CN102898288B - Difluorovinyl-ether-containing liquid crystal compound and composition and liquid crystal displayer thereof - Google Patents
Difluorovinyl-ether-containing liquid crystal compound and composition and liquid crystal displayer thereof Download PDFInfo
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- CN102898288B CN102898288B CN201210388534.7A CN201210388534A CN102898288B CN 102898288 B CN102898288 B CN 102898288B CN 201210388534 A CN201210388534 A CN 201210388534A CN 102898288 B CN102898288 B CN 102898288B
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 77
- 150000001875 compounds Chemical class 0.000 title claims abstract description 44
- 239000000203 mixture Substances 0.000 title claims abstract description 42
- MNCPYCODYCPASZ-UHFFFAOYSA-N 2-(2,2-difluoroethenoxy)-1,1-difluoroethene Chemical compound FC(F)=COC=C(F)F MNCPYCODYCPASZ-UHFFFAOYSA-N 0.000 title abstract 2
- 239000007788 liquid Substances 0.000 claims description 32
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 239000004983 Polymer Dispersed Liquid Crystal Substances 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 3
- 230000000704 physical effect Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- 229910000104 sodium hydride Inorganic materials 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 239000012043 crude product Substances 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 125000005843 halogen group Chemical group 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 150000001721 carbon Chemical group 0.000 description 6
- 125000004093 cyano group Chemical group *C#N 0.000 description 6
- 229960000935 dehydrated alcohol Drugs 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 5
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 5
- 210000002858 crystal cell Anatomy 0.000 description 5
- 239000003480 eluent Substances 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 125000005842 heteroatom Chemical group 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229960001866 silicon dioxide Drugs 0.000 description 5
- 239000012312 sodium hydride Substances 0.000 description 5
- -1 sodium hydride form sodium salt Chemical class 0.000 description 5
- 238000010189 synthetic method Methods 0.000 description 5
- XLEILMCZKMFZTO-UHFFFAOYSA-N 2,3-difluorooxirane Chemical class FC1OC1F XLEILMCZKMFZTO-UHFFFAOYSA-N 0.000 description 4
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 4
- 101150065749 Churc1 gene Proteins 0.000 description 4
- 102100038239 Protein Churchill Human genes 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- JLGADZLAECENGR-UHFFFAOYSA-N 1,1-dibromo-1,2,2,2-tetrafluoroethane Chemical compound FC(F)(F)C(F)(Br)Br JLGADZLAECENGR-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 239000012230 colorless oil Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 229960004756 ethanol Drugs 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004990 Smectic liquid crystal Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000006880 cross-coupling reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000001475 halogen functional group Chemical group 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 125000002769 thiazolinyl group Chemical group 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 125000005449 2-fluoro-1,4-phenylene group Chemical group [H]C1=C([*:2])C([H])=C(F)C([*:1])=C1[H] 0.000 description 1
- LCHYEKKJCUJAKN-UHFFFAOYSA-N 2-propylphenol Chemical compound CCCC1=CC=CC=C1O LCHYEKKJCUJAKN-UHFFFAOYSA-N 0.000 description 1
- RYVOZMPTISNBDB-UHFFFAOYSA-N 4-bromo-2-fluorophenol Chemical compound OC1=CC=C(Br)C=C1F RYVOZMPTISNBDB-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- 239000004991 Lytropic liquid crystal Substances 0.000 description 1
- 238000006411 Negishi coupling reaction Methods 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- 230000018199 S phase Effects 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- OPPWASLOVKWHCT-UHFFFAOYSA-N boric acid;phenol Chemical compound OB(O)O.OC1=CC=CC=C1 OPPWASLOVKWHCT-UHFFFAOYSA-N 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- IYRWEQXVUNLMAY-UHFFFAOYSA-N carbonyl fluoride Chemical compound FC(F)=O IYRWEQXVUNLMAY-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol group Chemical group [C@@H]1(CC[C@H]2[C@@H]3CC=C4C[C@@H](O)CC[C@]4(C)[C@H]3CC[C@]12C)[C@H](C)CCCC(C)C HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000008447 perception Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229960003742 phenol Drugs 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Abstract
The invention provides difluorovinyl-ether-containing liquid crystal compounds of a general formula (I) and a synthesis method, a composition and use thereof in liquid crystal elements. The novel liquid crystal compound provided by the invention has excellent chemical and physical properties, and lower optical anisotropy and higher dielectric anisotropy than other liquid crystal materials. The liquid crystal composition can be used in liquid crystal elements with the liquid crystal medium, such as TN, STN, TFT, VA, ECB, OCB, LCP, PDLC, BiNem, LC LENS, FFS and IPS liquid crystal elements.
