CN1185189C - Alkyl dicyclohexyl alkyne group liquid crystal and production method thereof - Google Patents

Abstract

The name of the present invention is an alkyl bicyclohexyl alkyne liquid crystal and a production method thereof. The object of the present invention is to provide a liquid crystal compound with low molecular melting point, wide liquid crystal phase range, good fat solubility and large optical anisotropy. What the present invention provides is the liquid crystal compound of following general formula (V); Its production method comprises the following steps: 1) prepare respectively (trans)-4-[(anti)-4-alkylcyclohexyl]cyclohexylacetylene and 4 -Alkyl-4'-bromotoluene or 4-fluoro-4'-bromotoluene or 3,4-difluoro-4'-bromotoluene or 3,4,5-trifluoro-4'-bromodiphenylacetylene; the alkyl group is methyl, ethyl, propyl, butyl or pentyl; 2) preparing the liquid crystal compound of formula (V).

Description

Alkyl bicyclohexyl alkyne liquid crystal and its production method

technical field

The invention relates to a liquid crystal material and a production method thereof.

Background technique

Liquid crystal materials are widely used in the field of information display, and their application in optical communication has also made progress (S.T.Wu, D.K.Yang. Reflective Liquid Crystal Displays. Wiley, 2001). With the further development of liquid crystal display technology and optical communication technology, people put forward new requirements for the performance of liquid crystal materials. Since it is impossible for any single-component liquid crystal to meet all the requirements of liquid crystal display, it is necessary to develop monomer liquid crystals with different properties, and then mix various liquid crystal compounds in appropriate proportions to obtain the best match of various characteristic parameters to meet the requirements. Different display requirements.

Optical anisotropy (Δn) is an important property of liquid crystals, which needs to be carefully regulated in liquid crystal displays. In recent years, large Δn liquid crystal materials have attracted attention, and some large Δn liquid crystal materials have been synthesized, but these materials are either directly connected by two carbon-carbon triple bonds in the molecule so that the stability is not ideal (R.A.Shenoy, M.E.Neubert etc., 2000 , Liq.Cryst., 27, 801.), or the molecular melting point is too high due to the many benzene rings in the molecule (C.Sekine, K.Iwa kura etc., 2001, Liq.Cryst., 28, 1375.), or Fat solubility is less than satisfactory.

Contents of the invention

The object of the present invention is to provide a liquid crystal compound with low molecular melting point, wide liquid crystal phase range, good fat solubility and large optical anisotropy.

What the present invention provides is the liquid crystal compound of following general formula (V):

Wherein, n=2-5; R=F or H; I=F or C _m H _2m+1 , m=2-5; X=F or H.

When R=H; X=H; I=C _m H _2m+1 , the compound of general formula (V) is the compound of formula (I):

Wherein, n=2-5; m=2-5.

When R=H; X=H; I=F, the compound of general formula (V) is the compound of formula (II):

Among them, n=2-5.

When X=H; R=F; I=F, the compound of general formula (V) is the compound of formula (III):

Among them, n=2-5. (III)

When R=F; X=F; I=F, the compound of general formula (V) is the compound of formula (IV):

Among them, n=2-5.

Specifically, the compound of the present invention may be one of the following family members:

1-{(trans)-4-[(trans)-4-ethylcyclohexyl]cyclohexylethynyl}-4-[4-methylphenylethynyl]benzene;

1-{(trans)-4-[(trans)-4-ethylcyclohexyl]cyclohexylethynyl}-4-[4-ethylphenylethynyl]benzene;

1-{(trans)-4-[(trans)-4-ethylcyclohexyl]cyclohexylethynyl}-4-[4-propylphenylethynyl]benzene;

1-{(trans)-4-[(trans)-4-ethylcyclohexyl]cyclohexylethynyl}-4-[4-butylphenylethynyl]benzene;

1-{(trans)-4-[(trans)-4-ethylcyclohexyl]cyclohexylethynyl}-4-[4-pentylphenylethynyl]benzene;

1-{(trans)-4-[(trans)-4-Propylcyclohexyl]cyclohexylethynyl}-4-[4-methylphenylethynyl]benzene;

1-{(trans)-4-[(trans)-4-Propylcyclohexyl]cyclohexylethynyl}-4-[4-ethylphenylethynyl]benzene;

1-{(trans)-4-[(trans)-4-Propylcyclohexyl]cyclohexylethynyl}-4-[4-propylphenylethynyl]benzene;

1-{(trans)-4-[(trans)-4-Propylcyclohexyl]cyclohexylethynyl}-4-[4-butylphenylethynyl]benzene;

1-{(trans)-4-[(trans)-4-Propylcyclohexyl]cyclohexylethynyl}-4-[4-pentylphenylethynyl]benzene;

1-{(trans)-4-[(trans)-4-butylcyclohexyl]cyclohexylethynyl}-4-[4-methylphenylethynyl]benzene;

1-{(trans)-4-[(trans)-4-butylcyclohexyl]cyclohexylethynyl}-4-[4-ethylphenylethynyl]benzene;

