Optically active fluorine-containing alcohol compounds and liquid crystal compounds therefrom

Abstract: An optically active fluorine-containing alcohol of where R₂ is a C₁₋₁₈ alkyl and n is 2 - 10, and liquid crystal compound of wherein R₁ and R₂ each is a C₁₋₁₈ alkyl, X is O, COO or OCO, Y is COO, OCO, CH₂O or OCH₂, Z is COO or O, (A) and (B) each is for example and p is zero or one, which is prepared from (I) above.

Description: The present invention relates to a novel optically active fluorine-containing alcohol compound which is useful as an intermediate for producing a liquid crystal compound. The present invention relates also to a novel fluorine-containing liquid crystal compound, prepared from the alcohol compound. Series of fluorine-containing liquid crystal compound have been patented (JP 63-307837, JP 64-3154) in the literature. Optically active alcohols for preparing the fluorine-containing liquid crystal compounds mentioned in JP 63-307837 are 1-trifiuoromethyl heptanol, 1-trifluoro-methyl nonyl alcohol, β-trifluoro-methyl-β-phenethyl alcohol, 1-trifluoromethyl-3-phenyl propanol, 1-phenyl-2-monofluoroethyl alcohol, 1-difluoromethylpentanol, 1-difluoromethylnonyl alcohol whereas optically active fluorine-containing liquid crystal compounds mentioned in JP 64-3154 are EP-A-0 327 349 discloses a compound, the structure of which is so that it neither have -CH 2 -CH 2 - linkage between and the chiral carbon, nor an alkoxy group at the right terminal. The Sc* phase range of the compound according to EP-A-0 327 349 is narrow. EP-A-0 301 511 discloses a compound that does not have an alkoxy group at the right terminal. The Sc* phase range of this compound according to EP-A-0 301 511 is narrow and it has unstable phase series. However, in the present invention novel optically active fluorine-containing alcohols which have an ether linkage on one end of an asymmetric carbon which is substituted by trifluoromethyl group, are mentioned. The present invention is also focussed to a novel fluorine-containing liquid crystal compounds synthesized from the novel optically active fluorine-containing alcohol. One of the general structure of optically active compounds having the formula (I) is shown below. where R 2 is a C 1-18 alkyl group and * shows an asymmetric carbon. Liquid crystal compounds (II) prepared from the (I) have the general structural formula as shown below: where R 1 and R 2 each is a C 1-18 alkyl group, and (A) and (B) each is a cyclic group selected from where one or two of the hydrogen atoms may be substituted by a halogen atom , preferably a fluorine or chlorine atom, more preferably a fluorine atom and p is zero or one. Typical compounds of the formula (I) are 4,4,4-trifluoro-3-methyloxybutanol, 4,4,4-trifluoro-3-ethyloxybutanol, 4,4,4-trifluoro-3-propyloxybutanol, 4,4,4-trifluoro-3-butoxybutanol, 4,4,4-trifluoro-3-pentyloxybutanol, 4,4,4-trifluoro-3-hexyloxybutanol, 4,4,4-trifluoro-3-heptyloxybutanol, 4,4,4-trifluoro-3-octyloxybutanol, 4,4,4-trifluoro-3-nonyloxybutanol, 4,4,4-trifluoro-3-decyloxybutanol, 4,4,4-trifluoro-3-undecyloxybutanol and 4,4,4-trifluoro-3-dodecyloxybutanol. Examples of the liquid crystal compounds of the formula (II) are 4,4,4-trifluoro-3-methyloxybutyloxycarbonylphenyl 4-alkyloxybiphenyl-4'-carboxylate, 4,4,4-trifluoro-3-ethyloxybutyloxycarbonyphenyl 4-alkyloxybiphenyl-4′-carboxylate, 4,4,4-trifluoro-3-propyloxybutyloxycarbonylphenyl 4-alkyloxybiphenyl-4′-carboxylate, 