Description
Technical field
The composition that the present invention relates to a kind of liquid crystalline cpd and comprise described liquid crystalline cpd, more particularly, the present invention relates to a kind of novel liquid crystalline cpd containing difluoroethylene ethers and the liquid-crystal composition that comprises described liquid crystalline cpd.
Background technology
In physics, material is divided into tri-state, i.e. solid-state, liquid state and gaseous state.At occurring in nature, that most of material variation with temperature only presents is solid-state, liquid state and three kinds of states of gaseous state, liquid crystal (Liquid Crystal) is a kind of new state of matter that is different from common solid-state, liquid state and gaseous state, it is the state of matter that can have liquid and crystal characteristic in certain temperature range concurrently, also be called mesomorphic phase or intermediary's phase, therefore be called again the 4th state of material.
The kind of liquid crystal is a lot, and the liquid crystal with synthetic naturally existing reaches thousands of kinds, but they are organic compound substantially.The condition forming by mesomorphic phase is carried out inducing classification, and liquid crystal can be divided into thermotropic liquid crystal, lytropic liquid crystals, induction liquid crystal and stream and cause liquid crystal.
At present, for the liquid crystal material showing, be all thermotropic liquid crystal substantially.Thermotropic liquid crystal is because of the difference of molecular arrangement order state, can be divided into smectic phase (Smectic) liquid crystal (claim not only layered liquid crystal), nematic phase (Nematic) liquid crystal (but also claiming nematic liquid crystal), cholesteryl phase (Cholestevic) liquid crystal (also referred to as spirrillum liquid crystal).The physical properties of these phases is known.The molecular characterization that is used for the compound of field of electro-optics, normally has a rigid backbone, and it comprises 1 of for example connection, 4-phenylene or 1,4-cyclohexylidene or heterocyclic system, its each other as far as possible away from position on by so-called mesomorphic group, as alkyl, alkoxyl group or cyano group replace.
Be used for the liquid crystal media in electrooptics field by the compositions of mixtures of these compounds, and wherein also use and do not there is the compound transforming from crystal to mesomorphic phase change.By liquid-crystal display mode, classify, liquid crystal compound can be divided into dynamic scattering mode (DS type), guest-host type (GH type), twisted nematic (TN type), super-twist nematic (STN type), film transistor type (TFT type) and strong dielectric type (FLC type) etc.Liquid crystal material has been widely used in the making of the liquid crystal display device such as robot calculator, meter device, instrument panel for motor vehicle, electronic memo, mobile telephone, computer, televisor at present.
Up to now, all this liquid crystal materials used have synthesized multiple compounds, visual its display mode or type of drive and uses thereof and be suitable for.Can to improving the demand of liquid crystal display device performance, also strengthen year by year on the other hand, for meeting this demand, need continual exploitation novel liquid crystal compound.
Summary of the invention
The object of this invention is to provide a kind of novel liquid crystalline cpd containing difluoroethylene ethers.
Another object of the present invention is to provide a kind of synthetic method of synthetic described liquid crystalline cpd.
Another object of the present invention is to provide a kind of composition that comprises described liquid crystalline cpd.
A further object of the present invention is to provide the application of a kind of described liquid-crystal composition in liquid crystal cell, can be used for the liquid crystal cell containing liquid crystal media, as the liquid crystal cell of the display formats such as TN, STN, TFT, VA, ECB, OCB, LCP, PDLC, BiNem, LC LENS, FFS and IPS.
