CA2033087A1 - Fluorinated cyclohexyl derivatives - Google Patents
Fluorinated cyclohexyl derivativesInfo
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- CA2033087A1 CA2033087A1 CA002033087A CA2033087A CA2033087A1 CA 2033087 A1 CA2033087 A1 CA 2033087A1 CA 002033087 A CA002033087 A CA 002033087A CA 2033087 A CA2033087 A CA 2033087A CA 2033087 A1 CA2033087 A1 CA 2033087A1
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- cyclohexyl
- denotes
- cyc
- formula
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- 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
- C09K19/3028—Cyclohexane rings in which at least two rings are linked by a carbon chain containing carbon to carbon single bonds
-
- 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
- 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
- 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)
- Liquid Crystal Substances (AREA)
Abstract
Abstract The invention relates to fluorinated cyclohexyl derivatives of formula I
I
wherein R1 denotes an alkyl residue with up to 12 carbon atoms wherein one or two non-adjacent CH2-groups may also be replaced by -O-, -O-CO-, -CO-O- and/or -CH=CH-, m is 0 or 1, and X is F, -CF3, -OCF3 or -OCHF2.
I
wherein R1 denotes an alkyl residue with up to 12 carbon atoms wherein one or two non-adjacent CH2-groups may also be replaced by -O-, -O-CO-, -CO-O- and/or -CH=CH-, m is 0 or 1, and X is F, -CF3, -OCF3 or -OCHF2.
Description
-- 2 0 3 ~ O ~ ~
Merck Patent Gesellschaft mit beschrankter ~aftung 6100 D a r m s t a d t Fluorinated Cyclohexyl Derivatives The invention relates to fluorinated cyclohexyl deri-vatives of formula I ~ -F
{ m wherein R1 denotes an alkyl residue with up to 12 carbon atoms wherein one or two non-adjacent CH2-groups may also be replaced by -O-, -O-CO-, -CO-O- and/or -CH=CH-, m is 0 or 1, and X is F, -CF3, -OCF3 or -OCHF2 and also to liquid crystalline media being a mixture of at least 2 compounds, characterized in that at least one compound is a fluorinated cyclohexyl derivative accord-ing to formula I.
The invention was based on the object of discovering new stable liquid crystal or mesogenic compounds which are suitable as components of liquid crystalline media and, in particular, have advantageous values for optical and dielectric anisotropy combined with low viscosity and high nematc~enity.
, ~ ~
:
.~
.,. ~ , .
, ~ , , 20330~7 Similar bicyclohexyl derivatives are described in Euro~
pean Patent 0 125 563: ~ -alkyl- ~ - ~ -CH2CH2- ~ -CN
alkY~ >~CH2CH2~~-F ;
C3H7- ~ ~ ~ -C~2CH2- ~ -CN
F F :;.
C3 ~ - ~ _ ~ -CH2CH2- ~ -CN ~ .
CH3 ~ ;
Similar cyclohexyl derivatives are described in German ~-10 Patent 32 33 641:
alkyl ~ -CH2CH2- ~ - F
These compounds, however, still pose some problems in the mixture development due to the occurrence of disturb-ing smectic phases and to the fact that the strongly p~-lar compounds exhibit high viscosities whereas the lowviscosity compounds have relatively low values for 1, and/or 1. In-addition, the laterally substituted species are not easily accessible.
It has now been found that fluorinated cyclohexyls of formula I are highly suitable as components of liquid crystalline media. In particular, they have especially advantageous values of optical and dielectric anisotropy ~ and ~"). It is also possible to obtain stable liquid crystal phases with a broad nematic mesophase range including a good deep temperature behaviour and a comparatively low viscosity with the aid of ~hese compounds.
~3~87~
Depending on the choice of the substituents, the compounds of the formula I can be used as the base materials from which liquid crystal media are predominantly composed;
however, it is also possible for compounds of the formula I
to be added to liquid crystal base materials of other classes of compounds, for example in order to influence the dielectric and/or optical anisotropy and/or the viscosity and/or the nematic mesophase range of such a dielectric.
The compounds of the formula I are colourless in the pure state and are liquid crystalline in a temperature range which is favourably placed for electrooptical use.
They are very stable towards chemicals, heat and light.
The invention thus relates to the fluorinated cyclohexyl derivatives of the formula I, to liquid crystalline media with at least two liquid crystalline components, wherein at least on component is a compound of the formula I and to liquid crystal display devices containing such media.
Above and below, R1 and X have the meaning given unless expressly indicated otherwise.
R1 i~ preferably alkyl, alkoxy, oxaalkyl, alkanoyloxy or alkenyl and can exhibit a straight-chain or branched structure.
Alkyl or alkoxy preferably are straight-chain and have 2, 3, 4, 5, 6 or 7 C atoms. Accordingly they are prefer-ably ethyl, propyl, butyl, pentyl, hexyl, heptyl, ethoxy,propoxy, butoxy, pentoxy, hexoxy or heptoxy, also methyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetra-decyl, pentadecyl, methoxy, octoxy, nonoxy, decoxy, un-decoxy, dodecoxy, tridecoxy or tetradecoxy.
