CN110437084A - A kind of compound and its covalent organic framework and preparation method of preparation - Google Patents
A kind of compound and its covalent organic framework and preparation method of preparation Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/06—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
- C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
- C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
- C07C217/84—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
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- 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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/06—Amines
- C08G12/08—Amines aromatic
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- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Abstract
The present invention provides the covalent organic framework and preparation method of a kind of compound and its preparation.The compound has structure shown in formula (I):Wherein, R is amino or nitro.The compound can be used as starting material or intermediate is used to prepare using structure shown in formula (II) as the covalent organic frame material of basic unit:
Description
Technical field
The present invention relates to machine technical field of function materials, and in particular to a kind of compound and its covalent organic frame of preparation
Structure and preparation method.
Background technique
Disclosing the information of the background technology part, it is only intended to increase understanding of the overall background of the invention, without certainty
It is considered as recognizing or implying in any form that information composition has become existing skill well known to persons skilled in the art
Art.
Covalent organic frame (COFs) is the novel porous crystalline state material of one kind constructed by organic structure ele by covalent bond
Material.Make COF that there is high crystallinity, uniform pores by the accurate reticular structure that covalent bond is constructed by organic architecture unit
Rate, lower density, big specific surface area, the features such as high stability and structure are adjustable.2005, Yaghi etc. utilized 1,4-
Autohemagglutination dehydrating condensation to benzene hypoboric acid and benzene hypoboric acid is reacted with what hydroxyl triphen was condensed, synthesized covalently has machine frame for the first time
Frame material COF-1 and COF-5, PXRD is analysis shows the material is two-dimentional crystalline material.Yaghi in 2007 etc. uses amine and benzaldehyde
Condensation reaction successfully develop a kind of novel covalent organic frame material COF-300, through powder diffraction data analysis shows,
The material has the crystallinity of height, forms a kind of diamond topological structure of five rare weight interpenetrating.COFs material for
Gas storage and separation, drug conveying, catalysis, energy conversion and storage etc. have very big application potential.
Summary of the invention
It is the purpose of the present invention is to provide a kind of novel acetylene compound and its synthetic method and its accordingly covalently organic
The preparation and property research of frame material, the compound be 2- (2- propargyl alcoholate) benzene-Isosorbide-5-Nitrae-diamines and it is described be based on 2-
The covalent organic framework of (2- propargyl alcoholate) benzene -1,4- diamine structure unit is a kind of covalently having for schiff base reaction formation
Machine frame, the frame aperture is uniform, compound with regular structure, and has good chemical stability and thermal stability.
Specifically, it is described that technical scheme is as follows:
In the first aspect of the present invention, the present invention provides a kind of compounds, with structure shown in formula (I):
Wherein, R is amino or nitro.
Wherein, when R is amino, its chemical name is 2- (2- propargyl alcoholate) benzene-Isosorbide-5-Nitrae-diamines；When R is nitro, chemistry
Entitled 4- nitro -2- (2- propargyl alcoholate) aniline.Two compounds can be by reduction reaction by nitre especially when R is nitro
Base is reduced to amino to which 2- (2- propargyl alcoholate) benzene -1,4- diamines be prepared by 4- nitro -2- (2- propargyl alcoholate) aniline.
In the second aspect of the present invention, the present invention provides the synthetic method of formula (I) compound, side's method includes 2-
Amino-5-nitrophenol reacts in solvent in the presence of a base with 3- propargyl bromide is prepared 4- nitro -2- (2- propargyl alcoholate)
Aniline；Alternatively, continuing reduction nitro obtains 4- nitro -2- (2- propargyl alcoholate) aniline.
In the embodiment of present invention preparation formula (I) compound, the alkali is selected from potassium carbonate, ammonium carbonate, cesium carbonate, iodine
Change sodium, sodium hydride, sodium ethoxide, Sodamide, potassium tert-butoxide, potassium hydroxide, Tetrabutylammonium bromide or ammonium hydroxide；Further preferably
Potassium carbonate, sodium ethoxide or potassium tert-butoxide.
In the embodiment of present invention preparation formula (I) compound, the solvent is selected from acetone, ethyl alcohol, toluene, tetrahydro furan
It mutters, N,N-dimethylformamide, N, accelerine, mineral oil, dimethyl sulfoxide, acetonitrile or 1,2- dimethoxy-ethane；
Further preferably anhydrous propanone, ethyl alcohol or acetonitrile.
