CN108117567A - A kind of four (4- boric acid phenyl) adamantane and preparation method thereof - Google Patents
A kind of four (4- boric acid phenyl) adamantane and preparation method thereof Download PDFInfo
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- CN108117567A CN108117567A CN201611082494.8A CN201611082494A CN108117567A CN 108117567 A CN108117567 A CN 108117567A CN 201611082494 A CN201611082494 A CN 201611082494A CN 108117567 A CN108117567 A CN 108117567A
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- adamantane
- boric acid
- acid phenyl
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- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 title claims abstract description 177
- 239000004327 boric acid Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims abstract description 19
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000013310 covalent-organic framework Substances 0.000 claims abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 52
- 238000003756 stirring Methods 0.000 claims description 50
- 238000006243 chemical reaction Methods 0.000 claims description 37
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 239000012043 crude product Substances 0.000 claims description 22
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000012265 solid product Substances 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000003809 water extraction Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- -1 triisopropyl borate ester Chemical class 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 3
- KCZDTZZRNNRKQE-UHFFFAOYSA-N 1-(4-bromophenyl)adamantane Chemical compound C1=CC(Br)=CC=C1C1(C2)CC(C3)CC2CC3C1 KCZDTZZRNNRKQE-UHFFFAOYSA-N 0.000 abstract 1
- DMMVHLXCUOFVFH-UHFFFAOYSA-N 1-(4-iodophenyl)adamantane Chemical compound C1=CC(I)=CC=C1C1(C2)CC(C3)CC2CC3C1 DMMVHLXCUOFVFH-UHFFFAOYSA-N 0.000 abstract 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 abstract 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 22
- 150000002148 esters Chemical class 0.000 description 19
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 19
- 238000012512 characterization method Methods 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 238000001819 mass spectrum Methods 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 6
- 125000006306 4-iodophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1I 0.000 description 5
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 239000013490 COF-103 Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 238000000119 electrospray ionisation mass spectrum Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The present invention provides a kind of four (4 boric acid phenyl) adamantane and preparation method thereof, four (4 boric acid phenyl) adamantane are first to be reacted by four (4 bromophenyl) adamantane or four (4 iodophenyl) adamantane with n-BuLi, nucleophilic substitution occurs with borate again, is finally obtained with dilute hydrochloric acid acidolysis.The obtained product four of the invention (4 boric acid phenyl) adamantane has that accessible phenyl ring number is more, symmetry is high, rigidity is good, and becoming synthesis has the new monomer material of COFs of more bigger serface.
Description
Technical field
The present invention relates to chemosynthesis technical fields, are related to a kind of four (4- boric acid phenyl) adamantane and preparation method thereof.
Background technology
Covalent organic framework material (Covalent Organic Frameworks, COFs) is since its is larger in recent years
Specific surface area, duct are homogeneous, and with characteristics such as high thermal stability and good chemical stabilities, in gas absorption with dividing
There is preferable application from, energy storage and catalysis etc., therefore once it is found that having attracted everybody concern.Three-dimensional COFs is most main
The side knead dough for being characterized in its duct inner structure unit is wanted also to can contact.Specific surface area is bigger, and active site is more.At present
COFs maximums BET specific surface area is 4210m2/g(COF-103).Yaghi once reported that the aromatic rings of exposure in porous material was got over
More, then its specific surface area is bigger.However the structural unit of the synthesis COFs reported at present is limited, therefore current synthesis has bigger
Overriding challenge existing for the COFs of specific surface area is exactly to design novel monomeric materials.
The interspersed number of plies of boric acid class COFs is few, and the active site of the gas absorption exposed and catalysis is relatively more.In addition
Adamantane compound is a kind of caged hydrocarbon compound of high degree of symmetry, rigid structure, after COFs is synthesized, tetrahedral structure
It remains to keep well.Therefore combine the advantages of boric acid and adamantane, it is more, right with accessible phenyl ring number to design
New monomer four (4- boric acid phenyl) adamantane that title degree is high, rigidity is good.
