JPH02501071A - Fluorinated oligophenyl compounds and their use in liquid crystal materials - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Fluorine oligophenyl compound and The number on the liquid crystal f The present invention relates to laterally fluorinated oligophenyl compounds and their It relates to the use of the compound in liquid crystal materials.

Liquid crystal materials are well known, and these are generally nematic (N ) or smectic, especially chiral smectic C(S;’) or It utilizes the electro-optical switching physical properties of smectites. These materials are , widely used in electro-optic display devices.

Such materials generally contain compounds selected such that the mixture exhibits the desired properties. It is a mixture of things. In particular, this property encompasses the following properties: white) suitable liquid crystal phase, e.g. s, s, s'', Sl, CC A wide temperature range over which the 57 or N phase persists, preferably at room temperature (approximately 20°C ).

(ii) low viscosity (■) Easy to manufacture (b) Good electro-optical response (v) S (long pitch and high spontaneity in the case of compounds or mixtures exhibiting phases) One or more types for forming a helical chiral phase having polarization efficiency Ps. With the above optically active compound, that is, a compound having an asymmetrically substituted carbon atom, Miscible, the compound or mixture exhibits an SA phase at a higher temperature than its S phase In this case, this S at the t-pole of the liquid crystal electro-optical device. This helps align the phases. It is also useful.

Fluorinated terphenyl compounds for use in liquid crystal materials are known. parable Ba: EP-A-8430494,3 contains the general formula (wherein R1 and R2 are independently , alkyl or alkoxy) The production of products and the use of this compound in nematic liquid crystal materials are described. Ru. GB-A-8725928 and 107'07890 contain these monomers. The use of fluorinated terphenyl compounds in S mixtures is described.

EP-^-0084194 is a terphenyl compound that is laterally difluorinated. Contains descriptions that refer to substances in general and conceptual terms, and also includes descriptions of compounds: Theoretically, it is covered for use in nematic mixtures.

PCT/’EP1117z’oO, which had not been published at the time of filing the patent application for the present invention. 515 is a conceptual general term that is considered to include difluorophenyl compounds. contains formulas, and also specifically used for nematic liquid crystal mixtures, especially Two types of compounds: It also mentions.

The present invention seeks to identify another class of useful difluorinated terphenyl compounds. and especially try to study their use in smectic liquid crystal materials. It is something that

According to the present invention, biphenyl, p-terphenyl or p-quar -Fluorinated derivatives of terphenyl are provided: [wherein a is 0 or 1, and where the terminal substituents R1, R2 and R3 are each independently an alkyl group each having up to 15 C atoms or are alkenyl groups, and these groups are optionally substituted by CM or at least one may be substituted with a halogen atom, and one C present in these groups H2 group or two or more non-adjacent CH2 groups are -o-, -s-, -co-, -o-co-.

Even if replaced by -CO-O-5-o-co-o- or -C=C- Often one of the radicals R1 and R2 may also represent a radical of the formula I can do it, Any one of the following pair of lateral substituents are both fluorine: (A , B), (C, D), ([1, E), (C, E), (a, C), (D, J), (D, K), (A, C), (C, J), (C', Do), (0 °, E), (Do, A), (C', E), (C', A) , (Do, J゛), (0°, Ni゛), (C', J'), (B, G), (A, G), all other lateral substituents are hydrogen or fluorine], The preferred structures described below are among others useful in liquid crystal mixtures and (also ) is based on its ease of manufacture.

A preferred general structure of the difluorinated terphenyl compound of formula I is the subformula Corresponds to the structure shown by I, 1 to J, 6: A preferred general structure of the trifluorinated terphenyl compound represented by formula 1 is that the moiety Corresponds to the formulas I, 7 to I, 12: In formula I, the smectic C phase containing the corresponding compound where a is 0 is shown. A particularly preferred composition is a difluorinated biphenyl compound of formula 1 (a=0 ) corresponds to the structures shown in sub-formulas 1.13 to I, 19. two In the following description, for the sake of brevity, Phe is assumed to be 1,4.

The compound of formula 1 is a liquid crystal mixture, preferably a twisted cell principle, a guest- Display fluids based on host effects, effects of aligned phase deformation or effects of dynamic scattering It can be used as a component of crystalline mixtures. Negative anisotropy of permittivity [Δε=ε, l - ε< (where εJ/ represents the dielectric constant parallel to the axis of the molecule, and ε The compound represented by formula 1 has the dielectric constant perpendicular to this axis) are aligned perpendicular to the applied electric field.

This effect has been known for a long time, and is used in various liquid crystal display devices, such as the dynamic scattering effect. or the effect of the deformation of the aligned phase, or the effect of the guest-host interaction. It is used to adjust the optical transparency of the display elements used.

EC8 effect (air-controlled birefringence) or DAP effect (deformation of aligned phase) A by H, F, 5chieckel and Fahre-nschon. ppl, Phys, Lett, (1971), p. 3912. .

J, Robert and F, CIerc paper [311180, Digest, Te-chn, Papers (1980), p. 80], the ECB effect For use in highly informative display devices, the liquid crystal phase has an elastic constant of a/Ks. with large numerical values, large optical anisotropy values Δn and −0,5 to −5,0 It has been shown that it must have an anisotropy value.

Electro-optic display elements based on the ECB effect exhibit homeotropic alignment, which is This means that the liquid crystal phase has negative dielectric anisotropy.

The to-phase used in electro-optic display elements based on this effect satisfies many requirements. These must have chemical stability against humidity and air, heat, and infrared radiation. , physical stability against visible and ultraviolet radiation, and alternating and direct current electric fields. It must have physical stability against

Furthermore, it can be used industrially. The liquid crystal membrane is applied to the phase at an appropriate temperature range. and low viscosity are required.

However, a suitable membrane range, high a/' value of 1, and high optical anisotropy There is a great need for liquid crystal phases with Δn, negative dielectric anisotropy and high stability. There is.

In another important embodiment of the present invention, the compound of formula 1 is chirally chiral. It is particularly suitable as a component of the dissolved smectic phase.

There is one or more chirally tilted smectic liquid crystal phases with ferroelectric properties. is a chiral compound suitable for substrate mixtures exhibiting two or more tilted smectic phases. It can be prepared by adding doping agents [[, ^, Veres Ho1. Cryst, Liq, Cryst, 89.327 pages ( 1982); J, Physique 44- by HoR, Brand et al. (Iett, ), page L-771 (1983)].

Such a phase was disclosed by C1ark and Lagerwa I+5 It can be used as a dielectric material for displays based on srtc-chikunoroshii. [N, A, CIark and S, T.

Appl, Phys, Lett, 3G, 889 pages by Lagerwall ( 1980); U.S. Pat. No. 4,367.924].

The object of the invention is to obtain fluorinated oligonucleotides of formula 1 suitable as components of liquid crystal mixtures. The goal is to discover phenyl compounds. In particular, using these compounds Thus, preparing liquid crystal mixtures with a wide membrane range and relatively low viscosity can do.

Furthermore, the compound of formula I has a chirally tilted smectic liquid crystal phase. Suitable as an ingredient.

The compounds of formula I have a wide range of uses. These compounds select substituents be used as a substrate constituting up to 50% of the liquid crystal mixture by Can be done. However, the compound of formula 1 can also be obtained from other types of compounds. dielectric anisotropy and/or optical anisotropy of such dielectrics. orientation and/or viscosity and/or spontaneous polarization and/or ) Menface range and/or tilt angle and/or pitch The compound of formula 1 which can affect the liquid crystal dielectric It is also suitable as an intermediate for producing other materials that are useful as components of.

The compounds of formula I are colorless in pure form. These compounds are chemicals, Very stable to heat and light.

Accordingly, the present invention relates to compounds of formula 1, in which a is 1, particularly compounds of formula I, 1- Regarding the compound represented by I, 6.

Furthermore, the present invention relates to compounds of the following formula 1°: [In the formula, A1 and A2 are each independently a 1.4-) unicine group; The group may be optionally substituted with 1 to 4 fluorines, R1 and R'11 each independently have up to 15 C atoms each an alkyl or alkenyl group, which groups are optionally substituted by CN and may be substituted by at least one halogen atom, and these One CH, group or two or more non-adjacent CH2 groups present in the group are -o -, -s-, -co-5-O-CO-.

Even if replaced by -CO-O-5-o-co-o- or -C=C- often, m is O or 1, n is 1.2 or 3, and The sum of m and n is 2 or 3].

Furthermore, the present invention contains at least two types of liquid crystal components, at least of which A liquid crystal composition, one of which is a compound represented by formula 1 (wherein a is 1); , in which at least one component is represented by formula 1 (in the formula, a represents O or 1) The present invention relates to a liquid crystal composition that exhibits a smectic C phase, which is a compound that exhibits a smectic C phase.

Furthermore, the present invention relates to a liquid crystal display element containing such a composition.

Throughout the description of this specification, R1, R2, R 3, A1, A2, m and n shall have the above meanings.

Therefore, the compound represented by formula I has three rings represented by sub-formulas Ia to Id below. Preferred compound having: R'-Phe-Phe-PheF2-R2IaR'J R'-PheF-Phe-PheF-R2 from he-PheFt-Phe-R2 IcR”-PheF-PheF-Phe-R2I d In the following subformulas Ie to Ij Compounds with four rings shown: R'-Phe-Phe-Phe-PheF2-R2I 6R'-Phe-P he-PheFz -Phe-R' I 1R1-PheF-Phe-Phe- PheF-R2I QR”-PheF-Phe-PheF-Phe-R2 engineering hR "-PheF-PheF-Phe-Phe-R' IiR'-Phe-PheF -PheF-Phe-R”　Ij and two rings represented by the following subformula Ik Compounds with: R''-PheF2-Phe-R2IB.

Throughout this specification, R1 and R2 are preferably alkyl or alkoxy In the compound represented by formula I°, A1 and A2 are Phe, P heF and PheFi. Preferably, there is more than one compound of formula 1°. It does not have many pheF2 groups.

n is preferably 1.2 or 3, especially 1.

m is preferably 0.

Throughout the specification, R1 and R2 are each preferably from 1 to 1 C atoms. Preferably those having 3, especially 3 to 12 C atoms represent alkyl.

In formula I, R1, R2 and R3 have 1 to 7 C atoms, preferably 1 to 7 C atoms. The corresponding compound having 5 atoms is suitable for the liquid crystal phase used in displays based on the ECB effect. Particularly suitable.

In formula 1, R1, R2 and R3 have 2 to 15 C atoms, preferably 2 C atoms Corresponding compounds having ~12 C atoms, especially 3 to 9 C atoms, are liquids exhibiting ferroelectric properties. In groups R1, R2 and R3 suitable for the crystal phase, one or two CH2 - group is -o-, -s-, -co-5-O-CO-1-CO-O-1-o-co- It can be replaced by o- or -02C-.

Preferably there is only one CH, group, particularly preferably -o-, -o-co-1- Replaced by CO-O- or -CmiC-.

R1, R2 and R3 are each an alkyl group, and one of the groups present in this group When the CHt group may be replaced by -0- (alkoxy or oxy saalkyl), or two non-adjacent CH2 groups replaced by 10- (alkoxyalkoxy or dioxaalkyl). These groups can be straight-chain or branched. Preferably, this group is directly It is chain-like and has 2.3.4.5.6.7.8.9 or 10 C atoms, so Preferably ethyl, propyl, butyl, pentyl, hexyl, heptyl, ethyl, cutyl, nonyl or decyl, ethoxy, propoxy, butoxy, pentoxy, Hexoxy, heptoxy, tunoxy, decyloxy, and also methyl, undecyloxy, Syl, dodecyl, tridecyl, tetradecyl, methoxy, undecyloxy, do Decyloxy, tridecyloxy or tetradecyloxy.

Oxaalkyl is preferably linear 2-oxapropyl (=methoxymethyl) , 2-(=ethoxymethyl) or 3-oxabutyl (=2-methoxyethyl) , 2-13- or 4-oxapentyl, 2-13-14- or 5-oxahe xyl, 2-13-14-55- or 6-oxaheptyl, 2-13-14- 55-16- or 7-oxaoctyl, 2-53-14-15-16-17- or 8-oxanonyl, 2-13-14-15-16-17-18- or 9 -Oxadecyl, 1,3-dioxabutyl (=methoxymethoxy), 1.3 -51.4-22.4-dioxapentyl, 1.3-1.4-11.5-12. 4-12.5-or 3.5-dioxahexyl, 1.3-51,4-11,5 -11,6-52,4-12.5-52.6-13.5-53.6- or 4. 6-dioxahebutyl.

R1, R2 and R3 are each an alkyl group, and one group present in this group When the CH2 group of is replaced by -S-, this thiaalkyl group directly It can be linear or branched. Preferably, this group is linear; 2-thiapropyl, 2- or 3-thiabutyl, 2-13- or 4-thiapene thyl, 2-13-54- or 5-thiahexyl, 2-13-14-15- or is 1 tyl to 6-thia, 2-53-14-15-16- or 7-thiaoctyl, 2-13-14-55-16-57- or 8-thyanonyl or 2-13- 14-15-16-57-18- or 9-thiadecyl.

Among the thialkyl groups, the ring Phe, PheF or A group in which the CH2 group adjacent to PMFt is replaced by -S- is preferred, Therefore, this group includes methylthio, ethylthio, propylthio, butylthio, and pentylthio. ruthio, hexylthio, heptylthio, octylthio, nonylthio or decyl Represents thio.

When R1, R2 and R3 are each an alkenyl group, this group is a linear Or it can be branched.

Preferably, this group is linear and has 2 to 10 C atoms. Therefore, this The group is vinyl, prop-1-5 or prop-1-2-enyl, boudo-1-52- or is boudo-3-enyl, bent-1-12-13- or bent-4-enyl, xy-1-12-13-14- or hex-5-enyl, hegt-1-12- 13-54-15- or hebdo-6-enyl, oct-1-12-13-14 -15-56- or oct-7-enyl, non-1-12-53-24-15 -16-17- or non-8-enyl, dec-1-12-13-14-25- 16-17-18- or dec-9-enyl.

Rs, R'x and R3 are each an alkyl group, and 1 present in this group When CH2 groups are replaced by 10-CO- or -CO-0- In addition, this group can be straight-chain or branched. Preferably this group is I[! It is monomorphic and has 2 to 6 C atoms. Therefore, this group is preferably a Cetyloxy, propionyloxy, butyryloxy, pentanoyloxy, xanoyloxy, acetyloxymethyl, 10 pionyloxymethyl, butyryl oxymethyl, pentanoyloxymethyl, 2-acetyloxyethyl, 2- Propionyloxyethyl, 2-butyryloxyethyl, 3-acetyloxypropylene Lopyl, 3-10 pionyloxy 10 pyr, 4-acetyloxybutyl, methoxy Cycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl pentoxycarbonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl methyl, propoxycarbonylmethyl, butoxycarbonylmethyl, 2-(methoxycarbonylmethyl) cycarbonyl)ethyl, 2-(ethoxycarbonyl)ethyl, 2-(10boxy carbonyl)ethyl, 3-(methoxycarbonyl)propyl, 3-(ethoxycarbonyl)ethyl carbonyl)propyl or 4-(methoxycarbonyl)butyl.

