CN102659533B - 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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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 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
- 239000000203 mixture Substances 0.000 claims abstract description 29
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 46
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 30
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 25
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 21
- 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
- 238000003756 stirring Methods 0.000 claims description 11
- 125000000217 alkyl group 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
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- -1 isobutyl ester Chemical class 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
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 4
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 230000003287 optical effect Effects 0.000 abstract description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 39
- 238000000605 extraction Methods 0.000 description 13
- 239000012074 organic phase Substances 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 11
- 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
- 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
- 239000000178 monomer Substances 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 7
- 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
- 150000001721 carbon Chemical group 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229960000935 dehydrated alcohol Drugs 0.000 description 4
- 125000005843 halogen group Chemical group 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
- 230000000694 effects Effects 0.000 description 3
- 238000013213 extrapolation Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000002769 thiazolinyl group Chemical group 0.000 description 2
- 0 C*c1ccc(CC(*C2CCC(*)CC2)C2)c2c1 Chemical compound C*c1ccc(CC(*C2CCC(*)CC2)C2)c2c1 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 CCCC(C1)Cc2c1ccc(/C(/F)=C(/c(cc1)ccc1-c(ccc(OCC)c1F)c1F)\F)c2 Chemical compound CCCC(C1)Cc2c1ccc(/C(/F)=C(/c(cc1)ccc1-c(ccc(OCC)c1F)c1F)\F)c2 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
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000012612 commercial material 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
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 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
- 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
- 238000005259 measurement Methods 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
- 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
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 of the component as liquid crystal media and its preparation method and application.
Background technology
Liquid crystal material is a kind of mesomorphic phase material between solid phase and liquid phase, is mainly used as the dielectric medium in indicating meter, and its reason is that the optical property of this kind of material changes by the voltage applied.Electrooptical devices based on liquid crystal is known in those skilled in the art, wherein can comprise various effect.The example of this kind of device has the liquid crystal cell of dynamic scattering, 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 (super birefringence effect) liquid crystal cell and OMI (interference of light film) liquid crystal cell.Modal indicating meter is based on Schadt-Helfrich effect and have twisted-nematic structure.In addition, also there is the liquid crystal cell of the electric field operation for being parallel to substrate and liquid crystal surface, such as IPS (switching in face) liquid crystal cell.Especially, TN, STN and IPS liquid crystal cell, especially TN and IPS liquid crystal cell is the Application Areas at present with commercial significance of medium of the present invention.
For liquid-crystal display, there is thermostability, good dielectric properties and more low viscous liquid crystalline cpd and liquid crystal media meets current needs.In order to expand the working range of liquid-crystal display, liquid crystal display material needs wide nematic temperature range, to meet the requirement that all can keep good display in various environment.
In recent years in large-size liquid crystal television, thin film transistor (TFT) display format of liquid crystal molecule (VA) arranged vertically is used widely.Its advantage is that visual angle is wide, fast response time, contrast gradient are larger.Traditional distortion-nematic-mode (TN) uses dielectric anisotropy to be just (Δ ε=ε
//-ε
⊥, Δ ε > 0) liquid crystal material, molecular long axis direction has polar group, makes long axis direction specific inductivity (ε
//) be greater than perpendicular electric constant (ε
⊥); And the liquid crystal material that VA pattern requirements adopts has the larger dielectric anisotropy of negativity value (Δ ε < 0) and larger optical anisotropy (Δ n).Have at present and develop the larger liquid crystalline cpd of many negativity values, as US6348244B, CN102153442, WO9919420, the Δ ε value of above-claimed cpd is very large, but Δ n is less, and resistivity and voltage retention are also very low.Therefore, existence provides the new needs with the negative liquid crystal material of higher dielectricity and optical anisotropy, high clearing point and wide nematic temperature range.
Summary of the invention
The object of this invention is to provide a kind of can as the indene derivative of the component of liquid crystal media, this compound can as negative liquid crystal material.
Another object of the present invention is to provide the preparation method of above-mentioned indene derivative.
Another object of the present invention is to provide a kind of liquid-crystal composition comprising indene derivative.
Another object of the present invention is to provide and a kind ofly comprises the liquid crystal cell of described liquid-crystal composition as integrant.
