CN102757793B - Liquid crystal compound and application thereof - Google Patents
Liquid crystal compound and application thereof Download PDFInfo
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- CN102757793B CN102757793B CN201210265488.1A CN201210265488A CN102757793B CN 102757793 B CN102757793 B CN 102757793B CN 201210265488 A CN201210265488 A CN 201210265488A CN 102757793 B CN102757793 B CN 102757793B
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 101
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 125000003545 alkoxy group Chemical group 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 10
- 150000001336 alkenes Chemical class 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 9
- -1 fluoro thiazolinyl Chemical group 0.000 claims description 6
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims 9
- 125000001475 halogen functional group Chemical group 0.000 claims 1
- 230000004044 response Effects 0.000 abstract description 4
- 230000003287 optical effect Effects 0.000 abstract description 3
- 239000012533 medium component Substances 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 54
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 27
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 150000001721 carbon Chemical group 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000005406 washing Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 7
- 239000004327 boric acid Substances 0.000 description 7
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 7
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- LHJSLDBKUGXPMI-UHFFFAOYSA-N tris(2-methylpropyl) borate Chemical compound CC(C)COB(OCC(C)C)OCC(C)C LHJSLDBKUGXPMI-UHFFFAOYSA-N 0.000 description 7
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000010025 steaming Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000000284 extract Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000003810 ethyl acetate extraction Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 238000010009 beating Methods 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012092 media component Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- YTXAYGAYACWVGD-UHFFFAOYSA-N palladium;hydrate Chemical compound O.[Pd] YTXAYGAYACWVGD-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 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
- BPAAKFGBSPZPQO-UHFFFAOYSA-N NC(CC1)CC=C1N Chemical compound NC(CC1)CC=C1N BPAAKFGBSPZPQO-UHFFFAOYSA-N 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
- 239000012230 colorless oil Substances 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
- 230000006872 improvement Effects 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
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- Liquid Crystal Substances (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a compound with a general formula (I), which can be used as a liquid crystal medium component, and an application thereof. The compound has the characteristics of higher dielectric property and optical anisotropy; and a display using the compound can obtain higher response speed. The invention further provides a liquid crystal composition, which includes one or more of the compounds, and a liquid crystal display element, which includes the liquid crystal composition.
Description
Technical field
The present invention relates to compound as the component of liquid crystal media and its preparation method and application.
Background technology
In liquid-crystal display, liquid crystal is used as dielectric medium, and its optical property is being executed reversibly variation under alive effect.With liquid crystal, as the electro-optic displays of medium, be that those skilled in the art are familiar with.These liquid-crystal displays use various electrooptic effects.TN (twisted nematic type) effect the most generally, have liquid crystal director uniformly, the nematic structure of about 90 ° of the initial orientation of plane and distortion substantially, STN (supertwist is listed as mutually) effect and SBE (supertwisted birefringent effect), have 180 ° of distortions or larger nematic structure.
The IPS that level of application increases recently (switching in face) effects etc. are enough uses dielectric positivity and dielectric negative liquid crystal medium in the mode similar to " guest/master " indicating meter, this in-plane-switching mode (as DE4000451, DE0588568) is particularly useful for the LCD of the upper watch-dog of modern table, and is conceived to the display application for multimedia application.
Because the operating voltage of liquid-crystal display should be low as much as possible conventionally, because use the liquid crystal media with large dielectric anisotropy absolute value, this liquid crystal media is conventionally mainly with in most cases even substantially by the liquid crystalline cpd with the dielectric anisotropy of respective symbol, the in the situation that of dielectric positivity medium the compound of positive dielectric anisotropy and the in the situation that of dielectric negativity medium the compound of negative dielectric anisotropy form.In the medium of type (dielectric positivity or dielectric negativity) separately, the electroneutral liquid crystalline cpd that is situated between is used with significant quantity at the most conventionally.Have that liquid crystalline cpd with the dielectric anisotropy of the dielectric anisotropy contrary sign of medium is conventionally few to be used or do not use.
