CN103555344B - Liquid crystal compound containing tetrahydro-thiopyran group and preparation method thereof, and liquid crystal composition - Google Patents
Liquid crystal compound containing tetrahydro-thiopyran group and preparation method thereof, and liquid crystal composition Download PDFInfo
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Abstract
The invention discloses a liquid crystal compound containing a tetrahydro-thiopyran group and a preparation method thereof and a liquid crystal composition. The liquid crystal compound is represented by a general formula I. The liquid crystal composition comprises no more than 40% but more than 0 of the compound as represented by the general formula I, 4 to 50% of a compound as represented by a general formula II, 5 to 50% of a compound as represented by a general formula III and 3 to 45% of a compound as represented by a general formula IV. The liquid crystal compound provided by the invention has low rotary viscosity gamma 1, great dielectric anisotropy, a wide nematic phase temperature range, good intermiscibility, light stability and thermal stability and is fairly applicable as a liquid crystal monomer; the liquid crystal composition containing the liquid crystal compound has a great liquid crystalline phase temperature range, appropriate optical anisotropy, small rotary viscosity and low starting voltage and is especially applicable to liquid crystal display elements of a TN mode, a VA mode, an IPS mode and a PDLC mode.
Description
Technical field
The present invention relates to a kind of liquid crystalline cpd containing sulfo-THP trtrahydropyranyl with and preparation method thereof and liquid-crystal composition containing this liquid crystalline cpd, belong to liquid crystalline cpd and Application Areas.
Background technology
In recent years, liquid-crystal display instead of traditional cathode-ray tube display, becomes the main product of current field of information display, is widely used in the various indicating meters such as instrument, computer, TV.According to the difference of liquid-crystal display mode, liquid crystal display device can be divided into the various modes such as twisted nematic (TN) pattern, super-twist nematic (STN) pattern, coplanar (IPS) pattern, vertical orientation (VA) pattern.
Thin Film Transistor-LCD (Thin Film Transistor Liquid Crystal Display, TFT-LCD), is 21 century one of the most rising technique of display, is all widely used in the field such as notebook computer, LCD TV.TFT-LCD is the Active Matrix LCD At introduced thin film transistor switch and formed on the basis of twisted nematic liquid crystal display (TN-LCD), overcome cross interference in passive matrix display, the shortcoming such as quantity of information is few, writing speed is slow, substantially improve display quality, therefore obtain fast development.
The advantage of TFT-LCD can be summarized as following 5 points: 1. service performance is good: low pressure applications, low driving voltage; Panelized, frivolous again, save a large amount of starting material and usage space; Reduce power consumption; Display quality from the simplest monochromatic character graphics to high resolving power, high color fidelity of reproduction, high brightness, high-contrast, the video display unit (VDU) of all size model of high response speed; Its display mode has direct viewing type, projection type, perspective formula and the multiple display modes such as reflective.2. environmental protection characteristic is good: TFT-LCD is radiationless, flicker free, harmless to the health of user, the particularly appearance of TFT-LCD electronic book, will bring paperless office into the mankind, and without the paper printing epoch, cause mankind's study, propagate and record the revolution of civilized mode.3. the scope of application is wide: TFT-LCD can normally use within the scope of-20 DEG C ~ 50 DEG C, and the TFT-LCD low-temperature working temperature through excess temperature consolidation process even can reach-80 DEG C.TFT-LCD not only can show as mobile terminal, terminal console display, and also can be used as large-curtain projecting TV set, is the full-size video display terminal of excellent property.4. the level of automation of manufacturing technology is high.5. TFT-LCD is easy to integrated and updates.
Liquid crystal material as one of important photoelectron material of liquid-crystal display, the effect important to the performance improving liquid-crystal display.The following performance of the equal demand fulfillment of liquid crystal material for showing: 1. good chemistry, physics and thermostability, to the stability of electric field and electromagnetic radiation; 2. viscosity (γ 1) is low; 3. there is suitable dielectric anisotropy △ ε; 4. suitable optical anisotropy △ n; 5. good with the intermiscibility of other liquid crystalline cpds.And as TFT-LCD liquid crystal material, there is the requirement higher than common liquid crystalline materials, except above-mentioned characteristic, also should have the performances such as wider nematic temperature range, very high resistivity, good anti-ultraviolet property, high electric charge conservation rate, low-steam pressure, low ion concns, reduce power consumption, low rotary viscosity.
Liquid crystal material as one of important photoelectron material of liquid-crystal display, the effect important to the performance improving liquid-crystal display.As display liquid crystal material, necessarily require wider nematic temperature range, higher stability, applicable rotary viscosity and the quick response to electric field.But up to the present, also do not find the single liquid crystalline cpd of any one can reach above-mentioned performance requriements, plurality of liquid crystals compound combination must be become liquid-crystal composition, the performance requriements of liquid crystal display material can be met.
In order to constantly meet the requirement of the display performances such as TN pattern, STN pattern, TFT-LCD, the liquid crystalline cpd as display develops into phenylcyclohexane class, phenylacetylene class, ethyl bridged bond class, end thiazolinyl class and various fluorine-containing aromatic ring class liquid crystalline cpd gradually from containing biphenyl nitrile, ester class, oxygen heterocyclic ring class, pyrimidine lopps liquid crystalline cpd.
Wherein, fluoro liquid crystals becomes the main component of TFT liquid-crystal display liquid crystal material owing to having the characteristics such as low viscosity, moderate dielectric anisotropy, high resistivity, high electric charge conservation rate.The sub-methoxyl group bridge of a difluoro (-CF is introduced in liquid crystal molecule
2o-) after, its nematic temperature range can be made to expand significantly, simultaneously rotary viscosity γ
1also decrease.In addition due to the sub-methoxyl group bridge of difluoro (-CF
2the contribution of moment of dipole O-), the moment of dipole of end group fluorine atom is also improved to some extent, thus the dielectric anisotropy △ ε of liquid crystal molecule is increased to some extent.What Merck KGaA and Japanese Chisso Corporation had disclosed that some have a different substituents has the sub-methoxyl group bridge of difluoro (-CF
2o-) liquid crystalline cpd (CN1717468A, CN101143808A, CN101157862A etc.), and be applied in liquid-crystal composition.
Along with the development of liquid-crystal display industry, people also increase gradually for the demand of the display material with different performance.Therefore, liquid crystalline cpd and the composition of continually developing new excellent performance have great importance to liquid-crystal display development.
Summary of the invention
The technical issues that need to address of the present invention are to provide a kind of liquid crystalline cpd containing sulfo-THP trtrahydropyranyl that be applicable to liquid-crystal display, that simultaneously have higher stability, wider nematic phase range, lower rotary viscosity and high dielectric anisotropy and liquid-crystal composition thereof.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
Liquid crystalline cpd containing sulfo-THP trtrahydropyranyl, its structure is as shown in formula I:
Wherein, R
1, R
2be respectively 1. following ~ 4. shown in any one in group:
①-H、-Cl、-F、-CN、-OCN、-OCF
3、-CF
3、-CHF
2、-CH
2F、-OCHF
2、-SCN、-NCS、-SF
5；
2. containing the alkyl of 1 ~ 15 carbon atom, the alkoxyl group containing 1 ~ 15 carbon atom, the thiazolinyl containing 2 ~ 15 carbon atoms, alkene oxygen base containing 2 ~ 15 carbon atoms;
3. one or more non-conterminous-CH
2-by-CH=CH-,-C ≡ C-,-COO-,-OOC-,
-O-or-S-substitute and Sauerstoffatom after substituting in group be not directly connected above-mentioned 2. shown in group;
4. arbitrarily H atom by fluorine atom or chlorine atom replace above-mentioned 2., 3. shown in group;
any one in singly-bound or following groups respectively:
Z
1, Z
2singly-bound ,-CH respectively
2-,-CH
2cH
2-,-(CH
2)
3-,-(CH
2)
4-,-CH=CH-,-C ≡ C-,-COO-,-OOC-,-CF
2o-,-OCH
2-,-CH
2o-,-OCF
2-,-CF
2cH
2-,-CH
2cF
2-,-CF
2cF
2-or-CF=CF-wherein any one;
N
1, n
2, n
3, n
4wherein arbitrary numerical value of 0,1,2 or 3 respectively, and n
1+ n
2+ n
3+ n
4≤ 5.
