JPS58110527A - Acetylene derivative - Google Patents

Abstract

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

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a general formula in which ring B is 1,4-phenyleneotak trans-1,
Represents a 4-In cyclohexane ring, with figures 1 to 3
represents a group having 6 members, which together with Sakai B has the formula [where All is trans-1,4-disubstituted cyclohexane, 1,4-disubstituted bicyclo[ 22,
2) Octane, represents a trans-2°5-disubstituted 1,3-dioxane bonded to ring B in the 2-position, or IIB represents a trans-1,4-disubstituted cyclohexane; When tfR" represents alkyl, 311A I"at such as 1,4-phenylene, fluoro-14-phenylene, 3,6-disubstituted pyridazine or 2 bonded to ring B in the 2-position;
represents a 5-disubstituted pyrimidine] or the central group of the formula [wherein ring A'HI, 4-7 enylene, fluoro-
1,4-)unicine, trans-1,4-disubstituted cyclohexane, 1°4-disubstituted bicyclo(24
21 octa/, 3.6-disubstituted pyridazine or trans-2, bonded in the 2-position with an ethylene group
5-disubstituted 1,3-dioxane or 2,5-
represents a disubstituted pyrimidine] or the central group of the formula [where ring A''#iI, 4-phenylene, fluoro-
1,4-phenylene, trans-1,4-disubstituted cyclohexane or 1,4-disubstituted bicyclo[
22,2:1 octane, and E represents an ester group] or a central group of the formula [cocote, together with ring A'FillB, 2°6-disubstituted tetralin or 2,6- 2 (equatorial K (
(equatorially) substituted) trans-
decalin] or the central group of the formula [where one of Liao A4, AI and B represents 1°4-phenylene and the others represent 1°4-phenylene 4L
<represents trans-1,4-disubstituted cyclohexane; or ring A"U pyridazine and ring B and 2
-represents a pyrimidine attached at position II, and y! IIA 4 and B represent 1,4-phenylene or trans-1,4-disubstituted cyclohexane; - combined 1, 3
-representing dioxane and ring BUI, representing 4-phenylenemodiketrans-1,4-disubstituted cyclohexane] or the central group of the formula [wherein rings A1 and A7 together represent 2°6- represents a disubstituted naphthalene, a 2,6-disubstituted tetralin or a 2,6-di(equatorially substituted)-transdecalin] or a central group of the formula [wherein rings AI and Ao are together 2゜represents 6-disubstituted naphthalene, 2,6-disubstituted tetralin or 2,6-disubstituted trans-decalin] [wherein , rings AIO, All and B represent the central group of 1,4-phenylene or ld) 5-1,4-diyl-substituted cyclohexane], and R' Fi is a straight chain containing 1 to 9 carbon atoms. R1 on a benzene, monofluorinated benzene or pyrimidine ring
represents a straight-chain alkoxy group containing 1 to 9 carbon atoms, and H*Fi hydrogen, cyano or carbon atoms 1 to 7
Novel naphenylacetylenes and cyclohexylphenylacetin M representing a linear alkyl group containing
KM.

In particular, the present invention relates to a process for the preparation of compounds of formula I as defined above, to liquid-crystal mixtures containing compounds of formula I and to their use for electro-optical devices.

As used herein, the term "linear alkyl group" refers to methyl, ethyl, furoyl, butyl, pentyl, hexyl, heptyl, octyl or nonyl, depending on the number of carbon atoms specified, as well as K The term "straight-chain alkoxy" refers to methoxy, ethoxy, propyloxy, butyloxy, pentyloxy, hexyloxy, heptyloxy, octyloxy or nonyloxy.

The groups substituted ~X (i.e., the ring system consisting of A and f#B) are shown herein as central groups, and the groups
The R meaning is shown as a wing group. , according to the definition of the central group there are at least two and at most four 6
has a membered ring, and thus in the case of the central group of formulas ■, ■ and ■, the two rings can also be fused (fused ring system).
, taken together, depending on the equatorial configuration of the substituents, form naphthalene, tetralin (1,2,3,4-tetrahydronaphthalene) or trans-tetralin (trans-decahydronaphthalene).

As used herein, "ester group EJ is group -co-
Represents o- and -o-co-.

Liquid crystals have recently gained considerable importance, primarily as dielectric materials in display devices, because the optical properties of such materials can be influenced by applied voltage. Electro-optical devices R#-i based on liquid crystals are well known to those skilled in the art and are capable of producing various effects such as dynamic divergence (dy
namic scatter-ring), deformation of aligned phases (DAP type), Shadt-Helfrich effect (rotating cells),
guest/host effect or cholesteric
-nematic) can be based on phase transition7.

Since liquid crystals are suitable as dielectrics for electro-optical displays, K must meet a number of requirements. For example, liquid crystals must have good chemical stability against environmental factors such as heat, air, moisture, etc., must be colorless, have a short response time and extremely high viscosity. The nematic or cholesteric mesophase must be maintained over the entire temperature range in which the liquid crystal cell is operated.
se) and must exhibit good contrast. Other characteristics, e.g. threshold voltage (thr
e-hold potential), dielectric anisotropy (
Depending on the type of cell used (dielect-ric anisotropy) and conductivity, different conditions must be met.

Generally, due to the inability to achieve all desired and to an extent contradictory properties by a single compound,
Attempts have primarily been made to optimize properties for a particular application by mixing several components. However, it is important in this case that the components do not undergo chemical reactions with each other and can be mixed well. Furthermore, the resulting mixture should have no smectic mesophases.

A series of liquid-crystalline compounds having, for example, alkyl, alkoxy, alkanoyloxy, alkoxycarbonyl and cyan groups as wing groups are already known. however,
A notable drawback of known liquid crystals is that compounds with a large mesophase range are generally relatively viscous, whereas compounds with a low viscosity have a small mesophase range or are simply monotropic (mo
It has only a notropic (notropic) mesophase.

Therefore, an object of the present invention is to provide new compounds that can further improve the properties of liquid crystal dielectrics.

Surprisingly, it has been found that the compounds provided by the present invention are mostly liquid crystalline themselves and have a predominantly nematic mesophase.

What is particularly surprising is that the introduction of an acetylene group into the wing group of one of the compounds provided by the invention generally results in a marked extension of the mesophase range or an increase in the clearing point. In addition, the nematic tendency is recognized to be stronger.

Furthermore, the remaining characteristic properties of the individual groups of compounds, such as the low viscosity of phenylcyclohexane, the low threshold voltage of phenyldioxane or phenyl. It is noteworthy that the dielectric anisotropy of rubirimidine is largely preserved. In addition, the compounds provided by the present invention have exceptionally good UV stability.

Therefore, due to the influence of the acetylene groups on the properties of the compounds provided by the invention, on the one hand, compared to known liquid crystals with a similar high mesophase range, improved properties, in particular improved viscosity; Novel liquid crystals with a large mesophase range can be produced with a large mesophase range and response times. On the other hand, compounds with only a small or monotropic mesophase range, such as phenyldioxane, phenylpyrimidine, cyclohexanecarboxylic acid phenyl ester, etc., have often been used in mixtures due to other favorable properties. Corresponding compounds provided by the present invention can be substituted with similar favorable properties and at the same time extended mesophase range. Furthermore, doping agents for the liquid crystal mixture
), but which do not themselves have liquid crystal properties (e.g., 2,6-disubstituted tetralins and trans-decalins, and many phenylcyclohexanes). or at least exhibit low clearing point suppression in mixtures with the corresponding compounds provided by the present invention.

Furthermore, the present invention greatly facilitates the selection of suitable liquid crystalline compounds with very different properties, which substantially facilitates the optimization of the mixture.

The following general formula is an example of a group of compounds provided by the present invention within the scope of Formula I above: XX■ where rings B and C are 1,4-phelene rings or trans-1, 4-disubstituted cyclohexane, and R1 and R1 have the above meanings, provided that IIB and CVi in formula Xx do not simultaneously represent 1,4-phenylene, and ring B in formula XXVK When R'' represents hydrogen or cyano, it shall not represent 1,4-phenylene.

Table 1 below shows variations in mesophase range or mesophase type for representative compounds provided by the present invention. Data for the structural formulas of the compounds are for formulas XX to xx■, where a (aromatic) U1 represents 4-phenylene and S (saturated) represents a trans-1,4-disubstituted cyclohexane group. represents. Compounds for comparison are chosen in which R2 represents a cyano group, which in each case differ from the compounds provided by the invention only in the absence of an acetylene group. To compensate for the effect of chain length, the remaining compound is grouped with −C−=−1 cm
Comparisons were made with compounds having groups -CH, CH, - instead of . N represents the nematic phase type, and S represents the smectic phase type. The monotropic clearing point is placed within ), and the actual circumscribed clearing point is indicated by an asterisk (★). The degree of mesophase range (ΔT) and the melting and clearing points are given in °C.

Preferred central groups in compounds of formula I are those of the above formulas 1, 2,
The radicals of the formulas ■, ■, ■ and X, especially the radicals of the formulas ■, ■ and ■. Compounds of the above formula XX-XXV are preferred for -. Formula XX
, one of fB and C is preferably transformer-1
, 4-disubstituted cyclohexane, while #i
1, 4-7 enylene, and in formula XXI, at least one of rings B and C is preferably trans-
Represents 1,4-disubstituted cyclohexane.

Furthermore, as a KW law, IIB is saturated, i.e. 31B
represents trans-1,4-disubstituted cyclohexane, or in the central group of formula V, 3JI! Preference is given to compounds of formula I in which B together with ring As represents tetralin or trans-decalin. however,
In formulas xxn and XXI, coral B is preferably coral 1
, represents 4-phenylene.

Furthermore, preference is given to compounds of formula I in which ring B is aromatic and R1 represents alkyl.

R2 preferably represents hydrogen, cyano, methyl, ethyl or propyl, especially hydrogen, cyano or methyl. R
1 preferably represents a linear alkyl group having 3 to 7 carbon atoms or a linear alkoxy group having 2 to 6 carbon atoms.

The compounds of formula I shown in the Examples below are examples of preferred compounds.

Compounds of formula I are based on the present invention F! If you follow AK, (a) R”
In order to produce a compound of formula Ⅰ in which represents hydrogen, in the general formula, X represents chlorine or bromine, and 1A, B
and R1 have the meanings given above, are reacted with a base or lithium amalgam and the reaction product is then hydrolyzed, or (b) R2 (c) reacting a compound of formula I in which R represents hydrogen with a base and subsequently with phenyl cyanate; Reacting the compound of I with a base and subsequently with an alkyl bromide or alkyl iodide, or (d) A together with 31B represents a central group of formula 1 and E represents an ester group -CO-O- In order to prepare compounds of formula I, reactive derivatives of the compound-tethered bamboo of the general formula, in which A2 and R1 have the meanings given above, are prepared by preparing compounds of the general formula B and R1 have the meanings given above. or a suitable salt thereof, but (pi
In order to prepare compounds of formula I in which A together with ring B represents the central group of formula (1) and E represents the ester group -0-Co-, in the general formula B and R2 have the abovementioned meanings. is esterified with a compound of the general formula or a suitable salt thereof, in which A2 and R1 have the meanings given above, or (n A together with FB) In order to prepare compounds of formula I representing a central group of formula (1), in the general formula A',
A. and R1 have the abovementioned meanings, and can be prepared by esterifying a compound of or a reactive derivative thereof with a compound of formula xvI above or a suitable salt thereof.

The reaction of the compound of formula (1) according to (a) of the present process can be carried out in a manner known per se. Preferred bases are butyllithium, lithium amide, sodium amide, and the like. If the base is a lithium amide or a sodium amide, liquid ammonia is advantageously used as the solvent; in the remaining cases, an inert chloride, a chloride, a chloride, etc. are used as the solvent.
Preference is given to using ethers such as diethyl ether or tetrahydrofuran. However, the reaction can also be carried out reductively using lithium amalgam instead of the base. For the reaction of compounds of formula Xff containing a pyrimidine or pyridazine ring, lithium amide or sodium amide is advantageously used; for the reaction of compounds of formula
Sodium amide or lithium amalgam are advantageously used.

Pressure and temperature are not critical for this reaction. Generally atmospheric pressure and temperatures between about -80°C and about 100°C are used. The subsequent hydrolysis is preferably carried out using distilled water, aqueous ammonium chloride solution, or the like.

