Disubstituted ethanes and their use in liquid crystal materials and devices

A fluorinated compound having a formula: ##STR1## R.sub.1 is hydrogen or alkyl having up to 12 carbon atoms; R.sub.2 is selected from hydrogen, alkyl having up to 12 carbon atoms, alkoxy having up to 12 carbon atoms, ##STR2## wherein R.sub.3 is hydrogen or alkyl having up to 12 carbon atoms, and wherein R.sub.4 is hydrogen, alkyl having up to 12 carbon atoms or alkoxy having up to 12 carbon atoms; ##STR3## represents a cyclohexane ring which is in the trans configuration if 1, 4-disubstituted; ##STR4## represents a benzene ring; each of X, Y and Z independently represents hydrogen or fluorine in one or more of the lateral benzene ring positions, provided that at least one of X, Y and Z is present representing fluorine; PA1 n=0 or 1 provided that when n=0 ##STR5## and R.sub.1 is alkyl; with the proviso that in Formula I when n is 1 and ##STR6## where R.sub.1 is n-alkyl and R.sub.2 is n-alkyl or n-alkoxy the total number of carbon plus oxygen atoms in the two groups R.sub.1 and R.sub.2 is less than 10.

The present invention relates to disubstituted ethanes and their use in 
liquid crystal materials and devices. 
The use of liquid crystal materials to exhibit electro-optical effects in 
display devices such as digital calculators, watches, meters and simple 
word displays is now well known. However known liquid crystal materials 
are not ideal in all respects and a considerable amount of work is 
currently being carried out in the art to improve their properties. 
Liquid crystal materials normally consist of generally selected mixture 
compositions and improved materials are obtained by forming new mixtures 
having an improved combination of properties. 
The composition of a liquid crystal mixture for electro-optical 
applications depends on the kind of display effect to be utilised and the 
particular properties required for that effect. Examples of various 
display effects are given below. For all kinds however, it is desirable 
for the mixture to show the best possible combination of certain general 
properties, eg as follows: 
(i) a liquid crystalline temperature range--including room temperature 
(20.degree. C.)--which is as wide as possible; 
(ii) a melting point (solid-to-liquid crystal transition temperature) which 
is as low as possible; 
(iii) a clearing point (liquid crystalline to isotropic liquid transition 
temperature) which is as high as possible; 
(iv) a positive or negative (as appropriate) dielectric anisotropy 
(permittivity measured parallel to the molecular axis less that measured 
perpendicular to the molecular axis) which is as great as possible in 
order to minimise the display voltage; 
(v) a viscosity which is as low as possible in order to minimise the 
display switching speeds; 
(vi) an electro-optical response which varies as little as possible with 
temperatures; 
(vii) a good chemical and photochemical stability. 
Examples of further particular properties useful in specific applications 
are as follows: 
(viii) a good multiplexibility; 
(ix) an ability to switch dielectric anisotropy with frequency; and 
(x) a birefringence of selected magnitude. 
The required combination of properties of a liquid crystal mixture 
composition is obtained by blending together components of different 
properties in the mixture. 
One combination of properties which is particularly difficult to achieve is 
that required for displays to be used on dashboards in automobiles, where 
a low viscosity essential for fast switching at temperatures as low as 
-20.degree. to -30.degree. C. must be combined with a high clearing point 
(&gt;90.degree. C.) and a high birefringence to prevent "bleed through" of 
light from the rear illumination through parts of the display that are 
off. 
In order to keep production costs to a minimum it is desirable to use the 
smallest number of components in the mixture consistent with the 
achievement of a satisfactory combination of the required properties. 
Therefore it is desirable that the individual components used show a 
number of the required properties. It is desirable that the mutual 
solubility of the individual component is good, also in order to minimise 
the number of components. 
The purpose of the present invention is to provide a class of novel liquid 
crystal compounds which provide suitable components for liquid crystal 
mixture compositions for electro-optical displays, particularly displays 
to be used on dashboards in automobiles. 
According to the present invention in a first aspect there is provided a 
fluorinated compound having a formula: 
##STR7## 
R.sub.1 is hydrogen or alkyl having up to 12 carbon atoms; R.sub.2 is 
selected from hydrogen, alkyl having up to 12 carbon atoms, alkoxy having 
up to 12 carbon atoms, 
##STR8## 
wherein R.sub.3 is hydrogen or alkyl having up to 12 carbon atoms, and 
wherein R.sub.4 is hydrogen, alkyl having up to 12 carbon atoms or alkoxy 
having up to 12 carbon atoms; 
##STR9## 
represents a cyclohexane ring which is in the trans configuration if 
1,4-disubstituted; 
##STR10## 
represents a benzene ring; each of X, Y, and Z independently represents 
hydrogen or fluorine in one or more of the lateral benzene ring positions, 
provided that at least one of X, Y and Z is present representing fluorine; 
n=0 or 1 provided that when n=0 
##STR11## 
and R.sub.1 is alkyl; with the proviso that in Formula I when n is 1 and 
##STR12## 
wherein R.sub.1 is n-alkyl and R.sub.2 is n-alkyl or n-alkoxy the total 
number of carbon atoms or carbon plus oxygen atoms in the two groups 
R.sub.1 and R.sub.2 is less than 10. 
For use in nematic liquid crystal mixtures each alkyl or alkoxy group 
included in the compound of Formula I is preferably straight chained. 
However for use in chiral nematic (optically active) mixtures one or more 
alkyl or alkoxy groups contained in the molecule may be a chiral group, eg 
of the form (+)--CH.sub.3 (CH.sub.2).sub.n CH(CH.sub.3)CH.sub.2, where n 
is from 1 to 8 and (+)-- represents a chiral group having a positive 
optical rotation angle, eg (+)-2-methylbutyl. 
Examples of some sub-classes of compound embraced by Formula I, including 
preferred sub-classes, are as follows: 
##STR13## 
where each R.sub.A is independently alkyl, for instance n-alkyl having 1 
to 12, eg 1 to 8 carbon atoms and each R.sub.B is independently hydrogen, 
alkyl or alkoxy, for instance n-alkyl or n-alkoxy having 1 to 12, eg 1 to 
8 carbon atoms. 
For compounds of Formula Ia and Ib above the proviso specified above 
applies, namely that if R.sub.A is n-alkyl and R.sub.B is n-alkyl or 
n-alkoxy the total number of carbon plus oxygen atoms (if any) in the two 
groups is less than 10. Preferably the total number of carbon plus oxygen 
atoms in the two groups R.sub.A and R.sub.B is between 4 and 8 inclusive. 
Compounds having the same generalised formulae as Formulae Ia and Ib but 
wherein the terminal n-alkyl groups or n-alkyl and n-alkoxy groups have a 
total of ten carbon atoms and ten carbon plus oxygen atoms respectively 
are proposed in European Patent Application No. 84194 published after the 
filing of UK Patent Application No. 8302119 from which priority is claimed 
herein. However no properties are disclosed or suggested for these 
proposed compounds in the said European Application. However, it is shown 
below that these compounds are considerably inferior to the corresponding 
compounds of Formulae Ia and Ib (to which the above proviso applies and 
which are not proposed in the said European Application) in terms of their 
injected smectic behaviour in mixtures with positive nematic compounds as 
explained below. The compounds proposed in said European Application are 
therefore excluded from the scope of the present invention. 
Compounds of Formulae Ia to Ij specified above in general are examples of 
compounds of Formula I which are useful as liquid crystal compounds whilst 
compounds of Formula Ik as follows: 
##STR14## 
are examples of compounds useful as intermediates in the synthesis of 
certain liquid crystal compounds of Formula I, particularly compounds of 
Formula Id and Ie, wherein X, Y and Z are H or F at least one being F. 
Compounds of Formula I can provide very attractive components of liquid 
crystal materials for electro-optical display applications. For example, 
compounds of the sub-classes of Formulae Ia and Ib above, wherein R.sub.A 
and R.sub.B are n-alkyl groups, show the properties described in the 
Examples and Tables below, where in certain preferred examples the 
following highly advantageous points can be noticed: 
(i) low melting points, generally less than 30.degree. C., which are 
advantageous in the formulation of liquid crystalline mixtures with low 
melting point; 
(ii) high clearing points in the vicinity of 100.degree. C., and an 
extraordinarily wide nematic range often of about 70 Celsius degrees, 
which are advantageous in the formulation of liquid crystalline mixtures 
with wide nematic range; 
(iii) the virtual absence of highly undesirable smectic phases; 
(iv) little tendency to form smectic phases in combination with nematic 
materials of positive dielectric anisotropy; 
(v) a high solubility in nematic materials of positive dielectric 
anisotropy; 
(vi) the property of elevating the clearing point when added to mixtures 
with positive nematic materials already containing a high clearing point 
component; 
(vii) a relatively low viscosity and the property of reducing the viscosity 
of known nematic mixtures; 
(viii) the ability to form the basis of mixtures with fast switching times 
at low temperatutes; 
(ix) a higher birefringence in comparison with other known materials with 
equivalent thermal and viscous properties: 
(x) a very low temperature dependence of threshold voltage; 
(xi) good chemical and photochemical stability. 
Such an attractive combination of properties offers the possibility of 
forming liquid crystal mixtures having properties superior to any known 
mixtures. 
Liquid crystal compounds containing the grouping 
##STR15## 
where R.sub.A and X are as defined above, are known, see for example, 
Published UK Patent Specification Nos 2023136A and 2093057A. However, in 
general, the novel compounds of Formula I, in particular those of Formula 
Ia and Ib unexpectedly show a better overall combination of desirable 
properties than such known compounds. 
For example, the compounds of Formula I can have a higher clearing point, 
without a significant corresponding increase in melting point and 
viscosity, compared with the known compounds of Formula A as follows: 
##STR16## 
where R'.sub.B is alkyl, alkoxy or cyano. 
Likewise, the compounds of Formula I have a lower melting point and 
viscosity and a better solubility in positive nematic materials than the 
known high clearing point additives of formula B and C as follows: R1 ? 
##STR17## 
Furthermore the compounds of Formula I are generally more versatile than 
the compounds of Formula B and may be added to or used as materials of 
negative dielectric anisotropy (as well as those of positive dielectric 
anisotropy) for use in certain specific applications described below. The 
compounds of Formula B are not generally suitable for this purpose because 
they have a high positive dielectric anisotropy. 