., .: - -. . :.. . .-, . . . . . - .. ... ... , .......... .. . .- .. ~, .. :..... ..
.- ~. . - - . -, - .. , . - . . .. . ....
Oxaalkyl is preferably straight-chain 2-oxapropyl (= methoxy-methyl), 2-(= ethoxymethyl) or 3-oxybutyl (= 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.
Alkenyl is preferably straight-chain and has 2 or 10 C atoms.
It is accordingly, in particular, vinyl, prop-l- or prop-2- ; -enyl, but-l-, -2- or -3-enyl, pent-1-, -2-, -3- or -4-enyl, hex-l-, -2-, -3-, -4- or -5-enyl, hept-l-, -2-, -3-, -4-, -5- or -6-enyl, oct-l-, -2-, -3-, -4-, -5- -6- or -7-enyl, non-l-, -2-, -3-, -4-, -5-, -6-, -7- or -8-enyl or dec-1-, -2-, -3-, -4-, -5-, -6-, -7-, -8- or -9-enyl.
Compounds of the formula I containing a branched terminal group can occasionally be of importance because of an improved solubility in the customary liquid crystal base materials, but in particular as chiral doping substances ~-if they are optically active.
Branched groups of this type as a rule contain not more than one chain branching. Preferred branched radicals ~re isopropyl, 2-butyl (= 1-methylpropyl), isobutyl (= 2-methylpropyl, 2-methylbutyl, isopentyl, (= 3-methylbutyl), - 2-methylpentyl, 2-ethylhexyl, 2-propylpentyl, 2-octyl, isopropoxy, 2-methylpropoxy, 2-methylbutoxy, 3-methylbut-oxy, 2-methylpentoxy, 3-methylpentoxy, 2-ethylhexoxy, 2-methylhexoxy, l-methylhexoxy, 1-methylheptoxy (= 2-octyl-oxy), 2-oxa-3-methylbutyl, 3-oxa-4-methylpentyl, 4-methyl-hexyl, 2-nonyl, 2-decyl, 2-dodecyl, 6-methyloctoxy, 6-methyloctanoyloxy, 4-methylheptyloxycarbonyl, 2-methylbuty-ryloxy, 3-methylvaleryloxy, 4-methylhexanoyloxy, 2-methyl-3-oxapentyl and 2-methyl-3-oxahexyl.
.~.. -, -, ,; .-,.. -.- . :.- - . , - . , . .:
--~ 20330~7 In the case of compounds with a branched terminal group R1, formula I includes both the optical antipodes and racemates as well as mixtures thereof.
m is preferably l. X is preferably -OCF3 or -OCHF2 and furthermore preferably -CF3.
Of the compounds of the formula I and subformulae thereof, those in which at least one of the radicals contained therein has one of the preferred meanings given are preferred.
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 Chemistryl, Georg Thieme Verlag, Stuttgart), and 15 in particular under reaction conditions which are known -an~ 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, ~uch that they are not isolated from the reac~
tion mixture but are immediately reacted further to give the compounds of the formula I.
A preferred route for preparation starts from the easily accessible Wittig reagent R1 ~ - ~ ¦-C~2P~Ph3Je, which is reacted with 2-fluoro-4-X-benzaldehyde under the known conditions for Wittig reaction. The cyclohexyl deriva-tives of formula I are easily obtained by catalytic hydro-genation (Pd-C) of the Wittig products.
, , , ., - , .
: ~ , , ' ; : ' -. ;. . . .
, ....... , . .
---` 20~3Q87 -:
An alternative route is shown in Scheme 1:
Scheme 1 R~ -C~=CH2 + Br- ~ -X :~
~ Heck reaction R~ _CH=CH_ ~ -X
m l~ ~2/Pd-C
Rl_~ ~ -C~12CH2 -~ -X
Other routes are apparent to the skilled worker. In addition it is possible to follow the above shown routes with a group X being different from the clesired one and to introduce the desired group X in the f inal step, e.g.
conversion of -CN to -COO~ and finally to -CF3 ~ also being possible to Use Br as a precurSor for CN3; or -OMe to -OH
and finally to -OCF3 or -OC~F2. All these steps and the corresponding reaction conditions are known to the skilled worker.
. " .. . .
,. : : : - , .. . . .
,. , ., , ,,~ . :
~.,~ :, : -- : , , In addition to one or more compounds for formula I the liquid crystal media according to the invention prefer- -ably contain 2-40 components and in particular 4-30 com-ponents. Liquid crystal media being composed of one or S more compounds of formula I and 7-25 other components ~are especially preferred.
