JPH08295884A - Smectic liquid crystal composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a liquid crystal composition useful for a rapid switching display based on ferroelectric characteristic which contains a specific compound as a component of a chirally tilted smectic liquid crystal phase and is excellent in chemical stability.

SOLUTION: The titled composition contains, as a component of a chirally tilted smectic liquid crystal phase, at least one compound selected from 4-(5- heptylpyrimidin-2-yl)-phenyl p-pentylbenzyl ether of formula I [wherein R¹ and R² are each 1-12C alkyl, or either of R¹ and R² is H, F, Cl, Br or CN; A¹ is -Pyr-Phe-, -Phe-Pyr-, -Pyr-Cy- (wherein Pyr is pyrimidine-2,5-diyl or the like; Phe is 1,4-phenylene; and Cy is trans-1,4-cyclohexylene) or the like; A² and A³ are each trans-1,4-cyclohexylene or 1,4-phenylene; Z¹ is -CH₂CH₂-, -CO-O-, -CH₂O- or the like; Z² is -CO-O-, -CH₂CH₂-, -CH₂O- or the like; m is 0 or 1; provided that compounds of formula II and III (wherein R¹ and R² are each 5-12C alkyl) are excluded] or the like.

COPYRIGHT: (C)1996,JPO

Description

Detailed Description of the Invention

The present invention is of the formula IR ¹ -A ¹ -Z ¹ -A ^2- [Z ² -A ³ ] _m -R ² I where R ¹ and R ² each have 1 to 12 C atoms. an alkyl group, at least one is optically active, the two or more CH ₂ groups that are not one CH ₂ group or adjacent present in the group -O -, - CO
-, - O-CO -, - O-COO -, - CO-O- and (or) may be replaced by -CH = CH-, or one of the radicals R ¹ and R ² are also H, F ,
Cl, Br or CN, A ¹ is -Pyr-Phe
-, -Phe-Pyr-, -Pyr-Cy- or -C
y-Pyr-, where Pyr is pyrimidine-2,5-diyl, pyridine-2,5-diyl, pyrazine-2,5-diyl or pyridazine-3,6-diyl, Phe
Is 1,4-phenylene, which is unsubstituted or has 1 or 2 F and / or Cl atoms and / or CH ₃ and / or CN groups as substituents. , Cy is trans-1,4-cyclohexylene, and A ² and A ³ are each trans-.
1,4-cyclohexylene or 1,4-phenylene, which is unsubstituted or has 1 or 2 F and / or Cl atoms and / or CH ₃ as substituents. And / or has a CN group,
And one or two or more CH groups present therein may be replaced by N, and Z ¹ is —CH ₂ C.
_{H 2 -, - CO-O} -, - O-CO -, - CH 2 -O- or -OCH ₂ - is and, Z ² is -CO-O -, - O- C
_{O -, - CH 2 CH 2} -, - CH 2 O -, - O-CH 2 - or a single bond, and the compound represented by m is 0 or 1] as a component of the smectic liquid crystal composition Regarding to use. It also relates to smectic liquid crystal compositions containing a compound of formula I, in particular a chirally tilted smectic phase.

A chiral tilted smectic liquid crystal composition having a ferroelectric property is a mixture of one or more tilted smectic phases containing a suitable chiral doping substance as a base material mixture [Mo by La Beresnev et al.
l, Cryst. Liq, Cryst, 89 , p. 327 (1982); HR Br
and J. Physique 44 (Lett.), L-771 (198
3 years)]]. Such compositions are based on the ferroelectric properties of chirally tilted compositions as described by Clark and Lagerwall in SS.
FLC Technology Principles [NA Clark and ST Lag
Appl. Phys. Lett. 36 , 899 (1980)
); U.S. Pat. No. 4,367,924], and can be used as a dielectric for a rapid switching display. In this phase, the elongated molecules are arranged in layers and these molecules have a tilt angle with respect to the layer line. As one progresses from layer to layer, the tilt direction changes to a small angle with respect to the axis perpendicular to the layers, resulting in the formation of a helical structure. In a display based on the principles of SSFLC technology, the smectic phase is arranged perpendicular to the plane of the cell. The spiral alignment of molecules in the tilt direction is suppressed by a very small gap (about 1-2 μm) on each surface. This forces the longitudinal axes of the molecules to align themselves in a plane parallel to the plane of the cell, creating two different tilt orientations. In such a liquid crystal composition having spontaneous polarizability, switching is achieved before and after between these two states when a suitable alternating electric field is applied. This switching process is significantly faster than conventional twisted cells (TN-LCDs) based on nematic liquid crystals.

The low stability of currently available materials with chiral tilted smectic phases (eg S _c *) to chemicals, heat and light is extremely disadvantageous for considerable applications. Another drawback of the currently available chiral-tilted smectic mixture-based displays is that their spontaneous polarization values are too small, which has a negative effect on the switching time profile of this display, and ( Or) The phase pitch and tilt no longer meet the display technology requirements. Furthermore, the temperature range of such a ferroelectric phase is usually too narrow, and mainly too high.

It has now been found that the use of compounds of the formula I as constituents of chirally tilted smectic mixtures makes it possible to substantially reduce the abovementioned disadvantages. The compounds of formula I are outstandingly suitable as constituents of chirally tilted smectic liquid crystal compositions. In particular, with the aid of these compounds, they have a favorable ferroelectric phase region, a particularly wide S _c * phase region, an excellent ability to supercool without crystallization to temperatures well below 0 ° C. Composition by (phase)
Has a melting point of 0 ° C. or higher, but can generally be subcooled to a temperature sufficiently lower than 0 ° C.), has a preferable pitch degree and a high spontaneous polarization value for such a composition (phase), and is particularly chemical. A highly stable chiral tilted smectic liquid crystal composition (liquid crystal phase) can be produced. P is nC / cm
Represents a spontaneous polarization value of ² units.

The compounds of formula I have a wide field of application. These compounds can be used as a base material mainly constituting a liquid crystal smectic material by appropriately selecting a substituent. However, the compounds of the formula I can also have, for example, the dielectric anisotropy and / or the optical anisotropy and / or the viscosity and / or the spontaneous polarization value and / or the phase region and / or of such dielectrics. Or) to change the tilt angle and / or pitch
It can be added to liquid crystal substrates from another group of compounds.

The invention therefore relates to the use of the compounds of the formula I as constituents of chirally tilted smectic liquid crystal compositions. The present invention also provides a smectic liquid crystal composition, in particular a chirally tilted smectic composition, containing at least one compound of formula I, and also a liquid crystal display device comprising such a composition (phase), In particular, it relates to an electro-optical display element.

For brevity, in the following description:
Cy is a 1,4-cyclohexylene group, and Ph
e is a 1,4-phenylene group, which optionally has 1 or 2 F and / or C as substituents.
optionally having 1 atom and / or CH ₃ and / or CN group [= Phe (F), Phe (Cl), P
_{he (CH 3), Phe (} CN) ].

The compounds of the formula I are especially those of the partial formula I
a, Ib, Ie and If (having 3 rings), and also Ic, Id, Ig, Ih, Ii and Ij (having 4 rings) are included: R ¹ -Pyr- Phe-Z ¹ -Phe-R ² Ia R ¹ -Pyr-Cy-Z ¹ -Phe-R ² Ib R ¹ -Pyr-Phe-Z ¹ -Phe-Z ² -A ³ -R ² Ic R ¹ -Pyr -Cy-Z ¹ -Phe-Z ² -A ³ -R ² Id R ¹ -Phe-Pyr-Z ¹ -Phe-R ² Ie R ¹ -Cy-Pyr-Z ¹ -Phe-R ² If R ^1- Phe-Pyr-Z ¹ -Phe-Z ² -A ³ -R ² Ig R ¹ -Cy-Pyr-Z ¹ -Phe-Z ² -A ³ -R ² Ih R ¹ -Phe-Pyr-Z ¹ -A ² -Z ² -Phe-R ² Ii R ¹ -Pyr-Phe-Z ¹ -A ² -Z ² -Phe-R ² Ij Among these compounds, compounds represented by the partial formulas Ia, Ic and Ie are preferable.

Preferred compounds of the sub-formula Ia include compounds of the sub-formulae Iaa to Iae: R ¹ -Pyr-Phe-OCH ₂ -Phe-R ² Iaa R ¹ -Pyr-Phe-CH ₂ CH ₂ -Phe-R ² Iab R ¹ -Pyr-Phe-CH ₂ O-Phe-R ² Iac R ¹ -Pyr-Phe-OCO-Phe-R ² Iad R ¹ -Pyr-Phe-COO-Phe-R ² Iae Of these compounds, the compounds of the partial formulas Iaa and Iad are particularly preferred. Iae is especially preferred.

Preferred compounds of formula Ib include compounds of formulas Iba to Ibc: R ¹ -Pyr-Cy-OCH ₂ -Phe-R ² Iba R ¹ -Pyr-Cy-CH ₂ CH ₂ -Phe-R ² Ibb R ¹ -Pyr-Cy-CH ₂ O-Phe-R ² Ibc Preferred compounds represented by the partial formula Ic are partial formulas Ica to
It is a compound represented by Icg: R ¹ -Pyr-Phe-OCH ₂ -Phe-OCO-Cy-R ² Ica R ¹ -Pyr-Phe-OCH ₂ -Phe-OCO-Phe-R ² Icb R ¹ -Pyr -Phe-OCH ₂ -Phe-Pyr-R ² Icc R ¹ -Pyr-Phe-OCO-Phe-Phe-R ² Icd R ¹ -Pyr-Phe-OCO-Phe-Pyr-R ² Ice R ¹ -Pyr- Phe-COO-Phe-Phe-R ² Icf R ¹ -Pyr-Phe-COO-Pyr-Phe-R ² Icg Among these compounds, partial formulas Ica, Icd, Ic
Especially preferred are the compounds designated e, Icf and Icg, especially Ice.

Preferred compounds of formula Ie include those of formulas Iea to Iee: R ¹ -Phe-Pyr-OCH ₂ -Phe-R ² Iea R ¹ -Phe-Pyr-CH ₂ CH ₂ -Phe-R ² Ieb R ¹ -Phe-Pyr-CH ₂ O-Phe-R ² Iec R ¹ -Phe-Pyr-OCO-Phe-R ² Ied R ¹ -Phe-Pyr-COO-Phe-R ² Iee Among these compounds, the compounds represented by the partial formulas Iea, Ied and Iee are particularly preferable.

Preferred compounds of formula If include those of the partial formulas Ifa to Ife: R ¹ -Cy-Pyr-OCH ₂ -Phe-R ² Ifa R ¹ -Cy-Pyr-CH ₂ CH ₂ -Phe-R ² Ifb R ¹ -Cy-Pyr-CH ₂ O-Phe-R ² Ifc R ¹ -Cy-Pyr-OCO-Phe-R ² Ifd R ¹ -Cy-Pyr-COO-Phe-R ² Ife Preferred compounds of the partial formula Ig are those of the partial formula Iga
Includes compounds represented by Igk: R ¹ -Phe-Pyr-OCH ₂ -Phe-Cy-R ² Iga R ¹ -Phe-Pyr-OCO-Phe-OCO-Phe-R ² Igb R ¹ -Phe-Pyr -OCO-Phe-OCO-Cy-R ² Igc R ¹ -Phe-Pyr-OCO-Phe-COO-Phe-R ² Igd R ¹ -Phe-Pyr-OCO-Phe-COO-Cy-R ² IgE R ¹ -Phe-Pyr-COO-Phe-COO-Phe-R ² Igf R ¹ -Phe-Pyr-COO-Phe-COO-Cy-R ² Igg R ¹ -Phe-Pyr-COO-Phe-OCO-Phe-R ² Igh R ¹ -Phe-Pyr-COO-Phe-OCO-Cy-R ² Igi R ¹ -Phe-Pyr-COO-Phe-Pyr-R ² Igj R ¹ -Phe-Pyr-OCO-Phe-Pyr-R ² Igk Among these compounds, the compound represented by the partial formula Igk is particularly preferable.