The reaction of a compound of the formula I in which R2 is hydrogen with a base and phenyl cyanate according to step (b) of the process can be carried out in a manner known per se. Preferred bases are butyllithium, lithium diisopropylamide, lithium atadohesodiumamide, and the like. If the base is lithium amide or sodium amide, liquid ammonia is preferably used as solvent; in the remaining cases, inert organic solvents, preferably ethers, such as diethyl ether or hytetrahydrofuran, are advantageously used as solvent.

For the reaction of compounds containing pyrimidine or pyridazine rings, lithium diisopropylamide is the preferred base, and for the reaction of compounds containing ester groups, lithium amide over sodium amide is the preferred base. Temperature and pressure are not critical; however,
'f generally between about -80°C and about -40°C! ! A degree and atmospheric pressure are preferred.

Additionally, the reaction of the compound of formula I in which R1 represents hydrogen with a base and an alkyl bromide or alkyl iodide according to (c) of the present process can be carried out according to methods known per se; The bases and solvents indicated for method (b) can be used. Preferably, hexamethylphosphoric triamide is added to the reaction mixture before alkylation with alkyl bromide or alkyl iodide. Atmospheric pressure and about -45
Temperatures between 0.degree. C. and the reflux temperature of the reaction mixture are advantageously used.

The esterification by (d14 (e) and ge) in this method can be carried out in a method known per se. Formula x■
, X■ and Xl are acid chlorides, bromides and anhydrides. Suitable salts of alcohols of formulas XVI and X■ are, for example, alkali metal salts, especially sodium salts. The reaction of alcohol and carboxylic acid can be carried out, for example, in the presence of an inert organic solvent or without such a solvent, 7 in the presence of a catalytic amount of a strong acid (for example sulfuric acid or if hydrohydric acid). Furthermore, one method includes, for example, the reaction of an acid chloride with an alcohol in the presence of an inert organic solvent such as diethyl ether, tetrahydrofuran, dimethylformamide, benzene, cyclohexane or carbon tetrachloride and/or an acid binder such as pyridine. It is. However, esterification of the carboxylic acid with an alcohol in the presence of N,N'-dicyclohexylcarbodiimide and 4-(dimethylamino)pyridine is preferred.

Temperature and pressure are critical; generally the esterification is carried out at atmospheric pressure and a temperature between room temperature and the boiling point of the esterification mixture. Acid chlorides and anhydrides can be prepared by methods known per se; for example, acid chlorides are obtained by reacting the corresponding acid with phosphorus mitakaide, phosphorus pentachloride, thionyl chloride, etc. The compounds can be obtained by reacting the corresponding acids with acetic acid hydrate, arhythyl chloride, ethyl chloroformate, etc.

(c) of the compound of formula XIV and of the present method
) is illustrated by the following reaction formula 1; Formula 11, where B, R' and carbon y1 child 1-7
Represents a straight-chain alkyl group containing .

Four
-= If the compound of formula xX■ contains an ester group, this group is reductively cleaved during the reaction with diisobutylaluminum hydride. In this case, the reaction is therefore carried out using the corresponding cyano-alcohol or the corresponding cyano-carboxylic acid as starting material and the resulting aldehyde is esterified in a manner known per se to form the compound of the formula XX [.

Compounds of formula XIV without an ester group and a pyrimidine or pyridazine ring can also be converted directly to compounds of formula 1b using, for example, butyllithium and then phenyl cyanate. Furthermore, compounds of formula XIV can be converted directly to compounds of formula 1c using, for example, sodium amide and alkyl bromide or alkyl iodide in ammonia.

Compounds of formula I containing a single pyrimidine or dioxane ring can be prepared by first introducing an acetylene group and then forming a heterocyclic ring. Examples of such reactions as well as formula x
The preparation of compounds of xxtv and xxxv (i.e. compounds of formulas XVI and 1 in which R2 represents hydrogen) is shown in the following reaction scheme 2; where B and R1 have the above meanings, and Tstip - Represents a tosyl group.

/ ,.

Compounds of formula xxxv can be prepared not only from compounds of formula xxx but also starting from corresponding compounds containing a methoxycarbonyl group in place of the cyano group.

Formulas XVI and X■ in which R2 represents cyano or alkyl
Formula 1 XXXTV and xxx to produce compounds of
The compound of v is reacted with a base and phenyl cyanate or an alkyl bromide or alkyl dinitride analogously to methods (b) and (c) above. However, also
In the same manner as the above methods (d) to (f), first, the formula XXX
It is also possible to esterify the compounds of IV and xxxv and then introduce a cyano or alkyl group.

Furthermore, compounds of formula x1 in which R'' represents hydrogen or alkyl can be prepared by converting the hydroxy group of p-hydroxybenzaldehyde or tahtrans-4-hydroxycyclohexanecarboxaldehyde in a manner known per se (for example in the presence of p-)luenesulfonic acid. (by dihydropyran in methylene chloride below) to the tetrahydropyranyloxy group, then convert the formyl group to an alkynyl group in a manner similar to Scheme 1, and finally to cleave the tetrahydropyranyl group. , by hydrolyzing the resulting compound with an acid (eg aqueous sulfuric acid).

ifc, p-(1-alkynyl)benzaldehyde and trans-4-(1-alkynyl)cyclohexanecarboxaldehyde, for example, p-(jethoxymethyl)benzaldehyde l is trans-(jethoxyl methyl ) can be prepared by converting the formyl group in cyclohexanecarboxaldehyde to an alkynyl group and then hydrolyzing the cetyl group (eg, with aqueous sulfuric acid). Next, the resulting aldehydes were treated with the corresponding 1, 3 in the same manner as in reaction formula 2.
- Can be converted to dioxane or dioxane (Jo
nes') oxidation to produce compounds of formula X■ in which R1 represents hydrogen or alkyl.

Furthermore, 4-iodophenol is converted to p-[(trimethylsilyl)ethynylphenol by ethynyltrimethylsilyl/ in the presence of bis-(triphenylphosphine)-haladium (■) dichloride, steel (I) lauride, and triethylamine. be able to. Next, add this compound.

For example, by reacting with potassium hydroxide in methanol/water, p-ethynylphenol (formula XXX where ring B is aromatic)
TV compound) or reacted with methyllithium in tetrahydrofuran/hexamethyl phosphate triamide and ferrous cyanate to form (p-hydroxyphenyl)propiolonitrile (where B is aromatic and R'' is A compound of formula XVI representing cyano) can be produced.

Most of the compounds of formula XX■ are known or can be prepared in analogy with known compounds.

The method for producing the remaining compound of formula XX■ is as follows:
In the formula, B and R1 have the meanings given in E, and ring C is 1,4-phenylene or trans-1,4
- represents a disubstituted cyclohexane, R represents a linear alkyl group containing 1 to 8 carbon atoms, and TS represents p
- represents a tosyl group, and the broken M (----) indicates that one of the bonds represented by K is a double bond.

−− ≧ 〉 − One country −
− (J (J
Yamarihachi
-IJ
Kōkō Threshold Stepter
In the reaction of compounds of formulas VLI and IJ by 3-
Benzyl-5-(2-hydroxyethyl)-4-methyl-1,3-thiaturium chloride is the preferred catalyst.

In the Bittig reaction to prepare compounds of formula L, one can start from compounds of formulas XXX and LI (as shown in Scheme 5) or the corresponding compounds in which the reactive group has been exchanged, i.e. the formyl group. is located on ring C and the group -CHtP''(CsHe), Br- is on IIB.

If one of rings B and C is aromatic and the other is saturated, the Bitteig reaction preferably combines a formyl group and an aromatic term on the saturated ring, and a group -CH,P" (C6
H3), using a compound having Br-.

Compounds of formula xxvi in which A and 11B together represent a central group of formulas 1 to 1 can also be prepared by the same process. The starting materials for the Pittich reaction are advantageous in this case [j: from the corresponding nitrile, for example by reducing the cyano group to the formyl group using diisobutylaluminum hydride and optionally further converting the formyl group to lithium hydride in tetrahydro7rane. base using aluminum
CH! It is prepared by reducing to OH and then continuing as in Equation 5.

Aldehydes of formulas LXVI and LXVI can also be obtained from the corresponding carboxylic acids by reaction with thionyl chloride followed by Rosenmund reduction.

Compounds of formula I can be used in the form of mixtures containing two or more compounds of formula I or in the form of other liquid-crystalline or non-liquid-crystalline substances, such as Schiff's base, azobenzenes, azoxybenzenes, benzoate. acid phenyls, cyclohexanecarboxylic acid phenols, cyclohexanecarboxylic acid cyclohexyl esters, biphenyls, ter7enyls, phenylcyclohexanes, cinnamic acid derivatives, phenylpyrimidines, diphenylpyrimidines, cyclohexylphenylpyrimidines, It can be used in the form of a mixture with substances from the group such as phenyldioxanes and 2-cyclohexyl-1-phenylethanes. Such materials are known to those skilled in the art, and many are commercially available.

One of the compounds of formula I in a mixture provided by the present invention
4' is generally a must, 1! You can choose according to your needs.

For example, a mixture provided by the invention can consist of two or more compounds of formula I. The mixtures provided by the invention advantageously contain at least about 1.1 g of the compound of formula I.

Furthermore, the mixtures provided by the present invention contain suitable optically active compounds (e.g. optically active biphenyl a) and /f
or dichroic colorants such as azo, azoxy and anthraquinone colorants. The amount of the compound depends on the solubility and desired pitch, color, and absorbance.
Determined by etc. The base optically active compound is preferably about 4 weights and the amount of dichroic colorant is preferably at most about 10 weights.

The production of liquid-crystal mixtures and electro-optical devices containing one or more compounds of the formula I can be carried out in a manner known per se.

The present invention also covers all novel compounds mentioned herein,
Concerning mixtures, production, uses and equipment.

The preparation of the compounds provided by the present invention will be explained in more detail based on the following examples. The abbreviations used for phase transitions have the following meanings: cti stands for crystalline phase, S stands for smectake phase, N stands for nematic phase, and I stands for isotropic phase, +'-p- stands for Represents two different liquid crystal correlation dislocation points. η represents viscosity (bulk viscosity).

Example 1 4-(2°2-dibromovinyl)4/-pentylbiphenyl 2, . in anhydrous tetrahydrofuran 50-. A solution of 609 was placed in a sulfonation flask at −78° C. under argon gas and treated within 5 minutes with 14.5 aj of a 1.2N solution of butyllithium in hexane. After the addition was complete, the mixture was warmed to -10 DEG C. within 10 minutes, then recooled to -78 DEG C. and then treated with a solution of 1.5114 phenyl cyanate in 10 DEG C. of anhydrous tetrahydrofuran. The mixture was then stirred for a further 30 minutes at -78°C, poured into 100 parts of water and extracted three times with 100 parts each of diethyl ether. The organic phase was washed twice with 5QIIj each of water, dried over magnesium sulfate and concentrated. The residue (151g) was subjected to low pressure chromatography (O,S Parr) on silica gel using hexane and then 20% ethyl acetate/petroleum ether, then recrystallized from methanol to give (4'- 1.02 g (58 °C) of pentyl-4-biphenylyl (purity: 99.6) was obtained; melting point (C-N) 51.0°C, clearing point (N-I) 120
．． 2℃.

4-(2,2-dipromohy=A used as starting material)
/ ) -4'-Pentylbiphenyl a Prepared as follows: (+) A solution of 6.23 g of 4'-pentyl-4-cyanobiphenyl in 50 d of anhydrous toluene at 0° C. under total argon gas. A 1.36N solution of diimbutylaluminum hydride in toluene was added to a reaction flask.
It was processed within 10 minutes. After the addition was complete, the mixture was stirred for a further 22 hours at room temperature, then carefully poured into 50 mL of IN sulfuric acid and extracted three times with 100 d each of diethyl ethyl. The organic phase was washed once with 50 - IN sulfuric acid and twice with 5 QwJ of Sphagnum moss, dried over magnesium sulfate and concentrated. The oily residue (6,0,9) was subjected to low pressure chromatography on silica gel using 10% ethyl acetate/petroleum ether to give 4-formyl-4'-pentylbiphenyl 1°99.71)5 as a colorless viscous oil. , 869 (93
) was obtained. Rf value [Toluene/ethyl acetate (19:1
)]: extract 0.49, product 0.28° (b) A solution of 15.39 ml of tetrabromomethane in 150 d of methylene chloride was placed in a sulfonation flask at 0° C. under argon gas and 50 11 d of methylene chloride was added. of triphenylphosphine 12.1 within 5 minutes. After the addition was complete, the clear organic reaction solution was stirred for 5 minutes at 0°C and then 4-formyl-4 in 50j of methylene chloride was added.
After stirring for a further 45 minutes at /-phenylene θ° C., the yellow-orange mixture was poured into 1000° C. of hexane, whereby the separated precipitate was separated (rinsed with hexane).

