CN111909090A - Compound containing abundant alkynyl, preparation method thereof and metal organic framework material - Google Patents
Compound containing abundant alkynyl, preparation method thereof and metal organic framework material Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 52
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 36
- 239000000463 material Substances 0.000 title claims abstract description 22
- 125000000304 alkynyl group Chemical group 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 10
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 16
- -1 methoxyphenyl Chemical group 0.000 claims description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 11
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 229930192474 thiophene Natural products 0.000 claims description 5
- 125000003944 tolyl group Chemical group 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 238000004729 solvothermal method Methods 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000013299 conductive metal organic framework Substances 0.000 abstract description 17
- 239000003446 ligand Substances 0.000 abstract description 13
- 238000003786 synthesis reaction Methods 0.000 abstract description 10
- 239000013078 crystal Substances 0.000 abstract description 9
- 238000012986 modification Methods 0.000 abstract description 7
- 230000002194 synthesizing effect Effects 0.000 abstract description 5
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 3
- 230000007246 mechanism Effects 0.000 abstract description 3
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000007832 Na2SO4 Substances 0.000 description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 239000000284 extract Substances 0.000 description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000010898 silica gel chromatography Methods 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethyl cyclohexane Natural products CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- PHXNXSOHPKDBSW-UHFFFAOYSA-N 1,3,5-tribromo-2,4,6-triiodobenzene Chemical compound BrC1=C(I)C(Br)=C(I)C(Br)=C1I PHXNXSOHPKDBSW-UHFFFAOYSA-N 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LLNQWPTUJJYTTE-UHFFFAOYSA-N 4-iodopyrazole Chemical compound IC=1C=NNC=1 LLNQWPTUJJYTTE-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical class N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- DYHSDKLCOJIUFX-UHFFFAOYSA-N tert-butoxycarbonyl anhydride Chemical compound CC(C)(C)OC(=O)OC(=O)OC(C)(C)C DYHSDKLCOJIUFX-UHFFFAOYSA-N 0.000 description 2
- GFHWWQDOPFLNRN-UHFFFAOYSA-N tert-butyl 4-(2-trimethylsilylethynyl)pyrazole-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1C=C(C#C[Si](C)(C)C)C=N1 GFHWWQDOPFLNRN-UHFFFAOYSA-N 0.000 description 2
- CJMALPDNJCWQAQ-UHFFFAOYSA-N tert-butyl 4-ethynylpyrazole-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1C=C(C#C)C=N1 CJMALPDNJCWQAQ-UHFFFAOYSA-N 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical group C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 description 2
- YWDUZLFWHVQCHY-UHFFFAOYSA-N 1,3,5-tribromobenzene Chemical compound BrC1=CC(Br)=CC(Br)=C1 YWDUZLFWHVQCHY-UHFFFAOYSA-N 0.000 description 1
- BXGYBSJAZFGIPX-UHFFFAOYSA-N 2-pyridin-2-ylethanol Chemical compound OCCC1=CC=CC=N1 BXGYBSJAZFGIPX-UHFFFAOYSA-N 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 102100032373 Coiled-coil domain-containing protein 85B Human genes 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 101000868814 Homo sapiens Coiled-coil domain-containing protein 85B Proteins 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- WHYQCQRHPQBZHM-UHFFFAOYSA-N pyrazole-1-carboxylic acid Chemical compound OC(=O)N1C=CC=N1 WHYQCQRHPQBZHM-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- RKFMLIZYBJXJEB-UHFFFAOYSA-N tert-butyl 3-iodopyrazole-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1C=CC(I)=N1 RKFMLIZYBJXJEB-UHFFFAOYSA-N 0.000 description 1
- WRCRIGRVTPLDDD-UHFFFAOYSA-N tert-butyl 4-iodopyrazole-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1C=C(I)C=N1 WRCRIGRVTPLDDD-UHFFFAOYSA-N 0.000 description 1
- UZIXCCMXZQWTPB-UHFFFAOYSA-N trimethyl(2-phenylethynyl)silane Chemical compound C[Si](C)(C)C#CC1=CC=CC=C1 UZIXCCMXZQWTPB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Abstract
The invention relates to the technical field of organic synthesis, in particular to a compound containing abundant alkynyl, a preparation method thereof and a metal organic framework material. The invention discloses a compound containing abundant alkynyl, which has a structure shown in a formula (I), wherein the compound contains pyrazole with abundant coordination sites, and a conjugated system of a ligand can be increased by post-modification thermal cyclization to form a ligand with stronger rigidity, so that the acid-base stability and the thermal stability of MOF are improved. The compound of the formula (I) contains abundant alkynyl, has good solubility, is favorable for synthesizing MOF single crystals, increases a conjugated system of a ligand through appropriate post-modification thermal cyclization, thereby improving the conductivity of the MOF, avoiding the problem that the ligand of a large conjugated system cannot synthesize conductive MOF with good crystallization due to poor solubility, and providing a basis for researching the charge transmission mechanism of the conductive MOF.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a compound containing abundant alkynyl, a preparation method thereof and a metal organic framework material.
