CN103333139A - Liquid crystal compounds containing tetrahydrofuran structure - Google Patents

Abstract

The invention discloses liquid crystal compounds containing tetrahydrofuran structure, and a preparation method and application thereof. The structural general formula of the compounds is disclosed as Formula I. The compounds have the advantages of stable structure, wide liquid-crystal-state temperature range and favorable low-temperature mutual solubility, can implement low threshold voltage and low rotary viscosity gamma 1 when being used in optical devices, and can improve the properties of the liquid crystal composition material and display device, thereby having an important meaning in quick response of display devices. The liquid crystal composition containing the compounds can be used for preparing liquid crystal displays with low drive voltage, wide temperature range and high response speed.

Description

One class contains the liquid crystalline cpd of tetrahydrofuran (THF) structure

Technical field

The invention belongs to liquid crystalline cpd and Application Areas, relate to a kind of liquid crystalline cpd that contains the tetrahydrofuran (THF) structure.

Background technology

For technical field of liquid crystal display, though 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, reduces driving voltage to reduce aspect such as power consumption.Liquid crystal material plays an important role to the performance of improving liquid-crystal display as one of important photoelectron material of liquid-crystal display.

Obtain very great development as the liquid crystal material that shows usefulness, a large amount of liquid crystalline cpds occurred.Develop into phenylcyclohexane class, phenylacetylene class, ethyl bridged bond class, end thiazolinyl liquid crystal and various fluorine-containing aromatic ring class liquid crystalline cpds etc. from biphenyl nitrile, ester class, oxygen heterocyclic ring class, pyrimidine lopps liquid crystalline cpd, constantly satisfy display performance requirements such as TN, STN, TFT-LCD.

Any demonstration all requires suitable temperature range with liquid crystal, wideer liquid crystal state temperature, and advantages of higher stability, relatively the viscosity of Shi Heing has response speed faster to electric field.Also should have performances such as wideer nematic phase, lower degree of birefringence, very high resistivity, good anti-ultraviolet property, high electric charge conservation rate and low-steam pressure.But also be used in the liquid-crystal display separately without any single liquid crystal monomer so far, and need not just can satisfy performance requriements with other compound combination.If two or more liquid crystal monomer is mixed, just can change the various types of properties of liquid crystal continuously, general TFT liquid crystal basically also portion mixed by multiple monomer liquid crystal.

In order to realize improving the liquid-crystal display performance, exploitation has lower rotary viscosity γ 1 (or even at low temperatures) in addition, and the mixed liquid crystal of higher dielectric anisotropy Δ ε is significant.Therefore the synthetic liquid crystal monomer with this performance of exploitation is still following important research direction.

Summary of the invention

The purpose of this invention is to provide a kind of liquid crystalline cpd that contains the tetrahydrofuran (THF) structure.

The liquid crystalline cpd that contains the tetrahydrofuran (THF) structure provided by the invention, its general structure be suc as formula shown in the I,

Among the described formula I, R ₁And R ₂Identical or different, all be selected from hydrogen atom, alkyl, alkoxyl group, substituted alkyl and alkoxyl group, Cl, F ,-CN ,-OCN ,-OCF ₃,-CF ₃,-CHF ₂,-OCHF ₂,-SCN ,-NCS and-SF ₅

Wherein, the total number of carbon atoms of described alkyl or alkoxyl group is 1-15;

Described substituted alkyl be in the alkyl at least one-CH ₂-by-CH=CH-,-C ≡ C-,-COO-,-OOC-, tetramethylene or-O-replace and group or at least one hydrogen atom in the alkyl replaced by fluorine or chlorine and group;

Described substituted alkoxyl group be in the alkoxyl group at least one-CH ₂-by-CH=CH-,-C ≡ C-,-COO-,-OOC-, tetramethylene or-O-replace and group or at least one hydrogen atom in the alkoxyl group replaced by fluorine or chlorine and group;

A ₁, A ₂, A ₃And A ₄Identical or different, all be selected from least a in the following radicals:

L ¹, L ²And L ³Identical or different, all be selected from singly-bound ,-CH=CH-,-C ≡ C-,-COO-,-OOC-,-CF ₂O-,-OCH ₂-,-CH ₂O-,-OCF ₂-,-CH ₂CH ₂-,-CF ₂CH ₂-,-CH ₂CF ₂-,-C ₂F ₄-,-CF=CF-and-(CH ₂) ₄-;

A, b and c all are selected from the integer of 0-3, and a+b+c≤5.

Formula I specifically can be the liquid crystalline cpd shown in the formula Ia-Id:

Among the described formula Ia-Id, R ₁, R ₂, A ₁, A ₂, A ₃, A ₄, L ₁, L ₂, L ₃Definition as hereinbefore; A, b, c represent 0,1,2,3 independently of one another, and a+b+c≤4.

Among the above-mentioned formula I, the alkyl of described C1-C15 specifically is 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, at least a in the alkyl of C1-C2 and the alkyl of C2-C3;

The alkoxyl group of described C1-C15 specifically is 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 C2-C10, the alkoxyl group of C3-C10, the alkoxyl group of C1-C10, at least a in the alkoxyl group of C1-C2 and the alkoxyl group of C2-C3;

More specifically, compound shown in the described formula I be formula I1 to the compound shown in the formula I14 any one:

Described formula I1 to formula I14, R ₁And R ₂Definition all identical with the definition among the aforementioned formula I ,-(F) expression has the fluorine atom substituting group on the phenyl ring or is hydrogen;

R ₁Be specially hydrogen, the total number of carbon atoms is the straight chained alkyl of 1-10 or the straight chain alkoxyl group that the total number of carbon atoms is 1-10;

R ₂Be specially hydrogen, the total number of carbon atoms and be the straight chained alkyl of 1-10, straight chain alkoxyl group that the total number of carbon atoms is 1-10, Cl, F ,-CN ,-OCF ₃,-CF ₃,-SCN ,-CHF ₂Or-OCHF ₂

More specifically, compound shown in the described formula I is specially following each compound:

L among the described formula I of preparation provided by the invention ₁For-CF ₂O, A ₁For

The time compound method, comprise the steps: (route 1) (work as L1=-CF2O-, A1 is

The time)

1) will -80 ℃ with

React with n-Butyl Lithium, the reaction diethyl ether solution that obtains adding again behind the product triethyl silicon hydrogen and boron trifluoride that finishes reacted 1-3 hour at-20～-25 ℃, and reaction finishes and obtains

2) with the step 1) gained

Reacted 20-40 minute at-50～-70 ℃ with n-Butyl Lithium and difluorodibromomethane, obtain

3) with step 2) gained

With

Reacted 2-5 hour at 50～70 ℃ with carbonate, obtain L among the described formula I ₁For-CF ₂O, A ₁For

The time compound;

Above-mentioned steps 1) to step 3), a in the described structural formula, R ₁, R ₂, A ₂, b, c, L ₂, L ₃, A ₃And A ₄Definition all with formula I in the definition identical.

In the aforesaid method step 1),

The molar ratio of n-Butyl Lithium, triethyl silicon hydrogen and boron trifluoride is 1: 1.1: 1.1: 2.2: 2.2;

Described step 2) in, With the molar ratio of n-Butyl Lithium and difluorodibromomethane be 1: 1.1: 1.5; In the described reactions steps, the time is 30 minutes;

In the described step 3),

With the molar ratio of carbonate be 1: 1-1.3: 2.

