GB2266714A - Liquid-crystalline alkoxymethylene compounds - Google Patents

Liquid-crystalline alkoxymethylene compounds Download PDF

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GB2266714A
GB2266714A GB9209709A GB9209709A GB2266714A GB 2266714 A GB2266714 A GB 2266714A GB 9209709 A GB9209709 A GB 9209709A GB 9209709 A GB9209709 A GB 9209709A GB 2266714 A GB2266714 A GB 2266714A
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compounds
ocf3
liquid crystalline
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alkyl
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David Coates
Mark John Goulding
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Merck Patent GmbH
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Merck Patent GmbH
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    • 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
    • C07C255/54—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and etherified 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
    • C07C255/55—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
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/14—Unsaturated ethers
    • C07C43/17—Unsaturated ethers containing halogen
    • C07C43/174—Unsaturated ethers containing halogen containing six-membered aromatic rings
    • C07C43/1747—Unsaturated ethers containing halogen containing six-membered aromatic rings containing six membered aromatic rings and other rings
    • 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
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C69/757—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • 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
    • 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

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  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Novel alkoxymethylene compounds of the Formula I, <IMAGE> [in which R<2> is F, Cl, CF3, OCF3, CN, OCF2H, CH=CF2, an unsubstituted alkyl or alkenyl radical or an alkyl or alkenyl radical substituted by CN, halogen or CF3, in which the radical contains up to 15 C atoms, wherein one or two non-adjacent CH2 groups may be replaced by -O-, -S-, -CO-O- or -O-CO-; R<1> is alkyl or alkenyl with up to 10 C atoms; Z is -CH2CH2-, -CH=CH-, -C IDENTICAL C-, -(CH2)4-, -COO-, -OCO- or -CH=CH-CH2CH2-; r is 0 to 7; and L<1>, L<2> and L<3> are H or F, at least one of L<1> and L<2> being F; with the proviso that when Z = -COO-, one of L<2> and L<3> is F and the other residue is H and L<1> is H, then R<2> is neither F nor Cl] are useful as components of liquid crystalline compositions. <IMAGE>

Description

Alkoxymethylene compounds The invention relates to novel alkoxymethylene compounds of the formula I,
in which R2 is F, Cl, CF3, OCF3, CN, OCF2H, CH=CF2, an unsub stituted alkyl or alkenyl radical or an alkyl or alkenyl radical substituted by CN, halogen or CF3, in which the radical contains up to 15 C atoms, wherein one or two non-adjacent CH2 groups may be replaced by -O-, -S-, -CO-O- or -O-CO-, R1 is alkyl or alkenyl with up to 10 C atoms, Z is -CH2CH2-, -CH=CH-, -(CH2)4-, -COO-, -OCO- or -CH=CH-CH2CH2-, r is 0 to 7, and L1, L2 and L3 are H or F, at least one of L and L2 being F, with the proviso that in the case Z = -COO-, one of L2 and L is F and the other residue is H and L1 is H, R2 is CF3, OCF3, CN, OCF2H, CH=CF2, an unsubstituted alkyl or alkenyl radical or an alkyl or alkenyl radical substituted by CN, halogen or CF3, in which the radical contains up to 15 C atoms, wherein one or two non-adjacent CH2 groups may be replaced by -O-, -S-, -CO-O- or -O-CO-.
The invention furthermore relates to the use of these compounds as components of liquid-crystalline media and to liquid-crystal and electrooptical display elements containing the liquid-crystalline media according to the invention Similar alkoxymethylene compounds are known for use in liquid crystal materials The JP 61-225147A covers compounds of the general formula
wherein a to e is H, F, C1 or Br, but at least one of them is halogen.
The JP 82-169099 and JP 61-207359A disclose fluorobiphenyl cyclohexanecarboxylates of the formula
The invention had the object of finding novel liquid-crystalline compounds which are suitable as components of liquidcrystalline media, in particular for nematic media having positive dielectric anisotropy.
