JP3111048B2 - Fluorinated oligophenyl compounds and their use in liquid crystal materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to laterally fluorinated oligophenyl compounds and the use of these compounds in liquid crystal materials. Liquid crystal materials are well known and these are generally known as nematic (N) or smectic, in particular chiral smectic C.
It utilizes the electro-optical switching properties of (S _C ^* ) or smectic I (S _I ^* ) phase (where asterisk * represents a chiral phase). These materials are widely used in electro-optical displays. Such materials are generally mixtures of compounds selected such that the mixture exhibits the desired properties. In particular, this property includes the following properties:

(I) a suitable liquid crystal phase, for example S _A ,
A broad temperature range in which the S _C , S _C ^* , S _I , S _I ^* or N phase persists, which preferably includes room temperature (about 20 ° C.). In the case of (ii) low viscosity and (iii) manufacturing is easy (iv) good electro-optic response (v) compounds showing an S _C phase or mixtures,
Long pitch and for forming a helical chiral phase with high spontaneous polarization efficiency P _S, one or two or more optically active compounds, i.e. miscibility with the compound having a carbon atom which is asymmetrically substituted. The compounds or mixtures, to indicate S _A phase at a temperature above its S _C phase,
It also is useful to help align the S _C phase at the electrode of the liquid crystal electro-optical device.

[0003] Fluorinated terphenyl compounds for use in liquid crystal materials are known. For example: EP-A-8
430494.3 has the general formula

[0004]

Embedded image

The preparation of monofluorinated terphenyl compounds of the formula wherein R ₁ and R ₂ are independently alkyl or alkoxy and the use of these compounds in nematic liquid crystal materials is described. GB-A-
The 8725928 and WO / 07890 use in _S ^{C *} mixture of these Monofutsu fluorinated terphenyls compounds are described. EP-A-0084194 contains a general and conceptual description of terphenyl compounds which have been laterally difluorinated.

[0006]

Embedded image

[0007] With respect to the use of nematic mixtures, it is theoretically included. PCT / EP87 / 0051, which was not published at the time of filing the patent application of the present invention
5 contains a conceptual general formula believed to encompass a difluorophenyl compound, and also includes two compounds specifically used in nematic liquid crystal mixtures:

[0008]

Embedded image Also mentioned.

The present invention seeks to identify another class of useful difluorinated terphenyl compounds, and more particularly to study their use in smectic liquid crystal materials. According to the present invention there is provided a fluorinated derivative of biphenyl, p-terphenyl or p-quarterphenyl of the formula I:

[0010]

Embedded image

Wherein a is 0 or 1, and wherein the terminal substituents R ¹ , R ² and R ³ are each independently an alkyl group having up to 15 C atoms or Alkenyl groups, these groups optionally being CN
Or at least one halogen atom may be substituted by one CH present in these groups.
_Two or two or more non-adjacent CH ₂ groups are -O-,
-S-, -CO-, -O-CO-, -CO-O-, -O
—CO—O— or —C≡C— may be replaced and ^{one of} the radicals R ¹ and R ² is also of the formula

[0012]

Embedded image 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 all other lateral substituents are hydrogen or fluorine, provided that the formula II

[Outside 1] (Wherein, R ¹ , R ² , A, B, C, D, E, G, J, K
And R ¹ and R ² are

[Outside 2] Wherein R ³ , C ′, D ′, G ′ and J ′ are all as defined above). ].

The preferred structures described below are based, inter alia , on their usefulness in liquid crystal mixtures and / or their ease of manufacture. Preferred general structures of the difluorinated terphenyl compounds of the formula I correspond to the structures of the subformulae I, 1 to I, 6:

[0015]

Embedded image Preferred general structures of the trifluorinated terphenyl compounds of the formula I correspond to the structures of the sub-formulas I, 7 to I, 12:

[0016]

Embedded image

Particularly preferred are compositions exhibiting the smectic C phase which contain the corresponding compound of formula I wherein a is 0. Preferred general structures of difluorinated biphenyl compounds of formula I (a = 0) are those of the subformulae I, 13-
I, corresponding to the structure shown in 19:

[0018]

Embedded image

In the following description, for brevity,
Phe represents a 1,4-phenylene group, and PheF is represented by the formula

Embedded image And PheF ₂ has the formula

Embedded image Represents a group represented by

The compounds of the formula I are preferably used as components of liquid-crystal mixtures, preferably for liquid-crystal mixtures based on the principle of twisted cells, the effect of guest-host effects, deformation of the ordered phase or effects of dynamic scattering. can do. Negative anisotropy of the permittivity [Δε = ε ＝ −ε⊥ <(where ε‖ represents the permittivity parallel to the axis of the molecule, and ε⊥ is the permittivity perpendicular to this axis. The compounds of formula I are aligned perpendicular to the applied electric field.

This effect has been known in the art, and it has been known in various liquid crystal display devices, for example, a display device using the effect of dynamic scattering, the effect of deformation of the alignment phase, or the effect of guest-host interaction. Used to adjust transparency. The ECB effect (electrically controlled birefringence) or the DAP effect (deformation of the ordered phase) is described in M.E. F. S
chieckel and K.C. Fahr-nschon
By Appl. Phys. Lett. (1971
Year), p. 3912.

J. Robert and F.M. Clerc's paper [SID 80, Digest. Te-chn. P
apers (1980), p. 80], that the liquid crystal phase has a large numerical value with respect to the elastic constant K ₃ / K ₁ , a large optical anisotropy value Δn, It has been shown that it must have a dielectric anisotropy value between -0.5 and -5.0.

Electro-optical display elements based on the ECB effect exhibit homeotropic alignment, which means that the liquid crystal phase has a negative dielectric anisotropy. The 1 _C phase used in electro-optic display elements based on this effect must meet many requirements. They must have chemical stability to humidity and air, physical stability to heat, infrared, visible and ultraviolet radiation and to AC and DC electric fields. In addition, an industrially usable 1 _C phase is required to have a liquid crystal mesophase in an appropriate temperature range and to have a low viscosity.

However, a suitable mesophase range,
There is a great demand for liquid crystal phases having high K ₃ / K ₁ values, high optical anisotropy Δn, negative dielectric anisotropy and high stability. In another important embodiment of the invention, the compounds of the formula I are particularly suitable as components of a chirally tilted smectic phase.

The chiral tilted smectic liquid crystal phase having ferroelectric properties can be prepared by adding an appropriate chiral doping agent to a substrate mixture exhibiting one or more tilted smectic phases. [L. A. Veresnov et al., Mol.
Cryst. Liq. Cryst. 89 , 327 (1982); R. J. Brand et al. Ph
ysque 44 (lett.), L-771 (1983)]. Such phases are Clark and L
agerwall, which can be used as a dielectric for displays based on SSFLC-technology [N. A. Clark and S.M. T. Lag
erwall Appl. Phys. Lett. 3
6 , 889 (1980); U.S. Pat. No. 4,367,
924].

It is an object of the present invention to find fluorinated oligophenyl compounds of the formula I which are suitable as components of liquid-crystal mixtures. In particular, the use of these compounds makes it possible to prepare liquid-crystal mixtures having a wide mesophase range and a relatively low viscosity. Furthermore, the compounds of the formula I are suitable as components of a chirally tilted smectic liquid crystal phase.

The compounds of the formula I have a wide range of applications. These compounds can be used as a base material constituting up to 50% of the liquid crystal mixture by selecting a substituent. However, the compounds of the formula I can also be added to liquid crystal substrates from other types of compounds to add dielectric and / or optical anisotropy and / or viscosity of such dielectrics, And / or
The spontaneous polarization, and / or the method range, and / or the tilt angle, and / or the pitch can be affected. The compounds of the formula I are also suitable as intermediates for producing other substances which are useful as components of liquid crystal dielectrics.

The compounds of the formula I are pure and colorless. These compounds are very stable to chemicals, heat and light. Accordingly, the present invention relates to compounds of the formula I (where a is 1), in particular compounds of the formulas I, 1 to I, 6. Furthermore, the present invention relates to compounds of formula I ′:

[0029]

Embedded image Wherein, A ¹ and A ² are each independently 1,4-phenylene group wherein the group may be substituted by 1-4 fluorine optionally, R ¹ and R ² Each independently is an alkyl or alkenyl group each having up to 15 C atoms, these groups optionally being
N, or by may be substituted by at least one halogen atom, and is one more CH ₂ groups not CH ₂ group or adjacent that present in the group -O -, - S-, -CO-, -O-CO-, -CO-
O—, —O—CO—O— or —C−C— may be replaced, m is 0 or 1, n is 1,
2 or 3 and the sum of m and n is 2 or 3
Is].

Further, the present invention provides a liquid crystal composition containing at least two kinds of liquid crystal components, at least one of which is a compound represented by the formula I (where a is 1), and Has at least one component of formula I wherein a
Represents a 0 or 1), and a liquid crystal composition showing a smectic C phase. Furthermore,
The present invention relates to a liquid crystal display device containing such a composition. Throughout the description of this specification, unless stated otherwise, R ¹ , R ² , R ³ , A ¹ , A ² , m and n
Has the above meaning.

Accordingly, the compounds of the formula I are preferred compounds having three rings of the following formulas Ia to Id: R ¹ -Phe-Phe-PheF ₂ -R ² Ia R ¹ -Phe- ^{_{PheF 2 -Phe-R 2 Ib R}} 1 -PheF-Phe-PheF-R 2 Ic R 1 -PheF-PheF-Phe-R 2 Id

Compounds having four rings represented by the following partial formulas Ie to Ij: R ¹ -Phe-Phe-Phe-PheF ₂ -R ² Ie R ¹ -Phe-Phe-PheF ₂ -Phe-R ² If R ¹ -PheF-Phe-Phe-PheF-R ² IgR ¹ -PheF-Phe-PheF-Phe-R ² Ih R ¹ -PheF-PheF-Phe-Phe-R ² Ii R ¹ -Phe-PheF- PheF-Phe-R ² Ij and compounds having two rings represented by the following partial formulas Ik: encompasses _{^{R 1 -PheF 2 -Phe-R 2}} Ik.

Throughout the specification, R ¹ and R ² preferably represent alkyl or alkoxy. Formula I '
In the compound shown by A, A ¹ and A ² are Phe, P
heF and PheF ₂ . Preferably, compounds of formula I 'can not have one more PheF ₂ groups. n is preferably 1, 2 or 3, especially 1. m is preferably 0.

Throughout the specification, R ¹ and R ² are each preferably from 1 to 13 C atoms, in particular 3 C atoms
Having ~ 12 represents preferred alkyl. In formula I, the corresponding compounds in which R ¹ , R ² and R ³ have 1 to 7, preferably 1 to 5, C atoms are particularly suitable for the liquid-crystal phases used in displays based on the ECB effect. . In the formula I, R ¹ , R ² and R ³ are each a C atom having 2 to 1 carbon atoms.
5, preferably 2 to 12 C atoms, especially 3 to 9 C atoms
Corresponding compounds having an individual are suitable for liquid crystal phases exhibiting ferroelectric properties.

In the groups R ¹ , R ² and R ³ , one or two CH ₂ groups are —O—, —S—, —CO—,
It can be replaced by -O-CO-, -CO-O-, -O-CO-O- or -C≡C-. Preferably, only one CH ₂ group is particularly preferably —O
-, -O-CO-, -CO-O- or -C≡C-.

R ¹ , R ² and R ³ are each an alkyl group, and one CH ₂ group present in this group may be replaced by —O— (alkoxy or oxaalkyl); or Two non-adjacent CHs
Where _two groups may be replaced by -O- (alkoxyalkoxy or dioxaalkyl), these groups may be straight-chain or branched. Preferably, this group is straight-chain, with C atoms 2, 3, 4,
5, 6, 7, 8, 9 or 10 and is therefore preferably ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy,
Heptoxy, nonoxy, decyloxy and also methyl, undecyl, dodecyl, tridecyl, tetradecyl, methoxy, undecyloxy, dodecyloxy, tridecyloxy or tetradecyloxy.

Oxaalkyl is preferably straight-chain 2-
Oxapropyl (= methoxymethyl), 2-(= ethoxymethyl) or 3-oxabutyl (= 2-methoxyethyl), 2-, 3- or 4-oxapentyl, 2-,
3-, 4- or 5-oxahexyl, 2-, 3-, 4
-, 5- or 6-oxaheptyl, 2-, 3-, 4
-, 5-, 6- or 7-oxaoctyl, 2-3
-, 4-, 5-, 6-, 7- or 8-oxanonyl,
2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-
Oxadecyl, 1,3-dioxabutyl (= methoxymethoxy), 1,3-, 1,4-, 2,4-dioxapentyl, 1,3-1,4-, 1,5-, 2,4-, 2,5
-Or 3,5-dioxahexyl, 1,3-, 1,4
-, 1,5-, 1,6-, 2,4-, 2,5-, 2,6
-, 3,5-, 3,6- or 4,6-dioxaheptyl.

R ¹ , R ² and R ³ are each an alkyl group, and one CH ₂ group present in this group is -S-
The thiaalkyl group can be straight-chain or branched when replaced by Preferably, this group is straight-chain, 2-thiapropyl, 2- or 3-thiabutyl, 2-, 3- or 4-thiapentyl, 2-, 3-, 4- or 5-thiahexyl, 2-,
3-, 4-, 5- or 6-thiaheptyl, 2-3
-, 4-, 5-, 6- or 7-thiaoctyl, 2-,
Represents 3-, 4-, 5-, 6-, 7- or 8-thianonyl or 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-thidecyl. Among the thiaalkyl groups,
The ring Phe, PheF or Phe present in this group
Preference is given to groups in which the CH ₂ group adjacent to F ₂ has been replaced by —S—. Thus, this group represents methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, heptylthio, octylthio, nonylthio or decylthio.

When R ¹ , R ² and R ³ are each an alkenyl group, this group can be straight-chain or branched. Preferably, this group is linear,
It has 2 to 10 C atoms. Therefore, this group is vinyl,
Prop-1- or prop-2-enyl, but-1
-, 2- or but-3-enyl, pent-1-, 2
-, 3- or pent-4-enyl, hex-1--2,
-, 3-, 4- or hex-5-enyl, hept-1
-, 2-, 3-, 4-, 5- or hept-6-enyl, oct-1-, 2-, 3-, 4-, 5-, 6- or oct-7-enyl, non-1- , 2-, 3-, 4
-, 5-, 6-, 7- or non-8-enyl, dec-
1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or dec-9-enyl.