1-{(trans)-4-[(trans)-4-butylcyclohexyl]cyclohexylethynyl}-4-[4-propylphenylethynyl]benzene;

1-{(trans)-4-[(trans)-4-butylcyclohexyl]cyclohexylethynyl}-4-[4-butylphenylethynyl]benzene;

1-{(trans)-4-[(trans)-4-butylcyclohexyl]cyclohexylethynyl}-4-[4-pentylphenylethynyl]benzene;

1-{(trans)-4-[(trans)-4-pentylcyclohexyl]cyclohexylethynyl}-4-[4-methylphenylethynyl]benzene;

1-{(trans)-4-[(trans)-4-pentylcyclohexyl]cyclohexylethynyl}-4-[4-ethylphenylethynyl]benzene;

1-{(trans)-4-[(trans)-4-pentylcyclohexyl]cyclohexylethynyl}-4-[4-propylphenylethynyl]benzene;

1-{(trans)-4-[(trans)-4-pentylcyclohexyl]cyclohexylethynyl}-4-[4-butylphenylethynyl]benzene;

1-{(trans)-4-[(trans)-4-pentylcyclohexyl]cyclohexylethynyl}-4-[4-pentylphenylethynyl]benzene;

1-{(trans)-4-[(trans)-4-ethylcyclohexyl]cyclohexylethynyl}-4-[4-fluorophenylethynyl]benzene;

1-{(trans)-4-[(trans)-4-Propylcyclohexyl]cyclohexylethynyl}-4-[4-fluorophenylethynyl]benzene;

1-{(trans)-4-[(trans)-4-butylcyclohexyl]cyclohexylethynyl}-4-[4-fluorophenylethynyl]benzene;

1-{(trans)-4-[(trans)-4-pentylcyclohexyl]cyclohexylethynyl}-4-[4-fluorophenylethynyl]benzene;

1-{(trans)-4-[(trans)-4-ethylcyclohexyl]cyclohexylethynyl}-4-[3,4-difluorophenylethynyl]benzene;

1-{(trans)-4-[(trans)-4-Propylcyclohexyl]cyclohexylethynyl}-4-[3,4-difluorophenylethynyl]benzene;

1-{(trans)-4-[(trans)-4-butylcyclohexyl]cyclohexylethynyl}-4-[3,4-difluorophenylethynyl]benzene;

1-{(trans)-4-[(trans)-4-pentylcyclohexyl]cyclohexylethynyl}-4-[3,4-difluorophenylethynyl]benzene;

1-{(trans)-4-[(trans)-4-ethylcyclohexyl]cyclohexylethynyl}-4-[3,4,5-trifluorophenylethynyl]benzene;

1-{(trans)-4-[(trans)-4-Propylcyclohexyl]cyclohexylethynyl}-4-[3,4,5-trifluorophenylethynyl]benzene;

1-{(trans)-4-[(trans)-4-butylcyclohexyl]cyclohexylethynyl}-4-[3,4,5-trifluorophenylethynyl]benzene;

1-{(trans)-4-[(trans)-4-pentylcyclohexyl]cyclohexylethynyl}-4-[3,4,5-trifluorophenylethynyl]benzene.

A second object of the present invention is to provide a method for producing liquid crystal compounds of the general formula (V).

A method for producing the compound described in general formula (V), comprising the following steps:

1) Preparation of (anti)-4-[(anti)-4-alkylcyclohexyl]cyclohexylacetylene and 4-alkyl-4'-bromotoluene or 4-fluoro-4'-bromotoluene respectively or 3,4-difluoro-4'-bromotoluene or 3,4,5-trifluoro-4'-bromotoluene; the alkyl group is methyl, ethyl, propyl, butyl or Amyl;

2) (trans)-4-[(trans)-4-Alkylcyclohexyl]cyclohexylacetylene and 4-alkyl-4'-bromotoluene or 4-fluoro-4'-bromotoluene or 3 , 4 difluoro-4'-bromotoluene or 3,4,5-trifluoro-4'-bromotoluene in tetrakis(triphenyl)phosphorous palladium dichloride, cuprous iodide and triphenyl Under the catalysis of phosphorus, 1-{(anti)-4-[(anti)-4-alkylcyclohexyl]cyclohexylethynyl}-4-[4-alkylphenylethynyl]benzene, 1-{( Trans)-4-[(trans)-4-Alkylcyclohexyl]cyclohexylethynyl}-4-[4-fluorophenylethynyl]benzene, 1-{(trans)-4-[(trans)- 4-Alkylcyclohexyl]cyclohexylethynyl}-4-[3,4-difluorophenylethynyl]benzene or 1-{(trans)-4-[(trans)-4-alkylcyclohexyl] Cyclohexylethynyl}-4-[3,4,5-trifluorophenylethynyl]benzene; the alkyl group is methyl, ethyl, propyl, butyl or pentyl.