L among the described formula I of preparation provided by the invention ₂For-CF ₂O, A ₂For

The time compound method, comprise the steps: (route 2)

(work as L2=-CF2O-, A2 is The time)

1) will

React at-50～-80 ℃ with n-Butyl Lithium, the reaction diethyl ether solution that obtains adding again behind the product triethyl silicon hydrogen and boron trifluoride that finishes reacted 1-3 hour at-20～-25 ℃, and reaction finishes and obtains

2) with the step 1) gained

With Carbonate and four triphenylphosphines close the palladium mixing to carry out back flow reaction 2-4 hour, and reaction finishes and obtains

3) with step 2) gained

N-Butyl Lithium and difluorodibromomethane reacted 20-40 minute, and reaction finishes and obtains

4) with the step 3) gained

With Reacted 2-5 hour at 50-70 ℃ with carbonate, reaction finishes and obtains L among the described formula I ₂For-CF ₂O, A ₂For

The time compound;

Above-mentioned steps 1) to step 4), the A in the described structural formula ₁, L ₁, a, R ₁, A ₂, b, c, L ₃, A ₃And A ₄Definition all with formula I in the definition identical.

In the aforesaid method step 1),

The molar ratio of n-Butyl Lithium, triethyl silicon hydrogen and boron trifluoride is 1: 1.1: 1.1: 2.2: 2.2;

Described step 2) in, With The amount ratio that carbonate and four triphenylphosphines close palladium is 1mol: 1.2mol: 2mol: 4g; Described carbonate is selected from least a in yellow soda ash and the salt of wormwood;

In the described step 3),

The molar ratio of n-Butyl Lithium and difluorodibromomethane is 1: 1.1: 1.5; In the described reactions steps, the time is 30 minutes;

In the described step 4),

With the molar ratio of carbonate be 1: 1～1.3: 2; Described carbonate is selected from least a in yellow soda ash and the salt of wormwood.

L among the described formula I of preparation provided by the invention ₃For-CF ₂O, A ₃For

The time compound method, comprise the steps: (route 3)

(work as L3=-CF2O-, A3 is The time)

1) will

React at-50～-80 ℃ with n-Butyl Lithium, the reaction diethyl ether solution that obtains adding again behind the product triethyl silicon hydrogen and boron trifluoride that finishes reacted 1-3 hour at-20～-25 ℃, and reaction finishes and obtains

2) with the step 1) gained

With

Carbonate and four triphenylphosphines close the palladium mixing to carry out back flow reaction 2-4 hour, and reaction finishes and obtains

3) with step 2) gained Potassium tert.-butoxide, n-Butyl Lithium and iodine react in-90 ℃, and reaction finishes and obtains

4) with described step 3) gained

With

Carbonate and four triphenylphosphines close the palladium mixing and carry out back flow reaction, and reaction finishes and obtains

5) with described step 4) gained

React at-50～-70 ℃ with n-Butyl Lithium and difluorodibromomethane, reaction finishes and obtains

6) with the step 5) gained

R ₂-A ₄OH and carbonate reacted 2-5 hour at 50-70 ℃, and reaction finishes and obtains L among the described formula I ₃For-CF ₂O, A ₃For

The time compound;

Above-mentioned steps 1) to step 6), the A in the described structural formula ₁, L ₁, a, R ₁, R ₂, L ₂, A ₂, b, c and A ₄Definition all identical with the definition among the formula I.

In the aforesaid method step 1),

The molar ratio of n-Butyl Lithium, triethyl silicon hydrogen and boron trifluoride is 1: 1.1: 1.1: 2.2: 2.2;

Described step 2) in,

With

The amount ratio that carbonate and four triphenylphosphines close palladium is 1mol: 1.2mol: 2mol: 4g; Described carbonate is selected from least a in yellow soda ash and the salt of wormwood;

In the described step 3),

The molar ratio of potassium tert.-butoxide, n-Butyl Lithium and iodine is 1: 1.1: 1.1: 1.: 1

With described step 4) gained

With

The ratio of carbonate and four triphenylphosphines is 1mol: 1.2mol: 2mol: 4g; Described carbonate is selected from least a in yellow soda ash and the salt of wormwood;

With described step 5) gained

With the mol ratio of n-Butyl Lithium difluorodibromomethane 1: 1.1: 1.5

In the described step 6), gained

R ₂-A ₄The molar ratio of OH and carbonate is 1: 1～1.3: 2; Described carbonate is selected from least a in yellow soda ash and the salt of wormwood.

L among the described formula I of preparation provided by the invention ₁For-CF ₂O, A ₁ Be 1,4-cyclohexyl, 1,4-phenylene or except 3,5-, two fluoro-1, other formulas I described fluoro-1 beyond the 4-phenylene, the method for compound during the 4-phenylene comprises the steps: (route 4)

1) will

React at-80 ℃ with n-Butyl Lithium, the reaction diethyl ether solution that obtains adding again behind the product triethyl silicon hydrogen and boron trifluoride that finishes reacted 1-3 hour at-20～-25 ℃, and reaction finishes and obtains

2) with the step 1) gained

With the n-Butyl Lithium mixing, and feed carbonic acid gas to saturated absorption, reacted 1-3 hour at-80 ℃ to-60 ℃, reaction finishes and obtains

3) with step 2) gained

Carry out dehydration reaction to the no coupling product water generates with 1,3-dimercaptopropane and trifluoromethanesulfonic acid backflow, obtain

4) with the step 3) gained

Add NEt at-70 ℃ ₃3HF and bromine were reacted 1-3 hour, and reaction finishes and obtains L among the described formula I ₁For-CF ₂O, A ₁ Be 1,4-cyclohexyl, 1,4-phenylene or except 3,5-, two fluoro-1, other formulas I described fluoro-1 beyond the 4-phenylene, compound during the 4-phenylene;

Above-mentioned steps 1) to step 4), the A in the described structural formula ₁, L ₁, a, R ₁, A ₂, b, c, L ₃And A ₃Definition all with formula I in identical.

In the aforesaid method step 1),

The molar ratio of n-Butyl Lithium, triethyl silicon hydrogen and boron trifluoride is 1: 1.1: 1.1: 2.2: 2.2;

Described step 2) in,

The molar ratio of n-Butyl Lithium and carbonic acid gas is 1: 1: 2-3;

In the described step 3),

The molar ratio of 1,3-dimercaptopropane and trifluoromethanesulfonic acid is 1: 1.3: 1.3;

In the described step 4),

NEt ₃The molar ratio of 3HF, bromine is 1: 1: 1.3: 1.3; Described at-70 ℃ of adding NEt ₃3HF and bromine are carried out in the reactions steps, and the time is 1 hour.

L among the described formula I of preparation provided by the invention ₁, L ₂And L ₃All be not-CF ₂The method of compound during O comprises the steps: (route 5)

Perhaps

1) will

React at-80 ℃ with n-Butyl Lithium, the reaction diethyl ether solution that obtains adding again behind the product triethyl silicon hydrogen and boron trifluoride that finishes reacts, and reaction finishes and obtains

2) with the step 1) gained

Carbonate and four triphenylphosphines close the palladium mixing and carry out back flow reaction, and reaction finishes and obtains

3) with step 2) gained

Potassium tert.-butoxide, n-Butyl Lithium and iodine mixing react at-90 ℃, and reaction finishes and obtains

4) with the step 3) gained

Carbonate and palladium-carbon catalyst mixing carried out back flow reaction 2-4 hour, and reaction finishes and obtains L among the described formula I ₁, L ₂And L ₃All be not-CF ₂Compound during O;

Perhaps, according to following steps 5) preparation:

5) with the step 1) gained

With

Carbonate and four triphenylphosphines close the palladium mixing and carry out back flow reaction, and reaction finishes and obtains L among the described formula I ₁, L ₂And L ₃All be not-CF ₂Compound during O;

Above-mentioned steps 1) to step 5), the A in the described structural formula ₁, a, R ₁, A ₂, b, c and A ₃Definition all with formula I in identical.

