JPS6069045A - Disubstituted ethane, liquid crystal material and use for device - Google Patents

Abstract

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

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to di-substituted ethane and its use in liquid crystal materials and devices.

The use of liquid crystal materials to produce electro-optical effects in display devices such as digital calculators, clocks, meters and simple word displays is known. However, no liquid crystal material is known that is ideal in all respects, and considerable effort is typically expended in the industry to improve its properties.

Liquid crystal materials generally consist of specially selected mixed compositions,
Material improvements have been made by forming new mixtures with improved properties.

The composition of the electro-optical liquid crystal mixture depends on the display effect to be utilized and the special properties required for that effect. Various display effects are illustrated below. For all types of display effects, it is desired that the mixture exhibits the best possible combination of the following general properties:
death~).

(1) The liquid crystal temperature range should be as wide as possible, including room temperature (20°C); (1) The melting point (solid-liquid crystal transition temperature) should be as low as possible; (Ill) The clearing point (liquid crystal - isotropic (OV) positive or negative (appropriate) dielectric anisotropy (conductivity measured parallel to the molecular axis minus electrical resistivity measured perpendicular to the molecular axis) should be as high as possible; (V) The viscosity is as low as possible to minimize the display switching rate; (the temperature change in the VO electro-optic response is as small as possible; ~1- Chemical and photochemical good stability; multiplexability further exemplifying special properties useful in special applications;
ity); (IXI) p-electronic anisotropy can be switched by the number of liquid crystals; Products are obtained by mixing components with different properties.

It has been particularly difficult to meet the various properties required for displays on automobile dashboards. In the above case, the viscosity must be low for rapid switching at low temperatures of -20 to -30°C, and the clearing point is high <(>9°C) and through the display part in the off state. It must have a high birefringence to prevent light from bleed through due to backside illumination.

In order to minimize manufacturing costs, it is desirable to have a minimum number of components in the mixture while still having a satisfactory combination of the desired properties. Therefore, the individual components used provide the desired properties w
It is desirable to have t&. Furthermore, in order to minimize the number of components, it is desirable that the individual components have good mutual solubility.

The object of the present invention is to provide new liquid crystal compounds which are suitable components for liquid crystal mixture compositions for displays to be used in electro-optical displays, in particular on automobile dashboards.

The fluorinated metal material of the present invention has the following formula I.

[In the formula, K) is heli- or →■-; R□ is hydrogen or an alkyl group having 1 to 12 carbon atoms: R2 is hydrogen, an alkyl group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms;
12 alkoxy groups, -R3, -CH, .C! H2
-(i) -R3 and +R, (wherein R3 is hydrogen or an alkyl group having 1 to 12 carbon atoms, R4 is hydrogen or a carbon number 1
-12 alkyl groups or alkoxy groups with a mass number of 1 to 12); (1) represents a cyclohexane ring in the trans position in the case of 1,4-disubstitution; 0 represents a benzene ring; represents; x, Y and z each independently represent hydrogen or fluorine at one or more side positions of the benzene ring, provided that X, Y
At least one of When n-alkyl and R2 is n-alkyl or n-alkoxy, the number of carbon atoms or the total number of carbon atoms and oxygen atoms in the R1 and R2 groups is less than 10. ] When used in nematic liquid crystal mixtures, the alkyl or alkyl group in the compound of formula I is preferably linear. However, chiral nematic (
When used in mixtures (optically active), one or more alkyl or alkoxy groups contained in the molecule are e.g.
2 (where n is 1 to 8, and (+-)- is a chiral group having a positive optical rotation angle, such as (+)-2
-representing methylbutyl).

Specific examples of compounds having formula I are shown below.

Rc◇CH,・CH2(◇-GXzuD"Rn Formula Ij
In the formula, each RA is independently an alkyl group, for example, a carbon number of 1 to 12
Preferably it is an n-alkyl group having 1 to 8 carbon atoms, and RI
l independently represents hydrogen, an alkyl group, or an alkoxy group, such as a p-alkyl group or n-alkoxy group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms.

In the case of compounds of formulas Ia and Ib, the proviso conditions described in general formula (1) also apply. That is, when R is an n-alkyl group and RT3 is an n-alkyl or n-alkoxy group, the total number of carbon atoms and oxygen atoms contained in the two groups is less than 10. Preferably, the total number of carbon atoms and oxygen atoms contained in RA and RB is 4 to 8.

A compound having the same general formula as formulas Ia and Ib,
The number of carbon atoms in the terminal n-alkyl group is 10, and the number of carbon atoms in the terminal n-alkyl group is 10.
- Compounds in which the total number of carbon atoms and oxygen atoms in the alkyl or n-alkoxy group 2 is 10 are 1 European patent application No. 84194 published after the filing of British patent application No. 8302119, which is the basis of the priority of this application proposed in No.

However, the properties of these compounds are not described or suggested in the European patent application. As shown below, these compounds have considerably inferior injected smectic behavior in mixtures with positive nematic compounds compared to the corresponding compounds of formulas Ia and Ib. The compounds proposed in said European patent application are therefore excluded from the scope of the present invention.

Compounds of formula Ia to Ij are examples of compounds of formula I useful as liquid crystal compounds, and compounds of formula Ik are examples of compounds of formula I that are useful as liquid crystal compounds, and compounds of formula Ik are examples of compounds of formula I, particularly compounds of formula Id and Ie, where X, Y and 2 is H or F, and at least one is F).

Compounds of formula I can be very interesting components in liquid crystal materials for electro-optical displays. For example, formulas Ia and Ib
The compound (wherein RA and R13 are p-alkyl groups) has the following excellent advantages as described in the Examples.

(1) It has a low melting point, generally below 30°C, which is advantageous in formulating liquid crystal mixtures with a low melting point; (1) It has a high clearing point, about 100°C, and a very wide nematic range, about about 70° C., which is advantageous for formulating liquid crystal mixtures with a wide nematic range: (lit) virtually no undesirable smectic phases; (lv) smectic phases in combination with nematic materials with positive induced anisotropy. (V) High solubility in nematic materials with positive induced anisotropy; Has the property of increasing the clearing point when added; 6111+ has a relatively low viscosity and has the property of reducing the viscosity of known nematic mixtures; 4t11) Can form the basis of mixtures with high switching times at low temperatures : Ox) High birefringence compared to other known materials with similar thermal properties and viscosity; (X) Extremely low temperature dependence of threshold voltage; [Phase]
The chemical and photochemical stability is good; because of the attractive combination of various properties mentioned above, liquid crystal mixtures can be formed which have superior properties compared to known mixtures.

RA and X are as defined above) are known (UK Patent Publication No.
(See specification No. 93057). However, in general, the formula l
In particular, the new compounds of formulas Ia and Ib unexpectedly possess an overall better combination of desirable properties compared to the known compounds as mentioned above.

For example, a compound having formula I can be expressed as
1 is an alkyl, alkoxy or cyano group), but the melting point and viscosity are not significantly increased in comparison.

Similarly, the compound having the formula I can be used as a known additive with a high clearing point having the formula C RA+CH, .C)(, -()-(D-CN In comparison, the melting point and viscosity are lower and the solubility for positive nematic materials is better.

Furthermore, compounds having formula I are generally more reactive than compounds having 2B, and may be added to materials with negative dielectric anisotropy used in certain specific applications, as described below. or can be used as the material. Compounds of formula B have a high positive dielectric anisotropy and are therefore generally unsuitable for this purpose.

The remarkable thermally insulating properties of the compounds having formula (1) originate from the influence of the pendant fluorine atoms, which suppress and eliminate undesirable smectic phases. This is clear from Tables 1 and 2, which compare the phase transitions of compounds with and without lateral fluorine atoms.

Comparison of properties of compounds having the formula in Table 1 RIR,X YK-N K-88-8R-N N-1"
2H6C3H? HH5598, 5121, 5C2H,
C3H, HF 21.3 78.3-85 C3H, C3H, HH67118119144C3H2
C3H, HF 40 107.7C3H, C3H, FH
59108 C3H7CJI, IHH132,5141,5C3H,
C, Ho, HF 28.1- 10529.7 Table 2 Comparison of properties of compounds having the formula R, R, X Y K-N K-B S-N N-IC3
H, C3H7HH172201258C3H7C3H7
HF 106.8 244 In Tables 1 and 2, 8.
N and I represent solid, smectic, nematic and isotropic phases, respectively, K-N, etc. represent the transition temperature ("C).

In the table, all alkyl chains are linear. S-8 represents a transition from a smectic phase to another phase.