It has been found that the compounds of the formula I are pre-eminently suitable as components of liquid-crystalline media. They can be used, in particular, to obtain liquidcrystalline media having broad nematic ranges, excellent nematogeneity down to low temperatures, excellent chemical stability, excellent elastic properties, a pronounced el with a positive dielectric anisotropy, low temperature dependence of the threshold voltage and/or low optical anisotropy. The novel compounds also exhibit good solubility for other components of media of this type and a high positive dielectric anisotropy at the same time as favourable viscosity. Furthermore, the compounds of the formula I can be used for lowering the viscosity of STN mixtures.
The compounds of the formula I facilitate both STN displays having a short response time and/or a very steep electro-optical characteristic line and displays having an active matrix which have excellent long-term stability.
In the pure state, the compounds of the formula I are colourless and form liquid-crystalline mesophases in a temperature range which is favourably located for electro-optical use.
The invention thus relates to the compounds of the formula I and to the use of the compounds of the formula I as components of liquid-crystalline media, to liquid-crystalline media containing at least one compound of the formula I, and to electro-optical displays which contain media of this type.
A few very particularly preferred smaller groups of compounds are those of the subformulae I1 to 113.
Among these, those of the formulae 11 and I3 are preferred.
The preferred compounds of the formula I1 include those of the partial formula I1a TO I10
The preferred compounds of the formula I3 include those of the partial formulae I3a to I30.
Above and below, R1, R, Z, L, L2, L3 and r are as defined, unless expressly stated otherwise.
Especially preferred are compounds wherein R2 is F, CF3 or OCF3 and/or L1 is F.
If Ri and R2 each are an alkyl radical, these radicals can be straight-chain or branched. Preferably, it is straight-chain and has 2, 3, 4, 5, 6, 7, 8, 9 or 10 C atoms and is accordingly preferably ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl. R2 may also be ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, nonoxy or decyloxy.
Compounds of the formula I with branched terminal groups R1 and R2 can occasionally be of importance because of the improved solubility in the custumary liquid crystal base materials, but in particular as chiral doping substances if they are optically active. Smectic compounds of this type are suitable as components for ferro-electric materials.
Branched groups of this type as a rule do not contain more than one chain branching. Preferred branched chain radicals R1 or R2 are isopropyl, 2-butyl (= l-methylpropyl), isobutyl (= 2-methylpropyl), 2-methylbutyl, isopentyl (= 3-methyl butyl), 2-methylpentyl, 3-methylpentyl, 2-ethylhexyl, 2-propylpentyl and for R1 also isopropoxy, 2-methylpropoxy, 2-methylbutoxy, 3-methylbutoxy, 2-methylpentoxy, 3-methylpentoxy, 2-ethylhexoxy, l-methylhexoxy, l-methylheptoxy, 2-oxa-3-methylbutyl, 3-oxa-4-methylpentyl, 4-methylhexyl, 2-nonyl, 2-decyl, 2-dodecyl, 6-methyloctoxy, 6-methyloctanoyloxy, 2-methylbutyryloxy, 3-methylvaleryloxy, 4-methylhexanoyloxy, 2-methyl-3-oxapentyl, 2-methyl-3-oxahexyl.
Compounds of the formula I wherein the terminal groups R1 and/or R2 are suitable for poly-condensation reactions are useful for the preparation of liquid crystalline polycondensates. Formula I includes both the racemates of these compounds and the optical antipodes, as well as mixtures thereof.
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. Variants which are known per se and are not mentioned in more detail here can also be used in this connection.
If desired, the starting materials 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.