By far the most remarkable property of the compounds of Formula I is the 
effect of the lateral fluorine atom in suppressing and eliminating 
undesirable smectic phases. This may be seen most readily by comparing the 
phase transitions of compounds without, and with the lateral fluorine 
atoms, in Tables 1 and 2 as follows: 
TABLE 1 
______________________________________ 
Comparative properties of compounds having the formula: 
##STR18## 
R.sub.1 
R.sub.2 X Y KN KS SS SN NI 
______________________________________ 
C.sub.2 H.sub.5 
C.sub.3 H.sub.7 
H H 55 98.5 121.5 
C.sub.2 H.sub.5 
C.sub.3 H.sub.7 
H F 21.3 78.3- 
78.5 
C.sub.3 H.sub.7 
C.sub.3 H.sub.7 
H H 67 118 119 114 
C.sub.3 H.sub.7 
C.sub.3 H.sub.7 
H F 40 107.7 
C.sub.3 H.sub.7 
C.sub.3 H.sub.7 
F H 59 108 
C.sub.3 H.sub.7 
C.sub.5 H.sub.11 
H H 132.5 141.5 
C.sub.3 H.sub.7 
C.sub.5 H.sub.11 
H F 28.1- 105 
29.7 
______________________________________ 
TABLE 2 
______________________________________ 
Comparative properties of compounds having the formula: 
##STR19## 
R.sub.1 
R.sub.2 X Y KN KS SN NI 
______________________________________ 
C.sub.3 H.sub.7 
C.sub.3 H.sub.7 
H H 172 201 258 
C.sub.3 H.sub.7 
C.sub.3 H.sub.7 
H F 106.8 244 
______________________________________ 
K, S, N and I in Tables 1 and 2 respectively represent solid, smectic, 
nematic and isotropic phases and K-N etc represent transition temperatures 
in degrees Celsius. The alkyl chains described in Tables 1 and 2 are all 
straight. S-S represents a transition from one type of smectic phase to 
another. 
Thus in the compounds without lateral fluorine atoms smectic phases are 
general and frequently persist above 100.degree. C., whereas such phases 
in the new class of compound of Formula I are very rare down to room 
temperature (20.degree. C.). Moreover by making eutectic mixtures of the 
new compounds the nematic range may be extended down to low temperatures. 
Thus a mixture of: 
______________________________________ 
##STR20## 
______________________________________ 
R.sub.1 = -n-C.sub.3 H.sub.7 
R.sub.2 = -n-C.sub.3 H.sub.7 
26% by weight 
R.sub.1 = -n-C.sub.3 H.sub.7 
R.sub.2 = -n-C.sub.5 H.sub.11 
35% by weight 
R.sub.1 = -n-C.sub.5 H.sub.11 
R.sub.2 = C.sub.2 H.sub.5 
39% by weight 
______________________________________ 
referred to in this Specification as Mixture E, has been found to show a 
nematic phase from the melting point of -13.5.degree. to the clearing 
point of 103.5.degree. C., without any formation of a smectic phase, and 
provides an advantageous basis for liquid crystal mixtures that have a low 
freezing point and will switch fast at low temperatures. 
Thus, according to one preferred feature of the invention a nematic or 
chiral nematic liquid crystal material comprises a mixture of two or more 
compounds of Formula I. Such a mixture may have an extremely wide nematic 
or chiral nematic temperature range. The mixture may contain homologues of 
the same sub-class, eg two or more compounds of Formula Ia. 
Alternatively, pairs of compounds may be formed having the same general 
structure but in different structural isomeric forms with regard to the 
position of the fluorine, eg in the groups X and Y. In other words one 
compound may have X=F and Y=H and the other has Y=F and X=H in an 
otherwise identical structure (eg of Formulae Ia and Ib). Such isomers 
have similar properties but a mixture of the two can give a very useful 
depression of melting point. 
The property of the lateral fluorine atom in unexpectedly suppressing 
smectic phases also extends to suppressing the formation of the type of 
smectic phase, known as an "injected smectic phase", the significance of 
which is described briefly as follows. 
The majority of commercially available electro-optical liquid crystal 
displays are twisted nematic displays which operate by the twisted nematic 
effect described below. 
If the light intensity output from a twisted nematic display is plotted 
against the voltage applied the curve obtained is desirably as steep as 
possible in the region of the so-called optical threshold (which 
corresponds to the liquid crystal molecules undergoing their most rapid 
change from the homogeneous configuration to the homeotropic 
configuration). The steepness of the light output versus voltage curve 
depends on the liquid crystal material used in the display. 
A large proportion of the twisted nematic displays currently available 
commercially are multiplexed displays, that is to say that individually 
addressed elements of the display are defined by the region between the 
inter-section of an electrode of one set on one side of the display panel 
and an electrode of another set on the other side of the panel, each 
electrode of each set being shared by all of the elements in a given row 
or column. Multiplexing allows a greater amount of information to be 
displayed on a restricted display area and allows the use of a smaller 
number of electrode connections per number of display elements to be 
addressed. 
In order to produce a liquid crystal material having an adequate 
multiplexibility for use in a multiplexed twisted nematic display it is 
generally recognised in the art that the most appropriate way of forming 
such a material is to mix together two nematic components one of which is 
formed of one or more compounds having a terminal cyano-group, referred to 
herein as a .-+.cyano-material", and one of which is formed of one or more 
compounds having no terminal cyano-group, referred to herein as "non-cyano 
material". The non-cyano material has a small dielectric anisotropy. The 
non-cyano material desirably forms at least 30% by weight of the overall 
mixture of the two components. 
The twisted nematic effect operates only when the liquid crystal material 
is in the nematic phase and not, for example, if the material is in a 
smectic phase. When a cyano material is mixed with non-cyano material, 
although the two pure materials may show only nematic liquid crystal phase 
by themselves, mixtures of them may show unwanted smectic phases known in 
the art as "injected smectic" phases which appear as areas on the 
temperature versus composition graph or phase diagram. Injected smectic 
phases tend to reach peaks on the phase diagram at compositions 
corresponding to more than 30% by weight of the non-cyano material which 
are often close to the compositions otherwise preferred for 
electro-optical operation. It is generally recognised in the art that for 
a given mixture of a cyano material and a non-cyano material, the smaller 
the area on the phase diagram taken up by any injected smectic phases and 
the lower the temperatures at which they occur, the more attractive the 
given mixture will appear for use in a multiplexed twisted nematic device. 
In any event materials for use in commercial twisted nematic effect 
displays should show a nematic phase down to about -10.degree. C. or 
beyond. In other words any mixture of a cyano material and a non-cyano 
material proposed for use in a twisted nematic display should not show 
injected smectic phases above this temperature. 
It is generally recognised by those skilled in the art that the steepness 
of the light output versus voltage curve specified above can generally be 
increased by using as liquid crystal materials in a twisted nematic 
display compositions having components with relatively long-chain terminal 
groups, such as n-alkyl and n-alkoxy groups, rather than homologues having 
shorter chain terminal groups. However, it is also generally recognised by 
those skilled in the art that compounds having relatively long-chain 
terminal groups generally show a greater tendency to form smectic phases 
than homologues having relatively short chain terminal groups. 
The cyano material in a twisted nematic display preferably comprises 
compounds of the cyanobiphenyl class, eg 4-n-alkyl-4'-cyanobiphenyls. 
These compounds are preferred (amongst other reasons) because of the 
relatively steep light output versus voltage curve they provide. However 
these compounds are also prone to forming injected smectic phases in 
mixtures with non-cyano materials. 
Thus in order for a given non-cyano material to be of greatest utility in 
current electro-optical displays it should, amongst other things, be 
capable of forming mixtures with widely used commercially available cyano 
materials, particularly those comprising cyanobiphenyl compounds, and its 
individual compounds should be capable of forming mixtures with the 
individual compounds of the cyano material with the minimum tendency to 
give injected smectic phases. 
Preferred examples of compounds of Formula I show little tendency to form 
injected smectic phases and as a consequence are highly suitable for use 
as "non-cyano" components in mixtures suitable for multiplexed twisted 
nematic displays also allowing the steepness of the threshold to be 
improved by the use of longer chained cyano-components. For example, a 
mixture of 90% by weight of the ternary eutectic mixture Mixture E, of 
Formula I compounds specified above with 10% by weight of 
4-cyano-4'-ethylbiphenyl or of 75% by weight of that ternary eutectic 
mixture with 25% by weight of 
trans-4-n-propyl-1-(4-cyanophenyl)-cyclohexane were found to show no 
injected smectic phases down to -40.degree. C. This property is clearly 
beneficial in the formation of mixtures required to switch quickly at low 
temperatures, such as those required by the automobile industry. 
In order to minimise the tendency to form smectic phases, particularly 
injected smectic phases, the overall number of carbon atoms in the two 
groups R.sub.1 and R.sub.2 in Formula I, particularly where these groups 
are n-alkyl groups and particularly in the two groups R.sub.A and R.sub.B 
in Formulae Ia and Ib, is preferably less than ten; desirably the overall 
number is between 4 and 8 inclusive. The number of carbon atoms in each of 
thse individual groups is preferably five or less. 
In mixtures of compounds of Formula I, eg mixtures containing compounds of 
Formula Ia and Ib wherein the terminal groups R.sub.A and R.sub.B are 
n-alkyl groups, the overall number of carbon atoms in the terminal groups 
of each compound is preferably in the inclusive range 4 to 8. Preferably, 
the individual compounds have different overall numbers of carbon atoms in 
their terminal groups which are all in this range, as in Mixture E 
specified above. 
The compounds of Formula I may be used in applications other than 
electro-optical applications which are known to be suitable for the use of 
nematic or chiral nematic liquid crystal compounds. For example, the 
compounds of Formula I may be incorporated as high clearing point 
components of temperature sensitive, eg thermochromic, materials, eg for 
use in the applications described in UK Published Patent Application Nos. 
2083244A and 2085585A. 
Compounds of Formula I may be prepared by synthetic routes involving 
procedures which are known per se, the overall route being new. For 
example, Routes 1 and 2 as follows may be used: 
##STR21## 
The starting materials for Routes 5, 6, 7 and 8 may be prepared as 
described in copending UK Patent Application No. 8319849. 
The compounds of Formula I have a relatively small dielectric anisotropy 
and may be added to liquid crystal materials of (greater) positive or 
negative dielectric anisotropy, known and referred to herein respectively 
as "positive" or "negative" materials in order to produce a mixture having 
amongst other things a suitable dielectric anisotropy. As is well known to 
those skilled in the art the dielectric anisotropy of the liquid crystal 
material is necessary to give electro-optical operation and its sign (for 
a given frequency) is chosen according to the kind of electro-optical 
device in which the material is to be used. 
