CN101948372B - 2-methoxyl-3,4-difluorobenzene, preparation method and application thereof - Google Patents
2-methoxyl-3,4-difluorobenzene, preparation method and application thereof Download PDFInfo
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- CN101948372B CN101948372B CN2010100337125A CN201010033712A CN101948372B CN 101948372 B CN101948372 B CN 101948372B CN 2010100337125 A CN2010100337125 A CN 2010100337125A CN 201010033712 A CN201010033712 A CN 201010033712A CN 101948372 B CN101948372 B CN 101948372B
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- difluorobenzene
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- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- RDOGTTNFVLSBKG-UHFFFAOYSA-N 1,2-difluoro-3-methoxybenzene Chemical compound COC1=CC=CC(F)=C1F RDOGTTNFVLSBKG-UHFFFAOYSA-N 0.000 title abstract 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims abstract description 3
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims abstract description 3
- 230000000694 effects Effects 0.000 claims description 4
- ODGIMMLDVSWADK-UHFFFAOYSA-N 4-trifluoromethylaniline Chemical compound NC1=CC=C(C(F)(F)F)C=C1 ODGIMMLDVSWADK-UHFFFAOYSA-N 0.000 claims description 3
- 239000012954 diazonium Substances 0.000 claims description 2
- 150000001989 diazonium salts Chemical class 0.000 claims description 2
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 17
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 abstract description 4
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 abstract description 2
- 235000010290 biphenyl Nutrition 0.000 abstract description 2
- 239000004305 biphenyl Substances 0.000 abstract description 2
- 230000021615 conjugation Effects 0.000 abstract description 2
- IOCGMLSHRBHNCM-UHFFFAOYSA-N difluoromethoxy(difluoro)methane Chemical group FC(F)OC(F)F IOCGMLSHRBHNCM-UHFFFAOYSA-N 0.000 abstract 4
- WRDGNXCXTDDYBZ-UHFFFAOYSA-N 2,3,4-trifluoroaniline Chemical compound NC1=CC=C(F)C(F)=C1F WRDGNXCXTDDYBZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000009825 accumulation Methods 0.000 abstract 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000012074 organic phase Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000010025 steaming Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- CSJLBAMHHLJAAS-UHFFFAOYSA-N diethylaminosulfur trifluoride Chemical compound CCN(CC)S(F)(F)F CSJLBAMHHLJAAS-UHFFFAOYSA-N 0.000 description 6
- 238000001819 mass spectrum Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 235000010338 boric acid Nutrition 0.000 description 5
- 239000007810 chemical reaction solvent Substances 0.000 description 5
- 238000004440 column chromatography Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000005619 boric acid group Chemical class 0.000 description 4
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229940126214 compound 3 Drugs 0.000 description 4
- -1 difluoro methylene ether Chemical compound 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000001246 bromo group Chemical group Br* 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- LTVOKYUPTHZZQH-UHFFFAOYSA-N difluoromethane Chemical group F[C]F LTVOKYUPTHZZQH-UHFFFAOYSA-N 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 2
- KMKYPCWSAHHPAQ-UHFFFAOYSA-N 3,4,6,6-tetrafluoro-8-(4-heptylphenyl)benzo[c]chromene Chemical compound FC1=C(C2=C(C3=C(C(O2)(F)F)C=C(C=C3)C2=CC=C(C=C2)CCCCCCC)C=C1)F KMKYPCWSAHHPAQ-UHFFFAOYSA-N 0.000 description 2
- KBGBFNKKHMATPJ-UHFFFAOYSA-N 3,4,6,6-tetrafluoro-8-(4-hexylphenyl)benzo[c]chromene Chemical compound FC1=C(C2=C(C3=C(C(O2)(F)F)C=C(C=C3)C2=CC=C(C=C2)CCCCCC)C=C1)F KBGBFNKKHMATPJ-UHFFFAOYSA-N 0.000 description 2
- IBAPHKWMDXUSKT-UHFFFAOYSA-N 3,4,6,6-tetrafluoro-8-(4-nonylphenyl)benzo[c]chromene Chemical compound FC1=C(C2=C(C3=C(C(O2)(F)F)C=C(C=C3)C2=CC=C(C=C2)CCCCCCCCC)C=C1)F IBAPHKWMDXUSKT-UHFFFAOYSA-N 0.000 description 2
- VTCAWPBUXHAZIT-UHFFFAOYSA-N 3,4,6,6-tetrafluoro-8-(4-octylphenyl)benzo[c]chromene Chemical compound FC1=C(C2=C(C3=C(C(O2)(F)F)C=C(C=C3)C2=CC=C(C=C2)CCCCCCCC)C=C1)F VTCAWPBUXHAZIT-UHFFFAOYSA-N 0.000 description 2
