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WO1998011173A1 - Liquid crystal materials - Google Patents

Liquid crystal materials Download PDF

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Publication number
WO1998011173A1
WO1998011173A1 PCT/KR1997/000169 KR9700169W WO9811173A1 WO 1998011173 A1 WO1998011173 A1 WO 1998011173A1 KR 9700169 W KR9700169 W KR 9700169W WO 9811173 A1 WO9811173 A1 WO 9811173A1
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Prior art keywords
independently
formula
formulas
group
chiral
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PCT/KR1997/000169
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French (fr)
Inventor
Vladimir St. Bezborodov
Valery Lapanik, Iv.
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Samsung Display Devices Co., Ltd.
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Priority to JP10513519A priority Critical patent/JP2001500502A/en
Priority to EP97939250A priority patent/EP0946672A1/en
Priority to AU41380/97A priority patent/AU4138097A/en
Publication of WO1998011173A1 publication Critical patent/WO1998011173A1/en

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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/215—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring having unsaturation outside the six-membered aromatic rings
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    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
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    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/673—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
    • C07C45/676—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton by elimination of carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/657—Unsaturated compounds containing a keto groups being part of a ring containing six-membered aromatic rings
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/657—Unsaturated compounds containing a keto groups being part of a ring containing six-membered aromatic rings
    • C07C49/683—Unsaturated compounds containing a keto groups being part of a ring containing six-membered aromatic rings having unsaturation outside the aromatic rings
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/753—Unsaturated compounds containing a keto groups being part of a ring containing ether groups, groups, groups, or groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/013—Esters of alcohols having the esterified hydroxy group bound to a carbon atom of a ring other than a six-membered aromatic ring
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
    • C09K19/126—Compounds containing at least one asymmetric carbon atom
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3098—Unsaturated non-aromatic rings, e.g. cyclohexene rings
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

  • the present invention relates to liquid crystal materials for use in ferroelectric liquid crystal display devices. More specifically, the invention relates to chiral, laterally substituted derivatives of cyclohexene, cyclohexane, benzene, biphenyl, terphenyl and quaterphenyl compounds, mixtures thereof, and liquid crystal displays utilizing the same.
  • Liquid crystal displays have been commonly employed in electronic devices for many years. In general, commercial displays operate by the twisted nematic (TN) or super twisted nematic (STN) technique. However, liquid crystal displays based on a ferroelectric technique are also known. Such displays have superior properties such as higher switching efficiencies in comparison to TN and STN displays. But ferroelectric liquid crystal displays have not been widely used in commercial or consumer applications, in spite of their advantages, due to their limited operable temperature range. Specifically, in order to utilize the ferroelectric effect, the liquid crystal material must exhibit a smectic C phase. Liquid crystal compounds that exhibit a smectic C phase do so over a narrow temperature range.
  • Liquid crystal compounds include derivatives of cyclohexane, cyclohexene, benzene, biphenyl, and terphenyl compounds. Such compounds are disclosed in Ferroelectrics 1991, vol. 114, p.
  • U.S. P. 4,784,793 addresses some of the problems encountered with ferroelectric liquid crystal materials and proposes the use of terpenoid derivatives, such as an ester of a terpenoid alcohol, as either a smectic host or a chiral dopant.
  • U.S. P. 5,382,380 and U.S. P. 5,494,605 both relate to p-terphenyl derivatives having lateral fluoro substitution. The compounds are described as exhibiting a smectic C phase over a wide temperature range.
  • the compounds of the prior art are not yet fully satisfactory and do not satisfy all of the requirements for some of the new applications for liquid crystal displays. Specifically, compounds are needed that will allow the formation of ferroelectric liquid crystal mixtures exhibiting a low crystalline to smectic C phase transition temperature as well as a wide smectic C phase and that has a stable orientation.
  • a further object of the invention is to provide a ferroelectric liquid crystal display device that is operable over a wide range of temperatures and at very low temperatures.
  • R 1 and $ are each independently selected from the group consisting of formulas S 1 , S 2 and S 3 : I I
  • Y 1 , Y 2 , Y 3 , and Y are each independently hydrogen, alkyl, F, CN, CF, or OCF 3 , n, p, and k are each independently an integer from 0 to 7. and m and 1 are each independently zero or 1, with the proviso that at least one of R 1 and R 2 is a chiral radical;
  • Z 1 and Z 2 are each independently a ring selected from the group consisting of formulas 2-11
  • a 1 , A 2 and A 3 are each independently a ring group selected from the group consisting of formulas 12-19:
  • the compounds of Formula (1) can have as few as one ring represented by Z 1 or a plurality of rings represented by Z 1 and any of A 1 -A 3 and/or Z 2 .
  • a is 0, then the substituent group R 1 is directly bonded to the group Z 1 .
  • b, c and d were each 0, the group R 2 would be directly bonded to the moiety Z 1 .
  • R 1 and R 2 are each independently represented by one of the formulas S 1 - S 3 with the proviso that at least one of R ! and R 2 is a chiral group.
  • R l and R 2 can both be chiral groups, although such is not required.
  • the compounds of Formula (1) are optically active.
  • a chiral moiety can be obtained by appropriately selecting the groups for the pair Y 1 and Y 2 or the pair Y 3 and Y 4 , as will be readily understood by workers skilled in the art.
  • the groups Y 1 -Y 4 are independently selected for R 1 and R 2 . That is, the Y 1 group of R 1 may be the same or different as the Y 1 group of R 2 .
  • the same is true of all other variables in the formulas S 1 - S 3 such that the values selected for R 1 are independent of the values selected for R 2 .
  • Y ] , Y 2 , Y 3 or Y 4 represents an alkyl, it may be straight or branched and typically has from 1 to 12 carbon atoms.
  • the alkyl group has from 1 to 8 carbon atoms.
  • examples of the alkyl group include methyl, ethyl, n-propyl, i-propyl, n-butyl, and t-butyl.
  • the subscripts n, p and k are each independently an integer from 0 to 7 while the subscripts m and 1 are each independently 0 or 1.
  • p and k, as well as 1, are 0.
  • Examples of chiral R 1 and R 2 groups include 2-methylbutyl, 2-methylpentyl, 2-methylhexyl, 4-methylhexyl, citronellyl, citronellyloxy, 2-methylhexyloxy, 2- methyloctyloxy, 2-cyanobutyloxy, and 2-fluorobutyloxy.
  • the non-chiral R 1 and R 2 groups include octyl, octyloxy, butyl, hexyl, hexyloxy, nonyl, nonyloxy, decyl, decyloxy, 2-octyloxyethyl, 2-octyloxyethyloxy, heptyloxymethyl, and heptyloxymethyloxy .
  • Z 1 and Z 2 each independently represent a six-membered ring selected from formulas 2-11 , each of which is substituted by a group X .
  • Each X independently represents O, F, Cl, OH, CN or a group represented by formulas L 1 - L 6 .
  • X can not be O on ring formulas 4, 5, and 8-11.
  • Z 2 is present (c is 1), each X group is independently selected.
  • L ' - L 6 examples include 2-methylbutyloxycarbonyl, 2-methylbutylcarbonyloxy, 2- methylhexyloxy, 2-methyloctyloxy, 2-methylbutyl, 2-methylbutyloxy, 2- chlorobutylcarbonyloxy, methyl, methyloxy, ethyl, and ethyloxy.