The liquid crystal media of prior art has relatively high operating voltage conventionally looks the time of response with relative, and these are unsuitable, particularly for the indicating meter that can form image.In addition, they are conventionally unsuitable for high service temperature and/or have unsuitable low-temperature stability, and relatively disadvantageous Δ n value, as US6348244B, and CN102153442, WO9919420, the Δ n of above-claimed cpd is less.
Up to now, do not have the known series of compounds with the middle phase of liquid crystal to comprise the single compound that meets all these requirements.The research and development in liquid crystal material field are still shouldered heavy responsibilities, and in order to improve the character of LCD element, are still making great efforts to develop the compounds that can optimize this class display.
Summary of the invention
The object of this invention is to provide a kind of compound that can be used as liquid crystal media component.
Another object of the present invention is to provide the preparation method of described compound.
Another object of the present invention is to provide a kind of liquid-crystal composition that comprises described compound.
A further object of the present invention is to provide and a kind ofly comprises that described liquid-crystal composition is as the liquid crystal display device of integrant.
For addressing the above problem, the invention provides following technical scheme:
An aspect of of the present present invention, provides a kind of compound that can be used as liquid crystal media component, and described compound has the structure shown in logical formula I:
Wherein,
R
1select free H, halogen, there is the halo of 1-7 carbon atom or the group that unsubstituted alkyl or alkoxyl group, the unsubstituted thiazolinyl with 2-7 carbon atom or alkene oxygen base form, wherein, described R
1in one or more CH
2group can be independently of one another by-O-,-CF=CH-,-CF=CF-,-COO-or-O-CO-substitutes, and every two Sauerstoffatoms are not connected to each other;
R
2select free H, Cl, CN, OCF
3, there is fluoro-alkyl or the fluoroalkyl of alkyl or the alkoxyl group of 1-7 carbon atom, the thiazolinyl with 2-7 carbon atom or alkene oxygen base, 1-4 carbon atom and there is the group that the fluoro thiazolinyl of 2-4 carbon atom forms;
L
1～L
12can be identical or different, be H or F independently of one another, wherein, described L
1～L
12in have at the most six for F.
In some preferred embodiments, described R
1choosing freely has the group that alkyl or the alkoxyl group of 1-7 carbon atom, the thiazolinyl with 2-7 carbon atom or alkene oxygen base form, wherein, and described R
1in one or more CH
2group can be independently of one another by-CF=CH-,-CF=CF-or-COO-substitutes.
In some preferred embodiments, described R
2select free H, OCF
3, there is the group that alkyl or the alkoxyl group of 1-7 carbon atom, the thiazolinyl with 2-7 carbon atom or alkene oxygen base form.
Preferably, the group that the freely following compound of described compound choosing forms:
Wherein, described R1 choosing freely has the group of alkyl or alkoxyl group or thiazolinyl or the alkene oxygen base composition of 2-5 carbon atom, and described R2 selects free OCF3, has the alkyl of 2-5 carbon atom or the group that alkoxyl group forms.
