CN103664868A - Oxathiane derivative as well as preparation method and application thereof - Google Patents
Oxathiane derivative as well as preparation method and application thereof Download PDFInfo
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- CN103664868A CN103664868A CN201310616007.1A CN201310616007A CN103664868A CN 103664868 A CN103664868 A CN 103664868A CN 201310616007 A CN201310616007 A CN 201310616007A CN 103664868 A CN103664868 A CN 103664868A
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- C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
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- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3491—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having sulfur as hetero atom
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- 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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- 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
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Abstract
The invention discloses an oxathiane derivative as well as a preparation method and an application thereof. A general formula of a structure of the compound is represented by the formula I. The compound has a more stable structure, wide liquid crystal temperature range, better low-temperature intersolubility and larger dielectric anisotropy delta epsilon, lower threshold voltage and low rotary viscosity gamma 1 can be achieved during use of an optical element, performance of a liquid crystal mixture material and a display can be improved, and accordingly, the compound is greatly significant in realization of quick response of the display; and a liquid crystal mixture containing the compound can be applied to preparation of a liquid crystal display which is low in driving voltage, wide in temperature range and high in response speed.
Description
Technical field
The invention belongs to liquid crystalline cpd and synthesize and Application Areas, relate to a kind of oxathiane derivative and preparation method thereof and application.
Background technology
Use the liquid-crystal display of liquid crystal compound to be widely used in instrument, computer, in the indicating meters such as TV.For technical field of liquid crystal display, although market is very huge in recent years, technology is also ripe gradually, and people also in continuous raising, are especially realizing response fast to the requirement of technique of display, reduce driving voltage to 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 improving the performance of 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 compound 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
As the liquid crystal material that shows use, obtain very great development, occurred a large amount of liquid crystalline cpds.From biphenyl nitrile, ester class, oxygen heterocyclic ring class, pyrimidine lopps liquid crystalline cpd, 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., constantly meet the display performance requirements such as TN, STN, TFT-LCD.
Any demonstration all requires wider liquid crystal state temperature with liquid crystal compound, 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.
Summary of the invention
The object of this invention is to provide a kind of oxathiane derivative and preparation method thereof and application.
Liquid crystalline cpd containing oxathiane provided by the invention, its general structure is suc as formula shown in I,
In described formula I, R
1and R
2for group shown in following A or 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, by described A containing-CH
2-any group in one or at least two non-conterminous-CH
2-by least one replacement in following group and and Sauerstoffatom not directly connected group :-CH=CH-,-C ≡ C-,-COO-,-OOC-, tetramethylene ,-O-and-S-;
C, at least one hydrogen in arbitrary group in described A or B is replaced by fluorine or chlorine and group;
all be selected from any one in singly-bound and following radicals:
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, c and d are the integer of 0-3, and a+b+c+d≤5;
A or b or c or d are 2 or 3 o'clock,
with
the group representing is all identical or different.
In above-mentioned formula I, 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 is as shown in the formula any one in I-1 to I-6:
In described formula I-1 to I-6, R
1, R
2,
definition as hereinbefore;
Compound shown in described formula I-1 is specially compound shown in formula I-7 or formula I-8:
Shown in described formula I-7, compound is specially compound shown in formula I-15:
Shown in described formula I-2, compound is specially compound shown in formula I-9:
Shown in described formula I-3, compound is specially compound shown in formula I-10:
Compound shown in described formula I-4 is specially compound shown in formula I-11 or formula I-12:
Shown in described formula I-11, compound is specially compound shown in formula I-16:
Shown in described formula I-5, compound is specially compound shown in formula I-13:
Shown in described formula I-6, compound is specially compound shown in formula I-14:
In described formula I-7 to I-14, R
1and R
2definition as hereinbefore;
Wherein, R
1be specially the straight chained alkyl of hydrogen or C1-C10;
R
2be specially Cl, F ,-OCF
3,-CF
3or-OCHF
2;
L
1to L
8all be selected from any one in hydrogen and fluorine.