Compounds of reasonably low melting point are preferred as high dielectric 
anisotropy components. For example, the compounds of the following known 
classes are suitable as positive materials: 
##STR22## 
where each R is independently n-alkyl or n-alkoxy and each R.sub.A is 
independently n-alkyl. 
Alternatively, or additionally, the compounds of Formula I may be added to 
other small dielectric anisotropy compounds, eg to reduce mixture melting 
point, viscosity or to improve multiplexibility. The following classes are 
examples of such other compounds: 
##STR23## 
where each R is independently n-alkyl or n-alkoxy 
each R.sub.A is independently n-alkyl 
each R' is independently n-alkyl, n-alkoxy or hydrogen 
X=H or F 
and Q=halogen, eg Cl or F 
Thus, one or more compounds of Formula I may be added to one or more 
compounds of Formula IIa to IIi optionally together with one or more 
compounds of Formula IIIa to IIIn. 
Additional high clearing point compounds may be included in such mixtures 
eg one or more compounds selected from the following classes: 
##STR24## 
where R, R.sub.A, X and Y are as specified above. 
Other specific known additives, eg chiral additives, such as 
##STR25## 
where R.sub.C =(+)-2-methylbutyl and R.sub.D =(+)-2-methylbutoxy, may be 
incorporated in the mixture where required. 
The liquid crystal material obtained by blending together compounds of 
Formula I with those of the other classes as specified may be any of the 
following: 
(i) a positive nematic material for use in twisted nematic effect devices 
including multiplexed devices; an example of such a device is given below; 
(ii) a negative material preferably also with a pleochroic dye, for use in 
Freedericksz effect devices (negative nematic type) in which the molecular 
arrangement may be changed from the homeotropic texture (OFF state) to the 
homogeneous texture (ON state) by an electric field; an example of such a 
device is given below; 
(iii) a positive nematic material, preferably also with a pleochroic dye, 
for use in Freedericksz effect devices (positive nematic type) in which 
the molecular arrangement may be changed from the homogeneous texture (OFF 
state) to the homeotropic texture (ON state) by an electric field; 
(iv) a negative material which is a cholesteric (chiral nematic) of 
suitable resistivity (about 10.sup.9 ohm-cm), for use in cholesteric 
memory mode devices in which the molecular arrangement may be changed from 
a homogeneous texture (OFF state) to a scattering focal conic texture (ON 
state) by an electric field; 
(v) a strongly negative material which is a cholesteric, preferably 
together also with a pleochroic dye, for use in cholesteric-to-nematic 
phase change effect devices (positive contrast type) in which the 
molecular arrangement may be changed from a weakly scattering, ie clear, 
surface aligned homeotropic texture (OFF state) to a strongly scattering 
twisted homogeneous texture (ON state) by an electric field; 
(vi) a positive material which is a cholesteric, preferably together also 
with a pleochroic dye, in cholesteric-to-nematic phase change effect 
devices (negative contrast type) in which the molecular arrangement may be 
changed from a scattering focal conic texture (OFF state) to a clear 
homeotropic texture (ON state) by an electric field; 
(vii) a negative nematic material of suitable resistivity (about 10.sup.9 
ohm-cm), in dynamic scattering effect devices in which the molecular 
arrangement may be changed from a clear homeotropic texture (OFF state) to 
a turbulent scattering texture (ON state) by an electric field; 
(viii) a nematic material in two frequency switching effect devices (which 
may be twisted nematic effect devices) in which the dielectric anistropy 
of the material may be changed from (at low frequency) positive (OFF 
state) to negative (ON state) by the application of a high frequency 
electric field; 
(ix) a material suitable for the device described in copending UK Patent 
Application No 8317355. 
The construction and operation of the above devices and the general kinds 
of material which are suitable for use in them are themselves known. 
Where a liquid crystal material is for use in a twisted nematic effect, 
cholesteric to nematic phase change effect (negative constrast type) or 
Freedericksz effect (positive nematic type) device the material preferably 
contains: 
Component A: one or more compounds of Formula I plus 
Component B: one or more compounds of Formula IIa to IIi optionally 
together with one or more of the following: 
Component C: one or more compounds of Formula IIIa to IIIn; 
Component D: one or more compounds of Formula IVa to IVl; 
Component E: one or more chiral additives. 
For the twisted nematic effect and Freedericksz (positive nematic) effect 
the following percentages of the various components may be used in the 
material (the overall sum of the percentages adding to 100%). 
Component A: 5 to 95% by weight (typically 5 to 75% by weight) 
Component B: 5 to 95% by weight (typically 10 to 50% by weight) 
Component C: 0 to 90% by weight (typically 5 to 25% by weight) 
Component D: 0 to 30% by weight (typically 0 to 20% by weight) 
Component E: 0 to 5% by weight (typically 0 to 1% by weight) 
For the phase change (negative contrast type) the following proportions may 
be used: 
Components A to D: in the percentages as specified above; 
Component E: 2 to 20% (typically 4 to 5%) by weight. 
For the Freedericksz (positive nematic) and phase change (negative contrast 
type) effects a pleochroic dye forming from 1.5 to 15% of the overall 
mixture is preferably added to the liquid crystal material. Suitable dyes 
are described in published UK Patent Application Nos. 2081736A, 208219A 
and 2093475A. Typically, each dye compound incorporated forms 1 to 3% by 
weight of the overall mixture. 
Liquid crystal mixtures including compounds of Formula I may be formed in a 
known way, eg simply by heating the constituent compounds together in the 
correct weight proportion to form an overall isotropic liquid (eg about 
100.degree. C.). 
To provide a more general example of a mixture embodying the invention at 
least one compound according to Formula I above may be mixed together with 
one or more compounds in any one or more of the following known families 
for use in one or more of the applications given above (the actual 
application(s) depending on the mixture's properties): 
##STR26## 
where 
##STR27## 
is a trans-1,4-disubstituted cyclohexane ring, 
##STR28## 
is a 1,4-disubstituted bicyclo(2,2,2)octane ring, X is a 1,4 phenylene 
group 
##STR29## 
a 4,4' biphenylyl group 
##STR30## 
a 2,6 naphthyl group 
##STR31## 
or trans-1,4-disubstituted cyclohexane ring, and Y.sub.1 is CN, or R' or 
halogen or CO.O--X--Y.sup.1 where Y.sup.1 is CN, or R' or OR'; where R and 
R' are alkyl groups; or a derivative of one of these wherein H is replaced 
by a halogen, eg F, in one of the benzene rings. 
Preferably, the compound(s) of Formula I comprises between 5 and 95% by 
weight of the mixture. 
According to the present invention in a second aspect a liquid crystal 
device includes two dielectric substrates at least one of which is 
optically transparent, a layer of liquid crystal material sandwiched 
between the substrates and electrodes on the inner surfaces of the 
substrates to enable an electric field to be applied across the layer of 
liquid crystal material to provide an electro-optic effect therein, 
characterised in that the liquid crystal material consists of or includes 
a compound according to Formula I above. 
The device according to the second aspect may be a twisted nematic effect 
device, which may or may not be operated in a multiplexed fashion, a 
cholesteric-to-nematic phase change effect device, a Freedericksz effect 
device or a two-frequency switching effect device, all constructed in a 
known manner or any of the other devices mentioned above. The various ways 
in which compounds according to Formula I may be used in these devices are 
outlined above and will be further apparent to those skilled in the art. 
Examples of the preparation and properties of compounds having Formula I 
will now be given. In these Examples the following symbols are used: 
mp=melting point 
K-N=crystal to nematic liquid crystal transition temperature 
N-I=nematic to isotropic liquid transition temperature 
bp=boiling point 
S=smectic 
S.sub.A =smectic A 
S-N=smectic to nematic transition temperature 
K-S=crystalline solid to smectic transition temperature 
Ch-I=cholesteric (chiral nematic) to isotropic liquid transition 
temperature; 
K-Ch=crystalline solid to cholesteric transition temperature 
S-Ch=smectic to cholesteric transition temperature 
.DELTA.n=birefringence measured at 589.6 nm at 20.degree. C. 
.eta.=extrapolated nematic viscosity at 20.degree. C. measured in solution 
with the material ZLI 1132 (available from E Merck Co.) 
glc=gas liquid chromatography 
EXAMPLE 1 
The preparation of 
1-(trans-4-n-pentylcyclohexyl)-2-(4-ethyl-2-fluoro-4-biphenylyl)-ethane by 
Route 1 given above. 
Step 1a1 
The preparation of 
4-(trans-4-n-pentylcyclohexylacetyl)-2'-fluoro-4'-ethyl-biphenyl by 
Friedel Crafts acylation: 
4-Ethyl-2-fluorobiphenyl (13.0 gram) was added in one portion to a stirred 
suspension of aluminium trichloride (9.54 gram) in dichloromethane (30 
ml), followed by a solution of trans-4-n-pentylcyclohexyl acetyl chloride 
(15 gram) in dichloromethane (30 ml), added dropwise over 30 minutes. 
After stirring at room temperature for 31/2 hours, the reaction mixture 
was poured onto ice (250 gram) and hydrochloric acid (25 ml) and the 
product was extracted with 350 ml and 250 ml portions of petroleum ether 
(boiling point 60.degree.-80.degree. C.). The combined extracts were 
washed with water (150 ml), dried over anhydrous sodium sulphate and 
evaporated to dryness. The residue (26.8 gram) was crystallised from 
industrial methylated spirits at 0.degree. C. to give 13.2 gram (51.5% 
yield) 4-(trans-4-n-pentylcyclohexylacetyl)-2'-fluoro-4'-ethylbiphenyl, 
melting point 72.degree.-73.degree. C. 
The following homologues of the product of Step 1a1 listed in Table 3 were 
prepared in an identical manner from homologous starting materials: 
TABLE 3 
______________________________________ 
Compounds of the formula: 
##STR32## 
mp or 
R.sub.1 R.sub.2 Yield KN NI (.degree.C.) 