Background
Metal organic framework Materials (MOFs) having permanent porosity, high crystallinity, excellent surface area, workAdjustable, etc., and shows wide applications in energy storage and conversion, gas adsorption and separation, catalysis, sensors, biomedicine, and proton/ion conductors. However, due to the lack of high conductivity or proton conductivity MOFs, MOFs have relatively few applications in electronic devices. The earliest conductive MOFs reported in 2009 by Kitagawa and collaborators, which showed excellent conductivity during the last five years of research: (>10-3S·cm-1) The MOF can be suitable for various fields, such as electrocatalysis, chemical resistance type sensors, super capacitors, batteries, electronic products and the like, so that the design and synthesis of the conductive MOF have good application prospects. To date, the possible charge transport patterns in conductive MOFs can be described from both chemical and physical perspectives: (1) from the principle of chemical design, the conductive MOF can be divided into two types of through spaces or through keys; (2) from a physical point of view, the hopping or band theory can reflect the intrinsic charge transport properties of conductive MOFs. The MOFs composed of pi-conjugated planar multidentate organic ligands have highly delocalized pi electrons to produce excellent conductivity, and the following formula shows that the organic monomers of the pi-conjugated conductive MOFs reported so far, with the expansion of the size of Polycyclic Aromatic Hydrocarbons (PAHs), the pi-pi interaction between adjacent layers is expected to be enhanced, and the electron delocalization is also improved.
Despite significant advances in recent years, conductive MOFs are still in the infancy stage, mainly facing the following challenges: (1) the lack of structural rigidity makes them sensitive to high temperatures and pressures and to strong acid/base conditions, severely hampering their future use; (2) due to the problem of poor ligand solubility of large conjugated systems, the synthesis and characterization of single crystals of conductive MOFs remains challenging, particularly for 2D conductive MOFs; (3) due to the lack of high quality crystalline samples, intrinsic charge transport studies of conductive MOFs remain rare, and defects in the structure and their effect on the electrical transport properties in MOFs are unclear.
Disclosure of Invention
The invention provides a compound containing abundant alkynyl and a preparation method thereof, which can be used as a ligand for synthesizing MOF materials and can effectively solve the problem of poor solubility of the ligand for synthesizing conductive MOF.
The specific technical scheme is as follows:
the invention provides a compound containing abundant alkynyl, which has a structure shown in a formula (I);
wherein R is selected from hydrogen, C1-C18 alkane, methylphenyl, methoxyphenyl, cyclohexyl, thiophene or furan.
The compound provided by the invention has pyrazole with rich coordination sites, and can increase a conjugated system of a ligand through post-modification thermal cyclization to form a ligand with stronger rigidity, so that the acid-base stability and the thermal stability of the MOF are improved. The compound of the formula (I) contains abundant alkynyl, has good solubility, is favorable for synthesizing MOF single crystals, synthesizes conductive MOF single crystals of a large conjugated system through appropriate post-modification thermal cyclization, and provides a basis for researching the charge transmission mechanism of the conductive MOF.
In the invention, R is selected from alkanes of C1-C18, and R is preferably n-butyl.
