JPH07110819B2 - Cyclohexenyl ethane compound - Google Patents

Description

TECHNICAL FIELD The present invention relates to a cyclohexenylethane compound, and more specifically, a derivative of cyclohexenylethane which is a compound suitable as one component of an electro-optical display material and the derivative thereof. The present invention relates to a liquid crystal composition containing

[Conventional technology]

In recent years, liquid crystals have become more important as dielectrics for display devices due to electro-optical effects based on the anisotropy of dielectric constant and refractive index. Display methods based on liquid crystals include, for example, dynamic scattering method, phase transition method, DAP method, guest-host method, TN method using 90 ° twist cell, 180 to 270 °
There are STN or SBE methods using twisted cells, and active matrix methods using TFT, which have recently attracted particular attention. Liquid crystal materials used in these display systems have various characteristics, for example, a wide liquid crystal phase temperature range, stability against environmental factors (moisture, heat, air, light, electricity, etc.), and colorless. , The anisotropy amount of the refractive index (hereinafter abbreviated as Δn) is a proper value, the elastic constant ratio is large (or small), the anisotropy amount of the dielectric constant (hereinafter abbreviated as Δε) is large, It is required to have a low viscosity, a high specific resistance, and a small change with time.

However, at present, there is no compound capable of sufficiently driving a display device with a single compound, and in fact, a liquid crystal mixture in which several kinds of liquid crystal compounds are mixed is used. for that reason,
It is also required that the liquid crystal compound has good compatibility with other liquid crystal mixtures.

In the present specification, the liquid crystal compound refers to a liquid crystal compound or a compound involved in some aspect for driving a liquid crystal display element.

In recent years, compounds having a cyclohexene ring have been introduced as liquid crystals. For example, Japanese Patent Laid-Open No. 1-1068
No. 30 and DE3717397A1 (However, R'represents an alkyl group or the like.), But the liquid crystal phase maximum temperature is low as a tricyclic compound.

In addition, U.S. Pat. Although a compound represented by (R represents an alkyl group) is disclosed, it is unstable to environmental factors.

[Problems to be Solved by the Invention]

In view of the above problems, an object of the present invention is to exhibit a wide liquid crystal phase, have good compatibility with existing liquid crystal compounds, and can widen the liquid crystal phase temperature range of a liquid crystal composition. And a liquid crystal compound having a cyclohexene ring, which is extremely stable against environmental factors, and a liquid crystal composition containing the liquid crystal compound.

[Means for Solving the Problems]

The cyclohexenylethane compound of the present invention has the general formula (In the formula [I], R represents an alkyl group having 1 to 10 carbon atoms,
X represents an alkyl group or an alkoxy group having 1 to 10 carbon atoms, a cyano group, a bromine atom or a fluorine atom, and Y
Represents a hydrogen atom or a fluorine atom, m is 0 or 1, and n is 0 or 1. ).

In the general formula [I], R preferably has 1 to 7 carbon atoms,
It is more preferably 1 to 5, and the alkyl group or alkoxy group of X preferably has 1 to 6 carbon atoms.

Further, the straight-chain alkyl group of R or the alkyl group or alkoxy group of X has the advantages of high liquid crystallinity and low viscosity, and the branched one has a high solubility in a conventional liquid crystal material. Especially when they are optically active (preferably having at most one branch) they can be used as chiral doping agents.

Further, among the general formula [I], particularly preferable ones are shown below.

(In these formulas, R and Y are the same as those in the formula [I]. Further, X ₁₁ represents an alkyl group or an alkoxy group having 1 to 10 carbon atoms, more preferably a straight chain having 1 to 6 carbon atoms. It represents an alkyl group or an alkoxy group.) Examples in which the compounds represented by these formulas are specifically disclosed are as follows.

That is, regarding the compound represented by the formula [Iaa], the compounds represented by the formulas [Iab] are disclosed in Examples 1, 2, 5 and 6, and the compounds represented by the formula [Iac] are disclosed in Examples 3, 4, 7 and 8. Are disclosed in Examples 9 and 10 and compounds of the formula [Iad] are disclosed in Examples 11 and 12. Further, the compound of the formula [Iba] is the compound No. 34 of Example 19, Example 20.
5 to 352, Compound Nos. 372 to 379 of Example 23 and Example 24
Disclosed in.

Further, the compound of the formula [Ibb] is represented by the compounds No. 353 to 361 of Example 20 and the compounds No. 380 to 388 of Example 24, and the compound of the formula [Ide] is disclosed in Examples 13 and 14. It

The cyclohexenylethane compound of the present invention exhibits a wide liquid crystal phase. Furthermore, other liquid crystal compounds such as ester-based, Schiff-based, ethane-based, acetylene-based, azoxy-based,
Biphenyl type, cyclohexane type, cyclohexene type,
Since it has excellent compatibility with existing liquid crystal compounds such as pyridine-based, pyrimidine-based, and dioxane-based compounds, a liquid crystal material suitable for various applications can be obtained by mixing these compounds or a mixture thereof.

One of the reasons why this compatibility is excellent is that it has a cyclohexene ring in the molecule.
It is also very stable against environmental factors (moisture, heat, air, light, electricity, etc.). It is considered that this is because an ethane bond exists between the cyclohexene ring and the benzene ring.

Among the compounds of the present invention, the compounds represented by the formulas [Iaa], [Iab], [Iba] and [Ibb] have a high clearing point, which enables the liquid crystal display device to operate at a high temperature. Further, since the compounds represented by the formulas [Iaa], [Iab] and [Iae] have low viscosities, the response speed of the liquid crystal display device can be improved. Also, [Iba], [I
Since the compounds represented by the formulas [bb] and [Ibc] have a large positive Δε, it is possible to reduce the driving voltage of the liquid crystal display device. Further, the compounds represented by the formulas [Iac], [Iad], and [Iaf] have a relatively large positive Δε and are excellent in stability, and thus are particularly suitable for an active matrix system using a TFT. . Furthermore, [Iac] and [I
The compound represented by ad] is excellent because it exhibits a liquid crystal phase in a preferable temperature range.

The production method of the compound of the present invention can show the following a) and b).

a) A compound of the general formula [I] in which X is other than a cyano group can be synthesized as follows.

