CN103880810A - Oxepane derivative - Google Patents
Oxepane derivative Download PDFInfo
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- CN103880810A CN103880810A CN201410108431.XA CN201410108431A CN103880810A CN 103880810 A CN103880810 A CN 103880810A CN 201410108431 A CN201410108431 A CN 201410108431A CN 103880810 A CN103880810 A CN 103880810A
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- 0 CC(c1c(*)c(CC*)cc(C2OCCC(*)CCC2)c1)S Chemical compound CC(c1c(*)c(CC*)cc(C2OCCC(*)CCC2)c1)S 0.000 description 1
- WBVQTMYUJCROHW-UHFFFAOYSA-N Cc(cc1)ccc1-c1ccc(-c(cc2F)cc(F)c2F)c(F)c1 Chemical compound Cc(cc1)ccc1-c1ccc(-c(cc2F)cc(F)c2F)c(F)c1 WBVQTMYUJCROHW-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D313/00—Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom
- C07D313/02—Seven-membered rings
- C07D313/04—Seven-membered rings not condensed with other rings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
- C09K19/44—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing compounds with benzene rings directly linked
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
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- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
Abstract
The invention discloses an oxepane derivative. The structural general formula of the compound is as shown in the formula I. The compound is stable in structure, has a wide liquid crystal state temperature range, good low-temperature intersolubility and large dielectric anisotropy theta epsilon, can be used for realizing a low threshold voltage and low rotary viscosity gamma 1 when being used in an optical device, can be used for improving the performances of a liquid crystal composition material and a display device, and has great significance in quick response of the display device. A liquid crystal composition containing the compound can be applied to preparation of liquid crystal display devices with low driving voltage, wide temperature range and quick response speed. The formula I is as shown in the specification.
Description
Technical field
The invention belongs to liquid crystalline cpd and synthesize and Application Areas, relate to a kind of oxygen heterocyclic ring heptane derivative.
Background technology
Use the liquid-crystal display of liquid-crystal composition to be widely used in the indicating meters such as instrument, computer, TV, for technical field of liquid crystal display, although market is very huge in recent years, technology is also ripe gradually, but people to the requirement of technique of display also in continuous raising, especially realizing response fast, reducing driving voltage and reduce the aspects such as power consumption.Liquid crystal material, as one of important photoelectron material of liquid-crystal display, plays an important role to the performance of improving liquid-crystal display.
Liquid crystal display device is divided into following modes according to display mode: twisted nematic (TN) pattern, supertwist nematic phase (STN) pattern, coplanar pattern (IPS), vertical orientation (VA) pattern.No matter which kind of display format all needs liquid-crystal composition to have following characteristic.
(1) chemistry, physical properties is stable.
(2) viscosity is low.
(3) there is suitable △ ε.
(4) suitable index of refraction △ n.
(5) good with the intermiscibility of other liquid crystalline cpds.
Obtain very great development as the liquid crystal material that shows use, occurred a large amount of liquid crystalline cpds.Develop into phenylcyclohexane class, phenylacetylene class, ethyl bridged bond class, end thiazolinyl liquid crystal and various fluorine-containing aromatic ring class liquid crystalline cpds etc. from biphenyl nitrile, ester class, oxygen heterocyclic ring class, pyrimidine lopps liquid crystalline cpd, constantly meet the display performance requirements such as TN, STN, TFT-LCD.
Any demonstration all requires wider liquid crystal state temperature with liquid-crystal composition, and higher stability, than better suited viscosity, has response speed faster to electric field.But be also used in liquid-crystal display separately without any single liquid crystal monomer so far, and need not just can meet performance requriements with other compound combination.If two or more liquid crystal monomer is mixed, just can change continuously the various types of properties of liquid crystal, general commodity liquid-crystal composition is also all mixed by various of monomer liquid crystal substantially.
Summary of the invention
The object of this invention is to provide a kind of oxygen heterocyclic ring heptane derivative.
Oxygen heterocyclic ring heptane derivative provided by the invention, its general structure is suc as formula shown in I,
In described formula I, R
1and R
2identical or different, be all selected from following group a, b or c:
A, be selected from H, Cl, F ,-CN ,-OCN ,-OCF
3,-CF
3,-CHF
2,-CH
2f ,-OCHF
2,-SCN ,-NCS ,-SF
5, C1-C15 alkoxyl group, the thiazolinyl of C2-C15 carbon atom and the alkene oxygen base of C2-C15 of alkyl, C1-C15 at least one;
B, contain-CH
2-described group a at least one-CH
2-be not directly connected by least one replacement in following group and Sauerstoffatom and group :-CH=CH-,-C ≡ C-,-COO-,-OOC-, cyclobutyl ,-O-and-S-;
In c, described group a or b at least one hydrogen replaced by fluorine or chlorine and group;
Z
1and Z
2all be selected from singly-bound ,-CH
2-,-CH
2-CH
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-,-C
2f
4-and-at least one in CF=CF-;
A, b and c are the integer of 0-3, and a+b+c≤5;
A or b are 2 or 3 o'clock,
the group representing is identical or different,
the group representing is identical or different,
the group representing can be identical can be different.