The invention also provides a preparation method of the compound containing abundant alkynyl, which comprises the following steps:
carrying out Sonogashira reaction on a compound of a formula (II), a compound of a formula (III), a catalyst and an organic solvent under an alkaline condition to obtain a compound of a formula (I);
wherein R is selected from hydrogen, C1-C18 alkane, methylphenyl, methoxyphenyl, cyclohexyl, thiophene or furan.
The preparation process of the compound of formula (I) provided by the invention is simple.
In the present invention, the molar ratio of the basic agent, the compound of formula (ii) to the compound of formula (iii) and the organic solvent of the catalyst, which provide the basic conditions, is (3-5): 1: (3-5): (0.11-0.35), preferably 3: 1: 3: 0.19.
in the present invention, the alkaline reagent providing the alkaline condition is preferably an inorganic base or an organic base, the inorganic base is preferably potassium carbonate, and the organic base is preferably diethylamine or triethylamine;
the catalyst comprises a palladium catalyst, an iodinated imino ketone and triphenyl phosphorus, and the molar ratio of the palladium catalyst to the iodinated imino ketone to the triphenyl phosphorus is (0.02-0.05): (0.04-0.1): (0.05-0.2), preferably 0.03: 0.06: 0.1;
the organic solvent is tetrahydrofuran or toluene.
In the invention, the atmosphere of the Sonogashira reaction is nitrogen or inert gas;
the Sonogashira reaction is carried out at a temperature of 60-90 ℃ for 24-36h, preferably at 65 ℃ for 24 h.
In the invention, after the Sonogashira reaction is finished, the compound of the formula (I) can be obtained by preferably dissolving the compound with DCM, washing the compound with a saturated sodium chloride solution, drying the compound with anhydrous sodium sulfate and then separating and purifying the dried compound.
In the invention, when R in the compound of formula (II) is C1-C18 alkane, methylphenyl, methoxyphenyl, cyclohexyl, thiophene or furan, the preparation of the compound of formula (II) is specifically as follows: reacting 1,3, 5-tribromo-2, 4, 6-triiodobenzene with a compound of formula (VI), a catalyst and an organic solvent under an alkaline condition to obtain a compound of formula (II);
in the present invention, when R in the compound of formula (II) is hydrogen, the compound of formula (II) is specifically prepared by: dissolving 1,3,5- [ (trimethylsilyl) ethynyl ] benzene and an alkaline reagent in an organic solvent for reaction to obtain a compound of a formula (II);
the alkaline agent is preferably potassium carbonate; the organic solvent is preferablyMethanol; the 1,3,5- [ (trimethylsilyl) ethynyl group]The molar ratio of benzene to alkaline reagent is 1: (3-6), preferably 1: 3; the reaction is preferably stirred at room temperature, the stirring speed is 300-500r/min, and the time is 6-10h, preferably 6 h; after the reaction is completed, preferably chloroform is used for extraction, and the extract is washed by saturated sodium chloride solution and Na2SO4Drying, and distilling under reduced pressure to remove the solvent to obtain the compound of formula (II).
The abundant alkynyl-containing compound provided by the invention and metal ions can form a metal organic framework material through coordination bonds, so that the invention also provides application of the abundant alkynyl-containing compound or the abundant alkynyl-containing compound prepared by the preparation method in preparation of the metal organic framework material.
The invention also provides a metal organic framework material A which has a structure shown as a formula (IV);
the metal organic framework material A is prepared from a compound shown in a formula (I) and metal salt through a solvothermal method;
in the present invention, the metal salt is selected from the group consisting of Ni (OAc)2·4H2O、NiCl·4H2O、Ni(NO3)2·4H2O、 Cu(OAc)2·H2O、Cu(NO3)2·3H2O、CuCl2·2H2O、Co(OAc)2·4H2O、 Co(NO3)2·6H2O or CoCl2·6H2O, whereby M in the compound of formula (IV) is selected from Ni, Cu or Co.
In the present invention, the preparation method of the metal organic framework material A by the solvothermal method of the compound of formula (I) and the metal salt is a conventional preparation method in the field.