The alkoxymethylene compounds may, for example, be prepared using general routes shown in the reactions schemes 1-2: Scheme 1
L1 L2 OHC eCO2 Et CH30-Br + ( OH ) 2 B XR2 NI KOH, Me3SiI OHC eCO2H ç\/pd A Pd (PPh3)4 NaBH4, r\ Me3SiI | DME, N2 CuSO4 Na2CO3 (aq. ) HOCH2 XCO2H L1 L2 R1- (O-CH2CH2 ) rI/ K2CO3 CH3OXXR2 acetone BBr3 /CHiC12 L3 R1 (O-CH2CH2) r~ CH2 eCO2H $ room temperature L1 L2 HO < -R2 L3 I (CF3CO)10, CH2C12 room temperature L1 L2 R1- (o-CH2CH2 ) rOCH2 Coo4XR2 L3 Scheme 2
KOH NaBH4 OHCYCO2Et 3 OHCCO2H Me3SiI Me3SiI/ CuS04 Ri- (O-CH2CH2) rI/K2CO3 HOCH222tC02H 3 acetone LiAlH4 R1- (O-CH2CH2) rOCH2{}\ Co2H THF rl R1- (O-CH2CH2) rOCH24tCH20H ) toluene KI R1- (O-CH2CH2) rOCH2ecH2OTs acetone PPh3 Ri- (O-CH2CH2) rOCH2OFCH2I CH3CN Wittig Synthesis Ri- (O-CH2CH2) r~OCH2eCH2(3PPh3Io Li OHC H2/Pd/C Ri- (O-CH2CH2) r~OCH2qFCH=CH4 THF
Ll n-BuTi, -70 OC R1- (O-CH2CH2) rOCH2&num;ffHCH2CH2 B (OCH3) 3,H2O2 F (CF3CO)2O Ri- (O-CH2CH2) rOCH2%HCH2CH2&num;OH pyridine, 0 OC L2 (OH) 2B < R2 L1 L3 R1- (O-CH2CH2) rOCH2%jCH2CH2OTf DME, Pd(PPh3)3 LiC1, Na2CO3 (ag.) L1 L2 Ri OCH2 CH2 CH2 L3 The liquid-crystalline media according to the invention preferably contain 2 to 40, in particular 4 to 30, components as further constituents besides one or more compounds according to the invention.These media very particularly preferably contain 7 to 25 components besides one or more compounds according to the invention. These further constituents are preferably selected from nematic or nematogenic (monotropic or isotropic) substances, in particular substances from the classes of the biphenyls, terphenyls, phenyl or cyclohexyl benzoates, phenyl or cyclohexyl esters of cyclohexanecarboxylic acid, phenyl or cyclohexyl esters of cyclohexylbenzoic acid, phenyl or cyclohexyl esters of cyclohexylcyclohexane- carboxylic acid, cyclohexylphenyl esters of benzoic acid, of cyclohexanecarboxylic acid and of cyclohexylcyclohexanecarboxylic acid, phenylcyclohexanes, cyclohexylbiphenyls, phenylcyclohexylcyclohexanes, cyclohexylcyclohexanes, cyclohexylcyclohexenes, cyclohexylcyclohexylcyclohexenes, 1, 4-bis- cyclohexylbenzenes, 4,4'-bis-cyclohexylbiphenyls, phenyl- or cyclohexylpyrimidines, phenyl- or cyclohexylpyridines, phenyl- or cyclohexyldioxanes, phenyl- or cyclohexyl-1,3dithianes, 1,2-diphenylethanes, 1,2-dicyclohexylethanes, l-phenyl-2-cyclohexylethanes, l-cyclohexyl-2- (4-phenylcyclo- hexyl)-ethanes, l-cyclohexyl-2-biphenylylethanes, l-phenyl-2cyclohexylphenylethanes and tolans.
The 1,4-phenylene groups in these compounds may also be fluorinated.
The most important compounds suitable as further constituents of 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-CH2CH2-E-R" 4 R' -L-C=C-E-R" 5 In the formulae 1, 2, 3, 4 and 5, L and E, which may be identical or different, are in each case, independently of one another, a divalent radical from the group formed by -Phe-, -Cyc-, -Phe-Phe, -Phe-Cyc-, -Cyc-Cyc-, -Pyr-, -Dio-, -G-Phe- and -G-Cyc- and their mirror images, where Phe is unsubstituted or fluorine-substituted 1,4-phenylene, Cyc is trans-1,4-cyclohexylene or 1,4-cyclohexenylene, Pyr is pyrimidine-1,5-diyl or pyridine-2,5-diyl, Dio is 1,3-dioxane-2,5diyl and G is 2-(trans-1,4-cyclohexyl)ethyl, pyrimidine-2,5diyl, pyridine-2,5-diyl or 1,3-dioxane-2,5-diyl.