Compounds of formula I having branched terminal groups R1, R2 and R3 are This may be important in some cases, as they have improved solubility in conventional liquid crystal substrates. However, if these are optically active, chiral doping This is particularly important in terms of quality. This type of smectate compound is used for ferroelectric materials. Suitable as an ingredient.

Branched groups of this type generally have at most one chain branch. Preferred branched chain The radical R], R2 or R3 is in-10vir, 2-butyl (=1-methylpropyl ), isobutyl (=2-methyl 10 pils), 2-methylbutyl, isobentyl 3-methylbutyl), 2-methylpentyl, 3-methylpentyl, 2-ethylh xyl, 2-propylpentyl, in-10boxy, 2-methylpropoxy, 2- Methylbutoxy, 3-methylbutoxy, 2-methylpentoxy, 3-methylpen Toxy, 2-ethylhexoxy, 1-methylhexoxy, l-methylhexoxy , 2-oxa-3-methylbutyl, 3-oxa-4-methylpentyl, 4-methy hexyl, 2-nonyl, 2-decyl, 2-dodecyl, 6-methyloctoxy, 6-methyloctanoyloxy, 5-methyl to 1-tyloxycarbonyl, 2-methyl Tylbutyryloxy, 3-methylvaleryloxy, 4-methylhexanoyloxy 2-chloropropionyloxy, 2-chloro-3-methylbutyryloxy, 2-chloro-4-methylvaleryloxy, 2-chloro-3-methylvaleryloxy cy, 2-methyl-3-oxapentyl, 2-methyl-3-oxahexyl, 2- Fluoro-3-methylvaleryloxy, 2-fluoro-3-methylbutoxy Ru.

R1, R11 and R3 are each an alkyl group, and 2 present in this group or three or more CH2 groups replaced by 10- and/or -CO-0- When substituted, this group can be linear or branched. . Preferably, this radical is branched and has 3 to 12 C atoms. Therefore, This group is preferably 2,2- and sucarboxymethyl, Ethyl, 3,3-bis-carboxy-propyl, 4,4-bis-carboxy-bu chill, 5.5- and sucarboxybentyl, 6.6- and sucarboxyhexyl sil, 7,7- and sucarboxyhbutyl, 8,8- and sucarboxyoc Chil, 9.9- and sucarboxynonyl, 10.10-bis-carboxy-de sil, bis-(methoxycarbonyl)-methyl, 2,2-bis-(methoxycarbonyl) carbonyl)-ethyl, 3,3-bis-(methoxycarbonyl)-10biru, 4,4 -bis-(methoxycarbonyl)-butyl, 5.5-bis-(methoxycarbonyl)-butyl )-pentyl, 6,6-bis-(methoxycarbonyl)-hexyl, 7.7- Bis-(methoxycarbonyl)-hebutyl, 8.8-bis-(methoxycarbonyl) )-octyl, bis-(ethoxycarbonyl)-methyl, 2,2-bis-(ethoxycarbonyl)-octyl, toxycarbonyl)-ethyl, 3,3-bis-(ethoxycarbonyl)-10pi 4,4-bis-(ethoxycarbonyl)-butyl, 5,5-bis-(ethoxycarbonyl)-butyl, cycarbonyl)-pentyl.

In formula I, the terminal groups R1, R2 and/or Ra are suitable for polycondensation reactions. The corresponding compounds of formula 1 are useful in the preparation of liquid crystal polycondensates. It includes both racemic and optically paired forms of compounds, and mixtures thereof.

The compound represented by formula 1 is described in the literature [e.g. Het by Houben-Weyl. Hoden der 0roanischen Cheieie (Georo-T published in standard academic books such as hieIIe Publishers, St. in particular by methods known per se, such as those suitable for the reactions mentioned. Produced under known reaction conditions. This is known per se and will be explained in detail here. Variants not mentioned can also be used in this case.

If desired, starting compounds can also be processed immediately without isolating them from the reaction mixture. and react with each other to produce the compound represented by formula 1 in situ. The compound represented by formula I°, which can also be It can be produced from lobenzene.

This compound was prepared by the method of H1^, Roe [J, Chen, Soc, CheI.

C0II11.22.582 (1965)] and then and react with the corresponding electronic reactant.

This series of reactions involved the 1-substituted-2,3-difluoroben obtained in this way. You can do this twice against Zen. In this way, 1 as shown in equation 1, 4-disubstituted-2,3-difluorobenzene derivatives can be obtained.

1.2-difluorobenzene or 1-substituted-2,3-difluorobenzene is For example, diethyl ether, tetrahydrofuran, dimethoxyethane, Ethers such as tert, -butyl methyl ether or dioxane is a hydrocarbon such as hexane, heptane, cyclohexane, benzene, toluene optionally in an inert solvent such as or a mixture of these solvents, e.g. tramethylethylenediamine (THEOA), hexamethylphosphoric acid triamide ( HHPTA) or N,N-dimethylpropylene-urea ([1NPtl) complexing agents such as phenyllithium, n-5 sec-1 or ter Organometallic reagents such as t-butyllithium, lithium tetramethylpiperidinidium The reaction is carried out at a temperature of -120°C to +50°C, preferably -78°C to 0°C.

2. The 3-difluorophenyl lithium compound has a temperature of -120°C to 0°C, preferably 0°C. For example, an ester, anhydride or carboxylic acid halide with the corresponding electronic reactant at °C. hydrogen oxide, halogen formate, or carbon dioxide. Particularly suitable electronic reactions The agent is a derivative of cyclohexanone.

In the case of reaction with aliphatic halides, lithium derivatives are The potassium derivative must undergo metal exchange at -80°C to -120°C using No.

In the case of reactions with aromatic halides, lithium derivatives can be used, for example, in transition metal catalysts. Gold on anine-, boron- or titanium-derivatives suitable for the cross-linking reaction below. exchange attributes.

The terphenyl compound represented by formula 1 is illustrated in FIGS. 1 to 8 of the accompanying drawings, for example. 0 which can be manufactured using the general formula F#11-10 shown herein Here, the case where RL and R2 are alkyl or alkoxy is exemplified. However, perfluoroalkyl congeners or perfluoroalkoxy congeners are It is understood that it can be manufactured on the road. Other methods for producing these compounds are known to those skilled in the art. In Equation 1, it is clear that the pair (D, ni) or (C, J) Corresponding terphenyl compounds in which both fluorine atoms are Raw material difluorophenol of Route 9 or known 1,3-difluoro-2-amide phenyl phenol and this precursor compound, for example, the known phenylboronic acid. Using the route of coupling these rings via the correspondingly 4-substituted It can be produced by adding a phenyl ring.

Difluorobiphenyl compounds of formula I can be prepared by a modification of routes 1 to 9. Coupling various intermediate compounds produced by these routes with phenyl compounds. For example, it can be produced as follows: (1F) (5B) (5A) (5A) (5B) (8C) Trifluoroterphenyl compounds can also be prepared e.g. by a modification of Routes 1-9. By coupling the resulting intermediates, e.g. Can be manufactured: (6C) Compounds of formula I often exhibit nematic properties that persist over a wide temperature range. It exhibits a smectic or smectic phase and is a useful component of liquid crystal mixtures.

Therefore, according to a second aspect of the invention, a mixture of compounds and of these compounds At least one of them is p-bee, p-ter- or ρ-quar as shown in formula 1. A terphenyl compound, preferably a compound selected from sub-formulas 1, 1 to 1, and 19. Certain liquid crystal materials are provided.

The liquid crystal phase according to the present invention consists of 2 to 25 components, preferably 3 to 15 components; At least one component is a compound of formula I.

The other ingredients are preferably nematic, smectic, nematogenic or sulfuric. Mectogenic substances, especially azoxybenzene compounds, benzylideneaniline compounds compound, biphenyl compound, p-terphenyl compound, phenyl or cyclohexy Rubenzoate compounds, phenyl or cyclohexyl cyclohexane carboxy Sylate compounds, phenylcyclohexane compounds, cyclohexyl biphenylation compound, cyclohexylcyclohexane compound, cyclohexylnaphthalene compound , 1.4-bis-cyclohexylbenzene compound, 4.4°- and sucyclohexylbenzene Silbiphenyl compounds, phenyl- or cyclohexylpyrimidine compounds, phenyl- or cyclohexyldithiane compounds, phenyl- or cyclohexy dioxane compounds, 1,2- and suphenylethane compounds, 1,2-bis-siloxane compounds, chlorohexylethane compound, 1-phenyl-2-cyclohexylethane compound, Optionally halogenated stilbene compounds, benzylphenyl ethers From the known substances of the group of compounds, tolan compounds and substituted cinnamic acid compounds selected.

Important compounds that can be used as components of the liquid crystal mixture according to the invention are of the following formula: ■ Characteristics that can be shown by [wherein and E are 1,4-disubstituted benzene, respectively] or cyclohexane ring, 1,4-disubstituted 1-cyanocyclohexane ring, 4, 4°-disubstituted biphenyl, phenylcyclohexyl or bicyclohexyl, 2,5-di-substituted pyrimidine, pyridine and 1,3-dioxane ring, 2,6-di-substituted pyrimidine, pyridine and 1,3-dioxane ring, Substituted naphthalenes, di- and tetrahydronaphthalenes, quinazolines and tetra A non-convertible or laterally fluorinated compound selected from the group including hydroquinazoline is a carbocyclic or heterocyclic ring system substituted with cyanogen, and G is -CH= CH-, -CH=CY-, -CmiC-1-co-o-, -co-s-.

-CH=N-1-N(0)=N-1-CH=N(0)-, -CH, -C)I2- , -CH2-0-1-CH2-5-, -COO-Phe-Coo- or C-C Alkyl, alkoxy, alkanoyloxy, alkoxy, which is a single bond and has cycarbonyl or alkoxycarbonyloxy, present in this group, One CH2 group not in va contact with oxygen is 10-+'-CH-CH- or 10 20- can be replaced by h, or these radicals R° and radicals One of R" is also one CM, -NO2, -CFa, -NC5, -F, -C j or −Br].

In most of these compounds, R'' and R'' are mutually exclusive, and these groups One of them is usually an alkyl or alkoxy group. However, the suggestion A variety of other substituents listed may also be used.

A number of such materials or mixtures thereof are commercially available. All of these substances The parts can be manufactured by methods known from the literature.

The liquid-crystalline phases according to the invention are prepared in a manner customary per se.

Generally, the components are dissolved in each other, preferably at elevated temperatures.

The liquid-crystalline phase according to the invention can be improved by using suitable additives. Can be modified for use with all types of liquid crystal display elements shown. Wear.

Such additives are known to those skilled in the art and are described in detail in the literature.

For example, to improve conductivity, conductive salts, preferably ethyl-dimethyl- Dodecyl-ammonium 4-hexyloxybenzoate, tetrabutylammonium Complex salts of nium tetraphenyl boronate or crown ether [this compound For example, 1. Ho1. by Haller et al. Cryst, Lia, Cryst, Vol. 24, pp. 249-258 (1973)] added. dichroic dyes can be added to create a colored guest-host system, or substances to change the dielectric anisotropy, viscosity and/or orientation of the nematic phase Can be added. Such substances are described, for example, in West German Published Patent Application No. 2,2 No. 09.127, No. 2,240,863, No. 2,321,632, No. No. 2,338,281, No. 2,450,088, No. 2,637,430 , No. 2,853.728 and No. 2,902,177. .

When the liquid crystal material is a nematic liquid crystal material, other components of this material are nematic. A wide variety of compounds are known to be useful components of liquid crystal materials. For example, sub-formulas 2.1 to 2.6 (wherein Ra and Rb are independently alkyl or Alkoxy) can be selected from compounds of the structure type Generally, the nematic liquid crystal material of this aspect of the invention contains up to about 25% by weight of formula 1 Contains a terphenyl compound shown in twisted nematic device (TN), Freedericksz effect device, cholesteric-nematic phase change effect In the case of the device, the material of the - group effectively binds a compound selected from formulas 2.1 to 2.6. It can contain. If a cholesteric phase is required, the alkyl group R One or both of a and Rb is, for example, a 2-methylbutyl group, It can contain carbon atoms.

The group of terphenyl compounds represented by formula 1 has electrically controlled birefringence (EC B) was found to be useful in liquid crystal materials using the effect. like this In the material, one or more terphenyl compounds represented by formula 1 are used. It contains up to about 50% by weight, typically up to about 25%. Such a mixture of groups is a compound represented by the following sub-formulas 3.1 to 3.6 (wherein Ra and Rb are alkyl or alkoxy) can effectively contain: The biphenyl compounds and monophenyl compounds of formula I are in the S phase. 6 Formula I found to be a useful component of liquid crystal materials using ferroelectric properties The group of terphenyl compounds shown as Therefore, the present invention relates to biphenyl compounds of formula I or or terphenyl compound. liquid showing phases Provide crystal materials. This liquid crystal material is composed entirely of biphenyl compounds represented by formula 1. and (or) consisting of two or more of the following terphenyl compounds. Can be done. One of the components of this mixture must be an asymmetric carbon This component must itself contain the bifurcated atoms of formula 1. phenyl or terphenyl compounds, but preferably formula It is not a compound represented by 1.

In addition to one or more terphenyl compounds of formula I, A mixture having an Sc phase and containing one or more biphenyl compounds is particularly preferred.

Such a mixture is a compound "aJ" represented by the following sub-formulas 4.1 to 4.8 (wherein, Ra and Rb represent alkyl or alkoxy represents 0). Can be done: Ra@-cox (X 怜Rb 4.3 In the compounds represented by formulas 4.1 to 4.8, one 1,4-phenylene group is Optionally substituted by fluorine, preferably fluorine. Preferred fluorinated compounds are those of formulas 4.9 and 4.10 below. It is: The smectic phase according to the invention also includes compounds of formula 1 and formula 4. In addition to compounds that exhibit negative dielectric anisotropy values (Δε≦−2), e.g. This compound of the present invention may contain compounds represented by formulas 5.1 to 5.3 below. In the Sfi fixtures and Sco mixtures of a, formulas I, 1 to I, 6, especially formulas I, 1 The terphenyl compounds represented by ,I,2 and It is a preferable component because it shows the following.

S of this aspect of the invention. The entire material or SF material is a biphenylene of formula I. In the case where the other components do not consist of S. Compounds known to be useful components of c and/or sc liquid crystal materials It is. Useful S'c liquid crystal materials include one of the terphenyl compounds represented by formula 1 or is one type of other compound containing two or more deca-symmetrically substituted carbon atoms, or It can consist of a mixture of two or more types.

In the S1* mixture of this aspect of the invention, R8 and R2 are preferably nematic Those with longer carbon chain lengths than those used in tick materials are preferred; For example, each of these groups preferably contains 5 or more carbon atoms. do. R1 and R2 are preferably n-alkaline in such a mixture. Kyl or n-alkoxy.