In the aforesaid method step 1),

The molar ratio of n-Butyl Lithium, triethyl silicon hydrogen and boron trifluoride is 1: 1.1: 1.1: 2.2: 2.2;

Described step 2) in,

The amount ratio that carbonate and four triphenylphosphines close palladium is 1mol: 1.2mol: 1.3mol: 4g; Described carbonate is selected from least a in yellow soda ash and the salt of wormwood;

In the described step 3),

The molar ratio of potassium tert.-butoxide, n-Butyl Lithium and iodine is 1: 1.1: 1.1: 1.1;

In the described step 4), The amount ratio of carbonate and palladium-carbon catalyst is 1mol: 1.1mol: 1.3mol; Described carbonate is selected from least a in yellow soda ash and the salt of wormwood;

In the described step 5),

With

The amount ratio that carbonate and four triphenylphosphines close palladium is 1mol: 1.2mol: 2mol: 4g; Described carbonate is selected from least a in yellow soda ash and the salt of wormwood.

In the above-mentioned route 1 to 5, described reaction is all carried out in solvent, and described solvent is selected from least a in toluene, ethanol, isopropyl alkane, octane-iso and the methylene dichloride; Described reaction is all carried out in inert atmosphere; Described inert atmosphere specifically can be nitrogen or argon gas atmosphere.

The present invention also provides a kind of liquid-crystal composition, and this liquid-crystal composition is to comprise liquid-crystal composition at least a in the compound shown in the formula I.

Above-mentioned liquid crystal compound, it comprises 1～5 kind of described liquid crystalline cpd of formula I, and be preferably described liquid-crystal composition and comprise the liquid crystalline cpd shown in the 1-4 kind formula I, more specifically be the 1-2 kind.

Shown in the described formula I in the compound at least a total mass account for the 1-90% of described liquid crystal compound gross weight, preferred 5-60%, more preferably 10-40% is specially 12-18%, 12-14%, 12.5-18% or 14-18%, more specifically is 12%, 12.5%, 14% or 18%.

Described liquid crystal compound is specially any one among the liquid crystal compound a to e:

Described liquid crystal compound a comprises the compound of following each mass parts or is made up of the compound of following each mass parts:

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

Described liquid crystal compound b comprises the compound of following each mass parts or is made up of the compound of following each mass parts:

Described liquid crystal compound b is specially the compound that comprises following each mass parts or is made up of the compound of following each mass parts:

Described liquid crystal compound c comprises the compound of following each mass parts or is made up of the compound of following each mass parts:

Described liquid crystal compound c is specially the compound that comprises following each mass parts or is made up of the compound of following each mass parts:

Described liquid crystal compound d comprises the compound of following each mass parts or is made up of the compound of following each mass parts:

Described liquid crystal compound d is specially the compound that comprises following each mass parts or is made up of the compound of following each mass parts:

Described liquid crystal compound e comprises the compound of following each mass parts or is made up of the compound of following each mass parts:

Described liquid crystal compound e is specially the compound that comprises following each mass parts or is made up of the compound of following each mass parts:

The liquid crystalline cpd that the invention described above provides or liquid crystal compound in preparation liquid crystal display material or electrooptics display material application and comprise liquid crystalline cpd or state at least a liquid crystal display material optical liquid crystal indicating meter in the liquid crystal compound, also belong to protection scope of the present invention.Described indicating meter specifically is TN, STN or TFT indicating meter.

The liquid crystalline cpd that contains the tetrahydrofuran (THF) structure provided by the invention, it has preferably stability, can realize lower threshold voltage and low rotary viscosity γ when using in optics ₁, significant for the quick response that realizes indicating meter, so be suitable for very much allocating liquid crystal compound.The liquid crystal compound that contains this type of liquid crystal monomer can be applicable to multiple indicating meter, is applicable to TN and STN indicating meter, also can be used for the TFT indicating meter.

Description of drawings

Fig. 1 is the mass spectrum of compound shown in the embodiment 2 preparation gained formula I.

Embodiment

Following embodiment is used for explaining the present invention, but the present invention is not limited only to following embodiment.Described method is ordinary method if no special instructions.Described material all can get from open commercial sources if no special instructions.GC represents gas chromatographic purity among the following embodiment, and MP represents fusing point, and MS represents mass spectrum, and Δ ε represents dielectric anisotropy, and Δ n represents optical anisotropy.

The gained compound utilizes GC-MS gained mass spectrum, and gas-chromatography is identified explanation.

The MS5975C type of GC-MS assay determination device Agilent company

GC is by the HP6820 type gas chromatographicanalyzer of Agilent company

Fusing point has the micro-thermal analyzer of WRX-1S, and setting temperature rise rate is 3 ℃/min

The physical property measurement method of compound:

1. optical anisotropy (the specific refractory power anisotropy is measured down Δ n at 25 ℃)

Be determined under 25 ℃, the light with wavelength 589nm utilizes Abb to carry out

After a direction rubs to the surface of headprism (Pri3m), sample is added drop-wise on the headprism.Specific refractory power (n ₁₁) be when polarization direction is parallel with frictional direction, to measure specific refractory power (n _⊥) be when polarization direction is vertical with frictional direction, to measure.The value of optical anisotropy (Δ n) is by Δ n=n ₁₁-n _⊥Calculate.

2. dielectric constant anisotropy (the Δ ∑ is measured down at the 25 ℃) HP4284a of Hewlett-Packard measures

Measure liquid crystal molecule at axial specific inductivity ∑ ₁₁, the specific inductivity (∑ of mensuration liquid crystal molecule short-axis direction _⊥), dielectric constant anisotropy Δ ∑=∑ ₁₁-∑ _⊥Calculate.

3. bulk viscosity η (cone and plate viscometer is measured, and measures unit: [mPas] down at 25 ℃)

4. rotary viscosity γ ₁[mPas], test condition is 25 ± 0.5 ℃.

Compound shown in embodiment 1, the preparation formula I

Step 1:

Add 46.3g (0.24mol) 3 in the 1L there-necked flask; 5-difluoro bromobenzene (reactant); the tetrahydrofuran (THF) of 400ml drying (solvent); under the nitrogen protection; be cooled to below-80 ℃; drip 96ml (0.24mol; 2.5N) n-Butyl Lithium (reactant); dripped Bi Baowen 1 hour; under the same temperature; splash into 0.216mol1; the mixing solutions of 4-butyrolactone (reactant) and 50ml dry tetrahydrofuran (solvent); drip to finish and stirred 30 minutes; naturally heat up, drip 200ml saturated aqueous ammonium chloride (adjusting pH value), separatory about 0 ℃; water extracts with 200ml ethyl acetate (solvent); the organic phase washing is spin-dried for, and obtains 43g (GC:89%) liquid; add products obtained therefrom above the 50g in another 1L there-necked flask; the methylene dichloride of 500ml drying (solvent) under the nitrogen protection, is cooled to-25～-20 ℃; drip 63.3ml (0.397mol; 2.2eq) triethyl silicon hydrogen (reactant), drip to finish Dropwise 5 0ml (0.397mol in the system; 2.2eq) boron trifluoride diethyl etherate (reactant); drip and finish-25～-20 ℃ of stirrings of maintenance 2 hours, rise to 0 ℃ naturally, add saturated aqueous solution of sodium bicarbonate (adjusting pH value) and do not emit to there being bubble; separatory; be washed to neutrality, be spin-dried for solvent, get (1-a) 35g; yield 88%, gas chromatographic purity 90%.

Step 2:

In reaction flask, add 0.1mol (1-b) (reactant), 200ml tetrahydrofuran (THF) (solvent), logical nitrogen protection; be cooled to-60 ℃, drip 0.11mol n-Butyl Lithium (reactant), drip process temperature control-55 ℃～-60 ℃; drip and finish, continued the temperature control stirring reaction 1 hour.Be cooled to-70 ℃, drip 0.15mol difluorodibromomethane (reactant), drip process temperature control-65 ℃～-70 ℃, drip and finish, continue the temperature control stirring reaction 30 minutes, and be warming up to room temperature, add 20ml concentrated hydrochloric acid (adjusting pH value)+50ml water (solvent) hydrolysis, separatory, 100ml methylene dichloride (solvent) extracts water, and the washing organic phase is to neutral, and solvent evaporated gets weak yellow liquid (1-c), yield 70%, gas chromatographic purity 78%.