R in described formula I
1and R
2definition in, the alkyl of described C1-C15 is specifically selected from the alkyl of C2-C15, the alkyl of C3-C15, the alkyl of C4-C15, the alkyl of C5-C15, the alkyl of C6-C15, the alkyl of C1-C7, the alkyl of C2-C7, the alkyl of C3-C7, the alkyl of C4-C7, the alkyl of C5-C7, the alkyl of C6-C7, the alkyl of C1-C6, the alkyl of C2-C6, the alkyl of C3-C6, the alkyl of C4-C6, the alkyl of C5-C6, the alkyl of C1-C5, the alkyl of C2-C5, the alkyl of C3-C5, the alkyl of C4-C5, the alkyl of C1-C4, the alkyl of C2-C4, the alkyl of C3-C4, the alkyl of C1-C3, the alkyl of C1-C10, the alkyl of C2-C10, the alkyl of C3-C10, the alkyl of C1-C10, at least one in the alkyl of C1-C2 and the alkyl of C2-C3,
The alkoxyl group of described C1-C15 is specifically selected from the alkoxyl group of C2-C15, the alkoxyl group of C3-C15, the alkoxyl group of C4-C15, the alkoxyl group of C5-C15, the alkoxyl group of C6-C15, the alkoxyl group of C1-C7, the alkoxyl group of C2-C7, the alkoxyl group of C3-C7, the alkoxyl group of C4-C7, the alkoxyl group of C5-C7, the alkoxyl group of C6-C7, the alkoxyl group of C1-C6, the alkoxyl group of C2-C6, the alkoxyl group of C3-C6, the alkoxyl group of C4-C6, the alkoxyl group of C5-C6, the alkoxyl group of C1-C5, the alkoxyl group of C2-C5, the alkoxyl group of C3-C5, the alkoxyl group of C4-C5, the alkoxyl group of C1-C4, the alkoxyl group of C2-C4, the alkoxyl group of C3-C4, the alkoxyl group of C1-C3, the alkoxyl group of C1-C10, the alkoxyl group of C2-C10, the alkoxyl group of C3-C10, the alkoxyl group of C1-C10, at least one in the alkoxyl group of C1-C2 and the alkoxyl group of C2-C3,
The thiazolinyl of described C2-C15 is specifically selected from least one in thiazolinyl, the thiazolinyl of C2-C8 and the thiazolinyl of C2-C3 of thiazolinyl, C3-C10 of thiazolinyl, the C2-C10 of thiazolinyl, the C3-C4 of thiazolinyl, the C2-C4 of thiazolinyl, the C4-C5 of thiazolinyl, the C3-C5 of thiazolinyl, the C2-C5 of thiazolinyl, the C5-C6 of thiazolinyl, the C4-C6 of thiazolinyl, the C3-C6 of thiazolinyl, the C2-C6 of thiazolinyl, the C1-C6 of thiazolinyl, the C6-C15 of thiazolinyl, the C5-C15 of thiazolinyl, the C4-C15 of C3-C15;
The alkene oxygen base of described C2-C15 is specifically selected from least one in alkene oxygen base, the alkene oxygen base of C2-C8 and the alkene oxygen base of C2-C3 of alkene oxygen base, C3-C10 of alkene oxygen base, the C2-C10 of alkene oxygen base, the C3-C4 of alkene oxygen base, the C2-C4 of alkene oxygen base, the C4-C5 of alkene oxygen base, the C3-C5 of alkene oxygen base, the C2-C5 of alkene oxygen base, the C5-C6 of alkene oxygen base, the C4-C6 of alkene oxygen base, the C3-C6 of alkene oxygen base, the C2-C6 of alkene oxygen base, the C6-C15 of alkene oxygen base, the C5-C15 of alkene oxygen base, the C4-C15 of C3-C15;
Concrete, compound shown in described formula I is formula I-1 to any one in compound shown in formula I-7:
Described formula I-1 to formula I-7, R
1, R
2, Z
1,
definition respectively with aforementioned formula I in R
1, R
2, Z
1,
definition identical;
Described
definition with
definition identical.
Compound shown in described formula I is more specifically any one in compound shown in formula I-8 to I-16:
Described formula I-8 to formula I-16, R
1for the straight chained alkyl of hydrogen or C1-C10;
R
2for Cl, F ,-OCF
3,-CF
3or OCHF
2;
L
1to L
8all be selected from any one in hydrogen and fluorine.
