[go: up one dir, main page]

GB2216523A - Dihalobenzene liquid crystalline compounds - Google Patents

Dihalobenzene liquid crystalline compounds Download PDF

Info

Publication number
GB2216523A
GB2216523A GB8905443A GB8905443A GB2216523A GB 2216523 A GB2216523 A GB 2216523A GB 8905443 A GB8905443 A GB 8905443A GB 8905443 A GB8905443 A GB 8905443A GB 2216523 A GB2216523 A GB 2216523A
Authority
GB
United Kingdom
Prior art keywords
trans
phe
difluoro
alkyl
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
GB8905443A
Other versions
GB2216523B (en
GB8905443D0 (en
Inventor
Volker Reiffenrath
R Joachim Krause
Georg Weber
R Ulrich Finkenzeller
R Andreas Waechtler
R Thomas Geelhaar
R David Coates
R Ian Charles Sage
R Simon Greenfield
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck Patent GmbH
Original Assignee
Merck Patent GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Merck Patent GmbH filed Critical Merck Patent GmbH
Publication of GB8905443D0 publication Critical patent/GB8905443D0/en
Publication of GB2216523A publication Critical patent/GB2216523A/en
Application granted granted Critical
Publication of GB2216523B publication Critical patent/GB2216523B/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C07D213/30—Oxygen atoms
    • 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
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/24—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/11—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound oxygen atoms bound to the same saturated acyclic carbon skeleton
    • C07C255/14—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound oxygen atoms bound to the same saturated acyclic carbon skeleton containing cyano groups and esterified hydroxy groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/50—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of non-condensed six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/55—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and esterified hydroxy groups bound to the carbon skeleton
    • 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
    • C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
    • C—CHEMISTRY; METALLURGY
    • 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
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/34—One oxygen atom
    • 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
    • C09K19/0403—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit the structure containing one or more specific, optionally substituted ring or ring systems
    • 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
    • C09K19/10—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
    • 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
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
    • 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
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
    • C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
    • 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
    • C09K19/3001—Cyclohexane rings
    • 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
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
    • 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
    • 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
    • C09K19/0403—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit the structure containing one or more specific, optionally substituted ring or ring systems
    • C09K2019/0407—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit the structure containing one or more specific, optionally substituted ring or ring systems containing a carbocyclic ring, e.g. dicyano-benzene, chlorofluoro-benzene or cyclohexanone
    • 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
    • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
    • 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
    • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
    • C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (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)
  • Pyridine Compounds (AREA)