The content of the invention
The invention solves primary technical problem be to provide a kind of new monomer four (4- boric acid phenyl) adamantane.
Four (4- boric acid phenyl) adamantane material of the present invention, structural formula are as follows：
A kind of preparation method of four (4- boric acid phenyl) adamantane, specifically carries out in accordance with the following steps：
(1) under nitrogen protection, n-BuLi is added dropwise into the tetrahydrofuran solution of four (4-X- phenyl) adamantane, control is anti-
Temperature -80~0 DEG C is answered, stirs 0.5~3h, rises to -20~25 DEG C of 30~120min of stirring thereafter；
The X is Br or I；
The concentration of described four (4-X- phenyl) adamantane is：0.0065~0.052moL/L
The molar ratio of four (4-X- phenyl) adamantane and n-BuLi is：1:5~89；
(2) reaction solution that (1) obtains is cooled to -80~0 DEG C, and triisopropyl borate ester is added dropwise thereto, stirring 30~
80min then heats to room temperature and stirs；Stir 10 it is small when tetrahydrofuran, n-BuLi and triisopropyl borate ester described in body
Product is than being 10~50:1~10：5~20.
(3) it is quenched with dilute hydrochloric acid, adjusts pH to 3~4, and 3~10h is stirred at 0~25 DEG C；
(4) tetrahydrofuran and the unreacted triisopropyl borate ester in second step reaction solution are removed with Rotary Evaporators, is obtained
To solid product；The solid product is dissolved with dichloromethane, then adds in water extraction, water phase is collected and filters, obtain four (4- boron
Sour phenyl) adamantane crude product；It will be in the crude product dimethyl sulfoxide, methanol, acetone of four (4- boric acid phenyl) adamantane
It is a kind of to be recrystallized, obtain four pure (4- boric acid phenyl) adamantane.
The concentration of (4-X- phenyl) adamantane is preferred four described in step (1)：0.0104~0.026moL/L, four (4-X-
Phenyl) molar ratio of adamantane and n-BuLi is preferably 1:17.9~59.5；Controlling reaction temperature is preferably -78~40 DEG C.
In step (2), the reaction temperature is preferably -78~40 DEG C；Three isopropyl of tetrahydrofuran, n-BuLi and boric acid
The volume ratio of ester is preferably 15~40:3~8：5~20；
Tune pH described in step (3) is preferably 3.3~3.8；8~10h is stirred at preferably 25 DEG C.In step (3), institute
The reagent of recrystallization four (the 4- boric acid phenyl) adamantane stated is preferably dimethyl sulfoxide or methanol.
A kind of application of four (4- boric acid phenyl) adamantane, it is characterised in that four described (the 4- boric acid phenyl) adamantane are used
In the new monomer material of COFs of the synthesis with more bigger serface.
The reaction equation of preparation method of the present invention is as follows：
Wherein, X is Br or I.
Compared with prior art, the present invention has following advantageous effect：
1st, the present invention for the first time combines adamantane and boric acid.The material not only has the caged rigid structure of high degree of symmetry,
Its tetrahedral structure remains to keep well after COFs is synthesized；And the COFs synthesized interts the gas that the number of plies is few, exposes
The active site of absorption and catalysis is relatively more, therefore the material is expected to become the new list of COFs of the synthesis with more bigger serface
Body material.
Description of the drawings
Fig. 1 is four (4- boric acid phenyl) adamantane1H-NMR.
Fig. 2 is Fourier transform infrared spectroscopy spectrogram.
Specific embodiment
The present invention is further described and explained with reference to specific embodiment, but does not limit the protection model of the present invention
It encloses.
Embodiment 1
The preparation of four (4- boric acid phenyl) adamantane
1. under the protection of first step nitrogen, to (0.4g, 0.52mmol) four (4- bromophenyl) of the structural formula as shown in formula (II)
The n-BuLi of 4mL is added dropwise in (31mL) tetrahydrofuran solution of adamantane, -78 DEG C of controlling reaction temperature stirs 0.5h, thereafter
Rise to 0 DEG C of stirring 50min；
2. the reaction solution that second step obtains the first step is cooled to -78 DEG C, and three isopropyl of boric acid of 5mL is added dropwise thereto
Ester stirs 30min, then heats to room temperature and be stirred overnight；
3. the 3rd step is quenched with dilute hydrochloric acid, pH is adjusted to 3.5, and stirs 9h at 0 DEG C.
