JPH0430382B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides novel liquid crystal components containing trans-1-alkenyl or trans-3-alkenyl side chains, i.e. In the formula, R ¹ represents hydrogen or linear alkyl; R ² represents -CN, -R, -COR, -COOR or also -OR, -OOCR or fluorine on an aromatic ring; and R represents alkyl; A is 1 to
represents a group of four six-membered rings which are in each case directly connected to each other and to ring B via one covalent bond, or alternatively -COO-, -OOC- or _-CH2 bonded via CH ₂ - in one or sometimes two positions; the 6-membered ring in A and ring B are 1,4-phenylene or trans-
1,4-cyclohexylene or one of these rings can also be a trans-2,5-disubstituted m-dioxane ring, a 2,5-disubstituted pyrimidine ring or a 3,6-disubstituted m-dioxane ring. represents a substituted pyrimidine ring, and up to two adjacent trans-1,4-cyclohexylene rings are directly bonded via one covalent bond; and m is the number 2, or ring B is trans-1, Insofar as it represents a 4-cyclohexylene or trans-2,5-disubstituted m-dioxane ring, it also represents the number 0.

The invention also relates to processes for the preparation of compounds of the above formula, to liquid phase mixtures containing the compounds of the above formula and to the use of compounds of the above formula for electro-optical purposes.

As used herein, the term "alkyl" includes straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, etc., as well as branched an alkyl group,
In particular 1-methylalkyl and 2-methylalkyl, such as isopropyl, isobutyl, sec-butyl, 1-methylbutyl, 2-methylbutyl, 1
-Methylpentyl, 2-methylpentyl, 1-methylhexyl, 2-methylhexyl, and the like.

Ring B is 1,4-phenylene, trans-1,4
-Cyclohexylene, trans-2,5-disubstituted m-dioxane ring, 2,5-disubstituted pyrimidine ring or 3,6-disubstituted pyridazine ring. Group A contains 1 to 4 six-membered rings. The ring in radical A can represent 1,4-phenylene and/or trans-1,4-cyclohexylene. When ring B represents 1,4-phenylene or trans-1,4-cyclohexylene, one of the rings in group A is also a trans-2,5-disubstituted m-dioxane ring,
2,5-disubstituted pyrimidine ring or 3,6
- can represent a disubstituted pyridazine ring. Each trans-1,4-cyclohexylene ring that may be present in the formula may be directly bonded via one covalent bond to at most one further trans-1,4-cyclohexylene ring.

The term "aromatic ring" as used herein refers to a benzene, pyrimidine or pyridazine ring. The term "heterocyclic ring" refers within the scope of the present invention to a pyrimidine, pyridazine or m-dioxane ring.

Liquid crystals have recently gained considerable importance, primarily as dielectrics in display devices, because the optical properties of such materials can be influenced by applied voltages. Electro-optical devices based on liquid crystals are well known to those skilled in the art and exhibit various effects, such as dynamic scattering.
scattering), deformation of aligned phases (DAP type),
Schadt-Helfrich
Effect (rotating cell), guest/host (guest/
host) effect or cholesteric-nematic phase transition (phase change effect)
It can be based on

Liquid crystals must meet a number of requirements to be suitable as dielectrics for electro-optical displays. For example, liquid crystals must have good chemical stability against environmental factors such as heat, moisture, air and electromagnetic radiation in the infrared, visible and ultraviolet regions. Furthermore, the liquid crystal should be colorless, should have a short response time, should not have a viscosity that is too high, should exhibit good contrast, and should exhibit no nematic or It has a cholesteric mesophase. Other properties must meet different conditions depending on the type of cell used; for example, liquid crystals used in rotating cells have a large positive anisotropy with a large dielectric constant (△ε=
The liquid crystal _used in the guest/host cell should _have a dielectric constant of should have large positive or negative anisotropy. Furthermore, in both cases it is desirable to have a low threshold potential and a conductivity as low as possible.

In general, it is not possible to achieve all desired and, to some extent, contradictory properties with one compound, so by mixing several components, the properties for a particular application can be optimized. Mainly attempts have been made to However, in this case,
It is important that the components do not chemically react with each other and have good miscibility. Furthermore, the resulting mixture should be free of smectic mesophases, at least at the temperatures at which the liquid crystal cell is operated.

Many liquid-crystalline compounds and doping agents for liquid-crystalline mixtures having, for example, alkyl, alkoxy, alkanoyloxy, alkoxycarbonyl and cyano groups as wing groups are already known.

The compounds provided by the present invention have sufficient stability against electromagnetic radiation and are trans-
It has been found that 1-alkenyl or trans-3-alkenyl side chains have a favorable influence on mesophase behavior. Furthermore, the compounds provided by the invention have good miscibility with known liquid crystal mixtures and also possess the remaining necessary properties mentioned above. Depending on the meaning of ring B and the radicals A and R ² , the compounds provided by the invention cover a wide range of very different electro-optical applications. For example, compounds containing pyrimidine rings and/or cyano groups have positive anisotropy in dielectric constant (△ε=ε ₁₁ −ε⊥>0, where ε ₁₁ represents the dielectric constant along the longitudinal axis of the molecule, and ε⊥ represents the permittivity perpendicular to this), and
On the other hand, the pyridazine ring imparts negative dielectric anisotropy to the compound. On the other hand, a compound that does not contain a cyano group and does not contain a pyrimidine or pyridazine ring has a low viscosity and a small absolute sum of dielectric anisotropy. Compounds containing m-dioxane rings are of primary importance for low threshold potentials and short response times. Most of the compounds provided by the present invention are liquid crystalline in themselves, and some have extremely large mesophase ranges. Compounds provided by the present invention having only a monotropic or hypothetical clearing point, for example A represents a 1,4-phenylene or 3,6-disubstituted pyridazine ring and ring B is trans-1 , 4-cyclohexylene and in which R ² represents alkyl or alkoxy, are primarily suitable as doping agents for liquid-crystal mixtures. The invention therefore considerably widens the selection of suitable liquid crystal components facilitating the optimization of special mixtures.

A preferred group of compounds provided by the present invention has the general formula In the formula, rings B ¹ , B ² , B ³ and B ⁴ represent 1,4-phenylene or trans-1,4-cyclohexylene; n represents the number 0 or 1; X ¹ , X ² ,
X ³ and X ⁴ represent one covalent bond, or alternatively one or two of these symbols -COO-,
-OOC- or _-CH2CH2- ; _up to two adjacent trans-1,4-cyclohexylene rings are directly bonded via one covalent bond,
and R ¹ , R ² , R and m have the above meanings.

Preferably, m in the formula represents the number 0.
A particularly preferred compound of the formula is one in which X ¹ represents one covalent bond, -COO- or -CH ₂ CH ₂ -, and the symbol
X ² , X ³ and X ⁴ represent one covalent bond, and the ring
B ¹ , B ² and B ³ represent 1,4-phenylene,
and R ² represents cyano, alkyl, or alkoxy on an aromatic ring. Furthermore, ring B ⁴
preferably represents trans-1,4-cyclohexylene when R ² represents alkyl, and ring B ⁴ preferably represents 1,4-phenylene when R ² represents cyano.

However, bicyclic and tricyclic compounds are of general interest, ie compounds of the formula in which A has one or two six-membered rings. Preferred compounds provided by the present invention therefore have the general formula where rings B, C and D represent 1,4-phenylene or trans-1,4-cyclohexylene, or alternatively one of these rings is trans-
2,5-disubstituted m-dioxane ring, 2,5
- represents a disubstituted pyrimidine ring or a 3,6-disubstituted pyridazine ring; symbols X ¹ and X ²
one represents one covalent bond, and the other represents -COO-, -OOC-, -CH ₂ CH ₂ - or ring B,
At least one of C and D is trans-1,4-
As long as it is different from cyclohexylene, it also represents one covalent bond; n represents the number 0 or 1; and R ¹ , R ² , R and m have the above meanings.

Ring B in formula and a is preferably trans-1,4-cyclohexylene or trans-
Represents a 2,5-disubstituted m-dioxane ring. Furthermore, in formula a, n preferably represents the number 0. Generally, m is ring B in trans-1,4-
When representing cyclohexylene or trans-2,5-disubstituted m-dioxane ring, the number 0 is represented.

Preferred compounds within the formula and a are of the general formula In the formula, rings B ¹ and B ² represent 1,4-phenylene or trans-1,4-cyclohexylene; one of the symbols X ¹ and X ² represents one covalent bond, and the other represents -COO-, -OOC-,-
CH ₂ CH ₂ - or, as long as at least one of rings B ¹ and B ² is different from trans-1,4-cyclohexylene, also represents one covalent bond; n is a number of 0
or 1; and R ¹ , R ² , R and m have the above meanings, a compound of the general formula In the formula, ring E represents a 2,5-disubstituted pyrimidine ring, and ring B ¹ represents 1,4-phenylene or trans-1,4-cyclohexylene; X ¹ is one covalent bond, - COO−, −OOC−
or -CH ₂ CH ₂ -; n is the number 0 or 1
and R ¹ , R ² , R and m have the above meanings, a compound of the general formula In the formula, ring B ¹ represents 1,4-phenylene or ^trans -1,4-cyclohexylene;
and X ² represent one covalent bond, or one of these symbols is -COO-, -OOC- or -
_CH2CH2- ; n represents the number 0 or 1; ^R3 represents the group -R, -COR, -COOR _or also -OR or -OOR on an aromatic ring; and
Compounds and general formulas in which R ¹ , R and m have the above meanings In the formula, rings B ¹ and B ² represent 1,4-phenylene or trans-1,4-cyclohexylene; n represents the number 0 or 1; and R ¹ , R ² ,
R and m have the above meanings.

Particularly preferred compounds of _the formula are those in which X ¹ is one covalent bond, -COO-, -OOC- or _-CH2CH2-
and X ² represents one covalent bond,
Rings B ¹ and B ² represent 1,4-phenylene and R ² represents cyano, alkyl or alkoxy. Furthermore, in the formula n preferably represents the number 0 and/or X ¹ preferably represents one covalent bond.

Particularly preferred compounds of the formula are those in which X ¹ is in the 5-position of the pyrimidine ring and represents one covalent bond. Preferred groups represented by R ² are alkyl, alkoxy and especially cyano. Preferably, n represents the number 1 and the ring
B ¹ represents 1,4-phenylene.

Particularly preferred compounds of the formula are those in which X ¹ and X ² represent one covalent bond or one of these symbols represents -CH ₂ CH ₂ - and R ³ represents alkyl or also alkoxy on the aromatic ring. , especially compounds in which X ¹ represents one covalent bond and n represents the number 0.

Particularly preferred compounds of formula b are those in which n represents the number 0 and R ² represents cyano, alkyl or also alkoxy on an aromatic ring.
Ring B preferably represents 1,4-phenylene.

The radical R in the above definitions of R ² and R ³ is preferably an alkyl radical containing 1 to 12 carbon atoms, in particular a straight-chain alkyl radical containing 1 to 12 carbon atoms.

Furthermore, preference is given in principle to compounds of the formula in which R ² represents cyano, alkyl or also alkoxy on an aromatic ring. Preferred alkyl and alkanoyl groups ^R2 or ^R3 are groups containing 3 to 7 carbon atoms, and preferred alkoxy, alkanoyloxy and alkoxycarbonyl groups ^R2 or ^R3 are groups containing 2 to 6 carbon atoms. .

The symbol R ¹ in the above formulas a, b, , and is preferably hydrogen or straight-chain C ₁ -C ₁₀ -alkyl, especially hydrogen or C ₁ -C ₅ -alkyl, when m represents the number 0. , and when m represents the number 2, hydrogen or linear C ₁ to _{C 8} −
Alkyl, especially _hydrogen or C1- _C3 -alkyl. Within the scope of the invention, therefore, the term "trans-1-alkenyl" includes in particular the radicals vinyl, trans-1-propenyl, trans-
1-butenyl, trans-1-pentenyl, trans-1-hexenyl, trans-1-heptenyl, trans-1-octenyl, trans-1-
nonenyl, trans-1-decenyl, trans-
Includes 1-undecenyl and trans-1-dodecenyl, and "trans-3-alkenyl"
In particular, the term 3-butenyl, trans-
3-pentenyl, trans-3-hexenyl, trans-3-heptenyl, trans-3-octenyl, trans-3-nonenyl, trans-3-
Included are decenyl, trans-3-undecenyl and trans-3-dodecenyl.

A more preferred group of compounds provided by the present invention and examples of preferred compounds are compounds within the scope of the formulas described in the reaction formulas and examples below.

