CN102659533A - Indene derivative used as component of liquid crystal medium, preparation method thereof and application thereof - Google Patents
Indene derivative used as component of liquid crystal medium, preparation method thereof and application thereof Download PDFInfo
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- CN102659533A CN102659533A CN2012101042159A CN201210104215A CN102659533A CN 102659533 A CN102659533 A CN 102659533A CN 2012101042159 A CN2012101042159 A CN 2012101042159A CN 201210104215 A CN201210104215 A CN 201210104215A CN 102659533 A CN102659533 A CN 102659533A
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 125000003454 indenyl group Chemical class C1(C=CC2=CC=CC=C12)* 0.000 title abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 131
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 38
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 34
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 210000002858 crystal cell Anatomy 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 150000001721 carbon Chemical group 0.000 claims description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical class CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- 239000007818 Grignard reagent Substances 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 150000004795 grignard reagents Chemical class 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 4
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 4
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- -1 under-78 °C~-40 °C Chemical compound 0.000 claims description 2
- 125000001475 halogen functional group Chemical group 0.000 claims 4
- 230000003287 optical effect Effects 0.000 abstract description 5
- 230000004044 response Effects 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 2
- 238000003810 ethyl acetate extraction Methods 0.000 description 13
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- 239000012074 organic phase Substances 0.000 description 12
- 239000012071 phase Substances 0.000 description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000004440 column chromatography Methods 0.000 description 8
- 238000001819 mass spectrum Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000000178 monomer Substances 0.000 description 6
- 239000013256 coordination polymer Substances 0.000 description 5
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000013213 extrapolation Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 2
- 0 **c1ccc(*C(C2)Cc3c2ccc(C(F)=C(F)I)c3)cc1 Chemical compound **c1ccc(*C(C2)Cc3c2ccc(C(F)=C(F)I)c3)cc1 0.000 description 1
- 241000024287 Areas Species 0.000 description 1
- PMLRYPYQSAIBPM-UHFFFAOYSA-N C1=CC=CC=C1.[I].[Br] Chemical compound C1=CC=CC=C1.[I].[Br] PMLRYPYQSAIBPM-UHFFFAOYSA-N 0.000 description 1
- ZWSDVPWMTNASDO-OCEACIFDSA-N CCCC1Cc2cc(/C(/F)=C(/c(cc3)ccc3-c(ccc(OCC)c3F)c3F)\F)ccc2C1 Chemical compound CCCC1Cc2cc(/C(/F)=C(/c(cc3)ccc3-c(ccc(OCC)c3F)c3F)\F)ccc2C1 ZWSDVPWMTNASDO-OCEACIFDSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
- 239000012141 concentrate Substances 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
- 239000012769 display material Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
Abstract
The invention provides an indene derivative which can be used as a component of a liquid crystal medium and has a general formula (I), a preparation method thereof and an application thereof. Above compound is a negative liquid crystal compound, has the characteristics of high dielectric property, optical anisotropy and clearing point, and wide nematic phase temperature range, and makes displays using the compound have the advantages of fast response speed and wide working range, and well display in various environments. The invention also provides one or more liquid crystal compositions containing the compound, and liquid crystal elements containing the liquid crystal composition(s).
Description
Technical field
The present invention relates to compound as the component of liquid crystal media.
Background technology
Liquid crystal material is a kind of mesomorphic phase material between solid phase and liquid phase, mainly is used as the dielectric medium in the indicating meter, and its reason is that the optical property of this type material can change through the voltage that applies.Electrooptics device based on liquid crystal is known in those skilled in the art, wherein can comprise various effects.The instance of this type device is liquid crystal cell, DAP (orientation is out of shape mutually) liquid crystal cell, guest/principal mode liquid crystal cell, the TN box with twisted-nematic structure, STN (supertwist is to row) liquid crystal cell, SBE (ultra birefringence effect) liquid crystal cell and OMI (interference of the light film) liquid crystal cell with dynamic scattering.Modal indicating meter is based on the Schadt-Helfrich effect and have the twisted-nematic structure.In addition, the liquid crystal cell that also exists the electric field be used to be parallel to substrate and liquid crystal face to operate, for example IPS (face intra) liquid crystal cell.Special, TN, STN and IPS liquid crystal cell, especially TN and IPS liquid crystal cell are the Application Areass that has commercial significance at present of medium of the present invention.