These additional components are preferably chosen from the nematic or nematogenic (monotropic or isotropic) substances; in particular from the classes of azoxy-benzenes, benzylideneanilines, biphenyls, terphenyls,phenyl or cyclohexyl benzoates, phenyl or cyclohexyl cyclohexanecarboxylates, phenyl or cyclohexyl cyclohexyl-benzoates, phenyl or cyclohexyl cyclohexylcyclohexane-carboxylates, cyclohexylphenyIbenzoates, cyclohexyl-phenyl cyclohexanecarboxylates, cyclohexylphenyl cyclo-hexylcyclohexanecarboxylates, phenylcyclohexanes, cyclohexylbiphenyls, phenylcyclohexylcyclohexanes, cyclohexylcyclohexanes, cyclohexylcyclohexenes, cyclo-hexylcyclohexylcyclohexene, 1,4-bis-cyclohexyIbenzenes, 4,4'-bis-cyclohexylbiphenyls, phenyl- or cyclohexyl-pyrimidines, phenyl- or cyclohexylpyridines, phenyl- or cyclohexyldioxanes, phenyl- or cyclohexyl-1,3-dithiane~, 1,2-diphenylethanes, 1,2-dicyclohexylethanes, l-phenyl-2-cyclohexylethanes, 1-cyclohexyl-2-(4-phenyl-cyclohexyl)-ethanes, 1-cyclohexyl-2-biphenylethanes, 1-phenyl-2-cyclo-hexyl-phenylethanes, optionally halogenated stilbenes, benzyl phenyl ethers, tolanes and substituted cinnamic acids.
The 1,4-phenylene groups of these compounds may be fluorinated.
,.,.. ,,: !. ~ ~. . . :
2~33Q87 The most important compounds which are possible consti~
tuents of liquid crystal media according to the invention can be characterized by the formalae 1, 2, 3, 4 and 5:
R'-L-U-R" 1 S R'-L-COO-U-R" 2 ..
R'-L-OOC-U-R" 3 R'-L-C-C-U-R" S
In the formulae 1, 2, 3, 4 and 5 L and U may be equal or different from each other. ~ and U independently from each other denote a bivalent residue selected from the group consisting of -Phe-, -Cyc-, -Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-, -Pyr-, -Dio-, -G-Phe-, -G-Cyc- and their mirror images; in this compilation of residues Phe denotes un-15 substituted or fluorinated 1,4-phenylen, Cyc trans- 1,4- :
cyclohexylene or 1,4-cyclohexenylen, Pyr pyrLmidine-2,5-diyl or pyridine-2,5-diyl, Dio 1,3-dioxane-2,5-diyl and G 2-(trans-1,4-cyclohexyl)-ethyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl or 1,3-dioxane-2,5-diyl.
One of the residue L and U is preferably Cyc, Phe or ~yr.
U preferably denotes Cyc, Phe or Phe-Cyc. The liquid crystal media according to the invention preferably con-tain one or more components selected from the compounds of formulae 1, 2, 3, 4 and 5 with L and U meaning Cyc, Phe and Pyr, said liquid crystal media further containing at the same time one ore more components selected from the compounds of formulae 1, 2, 3, 4 and 5 with one of the residues L and U denoting Cyc, Phe and Pyr and the other residue being selected from the group consisting of -Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-, -G-Cyc-, said liquid '.~ :. , ; , ;:;: . . . .
. .i, . . .
, . .... . . . . ~: .
,. - ~ . . . : ~
. ~ - . . . - . - .
~033087 crystal media containing in addition to this optionally one or more components selected from the compounds of formulae 1, 2, 3, 4 and 5 with L and U being selected from the group consisting of -Phe-Cyc-, -Cyc-Cyc-, -G-Phe- and -G-Cyc.
In a preferred subgroup of the compounds of formulae 1, 2, 3, 4 and 5 (subgroup 1~ R' and R" are independent-ly from each other alkyl, alkenyl, alkoxy, alkenoxy with up to 8 carbon atoms. R' and R" differ from one another in most of these compounds, one of the residues usually being alkyl or alkenyl. In another preferred subgroup of the com~ounds of formulae 1, 2, 3, 4 and 5 (subgroup 2) R" denotes -CN, -CF3, -F, -Cl or -NCS while R' has the meaning indicated in subgroup 1 and is preferably alkyl or alkenyl. Other variants of the envisaged substituents in the compounds of formulae 1, 2, 3, ~ and 5 are also customary. Many such substances are commercially available~
All these substances are obtainable by methods which are known from the literature or by analogous methods.
The liquid crystal media according to the invention pre-ferably contain in addition to components selected fro~
subgroup 1 also components of subgroup 2, the percentage of these components being as follows:
subgroup 1: 20 to 90 %, in particular 30 to 90 %
25 subgroup 2: 10 to 50 %, in particular 10 to 50 %
In ~hese liquid crystal media the percentages of the com-pounds according to the invention and the compounds of sub-group 1 and 2 may add up to give 100 %.
;. , -: .
, .
., . - . :: .
2~33087 The media according to the invention preferably contain -1 to 40 %, in particular 5 to 30 % of the compounds according to the invention. Media containing more than 40 %, in particular 45 to 90 % of the compounds accor-ding to the invention are further preferred. The media contain preferably 3, 4 or 5 compounds according to the invention.