  • L 1 - L 6 can represent chiral or non- chiral groups.
  • a 1 - A 3 are each independently selected from the ring formulas 12 - 19.
  • 1 - X 4 are independently selected for each of A 1 - A 3 and are H, F, or Cl.
  • the chiral, laterally substituted compounds of formula (1) are liquid crystal compounds that exhibit a chiral smectic C phase.
  • the compounds exhibit a chiral smectic C phase over a broad temperature range, such as over a range of at least 20°C, more preferably at least 30°C, and most preferably over at least 40 °C range.
  • the compounds exhibit a chiral smectic C phase at low temperatures, including ambient temperatures. Accordingly, it is preferred that the lower end of the chiral smectic C phase is 20 °C or less, more preferably 10°C or less, and most preferably, 5°C or less.
  • the smectic C phase temperature values can be determined by conventional techniques known in the art; i.e., heating the compounds to the isotropic liquid phase, and then observing the phases and their transition temperatures during cooling and then heating again.
  • the transition temperatures were determined using a Mettler FP5 hotstage and control unit in conjunction with a polarizing microscope and these values were confirmed using differential scanning calorimetry (Perkin-Elmer DSC- 7).
  • the compound of formula (1) is represented by one of the formulas 1.1 - 1.39 set forth below.
  • R 3 and R 4 represent a group of formulas L 1 - L 6
  • R 1 , R 2 , and X 1 - X 4 have the same definition as in formula (1).
  • R 1 and R 2 are each independently selected from the group consisting of formulas S 1 , S 2 and S 3 :
  • Y 1 , Y 2 , Y 3 , and Y 4 are each independently hydrogen, alkyl, F, CN, CF 3 or OCF 3 , n, p, and k are each independently an integer from 0 to 7, and m and 1 are each independently zero or 1 , with the proviso that at least one of R 1 and R 2 is a chiral radical;
  • Z 1 and Z 2 are each independently a ring selected from the group consisting of formulas 2-11
  • the compounds of formula (1) can be prepared by workers skilled in this art without undue experimentation through conventional reactions that are per se known in the art and from conventional and/or commercially available starting materials. However, preferred reaction schemes are set forth hereinbelow. Liquid crystal compounds according to the present invention can be obtained by the transformation of 3,6-disubstituted cyclohex-2-enones. Synthesis of these starting compounds is shown in scheme 1. For convenience and clarity the compounds are shown without the subscripts a - d, but such should be assumed to be present.
  • Scheme 1 The process consists of heating acetoacetic esters with hydrochloride 4- substituted ⁇ -N-dimethylaminoprophio-phenones in the presence of an alkaline hydroxide. The 3,6-disubstituted cyclohex-2-enones can then be transformed into
  • the 3,6-disubstituted cyclohex-2-enones can be transformed into the corresponding 4,4-disubstituted 3-hydroxybiphenyls, te ⁇ henyls and quate ⁇ henyls (Formula 27) by aromatization in the presence of 10% palladium on carbon at 200°C or by the boiling of them in alcohols in the presence of iodine.
  • the 3,6-disubstituted cyclohexanones can be transformed into the corresponding cis and trans alcohols (Formula 34) by reduction with NaBH 4 or LIA1H 4 in an appropriate solvent.
  • Fluorosubstituted compounds are prepared by heating ketones (Formula 24) with diethylaminosulfur trifluoride in benzene or methylene chloride and the resulting difluoroderivatives (Formula 36) are then treated with a base, advantageously KOH or with alcohalate.
  • the cyanounsaturated compounds (Formula 42, 43) are obtained by treating the ketones (Formula 24) with acetone cyanohydrine in the presence of tertiary amines or alkaline metal carbonates in dioxane or tetrahydrofuran and then by treating of the corresponding cyanoalcohols with POCl 3 in the presence of a tertiary aliphatic amine or pyridine.
  • the isomeric compounds (Formula 42, 43) are separated by crystallization.
  • the chlorine substituted compounds (Formulae 26, 30, 31) are obtained by heating ketone (Formula 23, 24) with PC1 5 , PCI, in hexane or benzene.
  • the isomeric compounds (Formula 30, 31) are separated by crystallization or used in a form of the isomeric mixtures.
  • Compounds of Formula 25 and 32 are obtained from ketone (Formula 23,
  • Compounds of Formula 36 are obtained by treating ketone 24 with triethyl orthoformate in the presence of p-toluenesulfonic acid in ethanol.
  • the chlorocyclohexane derivatives (Formula 33) are obtained by treating the corresponding alcohols (Formula 34) with PC1 5 , SOCl 2 , POCl 3 .
  • the fluorocyclohexane derivatives (Formula 40) are synthesized by treating the alcohols 34 with diethylaminosulfur trifluoride (DAST) in methylene chloride at temperature below 20°C.
  • DAST diethylaminosulfur trifluoride
  • the compounds of formula (1) are useful in liquid crystal display devices including TN, STN, and ferroelectric LC displays.
  • the compounds of Formula (1) are especially useful in creating compositions having various values of optical anisotropy and dielectric anisotropy as well as a wide temperature interval of the smectic C phase.
  • Compositions according to the present invention require at least two compounds, with at least one of them being a compound of Formula (1).
  • the compounds contained in the composition can be exclusively of formula (1) or a combination with other liquid crystal compounds.
  • compositions containing compounds of Formula (1) that have 2 or 3 rings show low or intermediate clearing temperatures.
  • Compositions containing compounds of Formula (1) that have 4 or 5 rings have a broadening of the smectic C phase, including broader than 100°C.
  • the compositions are useful in ferroelectric liquid crystal displays, TN, STN, and active matrix displays. The high chemical stability and resistivity of these mixtures enable the stable performance of the display.
  • the composition is a ferroelectric composition and exhibits a chiral smectic C phase over a broad temperature range, preferably over at least a 40 °C interval. Moreover, preferably the composition simultaneously exhibits a lower end of the chiral smectic C phase at 10°C or less, more preferably at 10°C or less, and most preferably at -30°C or less.
  • one or more compounds of Formula (1) is combined with at least one liquid crystal pyrimidine derivative.
  • the pyrimidine derivative exhibits a smectic C phase and is capable of forming a ferroelectric liquid crystal composition.
  • Such compounds include phenyl -substituted pyrimidines such as 2-alkoxyphenyl-5-alkylpyrimidines where the alkoxy and alkyl groups each contain from 1 to 12 carbon atoms.
  • the composition of the present invention can be used in any conventional liquid crystal display device.
  • such devices generally comprise two parallel electrodes, at least one of which is transparent, and having a layer of the liquid crystal composition disposed therebetween.
  • die liquid crystal layer is typically disposed between two parallel plates, one of which is transparent, that are in turn supported by (or surrounded by) the parallel electrodes. Between the parallel plates there may also be one or more of an aligning layer, isolating layer, and colored filter layer.
  • the display device is operated by the ferroelectric effect.
  • the compounds of formula (1) are useful in liquid crystal display devices including TN, STN, and ferroelectric LC displays.
  • the compounds of Formula (1) are especially useful in creating compositions having various values of optical anisotropy and dielectric anisotropy as well as a wide temperamre interval of the smectic C phase.
  • the compound of the present invention can be used in any conventional liquid crystal display device.