One aspect of the present invention, provide a kind of can as the indene derivative of the component of liquid crystal media, this compound has the structure shown in general formula (I):
Wherein,
R
1, R
2identical or different, be selected from by H, halogen, the halo with 1-7 carbon atom or unsubstituted alkyl or alkoxyl group independently of one another and there is the group that the halo of 2-7 carbon atom or unsubstituted alkane thiazolinyl or alcoxyl thiazolinyl form, wherein, at described R
1with described R
2in one or more CH
2group can be substituted by-CH=CH-,-O-,-CH=CF-,-CF=CH-,-CF=CF-,-CO-O-or-O-CO-independently of one another, and its prerequisite is that Sauerstoffatom is not directly connected to each other;
identical or different, be selected from independently of one another by
the group of composition, wherein, described in
in at least one be
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-,-CH=CH-and singly-bound composition group;
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 composition, wherein, at described R
1with described R
2in one or more CH
2group can be substituted by-CH=CH-,-O-,-CF=CF-or-CO-O-independently of one another, and its prerequisite is that Sauerstoffatom is not directly connected to each other.
In some preferred embodiments,
identical or different, be selected from independently of one another by
the group of composition, wherein, described in
in at least one be
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 of O-and singly-bound composition.
In some preferred embodiments, s, m are identical or different, represent 0 or 1 independently of one another separately, and 0≤s+m≤2.
Preferably, compound of the present invention is selected from the group be made up of following compound:
and
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 composition, wherein, at described R
1with described R
2in one or more CH2 groups can independently be substituted by-CH=CH-,-O-,-CF=CF-or-CO-O-separately, its prerequisite is that Sauerstoffatom is not directly 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 be made up of following compound:
Another aspect of the present invention provides a kind of method preparing compound of the present invention, comprises the steps:
1) solvent is made with tetrahydrofuran (THF), under nitrogen protection by the compound of general formula 1
React with magnesium powder, generate the grignard reagent of general formula 2,
Grignard reagent and the trifluorochloroethylene of described general formula 2 react 0.5-3 hour in stirring at room temperature, obtain the compound of general formula 3;
2) in tetrahydrofuran solvent ,-78 DEG C ~-40 DEG C, under nitrogen protection, the compound of general formula 3 and n-Butyl Lithium (nBuLi) are reacted 1-2 hour; After iodine being dissolved in tetrahydrofuran (THF), instillation comprises in the compound of general formula 3 and the system of n-Butyl Lithium, and reaction 0.5-2 hour, obtains the compound of general formula 4;
3) in tetrahydrofuran solvent, at-78 DEG C ~-40 DEG C, under nitrogen protection, by the compound of general formula 5
React with n-Butyl Lithium, boric acid three isobutyl ester, obtain the compound of general formula 6,
Then by compound back flow reaction 4-6 hour under tetra-triphenylphosphine palladium catalysis of the compound of general formula 6 and general formula 4, the compound of general formula (I) is obtained
Wherein, R
1and R
2identical or different, be selected from by H, halogen, the halo with 1-7 carbon atom or unsubstituted alkyl or alkoxyl group independently of one another and there is the group that the halo of 2-7 carbon atom or unsubstituted alkane thiazolinyl or alcoxyl thiazolinyl form, wherein, at described R
1with described R
2in one or more CH
2group can be substituted by-CH=CH-,-O-,-CH=CF-,-CF=CH-,-CF=CF-,-CO-O-or-O-CO-independently of one another, and its prerequisite is that Sauerstoffatom is not directly connected to each other;
identical or different, be selected from independently of one another by
the group of composition, wherein, described in
in at least one be
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-,-CH=CH-and singly-bound composition group;
S, m are identical or different, represent 0,1 or 2 independently of one another separately, and 0≤s+m≤3.
Another aspect of the present invention provides a kind of liquid-crystal composition, and this liquid-crystal composition comprises one or more of compound of the present invention.
Another aspect of the invention is to provide a kind of liquid crystal cell comprising liquid-crystal composition of the present invention.