- BJGKVCKGUBYULR-UHFFFAOYSA-N 3-bromo-2-methylbenzoic acid Chemical compound CC1=C(Br)C=CC=C1C(O)=O BJGKVCKGUBYULR-UHFFFAOYSA-N 0.000 description 2
- HTEAQCDTLFWKMQ-UHFFFAOYSA-N 8-(4-butylphenyl)-3,4,6,6-tetrafluorobenzo[c]chromene Chemical compound FC1=C(C2=C(C3=C(C(O2)(F)F)C=C(C=C3)C2=CC=C(C=C2)CCCC)C=C1)F HTEAQCDTLFWKMQ-UHFFFAOYSA-N 0.000 description 2
- MJYLKIYJWIEAET-UHFFFAOYSA-N 8-(4-decylphenyl)-3,4,6,6-tetrafluorobenzo[c]chromene Chemical compound FC1=C(C2=C(C3=C(C(O2)(F)F)C=C(C=C3)C2=CC=C(C=C2)CCCCCCCCCC)C=C1)F MJYLKIYJWIEAET-UHFFFAOYSA-N 0.000 description 2
- YRANXSSJXOERCX-UHFFFAOYSA-N 8-(4-ethylphenyl)-3,4,6,6-tetrafluorobenzo[c]chromene Chemical compound FC1=C(C2=C(C3=C(C(O2)(F)F)C=C(C=C3)C2=CC=C(C=C2)CC)C=C1)F YRANXSSJXOERCX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- UMVBURNNXFLFSN-UHFFFAOYSA-N [4-(3,4,6,6-tetrafluorobenzo[c]chromen-8-yl)phenyl]methanamine Chemical compound FC1=CC=C2C3=C(C(OC2=C1F)(F)F)C=C(C=C3)C3=CC=C(C=C3)CN UMVBURNNXFLFSN-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229960001701 chloroform Drugs 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- CFHGBZLNZZVTAY-UHFFFAOYSA-N lawesson's reagent Chemical compound C1=CC(OC)=CC=C1P1(=S)SP(=S)(C=2C=CC(OC)=CC=2)S1 CFHGBZLNZZVTAY-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- SLFVYFOEHHLHDW-UHFFFAOYSA-N n-(trifluoromethyl)aniline Chemical compound FC(F)(F)NC1=CC=CC=C1 SLFVYFOEHHLHDW-UHFFFAOYSA-N 0.000 description 2
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 2
- WIHIUTUAHOZVLE-UHFFFAOYSA-N 1,3-diethoxypropan-2-ol Chemical compound CCOCC(O)COCC WIHIUTUAHOZVLE-UHFFFAOYSA-N 0.000 description 1
- QPWYRLZKEZYNDS-UHFFFAOYSA-N B(O)(O)O.C(CCCC)C1=CC=CC=C1 Chemical compound B(O)(O)O.C(CCCC)C1=CC=CC=C1 QPWYRLZKEZYNDS-UHFFFAOYSA-N 0.000 description 1
- XVRSZRBGOKDECJ-UHFFFAOYSA-N Bc(ccc(F)c1F)c1OC Chemical compound Bc(ccc(F)c1F)c1OC XVRSZRBGOKDECJ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- PSCXEUSWZWRCMQ-UHFFFAOYSA-N F[S](F)F Chemical compound F[S](F)F PSCXEUSWZWRCMQ-UHFFFAOYSA-N 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- TWLNVQNCJFIEEU-UHFFFAOYSA-N [N].CC(C)=O Chemical compound [N].CC(C)=O TWLNVQNCJFIEEU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
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- 150000004795 grignard reagents Chemical class 0.000 description 1
- ZYCMDWDFIQDPLP-UHFFFAOYSA-N hbr bromine Chemical compound Br.Br ZYCMDWDFIQDPLP-UHFFFAOYSA-N 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
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Abstract
The invention discloses 2-methoxyl-3,4-difluorobenzene, a preparation method and application thereof. A structural formula of the provided 2-methoxyl-3,4-difluorobenzene is disclosed by a formula (3). The preparation method comprises the following steps of: preparing 2,3,4-trifluoroaniline into a diazo salt; and obtaining the 2-methoxyl-3,4-difluorobenzene disclosed by the formula (3) under the actions of methanol and cuprous bromide sequentially. The 2-methoxyl-3,4-difluorobenzene can be used for preparing a novel lateral difluoromethyl ether bridge-bond fluoroalkyl terphenyl liquid-crystal compound, and a structural general formula is disclosed by a formula (1). In the liquid-crystal compound, a difluoromethyl ether group is introduced into a terphenyl loop structure; owing to a C-F key electronegative accumulation function in the difluoromethyl ether group and the molecular long-axis lateral deviation position of the difluoromethyl ether group, the molecules have a larger vertical molecular axial dielectric constant (epsilon). Because the introduction of the difluoromethyl ether group destroys the conjugation of a biphenyl structure, the melting point of the novel lateral difluoromethyl ether bridge-bond fluoroalkyl terphenyl liquid-crystal compound is reduced, and the solubility is increased. The 2-methoxyl-3,4-difluorobenzene has a good application prospect in the field of liquid crystal display.
