CN105295953A

CN105295953A - Liquid crystalline compound containing 1,3-dioxane difluoro methylene oxygen group and preparation method and application thereof

Info

Publication number: CN105295953A
Application number: CN201510755109.0A
Authority: CN
Inventors: 曹建华; 华瑞茂
Original assignee: Shijiazhuang Chengzhi Yonghua Display Material Co Ltd
Current assignee: Shijiazhuang Chengzhi Yonghua Display Material Co Ltd
Priority date: 2015-11-09
Filing date: 2015-11-09
Publication date: 2016-02-03
Anticipated expiration: 2035-11-09
Also published as: CN105295953B

Abstract

The invention discloses a liquid crystalline compound containing a 1,3-dioxane difluoro methylene oxygen group and a preparation method and application thereof. In the compound molecular structure shown in the formula I, the liquid crystalline compound containing the 1,3-dioxane difluoro methylene oxygen linking group has higher dielectric anisotropy, and more importantly, the extremely high response speed, a clearing point and the lower rotary viscosity are achieved simultaneously. For blending a liquid crystalline mixture, the performance has the extremely important meaning.

Description

Liquid crystalline cpd containing 1,3-diox difluoro methylene oxygen groups and preparation method thereof and application

Technical field

The invention belongs to field of liquid crystals, relate to a kind of liquid crystalline cpd containing 1,3-diox difluoro methylene oxygen groups and preparation method thereof and application.

Background technology

At present, it is more and more wider that the range of application of liquid crystalline cpd is expanded, and it can be applicable in polytype indicating meter, electro-optical device, sensor.For liquid crystalline cpd of a great variety in above-mentioned display field, wherein nematic liquid crystal is most widely used.Nematic liquid crystal has been applied in passive TN, STN matrix display and has had in the system of tft active matrix.

For thin-film transistor technologies (TFT-LCD) Application Areas, although market is very huge in recent years, technology is also ripe gradually, people to the requirement of technique of display also in continuous raising, especially in realization response fast, driving voltage is reduced to reduce the aspects such as power consumption.Liquid crystal material as one of important photoelectron material of liquid-crystal display, the effect important to the performance improving liquid-crystal display.

As liquid crystal material, need to have good chemistry and thermostability and the stability to electric field and electromagnetic radiation.And as thin-film transistor technologies (TFT-LCD) liquid crystal material, not only need to have as outside upward stability, also should have the performances such as wider nematic temperature range, suitable degree of birefringence anisotropy, very high resistivity, good anti-ultraviolet property, high electric charge conservation rate and low-steam pressure.

For dynamic menu display application, as LCD TV, in order to realize high-quality display, eliminating display frame ghost and hangover, requiring that liquid crystal has very fast response speed, therefore require that liquid crystal has lower rotary viscosity γ ₁; In addition, in order to reduce equipment energy consumption, wish that the driving voltage of liquid crystal is low as far as possible, so the dielectric anisotropy △ ε improving liquid crystal is significant to mixed liquid crystal.

Summary of the invention

The object of this invention is to provide a kind of liquid crystalline cpd containing 1,3-diox difluoro methylene oxygen groups and preparation method thereof and application.

The liquid crystalline cpd containing 1,3-diox difluoro methylene oxygen groups provided by the invention, its general structure such as formula shown in I,

In described formula I, be selected from least one in Isosorbide-5-Nitrae-cyclohexylidene, Isosorbide-5-Nitrae-phenylene and fluoro Isosorbide-5-Nitrae-phenylene;

be selected from least one in Isosorbide-5-Nitrae-phenylene and fluoro Isosorbide-5-Nitrae-phenylene;

M is 0 or 1 or 2;

N is 0 or 1;

R ₁be selected from hydrogen, at least one in the straight chain allylic alkylation of C1-C25 that the alkoxyl group of C1-C25 that the alkyl of C1-C25 that fluorine, chlorine, cyano group, the alkyl of C1-C25, the alkoxyl group of C1-C25, the normal olefine base of C2-C25, fluorine replace, fluorine replace, fluorine replace and cyclopentyl;

R ₂and R ₃all be selected from H and F any one;

R ₄be selected from H ,-CH ₃with-CF ₃in any one;

L is selected from singly-bound, Sauerstoffatom ,-CH ₂-, at least one in-CH=CH-and-C ≡ C-;

X is 0 or 1 or 2 or 3 or 4, and when L is Sauerstoffatom ,-CH=CH-and-C ≡ C-, x is 1;

Y is selected from H, F, Cl ,-CF ₃,-CHF ₂,-OCF ₃with-OCHF ₂in any one.

