CN103880814A - 2-methyl-1,3-dioxepane derivative - Google Patents

2-methyl-1,3-dioxepane derivative Download PDF

Info

Publication number
CN103880814A
CN103880814A CN201410107774.4A CN201410107774A CN103880814A CN 103880814 A CN103880814 A CN 103880814A CN 201410107774 A CN201410107774 A CN 201410107774A CN 103880814 A CN103880814 A CN 103880814A
Authority
CN
China
Prior art keywords
formula
liquid crystal
compound
group
alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201410107774.4A
Other languages
Chinese (zh)
Inventor
韩耀华
史正
尚洪勇
殷科
张少勃
华瑞茂
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shijiazhuang Chengzhi Yonghua Display Material Co Ltd
Original Assignee
Shijiazhuang Chengzhi Yonghua Display Material Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shijiazhuang Chengzhi Yonghua Display Material Co Ltd filed Critical Shijiazhuang Chengzhi Yonghua Display Material Co Ltd
Priority to CN201410107774.4A priority Critical patent/CN103880814A/en
Publication of CN103880814A publication Critical patent/CN103880814A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D321/00—Heterocyclic compounds containing rings having two oxygen atoms as the only ring hetero atoms, not provided for by groups C07D317/00 - C07D319/00
    • C07D321/02—Seven-membered rings
    • C07D321/04—Seven-membered rings not condensed with other rings
    • C07D321/06—1,3-Dioxepines; Hydrogenated 1,3-dioxepines
    • 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
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Liquid Crystal Substances (AREA)

Abstract

The invention discloses a 2-methyl-1,3-dioxepane 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 delta 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