The concentrated solution F was crushed with 400 d of hexane, left at 0° C. for 18 hours, rinsed with hexane), and the solution F was concentrated. The residue (9,8 g) was subjected to low pressure chromatography (0,5 par) on silica gel with hexane to give 4-(2,2-dibromovinyl)-4'-pentylbiphenyl (purity 99.1) as colorless crystals. )5.
Obtained 15 g (554); melting point 95°C.

In a similar manner the following compounds could be prepared: (4'-propyl-4-biphenylyl)proviolonitrile, (4'-butyl-4-biphenylyl)propiolonitrile, (4/-hexyl- 4-biphenylyl)propioloethryl, (4/-hebutyl-4-biphenylyl)furoviolonitrile, (4'-ethoxy-4-biphenylyl)proviolonitrile, (4/-furobyloxy-4-biphenylyl)propiolo Nitrile, (4'-butyloxy-4-biphenylyl)propiolonitrile, (4'-pentyloxy-4-biphenylyl)propiolo, nitrile, (4'-hexyloxy-4-biphenylyl) ) Propiolonitrile.

Example 2 In a similar manner to Example 1, a solution of 4-(2,2-dibromovinyl)4/-pentylbiphenyl in anhydrous tetrahydrofuran is placed in a sulfonation flask and treated with a solution of butyllithium in hexane for 5 minutes. processed within.

After the addition is complete, the mixture is heated to -10°C within 10 minutes,
Then it was poured into water and extracted with diethyl ether. The organic phase was washed with water and saturated sodium chloride solution, dried over magnesium sulphate and concentrated. The residue was subjected to low pressure chromatography on silica gel with hexane and recrystallized from methanol to give 4-ethynyl-4'-pentylbiphenyl (purity 99.5%) as colorless crystals.
obtained; melting point (C-N) 56.4°C, clearing point (N-I)
82.7℃.

In a similar manner the following compounds could be prepared: 4-ethynyl-4/7''ropylbiphenyl, 4-ethynyl-4/7'tilbiphenyl, 4-: L f k-4
'-Hexylbiphenyl, 4-ethynyl-4'-hebutylbiphenyl, 4-ethynyl-4'-ethoxybiphenyl, 4-ethynyl-4'-7"ropyloxybiphenyl, 4-ethynyl-4'-butyloxy Biphenyl, 4-ethyl-4'-pentyloxybiphenyl, 4-ethynyl-4'-hexyloxybiphenyl 1 Example 3 β, β-Sifuromor p-() lance-4-pentylcyclohexyl)styrene in 150 m of anhydrous tetrahydrofuran A solution of 7.889 was placed in a sulfonation flask at −78° C. under argon gas and treated within 10 minutes with a 1.2 N solution of butyllithium in hexane. After the addition was complete, the mixture was heated to −78° C. Stirred for 1 hour at 0.degree. C. and another 1 hour at -10.degree. C. and extracted twice.The organic phase was washed with 100 ml of water and 100 ml of saturated sodium chloride solution, dried over magnesium sulfate and concentrated.The remaining crystallized The oil was subjected to low pressure chromatography (0.5 par) on silica gel with hexane to give 1-ethynyl-4-()lanth-4-pentylcyclohexyl)benzene (purity 99.31) as colorless crystals. 85); melting point (C-N) 39.4°C, clearing point 411°C.

The β,β-dibromo p-()lans-4-pentylcyclohexyl)styrene used as starting material was prepared as follows: 16.6 d of tetrabromomethane in 230 d of methylene chloride.
The solution of g at 0° C. under argon gas was placed in a replacement flask and treated in portions within 10 minutes with solid triphenylphosphine 26.29; this resulted in a clear dark orange solution. .

After the addition was complete, the mixture was stirred for a further 5 minutes at 0° C. and then a solution of p-()lans-4-pentylcyclohexyl)benzaldehyde 6.46.9 in 20-methylene chloride was added dropwise within 10 minutes. . After stirring for an additional hour at 0°C,
The orange mixture was poured into 750 d of hexane, whereby the separated precipitate was filtered out (rinsed with hexane). The concentrated filtrate (20,4J7) was triturated with 250-ml of warm hexane (rinsed with warm hexane) and the filtrate was concentrated.

The remaining oil (9,70,9) was purified by low pressure chromatography on silica gel with triethyl acetate/petroleum ether.
0.5 bar) to give β,β-dibromo p-(trans-4-pentylcyclohexyl) as colorless crystals.
8.08 g (78 hours) of styrene (M degree 97.51) was obtained; melting point 48°C.

The following compound could be prepared in a similar manner: 1-ethynyl-4-():5'n-4-globylcyclohexyl)benzene, melting point 39.9°C, 1-ethynyl-4-()lance -4-7'tylcyclohexyl)benzene, 1-ethynyl-4-(trans-4-hexylcyclohexyl)benzene, 1-ethynyl-4-(trans-4-heptylcyclohexyl)benzene, melting point (C-N) 37 .6°C, clearing point (N-I) 47.5°C.

Example 4 1-ethynyl- in anhydrous tetrahydrofuran 5011j
A solution of 1.2 g of 4-(trans-4-pentylcyclohexyl)benzene (prepared according to Example 3) was placed in a sulfonation flask at −40° C. under argon gas, and 1.2 g of 4-(trans-4-pentylcyclohexyl)benzene (prepared according to Example 3) was added to a sulfonation flask at 1.2 g of 4-(trans-4-pentylcyclohexyl)benzene (prepared according to Example 3). 2N solution4.
It was processed at 72m. After the addition was complete, the mixture was stirred for a further 15 minutes at -40°C, then treated with phenylcyane) 1.07117 at -78°C and stirred for a further 45 minutes at -78°C. The mixture was then poured into 5Qa/water and extracted three times with 50wLl each of diethyl ether. The organic phase was washed with 50 ml of water and 59*l of saturated sodium chloride solution, dried over magnesium sulphate and concentrated. The crystalline residue was subjected to low pressure chromatography (0.5 bar) on silica gel with triethyl acetate/petroleum ether to give p-(trans-4-pentylcyclohexyl)phenylbropiolonitrile (purity 99.5 bar) as colorless crystals. 6)1
．． I got 20.17 (91st section). It was crystallized once from methanol, and the melting point (C-N) was 49.7°C and the clearing point (N
-I) 687 ml of product having a temperature of 128.9°C were obtained.

In a similar manner the following compounds could be prepared: p-()trans-4-propylcyclohexyl)phenylproviolonitrile, p-(trans-4-7'tylcyclohexyl)phenylpropiolonitrile, p-( ) trans-4-hexylcyclohexyl)phenylpropiolonitrile, p-(trans-4-hebutylcyclohexyl)phenylpropiolonitrile.

Example 5 A solution of 1.55% of β,β-dibromo p-(2-(t-lance-4-pentylcyclo-\xyl)ethyl)styrene in 35% of anhydrous tetrahydrofuran was heated to about −45° C. under argon gas. was placed in a sulfonation flask and treated within 5 minutes with a 1.2N solution of butyllithium in hexane. After the addition was complete, the mixture was further heated at the same temperature for 9 hours.
The mixture was stirred for 0 minutes, then cooled to -78°C and treated with phenylcyane (0.79°C). The mixture was stirred for a further 3 hours at -78°C and
and extracted three times with 59 m each of diethyl ether/petroleum ether (i:t). The organic phase was washed with IN sodium hydroxide solution 5011j and with saturated sodium chloride solution 50-1, dried over magnesium sulfate and concentrated.

The residue (1,117) was dissolved in hexane on silica gel, then 3
Low pressure chromatography (0,5)(-L) with ethyl acetate/petroleum ether gave p as colorless crystals.
-[2-()Lance-4-pentylcyclohexyl)ethyl]phenylbroviolonitrile (purity 97.34)
740 wQ (69 t) was obtained which was further recrystallized from methanol; melting point (CN) 36.7°C, clearing point (N-I) 105.5°C.

β,β-dibromo p-(2-
(trans-4-pentylcyclohexyl)ethyl]styrene was prepared as follows: (a) 7.089 g of p-C2-()trans-4-pentylcyclohexyl)ethyl]benzonitrile in 50% of anhydrous toluene. The solution was placed in a sulfonation flask at 0°C under argon gas, heated so that the internal temperature did not exceed 5°C, and treated within 15 minutes with a 1.21 N solution of diisobutylaluminum hydride in toluene, 29w1. did. After the addition was complete, the mixture was stirred for a further 2 hours at room temperature and then carefully diluted with 0.5N sulfuric acid 5.
0 m and extracted three times with each iQ□+1 diethyl ether. The organic phase was washed twice with 50° each of half-saturated sodium chloride solution, dried over magnesium sulfate and concentrated. p-[2-(trans-4-
pentylcyclohexyl)ethyl] benzaldehyde (
6.20 g (87 g) of pure U97 was obtained, which was used without further purification; Rf value [toluene/ethyl acetate (19:1)]: extract o, 67, product 0. 54° (b) Tetrabromomethane 1a29L in 100m/methylene chloride) Riphenylphosphine 10.49
A mixture of J7 and 2.62 g of zinc dust was stirred at room temperature for 24 hours in a sulfonation flask under argon gas.

Thus, the color of the heterogeneous mixture changed from yellow-green to dark purple and then pale purple.

Next, p-[2-(trans-
A solution of 2.86 J7 of 4-pentylcyclohexyl)ethyl]benzaldehyde was added dropwise and the mixture was stirred at room temperature for 4 hours.
Stir for an hour and then pour into 700ml of pentane. The precipitate that separated out was rinsed separately with pentane), the concentrated filtrate (5.25 g) was triturated with 300 d of pentane, filtered and concentrated. The residue (4,81) was subjected to low pressure chromatography (0,5 par) on silica gel with 34 ethyl acetate/petroleum ether to give β,β-dibromo p-C2-()lans-4- as colorless crystals.
Pentylcyclohexyl)ethyl]styrene (purity 99
．． Section 8) Obtained 3.139 (71 regrets); Melting point 47.3
℃.

In a similar manner the following compound could be prepared: p-[2-(trans-4-furovylcyclohexyl)
Ethyl]phenylpropiolonitrile, p-[2-()
lance-4-7'ylcyclohexyl)ethyl]phenylprozeolonitrile, p-(2-()lance-4-hexylcyclohexyl)ethyl]phenylpropiolonitrile, p[2-(1;yyx-4-hbutyl) cyclohexyl)ethyl]phenylbropiolonitrile.

Implementation! 16 In a method similar to Example 5, β, β-dibromo p-[2-(trans-4-
A solution of pentylcyclohexyl)ethyl]styrene was placed in a sulfonation flask and treated within 5 minutes with a solution of butyllithium in hexane. After the addition was complete, the mixture was stirred for another 90 min at the same @2 temperature and then KIN hydroxylated).
Poured into IJum and extracted with petroleum ether. The organic phase was washed with water and saturated chloride solution, dried over magnesium sulfate and concentrated. The residue was subjected to low pressure chromatography on silica gel with hexane;
Pure 1-ethynyl-4-(2-()lans-4-pentylcyclobexyl)ethyl]benzene was obtained as colorless crystals*: s point (CN) 25.5°C, clearing point 42.
5℃.

In a similar manner the following compounds could be prepared: 1-ethynyl-4-[2-(trans-4-propylcyclohexyl)ethyl]benzene, 1-ethynyl-4-
(2-() lance-4-butylcyclohexyl)ethyl]benzene, melting point (C-N) 10.0°C, clearing point (
N-I) 25.2°C, η(22°C) = 13.5cp.

1-ethynyl-4-[2-()lance-4-hexylcyclohexyl)ethyl]benzene, 1-ethy-4-
(2-()lance-4-hebutylcyclohexyl)ethyl]benzene, melting point (C-N) 29.9°C, clearing point (N
-I) 49.3°C.