S mixtures can be prepared using terphenyl compounds of formula I. The discovery of the benefits of good S. phase and quick switch The rate of conversion is based on the prior art for exclusively nematic or ECB mixtures. This is totally unexpected. Indeed, nematic mixture or ECB mixture In general, there are instructions to exclude compounds that exhibit smectic properties. There is.

The preferred compound containing asymmetric carbon in the Sc material of this aspect of the invention is EP -1-methyl (20Ct") esterification to 1-methyl described in -^-0110299 or WO87107890 or British Patent Application 8729502, 8729503, including one or more compounds having an open group.

No. 86104328, naphthoic acid ester compounds are described in Wo No. 87106577, 14088102390, and the optically active amino acid -086102937 or British Patent No. 1! [Listed in 8620111 has been done.

The following sub-formula 6. ~6.6 (wherein, X represents an alkoxy group or an alkylamino group) , Y represents H, CF, or CH, m is O or 1, and n is 1 or 2 and p is 0 or 1) Particularly preferred substances are: Ra-(Phe)n-Phe-COO-20Ct”e, IRa-(phe) n-Phe-CHzC)12-COO-20Ct rate 6.4Ra-(Phe)n -(COO)m-Phe-(CO)s>-QC(CM)RIR26,6 Formula 6.1 In the compounds shown in ~6.6, one or more groups Phe are fluorine. may be substituted (Ra and Rb are as defined above, Rb is preferably or 01~Can-alkyl, cycloalkyl or branched alkyl .

Ra present in the above formula is preferably 05-Ct2n-alkyl or n-alkyl. oxy, especially n-octyloxy. Rb is preferably methyl or or Rb is preferably a general formula (where a is 0 or an integer from 1 to 6, and b and C are each independently an integer from 1 to 6, preferably less than b or C; one is 1), R1 and R2 each have a different number of carbon atoms or R1 and R2 together are preferably alicyclic Represents a group group, such as a group represented by the formula.

The S5 mixture of this aspect of the invention contains two or three compounds containing asymmetric carbon atoms. When containing more than one species, two or more of these compounds can effectively: have opposite optical characteristics, i.e. (+) and (-) optical rotation or D and and may have stereoisomerism. With this method, helical S copy The length of the rim can be controlled and/or the electrode and liquid of the electro-optical device It can help align with the crystalline material to create a useful SA phase.

- Contains 1 to 30% by weight of one or more pinging substances. of this mixture The remaining part is one or more compounds of formula 1, especially formulas I, 1-I, Compounds represented by 6 or represented by formulas 1, 13 and formulas I, 17 to 19 It can contain compounds such as The total amount is 100% by weight. In other words, Japanese and mixed The compound consists of 1 to 30% by weight of chiral doping substances (one or more types) and the remaining part is a compound represented by formula 1 4.1 to 4.10 or One or more compounds represented by formulas 5.1 to 5.3, and/or or a mixture of other known smectic C components or other suitable additives.

Generally, compounds represented by formulas 4.1 to 4.10 or 5.1 to 5.3 The weight percentage of the compound does not exceed 80% of the mixture.

The liquid crystal material of the invention can be used in liquid crystal electro-optic displays of known structure. .

The present invention is hereby referred to with reference to the accompanying drawings 1 to 8 showing the manufacturing routes 1 to 10 mentioned above. This will be explained by way of example.

Use the following abbreviations: ) = solid crystal N=nematic liquid crystal SA-Smek Tick A LCD Sc=Smectic C liquid crystal 13 Isotropic liquid Example 1 4-n-hexyloxy-4"-n-benzene 2°,5°-difluoro-ρ- Production of terphenyl lA4-n-hexyloxybromobenzene 1-bromohexane (>60 g) A solution in setone (ISOnj) was added to a solution in acetone (60011j) at room temperature. A stirred mixture of 4-bromophenol (71 g) and tcOs (120 g) Add dropwise to the mixture. The stirred mixture was heated for 43 hours (i.e. until Qtc was reacted). Heat to reflux until indicated completion).

The product was extracted twice into ether and the combined ether extracts were dissolved in water, 5% NaOH Wash with aqueous solution and then dry (HQSOa), remove the solvent under reduced pressure and remove the residue. Distill the distillate at bp=100-110°C10. InIIHQ), colorless liquid get.

1 4-n-hexyloxyphenylboronic acid anhydride THF (250nj) Grignard sample prepared from Hg (7.75 g) and IA (72 g) in The proposed solution was mixed with triiso-10-bilborate (109,1 g) under a dry N2 atmosphere. ) in anhydrous THE (40ij) into a stirred, cooled (-78°C) solution of and add. The stirred mixture was allowed to warm to room temperature overnight, then for 1 hour at room temperature. Stir with 10% HCj) (320nj). Product in ether 2 The accumulated ether extracts are washed with water and then dried (Hg5 On), the solvent was removed under reduced pressure to obtain a colorless solid, Imp=80-85<0>C.

N-bromosuccinimide (42 g) in dry CH2Cj2 (180 nj) of 2,5-difluoroaniline (30-96 g) was stirred and cooled (-10 °C ˜0° C.) solution in small portions over 1.5 hours. Stir the mixture at 0°C for 2 hours. Stir. The red solution is washed twice with large amounts of water and then dried (Ho5O a). The solvent was removed under reduced pressure to obtain a red solid, 11D=74N75°C.

ID2.5-difluoro-4-bromobiphenyl dry benzene (200nj) A solution of the IC in the solution was added to a stirred solution of impentyl nitrile (>33,6 g) in dry benzene. Add dropwise to the stirred, cooled (0°C) solution over 1.5 hours with stirring. I can do it. The mixture is heated to reflux for 1.5 hours and then allowed to cool. Aether the product The combined organic layer was extracted twice with water, sodium bicarbonate, 2M @ acid and water. and then drying (HIJSOa), the solvent was removed under reduced pressure and the crude The product is steam distilled to give a brown solid. This product was analyzed by column chromatography. Further purification by Ili (silica gel/dichloromethane) and Ili brown.

A solid with a low melting point is obtained.

4°-pentanoyl-2,5-difluoro-4-bromobiphenyl Grind AjCi's (25.4g) and add dry dichloromethane (120ml). To a stirred, cooled (0 °C) solution of valeroyl chloride (34.9 g) in I can do it. A solution of ID (13.2 g) in dry dichloromethane (120-) Add dropwise over 2 hours at 0°C. The mixture was stirred at room temperature for 48 hours and crushed Pour the separated aqueous layer onto ice/conc. HCJ and wash the separated aqueous layer twice with CHCIt, The combined organic layers are washed with water, NaHCOs, and water, then dried (H QSOa), the solvent was removed under reduced pressure and the resulting dark red oil was distilled under reduced pressure. Ku0. lmllHg, temperature not recorded), resulting in a low melting red-brown solid. The product was further purified by column chromatography (silica gel/'CH2Cb). , a low melting red-brown solid is obtained.

Above 4°-n-pentyl-2,5-difluoro-4-bromobiphenyl Triethylsilane (7.0 g) was dissolved in IB (8 mj) in trifluoroacetic acid (40 mj). , 0 g) added dropwise over 2 hours to a stirred solution of 6 The reaction mixture was stirred at room temperature overnight and then poured into the NaHCOs solution. Ru. The product was extracted twice into ether, the collected ether layers were washed with water, and then (MQSOa).

The solvent is removed under reduced pressure to give an orange-brown oil.

The crude product was distilled under reduced pressure at 110-120°C (short path, 0.011n direction). , a red oil is obtained.

-L94°-n-hexyloxy-4”-n-pentyl-2°,5°-difluoro IB in low-p-terphenylethanol (ISij) (0,9806 g ) was mixed with benzene (20ij) and 2M Na2 under dry fermentation at room temperature. IF (1,25 g) and tetrakis (trif) in COs (20 Ij) Stirred mixture of Palladium(0) (0,1392 g) Add it dropwise. The stirred mixture was heated for 23 hours (i.e., the raw material by Qtc analysis). heat to reflux (90-95°C) until it is confirmed that no material is present). , let the mixture cool and add 30% H2O2 (2a) as needed for 1 hour at room temperature. Stir. The product was extracted twice with ether and the combined organic extracts were washed with brine. Clean, then dry (Hg5Oa), remove the solvent under reduced pressure and evaporate the residue. Lamb chromatography on silica gel 7' petroleum ether (b.

240-60℃)-dichloromethane, 3-1] to obtain a colorless solid. 53. Recrystallize the product from ethanol to obtain colorless plates. ON 118. Office lady example 2 4. Preparation of 4”-di-n-benzene 2°, 5′-difluoro-p-terphenyl Construction and 4-pentanoyl-bromobenzenepentanoyl chloride (50 g), Stirring bromobenzene (1501j) and aluminum chloride (0.2g>, Add dropwise to the cooled (0° C.) mixture. The mixture was stirred at 0 °C for 1 h and 80 Heat for 2 hours at 0.degree. C., allow to cool, then pour into 18% hydrochloric acid. The product is CH Extracted twice in Cl5, the combined organic extracts were washed with water and then steam distilled. to remove chloroform and excess bromobenzene. The product is converted into chloroform. The combined organic phase is washed with water and then dried (H(]5O a) Remove the solvent under reduced pressure and distill the residue to bp 180~ at 2 OamHg. 184° C.) to obtain a colorless solid.

2B4-n-pentylbromobenzene 2A (77,1 g) in diethylene glycol (250 nj), hydrazine ha A mixture of idlate (46.4g) and KOH (590g) was heated at 130°C for 2 hours. Excess hydrazine hydrate was distilled off, and the temperature was raised to 200°C for 2 hours. enhance

The cooled mixture was poured into 18% HCj and the product was extracted twice into ether. , Wash the collected ether extract with water and then dry it (HIJSO4), The solvent was removed under reduced pressure and the residue was distilled to bp 145-148 at 20 niHg. °C) to obtain a colorless liquid (58.1 g, 80%).

Grignard reagent prepared from 2C4-n-pentylphenylboronic acid 2B Boron was prepared using triiso-10-bilborate in a manner similar to that described in IB. Convert to compound.

The product from 2C is combined with the product from IF in a manner similar to that described in IG. 4,4”-di-n-benzene 2°,5°-difluoro-p- Obtain terphenyl, 65. ON 86.0].

Example 3 4-n-hexyloxy-4'-n-pentyl-2,2'-difluoro-p -Production of terphenyl 1Δ 4-n-hexyloxy-2-fluorobromobenzene A solution of 1-bromohexane (9.33g) in acetone (20ij) at room temperature , 4-bromo-3-fluorophenol (9,0 Gg) in acetone (75 mj) ) and potassium carbonate (13.5 g) dropwise. stir The mixture was heated to reflux for 21 hours (i.e. until Qtc analysis indicated the reaction was complete). Let it flow. The product was extracted twice into ether and the combined ether extracts were diluted with water, 1 Wash with 0% sodium hydroxide, water and then dry (14 GlsOa).

The solvent was removed under reduced pressure and the residue was distilled to bp 100-105 at 0.1 miHg. °C), a colorless liquid is obtained.

4-hexyloxy-2-fluorophenylboronic acid A solution of n-butyllithium (10.0M in hexane, 3.30-) was heated with dry N2 Below, stir and cool 3A (9,0 g) in dry THE (70 ml). (−78° C.) solution dropwise. The stirred mixture was heated under these conditions for 2 hours. ．． maintained for 5 hours, then triiso-10 bilbora in dry THF (50ij) A cooled solution of 11.28 g of chloride (11.28 g) is added dropwise at -78°C. Stirred mixture The compound was warmed to room temperature overnight and then treated with 10% HCj (5011j) at room temperature. and stir for 1 hour. The product was extracted twice into ether and the combined ether extracts The effluent was washed with water and then dried (HQSO4), the solvent was removed under reduced pressure and An off-white solid is obtained.

3C4-n-hexyloxy-4''-n-pentyl-2,2''-difluoro The product from -p-terphenyl 3B was converted to 4'- in a manner similar to that described in IG. Coupling with bromo-2-fluoro-4-pentylbiphenyl.

The crude product was purified by column chromatography [silica gel fluorine petroleum fraction (bp = 40~ 60°C)-dichloromethane (3:l), and the resulting colorless solid was purified by evaporation. 45. Recrystallize from nol to obtain colorless waxy platelets. ON 131. 01゜ Example 4 4-n-octyloxy-4'-pentyl-2,2''-difluoro-ρ-ta -Manufacture of phenyl The method of use is the same as that for 3A.

amount: 4-bromo-4-fluorophenol 6.00g 1-bromooctane 7.4 0g K2COz 10.00g The product is distilled under reduced pressure to 0.5 bp = 140-142°C) , a colorless liquid is obtained.

4B4'-n-pentyl-2°-fluorobiphenyl-4-ylboronic acid Use a similar method as for 3B.

amount: 3°-bromo-2-fluoro-4-n-pentylbiphenyl 9.90 g Magnesium 0.871g Tri-isopropyl borate 11.66g Crude yield: 8.85g 4C4-n-octyloxy-4''-pentyl-2,2''-difluoro-p-ta -Phenyl Use the same method as for 1G.

amount: 4A 6.00g 4B 1.75g Tetrakis (triphenylphos) Fin) Palladium (0) 0.2979g product was subjected to column chromatography Further purification to obtain a colorless solid, 42.5 N 121.51° Example 5 4-n-hexyloxy-4''-n-pentyl-3,2''-difluoro-p-ta -Manufacture of phenyl 4-n-hexyloxy-3-fluorophenylboronic acid by the method described in IG and In a similar manner, 4°-bromo-2-fluoro-4-n-pentylbiphenyl and Let it pull.

The crude product was purified by column chromatography [silica gel 7' petroleum fraction (bp = 40~ 60°C) CHzCjt6:l], and the colorless solid obtained was purified by evaporation. Recrystallize from tanol-ethyl acetate (10:1) to obtain colorless plates, K 96.05c105.5N 139.01.

Example 6 4-n-hexyloxy-4”-n-pentyl-2°,3°-difluoro-p- Production of terphenyl 6A 2,3-difluorophenylboronic acid 1,2-difluorobenzene to 3B 6A was converted to 6A with tri-isopropyl borate in a manner similar to that described in Use the same method as for 1G.

amount: 1-bromo-4-pentylbenzene 3.80g6A 3.50g Tetrakis (triphenylphos) fin) Palladium (o) o, esi g Cup that produces biphenyl compounds Pulling was found to be faster for terphenyl compounds, and this reaction Complete within 5 hours.

The crude product was purified by column chromatography [silica gel/petroleum fraction (11p=40~ b A colorless liquid is obtained.

