GB2078727A - Anisotropic Cyclohexene Compounds and Liquid Crystal Mixtures Containing Them - Google Patents

Anisotropic Cyclohexene Compounds and Liquid Crystal Mixtures Containing Them Download PDF

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GB2078727A
GB2078727A GB8116687A GB8116687A GB2078727A GB 2078727 A GB2078727 A GB 2078727A GB 8116687 A GB8116687 A GB 8116687A GB 8116687 A GB8116687 A GB 8116687A GB 2078727 A GB2078727 A GB 2078727A
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BBC Brown Boveri AG Switzerland
BBC Brown Boveri France SA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
    • C07C17/2632—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions involving an organo-magnesium compound, e.g. Grignard synthesis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/18—Polycyclic aromatic halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/235—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring and to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C43/247—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring and to a carbon atom of a ring other than a six-membered aromatic ring containing halogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Liquid Crystal Substances (AREA)

Abstract

New anisotropic cyclohexene compounds of the formula <IMAGE> in which X<1> and X<2> are each a hydrogen or halogen atom or a nitrile group; Z is a simple covalent bond or a carboxyl, oxycarbonyl, methyleneoxy or oxymethylene group; Y<1> and Y<2> are each a C1-C12 alkyl, alkoxy, monoalkylamino or alkylthio group or a C2-C13 alkylcarbonyloxy, alkyloxycarbonyloxy group or a nitrile group, or one of Y<1> and Y<2> is a group of the formula: <IMAGE> in which Y<3> has the meaning defined for Y<1> or Y<2> and Z, X<1> and X<2> and X<3> have the meanings defined above, are suitable for use in liquid crystal mixtures.