As mentioned above, in the case of compounds that do not contain lateral fluorine atoms, the smectic phase generally and often persists at temperatures above 100°C, whereas in the case of compounds having the formula (1), the smectic phase is extremely rare at room temperature (20°C). It is seen in this. Thus, the nematic range can be extended to low temperatures by preparing eutectic mixtures of novel metals.

Rs 1-C, herein referred to as mixture EI
s R7R2-p-Cs R726 weight section R1-n-C
3H, R2wn-C1lH1□35fold [IRl-r4-
A mixture consisting of C, H□, R2-C, H, 39 molecules does not form a smectic phase (it forms a nematic phase in the range from a melting point of -13.5°C to a clearing point of 103.5°C). 7, which provides an advantageous basis for liquid-crystal mixtures with low settling points and which can be switched rapidly at low temperatures.

According to one preferred embodiment of the invention, therefore, the nematic or chiral liquid crystal material consists of a mixture containing two or more compounds of formula (1). The nematic or chiral nematic temperature range of such mixtures is extremely wide. This mixture contains congeners 1 of the same type of compound, e.g. two or more of the formula I
It may contain the compound of a.

It is also possible to combine compounds that have the same general formula but are structural isomers that differ, for example, in the position of the heptad in X and Y. That is, one compound is X-F and Y-H (e.g. in formulas Ia and Ib),
The other may be a compound having the same structure but with Y-F and X-H. Although the isomers have similar properties, mixing them can very effectively lower the melting point.

The action of the pendant atoms can unexpectedly suppress not only the smectic phase but also the formation of the smectic phase, known as the single-shot smectic phase.

The majority of commercially available electro-optic liquid crystal displays are twisted nematic displays that operate by the twisted nematic effect.

Plotting the light intensity output from a twisted nematic display against the applied voltage produces a curve in the so-called optical threshold region (corresponding to liquid crystal molecules undergoing a rapid change from homogeneous to homeotropic configuration). It is desirable that the slope be as steep as possible. Light output (lig
The slope of the htoutput ) versus voltage curve depends on the liquid crystal material used in the display.

The majority of currently commercially available twisted nematic displays are multiplexed displays, meaning that the individually addressed elements of the display have one set of electrodes on one side of the display panel and another set of electrodes on the other side of the panel. Each electrode in each set is shared by all elements in a given row or column) □Display over a limited display area by multiplexing The amount of information to be displayed is increased, and fewer electrode connections are used per number of total display elements addressed.

Suitable multiple Vx properties (mul, tipLex) used in multiplexed twisted nematic displays
To produce a liquid crystal material having a
Two types of nematic components, that is, one component is a compound having a cyano group at the end (hereinafter abbreviated as cyano material)
111 or more, and the other component is formed from one or more compounds that do not have a cyano group at the end (hereinafter abbreviated as 1 non-cyano material'). It is generally recognized in the art that this is the most appropriate method.

The non-cyano material has a small dielectric anisotropy. Preferably, this non-cyano material accounts for at least 30% by weight of the two-component mixture.

The twisted nematic effect occurs only when the liquid crystal material is in the nematic phase; for example, the effect is not exhibited when the material is in the smectic phase. When a cyano material is mixed with a non-cyano material, the mixture exhibits an undesirable smectic phase, known in the art as a single-shot smectic phase, and the smectic phase appears as an area on a temperature versus composition graph or phase diagram. appear. However, if each material is pure, it exhibits only a nematic liquid crystal phase. 30 heavy il1
The above compositions containing non-cyano materials are close to compositions that are considered preferable for electrochemical operation, but in this case they tend to reach a peak on the injection smectic phase diagram. According to common knowledge in the art, for a given mixture of cyano and non-cyano materials, the smaller the area on the phase diagram occupied by the smectic phase, the lower the temperature at which the smectic phase begins to appear. The more useful it is as a mixture for use in multiple Vx twisted nematic devices.

In any case, the materials used in commercially available twisted nematic effect displays must exhibit a nematic phase down to about -10°C or below. In other words, the mixture of cyano and non-cyano materials to be used in twisted nematic displays must not exhibit a single shot smectic phase at this temperature.

Conventional wisdom in the art is that the slope of the light output vs. voltage curve is generally lower for liquid crystal materials such as n-alkyl or n-alkoxy groups than for congeners with shorter chain end groups in twisted nematic displays. It is believed that the use of compositions containing components with long chain end groups can lead to instability. However, it is also recognized in the art that compounds with relatively long chain end groups generally have a greater tendency to form smectic phases than congeners with relatively short chain end groups. There is.

Preferably, the cyano material used in the twisted nematic disk clay comprises a cyanobiphenyl class of compounds, such as 4-n-alkyl-4'-cyanobiphenyl. Among other reasons, the above compounds are preferred because the slope of the light output versus voltage curve is relatively steep. However, these compounds exhibit a tendency to form injectable smectic phases in mixtures with non-cyano materials.

Therefore, given non-cyano materials are often utilized in conventional electro-optic displays.

It is particularly important to be able to form mixtures with widely available commercially available cyano materials, especially materials containing cyanobiphenyl compounds, and also to ensure that individual compounds are able to form mixtures with the cyano materials that have the least tendency to exhibit smectic phases. It must form a compound of

Preferred compounds of formula I have little tendency to form single-shot smectic phases, and therefore the compounds of the invention can be used as one non-cyano material in mixtures suitable for use in multiplexed twisted nematic displays. By using long chain cyano moieties, which are preferred compounds, the threshold slope can also be improved. For example, a mixture of 9 g of a mixture which is a ternary eutectic mixture of a compound of formula I and 10 g of 4-cyano-42-ethylbiphenyl;
or the ternary eutectic mixture 75% by weight and trans-4-n
-Propyl-1-(4-cyanophenyl)-cyclohexane in a mixture with 25% by weight showed no injection smectic phase even at -40°C. This property is extremely advantageous when formulating mixtures that meet the requirements of the automotive industry, such as rapid switching at low temperatures. Smectic phases, especially the tendency to form smectic phases, are extremely advantageous. In order to minimize the total number of carbon atoms in R8 and R2 in formula (III) (particularly when these groups are n-alkyl groups), especially in RA and RB in formulas I and Ib, the total number of carbon atoms is 10.
The total number is preferably less than 4 to 8.
It is. Preferably, the number of carbon atoms in each group is 5 or less.

formula! In the case of mixtures containing compounds of formulas Ia and Ib in which the terminal groups RA and RB are n-alkyl groups, the number of terminal carbon atoms in each compound is preferably from 4 to 8. As in the case of mixture E described above, it is more preferable that the number of carbon atoms in each terminal group of each compound differs within this range.

The compound having the formula (2) can also be used in fields other than electro-optical devices where it is preferred to use nematic or chiral nematic liquid crystal compounds. For example, a metal compound having formula I may be used, for example in British Patent Publication No. 208
It may also be incorporated as a high-clearing point component of temperature sensitive e.g. thermochromic materials used in the fields described in U.S. Pat.

Compounds of formula I may be prepared by synthetic routes involving procedures known per se. This route is entirely new. For example, the following routes 1 and 2 can be used.

Route I R2 is H, alkyl or alkoxy R, -+R3 Route 3 or F root 4' where R8 and R2 are the same or different alkyl groups, and -6Σt<E)- is 4 which is fluoro-substituted at the side position.
, 4'-biphenylyl.

Kanyu J R2-@-R2, X-H, Y! FR3-AlkylPR12-Alkyl, alkoxy or hydrogen R2-Shau%v X=-F, 'Y=H.

R1 building CH2, CHK
．． The starting materials for Parts 7 and 8 are from pending UK Patent Application No. 831.
No. 9849.

The compounds of formula I have a relatively small dielectric anisotropy, and in particular liquid crystals with positive or negative dielectric anisotropy (greater than the compounds of formula ■) to give mixtures with suitable dielectric anisotropy. It can be added to substances (materials) (these are known and referred to herein as "positive substances" or "negative substances," respectively). As is well known to those skilled in the art, the dielectric anisotropy of liquid crystal materials is necessary to obtain electro-optical operation (for a given amplitude r
The sign of the liquid crystal material (in terms of JJJ number) is chosen depending on the type of electro-optical device in which this material is used.

A compound with an appropriately low melting point is preferred as the highly dielectric anisotropic compound. For example, the following known classes of compounds are suitable as positive substances:

R-〇-(Lee CN formula na RA(l → σ) penN 2nb ~gu:pa) OCR formula Inc RA+CH,CH,shaCN formula I'd R←6su←(niX(N formula IIf RA-〇-(KotoCN Formula I [g R, -6)-00,0+CN Formula IIhR-<2)-c
o, o+CN Formula 1 where each R is n-alkyl or n-alkoxy, and each RA is n-alkyl.