In the embodiment of present invention preparation formula (I) compound, the combination of above-mentioned solvent and alkali can any combination, but
It is that, when the combination of alkali and solvent is selected from the following group, effect can be preferable: potassium carbonate+anhydrous propanone, potassium carbonate+tetrahydrofuran, carbon
Sour potassium+anhydrous propanone/toluene, potassium carbonate+N, accelerine, potassium carbonate+1,2- dimethoxy-ethane, sodium ethoxide+ethyl alcohol,
Potassium tert-butoxide+acetonitrile；Especially potassium carbonate+anhydrous propanone combination, yield are especially high.
In some embodiments of the present invention, the preparation of 4- nitro -2- (2- propargyl alcoholate) aniline includes below carrying out
Reaction: heating reflux reaction in anhydrous propanone is added in 2- Amino-5-nitrophenol, potassium carbonate and 3- propargyl bromide.2- amino -5- nitre
The molar ratio of base phenol and potassium carbonate is 1-3:2-6, preferably 1:2.
In some embodiments of the present invention, by 4- nitro -2- (2- propargyl alcoholate) aniline preparation formula (I) compound
Reaction includes: that 4- nitro -2- (2- propargyl alcoholate) benzene is dissolved in anhydrous Isosorbide-5-Nitrae-dioxane, and reflection system is dropped to 10 DEG C,
The concentrated hydrochloric acid solution of stannous chloride is added dropwise, reaction is stirred at room temperature, solution becomes yellow.4- nitro -2- (2- propargyl alcoholate) aniline
Molar ratio with stannous chloride is 1-1.2:5-6, preferably 1.04:6.
In some embodiments of the present invention, formula (I) compound is generated by following reaction route:
In the embodiment of present invention preparation formula (I) compound, the method also includes every steps to purify after reaction
The step of, purifying can be used method commonly used in the art and carry out, still, when using described in certain embodiments of the present invention
Purification process when effect can be especially good.
In some embodiments of the present invention, purification process of the present invention includes: preparation 4- nitro -2- (2- third
Alkynyloxy group) aniline is cooled to room temperature after reaction, and it filters, is purified after vacuum distillation with column chromatography, mobile phase is
The mixed solution of petroleum ether and ethyl acetate, wherein the volume ratio of petroleum ether and ethyl acetate is 3:1.
And In some embodiments of the present invention, purification process of the present invention includes: by 4- nitro -2- (2-
Propargyl alcoholate) aniline preparation formula (I) compound after reaction, with sodium hydrate aqueous solution neutralize, methylene chloride extraction, nothing
It being purified after the drying of water ammonium sulfate, vacuum distillation with column chromatography, mobile phase is the mixed solution of petroleum ether and ethyl acetate,
Wherein, the volume ratio of petroleum ether and ethyl acetate is 1:1.
In the third aspect of the present invention, the present invention provides formula (I) compounds to prepare as starting material or intermediate
Application in covalent organic frame material, wherein the covalent organic frame material is using structure shown in formula (II) as basic unit:
Covalent organic frame material of the present invention can have the structure as shown in formula (III):
Wherein, R isStructure, wherein a, b, c respectively indicate three connection sites, and a
Point is connect with formula (III)；n≥1.
When n is greater than 1, the connection type between multiple R groups is that the site a is connected with the site b or the site c, and multiple R groups can
Cyclic structure is connected into, as shown in formula (II).
It is described total the present invention provides a kind of preparation method of covalent organic frame material in the fourth aspect of the present invention
Valence organic framework materials using structure shown in formula (II) as basic unit, the preparation method using formula (I) compound as raw material or in
Mesosome, when R is nitro, nitro is reduced to after amino and the reaction preparation of 1,3,5- tri- (to Fonnylphenyl) benzene covalently has machine frame
Frame material；Or when R is amino, formula (I) compound and 1,3,5- tri- (to Fonnylphenyl) benzene reaction prepares covalently organic
Frame material.
When R is nitro, nitro can be reduced to amino by reduction reaction, thus by 4- nitro -2- (2- propine oxygen
Base) aniline is prepared 2- (2- propargyl alcoholate) benzene-Isosorbide-5-Nitrae-diamines, realize the conversion between formula (I) two compounds.The method
It can be as described in second aspect of the present invention.