One aspect of the present invention provides a kind of novel liquid crystal compound, and described compound has the structure shown in logical formula I:
Wherein,
R
1and R
2identical or not identical, independently of one another choosing freedom-H ,-F ,-Cl ,-CN ,-NCS ,-SCN ,-OCN ,-NCO,
the group that the thiazolinyl of the halo of the alkyl of the straight or branched of the halo of a 1-20 carbon atom or not halo or alkoxyl group and 2-20 carbon atom or the not straight or branched of halo or alkene oxygen base form, wherein, at described R
1with described R
2in at least one-CH
2-can by-O-,-S-,-SiH
2-,-CH=CH-,-C ≡ C-,-CF=CF-,-CH=CF-,
-CO-O-or-O-CO-substitutes, its prerequisite is that heteroatoms is not directly connected to each other;
Ring A
1, A
2, A
3, A
4, A
5and A
6identical or different, choosing independently of one another freely
the ring texture of the group forming;
Wherein,
Described ring texture can also meet following a), b), c) and d) at least one:
A) the one or more hydrogen atoms in described ring texture can by-D ,-F ,-Cl ,-CN ,-CF
3,-OCF
3,-CH
2f ,-OCH
2f ,-CF
2h ,-OCF
2h ,-OCH
3or-CH
3substitute;
B) one or more-CH in described ring texture
2-quilt-O-,-SiH
2-,-S-or-CO-substitutes, its prerequisite is that heteroatoms is not directly connected to each other;
C) in described ring texture, in aromatic ring structure one or more-CH-can substitute by N;
D) one or more in described ring texture
can be by
substitute;
Z
1, Z
3, Z
4and Z
5identical or different, select independently of one another free carbon-carbon single bond ,-CO-O-,-CF
2o-,-CH
2o-,-OCH
2-,-CH
2cH
2-,-CF
2cH
2-,-CF=CF-,-CH=CH-,-CH=CF-,-C
2f
4-,-(CH
2)
4-,-(CF
2)
4-,-OCF
2cF
2o-,-CF
2cF
2cF
2o-,-CH
2cH
2cF
2o-,-OCH
2cF
2o-,-CH
2cF
2oCH
2-,-CH=CHCF
2o-,-CF
2oCH=CH-,-CF
2oCF=CH-,-CF
2oCH=CF-,-CF=CFCF
2o-,-CF
2oCF=CF-,-CH=CHCH
2cH
2-,-CH
2cH=CHCH
2-,-C
2h
4oCH
2-,-OCH
2cH
2cH
2-,-CF=CF=CF=CF-,-C ≡ C-CF=CF-,-C ≡ C-CF=CF-C ≡ C-,-C ≡ C-,-CF=CF-C ≡ C-CF=CF-and-C ≡ C-CF
2the group that O-forms;
A be 0 or 1, b, c and d identical or different, be 0,1 or 2 independently of one another.
In some preferred embodiments, R
1and R
2identical or different, select independently of one another free H ,-F ,-Cl ,-CN ,-NCS,
the group that the thiazolinyl of the halo of the halo of 1-10 carbon atom or the alkyl of unsubstituted straight or branched or alkoxyl group and 2-10 carbon atom or the not straight or branched of halo or alkene oxygen base form, wherein, at described R
1with described R
2in at least one-CH
2-can by-O-,-CH=CH-,-C ≡ C-,-CF=CF-,-CH=CF-,
or-CO-O-is alternative, and its prerequisite is that heteroatoms is not directly connected to each other.
In some preferred embodiments, ring A
1, A
2, A
3, A
4, A
5and A
6identical or different, choosing independently of one another freely
the group forming.
In some preferred embodiments, ring A
1, A
2, A
3, A
4, A
5and A
6be independently from each other separately by
the ring texture of the group forming.
In some preferred embodiments, Z
1, Z
3, Z
4and Z
5identical or different, select independently of one another freedom-CO-O-,-CF
2o-,-CH
2o-,-OCH
2-,-CH
2cH
2-,-CF=CF-,-CH=CH-,-(CH
2)
4-,-C
2f
4-,-(CF
2)
4-,-OCF
2cF
2o-,-CF=CFCF
2the group that O-,-C ≡ C-and carbon-carbon single bond form.