Compound shown in the formula I that the invention described above provides, as follows one to three preparation and obtaining:
Method one
Method two
Method three
In addition, the above-mentioned liquid crystal compound that comprises arbitrary compound shown in aforementioned formula I, also belongs to protection scope of the present invention.
In this liquid crystal compound, also can contained II to compound shown in formula IV;
Certainly, this liquid crystal compound also can be only made up of to compound shown in formula IV formula I;
Described formula 11 to formula IV, R
1profit R
2all select at least one in alkoxyl group, the thiazolinyl of C2-C7 and the fluoroalkyl of C1-C5 of alkyl, C1-C7 of white oxygen, halogen ,-CN, C1-C7;
Described Z is all selected from singly-bound ,-CH
2-CH
2-,-CH=CH-,-C ≡ C-,-COO-,-OOC-,-OCH
2-,-CH
2o-,-CF
2o-and-OCF
2-at least one;
Described
all be selected from any one in singly-bound and following radicals:
X
1and X
2all be selected from any one in H and F;
A, b and c are all selected from the integer of 0-3.
Described formula II is to formula IV, and the alkyl of C1-C7 is specifically selected from least one in alkyl, the alkyl of C1-C2 and the alkyl of C2-C3 of alkyl, C1-C3 of alkyl, the C3-C4 of alkyl, the C2-C4 of alkyl, the C1-C4 of alkyl, the C4-C5 of alkyl, the C3-C5 of alkyl, the C2-C5 of alkyl, the C1-C5 of alkyl, the C5-C6 of alkyl, the C4-C6 of alkyl, the C3-C6 of alkyl, the C2-C6 of alkyl, the C1-C6 of alkyl, the C6-C7 of alkyl, the C5-C7 of alkyl, the C4-C7 of alkyl, the C3-C7 of C2-C7;
The alkoxyl group of described C1-C7 is specifically selected from the alkoxyl group of C2-C7, the alkoxyl group of C3-C7, the alkoxyl group of C4-C7, the alkoxyl group of C5-C7, the alkoxyl group of C6-C7, the alkoxyl group of C1-C6, the alkoxyl group of C2-C6, the alkoxyl group of C3-C6, the alkoxyl group of C4-C6, the alkoxyl group of C5-C6, the alkoxyl group of C1-C5, the alkoxyl group of C2-C5, the alkoxyl group of C3-C5, the alkoxyl group of C4-C5, the alkoxyl group of C1-C4, the alkoxyl group of C2-C4, the alkoxyl group of C3-C4, the alkoxyl group of C1-C3, at least one in the alkoxyl group of C1-C2 and the alkoxyl group of C2-C3,
The thiazolinyl of described C2-C7 is specifically selected from least one in thiazolinyl, the thiazolinyl of C3-C4 and the thiazolinyl of C2-C3 of thiazolinyl, C2-C4 of thiazolinyl, the C4-C5 of thiazolinyl, the C3-C5 of thiazolinyl, the C2-C5 of thiazolinyl, the C5-C6 of thiazolinyl, the C4-C6 of thiazolinyl, the C3-C6 of thiazolinyl, the C2-C6 of thiazolinyl, the C6-C7 of thiazolinyl, the C5-C7 of thiazolinyl, the C4-C7 of C3-C7;
The fluoroalkyl of described C1-C5 is specifically selected from least one in fluoroalkyl, the fluoroalkyl of C3-C4 and the fluoroalkyl of C2-C3 of fluoroalkyl, C2-C4 of fluoroalkyl, the C4-C5 of fluoroalkyl, the C3-C5 of fluoroalkyl, the C1-C3 of C1-C4;
Concrete, also can the serve as reasons formula I of following mass ratio of described liquid crystal compound forms to compound shown in formula IV:
Wherein, described formula I to the mass ratio of compound shown in formula IV be 3-30:4-60:10-60:3-45, be specially 6:40:32:22,10:20:42:28,12:22:32:35,13:20:50:17,14:34:32:20,16:8:51:25,6-16:8-40:31-51:20-35;
Above-mentioned liquid-crystal composition is specially following liquid-crystal composition a, b, c, d, e or f:
Described liquid crystal compound a comprises that the component of following each mass parts or the component by following each mass parts form:
Described liquid crystal compound a specifically comprises that the component of following each mass parts or the component by following each mass parts form:
Described liquid crystal compound b comprises that the component of following each mass parts or the component by following each mass parts form:
Described liquid crystal compound b specifically comprises that the component of following each mass parts or the component by following each mass parts form:
Described liquid crystal compound c comprises that the component of following each mass parts or the component by following each mass parts form:
Described liquid crystal compound c specifically comprises that the component of following each mass parts or the component by following each mass parts form:
Described liquid crystal compound d comprises that the component of following each mass parts or the component by following each mass parts form:
Described liquid crystal compound d specifically comprises that the component of following each mass parts or the component by following each mass parts form:
Described liquid crystal compound e comprises that the component of following each mass parts or the component by following each mass parts form:
Described liquid crystal compound e specifically comprises that the component of following each mass parts or the component by following each mass parts form:
Described liquid crystal compound f specifically comprises that the component of following each mass parts or the component by following each mass parts form:
Described liquid crystal compound f comprises that the component of following each mass parts or the component by following each mass parts form:
In addition; compound or liquid crystal compound shown in the formula 1 that the invention described above provides, preparing liquid crystal display device material or electrooptics display material or the electrooptics liquid-crystal display of compound shown in application in liquid crystal display device material or electrooptics display material or electrooptics liquid-crystal display and contained I or described liquid crystal compound, also belong to protection scope of the present invention.Wherein, described electrooptics liquid-crystal display is TN escope, VA escope, IPS escope or PDLC escope.
