CN103694214A - Dioxane derivatives as well as preparation method and application thereof - Google Patents
Dioxane derivatives as well as preparation method and application thereof Download PDFInfo
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- CN103694214A CN103694214A CN201310733010.1A CN201310733010A CN103694214A CN 103694214 A CN103694214 A CN 103694214A CN 201310733010 A CN201310733010 A CN 201310733010A CN 103694214 A CN103694214 A CN 103694214A
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- 0 CSc1ccc(*)cc1 Chemical compound CSc1ccc(*)cc1 0.000 description 4
- QRMPKOFEUHIBNM-UHFFFAOYSA-N CC1CCC(C)CC1 Chemical compound CC1CCC(C)CC1 QRMPKOFEUHIBNM-UHFFFAOYSA-N 0.000 description 2
- HQAUIACBEMLEDY-UHFFFAOYSA-N CC(C1)C#CC(C)C1F Chemical compound CC(C1)C#CC(C)C1F HQAUIACBEMLEDY-UHFFFAOYSA-N 0.000 description 1
- JYCSPTKUCPKTSR-UHFFFAOYSA-N CC(CCC=C1C)C(F)=C1F Chemical compound CC(CCC=C1C)C(F)=C1F JYCSPTKUCPKTSR-UHFFFAOYSA-N 0.000 description 1
- QFZFKXVGQIODJN-UHFFFAOYSA-N CC1C=CC(C)=CC1 Chemical compound CC1C=CC(C)=CC1 QFZFKXVGQIODJN-UHFFFAOYSA-N 0.000 description 1
- RPMUDXVQHUECRE-UHFFFAOYSA-N CC1COC(C)OC1 Chemical compound CC1COC(C)OC1 RPMUDXVQHUECRE-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
- C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes 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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- 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
- C09K2019/3422—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a six-membered ring
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- Crystallography & Structural Chemistry (AREA)
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- Nonlinear Science (AREA)
- Mathematical Physics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Liquid Crystal Substances (AREA)
Abstract
The invention discloses a liquid crystal compound containing dioxane derivatives. The compound has a general structural formula as shown in a formula I, is more stable in structure, wide in liquid crystal state temperature range, better in low-temperature intersolubility and larger in dielectric anisotropy delta epsilon, can achieve lower threshold voltage and low rotary viscosity gamma 1 during the use of an optical device and improve the performance of a liquid crystal composition and a display, and has great significance to quick response of the display. The liquid crystal composition containing the compound can be applied to preparation of the liquid crystal display with low drive voltage, wide temperature range and high response speed.
Description
Technical field
The invention belongs to liquid crystalline cpd and synthesize and Application Areas, relate to a kind of dioxane derivatives and preparation method thereof and application.
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, along with developing rapidly of modern display technology, liquid-crystal display has experienced after twisted nematic (TN) type, supertwist nematic phase (STN), and Thin Film Transistor-LCD (TFT-LCD) has become the Developing mainstream of flat pannel display.High-quality TFT-LCD requires high-contrast, high definition, high-speed response, high brightness and wide viewing angle.In addition, also require low power consumption.Therefore, require liquid crystal material must there is wider nematic temperature range, low liquid crystal viscosity, high voltage retention, suitable double refractive inde, high dielectric anisotropy and good with the intermiscibility of other liquid crystalline cpds.
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 also without any single liquid crystal monomer, be used in liquid-crystal display separately 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 dioxane derivatives and preparation method thereof and application.
Dioxane derivatives 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, the alkyl of C1-C15 is, at least one in the alkene oxygen base of the thiazolinyl of the alkoxyl group of C1-C15, C2-C15 and C2-C15;
B, contain-CH
2-described group a at least one-CH
2-by least one replacement in following group and Sauerstoffatom, be not directly connected 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, replaced and group;
Z
1, Z
2, Z
3and Z
4all 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, c and d are all selected from the integer of 0-3, and a+b+c+d≤5;
When a, b, c, d are 2 or 3,
the group representing is identical or different,
the group representing is identical or different,
the group representing is identical or different,
the group representing is identical or different.