R ¹ , R ² and R ³ are each an alkyl group, and one CH ₂ group present in this group is —O—
This group can be straight-chain or branched when replaced by CO- or -CO-O-. Preferably, this group is straight-chain and has 2 to 6 carbon atoms.
Have pieces. Thus, this group is preferably acetyloxy, propionyloxy, butyryloxy, pentanoyloxy, hexanoyloxy, acetyloxymethyl, propionyloxymethyl, butyryloxymethyl, pentanoyloxymethyl, 2-acetyloxyethyl, -Propionyloxyethyl, 2-butyryloxyethyl, 3-acetyloxypropyl, 3-propionyloxypropyl, 4-acetyloxybutyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, methoxycarbonylmethyl, Ethoxycarbonylmethyl, propoxycarbonylmethyl, butoxycarbonylmethyl, 2- (methoxycarbonyl) ethyl, 2-
(Ethoxycarbonyl) ethyl, 2- (propoxycarbonyl) ethyl, 3- (methoxycarbonyl) propyl, 3- (ethoxycarbonyl) propyl or 4-
(Methoxycarbonyl) butyl.

The compounds of the formula I, which have branched terminal groups R ¹ , R ² and R ³ , are optionally important because they have an improved solubility in conventional liquid-crystalline substrates. However, if they are optically active, they are particularly important as chiral doping substances.
This type of smectic compound is suitable as a component for ferroelectric materials.

Branched groups of this type generally have at most one chain branch. Preferred branched groups R ¹ , R ² and R ³ are isopropyl, 2-butyl (= 1-methylpropyl), isobutyl (= 2-methylpropyl), 2-methylbutyl, isopentyl (= 3-methylbutyl), 2
-Methylpentyl, 3-methylpentyl, 2-ethylhexyl, 2-propylpentyl, isopropoxy, 2-
Methylpropoxy, 2-methylbutoxy, 3-methylbutoxy, 2-methylpentoxy, 3-methylpentoxy, 2-ethylhexoxy, 1-methylhexoxy,
-Methylheptoxy, 2-oxa-3-methylbutyl,
3-oxa-4-methylpentyl, 4-methylhexyl, 2-nonyl, 2-decyl, 2-dodecyl, 6-methyloctoxy, 6-methyloctanoyloxy, 5-methylheptyloxycarbonyl, 2-methylbutyi Ryloxy, 3-methylvaleryloxy, 4-methylhexanoyloxy, 2-chloropropionyloxy, 2-chloro-3-methylbutyryloxy, 2-chloro-4-methylvaleryloxy, 2-chloro-3 -Methylvaleryloxy, 2-methyl-3-oxapentyl, 2-methyl-
3-oxahexyl, 2-fluoro-3-methylvaleryloxy, 2-fluoro-3-methylbutoxy.

R ¹ , R ² and R ³ are each an alkyl group, and two or more C 3
When the H ₂ group is -O- and (or) is replaced by -CO-O-, this group may be straight-chain or branched. Preferably, this group is branched and has 3 to 12 C atoms. Thus, this group is preferably bis-carboxy-methyl, 2,2-bis-carboxy-ethyl, 3,3-bis-carboxy-propyl, 4,4-bis-carboxy-butyl, 5,5-
Bis-carboxy-pentyl, 6,6-bis-carboxy-hexyl, 7,7-bis-carboxy-heptyl,
8,8-bis-carboxy-octyl, 9,9-bis-
Carboxy-nonyl, 10,10-bis-carboxy-
Decyl, bis- (methoxycarbonyl) -methyl, 2,
2-bis- (methoxycarbonyl) -ethyl, 3,3
-Bis- (methoxycarbonyl) -propyl, 4,4-
Bis- (methoxycarbonyl) -butyl, 5,5-bis- (methoxycarbonyl) -pentyl, 6,6-bis-
(Methoxycarbonyl) -hexyl, 7,7-bis-
(Methoxycarbonyl) -heptyl, 8,8-bis-
(Methoxycarbonyl) -octyl, bis- (ethoxycarbonyl) -methyl, 2,2-bis- (ethoxycarbonyl) -ethyl, 3,3-bis- (ethoxycarbonyl) -propyl, 4,4-bis- (ethoxy Carbonyl) -butyl, 5,5-bis- (ethoxycarbonyl)
-Pentyl.

The corresponding compounds of formula I wherein the terminal groups R ¹ , R ² and / or R ³ are groups suitable for polycondensation reactions are useful for the preparation of liquid crystal polycondensates. Formula I encompasses both racemic and optically enantiomers of these compounds, and mixtures thereof.

Compounds of formula I have been described in the literature [eg H
Method der by oben-Weyl
Organischen Chemie (Georg
-Standard publications such as Theme publisher, Stuttgart), in particular under known reaction conditions suitable for the reactions mentioned. Known per se,
Variants not described in detail here can also be used in this case.

If desired, the starting compounds can also be formed in situ, so that they are not further isolated from the reaction mixture but are immediately further reacted to give the compound of formula I. The compound of the formula I 'can be produced from 1,2-difluorobenzene as a starting compound.

This compound was prepared according to M. A. Roe's method
[J. Chem. Soc. Chem. Comm.2
2, P. 582 (1965)].
And then reacting with the corresponding electrophilic reactant.

This series of reactions is carried out by reacting the thus obtained 1-substituted-2,3-difluorobenzene with 2
Can be done once. Thus, a 1,4-disubstituted-2,3-difluorobenzene derivative represented by the formula I can be obtained. 1,2-difluorobenzene or 1-substituted-2,3-difluorobenzene are each
For example, diethyl ether, tetrahydrofuran, dimethoxyethane, tert. In an inert solvent such as ethers such as butyl methyl ether or dioxane or hydrocarbons such as hexane, heptane, cyclohexane, benzene, toluene or mixtures of these solvents, optionally, for example, tetramethylethylenediamine (TMEDA) Using complexing agents such as hexamethylphosphoric triamide (HMPTA) or N, N-dimethylpropylene-urea (DMPU), for example, phenyllithium, n-, sec-, or tert-butyllithium, lithium tetra It is reacted with an organometallic reagent such as methylpiperidinidi at a temperature of -120C to + 50C, preferably -78C to 0C.

The 2,3-difluorophenyllithium compound is reacted with the corresponding electrophilic reactant at -120 ° C to 0 ° C, preferably 0 ° C. Suitable electrophilic reactants are aldehyde compounds, ketone compounds, nitrile compounds, epoxide compounds, carboxylic acid derivatives such as esters, anhydrides or carboxylic halides, halogen formate or carbon dioxide. Particularly suitable electrophilic reactants are derivatives of cyclohexanone.

In the case of the reaction with an aliphatic halide, the lithium derivative is prepared by using potassium tert-butylate to form-
At 80C to -120C, the metal must be transmetalated to the potassium derivative. In the case of reaction with an aromatic halide, the lithium derivative is transmetallized, for example, to an aene-, boron- or titanium-derivative suitable for a cross-linking reaction under a transition metal catalyst.

The terphenyl compound of the formula I is
For example, the general routes 1 to 1 shown in the attached FIGS.
10 can be manufactured. In this specification,
R ₁And R _TwoIs alkyl or alkoxy
Illustrated for the perfluoroalkyl homolog or
Perfluoroalkoxy homologs can be prepared by a similar route
It is understood. Other methods for producing these compounds
Will be apparent to those skilled in the art. In formula I, a pair
Either (D, K) or (C, J)
The corresponding terphenyl compound, which is fluorine, is, for example,
Route 9 raw difluorophenol or known 1,
Using 3-difluoro-2-aminophenol, this
To the precursor compound, for example via the known phenylboronic acid
Coupling these ringsRouteUse the corresponding
By adding a 4-substituted phenyl ring.
Can be manufactured.

The difluorobiphenyl compounds of the formula I can be obtained by coupling the various intermediate compounds produced in these routes with the phenyl compounds by a modification of the routes 1 to 9, for example as follows: Can be manufactured:

[0053]

Embedded image

The trifluoroterphenyl compound can also be
By a modification of routes 1 to 9, for example, by coupling the resulting intermediate, it can be prepared, for example, as follows:

[0055]

Embedded image

The compounds of the formula I are often
It exhibits a nematic or smectic phase that persists over a wide temperature range and is a useful component of liquid crystal mixtures.
Thus, according to a second aspect of the present invention, it is a mixture of compounds, at least one of these compounds being a p-bi-, p-ter- or p-quarterphenyl compound of formula I, preferably Is a compound selected from partial formulas I, 1 to I, and 19, and a liquid crystal material is provided.

The liquid crystal phase according to the invention comprises 2 to 25, preferably 3 to 15, components, at least one of which is a compound of the formula I.

The other components are preferably nematic, smectic, nematogenic or smectogenic substances, especially azoxybenzene compounds, benzylideneaniline compounds, biphenyl compounds, p-terphenyl compounds, phenyl or cyclohexylbenzoate compounds, phenyl or cyclohexylcyclohexanecarboxylate compounds, Phenylcyclohexane compound,
Cyclohexylbiphenyl compound, cyclohexylcyclohexane compound, cyclohexylnaphthalene compound,
1,4-bis-cyclohexylbenzene compound, 4,
4'-bis-cyclohexylbiphenyl compound, phenyl- or cyclohexylpyrimidine compound, phenyl- or cyclohexyldithiane compound, phenyl- or cyclohexyldioxane compound, 1,2-bis-
Phenylethane compounds, 1,2-bis-cyclohexylethane compounds, 1-phenyl-2-cyclohexylethane compounds, optionally halogenated stilbene compounds, benzylphenyl ether compounds, tolan compounds and substituted cinnamic acid compounds Selected from the group of known substances.

Important compounds which can be used as components of the liquid-crystal mixtures according to the invention have the following formula III: R′-L-G-E-R ″, wherein L and E are 1,4-disubstituted benzene or cyclohexane ring, 1,4-disubstituted 1-cyanocyclohexane ring, 4,4-disubstituted biphenyl, phenylcyclohexyl or bicyclohexyl, 2,5-disubstituted pyrimidine, pyridine and 1,3-dioxane ring,
2,6-disubstituted naphthalene, di- and tetrahydronaphthalene, an unsubstituted or laterally substituted carbocyclic or heterocyclic ring system selected from the group comprising quinazoline and tetrahydroquinazoline, G is -CH = CH-, -CH = CY-,
-C≡C-, -CO-O-, -CO-S-, -CH = N
-, - N (O) = N -, - CH = N (O) -, - CH 2
_{-CH 2 -, - CH 2 -O-} , CH 2 -S -, - COO-
Phe-COO- or a CC single bond, Y is halogen, preferably chlorine or -CN,

R ′ and R ″ are each alkyl, alkoxy, alkanoyloxy, alkoxycarbonyl or alkoxycarbonyloxy having up to 18, preferably up to 10, C atoms, which are present in this group and adjacent to oxygen. One CH ₂ group not having —O—,
-CH = CH- or -C≡C-, or these groups R 'and R "
One of the also _{-CN, -NO 2, -CF 3,} -NC
S, -F, -Cl or -Br].

In most of these compounds, R 'and R "are different from one another, one of these radicals usually being an alkyl or alkoxy radical. However, various other substituents which have been proposed Many such substances or mixtures thereof are commercially available, and all of these substances can be prepared by methods known from the literature.

The liquid crystal phases according to the invention are prepared in a manner customary per se. In general, the components are dissolved with one another, preferably at an elevated temperature.

The liquid-crystal phases according to the invention can be modified by using suitable additives so that they can be used in all types of liquid-crystal display devices disclosed to date. Such additives are known to those skilled in the art and are described in detail in the literature. For example, to improve the conductivity, a conductive salt, preferably a complex salt of ethyl-dimethyl-dodecyl-ammonium 4-hexyloxybenzoate, tetrabutylammonium tetraphenylboranate or a crown ether [for this compound, for example, I . Haller et al., Mol.
Cryst. Liq. Cryst. 24 volumes, 249-
258 (1973)], to add a dichroic dye to form a colored guest-host system, or to alter the dielectric anisotropy, viscosity and / or orientation of the nematic phase. Can be added. Such materials are described, for example, in German Offenlegungsschrift Nos. 2,209,127 and 2,240,863,
No. 2,321,632, No. 2,338,281
No. 2,450,088 and No. 2,637,43
Nos. 0, 2,853,728 and 2,90
No. 2,177.

When the liquid crystal material is a nematic liquid crystal material, the other components of this material are a wide variety of compounds known to be useful components of nematic liquid crystal materials, for example, sub-formulas 2.1 to 2 .6 (where Ra and Rb are independently alkyl or alkoxy) can be selected from:

[0065]

Embedded image

In general, the nematic liquid crystal material of this aspect of the invention contains up to about 25% by weight of the terphenyl compound of Formula I. Twisted nematic device (T
In the case of N), the Freede-ricksz effect device and the cholesteric-nematic phase change effect device, the group of materials can effectively contain a compound selected from the formulas 2.1 to 2.6. If a cholesteric phase is required, one or both of the alkyl groups Ra or Rb may contain an asymmetric carbon atom, for example in a 2-methylbutyl group.

A group of terphenyl compounds of the formula I have been found to be useful in liquid crystal materials using the electrically controlled birefringence (ECB) effect. Such materials contain up to about 50% by weight, typically up to about 25%, of one or more of the terphenyl compounds of the formula I. Such a mixture of groups can effectively contain a compound of the following sub-formula 3.1-3.6, wherein Ra and Rb can be alkyl or alkoxy:

[0068]

Embedded image

Certain groups of biphenyl and terphenyl compounds of the formula I have been found to be useful components of liquid crystal materials using the ferroelectric properties of the S _C ^* phase. Certain terphenyl compounds of the formula I exhibit a smectic C phase which persists over a wide temperature range. Accordance connexion, the present invention provides a liquid crystal material exhibiting a S _C phase containing one or two or more of the biphenyl compound or terphenyls compound of formula I. The liquid crystal material can consist entirely of two or more of the biphenyl and / or terphenyl compounds of the formula I. One of the components of this mixture must contain an asymmetric carbon atom to provide the _SC ^* phase. This ingredient is itself
It can be a biphenyl or terphenyl compound of the formula I, but preferably is not a compound of the formula I.