______________________________________ 
C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
89.8% 77 5-78.3 
C.sub.2 H.sub.5 
-n-C.sub.3 H.sub.7 
76.3% 54-56 
C.sub.2 H.sub.5 
-n-C.sub.4 H.sub.9 
87% 65.8-66.7 
-n-C.sub.3 H.sub.7 
C.sub.2 H.sub.5 
74% 76-78 
-n-C.sub.3 H.sub.7 
-n-C.sub.3 H.sub.7 
86% 84-86 91-93 
-n-C.sub.3 H.sub.7 
-n-C.sub.4 H.sub.9 
82% 70-72.5 85.1-86.7 
-n-C.sub.3 H.sub.7 
-n-C.sub.5 H.sub.11 
86% 66.5-68 92-94 
- n-C.sub.4 H.sub.9 
CH.sub.3 81% 74.5-76.5 
87.4-88.1 
-n-C.sub.4 H.sub.9 
C.sub.2 H.sub.5 
84% 70-73 77 
-n-C.sub.4 H.sub.9 
-n-C.sub.3 H.sub.7 
83% 72 91.5 
-n-C.sub.4 H.sub.9 
-n-C.sub.4 H.sub.9 
78% 69.6-71 87.1-87.8 
-n-C.sub.5 H.sub.11 
H 66% 111-114 
______________________________________ 
Step 1b1 
The preparation of 
1-(trans-4-n-pentylcyclohexyl)-2-(4'-ethyl-2'-fluoro-4-biphenylyl)-ethane 
by Huang Minlon reduction: 
The ketone prepared in Step 1a1 (13.0 gram), 99% hydrazine hydrate (13 ml), 
potassium hydroxide (7 gram) and digol (100 ml) were heated with stirring 
under a reflux condenser at 120.degree.-125.degree. for 4 hours, after 
which the temperature was raised to 175.degree. by distillation of the 
excess hydrazine hydrate. The mixture was heated under reflux for 16 
hours, cooled and poured onto 500 gram ice water. The organic product was 
extracted with petroleum ether (bp 60.degree.-80.degree.: 2.times.250 ml), 
and the extract washed with water and dried over anhydrous sodium 
sulphate, and evaporated to give a yellow oil (13.8 gram). This was 
dissolved in petroleum spirit (bp 60.degree.-80.degree. C.) (60 ml) and 
adsorbed onto a column of basic alumina (40 gram) over silica gel (28 
gram). Elution with petroleum spirit (550 ml) gave the product as a 
nematic oil (10.9 gram) which was crystallised from industrial methylated 
spirits ( 30 ml) at -25.degree. C. 
1-(Trans-4-n-pentylcyclohexyl)-2-(4'-ethyl-2'-fluoro-4-biphenylyl)-ethane 
formed a colourless crystalline solid (8.3 grams--yield 67%) with K-N 
(melting point), N-I (clearing point) 103.50.degree. C.: its viscosity and 
birefringence at 589.6 nm both measured at 20.degree. C. on the 
supercooled liquid were 32.6 cSt and 0.145 respectively. 
The following homologues of the product of Step 1b1 listed in Table 4 were 
prepared by Huang Minlon reduction of the appropriate ketone in the manner 
described in Step 1b1. 
TABLE 4 
__________________________________________________________________________ 
Compounds of the formula: 
##STR33## 
SN or 
monotropic .eta. 
R.sub.1 
R.sub.2 
Yield 
KN S phase 
NI (.degree.C.) 
.DELTA.n 
(cst) 
__________________________________________________________________________ 
C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
84% 14-14.8.degree. 
65.7-66.2 
0.1395 
22.5 
C.sub.2 H.sub.5 
-n-C.sub.3 H.sub.7 
45% 21.3.degree. 
78.3-78.5 
0.1461 
24 
C.sub.2 H.sub.5 
-n-C.sub.4 H.sub.9 
80% -2.degree. 69-70.2 
0.1353 
26 
-n-C.sub.3 H.sub.7 
C.sub.2 H.sub.5 
83% 27-27.5.degree. 
96.8-97.1 19 
-n-C.sub.3 H.sub.7 
-n-C.sub.3 H.sub.7 
78% 39.8-40.5.degree. 
107.6-107.8 
23 
-n-C.sub.3 H.sub.7 
-n-C.sub.4 H.sub.9 
60% 13.1-13.6.degree. 
[2.degree.] 
96.4-96.8 
0.1432 
22.5 
-n-C.sub.3 H.sub.7 
-n-C.sub.5 H.sub.11 
51% 28.1-29.7.degree. 
105.1 24.5 
-n-C.sub.4 H.sub.9 
CH.sub.3 
63% 27-27,7.degree. 
104.5-105 28 
-n-C.sub.4 H.sub.9 
C.sub.2 H.sub.5 
60% 25.4% [3.5.degree.] 
93-93.7 
0.1395 
22 
-n-C.sub.4 H.sub.9 
-n-C.sub.3 H.sub.7 
70% 23.9-24.6.degree. 
103.1 0.1452 
25 
-n-C.sub.4 H.sub.9 
-n-C.sub.4 H.sub.9 
66.5% 24.2-24.5 
94.2-94.5 26.5 
-n-C.sub.5 H.sub.11 
H 85% 42.5-44.1.degree. 
49.6 30 
__________________________________________________________________________ 
4-Ethyl-2-fluoro biphenyl, which is one of the starting materials used in 
Step 1a1, was prepared as follows: 
4-Acetyl-2-fluorobiphenyl (150 gram), 99% hydrazine hydrate (150 ml), 
potassium hydroxide (105 gram), digol (900 ml) and xylene (150 ml) were 
heated at 125.degree. C. for 16 hours with stirring, after which the 
xylene and excess hydrazine hydrate were distilled until the internal 
temperature reached 165.degree. C. The mixture was heated under reflux for 
three hours, cooled to 40.degree. and poured into 5 liters of water. The 
product was extracted with petroleum ether (bp 60.degree.-80.degree., 
2.times.2 liter), the extract washed with water, dried over anhydrous 
sodium sulphate and evaporated. 4-Ethyl-2-fluorobiphenyl (95 gram, 68% 
theory) formed a colourless oil bp 130.degree./0.8 mm. Other 
4-Alkyl-2-fluorobiphenyls were prepared by reaction of 
2-fluoro-4-biphenylyl magnesium bromides with n-alkyl bromides and were 
colourless oils with the following properties listed in Table 5. 
TABLE 5 
______________________________________ 
Properties of 4-alkyl-2-fluorobiphenyls. 
Alkyl group Yield bp (.degree.C.) 
______________________________________ 
Methyl 58% 120.degree. at 6 torr 
-n-Propyl 61.5% 108.degree. at 0.15 torr 
-n-Butyl 65% 106.degree. at 7 torr 
-n-Pentyl 69% 152.degree. at 0.3 torr 
______________________________________ 
The following mixtures incorporating the product of Step 1b1 illustrate the 
usefulness of that compound. 
(a) with cyanobiphenyl components. The commercially available liquid 
crystal material E7, supplied by BDH Chemicals Ltd, which contains: 
51% 4-cyano-4'-n-pentyl biphenyl 
25% 4-cyano-4'-n-heptylbiphenyl 
16% 4-cyano-4'-n-octyloxybiphenyl 
8% 4-cyano-4"-n-pentyl-p-terphenyl 
was added to the product of Step 1b1 here designated as Compound A. In the 
resulting solution (Mixture A) Compound A formed 25% by weight of the 
weight of E7 present (ie 20% by weight of Compound A and 80% by weight of 
E7 overall). Various properties were measured for the resulting solution 
and these were compared with the corresponding properties for E7 alone. 
These comparative properties, which are listed in Table 1, are denoted in 
that Table by the abbreviations specified above together with: 
T.sub.F =a temperature at which the liquid crystalline material may be kept 
for 72 hours without freezing 
TABLE 6 
______________________________________ 
Comparative properties of E7 with and without Compound A. 
Result for E7 
with Compound A 
Property Result for E7 (20% Compound A + 
measured without Compound A 
80% E7) 
______________________________________ 
N-I (.degree.C.) 
60.5 69.5-71.0 
T.sub.F (.degree.C.) 
-10 -25 
.DELTA.n 0.225 0.210 
.eta. (cSt) 
40.0 37.5 
______________________________________ 
All four properties listed in Table 1 are improved by the addition of 
Compound A to E7. Furthermore, the mixture of E7 plus Compound A as 
specified above showed (like E7) no smectic phase at temperatures down to 
-20.degree. C. 
(b) With PCH components. A mixture was formed using 20% by weight of 
Compound A with 80% of the commercially available ZLI 1132 (supplied by E 
Merck Co.) of the following composition by weight (Mixture B). 
24% trans-4-n-propyl-1-(4-cyanophenyl)cyclohexane 
36% trans-4-n-pentyl-1-(4-cyanophenyl)cyclohexane 
25% trans-4-n-heptyl-1-(4-cyanophenyl)cyclohexane 
15% trans-4-n-pentyl-1-(4'-cyano-4-biphenylyl)cyclohexane 
Comparative properties for ZLI 1132 with and without Compound A were 
measured in the same way as specified above. These comparative properties 
are listed in Table 2 as follows: 
TABLE 7 
______________________________________ 
Comparative properties of ZLI 1132 with and without 
Compound A. 
Result for ZLI 1132 
with Compound A 
Property Result for ZLI 1132 
(20% Compound A 
measured without Compound A 
80% ZLI 1132) 
______________________________________ 
N-I (.degree.C.) 
71.3-74 79.5-82.5 
T.sub.F (.degree.C.) 
-6 -25 
.DELTA.n 0.140 0.140 
.eta. (cSt) 
27.5 26.5 
______________________________________ 
As seen in Table 7 three of the properties of ZLI 1132 are improved by the 
addition of Compound A and the fourth property, birefringence, is 
unchanged. 
In addition, the mixture of ZLI 1132 plus Compound A specified above showed 
no smectic phase down to -20.degree. C. 
(c) A fast-switching broad range mixture: A mixture, Mixture C, was 
prepared with the following components by weight. 
9.95% 4-cyano-4'-ethylbiphenyl 
4.98% Trans-4-n-propyl-1-(4-cyanophenyl)-cyclohexane 
4.98% 4-cyano-4'-n-propylbiphenyl 
6.96% 1-(Trans-4-n-Propylcyclohexyl)-2-(4'-cyano-4-biphenyl)-ethane 
2.98% 4'-Cyano-4-biphenylyl 4'-n-heptyl-4-biphenylcarboxylate 
18.11% 
1-(Trans-4-n-propylcyclohexyl)-2-(4'-n-propyl-2'-fluoro-4-biphenyl)-ethane 
24.38% 
1-(Trans-4-n-propylcyclohexyl)-2-(4'-n-pentyl-2'-flouro-4-biphenylyl)-etha 
ne 
27.17% 
1-(Trans-4-n-pentylcyclohexyl)-2-(4'-ethane-2'-fluoro-4-biphenylyl)-ethane 
0.48% (+)-4-Cyano-4'-(2-methylbutyl)-biphenyl 
and was found to have the following properties: 
______________________________________ 
KN: Not frozen after storing for 1 month at 
-35.degree. C. 