Description

SPECIFICATION Anisotropic Cyclohexene Compounds and Liquid Crystal Mixtures Containing Them This invention relates to anisotropic cyclohexene compounds and liquid crystal mixtures (LC mixtures) containing them.
It is known that binuclear or trinuclear compounds suitable for LC mixtures in LC indicators can be advantageously modified by replacing some or all of the aromatic nuclei of such compounds by trans-cyclohexyl rings (see for example German Offenlegungsschriften Nos. 26 36 684, 28 00 553 and German Auslegeschrift No. 24 29 093). LC mixtures with comparatively less optical anisotropy and reduced viscosity can be obtained with such trans-cyclohexyl compounds.
A disadvantage of the anisotropic trans-cyclohexyl compounds is that the preparation of these compounds by the generally required separation of the desired trans-isomers from the normally nonanisotropic cis-isomers and separation of the isomer mixtures generally obtained in the synthesis is complicated and is thus comparatively costly.
It is known, from European Patent Application No. 78 300649 (Publication No. 0,002,136), that this disadvantageous isomer separation can be omitted if, for LC mixtures, instead of the transcyclohexane compounds there are used the analogous 1,4-disubstituted cyclohexene compounds of the formula:
in which R is an alkyl group and n is 1 or 2. In these cyclohexene derivatives (V) the double bond of the cyclohexene ring is in the gamma-position relative to the electrophobic alkyl group R. In the compounds known from Japanese Laid Open Patent Application (No. 79 41 8401) of the formula:
the double bond of the cyclohexene ring is also in the gamma-position with respect to the electrophobic group R.
It was found that compounds of formulae (V) and (X) have, as compared to the trans-cyclohexane compounds, a high sensitivity to actinic radiation, e.g. day-light UV radiation, which is normally a disadvantage for the operation of LC indicators because the action of such radiation on the LC indicator has to be eliminated, e.g. by appropriate filters, or the LC mixture is chemically altered as a result of the action of the radiation.
It is an object of this invention to provide new anisotropic cyclohexene compounds which are suitable for use in LC mixtures and have a better stability towards actinic radiation, especially day-light UV radiation, than the known compounds of the formulae (V) and (X).
According to the invention there are provided, as new compounds, anisotropic cyclohexene compounds of the formula:
in which: X1 and X2 are the same or are different and each is hydrogen or halogen atom or a nitrile group; Z1 is a simple covalent bond (-) or a carboxyl (-COO-), oxycarbonyl (-OOC), methyleneoxy (-CH2O-) or oxymethylene (-OCH2-) linkage; and Y1 and Y2 are the same or are different and each is a C, C,2 alkyl, C1-C12 alkoxy, C1-C12 alklthio, C1-C12 monoalkylamino, alkyloxycarbonyloxy (in which the alkyl group is a C1-C12 alkyl group), alkoxycarbonyloxy (in which the alkoxy group is a C1-C12 alkoxy group) or a nitrile group, or one of Y1 and Y2 (preferably is a group of the formula:
in which: X', X2 and Z have the meanings defined above and Y3 has the meaning defined for Y1 or Y2 (other than a group of the formula 1 a, 1 b or 1 c).
Preferably y2, when not a group of the formula 1 a, 1 b or 1 c, is a nitrile, alkyl or alkoxy group and similarly the group Y3, when present, is preferably a nitrile, alkyl or alkoxy group. When any of Y1, Y2 or Y3 is or contains an alkyl group, that alkyl group is preferably a straight chain alkyl group.
Particular examples of binuclear compounds in accordance with the invention are those in which Xr and X2 are both hydrogen atoms; Z is a simple covalent bond; Y' is an n-propyl, n-pentyl, n-hexyl, nnonyl, ethoxy, n-butoxy, n-hexoxy, n-octoxy, ethylamino, n-butylamino, n-hexylamino or n-octylamino group; and Y2 iS a cyano, n-butoxy, n-butythio, n-butylamino or n-pentyl group.
Particular examples of trinuclear compounds in accordance with the invention are those in which X' and X2 are both hydrogen atoms; Z is a simple covalent bond; Y' is an n-propyl, n-pentyl, n-heptyl nnonyl, ethoxy, n-butoxy, n-hexoxy, n-octoxy, ethylthio, n-butylthio, n-hexylthio, n-octylthio, npropionyloxy, n-pentanoyloxy, n-heptanoxyloxy or n-nonanoyloxy group; and Y2 is a p-cyanophenyl, p (n-propyl)-phenyl, p-ethoxyphenyl, p-propionyloxyphenyl, p-ethylthiophenyl, or p-ethylaminophenyl group.
The reason for the greater UV stability of the compounds according to the invention of formula (1) as compared with the above mentioned known cyclohexene compounds of formulae (V) and (X) is still not completely clear, but it is assumed that on account of the alpha-position of the double bond in the cyclohexene ring in the compounds of formula (1) there are, in contrast to the known compounds of formulae (V) and (X), no double bonds conjugated with the phenyl ring and the bridge members Z-if the latter do not denote a simple covalent bond-and that the absence of conjugation of the alphacyclohexene double bond with other double bonds in the molecule of the compounds of formula (1) is the basic reason for the suprisingly better UV stability of these compounds.Thus, according to the invention, the advantage of the known compounds of formula (V) and (X) can be achieved without their disadvantage. The invention also provides LC mixtures which contain at least one compound of formula (1). Such mixtures according to the invention are preferably eutectic mixtures which consist in part or wholly of compounds of formula (1) and optionally also contain anisotropic compounds known per se.
An LC mixture according to the invention preferably contains at least about 5 mol % of at least one compound of formula (1). Thus compounds of formula (1) may be used individually or as a mixture in a manner known per se for LC mixtures. Depending on the manner of operation of the cell, the LC mixtures can be adapted according to the required values of the mixture (e.g. with respect to the dielectric and optical anistropy, viscosity and the like). The LC mixtures may also contain conventional additives such as dyes, pigments or cholesterol substances for, e.g. guest/host operation. Eutectic mixtures are as a rule preferred.
Compounds of formula (1) in which Z is a simple covalent bond may be prepared in accordance with the reaction scheme:
Compounds of formula (1) in which Z is carboxyl or oxycarbonyl linkage may be prepared in accordance with the reaction scheme:
Compounds of formula (1) in which Z is a methoxyleneoxy or oxymethylene linkage may be prepared in accordance with the reaction scheme:
In the above reaction schemes Xa, X2, yr and Y2 have the meanings defined above and Hal represents a halogen atom. Where the reactants contain a hydroxyl group this may be in the form of an alkali metal (e.g. sodium or potassium) hydroxylate group.
The scheme I involves a Grignard reaction to introduce a group Ya at the keto carbon atom of the starting cyclohexanone by converting the keto oxygen atom into a hydroxyl group and then splitting off water to form the alpha-double bond. Conversions of this type are well known and the starting cyclohexanones can be obtained from commercially available compounds (Y2=H) by introducing the desired R2 group by methods known per se.
The schemes Ila and llb lead to compounds according to the invention with a carboxyl group (scheme Ila) or an oxycarboxyl group (scheme llb) as the bridge member. The synthesis IS a conventional condensation, and suitable starting compounds are either known or may be obtained by known methods frorn known compounds, for example by converting known cyclohexanecarboxylic acids into their acid halides. The schemes Illa and Illb lead to compounds according to the invention with Z=-CH2O-, -O-CH2O. The starting compounds for the synthesis scheme (III) are either known per se or can be obtained by known methods from known compounds, e.g. by reducing the cyclohexenecarboxylic acids to the corresponding alcohols.
The new compounds of formula (I) according to the invention are anistropic, i.e. are either enantiotropically liquid crystalline or monotropically liquid crystalline; in the case of monotropically liquid crystalline substances the clear point (Tc) of the pure substance is lower than its melting point (Tm), but may be measured e.g. by supercooling in the pure monotropic substance, or may be calculated by investigating an enantiotropic mixture containing the monotropic substance and evaluating the mesomorphic contribution of the monotropic substance.
As is conventional in the art of liquid crystalline substances, such parameters are expressed as follows.
"K N I" where "K" indicates transition from the normal crystalline state into the mesomorphous or nematic ("N") state, while 'I" indicates transition from the nematic to the isotropic (normal liquid) state.
The actual transition temperature (degree Centigrade) are set between the symbols; when a temperature value between "N" and "I" is set in brackets, this indicates a monotropic transition.
In order that the invention may be well understood the following examples are given by way of illustration only.
Example 1 4-(4'-cyanophenyl)-cyclohexanone (20 g) was added to 90 ml of tetrahydrofuran at 0 C, followed by the addition of heptylmagnesium bromide (prepared from 2.9 g Mg and 17.8 g bromoheptane) in 60 ml of ether at O-50C while stirring. The reaction mixture was stirred for 2 hours at room temperature, and was then poured onto ice and extracted with methylene chloride. The organic phase was washed, dried, and concentrated by evaporation. The crude product (cis/trans mixture, 22 g) was dissolved in 25 ml of pyridine to split off water, and 5 ml of thionyl chloride was added at --200C. The reaction mixture was stirred for 30 minutes at OOC, and was then poured onto ice and extracted with methylene chloride. The organic phase was washed, dried and concentrated by evaporation.The crude product was chromatographed on silica gel.
The cyclohexene compound according to the invention thus obtained has the formula:
in which R'=n-heptyl and R2=CN, and can therefore be described as 4-cyano-4'-heptyl-1 ',2',3',6'tetrahydrobiphenyl: K 35.1 N (5.0)1 Comparison with the analogous known compound of the above formula (V) (R=n-heptyl, n=1; K 47.5, N 611) showed tha,t the new compound according to Example 1 had an improved UV stability.
Example 2 In a similar way to Example 1 but using n-nonylmagnesium bromide, the compound corresponding of formula (10) in which R'=n-CgH,0 and R2=CN was prepared, i.e. 4-cyano-4'-nonyl- 1 ',2',3',6'-tetrahydrobiphenyl: K 29.8 N (15.5)1 Examples 34 In a similar way to Example 1 and by using n-propyl- and n-pentylmagnesium bromide, the corresponding compounds of formula (10) can be prepared: (3): formula (10), R1=n-propyl, R2=CN and (4): formula (10), R'=n-pentyl, R2=CN.
By adopting the procedure described in Example 1 but using 4-(2',3'-dibromo-4'-butoxyphenyl) cyclohexanone, the corresponding 2,3-dibromo-4-butyloxy-4'-alkyl- 1 ',2',3 ,6'-tetrahydrobiphenyls can be obtained with the alkylmagnesium compounds specified in Examples 1-3, i.e. the following compounds of formula (II) can be obtained.
R=n-C5H11; R=n-C4H9O; X=X=Br R1=n-C,H,5; R2=n-C4HgO; X2=X2=Br R=n-C9H19; R=n-C4H9O; X=X=Br By analogy with the afore-described procedure and suitably altering the 4'-substituent of the phenylcyclohexanone compound and the alkylmagnesium bromide, the following 2,3-dibromo-4,4'- dialkyl-1 ',2',3',6'-tetrahydrobiphenyls according to the invention of formula (11) can be obtained.
R=n-C5H11; R=n-C5H11; X=X=Br R=n-C5H11; R=n-C7H15; X=X=Br R=n-C7H15; R=n-C5H11; X=X=Br R=n-C7H15; R=n-C7H15; X=X=Br By replacing Br with CN according to known methods (G. W. Gray s A. Mosley, J. Chem. Soc.
Perkin Trans. 2,97 (1976)) in the afore-described compounds, the following 2,3-dicyano-4-alkoxy-4'alkyl-1',2',3',6-tetrahydrobiphenyls or 2,3-dicyano-4,4'-dialkyl-1',2',3',6'-tetrahydrobiphenyls according to the invention of formula 11 can be obtained.
R=n-C5H11; R2=n-C4H90; X'=X2=CN R=n-C7H15; R2=n-C4H90; X'=X2=CN R=n-C5H11; R=n-C5H11; X=X=CN R=n-C5H15; R=n-C7H15; X=X=CN By using 4-[2',3'-dibromo-4'-(4"-penyl phenyl)-phenyl] cyclohexanone or 4-(2",3"-dibromo-4"pentyl-4'-biphenyl)-cyclohexanone, according to the procedure described in Example 1 the corresponding compounds of formula 12 or formula 13 respectively can be obtained.
R=C3H7; X=X2=Br 25 R=C5H11; X=X=Br By replacing Br with CN in the aforesaid compounds, the following 2',3'-dicyano-4,4'-dialkyl~ 1",2",3",6"-tetrahydro-terphenyls (12) or 2,3-dicyano-4,4"-dialkyl-1",2",3",6"-tetrahydro-terphenyls (13) respectively can be obtained.
R=C3H7; X=X=CN R=C5H11; X=X=CN