[In the above formula, X ₁ represents a fluorine atom, an alkyl group or an alkoxy group having 1 to 10 carbon atoms, and R, Y, m and n are the same as above. First, the phenine bromide derivative [II] is reacted with magnesium in an ether or THF solvent to prepare a Grignard reagent, and the cyclohexanone derivative [III] is added dropwise thereto. At this time, the reaction temperature is not particularly limited, but is preferably in the range of 0 ° C to 50 ° C. Then, the mixture is stirred for several hours to obtain a cyclohexanol derivative [IV]. Then, in a solvent such as toluene, with an acid catalyst such as p-toluenesulfonic acid, the cyclohexanol derivative [IV] for several hours,
A cyclohexenylethane compound [Ia], which is a compound of the present invention, is obtained by reacting at a reflux temperature.

b) When X is a cyano group in the general formula [I], it can be synthesized as follows.

That is, a phosphonium salt [V] synthesized by a conventional method
With a base such as potassium-tert-butoxide or n-butyllithium to give cyclohexanone derivative [II
I] is reacted. The obtained compound [VI] is oxidized with peracid such as metachloroperbenzoic acid to obtain epoxide [VII].
To get Next, the epoxide [VII] is reduced with a metal hydride such as lithium aluminum hydride or lithium triethylboron hydride, and then dehydrated with an acid catalyst such as paratoluenesulfonic acid to obtain a cyclohexene derivative [Ic]. Next, the compound [Ic] is cyanated with a cyanide such as cuprous cyanide to obtain the desired cyclohexenylethane compound [Ib].

The liquid crystal composition of the present invention contains at least two liquid crystals or a liquid crystal compound, at least one of which is a liquid crystal compound represented by the above formula (I).

As a compound used as a component of the liquid crystal composition of the present invention by mixing with the formula (I), there can be mentioned known compound groups represented by the following (i) to (xxxiii).

In formulas (i) to (xxxiii), X is The illustrated Y represents -CN, -F, -CF _3, and -OCF _3, R ₁ or OR _1, Z represents -H or -F, R and R ₁ represents an alkyl or alkenyl group ..

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

The symbols used in each example are as follows.

mp .: melting point clp .: clearing point [() indicates monotropic transition temperature. Example 1 [4- (trans-4-n-propylcyclohexyl)-{2-
(4-Methylphenyl) ethyl} cyclohexene [compound
Synthesis of No. 1 (X ₁₁ = methyl in the formula [Iaa], Y = H, R = n-propyl)] 2- (4-methylphenyl) ethyl bromide in a three-necked flask containing 0.9 g of magnesium and 5 ml of THF. 6.6 g of 30 ml
The THF solution was added dropwise at 20 ° C. in a nitrogen stream. Then, stir for 1 hour 4- (trans-4-n-propylcyclohexyl)
A 20 ml THF solution of 6.7 g of cyclohexanone was added dropwise at 20 ° C. After stirring for 5 hours, the mixture was cooled to 0 ° C. and 50 ml of 6N hydrochloric acid and 50 ml of toluene were added. After removing the aqueous layer, the solution was washed with 50 ml of a 1N sodium hydroxide aqueous solution, and then washed with water until the aqueous solution became neutral. The obtained toluene solution was dried over anhydrous magnesium sulfate and concentrated. To this was added 0.3 g of p-toluenesulfonic acid and 20 ml of toluene, and the mixture was heated under reflux for 1 hour. At this time, water that azeotropically distilled out was removed using a water draining tube. After cooling to 20 ° C., 50 ml of 0.5N aqueous sodium hydroxide solution and 50 ml of heptane were added, and the aqueous layer was removed. The extract was washed 3 times with 50 ml of saturated saline, dried over anhydrous magnesium sulfate, and concentrated. This was passed through a column filled with alumina with a heptane solvent to remove heptane and then distilled to obtain 6.2 g of white crystals. Further, it was recrystallized from a hexane solvent and dried to obtain 3.2 g of the title compound. Its chemical structure was confirmed by NMR.

mp.46 ° C. clp.120 ° C. (Example 2) The 2- (4-methylphenyl) ethyl bromide used in Example 1 was changed to a suitable phenethyl bromide derivative, and 4- (trans-4-n-propylcyclohexyl was used. ) Cyclohexanone was changed to a suitable cyclohexanone derivative, and the following compound was obtained by the method according to Example 1. ([Iaa]
In the formula, X ₁₁ = alkyl, Y = H) No. 2 4- (trans-4-ethylcyclohexyl)-
{2- (4-Methylphenyl) ethyl} cyclohexene mp.1 ℃ clp.91 ℃ Compound No.3 4- (trans-4-n-butylcyclohexyl)-{2- (4-methylphenyl) ethyl} cyclohexene No .4 4- (trans-4-n-pentylcyclohexyl)
-{2- (4-Methylphenyl) ethyl} cyclohexene mp.36 ℃ clp.125 ℃ No.5 4- (trans-4-n-hexylcyclohexyl)
-{2- (4-Methylphenyl) ethyl} cyclohexene No.6 4- (trans-4-ethylcyclohexyl)-
{2- (4-Ethylphenyl) ethyl} cyclohexene np.1 ℃ clp.107 ℃ No.7 4- (trans-4-n-propylcyclohexyl)
-{2- (4-Ethylphenyl) ethyl} cyclohexene clp.118 ℃ No.8 4- (trans-4-n-butylcyclohexyl)-
{2- (4-Ethylphenyl) ethyl} cyclohexene No.9 4- (trans-4-n-pentylcyclohexyl)
-{2- (4-Ethylphenyl) ethyl} cyclohexene clp.127 ℃ No.10 4- (trans-4-n-hexylcyclohexyl)-{2- (4-ethylphenyl) ethyl} cyclohexene No.11 4- (Trans-4-ethylcyclohexyl)-
{2- (4-n-Propylphenyl) ethyl} cyclohexene No.12 4- (trans-4-n-propylcyclohexyl- {2- (4-n-propylphenyl) ethyl} cyclohexene clp.128 ℃ No.13 4- (trans-4-n-butylcyclohexyl)
-{2- (4-n-Propylphenyl) ethyl} cyclohexene No.14 4- (trans-4-n-pentylcyclohexyl)-{2- (4-n-propylphenyl) ethyl} cyclohexene mp.35 ℃ clp .138 ℃ No.15 4- (trans-4-n-hexylcyclohexyl)-{2- (4-n-propylphenyl) ethyl} cyclohexene No.16 4- (trans-4-ethylcyclohexyl)-
{2- (4-n-Butylphenyl) ethyl} cyclohexene No.17 4- (trans-4-n-propylcyclohexyl)-{2- (4-n-butylphenyl) ethyl} cyclohexene clp.129 ℃ No. 18 4- (trans-4-n-butylcyclohexyl)
-{2- (4-n-Butylphenyl) ethyl} cyclohexene No.19 4- (trans-4-n-pentylcyclohexyl)-{2- (4-n-butylphenyl) ethyl} cyclohexene clp.139 ℃ No .20 4- (trans-4-n-hexylcyclohexyl)-{2- (4-n-butylphenyl) ethyl} cyclohexene No.21 4- (trans-4-ethylcyclohexyl)-
{2- (4-n-Pentylphenyl) ethyl} cyclohexene clp.103 ℃ No.22 4- (trans-4-n-propylcyclohexyl- {2- (4-n-pentylphenyl) ethyl} cyclohexene clp.128 ℃ No.23 4- (trans-4-n-butylcyclohexyl)
-{2- (4-n-Pentylphenyl) ethyl} cyclohexene No.24 4- (trans-4-n-pentylcyclohexyl)-{2- (4-n-pentylphenyl) ethyl} cyclohexene mp.16 ℃ clp .141 ℃ No.25 4- (trans-4-n-hexylcyclohexyl)-{2- (4-n-pentylphenyl) ethyl} cyclohexene No.26 4- (trans-4-ethylcyclohexyl)-
{2- (4-n-Hexylphenyl) ethyl} cyclohexene No.27 4- (trans-4-n-propylcyclohexyl)-{2- (4-n-hexylphenyl) ethyl} cyclohexene No.28 4- ( Trans-4-n-butylcyclohexyl)
-{2- (4-n-Hexylphenyl) ethyl} cyclohexene No.29 4- (trans-4-n-pentylcyclohexyl)-{2- (4-n-hexylphenyl) ethyl} cyclohexene No.30 4- (Trans-4-n-hexylcyclohexyl)-{2- (4-n-hexylphenyl) ethyl} cyclohexene [Iaa] The following compound having the formula of X ₁₁ = alkoxy and Y = H was obtained.