4,4,4-trifluoro-3-butyloxybutyloxycarbonylphenyl 4-alkyloxybiphenyl-4′-carboxylate, 4,4,4-trifluoro-3-pentyloxybutyloxycarbonylphenyl 4-alkyloxybiphenyl-4′-carboxylate, 4,4,4-trifluoro-3-hexyloxybutyloxycarbonylphenyl 4-alkyloxybiphenyl-4′-carboxylate, 4,4,4-trifluoro-3-heptyloxybutyloxycarbonylphenyl 4-alkyloxybiphenyl-4′-carboxylate, 4,4,4-trifluoro-3-octyloxybutyloxycarbonylphenyl 4-alkyloxybiphenyl-4′-carboxylate, 4,4,4-trifluoro-3-nonyloxybutyloxycarbonylphenyl 4-alkyloxybiphenyl-4′-carboxylate, 4,4,4-trifluoro-3-decyloxybutyloxycarbonylphenyl 4-alkyloxybiphenyl-4′-carboxylate, 4,4,4-trifluoro-3-undecyloxybutyloxycarbonylphenyl 4-alkyloxybiphenyl-4′-carboxylate, and 4,4,4-trifluoro-3-dodecyloxybutyloxycarbonylphenyl 4-alkyloxybiphenyl-4′-carboxylate. The corresponding compounds of pentyl esters,hexyl esters, heptyl esters and octyl esters to the butyl esters above may be mentioned. There are (R) isomers and (S) isomers in the optically active compounds (I) and liquid crystal compounds (II). preferable compounds are those having higher optical purity. The accompanying drawing shows IR spectrum of 4,4,4-trifluoro-3-hexyloxybutyloxycarbonylphenyl 4-octyloxybiphenyl-4′-carboxylate which is prepared by Example 2 mentioned below. The optically active fluorine-containing alcohols of the formula (I) are prepared, for example, by allowing alkyl esters of (R)-(+)- or (S)-(-)-4,4,4-trifluoro-3-hydroxy alkanoic acid to react with alkyl halides in DMF solvent in the presence of a catalyst, for example, silver oxide to obtain alkyl ester of (R)-(+)- or (S)-(-)-4,4,4-trifluoro-3-alkyloxyalkanoic acid and reducing the ester in THF solvent in the presence of a reducing agent, for example, aluminium lithium hydride until (R)-(+)- or (S)-(-)-4,4,4-trifluoro-3-alkoxyalkanol is obtained. Butanol compounds are obtained when the alkanoic acid is butanoic acid. Similarly, pentanol, hexanol, heptanol or octanol compounds are prepared when pentanoic acid, hexanoic acid, heptanoic acid or octanoic acid is used in place of the butanoic acid, respectively. Reaction scheme is as follows when, for instance, butanoic acid is used: Preparation scheme of the liquid crystal compounds (II) is, for instance, The present optically active fluorine-containing alcohol (I) is an intermediate useful for preparing a liquid crystal compound, particularly a ferro-electric liquid crystal. The present liquid crystal compound (II) is ferro-electric of bistable state or binary bistable state which shows a usual SmC* phase and electroclinic effect at an S A phase. The compound (II) is used for electro-optical devices, liquid crystal optical devices and other liquid crystal devices. Example 1 (1) Synthesis of ethyl 4,4,4-trifuoro-3-hexyloxybutylate A solution of ethyl (S)-(-)-4,4,4-trifluoro-3-hydroxybutylate (2.0 g, [α] 20 / D = -14.2°), silver oxide (2.5 g) and hexyl iodide (4.6 g) in DMF (50 ml) was kept at 60°C for 8 hours. The reactant was poured in ice water, precipitated substances were filtered off. Extraction was repeated with hexane. The hexane layer obtained was washed with water and the solvent was distilled off in an evaporater. An oily substance obtained was purified by silica gel chromatography to obtain the titled compound (0.88 g). (2) Synthesis of 4,4,4-trifluoro-3-hexyloxybutanol To a solution of ethyl (S)-(-)-4,4,4-trifluoro-3-hexyloxybutylate (0.88 g) in THF (20 ml) was slowly added LiAlH 4 (0.44 g) suspended in THF (10 ml) in ice water bath. The mixture