[0070] In addition to one or two or more terphenyls compounds of formula I, containing one or two or more biphenyl compounds of formula I, the mixture having an S _C phase are particularly preferred. Such mixtures are compounds of the following sub-formulae 4.1 to 4.8, wherein Ra and Rb can be alkyl or alkoxy, and X represents O or S, preferably O. Can effectively contain:

[0071]

Embedded image

In the compounds of the formulas 4.1 to 4.8, one 1,4-phenylene group may be substituted by halogen, preferably by fluorine. Equations 4.1 to 4.
Preferred fluorinated compounds represented by formula 8 are represented by the following formula 4.
9 and 4.10:

[0073]

Embedded image

The smectic phase according to the invention also has, in addition to the compound of the formula I and the compound of the formula 4, a negative dielectric anisotropy value.

[Number 1] (Δε ∠ -2) component showing a can contain, for example, compounds of formula 5.1 to 5.3 below:

[0075]

Embedded image

The S of this aspect of the invention _C mixture and S
^{* In a} _C mixture, formulas I, 1 to I, 6, especially
1, I, 2 and I, terphenyls compounds represented by 4, since they exhibit useful S _C phase, which is a preferred ingredient.

[0077] This aspect of the present invention _{S C} material or _S ^{C *}
Material Overall, if not made of biphenyl compounds or terphenyls compound represented by formula I, it is known that the other component is a useful component of S _C and (or) S _C ^* liquid crystal material Compound. Useful _SC
^{* The} liquid crystal material can be composed of one or more of the terphenyl compounds represented by the formula I, and one or more of a mixture of other compounds containing asymmetrically substituted carbon atoms.

The S of this aspect of the invention_C ^*Mixture smell
And R ₁And R _TwoIs preferably used for nematic materials.
Those with a longer carbon chain length than those used
For example, each of these groups preferably has up to 5
Or contains 6 or more carbon atoms. R ₁And R _TwoIs good
Preferably, in such a mixture, n-alkyl
Or n-alkoxy.

The discovery that S _C ^* mixtures can be prepared using the terphenyl compounds of the formula I and their advantages, namely a good S _C phase and a fast switching rate, are exclusively due to the nematic mixture or the ECB. This is entirely unexpected from the known art for mixtures. Indeed, nematic or ECB mixtures are generally indicated to exclude compounds that exhibit smectic properties.

Preferred compounds containing an asymmetric carbon in the S _C ^* material of this aspect of the invention are EP-A-0110.
299, 1-methylheptyl (20 ct ^* ) ester compound, or WO 87/07890 or British Patent Applications 8729502, 8729503, 87
29865 or 87229982

Embedded image And one or more compounds having the formula:

Derivatives of optically active lactic acid are described in WO 86/02
938 or PCT / GB87 / 00132. The optically active terpinoid derivative is WO86 /
04328, WO 87 /
06577, the mandelic ester compound is WO 88
/ 02390, and the derivative of the optically active amino acid is W
O 86/02937 or UK Patent Application 862011
1.

The following sub-formulas 6.1 to 6.6 (where X represents an alkoxy group or an alkylamino group, Y represents H, CF ₃ or CH ₃ , m represents 0 or 1, and n represents Is 1 or 2, and p is 0 or 1).

[0083]

Embedded image

In the compounds of formulas 6.1 to 6.6, one or more groups Phe may be substituted by fluorine, Ra and Rb are as defined above, and Rb is preferably a C ₁ -C ₄ n-alkyl, cycloalkyl or branched alkyl.

Ra present in the above formula is preferably C ₅
-C ₁₂ n- alkyl or n- alkoxy, especially n- octyloxy. Rb is preferably methyl, or Rb is preferably of the general formula

[0086]

Embedded image

(Where a is 0 or a is 1 to
And b and c are each independently
And an integer of 1 to 6, preferably b or c
At least one is 1). R ₁And R _TwoEach
Alkyl with different numbers of carbon atoms
Or R ₁And R _TwoAre together, preferably alicyclic
Group, for example, formula

[0088]

Embedded image Represents a group represented by

When the S _C ^* mixture of this aspect of the invention contains two or more of the compounds containing asymmetric carbon atoms, two or more of these compounds are effectively the opposite. , Ie having (+) and (−) optical rotation or D and L stereoisomerism. In this way, the helical _S ^{C *}
The length of the pitch can be controlled and / or to help align the electrodes of the electro-optical device with the liquid crystal material,
It can produce useful S _A phase.

[0090] In general, S _C ^* mixture of this aspect of the present invention is a chiral dopant (one or two or more) 1
Contains 30% by weight. The remainder of the mixture comprises one or more compounds of the formula I, in particular the compounds of the formula I, 1
To I, 6 or the compounds of the formulas I, 13 and I, 17 to I, 19 can be contained. The total amount is 100% by weight. Differently, S
_{The C} ^* mixture can consist of 1 to 30% by weight of the chiral doping substance (s), the remainder being the compound of the formula I plus the formula 4.1 to 4.10 or the formula 5.1 to 5.1. 5.3 or more, and / or other known smectic C
A mixture of components or other suitable additives. In general, compounds represented by formulas 4.1 to 4.10 or 5.
The weight percentage of compounds represented by 1 to 5.3 is 80% of the mixture.
Do not exceed%.

The liquid crystal material of the present invention can be used in a liquid crystal electro-optical display device having a known structure. The present invention will now be described with reference to the accompanying FIG.
This will be described by way of example with reference to FIGS. The following abbreviations are used: K = solid crystal N = nematic liquid crystal S _A = smectic A liquid crystal S _C = smectic C liquid crystal I = isotropic liquid

[0092]

[Example]

Example 1 4-n-hexyloxy-4 ″ -n-pentyl-2 ′,
Preparation of 5'-difluoro-p-terphenyl 1A 4-n-hexyloxybromobenzene 1-bromohexane (60 g) in acetone (150 m
1) at room temperature with 4-bromophenol (71 g) and K ₂ CO ₃ (12 g) in acetone (600 ml).
0 g) is added dropwise to the stirred mixture. The stirred mixture is heated to reflux for 43 hours (i.e., until glc indicates the reaction is complete). The product is extracted twice into ether and the combined ether extracts are washed with water, 5% aqueous NaOH and then dried (MgSO ₄ ). The solvent was removed under reduced pressure and the residue was distilled (bp = 100-110 ° C.).
/0.1 mmHg) to obtain a colorless liquid.

1B 4-n-hexyloxyphenylboronic acid A solution of a Grignard reagent prepared from Mg (7.75 g) and 1A (72 g) in anhydrous THF (250 ml) was dried under a dry N ₂ atmosphere under a tritium atmosphere. Add isopropyl borate (109.1 g) in a stirred, cooled (-78 ° C.) solution of anhydrous THF (40 ml) dropwise. The stirred mixture is allowed to warm to room temperature overnight and then stirred at room temperature for 1 hour with 10% HCl (320 ml). The product is extracted twice into ether and the combined ether extracts are washed with water and then dried (MgS
O ₄ ). The solvent is removed under reduced pressure to give a colorless solid, mp
= 80-85 ° C.

1C 4-Amino-2,5-difluorobromobenzene N-bromosuccinimide (42 g) was added to dry CH ₂ C
l ₂ (180 ml) in 2,5 - stirring of difluoroaniline (30~96g), cooled (-10 ° C. ~0
C) Add to the solution in small portions over 1.5 hours. The mixture is stirred at 0 ° C. for 2 hours. Red solution with plenty of water
Wash once and then dry (MgSO ₄ ). The solvent is removed under reduced pressure to give a red solid, mp = 74-75
° C.

1D 2,5-Difluoro-4-bromobiphenyl A solution of 1C in dry benzene (200 ml) was added to a stirred and cooled (0 ° C.) solution of isopentylnitrile (33.6 g) in dry benzene. While stirring, add dropwise over 1.5 hours. The mixture is heated at reflux for 1.5 hours and then allowed to cool. The product is treated with ether 2
Extract and collect the combined organic layers with water, sodium bicarbonate,
Wash sequentially with 2M hydrochloric acid and water, then dry (M
gSO _4). The solvent is removed under reduced pressure and the crude product is steam distilled to give a brown-black solid. The product is further purified by column chromatography (silica gel / dichloromethane) to give a dark brown, low melting solid.

1E 4′-Pentanoyl-2,5-difluoro-4-bromobiphenyl AlCl ₃ (25.4 g) was triturated with valeroyl chloride (34.9) in dry dichloromethane (120 ml).
g) and add to the cooled (0 ° C.) solution. A solution of 1D (13.2 g) in dry dichloromethane (120 ml) is added dropwise at 0 ° C. over 2 hours. The mixture is stirred at room temperature for 48 hours and poured onto crushed ice / conc. HCl. The separated aqueous layer is washed twice with CH ₂ Cl ₂ and the combined organic layers are washed with water, NaHCO ₃ , and water, and then dried (MgSO ₄ ). The solvent is removed under reduced pressure,
The resulting dark red oil was distilled under reduced pressure (0.1 mm
Hg, temperature not recorded), the resulting low melting red-
The brown solid is subjected to column chromatography (silica gel / C
Further purification by H ₂ Cl ₂ ) gives a low melting red-brown solid.

1F 4′-n-pentyl-2,5-difluoro-4-bromobiphenyl triethylsilane (7.0 g) was cooled (0 ° C.) to 1E (8.0 g) in trifluoroacetic acid (40 ml). ,
Add dropwise to the stirred solution over 2 hours. The reaction mixture was stirred at room temperature overnight, then NaHCO
₃ Pour into the solution. The product is extracted twice into ether and the combined ether layers are washed with water and then dried (MgSO ₄ ). The solvent is removed under reduced pressure to give an orange-brown oil. The crude product is distilled under reduced pressure (short path, 110-120 ° C. at 0.01 mm Hg) to give a red oil.

1G 4′-n-hexyloxy-4 ″-
n- pentyl-2 ', a solution of 1B in 5'-difluoro -p- terphenyls ethanol (15ml) (0.9806g), under dry N ₂ at room temperature, benzene (20ml)
And _{2M-Na 2 CO 3 (20} ml) solution of 1F (1.
25g) and tetrakis (triphenylphosphine)
Add dropwise to the stirred mixture of palladium (O) (0.1392 g). The stirred mixture is heated to reflux (90-95 ° C.) for 23 hours (i.e., until glc analysis shows no starting material). The mixture was allowed to cool and, if necessary, 30% H ₂ O ₂ (2 ml)
And stir at room temperature for 1 hour. The product twice with ether,
The extracted and collected organic extracts are washed with brine and then dried (MgSO ₄ ). The solvent was removed under reduced pressure, and the residue was subjected to column chromatography [silica gel / petroleum ether (bp = 40-60 ° C.)-Dichloromethane, 3-1].
And the resulting colorless solid is recrystallized from ethanol to give a colorless plate, K 53.0N 11
8.0 I.

Example 2 Preparation of 4,4 "-di-n-pentyl-2 ', 5'-difluoro-p-terphenyl 2A 4-Pentanoyl-bromobenzene Pentanoyl chloride (50 g) was mixed with bromobenzene (150 ml). Stir with aluminum chloride (0.2 g) and add dropwise to the cooled (0 ° C.) mixture, stir at 0 ° C. for 1 hour, heat at 80 ° C. for 2 hours, allow to cool, and then add 18% hydrochloric acid Pour the product into CH
Extract twice in Cl ₃ , wash the combined organic extracts with water, then steam distill to remove chloroform and excess bromobenzene. The product is treated with chloroform 2
Extracted once and the combined organic phases are washed with water and then dried (MgSO ₄ ). The solvent is removed under reduced pressure and the residue is distilled (bp 180-184 ° C at 20 mm Hg) to give a colorless solid.

2B 4-n-Pentylbromobenzene 2A (77.2) in diethylene glycol (250 ml).
1 g), a mixture of hydrazine hydrate (46.4 g) and KOH (590 g) was heated at 130 ° C. for 2 hours to remove excess hydrazine hydrate and to reduce the temperature to 2 ° C.
Time, increase to 200 ° C. Cool the mixture to 18% HC
and the product is extracted twice into ether, the combined ether extracts are washed with water and then dried (MgSO ₄ ). The solvent is removed under reduced pressure and the residue is distilled (bp 145-148 ° C at 20 mmHg) to give a colorless liquid (58.1 g, 80%).

The Grignard reagent prepared from 2C 4-n-pentylphenylboronic acid 2B is converted to a boron compound using tri-isopropyl borate in a manner similar to that described in 1B. The product from 2C is
Coupled with the product from 1F in a manner analogous to that described in 1) above to give 4,4 "-di-n-pentyl-2 ',
To obtain 5′-difluoro-p-terphenyl, K 6
5.0 N 86.0 I.

Example 3 4-n-hexyloxy-4 ″ -n-pentyl-2,
Preparation of 2 "-difluoro-p-terphenyl 3A 4-n-hexyloxy-2-fluorobromobenzene 1-bromohexane (9.3) in acetone (20 ml).
3g) at room temperature in 4-acetone (75 ml).
Add dropwise to a stirred mixture of bromo-3-fluorophenol (9.00 g) and potassium carbonate (13.5 g). The stirred mixture is allowed to stand for 21 hours (ie, glc
Heat to reflux until analysis indicates completion of the reaction). The product is extracted twice into ether and the combined ether extracts are washed with water, 10% sodium hydroxide, water and then dried (MgSO ₄ ). The solvent was removed under reduced pressure and the residue was distilled (bp 100-105 at 0.1 mm Hg).
C) to give a colorless liquid.