In some preferred embodiments, Z
1, Z
3, Z
4and Z
5be independently from each other separately by-CO-O-,-CF
2o-,-CH
2o-,-CH
2cH
2-,-CF=CF-,-CH=CH-,-C
2f
4-,-(CH
2)
4-,-(CF
2)
4-,-OCF
2cF
2o-,-CF=CFCF
2the group that O-,-C ≡ C-and carbon-carbon single bond form.
In some preferred embodiments, Z
1, Z
3, Z
4and Z
5be independently from each other separately by-CF
2o-,-CH
2o-,-CH
2cH
2-,-CF=CF-,-CH=CH-,-CF=CFCF
2the group that O-,-C ≡ C-and carbon-carbon single bond form.
In some preferred embodiments, a is 0 or 1; B+c+d≤3.
In some preferred embodiments, the compound of logical formula I is particularly preferably one or more in the group that following compound forms:
and
Wherein,
R
1and R
2identical or different, to select independently of one another free H ,-F ,-Cl ,-CN and the halo of 1-7 carbon atom or the alkyl of unsubstituted straight or branched or alkoxyl group to form group, wherein, at described R
1with described R
2in at least one-CH
2-can by-O-,-CH=CH-,-C ≡ C-,-CF=CF-,-CH=CF-,
or-CO-O-is alternative, and its prerequisite is that heteroatoms is not directly connected to each other.
Another object of the present invention provides a kind of method of preparing above-claimed cpd, comprises the steps:
The compound of general formula (III-2) and sodium hydride form sodium salt, then react with tetrafluorodibromoethane, obtain the compound of general formula (III-1); The compound process Lithium Aluminium Hydride reduction of general formula (III-1) obtains the compound of logical formula III.
The compound of logical formula III and sodium hydride form sodium salt, then react with the compound of general formula (IV), obtain the compound of logical formula I.
The compound of general formula (III-2) and logical formula III is mainly by commercially available intermediate or the synthetic method known is altogether synthetic obtains, and the synthetic method of wherein knowing altogether comprises that esterification, witting reaction, carbon-carbon cross coupling reaction (Suzuki coupling, Negishi coupling, Heck coupling, Sonogashira coupling and transition metal-catalyzed Grignard reagent cross-coupling reaction etc.) and reduction reaction etc. obtain.
The process of principal reaction is as follows:
1) in anhydrous dimethyl formamide solvent; under argon shield; the compound that adds general formula (III-2); add sodium hydride in batches; be warming up to 60 ℃ of reactions 1 hour; be cooled to after room temperature, then drip the dimethyl formamide solution of ethyl bromide difluoride, room temperature reaction obtains the compound of general formula (III-1) for 12 hours.
2) compound dissolution of general formula (III-1), in anhydrous acetonitrile, adds zinc powder under nitrogen protection, and the 10 ~ 12h that refluxes obtains the compound of logical formula III.
3) compound dissolution of logical formula IV is in anhydrous dimethyl formamide solvent, N
2under lower protection, add sodium hydride, be warming up to 60 ℃ of reaction 1h, add the compound of general formula (III-1), 60 ℃ are reacted 1h, obtain the compound of logical formula V.
Another object of the present invention provides a kind of liquid-crystal composition, comprises the liquid crystalline cpd described in one or more logical formula I.
In some embodiments, described liquid-crystal composition comprises a kind of to the liquid crystalline cpd described in five kinds of logical formula I, is preferably described liquid-crystal composition and comprises two kinds to the four kinds liquid crystalline cpds described in logical formula I.