A kind of liquid-crystal composition, comprises the compound shown at least one formula I, and the weight percentage of the compound shown in described formula I in liquid-crystal composition is for being less than or equal to 40% and non-vanishing; This liquid-crystal composition also includes the compound shown in general formula II, the compound shown in general formula III of 5% ~ 50% and the compound shown in general formulae IV of 3% ~ 45% that weight percentage is 4% ~ 50%,
Wherein,
R
3, R
4, R
5, R
6, R
7-CN ,-F respectively, the carbonatoms alkyl that is 1 ~ 7, the carbonatoms alkoxyl group that is 1 ~ 7, carbonatoms be 2 ~ 7 thiazolinyl or carbonatoms be any one in the fluoroalkyl of 1 ~ 5;
Z
3, Z
4singly-bound ,-CH respectively
2cH
2-,-CH=CH-,-C ≡ C-,-COO-,-OOC-,-CF
2o-,-OCH
2-,-CH
2o-,-OCF
2-wherein any one;
the arbitrary group in singly-bound or following groups respectively:
Y
1, Y
2-H or-F respectively;
N
5, n
6the arbitrary numerical value in 0,1,2 respectively.
Owing to have employed technique scheme, the technical progress acquired by the present invention is:
The invention discloses a kind of liquid crystalline cpd containing sulfo-THP trtrahydropyranyl, this liquid crystalline cpd Stability Analysis of Structures, not only there is the necessary general physical properties of liquid crystal material, and to light, thermally-stabilised, there is wider nematic temperature range, good with the intermiscibility of other compounds, especially the low rotary viscosity γ 1 that has of this type of liquid crystalline cpd and large dielectric anisotropy (△ ε >0), it is a kind of liquid crystal monomer being suitable for very much being used as liquid-crystal display, be particularly useful for preparation TN pattern, VA pattern, IPS pattern or PDLC mode LCD.When using it in liquid-crystal composition, can the optical anisotropy of effective adjustable liquid crystal display composition, and then reduce threshold voltage and the rotary viscosity of liquid-crystal composition, accelerate the time of response, obviously optimize the performance of liquid-crystal composition.
The present invention gives the preparation method of the described liquid crystalline cpd containing sulfo-THP trtrahydropyranyl, and its synthetic route is simple to operation, and reaction yield is higher, and production cost is low; Its use can reduce the preparation cost of liquid-crystal composition, has good industrial prospect.
Present invention also offers a kind of liquid-crystal composition, this liquid-crystal composition comprises the compound shown at least one formula I, the compound shown at least one general formula II, the compound shown in the compound shown at least one general formula III and at least one general formulae IV.Described liquid-crystal composition has larger liquid crystal phase temperature range and suitable optical anisotropy, and its rotary viscosity is little, trigger voltage is low, be applicable to various liquid-crystal display, electro-optical display and electrooptics liquid-crystal display, be particularly useful for TN escope, VA escope, IPS escope or PDLC escope, have broad application prospects and marketable value.
Embodiment
Below in conjunction with embodiment, the present invention is described in further details:
Percentage composition involved in following embodiment is weight percentage, and temperature unit is DEG C, the concrete meaning of other symbols and test condition as follows:
HPLC represents high-efficient liquid phase color spectral purity (%), testing tool: the HP1100 type high performance liquid chromatograph of Agilent company;
GC represents high resolution gas chromatography purity (%), testing tool: the HP6820 type gas chromatographicanalyzer of Agilent company;
GC-MS represents that gas chromatography mass spectrometry is composed, testing tool: Agilent company MS5975C type gas chromatograph-mass spectrometer;
1H-HMR represents nucleus magnetic hydrogen spectrum, testing tool: the DRX-500 nuclear magnetic resonance analyser of Bruker.Biospin company;
M.p. fusing point is represented, testing tool: the micro-thermal analyzer of WRX-1S, test condition: heat-up rate 3 DEG C/min;
C.p. the clearing point (DEG C) of liquid crystal is represented, testing tool: 1. plum Teller (Mettler) company FP-52 type melting point apparatus, heat-up rate 3 DEG C/min; 2. plum Teller (Mettler) company DSC822E type differential calorimetric turns round scanner, heat-up rate 1 DEG C/min;
Δ n represents optical anisotropy, △ n=n
o-n
e, wherein, n
ofor the specific refractory power of ordinary light, n
efor the specific refractory power of extraordinary ray, testing tool: Abbe refractometer, test condition: 589nm, 25 DEG C;
△ ε represents dielectric anisotropy, △ ε=ε
∥-ε
⊥, wherein, ε
∥for being parallel to the specific inductivity of molecular axis, ε
⊥for the specific inductivity perpendicular to molecular axis, testing tool: the HP4284A type LCR test set of Hewlett-Packard, test condition: 25 DEG C;
γ 1 represents rotary viscosity (mPas), testing tool: the Model6254 liquid crystal parameter comprehensive tester of company of Japanese Japan (TOYO), test condition: 20 ± 0.5 DEG C.
A liquid crystalline cpd containing sulfo-THP trtrahydropyranyl, its structure is as shown in formula I:
Wherein, R
1, R
2be respectively 1. following ~ 4. shown in any one in group:
①-H、-Cl、-F、-CN、-OCN、-OCF
3、-CF
3、-CHF
2、-CH
2F、-OCHF
2、-SCN、-NCS、-SF
5；
2. containing the alkyl of 1 ~ 15 carbon atom, the alkoxyl group containing 1 ~ 15 carbon atom, the thiazolinyl containing 2 ~ 15 carbon atoms, alkene oxygen base containing 2 ~ 15 carbon atoms;
3. one or more non-conterminous-CH
2-by-CH=CH-,-C ≡ C-,-COO-,-OOC-,
-O-or-S-substitute and Sauerstoffatom after substituting in group be not directly connected above-mentioned 2. shown in group;
4. arbitrarily H atom by fluorine atom or chlorine atom replace above-mentioned 2., 3. shown in group;
R
1arbitrary group preferably in-H, the alkyl containing 1 ~ 15 carbon atom, the alkoxyl group containing 1 ~ 15 carbon atom, the thiazolinyl containing 2 ~ 15 carbon atoms, the alkene oxygen base containing 2 ~ 15 carbon atoms;
R
2preferably from-H ,-Cl ,-F ,-CN ,-OCN ,-OCF
3,-CF
3,-CHF
2,-CH
2f ,-OCHF
2,-SCN ,-NCS ,-SF
5, the alkyl containing 1 ~ 15 carbon atom, the alkoxyl group containing 1 ~ 15 carbon atom, the thiazolinyl containing 2 ~ 15 carbon atoms, arbitrary group in the alkene oxygen base containing 2 ~ 15 carbon atoms;
any one in singly-bound or following groups respectively:
Z
1, Z
2singly-bound ,-CH respectively
2-,-CH
2cH
2-,-(CH
2)
3-,-(CH
2)
4-,-CH=CH-,-C ≡ C-,-COO-,-OOC-,-CF
2o-,-OCH
2-,-CH
2o-,-OCF
2-,-CF
2cH
2-,-CH
2cF
2-,-CF
2cF
2-or-CF=CF-wherein any one;
Z
1, Z
2preferably from singly-bound ,-CH
2-,-CH
2cH
2-,-(CH
2)
3-,-(CH
2)
4-,-CH=CH-,-C ≡ C-,-COO-,-OOC-,-CF
2o-,-OCH
2-,-CH
2o-,-OCF
2-wherein any one;
N
1, n
2, n
3, n
4wherein arbitrary numerical value of 0,1,2 or 3 respectively, and n
1+ n
2+ n
3+ n
4≤ 5.
Any one preferably in the compound shown in formula I-1 ~ formula I-7 of described liquid crystalline cpd,
Wherein,
R
1-H or the straight chained alkyl containing 1 ~ 10 carbon atom, preferably-H or the straight chained alkyl containing 1 ~ 6 carbon atom;
R
2-F ,-Cl ,-OCF
3,-CF
3,-CN ,-NCS ,-OCHF
2in arbitrary group, preferably-F ,-Cl ,-OCF
3,-CF
3, arbitrary group in-CN ,-NCS;
L
1, L
2, L
3, L
4, L
5, L
6, L
7, L
8-H or-F respectively.