Example 7 Trans-2-Cp in anhydrous tetrahydrofuran 8o-
A solution of 3.5 g of -(2,2-dibromovinyl)phenyl]-5-butyl-1,3-dioxane was placed in a sulfonation flask at -78°C under argon gas, .2N solution $13.4- within 5 minutes. After the addition is complete, add the mixture to 10"CK: 1
It was held for an hour, then cooled again to -78 DEG C. and treated with phenyl cyanate 1.2- within 5 minutes. The mixture was stirred for a further 30 minutes at -78 DEG C., poured into 100 ml of water and extracted three times with 100@l of diethyl ether. The organic phase was diluted with 100 d of water and 1 d of saturated sodium chloride solution.

d, dried over potassium carbonate, and concentrated. The residue (3,26j7) was purified on silica gel with petroleum ether/ethyl acetate/triethylamine (97:3:0.2).
low pressure chromatography (0.5 par) and p-(trans-5-butyl-1,3-dioxan-2-yl)phenylpropiolonitrile (purity 98.
Section 7) 1.18 g (504) was obtained. Recrystallized from 50m of λ xane as colorless crystals.
4) 1.03g was diluted; melting point (C-N) 54.3℃,
Clearing point (N-I) 108.7°C.

Tolan used as starting material, -2-Cp-(2,
2-dibromovinyl)phenyl]-5-butyl 1.3
-Dioxane was prepared as follows: (al) A solution of 491.17 p-(trans-5-butyl-1,3-dioxan-2-yl)benzonitrile in 5011j of anhydrous toluene was prepared under argon gas. 0℃
into a sulfonation flask and treated within 3 minutes with a 10-3N solution of diisobutylaluminum hydride in toluene. After the addition was complete, the mixture was stirred at room temperature for 22 hours, then carefully poured into 100 ml of potassium sodium tartrate solution and extracted three times with 100 ml of diethyl ether. Add the organic phase to 10% potassium sodium tartrate solution I
QIId1 was washed once with saturated sodium chloride solution 100117, dried over potassium carbonate and concentrated.

The residue (5,Fi 9') was purified on silica gel in petroleum ether/ethyl acetate/triethylamine (80:20:1).
Therefore, it was subjected to low pressure chromatography (O,S bar) to give p-()lanse-5-butyl- as a colorless viscous oil.
1,3-dioxan-2-1)benzaldehyde (purity 98.3) 5.08j7 was obtained), which was used without further purification: Rf value [toluene/ethyl acetate (
19:1)): extract 0.28, product 0.19° (bl) A solution of 13.6 g of tetrabromomethane in 150 d of methylene chloride was placed in a sulfonation flask at 0° C. under argon gas and chlorinated. Treated within 10 min with a solution of triphenylphosphine 21.51 J7 in 40 m of methylene. After the addition was complete, the clear orange solution was stirred for a further 5 min at 0 °C [7, then p-() in 30 m of methylene chloride.
lance-5-butyl-1,3-siokylin-2-yl)
A solution of 5.08 g of benzaldehyde was subjected to KM within 5 minutes. The mixture was then stirred at 0° C. for 30 minutes, the contents of the flask were poured into hexane:/800-, and the precipitate that had separated was filtered out (rinsed with hexane). The concentrated solution F was crushed with 400 d of hexane, left at 0° C. for 15 hours, filtered and rinsed with hexane), and the solution F was concentrated. The residue (8,29) was purified on silica gel in hexane and then petroleum ether/ethyl acetate/triethylamine (97:3:0
．． 5) was subjected to low-pressure chromatography (O,S bar) to obtain trans-2-CP-(
2,2-dibromovinyl)phenyl)-5-butyl-1
3.23 g of 3-dioxane (purity 95.1 width) was obtained; Rf value [petroleum ether/ethyl acetate (97:3)] 0
．． 17° In a similar manner the following compound could be prepared: p-(trans-5-propyl-1,3-dioxane-
2-(l)phenylpropiolonitrile, p-(trans-5-pentyl-1,3-dioxan-2-yl)phenylproviolonitrile, melting point (C-N) 60.3°C
, clearing point (N-I) 111.0°C, p-(trans-5-hexyl-1,3-dioxane-
2-yl)phenylproviolonitrile, p-(trans-5-heptyl-1,3-dioxan-2-yl)phenylbropiolonitrile.

Example 8 In a sulfonation flask equipped with a gas inlet, a dry ice condenser and a mechanical stirrer, about 100 g of ammonia is condensed under argon gas at -78° C. until the color tone is maintained. Treated with sodium metal. A spatula of iron nitrate was then added, the grayish mixture was treated in portions with 820q of sodium metal, and the resulting mixture was stirred for 30 minutes at 178 Uf. 2-(p-(2,2-dibromovinyl)phenyl)-5-pentylhylyzine 1 in diethylny7A, 10d
．． A solution of 029 was added dropwise within 5 minutes, the green-yellow mixture was then stirred at -78°C for 45 minutes to evaporate the ammonia, and the mixture was treated with 3°d of saturated cyclized ammonium solution and diluted with diethyl ether. Extracted three times at 50 m each. The organic phase was diluted twice with 50° each of water and once with saturated sodium chloride solution.
Washed twice, dried over magnesium sulfate, and concentrated. The resulting orange oil was diluted with 10 ml of ethyl acetate on silica gel.
Low pressure chromatography (0,5
2-(p-ethynylphenyl)-5-pentylpyrimidine 4471q (71
) was obtained; melting point: 7L3°C.

The 2-[p-(2,2-dibromovinyl)phenyl-5-pentylpyrimidine used as starting material was prepared as follows: (a) In a sulfonation flask equipped with a mechanical stirrer, the chloride Methylene 120sJt4'1) p-(5-pentyl-2-pyrimidinyl)benzonitrile 3,50
A solution of F was introduced at -78°C under argon gas and treated within 5 minutes with a 1.5N solution of diisobutylaluminum hydride in toluene.
A white precipitate formed shortly before the end of the addition). The mixture was stirred for a further 30 minutes at -78°C and then
@JV7 and extracted 3 times with 150 ml of diethyl ether each. The organic phase was washed twice with 100 g each of water and once with 100 g of saturated sodium chloride solution, dried over magnesium sulfate and concentrated. The residue (13!9) was subjected to low pressure chromatography (0.5 Parl) on silica gel with 10 ml of ethyl acetate/petroleum ether to give p-(5-pentyl-2-pyrimidinyl)benzaldehyde 2.0 as colorless crystals. ．． 08g (591g) was obtained and the kernel was used without further purification; Rf*() toluene/ethyl acetate (19:1); extract 0.29, product 0.22°(b) In a sulfonation flask equipped with a mechanical stirrer, 5.0% tetrabromoethane in 80% methidine chloride.
A solution of 44.9 was charged at 0° C. under argon gas and treated within 10 minutes with a solution of triphenylphosphine &6 g in 20-methylene chloride.

After the addition was complete, the clear orange solution was stirred for a further 5 minutes at 0°C and then p-(5-pentyl-2) in methylene chloride 15-
A solution of 2.08 g of -pyrimidinyl)benzaldehyde was added dropwise within 5 minutes. The mixture was stirred for a further 30 minutes at 0°C, then the contents of the flask was dissolved in 700 slK of hexane.
The precipitate separated by K was filtered out (rinsed with hexane).

The concentrated filtrate was crushed with 200 m of hexane, left at 0° C. for 18 hours, and then rinsed with hexane), and the filtrate was concentrated. The residue (λ79) was subjected to low pressure chromatography on silica gel with 31 ethyl acetate/petroleum ether (
2-(p-(
2,2-Dibromovinyl)phenyl]-5-pentylpyrimidine (purity 9454) Z70Jii' (80%) was obtained; melting point 74°C.

The following compounds were prepared in a similar manner: 2-(p-ethynylphenyl)-5-7' lovylpyrimidine, 2-(p-ethynylphenyl)-5-7'ylpyrimidine, 2-(p-ethynyl phenyl)-5-hexylpyrimidine, 2-(p-ethynylphenyl)-5-hebutylpyrimidine, 2-(p-ethynylphenyl)-5-ethoxypyrimidine, 2-(p-ethynylphenyl)-5-7 'Ropyloxypyrimidine, 2-(p-ethynylphenyl)-5-butyloxypyrimidine, 2-(p-ethynylphenyl)-5-pentyloxypyrimidine, 2-(p-ethynylphenyl)-5-hexyloxypyrimidine .

Example 9 2-(p-ethynylphenyl>-S-pentylhyrimidine (Example 8) in anhydrous tetrahydrofuran 301114
A solution of lithium diisopropylamide 152q (produced according to of diisopropylamine 0.
22 M-f) prepared by adding 0.89 m of a 1.6ON solution of butyllithium in hexane to the solution at 0°C)
was processed within 15 minutes. After 5 minutes, phenylcyane)
182 μt was added and the mixture was stirred at −78° C. for 90 minutes, then poured into 30 μm of water and 50 μm each of diethyl ether.
Extracted three times with j. Add saturated sodium chloride solution to the organic phase
0-, dried over magnesium sulfate, and concentrated. The residue was subjected to low pressure chromatography (0,4 bar) on silica gel with 5-pentyl acetate/petroleum ether to give p-(5-pentyl-2-
pyrimidinyl) phenyl prohydronitrile 88q(
221) t' was obtained. Recrystallization from methanol gave colorless needle-like crystals (purity 99.44); melting point (C-N) 7a2
°C, clearing point (N-I) 128.5 °C.

In a similar manner the following compounds could be prepared: p-(s-furopy-2-pyrimidinyl)phenylproviolonitrile, p-(5-butyl-2-pyrimidinyl)phenylproviolonitrile, p-(5 -Hexyl-2-pyrimidinyl)phenylpropiolonitrile, p-(5-hebutyl-2-pyrimidinyl)phenylpropionitrile, p-(5-ethoxy-2-pyrimidinyl)phenylpropiolonitrile, p-(5- Propyloxy-2-pyrimidinyl)phenylpropiolonitrile, p-(5-butyloxy-2-pyrimidinyl)phenylproviolonitrile, p-(5-pentyloxy-2-pyrimidinyl)phenylpropiolonitrile, p-(s- He*syloxy-2-pyrimidinyl)phenylproviolonitrile.

Example 10 (p-hydroxyphenyl)furopionitrile 14311F, trans-4-pentylcyclohexanecarvone 111218sv in methylene chloride 15d.

A mixture of N,N'-dicyclohexylcarbodiimide 227 and 4-(dimethylamino)pyry<X 12.2 was stirred in a round bottom flask under argon gas at room temperature. The yellow heterogeneous mixture was poured into 3 Qd of water and extracted twice with 30° each of methylene chloride. The organic phase was washed successively twice with 30 liters of water, twice with 3 qd of acetic acid and twice with 30 liters of water, dried over magnesium sulfate and concentrated. The residual solution (383w9) was diluted with 383w9 on silica gel.
Low-pressure chromatography (0,4 Parr) was performed on a dimethyl acetate/petroleum needle to obtain colorless crystals, p-(2
-cyanoethynyl) phenyl ester 270wg (84
1') was obtained. One crystallization from hexane gave ester (purity 99.7%) 219m+9 as colorless plate crystals; melting point (C-N) 76.8°C, clearing point (N-I")
) 153.2℃.

The (p-hydroxyphenyl)propiolonitrile used as starting material was prepared as follows: (a) 4-iodophenol 4.409 in triethylamine sow in a sulfonation flask equipped with a mechanical stirrer. ,
Ethynyltrimethylsilane 2.369, bis-(triphenylphosphine)-palladium(1) dichloride 28゛O
q and anhydrous iodized steel (I) 2019 was stirred at 50° C. for 4 hours under argon gas. The resulting gray-brown heterogeneous mixture was gently rinsed with diethyl ether),
The filtrate was then concentrated. Remaining brown-orange oil (5,89
9) was subjected to low pressure chromatography (0.5 bar) on silica gel with i0 ethyl acetate/petroleum ether to give an orange oil 4.40%, which after further bulb-tube distillation ( 135-160℃
10.4-0.3-Hli'), 3.25 g (864) of p-[()limethylsilyl)ethynylsiphenol were obtained as light yellowish waxy crystals; mp 60-63.
5℃.