Claims (5)

Claims
1. As new compounds, anisotropic cyclohexene compounds of the formula:
in which: X' and X2 are the same or are different and each is a hydrogen or halogen atom or a nitrile group; Z' is a simple covalent bond, or a carboxyl, oxycarbonyl, methyleneoxy or oxymethylene group; and Y' and Y2 are the same or are different and each is a C1-C12 alkyl, C1-C12 alkoxy, C1-C12 monoalkylamino, alkylcarbonyloxy (in which the alkyl group is a C1-C12 alkyl group), alklyoxycarbonylopxy) in which thealkyloxy group is a C1-C12 alkyl group), C1-C12 alkylthio or nitrile group or one of Y and Y is a group of the formula:
in which: Z, X' and X2 have the meanings defined above and Y3 has the meaning defined for Y' and Y.
2. Compounds as claimed in claim 1 in which Y2 is a group of the formula (1 a), (1 b) or (1 c).
3. Compounds as claimed in claim 1 in which Y2 or Y3 is a nitrile, alkyl or alkoxy group.
4. Compounds as claimed in claim 1 in which Y2 iS a nitrile group and Y' is not a nitrile group.
5. A liquid crystal mixture containing at least one compound as claimed in any one of claims 1-4.
GB8116687A 1980-06-02 1981-06-01 Anisotropic cyclohexene compounds and liquid crystal mixtures containing them Expired GB2078727B (en)

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CH425780A CH644574A5 (en) 1980-06-02 1980-06-02 ANISOTROPE CYCLOHEXEN COMPOUNDS AND LIQUID CRYSTAL MIXTURES.

