CN108117567B - Tetra (4-boranophenyl) adamantane and preparation method thereof - Google Patents
Tetra (4-boranophenyl) adamantane and preparation method thereof Download PDFInfo
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- LYJCLXIGWFHNIF-UHFFFAOYSA-N C1(=C2C(=CC=C1)B2)C2C1CC3CC(CC2C3)C1 Chemical compound C1(=C2C(=CC=C1)B2)C2C1CC3CC(CC2C3)C1 LYJCLXIGWFHNIF-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims abstract description 40
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 52
- 238000003756 stirring Methods 0.000 claims description 46
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 38
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- 239000012295 chemical reaction liquid Substances 0.000 claims description 32
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 26
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical compound CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-UHFFFAOYSA-N 0.000 claims description 26
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 239000012265 solid product Substances 0.000 claims description 22
- 239000012043 crude product Substances 0.000 claims description 21
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000010791 quenching Methods 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 claims 1
- 239000013310 covalent-organic framework Substances 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 7
- HTGPRXPCTBXRBH-UHFFFAOYSA-N 1,3,5,7-tetrakis(4-iodophenyl)adamantane Chemical compound C1=CC(I)=CC=C1C1(CC(C2)(C3)C=4C=CC(I)=CC=4)CC2(C=2C=CC(I)=CC=2)CC3(C=2C=CC(I)=CC=2)C1 HTGPRXPCTBXRBH-UHFFFAOYSA-N 0.000 abstract description 6
- SBWXPELEFUNJFA-UHFFFAOYSA-N 1,3,5,7-tetrakis(4-bromophenyl)adamantane Chemical compound C1=CC(Br)=CC=C1C1(CC(C2)(C3)C=4C=CC(Br)=CC=4)CC2(C=2C=CC(Br)=CC=2)CC3(C=2C=CC(Br)=CC=2)C1 SBWXPELEFUNJFA-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000178 monomer Substances 0.000 abstract description 5
- 239000004327 boric acid Substances 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- -1 boric acid ester Chemical class 0.000 abstract description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 31
- 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
- 239000008346 aqueous phase Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 238000004949 mass spectrometry Methods 0.000 description 5
- 238000004611 spectroscopical analysis Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000013490 COF-103 Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 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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Abstract
The invention provides tetra (4-boranophenyl) adamantane and a preparation method thereof, wherein the tetra (4-boranophenyl) adamantane is prepared by reacting tetra (4-bromophenyl) adamantane or tetra (4-iodophenyl) adamantane with n-butyllithium, then carrying out nucleophilic substitution reaction with boric acid ester, and finally carrying out acidolysis with dilute hydrochloric acid. The product tetra (4-boranophenyl) adamantane obtained by the method has more accessible benzene rings, high symmetry and good rigidity, and becomes a new monomer material for synthesizing COFs with larger specific surface area.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, and relates to tetra (4-boranophenyl) adamantane and a preparation method thereof.
Background
In recent years, Covalent Organic Frameworks (COFs) have attracted attention once discovered because of their characteristics of large specific surface area, uniform pore channels, high thermal stability, good chemical stability and the like, and have good applications in gas adsorption and separation, energy storage, catalysis and the like. The main feature of three-dimensional COFs is that the sides and faces of the structural units in the channels can be contacted. The larger the specific surface area, the more active sites. The current COFs have a maximum BET specific surface area of 4210m2(COF-103). Yaghi has reported that the more aromatic rings exposed in the porous material, the greater its specific surface area. However, the structural units for synthesizing COFs reported at present are limited, so that the current synthesis of COFs with larger specific surface area presents the first challenge of designing novel monomer materials.
The number of the insertion layers of the boric acid COFs is small, and relatively more active sites for gas adsorption and catalysis are exposed. In addition, the adamantane compound is a highly symmetrical cage-shaped hydrocarbon compound, has a rigid structure, and can well maintain the tetrahedron structure after the COFs are synthesized. Therefore, the advantages of boric acid and adamantane are combined to design a novel monomer tetra (4-boranophenyl) adamantane with more contactable benzene rings, high symmetry and good rigidity.