The media according to the invention are prepared in a manner which is customary per se. As a rule, the com-ponents are dissolved in one another, advantageouslyat elevated temperature. The liquid crystal media accor-ding to the invention can be modified by suitable addi-tives so that they can be used in all the types of liquid crystal display devices. Such additives are known to the expert and are described in detail in the liteL~ture (H. Kelker/R. ~atz, ~andbook of Liquid Crystals, Verlag Chemie, Weinheim, 1980). For example, it is possible to add pleochroic dyestuffs to prepare colored guest-host ~y~tems or substances for modifying the dielectric aniso-tropy, the viscosity and/or the orientation of the nematicphases.
The following examples are to be construed as merely illustrative and not limitative. m.p. = melting point, c.p. = clearing point. In the foregoing and in the fol-lowing all parts and percentages are by weight and thetemperatures are set forth in degrees Celsius. "Custo-mary work-up" means that water is added, the mixture i~ extracted with methylene chloride, the organic phase is seperated off, dried and evaporated, and the product is purified by crystallization and/or chromatography.
~, .. , ... , . . : .
. ~ ..... , ~ ,., . . .. ' ' '- .: ' .,.. ,.............. , ~-., ., , .. , :,: -- . -. ~ ,. . . : - , . .
:; ~ . , .- .-- .,,: : . , .
203~087 Further are:
C: crystalline-solid state, S: smectic phase (the index denoting the typ of smectic phase), N: nematic phase, ~ :
Ch: cholesteric phase, I: isotropic phase. The number :~
S being embraced by 2 of these symbols denotes the tem-perature of phase change.
ExamPles for Production Exam~le 1 Hydrogenation of 1-(4'-n-propylbicyclohexyl)-2-(2-fluoro-4-trifluoromethylphenyl)-et~ene yields after customary work up l-(4'-n-propylbicyclohexyl)-2-(2-fluoro-4-trifluoromethylphenyl)-ethane, C 79.5 N 104 I.
Exa~mples 2 to 11 :: :
The following compounds are obtained analogously:
(2) 1-(4'-n-pentylbicyclohexyl)-2-(2-fluoro-4-trifluoro-methylphenyl)-ethane (3) 1-(4'-n-pentylbicyclohexyl)-2-(2-fluoro-4-trifluoro-methoxyphenyl)-ethane (4) 1-(4'-n-propylbicyclohexyl)-2-(2-fluoro-4-trifluoro-methoxyphenyl)-ethane (5) 1-(4'-n-butylbicyclohexyl)-2-(2-fluoro-4-trifluoro-methoxyphenyl)-ethane (6) 1-(4'-n-propylbicyclohexyl)-2-(2-fluoro-4-difluoro-methoxyphenyl)-ethane (7) 1-(4'-n-butylbicyclohexyl)-2-(2-fluoro-4-difluoro-methoxyphenyl)-ethane '7''~' 2033087 I
Merck Patent Gesellschaft mit beschrankter ~aftung 6100 D a r m s t a d t Fluorinated Cyclohexyl Derivatives The invention relates to fluorinated cyclohexyl deri-vatives of formula I ~ -F
{ m wherein R1 denotes an alkyl residue with up to 12 carbon atoms wherein one or two non-adjacent CH2-groups may also be replaced by -O-, -O-CO-, -CO-O- and/or -CH=CH-, m is 0 or 1, and X is F, -CF3, -OCF3 or -OCHF2 and also to liquid crystalline media being a mixture of at least 2 compounds, characterized in that at least one compound is a fluorinated cyclohexyl derivative accord-ing to formula I.
The invention was based on the object of discovering new stable liquid crystal or mesogenic compounds which are suitable as components of liquid crystalline media and, in particular, have advantageous values for optical and dielectric anisotropy combined with low viscosity and high nematc~enity.
, ~ ~
:
.~
.,. ~ , .
, ~ , , 20330~7 Similar bicyclohexyl derivatives are described in Euro~
pean Patent 0 125 563: ~ -alkyl- ~ - ~ -CH2CH2- ~ -CN
alkY~ >~CH2CH2~~-F ;
C3H7- ~ ~ ~ -C~2CH2- ~ -CN
F F :;.
C3 ~ - ~ _ ~ -CH2CH2- ~ -CN ~ .
CH3 ~ ;
Similar cyclohexyl derivatives are described in German ~-10 Patent 32 33 641:
alkyl ~ -CH2CH2- ~ - F
These compounds, however, still pose some problems in the mixture development due to the occurrence of disturb-ing smectic phases and to the fact that the strongly p~-lar compounds exhibit high viscosities whereas the lowviscosity compounds have relatively low values for 1, and/or 1. In-addition, the laterally substituted species are not easily accessible.
It has now been found that fluorinated cyclohexyls of formula I are highly suitable as components of liquid crystalline media. In particular, they have especially advantageous values of optical and dielectric anisotropy ~ and ~"). It is also possible to obtain stable liquid crystal phases with a broad nematic mesophase range including a good deep temperature behaviour and a comparatively low viscosity with the aid of ~hese compounds.
