CN110423357A - Aryl boron phosphonate cage compound and its synthetic method, application - Google Patents
Aryl boron phosphonate cage compound and its synthetic method, application Download PDFInfo
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- CN110423357A CN110423357A CN201910741092.1A CN201910741092A CN110423357A CN 110423357 A CN110423357 A CN 110423357A CN 201910741092 A CN201910741092 A CN 201910741092A CN 110423357 A CN110423357 A CN 110423357A
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- aryl boron
- cage compound
- boron phosphonate
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- phosphonate
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
Abstract
The present invention provides a kind of aryl boron phosphonate cage compound and its synthetic method, application.The structure of the compound such as formula [(3,5-tBu2‑Ph)PO3B (m-CN-Ph)] shown in n；In formula: m o, n 4；Or m is p, n 6.Aryl boron phosphonate cage compound of the invention, surface are modified by tert-butyl and cyano, and thermal stability is good, are used as construction unit, using the functional group of apex angle, are built three-dimensional oversubscription subframe and are provided bigger possibility.
Description
Technical field
The present invention relates to molecule cage fields, in particular to aryl boron phosphonate cage compound and its synthetic method.
Background technique
It is very beneficial that molecular design method, which has the next-generation material of particular characteristic to exploitation,.Under balance controlled,
Small sub-component (monomer) self assembly of rigidity aggregates into big component, produces the green wood for keeping permanent porosity in the solid state
Material.Active force for connecting each monomer can be the strong covalent bond in polymer, be also possible to based on metal supermolecular or
The dynamic key of dynamic covalent bond chemistry, even weak supermolecule power, such as π-π interaction, halogen bond or hydrogen bond.According to molecule
The quantity and space arrangement of functional group in structural unit, either convergence are self-assembled into limited basket structure, or diverging self assembly
It can be obtained at unlimited polymer network, such as two-dimensional layer or three-dimensional framework.Based on this method, at the past thirties years, report
Road many porous organic polymers, metal supermolecular cage compound, metal organic frame (MOFs), hydrogen bond organic frame
(HOFs), the example of covalent organic cage compound and covalent organic frame (COFs).
Structure block as nanoscale is widely studied, and is used for different applications.Compared with odaaps, boron
The chemical property of phosphate cage was explored almost without people.It would therefore be highly desirable to provide a kind of borophosphate clathrate compound.
Summary of the invention
Based on this, the present invention is mainly to provide a kind of aryl boron phosphonate cage compound.The aryl boron phosphonate caged
The surface of compound is modified by tert-butyl and cyano, has good thermal stability.
The present invention is achieved by the following technical solutions:
The present invention provides a kind of aryl boron phosphonate cage compound, the structure of the compound such as formula [(3,5-tBu2-Ph)
PO3B (m-CN-Ph)] shown in n；In formula: m o, n 4；Or m is p, n 6.
Another object of the present invention is to provide a kind of preparation method of above-mentioned aryl boron phosphonate cage compound, packets
Include following steps:
(1) 3,5- di-t-butyl phenyl-phosphonic acid and cyanophenylboronic acid is added in the reaction vessel of Xiang Shengyou solvent, in lazy
It is reacted under property atmosphere；Cyanophenylboronic acid is 4- cyanophenylboronic acid or 2- cyanophenylboronic acid；
(2) organic solvent in reaction product obtained by step (1) is removed；
(3) drying steps (2) products therefrom is re-dissolved in the in the mixed solvent of toluene and n-hexane, and recrystallization obtains aryl
Boron phosphonate cage compound.
In wherein some embodiments, in step (1), 3, the 5- di-t-butyl phenyl-phosphonic acid and cyanophenylboronic acid rub
You are than being 1:(1-2).
It is organic molten needed for 3, the 5- di-t-butyl phenyl-phosphonic acid reaction of every 81mg in step (1) in wherein some embodiments
Agent 120ml-150ml.