3B A solution of n-butyllithium 4-hexyloxy-2-fluorophenylboronate (10.0M in hexane,
3.30 ml) under dry THF under dry THF (70
(3 ml) of 3A (9.0 g) and cooled (−7 g).
8 ° C.) Add dropwise to the solution. The stirred mixture is maintained under these conditions for 2.5 hours, then dried in THF (5.
0-ml) of tri-isopropyl borate (11.28).
The cooled solution of g) is added dropwise at -78 ° C. The stirred mixture is allowed to warm to room temperature overnight and then stirred at room temperature with 10% HCl (50 ml) for 1 hour. The product was extracted twice into ether and the combined ether extracts were washed with water, then dried (MgSO _4), and the solvent is removed under reduced pressure, off - obtain a solid white.

3C 4-n-hexyloxy-4 ″ -n
-The product from pentyl-2,2 "-difluoro-p-terphenyl 3B is coupled with 4'-bromo-2-fluoro-4-pentylbiphenyl in a manner similar to that described in 1G. By column chromatography [silica gel / petroleum fraction (bp = 40-60 ° C.)
Purify with dichloromethane 3: 1] and recrystallize the resulting colorless solid from ethanol to give a colorless waxy plate, K 45.0 N 131.0 I.

Example 4 4-n-octyloxy-4 "-pentyl-2,2"-
Preparation of difluoro-p-terphenyl 4A 4-n-octyloxy-2-fluoro-bromobenzene The method of use is the same as for 3A. Quantity: 4-Bromo-4-fluoro-phenol 6.00 g 1-bromo octane 7.40g K ₂ CO ₃ 10.00g product was distilled under reduced pressure (bp at 0.5 mmHg = 1
40-142 ° C.) to give a colorless liquid.

4B 4′-n-Pentyl-2′-fluorobiphenyl-4-ylboronic acid A method similar to that for 3B is used. Amount: 3'-bromo-2-fluoro-4-n-pentylbiphenyl 9.90 g magnesium 0.871 g tri-isopropyl borate 11.66 g Crude yield: 8.85 g

The same method is used as for 4C 4-n-octyloxy-4 ″ -pentyl-2,2 ″ -difluoro-p-terphenyl 1G. Amount: 4A 6.00 g 4B 1.75 g Tetrakis (triphenylphosphine) palladium (O) 0.297 g The product is purified by column chromatography to give a colorless solid, K 42.5 N 121.5 I.

Example 5 4-n-hexyloxy-4 ″ -n-pentyl-3,
Preparation of 2 "-difluoro-p-terphenyl 4-n-hexyloxy-3-fluorophenylboronic acid was converted to 4'-bromo-2 in a manner similar to that described in 1G.
Coupling with -fluoro-4-n-pentylbiphenyl. The crude product was subjected to column chromatography [silica gel / petroleum fraction (bp = 40-60 ° C.)-CH ₂ Cl
₂ 6: 1] to give the ethanol colorless solid obtained - ethyl acetate (10: 1) and recrystallized from to afford a colorless plate-like workpiece, K 96.0S _C 105.5 N 1
39.0 I.

Example 6 4-n-hexyloxy-4 ″ -n-pentyl-2 ′,
Preparation of 3'-difluoro-p-terphenyl 6A 2,3-Difluorophenylboronic acid 1,2-difluorobenzene is converted to 6A with tri-isopropyl borate in a manner similar to that described in 3B. The same method is used as for 6B 4-n-pentyl-2 ′, 3′-difluorobiphenyl 1G.

Amount: 1-bromo-4-pentylbenzene 3.80 g 6A 3.50 g tetrakis (triphenylphosphine) palladium (O) 0.651 g Coupling to form the biphenyl compound was found to be faster in the case of the terphenyl compound. The reaction is completed within 5 hours. The crude product was purified by column chromatography [silica gel / petroleum fraction (bp = 40-60)
_{℃) -CH 2 Cl 2 3:} 1] to afford a colorless liquid. The same method is used as for 6C 4'-n-pentyl-2,3-difluorobiphenyl-4-ylboronic acid 3B.

Amount: 6B 4.00 g n-butyllithium 1.50 ml, 10.0 M tri-isopropyl borate in hexane 5.70 g

6D 4-n-hexyloxy-4 ″ -pentyl-2 ′, 3 ′
-Difluoro-p-terphenyl Use the same method as for 1G. Amount: 1B 1.30 g 6C 2.0 g Tetrakis (triphenylphosphine) palladium (O) 0.312 g The crude product was obtained by column chromatography [silica gel / petroleum fraction (boiling point 40-60 ° C.): dichloromethane 6: 1. ]
And the resulting colorless solid is recrystallized from ethanol to give a colorless plate. K 53 ° S _C 6
5.5 ° N 149 ° I

Homologous compound 6E: 4-n-octyloxy-4 ″ -n-pentyl-2 ′, 3′-p-terphenyl is obtained in a similar route by 1-bromo-4-octyloxybenzene instead of 1B. It produced using this compound is prepared by the same method as in 1B:. amount: 4-bromo phenol 64.54 g 1-bromo-octane 60.00 g K ₂ CO ₃ 103.5 g of a colorless liquid, bp = 145 ° C./0.1 mmHg The method similar to that of 6D is used for the production of 6E.

Amount: 1-bromo-4-octoxybenzene 1.40 g 6C 1.90 g Tetrakis (triphenylphosphine) palladium (O) 0.3102 g The crude product was obtained by column chromatography [silica gel / petroleum fraction ( bp: 40-60 ° C.) — CH ₂ Cl ₂ 5: 1], and the resulting colorless solid is recrystallized from ethanol-ethyl acetate (4: 1) to give a colorless plate.
48.5 S _C 95.1 N 141.5 I.

Example 7 Preparation of 4,4 "-di-n-pentyl-2 ', 3'-difluoro-p-terphenyl Use the same method as for 1G. Amount: 1.30 g of 2B 2.10 g of 6C 0.28 g of tetrakis (triphenylphosphine) palladium (O) The crude product was purified by column chromatography [silica gel / petroleum fraction (bp: 40 to 60 ° C.) — CH ₂ Cl ₂ 5: 1] to obtain a crude product. The colorless solid obtained is recrystallized from ethanol to give a colorless plate, K 60 N 120 I.

Example 8 4-n-hexyloxy-4 "-n-pentyl-2,3
Preparation of 8 -Difluoro-terphenyl 8A 2,3-Difluorophenol F. A modified version of Hawthorne [J. Org. Chem. (1957), 22 , 1
001]. Amount: 6A 4.40 g 10% hydrogen peroxide 30 ml Product: off-white solid, mp: 34-36
° C.

8B A method similar to that for 2,3-difluoro-n-hexyloxybenzene 3A is used. The amount: 8A 7.00 g 1-bromo-hexane 10.72 g K ₂ CO ₃ and distilled 17.40g crude product obtain (bp 122 ℃ / 15mmHg) colorless liquid.

8C 4-n-hexyloxy-2,3-
The same method is used as for difluorophenylboronic acid 3B. Amount: 10.0 g of 8B 4.70 ml of n-butyllithium, 17.70 g of 10.0 M tri-isopropyl borate in hexane

8D 4-n-hexyloxy-4 ″ -n-pentyl-2,3
-Difluoro-p-terphenyl Use the same method as for 1G. Amount: 4-bromo-4'-pentylbiphenyl 1.40 g 8C 1.50 g Tetrakis (triphenylphosphine) palladium (O) 0.2868 g The crude product was obtained by column chromatography [silica gel / petroleum fraction (bp: 40-60 ° C.) — CH ₂ Cl ₂ 3: 1] and the resulting colorless solid is recrystallized from ethanol-ethyl acetate (10: 1) as colorless crystals, K
_{97.5 ° S C 145.5 ° N 166} ° I.

Example 8b 4-n-octyloxy-4 "-n-pentyl-2,3
Preparation of -Difluoro-p-terphenyl This compound, instead of 8B, is 1,2-difluoro-3-
Produced by a similar route using octoxybenzene. This starting compound is produced using the same method as in the case of 3A. The amount: 8A 7.00 g 1-bromo octane 12.55g K ₂ CO ₃ 17.40g crude product obtained distilled (bp 150 ℃ / 15mmHg) colorless liquid.

8E 4-n-octyloxy-2,3-
Prepare 8E using a method similar to that for difluorophenylboronic acid 8C. Amount: 1,2-difluoro-3-octoxybenzene 7.50 g n-butyllithium 3.10 ml, 10.0 M triisopropyl borate in hexane 11.66 g A colorless solid forms.

8F 4-n-octyloxy-4 ″ -n
-A method similar to that for pentyl-2,3-difluoro-p-terphenyl 8D. Amount: 4-bromo-4'-pentylbiphenyl 1.54 g 2,3-difluoro-4-octoxyphenylboronic acid 1.75 g Tetrakis (triphenylphosphine) palladium (O) 0.309 g The crude product is Purification by column chromatography [silica gel / petroleum fraction (bp: 40-60 ° C.) — CH ₂ Cl ₂ 3: 1], and the obtained colorless solid was recrystallized from ethanol-ethyl acetate (4: 1). To give colorless crystals, K 9
_{3.5 S C 144 S A 148 N} 159 I.

Example 9 4,4 "-Di-n-pentyl-2,6-difluoro-p
-Production of terphenyl 9A 1,3-difluoro-5- (1-hydroxy pen
Butyl) -benzene in dry THF (100 ml).
Difluoro-benzene (50.2 g, 0.26 mol)
And magnesium (7.25 g, 0.30 mol)
The stirred solution of the Grignard reagent
Under pentanal (1) in dry ether (75 ml)
(9.0 g, 0.22 mol) is added dropwise. Stirring
The stirred mixture was heated to reflux for 2 hours, cooled,
A saturated solution of ammonium (300 ml) is added. Product
Was extracted into ether (twice) and the collected ether extracts
Are washed with water and then dried (MgSO 4)_Four). solvent
Was removed under reduced pressure and the resulting pale orange liquid (5
1.1 g) are distilled to give a colorless liquid. Small amount of crude product
Is column chromatography [silica gel / dichlorometa]
To obtain a colorless liquid, 0.5 mmHg
Bp: 90 ° C.

9B 1,3-Difluoro-5-pent-1-enylbenzene Phosphorus (V) oxide (64.5 g, 0.45 mol) was added at room temperature to the compound 9A (3
(5.0 g, 0.175 mol). The mixture is stirred at room temperature overnight (glc analysis indicates absence of starting material) and then filtered.

9C 1,3-Difluoro-5-pentylbenzene 5% palladium on charcoal (4.0 g) is added at room temperature to the above filtrate [ie compound 9B in pentane (150 ml)]. The stirred mixture is allowed to stand at atmospheric pressure for 4 hours (ie,
Hydrogenate and filter the mixture (until glc analysis indicates absence of feed material). Most of the pentane is removed under reduced pressure and the last amount of pentane is distilled off at 38 ° C. (760 mm
Hg), the residue is then distilled to give a colorless liquid, 7
Bp at 60 mmHg: 200 ° C.

9D Solution of n-butyllithium 2,6-difluoro-5-pentylphenylboronic acid (10.4M in hexane;
(2.70 ml, 0.028 mol) are stirred under dry nitrogen and added dropwise to a cooled (−78 ° C.) solution of 9C in dry THF. The stirred mixture is maintained under these conditions for 2.5 hours and then dried in THF (50 m
l) tri-isopropyl borate (10.22 g,
(0.054 mol) is added dropwise at -78 ° C. The stirred mixture is warmed to room temperature overnight and then stirred with 10% hydrochloric acid (30 ml) for 1 hour. The product is extracted into ether (2 times) and the collected ether extracts are washed with water and then dried (MgS
O ₄ ). The solvent is removed under reduced pressure to give a colorless solid, m
p: 95-100 ° C.

9E 3-Pentyl-4 ″ -hexyloxy-2,6-difluoro-p-terphenyl 1G The same procedure is used as for 1G. Amount: 4-bromohexoxybiphenyl 1.30 g 9D 1.10 g 0.157 g of tetrakis (triphenylphosphine) palladium (O) The crude product was obtained by column chromatography [basic alumina /
Petroleum fraction containing gradually increasing amounts of dichloromethane (bp: 40-60 ° C.)] and the resulting colorless solid is recrystallized from ethanol to give a colorless plate, K 62 ° N 123 ° I.

9F Use the same method as for 4,4 ″ -dipentyl-2,6-difluoro-p-terphenyl 1G. Amount: 4-bromo-4′-pentylbiphenyl 1.40 g 9D 1.37 g 0.157 g of tetrakis (triphenylphosphine) palladium (O)

The crude product was purified by column chromatography [silica gel / petroleum fraction (bp: 40-60 ° C.) — CH ₂ C
l ₂ , 1: 1] to give a colorless liquid containing solids. The solid is filtered off and the petroleum fraction (bp: 40-6)
(0 ° C.). The solvent is removed under reduced pressure to obtain a colorless liquid, two impurities are removed by using a Kugelrohr distillation apparatus, and the obtained colorless solid is recrystallized from ethanol to obtain colorless crystals. K 50 °
N 82 ° I.

Example 10 Preparation of 4,4 "-di-n-alkyl-2 ', 3'-difluoro-p-terphenyl compound 10A 4-n-alkyl-1- (2,3-difluorophenyl) -cyclohexyl -1-ene compound 0.3 mol of n-butyllithium and n-hexane (188
ml) with 1,2-difluorobenzene (0.3 mol), tetrahydrofuran (THF) (60 ml).
0 ml) and tetramethylethylenediamine (TME
DA, 0.3 mol) cooled (−60 ° to −70 ° C.)
Add to solution. The stirred mixture is kept for 3 hours, then a mixture of 4-n-pentylcyclohexanone (0.32 mol) and tetrahydrofuran (100 ml) is added. After conventional work-up, the residue is dissolved in toluene (1000 ml) and boiled for 3 hours with p-toluenesulfonic acid (PTSA) in a Dean Stark trap. The solvent is removed under reduced pressure and the residue is distilled,
4-n-pentyl-1- (2,3-fluorophenyl)
-Cyclohex-1-ene as a colorless liquid, (b
p: 123 ° / 0.5 mmHg).