Alternatively (or in addition), the compound of formula ■ may be, for example:
Other compounds with low dielectric anisotropy can be added to lower the melting point, viscosity of the mixture or to improve diversity. Examples of such other compounds include the following classes of compounds:

R heel bar) R2md R, ◇◇-(D←Q formulalll5 R-guri←CH-N+R” 2mk R-4U→se→(D←R1 formula I [[1 Here, each R is each R is n-alkyl or n-alkoxy, each R is each n-alkyl, each R is each n-alkyl, n-alkoxy or hydrogen, X-H
or F and Q-halogen such as C1 or F.

Thus, one or more compounds of formulas 11a to 11a to
Optionally, more than 2 ma to mn compounds can be added to one or more compounds of 1.

Furthermore, the above mixture also contains other highly clear A (clear-1n).
g paint ) compounds may be included. Such compounds include, for example, selected from the following:
There are more than ff compounds.

R,0OOCN Formula IVa RA Momo-000-[Stock] αON Formula 1%'bR% c
o , o←S) → $N formula IVcR, (ΣBefusa) −
(S←CN Formula IVdR%co, o$CN Formula ■e R (baka) R formula I%'f where R, RA, X and Y are as described above.

Certain other known additives, such as chiral additives of the following formula, may be incorporated into the mixture if desired.

Rd-+0M, Rbe)0N where R6-(+)-2-methylbutyl, RD-(+)
-2-methylbutoxy.

The liquid crystal materials obtained by blending the compound of formula (1) with other compounds of the above-mentioned type are as follows.

(1) Positive nematic materials for use in twisted nematic effect devices, including diversified devices; examples of such devices are described below.

(1) Negative materials, preferably also containing pleochroic dyes, for use in Fr6e effect devices (negative nematic type): In such devices, the molecular alignment is changed from the homeotropic organization (OFF state) by an electric field to about - organization (ON state), examples of which are described below.

(11) Fr6edericksz (positive nematic type) whose molecular arrangement is converted from a homogeneous structure (OFF state) to a homeotropic structure (ON state) by an electric field
Positive nematic materials used in effect devices, preferably also containing pleochroic properties; OV) suitable resistivity (approximately 10' ohm-cm)
Negative material that is cholesteric (chiral nematic) with
Focal conic scattered from
) Used in cholesteric storage mode devices that are converted to tissue (ON state) (V) Residual material that is cholesteric, preferably also containing pleochroic dyes; Used in cholesteric-nematic phase change effect devices (positive contrast type) that change from a structure (OFF state) to a strongly scattering twisted uniform structure (ON state).

(vO A positive material that is cholesteric, preferably also containing a pleochroic dye; a cholesteric-nematic phase in which the molecular arrangement is transformed by an electric field from a scattered atomic organization (OFF state) to a clear homeotropic organization (ON state) Used for change effect devices (negative contrast type).

←Yu Nematic material with appropriate resistivity (approximately 10'ohm-cm); suitable for dynamic scattering effect devices in which the molecular arrangement changes from a clear homeotropic structure (OFF state) to a diffuse scattering structure (ON state) by an electric field. use.

&i) The antistatic anisotropy of the material is positive (OFF at low frequencies)
Nematic materials for use in two-frequency switching effect devices (which may be twisted nematic effect devices) that change from a negative (ON state) to a negative (ON state) upon application of a high frequency electric field; (4) described in co-pending British patent application no. Compatible with other devices.

The construction and operation of the devices described above and the general types of materials suitable for their use are known per se.

When using 'tL crystal materials in twisted nematic effect devices, cholesteric-nematic phase change effect (negative contrast type) devices or Fr1edθricksz effect (positive nematic type) devices, these materials preferably contain the following components: . That is, it contains at least 49,111 compounds of formula I (component A) and at least one compound of formulas 11a to 1 (component B), and optionally one or more of the following.

Component C: one or more compounds of formulas ma to l1ln; component D:
One or more compounds of formulas IVa to 1; Component E: 1 m or more of Kira I additive.

Twisted nematic effect and Freeder 1cksz
In the case of (positive nematic) effect, the proportions (9;) of the various components of the material are as follows (total to 100 yen):

Component A: 5 to 95 weight (typically 5 to 75 weight) Component B: 5 to 95 weight (typically 10 to 50 weight) Component C: θ to 90 weight (typically Component E: 0 to 5 weight ratio (in terms of weight, θ to 1 weight weight phase change (negative contrast) type), the following proportions may be used:

Components A-D: Above ratio Component E: 2 to 20 weight units (typically 4 to 5 weight units).

For Freedericksz (positive nematic) and phase change (negative contrast type) effects, it is preferred to add pleochroic dyes to the liquid crystal material forming 1.5 to 15 ml of the total mixture. Suitable dyes are listed in British Patent Application No. 2
No. 081736A, No. 208219A and No. 2093
No. 475A. Typically, each dye compound added makes up 1 to 3 weight parts of the total mixture.

Liquid crystal mixtures containing compounds of formula I may be formed in known manner. For example, appropriate weight proportions of the components may simply be heated together to form an overall isotropic liquid (e.g., about 10
0℃).

To provide an example of a more general mixture which is an aspect of the invention, at least one of the compounds of formula (The actual application will depend on the properties of the mixture).

IR()◇XY1 1n RO$y.

IV ROOOOY.

v++ FaXco, o-x-y.

vllll+o, o-x-y.

x + Ro-CX Politics I)y 1 xil R+C’= C building Y1 Xlil Ro8c=c+y1 XIV R building'CH-N-C)-Y.

)0/RO building CH-N (door.

Mausoleum R-min α) □-y, ;m+wl, 2 )4111 R% co, o-xl-y.

Xti+i RO$CO, O-X, -Y.

x+x R-(+-co, o-x, y.

xx R building CH, O (door.

xXI R(EE)4ON 2,2,2) octane ring, X is 1,4 phenylene group -(D-,4,4'
-biphenylyl group X) -12,6-naphthyl group-6
- or trans-1,4-disubstituted cyclohexane ring, Y is CN, R', agen or CO, 0-X-Y
(yl is CN, R' or OR', and R and R' are alkyl groups. Derivatives in which H of one benzene ring of the above compound is substituted with a halogen, such as F, may also be used.

Preferably, one or more compounds of formula
Weight ratio to weight acid.

In a second aspect of the invention, a liquid crystal device comprises two electrically shielding substrates, at least one of which is optically transparent, a layer of liquid crystal material sandwiched between the substrates, and a layer of liquid crystal material sandwiched between the substrates; comprising an electrode capable of applying an electric field across the layer of liquid crystal material to produce an electro-optic effect therein, characterized in that the liquid crystal material consists of or contains a compound of formula I above. do.

This second plane device may be a twisted nematic effect device, a cholesteric-nematic phase change effect device, a F
r6edericksz effect device or 2-frequency-
These may be configured in a known manner, as well as any of the other devices mentioned above.

Various methods of using compounds of Formula I in these devices are outlined above and will be apparent to those skilled in the art.

Examples relating to the preparation and properties of compounds having formula I are described below. The following abbreviations are used in the examples.

mp - Melting point - N - Transition temperature from crystal to nematic liquid crystal N - 4 - Transition temperature from nematic to isotropic liquid bp - Boiling point S Nichismectic SA Introsmectic A 3 - N - Transition temperature from smectic to nematic -8 - Transition temperature from crystalline solid to smectic ch - I - Transition temperature from cholesteric (chiral nematic) to isotropic liquid - ah - Transition temperature from crystalline solid to cholesteric, Q - ch - Smectic Transition temperature from to cholesteric Δn −589, Birefringence η at 20°C measured at 6 nm Extrapolated matic viscosity at 20°C measured in clear liquid with polishing material ZL11132 (available from EMerck) glc - Gas-one-liquid chromatography Example 1 1-(trans-4-n-pentylcyclohexyl)-2-(4-ethyl-2-fluoro-
Preparation of 4-(trans-4-piphenyyl)-ethane Step 1 of 1: 4-(trans-4) by Friedelkraff acylation
Preparation of -n-pentylcyclohexylacetyl) -2'-fluoro-4'-ethyl-biphenyl 4-ethyl-2-fluorobiphenyl (13,0 g) was dissolved in aluminum trichloride (9.0 g) in methylene chloride (aom).
, 5411) once to the stirred suspension, then trans-
4-n-pentylcyclohexylacetyl chloride (t
A solution of sj+) in methylene chloride (3 od) was added dropwise over 30 minutes. After stirring at room temperature for 3.5 hours, the reaction mixture was placed on ice (
250f? ) and hydrochloric acid (25F!Ll),
The product was poured into 350 g and then 250 ml of petroleum ether (b
p60-80°C). Combine the extracts and wash with water (t
sod) L, dried over anhydrous sodium sulfate and evaporated to dryness. The residue (2a, 5Ii) was crystallized from industrial methylated spirits at 50'C to give 4-(trans-4-n-pentylcyclohexylacetyl)-27-fluoro-4'- with mp 72-73°C. Ethylbiphenyl 1
3.2F (yield B, 1.5%) was obtained.