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-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-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 be specifically selected from the thiazolinyl of C3-C15, the thiazolinyl of the thiazolinyl of C4-C15, C5-C15, the thiazolinyl of the thiazolinyl of C6-C15, C1-C6, the thiazolinyl of the thiazolinyl of C2-C6, C3-C6, the thiazolinyl of the thiazolinyl of C4-C6, C5-C6, the thiazolinyl of the thiazolinyl of C2-C5, C3-C5, the thiazolinyl of the thiazolinyl of C4-C5, C2-C4, the thiazolinyl of the thiazolinyl of C3-C4, C2-C10, at least one in the thiazolinyl of the thiazolinyl of C3-C10, C2-C8 and the thiazolinyl of C2-C3;
The alkene oxygen base of described C2-C15 be specifically selected from the alkene oxygen base of C3-C15, the alkene oxygen base of the alkene oxygen base of C4-C15, C5-C15, the alkene oxygen base of the alkene oxygen base of C6-C15, C2-C6, the alkene oxygen base of the alkene oxygen base of C3-C6, C4-C6, the alkene oxygen base of the alkene oxygen base of C5-C6, C2-C5, the alkene oxygen base of the alkene oxygen base of C3-C5, C4-C5, the alkene oxygen base of the alkene oxygen base of C2-C4, C3-C4, the alkene oxygen base of the alkene oxygen base of C2-C10, C3-C10, at least one in the alkene oxygen base of the alkene oxygen base of C2-C8 and C2-C3;
Concrete, compound shown in described formula I be as shown in the formula I-1 to any one in formula I-16:
Described formula I-1 to formula I-16, R
1and R
2definition respectively with aforementioned R
1and R
2definition identical;
L
1, L
2, L
3, L
4, L
5, L
6, L
7and L
8all be selected from any one in hydrogen and fluorine.
Shown in described formula I-1, compound is specially
Shown in formula I-4, compound is specially
Shown in formula I-12, compound is specially
Compound shown in the formula I that the invention described above provides, its preparation method can be any one in following method one to four:
Wherein, when
z
2for-CF
2o-and c are the formula I of 0 o'clock, and its preparation method is as shown in method one:
When
z
3for-CF
2o-, c are 0 and Z
4formula I during for singly-bound, its preparation method is as shown in method two:
When
z
3for-CF
2o-, c are 0 and Z
4formula I during for singly-bound, its preparation method is as shown in method three:
When
z
2for-CF
2o-, c are 0 and Z
4formula I during for singly-bound, its preparation method is as shown in method four:
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 comprise formula II to compound shown in formula IV;
Certainly, this liquid crystal compound also can be only comprised of to compound shown in formula IV formula I;
Described formula II to formula IV, R
1, R
2and R
3all be selected from least one in halogen, the alkyl of-CN, C1-C7, the thiazolinyl of the alkoxyl group of C1-C7, cyclopentyl, suberyl, C2-C7 and the fluoroalkyl of C1-C5;
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;
Y
1and Y
2all be selected from least one in H and F;
P is the integer of 0-2, is specially 0 or 1 or 2;
P is 2 o'clock,
identical or different.
Concrete, described R
1, R
2and R
3in, the alkyl of C1-C7 is specially the alkyl of C1-C5 or the alkyl of the alkyl of C1-C4 or C1-C3 or the alkyl of the alkyl of C1-C2 or C2-C5 or the alkyl of the alkyl of C2-C4 or C2-C3 or the alkyl of the alkyl of C3-C5 or C3-C4 or the alkyl of C4-C5, is more specifically-C
2h
5or-C
4h
9or-C
3h
7or-CH
3;
The alkoxyl group of C1-C7 is specially the alkoxyl group of C1-C5 or the alkoxyl group of the alkoxyl group of C1-C4 or C1-C3 or the alkoxyl group of the alkoxyl group of C1-C2 or C2-C5 or the alkoxyl group of the alkoxyl group of C2-C4 or C2-C3 or the alkoxyl group of the alkoxyl group of C3-C5 or C3-C4 or the alkoxyl group of C4-C5, is more specifically-C
2h
5or-C
4h
9or-C
3h
7or-CH
3;
The thiazolinyl of C2-C7 is specially the thiazolinyl of C2-C5 or the thiazolinyl of the alkenyl of C2-C4 or C2-C3 or the thiazolinyl of the thiazolinyl of C3-C5 or C3-C4 or the thiazolinyl of C4-C5, is more specifically-C
2h
4or-C
4h
8or-C
3h
6;
The fluoroalkyl of C1-C5 is specially the fluoroalkyl of C1-C5 or the fluoroalkyl of the fluoroalkyl of C1-C4 or C1-C3 or the fluoroalkyl of the fluoroalkyl of C1-C2 or C2-C5 or the fluoroalkyl of the fluoroalkyl of C2-C4 or C2-C3 or the fluoroalkyl of the fluoroalkyl of C3-C5 or C3-C4 or the fluoroalkyl of C4-C5;
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 is 0-40:4-50:5-50:3-45 to the mass ratio of compound shown in formula IV, and the quality of compound shown in described formula I is not 0;
Described formula I is specially 8-19:20-36:31-50:5-33 or 9-12:24-36:31-40:17-32 to the mass ratio of compound shown in formula IV;
Above-mentioned liquid-crystal composition is specially following liquid-crystal composition a, b, c, d or e:
Described liquid-crystal composition a comprises the component of following each mass parts or is comprised of the component of following each mass parts:
Described liquid-crystal composition a is specifically by comprising the component of following each mass parts or being comprised of the component of following each mass parts:
Described liquid-crystal composition b comprises the component of following each mass parts or is comprised of the component of following each mass parts:
Described liquid-crystal composition b is specifically by comprising the component of following each mass parts or being comprised of the component of following each mass parts:
Described liquid-crystal composition c comprises the component of following each mass parts or is comprised of the component of following each mass parts:
Described liquid-crystal composition c is specifically by comprising the component of following each mass parts or being comprised of the component of following each mass parts:
Described liquid-crystal composition d comprises the component of following each mass parts or is comprised of the component of following each mass parts:
Described liquid-crystal composition d is specifically by comprising the component of following each mass parts or being comprised of the component of following each mass parts:
Described liquid-crystal composition e comprises the component of following each mass parts or is comprised of the component of following each mass parts:
Described liquid-crystal composition e is specifically by comprising the component of following each mass parts or being comprised of the component of following each mass parts:
In addition; application and the liquid crystal display device material that comprises compound shown in formula I or described liquid crystal compound or electrooptics display material or the electrooptics liquid-crystal display in preparing liquid crystal display device material or electrooptics display material or electrooptics liquid-crystal display of compound or liquid crystal compound shown in the formula I that the invention described above provides, also belongs to protection scope of the present invention.Wherein, described electrooptics liquid-crystal display is TN escope, VA escope, IPS escope or PDLC escope.
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, and good with other Compound Phase dissolubilities, especially this compound has low rotary viscosity γ
1characteristic with large dielectric anisotropy (△ ε >0).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
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described starting 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 CP represents clearing 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, GC-MS gained mass spectrum and 1H-NMR to identify and confirms structural correctness.The HP6820 type gas chromatographicanalyzer of GCYou Agilent company is measured, 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, the micro-thermal analyzer of WRX-1S is used in fusing point test, 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: using compound itself as sample, measure 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, according to the extrapotation shown in following formula, calculate extrapolated value
The weight percent of extrapolated value=[100 * (measured value of sample)-(weight percent of parent liquid crystal) * (measured value of parent liquid crystal)]/compound,
Thereby 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 standard of the industry, referring to < < liquid crystal device handbook > > aircraft industry press, publishes.
The physical property measurement method of compound:
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, on one side with the heating of 3 ℃/min speed, utilize polarizing microscope to observe phase-state change on one side, thereby determine phase kind.
2. utilize the differential calorimetric of Mei Tele company to turn round scanner DSC822e, with speed intensification or the cooling 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 (η measures mPa.s at 20 ℃), is used E type rotary viscosity design determining.
3. optical anisotropy (specific refractory power anisotropy is measured △ n 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 (n
11) be when polarization direction is parallel with frictional direction, to measure institute's value, specific refractory power (n
⊥) be when polarization direction is vertical with frictional direction, to measure institute's value, the value of optical anisotropy (△ n) is by △ n=n
11-n
⊥calculate.
4. dielectric constant anisotropy (△ ε measures at 25 ℃) is measured by Hewlett-Packard's HP4284a LCR test set.Measure liquid crystal molecule in the DIELECTRIC CONSTANT ε of long axis direction
‖, measure liquid crystal molecule at the specific inductivity (ε of short-axis direction
⊥), dielectric anisotropy △ ε is by △ ε=ε
‖-ε
⊥calculate.