For liquid-crystal display, have thermostability, good dielectric properties and more low viscous liquid crystalline cpd and liquid crystal media and meet current needs.In order to enlarge the working range of liquid-crystal display, liquid crystal display material needs wide nematic temperature range, in various environment, all can keep the good requirement that shows to satisfy.
In the large scale liquid crystal TV, thin film transistor (TFT) display format of liquid crystal molecule arranged vertical (VA) is used widely in recent years.Its advantage is that the visual angle is wide, response speed fast, contrast gradient is bigger.Traditional distortion-nematic-mode (TN) uses dielectric anisotropy to be (Δ ε=ε just
//-ε
⊥, Δ ε＞0) liquid crystal material, on the molecular long axis direction, have polar group, make long axis direction specific inductivity (ε
//) greater than perpendicular electric constant (ε
⊥); And the liquid crystal material that the VA pattern requires to be adopted has bigger dielectric anisotropy of negativity value (Δ ε＜0) and bigger optical anisotropy (Δ n).At present existingly developed the bigger liquid crystalline cpd of many negativity values, like US6348244B, CN102153442, WO9919420, the Δ ε value of above-claimed cpd is very big, but Δ n is less, and resistivity and voltage retention are also very low.Therefore, exist new needs with negative liquid crystal material of higher dielectricity and optical anisotropy, high clearing point and wide nematic temperature range are provided.
Summary of the invention
The purpose of this invention is to provide a kind of indene derivative that can be used as the component of liquid crystal media, this compound can be used as the negative liquid crystal material.
Another object of the present invention provides the preparation method of above-mentioned indene derivative.
Another purpose of the present invention provides a kind of liquid-crystal compsn that comprises indene derivative.
A purpose more of the present invention provides a kind of liquid crystal cell that comprises said liquid-crystal compsn as integrant.
One aspect of the present invention provides a kind of indene derivative that can be used as the component of liquid crystal media, and this compound has the structure shown in the general formula (I):
Wherein,
R
1, R
2Identical or different, be selected from by H, halogen, halo or unsubstituted alkyl or alkoxyl group independently of one another and have halo or the unsubstituted alkane thiazolinyl of 2-7 carbon atom or the group that the alcoxyl thiazolinyl is formed with 1-7 carbon atom, wherein, at said R
1With said R
2In one or more CH
2Group can be independently of one another by-CH=CH-,-O-,-CH=CF-,-CF=CH-,-CF=CF-,-CO-O-or-O-CO-substitutes, its prerequisite is that Sauerstoffatom directly is not connected to each other;
Identical or different, be selected from independently of one another by
The group of forming, wherein, said
In at least one do
Z
1And Z
2Identical or different, be independently from each other separately by-CO-O-,-O-CO-,-CF
2O-,-OCF
2-,-CH
2O-,-OCH
2-,-CH
2CH
2-,-(CH
2)
4-,-C
2F
4-,-CH
2CF
2-,-CF=CF-,-group that CH=CH-and singly-bound are formed;
S, m represent 0,1 or 2 separately independently of one another, and 0≤s+m≤3.
In some preferred embodiments, R
1, R
2Identical or different, be selected from independently of one another by-C
2H
5, n-C
3H
7, n-C
4H
9, n-C
5H
11And n-C
6H
13The group of forming, wherein, at said R
1With said R
2In one or more CH
2Group can be independently of one another by-CH=CH-,-O-,-CF=CF-or-CO-O-substitutes, its prerequisite is that Sauerstoffatom directly is not connected to each other.
In some preferred embodiments;
is identical or different; Be selected from the group of forming by
independently of one another; Wherein, at least one in said
is
In some preferred embodiments, Z
1And Z
2Identical or different, be selected from independently of one another by-OCH
2-,-CH
2O-,-OCF
2-,-CF
2The group that O-and singly-bound are formed.
In some preferred embodiments, s, m are identical or different, represent 0 or 1 separately independently of one another, and 0≤s+m≤2.
Preferably, compound of the present invention is selected from the group of being made up of following compound:
Wherein, R
1, R
2Be selected from independently of one another by-C
2H
5, n-C
3H
7, n-C
4H
9And n-C
5H
11The group of forming, wherein, at said R
1With said R
2In one or more CH2 groups can be separately independently by-CH=CH-,-O-,-CF=CF-or-CO-O-substitutes, its prerequisite is that Sauerstoffatom directly is not connected to each other; Z
2For-OCH
2-,-CH
2O-,-OCF
2-,-CF
2O-or singly-bound.