According to the invention, the compounds of formula (a) R ¹ represents primary alkyl containing at least 2 carbon atoms and R ² represents -CN, -R or also -OR on an aromatic ring or represents the element,
and the rings in which A is present are in each case directly bonded to each other and to ring B via one covalent bond, or alternatively via -CH ₂ CH ₂ - to one or possibly two. To prepare compounds of the formula that are bonded at two positions, the general formula In the formula, Y ¹ represents a leaving group; R ⁴ is -CN, -
R or also represents -OR or fluorine on an aromatic ring, and R represents alkyl; A ¹
represents a radical with 1 to 4 six-membered rings, which in each case are directly bonded to each other and to ring B via one covalent bond, or -
bonded in one or sometimes two positions via CH ₂ CH ₂ -; the 6-membered ring in A and ring B are 1,4-phenylene or trans-
1,4-cyclohexylene or one of these rings can also be a trans-2,5-disubstituted m-dioxane ring, a 2,5-disubstituted pyrimidine ring or a 3,6-disubstituted m-dioxane ring. represents a substituted pyridazine ring, and up to two adjacent trans-1,4-cyclohexylene rings are directly bonded via one covalent bond; and m is the number 2 or ring B is trans-1, 4-
Cyclohexylene or trans-2,5-
As long as it represents a disubstituted m-dioxane ring,
or (b) R ¹ represents methyl, R ² represents -CN, -R or alternatively represents -OR or fluorine on an aromatic ring and the rings present in A are in each case directly bonded to each other and to ring B via one covalent bond, or - To prepare a compound of formula in which CH ₂ CH ₂ − is bonded in one or possibly two positions, a compound of formula is reduced or (c) R ² and the rings present in A are in each case directly bonded to each other and to ring B via one covalent bond or also via one or optionally -CH ₂ CH ₂ - To produce a compound of the formula in which is attached at two positions, the general formula In the formula, R ¹ represents hydrogen or linear alkyl, and A ¹ , m and ring B have the meanings shown in the formula. (d) A is at least one group -COO- or -
To prepare compounds of the formula containing OOC- and/or in which R ² represents -COOR or -OOCR, the general formula A compound with the general formula Y ³ −A ³ −R ⁵ , where R ¹ represents hydrogen or linear alkyl; one of the symbols Y ² and Y ³ represents −COOH or −COCl, and the other represents − represents OH; A ² and A ³ each represent a group with 1 to 4 six-membered rings, or alternatively one of the groups A ² and A ³ may be absent, provided that A ² and A ³ together contain up to 4 rings; ring B
is optionally bonded directly via one covalent bond to the 6-membered ring present in A ² and as long as A ² and/or A ³ have several 6-membered rings;
These rings are in each case directly bonded to each other via one covalent bond, or one or, as the case may be, two of these bonds, unless A ³ is present, are -COO -, -OOC- or _-CH2CH2- ; the 6-membered ring in ^A2 and ^A3 and ring B represent 1,4-phenylene or trans-1,4 _- cyclohexylene, or and one of these rings represents a trans-2,5-disubstituted m-dioxane ring, a 2,5-disubstituted pyrimidine ring or a 3,6-disubstituted pyridazine ring,
and up to two adjacent trans-1,4-cyclohexylene rings are bonded via one covalent bond; m is the number 2 or ring B is trans-
1,4-cyclohexylene or trans-
Insofar as it represents a 2,5-disubstituted m-dioxane ring, it also represents the number 0; and R ⁵ is A ³
represents a 1 to 4 6-membered ring group, -CN,
-R, -COR, -COOR or also -OR, -OOCR or fluorine on an aromatic ring, or R ⁵ represents -R when A ³ is absent and R represents alkyl. (e) R ² is -CN, -R or also - on the aromatic ring.
OR or fluorine and the rings present in A are in each case directly bonded to each other and to ring B via one covalent bond, or alternatively one via -CH ₂ CH ₂ - or, as the case may be, in order to prepare compounds of the formula bonded in two positions, the general formula wherein A ¹ , R ⁴ , m and ring B have the meanings shown in the formula, is reacted with an alkyl triphenylphosphonium halide in the presence of a base, or (f) 6 in ring B or A To prepare a compound of the formula in which one of the member rings represents a trans-2,5-disubstituted m-dioxane ring, the general formula A compound of the general formula Y ⁵ -A ⁵ -R ² , where R ¹ represents hydrogen or straight-chain alkyl; R ² represents -CN, -R, -COR, -COOR or also -OR, -OOCR or fluorine, and R represents alkyl;
One of the symbols Y ⁴ and Y ⁵ represents -CH(CH ₂ OH) ₂ and the other represents -CHO or an acetal group; A ⁴ and A ⁵ each represent 1 to 4 1,4
- represents a phenylene or trans-1,4-cyclohexylene ring, or alternatively one of the groups A ⁴ and A ⁵ may be absent, provided that
A ⁴ and A ⁵ shall together contain up to 4 rings; Y ⁴ and Y ⁵ may be connected directly via one covalent bond to the 6-membered ring present in A ⁴ or A ⁵ , as the case may be. combine and A ⁴ and/or A ⁵
insofar as has several six-membered rings, these rings are in each case directly bonded afterwards via one covalent bond, or one or two of these bonds are -COO-, -OOC- Or −CH ₂ CH ₂
up to two adjacent trans-1,4-cyclohexylene rings are directly bonded via one covalent bond; and m is the number 2, or A ⁴ is absent, or trans-1 ，
Group R ¹ -CH=CH on the 4-cyclohexylene ring
When it represents -( _CH2 ) _n- , it can be produced by reacting with a compound of the following, which also represents the number 0.

The reaction of a compound of the formula with an alkylmagnesium halide (method a) can be carried out in a manner known per se. The term "halide" used in this connection refers to chloride, bromide or iodide, preferably bromide.
Dilithium tetrachlorochloride is the preferred catalyst. Y ¹ represents a leaving group commonly used in such reactions, such as alkanoyloxy, alkylsulfonyloxy, arylsulfonyloxy or halogen, such as acetoxy, methanesulfonyloxy, benzenesulfonyloxy, tosyloxy, naphthalenesulfonyloxy, bromine, iodine, etc. . The reaction is advantageously carried out in an ether such as dimethoxyethane, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane, diethyl ether and the like. The solvent is preferably tetrahydrofuran or a mixture of tetrahydrofuran and diethyl ether. Temperature and pressure can be maintained within a wide range. However, this reaction generally takes place at atmospheric pressure and around −80°C.
It is carried out at temperatures between 0C and room temperature. This reaction is preferably carried out at a temperature below about 0°C, especially about -15°C.

The reduction of compounds of the formula according to process (b) can be carried out according to methods known per se, for example by reacting a compound of the formula in which Y ¹ represents iodine with triphenylphosphonium iodide and a compound of the formula in which Y ¹ represents acetoxy. This can be done by reacting the compound with methanolic potassium hydroxide and triphenylphosphine-iodide. Such reactions are described, for example, in Chem. Ber. 109 , 1586 (1976).

The reaction of a compound of the formula with an alkylmagnesium halide (method c can be carried out in a manner similar to method (a)). However, generally this reaction is carried out at a somewhat elevated temperature, preferably from about 0°C to the reflux temperature of the reaction mixture.

The esterification of compounds of the formula with compounds of the formula (method d) can be carried out in methods known per se. Acid chlorides (obtainable from carboxylic acids, e.g. by heating with thionyl chloride)
The esterification can be carried out in, for example, diethyl ether, tetrahydrofuran, dimethylformamide, benzene, toluene, carbon tetrachloride, pyridine, or the like. Esterification of carboxylic acids is preferably carried out using 4-(dimethylamino)pyridine and N,
It is carried out in the presence of N'-dicyclohexylcarbodiimide or in the presence of oxalyl chloride and dimethylformamide. The temperature and pressure at which the esterification is carried out are not critical, and generally atmospheric pressure and temperatures between about -30°C and the boiling point of the reaction mixture are used.

The reaction of a compound of the formula with an alkyltriphenylphosphonium halide in the presence of a base (for example potassium carbonate) (method e) can also be carried out in a manner known per se. The term "halide" used in this connection refers to chloride, bromide or iodide, preferably bromide. This reaction is advantageously carried out in an inert organic solvent, such as an ether such as diethyl ether, tetrahydrofuran, dioxane, and the like.
Temperature and pressure are not critical, and generally the reaction is carried out at atmospheric pressure and temperatures from room temperature to the reflux temperature of the reaction mixture.

The reaction of a compound of the formula with a compound of the formula (method f) can be carried out in a manner known per se. The reaction of the diol with the aldehyde or its suitable acetal (for example dimethyl acetal) is advantageously carried out in an inert organic solvent in the presence of a catalytic amount of an organic or inorganic acid. Preferred solvents are hydrocarbons, especially aromatic hydrocarbons such as benzene, toluene, xylene and the like. Preferred acids are dry hydrogen chloride and sulfonic acids,
Especially p-toluenesulfonic acid. Temperature and pressure are not critical, but the reaction is preferably carried out at the reflux temperature of the reaction mixture and at atmospheric pressure. Generally, dioxane is obtained as a cis/trans mixture, from which a pure trans compound can be easily obtained by recrystallization. If necessary, the mother liquor can be converted with acid to a cis/trans equilibrium mixture and this can be recrystallized again.

According to process (e), when preparing compounds of the formula in which m represents the number 0 and ring B represents trans-1,4-cyclohexylene, the cyclohexane ring is almost exclusively in the trans-configuration. (approximately 98%); the process also uses as the starting material a mixture of cis/trans isomers (where m represents the number 0 and ring B is cis-1,4-cyclohexylene or trans-1,4-cyclohexylene). This applies when using a compound with the formula This process is therefore also an excellent method for preparing the corresponding trans-4-alkylcyclohexyl compounds by subsequent catalytic hydrogenation (e.g. with palladium, platinum or Raney nickel) in a manner known per se. offer possibilities.

Compounds of formula and are known or are homologs of known compounds.

The compounds of formulas, and are new and are likewise objects of the present invention. The production of the compounds of the formula and the production of the compounds of the formulas, , and are explained based on typical examples in the following reaction schemes 1 to 11; in the reaction scheme, R ⁶
represents a straight-chain alkyl, ^R7 represents hydrogen or a straight-chain alkyl, Ts represents p-tosyl, and Ring ^B1 represents 1,4-phenylene or trans-1,4-cyclohexylene. , and R ¹ , R ⁴ and R have the meanings given above. The starting materials required in these schemes are known or are homologs of known compounds.

If, instead of the cyano compound of formula XI, the corresponding alkyl, alkoxy or fluoro compound is used according to scheme 1, the penultimate step (
→) can be omitted, since alkyl, alkoxy and fluorine are not affected in the reduction with diisobutylaluminum hydride. The introduction of other leaving groups Y ¹ (in place of the acetoxy group in the formula or similar compounds) can be carried out according to methods known per se. Further, an example thereof is shown in Reaction Formula 6.

In the preparation of compounds of Ic and Ih in which R ¹ represents straight-chain alkyl according to Scheme 1 or 7 (method e), mixtures of cis- and trans-alkenyl compounds are generally obtained.
Such mixtures can be separated by chromatography on silica gel coated with silver nitrate. If desired, a cis-alkenyl compound (or a mixture containing primarily cis-alkenyl compounds) can be converted to the corresponding trans-alkenyl compound according to Scheme 6 or 7.

The reaction →e according to Reaction Formula 2 can be carried out in the same manner as Reaction Formula 1.

The preparation of acids and alcohols of formulas and the introduction of trans-3-alkenyl groups are illustrated in Reaction Schemes 3-5, 7 and 8. Additional acids of formula can also be obtained by saponification of nitriles of formula.

one of the rings represents a dioxane, pyrimidine or pyridazine ring and/or ring B is 1,4
The preparation of compounds of the formula -phenylene will be readily apparent from the above discussion of known methods for the preparation of such rings.

Generally, in the preparation of compounds of the formula containing an ester group or a dioxane ring, esterification or formation of the dioxane ring is advantageously carried out only as a final step. An example for the production of dioxanes provided by the present invention is shown in Reaction Scheme 9. The pyrimidines and pyridazines provided by the present invention can be obtained by first synthesizing the ring system according to known methods and then introducing an alkenyl group, or by using a compound already containing an alkenyl group in the formation of the heterocyclic ring. It can be obtained by The latter method is illustrated in more detail in Scheme 10 for certain pyrimidines.

In addition, compounds of the formula where R ² represents -OOCR are
According to the method described in Tetrahedron 36 , 557 (1980), from compounds of the formula in which R ² represents -COR,
It can be prepared by Baeyer-Villiger oxidation with a peracid (for example perbenzoic acid) followed by conversion of the resulting epoxide into double bonds.

When changing the cyano group to alkyl, alkoxy or fluorine, equations 1, 2, 6 and 7 apply equivalently. However, according to the usual reaction equation
It is advantageous to prepare compounds of the formula with different meanings for R ² and to subsequently introduce the desired group R ² in a manner known per se. Examples of these modified methods are shown in Reaction Scheme 11.

The starting materials necessary for preparing the fluorocompounds (R ² =fluorine) provided by the present invention are known compounds or homologs of known compounds or by methods known per se. from the corresponding amine by diazotization with nitrous and hydrochloric acid, conversion to diazonium tetrafluoroborate with sodium borofluoride, and subsequent heating. The amines can be obtained, for example, by Hoffmann, Curtius or Schmidt reduction starting from the corresponding carboxylic acids.

The preparation of compounds of the formula in which A represents a group of 2 to 4 6-membered rings [or the preparation of the corresponding starting materials required in processes (a) to (f)] may be further described in detail above using bicyclic It can be carried out in a similar manner to the production of the compound.

