WO1990014406A1

WO1990014406A1 - Fluorinated cyclohexyl derivatives

Info

Publication number: WO1990014406A1
Application number: PCT/EP1990/000741
Authority: WO
Inventors: David Coates; Ian Charles Sage; Simon Greenfield; Dieter Dorsch
Original assignee: Merck Patent GmbH
Current assignee: Merck Patent GmbH
Priority date: 1989-05-16
Filing date: 1990-05-08
Publication date: 1990-11-29
Anticipated expiration: 1991-11-16
Also published as: CA2033087A1; EP0425624A1; GB8911217D0; JPH03506038A

Abstract

The invention relates to fluorinated cyclohexyl derivatives of formula (I), wherein R1 denotes an alkyl residue with up to 12 carbon atoms wherein one or two non-adjacent CH¿2?-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

Fluorinated Cyclohexyl Derivatives

The invention relates to fluorinated cyclohexyl deri¬ vatives of formula I

wherein R denotes an alkyl residue with up to 12 carbon atoms wherein one or two non- adjacent CH₂-groups may also be replaced by -0-, -0-CO-, -CO-O- and/or -CH=CH-,

m is 0 or 1, and

X is F, -CF, -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 nematcgenity. Similar bicyclohexyl derivatives are described in Euro¬ pean Patent 0 125 563 :

Similar cyclohexyl derivatives are described in German Patent 32 33 641:

These compounds, however, still pose some problems in the mixture development due to the occurrence of disturb¬ ing s ectic phases and to the fact that the strongly pe- lar compounds exhibit high viscosities whereas the low viscosity compounds have relatively low values for ε„ and/or ε_L« 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 (Δε, εj_ and ε„). It is also possible to obtain stable liquid crystal phases with a broad ne atic mesophase range including a good deep temperature behaviour and a comparatively low viscosity with the aid of these compounds. Depending on the choice of the substituentε, 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, R and X have the meaning given unless expressly indicated otherwise.

R is 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-1- or prop-2- enyl, but-1-, -2- or -3-enyl, pent-1-, -2-, -3- or -4-enyl, hex-1-, -2-, -3-, -4- or -5-enyl, hept-1-, -2-, -3-, -4-, -5- or -6-enyl, oct-1-, -2-, -3-, -4-, -5- -6- or -7-enyl, non-1-, -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 are 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, 1-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-meth lbuty- ryloxy, 3-methylvaleryloxy, 4-methylhexanoyloxy, 2-methyl-3- oxapentyl and 2-methyl-3-oxahexyl. In the case of compounds with a branched terminal group R , formula I includes both the optical antipodes and race ates as well as mixtures thereof.

m is preferably 1. 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, ethoden 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 εe and are not mentioned in more detail here can also be used in this connection.

If desired, the starting materials can also be formed _t in situ, such 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 ittig reagent R - H>- <H> -CH₂P^φPh₃J^θ, which ^u 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. An alternative route is shown in Scheme 1:

Scheme 1

Heck reaction

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 desired one and to introduce the desired group X in the final step, e.g. conversion of -CN to -COOH and finally to -CF₃ (also being possible to use Br as a precursor for CN); or -OMe to -OH and finally to -OCF₃ or -OCHF₂. 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 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, cyclohexylphenylbenzoates, cyclohexyl- phenyl cyclohexanecarboxylates, cyclohexylphenyl cyclo¬ hexylcyclohexanecarboxylates, phenylcyclohexanes, cyclohexylbiphenyls, phenylcyclohexylcyclohexanes, cyclohexylcyclohexanes, cyclohexylcyclohexenes, cyclo- hexylcyclohexylcyclohexene, 1,4-bis-cyclohexylbenzenes, 4,4'-bis-cyclohex lbiphenyls, phenyl- or cyclohexyl- pyrimidines, phenyl- or cyclohexylpyridines, phenyl- or cyclohexyldioxanes, phenyl- or cyclohexyl-1,3-dithianes, 1,2-diphenylethanes, 1,2-dicyclohexylethanes, 1-phenyl- 2-cyclohexylethanes, l-cyclohexyl-2-(4-phenyl-cyclohexyl)- ethanes, l-cyclohexyl-2-biphenylethanes, l-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. 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 R^«-L-COO-TJ-R" 2