NI: 102.degree. C. 
Birefringence: 
0.1735 at 589.6 nm at 20.degree. C. 
Threshold voltage: 
2.85 volts 
T.sub.on 
400 ms measured in a twisted nematic electro- 
optical cell having a liquid crystal layer 
T.sub.off 
540 ms thickness of 7 .mu.m and driven at 8 volts RMS 
at -20.degree. C. 
______________________________________ 
T.sub.on and T.sub.off are respectively the times required to switch the 
cell ON and OFF respectively and are measured between 10 and 90% of the 
cell transmission. 
(d) Mixtures with minimal temperature variation of the threshold voltage. 
The following mixtures listed in Table 8 were prepared and their properties 
as stated were measured in a twisted nematic electro-optical cell having a 
liquid crystal layer thickness of 7 .mu.m. 
TABLE 8 
______________________________________ 
Liquid Crystal Mixtures 
Positive Ternary 
Mixture 
(% byComponent 
(% byeutectic 
voltage, VThreshold 
##STR34## 
Name weight) weight) (Volts) (mV % .degree.C..sup.-1) 
______________________________________ 
D1 5% K6 95% E 5.17 0.11 
D2 10% K6 90% E 3.67 0.15 
D3 5% PCH3 95% E 5.56 0.13 
D4 10% PCH3 90% E 4.09 0.16 
______________________________________ 
In Table 8 E represents the ternary eutectic mixture of Formula I compounds 
specified above, K6 represents 4-cyano-4'-n-ethylbiphenyl obtained from 
BDH Chemicals Ltd and PCH3 represents 
trans-4n-propyl-(4-cyanophenyl)cyclohexane obtained from E Merck Co., 
Darmstadt. 
The parameter -1./V) (dV/dT.sub.0.degree.-50.degree. C.) is a measure of 
the variation of threshold voltage with temperature over the range 
0.degree. C. to 50.degree. C., V being the threshold voltage at 20.degree. 
C. (required to give 90% transmission through the cell) and T being 
temperature. 
EXAMPLE 2 
The preparation of 
1-(trans-4-n-propylcyclohexyl)-2-[4'-(4-trans-n-propylcyclohexyl)-2'-fluor 
o-4-biphenylyl]-ethane by Route 2 specified above. 
Step 2a1: 1-2-(Fluoro-4-biphenylyl)-4-n-propylcyclohexan-1-ol 
A few ml of a solution of 4-bromo-2-fluorobiphenyl (50 gram) in diethyl 
ether (150 ml) was added to magnesium turnings (5.3 gram) and diethyl 
ether (25 ml) under nitrogen. A crystal of iodine was added and reaction 
was initiated by warming. The remainder of the solution of 
4-bromo-3-fluorobiphenyl was then added at a rate fast enough to sustain 
vigorous refluxing. After boiling for 1 hour, the solution of the Grignard 
reagent was cooled to 20.degree. C. and then a solution of 
4-n-propylcyclohexanone (27.9 gram) in diethyl ether (75 ml) was added 
over 30 minutes. After stirring for 1 hour, the mixture was poured onto 
15% hydrochloric acid (2 liter) and the product extracted with ether 
(2.times.300 ml). The combined extracts were washed with water, dried and 
evaporated. The residue was crystallised from petroleum ether (b.p. 
60.degree.-80.degree., 120 ml) to give 1-(2-fluoro-4-biphenylyl)-4-propyl 
cyclohexane-1-ol as pale yellow crystals, m.p. 45.degree.-72.degree. (37.2 
gram: 61.2% theory) (isomer ratio by glc 60.6: 39.4). 
Step 2b1: 1-(2-Fluoro-4-biphenylyl)-4-n-propylcyclohex-1-ene 
Phosphorous pentoxide (40 grams) was added to a cooled and stirred solution 
of the product from Step 2a1 (35.5 gram) in toluene (500 ml). The mixture 
was kept at room temperature for 4 hours and then added to 1 liter water. 
After stirring for 30 minutes, the organic layer was separated and the 
aqueous layer re-extracted with toluene (300 ml). The combined extracts 
were washed neutral, dried and evaporated to dryness under vacuum. The 
yellow residue was recrystallised from ethanol (200 ml) at 5.degree. C. to 
give 29.3 gram (88% theory) 
1-(2-fluoro-4-biphenyl)-4-n-propyl-cyclohex-1-ene mp. 60.1-60.4.degree. C. 
The product was found to be 99.5% pure by glc. 
Step 2c1: 2-Fluoro-4-(4-n-propylcyclohexyl)-biphenyl (mixed isomers) 
The corresponding cyclohexane from step 2b1 (7 gram), 5% palladium on 
charcoal (0.7 gram), and ethanol were stirred in an atmosphere of hydrogen 
at 40.degree. C. until uptake of hydrogen ceased. The catalyst was 
filtered off and the solvent evaporated to leave the product as a mixture 
of isomers determined by glc to be 64.5% cis- and 34.5: trans-. 
A solution of the mixed isomers (9 gram) prepared as above in dimethyl 
formamide (50 ml) was aded to a suspension of sodium hydride (2.4 gram) in 
dimethylformamide (50 ml). The mixture was heated and stirred at 
60.degree. C. for 20 hours and then added firstly to ethanol (100 ml) and 
then to water (1 liter). The product was extracted with petroleum ether 
(bp 60.degree.-80.degree. C. 2.times.200 ml) washed with water, dried and 
evaporated to dryness. The residue (9.1 gram) now consisted of 83% trans 
isomer and was purified by crystallisation from ethanol (30 ml) at 
5.degree. C. to give the trans- product (5.6 gram, 99.5% pure by glc), mp 
69.degree.-70.degree. C. 
Step 2d1: 
4-(Trans-4-n-propylcyclohexylacetyl)-2'-fluoro-4'-(trans-4-n-propylcyclohe 
xyl)-biphenyl 
The product from Step 2c1 was reacted with trans-4-n-propylcyclohexyl 
acetyl chloride as described in Step 1a1. 
4-(Trans-4-n-propylcyclohexylacetyl)-2'-fluoro-4'-trans-4-n-propylcyclohex 
yl)-biphenyl crystallised from petroleum ether (bpt. 60.degree.-80.degree.) 
(63% yield). The product had the following properties: 
K-S.sub.A =90.degree.; S.sub.A -N=179.degree.-180.degree.; 
N-I=220.degree.-223.degree.. It was found to be 99.8% oure by glc. 
The product of Step 2d1, and other examples of compounds of formula Ik 
which may be prepared analogously, are summarised in Table 2 as follows: 
TABLE 2 
______________________________________ 
Compounds of formula: 
##STR35## 
R.sub.1 
R.sub.3 
R.sub.4 
R.sub.1 
R.sub.3 
R.sub.4 
R.sub.1 
R.sub.3 
R.sub.4 
______________________________________ 
CH.sub.3 
H F n-C.sub.5 H.sub.11 
H F n-C.sub.9 H.sub.19 
H F 
CH.sub.3 
F H n-C.sub.5 H.sub.11 
F H n-C.sub.9 H.sub.19 
F H 
C.sub.2 H.sub.5 
H F n-C.sub.6 H.sub.13 
H F n-C.sub.10 H.sub.21 
H F 
C.sub.2 H.sub.5 
F H n-C.sub.6 H.sub.13 
F H n-C.sub.10 H.sub.21 
F H 
n-C.sub.3 H.sub.7 
H F n-C.sub.7 H.sub.15 
H F n-C.sub.11 H.sub.23 
H F 
n-C.sub.3 H.sub.7 
F H n-C.sub.7 H.sub.15 
F H n-C.sub.11 H.sub.23 
F H 
n-C.sub.4 H.sub.9 
H F n-C.sub.8 H.sub.17 
H F n-C.sub.12 H.sub. 25 
H F 
n-C.sub.4 H.sub.9 
F H n-C.sub.8 H.sub.17 
F H n-C.sub.12 H.sub.25 
F H 
______________________________________ 
Step 2e1: 
4-(Trans-4-n-propulcyclohexylacetyl)-2'-fluoro-4'-(trans-4-n-propylcyclohe 
xyl)-biphenyl 
The product from Step 2d1 (5 gram) and trans-4-n-propylcyclohexyl acetyl 
chloride (3.42 gram) in dichloromethane (30 ml) were added over a period 
of 40 minutes to a stirred suspension of aluminium trichloride in 
dichlormethane (15 ml) at 10.degree. C. After allowing the temperature to 
reach room temperature (20.degree. C.) the mixture was stirred for 4 
hours. It was then poured onto water (150 ml). Subsequently, the product 
was extracted with petroleum spirit (bp 60.degree.-80.degree. C; 
2.times.200 ml). This was washed with water, dried over anhydrous sodium 
sulphate and evaporated to dryness to give 7.7 grams of a yellow solid. 
The pure product was recrystallised from petroleum spirit at 10.degree. C. 
The yield was 4.9 gram (63%) and the purity 99.8%. 
Step 2f1: 
1-(Trans-4-n-propylcyclohexyl)-2-[2'-fluoro-4'-(trans-4-n-propylcyclyhexyl 
)-4-biphenyl]-ethane 
The ketone prepared to Step 2a1 (4.8 gram), 99% hydrazine hydrate (5 ml), 
potassium hydroxide (2 gram) and digol (35 ml) were heated with stirring 
under a reflux condenser at 120.degree.-125.degree. C. for 5 hours, after 
which the temperature was raised to 180.degree. C. by distillation of the 
excess hydrazine hydrate. The mixture was heated under reflux for 20 
hours, cooled and poured onto 300 ml water. The organic product was 
extracted with a 4:1 solution of petroleum spirit (bp 
60.degree.-80.degree.)/dichloromethane 2.times.(20 ml), and the extract 
washed with water and dried over anhydrous sodium sulphate, and evaporated 
to give 4.6 gram of solid. This was dissolved in petroleum spirit (by 
60.degree.-80.degree. C.) (60 ml) and absorbed onto a column of basic 
alumina (10 gram) over silica gel (5 gram). Elution with petroleum spirit 
(150 ml) gave 4.3 grams of the crude product. Following recrystallisation 
from petroleum spirit 3.4 gram of the product (found to be 99.9% pure) was 
obtained in 73% yield and showed K-N=106.degree.-108.degree. C. and 
N-I=244.degree. C. 