The liquid crystalline cpd of described preferred formula I-1 is most preferably from following compounds:
The liquid crystalline cpd of described preferred formula I-4 is most preferably from following compounds:
The liquid crystalline cpd of described preferred formula I-5 is most preferably from following compounds:
The liquid crystalline cpd of described preferred formula I-7 is most preferably from following compounds:
The liquid crystalline cpd containing sulfo-THP trtrahydropyranyl shown in formula I can be obtained by known chemical synthesis process, and synthetic method is see following documents:
（1）B Ekkehard,H Reinhard,K Hansadolf et al.US:5045229,1991.；
（2）M.Kuroboshi et al.，Chem.Lett.,1992,827；
（3）W.H.Bunnelle et al.,J.Org.Chem.1990,55,768.；
（4）Peer.Kirsch et al.,Angew.Chem.Int.Ed.2001.40，1480-1484.。
Shown in described preferred formula I-1, formula I-2, formula I-3, formula I-4, formula I-5, formula I-6, formula I-7, the preparation method of compound is selected from following three routes:
When shown in preparation formula I-1, formula I-2, formula I-3 during compound, adopt route A:
In route A, the actual conditions of each step reaction is respectively:
Prepare intermediate b:
Reaction raw materials a, reactant methyl acrylate, trimethylsilyl diethylamine and MEHQ, solvent acetonitrile are dropped in reactor, carries out back flow reaction under nitrogen protection; Reaction terminates rear solvent evaporated, adds Glacial acetic acid and water, proceeds back flow reaction; Reaction terminates rear cooling, adds that methyl tertiary butyl ether carries out extracting, separatory; By the solvent evaporate to dryness in organic layer, obtain evaporate to dryness thing;
In evaporate to dryness thing, add solvent methanol, under control temperature is 0 DEG C ~ 10 DEG C conditions, adds sodium borohydride, carries out reduction reaction; After reaction terminates, add that water and methyl tertiary butyl ether carry out extracting, separatory, by the solvent evaporate to dryness in organic layer, obtain secondary evaporate to dryness thing;
In secondary evaporate to dryness thing, add catalyzer tosic acid and solvent toluene, carry out back flow reaction; Add after reaction terminates that water and toluene carry out extracting, separatory, by the solvent evaporate to dryness in organic layer, obtain intermediate b crude product, after refining, namely obtain intermediate b;
Prepare intermediate c:
Intermediate b, reactant trimethylammonium iodate silicon and methylene chloride are dropped in reactor, 25 ± 5 DEG C of reactions; Add water after reaction terminates, separatory; By the solvent evaporate to dryness in organic layer, obtain evaporate to dryness thing;
Reactant oxalyl chloride and solvent benzol is added, 25 ± 5 DEG C of stirring reactions in above-mentioned evaporate to dryness thing; Reaction terminates rear solvent evaporated, adds methylene dichloride and triethylamine, then in reaction solution, passes into hydrogen sulfide and react; Sodium hydrogen carbonate solution is added, separatory after reaction terminates; By the solvent evaporate to dryness in organic layer, obtain intermediate c;
Prepare intermediate d:
Under temperature control-50 ± 5 DEG C of conditions, by the instillation of reactant butyllithium containing in the tetrahydrofuran solution of Isosorbide-5-Nitrae-dibromobenzene, drip the tetrahydrofuran solution continuing to drip intermediate c after finishing, stirring reaction; Add water after reaction terminates separatory; By the solvent evaporate to dryness in organic layer, obtain evaporate to dryness thing;
Above-mentioned evaporate to dryness thing is dissolved in methylene dichloride, at-75 ± 5 DEG C, instills reactant triethyl silicane and boron trifluoride diethyl etherate, and keep this temperature to react; Reaction terminates rear intensification, adds saturated sodium bicarbonate solution and is hydrolyzed, and then carries out extracting, separatory; By the solvent evaporate to dryness in organic layer, obtain intermediate d crude product; Namely intermediate d is obtained after recrystallization;
Prepare intermediate e:
Under temperature control-75 ± 5 DEG C of conditions, by the instillation of reactant butyllithium containing in the tetrahydrofuran solution of intermediate d, drip the tetrahydrofuran solution continuing dropwise reaction thing trimethyl borate after finishing; Be warming up to-20 ± 5 DEG C after being added dropwise to complete, add hydrochloric acid and stirring reaction, carry out extracting after reaction terminates, separatory; By the solvent evaporate to dryness in organic layer, obtain intermediate e crude product, after recrystallization, namely obtain intermediate e;
Prepare intermediate f:
Tetrahydrofuran (THF), water and hydrogen peroxide is added, 40 ± 5 DEG C of reactions in intermediate e; Add water and methylene dichloride carries out separatory after reaction terminates, by the solvent evaporate to dryness in organic layer, obtain intermediate f crude product, after recrystallization, namely obtain intermediate f;
Prepare intermediate g:
In intermediate f, add catalyzer 5% palladium charcoal and solvent toluene, 25 ± 5 DEG C, carry out catalytic hydrogenation reaction under 0.25 ± 0.05Mpa condition; After reaction terminates, filtration catalizer, and solvent evaporated, namely obtain intermediate g;
Prepare intermediate h:
Under temperature control-75 ± 5 DEG C of conditions, by the instillation of reactant butyllithium containing in the tetrahydrofuran solution of reactant 2-trimethyl silyl-1,3-dithiane, drip after finishing and slowly rise to 0 DEG C; Then-75 ± 5 DEG C are again cooled to, the tetrahydrofuran solution of instillation containing intermediate g; Be warming up to-25 ± 5 DEG C after being added dropwise to complete, continue stirring reaction; After question response terminates, add water and carry out separatory, by the solvent evaporate to dryness in organic layer, obtain intermediate h crude product, after recrystallization, obtain intermediate h;
Prepare finished product I:
Under temperature control-20 ± 5 DEG C of conditions, by the instillation of reactant trifluoromethanesulfonic acid containing in the dichloromethane solution of intermediate h, continue after stirring reaction 30min to be cooled to-75 ± 5 DEG C; Under this temperature condition, first instillation includes the dichloromethane solution of reactant 3,4,5-trifluoromethyl phenol and triethylamine, then adds reactant NEt fast
33HF; Temperature control-75 ± 5 DEG C, instillation includes the dichloromethane solution of bromine, continues stirring reaction at this temperature; Be warming up to 0 ± 5 DEG C after reaction terminates, reaction solution poured in mixture of ice and water, regulate pH value to 5 ~ 8 of reactant system with sodium hydroxide solution, then carry out separatory; By the solvent evaporate to dryness in organic layer, obtain finished product I crude product, through column chromatography and recrystallization, obtain finished product I.
L in formula I-4, formula I-6
5, L
6be all-H, the L in formula I-5, formula I-7
7, L
8when being all-H, route B is adopted to synthesize:
In route B, the actual conditions of each step reaction is respectively:
The method being prepared intermediate e by raw material a prepares the method for intermediate e with route A Raw a;
Prepare finished product I:
Reactant is added in intermediate e
catalyzer tetra-triphenylphosphine palladium and sodium carbonate, solvent toluene, second alcohol and water, temperature rising reflux reacts; After question response terminates, add water separatory, by the solvent evaporate to dryness in organic layer, obtains finished product I crude product; Through column chromatography and recrystallization, obtain finished product I.