R'-L-OOC-U-R" 3

R'- -α^O^-U-R" 4

R'-L-C≡C-U-R" 5

In the formulae 1, 2, 3, 4 and 5 L and U may be equal or different from each other. L 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- substituted or fluorinated 1,4-phenylen, Cyc trans- 1,4- cyclohexylene or 1,4-cyclohexenylen, Pyr pyrimidine-2,5- diyl or pyridine-2,5-diyl, Dio l,3-dioxane-2,5-diyl and G 2-(trans-l,4-cyclohexyl)-ethyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl or l,3-dioxane-2,5-diyl.

One of the residues L and U is preferably Cyc, Phe or ζ r. 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 ϋ 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 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 ϋ 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) R¹ 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 compounds of formulae 1, 2, 3, 4 and 5 (subgroup 2) R" denotes -CN, -CF₃, -F, -Cl or -NCS while R¹ 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, 4 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 from 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 % subgroup 2: 10 to 50 %, in particular 10 to 50 %

In these 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 %. 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, advantageously at 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 literature

(H. Kelker/R. Hatz, Handbook of Liquid Crystals, Verlag Chemie, Weinhei , 1980). For example, it is possible to add pleochroic dyestuffs to prepare colored guest-host systems or substances for modifying the dielectric aniso- tropy, the viscosity and/or the orientation of the nematic phases.

The following examples are to be construed as merely illustrative and not limitative, m.p. = melting point, cp. = clearing point. In the foregoing and in the fol- lowing all parts and percentages are by weight and the temperatures are set forth in degrees Celsius. "Custo¬ mary work-up" means that water is added, the mixture is extracted with ethylene chloride, the organic phase is seperated off, dried and evaporated, and the product is purified by crystallization and/or chromatograph . 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 being embraced by 2 of these symbols denotes the tem¬ perature of phase change.

Examples for production

Example 1

Hydrogenation of l-(4'-n-propylbicyclohexyl)-2-(2- fluoro-4-trifluoromethylphenyl)-eth€ne yields after customary work up 1-(4*-n-propylbicyclohexyl)-2-(2- fluoro-4-trifluoromethylphenyl)-ethane, C 79.5 N 104 I.

Examples 2 to 11

The following compounds are obtained analogously:

(2) l-(4'-n-pentylbicyclohexyl)-2-(2-fluoro-4-trifluoro- methylphenyl)-ethane

(3) 1-(4'-n-pentylbicyclohexyl)-2-(2-fluoro-4-trifluoro- methoxyphenyl)-ethane

(4) l-(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 (8) 1-(4^»-n-pentylbicyclohexyl)-2-(2-fluoro-4-difluoro- methoxyphenyl)-ethane

(9) 1-(4'-n-pentylbicyclohexyl)-2-(2,4-difluorophenyl)- ethane (10) l-(4^,-n-butylbicyclohexyl)-2-(2,4-difluorophenyl)- ethane (11) 1-(4^f-n-propylbicyclohexyl)-2-(2 ,4-difluorophenyl)- ethane

Examples of compositions

Example A

A liquid crystalline medium consisting of

15 % of l-(4'-n-propylbicyclohexyl)-2-(2-fluoro-4-tri- fluoromethylphenyl)-ethane and 85 % of a mixture containing 2 - % 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.

Claims

1. Fluorinated cyclohexyl derivatives of formula I

m is 0 or 1, and

X is F, -CF , -OCF._J or -OCHF,

Cyclohexyl derivatives of claim 1, wherein X denotes

-OCF₃ or -OCHF₂.

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 R 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 claim 6.