One of the radicals L and E is preferably Cyc, Phe or Pyr. E is preferably Cyc, Phe or Phe-Cyc. The media according to the invention preferably contain one or more components selected from the compounds of the formulae 1, 2, 3, 4 and 5 in which L and E are selected from the group comprising Cyc, Phe and Pyr and simultaneously one or more components selected from the compounds of the formulae 1, 2, 3, 4 and 5 in which one of the radicals L and E is selected from the group comprising Cyc, Phe and Pyr and the other radical is selected from the group comprising -Phe-Phe, -Phe-Cyc-, -Cyc-Cyc-, -G-Phe- and -G-Cyc-, and optionally one or more components selected from the compounds of the formulae 1, 2, 3, 4 and 5 in which the radicals L and E are selected from the group comprising -Phe-Cyc-, -Cyc-Cyc-, -G-Phe- and -G-Cyc-.
In the compounds of the sub-formulae la, 2a, 3a, 4a and 5a, R' and R" are in each case, independently of one another, alkyl, alkenyl, alkoxy, alkenyloxy or alkanoyloxy having up to 8 carbon atoms. In most of these compounds, R' and R" are different from one another, one of these radicals usually being alkyl or alkenyl. In the compounds of the sub-formulae ib, 2b, 3b, 4b and 5b, R" is -CN, -CF3, -OCHF2, -OCF3, F, Cl or -NCS; in this case, R has the meaning given for the compounds of the sub-formulae la to 5a and is preferably alkyl or alkenyl. R" is particularly preferably selected from the group consisting of -F, Cl, CF3, -OCHF2 and -OCF3. However, other variants of the proposed substituents in the compounds of the formulae 1, 2, 3, 4 and 5 are also common.Many such substances or alternatively mixtures thereof are commerically available. All these substances can be obtained by methods which are known from the literature or analogously thereto.
Besides components from the group comprising the compounds la, 2a, 3a, 4a and 5a (Group 1), the media according to the invention also preferably contain components from the group comprising the compounds lb, 2b, 3b, 4b and 5 b (Group 2), whose proportions 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 of the compounds from Groups 1 and 2 adding up to 100 %.
The media according to the invention preferably contain 1 to 40 %, in particular preferably 5 to 30 %, of compounds according to the invention. Further preferred media are those which contain more than 40 %, in particular 45 to 90 %, of compounds according to the invention. The media preferably contain three, four or five compounds according to the inven tion.
The media according to the invention are prepared in a manner which is customary per se. In general, the components are dissolved in one another, expediently at elevated temperature. By means of suitable additives, the liquid-crystalline phases can be modified in accordance with the invention in a manner such that they can be used in all types of liquidcrystal display elements which have hitherto been disclosed.
Additives of this type are known to those skilled in the art and are described in detail in the literature (H. Kelker/R.
Hatz, Handbook of Liquid Crystals, Verlag Chemie, Weinheim, 1980). For example, pleochroic dyes can be added for the production of coloured guest-host systems, or substances can be added to modify the dielectric anisotropy, the viscosity and/or the orientation of the nematic phases.
The examples below are intended to illustrate the invention without representing a limitation. mp. = melting point, cp. = clear point. Above and below, percentages are per cent by weight; all temperatures are indicated in degrees Celsius.
"Customary work-up" means that water is added, the mixture is extracted with methylene chloride, the organic phase is separated off, dried and evaporated, the product is purified by crystallization and/or chromatography.
In addition, the abbreviations have the following meanings: C: crystalline-solid state, S: smectic phase (the index characterizes the phase type), N: nematic state, Ch: cholesteric phase, I: isotropic phase. The number between two symbols indicates the conversion temperature in degrees Celsius.