Description

1 - Oihalogenobenzene derivatives 2216523
DESCRIPTION
The invention relates to dihalogenobenzene derivatives of the formula I R 1-A 1-Z 1-A 2 (Z 2-A 3)n-R I wherein R 1 2 R and R E R 3 and R 4 Z 1 and z 2 A 1, A 2 and A 3 in each case independently of one another are a straight-chain or branched alkyl or perfluoroalkyl group having in each case 1-15 C atoms, it also being possible for one or more CH 2 or CF 2 groups to be replaced by a grouping chosen from the group comprising -0 O-, -S co, -0-CO-, -S-CO-, -O-COO-, -CO-S-, -CO-O-, -E-, -CH- halogeno and -CHCN or a combination of two of these groupings, two hetero atoms not being linked directly, and one of the radicals R 1 and R 2 is also H, F, Cl, Br, CN, COOH, OH, SH, NH 2, NO 2, -NCS, NC or SF 5, is CR 3 =CR 4, CR 3-CR 4 or CC, \ 0/ 0 in each case independently of one another are H, alkyl having 1-6 C atoms, F, Cl, Br, CF 3 or CN, in each case independently of one another -CO-O-, -O-CO-, -CH 2 CH 2-, -CH 2-O-, -O-CH 2-, -N=CH 2-, -CH 2 =N-, -CH 2-CO-, -CO-CH 2-, -N=N-, -NO=N-, -N=NO-, -C-C or a single bond, in each case indeoendently of one another' 2 - are a 1,4-phenylene group which is unsub- stituted or substituted by one or more halogen, nitrile and/or alkyl substituents, it also being possible for one or more CH groups to be replaced by N, a 1,4-cyclo- hexylene group, it also being possible for one or two non-adjacent CH 2 groups to be replaced by 0 and/or S, or a 1,4-cyclohex- enylene group, 1,4-bicyclo( 2,2,2)octylene group, piperidine-1,4-diyl group, naphtha- lene-2,6-diyl group, decahydronaphthalene- 2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group and n is 0, 1, 2 or 3, with the provisos that a) at least one of the rings A 1, A and A is 2,3- dihalogeno-1,4-phenylene and b) if one of the rings A 1, A 2 and A 3 is a 2,3-dichloro- 1,4-phenylene group, Z 1 and Z 2 in each case independently of one another are only -CH 2 CH 2-, -CH 20-, -0-CH 2-, -N=CH 2-, -CH 2 =N-, -CH 2-CO-, -CO-CH 2-, -N=N-, -NO=N-, -N=NO-, -C-C or a single bond, or one of the radicals R 1 and R 2 is only F, Cl, Br, CN, NCS, NC or SF 5, c) if one of the rings A 1, A 2 and A 3 is a 2,3-di- fluoro-1,4-phenylene group and the other rings A 1, A 2 and A 3 are 1,4-phenylene groups, at least one group Z 1 and Z 2 is other than a single bond, or one of the radicals R 1 and R 2 is only F, Cl, Br, CN, NCS, NC or SF 5, and d) if one of the rings A 1, A and A is a 2,3-di- fluoro-1,4-phenylene group, one of the rings A 1 A 2 and A 3 is a 1,4-phenylene group and one of the rings A 1, A 2 and A 3 is a cyclohexylene group, at least one group Z 1 and Z 2 is other than a single bond.
For simplicity, in the fol Lowing text Cyc is a 1,4-cyclohexylene group, CCN is a 1-( 4)-cyano-1,4-cyclo- hexylene group, Che is a 1,4-cyclohexenylene group, Dio 3 - is a 1,3-dioxane-2,5-diyl group, Dit is a 1,3-dithiane- 2,5-diyl group, Bco is a 1,4-bicyclo C 2 2 2 loctylene group, Pip is a piperidine-1,4-diyl group, Phe is a 1,4- phenylene group, Pyd is a pyridine-2,5-diyl group, Pyr is a pyrimidine-2,5-diyl group and Pyn is a pyridazine-2,5- diyl group, it being possible for these groups to be un- substituted or substituted Phe X is a group of the X formula wn, wherein X below is preferably chlorine or fluorine.
XX 2 _ -,Phe X 2 is a group of the formula wherein X 1 and X 2 below are preferably chlorine and/ or fluorine.
The compounds of the formula I can be used as components of liquid crystal phases, in particular for displays based on the principle of the twisted cell, the guest-host effect, the effect of deformation of aligned phases or the effect of dynamic scattering.
Compounds of the formula I having negative anisotropy of the dielectric constant (AE = Ell El < 0, E 11 being the dielectric constant along the longitudinal molecular axis and el being the dielectric constant perpendicular thereto) are aligned in an electrical field with their longitudinal molecular axes perpendicular to the direction of the field This effect is known and is utilized for controlling optical transparency in various liquid crystal displays, thus, for example, in liquid crystal cells of the light scattering type (dynamic scattering), of the so-called DAP type (deformation of aligned phases) or of the guest/host type (guest/host interaction).
When a liquid crystal having positive dielectric anisotropy is used, homogeneous orientation thereof (which is achieved by treatment of the plate surface) is adjusted homoeotropically by applying a voltage, that is to say the cell is switched from "coloured" to "colour- less" Colourless symbols are displayed on a cotoured 4 - background in this way In contrast, when a Liquid crystal of negative dielectric anisotropy is used, homo- eotropic orientation thereof is adjusted (by treatment of the plate surface) by applying a voltage parallel to the electrode surfaces, which allows display of coloured pictorial elements on a colourless background.
Two-frequency matrix addressing has furthermore been proposed to improve the multiplex circumstances in multiplex activation of liquid crystal displays, in par- ticular of twisted cells and guest/host cells (for example German Offenlegungsschriften 28 56 134 and 29 07 940).
The fact that the dielectric anisotropy of liquid crystals which have positive anisotropy of the dielectric constant on application of a low-frequency voltage becomes negative under high frequencies is utilized here.
In order to keep the capacitive losses small, the "cross- over frequency" fc (dielectric relaxation frequency at which Ei 1 becomes e L) of such liquid crystals should be as low as possible and should not be above, for example, k Hz The absolute value of the dielectric anisotropy should furthermore be as large as possible both below and above the cross-over frequency It has been found, how- ever, that the substances which are particularly suitable for the two-frequency method in general have a lower absolute dielectric anisotropy at frequencies above the cross-over frequency than at those below the cross-over frequency This disadvantage could be eliminated by addition of compounds having negative dielectric aniso- tropy and suitable relaxation properties.
Compounds of the formula I are furthermore suit- able as components of chirally tilted smectic phases.
Chirally tilted smectic liquid crystal phases with ferroelectric properties can be prepared by adding a suitable chiral doping substance to base mixtures con- taining one or more tilted smectic phases (L A Veresnev et al, Mol Cryst Liq Cryst 89, 327 ( 1982); and H.R Brand et al, J Physique 44 (lett), L-771 ( 1983)).
- Such phases can be used as dielectrics for fast-switching displays based on the principle, described by Clark and Lagerwall, of SSFLC technology (N A Clark and S.T Lagerwall, Appl Phys Lett 36, 899 ( 1980); and USP 4,367,924) on the basis of the ferroelectric properties of the chirally tilted phase.
A number of liquid crystal compounds having weakly negative dielectric anisotropy have already been synthesized to date In contrast, still relatively few liquid crystal components having high negative anisotropy of the dielectric constant are known In addition, the latter in general have disadvantages such as, for example, poor solubility in mixtures, high viscosity, high melting points and chemical instability There is therefore a need for further compounds having negative dielectric anisotropy, which enable the properties of mixtures for the most diverse electrooptical applications to be further improved.
Liquid crystal components having negative di- electric anisotropy and containing two or three rings linked via carboxyl groups or a covalent bond and one or more side groups, such as halogen, cyano or nitro groups, are known from DE 22 40 864, DE 26 13 293, DE 28 35 662, DE 28 36 086 and EP 023,728.
The compounds claimed here are included in a wide formula in EP 084,194 However, no individual compounds of the formula according to the invention are mentioned therein From the prior art, the expert has thus not been able either to deduce synthesis possibilities for the compounds claimed in a simple manner, or to recognise that the compounds according to the invention have pre- dominantly favourably located mesophase ranges and are distinguished by a high negative dielectric anisotropy coupled with a low viscosity.
That publication also lacks any indication at all of the possibility of using the compounds according to the invention in displays based on SSFLC technology, since the compounds claimed therein have low smectic tendencies.
Dibenzoates of 2,3-dichlorohydroquinone are moreover known (for example Bristol et al, J Org.
Chem 39, 3138 ( 1974) or Clanderman et al, J Am Chem.
S Soc 97, 1585 ( 1975)), but these are monotropic or have very small mesophase ranges The 4-hydroxy-2,3-dichloro- benzoates which are described by Eidenschink et al.
(Angew Chem 89, 103 ( 1977)) also have only narrow mesophase ranges.
PCT/EP 87/00515 contains a general formula which also includes difluorophenyl compounds, and 4-ethoxy-4 ''- pentyl-2,3-difluoroterphenyl is described therein as a constituent of ECB mixtures.
Because of their high viscosity, the 4-alkyl-2,3- dichloropheny L-4 '-alkylbicyclohexyl-4-carboxylates known from DE OS 29 33 563 cannot be used industrially.
The invention was based on the object of dis- covering stable liquid crystal or mesogenic compounds having a high negative dielectric anisotropy and at the same time a low viscosity.
It has been found that the compounds of the for- mula I are outstandingly suitable as components of liquid crystal phases In particular, stable liquid crystal phases having a broad mesophase range and a comparatively low viscosity can be prepared with the aid of these com- pounds.
The compounds of the formula I are furthermore suitable as components of chirally tilted smectic liquid crystal phases.
By providing the compounds of the formula I, the range of liquid crystal substances which are suitable under various technological aspects for the preparation of liquid crystal mixtures is moreover quite generally considerably widened.
The compounds of the formula I have a wide range of applications Depending on the choice of the sub- stituents, these compounds can be used as base materials 7 - from which liquid crystal phases are predominantly composed; however, compounds of the formula I can also be added to liquid crystal base materials from other classes of compound, for example in order to vary the dielectric and/or optical anisotropy and/or the viscosity and/or the spontaneous polarization and/or the phase ranges and/or the tilt angle and/or the pitch of such a dielectric.
The compounds of the formula I are furthermore suitable as intermediates for the preparation of other substances which can be used as constituents of liquid crystal dielectrics.
The compounds of the formula I are colourless in the pure state and form liquid crystal mesophases in a temperature range which is favourably located for electrooptical use They are very stable towards chemi- cals, heat and light.
The invention thus relates to the compounds of the formula I, in particular the compounds of the formulae A, 8 and C RS ()m_( _) o CO-o OR 6 A (F) F R 5-COO(F OR 6 B F F R 5-0 g CO-O R 6 C wherein R 5 and R 6 in each case independently of one another are alkyl having 1-15 C atoms and m, p and o are O or 1.
The invention furthermore relates to the use of the compounds of the formula I as components of Liquid crystal media The invention moreover relates to liquid crystal media containing at Least one compound of the 8 - formula I and Liquid crystal di Splay elements containing such phases Such phases have particularly advantageous elastic constants and, because of their low values, are particularly suitable for TFT mixtures.
Above and below, R 1 R 2 A 1 A 2 A 3, 1 2 and Ao anbo R R A,,z, z and n have the meaning given, unless expressly indicated otherwise.
The compounds of the formula I accordingly include compounds having two rings, of the part formulae la and lb:
RI-A -Z -A 2 -R 2 R 1 -_A -_A 2 _R 2 Ia Ib, compounds having three rings, of the part formulae Ic to Ie:
R-A I-A 2 _A 3 _R 2 R-A -zl-A 2 _-A 3 _R 2 R -_A -zl -A 2 _Z 2 _A -3 _R 2 Ic Id Ie, compounds having four rings, of the part formulae Ik:
R 1-A 1-A 2 _A 3 _A 3 R 2 If Ri-Ai-zl-A 2 _A 3 _A 3-R 2 Ig Ri-A-A 2 _-Z 2 _A 3-A 3-R 2 Ih R 1-A 1-Z-A 2 _-Z 2 _A 3-A 3-R Ii Ri-AI-zl-A 2 _A 3-Z 2 _A 3-R Ij R 1-_Ai_-z -A 2 _-z 2 -A 3 _z 2 _A 3 _R 2 Ik If to and compounds having five rings, of the part to It:
Ri-Ai A 2 _A 3 _A 3-A 3 _R 2 R 1-Ai Zl A 2 _A 3 _A 3 _A 3-R R 1 A 1-A 2 _Z 2 _A 3 _A 3 _A 3 _R 2 R -A-Zl-A 2 _-z 2 _-A 3 _-A 3 _A 3 -R 2 R _A 1 _z 1 _A 2 _A 3 _z 2 _A 3 A 3 R 2 formulae II I 1 Im In Io Ip 9 - R 1-A 1-z 1-A 2 _A 3 _A 3 _z 2 A 3 R 2 Iq R 1 1-1 z 2 _ 22 3 2 3 3 _R 2 Ir R 1-Ai-Z 1-A 2-Z 2-A 3-Z 2-A 3-A 3-R 2 r 1 -1 1 z2 2 3 3 z 2 3 R 2 Is R 1-Ai-zl-A 2-Z 2-A 3-A 3-Z 2-A 3-R 2 s R 1 A 11 A 2 _ 2 _ 3 _ 2 _ 3 _ 2 _ 3 _R 2 it.
R 1-AZA 2-Z 2A 3-Z 2 A 3 -Z 2A 3 -R 2 It In the compounds of the formulae above and below, R 1 and R are preferably a Lkyl, or furthermore alkoxy having 1-12 C atoms.
Compounds of the formulae above and below in which one of the radicals R 1 and R 2 is CN, F or Cl are furthermore preferred.
A 1, A 2 and A 3 are preferably Phe X 2, Cyc, Phe, Dio or Pyr; the compound of the formula I preferably contains not more than in each case one of the radicals Dio, Dit, Pip, Bi, Pyn, Pyr or 2,3-dihalogeno-1,4phenylene.
In accordance with the proviso that at least one of the rings A 1, A 2 and A is 2,3-dihalogeno-1,4- phenylene, at least one of these rings can also be 2- fluoro-3-chloro-l,4-phenylene, 2-fluoro-3-bromo-1,4- phenylene, 2-fluoro-3-iodo-1,4-phenylene, 2-chloro-3- bromo-1,4-phenylene, 2-chloro-3-iodo-1,4-phenylene, 2- bromo-3-iodo-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,3-dichloro-1,4-phenylene, 2,3-dibromo-1,4-phenylene or 2,3-diiodo-1,4-phenylene The 2,3-dihalogeno-1,4-phenyl- ene rings in which the halogen substituents are identi- cal, such as 2,3-difluoro-1,4-phenylene or 2,3-dichloro1,4-phenylene, are preferred here, and 2,3-difluoro-1,4- phenylene is particularly preferred.
n is preferably 0, 1 or 2, and particularly preferably 1.
1 2 The groups Z and Z, which can be identical or different, are preferably single bonds, and secondly preferably -CO-O-, -0-CO-, -CEC or -CH 2 CH 2 group.
Particularly preferred compounds of the formula I are those wherein all the groups Z 1 and Z 2 are single bonds 12 or only one group Z 1 or Z 2 is -CO-O-, -0-CO-, -C-C- or -CH 2 CH 2-.
- In the case of 2,3-difluoro-1,4-phenylene com- pounds, the groups Z 1 or Z 2 adjacent to the Phe X 2 group are preferably single bonds, -C-C-, -O-CO-, -CO-O-or -CH 2 CH 2 groups.
In the case of the 2,3-dichloro-1,4-phenylene compounds, the groups Z 1 or Z 2 adjacent to the Phe X 2 group are preferably single bonds or -CO-O or -O-CO- groups.
12 R and R in the formulae above and below pre- ferably have 2-10 C atoms, in particular 3-7 C atoms.
One or two CH 2 or CF 2 groups in R 1 and R 2 can also be replaced Preferably, only one CH 2 group is replaced by -0-, -CO-, -C-C-, -S-, -CH=CH-, -CH-halogeno or -CHCN-, in particular by -0-, -CO or -C=C-.
In the formulae above and below, R 1 and R 2 are preferably alkyt, alkoxy or another oxaalkyl group, and furthermore also alkyl groups in which one or more CH 2 groups can be rep Laced by a grouping chosen from the group comprising -0-, -O-CO-, -C=C-, -CH=CH-, -CH-halo- geno and -CHCN or by a combination of two suitable groupings, hetero atoms not being linked directly to one another.
12 One of the radicals R and R 2 is preferably also halogen or CN Halogen is F, Cl or Br, preferably F If none of the radicals R 1 and R 2 is halogen or CN, R 1 and R 2 together preferably have 4-16 C atoms, in particular 4-10 C atoms.
If R 1 and R 2 are alkyl radicals having in each case 4-14 C atoms, in which one ("alkoxy" or "oxa- alkyl") or two ("alkoxyalkoxy" or "dioxaalkyl") non- adjacent CH 2 groups can be replaced by O atoms, they can be straight-chain or branched Preferably, they are straight-chain and have 2, 3, 4, 5, 6 or 7 C atoms, and accordingly are preferably ethyl, propyl, butyl, pentyl, hexyl, heptyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy or heptoxy, or furthermore methyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, 1 1 - tridecyloxy or tetradecyloxy.
Oxaalkyl is preferably straight-chain 2-oxapropyl (= methoxymethyl), 2 (= ethoxymethyl) or 3-oxabutyl (= 2-methoxyethyl), 2-, 3 or 4-oxapentyl, 2-, 3-, 4 or 5-oxahexyl, 2-, 3-, 4-, 5 or 6-oxaheptyl, 2-, 3-, 4-, 5-, 6 or 7-oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7 or 8-oxa- nony L, 2-, 3-, 4-, 5-, 6-, 7-, 8 or 9-oxadecyl, 1,3- dioxabutyl (= methoxymethoxy), 1,3-, 1,4-, 2,4-dioxa- pentyl, 1,3-, 1,4-, 1,5-, 2,4-, 2,5 or 3,5-dioxahexyl or 1,3-, 1,4-, 1,5-, 1,6-, 2,4-, 2,5-, 2,6-, 3,5-, 3,6- or 4,6-dioxaheptyl.
If R 1 and R 2 are an alkyl radical in which a CH 2 group is replaced by -S-, this can be straight-chain or branched Preferably, this thiaalkyl radical having 1-10 C atoms is straight-chain and is 2-thiapropyl, 2 or 3-thiabutyl, 2-, 3 or 4-thiapentyl, 2-, 3-, 4 or 5-thia- hexyl, 2-, 3-, 4-, 5 or 6-thiaheptyl, 2-, 3-, 4-, 5-, 6- or 7-thiaoctyl, 2-, 3-, 4-, 5-, 6-, 7 or 8-thianonyl or 2-, 3-, 4-, 5-, 6-, 7-, 8 or 9-thiadecyl.
Alkyl radicals R 1 or R 2 in which the CH 2 group adjacent to the group A 1, A 2 and/or A 3 is replaced by -S and which are therefore preferably methylthio, ethyl- thio, propylthio, butylthio, pentylthio, hexylthio, heptylthio, octylthio, nonylthio or decylthio, are parti- cularly preferred.
If R 1 and R 2 are an alkyl radical in which a 3 4 CH 2 group is replaced by -CR = CR 4-, the radicals R 3 and R 4 are preferably identical and are hydrogen.
This alkenyl radical can be straight-chain or branched.
Preferably, it is straight-chain and has 2 to 10 C atoms.
It is accordingly in particular vinyl, prop-l or prop- 2-enyl, but-1-, -2 or -3-enyl, pent-l-, -2-, -3 or -4- enyl, hex-1-, -2-, -3-, -4 or -5-enyl, hept-1-, -2-, -3-, -7-enyl, non-l-, -2-, -3-, -4-, -5-, -6-, -7 or -8-enyl or dec-l-, -2-, -3-, -4-, -5-, -6-, -7-, -8 or -9-enyl.
If R 1 and R 2 are an alkyl radical in which a CH 2 group is replaced by -0-CO or -CO-O-, this can oe 12 - straight-chain or branched Preferably, it is straight- chain and has 2 to 6 C atoms It is accordingly in particular acetyloxy, propionyloxy, butyryloxy, pentan- oyloxy, hexanoyloxy, acetyloxymethyl, propionyloxymethyl, butyryloxymethyl, pentanoyloxymethyl, 2-acetyloxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 3-acetyloxy- propyl, 3-propionyloxypropyl, 4-acetyloxybutyl, methoxy- carbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbon- yl, pentoxycarbonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, butoxycarbonylmethyl, 2-(methoxycarbonyl)ethyl, 2-(ethoxycarbonyl)ethyl, 2(propoxycarbonyl)ethyl, 3-(methoxycarbonyl)propyl, 3(ethoxycarbonyl)propyl and 4-(methoxycarbonyl)-butyl If R 1 and R 2 are an alkyl radical in which a CH 2 group is replaced by -CR 3 = CR 4 and an adjacent CH 2 group is replaced by -CO-, -0-CO or -0-CO-, R and R 4 are preferably hydrogen or methyl.
Preferably, this (meth)acryloyloxyalkyl radical is straight-chain and has 4 to 13 C atoms It is accord- ingly in particular acryloyloxymethyl, 2-acryloyloxy- ethyl, 3-acryloyloxypropyl, 4-acryloyloxybutyl, 5-acryloyloxypentyl, 6-acryloyloxyhexyl, 7-acryloyloxyheptyl, 8-acryloyloxyoctyl, 9-acryloyloxynonyl, 10-acryloyloxy- decyl, methacryloyloxymethyl, 2-methacryloyloxyethyl, 3- methacryloyloxypropyl, 4-methacryloyloxybutyl, 5-meth- acryloyloxypentyl, 6-methacryloyloxyhexyl, 7-methacryloyloxyheptyl, 8-methacryloyloxyoctyl or 9-methacryloy L- oxynonyl.
Compounds of the formula I which have end group substituents R 1 and/or R 2 which are suitable for poly- merization reactions are suitable for the preparation of liquid crystal polymers.
Compounds of the formula I having branched end group substituents R 1 and/or R 2 may occasionally be of importance because of a better solubility in the customary liquid crystal base materials, but in particular as chiral doping substances, if they are optically active Smectic compounds of this type are suitab Le as 13 - components of ferroelectric materials.
Branched groups of this type as a rule contain not more than one chain branching Preferred branched radicals R 1 and/or R 2 are isopropyl, 2-butyl (= 1- methylpropyl), isobutyl (= 2-methylpropyl), 2-methyl- butyl, isopentyl (= 3-methylbutyl), 2-methylpentyl, 3- methylpentyl, 2-ethylhexyl, 2-propylpentyl, isopropoxy, 2-methylpropoxy, 2-methylbutoxy, 3-methylbutoxy, 2- methylpentoxy, 3-methylpentoxy, 2-ethylhexoxy, 1-methyl- hexoxy, 1-methylheptoxy, 2-oxa-3-methylbutyl, 3-oxa-4methylpentyl, 4-methylhexyl, 2-nonyl, 2-decyl, 2-dodecy L, 6-methyloctoxy, 6-methyloctanoyloxy, 5-methylheptyloxy- carbonyl, 2-methylbutyryloxy, 3-methylvaleryloxy, 4- methylhexanoyloxy, 2-chloropropionyloxy, 2-chloro-3- methylbutyryloxy, 2-chloro-4-methylvaleryloxy, 2-chloro3-methylvaleryloxy, 2-methyl-3-oxapentyl, 2-methyl-3-oxa- hexyl, 2-fluoro-3-methylvaleryloxy and 2-fluoro-3-methyl- butoxy.
If R 1 and R 2 are an alkyl radical in which two or more CH 2 groups are replaced by -0 and/or -CO-O-, this can be straight-chain or branched Prefer- ably, it is branched and has 3 to 12 C atoms It is accordingly in particular bis-carboxy-methyl, 2,2-bis- carboxy-ethyl, 3,3-bis-carboxy-propyl, 4,4-bis-carboxy- butyl, 5,5-bis-carboxy-pentyl, 6,6-bis-carboxy-hexyl, 7,7-bis-carboxy-heptyl, 8,8-bis-carboxy-octyl, 9,9-bis- carboxy-nonyl, 10,10-bis-carboxy-decyl, bis-(methoxycarbonyl)-methyl, 2,2-bis-(methoxycarbonyl)-ethyl, 3,3bis-(methoxycarbonyl)-propyl, 4,4-bis-(methoxycarbonyl)- butyl, 5,5-bis-(methoxycarbonyl)-pentyl, 6,6-bis- (methoxycarbonyl)-hexyl, 7,7-bis-(methoxycarbonyl)- heptyl, 8,8-bis-(methoxycarbonyl)-octyl, bis-(ethoxy- carbonyl)-methyl, 2,2-bis-(ethoxycarbonyl)-ethyl, 3,3bis-(ethoxycarbonyl)-propyl, 4,4-bis-(ethoxycarbonyl)- butyl or 5,5-bis-(ethoxycarbonyl)-pentyl.
Compounds of the formula I which have end group substituents R 1 and/or R 2 which are suitable for poly- condensation reactions are suitable for the preparation 14 - of Liquid crystal polycondensates.
Formula I includes both the racemates of these compounds and the optical antipodes as welt as mixtures thereof.
Of the compounds of the formulae I and Ia to It, those in which at least one of the radicals contained therein has one of the meanings given as preferred are preferred.
Of the dinuclear compounds of the part formulae Ia to Ib, those of the part formulae Iaa to Ial and Iba to Ibf are preferred:
R 1-Phe X 2-CH 2 CH 2-Phe-R 2 Iaa 1 22 2 2 R-Phe X -CO-O-Phe-R Iab R 1 -Phe X 2-O-CO-Phe-R Iac R 1-Phe X 2-C-C-Phe-R Iad R-Phe X 2-CH 2 CH 2-Cyc-R Iae R 1 -Phe X 2-O-CO-Cyc-R Iaf R 1-Phe X 2-C=C-Cyc-R Iag R 1-Phe X 2-CO-O-Cyc-R 2 Iah R -Phe X Iah R 1 Phe X 2 -CHCH -Phe X-R 2 Iai 1 2 2 2 2 R 1-Phe X -O-CO-Phe X-R Iaj R-Phe X 2-O-CO-Phe X-R Iak 1 22 R -Phe X 2-C=C-Phe X-R Ial R 1-Phe X 2-Cyc-R 2 Iba R 1-Phe X -Bco-R Ibb 2 Ib 2 R-Phe X 2-Pyr-R Ibc R 1-Phe X 2-Pyd-R Ibd R 1-Phe X -Che-R Ibe R-Phe X 2-CCN-R Ibf Of the trinuclear compounds of the part formulae Ic to Ie, those of the part formulae Ica to leb are preferred:
- Rl-Phe X -A 2-A -R Ica 112 3 2 R -A -Phe X -A -R I cb Rl_-Phe X -Z i-A 2 _A 3 _-R 2 Ida R -A -Z -Phe X -A 3 -R 2 Idb R 1-Ai-zl-A 2-phex -R Idc R 1 -Phe X -Z -A -Z -A -R Ilea R-A -Z i-Phe XZ 2-A 3 _R 2 Ieb Of the preferred compounds of the part formulae Ida to Idc, those of the part formulae Idl to Id 6 are particularly preferred:
F F R 1 _ c O R 2 Idi 2 2 F K CH CH 2 Id 3 FF F F F R 1 $ -Oc OKG R Id S F F R O -0-Co O R 2 Id 6 (l Of the tetranuclear compounds of the part formulae If to Ik, those of the part formulae I 1 to 18 are preferred:
Ri-Phe X -A 2-A 3-A 3-R I 1 R -A -Phe X -A -A -R I 2 R 1-Phe X -Zi-A 2-A 3-A 3-R 2 I 3 1 12 i 33 2 R-Ah-Z -Phe X A -A -R I 4 I 1 1 22 332 R-A -Z -P Ahe X -A-A 3 -R IS 1 1 1 32 R-A -Z -A -A -Phe X_-R I 6 Rl A 1-Z 123 -phe X 3 R 2 16 RI 233 7 R 1-Phe X-A 2-Z 2-A -A 3 R 2 I 7 R 1 _A 1-Phe X-Z 2 -A 3-A 3 _R 2 I 8 In the above compounds of the part formulae Iaa to I 8, Phe X 2 is preferably 2,3-difluoro-1,4-phenylene 1 2 or 2,3-dichloro-1,4-phenylene The groups A, A and A 3 in the compounds of the part formulae Ica to I 8 are preferably trans-1,4-cyclohexylene (Cyc), 1,4-cyclo- hexylene (Che), 1,4-phenylene (Phe), 1,4-bicyclo C 2 2 2 loctylene (Bco), 2 or 3-halogeno-1,4-phenylene (Phe X), dioxane-2,5-diyl (Dio), dithiane-2,5-diyl (Dit) or pyrimidine-2,5-diyl (Pyr) Those of the abovementioned formulae which contain one or more groups CCN, Dio, Dit and/or Pyr in each case include the two possible 2,5- (Dio,Dit,Pyr) or 1,4-(CCN) position isomers.
The following small groups II to XVI of compounds in which Phe X 2 is 2,3-difluoro-1,4-phenylene or 2,3- dichloro-1,4-phenylene are particularly preferred.
Alkyl is preferably straight-chain methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl; and oxaalkyl is preferably straight-chain 2-oxa- propyl (= methoxymethyl), 2 (= ethoxymethyl) or 3-oxa- butyl ( 2-methoxyethyl), 2-, 3 or 4-oxapentyl, 2-, 3-, 4 or 5-oxahexyl, 2-, 3-, 4-, 5 or 6-oxaheptyl, 2-, 3-, 4-, 5-, 6 or 7-oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7 or 8- oxanonyl or 2-, 3-, 4-, 5-, 6-, 7-, 8 or 9-oxadecyl.
i 7 - Alkoxy is preferably straight-chain methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octyl- oxy, nonyloxy or decyloxy.
Halogen is preferably chlorine or fluorine, par- ticularly preferably fluorine.
II alkyl-Phe X 2-Cyc-alkyl alkyl-Phe X 2-Cyc-alkoxy alkyl-Phe X 2-Cyc-CO-O-alkyl alkyl-Phe X 2-Cyc-O-CO-alkyl halogeno-Phe X 2-Cyc-alkyl nitrile-Phe X 2-Cyc-alkyl halogeno-Phe X 2-Cyc-CO-O-alkyl alkyl-Phe X 2-Cyc-oxaalkyl alkyl-Phe X 2-CCN-alkyl alkyl-Phe X 2-Che-alkyl III alkyl-Phe X 2-Pyr-alkyl halogeno-Phe X 2-Pyr-alkyl nitrile-Phe X 2-Pyr-alkyl alkoxy-Phe X 2-Pyr-alkyl IV alkyl-Phe X 2-Cyc-Phe-alkyl alkyl-Phe X 2-Cyc-Phe-alkoxy halogeno-Phe X 2-Cyc-Phe-alkyl alkyl-Phe X 2-Cyc-Phe-CO-O-alkyl alkyl-Phe X 2-Cyc-Phe-O-CO-alkyl alkyl-Phe X 2-Cyc-Phe-CN alkyl-Phe X 2-Cyc-Phe X-CN alkyl-Phe X 2-Phe-Cyc-alkyl alkyl-Phe X 2-Cyc-Cyc-alkyl alkyl-Phe X 2-Cyc-Cyc-CN halogeno-Phe X 2-Cyc-Cyc-alkyl alkyl-Phe-Phe X 2-Cyc-alkyl alkyl-Phe-Phe X 2-Cyc-CO-O-alkyl I i -J 8 - nitrile-Phe-Phe X 2-Cyc-alkyl alky L-Phe X-Phe X 2-Cyc-alkyl V alkyl-Phe X 2-Phe-Phe-Cyc-alkyl alkyl-Phe X 2-Phe-Phe-Cyc-CN alkyl-Phe X 2-Cyc-Phe-Cyc-alkyl halogeno-Phe X 2-Cyc-Phe-Cyc-alkyl alky 1-Phe-Cyc-Phe X 2-Cyc-alkyl alkyl-Phe X-Cyc-Phe X 2-Cyc-alkyl nitrile-Phe X-Cyc-Phe X 2-Cyc'-alkyl nitr i le-Phe-Cyc-Phe X 2-Cyc-CO-O-alkyl VI alkyl-Phe X 2-CO-O-Phe-alkyl alkyl-Phe X 2-CO-O-Phe-CN alkyl-Phe X 2-CO-O-Phe-SF 5 alkyl-Phe X 2-O-CO-Phe-alkyl alkyl-Phe X 2-O-CO-Phe-alkoxy alkyl-Phe X 2-CH 2 CH 2-Phe-alkyl alkyl-Phe X 2-CH 2 CH 2-Phe-CN halogeno-Phe X 2-CH 2 CH 2-Phe-alkyl alkyl-Phe X 2-CH 2 CH 2-Phe-alkoxy alkyl-Phe X 2-CH 2 CH 2-Phe-alkyl halogeno-Phe X 2-O-CO-Phe-alkyl VII alkyl-Phe X 2-CH 2 CH 2-Phe X-CN halogeno-Phe X 2-CH 2 CH 2-Phe X-CN alkyl-Phe X 2-CO-O-Phe X-alkyl alkyl-Phe X 2-0-CO-Phe X-alkyl VIII alkyl-Phe X 2-CO-O-Cyc-alkyl alkyl-Phe X 2-O-CO-Cyc-alkyl halogenc-Phe X 2-O-CO-Cyc-alkyl alkyl-Phe X 2-CH 2 CH 2-Cyc-alkyl alkyl-Phe X 2-CH 2 CH 2-Dio-alkyl alkyl-Phe X 2-CEC-Cyc-CN IXalkyl-Phe X 2-CO-O-Phe-Phe-alkyl alkyl-Phe X 2-CO-O-Phe-Phe-alkoxy alkyl-Phe X 2-O-CO-Phe-Phe-alkyl alky L-Phe X 2-CH 2 CH 2-Phe-Phe-alkyl halogeno-Phe X 2-CH 2 CH 2-Phe-Phe-alkyl halogeno-Phe X 2-O-CO-Phe-Phe-a Lkyl nitrile-Phe X 2-CO-O-Phe-Phe-alkyl lq- Alkyl-Phe X 2-CH 2 CH 2-Phe-Phe-CN Alkyl-Phe X 2-CH 2 CH 2-Phe-Phe-Halogen Alkoxy-Phe X 2-CH 2 CH 2-Phe-Phe-Halogen Alkoxy-Phe X 2-CH 2 CH 2-Phe-Phe-CN Alkoxy-Phe X 2-CH 2 CH 2-Phe-Phe-Alkyl Nitril-Phe X 2-CH 2 CH 2-Phe-Phe-Alkyl X alkyl-Phe X 2-CO-O-Cyc-Phe-alkyl alkyl-Phe X 2-CO-O-Phe-Cyc-alkyl hatogeno-Phe X2-CO-O-Phe-Cyc-alkyl halogeno-Phe X 2-O-CO-Cyc-Phe-alkyl alkyl-Phe X 2-CH 2 CH 2-Phe-Cyc-alkyl alkyl-Phe X 2-CH 2 CH 2-Phe-Cyc-CN nitrile-Phe X 2-CO-O-Phe-Cyc-alkyl alkyl-Phe X 2-O-CO-Phe-Cyc-alkyl alkyl-Phe X 2-0-CO-Cyc-Phe-alkyl halogeno-Phe X 2-O 0-CO-Cyc-Phe-alkyl XI alkyl-Phe X 2-CO-O-Cyc-Cyc-alky L alkyl-Phe X 2-O-CO-Cyc-Cyc-alkyl halogeno-Phe X 2-O-CO-Cyc-Cyc-alkyl alkyl-Phe X 2-CH 2 CH 2-Cyc-Cyc-alkyl alkyl-Phe X 2-CH 2 CH 2-Cyc-CCN-alkyl XII alkyl-Phe X 2-CH 2 CH 2-Pyd-Phe-a Lkoxy alkyl-Phe X 2-CO-O-Phe-Pyd-alkyl XIII alkyl-Phe-CO-O-Phe X 2-Phe-alkyl alkyl-Phe-CH 2 CH 2-Phe X 2-Phe-alky L halogeno-Phe-CO-O-Phe X 2-Phe-alkyl halogeno-Phe-O-CO-Phe X 2-Phe-alkyl alkyl-Cyc-CH 2 CH 2-Phe X 2-Phe-alkyl alkyl-Phe-CH 2 CH 2-Phe X 2-Cyc-alkyl alkyl-Cyc-CH 2 CH 2-Phe X 2-Cyc-alkyl Alkyl-Phe-CH 2 CH 2-Phe X 2-Phe-Alkoxy Alkyl-Phe-CH 2 CH 2-Phe X 2-Phe-CN Alkyl-Phe-CH 2 CH 2-Phe X 2-Phe-Halogen Alkoxy-Phe-CH 2 CH 2-Phe X 2-Phe-Halogen Alkoxy-Phe-CH 2 CH 2-Phe X 2-Phe-CN Alkoxy-Phe-CH 2 CH 2-Phe X 2-Phe-Alkyl Ni tril-Phe-CH 2 CHI-Phe X Phe-Alkyl 2 2 L XlV alkyl-Phe X 2-Phe-CO-O-Phe-halogeno alkyl-Phe X 2-Phe-CO-O-Phe-alkyl alky L-Phe X 2-Phe-CH 2 CH 2-Phe-alkyl alkyt-Phe X 2-Phe-CH 2 CH 2-Cyc-alkyl alkyl-Phe X 2-Cyc-CH 2 CH 2-Phe-alkyl alkyt-Phe X 2-Cyc-CH 2 CH 2-Cyc-alkyl Alkyl-Phe X 2-Phe-CH 2 CH 2-Phe-Alkyl Alkyl-Phe X 2-Phe-CH 2 CH 2-Phe-Halogen Alkyl-Phe X 2-Phe-CH 2 CH 2-Phe-CN Alkyl-Phe X 2-Phe-CH 2 CH 2-Phe-Alkoxy Nitril-Phe X 2-Phe-CH 2 CH 2-Phe-Alkoxy Halogen-Phe X 2-Phe-CH 2 CH 2-Phe-Alkoxy Halogen-Phe X 2-Phe-CH 2 CH 2-Phe-Alkyl Nitril-Phe X 2-Phe-CH 2 CH 2-Phe-Alkyl 2 XV a Lkyt-Phe X 2-CO-0-Phe-CO-0-Phe-a Lky L halogeno-Phe X 2-CO-0-Phe-CO-0-Phe-a Lky L halogeno-Phe X 2-CO-0-Phe-O-CO-Phe-alkyl a Ltkyl-Phe X 2-C 0-0 h C-Phe C-Phe-alkyl a Lky L-Phe-CO-0-Phe X 2-0-CO-Phe-a Lkyl ha Logeno-Phe-C 0-0-Phe X 2-0-C 0-Phe-alky L halogeno-Phe-CO-O-Phe X 2-OCO-Cyc-a Lky L alky L-Phe-CO-O-Phe X 2-OCO-Cyc-alkyl g Il halogeno-Phe X 2-OCH 2-Cyc-Cyc-alkyl halogeno-Phe X 2-OCH 2-Cyc-CH 2 CH 2-Cyc-alkyl alkoxy-Phe X 2-OCH 2-Cyc-CH 2 CH 2-Phe-alkyl alkoxy-Phe X 2-OCH 2 Phe-CH 2 CH 2-Phe-alkyl alkoxy-Phe X 2-OCH 2-Phe-CO-0 O-Phe-alkyl alkoxy-Phe X 2-OCH 2-Cyc-CO-O-Phe-alkyl alkoxy-Phe X 2-OCH 2-Cyc-CH 2 CH 2-Cyc-alkyl The compounds of the formula I are prepared by methods which are known per se, such as are described in the literature (for example in the standard works, such as Houben-Weyl, Methoden der Organischen Chemie (Methods of Organic Chemistry), Georg-Thieme-Verlag, Stuttgart), and in particular under reaction conditions which are known and suitable for the reactions mentioned In these reactions, it is also possible to utilize variants which are known per se but are not mentioned here in more detail.
If desired, the starting substances can also be formed in situ such that they are not isolated from the reaction mixture but are immediately reacted further to give the compounds of the formula I.
Compounds of the formula I wherein one of the groups A, A or A is 2,3-difluoro-1,4-phenylene are accessible starting from 1,2-difluoro-benzene.
This is metallized by known processes (for example A M Roe et al, J Chem Soc Chem Comm, 22, 582 ( 1965)) and the product is reacted with the corres- ponding electrophile This reaction sequence can be carried out a second time on the 1-substituted 2,3-di- fluorobenzene thus obtained and 1,4-disubstituted 2,3-di- fluorobenzene derivatives of the formula I are in this way obtained The 1,2-difluorobenzene or 1-substituted 2,3-difluorobenzene is reacted with phenyllithium, lithiumtetramethylpiperidine or n-, sec or tert -butyl- lithium in an inert solvent, such as diethyl ether, tetrahydrofuran, dimethoxyethane, tert -butyl methyl ether or dioxane, hydrocarbons, such as hexane, heptane, cyclohexane, benzene or toluene, or mixtures of these 22 solvents, if appropriate with the addition of a complex- ing agent, such as tetramethylethylenediamine or hexa- methylphosphoric acid triamide, at temperatures of -100 C to + 50 C, preferably -78 C to O C.
The lithium-2,3-difluorophenyl compounds are reacted with the corresponding electrophiles at -100 C to O C, preferably at -50 C Suitable electrophiles are aldehydes, ketones, nitriles, epoxides, carboxylic acid derivatives, such as esters, anhydrides or halides, halogenoformic acid esters or carbon dioxide.
For reaction with aliphatic or aromatic halogen compounds, the lithium-2,3-difluorophenyl compounds are transmetallized and the products are coupled under transition metal catalysis The zinc (compare DE OS 36 32 410) or the titanium-2,3-difluorophenyl compounds (compare DE OS 37 36 489) are particularly suitable for this.
The compounds of the formula I can be prepared by reducing a compound which otherwise corresponds to the formula I but contains one or more reducible groups and/ or C-C bonds instead of H atoms.
Preferred possible reducible groups are carbonyl groups, in particular keto groups, and furthermore, for example, free or esterified hydroxyl groups or aromatically bonded halogen atoms Preferred starting substances for the reduction correspond to the formula I, but can contain a cyclohexene ring or cyclohexanone ring instead of a cyclohexane ring and/or a -CH=CH group instead of a -CH 2 CH 2 group and/or a -CO group instead of a -CH 2 group and/or a free or a functionally modified (for example in the form of its p-toluenesulfonate) OH group instead of an H atom.
The reduction can be carried out, for example, by catalytic hydrogenation at temperatures between about 00 and about 200 under pressures between about 1 and bar in an inert solvent, for example an alcohol, such as methanol, ethanol or isopropanol, an ether, such as tetrahydrofuran (THF) or dioxane, an ester, such as ethy L 23 - acetate, a carboxylic acid, such as acetic acid, or a hydrocarbon, such as cyclohexane Catalysts which are advantageously suitable are noble metals, such as Pt or Pd, which can be used in the form of oxides (for example Pt O 2 or Pd O), on a support (for example Pd-on-charcoal, -calcium carbonate or -strontium carbonate) or in finely divided form.
Ketones can also be reduced by the Clemmensen method (using zinc, amalgamated zinc or tin and hydro- chloric acid, advantageously in aqueous-alcoholic solu- tion or in a heterogeneous phase system using water/ toluene at temperatures between about 80 and 120 ) or the Wolff-Kishner method (using hydrazine, advantageously in the presence of an alkali, such as KOH or Na OH, in a high-boiling solvent, such as diethylene glycol or tri- ethylene glycol, at temperatures between about 100 and 2000) to give the corresponding compounds of the formula I containing alkyl groups and/or -CH 2 CH 2- bridges.
Reductions using complex hydrides are furthermore possible For example, arylsulfonyloxy groups can be removed by reduction with Li AIH 4, and in particular p- toluenesulfonyloxymethyl groups can be reduced to methyl groups, advantageously in an inert solvent, such as diethyl ether or THF, at temperatures between about 0 and Double bonds (also in the presence of CN groups) can be hydrogenated with Na BH 4 or tributyltin hydride in methanol.
Esters of the formula I can also be obtained by esterification of corresponding carboxylic acids (or their reactive derivatives) with alcohols or phenols (or their reactive derivatives).
Particularly suitable reactive derivatives of the carboxylic acids mentioned are the acid halides, above all the chlorides and bromides, and furthermore the anhydrides, for example also mixed anhydrides, azides or esters, in particular alkyl esters having 1-4 C atoms in the alkyl group.
a 4- Possible reactive derivatives of the alcohols and phenols mentioned are, in particular, the corresponding metal alcoholates and phenolates, preferably of an alkali metal, such as Na or K.
The esterification is advantageously carried out in the presence of an inert solvent Particularly suit- able solvents are ethers, such as diethyl ether, di-n- butyl ether, THF, dioxane or anisole, ketones, such as acetone, butanone or cyclohexanone, amides, such as DMF or phosphoric acid hexamethyltriamide, hydrocarbons, such as benzene, toluene or xylene, halogenohydrocarbons, such as carbon tetrachloride or tetrachloroethylene, and sulfoxides, such as dimethyl sulfoxide or sulfolane.
Water-immiscible solvents can advantageously be used at the same time for azeotropic removal by distillation of the water formed during the esterification An excess of an organic base, for example pyridine, quinoline or triethylamine, may occasionally also be used as the sol- vent for the esterification The esterification can also be carried out in the absence of a solvent, for example by simply heating the components in the presence of sodium acetate The reaction temperature is usually bet- ween -50 and + 2500, preferably between -20 and + 800.
At these temperatures, the esterification reactions are as a rule ended after 15 minutes to 48 hours.
In detail, the reaction conditions for the esterification largely depend on the nature of the start- ing substances used Thus, a free carboxylic acid is as a rule reacted with a free alcohol or phenol in the pre- sence of a strong acid, for example a mineral acid, such as hydrochloric acid or sulfuric acid A preferred reac- tion procedure is to react an acid anhydride or, in par- ticular, an acid chloride with an alcohol, preferably in a basic medium, bases which are of importance being, in particular, alkali metal hydroxides, such as sodium hydroxide or potassium hydroxide, alkali metal carbonates or bicarbonates, such as sodium carbonate, sodium bi- carbonate, potassium carbonate or potassium bicarbonate, alkal i metal acetates, such as sodium acetate or potas- sium acetate, alkaline earth metal hydroxides, such as calcium hydroxide, or organic bases, such as triethy L- amine, pyridine, lutidine, collidine or quinoline.
Another preferred embodiment of the esterification com- prises a procedure in which the alcohol or phenol is first converted into the sodium or potassium alcoholate or phenolate, for example by treatment with ethanolic sodium hydroxide solution or potassium hydroxide solution, this alcoholate or phenolate is isolated and suspended in acetone or diethyl ether together with sodium bi- carbonate or potassium carbonate, while stirring, and a solution of acid chloride or anhydride in diethyl ether, acetone or DMF is added to this suspension, advantage- ously at temperatures between about -25 and + 20 To prepare nitriles of the formula I (wherein R 2 1 2 3 and/or R are CN and/or wherein A, A and/or A is substituted by at least one CN group), corresponding acid amides, for example those in which the radical X is replaced by a CONH 2 group, can be dehydrated The amides are obtainable, for example, from corresponding esters or acid halides by reaction with ammonia.
Examples of suitable dehydrating agents are inorganic acid chlorides, such as SOCL 2, P C 13, PCL 5, POCL 3, 502 C 12 or COCL 2, and furthermore P 205, P 255, AI C 13 (for example as a double compound with Na Cl), aromatic sulfonic acids and sulfonic acid halides This reaction can be carried out in the presence or absence of an inert solvent at temperatures between about 00 and 1500; possible solvents are, for example, bases, such as pyridine or triethylamine, aromatic hydrocarbons, such as benzene, toluene or xylene, or amides, such as DMF.
To prepare the abovementioned nitriles of the formula I, corresponding acid halides, preferab Ly the chlorides, can also be reacted with sulfamide, advan- tageously in an inert solvent, such as tetramethylenesulfone, at temperatures between about 80 and 150 , preferably at 120 After customary working up, the nitrites can be isolated directly.
Ethers of the formula I (wherein R 1 and/or R 2 is an alkoxy group and/or wherein Z 1 and/or Z 2 is a -OCH 2 or a -CH 2 00 group) are obtainable by etherifi- cation of corresponding hydroxy compounds, preferably corresponding phenols, the hydroxy compound advantage- ously first being converted into the corresponding metal derivative, for example into the corresponding alkali metal alcoholate or alkali metal phenolate by treatment with Na H, Na NH 2, Na OH, KOH, Na 2 CO 3 or K 2 CO 3 This derivative can then be reacted with the corresponding alkyl halide or sulfonate or dialkyl sulfate, advan- tageously in an inert solvent, such as acetone, 1,2-di- methoxyethane, dimethylformamide or dimethyl sulfoxide or an excess of aqueous or aqueous-alcoholic Na OH or KOH, at temperatures between about 200 and 1000.
To prepare nitrites of the formula I (wherein R and/or R 2 is CN and/or wherein A 1, A 2 and/or A 3 is substituted by at least one CN group), corresponding chlorine or bromine compounds of the formula I (wherein R 1 and/or R 2 is Cl or Br and/or wherein A 1, A 2 and/ or A 3 is substituted by at least one Cl or Br atom) can also be reacted with a cyanide, advantageously with a metal cyanide, such as Na CN, KCN or Cu 2 (CN)2, for example in the presence of pyridine, in an inert solvent, such as dimethylformamide or N-methylpyrrolidone, at temperatures between 20 and 200 .
Compounds of the formula I wherein R 1 or R 2 is F, Cl, Br or CN can also be obtained from the corres- ponding diazonium salts by replacement of the diazonium group by a fluorine, chlorine or bromine atom or by a CN group, for example by the methods of Schiemann or Sand- meyer The diazonium salts can be prepared, for example, by nitration of compounds which correspond to the formula I but contain one (or two) hydrogen atom(s) instead of the radicals R 1 and/or R 2, reduction to the corres- ponding amines and diazotization, for example with Na NO 2 27- or KNO 2 in aqueous solution at temperatures between about -10 and + 10 .
To replace the diazonium group by fluorine, the compounds can be diazotized in anhydrous hydrofluoric acid and then heated, or they are reacted with tetrafluo- boric acid to give the diazonium tetrafluoborates, which are then decomposed by heat.
Replacement by Cl, Br or CN is advantageously effected by reaction of the aqueous diazonium salt solu- tion with Cu 2 C 12, Cu 2 Br 2 or Cu 2 (CN)2 by the Sandmeyer method.
Compounds of the formula I wherein R 1 or R 2 is SF 5 can be prepared in accordance with DE-OS 37 21 268.
Isothiocyanates of the formula I wherein R 1 or R 2 is -NCS are prepared in accordance with DE-OS 37 11 510.
The isonitriles of the formula I wherein R 1 or R 2 is -CN are prepared by a method analogous to that in DE-OS 36 33 403.
The tolanes and alkyne compounds (R 1 and/or R 2 is an alkyl group, one or more CH 2 groups being replaced by -CEC-, or z 1 and/or Z 2 = -CEC-) are prepared, for example, by reaction of the corresponding halogen com- pound with an acetylide in a basic solvent under transi- tion metal catalysis; palladium catalysts can preferably be used here, in particular a mixture of bis-(triphenyl- phosphine)palladium(II) chloride and copper iodide in piperidine as the solvent.
The liquid crystal media according to the in- vention preferably contain 2 to 40, in particular 4 to 30, components as other constituents in addition to one or more compounds according to the invention These media especially preferably contain 7 to 25 components in addi- tion to one or more compounds according to the invention.
These other constituents are preferably chosen from the nematic or nematogenic (monotropic or isotropic) substances, in particular substances from the classes of azoxybenzenes, benzylideneanilines, biphenyls, terohenyls, chenyl or cyclohexyl benzoates, phenyl or cyclohexyl cyclohexanecarboxylates, pheny L or cyclohexyl cyclohexylbenzoates, phenyl or cyclohexyl cyclohexanecarboxylates, cyclohexylphenyl benzoates, cyclohexanecarboxylate or cyclohexylcyclohexane- carboxylate, phenylcyclohexanes, cyclohexylbiphenyls, phenylcyclohexylcyclohexanes, cyclohexylcyclohexanes, cyclohexylcyclohexenes, cyclohexylcyclohexylcyclohexenes, 1,4-bis-cyclohexylbenzenes, 4,4 '-bis-cyclohexylbiphenyls, phenyl or cyclohexyl-pyrimidines, phenyl or cyclohexyl- pyridines, phenyl or cyclohexyl-dioxanes, phenyl or cyclohexyl-1,3-dithianes, 1,2-diphenylethanes, 1,2-di- cyclohexylethanes, 1-phenyl-2-cyclohexylethanes, 1-cyclo- hexyl-2-( 4-phenylcyclohexyl)ethanes, 1-cyclohexyl-2-bi- phenylylethanes, 1-pheny 12-cyclohexylphenylethanes, op- tionally halogenated stilbenes, benzyl phenyl ethers, tolanes and substituted cinnamic acids The 1,4-phenyl- ene groups in these compounds can also be fluorinated.
The most important compounds possible as other constituents of the media according to the invention can be characterized by the formulae 1, 2, 3, 4 and 5:
R'-L-E-R" 1 R'-L-COO-E-R" 2 R'-L-OOC-E-R" 3 R'-L-CH 2 CH 2-E-R" 4 R'-L-CEC-E-R" 5 In the formulae 1, 2, 3, 4 and 5, L and E, which can be identical or different, in each case independently of one another are a bivalent radical from the group comprising -Phe-, -Cyc-, -Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-, -Pyr-, -Dio-, -G-Phe and -G-Cyc and mirror images thereof, wherein Phe is 1,4-phenylene which is unsubsti- tuted or substituted by fluorine, Cyc is trans-1,4-cyclo- hexylene or 1,4-cyclohexenylene, Pyr is pyrimidine-2,5- diyl or pyridine-2,5-diyl, Dio is 1,3-dioxane-2,55-diyl and G is 2-(trans-1,4-cyclohexyl)-ethyl, pyrimidine-2,5- diyl, pyridine-2,5-diyl or 1,3-dioxane-2,5-diyl.