In wherein some embodiments, in step (1), the inert gas is nitrogen.
In wherein some embodiments, in step (1), the temperature of the reaction is 140 DEG C -155 DEG C, the reaction when
Between be 4h-8h.Time is too short, and not exclusively, the time is too long for reaction, and 3,5- di-t-butyl phenyl-phosphonic acid autohemagglutination can be made to form by-product.
In wherein some embodiments, in step (1), step (2), the organic solvent is dry toluene.This is to pass
Important, if not dry toluene, reaction cannot be carried out sufficiently, had raw material and be mixed in final product.
In wherein some embodiments, in step (3), the volume ratio of the in the mixed solvent toluene and n-hexane is 1:
(1-6).Not within this range, product can not be completely dissolved ratio, can not be recrystallized.
In wherein some embodiments, in step (3), the recrystallization (not in this temperature, is obtained using 25 DEG C -35 DEG C
Less than the crystal of well-crystallized), the time of recrystallization is 1d-3d.
Another object of the present invention is to provide the above-mentioned aryl boron phosphonate cage compound of one kind as construction unit
Application in heat stable material is prepared building Magnetic Properties of Three-Dimensional Supramolecular Complex frame.
Compared with prior art, the present invention have it is following the utility model has the advantages that
Aryl boron phosphonate cage compound of the invention, surface are modified by tert-butyl and cyano, and thermal stability is good, are made
It builds three-dimensional oversubscription subframe using the functional group of apex angle for construction unit and provides bigger possibility.
Detailed description of the invention
Fig. 1 is [(3,5- prepared by the present inventiontBu2-Ph)PO3B(p-CN-Ph)]6Basic cell structure figure.
Fig. 2 is [(3,5- prepared by the present inventiontBu2-Ph)PO3B(o-CN-Ph)]4Basic cell structure figure.
Fig. 3 is [(3,5- prepared by the present inventiontBu2-Ph)PO3B(p-CN-Ph)]6Accumulation graph.
Fig. 4 is [(3,5- prepared by the present inventiontBu2-Ph)PO3B(o-CN-Ph)]4Accumulation graph.
Fig. 5 is [(3,5- prepared by the present inventiontBu2-Ph)PO3B(p-CN-Ph)]6Thermal multigraph.
Fig. 6 is [(3,5- prepared by the present inventiontBu2-Ph)PO3B(o-CN-Ph)]4Thermal multigraph.
Fig. 7 is [(3,5- prepared by the present inventiontBu2-Ph)PO3B(p-CN-Ph)]6、[(3,5-tBu2-Ph)PO3B(o-CN-
Ph)]4Structural schematic diagram.
Specific embodiment
It to facilitate the understanding of the present invention, below will be to invention is more fully described.But the present invention can be to be permitted
Mostly different form is realized, however it is not limited to embodiment described herein.On the contrary, purpose of providing these embodiments is makes
It is more thorough and comprehensive to the understanding of the disclosure.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases
Any and all combinations of the listed item of pass.
The preparation of embodiment 1,3,5- di-t-butyl phenyl-phosphonic acid organic ligand
The present embodiment is related to the preparation method of one kind 3,5- di-t-butyl phenyl-phosphonic acid organic ligand, specifically includes following step
It is rapid:
(1) by 3, the 5- di-t-butyl bromobenzene of 1.61gWith the Dehydrated nickel chloride (NiCl of 0.1g2) plus
Enter the triethyl phosphite to 1.4mlIn, reaction 36 hours is carried out at nitrogen atmosphere, 160 DEG C,
After dropping to room temperature, uses the ethyl acetate and n-hexane that ratio is 1:1 as eluant, eluent, crude product is carried out with silica gel column chromatography
It isolates and purifies.
(2) product after purification is added in the hydrochloric acid of 6M/L, and after reacting 24 hours at 110 DEG C, rotary evaporation removes molten
3, the 5- di-t-butyl phenyl-phosphonic acid of 1.32g, yield 82% are obtained after agent.