No.31 4- (trans-4-ethylcyclohexyl)-
{2- (4-Methoxyphenyl) ethyl} cyclohexene mp.51 ℃ clp.114 ℃ No.32 4- (trans-4-n-propylcyclohexyl- {2- (4-methoxyphenyl) ethyl} cyclohexene mp.64 ℃ clp.139 ℃ No.33 4- (trans-4-n-butylcyclohexyl)
-{2- (4-Methoxyphenyl) ethyl} cyclohexene mp.45 ℃ clp.134 ℃ No.34 4- (trans-4-n-pentylcyclohexyl)-{2- (4-methoxyphenyl) ethyl} cyclohexene mp .55 ℃ clp.142 ℃ No.35 4- (trans-4-n-hexylcyclohexyl)-{2- (4-methoxyphenyl) ethyl} cyclohexene No.36 4- (trans-4-ethylcyclohexyl)-
{2- (4-Ethoxyphenyl) ethyl} cyclohexene No.37 4- (trans-4-n-propylcyclohexyl)-{2- (4-ethoxyphenyl) ethyl} cyclohexene No.38 4- (trans-4- n-butylcyclohexyl)
-{2- (4-Ethoxyphenyl) ethyl} cyclohexene No.39 4- (trans-4-n-pentylcyclohexyl)-{2- (4-ethoxyphenyl) ethyl} cyclohexene No.40 4- (trans-4 -n-Hexylcyclohexyl)-{2- (4-ethoxyphenyl) ethyl} cyclohexene No.41 4- (trans-4-ethylcyclohexyl)-
{2- (4-n-propoxyphenyl) ethyl} cyclohexene No.42 4- (trans-4-n-propylcyclohexyl- {2- (4-n-propoxyphenyl) ethyl} cyclohexene No.43 4- (trans -4-n-butylcyclohexyl)
-{2- (4-n-Propoxyphenyl) ethyl} cyclohexene No.44 4- (trans-4-n-pentylcyclohexyl)-{2- (4-n-propoxyphenyl) ethyl} cyclohexene No.45 4- (Trans-4-n-hexylcyclohexyl)-{2- (4-n-propoxyphenyl) ethyl} cyclohexene No.46 4- (trans-4-ethylcyclohexyl)-
{2- (4-n-Butyloxyphenyl) ethyl} cyclohexene No.47 4- (trans-4-n-propylcyclohexyl)-{2- (4-n-butyloxyphenyl) ethyl} cyclohexene No.48 4 -(Trans-4-n-butylcyclohexyl)
-{2- (4-n-Butyloxyphenyl) ethyl} cyclohexene No.49 4- (trans-4-n-pentylcyclohexyl)-{2- (4-n-butyloxyphenyl) ethyl} cyclohexene No.50 4- (trans-4-n-hexylcyclohexyl)-{2- (4-n-butyloxyphenyl) ethyl} cyclohexene No.51 4- (trans-4-ethylcyclohexyl)-
{2- (4-n-Pentyloxyphenyl) ethyl} cyclohexene No.52 4- (trans-4-n-propylcyclohexyl)-{2- (4-n-pentyloxyphenyl) ethyl} cyclohexene No.53 4 -(Trans-4-n-butylcyclohexyl)
-{2- (4-n-Pentyloxyphenyl) ethyl} cyclohexene No.54 4- (trans-4-n-pentylcyclohexyl)-{2- (4-n-pentyloxyphenyl) ethyl} cyclohexene No.55 4- (trans-n-hexylcyclohexyl)
-{2- (4-n-Pentyloxyphenyl) ethyl} cyclohexene No.56 4- (trans-4-ethylcyclohexyl)-
{2- (4-n-hexyloxyphenyl) ethyl} cyclohexene No.57 4- (trans-4-n-propylcyclohexyl)-{2- (4-n-hexyloxyphenyl) ethyl} cyclohexene No.58 4 -(Trans-4-n-butylcyclohexyl)
-{2- (4-n-Hexyloxyphenyl) ethyl} cyclohexene No.59 4- (trans-4-n-pentylcyclohexyl)-{2- (4-n-hexyloxyphenyl) ethyl} cyclohexene No.60 4- (trans-4-n-hexylcyclohexyl)-{2- (4--n-hexyloxyphenyl) ethyl}
Cyclohexene (Example 3) 4- {2- (trans-4-n-propylcyclohexyl) ethyl}-{2- (4-ethylphenyl) ethyl} cyclohexene [Compound No. 61 (X ₁₁ = in [Iab] formula Ethyl, Y = H)]
Synthesis of 2- (4-methylphenyl) ethyl bromide used in Example 1 to 2- (4-ethylphenyl) ethyl bromide and 4- (trans-4-n-propylcyclohexyl) cyclohexanone to 4- {2 Example 1 in place of-(trans-4-n-propylcyclohexyl) ethyl} cyclohexanone
It was obtained by a method similar to.