Dioxepane derivative
Technical field
The invention belongs to liquid crystalline cpd and synthesize and Application Areas, relate to a kind of Dioxepane 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 Dioxepane derivative.
Dioxepane derivative provided by the invention, its general structure is suc as formula shown in I,
Figure BDA0000480146110000011
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 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 or deuterium and group;
Figure BDA0000480146110000012
all be selected from least one in singly-bound and following radicals:
Figure BDA0000480146110000021
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,
Figure BDA0000480146110000022
the group representing is identical or different,
Figure BDA0000480146110000023
the group representing is identical or different,
Figure BDA0000480146110000024
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:
Figure BDA0000480146110000025
Figure BDA0000480146110000031
Described formula I-1 to formula I-4, R 1, R 2, Z 1, definition respectively with aforementioned formula I in R 1, R 2, Z 1, c, definition identical;
Described
Figure BDA0000480146110000034
definition with
Figure BDA0000480146110000035
definition identical.
Compound shown in described formula I is more specifically formula I-8 to any one in compound shown in I-16:
Figure BDA0000480146110000036
Figure BDA0000480146110000041
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
Figure BDA0000480146110000042
Method two
Method three
Figure BDA0000480146110000052
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;
Figure BDA0000480146110000053
Described formula II to formula IV, R 1, R 2and R 3all 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 1be 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:
Figure BDA0000480146110000061
X, Y, U and V are all selected from any one in H and F;
D is 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 0-30:5-60:5-60:3-45, be specially 14:18:45:23,14:30:11:45,14:15:32:39,14:20:30:36,17:35:21:27,9:22:32:37 or 9-17:15-35:11-45:23-45; And the quality of compound shown in described formula I is not 0.
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:
Figure BDA0000480146110000062
Figure BDA0000480146110000071
Described liquid crystal compound a specifically comprises that the component of following each mass parts or the component by following each mass parts form:
Figure BDA0000480146110000072
Figure BDA0000480146110000081
Described liquid crystal compound b comprises that the component of following each mass parts or the component by following each mass parts form:
Figure BDA0000480146110000082
Figure BDA0000480146110000091
Described liquid crystal compound b specifically comprises that the component of following each mass parts or the component by following each mass parts form:
Figure BDA0000480146110000092
Figure BDA0000480146110000101
Described liquid crystal compound c comprises that the component of following each mass parts or the component by following each mass parts form:
Figure BDA0000480146110000102
Figure BDA0000480146110000111
Described liquid crystal compound c specifically comprises that the component of following each mass parts or the component by following each mass parts form:
Figure BDA0000480146110000112
Figure BDA0000480146110000121
Described liquid crystal compound d comprises that the component of following each mass parts or the component by following each mass parts form:
Figure BDA0000480146110000122
Described liquid crystal compound d specifically comprises that the component of following each mass parts or the component by following each mass parts form:
Figure BDA0000480146110000132
Figure BDA0000480146110000141
Described liquid crystal compound e comprises that the component of following each mass parts or the component by following each mass parts form:
Figure BDA0000480146110000142
Figure BDA0000480146110000151
Described liquid crystal compound e specifically comprises that the component of following each mass parts or the component by following each mass parts form:
Figure BDA0000480146110000152
Figure BDA0000480146110000161
In addition; compound or liquid crystal compound shown in the formula I 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 compound provided by the invention can utilize known method to be prepared conventionally, for example, by the method etc. of at high temperature dissolving, 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, and 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, and △ ε represents dielectric anisotropy, and △ 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 to identify and confirms 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 ℃/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:
Figure BDA0000480146110000171
Figure BDA0000480146110000181
The determination of physical appearance method of liquid crystalline cpd is carried out according to the standard of the industry, publishes the physical property measurement method of compound referring to " liquid crystal device handbook " aircraft industry press:
Phase structure and transmit temperature (℃) 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 ℃/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 ℃/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 1 measures at 20 ℃), is used Toyo6254 comprehensive tester.
3. (specific refractory power anisotropy is measured △ n) to optical anisotropy at 25 ℃, is determined at 25 ℃, 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 (n11) is in the time that polarization direction is parallel with frictional direction, to measure institute's value, and specific refractory power (n ⊥) is in the time that polarization direction is vertical with frictional direction, to measure institute's value, and optical anisotropy (calculated by △ n=n11-n ⊥ by △ value n).
4. dielectric constant anisotropy (△ ε measures at 25 ℃) 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 (synthetic route 1) of embodiment 1, chemical compounds I-17
Figure BDA0000480146110000182
Step 1:
Figure BDA0000480146110000183
In 1L there-necked flask, add 44.4g(0.24mol) p-bromobenzaldehyde (reactant), the toluene (solvent) that BDO 21.6g (0.24mol) (reactant) 400ml is dry, tosic acid 2g, reflux 4 hours, the water that separates generation, is cooled to room temperature, 100ml washing, solvent evaporated, obtain (I-17-a) 55.5g, yield 90%, gas chromatographic purity 98%.
Step 2
In reaction flask, add 25.7g (0.1mol) (I-17-a) (reactant); 150ml tetrahydrofuran (THF) (solvent); logical nitrogen protection; be cooled to-60 ℃; drip sherwood oil (solvent) solution of 0.2mol n-Butyl Lithium (reactant); in 1 hour, dropwise ,-50 ℃ of stirring reactions 30 minutes.Then be cooled to-60 ℃, 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) 17.8g, yield 80%, liquid chromatography purity 97%.
Step 3 synthetic
In reaction flask, add 24.4g(0.11mol) (I-17-b) (reactant), 38.9g(0.1mol) P2(reactant) (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-17,34g yield 70%
The structural confirmation data of this product are as follows:
GC：99.9%
MP：68℃
MS：m/s%486(1.7),339(100),267(7.9),239(4.8),
1H-NMR：δ（ppm）1.54(m,4H),3.65(m,4H)5.48(s,1H),6.89(m,2H),7.22(d,1H),7.40(m,4H)；
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：21.3（20℃，589nm）
△n：0.119（20℃，1000Hz）
As from the foregoing, this monocrystalline has larger specific inductivity, suitable specific refractory power, can apply with mixed liquid crystal in.
Synthetic (synthetic route 2) of embodiment 2, chemical compounds I-18
Step 1
Figure BDA0000480146110000192
In reaction flask, add 0.1mol(I-17-a); fluorobenzoic boric acid between 0.12mol (reactant); 0.13mol 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 ℃ of frozen recrystallizations after 3 times of petroleum ether dissolutions, suction strainer, obtains white crystal 24.5g(I-18-a).Yield 90%, gas chromatographic purity 99.5%.
Step 3
Figure BDA0000480146110000201
In reaction flask, add 27.2g (0.1mol) (I-18-a) (reactant); 0.11mol potassium tert.-butoxide; 80ml tetrahydrofuran (THF) (solvent); logical nitrogen protection; be cooled to-90 ℃; sherwood oil (solvent) solution that drips 0.12mol n-Butyl Lithium (reactant), dropwised in 1 hour ,-90 ℃ of stirring reactions 30 minutes.Still temperature control, to-90 ℃, 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 ℃, 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 ℃ of frozen recrystallizations after 2 times of sherwood oil heating for dissolving, suction strainer, obtains white crystal 19g(I-18-b).Yield 60%, liquid chromatography purity 99.5%.
Synthesizing of step 4 chemical compounds I-18
In reaction flask, add 34.8g(0.11mol) I-18-b(reactant), 38.9g(0.1mol) gP2(reactant) (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-18,40.6g yield 70%
The structural confirmation data of this product are as follows:
MS：m/s%333(5.3)361（8.9）433(100)580（1.4）
1H-NMR：δ（ppm）1.54(m,4H),3.65(m,4H)5.48(s,1H),6.89(m,2H),7.02（d,1H）7.22(d,2H),7.40(m,4H),7.58(d,1H)7.83(m,1H)；
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：158℃；
△ε：20.6（20℃，589nm）
△n：0.145（20℃，1000Hz）
As from the foregoing, this monocrystalline has larger specific inductivity, and suitable specific refractory power, can be applicable in mixed liquid crystal.
Synthesizing of embodiment 3, chemical compounds I-19
Step 1
Figure BDA0000480146110000203
The 25.7g (0.1mol) (I-17-a) (reactant) that adds step to obtain in reaction flask, 120ml tetrahydrofuran (THF) (solvent), sealing is installed stirs, logical nitrogen replacement air, be cooled to-70 ℃, 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 (regulate 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 20g(I-19-a).Yield 90%, liquid chromatography purity 98.0%.
Step 2
Figure BDA0000480146110000211
In reaction flask, add 22.2g (0.1mol) (I-19-a), glacial acetic acid 100ml, 5%Pt/C10g, stir lower atmospheric hydrogenation 6 hours, remove by filter catalyzer, solvent evaporated, add 50ml toluene recrystallization, yield 50% obtains 11.3g(I-19-b)
Step 3
Figure BDA0000480146110000212
In reaction flask, add 22.6g (0.1mol) (I-19-b), 30ml toluene (solvent) and 30ml octane-iso (solvent), add 14g1, 3-dimercaptopropane (reactant), under stirring, above-mentioned suspension is heated to 50 ℃, 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 ℃, between 70-90 ℃, 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) 31.5g (I-19-c).Yield 70%