Preferably, one of the radicals L and E is Cyc, Phe or Pyr E is preferably Cyc, Phe or Phe-Cyc The media according to the invention preferably contain one or more components chosen from the compounds of the formulae 1, 2, 3, 4 and 5 wherein L and E are chosen from the group comprising Cyc, Phe and Pyr and at the same time one or more components chosen from the compounds of the formulae 1, 2, 3, 4 and 5 wherein one of the radicals L and E is chosen from the group comprising Cyc, Phe and Pyr and the other radical is chosen from the group com- prising -Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-, -G-Phe and -G- Cyc-, and if appropriate one or more components chosen from the compounds of the formulae 1, 2, 3, 4 and 5 wherein the radicals L and E are chosen from the group comprising -Phe-Cyc-, -Cyc-Cyc-, -G-Phe and -G-Cyc-.
R' and R" in the compounds of the part formulae la, 2 a, 3 a, 4 a and 5 a in each case independently of one another are alkyl, alkenyl, alkoxy, alkenyloxy or alkan- oyloxy having up to 8 carbon atoms In most of these compounds, R' and R" differ from one another, one of these radicals usually being alkyl or alkenyl In the compounds of the part formulae lb, 2 b, 3 b, 4 b and Sb, R" is -CN, -CF 3, F, Cl or -NCS; R here has the meaning given in the case of the compounds of the part formulae la to a, and is preferably alkyl or alkenyl However, other variants of the envisaged substituents in the compounds of the formulae 1, 2, 3, 4 and 5 can also be used Many such substances or even mixtures thereof are commercially available All these substances are obtainable by methods which are known from the literature or by analo- gous methods.
The media according to the invention preferably also contain, in addition to components from the group of compounds la, 2 a, 3 a, 4 a and 5 a (group 1), components from the group of compounds lb, 2 b, 3 b, 4 b and 5 b (group 2), the proportions of which are preferably as follows:
Group 1: 20 to 90 %, in particular 30 to 90 %, Group 2: 10 to 80 %, in particular 10 to 50 %, the sum of the proportions of the compounds according to - the invention and the compounds from groups 1 and 2 making up to 100 %.
The media according to the invention preferably contain 1 to 40 %, particularly preferably 5 to 30 %, of compounds according to the invention Media containing more than 40 %, in particular 45 to 90 %, of compounds according to the invention are furthermore preferred.
The media preferably contain three, four or five com- pounds according to the invention.
The media according to the invention are prepared in a manner which is customary per se As a rule, the components are dissolved in one another, advantageously at elevated temperature The liquid crystal phases according to the invention can be modified by suitable additives so that they can be used in all the types of liquid crystal display elements disclosed to date Such additives are known to the expert and are described in detail in the literature (h Kelker/R Hatz, Handbook of Liquid Crystals, Verlag Chemie, Weinheim, 1980) For example, it is possible to add pleochroic dyestuffs to prepare coloured guest-host systems or substances for modifying the dielectric anisotropy, the viscosity and/or the orientation of the nematic phases.
The following examples are intended to illustrate the invention without limiting it mp = melting point, cp = clear point Percentage data above and below are percentages by weight; all the temperatures are stated in degrees Celsius "Customary working up" means: water is added, the mixture is extracted with methylene chlor- ide, the organic phase is separated off, dried and evaporated and the product is purified by crystallization and/or chromatography.
Further abbreviations have the following meanings:
C: crystalline-solid state, S: smectic phase (the index identifies the phase type), N: nematic state, Ch: choles- teric phase, I: isotropic phase The number between two symbols indicates the transition temperature in degrees Celsius.
-.3- Example 1
A mixture of 10 mmol of dicyclohexylcarbodiimide and 1 5 ml of toluene is added to a mixture of 10 mmol of p-pentylbenzoic acid,10 mmol 2,3,4-trifluorophenol (prepared from 1,2,3-trifluorobenzene in accordance with the literature: A M Roe et al, Chem Comm 1965, 582, by metalation with n-butyl Lithium at -50 C analogously to Example 2 and subsequent oxygenation with atmospheric oxygen), 1 mmol of 4-dimethylaminopyridine and 15 0 ml of toluene After the mixture has been stirred at room temperature for 4 hours, 20 mg of oxalic acid are added and the mixture is stirred for a further 30 minutes.
Customary working up gives 2,3,4-trifluorophenyl p-pentyl- benzoate.
Example 2
12.5 ml of a 0 8 molar solution of n-butyllithium in hexane/tetrahydrofuran ( 1:1) are added to a mixture of 10 mmol of 1,2,3-trifluorobenzene and 5 ml of tetra- hydrofuran at -78 C After the reaction mixture has been warmed to -50 C, it is stirred for 7 hours The carboxylic acid obtained after introducing dried, gaseous carbon dioxide, acidification and customary working up is treated with trans-4-pentylcyclohexanol analogously to Example 14 Customary working up gives trans-4-pentyl- cyclohexyl 2,3,4-trifluorobenzoate.
Example 3
A mixture of 10 mmol of 1-( 2,3,4-trifluorophenyl)- 4-propylcyclohex-1-ene (prepared from 2,3,4-trifluoro- phenyllithium and 4-propylcyclohexanone and subsequent dehydration with p-toluenesulfonic acid), 0 1 g of palladium-on-active charcoal ( 1 %) and 15 ml of toluene is hydrogenated to saturation at room temperature After filtration and removal of the solvent, the residue is dissolved in 15 ml of dimethyl sulfoxide, 1 2 g of gotas- sium tert -butanolate are added and the mixture is stirred at room temperature for 2 hours Acidification and customary working up give trans-i-( 2,3,4-tritlioro- nhenyl)-A-props cycloh ?xane.
The following compounds are prepared analogously:
trans-1-( 2,3,4-trifluorophenyl)-4-ethylcyclohexane trans-1-( 2,3,4-trifluorophenyl)-4-butylcyclohexane trans-1-( 2,3,4-trifluorophenyl)-4-pentylcyclohexane trans-1-( 2,3,4-trifluorophenyl)-4-hexylcyclohexane trans-1-( 2,3,4-trifluorophenyl)-4-heptylcyclohexane trans-1-( 2,3,4-trifluorophenyl)-4-octylcyclohexane trans-1-( 4-propyl-2,3-difluorophenyl)-4-ethylcyclohexane trans-1-( 4-propyl-2,3-difluorophenyl)-4-propylcyclohexane trans-1-( 4-propyl-2,3-difluorophenyl)-4-butylcyclohexane trans-1-( 4-propyl-2,3-difluorophenyl)-4-pentylcyclohexane trans-1-( 4-propyl-2,3-difluorophenyl)-4-hexylcyclohexane trans-1-( 4-propyl-2,3-difluorophenyl)-4-heptylcyclohexane trans-1-( 4-propyl-2,3-difluorophenyl)-4-octylcyclohexane trans-1-( 4-pentyl-2,3-difluorophenyl)-4-ethylcyclohexane trans-1-( 4-pentyl-2,3-difluorophenyl)-4-propylcyclohexane trans-1-( 4-pentyl-2,3-difluorophenyl)-4-butylcyclohexane trans-1-( 4-pentyl-2,3-difluorophenyl)-4-pentylcyclohexane trans-1-( 4-pentyl-2,3-difluorophenyl)-4-hexylcyclohexane trans-1-( 4-pentyl-2,3-difluorophenyl)-4-heptylcyclohexane trans-1-( 4-pentyl-2,3-difluorophenyl)-4-octylcyclohexane trans-1-( 4-ethoxy-2,3-difluorophenyl)-4-ethylcyclohexane trans-1-( 4-ethoxy-2,3-difluorophenyl)-4-propylcyclohexane trans-1-( 4-ethoxy-2,3-difluorophenyl)-4-butylcyclohexane trans-1-( 4-ethoxy-2,3-difluorophenyl)-4-pentylcyclohexane trans-1-( 4-ethoxy-2,3-difluorophenyl)-4-hexylcyclohexane trans-1-( 4-ethoxy-2,3-difluorophenyl)-4-heptylcyclohexane trans-1-( 4-ethoxy-2,3-difluorophenyl)-4-octylcyclohexane trans-1-( 4-octyloxy-2,3-difluorophenyl)-4-ethylcyclo- hexane trans-1-( 4-octyloxy-2,3-difluorophenyl)-4-propylcyclo- hexane trans-1-( 4-octyloxy-2,3-difluorophenyl)-4-butylcyclohex- ane trans-1-( 4-octyloxy-2,3-difluorophenyl)-4-pentylcyclo- h Exane trans-1-( 4-octyloxy-2,3-difluorophenyl)-4 hexylcyclohex- ane trans-1-( 4-octyloxy-2,3-difluorophenyl)-4-heptylcyc Lo- hexane trans-1-( 4-octyloxy-2,3-difluorophenyl)-4-octylcyclohex- ane trans-trans-4 '-( 4-pentyl-2,3-difluorophenyl)-4-ethyl- bicyclohexane trans-trans-4 '-( 4-pentyl-2,3-difluorophenyl)-4-propyl- bicyclohexane trans-trans-4 '-( 4-pentyl-2,3-difluorophenyl)-4-butyl- bicyclohexane trans-trans-4 '-( 4-pentyl-2,3-difluorophenyl)-4-pentyl- bicyclohexane trans-trans-4 '-( 4-penty L-2,3-difluorophenyl)-4-hexyl- bicyclohexane trans-trans-4 '-( 4-penty L-2,3-difluorophenyl)-4-hepty L- bicyclohexane trans-trans-4 '-( 4-pentyl-2,3-difluorophenyl)-4-octyl- bicyclohexane trans-trans-4 '-( 2,3-difluorophenyl)-4-ethylbicyclohexane trans-trans-4 '-( 2,3-difluorophenyl)-4-propylbicyclohexane C 410 SB 810 N 96 40 I trans-trans-4 '-( 2,3-difluorophenyl)-4-butylbicyclohexane trans-trans-4 '-( 2,3-difluorophenyl)-4-pentylbicyclohexane trans-trans-4 '-( 2,3-difluorophenyl)-4-hexylbicyclohexane tran S-trans-4 '-( 2,3-difluorophenyl)-4-heptylbicyclohexane trans-trans-4 '-( 2,3-difluorophenyl)-4-octylbicyclohexane Example 4 a) 4-Ethoxy-2,3-difluorobenzaldehyde ml of a solution of O 2 mol of n-butyllithium in hexane are added to a mixture of 0 2 mol of 2,3-difluorophenetol, 0 2 mol of tetramethylethylenediamine and 400 ml of tetrahydrofuran at -78 C and the mixture is stirred at -60 C for 2 hours A mixture of 0 2 mol of N-formylpiperidine and 20 ml of tetrahydrofuran is added dropwise to this mixture After warming to -20 C and customary working up, the aldehyde is obtained as a colourless solid, mp 70 C.
34- b) 4-Ethoxy-2,3-difluorobenzonitrile A mixture of 0 12 mol of hydroxylamine-0-sulfonic acid and 50 ml of water is added to a mixture of 0 1 mol of 4-ethoxy-2,3-difluorobenzaldehyde and 100 ml of water at 30 C and the mixture is stirred for 1 hour After heating at 65 C for 2 hours and customary working up, the nitrile is obtained as a colourless solid, mp 45 O C.
c) 2,3-Difluoro-4-cyanophenol A mixture of 0 1 mol of 4-ethoxy-2,3-difluoro- benzonitrile, 0 12 mol of aluminium chloride and 150 ml of toluene is heated at the boiling point for 2 hours.
Customary working up gives the phenol as a colourless solid, mp 145 C.
Example 5
A mixture of 0 11 mol of dicyclohexylcarbodiimide and 20 ml of toluene is added to a mixture of 0 1 mol of p-pentylbenzoic acid, 0 1 mol of 2,3-difluoro-4-cyano- phenol (prepared according to Example 4), 1 5 g of 4- N,N-dimethylaminopyridine and 200 ml of toluene After the mixture has been stirred at room temperature for 4 hours, 0 4 g of oxalic acid is added and stirring is continued for a further 30 minutes Customary working up gives 4-( 4-pentylbenzoyloxy)-2,3-difluorobenzonitrile, mp 33 C.
The following compounds are prepared analogously:
4-( 4-ethylbenzoyloxy)-2,3-difluorobenzonitrile 4-( 4-propylbenzoyloxy)-2,3-difluorobenzonitrile 4-( 4-butylbenzoyloxy)-2,3-difluorobenzonitrile 4-( 4-hexylbenzoyloxy)-2,3-difluorobenzonitrile 4-( 4-heptylbenzoyloxy)-2,3-difluorobenzonitrile 4-( 4-octylbenzoyloxy)-2,3-difluorobenzonitrile 4-(4-(trans-4-ethylcyclohexyl)-benzoyloxy)-2,3-difluoro- benzonitrile 4-( 4-(trans-4-propylcyclohexyl)-benzoyloxy)-2,3-difluoro- benzonitrile, C 98 N 105 9 I 4-( 4-(trans-4-butylcyclohexyl)-benzoyloxy)-Z,3-difluorobenzonitrile 4-( 4-(trans-4-pentylcyclohexyl)-benzoyloxy)-2,3-difluorobenzonitrile 4-( 4-(trans-4-hexylcyclohexyl)-benzoyloxy)-2,3-difluorobenzonitrile 4-( 4-(trans-4-heptylcyclohexyl)-benzoyloxy)-2,3-difluorobenzonitrile 4-( 4-(trans-4-octylcyclohexyl)-benzoyloxy)-2,3-difluorobenzonitrile Example 6
A mixture of 0 1 mol of trans-4-octylcyclohexane- carbonyl chloride (prepared from the carboxylic acid with oxalyl chloride in toluene) and 75 ml of methylene chloride is added to a mixture of 0 1 mol of 2,3-difluoro-4-cyanophenol (prepared according to Example 4), 0.12 mol of pyridine, 10 mmol of 4-N,N-dimethylamino- pyridine and 250 ml of methylene chloride After the mixture has been stirred at room temperature for 10 hours, it is washed with dilute hydrochloric acid, saturated sodium bicarbonate solution and water Cus- tomary working up gives 4-(trans-4-octylcyclohexanecar- bonyloxy)-2,3-difluorobenzonitrile.
Example 7 a) 1-( 4-Pentylcyclohex-1-enyl)-2,3-difluorobenzene A solution of 0 525 mol of n-butyllithium in 320 ml of hexane is added to a mixture of 0 5 mol of 1,2- difluorobenzene, 1,000 ml of tetrahydrofuran and 0 5 mo Lt of tetramethylethylenediamine at -78 C After the mix- ture has been stirred at -60 C for 3 hours, 0 525 mol of 4-pentylcyclohexanone dissolved in 100 ml of tetra- hydrofuran is added dropwise and the mixture is allowed to warm slowly to room temperature The alcohol obtained after neutralization is dissolved, without purification, in 250 ml of toluene and heated with 2 g of p-toluene- sulfonic acid for 3 hours using a water separator Cus- tomary working up gives 1-( 4-pentylcyclohex-1-enyl)-2,3diftuorobenzene of boiling point 123 C/0 5 mm Hg.
b) 4-( 4-Pentylcyclohex-1-enyl)-2,3-difluorobenzaldehyde 0.12 mol of N-formylpiperidine in 20 ml of tetra- hydrofuran is added to 0 1 mol of 4-( 4-pentylcyclohex-i- _ 2 S - enyl)-2,3-difluorophenyllithium (prepared from the ben- zene with n-butyllithium in tetrahydrofuran/tetramethylethylenediamine analogously to Example 7 a)) at -70 C and the mixture is warmed to -20 C in the course of 1 hour Acidification and customary working up give the aldehyde.
c) 4-( 4-Pentylcyclohex-1-enyl)-2,3-difluorobenzonitrile A mixture of 0 12 mol of hydroxylamine-O-sulfonic acid and 50 ml of water is added to a mixture of 0 1 mol of the aldehyde and 100 ml of water at 30 C After the mixture has been stirred at room temperature for 1 hour, it is heated at 65 C for 2 hours Cooling and custom- ary working up give the nitrile as a white solid.
d) Oxidation with 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) 0.2 mo L of DDQ is added to a mixture of 0 1 mol of the cyclohexene derivative from Example 7 c) and ml of toluene and the mixture is heated at the boil- ing point for 2 hours Cooling and customary working up give 4-pentyl-4 '-cyano-2 ',3 '-difluorobiphenyl.
The following compounds are prepared analogously:
4-ethyl-4 '-cyano-2 ',3 '-difluorobiphenyl 4-propyl-4 '-cyano-2 ',3 '-difluorobiphenyl 4-butyl-4 '-cyano-2 ',3 '-difluorobiphenyl 4-hexyl-4 '-cyano-2 ',3 '-difluorobiphenyl 4-heptyl-4 '-cyano-2 ',3 '-difluorobiphenyl 4-octyl-4 '-cyano-2 ',3 '-difluorobiphenyl 4-(trans-4-ethylcyclohexyl)-4 '-cyano-2 ',3 '-difluoro- biphenyl 4-(trans-4-propylcyclohexyl)-4 '-cyano-2 ',3 '-difluoro- biphenyl 4-(trans-4-butylcyclohexyl)-4 '-cyano-2 ',3 '-difluoro- biphenyl 4-(trans-4-pentylcyclohexyl)-4 '-cyano-2 ',3 '-difluoro- biphenyl, C 84 N 1680 I 4-(trans-4-hexylcyclohexyl)-4 '-cyano-2 ',3 '-difluoro- biphenyl 4-(trans-4-hertylcyclohexyl)-4 '-cyano-2 ',3 '-difluoro biphenyl 4-(trans-4-octylcyclohexyl)-4 '-cyano-2 ',3 '-difluoro- biphenyl Example 8 a) 1-( 2,3-Difluorophenyl)-2-(trans-4-pentylcyclohexyl)- ethane A solution of 0 21 moat of n-butyllithium in ml of hexane is added to a mixture of 0 25 mol of 1,2-difluorobenzene, 0 20 mol of potassium tert -butan- olate and 200 ml of tetrahydrofuran at -100 C After the mixture has been stirred for 10 minutes, a mixture of 0.2 mol of 2-(trans-4-pentylcyclohexyl)-ethyl iodide, 0.2 mol of dimethylaminepropyleneurea and 50 ml of tetra- hydrofuran is added at -90 'C After the mixture has been stirred at -40 C for 1 hour, customary working up gives the ethane derivative of boiling point 135 C/0 5 mm Hg, in addition to a little 1,4-di-( 2-trans-4-pentylcyclohexyt)-ethyl)-2,3-difluorobenzene as a by-product, of C 64 C N 106 70 I.
b) 4-( 2-(Trans-4-pentylcyclohexyl)-ethyl)-2,3-difluoro- benzonitrile.
0.1 mot of the ethane derivative are deprotonated in accordance with Example 7 a), formylated in accordance with Example 7 b) and reacted with 0 12 mo Lt of hydroxyl- amine-0-sulfonic acid in accordance with Example 7 c).
Customary working up gives the nitrite as a colourless solid, C 13 N 28 5 I.
Example 9
0.1 moat of 2,3-difluoro-4-ethoxyphenot (which can be prepared from 2,3-difluorophenol by alkylation with diethyl sulfate/potassium carbonate in dimethylformamide, lithiation at -70 to -80 , reaction with N-methylpiperidine and oxidation of the aldehyde by the Baeyer- Viliger method with performic acid) and 0 1 mol of pyri- dine are dissolved in 100 ml of toluene O 1 mot of trans-4-pentylcyclohexanecarbonyl chloride is added drop- wise at 800 and the mixture is subsequently stirred for 3 hours The: ri e hydrochloride which h S Drec 'ita- _ _ __ B_ ted is filtered off with suction, the toluene is dis- tilled off and the 2,3-difluoro-4-ethoxyphenyl trans-4- pentylcyclohexanoate which remains is purified by crys- tallization from ethanol, C 48 N 62 5 I.
The following compounds are prepared analogously:
2,3-difluoro-4-ethoxyphenyl trans-4-propylcyclohexanoate, mp 50 C 520 2,3-difluoro-4-propoxyphenyl trans-4-propylcyclohexanoate 2,3-difluoro-4-butoxyphenyl trans-4-propylcyclohexanoate 2,3-difluoro-4-pentyloxyphenyl trans-4-propylcyclohexan- oate 2,3-difluoro-4-hexyloxyphenyl trans-4-propylcyclohexan- oate 2,3-difluoro-4-heptyloxyphenyl trans-4-propylcyclohexan- oate 2,3-difluoro-4-octyloxyphenyl trans-4-propylcyclohexan- oate 2,3-difluoro-4-propoxyphenyl trans-4-pentylcyclohexanoate 2,3-difluoro-4-butoxyphenyl trans-4-pentylcyclohexanoate 2,3-difluoro-4-pentyloxyphenyl trans-4-pentylcyclohexan- oate 2,3-difluoro-4-hexyloxyphenyl trans-4-pentylcyclohexan- oate 2,3-difluoro-4-heptyloxyphenyl trans-4-pentylcyclohexan- oate 2,3-difluoro-4-octyloxyphenyl trans-4-pentylcyclohexan- oate Example 10
2,3-Difluoro-4-ethoxyphenyl trans-4-(trans-4propylcyclohexyl)-cyclohexanoate is obtained analogously to Example 9 from the same phenol by reaction with 4(trans-4-propylcyclohexyl)-cyclohexanecarbonyl chloride, C 69 30 SC 146 9 SA 152 7 N 156 I.
The following compounds are prepared analogously:
2,3-difluoro-4-propoxyphenyl trans-4-(trans-4-propylcyclohexyl)-cyclohexanoate 2,3-difluoro-4-butoxyphenyl trans-4-(trans-4-propyl- cyc Lohexy L)-cyc Lohexanoate SI?2,3-difluoro-4-pentyloxyphenyl trans-4-(trans-4-propylcyclohexyl)-cyclohexanoate 2,3-difluoro-4-hexyloxyphenyl trans-4-(trans-4-propyl- cyclohexyl)-cyclohexanoate 2,3-difluoro-4-heptyloxyphenyl trans-4-(trans-4-propylcyclohexyl)-cyclohexanoate 2,3-difluoro-4-octyloxyphenyl trans-4-(trans-4-propyl- cyclohexyl)-cyclohexanoate 2,3-difluoro-4-ethylphenyl trans-4-(trans-4-propy Lcyclohexyl)-cyclohexanoate 2,3-difluoro-4-propylphenyl trans-4-(trans-4-propyl- cyclohexyl)-cyclohexanoate 2,3-difluoro-4-butylphenyl trans-4-(trans-4-propylcyclohexyl)-cyclohexanoate 2,3-difluoro-4-pentylphenyl trans-4-(trans-4-propyl- cyclohexyl)-cyclohexanoate, C 500 SB 98 SA 1150 N 178 7 I 2,3-difluoro-4-hexylphenyl trans-4-(trans-4-propylcyclohexyl)-cyclohexanoate 2,3-difluoro-4-heptylphenyl trans-4-(trans-4-propyl- cyclohexyl)-cyclohexanoate 2,3-difluoro-4-octylphenyl trans-4-(trans-4-propylcyclohexyl)-cyclohexanoate 2,3-difluoro-4-ethoxyphenyl trans-4-butylcyclohexanoate, C 49 N ( 48 2 ) I 2,3-difluoro-4-octyloxyphenyl trans-4-pentylcyclo- hexanoate, C 59 SA ( 55 ) I 2,3-difluoro-4-octyloxyphenyl trans-4-heptylcyclo- hexanoate, C 53 N 65 7 I 2,3-difluoro-4-ethoxyphenyl trans-4-(trans-4-butylcyclohexyl)-cyclohexanoate 2,3-difluoro-4-ethoxyphenyl trans-4-(trans-4-penty L- cyclohexyl)-cyclohexanoate 2,3-difluoro-4-ethoxyphenyl trans-4-(trans-4-hexylcyclohexyl)-cyclohexanoate 2,3-difluoro-4-ethoxyphenyl trans-4-(trans-4-heptyl- cyclohexyl)-cyclohexanoate 2,3-difluoro-4-ethoxyphenyl trans-4-(trans-4-octylcyclohexyl)-cyclohexanoate Example 11
0.1 mo Lt of 4-hexyloxybenzoic acid, 0 01 mo Lt of dimethylaminopyridine and 0 1 mol of 2,3-difluoro-4-octyl- oxyphenol (which can be prepared from 2,3-difluorooctyl- oxybenzene by lithiation at -70 to -80 and dropwise addition of a solution, prepared from 0 12 mol of t- butyl hydroperoxide and 0 12 mol of butyllithium, of lithium t-butyl peroxide in ether) are initially intro- duced into 150 ml of methylene chloride, a solution of 0.1 mo L of dicyclohexylcarbodiimide in 30 ml of methylene chloride is added dropwise at 10 , while stirring, and the mixture is then subsequently stirred at room tempera- ture for 15 hours The mixture is filtered over silica gel and the solvent is evaporated off to give 2,3-difluoro-4-octyloxyphenyl 4-hexyloxybenzoate as the residue.
The following compounds are prepared analogously:
2,3-difluoro-4-octyloxyphenyl p-( 4-heptyloxy-3-fluoro- phenyl)-benzoate, C 69 3 SC 146 9 SA 152 7 N 156 I 2,3-difluoro-4-octy Loxyphenyl p-( 4-octyloxy-3-fluoro- phenyl)-benzoate 2,3-difluoro-4-octyloxyphenyl p-( 4-nonyloxy-3-fluoro- phenyl)-benzoate, C 71 7 SC 146 SA 149 8 N 150 2 I 2,3-difluoro-4-octyloxyphenyl phenyl)-benzoate 2,3-difluoro-4-nonyloxyphenyl phenyl)-benzoate 2,3-difluoro-4-nonyloxyphenyl phenyl)-benzoate 2,3-difluoro-4-nonyloxyphenyl phenyl)-benzoate 2,3-difluoro-4-nonyloxyphenyl phenyl)-benzoate 2,3-difluoro-4-decyloxyphenyl phenyl)-benzoate 2,3-difluoro-4-decyloxy Dheny L p-( 4-decyloxy-3-fluoro- p-( 4-heptyloxy-3-fluoro- p-( 4-octyloxy-3-fluoro- p-( 4-nonyloxy-3-fluoro- p-( 4-decyloxy-3-fluoro- p-( 4-hep: oxy-3-fluoro- p-( 4-octyloxy-3-f Luoro- phenyl)-benzoate 2,3-difluoro-4-decyloxyphenyl p-( 4-nonyloxy-3-fluoro- phenyl)-benzoate 2,3-difluoro-4-decyloxyphenyl p-( 4-decyloxy-3-f Luoro- phenyl)-benzoate 4-heptyloxy-2,3-difluorophenyl p-hexylbenzoate 4-heptyloxy-2,3-difluorophenyl p-heptylbenzoate 4-heptyloxy-2,3-difluorophenyl p-octylbenzoate, mp 43 5 4-heptyloxy-2,3-difluorophenyl p-nonylbenzoate 4-heptyloxy-2,3-difluorophenyl p-decylbenzoate 4-heptyloxy-2,3-difluoropheny L p-hexyloxybenzoate 4-heptyloxy-2,3-difluorophenyl p-heptyloxybenzoate 4-heptyloxy-2,3-difluorophenyl p-octyloxybenzoate, C 530 (Sc 39 ) N 570 I 2,3-difluoro-4-heptyloxyphenyl p-( 4-hexyl-3-fluorophenyl)- benzoate 2,3-difluoro-4-heptyloxyphenyl p-( 4-heptyl-3-fluoro- phenyl)-benzoate 2,3-difluoro-4-heptyloxyphenyl p-( 4-octyl-3-fluorophenyl)- benzoate, C 60 Sc 150 SA 155 N 157 I 2,3-difluoro-4-heptyloxyphenyl p-( 4-hexylphenyl)-benzoate 2,3-difluoro-4-heptyloxyphenyl p-( 4-heptylphenyl)-benzoate 2,3-difluoro-4-heptyloxyphenyl p-( 4-octylphenyl)-benzoate, C 86 Sc 125 SA 131 N 145 I 2,3-difluoro-4-heptyloxyphenyl p-( 4-hexyloxypheny L)- benzoate 2,3-difluoro-4-heptyloxyphenyl p-( 4-heptyloxyphenyl)- benzoate 2,3-difluoro-4-heptyloxyphenyl p-( 4-octyloxyphenyl)- benzoate, C 94 Sc 157 SA 166 N 174 I 4-octyloxy-2,3-difluorophenyl p-hexylbenzoate 4-octyloxy-2,3-difluorophenyl p-heptylbenzoate 4-octyloxy-2,3-difluorophenyl p-octylbenzoate 4-octyloxy-2,3-difluorophenyl p-nonylbenzoate 4-octyloxy-2,3-difluorophenyl p-hexyloxybenzoate 4-octyloxy-2,3-difluorophenyl p-heptyloxybenzoate 4-octyloxy-2,3-difluorophenyl p-octyloxybenzoate, C 510 Sc ( 39 ) N 59 8 I 4-octyloxy-2,3-difluorophenyl p-nonyloxybenzoate, C 53 6 SC ( 49 ) N 59 3 I 4-octyloxy-2,3-difluorophenyl trans-4-pentylcyclohexylcarboxylate, C 30 N 60 I 4-octyloxy-2,3-difluorophenyl trans,trans-4 '-pentyl-bi- cyclohexyl-4-carboxylate, C 58 SC ( 38 ) SA 167 N 182 5 I 4-oct/loxy-2,3-difluoropheny L 4-(trans-4-pentylcyclohexyl)-benzoate, C 62 SC 63 SA 100 N 152 2 I 4-heptyloxy-2,3-difluorophenyl p-octyloxybenzoate, C 53 N 57 I 4-heptyloxy-2,3-difluorophenyl p-octylbenzoate, C 43 5 I Example 12