Compared with other liquid crystalline cpds of negative liquid crystal compound and prior art of general formula provided by the invention (I), there is higher dielectricity, refractive anisotrop, high clearing point and wide nematic temperature range, and chemical property is all stable; In the negative liquid crystal preparation of compounds of general formula (I), raw material is easy to get, and synthetic route is simple, is applicable to large-scale industrial and produces, be beneficial to the use as display liquid crystal material, can be used for the time of response of improving liquid-crystal composition; Expand operating temperature range.
Accompanying drawing explanation
Fig. 1 is the synthetic route chart of Compound I-1-1.
Fig. 2 is Compound I-1-1
1h NMR schemes.
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 schemes.
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 schemes.
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 schemes.
Figure 12 is the mass spectrum of Compound I-4-1.
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 the present invention is described, and are not used for limiting the present invention.When not departing from purport of the present invention or scope, other combination and the various improvement in design of the present invention can be carried out.
In following examples, the code name of writing a Chinese character in simplified form of each test event is expressed as:
Cp (DEG C) clearing point (to row-isotropic phase transition temperature)
Δ n optical anisotropy (589nm, 20 DEG C)
Δ ε dielectric anisotropy (1KHz, 25 DEG C)
Wherein, refractive anisotrop use Abbe refractometer under sodium lamp (589nm) light source, 20 DEG C test; Measurement box is TN90 type, thick 7 μm of box.
Reagent used in the present invention and other raw materials are commercially available commercial materials.
Embodiment 1
The synthetic route of preparation Compound I-1-1 represents in FIG, and its concrete technology step is as follows:
1) compound of synthesis type 1
(formula 1)
(formula 2)
Mg powder and the 0.05g iodine of 8g is added, 10mL tetrahydrofuran (THF) (THF), nitrogen protection in 500mL there-necked flask.By the compound dissolution of the formula 2 of 45g in 200mL tetrahydrofuran solution, slowly the tetrahydrofuran solution of the compound of formula 2 is added to above-mentioned reaction system, after question response causes, continue the tetrahydrofuran solution of the compound dripping remaining formula 2, drip and finish, the micro-backflow 3h that boils of maintenance system, is cooled to room temperature.40g trifluorochloroethylene is slowly passed in cooled reaction system, stirring at room temperature 12h.
Reaction uses dilute hydrochloric acid cancellation, extraction into ethyl acetate, and organic phase anhydrous sodium sulfate drying, is spin-dried for solvent, and underpressure distillation obtains colourless liquid 30g, yield 60%, is the compound of formula 1.
2) compound of synthesis type 3
(formula 3)
Add the compound of the formula 1 of 30g in 500mL there-necked flask, 100mL THF, nitrogen protection, subcooling, to the n-Butyl Lithium (n-BuLi, 2.4mol/L) instilling 45mL at-78 DEG C, drips Bi Fanying 1h.28g iodine is dissolved in 100mL THF, and temperature controls to be added dropwise in reaction system below-60 DEG C, drips Bi Fanying 2h.
Reaction uses dilute hydrochloric acid cancellation, extraction into ethyl acetate, and organic phase anhydrous sodium sulfate drying, is spin-dried for solvent, with sherwood oil moving phase chromatography over CC, obtains Vandyke brown liquid 25g, is the compound of formula 3.
3) compound of synthesis type 5
(formula 4)
(formula 5)
Add the compound of the formula 4 of 5.2g in 100mL round-bottomed flask, 30mL THF, nitrogen protection, low temperature, to the n-Butyl Lithium (n-BuLi, 2.4mol/L) instilling 13mL at-78 DEG C, drips Bi Fanying 2h.Boric acid three isobutyl ester of 14g is dissolved in 20mL THF, is added dropwise in reaction system in-78 DEG C, drip Bi Ziran and rise to room temperature, stirring reaction 2h.
By cancellation reaction in reaction solution impouring dilute hydrochloric acid, stir 30min, extraction into ethyl acetate, is spin-dried for organic solvent, resistates petroleum ether, and suction filtration obtains white solid 5g, is the compound of formula 5.
4) synthetic compound I-1-1
The compound of the compound of the formula 3 of 3.5g, the formula 5 of 2.2g is added, 30mL glycol dimethyl ether, 10mL wet chemical (2molL in 100mL round-bottomed flask
-1), 0.3g Tetrabutyl amonium bromide, 0.2g Pd (PPh
3)
4, nitrogen protection, back flow reaction 5h.