Preferred compounds of formula Ii include those of formulas Iia to Iid: R ¹ -Phe-Pyr-OCH ₂ -Phe-Phe-R ² Iia R ¹ -Phe-Pyr-OCH. ₂ -Phe-CH ₂ O-Phe-R ² Iib R ¹ -Phe-Pyr-CH ₂ O-Phe-Phe-R ² Iic R ¹ -Phe-Pyr-OCO-Phe-Phe-R ² Iid Partial Formula Ij Preferred compounds represented by are partial formulas Ija-
Ijd includes compounds: R ¹ -Pyr-Phe-OCH ₂ -Phe-Phe-R ² Ija R ¹ -Pyr-Phe-OCO-Phe-Phe-R ² Ijb R ¹ -Pyr-Phe-COO. -Pyr-Phe-R ² Ijc R ¹ -Pyr-Phe-COO-Phe-Phe-R ² Ijd In the compounds represented by the formulas mentioned above and below, R ¹
And R ² is preferably alkyl or alkoxy, and also oxaalkyl, alkanoyloxy or alkoxycarbonyl.

A ¹ is preferably -Pyr-Phe- or Phe-Pyr-, particularly preferably -Pyr-.
A Phe-, and -A ¹ - is furthermore preferably formula 1-4:

[Chemical 7] Is a structuring element selected from the group consisting of:

The groups of formulas 1 and 2 are particularly preferred. A ² is preferably unsubstituted 1,4-phenylene or trans-1,4-cyclohexylene. Z ¹ is preferably -OCH ₂ -, - a O-CO- or -CO-O. m is preferably 0. Z ² is preferably a single bond, —CO—O or —O—CO—, and particularly preferably —.
It is O-CO-. A ³ is preferably Cy or Phe
Is.

The alkyl radicals in the radicals R ¹ and / or R ² can be straight-chain or branched. These groups are preferably straight-chain and comprise C atoms 5, 6,
It has 7, 8, 9, 10, 11 or 12 and is therefore preferably pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl, and also methyl, ethyl, propyl or butyl.

R ¹ and / or R ² are alkyl groups, and one CH ₂ group (“alkoxy” or “oxaalkyl”) or two CH ₂ present in these groups is present.
_{When two} radicals (“alkoxyalkoxy” or “dioxaalkyl”) are replaced by O atoms, these radicals can be straight-chain or branched.
These groups are preferably straight-chain and have 5 C atoms,
Having 6, 7, 8, 9, 10, 11 or 12 and therefore preferably pentoxy, hexoxy, heptoxy, octoxy, nonoxy, decoxy, undecoxy, dodecoxy, 2-, 3- or 4-oxapentyl, 2- Three
-, 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- or 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, 1,
4-dioxaoctyl, 1,4,7-trioxaoctyl, 1,4-dioxanonyl or 1,4-dioxadecyl.

In the compounds of formula I, the alkenyl group is preferably of the formula

Embedded image (Wherein n2 is 0 to 10, preferably 2 to 10, and n1 is 0 to 5, preferably 0).

The compounds of formula I and the sub-formulae above and below which contain branched side groups R ¹ or R ² are optionally suitable because of their high solubility in conventional liquid-crystal substrates. Significantly, but especially when they are optically active, they are important as chiral doping materials for chirally tilted smectic phases. However, such compounds are also suitable as constituents of the nematic liquid crystal phase, in particular for preventing inversion twisting. Branched groups of this type generally have at most one chain branch. Suitable branched groups are isopropyl, 2-butyl (= 1-methylpropyl), isobutyl (= 2-methylpropyl), isobutyl (= 2-methylpropyl), 2-methylbutyl, isopentyl (= 3-methylbutyl). , 2-methylpentyl, 3-methylpentyl,
2-ethylhexyl, 2-propylpentyl, 2-octyl, isopropoxy, 2-methylpropoxy, 2-methylbutoxy, 3-methylbutoxy, 2-methylpentoxy, 3-methylpentoxy, 2-ethylhexoxy,
1-methylhexoxy, 1-methylheptoxy, 2-oxa-3-methylbutyl, 3-oxa-4-methylpentyl and 2-octyloxy.

The asymmetric carbon atom is preferably two differently substituted C atoms, one H atom and halogen (especially F, Cl or Br), an alkyl or alkoxy having 1 to 5 C atoms each. And a substituent selected from the group consisting of a group and CN. Such an optically active organic group preferably has the formula

[Chemical 9] [In Formula, X is -CO-O-, -O-CO-, -O-CO-
O-, -CO-, -O-, -S-, -CH = CH-,-
CH = CH-COO- or a single bond, Q is an alkylene having 1 to 5 C atoms, and a CH ₂ group not bonded to X present in this group is also -O-, -CO.
-, -O-CO-, -CO-O- or -CH = CH-
Or Q is a single bond, Y is CN, halogen, methyl or methoxy, and R is an alkyl group different from Y having 1 to 18 C atoms. 1 C present in the group
H ₂ group or _two non-adjacent CH ₂ groups are —O—, —
CO-, -O-CO-, -CO-O- and / or
Optionally substituted by -CH = CH-].

X is preferably --CO--O--, --O--CO.
-, -O-, -CH = CH-COO- (trans) or a single bond. -O-, -CO-O- and -O-C
O- is particularly preferred. Q is preferably alkylene or a single bond and particularly preferably -CH ₂ having 1-5 C atoms
- it is - CH ₂ CH ₂ or a single bond. Y is preferably CH _3, -CN or Cl, particularly preferably -CN or Cl. R is preferably straight-chain alkyl having 1 to 10, in particular 1 to 7 C atoms, the CH ₂ group being bonded to the asymmetric C atom present in these groups being optionally --O-- , -O-CO- or -CO-O-.

R ² in formula I is preferably an optically active group. Here, a particularly preferred optically active group has the formula

[Chemical 10] [Wherein X is -O -, - CO-O- or a -O-CO-, Q is -CH ₂ - or a single bond, Y is CH _3, and R is C atoms 7 CH ₂ groups attached to an asymmetric C atom present in these groups are straight chain alkyl groups having -O-, -CO-O- or -O-.
Replaced by CO-].

Of the compounds of formula I and sub-formulas mentioned herein, those in which at least one of the radicals contained therein has one of the abovementioned preferred meanings are preferred. A particularly preferred narrow group of compounds includes compounds of formulas I1-I56
There is a compound represented by: R-Pyr-Phe-OCH ₂ -Phe-R ′ I 1 R-Pyr-Phe-CH ₂ O-Phe-R ′ I 2 R-Pyr-Phe-OCO-Phe-R ′ I 3 R -Pyr-Phe-COO-Phe- R 'I4 R-Pyr-Phe-CH 2 CH 2 -Phe-R' I5 R-Phe-Pyr-OCH 2 -Phe-R 'I6 R-Phe-Pyr-CH 2 O-Phe-R ′ I7 R-Phe-Pyr-OCO-Phe-R ′ I8 R-Phe-Pyr-COO-Phe-R ′ I9 R-Phe-Pyr-CH ₂ CH ₂ -Phe-R ′ I10

R-Pyr-Phe-OCH ₂ -Cy-R ′ I11 R-Pyr-Phe-CH ₂ O-Cy-R ′ I12 R-Pyr-Phe-OCO-Cy-R ′ I13 R-Pyr-Phe -COO-Cy-R 'I14 R-Pyr-Phe-CH ₂ CH ₂ -Cy-R' I15 R-Phe-Pyr-OCH ₂ -Cy-R 'I16 R-Phe-Pyr-CH ₂ O-Cy- R'I17 R-Phe-Pyr-OCO-Cy-R 'I18 R-Phe-Pyr-COO-Cy-R' I19 R-Phe-Pyr-CH ₂ CH ₂ -Cy-R 'I20 R-Pyr-Phe -OCH ₂ -Phe-OCO-Cy-R ′ I21 R-Pyr-Phe-OCH ₂ -Phe-OCO-Phe-R ′ I22 R-Phe-Pyr-OCH ₂ -Phe-OCO-Cy-R ′ I23 R -Phe-Pyr-OCH ₂ -Phe-OCO-Phe-R ′ I24 R-Pyr-Phe-OCO-Phe-OCO-Cy-R ′ I25 R-Pyr-Phe-COO-Phe-OCO-Cy-R ′ I26 R-Phe-Pyr-OCO-Phe-OCO-Cy-R ′ I27 R-Phe-Pyr-COO-Phe-OCO-Cy-R ′ I28 R-Pyr-Phe-OCO-Phe-OCO-Phe-R ′ I29 R-Pyr-Phe-COO-Phe-OCO-Phe-R ′ I30 R-Pyr-Phe-OCO-Phe-OCO-Phe-R ′ I31 R-Phe-Pyr-COO-Phe-OCO-Phe- R'I32 R-Pyr-Phe-OCH ₂ -Phe-Cy-R 'I33 R-Pyr-Phe-OCH ₂ -Phe-Phe-R' I34 R-Pyr-Phe-OCH ₂ -Phe-Pyr-R ' I35 R-Pyr-Phe-OCO-Phe-Cy-R 'I36 R-Pyr-Phe-OCO-Phe-Phe-R' I37 R-Pyr-Phe-OCO-Phe-Pyr-R 'I38

R-Phe-Pyr-OCH ₂ -Phe-Cy-R ′ I39 R-Phe-Pyr-OCH ₂ -Phe-Phe-R ′ I40 R-Phe-Pyr-OCH ₂ -Phe-Pyr-R ′ I41 R-Phe-Pyr-OCO--Phe-Cy-R ′ I42 R-Phe-Pyr-OCO-Phe-Phe-R ′ I43 R-Phe-Pyr-OCO-Phe-Pyr-R ′ I44 R-Phe -Pyr-OCH ₂ -Pyr-Phe-R ′ I45 R-Phe-Pyr-OCO-Pyr-Phe-R ′ I46 R-Pyr-Phe-OCO-Phe (F) -R ′ I47 R-Pyr-Phe- COO-Phe (F) -R ′ I48 R-Phe-Pyr-OCO-Phe (F) -R ′ I49 R-Pyr-Phe-CH ₂ O-Phe (F) -R ′ I50 R-Pyr-Phe ( F) -OCO-Phe-R ′ I51 R-Pyr-Phe (F) -OCO-Cy-R ′ I52 R-Pyr-Phe (F) -COO-Phe-R ′ I53 R-Pyr-Phe (F) -COO-Cy-R 'I54 R-Pyr-Phe-COO-Phe (2-CN) -R' I55 R-Pyr-Phe-COO-Phe (2-CN, 3-CN) -R 'I56 The above formula In I1 to I56, R and R'are preferably linear alkyl, alkoxy, alkanoyloxy or alkoxycarbonyl groups each having 5 to 12 C atoms.