More preferably, compound of the present invention is selected from the group of being made up of following compound:
Another aspect of the present invention provides a kind of method for preparing compound of the present invention, comprises the steps:
1) make solvent with THF, under nitrogen protection with the compound of general formula 1
With the reaction of magnesium powder, generate the grignard reagent of general formula 2,
The grignard reagent of said general formula 2 and trifluoro-ethylene obtain the compound of general formula 3 stirring at room reaction 0.5-3 hour;
(general formula 3)
2) in tetrahydrofuran solvent, under-78 ℃～-40 ℃, nitrogen protection, with the compound of general formula 3 and n-Butyl Lithium (nBuLi) reaction 1-2 hour; Iodine is dissolved in the system that splashes into the compound that comprises general formula 3 and n-Butyl Lithium behind the THF, reacted 0.5-2 hour, obtain the compound of general formula 4;
(general formula 4)
3) in tetrahydrofuran solvent, at-78 ℃～-40 ℃, under the nitrogen protection, with the compound of general formula 5
With n-Butyl Lithium, the reaction of boric acid three isobutylates, obtain the compound of general formula 6,
(general formula 6)
Then the compound of general formula 6 and the compound of general formula 4 were reacted 4-6 hour in tetra-triphenylphosphine palladium catalysis refluxed, obtain the compound of general formula (I)
Wherein, R
1And R
2Identical or different, be selected from by H, halogen, halo or unsubstituted alkyl or alkoxyl group independently of one another and have halo or the unsubstituted alkane thiazolinyl of 2-7 carbon atom or the group that the alcoxyl thiazolinyl is formed with 1-7 carbon atom, wherein, at said R
1With said R
2In one or more CH
2Group can be independently of one another by-CH=CH-,-O-,-CH=CF-,-CF=CH-,-CF=CF-,-CO-O-or-O-CO-substitutes, its prerequisite is that Sauerstoffatom directly is not connected to each other;
Identical or different, be selected from independently of one another by
The group of forming, wherein, said
In at least one do
Z
1And Z
2Identical or different, be independently from each other separately by-CO-O-,-O-CO-,-CF
2O-,-OCF
2-,-CH
2O-,-OCH
2-,-CH
2CH
2-,-(CH
2)
4-,-C
2F
4-,-CH
2CF
2-,-CF=CF-,-group that CH=CH-and singly-bound are formed;
S, m are identical or different, represent 0,1 or 2 separately independently of one another, and 0≤s+m≤3.
Another aspect of the present invention provides a kind of liquid-crystal compsn, and this liquid-crystal compsn comprises a kind of or more kinds of compound of the present invention.
Another aspect of the present invention provides a kind of liquid crystal cell that comprises liquid-crystal compsn of the present invention.
Other liquid crystalline cpds of negative liquid crystal compound and prior art of general formula provided by the invention (I) are compared, and have higher dielectricity, specific refractory power anisotropy, high clearing point and wide nematic temperature range, and chemical property is all stable; In the negative liquid crystal compound process of general formula (I), raw material is easy to get, and synthetic route is simple, is fit to large-scale industrial production, is beneficial to as the use that shows with liquid crystal material, the time of response that can be used for improving liquid-crystal compsn; Enlarge operating temperature range.
Description of drawings
Fig. 1 is the synthetic route chart of compound I-1-1.
Fig. 2 is compound I-1-1
1H NMR figure.
Fig. 3 is the mass spectrum of compound I-1-1.
Fig. 4 is the synthetic route chart of compound I-2-1.
Fig. 5 is compound I-2-1
1H NMR figure.
Fig. 6 is the mass spectrum of compound I-2-1.
Fig. 7 is the synthetic route chart of compound I-3-1.
Fig. 8 is compound I-3-1
1H NMR figure.
Fig. 9 is the mass spectrum of compound I-3-1.
Figure 10 is the synthetic route chart of compound I-4-1.
Figure 11 is compound I-4-1
1H NMR figure.
Figure 12 is the mass spectrum of compound I-4-1.
Embodiment
Below will combine specific embodiments that the present invention is described.Need to prove that following embodiment is an example of the present invention, only be used for explaining the present invention, and be not used for limiting the present invention.Under the situation that does not depart from purport of the present invention or scope, can carry out the present invention and conceive interior other combination and various improvement.