Similarly, the following compound is obtained: 4-ethyl-1- (2,3-difluorophenyl) -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) -cyclohex-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)-
Cyclohex-1-ene 4-ethoxy-1- (2,3-difluorophenyl)-
Cyclohex-1-ene

4-propoxy-1- (2,3-difluorophenyl) -cyclohex-1-ene 4-butoxy-1- (2,3-difluorophenyl)-
Cyclohex-1-ene 4-pentoxy-1- (2,3-difluorophenyl)
-Cyclohex-1-ene 4-hexoxy-1- (2,3-difluorophenyl)
-Cyclohex-1-ene 4-heptoxy-1- (2,3-difluorophenyl)
-Cyclohex-1-ene

4-octoxy-1- (2,3-difluorophenyl) -cyclohex-1-ene 4-nonoxy-1- (2,3-difluorophenyl)-
Cyclohex-1-ene 4-decoxy-1- (2,3-difluorophenyl)-
Cyclohex-1-ene 4-undecoxy-1- (2,3-difluorophenyl) -cyclohex-1-ene

10B 4-Alkyl-2 ′, 3′-difluorobiphenyl compound 4-pentyl-1- (2,3-difluoro-phenyl)
0.1 mol of cyclohex-1-ene and 500 parts of toluene
to the mixture with 0.2 ml of 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ).
Reflux for hours. After finishing in the usual way, 2 ',
3′-Difluorobiphenyl is obtained, bp: 125 ° C./0.5 mmHg. Similarly, the following compounds are obtained:

4-ethyl-2 ′, 3′-difluorobiphenyl 4-propyl-2 ′, 3′-difluorobiphenyl 4-butyl-2 ′, 3′-difluorobiphenyl 4-hexyl-2 ′, 3 '-Difluorobiphenyl 4-heptyl-2', 3'-difluorobiphenyl 4-octyl-2 ', 3'-difluorobiphenyl 4-nonyl-2', 3'-difluorobiphenyl

4-decyl-2 ′, 3′-difluorobiphenyl 4-ethoxy-2 ′, 3′-difluorobiphenyl 4-propoxy-2 ′, 3′-difluorobiphenyl 4-butoxy-2 ′, 3 '-Difluorobiphenyl 4-pentoxy-2', 3'-difluorobiphenyl

4-hexoxy-2 ′, 3′-difluorobiphenyl 4-heptoxy-2 ′, 3′-difluorobiphenyl 4-octoxy-2 ′, 3-difluorobiphenyl 4-nonoxy-2 ′, 3 ′ -Difluorobiphenyl 4-decoxy-2 ', 3'-difluorobiphenyl 4-dodecoxy-2', 3'-difluorobiphenyl

In the same manner, alkyl-
Using (or alkoxy) -2,3-difluorobenzene, the following 4,4-dialkyl- (or alkoxy) -2,3-difluorobiphenyl compound is obtained:

4-octyloxy-4'-pentyl-
2,3-difluorobiphenyl K14 (N13.
5) I 4-octyloxy-4′-heptyl-2,3-difluorobiphenyl K24 (S _C 6 S _A 13 N 2
3) 4-Nonyloxy-4'-decyl-2, -difluorobiphenyl K 47I 4-ethoxy-4'-pentyl-2,3-difluorobiphenyl K-10I

4-pentyloxy-4'-octyloxy-2,3-difluorobiphenyl K 8.0 S _A
12.0 N 18.0 I 4-heptyloxy-4'-pentyl-2,3-difluorobiphenyl K0.5 I 4-nonyloxy-4'-octyloxy-2,3-difluorobiphenyl K 25.0 (S _C 11.5)
S _A 33.0 N 34.0 I

10C 4,4 ″ -dialkyl-2 ′,
3′-Difluoro-p-terphenyl compound 4-pentyl-2 ′, 3′-difluorobiphenyl
One mole is deprotonated with n-butyllithium in THF / TMEDA according to Example 10A and then reacted with 0.1 mole of 4-propylcyclohexanone. Example 10
According to B, after oxidation with DDQ 0.2 mol, 4-pentyl-4 "-propyl-2 ', 3'-difluoro-p-
Terphenyl is obtained. Similarly, the following compounds are obtained:

4-ethyl-4 ″ -propyl-2 ′, 3 ′
-Difluoro-p-terphenyl 4-propyl-4 "-propyl-2 ', 3'-difluoro-p-terphenyl K94N133I4-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-heptyl-4 "-propyl- 2 ', 3'-difluoro-p-terphenyl 4-octyl-4 "-propyl-2', 3'-difluoro-p-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-ethoxy-4"-propyl-2',3'-difluoro-p-terphenyl 4-propoxy- 4 "-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-heptoxy-4"-propyl-2',3'-difluoro-p-terphenyl

4-octoxy-4 "-propyl-2 ',
3'-difluoro-p-terphenyl 4-nonoxy-4 "-propyl-2 ', 3'-difluoro-p-terphenyl 4-decoxy-4"-propyl-2',3'-difluoro-p-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-p-terphenyl 4-pentyl-4 ″ -pentyl-2 ′, 3′-difluoro-p-terphenyl K 60 0.0 ° N 120.0
° I

4-hexyl-4 ″ -pentyl-2 ′,
3′-Difluoro-p-terphenyl 4-heptyl-4 ″ -pentyl-2 ′, 3′-difluoro-p-terphenyl K 36.5 (S _C 24.
0) N 110.5 I 4-octyl-4 "-pentyl-2 ', 3'-difluoro-p-terphenyl 4-nonyl-4"-pentyl-2',3'-difluoro-p-terphenyl 4-decyl -4 "-pentyl-2 ', 3'-difluoro-p-terphenyl 4-dodecyl-4"-pentyl-2',3'-difluoro-p-terphenyl 4-ethoxy-4 "-pentyl-2 ', 3 '-Difluoro-p-terphenyl 4-propoxy-4 "-pentyl-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 K53 0.0 ° S _C 6
5.5 ° N 149.0 ° I 4-Heptoxy-4 ″ -pentyl-2 ′, 3′-difluoro-p-terphenyl 4-octoxy-4 ″ -pentyl-2 ′, 3′-difluoro-p-terphenyl K 48.5 ° S _C 9
5.1 ° N 141.5 ° I 4-Nonoxy-4 ″ -pentyl-2 ′, 3′-difluoro-p-terphenyl 4-decoxy-4 ″ -pentyl-2 ′, 3′-difluoro-p-terphenyl 4-dodecoxy-4 "-pentyl-2 ', 3'-difluoro-p-terphenyl

4-Nonyl-4 "-heptyl-2 ', 3'
-Difluoro-p-terphenyl K 49.0 S _C
77.0 S _A 93.0 N 108.5 I 4- ethyl-4 "- octyl-2 ', 3'-difluoro -p- terphenyls 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-heptyl-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"- Ok -2 ', 3'-difluoro-p-terphenyl 4-ethoxy-4 "-octyl-2', 3'-difluoro-p-terphenyl 4-propoxy-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- Heptoxy-4 "-octyl-2 ', 3'-difluoro-p-terphenyl 4-octoxy-4"-octyl-2',3'-difluoro-p-terphenyl 4-nonoxy-4 "-octyl-2 ', 3'-difluoro-p-terphenyl 4-decoxy-4 "-octyl-2 ', 3'-difluoro-p-terphenyl 4-dodecoxy-4"-octyl-2',3'-difluoro-p-terphenyl

4-nonoxy-4 "-ethoxy-2 ',
3'-difluoro-p-terphenyl 4-decoxy-4 "-ethoxy-2 ', 3'-difluoro-p-terphenyl 4-dodecoxy-4"-ethoxy-2',3'-difluoro-p-terphenyl 4- Ethyl-4 "-heptoxy-2 ', 3'-difluoro-p-terphenyl 4-butyl-4"-heptoxy-2',3'-difluoro-p-terphenyl 4-hexyl-4 "-heptoxy-2 ', 3′-difluoro-p-terphenyl 4-heptyl-4 ″ -heptoxy-2 ′, 3′-difluoro-p-terphenyl 4-nonyl-4 ″ -heptoxy-2 ′, 3′-difluoro-p-terphenyl 4- Dodecyl-4 "-heptoxy-2 ', 3'-difluoro-p-terphenyl

4-ethoxy-4 ″ -heptoxy-2 ′,
3′-difluoro-p-terphenyl 4-propoxy-4 ″ -heptoxy-2 ′, 3′-difluoro-p-terphenyl 4-butoxy-4 ″ -heptoxy-2 ′, 3′-difluoro-p-terphenyl 4- Pentoxy-4 "-heptoxy-2 ', 3'-difluoro-p-terphenyl 4-hexoxy-4"-heptoxy-2',3'-difluoro-p-terphenyl

4-Heptoxy-4 "-heptoxy-
2 ', 3'-difluoro-p-terphenyl 4-octoxy-4 "-heptoxy-2', 3'-difluoro-p-terphenyl 4-nonoxy-4" -heptoxy-2 ', 3'-difluoro-p- Terphenyl 4-decoxy-4 "-heptoxy-2 ', 3'-difluoro-p-terphenyl 4-dodecoxy-4"-heptoxy-2',3'-difluoro-p-terphenyl

Example 11 4,4 ""-di-n-alkyl-2 ', 3'-difluoro-p-quarterphenyl compound 4-pentyl-2', 3'-difluorobiphenyl (0.1 mol, This compound is prepared according to Example 10B), deprotonated according to Example 10A and then 4- (p
-Propylphenyl) -cyclohexanone 0.1 mol. After oxidation with 0.2 mol of DDQ according to Example 10B, 4'-pentyl-4 "'-propyl-2',
3'-Difluoro-p-quarterphenyl is obtained. Similarly, the following compounds are obtained:

4-ethyl-4 ″ ′-propyl-2 ′,
3'-difluoro-p-quarterphenyl 4-propyl-4 "'-propyl-2', 3'-difluoro-p-quarterphenyl 4-butyl-4"'-propyl-2',3'-difluoro -P-quarterphenyl 4-hexyl-4 "'-propyl-2', 3'-difluoro-p-quarterphenyl 4-heptyl-4"'-propyl-2',3'-difluoro-p-quarter Phenyl

4-octyl-4 "'-propyl-2',
3'-difluoro-p-quarterphenyl 4-nonyl-4 "'-propyl-2', 3'-difluoro-p-quarterphenyl 4-decyl-4"'-propyl-2',3'-difluoro -P-quarterphenyl 4-dodecyl-4 "'-propyl-2', 3'-difluoro-p-quarterphenyl 4-ethoxy-4"'-propyl-2',3'-difluoro-p-quarter Phenyl

4-propoxy-4 "'-propyl-
2 ', 3'-Difluoro-p-quarterphenyl 4-butoxy-4 "'-propyl-2 ', 3'-difluoro-p-quarterphenyl 4-pentoxy-4"'-propyl-2 ', 3 '-Difluoro-p-quarterphenyl 4-hexoxy-4 "'-propyl-2 ', 3'-difluoro-p-quarterphenyl 4-heptoxy-4"'-propyl-2 ', 3'-difluoro- p-quarterphenyl

4-octoxy-4 "'-propyl-
2 ', 3'-Difluoro-p-quarterphenyl 4-nonoxy-4 "'-propyl-2 ', 3'-difluoro-p-quarterphenyl 4-decoxy-4"'-propyl-2 ', 3 '-Difluoro-p-quarterphenyl 4-ethyl-4 "'-octyl-2 ', 3'-difluoro-p-quarterphenyl 4-propyl-4"'-octyl-2 ', 3'-difluoro- p-quarterphenyl

4-butyl-4 "'-octyl-2',
3'-difluoro-p-quarterphenyl 4-pentyl-4 "'-octyl-2', 3'-difluoro-p-quarterphenyl 4-hexyl-4"'-octyl-2',3'-difluoro -P-quarterphenyl 4-heptyl-4 "'-octyl-2', 3'-difluoro-p-quarterphenyl 4-octyl-4"'-octyl-2',3'-difluoro-p-quarter Phenyl

4-nonyl-4 "'-octyl-2',
3'-difluoro-p-quarterphenyl 4-decyl-4 "'-octyl-2', 3'-difluoro-p-quarterphenyl 4-dodecyl-4"'-octyl-2',3'-difluoro -P-quarterphenyl 4-ethoxy-4 "'-octyl-2', 3'-difluoro-p-quarterphenyl 4-propoxy-4"'-octyl-2',3'-difluoro-p-quarter Phenyl

4-butoxy-4 ″ ′-octyl-2 ′,
3'-Difluoro-p-quarterphenyl 4-pentoxy-4 "'-octyl-2', 3'-difluoro-p-quarterphenyl 4-hexoxy-4"'-octyl-2',3'-difluoro -P-quarterphenyl 4-heptoxy-4 "'-octyl-2', 3'-difluoro-p-quarterphenyl 4-octoxy-4"'-octyl-2',3'-difluoro-p-quarter Phenyl

4-nonoxy-4 ″ ′-octyl-2 ′,
3'-difluoro-p-quarterphenyl 4-decoxy-4 "'-octyl-2', 3'-difluoro-p-quarterphenyl 4-ethyl-4"'-ethoxy-2',3'-difluoro -P-quarterphenyl 4-propyl-4 "'-ethoxy-2', 3'-difluoro-p-quarterphenyl 4-butyl-4"'-ethoxy-2',3'-difluoro-p-quarter Phenyl

4-pentyl-4 ″ ′-ethoxy-2 ′,
3'-difluoro-p-quarterphenyl 4-hexyl-4 "'-ethoxy-2', 3'-difluoro-p-quarterphenyl 4-heptyl-4"'-ethoxy-2',3'-difluoro -P-quarterphenyl 4-octyl-4 "'-ethoxy-2', 3'-difluoro-p-quarterphenyl 4-nonyl-4"'-ethoxy-2',3'-difluoro-p-quarter Phenyl

4-decyl-4 "'-ethoxy-2',
3'-difluoro-p-quarterphenyl 4-dodecyl-4 "'-ethoxy-2', 3'-difluoro-p-quarterphenyl 4-ethoxy-4"'-ethoxy-2',3'-difluoro -P-quarterphenyl 4-propoxy-4 "'-ethoxy-2', 3'-difluoro-p-quarterphenyl 4-butoxy-4"'-ethoxy-2',3'-difluoro-p-quarter Phenyl