Shown in above-mentioned formula I, the preparation method of compound can be method shown in method one or two:
Wherein, the flow process of method one is as follows:
The method one specifically comprises the steps:
1) by 1mol
the hydrobromic acid aqueous solution that is 48% with 2mol mass percentage concentration under sulphuric acid catalysis 80 ℃ react and obtain for 48 hours
after, then with 1.1mol thiocarbamide back flow reaction 6 hours in ethanol, obtain
2) by 1mol
with 1mol
in toluene solvant, mix, then 8.3g tosic acid does under the condition of catalyzer, reflux and carry out dehydration reaction 4 hours, react complete and obtain
after, then by gained
tetrahydrofuran solution cool to-70 ℃ to-60 ℃, add the butyllithium of 1mol, after adding, in-50 ℃ of reactions 30 minutes, then be cooled to-60 ℃ and add 1.3mol trimethyl borate to mix to react 1 hour, rise to room temperature and add 2mol hydrochloric acid reaction 20 minutes,
3) by step 2) gained 1.1mol
with 1mol
150g carbonate, 3g tetra-triphenylphosphines close palladium and mix and carry out back flow reaction 4 hours in the mixed solution being mixed with equal-volume by toluene, second alcohol and water, react complete and obtain
The flow process of method two is as follows:
The method two specifically comprises the steps:
1) by 1mol
with 1mol
in toluene solvant, mix, 8.3g tosic acid is done under the condition of catalyzer, refluxes and carries out dehydration reaction 4 hours, reacts complete and obtains
after, then by gained 1mol
with equal-volume, mix in second alcohol and water with 50g sodium hydroxide and mixed solution in back flow reaction 4 hours, react complete and add hcl acidifying to obtain after being cooled to room temperature
2) by step 1) gained 1mol
in reflux in toluene, carry out dehydration reaction to reacting complete with 1.3mol dimercaptopropane, 1.3mol trifluoromethanesulfonic acid, obtain
again with 1mol
under 1mol triethylamine, 4mol hydrogen fluoride triethylamine and 4mol bromine, in-70 ℃ of reactions, after 2 hours, react complete and obtain
In addition, the liquid crystal compound that comprises the formula I compound that the invention described above provides, also belongs to protection scope of the present invention.
The present invention also provides a kind of liquid crystal compound, and this mixture comprises compound shown in formula I, formula II at least one in shown in formula IV:
Described formula II to formula IV, R
1, R
2and R
3all be selected from least one in hydrogen, halogen, the alkyl of-CN, C1-C7, the thiazolinyl of the alkoxyl group of C1-C7, 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.
Above-mentioned formula II is to formula IV, in above-mentioned formula I, the alkyl of described C1-C7 be specifically selected from the alkyl of C2-C7, the alkyl of the alkyl of C3-C7, C4-C7, the alkyl of the alkyl of C5-C7, C6-C7, the alkyl of the alkyl of C1-C6, C2-C6, the alkyl of the alkyl of C3-C6, C4-C6, the alkyl of the alkyl of C5-C6, C1-C5, the alkyl of the alkyl of C2-C5, C3-C5, the alkyl of the alkyl of C4-C5, C1-C4, the alkyl of the alkyl of C2-C4, C3-C4, at least one in the alkyl of the alkyl of C1-C3, C1-C2 and the alkyl of C2-C3;
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 fluoroalkyl of described C2-C5 be specifically selected from the fluoroalkyl of C3-C5, the fluoroalkyl of the fluoroalkyl of C4-C5, C2-C4, at least one in the fluoroalkyl of the fluoroalkyl of C3-C4 and C2-C3;
Above-mentioned liquid crystal compound also can be comprised of at least one in compound shown in formula IV described formula I, formula II.
Shown in described formula I, the mass fraction of compound is 2-40 part, is specially 4-20 part, is more specifically 8,12,12.5,14,8-14,8-12 or 12-14 part;
Shown in described formula II, the mass parts of compound is 4-50 part, is specially 10-40 part, is more specifically 20,23,24,36,20-36,23-36,24-36,20-24,20-23 or 23-36 part;
Shown in described formula III, the mass parts of compound is 5-50 part, is specially 20-50 part, is more specifically 35,35.5,36,47,50,35-50,36-47 or 47-50 part;
Shown in described formula IV, the mass parts of compound is 3-45 part, is specially 10-40 part, is more specifically 13,16,17,32,33,13-33,16-32 or 17-33 part.