The code name of writing a Chinese character in simplified form of each test event is expressed as respectively in following examples:
Cp (℃) clearing point (to row-isotropic phase transition temperature)
Δ n optical anisotropy (589nm, 20 ℃)
Δ ε dielectric anisotropy (1KHz, 25 ℃)
Wherein, the specific refractory power anisotropy use Abbe refractometer under sodium lamp (589nm) light source, 20 ℃ test; The dielectric testing cassete is the TN90 type, the thick 7 μ m of box.
Reagent used in the present invention and other raw materials are commercially available commercial materials.
The synthetic route of preparation compound I-1-1 representes that in Fig. 1 its concrete process step is following:
1) compound of synthesis type 1
The Mg powder and the 0.05g iodine that add 8g in the 500mL there-necked flask, 10mL THF (THF), nitrogen protection.In the 200mL tetrahydrofuran solution, slowly the tetrahydrofuran solution with the compound of formula 2 adds to above-mentioned reaction system, after question response causes with the compound dissolution of the formula 2 of 45g; Continue the tetrahydrofuran solution of the compound of the remaining formula 2 of dropping; Drip and finish, the little backflow 3h that boils of maintenance system is cooled to room temperature.The 40g trifluorochloroethylene slowly is passed in the cooled reaction system, stirring at room 12h.
The Hydrogen chloride cancellation is used in reaction, ethyl acetate extraction, and organic phase is used anhydrous sodium sulfate drying, revolves dried solvent, and underpressure distillation gets colourless liquid 30g, and yield 60% is the compound of formula 1.
2) compound of synthesis type 3
The compound that adds the formula 1 of 30g in the 500mL there-necked flask, 100mL THF, nitrogen protection, subcooling splashes into the n-Butyl Lithium of 45mL under-78 ℃, and (n-BuLi 2.4mol/L), drips Bi Fanying 1h.28g iodine is dissolved in 100mL THF, and temperature is controlled at below-60 ℃ and splashes in the reaction system, drips Bi Fanying 2h.
The Hydrogen chloride cancellation is used in reaction, ethyl acetate extraction, and organic phase is used anhydrous sodium sulfate drying, revolves dried solvent, purifies with sherwood oil moving phase column chromatography, gets Vandyke brown liquid 25g, is the compound of formula 3.
3) compound of synthesis type 5
The compound that adds the formula 4 of 5.2g in the 100mL round-bottomed flask, 30mL THF, nitrogen protection, low temperature splashes into the n-Butyl Lithium of 13mL under-78 ℃, and (n-BuLi 2.4mol/L), drips Bi Fanying 2h.Boric acid three isobutylates of 14g are dissolved among the 20mL THF, splash in the reaction system in-78 ℃, drip a Bi Ziran and rise to room temperature, stirring reaction 2h.
With cancellation reaction in the reaction solution impouring Hydrogen chloride, stir 30min, ethyl acetate extraction revolves dried organic solvent, and resistates is used petroleum ether, and suction filtration gets white solid 5g, is the compound of formula 5.
4) synthetic compound I-1-1
The compound of the formula 5 of the compound of the formula 3 of adding 3.5g, 2.2g in the 100mL round-bottomed flask, 30mL glycol dimethyl ether, 10mL wet chemical (2molL
-1), 0.3g Tetrabutyl amonium bromide, 0.2g Pd (PPh
3)
4, nitrogen protection, back flow reaction 5h.
Reaction water cancellation, ethyl acetate extraction, organic phase use anhydrous sodium sulfate drying, revolves dried solvent, sherwood oil is that the moving phase column chromatography is separated, elutriant concentrate light black oily matter 1.8g, the absolute ethyl alcohol recrystallization must white needle-like crystals 1.3g, purity 99.65%.Make compound I-1-1.MS：m/z：393。
The nuclear magnetic resonance spectrum of compound I-1-1 does
1H-NMR (300MHz, CDCl
3): 7.612-7.704 (1H, d); 7.475-7.553 (1H, d); 7.296-7.374 (1H, d); 7.196-7.215 (1H, d); 6.756-6.842 (1H, s); 4.056-4.089 (2H, t); 3.007-3.159 (2H, m), 2.636-2.704 (2H, m); 2.453-2.558 (1H, m), 1.786-1.956 (2H, q); 1.334-1.558 (4H, m); 1.002-1.135 (3H, t); 0.899-0.999 (3H, t).