~3~87~
Depending on the choice of the substituents, the compounds of the formula I can be used as the base materials from which liquid crystal media are predominantly composed;
however, it is also possible for compounds of the formula I
to be added to liquid crystal base materials of other classes of compounds, for example in order to influence the dielectric and/or optical anisotropy and/or the viscosity and/or the nematic mesophase range of such a dielectric.
The compounds of the formula I are colourless in the pure state and are liquid crystalline in a temperature range which is favourably placed for electrooptical use.
They are very stable towards chemicals, heat and light.
The invention thus relates to the fluorinated cyclohexyl derivatives of the formula I, to liquid crystalline media with at least two liquid crystalline components, wherein at least on component is a compound of the formula I and to liquid crystal display devices containing such media.
Above and below, R1 and X have the meaning given unless expressly indicated otherwise.
R1 i~ preferably alkyl, alkoxy, oxaalkyl, alkanoyloxy or alkenyl and can exhibit a straight-chain or branched structure.
Alkyl or alkoxy preferably are straight-chain and have 2, 3, 4, 5, 6 or 7 C atoms. Accordingly they are prefer-ably ethyl, propyl, butyl, pentyl, hexyl, heptyl, ethoxy,propoxy, butoxy, pentoxy, hexoxy or heptoxy, also methyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetra-decyl, pentadecyl, methoxy, octoxy, nonoxy, decoxy, un-decoxy, dodecoxy, tridecoxy or tetradecoxy.
., .: - -. . :.. . .-, . . . . . - .. ... ... , .......... .. . .- .. ~, .. :..... ..
.- ~. . - - . -, - .. , . - . . .. . ....
Oxaalkyl is preferably straight-chain 2-oxapropyl (= methoxy-methyl), 2-(= ethoxymethyl) or 3-oxybutyl (= 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.
Alkenyl is preferably straight-chain and has 2 or 10 C atoms.
It is accordingly, in particular, vinyl, prop-l- or prop-2- ; -enyl, but-l-, -2- or -3-enyl, pent-1-, -2-, -3- or -4-enyl, hex-l-, -2-, -3-, -4- or -5-enyl, hept-l-, -2-, -3-, -4-, -5- or -6-enyl, oct-l-, -2-, -3-, -4-, -5- -6- or -7-enyl, non-l-, -2-, -3-, -4-, -5-, -6-, -7- or -8-enyl or dec-1-, -2-, -3-, -4-, -5-, -6-, -7-, -8- or -9-enyl.
Compounds of the formula I containing a branched terminal group can occasionally be of importance because of an improved solubility in the customary liquid crystal base materials, but in particular as chiral doping substances ~-if they are optically active.
Branched groups of this type as a rule contain not more than one chain branching. Preferred branched radicals ~re isopropyl, 2-butyl (= 1-methylpropyl), isobutyl (= 2-methylpropyl, 2-methylbutyl, isopentyl, (= 3-methylbutyl), - 2-methylpentyl, 2-ethylhexyl, 2-propylpentyl, 2-octyl, isopropoxy, 2-methylpropoxy, 2-methylbutoxy, 3-methylbut-oxy, 2-methylpentoxy, 3-methylpentoxy, 2-ethylhexoxy, 2-methylhexoxy, l-methylhexoxy, 1-methylheptoxy (= 2-octyl-oxy), 2-oxa-3-methylbutyl, 3-oxa-4-methylpentyl, 4-methyl-hexyl, 2-nonyl, 2-decyl, 2-dodecyl, 6-methyloctoxy, 6-methyloctanoyloxy, 4-methylheptyloxycarbonyl, 2-methylbuty-ryloxy, 3-methylvaleryloxy, 4-methylhexanoyloxy, 2-methyl-3-oxapentyl and 2-methyl-3-oxahexyl.
.~.. -, -, ,; .-,.. -.- . :.- - . , - . , . .:
--~ 20330~7 In the case of compounds with a branched terminal group R1, formula I includes both the optical antipodes and racemates as well as mixtures thereof.
m is preferably l. X is preferably -OCF3 or -OCHF2 and furthermore preferably -CF3.
Of the compounds of the formula I and subformulae thereof, those in which at least one of the radicals contained therein has one of the preferred meanings given are preferred.
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 Chemistryl, Georg Thieme Verlag, Stuttgart), and 15 in particular under reaction conditions which are known -an~ 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, ~uch that they are not isolated from the reac~
tion mixture but are immediately reacted further to give the compounds of the formula I.
A preferred route for preparation starts from the easily accessible Wittig reagent R1 ~ - ~ ¦-C~2P~Ph3Je, which is reacted with 2-fluoro-4-X-benzaldehyde under the known conditions for Wittig reaction. The cyclohexyl deriva-tives of formula I are easily obtained by catalytic hydro-genation (Pd-C) of the Wittig products.
, , , ., - , .
: ~ , , ' ; : ' -. ;. . . .
, ....... , . .