Step 4
Figure BDA0000480146110000213
In reaction flask, add 24.2g (0.1mol) 2,3 ', 4 ', 5 '-tetrafluoro biphenyl-4-phenol (reactant), the mixing solutions of 0.12mol triethylamine (reactant) and 130ml methylene dichloride (solvent) is also cooled to-70 ℃, drips the solution of the 120ml methylene dichloride (solvent) of above-mentioned 45g (0.1mol) (I-19-c) crystal (reactant), within 45 minutes, adds, stir after one hour in this temperature, in 5 minutes, add 0.4mol NEt 33HF(reactant).Then at-70 ℃, in one hour, add 30ml methylene dichloride (solvent) solution of 0.4mol bromine (reactant), then at-70 ℃, continue reaction one hour, be warming up to 0 ℃, 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 21.3g(I-19), yield 45%, GC:99.8%.
The structural confirmation data of this product are as follows:
MP：56℃
MS：m/s%69(78.5)83(89.4)232(100)474(76.8)
1H-NMR：δ（ppm）1.28(m,4H),1.54(m,8H),2.08(m,1H),2.48(m,1H),3.65(m,4H)4.18(d,1H),6.83(m,2H),7.27（m,2H）7.66(m,1H)；
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:
△ε：18.0（20℃，589nm）
△n：0.18（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:
Figure BDA0000480146110000231
Figure BDA0000480146110000241
Figure BDA0000480146110000251
Figure BDA0000480146110000271
Embodiment 4, liquid crystal compound a
According to following weight part, each component is mixed, obtains liquid crystal compound a provided by the invention:
Figure BDA0000480146110000272
Figure BDA0000480146110000281
The performance perameter of this liquid crystal compound a is as follows:
CP：97℃；△n：0.110；△ε：6.5；γ 1：68；
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:
Figure BDA0000480146110000282
Figure BDA0000480146110000291
The performance perameter of this liquid crystal compound g is as follows:
CP：88℃；△n：0.105；△ε：4.2；γ 1：65；
With liquid crystal compound a contrast, if do not add compound shown in formula I provided by the invention, the Δ 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:
Figure BDA0000480146110000301
The performance perameter of this liquid crystal compound b is as follows:
CP：85℃；△n：0.100；△ε：6.5；γ 1：66；
As from the foregoing, this mixture 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, obtains liquid crystal compound c provided by the invention:
Figure BDA0000480146110000302
Figure BDA0000480146110000311
The performance perameter of this liquid crystal compound c is as follows:
CP：95℃；△n：0.085；△ε：6.0；γ 1：75；
As from the foregoing, this mixture 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:
Figure BDA0000480146110000312
Figure BDA0000480146110000321
The performance perameter of this liquid crystal compound d is as follows:
CP：95℃；△n：0.100；△ε：7.8；γ 1：58；
As from the foregoing, this mixture 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, obtains liquid crystal compound e provided by the invention:
Figure BDA0000480146110000322
Figure BDA0000480146110000331
The performance perameter of this liquid crystal compound e is as follows:
CP：103℃；△n：0.0105；△ε：7.2；γ 1：68；
As from the foregoing, this mixture 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:
Figure BDA0000480146110000332
Figure BDA0000480146110000341
Figure BDA0000480146110000351
The performance perameter of this liquid crystal compound f is as follows:
CP：90℃；△n：0.110；△ε：7.6；γ 1：65；
As from the foregoing, this mixture 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,
Figure FDA0000480146100000011
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 or deuterium and group;
Figure FDA0000480146100000012
all be selected from least one in singly-bound and following radicals:
Figure FDA0000480146100000013
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,
Figure FDA0000480146100000014
the group representing is identical or different,
Figure FDA0000480146100000015
the group representing is identical or different,
Figure FDA0000480146100000016
the group representing is identical or 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:
Figure FDA0000480146100000017
Figure FDA0000480146100000021
Described formula I-1 to formula I-4, R 1, R 2, Z 1,
Figure FDA0000480146100000022
definition respectively with claim 1 in R 1, R 2, Z 1,
Figure FDA0000480146100000023
definition identical;
Described
Figure FDA0000480146100000024
definition with
Figure FDA0000480146100000025
definition identical;
Compound shown in described formula I is specially formula I-8 to any one in compound shown in I-16:
Figure FDA0000480146100000026
Figure FDA0000480146100000031
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:
Figure FDA0000480146100000032
Figure FDA0000480146100000041
Described formula II to formula IV, R 1, R 2and R 3all 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 1all be 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, Y, U and V are all selected from any one in H and F;
D is 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 0-30:5-60:5-60:3-45; And the quality of compound shown in described formula I is not 0.
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.
CN201410107774.4A 2014-03-21 2014-03-21 2-methyl-1,3-dioxepane derivative Pending CN103880814A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410107774.4A CN103880814A (en) 2014-03-21 2014-03-21 2-methyl-1,3-dioxepane derivative