4-pentoxy-4 "'-ethoxy-
2 ', 3'-Difluoro-p-quarterphenyl 4-hexoxy-4 "'-ethoxy-2 ', 3'-difluoro-p-quarterphenyl 4-heptoxy-4"'-ethoxy-2 ', 3 '-Difluoro-p-quarterphenyl 4-octoxy-4 "'-ethoxy-2 ', 3'-difluoro-p-quarterphenyl 4-nonoxy-4"'-ethoxy-2 ', 3'-difluoro- p-quarterphenyl

4-decoxy-4 ″ ′-ethoxy-2 ′,
3'-difluoro-p-quarterphenyl 4-ethyl-4 "'-heptoxy-2', 3'-difluoro-p-quarterphenyl 4-propyl-4"'-heptoxy-2',3'-difluoro -P-quarterphenyl 4-butyl-4 "'-heptoxy-2', 3'-difluoro-p-quarterphenyl 4-pentyl-4"'-heptoxy-2',3'-difluoro-p-quarter Phenyl

4-hexyl-4 "'-heptoxy-
2 ', 3'-Difluoro-p-quarterphenyl 4-heptyl-4 "'-heptoxy-2 ', 3'-difluoro-p-quarterphenyl 4-octyl-4"'-heptoxy-2 ', 3 '-Difluoro-p-quarterphenyl 4-nonyl-4 "'-heptoxy-2 ', 3'-difluoro-p-quarterphenyl 4-decyl-4"'-heptoxy-2 ', 3'-difluoro- p-quarterphenyl

4-dodecyl-4 "'-heptoxy-
2 ', 3'-Difluoro-p-quarterphenyl 4-ethoxy-4 "'-heptoxy-2 ', 3'-difluoro-p-quarterphenyl 4-propoxy-4"'-heptoxy-2 ', 3 '-Difluoro-p-quarterphenyl 4-butoxy-4 "'-heptoxy-2 ', 3'-difluoro-p-quarterphenyl 4-pentoxy-4"'-heptoxy-2 ', 3'-difluoro- p-quarterphenyl

4-hexoxy-4 "'-heptoxy-
2 ', 3'-Difluoro-p-quarterphenyl 4-heptoxy-4 "'-heptoxy-2 ', 3'-difluoro-p-quarterphenyl 4-octoxy-4"'-heptoxy-2 ', 3 '-Difluoro-p-quarterphenyl 4-nonoxy-4 "'-heptoxy-2 ', 3'-difluoro-p-quarterphenyl 4-decoxy-4"'-heptoxy-2 ', 3'-difluoro- p-quarterphenyl

Example 12 4,4 "-Dialkyl-2,3-difluoro-p-ter
Production of phenyl compounds 12A 1- (2,3-difluorophenyl) -4-
(P-Alkylphenyl) -cyclohex-1-ene conversion
Compound 1,2-difluorobenzene (0.1 mol) and TH
F-mixture at −70 ° C. with n-butyllithium.
Mixture of aluminum (0.105 ml) and hexane (60 ml)
Add. After stirring for 6 hours, 4- (p-propylf
(Enyl) -cyclohexanone (0.1 mol) and THF5
Add the mixture with 0 ml. After stirring for 2 hours, room temperature
Warm up to PTSA and boil as described in Example 10A
And then finished in a conventional manner to give 1- (difluoro-
Enyl) -4- (p-propylphenyl) -cyclohexyl
To obtain C-1-ene. Similarly, the following compound is obtained.
Is:

1- (2,3-difluorophenyl) -4
-(P-ethylphenyl) -cyclohex-1-ene 1- (2,3-difluorophenyl) -4- (p-butylphenyl) -cyclohex-1-ene 1- (2,3-difluorophenyl) -4 -(P-pentylphenyl) -cyclohex-1-ene 1- (2,3-difluorophenyl) -4- (p-hexylphenyl) -cyclohex-1-ene 1- (2,3-difluorophenyl) -4- (p-heptylphenyl) -cyclohex-1-ene

1- (2,3-difluorophenyl) -4
-(P-octylphenyl) -cyclohex-1-ene 1- (2,3-difluorophenyl) -4- (p-nonylphenyl) -cyclohex-1-ene 1- (2,3-difluorophenyl) -4- (p-decylphenyl) -cyclohex-1-ene 1- (2,3-difluorophenyl) -4- (p-dodecylphenyl) -cyclohex-1-ene 1- (2,3-difluorophenyl (Enyl) -4- (p-ethoxyphenyl) -cyclohex-1-ene

1- (2,3-difluorophenyl) -4
-(P-pentoxyphenyl) -cyclohex-1-ene 1- (2,3-difluorophenyl) -4- (p-octoxyphenyl) -cyclohex-1-ene 1- (2,3- Difluorophenyl) -4- (p-dodecylphenyl) -cyclohex-1-ene 1- (2,3-difluorophenyl) -4- (4-ethylbiphenyl-4′-yl) -cyclohex-1-ene 1- (2,3-difluorophenyl) -4- (4-pentylbiphenyl-4′-yl) -cyclohex-1-ene

1- (2,3-difluorophenyl) -4
-(4-octylbiphenyl-4'-yl) -cyclohex-1-ene 1- (2,3-difluorophenyl) -4- (4-dodecylbiphenyl-4'-yl) -cyclohex-1- Ene 1- (2,3-difluorophenyl) -4- (4-pentoxybiphenyl-4′-yl) -cyclohex-1-
En

12B 4 ″ -Alkyl-2,3-difluoro-p-terphenyl compound 1- (2,3-difluorophenyl) -4- (p-propylphenyl) -cyclohex-1-ene (0.1 Mol) is oxidized with DDQ (0.2 mol) according to Example 9B.
After finishing in a conventional manner, 4 "-propyl-2,3-
K 121 I to give difluoro-p-terphenyl.
. Similarly, the following compounds are obtained:

4 "-ethyl-2,3-difluoro-p-
Terphenyl 4 "-butyl-2,3-difluoro-p-terphenyl 4" -pentyl-2,3-difluoro-p-terphenyl 4 "-hexyl-2,3-difluoro-p-terphenyl 4" -heptyl-2, 3-difluoro-p-terphenyl 4 "-octyl-2,3-difluoro-p-terphenyl

4 "-nonyl-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-p-terphenyl 4 "-octoxy-2,3-difluoro-p-terphenyl 4" -dodecyloxy-2,3-difluoro-p-terphenyl 4 "'-ethyl-2,3-difluoro-p- Quarter phenyl

4 "'-pentyl-2,3-difluoro-
p-quarterphenyl 4 ""-octyl-2,3-difluoro-p-quarterphenyl 4 ""-dodecyl-2,3-difluoro-p-quarterphenyl 4 ""-pentoxy-2,3-difluoro -P-quarterphenyl

12C 4,4 ″ -Dialkyl-2,3-
Difluoro-p-terphenyl compound 65 ml of hexane of n-butyllithium (0.1 mol)
The solution in -100 ° C. was treated with 4 ″ -propyl-2,3-difluoro-p-terphenyl (0.1 mol), potassium t-butylate (0.1 mol) and 200 ml of THF.
To the mixture. After stirring at −100 ° C. for 5 minutes,
A mixture of bromopentane (0.1 mol) and N, N-dimethylpropylene urea (0.1 mol, DMPU) is added. After warming to -30 DEG C. and then working up in the customary manner, 4 "-propyl-4-pentyl-2,3-difluoro-p-terphenyl is obtained. Similarly, the following compounds are 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-p
-Terphenyl 4 "-pentyl-4-pentyl-2,3-difluoro-
p-Terphenyl K80.0 S _C 115.5 S _A
131.5 N 142.0 I

4 ″ -Hexyl-4-pentyl-2,3-
Difluoro-p-terphenyl 4 "-heptyl-4-pentyl-2,3-difluoro-
p-Terphenyl K65.5 S _C 117.0 S _A
135.0 N 136.0 I 4 "-octyl-4-pentyl-2,3-difluoro-
p-terphenyl 4 "-nonyl-4-pentyl-2,3-difluoro-p
-Terphenyl 4 "-decyl-4-pentyl-2,3-difluoro-p
-Terphenyl

4 "-Dodecyl-4-pentyl-2,3-
Difluoro-p-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 K 100.5 S _C 156.5
S _A 166.5 N 171.5 I4 "- octoxy-4-pentyl-2,3-difluoro -p- terphenyls _{K 87.5 S C 155.5 S A 165.0} N
165.7 I

4 "-(4-methylhexyl) -4-pentyl-2,3-difluoro-p-terphenyl K7
1.0 SC 120.0 N 128.0 I 4 "-dodecyloxy-4-pentyl-2,3-difluoro-p-terphenyl 4" -ethyl-4-propyl-2,3-difluoro-p
-Terphenyl 4 "-propyl-4-propyl-2,3-difluoro-
p-Terphenyl K133 N 150 I

4 "-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 "-heptyl-4-propyl-2,3-difluoro-
p-terphenyl 4 "-octyl-4-propyl-2,3-difluoro-
p-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 "-ethoxy-4-propyl-2,3-difluoro-
p-terphenyl 4 "-pentoxy-4-propyl-2,3-difluoro-p-terphenyl 4" -octoxy-4-propyl-2,3-difluoro-p-terphenyl 4 "-dodecyloxy-4-propyl-2 , 3-Difluoro-p-terphenyl

4 "-ethyl-4-octyl-2,3-difluoro-p-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 "-heptyl-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 "-pentoxy-4-octyl-2,3-difluoro-p-terphenyl 4" -octoxy-4-octyl-2,3-difluoro-p-terphenyl 4 "-dodecyloxy-4-octyl-2 , 3-Difluoro-p-terphenyl

4 ″ -pentyl-4-heptyl-2,3-
Difluoro-p-terphenyl K55.0 S _C 1
_{05.5 S A 130.5 N 135.0 I 4} "- propyl-4-nonyl-2,3-difluoro -p
-Terphenyl K63.0 S _C 84.5 S _A 1
16.5 N 129.0 I 4 "-ethyl-4-dodecyl-2,3-difluoro-p
-Terphenyl 4 "-propyl-4-dodecyl-2,3-difluoro-
p-terphenyl 4 "-butyl-4-dodecyl-2,3-difluoro-p
-Terphenyl 4 "-pentyl-4-dodecyl-2,3-difluoro-
p-terphenyl 4 "-hexyl-4-dodecyl-2,3-difluoro-
p-terphenyl

4 ″ -Heptyl-4-dodecyl-2,3-
Difluoro-p-terphenyl 4 "-octyl-4-dodecyl-2,3-difluoro-
p-terphenyl 4 "-nonyl-4-dodecyl-2,3-difluoro-p
-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-p-terphenyl 4" -octoxy-4-dodecyl-2,3-difluoro-p-terphenyl 4 "-dodecyloxy-4-dodecyl-2 , 3-Difluoro-p-terphenyl

4 "'-ethyl-4-propyl-2,3-
Difluoro-p-terphenyl 4 ""-pentyl-4-propyl-2,3-difluoro-p-terphenyl 4 ""-octyl-4-propyl-2,3-difluoro-p-terphenyl 4 ""-dodecyl-4 -Propyl-2,3-difluoro-p-terphenyl 4 "'-pentoxy-4-propyl-2,3-difluoro-p-terphenyl 4"'-ethyl-4-pentyl-2,3-difluoro-
p-terphenyl 4 "'-pentyl-4-pentyl-2,3-difluoro-p-terphenyl

4 "'-octyl-4-pentyl-2,3
-Difluoro-p-terphenyl 4 ""-dodecyl-4-pentyl-2,3-difluoro-p-terphenyl 4 ""-pentoxy-4-pentyl-2,3-difluoro-p-terphenyl 4 ""-ethyl- 4-octyl-2, -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-p-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 Preparation of 4-alkoxy-4 "-alkyl-2,3-difluoro-p-terphenyl compound 1,2-difluoro-3-ethoxybenzene (0.2 mol) was dissolved in THF / TMEDA according to Example 10A. With n-butyllithium and then reacted with 4- (p-propylphenyl) -cyclohexanone (0.2 mol) according to Example 10C, PT according to Example 10A.
After elimination with SA and subsequent oxidation with DDQ, 4-ethoxy-4 "-propyl-2,3-difluoro-p-terphenyl is obtained. Similarly, the following compounds are obtained:

4-Propoxy-4 "-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-heptoxy-4 "-propyl-2, 3-difluoro-p-terphenyl 4-octoxy-4 "-propyl-2,3-difluoro-p-terphenyl 4-nonoxy-4" -propyl-2,3-difluoro-
p-terphenyl

4-decyloxy-4 "-propyl-2,
3-Difluoro-p-terphenyl 4-dodecyloxy-4 "-propyl-2, -difluoro-p-terphenyl 4-ethoxy-4" -pentyl-2,3-difluoro-p-terphenyl K 105 S _C 135 N 1
85.1 I 4-Propoxy-4 "-pentyl-2,3-difluoro-p-terphenyl 4-butoxy-4" -pentyl-2,3-difluoro-
p- terphenyls 4-pentoxy-4 "- pentyl-2,3-difluoro -p- terphenyls 4 hexoxy-4" - pentyl-2,3-difluoro -p- terphenyls K 97.5 ° S _C 145.5 °
N 166.0 ° I

4-Heptoxy-4 "-pentyl-2,3
-Difluoro-p-terphenyl 4-octoxy-4 "-pentyl-2,3-difluoro-p-terphenyl K 93.5 ° S _C 144.0
_{° S A 148.0 ° N 159.0 °} I 4- nonoxy 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-propoxy-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-heptoxy-4" -octyl-2,3-difluoro-p-terphenyl 4-octoxy-4 "-octyl -2,3-difluoro-p-terphenyl 4-nonoxy-4 "-octyl-2,3-difluoro-
p-terphenyl 4-decyloxy-4 "-octyl-2,3-difluoro-p-terphenyl 4-dodecyloxy-4" -octyl-2,3-difluoro-p-terphenyl