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US4405488A (en) * 1980-10-09 1983-09-20 Chisso Corporation Liquid-crystalline halogenobenzene derivatives
US4415470A (en) * 1980-11-10 1983-11-15 Merck Patent Gesellschaft Mit Beschrankter Haftung Liquid crystalline fluorine-containing cyclohexylbiphenyls and dielectrics and electro-optical display elements based thereon
US4422951A (en) * 1981-04-02 1983-12-27 Chisso Corporation Liquid crystal benzene derivatives
US4505837A (en) * 1980-02-22 1985-03-19 Merck Patent Gesellschaft Mit Beschrankter Haftung Liquid crystalline phenylcyclohexene derivatives
US4514317A (en) * 1982-02-04 1985-04-30 Merck Patent Gesellschaft Mit Beschrankter Haftung Anisotropic compounds and liquid crystal mixtures
US4536321A (en) * 1983-02-18 1985-08-20 Chisso Corporation Fluorobenzene derivatives and liquid crystal compositions containing the same
US4550981A (en) * 1982-09-30 1985-11-05 Hoffmann-La Roche Inc. Liquid crystalline esters and mixtures
WO1986002925A1 (en) * 1984-11-14 1986-05-22 Nauchno-Issledovatelsky Institut Prikladnykh Fizic LIQUID CRYSTAL 4-n-PENTYL-PHENYL ETHERS OF 4'-(TRANS-4''-n-ALKYLCYCLOHEX-2-ENOYLOXY) BENZOIN ACIDS
WO1986002926A1 (en) * 1984-11-14 1986-05-22 Nauchno-Issledovatelsky Institut Prikladnykh Fizic LIQUID CRYSTAL 4-(4'-CYANODIPHENYL) ETHERS OF TRANS-4''-n-ALKYLCYCLOHEX-2-ENCARBOXYLIC ACIDS AND LIQUID CRYSTAL COMPOSITION FOR ELECTROOPTICAL INFORMATION PRESENTING DEVICES BASED ON THESE COMPOUNDS
US4605520A (en) * 1985-01-25 1986-08-12 Nauchno-Issledovatelsky Institut Prikladnykh Fizicheskikh Problem Imeni A.N. Sevchenko Liquid crystal 4-(4'-cyanodiphenyl) esters of trans-4"-N-alkylocyclohex-2-enecarboxylic acids
US4605510A (en) * 1985-01-25 1986-08-12 Nauchno-Issledovatelsky Institut Prikladnykh Problem Imeni A.N. Sevchenko Liquid crystal composition for electrooptical devices for presentation of information
US4621901A (en) * 1984-07-12 1986-11-11 Hoffmann-La Roche Inc. Novel liquid crystal mixtures
US4659499A (en) * 1984-12-31 1987-04-21 Crystaloid Electronics Company Liquid crystal materials
US4659502A (en) * 1984-01-17 1987-04-21 Merck Patent Gesellschaft Mit Beschrankter Haftung Ethane derivatives
US4696549A (en) * 1983-07-22 1987-09-29 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Compounds containing a fluorobiphenylyl group and their use in liquid crystal material and devices
US4698177A (en) * 1985-04-16 1987-10-06 Dainippon Ink And Chemicals, Inc. Cyclohexylcyclohexene derivatives
US4704005A (en) * 1982-10-21 1987-11-03 Hoffmann-La Roche Inc. Dicyano compounds
US4710315A (en) * 1984-04-16 1987-12-01 Merck Patent Gesellschaft Mit Beschrankter Haftung Anisotropic compounds and liquid crystal mixtures therewith
US5013478A (en) * 1983-03-16 1991-05-07 Hoffmann-La Roche Inc. Liquid crystals
US5068389A (en) * 1986-03-14 1991-11-26 Merck Patent Gesellschaft Mit Beschrankter Haftung Tertiary alcohols
EP1897928A1 (en) 2006-09-06 2008-03-12 Chisso Corporation Chlorofluorobenzene liquid crystal compound, liquid crystal composition and liquid crystal display device
WO2012130380A1 (en) * 2011-03-29 2012-10-04 Merck Patent Gmbh Liquid-crystalline medium