Q) 3 p- in hexamethylphosphoric triamide 5d
C(trimethylsilyl)ethynylsiphenol 381w
The solution of II was treated in a sulfonation flask under argon gas at -5 DEG C. with 2.5 mm of a 1.75 M solution of methyllithium in diethyl ether. 15 days after addition
At 1 minute, the mixture, which became a red slurry, was diluted with anhydrous tetrahydrofuran and then stirred at room temperature for 3 hours. The mixture was cooled to -30°C and phenyl cyanate 32
2μt was added. The brown-orange clear solution was warmed to 0° C. within 60 minutes, then poured into 50° of KIN hydrochloric acid and extracted three times with 5 QWd each of diethyl ether. The organic phase was further washed three times with 50° each of water (with the addition of a small amount of sodium chloride solution), dried over magnesium sulfate and concentrated.

The orange residue (5701q) was low pressure chromatographed (0,4 Parr) on silica gel with 151% ethyl acetate/petroleum ether and then 20% ethyl acetate/petroleum ether to give (p-hydroxyphenyl) as light yellowish crystals. ) 160 wIg (56 kg) of gropiolonitrile were obtained; melting point 134-137°C.

The following compound could be produced in a similar manner.
-(2-cyanoethynyl)phenyl ester, trans-4-7'tylcyclohexanecarboxylic acid p-
(2-cyanoethynyl)phenyl ester, trans-
4-hexylcyclohexanecarboxylic acid p-(2-cyanoethynyl)phenyl ester, trans-4-hebutylcyclohexane/carboyap
-(2-cyanoethynyl) phenyl ester, p-7'ropylbenzoic acid p'-(2-cyanoethynyl)
Phenyl ester, 1)-7” thiA4zoic acid p'-(2-cyanoethynyl)
Phenyl ester, p-hexylbenzoic acid Np'-(2,-cyanoethynyl) phenyl ester, p-hexylbenzoic acid p'-(2-cyanoethynyl) phenyl ester, p-hebutylbenzoic acid p'- (2-cyanoethynyl) phenyl ester, p-ethoxybenzoic acid p/ (2-cyanoethynyl)
Phenyl ester, p-propyloxybenzoic acid p'-(2-cyanoethynyl) phenyl ester, p-butyloxybenzoic acid p'-(2-cyanoethynyl) phenyl ester, p-pentyloxybenzoic acid p'-(2- cyanoethynyl) phenyl ester, p-hexyloxybenzoic acid p'-(2-cyanoethynyl) phenyl ester.

Example 11 p-[()limethylsilyl)ethynylphenol (prepared according to Example 1o) 3821I in a 1:1 mixture of methanol and IN aqueous potassium hydroxide solution 15-
A solution of F in a round bottom flask under argon gas for 45 min.
Stirred for 1 minute at room temperature.

The methanol was then removed on a rotary evaporator and the residue was extracted three times with 30 ml each of diethyl ether after addition of 30 m of IN hydrochloric acid. The organic phase was washed twice with sphagnum 30°C and once with saturated sodium chloride solution 3ON, dried over magnesium sulfate and concentrated. p-Ethynylphenol 207M9 (88,9) is obtained as a colorless oil (decomposes quickly in pure state), which is immediately taken up in diethyl ether 50- and trans-4-pentylcyclohexanecarboxylic acid 43681. %N, N'-dicyclohexylcarbodiimide 454 and 4-(dimethylamino)2lysine 24.4111P.

The mixture was stirred at room temperature for 18 hours and then filtered. F
The liquid was treated with 50 ml of water and 50 11 ml each of diethyl ether.
Extracted three times. The organic phase is diluted with water and saturated salt)
Washed with 50 mL of IJ solution, dried over magnesium sulfate, and concentrated. The residue (847 II g) was subjected to low pressure chromatography (0,4 bar) on silica gel with ethyl acetate/petroleum ether to give trans-4-pentylcyclohexane carbon ep-ethylphenyl ester (MJf 98.5%) as colorless crystals. 2
77#9 (46%) was obtained, which was further recrystallized from methanol (purity 99.1); melting point (C-N
) 50.6°C, clearing point (N-I) 78.5°C.

Nidoran-4-propylcyclohexanecarboxylic acid W9p was able to produce the following compound in a similar manner.
-ethynyl phenyl ester, trans-4-butylcyclohexanecarboxylic acid p-ethynyl phenyl ester, trans-4-hexylcyclohexanecarboxylic acid p-
Ethynylphenyl ester, trans-4-hebutylcyclohexanecarboxylic acid p-
Ethynylphenyl ester, p-propyl rest! acid p',-ethynylphenyl ester, p-butylbenzoic acid p/-ethynylphenyl ester, p-pentylbenzoic acid p'-ethynylphenyl ester, p-hexylbenzoic acid up'-ethylphenyl ester, p-heptyl Ankoep'-ethylphenyl ester, p-Z toxybenzoic acid p'-ethynylphenyl ester, p-propyloxybenzoic acid p'-ethynylphenyl ester, p-butyloxybenzoic acid p'-ethylphenyl p-pentyl oxybenzoic acid p'-ethynyl phenyl ester, p-hexyloxybenzoic acid p'-ethynyl phenyl ester, p-hepnaloxybenzoic acid p'-ethynyl phenyl ester.

Example 12 1-[trans-4 in anhydrous tetrahydrofuran 60-
-(2,2-cyclovinyl)cyclohegysyl]-4-
A solution of 480 wIg of pentylbenzene was placed in a sulfonation flask at -78°C under argon gas, and a solution of 3.2117 wIg of butyllithium in hexane was added to a sulfonation flask under argon gas.
Processed within minutes. After the addition was complete, the mixture was heated to -78°C for 2 hours.
．． Stirred for 5 hours, then poured 150 JaJIC of water and extracted three times with 15011J each of petroleum ether. The organic phase is mixed with 10 parts of water.
Washed with OII7, dried over magnesium sulfate and concentrated. The residue (3101v) was low pressure chromatographed on silica gel with hexane (0.5 par).
1-(trans-4-ethynylcyclohexyl)-4-pentylbenzene (M195,
(1) Obtained 255Mg (8&54); Rf value (hexane): 0.10° 1-[trans=4-(2,2-
Dibromovinyl[cyclohairacyl]-4-pentylbenzene was prepared as follows: (a) methylene chloride 6011 in a sulfonation flask equipped with a mechanical stirrer.
A solution of 2.0 g of trans-4-(p-pentylphenyl)cyclohexanecarbonitrile in / was added at −78° C. under argon gas to 13.2 g of a 1.5 M solution of diisobutylaluminum hydride in toluene. Processed within 3 minutes. The mixture was then stirred for 2 hours while gradually warming to room temperature, then carefully poured into 100 ml of potassium sodium tartrate solution and extracted three times with 200 ml each of diethyl ether. The organic phase was washed twice with 100 ml of Sphagnum moss, dried over potassium carbonate and evaporated. Trans-4-, (p-pentylphenyl) as viscous oil
Cyclohexanecarboxaldehyde (purity 86.1
%) was obtained and used without further purification: R
1 value [toluene/ethyl acetate (19:1)): extract 0
．． 58, product 0.54° (b) Tetrabromomethane in methylene chloride 60-5.
0g of the solution was placed in a sulfonation flask at -10°C under argon gas and treated within 5 minutes with a solution of 7.99g of triphenylphosphine in 2011j of methylene chloride. The resulting clear orange solution was stirred for a further 1 min at -10°C and then dissolved in trans-4-(p-
A solution of 1.95 g of (pentylphenyl)cyclohexanecarboxaldehyde was added dropwise within 3 minutes. The mixture was left at 18 DEG C. overnight, then poured into 600 ml of hexane and the precipitate that separated was filtered off (rinsed with hexane).

The concentrated f liquid was crushed with 300d of hexane, -18
Leave for 30 minutes at ℃, then rinse with hexane in the oven), F
The liquid was concentrated. The residue (1,87J7) was subjected to low pressure chromatography (0,5 bar) on silica gel with hexane to give 1-[trans-4-(2
,2-cyfromovinyl)cyclohexyl]-4-pentylbenzene (purity: 95.8) 503 capes were obtained: melting point 5
3-37.7°C.

The following compounds could be prepared in a similar manner:
- 1-(trans-4-ethynylcyclohexyl)-4-
Propylbenzene, 1-(5-4-ethynylcyclohexyl)-4-
Butylbenzene, 1-(trans-4-ethynylcyclohexyl)-4-
Hexylbenzene, 1-(-) lance-4-ethynylcyclohexyl)-4
-heptylbenzene, 1-(trans-4-ethynylcyclohexyl)-4-
Ethoxybenzene, 1-(trans-4-ethynylcyclohexyl)-4-
7'ropyloxybenzene, 1-(trans-4-ethynylcyclohexyl)-4-
Butyloxybenzene, 1-(trans-4-ethynylcyclohexyl)-4-
Pentyloxybenzene, 1-(trans-4-ethynylcyclohexyl)-4-
Hexyloxybenzene, trans-1-()trans-4-ethynylcyclohexyl)-4-7'ropylcyclohexane, trans-1-
(trans-4-ethynylcyclohexyl)-4-butylcyclohexane, trans-1-()trans-4-ethynylcyclohexyl)-4-pentylcyclohexane, trans-1-(trans-4-ethynylcyclohexyl)-4-hexyl Leclohexane, trans-1-
(trans-4-ethynylcyclohexyl)-4-hebutylcyclohexane.

Example 13 1-(trans-4) in anhydrous tetrahydrofuran 60-
-ethynylcyclohexyl)-4-pentylbenzene (
A solution of 254111f (prepared according to Example 12) was placed in a 100-volume sulfonation flask under argon gas T at -45 DEG C. and 1.5% of butyllithium in hexane was added. One treatment with ON solution 1.2- within 1 minute. After the addition was complete, the mixture was stirred for a further 15 minutes at -45°C, then cooled to -78°C, and 1827 ml of phenylcyanate was added.
Processed with. The mixture was stirred for a further 90 minutes at -78°C, then 200 mK of water was poured in and 100 mK of diethyl ether was added.
− was extracted three times. The organic phase was washed twice with Sphagnum 100- and once with saturated chloride solution, dried over magnesium sulfate and concentrated. The residue (380 μ) was subjected to low pressure chromatography (05 bar) on silica gel with 2% ethyl acetate/petroleum ether to give trans-4-(p-pentylphenyl)cyclohexane fluoronitrile (purity 97.3) as colorless crystals. regret)
18611IP (66,1) was obtained, which was further recrystallized from hexane (purity 99.3); melting point (C
-I) 46.9°C, clearing point (N-I) 45.4°C 0 The following compound could be produced in the same manner.

trans-4-(p-propylphenyl)cyclohexaneproviolonitrile, trans-4-(p-butylphenyl)cyclohexaneproviolonitrile, trans-4-(p-hexyl7!nyl)cyclohexaneproviolonitrile, trans-4-(p-hebutylphenyl)cyclohexanepropiolonitrile, trans-4-(p-ethoxyphenyl)cyclohexanepropiolonitrile, trans/su-4-(p-propyloxyphenyl)cyclohexanepropiolonitrile, trans -4-(p-Butyloxyphenyl)cyclohexanepropiolonitrile, trans-4-(p-pentyloxyphenyl)cycloλxanebropiolo-tolyl, trans-4-(p-hexyloxyphenyl)cyclohexanepropiolonitrile, trans -4-(trans-4-7'cyclohexyl)cyclohexaneprobiolonitrile, trans-
4-()lance-4-7'tylcyclohexyl)cyclohexanepropiolonitrile, trans-4-()lance-4-pentylcyclohexyl)cyclohexaneproviolonitrile, trans-4-()lance-4-hexylcyclohexyl) Cyclohexanepropiolonitrile, trans-4-(trans-4-heptylcyclohexyl)cyclohexanepropiolonitrile, Example 1
4 Trans-1-(
2,2-dibromovinyl)-4-[:2-(trans-
A solution of 66J7 in 4-pentylcyclohexyl)ethylcyclolambda Treated with IN solutions 1 & 2- within 10 minutes. After the addition was complete, the mixture was stirred at -78°C for 2 hours and then added with 1 liter of water.
00- and extracted three times with 100 d each of petroleum ether. The organic phase was washed twice with 50 m each of water and once with 50 m of saturated sodium chloride solution, dried over magnesium sulfate,
and concentrated. The residue (1,91) was chromatographed on silica gel with hexane at low pressure (-(0, s bar)) and purified with a trans/cis epitope mixture (approx. 9:1).
), 1.48.9 (881) of trans-1-ethynyl-4-(2-()trans-4-pentylcyclohexyl)ethylcocyclohexane was obtained. Methanol 5Q
Fractional crystallization from d yields pure trans-1- as colorless crystals.
Ethynyl-4-[2-(trans-4-pentylcyclohexyl)ethylcocyclohexane 583sp was obtained;
Melting point (C-N) 51.3°C, clearing point (N-I) 68.0
℃.