was stirred at 0°C for 2 hours and then additionally stirred at room temperature for 8 hours. Aqueous hydrochloric acid solution was added to decompose the unaltered LiAlH 4 and solution mixture was extracted with ether. The ether layer was washed with water, dried and distilled to remove the solvent. A product obtained (0.84 g) was mainly composed of the titled compound. Example 2 (1) Synthesis of 4,4,4-trifluoro-3-hexyloxybutyl 4′-hydroxybenzoate To a solution of 4,4,4-trifluoro-3-hexyloxybutanol (0.4 g) and triethyl amine (0.19 g) in methylene chloride (15 ml) was added dropwise a solution of benzyloxybenzoic acid chloride (0.48 g) in methylene chloride (5 ml). The mixture was stirred at room temperature for 12 hours. After the reaction was over, the reactant was poured in ice water. The mixture was extracted with ether. After the ether layer was washed with water, the layer was subjected to distillation to remove the solvent and then purified by silica gel chromatography to obtain 4,4,4-trifluoro-3-hexyloxybutyl 4′-benzyloxybenzoate (0.60 g). The product was subjected to a usual removal step of benzyl group to obtain the titled compound (0.43 g). (2) Synthesis of 4,4,4-trifluoro-3-hexyloxybutyloxycarbonylphenyl 4-octyloxybiphenyl-4′-carboxylate To a solution of (S)-(-)-4,4,4-trifluoro-3-hexyloxybutyl 4′-hydroxybenzoate (0.43 g) and triethyl amine (0.13 g) in methylene chloride (10 ml) was gradually added a solution of 4-octyloxybiphenyl-4′-carboxylic acid chloride (0.37 g) in methylene chloride (10 ml) while being ice cooled. The mixture was stirred at room temperature for 8 hours. After the reaction was over, the reactant was poured in ice water and then extracted with ether. The ether layer was thoroughly washed with water, dried and distilled in order to remove the solvent. The product obtained was purified by silica gel chromatography to obtain the titled compound (0.25 g, [α] 20 / D= -6.54°). The phase transition temperature and microscopic texture of the liquid crystal were determined by using Differential scanning calorimetory and polarizing microscope equipped with temperature-controlled hot stage. The phase transition temperatures are shown below:

Claims: Optically active compound of the formula (I) wherein R 2 is an alkyl group of C 1 -C 18 and * shows an asymmetric carbon. Optically active compound according to claim 1, wherein R 2 is an alkyl group of C 1 -C 12 . Liquid crystal compound of the formula (II) wherein R 1 and R 2 each is an alkyl group of C 1 -C 18 , (A) and (B) each is a cyclic group selected from where one or two of the hydrogen atoms may be substituted by a halogen atom and p is zero or one. Liquid crystal compound according to claim 3, wherein the halogen atom is selected from fluorine and chlorine atoms. Liquid crystal compound according to claim 3, wherein the halogen atom is an fluorine atom. A ferroelectric liquid crystal compound of the formula III: wherein R 1 and R 2 each is an alkyl group of C 1 - C 18 . A ferroelectric liquid crystal compound of the following formula

Inventors: SADAMUNE YASUNORI, SUZUKI YOSHIICHI, YAMAKAWA NORIKO, SADAMUNE, YASUNORI, SUZUKI, YOSHIICHI, YAMAKAWA, NORIKO, SADAMUNE, YASUNORI, C/O SHOWA SHELL SEKIYU K.K., SUZUKI, YOSHIICHI, C/O SHOWA SHELL SEKIYU K.K., YAMAKAWA, NORIKO, C/O SHOWA SHELL SEKIYU K.K.
Applicants: SHOWA SHELL SEKIYU, SHOWA SHELL SEKIYU KABUSHIKI KAISHA
Application year: 1990
Main classification: C07C43
IPC codes: C09K19, C07C69, C07C43