clp.94 ° C. (Example 4) The 2- (4-ethylphenyl) ethyl bromide used in Example 3 was changed to a suitable phenethyl bromide derivative, and 4-
The following compound was obtained by a method similar to that of Example 1 by replacing {2- (trans-4-n-propylcyclohexyl) ethyl} cyclohexanone with a suitable ethylcyclohexanone derivative. [(Iab] in the formula, X ₁₁ = alkyl, Y = H) No. 62 4- {2- (trans-4-ethylcyclohexyl) ethyl}-{2- (4-methylphenyl) ethyl} cyclohexene No. 63 4 -{2- (trans-4-n-propylcyclohexyl) ethyl}-{2- (4-methylphenyl) ethyl} cyclohexene No.64 4- {2- (trans-4-n-butylcyclohexyl) ethyl}- {2- (4-Methylphenyl) ethyl} cyclohexene No.65 4- {2- (trans-4-n-pentylcyclohexyl) ethyl}-{2- (4-meethylphenyl) ethyl}
Cyclohexene No.66 4- {2- (trans-4-n-hexylcyclohexyl) ethyl}-{2- (4-methylphenyl) ethyl} cyclohexene No.67 4- {2- (trans-4-ethylcyclohexyl) Ethyl}-{2- (4-ethylphenyl) ethyl} cyclohexene No.68 4- {2- (trans-4-n-butylcyclohexyl) ethyl}-{2- (4-ethylphenyl) ethyl} cyclohexene No. 69 4- {2- (trans-4-n-pentylcyclohexyl) ethyl}-{2- (4-ethylphenyl) ethyl} cyclohexene No.70 4- {2- (trans-4-n-hexylcyclohexyl) ethyl }-{2- (4-Ethylphenyl) ethyl} cyclohexene No.71 4- {2- (trans-4-ethylcyclohexyl) ethyl}-{2- (4-n-propylphenyl) ethyl}
Cyclohexene No.72 4- {2- (trans-4-n-propylcyclohexyl) ethyl}-{2- (4-n-propylphenyl) ethyl} cyclohexene No.73 4- {2- (trans-4-n -Butylcyclohexyl) ethyl}-{2- (4-n-propylphenyl) ethyl}
Cyclohexene No.74 4- {2- (trans-4-n-pentylcyclohexyl) ethyl}-{2- (4-n-propylphenyl) ethyl} cyclohexene No.75 4- {2- (trans-4-n -Hexylcyclohexyl) ethyl}-{2- (4-n-propylphenyl) ethyl} cyclohexene No.76 4- {2- (trans-4-ethylcyclohexyl) ethyl}-{2- (4-n-butylphenyl ) Ethyl} cyclohexene No. 77 4- {2- (trans-4-n-propylcyclohexyl) ethyl}-{2- (4-n-butylphenyl) ethyl}
Cyclohexene No.78 4- {2- (trans-4-n-butylcyclohexyl) ethyl}-{2- (4-n-butylphenyl) ethyl} cyclohexene No.79 4- {2- (trans-4-n -Pentylcyclohexyl) ethyl}-{2- (4-n-butylphenyl) ethyl}
Cyclohexene No.80 4- {2- (trans-4-n-hexylcyclohexyl) ethyl}-{2- (4-n-butylphenyl) ethyl}
Cyclohexene No.81 4- {2- (trans-4-ethylcyclohexyl) ethyl}-{2- (4-n-pentylphenyl) ethyl}
Cyclohexene No.82 4- {2- (trans-4-n-propylcyclohexyl) ethyl}-{2- (4-n-pentylphenyl) ethyl} cyclohexene No.83 4- {2- (trans-4-n -Butylcyclohexyl) ethyl}-{2- (4-n-pentylphenyl) ethyl}
Cyclohexene No.84 4- {2- (trans-4-n-pentylcyclohexyl) ethyl}-{2- (4-n-pentylphenyl) ethyl} cyclohexene No.85 4- {2- (trans-4-n -Hexylcyclohexyl) ethyl}-{2- (4-n-pentylphenyl) ethyl} cyclohexene No.86 4- {2- (trans-4-ethylcyclohexyl) ethyl}-{2- (4-n-hexylphenyl )ethyl}
Cyclohexene No.87 4- {2- (trans-4-n-propylcyclohexyl) ethyl}-{2- (4-n-hexylphenyl) ethyl} cyclohexene No.88 4- {2- (trans-4-n -Butylcyclohexyl) ethyl}-{2- (4-n-hexylphenyl) ethyl}
Cyclohexene No.89 4- {2- (trans-4-n-pentylcyclohexyl) ethyl}-{2- (4-n-hexylphenyl) ethyl} cyclohexene No.90 4- {2- (trans-4-n -Hexylcyclohexyl) ethyl}-{2- (4-n-hexylphenyl) ethyl} cyclohexene [Iab] The following compound having the formula of X ₁₁ = alkoxy and Y = H was obtained.