Analogues of the products of step lal shown in Table 3 are:
Prepared in a similar manner from similar starting materials.

Table 3: 1-(trans-4-n-pentylcyclohexyl)-2-(4'-ethyl-2'-
Preparation of fluoro-4-biphenylyl)-ethane The ketone (13,0,9,l, prepared in step 1)
99 hydrazine hydrate (131R1), potassium hydroxide (7g) and digol (100at)
4 to 120-125°C under a reflux condenser with stirring.
The mixture was heated for an hour, after which the excess hydrazine hydrate was distilled off and the temperature was raised to 175°C. The mixture was heated to reflux for 16 hours, then cooled and poured into 5ooIi of ice water. Organic products were converted into petroleum ether/L/(bp60-80″, 2
0 ml), the extract was washed with water, dried over anhydrous sodium sulfate and evaporated to give a yellow oil (1a, s I
)was gotten. (bp, 60~
(80° C.) (aom) and adsorbed onto a column of basic alumina (4011) on silica gel (28 g).

Elution with petroleum spirits (550 mJ) gave the product (xo, 19) as a nematic oil, which was crystallized at -25°C from industrial methylated spirit (aom).

1-() lance-4-n-pentylcyclohexyl)
-2-(4'-Ethyl-2'-fluoro-4-biphenylyl)-ethane is a colorless crystalline solid (8
, 3g, yield 67 yen). Also, with supercooled liquid, 2
The viscosity and birefringence at 589.6 nm measured at 0°C were 32.6c8t and 0°145, respectively.

Analogues of the products of step lbl shown in Table 4 were prepared by fanminlon reduction of the appropriate ketones in the manner described in step lbl.

Table 4 Formula: % Formula % Potassium hydroxide (105Ji'), Digol (900
d) and xylene (150rrLl) with stirring.
It was heated to 25°C for 16 hours, after which the xylene and excess hydrazine hydrate were distilled off until the internal temperature reached 165°C. The mixture was heated to reflux for 3 hours, cooled to 406
Pour into water 51.

The product was converted into petroleum ether (bp60-80°, 2Xl/)
The extract was washed with water, dried over anhydrous sulfuric acid, and evaporated. 4-ethyl-2-fluorobiphenyl (9s 11, theoretical factor 68) has a bp of 130
'10. It was a colorless oil from S. other 4-alkyl-
2-Fluorobiphenyl was produced by the reaction of 2-fluoro-4-biphenylylmagnesium bromide with n-alkyl bromide, and was a colorless oil with the properties shown in Table 5.

Table 5 Methi/I/ 58 yen 120n6 torn-propy/l/ 61.5 qblo s7 o, t 5 to
rrp-buty #65% 160-7 torrU-pentyl 694 152-0.3 torr step l
The usefulness of the product is illustrated in the following mixture containing the product of bl.

In the case of la + cyanopyphenyl component, 51 units 41 cyano-4'-n-pentylbiphenyl 25 units 4-cyano-4'-n-hebutylbiphenyl 16 units 4-cyano-4'-n-octyloxybiphenyl 8 units 4 - Commercially available liquid crystal product i from BDH Chemical Company containing cyano-4'-n-benzene-p-terphenyl! Various properties of a solution of jE7 added to the product of step IBL, herein designated as compound A, were measured and these were compared with the corresponding properties of E7 alone. The abbreviations in the property column shown in Table 6 are as above or below: TF=Temperature at which the liquid crystal material can be maintained for 12 hours without freezing Table 6 Property comparison N-I ('C) 6Q, 5 69.5-71. OTF
('C) -10-25 Δn O,2250,210 η(cst) 4 o, Oa 7.5 All four properties shown in Table 6 were improved by adding compound A to E7. There is.

Furthermore, as mentioned above, the mixture of compound A and E7 is (E7
) showed no smectic phase even when the temperature was lowered to -20°C.

[bl P In the case of the CH component, commercially available ZL11132 (E, sold by Merck & Co., Ltd.) has the following weight composition of 20 weight units A and 80 weight units.
A mixture (mixture B) was prepared using the following.

24qb) Lance-4-1! -propyl-1-(4-
cyanophenyl)cyclohexane 36 units trans-4-9-pentyl-1-(4-cyanophenyl)cyclohexane 25 units trans-4-9-hegtyl-1-(4-cyanophenyl)cyclohexane 15 units trans-4-pentyl ZL11132 containing -1-(4'-cyano-4-biphenyly/I/)cyclohexane compound A and ZL not containing it
11132 were measured and compared using the same method as above. The results are shown in Table 7.

Table 7 N-I (“C) 71.3-74 79.5-82.5
T, (''C) -6-25 Δn O, 1400, 140 η (cst,) 27.5 26.5 According to Table 7, the above three properties of ZL11132 were improved by the addition of Compound A. The fourth property, birefringence, is at the same level.

Furthermore, the previous mixture of Compound A and ZL11132 did not show a smectic phase even when the temperature was lowered to -20°C.

tC1 fast-switch H) mixture (mixture C) was prepared with the following weight composition: 9.9596 4-cyano-42-ethylbiphenyl 4.98 trans-4-n-propyl -1-(4-
cyanophenyl)-cyfurohexane 4.98 4-cyano-4'-n-furobylbiphenyl 6.96 1-(上之Z晟-4-!1-Propylcyclohexyl)-2-(4'-cyano- 4-biphenylyl)- ethane 2.981 4'-cyano-4-biphenylyl 4'-hebutyl-4-pinenylcarboxylate 18.11 1-(trans-4-!!-propylcyclohexyl)- 2-(4'-dan-propyl-2'-fluoro-4-biphenylyl)-ethane24, asqb t-()lan-4-9-propylcyclohexyl)-2-(4'-n-pentyl-2' -Fluoro-4-biphenylyl)-ethane 27.17 1-(trans-4-X!-pentylcyclohexyl) -2-(4'-ethane-2'-fluoro-4-biphenylyl)-ethane 0. 48. (g)-4-Cyano-4'-(2-methylbutyl)-biphenyl It was found that the above mixture has the following properties: -N does not freeze even when stored at 35°C for one month. -I: 102℃ Multilayer OIT: 20℃, 589.6 n+te 0.1735
Threshold voltage: 2.85 volts Measured by driving an electro-optic cell at -20°C with 8 volts RMB Ton and Toff are the times required to turn the cell ON and OFF, respectively, and the cell transmittance from 10 to 90 yen. It was measured with

Mixture with minimum temperature change in tdl threshold voltage The mixture shown in Table 8a was left for 3s, and its properties were determined by thickness? Measurements were made in a twisted nematic electro-optic cell with an am liquid crystal layer.

Table 8a Liquid crystal mixture D210 6 90'fiE 3.67 0.15D
3 5 Sorry PCH395 E5.56 0.13D410
Section PCH390 Section F 4.09 0.16 In Table 8a,
E represents a ternary eutectic mixture of the compounds of formula I above; K
6 is 4-cyano-4'- obtained from BDH Chemical Company.
n-ethylbiphenyl, DCH3 is trans-4-0,n obtained from E.Merck, Dermstat.
-Propyl-(4-cyanophenyl)cyclohexane.

2 is the threshold voltage at 20° C. (necessary because the transmittance of the cell is 90), and T is the temperature.