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Abstract

Chiral liquid crystalline compounds of Formula (1): R1-(A')a-21-(A2)b-(22)c-(A3)d-R2 are particularly useful in a ferroelectric liquid crystal display device. These cyclic-containing compounds are chiral and contain lateral substituents. The compounds exhibit a low temperature smectic C phase and have a broad smectic C phase region.

Description

LIQUID CRYSTAL MATERIALS
Technical Field
The present invention relates to liquid crystal materials for use in ferroelectric liquid crystal display devices. More specifically, the invention relates to chiral, laterally substituted derivatives of cyclohexene, cyclohexane, benzene, biphenyl, terphenyl and quaterphenyl compounds, mixtures thereof, and liquid crystal displays utilizing the same.
Background Art
Liquid crystal displays have been commonly employed in electronic devices for many years. In general, commercial displays operate by the twisted nematic (TN) or super twisted nematic (STN) technique. However, liquid crystal displays based on a ferroelectric technique are also known. Such displays have superior properties such as higher switching efficiencies in comparison to TN and STN displays. But ferroelectric liquid crystal displays have not been widely used in commercial or consumer applications, in spite of their advantages, due to their limited operable temperature range. Specifically, in order to utilize the ferroelectric effect, the liquid crystal material must exhibit a smectic C phase. Liquid crystal compounds that exhibit a smectic C phase do so over a narrow temperature range. Moreover, the smectic C phase tends to be exhibited only at a relatively high temperature; i.e, above ambient temperature. Accordingly, designing a ferroelectric liquid crystal display for general consumer electronics becomes impractical. Liquid crystal compounds include derivatives of cyclohexane, cyclohexene, benzene, biphenyl, and terphenyl compounds. Such compounds are disclosed in Ferroelectrics 1991, vol. 114, p. 357; JP 04 216 525 (1992); EP 86/00529 (1987); DE 3608500 (1987); WO 87/05015 (1987); WO 87/01717; WO 87/05017; DE 3706766; JP 88 300 885.6 (1988); J. Am. Che. Soc. 1986, vol. 108, p. 5210; GB 2181429; JP 05 17409; JP 07 258642. Many of these compounds do not exhibit a smectic C phase and instead exhibit only a nematic phase. Accordingly, these compounds are useful only in TN or STN displays and are not operable as ferroelectric liquid crystal materials. The compounds that do exhibit a smectic C phase tend to suffer from the above-mentioned temperature drawbacks as well as having an unstable orientation.
U.S. P. 4,784,793 addresses some of the problems encountered with ferroelectric liquid crystal materials and proposes the use of terpenoid derivatives, such as an ester of a terpenoid alcohol, as either a smectic host or a chiral dopant. U.S. P. 5,382,380 and U.S. P. 5,494,605 both relate to p-terphenyl derivatives having lateral fluoro substitution. The compounds are described as exhibiting a smectic C phase over a wide temperature range. However, the compounds of the prior art are not yet fully satisfactory and do not satisfy all of the requirements for some of the new applications for liquid crystal displays. Specifically, compounds are needed that will allow the formation of ferroelectric liquid crystal mixtures exhibiting a low crystalline to smectic C phase transition temperature as well as a wide smectic C phase and that has a stable orientation.
Disclosure of the Invention
It is an object of the present invention to provide chiral liquid crystal compounds that exhibit a low transition temperature from the crystalline to smectic C phase, that exhibit the smectic C phase over a wide temperature range, and that provide stable orientation over time.
It is another object of the invention to provide a ferroelectric mixture that exhibits a smectic C phase over a broad temperature range and at low temperatures.
A further object of the invention is to provide a ferroelectric liquid crystal display device that is operable over a wide range of temperatures and at very low temperatures.
These and other objects of the present invention are achieved by a chiral liquid crystalline compound of formula (1):
R1— (A1 ) a— Z1— ( A2 ) b— ( Z2 ) c— (A3 ) d— R2 ( l ) wherein a, b, c, and d are each independently zero or 1;
R1 and $ are each independently selected from the group consisting of formulas S1, S2 and S3 : I I
HC (CH2) „— (O) m C (CH2) k (O) r (CH2) (S1
Y Y4
Y1
C=CH (CH,)n (0)m C — (CH2), (O), (CH2)n
Yl
Y1
HC — (CH, C O } _ — C CH=CH — • ( CH, ) (0) (CH, (S3
Y Y4
wherein Y1, Y2, Y3, and Y are each independently hydrogen, alkyl, F, CN, CF, or OCF3, n, p, and k are each independently an integer from 0 to 7. and m and 1 are each independently zero or 1, with the proviso that at least one of R1 and R2 is a chiral radical;
Z1 and Z2 are each independently a ring selected from the group consisting of formulas 2-11
Figure imgf000005_0001
(2) (3) (4) (5)
Figure imgf000005_0002
Figure imgf000005_0003
Figure imgf000005_0004
(10) (11) wherein X represents O, F, Cl, OH, CN, or a group represented by formulas L1- L6:
(L1)
Figure imgf000006_0002
C=CH— (CH2) n— (O) m— C— (CH2) k— (0} ,— (CH2) ( 2
Y4
Y'
HC— ( CH2 ) n— ( O ) m — C — CH=CH — ( CH2 ) k— ( O ) ,— ( CH2 ) ( 3
γl γ3 i I
HC— (CH2)n— (0)m— C— (CH2)k— (O),— (CH2)p— COO— ( 4) γ2 γ
Y1 γ3
I I
C=CH— (CH2) — (O) m— C— (CH2) k— (O) ,— { CH2) p— COO— ( )
Y2 γ»
H
Figure imgf000006_0001
wherein Y1, Y2, Y3, Y4, n, p, k, m and 1 have the same meanings as above in formulas S'-S3;
A1, A2 and A3 are each independently a ring group selected from the group consisting of formulas 12-19:
Figure imgf000007_0001
ds)
( 14 )
Figure imgf000007_0002
Figure imgf000007_0003
wherein X1, X2, X3 and X 4 are each independently H, F, or Cl and B and B1 are each independently a single bond, -CH2CH2-, -CH=CH-, -C ≡C-, -OCH,-, or -CH2O-; with the proviso that when the ring structure formed by any three of A1, Z1 , A2, Z2 and A3 is teφhenyl, then none of X, X1 , X2 , X3 and X4 represent F.
Best mode for carrying out the Invention The present invention relates to a chiral liquid crystalline compound of
Formula (1): R1— (A1 ) a— Z1— (A2) b— ( Z2 ) c— (A3 ) d— R2 ( 1 )
Because a, b, c and d are each independently 0 or 1 , the compounds of Formula (1) can have as few as one ring represented by Z1 or a plurality of rings represented by Z1 and any of A1 -A3 and/or Z2 . When a is 0, then the substituent group R1 is directly bonded to the group Z1. Similarly, if b, c and d were each 0, the group R2 would be directly bonded to the moiety Z1 .
R1 and R2 are each independently represented by one of the formulas S1 - S3 with the proviso that at least one of R! and R2 is a chiral group. In this regard, it is specifically contemplated that Rl and R2 can both be chiral groups, although such is not required. By requiring at least one of R1 and R2 to be a chiral group, the compounds of Formula (1) are optically active.