0 1 mol of 2,3-difluoro-4-butoxyphenol, 0 11 mol of trans-4-pentylcyclohexylmethyl bromide and 0 11 mol of potassium carbonate are heated at 100 in 100 ml of dimethylformamide (DMF) for 16 hours After cooling, the inorganic salts are filtered off with suction, the filtrate is concentrated and water is added Extraction with methylene chloride gives 1-butoxy-2,3-difluoro-4(trans-4-pentylcyclohexylmethoxy)benzene.
The following compounds are prepared analogously:
1-ethoxy-2,3-difluoro-4-(trans-4-pentylcyclohexyl- methoxy)-benzene, C 38 I 1-propoxy-2,3-difluoro-4-(trans-4-pentylcyclohexyl- methoxy)-benzene 1-pentyloxy-2,3-difluoro-4-(trans-4-pentylcyclohexyl- methoxy)-benzene 1-hexyloxy-2,3-difluoro-4-(trans-4-pentylcyclohexyl- methoxy)-benzene 1-heptyloxy-2,3-difluoro-4-(trans-4-pentylcyclohexyl- methoxy)-benzene 1-octyloxy-2,3-difluoro-4-(trans-4-pentylcyclohexyl- methoxy)-benzene 1-ethyl-2,3-difluoro-4-(trans-4-pentylcyclohexyl- methoxy)-benzene 1-propyl-2,3-difluoro-4-(trans-4-pentylcyclohexyl- methoxy)-benzene 1-butyl-2,3-difluoro-4-(trans-4-pentylcyclohexyl- methoxy)-benzene 1-pentyl-2,3-difluoro-4-(trans-4-pentylcyclohexyl- methoxy)-benzene 1-hexyl-2,3-difluoro-4-(trans-4-pentylcyclohexyl- methoxy)-benzene 1-heptyl-2,3-difluoro-4-(trans-4-pentylcyclohexyl- methoxy)-benzene 1-octyl-2,3-difluoro-4-(trans-4-pentylcyclohexyl- methoxy)-benzene 1-ethyl-2,3-difluoro-4-(trans,trans-4 '-propylbicyclohexyl-4-ylmethoxy)-benzene 1-propyl-2,3-difluoro-4-(trans,trans-4 '-propylbicyclo- hexyl-4-ylmethoxy)-benzene 1-butyl-2,3-difluoro-4-(trans,trans-4 '-propylbicyclohexyl-4-ylmethoxy)-benzene 1-pentyl-2,3-difluoro-4-(trans,trans-4 '-propylbicyclo- hexyl-4-ylmethoxy)-benzene, C 36 SA 66 N 117 1 I 1-hexyl-2,3-difluoro-4-(trans,trans-4 '-propylbicyclohexyl-4-ylmethoxy)-benzene 1-heptyl-2,3-difluoro-4-(trans,trans-4 '-propylbicyclo- hexyl-4-ylmethoxy)-benzene 1-octyl-2,3-difluoro-4-(trans,trans-4 '-propylbicyclohexyl-4-ylmethoxy)-benzene 1,2,3-trifluoro-4-(trans-4-(trans-4-propylcyclohexyl)cyclohexylmethoxy)-benzene, C 68 N 105 2 I 1,2,3-trifluoro-4-(trans-4-(trans-4-ethylcyclohexyl)cyclohexylmethoxy)-benzene 1,2,3-trifluoro-4-(trans-4-(trans-4-butylcyclohexyl)cyclohexylmethoxy)-benzene 1,2,3-trifluoro-4-(trans-4-(trans-4-pentylcyclohexyl)cyclohexylmethoxy)-benzene, C 81 N 111 5 I 1,2,3-trifluoro-4-(trans-4-(trans-4-hexylcyclohexyl)cyclohexylmethoxy)-benzene 1,2,3-trifluoro-4-(trans-4-(trans-4-heptylcyclohexyl)cyclohexylmethoxy)-benzene 1,2,3-trifluoro-4-(trans-4-(trans-4-octylcyclohexyl)cyclohexylmethoxy)-benzene 44- Example 13
0.05 mo L of 2,3-difluorohydroquinone and 0 1 mol of pyridine are dissolved in 100 ml of toluene 0 1 mol of trans-4-butylcyclohexanecarbonyl chloride is added dropwise at 80 and the mixture is subsequently stirred for 3 hours Customary working up gives 2,3-difluoro1,4-bis-(trans-4-butylcyclohexanoyloxy)-benzene.
The following compounds are prepared analogously:
2,3-difluoro-1,4-bis-(trans-4-ethylcyclohexanoyloxy)- benzene 2,3-difluoro-1,4-bis-(trans-4-propylcyclohexanoyloxy)- benzene 2,3-difluoro-1,4-bis-(trans-4-pentylcyclohexanoyloxy)- benzene, C 87 N 208 I 2,3-difluoro-1,4-bis-(trans-4-hexylcyclohexanoyloxy)- benzene 2,3-difluoro-1,4-bis-(trans-4-heptylcyclohexanoyloxy)- benzene 2,3-difluoro-1,4-bis-(trans-4-octylcyclohexanoyloxy)- benzene, C 80 SC 123 N 177 I Example 14
0.1 mol of 2,3-difluoro-4-ethoxybenzoic acid (which can be prepared from 2,3-difluorophenol by alkyla- tion with diethyl sulfate/potassium carbonate in dimethyl- formamide, metalation of the 2,3-difluorophenetol in the 4-position with butyllithium/tetramethylethylenediamine in tetrahydrofuran at -70 to -80 and reaction with solid carbonic acid), 0 01 mot of 4-dimethylaminopyridine and 0.1 mol of 2-pentyl-5-hydroxypyridine are initially introduced into 150 ml of methylene chloride, a solution of 0 1 mol of dicyclohexylcarbodiimide in 30 ml of methylene chloride is added dropwise at 10 , while stirring, and the mixture is then subsequently stirred at room temperature for 15 hours The mixture is filtered with suction over silica gel to give, after customary working up, 5-( 2-pentylpyridyl) 2,3-di-fluoro4-ethoxybenzoate.
The following compounds are prepared analogously 2-( 5-octy Lpyridyl) 2,3-difluoro-4-heptyloxybenzoate 2-( 5-nonylpyrimidyl)2,3-difluoro-4-nonyloxybenzoate 2-( 5-( 2-(trans-4-heptylcyclohexyl)-ethyl)-pyrimidyl)2,3difluoro-4-octyloxybenzoate, C 73 SC 115 N 1340 I Example 15
Lithiation of o-difluorobenzene at -70 to -800 and reaction with propionaldehyde, dehydration of the secondary alcohol formed and subsequent hydrogenation of the double bond gives 2,3-difluoropropylbenzene Renewed metalation and reaction with dry ice gives 2,3-di- fluoro-4-propylbenzoic acid 4-( 5-Heptylpyrimidin-2-yl)phenyl 2,3-difluoro-4-propylbenzoate is obtained from this acid analogously to Example 1 by esterification with 2-( 4-hydroxyphenyl)-5-heptylpyrimidine and dicyclohexyl- carbodiimide, C 69 N 1380 I.
The following compound is prepared analogously:
4-( 5-heptylpyrimidin-2-yl)-phenyl 2,3-difluoro-4-octyl- oxybenzoate Example 16
0 1 mol of 2,3-difluoro-4-ethoxybenzoic acid (which can be prepared from 2,3-difluorophenol by alkyla- tion with diethyl sulfate/potassium carbonate in di- methylformamide, metalation of the 2,3-difluorophene- tol in the 4-position using butyllithium/tetramethyl- ethylenediamine in tetrahydrofuran at -70 to -80 and reaction with solid carbonic acid), O 01 mo L of 4-di- methy Laminopyridine and 0 1 mol of 4-hydroxy-4 '-pentylbiphenyl are initially introduced into 150 ml of methyl- ene chloride, a solution of 0 1 mol of dicyclohexylcarbo- diimide in 30 ml of methylene chloride is added dropwise at 10 , while stirring, and the mixture is then subse- quently stirred at room temperature for 15 hours It is filtered with suction over silica gel and the solvent is evaporated to give 4-( 4 '-pentylbiphenylyl) Z,3-difluoro- 4-ethoxybenzoate as the residue, which is purified by crystallization, C 940, N 206 60 I The following compounds are prepared analogously:
trans-4-hexylcyclohexyl 2,3-difluoro-4-( 2-(trans-4- pentylcyclohexy L)-ethyl)-benzoate, C 49 SA 55 N 118 I 4-pentylphenyl 2,3-difluoro-4-( 2-(trans-4-pentylcyclo- hexyl)-ethyl)-benzoate, C 45 SA 92 N 130 3 I 4-propylphenyl 2,3-difluoro-4-( 4-pentylcyclohex-1-enyl)benzoate, C 31 SA 63 N 150 8 I Example 17
4-Pentylphenyl 2,3-difluoro-4-ethoxybenzoate is obtained analogously to Example 16 by reaction of 2,3-di- fluoro-4-ethoxybenzoic acid with 4-pentylphenol, C 610, N ( 50 7 ) I.
The following compounds are prepared analogously:
p-octylphenyl 4-octyloxy-2,3-difluorobenzoate, C 37 SC N 57 1 I 4-(trans-4-pentylcyclohexyl)-phenyl 4-octyloxy-2,3-di- fluorobenzoate, C 58 Sc 96 N 160 8 I trans,trans-4 '-pentylbicyclohex-4-yl 4-octyloxy-2,3difluorobenzoate, C 90 SC 98 N 170 3 I 4-(trans-4-ethylcyclohexyl)-phenyl 4-propyl-2,3-difluoro- benzoate, C 70 N 134 9 I trans,trans-4 '-propylbicyclohexyl-4-yl 4-propyl-2,3-di- f Luorobenzoate, C 64 N 165 2 I ( 4 '-pentylbiphenyl-4-yl) 4-propyl-2,3-difluorobenzoate, C 74 SC 86 N 160 1 I (trans-4-propylcyclohexyl) 4-ethoxy-2,3-difluorobenzoate, C 93 N ( 48) I Example 18
4-( 2,3-Difluoro-4 '-propylbiphenylyl) 2,3-di- fluoro-4-pentylbenzoate is obtained analogously The 4- hydroxy-2,3-difluoro-4 '-propylbiphenyl needed for this is prepared as follows:
2,3-Difluoro-4 '-propylbiphenyl is obtained by lithiation of o-difluorobenzene at -70 to -80 , reaction with 4-propylcyclohexanone, dehydration of the tertiary alcohol and subsequent aromatization of the cyclohexene ring Renewed metalation and reaction with N-formylpiperidine gives 2,3-difluoro-4 '-propylbi- phenyl-4-carbaldehyde The aldehyde is oxidized with 3- 47- chloroperbenzoic acid in methylene chloride in accordance with the Baeyer-Villiger method to give the formate, which is then hydrolyzed under alkaline conditions to give the desired phenol.
Example 19
2,3-Difluorooctylbenzene is obtained by lithia- tion of o-difluorobenzene at -70 to -80 , reaction with octanal, dehydration and hydrogenation Renewed metalation and reaction with N-formylpiperidine to give the aldehyde, oxidation thereof by the Bayer-Villiger method to give the formate and subsequent hydrolysis gives 4-octyl-2,3-difluorophenol.
0.1 mol of the phenol and 0 1 mol of pyridine are dissolved in 100 ml of toluene 0 1 mo L of 4-hexyloxy- benzoyl chloride, dissolved in 50 ml of toluene, is added dropwise at 80 and the mixture is subsequently stirred for 3 hours The pyridine hydrochloride which has pre- cipitated is filtered off with suction, the toluene is distilled off and the 2,3-difluoro-4-octylphenyl 4- hexyloxybenzoate which remains is purified by crystal- lization.
The following compounds are prepared analogously:
2,3-difluoro-4-octylphenyl 4-octyloxybenzoate 2,3 ifluoro-4-decylphenyl 4-octyloxybenzoate 2,3-difluoro-4-pentylphenyl 4-ethoxybenzoate, C 42 N ( 260) I 2,3-difluoro-4-pentylphenyl 4-propoxybenzoate 2,3-difluoro-4-pentylphenyl 4-butoxybenzoate 2,3-difluoro-4-pentylphenyl 4-pentyloxybenzoate 2,3-difluoro-4-pentylphenyl 4-octyloxybenzoate Example 20
0.1 mol of 2-fluoro-4-butyloxybenzoic acid (pre- pared from 3-fluoro-4-cyanophenol by alkylation with butyl bromide/potassium carbonate in dimethylformamide and subsequent hydrolysis of the nitrile via the imido ester), 0 01 mo Lt of dimethylaminopyridine and 0 1 mol of 2,3-difluoro-4-octylphenol are initially introduced into ml of methylene chloride, a solution of 0 1 mol of 4-19 dicyclohexylcarbodiimide in 30 ml of methylene chloride is added dropwise at 100, while stirring, and the mix- ture is then subsequently stirred at room temperature for hours The mixture is filtered over silica gel and the solvent is evaporated to give 2,3-difluoro-4-octyl- phenyl 2-fluoro-4-butyloxybenzoate as the residue.
Example 21
2,3-Difluorooctylbenzene is obtained by lithia- tion of o-difluorobenzene and reaction with octanal, dehydration and hydrogenation, and 4-octyl-2,3-difluoro- phenol is obtained therefrom via the formyl compound in accordance with Example 19.
0.1 mo L of this phenol, 0 1 mo L of trans-4-buty L- cyclohexanecarboxy Lic acid and 0 01 mol of 4-dimethyl- aminopyridine are initially introduced into 150 ml of methylene chloride, a solution of 0 1 mol of dicyclo- hexylcarbodiimide in 30 m L of methylene chloride is added dropwise at 10 , while stirring, and the mixture is then subsequently stirred at room temperature for 15 hours The mixture is filtered over silica gel with suction and the solvent is evaporated off to give Z,3difluoro-4-octylphenyl trans-4-butylcyclohexanoate as the residue.
Example 22
Analogously to Example 20, 2,3-difluoro-4-pentyl- phenol is obtained and is esterified with trans-4-(trans4-pentylcyclohexyl)-cyclohexanecarboxylic acid Custom- ary working up gives 2,3-difluoro-4-pentylphenyl trans4-(trans-4-pentylcyclohexyl)-cyclohexylcarboxylate, C 13 N 28 5 I.
The following compounds are prepared analogously:
2,3-difluoro-4-pentylphenyl trans-4-ethylcyclohexyl- carboxylate 2,3-difluoro-4-pentylpheny L trans-4-propylcyc Lohexyl- carboxy Late 2,3-difluoro-4-pentylphenyl trans-4-butylcyclohexyl- carboxy Late 2,3-dif Luoro-4-pentylphenyl trans-4-hexylcyc Lohexy L- carboxylate 2,3-difluoro-4-pentylphenyl carboxylate 2,3-difluoro-4-pentylphenyl carboxylate 2,3-difluoro-4-pentylphenyl cyclohexyl-4-carboxylate 2,3-difluoro-4-pentylphenyl cyclohexyl-4-carboxylate 2,3-difluoro-4-pentylphenyl cyclohexyl-4-carboxylate 2,3-difluoro-4-penty Lphenyl cyclohexyl-4-carboxylate, S 2,3-difluoro-4-pentylphenyl cyclohexyl-4-carboxylate 2,3-difluoro-4-pentylphenyl cyclohexyl-4-carboxylate 2,3-difluoro-4-pentylphenyl cyclohexyl-4-carboxylate 2,3-difluoro-4-pentylphenyl hexyl)-benzoate 2,3-difluoro-4-pentylphenyl benzoate 2,3-difluoro-4-pentylphenyl benzoate 2,3-difluoro-4-pentylphenyl benzoate, C 74 N 147 I 2,3-difluoro-4-pentylphenyl benzoate 2,3-difluoro-4-pentylphenyl benzoate 2,3-difluoro-4-pentylphenyl benzoate trans-4-heptylcyclohexyltrans-4-octylcyclohexyl- tr ns-trans-4 -ethylbi- trans-trans-4 -propylbitrans-trans-4 -butylbi- trans-trans-4 -pentylbi- A 115 N 180 I trans-trans-4 -hexylbi- trans-trans-4 -heptylbi- trans-trans-4 -octylbitrans-4-(trans-4-ethylcyclo- 4-(trans-4-propylcyclohexyl)- 4-(trans-4-buty Lcyclohexyl)- 4-(trans-4-pentylcyc Lohexyl)- 4-(trans-4-hexylcyclohexyl)4-(trans-4-heptylcyclohexyl)- 4-(trans-4-octylcyclohexyl)- Example 23 ml of a 20 % solution of diisobutylaluminium hydride in hexane are added to a solution of 0 01 mol of 1-hexyne and 5 ml of hexane and the mixture is heated at for 3 hours It is then cooled to 25 , 6 3 ml of a 15 % solution of butyllithium in hexane are added dropwise, after 30 minutes 0 01 mol of 2,3-di- fluoro-4-(trans-4-pentylcyclohexyl)-methoxybenzyl bromide, dissolved in 15 ml of tetrahydrofuran, are added dropwise and the mixture is heated under reflux for 12 hours.
Working up gives 2,3-difluoro-4-(trans-4-pentylcyclohexyl)-methoxy-trans-hept-2-enylbenzene.
The benzyl bromide required is prepared from 2,3difluoro-(trans-4-pentylcyclohexyl)-methoxybenzene by lithiation, reaction with N-formylpiperidine, reduc- tion of the aldehyde with sodium borohydride and reaction of the benzyl alcohol with dibromotriphenylphosphorane.
Example 24
0 2 mol of 1-( 4-ethoxy-2,-3-difluorophenyl)-4(trans-4-n-propylcyclohexylethyl)-cyclohex-1-ene (obtain- able as follows: 131 ml of a 1 6 N solution of butyl- lithium in n-hexane are added dropwise to a solution of 0.2 mol of ethoxy-2,3-difluorobenzene and 0 2 mol of tetramethylethylenediamine in 400 ml of tetrahydrofuran at -70 C, with exclusion of moisture and under a nitro- gen atmosphere The mixture is then stirred at -70 C for 4 hours and 0 11 mol of 4-(trans-4-n-propylcyclo- hexylethyl)-cyclohexanone in 100 ml of THF are subse- quently slowly added The reaction mixture is allowed to warm slowly to room temperature and is hydrolysed with 1.5 l of a saturated ammonium chloride solution The mixture is extracted with ether and the ether phase is washed several times with water, dried and evaporated.
The residue is taken up in 700 ml of ethanol, 70 ml of concentrated HCL are added and the mixture is boiled under reflux for 3 hours 1 5 l of water are then added and the mixture is extracted with methyl tert -butyl ether The ether phase is washed neutral, dried and evaporated and the residue is recrystallized The pro- duct (having a mp of 73 and a cp of 139 ) and 50 g of DDQ are boiled under reflux in 250 ml of toluene for ore hour After cool ing, the reaction mixture is filtered with toluene over sit ic 3 gel, the filtrate is evaporate C and the residue is purified by chromatography 1-(trans- 4-Propylcyclohexyl)-2-( 4 '-ethoxy-2 ',3 '-difluorobiphenyl- 4-yl)-ethane is obtained, C 64 N 144 I.
Example 25
125 ml of a 1 6 N solution of n-8 u Li in hexane are added dropwise to a solution of 0 2 mol of trans-4-npropylcyclohexylethyl-2,3-difluorobenzene (which can be prepared by alkylation of 2,3-difluorobenzene with trans- 4-n-propylcyclohexylethyl iodide at -85 O C in the pre- sence of Bu Li/potassium tert -butylate (t-Bu OK)/1,3- dimethyltetrahydro-2 ( 1 H)-pyrimidinone (DMPU) and 0 2 mol of TMEDA in 400 ml of THF at -70 C), with exclusion of moisture and under a nitrogen atmosphere The mixture is stirred at -70 for 4 hours and 0 2 mol of 4-pentyloxy- cyclohexanone are then added The reaction mixture is allowed to warm to room temperature and is then hydro- lysed with dilute HCL, and the product is isolated in the customary manner The product is taken up in toluene and the mixture is heated at the boil in the presence of p-toluenesulfonic acid, using a water separator.
The toluene phase is then washed neutral with water and dried and 0 4 molof DDQ are added The reaction mixture is brought to the boil When the reaction has ended, the mixture is filtered over a silica gel column and is then worked up in the customary manner The pro- duct is purified by crystallization and chromatography.
1-(trans-4-Propyl)-cyclohexyl)-2-( 4 '-pentyloxy-2,3-difluorobiphenyl-4-yl)-ethane is obtained.
The following compounds are prepared analogously:
1-(trans-4-ethylcyclohexyl)-2-( 4 '-pentyloxy-2,3-difluorobiphenyl-4-yl)-ethane 1-(trans-4-butylcyclohexyl)-2-( 4 '-pentyloxy-2,3-difluoro- biphenyl-4-yl)-ethane 1-(trans-4-pentylcyclohexyl)-2-( 4 '-pentyloxy-2,3-difluorobiphenyl-4-yl)-ethane 1-(trans-4-hexylcyclohexyl)-2-( 4 '-pentyloxy-2,3-difluoro- biphenyl-4-yl)-ethane 1-(trans-4-heptylcyc Lohexyl)-2-( 4 '-pentyloxy-2,3-dif L Uoro- biphenyl-4-yl)-ethane 1-(trans-4-octylcyclohexyl)-2-( 4 '-pentyloxy-2,3-difluorobiphenyl-4-yl)-ethane 1-(trans-4-ethylcyclohexyl)-2-( 4-ethoxy-2,3-difluoro- phenyl)-ethane 1-(trans-4-propylcyclohexyl)-2-( 4-ethoxy-2,3-difluoro- phenyl)-ethane 1-(trans-4-butylcyclohexyt)-2-( 4-ethoxy-2,3-difluoro- phenyl)-ethane 1-(trans-4-pentylcyclohexyl)-2-( 4-ethoxy-2,3-difluoro- phenyl)-ethane, C 49 N ( 20 ) I 1-(trans-4-pentylcyclohexyl)-2-( 4-hexanoyloxy-2,3-difluorophenyl)-ethane, C 45 N ( 26 4 ) I 1-(trans-4-pentylcyclohexyl)-2-( 4-(trans-4-pentylcyclohexylcarbonyloxy)-2,3-difluorophenyl)-ethane, C 580 N 151 8 I 1-(trans-4-pentylcyclohexyl)-2-( 4-( 4-octyloxybenzoyloxy)2,3-difluorophenyl)-ethane, C 51 N 138 I 1-(trans-4-pentylcyclohexyl)-2-( 4-(trans-4-pentylcyclohexylmethoxy)-2,3-difluorophenyl)-ethane, C 76 SA ( 72 ) N 109 4 I 1-(trans-4-pentylcyclohexyl)-2-( 4 '-pentyl-2,3-difluorobiphenyl-4-yl)-ethane, C 22 N 106 7 I 1-( 4-(trans-4-pentylcyclohexyl)-phenyl)-2-( 4-ethoxy-2,3difluorophenyl)-ethane, C 49 SB ( 31 ) N 107 3 I 1-( 4-(trans-4-propylcyclohexyl)-phenyl)-2-( 4-ethoxy-2,3difluorophenyl)-ethane, C 75 N 99 5 I Example 26
0.1 mol of dicyclohexylcarbodiimide (DCC) dis- solved in CH 2 C 12 is added to 0 1 mol of 4 '-pentyl- 2,3-difluorobiphenyl-4-ol (which can be prepared from 4 '- pentyl-2,3-difluoro-4-methoxy-biphenyl by ether cleavage with H Br/glacial acetic acid), O 1 mol of trans-4-npentyl-cyclohexanecarboxylic acid and a catalytic amount of 4-N,N'-dimethylaminopyridine (DMAP) in 300 ml of CH 2 Cl Z 2 at 0 C, with exclusion of moisture The mix- ture is then stirred at room temperature for 12 hours, the dicyclohexylurea which has precipitated is separated off and the product is worked up in the customary manner.
The product is purified by crystallization 4 '-Pentyl-2,3difluorobiphenyl-4-yl trans-4-n-Pentylcyclohexanecarboxyl- ate is obtained, C 440 N 159 1 I.
Example 27
0.1 mol of 4 '-n-pentyl-2,3-difluorobiphenyl-4-ol and 0 1 mol of trans-4-n-pentylcyclohexylmethyl iodide are heated in the presence of 0 12 mol of anhydrous K 2 C 03 in dimethylformamide (DMF) until the mixture boils gently When the reaction has ended, the mixture is worked up in the customary manner and the product is purified by chromatography and crystallization Trans- 4-n-pentylcyclohexylmethyl 4 '-pentyl-2,3-difluorobi- phenyl-4-yl ether is obtained.
Example 28
13.6 g of p-propylphenol and 32 g of 2,3-di- fluoro-4-pentyloxybiphenyl-4 '-carboxylic acid (prepara- tion of 4-pentyloxy-2,3-difluorobiphenyl-4 '-carboxylic acid: pentyloxy-2,3-difluorobenzene is metalated with an equimolar amount of butyllithium and TMEDA under the customary conditions at -70 C in THF, and the reaction mixture is then stirred at -70 C for 4 hours and reacted with an equimolar amount of chlorotriisopropyl orthotitan- ate at the same temperature The reaction mixture is allowed to warm slowly to -30 O C, an equimolar amount of ethyl cyclohexanone-4-carboxylate is then added and the mixture is stirred for 12 hours while warming slowly to room temperature The reaction mixture is hydrolysed with ice-cold dilute hydrochloric acid, stirred briefly-and filtered over celite The filtrate is extrac- ted with MTB ether and the organic phase is dried and evaporated The residue is taken up in ethanol, a little hydrochloric acid is added and the mixture is boiled under reflux for 12 hours After addition of water, the product is isolated in the customary manner and heated at the boiling point together with twice the molar amount of DDQ in toluene The mixture is then worked up in the customary manner and the ester is hydrolysed with a small excess of ethanolic KOH at room temperature The acid is purified by crystallization) are initially introduced into 250 ml of methylene chloride together with a catalytic amount of DMAP, and a solution of 0 1 mol of DCC in methylene chloride is added dropwise at O C The reaction mixture is stirred at room tem- perature for 12 hours, the dicyclohexylurea which has precipitated is then filtered off with suction and the organic phase is worked up in the customary manner.
p-Propylphenyl 4-pentyloxy-2,3-difluorobiphenyl-4 '- carboxylate is obtained.
The following compounds are prepared analogously:
p-hexylphenyl 4-pentyloxy-2,3-difluorobiphenyl-4 '-carboxy- late p-hexylphenyl 4-heptyloxy-2,3-difluorobiphenyl-4 '-carboxy- late p-hexylphenyl 4-octyloxy-2,3-difluorobiphenyl-4 '-carboxy- late p-hexylphenyl 4-nonyloxy-2,3-difluorobiphenyl-4 '-carboxy- late p-heptylphenyl 4-octyloxy-2,3-difluorobiphenyl-4 '-ylcarboxy late p-octylphenyl 4-octyloxy-2,3-difluorobiphenyl-4 '-ylcarboxy- late, C 1 58 6 C 2 63 6 SC 121 SA 139 1 N 144 5 I p-nonylphenyl 4-octyloxy-2,3-difluorobiphenyl-4 '-ylcarboxy- late p-hexyloxyphenyl 4-octyloxy-2,3-difluorobiphenyl-4 '-ylcar- boxylate p-heptyloxyphenyl 4-octyloxy-2,3-difluorobiphenyl-4 '-ylcar- boxylate p-octyloxyphenyl 4-octyloxy-2,3-difluorobiphenyl-4 '-ylcar- boxylate, C 83 8 SC 151 70 SA 154 9 N 165 40 I 4-octyl-2-fluorophenyl 4-octyloxy-2,3-difluorobiphenyl4 '-ylcarboxylate, C 56 7 SC 103 N 141 6 I 4-octy L-3-fluorophenyl 4-octyloxy-2,3-difluorobiphenyl- 4 '-ylcarboxylate, C 45 20 SC 84 3 N 120 70 I 4-heptyl-3-fluorophenyl 4-octyloxy-2,3-difluorobiphenyl- 4 '-ylcarboxylate, C 44 7 Sc ( 41 ) SA 146 I i i - 54-octyloxy-3-fluorophenyl 4-octyloxy-2,3-difluorobiphenyl- 4 '-ylcarboxylate, C 83 6 SC 116 SA 162 9 I Example 29
39 g of 1-( 4-ethoxy-2,3-difluorophenyl)-4-( 4trans-propyl-cyclohexylethyl)cyclohex-1-ene (preparation:
131 ml of a 1 6 N solution of butyllithium (Bu Li) in n- hexane are added dropwise to a solution of 31 6 g of ethoxy-2,3-difluorobenzene and 23 2 g of tetramethyl- ethylenediamine (TMEDA) in 400 ml of tetrahydrofuran (THF) at -70 C, with exclusion of moisture and under a nitrogen atmosphere The mixture is then stirred at -70 C for 4 hours and 50 g of 4-(trans-4-n-propylcyclo- hexylethyl)-cyclohexanone in 100 ml of THF are subse- quently slowly added The reaction mixture is allowed to warm slowly to room temperature and is then hydrolysed with 1 5 l of a saturated ammonium chloride solution.
The mixture is extracted with ether and the ether phase is washed several times with water, dried and evaporated.