Step 3:

In reaction flask, add 0.01mol (1-c) (reactant), 50mlDMSO (solvent), 0.02mol Anhydrous potassium carbonate (reactant), 0.012mol2,3 ', 4 ', 5 '-tetrafluoro biphenyl-4-phenol (reactant) is heated with stirring to 65～70 ℃ of reactions 2 hours.Be cooled to room temperature, cross filter solid, and with 30ml methylene dichloride (solvent) flush cake, filtrate adds 100ml water, stirs, separatory extracts water layer with 20ml methylene dichloride (solvent), and the washing organic phase is to neutrality, solvent evaporated.Enriched material is dissolved in 50ml toluene (solvent), crosses the silicagel column decolouring, with toluene (solvent) wash-out, collection elutriant and steaming desolventize, and gains dehydrated alcohol (solvent) recrystallization 3 times obtain white needle-like crystals (1-d), yield 40%, gas chromatographic purity 99.8%.

The structure verification data of this product are as follows:

MP：55℃

MS：m/s％189(5.3)，191(8.2)，233(100)，474(2.4)

As from the foregoing, this product structure is correct, is the compound of ownership formula I.

The liquid crystal property detected result of this compound is as follows:

Δε：18.0V

Δn：0.165。

η：38

As from the foregoing, this compound has bigger specific inductivity and moderate specific refractory power, and less viscosity can be applicable in the mixed liquid crystal.

According to the method for previous embodiment 1, only the substituting group in the reactant is carried out corresponding replacement according to the substituting group in the target product, obtain the compound of following ownership formula I.

Compound shown in embodiment 2, the preparation formula I

Step 1:

Add 56.64g (0.24mol) 1 in the 1L there-necked flask; 4-dibromobenzene (reactant); the tetrahydrofuran (THF) of 400ml drying (solvent); under the nitrogen protection; be cooled to below-80 ℃; drip 96ml (0.24mol; 2.5N) n-Butyl Lithium (reactant); dripped Bi Baowen 1 hour; under the same temperature; splash into 0.216mol1; the mixing solutions of 4-butyrolactone (reactant) and 50ml dry tetrahydrofuran (solvent) drips to finish and stirred 30 minutes, heats up naturally; drip 200ml saturated aqueous ammonium chloride (adjusting pH value) about 0 ℃; separatory, water extracts with 200ml ethyl acetate (solvent), the organic phase washing; be spin-dried for; obtain 50g (GC:89%) liquid, add products obtained therefrom above the 50g, the methylene dichloride of 500ml drying (solvent) in another 1L there-necked flask; under the nitrogen protection; be cooled to-25～-20 ℃, drip 63.3ml (0.397mol, 2.2eq) triethyl silicon hydrogen (reactant); drip and finish; (0.397mol, the 2.2eq) diethyl ether solution of boron trifluoride (reactant) drip to finish and keep-25～-20 ℃ to stir 2 hours Dropwise 5 0ml in the system; naturally rise to 0 ℃; add saturated aqueous solution of sodium bicarbonate (adjusting pH value) and do not emit to there being bubble, separatory is washed to neutrality; be spin-dried for solvent; with 2 times of ethanol (solvent) recrystallization, suction filtration, get near-white crystal powder (2-a) 28g; yield 70%, gas chromatographic purity 99%.

Step 2:

Add 0.1mol (2-a) in the reaction flask; 0.12mol3; 5-two fluorobenzoic boric acids (reactant); 0.2mol yellow soda ash (reactant), 80ml toluene (solvent), 60ml ethanol (solvent); 60ml water (solvent); under the logical nitrogen protection, add 0.4g tetrakis triphenylphosphine palladium (catalyzer), be heated with stirring to back flow reaction 3 hours.Be cooled to room temperature, separatory extracts water with 50ml toluene (solvent), and the organic phase merging is washed to neutrality.Solvent evaporated, gains are dissolved in 100ml toluene, cross the silicagel column decolouring, with toluene (solvent) wash-out, collect elutriant and solvent evaporated, obtain white solid (2-b).Yield 90%, gas chromatographic purity 98.0%.

Step 3:

In reaction flask, add 0.1mol (2-b) (reactant), 200ml tetrahydrofuran (THF) (solvent), logical nitrogen protection; be cooled to-60 ℃, drip 0.11mol n-Butyl Lithium (reactant), drip process temperature control-55 ℃～-60 ℃; drip and finish, continued the temperature control stirring reaction 1 hour.Be cooled to-70 ℃, drip 0.15mol difluorodibromomethane (reactant), drip process temperature control-65 ℃～-70 ℃, drip and finish, continue the temperature control stirring reaction 30 minutes, and be warming up to room temperature, add 20ml concentrated hydrochloric acid (adjusting pH value)+50ml water (solvent) hydrolysis, separatory, 100ml methylene dichloride (solvent) extracts water, and the washing organic phase is to neutral, and solvent evaporated gets weak yellow liquid (2-c), yield 70%, gas chromatographic purity 78%.

Step 4:

In reaction flask, add 0.01mol (1-c) (reactant), 50mlDMSO (solvent), 0.02mol Anhydrous potassium carbonate (reactant), 0.012mol3,4,5-trifluoromethyl phenol (reactant) is heated with stirring to 65～70 ℃ of reactions 2 hours.Be cooled to room temperature, cross filter solid, and with 30ml methylene dichloride (solvent) flush cake, filtrate adds 100ml water, stirs, separatory extracts water layer with 20ml methylene dichloride (solvent), and the washing organic phase is to neutrality, solvent evaporated.Enriched material is dissolved in 50ml toluene (solvent), crosses the silicagel column decolouring, with toluene (solvent) wash-out, collection elutriant and steaming desolventize, and gains dehydrated alcohol (solvent) recrystallization 3 times obtain white needle-like crystals (2-d), yield 40%, gas chromatographic purity 99.5%.

The structure verification data of this product are as follows:

MP：83℃

MS:m/s%170 (2.4) 239 (10.9) 252 (3.5) 267 (10.7) 279 (4.1) 309 (100) 456 (1.2), and mass spectrum as shown in Figure 1.

As from the foregoing, this product structure is correct, is the compound of ownership formula I.

The liquid crystal property detected result of this compound is as follows:

Δε：20.0V

Δn：0.16。

η：20

As from the foregoing, this compound has bigger specific inductivity and moderate specific refractory power, and less viscosity can be applicable in the mixed liquid crystal.

According to the method for previous embodiment 2, only the substituting group in the reactant is carried out corresponding replacement according to the substituting group in the target product, obtain the compound of following ownership formula I:

Compound shown in embodiment 3, the preparation formula I

Step 1

Add 0.1mol (1-a) in the reaction flask; a 0.12mol fluorobenzoic boric acid (reactant); 0.2mol yellow soda ash (reactant); 80ml toluene (solvent); 60ml ethanol (solvent), 60ml water (solvent) is under the logical nitrogen protection; add 0.4g tetrakis triphenylphosphine palladium (catalyzer), be heated with stirring to back flow reaction 3 hours.Be cooled to room temperature, separatory extracts water with 50ml toluene (solvent), and the organic phase merging is washed to neutrality.Solvent evaporated, gains are dissolved in 100ml toluene, cross the silicagel column decolouring, with toluene (solvent) wash-out, collect elutriant and solvent evaporated, and with-20 ℃ of frozen recrystallizations behind 3 times of petroleum ether dissolutions, suction strainer obtains white crystal (3-a).Yield 90%, gas chromatographic purity 99.5%.