Reaction shrend is gone out, extraction into ethyl acetate, and organic phase anhydrous sodium sulfate drying, is spin-dried for solvent, and sherwood oil is moving phase pillar layer separation, and elutriant concentrates to obtain light black oily matter 1.8g, and dehydrated alcohol recrystallization, obtains white needle-like crystals 1.3g, purity 99.65%.Obtained Compound I-1-1.MS：m/z：393。
The nuclear magnetic resonance spectrum of Compound I-1-1 is
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 is shown in Fig. 2.
The mass spectrum of Compound I-1-1 is shown in Fig. 3.
Embodiment 2
The synthetic route of preparation Compound I-2-1 represents in the diagram, and its concrete technology step is as follows:
1) step 1 in embodiment 1 is adopted) ~ 2) compound of preparation formula 3.
2) compound of synthesis type 6
(formula 6)
(formula 7)
(formula 8)
(formula 9)
Formula 8 compound of the compound of the formula 7 of 9.3g, 6.4g is added, 100mL glycol dimethyl ether, 35mL wet chemical (2molL in 250mL round-bottomed flask
-1), 0.5g Tetrabutyl amonium bromide, 0.4g Pd (PPh
3)
4, nitrogen protection, backflow 5h.Reaction shrend is gone out, extraction into ethyl acetate, and organic phase anhydrous sodium sulfate drying, is spin-dried for solvent, and sherwood oil is moving phase pillar layer separation, and elutriant concentrates to obtain colourless liquid 7.6g, the compound of obtained formula 9.
Add in 250mL round-bottomed flask (formula 9) of 7.6g, 60mL THF, nitrogen protection, low temperature instills 42mL n-BuLi at-78 DEG C, drips Bi Fanying 2h.Be dissolved in 20mLTHF by 16g boric acid three isobutyl ester ,-78 DEG C are added dropwise in reaction system, drip to finish to stir 2h.By in reaction solution impouring dilute hydrochloric acid, stir 30min, extraction into ethyl acetate, is spin-dried for organic phase, resistates petroleum ether, and suction filtration obtains white solid 5g, the compound of obtained formula 6.
3) synthetic compound I-2-1
The compound of the formula 3 of 3.5g is added, the compound of the formula 6 of 2.6g, 30mL glycol dimethyl ether, 10mL wet chemical (2molL in 100mL round-bottomed flask
-1), 0.3g Tetrabutyl amonium bromide, 0.2g Pd (PPh
3)
4, nitrogen protection, backflow 5h.
Reaction shrend is gone out, extraction into ethyl acetate, and organic phase anhydrous sodium sulfate drying, is spin-dried for solvent, and sherwood oil is moving phase pillar layer separation, obtains gray solid 3g, and dehydrated alcohol recrystallization, obtains white needle-like crystals 2.2g, purity 99.69%, obtained Compound I-2-1.MS：m/z：439。
The nuclear magnetic resonance spectrum of Compound I-2-1 is
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 is shown in Fig. 5
The mass spectrum of Compound I-2-1 is shown in Fig. 6.
Embodiment 3
The synthetic route of preparation Compound I-3-1 represents in the figure 7, and its concrete technology step is as follows:
1) processing step 1 in embodiment 1 is adopted) ~ 2) compound of preparation formula 3.
2) compound of synthesis type 10
(formula 10)
(formula 11)
Add the compound of the formula 11 of 6g in 250mL round-bottomed flask, 8.5g is to benzene bromine iodine, and 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 shrend is gone out, extraction into ethyl acetate, and organic phase anhydrous sodium sulfate drying, is spin-dried for solvent, and sherwood oil is moving phase pillar layer separation, and elutriant concentrates to obtain white solid 8.5g, the compound of obtained formula 10.
3) compound of synthesis type 12
(formula 12)
Add the compound of the formula 10 of 8.5g in 250mL round-bottomed flask, 60ml THF, nitrogen protection, low temperature instills 13mL n-BuLi at-78 DEG C, drips Bi Fanying 2h.Be dissolved in 20mLTHF by 13g boric acid three isobutyl ester, temperature controls to be added dropwise in reaction system below-60 DEG C, drips to finish to stir 2h.Poured into by reaction solution in hydrochloric acid, stir 30min, extraction into ethyl acetate, is spin-dried for organic phase, resistates petroleum ether, and suction filtration obtains white solid 7.7g, the compound of obtained formula 12.