4. the 4th step removes three isopropyl of tetrahydrofuran and unreacted boric acid in second step reaction solution with Rotary Evaporators
Ester obtains solid product.The solid product is dissolved with dichloromethane, then adds in water extraction, water phase is collected and filters, obtain four
The crude product of (4- boric acid phenyl) adamantane.The crude product with methanol of four (4- boric acid phenyl) adamantane is recrystallized, is obtained
To four pure (4- boric acid phenyl) adamantane, yield 50%.
Obtained product is characterized using mass spectrum, nucleus magnetic hydrogen spectrum,1H-NMR is as shown in Figure 1, Fourier transform infrared spectroscopy
Spectrogram is as shown in Figure 2.
Structural characterization data are as follows：
Electrospray ionization mass spectrum ESI-MS characterization results are, the molecular weight that cation mode measures is 616.28 and four (4- boric acid
Phenyl) adamantane molecular weight it is consistent.
Hydrogen is composed1H-NMR(400MHz,DMSO,ppm):7.96(s,8H,OH),7.78(d,8H),7.54(d,8H),2.09
(s,12H)。
IR(KBr,v/cm-1) characterization result be 3419.2,3083.6,2925.4,2898.4,2846.9,1611.5,
1404.7,1342.4,1125.0,1016.3,829.3,751.7,715.2,653.7。
Therefore it proves successfully to have obtained four (4- boric acid phenyl) adamantane through characterization.
Embodiment 2
The preparation of four (4- boric acid phenyl) adamantane
1. under the protection of first step nitrogen, to (0.4g, 0.42mmol) four (4- iodophenyl) of the structural formula as shown in formula (II)
The n-BuLi of 4mL is added dropwise in (35mL) tetrahydrofuran solution of adamantane, -78 DEG C of controlling reaction temperature stirs 0.5h, thereafter
Rise to 0 DEG C of stirring 50min；
2. the reaction solution that second step obtains the first step is cooled to -78 DEG C, and three isopropyl of boric acid of 5mL is added dropwise thereto
Ester stirs 30min, then heats to room temperature and be stirred overnight；
3. the 3rd step is quenched with dilute hydrochloric acid, pH is adjusted to 3.8, and stirs 9h at 0 DEG C.
4. the 4th step removes three isopropyl of tetrahydrofuran and unreacted boric acid in second step reaction solution with Rotary Evaporators
Ester obtains solid product.The solid product is dissolved with dichloromethane, then adds in water extraction, water phase is collected and filters, obtain four
The crude product of (4- boric acid phenyl) adamantane.The crude product with methanol of four (4- boric acid phenyl) adamantane is recrystallized, is passed through
Mass spectrum, nucleus magnetic hydrogen spectrum and IR Characterization product be four (4- boric acid phenyl) adamantane, yield 38%.
Embodiment 3
The preparation of four (4- boric acid phenyl) adamantane
1. under the protection of first step nitrogen, to (0.4g, 0.52mmol) four (4- bromophenyl) of the structural formula as shown in formula (II)
The n-BuLi of 3mL is added dropwise in (40mL) tetrahydrofuran solution of adamantane, -78 DEG C of controlling reaction temperature stirs 1.5h, thereafter
Rise to 0 DEG C of stirring 30min；
2. the reaction solution that second step obtains the first step is cooled to -78 DEG C, and three isopropyl of boric acid of 2mL is added dropwise thereto
Ester stirs 40min, then heats to room temperature and stir 10h；
3. the 3rd step is quenched with dilute hydrochloric acid, adjusts pH to 3.3 and stir 10h at 25 DEG C.