Standan 4°-n-benzene-2,3-difluorobiphenyl-4-ylboronic acid Use a similar method as for 3B.

amount: 6 B 4.00g n-Butyllithium 1.50 ij, 10. ON tree iso 10 bit Ruborate 5.70g 4-rhohexyloxy-4゛-pentyl-2゛ , 3°-difluoro-p-terphenyl Use the same method as for 1G.

amount: Tetrakis (triphenylphos) Fin) Palladium (0) 0.312 g Crude product was subjected to column chromatography [Silica gel fluorocarbon (boiling point 40-60'C) dichloromethane 6:1] The colorless solid obtained was recrystallized from ethanol to produce a colorless plate-like substance. get.

K [email protected]° N149° 1 homologous compound 6E: 4-n-octyloxy-4''-n-pentyl-2°,3゛-p-terphenyl followed a similar route, using 1-bromo-4-octyloxybenzene instead of IB. and manufacture it.

This compound is prepared by the same method as for IB: quantity 2 4-bromophenol 64.54 g Special table 12-501071 (15) 1-bromooctane 60.00g K2COi 103.5 g Colorless liquid, 1) p=145°C 10.1 inh.

For the manufacture of 6E, a method similar to that for 6D is used.゛Quantity 2 1-Bromo-4-octoxybenzene 1.40g6 C1,90g Tetrakis (triphenylphos) Fin) Palladium (0) 0.31Q2g Crude product was subjected to column chromatography [Silica gel fluorocarbon material (bc+: 4G ~ 60℃) CH2Cj! z　 The colorless solid obtained was purified by ethanol-ethyl acetate (4:1). ) to obtain colorless platelets, 4 g, 55C95, IN 141 ．． 5　1゜ Example 7 4,4”-di-n-pentyl-2°,3′-difluoro-p-terphenyl Manufacturing of Use the same method as for 1G.

l: Tetrakis (triphenylphos) Palladium (0) 0.28g The crude product was purified by column chromatography Lica gel/petroleum fraction (bp: 40-60℃) -C) lzcj* 5: 1 ], and the obtained colorless solid was recrystallized from ethanol to obtain a colorless plate. 60 N 120].

Example 8 4-n-hexyloxy-4”-〇-benthyl-2,3-difluoro-terphene Niru's W3Si Day A 2,3-difluorophenol The method used was a modification of H, F, uawtharne [J, Org, Chem .

(1957), Tachi, p. 1001] There is.

amount: 6A 4.40g 10% hydrogen peroxide 30nj Product: Off-white solid, np: 34-36°C.

Godan Same as for 2,3-difluoro-n-hexyloxybenzene 3A use the law.

amount: 8 A 7.00g 1-bromohexane 10.72 g K2COi 17.40g The crude product was distilled to give a colorless liquid (bp 122°C/15nlHQ).

8C4-n-hexyloxy-2,3-difluorophenylboronic acid Use a similar method as for 3B.

amount: 8B IQ, 0g n-Butyllithium 4.70 Ilj, 10.0H triisopropylene in Hemason Lopylborate 17.70 g [4-n-hexyloxy-4”-n-pene] Using a similar method as for thiru-2,3-difluoro-p-terphenyl 1G Ru.

amount: 4-Bromo 4'-pentylbiphenyl 1.40g8C1.50g Tetrakis(triphenylphosphine)palladium(0) 0.2868g The crude product was purified by column chromatography [silica gel/petroleum fraction (bD: 40-60 °C)-CH2Cj23:1], and the resulting colorless solid was purified by ethanol Recrystallized as colorless crystals from alcohol-ethyl acetate (10:1), K 97.5 ° 5c145.5°N 166'].

Example 8b 4-n-octyloxy-4''-n-pentyl-2,3-difluoro-p-ter Manufacture of phenyl This compound uses 1,2-difluoro-3-octoxybenzene instead of 8B. This raw material compound is produced using the same route as 3A. manufactured using a method.

l: 8A 7.00g 1-bromooctane 12.55g KzCOi 17.40g The crude product is distilled at 150°C/'1511118! J) Obtain colorless liquid .

8E4-n-octyloxy-2,3-difluorophenylboronic acid 8E is made using a similar method as for 8C.

amount: 1,2-difluoro-3- Octoxybenzene 7.50g n-Butyllithium 3.10 lIj, 10.0M triiso-10bi Ruborate 11.66 g colorless solid is produced.

8F4-n-octyloxy-4'-n-pentyl-2,3-difluoro-p- Similar method as for terphenyl 8D.

amount: 4-Bromo-41-pentylbiphenyl 1.54g2.3-difluoro-4- octoxy Phenylboronic acid 1.75g Tetrakis (triphenylphos) Fin) Palladium (0) 0.309 g Crude product was subjected to column chromatography [Silica gel/petroleum fraction (bp: 40-b The colorless solid obtained was recrystallized from ethanol-ethyl acetate (4:1), 93.5 Sc144SA14g N159] to obtain colorless crystals.

Example 9 Production of 4.4”-di-n-benzene-2,6-difluoro-ρ-terphenyl 9A 1,3-difluoro-5-(1-hydroxypentyl)-benzene 1-bromo-3,5-difluoro-benze in dry THF (100 IIJ) (50.2 g, 0.26 mol) and magnesium (7.25 g, 0.30 mol) A stirred solution of Grignard reagent prepared from 'M solution of pentanal (19.0 g, 0.22 mol) in dry ether (75ij) Add dropwise. The stirred mixture was heated to reflux for 2 hours, cooled and treated with ammonium chloride. Add a saturated solution of Monium (300 mj). Extract the product into ether 2 times), the collected ether extracts were washed with water and then dried (HgSO<) The solvent was removed under reduced pressure, and the resulting pale orange liquid <51.1 g> was distilled. , a colorless liquid is obtained. A small amount of crude product was collected by column chromatography [silica gel 7' dichloromethane] to give a colorless liquid, b at 0.5+uHg p: 90°C.

9B 1,3-difluoro-5-bent-1-enylbenzene Phosphorous (V) oxide (64.5 g, 0.45 mol) was added to dry pentane (15 mol) at room temperature. Stirred solution of compound 9A (35.0 g - 0.175 mol) in 0.011j) Add to. The mixture was stirred at room temperature overnight and red analysis indicated the absence of starting material. ), then pass.

90 1.3-difluoro-5-pentylbenzene 5% palladium on charcoal (4, 0 g) at room temperature from the above P solution [i.e. compound 9B in pentane (15011j)] ] Add to. The stirred mixture was heated at atmospheric pressure for 4 hours (i.e. GLC analysis Hydrogenate the mixture until it shows the absence of oxidation. most of the pentane Remove under reduced pressure and distill off the last amount of pentane at 38°C.76011118+1) , the residue is then distilled to obtain a colorless liquid, b at 760 mlHg. a: 200℃.

9D 2.6-difluoro-5-pentylphenylboronic acid Solution of n-butyllithium (10.4M in hexane; 2.70 of, 0 ．． 028 mol) was stirred under dry nitrogen and cooled to 90% (- 78° C.) solution dropwise. The stirred mixture was heated under these conditions for 2.5 hours. Tri-isopropylborer in IF (50 iJ) and then dried (10.22 g, 0.054 mol) was added dropwise at -78°C. Add. The stirred mixture was allowed to warm to room temperature overnight, then 10% salt! ( 30mj) for 1 hour. The product was extracted into ether twice) and collected. The collected ether extract was washed with water and then dried (Hg5Oa) to remove the solvent. Removal under reduced pressure gives a colorless solid, np: 95-100<0>C.

9E 3-pentyl-4″-hexyloxy-2,6-difluoro-p-turf phenyl Use the same method as for 1G.

amount: 4-Bromohexoxybiphenyl 1.30g9 D 1.10g Tetrakis (triphenylphos) Fin) Palladium (0) 0.157 g Crude product was subjected to column chromatography basic alumina/'petroleum distillate containing gradually increasing amounts of dichloromethane ( bp: 40-60°C)], and the resulting colorless solid was re-purified from ethanol. Crystallize to obtain a colorless plate-like substance, K62′″ N123″″ 1° Use the same method as for 1G.

amount: 4-Bromo-4°-pentylbiphenyl 1.40g9 D 1.37g Tetrakis (triphenylphos) Fin) Palladium (0) 0.157 g Crude product was subjected to column chromatography [Silica gel/petroleum fraction (bp: 40-60°C)-c++, c12.1: 1 ] to obtain a colorless liquid containing solids. Separate solids from P and distillate into petroleum distillate. (bp: 40-60°C). The solvent is removed under reduced pressure to obtain a colorless liquid, By using Kugelrohr distillation equipment, two types of impurities are removed, The obtained colorless solid is recrystallized from ethanol to obtain colorless crystals.

50＠N 82°I, Example 10 4.4"-di-n-alkyl-2",3"-difluoro-p-terphenyl compound manufacturing of things 4-n-alkyl-1-(2,3-difluorophenyl)-cyclohexy- 1-ene compound n-butyllithium 0.3 mol and n-hexane (18811j ), 1,2-difluorobenzene (0.3 mol), tetrahydrofurobenzene (0.3 mol), Ran (THE) (600nN) and tetramethylethylenediamine (TH ED^, 0.3 mol) into a cooled (-60" to -70°C) solution. Stir. The mixture was kept for 3 hours and then added with 4-n-pentylcyclohexanone (0,32 mol) and tetrahydrofuran (100 iJ). conventional finish After treatment, the residue was dissolved in toluene (1000IIj) and diluted with Dean Groove for 3 hours with p-toluenesulfonic acid (PTSA) in a Stark trap. cause The solvent was removed under reduced pressure and the residue was distilled to give 4-n-pentyl-1-(2 , 3-fluorophenyl)-cyclohex-1-ene, obtained as a colorless liquid ( bp: 123 @ 10.5 anHg).

Similarly, the following compound is obtained: 4-ethyl-1-(2,3-difluoro phenyl)-cyclohex-1-ene 4-propyl-1-(2,3-difluorophenyl)-cyclohex-1-ene 4-butyl-1-(2,3-difluorophenyl)-cyclohex-1-ene 4-hexyl-1-(2,3-difluorophenyl)-cyclohex-1-ene 4-heptyl-1-(2,3-difluorophenyl)-cyclohex-1-ene 4-octyl-1-(2,3-difluorophenyl)-cyclohexy-1-ene 4-nonyl-1-(2,3-difluorophenyl)-cyclohex-1-ene 4-decyl-1-(2,3-difluorophenyl)-cyclohex-1-ene 4-dodecyl-1-(2,3-difluorophenyl)-cyclohexy-1-ene 4-Ethoxy-1-<2.3-difluorophenyl)-cyclohex-1-ene 4-10boxy-1-(2,3-difluorophenyl)-cyclohexy-1-e hmm 4-Butoxy-1-(2,3-difluorophenyl)-cyclohexy-1-ene 4-Pentoxy-1-(2,3-difluorophenyl)-cyclohexy-1-eth hmm 4-hexoxy-1-(2,3-difluorophenyl)-cyclohexy-1-eth hmm 4-he1toxy-1-(2,3-difluorophenyl)-cyclohexy-1-eth hmm 4-Octoxy-1-(2,3-difluorophenyl)-cyclohexy-1-eth hmm 4-Tunoxy-1-(2,3-difluorophenyl)-cyclohex-1-ene 4-decoxy-1-(2,3-difluorophenyl)-cyclohex-1-ene 4-Undecoxy-1-(2,3-difluorophenyl)-cyclohexy-1- en 10B4-alkyl-2°,3°-difluorobiphenyl compound 4-Pentyl-1-(2,3-difluoro-phenyl)-cyclohexy-1-e 2,3-dichloro-5,6- Add 0.22 mol of dithiatu p-benzoquinone (000) and reflux for 2 hours. . After working up in a customary manner, 2',3'-difluorobiphenyl is obtained, bp: 12S°C/Q, 5siHg.

In the same way, the following compound is obtained: 4-ethyl-2°, 3′-difluorobin Phenyl 4-propyl-2', 3°-difluorobiphenyl 4-butyl-2', 3°-difluorobiphenyl 4-hexyl-2°,3°-difluorobiphenyl 4-hebutyl-2°, 3°-difluorobiphenyl 4-octyl-2', 3°- Difluorobiphenyl 4-nonyl-2°,3°-difluorobiphenyl 4-decyl 2'', 3°-difluorobiphenyl 4-ethoxy-2'', 3°-difluoro biphenyl 4-propoxy-2°,3°-difluorobiphenyl 4-butoxy- 2°,3°-difluorobiphenyl 4-pentoxy-2°,3°-difluorobiphenyl Phenyl 4-hexoxy-2°,3°-difluorobiphenyl 4-hebutoxy- 2',3''-difluorobiphenyl 4-octoxy-2',3'-difluorobiphenyl Phenyl 4-tunoxy-2°, 3′-difluorobiphenyl 4-decoxy-2° , 3″-difluorobiphenyl 4-dodecoxy 2°,3°-difluorobiphenyl Similarly, alkyl-(or alkoxy)-2,3- Using difluorobenzene, the following 4,4°-dialkyl- (or alkoxy) c) Obtain a -2,3-difluorobiphenyl compound: 4-octyloxy-4-benzene-2,3-difluorobiphenyl K 1 4(813,5) 14-octyloxy-4゛-to-1-thyl-2,3-difluoro Robiphenyl 24 (Sc6 5A13 N 23) 14-nonyloxy -4°-decyl-2,3-difluorobiphenyl K 471 4-Ethoxy-4°-pentyl-2,3-difluorobiphenyl K-101 4-pentyloxy-4”-octyloxy-2,3-difluorobiphenyl K 8. O5AI2. ON 18.014-Heptyl-O-C 4゛-Benthru 0.5I to 2.3-difluorobiphenyl 2 to 4-nonyloxy-4°-octyloxy-2,3-difluorobiphenyl 5.0 (Sc11.5) 5A33. ON 34. Odandan 4, 4”-ji Alkyl-2'',3°-difluoro-p-terphenyl compound 0.1 mol of 4-pentyl-2',3'-difluorobiphenyl according to Example 10A. Deprotonation with n-butyllithium in THE/THEDA followed by 4 - Reaction with 0.1 mol of propylcyclohexanone According to Example 10B, DDQ After oxidation with 2 moles of O, 4-pentyl-4'-propyl-2',3'-di Fluoro-p-terphenyl is obtained.