In measured value, when usining liquid crystalline cpd itself during as sample, record income value as experimental value, when usining the mixture of liquid crystalline cpd and parent liquid crystal during as sample, the value that record is obtained by extrapotation is as experimental value.
Embodiment 1,
synthetic (method one)
Step 1: I-17-a's is synthetic
In reaction flask, add 68g(1mol) sodium ethylate, 1L dehydrated alcohol, under stirring, add dimethyl malonate 132g (1mol) reflux 1 hour, 149g(1mol) cyclopentyl bromide (reactant) is added drop-wise in reaction flask, return stirring 2 hours, add 1L water, 1L normal heptane, processes according to a conventional method, merges organic phase and is spin-dried for solvent, underpressure distillation obtains product 160g, yield 80%.
Step 2: I-17-b's is synthetic
To 2L there-necked flask, add 38g lithium aluminum hydride, tetrahydrofuran (THF) 1L, stirs the lower 160g(0.8mol of dropping) I-17-a(reactant), heated and stirred back flow reaction 8 hours, cool to 0 ℃, splash into the solution that 105g Seignette salt and 300g water prepare, standing 10 minutes, pour out organic phase.Solvent evaporate to dryness obtains product 103.7g, yield 90%.
Step 3: I-17-c's is synthetic
To 1L there-necked flask, add 103.7g(0.72mol) I-11-b(reactant), 400ml toluene (solvent), the p-bromobenzaldehyde of 0.8mol, 5g tosic acid is opened heated and stirred, reflux water-dividing 4 hours, and reaction solution is washed to neutrality, add 100g anhydrous sodium sulfate drying, carry out column chromatography, be spin-dried for solvent, add dehydrated alcohol recrystallization to obtain product I-17-c138.8g, GC:95%, yield 62%.
Step 4: I-17-d's is synthetic
The I-17-c of 31.1g (0.1mol) is dissolved in the tetrahydrofuran (THF) (solvent) of 200ml and is cooled to-70 ℃. first drip the butyllithium (reactant) of 40ml2.5M (0.1mol), drip subsequently the trimethyl borate (reactant) of 13.5g (0.13mol) at the tetrahydrofuran solution of 50ml, at-60 ℃ of mixtures, stir 30 minutes, naturally be warming up to-20 ℃, add 2N hydrochloric acid 100ml, stir 1 hour, process according to a conventional method, thick product recrystallization in normal heptane, obtain 19.3g product, yield 70%.
Step 5: I-17-e's is synthetic
The I-17-d(reactant of 27.6g (0.1mol)) add in the tetrahydrofuran (THF) (solvent) of 300ml, add 50ml water 30ml30% hydrogen peroxide, at 45 ℃, stir 2 hours, mixture adds methylene dichloride 100ml, 200ml water is processed routinely, and thick product recrystallization in normal heptane, obtains product I-17-e22.3g, GC:99%, yield 90%.
Step 6: I-17-f's is synthetic
24.8g (0.1mol) I-17-e is dissolved in 200ml toluene (solvent) and adds 5g5%pd/C hydrogenation 10 hours under 0.25MPa, and conventional processing obtains product, obtains 22.9g product I-17-f, GC:98%, yield 90%.
Step 7: I-17-g's is synthetic
The butyllithium of 40ml2.5M (0.1mol) is added drop-wise to 19.2g(0.1mol at-70 ℃) 2-trimethyl silyl-1,3-dithiane is in the solution of 75ml tetrahydrofuran (THF) (solvent), mixture rises to 0 ℃ through the time of 4 hours., then be chilled to-70 ℃, the I-17-f of 25.4g (0.1mol) is dripped at the solution of the tetrahydrofuran (THF) of 250ml, mixture rises to room temperature, stirring 18 hours, carries out conventional aftertreatment.Crude product is recrystallization from normal heptane, obtains white crystal I-17-g32g, yield 90%.