L in formula I-4, formula I-6
5, L
6at least one is-F, the L in formula I-5, formula I-7
7, L
8when at least one is-F, route C is adopted to synthesize:
In route C, the actual conditions of each step reaction is respectively:
The method being prepared intermediate c by raw material a prepares the method for intermediate c with route A Raw a;
Prepare intermediate d ':
Under temperature control-50 ± 5 DEG C of conditions, by the instillation of reactant butyllithium containing in the tetrahydrofuran solution of 3-bromofluorobenzene, drip the tetrahydrofuran solution continuing to drip intermediate c after finishing, stirring reaction; Add water after reaction terminates separatory, by the solvent evaporate to dryness in organic layer, obtains evaporate to dryness thing;
Above-mentioned evaporate to dryness thing is dissolved in methylene dichloride, at-75 ± 5 DEG C, instills reactant triethyl silicane and boron trifluoride diethyl etherate, and react under keeping this temperature; Reaction terminates rear intensification, adds saturated sodium bicarbonate solution and is hydrolyzed, separatory, by the solvent evaporate to dryness in organic layer, namely obtain intermediate d ';
Prepare intermediate e ':
Under temperature control-95 ± 5 DEG C of conditions, the instillation of reactant butyllithium is contained in the tetrahydrofuran solution of intermediate d ' and potassium tert.-butoxide, drip the tetrahydrofuran solution of continuation dropwise reaction thing trimethyl borate after finishing; Be warming up to-20 ± 5 DEG C after being added dropwise to complete, add hydrochloric acid and water, stirring reaction 30min; Reaction terminates rear separatory, by the solvent evaporate to dryness in organic layer, namely obtains intermediate e ';
Prepare finished product I:
Reactant is added in intermediate e '
catalyzer tetra-triphenylphosphine palladium and sodium carbonate, solvent toluene, second alcohol and water, temperature rising reflux reacts; After question response terminates, add water separatory, by the solvent evaporate to dryness in organic layer, obtains finished product I crude product; Through column chromatography and recrystallization, obtain finished product I.
A kind of liquid-crystal composition, comprises the compound shown at least one formula I, and the weight percentage of the compound shown in described formula I in liquid-crystal composition is for being less than or equal to 40% and non-vanishing; Also comprise the compound shown in general formula II, the compound shown in general formula III of 5% ~ 50% and the compound shown in general formulae IV of 3% ~ 45% that weight percentage is 4% ~ 50%,
Wherein,
R
3, R
4, R
5, R
6, R
7-CN ,-F respectively, the carbonatoms alkyl that is 1 ~ 7, the carbonatoms alkoxyl group that is 1 ~ 7, carbonatoms be 2 ~ 7 thiazolinyl or carbonatoms be any one in the fluoroalkyl of 1 ~ 5;
Z
3, Z
4singly-bound ,-CH respectively
2cH
2-,-CH=CH-,-C ≡ C-,-COO-,-OOC-,-CF
2o-,-OCH
2-,-CH
2o-,-OCF
2-wherein any one;
the arbitrary group in singly-bound or following groups respectively:
Y
1, Y
2-H or-F respectively;
N
5, n
6the arbitrary numerical value in 0,1,2 respectively.
Described liquid-crystal composition preferably comprises that weight percentage is the liquid crystalline cpd shown in the formula I of 8% ~ 19%, the liquid crystalline cpd shown in general formula II of 20% ~ 36%, the liquid crystalline cpd shown in general formula III of 31% ~ 47% and 5% ~ 33% the liquid crystalline cpd shown in general formulae IV.
Starting material used in the following embodiments, if no special instructions, are open commercial sources and obtain.
The performance test mode of what following embodiment obtained have formula I product is divided into following two kinds:
1) using itself as sample testing m.p., c.p., HPLC, GC, MS, 1H-NMR;
2) product is mixed as sample with parent liquid crystal, carry out test △ ε, △ n according to the specification on " liquid crystal device handbook " (author: JSPS 142 council) that in August, 1992, aircraft industry press published; Concrete testing method is: first by the liquid crystalline products of 15% with 85% parent liquid crystal mix and make sample and test, then according to the test value of gained sample, draw extrapolated value by calculation by extrapolation, be the performance data of made product.The calculation formula of extrapolated value is: the weight percentage of extrapolated value=[100 × (test value of sample)-(weight percentage of parent liquid crystal) × (test value of parent liquid crystal)]/compound.
Parent liquid crystal used is composed as follows:
Embodiment 1
Prepare chemical compounds I-a:
Its synthetic route is:
Its concrete preparation process is as follows:
The preparation of 1.1 intermediate I-a-1:
In 250ml reaction flask, add 9.5g(0.11mol) valeraldehyde, 9.5g(0.11mol) methyl acrylate, 16g(0.11mol) trimethylsilyl diethylamine, 1g MEHQ and 130ml acetonitrile (solvent), backflow is warming up to, back flow reaction 24h under nitrogen protection; Reaction terminates rear cooling, and steaming desolventizes; Then in reaction flask, add 22ml Glacial acetic acid and 44ml water, again heat up, back flow reaction 2h; Be cooled to room temperature after reaction terminates, add 100ml methyl tertiary butyl ether and 100ml water, extraction separatory; Water layer 50ml × 2 methyl tertiary butyl ether extractions (namely each with the extraction of 50ml methyl tertiary butyl ether, coextraction 2 times; Lower same), merge organic layer; First wash organic layer with water, then with 50ml sodium bicarbonate aqueous solution washing organic layer to neutral, add anhydrous sodium sulfate drying; Filtering siccative, obtains 13.4g red liquid (GC:86.8%) after solvent evaporated;
The 13.4g red liquid of gained and 60ml anhydrous methanol are dropped in 100ml reaction flask, ice-water bath borehole cooling; Under control temperature of reaction is less than 10 DEG C of conditions, add 1.35g(0.0345mol, 0.5eq several times) sodium borohydride, add rear continuation stirring reaction 30min; Then remove ice-water bath, slowly rise to room temperature, and stirring reaction 1h at ambient temperature.Reaction terminates to add 100ml methyl tertiary butyl ether and 100ml water in backward reaction flask, extraction separatory; Water layer 50ml × 2 methyl tertiary butyl ether extractions, merge organic layer and wash; 13g yellow liquid is obtained after solvent evaporated;
The 13g yellow liquid of gained, 0.1g tosic acid and 100ml toluene being dropped into is provided with in the 250ml reaction flask of water trap, heats up, 110 DEG C of reaction 2h; Steam only until most of methyl alcohol, temperature of reaction is risen to 120 DEG C, continue reaction; After steaming 50ml reaction solution, add 50ml toluene, and then after steaming 50ml reaction solution, stop heating up and Slow cooling; Add 100ml toluene and 100ml water extraction separatory, organic layer is solvent evaporated after washing, and use silicagel column to carry out refining (leacheate is sherwood oil: methyl tertiary butyl ether=4:1), obtain 8.3g product, i.e. intermediate I-a-1(5-propyl group tetrahydropyrans-2-ketone); Yield 72.4%; GC:85%.
The preparation of 1.2 intermediate I-a-2
14.2g(0.1mol is added in reaction flask) intermediate I-a-1,100ml methylene dichloride and 21g(0.105mol) trimethylammonium iodate silicon, 25 ± 5 DEG C of stirring reaction 10h; After reaction terminates, add 100ml water extraction separatory, separate organic layer; After water layer dichloromethane extraction, merge organic layer, then use the water washing organic layer of 50ml × 4; 20g anhydrous sodium sulfate drying 2h is added, by solvent evaporate to dryness after filtering siccative in organic layer;
In above-mentioned evaporate to dryness thing, add 100ml benzene dissolve, and then add 50.8g(0.4mol) oxalyl chloride, 25 ± 5 DEG C of stirring reaction 10h; Reaction terminates rear solvent evaporated, adds 100ml methylene dichloride and 300ml triethylamine, pass into 5.1g(0.15mol under stirring in evaporate to dryness thing) hydrogen sulfide reacts; After it reacts completely, add 500ml saturated ammonium chloride solvent and carry out separatory, separate organic layer; After water layer 100ml × 2 methylene dichloride extracts, merge organic layer, add 50g anhydrous sodium sulfate drying; By solvent evaporate to dryness after filtering siccative, obtain evaporate to dryness thing 79g, i.e. intermediate I-a-2; Yield 50%.