Step 2

In reaction flask, add 0.1mol (3-b) (reactant); 0.11mol potassium tert.-butoxide; 80ml tetrahydrofuran (THF) (solvent); logical nitrogen protection; be cooled to-90 ℃; drip sherwood oil (solvent) solution of 0.12mol n-Butyl Lithium (reactant), dropwise in 1 hour ,-90 ℃ of stirring reactions 30 minutes.Still temperature control dripped 70ml tetrahydrofuran (THF) (solvent) solution of 0.11mol iodine (reactant), after adding to-90 ℃ in 1 hour, continued the temperature control stirring reaction 1 hour, be warming up to 0 ℃, with aqueous solution of sodium bisulfite (reductive agent) except excessive iodine in the dereaction, add water washing after, sherwood oil (solvent) extracts and separatory, the washing organic phase is to neutral, after the solvent evaporated, with-20 ℃ of frozen recrystallizations after 2 times of sherwood oils and the 1 times of dehydrated alcohol heating for dissolving, suction strainer obtains white crystal (3-b).Yield 60%, gas chromatographic purity 99.5%.

Step 3:

Add 0.1mol (3-b) in the reaction flask; 0.12mol3; 5-two fluorobenzoic boric acids (reactant); 0.2mol yellow soda ash (reactant), 80ml toluene (solvent), 60ml ethanol (solvent); 60ml water (solvent); under the logical nitrogen protection, add 0.4g tetrakis triphenylphosphine palladium (catalyzer), be heated with stirring to back flow reaction 3 hours.Be cooled to room temperature, separatory extracts water with 50ml toluene (solvent), and the organic phase merging is washed to neutrality.Solvent evaporated, gains are dissolved in 100ml toluene, cross the silicagel column decolouring, with toluene (solvent) wash-out, collect elutriant and solvent evaporated, obtain white solid (3-c).Yield 90%, gas chromatographic purity 98.0%.

Step 4

In reaction flask, add 0.1mol (3-c) (reactant), 200ml tetrahydrofuran (THF) (solvent), logical nitrogen protection; be cooled to-60 ℃, drip 0.11mol n-Butyl Lithium (reactant), drip process temperature control-55 ℃～-60 ℃; drip and finish, continued the temperature control stirring reaction 1 hour.Be cooled to-70 ℃, drip 0.15mol difluorodibromomethane (reactant), drip process temperature control-65 ℃～-70 ℃, drip and finish, continue the temperature control stirring reaction 30 minutes, and be warming up to room temperature, add 20ml concentrated hydrochloric acid (adjusting pH value)+50ml water (solvent) hydrolysis, separatory, 100ml methylene dichloride (solvent) extracts water, and the washing organic phase is to neutral, and solvent evaporated gets faint yellow solid (3-d), yield 90%, gas chromatographic purity 78%.

Step 5:

In reaction flask, add 0.01mol (2-d) (reactant), 50mlDMSO (solvent), 0.02mol Anhydrous potassium carbonate (reactant), 0.012mol3,4,5-trifluoromethyl phenol (reactant) is heated with stirring to 65～70 ℃ of reactions 2 hours.Be cooled to room temperature, cross filter solid, and with 30ml methylene dichloride (solvent) flush cake, filtrate adds 100ml water, stirs, separatory extracts water layer with 20ml methylene dichloride (solvent), and the washing organic phase is to neutrality, solvent evaporated.Enriched material is dissolved in 50ml toluene (solvent), crosses the silicagel column decolouring, with toluene (solvent) wash-out, collection elutriant and steaming desolventize, and gains dehydrated alcohol (solvent) recrystallization 3 times obtain white needle-like crystals (3-e), yield 40%, gas chromatographic purity 99.5%.

The structure verification data of this product are as follows:

MP：86℃CP：152℃

MS：m/s％333(10.2)361(10.5)403(100)550(1.3)

As from the foregoing, this product structure is correct, is the compound of ownership formula I.

The liquid crystal property detected result of this compound is as follows:

Δε：23.0V

Δn：0.19

η：48

As from the foregoing, this compound has bigger specific inductivity and moderate specific refractory power, and less viscosity can be applicable in the mixed liquid crystal

According to the method for previous embodiment 3, only the substituting group in the reactant is carried out corresponding replacement according to the substituting group in the target product, obtain the compound of following ownership formula I:

Compound shown in embodiment 4, the preparation formula I

Step 1

Specifically with step 1. among the top embodiment 2

Step 2

Add the 0.1mol (2-a) (reactant) that step obtains in the reaction flask, 120ml tetrahydrofuran (THF) (solvent), sealing is installed stirs, logical nitrogen replacement air, be cooled to-70 ℃, dripping 0.1mol concentration is the butyllithium (reactant) of 2.5M, adds back 20 minutes, feeds dry carbon dioxide (reactant), to saturated, reaction is 2 hours under this temperature, this reaction solution is poured into hydrolysis in the beaker of 20ml concentrated hydrochloric acid (adjusting pH value) and 100ml water, separatory, 50ml ethyl acetate (solvent) is extracted water once, merge organic phase, saturated common salt is washed to neutrality, anhydrous sodium sulphate (siccative) drying, concentrate and eliminate solvent, obtain light yellow solid, with 2 times of toluene and 1 times of ethyl acetate (solvent) recrystallization once, obtain white crystal (4-a).Yield 90%, liquid chromatography purity 98.0%.

Step 3

Add 0.1mol (4-a) in the reaction flask; 30ml toluene (solvent) and 30ml octane-iso (solvent); add 14g1; 3-dimercaptopropane (reactant); stir down above-mentioned suspension is heated to 50 ℃; in 30 minutes, add trifluoromethanesulfonic acid (reactant) 19.5g; being warming up to after adding refluxes carries out dehydration reaction; tell the water of generation; after treating the clean water byproduct of branch; cool to 90 ℃, between 70-90 ℃, add methyl tertiary butyl ether (solvent) 100ml in 45 minutes, continue cooling; separate out crystal; filter under nitrogen protection, the crystal that obtains washs with methyl tertiary butyl ether (solvent) (25ml * 4), and vacuum-drying obtains orange crystal (dithiane fluoroform sulphonate) (4-b).

Step 4

In reaction flask, add 0.1mol3,4,5-trifluoromethyl phenol (reactant), 0.1mol the mixing solutions of triethylamine (reactant) and 130ml methylene dichloride (solvent) also is cooled to-70 ℃, drip the solution of the 120ml methylene dichloride (solvent) of above-mentioned 0.1mol (4-b) crystal (reactant), added in 45 minutes, and after this temperature stirs one hour, added 0.4mol NEt in 5 minutes ₃3HF (reactant).Then under-70 ℃, 30ml methylene dichloride (solvent) solution that adds 0.4mol bromine (reactant) in one hour, continue reaction one hour down at-70 ℃ then, be warming up to 0 ℃, reaction solution is poured in 32% 160ml aqueous sodium hydroxide solution (adjusting pH value) and the 300g ice, come pH value to 5～8 of conditioned reaction liquid by dripping about 45g32% aqueous sodium hydroxide solution.Water extracts with 80ml methylene dichloride (solvent) behind the separatory, and merge organic phase and filter with 4g diatomite (discoloring agent), washing, decompression is solvent evaporated down.Sherwood oil (solvent) recrystallization obtains white crystal product (4-c) behind the crude product column chromatography that obtains, yield 45%, and the structure verification data of this product are as follows:

GC：99.8％。

MP：35℃

MS：m/s％146(11.04)162(8.84)188(5.66)223(20.57)2672(100)344(5.87)

As from the foregoing, this product structure is correct, is the compound of ownership formula I.

The liquid crystal property detected result of this compound is as follows:

Δε：18.0V

Δn：0.18

η：14

As from the foregoing, this compound has bigger specific inductivity and moderate specific refractory power, and less viscosity can be applicable in the mixed liquid crystal.