No.91 4- {2- (trans-4-ethylcyclohexyl) ethyl}-{2- (4-methoxyphenyl) ethyl} cyclohexene No.92 4-{{2- (trans-4-n-propylcyclohexyl) Ethyl}-{2- (4-methoxyphenyl) ethyl} cyclohexene No. 93 4- {2- (trans-4-n-butylcyclohexyl) ethyl}-{2- (4-methoxyphenyl) ethyl} cyclohexene No. 94 4- {2- (trans-4-n-pentylcyclohexyl) ethyl}-{2- (4-methoxyphenyl) ethyl}
Cyclohexene No.95 4- {2- (trans-4-n-hexylcyclohexyl) ethyl}-{2- (4-methoxyphenyl) ethyl}
Cyclohexene No.96 4- {2- (trans-4-ethylcyclohexyl) ethyl}-{2- (4-ethoxyphenyl) ethyl} cyclohexene No.97 4- {2- (trans-4-n-propylcyclohexyl) Ethyl}-{2- (4-ethoxyphenyl) ethyl}
Cyclohexene No.98 4- {2- (trans-4-n-butylcyclohexyl) ethyl}-{2- (4-ethoxyphenyl) ethyl} cyclohexene No.99 4- {2- (trans-4-n-pentyl Cyclohexyl) ethyl}-{2- (4-ethoxyphenyl) ethyl}
Cyclohexene No.100 4- {2- (trans-4-n-hexylcyclohexyl) ethyl}-{2- (4-ethoxyphenyl) ethyl}
Cyclohexene No.101 4- {2- (trans-4-ethylcyclohexyl) ethyl}-{2- (4-n-propoxyphenyl) ethyl} cyclohexene No.102 4- {2- (trans-4-n-propyl) Cyclohexyl) ethyl}-{2- (4-n-propoxyphenyl) ethyl} cyclohexene No. 103 4- {2- (trans-4-n-butylcyclohexyl) ethyl}-{2- (4-n-propoxyphenyl) ) Ethyl} cyclohexene No. 104 4- {2- (trans-4-n-pentylcyclohexyl) ethyl}-{2- (4-n-propoxyphenyl) ethyl} cyclohexene No. 105 4- {2- (trans- 4-n-hexylcyclohexyl) ethyl}-{2- (4-n-propoxyphenyl) ethyl} cyclohexene No. 106 4- {2- (trans-4-ethylcyclohexyl) ethyl}-{2- (4-n -Butyloxyphenyl) ethyl} cyclohexene No.107 4- 2- (trans-4-n-propylcyclohexyl) ethyl}-{2- (4-n-butyloxyphenyl) ethyl} cyclohexene No. 108 4- {2- (trans-4-n-butylcyclohexyl) ethyl} -{2- (4-n-Butyloxyphenyl) ethyl} cyclohexene No.109 4- {2- (trans-4-n-pentylcyclohexyl) ethyl}-{2- (4-n-butyloxyphenyl) ethyl } Cyclohexene No.110 4- {2- (trans-4-n-hexylcyclohexyl) ethyl}-{2- (4-n-butyloxyphenyl) ethyl} cyclohexene No.111 4- {2- (trans-4 -Ethylcyclohexyl) ethyl}-{2- (4-n-pentyloxyphenyl) ethyl} cyclohexene No.112 4- {2- (trans-4-n-propylcyclohexyl) ethyl}-{2- (4-n -Pentyloxyphenyl)
Ethyl} cyclohexene No.113 4- {2- (trans-4-n-butylcyclohexyl) ethyl}-{2- (4-n-pentyloxyphenyl) ethyl} cyclohexene No.114 4- {2- (trans- 4-n-pentylcyclohexyl) ethyl}-{2- (4-n-pentyloxyphenyl)
Ethyl} cyclohexene No.115 4- {2- (trans-4-n-hexylcyclohexyl) ethyl}-{2- (4-n-pentyloxyphenyl)
Ethyl} cyclohexene No.116 4- {2- (trans-4-ethylcyclohexyl) ethyl}-{2- (4-n-hexyloxyphenyl) ethyl} cyclohexene No.117 4- {2- (trans-4- n-Propylcyclohexyl) ethyl}-{2- (4-n-hexyloxyphenyl)
Ethyl} cyclohexene No.118 4- {2- (trans-4-n-butylcyclohexyl) ethyl}-{2- (4-n-hexyloxyphenyl) ethyl} cyclohexene No.119 4- {2- (trans- 4-n-pentylcyclohexyl) ethyl}-{2- (4-n-hexyloxyphenyl)
Ethyl} cyclohexene No.120 4- {2- (trans-4-n-hexylcyclohexyl) ethyl}-{2- (4-n-hexyloxyphenyl)
Ethyl} cyclohexene (Example 5) 4- (trans-4-n-propylcyclohexyl)-{2-
(3-Fluoro-4-n-propylphenyl) ethyl} cyclohexene [Compound No. 121 (X ₁₁ = propyl, Y in the formula [Iaa]
= F)]) To a three-necked flask containing 0.9 g of magnesium and 5 ml of THF, a solution of 8.1 g of 2- (3-fluoro-4-n-propylphenyl) ethyl bromide in 30 ml of THF was added dropwise at 20 ° C in a nitrogen stream. Then, the mixture was stirred for 1 hour, and a 20 ml THF solution of 6.7 g of 4- (trans-4-n-propylcyclohexyl) cyclohexanone was added dropwise at 20 ° C. After stirring for 5 hours, the mixture was cooled to 0 ° C. and 50 ml of 6N hydrochloric acid and 50 ml of toluene were added. After removing the aqueous layer, the solution was washed with 50 ml of a 1N sodium hydroxide aqueous solution, and then washed with water until the aqueous solution became neutral. The obtained toluene solution was dried over anhydrous magnesium sulfate and concentrated. P-
Add 0.3 g of toluenesulfonic acid and 20 ml of toluene, and add 1.
Heated to reflux for hours. At this time, water that azeotropically distilled out was removed using a water draining tube. After cooling to 20 ° C., 50 ml of 0.5N aqueous sodium hydroxide solution and 50 ml of heptane were added, and the aqueous layer was removed. The extract was washed 3 times with 50 ml of saturated saline, dried over anhydrous magnesium sulfate, and concentrated. This was passed through a column filled with alumina with a heptane solvent to remove heptane and then distilled.
7.6 g of white crystals were obtained. The crystals were recrystallized from a hexane solvent and dried to obtain 3.9 g of the title compound. Its chemical structure is NMR
Confirmed in.