The liquid crystal property of compound I-1-1:
Δn：0.198 Δε：10.5 Cp：49.2℃
Compound I-1-1's
1H NMR figure sees Fig. 2.
The mass spectrum of compound I-1-1 is seen Fig. 3.
The synthetic route of preparation compound I-2-1 representes that in Fig. 4 its concrete process step is following:
1) step 1)～2 among the employing embodiment 1) compound of preparation formula 3.
2) compound of synthesis type 6
(formula 7)
Add the compound of the formula 7 of 9.3g, formula 8 compounds of 6.4g, 100mL glycol dimethyl ether, 35mL wet chemical (2molL in the 250mL round-bottomed flask
-1), 0.5g Tetrabutyl amonium bromide, 0.4g Pd (PPh
3)
4, nitrogen protection, backflow 5h.Reaction water cancellation, ethyl acetate extraction, organic phase use anhydrous sodium sulfate drying, revolves dried solvent, sherwood oil is that the moving phase column chromatography is separated, elutriant concentrated colourless liquid 7.6g, make the compound of formula 9.
(formula 9) that adds 7.6g in the 250mL round-bottomed flask, 60mL THF, nitrogen protection, low temperature splashes into 42mL n-BuLi under-78 ℃, drip Bi Fanying 2h.16g boric acid three isobutylates are dissolved among the 20mLTHF, and-78 ℃ splash in the reaction system, drip to finish to stir 2h.In reaction solution impouring Hydrogen chloride, stir 30min, ethyl acetate extraction revolves dried organic phase, and resistates is used petroleum ether, and suction filtration gets white solid 5g, makes the compound of formula 6.
3) synthetic compound I-2-1
The compound that adds the formula 3 of 3.5g in the 100mL round-bottomed flask, the compound of the formula 6 of 2.6g, 30mL glycol dimethyl ether, 10mL wet chemical (2molL
-1), 0.3g Tetrabutyl amonium bromide, 0.2g Pd (PPh
3)
4, nitrogen protection, backflow 5h.
The cancellation of reaction water, ethyl acetate extraction, organic phase is used anhydrous sodium sulfate drying, revolves dried solvent, and sherwood oil separates for the moving phase column chromatography, gets gray solid 3g, and the absolute ethyl alcohol recrystallization gets white needle-like crystals 2.2g, and purity 99.69% makes compound I-2-1.MS：m/z：439。
The nuclear magnetic resonance spectrum of compound I-2-1 does
1H-NMR (300MHz, CDCl
3), δ (ppm): 7.443-7.615 (4H, m); 7.275-7.386 (5H, m); 3.024-3.165 (2H, q); 2.712-2.189 (2H, d); 2.632-2.684 (2H, d); 2.461-2.576 (1H, m); 1.365-1.576 (4H, m); 1.268-1.324 (3H, t); 0.904-0.986 (3H, t).
The liquid crystal property of compound I-2-1:
Δn：0.301 Δε：7.6 Cp：151.2℃
Compound I-2-1's
1H NMR figure sees Fig. 5
The mass spectrum of compound I-2-1 is seen Fig. 6.
The synthetic route of preparation compound I-3-1 representes that in Fig. 7 its concrete process step is following:
1) compound of preparation formula 3 process step 1 among the employing embodiment 1)～2).
2) compound of synthesis type 10
The compound that adds the formula 11 of 6g in the 250mL round-bottomed flask, 8.5g are to benzene bromine iodine, and the 100mL glycol dimethyl ether dissolves, 30mL wet chemical (2molL
-1), 0.5g Tetrabutyl amonium bromide, 0.4g Pd (PPh
3)
4, nitrogen protection, back flow reaction 5h.Reaction water cancellation, ethyl acetate extraction, organic phase use anhydrous sodium sulfate drying, revolves dried solvent, sherwood oil is that the moving phase column chromatography is separated, elutriant concentrated white solid 8.5g, make the compound of formula 10.