For example, when the metal salt is Ni (OAc)2·4H2O, the document "Cubic Octanuclear Ni (II) Clusters in high throughput Porous-Based Materials" (J.Am.chem. Soc.,2010,132,23, 7902-7904) The method in (1) is carried out: to Ni (OAc)2·4H2To a solution of O (0.087g, 0.35mmol) in DMF (7mL) was added the compound of formula (I) with stirring at room temperature. The mixture was heated to 60 ℃ and triethylamine (1.5mL) was then added dropwise to the mixture over 1 minute, the reaction was then held at reflux for 6 hours, the green precipitate was filtered off, washed successively with aliquots of methanol (2X 10mL) and dried under vacuum at 130 ℃ for 1h to give the polycrystalline green product.
The invention also provides another metal-organic framework material B which has a structure shown in a formula (V); the metal organic framework material B is prepared by post-modifying and hot cyclization of the metal organic framework material A;
in the present invention, the thermal cyclization treatment is performed by a method described in the literature "systematic improvement of stability by in situ linker cyclization of a metal-organic framework" (chem. Commun., 2018,54, 9470-9473): 100mg of the crystals prepared according to formula (IV) were washed with DMF (3X 2mL) and immersed in acetonitrile (3X 3mL, replaced by fresh acetonitrile after 12 hours each). The resulting crystals were filtered and then evacuated at 70 ℃ for 8 hours. The crystal sample was then heated in an oven at 320 ℃ for 3 hours under argon atmosphere at a heating rate of 3 ℃/min to give the compound of formula (v). The metal organic framework material B provided by the invention has a large conjugated system, good crystallinity and excellent conductivity.
According to the technical scheme, the invention has the following advantages:
the invention provides a compound containing abundant alkynyl, which has a structure shown in a formula (I), wherein the compound contains pyrazole with abundant coordination sites, and a conjugated system of a ligand can be increased by post-modification thermal cyclization to form a ligand with stronger rigidity, so that the acid-base stability and the thermal stability of MOF are improved. The compound of the formula (I) contains abundant alkynyl, has good solubility, is favorable for synthesizing MOF single crystals, increases a conjugated system of a ligand through appropriate post-modification thermal cyclization, thereby improving the conductivity of the MOF, avoiding the problem that the ligand of a large conjugated system cannot synthesize conductive MOF with good crystallization due to poor solubility, and providing a basis for researching the charge transmission mechanism of the conductive MOF.
Detailed Description
In order to make the objects, features and advantages of the present invention more obvious and understandable, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it should be apparent that the embodiments described below are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example Synthesis of 11, 3, 5-tribromo-2, 4, 6-triiodobenzene
At room temperature, 410mL of concentrated H was added over 15 minutes2SO4Periodic acid (27.36g, 120mmol) was added in small portions; after periodic acid is dissolved, KI (59.78g, 360mmol) is added in portions in 1h under ice bath conditions (0 ℃); adding 1,3, 5-tribromobenzene (12.59g, 40.0mmol) into the obtained solution in batches under ice bath condition (0 deg.C) within 25 min; after stirring the solution at room temperature for 72h, the resulting concentrated mixture was diluted with water, the resulting precipitate was filtered and washed with water and then MeOH; the solid was triturated with MeOH, filtered, and recrystallized from a pyridine-ethanol system to give pale yellow needle-like crystals (18.46g, yield: 66%).13C NMR(100MHz，DMSO-d6),＝138.6，108.2 ppm。
Example synthesis of 21, 3, 5-tribromo-2, 4, 6-tris [ (trimethylsilyl) ethynyl ] benzene