Moreover, the present invention also relates to the general formula In the formula, R ⁸ represents linear C ₁ -C ₁₂ -alkyl, trans-4-(trans-5-alkyl-m
-Preparation of dioxan-2-yl)cyclohexanecarbonitrile and compounds of the above formula L, liquid crystal mixtures containing these compounds and electron-
Concerning its use for optical purposes.

The compounds of formula L exhibit at the same time a large positive anisotropy of the dielectric constant, a small optical anisotropy, a low viscosity (especially when used as a mixture), a low threshold potential and a short response time, as well as an improved mesophase behavior. have. Furthermore, the compounds have a high degree of chemical stability and only a low conductivity, are colorless, have good compatibility with all conventional liquid crystals, and exhibit a high contrast in display devices. The compounds provided by the present invention are therefore eminently suitable as liquid crystalline dielectrics in electro-optical display devices, such as rotating cells and guest/host cells, especially rotating cells.

Preferred compounds of formula L are those in which R ⁸ is on a linear chain;
It represents _C3 - _C8 -alkyl.

Compounds of formula L have the general formula In the formula, R ⁸ has the above meaning, and can be prepared by reacting the compound with trans-4-cyanocyclohexanecarboxaldehyde or a suitable acetal thereof. This reaction can be carried out in a manner similar to method (f) above.

The compounds of the formula and the compound of the formula L may be combined with other liquid crystalline or non-liquid crystalline substances, such as Schiff's base, asobenzenes, azoxybenzenes, phenyl benzoates, cyclohexanecarboxylic acid phenyl esters, cyclohexanecarboxylic acid cyclohexyl esters, biphenyls, terphenyls,
From the group of phenylcyclohexils, cinnamic acid derivatives, phenylpyrimidines, diphenylpyrimidines, cyclohexylphenylpyrimidines, phenyldioxanes, 2-cyclohexyl-1-phenylethanes, 1,2-dicyclohexylethanes, etc. It can be used in the form of a mixture with other substances. Such materials are well known to those skilled in the art, and many are commercially available. However, when using non-liquid crystal components, care should be taken to use sufficient amounts of additional liquid crystal compounds so that the total mixture has a sufficiently large mesophase range. Of course, the mixture provided by the invention may also contain at the same time one or more compounds of formula and one or more compounds of formula L.

In view of the favorable properties of the compounds of formula and their good miscibility, the mixture provided by the invention may also consist solely of two or more compounds of formula. Accordingly, the mixtures provided by the present invention advantageously contain about 1 to 1 of compounds of formula
100% by weight, preferably about 5-70% by weight, especially about
Contains 10-50% by weight. In addition to compounds of one or more formulas, the mixture provided by the invention optionally preferably contains one or more compounds of the following general formulas: In the formula, ring B ¹ represents 1,4-phenylene or trans-1,4-cyclohexylene, and R ⁹
represents linear _C2 - _C7 -alkyl, ^R10 represents cyano or linear _C1 - _C6 -alkoxy, ^R11 represents cyano or linear _C1 - _C7 -alkyl or _C1 - _C7 -alkoxy, and ^R12 and ^R13 represent straight-chain _C1-7 -alkyl; p represents 0 or 1 _; ^R14 is trans-4-alkylcyclohexyl; 4′-alkyl-
4-biphenylyl, p-(trans-4-alkylcyclohexyl)phenyl, 2-(trans-
4-alkylcyclohexyl)ethyl or p-
[2-(trans-4-alkylcyclohexyl)
ethyl]phenyl, and R ¹⁵ represents trans-4-alkylcyclohexyl,
R ¹⁴ represents trans-4-alkylcyclohexyl, and R ¹⁵ represents p-(trans-4-alkylcyclohexyl)phenyl, p-[2-(trans-4-alkylcyclohexyl)ethyl]phenyl or 4′-(trans-4-alkylcyclohexyl)ethyl]phenyl. -4-alkylcyclohexyl)-4-biphenylyl, or R ¹⁴ represents p-alkylphenyl and R ¹⁵ represents p-[2-(trans-4-alkylcyclohexyl)ethyl]phenyl, and
The alkyl group in R ¹⁴ and R ¹⁵ is a linear C ₁ -
C ₇ -alkyl; one of the symbols Z ¹ and Z ² is -
COO− or −OOC−, and the symbol Z ¹ ,
The remainder of Z ² , Z ³ and Z ⁴ represent one covalent bond, or alternatively one of these symbols is -CH ₂ CH ₂
- represents; rings B ¹ and B ⁵ in formula C are of the formula or trans-1,4-cyclohexylene; rings B ² , B ³ and B ⁴ are groups of formula C or they are connected by one covalent bond to at least one of the other two of these rings; also represents trans-1,4-cyclohexylene; or represents methyl; R ¹⁶ and
R ¹⁷ is linear C ₁ -C ₇ alkyl or also of formula C
represents a linear C ₁ -C ₇ -alkoxy on the ring.

Compounds of formula L-C are known or are homologs of known compounds.

The esters of formula C are new, but they can be obtained according to esterification methods known per se. The starting materials necessary for preparing the esters of formula C are known or are analogs of known compounds and can be prepared according to known methods.

A mixture of compounds of formula L is a mixture of compounds of formula L
In addition to one or more compounds of the formula LC preferably contains one or more compounds of the formula LC. The amount of compound of formula L advantageously ranges from about 1 to 50% by weight, preferably from about 5 to 30% by weight.
It is.

Furthermore, the mixtures provided by the invention may contain suitable optically active compounds (e.g. optically active biphenyls) and/or dichroic colorants (e.g. azo, azoxy or anthraquinone colorants). . The amount of such compound is determined by the solubility,
Determined by desired pitch, color, extinction, etc. Preferably the amount of optically active compound is up to about 4% by weight and the amount of dichroic coloring material is up to about 10% by weight.

The liquid crystal mixture provided by the invention can be produced in a manner known per se, for example by heating the mixture of the individual components to a temperature slightly above the clearing point and then cooling the mixture. I can do it.

The production of electro-optical devices containing the mixture provided by the invention as dielectric can also be carried out in a manner known per se, for example by emptying suitable cells.
This can then be carried out by introducing the mixture into the emptied cell.

The present invention also relates to all novel compounds, mixtures, processes, uses and devices described herein.

Mixtures 1-4 below are examples of preferred mixtures provided by the present invention. V ₁₀ represents the threshold potential for 10% transmission, η represents the viscosity (bulk viscosity), t _po represents the switch-on time, and t _pff represents the switch-off time (2.5 V ₁₀ and tilt angle 0 (by rotation cell with °).
Measurements were performed at 22°C.

Mixture 1 4-ethoxy-1-[2-(trans-4-pentylcyclohexyl)ethyl]benzene 19.0% by weight, 4-cyano-4″-pentyl-p-terphenyl
3.5% by weight, 4-cyano-4'-(trans-4-pentylcyclohexyl)biphenyl 3.5% by weight, p-[trans-4-(2-(trans-4-pentylcyclohexyl)ethyl)cyclohexyl]benzonitrile 3.0% by weight %, 1-[2-(trans-4-butylcyclohexyl)ethyl]-4-(trans-4-pentylcyclohexyl)benzene 8.0% by weight, p-[trans-4-(trans-1-butenyl)cyclohexyl]benzo Nitrile 23.0% by weight, p-[trans-4-(trans-1-pentenyl)cyclohexyl]benzonitrile 40.0% by weight; melting point <-20°C, clearing point 78°C, nematetake; V ₁₀
= 2.18V, _tpo = 23ms, _tpff = 41ms.

Mixture 2 10.0% by weight of p-(5-butyl-2-pyrimidinyl)benzonitrile, 4.0% by weight of p-(5-heptyl-2-pyrimidinyl)benzonitrile, 9.0% by weight of trans-4-butylcyclohexanecarboxylic acid-pentyloxyphenyl ester % by weight, trans-4-pentylcyclohexanecarboxylic acid p-propoxyphenyl ester 13.0% by weight, 4-ethoxy-1-[2-(trans-4-propylcyclohexyl)ethyl]benzene 21.0% by weight, 4-cyano-4 '-(trans-4-pentylcyclohexyl)biphenyl 4.0% by weight, p-[5-(trans-4-ethylcyclohexyl)-2-pyrimidinyl]benzonitrile 6.0% by weight, p-[trans-4-(trans-1 -propenyl)cyclohexyl]benzonitrile 6.5% by weight, p-[trans-4-(trans-1-butenyl)cyclohexyl]benzonitrile 26.5% by weight, melting point <-20°C, clearing point 60°C, nemateque; η=
26.5cp, _V10 = 1.50V.

Mixture 3 p-(5-butyl-2-pyrimidinyl)benzonitrile 17.5% by weight, p-(5-peptyl-2-pyrimidinyl)benzonitrile 10.0% by weight, p-ethylbenzoic acid p'-cyanophenyl ester 6.5% by weight %, 4-cyano-4'-(trans-4-pentylcyclohexyl)biphenyl 8.0% by weight, p-[5-(trans-4-ethylcyclohexyl)-2-pyrimidinyl]benzonitrile 10.0% by weight, p-[trans -4-(trans-1-propenyl)cyclohexyl]benzonitrile 14.5% by weight, p-[trans-5-(trans-1-pentenyl)-m-dioxan-2-yl]benzonitrile 9.5% by weight, p-[ trans-5-(trans-1-hexenyl)-m-dioxan-2-yl]benzonitrile 24.0% by weight; melting point approximately -10°C, clearing point 80.4°C, nematic;
_V10 = 1.31V.

Mixture 4 p-(5-butyl-2-pyrimidinyl)benzonitrile 16.3% by weight, p-(5-peptyl-2-pyrimidinyl)benzonitrile 9.3% by weight, p-ethylbenzoic acid p'-cyanophenyl ester 6.1% by weight %, 4-ethyl-1-[2-(trans-4-propylcyclohexyl)ethyl]benzene 7.0% by weight, 4-cyano-4′-(trans-4-pentylcyclohexyl)biphenyl 7.4% by weight, p-[5 -(trans-4-ethylcyclohexyl)-2-pyrimidinyl]benzonitrile 9.3% by weight, p-[trans-4-(trans-1-propenyl)cyclohexyl]benzonitrile 13.5% by weight, p-[trans-5-( 8.8% by weight of trans-1-pentenyl)-m-dioxan-2-yl]benzonitrile, 22.3% by weight of p-[trans-5-(trans-1-hexenyl)-m-dioxan-2-yl]benzonitrile; Melting point <-20℃, clearing point 72℃, nematic; V ₁₀
=1.29V.

The preparation of the compounds provided by the present invention is illustrated in further detail by the following examples. In the examples, C represents the crystalline phase, S represents the smectate phase, S _B represents the smectate B phase, N represents the nematic phase, and I represents the isotropic phase.

Example 1 Ethylmagnesium bromide (172 mg magnesium) in 20 ml anhydrous tetrahydrofuran at -78° C. with argon bubbling into a sulfonation flask equipped with a thermometer, addition funnel and serum cup.
and 530 μl of ethyl bromide), and sequentially 3.6 ml of a 0.48 M solution of dilithium tetrachlorocrate in anhydrous tetrahydrofuran and anhydrous tetrahydrofuran.
p-[trans-4-(3-acetoxy-
It was treated with a solution of 500 mg of trans-1-propenyl)cyclohexyl]benzonitrile. After the addition was complete, the mixture was warmed to -15 DEG C. and stirred at this temperature for 1.5 hours, then treated with 20 ml of saturated ammonium chloride solution and stirred for a further 1 hour at room temperature. The dark blue aqueous phase was separated and extracted twice with 50 ml each of diethyl ether. The organic phase was washed twice with 50 ml each of water, dried over magnesium sulphate and concentrated. The residue (0.4 g) was subjected to low pressure chromatography (0.5 bar) on silica gel with ethyl acetate/petroleum ether (3:97 parts by volume) to give the crude p-[trans-4-(trans-1-pentenyl) ) Cyclohexyl]benzonitrile (375 mg) was obtained, which according to gas chromatographic analysis was p-
[trans-4-(trans-1-pentenyl)cyclohexyl]propiophenone 8.5% and p-
It was contaminated with 4.0% of [trans-4-(1-vinylpropyl)cyclohexyl]benzonitrile.
This crude product was treated with an excess of sodium borohydride in methanol (to reduce the propofenone) at 0°C, treated with ethyl acetate/petroleum ether (1:9 parts by volume) on silica gel. followed by low pressure chromatography (0.5 bar) and finally recrystallization from methanol at -78°C to yield p-[trans-4-(trans-1-pentenyl)cyclohexyl]benzonitrile with a purity of 98.6%. ; Melting point (C-N) 15.5°C, clearing point (N-I) 57.0°C.

The crude product was chromatographically separated on silica gel with ethyl acetate/petroleum ether (1:9 parts by volume) and the 1-
(1-hydroxypropyl)-4-[trans-4
-(trans-1-pentenyl)cyclohexyl]
Benzene was obtained, which was dissolved in acetone at 0° C. and oxidized to the ketone by addition of chromic acid (until the orange color was retained). Excess chromic acid was destroyed with isopropanol. After treatment and recrystallization, the final pure p-[trans-4
-(trans-1-pentenyl)cyclohexyl]
Propiofenone was obtained.