According to the method for previous embodiment 4, only the substituting group in the reactant is carried out corresponding replacement according to the substituting group in the target product, obtain the compound of following ownership formula I:

Compound shown in embodiment 5, the preparation formula I

Step 1

Add 0.1mol (3-b) in the reaction flask, glacial acetic acid 100ml, 5%Pt/C10g, atmospheric hydrogenation is 6 hours under stirring, and removes by filter catalyzer, and solvent evaporated adds 50ml toluene recrystallization, and yield 50% gets (5-a)

Step 2

Add 0.1mol (2-b) in the reaction flask; 30ml toluene (solvent) and 30ml octane-iso (solvent); add 14g1; 3-dimercaptopropane (reactant); stir down above-mentioned suspension is heated to 50 ℃; in 30 minutes, add trifluoromethanesulfonic acid (reactant) 19.2g, be warming up to backflow after adding, tell the water of generation; after treating the branch water purification; cool to 90 ℃, between 70-90 ℃, add methyl tertiary butyl ether (solvent) 100ml in 45 minutes, continue cooling; separate out crystal; filter under nitrogen protection, the crystal that obtains washs with methyl tertiary butyl ether (solvent) (25ml * 4), and vacuum-drying obtains orange crystal (dithiane fluoroform sulphonate) (5-b).

Step 3

In reaction flask, add 0.1mol2,3 ', 4 ', 5 '-tetrafluoro biphenyl-4-phenol (reactant), 0.1mol the mixing solutions of triethylamine (reactant) and 130ml methylene dichloride (solvent) also is cooled to-70 ℃, drips the solution of the 120ml methylene dichloride (solvent) of above-mentioned 0.1mol (4-b) crystal (reactant), adds in 45 minutes, after this temperature stirs 1 hour, add 0.4mol NEt in 5 minutes ₃3HF (reactant).Then under-70 ℃, 30ml methylene dichloride (solvent) solution that adds 0.4mol bromine (reactant) in one hour, continue reaction one hour down at-70 ℃ then, be warming up to 0 ℃, reaction solution is poured in 32% 160ml aqueous sodium hydroxide solution (adjusting pH value) and the 300g ice, come pH value to 5～8 of conditioned reaction liquid by dripping about 45g32% aqueous sodium hydroxide solution.Water extracts with 80ml methylene dichloride (solvent) behind the separatory, and merge organic phase and filter with 4g diatomite (discoloring agent), washing, decompression is solvent evaporated down.Sherwood oil (solvent) recrystallization obtains white crystal product (5-c), yield 45%, GC:99.5% behind the crude product column chromatography that obtains.

The structure verification data of this product are as follows:

MP：53℃

MS：m/s％69(79.3)202(100)188(5.66)242(32.5)444(84.3)

As from the foregoing, this product structure is correct, is the compound of ownership formula I.

The liquid crystal property detected result of this compound is as follows:

Δε：18.0V

Δn：0.10

η：35

As from the foregoing, this compound has bigger specific inductivity and moderate specific refractory power, and less viscosity can be applicable in the mixed liquid crystal.

According to the method for previous embodiment 5, only the substituting group in the reactant is carried out corresponding replacement according to the substituting group in the target product, obtain the compound of following ownership formula I:

Compound shown in embodiment 6, the preparation formula I

The synthetic method of present embodiment prepares following compound with reference to the partial reaction of embodiment 3.

Step 1

Add 0.05mol (3-b) (reactant) in the reaction flask, 0.06mol3,4,5-trifluoro-benzene boric acid (reactant), 0.1mol yellow soda ash (reactant), 100ml toluene (solvent), 40ml water (solvent), 0.1g tetra-triphenylphosphine palladium (catalyzer) was heated with stirring to back flow reaction 3 hours.Be cooled to room temperature, separatory extracts water with 20ml toluene (solvent), and the organic phase merging is washed to neutrality.Solvent evaporated, gains are dissolved in 80ml sherwood oil (solvent), cross silicagel column (discoloring agent) decolouring, with sherwood oil (solvent) wash-out, collect elutriant and solvent evaporated, solvent evaporated, gains with 2 times of toluene and 2 times of petroleum ether dissolutions after ,-20 ℃ of frozen recrystallizations 3 times, suction strainer, get white crystal product (6-a), yield 80%, gas chromatographic purity 99.8%.

The structure verification data of this product are as follows:

MS：m/z％139(2.77)182(3.41)225(9.94)319(100)372(M ⁺5.6)

MP：102℃

As from the foregoing, this product structure is correct, is the compound of ownership formula I.

The liquid crystal property detected result of this compound is as follows:

Δε：15.3(20℃，589nm)

Δn：0.14(20℃，1000Hz)

η：54

As from the foregoing, this compound has bigger specific inductivity and moderate specific refractory power, and less viscosity can be applicable in the mixed liquid crystal.

Compound shown in embodiment 7, the preparation formula I

The synthetic method of present embodiment prepares following compound with reference to the partial reaction of embodiment 2.

Step 1

Add 0.05mol (2-a) (reactant) in the reaction flask, 0.06mol4-oxyethyl group-2,3-two fluorobenzoic boric acids (reactant), 0.1mol yellow soda ash (reactant), 100ml toluene (solvent), 40ml water (solvent), 0.1g tetra-triphenylphosphine palladium (catalyzer) was heated with stirring to back flow reaction 3 hours.Be cooled to room temperature, separatory extracts water with 20ml toluene (solvent), and the organic phase merging is washed to neutrality.Solvent evaporated, gains are dissolved in 80ml sherwood oil (solvent), cross silicagel column (discoloring agent) decolouring, with sherwood oil (solvent) wash-out, collect elutriant and solvent evaporated, solvent evaporated, gains with 2 times of toluene and 2 times of petroleum ether dissolutions after ,-20 ℃ of frozen recrystallizations 3 times, suction strainer, get white crystal product (6-a), yield 80%, gas chromatographic purity 99.8%.

The structure verification data of this product are as follows:

MS：m/z％234(32.7)262(20.5)276(2.5)304(100)372

MP：45℃

As from the foregoing, this product structure is correct, is compound shown in the formula II of ownership formula I.

The liquid crystal property detected result of this compound is as follows:

Δε：-6.4(20℃，589nm)

Δn：0.119(20℃，1000Hz)

η：60

As from the foregoing, this compound has bigger negative permittivity and moderate specific refractory power, and less viscosity can be applicable in the mixed liquid crystal.

According to previous embodiment 6,7 method, only the substituting group in the reactant is carried out corresponding replacement according to the substituting group in the target product, obtain the compound of following ownership formula I:

Embodiment 8, preparation liquid crystal compound a

With each compound mixing, obtain liquid crystal compound a according to following mass parts:

Embodiment 2 preparation gained

The performance test results of this liquid crystal compound a is as follows:

Cp：96℃；Δn＝0.13；Δε＝4.2；γ ₁＝85；

As from the foregoing, said composition has high clearing point, suitable optical anisotropy, and low rotary viscosity and response speed faster are in liquid-crystal display.

Embodiment 9, preparation liquid crystal compound b

With each compound mixing, obtain liquid crystal compound b according to following mass parts:

Embodiment 1 preparation gained

The performance test results of this liquid crystal compound b is as follows:

Cp：87℃；Δn＝0.123；Δε＝5.1；γ ₁＝65；

As from the foregoing, said composition has high clearing point, suitable optical anisotropy, and low rotary viscosity and response speed faster are in liquid-crystal display.

Embodiment 10, preparation liquid crystal compound c

With each compound mixing, obtain liquid crystal compound c according to following mass parts:

Embodiment 3 preparation gained

The performance test results of this liquid crystal compound c is as follows:

Cp：87℃；Δn＝0.105；Δε＝7.2；γ ₁＝65；

As from the foregoing, said composition has high clearing point, suitable optical anisotropy, and low rotary viscosity and response speed faster are in liquid-crystal display.