4. the 4th step removes three isopropyl of tetrahydrofuran and unreacted boric acid in second step reaction solution with Rotary Evaporators
Ester obtains solid product.The solid product is dissolved with dichloromethane, then adds in water extraction, water phase is collected and filters, obtain four
The crude product of (4- boric acid phenyl) adamantane.The crude product of four (4- boric acid phenyl) adamantane is tied again with dimethyl sulfoxide
Crystalline substance, through mass spectrum, nucleus magnetic hydrogen spectrum and IR Characterization product be four (4- boric acid phenyl) adamantane, yield 52%.
Embodiment 4
The preparation of four (4- boric acid phenyl) adamantane
1. under the protection of first step nitrogen, to (0.4g, 0.42mmol) four (4- iodophenyl) of the structural formula as shown in formula (II)
The n-BuLi of 5mL is added dropwise in (50mL) tetrahydrofuran solution of adamantane, -78 DEG C of controlling reaction temperature stirs 1.5h, thereafter
Rise to 0 DEG C of stirring 30min；
2. the reaction solution that second step obtains the first step is cooled to -78 DEG C, and three isopropyl of boric acid of 10mL is added dropwise thereto
Ester stirs 40min, then heats to room temperature and stir 10h；
3. the 3rd step is quenched with dilute hydrochloric acid, pH is adjusted to 3.0, and stirs 10h at 25 DEG C.
4. the 4th step removes three isopropyl of tetrahydrofuran and unreacted boric acid in second step reaction solution with Rotary Evaporators
Ester obtains solid product.The solid product is dissolved with dichloromethane, then adds in water extraction, water phase is collected and filters, obtain four
The crude product of (4- boric acid phenyl) adamantane.The crude product of four (4- boric acid phenyl) adamantane is tied again with dimethyl sulfoxide
Crystalline substance, through mass spectrum, nucleus magnetic hydrogen spectrum and IR Characterization product be four (4- boric acid phenyl) adamantane, yield 52%.
Embodiment 5
The preparation of four (4- boric acid phenyl) adamantane
1. under the protection of first step nitrogen, to (0.4g, 0.52mmol) four (4- bromophenyl) of the structural formula as shown in formula (II)
The n-BuLi of 10mL is added dropwise in (50mL) tetrahydrofuran solution of adamantane, -40 DEG C of controlling reaction temperature stirs 0.5h,
After rise to 0 DEG C stirring 50min；
2. the reaction solution that second step obtains the first step is cooled to -78 DEG C, and three isopropyl of boric acid of 15mL is added dropwise thereto
Ester stirs 30min, then heats to room temperature and be stirred overnight；
3. the 3rd step is quenched with dilute hydrochloric acid, adjusts pH to 3.8 and stir 3h at 0 DEG C.
4. the 4th step removes three isopropyl of tetrahydrofuran and unreacted boric acid in second step reaction solution with Rotary Evaporators
Ester obtains solid product.The solid product is dissolved with dichloromethane, then adds in water extraction, water phase is collected and filters, obtain four
The crude product of (4- boric acid phenyl) adamantane.The crude product of four (4- boric acid phenyl) adamantane is tied again with dimethyl sulfoxide
Crystalline substance, through mass spectrum, nucleus magnetic hydrogen spectrum and IR Characterization product be four (4- boric acid phenyl) adamantane, yield 30%.
Embodiment 6
The preparation of four (4- boric acid phenyl) adamantane
1. under the protection of first step nitrogen, to (0.4g, 0.42mmol) four (4- iodophenyl) of the structural formula as shown in formula (II)
The n-BuLi of 12mL is added dropwise in (60mL) tetrahydrofuran solution of adamantane, -40 DEG C of controlling reaction temperature stirs 0.5h,
After rise to 0 DEG C stirring 50min；
2. the reaction solution that second step obtains the first step is cooled to -78 DEG C, and three isopropyl of boric acid of 25mL is added dropwise thereto
Ester stirs 30min, then heats to room temperature and be stirred overnight；
3. the 3rd step is quenched with dilute hydrochloric acid, pH is adjusted to 3.3, and stirs 3h at 0 DEG C.