4-ethoxy-4 "-dodecyl-2,3-
Difluoro-p-terphenyl 4-propoxy-4 "-dodecyl-2,3-difluoro-p-terphenyl 4-butoxy-4" -dodecyl-2,3-difluoro-
p-terphenyl 4-pentoxy-4 "-dodecyl-2,3-difluoro-p-terphenyl 4-hexoxy-4" -dodecyl-2,3-difluoro-p-terphenyl 4-heptoxy-4 "-dodecyl-2, 3-difluoro-p-terphenyl 4-octoxy-4 "-dodecyl-2,3-difluoro-p-terphenyl 4-nonoxy-4" -dodecyl-2,3-difluoro-
p-Terphenyl 4-decyloxy-4 "-dodecyl-2,3-difluoro-p-terphenyl 4-dodecyloxy-4" -dodecyl-2,3-difluoro-p-terphenyl

4-octoxy-4 "-(4-methylhexyl) -2,3-difluoro-p-terphenyl K
71.0 S _C 120.0 N 128.0 I 4- ethoxy-4 "- ethoxy-2,3-difluoro -
p-Terphenyl 4-propoxy-4 "-ethoxy-2,3-difluoro-p-terphenyl 4-butoxy-4" -ethoxy-2,3-difluoro-
p-terphenyl 4-pentoxy-4 "-ethoxy-2,3-difluoro-p-terphenyl 4-hexoxy-4" -ethoxy-2,3-difluoro-p-terphenyl 4-heptoxy-4 "-ethoxy-2, 3-difluoro-p-terphenyl 4-octoxy-4 "-ethoxy-2,3-difluoro-p-terphenyl 4-nonoxy-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-p-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-heptoxy-4" -pentoxy-2,3-difluoro-p-terphenyl 4-octoxy- 4 "-pentoxy-2,3-difluoro-p-terphenyl 4-nonoxy-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-terphenyl 4-propoxy -4 "-dodecyloxy-2,3-difluoro-p-terphenyl 4-butoxy-4" -dodecyloxy-2,3-difluoro-p-terphenyl 4-pentoxy-4 "-dodecyloxy-2,3-difluoro -P-terphenyl

4-hexoxy-4 "-dodecyloxy-
2,3-difluoro-p-terphenyl 4-heptoxy-4 "-dodecyloxy-2,3-difluoro-p-terphenyl 4-octoxy-4" -dodecyloxy-2,3-difluoro-p-terphenyl 4-nonoxy -4 "-dodecyloxy-2,3-difluoro-p-terphenyl 4-decyloxy-4" -dodecyloxy-2,3-difluoro-p-terphenyl 4-dodecyloxy-4 "-dodecyloxy-2,3-
Difluoro-p-terphenyl 4-octoxy-4 "-pentyl-2,3,2" -trifluoro-p-terphenyl K 58.0 S _C 6
1.5 N 119.5 I

4-ethoxy-4 "'-propyl-2,3
-Difluoro-p-quarterphenyl 4-propoxy-4 "'-propyl-2,3-difluoro-p-quarterphenyl 4-butoxy-4"'-propyl-2,3-difluoro-p-quarterphenyl 4-pentoxy-4 ""-propyl-2,3-difluoro-p-quarterphenyl 4-hexoxy-4 ""-propyl-2,3-difluoro-p-quarterphenyl 4-heptoxy-4 ""- Propyl-2,3-difluoro-p-quarterphenyl

4-octoxy-4 "'-propyl-2,
3-difluoro-p-quarterphenyl 4-nonoxy-4 ""-propyl-2,3-difluoro-p-quarterphenyl 4-decyloxy-4 ""-propyl-2,3-difluoro-p-quarterf Enyl 4-dodecyloxy-4 "'-propyl-2,3-difluoro-p-quarterphenyl 4-ethoxy-4"'-pentyl-2,3-difluoro-p-quarterphenyl 4-propoxy-4 "'-Pentyl-2,3-difluoro-p-quarterphenyl

4-butoxy-4 "'-pentyl-2,3
-Difluoro-p-quarterphenyl 4-pentoxy-4 "'-pentyl-2,3-difluoro-p-quarterphenyl 4-hexoxy-4"'-pentyl-2,3-difluoro-p-quarterphenyl 4-Heptoxy-4 "'-pentyl-2,3-difluoro-p-quarterphenyl 4-octoxy-4"'-pentyl-2,3-difluoro-p-quarterphenyl 4-nonoxy-4 "'- Pentyl-2,3-difluoro-p-quarterphenyl

4-decyloxy-4 "'-pentyl-
2,3-difluoro-p-quarterphenyl 4-dodecyloxy-4 "'-pentyl-2,3-difluoro-p-quarterphenyl 4-ethoxy-4"'-octyl-2,3-difluoro-p -Quarterphenyl 4-propoxy-4 "'-octyl-2,3-difluoro-p-quarterphenyl 4-butoxy-4"'-octyl-2,3-difluoro-p-quarterphenyl

4-pentoxy-4 "'-octyl-2,
3-difluoro-p-quarterphenyl 4-hexoxy-4 "'-octyl-2,3-difluoro-p-quarterphenyl 4-heptoxy-4"'-octyl-2,3-difluoro-p-quarterf Enyl 4-octoxy-4 ""-octyl-2,3-difluoro-p-quarterphenyl 4-nonoxy-4 ""-octyl-2,3-difluoro-p-quarterphenyl 4-decyloxy-4 "" -Octyl-2,3-difluoro-p-quarterphenyl

4-Dodecyloxy-4 "'-octyl-
2,3-difluoro-p-quarterphenyl 4-ethoxy-4 "'-dodecyl-2,3-difluoro-p-quarterphenyl 4-propoxy-4"'-dodecyl-2,3-difluoro-p- Quarterphenyl 4-butoxy-4 ""-dodecyl-2,3-difluoro-p-quarterphenyl 4-pentoxy-4 ""-dodecyl-2,3-difluoro-p-quarterphenyl 4-hexoxy-4 "'-Dodecyl-2,3-difluoro-p-quarterphenyl

4-Heptoxy-4 "'-dodecyl-2,
3-difluoro-p-quarterphenyl 4-octoxy-4 "'-dodecyl-2,3-difluoro-p-quarterphenyl 4-nonoxy-4"'-dodecyl-2,3-difluoro-p-quarterf Enyl 4-decyloxy-4 "'-dodecyl-2,3-difluoro-p-quarterphenyl 4-dodecyloxy-4"'-dodecyl-2,3-difluoro-p-quarterphenyl 4-ethoxy-4 "'-Ethoxy-2,3-difluoro-p-quarterphenyl

4-propoxy-4 "'-ethoxy-2,
3-difluoro-p-quarterphenyl 4-butoxy-4 "'-ethoxy-2,3-difluoro-p-quarterphenyl 4-pentoxy-4"'-ethoxy-2,3-difluoro-p-quarterf Enyl 4-hexoxy-4 ""-ethoxy-2,3-difluoro-p-quarterphenyl 4-heptoxy-4 ""-ethoxy-2,3-difluoro-p-quarterphenyl 4-octoxy-4 "" -Ethoxy-2,3-difluoro-p-quarterphenyl 4-nonoxy-4 "'-ethoxy-2,3-difluoro-p-quarterphenyl

4-decyloxy-4 "'-ethoxy-
2,3-difluoro-p-quarterphenyl 4-dodecyloxy-4 "'-ethoxy-2,3-difluoro-p-quarterphenyl 4-ethoxy-4"'-pentoxy-2,3-difluoro-p -Quarterphenyl 4-propoxy-4 "'-pentoxy-2,3-difluoro-p-quarterphenyl 4-butoxy-4"'-pentoxy-2,3-difluoro-p-quarterphenyl 4-pentoxy- 4 "'-pentoxy-2,3-difluoro-p-quarterphenyl

4-hexoxy-4 "'-pentoxy-
2,3-difluoro-p-quarterphenyl 4-heptoxy-4 "'-pentoxy-2,3-difluoro-p-quarterphenyl 4-octoxy-4"'-pentoxy-2,3-difluoro-p- Quarterphenyl 4-nonoxy-4 "'-pentoxy-2,3-difluoro-p-quarterphenyl-4-decyloxy-4"'-pentoxy-2,3-difluoro-p-quarterphenyl 4-dodecyloxy- 4 "'-pentoxy-2,3-difluoro-p-quarterphenyl

4-ethoxy-4 "'-dodecyloxy-
2,3-difluoro-p-quarterphenyl 4-propoxy-4 "'-dodecyloxy-2,3-difluoro-p-quarterphenyl 4-butoxy-4"'-dodecyloxy-2,3-difluoro- p-quarterphenyl 4-pentoxy-4 "'-dodecyloxy-2,3-difluoro-p-quarterphenyl

4-hexoxy-4 ""-dodecyloxy-2,3-difluoro-p-quarterphenyl 4-heptoxy-4 ""-dodecyloxy-2,3-difluoro-p-quarterphenyl 4-octoxy -4 "'-dodecyloxy-2,3-difluoro-p-quarterphenyl 4-nonoxy-4"'-dodecyloxy-2,3-difluoro-p-quarterphenyl 4-decyloxy-4 "'-dodecyl Oxy-2,3-
Difluoro-p-quarterphenyl 4-dodecyloxy-4 "'-dodecyloxy-2,3
-Difluoro-p-quarterphenyl

Example 14 Ferroelectric smectic C liquid crystal mixture containing difluoroterphenyl compound 14A 4-n-octyloxy-2,3-difluoro-4 "-
n-pentyl-p-terphenyl 95 wt% (+)-(1-cyano-2-methylpropyl) -4′-
Octyloxybiphenyl-4-ylcarboxylate 5 wt% The optically active compounds in this mixture are of the L configuration.
The mixture had a liquid crystal transition below _{(℃) K 85.9 S C 125.4} S A 143.2 N
150.6 I The S _C phase was subcooled to 76 ° C..

[0215]

[Table 1]

Mixture 14B 4-n-hexyloxy-4 ″ -pentyl-2 ′, 3 ′
-Difluoro-p-terphenyl 45 wt% 4-n-octyloxy-4 ″ -pentyl-2 ′, 3 ′
-Difluoro-p-terphenyl 45 wt% (+)-(1-cyano-2-methylpropyl) -4'-
Octyloxybiphenyl-4-ylcarboxylate 6.25 wt% (-)-(1-cyano-2-methylpropyl) -4'-
3.75 wt% of octyloxybiphenyl-4-ylcarboxylate This mixture showed the following liquid crystal transition (° C.):> 20
S _C 84.7 S _A 98.6 N 128 I That is, this mixture exhibited an S _C phase at room temperature.

[0219]

[Table 2]

Using a liquid crystal electro-optic cell having a known structure,
The mixture 14B was applied to a cell having a voltage of 20 volts and a cell having a pitch of 2 μm by a polyimide oriented film, and having a voltage of about 10 μm.
A switching time of 0 μsec was indicated.

Example 15 4-n-hexyloxy-4 ″ -n-pentyl-2 ′,
A 1: 1 (by weight) mixture of 3′-difluoro-p-terphenyl and 4-n-octyloxy-4 ″ -n-pentyl-2 ′, 3′-difluoro-p-terphenyl is 28 ° C.
S _C 79.1 N showing an S _C phase that is supercooled to
142.4 I. The birefringence of this mixture was 0.19.

Example 16 A mixture containing the following liquid crystal components is prepared: 4-octyl-4 "-propyl-2'-fluoro-p-
Terphenyl 29.45% 4-heptyl-4 "-propyl-2'-fluoro-p-
Terphenyl 19.80% L-(-)-4-hexoxy-4 "-(2-methylbutyl) -2'-fluoro-p-terphenyl 29.40
% S-(+)-2-octyl 4'-octoxybiphenyl-4-ylcarboxylate 6.45% 4-octoxy-4 "-pentyl-2 ', 3'-difluoro-p-terphenyl 5.00 %

Example 17 A mixture containing the following liquid crystal components is prepared: 4-octyl-4 "-propyl-2'-fluoro-p-
Terphenyl 41.55% L-(-)-4-hexoxy-4 "-(2-methylbutyl) -2'-fluoro-p-terphenyl 41.75
% S-(+)-2-octyl 4'-octoxybiphenyl-4-ylcarboxylate 11.70% 4-octoxy-4 "-pentyl-2,3-difluoro-p-terphenyl 5.00%

Example 18 A mixture containing the following liquid crystal components is prepared: 4-octyl-4 "-pentyl-2'-fluoro-p-
Terphenyl 72.00% S-(+)-2-octyl 4′-octoxybiphenyl-4-ylcarboxylate 4.50% 2-fluoro-4-pentylphenyl 4-octoxybenzoate 13.50% 4 -Octoxy-4 "-pentyl-2,3-difluoro-p-terphenyl 5.00% 4-Octoxy-4" -pentyl-2 ', 3'-difluoro-p-terphenyl 5.00%

Example 19 A mixture for ECB prepared to contain the following liquid crystal components had a clearing point at 86 ° C., Δε: −1.5, Δn: +
Shows 0.185: 4,4'-dipropyl-2,3-difluorobiphenyl 20% 4,4'-dipentyl-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-Fluorobiphenyl 4% 4-ethyl-4'-methoxytran 3% 4-methoxy-4'-methyltran 3%

Example 20 A mixture for ECB prepared to contain the following liquid crystal components had a clearing point of 82 ° C., Δε: −1.7, Δn: +
Shows 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-terphenyl 15% 4-pentyl-4 "-octyloxy-2', 3'-difluoro-p-terphenyl 15%

4- (trans-4-propylcyclohexyl) -methoxybenzene 15% 4- (trans-4-propylcyclohexyl) -ethoxybenzene 15% 4,4'-bis- (trans-4-propylcyclohexyl) -2 -Fluorobiphenyl 4% 4,4'-bis- (trans-4-pentylcyclohexyl) -2-fluorobiphenyl 3% 4- (trans-4-propylcyclohexyl) -4 '
-(Trans-pentylcyclohexyl) -2-fluorobiphenyl 3%

Example 21 A mixture for ECB prepared to contain the following liquid crystal components had a clear point of 91 ° C., Δε: −1.5, Δn: +
Shows 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-terphenyl 15% 4-pentyl-4 "-octyloxy-2,3'-difluoro-p-terphenyl 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 ′
-Propoxytran 5%

Example 22 A ferroelectric mixture containing a difluoroterphenyl compound is prepared based on a eutectic host (Host I) containing the following components: 4-hexyloxy-4 "-pentyl-2 ', 3'-difluoro-p-terphenyl 37.25 wt% 4-hexyloxy-4 "-pentyl-2,3-difluoro-p-terphenyl 13.6 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 I 70 wt% 4-octyloxy-4'-pentyl-2,3-difluorobiphenyl 20 wt% (+)-(1-cyano-2-methylpropyl) -4'-
Octyloxy-biphenyl-4-yl-carboxylate 6.25 wt% (-)-(1-cyano-2-methylpropyl) -4'-
Octyloxy - biphenyl-4-yl - carboxylate _{3.75wt% S C 60 S A 79.7} N 109.4 I and ^{_{P S 6.6nC / cm 2 (30}} ℃), S C tilt angle 2
1.5 °. This mixture was prepared using the electro-optic cell of Example 14 at about 40
The figure shows the switching time in μsec.