Trans-1-(2,2-dibromovinyl)-4-C2-()trans-4-pentylcyclohexyl)ethylcocyclohexane used as a starting material was prepared as follows: (a) Methylene chloride 100 -Middle transformer-4-(
A solution of 2.39% of 2-(trans-4-pentylcyclohexyl)ethylcocyclohexanecarbonitrile was placed in a sulfonated flask at -78°C under argon gas, and 1.5M of hydrogen, diisobutylaluminum oxide in toluene was added. 10.5 mg of the solution was squeezed within 3 minutes. The mixture was then stirred for a further 4 hours at -78°C and then carefully added with a solution of 10 brium sodium tartrate 5QsIj.
and extracted three times with 100 ml of diethyl ether. The organic phase was washed twice with 59 aj portions of water and once with 59 ml of saturated sodium chloride solution, dried over magnesium sulfate and concentrated. The residue (2,19) was subjected to low pressure chromatography (0,5 bar) VC on silica gel with 51 ethyl acetate/petroleum ether and trans-4-(
1.95 g (8
4,41), which according to NMR spectral analysis shows that the corresponding synthetic cis aldehyde is about 104
was used without further purification; Rf value (
10 ml ethyl acetate/petroleum ether): 0.49°(b)
[Tetrabromomethane 44 in methylene chloride 80aZ
The solution of Ii was placed in a sulfonation flask at -15 DEG C. under argon gas and treated within 5 minutes with a solution of 7.09 grams of triphenylphosphine in 20 grams of methylene chloride. The clear, dark orange solution was stirred at -5°C for an additional KIO min.
Trans-4-(2-(
A solution of 1.959 trans-4-pentylcyclohexyl)ethylcocyclohexanecarboxaldehyde was added to 1
It was dropped within 0 minutes. The mixture was stirred for a further 10 minutes at 0° C. and then poured into hexane 60011j, whereby the precipitate that had separated was separated out (rinsed with hexane).

The concentrated filtrate was crushed with 300 ml of hexane, allowed to stand at 0°C for 30 minutes, rinsed with hexane in an oven), and the ν liquid was concentrated.

The residue (3,0,9) was subjected to low pressure chromatography (0,5 Parr) on silica gel with hexane and trans-1-(2,2-dibromovinyl)-4-(2-(
5-4-pentylcyclohexyl)ethylcocyclohexane Z68J7 (89, Section 2) was obtained, which according to NMR spectroscopy contained approximately 10 portions of the corresponding epimeric cis compound, and which was further purified. Nidoran-1-ethynyl-4-C2- (trans-4-
propylcyclohexyl)ethylcocyclohexane, trans-1-ethynyl-4-(2-()trans-4-
butylcyclohegycyl)ethylcocyclohexane, trans-1-ethynyl-4-[2-(trans-4-
hexylcyclohexyl)ethylcocyclohexane, trans-1-ethynyl-4-[2-(trans-4-
1-butylcyclohexyl)ethylcocyclohexane, 1-propyl-4-(2-()lans-4-ethynylcyclobexyl)ethyl]bene layer, 1-butyl-4-
[2-() lance-4-ethynylcyclohexyl)ethyl]benzene, 1-pentyl-4-(2-() lance-
4-ethynylcyclohexyl)ethyl]4zene, 1-
hegycyl-4-(2-()lans-4-ethynylcyclohexyl)ethyl]benzene, 1-hebutyl-4-[2
-() lance-4-ethynylcyclohexyl)ethyl]
Benzene, l-ethoxy-4-[2-() lance-4-
ethynylcyclohexyl)ethyl]benzene, ]-broloxy-4-(2-(trans-4-ethynylcyclohexyl)ethyl)penvin, 1-butyloxy-4
-[2-()trans-4-ethynylcyclohexyl)ethyl]benzene, 1-pentyloxy-4-C2-(trans-4-ethynylcyclohexyl)ethyl]benzene, 1-\xyloxy-4-C2-( Trans-4-
ethynylcyclohexyl)ethyl] pen 1 in.

Example 15 Trans-1-ethynyl-4-(2-(trans-4-pentylcyclohexyl)ethylcocyclohexane (prepared according to Example 14) in a 4=1 mixture of anhydrous tetrahydrofuran and hexamethylphosphoric triamide 751117 A solution of ~750° C. under argon gas was placed in a sulfonation flask at −45° C. and treated within 2 minutes with 3.3 d of a 1.ON solution of butyllithium in hexane. Stir for an additional hour at °C.
Next, cool to -78°C and add 490 μl of phenyl cyanate.
processed at once. The mixture was then stirred for an additional 2.5 hours at -78°C and poured into 2+1 water (lsa#).
Extraction was carried out three times with 150 d each of dichloroethyl ether. The +pt phase was washed twice with 150 mj of sphagnum moss and once with 140 mj of #1 hydrated sodium chloride solution, dried over Pj magnesium sulfate, and concentrated. The residue (2,6 l) was subjected to low-pressure chromatography (0,5 bar) on silica gel with hexane and sequentially chromatographed trans-1-ethynyl-4-(:2
-(trans-4-pentylcyclohexyl)ethylcocyclohexane 19411q (25,8 嬬) and trans-4-(2-()trans-4-pentylcyclohexyl)ethyl]cyclohexanebropiolonitrile (purity 98.91) 284 ~(34,84) was obtained. Recrystallize the nitrile from methanol to obtain colorless crystals (purity 99
．． 4) was obtained: melting point CC-N) 51.4°C and clearing point (N-I) 1117°C.

Nidoran-4- was prepared in the same manner by removing the following compound.
(2-(trans-4-propylcyclohexyl)ethyl]cycloλxaneproftenlonitrile, trans-4-(2-(trans-4-butylcyclohexyl)ethyl)cyclohexanepropiolonitrile, trans-4-C2- (trans-4-hexylcyclohexyl)ethyl]cyclohexaneproviolonitrile, trans-4-C2-(trans-4-hebutylcyclohexyl)cyclohexyl]cyclohexanepropiolonitrile, trans-4-[2-(T) -propylphenyl)ethyl]cyclohexanebu-piolonitrile, trans-
4-(2-(p-butylphenyl)ethyl)cyclohexane-violonitrile, trans-4-(2-(p-
pentylphenyl)ethyl]cyclohexanepropiolo,; tolyl, trans-4-(2-(p-hexyl phenyl)ethyl)cyclohexaneproviolonitrile,
trans-, i-(:2-(p-hebutylphenyl)ethyl]cyclohexanepropiolotolyl, trans-
4-(2-(p-ethoxyphenyl)ethyl]cyclohexaneproviolonitrile, trans-4-(2-(p-ethoxyphenyl)ethyl)
-propyloxyphenyl)ethyl]cyclohexaneproviolonitrile, trans-4-[2-(p-7'tyloxyphenyl)xfyl]cyclohexaneproviolonitrile, trans-4-(2-(p-pentyloxyphenyl)
Ethyl]cyclohexaneprobiolo: tolyl, trans-4-[2-(p-hexyloxyphenyl)
Second move ~] Cyclohexaneproviolonitrile.

Example 16 1-ethynyl- in 90w1l of anhydrous tetrahydrofuran
A solution of 55 g of 4-()lance-4-pentylcyclohexyl)benzene (according to Example 3), manufactured by J. Treated within 5 minutes with a 1.ON solution of lithium [7]. The clear yellow mixture was stirred at -20°C for 30 minutes and then treated sequentially with 101 hexamethylphosphoric triamide and 747 μl of methyl iodide. After warming to room temperature, the dark purple mixture was stirred for a further 4 hours, then poured into 150 ml of water and extracted three times with 150 d each of petroleum ether.The organic phase was reduced to 20 vol. of water.
Washed twice with 01Il, dried over magnesium sulfate, and concentrated. The residue (3.01 g) was subjected to low-pressure chromatography (0.5 Parr) on silica gel with hexane, and sequentially chromatographed with 1-Kotenilu-4-(trans-
4-pentylcyclohexyl)benzene 806■(”(
Mixture of 431■ (16, 3rd Section) Line K
l-(1-propynyl)-4-(trans-4-pentylcyclohexyl)benzene 601■ (section 22, 4) was obtained. The last 7 lactations were recrystallized from 50 ml of methanol to give 1-(1-propynyl)- as colorless crystals.
464 m9 of 4-() lance-4-pentylcyclohexyl)benzene was obtained; melting point (C-N>41.6°C, clearing point (N-I) 64.9°C; η (22°C) = 23 cp: η
(45°C) = 7.7 cp.

The following compound could be prepared using a similar h method: 1-(1-propynyl)-4-(tran,su-4-propylcyclohexyl)benzene, melting point (C-N) 45.
1°C, clearing point (N-I') 53.7°C, 1-(1-propynyl)-4-(trans-4-butylcyclohexyl)benzene, 1-(1-propynyl)-4-(trans-4) -hexylcyclohexyl)benzene, 1-(1-propynyl)
-4-(trans-4-hebutylcyclohexyl)benzene, 8 points (('-N) 43.5°C, clearing point (N-I)
66.8°C, 1-(1-butynyl)-4-(trans-
4-propylcyclohexyl)benzene, 1-(1-butynyl)-4-()lanth-4-butylcyclohexyl)benzene, 1-(1-ethynyl)-4-(tran-(-4-pentylcyclohexyl)henjin, F”1 point (('-N)2
9.5℃, clearing point (N-I) 31.4℃, 1- (1-
Ql - < Trans
-4-hexylcyclohexyl rb )benzene, 1-(
1-ethynyl)-4-(tran-°-4-hebutylcyclohexyl)ben l/n, 1-(l-pentynyl)-4
-(trans-4-furobylcyclohexyl)benzene, 1-(1-pentynyl)-4-()u/4-butylcyclohexyl)benzene, 1-(1-benzonyl)-4-(trans-4-pentyl) cyclohexyl)benzene, 8 points (C-N) 20.0
°C, clearing point (N-I) 31.3 °C, 1-(1-pentynyl)-4-()lance-4-hexylcyclohexyl)
Benzene, 1-(1-pentynyl)-4-(trans-
4-hebutylcyclohexyl)benzene, 4-(1--
10 vinyl)-4'-pentylbiphenyl, melting point (C-
8) 60°5°C, clearing point (S-I) 83.4°C, 1-(1-propynyl)-4-(2-(trans-4-
7'Tylcyclohexyl)ethyl]benzene, melting point ((
'-N) 33.1°C, clearing point (N-I) 38.6°C, 1-(1-propynyl)-4-(2-(trans-4-
Pentylcyclohexyl)ethyl]benzene, melting point (C
-N) 46.8℃, clearing point (N-I) 55.3℃, η(
22°C) = 18cp.

1-(1-propynyl)-4-[2-(trans-4-
hebutylcyclohexyl)ethyl]benzene, melting point (C
-N) 44.4°C, clearing point (N-I) 58.0°C, 1-(1-butynyl)-4-[2-()lance-4-7
'fkcyclohexyl)ethyl]benzene, melting point (C-
N) 6.1°C, clearing point (N-I)9. ', ℃, 1-(1
-pentynyl)-4-(2-()trans-4-butylcyclohexyl)ethyl]benzene, melting point 14.3°C, clearing point 22.6°C, 1-[2-[trans-4-(1-pentynyl)] Cyclohexyl]ethynyl]-4-propyleneoxybenzene, melting point (C-8) 21.6°C, clearing point (S
-I) 25.3°C.