The residue is taken up in 700 ml of ethanol, 70 ml of con- centrated HCL are added and the mixture is boiled under reflux for 3 hours 1 5 l of water are then added and the mixture is extracted with methyl tert -butyl ether (MTB ether) The ether phase is washed until neutral, dried and evaporated and the residue is recrystallized) are dissolved in 250 ml of THF and hydrogenated in the presence of 4 g of 5 % Pd-C at 34 C under a hydrogen pressure of 0 5 bar The mixture is then filtered, the solution is evaporated and trans-4-(trans-4-n-propylcyclohexylethyl)-4-(ethoxy-2,3-difluorophenyl)-cyclohexane is isolated chromatographically by crystallization, C 760 SB 79 N 186 I.
The following compounds are prepared analogously:
trans-4-(trans-4-ethylcyclohexylethyl)-( 4-ethoxy-2,3difluorophenyl)-cyclohexane trans-4-(trans-4-butylcyclohexylethyl)-( 4-ethoxy-2,3- difluorophenyl)-cyclohexane trans-4-(trans-4-pentylcyclohexylethyl)-( 4-ethoxy-2,3difluorophenyl)-cyclohexane trans-4-(trans-4-hexylcyclohexylethyl)-( 4-ethoxy-2,3- difluorophenyl)-cyclohexane trans-4-(trans-4-heptylcyclohexylethyl)-( 4-ethoxy-2,3difluorophenyl)-cyclohexane trans-4-(trans-4-octylcyclohexylethyl)-( 4-ethoxy-2,3- difluorophenyl)-cyclohexane trans-4-(trans-4-ethylcyclohexylethyl)-( 4-octyloxy-2,3difluorophenyl)-cyclohexane tr:ns-4-(trans-4-butylcyclohexylethyl)-( 4-octyloxy-2,3- difluorophenyl)-cyclohexane trans-4-(trans-4-pentylcyclohexylethyl)-( 4-octyloxy-2,3difluorophenyl)-cyclohexane trans-4-(trans-4-hexylcyclohexylethyl)-( 4-octyloxy-2,3- difluorophenyl)-cyclohexane trans-4-(trans-4-heptylcyclohexylethyl)-( 4-octyloxy-2,3difluorophenyl)-cyclohexane trans-4-(trans-4-propylcyclohexylethyl)-( 4-octyloxy-2,3- difluorophenyl)-cyclohexane trans-4-(trans-4-octylcyclohexylethyl)-( 4-octyloxy-2,3difluorophenyl)-cyclohexane Example 30
* 0.1 mol of 2,3-difluoro-4-nonyloxybenzamidine hydrochloride (prepared from 2,3-difluoro-4-nonyloxy- benzoyl chloride by conversion into the amide, dehydration thereof to give the nitrite, reaction of the nitrite with ethanol and hydrogen chloride gas and subsequent reaction of the imido ester with ammonia), 0 1 mol of nonylmalonodi- aldehyde tetramethylacetal and 50 ml of DMF are heated at for 12 hours The reaction mixture is then taken up in methylene chloride, washed until neutral with sodium bicarbonate solution and water and dried and the solvent is distilled off 2-( 2,3-Difluoro-4-nonyloxyphenyl)-5- nonylpyrimidine is obtained as the residue and is re- crystallized from ethanol, C 410 SC 54 I.
The following compounds are prepared analogously:
2-( 2,3-difluoro-4-octyloxyphenyl)-5-nonylpyrimidine 2-( 2,3-difluoro-4-heptyloxyphenyl)-5-nonylpyrimidine 2-( 2,3-difluoro-4-hexyloxyphenyl)-5-nonylpyrimidine 2-( 2,3-difluoro 574-pentyloxyphenyl) nonylpyrimidine 2-( 2,3-difluoro-4-penbutyoxyphenyl)-5-nonylpyrimidine 2-( 2,3-difluoro-4-prbutopoxypheny L)-5-nonylpyrimidine 2-( 2,3-difluoro-4-prethopoxyphenyl)-5-nonylpyrimidine 2-( 2,3-difluoro-4-ethoxylphenyl)-5-nonylpyrimidine 2-( 2,3-difluoro-4-ethpropylphenyl)-5-nonylpyrimidine 2-( 2,3-difluoro-4-prbutopylphenyl)-5-nonylpyrimidine 2-( 2,3-difluoro-4-penbutylphenyl)-5-nonylpyrimidine 2-( 2,3-difluoro-4-hexntylphenyl)-5-nonylpyrimidine 2-( 2,3-difluoro-4-heptylphenyl)-5-nonylpyrimidine 2-( 2,3-difluoro-4-hoctylphenyl)-5-nonylpyrimidine 2-( 2,3-dif Luoro-4-octy Lphenyl)-5-nony Lpyrimidine 2-( 2 ',3 '-difluoro-4 '-ethylbiphenyl-4-y L)-5-heptyl- pyr i m id ine 2-( 2 ',3 '-dif Luoro-4 '-propylbiphenyl-4-yl)-5-heptyl- pyrimidine 2-( 2 ',3 '-difluoro-4 '-butylbiphenyl-4-yl)-5-heptyl- pyrimidine 2-( 2 ',3 '-difluoro-4 '-pentylbiphenyl-4-yl)-5-heptyl- pyrimidine 2-( 2 ',3 '-difluoro-4 '-hexylbiphenyl-4-yl)-5-heptyl- pyr imid mine 2-( 2 ',3 '-difluoro-4 '-heptylbiphenyl-4-yl)-5-heptyl- pyr imidine 2-( 2,3 '-difluoro-4 '-octylbiphenyl-4-yl)-5-heptyl- pyrimidine, C 64 SC 90 N 188 I.
Example 31
2,3-Difluoro-4-( 5-butylpyrimidin-2-yl)-4 '-propyl- biphenyl is obtained by reaction of 2,3-difluoro-4 '- propyl-biphenyl-4-carbamidine hydrochloride (the biphenyl- carboxylic acid required for this is obtained analogously to Example 28) with butylmalonodialdehyde tetramethyl- acetal in DMF, after customary working up.
Example 32
A solution of 0 1 mo L of n-Bu Li in hexane is added droowise to a solution of 0 1 mo Lt of 2,3-diftuoro- nonyloxybenzene and 0 1 mol of TMEDA in 200 ml of THF at -60 to -70 C in the course of half an hour, while stir- ring The mixtue is St rred t this temperature ror a further 2 hours and a solution of O 05 mol of Zn Br 2 (anhydrous) in 100 ml of THF is then added dropwise at the same temperature After a further hour, a solution of 0 1 mol of 2-bromo-5-methylpyridine and 2 mo L % ( 0 002 mol) of bis-triphenylphosphinenickel(II) chloride, dissolved in 50 ml of THF, is slowly added and the mix- ture is subsequently stirred for a further 16 hours, during which the temperature is allowed to reach room temperature slowly Water is added and the mixture is worked up by extraction The crude product is purified by recrystallization and chromatography 2-( 2,3-Difluoro-4-nonyloxyphenyl)-5-methylpyridine is obtained.
The following compounds are prepared analogously:
2-( 2,3-difluoro-4-octyloxybiphenyl)-5-methylpyridine 2-( 2,3-difluoro-4-octyloxybiphenyl)-5-ethylpyridine 2-( 2,3-difluoro-4-octyloxybiphenyl)-5-propylpyridine 2-( 2,3-difluoro-4-octyloxybiphenyl)-5-butylpyridine 2-( 2,3-difluoro-4-octyloxybiphenyl)-5-pentylpyridine 2-( 2,3-difluoro-4-octyloxybiphenyl)-5-hexylpyridine 2-( 2,3-difluoro-4-octyloxybiphenyl)-5-heptylpyridine 2-( 2,3-difluoro-4-octyloxybiphenyl)-5-octylpyridine SC 26 N 38 5 I Example 33
0.1 mol of DCC, dissolved in methylene chloride, is added to a mixture of 0 1 mol of 4 '-heptyloxy-2,3-di- fluorobiphenylcarboxylic acid (preparation: 0 1 mol of 2,3-difluoro-4 '-heptyloxybiphenyl and 0 1 mol of TMEDA are dissolved in 200 ml of THF and the solution is cooled to -78 C and reacted with 0 105 mol of a 1 6 N solution of Bu Li in hexane at this temperature The reaction mix- ture is stirred at -78 C for 3 hours and is then poured all at once onto 200 g of crushed dry ice Customary working up gives 4 '-heptyloxy-2,3-difluoro-biphenyl-4- carboxylic acid), 0 1 mol of optically active 2-cyano-2- methylhexan-1-ol (which can be prepared from optically active ethyl 2-methyl-2-butylcyanoacetate by reduction with Li BH 4) and a catalytic amount of 4-N,N'-di- methylaminopyridine (DMAP) in 200 ml of methylene L 513- chloride at O C The mixture is then stirred at room temperature for 12 hours It is worked up in the custom- ary manner and the product is purified by crystallization.
Optically active 2-cyano-2-methylhexyl 4 '-heptyloxy-2,3difluorobiphenyl-4-carboxylate is obtained.
Example 34
0.17 mol of diethyl azodicarboxylate (DEAD), dis- solved in THF, is added to a solution of 0 15 mol of 4 '- heptyloxy-2,3-difluorobiphenyl-4-ol, 0 17 mol of L(-)- ethyl lactate and 0 15 mo L of triphenylphosphine in 400 ml of THF During this addition, the reaction temperature should not exceed 50 C The mixture is stirred at 50 C for 1 hour and then at room temperature overnight.
The solvent is then distilled off, the residue is dis- solved in hot toluene and the solution is subsequently allowed to cool slowly The triphenylphosphine oxide which has precipitated is filtered off with suction, the filtrate is concentrated and the residue is purified by chromatography Ethyl 2-l 4-(p-heptyloxyphenyl)-2,3-difluorophenoxyl-propionate is obtained.
Example 35
A solution of 0 1 mol of DCC in methylene chloride is added to a mixture of 0 1 mol of 4 '-heptyl- oxy-2,3-difluorobiphenyl-4-ol, 0 1 mol of optically active 2-chloro-3-methylbutyric acid (prepared from valine) and a catalytic amount of DMAP in 250 ml of methylene chloride at O C The mixture is then stirred at room temperature for 12 hours, the precipitate is sub- sequently filtered off with suction and the filtrate is worked up in the customary manner to give 4-(p-heptyloxy- phenyl)-2,3-difluorophenyl 2-chloro-3-methylbutyrate.
Example 36
0.0055 mol of 4-octylbicyclol 2,2,2 loctylcarboxyl chloride is added to a mixture of O 0055 mol of 4 '-octyl- oxy-2 ',3 '-difluorobiphenyl-4-ol (prepared by hydrogenoly- tic cleavage of 4 '-octyloxy-2 ',3 '-difluoro-4-benzyloxy- biphenyl, which is obtained by coupling of 4-octy Loxy- 2,3-difluorophenyl diisopropyloxytitanate to p-benzyloxybromobenzene with tetrakis(triphenytphosphine)palladium ( 0) as the catalyst), 20 ml of methylene chloride and 1 ml of triethylamine After the mixture has been stirred S at 20 for 24 hours, customary working up gives 4 '-octyl- oxy-2 ',3 '-dif Luorobiphenyl-4-yl 4-octylbicyclo-l 2,2,2 l- octylcarboxylate, C 57 1 SC 128 5 SA 156 N 177 5.
The following compounds are prepared analogously:
4 '-octyloxy-2 ',3 '-difluorobiphenyl-4-yl trans-4-heptylcyclohexylcarboxylate, C 53 SC 132 8 SA 144 4 N 1620 I 4 '-octyloxy-2 ',3 t-difluoro-4-acetyloxybipheny L 4 '-octyloxy-2 ',3 '-difluoro-4-propionyloxybiphenyl 4 '-octyloxy-2 ',3 '-difluoro-4-butyryloxybiphenyl 4 '-octyloxy-2 ',3 '-difluoro-4-pentanoyloxybiphenyl 4 '-octyloxy-2 ',3 '-difluoro-4-hexanoyloxybiphenyl 4 '-octyloxy-2 ',3 '-difluoro-4-heptanoyloxybiphenyl, C 62 9 I 4 '-octyloxy-2 ',3 '-difluoro-4-octanoyloxybiphenyl, C 54 9 SC 63 O N 66 5 I 4 '-octyloxy-2 ',3 '-difluoro-4-nonanoyloxybiphenyl, C 58 SC 63 10 N 63 50 I 4 '-octyloxy-2 ',3 '-difluoro-4-( 4-methylhexanoyloxy)-bi- phenyl C 38 SC ( 32 5 ) N ( 35 5 ) I 4 '-octyloxy-2 ',3 '-difluoro-4-decanoyloxy, C 51 8 SC 710 I Example 37
A mixture of 0 2 mol of 4-( 4-trans-pentylcyclo- hexyl)-1-( 4-octyloxy-2,3-difluorophenyl)-cyclohex-1-ene (prepared from 4-octyloxy-2,3-difluorophenyllithium and 4-trans-4-pentylcyclohexyl)-cyclohexanone and subsequent dehydration with p-toluenesulfonic acid), 400 ml of toluene and 0 4 mol of DDQ is heated at the boiling point for 2 hours After cooling, 4 '-(trans-4-pentylcyclohexyl)-4-octyloxy-2,3-difluorobiphenyl is obtained, C 530 SC 58 SA 127 N.
The following compounds are prepared analogously:
4 '-(trans-4-pentylcyclohexyl)-4-heptyloxy-2,3-difluoro- biphenyl 61 - 4 '-(trans-4-pentylcyclohexyl)-4-hexyloxy-2,3-difluorobi- phenyl 4 '-(trans-4-pentylcyclohexyl)-4-pentyloxy-2,3-difluoro- biphenyl 4 '-(trans-4-pentylcyclohexyl)-4-butoxy-2,3-difluorobi- phenyl 4 '-(trans-4-pentylcyclohexyl)-4-propoxy-2,3-difluorobi- phenyl 4 '-(trans-4-pentylcyclohexyl)-4-ethoxy-2,3-difluorobi- phenyl 4 '-(trans-4-pentylcyclohexyl)-4-ethyl-2,3-difluorobi- phenyl 4 '-(trans-4-pentylcyclohexyl)-4-propyl-2,3-difluorobi- phenyl 4 '-(trans-4-pentylcyclohexyl)-4-butyl-2,3-difluorobi- phenyl 4 '-(trans-4-pentylcyclohexyl)-4-pentyl-2,3-difluorobi- phenyl 4 '-(trans-4-pentylcyclohexyl)-4-hexyl-2,3-difluorobi- phenyl 4 '-(trans-4-pentylcyclohexyl)-4-heptyl-2,3-difluorobi- phenyl 4 '-(trans-4-pentylcyclohexyl)-4-octyl-2,3-difluorobi- phenyl Example 38
A solution of 0 2 mol of n-butyllithium in 65 ml of hexane is added to a mixture of 0 1 mol of 1,2-di- fluorobenzene, 0 2 mo L of potassium tert -butylate and ml of tetrahydrofuran at -100 C After the mixture has been stirred for 10 minutes, a mixture of 0 2 mo L of 4-propylcyclohexanone and 20 ml of tetrahydrofuran is added at -90 C After the mixture has been stirred at -40 C for 2 hours, it is warmed to room temperature and ml of 2 normal hydrochloric acid solution are added.
Heating for 2 hours and customary working up give 1,4- bis-( 4-propylcyclohex-1-enyl)-2,3-difluorobenzene, C 590 N 120 5 I.
The following compounds are prepared analogously:
61- 1,4-bis-( 4-ethylcyclohex-1-enyl)-2,3-difluorobenzene 1,4-bis-( 4-butylcyclohex-1-enyl)-2,3-difluorobenzene 1,4-bis-( 4-pentylcyclohex-1-enyl)-2,3-difluorobenzene 1,4-bis-( 4-hexylcyclohex-1-enyl)-2,3-difluorobenzene 1,4-bis-( 4-heptylcyclohex-1 l-enyl)-2,3-difluorobenzene 1,4-bis-( 4-octy Lcyc Lohex-1-enyl)-2,3-difluorobenzene Example 39
A mixture of 0 1 mol of (trans-4-pentylcyclo- hexyl)-acetyl chloride and 20 ml of toluene is added to a mixture of 0 1 mol of 4-octyloxy-2,3-difluorophenyl- boric acid (prepared from 4-octyloxy-2,3-difluorophenyl- lithium and triisopropyl borate and subsequent hydrolysis with dilute hydrochloric acid), 0 2 mol of sodium carbon- ate, 0 01 mol of tetrakis-(triphenylphosphine)palladium ( 0) and 150 ml of toluene at O C After the mixture has been stirred at room temperature for 2 hours, customary working up gives 1-( 4-octyloxy-2,3-difluorophenyl)-2- (trans-4-pentylcyclohexyl)-ethan-1-one, C 59 o SA ( 550) I.
The following compounds are prepared analogously:
1-( 1-octyloxy-2,3-difluorophenyl)-2-(trans-4-ethylcyclohexyl)-ethan-1-one 1-( 1-octyloxy-2,3-difluorophenyl)-2-(trans-4-propylcyclohexyl)-ethan-1-one 1-( 1-octyloxy-2,3-difluorophenyl)-2-(trans-4-butyl- cyclohexyl)-ethan-1-one 1-( 1-octyloxy-2,3-difluorophenyl)-2-(trans-4-hexyl- cyclohexyl)-ethan11-one 1-( 1-octyloxy-2,3-difluorophenyl)-2-(trans-4-heptylcyclohexyl)-ethan-1-one 1-( 1-octyloxy-2,3-difluorophenyl)-2-(trans-4-octyl- cyclohexyl)-ethan-1-one 1-( 1-pentyloxy-2,3-difluorophenyl)-2-(trans-4-ethylcyclohexyl)-ethan-1-one 1-( 1-pentyloxy-2,3-difluorophenyl)-2-(trans-4-propyl- cyclohexyl)-ethan-1-one 1-( 1-pentyloxy-2,3-difluorophenyl)-2-(trans-4-butylcyclohexyl)-ethan-1-one 1-( 1-pentyloxy-2,3-difluorophenyl)-2-(trans-4-hexyl- cyclohexyl)-ethan-1-one 1-( 1-pentyloxy-2,3-difluorophenyl)-2-(trans-4-heptylcyclohexyl)-ethan-1-one 1-( 1-pentyloxy-2,3-difluorophenyl)-2-(trans-4-octyl- cyclohexyl)-ethan-1-one Example 40
A mixture of 0 1 mo L of 4-octyloxy-2,3-difluoro- aniline (prepared from the corresponding amide by a Hoffmann rearrangement), 0 1 mol of 4-propylbenzaldehyde, 0 01 mol of p-toluenesulfonic acid and 200 ml of toluene is heated at the boiling point for 2 hours using a water separator Customary working up gives ( 4-octyloxy-2,3difluorophenyl)-4-propylbenzylideneamine.
The following compounds are prepared analogously:
( 4-octyloxy-2,3-difluorophenyl)-4-ethylbenzylideneamine ( 4-octyloxy-2,3-difluorophenyl)-4-butylbenzylideneamine ( 4-octyloxy-2,3-difluorophenyl)-4-pentylbenzylideneamine ( 4-octyloxy-2,3-difluorophenyl)-4-hexylbenzylideneamine ( 4-octyloxy-2,3-difluorophenyl)-4-heptylbenzylideneamine ( 4-octyloxy-2,3-difluorophenyl)-4-octylbenzylideneamine ( 4-pentyloxy-2,3-difluorophenyl)-4-ethylbenzylideneamine ( 4-pentyloxy-2,3-difluorophenyl)-4-propylbenzylidene- amine ( 4-pentyloxy-2,3-difluorophenyl)-4-butylbenzylideneamine ( 4-pentyloxy-2,3-difluorophenyl)-4-pentylbenzylideneamine ( 4-pentyloxy-2,3-difluorophenyl)-4-hexylbenzylideneamine ( 4-pentyloxy-2,3-difluorophenyl)-4-heptylbenzylideneamine ( 4-pentyloxy-2,3-difluorophenyl)-4-octylbenzylideneamine 64- Example 41
66 ml of a 1 6 N solution of butyllithium in n-hexane are added dropwise to a solution of 0 1 mol of 2,3-difluoro- phenetole and 0 1 mol of TMEDA in 200 ml of THF at -70 C.
After stirring for 4 hours at -70 C 0 1 mol of 4-acetyl- 4 '-propylbiphenyle in 50 ml of THF are added After customary working up the product and 2 g of p-toluenesulfonic acid are dissolved in 200 ml of toluene and the mixtung is heated under reflux for 0 5 hours Working up gives 1-( 4-ethoxy- 2,3-difluorphenyl)-l-( 4 '-propylbiphenyl-4-yl)-ethene.
0.065 mol of bromine are added to a stirred solution of 0.065 mol of this ethen derivative in a mixture of 100 ml of dichloromethane and 50 ml of acetonitrile After addition of 10 g of triethylamine and customary working up the crude product is dissolved in 50 ml of THF 0 13 mol of lithium diisopropylamide in 120 ml of THF are added dropwise to this solution at -50 C Customary working up gives 1-( 4-Ethoxy- 2,3-difluorophenyl)-2-( 4 '-propylbiphenyl-4-yl)-ethine.
0.031 mol of this ethine-derivative and 3 g of Pd-C ( 5 %) are suspended in 100 ml of THF and hydrogenated at room- temperature under a hydrogen pressure of 1 bar Customary working up gives 1-( 4-ethoxy-2,3-difluorophenyl)-2-( 4 '- propylbiphenyl-4-yl)-ethane.
The following compounds are prepared analogously:
1-( 4-ethoxy-2,3-difluorophenyl)-2-( 4 '-ethylbiphenyl-4-yl)- ethane 1-( 4-ethoxy-2,3-difluorophenyl)-2-( 4 '-butylbiphenyl-4-yl)- ethane 1-( 4-ethoxy-2,3-difluorophenyl)-2-( 4 '-pentylbiphenyl-4-yl)- ethane PAT LOG 9 100189 1-( 4-ethoxy-2,3-difluorophenyl)-2-( 4 '-hexylbiphenyl-4-yl)ethane 1-( 4-ethoxy-2,3-difluorophenyl)-2-( 4 '-heptylbiphenyl-4-yl)ethane 1-( 4-ethoxy-2,3-difluorophenyl)-2-( 4 '-octylbiphenyl-4-yl)ethane 1-( 4-propyl-2,3-difluorophenyl)-2-( 4 '-ethylbiphenyl-4-yl)ethane 1-( 4-propyl-2,3-difluorophenyl)-2-( 4 '-propylbiphenyl-4-yl)ethane 1-( 4-propyl-2,3-difluorophenyl)-2-( 4 '-butylbiphenyl-4-yl)ethane 1-( 4-propyl-2,3-difluorophenyl)-2-( 4 '-pentylbiphenyl-4-yl)ethane 1-( 4-propyl-2,3-difluorophenyl)-2-( 4 '1-hexylbiphenyl-4-yl)ethane 1-( 4-propyl-2,3-difluorophenyl)-2-( 4 '-heptylbiphenyl-4-yl)ethane 1-( 4-propyl-2,3-difluorophenyl)-2-( 4 '-octylbiphenyl-4-yl)ethane Example 42
A 4-(trans-4-Pentylcyclohexylmethoxy)-2,3-difluorophenyl- boronic acid A solution of n-butyllithium in hexane ( 60 ml, 1 6 mol/1) is added to a mixture of 3-(trans-4- pentylcyclohexylmethoxy)-1,2-difluorobenzene (obtained from 4-trans-pentylcyclohexylmethylbromide and 2,3difluorophenole as example 4), 200 ml of THF and 0.1 mol of TMEDA at -70 C is stirred for 4 hours.
Then a solution of 0 11 mol of trimethylborate in ml THF is added After warming up to room tempera- ture a solution of hydrochloirc acid ( 300 ml, 10 %) is added Customary working up gives the product as a solid.
B 4 '-(trans-4-Pentylclycohexylmethoxy)-2 ',3 ',4-tri- fluorobiphenyle 0.05 mol of the boronic acid ( 42 A) in 100 ml ethanole are coupled with 0 05 ml of p-fluorojodobenzene and with tetrakis (triphenylphosphin)palladium ( 0) as cata- lysator in a mixture of toluene ( 50 ml) and a laqueous solution of sodium carbonate ( 50 ml, 2 mol/1) (V.
Snieckus et al Tetrahedron Letters 28, No 43, 5093-5096, 1987).
The product is obtained as a solid K 85 N 102 I.
The following compounds are prepared analogously:
4 '-(trans-4-ethylcyclohexylmethoxy)-2 ',3 ',4-trifluoro- biphenyle 4 '-(trans-4-propylcyclohexylmethoxy)-2 ',3 ',4-trifluoro- biphenyle 4 '-(trans-4-butylcyclohexylmethoxy)-2 ',3 ',4-trifluoro- biphenyle 4 '-(trans-4-hexylcyclohexylmethoxy)-2 ',3 ',4-trifluoro- biphenyle 4 '-(trans-4-heptylcyclohexylmethoxy)-2 ',3 ',4-trifluoro- biphenyle 4 '-(trans-4-octylcyclohexylmethoxy)-2 ',3 ',4-trifluoro- biphenyle With p-iodo-(trifluoromethoxy)-benzene as starting material are obtained:
4 '-(trans-4-ethylcyclohexylmethoxy)-2 ',3 '-difluoro-4-trifluoromethoxybiphenyle 4 '-(trans-4-propylcyclohexylmethoxy)-2 ',3 '-difluoro-4-tri- fluoromethoxybiphenyle 4 '-(trans-4-butylcyclohexylmethoxy)-2 ',3 '-difluoro-4-trifluoromethoxybiphenyle 4 '-(trans-4-pentylcyclohexylmethoxy)-2 ',3 '-difluoro-4-tri- fluoromethoxybiphenyle, K 52 SA 76 N 108 I 4 '-(trans-4-hexylcyclohexylmethoxy)-2 ',3 '-difluoro-4-trifluoromethoxybiphenyle 4 '-(trans-4-heptylcyclohexylmethoxy)-2 ',3 '-difluoro-4-tri- fluoromethoxybiphenyle 4 '-(trans-4-octylcyclohexylmethoxy)-2 ',3 '-difluoro-4-trifluoromethoxybiphenyle With p-bromo-(trifluoromethyl)-benzene as stating material one obtained:
4 ' -(trans-4-ethylcyclohexylmethoxy)-2 ',3 '-difluoro-4-trifluoromethylbiphenyle 4 ' -(trans-4-propylcyclohexylmethoxy)-2 ',3 '-difluoro-4-tri- fluoromethylbiphenyle 4 ' -(trans-4-butylcyclohexylmethoxy)-2 ',3 '-difluoro-4-trifluoromethylbiphenyle 4 ' -(trans-4-pentylcyclohexylmethoxy)-2 ',3 '-difluoro-4-tri- fluoromethylbiphenyle, K 72 N 90 I 4 ' -(trans-4-hexylcyclohexylmethoxy)-2 ',3 '-difluoro-4-trifluoromethylbiphenyle 4 ' -(trans-4-heptylcyclohexylmethoxy)-2 ',3 '-difluoro-4-tri- fluoromethylbiphenyle 4 '-(trans-4-octylcyclohexylmethoxy)-2 ',3 '-difluoro-4-trifluoromethylbiphenyle 67- Example A
A liquid crystal medium consisting of 8 % of 2-p-heptyloxyphenyl-5-octylpyrimidine, % of 2-p-octyloxyphenyl-5-octylpyrimidine, 14 Z of 2-p-nonyloxyphenyt-5-octylpyrimidine, 3 % of 2-p-hexyloxyphenyl-5-nonylpyrimidine, 23 % of 2-p-nonyloxyphenyl-5-nonylpyrimidine, 7 Z of 2-( 2,3-difluoro-4-nonyloxyphenyl)-5-octylpyrimidine, 9 % of 2-( 2,3-difluoro-4-nonyloxyphenyl)-5-nonylpyrimidine, 8 % of 2-(p-pentyloxyphenyl)-5 S-(p-octylphenyl)-1,3,4- thiadiazole, 8 % of 2-(p-heptyloxyphenyl)-5-(p-octylphenyl)-1,3,4- thiadiazole and % of optically active 4 '-octyloxybiphenyl-4-yl 2-cyano2-methylhexanecarboxylate shows Sc 61 SA 66 Ch 72 I and a spontaneous polariza- tion of 18 n C/cm 2 at room temperature.
Example B
A liquid crystal medium consisting of 4 % of 2-p-octy Loxyphenyl-5-heptylpyrimidine, 4 % of 2-p-nonyloxyphenyl-5-heptylpyrimidine, 7 % of 2-p-hexyloxyphenyl-5-nonylpyrimidine, 12 % of 2-p-heptyloxyphenyl-5-nonylpyrimidine, % of 2-p-nonyloxyphenyl-5-nonylpyrimidine, 8 % of 2-( 2,3-difluoro-4-nonyloxyphenyl)-5-nonylpyrimi- dine, 8 % of 2-( 2,3-dif Luoro-4-octyloxybiphenyl-4 '-yl)-5- heptylpyrimidine, 8 % of r-1-cyano-cis-4-( 4 '-octyloxybiphenyl-4-yl)-1- octylcyclohexane, 7 % of 2-(p-heptyloxyphenyl)-5-(p-pentylphenyl)-1,3,4- thiadiazole, 7 % of2-(p-octyloxyphenyl)-5-(p-heptylphenyl)-1,3,4- thiadiazole and 10 % of chiral ethyl 2-lp-( 5-nonylpyrimidin-2-yl)-phenoxyl- propionate shows Sc 58 SA 64 Ch 75 I and a spontaneous polarization of 10 n C/cm at room temperature.
4 q - Example C
A liquid crystal medium consisting of 12.5 % of 4-heptyloxy-2,3-difluorophenyl 4 '-octyloxy- biphenyl-4-ylcarboxylate 14 2 % of 4-heptyloxy-2,3-difluorophenyl 4-octyloxy- benzoate 12.5 % of 4-heptyl-2-fluorophenyl 4 '-heptyloxybiphenyl-4- ylcarboxylate 12.5 % of 4-heptyl-2-fluorophenyl 4 '-heptyloxy-2 '-fluoro- biphenyl-4-ylcarboxylate 14.2 % of 4-octyloxy-3-fluorophenyl 4-octyloxybenzoate 12.34 % of 4-pentyl-2-fluorophenyl 4-octyloxybenzoate 14.24 % of 4-octyloxy-3-fluorophenyl 4-heptyloxybenzoate 5.04 % of chiral 4-( 2-methylbutyl)-phenyl 4 '-octylbi- phenyl-4-ylcarboxylate and 2.48 % of chiral 1-cyano-2-methylpropyl 4 '-octyloxy- biphenyl-4-ylcarboxylate shows SC 66 4 SA 73 Ch 97 2 I and a spontaneous polarization of 9 n C/cm 2 at 30 C Example D
A liquid crystal medium consisting of 16.87 % of 4-heptyl-2-fluorophenyl 4 '-heptyloxybiphenyl- 4-ylcarboxylate 16.87 % of 4-heptyl-2-fluorophenyl 4 '-heptyloxy-2 '-fluoro- biphenyl-4-ylcarboxylate 16.87 % of 4-octyl-2-fluorophenyl 4 '-octyloxy-2 ',3 '-difluorobiphenyl-4-ylcarboxylate 14 % of 4-octyloxy-3-fluorophenyl 4-octyloxybenzoate 14 % of 4-hexyloxy-3-fluorophenyl 4-octyloxybenzoate 10 % of 4-octyloxy-2-fluorophenyl 4-pentylbenzoate 9 % of 4-heptyl-3-fluorophenyl 4 '-octyloxy-2 ',3 '-difluorobiphenyl-4-ylcarboxylate and 2.4 % of chiral 1-cyano-2-methylpropyl 4 '-octyloxy- biphenyl-4-ylcarboxylate shows SC 71 8 SA 81 Ch 103 8 I and a high spontaneous polarization.
Example E
A liquid crystal medium is formulated containing the following compounds:
13.5 % 21 6 % 32.4 % 22.5 % 10.0 % 4 '-(trans-4-pentylcyclohexyl)-4-cyanobiphenyle, 4 -(trans-4-pro; 1 lcyclohexyl)-benzonitrile, 4 -(trans-4-pentylcyclohexyl)-benzonitrile, 4 -(trans-4-heptylcyclohexyl)-benzonitrile and 4-ethoxy-2,3-difluoro-4 '-trifluoromethoxybiphenyle- This medium exhibits the following physical properties:
clearing point 58 3 C, q ( 20 C) 26 0 mm 2/s As + 13 1, An 0 1358 r,r amA1 11 N i(C Nin N1 iN n -7/-