The preparation of 1.3 intermediate I-a-3
In reaction flask, add 23.6g(0.1mol) Isosorbide-5-Nitrae-dibromobenzene and 250ml tetrahydrofuran (THF), be cooled to-60 DEG C ~-50 DEG C after stirring and dissolving, do not drip 40ml2.5M(0.1mol higher than the condition of-50 DEG C in guarantee system temperature) butyllithium; Then continue to drip 15.8g(0.1mol) tetrahydrofuran solution (15.8g intermediate I-a-2 is dissolved in 50ml tetrahydrofuran (THF)) of intermediate I-a-2, drips complete stirring reaction 30min; Naturally be warming up to-20 DEG C, add 50ml water and carry out separatory, discard water layer, organic layer 50ml × 4 water washings, obtain thick product after solvent evaporated;
Thick product is dissolved in 40ml methylene dichloride, is cooled to-85 DEG C ~-75 DEG C; Temperature control, not higher than under-70 DEG C of conditions, first adds 40ml triethyl silicane, and then drips 40ml boron trifluoride ether solution, drips complete stirring reaction 1h; Be warming up to-10 DEG C after reaction terminates, add saturated sodium bicarbonate solution and be hydrolyzed, separatory; Aqueous phase 20ml dichloromethane extraction, merges organic layer; Wash organic layer secondary with 40ml, then by the solvent evaporate to dryness in organic layer, obtain the product including 9:1 cis-trans-isomer; Again at-20 DEG C, recrystallization is carried out to this product hexane, obtain finished product 15g, be i.e. intermediate I-a-3; Yield 50%.
The preparation of 1.4 intermediate I-a-4
Intermediate I-the a-3 of 29.9g (0.1mol) is dissolved in 200ml tetrahydrofuran (THF), is cooled to-80 DEG C ~-70 DEG C; First instill the 2.5M butyllithium (0.1mol) of 40ml, and then drip the tetrahydrofuran solution (being dissolved in 50ml tetrahydrofuran (THF) by 13.5g trimethyl borate) of 13.5g (0.13mol) trimethyl borate; After dropwising, mixture is slowly warming up to-20 DEG C, adds 2N hydrochloric acid 100ml, stirring reaction 1h; Carry out separatory, aqueous phase 100ml extraction into ethyl acetate after reaction terminates, merge organic layer, 100ml × 2 are washed, and by the solvent evaporate to dryness in organic layer, obtain the thick product of intermediate I-a-4; Again thick product is carried out recrystallization in normal heptane, obtain finished product 18.5g, be i.e. intermediate I-a-4; Yield 70%; HPLC:97%.
1.5 the preparation of intermediate I-a-5
26.5g(0.1mol is added in reaction flask) intermediate I-a-4,300ml tetrahydrofuran (THF), 50ml water and 30ml30% hydrogen peroxide, temperature control 40 ± 5 DEG C of stirring reaction 2h; Reaction terminates to add 100ml methylene dichloride and 200ml water in backward reaction flask, and separatory after stirring 10min, separates organic layer, water layer 100nl dichloromethane extraction, merges organic layer; Then with water, organic layer washing is extremely neutral, obtain thick product after solvent evaporated; With 2 times of ethanol, recrystallization is carried out to thick product, obtain finished product 19g, be i.e. intermediate I-a-5; Yield 80%.
1.6 the preparation of intermediate I-a-6
By 23.7g(0.1mol) intermediate I-a-5 is dissolved in 200ml toluene, adds 5g5% palladium carbon catalyst, shortening 10h under 0.25MPa pressure; Filtration catalizer, by solvent evaporate to dryness, obtains product 23g, i.e. intermediate I-a-6; Yield 95.4%.
The preparation of 1.7 intermediate I-a-7
19.2g(0.1mol is added in reaction flask) 2-trimethyl silyl-1,3-dithiane and 75ml tetrahydrofuran (THF), be cooled to-80 DEG C ~-70 DEG C after dissolving; Control temperature, not higher than under-70 DEG C of conditions, instills 40m2.5M(0.1mol) butyllithium; Within the 4h time, system is warming up to 0 DEG C after dropwising, and then be cooled to-70 DEG C ~-80 DEG C, the tetrahydrofuran solution (24.1g intermediate I-a-6 is dissolved in 250ml tetrahydrofuran (THF)) of instillation 24.1g (0.1mol) intermediate I-a-6, drip after finishing and slowly rise to room temperature, 25 ± 5 DEG C of stirring reaction 18h; After reaction terminates, add 100ml water and carry out separatory, discard water layer, by evaporate to dryness after organic layer drying, obtain thick product; With normal heptane, recrystallization is carried out to thick product again, obtain white crystal 20.6g, be i.e. intermediate I-a-7; Yield 60%.
The preparation of 1.8 chemical compounds I-a
In reaction flask, add intermediate I-a-7 and the 50ml methylene dichloride of 34.3g (0.1mol), after stirring and dissolving, be cooled to-30 DEG C ~-20 DEG C; Control temperature, not higher than under the condition of-20 DEG C, instills 15g(0.1mol) trifluoromethanesulfonic acid, drips stirring reaction 30min after finishing; Then-70 DEG C ~-80 DEG C are cooled to, first instill 3 of 19.2g (0.13mol), 4, the dichloromethane solution of the triethylamine of 5-trifluoromethyl phenol and 30.3g (0.3mol) is (by 3 of 19.2g, 4,5-trifluoromethyl phenol and 30.3g triethylamine are dissolved in 20ml methylene dichloride), then within 5min, add 63.2g(0.4mol) NEt
33HF; Then control temperature is not higher than under the condition of-70 DEG C, in 1h, add 64g(0.4mol) dichloromethane solution (64g bromine is dissolved in 30ml methylene dichloride) of bromine, add rear temperature control less than-70 DEG C stirring reaction 1h;
Be warming up to 0 DEG C after reaction terminates, reaction solution poured in 160ml32% sodium hydroxide solution and 300g ice, drip pH value to 5 ~ 8 of 32% sodium hydroxide solution regulation system, about consume 45g32% sodium hydroxide solution; Leave standstill separatory, separatory organic layer, extracts water layer 80ml methylene dichloride, merges organic layer; In organic layer, add 4g diatomite decolour, evaporated under reduced pressure solvent after filtering diatomite, obtains thick product; Thick for gained product is first carried out column chromatography, and then carries out recrystallization with sherwood oil, obtain white crystal 21g, yield 50%.
White crystal obtained by Example 1 detects, and its detected result is as follows:
GC：99.9%；
m.p.：32.5℃；
MS：m/s（%）
422（25），274（23），148（100），87（67）；
1H-NMR：δ（ppm）
0.90（3H），1.28（m，8H），1.53（m，6H），1.75（m，4H），2.36（m，1H），2.49（m，2H），2.61（m，1H），6.89（m，2H）；
△ε：13.6（20℃，589nm）；
△n：0.064（20℃，1000Hz）；
Prove through above-mentioned detected result, gained white crystal is really
Embodiment 2
Prepare chemical compounds I-b:
The preparation of chemical compounds I-b is that its synthetic route is with the intermediate I-a-4 of preparation in embodiment 1 for starting raw material carries out:
Its concrete preparation process is as follows:
The preparation of 2.1 intermediate I-a-4:
Intermediate I-a-4 is prepared according to the preparation method of step 1.1 ~ step 1.4 in embodiment 1.
2.2 reactant I-b-1
preparation:
According to document Peer.Kirsch et al., the method in Angew.Chem.Int.Ed., 2001.40.1480 is synthesized.
The preparation of 2.3 chemical compounds I-b
29.2g(0.11mol is added in reaction flask) intermediate I-a-4,38.9g(0.1mol) reactant I-b-1,0.3g tetra-triphenylphosphine palladium, 15g sodium carbonate, 100ml toluene, 100ml water and 100ml ethanol, backflow is warming up to, back flow reaction 4h under stirring; Reaction terminates rear cooling, adds 100ml water and carries out separatory, discard water layer, organic layer evaporate to dryness is obtained crude product;
Gained crude product is first carried out column chromatography, and then carries out recrystallization, obtain finished product 37g, yield 70%.
White crystal obtained by Example 2 detects, and its detected result is as follows:
GC：99.9%；
m.p.：68℃；
MS：m/s（%）
528（2.8），381（100），283（21.3），265（6.5）；
1H-NMR：δ（ppm）
0.90（t，3H），1.29（m，4H），1.54（m，1H），1.78（m，3H），2.12（m，1H），2.36（m，1H），2.61（m，1H），3.80（t，1H），6.89（m，2H），7.22（d，2H），7.38（m，4H）；
△ε：22.3（20℃，589nm）；
△n：0.129（20℃，1000Hz）；
c.p.：85℃。
Prove through above-mentioned detected result, gained white crystal is really
Embodiment 3
Prepare chemical compounds I-c:
The preparation of chemical compounds I-c is that its synthetic route is with the intermediate I-a-2 of preparation in embodiment 1 for starting raw material carries out:
Its concrete preparation process is as follows:
The preparation of 3.1 intermediate I-a-2:
Intermediate I-a-2 is prepared according to the preparation method of step 1.1 ~ step 1.2 in embodiment 1.