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410107774.4A CN103880814A (en) 2014-03-21 2014-03-21 2-methyl-1,3-dioxepane derivative

Publications (1)

Publication Number Publication Date
CN103880814A true CN103880814A (en) 2014-06-25

Family

ID=50949981

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410107774.4A Pending CN103880814A (en) 2014-03-21 2014-03-21 2-methyl-1,3-dioxepane derivative

Country Status (1)

Country Link
CN (1) CN103880814A (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110233463A1 (en) * 2008-09-17 2011-09-29 Tetragon Lc Chemie Ag Chiral compounds, cholesteric and ferroelectric liquid crystal compositions comprising these chiral compounds, and liquid crystal displays comprising these liquid crystal compositions
CN102307967A (en) * 2009-02-06 2012-01-04 默克专利股份有限公司 Liquid crystalline medium and liquid crystal display
CN103467253A (en) * 2012-09-24 2013-12-25 石家庄诚志永华显示材料有限公司 Cycloheptane derivative as well as preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110233463A1 (en) * 2008-09-17 2011-09-29 Tetragon Lc Chemie Ag Chiral compounds, cholesteric and ferroelectric liquid crystal compositions comprising these chiral compounds, and liquid crystal displays comprising these liquid crystal compositions
CN102307967A (en) * 2009-02-06 2012-01-04 默克专利股份有限公司 Liquid crystalline medium and liquid crystal display
CN103467253A (en) * 2012-09-24 2013-12-25 石家庄诚志永华显示材料有限公司 Cycloheptane derivative as well as preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN103333139B (en) One class contains the liquid crystalline cpd of tetrahydrofuran (THF) structure
KR102250503B1 (en) A compound, a liquid crystal medium containing the same, and a liquid crystal mixture, a liquid crystal display material, or a method of manufacturing an electro-optical display material
CN103058968B (en) Liquid crystalline cpd containing the sub-methoxyl group bridge of cumarone and difluoro and preparation method thereof and application
CN103602337B (en) Cyclohexane derivatives, preparation method thereof and applications thereof
CN103467253B (en) Cycloheptane derivative and preparation method thereof and application
CN102627534B (en) Compounds including indene and difluoroethylene bridge bond, preparation method thereof and application thereof
CN103320144B (en) Liquid crystalline cpd containing coumaran and preparation method thereof and application
TW201139354A (en) Liquid-crystalline compounds and liquid-crystalline media
CN103694214A (en) Dioxane derivatives as well as preparation method and application thereof
CN103772138A (en) Liquid crystal monomer containing deuterium substitution
CN105294526A (en) High-birefringence liquid crystal compound, preparing method and composition of high-birefringence liquid crystal compound
CN103058886B (en) Poly-fluorine poly-cyanogen liquid crystal compound as well as preparation method and application thereof
CN103333146A (en) Liquid crystal compounds containing 2-alkyltetrahydropyrane structure, and preparation method and application thereof
CN103787845A (en) Deuterium-substituted difluoro-oxymethane derivative
CN103724168A (en) Difluoro methoxy bond derivative containing deuterium as well as preparation method and application of derivative
CN103664868A (en) Oxathiane derivative as well as preparation method and application thereof
CN103058836A (en) Liquid crystal compound containing indan and difluoro methylenedioxy bridge, as well as preparation method and application thereof
CN103058947A (en) Liquid crystal compound containing benzoxazole and difluoromethylenedioxy bridged linkage and preparation method and application thereof
CN103880810A (en) Oxepane derivative
CN105418362B (en) A kind of compound, liquid-crystal composition and liquid crystal display
CN103467251B (en) Adamantane derivative and preparation method thereof and application
CN103319444B (en) Liquid crystalline cpd containing 4-tetrahydropyrans structure and preparation method thereof and application
CN103087038A (en) Liquid crystal compound containing benzo-1, 3-dioxolane and difluoro-methylenedioxy bridge
CN103087037B (en) Liquid crystalline cpd containing the sub-methoxyl group linking group of DOX and difluoro and preparation method thereof and application
JP6166313B2 (en) Liquid crystal compound, liquid crystal composition, and liquid crystal display device

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C12 Rejection of a patent application after its publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20140625