Example 6 The 2- (3-fluoro-4-n-propylphenyl) ethyl bromide used in Example 5 was converted to a suitable fluorophenethyl bromide derivative, and 4- (trans-4-n-propylcyclohexyl) cyclohexanone. Was replaced with a suitable cyclohexanone derivative, and the following compound was obtained by the method according to Example 1. (In formula [Iaa] X ₁₁ alkyl, Y = F) No. 122 4- (trans-4-ethylcyclohexyl)-
{2-3-Fluoro-4-methylphenyl) ethyl} cyclohexene No.123 4- (trans-4-n-propylcyclohexyl)-{2- (3-fluoro-4-methylphenyl) ethyl}
Cyclohexene No.124 4- (trans-4-n-butylcyclohexyl)
-{2- (3-Fluoro-4-methyphenyl) ethyl} cyclohexene No.125 4- (trans-4-n-pentylcyclohexyl)-{2- (3-fluoro-4-methylphenyl) ethyl}
Cyclohexene No. 126 4- (trans-4-n-hexylcyclohexyl)-{2- (3-fluoro-4-methylphenyl) ethyl}
Cyclohexene No.127 4- (trans-4-ethylcyclohexyl)-
{2- (3-Fluoro-4-ethylphenyl) ethyl} cyclohexene No.128 4- (trans-4-n-propylcyclohexyl)-{2- (3-fluoro-4-ethylphenyl) ethyl}
Cyclohexene No.129 4- (trans-4-n-butylcyclohexyl)
-{2- (3-Fluoro-4-ethylphenyl) ethyl} cyclohexene No.130 4- (trans-4-n-pentylcyclohexyl)-{2- (3-fluoro-4-ethylphenyl) ethyl}
Cyclohexene No.131 4- (trans-4-n-hexylcyclohexyl)-{2- (3-fluoro-4-ethylphenyl) ethyl}
Cyclohexene No.132 4- (trans-4-ethylcyclohexyl)-
{2- (3-Fluoro-4-n-propylphenyl) ethyl} cyclohexene No.133 4- (trans-4-n-butylcyclohexyl)
-{2- (3-Fluoro-4-n-propylphenyl) ethyl}
Cyclohexene No.134 4- (trans-4-n-pentylcyclohexyl)-{2- (3-fluoro-4-n-propylphenyl) ethyl} cyclohexene No.135 4- (trans-4-n-hexylcyclohexyl) -{2- (3-Fluoro-4-n-propylphenyl) ethyl} cyclohexene No.136 4- (trans-4-n-ethylcyclohexyl)
-{2- (3-Fluoro-4-butylphenyl) ethyl} cyclohexene No.137 4- (trans-4-n-propylcyclohexyl)-{2- (3-fluoro-4-n-butylphenyl) ethyl} Cyclohexene No.138 4- (trans-4-n-butylcyclohexyl)
-{2- (3-Fluoro-4-n-butylphenyl) ethyl} cyclohexene No.139 4- (trans-4-n-pentylcyclohexyl)-{2- (3-fluoro-4-n-butylphenyl) Ethyl} cyclohexene No.140 4- (trans-4-n-hexylcyclohexyl)-{2- (3-fluoro-4-n-butylphenyl) ethyl} cyclohexene No.141 4- (trans-4-ethylcyclohexyl) -
{2- (3-Fluoro-4-n-pentylphenyl) ethyl} cyclohexene No.142 4- (trans-4-n-propylcyclohexyl)-{2- (3-fluoro-4-n-pentylphenyl) ethyl } Cyclohexene No.143 4- (trans-4-n-butylcyclohexyl)
-{2- (3-Fluoro-4-n-pentylphenyl) ethyl}
Cyclohexene No.144 4- (trans-4-n-pentylcyclohexyl)-{2- (3-fluoro-4-n-pentylphenyl) ethyl} cyclohexene No.145 4- (trans-4-n-hexylcyclohexyl) -{2- (3-Fluoro-4-n-pentylphenyl) ethyl} cyclohexene No.146 4- (trans-4-ethylcyclohexyl)-
{2- (3-Fluoro-4-n-hexylphenyl) ethyl} cyclohexene No.147 4- (trans-4-n-propylcyclohexyl)-{2- (3-fluoro-4-n-hexylphenyl) ethyl } Cyclohexene No.148 4- (trans-4-n-butylcyclohexyl)
-{2- (3-Fluoro-4-n-hexylphenyl) ethyl}
Cyclohexene No.149 4- (trans-4-n-pentylcyclohexyl)-{2- (3-fluoro-4-n-hexylphenyl) ethyl} cyclohexene No.150 4- (trans-4-n-hexylcyclohexyl) -{2- (3-Fluoro-4-n-hexylphenyl) ethyl} cyclohexene [Iaa] In the formula, the following compound having X ₁₁ = alkoxy and Y = F was obtained.

No.151 4- (trans-4-ethylcyclohexyl)-
{2- (3-Fluoro-4-methoxyphenyl) ethyl} cyclohexene No.152 4- (trans-4-n-propylcyclohexyl)-{2- (3-fluoro-4-methoxyphenyl) ethyl} cyclohexene No. 153 4- (trans-4-n-butylcyclohexyl)
-{2- (3-Fluoro-4-methoxyphenyl) ethyl} cyclohexene No.154 4- (trans-4-n-pentylcyclohexyl)-{2- (3-fluoro-4-methoxyphenyl) ethyl} cyclohexene No .155 4- (trans-4-n-hexylcyclohexyl)-{2- (3-fluoro-4-methoxyphenyl) ethyl} cyclohexene No.156 4- (trans-4-ethylcyclohexyl)-
{2- (3-Fluoro-4-ethoxyphenyl) ethyl} cyclohexene No.157 4- (trans-4-n-propylcyclohexyl)-{2- (3-fluoro-4-ethoxyphenyl) ethyl} cyclohexene No. 158 4- (trans-4-n-butylcyclohexyl)
-{2- (3-Fluoro-4-ethoxyphenyl) ethyl} cyclohexene No.159 4- (trans-4-n-pentylcyclohexyl)-{2- (3-fluoro-4-ethoxyphenyl) ethyl} cyclohexene No .160 4- (trans-4-n-hexylcyclohexyl)-{2- (3-fluoro-4-ethoxyphenyl) ethyl} cyclohexene No.161 4- (trans-4-ethylcyclohexyl)-
{2- (3-Fluoro-4-n-propoxyphenyl) ethyl}
Cyclohexene No.162 4- (trans-4-n-propylcyclohexyl)-{2- (3-fluoro-4-n-propoxyphenyl) ethyl} cyclohexene No.163 4- (trans-4-n-butylcyclohexyl)
-{2- (3-Fluoro-4-n-propoxyphenyl) ethyl} cyclohexene No.164 4- (trans-4-n-pentylcyclohexyl)-{2- (3-fluoro-4-n-propoxyphenyl) Ethyl} cyclohexene No.165 4- (trans-4-n-hexylcyclohexyl)-{2- (3-fluoro-4-n-propoxyphenyl) ethyl} cyclohexene No.166 4- (trans-4-ethylcyclohexyl) -
{2- (3-Fluoro-4-n-butyloxyphenyl) ethyl} cyclohexene No.167 4- (trans-4-n-propylcyclohexyl)-{2- (3-fluoro-4-n-butyloxyphenyl) )
Ethyl} cyclohexene No.168 4- (trans-4-n-butylcyclohexyl)
-{2- (3-Fluoro-4-n-butyloxyphenyl) ethyl} cyclohexene No.169 4- (trans-4-n-pentylcyclohexyl)-{2- (3-fluoro-4-n-butyloxy Phenyl)
Ethyl} cyclohexene No.170 4- (trans-4-n-hexylcyclohexyl)-{2- (3-fluoro-4-n-butyloxyphenyl)
Ethyl} cyclohexene No.171 4- (trans-4-ethylcyclohexyl)-
{2- (3-Fluoro-4-n-pentyloxyphenyl) ethyl} cyclohexene No.172 4- (trans-4-n-propylcyclohexyl)-{2- (3-fluoro-4-n-pentyloxyphenyl) ) Ethyl} cyclohexene No.173 4- (trans-4-n-butylcyclohexyl)
-{2- (3-Fluoro-4-n-pentyloxyphenyl) ethyl} cyclohexene No.174 4- (trans-4-n-pentylcyclohexyl)-{2- (3-fluoro-4-n-pentyloxy (Phenyl) ethyl} cyclohexene No.175 4- (trans-4-n-hexylcyclohexyl)-{2- (3-fluoro-4-n-pentyloxyphenyl) ethyl} cyclohexene No.176 4- (trans-4- Ethylcyclohexyl)-
{2- (3-Fluoro-4-n-hexyloxyphenyl) ethyl} cyclohexene No.177 4- (trans-4-n-propylcyclohexyl)-{2- (3-fluoro-4-n-hexyloxyphenyl) ) Ethyl} cyclohexene No.178 4- (trans-4-n-butylcyclohexyl)
-{2- (3-Fluoro-4-n-hexyloxyphenyl) ethyl} cyclohexene No.179 4- (trans-4-n-pentylcyclohexyl)-{2- (3-fluoro-4-n-hexyloxy (Phenyl) ethyl} cyclohexene No. 180 4- (trans-4-n-hexylcyclohexyl)-{2- (3-fluoro-4-n-hexyloxyphenyl) ethyl} cyclohexene (Example 7) 4- {2- (Trans-4-n-propylcyclohexyl) ethyl}-{2- (3-fluoro-4-n-propylphenyl) ethyl} cyclohexene [Compound No.181 ([Iab] X ₁₁ =
Propyl, Y = F)] 4- (trans-n-propylcyclohexyl) cyclohexanone used in Example 5 was changed to 4- {2- (trans-4-n-propylcyclohexyl) ethyl} cyclohexanone to give 2 -(3-Fluoro-4-n-propylphenyl) ethyl bromide was reacted and obtained by the method according to Example 1.