The 1,3, 5-tribromo-2, 4, 6-tris prepared in example 1 was usedIodobenzene (5.0g, 7.2mmol), triethylamine (18 mL), [ PdCl [ ]2(PPh3)2](3 mol% for 1,3, 5-tribromo-2, 4, 6-triiodobenzene) and CuI (6 mol% for 1,3, 5-tribromo-2, 4, 6-triiodobenzene) were added sequentially to a dry three-necked flask; a solution of trimethylsilylacetylene (2.46g, 2.5mmol) in DIPA (9mL) was added dropwise followed by PPh3(10 mol%) to give a mixture; heating the mixture to 80 ℃, adding THF (9mL) after 1h, and reacting for 24h under the protection of argon; after completion of the reaction, the mixture was filtered through Celite, diluted with water (35mL), extracted with chloroform (35 mL. times.3), and the extract was washed with brine (50 mL. times.3) and then Na2SO4(anhydrous) drying; after the solvent was removed by distillation under the reduced pressure, the product was purified by silica gel chromatography (eluting with hexane) to obtain a white solid (3.0 g, yield: 71%).1H NMR(400MHz，CDCl3)：＝0.26[s，27H]ppm。13C NMR(100MHz，CDCl3)：＝-0.2，104.7，106.5，126.1，134.5ppm。
Example 31, 3, 5-tribromo-2, 4, 6-triethylynylbenzene
1,3,5- [ (trimethylsilyl) ethynyl group]Benzene (6.25g, 30mmol) was dissolved in 100mL of methanol, and potassium carbonate (12.45g, 90mmol) was added to the solution; the reaction mixture was stirred at room temperature at a stirring rate of 300-500r/min for 6h, deionized water was added after the reaction was completed, chloroform (35 mL. times.3) was used for extraction, and the extract was washed with a saturated sodium chloride solution (50 mL. times.3) and Na2SO4(anhydrous) drying; the solvent was distilled off under reduced pressure to obtain a white product (4.0g, yield: 96%).1H NMR(400MHz，CDCl3)：＝4.01(s，3H)ppm。13C NMR(100MHz，CDCl3)：＝134.4、127.1、82.3、81.4ppm。
EXAMPLE 44 Synthesis of iodo-1H-pyrazole-1-carboxylic acid tert-butyl ester
4-iodopyrazole (7.85g, 40.4mmol) was dissolved in THF (120mL) and Et was added3N (8.5 mL, 60.5mmol) and di-tert-butyl dicarbonate (9.7g, 44.5 mmol); the reaction was stirred at room temperature for 3 h, THF was removed by distillation under the reduced pressure, deionized water was added, extraction was performed with ethyl acetate (35 mL. times.3), and the extract was washed with saturated sodium chloride solution (50 mL. times.3) and Na2SO4(anhydrous) drying; distillation under reduced pressure gave a crude product as an oil which was purified by silica gel chromatography eluting with ethyl acetate/cyclohexane solution (1:4) to give 4-iodo-1H-pyrazole tert-butyl-1-carboxylate (11.66g, 98%).1H NMR(400MHz， CDCl3)：＝1.68(s，9H)，7.73(s，1H)，8.17(s，1H)。
Example Synthesis of tert-butyl 54- ((trimethylsilyl) ethynyl) -1H-pyrazole-1-carboxylate
Tert-butyl 4-iodo-1H-pyrazole-1-carboxylate (4.67g, 15.9 mmol) obtained in example 4 and trimethylsilylacetylene (2.18g, 22.2mmol) were dissolved in DMF (22mL) under nitrogen; diisopropylamine (2.9mL, 20.7mmol), CuI (197mg, 1.03mmol), triphenylphosphine (832mg, 3.18mmol) and palladium acetate (239mg, 1.06mmol) were added under nitrogen; the reaction was heated at 60 ℃ for 1.25h, cooled, deionized water was added, extraction was performed with diethyl ether (35 mL. times.3), and the extracts were washed with saturated sodium chloride solution (50 mL. times.3) and Na2SO4(anhydrous) drying; distillation under reduced pressure gave a crude product as an oil, which was purified by silica gel chromatography eluting with ethyl acetate/cyclohexane solution (1:4) to give tert-butyl 4- ((trimethylsilyl) ethynyl) -1H-pyrazole-1-carboxylate (3.88g, yield: 92%).1H NMR(400MHz，CDCl3)：＝0.25(s，6H)，1.67(s，9H)，7.77(d，1H)， 8.20(d，1H)。
Example Synthesis of 64-ethynyl-1H-pyrazole-1-carboxylic acid tert-butyl ester