In embodiments of the present invention, the preparation method of the covalent organic frame material includes: by formula (I) compound
(R is amino) and 1,3,5- tri- (to Fonnylphenyl) benzene dissolve in a solvent, reacted under nitrogen protection, after reaction from
The heart, drying obtain covalent organic frame material.
In embodiments of the present invention, the preparation method of the covalent organic frame material includes: by formula (I) compound
(R is nitro) carries out after reduction reaction obtains formula (I) compound that R is amino, then with 1,3,5- tri- (to Fonnylphenyl) benzene
Dissolution in a solvent, is reacted under nitrogen protection, is centrifuged after reaction, and drying obtains covalent organic frame material.
In some embodiments of the present invention, in the preparation method of the covalent organic frame material, solvent is neighbour two
The mixed solution of chlorobenzene, n-butanol and aqueous acetic acid.
In some embodiments, the volume ratio of the o-dichlorohenzene and n-butanol is 2-5:2-5, preferably 1:1.One
In a little embodiments, the volume ratio 1-3:0.2-1 of the n-butanol and aqueous acetic acid is further 1-2:0.2-0.5, preferably
For 1:0.2.In some embodiments, the concentration of the aqueous acetic acid is 2-8mol/L, preferably 6mol/L.
In embodiments of the present invention, inventor passes through screening discovery o-dichlorohenzene, n-butanol and aqueous acetic acid
The dicyandiamide solution of composition is beneficial to the generation of organic framework of the present invention, replaces or remove any of them solvent, all
It may result in the deviation in structure.Also, it is found in the research of inventor, the stability that solvent compares the structure generated has
Extreme influence, inventor speculate that the composition of dicyandiamide solution will affect the crystalline state of organic framework and then influence the steady of structure
It is qualitative.For example, in certain embodiments of the present invention, when o-dichlorohenzene is not less than n-butanol, such as when volume ratio 2-5:2,
The crystalline state of its obtained frame structure is better than the situation of n-butanol excess, but especially in o-dichlorohenzene and n-butanol dosage phase
Meanwhile obtained organic framework crystalline state is best, structure is most stable.And the dosage of acetum also will affect product knot
The crystalline state of structure.Specifically, in embodiments of the present invention, when n-butanol is in excess in the volume of aqueous acetic acid, crystallization
State can be more preferable, and when the volume ratio 1-2:0.2-0.5, particularly 1:0.2 of n-butanol and acetum, the stability of structure is best,
Can be kept under 320 DEG C of high temperature stable structure and keep to common organic solvent (such as tetrahydrofuran, methanol, ethyl alcohol,
Acetone, acetonitrile, n,N-Dimethylformamide etc., but not limited to this) structural stability.The height of stability, in the present invention
It especially shows to thermal stability and to the stability of organic solvent.
In some embodiments, the reaction temperature is 100-150 DEG C, preferably 120 DEG C.
In embodiments of the present invention, reaction temperature is also to influence frame structure crystalline state of the present invention and stability
An important factor for, it is found in the research of inventor, when reaction temperature is not higher than 150 degrees Celsius, is not less than 100 degrees Celsius,
Structure of the invention can be generated, but crystalline state is variant, when reaction temperature is 120 DEG C, the knot of obtained reaction product
Crystalline state is best, structural stability also highest.
In some embodiments, the reaction time is 48-72 hours, preferably 72 hours.
In the fifth aspect of the invention, the present invention also provides preparation methods described in above-mentioned fourth aspect to be prepared
Covalent organic frame material, using formula (II) compound as basic unit, or have formula (III) shown in structure.
In the fifth aspect of the invention, the present invention also provides above-mentioned covalent organic frame materials stores and divides in gas
From the application in the conveying of, drug, catalysis or energy conversion and storage art.