Example 8 The 2- (3-fluoro-4-n-propylphenyl) ethyl bromide used in Example 7 was converted to the appropriate fluorophenethyl bromide derivative and 4- {2- (trans-4-n-propyl). By replacing cyclohexyl) ethyl} cyclohexanone with an appropriate ethylcyclohexanone derivative, the following compound was obtained by the method according to Example 1. (In formula [I ab] X ₁₁ = alkyl, Y = F) No. 182 4- {2- (trans-4-ethylcyclohexyl) ethyl}-{2- (3-fluoro-4-methylphenyl)
Ethyl} cyclohexene No.183 4- {2- (trans-4-n-propylcyclohexyl) ethyl}-{2- (3-fluoro-4-methylphenyl) ethyl} cyclohexene No.184 4- {2- (trans -4-n-Butylcyclohexyl) ethyl}-{2- (3-fluoro-4-methylphenyl)
Ethyl} cyclohexene No.185 4- {2- (trans-4-n-pentylcyclohexyl) ethyl}-{2- (3-fluoro-4-methylphenyl) ethyl} cyclohexene No.186 4- {2- (trans -4-n-Hexylcyclohexyl) ethyl}-{2- (3-fluoro-4-methylphenyl) ethyl} cyclohexene No.187 4- {2- (trans-4-ethylcyclohexyl) ethyl}-{2- ( 3-fluoro-4-ethylphenyl)
Ethyl} cyclohexene No.188 4- {2- (trans-4-n-propylcyclohexyl) ethyl}-{2- (3-fluoro-4-ethylphenyl) ethyl} cyclohexene No.189 4- {2- (trans -4-n-Butylcyclohexyl) ethyl}-{2- (3-fluoro-4-ethylphenyl)
Ethyl} cyclohexene No.190 4- {2- (trans-4-n-pentylcyclohexyl) ethyl}-{2- (3-fluoro-4-ethylphenyl) ethyl} cyclohexene No.191 4- {2- (trans -4-n-hexylcyclohexyl) ethyl}-{2- (3-fluoro-4-ethylphenyl) ethyl} cyclohexene No.192 4- {2- (trans-4-ethylcyclohexyl) ethyl}-{2- ( 3-Fluoro-4-n-propylphenyl) ethyl} cyclohexene No.193 4- {2- (trans-4-n-butylcyclohexyl) ethyl}-{2- (3-fluoro-4-n-propylphenyl) Ethyl} cyclohexene No.194 4- {2- (trans-4-n-pentylcyclohexyl) ethyl}-{2- (3-fluoro-4-n-propylphenyl) ethyl} cyclohexene No.195 4- {2- (Trans-4-n-hexylcyclohexyl) ethyl}-{2- (3- Luoro-4-n-propylphenyl) ethyl} cyclohexene No.196 4- {2- (trans-4-ethylcyclohexyl) ethyl}-{2- (3-fluoro-4-n-butylphenyl) ethyl} cyclohexene No .197 4- {2- (trans-4-n-propylcyclohexyl) ethyl}-{2- (3-fluoro-4-n-butylphenyl) ethyl} cyclohexene No.198 4- {2- (trans-4 -n-Butylcyclohexyl) ethyl}-{2- (3-fluoro-4-n-butylphenyl) ethyl} cyclohexene No.199 4- {2- (trans-4-n-pentylcyclohexyl) ethyl}-{2 -(3-Fluoro-4-n-butylphenyl) ethyl} cyclohexene No.200 4- {2- (trans-4-n-hexylcyclohexyl) ethyl}-{2- (3-fluoro-4-n-butyl Phenyl) ethyl} cyclohexene No.201 4- {2- (trans-ethylcyclohexyl )
Ethyl}-{2- (3-fluoro-4-n-pentylphenyl)
Ethyl} cyclohexene No.202 4- {2- (trans-n-propylcyclohexyl) ethyl}-{2- (3-fluoro-4-n-pentylphenyl) ethyl} cyclohexene No.203 4- {2- (trans -N-Butylcyclohexyl) ethyl}-{2- (3-fluoro-4-n-pentylphenyl) ethyl} cyclohexene No.204 4- {2- (trans-n-pentylcyclohexyl) ethyl}-{2- ( 3-Fluoro-4-n-pentylphenyl) ethyl} cyclohexene No.205 4- {2- (trans-n-hexylcyclohexyl) ethyl}-{2- (3-fluoro-4-n-pentylphenyl) ethyl} Cyclohexene No.206 4- {2- (trans-4-ethylcyclohexyl) ethyl}-{2- (3-fluoro-4-n-hexylphenyl) ethyl} cyclohexene No.207 4- {2- (trans-4 -n-Propylcyclohexyl) ethyl}-{2- (3- Fluoro-4-n-hexylphenyl) ethyl} cyclohexene No.208 4- {2- (trans-4-n-butylcyclohexyl) ethyl}-{2- (3-fluoro-4-n-hexylphenyl) ethyl} Cyclohexene No.209 4- {2- (trans-4-n-pentylcyclohexyl) ethyl}-{2- (3-fluoro-4-n-hexylphenyl) ethyl} cyclohexene No.210 4- {2- (Trans-4-n-hexylcyclohexyl) ethyl}-{2- (3-fluoro-4-n-hexylphenyl) ethyl} cyclohexene [I ab] The following compound with X ₁₁ = alkoxy and Y = F Obtained.