---` 20~3Q87 -:
An alternative route is shown in Scheme 1:
Scheme 1 R~ -C~=CH2 + Br- ~ -X :~
~ Heck reaction R~ _CH=CH_ ~ -X
m l~ ~2/Pd-C
Rl_~ ~ -C~12CH2 -~ -X
Other routes are apparent to the skilled worker. In addition it is possible to follow the above shown routes with a group X being different from the clesired one and to introduce the desired group X in the f inal step, e.g.
conversion of -CN to -COO~ and finally to -CF3 ~ also being possible to Use Br as a precurSor for CN3; or -OMe to -OH
and finally to -OCF3 or -OC~F2. All these steps and the corresponding reaction conditions are known to the skilled worker.
. " .. . .
,. : : : - , .. . . .
,. , ., , ,,~ . :
~.,~ :, : -- : , , In addition to one or more compounds for formula I the liquid crystal media according to the invention prefer- -ably contain 2-40 components and in particular 4-30 com-ponents. Liquid crystal media being composed of one or S more compounds of formula I and 7-25 other components ~are especially preferred.
These additional components are preferably chosen from the nematic or nematogenic (monotropic or isotropic) substances; in particular from the classes of azoxy-benzenes, benzylideneanilines, biphenyls, terphenyls,phenyl or cyclohexyl benzoates, phenyl or cyclohexyl cyclohexanecarboxylates, phenyl or cyclohexyl cyclohexyl-benzoates, phenyl or cyclohexyl cyclohexylcyclohexane-carboxylates, cyclohexylphenyIbenzoates, cyclohexyl-phenyl cyclohexanecarboxylates, cyclohexylphenyl cyclo-hexylcyclohexanecarboxylates, phenylcyclohexanes, cyclohexylbiphenyls, phenylcyclohexylcyclohexanes, cyclohexylcyclohexanes, cyclohexylcyclohexenes, cyclo-hexylcyclohexylcyclohexene, 1,4-bis-cyclohexyIbenzenes, 4,4'-bis-cyclohexylbiphenyls, phenyl- or cyclohexyl-pyrimidines, phenyl- or cyclohexylpyridines, phenyl- or cyclohexyldioxanes, phenyl- or cyclohexyl-1,3-dithiane~, 1,2-diphenylethanes, 1,2-dicyclohexylethanes, l-phenyl-2-cyclohexylethanes, 1-cyclohexyl-2-(4-phenyl-cyclohexyl)-ethanes, 1-cyclohexyl-2-biphenylethanes, 1-phenyl-2-cyclo-hexyl-phenylethanes, optionally halogenated stilbenes, benzyl phenyl ethers, tolanes and substituted cinnamic acids.
The 1,4-phenylene groups of these compounds may be fluorinated.
,.,.. ,,: !. ~ ~. . . :
2~33Q87 The most important compounds which are possible consti~
tuents of liquid crystal media according to the invention can be characterized by the formalae 1, 2, 3, 4 and 5:
R'-L-U-R" 1 S R'-L-COO-U-R" 2 ..
R'-L-OOC-U-R" 3 R'-L-C-C-U-R" S
In the formulae 1, 2, 3, 4 and 5 L and U may be equal or different from each other. ~ and U independently from each other denote a bivalent residue selected from the group consisting of -Phe-, -Cyc-, -Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-, -Pyr-, -Dio-, -G-Phe-, -G-Cyc- and their mirror images; in this compilation of residues Phe denotes un-15 substituted or fluorinated 1,4-phenylen, Cyc trans- 1,4- :
cyclohexylene or 1,4-cyclohexenylen, Pyr pyrLmidine-2,5-diyl or pyridine-2,5-diyl, Dio 1,3-dioxane-2,5-diyl and G 2-(trans-1,4-cyclohexyl)-ethyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl or 1,3-dioxane-2,5-diyl.
One of the residue L and U is preferably Cyc, Phe or ~yr.
U preferably denotes Cyc, Phe or Phe-Cyc. The liquid crystal media according to the invention preferably con-tain one or more components selected from the compounds of formulae 1, 2, 3, 4 and 5 with L and U meaning Cyc, Phe and Pyr, said liquid crystal media further containing at the same time one ore more components selected from the compounds of formulae 1, 2, 3, 4 and 5 with one of the residues L and U denoting Cyc, Phe and Pyr and the other residue being selected from the group consisting of -Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-, -G-Cyc-, said liquid '.~ :. , ; , ;:;: . . . .
. .i, . . .
, . .... . . . . ~: .
,. - ~ . . . : ~
. ~ - . . . - . - .
~033087 crystal media containing in addition to this optionally one or more components selected from the compounds of formulae 1, 2, 3, 4 and 5 with L and U being selected from the group consisting of -Phe-Cyc-, -Cyc-Cyc-, -G-Phe- and -G-Cyc.
In a preferred subgroup of the compounds of formulae 1, 2, 3, 4 and 5 (subgroup 1~ R' and R" are independent-ly from each other alkyl, alkenyl, alkoxy, alkenoxy with up to 8 carbon atoms. R' and R" differ from one another in most of these compounds, one of the residues usually being alkyl or alkenyl. In another preferred subgroup of the com~ounds of formulae 1, 2, 3, 4 and 5 (subgroup 2) R" denotes -CN, -CF3, -F, -Cl or -NCS while R' has the meaning indicated in subgroup 1 and is preferably alkyl or alkenyl. Other variants of the envisaged substituents in the compounds of formulae 1, 2, 3, ~ and 5 are also customary. Many such substances are commercially available~
All these substances are obtainable by methods which are known from the literature or by analogous methods.