The p-[trans-4-(3
-acetoxy-trans-1-propenyl)cyclohexyl]benzonitrile was prepared as follows: (a) Argon in a sulfonation flask equipped with a thermometer, mechanical stirrer, addition funnel and solid material addition tube. While aerating, add 10.4 g of triphenyl-methoxymethyl-phosphonium chloride.
-suspended in 60 ml of butyl methyl ether, -10
It was treated with 3.6 g of solid potassium tert-butyrate within 10 minutes at <RTIgt;C. After the addition is complete, the mixture is
After stirring for a further 30 minutes at 10 DEG C. to 0 DEG C., the dark orange homogeneous mixture was then treated at 0 DEG C. with a solution of 4.2 g of 4-(p-cyanophenyl)cyclohexanone in 50 ml of anhydrous tetrahydrofuran. The mixture was subsequently stirred for a further 2 hours at room temperature, then poured into 500 ml of hexane and filtered. The concentrated residue (7.1 g) was diluted with ethyl acetate/ethyl acetate on silica gel.
Low pressure chromatography (0.5 bar) with petroleum ether (5:95 parts by volume) gave 4.5 g (94%) of p-[4-(methoxymethylene)cyclohexyl]benzonitrile as a colorless oil; purity 95%, R _f value (ethyl acetate/petroleum ether, 1:9 parts by volume) 0.30.

(b) A mixture of 4.2 g of p-[4-(methoxymethylene)cyclohexyl]benzonitrile and 100 ml of tetrahydrofuran/2N hydrochloric acid (4:1 parts by volume) was heated under reflux for 30 minutes in a round bottom flask. The mixture was then poured into 100 ml of water and extracted three times with 100 ml each of diethyl ether. The organic phase was washed once with 100 ml of water, dried over magnesium sulphate and concentrated. 4- as a colorless oil
3.9 g (100%) of (p-cyanophenyl)cyclohexanecarboxaldehyde was obtained, which was used in the next step without further purification: trans/cis ratio approximately 3:1, R _f value (ethyl acetate/
Petroleum ether, 3:7 parts by volume) 0.41. Recrystallization from hexane yielded pure trans-4-(p-cyanophenyl)cyclohexanecarboxaldehyde; melting point 57.1°C.

(c) 4-(p-
3.9 g of cyanophenyl) cyclohexanecarboxaldehyde and 272 g of powdered potassium carbonate
mg of the mixture were placed in a sulfonation flask equipped with a solid material addition tube at room temperature under argon bubbling and treated within 15 minutes with 7.6 g of solid ethoxycarbonylmethylene-triphenylphosphorane. The mixture was subsequently stirred at room temperature for 2 hours, then the ethanol was removed on a rotary evaporator and the residue was dissolved in water.
The mixture was added to a 100 ml volume and extracted three times with 100 ml of methylene chloride each. The organic phase was washed twice with 100 ml of water, dried over magnesium sulphate and concentrated.
The residue (12 g) was chromatographed on silica gel at low pressure (0.5 bar) with toluene/petroleum ether/ethyl acetate (5:4:1 parts by volume).
5.2 g of a crystalline mass was obtained from which, after crystallization from 500 ml of hexane, 3.9 g of ethyl trans-3-[trans-4-(p-cyanophenyl)cyclohexyl]acrylate was obtained as colorless crystals with a melting point of 125°C. g (75%) was obtained.

(d) Ethyl trans-3- in 25 ml of methylene chloride
A solution of 1.0 g of [trans-4-(p-cyanophenyl)cyclohexyl]acrylate was placed in a sulfonation flask equipped with a thermometer and a serum cap at -78°C under argon bubbling;
Treated within 10 minutes with 15.0 ml of a 0.84 M solution of diisobutylaluminum hydride in toluene. After the addition was complete, the mixture was warmed to -10 DEG C., stirred for a further 30 minutes at this temperature, poured into 100 ml of 0.2N sulfuric acid and extracted twice with 50 ml each of methylene chloride. The organic phase was washed with 50 ml of water, dried over magnesium sulphate and concentrated. The residue (approximately 850 mg) was dissolved in 30 ml of methylene chloride, and then dissolved in 0.5 ml of acetic anhydride.
ml and 45 mg of 4-(dimethylamino)pyridine. This mixture was stirred at room temperature for 1 hour,
Next, it was poured into 50 ml of a saturated aqueous copper sulfate solution, and extracted twice with 50 ml each of methylene chloride. The organic phase was washed twice with 50 ml each of water, dried over magnesium sulphate and concentrated. The residue (0.95 g) was dissolved in ethyl acetate/petroleum ether (1:9 parts by volume) on silica gel.
Low pressure chromatography (0.5 bar)
to obtain 720 mg (71%) of p-[trans-4-(3-acetoxy-trans-1-propenyl)cyclohexyl]benzaldehyde;
Purity 99.9%, R _f value (ethyl acetate/petroleum ether, 1:9 parts by volume) 0.31.

(e) A solution of 513 mg of hydroxylammonium chloride in 5 ml of water is placed in a sulfonation flask equipped with a mechanical stirrer under argon bubbling and dissolved in p-[trans-
4-(3-acetoxy-trans-1-propenyl)cyclohexyl]benzaldehyde 2.0
It was treated with a solution of g. This mixture was stirred for 1 hour, then sequentially 350 mg of copper sulfate pentahydrate and 2.1 ml of triethylamine in 10 ml of methylene chloride.
treated with a solution of After the initial ink-like blue color of the copper-pyridine complex changed to olive-green, 1.74 g of dicyclohexylcarbodiimide in 20 ml of methylene chloride were added. The mixture was then stirred for a further 3 hours at room temperature and filtered. liquid to water
The mixture was poured into 100 ml and extracted three times with 100 ml each of methylene chloride. The organic phase was washed twice with 50 ml each of water, dried over magnesium sulphate and concentrated. The residue (2.75 g) was subjected to low pressure chromatography (0.5 bar) on silica gel with toluene/ethyl acetate (9:1 parts by volume) to give p-[tras-4-(3-acetoxy-trans) as colorless crystals. 2.26 g (114%) of -1-propenyl)cyclohexyl]benzonitrile were obtained, which contained a portion of dicyclohexylcarbodiimide as the only impurity. This material was processed without further purification. R _f value (toluene/ethyl acetate, 9:1 parts by volume) 0.33.

The following compound was prepared in a similar manner: p-[trans-4-(trans-1-butenyl)cyclohexyl]benzonitrile, melting point (C
-N) 44.2°C, clearing point (N-I) 49.5°C.

Example 2 A mixture of 235 mg p-[trans-4-(trans-1-pentenyl)cyclohexyl)propiophenone (prepared according to Example 1), 0.161 ml hydrazine hydrate, 5 ml diethylene glycol and 5 ml ethanol was prepared. , heated under reflux for 30 min under an argon atmosphere in a round bottom flask equipped with a reflux condenser. The mixture was then treated with 195 mg of solid potassium hydroxide and then slowly heated to 200° C. while distilling off the ethanol and kept at this temperature for 2 hours. The cooled mixture was poured into 50 ml of water and extracted three times with 50 ml each of petroleum ether. 50% each of organic phase and water
Washed 3 times with ml and dried over magnesium sulfate,
and concentrated. The residue was subjected to low pressure chromatography (0.5 bar) on a short column of silica gel with hexane to give 185 mg (83 %)
Purity 98.6%, melting point (C-I) 7.0°C.

Example 3 A mixture of 3.8 g of 4-(p-cyanophenyl)cyclohexanecarboxaldehyde (prepared according to Example 1), 10.3 g of propyltriphenylphosphonium bromide, and 12.3 g of potassium carbonate was placed in a reflux condenser while bubbling with argon. The mixture was heated under reflux for 25 hours in a round bottom flask equipped with a.
The cooled mixture was then filtered and concentrated. The residue was taken up in 150 ml of water and extracted three times with 150 ml each of diethyl ether. The organic phase was washed twice with 100 ml each of water, dried over magnesium sulphate and evaporated. The residue (10.5 g) was subjected to low pressure chromatography (0.5 bar) with ethyl acetate/petroleum ether (3:97 parts by volume), yielding 2.35 g (55%) of a colorless semi-crystalline mass, which According to gas chromatography, p-[trans-4-(cis-1-butenyl)cyclohexyl]
Benzonitrile 80.3% by weight, p-[trans-4
-(trans-1-butenyl)cyclohexyl]
17.5% by weight of benzonitrile and p-[cis-4-
It consisted of 2.2% by weight of (cis-1-butenyl)cyclohexyl]benzonitrile. This material was further subjected to low pressure chromatography (0.5 bar) on silica gel coated with 10% silver nitrate using ethyl acetate/petroleum ether (3:97 parts by volume).
Next, crystallize from methanol at -78°C to obtain pure p-
[trans-4-(trans-1-butenyl)cyclohexyl]benzonitrile could be isolated; melting point (C-N) 44.2°C, clearing point (N-I)
49.5°C Example 4 (a) 4.0 g of 4-(p-cyanophenyl)cyclohexanecarboxaldehyde (prepared according to Example 1) was charged with bubbling of argon.
in a sulfonation flask equipped with a thermometer.
Dissolved in 50 ml of 0.1N methanolic potassium hydroxide solution, this solution was treated in portions with 711 mg of sodium borohydride within 20 minutes at 0°C. The mixture was stirred for an additional 10 minutes at 0° C., neutralized with 1N hydrochloric acid, and concentrated on a rotary evaporator. Water the residue
The mixture was added to a 200 ml volume and extracted three times with 100 ml of methylene chloride each. The organic phase was washed twice with 100 ml each of water;
Dry over magnesium sulfate and concentrate. The residue (4.2 g) was crystallized once from 90 ml of ethyl acetate/petroleum ether (1:2 parts by volume) at 0°C to give p-[trans-4-(hydroxymethyl)cyclohexyl]benzo as colorless crystals with a melting point of 109.8°C. Obtained 3.27 g (77%) of nitrile; purity 99.4%.

(b) A solution of 3.0 g of p-[trans-4-(hydroxymethyl)cyclohexyl]benzonitrile in 5 ml of pyridine at 0°C under argon bubbling.
It was placed in a sulfone flask equipped with a mechanical stirrer, thermometer and addition funnel and treated within 5 minutes with a solution of 4.4 g of p-tosyl chloride in 10 ml of pyridine. After the addition was complete, the cooling bath was removed and the mixture was stirred at room temperature for 15 hours. The pyridine was removed from this mixture in a rotary evaporator, the residue was taken up in 100 ml of water and diluted with 100 ml each of methylene chloride.
Extracted twice. The organic phase was washed twice with 100 ml each of water;
Dry over magnesium sulfate and concentrate. The residue (5.0 g) was subjected to low pressure chromatography (0.5 bar) on silica gel with ethyl acetate/petroleum ether (1:4 parts by volume).
4.35 g (95%) of p-[trans-4-(p-tosyloxymethyl)cyclohexyl]benzonitrile were obtained as colorless crystals; R _f value (ethyl acetate/petroleum ether, 3:7 parts by volume) 0.38.

(c) 3.8 g of p-[trans-4-(P-tosyloxymethyl)cyclohexyl]benzonitrile,
A mixture of 2.3 g of sodium iodide and 100 ml of acetone was heated under reflux for 15 hours with argon bubbling in a round bottom flask equipped with a reflux condenser. After filtration and concentration of the mixture on a rotary evaporator, the residue was taken up in 100 ml of water and extracted three times with 100 ml each of diethyl ether. The organic phase was washed twice with 100 ml each of water, dried over magnesium sulphate and concentrated. The residue was subjected to low pressure chromatography (0.5 bar) on silica gel with toluene and p-
3.19 g (95%) of [trans-4-(iodomethyl)cyclohexyl]benzonitrile was obtained; R _f
Value (ethyl acetate/petroleum ether, 1:9 parts by volume) 0.30.

Example 5 A suspension of 2.51 g of methyltriphenylphosphonium bromide in 80 ml of anhydrous tetrahydrofuran was placed at −20° C. under argon in a sulfonation flask equipped with a dropping funnel and a thermometer, and a suspension of butyllithium in hexane was added. Treated with 7.6 ml of 0.8M solution. After stirring for 30 minutes at -20°C, a solution of 1.0 g of trans-4-(p-cyanophenyl)cyclohexanecarboxaldehyde in 10 ml of anhydrous tetrahydrofuran was added dropwise to the yellow mixture at -20°C within 5 minutes; The yellow color disappeared. The mixture was stirred for an additional 30 min at -20°C, then diluted with 100% water
ml and extracted three times with 100 ml each of diethyl ether. The organic phase was washed twice with 100 ml each of water, dried over magnesium sulphate and concentrated. The residue (2.3 g) was subjected to low pressure chromatography (0.5 bar) on silica gel with ethyl acetate/petroleum ether (3:97 parts by volume) to give p-(trans-4-vinylcyclohexyl)benzonitrile as colorless crystals. Obtained 897 mg (91%); purity 99.4%.
Further crystallization from 22ml of methanol, purity 99.95%
p-(trans-4-vinylcyclohexyl)
Benzonitrile was obtained; melting point (C-I) 56.4
℃, clearing point 28.5℃.