Embodiment 11, preparation liquid crystal compound d

With each compound mixing, obtain liquid crystal compound d according to following mass parts:

Embodiment 3 preparation gained

Embodiment 2 preparation gained

The performance test results of this liquid crystal compound d is as follows:

Cp：87℃；Δn＝0.112；Δε＝7.7；γ ₁＝65；

As from the foregoing, said composition has high clearing point, suitable optical anisotropy, and low rotary viscosity and response speed faster are in liquid-crystal display.

Embodiment 12, preparation liquid crystal compound e

With each compound mixing, obtain liquid crystal compound e according to following mass parts:

Embodiment 2 preparation gained

Embodiment 3 preparation gained

The performance test results of this liquid crystal compound e is as follows:

Cp：87℃；Δn＝0.110；Δε＝6.9；γ ₁＝63；

As from the foregoing, said composition has high clearing point, suitable optical anisotropy, and low rotary viscosity and response speed faster are in liquid-crystal display.

Claims (15)

1. compound shown in the formula I,

Formula I

Among the described formula I, R ₁And R ₂Identical or different, all be selected from hydrogen atom, alkyl, alkoxyl group, substituted alkyl and alkoxyl group, C1, F ,-CN ,-OCN ,-OCF ₃,-CF ₃,-CHF ₂,-OCHF ₂,-SCN ,-NCS and-SF ₅

Wherein, the total number of carbon atoms of described alkyl or alkoxyl group is 1-15;

Described substituted alkyl be in the alkyl at least one-CH ₂-by-CH=CH-,-C ≡ C-,-COO-,-OOC-, tetramethylene or-O-replace and group or at least one hydrogen atom in the alkyl replaced by fluorine or chlorine and group;

Described substituted alkoxyl group be in the alkoxyl group at least one-CH ₂-by-CH=CH-,-C ≡ C-,-COO-,-OOC-, tetramethylene or-O-replace and group or at least one hydrogen atom in the alkoxyl group replaced by fluorine or chlorine and group;

A ₁, A ₂, A ₃And A ₄Identical or different, all be selected from least a in the following radicals:

L ¹, L ²And L ³Identical or different, all be selected from singly-bound ,-CH=CH-,-C ≡ C-,-COO-,-OOC-,-CF ₂O-,-OCH ₂-,-CH ₂O-,-OCF ₂-,-CH ₂CH ₂-,-CF ₂CH ₂-,-CH ₂CF ₂-,-C ₂F ₄-,-CF=CF-and-(CH ₂) ₄-at least a;

A, b and c all are selected from the integer of 0-3, and a+b+c≤5.

2. compound according to claim 1 is characterized in that: any one that compound shown in the described formula I is formula I1 to the compound shown in the formula I14:

Formula I1

Formula I2

Formula I3 Formula I4

Formula I5

Formula I6

Formula I7

Formula I8

Formula I9

Formula I10

Formula I11

Formula I12

Formula I13

Formula I14

Described formula I1 to formula I14, R ₁And R ₂Definition all identical with claim 1 ,-(F) expression has the fluorine atom substituting group on the phenyl ring or is hydrogen;

R ₁Be specially hydrogen, the total number of carbon atoms is the straight chained alkyl of 1-10 or the straight chain alkoxyl group that the total number of carbon atoms is 1-10;

R ₂Be specially hydrogen, the total number of carbon atoms and be the straight chained alkyl of 1-10, straight chain alkoxyl group that the total number of carbon atoms is 1-10, C1, F ,-CN ,-OCF ₃,-CF ₃,-SCN ,-CHF ₂Or-OCHF ₂

3. one kind prepares L among claim 1 or the 2 described formula I ₁For-CF ₂O, A ₁For The time compound method, comprise the steps:

1) will

-80 ℃ with

React with n-Butyl Lithium, the reaction diethyl ether solution that obtains adding again behind the product triethyl silicon hydrogen and boron trifluoride that finishes reacted 1-3 hour at-20～-25 ℃, and reaction finishes and obtains

2) with the step 1) gained

Reacted 20-40 minute at-50～-70 ℃ with n-Butyl Lithium and difluorodibromomethane, obtain

3) with step 2) gained

With

Reacted 2-5 hour at 50～70 ℃ with carbonate, obtain L among the described formula I ₁For-CF ₂O, A ₁For

The time compound;

Above-mentioned steps 1) to step 3), a in the described structural formula, R ₁, R ₂, A ₂, b, c, L ₂, L ₃, A ₃And A ₄Definition all identical with claim 1 definition.

4. method according to claim 3 is characterized in that: in the described step 1),

The molar ratio of n-Butyl Lithium, triethyl silicon hydrogen and boron trifluoride is 1: 1.1: 1.1: 2.2: 2.2;

Described step 2) in,

With the molar ratio of n-Butyl Lithium and difluorodibromomethane be 1: 1.1: 1.5; In the described reactions steps, the time is 30 minutes;

In the described step 3),

With the molar ratio of carbonate be 1: 1-1.3: 2.

5. one kind prepares L among claim 1 or the 2 described formula I ₂For-CF ₂O, A ₂For

The time compound method, comprise the steps:

1) will

React at-50～-80 ℃ with n-Butyl Lithium, the reaction diethyl ether solution that obtains adding again behind the product triethyl silicon hydrogen and boron trifluoride that finishes reacted 1-3 hour at-20～-25 ℃, and reaction finishes and obtains

2) with the step 1) gained

With

Carbonate and four triphenylphosphines close the palladium mixing and carry out cocurrent flow reaction 2-4 hour, and reaction finishes and obtains

3) with step 2) gained

N-Butyl Lithium, difluorodibromomethane reacted 20-40 minute, and reaction finishes and obtains

4) with the step 3) gained With

Reacted 2-5 hour at 50-70 ℃ with carbonate, reaction finishes and obtains L among the described formula I ₂For-CF ₂O, A ₂For

The time compound;

Described step 1) to step 4), the A in the described structural formula ₁, L ₁, a, R ₁, A ₂, b, c, L ₃, A ₃And A ₄Definition all identical with claim 1 definition.

6. method according to claim 5 is characterized in that:

The molar ratio of n-Butyl Lithium, triethyl silicon hydrogen and boron trifluoride is 1: 1.1: 1.1: 2.2: 2.2;

Described step 2) in,

With

The amount ratio that carbonate and four triphenylphosphines close palladium is 1mol: 1.2mol: 2mol: 4g; Described carbonate is selected from least a in yellow soda ash and the salt of wormwood;

In the described step 3),

The molar ratio of n-Butyl Lithium and difluorodibromomethane is 1: 1.1: 1.5; In the described reactions steps, the time is 30 minutes;

In the described step 4),

With the molar ratio of carbonate be 1: 1～1.3: 2; Described carbonate is selected from least a in yellow soda ash and the salt of wormwood.

7. one kind prepares L among claim 1 or the 2 described formula I ₃For-CF ₂O, A ₃For

The time compound method, comprise the steps:

1) will

React at-50～-80 ℃ with n-Butyl Lithium, the reaction diethyl ether solution that obtains adding again behind the product triethyl silicon hydrogen and boron trifluoride that finishes reacted 1-3 hour at-20～-25 ℃, and reaction finishes and obtains

2) with the step 1) gained

With

Carbonate and four triphenylphosphines close the palladium mixing and carry out cocurrent flow reaction 2-4 hour, and reaction finishes and obtains

3) with step 2) gained

Potassium tert.-butoxide, n-Butyl Lithium and iodine react in-90 ℃, and reaction finishes and obtains

4) with described step 3) gained Carbonate and four triphenylphosphines close the palladium mixing and carry out the cocurrent flow reaction, and reaction finishes and obtains

5) with described step 4) gained React at-50～-70 ℃ with n-Butyl Lithium and difluorodibromomethane, reaction finishes and obtains

6) with the step 5) gained Reacted 2-5 hour at 50-70 ℃ with carbonate, reaction finishes and obtains L among the described formula I ₃For-CF ₂O, A ₃For

The time compound;

Above-mentioned steps 1) to step 6), the A in the described structural formula ₁, L ₁, a, R ₁, R ₂, L ₂, A ₂, b, c and A ₄Definition all identical with the definition in the claim 1.