Example 2 1-(trans-4-n-propylcyclohexyl>-2-(4'-(4-)trans-n-
Propylcyclohexyl)-2'-fluoro-4-biphenylyl]-ethane production step 2-1: 1-2-(fluoro-4-biphenylyl)-4-n-
Propylcyclohecan-1-ol 4-bromo-2-
Diethyl ether (1) of fluorobiphenyl (50I)
5 oml) solution number rnl, magnesium shavings (S,
ag) and diethyl ether (25m) under nitrogen. The reaction was started by adding iodine crystals and heating. The remainder of the 4-promo-3-fluorobiphenyl solution was then added at a rate sufficient to maintain vigorous reflux. After boiling for 1 hour, the solution of Grignard reagent was
℃, and then a solution of 4-n-propyl microhexanone (27,91) in diethyl ether (75 ml) was added over 30 minutes. After stirring for 1 hour, the mixture was poured over 15% hydrochloric acid (21) to remove the product. ether (2 x 3001
1Il). The combined extracts were washed with water, dried and evaporated. The residue was dissolved in petroleum ether (bp6g-80
mp45-72° (
1-(2-fluoro-4-biphenylyl)-4-propylcyclohexan-1-ol (isomer ratio ao, s: a by glc) as pale yellow crystals of 37.2 g, theoretical amount 61.2 9.4) was obtained.

Step 2b1: 1-(2-fluoro-4-biphenylyl)-4-n-
70 pills microhex-1-2 phosphorus pentoxide (4019
) of the product of step 2al (35,5Ii) in cooled stirred toluene (5o.

--) added to the solution. The mixture was kept at room temperature for 4 hours and then added to water 11I. After stirring for 30 minutes, the organic layer was separated and the aqueous layer was re-extracted with toluene (aoomJ). The combined extracts were washed neutral, dried and evaporated to dryness under reduced pressure. The yellow residue was crystallized from ethanol (2,00m) at 5°C to give 1-(2-7/l/l/l with mp 60.1-60.4°C).
(4-biphenylyl)-4-11-70 pyl-cyclohexa-1-2, 729.31 (theoretical amount of 88 yen)
I got it. The product had a purity of 99.54 by glc.

Step 2cl di2-fluoro-4-(4-n-propylcyclohexyl)-biphenyl (isomer mixture) corresponding cyclohexene (7,9) from step 2hl, 5 on charcoal
Add palladium (0,711) and ethanol to 1. The mixture was stirred at 40° C. under a hydrogen atmosphere until hydrogen absorption stopped. The catalyst was separated from the P and the solvent was evaporated to give a product which was an isomer mixture of cis-isomer 64.51 and trans-isomer 34.51 as determined by glc.

A dimethylformamide (soy) solution of the isomer mixture (9 g) prepared as above was added to sodium hydride (soy).
2,4II) in dimethylformamide (50ml). The mixture was heated and stirred at 60°C for 20 hours,
Next, first add eta/-# (1oomJ) and then add water (
11). The product was converted into petroleum ether (bp6o~8
Extracted at 0° C. (zx2oomJ), washed with water, dried and evaporated to dryness. The residue (9,11) consists of the 83 trans isomer and is purified by crystallization from ethanol (30°C) at 5°C to give a Tryx product (%mp 69-70°C).
5,611g1c with a N degree of 99.51) was obtained.

4-()trans-4-η-propylcyclohexylacetyl)-2'-fluoro-4'-(trans-4-n-
The product from step 2cl (propylcyclohexyl)-biphenyl was reacted with trans-4-n-10vylcyclohexylacetyl chloride as described in step 1a1. 4-() Lance-4-n
-propylcyclohexylacetyl) -21-fluoro-4/) lance-4-n-propylcyclohexyl)-biphenyl in petroleum ether (bp60 80')
(yield: 63%). The product had the following properties: -8-90''; 5A-N = 179-180°;
．． It was Section 8.

The product of step 2dl and other examples of compounds of formula IK that can be similarly prepared are summarized in Table 8b below @ Table 8b Formula: %Formula %: () lance-4-n-propylcycloheΦ The product of step 2 dl (59) and trans-4-n-propylcyclohexylacetyl chloride (a, 1zIi) in methylene chloride (30 FJ) were dissolved in aluminum trichloride in methylene chloride (1 smJ) over 40 min. ) was added to the stirred suspension at 10°C.

After the temperature reached room temperature (20°C), the mixture was stirred for 4 hours. It was then poured into water (1501 nl). continue,
(bl) 60-80°, 2X
2Q0ml). This was washed with water, dried over anhydrous sodium sulfate, and evaporated to dryness to give 7.719 yellow solid. The pure product was obtained by recrystallization from petroleum spirit at 10°C. The yield was 4.9JF [639! +) and the line section was 99.8.

Step 2f1: 1-() lance-4-n-propylcyclohexyl)-
2-[-2'-fluoro-4'-()! Lance 4-n
-propylcyclohexyl)-4-biphenylylcethane (4,8,9) prepared in step 2al, 99
Hydrazine hydrate (5 g), potassium hydroxide (2 g) and digol (300 g) were mixed under a reflux condenser with stirring for 12 g.
It was heated to 0-125°C for 5 hours and then the temperature was increased to 180°C by distilling off the excess hydrazine hydrate. The mixture was heated to reflux for 20 hours, cooled and poured onto 300 d of water. The organic product is converted into petroleum spirit (bp 60-
Extracted with a 4:1 solution of 80/methylene chloride (2X2Q-), washed the extract with water, dried over anhydrous sodium sulfate,
Evaporation gave solid 4.611. This was dissolved in petroleum spirit (bp 60-80°C) (60 g) and adsorbed onto a column of basic alumina (10 g) on silica gel (51). Elution with petroleum spirit (150 ml) yielded the crude material 4. 3g of product was obtained.Next, recrystallization from petroleum spirit yielded 3.4g of product (purity: 99.9) in a yield of 73%.
obtained at K-N-106~108°C, N-I=244
It was ℃.

Example 3 Preparation of 1-(trans-4-n-propylcyclohexyl)-2-(2-fluoro-4'-n-propy/l/-4-biphenylyl)-ethane by route 3 Step 3a1: 2 -Fluoro-4-(trans-4-n-propylcyclohexy/I/)biphenyl 4-bromo-2-fluorobipheny A/(38.1 g) in tetrahydrofuran (6
0 ml) solution was diluted with tetrahydrofuran (2 ml) over 20 minutes.
Magnesium shavings (4II) suspended in omz)
In addition, the reaction was initiated by addition of iodine crystals and warming as usual. The Grignard reagent was combined with trans-4-propylcyclohexylacetyl chloride (4079) and tetrahydro7rane of cuprous chloride (O04#) (20
It was added to the 0aA solution over 90 minutes at -60°C with stirring. After being allowed to warm up to room temperature for 2 hours, the mixture was decomposed with water and the product was dissolved in petroleum ether (bp 60”80
°). The compound was recrystallized twice from ethanol at 5°C to give a product (20,6
g, 40 times the theoretical amount). The product has a glc of 9
9. The purity was s4.

Step 3b1: 1-(2-fluoro-4-biphenyly/I/)-2-
() lance-4-n-propylcyclohexyl)-etha/ The ketone prepared in step 3a was reduced as described in step 1bi to give the product in glc+, sl purity in 71% yield. The product is mp-4e, 5-4
8" (N-IC37-a 9.8')).

1-(2-fluoro-4'-propionyl-4-biphenylyl)-2-()lans-4-n-propylcyclohexyl)-ethane 4'-propionyl group is added to the product of step 31)1 in step lal was introduced by the procedure using the Friedel-Craf reaction described in . The desired product was obtained in 90% yield and 99.7% purity by GLC. The product had the following properties: ni-N 74.4-74.8"N-I-165,4-165.8"Step 3d1
: 1-(2-Fluoro-4'-n-propyl-4-piphenylyl)-2-()lans-4-n-furovircyclohexyAI)-ethane The ketone prepared in step 3C1 was described in step lbl Reduction was performed using the fanminolone method to obtain a product with a yield of 3o1 and a purity of 99.8 by GLC. The product had K-N-s9''N-1-108°.

The following analogs were prepared in a similar reaction.

Table 9 Preparation of a compound of formula: according to Route 4 above Step 4a1: Friedelkraff acylation using % 2-fluorobiphenyl in place of 4-ethyl-2-fluorobiphenyl and further present in methylene chloride except that the molar amount of aluminum trichloride used is twice the molar amount of trans-4-n-pentylcyclohexylacetyl chloride.

The same procedure as step lal was carried out.

Step 4b1=Fang Minglong reduction was performed essentially as in step 1b1 above.

Compounds of formula If with other alkyl groups may be synthesized in an analogous manner.

Example 4' Preparation of a compound of formula: following route 4' The following steps 4'81 to 4'e1 are each step 4'
This is a specific example of 8 to 4'e.

Step 4'al: Preparation of the Grignard reagent This step was carried out in a similar manner to the preparation of the Grignard reagent in step lal, ie the starting material 4-promo-2-fluorobiphenyl.