EXAMPLE 3 
The preparation of 
1-(trans-4-n-propylcyclohexyl)-2-(2-fluoro-4'-n-propyl-4-biphenylyl)-ethan 
e by Route 3 above 
Step 3a1: 2-Fluoro-4-(trans-4-n-propylcyclohexyl)biphenyl 
A solution of 4-bromo-2-fluorobiphenyl (38.1 gram) in tetrahydrofuran (60 
ml) was added over 20 minutes to magnesium turnings (4 gram) suspended in 
tetrahydrofuran (20 ml), reaction being initiated by adding a crystal of 
iodine and warming as usual. This Grignard reagent was now added to a 
solution of trans-4-propylcyclohexylacetyl chloride (40 gram) and cuprous 
chloride (0.4 gram) in tetrahydrofuran (200 ml) with stirring at 
-60.degree. C. over 90 minutes. After allowing to warm to room temperature 
over two hours, the mixture was decomposed with water and the product 
extracted with petroleum ether (bpt. 60.degree.-80.degree.). The crude 
material was recrystallized twice from ethanol at 5.degree. C. to give the 
product (20.6 gram, 40% theory), m.p. 96.5.degree.-97.3.degree. C., which 
was found to be 99.6 pure by glc. 
Step 3b1: 1-(2-fluoro-4-biphenylyl)-2-(trans-4-n-propylcyclohexyl)-ethane 
The ketone produced in Step 3a was reduced as described in Step 1b1 to give 
the product in 71% yield, 99.8% pure by glc. The product was found to have 
mp=46.5.degree.-48.degree. (N-I [37.degree.-39.8.degree.]). 
Step 3c1: 
1-(2-Fluoro-4'-propionyl-4-biphenylyl)-2-(trans-4-n-propylcyclohexyl)-etha 
ne 
The 4'propionyl- group was introduced into the product of Step 3b1 by the 
technique for carrying out Friedel-Craft reactions described in Step 1a1. 
The desired product was obtained in 90% yield, 99.7% pure by glc. The 
product showed the following properties: 
K-N=74.4.degree.-74.8.degree.; N-I=165.4.degree.-165.8.degree. C. 
Step 3d1: 
1-(2-Fluoro-4'-n-propyl-4-biphenylyl)-2-(trans-4-n-propylcyclohexyl)-ethan 
The ketone produced by Step 3c1 was reduced by the Huang-Minlon procedure 
described in step 1b1 to give the product in 30% yield, 99.8% pure as 
determined by glc. The product had K-N=59.degree., N-I=108.degree.. 
The following homologues were prepared by identical sequences of reactions. 
TABLE 9 
______________________________________ 
Compounds having the formula: 
##STR36## 
Extrapolated 
monotropic nematic 
KN smectic NI viscosity at 
R.sub.1 
R.sub.2 (.degree.C.) 
phase (.degree.C.) 
20.degree. C. (cSt) 
______________________________________ 
C.sub.2 H.sub.5 
-n-C.sub.3 H.sub.7 
34 80 25.5 
-n C.sub.3 H.sub.7 
C.sub.2 H.sub.5 
34 [15] 97 
-n C.sub.5 H.sub.11 
H 39 53 
______________________________________ 
EXAMPLE 4 
The preparation of the compound of formula: 
##STR37## 
by Route 4 given above. 
Step 4a1 
This Friedel Crafts acrylation was carried out as in Step 1a1 except that 
2-fluorobiphenyl was used in place of 4-ethyl-2-fluorobiphenyl and that 
the molar amount of aluminum trichloride in dichloromethane present was 
doubled as was the amount of trans-4-n-pentylcyclohexylacetyl chloride. 
Step 4b1 
This Huang Minlon reduction was carried out in essentially the same way as 
Step 1b1 above. 
Compounds of Formula If containing other alkyl groups may be made in an 
analogous way. 
EXAMPLE 4' 
The preparation of the compound of formula 
##STR38## 
by Route 4' above. Steps 4'a1 to 4'e1 as follows are specific examples of 
Steps 4'a to 4'e respectively. 
Step 4'a1: Production of the Grignard reagent 
This step was carried out in a manner similar to the production of the 
Grignard reagent is Step 1a1 above, 4-bromo-2-fluorobiphenyl as starting 
material. 
Step 4'b1 
This step was carried out by the conventional reaction of trans-4-n-butyl 
cyclohexyl acetyl chloride together with the Grignard reagent produced in 
Step 4'a1 in the presence of tetrahydrofuran at a temperature of 
-78.degree. C. in the manner described by F Sato, M Inoue, K Oguro and M 
Sato in Tetrahedron Letters (1979) pages 4303 to 4306. 
Step 4c1: Reduction 
This step was carried out in a manner similar to the reduction in Step 1b1 
above. The product, of formula: 
##STR39## 
showed the following properties: C-I=44.degree. C. N-I=(36.6.degree. C.). 
Step 4'd1: Friedel Crafts acylation 
The step was carried out in a manner similar to Step 1a1 above. The 
product, of formula: 
##STR40## 
showed the properties=C-S=110.degree. C; S-N=185.7.degree. C. and 
N-I=190.1.degree. C. 
Step 4'e1: Reduction 
This step was carried out in a manner similar to step 1b1 above. The 
product was of formula: 
##STR41## 
Compounds of Formula If containing other alkyl groups may be made in an 
analogous way. 
The compounds which may be made in the manner described in Examples 1 to 4 
and 4' are summarized in Tables 10 to 13 respectively, as follows: 
TABLE 10 
______________________________________ 
Compounds of the formula: 
##STR42## 
R.sub.1 R.sub.2 
______________________________________ 
C.sub.m H.sub.2m+1 
C.sub.p H.sub.2p+1 
C.sub.m H.sub.2m+1 
OC.sub.p H.sub.2p+1 
C.sub.m H.sub.2m+1 
H 
______________________________________ 
where 
m includes all integer values from 0 to 12 inclusive and 
p includes all integer values from 1 to 12 inclusive. 
TABLE 11 
______________________________________ 
Compounds of the formula: 
##STR43## 
R.sub.1 R.sub.3 X Y 
______________________________________ 
n-C.sub.m H.sub.2m+1 
n-C.sub.p H.sub.2p+1 
H F 
n-C.sub.m H.sub.2m+1 
n-C.sub.p H.sub.2p+1 
F H 
______________________________________ 
where 
m includes all integer values from 0 to 12 inclusive and 
p includes all integer values from 0 to 12 inclusive. 
TABLE 12 
______________________________________ 
Compounds of the formula: 
##STR44## 
R.sub.1 R.sub.2 
______________________________________ 
C.sub.m H.sub.2m+1 
C.sub.p H.sub.2p+1 
C.sub.m H.sub.2m+1 
OC.sub.p H.sub.2p+1 
C.sub.m H.sub.2m+1 
H 
______________________________________ 
TABLE 13 
__________________________________________________________________________ 
Compounds of the formula: 
##STR45## 
R.sub.1 R.sub.2 X Y 
__________________________________________________________________________ 
C.sub.m H.sub.2m+1 
C.sub.p H.sub.2p+1 
F H 
C.sub.m H.sub.2m+1 
C.sub.p H.sub.2p+1 
H F 
__________________________________________________________________________ 
where 
m includes all integer values from 0 to 12 inclusive and 
p includes all integer values from 0 to 12 inclusive. 
EXAMPLE 5 
The preparation of 
1-(trans-4-n-propylcychohexyl)-2-(2'-fluoro-4'-n-propyl-p-terphenylyl)etha 
ne by Route 5 above. 
Step 5a1: The preparation of 3'-Fluoro-4-propyl-p-terphenyl 
A solution of 4-(4-n-propylcyclohexenyl)-2-fluorobiphenyl (20 gram) in 
toluene (120 ml) was added over a 25 minute period with stirring to a 
suspension of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (34 gram) in 
toluene (200 ml). The temperature rose from 19.degree. C. to 24.degree. C. 
over the addition, after which time the reaction mixture was heated under 
reflux (114.degree. C.) for 3 hours. The reaction mixture was cooled, 
filtered, the filtrate and toluene washings (100 ml) were combined and 
then washed with saturated sodium metabisulphite solution (250 ml). The 
organic extract was further washed with water (2.times.250 ml), dried and 
evaporated to dryness to give a brown residue (20.1 gram). The residue was 
dissolved in dichloromethane (120 mls) and adsorbed onto a column of basic 
alumina (60 gram) over silica gel (60 gram). Elution with dichloromethane 
(450 ml) gave on evaporation of the solvent an off white solid (14 gram) 
which was recrystallised from ethanol (80 mls) to yield a white 
crystalline product (12.8 gram) m.p. 75.degree.-77.degree. C. 
Step 5b1: The preparation of 
4-(trans-4-n-Propylcyclohexylacetyl)-2'-fluoro-4"propyl-p-terphenyl 
A mixture of 3'-fluoro-4-propyl-p-terphenyl (4 gram) and 
trans-4-n-propyl-cyclohexylacetyl chloride (2.8 gram) in dichloromethane 
(15 ml) was added over 20 minutes to a cooled 10.degree. C.) stirred 
suspension of anhydrous aluminum chloride (2.02 gram) in dichloromethane 
(10 ml). After the addition the reaction mixture was allowed to warm to 
23.degree. C. and left stirring for 18 hours. The resulting solution was 
added to a 10% hydrochloric acid solution (100 ml) and extracted 
successively with petroleum spirit (bp 60-80:2.times.100 ml). The organic 
extract was then washed with water (120 ml), dried over anhydrous sodium 
sulphate, filtered and evaporated to dryness. The yellow oily solid (7 
gram) was dissolved in dichloromethane (50 ml) and adsorbed onto a column 
of basic alumina (20 gram) over silica gel (10 gram). Elution with 
dichloromethane gave on evaporation of the solvent a yellow solid (5 
gram). Recrystallisation from dichloroethane (10 gram) gave a crystalline 
material (2.5 gram) which had the properties: K-S=120-126; 
S-N=200.degree.-204.degree. C.; N-I=225.degree.-227.degree. C. 
Step 5c1: The preparation of 
1-(trans-4-n-Propylcyclohexyl)-2-(2'-fluoro-4"-propyl-p-4-terphenyl)ethane 
The ketone prepared in Step 5b1 (1.8 gram), 99% hydrazine (2 ml) potassium 
hydroxide (1 gram) and digol (30 ml) were heated with stirring at 
120.degree. C. for 17 hours, after which time the temperature was raised 
by distillation of excess hydrazine hydrate/digol mixture to 180.degree. 