8. method according to claim 5 is characterized in that: in the described step 1),

The molar ratio of n-Butyl Lithium, triethyl silicon hydrogen and boron trifluoride is 1: 1.1: 1.1: 2.2: 2.2;

Described step 2) in,

With

The amount ratio that carbonate and four triphenylphosphines close palladium is 1mol: 1.2mol: 2mol: 4g; Described carbonate is selected from least a in yellow soda ash and the salt of wormwood;

In the described step 3),

The molar ratio of potassium tert.-butoxide, n-Butyl Lithium and iodine is 1: 1.1: 1.1: 1.: 1

In the described step 4),

With The ratio of carbonate and four triphenylphosphines is 1mol: 1.2mol: 2mol: 4g; Described carbonate is selected from least a in yellow soda ash and the salt of wormwood;

In the described step 5),

With the mol ratio of n-Butyl Lithium, difluorodibromomethane 1: 1.1: 1.5

In the described step 6), gained

With the molar ratio of carbonate be 1: 1～1.3: 2; Described carbonate is selected from least a in yellow soda ash and the salt of wormwood.

9. one kind prepares L among claim 1 or the 2 described formula I ₁For-CF ₂O, A ₁Be 1,4-cyclohexyl, 1,4-phenylene or except 3,5-, two fluoro-1, other formulas I described fluoro-1 beyond the 4-phenylene, the method for compound during the 4-phenylene comprises the steps:

1) will

React at-80 ℃ with n-Butyl Lithium, the reaction diethyl ether solution that obtains adding again behind the product triethyl silicon hydrogen and boron trifluoride that finishes reacted 1-3 hour at-20～-25 ℃, and reaction finishes and obtains

2) with the step 1) gained

With the n-Butyl Lithium mixing, and feed carbonic acid gas to saturated absorption, reacted 1-3 hour at-80 ℃ to-60 ℃, reaction finishes and obtains

3) with step 2) gained

Carry out dehydration reaction to the no coupling product water generates with 1,3-dimercaptopropane and trifluoromethanesulfonic acid backflow, obtain

4) with the step 3) gained Add NEt at-70 ℃ ₃3HF and bromine were reacted 1-3 hour, and reaction finishes and obtains L among the described formula I ₁For-CF ₂O, A ₁Be 1,4-cyclohexyl, 1,4-phenylene or except 3,5-, two fluoro-1, other formulas I described fluoro-1 beyond the 4-phenylene, compound during the 4-phenylene;

Above-mentioned steps 1) to step 4), the A in the described structural formula ₁, L ₁, a, R ₁, A ₂, b, c, L ₃All identical with claim 1 definition with the definition of A3.

10. method according to claim 9 is characterized in that: in the described step 1),

The molar ratio of n-Butyl Lithium, triethyl silicon hydrogen and boron trifluoride is 1: 1.1: 1.1: 2.2: 2.2;

Described step 2) in, The molar ratio of n-Butyl Lithium and carbonic acid gas is 1: 1: 2-3;

In the described step 3),

The molar ratio of 1,3-dimercaptopropane and trifluoromethanesulfonic acid is 1: 1.3: 1.3;

In the described step 4),

NEt ₃The molar ratio of 3HF, bromine is 1: 1: 1.3: 1.3; Described at-70 ℃ of adding NEt ₃3HF and bromine are carried out in the reactions steps, and the time is 2 hours.

11. one kind prepares L among claim 1 or the 2 described formula I ₁, L ₂And L ₃All be not-CF ₂The method of compound comprises the steps: during O

1) will React at-80 ℃ with n-Butyl Lithium, the reaction diethyl ether solution that obtains adding again behind the product triethyl silicon hydrogen and boron trifluoride that finishes reacts, and reaction finishes and obtains

2) with the step 1) gained

Carbonate and four triphenylphosphines close the palladium mixing and carry out the cocurrent flow reaction, and reaction finishes and obtains

3) with step 2) gained

Potassium tert.-butoxide, n-Butyl Lithium and iodine mixing react at-90 ℃, and reaction finishes and obtains

4) with the step 3) gained

Carbonate and palladium-carbon catalyst mixing carried out back flow reaction 2-4 hour, and reaction finishes and obtains L among the described formula I ₁, L ₂And L ₃All be not-CF ₂Compound during O;

Perhaps, according to following steps 5) preparation:

5) with the step 1) gained Carbonate and four triphenylphosphines close the palladium mixing and carry out the cocurrent flow reaction, and reaction finishes and obtains L among the described formula I ₁, L ₂And L ₃All be not-CF ₂Compound during O;

Described step 1) to step 5), the A in the described structural formula ₁, a, R ₁, A ₂, b, c and A ₃Definition all identical with claim 1 definition.

12. method according to claim 11 is characterized in that: in the described step 1), in the step 1),

The molar ratio of n-Butyl Lithium, triethyl silicon hydrogen and boron trifluoride is 1: 1.1: 1.1: 2.2: 2.2;

Described step 2) in,

The amount ratio that carbonate and four triphenylphosphines close palladium is 1mol: 1.2mol: 1.3mol: 4g; Described carbonate is selected from least a in yellow soda ash and the salt of wormwood;

In the described step 3),

The molar ratio of potassium tert.-butoxide, n-Butyl Lithium and iodine is 1: 1.1: 1.1: 1.1;

In the described step 4),

The amount ratio of carbonate and palladium-carbon catalyst is 1mol: 1.1mol: 1.3mol; Described carbonate is selected from least a in yellow soda ash and the salt of wormwood;

In the described step 5),

The amount ratio that carbonate and four triphenylphosphines close palladium is 1mol: 1.2mol: 2mol: 4g; Described carbonate is selected from least a in yellow soda ash and the salt of wormwood.

13. comprise at least a liquid crystal compound in claim 1 or the 2 arbitrary described compounds; Or,

Contain 1-5 kind claim 1 or 2 described compounds in the described liquid crystal compound, be specially and contain 2-4 kind claim 1 or 2 described compounds; Or,

At least a total mass accounts for the 1-90% of described liquid crystal compound gross weight in described claim 1 or the 2 arbitrary described compounds, is specially 5-60%, more specifically is 10-40%.

14. liquid crystal compound according to claim 13 is characterized in that: described liquid crystal compound is any one among the liquid crystal compound a to e:

Described liquid crystal compound a comprises the compound of following each mass parts or is made up of the compound of following each mass parts:

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

Described liquid crystal compound b comprises the compound of following each mass parts or is made up of the compound of following each mass parts:

Described liquid crystal compound b is specially the compound that comprises following each mass parts or is made up of the compound of following each mass parts:

Described liquid crystal compound c comprises the compound of following each mass parts or is made up of the compound of following each mass parts:

Described liquid crystal compound c is specially the compound that comprises following each mass parts or is made up of the compound of following each mass parts:

Described liquid crystal compound d comprises the compound of following each mass parts or is made up of the compound of following each mass parts:

Described liquid crystal compound d is specially the compound that comprises following each mass parts or is made up of the compound of following each mass parts:

Described liquid crystal compound e comprises the compound of following each mass parts or is made up of the compound of following each mass parts:

Described liquid crystal compound e is specially the compound that comprises following each mass parts or is made up of the compound of following each mass parts:

15. the application of the arbitrary described liquid crystal compound of the described liquid crystalline cpd of claim 1-2 or claim 13-14 in preparation liquid crystal display material or electrooptics display material; Or,

Comprise at least a liquid crystal display material optical liquid crystal indicating meter in the arbitrary described liquid crystal compound of the described liquid crystalline cpd of claim 1-3 or claim 13-14; Or,

Described indicating meter specifically is TN, STN or TFT indicating meter.

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