CN103755650B - Triazole functionalized 4,4 '-difluorodiphenyl sulfone compound and synthetic method thereof - Google Patents
Triazole functionalized 4,4 '-difluorodiphenyl sulfone compound and synthetic method thereof Download PDFInfo
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- CN103755650B CN103755650B CN201310505487.4A CN201310505487A CN103755650B CN 103755650 B CN103755650 B CN 103755650B CN 201310505487 A CN201310505487 A CN 201310505487A CN 103755650 B CN103755650 B CN 103755650B
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- difluorodiphenyl sulfone
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- 150000003852 triazoles Chemical class 0.000 title claims abstract description 19
- -1 4,4 '-difluorodiphenyl sulfone compound Chemical class 0.000 title claims abstract description 16
- 238000010189 synthetic method Methods 0.000 title description 5
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000003457 sulfones Chemical class 0.000 claims abstract description 13
- PLVUIVUKKJTSDM-UHFFFAOYSA-N 1-fluoro-4-(4-fluorophenyl)sulfonylbenzene Chemical compound C1=CC(F)=CC=C1S(=O)(=O)C1=CC=C(F)C=C1 PLVUIVUKKJTSDM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003921 oil Substances 0.000 claims description 6
- 239000012044 organic layer Substances 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 6
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical group C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 claims description 6
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 101000738322 Homo sapiens Prothymosin alpha Proteins 0.000 claims description 3
- 102100033632 Tropomyosin alpha-1 chain Human genes 0.000 claims description 3
- 101150003085 Pdcl gene Proteins 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 15
- 238000003786 synthesis reaction Methods 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 229920002492 poly(sulfone) Polymers 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 4
- 239000004020 conductor Substances 0.000 abstract description 4
- 229930185605 Bisphenol Natural products 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 3
- 230000001458 anti-acid effect Effects 0.000 abstract description 3
- 239000003963 antioxidant agent Substances 0.000 abstract description 3
- 230000003078 antioxidant effect Effects 0.000 abstract description 3
- 235000006708 antioxidants Nutrition 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- 238000006068 polycondensation reaction Methods 0.000 abstract description 3
- 125000001246 bromo group Chemical group Br* 0.000 abstract description 2
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 11
- 239000012528 membrane Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000446 fuel Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000004440 column chromatography Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000013517 stratification Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229920006258 high performance thermoplastic Polymers 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/04—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles
- C07D249/06—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles with aryl radicals directly attached to ring atoms
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The present invention relates to a kind of triazole functionalized 4,4 '-difluorodiphenyl sulfone compound and preparation method thereof, the structural formula of this compound is:
.This compounds with 4,4 '-difluorodiphenyl sulfone for raw material, by Reactive Synthesis such as bromo, coupling, clicks, in four steps, comprise 3,3 '-two bromo-4, the synthesis of 4 '-difluorodiphenyl sulfone, 3,3 '-two trimethyl silicon based ethynyl-4,4 '-difluorodiphenyl sulfone synthesizes, 3, the synthesis of 3 '-diacetylene-4,4 '-difluorodiphenyl sulfone, triazole functionalized 4, the synthesis of 4 '-difluorodiphenyl sulfone.Compound synthesized by the present invention can carry out polycondensation with bisphenol compound, obtain polymer polysulfone material, the skeleton structure of polysulfones makes it have excellent resistance alcohol effect and anti-oxidant, antiacid catalytic hydrolysis performance, and excellent mechanical property and thermostability, and triazole basic functionality provides proton defect, can be used for preparing acid-alkali both sexes high temperature proton conducting material.
Description
Technical field
The present invention relates to a kind of 4,4 '-difluorodiphenyl sulfone compound and synthetic method thereof, particularly a kind of triazole functionalized 4,4 '-difluorodiphenyl sulfone compound and synthetic method thereof.