Example 6 A suspension of 3.6 g of butyl triphenylphosphonium bromide in 40 ml of tert-butyl methyl ether is prepared at room temperature under argon bubbling in a sulphone equipped with a thermometer, a mechanical stirrer, a dropping funnel and a tube for adding solid material. The mixture was placed in a reaction flask, treated with 1.01 g of potassium t-butyrate, and further stirred at room temperature for 1 hour. The deep orange heterogeneous mixture was then cooled to -60 DEG C. and treated within 15 minutes with a solution of 1.28 g of trans-4-(p-cyanophenyl)cyclohexanecarboxaldehyde in 10 ml of t-butyl methyl ether. The mixture was stirred for a further 60 minutes while gradually warming to -30 DEG C., then poured into 100 ml of water and extracted three times with 50 ml each of diethyl ether. 50% water to organic phase
Wash once with ml and dry over magnesium sulfate,
and concentrated. The residue (3.45 g) was subjected to low pressure chromatography (0.5 bar) on silica gel with ethyl acetate/petroleum ether (3:97 parts by volume) to give p-[trans-4-(1-
1.52 g (99%) of trans-1-pentenyl/cis-1-pentenyl]benzonitrile (trans-1-pentenyl/cis-1-pentenyl ratio approximately 5:95) were obtained; R _f value (ethyl acetate/petroleum ether, 3:97 parts by volume). )
0.19.

The following compounds were prepared in a similar manner: p-[trans-4-(1-propenyl)cyclohexyl]benzonitrile, p-[trans-4-(1-butenyl)cyclohexyl]benzonitrile, p-[trans- 4-(1-hexenyl)cyclohexyl]benzonitrile, p-[trans-4-(1-heptenyl)cyclohexyl]benzonitrile.

Example 7 p-[trans-
3.79 g of 4-(1-hexenyl)cyclohexyl]benzonitrile (prepared according to Example 6; trans-1-hexenyl/cis-1-hexenyl ratio approximately 5:95) and 758 g of benzenesulfonic acid.
The mixture was boiled under reflux for 15 hours while bubbling with argon in a round bottom flask equipped with a stirrer and a reflux condenser. A further 379 mg of benzenesulfonic acid were then added and the mixture was heated under reflux for a further 4 hours. The cooled mixture was poured into 50 ml of 1N sodium hydroxide solution and extracted three times with 100 ml each of hexane. The organic phase was washed twice with 50 ml each of water, dried over magnesium sulphate and concentrated. Quantitatively obtained balanced olefin mixture (ratio of trans-1-hexenyl/cis-1-hexenyl
80.4:19.6) was crystallized three times from methanol, with a melting point (C-N) of 14.3°C and a clearing point (N-I) of 39.5°C.
p-[trans-4-(trans-1-hexenyl)cyclohexyl]bezonitrile (cis-1-
1.74 g (46%) containing 0.3% hexenyl isomer was obtained. The mother liquor was not treated. However, if necessary, it could be re-equilibrated and the equilibrated mixture could be crystallized.

The following compound was prepared in a similar manner: p-[trans-4-(trans-1-propenyl)cyclohexyl]benzonitrile; melting point (C
-N) 66.3°C, clearing point (N-I) 73.0°C, p-[trans-4-(trans-1-butenyl)cyclohexyl]benzonitrile; melting point (C
-N) 45.1°C, clearing point (N-I) 51.8°C, p-[trans-4-(trans-1-pentenyl)cyclohexyl]benzonitrile; melting point (C
-N) 15.6℃, clearing point (N-I) 58.5℃, p-[trans-4-(trans-1-heptenyl)cyclohexyl]benzonitrile; melting point (C
-N) 17.9°C, clearing point (N-I) 49.2°C.

Example 8 A mixture of 2.75 g of p-[trans-4-(erythro-1,2,-dibromopentyl)cyclohexyl]benzonitrile and 20 ml of glacial acetic acid was prepared at room temperature under argon bubbling with a mechanical stirrer and a thermometer. The mixture was treated with 2.42 g of zinc powder in a sulfonation flask and then stirred for 2 hours, which brought the mixture to 33° C. and the extract gradually went into solution. Then pour the mixture into 100ml of water and 100ml each of petroleum ether.
Extracted three times. The organic phase was washed twice with 100 ml each of water and once with 50 ml of saturated sodium carbonate solution, dried over magnesium sulphate and concentrated. 1.43 g (99%) of p-[trans-4-(trans-1-pentenyl)cyclohexyl]benzonitrile was thus obtained with a purity of 99.5%; melting point (C-
N) 15.6°C, clearing point (N-I) 58.5°C.

The starting material p-[trans-4-(erythro-1,2-dibromopentyl)cyclohexyl]benzonitrile was prepared as follows: (a) A thermometer, addition funnel and mechanical stirrer were used. 1.51 g of 90% m-chloroperbenzoic acid in 60 ml of methylene chloride and 3.0 g of powdered potassium carbonate were placed in a sulfonation flask at 0° C. while bubbling with argon.
[trans-4-(1-pentenyl)cyclohexyl]benzonitrile (prepared according to Example 6; trans-1-pentyl/cis-1
- Pentenyl ratio approximately 5:95) 15 in 2.0 g solution
Processed within minutes. The cooling bath was then removed and the mixture was heated for an additional 90 min each after a total of 75 and 105 min.
% m-chloroperbenzoic acid 0.75 g. This mixture was stirred for an additional 60 min at room temperature, then 10%
(weight/volume) poured into 50 ml of sodium thiosulfate solution and extracted three times with 100 ml each of methylene chloride.
The organic phase was washed with 50 ml of saturated sodium bicarbonate solution, dried over magnesium sulphate and concentrated. Thus p-[trans-4-(1,2-epoxypentyl)cyclohexyl]benzonitrile (trans-1,2-
2.1 g (98%) of epoxypentyl/cis-1,2-epoxypentyl with a ratio of approximately 5:95 was obtained; R _f value (ethyl acetate/petroleum ether, 10:
90 parts by volume): trans-1,2-epoxypentyl isomer 0.17, cis-1,2-epoxypentyl isomer 0.14.

(b) A solution of 2.46 g of triphenylphosphine in 30 ml of methylene chloride is placed in a round-bottomed flask equipped with a dropping funnel at 0° C. with argon bubbling;
Treated dropwise with an approximately 1M solution of bromine in methylene chloride until a slight yellow color remained. The solution was then carefully concentrated on a rotary evaporator and then dried under high vacuum. Pour the resulting crystalline residue into 30 ml of benzene.
treated with a solution of 2.1 g of p-[trans-4-(1,2-epoxypentyl)cyclohexyl]benzonitrile in 10 ml of benzene,
It was then heated under reflux for 3 hours. The hot solution was filtered over silica gel with toluene to give 3.0 g of crude crystalline product, which was filtered over silica gel with hexane/toluene (1:1 parts by volume).
Low pressure chromatography (0.5 bar)
After application, 2.61 g (81%) of almost pure p-[trans-4-(erythro-1,2-dibromopentyl)cyclohexyl]benzonitrile was obtained as colorless crystals. Recrystallized from 90 ml of petroleum ether/ethyl acetate (2:1 parts by volume),
2.09 g of extremely pure erythrodibromide (65
%); melting point 140.9°C.

The following compound was prepared in a similar manner: p-[trans-4-(trans-1-propenyl)cyclohexyl]benzonitrile; melting point (C
-N) 66.3°C, clearing point (N-I) 73.0°C, p-[trans-4-(trans-1-butenyl)cyclohexyl]benzonitrile; melting point (C
-N) 45.1°C, clearing point (N-I) 51.8°C, p-[trans-4-(trans-1-hexenyl)cyclohexyl]benzonitrile; melting point (C
-N) 14.4°C, clearing point (N-I) 39.2°C, p-[trans-4-(trans-1-heptenyl)cyclohexyl]benzonitrile; melting point (C
-N) 17.9°C, clearing point (N-I) 49.2°C.

Example 9 In the same manner as in Examples 1, 5, 6 and 8, 4-
[2-(p-cyanopheryl)ethyl]cyclohexanone is converted to trans-4-[2-(p-cyanophenyl)ethyl]cyclohexanecarboxaldehyde, and the latter is converted to p-[2-(trans-
It was converted to 4-(trans-1-alkenyl)cyclohexyl)ethyl]benzonitrile.

4-[2-(p-cyanophenyl)ethyl]cyclohexanone used as a starting material was prepared as follows: (a) 149 g of methoxymethyl-triphenylphosphonium chloride and 860 mg of t-butyl methyl ether were stirred at room temperature. This suspension was then placed in a sulfonation flask under nitrogen gas flow, and the suspension was
Cool to 10℃ and add 51.6 g of potassium t-butyrate.
processed within 10 minutes. This suspension is heated to -10℃~
It was stirred for a further 30 minutes at 0 DEG C. and then treated dropwise at 0 DEG C. with a solution of 47.3 g of 4,4-ethylenedioxycyclohexanone in 720 ml of tetrahydrofuran within 45 minutes. The orange suspension was stirred for a further 2 hours at room temperature, then poured into hexane 5, stirred for 10 minutes and filtered off with suction. Concentrate the liquid under vacuum to yield a yellowish-brown oil (104.1 g)
was treated with 500 ml of hexane and filtered off with suction. Concentrate the liquid under vacuum to a yellow-brown oil 61.7
g was obtained. The crude product was purified on silica gel with methylene chloride/acetone (98:2 and 95:2).
5 parts by volume) to give 1,1-ethylenedioxy-4-(methoxymethylene)cyclohexane as a colorless oil.
53.5g was obtained.

(b) 1,1-ethylenedioxy-4-(methoxymethylene)cyclohexane 28.2g, glacial acetic acid 77.0g
ml and 385 ml of water was heated under reflux in a round bottom flask for 1 hour with nitrogen bubbling. The yellowish clear solution was then cooled to room temperature and watered with water.
It was diluted with 800 ml and extracted three times with 700 ml each of methylene chloride. The organic phase was washed twice with 500 ml each of 10% (w/v) sodium carbonate solution, dried over sodium sulfate, filtered and concentrated. The resulting brownish liquid (18.5g) was chromatographically separated on silica gel using methylene chloride as eluent to yield 16.7g of 4-formylcyclohexanone as a brownish liquid.

(c) 63.3 g of p-cyanobenzyl-triphenylphosphonium chloride, 17.2 g of potassium t-butyrate and 195 ml of ethylene glycol dimethyl ether are placed in a sulfonation flask with stirring and nitrogen bubbling, thereby bringing the internal temperature to 44°C. rose to This brown suspension was heated to 0°C.
4-formylcyclohexanone in 100 ml of ethylene glycol dimethyl ether, cooled to
16.7 g of solution was processed within 2 minutes. The cooling bath was then removed and the mixture was stirred at room temperature for an additional 3.5 hours. The suspension was then poured into 500 ml of water and extracted three times with 600 ml each of methylene chloride. organic phase
10% (wt/vol) sodium chloride solution 500 each
Wash twice with ml and dry over sodium sulfate,
Strained and concentrated, 76.9g brownish paste
was gotten. The crude product was chromatographically separated on silica gel using methylene chloride as eluent and 4-
33.0 g of [2-(p-cyanophenyl)vinyl]cyclohexanone was obtained.

(d) 4-[2-(p-cyanophenyl)vinyl]cyclohexanone 33.0 g, toluene 520 ml, ethanol 260 ml and palladium/carbon (5%) 3.2
g mixture was placed in a round bottom flask equipped with a magnetic stirrer at room temperature and the mixture was hydrogenated until hydrogen uptake ceased. The black suspension was then filtered off with suction (rinsed with toluene) and the liquid was concentrated under vacuum. The resulting somewhat cloudy yellowish oil (34.1
g) was separated by chromatography on silica gel. Methylene chloride/hexane (1:
1 part by volume), methylene chloride/hexane (8:2
(parts by volume) and eluted with methylene chloride to give a yellowish oil.
25.6 g were obtained, which was crystallized from t-butyl methyl ether. Thus the melting point is 62.5 ~
22.6 g of 4-[2-(p-cyanophenyl)ethyl]cyclohexanone as colorless crystals at 64.3°C
was gotten.

The following compound was prepared in a similar manner: p-[2-(trans-4-(trans-1-propenyl)cyclohexyl)ethyl]benzonitrile; melting point (C-I) 61.3°C, clearing point (N-I )
54.2°C, p-[2-(trans-4-(trans-1-butenyl)cyclohexyl)ethyl]benzonitrile; melting point (C-I) 42.6°C, clearing point (N-I)
39.7℃, p-[2-(trans-4-(trans-1-pentenyl)cyclohexyl)ethyl]benzonitrile; melting point (C-N) 25.1℃, clearing point (N-I)
47.5°C, p-[2-(trans-4-(trans-1-hexenyl)cyclohexyl)ethyl]benzonitrile; melting point (C-N) 16.8°C and 19.7°C (2 modifications), clearing point (N-I) 34.6℃, p-[2-(trans-4-(trans-1-heptenyl)cyclohexyl)ethyl]benzonitrile; melting point (C-N) 31.6℃, clearing point (N-I)
43.6℃.