Embodiment 2, [(3,5-tBu2-Ph)PO3B(p-CN-Ph)]6Preparation
The present embodiment is related to [(3,5-tBu2-Ph)PO3B(p-CN-Ph)]6The preparation side of (result schematic diagram is referring to Fig. 7)
Method specifically comprises the following steps:
(1) the 4- cyanophenylboronic acid of 3, the 5- di-t-butyl phenyl-phosphonic acid of 81mg obtained in embodiment 1 and 45mg are added
In round-bottomed flask equipped with 120ml toluene, a water segregator is connected on flask, water segregator reconnects a spherical condensation tube, makes
Carry out reaction under nitrogen atmosphere with three discharge technique of threeway, 145 DEG C of reaction 5h.
(2) step (1) after reaction, removes the toluene solvant in reaction product using rotary evaporation, obtains white powder
End.
(3) by after the vacuum drying of white powder obtained by step (2), be dissolved in toluene: n-hexane is the mixed solvent of 1:5
In, it recrystallizes at room temperature；After three days, colorless and transparent square crystal, i.e. aryl boron phosphonate cage compound are obtained.
The structure of gained aryl boron phosphonate cage compound is by Agilent Technologies SuperNova
Single crystal diffractometer test determination, test result shows:
[(3,5-tBu2-Ph)PO3B(p-CN-Ph)]6Crystal belong to anorthic system, space group P-1, cell parameter isα=104.94 °, β=102.13 °, γ=106.57 °, unit cell volume
For
Gained aryl boron phosphonate cage compound is a cage structure, and surface is modified by tert-butyl and cyano, the cage
Shape compound can be described as by the [(3,5- of two Unit 12tBu2-Ph)PO3B(p-CN-Ph)]3The dimer of big ring composition,
It is keyed between two big ring by P-O-B.
In this example, the 4- cyanophenylboronic acid heats in advance to be dissolved in distilled water, after being cooled to room temperature, is obtained colorless and transparent
Strip crystal, filtering, carries out subsequent experimental again after vacuum drying.
In this example, the toluene and n-hexane carry out purification process in advance.It is added into metallic sodium heating stirring, two
Benzophenone is heated to reflux after becoming blue to benzophenone as indicator, then is evaporated under reduced pressure out anhydrous toluene and n-hexane.
The basic cell structure figure of aryl boron phosphonate cage compound obtained in this example is shown in Fig. 1, is one
Cage structure, surface are modified by tert-butyl and cyano, which can be described as by [(the 3,5- of two 12 yuantBu2-
Ph)PO3B(p-CN-Ph)]3The dimer of big ring composition passes through P-O-B key connection between two big ring.
The accumulation graph of aryl boron phosphonate cage compound obtained in this example is shown in that Fig. 3, each caged unit are direct
Three-dimensional Supramolecular Network frame is formed by π-π and hydrogen bond action.
Test the thermal stability of gained aryl boron phosphonate cage compound crystal, aryl boron obtained in this example
The thermal multigraph of phosphonate cage compound is shown in Fig. 5, and 30 DEG C -120 DEG C have about 10.1% weight to lose, and is attributed to toluene and just
Hexane solvent molecule loses, and crystal structure just collapses completely up to 300 DEG C or so, shows that crystal has good thermostabilization
Performance.
Embodiment 3, [(3,5-tBu2-Ph)PO3B(o-CN-Ph)]4Preparation
The present embodiment is related to [(3,5-tBu2-Ph)PO3B(o-CN-Ph)]4The preparation side of (result schematic diagram is referring to Fig. 7)
Method specifically comprises the following steps:
(1) by 3, the 5- di-t-butyl phenyl-phosphonic acid of 81mg obtained in embodiment 1 respectively with the 2- cyanophenylboronic acid of 45mg
It is added in the round-bottomed flask equipped with 120ml toluene, a water segregator is connected on flask, water segregator reconnects a bulb condensation
Pipe carries out reaction under nitrogen atmosphere using three discharge technique of threeway, 145 DEG C of reaction 5h.