Similarly, the following compound is obtained: 4-ethyl-4"-propyl-2°,3 ゛-difluoro-p-terphenyl 4-propyl-4″-propyl-2°,3°-difluoro-p-terphenyl K　94　N　13314-Butyl-4''-propyl-2゛,3　-difluoro -p-terphenyl 4-pentyl-4″-propyl-2°,3°-difluoro-p-terphenyl 4-hexyl-4゛°-propyl-2°,3°-difluoro-p-terphenyl 4-hebutyl-4゛°-propyl-2°,3°-difluoro-p-terphenyl 4-octyl-4'-propyl-2',3'-difluoro-p-terphenyl 4-nonyl-4-per-propyl-2',3'-difluoro-p-terphenyl 4-decyl-4'-propyl-2',3'-difluoro-p-terphenyl 4-Dodecyl-4°°-propyl-2′,3°-difluoro-p-terphenyl 4-Ethoxy-4°°-propyl-2′,3°-difluoro-p-terphenyl 4-propoxy-4゛°-propyl-2°,3°-difluoro-p-terpheni le 4-Butoxy-4'-propyl-2',3'-difluoro-p-terphenyl 4-Pentoxy-4゛°-propyl-2°,3゛-difluoro-p-terpheni le 4-Hexoxy-4'°-propyl-2',3'-difluoro-p-terpheni le 4-he1toxy-4゛°-propyl-2°,3°-difluoro-ρ-terpheni le 4-octoxy-4°-propyl-2',3'-difluoro-p-terphene Nil 4-Tunoxy-4″°-propyl-2°,3°-difluoro-ρ-terphenyl 4-decoxy-4”-propyl-2゛,3°-difluoro-ρ-terphenyl 4-dodecoxy-4”-propyl-2°,3°-difluoro-p-terphenyl 4-ethyl-4″-pentyl-2°,3°-difluoro-p-terphenyl 4-propyl-4'-pentyl-2',3'-difluoro-p-terphenyl 4-Butyl-4”-pentyl-2゛,3°-difluoro=ρ-terphenyl 4-pentyl-4”-pentyl-2°,3°-difluoro-p-terphenyl 60.0° N 120.0° I4-hexyl-4"-pentyl 2°, 3° -difluoro=P-terphenyl 4-hebutyl-4"-pentyl 2°,3"-difluoro-p-terphenyl K　36.5　(Sc24.0)　8110.514-octyl-4゛-pliers Ru-2°,3°-difluoro-p-terphenyl 4-nonyl-4″-pentyl-2°,3°-difluoro-p-terphenyl 4-decyl-4″-pentyl-2°,3°-difluoro-ρ-terphenyl 4-dodecyl-4'-pentyl-2',3'-difluoro-p-terphenyl 4-Ethoxy-4'-pentyl-2',3'-difluoro-p-terphenyl 4-10boxy-4”-pentyl-2°,3°-difluoro-ρ-terphenyl 4-Butoxy-4゛°-pentyl-2',3'-difluoro-p-terphenyl 4-pentoxy-4°°-pentyl-2°,3°-difluoro-p-terphenylene le 4-hexoxy-4''-pentyl-2',3'-difluoro-p-terphenyl 53.0° to 5c65.5″″N 149.0@14-to 1toxy-4゛ -pentyl-2',3'-difluoro-p-terphenyl 4-octoxy-4”-pentyl-2’,3’-difluoro-p-terpheni 4g in Le, [email protected]°N 141.5''' 14-Thorny-4'' -pentyl-2°,3′-difluoro-p-terphenyl 4-decoxy-4''-pentyl-2',3'-difluoro-p-terphenyl 4-dodecoxy-4”-pentyl-2°,3′-difluoro-p-terphenylene le 4-nonyl-4゛°-hebutyl-2°,3°-difluoronyl-terphenyl K49. O5c77.05A93. ON 108.514-ethyl-4゛-o Cutyl-2゛,3゛-difluoro-ρ-terphenyl 4-propyl-4'-octyl-2',3'-difluoro-p-terphenyl 4-Butyl-4'octyl-2',3'-difluoro-p-terphenyl 4-pentyl-4゛°-octyl-2°,3°-difluoro-p-terphenyl 4-hexyl-4'-octyl-2', 3'-difluoro-p-terphenyl 4-Hebutyl-4"-octyl-2°,3°-difluoro-p-terphenyl 4-octyl-4'-octyl-2',3'-difluoro-p-terphenyl 4-nonyl-4"-octyl-2°,3"-difluoro-p-terphenyl 4-decyl-4”-octyl-2°,3°-difluoro-p-terphenyl 4-dodecyl-4°゛-octyl-2°,3°-difluoro-p-terphenyl 4-ethoxy-4'-octyl-2',3'-difluoro-p-terphenyl 4-Globoxy 4゛°-octyl-2゛, 3°-difluoro-p-terpheni le 4-Butoxy-4'-octyl-2',3'-difluoro-p-terphenyl 4-Pentoxy-4peroctyl-2',3'-difluoro-p-terphenyl 4-Hexoxy-4'-octyl-2',3'-difluoro-p-terphenyl 4-h1toxy-4'-octyl-2',3'-difluoro-p-terphenyl 4-octoxy-4”-octyl-2°,3°-difluoro-p-terphenyl 4-Tunoxy-4゛°-octyl-2°,3°-difluoro-p-terphenyl 4-Acoxy-4″-octyl-2°,3′-difluoro-p-terphenyl 4-dodecoxy4″-octyl-2°,3°-difluoro-p-terphenyl 4-Tunoxy-4゛°-ethoxy-2°,3°-difluoro-p-terphenyl 4-Thecoxy-4′-ethoxy-2°,3′-difluoro-p-terphenyl 4-dodecoxy 4'-ethoxy-2', 3'-difluoro-ρ-terphenyl 4-ethyl-4゛°-to1toxy-2°,3゛-difluoro-p-terphenyl 4-Butyl-4'-to-1toxy-2',3'-difluoro-p-terphenyl 4-hexyl-4゛°-to-1toxy-2°,3°-difluoro-p-terpheni le 4-he1 thyl-4゛°-1toxy-2°,3°-difluoro-p-terpheni le 4-nonyl-4″-hebutoxy-2’,3’-difluoro-p-terphenyl 4-Dodecyl-4゛°-hebutoxy-2°,3°-difluoro-p-terpheni le 4-ethoxy-4“-to-1-toxy-2°,3°-difluoro-p-terphenyl 4-10boxy-4゛-hebutoxy-2°,3°-difluoro-ρ-terpheni le 4-Butoxy-4”-hebutoxy-2°,3°-difluoro-ρ-terphenyl 4-Pentoxy-4N- to 1-toxy-2',3'-difluoro-p-terpheni le 4-hexoxy-4″-heptoxy-2°,3°-difluoro-p-terpheni le 4-hebutoxy-4”-1toxy-2°,3°-difluoro-p-terpheni le 4-octoxy-4″-hebutoxy-2°,3′-difluoro-p-terpheni le 4-Thornoxy-4°゛-to1toxy-2゛,3°-difluoro-p-terpheni le 4-decoxy-4゛°-to-1toxy-2°,3°-difluoro-p-terpheni le 4-Dodecoxy-4"-hebutoxy-2°,3°-difluoro-p-terpheny le Example 11 4.4″゛-di-n-alkyl-2°,3°-difluoro-P-quarterfe nil compound 4-pentyl-2°,3°-difluorobiphenyl (0.1 mol, this compound is prepared according to Example 10B) was deprotonated according to Example 10A and then 4-(p -propylphenyl)-cyclohexanone in Example 10B. Therefore, after oxidizing with 2 moles of DDQ O, 4'-pentyl-4'''-propyl 2',3'-difluoro-p-quarterphenyl is obtained.

In the same way, the following compound is obtained: 4-ethyl-4"-70 pyl-2",3 °-difluoro-p-quarterphenyl 4-propyl-4″°-propyl-2″,3°-difluoro-p-quarterf phenyl 4-Butyl-4゛°゛-propyl-2°,3°-difluoro-p-quaterf phenyl 4-hexyl-4″'-10pyr-2°,3°-difluoro-p-quaterf phenyl 4-hebutyl-4″-propyl-2°, 3″-difluoro-p-quaterf phenyl 4-octyl-4″°-probyl-2′,3°-difluoro-p-quaterf phenyl 4-nonyl-4″°-propyl-2″,3°-difluoro-p-quarterphene Nil 4-decyl-4゛°°-propyl-2゛,3°-difluoro-ρ-quaterf phenyl 4-Dodecyl-4”°-propyl-2゛,3°-difluoro=p-quarterf phenyl 4-Ethoxy-4"°-propyl-2°,3°-difluoro-p-quaterf phenyl 4-10 boxy-4”-propyl-2°, 3”-difluoro-p-quarter phenyl 4-Butoxy-4”-propyl-2°,3°-difluoro-p-quaterphene Nil 4-pentoxy-4”-propyl-2°,3°-difluoro-p-quarter phenyl 4-Hexoxy-4″°-propyl-2″,3°-difluoronyl-quarter phenyl 4-he1-toxy-4″°-propyl-2’,3’-difluoro-p-quarter phenyl 4-octoxy-4”-propyl-2°, 3’-difluoro=p-quarter phenyl 4-Thornoxy-4”-propyl-2°,3°-difluoro-p-quaterf phenyl 4-thekoxy-4°゛°-propyl-2°,3°-difluoro-p-quarter phenyl 4-ethyl-4p-octyl-2,3-difluoro-p-quarterphene Nil 4-propyl-4"-octyl-2',3'-difluoro-p-quaterphene Nil 4-Butyl-4"°-octyl-2°,3°-difluoro-P-quaterphene Nil 4-Benchru 4゛°°-octyl-2°, 3°-difluoro-P-quarter phenyl 4-hexyl-4°°°-octyl-2°,3”-difluoro-p-quarter phenyl 4-hebutyl-4′°-octyl-2°,3°-difluoro-p-quaterf phenyl 4-octyl-4゛°゛-octyl-2°, 3゛-difluoro-p-quarter phenyl 4-nonyl-4″゛°-octyl-2°,3゛-difluoro-p-quaterf phenyl 4-decyl-4”°-octyl-2゛,3°-difluoro-p-quarterfe Nil 4-dodecyl-4′°°-octyl-2°, 3°-difluoro-ρ-quarter phenyl 4-Ethoxy-4°゛°-octyl-2°, 3°-difluoro-ρ-quarter phenyl 4-10boxy-4”-octyl-2°,3°-difluoro-p-quarter phenyl 4-Butoxy-4°゛°-octyl-2°,3°-difluoro-p-quarter phenyl 4-pentoxy-4°“°-octyl-2°,3゛-difluoro-p-quarter -Phenyl 4-hexoxy-4"°-octyl-2",3°-difluoro-p-quarter phenyl 4-hebutoxy-4”°-octyl-2°,3°-difluoro-p-quarter phenyl 4-octoxy-4°°°-octyl-2゛,3°-difluoro-p-quarter -Phenyl 4-Thornoxy-4″°-octyl-2°,3°-difluoro-p-quaterf phenyl 4-decoxy-4”°-octyl-2°,3°-difluoro-p-quaterf phenyl 4-ethyl-4゛°゛-ethoxy-2゛, 3°-difluoro-p-quaterf phenyl 4-10 pyl-4゛°°-ethoxy-2°,3°-difluoro-p-quarter phenyl 4-Butyl-4”°-ethoxy 2°,3°-difluoro-p-quaterphene Nil 4-Benchru 4”-ethoxy 2°, 3”-difluoro-p-quaterf phenyl 4-hexyl-4゛°゛-ethoxy-2゛, 3°-difluoro-p-quarter phenyl 4-Hebutyl-4゛゛-ethoxy-2°,3°-difluoro-p-quaterf phenyl 4-octyl-4″°-ethoxy-2°,3°-difluoro-p-quaterf phenyl 4-nonyl-4″°-ethoxy-2°,3°-difluoro-p-quaterphene Nil 4-decyl-4°“°-ethoxy2°,3°-difluoro-p-quaterf phenyl 4-Dodecyl-4″°-ethoxy-2°,3′-difluoro-P-quaterf phenyl 4-Ethoxy-4°°°-ethoxy-2°,3′-difluoro-p-quarter phenyl 4-propoxy-4″°-ethoxy-2″,3″-difluoro-p-quarter phenyl 4-Butoxy-4゛°°-ethoxy-2°,3°-difluoro-p-quarter phenyl 4-pentoxy-4″-ethoxy-2°,3°-difluoro-p-quarter phenyl 4-hexoxy-4゛°-ethoxy-2°, 3゛-difluoro-p-qua Terphenyl 4-hebutoxy-4″°-ethoxy-2°,3°-difluoro-p-quarter phenyl 4-octoxy-4”°-ethoxy 2°, 3°-difluoro-ρ-quarter phenyl 4-Thornoxy-4°゛°-ethoxy-2°,3°-difluoro-p-quarter phenyl 4-thekoxy-4°゛°-ethoxy-2°,3°-difluoro-p-quarter phenyl 4-ethyl-4″-to 1toxy-2°, 3°-difluoro p-quarterf phenyl 4-propyl-4′°-1toxy-2°,3°-difluoro-p-quarter phenyl 4-Butyl-4゛°-to1toxy-2°,3°-difluoro-p-quaterf phenyl 4-pentyl-4”-heptoxy 2°, 3°-difluoro-p-quarter phenyl 4-hexyl-4″°-1toxy-2″, 3°-difluoro-p-quarter phenyl 4-hebutyl-4”-1toxy-2°,3°-difluoro-p-quaterf phenyl 4-octyl-4"°-hebutoxy-2°,3°-difluoro-p-quarter phenyl 4-nonyl-4″°-1toxy-2°,3°-difluoronyl-quaterf phenyl 4-decyl-4゛゛-to 1toxy-2゛, 3°-difluoro-ρ-quaterf phenyl 4-dodecyl-4′°-1toxy-2′,3°-difluoro-p-quarter phenyl 4-ethoxy-4”°-1 toxy-2°, 3′-difluoro-ρ-quarter phenyl 4-propoxy-4゛°゛-hebutoxy-2°,3°-difluoro-ρ-qua Terphenyl 4-butoxy-4°゛°-to1toxy-2°,3°-difluoro-p-quarter -Phenyl 4-pentoxy-4゛°-to 1toxy-2゛, 3°-difluoro-p-quarter -Phenyl 4-hexoxy-4”-to 1-toxy-2°, 3°-difluoro-ρ-quarter phenyl 4-hebutoxy-4”°-1toxy-2°,3°-difluoro-p-quarter -Phenyl 4-octoxy-4"°-to 1-toxy-2°, 3°-difluoro-p-quarter -Phenyl 4-Thornoxy-4゛°-to 1toxy-2°, 3゛-difluoro-p-quarter phenyl 4-decoxy-4゛°°-to1toxy-2°,3°-difluoro-p-quarter -Phenyl Example 12 Production of 4,4'-dialkyl-2,3-difluoro-p-terphenyl compound 1-(2,3-difluorophenyl)-4-(p-alkylphenyl)-silyl Chlohex-1-ene compound 1. In a mixture of 2-difluorobenzene (0.1 mol) and THE IQOnj At -70°C, n-butyllithium (0,105+tJ) and hexane 60 ij Add the mixture. After stirring for 6 hours, 4-(p-propylphenyl)-silane A mixture of clohexanone (0.1 mol) and THF 50Ilj is added. 2 After stirring for an hour, warm to room temperature and add PTSA and boiling water as described in Example 10A. and then worked up in a conventional manner to obtain l-(difluoro-phenyl)-4-(p-propylene). (ropylphenyl)-cyclohex-1-ene is obtained.