Example 10 Trans-4-(trans-1-pentenyl)
Cyclohexanol 200mg, trans-4-pentylcyclohexanecarboxylic acid 245.9mg, dicyclohexylcarbodiimide 293mg, 4-(dimethylamino)pyridine 14.16mg and methylene chloride 3ml
The mixture was stirred at room temperature for 25 hours. The mixture was then diluted with diethyl ether, the precipitated urea was separated off, and the liquid was concentrated. Dilute the residue with methylene chloride 40
ml and washed with 5% hydrochloric acid, sodium bicarbonate solution and sodium chloride solution. The aqueous phase was back extracted with methylene chloride. The organic phase was dried over magnesium sulfate, filtered and concentrated. The resulting white residue (450 mg) was subjected to low pressure chromatography on silica gel with diethyl ether/petroleum ether (3:97 parts by volume) to give 348 mg of white transparent needles, which were dissolved in methanol 20
Recrystallized from ml. There was thus obtained 289 mg of trans-4-pentylcyclohexanecarboxylic acid trans-4-(trans-1-pentenyl)cyclohexyl ester; melting point (C-S) 39.8°C, clearing point (S-I) 66.5°C.

Trans-4-(trans-1-pentenyl)cyclohexanol used as a starting material was prepared as follows: (a) 261.2 g of methoxymethyl-triphenylphosphonium chloride was suspended in 550 ml of t-butyl methyl ether. , treated with 90.53 g of potassium t-butyrate at -10°C. Remove the cooling bath;
This mixture was stirred at room temperature for 1 hour. This suspension was mixed with 70% of 4,4-ethylenedioxycyclohexanone in 350 ml of tetrahydrofuran at -10°C.
g and stirred for 1 hour at room temperature, then treated with water and extracted three times with diethyl ether. The organic phase was washed twice with water and the aqueous phase was back extracted with diethyl ether. The combined organic phases were dried over magnesium sulphate and concentrated. The resulting crystalline residue was dissolved in ethyl acetate, diluted with petroleum ether, filtered and the solvent was removed. The resulting yellow oil (100g) was distilled and 1,1-ethylenedioxy-
4-(methoxymethylene)cyclohexane 75.28
g (91.17%).

(b) A mixture of 10.55 g of 1,1-ethylenedioxy-4-(methoxymethylene)cyclohexane, 130 ml of water and 200 ml of glacial acetic acid was heated under reflux for 1 hour. The solvent was then distilled off on a rotary evaporator and the distillate was extracted twice with methylene chloride. The distillation residue (yellow oil) was diluted with 200 ml of water, neutralized with sodium carbonate solution and extracted three times with methylene chloride. The organic phase was washed with saturated sodium carbonate solution and the aqueous phase was back extracted with methylene chloride. The organic phase was dried over magnesium sulphate and evaporated. The remaining yellow oil was distilled and heated at 70°C/0.15 Torr.
6.7 g (93%) of formylcyclohexanone was obtained.

(c) A solution of 36.72 g of triphenylphosphine in 200 ml of methylene chloride was dissolved in carbon tetrabromide at -20°C.
Gradually treated with 23.22g and stirred for an additional 10 minutes.
The mixture was then transferred via cannula to 4-formylcyclohexanone in 100 ml of methylene chloride.
It was added dropwise to 6.30 g of a solution cooled to -60°C. The mixture was stirred for an additional 15 minutes at -60°C and then partitioned between water/methylene chloride. The aqueous phase was extracted twice more with methylene chloride. The organic phase was washed twice with water, dried over magnesium sulphate and evaporated. The resulting pale yellow oil (16 g) was subjected to low pressure chromatography on silica gel with ethyl acetate/petroleum ether (10:90 parts by volume).
12.08 g (85.8%) of 4-(2,2-dibromovinyl)cyclohexanone was obtained as a pale yellow liquid.

(d) 2 g of 4-(2,2-dibromovinyl)cyclohexanone, 3.43 g of ethylene glycol, p-
Toluenesulfonic acid 0.202g and benzene 240ml
The mixture was boiled under reflux for 5 hours using a water separator. The mixture was then treated with potassium carbonate, stirred briefly and left overnight. The mixture was then filtered and the solvent was removed from the liquid on a rotary evaporator. The residue was taken up in 200 ml of methylene chloride and washed twice with dilute sodium hydroxide solution and once with water. The aqueous phase was back extracted with methylene chloride. The organic phase was dried over magnesium sulfate,
filtered and evaporated. Thus, 1,1-ethylenedioxy-
14 g of 4-(2,2-dibromovinyl)cyclohexane was obtained.

(e) 1,1-ethylenedioxy-4-(2,2-dibromovinyl) in 70 ml of tetrahydrofuran.
A solution of 14 g of cyclohexane was cooled to -20°C,
Butyllithium in hexane at this temperature
Treated slowly with 76.62 ml of 1.4M solution (exothermic reaction). Remove the cooling bath and let the mixture cool within about 20 minutes.
Warmed to 20°C. The mixture was then treated with 150 ml of water and extracted three times with diethyl ether. The organic phase was washed twice with water and the wash water was back extracted with diethyl ether. The organic phase was dried over magnesium sulphate, filtered and evaporated. The resulting yellow liquid (8 g) was diluted with ethyl acetate/ethyl acetate on silica gel.
Low pressure chromatography with petroleum ether (7:93 parts by volume) as a clear liquid
6.5 g (91%) of -ethynyl-1,1-ethylenedioxycyclohexane were obtained.

(f) 4-ethynyl- in 40 ml of tetrahydrofuran
1,1-ethylenedioxycyclohexane 6.5
The solution of g was treated with 39.1 ml of a 1.4M solution of butyllithium in hexane at -20°C. The mixture was then diluted with hexamethylphosphoric triamide 60 at 0°C.
ml (temperature rose briefly to 26° C.) and then treated dropwise with 6.5 ml of propyl iodide. The cooling bath was removed and the mixture was allowed to warm to room temperature. A white precipitate formed. After 30 minutes, pour the mixture into water.
150 ml and extracted three times with hexane. The organic phase was washed three times with water and the wash water was back extracted with hexane. The organic phase was dried over magnesium sulphate, filtered and the solvent was removed on a rotary evaporator. The resulting yellow liquid (9 g) was subjected to low pressure chromatography on silica gel with ethyl acetate/petroleum ether (10:90 parts by volume) and treated with activated carbon to give 1,1-ethylenedioxy- 6.23 g (76.5%) of 4-(1-pentynyl)cyclohexane was obtained.

(g) A solution of 4.5 g of 1,1-ethylenedioxy-4-(1-pentynyl)cyclohexane in 54 ml of tetrahydrofuran is mixed with about 50 ml of precondensed ammonium in a sulfonation flask equipped with a magnetic stirrer. Dropwise treated. The mixture was then treated in portions within 7 hours with 1.3 g of sodium at -78°C. 1.5 hours after the last addition, the ammonia was evaporated off, the mixture was neutralized with 25% hydrochloric acid and left overnight. Then mix the mixture with water/
Partitioned three times in diethyl ether. The aqueous phase was back extracted with diethyl ether. The organic phase was dried over magnesium sulfate and then freed of solvent on a rotary evaporator. The resulting pale yellow liquid (3.8 g) was treated with 200 ml of acetone and 0.1 ml of concentrated sulfuric acid. This mixture was heated under reflux for 10 minutes, treated with water,
Acetone was removed on a rotary evaporator. The residue was partitioned three times between methylene chloride/water. The aqueous phase was back extracted with methylene chloride. The organic phase was dried over magnesium sulphate and evaporated. The resulting yellow liquid (3.5 g) was diluted with ethyl acetate/ethyl acetate on silica gel.
Chromatographically separated with petroleum ether (7:93 parts by volume), the 4-
3.0 g (83.5%) of (trans-1-pentenyl)cyclohexanone was obtained.

(h) 1.63 g of 4-(trans-1-pentenyl)cyclohexanone was dissolved in 8 ml of diethyl ether and 14 ml of ethanol. This solution was then treated dropwise with about 70 ml of ammonia and in portions with a lithium wire (about 1.3 g of lithium) until the color of the mixture remained constant for 1.5 hours. Thereafter, the ammonia was evaporated off and the mixture was acidified with ammonium chloride and hydrochloric acid and left for 3 days. The mixture was then partitioned between diethyl ether/water and the aqueous phase was back extracted with diethyl ether.
The organic phase was dried over magnesium sulphate, filtered and the solvent was removed on a rotary evaporator. The resulting yellow oil was subjected to low pressure chromatography on silica gel with ethyl acetate/petroleum ether (10:90 parts by volume) as a pale yellow viscous oil in trans-
1.47 g (89.1%) of 4-(trans-1-pentenyl)cyclohexanol was obtained.

The following compound was prepared in a similar manner: trans-4-(trans-1-pentenyl) trans-4-propylcyclohexanecarboxylate
Cyclohexyl ester; melting point (C-S) 23.8
℃, clearing point (S-I) 50.7℃, trans-4-butylcyclohexanecarboxylic acid trans-4-(trans-1-pentenyl)
Cyclohexyl ester; melting point (C-S) 26.2
℃, clearing point (SI) 65.0℃.

Example 11 Trans-4-(trans-1-pentenyl)
A mixture of 800 mg of cyclohexanecarboxylic acid, 675.64 mg of p-ethoxyphenol, 1.01 g of dicyclohexylcarbodiimide and 49.79 mg of 4-(dimethylamino)pyridine was suspended in 14.5 ml of methylene chloride and stirred at room temperature for 20 hours. The mixture was then diluted with diethyl ether and the precipitated urea was separated off.
The liquid was concentrated. The residue was taken up in hexane and washed with dilute hydrochloric acid, sodium bicarbonate and water. The aqueous phase was back extracted with hexane. The organic phase was dried over magnesium sulphate and evaporated. The resulting residue was subjected to low pressure chromatography on silica gel with ethyl acetate/petroleum ether (3:97 parts by volume) to give 1.080 g of trans-4-(trans-1-pentenyl)cyclohexanecarboxylic acid p-ethoxyphenyl ester. (83.8%). After recrystallization from 40 ml of hexane, the product is in the form of clear crystals.
880 mg was obtained; melting point (CN) 57.2°C, clearing point (N-I) 93.1°C.

Trans-4-(trans-1-pentenyl)cyclohexanecarboxylic acid used as a starting material was produced as follows.

(a) 7 g of methoxymethyl-triphenylphosphonium chloride was added to 35 g of t-butyl methyl ether.
ml and treated with 2.43 g of potassium t-butyrate at -20°C. Mix this mixture at room temperature for 1
4-(trans-1-pentenyl) in 18 ml of tetrahydrofuran at -20°C.
It was treated dropwise with a solution of 2 g of cyclohexanone and stirred for a further 1 hour at room temperature. The mixture was then treated with water and extracted three times with 50 ml each of diethyl ether. The extract was washed with water, and the washing water was back extracted with diethyl ether. The organic phase was dried over magnesium sulphate and the solvent was removed. The residue was dissolved in ethyl acetate, the solution was diluted with petroleum ether, the precipitated triphenylphosphine oxide was separated off and concentrated again. This separation method for triphenylphosphine oxide was repeated two more times, and the resulting 1-(methoxymethylene)-
The crude product of 4-(trans-1-pentenyl)cyclohexane was processed without further purification.

(b) 1-(methoxymethylene)-4-(trans-
2.75 g of 1-pentenyl)cyclohexane [crude product according to clause (a)] in tetrahydrofuran/
under reducing conditions with 100 ml of 2N hydrochloric acid (4:1 parts by volume).
Heat for 30 minutes and then stir at room temperature overnight. The mixture was then treated with 100 ml of water and extracted three times with 100 ml each of diethyl ether. The extract was washed with dilute sodium bicarbonate solution and water, and the aqueous phase was back extracted with diethyl ether. The organic phase was dried over magnesium sulphate and evaporated. The resulting yellowish liquid (2.5 g) was subjected to low pressure chromatography on silica gel with petroleum ether and ethyl acetate/petroleum ether (3:97 parts by volume) to obtain 4-(trans-1-pentenyl).
Cyclohexanecarboxaldehyde 1.65g
(76%).

(c) 4-(trans-1-pentenyl)cyclohexanecarboxaldehyde in 120 ml of acetone.
1.6 g of the solution was cooled to −10° C., treated dropwise with 8N chromic acid (approximately 10 ml) until the color of the mixture remained brown-orange, and stirred for 1 hour. Excess amount of chromic acid was destroyed by addition of isopropanol. The green solution was partitioned three times between water/methylene chloride. The organic extract was washed twice with water, and the wash water was back-extracted with methylene chloride.
The organic phase was dried over magnesium sulphate and evaporated. The pale brown crystalline residue (2.01 g) was partially dissolved in 20 ml of petroleum ether. The undissolved residue was separated and the separate liquid was evaporated. The resulting residue was recrystallized from 60 ml of petroleum ether at -78°C.
866 mg (49.5%) of (trans-1-pentenyl)cyclohexanecarboxylic acid was obtained.