Background technology
Fuel cell (FC) a kind ofly will be stored in the high efficiency energy conversion system that converts chemical energy in fuel and oxygenant is electric energy, is a kind of up-and-coming efficient green energy.Proton Exchange Membrane Fuel Cells (protonexchangemembranefuelcell, PEMFC) adopt polymeric film as ionogen, have cold-starting, energy transformation ratio high, reveal without electrolytic solution, the advantage such as the life-span is long, be the generally acknowledged first-selected power supply promising to be military affairs, electromobile, space flight and regional power station most.Eelctro-catalyst and proton exchange membrane are the critical materials of Proton Exchange Membrane Fuel Cells.Wherein, the effect of anode electrocatalyst is the oxidizing reaction of catalytic fuel; The effect of electrocatalyst for cathode is the effect of the reduction reaction proton exchange membrane of catalytic oxygen is isolation fuel and oxygenant, and carries protogenic migrating channels.
The main obstacle hindering PEMFC to promote the use of is the expensive price, particularly eelctro-catalyst of PEMFC and the high price of these two kinds of core materials of proton exchange membrane.But, if the working temperature of PEMFC can be brought up to 120 to 180 DEG C, then electrode reaction speed will be accelerated greatly, can reduce the Pt consumption in eelctro-catalyst, the eelctro-catalyst of other cheapness even can be used to substitute expensive Pt catalyzer, greatly reduce the cost of PEMFC.PEMFC is when hot operation, and the tolerance of eelctro-catalyst to impurity such as the CO in hydrogen will improve greatly, can simplify the purifying process of hydrogen, even can directly utilize reformed gas to make fuel, expands the source of hydrogen.Meanwhile, at the PEMFC of the gaseous state warm area work of water, the management of its hydro-thermal will be more convenient.Therefore, exploitation is efficient, the novel proton exchange membranes of low cost, and particularly non-fluorine proton exchange membrane that is high temperature resistant, that can run in anhydrous conditions just becomes fuel cell technology key issue urgently to be resolved hurrily.
The contrast of tradition proton exchange membrane and high temperature proton exchange film, traditional must contain aqueous solvent, and proton conductivity affects very large by water content, and water content reduces will make specific conductivity sharply decline.High temperature proton exchange film is anhydrous condition, but needs any proton and the material accepting proton, the migration and proton can circulate between donor and acceptor.In acid-alkali compound proton exchange membrane, acidic-group provides proton conducting, and basic group forms proton defect.Between hydrogen bond donor and donor, form hydrogen bond network, be convenient to proton transport.
Polyether sulphone is the aromatic series high-performance thermoplastic engineering plastics of a class containing sulfuryl on molecular backbone chain, there is excellent resistance alcohol effect and anti-oxidant, antiacid catalytic hydrolysis performance, in addition also there is excellent mechanical property and thermostability, therefore may be used for preparing soda acid both sexes high temperature proton conducting material.
Summary of the invention
An object of the present invention there are provided a kind of triazole functionalized 4,4 '-difluorodiphenyl sulfone compound.
Two of object of the present invention is the synthetic method providing this compounds.