Example 17 β,β-dibromo p-[2-()lans-4-pentylcyclohexyl) in anhydrous tetrahydrofuran 32-
ethyl]styrene (produced according to Example sK) 1
．． 42 g of the solution was placed in a sulfonation flask at about -45 DEG C. under argon gas and treated within 5 minutes with 8.0 of a 1.2N solution of butyllithium in hexane. At the end of the addition, the reaction mixture was stirred at this temperature for a further 90 minutes and treated sequentially with 3.2 U of hexamethylphosphoric triamide and 40 U of butyl iodide. After warming to room temperature, the mixture was stirred for a further 24 hours and then added with 5 Qm water.
and extracted three times with 50% each portion of petroleum ether. The organic phase was treated twice with 50 g each of water and 50 d of saturated sodium chloride solution.
once with water, dried over magnesium sulfate, and concentrated. The residue (1,07 g) was subjected to low pressure chromatography on silica gel using hexane as eluent (0,5 g).
Pearl) to give 1-(1-pentynyl)-4-(2-()-7n-4-pentylcyclohexyl)ethyl]benzene 840IIli (81%) as colorless crystals (purity 98.9% by gas chromatography). 34)
.

Recrystallized from methanol 75m, melting point (C-I) 37.
8℃ and clearing point (S-I) 30.9℃.
634q of (pentynyl)-4-(2-(trans-4-pentylcyclohexyl)ethyl)benzene was obtained.

Example 18 A solution of 2.87.9 ml of 4-[2-[trans-4-(2,2-dibromovinyl)cyclohexyl]ethyl], a/-pentylbiphenyl in 100 d of anhydrous tetrahydrofuran was evaporated under argon gas. Placed in a sulfonation flask at 20° C. and treated within 15 minutes with 20.6-20.6 N of a 0.8 N solution of butyllithium in hexane (slightly exothermic reaction).
. The mixture was then stirred for 1.5 hours while gradually warming to 0°C, then poured into 100% of water and 1% each of diethyl ether.
Extracted 3 times with 00-. The organic phase was washed twice with 100° each of water, dried over magnesium sulfate and concentrated.

The residue (1,98,9) was subjected to low-pressure chromatography (0,5 Parr) on silica gel using lancetyl acetate/petroleum ether as eluent to give 4-(2-()lance-4- ethynylcyclohexyl)ethyl]-4'-
1.94 g (98%) of pentylbiphenyl was obtained. The crystals were recrystallized twice from ethanol and subjected to repeated low-pressure chromatography (0.5 par) using hexane as the eluent to obtain a mixed fraction of 732 mm and a melting point (C
-8) 66.0°C, transposition point (S-8) 107°C, transposition point (S-N) 115°5°C and clearing point (N-I) 126.
Pure 4-[:2-()lance-4-ethynylcyclohexyl)ethyl)-4'-pentylbiphenyl 6 with 4°C
Obtained Cape 84.

4-[2-() lance-4-(2
,2-cyclohexyl]-4
'-Pentylpiphenyl was prepared as follows: (4-cyano-4I- in (trans)methylene chloride 150-
A solution of 1 og of pentylbiphenyl was placed in a sulfonation flask at -78°C under argon gas and 54 ml of a 1.5N solution of diisobutylaluminum hydride in toluene was added.
was processed within 15 minutes.

The mixture was then stirred for a further 30 minutes at -78°C and then carefully poured into 50 l of 2N hydrochloric acid and 100 d each of methylene chloride.
Extracted three times. The organic phase was washed twice with 10 liters of water, dried over magnesium sulfate and concentrated. The oily residue (22,0J7) was chromatographed on silica gel at low pressure with 3% ethyl acetate/petroleum ether. (0
, 5 pearls) 4'-pentyl-4-biphenylylcarboxaldehyde (purity 98) as a colorless viscous oil.
L) 10.0 g (99%) Ti; R1 value (3% ethyl acetate/petroleum ether): 0.13° (b) Lithium aluminum hydride 1.59 in a sulfonation flask under total argon gas It was suspended in 150 d of anhydrous tetrahydrofuran and treated at room temperature with a solution of 4'-pentyl-4-biphenylylcarboxaldehyde to, og in anhydrous tetrahydrofuran 20&Z within 15 minutes, then stirred for 1 hour at room temperature. The reaction mixture was then quenched with 2N hydrochloric acid (50°C) and extracted three times with 10° each of diethyl ether. The organic phase was diluted with 50+j of water each.
Washed twice [7, dried over magnesium sulfate and concentrated. 4-(Hydroxy)i as a colorless crystalline oil
f A/ ) ++ 4'-henthylbiphenyl (
Pure 1 [9 & 2%) 9.4,1931) was obtained and used without further purification: Rf value (10 ethyl acetate/petroleum ether): 0.05° (C) methylene chloride 15 A solution of 9.49 4-(hydroxymethyl)-4-pentylbiphenyl in 〇- was placed in a sulfonation flask at 0°C under argon gas, and treated with 62M aqueous hydrogen bromide solution 3,4- within 5 minutes. Processed. The mixture was stirred for a further 15 hours at room temperature, then poured into 50 mK of 54 sodium bicarbonate solution and diluted with methylene chloride.
Extracted three times. The organic phase was washed twice with 100° each of water;
Dry over magnesium sulfate and condense. Residue (
8 g) was chromatographed on silica gel by low pressure chromatography (
0,5 pearls) to give 7.5 g (64 pearls) of 4-(bromomethyl")-4'-pentylbiphenyl as a colorless oil; Rf value (10 m ethyl acetate/petroleum ether)
:0.59°(d) A solution of 11.6 g of triphenylphosphine in 200 wJ of ethyl acetate was placed in a sulfonation flask under argon gas, and 4-(7
Treated within 10 minutes at room temperature with a solution of 7.59% of 'lomomethyl)-4'-pentylbiphenyl.

The reaction mixture was then stirred for a further 18 hours at room temperature, and the separated Bitztig salt was filtered off, washed with ethyl acetate and kept constant.
<Dry at 50° C./12 Torr until completely dry. (4'-pentyl-4-biphenylyl)methyl-triphenylphosphonium puromy)'7.6.9' (section 56) was obtained as a colorless powder with a melting point of 202-204°C. Melting point 202-204.5℃ from the filtrate concentrated to 50-
bromide 139 (24) could be further isolated.

(e) (4/-pentyl-4-biphenylyl)methyl-triphenylphosphonium bromide in 200 m of t-butyl methyl ether in a sulfonation flask equipped with a temperature needle, dropping funnel and solid material addition tube.8.
7 g of the suspension were introduced at 0° C. and treated with solid potassium t-butyrev) 1.6 J7 within 5 minutes. Then reduce the mixture to 0
After stirring for an additional 30 minutes at <0>C, a solution of 1.3'# of trans-4-cyanocyclohexanecarboxaldehyde in 30wd of 1-butyl methyl ether was added dropwise. After the addition was complete, the cooling bath was removed, the mixture was stirred for a further 2 hours, poured with 150 mgK of water and extracted three times with 150 mg each of diethyl ether. The organic phase was washed once with 15011j of water and once with 15Qsd of saturated sodium chloride solution, dried over magnesium sulfate and concentrated [7].

The residue (8.06 L) was crushed with 10 g of ethyl acetate/300 g of petroleum ether.1. And I was treated to a warm welcome. concentrated ν
The solution was subjected to low pressure chromatography (0,5 bar) on silica gel with 104 ethyl acetate/petroleum ether to give 4-(2-(trans-4-cyanocyclohexyl)
20 g of colorless crystals of ethynyl]-4'-pentylbifer (cis/trans mixture) were obtained. The initially separated triphenylphosphine oxyto was triturated with 20% ethyl acetate/petroleum ether, filtered, and the concentrated solution was low-pressure chromatographed on silica gel with 20% ethyl acetate/petroleum ether as eluent. Further product 1.41J7 was obtained by graphy.

Rf value (10% ethyl acetate/petroleum ether): 0°25
and 0.18 (cis and trans products, respectively).

Ge14-(2-(trans-4-cyanocyclohexyl)ethynyl-4'-pentylbiphenyl λ4.9)
It was dissolved in 1504 ml of toluene/ethanol (volume ratio 4:1), treated with 10 ml of palladium/carbon 3QQag, and hydrogenated at normal pressure and room temperature until the absorption of hydrogen was completed. The mixture was heated and the concentrated solution F was subjected to low pressure chromatography (0.5 bar) on silica gel with 5-ethyl acetate/petroleum ether as eluent to give 4-(2-(trans-4) as colorless crystals. -cyanocyclohexyl)
3.08 g of ethyl 4/-pentylbiphenyl was obtained (purity 99.2; yield 86% based on nidorans-4-cyanocyclohexanecarboxaldehyde) c
, the sample was recrystallized from ethanol and the melting point (C-8)
59.7℃, dislocation point (S-8) 68.1℃, dislocation point (S-8)
-N) 89.0°C and clearing point (N-I) 134.5°C.

For sulfonation of a solution of 2.6.9 of 4-C2-(trans-4-cyanocyclohexyl)ethyl]-4'-pentylpiphenyl in 100 methylene chloride at -78°C under argon gas. 9.5-N solution of diisobutylaluminum hydride in toluene in a flask.
It was processed within 5 minutes.

The kernel mixture was then stirred for an additional 4.5 hours at -78°C and
The mixture was poured into 100 g of potassium sodium tartrate solution and extracted three times with 100 g each of methylene chloride.

10 g of organic phase 6 potassium sodium tartrate solution 100 g
d once, dried over magnesium sulfate, and concentrated. The residue (L93J7) was subjected to low pressure chromatography on silica gel with ethyl acetate as eluent (0
, 5 bar) to form trans-4- as colorless crystals.
(2-(4'-benthyl-4-biphenylyl)ethylcocyclohexanecarboxaldehyde 133g
4) zRf value obtained (10% ethyl acetate/petroleum ether): 0.38° (h) In a sulfonation flask equipped with a thermometer, dropping funnel and solid material addition tube, 60 m of methylene chloride was added.
A solution of 6.79% of triphenylphosphine in the solution was added at -20°C under argon gas, and 4.3% of tetrabromomethane was added to the solution at -20°C under argon gas.
g within 5 minutes. The clear orange solution was stirred for a further 10 min at -15°C and then trans-4-[2(4/-pentyl-4-biphenylyl) in methylene chloride JQm
Ethylcocyclohexanecarboxaldehyde 2.33
g solution was added dropwise within 10 minutes at -5°C. The mixture was stirred for a further 10 minutes at -5°C and then
The precipitated triphenylphosphine oxyto was separated by filtration. The concentrated filtrate was diluted with hexane 300-
It was also crushed, offshored, and concentrated. Residue (3,5
9) was subjected to low pressure chromatography (0,5 par) on silica gel with 1 oz. ethyl acetate/petroleum ether to give 4-[2-[)lanse-4-(2,
2-Ciflomovinyl) Schiftetrahexyl]ethyl], s/
- obtained pentylbiphenyl λ87J7 (87%); R
f value (34 ethyl acetate/petroleum ether): 0.49° The following compound was prepared in a similar manner: 1-C2-() lance-4-ethynylcyclohexyl)
ethyl]-4-pentylbenzene, melting point 34.8°C, 1-C2-(trans-4-ethynylcyclohexyl)
ethyl]-4-phthyloxybenzene, melting point 39.5°C
.

Example 19 1-(2-(trans-4) in diethyl ether 50-
-Ethynylcyclohexyl)ethyl]-4-pentylbenzene (prepared according to Example 18) A solution of SOO cape was placed in a sulfonation flask at -25°C under argon gas and 0.0% of butyllithium in hexane was added. 8N
Solution 3.9- was treated within 5 minutes. After the addition was complete, the mixture was stirred for a further 45 minutes at 0.degree. C., then cooled to -78.degree. C. and treated within 10 minutes with 420 sl of phenyl di7nate in 20 ml of anhydrous diethyl ether. The mixture was stirred for a further 30 minutes at -78 DEG C., then poured into 100 ml of water and extracted three times with 100 ml of diethyl ether. The organic phase was washed twice with 100 d of Sphagnum moss and once with 100 d of saturated sodium chloride solution, dried over magnesium sulfate,
and concentrated. Residue i (1,13 g) was subjected to low pressure chromatography (0,5 par) on silica gel with 3'[ethyl acetate/petroleum ether] and added to the recovered extract 630 cape to give a colorless crystallizing oil 1421'9. According to gas chromatography, this product contained 76% of trans-4-[2-(p-pentylphenyl]cyclohexanepropiolonitrile.Each was crystallized twice from methanol at -20°C. to obtain 50 μm of pure nitrile; melting point (CN): 36.5°C, clearing point (
N-Engineering) 4a, o℃.