Above-mentioned R ₁definition in, in the alkyl of the C1-C25 that the alkyl of described C1-C25 and fluorine replace, the alkyl of C1-C25 is more specifically selected from least one in the alkyl of the alkyl of C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C2-C6, the alkyl of C2-C25, the alkyl of C3-C14, the alkyl of C4-C24, the alkyl of C5-C23, the alkyl of C6-C22, the alkyl of C7-C20 and C8-C15;

In the alkoxyl group of the C1-C25 that the alkoxyl group of described C1-C25 and fluorine replace, the alkoxyl group of C1-C25 is more specifically selected from least one in the alkoxyl group of the alkoxyl group of C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C2-C6, the alkoxyl group of C2-C25, the alkoxyl group of C3-C14, the alkoxyl group of C4-C24, the alkoxyl group of C5-C23, the alkoxyl group of C6-C22, the alkoxyl group of C7-C20 and C8-C15;

In the normal olefine base of the C2-C25 that the normal olefine base of above-mentioned C2-C25 and fluorine replace, the normal olefine base of C2-C25 is more specifically selected from C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, the normal olefine base of C2-C6, the normal olefine base of C2-C25, the normal olefine base of C3-C14, the normal olefine base of C4-C24, the normal olefine base of C5-C23, the normal olefine base of C6-C22, at least one in the normal olefine base of C7-C20 and the normal olefine base of C8-C15,

Concrete, compound shown in described formula I is specifically selected from formula I1 to any one in formula I50:

In above-mentioned formula I1-I50, R ₁definition and formula I in R ₁definition identical;

Shown in the described formula I of preparation provided by the invention, the method for compound, comprises the steps:

Will condensation reaction is carried out in triethylamine mixing, reacts complete and carries out fluoridation with hydrogen fluoride pyridine and bromine again, obtain compound shown in described formula I after completion of the reaction;

Described in, R ₁, R ₂, R ₃, R ₄, y, m are all identical with the definition in previously described formula I with the definition of n.

In aforesaid method, described in the mole dosage that feeds intake of triethylamine, pyridine hydrogen fluoride, bromine, than being 1:1-2:1-2:1-5:1-5, is specially 1:1.1:1.3:4:4;

In described step of condensation, temperature is-100-30, is specially-80 DEG C; Time is 1-5 hour, is specially 1 hour;

Describedly carry out in fluorination reaction step with hydrogen fluoride pyridine and bromine, temperature is-100-30 DEG C, is specially-80 DEG C; Time is 0.5-3 hour, is specially 2 hours;

Described reaction is carried out all in a solvent; Described solvent is specifically selected from least one in tetrahydrofuran (THF), DMF, dimethyl sulfoxide (DMSO), ethanol, methyl alcohol, methylene dichloride and toluene.

In aforesaid method, as initial reactant can as follows one or method two preparation and obtain:

Wherein, be connected with 1,3-alkyl dioxin for at least one in Isosorbide-5-Nitrae-phenylene and fluoro Isosorbide-5-Nitrae-phenylene, when m is 1 or 2, can as follows one preparation and obtain:

1) will mix with methylcarbonate and carry out condensation reaction, react complete and obtain

2) by described step 1) gained carry out reduction reaction with Lithium Aluminium Hydride, react complete and obtain

3) by described step 2) gained with carry out condensation reaction, react complete and obtain

4) by described step 3) gained be hydrolyzed with lithium hydroxide and react, react complete and obtain

5) by described step 4) gained react under triflic acid catalyzes with 1,3-dimercaptopropane, react complete and obtain

The step 1 of described method one) in, described in the mole dosage that feeds intake of sodium hydride, methylcarbonate, than being 1:1-2:1-5, is specially 1:1.5:4; Temperature is 0-65 DEG C, is specially 0-30 DEG C, and the time is 1-20 hour, is specially 18 hours;

The step 2 of described method one), described step 1) gained compare for 1:2-3 with the mole dosage that feeds intake of described Lithium Aluminium Hydride, be specially 1:2.2; In described reduction reaction step, temperature is-10-30 DEG C, is specially-10-room temperature, and the time is 1-10 hour, is specially 6 hours;