Claims (12)

Patent Claims
1 A Dihalogenobenzene derivative of the formu La I R 1-A 1-Z 1-A 2-(Z 2-A 3)n-R I wherein R 1 and R 2 E R 3 and R 4 Z 1 and Z 2 A 1, A 2 and A 3 in each case independently of one another are a straight-chain or branched alkyl or perfluoroalkyl group having in each case 1-15 C atoms, it also being possible for one or more CH 2 or CF 2 groups to be replaced by a grouping chosen from the group comprising -0-, -S co, -CO-, -O-CO-, -S-CO-, -O-COO-, -CO-S-, -CO-O-, -E-, -CH- halogeno and -CHCN or a combination of two of these groupings, two hetero atoms not being linked directly, and one of the radicals R 1 and R 2 is also H, F, Cl, Br, CN, COOH, OH, SH, NH 2, NO 2, -NCS, NC or SF 5, 3 4 3 _ is CR 3 = CR 4, CR 3-CR 4 or C=C, \ 0/ in each case independently of one another are H, alkyl having 1-6 C atoms, F, Cl, Br, CF 3 or CN, in each case independently of one another -CO-O-, -O-CO-, -CH 2 CH 2-, -CH 2-O-, -O-CH 2-, -N=CH 2-, -CH 2 =N-, -CH 2-CO-, -CO-CH 2-, -N=N-, -NO=N-, -N=NO-, -CEC or a single bond, in each case independently of one another are a 1,4-phenylene group which is unsub- stituted or substituted by one or more halogen, nitrile and/or alkyl substituents, it also being possible for one or more CH groups to be replaced by N, a 1,4-cyclo- hexylene group, it also being possible for one or two non-adjacent CH 2 groups to be replaced by O and/or S, or a 1,4-cyclohex- enylene group, 1,4-bicyclo( 2,2,2) octylene group, piperidine-1,4-diyl group, naphtha- lene-2,6-diyl group, decahydronaphthalene- 2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group and n is 0, 1, 2 or 3, with the provisos that a) at least one of the rings A A 2 and A 3 is 2,3- dihalogeno-1,4-phenylene and b) if one of the rings A 1, A 2 and A 3 is a 2,3-dichloro- 1,4-phenylene group, Z 1 and Z 2 in each case independently of one another are only -CH 2 CH 2-, -CH 20-, -0-CH 2-, -N=CH 2-, -CH 2 =N-, -CH 2-CO-, -CO-CH 2-, -N=N-, -NO=N-, -N=NO-, -C-C or a single bond, or one of the radicals R 1 and R 2 is only F, Cl, Br, CN, NCS, NC or SF 5, c) if one of the rings A 1, A 2 and A 3 is a 2,3-di- fluoro-1,4-phenylene group and the other rings A 1, A 2 and A 3 are 1,4-phenylene groups, at least one group Z 1 and Z 2 is other than a single bond, or one of the radicals R 1 and R 2 is only F, Cl, Br, CN, NCS, NC or SF 5, and d) if one of the rings A 1, A 2 and A 3 is a 2,3-di- fluoro-1,4-phenylene group, one of the rings A 1, A 2 and A 3 is a 1,4-phenylene group and one of the rings A 1 A 2 and A 3 is a cyclohexylene group, at least one group Z 1 and Z 2 is other than a single bond.
2 A Dihalogenobenzene derivative of the formula I according to Claim 1, characterized in that the group A 3 or A 2 adjacent to the radical R 2 is 2,3-di- halogeno-1,4-phenylene.
3 A Dihalogenobenzene derivative according to Claim 2, characterized in that R 1 is alkyl and R 2 is F.
4 A Dihalogenobenzene derivative according to one of Claims 1 to 3, characterized in that 2,3-dihalogeno-1,4- phenylene is 2,3-difluoro-1,4-phenylene.
A dihalogenobenzene derivative of the formulae Idl, Id 2 and Id 3 R 1 g CH 2 C Hr _Q) -(j) -R 2 Idl- FF F 0 1 d 2 F F F -Rw @ X2 Id 3 Ri (D -CH 2 CH 2 _ _ 2- Rl-Kq -CH 2 CHF 2a D I d 3 wherein R 1 and R 2 have the meaning given in Claim 1.
6 A Dihalogenobenzene derivative of the formulae A, B and C F F _ ( )m@) -CO-O OR 6 A (F)p F F OR B R _COO _ _ _OR 6 B F F RS _ O (D -CO-O (D R 6 C wherein R and R 6 in each case independently of one another are alkyl having 1-15 C atoms and m, p and o are O or 1.
7 Use of the compounds of the formula I as compon- ents of liquid crystal media;
8 A Liquid crysta Lmedium with at least two liquid crystal components, characterized in that at Least one component is a compound of the formulae I, Idl, Id 2, ld 3, A, B or C.
9 A Liquid crystal display element, characterized in that it contains a liquid crystalfl=dium according to Claim 8.
An Electrooptical display element according to Claim 9 characterized in that it contains a liquid crystal medium according to Claim 8 as the dielectric.
11 A dihalogenobenzene derivative substantially as hereinbefore described in examples 1-42.
12 A liquid crystal medium substantially-as hereinbefore described in examples A-E.
Published 1989 at The Patent Office, State House, 68 71 High H Eolbo London W Cl R 4 TP Further copies maybe obtained from The Patent Ofice.
Sales Branch, St Mary Cray, Orpilngton, Kent BR 5 3RD Printed by Multiplex techniques Itd, St Mary Cray, Kent, Con 1/87
GB8905443A 1988-03-10 1989-03-09 Dihalogenobenzene liquid crystalline compounds Expired - Fee Related GB2216523B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE3807908 1988-03-10