More preferably, the group that the freely following compound of described compound choosing forms:
Another aspect of the present invention is to provide a kind of method of preparing described compound, comprises the steps:
1) under-65 ~-70 ℃, nitrogen protection, n-Butyl Lithium (n-BuLi, 2.4mol/L) is slowly dropped to the change of formula a
In the tetrahydrofuran (THF) of compound (THF) solution,
Drip Bi Fanying 2 hours, slowly drip boric acid three isobutyl esters (triisobutyl borate) to above-mentioned reaction system, constant temperature, in-65 ~-70 ℃, obtains the compound of formula b;
2) nitrogen protection, successively by the compound of the compound of formula b, formula c,
Glycol dimethyl ether (DME), sodium carbonate (Na
2cO
3, 2mol/L), tetrakis triphenylphosphine palladium (Pd (PPh
3)
4) be placed in eggplant-shape bottle, be slowly warming up to 85 ℃ (± 2 ℃), react 2 hours, obtain the compound of formula d;
3) under-65 ~-70 ℃, nitrogen protection, by n-Butyl Lithium (n-BuLi, 2.4mol/L) slowly drop in tetrahydrofuran (THF) (THF) solution of the compound of formula d, drip Bi Fanying 2 hours, slowly drip boric acid three isobutyl esters (triisobutyl borate) to above-mentioned reaction system, constant temperature, in-65 ~-70 ℃, obtains the compound of formula e;
4) nitrogen protection, successively by the compound of the compound of formula e, formula f,
Sodium carbonate (Na
2cO
3, 2mol/L), toluene, ethanol, water and tetrakis triphenylphosphine palladium (Pd (PPh
3)
4) be placed in there-necked flask, heating, stopped reaction after stable backflow 6 hours, obtains the compound of formula g;
5) under-65 ~-70 ℃, nitrogen protection, by n-Butyl Lithium (n-BuLi, 2.4mol/L) slowly drop in tetrahydrofuran (THF) (THF) solution of the compound of formula g, drip Bi Baowen at-65 ~-70 ℃ 1 hour, slowly drip boric acid three isobutyl esters (triisobutyl borate) to above-mentioned reaction system, drip Bi Baowen and after 1 hour, be naturally warming up to-50 ℃ at-65 ~-70 ℃, obtain the compound of formula h;
5) nitrogen protection, successively by the compound of the compound of formula h, formula i,
Sodium carbonate (Na
2cO
3, 2mol/L), toluene, ethanol, water and tetrakis triphenylphosphine palladium (Pd (PPh
3)
4) being placed in there-necked flask, heating, stops heating after stable backflow 6 hours, and is cooled to 40 ~ 50 ℃, obtains compound (I).
Wherein:
R
1select free H, halogen, there is the halo of 1-7 carbon atom or the group that unsubstituted alkyl or alkoxyl group, the unsubstituted thiazolinyl with 2-7 carbon atom or alkene oxygen base form, wherein, described R
1in one or more CH
2group can be independently of one another by-O-,-CF=CH-,-CF=CF-,-COO-or-O-CO-substitutes, and every two Sauerstoffatoms are not connected to each other;
R
2select free H, Cl, CN, OCF
3, there is fluoro-alkyl or the fluoroalkyl of alkyl or the alkoxyl group of 1-7 carbon atom, the thiazolinyl with 2-7 carbon atom or alkene oxygen base, 1-4 carbon atom and there is the group that the fluoro thiazolinyl of 2-4 carbon atom forms;
L
1～L
12can be identical or different, be H or F independently of one another, wherein, described L
1～L
12in have at the most six for F.
Another aspect of the present invention is to provide a kind of liquid-crystal composition that comprises one or more of described compounds.
Another aspect of the present invention is to provide and a kind ofly comprises that described liquid-crystal composition is as the liquid crystal display device of integrant.
Other liquid crystalline cpds of liquid crystalline cpd and prior art of general formula provided by the invention (I) are compared, and have response speed faster, and chemical property is all stable; In the liquid crystalline cpd preparation process of general formula (I), raw material is easy to get, and synthetic route is simple, is applicable to large-scale industrial and produces, and is beneficial to as the use showing with liquid crystal material, the time of response that can be used for improving liquid-crystal composition.
Accompanying drawing explanation
Fig. 1 is Compound I-2-1
1h NMR figure.
Fig. 2 is Compound I-4-5
1h NMR figure.
Fig. 3 is Compound I-5-2
1h NMR figure.
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.
In following examples, the code name of writing a Chinese character in simplified form of each test event is expressed as:
Cp (℃) clearing point (to row-isotropic phase transition temperature)
Δ n optical anisotropy (589nm, 20 ℃)
Δ ε dielectric anisotropy (1KHz, 25 ℃)
The character voltage of V90 saturation voltage=when 90% relative contrast (normal white mode)
The character voltage of V10 threshold voltage=when 10% relative contrast (normal white mode)
Wherein, specific refractory power anisotropy use Abbe refractometer under sodium lamp (589nm) light source, 20 ℃ test; Measurement box is TN90 type, the thick 7 μ m of box.
V10 test condition: C/1KHZ, JTSB7.0.
Reagent used in the present invention and other raw materials are commercially available commercial materials.