Disclosure of Invention
The invention aims to provide a new monomer tetra (4-boranophenyl) adamantane.
The structural formula of the tetra (4-boranophenyl) adamantane material is shown as follows:
the preparation method of tetra (4-boranophenyl) adamantane specifically comprises the following steps:
(1) under the protection of nitrogen, dropwise adding n-butyllithium into a tetrahydrofuran solution of tetra (4-X-phenyl) adamantane, controlling the reaction temperature to be-80-0 ℃, stirring for 0.5-3 h, then raising the temperature to-20-25 ℃, and stirring for 30-120 min;
the X is Br or I;
the concentration of the tetra (4-X-phenyl) adamantane is as follows: 0.0065-0.052 moL/L
The molar ratio of the tetra (4-X-phenyl) adamantane to the n-butyllithium is as follows: 1: 5-89;
(2) cooling the reaction liquid obtained in the step (1) to-80-0 ℃, dropwise adding triisopropyl borate into the reaction liquid, stirring for 30-80 min, and then heating to room temperature and stirring; stirring for 10 hours, wherein the volume ratio of tetrahydrofuran to n-butyllithium to triisopropyl borate is 10-50: 1-10: 5 to 20.
(3) Quenching with dilute hydrochloric acid, adjusting the pH to 3-4, and stirring at 0-25 ℃ for 3-10 h;
(4) removing tetrahydrofuran and unreacted triisopropyl borate in the reaction liquid in the second step by using a rotary evaporator to obtain a solid product; dissolving the solid product with dichloromethane, adding water for extraction, collecting water phase, and filtering to obtain crude product of tetra (4-boranophenyl) adamantane; recrystallizing the crude product of the tetra (4-boranophenyl) adamantane by using one of dimethyl sulfoxide, methanol and acetone to obtain pure tetra (4-boranophenyl) adamantane.
The concentration of said tetrakis (4-X-phenyl) adamantane in the step (1) is preferably: 0.0104-0.026 moL/L, the preferable molar ratio of tetra (4-X-phenyl) adamantane to n-butyllithium is 1: 17.9-59.5; the reaction temperature is preferably controlled to be-78-40 ℃.
In the step (2), the reaction temperature is preferably-78-40 ℃; the volume ratio of tetrahydrofuran to n-butyllithium to triisopropyl borate is preferably 15-40: 3-8: 5-20;
the pH value is preferably adjusted to 3.3-3.8 in the step (3); preferably stirring for 8-10 h at 25 ℃. In the step (3), the reagent for recrystallizing the tetra (4-boranophenyl) adamantane is preferably dimethyl sulfoxide or methanol.
Use of tetrakis (4-boranophenyl) adamantane, characterized in that it is used for the synthesis of new monomeric materials of COFs with a greater specific surface area.
The reaction formula of the preparation method is as follows:
wherein X is Br or I.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention combines adamantane and boric acid for the first time. The material not only has a highly symmetrical cage-shaped rigid structure, but also can well maintain the tetrahedral structure after the COFs are synthesized; and the synthesized COFs have fewer interpenetration layers, and the exposed active sites for gas adsorption and catalysis are relatively more, so that the material is expected to become a new monomer material for synthesizing the COFs with larger specific surface area.
Drawings
FIG. 1 is a scheme of tetrakis (4-boranophenyl) adamantane1H-NMR.
FIG. 2 is a Fourier transform infrared spectrogram.
Detailed Description
The invention will be further described and illustrated with reference to specific examples, which do not limit the scope of the invention.
Example 1
Preparation of tetrakis (4-boranophenyl) adamantane
1. Under the protection of nitrogen, dropwise adding 4mL of n-butyllithium into a tetrahydrofuran (31mL) solution of tetra (4-bromophenyl) adamantane (0.4g,0.52mmol) shown in a structural formula (II), controlling the reaction temperature to be-78 ℃, stirring for 0.5h, raising the temperature to 0 ℃, and stirring for 50 min;
2. secondly, cooling the reaction liquid obtained in the first step to-78 ℃, dropwise adding 5mL of triisopropyl borate into the reaction liquid, stirring the mixture for 30min, then heating the mixture to room temperature and stirring the mixture overnight;
3. the third step was quenched with dilute hydrochloric acid, adjusted to pH 3.5 and stirred at 0 ℃ for 9 h.