Wherein, the preparation of (anti)-4-[(anti)-4-alkylcyclohexyl]cyclohexylacetylene comprises the following steps:

1) Using (anti)-4-[(anti)-4-alkylcyclohexyl]cyclohexylcarboxylic acid as raw material to prepare (anti)-4-[(anti)-4-ethylcyclohexyl]cyclohexylmethanol;

2) Preparation of (anti)-4-[(anti)-4-alkylcyclohexyl]cyclohexylcarbaldehyde;

3) Preparation of (trans)(trans)-4-[(trans)-4-alkylcyclohexyl]cyclohexyl-β,β'-dibromoethylene;

4) Preparation of (anti)-4-[(anti)-4-alkylcyclohexyl]cyclohexylacetylene;

Described preparation 4-alkyl-4'-bromotoluene comprises the following steps:

1) Using 2-methyl-3-alkyn-2-ol and p-alkylbromobenzene as raw materials, under the catalysis of tetrakis (triphenyl) phosphorus palladium dichloride, cuprous iodide and triphenyl phosphorus 2-methyl-4-(4-alkylphenyl)-3-alkyn-2-ol;

2) preparing p-alkylphenylacetylene;

3) Preparation of 4-alkyl-4'-bromotoluene;

Described preparation 4-fluoro-4'-bromotoluene comprises the following steps:

1) Using 2-methyl-3-alkyne-2-ol and 4-fluorobromobenzene as raw materials, under the catalysis of tetrakis(triphenyl)phosphorous palladium dichloride, cuprous iodide and triphenylphosphine 2-methyl-4-(4-fluorophenyl)-3-alkyn-2-ol is generated;

2) Preparation of 4-fluorophenylacetylene;

3) Preparation of 4-fluoro-4'-bromotoluene;

Described preparation 3,4-difluoro-4'-bromotoluene comprises the following steps:

1) With 2-methyl-3-alkyne-2-alcohol and 3,4-difluorobromobenzene as raw materials, tetrakis(triphenyl)phosphorous palladium dichloride, cuprous iodide and triphenylphosphine Under the catalysis of 2-methyl-4-(3,4-difluorophenyl)-3-alkyn-2-alcohol;

2) Preparation of 3,4-difluorophenylacetylene;

3) Preparation of 3,4-difluoro-4'-bromotoluene;

Described preparation 3,4,5-trifluoro-4'-bromotoluene comprises the following steps:

1) With 2-methyl-3-alkyn-2-alcohol and 3,4,5-trifluorobromobenzene as raw materials, in tetrakis(triphenyl)phosphorous palladium dichloride, cuprous iodide and triphenyl Generating 2-methyl-4-(3,4-difluorophenyl)-3-alkyn-2-alcohol under the catalysis of base phosphorus;

2) Preparation of 3,4,5-trifluorophenylacetylene;

3) Preparation of 3,4,5-trifluoro-4'-bromotoluene.

The route step of synthetic compound of the present invention can be expressed with following formula:

In liquid crystal molecules, compared with benzene rings, cyclohexyl groups can reduce the melting point of molecules, broaden the range of liquid crystal phases, and increase the fat solubility; the introduction of lateral fluorine atoms can maintain some excellent characteristics of liquid crystals, and at the same time suppress orderly near The generation of crystalline phases enhances the dielectric anisotropy of liquid crystals.

The present invention will be further described below in conjunction with embodiment.

Detailed ways

Example 1, Preparation of 1-{(anti)-4-[(anti)-4-propylcyclohexyl]cyclohexylethynyl}-4-[4-butylphenylethynyl]benzene

The preparation of 1-{(anti)-4-[(anti)-4-propylcyclohexyl]cyclohexylethynyl}-4-[4-butylphenylethynyl]benzene comprises the following steps:

1. Preparation of (anti)-4-[(anti)-4-propylcyclohexyl]cyclohexylmethanol

Add 100ml of tetrahydrofuran (THF) and 7.6g of lithium aluminum hydride to a 250ml reaction flask, stir at room temperature, and slowly add 50ml of (trans)-4-[(trans)-4-propylcyclohexyl]cyclohexylcarboxylic acid dropwise THF solution, after the dropwise addition, continued to stir at room temperature for 4 hours, added dropwise 40ml of 40% potassium sodium tartrate solution to the reaction flask, collected the organic layer, and removed the solvent by rotary evaporation to obtain a light yellow solid crude product, which was washed with hexane After recrystallization, 19.8 g of white solid (trans)-4-[(trans)-4-propylcyclohexyl]cyclohexylmethanol was obtained, the purity by gas chromatography analysis: 99.2%, and the yield: 88.4%.