Preparation Compound I-2-1 synthetic route represent as follows,
Its concrete technology step is as follows:
1) compound of synthesis type 2
The compound dissolution of the formula of 22.8g 1, in tetrahydrofuran (THF) (THF) solution of 200ml, is cooled to-65 ~-70 ℃ by above-mentioned solution, nitrogen protection with ethanol and dry ice.Slowly by the n-Butyl Lithium (n-BuLi of 83.3ml, 2.4mol/L) drop in tetrahydrofuran (THF) (THF) solution of the compound of formula 1, drip Bi Fanying 2 hours, solution is become yellow muddy from clarification, boric acid three isobutyl esters (triisobutyl borate) that continue slowly to drip 92g are to above-mentioned reaction system, maintain the temperature at-65 ~-70 ℃, solution is by the clarification that becomes colorless of yellow muddiness, then becomes white opacity.
Reaction frozen water cancellation, ethyl acetate extraction, washing, saturated common salt washing, anhydrous sodium sulfate drying, filters.Be spin-dried for organic phase, add sherwood oil making beating, ultrasonic, filter, oil pump is drained, and obtains white solid 12g, is formula 2 compounds.
Mp：93.24~98.35℃；
MS m/z：158(M
+)；
1H-NMR(d
6-DMSO)δ：8.36(s,2H);6.53~7.45(m,3H)。
2) compound of synthesis type 4
(formula 3)
(formula 4)
The compound that adds the formula 2 of 7.9g in 500ml eggplant-shape bottle, the compound of the formula 3 of 11.25g, the glycol dimethyl ether of 100ml (DME), the sodium carbonate (Na of 50ml
2cO
3, 2mol/L), the tetrakis triphenylphosphine palladium of 0.6g (Pd (PPh
3)
4), nitrogen protection, slowly rises to temperature 85 ℃ (± 2 ℃), reacts 2 hours.
The cancellation of reaction water, ethyl acetate extraction, washes, a small amount of saturated common salt washing, anhydrous sodium sulfate drying 1 hour, filters, and concentrated rear column chromatography (sherwood oil wash-out), is spin-dried for, and obtains colorless oil 10.2g, is formula 4 compounds.
MS m/z：258(M
+)
3) compound of synthesis type 5
The compound dissolution of the formula of 22.8g 4, in 30ml tetrahydrofuran (THF) (THF) solution, is cooled to-65 ~-70 ℃ by above-mentioned solution, nitrogen protection with ethanol and dry ice.Slowly by the n-Butyl Lithium (n-BuLi of 6.25ml, 2.4mol/L) drop in tetrahydrofuran (THF) (THF) solution of the compound of formula 4, drip Bi Fanying 2 hours, solution from orange red become orange-yellow, boric acid three isobutyl esters (triisobutyl borate) that continue slowly to drip 7.9g are to above-mentioned reaction system, maintain the temperature at-65 ~-70 ℃, solution from orange become pale yellow, until colourless.
Reaction frozen water cancellation, ethyl acetate extraction, washing, saturated common salt washing, anhydrous sodium sulfate drying, filters.Be spin-dried for organic phase, add sherwood oil making beating, ultrasonic, filter, oil pump is drained, and obtains white solid 2g, is formula 5 compounds.
MS m/z：302(M
+)；
1H-NMR(d
6-DMSO)δ：8.34~8.39(d,2H);7.18~7.39(m,5H);2.97~3.06(m,2H);2.48~2.59(m,2H);2.27~2.37(m,1H);1.42~1.49(m,2H);0.90~0.95(t,3H)。
4) synthetic compound I-2-1
The compound that adds the formula 5 of 1.09g in 50ml eggplant-shape bottle, the compound of the formula 6 of 0.97g, the glycol dimethyl ether of 20ml (DME), the sodium carbonate (Na of 3ml
2cO
3, 2mol/L), the tetrakis triphenylphosphine palladium of 0.6g (Pd (PPh
3)
4), nitrogen protection, slowly rises to temperature 85 ℃ (± 2 ℃), reacts 2 hours.