(2) step (1) after reaction, removes toluene solvant using rotary evaporation, obtains white powder.
(3) by after the vacuum drying of step (2) white powder, be dissolved in toluene: n-hexane is the in the mixed solvent of 1:5,
It recrystallizes at room temperature；After one day, colorless and transparent square crystal, i.e. aryl boron phosphonate cage compound are obtained.
The structure of gained aryl boron phosphonate cage compound is by Agilent Technologies SuperNova
Single crystal diffractometer test determination, test result shows:
[(3,5-tBu2-Ph)PO3B(o-CN-Ph)]4Crystal belong to tetragonal crystal system, space group I-4, cell parameter isα=β=γ=90 °, unit cell volume are
Gained aryl boron phosphonate cage compound is a cube of basket structure, and surface is modified by tert-butyl and cyano, should
Cage compound can be described as by two 8 yuan of [(3,5-tBu2-Ph)PO3B(o-CN-Ph)]2The dimer of big ring composition,
It is keyed between two big ring by P-O-B.
In this example, the basic cell structure figure of aryl boron phosphonate cage compound obtained is shown in Fig. 2, is one
Cube basket structure, surface are modified by tert-butyl and cyano, which can be described as by [(the 3,5- of two 8 yuantBu2-
Ph)PO3B(o-CN-Ph)]2The dimer of big ring composition passes through P-O-B key connection between two big ring.
The structure chart of aryl boron phosphonate cage compound obtained in this example is shown in that Fig. 4, each caged unit are direct
Three-dimensional Supramolecular Network frame is formed by π-π and hydrogen bond action.
Test the thermal stability of gained crystal, the thermogravimetric of aryl boron phosphonate cage compound obtained in this example
Figure is shown in Fig. 6, and 30 DEG C -115 DEG C have about 9.9% weight to lose, and is attributed to losing for toluene and n-hexane solvent molecule, crystal
Structure is just collapsed completely up to 300 DEG C or so, shows that crystal has good thermal stability.
Embodiment 4
The present embodiment is the change case of embodiment 2, and variation place is as follows:
In step (1), the temperature of the reaction is 140 DEG C, and the time of the reaction is 4h.
In step (3), the volume ratio of the in the mixed solvent toluene and n-hexane is 1:1.
In step (3), the recrystallization uses 25 DEG C, and the time of recrystallization is 1d.
Final result is the same as embodiment 2.
Embodiment 5
The present embodiment is the change case of embodiment 2, and variation place is as follows:
In step (1), the temperature of the reaction is 155 DEG C, and the time of the reaction is 8h.
In step (3), the volume ratio of the in the mixed solvent toluene and n-hexane is 1:6.
In step (3), the recrystallization uses 35 DEG C, and the time of recrystallization is 3d.
Final result is the same as embodiment 2.
Comparative example 1
This comparative example is the comparative example of embodiment 2, and comparison place includes:
In step (1), the temperature of the reaction is 160 DEG C, and the time of the reaction is 9h.
As a result, the time is too long, 3,5- di-t-butyl phenyl-phosphonic acid autohemagglutination can be made to form by-product.
Comparative example 2
This comparative example is the comparative example of embodiment 2, and comparison place includes: step (1), in step (2), the organic solvent
Toluene is replaced using dimethylbenzene.
As a result, reaction cannot be carried out sufficiently, many raw materials are mixed in final product.
Comparative example 3
This comparative example is the comparative example of embodiment 2, and comparison place includes:
In step (3), the volume ratio of in the mixed solvent toluene and n-hexane is 1:0.5, and recrystallization temperature uses 22 DEG C.