The following compounds can be obtained from the corresponding carboxylic acids in a similar manner:

(trans)-4-[(trans)-4-ethylcyclohexyl]cyclohexylmethanol

(trans)-4-[(trans)-4-butylcyclohexyl]cyclohexylmethanol

(trans)-4-[(trans)-4-pentylcyclohexyl]cyclohexylmethanol

2. Preparation of (anti)-4-[(anti)-4-propylcyclohexyl]cyclohexylcarbaldehyde

Add 100ml of dichloromethane, 19.8g of (trans)-4-[(trans)-4-propylcyclohexyl]cyclohexylmethanol, 28.4g of chromium trioxide pyridine hydrochloride obtained in the above step 1 in a 250ml reaction flask (PCC), after stirring at room temperature for 2 hours, add 100ml of anhydrous diethyl ether, continue to stir for 1 hour, let stand, decant the solution, remove the solvent by rotary evaporation, distill the residue under reduced pressure, collect 150 ℃ / 5mmHg colorless liquid (reverse) - 15.8 g of 4-[(trans)-4-propylcyclohexyl]cyclohexylcarbaldehyde, gas chromatography analysis purity: 98.1%, yield: 79.8%.

The following compounds can be prepared from the corresponding alcohols in a similar manner:

(trans)-4-[(trans)-4-ethylcyclohexyl]cyclohexylcarbaldehyde

(trans)-4-[(trans)-4-butylcyclohexyl]cyclohexylcarbaldehyde

(trans)-4-[(trans)-4-pentylcyclohexyl]cyclohexylcarbaldehyde

3. Preparation of (anti)(anti)-4-[(anti)-4-propylcyclohexyl]cyclohexyl-β,β-dibromoethylene

Add 150ml of dichloromethane solution containing 68.9g of triphenylphosphine into a 500ml reaction flask, cool to minus 20°C, add dropwise 100ml of dichloromethane solution containing 48.6g of carbon tetrabromide under stirring, and keep the temperature below minus 10 DEG C, continue to drop 20ml and contain the dichloromethane solution of (trans)-4-[(trans)-4-propylcyclohexyl]cyclohexylformaldehyde that 15.8g above-mentioned step 2 obtains, and reaction finishes, and reaction bottle is under subzero After standing at 20°C for 12 hours, decant the upper layer of the brown-red solution into 1000ml of hexane, let it stand for 3 hours, decant the supernatant, remove the solvent by rotary evaporation, distill the residue under reduced pressure, and collect the colorless liquid at 160°C/150Pa ( trans)(trans)-4-[(trans)-4-propylcyclohexyl]cyclohexyl-β,β′-dibromoethylene 23.2g, gas chromatography analysis purity: 98.6%, yield 86.3%.

The following compounds can be obtained from the corresponding aldehydes in a similar manner:

(Trans)-4-[(Trans)-4-Ethylcyclohexyl]cyclohexyl-β,β′-dibromoethylene

(trans)-4-[(trans)-4-butylcyclohexyl]cyclohexyl-β,β'-dibromoethylene

(trans)-4-[(trans)-4-pentylcyclohexyl]cyclohexyl-β,β'-dibromoethylene

4. Preparation of (anti)-4-[(anti)-4-propylcyclohexyl]cyclohexylacetylene

In a 100ml reaction flask, add 50ml of tetrahydrofuran solution containing 23.2g of (anti)(anti)-4-[(anti)-4-propylcyclohexyl]cyclohexyl-β,β'-dibromoethylene obtained in the above step 3 , magnetically stir the solution, seal the reaction bottle, and slowly inject 45.5ml of 2.78M n-butyllithium hexane solution below minus 78°C, after adding n-butyllithium, continue the reaction for 1 hour, then pour the reaction solution into 400ml of water, Wash the aqueous layer with 3×150ml hexane, combine the organic layers, wash the organic layer with 2×150ml water, and then wash it with 150ml saturated brine, collect the organic layer, remove the solvent by rotary evaporation, and distill the residue under reduced pressure. Color liquid (trans)-4-[(trans)-4-propylcyclohexyl]cyclohexylacetylene 9.2 g, gas chromatography analysis purity: 99.3%, yield 68.7%.

The following compounds can be obtained from corresponding starting materials in a similar manner:

(trans)-4-[(trans)-4-ethylcyclohexyl]cyclohexylacetylene

(trans)-4-[(trans)-4-butylcyclohexyl]cyclohexylacetylene

(trans)-4-[(trans)-4-pentylcyclohexyl]cyclohexylacetylene

5. Preparation of 2-methyl-4-(4-methylphenyl)-3-butyn-2-ol

Add 100ml triethylamine, 8.4g 2-methyl-3-butyn-2-alcohol, 17.1g p-methylbromobenzene, 0.4g tetrakis(triphenyl)phosphorous palladium dichloride, 0.4g to a 250ml reaction flask g cuprous iodide, 0.8g triphenylphosphine, stirred and refluxed for 12 hours, cooled to room temperature, added 50ml saturated ammonium chloride solution and 50ml dichloromethane, stirred for a few minutes, separated, and the water layer was washed with 3×40ml dichloromethane Wash with methane, combine the organic layers, wash the organic layer with 3×50ml water, collect the organic layer, dry with anhydrous sodium sulfate for one night, remove the solvent by rotary evaporation, distill the residue under reduced pressure, collect the 95°C/150Pa fraction to obtain a colorless liquid 12.1 g of 2-methyl-4-(4-methylphenyl)-3-butyn-2-ol, gas chromatography analysis purity: 97.5%, yield: 69.5%