(d) A mixture of 1.29 g of 4-(trans-1-pentenyl)cyclohexanecarboxylic acid and 20 ml of an 11% (wt/vol) solution of potassium hydroxide in diethyl glycol was boiled under reflux for 2 hours while bubbling with argon. . The mixture was then made slightly acidic with 25% hydrochloric acid and partitioned three times between water/methylene chloride. Wash the organic extract with water. The wash water was back extracted with methylene chloride. The organic phase was dried over magnesium sulfate and the solvent was removed on a rotary evaporator. The resulting dark brown crystalline oil (1.17 g) was
Recrystallization from 50 ml of petroleum ether at 78°C gave 0.44 g of trans-4-(trans-1-pentenyl)cyclohexanecarboxylic acid as pale brown crystals. Crude cis/trans-4-(trans-1-pentenyl)cyclohexanecarboxylic acid
The mother liquor containing 0.695g was not treated.

Example 12 A suspension of 6.64 g of methyltriphenylphosphonium bromide in 80 ml of t-butyl methyl ether is solidified within 3 minutes at -10° C. in a sulfonation flask equipped with a mechanical stirrer and under argon bubbling. Treated with 2.12 g of potassium t-butyrate. The mixture was stirred for a further 1 hour at room temperature and then treated within 5 minutes with a solution of 3.0 g of 3-[trans-4-(p-cyanophenyl)cyclohexyl]propionaldehyde in 20 ml of t-butyl methyl ether at 0°C. Treated and stirred for an additional 15 minutes at room temperature.
The mixture was then partitioned three times between diethyl ether/water. The organic extracts were washed twice with water, dried over magnesium sulphate, filtered and evaporated.
To separate the triphenylphosphine oxide, the residue was dissolved in ethyl acetate, the solution was diluted with petroleum ether, filtered and evaporated.
The resulting pale brown oil (4.38 g) was chromatographically separated on silica gel with ethyl acetate/petroleum ether (3:97 parts by volume) to give 2.83 g of white crystals. Recrystallization from methanol and treatment of the mother liquor finally yielded a total of 2.116 g of p-
[trans-4-(3-butenyl)cyclohexyl]benzonitrile was obtained; melting point (C-N) 49.5
℃, clearing point (N-I) 52.5℃.

3-[trans-4-(p
-cyanophenyl)cyclohexyl]propionaldehyde was prepared as follows: (a) Sulfonation of a suspension of 29.0 g of methoxymethyl-triphenylphosphonium chloride in 200 ml of t-butyl methyl ether with a mechanical stirrer. 9.7 g of potassium t-butyrate was added to the
Processed within minutes. The orange suspension was stirred at about 0°C for 1 hour, then at -10°C within 10 minutes.
trans-4- in 90 ml of butyl methyl ether
(p-cyanophenyl)cyclohexanecarboxaldehyde 12.0g solution was added dropwise to
Stirred for an additional 45 minutes at °C. The mixture was then partitioned three times between diethyl ether/water. The organic extracts were washed twice with water, dried over magnesium sulphate, filtered and evaporated. To separate the triphenylphosphine oxide, the residue was dissolved in ethyl acetate, the solution was diluted with petroleum ether, filtered and evaporated. The yellowish crystalline residue (16.3 g) was chromatographically separated on silica gel with ethyl acetate/petroleum ether (5:95 parts by volume) to give p-[trans-4-(2-methoxy) as white crystals. Vinyl)cyclohexyl]benzonitrile 10.1g (74%)
I got it.

(b) p-[trans-4-(2-methoxyvinyl)cyclohexyl]benzonitrile in 200 ml of tetrahydrofuran/2N hydrochloric acid (4:1 parts by volume)
The 10.1 g solution was heated under reflux for 1 hour with stirring. Next, this mixture was mixed with diethyl ether/
Partitioned into water three times. The organic extracts were washed with water, dried over magnesium sulphate, filtered and evaporated. 2-[trans-4-(p-cyanophenyl) as a light yellowish crystalline residue.
9.8 g of cyclohexyl]acetaldehyde was obtained.

(c) A suspension of 22.2 g of methoxymethyl-triphenylphosphonium chloride in 150 ml of tert-butyl methyl ether at 0° C. within 3 minutes while bubbling with argon in a sulfonation flask equipped with a mechanical stirrer. was treated with 7.4 g of solid potassium t-butyrate. This orange suspension was stirred for 1 hour at 0°C, then 100ml of tetrahydrofuran
9.8 g of 2-[trans-4-(p-cyanophenyl)cyclohexyl]acetaldehyde in
The solution was added dropwise within 10 minutes. The suspension was then gradually warmed to room temperature while stirring. After 15 hours, the suspension was partitioned three times between diethyl ether/water. The organic extracts were washed twice with water, dried over magnesium sulphate, filtered and evaporated. To separate the triphenylphosphine oxide, the residue was dissolved in ethyl acetate, the solution was diluted with petroleum ether, filtered and evaporated. The resulting yellowish oil (13.7 g) was diluted with ethyl acetate/petroleum ether (5:95) on silica gel.
chromatographically separated by (parts by volume);
10.5 g (96%) of p-[trans-4-(3-methoxy-2-propenyl)cyclohexyl]benzonitrile was obtained as a colorless oil.

(d) A solution of 10.5 g of p-[trans-4-(3-methoxy-2-propenyl)cyclohexyl]benzonitrile in 200 ml of tetrahydrofuran/2N hydrochloric acid (4:1 parts by volume) was refluxed for 45 minutes with stirring. Heated. The mixture was then partitioned three times between diethyl ether/water. The organic extract was washed twice with water, dried over magnesium sulfate,
filtered and evaporated. The white crystalline residue (9.9 g) was chromatographically separated on silica gel with ethyl acetate/petroleum ether (10:90 and 30:70 parts by volume) to give 3- as white crystals.
[trans-4-(p-cyanophenyl)cyclohexyl]propionaldehyde 9.4g (95%)
I got it.

Example 13 p-[trans-4-(erythro-3,4-dibromopentyl) in 100 ml of glacial acetic acid with argon bubbling in a round bottom flask equipped with a mechanical stirrer.
A solution of 9.54 g of [cyclohexyl]benzonitrile was treated with 9.8 g of zinc powder. This mixture at room temperature
Stirred for 30 minutes, then partitioned three times into petroleum ether/water. The organic extracts were washed twice with water, dried over magnesium sulfate, filtered, and concentrated.
Oily residue (5.56 g) coated with silver nitrate on silica gel (500 ml of a 0.2 M solution of silver nitrate in acetonitrile)
chromatographically separated using diethyl ether/hexane (1:9 parts by volume) as eluent, 3.2 g of crude product was obtained as white crystals. methanol
After recrystallization from 80 ml, 1.65 g (28%) of p-[trans-4-(trans-3-pentenyl)cyclohexyl]benzonitrile was obtained as white crystals.
The mother liquor and the impure fraction from the keromatographic separation were combined and purified again on silica gel coated with silver nitrate using diethyl ether/hexane (1:9 parts by volume) as eluent. The resulting crystalline product (1.5 g) was recrystallized from 40 ml of methanol to give an additional 0.65 g of p-[trans-4-(trans-3-pentenyl)cyclohexyl]benzonitrile as white crystals; melting point (C −
N) 59.8°C, clearing point (N-I) 73.7°C.

p-[trans-4-(erythro-3,4-dibromopentyl)cyclohexyl]benzonitrile used as starting material was prepared as follows: (a) in a sulfonation flask equipped with a mechanical stirrer. A suspension of 14.8 g of ethyl triphenylphosphonium bromide in 150 ml of t-butyl methyl ether was heated at -10° C. within 5 minutes to form 4.54 g of solid potassium t-butyrate while bubbling with argon.
It was treated with g. The suspension was stirred at room temperature for 1 hour and then at 0° C. within 5 minutes a solution of 6.4 g of 3-[trans-4-(p-cyanophenyl)cyclohexyl]propionaldehyde in 40 ml of t-butyl methyl ether. and further 15 min at room temperature.
Stir for hours. The mixture was then partitioned three times between diethyl ether/water. Organic extract with water 2
Washed twice, dried over magnesium sulfate, filtered and concentrated. To separate triphenylphosphine oxide, the residue was dissolved in ethyl acetate, this solution was diluted with petroleum ether,
filtered and concentrated. The resulting yellowish oil (8.55 g) was chromatographically separated on silica gel with ethyl acetate/petroleum ether (3:97 parts by volume) to give p-[trans-4-(3-pentenyl) as white crystals. cyclohexyl]
5.93 g (89%) of benzonitrile was obtained.

(b) A solution of 4.49 g of 90% m-chromium perbenzoic acid in 100 ml of methylene chloride was treated with 11.3 g of powdered carbonic acid. This mixture was dissolved in p-[trans-4-(3-
pentenyl)cyclohexyl]benzonitrile
Treated with 5.93 g of solution and stirred for a further 2 hours at room temperature. The mixture was then further treated with 4.49 g of 90% m-chloroperbenzoic acid and the resulting mixture was further stirred. After a total of 70 hours, the mixture was partitioned three times into methylene chloride/10% sodium thiosulfate solution. The organic extracts were washed with sodium thiosulfate solution and water, dried over magnesium sulfate, filtered and concentrated. The resulting light yellowish oil (6.3 g) was purified on silica gel with ethyl acetate/
Chromatographic separation with petroleum ether (10:90 parts by volume) yields 6.27 g (99.5
%) was obtained.

(c) Triphenylphosphine in 80 ml of methylene chloride
7.4 g of the solution was treated dropwise with a solution of 1.5 ml of bromine in 20 ml of methylene chloride under argon bubbling until a yellow color remained. The mixture was then evaporated on a rotary evaporator and the residue was dried under high vacuum for 1 hour. The yellow crystalline residue was suspended in 120 ml of benzene.
This suspension was treated with 6.27 g of p-[trans-4-(3,4-epoxypentyl)cyclohexyl]benzonitrile and heated under reflux for 1 hour with stirring. The mixture was then filtered over silica gel using toluene as eluent. Finally, the product-containing fractions are concentrated and p-[trans-4-(erythro-
3,4-dibromopentyl)cyclohexyl]
9.54 g (99.1%) of benzezonitrile was obtained.

Example 14 A solution of methylmagnesium iodide in diethyl ether (prepared from 384 mg of magnesium strips and 0.984 ml of methyl iodide in 30 ml of diethyl ether) was dissolved at room temperature in p-[trans-4-
(trans-1-pentenyl)cyclohexyl]
A solution of 2.0 g of benzonitrile was added dropwise. 30 ml of toluene were then added to the mixture, the diethyl ether was distilled off and the resulting mixture was heated under reflux for a further 1.5 hours. The mixture was then carefully treated with saturated ammonium chloride solution at 0° C. and partitioned three times between diethyl ether/water. The organic extract was washed twice with water, dried over magnesium sulfate,
filtered and evaporated. Yellow crystalline residue (2.6
g) was chromatographically separated on silica gel with ethyl acetate/petroleum ether (5:95 parts by volume) to give p-[trans-4-
(trans-1-pentenyl)cyclohexyl]
1.85 g (87%) of acetophenone was obtained.

Example 15 16 ml of ethanol and 16 ml of diethylene glycol
A solution of 1.35 g of p-[trans-4-(trans-1-pentenyl)cyclohexyl]acetophenone was added to hydrazine hydrate while bubbling with argon.
0.486 ml and heated under reflux with stirring for 1.5 hours (bath temperature 110° C.). The mixture was then treated with 550 mg of solid potassium hydroxide, the bath temperature was raised to 210° C., and the ethanol was distilled off. After 2.5 hours at 210℃,
The reaction was stopped and the mixture was partitioned three times between water/petroleum ether. The organic extracts were washed twice with water, dried over magnesium sulphate and evaporated. The residue (1.23 g) was chromatographically separated on silica gel using hexane as eluent to give 4-ethyl-1-[trans-4-(trans-1-pentenyl)cyclohexyl]benzene as a colorless oil.
Obtained 1.16 g (91%); melting point (C-I) -31°C.

The following compounds were prepared in a similar manner: 4-propyl-1-[trans-4-(trans-1-pentenyl)cyclohexyl]benzene;
Melting point (C-I) 7.0°C, 4-ethyl-1-[2-(trans-4-(trans-1-propenyl)cyclohexyl)ethyl]benzene; Melting point (C-I) 1.7°C, clear point -
26℃.

Example 16 404.4 mg of phosphorous tetraiodide in 5 ml of methylene chloride
A suspension of 4-ethoxy-1-[trans-
A solution of 205 mg of 4-(1,2-epoxypentyl)cyclohexyl]benzene and 0.703 ml of pyridine was added dropwise within 5 minutes. The suspension was heated under reflux with stirring, and after 2 hours an additional 40.44 mg of phosphorous tetraiodide was added. After stirring under reflux for a total of 19 hours, the reaction was stopped and the mixture was treated with 1N hydrochloric acid and
Extracted three times with diethyl ether. The organic extract was washed successively with 1N hydrochloric acid, sodium thiosulfate solution and water, dried over magnesium sulfate, filtered,
and evaporated. The residue (0.2 g) was chromatographically separated on silica gel using ethyl acetate/petroleum ether (3:97 parts by volume) as eluent to give 4-ethoxy-1-[trans-4-(trans-1- 120 mg of (pentenyl)cyclohexyl]benzene was obtained. After recrystallization from 10ml of ethanol,
Melting point (C-N) 32.2℃ and clearing point (N-1) 54.9
The product was obtained as white crystals at .