Similarly, the following compound is obtained: 1-(2,3-difluorophenyl)- 4-(p-ethylphenyl)-cyclohex-1-ene 1-(2,3-difluoro lophenyl)-4-(p-butylphenyl)-cyclohex-1-ene 1-(2 ,3-difluorophenyl)-4-(p-pentylphenyl)-cyclohexy- 1-ene 1-(2,3-difluorophenyl)-4-(p-hexylphenyl) -cyclohex-1-ene 1-(2,3-difluorophenyl)-4-(p-he butylphenyl)-cyclohex-1-ene 1-(2,3-difluorophenyl )-4-(p-octylphenyl)-cyclohex-1-ene 1-(2,3-di Fluorophenyl)-4-(p-nonylphenyl)-cyclohex-1-ene 1 -(2,3-difluorophenyl)-4-(p-decylphenyl)-cyclohexyl Sc-1-ene 1-(2,3-difluorophenyl)-4-<p-dodecylphenyl )-cyclohex-1-ene 1-(2,3-difluorophenyl)-4-(p -ethoxyphenyl)-cyclohex-1-ene 1-(2,3-difluorophe nyl)-4-(p-pentoxyphenyl)-cyclohex-1-ene 1-(2, 3-difluorophenyl)-4-<p-octoxyphenyl)-cyclohexy- 1-ene 1-(2,3-difluorophenyl)-4-(ρ-dodecylphenyl) -Fuclohex-1-ene 1-<2,3-difluorophenyl)-4-(4-ene tylbiphenyl-4°-yl)-cyclohex-1-ene 1-(2,3-diflu (orophenyl)-4-<4-pentylbiphenyl-4°-yl)-cyclohex Sc-1-ene 1-<2.3-difluorophenyl)-4-(4-octylbife Nyl-4'-yl)-cyclohex-1-ene 1-(2,3-difluorophenylate) )-4-(4-dodecylbiphenyl-4'-yl)-cyclohex-1-ethyl 1-(2,3-difluorophenyl)-4-(4-pentoxybiphenyl-4 °-yl)-cyclohex-1-ene Bean paste 4'-alkyl-2,3-difluoro=ρ-terphenyl compound 1-(2,3-difluorophenyl)-4-(p-70bilphenyl)-cyclo Oxidation of hex-1-ene (0.1 mol) with DDQ (0.2 mol) according to Example 9B do. After working up in a conventional manner, 4"-propyl-2,3-difluoro-ρ- Obtain terphenyl, K 1211.

Similarly, the following compound is obtained: 4″-ethyl-2,3-difluoro-p -terphenyl 4''-butyl-2,3-difluoro=p-terphenyl 4''-pe 2,3-difluoro-p-terphenyl 4°°-hexyl-2,3-di Fluoro-ρ-terphenyl 4”-hebutyl-2,3-difluoro-p-turf phenyl 4°°-octyl-2,3-difluoro-p-terphenyl 4pernonyl -2,3-difluoro-p-terphenyl 4'-decyl-2,3-difluoro- p-terphenyl 4°゛-dodecyl-2,3-difluoro-p-terphenyl 4 °゛-ethoxy-2,3-difluoro-p-terphenyl 4゛°-pentoxy- 2,3-difluoro-ρ-terphenyl 4゛°-octoxy-2,3-difluoro-ρ-terphenyl 4"-dodecyloxy-2,3-difluoro-p-terphenyl 4'°-ethyl-2,3-difluoro-ρ-quarterphenyl 4゛°-pentyl-2,3-difluoro-P-quarterphenyl 4”°-octyl-2,3-difluoro-p-quarterphenyl 4′°°-dodecyl-2,3-difluoro-ρ-quarterphenyl 4”°-pentoxy2,3-difluoro-p-quarterphenyl 4.4”-dialkyl-2,3-difluoro-P-terphenyl compound A solution of n-butyllithium (0.1 mol) in hexane 65IIj was heated to -100°C. and 4°゛-propyl-2,3-difluoro-ρ-terphenyl (0.1 mol) , a mixture of potassium t-butyrate (0.1 mol) and THE 200IIj Add to.

After stirring for 5 minutes at -100°C, bromopentane (0.1 mol) and N,N-di A mixture with methylpropylene urea (0.1 mol, DHPtl) is added. -3 After warming to 0°C and working up in the conventional manner, 4'-propyl-4-pliers -2,3-difluoro-p-terphenyl is obtained.

In the same way, the following compound is obtained: 4"-ethyl-4-pentyl-2.3- difluoro-p-terphenyl 4'-propyl-4-pentyl-2,3-difluoro-p-terphenyl 4゛°-Butyl-4-pentyl-2,3-difluoro-ρ-terphenyl 4'-pentyl-4-pentyl-2,3-difluoro-p-terphenyl 8 0.05c115.5 5A131.5 N 142.04゛°-hexyl-4 -pentyl-2,3-difluoro-ρ-terphenyl 4'-hebutyl-4-pentyl-2,3-difluoro-p-terphenyl 6 5.55c117.0 5A135. ON 136.04°゛-Octyl-4- Pentyl-2,3-difluoronyl-terphenyl 4″-nonyl-4-pentyl-2,3-difluoro-ρ-terphenyl 4"-decyl-4-pentyl-2,3-difluoronyl-terphenyl 4"-dodecyl-4-pentyl-2,3-difluoro-ρ-terphenyl 4"-Ethoxy-4-pentyl-2,3-difluoro-p-terphenyl 4゛°-Pentoxy-4-pentyl-2,3-difluoro-p-terphenyl 4"-hexoxy-4-pentyl-2,3-difluoro-p-terphenyl 100.5 5c156.5 5A166.5N 171.51 4”-octoxy-4-pentyl-2,3-difluoronyl-terphenyl K 87.55c155.5 5A165. ON 165.71 4″-(4-methylhexyl)-4-pentyl-2,3-difluoro-p-ter 71.05c120 for phenyl. ON 12g, 0 1 4″-dodecyloxy-4-pentyl-2,3-difluoro-ρ-terphenyl 4″-Ethyl-4-propyl-2,3-difluoro-P-terphenyl 1 to 4”-propyl-4-propyl-2,3-difluoro-p-terphenyl 33 N 15014'°-Butyl-4-propyl-2,3-difluoro-p- Terphenyl 4”-pentyl-4-propyl-2,3-difluoro-p-terphenyl 4°°-hexyl-4-propyl-2,3-difluoro-p-terphenyl 4″-hebutyl-4-propyl-2,3-difluoro-p-terphenyl 4”-octyl-4-propyl-2,3-difluoro-ρ-terphenyl 4゛°-nonyl-4-propyl-2,3-difluoro-p-terphenyl 4゛°-decyl-4-propyl-2,3-difluoro-p-terphenyl 4°゛-dodecyl-4-propyl-2,3-difluoro-p-terphenyl 4”-nitoxy-4-propyl-2,3-difluoronyl-terphenyl 4°°-Pentoxy-4-propyl-2,3-difluoro-P-terphenyl 4'-Octoxy-4-propyl-2,3-difluoro-ρ-terphenyl 4゛°-dodecyloxy-4-propyl-2,3-difluoro-p-terpheni le 4”-propyl-4-octyl-2,3-difluoro-p-terphenyl 4”-butyl-4-octyl-2,3-difluoro-p-terphenyl 4″-pentyl-4-octyl-2,3-difluoro-p-terphenyl 4'-hexyl-4-octyl-2,3-difluoro-p-terphenyl 4"-hebutyl-4-octyl-2,3-difluoro-p-terphenyl 4'-octyl-4-octyl-2,3-difluoro-P-terphenyl 4-pernonyl-4-octyl-2,3-difluoro-p-terphenyl 4″-decyl-4-octyl-2,3-difluoro-p-terphenyl 4'-dodecyl-4-octyl-2,3-difluoro-p-terphenyl 4″-Ethoxy-4-octyl-2,3-difluoro-p-terphenyl 4°°-pentoxy-4-octyl-2,3-difluoro-ρ-terphenyl Di-octoxy-4-octyl-2,3-difluoro-p-terphenyl 4”-dodecyloxy-4-octyl-2,3-difluoro-p-terphenyl 4″-pentyl-4-hegtyl-2,3-difluoro-p-terphenyl 5 5. OS 105.5 5A130.5 N 135.0■ 4”-propyl-4-nonyl-2,3-difluoro-p-terphenyl K 6 3. OS 84.55A116.5N 129.0 I4"-ethyl-4-de Decyl-2,3-difluoro-p-terphenyl 4”-70 pyl-4-dodecyl-2,3-difluoro-ρ-terphenyl di-butyl-4-dodecyl-2,3-difluoro-p-terphenyl Di-pentyl-4-dodecyl-2,3-difluoro-p-terphenyl 4”-hexyl-4-dodecyl-2,3-difluoro-p-terphenyl 4″-hebutyl-4-dodecyl-2,3-difluoro-p-terphenyl 4”-octyl-4-dodecyl-2,3-difluoro-p-terphenyl 4″-nonyl-4-dodecyl-2,3-difluoro-ρ-terphenyl 4"-decyl-4-dodecyl-2,3-difluoro-p-terphenyl 4”-dodecyl-4-dodecyl-2,3-difluoro-p-terphenyl 4”-ethoxy-4-dodecyl-2,3-difluoro-p-terphenyl 4″-pentoxy-4-dodecyl-2,3-difluoro-ρ-terphenyl 4”-octoxy-4-dodecyl-2,3-difluoro-P-terphenyl 4°゛-dodecyloxy-4-dodecyl-2,3-difluoro-p le 4゛°°-ethyl-4-propyl-2,3-difluoro-p-terphenyl 4″°-pentyl-4-propyl-2,3-difluoronyl-terphenyl 4"°-octyl-4-propyl-2,3-difluoro-p-terphenyl 4”°-dodecyl-4-propyl-2,3-difluoro-p-terphenyl 4″°-pentoxy-4-10 pyl-2,3-difluoro-ρ-terphenyl 4''°-ethyl-4-pentyl-2,3-difluoro-P-terphenyl 4”°-benthyl-4-pentyl-2,3-difluoro-p-terphenyl 4゛°-octyl-4-pentyl-2,3-difluoro-p-terphenyl 4"°-dodecyl-4-benzene-2,3-difluoro-p-terphenyl Di-pentoxy-4-benthyl-2,3-difluoro-p-terphenyl 4゛°°-ethyl-4-octyl-2,3-difluoro-p-terphenyl 4″°-pentyl-4-octyl-2,3-difluoro-P-terphenyl 4″°-octyl-4-octyl-2,3-difluoro-P-terphenyl 4″°-dodecyl-4-octyl-2,3-difluoro-p-terphenyl 4'°-Pentoxy-4-octyl-2,3-difluoro-ρ-terphenyl 4”°-ethyl-4-dodecyl-2,3-difluoro-p-terphenyl 4″°-pentyl-4-dodecyl-2,3-difluoro-p-terphenyl 4”°-octyl-4-dodecyl-2,3-difluoro-p-terphenyl 4°°°-dodecyl-4-dodecyl-2,3-difluoro-p-terphenyl 4”°-pentoxy-4-dodecyl-2,3-difluoro-p-terphenyl Example 13 4-alkoxy-4'-alkyl-2,3-difluoro-p-terphenyl compound manufacturing of things 1.2-difluoro-3-ethoxybenzene (0.2 mol) was added to T according to Example 10A. Deprotonation with n-butyllithium in HE/THEDA followed by Example 1 4-(p-propylphenyl)-cyclohexanone (0,2 mol) according to 0C Following Example 10A, the reaction was performed with PTSA, followed by acidification with DDQ. After conversion, 4-ethoxy-4°°-propyl-2,3-difluoro-p-ter Get phenyl.