4. And fourthly, removing tetrahydrofuran and unreacted triisopropyl borate in the reaction liquid in the second step by using a rotary evaporator to obtain a solid product. The solid product was dissolved with dichloromethane, then extracted by adding water, the aqueous phase was collected and filtered to give a crude product of tetrakis (4-boranophenyl) adamantane. The crude tetrakis (4-boranophenyl) adamantane was recrystallized from methanol to give pure tetrakis (4-boranophenyl) adamantane in 50% yield.
The obtained product is characterized by mass spectrum and nuclear magnetic hydrogen spectrum,1H-NMR is shown in FIG. 1, and Fourier transform infrared spectrum is shown in FIG. 2.
The structural characterization data is as follows:
ESI-MS (electrospray ionization mass spectrometry) characterization showed that the molecular weight measured in the cation mode was 616.28, which is consistent with the molecular weight of tetrakis (4-boranophenyl) adamantane.
Hydrogen spectrum1H-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 results were 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, the tetra (4-boranophenyl) adamantane is proved to be successfully obtained by characterization.
Example 2
Preparation of tetrakis (4-boranophenyl) adamantane
1. Under the protection of nitrogen, dropwise adding 4mL of n-butyllithium into a tetrahydrofuran (35mL) solution of tetra (4-iodophenyl) adamantane (0.4g,0.42mmol) shown in a structural formula (II), controlling the reaction temperature to be-78 ℃, stirring for 0.5h, raising the temperature to 0 ℃, and stirring for 50 min;
2. secondly, cooling the reaction liquid obtained in the first step to-78 ℃, dropwise adding 5mL of triisopropyl borate into the reaction liquid, stirring the mixture for 30min, then heating the mixture to room temperature and stirring the mixture overnight;
3. the third step was quenched with dilute hydrochloric acid, adjusted to pH 3.8 and stirred at 0 ℃ for 9 h.
4. And fourthly, removing tetrahydrofuran and unreacted triisopropyl borate in the reaction liquid in the second step by using a rotary evaporator to obtain a solid product. The solid product was dissolved with dichloromethane, then extracted by adding water, the aqueous phase was collected and filtered to give a crude product of tetrakis (4-boranophenyl) adamantane. The crude product of tetrakis (4-boranophenyl) adamantane was recrystallized from methanol and characterized by mass spectrometry, nuclear magnetic hydrogen spectrometry and infrared as tetrakis (4-boranophenyl) adamantane with a yield of 38%.
Example 3
Preparation of tetrakis (4-boranophenyl) adamantane
1. Under the protection of nitrogen, 3mL of n-butyllithium is dripped into a tetrahydrofuran (40mL) solution of tetra (4-bromophenyl) adamantane (0.4g,0.52mmol) shown in a structural formula (II), the reaction temperature is controlled to be-78 ℃, the mixture is stirred for 1.5h, and then the temperature is raised to 0 ℃ and the mixture is stirred for 30 min;
2. secondly, cooling the reaction liquid obtained in the first step to-78 ℃, dropwise adding 2mL of triisopropyl borate into the reaction liquid, stirring the mixture for 40min, and then heating the mixture to room temperature and stirring the mixture for 10 h;
3. the third step was quenched with dilute hydrochloric acid, adjusted to pH 3.3 and stirred at 25 ℃ for 10 h.
4. And fourthly, removing tetrahydrofuran and unreacted triisopropyl borate in the reaction liquid in the second step by using a rotary evaporator to obtain a solid product. The solid product was dissolved with dichloromethane, then extracted by adding water, the aqueous phase was collected and filtered to give a crude product of tetrakis (4-boranophenyl) adamantane. The crude product of tetrakis (4-boranophenyl) adamantane was recrystallized from dimethyl sulfoxide, and the product was characterized by mass spectrometry, nuclear magnetic hydrogen spectrometry and infrared as tetrakis (4-boranophenyl) adamantane with a yield of 52%.