As a result, product can not be completely dissolved, can not be recrystallized.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. aryl boron phosphonate cage compound, which is characterized in that the structure of the compound such as formula [(3,5-tBu2-Ph)PO3B
(m-CN-Ph)]nIt is shown；In formula: m o, n 4；Or m is p, n 6.
2. the preparation method of aryl boron phosphonate cage compound described in claim 1, which is characterized in that including walking as follows
It is rapid:
(1) 3,5- di-t-butyl phenyl-phosphonic acid and cyanophenylboronic acid is added in the reaction vessel of Xiang Shengyou solvent, in indifferent gas
It is reacted under body atmosphere；Cyanophenylboronic acid is 4- cyanophenylboronic acid or 2- cyanophenylboronic acid；
(2) organic solvent in reaction product obtained by step (1) is removed；
(3) drying steps (2) products therefrom is re-dissolved in the in the mixed solvent of toluene and n-hexane, and recrystallization obtains aryl boron phosphine
Hydrochlorate cage compound.
3. the preparation method of aryl boron phosphonate cage compound as claimed in claim 2, which is characterized in that in step (1), institute
The molar ratio for stating 3,5- di-t-butyl phenyl-phosphonic acid and cyanophenylboronic acid is 1:(1-2).
4. the preparation method of aryl boron phosphonate cage compound as claimed in claim 2, which is characterized in that in step (1), often
Organic solvent 120ml-150ml needed for 3, the 5- di-t-butyl phenyl-phosphonic acid of 81mg reacts.
5. the preparation method of aryl boron phosphonate cage compound as claimed in claim 2, which is characterized in that in step (1), institute
Stating inert gas is nitrogen.
6. the preparation method of aryl boron phosphonate cage compound as claimed in claim 2, which is characterized in that in step (1), institute
The temperature for stating reaction is 140 DEG C -155 DEG C, and the time of the reaction is 4h-8h.
7. the preparation method of aryl boron phosphonate cage compound as claimed in claim 2, which is characterized in that step (1), step
(2) in, the organic solvent is dry toluene.
8. the preparation method of aryl boron phosphonate cage compound as claimed in claim 2, which is characterized in that in step (3), institute
The volume ratio for stating in the mixed solvent toluene and n-hexane is 1:(1-6).
9. the preparation method of aryl boron phosphonate cage compound as claimed in claim 2, which is characterized in that in step (3), institute
Recrystallization is stated using 25 DEG C -35 DEG C, the time of recrystallization is 1d-3d.
10. aryl boron phosphonate cage compound described in claim 1 is building Magnetic Properties of Three-Dimensional Supramolecular Complex frame as construction unit
Prepare the application in heat stable material.
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| CN108467413A (en) * | 2018-03-27 | 2018-08-31 | 北京师范大学 | Cage compound, molecular capsule based on bowl alkene and the preparation method and application thereof |
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2019
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|---|---|---|---|---|
| US7989527B2 (en) * | 2003-03-20 | 2011-08-02 | Universite Laval | Polymer nanocomposites based on synthesized lamellar nanoparticles |
| CN108148205A (en) * | 2016-12-02 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of preparation method of the integral material based on organic molecule cage |
| CN108467413A (en) * | 2018-03-27 | 2018-08-31 | 北京师范大学 | Cage compound, molecular capsule based on bowl alkene and the preparation method and application thereof |
Non-Patent Citations (2)
| Title |
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| JULIAN ZAPICO等: "Borophosphonate cages as element-blocks: ab initio calculation of the electronic structure of a simple borophosphonate, [HPO3BH]4, and synthesis of two novel borophosphonate cages with polymerizable groups", 《CHEMISTRY LETTERS》 * |
| QIAN LIU等: "Synthesis of Boro -phosphonate Cage Compounds: Influence of Substituent and Concentration Effects on Product Distribution in Condensation Reactions of Aryl Phosphonic Acids and Boronic Acids", 《AMERICAN CHEMICAL SOCIETY》 * |
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Application publication date: 20191108 |