Step 8: I-17's is synthetic
The trifluoromethayl sulfonic acid (reactant) of 15g (0.1mol) is added drop-wise to the I-17-g(reactant of 35.4g (0.1mol) at-20 ℃) in the solution of the methylene dichloride of 50ml, stir 30 minutes, then cooling-70 ℃. first add 3 of 19.2g (0.13mol), 4, the triethylamine of 5-trifluoromethyl phenol (reactant) and 30.3g (0.3mol), at the solution of the methylene dichloride of 20ml, adds 63.2g (0.4mol) NEt in 5 minutes
33HF(reactant).Then at-70 ℃, 30ml methylene dichloride (solvent) solution that adds 64g (0.4mol) bromine (reactant) in one hour, 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, by dripping about 45g32% aqueous sodium hydroxide solution, regulated pH value to 5～8 of reaction solution.After separatory, water extracts with 80ml methylene dichloride (solvent), merges organic phase and filters with 4g diatomite (discoloring agent), washing, the lower solvent evaporated of decompression.Sherwood oil (solvent) recrystallization after the crude product column chromatography obtaining, obtains white crystal product (I-17) 21.6g, yield 50%.
The structural confirmation data of this product are as follows:
GC：99.9%；
MS：m/s%434（M
+54.6）286(57.9)148(100)69(78.4)
1H-NMR：δ（ppm）
1.29(m,6H)1.53(m,12H)2.08(m,1H)2.48(m,1H)3.64(m,2H)3.88(m,2H)4.68(d,1H)6.89(m,2H)
As from the foregoing, this product structure is correct, is compound shown in formula I-17.
The liquid crystal property of this product is as follows:
MP：32.5℃；
△ε：13.6（25℃，589nm）；
△n：0.064（25℃，1000Hz）。
As from the foregoing, this compound has suitable fusing point, suitable optical anisotropy, and higher dielectric anisotropy, has good liquid crystal property.
Embodiment 2, compound
synthetic (method two)
In reaction flask, add 30.4g(0.11mol) (I-17-d) (reactant), 38.9g(0.1mol)
(reactant) (according to Peer.Kirsch et al., Angew.Chem.Int.Ed.2001.40.1480. is synthetic), tetrakis triphenylphosphine palladium 0.3g(catalyzer), sodium carbonate 15g(catalyzer), toluene 100ml(solvent), water 100ml, ethanol 100ml(solvent), reflux 4 hours, adds 100ml water, separatory, organic phase evaporate to dryness, through column chromatography, recrystallization obtains product 37.8g, yield 70%.
The structural confirmation data of this product are as follows:
GC：99.9%；
MS：m/s%540(M
+1.2)393(100)267(82.3)239(57.8)
1H-NMR：δ（ppm）
1.35(m,2H)1.56(m,8H)3.64(m,2H)3.88(m,2H)5.98(s,1H)6.89(m,2H)7.22(d,2H)7.40(m,4H)
As from the foregoing, this product structure is correct, is compound shown in formula I-18.
The liquid crystal property of this product is as follows:
MP：73℃
CP：146℃，151℃；
△ε：22.3（25℃，589nm）；
△n：0.129（25℃，1000Hz）。
As from the foregoing, this compound has suitable fusing point, suitable optical anisotropy, and higher dielectric anisotropy, has good liquid crystal property.
Embodiment 3,
synthetic (method three)
Step 1: I-19-a's is synthetic
In the there-necked flask of 500ml, add the 3-fluorobenzaldehyde (reactant) of 0.1mol I-17-b and 12.4g (0.1mol) in the solution of 250ml toluene (solvent), then add 2g tosic acid, mixture stirring and refluxing 3 hours, cools to 20 ℃ naturally, adds 50ml water, separatory, organic phase is with after 4 * 50ml washing, and solvent evaporated, obtains I-19-a
Step 2: I-19-b's is synthetic
By 40ml2.5M(0.1mol) butyllithium (reactant) at-60 ℃, be added drop-wise to 25g (0.1mol) I-19-a (reactant) 11.2g (0.1mol) potassium tert.-butoxide (reactant) in the solution of 250ml tetrahydrofuran (THF) (solvent), then drip 13.5g (0.13mol) trimethyl borate (reactant) at the solution of 50ml tetrahydrofuran (THF) (solvent), at-60 ℃ of mixtures, stir 30 minutes, naturally be warmed up to-20 ℃, add 50ml water, 10ml concentrated hydrochloric acid, stir 30 minutes, separatory, organic phase is with after 4 * 50ml washing, solvent evaporated, obtains I-19-b;
Step 3: I-19's is synthetic
In reaction flask, add 32.3g(0.11mol) (I-19-b) (reactant), 38.9g(0.1mol)
(reactant) (according to Peer.Kirsch et al., Angew.Chem.Int.Ed.2001.40.1480. is synthetic), tetrakis triphenylphosphine palladium 0.3g(catalyzer), sodium carbonate 15g(catalyzer), toluene 100ml(solvent), water 100ml, ethanol 100ml(solvent), reflux 4 hours, adds 100ml water, separatory, organic phase evaporate to dryness, through column chromatography, recrystallization obtains product 41.8g, yield 75%.