The preparation of 3.2 intermediate I-c-1:
In reaction flask, add 17.5g(0.1mol) 3-bromofluorobenzene and 250ml tetrahydrofuran (THF), be cooled to-60 DEG C ~-50 DEG C after stirring and dissolving, do not drip 40ml2.5M(0.1mol higher than the condition of-50 DEG C in guarantee system temperature) butyllithium; Then continue to drip 15.8g(0.1mol) tetrahydrofuran solution (15.8g intermediate I-a-2 is dissolved in 50ml tetrahydrofuran (THF)) of intermediate I-a-2, drips complete stirring reaction 30min; Naturally be warming up to-20 DEG C, add 50ml water and carry out separatory, discard water layer, organic layer 50ml × 4 water washings, obtain thick product after solvent evaporated;
Thick product is dissolved in 40ml methylene dichloride, is cooled to-85 DEG C ~-75 DEG C; Temperature control, not higher than under-70 DEG C of conditions, first adds 40ml triethyl silicane, and then drips 40ml boron trifluoride ether solution, drips complete stirring reaction 1h; Be warming up to-10 DEG C after reaction terminates, add saturated sodium bicarbonate solution and be hydrolyzed, discard water layer after leaving standstill separatory, by the solvent evaporate to dryness in organic layer, obtain finished product 19g, i.e. intermediate I-c-1; Yield 80%.
The preparation of 3.3 intermediate I-c-2
23.8g(0.1mol is added in reaction flask) intermediate I-c-2,11.2g(0.1mol) potassium tert.-butoxide and 250ml tetrahydrofuran (THF), be cooled to-70 DEG C ~-60 DEG C after stirring and dissolving; The tetrahydrofuran solution (13.5g trimethyl borate is dissolved in 50ml tetrahydrofuran (THF)) of 13.5g (0.13mol) trimethyl borate is instilled, temperature control-60 ± 5 DEG C of stirring reaction 30min under stirring; Reaction terminates naturally to be warming up to-20 DEG C afterwards, adds 50ml water and 10ml concentrated hydrochloric acid, and stir separatory after 30min, discard water layer, washed by the water of organic layer 50ml × 4, then solvent evaporated obtains finished product 14.2g, i.e. intermediate I-c-2; Yield 50%; HPLC:97%.
3.4 the preparation of chemical compounds I-c
In reaction flask, add 31.2g(0.11mol) intermediate I-c-2,38.9g(0.1mol) reactant I-b-1(prepared by step 2.2 in embodiment 2), 0.3g tetra-triphenylphosphine palladium, 15g sodium carbonate, 100ml toluene, 100ml water and 100ml ethanol, backflow is warming up to, back flow reaction 4h under stirring; Reaction terminates rear cooling, adds 100ml water and carries out separatory, discard water layer, organic layer evaporate to dryness is obtained crude product;
Gained crude product is first carried out column chromatography, and then carries out recrystallization, obtain finished product 38.2g, yield 70%.
White crystal obtained by Example 3 detects, and its detected result is as follows:
GC：99.9%；
m.p.：65℃；
MS：m/s（%）
546（3.6），399（100），301（15.7），283（8.5）；
1H-NMR：δ（ppm）
0.90（t，3H），1.29（m，4H），1.54（m，1H），1.78（m，3H），2.12（m，1H），2.36（m，1H），2.61（m，1H），3.80（t，1H），6.89（m，3H），7.12（d，1H）7.22（d，2H）7.72（t，1H）；
△ε：22.3（20℃，589nm）；
△n：0.129（20℃，1000Hz）；
c.p.：75℃。
Prove through above-mentioned detected result, the material of gained is really
As can be seen from above-described embodiment 1 ~ 3, the liquid crystalline cpd containing sulfo-THP trtrahydropyranyl with formula I structure provided by the invention, having wider nematic temperature range and larger dielectric anisotropy, is a kind of liquid crystal monomer being suitable for very much being used as liquid-crystal display.Above-described embodiment 1 ~ 3 merely provides the liquid crystalline cpd synthetic method that three kinds have formula I structure, and other liquid crystalline cpds shown in formula I all can synthesize by said synthesis route.
On the preparation process basis of above-described embodiment 1 ~ 3, reactant consumption expanded on year-on-year basis or reduces, all not affecting the quality of obtained liquid crystalline cpd.
In the following examples 4 ~ 11, take in proportion respectively formula I, II, the liquid crystalline cpd shown in III, IV, obtained liquid-crystal composition after mixing.The liquid crystalline cpd shown in general formula II, III, IV used all can be synthesized by known method, or is obtained by commercial sources.The preparation method of liquid-crystal composition takes ordinary method, such as, at high temperature dissolved by the liquid crystal monomer of various component and mix in a solvent, then steam at reduced pressure conditions and desolventize, obtain liquid-crystal composition; Or take the methods such as heating, ultrasonic wave, suspension to be mixed in proportion by liquid crystal monomer obtained.Then the liquid-crystal composition of gained is filled between liquid-crystal display two substrates and carries out performance test.
Embodiment 4
In liquid-crystal composition each component and proportioning as shown in table 1:
The component proportion of the liquid-crystal composition of table 1 embodiment 4
The liquid-crystal composition of Example 4 carries out performance test, and its test result is: Δ n:0.105; △ ε: 7.2; γ 1:65; C.p:87 DEG C.
Embodiment 5
In liquid-crystal composition each component and proportioning as shown in table 2:
The component proportion of the liquid-crystal composition of table 2 embodiment 5
The liquid-crystal composition of Example 5 carries out performance test, and its test result is: Δ n:0.125; △ ε: 7.8; γ 1:65; C.p:94 DEG C.
Embodiment 6
In liquid-crystal composition each component and proportioning as shown in table 3:
The component proportion of the liquid-crystal composition of table 3 embodiment 6
The liquid-crystal composition of Example 6 carries out performance test, and its test result is: Δ n:0.105; △ ε: 7.2; γ 1:65; C.p:87 DEG C.
Embodiment 7
In liquid-crystal composition each component and proportioning as shown in table 4:
The component proportion of the liquid-crystal composition of table 4 embodiment 7
The liquid-crystal composition of Example 7 carries out performance test, and its test result is: Δ n:0.112; △ ε: 7.7; γ 1:65; C.p:87 DEG C.
Embodiment 8
In liquid-crystal composition each component and proportioning as shown in table 5 below:
The component proportion of the liquid-crystal composition of table 5 embodiment 8
The liquid-crystal composition of Example 8 carries out performance test, and its test result is: Δ n:0.110; △ ε: 6.9; γ 1:63; C.p:87 DEG C.
Embodiment 9
In liquid-crystal composition each component and proportioning as shown in table 6 below:
The component proportion of the liquid-crystal composition of table 6 embodiment 9
The liquid-crystal composition of Example 9 carries out performance test, and its test result is: Δ n:0.105; △ ε: 7.1; γ 1:65; C.p:85 DEG C.
Embodiment 10
In liquid-crystal composition each component and proportioning as shown in table 7 below:
The component proportion of the liquid-crystal composition of table 7 embodiment 10
The liquid-crystal composition of Example 10 carries out performance test, and its test result is: Δ n:0.111; △ ε: 7.5; γ 1:68; C.p:90 DEG C.
Embodiment 11
In liquid-crystal composition each component and proportioning as shown in table 8 below:
The component proportion of the liquid-crystal composition of table 8 embodiment 11
The liquid-crystal composition of Example 11 carries out performance test, and its test result is: Δ n:0.120; △ ε: 7.3; γ 1:62; C.p:92 DEG C.
From the performance perameter of the liquid-crystal composition shown in embodiment 4 ~ 11, liquid-crystal composition provided by the invention has high clearing point, suitable optical anisotropy, low rotary viscosity and response speed faster, be applicable to manufacture liquid-crystal display, be specially adapted to manufacture TFT-LCD liquid-crystal display.