Liquid-crystal composition of the present invention utilizes known method to be prepared conventionally, the method of for example necessary composition at high temperature being dissolved etc., in addition, can add the additive that professional knows in the technical field of the invention according to purposes, as, optically active substance, dyestuff, oxidation inhibitor, uv-absorbing agent, static inhibitor etc.
Liquid crystalline cpd shown in formula I provided by the invention, has the necessary general physical properties of compound; To light, thermally-stabilised, wider nematic phase, good with other Compound Phase dissolubilities, especially this compound has low rotary viscosity γ
1characteristic with large dielectric anisotropy (△ ε >0).Synthetic this compounds is for low rotary viscosity γ
1significant with the exploitation of the monomer liquid crystal compound of high dielectric anisotropy △ ε.The liquid-crystal composition that contains compound shown in formula I, the temperature range of its mesomorphic phase is wide, and viscosity is little, has suitable specific refractory power anisotropy and low start voltage, has important using value.
Embodiment
Embodiment is used for explaining the present invention below, but the present invention is not limited only to embodiment below.Described method is ordinary method if no special instructions.Described material all can obtain from open commercial sources if no special instructions.In embodiment, GC represents gas chromatographic purity below, and HPLC represents liquid chromatography purity, and MP represents fusing point, and MS represents mass spectrum, and 1H-NMR represents nucleus magnetic hydrogen spectrum, △
εrepresent dielectric anisotropy, △ n represents optical anisotropy.
Product shown in following embodiment gained formula I all utilizes gas-chromatography, liquid chromatography, GC-MS gained mass spectrum and 1H-NMR qualification to confirm structural correctness.GC is measured by the HP6820 type gas chromatographicanalyzer of Agilent company, it is the MS5975C type of Agilent company that GC-MS analyzes determinator, 1H-NMR is measured by the DRX-500 analytical equipment of Bruker.Biospin company, fusing point test is used the micro-thermal analyzer of WRX-1S, and setting temperature rise rate is 3 DEG C/min.
Shown in following embodiment gained formula I, the physical property of product all makes to measure in two ways: measure compound itself as sample and compound is mixed as sample and measured with parent liquid crystal.Compound is mixed as the mode of Specimen Determination compound physical property with parent liquid crystal and be: first 15% liquid crystalline cpd is mixed to make sample with 85% parent liquid crystal, then according to the measured value of gained sample, calculate extrapolated value according to the extrapotation shown in following formula
The weight percent of extrapolated value=[100 × (measured value of sample)-(weight percent of parent liquid crystal) × (measured value of parent liquid crystal)]/compound, thus draw the physical property of monomer liquid crystal compound.
Parent liquid crystal used is composed as follows:
The determination of physical appearance method of liquid crystalline cpd is carried out according to the specification of the industry, publishes referring to " liquid crystal device handbook " aircraft industry press
The physical property measurement method of compound:
Phase structure and transmit temperature (DEG C) mensuration
1. possessing polarizing microscope melting point apparatus [plum Teller (Mettler) FP-52 of company type], on hot-plate, place compound, with the heating of 3 DEG C/min speed, utilize polarizing microscope to observe phase-state change on one side on one side, thereby determine phase kind.
2. utilize the differential calorimetric of Mei Tele company to turn round scanner DSC822e, heat up or cooling with the speed of 1 DEG C/min, utilize extrapotation to obtain and follow the heat absorption crest of phase change or the starting point of heating crest of sample, thereby determine tansition temperature.
Crystallization is expressed as C, and smectic phase is S, and nematic phase is N, and liquid is I.
2. viscosity (γ
1at 20 DEG C, measure), use Toyo6254 comprehensive tester.
3. (specific refractory power anisotropy is measured △ n) to optical anisotropy at 25 DEG C, is determined at 25 DEG C, with the light of wavelength 589nm, uses Abbe refractometer to measure △
n.After a direction rubs to the surface of headprism (Pri3m), sample is added drop-wise on headprism.Specific refractory power (n
11) be in the time that polarization direction is parallel with frictional direction, to measure institute's value, specific refractory power (n
⊥) be in the time that polarization direction is vertical with frictional direction, to measure institute's value, (△ value n) is by △ n=n for optical anisotropy
11-n
⊥calculate.