Example 4
Preparation of tetrakis (4-boranophenyl) adamantane
1. In the first step, under the protection of nitrogen, 5mL of n-butyllithium is dropwise added into a 50mL tetrahydrofuran solution of tetra (4-iodophenyl) adamantane (0.4g,0.42mmol) with the structural formula shown in formula (II), the reaction temperature is controlled to be-78 ℃, the mixture is stirred for 1.5h, and then the mixture is heated to 0 ℃ and stirred for 30 min;
2. secondly, cooling the reaction liquid obtained in the first step to-78 ℃, dropwise adding 10mL of triisopropyl borate into the reaction liquid, stirring the mixture for 40min, and then heating the mixture to room temperature and stirring the mixture for 10 h;
3. the third step was quenched with dilute hydrochloric acid, adjusted to pH 3.0 and stirred at 25 ℃ for 10 h.
4. And fourthly, removing tetrahydrofuran and unreacted triisopropyl borate in the reaction liquid in the second step by using a rotary evaporator to obtain a solid product. The solid product was dissolved with dichloromethane, then extracted by adding water, the aqueous phase was collected and filtered to give a crude product of tetrakis (4-boranophenyl) adamantane. The crude product of tetrakis (4-boranophenyl) adamantane was recrystallized from dimethyl sulfoxide, and the product was characterized by mass spectrometry, nuclear magnetic hydrogen spectrometry and infrared as tetrakis (4-boranophenyl) adamantane with a yield of 52%.
Example 5
Preparation of tetrakis (4-boranophenyl) adamantane
1. Under the protection of nitrogen, dropwise adding 10mL of n-butyllithium into a 50mL tetrahydrofuran solution of tetra (4-bromophenyl) adamantane (0.4g,0.52mmol) with a structural formula shown as a formula (II), controlling the reaction temperature to 40 ℃, stirring for 0.5h, raising the temperature to 0 ℃, and stirring for 50 min;
2. secondly, cooling the reaction liquid obtained in the first step to-78 ℃, dropwise adding 15mL of triisopropyl borate into the reaction liquid, stirring the mixture for 30min, then heating the mixture to room temperature and stirring the mixture overnight;
3. the third step was quenched with dilute hydrochloric acid, adjusted to pH 3.8 and stirred at 0 ℃ for 3 h.
4. And fourthly, removing tetrahydrofuran and unreacted triisopropyl borate in the reaction liquid in the second step by using a rotary evaporator to obtain a solid product. The solid product was dissolved with dichloromethane, then extracted by adding water, the aqueous phase was collected and filtered to give a crude product of tetrakis (4-boranophenyl) adamantane. The crude product of the tetra (4-boranophenyl) adamantane is recrystallized by dimethyl sulfoxide, and the product is characterized by mass spectrum, nuclear magnetic hydrogen spectrum and infrared, and the yield is 30 percent.
Example 6
Preparation of tetrakis (4-boranophenyl) adamantane
1. In the first step, under the protection of nitrogen, 12mL of n-butyllithium is dripped into a tetrahydrofuran (60mL) solution of tetra (4-iodophenyl) adamantane (0.4g,0.42mmol) shown in a structural formula (II), the reaction temperature is controlled to be-40 ℃, the stirring is carried out for 0.5h, and then the temperature is raised to 0 ℃ and the stirring is carried out for 50 min;
2. secondly, cooling the reaction liquid obtained in the first step to-78 ℃, dropwise adding 25mL of triisopropyl borate into the reaction liquid, stirring the mixture for 30min, then heating the mixture to room temperature and stirring the mixture overnight;
3. the third step was quenched with dilute hydrochloric acid, adjusted to pH 3.3 and stirred at 0 ℃ for 3 h.