For achieving the above object, the present invention adopts following reaction mechanism:
According to above-mentioned reaction mechanism, the present invention adopts following technical scheme:
A kind of triazole functionalized 4,4 '-difluorodiphenyl sulfone compound, is characterized in that structural formula is:
。
A kind of prepare above-mentioned triazole functionalized 4, the method for 4 '-difluorodiphenyl sulfone compound, the concrete steps of the method are:
A. by 4, after 4 '-difluorodiphenyl sulfone and N-bromo-succinimide press the mixed in molar ratio of 1:2.2 ~ 1:2.5, add the vitriol oil of catalyst levels, normal-temperature reaction, after determining end by a plate, solution is poured in frozen water, throw out use water, n-hexane, separating-purifying obtains 3, and 3 '-two bromo-4,4 '-difluorodiphenyl sulfone, its structural formula is:
;
B., under air tight condition and inert atmosphere, by step a gained 3,3 '-two bromo-4,4 '-difluorodiphenyl sulfone and trimethylsilyl acetylene are dissolved in tetrahydrofuran (THF) by the mol ratio of 1:2.2 ~ 1:3, then add CuI, PdCl of catalyst levels
2(PPh
3)
2and Et
3n, stirring reaction is complete to reactant reaction, and filtration is spin-dried for, and separating-purifying obtains 3,3 '-two trimethyl silicon based ethynyl-4,4 '-difluorodiphenyl sulfone, and its structural formula is:
;
c.by step b gained 3,3 '-two trimethyl silicon based ethynyl-4,4 '-difluorodiphenyl sulfone and tetrabutyl ammonium fluoride are dissolved in tetrahydrofuran (THF) by the mol ratio of 1:2 ~ 1:2.5, stirring at normal temperature reaction is complete to reactant reaction, extraction, organic layer saturated common salt water washing, 3 are obtained after drying, separating-purifying, 3 '-diacetylene-4,4 '-difluorodiphenyl sulfone, its structural formula is:
;
D. under inert atmosphere, by step c gained 3,3 '-diacetylene-4,4 '-difluorobenzene sulfone and trimethylacetic acid nitrine methyl esters or TMSA are dissolved in tetrahydrofuran (THF) by the mol ratio of 1:2 ~ 1:2.5, then add the CuSO of catalyst levels successively
4, NaAsc, stirring reaction is complete to reactant reaction, and after extraction, organic layer cleans with the ammoniacal liquor of 5% again, anhydrous MgSO
4drying, filtration is spin-dried for, and separating-purifying obtains triazole functionalized 4,4 '-difluorodiphenyl sulfone.
Triazole synthesized by the present invention functionalized 4,4 '-difluorodiphenyl sulfone can carry out polycondensation with bisphenol compound, obtains the polysulfone material containing basic functionality, for the preparation of acid-alkali both sexes high temperature proton conducting material.
Accompanying drawing explanation
Fig. 1 is 3,3 '-two bromo-4,4 '-difluorodiphenyl sulfone
1hNMR collection of illustrative plates
Fig. 2 is 3,3 '-two bromo-4, the mass spectrum of 4 '-difluorodiphenyl sulfone
Fig. 3 is 3,3 '-trimethyl silicon based ethynyl-4,4 '-difluorodiphenyl sulfone
1hNMR collection of illustrative plates
Fig. 4 is 3,3 '-diacetylene-4,4 '-difluorodiphenyl sulfone
1hNMR collection of illustrative plates
Fig. 5 is 3, the mass spectrum of 3 '-diacetylene-4,4 '-difluorodiphenyl sulfone
Fig. 6 be triazole functionalized 4,4 '-difluorodiphenyl sulfone
1hNMR collection of illustrative plates.
specific implementation method
Below in conjunction with embodiment, the present invention is described in detail.
embodiment one
The present embodiment with 4,4 '-difluorodiphenyl sulfone for raw material, by Reactive Synthesis target products such as bromo, coupling, clicks, (1) step is 3,3 '-two bromo-4, and the synthesis of 4 '-difluorodiphenyl sulfone, (2) step is 3,3 '-two trimethyl silicon based ethynyl-4,4 '-difluorodiphenyl sulfone synthesis, (3) step is 3,3 '-diacetylene-4, the synthesis of 4 '-difluorodiphenyl sulfone, (4) step is the synthesis of functionalized 4, the 4 '-difluorodiphenyl sulfone of triazole.
Experimental procedure:
(1) in 50ml round-bottomed flask, 18.32g4 is added, 4 '-difluorodiphenyl sulfone and the dense H of 45ml
2sO
4, stirring at normal temperature, makes 4, and 4 '-difluorodiphenyl sulfone dissolves completely, then in above-mentioned solution, adds 28.26gNBS.Point plate tracking reaction process, after about 6h, reaction terminates, and pours in the beaker filling 350g frozen water, after ice cube all melts, obtain yellow-white cloudy mixture by solution after reaction.Mixture sand core funnel low pressure suction filtration, then priority use water, n-hexane, obtain faint yellow solid.Re crystallization from toluene obtains white solid, productive rate 92.5%, characterizes and sees Fig. 1 and Fig. 2.