Description
Technical field
The present invention relates to 2-methoxyl group-3,4-difluoro bromobenzene and preparation method thereof and its application in the preparation liquid crystalline cpd.
Background technology
Develop rapidly along with TFT liquid-crystal display (Thin Solid Film); Requirement to the high-performance liquid crystal material is more and more urgent, especially for obtaining wideer operating temperature range, reduces driving voltage; Realize the reduce power consumption of display device; The development dielectric anisotropy is big, and fusing point is low, and the wide high-performance liquid crystal material of mesomorphic TR is that TFT is with liquid crystal material research direction from now on.
In the liquid crystalline cpd design process, reasonably introduce difluoro methylene ether end group or linking group, the effect that can play is following:
1. broadening nematic temperature range
2. increase dielectric anisotropy value (Δ ε)
3. improve the solubility property of liquid crystalline cpd
4. reduce rotary viscosity (γ
1)
5. improve voltage retention (VHR)
The liquid crystalline cpd that the people such as Bartmann Ekkehard of Germany Merck company will have
structure is used for mixed liquid crystal (German patent DE 19531165,1995); The liquid crystalline cpd that first-class people of the loose well autumn of Japan Chisso company will have
structure is used for mixed liquid crystal (Chinese patent CN1158602,1995); The liquid crystalline cpd that the same people such as Andou Tugumiti of Chisso company in addition will have
structure is used for mixed liquid crystal (European patent EP 0844229,1998); All these materials have all shown good physicals.
Summary of the invention
The purpose of this invention is to provide 2-methoxyl group-3,4-difluoro bromobenzene and preparation method thereof.
2-methoxyl group-3 provided by the present invention, 4-difluoro bromobenzene, its structural formula be suc as formula shown in (3),
Formula (3).
Compound 2-methoxyl group-3 shown in the formula (3), the preparation method of 4-difluoro bromobenzene is following:
With 2,3, the 4-trifluoromethyl aniline is prepared into diazonium salt, under the effect of methyl alcohol, cuprous bromide, obtains compound 2-methoxyl group-3 shown in the formula (3), 4-difluoro bromobenzene then successively earlier.
Compound 2-methoxyl group-3 provided by the present invention, 4-difluoro bromobenzene can be used for preparing one type of novel side difluoro methylene ether bridged bond fluoro-alkyl terphenyl liquid crystalline cpd.
The structural formula of said side difluoro methylene ether bridged bond fluoro-alkyl terphenyl liquid crystalline cpd is suc as formula shown in (1),
Formula (1)
Wherein, R is the straight or branched alkyl.
It is 1～10 straight or branched alkyl that said R is preferably carbonatoms.
More specifically, said side difluoro methylene ether bridged bond fluoro-alkyl terphenyl liquid crystalline cpd comprises following substances:
3,4,6,6-tetrafluoro-8-(4-aminomethyl phenyl)-6H-benzo [c] chromene,
3,4,6,6-tetrafluoro-8-(4-ethylphenyl)-6H-benzo [c] chromene,
3,4,6,6-tetrafluoro-8-(4-propyl group phenyl)-6H-benzo [c] chromene,
3,4,6,6-tetrafluoro-8-(4-butyl phenyl)-6H-benzo [c] chromene,
3,4,6,6-tetrafluoro-8-(4-amyl group phenyl)-6H-benzo [c] chromene,
3,4,6,6-tetrafluoro-8-(4-hexyl phenyl)-6H-benzo [c] chromene,
3,4,6,6-tetrafluoro-8-(4-heptyl phenyl)-6H-benzo [c] chromene,
3,4,6,6-tetrafluoro-8-(4-octyl phenyl)-6H-benzo [c] chromene,
3,4,6,6-tetrafluoro-8-(4-nonyl phenyl)-6H-benzo [c] chromene,
3,4,6,6-tetrafluoro-8-(4-decyl phenyl)-6H-benzo [c] chromene.