3) compound of synthesis type 12
The compound that adds the formula 10 of 8.5g in the 250mL round-bottomed flask, 60ml THF, nitrogen protection, low temperature splashes into 13mL n-BuLi under-78 ℃, drip Bi Fanying 2h.13g boric acid three isobutylates are dissolved among the 20mLTHF, and temperature is controlled at below-60 ℃ and splashes in the reaction system, drips to finish to stir 2h.Reaction solution is poured in the hydrochloric acid, stirred 30min, ethyl acetate extraction revolves dried organic phase, and resistates is used petroleum ether, and suction filtration gets white solid 7.7g, makes the compound of formula 12.
4) synthetic compound I-3-1
The compound that adds the formula 3 of 2.8g in the 100mL round-bottomed flask, the compound of the formula 12 of 2.9g, 30mL glycol dimethyl ether, 8mL wet chemical (2molL
-1), 0.3g Tetrabutyl amonium bromide, 0.2g Pd (PPh
3)
4, nitrogen protection, back flow reaction 5h.
The cancellation of reaction water, ethyl acetate extraction, organic phase is used anhydrous sodium sulfate drying, revolves dried solvent, and sherwood oil separates for the moving phase column chromatography, gets gray solid 3g, and the absolute ethyl alcohol recrystallization gets white needle-like crystals 2.2g, and purity 99.16% makes compound I-3-1.MS：m/z：455。
The nuclear magnetic resonance spectrum of compound I-3-1 does
1H-NMR (300MHz, CDCl
3), δ (ppm): 7.809-7.837 (2H, d); 7.537-7.6.7 (4H, m), 7.169-7.177 (1H, d), 7.113-7.148 (1H, q); 6.793-6.842 (1H, t), 4.138-4.207 (2H, q), 3.038-3.131 (2H, m); 2.593-2.670 (2H, q), 2.446-2.577 (1H, m), 1.495-1.555 (5H; M), and 1.375-1.472 (2H, m), 0.931-0.978 (3H, t).
The liquid crystal property of compound I-3-1:
Δn：0.372 Δε：10 Cp：229.2℃
Compound I-3-1's
1HNMR figure sees Fig. 8.
The mass spectrum of compound I-3-1 is seen Fig. 9.
The synthetic route of preparation compound I-4-1 representes that in Figure 10 its concrete process step is following:
1) compound of preparation formula 3 process step 1 among the employing embodiment 1)～2)
2) compound of synthesis type 13
The compound that adds the formula 14 of 7g in the 250mL round-bottomed flask, the compound of the formula 15 of 7g, the dissolving of 100mL glycol dimethyl ether, 30mL wet chemical (2molL
-1), 0.5g Tetrabutyl amonium bromide, 0.4g Pd (PPh
3)
4, nitrogen protection, back flow reaction 5h.Reaction water cancellation, ethyl acetate extraction, organic phase use anhydrous sodium sulfate drying, revolves dried solvent, sherwood oil is that the moving phase column chromatography is separated, elutriant concentrated white solid 3.6g, make the compound of formula 13.
3) compound of synthesis type 16
The compound that adds the formula 13 of 4.8g in the 250mL round-bottomed flask, 60ml THF, nitrogen protection, low temperature splashes into 8.6mL n-BuLi under-78 ℃, drip Bi Fanying 2h.8.2g boric acid three isobutylates are dissolved among the 20mLTHF, and temperature is controlled at below-60 ℃ and splashes in the reaction system, drips to finish to stir 2h.Reaction solution is poured in the hydrochloric acid, stirred 30min, ethyl acetate extraction revolves dried organic phase, and resistates is used petroleum ether, and suction filtration gets white solid 5.8g, makes the compound of formula 16.
4) synthetic compound I-4-1
The compound that adds the formula 3 of 3.5g in the 100mL round-bottomed flask, the compound of the formula 16 of 3.2g, 30mL glycol dimethyl ether, 10mL wet chemical (2molL
-1), 0.3g Tetrabutyl amonium bromide, 0.2g Pd (PPh
3)
4, nitrogen protection, backflow 5h.
The cancellation of reaction water, ethyl acetate extraction, organic phase is used anhydrous sodium sulfate drying, revolves dried solvent, and sherwood oil separates for the moving phase column chromatography, gets gray solid 2g, and the absolute ethyl alcohol recrystallization gets white needle-like crystals 1.3g, and purity 99.20% makes compound I-4-1.MS：m/z：491。
The nuclear magnetic resonance spectrum of compound I-4-1 does
1H-NMR (300MHz, CDCl
3), δ (ppm): 7.537-7.599 (2H, m); 7.351-7.399 (1H, m); 7.176-7.292 (2H, m); 7.060-7.114 (1H, m); 6.808-6.868 (1H, m); 4.152-4.222 (2H, q); 3.041-3.129 (2H, m); 2.589-2.659 (2H, m); 2.446-2.546 (1H, m); 1.409-1.564 (5H, m); 1.370-1.393 (2H, m); 0.950-0973 (3H, m).