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US4357078A (en) * 1980-01-30 1982-11-02 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Liquid crystal compounds containing an alicyclic ring and exhibiting a low dielectric anisotropy and liquid crystal materials and devices incorporating such compounds
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CA1106406A (en) * 1977-11-21 1981-08-04 Takashi Inukai Liquid crystal compounds
JPS54106453A (en) * 1978-02-08 1979-08-21 Chisso Corp P-(4-alkyl-1-cyclohexenyl)benzoic acid p-cyanophenyl ester
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US4505837A (en) * 1980-02-22 1985-03-19 Merck Patent Gesellschaft Mit Beschrankter Haftung Liquid crystalline phenylcyclohexene derivatives
US4405488A (en) * 1980-10-09 1983-09-20 Chisso Corporation Liquid-crystalline halogenobenzene derivatives
US4415470A (en) * 1980-11-10 1983-11-15 Merck Patent Gesellschaft Mit Beschrankter Haftung Liquid crystalline fluorine-containing cyclohexylbiphenyls and dielectrics and electro-optical display elements based thereon
US4545922A (en) * 1980-11-10 1985-10-08 Merck Patent Gesellschaft Mit Beschrankter Haftung Liquid crystalline fluorine-containing cyclohexylbiphenyls and dielectrics and electro-optical display elements based thereon
US4422951A (en) * 1981-04-02 1983-12-27 Chisso Corporation Liquid crystal benzene derivatives
US4514317A (en) * 1982-02-04 1985-04-30 Merck Patent Gesellschaft Mit Beschrankter Haftung Anisotropic compounds and liquid crystal mixtures
US4550981A (en) * 1982-09-30 1985-11-05 Hoffmann-La Roche Inc. Liquid crystalline esters and mixtures
US4704005A (en) * 1982-10-21 1987-11-03 Hoffmann-La Roche Inc. Dicyano compounds
US4536321A (en) * 1983-02-18 1985-08-20 Chisso Corporation Fluorobenzene derivatives and liquid crystal compositions containing the same
US5013478A (en) * 1983-03-16 1991-05-07 Hoffmann-La Roche Inc. Liquid crystals
US4696549A (en) * 1983-07-22 1987-09-29 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Compounds containing a fluorobiphenylyl group and their use in liquid crystal material and devices
US4659502A (en) * 1984-01-17 1987-04-21 Merck Patent Gesellschaft Mit Beschrankter Haftung Ethane derivatives
USRE36849E (en) * 1984-04-16 2000-09-05 Merck Patent Gmbh Anisotropic compounds and liquid crystal mixtures therewith
US4710315A (en) * 1984-04-16 1987-12-01 Merck Patent Gesellschaft Mit Beschrankter Haftung Anisotropic compounds and liquid crystal mixtures therewith
US4621901A (en) * 1984-07-12 1986-11-11 Hoffmann-La Roche Inc. Novel liquid crystal mixtures
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GB2182656A (en) * 1984-11-14 1987-05-20 Nii Prikladnych Liquid-crystal 4-n-pentyl-phenyl ethers of 4'-(trans-4 -n-alkylcyclohex-2-enoyloxy)benzoin acids
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JPS5738729A (en) 1982-03-03
CH644574A5 (en) 1984-08-15
DE3023368A1 (en) 1981-12-10
GB2078727B (en) 1984-05-23
DE3023368C2 (en) 1989-09-21

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