The preparation method of formula (1) compound comprises the steps:
1) compound 2 shown in the preparation formula (4) '-methoxyl group-3 ', 4 '-two fluorobenzoic boric acids
Compound shown in the formula (3) and MAGNESIUM METAL 99 reaction are generated Grignard reagent, with the trimethyl borate reaction, obtain compound 2-methoxyl group-3 shown in the formula (4) after the hydrolysis, 4-two fluorobenzoic boric acids then;
2) compound 2 shown in the preparation formula (6) '-methoxyl group-3 ', 4 '-DfBP-2-methyl-formiate
Compound shown in the formula (4) and 2-methyl-bromobenzoate are carried out linked reaction under catalyst action, obtain compound 2 shown in the formula (6) '-methoxyl group-3 ', 4 '-DfBP-2-methyl-formiate; Said catalyzer be selected from following any one: four (triphenylphosphines) close palladium (0), two (triphenylphosphine) palladium chloride (II), palladium (II), and palladium/carbon catalyst;
(formula 4) (formula 6)
3) compound shown in the preparation formula (7)
Compound shown in the formula (6) is carried out ring closure reaction under the boron tribromide effect, obtain compound 3 shown in the formula (7), 4-two fluoro-6H-benzo [c] chromene-6-ketone;
4) compound shown in the preparation formula (9)
With red precipitate and mass concentration is that 98% sulfuric acid is catalyzer, uses bromine that compound shown in the formula (7) is carried out bromo, obtains compound 3 shown in the formula (8), 4-two fluoro-8-bromo-6H-benzo [c] chromene-6-ketone; Make that compound carries out linked reaction shown in 4-korenyl boric acid and the formula (8) under catalyst action, obtain compound 3 shown in the formula (9), 4-two fluoro-8-(4-alkyl phenyl)-6H-benzo [c] chromene-6-ketone; Said catalyzer be selected from following any one: four (triphenylphosphines) close palladium (0), two (triphenylphosphine) palladium chloride (II), palladium (II), and palladium/carbon catalyst;
(formula 7) (formula 8)
5) under the refluxing toluene condition, make compound shown in the formula (9) and Lawesson reagent carry out thio reaction and obtain compound 3 shown in the formula (10), 4-two fluoro-8-(4-alkyl phenyl)-6H-benzo [c] chromene-6-thioketones;
(formula 9) (formula 10)
Wherein, the R in formula 9 and the formula 10 is the straight or branched alkyl;
6) compound shown in the formula (10) and diethylaminosulfurtrifluoride (DAST) are carried out fluoro-reaction, obtain compound shown in the formula (1).
Wherein, step 2) in the said linked reaction, temperature of reaction can be 50 ℃-100 ℃, and reaction solvent can be benzene, water and absolute ethyl alcohol.
In the said ring closure reaction of step 3), temperature of reaction can be-80 ℃-30 ℃, and reaction solvent can be methylene dichloride, trichloromethane or tetracol phenixin.
In the said linked reaction of step 4), temperature of reaction can be 50 ℃-100 ℃, and reaction solvent can be benzene, water and absolute ethyl alcohol.
In the said thio reaction of step 5), temperature of reaction can be 20 ℃-120 ℃, and reaction solvent can be benzene or toluene.
In the said fluoro-reaction of step 6), temperature of reaction is 20 ℃-100 ℃, and reaction solvent is methylene dichloride, trichloromethane or tetracol phenixin.
Advantages such as it is suitable that compound shown in the formula (1) has dielectric anisotropy (Δ ε), and specific refractory power anisotropy (Δ n) is bigger are a kind of well behaved liquid crystal display materials.
Compound has been introduced the difluoro methylene ether group shown in the formula (1) in the terphenyl ring structure, has obtained one type of new compound.Because the molecular long axis lateral deviation position that is in of the electronegative cumulative function of C-F key and this group makes this quasi-molecule have the axial specific inductivity (ε of bigger perpendicular molecules in this group
⊥), and, the fusing point of this compounds is reduced because the introducing of difluoro methylene ether group has destroyed the conjugation of biphenyl structural, and solubility property increases, and such material has good prospects for application in field of liquid crystal display.
Description of drawings
Fig. 1 is the 2-methoxyl group-3 of embodiment 1 preparation, the infrared spectrogram of 4-difluoro bromobenzene.
Fig. 2 is the 2-methoxyl group-3 of embodiment 1 preparation, the hydrogen nuclear magnetic resonance spectrogram of 4-difluoro bromobenzene.
Fig. 3 is the 2-methoxyl group-3 of embodiment 1 preparation, the mass spectrum of 4-difluoro bromobenzene.
Fig. 4 be 2 of embodiment 3 preparation '-methoxyl group-3 ', 4 '-infrared spectrogram of DfBP-2-methyl-formiate.
Fig. 5 be 2 of embodiment 3 preparation '-methoxyl group-3 ', 4 '-the hydrogen nuclear magnetic resonance spectrogram of DfBP-2-methyl-formiate.