In the Formulas S'-S3, a chiral moiety can be obtained by appropriately selecting the groups for the pair Y1 and Y2 or the pair Y3 and Y 4 , as will be readily understood by workers skilled in the art. The groups Y1 -Y 4 are independently selected for R1 and R2. That is, the Y1 group of R1 may be the same or different as the Y1 group of R2. The same is true of all other variables in the formulas S1 - S3 such that the values selected for R 1 are independent of the values selected for R2. When Y ] , Y2 , Y3 or Y4 represents an alkyl, it may be straight or branched and typically has from 1 to 12 carbon atoms. More preferably, the alkyl group has from 1 to 8 carbon atoms. Examples of the alkyl group include methyl, ethyl, n-propyl, i-propyl, n-butyl, and t-butyl. The subscripts n, p and k are each independently an integer from 0 to 7 while the subscripts m and 1 are each independently 0 or 1. Preferably, p and k, as well as 1, are 0.
Examples of chiral R1 and R2 groups include 2-methylbutyl, 2-methylpentyl, 2-methylhexyl, 4-methylhexyl, citronellyl, citronellyloxy, 2-methylhexyloxy, 2- methyloctyloxy, 2-cyanobutyloxy, and 2-fluorobutyloxy. The non-chiral R1 and R2 groups include octyl, octyloxy, butyl, hexyl, hexyloxy, nonyl, nonyloxy, decyl, decyloxy, 2-octyloxyethyl, 2-octyloxyethyloxy, heptyloxymethyl, and heptyloxymethyloxy .
Z1 and Z2 each independently represent a six-membered ring selected from formulas 2-11 , each of which is substituted by a group X . Each X independently represents O, F, Cl, OH, CN or a group represented by formulas L1 - L6. When X is O, as opposed to OH, it is connected to the ring by a double bond. Accordingly, X can not be O on ring formulas 4, 5, and 8-11. When Z2 is present (c is 1), each X group is independently selected.
In formulas L1 - L6, the variables Y1 , Y2 , Y3 , Y4 , n, p, k, m and 1 have the same definitions as in formulas S1 - S 3. However, for emphasis and clarity, mention is again made of the fact that in this application, a group such as Y1 can have different values with regard to each substituent and each formula. Examples of L ' - L6 include 2-methylbutyloxycarbonyl, 2-methylbutylcarbonyloxy, 2- methylhexyloxy, 2-methyloctyloxy, 2-methylbutyl, 2-methylbutyloxy, 2- chlorobutylcarbonyloxy, methyl, methyloxy, ethyl, and ethyloxy. As can be seen from the formulas and the above examples, L1 - L6 can represent chiral or non- chiral groups. A1 - A3 are each independently selected from the ring formulas 12 - 19. X
1 - X4 are independently selected for each of A1 - A3 and are H, F, or Cl. B and B ' are luiking groups selected from a single bond, -CH2CH2-, -CH=CH-, -C ≡C-, -OCH2-, or -CH2O-.
The chiral, laterally substituted compounds of formula (1) are liquid crystal compounds that exhibit a chiral smectic C phase. Preferably, the compounds exhibit a chiral smectic C phase over a broad temperature range, such as over a range of at least 20°C, more preferably at least 30°C, and most preferably over at least 40 °C range. Also it is preferred that the compounds exhibit a chiral smectic C phase at low temperatures, including ambient temperatures. Accordingly, it is preferred that the lower end of the chiral smectic C phase is 20 °C or less, more preferably 10°C or less, and most preferably, 5°C or less. The smectic C phase temperature values can be determined by conventional techniques known in the art; i.e., heating the compounds to the isotropic liquid phase, and then observing the phases and their transition temperatures during cooling and then heating again. In the present application the transition temperatures were determined using a Mettler FP5 hotstage and control unit in conjunction with a polarizing microscope and these values were confirmed using differential scanning calorimetry (Perkin-Elmer DSC- 7).
Preferably, the compound of formula (1) is represented by one of the formulas 1.1 - 1.39 set forth below. In these formulas, R3 and R4 represent a group of formulas L1 - L6 , while R1 , R 2 , and X1 - X 4 have the same definition as in formula (1).
Figure imgf000011_0001
Formula 1.1 Formula 1.2
Figure imgf000011_0002
Formula 1.3 Formula 1.4
Figure imgf000011_0003
Formula 1.5 Formula 1.6
Figure imgf000011_0004
Formula 1.7 Formula 1.8
Figure imgf000011_0005
Formula 1.9 Formula 1.10
Figure imgf000011_0006
Formula 1.11 Formula 1.12
Figure imgf000011_0007
Formula 1.13 Formula 1.14
Figure imgf000012_0001
Formula 1.15 Formula 1.16
Figure imgf000012_0002
Formula 1.23 Formula 1.24
Figure imgf000012_0003
Formula 1.26
Figure imgf000013_0001
Formula 1.27 Formula 1.28
Figure imgf000013_0002
Formula 1.29 Formula 1.30
Figure imgf000013_0003
Figure imgf000013_0005
Figure imgf000013_0004
Formula 1.31 Formula 1.32
Figure imgf000013_0006
Formula 1.33
Figure imgf000013_0007
Formula 1.34
Figure imgf000013_0008
Formula 1.35 R1 and R2 are each independently selected from the group consisting of formulas S1, S2 and S3:
Y1 Y3 t I HC — (CH2) „— (0) m C (CH2) k— (O) , — (CH2) p- (S1
C=CH— ( CH2) n (O) m— C— ( CH2) k (O) ,— ( CH2) , (S2
I I
Y2 Y4
k-(0) ,-(CH2) - (s3)
Figure imgf000014_0001
wherein Y1, Y2, Y3, and Y4 are each independently hydrogen, alkyl, F, CN, CF3 or OCF3, n, p, and k are each independently an integer from 0 to 7, and m and 1 are each independently zero or 1 , with the proviso that at least one of R1 and R2 is a chiral radical;
Z1 and Z 2 are each independently a ring selected from the group consisting of formulas 2-11
The compounds of formula (1) can be prepared by workers skilled in this art without undue experimentation through conventional reactions that are per se known in the art and from conventional and/or commercially available starting materials. However, preferred reaction schemes are set forth hereinbelow. Liquid crystal compounds according to the present invention can be obtained by the transformation of 3,6-disubstituted cyclohex-2-enones. Synthesis of these starting compounds is shown in scheme 1. For convenience and clarity the compounds are shown without the subscripts a - d, but such should be assumed to be present.
COCH3
Ri-Ai -CH + (CH3)2NCH2CH2OC -A2-Z? -A3 -R2
COOC2H5
Formula 20 Formula 21
Figure imgf000015_0001
Formula 22
Figure imgf000015_0002
Formula 23
Figure imgf000015_0003
Formula 24
Scheme 1 The process consists of heating acetoacetic esters with hydrochloride 4- substituted β-N-dimethylaminoprophio-phenones in the presence of an alkaline hydroxide. The 3,6-disubstituted cyclohex-2-enones can then be transformed into
3,6-disubstituted cyclohexanones (Formula 24) by reduction with hydrogen in the presence of 10% palladium on carbon.
As shown in schemes 2 and 3, other compounds of formula (1) can be readily obtained from the compounds of Formulas 23 and 24. Again, for convenience, the subscripts a - d have been omitted from these schemes. However, the schemes embrace any one or more of a - d being zero. In detail, the 3,6-disubstituted cyclohex-2-enones can be transformed into the corresponding 4,4-disubstituted 3-hydroxybiphenyls, teφhenyls and quateφhenyls (Formula 27) by aromatization in the presence of 10% palladium on carbon at 200°C or by the boiling of them in alcohols in the presence of iodine. The 3,6-disubstituted cyclohexanones can be transformed into the corresponding cis and trans alcohols (Formula 34) by reduction with NaBH4 or LIA1H4 in an appropriate solvent.
