1-(2-bromoethyl)-4-(trifluoromethoxy)benzene

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A Grignard reagent prepared from the above 2-(4-trifluoromethoxyphenyl)bromoethane (7.0 g, 30.3 mmol) and dried Mg (0.74 g, 30.4 mmol) in an ether solvent (40 ml) was cooled down to 0° C., followed by dropwise adding thereto a 30 ml ether solution of 4-(4-(2-fluoroethyl)cyclohexyl)cyclohexanone (2.2 g, 9.7 mmol) prepared at the third step, stirring the mixture at 0° C. for 3 hours, adding 6N HCl to the reaction solution, extracting the resulting product with toluene, washing the extraction solution successively with a saturated aqueous solution of sodium bicarbonate and water, drying over magnesium sulfate, distilling off the solvent, adding toluene (100 ml) and Amberlist (500 mg) to the resulting yellow oily substance, refluxing the mixture for 4 hours, while removing water formed by the reaction by means of Dean-Stark, filtering off Amberlist, distilling off the solvent, purifying the residue according to column chromatography treatment using toluene as a developing solvent, on silica gel, to isolate 4-(4-(2-fluoroethyl)cyclohexyl)-1-(2-(4-trifluoromethoxyphenyl)ethyl)-1-cyclohexene (1.8 g, 4.5 mmol), hydrogenating this product (1.2 g, 3.0 mmol) in the presence of 5% Pd/C catalyst (0.12 g) in ethanol solution, filtering off the catalyst, distilling off the solvent under reduced pressure, and recrystallizing the residue, to isolate only trans-form of colorless 1-(2-(4-(4-(2-fluoroethyl)-cyclohexyl)cyclohexyl)ethyl-4-trifluoromethoxybenzene (0.37 g, 0.90 mmol) exhibiting smectic phase. The yield of this product from 4-(4-(2-fluoroethyl)chclohexyl)cyclohexanone was 9.3%. by dropwise adding extracting the resulting product with toluene washing the extraction solution successively with a saturated aqueous solution of sodium bicarbonate and water drying over magnesium sulfate distilling off the solvent adding toluene (100 ml) and Amberlist (500 mg) to the resulting yellow oily substance refluxing the mixture for 4 hours while removing water formed by the reaction by means of Dean-Stark filtering off Amberlist distilling off the solvent purifying the residue

Conditions: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 2-(4-trifluoromethyloxyphenyl)ethyl bromide (10.0 g, 0.037 mol) prepared in the same manner as in Example 1 except that 4-trifluoromethylbromobenzene was replaced by 4-trifluoromethyloxybromobenzene, with THF (50 ml), was heated at 90° C. for 40 minutes in a sealed tube reactor, to obtain a yellow, uniform solution, followed by adding this solution to a THF (40 ml) solution of 4-(4-pentylcyclohexyl)cyclohexanone (9.27 g, 0.037 mol), stirring the mixture at room temperature for 2 hours, feeding the reaction substance into a saturated aqueous solution of NH4Cl, twice extracting with ethyl acetate (50 ml), washing the resulting organic layer with an aqueous solution of NaCl, drying over anhydrous MgSO4, removing the anhydrous MgSO4, distilling off the solvent under reduced pressure, to obtain a pale yellow, oily 1-(2-(4-trifluoromethyloxyphenyl)ethyl-4-(4-pentylcyclohexyl)cyclohexanol (19.7 g), adding thereto toluene (50 ml) and Amberlyst (0.9 g), heating the mixture under reflux for one hour, while removing formed water, allowing the resulting substance to cool, feeding it to a saturated aqueous solution of NH4Cl, twice washing the separated organic layer with water, drying over anhydrous MgSO4, filtering off the anhydrous MgSO4, distilling off the solvent under reduced pressure, subjecting the residue to column chromatography (silica gel, eluent: heptane) and twice recrystallizing from a mixed solvent of ethanol (10 ml) with benzene (1 ml), to obtain 1-(2-(4-trifluoromethyloxyphenyl)ethyl)-4-(4-pentylcyclohexyl)cyclohexene (1.0 g). Yield: 6%. to obtain a yellow, uniform solution twice extracting with ethyl acetate (50 ml) washing the resulting organic layer with an aqueous solution of NaCl drying over anhydrous MgSO4 removing the anhydrous MgSO4 distilling off the solvent under reduced pressure

Conditions: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 2-(4-trifluoromethyloxyphenyl)ethyl bromide (10.0 g, 0.037 mol) prepared in the same manner as in Example 1 except that 4-trifluoromethylbromobenzene was replaced by 4-trifluoromethyloxybromobenzene, with THF (50 ml), was heated at 90° C. for 40 minutes in a sealed tube reactor, to obtain a yellow, uniform solution, followed by adding this solution to a THF (40 ml) solution of 4-(4-pentylcyclohexyl)cyclohexanone (9.27 g, 0.037 mol), stirring the mixture at room temperature for 2 hours, feeding the reaction substance into a saturated aqueous solution of NH4Cl, twice extracting with ethyl acetate (50 ml), washing the resulting organic layer with an aqueous solution of NaCl, drying over anhydrous MgSO4, removing the anhydrous MgSO4, distilling off the solvent under reduced pressure, to obtain a pale yellow, oily 1-(2-(4-trifluoromethyloxyphenyl)ethyl-4-(4-pentylcyclohexyl)cyclohexanol (19.7 g), adding thereto toluene (50 ml) and Amberlyst (0.9 g), heating the mixture under reflux for one hour, while removing formed water, allowing the resulting substance to cool, feeding it to a saturated aqueous solution of NH4Cl, twice washing the separated organic layer with water, drying over anhydrous MgSO4, filtering off the anhydrous MgSO4, distilling off the solvent under reduced pressure, subjecting the residue to column chromatography (silica gel, eluent: heptane) and twice recrystallizing from a mixed solvent of ethanol (10 ml) with benzene (1 ml), to obtain 1-(2-(4-trifluoromethyloxyphenyl)ethyl)-4-(4-pentylcyclohexyl)cyclohexene (1.0 g). Yield: 6%. to obtain a yellow, uniform solution twice extracting with ethyl acetate (50 ml) washing the resulting organic layer with an aqueous solution of NaCl drying over anhydrous MgSO4 removing the anhydrous MgSO4 distilling off the solvent under reduced pressure