The step 3 of described method one), described step 2) gained with the mole dosage ratio that feeds intake of boron trifluoride is 1:1-2:0.1-1, and be specially 1:1:0.5, temperature is 0-30 DEG C, is specially room temperature, and the time is 1-10 hour, is specially 4 hours;

The step 4 of described method one) in, described step 3) gained compare for 1:1-5 with the mole dosage that feeds intake of lithium hydroxide, be specially 1:2; Temperature is 0-65 DEG C, is specially room temperature, and the time is 1-12 hour, is specially 10 hours; In described hydrolysis reaction step, the consumption volume ratio that feeds intake of described tetrahydrofuran (THF), methyl alcohol, water is 1:0.5-1:0.5-1, is specially 1:0.5:0.5;

The step 5 of described method one) in, described step 4) gained compare for 1:1-2:1-2 with the mole dosage that feeds intake of 1,3-dimercaptopropane, trifluoromethanesulfonic acid, be specially 1:1.1:1.2, temperature is 100-120 DEG C, is specially 110 DEG C, and the time is 1-10 hour, is specially 5 hours;

Be connected with 1,3-alkyl dioxin for Isosorbide-5-Nitrae-cyclohexylidene, when m is 0 or 1 or 2, or be connected with 1,3-alkyl dioxin for the Isosorbide-5-Nitrae-phenylene of Isosorbide-5-Nitrae-phenylene or fluoro, when m is 0, can as follows two preparation and obtain:

1) will (X=chlorine, bromine, iodine) and diethyl malonate mix and carry out condensation reaction under sodium hydride catalysis, react complete and obtain

The step 1 of described method two) in, described in the mole dosage that feeds intake of (X=chlorine, bromine, iodine), sodium hydride, diethyl malonate, than being 1:1-2:1-5, is specially 1:2:2.5; Temperature is 0-65 DEG C, is specially 0-room temperature, and the time is 1-20 hour, is specially 14 hours;

The step 2 of described method two), described step 1) gained compare for 1:2-3 with the mole dosage that feeds intake of described Lithium Aluminium Hydride, be specially 1:2.2; In described reduction reaction step, temperature is-10-30 DEG C, is specially-10-room temperature, and the time is 1-10 hour, is specially 6 hours;

The step 3 of described method two), described step 2) gained with the mole dosage ratio that feeds intake of boron trifluoride is 1:1-2:0.1-1, and be specially 1:1:0.5, temperature is 0-30 DEG C, is specially room temperature, and the time is 1-10 hour, is specially 4 hours;

The step 4 of described method two) in, described step 3) gained compare for 1:1-5 with the mole dosage that feeds intake of lithium hydroxide, be specially 1:2; Temperature is 0-65 DEG C, is specially room temperature, and the time is 1-12 hour, is specially 10 hours; In described hydrolysis reaction step, the consumption volume ratio that feeds intake of described tetrahydrofuran (THF), methyl alcohol, water is 1:0.5-1:0.5-1, is specially 1:0.5:0.5;

The step 5 of described method two) in, described step 4) gained compare for 1:1-2:1-2 with the mole dosage that feeds intake of 1,3-dimercaptopropane, trifluoromethanesulfonic acid, be specially 1:1.1:1.2, temperature is 100-120 DEG C, is specially 110 DEG C, and the time is 1-10 hour, is specially 5 hours;

Above-mentioned preparation formula I and complete reaction scheme as shown in Figure 1.

The step 1 of aforesaid method one and method two) to step 5) in, R ₁, R ₂, R ₃, R ₄, A, B, Y, m be all identical with the definition in previously described formula I with the definition of n.

Above-mentioned reaction scheme reaction in steps carry out all in a solvent; Described solvent specifically can be selected from least one in tetrahydrofuran (THF), DMF, dimethyl sulfoxide (DMSO), ethanol, methyl alcohol, methylene dichloride and toluene.

In addition; the liquid crystal compound of the compound shown in the application prepared in liquid crystal compound, liquid crystal display device material or electro-optical display part material and contained I of compound shown in the formula I that the invention described above provides, liquid crystal display device material or electro-optical display part material, also belong to protection scope of the present invention.