Fluorosubstituted compounds (Formula 38-39) are prepared by heating ketones (Formula 24) with diethylaminosulfur trifluoride in benzene or methylene chloride and the resulting difluoroderivatives (Formula 36) are then treated with a base, advantageously KOH or with alcohalate.
Figure imgf000017_0001
Formula 26
Formula 25
Figure imgf000017_0002
Formula 23
— ZZ—A3_R2
Figure imgf000017_0003
Formula 28 Formula 27
OR4
Ri-Ai— ' _A2 — Z2-A3— R2
Formula 29
Scheme 2
Figure imgf000018_0001
Pαπnul- 44
Scheme 3
The cyanounsaturated compounds (Formula 42, 43) are obtained by treating the ketones (Formula 24) with acetone cyanohydrine in the presence of tertiary amines or alkaline metal carbonates in dioxane or tetrahydrofuran and then by treating of the corresponding cyanoalcohols with POCl3 in the presence of a tertiary aliphatic amine or pyridine. The isomeric compounds (Formula 42, 43) are separated by crystallization. The chlorine substituted compounds (Formulae 26, 30, 31) are obtained by heating ketone (Formula 23, 24) with PC15, PCI, in hexane or benzene. The isomeric compounds (Formula 30, 31) are separated by crystallization or used in a form of the isomeric mixtures. Compounds of Formula 25 and 32 are obtained from ketone (Formula 23,
34) by treating them with Grignard reagent in anhydrous etheral solution. Then the corresponding alcohols are heated in the presence of catalytic amount of acids, advantageously p-toluenesulfonic acid, in toluene solution.
Compounds of Formula 36 are obtained by treating ketone 24 with triethyl orthoformate in the presence of p-toluenesulfonic acid in ethanol.
The chlorocyclohexane derivatives (Formula 33) are obtained by treating the corresponding alcohols (Formula 34) with PC15, SOCl2, POCl3.
The fluorocyclohexane derivatives (Formula 40) are synthesized by treating the alcohols 34 with diethylaminosulfur trifluoride (DAST) in methylene chloride at temperature below 20°C.
Using the above mentioned methods, one can easily obtain cyclohexene, cyclohexane, benzene, biphenyl, teφhenyl and quateφhenyl derivatives which until now were difficult to obtain and to investigate.
The compounds of formula (1) are useful in liquid crystal display devices including TN, STN, and ferroelectric LC displays. The compounds of Formula (1) are especially useful in creating compositions having various values of optical anisotropy and dielectric anisotropy as well as a wide temperature interval of the smectic C phase. Compositions according to the present invention require at least two compounds, with at least one of them being a compound of Formula (1). The compounds contained in the composition can be exclusively of formula (1) or a combination with other liquid crystal compounds.
Compositions containing compounds of Formula (1) that have 2 or 3 rings show low or intermediate clearing temperatures. Compositions containing compounds of Formula (1) that have 4 or 5 rings have a broadening of the smectic C phase, including broader than 100°C. The compositions are useful in ferroelectric liquid crystal displays, TN, STN, and active matrix displays. The high chemical stability and resistivity of these mixtures enable the stable performance of the display.
Preferably the composition is a ferroelectric composition and exhibits a chiral smectic C phase over a broad temperature range, preferably over at least a 40 °C interval. Moreover, preferably the composition simultaneously exhibits a lower end of the chiral smectic C phase at 10°C or less, more preferably at 10°C or less, and most preferably at -30°C or less.
In one embodiment, one or more compounds of Formula (1) is combined with at least one liquid crystal pyrimidine derivative. Preferably the pyrimidine derivative exhibits a smectic C phase and is capable of forming a ferroelectric liquid crystal composition. Such compounds include phenyl -substituted pyrimidines such as 2-alkoxyphenyl-5-alkylpyrimidines where the alkoxy and alkyl groups each contain from 1 to 12 carbon atoms.
The composition of the present invention can be used in any conventional liquid crystal display device. As understood by workers skilled in this art, such devices generally comprise two parallel electrodes, at least one of which is transparent, and having a layer of the liquid crystal composition disposed therebetween. In more detail, die liquid crystal layer is typically disposed between two parallel plates, one of which is transparent, that are in turn supported by (or surrounded by) the parallel electrodes. Between the parallel plates there may also be one or more of an aligning layer, isolating layer, and colored filter layer. In a preferred embodiment, the display device is operated by the ferroelectric effect.
The invention will now be described with reference to various examples.
However the invention should not be construed as being limited to the examples.
EXAMPLE 1.
3-(4-octyloxyphenyl-6-(2-methylbutyl)cyclohex-2-enone (Formula 23)
A mixture 0.1 mol of hydrochloride of /3-N-dimethylaminoethyl 4- octyloxypropiophenone, 0.12 mol of 2-(2-methylbutyl)acetoacetic ester, 0.25 mol sodium isopropylate in 200 ml anhydrous isopropanol was refluxed for 5 hours. The mixture was cooled and acidified with 20% solution of sulfuric acid. The oily substance from the mixture was extracted with diethyl ether. The extract was washed with water, dried over anhydrous Na2SO4 and filtrated. The residue obtained after the evaporation of the solvent was purified by crystallization from isopropanol. Yield 63% .
Using this method, the following compounds were prepared:
3-phenyl-6-(2-methylbutyl)cyclohex-2-enone,
3-(4-octyloxyphenyl)-6-(2-methylbutyl)cyclohex-2-enone,
3-(4-(2-methylbutyl)phenyl)-6-octylcyclohex-2-enone, 3-(4-citronellyloxyphenyl)-6-heptylcyclohex-2-enone,
3-(4-octyloxybiphenyl-4)-6-(2-methylbutyl)cyclohex-2-enone,
3-(4-citronelly loxybiphenyl-4)-6-(hexyl-21 )cyclohex-2-enone ,
3-(4-(2-methylbutyl)styryl-6-octylcyclohex-2-enone,
3-(4-citronellyloxystyryll)-6-heptylcyclohex-2-enone, 3-(4-octyloxystyryl)-6-citronellylcyclohex-2-enone,
3-(4-octyloxystyryl)-6-citronellylcyclohex-2-enone,
3-(4-pentylbiphenyl)-6-citronellycyclohex-2-enone (having m.p. 15 SmC 87 SmA 155 I), l ,4-bis-(3-citronellycyclox-2-enonoyl-6)benzene, 4,4-bis-(3-citronellycyclox-2-enonoyl-6)biphenyl,
3-(4-citronellyloxybiphenyl)-6-(2-cyanoethyl)cyclohex-2-enone,
3-(4-(2-methylbutyl)biphenyl)-6-(trans-4-butylcyclohexylethyl-2)cyclohex-2-enone, and
3-(trans-4-(2-methylbutyl)cyclohexylphenyl)-6-(trans-4-octylcyclohexyl)cyclohex-2- enone.