4. dielectric constant anisotropy (△ ε measures at 25 DEG C) is measured by Hewlett-Packard's HP4284a LCR test set.Measure the DIELECTRIC CONSTANT ε ‖ of liquid crystal molecule at long axis direction, measure the specific inductivity (ε of liquid crystal molecule at short-axis direction
⊥), dielectric anisotropy △ ε is by △ ε=ε ‖-ε
⊥calculate.
In measured value, when using liquid crystalline cpd itself as sample, record income value as experimental value, when the mixture using liquid crystalline cpd and mother liquor crystalline substance is during as sample, the value that record is obtained by extrapotation is as experimental value.
Synthetic (method 1) of embodiment 1, chemical compounds I-17
Step 1:
In 1L there-necked flask, add 56.649 (0.24m01) 1, 4-dibromobenzene (reactant), the tetrahydrofuran (THF) (solvent) that 400m1 is dry, under nitrogen protection, be cooled to below-80 DEG C, drip 96ml(0.24mol, 2.5N) n-Butyl Lithium (reactant), drip Bi Baowen 1 hour, at same temperature, splash into 24.6g(0.216mol) mixing solutions of caprolactone (reactant) and 50ml dry tetrahydrofuran (solvent), drip to finish and stir 30 minutes, naturally heat up, 0 DEG C of left and right drips 200ml saturated aqueous ammonium chloride (regulating pH value), separatory, 200ml ethyl acetate (solvent) extraction for water, organic phase washing, be spin-dried for, obtain 58g(GC:89%) liquid, in another 1L there-necked flask, add products obtained therefrom above 58g, the methylene dichloride (solvent) that 500ml is dry, under nitrogen protection, be cooled to-25～-20 DEG C, drip 63.3ml(0.397mol, 2.2eq) triethyl silicon hydrogen (reactant), drip and finish, in system, drip 50ml(0.397mol, 2.2eq) boron trifluoride diethyl etherate (reactant), dripping to finish keeps-25～-20 DEG C to stir 2 hours, naturally rise to 0 DEG C, add saturated aqueous solution of sodium bicarbonate (adjusting pH value) to emitting without bubble, separatory, be washed to neutrality, be spin-dried for solvent, with 2 times of ethanol (solvent) recrystallization, suction filtration, obtain near-white crystal powder (I-17-a) 38.5g, yield 70%, gas chromatographic purity 99%.
Step 2
In reaction flask, add 25.5g (0.1mol) (I-17-a) (reactant); 150ml tetrahydrofuran (THF) (solvent); logical nitrogen protection; be cooled to-60 DEG C; drip sherwood oil (solvent) solution of 0.2mol n-Butyl Lithium (reactant); in 1 hour, dropwise ,-50 DEG C of stirring reactions 30 minutes.Then be cooled to-60 DEG C, in 1 hour, drip 70ml tetrahydrofuran (THF) (solvent) solution of 13g (0.13mol) trimethyl borate (reactant), after adding, continue temperature control stirring reaction 1 hour, be warming up to room temperature, add 0.2mol hydrochloric acid to stir 20 minutes, add after water washing, ethyl acetate 50ml(solvent) extract and separatory, washing organic phase, to neutral, after solvent evaporated, obtains compound (I-17-b) 17.6g, yield 80%, liquid chromatography purity 97%.
Step 3
In reaction flask, add (I-17-b) (reactant) of 24.2g (0.11mol), 38.9g (0.1mol) P2 (reactant) is (according to Peer.Kirsch et al., Angew.Chem.Int.Ed.2001.40.1480. synthetic), tetra-triphenylphosphine palladium 0.3g(catalyzer), sodium carbonate 15g(catalyzer), toluene 100ml(solvent), water 100ml, ethanol 100ml(solvent), reflux 4 hours, add 100ml water, separatory, organic phase evaporate to dryness, through column chromatography, recrystallization obtains product I-17,33.9g yield 70%
The structural confirmation data of this product are as follows:
MP：73℃
MS：m/s%265(5.4)，267(7.8)，337(100)，484(1.4)
As from the foregoing, this product structure is correct, is compound shown in the formula I-17 of ownership formula I.
The liquid crystal property of this product is as follows:
△ε：21.0（20℃，589nm）
△n：0.19（20℃，1000Hz）
As from the foregoing, this monocrystalline has larger specific inductivity, suitable specific refractory power, can apply with mixed liquid crystal in.