According to the other blending ingredients of liquid-crystal composition of the present invention, can be conventionally known mesomorphic compound, can mixedly form the compound of mesomorphic phase with its pure state or with other components.Some this type of compound is for example being mentioned in D E1804894 and CN1158602A.Preferably, in some embodiments, described liquid-crystal composition also comprises the liquid crystalline cpd of at least one logical formula II:
Wherein,
R
3and R
4identical or different, select independently of one another freedom-H ,-F ,-Cl ,-CN ,-NCS ,-SCN ,-OCN ,-NCO ,-OCH=CF
2with the halo of 1-20 carbon atom or group that alkyl of the straight or branched of halo or alkoxyl group do not form, wherein, at described R
3with described R
4in at least one-CH
2-can by-O-,-S-,-SiH
2-,-CH=CH-,-C ≡ C-,-CF=CF-,-CH=CF-,
-CO-O-or-O-CO-substitutes, its prerequisite is that heteroatoms is not directly connected to each other;
B
1, B
2and B
3and B
4identical or different, choosing independently of one another freely
fluoro-Isosorbide-5-Nitrae-the phenylene of 2,3-bis-, the fluoro-Isosorbide-5-Nitrae-phenylene of 3-, the chloro-3-of 2-fluoro-1,4-phenylene, the fluoro-Isosorbide-5-Nitrae-phenylene of 2-, 2,6-bis-fluoro-1,4-phenylene, 3, the fluoro-Isosorbide-5-Nitrae-phenylene of 5-bis-, indane-2,5-bis-bases, piperidines-Isosorbide-5-Nitrae-bis-base, naphthalene-2,6-bis-bases, perhydronaphthalene-2,6-bis-bases and 1,2,3,4-naphthane-2, the group that 6-bis-bases form, described in
in one or two non-conterminous-CH
2-can by-O-or-S-substitutes, described in
upper one or more H can be replaced by F independently of one another, described in
in one or two non-conterminous-CH-can be substituted by N, described in
in one or two non-conterminous-CH
2-can be substituted by O, described in
upper one or more H can be replaced by F independently of one another;
Y
1, Y
2and Y
3identical or different, select independently of one another freedom-OCO-,-CO-O-,-CF
2o-,-CH
2o-,-OCH
2-,-CH
2cH
2-,-CF
2cH
2-,-CF=CF-,-CH=CH-,-CH (CH
3) CH
2-,-CH
2cH (CH
3)-,-(CH
2)
3o-,-O (CH
2)
3-,-COS-,-SCO-,-CH=CF-,-C
2f
4-,-(CH
2)
4-,-C
4f
8-,-OCF
2cF
2o-,-CF
2cF
2cF
2o-,-CH
2cH
2cF
2o-,-CH
2cF
2oCH
2-,-CH=CHCF
2o-,-CF
2oCH=CH-,-CF
2oCF=CH-,-CF
2oCH=CF-,-CF=CFCF
2o-,-CF
2oCF=CF-,-CH=CHCH
2cH
2-,-C
2h
4oCH
2-,-CH
2cH=CHCH
2-,-OCH
2cH
2cH
2-,-CF=CF-CF=CF-,-C ≡ C-CF=CF-,-C ≡ C-CF=CF-C ≡ C-,-CF=CF-C ≡ C-CF=CF-,-C ≡ C-CF
2the group that O-,-C ≡ C-and singly-bound form, wherein, at described Y
1and Y
2in any one-CH
2-can be by-SiH
2-substitute;
M, n and p are identical or different, are 0,1 or 2 independently of one another.
The group that the freely following compound of described liquid crystalline cpd choosing forms:
and
In some embodiments, described liquid-crystal composition comprises the compound accounting for described in the logical formula I of described liquid-crystal composition gross weight 5-50%; Account for the compound described in the logical formula II of described liquid-crystal composition gross weight 50-95%, preferably account for the compound described in the logical formula I of described liquid-crystal composition gross weight 10-30%; Account for the compound described in the logical formula II of described liquid-crystal composition gross weight 70-90%.
Another object of the present invention is to provide a kind of liquid-crystal display, and described liquid-crystal display comprises the liquid-crystal composition that contains liquid crystalline cpd of the present invention.
A further object of the present invention is to provide a kind of novel liquid crystalline cpd containing difluoroethylene ethers, it is suitable as the composition of liquid crystal media, can be applicable to the liquid crystal cell containing liquid crystal media, as the liquid crystal cell of the display formats such as TN, STN, TFT, VA, ECB, OCB, LCP, PDLC, BiNem, LC LENS, FFS and IPS.
The novel liquid crystalline cpd containing six hydrogen indenes classes provided by the invention has good chemistry and physical properties, has lower viscosity, larger optical anisotropy and larger dielectric anisotropy than other liquid crystal material.