The structural confirmation data of this product are as follows:
GC：99.9%；
MS：m/s%588(M
+1.1)411(100)285(81.4)257(61.0)；
1H-NMR：δ（ppm）
1.35(m,2H)1.56(m,8H)3.64(m,2H)3.88(m,2H)5.98(s,1H)6.89(m,2H)6.96(d,1H)7.19(d,1H)7.22(d,2H)7.70(m,1H)
As from the foregoing, this product structure is correct, is compound shown in formula I-19.
The liquid crystal property of this product is as follows:
MP：65℃；
CP：85℃；
△ε：22.3（25℃，589nm）；
△n：0.129（25℃，1000Hz）。
As from the foregoing, this compound has suitable fusing point, suitable optical anisotropy, and higher dielectric anisotropy, has good liquid crystal property.
Embodiment 4,
synthetic (method four)
Step 1: I-20-a's is synthetic
In the there-necked flask of 500ml, add 3 of 0.1mol I-17-b and 14.2g (0.1mol), 5-difluorobenzaldehyde (reactant), in the solution of 250ml toluene (solvent), then adds 2g tosic acid, mixture stirring and refluxing 3 hours, naturally cool to 20 ℃, add 50ml water, separatory, organic phase is with after 4 * 50ml washing, solvent evaporated, obtains I-20-a.
Step 2: I-20-b's is synthetic
By 40ml2.5M(0.1mol) butyllithium (reactant) at-60 ℃, be added drop-wise to 26.8g (0.1mol) I-14-a (reactant) 11.2g (0.1mol) potassium tert.-butoxide (reactant) in the solution of 250ml tetrahydrofuran (THF) (solvent), then drip 27.3g (0.13mol) difluorodibromomethane (reactant) at the solution of 50ml tetrahydrofuran (THF) (solvent), at-60 ℃ of mixtures, stir 30 minutes, naturally be warmed up to-20 ℃, add 50ml water, 10ml concentrated hydrochloric acid, stir 30 minutes, separatory, organic phase is with after 4 * 50ml washing, solvent evaporated, obtains I-20-b.
Step 3: I-20's is synthetic
In reaction flask, add 39.7g(0.1mol) (I-14-d) (reactant), 14.8g(0.1mol)
(reactant), sodium carbonate 15g(catalyzer), DMF 300ml(solvent), 60 ℃ of stirring reactions are 4 hours, be cooled to 30 ℃, add 100ml water, 20ml concentrated hydrochloric acid, 200ml toluene, separatory, organic phase evaporate to dryness, through column chromatography, recrystallization obtains product 32.5g, yield 70%.
The structural confirmation data of this product are as follows:
GC：99.9%；
MS：m/s%464(M
+0.5)317(100)191(17.0)163(38.5)67(41.6)；
1H-NMR：δ（ppm）
1.50(m,10H)3.63(d,2H)3.88(d,2H)5.98(s,1H)6.23(m,2H)6.60(d,2H)
As from the foregoing, this product structure is correct, is compound shown in formula I-20.
The liquid crystal property of this product is as follows:
MP：76℃；
△ε：21.3（25℃，589nm）；
△n：0.125（25℃，1000Hz）。
As from the foregoing, this compound has suitable fusing point, suitable optical anisotropy, and higher dielectric anisotropy, has good liquid crystal property.
With reference to the method for above-described embodiment 1-4, only according to substituent definition in product, replace the substituting group in respective reaction thing, 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：89℃；△n：0.105；△ε：8.0；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.
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：94℃；△n：0.115；△ε：9.0；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 6, liquid crystal compound c
According to following weight part, each component is mixed, obtains liquid crystal compound c provided by the invention:
The performance perameter of this liquid crystal compound c is as follows:
cp：87℃；△n：0.105；△ε：7.2；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.
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：97℃；△n：0.112；△ε：8.7；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.