Step 4'bl: The heathering step consists of combining trans-4-n-butylcyclohexylacetyl chloride and the Grignard reagent produced in step 4'a1 in the presence of tetrahydrofuran at a temperature of -7
At 8°C, F 5ato , M Inoue ,
K Oguro and Msat.

is T@trahedron Letters (197
9) A conventional reaction was carried out according to the method described on pages 4303-4306.

Step 4cl: The i principal step was performed in a similar manner to the reduction in step lb1. The compound of formula: had the following properties: C-1-44°C N-I-(36,6°C).

Step 4'd1: Friedelkraff acylation reaction This step was carried out in a similar manner to step lal. The compound of formula: had the following first-order properties: It was done in a similar way. The product was a compound of formula:

Compounds of formula If with other alkyl groups may be synthesized in an analogous manner.

Compounds that can be synthesized by the methods described in Examples 1 to 4 and 4' are summarized in Tables 10 to 13, respectively.

Table 10: formula: R1R.

CmH2m” I CpH2p + 1CInH2m+
1 oCpH2p+1 CmHgm+□H In the formula, m is an integer of 0 to 12, and p is an integer of 1 to 12.

Plate ± construction: Formula: % formula % In the formula, 1m is an integer from 0 to 12, and p is an integer from 0 to 12.

Formula: % Formula %: Formula: RI R2X Y CmH2m+x CpH,p+, F HCmH2m+
I CpH2p+I HF In the formula, %m is an integer from 0 to 12, and p is an integer from 0 to 12.

Example 5 1-(trans-4-n-propyl A) according to route 5
・cyclohexyl) -2-(2'-7/I/ oro-
Production of 4'-n-70 pyl-p-1-phenylyl)ethane Step 5 a1: Production of 3'-fluoro-4-propyl-p-terphenyl 4-(4-n-propylcyclohexenyl)- 2-fluorobiphenyl (200) toluene (120rn))
The solution was diluted with 2,3-dichloro- with stirring over 25 minutes.
5,6-dicyatho-1,4-benzoquinone (DDQ) (
3411) in toluene (200, ml). The temperature rose from 19°C to 24°C during the addition, after which the reaction mixture was heated to reflux (114°C) for 3 hours. The reaction mixture was cooled, filtered, the r liquid and toluene wash (100 ml) combined, and then washed with saturated isomeric sodium bisulfite solution (2501/). The organic extract was further washed with water (2×250 WLl), dried and evaporated to dryness to give a brown residue (20,11). The residue was dissolved in methylene chloride (1
2 omJ) and adsorbed onto a column of basic alumina (soli) on silica gel (aoJil).

Elution with methylene chloride (4som) and evaporation of the solvent gave an off-white solid (149).

This was recrystallized from ethanol (golIL7).
A white crystalline material (12,81) with p75-77°C was obtained.

Step 5bl: 4-() lance-4-n-propylcyclohexylacetyl)-2'-fluoro-4''-
Propyl-p-terphenylnoproduced methylene chloride (1s
The mixture of 3'-fluoro-4-propyl-p-terphenyl (4II) and trans-4-n-propyl-cyclohexylacetyl chloride (2,811) in d) was added to the chloride of anhydrous aluminum chloride (2,021). Methylene (1oWtl) was added to the cooled (10°C) stirred suspension over 20 minutes. After the addition, the reaction mixture was warmed to 23°C,
Stirred for 18 hours. The obtained solution was diluted with a 10% hydrochloric acid solution (1
0om) followed by petroleum spirits (bp60-8
The organic extract was then washed with water (120 mJ), dried over anhydrous sodium sulfate, filtered and then evaporated to dryness. A yellow oily solid (7
g) was dissolved in methylene chloride (50 WLl) and adsorbed onto a column of basic alumina (20 g) on silica gel (10 g). Elution with methylene chloride and evaporation of the solvent gave a yellow solid (sII). Recrystallization from methylene chloride (10,7) gives a crystalline material (2,51
) was obtained, and the material had the following properties: -8-120-126 S-N 200-204°C N-1-225-227°C.

Step 501: Preparation of 1-() lance-4-n-propylcyclohexyl)-2-(2'-7#, t-rho4''-propyl-p-4-terphenyl)ethane The ketone ( 1,s+7)99%
Hydrazine (2 ml), potassium hydroxide (119) and digol (3 od) were heated to 120°C with stirring for 17 hours, then the temperature was raised to 180°C by distillation of the excess hydrated hydrazine/digol mixture. The resulting solution was heated to reflux at 180-182°C for 5 hours, then refluxed for 6 hours.
Cooled to 0°C and poured onto ice water (roog).

(bp60-80・150
m/) and methylene chloride (3Op),
Wash with water (2X 50 TrLl), dry and evaporate the solvent. The yellow residue (1,79) was dissolved in a 1=1 mixture of methylene chloride and petroleum spirit (bp 60 80) 2 (
B+J and adsorbed onto a column of basic alumina (6Ii) on silica gel (4fI). Elution with the same solvent mixture (70 mJ) and evaporation of the solvent gave a crystalline material (1,31i'). Petroleum Sviritu) (
Recrystallization at 10°C from bp 60-80.7-) gives a white solid (1 g) with the following properties: I got it.

as shown in one or more of the routes or similar route tables above;

Table 13a.

Formula: %Formula%F In the formula, -m is an integer from 0 to 12, and p is an integer from 1 to 12.

In the following examples, examples 6-8, the terminal groups R1 and R
The preparation of compounds of formula I in which one of 2 is chiral is described.

Example 6: (+)-1-() Lance-4-n- according to route 1
Butylcyclohexyl→-2-(2'-fluoro-4'
Preparation of -(2-methylbuty)-4-biphenylyl]-ethane Step P: Preparation of (+)-2-fluoro-4-(2-methylbutyl)-biphenyl 4-bromo-2-fluorobiphenyl (9oF) of? 10m of trahydrofuran (9om) solution was mixed with magnesium turnings (9,aII) and tetrahydrofuran (2o
m) under nitrogen. The reaction was started by adding a single crystal of iodine and heating. Then 4-bromo-2
-The remainder of the fluorobiphenyl solution was added dropwise over % time. After heating under reflux for 1 hour, the solution of Grignard reagent was
Cooled to ℃. 2-methylbutylphenylsulfonate (150,9) in tetrahydrofuran (140+a/)
Add 10 g of solution to the reaction mixture, then add cuprous chloride (3 g) to the reaction mixture.
II) was added. The remainder of the phenyl sulfonate solution is
Added over 0 minutes. The temperature of the resulting gray/green reaction mixture rose to 45° C. and was then heated for 1 hour to raise the temperature to boiling point. The reaction was allowed to cool to room temperature, then 20
A volumetric volume of hydrochloric acid (2,57) was added and the product was extracted with methylene chloride (2X5001d). Wash the organic layer with water (2X5
After drying with anhydrous sodium sulfate (1511) and evaporation of the solvent, an organic liquid residue was obtained. Upon cooling, a white solid crystallized from the residue. After filtration, the residue (ss
, 6#) was fractionally distilled under reduced pressure (o, s torr ) to obtain a colorless liquid (65Ji'). It had a purity of 98.84 according to GLC. bp is 0.5torr
The temperature was 120°C. Optical rotation is +14.62” (solvent)
Met.

Step 1 R2: (→-4-(trans-4-n-butylcyclohexyl-acetyl) -2'-fluoro-
Preparation of 4'-(2-methylbutyl)biphenyl(+)-2-Fluoc in methylene chloride (20td)
+-4-(2-Methylbutyl)biphenyl (1o#) and trans-4-n-butylcyclohexylacetyl chloride (9,4g) f)8 compound was added over 20 minutes to anhydrous aluminum chloride (6,x,?). ) Methylev chloride C20
m1) added to the cooled (5-10°C) stirred suspension. After the addition, the reaction mixture was allowed to warm to 23° C. and stirred for 17 hours. Add the resulting solution to water (200+n/),
Next is petroleum spirit (bp60-80'xsomj+
toom/). The organic extract was then washed with water (2
00 mJ)t, dried over anhydrous sodium sulfate (51i) and evaporated. The yellow crystalline residue (17.9#) was recrystallized from ethanol-/' (35m/) at 25°C to give the product (14.8g, yield 85%). The product is mp
71.4-72.1°C, actual Ch-I (68,
5-68.8°C), and the purity by GLC is 99.
It was 5%.

-butylcyclohexyl)-2-(zr-fluoro-4
Ketone (14,411), hydrazine 99-hydrazine hydrate (14,41114), potassium hydroxide (7,2
, 9) and Digor (120x/) were heated to 125° C. for 4 hours under a reflux condenser with stirring.