Embodiment
Below with reference to specific embodiments, the present invention is described.It should be noted that, the following examples are example of the present invention, are only used for illustrating the present invention, and are not used for limiting the present invention.In the situation that not departing from purport of the present invention or scope, can carry out other combination and various improvement in design of the present invention.
For ease of expressing, in following embodiment, the listed coded representation of table 1 for the unit structure of liquid crystalline cpd:
The unit structure code of table 1 liquid crystalline cpd
The compound of following structural formula of take is example:
This structural formula, as represented by code listed in Table 1, can be expressed as: 3PUQUF, and the Q in code represents difluoro methylene oxygen base; C in code represents cyclohexyl; U in code represents 2,5-, bis-fluoro phenylenes.
Embodiment 1
The synthetic route of the compound H CLC-12 of preparation is as follows,
Its concrete technology step is as follows:
1) HCLC-12-2's is synthetic
500mL there-necked flask, adds 21.8g the third ring phenol, 200mL dimethyl formamide (DMF); dissolve, under nitrogen protection, add 8g60% sodium hydride (NaH), be warming up to 60 ℃ of reaction 1h; be cooled to 30 ℃, drip tetrafluorodibromoethane 31.2g, add room temperature reaction 12h.Add ethyl acetate 200ml, water 200ml, layering, water layer with the extraction of 200ml ethyl acetate, merges organic layer again, washes 2 times, salt solution washed twice, the dry crude product 38.5g that concentrates to obtain, the thick post of crossing of sherwood oil obtains 34g.GC:98.8%, yield 85.6%.
2) HCLC-12-1's is synthetic
In 250ml reaction flask, add 20gHCLC-12-2,6g zinc powder and 100ml acetonitrile, refluxed under nitrogen 11h, is cooled to room temperature, and suction filtration is spin-dried for to obtain crude product.Crude product adds after petroleum ether dissolution, and sherwood oil strips post, is spin-dried for to obtain product 13.4g.Yield 89%, GC:86.3%.
3) HCLC-12's is synthetic
In 250ml reaction flask, add 1.9g60% sodium hydride NaH, 3.2g2, the fluoro-4-thanatol of 3-bis-and 100mlDMF, N
2under be warming up to 60 ℃ reaction 1h, add 6g HCLC-12-1,60 ℃ of reaction 6h, add water 300ml, ethyl acetate 200ml extraction, washing, salt water washing, dry, concentrated, sherwood oil ether column chromatography obtains 8.4g colorless oil, with 10ml ethanol recrystallization at-30 ℃, obtain water white transparency oily thing 1.97g, GC:99.7%, yield 25% for four times again.
1H?NMR(300MHz,CDCl
3)δ7.50-7.21(m,2H),6.94-6.76(m,2H),6.55-6.60(m,2H),4.09(q,J=11.8Hz,2H),2.69-2.73(m,1H),1.89-1.09(m,16H),0.93-0.82(m,3H)。
Embodiment 2
The synthetic route of the compound H CLC-12K of preparation is as follows,
[4,4-bis-fluoro-(3,4,5-trifluoromethoxy phenoxy base) methyl]-3,5-difluorobenzene boric acid can be with prior art perception method synthetic (its synthetic method can reference European Journal of Organic Chemistry, 2008, V20p3479 – 3487) altogether.
Its concrete technology step is as follows:
1) HCLC-12K-4's is synthetic
250mL there-necked flask, adds 15g n-propyl phenol and 150mL DMF, dissolves, and adds 4.4g sodium hydride (NaH) under nitrogen protection, is warming up to 60 ℃ of reaction 1h, is cooled to 30 ℃, drips tetrafluorodibromoethane 36g, adds room temperature reaction 12h.Add ethyl acetate 200ml, water 200ml, layering, water layer with the extraction of 200ml ethyl acetate, merges organic layer again, washes 2 times, salt solution washed twice, the dry crude product 30g that concentrates to obtain, the thick post of crossing of sherwood oil obtains 22.5g.GC:96.5%, yield 64.8%.
2) HCLC-12K-3's is synthetic
In 250ml reaction flask, add 22.5g HCLC-12K-4,10g zinc powder and 150ml acetonitrile, refluxed under nitrogen 11h, is cooled to room temperature, and suction filtration is spin-dried for to obtain crude product.Crude product is crossed post after adding petroleum ether dissolution, is spin-dried for to obtain product 9.6g.Yield 62.3%, GC:85.8%.