Concrete, above-mentioned liquid crystal compound is specially following liquid crystal compound a, b, c, d or e:
Described liquid crystal compound a comprises the component of following each mass parts or is comprised of the component of following each mass parts:
Described liquid crystal compound a specifically comprises the component of following each mass parts or is comprised of the component of following each mass parts:
Described liquid crystal compound b comprises the component of following each mass parts or is comprised of the component of following each mass parts:
Described liquid crystal compound b specifically comprises the component of following each mass parts or is comprised of the component of following each mass parts:
Described liquid crystal compound c comprises the component of following each mass parts or is comprised of the component of following each mass parts:
Described liquid crystal compound c specifically comprises the component of following each mass parts or is comprised of the component of following each mass parts:
Described liquid crystal compound d comprises the component of following each mass parts or is comprised of the component of following each mass parts:
Described liquid crystal compound d specifically comprises the component of following each mass parts or is comprised of the component of following each mass parts:
Described liquid crystal compound e comprises the component of following each mass parts or is comprised of the component of following each mass parts:
Described liquid crystal compound e specifically comprises the component of following each mass parts or is comprised of the component of following each mass parts:
Liquid crystal display material or electrooptics display material or the electrooptics liquid-crystal display of at least one shown in application in preparing liquid crystal display 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 and protection I in compound and 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 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 compound that contains compound shown in formula I, the temperature range of 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.
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.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:
1, using compound itself as sample, measure and compound is mixed as sample and measured with parent liquid crystal.
2, compound is mixed as the mode of Specimen Determination compound physical property with parent liquid crystal 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, thus draw the physical property of monomer liquid crystal compound.
In parent liquid crystal used, each component structure formula and quality percentage composition are 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: γ
1be illustrated in the rotary viscosity (cP) of measuring material at 20 ℃, use Toyo6254 comprehensive tester.
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 the mixture with liquid crystalline cpd and mother liquor crystalline substance, during as sample, the value that record is obtained by extrapotation is as experimental value.
Embodiment 1, compound
synthetic (method one) of (I-15)
Synthesizing of step 1 2-brooethyl amylalcohol (I-15-a)
In 1L there-necked flask, add 35.4g (0.3mol) 2-propyl group-1, ammediol (reactant), the hydrobromic acid aqueous solution (reactant) that 100g(0.6mol) mass percentage concentration is 48%, the 5g vitriol oil (catalyzer), adds 80 ℃ of reactions of 400ml normal hexane (solvent) 48 hours.Separatory after cooling, organic phase is washed to neutrality, the lower solvent evaporated of decompression, underpressure distillation obtains product.GC85%; Yield 80%.
Synthesizing of step 2 2-thiopurine methyltransferase amylalcohol (I-15-b)
Under nitrogen protection; 36.2g (0.2mol) 2-propyl group-3-bromopropyl alcohol (reactant); 16.7g(0.22mol) thiocarbamide (reactant) adds in 300ml ethanol and refluxes 6 hours; solvent evaporated; be precipitated thing and add extracted with diethyl ether, diethyl ether solution adds the sodium hydroxide solution of 200ml20% under protection of inert gas, to boil 2 hours.
After cooling by reaction mixture acidifying, and by extracted with diethyl ether three times, washing, dry, solvent evaporated, underpressure distillation obtains product.GC84% yield 85%.
Step 3
(I-15-c's) is synthetic
In 1L there-necked flask, add 44.4g(0.24mol) p-bromobenzaldehyde (reactant), the toluene (solvent) that 2-thiopurine methyltransferase amylalcohol 32.2g (0.24mol) (reactant) 400ml is dry, tosic acid 2g, reflux 4 hours, separates the water of generation, be cooled to room temperature, 100ml washing, solvent evaporated, 2 times of ethyl alcohol recrystallizations obtain compound (I-14-c) 43g, yield 60%, gas chromatographic purity 98%.
Step 4
(I-15-d's) is synthetic
In reaction flask, add 30.1g (0.1mol) (I-15-c) (reactant); 150ml tetrahydrofuran (THF) (solvent); logical nitrogen protection; be cooled to-60 ℃; drip sherwood oil (solvent) solution of 0.1mol 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 also separatory, washing organic phase, to neutral, after solvent evaporated, obtains compound (I-14-d) 21.2g, yield 80%, liquid chromatography purity 97%.