Tert-butyl 4- ((trimethylsilyl) ethynyl) -1H-pyrazole-1-carboxylate (3.88g, 14.69mmol) prepared in example 5 was dissolved in THF (40mL) and cooled to 0-5 ℃; a 1M THF solution of tetrabutylammonium fluoride (16mL, 16mmol) was added and the reaction was stirred for 20 min; THF was removed by distillation under the reduced pressure, deionized water was added, extraction was performed with ethyl acetate (35 mL. times.3), and the extract was washed with a saturated sodium chloride solution (50 mL. times.3) and then with Na2SO4(anhydrous) drying; distillation under reduced pressure gave a crude product as an oil which was purified by silica gel chromatography eluting with ethyl acetate/cyclohexane solution (1:4) to give 4-ethynyl-1H-pyrazole-1-carboxylic acid tert-butyl ester (2.33g, 82%).1H NMR(400MHz，CDCl3)：＝ 1.68(s，9H)，3.11(s，1H)，7.79(s，1H)，8.24(s，1H)。
EXAMPLE 7 Synthesis of tri-tert-butyl 4,4',4 "- ((2,4, 6-triethynylbenzene-1, 3, 5-triyl) tris (acetylene-2, 1-diyl)) tris (1H-pyrazole-1-carboxylate)
1,3, 5-tribromo-2, 4, 6-triethylynylbenzene (3.9g, 10.1mmol) obtained in example 4, tert-butyl 4-ethynyl-1H-pyrazole-1-carboxylate (7.77g, 40.4mmol) obtained in example 6, PaCl were added under nitrogen protection2(PPh3)2(3mol％)，PPh3(10 mol%), CuI (6 mol%), triethylamine (15mL), THF (15mL), reacted at 65 ℃ for 2 h; after the reaction was completed, deionized water was added, DCM (35 mL. times.3) was used for extraction, and the extract was washed with saturated sodium chloride solution (50 mL. times.3) and Na2SO4(anhydrous) drying; the solvent was removed by distillation under the reduced pressure, and the product was purified by silica gel chromatography, eluting with ethyl acetate/cyclohexane solution (1: 2), to give a yellow solid (5.3g, 73%).1H NMR(400MHz，CDCl3)：＝ 1.63(s，27H)，4.01(s，3H)，8.37(s，3H)，8.78(s，3H)。
The above-mentioned embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A compound containing abundant alkynyl, which has a structure shown in a formula (I);
wherein R is selected from hydrogen, C1-C18 alkane, methylphenyl, methoxyphenyl, cyclohexyl, thiophene or furan.
2. The rich alkynyl containing compound of claim 1, wherein said R is selected from n-butyl.
3. A preparation method of a compound containing abundant alkynyl is characterized by comprising the following steps:
carrying out Sonogashira reaction on a compound of a formula (II), a compound of a formula (III), a catalyst and an organic solvent under an alkaline condition to obtain a compound of a formula (I);
wherein R is selected from hydrogen, C1-C18 alkane, methylphenyl, methoxyphenyl, cyclohexyl, thiophene or furan.
4. The process according to claim 3, wherein the basic conditions are provided in a molar ratio of basic reagent, compound of formula (II) to compound of formula (III), catalyst and organic solvent of (3-5): 1: (3-5): (0.11-0.35).
5. The method according to claim 3, wherein the catalyst comprises a palladium-based catalyst, a ketone iodide and triphenylphosphine.
6. The method according to claim 5, wherein the palladium-based catalyst, the iodonium ketone and the triphenylphosphine are present in a molar ratio of (0.02 to 0.05): (0.04-0.1): (0.05-0.2).
7. The process according to claim 3, wherein the Sonogashira reaction is carried out at a temperature of 60-90 ℃ for a time of 24-36 h.
8. Use of the abundant alkynyl compound of claim 1 or 2 or the abundant alkynyl compound prepared by the preparation method of any one of claims 3 to 7 in the preparation of metal organic framework materials.
9. A metal organic framework material A is characterized by having a structure shown as a formula (IV);
the metal organic framework material A is prepared from the abundant alkynyl-containing compound of claim 1 or 2 or the abundant alkynyl-containing compound prepared by the preparation method of any one of 3 to 7 and metal salt by a solvothermal method;
wherein M is selected from Ni, Cu or Co.
10. A metal-organic framework material B is characterized in that the structure is shown as a formula (V);
the metal-organic framework material B is prepared by post-modifying thermal cyclization of the metal-organic framework material A according to claim 9;
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