4-Ethoxy-1-[trans-4-(1,2-epoxypentyl)cyclohexyl]benzene used as starting material was prepared as follows: (a) p-[trans-4 in 90 ml of methylene chloride. −
(trans-1-pentenyl)cyclohexyl]
A solution of 2.63 g of acetophenone was sequentially added with 7.46 g of m-chloroperbenzoic acid while bubbling with argon at 0°C.
and 100 mg of 2,6-di(t-butyl)-p-cresol. The mixture was stirred for 40 hours at room temperature with exclusion of light. The mixture was then partitioned into methylene chloride/10% sodium thiosulfate solution and the organic phase was washed once with 10% sodium thiosulfate solution and twice with sodium bicarbonate solution. The aqueous phase was back extracted three times with methylene chloride. The combined organic phases were dried over magnesium sulphate, filtered and evaporated. The yellow oily residue of 4-acetoxy-1-[trans-4-(1,2-epoxypentyl)cyclohexyl]benzene was dissolved in 1N methanolic potassium hydroxide solution.
The mixture was dissolved in 100 ml and stirred at room temperature for 1 hour. The mixture was then adjusted to a pH value of approximately 8 with 25% hydrochloric acid;
Partitioned between diethyl ether/water. The aqueous phase was extracted three times with diethyl ether. The organic phase was dried over magnesium sulphate, filtered and evaporated. The resulting brown oil (2.96 g) was chromatographically separated on silica gel with ethyl acetate/petroleum ether (10:90 parts by volume) to give p-[trans-4-(1,2- epoxypentyl)cyclohexyl]phenol
2.16g was obtained.

(b) p-[trans-4-(1,
A solution of 1.6 g of 2-epoxypentyl)cyclohexylphenol was mixed with 1.89 ml of ethyl iodide and powdered potassium carbonate while bubbling with argon.
Processed with 3.24g. While stirring this mixture
Heated under reflux for 24 hours, evaporated on a rotary evaporator and the residue was partitioned between diethyl ether/water. The aqueous phase was extracted three times with diethyl ether.
The organic phase was washed twice with water, dried over magnesium sulphate, filtered and evaporated. The resulting yellowish oil (1.76 g) was chromatographically separated on silica gel with ethyl acetate/petroleum ether (5:95 parts by volume) to give 4% as an oily liquid.
-Ethoxy-1-[trans-4-(1,2-epoxypentyl)cyclohexyl]benzene
1.45g (82%) was obtained.

Example 17 A mixture of 1.00 g of 2-(trans-1-pentenyl)-1,3-propanediol, 1.11 g of p-butoxybenzaldehyde, 3 drops of 2N sulfuric acid and 40 ml of toluene was heated under reflux for 2 hours with water separation. did. The mixture was then treated with 7 drops of triethylamine, allowed to cool, washed three times with 5 ml each of saturated sodium bicarbonate solution and 10 ml water, dried over sodium carbonate, rolled and concentrated. The semi-crystalline residue (1.86 g) was chromatographed on silica gel with hexane/diethyl ether (97:3 parts by volume). Fractions containing the product were pooled (0.99 g) and recrystallized twice from hexane at -25°C. Pure trans-2-(p-butoxyphenyl)-5-(trans-1-pentenyl)-m-
0.44 g of dioxane was obtained; melting point (CN)
60.6°C, clearing point (N-I) 61.9°C.

2-(trans-1-pentenyl)-1,3-propanediol used as starting material was prepared as follows: 2-(trans-1-pentenyl)-1,3-propanediol in 75 ml of tetrahydrofuran.
A solution of 16.1 g of diethyl 1-pentenyl) malonate (Tetrahedron Lett. 1979 , 861) was
5°C within 1 hour with stirring under an inert atmosphere
and added dropwise to a suspension of 5.3 g of lithium aluminum hydride in 200 ml of dry tetrahydrofuran.
The mixture was stirred for a further 3.5 hours at room temperature, then sequentially with 15 ml of acetone and saturated sodium bicarbonate solution.
Dropwise treatment was carried out using 20 ml. The mixture was filtered, the liquid was concentrated, and the residue (8.2 g) was heated at 150°C/approx.
Distilled in 1Toor. 6.5 g of 2-(trans-1-pentenyl)-1,3-propanediol were obtained as a colorless oil.

The following compound was prepared in a similar manner: p-[trans-5-(trans-1-propenyl)-m-dioxan-2-yl]benzonitrile; melting point (C-I) 97°C, clearing point (N -I)73
°C, p-[trans-5-(trans-1-butenyl)-m-dioxan-2-yl]benzonitrile; melting point (C-I) 92.2 °C, p-[trans-5-(trans-1-pentenyl) )-m-dioxan-2-yl]benzonitrile; melting point (C-I) 67.2°C, clearing point (N-I)
59.1°C, p-[trans-5-(trans-1-hexenyl)-m-dioxan-2-yl]benzonitrile; melting point (C-I) 50.5°C, clearing point (N-I)
37.0°C, p-[trans-5-(trans-1-heptenyl)-m-dioxan-2-yl]benzonitrile; melting point (C-I) 49.3°C, clearing point (N-I)
49.2℃, trans-2-(p-ethoxyphenyl)-5-
(trans-1-pentenyl)-m-dioxane;
Melting point (C-I) 66.3℃, clearing point (N-I) 64.4
°C, trans-2-(p-ethoxyphenyl)-5-
(trans-1-hexenyl)-m-dioxane;
Melting point (C-I) 56.7℃, clearing point (N-I) 47.5
°C, trans-2-(p-butoxyphenyl)-5-
(trans-1-propenyl)-m-dioxane;
Melting point (C-N) 59.5℃, clearing point (N-I) 61.2
°C, trans-2-(p-butoxyphenyl)-5-
(trans-1-hexenyl)-m-dioxane;
Melting point (C-N) 30.5℃, S _B -N 30.3℃, clearing point (N-I) 48.4℃, trans-2-(p-propylphenyl)-5-
(trans-1-prepenyl)-m-dioxane;
Melting point (C-I) 57.8°C, trans-2-(p-propylphenyl)-5-
(trans-1-pentenyl)-m-dioxane;
Melting point (C-I) 45.2℃, clearing point (S _B -I) 35.3
°C, trans-2-(trans-4-butylcyclohexyl)-5-(trans-1-propenyl)-
m-dioxane; melting point (C-N) 47.3°C, clearing point (N-I) 48.4°C, trans-2-(trans-4-propylcyclohexyl)-5-(trans-1-pentenyl)
-m-dioxane; melting point (C-S _B 31.2°C, clearing point (S _B -I) 85.7°C.

Reference Example 1 2.00 g of trans-4-cyanocyclohexanecarboxaldehyde, 2.13 g of 2-pentyl-1,3-propanediol and p in 100 ml of benzene.
- A mixture of 65 mg of toluenesulfonic acid was heated under reflux for 3 hours in a round bottom flask equipped with a water separator and a reflux condenser with argon bubbling and water separation. The mixture was then treated with 3.0 g of potassium carbonate, stirred at room temperature for 16 hours, then filtered and the liquid was concentrated. The crystalline residue (4.1 g) was recrystallized from hexane at 0°C to give 1.47 g of trans-4-(trans-5-pentyl-m-dioxan-2-yl)cyclohexanecarbonitrile as colorless crystals at 99.1% purity. 38%). After further recrystallization from hexane at 0°C, the purity increased to 99.9%; melting point (C-N) 45.6°C, clearing point (N-I)
46.7℃.

The following compound was prepared in a similar manner: trans-4-(trans-5-propyl-m
-dioxan-2-yl)cyclohexanecarbonitrile; melting point (C-I) 63.6°C, clearing point (N-
I) 39.3°C, trans-4-(trans-5-
butyl-m-dioxan-2-yl)cyclohexanecarbonitrile; melting point (C-N) 33.2°C, clearing point 35.6°C, trans-4-(trans-5-heptyl-m)
-dioxane-2-yl)cyclohexanecarbonitrile; melting point (C-I) 56.3°C, clearing point (N-
I) 45.0℃.

Claims (1)

[Claims] 1. General formula In the formula, R ¹ represents hydrogen or linear alkyl; R ² represents -CN, -R, -COR, -COOR or also -OR, -OOCR or fluorine on an aromatic ring; and R represents alkyl; A is 1 to
represents a group of four six-membered rings which are in each case directly connected to each other and to ring B via one covalent bond, or alternatively -COO-, -OOC- or _-CH2 bonded via CH ₂ - in one or sometimes two positions; the 6-membered ring in A and ring B are 1,4-phenylene or trans-
represents 1,4-cyclohexylene, or alternatively one of these rings represents a trans-2,5-disubstituted m-dioxane ring or a 2,5-disubstituted pyrimidine ring, and up to two adjacent trans-1,4-cyclohexylene rings are directly linked via one covalent bond; and m
is the number 2 or the number 0 insofar as ring B represents a trans-1,4-cyclohexylene or trans-2,5-disubstituted m-dioxane ring. 2 General formula where rings B, C and D represent 1,4-phenylene or trans-1,4-cyclohexylene, or alternatively one of these rings is trans-
represents a 2,5-disubstituted m-dioxane ring or a 2,5-disubstituted pyrimidine ring; one of the symbols X ¹ and X ² represents one covalent bond,
and the other is −COO−, −OOC−, −CH ₂ CH ₂ −
Or, as long as at least one of rings B, C and D is different from trans-1,4-cyclohexylene,
Also represents one covalent bond; n is the number 0 or 1
and R ¹ , R ² , R and m have the meanings given in claim 1. 3. The compound according to claim 1 or 2, wherein ring B represents a trans-1,4-cyclohexylene or trans-2,5-disubstituted m-dioxane ring. 4 General formula In the formula, rings B ¹ and B ² represent 1,4-phenylene or trans-1,4-cyclohexylene; one of the symbols X ¹ and X ² represents one covalent bond, and the other represents -COO-, −OOC−,−
CH ₂ CH ₂ - or, as long as at least one of rings B ¹ and B ² is different from trans-1,4-cyclohexylene, also represents one covalent bond; n is a number of 0
or 1; and R ¹ , R ² , R and m have the meanings given in claim 1. 5 X ¹ represents one covalent bond, -COO-, -OOC- or -CH ₂ CH ₂ -, X ² represents one covalent bond, and rings B ¹ and B ² represent 1,4-phenylene. A compound according to claim 4. 6 General formula In the formula, rings B ¹ and B ² represent 1,4-phenylene or trans-1,4-cyclohexylene; n represents the number 0 or 1; and R ¹ , R ² ,
The compound according to claim 1, wherein R and m have the meanings described in claim 1. 7. The compound according to claim 6, wherein ring B ¹ represents 1,4-phenylene. 8 General formula In the formula, ring E represents a 2,5-disubstituted pyrimidine ring, and ring B ¹ represents 1,4-phenylene or trans-1,4-cyclohexylene; X ¹ is one covalent bond, - COO−, −OOC−
or -CH ₂ CH ₂ -; n is the number 0 or 1
and R ¹ , R ² , R and m have the meanings given in claim 1. Claim 8 in which 9 X ¹ is present in the 5-position of the pyrimidine ring and represents one covalent bond.
Compounds described in Section. 10 Claims 2 to 9 in which n represents the number 0
A compound according to any of the paragraphs. 11. A compound according to any one of claims 1 to 10, wherein 11R represents linear _C1 - _C12 -alkyl. 12 Claims 1 to 12 in which R ² represents cyano, alkyl or alkoxy on an aromatic ring
A compound according to any one of Item 11. 13. Compounds according to claim 12, wherein ^R2 represents cyano, _C3 - _C7 -alkyl or _C2 - _C6 -alkoxy on an aromatic ring. 14 m represents the number 0, R ¹ represents hydrogen or linear C ₁ -C ₁₀ -alkyl, and m
represents the number 2, R ¹ is hydrogen or a linear
Claim 1 representing _C1 - _C8 -alkyl
A compound according to any one of items 1 to 13. 15 m represents the number 0, R ¹ represents hydrogen or linear C ₁ -C ₅ -alkyl, and m
represents the number 2, R ¹ is hydrogen or a linear
Claim 1 representing C ₁ -C ₃ -alkyl
Compound according to item 4. 16 Consists of at least two types of compounds, at least one of which has the general formula In the formula, R ¹ represents hydrogen or linear alkyl; R ² represents -CN, -R, -COR, -COOR or also -OR, -OOCR or fluorine on an aromatic ring; and R represents alkyl; A is 1 to
represents a group of four six-membered rings which are in each case directly connected to each other and to ring B via one covalent bond, or alternatively -COO-, -OOC- or _-CH2 bonded via CH ₂ - in one or sometimes two positions; the 6-membered ring in A and ring B are 1,4-phenylene or trans-
represents 1,4-cyclohexylene, or alternatively one of these rings represents a trans-2,5-disubstituted m-dioxane ring or a 2,5-disubstituted pyrimidine ring, and up to two adjacent trans-1,4-cyclohexylene rings are directly linked via one covalent bond; and m
is characterized in that it is a compound of the number 2, or as long as ring B represents a trans-1,4-cyclohexylene or trans-2,5-disubstituted m-dioxane ring, and also represents the number 0. liquid crystal mixture.