Although the present invention only lists particular compound and the proportioning consumption (weight percentage) thereof of above-mentioned 8 embodiments, and carried out performance test, but liquid-crystal composition of the present invention can on the basis of above-described embodiment, utilize formula I involved in the present invention, II, the liquid crystalline cpd shown in III, IV expands further and revises, by suitably adjusting its proportioning consumption, all object of the present invention can be reached.
Claims (6)
1. containing the liquid crystalline cpd of sulfo-THP trtrahydropyranyl, it is characterized in that: described liquid crystalline cpd is any one in compound shown in formula I-1 ~ formula I-7,
In formula,
R
1-H or the straight chained alkyl containing 1 ~ 10 carbon atom;
R
2-F ,-Cl ,-OCF
3,-CF
3,-CN ,-NCS ,-OCHF
2in arbitrary group;
L
1, L
2, L
3, L
4, L
5, L
6, L
7, L
8-H or-F respectively.
2. the liquid crystalline cpd containing sulfo-THP trtrahydropyranyl according to claim 1, is characterized in that: in the liquid crystalline cpd shown in described formula I-1 ~ formula I-7,
R
1-H or the straight chained alkyl containing 1 ~ 6 carbon atom;
R
2-Cl ,-F ,-OCF
3,-CF
3, arbitrary group in-CN ,-NCS.
3. the preparation method of the liquid crystalline cpd containing sulfo-THP trtrahydropyranyl described in any one of claim 1 or 2, is characterized in that: its reaction scheme is:
When shown in preparation formula I-1, formula I-2, formula I-3 during compound, adopt route A:
In route A, the actual conditions of each step reaction is respectively:
Prepare intermediate b:
Reaction raw materials a, reactant methyl acrylate, trimethylsilyl diethylamine and MEHQ, solvent acetonitrile are dropped in reactor, carries out back flow reaction under nitrogen protection; Reaction terminates rear solvent evaporated, adds Glacial acetic acid and water, proceeds back flow reaction; Reaction terminates rear cooling, adds that methyl tertiary butyl ether carries out extracting, separatory; By the solvent evaporate to dryness in organic layer, obtain evaporate to dryness thing;
In evaporate to dryness thing, add solvent methanol, under control temperature is 0 DEG C ~ 10 DEG C conditions, adds sodium borohydride, carries out reduction reaction; After reaction terminates, add that water and methyl tertiary butyl ether carry out extracting, separatory, by the solvent evaporate to dryness in organic layer, obtain secondary evaporate to dryness thing;
In secondary evaporate to dryness thing, add catalyzer tosic acid and solvent toluene, carry out back flow reaction; Add after reaction terminates that water and toluene carry out extracting, separatory, by the solvent evaporate to dryness in organic layer, obtain intermediate b crude product, after refining, namely obtain intermediate b;
Prepare intermediate c:
Intermediate b, reactant trimethylammonium iodate silicon and methylene chloride are dropped in reactor, 25 ± 5 DEG C of reactions; Add water after reaction terminates, separatory; By the solvent evaporate to dryness in organic layer, obtain evaporate to dryness thing;
Reactant oxalyl chloride and solvent benzol is added, 25 ± 5 DEG C of stirring reactions in above-mentioned evaporate to dryness thing; Reaction terminates rear solvent evaporated, adds methylene dichloride and triethylamine, then in reaction solution, passes into hydrogen sulfide and react; Sodium hydrogen carbonate solution is added, separatory after reaction terminates; By the solvent evaporate to dryness in organic layer, obtain intermediate c;
Prepare intermediate d:
Under temperature control-50 ± 5 DEG C of conditions, by the instillation of reactant butyllithium containing in the tetrahydrofuran solution of Isosorbide-5-Nitrae-dibromobenzene, drip the tetrahydrofuran solution continuing to drip intermediate c after finishing, stirring reaction; Add water after reaction terminates separatory; By the solvent evaporate to dryness in organic layer, obtain evaporate to dryness thing;
Above-mentioned evaporate to dryness thing is dissolved in methylene dichloride, at-75 ± 5 DEG C, instills reactant triethyl silicane and boron trifluoride diethyl etherate, and keep this temperature to react; Reaction terminates rear intensification, adds saturated sodium bicarbonate solution and is hydrolyzed, and then carries out extracting, separatory, by the solvent evaporate to dryness in organic layer, obtains intermediate d crude product; Namely intermediate d is obtained after recrystallization;
Prepare intermediate e:
Under temperature control-75 ± 5 DEG C of conditions, by the instillation of reactant butyllithium containing in the tetrahydrofuran solution of intermediate d, drip the tetrahydrofuran solution continuing dropwise reaction thing trimethyl borate after finishing; Be warming up to-20 ± 5 DEG C after being added dropwise to complete, add hydrochloric acid and stirring reaction, carry out extracting after reaction terminates, separatory; By the solvent evaporate to dryness in organic layer, obtain intermediate e crude product, after recrystallization, namely obtain intermediate e;
Prepare intermediate f:
Tetrahydrofuran (THF), water and hydrogen peroxide is added, 40 ± 5 DEG C of reactions in intermediate e; Add water and methylene dichloride carries out separatory after reaction terminates, by the solvent evaporate to dryness in organic layer, obtain intermediate f crude product, after recrystallization, namely obtain intermediate f;
Prepare intermediate g:
In intermediate f, add catalyzer 5% palladium charcoal and solvent toluene, 25 ± 5 DEG C, carry out catalytic hydrogenation reaction under 0.25 ± 0.05Mpa condition; After reaction terminates, filtration catalizer, and solvent evaporated, namely obtain intermediate g;
Prepare intermediate h:
Under temperature control-75 ± 5 DEG C of conditions, by the instillation of reactant butyllithium containing in the tetrahydrofuran solution of reactant 2-trimethyl silyl-1,3-dithiane, drip after finishing and slowly rise to 0 DEG C; Then-75 ± 5 DEG C are again cooled to, the tetrahydrofuran solution of instillation containing intermediate g; Be warming up to-25 ± 5 DEG C after being added dropwise to complete, continue stirring reaction; After question response terminates, add water and carry out separatory, by the solvent evaporate to dryness in organic layer, obtain intermediate h crude product, after recrystallization, obtain intermediate h;
Prepare finished product I:
Under temperature control-20 ± 5 DEG C of conditions, by the instillation of reactant trifluoromethanesulfonic acid containing in the dichloromethane solution of intermediate h, continue after stirring reaction 30min to be cooled to-75 ± 5 DEG C; Under this temperature condition, first instillation includes the dichloromethane solution of reactant 3,4,5-trifluoromethyl phenol and triethylamine, then adds reactant NEt fast
33HF; Temperature control-75 ± 5 DEG C, instillation includes the dichloromethane solution of bromine, continues stirring reaction at this temperature; Be warming up to 0 ± 5 DEG C after reaction terminates, reaction solution poured in mixture of ice and water, regulate pH value to 5 ~ 8 of reactant system with sodium hydroxide solution, then carry out separatory; By the solvent evaporate to dryness in organic layer, obtain finished product I crude product, through column chromatography and recrystallization, obtain finished product I;
L in formula I-4, formula I-6
5, L
6be all-H, the L in formula I-5, formula I-7
7, L
8when being all-H, route B is adopted to synthesize:
In route B, the actual conditions of each step reaction is respectively:
Prepare intermediate b:
Reaction raw materials a, reactant methyl acrylate, trimethylsilyl diethylamine and MEHQ, solvent acetonitrile are dropped in reactor, carries out back flow reaction under nitrogen protection; Reaction terminates rear solvent evaporated, adds Glacial acetic acid and water, proceeds back flow reaction; Reaction terminates rear cooling, adds that methyl tertiary butyl ether carries out extracting, separatory; By the solvent evaporate to dryness in organic layer, obtain evaporate to dryness thing;
In evaporate to dryness thing, add solvent methanol, under control temperature is 0 DEG C ~ 10 DEG C conditions, adds sodium borohydride, carries out reduction reaction; After reaction terminates, add that water and methyl tertiary butyl ether carry out extracting, separatory, by the solvent evaporate to dryness in organic layer, obtain secondary evaporate to dryness thing;