Step 5
synthesizing of (I-15)
In reaction flask, add 29.2g(0.11mol) (I-15-d) (reactant), 38.9g(0.1mol)
(reactant), tetra-triphenylphosphine palladium 0.3g(catalyzer), sodium carbonate 15g(catalyzer) and, 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 I, 37g yield 70%
Experimental result is as follows:
GC：99.9%
MP：68℃
MS：m/s%530(1.2),383(100),282(56),266(78),238(30),144(15)；
1H-NMR：δ（ppm）0.90(t,3H),1.30(m,4H),2.08(m,1H)2.40(m,2H),3.33(m,2H),5.17(s,1H),6.89(m,2H),7.22(d,2H),7.40(s,4H)；
As from the foregoing, this product structure is correct, is compound shown in formula I.
The liquid crystal property of this compound is as follows:
△ε：22.3（20℃，589nm）
△n：0.129（20℃，1000Hz）
γ
1：101。
As from the foregoing, this compound has larger specific inductivity, and moderate specific refractory power, and less viscosity, can be applicable in mixed liquid crystal.
Embodiment 2,
synthetic (method two) of (I-16)
Step 1:
(I-16-a's) is synthetic
In 1L there-necked flask, add 40.8g(0.24mol) 4-formyl radical methyl cyclohexanecarboxylaand (reactant), the dry toluene (solvent) of 2-thiopurine methyltransferase amylalcohol 32.2g (0.24mol) (reactant) 400ml of embodiment 1 step 2 gained, tosic acid 2g, reflux is carried out dehydration reaction 4 hours, separate the water of generation, be cooled to room temperature, 100ml washing, solvent evaporated toluene, add 200ml ethanol (solvent), 200ml water (solvent) 12g sodium hydroxide (reactant) reflux 4 hours, cool to room temperature, add concentrated hydrochloric acid 30ml(reactant) neutralize to obtain compound (I-16-a) 39.1g, yield 60%.
Step 2
In reaction flask, add 0.1mol (I-16-a), 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, being warming up to refluxes carries out dehydration reaction, separate the water of generation, after minute water purification, react complete, 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) (I-16 – b).
In reaction flask, add again 0.1mol3,4,5-trifluoromethyl phenol (reactant), the mixing solutions of 0.1mol triethylamine (reactant) and 130ml methylene dichloride (solvent) is also cooled to-70 ℃, drip the solution of the 120ml methylene dichloride (solvent) of above-mentioned 0.1mol (I-15 – b) crystal (reactant), within 45 minutes, add, in this temperature, stir after 1 hour, in 5 minutes, add 0.4mol NEt
33HF(reactant).Then at-70 ℃, 30ml methylene dichloride (solvent) solution that adds 0.4mol bromine (reactant) in 1 hour, then at-70 ℃, continue reaction 1 hour, be warming up to 0 ℃, reaction solution is poured in 32% 160ml aqueous sodium hydroxide solution (regulating 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-16) 19g, yield 45%, GC:99.9%.
MS：m/s%424(23),276(50),144(48),70(56),55(100),42(47)；
1H-NMR：δ（ppm）0.90(t,3H),1.29(m,8H),1.52(m,4H)2.05(m,2H),2.40(m,3H),3.33(m,2H),3.87(d,1H),6.89(m,2H),
MP：50.5℃
As from the foregoing, this product structure is correct, is compound shown in formula I.
The liquid crystal property of this compound is as follows:
△ε：21.3（20℃，589nm）
△n：0.094（20℃，1000Hz）。
γ
1：112。
As from the foregoing, this compound has larger specific inductivity and moderate specific refractory power, and less viscosity, can be applicable in mixed liquid crystal.
With reference to embodiment 1 and 2, only according to the group in the corresponding replacement reaction materil structure of the structural formula of product formula, obtain as shown in the formula compound shown in I:
Embodiment 3
According to each component and weight percentage shown in table 1, mix, obtain liquid crystal compound a provided by the invention;
The composition of table 1, liquid crystal compound a
The performance test results of this liquid crystal compound a is as shown in table 2:
The performance test results of table 2, liquid crystal compound a
As seen from table, this mixture has high clearing point, suitable optical anisotropy, and low rotary viscosity and faster response speed, in liquid-crystal display.
According to the proportioning of this each component of embodiment, only do not add
with
obtain liquid crystal compound f, the performance test results of this liquid crystal compound f is as shown in table 3:
The performance test results of table 3, liquid crystal compound f
As seen from table, if do not add compound
with
the specific inductivity of liquid crystal compound can reduce greatly.