The above formula represents two possible 2,2 for the pyridine-2,5-diyl or pyrimidine-2,5-diyl group.
Includes 5-positional isomers. This group is preferably attached to R ¹ in the 5-position. The compounds of the formula I which have no S _c phase are likewise suitable as constituents of the smectic phases according to the invention.

All compounds of formula I have been described in the literature [eg Methoden der Organischen Chem by Houben-Weyl.
ie (Method of Organic Chemistry), Georg Thieme Publisher (Stuttgar
can be prepared by methods known per se, such as those described in standard academic textbooks (e.g. city), more precisely under known reaction conditions which are suitable for the reaction mentioned. Variants which are known per se, but are not mentioned here in greater detail, can also be used.

The person skilled in the art can adapt the synthetic method which is appropriate from the description in the literature by a conventional method [for example, for compounds having 1,4-cyclohexylene and 1,4-phenylene groups, published German patent application in West Germany]. A few
44,732, 2,450,088, 2,429,093,
2,502,904,2,636,684,2,701,59
1 and 2,752,975; West German Patent 2,6 for compounds having a pyrimidine-2,5-diyl group.
41,724; West Germany published patent application 2, for compounds having a 1,3-dioxane-2,5-diyl group.
944,905 and 3,227,916); D for compounds having a 1,3-dithiane-2,5-diyl group
D 160,061; 1,4-bicyclo (2,2,2)-
US Pat. No. 4,26 for compounds having an octylene group.
The 1,652 and 4,219,256; and -CH ₂ C
Reference may be made to published German patent application 3,201,721 for compounds having an H ₂ -crosslinking member.

The starting compounds can also, if desired, be formed in situ in such a way that they are not isolated from the reaction mixture but are immediately further reacted to give the compounds of the formula I.

In general, two corresponding sub-compounds [eg (1) and (2) (Scheme 1) or (3) and (4)]
(Scheme 2)] is condensed to form a compound of formula I : Scheme I :

[Chemical 11]

Reaction formula 2 :

[Chemical 12] —M ¹ L ¹ and —M ² L ² are, for example, malonic acid derivatives (eg malondialdehyde), amidines, aldehydes, 1,3-propanediol and / or 1,3-
Represents a condensable moiety corresponding to propanedithiol. L ¹ L ² is one or more groups to be removed.

-M ³ L ³ and -M ⁴ L ⁴ are, for example, -C
OOH, -CO-halogen, -OH, -O metal, -CH
₂ - halogen, -CH ₂ - metal, -CH ₂ -OH, -CH ₂
It represents a condensable moiety selected from the group consisting of -O-metal, -metal and -halogen. L ³ and L ⁴ are leaving groups. L ³ L ⁴ is a group to be removed such as H ₂ O, H-halogen or metal-halogen.

However, the synthesis of compounds of formula I may also be carried out by the corresponding intramolecular condensation [eg condensation of 1,4-diketones with hydrazine (eg West German published patent 3,238, 350) or a butadiene derivative with, for example, an acetylene dicarboxylic acid derivative (for example, Japanese Patent Laid-Open No. 58-144,3).
27; Japanese Patent Laid-Open No. 58-146,543].

The starting compound is known or can be obtained by the same method as the method for producing the known compound. The routine method allows the person skilled in the art from the prior art information to adapt the method of synthesis and / or the appropriate starting material.

The formula I covers most of the known compounds, for example the preferred pyrimidine derivatives are West German patent applications P 3,401,321, P 3,404,116, P
3,500,909 and P 3,506,446, West German published patent application 3,315,295, European published patent application 84,194 and US 4,311,61.
0 (European Patent 25,119).

However, the present invention also provides novel pyrimidine derivatives of formula II: R ¹ -A ¹ -Pyr-Z ¹ -A ^2- [Z ² -A ³ ] _m -R ² II wherein R ¹ And R ² are each an alkyl group having 1 to 12 C atoms, one C being present in these groups.
H ₂ group or _two non-adjacent CH ₂ groups are —O—, —
CO-, -O-CO-, -CO-O- or -CH = C
Optionally substituted by H-, and one of the groups R ¹ and R ² can also be H, F, Cl, Br or CN, Pyr is pyrimidine-2,5-diyl and A ² And A ³ are each trans-1,4-cyclohexylene, or are unsubstituted or substituted with 1 or 2 F and / or Cl atoms and / or CH ₃ and / or CN groups. ¹ , 4-phenylene having 1 or 2, wherein A ¹ has 1 or 2 F and / or Cl atoms which are unsubstituted or substituted, and / or CH ₃ and / or CN groups. , 4-phenylene, Z ¹ is —OCH ₂ — or —O—CO—, and Z ² is —CO—O—, —O—.
_{CO -, - CH 2 CH 2} -, - CH 2 O -, - O-CH 2 -
Or a single bond and m is 0 or 1] and a compound of formula II, a liquid crystal phase containing a compound of formula II and its use as a constituent of a liquid crystal phase.

The compounds of formula II have a high chemical stability. These compounds are colorless and easily miscible with all customary liquid crystal compounds. The use of these compounds in the liquid crystal phase results in a wider mesophase range and improved spontaneous polarization values in the chirally tilted smectic phase. Therefore, the phase according to the invention is SS
Very well suited for display liquid crystal phases based on the principles of FLC technology. However, these compounds are also suitable for other electro-optical display elements such as TN cells or guest / host cells. In this case, these compounds act not only to increase the mesophase range, but also to prevent reversal twist and to improve elastic properties.

R ¹ and R ² are preferably 3 to 10 C atoms.
And alkyl or alkoxy groups each having an individual number. These are preferably linear. However,
Another preferred compound is a compound of formula II in which ^one of the groups R ¹ and R ² is a chain alkyl or alkoxy group. A ² and A ³ are preferably trans-
It is 1,4-cyclohexylene or unsubstituted 1,4-phenylene. A ¹ is preferably unsubstituted 1,4-phenylene. m is preferably 0.

Formula II includes particularly preferred compounds of the following partial formulas IIa-IIf: R ¹ -Phe-Pyr-OCH ₂ -Phe-R ² IIa R ¹ -Phe-Pyr-OCO-Phe-R ² IIb R ¹ -Phe-Pyr-OCH ₂ -Cy-R ² IIc R ¹ -Phe-Pyr-OCO-Cy-R ² IId R ¹ -Phe-Pyr-OCO-Phe-OCO-Phe-R ² IIe R ¹ -Phe-Pyr-OCO-Phe- COO-Phe-R 2 IIf of these, subexpression IIa, IIb, compounds represented by IIc and IId are particularly preferred. Very particularly preferred compounds are those of the partial formulas IIa and IIb.

The compounds of the formula II are obtained, for example, by esterifying the corresponding carboxylic acid compound or one of its reactive derivatives with the corresponding alcohol compound or its reactive derivative, or by etherification of the corresponding hydroxy compound. , Or a corresponding amidine compound or a derivative thereof with a 2-acetylalkanal dialkyl acetal or a reactive derivative thereof.

The present invention further provides a novel tetranuclear compound represented by the following formula III and a compound represented by the formula III, a liquid crystal phase containing the compound represented by the formula III, and a component of the liquid crystal phase. R ¹ -A ¹ -Z ³ -A ¹ ′ -R ² III, wherein R ¹ and R ² are each an alkyl group having 1 to 12 C atoms and are present in these groups. Do one C
H ₂ group or _two non-adjacent CH ₂ groups are —O—, —
CO-, -O-CO-, -O-COO-, -CO-O-
And (or) may be replaced by -CH = CH-, A ¹ and A ¹ 'are each -Pyr-Ph
e-, -Phe-Pyr-, -Pyr-Cy- or-
Cy-Pyr-, where Pyr is pyrimidine-2,5-
Is diyl, Phe is unsubstituted or as a substituent 1
1,4-phenylene having 1 or 2 F and / or Cl atoms and / or CH ₃ and / or CN groups, Cy is trans-1,4-cyclohexylene, and Z ³ It is -CO-O- or -CH ₂
O-].

The compound of formula III has high chemical stability. These compounds are colorless and easily miscible with all customary liquid crystal compounds. The use of these compounds in the liquid crystal phase results in a wider mesophase range and improved spontaneous polarization values in the chirally tilted smectic phase. Therefore, this phase according to the invention is very well suited to a liquid crystal phase for display based on the principles of SSFLC technology. However, they are also suitable for other electro-optical display elements such as TN cells or guest / host cells. In this case, in addition to expanding the mesoface range, they act to prevent reversal twist and to improve elastic physical properties.

R ¹ and R ² are preferably 3 to 10 C atoms.
And alkyl or alkoxy groups each having an individual number. These are preferably linear. However,
Another preferred compound of formula III is ^{one in which one} of the groups R ¹ and R ² is a chain alkyl or alkoxy group, A ¹ and A ¹ ′ are preferably —Pyr.
-Phe- or -Phe-Pyr-.

Formula III includes particularly preferred compounds of the following partial formulas IIIa-IIId: R ¹ -Pyr-Phe-COO-Phe-Pyr-R ² IIIa R ¹ -Pyr-Phe-COO-Pyr- Phe-R ² IIIb R ¹ -Pyr-Phe-CH ₂ O-Phe-Pyr-R ² IIIc R ¹ -Pyr-Phe-CH ₂ O-Pyr-Phe-R ² IIId The compound represented by the formula III is, for example, By esterifying the corresponding carboxylic acid compound or its reactive derivative with the corresponding alcohol compound or its reactive derivative, or by etherifying the corresponding hydroxy compound, or by converting the corresponding amidine compound or its derivative into It can be produced by reacting with acetylalkanal dialkyl acetal or its reactive derivative.

A preferred constituent of the phase according to the invention is a compound of the formula IV: R ¹ -A ¹ -Z ¹ -A ^2- [Z ² -A ³ ] _m -R ² IV [wherein R ¹ and R ² are each an alkyl group having 1 to 12 C atoms, one C being present in these groups
H ₂ group or two or more non-adjacent CH ₂ groups are —O
-, -CO-, -O-CO-, -O-COO-, -CO
-O- and (or) may be replaced by -CH = CH-, and one also has the radicals R ¹ and ^{R 2, H, F, Cl} , can be Br or CN,
A ¹ is an unsubstituted or 1 or 2 F as a substituent.
And / or Cl and / or Br atoms and / or CH ₃ and / or CN 4,4 ′
-Biphenylyl, wherein one or more CH groups present in this group are replaced by N, A ²
And A ³ are each trans-1,4-cyclohexylene, or are one or two unsubstituted or substituted F and / or Cl atoms and / or Br atoms and / or CH ₃ And / or
1,4-phenylene having a CN group, wherein one or more CH groups present in this group may also be replaced by N, Z ¹ is —CH ₂ CH ₂ —, —C
O-O -, - O- CO -, - CH 2 O- or -OCH ₂
And Z ² is —CO—O—, —O—CO—, —CH ₂
CH ₂ —, —CH ₂ O—, —O—CH ₂ — or a single bond, and m is 0 or 1, provided that the compound has at least one laterally substituted 1,4-phenylene group. Have].

The compounds of formula IV have a high chemical stability. These compounds are colorless and easily miscible with all customary liquid crystal compounds. Their use in the liquid crystal phase results in a wider mesophase range and improved spontaneous polarization values in the chirally tilted smectic phase. Therefore, this phase according to the invention is SSFL
Very well suited as a liquid crystal phase for display based on the principles of C technology. However, these phases are also suitable for other electro-optical display elements, for example TN cells or guest / host cells. In this case, in addition to enlarging the mesoface,
In particular, it acts to prevent reverse twist and improve elastic properties.