Fig. 6 be 2 of embodiment 3 preparation '-methoxyl group-3 ', 4 '-mass spectrum of DfBP-2-methyl-formiate.
Fig. 7 is 3 of embodiment 4 preparations, the infrared spectrogram of 4-two fluoro-6H-benzo [c] chromene-6-ketone.
Fig. 8 is 3 of embodiment 4 preparations, the hydrogen nuclear magnetic resonance spectrogram of 4-two fluoro-6H-benzo [c] chromene-6-ketone.
Fig. 9 is 3 of embodiment 4 preparations, the mass spectrum of 4-two fluoro-6H-benzo [c] chromene-6-ketone.
Figure 10 is 3 of embodiment 6 preparations, the infrared spectrogram of 4-two fluoro-8-(4-amyl group phenyl)-6H-benzo [c] chromene-6-ketone.
Figure 11 is 3 of embodiment 6 preparations, the mass spectrum of 4-two fluoro-8-(4-amyl group phenyl)-6H-benzo [c] chromene-6-ketone.
Figure 12 is 3 of embodiment 6 preparations, the DSC figure of 4-two fluoro-8-(4-amyl group phenyl)-6H-benzo [c] chromene-6-ketone.
Figure 13 is 3 of embodiment 7 preparations, the infrared spectrogram of 4-two fluoro-8-(4-amyl group phenyl)-6H-benzo [c] chromene-6-thioketones.
Figure 14 is 3 of embodiment 7 preparations, the mass spectrum of 4-two fluoro-8-(4-amyl group phenyl)-6H-benzo [c] chromene-6-thioketones.
Figure 15 is 3 of embodiment 7 preparations, the DSC figure of 4-two fluoro-8-(4-amyl group phenyl)-6H-benzo [c] chromene-6-thioketones.
Figure 16 is the infrared spectrogram of formula 1 compound of embodiment 8 preparations.
Figure 17 is the mass spectrum of formula 1 compound of embodiment 8 preparations.
Figure 18 is the DSC figure of formula 1 compound of embodiment 8 preparations.
Embodiment
Following embodiment is convenient to understand better the present invention, but does not limit the present invention.Experimental technique among the following embodiment like no specified otherwise, is ordinary method.Used test materials among the following embodiment like no specified otherwise, is to buy from conventional reagent shop and obtains.
In the 500mL beaker, stir down, (mass concentration: 50%) add 92g 2,3 in the sulphuric acid soln, the 4-trifluoromethyl aniline obtains white trifluoromethyl aniline vitriol mashed prod in batches to cold 160g.Stir down, control reaction temperature is less than 30 ℃, and (mass concentration: add the 47g Sodium Nitrite 98%), reinforced finishing kept stirring at room 30 minutes, was warming up to 70～75 ℃, stirred 1 hour, and be subsequent use in batches to the 320g vitriol oil.Controlled temperature stirs down with in the trifluoromethyl aniline vitriol mashed prod adding products therefrom sulfuric acid nitrosyl less than 30 ℃.Above-mentioned products therefrom is poured in the 2000mL beaker, and 20～30 ℃ of control reacting liquid temperatures stir down, and to wherein adding the 1.6L anhydrous methanol, reinforced finishing kept room temperature 35 minutes again.
Controlled temperature adds in 0.8mol cuprous bromide-hydrobromic acid solution with methyl alcohol reaction products therefrom above-mentioned less than 20 ℃ in batches.Reinforced finishing, stirring at room 30 minutes refluxed 2 hours.Reaction solution is reduced to room temperature, to wherein adding 1.6L water, and separatory, water is with 350mL * 3 dichloromethane extraction three times.Merge organic phase, deionized water wash is to neutrality, anhydrous sodium sulfate drying.Steam with Rotary Evaporators and to desolventize, the gained bullion is placed in-15 ℃ the refrigerator-freezer, suction filtration after 12 hours, the elimination solid, 108～112 ℃ of cuts are collected in the distillation of gained filtrate decompression, must 49.5g 2-methoxyl groups-3,4-difluoro bromobenzene (GC purity 95%), yield 35%.
The structural identification data are following:
IR(KBr)v
max/cm
-1：3095，3018，2945，2833，1612，1487，1470，1242，1055，798；
1HNMR(300MHz)δ：7.25(m，1H)，6.82(m，1H)，3.99(s，3H)；
MS(m/z)：223(M
+)，209，181。
The 1L there-necked flask is furnished with stirring rake, TM, constant pressure funnel and protects with drying tube.With 66.90g (0.30mol) 2-methoxyl group-3,4-difluoro bromobenzene and 200mL THF wiring solution-forming are subsequent use.In there-necked flask, drop into a granule iodine, 7.92g (0.33mol) magnesium chips and 100mL THF drip a little 2-methoxyl group-3, and the tetrahydrofuran solution of 4-difluoro bromobenzene causes grignard reaction with hair dryer, drip the tetrahydrofuran solution of residue bromobenzene.Whole dropping process is not higher than 30 ℃ with the ice-water bath control reaction temperature, drip to finish, and keeps 30～35 ℃ of reaction solutions 1.5 hours.
