysis using 2,2'- dicyano -4,4'- biphenyl dicarboxylic acid dimethyl ester to replace
Polycarboxylic acid organic ligand, that is, 2,2'- dicyano -4,4'- biphenyl dicarboxylic acid.
Concrete operations are as follows: Weigh Compound b 2,2'- dicyano -4,4'- biphenyl dicarboxylic acid dimethyl ester (0.13g,
0.4mmol) in 50mL single port bottle, 5mL ethyl alcohol is added, stirs at room temperature, the 1mol/LNaOH of 1.1mL is added dropwise dropwise
Organic solvent is removed under reduced pressure after reacting 24 hours at room temperature in solution, and 20mL distilled water is then added, is placed in 0 DEG C of ice water
In bath, 15% dilute hydrochloric acid solution is added dropwise, adjusting pH value of solution to 1 continues stirring 30 minutes, and suction filtration obtains white powder, and
It is washed respectively three times with 30mL distilled water and 30mL n-hexane, dries and organic ligand L can be obtained, i.e. dicyano -4 2,2'-,
4'- biphenyl dicarboxylic acid 0.09g, yield are 77.9% (with compound b 2,2'- dicyano -4,4'- biphenyl dicarboxylic acid dimethyl ester
Meter).
Nuclear-magnetism detection is carried out to obtained target product organic ligand L, testing result is shown in Fig. 3 and Fig. 4.
Fig. 3 is the nucleus magnetic hydrogen spectrum figure of organic ligand L in the embodiment of the present invention.
As shown in figure 3,1H NMR (600MHz, DMSO) δ 13.83 (s, 2H), 8.50 (s, 2H), 8.37 (dd, J=8.1,
1.5Hz, 2H), 7.88 (d, J=8.4Hz, 2H).
Because of the high symmetry of the structure of organic ligand L, it only will appear the peak of four kinds of hydrogen environment in hydrogen spectrum, still
The total number of H is consistent with the total number for the H for being theoretically synthesized ligand, is all for 8 H.The wherein list at δ=13.83ppm (2H)
Peak is the characteristic absorption peak of carboxylic acid hydrogen on phenyl ring, bimodal, 8.37ppm (2H) bimodal, 7.88ppm of 8.50ppm (2H)
The bimodal hydrogen signal for being respectively belonging to 6 positions on phenyl ring of (2H).
Fig. 4 is the nuclear-magnetism carbon spectrogram of organic ligand L in the embodiment of the present invention.
As shown in figure 4,13C NMR (151MHz, DMSO), δ 165.78,144.54,134.41,134.31,132.96,
131.67,117.11,112.51。
The total number of C is consistent with the total number for the C for being theoretically synthesized ligand, is all wherein δ=165.78ppm for 16 C
(2C) is the characteristic absorption peak of two carboxylic acid carbon, the unimodal characteristic absorption peak for cyano carbon at 117.11ppm (2C),
The unimodal absorption peak for carbon on the phenyl ring that is connected with cyano at 112.51ppm (2C), 144.54ppm (2C), 134.41ppm
(2C), 134.31ppm (2C), 132.96ppm (2C), 131.67ppm (2C) are respectively belonging to the letter of other 10 carbon on phenyl ring
Number absorption peak.
Therefore, by Fig. 3 and Fig. 4 it is found that target product is organic ligand L 2,2'- dicyano -4,4'- biphenyl diformazan
Acid.
The action and effect of embodiment
The present embodiment is first raw material with biphenyl dicarboxylic acid dimethyl ester, and in shading environment, iodination reaction occurs with elemental iodine；
Then in inert gas environment, cyanogenation is occurred by microwave method and cuprous cyanide；Dicyanogen methyl isophorone is obtained using hydrolysis to take
The polycarboxylic acid organic ligand in generation, that is, 2,2'- dicyano -4,4'- biphenyl dicarboxylic acid.Only need three steps simple from raw material to target product
Single organic reaction reacts simple and blanket synthetic route and by the introducing of dicyanogen methyl isophorone obtains that metallic framework can be synthesized
The organic ligand of material, so that enriched with the type of method synthesis metal-organic framework materials later.
In addition, during reacting with elemental iodine, joined silver sulfate in step 1, so that the decomposition reaction of elemental iodine adds
Speed carries out, to be conducive to the progress of the iodine substitution reaction on phenyl ring.Meanwhile in the reaction of this step, first using the concentrated sulfuric acid as solvent,
Afterwards again using the concentrated sulfuric acid as catalyst, reduce the type of substance in reaction system, and then reduce the impurity in reaction system,
Be conducive to the purification of product.
In addition, by nuclear-magnetism detection it is found that the reaction product purity of every step reaction is all very high, and reaction yield is all higher,
The prospect promoted with scale.
In addition, reaction condition is mild, required temperature is 0 DEG C~120 DEG C, and easy to operate, separating-purifying only needs to chromatograph
It isolates and purifies or filtering and washing, it is simple and easy.
In addition, used raw material and solvent are cheap, it is readily available, and do not need any post-processing and can be used.
Above embodiment is preferred case of the invention, the protection scope being not intended to limit the invention.
Claims (5)
1. a kind of preparation method for the polycarboxylic acid organic ligand that dicyanogen methyl isophorone replaces, which comprises the following steps:
Step 1, anti-with elemental iodine using the concentrated sulfuric acid as reaction dissolvent using biphenyl dicarboxylic acid dimethyl ester as raw material under dark conditions
Crude product should be obtained, the crude product is added in methanol, uses the concentrated sulfuric acid as catalyst, back flow reaction obtains 2,2'- bis-
Iodo- 4,4'- biphenyl dicarboxylic acid dimethyl ester；
Step 2, in an inert atmosphere, by iodo- 4, the 4'- biphenyl dicarboxylic acid dimethyl ester of 2, the 2'- bis-, four triphenylphosphines
Palladium, cuprous cyanide and anhydrous DMF are added in microwave reaction pipe, and temperature reaction obtains 2,2'- dicyano -4,4'- biphenyl two
Formic acid dimethyl ester；
Step 3, dicyanogen methyl isophorone is obtained by hydrolysis using 2,2'- dicyano -4,4'- biphenyl dicarboxylic acid dimethyl ester to replace
Polycarboxylic acid organic ligand, that is, 2,2'- dicyano -4,4'- biphenyl dicarboxylic acid.
2. the preparation method for the polycarboxylic acid organic ligand that dicyanogen methyl isophorone according to claim 1 replaces, it is characterised in that:
Wherein, in step 1, temperature when reacting with elemental iodine is 80 DEG C, and the reaction time is for 24 hours.
3. the preparation method for the polycarboxylic acid organic ligand that dicyanogen methyl isophorone according to claim 1 replaces, it is characterised in that:
Wherein, in step 1, the molar ratio of the biphenyl dicarboxylic acid dimethyl ester and the elemental iodine is 1:1.8~1:2.5.
4. the preparation method for the polycarboxylic acid organic ligand that dicyanogen methyl isophorone according to claim 1 replaces, it is characterised in that:
Wherein, in step 2, iodo- 4, the 4'- biphenyl dicarboxylic acid dimethyl ester of 2, the 2'- bis-, the tetra-triphenylphosphine palladium, the cyanogen
Changing cuprous molar ratio is 50:150:1.
5. the preparation method for the polycarboxylic acid organic ligand that dicyanogen methyl isophorone according to claim 1 replaces, it is characterised in that:
Wherein, in step 2,120 DEG C of reaction 1h is warming up to and obtain 2,2'- dicyano -4,4'- biphenyl dicarboxylic acid dimethyl ester.
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