R ¹ and R ² are preferably 3 to 10 C atoms.
And alkyl or alkoxy groups each having an individual number. These groups are preferably straight-chain. However, another preferred compound of formula III is a compound in which one of the radicals R ¹ and R ² is a chain alkyl or alkoxy group. Pyr is preferably attached to Phe at position 2. Z ¹ is preferably -CO-O-, -O-.
CO -, - CH ₂ O- or -OCH ₂ -, and particularly preferably not -O-CO- or -CO-O-. m is preferably 0.

The phenylene group which is laterally substituted is preferably [= Phe (F)] or CN by an F atom.
1,4-phenylene group substituted by a group [= Phe (CN)]. Furthermore, as a preferred compound, a compound having a 2,3-dicyano-1,4-phenylene group [= Phe (CN) ₂ ], especially a derivative of 2,3-dicyanohydroquinone [= Phe (2-CN, 3- CN)].

Formula IV includes particularly preferred compounds of the partial formulas IVa-IVm: R ¹ -Pyr-Phe-OCO-Phe (F) -R ² IVa R ¹ -Pyr-Phe-COO-Phe (F ) -R ² IVb R ¹ -Pyr-Phe-OCO-Phe (CN) -R ² IVc R ¹ -Pyr-Phe-COO-Phe (CN) -R ² IVd R ¹ -Phe-Pyr-OCO-Phe ( F) -R ² IVe R ¹ -Phe-Pyr-COO-Phe (F) -R ² IVf R ¹ -Phe-Pyr-OCO-Phe (CN) -R ² IVg R ¹ -Phe-Pyr-COO-Phe (CN) -R ² IVh R ¹ -Pyr-Phe (F) -COO-A ² -R ² IVi R ¹ -Pyr-Phe (F) -OCO-A ² -R ² IVj R ¹ -Pyr-Phe ( F) -OCH ₂ -A ² -R ² IVk R ¹ -Phe (F) -Pyr-OCO-A ² -R ² IVl R ¹ -Pyr-Phe-COO-Phe (Z-CN, 3-CN)- R ² IVm In the sub-formulae IVa, IVc, IVe and IVm, R ² is preferably alkoxy having 4 to 10 C atoms.

Partial formulas IVa, IVb, IVd, IVi, IVj, IV
Especially preferred are the compounds of the formulas k and IVm, in which the partial formula
Particular preference is given to compounds of the formula IVa and IVb, also IVm. The compound represented by the formula IV is obtained by, for example, esterifying a corresponding carboxylic acid compound or one of its reactive derivatives with a suitable alcohol compound or one of its reactive derivatives, or an ester of a corresponding hydroxy compound. By reacting the corresponding amidine compound or its derivative with a 2-acetyl-alkanal dialkyl acetal compound or one of its reactive derivatives, or by converting the diazonium group in the corresponding diazonium salt compound to C
It can be prepared by substitution with 1, F or CN or by reacting the corresponding chlorine or bromine compound with a cyanide compound.

All compounds of the formulas II, III and IV and also of the corresponding partial formulas are preferred constituents of the formula I for smectic phases according to the invention. For the compounds of the formulas II, III and IV, the preferred meanings given above for the compounds of the group of the formula I likewise apply.

Ferroelectric liquid crystal phases according to the present invention include at least one of the compounds of formula I, from 2 to 15,
It preferably contains 3 to 12 kinds of constituent components. These additional components are preferably selected from the compounds of formulas II-IV:

[Chemical 13] [Wherein R ⁴ and R ⁵ are each, independently of one another, n-alkyl having 5 to 12 C atoms, and R ⁶ , R ⁷ , R ⁸ and R ⁹ are each, independently of one another. , C
A straight-chain or branched, optionally chiral alkyl, alkoxy, alkoxycarbonyl or alkanoyloxy group having 5 to 12, in particular 6 to 10, the ring A being 1,4-phenylene or trans- 1,
4-cyclohexylene, and n is 0 or 1.
All these substances can be prepared by methods known from the literature.

A further preferred ferroelectric phase according to the invention is a phase containing at least one of the compounds of the formula V: R ¹ -Q ¹ -A- (Q ² ) _q -R ² [wherein R ¹ and R ² are each, independently of one another, a straight-chain alkyl radical having 1 to 15 C atoms, one CH ₂ radical being present in these radicals or not being adjacent 2
One or more CH ₂ groups also include —O—, —S—, —CO—,
_{CHCH 3 -O -, - CHCH 3} -, - CH- halogen -, CHCN -, - O- CO -, - O-COO -, - C
Optionally substituted by O—O— and / or —CH═CH—, A is

Embedded image And q is 0 or 1, Q ¹ and Q ² are each independently of the other-(A ⁰ -Z ⁰ ) _p- , and A ⁰ is 1 or 2 as an unsubstituted or substituent group. 1,4-having at least one halogen atom, CH ₃ and / or nitrile group
Cyclohexylene, one C present in this group
The H ₂ group or two CH ₂ groups which are not adjacent to each other can also be —O.
-And / or-S-, and / or

[Chemical 15] May be replaced by (Cy), or A
⁰ is 1,4-phenylene having one or more halogen atoms, CH ₃ and / or a nitrile group which is unsubstituted or substituted, and one or more of which are present in this group. The CH group may be replaced by N (Ph), and yet another one of A ⁰ is optionally replaced by halogen or CN 2,
6-naphthylene (Na) or tetrahydro-2,6-
Naphthylene (4H-Na), Z ⁰ , Z ¹ and Z ^2.
Are each independently -CO-O-, -O-CO
_{-, - CH 2 O -,} - OCH 2 -, - CH 2 CH 2 -, - C
HCNCH ₂ —, —CH ₂ —CHCN— or a single bond, and p is 1, 2 or 3, or A =
0 in the case of tetra- or octahydrophenanthrene, where A =

Embedded image At least one of the groups Z ⁰ is —CHCN
CH ₂ — or —CH ₂ CHCN— and / or at least one of the CH ₂ groups present in at least one of the radicals R ¹ and R ² is replaced by —CHCN—.

The compounds of formula V can have straight-chain or branched side-chain groups R ¹ and / or R ² . The compound having a branched side chain group can be used in a racemic form or as an optically active compound. The non-chiral base mixture of the compound of formula V and optionally another non-chiral component is chiral tilted by doping with the chiral compound of formula I, or even with another chiral compound. A smectic phase can be obtained.

Particularly preferred subgroups of compounds include compounds of formulas V1-V18:

[Chemical 17]

[0056]

Embedded image

Another particularly preferred narrow group of compounds is of formula V
Compounds represented by 19 to V22 are: R ¹ -A ⁰ -Cy- (CH ₂ ) _r -CHCN-C _s H _{2s + 1} V19 R ¹ -A ⁰ -A ⁰ -Cy- (CH ₂ ) _r- CHCN-C _s H _{2s + 1} V20 R ¹ -A ⁰ -A ⁰ -CHCN-CH ₂ -Cy-R ² V21 R ¹ -A ⁰ -A ⁰ -CH ₂ -CHCN-Cy-R ² V22 (Each formula Where r is 0, 1, 2 or 3 and (r +
s) is 1-14). The compounds of formula V which do not have a S _c phase are also suitable as constituents of the smectic phase according to the invention.

All compounds of formula V are described in the literature [eg Methoden der Organischen Chem by Houben-Weyl.
ie (Method of Organic Chemistry), Georg-Thieme Publisher (Stuttgar
can be prepared by methods known per se, such as those described in standard academic textbooks (e.g. city), more precisely under reaction conditions known per se suitable for the reaction mentioned. Use can also be made here of variants known per se which are not mentioned here in greater detail.

Formula V includes primarily known compounds.
For example, this preferred compound is a West German patent.
Application 3,231,707,3,319,781,3,320,
024, 3,407,013, 3,443,029, 3,3
32,690,3,332,691,3,332,692,
2,933,563,2,853,728,2,613,29
3,3,401,320,3,136,624,3,040,
632, 3,205,766, 2,240,864, 2,9
37,700,3,410,734,3,324,686,
Published European patent application 085,995, Europe
Published Patent Application 0,084,194, DD 116,732,
FR 2,425,469, FR 2,419,966, US
Patent 4,237,026, US Patent 3,953,491, U
S. Patent No. 4,225,454 or H.J. Deutscher et al.
J. Prakt. Chemie, 321, 569 (1979)
And J.C. Dubois et al. Mol. Cryst. Liq. Cryst.
47, 193 (1978).

Suitable constituents of the phases according to the invention include or

[Chemical 19] (Wherein R ¹ and R ² have the meanings defined for formula V).

The phase according to the invention preferably contains at least 3, especially at least 5, compounds of the formula I. A particularly preferred chiral tilted smectic liquid crystal phase according to the invention is one in which the non-chiral substrate mixture is in addition to the compound of formula I at least one of the other components having a negative or small positive dielectric anisotropy. Is a phase containing. Preference is given mainly to the phases according to the invention which contain exclusively the optically active component.
These other constituents in the non-chiral base mixture can make up 1 to 50%, preferably 10 to 25% of the base mixture. The compounds of the following partial formulas Va to Vj are suitable as further components with a small positive or negative dielectric anisotropy:

[0062]

Embedded image

In the above formulas, R ⁴ and R ⁵ are each preferably linear alkyl, alkoxy, alkanoyloxy or alkoxycarbonyl having 3 to 12 C atoms. X is preferably 0. Particularly preferred compounds are those of the partial formulas Va, Vb, Vd and Vf, wherein R ⁴ and R ⁵ are each a straight-chain alkyl or alkoxy each having 5 to 10 C atoms.

The compounds of the partial formulas Vc, Vh and Vi are suitable as additive substances for lowering the melting point and are usually added to the base mixture in a proportion of at most 5%, preferably 1 to 3%. R ⁴ and R ⁵ in the compounds of the partial formulas Vc, Vh and Vi are preferably C atoms 2
Is a straight-chain alkyl having -7, preferably 3-5. Another compound suitable for lowering the melting point in the phase according to the invention is a compound of the formula:

[Chemical 21] Where R ⁴ and R ⁵ have the preferred meanings given above for Vc, Vh and Vi.

Structural element A, B or C

[Chemical formula 22] The compound having is also suitable as another component having a negative dielectric anisotropy.

Preferred compounds of this type are of formulas VIa, VIb
And VIc:

[Chemical formula 23] In each of the above formulas, R'and R "are preferably C
It is a straight-chain alkyl or alkoxy group each having 2 to 10 atoms. Q ¹ and Q ² are 1.4
-Phenylene, trans-1,4-cyclohexylene,
4,4'-biphenylyl, 4- (trans-4-cyclohexyl) -phenyl, trans, trans-4,4'-
Represents bicyclohexyl or the radicals Q ¹ and Q ²
One of the can also be a single bond.

Q ³ and Q ⁴ are respectively 1,4-phenylene, 4,4'-biphenylyl or trans-1,4-
It is cyclohexylene. One of the groups Q ³ and Q ⁴ can also be a 1,4-phenylene group in which at least one CH group present in the group is replaced by N. R '''is a structure

[Chemical formula 24] Is an optically active group containing an asymmetric carbon atom having
Particularly preferred compounds of formula VIc are those of formula VIc
c '

[Chemical 25] (In the formula, A is 1,4-phenylene or trans-1,4-
Is cyclohexylene, and n is 0 or 1).