4) synthetic compound I-3-1
The compound of the formula 3 of 2.8g is added, the compound of the formula 12 of 2.9g, 30mL glycol dimethyl ether, 8mL wet chemical (2molL in 100mL round-bottomed flask
-1), 0.3g Tetrabutyl amonium bromide, 0.2g Pd (PPh
3)
4, nitrogen protection, back flow reaction 5h.
Reaction shrend is gone out, extraction into ethyl acetate, and organic phase anhydrous sodium sulfate drying, is spin-dried for solvent, and sherwood oil is moving phase pillar layer separation, obtains gray solid 3g, and dehydrated alcohol recrystallization, obtains white needle-like crystals 2.2g, purity 99.16%, obtained Compound I-3-1.MS：m/z：455。
The nuclear magnetic resonance spectrum of Compound I-3-1 is
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), 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 is shown in Fig. 8.
The mass spectrum of Compound I-3-1 is shown in Fig. 9.
Embodiment 4
The synthetic route of preparation Compound I-4-1 represents in Fig. 10, and its concrete technology step is as follows:
1) processing step 1 in embodiment 1 is adopted) ~ 2) compound of preparation formula 3
2) compound of synthesis type 13
(formula 13)
(formula 14)
(formula 15)
Add the compound of the formula 14 of 7g in 250mL round-bottomed flask, the compound of the formula 15 of 7g, 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 shrend is gone out, extraction into ethyl acetate, and organic phase anhydrous sodium sulfate drying, is spin-dried for solvent, and sherwood oil is moving phase pillar layer separation, and elutriant concentrates to obtain white solid 3.6g, the compound of obtained formula 13.
3) compound of synthesis type 16
(formula 16)
Add the compound of the formula 13 of 4.8g in 250mL round-bottomed flask, 60ml THF, nitrogen protection, low temperature instills 8.6mL n-BuLi at-78 DEG C, drips Bi Fanying 2h.Be dissolved in 20mLTHF by 8.2g boric acid three isobutyl ester, temperature controls to be added dropwise in reaction system below-60 DEG C, drips to finish to stir 2h.Poured into by reaction solution in hydrochloric acid, stir 30min, extraction into ethyl acetate, is spin-dried for organic phase, resistates petroleum ether, and suction filtration obtains white solid 5.8g, the compound of obtained formula 16.
4) synthetic compound I-4-1
The compound of the formula 3 of 3.5g is added, the compound of the formula 16 of 3.2g, 30mL glycol dimethyl ether, 10mL wet chemical (2molL in 100mL round-bottomed flask
-1), 0.3g Tetrabutyl amonium bromide, 0.2g Pd (PPh
3)
4, nitrogen protection, backflow 5h.
Reaction shrend is gone out, extraction into ethyl acetate, and organic phase anhydrous sodium sulfate drying, is spin-dried for solvent, and sherwood oil is moving phase pillar layer separation, obtains gray solid 2g, and dehydrated alcohol recrystallization, obtains white needle-like crystals 1.3g, purity 99.20%, obtained Compound I-4-1.MS：m/z：491。
The nuclear magnetic resonance spectrum of Compound I-4-1 is
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 is shown in Figure 11.
The mass spectrum of Compound I-4-1 is shown in Figure 12.
performance comparision
For ease of expressing, the coded representation listed by unit structure table 1 of following liquid crystalline cpd:
The unit structure code of table 1 liquid crystalline cpd
For following structure:
Coded representation in this structure table 1: then can be expressed as 3PTWTP3, and for example:
Then can be expressed as nCPTPOm, the n in code represents the C atomicity of left end alkyl, and such as n is " 3 ", namely represents that this alkyl is-C
3h
7; C in code represents cyclohexyl; O represention oxygen atom in code; P in code represents phenylene; M in code represents the C atomicity of right-hand member alkyl, and such as m is " 1 ", namely represents that the alkyl of right-hand member is-CH
3.