Above-mentioned reaction solution is cooled to-70 ℃ with the liquid nitrogen acetone soln, drips the solution that 34.32g (0.33mol) trimethyl borate and 150mL THF are made into.Drip and finish, kept 2 hours for-70 ℃, stirring reaction liquid rises to room temperature naturally.
Embodiment 3,2 '-methoxyl group-3 ', the preparation of 4 '-DfBP-2-methyl-formiate
The 1L there-necked flask is equipped with stirring rake, TM, reflux condensing tube, nitrogen bag and balloon protection.With 34.97g (186mmol) 2-methoxyl group-3,4-two fluorobenzoic boric acids, 39.99g (186mmol) 2-methyl-bromobenzoate, 5.39g (4.67mmol) Pd (PPh
3)
4, 50.40g (475mmol) soda ash light, 260mL benzene; In the disposable input there-necked flask of 260mL water and 235mL ethanol; Reflux, thin plate tracking monitor (developping agent: volume ratio is 1: 10 ETHYLE ACETATE and a sherwood oil mixed solvent) during reaction, raw material to be confirmed disappears; Stop to reflux, return time is 11 hours.Cooling reaction liquid adds about 50mL water to room temperature.Behind the standing demix, tell organic phase, water is with 150mL * 3 benzene extraction three times.Merge organic phase, water washing once, organic phase use anhydrous sodium sulfate drying, steaming with Rotary Evaporators must black bullion 66g after desolventizing.The gained bullion is with silica gel/aluminum oxide (10: 1) column chromatography purification, and leacheate use volume ratio is 1: 10 ETHYLE ACETATE and a sherwood oil mixed solvent.Leacheate is desolventized with the Rotary Evaporators steaming, get solid crude product 58.5g.Bullion is used the 100mL ethyl alcohol recrystallization, and Tc-15 ℃ obtains white crystal (2 '-methoxyl group-3 ', 4 '-DfBP-2-methyl-formiate) 45g (GC purity 98.6%), yield 87%.
The structural identification data are following:
IR(KBr)v
max/cm
-1：3064，3032，3008，2954，1720，1479，1259，1051；
1HNMR(300MHz)δ：7.93(d，1H)，7.55(m，1H)，7.44(m，1H)，7.26(d，1H)，6.89-6.93(m，2H)，3.71(s，3H)，3.68(s，3H)；
MS(m/z)：278(M
+)，247，232，204。
The 1L there-necked flask is furnished with stirring rake, TM, constant pressure funnel and drying tube.To wherein add 2 '-methoxyl group-3 ', 4 '-DfBP-2-methyl-formiate 32.0g (115mmol) and 340mL methylene dichloride.Keep reacting liquid temperature at 0～10 ℃, the mixing solutions that is made into to wherein Dropwise 5 7.5g (230mmol) boron tribromide and 100mL methylene dichloride.Drip and finish, keep 0～10 ℃, stirred 10 hours, stirring down, nature rises to room temperature.Drip saturated sodium bicarbonate aqueous solution to reaction solution to there-necked flask and be weakly alkaline.Tell organic phase, water is with 300mL * 3 dichloromethane extractions three times.Merge organic phase, water washing is to neutral, anhydrous sodium sulfate drying, with Rotary Evaporators steam after desolventizing product 26.2g (GC purity 98.93%), yield 99%.
The structural identification data:
IR(KBr)v
max/cm
-1：3093，3043，1751，1574，1473，1290，1269；
1HNMR(300MHz)δ：8.40(d，1H)，8.03(d，1H)，7.85(t，1H)，7.76(m，1H)，7.61(t，1H)，7.15(m，1H)；
MS(m/z)：232(M
+)，204。
In the 100mL there-necked flask of being furnished with whisking appliance, TM and reflux condensing tube; Add 10g (43mmol) 3,4-two fluoro-6H-benzo [c] chromene-6-ketone, 6.9g (43mmol) liquid bromine; 18.6g (86mmol) red precipitate and 4.3mL 98% vitriol oil, the 260mL tetracol phenixin.Reflux 10 hours, filtered while hot, filter cake is with hot tetracol phenixin drip washing.Organic phase is desolventized with the Rotary Evaporators steaming, get rice white bullion 8g.Identify that through GC-MS product is two kinds of bromos 3, the mixture of 4-two fluoro-6H-benzo [c] chromene-6-ketone, this mixture is not done purifying, directly drops into next step reaction.