DAST Diethylaminosulfur trifluoride DCC Dicyclohexylcarbodiimide DDQ Dichlorodicyanobenzoquinone DIBALH Diisobutylaluminium hydride DMSO Dimethyl sulfoxide POT Potassium tertiary-butanolate THF Tetrahydrofuran pTSOH p-Toluenesulfonic acid Example 1 Step 1.1
A solution of 0005 mol 2-fluoro-4-methoxy-1-bromobenzene in ethanol is added dropwise to a stirred mixture of 40 ml 0.05 mol p-4-trifluoromethoxyphenylboronic acid and 1 g tetrakis(triphenylphosphine)palladium(0) in 100 ml DME and 50 ml Na2CO3 at room temperature under dry N2. The stirred mixture is heated under reflux until glc analysis confirmed absence of starting materials.The products is extracted with ether and dried (MgSO4) The solvent is removed and the residue is purified by column chromatography and crystalliza- tion Stes 1.2
BBr3 is added to 0.01 mol 4'-trifluoromethoxy-3'-fluoro-4- methoxybiphenyl dissolved in 30 ml CH2C12. The reaction is stirred at room temperature and after customary work-up the 4'-trifluoromethoxy-3'-fluoro-4-hydroxybiphenyl is obtained.
Sten 1.3
The 4'-trifluoromethoxy-2-fluoro-4-hydroxybiphenyl dissolved in CH2C12 is coupled with 4-(2-oxa-hexyl)cyclohexane acid in the presence of trifluoromethanesulforic anhydride. The reaction mixture is stirred at room temperature. After customary work-up the solvent is removed and the residue is purified by column chromatography and crystallization.
Analogously are obtained the following compounds of the formula
R R L L L C2H5 F F H H C2H5 F H F F C2H5 F F F H C2H5 F F F F C2H5 Cl F H H C2H5 Cl H F H C2H5 Cl F F H %H5 Cl F F F C2H5 CF3 F H H C2H5 CF3 H F H C2H5 CF3 F F H C2H5 CF3 F F F C2H5 OCF3 F H H C2H5 OCF3 H F H C2H5 OCF3 F F H C2H5 OCF3 F F F C2H5 CN F H H C2H5 CN X F H C2H5 CN F F H C2H5 CN F F F C2H5 CH=CF2 F H H n-C3H7 F F H H n-C3H7 F H F F n-C3H7 F F F H n-C3H7 F F F F n-C3H7 Cl F H H R1 R2 L1 L2 L3 n-C3H7 Cl H F H n-C3H7 Cl F F H n-C3H7 Cl F F F n-C3H7 CF3 F H H n-C3H7 CF3 H F H n-C3H7 CF3 F F H n-C3H7 CF3 F F F n-C3H7 OCF3 F H H n-C3H7 OCF3 H F H n-C3H7 OCF3 F F H n-C3H7 OCF3 F F F n-C3H7 CN F H H n-C3H7 CN H F H n-C3H7 CN F F H n-C3H7 CN F F F n-C3H7 CH=CF2 F H H n-C3H7 CH=CF2 H F H n-C3H7 CH=CF2 F F H n-C3H7 CH=CF2 F F F n-C3H7 OCH3 F H H n-C3H7 C2H5 F H H n-C5H11 C2H5 F H H n-C5H11 C3H7 F H H n-C5H11 F F H H n-C5H11 F H F F n-C5H11 F F F H R R L L L n-C5H11 F F F F n-C5H11 Cl F H H n-CsHll Cl H F H n-C5Hll Cl F F H n-C5H11 Cl F F F n-C5H11 CF3 F H H n-C5H11 CF3 H F H n-C5H11 CF3 F F H n-C5H11 CF3 F F F n-C5H11 OCF3 F H H n-C5H11 OCF3 H F H n-C5H11 OCF3 F F H n-C5H11 OCF3 F F F n-C5Hll CN F H H n-C5H11 CN H F H n-C5H11 CN F F H n-C5H11 CN F F F n-C5H11 CH=CF2 F H H n-C7H15 CH=CF2 F H H n-C7H15 F F H H n-C7Hl5 F H F F n-C7H15 F F F H n-C7H15 F F F F n-C7Hl5 Cl F H H n-C7H15 Cl H F H n-C7H15 Cl F F H R R L L L n-C7H15 Cl F F F n-C7H15 CF3 F H H n-C7Hl5 CF3 H F H n-C7Hl5 CF3 F F H n-C7H15 CF3 F F F n-C7H15 OCF3 F H H n-C7H15 OCF3 H F H n-C7H15 OCF3 F F H n-C7H15 OCF3 F F F n-C7H15 CN F H H n-C7Hl5 CN H F H n-C7Hl5 CN F F H n-C7H15 CN F F F n-C7H15 CH=CF2 F H H n-C7H15 CH=CF2 H F H n-C7H15 CH=CF2 F F H n-C7H15 CH=CF2 F F F n-C7H15 n-C7H11 F H H example 2 Stes 2.1
0.013 mol 4'-(2-oxa-pentyl) cyclohexylethyl-4-[3-fluorohydroxybenzene] (prepared as described in scheme 2) is dissolved in 30 ml pyridine. 0.014 mol trifluoromethanesulfonic anhydride is added dropwise at O OC. This reaction mixture is left to stand for 16 hrs. Then the mixture is added to H20 and after customary work-up the triflate is obtained.