The following compound was prepared in a similar manner (nidoran-4,-C2-(p-)f-oxyphenyl)
ethyl]cyclohexaneglopiolonitrile; melting point (C
-N) 66.6°C, clearing point (N-I) 76.7°C.

Example 20 A mixture of 122 Mg of trans-4-ethynylcyclohexanecarboxylic acid, 145 μg of trans-4-pentylcyclohexanol, 206 wq of dicyclohexylcarbodiimide and 12.211 F of 4-(dimethylamino)pyridine in 10 methylene chloride was prepared at room temperature. The mixture was stirred for 21 hours. The separated white precipitate was filtered, the ν solution was poured with 50 ml of water, and extracted three times with 50 ml each of methylene chloride.The organic phase was extracted once with 50 ml of water, twice with 30 ml each of 5 ml of acetic acid, and extracted with water. 3
Washed twice with 0-, dried over magnesium sulfate, and concentrated. The residue was subjected to low pressure chromatography (0,5 Parr) on silica gel with 5-ethyl acetate/petroleum ether as a colorless crystallizing oil.
(ethynylcyclohexanecarboxylic acid) lance-4-pentylcyclohexyl ester 159,111g (651
) was obtained. Isobrono (further crystallization from alcohol at -20°C gave the analytically pure ester; melting point (C-I) 5
4.2°C, clearing point (N-I) 40.5°C.

The trans-4-ethynylcyclohexanecarboxylic acid used as starting material was prepared as follows: (a) Tetrabromomethane in methylene chloride IQOd 24. (Pour a solution of H7 into a sulfonation flask at -15°C under argon gas, add methylene chloride 5011j
of triphenylphosphine within 10 minutes. The clear orange solution was stirred for a further 10 minutes at -10 DEG C. and to it was added dropwise at -5 DEG C. within 10 minutes a solution of 5.0 g of trans-4-aneanocyclohexanecarpoxyaldehyde in 200 methylene chloride. This mixture is 0
The mixture was stirred for an additional 30 minutes at 0.degree. C., then poured with 1 tK of ethyl acetate/petroleum ether, and the precipitated triphenylphosphine oxide was removed by filtration. 10% of concentrated F solution
It was crushed again with 500 d of ethyl acetate/petroleum ether, furnaced and concentrated.

The residue (14,9) was subjected to low pressure chromatography on silica gel with 10q6 ethyl acetate/petroleum ether (0,
5 bar), 11.0 g of trans-4-(2°2-dibromovinyl)cyclohexanecarbonitrile were obtained, which was still contaminated with triphenylphosphine. This material was purified on silica gel with triethyl acetate/
A second low pressure chromatography with petroleum ether gave pure trans-4-(
9.04 g (854) of 2,2-dibromovinyl)cyclohexanecarbonitrile was obtained.

(b) 1.71 g of trans-4-(2,2-dibromovinyl)cyclohexanecarbonitrile and lithium amalgam (1,5
1) The mixture of 8.14J7 was stirred at room temperature for 68 hours in a round bottom flask under argon gas. Then FT the mixture
I had an IM. The furnace solution was poured with 1501 IjK of water and extracted three times with 100 d each of diethyl ether. The organic phase is washed once with 150 g of water, dried over magnesium sulfate and concentrated to give a crystallizing oil (trans-4-ethynylcyclohexanecarbonitrile)1. I got oB.

(cl) above 'ff (b)
:1 mixture and heated under reflux for 3.25 hours. The cooled mixture was poured into water 5011j and extracted twice with 50 ml of diethyl ether. Add 50% of 2N sulfuric acid to the aqueous phase.
117 and extracted three times with 100 d each of diethyl ether. The organic phase was dissolved in saturated sodium chloride solution 1001I.
Washed once with J.j., dried over magnesium sulfate-E, and concentrated. Further crystallization from hexane, melting point 161
Pure trans-4-ethynylcyclohexanecarboxylic acid was obtained at ~162°C.

Nidoran-4-ethynylcyclohexanecarboxylic acid p-
Hexyloxyphenyl ester, melting point (C-I) 49
．． 8°C, clearing point (N-I) 34.5°C.

Continued from page 1 of Ngesellschaft Priority claim September 23, 1982 ■Switzerland (CH)
■5623782-3

Claims (1)

[Claims] 1. In the general formula, ring B is 1,4-phenylene or trans-1,
represents a 4-disubstituted cyclohexane ring, A is 1-
It represents a group having three 6-membered groups, which group together with IIB has the formula [where A13 is trans-1,4-disubstituted cyclohexane, 1,4-2[1! bicyclo(212]octane, trans-2゜5-disubstituted 1,3-dioxane linked in the 2-position t with IIB, or ring B is trans-1,4-disubstituted When it represents cyclohexane or R3 represents alkyl, ring AI'' can also be combined with WIB and 1,4-phenylene, fluoro-1,4-phenylene, 3,6-disubstituted pyridazine or RuB and 2- represents a 2,5-disubstituted pyrimidine bonded at the central group or formula [where ring A1 is 1,4-phenylene, fluoro-1
,4-phenylene, trans-1,4-disubstituted cyclohexane, 1,4-disubstituted bicyclo[2,1
2] octane, 3.6-disubstituted pyridazine or trans-2, bonded at the 2-position with an ethyl group;
5-disubstituted 91,3-dioxane or 2,5-
represents a disubstituted pyrimidine] or a central group of the formula [where II A * is 1,4-phenylene, fluoro-1,4-)22V, trans-1°4-disubstituted cyclohexane or 1. represents a 4-disubstituted bicyclo(242) octane, and E represents an ester group] or the central group of the formula [wherein Aa, together with IIB, represents a 2.6-disubstituted bicyclo(242) octane. Tetralin or 2.6-2 (equatorially (eq.
uatorial Iy) represents a substituted) trans-decalin] is the central group of the formula 4-U) Represents lance-1,4-disubstituted cyclohexane: or ring 1 represents pyrimidine linked in the 2-position with pyridazine or IIB, and 31 A 4 and B represent 1,4 - Phenylene or trans-1,4-disubstituted cyclohexane; and ring B represents 1,4-phenylene or trans-1,4-disubstituted cyclohexane] [where @ AI and A7 taken together represents a central group or formula of 2゜6-disubstituted naphthalene, 2,6-disubstituted tetralin or 2,6-disubstituted (equatorially substituted)-transdecalin. A1 and AI together represent 2゜6-disubstituted naphthalene, 2,6-disubstituted tetralin or 2,6-disubstituted trans-decalin. or represents the central group of the formula [where rings AS', A'' and B represent 1,4-phenylene i*FJ:, 5-1,4-disubstituted cyclohexane], and R'Fi carbon represents a straight-chain alkyl group containing from 1 to 9 atoms, or represents a straight-chain alkoxy group containing from 1 to 9 carbon atoms, or benzene, also monofluorinated benzene, t, < n RsFi on top of the pyrimidine; and R1 is hydrogen, cyano or carbon atom 1
A compound representing a linear alkyl group containing ~7. 2. Natte type 11. with A73ZmlB. I
, ■, ■, ■, or the compound according to claim 1, which represents a central group of Fix. 3. A is combined with JJIB to form the formula ■, ■ or ■
2. A compound according to claim 2, which represents a central group of 4. A together with gJB (a) a trans-2,5-disubstituted 1,3 in which ring All is bonded in the 2-position to a trans-1,4-disubstituted cyclohexane ring B; -represents dioxane or? When B represents trans-1°4-disubstituted cyclohexane, and ij:R1 represents alkyl, It A 1 m also represents l! B and 1.4
-phenylene or Fi, 2 bonded in the 2-position
, a central group of formula R representing a 5-disubstituted pyrimidine, (b) mA is 1.4-7 enylene or trans-1,
The central group of the formula (2) represents a 4-disubstituted cyclo1xane, or (C)IIA'' represents a 1,4-7enylene 7-1,4-disubstituted cyclohexane, and E is an ester group. The compound according to claim 3, wherein the central group of formula (1) represents: Representation: R8
represents a straight-chain alkyl group containing 1 to 7 carbon atoms; or at least one of rings B and C is trans-1
, 4-disubstituted cyclohexane,
A compound according to claim 1, wherein R2 also represents hydrogen or cyanide; and Rt has the meaning as defined in claim 1. 6. The compound according to claim 5, wherein one of rings B and C represents trans-1,4-disubstituted cyclohexane and the other represents 1,4-phenylene. 7. In the general formula, ring C is 1,4-phenylene or trans-1,
4-disubstituted cyclohexane, and ring B
, R' and R2 have the meanings given in claim 1. 8, at least one of pB and C is trans-1,4-
8. A compound according to claim 7 representing a disubstituted cyclo1xane. 9. In the general formula, ring C is 1,4-phenylene or trans-1,
4-represents a disubstituted cyclohexane, and II
A compound according to claim 1, which is a compound having the meaning given in claim 1. 10. In the general formula, 'R#C is 1, 4-phenylene or trans-
Compound 11 according to claim 1, which represents a 1,4-disubstituted cyclohexane, and IIB, R' and octafold have the meanings given in claim 1; The compound according to claim 1, which is a compound of the following formula, wherein rings B, R1 and R have the meanings described in claim 1. 1z General formula In the formula, WB is 1,4-7 enylene or 7-1.
4-disubstituted cyclohexane; R''t: represents a linear alkyl group containing 1 to 7 carbon atoms, or IIB represents trans-1,4-disubstituted cyclohexane; A compound as claimed in claim 1, wherein R't; It also represents hydrogen or cyano; and R'Fi has the meaning as defined in claim 1. 13. In the general formula, C is 1,4-phenylene or trans-1,
4-disubstituted cyclohexane, and ring B
The compound according to claim 1, wherein %R1 and R2 have the meanings given in claim 1. 14. Claims 1 to 1 in which 11B is saturated
A compound according to any one of Item 3. 15. The compound according to claim 9, wherein Rui B represents 1,4-phenylene. 16. A compound according to any one of claims 1 to 15, wherein R'' represents hydrogen, cyano, methyl, ethyl or propyl, preferably hydrogen, cyano-span-methyl. 17. R' represents 3 carbon atoms. represents a chain-like alkyl group containing ~7 carbon atoms, or R1 on an aromatic ring has 2 to 7 carbon atoms;
17. The compound according to any one of claims 1 to 16, which represents a linear alkoxy group containing 6 alkoxy groups. 18. At least one component is
A liquid-crystalline mixture comprising at least two components which are compounds of formula I as defined in paragraph 1. 19. In the general formula, A, B, R' and R'' have the meanings described in claim 1, for producing the compound of (a) a formula in which R'' represents hydrogen; To prepare a compound of formula I, a compound of formula 5 in which X represents chlorine or bromine and A, B and R1 have the meaning given in claim 1 is combined with a base or lithium amalgam. react,
The reaction product is then hydrolyzed or (b) a compound of formula I in which R'' represents hydrogen is reacted with a base and subsequently with phenyl cyanate to produce a compound of formula I in which R'' represents cyano. , (c) reacting a compound of formula I, in which R" represents hydrogen, with a base and subsequently with an alkyl bromide or alkyl iodide, in order to prepare a compound of formula I, in which R" represents a linear alkyl group; (d) Formula I in which A together with ffB represents the central group of formula ■ and E represents the ester group -CO-O-
In order to prepare a compound of the general formula, At and R1
has the meaning given in claim 1, or a reactive derivative thereof; wherein B and R2 have the meaning given in claim 1, or a suitable salt thereof; or esterify with (e
) A and ring B form a button and represent the central group of 2■,
In order to produce a compound of formula I in which E represents an ester group -0-CO-, a compound of the general formula or its reactivity, in which B and R1 have the meanings given in claim 1, is prepared. The derivative is esterified with a compound of the general formula, or a suitable salt thereof, in which AI and R1 have the meanings given in claim 1, or (f) A is combined with ring B. In order to prepare compounds of formula I representing a central group of formula 1, in the general formula A', A
' and R1 have the meaning as defined in claim 1, or a reactive derivative thereof is esterified with a compound of formula x or a suitable salt thereof, A method for producing the compound of I. 20. Electro-optica
l) Use of a compound of formula I according to claim 1 for a device.