The following compounds can be obtained from the corresponding reactants in a similar manner:

2-Methyl-4-(4-ethylphenyl)-3-butyn-2-ol

2-Methyl-4-(4-propylphenyl)-3-butyn-2-ol

2-Methyl-4-(4-butylphenyl)-3-butyn-2-ol

2-Methyl-4-(4-pentylphenyl)-3-butyn-2-ol

6. Preparation of p-butylphenylacetylene

Add 100ml of toluene, 12.1g of 2-methyl-4-(4-methylphenyl)-3-butyn-2-alcohol and 4g NaOH obtained in the above step 5 to a 250ml reaction flask, reflux for 4 hours, and rotate to evaporate The solvent was removed, the residue was distilled under reduced pressure, and the fraction at 35°C/150Pa was collected to obtain 9.2 g of p-butylphenylacetylene as a colorless liquid. Purity by gas chromatography: 98.8%, yield: 80%

The following compounds can be obtained from the corresponding reactants in a similar manner:

p-methylphenylacetylene

p-Ethylphenylacetylene

p-Propylphenylacetylene

p-Amylphenylacetylene

7. Preparation of 4-butyl-4'-bromotoluene

Add 100ml of triethylamine, 9.2g of p-butylphenylacetylene obtained in the above step 6, 22.6g of p-bromoiodobenzene, 0.3g of tetrakis(triphenyl)phosphorous palladium dichloride, 0.3g of phosphonium iodide in a 250ml reaction flask Copper, 0.6g triphenylphosphine, stirred and refluxed for 12 hours, cooled to room temperature, added 50ml saturated ammonium chloride solution and 50ml dichloromethane, stirred for a few minutes, separated, the water layer was washed with 3×40ml dichloromethane, combined The organic layer was washed with 3×50ml water, the organic layer was collected, dried overnight with anhydrous sodium sulfate, the solvent was removed by rotary evaporation, and the residue was recrystallized with n-hexane, and then separated by silica gel column chromatography to obtain a white solid 4-butane Base-4'-bromodiphenylacetylene 16.8g, gas chromatography analysis purity: 98.8%, yield: 77.8%

The following compounds were prepared by reacting the corresponding alkynes with p-bromoiodobenzene in a similar manner:

4-Methyl-4'-bromotoluene

4-Ethyl-4'-bromotoluene

4-Propyl-4'-bromotoluene

4-Pentyl-4'-bromotoluene

4-fluoro-4'-bromotoluene

3,4 Difluoro-4'-bromotoluene

3,4,5-Trifluoro-4'-bromotoluene

8. Preparation of 1-{(trans)-4-[(trans)-4-propylcyclohexyl]cyclohexylethynyl}-4-[4-butylphenylethynyl]benzene

Add 40ml of triethylamine, 0.5g of (trans)-4-[(trans)-4-propylcyclohexyl]cyclohexylacetylene obtained in the above step 4, and 0.6g of 4-butan obtained in the above step 7 into a 100ml reaction flask Base-4'-bromodiphenylacetylene, 0.02g tetrakis(triphenyl)phosphorus palladium dichloride, 0.02g cuprous iodide, 0.04g triphenylphosphine, stir and reflux for 12 hours, cool to room temperature, add 20ml saturated Ammonium chloride solution and 20ml of dichloromethane, stirred for a few minutes, separated, the aqueous layer was washed with 3×20ml of dichloromethane, the organic layer was combined, and the organic layer was washed with 3×50ml of water, the organic layer was collected and dried with anhydrous sodium sulfate Overnight, the solvent was removed by rotary evaporation, and the residue was recrystallized with n-hexane, and then separated by silica gel column chromatography to obtain a white solid 1-{(trans)-4-[(trans)-4-propylcyclohexyl]cyclohexylacetylene 0.6 g of phenyl)-4-[4-butylphenylethynyl]benzene, gas chromatography analysis purity: 99.7%, yield: 66.5%.

Structural identification: MS (M/Z): 464 (M ⁺ ); elemental analysis: calculated value C99.91 H0.09 found value C99.89H0.09; HNMR (CDCl ₃ /TMS): 7.39 (d, 4H), 7.31(d, 2H), 7.15(d, 2H), 2.62(t, 2H), 0.88, 2.34(d, 2H), 0.83～2.03(m, 32H)

Phase transition temperature: C 79.21S127.98 N 176.67I

The identification results showed that the obtained compound was indeed the target compound.