Example 2
3-(4-octyloxyphenyl-6-(2-methylbutyl)cyclohexanone (Formula 24) 0.1 mol of 3-(4-octyloxyphenyl-6-(2-methylbutyl)cyclohex-2-enone and 5 g of KOH were dissolved in 150 ml isopropanol and hydrogenated with gaseous hydrogen at 50 °C in the presence of 1 g of catalyzer (10% Pd/C) until hydrogen was not absorbed any longer. Then the catalyzer was filtrated off and the solvent was evaporated. The residue was poured into water and extracted with hexane. After hexane was evaporated, the residue was several times recrystallized from ethanol. Yield 47%.
Using this method the following compounds were prepared:
3-phenyl-6-(2-methylbutyI)cyclohexanone,
3-(4-octyloxyphenyl)-6-(2-methylbutyl)cyclohexanone,
3 -(4- (2-methy lbuty l)pheny l)-6-octy ley c lohexanone , 3-(4-octyloxybiphenyl-4)-6-(2-methylbutyl)cyclohexanone,
3-(2-(4-citronellyloxyphenyl)ethyl)-6-heptylcyclohexanone, l ,4-bis-(3-(2-methylhexyl)lcycloxanonoyl-6)benzene,
4,4-bis-(3-(2-methylbutyl)cycloxanonoyl-6)biphenyl,
3-(4-(2-methylbutyl)biphenyl)-6-(trans-4-butylcyclohexylethyl-2)cyclohexanone, and 3-(trans-4-(2-methylbutyl)cyclohexylphenyl)-6-(trans-4-octylcyclohexyl) cyclohexanone.
Example 3.
Synthesis of l-(2-methylbutyl)-2-cyano-4-(4-octyloxybiphenyl)cyclohex-l-ene (Formula 42)
A mixture of 0.5 mol of 3-cis-citronellyl-6-(4-octyloxybiphenyl)cyclohexanone, 0.2 mol acetone cyanohydrine, 0.2 mol triethylamine and 40 ml of tetrahydrofuran was left for 24 h at room temperature. After the addition of 100 ml of benzene, the mixture was diluted with water and diluted hydrochloric acid and dried over anhydrous sodium sulfate. Thereafter the mixture was filtrated and benzene was evaporated. To the residue 4 ml pyridine and 0.1 mol POCl3 was added and the resulting mixture was heated while boiling 7 hours. Then the mixture was poured into water with ice and the product was extracted into benzene. The extract was washed with water and with diluted hydrochloric acid, dried over MgSO4 and filtrated. After the evaporation of benzene, the residue was crystallized from methanol-isopropanol mixture. Yield 38% . Example 4.
Synthesis of l-cyano-3-trans-(4-octyloxybiphenyl)-6-(2-methylbutyl)cyclohex- 1 -ene
(Formula 43)
A mixture of 0.05 mol of 3-trans-citronellyl-6-(4-octyloxybiphenyl)cyclohexanone, 0.2 mol acetone cyanohydrine, 0.2 mol triethylamine and 40 ml of tetrahydrofurane was left for 24 h at room temperature. After the addition of 100 ml of benzene, the mixture was diluted with water and diluted hydrochloric acid and dried over anhydrous sodium sulfate. Thereafter the mixture was filtrated and benzene was evaporated. To the residue 4 ml pyridine and 0.1 mol POCl3 was added and the resulting mixture was heated while boiling 7 hours. Then the mixture was poured into water with ice and the product was extracted into benzene. The extract was washed with water and with diluted hydrochloric acid, dried over MgSO4 and filtrated. After the evaporation of benzene, the residue was crystallized from methanol-isopropanol mixture. Yield 45% .
Example 5
Synthesis of l-(2-methylbutyl)-2-cyano-4-(4-octyloxybiphenyl)cyclohexane (Formula
44)
A mixture of the corresponding cyanocompounds (0.03 mol) prepared as described in example 4 was dissolved in a tetrahydrofuran-isopropanol (10: 1) mixture. To the resulting mixture 0.2 g of Pd/C (10%) was added and connected to a source of hydrogen. The mixture was stirred until hydrogen was no longer absorbed. After that the catalyzer was filtrated off and the solvents distilled off and the product was crystallized from a methanol-isopropanol mixture. Yield 38% .
Example 6
Synthesis of l-(2-methylbutyl)-2-chloro-4-(4-octyloxybiphenyl)cyclohex-l-ene
(Formula 30)
A mixture 0.03 mol cis-3-(2-methylbutyl)-6-(4-octyloxybiphenyl)cyclohexanone, 0.07 mol PCI, NaSO and 50 ml benzene was heated while boiling and after cooling it was treated with 10% solution of KOH. Thereafter the organic layer separated, washed with water, dried over anhydrous MgS04 and filtrated through a layer of Al2O3. After the evaporation of the solvent, the oily liquid was crystallized from methanol-isopropanol mixture. Yield 48% .
Example 7.
Synthesis of l-(2-methylbutyl)-2-methyl-4-(4-octyloxybiphenyl)cyclohex-l-ene (Formula 32)
To 0.04 mol methylmagnesium iodide in 200 ml of diethyl ether. 0.03 mol cis-3-2- (2-methylbutyl)-6-4-octyloxybiphenyl)cyclohexanone was added and stirred for 4 hours. The resulting magnesium salt was decomposed with 20% solution of H2SO4 and the organic layer was separated and dried over Na2SO4. Then the solvent was evaporated and 50 ml of toluene and catalytic amount of p-toluenesulphonic acid were added to the residue and heated using azetropic head until water stopped to evolve. Then the mixture was cooled and diluted with water. The toluene layer was separated, dried over Na2SO4 and filtrated. The residue was dissolved in hexane and the crude product was purified by column chromatography and recrystallized from isopropyl alcohol. Yield 70%.
Example 8.
Synthesis of l-(2-methylbutyl)-2-ethoxy-4-(4-octyloxybiphenyl)cyclohex-l-ene (Formula 36)
A mixture containing 0.05 mol of cis-3-(2-methylbutyl)-6-4-octyloxybiphenyl) cyclohexanone, 0.15 mol ethyl ester of orthoformic acid, catalytic amounts of p- toluenesulphonic acid and 150 ml ethyl alcohol was stirred for 6 h. Thereafter it was diluted with water and extracted with benzene. After separating the benzene layer was washed with water and dried with Na2SO4. The oily residue left after distilling of benzene was dissolved in hexane and eluted on a column filled with silica gel collecting the fractions. On the basis of chromatographic analysis the fractions containing pure product were joined, solvent was evaporated. Yield 48% . Example 9.
Synthesis of trans-l-(2-methylbutyl)-2,2-difluoro-4-(4-octyloxybiphenylcyclohexane
(Formula 37)
A mixture containing 0.01 mol trans-3-(2-methylbutyl)-6-(4-octyloxybiphenyl) cyclohexanone, 0.01 mol diethylaminosulfur trifluoride (DAST) and 15 ml benzene was heated while boiling 24 hours. Thereafter the mixture was poured into water, benzene layer was separated, washed with water, dried with MgSO4 and filtrated. The crude product remained after the evaporation of the solvent was recrystallized from isopropanol. Yield 60% .
Example 10.
Synthesis of l-(2-methylbutyl)-2-fluoro-4-(4-octyloxybiphenyl)cyclohex-l-ene
(Formula 39)
A mixture 0.01 mol of trans-l-(2-methylbutyl)-2,2-difluoro-4-(4-octyloxybiphenyl) cyclohexane, 0.05 mol KOH and 30 ml ethylene glycol was stirred at 130°C for 8 hours, thereafter it was diluted with water and extracted with benzene. The benzene layer was washed with water, dried with MgSO4, filtrated. The residue left after the evaporation of the solvent was recrystallized from isopropanol. Yield 47%.