The liquid crystal media according to the invention pre-ferably contain in addition to components selected fro~
subgroup 1 also components of subgroup 2, the percentage of these components being as follows:
subgroup 1: 20 to 90 %, in particular 30 to 90 %
25 subgroup 2: 10 to 50 %, in particular 10 to 50 %
In ~hese liquid crystal media the percentages of the com-pounds according to the invention and the compounds of sub-group 1 and 2 may add up to give 100 %.
;. , -: .
, .
., . - . :: .
2~33087 The media according to the invention preferably contain -1 to 40 %, in particular 5 to 30 % of the compounds according to the invention. Media containing more than 40 %, in particular 45 to 90 % of the compounds accor-ding to the invention are further preferred. The media contain preferably 3, 4 or 5 compounds according to the invention.
The media according to the invention are prepared in a manner which is customary per se. As a rule, the com-ponents are dissolved in one another, advantageouslyat elevated temperature. The liquid crystal media accor-ding to the invention can be modified by suitable addi-tives so that they can be used in all the types of liquid crystal display devices. Such additives are known to the expert and are described in detail in the liteL~ture (H. Kelker/R. ~atz, ~andbook of Liquid Crystals, Verlag Chemie, Weinheim, 1980). For example, it is possible to add pleochroic dyestuffs to prepare colored guest-host ~y~tems or substances for modifying the dielectric aniso-tropy, the viscosity and/or the orientation of the nematicphases.
The following examples are to be construed as merely illustrative and not limitative. m.p. = melting point, c.p. = clearing point. In the foregoing and in the fol-lowing all parts and percentages are by weight and thetemperatures are set forth in degrees Celsius. "Custo-mary work-up" means that water is added, the mixture i~ extracted with methylene chloride, the organic phase is seperated off, dried and evaporated, and the product is purified by crystallization and/or chromatography.
~, .. , ... , . . : .
. ~ ..... , ~ ,., . . .. ' ' '- .: ' .,.. ,.............. , ~-., ., , .. , :,: -- . -. ~ ,. . . : - , . .
:; ~ . , .- .-- .,,: : . , .
203~087 Further are:
C: crystalline-solid state, S: smectic phase (the index denoting the typ of smectic phase), N: nematic phase, ~ :
Ch: cholesteric phase, I: isotropic phase. The number :~
S being embraced by 2 of these symbols denotes the tem-perature of phase change.
ExamPles for Production Exam~le 1 Hydrogenation of 1-(4'-n-propylbicyclohexyl)-2-(2-fluoro-4-trifluoromethylphenyl)-et~ene yields after customary work up l-(4'-n-propylbicyclohexyl)-2-(2-fluoro-4-trifluoromethylphenyl)-ethane, C 79.5 N 104 I.
Exa~mples 2 to 11 :: :
The following compounds are obtained analogously:
(2) 1-(4'-n-pentylbicyclohexyl)-2-(2-fluoro-4-trifluoro-methylphenyl)-ethane (3) 1-(4'-n-pentylbicyclohexyl)-2-(2-fluoro-4-trifluoro-methoxyphenyl)-ethane (4) 1-(4'-n-propylbicyclohexyl)-2-(2-fluoro-4-trifluoro-methoxyphenyl)-ethane (5) 1-(4'-n-butylbicyclohexyl)-2-(2-fluoro-4-trifluoro-methoxyphenyl)-ethane (6) 1-(4'-n-propylbicyclohexyl)-2-(2-fluoro-4-difluoro-methoxyphenyl)-ethane (7) 1-(4'-n-butylbicyclohexyl)-2-(2-fluoro-4-difluoro-methoxyphenyl)-ethane '7''~' 2033087 I
(8) 1-(4'-n-pentylbicyclohexyl)-2-(2-fluoro-4-difluoro-methoxyphenyl)-ethane (9) 1-(4'-n-pentylbicyclohexyl)-2-(2,4-difluorophenyl)-ethane (10) 1-(4'-n-butylbicyclohexyl)-2-(2,4-difluorophenyl)-ethane (11) 1-(4'-n-propylbicyclohexyl)-2-(2,4-difluorophenyl)-ethane Examples of compositions ExamPle A
A liquid crystalline medium consisting of 15 % of 1-(4'-n-propylbicyclohexyl~-2-(2-fluoro-4-tri-fluoromethylphenyl)-ethane and 85 % of a mixture containing 24 % p-(trans-4-propylcyclohexyl)-benzonitrile, 36 % p-(trans-4-pentylcyclohexyl)-benzonitrile, 25 % p-(trans-4-heptylcyclohexyl)-benzonitrile and 15 % 4-cyano-4'-(trans-4-pentylcyclohexy ~biphenyl shows N 73.5 I.
.; : . - .