The following compounds were prepared in an analogous manner from the corresponding reactants:

1-{(trans)-4-[(trans)-4-ethylcyclohexyl]cyclohexylethynyl}-4-[4-methylphenylethynyl]benzene

1-{(trans)-4-[(trans)-4-ethylcyclohexyl]cyclohexylethynyl}-4-[4-ethylphenylethynyl]benzene

1-{(trans)-4-[(trans)-4-ethylcyclohexyl]cyclohexylethynyl}-4-[4-propylphenylethynyl]benzene

1-{(trans)-4-[(trans)-4-ethylcyclohexyl]cyclohexylethynyl}-4-[4-butylphenylethynyl]benzene

1-{(trans)-4-[(trans)-4-ethylcyclohexyl]cyclohexylethynyl}-4-[4-pentylphenylethynyl]benzene

1-{(trans)-4-[(trans)-4-propylcyclohexyl]cyclohexylethynyl}-4-[4-methylphenylethynyl]benzene

1-{(trans)-4-[(trans)-4-propylcyclohexyl]cyclohexylethynyl}-4-[4-ethylphenylethynyl]benzene

1-{(trans)-4-[(trans)-4-propylcyclohexyl]cyclohexylethynyl}-4-[4-propylphenylethynyl]benzene

1-{(trans)-4-[(trans)-4-propylcyclohexyl]cyclohexylethynyl}-4-[4-pentylphenylethynyl]benzene

1-{(trans)-4-[(trans)-4-butylcyclohexyl]cyclohexylethynyl}-4-[4-methylphenylethynyl]benzene

1-{(trans)-4-[(trans)-4-butylcyclohexyl]cyclohexylethynyl}-4-[4-ethylphenylethynyl]benzene

1-{(trans)-4-[(trans)-4-butylcyclohexyl]cyclohexylethynyl}-4-[4-propylphenylethynyl]benzene

1-{(trans)-4-[(trans)-4-butylcyclohexyl]cyclohexylethynyl}-4-[4-butylphenylethynyl]benzene

1-{(trans)-4-[(trans)-4-butylcyclohexyl]cyclohexylethynyl}-4-[4-pentylphenylethynyl]benzene

1-{(trans)-4-[(trans)-4-pentylcyclohexyl]cyclohexylethynyl}-4-[4-methylphenylethynyl]benzene

1-{(trans)-4-[(trans)-4-pentylcyclohexyl]cyclohexylethynyl}-4-[4-ethylphenylethynyl]benzene

1-{(trans)-4-[(trans)-4-pentylcyclohexyl]cyclohexylethynyl}-4-[4-propylphenylethynyl]benzene

1-{(trans)-4-[(trans)-4-pentylcyclohexyl]cyclohexylethynyl}-4-[4-butylphenylethynyl]benzene

1-{(trans)-4-[(trans)-4-pentylcyclohexyl]cyclohexylethynyl}-4-[4-pentylphenylethynyl]benzene

Example 2, Preparation of 1-{(anti)-4-[(anti)-4-propylcyclohexyl]cyclohexylethynyl}-4-[3,4-difluorophenylethynyl]benzene

Preparation of 1-{(anti)-4-[(anti)-4-propylcyclohexyl]cyclohexylethynyl}-4-[3,4-difluorophenylethynyl]benzene comprises the following steps:

1. Preparation of 2-methyl-4-(3,4-difluorophenyl)-3-butyn-2-ol

Add 100ml triethylamine, 8.4g 2-methyl-3-butyn-2-alcohol, 19.2g p-3,4-difluorobromobenzene, 0.4g tetrakis(triphenyl)phosphodiol to a 250ml reaction flask Palladium chloride, 0.4g cuprous iodide, 0.8g triphenylphosphine, stir and reflux for 12 hours, cool to room temperature, add 50ml saturated ammonium chloride solution and 50ml dichloromethane, stir for a few minutes, separate liquid, and use Wash with 3×40ml dichloromethane, combine the organic layers, wash the organic layer with 3×50ml water, collect the organic layer, dry with anhydrous sodium sulfate overnight, remove the solvent by rotary evaporation, distill the residue under reduced pressure, collect the 95°C/150Pa fraction, 18.3 g of colorless liquid 2-methyl-4-(3,4-difluorophenyl)-3-butyn-2-ol was obtained, the purity by gas chromatography analysis: 98.4%, the yield: 82.1%

The following compounds can be obtained from the corresponding reactants in a similar manner:

2-Methyl-4-(4-fluorophenyl)-3-butyn-2-ol

2-Methyl-4-(3,4,5-trifluorophenyl)-3-butyn-2-ol

2. Preparation of 3,4-difluorophenylacetylene

Add 100ml toluene, 18.3g 2-methyl-4-(3,4-difluorophenyl)-3-butyn-2-alcohol, 4g NaOH that above step 1 obtains in 250ml reaction bottle, reflux 4 hours, The solvent was removed by rotary evaporation, the residue was distilled under reduced pressure, and the fraction at 35°C/150Pa was collected to obtain 8.6 g of colorless liquid 3,4-difluorophenylacetylene. Purity by gas chromatography: 98.2%, yield: 77.5%

The following compounds can be obtained from the corresponding reactants in a similar manner:

4-Fluorophenylacetylene

3,4,5-Trifluorophenylacetylene

3. Preparation of 3,4 difluoro-4'-bromotoluene

Add 100ml of triethylamine, 8.6g of 3,4-difluorophenylacetylene obtained in the above step 6, 17.9g of p-bromoiodobenzene, 0.3g of tetrakis(triphenyl)phosphorous palladium dichloride, 0.3g Cuprous iodide, 0.6g triphenylphosphine, stirred and refluxed for 12 hours, cooled to room temperature, added 50ml of saturated ammonium chloride solution and 50ml of dichloromethane, stirred for a few minutes, separated, and used 3×40ml of dichloromethane for the aqueous layer Wash, combine the organic layers, wash the organic layer with 3×50ml water, collect the organic layer, dry it with anhydrous sodium sulfate overnight, remove the solvent by rotary evaporation, recrystallize the residue with n-hexane, and then separate it by silica gel column chromatography to obtain a white solid 13.9 g of 3,4-difluoro-4'-bromotoluene, gas chromatography analysis purity: 98.8%, yield: 77.8%

The following compounds can be obtained from the corresponding reactants in a similar manner:

4-fluoro-4'-bromotoluene

3,4,5-Trifluoro-4'-bromotoluene

4. Preparation of 1-{(anti)-4-[(anti)-4-propylcyclohexyl]cyclohexylethynyl}-4-[3,4-difluorophenylethynyl]benzene

In a 100ml reaction flask, add 40ml of triethylamine, 0.5g of (trans)-4-[(trans)-4-propylcyclohexyl]cyclohexylacetylene obtained in step 4 in Example 1, and 0.6g of the above-mentioned step 3 obtained 3,4 difluoro-4'-bromodiphenylacetylene, 0.02g tetrakis(triphenyl)phosphorous palladium dichloride, 0.02g cuprous iodide, 0.04g triphenylphosphine, stirred and refluxed for 12 hours, cooled to room temperature , add 20ml of saturated ammonium chloride solution and 20ml of dichloromethane, stir for a few minutes, separate the layers, wash the water layer with 3×20ml of dichloromethane, combine the organic layer, wash the organic layer with 3×50ml of water, collect the organic layer, and use Dry over sodium sulfate with water, remove the solvent by rotary evaporation, recrystallize the residue with n-hexane, and then separate it by silica gel column chromatography to obtain a white solid 1-{(trans)-4-[(trans)-4-propylcyclohexyl ]cyclohexylethynyl}-4-[3,4-difluorophenylethynyl]benzene 0.6 g, gas chromatography analysis purity: 99.2%, yield: 65.9%.

Structural identification: MS (M/Z): 444 (M ⁺ ); elemental analysis: calculated value C83.78 H7.66 F8.56 measured value C83.56 H7.71 F8.73; HNMR (CDCl ₃ /TMS): 7.07～7.41(m, 7H), 2.34(d, 2H), 0.83～2.03(m, 25H)

Phase transition temperature: C 82.68S117.21 N 138.27I

The identification results showed that the obtained compound was indeed the target compound.

The following compounds can be obtained from the corresponding reactants in a similar manner:

1-{(trans)-4-[(trans)-4-ethylcyclohexyl]cyclohexylethynyl}-4-[4-fluorophenylethynyl]benzene

1-{(trans)-4-[(trans)-4-propylcyclohexyl]cyclohexylethynyl}-4-[4-fluorophenylethynyl]benzene

1-{(trans)-4-[(trans)-4-butylcyclohexyl]cyclohexylethynyl}-4-[4-fluorophenylethynyl]benzene

1-{(trans)-4-[(trans)-4-pentylcyclohexyl]cyclohexylethynyl}-4-[4-fluorophenylethynyl]benzene

1-{(trans)-4-[(trans)-4-ethylcyclohexyl]cyclohexylethynyl}-4-[3,4-difluorophenylethynyl]benzene

1-{(trans)-4-[(trans)-4-butylcyclohexyl]cyclohexylethynyl}-4-[3,4-difluorophenylethynyl]benzene

1-{(trans)-4-[(trans)-4-pentylcyclohexyl]cyclohexylethynyl}-4-[3,4-difluorophenylethynyl]benzene

1-{(trans)-4-[(trans)-4-ethylcyclohexyl]cyclohexylethynyl}-4-[3,4,5-trifluorophenylethynyl]benzene

1-{(trans)-4-[(trans)-4-propylcyclohexyl]cyclohexylethynyl}-4-[3,4,5-trifluorophenylethynyl]benzene

1-{(trans)-4-[(trans)-4-butylcyclohexyl]cyclohexylethynyl}-4-[3,4,5-trifluorophenylethynyl]benzene

1-{(trans)-4-[(trans)-4-pentylcyclohexyl]cyclohexylethynyl}-4-[3,4,5-trifluorophenylethynyl]benzene

Claims (7)

1, the compound of logical formula V:

Wherein, n=2-5; R=F or H; I=F or C _mH _2m+1, m=2-5; X=F or H.

2, compound according to claim 1 is characterized in that: described compound is the compound of general formula (I)

Wherein, n=2-5; M=2-5.

3, compound according to claim 1 is characterized in that: described compound is the compound of general formula (II)

Wherein, n=2-5.

4, compound according to claim 1 is characterized in that: described compound is the compound of general formula (III)

Wherein, n=2-5.

5, compound according to claim 1 is characterized in that: described compound is the compound of general formula (IV)

Wherein, n=2-5.