C. The resulting solution was heated under reflux for 5 hours at 
180.degree.-182.degree. C., then cooled to 60.degree. C. and poured into 
ice water (100 gram). The organic product was extracted with a mixture of 
petroleum spirit (bp 60-80 150 ml) and dichloromethane (30 ml), washed 
with water (2.times.50 ml) and the solvent dried and evaporated. The 
yellow residue (1.7 gram) was dissolved in 20 ml of a 1:1 mixture of 
dichloromethane and petroleum spirit (bp 60-80 ) and adsorbed onto a 
column of basic alumina (6 gram) over silica gel (4 gram). Elution with 
the same solvent mixture (70 ml) gave on evaporation of solvent a 
crystalline material (1.3 gram). Recrystallisation from petroleum spirit 
(bp. 60-80:7 ml) at 10.degree. C. a white solid (1 gram) which had the 
following properties: 
K-S=81-84.degree. C. S-N=86-88.degree. C. N-I=248.degree.-252.degree. C. 
Examples of further compounds which may be prepared by one or more of the 
Routes specified above, or analogous routes, are summarised in Table 13a 
as follows: 
TABLE 13a 
______________________________________ 
Compounds of the formula: 
##STR46## 
R.sub.1 
##STR47## X 
______________________________________ 
C.sub.m H.sub.2m+1 
##STR48## F 
C.sub.m H.sub.2m+1 
##STR49## F 
C.sub.m H.sub.2m+1 
##STR50## F 
C.sub.m H.sub.2m+1 
##STR51## F 
C.sub.m H.sub.2m+1 
##STR52## F 
C.sub.m H.sub.2m+1 
##STR53## H 
C.sub.m H.sub.2m+1 
##STR54## H 
C.sub.m H.sub.2m+1 
##STR55## H 
C.sub.m H.sub.2m+1 
##STR56## H 
C.sub.m H.sub.2m+1 
##STR57## H 
C.sub.m H.sub.2m+1 
##STR58## H 
C.sub.m H.sub.2m+1 
##STR59## H 
C.sub.m H.sub.2m+1 
##STR60## H 
C.sub.m H.sub.2m+1 
##STR61## H 
______________________________________ 
where 
m includes all integer values from 0 to 12 inclusive and 
p includes all integer values from 1 to 12 inclusive. 
The following examples, Example 6 to 8 illustrate the production of 
compounds of Formula I wherein one of the terminal groups R.sub.1 and 
R.sub.2 is chiral. 
Example 6: 
The preparation of 
(+)-1-(trans-4-n-butylcyclohexyl)-2-[2'-fluoro-4'(2-methylbutyl)-4-bipheny 
l]-ethane by Route 1 above: 
Step P: 
The preliminary preparation of (+)-2 Fluoro-4-(2-methylbutyl)-biphenyl 
10 ml of a solution of a 4-bromo-2-fluorobiphenyl (90 gram) in 
tetrahydrofuran (90 ml) was added to magnesium turnings (9.6 gram) and 
tetrahydrofuran (20 ml) under nitrogen. A single crystal of iodine was 
added and the reaction was initiated by warming. The remainder of the 
solution of 4-bromo-2-fluorobiphenyl was then added dropwise over 1/2 
hour. After heating under reflux for 1 hour, the solution of the Grignard 
reagent was cooled to 25.degree. C. 10 ml of a solution of 
2-methylbutylphenylsulphonate (150 gram) in tetrahydrofuran (140 ml) was 
then added to the reaction mixture followed by cuprous chloride (3 gram). 
The remainder of the phenylsulphonate solution was added over a 40 minute 
period. The temperature of the resulting grey/green reaction mixture rose 
to 45.degree. C. which was then elevated by heating to boiling for 1 hour. 
The reaction was allowed to cool to room temperature, then added to a 20% 
(by volume) hydrochloric acid solution (2.5 liters) and the product 
extracted with dichloromethane (2.times.500 ml). The organic layer was 
washed with water (2.times.500 ml) dried over anhydrous sodium sulphate 
(15 gram) and the solvent evaporated to give an orange liquid residue. On 
cooling some white solid crystallised out from the residue. After 
filtration the residue (88.6 gram) was fractionally distilled under vacuum 
(0.5 torr) to give a colourless liquid (65 gram). This was found to be 
98.8% pure by glc. The bp was 120.degree. C. at 0.5 torr. The optical 
rotation was +14.62.degree. (solvent). 
Step 1a2: The preparation of 
(+)-4-(trans-4-n-Butylcyclohexylacetyl)-2'-fluoro-4'-(2-methylbutyl)biphen 
yl 
A mixture of (+)-2-Fluoro-4(2-methylbutyl)biphenyl (10 gram) and 
trans-4-n-butylcyclohexylacetyl chloride (9.4 gram) in dichloromethane (20 
ml) was added over 20 minutes to a cooled (5.degree.-10.degree. C.), 
stirred suspension of anhydrous aluminium chloride 6.1 gram) in 
dichloromethane (20 ml). After the addition the reaction mixture was 
allowed to warm to 23.degree. C. and left stirring for 17 hours. The 
resulting solution was added to water (200 ml), extracted successively 
with petroleum spirit (bp. 60.degree.-80.degree.:180 ml +100 ml). The 
organic extract was then washed with water (200 ml), dried over anhydrous 
sodium sulphate (5 gram) and evaporated. The yellow crystalline residue 
(17.9 gram) was recrystallised from ethanol (35 ml) at 25.degree. C. to 
give the product (14.8 gram; 85% yield). The product had 
mp=71.4.degree.-72.1.degree. C.; VirtualCH-I, (68.5.degree.-68.8.degree. 
C.). It was found to be 99.5 % pure by glc. 
Step 1b2: The preparatin of 
(+)-1-trans-4-n-Butylcyclohexyl)2-[2'-fluoro-4'(2-methylbutyl)-4-biphenyly 
l]-ethane 
The ketone prepared above (14.4 gram), 99% hydrazine hydrate (14.4 ml) 
potassium hydroxide (7.2 gram) and digol (120 ml) were heated and stirring 
under a reflux condenser at 125.degree. C. for 4 hours, after which time 
temperature was raised to 175.degree. C. by distillation of the excess 
hyrazine hydrate. The mixture was then heated under reflux for 17 hours, 
cooled to 60.degree. C. and poured onto ice water (500 gram). The organic 
product was extracted with petroleum spirit (bp. 
60.degree.-80.degree.:2.times.200 ml), the extract washed with water 
(2.times.200 ml) and dried over anhydrous sodium sulphate. Evaporation of 
the solvent yielded a yellow oil (14.1 gram). This was dissolved in 
petroleum spirit (bp. 60-80:100 ml) and absorbed onto a column of basic 
alumina (50 gram) over silica gel (20 gram). Elution with petroleum spirit 
(320 ml) gave on evaporation of the solvent a colourless oil (11.7 gram). 
Crystallisation from propan-1-ol (70 ml) at -50.degree. C. gave a chiral 
nematic material 9.4 gram; 68% yield). This was found to be 99.8% pure by 
glc. 
The product had the properties: 
S-CH,=6.degree. C.; Ch-I 72.degree. C. 
Helical molecular pitch=0.23 microns 
EXAMPLE 7 
The preparation of 1-(trans-4-ethylcyclohexy)-2-[ 
2'-fluoro-4'-(2-methylbutyl)-4-biphenylyl]ethane by Route 1 above 
Step 1a3 
The preparation of 
4-(trans-4-ethylcyclohexylacetyl)-2'-fluoro-4'(2-methylbutyl)biphenyl 
This was carried out in a manner analogous to Step 1a2 using 
4-ethylcyclohexyl acetyl chloride as starting material. 
The product had the properties: 
Mp=40.degree.-42.degree. C.; virtual Ch-I=(27.5.degree. C.) 
Step 1b3 
The preparation of 
1-(trans-4-ethylcyclohexyl))-2-[2'-fluoro-4'-(2-methylbutyl)-4-biphenylyl] 
ethane 
This was carried out in a manner analogous to Step 1b2 above. 
This product had the properties: 
S-Ch=-11.degree. C. Ch-I=45.degree. C. 
EXAMPLE 8 
The preparation of 
1-(trans-4-n-heptylcyclohexyl)-2-[2'-fluoro-4'-(2-methylbutyl)4-biphenylyl 
]ethane by Route 1 above 
Step 1a4 
The preparatin of 
4-(trans-4-n-heptylcyclohexylacetyl)-2'-fluoro-4'(2-methylbutyl)biphenyl 
This was carried out in a manner analogous to Step 1a2 above. 
The product had the properties: 
K-Ch=69.8.degree.-70.3.degree. C.; Ch-I=74.1.degree.-74.3.degree. C. 
Step 1b4 
The preparation of 
1-(trans-4-n-heptylcyclohexyl)-2-[2'-fluoro-4'-(2-methylbutyl)-4-biphenyly 
l]ethane 
This was carried out in a manner analogous to Step 1b2 above. 
The product had the properties: 
S-Ch=52.degree. C. Ch-I=79.degree. C. 
Examples of chiral nematic compounds which may be produced in a manner 
similar to the above examples are summarised in Table 13b as follows: 
TABLE 13b 
______________________________________ 
Compounds of formula: 
##STR62## 
where 2MeBu = (+)-2-methylbutyl 
R.sub.1 
##STR63## X 
______________________________________ 
C.sub.m H.sub.2m+1 
##STR64## F 
C.sub.m H.sub.2m+1 
##STR65## F 
C.sub.m H.sub.2m+1 
##STR66## F 
C.sub.m H.sub.2m+1 
##STR67## F 
C.sub.m H.sub.2m+1 
##STR68## F 
C.sub.m H.sub.2m+1 
##STR69## H 
C.sub.m H.sub.2m+1 
##STR70## H 
C.sub.m H.sub.2m+1 
##STR71## H 
C.sub.m H.sub.2m+1 
##STR72## H 
C.sub.m H.sub.2m+1 
##STR73## H 
C.sub.m H.sub.2m+1 
##STR74## H 
______________________________________ 
where m includes all values from 0 to 12 inclusive. 