Synthetic (method 2) of embodiment 2, chemical compounds I-18
Step 1
In reaction flask, add 25.5g (01mol) (I-17-a); fluorobenzoic boric acid between 0.12mol (reactant); 0.13m0l sodium carbonate (reactant); 80ml toluene (solvent); 60ml ethanol (solvent), 60ml water (solvent), under logical nitrogen protection; add 0.4g tetrakis triphenylphosphine palladium (catalyzer), be heated with stirring to back flow reaction 3 hours.Be cooled to room temperature, separatory, with 50ml toluene (solvent) extraction water, organic phase merging is washed to neutrality.Solvent evaporated, gains are dissolved in 100ml toluene, cross silicagel column decolouring, with toluene (solvent) wash-out, collect elutriant solvent evaporated, with-20 DEG C of frozen recrystallizations after 3 times of petroleum ether dissolutions, suction strainer, obtains white crystal 24.3g(I-18-a).Yield 90%, gas chromatographic purity 99.5%.
Step 2
In reaction flask, add (I-18-a) (reactant) of 27g (001mol); 0.11mol potassium tert.-butoxide; 80ml tetrahydrofuran (THF) (solvent); logical nitrogen protection; be cooled to-90 DEG C; sherwood oil (solvent) solution that drips 0.12mol n-Butyl Lithium (reactant), dropwised in 1 hour ,-90 DEG C of stirring reactions 30 minutes.Still temperature control, to-90 DEG C, dripped 70ml tetrahydrofuran (THF) (solvent) solution of 0.11mol trimethyl borate (reactant), after adding in 1 hour, continue temperature control stirring reaction 1 hour, be warming up to 0 DEG C, add 100ml water and 20ml concentrated hydrochloric acid, stir 20 minutes, separatory, sherwood oil (solvent) extracts and separatory, and washing organic phase is to neutral, after solvent evaporated, with-20 DEG C of frozen recrystallizations after 2 times of sherwood oil heating for dissolving, suction strainer, obtains white crystal 18.8g(I-18-b).Yield 60%, liquid chromatography purity 99.5%.
Synthesizing of step 3 chemical compounds I-18
In reaction flask, add 34.5g (0.11mol) I-18-b (reactant), 38.9g (0.1mol) gP2 (reactant) is (according to Peer.Kirsch et al., Angew.Chem.Int.Ed.2001.40.1480. synthetic), tetra-triphenylphosphine palladium 0.3g(catalyzer), sodium carbonate 15g(catalyzer), toluene 100ml(solvent), water 100ml, ethanol 100ml(solvent), reflux 4 hours, add 100ml water, separatory, organic phase evaporate to dryness, through column chromatography, recrystallization obtains product I-18,40.4g yield 70%
The structural confirmation data of this product are as follows:
MP：78℃
MS：m/s%359(4.7)361（6.3）431(100)578（1.2）
As from the foregoing, this product structure is correct, is compound shown in the formula I-18 of ownership formula I.
The liquid crystal property of this product is as follows:
CP：142℃；
△ε：22.1（20℃，589nm）
△n：0.22（20℃，1000Hz）
As from the foregoing, this monocrystalline has larger specific inductivity, suitable specific refractory power, can apply with mixed liquid crystal in.
Synthetic (method 3) of embodiment 3, chemical compounds I-19
Step 1
(I-17-a) (reactant) of 25.5g (0.1mol) that adds step to obtain in reaction flask, 12Oml tetrahydrofuran (THF) (solvent), sealing is installed stirs, logical nitrogen replacement air, be cooled to-70 DEG C, drip the butyllithium (reactant) that 0.1mol concentration is 2.5M, add latter 20 minutes, pass into dry carbon dioxide (reactant), to saturated, at this temperature, react 2 hours, this reaction solution is poured in the beaker of 20ml concentrated hydrochloric acid (adjusting pH value) and 100ml water and be hydrolyzed, separatory, 50ml ethyl acetate (solvent) is extracted water once, merge organic phase, saturated common salt is washed to neutrality, anhydrous sodium sulphate (siccative) is dry, the concentrated solvent that eliminates, obtain light yellow solid, with 2 times of toluene and 1 times of ethyl acetate (solvent) recrystallization once, obtain white crystal 19.8g(I-19-a).Yield 90%, liquid chromatography purity 98.0%.
Step 2
In reaction flask, add 22g (0.1mol) (I-19-a), glacial acetic acid 100ml, 5%Pt/C10g, stirs lower atmospheric hydrogenation 6 hours, removes by filter catalyzer, and solvent evaporated, adds 50ml toluene recrystallization, yield 50% obtains 11g(I-19-b)
Step 3
In reaction flask, add 22g (0.1m01) (I-19-b), the sharp 30m1 octane-iso of 30m1 toluene (solvent) (solvent), add 14g1, 3-dimercaptopropane (reactant), under stirring, above-mentioned suspension is heated to 50 DEG C, in 30 minutes, add trifluoromethanesulfonic acid (reactant) 19.2g, after adding, be warming up to backflow, separate the water of generation, after point water purification, cool to 90 DEG C, between 70-90 DEG C, in 45 minutes, add methyl tertiary butyl ether (solvent) 100ml, continue cooling, crystallize out, under nitrogen protection, filter, methyl tertiary butyl ether for crystal (solvent) (25ml × 4) washing obtaining, vacuum-drying obtains orange crystal (dithiane fluoroform sulphonate) 31.3g (I-19-c).Yield 70%.