4. the 4th step removes three isopropyl of tetrahydrofuran and unreacted boric acid in second step reaction solution with Rotary Evaporators
Ester obtains solid product.The solid product is dissolved with dichloromethane, then adds in water extraction, water phase is collected and filters, obtain four
The crude product of (4- boric acid phenyl) adamantane.The crude product of four (4- boric acid phenyl) adamantane is tied again with dimethyl sulfoxide
Crystalline substance, through mass spectrum, nucleus magnetic hydrogen spectrum and IR Characterization product be four (4- boric acid phenyl) adamantane, yield 29%.
Embodiment 7
The preparation of four (4- boric acid phenyl) adamantane
1. under the protection of first step nitrogen, to (0.4g, 0.42mmol) four (4- iodophenyl) of the structural formula as shown in formula (II)
The n-BuLi of 4mL is added dropwise in (35mL) tetrahydrofuran solution of adamantane, -78 DEG C of controlling reaction temperature stirs 2h, rises thereafter
To 0 DEG C of stirring 30min；
2. the reaction solution that second step obtains the first step is cooled to -78 DEG C, and three isopropyl of boric acid of 15mL is added dropwise thereto
Ester stirs 30min, then heats to room temperature and stir 10h；
3. the 3rd step is quenched with dilute hydrochloric acid, pH is adjusted to 3.3, and stirs 3h at 0 DEG C.
4. the 4th step removes three isopropyl of tetrahydrofuran and unreacted boric acid in second step reaction solution with Rotary Evaporators
Ester obtains solid product.The solid product is dissolved with dichloromethane, then adds in water extraction, water phase is collected and filters, obtain four
The crude product of (4- boric acid phenyl) adamantane.The crude product of four (4- boric acid phenyl) adamantane is tied again with dimethyl sulfoxide
Crystalline substance, through mass spectrum, nucleus magnetic hydrogen spectrum and IR Characterization product be four (4- boric acid phenyl) adamantane, yield 40%.
Embodiment 8
The preparation of four (4- boric acid phenyl) adamantane
1. under the protection of first step nitrogen, to (0.4g, 0.52mmol) four (4- bromophenyl) of the structural formula as shown in formula (II)
The n-BuLi of 4mL is added dropwise in (35mL) tetrahydrofuran solution of adamantane, -40 DEG C of controlling reaction temperature stirs 0.5h, thereafter
Rise to 0 DEG C of stirring 50min；
2. the reaction solution that second step obtains the first step is cooled to -40 DEG C, and three isopropyl of boric acid of 15mL is added dropwise thereto
Ester stirs 30min, then heats to room temperature and be stirred overnight；
3. the 3rd step is quenched with dilute hydrochloric acid, pH is adjusted to 4.0, and stirs 3h at 25 DEG C.
4. the 4th step removes three isopropyl of tetrahydrofuran and unreacted boric acid in second step reaction solution with Rotary Evaporators
Ester obtains solid product.The solid product is dissolved with dichloromethane, then adds in water extraction, water phase is collected and filters, obtain four
The crude product of (4- boric acid phenyl) adamantane.The crude product of four (4- boric acid phenyl) adamantane with acetone is recrystallized, is passed through
Mass spectrum, nucleus magnetic hydrogen spectrum and IR Characterization product be four (4- boric acid phenyl) adamantane, yield 16%.
Embodiment 9
The preparation of four (4- boric acid phenyl) adamantane
1. under the protection of first step nitrogen, to (0.4g, 0.42mmol) four (4- iodophenyl) of the structural formula as shown in formula (II)
The n-BuLi of 4mL is added dropwise in (35mL) tetrahydrofuran solution of adamantane, -78 DEG C of controlling reaction temperature stirs 0.5h, thereafter
Rise to 0 DEG C of stirring 50min；
2. the reaction solution that second step obtains the first step is cooled to -40 DEG C, and three isopropyl of boric acid of 15mL is added dropwise thereto
Ester stirs 30min, then heats to room temperature and stir 10h；
3. the 3rd step is quenched with dilute hydrochloric acid, pH is adjusted to 3.9, and stirs 3h at 0 DEG C.