The dielectrics according to the invention can be manufactured in a manner which is conventional per se. In general, the components are dissolved in one another, preferably at elevated temperature. With suitable additives, the liquid crystal phases can be modified according to the invention in such a way that they can be used in all conventionally known liquid crystal display devices.

The following examples are intended to illustrate the invention without limiting it. mp = melting point, cp = clearing point. Throughout this specification, percentage data are percentages by weight; all temperature data are given in degrees Celsius (° C). Numerical values relating to spontaneous polarization are shown at room temperature. Furthermore, C means a solid crystalline state, S means a smectic phase (this index characterizes the phase type), N means a nematic state, Ch
Means cholesteric phase and I means isotropic phase. The number between the two symbols indicates the conversion temperature in degrees Celsius. The term "finished in conventional manner" shall have the following meanings: add water, extract the mixture with methylene chloride, separate the phases, dry the organic phase and then evaporate, crystallize the product. And / or chromatographically.

Examples Example 1 4- (5-heptylpyrimidin-2-yl) -phenyl p-pentylbenzyl ether 18%, 4- (5-heptylpyrimidin-2-yl) -phenyl p-hexylbenzyl ether 26 %, 4- (5-nonylpyrimidin-2-yl) -phenyl p-pentylbenzyl ether 13%, 4- (5-nonylpyrimidin-2-yl)
-Phenyl p-hexyl benzyl ether 4%, 2-
p-nonyloxyphenyl-5-nonylpyrimidine 2
4%, p- (5-nonylpyrimidin-2-yl) -phenyl p- (5-pentylpyrimidin-2-yl) -benzoate 8% and p- (5-heptylpyrimidin-
2-yl) -phenyl p- (5-heptylpyrimidine-
The liquid crystal phase consisting of 2-yl) -benzoate 7% is C /
It has S _c 13 °, S _c / N 64 ° and N / I 124 °.

Example 2 4- (5-heptylpyrimidin-2-yl) -phenyl p-pentylbenzyl ether 18%, 4- (5-heptylpyrimidin-2-yl) -phenyl p-hexylbenzyl ether 22%, 4 -(5-nonylpyrimidin-2-yl) -phenyl p-pentylbenzyl ether 13%, 4- (5-nonylpyrimidin-2-yl)
-Phenyl p-hexyl benzyl ether 10%, 2
-P-undecyloxyphenyl-5-heptylpyrimidine 21%, 2- (p-pentylphenyl) -pyrimidin-5-yl p-octylbenzyl ether 5%,
2- (p-hexylphenyl) -pyrimidin-5-yl p-nonylbenzyl ether 5% and 4- (5-octylpyrimidin-2-yl) -phenyltrans-4
A liquid crystal phase composed of 6% of pentylcyclohexyl methyl ether has C / S _c 6 °, S _c / N 63.5 ° and N
/ I 96 °.

Example 3 4- (5-heptylpyrimidin-2-yl) -phenyl p-pentylbenzyl ether 12%, 4- (5-heptylpyrimidin-2-yl) -phenyl p-hexylbenzyl ether 15%, 4 -(5-nonylpyrimidin-2-yl) -phenyl p-hexylbenzyl ether 10%, 2-p-nonyloxyphenyl-5-nonylpyrimidine 8%, 2-p-decyloxyphenyl-
5-octylpyrimidine 16%, p- (5-hexylpyrimidin-2-yl) -phenyl p- (5-pentylpyrimidin-2-yl) -benzoate 13%, 2-
(P-Pentylphenyl) -pyrimidin-2-yl p-
Nonylbenzyl ether 12%, 2-p-undecyloxyphenyl-5-heptylpyrimidine 5%, 4-
(5-Octylpyrimidin-2-yl) -phenyltrans-4-hexylcyclohexyl methyl ether 4
% And 4- (5-nonylpyrimidin-2-yl) -phenyltrans-4-pentylcyclohexylmethylether 5% have a liquid crystal phase of C / S _c −1 °, S _c /
N 63 ° and N / I 94 °.

Example 4 4- (5-hexylpyrimidin-2-yl) -phenyl p-hexylbenzyl ether 20%, 4- (5-heptylpyrimidin-2-yl) -phenyl p-pentylbenzyl ether 15%, 4 -(5-nonylpyrimidin-2-yl) -phenyl p-hexylbenzyl ether 10%, 4- (5-heptylpyrimidin-2-yl) -phenyl p-hexylbenzyl ether 4%,
4- (5-nonylpyrimidin-2-yl) -phenyl p
-Pentylbenzyl ether 16%, 2-p-nonyloxyphenyl-5-heptylpyrimidine 10%, 2
-P-nonyloxyphenyl-5-nonylpyrimidine
7%, p-hexyloxyphenyl trans-4-pentylcyclohexanecarboxylate 8% and p-
Heptylphenyl p-decyloxybenzoate 10
% Liquid crystal phase has C / S _c 0 °, S _c / N 79 ° and N / I 87 °.

Example 5 4- (5-hexylpyrimidin-2-yl) -phenyl p-hexylbenzyl ether 18%, 4- (5-heptylpyrimidin-2-yl) -phenyl p-pentylbenzyl ether 14%, 4 -(5-hexylpyrimidin-2-yl) -phenyl p-pentylbenzyl ether 10%, 4- (5-nonylpyrimidin-2-yl) -phenyl p-hexylbenzyl ether 10
%, 4- (5-heptylpyrimidin-2-yl) -phenyl p-hexylbenzyl ether 20%, 4- (5
-Nonylpyrimidin-2-yl) -phenyl p-pentylbenzyl ether 10%, 2-p-decyloxyphenyl-5-octylpyrimidine 6%, p-heptylphenyl p-decyloxybenzoate 7% and p
-Butyloxyphenyl p- (p-decyloxybenzoyloxy) -benzoate 5% consists of a liquid crystal phase of C
/ S _c 12 °, S _c / N 96 ° and N / I 107 °
Have.

Example 6 4- (5-hexylpyrimidin-2-yl) -phenyl p-hexylbenzyl ether 27%, 4- (5-heptylpyrimidin-2-yl) -phenyl p-pentylbenzyl ether 14%, 4 -(5-hexylpyrimidin-2-yl) -phenyl p-pentylbenzyl ether 7%, 4- (5-nonylpyrimidin-2-yl)
-Phenyl p-hexyl benzyl ether 2%, 4-
(5-heptylpyrimidin-2-yl) -phenyl p-
Hexylbenzyl ether 18%, 4- (5-nonylpyrimidin-2-yl) -phenyl p-pentylbenzyl ether 7%, 2-p-heptyloxyphenyl-
5-octylpyrimidine 4%, p-hexyloxyphenyl trans-4-pentylcyclohexanecarboxylate 2%, 4'-pentylbiphenyl-4-yl p-pentylbenzoate 10% and 4'-pentylbiphenyl-4-yl p-. Hexyl benzoate 9
The liquid crystal phase consisting of% has C / S _c 9 °, S _c / N 82 ° and N / I 116 °.

Example 7 4- (5-hexylpyrimidin-2-yl) -phenyl p-pentylbenzyl ether 16%, 4- (5-heptylpyrimidin-2-yl) -phenyl p-pentylbenzyl ether 26%, 4 -(5-Heptylpyrimidin-2-yl) -phenyl p-hexylbenzyl ether 36%, 4- (5-nonylpyrimidin-2-yl) -phenyl p-pentylbenzyl ether 18%
And a liquid crystal phase consisting of 4- (5-nonylpyrimidin-2-yl) -phenyl p-hexylbenzyl ether 4% has C / S _c 8 °, S _c / N 84.5 ° and N / I 1.
With 04 °.

Example 8 4- (5-hexylpyrimidin-2-yl) -phenyl p-hexylbenzyl ether 30%, 4- (5-heptylpyrimidin-2-yl) -phenyl p-pentylbenzyl ether 15%, 4 -(5-Hexylpyrimidin-2-yl) -phenyl p-pentylbenzyl ether 8%, 4- (5-nonylpyrimidin-2-yl)
-Phenyl p-hexyl benzyl ether 2%, 4-
(5-heptylpyrimidin-2-yl) -phenyl p-
A liquid crystal phase consisting of hexylbenzyl ether 21%, 4- (5-nonylpyrimidin-2-yl) -phenyl p-pentylbenzyl ether 8% and 2-p-nonyloxyphenyl-5-nonylpyrimidine 16% is C /
It has S _c -5 °, S _c / N 81 ° and N / I 99 °.

Example 9 4- (5-hexylpyrimidin-2-yl) -phenyl p-hexylbenzyl ether 27%, 4- (5-heptylpyrimidin-2-yl) -phenyl p-pentylbenzyl ether 14%, 4 -(5-hexylpyrimidin-2-yl) -phenyl p-pentylbenzyl ether 7%, 4- (5-nonylpyrimidin-2-yl)
-Phenyl p-hexyl benzyl ether 2%, 4-
(5-heptylpyrimidin-2-yl) -phenyl p-
Hexylbenzyl ether 18%, 4- (5-nonylpyrimidin-2-yl) -phenyl p-pentylbenzyl ether 7%, 2-p-nonyloxyphenyl-5
A liquid crystal phase consisting of 14% nonylpyrimidine and 10% R-4- (5-hexylpyrimidin-2-yl) -phenyl 2-chloropropionate is C / S _c * -4.
°, S _c * / Ch 64.7 ° and Ch / I 92.5 °
Have.

The spontaneous polarization values (nC / cm ² ) and pitch height (μm) of this phase are shown in the following table at various temperatures:

Example 10 2-p-nonyloxyphenyl-5-nonylpyrimidine 31%, 2-p-decyloxyphenyl-5-octylpyrimidine 9%, 2-p-octyloxyphenyl-5-octylpyrimidine 14%, 2-p-nonyloxyphenyl-5-heptylpyrimidine 18%, 2-
p-heptyloxyphenyl-5-heptylpyrimidin 13%, 4- (5-octylpyrimidin-2-yl)
A liquid crystal phase consisting of 10% of 4-phenyl-2-fluoro-4-decyloxybenzoate and 5% of 4- (5-decylpyrimidin-2-yl) -phenyl-2-fluoro-4-hexyloxybenzoate has a C / S _{c of} 7 °. , S _c /
It has S _A 57 °, S _A / N 67 °, and N / I 70.5 °.

Example 11 2-p-nonyloxyphenyl-5-nonylpyrimidine 28%, 2-p-nonyloxyphenyl-5-octylpyrimidine 3%, 2-p-heptyloxyphenyl-5-octylpyrimidine 25%, 2-p-heptyloxy-5-heptylpyrimidine 10%, 2-p-decyloxy-5-heptylpyrimidine 5%, 4- (5
-Octylpyrimidin-2-yl) -phenyl 2-fluoro-4-decyloxybenzoate 9%, 4- (5
-Heptylpyrimidin-2-yl) -phenyl 3-fluoro-4-heptyloxybenzoate 10% and 2-fluor-4-nonylphenyl 4- (5-decylpyrimidin-2-yl) -benzoate 10% Is C / S _c 13 °, S _c / S _A 64 °, S _A / N
It has 68 ° and N / I 83 °.