Step 4
In reaction flask, add 24.2g(0.1mol) 2,3 ', 4 ', 5 '-tetrafluoro biphenyl-4-phenol (reactant), the mixing solutions of 0.1mol triethylamine (reactant) and 130ml methylene dichloride (solvent) is also cooled to-70 DEG C, drips above-mentioned 44.8g(0.1mol) solution of the 120ml methylene dichloride (solvent) of (I-19-c) crystal (reactant), within 45 minutes, add, stir after one hour in this temperature, in 5 minutes, add 0.4mol NEt
33HF(reactant).Then at-70 DEG C, add 0.4m in one hour
o30ml methylene dichloride (solvent) solution of l bromine (reactant), then at-70 DEG C, continue reaction one hour, be warming up to 0 DEG C, reaction solution is poured in 32% 160ml aqueous sodium hydroxide solution (adjusting pH value) and 300g ice, regulated pH value to 5～8 of reaction solution by dripping about 45g32% aqueous sodium hydroxide solution.After separatory, water extracts with 80ml methylene dichloride (solvent), merges organic phase 4g diatomite (discoloring agent) and filters, washing, the lower solvent evaporated of decompression.After the crude product column chromatography obtaining, sherwood oil (solvent) recrystallization, obtains white crystal product 21.2g(I-19), yield 45%, GC:99.8%.
The structural confirmation data of this product are as follows:
MP：48℃
MS：m/s%81(87.4)97(96.2)230(100)472(52.3)
As from the foregoing, this product structure is correct, is compound shown in the formula I-19 of ownership formula I.
The liquid crystal property of this product is as follows:
CP：142℃；
△ε：18.0（20℃，589nm）
△n：0.17（20℃，1000Hz）
As from the foregoing, this monocrystalline has larger specific inductivity, suitable specific refractory power, can apply with mixed liquid crystal in.
With reference to the method for above-described embodiment 1-3, only replace the substituting group in respective reaction thing according to substituent definition in product, obtain as shown in the formula each compound shown in I:
Embodiment 4, liquid crystal compound a
According to following weight part, each component is mixed, obtains liquid crystal compound a provided by the invention:
The performance perameter of this liquid crystal compound a is as follows:
CP：97℃；△n：0.085；△ε：7.0；γ
1：60；
As from the foregoing, said composition has high clearing point, suitable optical anisotropy, and low rotary viscosity and faster response speed, in liquid-crystal display.
According to above-mentioned composition, only do not add the component of two ownership formula I compounds, also according to following weight part, each component is mixed, obtain liquid crystal compound g in contrast:
The performance perameter of this liquid crystal compound g is as follows:
CP：87℃；△n：0.095；△ε：4.2；γ
1：62；
With liquid crystal compound a contrast, if do not add compound shown in formula I provided by the invention, the ε of liquid crystal compound obviously reduces.
Embodiment 5, liquid crystal compound b
According to following weight part, each component is mixed, obtains liquid crystal compound b provided by the invention:
The performance perameter of this liquid crystal compound b is as follows:
CP：102℃；△n：0.110；△ε：5.2；γ
1：65；
As from the foregoing, said composition has high clearing point, suitable optical anisotropy, and low rotary viscosity and faster response speed, in liquid-crystal display.
Embodiment 6, liquid crystal compound c
According to following weight part, each component is mixed, obtain liquid crystal compound provided by the invention
c:
The performance perameter of this liquid crystal compound c is as follows:
CP：95℃；△n：0.098；△ε：6.5；γ
1：58；
As from the foregoing, said composition has high clearing point, suitable optical anisotropy, and low rotary viscosity and faster response speed, in liquid-crystal display.
Embodiment 7, liquid crystal compound d
According to following weight part, each component is mixed, obtains liquid crystal compound d provided by the invention:
The performance perameter of this liquid crystal compound d is as follows:
CP：80℃；△n：0.080；△ε：4.5；γ
1：56；
As from the foregoing, said composition has high clearing point, suitable optical anisotropy, and low rotary viscosity and faster response speed, in liquid-crystal display.
Embodiment 8, liquid crystal compound e
According to following weight part, each component is mixed, obtain liquid crystal compound provided by the invention
e:
The performance perameter of this liquid crystal compound e is as follows:
CP：85℃；△n：0.010；△ε：7.0；γ
1：70；
As from the foregoing, said composition has high clearing point, suitable optical anisotropy, and low rotary viscosity and faster response speed, in liquid-crystal display.