Mixture 22B Host I 90 wt% (+)-(1-cyano-2-methylpropyl) -4'-
Octyloxy-biphenyl-4-yl-carboxylate 6.75 wt% (-)-(1-cyano-2-methylpropyl) -4'-
Octyloxy-biphenyl-4-yl-carboxylate 3.75 wt% K <20 S _C 90.4 S _A 109.6 N 1
_{33 I, P S 8.9nC / cm} 2 (30 ℃), S C tilt angle 23.5, switching-time about 90Myusec.

Mixture 22C Host I 90 wt% (+)-(1-cyano-2-methylpropyl) -4'-
Octyloxy-biphenyl-4-yl-carboxylate 5.63 wt% (-)-(1-cyano-2-methylpropyl) -4'-
Octyloxy - biphenyl-4-yl - carboxylate _{4.37wt% S C 93 S A 109.6} N 133 I, P S
4.24 nC / cm ² (30 ° C.), S _C tilt angle 23.5
°, switching time approx. 260 μsec.

Mixture 22D Host I 70 wt% 4-octyloxy-4'-pentyl-2,3-difluorobiphenyl 20 wt% (+)-(1-cyano-2-methylpropyl) -4'-
Octyloxy-biphenyl-4-yl-carboxylate 5.63 wt% (-)-(1-cyano-2-methylpropyl) -4'-
Octyloxy - biphenyl-4-yl - carboxylate _{4.37wt% S C 60 S A 79.7} N 109.4 I, P S
^{2.7nC / cm 2 (30 ℃)} , S C tilt angle 19.
5. Switching time about 75 μsec.

Mixture 22E Host I 45 wt% 4,4 ″ -dipentyl-2 ′, 3′-difluoro-p-
Terphenyl 45 wt% (+)-(1-cyano-2-methylpropyl) -4′-
Octyloxy-biphenyl-4-yl-carboxylate 6.25 wt% (-)-(1-cyano-2-methylpropyl) -4'-
Octyloxy - biphenyl-4-yl - carboxylate _{3.75wt% S C 60.5 S A 87.1} N 114.7 I,
P _S 5.6nC / cm ² _{S C} tilt angle 22 °, switching-time 54Myusec.

Example 23 A ferroelectric mixture containing a difluoroterphenyl compound is prepared based on a host (Host II) containing the following components: 4-heptyl-5 "-pentyl-2,3-difluoro −
p-Terphenyl 33.33 wt% 4 ', 4 "-dipentyl-2,3-difluoro-p-terphenyl 33.33 wt% 4', 4" -dipentyl-2 ', 3'-difluoro-p
-Terphenyl 33.33 wt%

Mixture 23A Host II 90.00 wt% (+)-(1-cyano-2-methylpropyl) -4'-
Octyloxy-biphenyl-4-yl-carboxylate 6.25 wt% (-)-(1-cyano-2-methylpropyl) -4'-
Octyloxy - biphenyl-4-yl - carboxylate _{3.75wt% S C 60 S A 105} N 115 I, P S
^{7.2nC / cm 2 (30 ℃)} , S C tilt angle 21.5
°, switching time 17 μsec.

Mixture 23B Host II 90.00 wt% (+)-(1-cyano-2-methylpropyl) -4'-
Octyloxy - biphenyl-4-yl - carboxylate _{10.00wt% S C 59 S A 105.4} N 116 I, P S
^{30nC / cm 2 (30 ℃)} , S C tilt angle 21.5 °,
Switching time 4 μsec.

Mixture 23C Host II 97.5 wt% (+)-(1-cyano-2-methylpropyl) -4'-
Octyloxy - biphenyl-4-yl - carboxylate _{2.5wt% S C 86.7 S A 107.1} N 124.7, P
_S 7.0 nC / cm ² (30 ° C.), S _C tilt angle 23
°, switching time about 70 μsec.

Example 24 A ferroelectric mixture containing different amounts of a difluoroterphenyl compound and a chiral dopant is prepared. Mixture 24A 4-heptyl-4 "-nonyl-2,3-difluoro-p
-Terphenyl 97.5 wt% (+)-(1-cyano-2-methylpropyl) -4'-
Octyloxy-biphenyl-4-yl-carboxylate 2.5 wt% K 48 S _C 62.6 S _A 92.5 N 10
3.8 I, P _S 2.9 (at 50 ° C.), switching time 15 μsec.

Mixture 24B 4-Pentyl-4 "-(4-methylhexyl) -2,3
-Difluoro-p-terphenyl 90 wt% (+)-(1-cyano-2-methylpropyl) -4'-
Octyloxy-biphenyl-4-yl-carboxylate 6.2 wt% (-)-(1-cyano-2-methylpropyl) -4'-
Octyloxy-biphenyl-4-yl-carboxylate 3.8 wt% K 56.1 S _C 80.9 S _A 82.7 N 8
9.4 I, S _C tilt angle 26 °.

Mixture 24C 4-Pentyl-4 "-heptyl-2 ', 3'-difluoro-p-terphenyl 29.25 wt% 4-Heptyl-4"-nonyl-2',3'-difluoro-p-terphenyl 34.125 wt% 4-heptyl-4 "-pentyl-2,3-difluoro-
p-Terphenyl 19.50 wt% 4-pentyl-4 "-heptyl-2,3-difluoro-
14.625 wt% of p-terphenyl (+)-(1-cyano-2-methylpropyl) -4′-
Octyloxy - biphenyl-4-yl - carboxylate _{2.50wt% S C 68 S A 94.2} N 111 I, P S
5.9 nC / cm ² (30 ° C.), S _C tilt angle 22.5 °
Switching time about 40 μsec.

Mixture 24D 4,4 "-dipentyl-2 ', 3'-difluoro-p-
Terphenyl 45 wt% 4,4 "-dipentyl-2,3-difluoro-p-terphenyl 22.5 wt% 4-heptyl-4" -pentyl-2,3-difluoro-
p-terphenyl 22.5 wt% (+)-(1-cyano-2-methylpropyl) -4′-
Octyloxy-biphenyl-4-yl-carboxylate 6.2 wt% (-)-(1-cyano-2-methylpropyl) -4'-
Octyloxy - biphenyl-4-yl - carboxylate _{3.8 wt% S C 43.6 S A} 95.5 N 109.5 I,
P _S 5.1 nC / cm ² (at 25 ° C.).

Mixture 24E 4-heptyl-4 "-pentyl-2 ', 3'-difluoro-p-terphenyl 48.5 wt% 4-heptyl-4" -pentyl-2,3-difluoro-
p-terphenyl 24.25 wt% 4,4 "-dipentyl-2,3-difluoro-p-terphenyl 24.25 wt% (+)-(1-cyano-2-methylpropyl) -4'-
Octyloxy-biphenyl-4-yl-carboxylate 3.0 wt% S _C 75 S _A 91 N 116 I, P _S 7.9
^{nC / cm 2 (30 ℃)} , S C tilt angle 23 °.

[Brief description of the drawings]

FIG.

Embedded image 1 shows a manufacturing route (path 1).

FIG. 2

Embedded image The manufacturing path (path 2) of FIG.

FIG. 3

Embedded image The manufacturing route (path 3) is shown.

FIG. 4

Embedded image Manufacturing route (path 4) and

Embedded image Is shown in FIG.

FIG. 5

Embedded image Manufacturing route and

Embedded image Are shown (path 6 and path 7).

FIG. 6

Embedded image The manufacturing path (path 8) of FIG.

FIG. 7

Embedded image The manufacturing path (path 9) of FIG.

FIG. 8

Embedded image

Embedded image

Embedded image The manufacturing route (path 10) of FIG.

──────────────────────────────────────────────────続 き Continued on the front page (31) Priority claim number Japanese Patent Application No. 62-505735 (32) Priority date September 9, 1987 (September 9, 1987) (33) Priority claim country Japan (JP) (73) Patent holder 591032596 Frankfurter Str. 250, D-64293 Darmstadt, Federal Republic of Germany (72) Inventor Gray, George W. William Northumberside HU16 4DZ Cotteingham, England Newgate Street, Glenwoods (unnumbered) (72) Inventor Hard, Michael England North Humberside HU4 7BZ Hull, Anravi Park Road South 222 (72) Inventor Lacey, Devitted North Humberside HU18 9NN Hull, Kildale Closes 19 (72) Inventor Toin, Kenneth Jillson North Humberside HU6, UK 8QW Hull, Hall Road 25 (72) Inventor Lifenrad, Forker D-6101 Rosdorf, Germany Järnshuitrasse 18 (72) Inventor Wützhtler, Andreas Federal Republic of Germany D-6103 Griesheim, Goethestrasse 34 (72) Inventor Krause, Joachim Germany D-6110 Davek, Samuel-Moses-Schüthrace 14 (72) Inventor Finkentzer, Ulrich D, Germany -6831 Plankshu Tat, Valtoppuat 74 (72) Inventor Galehar, Thomas D-6500 Mainz, Germany D-6500 Mainz, Trayansicht 12 (58) Fields studied (Int.Cl. ⁷ , DB name) C07C 25/18 C07C 43/225 C09K 19/12 C09K 19/44 G02F 1/13 500 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (20)

(57) [Claims] 1. A compound of the formula I Wherein a is 0 and wherein the terminal substituent R ¹ ,
R ² and R ³ are each independently an alkyl or alkenyl group, each having up to 15 C atoms, which groups are optionally substituted by CN or by at least one halogen atom. May be
Is one more CH ₂ groups not CH ₂ group or adjacent that present in the group -O -, - S -, - CO
—, —O—CO—, —CO—O—, —O—CO—O— or —C≡C—, and the group R
¹ and ^one of the radicals R ² are also of the formula Wherein at least one of the following pair of lateral substituents is 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'), (A, G), and all other lateral substituents are hydrogen or fluorine.] II (Wherein, R ¹ , R ² , A, B, C, D, E, G, J, K
And R ¹ and R ² are Wherein R ³ , C ′, D ′, G ′ and J ′ are all as defined above). 2. The terminal substituents R ¹ and R ² or the group R ¹
And one of the groups R ² and the group R ³ are independently alkoxy, alkyl, each having up to 15 C atoms,
The derivative according to claim 1, which is a perfluoroalkyl or perfluoroalkoxy. 3. (C, D) is both fluorine, R ¹ is ethoxy and R ² is n-pentyl, or (B, C) is both fluorine;
P wherein R ¹ is ethoxy and R ² is n-propyl
3. The derivative according to claim 2, excluding terphenyl compounds. 4. The derivative according to claim 1, wherein only one pair of lateral substituents is fluorine, and all other lateral substituents are hydrogen. 5. The derivative according to claim 4, wherein said derivative is a difluoroterphenyl compound. 6. The at least one of claims 1, 2 or 3, wherein only one pair of lateral substituents is fluorine and one of the other lateral substituents is fluorine. Derivatives. 7. The derivative according to claim 6, wherein the derivative is a trifluoroterphenyl compound. 8. The derivative according to claim 1, wherein the terminal substituents are each independently n-alkyl or n-alkoxy having 5 to 12 C atoms. 9. The derivative according to claim 1, wherein at least one of the terminal substituents is a chiral alkyl or alkoxy group having 5 to 12 C atoms. 10. A compound of the formula I ′ Wherein A ¹ and A ² are each independently 1,4
A phenylene group, which may be optionally substituted by 1 to 4 fluorines, wherein R ¹ and R ² are each independently an alkyl group having up to 15 C atoms or Alkenyl groups, which may be optionally substituted by CN or by at least one halogen atom, and wherein one CH ₂ group or non-adjacent 2 the number or more CH ₂ groups -O -, - S -, - CO -, - O-CO-,
May be replaced by -CO-O-, -O-CO-O- or -C≡C-, m is 0, n is 1 and the sum of m and n is 1 ] The derivative | guide_body of Claim 1 characterized by these. 11. The derivative according to claim 1, wherein the terminal substituents are each independently normal alkyl or alkoxy having 1 to 7 carbon atoms. 12. A liquid crystal composition comprising at least two liquid crystal components, wherein at least one component is the compound according to at least one of claims 1 to 11. 13. The composition of claim 1, which is a nematic composition.
3. The liquid crystal composition according to 2. 14. The liquid crystal composition according to claim 12, which is a chirally tilted smectic composition. 15. A compound of formula I in addition to at least one compound of formula I according to claim 1. Wherein a is 0 or 1, and R ¹ , R ² , A,
B, C, D, E, G, J and K have the meaning of claim 1.] The compound according to claim 14, which contains at least one compound represented by the formula: Smectic composition. 16. A compound of formula I which is a group of the following biphenyl compounds: 16. The chirally tilted smectic composition of claim 15, wherein the composition is selected from the group consisting of: 17. In addition to at least one compound of the formula I, a compound of the formula Wherein R _A is alkyl or alkoxy, R _B is alkyl, and (F) indicates that the ring may have a lateral fluorine substituent, and n is 1 or 2. And m is 0 or 1.] The liquid crystal composition according to at least one of claims 14 to 16, comprising at least one compound represented by the following formula: 18. R _B is C ₁ -C ₄ n-alkyl or cyclohexyl, or R _B is of the structural formula: Wherein a is 0 or 1-6 and b and c
The liquid crystal composition according to claim 17, wherein each is independently a branched or chiral alkyl represented by the formula: 19. A liquid crystal display device comprising the liquid crystal phase according to at least one of claims 12 to 18. 20. An electro-optical display device comprising the liquid crystal phase according to at least one of claims 12 to 18.