(2) by 2g3,3 '-two bromo-4,4 '-difluorodiphenyl sulfone adds in tube sealing, uses N
2gas fills ventilation 4 ~ 5 times, then at N
20.056gCuI, 0.2gPdCl is added successively under protection
2(PPh
3)
2, 16mlEt
3n, 9mlTHF and 1.192g trimethylsilyl acetylene, 45 DEG C of reactions, some plate observing response process, 7h reacts completely, and naturally cools to room temperature after reaction unit being shifted out oil bath, then product sand core funnel suction filtration, and by dichloromethane rinse twice, obtains filtrate.Filtrate is added a certain amount of silica gel, and 40 DEG C revolve steaming, and column chromatography for separation obtains 3,3 '-two trimethyl silicon based ethynyl-4,4 '-difluorodiphenyl sulfone, and crossing post leacheate is sherwood oil: methylene dichloride=8:5, and productive rate is 64.64 ﹪, characterize and see Fig. 3.
(3) by 1.5g3,3 '-two trimethyl silicon based ethynyl-4,4 '-difluorodiphenyl sulfone is dissolved in 15mlTHF, then add and add 1.197g tetrabutyl ammonium fluoride again in solution, stirring at normal temperature is reacted, and adds 50ml ethyl acetate and 15ml water, and carry out separatory operation after reacting completely.Lower floor is water white aqueous phase, and upper strata is brown light tone organic phase.Organic phase adds appropriate anhydrous Na
2sO
4carry out drying treatment.Filtration after drying completes, adds a certain amount of silica gel by filtrate, and 40 DEG C revolve steaming, column chromatography for separation obtains 3,3 '-two trimethyl silicon based ethynyl-4,4 '-difluorodiphenyl sulfone, crossing post leacheate is sherwood oil: methylene dichloride=8:5, and productive rate is 54.03 ﹪, characterizes and sees Fig. 4 and Fig. 5.
(4) by 0.5g3,3 '-diacetylene-4,4 '-difluorodiphenyl sulfone adds in round-bottomed flask, fills and changes nitrogen, add 0.0264gCuSO successively under nitrogen protection
4, 1.64gNaAsc, 5mlTHF and 0.649g trimethylacetic acid nitrine methyl esters, some plate observing response process, until react completely, add ethyl acetate and water stratification, organic layer cleans with the ammoniacal liquor of 5% again, anhydrous MgSO
4drying, filtration is spin-dried for, and column chromatography for separation obtains triazole functionalized 4,4 '-difluorodiphenyl sulfone, and structural formula is
, crossing post leacheate is methylene dichloride: ethyl acetate=40:1, and productive rate is 74.21 ﹪, characterizes and sees Fig. 6.
embodiment two
(1) 3,3 '-two bromo-4, the synthesis of 4 '-difluorodiphenyl sulfone: with embodiment one
(2) 3,3 '-two trimethyl silicon based ethynyl-4,4 '-difluorodiphenyl sulfone synthesis: with embodiment one
(3) get 1.2g3,3 '-two trimethyl silicon based ethynyl-4,4 '-difluorodiphenyl sulfone is dissolved in 15mlTHF, then adds and add 1.508gKOH again in solution, and stirring at normal temperature is reacted, and adds 50ml ether and 15ml water, and carry out separatory operation after reacting completely.Organic phase adds appropriate anhydrous Na
2sO
4carry out drying treatment.Filtration after drying completes, adds a certain amount of silica gel by filtrate, and 40 DEG C revolve steaming, and column chromatography for separation obtains 3,3 '-two trimethyl silicon based ethynyl-4,4 '-difluorodiphenyl sulfone, and crossing post leacheate is sherwood oil: methylene dichloride=8:5, productive rate is 40.8 ﹪.