Embodiment 9, liquid crystal compound f
According to following weight part, each component is mixed, obtains liquid crystal compound f provided by the invention:
The performance perameter of this liquid crystal compound f is as follows:
CP：100℃；△n：0.120；△ε：7.6；γ
1：60；
As from the foregoing, said composition has high clearing point, suitable optical anisotropy, and low rotary viscosity and faster response speed, in liquid-crystal display.
Claims (8)
1. compound shown in formula I,
In described formula I, R
1and R
2identical or different, be all selected from following group a, b or c:
A, be selected from H, Cl, F ,-CN ,-OCN ,-OCF
3,-CF
3,-CHF
2,-CH
2f ,-OCHF
2,-SCN ,-NCS ,-SF
5, C1-C15 alkoxyl group, the thiazolinyl of C2-C15 carbon atom and the alkene oxygen base of C2-C15 of alkyl, C1-C15 at least one;
B, contain-CH
2-described group a at least one-CH
2-be not directly connected by least one replacement in following group and Sauerstoffatom and group :-CH=CH-,-C ≡ C-,-COO-,-OOC-, cyclobutyl ,-O-and-S-;
In c, described group a or b at least one hydrogen by fluorine or chlorine or deuterated replacement and group;
Z
1and Z
2all be selected from singly-bound ,-CH
2-,-CH
2-CH
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-,-C
2f
4-and-at least one in CF=CF-;
A, b and c are the integer of 0-3, and a+b+c≤5;
A or b are 2 or 3 o'clock,
the group representing is identical or different,
the group representing is identical or different,
the group representing can be identical can be different.
2. compound according to claim 1, is characterized in that: compound shown in described formula I is formula I-1 to any one in compound shown in formula I-7:
Described formula I-1 to formula I-7, R
1, R
2, Z
1,
definition respectively with claim 1 in R
1, R
2, Z
1,
definition identical;
Described
definition with
definition identical;
Compound shown in described formula I is specially any one in compound shown in formula I-8 to I-16:
Described formula I-8 to formula I-16, R
1for the straight chained alkyl of hydrogen or C1-C10;
R
2for Cl, F ,-OCF
3,-CF
3or-OCHF
2;
L
1to L
8all be selected from any one in hydrogen and fluorine.
3. comprise the liquid crystal compound of the arbitrary described compound of claim 1-2.
4. the liquid crystal compound being formed to compound shown in formula IV by the arbitrary described compound of claim 1-2 and formula II:
Described formula II to formula IV, R
1and R
2all be selected from least one in alkoxyl group, the thiazolinyl of C2-C7 and the fluoroalkyl of C1-C5 of alkyl, C1-C7 of hydrogen, halogen ,-CN, C1-C7;
Described Z is selected from singly-bound ,-CH
2-CH
2-,-CH=CH-,-C ≡ C-,-COO-,-OOC-,-OCH
2-,-CH
2o-,-CF
2o-and-OCF
2-at least one;
Described
with
all be selected from any one in singly-bound and following radicals:
Y
1and X
2all be selected from any one in H and F;
A, b and c are all selected from the integer of 0-3.
5. liquid crystal compound according to claim 4, is characterized in that: described formula I to the mass ratio of compound shown in formula IV be 3-30:4-60:10-60:3-45.
6. the arbitrary described liquid crystalline cpd of claim 1-2 or the arbitrary described liquid crystal compound of claim 3-5 are in the application of preparing in liquid crystal display material or electrooptics display material or electrooptics liquid-crystal display.
7. comprise at least one liquid crystal display material or electrooptics display material or the electrooptics liquid-crystal display in liquid crystalline cpd described in claim 1-2 or the arbitrary described liquid crystal compound of claim 3-5.
8. application according to claim 6 or indicating meter claimed in claim 7, is characterized in that: described electrooptics liquid-crystal display is TN escope, VA escope, IPS escope or PDLC escope.
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| CN104479689A (en) * | 2014-12-29 | 2015-04-01 | 石家庄诚志永华显示材料有限公司 | Liquid crystal composition |
| CN106543178A (en) * | 2015-09-16 | 2017-03-29 | 阜阳欣奕华材料科技有限公司 | A kind of compound, liquid-crystal composition and liquid crystal display |
| CN118206434A (en) * | 2024-05-21 | 2024-06-18 | 中节能万润股份有限公司 | Preparation method of alkyl (alkyl cyclohexyl methoxy) cyclohexane |
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| CN118206434B (en) * | 2024-05-21 | 2024-07-23 | 中节能万润股份有限公司 | Preparation method of alkyl (alkyl cyclohexyl methoxy) cyclohexane |
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