The cancellation of reaction water, ethyl acetate extraction, washing, a small amount of saturated common salt washing, anhydrous sodium sulfate drying 1 hour, filters, concentrated rear column chromatography, purple fluorescence point is spin-dried for, oil pump is drained, ethanol, sherwood oil recrystallization, and suction filtration obtains needle-like white crystal 0.53g, after secondary crystal, obtain crystal 0.35g, make I-2-1 compound.
MS m/z：452(M
+)。
The nuclear magnetic resonance spectrum of chemical compounds I-2-1 is
1h-NMR (CDCl
3) δ: 7.24 ~ 7.73 (m, 13H); 3.08 ~ 3.18 (m, 2H); 2.43 ~ 2.72 (m, 5H); 1.54 ~ 1.76 (m, 4H); 0.99 ~ 1.05 (m, 6H).
The liquid crystal property of chemical compounds I-2-1:
Δn:0.32Mp：122.2℃；Cp:246.7℃
Chemical compounds I-2-1's
1h NMR figure is shown in Fig. 1.
Prepare similarly the compound of following structural formula:
Preparation Compound I-4-5 synthetic route represent as follows,
Its concrete technology step is as follows:
1) processing step 1 in the employing embodiment 1) ~ 3) compound of preparation formula 8
2) compound of synthesis type 9
(formula 9)
The compound that adds the formula 7 of 60g in 2000ml there-necked flask, the compound of the formula 8 of 112.4g, the sodium carbonate of 72.7g, the tetrakis triphenylphosphine palladium of 4g (Pd (PPh
3)
4), the toluene of 600ml, the ethanol of 300ml, the water of 300ml, nitrogen protection, heating, stopped reaction after stable backflow 6 hours.Above-mentioned reaction solution is poured into water, and separatory, extracts, washing, and steaming desolventizes, and through column chromatography, purify and obtain white solid 77.8g, be the compound of formula 9.
Theoretical yield: 115.88g actual output: 77.8g yield: 67.2%GC:95.96%
3) compound of synthesis type 10
(formula 10)
The compound that adds the formula 9 of 33.8g in 1000ml there-necked flask, 300ml tetrahydrofuran (THF) (THF), the potassium tert.-butoxide of 11g; nitrogen protection; subcooling is to the n-Butyl Lithium (n-BuLi, 2.4mol/L) that drips 50ml at-65 ~-70 ℃, drips Bi Baowen at-65 ~-70 ℃ 1 hour.Drip boric acid three isobutyl esters (triisobutyl borate) of 30g in above-mentioned reaction system, drip Bi Baowen at-65 ~-70 ℃ 1 hour, naturally after being warming up to-50 ℃ (± 2 ℃), above-mentioned reaction solution is poured in 500ml water, acidifying, separatory, extracts, washing, steaming desolventizes rear by 90-120 ℃ of petroleum ether, and suction strainer obtains faint yellow solid 24g, is the compound of formula 10.
Theoretical yield: 38.2g actual output: 24g yield: 62.8%
4) synthetic compound I-4-5
The compound that adds the formula 10 of 12.7g in 1000ml there-necked flask, the compound of the formula 11 of 7.3g, the sodium carbonate of 7.8g, the tetrakis triphenylphosphine palladium of 0.4g (Pd (PPh
3)
4), the toluene of 200ml, the ethanol of 100ml, the water of 100ml, nitrogen protection, reaction heating, stopped reaction after stable backflow 6 hours.Above-mentioned reaction solution is poured in 500ml water, and separatory, extracts, washing, and steaming desolventizes, and through column chromatography, purifies and obtains white solid 7.5g, makes Compound I-4-5.
Theoretical yield: 15.16g actual output: 7.5g yield: 49.67%
GC：98.86% DSC：C89.3N233.5I
The liquid crystal property of Compound I-4-5:
Δn:0.30
Chemical compounds I-4-5's
1h NMR figure is shown in Fig. 2.