Example 12 2-p-nonyloxyphenyl-5-nonylpyrimidine 30%, 2-p-decyloxyphenyl-5-octylpyrimidine 15%, 2-p-octyloxyphenyl-5-octylpyrimidine 15%, 2-p-nonyloxyphenyl-5-heptylpyrimidine 12%, 3
-Fluor-4-hexylphenyl 4- (5-octylpyrimidin-2-yl) -benzoate 10%, 2-
Cyano-4-decylphenyl 4- (5-decylpyrimidin-2-yl) -benzoate 3%, 2- (4-heptylphenyl) -pyrimidin-5-yl 2-fluoro-
4-Heptylbenzoate 6% and 2- (4-octylphenyl) -pyrimidin-5-yl-3-fluoro-
The liquid crystal phase composed of 4-hexylbenzoate 9% is C /
S _c 16 °, S _c / S _A 59 °, S _A / N 63 °, N /
I 79 °.

Example 13 2-p-nonyloxyphenyl-5-nonylpyrimidine 30%, 2-p-decyloxyphenyl-5-octylpyrimidine 15%, 2-p-octyloxyphenyl-5-octylpyrimidine 20%, 2-p-nonyloxyphenyl-5-heptylpyrimidine 15%, 2
A liquid crystal phase consisting of -p-heptyloxyphenyl-5-heptylpyrimidine 10% and 2-fluoro-4- (5-octylpyrimidin-2-yl) -phenyl 4-octylbenzoate 10% had a C / S _{c of} 4 °, S _c / S _A
22 °, S _A / N 65 °, N / I 74 °.

Example 14 4- (5-hexylpyrimidin-2-yl) -phenyl p-hexylbenzyl ether 33%, 4- (5-heptylpyrimidin-2-yl) -phenyl p-pentylbenzyl ether 15%, 4 -(5-hexylpyrimidin-2-yl) -phenyl p-pentylbenzyl ether 10%, 4- (5-nonylpyrimidin-2-yl) -phenyl p-hexylbenzyl ether 3%,
4- (5-heptylpyrimidin-2-yl) -phenyl p-hexylbenzyl ether 24%, 4- (5-octylpyrimidin-2-yl) -phenyl 2-fluoro-4-heptyloxybenzoate 10% and 3-
The liquid crystal phase consisting of 5% of fluoro-4-octylphenyl 4- (5-decylpyrimidin-2-yl) -benzoate has C / S _c 3 °, S _c / N 75 °, N / I 98 °.

Example 15 4- (5-hexylpyrimidin-2-yl) -phenyl p-hexylbenzyl ether 32%, 4- (5-heptylpyrimidin-2-yl) -phenyl p-pentylbenzyl ether 16%, 4 -(5-hexylpyrimidin-2-yl) -phenyl p-pentylbenzyl ether 9%, 4- (5-nonylpyrimidin-2-yl)
-Phenyl p-hexyl benzyl ether 2%, 4-
(5-nonylpyrimidin-2-yl) -phenyl p-pentylbenzyl ether 18%, 4- (5-heptylpyrimidin-2-yl) -phenyl 3-fluoro-4-
Heptyloxybenzoate 13%, 2-Fluor-
4-nonylphenyl 4- (5-decylpyrimidine-2-
1) -benzoate 5% and 2-cyano-4-octylphenyl 4- (5-nonylpyrimidin-2-yl) -benzoate 5% have a liquid crystal phase of C / S _c −.
1 °, S _c / N 77 °, N / I 94 °.

Example 16 4- (5-heptylpyrimidin-2-yl) -phenyl p-pentylbenzyl ether 17%, 4- (5-heptylpyrimidin-2-yl) -phenyl p-hexylbenzyl ether 25%, 4 -(Nonylpyrimidine-
2-yl) -phenyl p-pentylbenzyl ether
13%, 4- (nonylpyrimidin-2-yl) -phenyl p-hexylbenzyl ether 4%, 2- (4-nonylphenyl) -pyrimidin-5-yl) 2-fluoro-4-heptylbenzoate 11%, 2 -Fluor-
4- (5-decylpyrimidin-2-yl) -phenyl 4
-Octylbenzoate 10%, 4- (5-heptylpyrimidin-2-yl) -phenyl 2-fluoro-4-
Heptyloxybenzoate 15% and 2-fluoro-4-nonylphenyl 4- (5-nonylpyrimidine-
2-yl) -benzoate 5% liquid crystal phase is C /
It has S _c 5 °, S _c / N 75 °, N / I 97 °.

Example 17 4- (5-hexylpyrimidin-2-yl) -phenyl p-hexylbenzyl ether 33%, 4- (5-heptylpyrimidin-2-yl) -phenyl p-pentylbenzyl ether 18%, 4 -(5-hexylpyrimidin-2-yl) -phenyl p-pentylbenzyl ether 10%, 4- (5-nonylpyrimidin-2-yl) -phenyl p-hexylbenzyl ether 3%,
4- (5-heptylpyrimidin-2-yl) -phenyl p-hexylbenzyl ether 25%, 5- (4-octylphenyl) -pyrimidin-2-yl 3-fluoro-4-octylbenzoate 4% and 2-fluoro A liquid crystal phase composed of -4- (5-decylpyrimidin-2-yl) -phenyl 4-heptylbenzoate 7% is C /
It has S _c 10 °, S _c / N 77 ° and N / I 100 °.

Example 18 5-Methoxy-2- (4-n-octylphenyl) -pyrimidine 0.65 g [This compound is obtained by condensing methyl β-hydroxy-α-methoxyacrylate with 4-n-octylbenzamidine hydrochloride. the resulting 4-hydroxy-5-methoxy-pyrimidine is reacted with P ₂ S _5, the resulting 4-mercapto pyrimidine accordance JH Chesterfield other (J. Chem. Soc., pp 4590 [1960]), using Raney nickel Obtained by reduction] and 1.0 g of KOH in 15 ml of ethylene glycol are boiled for 10 hours. 10 ml of water to the cooled solution
Then acidified with glacial acetic acid and 5 with ether.
Extract twice. After customary work up, 5-hydroxy-2- (4-n-octylphenyl) -pyrimidine is obtained. (Similarly, other homologous compounds are obtained). Obtained 5- in 2.5 ml of dimethylformamide
0.22 g of hydroxy-2- (4-n-octylphenyl) -pyrimidine, 0.25 g of 4-n-heptylbenzoyl chloride and 0.15 g of potassium carbonate are then added to 10
Heat at 0 ° C. for 12 hours with stirring. The salts are removed by suction filtration, the filtrate is concentrated, the residue is taken up in ether and washed with water until neutral. Finished in the conventional way, 2
-(4-n-octylphenyl) -pyrimidin-5-yl 4-n-heptylbenzoate is obtained.

Similarly, the following compound is prepared: 2- (4-propylphenyl) -pyrimidin-5-yl-4-propylbenzoate 2- (4-pentylphenyl) -pyrimidin-5-yl-4-propylbenzoate 2 -(4-Hexylphenyl) -pyrimidin-5-yl 4-propylbenzoate 2- (4-heptylphenyl) -pyrimidin-5-yl 4-propylbenzoate 2- (4-octylphenyl) -pyrimidin-5-yl-4 -Propylbenzoate 2- (4-nonylphenyl) -pyrimidin-5-yl 4
-Propylbenzoate 2- (4-decylphenyl) -pyrimidin-5-yl 4
-Propylbenzoate 2- (4-propylphenyl) -pyrimidin-5-yl 4-hexylbenzoate

2- (4-Pentylphenyl) -pyrimidin-5-yl-4-hexylbenzoate 2- (4-hexylphenyl) -pyrimidin-5-yl-4-hexylbenzoate 2- (4-heptylphenyl) -pyrimidine- 5-yl 4-hexylbenzoate 2- (4-octylphenyl) -pyrimidin-5-yl 4-hexylbenzoate 2- (4-nonylphenyl) -pyrimidin-5-yl 4
-Hexylbenzoate 2- (4-decylphenyl) -pyrimidin-5-yl 4
-Hexylbenzoate 2- (4-propylphenyl) -pyrimidin-5-yl 4-heptylbenzoate 2- (4-pentylphenyl) -pyrimidin-5-yl 4-heptylbenzoate 2- (4-hexylphenyl) -pyrimidine- 5-yl 4-heptylbenzoate 2- (4-heptylphenyl) -pyrimidin-5-yl 4-heptylbenzoate 2- (4-octylphenyl) -pyrimidin-5-yl 4-heptylbenzoate 2- (4-nonylphenyl ) -Pyrimidin-5-yl 4
-Heptylbenzoate 2- (4-decylphenyl) -pyrimidin-5-yl 4
-Heptyl benzoate

2- (4-Propylphenyl) -pyrimidin-5-yl 4-octylbenzoate 2- (4-pentylphenyl) -pyrimidin-5-yl 4-octylbenzoate 2- (4-hexylphenyl) -pyrimidine- 5-yl 4-octylbenzoate 2- (4-heptylphenyl) -pyrimidin-5-yl 4-octylbenzoate 2- (4-octylphenyl) -pyrimidin-5-yl 4-octylbenzoate 2- (4-nonylphenyl ) -Pyrimidin-5-yl 4
-Octylbenzoate 2- (4-decylphenyl) -pyrimidin-5-yl 4
-Octylbenzoate 2- (4-propylphenyl) -pyrimidin-5-yl-4-nonylbenzoate 2- (4-pentylphenyl) -pyrimidin-5-yl-4-nonylbenzoate 2- (4-hexylphenyl) -pyrimidine- 5-yl 4-nonylbenzoate 2- (4-heptylphenyl) -pyrimidin-5-yl 4-nonylbenzoate 2- (4-octylphenyl) -pyrimidin-5-yl 4-nonylbenzoate 2- (4-nonylphenyl ) -Pyrimidin-5-yl 4
-Nonylbenzoate 2- (4-decylphenyl) -pyrimidin-5-yl 4
-Nonylbenzoate 2- (4-propylphenyl) -pyrimidin-5-yl-4-decylbenzoate 2- (4-pentylphenyl) -pyrimidin-5-yl-4-decylbenzoate 2- (4-hexylphenyl) -pyrimidine- 5-yl 4-decylbenzoate 2- (4-heptylphenyl) -pyrimidin-5-yl 4-decylbenzoate 2- (4-octylphenyl) -pyrimidin-5-yl 4-decylbenzoate 2- (4-nonylphenyl ) -Pyrimidin-5-yl 4
-Decylbenzoate 2- (4-decylphenyl) -pyrimidin-5-yl 4
-Decyl benzoate

Example 19 5-Hydroxy-2- (4-n-hexylphenyl)-
A mixture of 10.2 g of pyrimidine, 8.6 g of 4-n-propylbenzyl bromide, 8.6 g of potassium carbonate and 50 ml of dimethylformamide is warmed at 90 ° for 10 hours. Finished in conventional manner, 2- (4-n-hexylphenyl)
-Pyrimidin-5-yl pn-propylbenzyl ether is obtained.