3) HCLC-12K-2's is synthetic
In the single port bottle of 1L dried and clean, add 20g para hydroxybenzene boric acid, the fluoro-4-iodine tribromophenyl of 43.5g3-, 30.5g anhydrous sodium carbonate, 144mL deionized water, 160mL toluene and 80mL dehydrated alcohol, after using argon replaces emptying, add 0.5g Pd[P (Ph)
3]
4.Reflux 6h under argon shield; the cooling rear separatory of reaction solution, 20g anhydrous sodium sulfate drying, organic phase is steamed toluene to the greatest extent; cross silicagel column; with sherwood oil and the eluent ethyl acetate of 3:1, chromatographic solution steams solvent to the greatest extent with Rotary Evaporators, obtains 42g light yellow solid; crude product is used 100mL dehydrated alcohol and 100ml toluene recrystallization again; obtain 31.5g white solid, GC content 99.6%, yield 82%.
4) HCLC-12K-1's is synthetic
In the single port bottle of 250mL dried and clean, add 6g HCLC-12K-2,8g[4,4-bis-fluoro-(3,4,5-trifluoromethoxy phenoxy base) methyl]-3,5-difluorobenzene boric acid, 4.8g anhydrous sodium carbonate, 25mL deionized water, 100mL toluene and 25mL dehydrated alcohol, after emptying by argon replaces, add 0.5g Pd[P (Ph)
3]
4.Reflux 12h under argon shield; the cooling rear separatory of reaction solution; organic phase is steamed toluene to the greatest extent, crosses silicagel column, with sherwood oil and the eluent ethyl acetate of 3:1; chromatographic solution steams solvent to the greatest extent with Rotary Evaporators; obtain 11g light yellow solid, crude product is used 20mL toluene and 10mL dehydrated alcohol recrystallization again, obtains 9.5g white solid; GC content 99.7%, yield 85%.
5) HCLC-12K's is synthetic
In 100ml reaction flask, add 0.7g60%NaH, 5g HCLC-12K-1,50ml DMF, N
2under be warming up to 60 ℃ reaction 1h, add 3.0gHCLC-12K-3,60 ℃ reaction 1h, add water 100ml, ethyl acetate 200ml extraction, washing, salt water washing, dry, concentrated, cross silicagel column, sherwood oil and eluent ethyl acetate with 5:1, chromatographic solution steams solvent to the greatest extent with Rotary Evaporators and obtains 6.4g colorless oil, then uses 15ml toluene, and 20ml ethyl alcohol recrystallization obtains white solid 2.9g four times, GC:99.6%, yield 42%.
1H?NMR(300MHz,CDCl
3)δ7.94(dd,J=15.0,10.1Hz,1H),7.71(dd,J=16.0,3.0Hz,1H),7.62–7.53(m,2H),7.36–7.28(m,,2H),7.08–6.97(m,3H),6.95–6.76(m,6H),2.61(t,J=15.5Hz,2H),1.74–1.55(m,2H),0.94(t,J=13.2Hz,3H)。
Embodiment 3
The synthetic route of the compound H CLC-12M of preparation is as follows,
Its concrete technology step is as follows:
1) HCLC-12M-1's is synthetic
In the single port bottle of 250mL dried and clean, add 4g p bromophenol, 7.8g[4,4-bis-fluoro-(3,4,5-trifluoromethoxy phenoxy base) methyl]-3,5-difluorobenzene boric acid, 4.8g anhydrous sodium carbonate, 25mL deionized water, 100mL toluene and 25mL dehydrated alcohol, after emptying by argon replaces, add 0.5g Pd[P (Ph)
3]
4.Reflux 12h under argon shield; the cooling rear separatory of reaction solution; organic phase is steamed toluene to the greatest extent, crosses silicagel column, with sherwood oil and the eluent ethyl acetate of 3:1; chromatographic solution steams solvent to the greatest extent with Rotary Evaporators; obtain 9.2g light yellow solid, crude product is used 20mL dehydrated alcohol recrystallization twice again, obtains 8.1g white solid; GC content 99.6%, yield 87%.