Publications (3)

Publication Number Publication Date
GB8905443D0 GB8905443D0 (en) 1989-04-19
GB2216523A true GB2216523A (en) 1989-10-11
GB2216523B GB2216523B (en) 1991-12-11

Family

ID=6349347

Family Applications (1)

Application Number Title Priority Date Filing Date
GB8905443A Expired - Fee Related GB2216523B (en) 1988-03-10 1989-03-09 Dihalogenobenzene liquid crystalline compounds

Country Status (5)

Country Link
JP (1) JPH024725A (en)
CH (1) CH678334A5 (en)
DD (1) DD283641A5 (en)
GB (1) GB2216523B (en)
IT (1) IT1232356B (en)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990008756A1 (en) * 1989-01-27 1990-08-09 MERCK Patent Gesellschaft mit beschränkter Haftung Diphenylethanes
US5171473A (en) * 1989-10-18 1992-12-15 Hoffmann-La Roche Inc. Liquid crystal compounds having a terminal 1-alkynyl residue
US5250220A (en) * 1989-08-12 1993-10-05 Merck Patent Gesellschaft Mit Beschrankter Haftung 2,5-disubstituted heterocyclic compounds, and a liquid-crystalline medium
US5264149A (en) * 1989-10-18 1993-11-23 Hoffmann-La Roche Inc. Liquid crystal compounds having a terminal 1-alkynyl residue
EP0625513A1 (en) * 1993-05-17 1994-11-23 Canon Kabushiki Kaisha Mesomorphic compound, liquid crystal composition containing it, liquid crystal device using the composition, display apparatus and method
GB2310669A (en) * 1996-02-27 1997-09-03 Merck Patent Gmbh Liquid-crystalline medium having positive dielectric anisotropy and an electro-optical liquid-crystal display containing such a medium
US5798058A (en) * 1994-07-01 1998-08-25 Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Gt. Britain & N. Ireland Of Defence Evaluation And Research Agency Liquid crystal compounds, mixtures and devices
EP0982386A1 (en) * 1997-02-24 2000-03-01 Chisso Corporation Liquid crystal compound having negative dielectric anisotropy, liquid crystal composition containing said liquid crystal compound and liquid crystal display device using said composition
WO2001058858A1 (en) * 2000-02-07 2001-08-16 Merck Patent Gmbh Benzoic acid esters, and liquid-crystalline medium
EP1362839A2 (en) * 1998-06-02 2003-11-19 Chisso Corporation Liquid crystal composition having a delta-epsilon- of not less than zero and liquid crystal display device
EP1739151A1 (en) 2005-07-01 2007-01-03 MERCK PATENT GmbH Mesogenic compounds, liquid crystal medium and liquid display
EP1897928A1 (en) * 2006-09-06 2008-03-12 Chisso Corporation Chlorofluorobenzene liquid crystal compound, liquid crystal composition and liquid crystal display device
EP1903090A2 (en) 2006-09-06 2008-03-26 Chisso Corporation Cyclohexene derivative having alkenyl, liquid crystal composition and liquid crystal display device
US8394294B2 (en) 2008-06-09 2013-03-12 Jnc Corporation Four-ring liquid crystal compound having lateral fluorine, liquid crystal composition and liquid crystal display device

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH089565B2 (en) * 1989-07-20 1996-01-31 三洋化成工業株式会社 Liquid crystal compound
JP2977410B2 (en) * 1993-04-26 1999-11-15 シャープ株式会社 Ferroelectric liquid crystal composition and device using the same
US5457551A (en) * 1993-10-08 1995-10-10 Planar Systems, Inc. Frame response compensated, video rate addressable liquid crystal passive matrix display system
EP1043299B1 (en) 1996-04-02 2008-10-15 Chisso Corporation Liquid crystalline compound, liquid crystal composition comprising the liquid crystalline compound, and liquid crystal display device using the liquid crystal composition
TWI319762B (en) 2002-09-27 2010-01-21 1,7,8-trifluoro-2-naphthol and manufacturing methods for liquid crystal compositions containing the same
TWI405841B (en) 2004-12-15 2013-08-21 Dainippon Ink & Chemicals Nematic liquid crystal composition and liquid crystal display element using the same
TWI378139B (en) 2005-01-27 2012-12-01 Dainippon Ink & Chemicals A difluorobenzene derivative and a nematic liquid crystal composition using the same
KR20070112395A (en) * 2005-03-17 2007-11-23 짓쏘 가부시끼가이샤 Liquid crystal composition and liquid crystal display device
CN101142160B (en) 2005-03-17 2011-04-13 大日本油墨化学工业株式会社 Difluorobenzene derivative and liquid crystal composition by using the same
CN101351432B (en) 2006-01-06 2011-08-31 智索株式会社 Monofluorinated terphenyl compound having alkenyl, liquid crystal composition and liquid crystal display element
JP5422898B2 (en) * 2007-03-08 2014-02-19 Ｊｎｃ株式会社 Novel compound having 2,2,2-bicyclooctane bonded to halogenated alkyl group and liquid crystal composition using the same
US8187494B2 (en) * 2007-09-06 2012-05-29 Jnc Corporation Four- or five-ring liquid crystal compound having lateral fluorine, liquid crystal composition, and liquid crystal display device
EP2266941B1 (en) * 2008-04-09 2014-03-05 JNC Corporation Tricyclic liquid crystalline compound having lateral fluorine, liquid crystal composition and liquid crystal display device
EP2272837B1 (en) 2008-05-09 2014-12-17 JNC Corporation Liquid crystalline compound with negative dielectric anisotropy, liquid crystal composition, and liquid crystal display device
JP5526762B2 (en) 2009-02-17 2014-06-18 Ｊｎｃ株式会社 Liquid crystalline compound having negative dielectric anisotropy, liquid crystal composition using the same, and liquid crystal display device
WO2010095506A1 (en) 2009-02-19 2010-08-26 チッソ株式会社 Tetracyclic liquid-crystalline compound having tetrahydropyran and 2,2',3,3'-tetrafluorobiphenyl, liquid-crystal composition, and liquid-crystal display element
WO2011021531A1 (en) 2009-08-18 2011-02-24 ローム株式会社 Input/output device, mobile device, and information displaying device
TWI468381B (en) 2009-08-18 2015-01-11 Jnc Corp Decalin compound, liquid crystal composition containing the same, and liquid crystal display element containing the liquid crystal composition
TWI480363B (en) 2009-08-19 2015-04-11 Jnc Corp Tetrahydropyran compound, liquid crystal composition and liquid crystal display device
US9109157B2 (en) 2009-10-01 2015-08-18 Jnc Corporation Liquid crystal compound having negative dielectric anisotropy, liquid crystal composition and liquid crystal display device using the same
JP6252592B2 (en) 2013-09-19 2017-12-27 Jnc株式会社 Liquid crystalline compound having negative dielectric anisotropy having tetrafluorocyclohexadiene skeleton, liquid crystal composition, and liquid crystal display device
JP6575177B2 (en) * 2014-07-25 2019-09-18 Dic株式会社 Production method by catalytic hydrogen reduction
JP6493678B2 (en) * 2014-07-31 2019-04-03 Jnc株式会社 Liquid crystalline compound, liquid crystal composition and liquid crystal display device

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2063250A (en) * 1979-10-02 1981-06-03 Bdh Chemicals Ltd Liquid crystal esters
EP0064193A1 (en) * 1981-04-30 1982-11-10 MERCK PATENT GmbH 4,4'-Bis-(cyclohexyl)-biphenyl derivatives that contain fluorine, dielectrics containing them, and electro-optical indicator element
WO1985004874A1 (en) * 1984-04-16 1985-11-07 Merck Patent Gmbh Anisotropic compounds and liquid crystal mixtures therewith

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2063250A (en) * 1979-10-02 1981-06-03 Bdh Chemicals Ltd Liquid crystal esters
EP0064193A1 (en) * 1981-04-30 1982-11-10 MERCK PATENT GmbH 4,4'-Bis-(cyclohexyl)-biphenyl derivatives that contain fluorine, dielectrics containing them, and electro-optical indicator element
WO1985004874A1 (en) * 1984-04-16 1985-11-07 Merck Patent Gmbh Anisotropic compounds and liquid crystal mixtures therewith

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5093026A (en) * 1989-01-27 1992-03-03 Merck Patent Gesellschaft Mit Beschrankter Haftung Biphenylylethanes
WO1990008756A1 (en) * 1989-01-27 1990-08-09 MERCK Patent Gesellschaft mit beschränkter Haftung Diphenylethanes
US5250220A (en) * 1989-08-12 1993-10-05 Merck Patent Gesellschaft Mit Beschrankter Haftung 2,5-disubstituted heterocyclic compounds, and a liquid-crystalline medium
US5171473A (en) * 1989-10-18 1992-12-15 Hoffmann-La Roche Inc. Liquid crystal compounds having a terminal 1-alkynyl residue
US5264149A (en) * 1989-10-18 1993-11-23 Hoffmann-La Roche Inc. Liquid crystal compounds having a terminal 1-alkynyl residue
EP0625513A1 (en) * 1993-05-17 1994-11-23 Canon Kabushiki Kaisha Mesomorphic compound, liquid crystal composition containing it, liquid crystal device using the composition, display apparatus and method
US5580488A (en) * 1993-05-17 1996-12-03 Canon Kabushiki Kaisha Mesomorphic compound liquid crystal composition containing the compound, liquid crystal device using the composition, display apparatus and display method
US5798058A (en) * 1994-07-01 1998-08-25 Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Gt. Britain & N. Ireland Of Defence Evaluation And Research Agency Liquid crystal compounds, mixtures and devices
GB2310669B (en) * 1996-02-27 2000-09-27 Merck Patent Gmbh An electrooptical liquid crystal display of the IPS type containing a liquid crystalline medium having positive dielectric anisotropy and such a medium
GB2310669A (en) * 1996-02-27 1997-09-03 Merck Patent Gmbh Liquid-crystalline medium having positive dielectric anisotropy and an electro-optical liquid-crystal display containing such a medium
EP0982386A1 (en) * 1997-02-24 2000-03-01 Chisso Corporation Liquid crystal compound having negative dielectric anisotropy, liquid crystal composition containing said liquid crystal compound and liquid crystal display device using said composition
EP1362839A2 (en) * 1998-06-02 2003-11-19 Chisso Corporation Liquid crystal composition having a delta-epsilon- of not less than zero and liquid crystal display device
EP1362839A3 (en) * 1998-06-02 2006-06-07 Chisso Corporation Liquid crystal composition having a delta-epsilon- of not less than zero and liquid crystal display device
WO2001058858A1 (en) * 2000-02-07 2001-08-16 Merck Patent Gmbh Benzoic acid esters, and liquid-crystalline medium
EP1739151A1 (en) 2005-07-01 2007-01-03 MERCK PATENT GmbH Mesogenic compounds, liquid crystal medium and liquid display
EP1897928A1 (en) * 2006-09-06 2008-03-12 Chisso Corporation Chlorofluorobenzene liquid crystal compound, liquid crystal composition and liquid crystal display device
EP1903090A2 (en) 2006-09-06 2008-03-26 Chisso Corporation Cyclohexene derivative having alkenyl, liquid crystal composition and liquid crystal display device
EP1903090A3 (en) * 2006-09-06 2009-01-07 Chisso Corporation Cyclohexene derivative having alkenyl, liquid crystal composition and liquid crystal display device
US7510749B2 (en) 2006-09-06 2009-03-31 Chisso Corporation Cyclohexene derivative having alkenyl, liquid crystal composition and liquid crystal display device
US7695777B2 (en) 2006-09-06 2010-04-13 Chisson Corporation Chlorofluorobenzene liquid crystal compound, liquid crystal composition and liquid crystal display device
US8394294B2 (en) 2008-06-09 2013-03-12 Jnc Corporation Four-ring liquid crystal compound having lateral fluorine, liquid crystal composition and liquid crystal display device

Also Published As

Publication number Publication date
CH678334A5 (en) 1991-08-30
GB2216523B (en) 1991-12-11
JPH024725A (en) 1990-01-09
DD283641A5 (en) 1990-10-17
GB8905443D0 (en) 1989-04-19
IT8947727A0 (en) 1989-03-09
IT1232356B (en) 1992-01-28

Similar Documents

Publication Publication Date Title
GB2216523A (en) Dihalobenzene liquid crystalline compounds
US5279764A (en) Dihalogenobenzene derivatives
US5064569A (en) Optically active compounds
US4551264A (en) Polyhalogenoaromatic compounds for liquid crystal compositions
JP2787360B2 (en) Difluoromethyl compound
US5211878A (en) Difluorobenzonitrile derivatives
US4846998A (en) Cyclohexane derivatives
US4886620A (en) Smectic liquid-crystalline phases
EP0313604B1 (en) Electro-optical liquid crystal display element
US4925590A (en) Derivatives of 4-cyano-2,3-difluorophenol
JP2567288B2 (en) 2,3-difluorohydroquinone derivative
US5204019A (en) 2,3-difluorobiphenyls
DE3906058C2 (en) 2,3-difluorophenol derivatives and their use
US4897216A (en) 2,3-difluorophenol derivatives
US5454975A (en) Cyanophenylpyri (MI)dine derivatives and liquid-crystalline medium
WO1988009322A1 (en) Cyclobutane derivatives
EP0445248B1 (en) Pyridine derivatives
US5248447A (en) 2,3-difluorohydroquinone derivatives
JPH1112199A (en) Cyclohexane derivative and liquid crystal medium
US5230827A (en) Derivatives of 2,3-difluorobenzoic acid
JPH04210931A (en) Chlorotolan
DE3906019A1 (en) Dihalobenzene derivatives
US5482653A (en) Fluoro-chloro-benzene derivatives
US5204017A (en) Difluorobenzonitriles and liquid-crystalline medium
KR920000415B1 (en) Tolanes

Legal Events

Date Code Title Description
PCNP Patent ceased through non-payment of renewal fee

Effective date: 20030309