Present invention also offers a kind of liquid crystal compound, this liquid crystal compound is made up of to component d component a;

Wherein, component a is compound shown in the arbitrary described formula I of claim 1-2;

Components b be selected from compound shown in formula II any one;

Amount of component b be selected from compound described in formula III any one;

Component d be selected from compound shown in formula IV any one;

Described formula II in formula IV, R ₁, R ₂and R ₃all be selected from least one in the fluoroalkyl of hydrogen, halogen ,-CN, the alkyl of C1-C7, the alkoxyl group of C1-C7, the thiazolinyl of C2-C7 and C1-C5;

Z is all selected from singly-bound ,-COO-,-CH ₂o-and-CH ₂cH ₂-at least one;

all be selected from least one in singly-bound and following radicals:

Y ₁and Y ₂all be selected from least one in H and F;

P is the integer of 1-3;

When P is 2, identical or different.

The formula II of above-mentioned liquid crystal compound is in formula IV, and the alkyl of C1-C7 is specifically selected from least one in the alkyl of 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-C2 and 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 thiazolinyl of described C2-C7 is specifically selected from least one in the thiazolinyl of the thiazolinyl of C3-C7, the thiazolinyl of C4-C7, the thiazolinyl of C5-C7, the thiazolinyl of C6-C7, the thiazolinyl of C2-C6, the thiazolinyl of C3-C6, the thiazolinyl of C4-C6, the thiazolinyl of C5-C6, the thiazolinyl of C2-C5, the thiazolinyl of C3-C5, the thiazolinyl of C4-C5, the thiazolinyl of C2-C4, the thiazolinyl of C3-C4 and C2-C3;

The fluoroalkyl of described C1-C5 is specifically selected from least one in the fluoroalkyl of the fluoroalkyl of C1-C3, the fluoroalkyl of C1-C4, the fluoroalkyl of C1-C2, the fluoroalkyl of C3-C5, the fluoroalkyl of C4-C5, the fluoroalkyl of C2-C5, the fluoroalkyl of C2-C4, the fluoroalkyl of C3-C4 and C2-C3;

The mass parts of described component a is 2-40 part, is specially 4-20 part, is more specifically 14 parts;

The mass parts of described components b is 4-50 part, is specially 10-40 part, is more specifically 23 parts;

The mass parts of described amount of component b is 5-50 part, is specially 20-50 part, is more specifically 50 parts;

The mass parts of described component d is 3-45 part, is specially 10-40 part, is more specifically 13 parts.

Described liquid crystal compound can be specifically the liquid crystal compound a be made up of the compound of following each mass parts:

Described liquid crystal compound a is specially and is made up of the compound of following each mass parts:

The liquid crystal compound of compound described in the application in liquid crystal display device material or electro-optical display part material of compound shown in the formula I that the invention described above provides and liquid crystal compound and contained I, liquid crystal display device material or electro-optical display part material, also belong to protection scope of the present invention.

Liquid crystalline cpd generally is all deployed into mixture to use, general mixture all requires to have higher clearing point and lower rotary viscosity, and the clearing point of mixture and rotary viscosity determine consisting of the clearing point of composition (monomer liquid crystal) and rotary viscosity and content thereof.Containing the sub-methoxyl group linking group of difluoro (-CF ₂o-) although liquid crystalline cpd have lower rotary viscosity, its clearing point comparatively containing other linking groups as (-CH ₂o-,-C ≡ C-,-COO-,-CH ₂cH ₂-) the clearing point of liquid crystalline cpd low, this for the higher clearing point of allotment mixture be disadvantageous, the present inventor finds will containing difluoro Asia methoxyl group linking group (-CF ₂the aromatic base of liquid crystalline cpd O-) changes alkyl dioxin into, also be compound shown in formula I provided by the invention, its rotary viscosity is lower compared with aromatic base, and there is the response speed be exceedingly fast, also technique is simple, production cost is low for its synthetic method, and liquid crystal compound allotment to lower rotary viscosity has very important practical significance.

Accompanying drawing explanation

Fig. 1 is the synthetic route of compound shown in formula I.

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 MP represents fusing point, and CP represents clearing point, and MS represents mass spectrum, and △ ε represents dielectric anisotropy, and △ n represents optical anisotropy.The method measuring GC, MP, CP, MS, △ ε and △ n is ordinary method.