Similarly, the following compounds are obtained: 4-10boxy4"-propyl-2,3-difluoro-p-terphenyl 4-butoxy-4"-propyl-2,3-difluoro-p-terphenyl 4 -Pentoxy-4"-propyl-2,3-difluoro-p-terphenyl 4-hexoxy-4"-propyl-2,3-difluoro-p-terphenyl 4-hebutoxy-4"-propyl-2,3 -difluoro-p-terphenyl 4-octoxy-4''-propyl-2,3-difluoro-p-terphenyl 4-tunoxy-4'°-propyl-2,3-difluoro-p-terphenyl 4-decyloxy- 4°°-propyl-2,3-difluoro-p-terphenyl 4-dodecyloxy-4"-propyl-2,3-difluoro-p-terphenyl 4-ethoxy-4"-pentyl-2,3-difluoro- P-terphenyl K 105 5c135 N 185.114-Globoxy4'-benthyl-2.3-difluoro-p-terphenyl 4-butoxy-4''-pentyl-2,3-difluoro-p-terphenyl 4-pentoxy -4''-pentyl-2,3-difluoro-p-terphenyl 4-hexoxy-4°°-pentyl-2,3-difluoro-p-terphenyl Note 595c145.5°N 166.0@]4-to1 Toxi-4°゛-pen Thiru-2,3-difluoro-p-terphenyl 4-octoxy-4"-pentyl-2,3-difluoro-p-terphenyl 93.5' 5c144.0' 5A148.0"N 159.0" 1 4 -Thornoxy-4'-pentyl-2,3-difluoro-p-terphenyl 4-decyloxy-4'-pentyl-2,3-difluoro-p-terphenyl 4-dodecyloxy-4'-pentyl-2,3 -difluoro-p-terphenyl 4-ethoxy-4'-octyl-2,3-difluoro-p-terphenyl 4-10boxy-4''-octyl-2,3-difluoro-p-terphenyl 4-butoxy- 4'-octyl-2,3-difluoro-p-terphenyl 4-pentoxy-4'-octyl-2,3-difluoro-p-terphenyl 4-hexoxy-4''-octyl-2,3-difluoro-p -terphenyl 4-he1toxy-4'''-octyl-2,3-difluoro-p-terphenyl 4-octoxy-4''-octyl-2,3-difluoro-p-terphenyl 4-tunoxy-4'' -octyl-2,3-difluoro-p-terphenyl 4-decyloxy-4''-octyl-2,3-difluoro-p-terphenyl 4-dodecyloxy-4''-octyl-2,3-difluoro-p −Taafeni 4-ethoxy-4"-dodecyl-2,3-difluoro-p-terphenyl 4-10boxy-4"-dodecyl-2,3-difluoro-p-terphenyl 4-butoxy-4"-dodecyl-2 ,3-difluoro-p-terphenyl 4-pentoxy-di-dodecyl-2,3-difluoro-p-terphenyl 4-hexoxy-4''-dodecyl-2,3-difluoro-p-terphenyl 4-he1-toxy -4''-dodecyl-2,3-difluoro-p-terphenyl 4-octoxy-4''-dodecyl-2,3-difluoro-p-terphenyl 4-Tunoxy-4''-dodecyl-2,3-difluoro- p-terphenyl 4-decyloxy-4''-dodecyl-2,3-difluoro-p-terphenyl 4-dodecyloxy-4''-dodecyl-2,3-difluoro-ρ-terphenyl 4-octoxy-4''- (4-Methylhexyl)-2,3-difluoro-p-terphenyl 71.05c120. ON 128.01 4-Ethoxy-4°°-ethoxy-2,3-difluoro-P-terphenyl 4-10boxy-4″-ethoxy-2,3-difluoronyl-terphenyl 4-butoxy-di-ethoxy -2,3-difluoro-p-terphenyl 4-pentoxy-4"-ditoxy-2,3-difluoro-p-terphenyl 4-hexoxy-4"-ethoxy-2,3-difluoro-p-terphenyl 4-he1toxy-4″-ethoxy-2,3-difluoro-p-terphenyl 4-octoxy-4″-ethoxy-2,3-difluoro-p-terphenyl 4-Tunoxy-4″-ethoxy-2 ,3-difluoro-p-terphenyl 4-decyloxy-4'°-ethoxy-2,3-difluoro-p-terphenyl 4-dodecyloxy-4'°-ethoxy-2,3-difluoro-p-terphenyl 4-ethoxy-4"-pentoxy-2,3-difluoro-p-terphenyl 4-propoxy-4"-pentoxy-2,3-difluoro-ρ-terphenyl 4-butoxy-4"-pentoxy-2, 3-difluoro-p-terphenyl 4-pentoxy-4'-pentoxy-2,3-difluoro-p-terphenyl 4-hexoxy-4"-pentoxy-2,3-difluoro-p-terphenyl 4-to Butoxy-4'-pentoxy-2,3-difluoro-p-terphenyl 4-octoxy-4'-pentoxy-2,3-difluoro-p-terphenyl 4-Tunoxy-4"-pentoxy-2,3- Difluoro-p-terphenyl 4-decyloxy-4"-pentoxy-2,3-difluoro-p-terphenyl 4-dodecyloxy-4"-pentoxy-2,3-difluoro-p-terphenyl 4-Ethoxy-4°°-dodecyloxy-2,3-difluoro-p-terpheni 4-propoxy-4°”-dodecyloxy-2,3-difluoro-p-terphene Nyl 4-butoxy-4"-dodecyloxy-2,3-difluoronyl-terphenyl 4-pentoxy-4"-dodecyloxy-2,3-difluoro-p-terphenyl 4-hexoxy-4″-dodecyloxy-2,3-difluoro-p-terphenylene 4-to-1 toxic di-dodecyloxy-2,3-difluoro-p-terphenyl 4-octoxy-4'-dodecyloxy-2,3-difluoro-p-terphenyl 4-Tunoxy-4゛°-dodecyloxy-2,3-difluoro-p-terpheni 4-decyloxy-4'°-dodecyloxy-2,3-difluoro-p-turf phenyl 4-dodecyloxy-4″-dodecyloxy-2,3-difluoro-p-turf phenyl 4-octoxy-4'-pentyl-2.3.2'-trifluoro-p-terphene Nil 58. O5c61.5 N 119.514-Ethoxy-4″°-Pro Biru-2,3-difluoro-p-quaterphenyl 4-10boxy-4''-propyl-2,3-difluoro-p-quaterphenyl 4-Butoxy-4”-propyl-2,3-difluoro-p-quaterphenylene 4-pentoxy-4'-probyl-2,3-difluoro-p-quaterphae Nyl 4-hexoxy-4”-propyl-2,3-difluoro-P-quaterphene Nyl 4-he1toxy-4''°-propyl-2,3-difluoro p-quaterf phenyl 4-octoxy-4'°-proyl-2,3-difluoro-p-quaterphene 4-Tunoxy-4”’-70pyru-2,3-difluoro-p-quaterphenylene 4-decyloxy-4'°-propyl-2,3-difluoro-p-quarter Phenyl 4-dodecyloxy-4'°-propyl-2,3-difluoro-p-quarter Phenyl 4-ethoxy-4'° °-Pentyl-2,3-difluoro-p-quaterphene 4-propoxy-4”-pentyl-2,3-difluoro-p-quarterphenyl 4-Butoxy-4”°-benthyl-2,3-difluoro-p-quarterphenylene 4-pentoxy-4”°-benthyl-2,3-difluoro-p-quarterfe 4-hexoxy-4゛°-pentyl-2,3-difluoro-p-quarterphene Nyl 4-hebutoxy-4°°°-pentyl-2,3-difluoro-p-quaterf phenyl 4-octoxy-4゛°°-pentyl-2,3-difluoro-p-quaterf phenyl 4-tunoxy-4゛°-pentyl-2,3-difluoro-ρ-quaterphenyl 4-decyloxy-4′°°-pentyl-2,3-difluoro-p-quarter phenyl 4-dodecyloxy-4″°-pentyl-2,3-difluoro-p-quarter phenyl 4-ethoxy-4″- Octyl-2,3-difluoro-p-quaterphenyl 4-propoxy-4″°-octyl-2,3-difluoro-p-quaterphenyl Nyl 4-butoxy-4''-octyl-2,3-difluoro-p-quartertzuni 4-pentoxy-4”°-octyl-2,3-difluoro-ρ-quaterphene Nyl 4-hexoxy-4゛°°-octyl-2,3-difluoro-p-quaterf phenyl 4-hebutoxy-4°°°-octyl-2,3-difluoro-p-quaterf phenyl 4-octoxy-4″-octyl-2,3-difluoro-ρ-quaterphene 4-Tunoxy-4″-octyl-2,3-difluoro-ρ-quaterphenylene 4-decyloxy-4°°°-octyl-2,3-difluoro-p-quarter Phenyl 4-dodecyloxy-4”°-octyl-2,3-difluoro-p-quarter Phenyl 4-ethoxy-4”°- Dodecyl-2,3-difluoro-p-quaterphenylene 4-10boxy-4"°-dodecyl-2,3-difluoro-p-quaterphene Nyl 4-butoxy-4゛°-dodecyl-2,3-difluoro-ρ-quaterphenylene 4-pentoxy-4″°-dodecyl-2,3-difluoro-p-quaterphene Nyl 4-hexoxy-4゛°°-dodecyl-2,3-difluoro-p-quaterf phenyl 4-hebutoxy-4゛°°-dodecyl-2,3-difluoro-P-quaterf phenyl 4-octoxy-41-dodecyl-2,3-difluoro-p-quaterpheny 4-Tunoxy-41-dodecyl-2,3-difluoro-p-quaterphenylene 4-decyloxy-4°゛°-dodecyl-2,3-difluoro-p-quarter Phenyl 4-dodecyloxy-4′′°-dodecyl-2,3-difluoro-p-quarter -Phenyl 4-ethoxy-4゛°°-ethoxy-2,3-difluoro-p-quaterphene Nyl 4-10boxy-4゛°°-ethoxy-2,3-difluoro-P-quaterf phenyl 4-butoxy-4°°°-ethoxy-2,3-difluoro-p-quaterphene Nyl 4-pentoxy-4°゛°-ethoxy-2,3-difluoro-p-quaterf phenyl 4-hexoxy-4°°°-ethoxy-2,3-difluoro-p-quaterf phenyl 4-hebutoxy-4”-ethoxy-2,3-difluoro-p-quaterpheny 4-octoxy-41-ethoxy-2,3-difluoro-p-quaterphenylene 4-Tunoxy-4″°-ethoxy-2,3-difluoronyl-quaterphenylene 4-decyloxy-4°°゛-ethoxy-2,3-difluoro-p-quarter Phenyl 4-dodecyloxy-4”°-ethoxy2,3-difluoro-P-quarter Phenyl 4-ethoxy-4”-pentoxy -2,3-difluoro-p-quaterphenylene 4-propoxy-4”-pentoxy-2,3-difluoro-p-quaterphene Nyl 4-butoxy-4"°-pentoxy2,3-difluoro-ρ-quaterphene Nyl 4-pentoxy-4”°-pentoxy2,3-difluoro-p-quaterf Phenyl 4-hexoxy-4'°°-pentoxy-2,3-difluoro-p-quarter Phenyl 4-hexoxy-4'-pentoxy-2,3-difluoro-p-quarter phenyl 4-octoxy-4°”°-pentoxy2,3-difluoro-p-quarter phenyl 4-octoxy-4″°-pentoxy-2,3-difluoro-p-quarterphene Nyl 4-decyloxy-4"°-pentoxy2,3-difluoro-p-quarter Phenyl 4-dodecyloxy-4"°-pentoxy-2,3-difluoro-p-quater Terphenyl 4-ethoxy-4゛°-dodecyloxy-2,3-difluoro-p-quarter Phenyl 4-10boxy-4゛°°-dodecyloxy-2,3-difluoro-p-quarter Terphenyl 4-butoxy-4''-dodecyloxy-2,3-difluoro-p-quarter Phenyl 4-pentoxy-4''-dodecyloxy-2,3-difluoro-p-quarter -Phenyl 4-hexoxy-4゛°°-dodecyloxy-2,3-difluoro-p-qua Terphenyl 4-hebutoxy-4"-dodecyloxy-2,3-difluoro-p-quarter Phenyl 4-octoxy-4"°-dodecyloxy-2,3-difluoro-p-quarter -Phenyl 4-decyloxy-4°"-dodecyloxy-2,3-difluoro-p-quarter Phenyl 4-decyloxy-4"°-dodecyloxy-2,3-difluoro-p-quater Terphenyl 4-dodecyloxy-4″°-dodecyloxy-2,3-difluoro-ρ-qua -terphenyl Example 14 Ferroelectric Smectic C liquid crystal mixture containing difluoroterphenyl compound Mixture 14A 4-n-octyloxy-2,3-difluoro-4"-n-benthyl-p-terphenyl 95 wt% (+)-( 1-Cyano-2-methyl 10-pyru)-4°-octyloxybiphenyl-4-ylcarboxylate 5 wt% The optically active compounds in this mixture are of the ladder configuration.

This mixture showed the following liquid crystal transition ('C)K 85.95c125.4 5 A143.2 N 150.61 This S. The phase was cooled down to 76°C.

120 7.8 18.0 100 14.6 25 95 16.0 27 90 16.9 28 80 19.0 Mixture 14B 4-n-hexyloxy-4″-pentyl-2°,3°-difluoro-p-ter Phenyl 45 wt% 4-n-octyloxy-4”-pentyl 2°, 3° -Difluoro-P-terphenyl 45 wt% (+)-(1-cyano-2-meth 10-pyru)-4°-octyloxybiphenyl-4-ylcarboxylate 6.25 wt% (-)-(1-cyano-2-methylpropyl)-4'-octyloxybife Nyl-4-ylcarboxylate 3.75 wt% This mixture showed the following liquid crystal transition (°C): >205c84.75A98.6 N 12g! That is, this mixture is S at room temperature. It showed the phase.

84 0.12 82 1.12 9.0 80 2.8 10.0 75 2.93 14.0 70 3.75 15.0 65 4.32 60 4.87 18.0 55 5, 4 50 5.83 20.0 45 6.4 40 6.9 22.5 35 7.28 22.5 30 7.74 23.5 25 8.08 Using a well-known liquid crystal electro-optic cell of S construction, mixture 14B was applied at an applied voltage of 20 volts. and about 100 μs in cells with 2 μm spacing made of polyimide oriented film. EC switching time is shown.

Example 15 4-n-hexyloxy-4''-n-pentyl-2',3'-difluoro-p- Terphenyl and 4-n-octyloxy-4”-n-pentyl-2°, 3°-di A 1:1 (by weight) mixture of fluoro-p-terphenyl was supercooled to 28°C. S showed the S phase. 79. IN 142.41. The birefringence of this mixture is It was 0.19.

Example 16 Prepare a mixture containing the following liquid crystal components: 4-octyl-4°“-propyl -2'-Fluoro-p-terphenyl, 29.45% 4-he1thyl-4n-propyl-2°-fluoro-p-terphenyl 19.8 0% L-(-)-4-hexoxy-4''-(2-methylbutyl)-2°-fluoro -p-terphenyl 29.40% S-(+) -2-octyl 4°-octyl Cibiphenyl-4-ylcarboxylate 6.45% 4-octoxy-4'- Pentyl 2°, 3°-difluoro-ρ-terphenyl 5.00% Example 17 Prepare a mixture containing the following liquid crystal components = 4-octyl-4'-propyl- 2°-Fluoro-p-terphenyl 41.55% L-(-)-4-hexoxy-4°“-(2-methylbutyl)-2′-fluoro Lo-ρ-terphenyl 41.75% S-(+)-2-octyl 4°-octyl Cibiphenyl-4-ylcarboxylate 11.70% 4-octoxy-4° °-Pentyl-2.3-difluoro-P-terphenyl 5.00% Example 18 Prepare a mixture containing the following liquid crystal components = 4-octyl-4″°-pentyl -2°-Fluoro-p-terphenyl 72.00% S-(+)-2-octyl 4°-octoxybiphenyl-4-ylcarboxylene 4.50% 2-fluoro-4-pentylphenyl 4-octoxybenzoe 13.50% 4-octoxy-4°°-pentyl-2,3-difluoronyl-terphenyl 5.00% 4-octoxy-4°-pentyl-2°,3°-difluoro-p-terphenylene Le 5.00% Example 19 A mixture for ECB prepared containing the following liquid crystal components has a clearing point of 86°C. , Δε knee 1.5, Δn: +0.185: 4.4°-dis0pyru-2.3-difluorobiphenyl 20% 4.4°-dibenthyl-2.3-difluorobiphenyl 20% 4.4”-dipropyl-2,3-difluoro-p-terphenyl 20% 4-(trans-4-propylcyclohexyl)-methoxybenzene 15% 4-(trans-4-propylcyclohexyl)-ethoxybenzene 15% 4.4°-bis-(trans-4-propylcyclohexyl)-2-fluorobi Phenyl 4% 4-ethyl-4°-methoxytran 3% 4-methoxy-4°-methyltran 3% example 20 A mixture for ECB prepared containing the following liquid crystal components is transparent at 82°C. point, Δt knee 1.7, Δn: +0.17: 4-propyloxy-4'-propyl-2,3-difluorobiphenyl 15% 4-pentyloxy-4°-pentyl-2,3-difluorobiphenyl 15% 4-pentyl-4″-hexyloxy-2°,3°-difluoro-p-terphene Nil 15% 4-pentyl-4”-octyloxy-2゛,3°-difluoro-p-terphene Nil 15% 4-(trans-4-propylcyclohexyl)-methoxybenzene 15% 4-(trans-4-10 pylcyclohexyl)-ethoxybenzene 15% 4.4°-bis-(trans-4-propylcyclohexyl)-2-fluorobi Phenyl 4% 4.4°-bis-(trans-4-pentylcyclohexyl)-2-fluorobi Phenyl 3% 4-(trans-4-propylcyclohexyl)-4'-(trans-pentyl cyclohexyl)-2-fluorobiphenyl 3% Example 21 A mixture for ECB prepared containing the following liquid crystal components has a clearing point of 91°C. , Δε knee 1.5, Δn: +0.23: 4-propyloxy-4'-propyl-2,3-difluorobiphenyl 15% 4-pentyloxy-4'-pentyl-2,3-difluorobiphenyl 15% 4-Pentyl-4″-hexyloxy-2,3°-difluoro-p-terpheni Le 15% 4-pentyl-4"-octyloxy-2,3°-difluoro-p-terpheni Le 15% 4-(trans-4-propylcyclohexyl)-methoxybenzene 17% 4-ethyl-4°-methoxytran 4% 4-ethoxy-4°-methyltran 4% 4-(trans-4-propylcyclohexyl)-4′-methoxytran 5% 4-(trans-4-propylcyclohexyl)-4-ethoxytran 5% 4-(trans-4-propylcyclohexyl)-4゛-10boxitrane 5 % Example 22 A ferroelectric mixture containing a difluoroterphenyl compound containing the following components: Prepare a eutectic host (Host I) as a base material: 4-hexyloxy-4"-pentyl-2°,3°-difluoro-p-terphene Nyl 37.25 wt% 4-hexyloxy-4'-pentyl-2.3-diph Fluoro-p-terphenyl 13.60 wt% 4-octyloxy-4°°- Pentyl-2°, 3′-difluoro-P-terphenyl 40.8 wt% 4- Octyloxy-4"-pentyl-2,3-difluoro-p-terphenyl 8 ．． 35 wt% mixture 22A Host F 0wt% 4-octyloxy-4'-pentyl-2,3-difluorobiphenyl 20 wt% (+)-(1-cyano-2-methyl10-pyl)-4'-octyloxy-bife Nyl-4-ylcarpoxylate)-6,25wt% (−)-(1-cyano-2-methyl-10vir)-4°-octyloxy-biphe Nyl-4-yl-carboxylate 3.75wt% 5c605A79.7 N 109.41 and Ps 6.6nC/cj (3 0°C), Sc tilt angle 21.5°, this mixture was prepared using the electro-optic cell of Example 14. This indicates a switching time of approximately 40 μsec.