After that, excess hydrazine hydrate is distilled and the temperature is reduced to 175℃.
It was raised to . The mixture was then heated to reflux for 17 hours, cooled to 60° C. and poured onto ice water (sooy). The organic product was dissolved in petroleum spirit (bp60-80°, 2xz
ood) and washed the extract with water (2,X 200 g)
1, anhydrous sulfuric acid). Evaporation of the solvent gave a yellow oil (14,11). This was dissolved in petroleum spirit (bp 60-80”, toom) and adsorbed onto a column of basic alumina (sob) on silica gel (20jl).
) and evaporation of the solvent yielded a colorless oil (11,7
, 9) were obtained. Propan-1-ol (
When crystallized from 7omb), a xylic nematic substance 9
．． A yield of 4.9 (yield: 68) was obtained. This substance is glc
According to the study, the purity was 99.8%.

The properties of the products were as follows: 5-Ch-6°C Ch-I 72°C Helical molecular pitch 0.23 microns Example 7 1-(trans-4-ethylcyclohexyl) by route 1 above. -2-(2'-fluoro-4'-(2-methylbutyl)-4-biphenylyltoethane production step xa3: 4-()lans-4-ethylcyclohexylacetyl)-2'-fluoro-4'- Preparation of (2-methylbutyl)biphenyl This step was carried out in a similar manner to step 1a2 using 4-ethylcyclohexylacetyl chloride as the starting material.

The product had the following properties: mp -40-=42°C Practical Ch-I mo(27,5°C) cyclohexyl)-2-(2'-fluoro-4'-(
Preparation of 2-methylbutyl)-4-biphenylyltoethane This step was carried out in a similar manner to step 1b2.

The properties of the products are as follows: 8-Ch--11°C Ch-I-45°C Example 8 1-(trans-4-n-hebutylcyclohexyl)-2-(2'-Fluoro-4'-(
M preparation step 1a4 of 2-methylbutyl)-4-biphenylyltoethane: 4''()lance-4-n-butylcyclohexylacetyl)-2'-fluoro-4'-(
Preparation of 2-Methylphylumbiphenyl This step was carried out in a similar manner to step 1a2.

The properties of the product are as follows: -Ch 69.8-70.3°C Ch-I 74.1-74.3°C Step 1b4: 1-(trans-4-n-heptylcyclohexyl ) -2-[2'-fluoro-4' -(
Preparation of 2-methylbutyl)-4-biphenylyltoethane This step was carried out in a similar manner to step 1b2.

The products had the following properties: 8-Ch-52°C Ch-I-79°C Examples of chiral nematic compounds that can be synthesized in a similar manner to the above examples are shown below in Table 13b. .

Expression 13b: % formula %) However, 2M5Bu-(+)-2-methylbutyA'm is O
~12 values.

The following experiment shows that the formula is RA-n-alkyl and Rnmn-alkyl and has fewer than 10 carbon atoms in RA and RB! The advantages of the compound of a were compared with the same compound of formula Ia where RA and RB are both n-pentyl, ie the total number of carbon atoms in RA and RB is 10. 80 parts by weight of each investigated compound were divided into 10 parts by weight of cyanobiphenyl of the formula: % formula % ( ) and the formula; n-C3H7
Each mixture was formed by mixing with 10 weights of cyanobiphenylylethane of +CH, 1CH2 N2.

Next, the smectic-nematic (
8-N) The transition temperature was measured. From the transition temperature, it was found that the compound has a tendency to form a single shot smectic phase. The lower the 8-N temperature, the more preferable the compound is. The results obtained are shown in Table 14 below.

Table 14: Smectic-nematic transition temperature (8-N) in a mixture containing the compound of formula: Compounds investigated In Table 14, compounds marked with * and ** are comparative examples outside the scope of the present invention. , S-N value is clearly inferior to other compounds listed in Table 14.

Similar results, R, -n-alkyl and R, -no-
Compounds of formula 1a and Ib which are alkoxy and have a total number of carbon atoms plus oxygen atoms in the radicals R1 and R2 of 10 or more have also been obtained.

Specific examples of materials and devices embodying the present invention will be described based on the accompanying drawings.

The slides of FIGS. 1-4 are formed from front and rear glass slides 2.3 held apart by spacers 4 at a distance of about 77 m and held together by epoxy adhesive. A liquid crystal substance 12 is filled in the space between the slide 2.3 and the spacer 4. In front of the glass slide 2 under the fluorocarbon, a front polarizer 5 is placed so that the polarization axis is horizontal. Place them in an array. Place the reflector 7 behind the slide 3.

A rear polarizer 6 or analyzer is placed between the slide 3 and the reflector 7. I A tin oxide electrode 8.9, typically 100X thick, is applied as a complete film to the inner surface of the slide 2.3 and etched into the shape shown in FIG. 3.4. The display has 7 bars per digit 1o and a decimal point 11 between each digit. As shown in FIG. 3, the rear electrode structure consists of three electrodes X,,X,,X,. Similarly, the front electrode structure has three electrodes Y for each number and decimal point.
It consists of □, Y, , Y3... Examine the 6 electrodes for each number and make the appropriate X.

By applying an appropriate voltage to the Y electrode, each of the eight elements is shown to have an independently applied voltage.

Before assembly, the electrode slide 2.3 was cleaned and immersed in a 0.2-ficl polyvinyl alcohol (PVA) aqueous solution. When dry, the slides are rubbed in a certain direction with a soft cloth, and then assembled so that the rubbing directions are perpendicular to each other and parallel to the optical axes of the adjacent polarizers, that is, the polarizers intersect. Nematic liquid crystal material 12
When introduced between slides 2 and 3, the molecules on the slide surface line up along the direction of rubbing on each slide and gradually twist between the slides.

When no voltage is applied to cell 1, the light passes through front polarizer 5.
, through cell 1 (during which the plane of polarization rotates 90°), and through rear polarizer 6.

It is reflected by the reflective surface 7 and reaches the observer. (See Figure 1. The observer is at an angle of 45° to z@ perpendicular to the X and Y axes in the plane of the slides 2, 3.) Two electrodes 8.9
When a voltage higher than the threshold is applied between them, the liquid crystal layer 12 loses its optical activity and the molecules smear perpendicularly to the slide 2.3. 20,000 1
+ −+ x ν l) Exposure self-emission −11 ÷ light is reflective plate 7
, it does not reach the observer, and the observer sees only a dark display of the number 100 or more bars.

As shown in FIGS. 5, 6 and 7, voltages are applied in a line scanning manner at three consecutive time intervals.

Each X electrode is set to a potential of 3V/2 in turn, while the remaining X electrodes are set to -V/2K. During this time, the Y electrode is set to -3V/2 or V/2. If 3v/2 and -3v/2 match at the crossing point, a voltage of 3cm will be applied to the liquid crystal layer 12. At other points the voltage is V or -1. When 3V/2 is scanned to the X electrode, the appropriate Y
The selected crossing point is turned on by applying -3v/2 to the electrode (indicated by a black circle in the figure), the voltage V
is, for example, a 100 Hz square wave alternating current signal, and the sign represents the phase.

It will be apparent to those skilled in the art that the devices shown in Figures 1-7 are diversified displays because the electrodes are distributed between on and off intersections or display elements.

Materials embodying the invention suitable for use in material 12 of the device described above include mixtures C, D□, D2. D
3 or D4 and Mixture 1 shown in Table 15 below.

Table 15 Mixture 1 Compound Weight range C2H, (■唖)-CN n-C4H,% CN C2H,% 0N n-C4He (H only) ocN A small amount of optically active substance is added to the nematic substance to form molecules of the liquid crystal layer. A desired twist may be created. Using this treatment and appropriate slide surface preparation, British Patent Application Nos. 1,472.247 and 1,478,592
The display patch problem taught in No. 1 can be avoided.

Suitable optically active substances are: from about 0.1 to
015 of 0.5 weight range and about 0.01 to 0.05 weight range Ck315°C15 is CB15 and a small amount of pleochroic dye, for example, Japanese Patent Publication No. 2093475
You may also add 2M of Dye Mixture 2 described in the above issue to increase contrast.