Example 11.
Synthesis of 2-(2-methylbutyl)-5-(4-octyloxybiphenyl)cyclohexan-l-ol (Formula 34).
The mixture 0.05 mol of trans-3-(2-methylbutyl)-6-4-octyloxybiphenyl) cyclohexanone, 0.05 mol sodium borohydride and 100 ml isopropyl alcohol was stirred at 50-60°C for 8 h. After the reaction mixture was acidified with hydrochloric acid and extracted into ether. The etheral extract was washed with water and dried MgSO4. The solvent was removed in vacuo and the crude product was recrystallized from hexane. Yield 85%. Example 12.
Synthesis of l-(2-medιylbutyl)-2-fluoro-4-(4-octyloxybiphenyl)cyclohexane (Formula
40)
To 0.05 mol of 2-(2-memylbutyl)-(4-octyloxybiphenyl)cyclohexan-l-ol in 15 ml CH Cl was added 0.05 mol of diethylaminosulfur trifluoride (DAST) at - 70°C. Thereafter, the cooling was stopped and the mixmre was allowed to room temperature, poured into water and layers were separated. The organic layer was dried with Na2SO4, filtrated. After the evaporation of the solvent, the crude product was recrystallized from ethanol. Yield 50% .
Example 13.
Synthesis of 4-(2-methylbutyl)-3-hydroxy-4-octyloxyteφhenyl (Formula 27)
0.1 mol of 3-(4-octyloxyphenyl-6-(2-methylbutyl)cyclohex-2-enone were hydrogenated at 200 °C in the presence of 1 g of catalyzer (10% Pd/C). The reaction mixture was dissolved in ether and then the catalyzer was filtrated off and the solvent was evaporated. The residue was several times recrystallized from toluene. Yield 47%.
Example 14.
Synthesis of l-(2-methylbutyl)-2-chloro-4-(4-octyloxybiphenyl)cyclohexane
(Formula 33)
A mixture 0.05 mol of 2-(2-methylbutyl)-5-(4-octyloxybiphenyl)cyclohexan-l-ol, 0.05 mol SOCl2 in 35 ml benzene was heated at 30°C O.05 h. Thereafter, the heating was stopped and the mixture poured into water. Thereafter, the organic layer was separated, washed with water, dried over anhydrous MgSO4 and filtrated. After the evaporation of the solvent, the oily liquid was crystallized from methanol- isopropanol mixture. Yield 57% .
Example 14. Synthesis of 4-(2-methylbutyl)-3-chloro-4-octyloxyteφhenyl (Formula 26)
0.1 mol of 3-(4-octyloxyphenyl-6-(2-methylbutyl)cyclohex-2-enone, 0.01 mol PC1S. In 30 ml benzene was boiled 4 h. Thereafter, the heating was stopped and the mixture poured into 10% solution of KOH. Thereafter, the organic layer was separated, washed with water, dried over anhydrous MgSO4 and filtrated. After the evaporation of the solvent, the oil liquid was crystallized from isopropanol mixmre. Yield 65% .
Using this method the following compounds were prepared
4-citronellyl-3-chloro-4-octyloxyteφhenyl m.p. 5 SmC 67 SmA 105 I
Example 16.
Synthesis of 4-(2-methylbutyl)-3-citronyllyloxy-4-octyloxyteφhenyl (Formula 29).
A mixture of 0.01 mol of 4-(2-methylbutyl)-3-hydroxy-4-octyloxyteφhenyl, 0.012 mol citronellile bromide, 0.02 mol KOH and 50 ml isopropyl alcohol was boiled 5 h. Thereafter, it was diluted with water and extracted with benzene. The benzene layer was washed with water, dried with MgSO4, filtrated. The residue left after the evaporation of the solvent was recrystallized from isopropanol. Yield 64% .
Example 17.
Synthesis of 2-(2-methylbutyl)-5-(4-octyloxybiphenyl)-l-(2-methylbutyl carbonyloxy)cyclohexane (Formula 35)
To 0.01 mol 2-(2-methylbutyl)-5-(4-octyloxybiphenyl)cyclohexan-l-ol and 0.12 mol 2-methyl-butyτol chloride in 50 ml anhydrous ether 0.02 mol pyridine was added.
After 12 h the reaction mixture was acidified with hydrochloric acid and separated.
The emeral layer was washed with water and dried MgSO4. The solvent was removed in vacuo and the crude product was recrystallized from ethanol. Yield
45% .
Example 18. Mixmre A of the following composition:
2-(4-Heptyloxyphenyl)-5-heptylpyrimidine - 5% 2-(4-Octyloxyphenyl)-5-heptylpyrimidine - 10% 2-(4-Nonyloxyphenyl)-5-heptylpyrimidine - 15 % 2-(4-Octyloxyphenyl)-5-octylpyrimidine - 20% 2-(4-Decycloxyphenyl)-5-octylpyrimidine - 30% 2-(4-Hexyloxyphenyl)-5-nonylpyrimidine - 20%
m.p. 10 SmC 51 SmA 63 N 69 I
Example 19.
Mixmre B of the following composition:
Mixture A - 90% 4-citronellyl-3-chloro-4-octyloxy teφhenyl - 10% m.p. -5 SmC 59 SmA 61 N 65 I
The invention having been thus described it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the following claims.
Industrial Applicability The compounds of formula (1) are useful in liquid crystal display devices including TN, STN, and ferroelectric LC displays. The compounds of Formula (1) are especially useful in creating compositions having various values of optical anisotropy and dielectric anisotropy as well as a wide temperamre interval of the smectic C phase. The compound of the present invention can be used in any conventional liquid crystal display device.

Claims

What is claimed is:
1. A chiral liquid crystalline compound of formula (1):
R1— (A1),— Z1— (A2)b— (Z2)c— <A3)d— R2 (1) wherein a, b, c, and d are each independently zero or 1; R1 and R are each independently selected from the group consisting of formulas S1, S2 and S3:
yl γ3
H IC-(CH2)n-(0)m-C I-(CH2)k-(0) -(CH2)p- (S1)
I I γ2 Y4
yl γ3
I I
C=CH- (CH2) „- (O) m-C-(CH2) k- (O) - (CH2) .- (S2)
Figure imgf000030_0001
HC- ( CH2 )' n- ( O ) m-C-CH=CH- ( CH2 ) k- ( O ) ,- { CH2 ) - (S3)
wherein Y1, Y2, Y3, and Y4 are each independently hydrogen, alkyl, F, CN, CF3 or OCFj, n, p, and k are each independently an integer from 0 to 7, and m and 1 are each independently zero or 1 , with the proviso that at least one of R1 and R2 is a chiral radical;
Z1 and Z2 are each independently a ring selected from the group consisting of formulas 2-11
Figure imgf000031_0001
(2) (3) (4) (5)
Figure imgf000031_0002
(6) (7) (8)
Figure imgf000031_0003
(9) (10) (11)
wherein X represents O, F, Cl, OH, CN, or a group represented by formulas L1 L6:
Y1
HC- (CH2) n- (0) m-C- (CH2) k- (0) ,- (CH2) - (L1)
Y4
yl γ3
I I
C=CH- (CH2) „- (O) m-C- (CH2) k- (O) ,- (CH2) . ( 2
Y'
HC- (CH2) n- (O) m-C-CH=CH- (CH2) k- (O) ,- (CH2) .- (L3)
Ϋ4 yl γ3
HC- ( CH2 ) „- ( O ) m-C- ( CH2 ) k- ( O ) - ( CH2 ) ,-COO- γ !22 I γ4
Y1 Y3
I I
C=CH- (CH2) n- (O) m-C- (CH2) k- (O) - (CH2) p-CO - (L5 γ2 γ4
yl γ3
H { CH2 ) k- ( O ) - ( CH2 ) p-COO- ( L6
Figure imgf000032_0001
wherein Y1, Y2, Y , Y4 , n, p, k, m and 1 have the same definitions as above in formulas S'-S3;
A1, A2 and A3 are each independently a ring group selected from the group consisting of formulas 12-19:
Figure imgf000032_0002
(15)
(14)
Figure imgf000032_0003
(16) (17)
Figure imgf000033_0001
wherein X1, X 2, X 3 and X4 are each independently H, F, or Cl and B and B are each independently a single bond, -CH2CH2-, -CH =CII-, -C ≡C-, -OCH -, or - CH2O-; with the proviso that when the ring structure formed by three of A1. Z1 , A2 , Z2 and A3 is teφhenyl, then none of X, X' , X2 , X and X represent F.