Embodiment 4
According to each component and weight percentage shown in table 4, mix, obtain liquid crystal compound b provided by the invention;
The composition of table 4, liquid crystal compound b
The performance test results of this liquid crystal compound b is as shown in table 5:
The performance test results of table 5, liquid crystal compound b
As seen from table, this mixture has high clearing point, suitable optical anisotropy, and low rotary viscosity and faster response speed, in liquid-crystal display.
Embodiment 5
According to each component and weight percentage shown in table 6, mix, obtain liquid crystal compound c provided by the invention;
The composition of table 6, liquid crystal compound c
The performance test results of this liquid crystal compound c is as shown in table 7:
The performance test results of table 7, liquid crystal compound c
As seen from table, this mixture has high clearing point, suitable optical anisotropy, and low rotary viscosity and faster response speed, in liquid-crystal display.
Embodiment 6
According to each component and weight percentage shown in table 8, mix, obtain liquid crystal compound d provided by the invention;
The composition of table 8, liquid crystal compound d
The performance test results of this liquid crystal compound d is as shown in table 9:
The performance test results of table 9, liquid crystal compound d
As seen from table, this mixture has high clearing point, suitable optical anisotropy, and low rotary viscosity and faster response speed, in liquid-crystal display.
Embodiment 7
According to each component and weight percentage shown in table 10, mix, obtain liquid crystal compound e provided by the invention;
The composition of table 10, liquid crystal compound e
The performance test results of this liquid crystal compound e is as shown in table 11:
The performance test results of table 11, liquid crystal compound e
| Cp | 87℃ |
| Δn | 0.110 |
| Δε | 6.9 |
| γ 1 | 63 |
As seen from table, this mixture has high clearing point, suitable optical anisotropy, and low rotary viscosity and faster response speed, in liquid-crystal display.
Claims (10)
1. compound shown in formula I,
In described formula I, R
1and R
2for group shown in following A or 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, by described A containing-CH
2-any group in one or at least two non-conterminous-CH
2-by least one replacement in following group and and Sauerstoffatom not directly connected group :-CH=CH-,-C ≡ C-,-COO-,-OOC-, tetramethylene ,-O-and-S-;
C, at least one hydrogen in arbitrary group in described A or B is 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, c and d are the integer of 0-3, and a+b+c+d≤5;
A or b or c or d are 2 or 3 o'clock,
with
the group representing is all identical or different.
2. compound according to claim 1, is characterized in that: compound shown in described formula I is for as shown in the formula any one in I-1 to I-6:
In described formula I-1 to I-6, R
1, R
2,
definition identical with claim 1;
Compound shown in described formula I-1 is specially compound shown in formula I-7 or formula I-8:
Shown in described formula I-2, compound is specially compound shown in formula I-9:
Shown in described formula I-3, compound is specially compound shown in formula I-10:
Compound shown in described formula I-4 is specially compound shown in formula I-11 or formula I-12:
Shown in described formula I-5, compound is specially compound shown in formula I-13:
Shown in described formula I-6, compound is specially compound shown in formula I-14:
In described formula I-7 to I-14, R
1and R
2definition identical with claim 1;
Wherein, R
1be specially the straight chained alkyl of hydrogen or C1-C10;
R
2be specially Cl, F ,-OCF
3,-CF
3or-OCHF
2;
L
1to L
8all be selected from any one in hydrogen and fluorine.
3. the liquid crystal compound that comprises the arbitrary described formula I compound of claim 1 or 2.
4. a liquid crystal compound, comprises compound shown in the arbitrary described formula I of claim 1 or 2, formula II at least one in compound shown in formula IV:
Described formula II to formula IV, R
1, R
2and R
3all be selected from least one in hydrogen, halogen, the alkyl of-CN, C1-C7, the thiazolinyl of the alkoxyl group of C1-C7, 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 liquid crystal compound is comprised of at least one in compound shown in formula IV described formula I, formula II.
6. according to the liquid crystal compound described in claim 4 or 5, it is characterized in that: shown in described formula I, the mass fraction of compound is 2-40 part, be specially 4-20 part;
Shown in described formula II, the mass parts of compound is 4-50 part, is specially 10-40 part;
Shown in described formula III, the mass parts of compound is 5-50 part, is specially 20-50 part;
Shown in described formula IV, the mass parts of compound is 3-45 part, is specially 10-40 part.