In a similar manner, the following compound is prepared: 2- (4-butylphenyl) -pyrimidin-5-yl p
-Propylbenzyl ether 2- (4-butylphenyl) -pyrimidin-5-yl p
-Pentylbenzyl ether 2- (4-butylphenyl) -pyrimidin-5-yl p
-Hexyl benzyl ether 2- (4-butylphenyl) -pyrimidin-5-yl p
-Heptyl benzyl ether 2- (4-butylphenyl) -pyrimidin-5-yl p
-Octyl benzyl ether

2- (4-Butylphenyl) -pyrimidin-5-yl p-nonylbenzyl ether 2- (4-butylphenyl) -pyrimidin-5-yl p
-Decylbenzyl ether 2- (4-pentylphenyl) -pyrimidin-5-yl p-propylbenzyl ether 2- (4-pentylphenyl) -pyrimidin-5-yl p-pentylbenzyl ether 2- (4-pentylphenyl) -Pyrimidin-5-yl p-hexylbenzyl ether 2- (4-pentylphenyl) -pyrimidin-5-yl p-heptylbenzyl ether 2- (4-pentylphenyl) -pyrimidin-5-yl p-octylbenzyl ether 2 -(4-Pentylphenyl) -pyrimidin-5-yl p-nonylbenzyl ether 2- (4-pentylphenyl) -pyrimidin-5-yl p-decylbenzyl ether 2- (4-hexylphenyl) -pyrimidine-5 Yl p-propylbenzyl ether 2- (4-hexyl Phenyl) -pyrimidin-5-yl p-pentylbenzyl ether 2- (4-hexylphenyl) -pyrimidin-5-yl p-hexylbenzyl ether 2- (4-hexylphenyl) -pyrimidin-5-yl p-heptylbenzyl Ether 2- (4-hexylphenyl) -pyrimidin-5-yl p-octylbenzyl ether

2- (4-hexylphenyl) -pyrimidin-5-yl p-nonylbenzyl ether 2- (4-hexylphenyl) -pyrimidin-5-yl p-decylbenzyl ether 2- (4-heptylphenyl)- Pyrimidin-5-yl p-propylbenzyl ether 2- (4-heptylphenyl) -pyrimidin-5-yl p-pentylbenzyl ether 2- (4-heptylphenyl) -pyrimidin-5-yl p-hexylbenzyl ether 2- (4-heptylphenyl) -pyrimidin-5-yl p-heptylbenzyl ether 2- (4-heptylphenyl) -pyrimidin-5-yl p-octylbenzyl ether 2- (4-heptylphenyl) -pyrimidin-5-yl p-nonylbenzyl ether 2- (4-heptylphenyl)- Limidin-5-yl p-decylbenzyl ether 2- (4-octylphenyl) -pyrimidin-5-yl p-propylbenzyl ether 2- (4-octylphenyl) -pyrimidin-5-yl p-pentylbenzyl ether 2- (4-octylphenyl) -pyrimidin-5-yl p-hexylbenzyl ether 2- (4-octylphenyl) -pyrimidin-5-yl p-heptylbenzyl ether 2- (4-octylphenyl) -pyrimidin-5-yl p-octyl benzyl ether

2- (4-octylphenyl) -pyrimidin-5-yl p-nonylbenzyl ether 2- (4-octylphenyl) -pyrimidin-5-yl p-decylbenzyl ether 2- (4-nonylphenyl)- Pyrimidin-5-yl p
-Propylbenzyl ether 2- (4-nonylphenyl) -pyrimidin-5-yl p
-Pentylbenzyl ether 2- (4-nonylphenyl) -pyrimidin-5-yl p
-Hexylbenzyl ether 2- (4-nonylphenyl) -pyrimidin-5-yl p
-Heptyl benzyl ether 2- (4-nonylphenyl) -pyrimidin-5-yl p
-Octylbenzyl ether 2- (4-nonylphenyl) -pyrimidin-5-yl p
-Nonylbenzyl ether 2- (4-nonylphenyl) -pyrimidin-5-yl p
-Decylbenzyl ether 2- (4-decylphenyl) -pyrimidin-5-yl p
-Propylbenzyl ether 2- (4-decylphenyl) -pyrimidin-5-yl p
-Pentylbenzyl ether 2- (4-decylphenyl) -pyrimidin-5-yl p
-Hexyl benzyl ether 2- (4-decylphenyl) -pyrimidin-5-yl p
-Heptyl benzyl ether 2- (4-decylphenyl) -pyrimidin-5-yl p
-Octylbenzyl ether 2- (4-decylphenyl) -pyrimidin-5-yl p
-Nonylbenzyl ether 2- (4-decylphenyl) -pyrimidin-5-yl p
-Decyl benzyl ether

Example 20 14.2 g of 4- (5-hexylpyrimidin-2-yl) -benzoic acid [This compound can be obtained from 4- (5-hexylpyrimidin-2-yl) -benzonitrile by saponification. Is refluxed with 120 g of thionyl chloride in 120 ml of toluene until the generation of hydrogen chloride stops. The volatile components are removed from the mixture under reduced pressure. The residue is taken up in 180 ml of dichloromethane, 10 ml of triethylamine and 4- (5-octylpyrimidine-2-
Yl) -phenol 14.2 g (this compound can be obtained from 4-hydroxybenzamidine hydrochloride and methyl α-octyl-β-hydroxyacrylate)
Add. After stirring for 20 hours at 20 °, the precipitated triethylammonium chloride is filtered off and the filtrate is concentrated. 4- (5-Octylpyrimidin-2-yl) -phenyl 4- (5-hexylpyrimidin-2-yl) -benzoate crystallizes out.

The following compound is prepared analogously to this method: 4- (5-propylpyrimidin-2-yl) -phenyl 4- (5-propylpyrimidin-2-yl) -benzoate 4- (5-pentyl Pyrimidin-2-yl) -phenyl 4- (5-propylpyrimidin-2-yl) -benzoate 4- (5-hexylpyrimidin-2-yl) -phenyl 4- (5-propylpyrimidin-2-yl) -benzoate 4- (5-heptylpyrimidin-2-yl) -phenyl 4- (5-propylpyrimidin-2-yl) -benzoate 4- (5-octylpyrimidin-2-yl) -phenyl 4- (5-propylpyrimidin- 2-yl) -benzoate 4- (5-nonylpyrimidin-2-yl) -phenyl 4
-(5-propylpyrimidin-2-yl) -benzoate

4- (5-decylpyrimidin-2-yl)
-Phenyl 4- (5-propylpyrimidin-2-yl)
-Benzoate 4- (5-propylpyrimidin-2-yl) -phenyl 4- (5-pentylpyrimidin-2-yl) -benzoate 4- (5-pentylpyrimidin-2-yl) -phenyl 4- (5-pentyl Pyrimidin-2-yl) -benzoate 4- (5-hexylpyrimidin-2-yl) -phenyl 4- (5-pentylpyrimidin-2-yl) -benzoate 4- (5-heptylpyrimidin-2-yl) -phenyl 4- (5-pentylpyrimidin-2-yl) -benzoate 4- (5-octylpyrimidin-2-yl) -phenyl 4- (5-pentylpyrimidin-2-yl) -benzoate 4- (5-nonylpyrimidin- 2-yl) -phenyl 4
-(5-Pentylpyrimidin-2-yl) -benzoate 4- (5-decylpyrimidin-2-yl) -phenyl 4
-(5-Pentylpyrimidin-2-yl) -benzoate 4- (5-propylpyrimidin-2-yl) -phenyl 4- (5-hexylpyrimidin-2-yl) -benzoate 4- (5-pentylpyrimidin-2 -Yl) -phenyl 4- (5-hexylpyrimidin-2-yl) -benzoate 4- (5-hexylpyrimidin-2-yl) -phenyl 4- (5-hexylpyrimidin-2-yl) -benzoate 4- ( 5-heptylpyrimidin-2-yl) -phenyl 4- (5-hexylpyrimidin-2-yl) -benzoate 4- (5-octylpyrimidin-2-yl) -phenyl 4- (5-hexylpyrimidin-2-yl) ) -Benzoate

4- (5-nonylpyrimidin-2-yl)
-Phenyl 4- (5-hexylpyrimidin-2-yl)
-Benzoate 4- (5-decylpyrimidin-2-yl) -phenyl 4
-(5-Hexylpyrimidin-2-yl) -benzoate 4- (5-propylpyrimidin-2-yl) -phenyl 4- (5-heptylpyrimidin-2-yl) -benzoate 4- (5-pentylpyrimidin-2 -Yl) -phenyl 4- (5-heptylpyrimidin-2-yl) -benzoate 4- (5-hexylpyrimidin-2-yl) -phenyl 4- (5-heptylpyrimidin-2-yl) -benzoate, melting point: 97 °, boiling point: 276 ° 4- (5-heptylpyrimidin-2-yl) -phenyl 4- (5-heptylpyrimidin-2-yl) -benzoate 4- (5-octylpyrimidin-2-yl) -phenyl 4 -(5-Heptylpyrimidin-2-yl) -benzoate 4- (5-nonylpyrimidin-2-yl) -phenyl 4
-(5-Heptylpyrimidin-2-yl) -benzoate 4- (5-decylpyrimidin-2-yl) -phenyl 4
-(5-Heptylpyrimidin-2-yl) -benzoate 4- (5-propylpyrimidin-2-yl) -phenyl 4- (5-octylpyrimidin-2-yl) -benzoate 4- (5-pentylpyrimidin-2 -Yl) -phenyl 4- (5-octylpyrimidin-2-yl) -benzoate 4- (5-hexylpyrimidin-2-yl) -phenyl 4- (5-octylpyrimidin-2-yl) -benzoate 4- ( 5-heptylpyrimidin-2-yl) -phenyl 4- (5-octylpyrimidin-2-yl) -benzoate 4- (5-octylpyrimidin-2-yl) -phenyl 4- (5-octylpyrimidin-2-yl) ) -Benzoate

4- (5-nonylpyrimidin-2-yl)
-Phenyl 4- (5-octylpyrimidin-2-yl)
-Benzoate 4- (5-decylpyrimidin-2-yl) -phenyl 4
-(5-Octylpyrimidin-2-yl) -benzoate 4- (5-propylpyrimidin-2-yl) -phenyl 4- (5-nonylpyrimidin-2-yl) -benzoate 4- (5-pentylpyrimidin-2 -Yl) -phenyl 4- (5-nonylpyrimidin-2-yl) -benzoate 4- (5-hexylpyrimidin-2-yl) -phenyl 4- (5-nonylpyrimidin-2-yl) -benzoate 4- ( 5-heptylpyrimidin-2-yl) -phenyl 4- (5-nonylpyrimidin-2-yl) -benzoate 4- (5-octylpyrimidin-2-yl) -phenyl 4- (5-nonylpyrimidin-2-yl) ) -Benzoate 4- (5-nonylpyrimidin-2-yl) -phenyl 4
-(5-nonylpyrimidin-2-yl) -benzoate 4- (5-decylpyrimidin-2-yl) -phenyl 4
-(5-nonylpyrimidin-2-yl) -benzoate 4- (5-propylpyrimidin-2-yl) -phenyl 4- (5-decylpyrimidin-2-yl) -benzoate 4- (5-pentylpyrimidin-2 -Yl) -phenyl 4- (5-decylpyrimidin-2-yl) -benzoate 4- (5-hexylpyrimidin-2-yl) -phenyl 4- (5-decylpyrimidin-2-yl) -benzoate 4- ( 5-heptylpyrimidin-2-yl) -phenyl 4- (5-decylpyrimidin-2-yl) -benzoate 4- (5-octylpyrimidin-2-yl) -phenyl 4- (5-decylpyrimidin-2-yl) ) -Benzoate 4- (5-nonylpyrimidin-2-yl) -phenyl 4
-(5-decylpyrimidin-2-yl) -benzoate 4- (5-decylpyrimidin-2-yl) -phenyl 4
-(5-decylpyrimidin-2-yl) -benzoate

Example 21 p- (5-heptylpyrimidin-2-yl) -phenyl p-pentylbenzyl ether 11%, p- (5-heptylpyrimidin-2-yl) -phenyl p-hexylbenzyl ether 15%, p -(5-nonylpyrimidin-2-yl) -phenyl p-pentylbenzyl ether 18%, p- (5-nonylpyrimidin-2-yl)
-Phenyl p-heptyl benzyl ether 14%, 2
-P-nonyloxyphenyl-5-nonylpyrimidine
23%, 4- (5-heptylpyrimidin-2-yl)-
Phenyl p-hexyloxybenzoate 5%, 4-
(5-octylpyrimidin-2-yl) -phenyl p-
A liquid crystal phase consisting of 4% octyloxy-m-fluorobenzoate and 10% R-4- (5-hexylpyrimidin-2-yl) -phenyl 2-chloropropionate has a C 4 ° S _c * 76 ° Ch 95. With ° I.