4. And fourthly, removing tetrahydrofuran and unreacted triisopropyl borate in the reaction liquid in the second step by using a rotary evaporator to obtain a solid product. The solid product was dissolved with dichloromethane, then extracted by adding water, the aqueous phase was collected and filtered to give a crude product of tetrakis (4-boranophenyl) adamantane. The crude product of the tetra (4-boranophenyl) adamantane is recrystallized by dimethyl sulfoxide, and the product is characterized by mass spectrum, nuclear magnetic hydrogen spectrum and infrared, and the yield is 29 percent.
Example 7
Preparation of tetrakis (4-boranophenyl) adamantane
1. Under the protection of nitrogen, dropwise adding 4mL of n-butyllithium into a tetrahydrofuran (35mL) solution of tetra (4-iodophenyl) adamantane (0.4g,0.42mmol) shown in a structural formula (II), controlling the reaction temperature to be-78 ℃, stirring for 2h, raising the temperature to 0 ℃, and stirring for 30 min;
2. secondly, cooling the reaction liquid obtained in the first step to-78 ℃, dropwise adding 15mL of triisopropyl borate into the reaction liquid, stirring the mixture for 30min, and then heating the mixture to room temperature and stirring the mixture for 10 h;
3. the third step was quenched with dilute hydrochloric acid, adjusted to pH 3.3 and stirred at 0 ℃ for 3 h.
4. And fourthly, removing tetrahydrofuran and unreacted triisopropyl borate in the reaction liquid in the second step by using a rotary evaporator to obtain a solid product. The solid product was dissolved with dichloromethane, then extracted by adding water, the aqueous phase was collected and filtered to give a crude product of tetrakis (4-boranophenyl) adamantane. The crude product of the tetra (4-boranophenyl) adamantane is recrystallized by dimethyl sulfoxide, and the product is characterized by mass spectrum, nuclear magnetic hydrogen spectrum and infrared, and the yield is 40 percent.
Example 8
Preparation of tetrakis (4-boranophenyl) adamantane
1. Under the protection of nitrogen, dropwise adding 4mL of n-butyllithium into a tetrahydrofuran (35mL) solution of tetra (4-bromophenyl) adamantane (0.4g,0.52mmol) shown in a structural formula (II), controlling the reaction temperature to 40 ℃, stirring for 0.5h, raising the temperature to 0 ℃, and stirring for 50 min;
2. secondly, cooling the reaction liquid obtained in the first step to-40 ℃, dropwise adding 15mL of triisopropyl borate into the reaction liquid, stirring the mixture for 30min, then heating the mixture to room temperature and stirring the mixture overnight;
3. the third step was quenched with dilute hydrochloric acid, adjusted to pH 4.0 and stirred at 25 ℃ for 3 h.
4. And fourthly, removing tetrahydrofuran and unreacted triisopropyl borate in the reaction liquid in the second step by using a rotary evaporator to obtain a solid product. The solid product was dissolved with dichloromethane, then extracted by adding water, the aqueous phase was collected and filtered to give a crude product of tetrakis (4-boranophenyl) adamantane. The crude product of tetrakis (4-boranophenyl) adamantane was recrystallized from acetone and the product was characterized by mass spectrometry, nuclear magnetic hydrogen spectrometry and infrared as tetrakis (4-boranophenyl) adamantane with a yield of 16%.
Example 9
Preparation of tetrakis (4-boranophenyl) adamantane
1. Under the protection of nitrogen, dropwise adding 4mL of n-butyllithium into a tetrahydrofuran (35mL) solution of tetra (4-iodophenyl) adamantane (0.4g,0.42mmol) shown in a structural formula (II), controlling the reaction temperature to be-78 ℃, stirring for 0.5h, raising the temperature to 0 ℃, and stirring for 50 min;
2. secondly, cooling the reaction liquid obtained in the first step to-40 ℃, dropwise adding 15mL of triisopropyl borate into the reaction liquid, stirring the mixture for 30min, and then heating the mixture to room temperature and stirring the mixture for 10 h;
3. the third step was quenched with dilute hydrochloric acid, adjusted to pH 3.9 and stirred at 0 ℃ for 3 h.