It is that one kind passes through schiff bases based on 2- (2- propargyl alcoholate) benzene-covalent organic frame of Isosorbide-5-Nitrae-diamine structure unit
The covalent organic frame generated is reacted, by strict control solution ratio and reaction temperature, obtaining a kind of crystalline state well covalently has
Machine frame can still keep original structure insoluble in common are machine solution at high temperature, chemical stability with higher and
Thermal stability, and preparation method is simple, because it can have light by modifying after the method for rear modification with alkynyloxy group functional group
The molecular structure of the functions such as electricity, catalysis, energy storage, and can recycle repeatedly, it is energy saving, protect environment.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present application, and the application's shows
Meaning property embodiment and its explanation are not constituted an undue limitation on the present application for explaining the application.Hereinafter, coming in conjunction with attached drawing detailed
Describe bright embodiment of the present invention in detail, in which:
Fig. 1 is the nuclear magnetic resonance spectroscopy of compound 4- nitro -2- (2- propargyl alcoholate) aniline in embodiment 1.
Fig. 2 is the carbon-13 nmr spectra of compound 4- nitro -2- (2- propargyl alcoholate) aniline in embodiment 1.
Fig. 3 is the nuclear magnetic resonance spectroscopy of compound 2- (2- propargyl alcoholate) benzene -1,4- diamines in embodiment 1.
Fig. 4 is the carbon-13 nmr spectra of compound 2- (2- propargyl alcoholate) benzene -1,4- diamines in embodiment 1.
Fig. 5 is polycrystalline X-ray diffraction (PXRD) figure of the covalent organic frame material COF-MQ1 in embodiment 2.
Fig. 6 is the thermal gravimetric analysis curve figure (TGA) of the covalent organic frame material COF-MQ1 in embodiment 2.
Fig. 7 is the infrared spectrogram of the covalent organic frame material COF-MQ1 in embodiment 2, wherein a spectrogram is corresponding
It is the infrared absorption curve of COF-MQ1, it is the infrared absorption curve of 1,3,5- tri- (to Fonnylphenyl) benzene, c that b spectrogram is corresponding
It is the absorption curve of 2- (2- propargyl alcoholate) benzene -1,4- diamines that spectrogram is corresponding.
The SEM figure that Fig. 8 is the covalent organic frame material COF-MQ1 in embodiment 2.
Fig. 9 be embodiment 3 in COF-QM1 impregnated three days in a variety of different solvents after XRD comparison diagram.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to conventional strip
Part or according to the normal condition proposed by manufacturer.
Unless otherwise defined, it anticipates known to all professional and scientific terms as used herein and one skilled in the art
Justice is identical.Reagent or raw material used in the present invention can be bought by conventional route and be obtained, unless otherwise specified, institute of the present invention
The reagent or raw material used is used according to this field usual manner or is used according to product description.In addition, any and institute
The similar or impartial method of contents and material can be applied to the method for the present invention.Preferable implementation method described in the text with
Material is for illustrative purposes only.
Embodiment 1The synthesis of compound 2- (2- propargyl alcoholate) benzene -1,4- diamines
(1) 2- Amino-5-nitrophenol (0.46g, 3.0mmol), potassium carbonate (0.83g, 6.0mmol) and 3- propargyl bromide
Anhydrous propanone (20ml) is added in (0.5ml).It is heated to reflux 12 hours, is cooled to room temperature, filter.Column chromatography is used after vacuum distillation
It is purified (petrol ether/ethyl acetate=3/1, volume ratio) and obtains 4- nitro -2- (2- propargyl alcoholate) aniline of 0.53g, produced
Rate: 92%.1H NMR(d6- DMSO, 400MHz): δ=3.63 (t, 1H), 4.93 (s, 1H), 6.43 (s, 1H), 6.69-6.71
(d,2H),7.73(s,1H),7.75-7.78(d,1H)ppm.13C-NMR(d6-DMSO,128MHz):56.57,79.17,
79.43,108.27,111.94,120.72,135.78,142.57,1 46.76.Its nuclear magnetic resonance spectroscopy, carbon spectrum are respectively such as Fig. 1
With shown in Fig. 2.
(2) 4- nitro -2- (2- propargyl alcoholate) aniline (0.2g, 1.04mmol) is dissolved in anhydrous 1,4- dioxane
In (15ml), reflection system is dropped to 10 DEG C, is added dropwise to concentrated hydrochloric acid (3ml) solution of stannous chloride (1.4g, 6.0mmol).Room
Temperature stirring 48 hours, solution becomes yellow.It being neutralized, is extracted with dichloromethane with sodium hydrate aqueous solution, anhydrous sodium sulfate is dry,
(petrol ether/ethyl acetate=1/1, volume ratio), which is purified, with column chromatography after vacuum distillation obtains 0.15g 2- (2- propine
Oxygroup) benzene -1,4- diamines, yield: 90%.1H NMR(d6- DMSO, 400MHz): δ=3.56 (t, 1H), 3.88 (s, 1H),
4.31(s,1H),4.64(s,1H),6.26(s,1H),6.40(d,1H)ppm.13CNMR:56.03,78.21,79.85,
101.50,108.54,117.08,126.73,139.85,146.28。HRMS(ESI,m/z)calculated for C9H10N2O
[M+Na+]185.0691,found:185.0698.Its nuclear magnetic resonance spectroscopy, carbon spectrum are as shown in Figure 3 and Figure 4 respectively.