SteP 2.2
The triflate is coupled with 3,4-difluorophenylboronic acid in an analogous manner as described in step 1.1.
Analogously are obtained the following compounds of the formula
R1 R2 L1 L2 L3 C2H5 F F H H C2H5 F H F H C2H5 F F F H C2H5 F F F F C2H5 Cl F H H C2H5 Cl H F H C2H Cl F F H C2H5 Cl F F F C2H5 CF3 F H H C2H5 CF3 H F H C2H5 CF3 F F H C2H5 CF3 F F F C2H5 OCF3 F H H C2H5 OCF3 H F H C2H5 OCF3 F F H C2H5 OCF3 F F F C2H5 CN F H H C2H5 CN H F H C2H5 CN F F H C2H5 CN F F F C2H5 CH=CF2 F H H n-C3H7 F F H H n-C3H7 F H F H n-C3H7 F F F H n-C3H7 F F F F R R L L L n-C3H7 Cl F H H n-C3H7 Cl H F H n-C3H7 Cl F F H n-C3H7 Cl F F F n-C3H7 CF3 F H H n-C3H7 CF3 H F H n-C3H7 CF3 F F H n-C3H7 CF3 F F F n-C3H7 OCF3 F H H n-C3H7 OCF3 H F H n-C3H7 OCF3 F F H n-C3H7 OCF3 F F F n-C3H7 CN F H H n-C3H7 CN H F H n-C3H7 CN F F H n-C3H7 CN F F F n-C3H7 CH=CF2 F H H n-C3H7 CH=CF2 H F H n-C3H7 CH=CF2 F F H n-C3H7 CH=CF2 F F F n-C3 H7 OCH3 F H H n-C3H7 C2H5 F H H n-CsHll C2H5 F H H n-C5H11 n-C3H7 F H H n-C5H11 F F H H R R L L n-C5H11 F H F H n-C5H11 F F F H n-C5H11 F F F F n-C5H11 Cl F H H n-C5H11 Cl H F H n-C5H11 Cl F F H n-C5H11 Cl F F F n-C5H11 CF3 F H H n-C5H11 CF3 H F H n-C5H11 CF3 F F H n-C5H11 CF3 F F F n-C5H11 OCF3 F H H n-C5H11 OCF3 H F H n-C5H11 OCF3 F F H n-C5H11 OCF3 F F F n-C5H11 CN F H H n-C5H11 CN H F H n-C5H11 CN F F H n-C5H11 CN F F F n-CsHll CH=CF2 F H H n-C7H15 CH=CF2 F H H n-C7H15 F F H H n-C7H15 F H F H n-C7H15 F F F H n-C7H15 F F F F n-C7H15 Cl F H H R R L L L n-C7H15 Cl H F H n-C7Hl5 Cl F F H n-C7H15 Cl F F F n-C7H15 CF3 F H H n-C7H15 CF3 H F H n-C7H15 CF3 F F H n-C7H15 CF3 F F F n-C7Hl5 OCF3 F H H n-C7H15 OCF3 H F H n-C7H15 OCF3 F F H n-C7H15 OCF3 F F F n-C7H15 CN F H H n-C7Hl5 CN H F H n-C7H15 CN F F H n-C7Hl5 CN F F F n-C7H15 CH=CF2 F H H n-C7Hl5 CH=CF2 H F H n-C7Hl5 CH=CF2 F F H n-C7H15 CH=CF2 F F F n-C7H15 n-C7H11 F H H

Claims (8)

  1. Claims 1. Alkoxymethylene compounds of the formula I,
    in which R2 is F, Cl, CF3, OCF3, CN, OCF2H, CH=CF2, an unsubstituted alkyl or alkenyl radical or an alkyl or alkenyl radical substituted by CN, halogen or CF3, in which the radical contains up to 15 C atoms, wherein one or two non adjacent CH2 groups may be replaced by -O-, -S-, -CO-O- or -O-CO-, R is alkyl or alkenyl with up to 10 C atoms, Z is -CH2CH2-, -CH=CH-, -Cec-, -(CH2)4-, -COO-, -OCO- or -CH=CH-CH2CH2-, r is O to 7, and L1, L2 and L3 are H or F, at least one of L1 and L2 being F, with the proviso that in the case Z = -COO-, one of L2 and L3 is F and the other residue is H and L1 is H, R2 is CF3, OCF3, CN, OCF2H, CH=CF2, an unsubstituted alkyl or alkenyl radical or an alkyl or alkenyl radical subst- tuted by CN, halogen or CF3, in which the radical con tains up to 15 C atoms, wherein one or two non-adjacent CH2 groups may be replaced by -O-, -S-, -CO-O- or -O-CO-.