,,.. ,.~ ~, ,. ...... - . - .
,:,, . ., , . - .: : , -,.,. ., : . . .
" . .. .. .
r; ~' . ~ . : '
A liquid crystalline medium consisting of 15 % of 1-(4'-n-propylbicyclohexyl~-2-(2-fluoro-4-tri-fluoromethylphenyl)-ethane and 85 % of a mixture containing 24 % p-(trans-4-propylcyclohexyl)-benzonitrile, 36 % p-(trans-4-pentylcyclohexyl)-benzonitrile, 25 % p-(trans-4-heptylcyclohexyl)-benzonitrile and 15 % 4-cyano-4'-(trans-4-pentylcyclohexy ~biphenyl shows N 73.5 I.
.; : . - .
,,.. ,.~ ~, ,. ...... - . - .
,:,, . ., , . - .: : , -,.,. ., : . . .
" . .. .. .
r; ~' . ~ . : '
Claims (6)
1. Fluorinated cyclohexyl derivatives of formula I
I
wherein R1 denotes an alkyl residue with up to 12 carbon atoms wherein one or two non-adjacent CH2-groups may also be replaced by -O-, -O-CO-, -CO-O- and/or -CH=CH-, m is 0 or 1, and X is F, -CF3, -OCF3 or -OCHF2.
I
wherein R1 denotes an alkyl residue with up to 12 carbon atoms wherein one or two non-adjacent CH2-groups may also be replaced by -O-, -O-CO-, -CO-O- and/or -CH=CH-, m is 0 or 1, and X is F, -CF3, -OCF3 or -OCHF2.
2. Cyclohexyl derivatives of claim 1, wherein X denotes -OCF3 or -OCHF2.
3. Cyclohexyl derivatives of claim 1, wherein X denotes -CF3.
4. Cyclohexyl derivatives of claim 1, wherein X denotes F.
5. Cyclohexyl derivatives of at least one of claims 1 to 4, wherein R1 denotes an unbranched alkyl residue of 2 to 7 carbon atoms.
6. Liquid crystalline medium being a mixture of at least two compounds, characterized in that at least one com-pound is a fluorinated cyclohexyl derivative accord-ing to claim 1.
7. Liquid crystal display device, characterized in that it contains a liquid crystalline medium according to claim 6.
8. Electrooptical display device, characterized in that it contains a liquid crystalline medium according to
6. Liquid crystalline medium being a mixture of at least two compounds, characterized in that at least one com-pound is a fluorinated cyclohexyl derivative accord-ing to claim 1.
7. Liquid crystal display device, characterized in that it contains a liquid crystalline medium according to claim 6.
8. Electrooptical display device, characterized in that it contains a liquid crystalline medium according to
claim 6.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8911217.1 | 1989-05-16 | ||
| GB898911217A GB8911217D0 (en) | 1989-05-16 | 1989-05-16 | Fluorinated cyclohexyl derivatives |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2033087A1 true CA2033087A1 (en) | 1990-11-17 |
Family
ID=10656817
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002033087A Abandoned CA2033087A1 (en) | 1989-05-16 | 1990-05-08 | Fluorinated cyclohexyl derivatives |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0425624A1 (en) |
| JP (1) | JPH03506038A (en) |
| CA (1) | CA2033087A1 (en) |
| GB (1) | GB8911217D0 (en) |
| WO (1) | WO1990014406A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0521420A1 (en) * | 1991-07-04 | 1993-01-07 | MERCK PATENT GmbH | Fluorinated cyclohexyl derivatives |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3317597A1 (en) * | 1983-05-14 | 1984-11-15 | Merck Patent Gmbh, 6100 Darmstadt | BICYCLOHEXYLETHANE |
| DE3614778A1 (en) * | 1986-05-02 | 1987-11-05 | Merck Patent Gmbh | Smectic liquid crystal phases |
| DE3732284A1 (en) * | 1987-09-25 | 1989-04-13 | Merck Patent Gmbh | SUBSTITUTED PHENYLTRIFLUORMETHYLETHER |
| DE3736489A1 (en) * | 1987-10-28 | 1989-05-11 | Merck Patent Gmbh | CROSS COUPLING OF TITAN ORGANYLEN |
| DE3887084D1 (en) * | 1987-11-06 | 1994-02-24 | Hoffmann La Roche | Halogenated benzene derivatives. |
-
1989
- 1989-05-16 GB GB898911217A patent/GB8911217D0/en active Pending
-
1990
- 1990-05-08 WO PCT/EP1990/000741 patent/WO1990014406A1/en not_active Application Discontinuation
- 1990-05-08 JP JP2506924A patent/JPH03506038A/en active Pending
- 1990-05-08 CA CA002033087A patent/CA2033087A1/en not_active Abandoned
- 1990-05-08 EP EP90906983A patent/EP0425624A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| GB8911217D0 (en) | 1989-07-05 |
| EP0425624A1 (en) | 1991-05-08 |
| JPH03506038A (en) | 1991-12-26 |
| WO1990014406A1 (en) | 1990-11-29 |
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