2) HCLC-12M's is synthetic
In 100ml reaction flask, add 0.7g60%NaH, 5g HCLC-12M-1 and 50ml DMF, N
2under be warming up to 60 ℃ reaction 1h, add 2.6g HCLC-12K-3,60 ℃ reaction 1h, add water 100ml, ethyl acetate 200ml extraction, washing, salt water washing, dry, concentrated, cross silicagel column, with sherwood oil and the eluent ethyl acetate of 5:1, chromatographic solution steams solvent to the greatest extent with Rotary Evaporators and obtains 6.9g colorless oil, with 20ml sherwood oil and 20ml ethyl alcohol recrystallization, obtain white solid 2.9g four times again, GC:99.6%., yield 39%.
1H?NMR(300MHz,CDCl
3)δ7.62–7.53(m,2H),7.29–7.35(m,2H),7.06–6.97(m,2H),6.93–6.76(m,6H),2.61(t,J=15.6Hz,2H),1.74–1.55(m,2H),0.94(t,J=13.2Hz,3H)。
Embodiment 4
The synthetic route of the compound H CLC-12N of preparation is as follows,
When synthetic HCLC-12N-1, according to the method for synthetic HCLC-12M-1, with the fluoro-4-bromophenol of 3-, replace p bromophenol synthetic, then can obtain white solid HCLC-12N according to the synthetic method of compound H CLC-12M.
1H?NMR(300MHz,CDCl
3)δ7.62-7.57(m,1H),7.27-7.09(m,5H),6.95-6.83(m,4H),6.53-6.62(m,1H),2.62(t,J=15.6Hz,2H),1.68-1.55(m,2H),0.93(t,J=13.2Hz,3H)。
Embodiment 5 is the performance test results of liquid-crystal composition of the present invention below:
In following examples test event to write a Chinese character in simplified form code name as follows:
Cp(℃): clearing point (to row-isotropic phase transition temperature)
η: kinetic viscosity (mm
2s
-1, 20 ℃, except as otherwise noted)
Δ n: optical anisotropy (589nm, 20 ℃)
Δ ε: dielectric anisotropy (1KHz, 25 ℃)
Embodiment 5
Table 2 is the relevant parameter that HCLC-12K and HCLC-12M are configured to liquid-crystal composition and obtain:
Claims (8)
1. a liquid crystalline cpd, the group of the freely following compound composition of described liquid crystalline cpd choosing:
Wherein, R
1the alkyl of the straight or branched of 1-7 carbon atom, R
2be-F.
2. the liquid-crystal composition that comprises at least one liquid crystalline cpd according to claim 1.
3. liquid-crystal composition according to claim 2, is characterized in that, described liquid-crystal composition comprises a kind of to five kinds of liquid crystalline cpds according to claim 1.
4. liquid-crystal composition according to claim 3, is characterized in that, described liquid-crystal composition comprises two kinds to four kinds liquid crystalline cpds according to claim 1.
5. liquid-crystal composition according to claim 2, is characterized in that, described liquid-crystal composition also comprises the liquid crystalline cpd of the general formula II of at least one group of selecting freely following compound composition:
and
6. liquid-crystal composition according to claim 5, is characterized in that, described liquid-crystal composition comprises the liquid crystalline cpd according to claim 1 that accounts for described liquid-crystal composition gross weight 5-50%; Account for the liquid crystalline cpd of the described general formula II of described liquid-crystal composition gross weight 50-95%.
7. liquid-crystal composition according to claim 6, is characterized in that, described liquid-crystal composition comprises the liquid crystalline cpd according to claim 1 that accounts for described liquid-crystal composition gross weight 10-30%; Account for the liquid crystalline cpd of the described general formula II of described liquid-crystal composition gross weight 70-90%.
8. a liquid-crystal display, described liquid-crystal display comprises according to the liquid-crystal composition one of claim 2-7 Suo Shu.
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| CN104402683B (en) * | 2014-11-21 | 2017-02-01 | 石家庄诚志永华显示材料有限公司 | Liquid crystal compound and liquid crystal mixture containing same |
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