4. And fourthly, removing tetrahydrofuran and unreacted triisopropyl borate in the reaction liquid in the second step by using a rotary evaporator to obtain a solid product. The solid product was dissolved with dichloromethane, then extracted by adding water, the aqueous phase was collected and filtered to give a crude product of tetrakis (4-boranophenyl) adamantane. The crude product of tetrakis (4-boranophenyl) adamantane was recrystallized from acetone and the product was characterized by mass spectrometry, nuclear magnetic hydrogen spectrometry and infrared as tetrakis (4-boranophenyl) adamantane with a yield of 15%.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (5)
1. A preparation method of tetra (4-boranophenyl) adamantane is characterized by comprising the following steps:
(1) under the protection of nitrogen, dropwise adding n-butyllithium into a tetrahydrofuran solution of tetra (4-X-phenyl) adamantane, controlling the reaction temperature to be-80-0 ℃, stirring for 0.5-3 h, then raising the temperature to-20-25 ℃, and stirring for 30-120 min;
the X is Br or I;
the concentration of the tetra (4-X-phenyl) adamantane is as follows: 0.0065-0.052 mol/L
The molar ratio of the tetra (4-X-phenyl) adamantane to the n-butyllithium is as follows: 1: 5-89;
(2) cooling the reaction liquid obtained in the step (1) to-80-0 ℃, dropwise adding triisopropyl borate into the reaction liquid, stirring for 30-80 min, and then heating to room temperature and stirring; stirring for 10 hours; the volume ratio of tetrahydrofuran to n-butyllithium to triisopropyl borate is 10-50: 1-10: 5-20;
(3) quenching with dilute hydrochloric acid, adjusting the pH to 3-4, and stirring at 0-25 ℃ for 3-10 h;
(4) removing tetrahydrofuran and unreacted triisopropyl borate in the reaction system by using a rotary evaporator to obtain a solid product; dissolving the solid product with dichloromethane, adding water for extraction, collecting water phase, and filtering to obtain crude product of tetra (4-boranophenyl) adamantane; recrystallizing the crude product of the tetra (4-boranophenyl) adamantane by using one of dimethyl sulfoxide, methanol and acetone to obtain pure tetra (4-boranophenyl) adamantane;
the structural formula of the tetra (4-boranophenyl) adamantane is as follows:
2. the process for producing tetrakis (4-boranophenyl) adamantane according to claim 1, characterized in that: the concentration of the tetra (4-X-phenyl) adamantane in the step (1) is as follows: 0.0104-0.026 mol/L, and the molar ratio of tetra (4-X-phenyl) adamantane to n-butyllithium is 1: 17.9-59.5; the volume ratio of tetrahydrofuran to n-butyllithium to triisopropyl borate is (15-40: 3-8): 5-20 ℃, and controlling the reaction temperature to be-78 to-40 ℃.
3. The process for producing tetrakis (4-boranophenyl) adamantane according to claim 1, characterized in that: in the step (2), the reaction temperature is-78 to-40 ℃.
4. The process for producing tetrakis (4-boranophenyl) adamantane according to claim 1, characterized in that: adjusting the pH value to 3.3-3.8 in the step (3); stirring for 8-10 h at 25 ℃.
5. The process for producing tetrakis (4-boranophenyl) adamantane according to claim 1, characterized in that: in the step (3), the reagent for recrystallizing the tetra (4-boranophenyl) adamantane is dimethyl sulfoxide or methanol.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103804196A (en) * | 2012-11-06 | 2014-05-21 | 中国科学院理化技术研究所 | Star-shaped adamantane derivative molecular glass and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103804196A (en) * | 2012-11-06 | 2014-05-21 | 中国科学院理化技术研究所 | Star-shaped adamantane derivative molecular glass and preparation method and application thereof |
| CN103374024A (en) * | 2013-07-02 | 2013-10-30 | 华南理工大学 | Arylboronic acid derivatives and preparation method thereof |
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