7. according to the arbitrary described liquid crystal compound of claim 4-6, it is characterized in that: described liquid crystal compound is following liquid crystal compound a, b, c, d or e:
Described liquid crystal compound a comprises the component of following each mass parts or is comprised of the component of following each mass parts:
Described liquid crystal compound a specifically comprises the component of following each mass parts or is comprised of the component of following each mass parts:
Described liquid crystal compound b comprises the component of following each mass parts or is comprised of the component of following each mass parts:
Described liquid crystal compound b specifically comprises the component of following each mass parts or is comprised of the component of following each mass parts:
Described liquid crystal compound c comprises the component of following each mass parts or is comprised of the component of following each mass parts:
Described liquid crystal compound c specifically comprises the component of following each mass parts or is comprised of the component of following each mass parts:
Described liquid crystal compound d comprises the component of following each mass parts or is comprised of the component of following each mass parts:
Described liquid crystal compound d specifically comprises the component of following each mass parts or is comprised of the component of following each mass parts:
Described liquid crystal compound e comprises the component of following each mass parts or is comprised of the component of following each mass parts:
Described liquid crystal compound e specifically comprises the component of following each mass parts or is comprised of the component of following each mass parts:
8. compound shown in the arbitrary described formula I of claim 1-2 or the application of the arbitrary described liquid crystal compound of claim 3-7 in preparing liquid crystal display material or electrooptics display material or electrooptics liquid-crystal display.
9. comprise at least one liquid crystal display material or electrooptics display material or the electrooptics liquid-crystal display in compound shown in the arbitrary described formula I of claim 1-2 and the arbitrary described liquid crystal compound of claim 3-7.
10. indicating meter according to claim 8 or claim 9, is characterized in that: described electrooptics liquid-crystal display is TN escope, VA escope, IPS escope or PDLC escope.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2017079867A1 (en) * | 2015-11-09 | 2017-05-18 | Dic Corporation | Polymerizable compound and optically anisotropic body |
| US11186669B2 (en) | 2015-01-16 | 2021-11-30 | Dic Corporation | Polymerizable composition and optically anisotropic body using same |
| US11261378B2 (en) | 2014-12-25 | 2022-03-01 | Dic Corporation | Polymerizable compound and optically anisotropic object |
| US11697695B2 (en) | 2015-01-16 | 2023-07-11 | Dic Corporation | Polymerizable composition and optically anisotropic body using same |
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| CN101631759A (en) * | 2007-02-28 | 2010-01-20 | 智索株式会社 | Has CF 2O is in conjunction with five rings liquid crystalline cpd, liquid-crystal composition and the liquid crystal display device of base |
| CN102964226A (en) * | 2012-12-14 | 2013-03-13 | 石家庄诚志永华显示材料有限公司 | Liquid crystal compound containing cyclobutyl and difluoromethylenedioxy connecting radical as well as preparation method and application thereof |
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| CN101631759A (en) * | 2007-02-28 | 2010-01-20 | 智索株式会社 | Has CF 2O is in conjunction with five rings liquid crystalline cpd, liquid-crystal composition and the liquid crystal display device of base |
| CN102964226A (en) * | 2012-12-14 | 2013-03-13 | 石家庄诚志永华显示材料有限公司 | Liquid crystal compound containing cyclobutyl and difluoromethylenedioxy connecting radical as well as preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US11261378B2 (en) | 2014-12-25 | 2022-03-01 | Dic Corporation | Polymerizable compound and optically anisotropic object |
| US11186669B2 (en) | 2015-01-16 | 2021-11-30 | Dic Corporation | Polymerizable composition and optically anisotropic body using same |
| US11697695B2 (en) | 2015-01-16 | 2023-07-11 | Dic Corporation | Polymerizable composition and optically anisotropic body using same |
| WO2017079867A1 (en) * | 2015-11-09 | 2017-05-18 | Dic Corporation | Polymerizable compound and optically anisotropic body |
| JP2017088591A (en) * | 2015-11-09 | 2017-05-25 | Dic株式会社 | Polymerizable compound and optical anisotropic body |
| US10919870B2 (en) | 2015-11-09 | 2021-02-16 | Dic Corporation | Polymerizable compound and optically anisotropic body |
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