In the there-necked flask of being furnished with electric mixer, TM, reflux condensing tube, nitrogen protection; Add 26.0g (83.6mmol) bromo 3,4-two fluoro-6H-benzo [c] chromene-6-ketone, 19.2g (100.3mmol) 4-amylbenzene boric acid; 22.5g soda ash light; 115mL benzene, 110mL ethanol, 110mL water and 0.88g (0.76mmol) Pd (Ph
3P)
4, refluxed 14 hours, reduce to room temperature.Tell organic phase, water extracts three times with 150mL * 3 benzene.Merge organic phase, water washing is to neutral, and anhydrous sodium sulfate drying desolventizes with the Rotary Evaporators steaming, and the gained bullion is with silica gel/aluminum oxide (10: 1) column chromatography purification, and leacheate is that volume ratio is 1: 10 ETHYLE ACETATE and a sherwood oil mixed solvent.In the column chromatography process, thin-layer chromatography monitoring, leacheate Fractional Collections, the R of title product
fBe about 0.6, will contain the title product leacheate and desolventize, get bullion 15.7g, add the crystallization of 75mL ETHYLE ACETATE, get white plates crystal 6 .3g, yield 19.9% with the Rotary Evaporators steaming.
The structural identification data:
IR(KBr)v
max/cm
-1：2960，2929，2856，1749，1560，1485，1468，1261，1041；
1HNMR(300MHz)δ：8.59(s，1H)，8.12-8.02(m，2H)，7.78(m，1H)，7.59(d，2H)，7.30(d，2H)，7.15(m，1H)，2.66(t，2H)，1.68(m，2H)，1.35(m，4H)，0.91(t，3H)；
MS(m/z)：378(M
+)，321。
This compound has mesomorphic phase, and related data is following: Δ ε=3.90, ε
⊥=19.10 (using LCR Meter to measure); Δ n=0.25 (using the Abbe refractometer to measure); γ
1=446mPas (using Toyo6254 liquid crystal comprehensive tester to measure); Liquid crystal phase temperature range (DSC): C111.3 ℃ of N188.5 ℃ of I (dsc measurement).
Can obtain with identical method:
3,4-two fluoro-8-(4-aminomethyl phenyl)-6H-benzo [c] chromene-6-ketone,
3,4-two fluoro-8-(4-ethylphenyl)-6H-benzo [c] chromene-6-ketone,
3,4-two fluoro-8-(4-propyl group phenyl)-6H-benzo [c] chromene-6-ketone,
3,4-two fluoro-8-(4-butyl phenyl)-6H-benzo [c] chromene-6-ketone,
3,4-two fluoro-8-(4-hexyl phenyl)-6H-benzo [c] chromene-6-ketone,
3,4-two fluoro-8-(4-heptyl phenyl)-6H-benzo [c] chromene-6-ketone,
3,4-two fluoro-8-(4-octyl phenyl)-6H-benzo [c] chromene-6-ketone,
3,4-two fluoro-8-(4-nonyl phenyl)-6H-benzo [c] chromene-6-ketone,
3,4-two fluoro-8-(4-decyl phenyl)-6H-benzo [c] chromene-6-ketone.
Embodiment 7,3, the preparation of 4-two fluoro-8-(4-amyl group phenyl)-6H-benzo [c] chromene-6-thioketones
The 250mL there-necked flask is furnished with stirring rake, TM, reflux condensing tube and nitrogen protection device.With 5.0g (13.2mmol) 3,4-two fluoro-8-(4-amyl group phenyl)-6H-benzo [c] chromene-6-ketone, 10.7g (26.4mmol) Lao Weisheng reagent (Lawesson reagent) and 100mL toluene added in the there-necked flask, nitrogen protection refluxed 72 hours.Reduce to room temperature, add the dilution of 110mL benzene and 80mL sherwood oil, suction filtration is removed solid.Organic phase is steamed with Rotary Evaporators and is desolventized, and the gained bullion is with silica gel/aluminum oxide (10: 1) column chromatography purification, and leacheate use volume ratio is 1: 10 ETHYLE ACETATE and a sherwood oil mixed solvent.Leacheate steams with Rotary Evaporators and desolventizes, and obtains yellow solid bullion 4.5g.This bullion is used the 50mL re-crystallizing in ethyl acetate, obtain the yellow trichite (GC purity 94.0%) of 0.9g.Yield 17.3%.