It reacts as follows:
On the basis of the preparation method of above-described embodiment 1, solvent, the alkali of step (1) are screened, especially verified
The combination of following alkali+solvent, comprising: potassium carbonate+tetrahydrofuran, potassium carbonate+anhydrous propanone/toluene, potassium carbonate+N, N- diformazan
Base aniline, potassium carbonate+1,2- dimethoxy-ethane, sodium ethoxide+ethyl alcohol, potassium tert-butoxide+acetonitrile, as a result, it has been found that, in embodiment 1
On the basis of, by alkali and solvent is changed to sodium ethoxide+ethyl alcohol by potassium carbonate+anhydrous propanone or potassium tert-butoxide+acetonitrile, yield have
The reduction of 20-30%；On the basis of embodiment 1, solvent and alkali are changed to potassium carbonate+tetrahydrofuran, potassium carbonate+anhydrous third
Ketone/toluene, potassium carbonate+n,N-Dimethylaniline or potassium carbonate+1,2- dimethoxy-ethane, yield have at least 10% drop
It is low.
Embodiment 2
2- (2- propargyl alcoholate) benzene-Isosorbide-5-Nitrae-diamines (9.7mg, 0.06mol) and 1 is added into the pipe of 10ml, 3,5- tri- is (right
Fonnylphenyl) benzene (15.6mg, 0.04mmol) and it is added o-dichlorohenzene (1ml) and n-butanol (1ml) obtains brown color precipitating,
The acetum of 0.2ml is added into above-mentioned mixed solution, by the seal of tube.It carries out freeze-thaw three times to recycle, in 120 DEG C of oil
It is heated 3 days in bath.Reaction terminates, and centrifugation obtains tan precipitate, and precipitating is washed three times with tetrahydrofuran, then uses Soxhlet extraction
Device (methanol, acetone, tetrahydrofuran) is sufficiently washed, and 120 degrees Celsius are dried in vacuo 12 hours, is obtained 11mg and is based on 2- (2-
Propargyl alcoholate) benzene-Isosorbide-5-Nitrae-diamine structure unit covalent organic frame material (it is expressed as COF-MQ1, whereinIt indicates to repeat single
Member), the x-ray diffraction pattern of covalent organic frame material COF-MQ1 is as shown in Figure 5, infrared spectrogram is as described in Figure 7, SEM figure
As shown in Figure 8, thermal gravimetric analysis curve figure is as shown in Figure 6.
It reacts as follows:
On the basis of above-described embodiment 2, (single argument) is screened to dicyandiamide solution and reaction temperature, is especially tested
The composition of following dicyandiamide solution is demonstrate,proved, comprising: (1) o-dichlorohenzene (1ml) and n-butanol (1ml), acetum (1ml)；(2) adjacent
Dichloro-benzenes (1ml) and n-butanol (2.5ml), acetum (0.2ml)；(3) o-dichlorohenzene (2ml) and n-butanol (1ml), acetic acid
Solution (0.2ml), and demonstrate reaction temperature: (1) 100 DEG C；(2)150℃；(3)90℃；(4)160℃.
As a result, it has been found that about dicyandiamide solution, when o-dichlorohenzene is not less than n-butanol, the crystalline state of obtained frame structure
It is better than the situation of n-butanol excess, but when o-dichlorohenzene is identical as n-butanol dosage, obtained organic framework is brilliant
State is best, and structure is most stable.And when n-butanol is in excess in the volume of aqueous acetic acid, crystalline state can be more preferable, especially 1:
When 0.2, the stability of structure is best.About reaction temperature, when reaction temperature is not higher than 150 degrees Celsius, not less than 100 degrees Celsius
When, structure of the invention can be generated, but crystalline state is variant, when reaction temperature is 120 DEG C, obtained reaction product
Crystalline state is best.