In secondary evaporate to dryness thing, add catalyzer tosic acid and solvent toluene, carry out back flow reaction; Add after reaction terminates that water and toluene carry out extracting, separatory, by the solvent evaporate to dryness in organic layer, obtain intermediate b crude product, after refining, namely obtain intermediate b;
Prepare intermediate c:
Intermediate b, reactant trimethylammonium iodate silicon and methylene chloride are dropped in reactor, 25 ± 5 DEG C of reactions; Add water after reaction terminates, separatory; By the solvent evaporate to dryness in organic layer, obtain evaporate to dryness thing;
Reactant oxalyl chloride and solvent benzol is added, 25 ± 5 DEG C of stirring reactions in above-mentioned evaporate to dryness thing; Reaction terminates rear solvent evaporated, adds methylene dichloride and triethylamine, then in reaction solution, passes into hydrogen sulfide and react; Sodium hydrogen carbonate solution is added, separatory after reaction terminates; By the solvent evaporate to dryness in organic layer, obtain intermediate c;
Prepare intermediate d:
Under temperature control-50 ± 5 DEG C of conditions, by the instillation of reactant butyllithium containing in the tetrahydrofuran solution of Isosorbide-5-Nitrae-dibromobenzene, drip the tetrahydrofuran solution continuing to drip intermediate c after finishing, stirring reaction; Add water after reaction terminates separatory; By the solvent evaporate to dryness in organic layer, obtain evaporate to dryness thing;
Above-mentioned evaporate to dryness thing is dissolved in methylene dichloride, at-75 ± 5 DEG C, instills reactant triethyl silicane and boron trifluoride diethyl etherate, and keep this temperature to react; Reaction terminates rear intensification, adds saturated sodium bicarbonate solution and is hydrolyzed, and then carries out extracting, separatory, by the solvent evaporate to dryness in organic layer, obtains intermediate d crude product; Namely intermediate d is obtained after recrystallization;
Prepare intermediate e:
Under temperature control-75 ± 5 DEG C of conditions, by the instillation of reactant butyllithium containing in the tetrahydrofuran solution of intermediate d, drip the tetrahydrofuran solution continuing dropwise reaction thing trimethyl borate after finishing; Be warming up to-20 ± 5 DEG C after being added dropwise to complete, add hydrochloric acid and stirring reaction, carry out extracting after reaction terminates, separatory; By the solvent evaporate to dryness in organic layer, obtain intermediate e crude product, after recrystallization, namely obtain intermediate e;
Prepare finished product I:
Reactant is added in intermediate e
catalyzer tetra-triphenylphosphine palladium and sodium carbonate, solvent toluene, second alcohol and water, temperature rising reflux reacts; After question response terminates, add water separatory, by the solvent evaporate to dryness in organic layer, obtains finished product I crude product; Through column chromatography and recrystallization, obtain finished product I;
L in formula I-4, formula I-6
5, L
6at least one is-F, the L in formula I-5, formula I-7
7, L
8when at least one is-F, route C is adopted to synthesize:
In route C, the actual conditions of each step reaction is respectively:
Prepare intermediate b:
Reaction raw materials a, reactant methyl acrylate, trimethylsilyl diethylamine and MEHQ, solvent acetonitrile are dropped in reactor, carries out back flow reaction under nitrogen protection; Reaction terminates rear solvent evaporated, adds Glacial acetic acid and water, proceeds back flow reaction; Reaction terminates rear cooling, adds that methyl tertiary butyl ether carries out extracting, separatory; By the solvent evaporate to dryness in organic layer, obtain evaporate to dryness thing;
In evaporate to dryness thing, add solvent methanol, under control temperature is 0 DEG C ~ 10 DEG C conditions, adds sodium borohydride, carries out reduction reaction; After reaction terminates, add that water and methyl tertiary butyl ether carry out extracting, separatory, by the solvent evaporate to dryness in organic layer, obtain secondary evaporate to dryness thing;
In secondary evaporate to dryness thing, add catalyzer tosic acid and solvent toluene, carry out back flow reaction; Add after reaction terminates that water and toluene carry out extracting, separatory, by the solvent evaporate to dryness in organic layer, obtain intermediate b crude product, after refining, namely obtain intermediate b;
Prepare intermediate c:
Intermediate b, reactant trimethylammonium iodate silicon and methylene chloride are dropped in reactor, 25 ± 5 DEG C of reactions; Add water after reaction terminates, separatory; By the solvent evaporate to dryness in organic layer, obtain evaporate to dryness thing;
Reactant oxalyl chloride and solvent benzol is added, 25 ± 5 DEG C of stirring reactions in above-mentioned evaporate to dryness thing; Reaction terminates rear solvent evaporated, adds methylene dichloride and triethylamine, then in reaction solution, passes into hydrogen sulfide and react; Sodium hydrogen carbonate solution is added, separatory after reaction terminates; By the solvent evaporate to dryness in organic layer, obtain intermediate c;
Prepare intermediate d ':
Under temperature control-50 ± 5 DEG C of conditions, by the instillation of reactant butyllithium containing in the tetrahydrofuran solution of 3-bromofluorobenzene, drip the tetrahydrofuran solution continuing to drip intermediate c after finishing, stirring reaction; Add water after reaction terminates separatory, by the solvent evaporate to dryness in organic layer, obtains evaporate to dryness thing;
Above-mentioned evaporate to dryness thing is dissolved in methylene dichloride, at-75 ± 5 DEG C, instills reactant triethyl silicane and boron trifluoride diethyl etherate, and react under keeping this temperature; Reaction terminates rear intensification, adds saturated sodium bicarbonate solution and is hydrolyzed, separatory, by the solvent evaporate to dryness in organic layer, namely obtain intermediate d ';
Prepare intermediate e ':
Under temperature control-95 ± 5 DEG C of conditions, the instillation of reactant butyllithium is contained in the tetrahydrofuran solution of intermediate d ' and potassium tert.-butoxide, drip the tetrahydrofuran solution of continuation dropwise reaction thing trimethyl borate after finishing; Be warming up to-20 ± 5 DEG C after being added dropwise to complete, add hydrochloric acid and water, stirring reaction 30min; Reaction terminates rear separatory, by the solvent evaporate to dryness in organic layer, namely obtains intermediate e ';
Prepare finished product I:
Reactant is added in intermediate e '
catalyzer tetra-triphenylphosphine palladium and sodium carbonate, solvent toluene, second alcohol and water, temperature rising reflux reacts; After question response terminates, add water separatory, by the solvent evaporate to dryness in organic layer, obtains finished product I crude product; Through column chromatography and recrystallization, obtain finished product I.
4. a liquid-crystal composition, is characterized in that: described liquid-crystal composition comprises the liquid crystalline cpd shown in formula I described in any one of at least one claim 1 ~ 2; The weight percentage of liquid crystalline cpd shown in described formula I in liquid-crystal composition is for being less than or equal to 40% and non-vanishing.
5. a kind of liquid-crystal composition according to claim 4, it is characterized in that: described liquid-crystal composition also includes the compound shown in general formula II, the compound shown in general formula III of 5% ~ 50% and the compound shown in general formulae IV of 3% ~ 45% that weight percentage is 4% ~ 50%
Wherein,
R
3, R
4, R
5, R
6, R
7-CN ,-F respectively, the carbonatoms alkyl that is 1 ~ 7, the carbonatoms alkoxyl group that is 1 ~ 7, carbonatoms be 2 ~ 7 thiazolinyl or carbonatoms be any one in the fluoroalkyl of 1 ~ 5;
Z
3, Z
4singly-bound ,-CH respectively
2cH
2-,-CH=CH-,-C ≡ C-,-COO-,-OOC-,-CF
2o-,-OCH
2-,-CH
2o-,-OCF
2-wherein any one;
the arbitrary group in singly-bound or following groups respectively:
the arbitrary group in following groups:
Y
1, Y
2-H or-F respectively;
N
5, n
6the arbitrary numerical value in 0,1,2 respectively.
6. a kind of liquid-crystal composition according to claim 5, is characterized in that: described liquid-crystal composition comprises that weight percentage is the liquid crystalline cpd shown in the formula I of 8% ~ 19%, the liquid crystalline cpd shown in general formula II of 20% ~ 36%, the liquid crystalline cpd shown in general formula III of 31% ~ 47% and 5% ~ 33% the liquid crystalline cpd shown in general formulae IV.
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