Example 22 3-p-Hexyloxyphenyl-5-heptylpyrimidine 3%, 2-p-heptyloxyphenyl-5-heptylpyrimidine 3%, 2-p-octyloxyphenyl-5-heptylpyrimidine 3%, 2-p-nonyloxyphenyl-5-heptylpyrimidine 3%, 2-
p-hexyloxyphenyl-5-nonylpyrimidine
6%, 2-p-nonyloxyphenyl-5-nonylpyrimidine 15%, 1- (p-hexylphenyl) -2-
(P- (5-heptylpyrimidin-2-yl) -phenyl) -ethane 16%, 1- (p-octyl-m-fluorophenyl) -2- (p- (5-octylpyrimidin-2-yl) -Phenyl) -ethane 19%, optically active 4- (5-nonylpyrimidin-2-yl) -phenyl 3-chloro-4- (2-octyloxy) -benzoate 15% and optically active 1-p. -(2-Octyloxycarbonyl) -phenyl-2- (p- (5-heptylpyrimidin-2-yl) -phenyl) -ethane
The liquid crystal phase consisting of 17% has a C 9 ° S _c * 74 ° Ch 89
Indicates ° I.

Example 23 4-p-heptyloxyphenyl-5-octylpyrimidine 4%, 2-p-octyloxyphenyl-5-octylpyrimidine 4%, 2-p-nonyloxyphenyl-5-octylpyrimidine 4%, p- (5-nonylpyrimidin-2-yl) -phenyl p-pentylbenzyl ether 16%, p- (5-nonylpyrimidine-2
-Yl) -phenyl p-heptyl benzyl ether 1
1%, 5- (p-octylphenyl) -pyrimidine-2
-Yl p-octyloxybenzoate 13%, 5-
(P-heptylphenyl) -pyrimidin-2-yl p-
Hexyloxybenzoate 16%, 5- (p-octylphenyl) -pyrimidin-2-yl p-heptyloxy-m-fluorobenzoate 11% and 2-p.
A liquid crystal phase consisting of 21% nonyloxyphenyl-5-pyrimidine exhibits C 5 ° S _c .

Example 24 p- (5-heptylpyrimidin-2-yl) -phenyl p-pentylbenzyl ether 11%, p- (5-heptylpyrimidin-2-yl) -phenyl p-hexylbenzyl ether 9%, p -(5-nonylpyrimidin-2-yl) -phenyl p-pentylbenzyl ether 12%, p- (5-nonylpyrimidin-2-yl)-
Phenyl p-heptyl benzyl ether 10%, 2-
p-nonyloxyphenyl-5-nonylpyrimidine 2
0%, 1- (trans-4-heptylcyclohexyl)
-2- (p- (5-octylpyrimidin-2-yl)-
Phenyl) -ethane 9%, 1- (trans-4-octylcyclohexyl) -2- (p- (5-nonylpyrimidin-2-yl) -phenylethane 8%, optically active 1- (p- (2 -Octyloxycarbonyl) -phenyl) -2- (p- (5-heptylpyrimidin-2-yl) -phenyl) -ethane 10% and 1- (p-heptyloxy-m-fluorphenyl) -2- ( p-
(5-heptylpyrimidin-2-yl) -phenyl)-
The liquid crystal phase consisting of 11% ethane is C 3 ° S _c * 72 °
It shows Ch 93 ° I.

Example 25 2-p-heptyloxyphenyl-5-heptylpyrimidine 3%, 2-p-octyloxyphenyl-5-heptylpyrimidine 3%, p- (5-heptylpyrimidin-2-yl) -phenyl p -Pentylbenzyl ether 7%, p- (5-heptylpyrimidin-2-yl)
-Phenyl p-hexyl benzyl ether 5%, 2-
p-nonyloxyphenyl-5-nonylpyrimidine 2
0%, R-4- (5-hexylpyrimidin-2-yl)
-Phenyl 2-chloropropionate 10%, 1-
(P-hexylphenyl) -2- (p-5-heptylpyrimidin-2-yl) -phenyl) -ethane 8%, 1
-(P-octylphenyl) -2- (p-5-heptylpyrimidin-2-yl) -phenyl) -ethane 13
%, 1- (p-heptylphenyl) -2- (p- (5-
Nonylpyrimidin-2-yl) -phenyl) -ethane
11% and 1- (p-octylphenyl) -2- (p
-(5-nonylpyrimidin-2-yl) -phenyl)-
Liquid crystal phase consisting of 9% ethane is C 8 ° S _c * 74 ° C
h 88 ° I.

Example 26 2-p-Hexyloxyphenyl-5-heptylpyrimidine 3%, 2-p-heptyloxyphenyl-5-heptylpyrimidine 3%, 2-p-octyloxyphenyl-5-heptylpyrimidine 3%, 2-p-nonyloxyphenyl-5-heptylpyrimidine 3%, 2-
p-hexyloxyphenyl-5-nonylpyrimidine
6%, 2-p-nonyloxyphenyl-5-nonylpyrimidine 24%, 5- (p-nonylphenyl) -pyrimidin-2-yl p-hexylbenzoate 20%, 5
-(P-nonylphenyl) -pyrimidin-2-yl p-
Heptylbenzoate 10%, p- (5-heptylpyrimidin-2-yl) -phenyl p-hexylbenzyl ether 10%, p- (5-nonylpyrimidine-2-
) -Phenyl p-heptyl benzyl ether 8%
And optically active ethyl 2- [p- (5-nonylpyrimidin-2-yl) -phenoxy] propanoate 1
A liquid crystal phase composed of 0% has a C-8 ° _Sc * 71 ° Ch 8
Spontaneous polarization value P _{s of} 8 ° C and 8 nC / cm ² at 20 °
Have.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Höpfow, Reinhardt D-1000 Berlin 27, Germany 27, Schauflerpf 22 Adder (72) Inventor Pauille, Axel D-6104 Seeheim, Rosenweg 7 Germany (72) Inventor Eidenthink, Rudolf D-6115 Miyunster, Korn Blumenschuttraße 1 (72) Inventor Krause, Joachim Germany D-6110 Deiburg, Samuel-Moses-Schyutraße 14 (72) Inventor Weetz Hitler, Andreas Germany D-6103 Griesheim, Goetheshutraße 34

Claims (5)

[Claims] 1. The formula I R ¹ -A ¹ -Z ¹ -A ^2- [Z ² -A ³ ] _m -R ² I [wherein R ¹ and R ² are each alkyl having 1 to 12 C atoms]. a group, at least one is optically active, the two or more CH ₂ groups that are not one CH ₂ group or adjacent present in the group -O -, - CO
-, - O-CO -, - O-COO -, - CO-O- and (or) may be replaced by -CH = CH-, or one of the radicals R ¹ and R ² are also H, F ,
Cl, Br or CN, A ¹ is -Pyr-Phe
-, -Phe-Pyr-, -Pyr-Cy- or -C
y-Pyr-, where Pyr is pyrimidine-2,5-diyl, pyridine-2,5-diyl, pyrazine-2,5-diyl or pyridazine-3,6-diyl, Phe
Is 1,4-phenylene, which is unsubstituted or has 1 or 2 F and / or Cl atoms and / or CH ₃ and / or CN groups as substituents. , Cy is trans-1,4-cyclohexylene, and A ² and A ³ are each trans-.
1,4-cyclohexylene or 1,4-phenylene, which is unsubstituted or has 1 or 2 F and / or Cl atoms and / or CH as substituents _One and more than one C having ₃ and / or CN groups and present therein
The H group may be replaced by N, and Z ¹ is -C.
_{H 2 CH 2 -, - CO} -O -, - O-CO -, - CH 2 -
O- or -OCH ₂ - is and, Z ² is -CO-O -, -
_{O-CO -, - CH 2} CH 2 -, - CH 2 O -, - O-C
H ₂ — or a single bond, and m is 0 or 1, with the exception of compounds of the formula: embedded image R ¹ and R ² in each formula are C _{5 to} C ₁₂ alkyl], containing at least one compound as a component of a chiral tilted smectic liquid crystal phase, A liquid crystal composition useful for a switching display. 2. In formula I, Pyr is pyrimidine-
The liquid crystal composition according to claim 1, which is 2,5-yl. 3. In formula I, Pyr is The liquid crystal composition according to claim 2, which is 4. The formula I R ¹ -A ¹ -Z ¹ -A ^2- [Z ² -A ³ ] _m -R ² I [wherein R ¹ and R ² are each alkyl having 1 to 12 C atoms]. a group, at least one is optically active, the two or more CH ₂ groups that are not one CH ₂ group or adjacent present in the group -O -, - CO
-, - O-CO -, - O-COO -, - CO-O- and (or) may be replaced by -CH = CH-, or one of the radicals R ¹ and R ² are also H, F ,
Cl, Br or CN, A ¹ is -Pyr-Phe
-, -Phe-Pyr-, -Pyr-Cy- or -C
y-Pyr-, where Pyr is pyrimidine-2,5-diyl, pyridine-2,5-diyl, pyrazine-2,5-diyl or pyridazine-3,6-diyl, Phe
Is 1,4-phenylene, which is unsubstituted or has 1 or 2 F and / or Cl atoms and / or CH ₃ and / or CN groups as substituents. , Cy is trans-1,4-cyclohexylene, and A ² and A ³ are each trans-.
1,4-cyclohexylene or 1,4-phenylene, which is unsubstituted or has 1 or 2 F and / or Cl atoms and / or CH as substituents _One and more than one C having ₃ and / or CN groups and present therein
The H group may be replaced by N, and Z ¹ is -C.
_{H 2 CH 2 -, - CO} -O -, - O-CO -, - CH 2 -
O- or -OCH ₂ - is and, Z ² is -CO-O -, -
_{O-CO -, - CH 2} CH 2 -, - CH 2 O -, - O-C
H ₂ — or a single bond, and m is 0 or 1; with the exception of compounds of the formula: In each formula, R ¹ and R ² are C ₅ -C ₁₂ alkyl] and at least one compound of the formula VIc: R′-Q ³ -Q ⁴ -R ′ ″ ″ VIc [R ′ in the formula Is a linear alkyl or alkoxy group having 2 to 10 C atoms, respectively, and Q ³ and Q ⁴ are 1,4-phenylene, 4,4′-biphenylyl or trans-1,4-cyclohexylene, respectively. And one of the groups Q ³ and Q ⁴ also contains at least one C
It may also be 1,4-phenylene in which the H group is replaced by N, R '''is a formula having an asymmetric carbon atom, Which is an optically active group having a structure represented by [1] and is contained as a component of a chiral tilted smectic liquid crystal phase, and is useful as a rapid switching display also based on ferroelectric properties. Liquid crystal composition. 5. A compound of formula VIc is represented by formula VIc ': [In the formula, Is 1,4-phenylene or trans-1,4-cyclohexylene, and n is 0 or 1.], The liquid crystal composition according to claim 4.