(the R of Compound I 2 shown in embodiment 1, formula I ₁=C ₃h ₇)

Step 1

22g (60% is added in 2L reaction flask, 0.555mol) sodium hydride, 300ml anhydrous tetrahydro furan, be placed in cryostat, be cooled to 0 DEG C, drip 106.5g (0.37mol) (I-0) and 300ml anhydrous tetrahydro furan, within about 2 hours, add, react after 1 hour, be added dropwise to 180ml (1.48mol) methylcarbonate, stirring is raised to room temperature reaction 18 hours, pour in the frozen water of 2Kg, separate organic phase, 200ml extraction into ethyl acetate three times, merge organic phases washed with water twice, evaporated under reduced pressure solvent, obtain oily matter, decolour with short silicagel column again, ethyl acetate-light petrol wash-out, evaporated under reduced pressure solvent, obtain 73g white solid (I-1), yield: 55%

Step 2

Add in 1L there-necked flask 70g (0.194mol) (I-1), 550ml dry tetrahydrofuran, be placed in cryostat, be cooled to-10 DEG C, add 16.2g (0.426mol) Lithium Aluminium Hydride in batches, react after 1 hour, be raised to stirring at room temperature and react 6 hours, then be cooled to-10 DEG C, be added dropwise to 16ml (25%) aqueous sodium hydroxide solution, room temperature reaction is after 1 hour, suction filtration, and filter cake ethyl acetate is washed, neat solvent is steamed under filtrate decompression, obtain 50.8g (I-2), white solid, yield: 95%

Step 3

Add in 1L there-necked flask 50g (0.181mol) (I-2), 20g (80%, 0.181mol) glyoxalic acid methylester toluene solution, 300ml toluene, stirring at room temperature is dissolved, be added dropwise to 11.5ml (98%, 90.5mmol) Eorontrifluoride etherate solution, stirring reaction 4 hours, be added dropwise to the ice water solution that 300ml sodium carbonate is saturated, separate organic phase, aqueous phase toluene extracting twice, merge organic phase, wash with water, saturated salt is washed, neat solvent is steamed under decompression, residue over silica gel column separating purification, clean with 50% ethyl acetate and sherwood oil, neat solvent is steamed under decompression, obtain trans (I-3) 28.2g, white solid, yield 45%

Step 4

Add in 500mL there-necked flask 25g (72.2mmol) (I-3), 100ml tetrahydrofuran (THF), 50ml methyl alcohol, 50ml water, add 6g (0.14mol) lithium hydroxide, stirring at room temperature reacts 10 hours, and decompression is lower steams except tetrahydrofuran (THF) and methanol solvate, drip 1M dilute hydrochloric acid and be adjusted to acidity, suction filtration, filter cake washes with water, vacuum-drying, obtain 20.8g white solid (I-4), yield: 87%

Step 5

Add in 500mL there-necked flask 20g (60.2mmol) (I-4), 7g (66.2mmol) 1,3-dimercaptopropane, 10.8g (72.2mmol) trifluoromethanesulfonic acid, 250ml toluene, reflux divides water, after 5 hours, drop to room temperature, obtain the toluene solution of product I-5, yield 100%

Step 6

9.8g (66.2mmol) 3 is added in 1L there-necked flask, 4, 5-trifluoromethyl phenol, 7.3g (72.2mmol) triethylamine, 200ml methylene dichloride, be placed in cryostat, be cooled to-80 DEG C, be added dropwise to the toluene solution of I-5 prepared by step, half an hour adds, after 1 hour, still drip 31ml hydrogen fluoride pyridine (70% at-80 DEG C, 0.24mol) solution, half an hour adds, the solution of 38.5g (0.24mol) bromine and 100ml methylene dichloride is still dripped at-80 DEG C, add rear insulated and stirred and react 2 hours, remove cryostat, naturally room temperature is raised to, add 500ml water, separatory, aqueous phase 100ml dichloromethane extraction secondary, merge organic layer, neat solvent is steamed under decompression, obtain yellow solid, ethyl alcohol recrystallization twice, obtain 19g, white solid (I2, R ₁=C ₃h ₇), yield: 65%

Compounds content Gc:99.95%

Melting point compound MP:48 DEG C

Compound clearing point CP:20 DEG C

The liquid crystal property of this compound is as follows:

Δn[589nm,20℃]：0.165

Δε[KHz,20℃]:22.5

Prepared by compound (I2, R shown in gained formula I to this embodiment ₁=C ₃h ₇) carry out liquid crystal property test, concrete steps comprise: compound (I2, R shown in gained formula I prepared by this embodiment ₁=C ₃h ₇) to be dissolved in clearing point CP be in the parent of 80 DEG C for ratio with 10%, the clearing point CP of test gained liquid crystal compound, acquired results CP is 83.4 DEG C;

As from the foregoing, this embodiment is utilized to prepare the allotment of compound shown in gained formula I parent liquid crystalline cpd, compared with the liquid crystalline cpd of existing this area similar structures used, the clearing point CP of gained liquid crystal compound can be significantly improved, and in field of liquid crystal display, require that the clearing point of liquid crystal display device material used or electro-optical display part material is high as far as possible, compound shown in visible formula I provided by the invention is preparing liquid crystal display device material or electro-optical display part Material Field has important using value.

(the R of Compound I 45 shown in embodiment 2, preparation formula I ₁=C ₃h ₇)

Step 1

The synthetic operation of Compound I-1 is same as the step 1 of embodiment 1, yield 78%

Step 2

The synthetic operation of Compound I-2 is same as the step 2 of embodiment 1, yield 89%

Step 3

The synthetic operation of Compound I-3 is same as the step 3 of embodiment 1, obtains trans 1-3, yield 57%

Step 4

The synthetic operation of Compound I-4 is same as the step 4 of embodiment 1, obtains 1-4, yield 97%

Step 5

The synthetic operation of Compound I-5 is same as the step 5 of embodiment 1, obtains the toluene solution of 1-5, yield 100%

Step 6

143g (0.55mol) 2 is added in 3L there-necked flask, 3', 4', 5', 6-five fluoro-[1, 1'-biphenyl]-4-phenol, 65.7g (0.65mol) triethylamine, 1000ml methylene dichloride, be placed in cryostat, be cooled to-80 DEG C, be added dropwise to I-5 (0.5mol) toluene solution prepared by step 5, within 2 hours, add, after 1 hour, still drip 257.5ml hydrogen fluoride pyridine (70% at-80 DEG C, 2mol) solution, half an hour adds, the solution of 320g (2mol) bromine and 200ml methylene dichloride is still dripped at-80 DEG C, add rear insulated and stirred and react 2 hours, remove cryostat, naturally room temperature is raised to, add 1000ml water, separatory, aqueous phase 200ml dichloromethane extraction secondary, merge organic layer, neat solvent is steamed under decompression, obtain yellow liquid, ethyl alcohol recrystallization twice, obtain 171.6g white solid (I45, R ₁=C ₃h ₇), yield: 66.8%

Compounds content Gc:99.93%

Melting point compound MP:68 DEG C

Compound clearing point CP:24 DEG C

The liquid crystal property of this compound is as follows:

Δn[589nm,20℃]：0.16

Δε[KHz,20℃]：19

Prepared by compound (I45, R shown in gained formula I to this embodiment ₁=C ₃h ₇) carry out liquid crystal property test, concrete steps comprise: compound (I45, R shown in gained formula I prepared by this embodiment ₁=C ₃h ₇) to be dissolved in clearing point CP be in the parent of 80 DEG C for ratio with 10%, the clearing point CP of test gained liquid crystal compound, acquired results CP is 84.5 DEG C;

(the R of Compound I 44 shown in embodiment 3, preparation formula I ₁=C ₃h ₇)

Step 1

178g (60% is added in 5L reaction flask, 3.7mol) sodium hydride, 1000ml anhydrous tetrahydro furan, be placed in cryostat, be cooled to 0 DEG C, drip 704ml (4.66mol) diethyl malonate, about add half an hour, react after 1 hour, add 350.6g (1.86mol) (I-0) and 500ml tetrahydrofuran solution, stirring is raised to room temperature reaction 14 hours, pour in the frozen water of 2Kg, separate organic phase, 200ml extraction into ethyl acetate three times, merge organic phases washed with water twice, evaporated under reduced pressure solvent, obtain oily matter, decolour with short silicagel column again, sherwood oil wash-out, evaporated under reduced pressure solvent, obtain 493g colourless liquid (I-1), yield: 85%

Step 2

The synthetic operation of Compound I-2 is same as the step 2 of embodiment 1, yield 87%