The structural identification data are following:
IR(KBr)v
max/cm
-1：3093，3028，2922，2852，1531，1479，1464，1261，1217；
1HNMR(300MHz)δ：8.97(s，1H)，8.10-7.98(m，2H)，7.79(m，1H)，7.59(d，2H)，7.30(d，2H)，7.21(m，1H)，2.67(t，2H)，1.70(m，2H)，1.34(m，4H)，0.91(t，3H)；
MS(m/z)：394(M
+)，337。
Can obtain with identical method:
3,4-two fluoro-8-(4-aminomethyl phenyl)-6H-benzo [c] chromene-6-thioketones,
3,4-two fluoro-8-(4-ethylphenyl)-6H-benzo [c] chromene-6-thioketones,
3,4-two fluoro-8-(4-propyl group phenyl)-6H-benzo [c] chromene-6-thioketones,
3,4-two fluoro-8-(4-butyl phenyl)-6H-benzo [c] chromene-6-thioketones,
3,4-two fluoro-8-(4-hexyl phenyl)-6H-benzo [c] chromene-6-thioketones,
3,4-two fluoro-8-(4-heptyl phenyl)-6H-benzo [c] chromene-6-thioketones,
3,4-two fluoro-8-(4-octyl phenyl)-6H-benzo [c] chromene-6-thioketones,
3,4-two fluoro-8-(4-nonyl phenyl)-6H-benzo [c] chromene-6-thioketones,
3,4-two fluoro-8-(4-decyl phenyl)-6H-benzo [c] chromene-6-thioketones.
The 100mL there-necked flask is furnished with magnetic agitation, TM and the protection of nitrogen bag.Add 1.00g (2.53mmol) 3,4-two fluoro-8-(4-amyl group phenyl)-6H-benzo [c] chromene-6-thioketones and 30mL methylene dichloride are injected 0.81g (5.06mmol) diethylin sulfur trifluoride (DAST) with syringe in batches in there-necked flask.Kept room temperature 22 hours.Drip saturated sodium bicarbonate solution, be neutralized to alkalescence.Tell organic phase, water is with 20mL * 3 dichloromethane extractions three times.Merge organic phase, water washing is to neutral, and anhydrous sodium sulfate drying desolventizes with the Rotary Evaporators steaming, gets bullion 0.70g.The gained bullion is with silica gel/aluminum oxide (10: 1) column chromatography purification, and leacheate is that volume ratio is 1: 10 ETHYLE ACETATE and a sherwood oil mixed solvent.Leacheate steams with Rotary Evaporators and desolventizes, and obtains bullion 0.40g, and it is 1: 1 ETHYLE ACETATE and sherwood oil mixed solvent recrystallization that this bullion is used volume ratio, obtains white needle-like crystals 0.28g (GC purity 99.0%), yield 27.6%.
The structural identification data are following:
IR(KBr)v
max/cm
-1：3097，3022，2927，2852，1533，1473，1471，1257，1032；
1HNMR(300MHz)δ：7.98(s，1H)，7.91-7.84(m，2H)，7.62(m，1H)，7.57(d，2H)，7.30(d，2H)，7.06(m，1H)，2.67(t，2H)，1.66(m，2H)，1.35(m，4H)，0.91(t，3H)；
MS(m/z)：400(M+)，343，293。
This compound has monotropic mesomorphic phase, and related data is following: Δ ε=3.40, ε
⊥=17.30 (using LCR Meter to measure); Δ n=0.20 (using the Abbe refractometer to measure); γ
1=371mpas (using Toyo6254 liquid crystal comprehensive tester to measure); Liquid crystal phase temperature range (DSC): C59.8 ℃ of (N31.9 ℃) I (dsc measurement).
Can obtain with identical method:
3,4,6,6-tetrafluoro-8-(4-aminomethyl phenyl)-6H-benzo [c] chromene,
3,4,6,6-tetrafluoro-8-(4-ethylphenyl)-6H-benzo [c] chromene,
3,4,6,6-tetrafluoro-8-(4-propyl group phenyl)-6H-benzo [c] chromene,
3,4,6,6-tetrafluoro-8-(4-butyl phenyl)-6H-benzo [c] chromene,
3,4,6,6-tetrafluoro-8-(4-hexyl phenyl)-6H-benzo [c] chromene,
3,4,6,6-tetrafluoro-8-(4-heptyl phenyl)-6H-benzo [c] chromene,
3,4,6,6-tetrafluoro-8-(4-octyl phenyl)-6H-benzo [c] chromene,
3,4,6,6-tetrafluoro-8-(4-nonyl phenyl)-6H-benzo [c] chromene,
3,4,6,6-tetrafluoro-8-(4-decyl phenyl)-6H-benzo [c] chromene.
Claims (1)
1. the preparation method of compound shown in the formula (3) comprises the steps: elder generation with 2,3, and the 4-trifluoromethyl aniline is prepared into diazonium salt, under the effect of methyl alcohol, cuprous bromide, obtains compound shown in the formula (3) then successively:
(formula 3).
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