The liquid crystal property of compound:
Δn：0.281 Δε：14.8 Cp：159.2
Compound I-4-1's
1H NMR figure sees Figure 11.
The mass spectrum of compound I-4-1 is seen Figure 12.
Performance relatively
For ease of expressing, the unit structure of following liquid crystalline cpd is with the listed coded representation of table 1:
The unit structure code of table 1 liquid crystalline cpd
With following structure is example:
This structure is with the coded representation in the table 1: then can be expressed as 3PTWTP3, and for example:
Then can be expressed as nCPTPOm, the n in the code representes the C atomicity of left end alkyl, and for example n is " 3 ", representes that promptly this alkyl is-C
3H
7C in the code represents cyclohexyl; O represention oxygen atom in the code; P in the code represents phenylene; M in the code representes the C atomicity of right-hand member alkyl, and for example m is " 1 ", representes that promptly the alkyl of right-hand member is-CH
3
Monomer extrapolation testing method:
With monomer and parent liquid-crystal compsn (Δ n:0.126; Δ ε: 10.5; CP:82.2) according to after the weight ratio mixing in 1: 9, carry out performance test, calculate monomeric each item performance according to linear gauge then.
(1) to be dissolved in each item performance that records behind the above-mentioned parent liquid-crystal compsn following for monomer 3IPWO2:
Δn：0.1397 Δε：10.43 CP：91
This monomer extrapolation performance is following:
Δn：0.263 Δε：9.8 CP：170.2
(2) monomer 3IV (2F) PWO2 (it is following that compound I-3-1) is dissolved in each item performance that records behind the above-mentioned parent liquid-crystal compsn:
Δn：0.1506 Δε：10.45 CP：96.9
This monomer extrapolation performance is following:
Δn：0.372 Δε：10 CP：229.2
Can find out that from (1), (2) data compound provided by the invention has good dielectricity, specific refractory power and high clearing point.This type of liquid crystalline cpd can make the liquid-crystal display of using this compound have speed of answer faster, enlarges the working range of liquid-crystal display, makes liquid-crystal display in various environment, all can keep good demonstration.
Claims (10)
1. compound with general formula (I):
Wherein,
R
1, R
2Identical or different, be selected from by H, halogen, halo or unsubstituted alkyl or alkoxyl group independently of one another and have halo or the unsubstituted alkane thiazolinyl of 2-7 carbon atom or the group that the alcoxyl thiazolinyl is formed with 1-7 carbon atom, wherein, at said R
1With said R
2In one or more CH2 groups can be independently of one another by-CH=CH-,-O-,-CH=CF-,-CF=CH-,-CF=CF-,-CO-O-or-O-CO-substitutes, its prerequisite is that Sauerstoffatom directly is not connected to each other;
Identical or different, be selected from independently of one another by
The group of forming, wherein, said
In at least one do
Z
1And Z
2Identical or different, be independently from each other separately by-CO-O-,-O-CO-,-CF
2O-,-OCF
2-,-CH
2O-,-OCH
2-,-CH
2CH
2-,-(CH
2)
4-,-C
2F
4-,-CH
2CF
2-,-CF=CF-,-group that CH=CH-and singly-bound are formed;
S, m represent 0,1 or 2 separately independently of one another, and 0≤s+m≤3.
2. according to the said compound of claim 1, it is characterized in that said R
1, R
2Identical or different, be selected from independently of one another by-C
2H
5, n-C
3H
7, n-C
4H
9, n-C
5H
11And n-C
6H
13The group of forming, wherein, at said R
1With said R
2In one or more CH
2Group can be independently of one another by-CH=CH-,-O-,-CF=CF-or-CO-O-substitutes, its prerequisite is that Sauerstoffatom directly is not connected to each other.
3. according to the said compound of claim 1; It is characterized in that; Said
is identical or different; Be selected from the group of forming by
independently of one another; Wherein, at least one in said
is
4. according to the said compound of claim 1, it is characterized in that said Z
1And Z
2Identical or different, be selected from independently of one another by-OCH
2-,-CH
2O-,-OCF
2-,-CF
2The group that O-and singly-bound are formed.