6, the method for the described compound of a kind of production claim 1 may further comprise the steps:

1) preparation (instead)-4-[(is anti-respectively)-the 4-alkyl-cyclohexyl] cyclohexyl-acetylene and 4-alkyl-4 ' bromine tolane or 4-fluoro-4 ' bromine tolane or 3,4-two fluoro-4 ' bromine tolane or 3,4,5-three fluoro-4 ' bromine tolane; Described alkyl is methyl, ethyl, propyl group, butyl or amyl group;

2) (instead)-4-[(is anti-)-the 4-alkyl-cyclohexyl] cyclohexyl-acetylene and 4-alkyl-4 ' bromine tolane or 4-fluoro-4 ' bromine tolane or 3,4 two fluoro-4 ' bromine tolane or 3,4, ' the bromine tolane is at four (triphenyl) phosphorus palladium chloride for 5-three fluoro-4,1-{ (instead)-4-[(is anti-for the following generation of the catalysis of cuprous iodide and triphenyl phosphorus)-the 4-alkyl-cyclohexyl] the cyclohexyl-acetylene base }-4-[4-alkyl phenyl ethynyl] benzene, 1-{ (instead)-4-[(is anti-)-the 4-alkyl-cyclohexyl] the cyclohexyl-acetylene base }-4-[4-fluorophenyl ethynyl] benzene, 1-{ (instead)-4-[(is anti-)-the 4-alkyl-cyclohexyl] the cyclohexyl-acetylene base }-4-[3,4-difluorophenyl ethynyl] benzene or 1-{ (instead)-4-[(is anti-)-the 4-alkyl-cyclohexyl] the cyclohexyl-acetylene base-4-[3,4,5-trifluorophenyl ethynyl] benzene; Described alkyl is methyl, ethyl, propyl group, butyl or amyl group.

7, method according to claim 6 is characterized in that:

Described preparation (instead)-4-[(is anti-)-the 4-alkyl-cyclohexyl] cyclohexyl-acetylene may further comprise the steps:

1) anti-with (instead)-4-[()-the 4-alkyl-cyclohexyl] hexahydrobenzoic acid is raw material, (instead)-4-[(is anti-in preparation)-4-ethyl cyclohexyl] hexahydrobenzyl alcohol;

2) preparation (instead)-4-[(is anti-)-the 4-alkyl-cyclohexyl] hexahydrobenzaldehyde;

3) preparation (instead) (instead)-4-[(is anti-)-the 4-alkyl-cyclohexyl] cyclohexyl-β, β '-sym-dibromoethane;

4) preparation (instead)-4-[(is anti-)-the 4-alkyl-cyclohexyl] cyclohexyl-acetylene;

Described preparation 4-alkyl-4 ' the bromine tolane may further comprise the steps:

1) pure and mild with 2-methyl-3-alkane alkynes-2-is raw material to the alkyl bromobenzene, generates 2-methyl-4-(4-alkyl phenyl)-3-alkane alkynes-2-alcohol under the catalysis of four (triphenyl) phosphorus palladium chloride, cuprous iodide and triphenyl phosphorus;

2) preparation is to alkylbenzene acetylene;

3) preparation 4-alkyl-4 ' bromine tolane;

Described preparation 4-fluoro-4 ' the bromine tolane may further comprise the steps:

1) is raw material with 2-methyl-fluorine-based bromobenzene of the pure and mild 4-of 3-alkane alkynes-2-, under the catalysis of four (triphenyl) phosphorus palladium chloride, cuprous iodide and triphenyl phosphorus, generates 2-methyl-4-(4-fluorophenyl)-3-alkane alkynes-2-alcohol;

2) preparation 4-fluorobenzene acetylene;

3) preparation 4-fluoro-4 ' bromine tolane;

Described preparation 3,4-two fluoro-4 ' the bromine tolane may further comprise the steps:

1) pure and mild 3 with 2-methyl-3-alkane alkynes-2-, 4-two fluorine-based bromobenzenes are raw material, generate 2-methyl-4-(3, the 4-difluorophenyl)-3-alkane alkynes-2-alcohol under the catalysis of four (triphenyl) phosphorus palladium chloride, cuprous iodide and triphenyl phosphorus;

2) preparation 3,4-difluoro phenylacetylene;

3) preparation 3,4-two fluoro-4 ' bromine tolane;

Described preparation 3,4,5-three fluoro-4 ' the bromine tolane may further comprise the steps:

1) pure and mild 3,4 with 2-methyl-3-alkane alkynes-2-, 5-three fluorine-based bromobenzenes are raw material, generate 2-methyl-4-(3, the 4-difluorophenyl)-3-alkane alkynes-2-alcohol under the catalysis of four (triphenyl) phosphorus palladium chloride, cuprous iodide and triphenyl phosphorus;

2) preparation 3,4,5-trifluoro-benzene acetylene;

3) preparation 3,4,5-three fluoro-4 ' bromine tolane;

Abovementioned alkyl is methyl, ethyl, propyl group, butyl or amyl group.