4. the 4th step removes three isopropyl of tetrahydrofuran and unreacted boric acid in second step reaction solution with Rotary Evaporators
Ester obtains solid product.The solid product is dissolved with dichloromethane, then adds in water extraction, water phase is collected and filters, obtain four
The crude product of (4- boric acid phenyl) adamantane.The crude product of four (4- boric acid phenyl) adamantane with acetone is recrystallized, is passed through
Mass spectrum, nucleus magnetic hydrogen spectrum and IR Characterization product be four (4- boric acid phenyl) adamantane, yield 15%.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring the substantive content of the present invention.
Claims (7)
- One kind four 1. (4- boric acid phenyl) adamantane, it is characterised in that molecular structural formula is as follows：
- The preparation method of one kind four 2. (4- boric acid phenyl) adamantane, it is characterised in that carry out in accordance with the following steps：(1) under nitrogen protection, n-BuLi, control reaction temperature are added dropwise into the tetrahydrofuran solution of four (4-X- phenyl) adamantane - 80~0 DEG C of degree stirs 0.5~3h, rises to -20~25 DEG C of 30~120min of stirring thereafter；The X is Br or I；The concentration of described four (4-X- phenyl) adamantane is：0.0065~0.052moL/L；The molar ratio of four (4-X- phenyl) adamantane and n-BuLi is：1:5~89；(2) reaction solution that (1) obtains is cooled to -80~0 DEG C, and triisopropyl borate ester is added dropwise thereto, stirring 30~ 80min then heats to room temperature and stirs；Stir 10 it is small when；The body of the tetrahydrofuran, n-BuLi and triisopropyl borate ester Product is than being 10~50:1~10：5~20；(3) it is quenched with dilute hydrochloric acid, adjusts pH to 3~4, and 3~10h is stirred at 0~25 DEG C；(4) tetrahydrofuran and the unreacted triisopropyl borate ester in second step reaction solution are removed with Rotary Evaporators, consolidate Body product；The solid product is dissolved with dichloromethane, then adds in water extraction, water phase is collected and filters, obtain four (4- boric acid benzene Base) adamantane crude product；By one kind in the crude product dimethyl sulfoxide, methanol, acetone of four (4- boric acid phenyl) adamantane It is recrystallized, obtains four pure (4- boric acid phenyl) adamantane.
- 3. the preparation method of four (4- boric acid phenyl) adamantane described in accordance with the claim 2, it is characterised in that：In step (1) The concentration of described four (4-X- phenyl) adamantane is preferred：0.0104~0.026moL/L, four (4-X- phenyl) adamantane and positive fourth The molar ratio of base lithium is preferably 1:17.9~59.5；The preferred volume of the tetrahydrofuran, n-BuLi and triisopropyl borate ester Than for 15~40:3~8：5~20, controlling reaction temperature is preferably -78~40 DEG C.
- 4. the preparation method of four (4- boric acid phenyl) adamantane described in accordance with the claim 2, it is characterised in that：In step (2), The reaction temperature is preferably -78~40 DEG C.
- 5. the preparation method of four (4- boric acid phenyl) adamantane described in accordance with the claim 2, it is characterised in that：In step (3) The tune pH is preferably 3.3~3.8；8~10h is stirred at preferably 25 DEG C.
- 6. the preparation method of four (4- boric acid phenyl) adamantane described in accordance with the claim 2, it is characterised in that：In step (3), The reagent of described recrystallization four (the 4- boric acid phenyl) adamantane is preferably dimethyl sulfoxide or methanol.
- 7. the application of four (4- boric acid phenyl) adamantane of one kind as described in claim 1, it is characterised in that four (the 4- boric acid Phenyl) adamantane for synthesize with more bigger serface COFs new monomer material.
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| CN115524427A (en) * | 2022-11-28 | 2022-12-27 | 质谱生物科技有限公司 | Detection method of catecholamine hormones |
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