5. according to the said compound of claim 1, it is characterized in that said s, m is identical or different, representes 0 or 1 independently of one another, and 0≤s+m≤2.
6. according to the said compound of claim 1, said compound is selected from the group of being made up of following compound:
Wherein, said R
1, R
2Identical or different, be selected from independently of one another by-C
2H
5, n-C
3H
7, n-C
4H
9And n-C
5H
11The group of forming, wherein, at said R
1With said R
2In one or more CH
2Group can be separately independently by-CH=CH-,-O-,-CF=CF-or-CO-O-substitutes, its prerequisite is that Sauerstoffatom directly is not connected to each other; Z
2For-OCH
2-,-CH
2O-,-OCF
2-,-CF
2O-or singly-bound.
7. according to the said compound of claim 1, said compound is selected from the group of being made up of following compound:
8. a method for preparing like any one described compound in the claim 1 to 7 comprises the steps:
1) make solvent with THF, under nitrogen protection with the compound of general formula 1
With the reaction of magnesium powder, generate the grignard reagent of general formula 2,
The grignard reagent of said general formula 2 and trifluoro-ethylene obtain the compound of general formula 3 stirring at room reaction 0.5-3 hour;
2) in tetrahydrofuran solvent, under-78 ℃～-40 ℃, nitrogen protection, with the compound of general formula 3 and n-Butyl Lithium (nBuLi) reaction 1-2 hour; Iodine is dissolved in the system that splashes into the compound that comprises general formula 3 and n-Butyl Lithium behind the THF, reacted 0.5-2 hour, obtain the compound of general formula 4;
3) in tetrahydrofuran solvent, at-78 ℃～-40 ℃, under the nitrogen protection, with the compound of general formula 5
With n-Butyl Lithium, the reaction of boric acid three isobutylates, obtain the compound of general formula 6,
Then the compound of general formula 6 and the compound of general formula 4 were reacted 4-6 hour in tetra-triphenylphosphine palladium catalysis refluxed, obtain the compound of general formula (I)
Wherein, R
1And R
2Identical or different, be selected from by H, halogen, halo or unsubstituted alkyl or alkoxyl group independently of one another and have halo or the unsubstituted alkane thiazolinyl of 2-7 carbon atom or the group that the alcoxyl thiazolinyl is formed with 1-7 carbon atom, wherein, at said R
1With said R
2In one or more CH
2Group can be independently of one another by-CH=CH-,-O-,-CH=CF-,-CF=CH-,-CF=CF-,-CO-O-or-O-CO-substitutes, its prerequisite is that Sauerstoffatom directly is not connected to each other;
Z
1And Z
2Identical or different, be independently from each other separately by-CO-O-,-O-CO-,-CF
2O-,-OCF
2-,-CH
2O-,-OCH
2-,-CH
2CH
2-,-(CH
2)
4-,-C
2F
4-,-CH
2CF
2-,-CF=CF-,-group that CH=CH-and singly-bound are formed;
S, m are identical or different, represent 0,1 or 2 separately independently of one another, and 0≤s+m≤3.
9. a liquid-crystal compsn comprises a kind of or more kinds of like each the described compound in the claim 1 to 7.
10. liquid crystal cell that comprises liquid-crystal compsn as claimed in claim 9.
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| CN106675575A (en) * | 2015-11-06 | 2017-05-17 | 江苏和成显示科技股份有限公司 | Dielectric negative liquid crystal compound as well as preparation method and application thereof |
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| CN103351275B (en) * | 2013-07-01 | 2015-06-10 | 江苏和成显示科技股份有限公司 | Liquid crystal compound including polyfluoroindan, composition thereof and application |
| CN106675575A (en) * | 2015-11-06 | 2017-05-17 | 江苏和成显示科技股份有限公司 | Dielectric negative liquid crystal compound as well as preparation method and application thereof |
| CN106675575B (en) * | 2015-11-06 | 2018-12-18 | 江苏和成显示科技有限公司 | A kind of dielectric negative liquid crystal compound and the preparation method and application thereof |
| CN108690640A (en) * | 2018-07-17 | 2018-10-23 | 烟台显华化工科技有限公司 | A kind of compound and liquid crystal media of the ring containing indenes |
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