Mixture 22B Host I 90wt% (+)-(1-cyano-2-methylpropyl)-4°-octyloxy-biphene Nyl-4-yl-carboxylate) 6.75wt% (-)-(1-cyano-2-methylpropyl)-4°-octyloxybiphetamine Nyl-4-yl-carboxylate 3.75 wt% <205c90.4S, 109.6N 1331, Ps8.9nC/ aJ (30℃), Sc tilt angle 23.5, switching time approximately 90μsec .

Mixture 22C Host I 90wt% (+)-(1-cyano-2-methyl-10 pyru)-4°-octyloxy-bifu Phenyl-4-yl-carboxylate 5.63 wt% (-)-(1-cyano-2-methyl 10 pyr)-4'-octyloxy-bif Phenyl-4-ylcarpoxylate 4.37 wt% S 93 S 109.6 N 1331, Ps4.24nC/aJ (30 ℃), CA Sc tilt angle 23.5°, switching time approximately 260μsec.

Mixture 22D host I7owt% 4-octyloxy-4°-pentyl-2,3-difluorobiphenyl 20 wt% (+)-(1-cyano-2-methyl 10 pyr)-4°-octyloxy-biphetamine Nyl-4-yl-carboxylate 5.63 wt% (−)-(1-cyano-2-methyl-10vir)-4°-octyloxy-biphe Nyl-4-yl-carboxylate 4.37 wt% 5c605A79.7 N 109.41. Ps2.7 nC/cj (30℃ ), Sc torsion angle 19.5, switching time approximately 75 μsec.

Mixture 22E Host I 45wt% 4,4”-dibenthyl 2°,3°-difluoro-p-terphenyl 45 wt% (+)-(1-cyano-2-methylpropyl)-4゛~octyloxy-biphene Nyl-4-ylcarboxylene) 6.25 *t% (−)-(,1-cyano-2-methyl-10vir)-4°-octyloxy-bif Phenyl-4-yl-carboxylate 3.75wt% S 60.5 S 87. IN 114.71. P 5.6 nC/aa Sc Neshi CA S The deflection angle is 22°, and the switching time is 54 μsec.

Example 23 A ferroelectric mixture containing a difluoroterphenyl compound containing the following components: Prepare a host (host ■) as a base material: 4-Hebutyl-5'-pentyl-2,3-difluoro-p-terphenyl 33 ．． 33 wt% 4°, 4″-dipentyl-2,3-difluoro-p-terphenyl 33.33 wt% 4°, 4″-dibenthyl 2°, 3°-difluoro-p-terphenyl 33. 33 wt% Mixture 23A Host n 90.00 wt% (+)-(1-cyano-2-methyl 10 pyr)-4°-octyloxy-bife Nyl-4-yl-carboxylate 6.25 wt% (-)-(1-cyano-2-methyl 10 pyr)-4°-octyloxy-biphetyl Nyl-4-yl-carboxylate 3.75 wt% S 603 10581151. Ps7.2nC/cJ (30℃), C^ Sc twist angle 21.5°, switching time 17μsec.

Mixture 23B Host II 90.00 wt% (+)-(1-cyano-2-methyl 10 pyr)-4°-octyloxy-bife Nyl-4-yl-carboxylate 10.00 wt% S 59 S 105.4 N 1161, Ps 30nC/'aJ (30 ℃), CA Sc twist angle 21.5°, switching time 4μsec.

Mixture 23C Host l, 97.5t% (+)-(1-cyano-2-methyl 10 pyr)-4°-octyloxy-bife Nyl-4-yl-carboxylate 2.5 wt% 3 86.7 S 107. IN 124.7, Ps 7. OnC/ad (30°C), CA Sc torsion angle 23°, switching time approximately 7usec.

Example 24 containing varying amounts of difluoroterphenyl compounds and chiral doping agents. A ferroelectric mixture is prepared.

Mixture 24A 4-Hebutyl-4''-nonyl-2,3-difluoro-p-terphenyl 97. 5 wt% (+)-(1-cyano-2-methyl 10 pyr)-4°-octyloxy-bife Nyl-4-yl-carboxylate 2.5 wt% 485c62.6 S^92.5 N 103.8], Ps2.9 (50 ℃), switching time 15 μsec.

Mixture 24B 4-pentyl-4°-(4-methylhexyl)-2,3-difluoro-ρ- Terphenyl 90 wt% (+)-(1-cyano-2-methylpropyl)- 4'-octyloxy-biphenyl-4-yl-carboxylate 6.2wt% (-)-(1-cyano-2-methylpropyl)-4'-octyloxy-bif Phenyl-4-yl-carboxylate 3.8wt% 56. IS 80.95A82.7N 89.41, Sc twist angle 26 °.

Mixture 24C 4-pentyl-4'-hebutyl-2°,3°-difluoro-p-terphenyl 29.25 wt% 4-hebutyl-4”-nonyl-2°,3°-difluoro-p -terphenyl 34.125 wt% 4-hebutyl-4°°-pentyl2. 3-difluoro-p-terphenyl 19.50 wτ% 4-pentyl-4°°-heptyl-2,3-difluoro-p-terphenyl i 4.625 wt% (+)-(1-cyano-2-methylpropyl)-4°-oc Tyloxy-biphenyl-4-yl carboxylate 2.50 wt% 50685A94.2 N 1111. Ps5.9 nC/cj (30℃), Sc twist angle 22.5°Switching time approximately 40μsec.

Mixture 24D 4.4”-dibenthyl 2°, 3°-difluoro-p-terphenyl As w t% 4.4″-dipentyl-2,3-difluoro-p-terphenyl 22.5 w t% 4-hebutyl-4″-pentyl-2,3-difluoro-p-terphenyl 22 ．． 5 wt% (+)-(1-cyano-2-methylpropyl)-4°-octyloxy-biphene Nyl-4-yl-carboxylate 6.2 wt% (−)-(1-cyano-2-methylpropyl)-4°-octyloxy-biphetyl Nyl-4-yl-carboxylate 3.8 wt% S 43.65A95.5N 109.51. Ps5.1 nC/cj (2 at 5°C).

Mixture 24E 4-hebutyl-4'-pentyl-2',3'-difluoro-p-terphenyl 48.5 wt% 4-Hebutyl-4°°-pentyl-2,3-difluoro-P-terphenyl 2 4.25 wt% 4.4”-dipentyl-2.3-difluoro-p-terphenyl 24.25 wt% (+)-(1-cyano-2-methylpropyl)-4°-octyloxybiphene Nyl-4-yl-carboxylate 3. Owt% 5c755A91N 1161. Ps7.9 nC/cJ (30℃), s c Helix angle 23°.

Route 1 111 = alkyl R' = alkyl or alkoxy R″: alkyl Route 3 3B R = alkyl or alkoxy R′=alkyl Mu C Routes 6 and 7 R′=alkyl Route 8 R; alkyl or alkoxy R′=alkyl Route 10 m-m-m^1-Meng Yiyi Yi-+-w-, PCT/EP88100724 International Coordination inspection report

Claims (26)

[Claims] 1. Formula I ▲There are mathematical formulas, chemical formulas, tables, etc.▼I [wherein a is 1, and where the terminal substituents R1, R2 and R3 are each independently an alkyl or alkyl group each having up to 15 C atoms; and these groups are optionally substituted by CN or by at least one halide. One CH2 present in these groups may be substituted by a rogene atom. group or two or more non-adjacent CH2 groups are -O-, -S-, -CO-, -O -CO-, -CO-O-, -O-CO-O- or -C≡C- and one of the groups R1 and R2 may also have the formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ can represent a group represented by Any one of the following pair of lateral substituents are both fluorine: (A, B), (C, D), (D, E), (C, E), (B, C), (D, J), (D,K), (A,C), (C,J), (C',D'), (D',E), (D' , A), (C', E), (C', A), (D', J'), (D', K'), (C ', J'), (B, G), (A, G), and other lateral substituents are all water elemental or fluorine] A fluorinated oligophenyl compound represented by 2. one of the terminal substituents R1 and R2 or the group R3 and the group R1 and the group R2 alkoxy, alkyl, para, each having up to 15 C atoms, independently of - fluoroalkyl or perfluoroalkoxy. 3. (C, D) are both fluorine, R1 is ethoxy and R2 is n-pentyl, or (B, C) are both fluorine and R1 is excluding p-terphenyl compounds which are ethoxy and R2 is n-proyl , the derivative of claim 2. 4. Only one pair of lateral substituents are fluorine, and the other lateral substituents are The derivative according to at least one of claims 1 to 3, characterized in that all of the derivatives are hydrogen. 5. A claim characterized in that the derivative is a difluoroterphenyl compound. Derivative of term 4. 6. The following groups of terphenyl compounds: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ I, 1 ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ I, 2 ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼I,3▲There are mathematical formulas, chemical formulas, tables, etc.▼I,4▲There are mathematical formulas, chemical formulas, tables, etc. ▼I, 5▲There are mathematical formulas, chemical formulas, tables, etc.▼Claim 5 selected from I, 6 derivatives of. 7. Only one pair of lateral substituents is fluorine, and the other lateral substituents are At least one of claims 1, 2 or 3, wherein one of the elements is fluorine. Derivative of term. 8. The claim is characterized in that the derivative is a trifluorocuphenyl compound. Derivative of claim 7. 9. formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The derivative according to claim 8, characterized in that it is represented by: 10. n-alkyl in which the terminal substituents each independently have 5 to 12 C atoms; or n-alkoxy, according to at least one of claims 1 to 9. derivative. 11. chiral in which at least one of the terminal substituents has 5 to 12 C atoms; Claims 1 to 10 characterized in that it is an alkyl group or an alkoxy group. At least one derivative. 12. Formula I' ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I') [In the formula, A1 and A2 are respectively and independently a 1,4-phenylene group, which optionally contains 1 to 4 fluorine atoms. may be replaced by R1 and R2 are each independently atom having up to 15 C atoms; alkyl or alkenyl groups, which groups are optionally substituted by CN or optionally substituted by at least one halogen atom, and these groups One CH2 group or two or more non-adjacent CH2 groups present in -O- , -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O- or - It may be replaced by C≡C-, m is 0 or 1, n is 1, 2 or 3, and The sum of m and n is 2 or 3] The derivative according to claim 1, characterized in that it is represented by: 13. The p-terphene according to claim 12, characterized in that the sum of m and n is 2. Derivatives of le. 14. normal in which the terminal substituents each independently have 1 to 7 carbon atoms; at least one of claims 1 to 11, characterized in that it is alkyl or alkoxy of or at least one of claims 12 and 13. 15. 15. Use of a compound according to at least one of claims 1 to 14 as a component of a liquid crystal phase. 16. A liquid crystal composition containing at least two types of liquid crystal components, the liquid crystal composition comprising at least one of the liquid crystal components. A liquid characterized in that the seed component is a compound according to at least one of claims 1 to 14. crystal composition. 17. 17. The liquid crystal composition according to claim 16, which is a nematic composition. 18. 17. A chirally tilted smectate composition according to claim 16. liquid crystal composition. 19. Chirally tilted smectay containing at least two liquid crystal components A composition of matter wherein at least one component is of formula I ▲There are mathematical formulas, chemical formulas, tables, etc.▼I [wherein a is 0 or 1, and R1, R2, A, B, C, D, E, G, J and K have the meanings given in claim 1] Chirally tilted smectates characterized by being a compound represented by composition. 20. Claims characterized in that in the compound of formula I, a represents 0. 20. The chirally tilted smectate composition according to 19. 21. The compounds of formula I belong to the following group of biphenyl compounds: ▲There are mathematical formulas, chemical formulas, tables, etc.▼I,13▲There are mathematical formulas, chemical formulas, tables, etc.▼ I, 14▲There are mathematical formulas, chemical formulas, tables, etc.▼I,15▲There are mathematical formulas, chemical formulas, tables, etc. ▼I,16▲There are mathematical formulas, chemical formulas, tables, etc.▼I,17▲Mathematical formulas, chemical formulas, There are tables, etc.▼I, 18▲There are mathematical formulas, chemical formulas, tables, etc.▼Choose from I, 19 The chirally tilted smectates according to claim 19, characterized in that: composition. 22. In formula I, in addition to at least one corresponding compound in which a represents 0 , containing at least one corresponding compound in which a represents I in formula I; The chirally tilted smectate composition according to claim 19, characterized in that thing. 23. In addition to at least one compound of formula I, ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ [wherein RA is alkyl or alkoxy, RB is alkyl, and (F) represents that this ring may have a lateral fluorine substituent, and n is 1 or 2, m is 0 or 1] The liquid crystal according to at least one of claims 18 to 22, characterized in that it contains seeds. Composition. 24. RB is C1-C4n-alkyl or cyclohexyl, or RB is the structural formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (wherein a is 0 or 1-6, and b and C are each independently 1-6) 6) A claim characterized in that it is a branched or chiral alkyl represented by 24. The liquid crystal composition according to 23. 25. It is characterized by containing the liquid crystal phase according to at least one of claims 16 to 24. A liquid crystal display element. 26. It is characterized by containing the liquid crystal phase according to at least one of claims 16 to 24. An electro-optic display element.