The following experiment was carried out to demonstrate the superiority of 
compounds of Formula Ia having R.sub.A =n-alkyl and R.sub.B =n-alkyl and 
less than 10 carbon atoms in R.sub.A and R.sub.B together compared with 
the compounds of the same formula but with R.sub.A and R.sub.B both 
n-pentyl, ie a total of 10 carbon atoms in R.sub.A and R.sub.B. Each 
compound under investigation (80% by weight) was separately formed into a 
mixture together with 10% by weight of the cyanobiphenyl of formula: 
##STR75## 
together with 10% by weight of the cyanobiphenylyl ethane of formula: 
##STR76## 
The smectic-to-nematic (S-N) transition temperature of each of the 
resulting mixtures was then measured. This transition temperature gives a 
good indication of the tendency of the compound under investigation to 
form injected smectic phases. The lower the S-N temperature the better is 
the compound under investigation. The results obtained are listed in Table 
14 as follows. 
TABLE 14 
______________________________________ 
Investigation of the smectic-to-nematic transition 
temperatures (SN) in mixtures for compounds of formula: 
##STR77## 
Compound under investigation 
m p X Y SN of mixture (.degree.C.) 
______________________________________ 
2 2 H F -17.5 
2 3 H F -15.2 
2 4 H F 14.6 
2 5 H F 19.6 
3 2 H F -22.0 
3 3 H F &lt;-15.0 
3 4 H F 29.8 
3 5 H F 31.0 
4 1 H F &lt;-30.0 
4 2 H F 16.0 
4 3 H F 28.6 
4 4 H F 53.0 
5 0 H F &lt;-10 
5 2 H F 6.4 
5 5* H F 67.5 
2 3 F H 1.7 
3 2 F H -7.0 
3 3 F H 18.5 
5 5** F H 76.0 
______________________________________ 
The compounds marked * and ** in Table 14 are comparative examples not 
falling within the scope of the present invention and are clearly 
inferior, in terms of the S-N value, to the other compounds listed in 
Table 14. 
Similar results are obtained for compounds of Formulae Ia and Ib having 
R.sub.1 =n-alkyl and R.sub.2 =n-alkoxy when the total number of carbon 
plus oxygen atoms in the groups R.sub.1 and R.sub.2 is 10 or more.

The display of FIGS. 1 to 4 comprises a cell 1, formed of two, front and 
back, glass slides 2, 3 respectively, spaced about 7 .mu.m apart by a 
spacer 4 all held together by an epoxy resin glue. A liquid crystal 
material 12 fills the gap between the slides 2, 3 and the spacer 4. In 
front of the front glass slide 2 is a front polariser 5 arranged with its 
axis of polarisation axis horizontal. A reflector 7 is arranged behind the 
slide 3. A rear polariser 6 or analyser is arranged between the slide 3 
and reflector 7. 
Electrodes 8, 9 of tin oxide typically 100 .ANG. thick are deposited on the 
inner faces of the slides 2, 3 as a complete layer and etched to the 
shapes shown in FIGS. 3, 4. The display has seven bars per digit 10 plus a 
decimal point 11 between each digit. As shown in FIG. 3 the rear electrode 
structure is formed into three electrodes x.sub.1, x.sub.2, x.sub.3. 
Similarly the front electrode structure is formed into three electrodes 
per digit and decimal point y.sub.1, y.sub.2, y.sub.3 . . . Examination of 
the six electrodes per digit shows that each of the eight elements can 
independently have a voltage applied thereto by application of suitable 
voltage to appropriate x, y electrodes. 
Prior to assembly the slides 2, 3 bearing the electrodes are cleaned then 
dipped in a solution of 0.2% by weight of poly-vinyl alcohol (PVA) in 
water. When dry, the slides are rubbed in a single direction with a soft 
tissue then assembled with the rubbing directions orthogonal to one 
another and parallel to the optical axis of the respective adjacent 
polarisers, ie so that the polarisers are crossed. When the nematic liquid 
crystal material 12 is introduced between the slides 2, 3 the molecules at 
the slide surfaces lie along the respective rubbing directions with a 
progressive twist between the slides. 
When zero voltage is applied to the cell 1 light passes through the front 
polariser 5, through the cell 1 (whilst having its plane of polarisation 
rotated 90.degree.) through its rear polariser 6 to the reflector 7 where 
it is reflected back again to an observer (shown in FIG. 1 at an angle of 
45.degree. to the axis Z normal to axes X and Y in the plane of the slides 
2, 3). When a voltage above a threshold value is applied between two 
electrodes 8, 9 the liquid crystal layer 12 loses its optical activity, 
the molecules being re-arranged to lie perpendicular to the slides 2, 3, 
ie along the axis Z. Thus light at the position does not reach the 
reflector 7 and does not reflect back to the observer who sees a dark 
display of one or more bars of a digit 10. 
Voltages are applied as follows as shown in FIGS. 5, 6 and 7 for three 
successive time intervals in a linescan fashion. An electrical potential 
of 3 V/2 is applied to, ie scanned down, each x electrode in turn whilst - 
V/2 is applied to the remaining x electrodes. Meanwhile -3 V/2 or V/2 is 
applied to the y electrodes. A coincidence of 3 V/2 and -3 V/2 at an 
intersection results in a voltage 3 V across the liquid crystal layer 12. 
Elsewhere the voltage is V or -V. Thus by applying -3 V/2 to appropriate y 
electrodes as 3 V/2 is scanned down the x electrodes selected 
intersections are turned ON as indicated by solid circles. The electric 
voltage V is an ac signal of eg 100 Hz square wave, and the sign indicates 
the phase. 
It will be apparent to those skilled in the art that the device shown in 
FIGS. 1 to 7 is a multiplexed display because the electrodes are shared 
between ON and OFF intersections or display elements. 
Materials embodying the invention which are suitable for use as the 
material 12 in the above device are Mixtures C, D1, D2, D3 or D4 specified 
above or Mixture 1 specified in Table 15 as follows. 
TABLE 15 
______________________________________ 
Mixture 1 
Weight 
Per- 
Compound centage 
______________________________________ 
##STR78## 15 
##STR79## 15 
##STR80## 15 
##STR81## 15 
##STR82## 20 
##STR83## 20 
______________________________________ 
Small amounts of an optically active material may be added to the nematic 
material to induce a preferred twist in the molecules in the liquid 
crystal layer. This and the use of appropriate slide surface treatment 
removes the problems of display patchiness as taught in UK Patent Ser. 
Nos. 1,472,247 and 1,478,592. 
Suitable optically active materials are: 
C15: about 0.1-0.5% by weight and CB15: about 0.01% to 0.05% by weight. 
##STR84## 
Small amounts of pleochroic dye may be added to enhance the display 
constrast, eg 2% by weight of dye Mixture 2 specified in UK Patent 
Specification No. 2093475A. One polariser is removed in this case. 
In another embodiment mixtures embodying the second aspect of the invention 
may be used in a Freedericksz effect cell. Such a cell may be constructed 
by sandwiching the liquid crystal material between glass slides having 
electrode films deposited on their inner surfaces as in the above device. 
However, in this case the polarisers are not necessary; the glass slide 
inner surfaces are treated with a coating of lecithin and the liquid 
crystal material is a negative material whose molecules are aligned in the 
OFF state perpendicular to the slide substrates (homeotropic texture) by 
the lecithin coating. Application of an appropriate electric field across 
the material in the ON state re-arranges the molecules parallel to the 
slide surfaces (homogeneous texture). A pleochroic dye may be incorporated 
in the liquid crystal material to enhance the contrast between the ON and 
OFF states. 
A Freedericksz effect cell made in the above way may incorporate Mixture 3 
below, the cell spacing being 10 .mu.m. 
TABLE 16 
______________________________________ 
Mixture 3 
Weight 
Per- 
Compound centage 
______________________________________ 
##STR85## 30 
##STR86## 30 
##STR87## 20 
##STR88## 20 
Compound J = 
##STR89## 
______________________________________ 
may optionally be added to Mixture 3 (up to 3% by weight of Mixture 3) as a 
negative additive. 
The preparation of Compound J is described in published UK Patent 
Application No. 2061256A. About 1% by weight of a the dye mixture 
specified above may be added to Mixture 3 to give a dyed mixture. (Mixture 
3A) 
When a voltage is applied across the cell, the colour changes from a weakly 
absorbing state to a strongly absorbing state. 
In an alternative embodiment of the invention a (cholesteric-to-nematic) 
phase change effect device incorporates a material as defined above. 
A cell is prepared containing a long helical pitch cholesteric material 
sandwiched between electrode-bearing glass slides as in the twisted 
nematic cell described above. However the polarisers and surface 
preparations for homogeneous alignment, eg treatment of the glass slide 
surfaces with SiO, are not used in this case. 
If the glass slides are untreated and the liquid crystal material has a 
positive dielectric anisotropy (.DELTA..epsilon.) the liquid crystal 
material is in a twisted focal conic molecular texture in the OFF state 
which scatters light. The effect of an electric field applied between a 
pair of electrodes on the respective inner surface of the glass slides is 
to convert the region of liquid crystal material between the electrodes 
into the ON state which is a homeotropic nematic texture which is less 
scattering then the OFF state. This is a `negative contrast` type of phase 
change effect device. 
If the inner glass slide surfaces are treated, eg with a coating of 
lecithin, to give alignment perpendicular to those surfaces, and the 
liquid crystal material has .DELTA..epsilon. negative the material in the 
OFF state is in a homeotropic texture which has little scattering effect 
on incident light. If an electric field is applied between a pair of 
electrodes on the respective inner surfaces of the glass slides the region 
of liquid crystal material between the electrodes is converted to a 
twisted homogeneous texture which scatters light (the ON state). This is a 
`positive contrast` type of phase change effect device. 
The contrast between the two states in each case may be enhanced by the 
addition of a small amount of a suitable pleochroic dye (eg 1% by weight 
of the dye mixture specified above in the case where .DELTA..epsilon. is 
positive) to the liquid crystal material. 
A suitable positive dielectric anisotropy material, Mixture 4, embodying 
the invention for use in a phase change effect (negative contrast type) 
device is: 
TABLE 17 
______________________________________ 
Mixture 4 
Weight 
Per- 
Compound centage 
______________________________________ 
##STR90## 50 
##STR91## 23 
##STR92## 4 
(R.sub.c = (+)-2-methylbutyl) 
##STR93## 23 
______________________________________ 
A suitable negative dielectric anisotropy material embodying the invention 
for use in a phase change effect (positive contrast type) device, Mixture 
5, is as follows: 
TABLE 18 
______________________________________ 
Mixture 5 
Weight 
Per- 
Material centage 
______________________________________ 
Mixture 3 99 
##STR94## 1 
(R.sub.c = (+)-2-methylbutyl) 
______________________________________ 
As an alternative to the chiral compound specified in Table 18 a chiral 
compound of Formula I may be used.