3 stability experiment of embodiment
Can be seen that the covalent organic frame by the thermal gravimetric analysis curve of COF-MQ1 material shown in fig. 6 can stablize
At 320 DEG C without obvious weightlessness, show its good thermal stability.
In addition, the present embodiment also demonstrates the chemical stability of COF-MQ1 material: 5mg COF-MQ1 being taken to be added to 6 respectively
In the bottle of a 20mL, tetrahydrofuran, methanol, ethyl alcohol, acetone, acetonitrile, the N of 15mL, N- bis- are separately added into six bottles
Methylformamide.It is centrifuged and dries after being placed at room temperature for three days, survey its XRD, as shown in figure 9, COF-MQ1 material is in above-mentioned solvent
Structure still remains original frame structure there is no collapsing.Show that COF-MQ1 material is stablized in these organic solvents
Property is good.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, although referring to aforementioned reality
Applying example, invention is explained in detail, for those skilled in the art, still can be to aforementioned each implementation
Technical solution documented by example is modified or equivalent replacement of some of the technical features.It is all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of compound, with structure shown in formula (I):
Wherein, R is amino or nitro.
The preparation method of formula 2. (I) compound, the method includes 2- Amino-5-nitrophenol and 3- propargyl bromides in the presence of a base
4- nitro -2- (2- propargyl alcoholate) aniline is prepared in reaction in solvent；Alternatively, continuing reduction nitro obtains 2- (2- propine
Oxygroup) benzene -1,4- diamines.
3. preparation method according to claim 2, which is characterized in that the alkali be selected from potassium carbonate, ammonium carbonate, cesium carbonate,
Sodium iodide, sodium hydride, sodium ethoxide, Sodamide, potassium tert-butoxide, potassium hydroxide, Tetrabutylammonium bromide or ammonium hydroxide；
Preferably, the solvent is selected from acetone, ethyl alcohol, toluene, tetrahydrofuran, n,N-Dimethylformamide, N, N- dimethyl benzene
Amine, mineral oil, dimethyl sulfoxide, acetonitrile or 1,2- dimethoxy-ethane.
4. preparation method according to claim 2 or 3, which is characterized in that the method also includes every steps after reaction
The step of purifying.
5. application of formula (I) compound as starting material or intermediate in preparation covalent organic frame material, wherein described
Covalent organic frame material is using structure shown in formula (II) as basic unit:
6. a kind of preparation method of covalent organic frame material, the covalent organic frame material is using structure shown in formula (II) as base
This unit, the preparation method is using formula (I) compound as raw material or intermediate, when R is nitro, nitro after carrying out reduction with 1,3,
(to the Fonnylphenyl) benzene of 5- tri- reaction preparation covalent organic frame material；Or when R is amino, formula (I) compound and 1,
(to the Fonnylphenyl) benzene of 3,5- tri- reaction preparation covalent organic frame material.
7. preparation method according to claim 6, which is characterized in that the described method includes: when R is amino, by formula (I)
Compound and 1,3,5- tri- (to Fonnylphenyl) benzene dissolve in a solvent, react under nitrogen protection, be centrifuged after reaction, dry
It is dry to obtain covalent organic frame material；
Alternatively, when R is nitro, after reduction nitro is amino, then with 1,3,5- tri- (to Fonnylphenyl) benzene are dissolved in solvent
In, it reacts under nitrogen protection, is centrifuged after reaction, drying obtains covalent organic frame material.
8. preparation method according to claim 7, which is characterized in that the solvent is o-dichlorohenzene, n-butanol and acetic acid
The mixed solution of aqueous solution；
Preferably, the volume ratio of the o-dichlorohenzene and n-butanol is 2-5:2-5；
Preferably, the volume ratio 2-5:0.4-1 of the n-butanol and aqueous acetic acid；
Preferably, the concentration of the aqueous acetic acid is 2-8mol/L；
Preferably, the reaction temperature is 100-150 DEG C；
Preferably, the reaction time is 48-72 hours.
9. the covalent organic frame material that preparation method described in any one of claim 6 to 8 is prepared.
10. covalent organic frame material as claimed in claim 9 is stored in gas and separation, drug conveying, catalysis or energy turn
It changes and the application in storage art.
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