(4) triazole functionalized 4, the synthesis of 4 '-difluorodiphenyl sulfone: with embodiment one
embodiment three
(1) 3,3 '-two bromo-4, the synthesis of 4 '-difluorodiphenyl sulfone: with embodiment one
(2) 3,3 '-two trimethyl silicon based ethynyl-4,4 '-difluorodiphenyl sulfone synthesis: with embodiment one
(3) 3, the synthesis of 3 '-diacetylene-4,4 '-difluorodiphenyl sulfone: with embodiment one
(4) by 0.5g3,3 '-diacetylene-4,4 '-difluorodiphenyl sulfone adds in round-bottomed flask, fills and changes nitrogen, add 0.0264gCuSO successively under nitrogen protection
4, 1.64gNaAsc, 5mlTHF and 0.476g TMSA, some plate observing response process, until react completely, add ethyl acetate and water stratification, organic layer cleans with the ammoniacal liquor of 5% again, anhydrous MgSO
4drying, filtration is spin-dried for, and column chromatography for separation obtains triazole functionalized 4,4 '-difluoro
twobenzene sulfone.
Compound synthesized by the present invention can carry out polycondensation with bisphenol compound, obtain polymer polysulfone material, the skeleton structure of polysulfones makes it have excellent resistance alcohol effect and anti-oxidant, antiacid catalytic hydrolysis performance, and excellent mechanical property and thermostability, and triazole basic functionality provides proton defect, can be used for preparing acid-alkali both sexes high temperature proton conducting material.
Claims (1)
1. a triazole functionalized 4, the preparation method of 4 '-difluorodiphenyl sulfone compound, the structural formula of this compound is:
；
It is characterized in that the concrete steps of the method are:
A. by 4, after 4 '-difluorodiphenyl sulfone and N-bromo-succinimide press the mixed in molar ratio of 1:2.2 ~ 1:2.5, add the vitriol oil of catalyst levels, normal-temperature reaction, after determining end by a plate, solution is poured in frozen water, throw out use water, n-hexane, separating-purifying obtains 3, and 3 '-two bromo-4,4 '-difluorodiphenyl sulfone, its structural formula is:
;
B., under air tight condition and inert atmosphere, by step a gained 3,3 '-two bromo-4,4 '-difluorodiphenyl sulfone and trimethylsilyl acetylene are dissolved in tetrahydrofuran (THF) by the mol ratio of 1:2.2 ~ 1:3, then add CuI, PdCl of catalyst levels
2(PPh
3)
2and Et
3n, stirring reaction is complete to reactant reaction, and filtration is spin-dried for, and separating-purifying obtains 3,3 '-two trimethyl silicon based ethynyl-4,4 '-difluorodiphenyl sulfone, and its structural formula is:
;
By step b gained 3,3 '-two trimethyl silicon based ethynyl-4,4 '-difluorodiphenyl sulfone and tetrabutyl ammonium fluoride are dissolved in tetrahydrofuran (THF) by the mol ratio of 1:2 ~ 1:2.5, stirring at normal temperature reaction is complete to reactant reaction, extraction, organic layer saturated common salt water washing, 3 are obtained after drying, separating-purifying, 3 '-diacetylene-4,4 '-difluorodiphenyl sulfone, its structural formula is:
;
D. under inert atmosphere, by step c gained 3,3 '-diacetylene-4,4 '-difluorobenzene sulfone and trimethylacetic acid nitrine methyl esters or TMSA are dissolved in tetrahydrofuran (THF) by the mol ratio of 1:2 ~ 1:2.5, then add the CuSO of catalyst levels successively
4, NaAsc, stirring reaction is complete to reactant reaction, and after extraction, organic layer cleans with the ammoniacal liquor of 5% again, anhydrous MgSO
4drying, filtration is spin-dried for, and separating-purifying obtains triazole functionalized 4,4 '-difluorodiphenyl sulfone.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310505487.4A CN103755650B (en) | 2013-10-24 | 2013-10-24 | Triazole functionalized 4,4 '-difluorodiphenyl sulfone compound and synthetic method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310505487.4A CN103755650B (en) | 2013-10-24 | 2013-10-24 | Triazole functionalized 4,4 '-difluorodiphenyl sulfone compound and synthetic method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN103755650A CN103755650A (en) | 2014-04-30 |
| CN103755650B true CN103755650B (en) | 2016-03-30 |
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