Prepare similarly the compound of following structural formula:
DSC：C86.6N217.3I Δn:0.30
Preparation Compound I-5-2 synthetic route represent as follows,
Its concrete technology step is as follows:
1) processing step 1 in the employing embodiment 1) ~ 3) compound of preparation formula 13
2) compound of synthesis type 14
The compound that adds the formula 12 of 56.6g in 1000ml there-necked flask, the compound of the formula 13 of 59.6g, the sodium carbonate of 42.4g, the toluene of 300ml, the ethanol of 200ml, the water of 200ml, nitrogen protection, then add the tetrakis triphenylphosphine palladium (Pd (PPh of 2.3g
3)
4), heating, stopped reaction after stable backflow 6 hours, separatory, extracts, washing, steaming desolventizes, and through column chromatography, purify and obtain white solid 70g, be the compound of formula 14.
GC:99.8% theoretical yield: 81.8g, actual output: 70g, yield: 85%
3) compound of synthesis type 15
(formula 15)
The compound that adds the formula 14 of 70g in 500ml there-necked flask, the tetrahydrofuran (THF) of 200ml (THF), nitrogen protection, be cooled to-73 ~-78 ℃, drip the n-Butyl Lithium (n-BuLi of 84ml, 2.4mol/L), drip Bi Baowen at-73 ~-78 ℃ 1 hour, then the boric acid of 51g three isobutyl esters (triisobutyl borate) are dropped to above-mentioned reaction system, drip Bi Baowen at-73 ~-78 ℃ 1 hour, naturally be warming up to after-50 ℃ (± 2 ℃), above-mentioned reaction solution is slowly poured in 500ml water, acidifying, separatory, steaming desolventizes rear by 90-120 ℃ of petroleum ether, suction strainer, obtain white solid 51g, compound for formula 15.
Theoretical yield: 64g.Actual output: 51g.Yield: 80%
4) synthetic compound I-5-2
(formula 16)
The compound that adds the formula 15 of 51g in 500ml there-necked flask, the compound of the formula 16 of 40.7g, the sodium carbonate of 29.8g, 150ml toluene, 75ml ethanol, 150ml water, nitrogen protection, then add the tetrakis triphenylphosphine palladium (Pd (PPh of 1.5g
3)
4), heating, stops heating after stable backflow 6 hours.Above-mentioned reaction solution is slowly poured in 150ml water, and separatory, extracts, washing, and steaming desolventizes, and through column chromatography, purify and obtain white solid 60g, be Compound I-5-2.
Theoretical yield: 70.4g, actual output: 60g, yield: 85%.
DSC：C148.8S223.7N232.9
The liquid crystal property of Compound I-5-2:
Δn:0.26 Δε:16.3
Compound I-5-2's
1hNMR figure is shown in Fig. 3.
Prepare similarly the compound of following structural formula:
DSC：C138S185.2N236.7 Δn:0.266 Δε:13.8
Prepare liquid-crystal composition
For ease of expressing, the listed coded representation of table 1 for the unit structure of following liquid crystalline cpd:
The unit structure code of table 1 liquid crystalline cpd
Take following structure as example:
Coded representation in table 1 for this structure: can be expressed as 3PTWTP3, and for example:
Can be expressed as nCPTPOm, the n in code represents the C atomicity of left end alkyl, and for example n is " 3 ", 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 for example m is " 1 ", represents that the alkyl of right-hand member is-CH
3.
With listed each component of table 2, prepare liquid-crystal composition.Wherein, 3IGGP3,3IGPUOCF3 derive from respectively embodiment 2,3, and other each components are known or its preparation method can easily be obtained from prior art is derivative by association area those of skill in the art, because their standard technologies based on being described in document.
Liquid-crystal composition of the present invention can be prepared in a conventional manner.Conventionally, the component that wherein content is less is dissolved in the main ingredient that content is larger under suitably heating up, or described each component is mixed in organic solvent, described organic solvent is as acetone, chloroform or methyl alcohol, and after fully mixing, remove again desolventizing, for example pass through distillating method.