  2. 2. Derivatives of Claim 1 which are selected from the fol lowing group of alkoxymethylene compounds
  3. 3. Use of the compounds of the formula I as components of liquid crystalline phases.
  4. 4. Liquid crystalline medium containing at least two liquid crystalline components, characterized in that it contains one component of the formula I.
  5. 5. Liquid crystalline composition according to Claim 4 which is a nematic composition.
  6. 6. Liquid crystalline composition according to Claim 4 which is a chiral tilted smectic composition.
  7. 7. Liquid crystalline display element, characterized in that it contains a liquid crystalline medium according to Claim 4.
  8. 8. Electrooptical display element, characterized in that it contains a liquid crystalline phase according to Claim 4.
GB9209709A 1992-05-06 1992-05-06 Alkoxymethylene compounds Expired - Fee Related GB2266714B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996005159A1 (en) * 1994-08-06 1996-02-22 Merck Patent Gmbh Benzene derivatives and liquid crystal medium
EP0728830A2 (en) * 1995-02-22 1996-08-28 Chisso Corporation Liquid crystal composition and liquid crystal display device
EP0761799A1 (en) * 1995-09-11 1997-03-12 Chisso Corporation Liquid crystalline compound substituted with fluorine containing group, liquid crystal composition, and liquid crystal display device
US6013198A (en) * 1995-09-11 2000-01-11 Chisso Corporation Liquid crystalline compound replaced by fluorine containing group, liquid crystal composition, and liquid crystal display device

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996005159A1 (en) * 1994-08-06 1996-02-22 Merck Patent Gmbh Benzene derivatives and liquid crystal medium
EP0728830A2 (en) * 1995-02-22 1996-08-28 Chisso Corporation Liquid crystal composition and liquid crystal display device
EP0728830A3 (en) * 1995-02-22 1996-09-04 Chisso Corp
EP0738709A2 (en) * 1995-02-22 1996-10-23 Chisso Corporation Ester derivate, liquid crystal composition and liquid crystal display element
EP0738709A3 (en) * 1995-02-22 1997-07-16 Chisso Corp Ester derivate, liquid crystal composition and liquid crystal display element
US5755994A (en) * 1995-02-22 1998-05-26 Chisso Corporation Ester derivative, liquid crystal composition and liquid crystal display element
KR100294288B1 (en) * 1995-02-22 2001-09-17 고토 기치 Ester compounds, liquid crystal compositions and liquid crystal display elements containing them
EP0761799A1 (en) * 1995-09-11 1997-03-12 Chisso Corporation Liquid crystalline compound substituted with fluorine containing group, liquid crystal composition, and liquid crystal display device
US6013198A (en) * 1995-09-11 2000-01-11 Chisso Corporation Liquid crystalline compound replaced by fluorine containing group, liquid crystal composition, and liquid crystal display device

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GB2266714B (en) 1995-11-29
GB9209709D0 (en) 1992-06-17

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