Monomer extrapolation measure method:
By monomer and parent liquid-crystal composition (Δ n:0.126; Δ ε: 10.5; CP:82.2), after mixing according to weight ratio 1: 9, carry out performance test, then calculate the properties of monomer according to linear gauge.
(1) properties that records after being dissolved in above-mentioned parent liquid-crystal composition of monomer 3IPWO2 is as follows:
Δn：0.1397 Δε：10.43 CP：91
This monomer extrapolation performance is as follows:
Δn：0.263 Δε：9.8 CP：170.2
(2) properties recorded after monomer 3IV (2F) PWO2 (Compound I-3-1) is dissolved in above-mentioned parent liquid-crystal composition is as follows:
Δn：0.1506 Δε：10.45 CP：96.9
This monomer extrapolation performance is as follows:
Δn：0.372 Δε：10 CP：229.2
As can be seen 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 this compound of application have speed of answer faster, expands the working range of liquid-crystal display, makes liquid-crystal display all can keep good display in various environment.
Claims (10)
1. one kind has the compound of general formula (I):
Wherein,
R
1, R
2identical or different, be selected from the group be made up of the alkyl or alkoxyl group with 1-7 carbon atom independently of one another;
identical or different, be selected from independently of one another by
the group of composition, wherein, described in
with
in at least one be
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-,-CH=CH-and singly-bound composition group;
S, m represent 0,1 or 2 separately independently of one another, and 0≤s+m≤3.
2. compound according to claim 1, is characterized in that, described 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 composition.
3. compound according to claim 1, is characterized in that, described in
identical or different, be selected from independently of one another by
the group of composition, wherein, described in
in at least one be
4. compound according to claim 1, is characterized in that, described Z
1and Z
2identical or different, be selected from independently of one another by-OCH
2-,-CH
2o-,-OCF
2-,-CF
2the group of O-and singly-bound composition.
5. compound according to claim 1, it is characterized in that, described s, m are identical or different, represent 0 or 1 independently of one another, and 0≤s+m≤2.
6. compound according to claim 1, described compound is selected from the group be made up of following compound:
Wherein, described 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 composition; Z
2for-OCH
2-,-CH
2o-,-OCF
2-,-CF
2o-or singly-bound.
7. compound according to claim 1, described compound is selected from the group be made up of following compound:
8. prepare the method as the compound in claim 1 to 7 as described in any one, comprise the steps:
1) solvent is made with tetrahydrofuran (THF), under nitrogen protection by the compound of general formula 1
React with magnesium powder, generate the grignard reagent of general formula 2,
Grignard reagent and the trifluorochloroethylene of described general formula 2 react 0.5-3 hour in stirring at room temperature, obtain the compound of general formula 3;
2) in tetrahydrofuran solvent ,-78 DEG C ~-40 DEG C, under nitrogen protection, the compound of general formula 3 and n-Butyl Lithium (nBuLi) are reacted 1-2 hour; After iodine being dissolved in tetrahydrofuran (THF), instillation comprises in the compound of general formula 3 and the system of n-Butyl Lithium, and reaction 0.5-2 hour, obtains the compound of general formula 4;
3) in tetrahydrofuran solvent, at-78 DEG C ~-40 DEG C, under nitrogen protection, by the compound of general formula 5
React with n-Butyl Lithium, boric acid three isobutyl ester, obtain the compound of general formula 6,
Then by compound back flow reaction 4-6 hour under tetra-triphenylphosphine palladium catalysis of the compound of general formula 6 and general formula 4, the compound of general formula (I) is obtained
Wherein, R
1and R
2identical or different, be selected from the group be made up of the alkyl or alkoxyl group with 1-7 carbon atom independently of one another;
identical or different, be selected from independently of one another by
the group of composition, wherein, described in
in at least one be
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-,-CH=CH-and singly-bound composition group;
S, m are identical or different, represent 0,1 or 2 independently of one another separately, and 0≤s+m≤3.
9. a liquid-crystal composition, comprises one or more of compound as described in any one in claim 1 to 7.
10. one kind comprises the liquid crystal cell of liquid-crystal composition as claimed in claim 9.
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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 |
| 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 |
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