The weight percentage of table 2 liquid-crystal composition and component thereof
| The component of liquid-crystal composition | The weight percentage of each component (%) |
| |
6 |
| |
6 |
| |
8 |
| |
8 |
| |
6 |
| 3CCV | 44 |
| |
5 |
| |
5 |
| |
6 |
| |
3 |
| |
3 |
The measured properties of this liquid-crystal composition is as follows:
Δn：0.114
Δε：3.08
C
P：78
V90:3.284。
Claims (6)
1. a compound with general formula (I):
Wherein,
R
1be selected from the group of halo or unsubstituted alkyl or the alkoxyl group composition with 1-7 carbon atom;
R
2select free H, Cl, CN, OCF
3, there is fluoro-alkyl or the fluoroalkyl of alkyl or the alkoxyl group of 1-7 carbon atom, the thiazolinyl with 2-7 carbon atom or alkene oxygen base, 1-4 carbon atom and there is the group that the fluoro thiazolinyl of 2-4 carbon atom forms;
L
1～L
12can be identical or different, be H or F independently of one another, wherein, described L
1～L
12in have at the most six for F.
2. compound according to claim 1, is characterized in that, described R
2select free H, OCF
3, there is the group that alkyl or the alkoxyl group of 1-7 carbon atom, the thiazolinyl with 2-7 carbon atom or alkene oxygen base form.
3. compound according to claim 1 and 2, is characterized in that, the group that the freely following compound of described compound choosing forms:
Wherein, described R
1choosing freely has the alkyl of 2-5 carbon atom or the group that alkoxyl group forms, described R
2select free OCF
3, there is the group that the alkyl of 2-5 carbon atom or alkoxyl group form.
4. compound according to claim 3, is characterized in that, the group that the freely following compound of described compound choosing forms:
5. a liquid-crystal composition, is characterized in that, comprises in claim 1-4 the liquid crystalline cpd described in any one.
6. a liquid crystal display device that comprises liquid-crystal composition as claimed in claim 5.
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| CN104673324B (en) * | 2013-11-27 | 2017-05-03 | 江苏和成显示科技股份有限公司 | Liquid crystal composition and display device comprising liquid crystal composition |
| TWI487779B (en) * | 2013-12-31 | 2015-06-11 | Daxin Materials Corp | Liquid crystal composition and liquid crystal display device |
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|---|---|---|---|---|
| DE4303634A1 (en) * | 1993-02-09 | 1994-08-11 | Merck Patent Gmbh | Indane derivatives |
| DE4409526A1 (en) * | 1994-03-21 | 1995-09-28 | Merck Patent Gmbh | Novel indane derivs. |
| WO2011010843A1 (en) * | 2009-07-21 | 2011-01-27 | Rohm And Haas Electronic Materials Korea Ltd. | Novel organic electroluminescent compounds and organic electroluminescent device using the same |
| CN102408896A (en) * | 2010-09-21 | 2012-04-11 | 达兴材料股份有限公司 | Liquid crystal compound and liquid crystal mixture |
| CN102477305A (en) * | 2010-11-25 | 2012-05-30 | 达兴材料股份有限公司 | Liquid crystal compound and liquid crystal mixture |
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| JP3430548B2 (en) * | 1993-03-10 | 2003-07-28 | 旭硝子株式会社 | Fluorine-containing indane ring derivative compound and liquid crystal composition containing the same |
| JP4240841B2 (en) * | 2001-04-27 | 2009-03-18 | キヤノン株式会社 | Organic light emitting device |
| EP2215185A1 (en) * | 2007-11-23 | 2010-08-11 | Gracel Display Inc. | Luminescent compounds and electroluminescent device using the same |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4303634A1 (en) * | 1993-02-09 | 1994-08-11 | Merck Patent Gmbh | Indane derivatives |
| DE4409526A1 (en) * | 1994-03-21 | 1995-09-28 | Merck Patent Gmbh | Novel indane derivs. |
| WO2011010843A1 (en) * | 2009-07-21 | 2011-01-27 | Rohm And Haas Electronic Materials Korea Ltd. | Novel organic electroluminescent compounds and organic electroluminescent device using the same |
| CN102408896A (en) * | 2010-09-21 | 2012-04-11 | 达兴材料股份有限公司 | Liquid crystal compound and liquid crystal mixture |
| CN102477305A (en) * | 2010-11-25 | 2012-05-30 | 达兴材料股份有限公司 | Liquid crystal compound and liquid crystal mixture |
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