Embodiment 8, liquid crystal compound e
According to following weight part, each component is mixed, obtains liquid crystal compound e provided by the invention:
The performance perameter of this liquid crystal compound e is as follows:
cp：95℃；△n：0.110；△ε：7.5；γ
1：70；
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,
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, the alkyl of C1-C15 is, at least one in the alkene oxygen base of the thiazolinyl of the alkoxyl group of C1-C15, C2-C15 and C2-C15;
B, contain-CH
2-described group a at least one-CH
2-by least one replacement in following group and Sauerstoffatom, be not directly connected 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, replaced and group;
Z
1, Z
2, Z
3and Z
4all 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, c and d are all selected from the integer of 0-3, and a+b+c+d≤5;
When a, b, c, d are 2 or 3,
the group representing is identical or different,
the group representing is identical or different,
the group representing is identical or different,
the group representing is identical or different.
2. compound according to claim 1, is characterized in that: compound shown in described formula I for as shown in the formula I-1 to any one in formula I-16:
Described formula I-1 to formula I-15, R
1and R
2definition respectively with claim 1 in R
1and R
2definition identical;
L
1, L
2, L
3, L
4, L
5, L
6, L
7and L
8all be selected from any one in hydrogen and fluorine.
3. the liquid crystal compound that comprises 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
1, R
2and R
3all be selected from least one in halogen, the alkyl of-CN, C1-C7, the thiazolinyl of the alkoxyl group of C1-C7, cyclopentyl, suberyl, C2-C7 and the fluoroalkyl of C1-C5;
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;
Y
1and Y
2all be selected from least one in H and F;
P is the integer of 0-2;
P is 2 o'clock,
identical or different.
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 0-40:4-50:5-50:3-45; Wherein, 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 application of the arbitrary described liquid crystal compound of claim 3-5 in preparing 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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| CN103820127A (en) * | 2014-01-25 | 2014-05-28 | 石家庄诚志永华显示材料有限公司 | Positive dielectric liquid crystal composition |
| CN103923662A (en) * | 2014-04-03 | 2014-07-16 | 石家庄诚志永华显示材料有限公司 | Dielectric positive liquid-crystal composition |
| CN104045527A (en) * | 2014-04-23 | 2014-09-17 | 石家庄诚志永华显示材料有限公司 | Difluoromethoxy-bridged derivative and preparation method and application |
| 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 |
| CN104830347A (en) * | 2015-04-14 | 2015-08-12 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal compound containing 4,6-dimethyl-1,3-dioxane ring, preparation method and applications thereof |
| CN105481824A (en) * | 2014-09-16 | 2016-04-13 | 石家庄诚志永华显示材料有限公司 | Liquid crystal compound containing 5-cyclobutyl-1,3-dioxy cyclohexane structure, preparation method and applications thereof |
| US9422477B2 (en) | 2014-10-29 | 2016-08-23 | Samsung Display Co., Ltd. | Liquid crystal compositon and liquid crystal display including the same |
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| CN103820127A (en) * | 2014-01-25 | 2014-05-28 | 石家庄诚志永华显示材料有限公司 | Positive dielectric liquid crystal composition |
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| CN103923662A (en) * | 2014-04-03 | 2014-07-16 | 石家庄诚志永华显示材料有限公司 | Dielectric positive liquid-crystal composition |
| CN103923662B (en) * | 2014-04-03 | 2015-10-28 | 石家庄诚志永华显示材料有限公司 | A kind of Dielectric positive liquid crystal composition |
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| CN105481824A (en) * | 2014-09-16 | 2016-04-13 | 石家庄诚志永华显示材料有限公司 | Liquid crystal compound containing 5-cyclobutyl-1,3-dioxy cyclohexane structure, preparation method and applications thereof |
| US9422477B2 (en) | 2014-10-29 | 2016-08-23 | Samsung Display Co., Ltd. | Liquid crystal compositon and liquid crystal display including the same |
| 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 |
| CN104830347A (en) * | 2015-04-14 | 2015-08-12 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal compound containing 4,6-dimethyl-1,3-dioxane ring, preparation method and applications thereof |
| US9567525B2 (en) | 2015-04-30 | 2017-02-14 | Samsung Display Co., Ltd. | Liquid crystal composition, liquid crystal display including the same and method of manufacturing thereof |
| CN110376302A (en) * | 2019-07-17 | 2019-10-25 | 深圳海王医药科技研究院有限公司 | The method of fluorobenzaldehyde and fluorobenzene cinnamic acid between a kind of detection of gas chromatography-mass spectrography |
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