Other specific mixtures embodying the second aspect of the invention are Fr.
It may be used for eeder 1cksz effect type cells. The cell consists of a sandwich of liquid crystal material between a glass slide having an electrode film on the internal surface, as in the device described above. However, in this case, a polarizer is not necessarily necessary; the inner surface of the glass slide is treated with a lecithin coating, and the liquid crystal material is a negative material, and the lecithin coating ensures that all molecules are perpendicular to the slide substrate (homeotropic orientation). ) are arranged in the off state. When an appropriate electric field is applied to the material in the on state, the molecules rearrange parallel to the slide surface (homogeneous orientation). Pleochroic dyes may be incorporated into the liquid crystal material to enhance the contrast between the on and off states.

The Fr6edericksz effect cell made as described above may incorporate the following mixture 3;
．． 0 am intervals.

Table 16 Mixture 3 n-C5H, (arrow CH6, CH2% C2H5 Compound J: may be added to Mixture 3 (Mixture 303 weight range) as a negative additive.

The preparation of compound J is described in British Patent Publication No. CD2061256. Approximately 1 part by weight of known dye mixtures may be added to Mixture 3 to form a colored mixture (Mixture 3A).

When a voltage is applied to the cell, the color changes from a weakly absorbing state to a strongly absorbing state.

Another embodiment of the invention incorporates the above-described materials into a (cholesteric-nematic) phase change effect device.

A cell is prepared containing a long helical pitch of cholesteric material sandwiched between electrodes with a glass slide similar to the twisted nematic cell described above. However, in this case no surface preparation for homogeneous alignment, e.g. glass slide surface treatment with 8i0 and polarizers are used.

If the glass slide is untreated and the liquid crystal material has a positive dielectric anisotropy (ΔE), the liquid crystal material has a twisted 7-monochalconic molecular orientation in the off state which scatters light. The effect of an electric field applied between a pair of electrodes on the interior surface of each glass slide is to change the region of liquid crystal material between the electrodes into an off-state into a homeotropic nematic orientation that is less scattering than the off-state. This is a negative contrast phase change effect device.

If the internal surface of the glass slide is treated with a coating of lecithin, for example, so that the liquid crystal material has a negative ΔE and is oriented perpendicular to the surface, then the material in the off state is in a homeotropic orientation with a small scattering effect on the incident light. be. Applying an electric field between a pair of electrodes on the interior surface of each glass slide changes the region of liquid crystal material between the electrodes (in the off state) into a twisted homogeneous orientation that scatters light.

This is a positive contrast phase change effect device.

The contrast between the two states in each case is determined by adding a small amount of a suitable pleochroic dye to the liquid crystal material (e.g. 1 if ΔE is positive).
Positive dielectric anisotropy materials embodying the present invention used in phase change effect (negative contrast) devices may be enhanced by adding (by weight % dye mixtures) 4 is as follows.

Table 17 Mixture 4 Compound Weight CB t s -R$ CN (Rc-=(+) -2
-Methylbutyl) Suitable negative dielectric anisotropic materials, mixtures 5 embodying the present invention, used in the four-phase change effect type (positive contrast type) are as follows.

Table 18 Mixture r Substance Weight Mixture 3 99 uc$co, o-C) Rol (Ro-(+)-2-methylbutyl) Using xyl compounds of formula I in place of the xyl substances listed in Table 18 obtain.

[Brief explanation of drawings]

Figure 1 is a partial view of a twisted nematic digital display, Figure 2 is a sectional view of the display in Figure 1, Figure 3 is a diagram of the shape of the rear electrode in Figure 1, and Figure 4 is the figure in Figure 1. Figure 5.6.7 is an illustration of the device of Figures 1-4 showing typical voltages. 1... Cell, 2. ．． 3...Glass slide, 4.
...Spacer, 5,6...Polarizer, 7...Reflector, 8.9...Electrode, 12...Liquid crystal substance. Applicant United Kingdom Application Artificial Intelligence Merck Patent Gesellschaft
Mitsut Beschrenchtel Hattrang Agent
Patent Attorney Yoshio Kawaguchi Agent Patent Attorney Kinzai Continuation of Gen No. 1 True Priority Claim [Phase] 1 Guo Tame October 24 IO United Kingdom O
Inventors: David Ian Bishop 0 Inventors Andrew David Pearson 0 Inventors Ian Charles Sarge @ Inventors George William Gray 0 Inventors David 942 0 Inventors Kenneth Johnson 0 Inventors Damien Zierard McDonnell (GB)@8328370 19 Solenyu Water Drive, Hamworthey, Poole, Dorset, United Kingdom Ettrick House, Branksome Bourke, Ettrick Road, Poole, Dorset, United Kingdom , Flat 5 (no street address), UK, Dorset, Poole, Hamworthey, Fresunyu Water Drive m, UK, Bumperside H Knee 16.4
・Newgate Street, Cottingham, D.W. 3. Killdill Crow, Bumperside, Hull, United Kingdom 19. Bumperside H. Knee, United Kingdom 6.8.
Ki 1 - W, Hull, Hall Road, 25 England, Worcestershire, Malvern, Upper Square Eighth Road, Eaton Burst, Flat 10 No. 2) No. 2), 2 strokes 17, "r71-1 -X; H11jj sum 5
℃) <December 2814 Commissioner of the Patent Office Wakasugi Wainu 1, Indication of tenancy 11j1wa55] year'l! l :'r
Application No. 11809f; 2, Title of the invention Di-substitution 2 [Kushi! 1M 'U' l This is the name of the person who made the correction.
゛Squirrel country (1 idiot) 4. Agent Shin-Vi 1-111 Sou 1, Shinjuku-ku, Tokyo
No. 4 Yamada Jiru 5, date of amendment order Shiro Suke

Claims (1)

[Claims] Equation (1)! [In the formula, -($-!-@= or ←; R is hydrogen or an alkyl group having 1 to 12 carbon atoms; R2 is hydrogen, an alkyl group having 1 to 12 carbon atoms, a carbon number l
to 12 alkoxy groups. (In the formula, R1 is hydrogen or an alkyl group having 1 to 12 carbon atoms, and R4 is hydrogen or an alkyl group having 1 to 12 carbon atoms.
2 alkyl groups or alkoxy groups having 1 to 12 carbon atoms); O represents a cyclohexane ring in the trans position in the case of 1,4-disubstitution; 0 represents a benzene ring ; X, Y and 2 each independently represent hydrogen or fluorine at one or more side positions of the benzene ring, provided that at least one of X, Y and 2 is fluorine; at n-0 or 1; Yes, if n-0, -()-R2 is sustenance and RIJ is Aryayaka, ah.
? However, the ceremony! In , n 1, ÷ R3 is SRs where R1 is an n-alkyl group and R2 is n
- in the case of an alkyl or n-alkoxy group, the total number of carbon and oxygen atoms in R3 and R3 is less than 10. (2) Formula (wherein RA is an n-alkyl group, RB is an n-alkyl or n-alkoxy group, the total number of carbon atoms and oxygen atoms in RA and RB is less than 10, The compound according to claim 1, item Ll., wherein Y is biphenyl selected from H and F, and at least one of X and Y is fluorine. (The total number of carbon atoms and oxygen atoms in 31R and R1 is 4
8. The compound according to claim 2, which is (4) Formula (wherein RA is an n-alkyl group, RB is a chiral alkyl group, X and Y are selected from H and F, and
and at least one of F is F)
Compounds described in Section. Claims having the formula (5) (wherein R2 is an alkyl group, X, Y and Z are each independently selected from H and F, and at least one of X, Y and 2 is fluorine) A compound according to item 1. (6) Formula (wherein R1 is an n-alkyl group, R is an n-alkyl or n-alkoxy group, X, Y, Z and W are respectively selected from F and H, and X, Y, Z The compound according to claim 1, which is a terphenyl having a small amount of and a small amount of W (both of which are F). represents a trans-1,4-dilt-substituted cyclohexane ring; % represents biphenyl having at least one fluorine @ substituent at the side position of the biphenyl axis; Q is H or -CH3.CH, number R, (in the formula , R2 is an alkyl group; and n is 0 or 1). Claim 1g
4. The compound described in 4. The compound according to claim 7, which is (9) The chemical food according to claim 7, wherein R and R3 are each independently an n-alkyl group. aG A liquid crystal composition comprising a mixture of metal oxides of formula I as claimed in claim 1. A liquid crystal composition comprising a mixture of compounds of formula (1) according to claim 3. - R2 of each compound in the composition is an n-alkyl group,
112. The composition of claim 111, wherein the total number of carbon atoms in R1 and R2 differs from compound to compound. R3: two electrically shielding substrates, at least one of which is optically transparent; a liquid crystal material layer sandwiched between the substrates; A liquid crystal device comprising an electrode capable of applying an electric field, wherein the liquid crystal material contains at least one compound according to claim 1.