Step 3

The synthetic operation of Compound I-3 is same as the step 3 of embodiment 1, obtains trans 1-3, yield 65%

Step 4

The synthetic operation of Compound I-4 is same as the step 4 of embodiment 1, obtains 1-4, yield 63%

Step 5

Step 6

Compound I 44 (R ₁=C ₃h ₇) synthetic operation be same as the step 6 of embodiment 2, ethyl alcohol recrystallization for several times, yield 65%

Compounds content Gc:99.95%

Melting point compound MP:63 DEG C

Compound clearing point CP:28 DEG C

The liquid crystal property of this compound is as follows:

Δn[589nm,20℃]：0.15

Δε[KHz,20℃]：23

This embodiment prepares liquid crystal property test and the previous embodiment 1 gained liquid crystalline cpd I44 (R of compound shown in gained formula I ₁=C ₃h ₇), test result without substantive difference, no longer Ao Shu herein.

Embodiment 4,

According to each component shown in table 1 and weight percentage mixing, 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, be applicable in liquid-crystal display.

Reference examples 1, liquid crystal compound thing b

Component in this liquid crystal compound b is compared with the component of liquid crystal compound a, and do not have compound shown in formula I1 in annex solution crystal composite a and formula I9, other components do not become.

The composition of table 3, liquid crystal compound b

The performance test results of liquid crystal compound b is as shown in table 4:

The performance test results of table 4, liquid crystal compound b

Contrasted from table 4 and table 2, if do not add Compound I 1 and I9, then the specific inductivity of liquid crystal compound thing can reduce greatly.

Claims

1. compound shown in formula I,

M is 0 or 1 or 2;

N is 0 or 1;

R ₁be selected from hydrogen, at least one in straight chain allylic alkylation that the total number of carbon atoms that alkoxyl group that the total number of carbon atoms that alkyl that the total number of carbon atoms that normal olefine base that alkoxyl group that alkyl that fluorine, chlorine, cyano group, the total number of carbon atoms are C1-C25, the total number of carbon atoms are C1-C25, the total number of carbon atoms are C2-C25, fluorine replace is C1-C25, fluorine replace is C1-C25, fluorine replace is C2-C25 and cyclopentyl;

R ₂and R ₃all be selected from H and F any one;

R ₄be selected from H ,-CH ₃with-CF ₃in any one;

Y is selected from H, F, Cl ,-CF ₃,-CHF ₂,-OCF ₃with-OCHF ₂in any one.

2. compound according to claim 1, is characterized in that: shown in described formula I, compound is selected from formula I1 to any one in formula I50:

In above-mentioned formula I1-I50, R ₁definition and formula I in R ₁definition identical.

3. prepare a method for compound shown in formula I described in claim 1 or 2, comprise the steps:

Described in, R ₁, R ₂, R ₃, R ₄, y, m are all identical with the definition in claim 1 with the definition of n.

4. method according to claim 3, is characterized in that: described in the mole dosage that feeds intake of triethylamine, hydrogen fluoride pyridine, bromine, than being 1:1-2:1-2:1-5:1-5, is specially 1:1.1:1.3:4:4;

5. a liquid crystal compound, is made up of to component d component a;

Components b be selected from compound shown in formula II any one;

Component d be selected from compound shown in formula IV any one;

all be selected from least one in singly-bound and following radicals:

Y ₁and Y ₂all be selected from least one in H and F;

P is the integer of 1-3;

When P is 2, identical or different.

6. liquid crystal compound according to claim 5, is characterized in that: the mass parts of described component a is 2-40 part, is specially 4-20 part;

The mass parts of described components b is 4-50 part, is specially 10-40 part;

The mass parts of described amount of component b is 5-50 part, is specially 20-50 part;

The mass parts of described component d is 3-45 part, is specially 10-40 part.

7. the liquid crystal compound according to claim 5 or 6, is characterized in that: described liquid crystal compound is the liquid crystal compound a be made up of the compound of following each mass parts:

8. in compound shown in the arbitrary described formula I of claim 1-2 or claim 5-7, the application in liquid crystal display device material or electro-optical display part material prepared by arbitrary described liquid crystal compound.

9. comprise liquid crystal display device material or the electro-optical display part material of arbitrary described liquid crystal compound in compound shown in the arbitrary described formula I of claim 1-2 or claim 5-7.