2. The compound according to claim 1 , wherein R1 and R2 are both chiral radicals .
3. The compound according to claim 1 , wherein X is represented by one of formulas L'-L6.
4. The compound according to claim 3, wherein c and d are both zero.
5. The compound according to claim 1 , wherein at least one of a and b is 1.
6. The compound according to claim 1 , wherein R1 and R2 are each independently represented by formula S1.
7. The compound according to claim 1 , wherein said compound exhibits a chiral smectic C phase.
8. The compound according to claim 7, wherein said compound exhibits a chiral smectic C phase over a temperamre interval having a range of at least about 40 °C.
9. The compound according to claim 7, wherein said compound exhibits a lower end of said chiral smectic C phase at a temperamre of 10°C or less.
10. A liquid crystal composition, comprising: at least one compound of formula 1 :
(A ( Z2 ) c ( A3 -R- ( 1 ) wherein a, b, c, and d are each independently zero or 1 ; R1 and R2 are each independently selected from the group consisting of formulas S\ S2 and S 3 :
γl γ3
I I
HC — (CH2) „ (0) m C (CH2) k— (O) , — (CH2) p (S1)
Y4
C=CH — (CH2) n (O) m — C— (CH2) k — (O) ,— (CH2) 2\ γ2 γ4
(CH2) k- (O) ,- (CH2) - (s-
Figure imgf000034_0001
wherein Y1, Y2, Y3, and Y4 are each independently hydrogen, alkyl, F, CN, CF3 or OCF3, n, p, and k are each independently an integer from 0 to 7, and m and 1 are each independently zero or 1 , with the proviso that at least one of R1 and R2 is a chiral radical;
Z1 and Z 2 are each independently a ring selected from the group consisting of formulas 2-11
Figure imgf000035_0001
(2) (3) (4) (5)
Figure imgf000035_0002
Figure imgf000035_0003
wherein X represents O, F, Cl, OH, CN, or a group represented by formulas L1 L6: γl Y3
HC— (CH2) n— (O) ra— C— (CH2) k— (O) j— (CH2) p— (L1)
C=CH ( CH2) n— (0) m— C— ( CH2) k (O) ,— ( CH2) ( 2)
Ϋ4
γl γ3
HC- ( CH2 ) π- ( O ) m-C-CH=CH- ( CH2 ) k- ( 0 ) ,- ( CH2 ) p- ;L3) γ2 γ y. y3
I I
HC— (CH2) n (O) m C (CH2) (O) , — (CH2) — COC ( 4
Y Y4
C=CH- (CH2) n- (O) m-C- (CH2) k- (O) ,- (CH2) p-COO- 1 5) γ2 γ4
HC- ( CH2 ) n- ( O ) m-C-CH=CH- ( CH2 ) k- ( O ) , I- ( \ C ^Hn22 ) 1 -COO- ( 6
Y4
wherein Y1, Y2, Y3 , Y4 , n, p, k, m and 1 have the same meanings as above in formulas SJ-S3;
A1, A2 and A3 are each independently a ring group selected from the group consisting of formulas 12-19:
Figure imgf000036_0001
(15)
(14)
Figure imgf000036_0002
αβ) (17)
Figure imgf000037_0001
wherein X1, X2, X3 and X are each independently H, F, or Cl and B and *B are each independently a single bond, -CH2CH2-, -CH = CH-, -C ≡ C-, -OCH 2 -, or - CH2O-; with the proviso that when e ring structure formed by three of A1, Z\ A2 , Z2 and A3 is teφhenyl, then none of X, X1 , X 2 , X3 and X4 represent F; wherein said composition exhibits a chiral smectic C phase.
11. The composition according to claim 10, further comprising at least one pyrimidine compound.
12. The composition according to claim 11 , wherein said composition exhibits a chiral smectic C phase and has a lower limit at a temperamre of -30 °C or less.
13. The composition according to claim 12, wherein said composition exhibits a chiral smectic C phase over a temperamre interval having a range of at least 40°C.
14. A liquid crystal display, comprising: two parallel plate electrodes, at least one of which is transparent; and a liquid crystalline layer comprising the composition according to claim 10, disposed between said plates.
15. The liquid crystal display according to claim 14, which further comprises an aligning or isolating layer, or both, disposed between said plates.
PCT/KR1997/000169 1996-09-12 1997-09-11 Liquid crystal materials WO1998011173A1 (en)

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KR100325849B1 (en) * 1999-03-03 2002-03-07 김순택 3-aryl-6-substituted cyclohex-2-enones, liquid crystal composition comprising the same and liquid crystal display device using the liquid crystal composition
CN114106850A (en) * 2021-12-17 2022-03-01 苏州汉朗光电有限公司 Positive liquid crystal composition and application thereof in liquid crystal display device

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KR20040078712A (en) * 2003-03-04 2004-09-13 삼성전자주식회사 Cyclohexane derivative, nematic liquid crystal composition comprising the same, and liquid crystal display using the nematic liquid crystal composition
JP2014025045A (en) * 2011-09-07 2014-02-06 Dainippon Printing Co Ltd Ferroelectric liquid crystal composition and liquid crystal display
JP2014015595A (en) * 2011-09-07 2014-01-30 Dainippon Printing Co Ltd Ferroelectric liquid crystal composition and liquid crystal display device
JP2013067775A (en) * 2011-09-07 2013-04-18 Dainippon Printing Co Ltd Ferroelectric liquid crystal composition and liquid crystal display element

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KR100325849B1 (en) * 1999-03-03 2002-03-07 김순택 3-aryl-6-substituted cyclohex-2-enones, liquid crystal composition comprising the same and liquid crystal display device using the liquid crystal composition
CN114106850A (en) * 2021-12-17 2022-03-01 苏州汉朗光电有限公司 Positive liquid crystal composition and application thereof in liquid crystal display device
CN114106850B (en) * 2021-12-17 2022-11-18 重庆汉朗精工科技有限公司 Positive liquid crystal composition and application thereof in liquid crystal display device

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