No.211 4- {2- (trans-4-ethylcyclohexyl) ethyl}-{2- (3-fluoro-4-methoxyphenyl) ethyl} cyclohexene No.212 4- {2- (trans-4-n- Propylcyclohexyl) ethyl}-{2- (3-fluoro-4-methoxyphenyl) ethyl} cyclohexene No.213 4- {2- (trans-4-n-butylcyclohexyl) ethyl}-{2- (3-fluoro -4-Methoxyphenyl) ethyl} cyclohexene No.214 4- {2- (trans-4-n-pentylcyclohexyl) ethyl}-{2- (3-fluoro-4-methoxyphenyl) ethyl} cyclohexene No.215 4 -{2- (trans-4-n-hexylcyclohexyl) ethyl}-{2- (3-fluoro-4-methoxyphenyl) ethyl} cyclohexene No.216 4- {2- (trans-4-ethylcyclohexyl) ethyl }-{2- (3-Fluoro-4-ethoxyphenyl ) Ethyl} cyclohexene No.217 4- {2- (trans-4-n-propylcyclohexyl) ethyl}-{2- (3-fluoro-4-ethoxyphenyl) ethyl} cyclohexene No.218 4- {2- ( Trans-4-n-butylcyclohexyl) ethyl}-{2- (3-fluoro-4-ethoxyphenyl) ethyl} cyclohexene No. 219 4- {2- (trans-4-n-pentylcyclohexyl) ethyl}-{ 2- (3-Fluoro-4-ethoxyphenyl) ethyl} cyclohexene No.220 4- {2- (trans-4-n-hexylcyclohexyl) ethyl}-{2- (3-fluoro-4-ethoxyphenyl) ethyl } Cyclohexene No.221 4- {2- (trans-4-ethylcyclohexyl) ethyl}-{2- (3-fluoro-4-n-propoxyphenyl) ethyl} cyclohexene No.222 4- {2- (trans- 4-n-propylcyclohexyl) ethyl}-{2 -(3-Fluoro-4-propoxyphenyl) ethyl} cyclohexene No.223 4- {2- (trans-4-n-butylcyclohexyl) ethyl}-{2- (3-fluoro-4-n-propoxyphenyl) Ethyl} cyclohexene No.224 4- {2- (trans-4-n-pentylcyclohexyl) ethyl}-{2- (3-fluoro-4-n-propoxyphenyl) ethyl} cyclohexene No.225 4- {2- (Trans-4-n-hexylcyclohexyl) ethyl}-{2- (3-fluoro-4-n-propoxyphenyl) ethyl} cyclohexene No.226 4- {2- (trans-4-ethylcyclohexyl) ethyl}- {2- (3-Fluoro-4-n-butyloxyphenyl) ethyl} cyclohexene No.227 4- {2- (trans-4-n-propylcyclohexyl) ethyl}-{2- (3-fluoro-4- n-Butyloxyphenyl) ethyl} cyclohexene No.228 4- {2- Trans-4-n-butylcyclohexyl) ethyl}-{2- (3-fluoro-4-n-butyloxyphenyl) ethyl} cyclohexene No.229 4- {2- (trans-4-n-pentylcyclohexyl) ethyl }-{2- (3-Fluoro-4-n-butyloxyphenyl) ethyl} cyclohexene No.230 4- {2- (trans-4-n-hexylcyclohexyl) ethyl}-{2- (3-fluoro- 4-n-Butyloxyphenyl) ethyl} cyclohexene No.231 4- {2- (trans-4-ethylcyclohexyl) ethyl}-{2- (3-fluoro-4-n-pentyloxyphenyl) ethyl} cyclohexene No .232 4- {2- (trans-4-n-propylcyclohexyl) ethyl}-{2- (3-fluoro-4-n-pentyloxyphenyl) ethyl} cyclohexene No.233 4- {2- (trans- 4-n-butylcyclohexyl) ethyl}-{2- (3-full Ro-4-pentyloxyphenyl) ethyl} cyclohexene No.234 4- {2- (trans-4-n-pentylcyclohexyl) ethyl}-{2- (3-fluoro-4-n-pentyloxyphenyl) ethyl} Cyclohexene No.235 4- {2- (trans-4-n-hexylcyclohexyl) ethyl}-{2- (3-fluoro-4-n-pentyloxyphenyl) ethyl} cyclohexene No.236 4- {2- ( Trans-4-ethylcyclohexyl) ethyl}-{2- (3-fluoro-4-n-hexyloxyphenyl) ethyl} cyclohexene No.237 4- {2- (trans-4-n-propylcyclohexyl) ethyl}- {2- (3-Fluoro-4-n-hexyloxyphenyl) ethyl} cyclohexene No.238 4- {2- (trans-4-n-butylcyclohexyl) ethyl}-{2- (3-fluoro-4- n-hexyloxyphenyl) ethyl} cyclohexene No.239 4- {2- (trans-4-n-pentylcyclohexyl) ethyl}-{2- (3-fluoro-4-n-hexyloxyphenyl) ethyl} cyclohexene No.240 4- {2- (trans -4-n-Hexylcyclohexyl) ethyl}-{2- (3-fluoro-4-n-hexyloxyphenyl) ethyl} cyclohexene (Example 9) 4- (trans-4-n-propylcyclohexyl)-{2 -
Synthesis of (4-fluorophenyl) ethyl} cyclohexene [Compound No. 241 (Y = H, R = propyl in [I ac]]] 2- (4-methylphenyl) ethyl bromide used in Example 1 instead of (4-fluorophenyl) ethyl bromide, 4- (trans -4-n ^- - propylcyclohexyl)
Cyclohexanone was reacted and obtained by the method according to Example 1.

mp.25 ° C. clp.95 ° C. (Example 10) The 2- (4-fluorophenyl) ethyl bromide used in Example 9 was converted to a suitable fluorophenylethyl bromide derivative, and 4- (trans-4-n-propyl). By replacing cyclohexyl) cyclohexanone with a suitable cyclohexanone derivative, the following compound was obtained by the method according to Example 1.

([I ac] Y = H) No.242 4- (trans-4-methylcyclohexyl)-
{2- (4-Fluorophenyl) ethyl} cyclohexene No.243 4- (trans-4-ethylcyclohexyl)-
{2- (4-Fluorophenyl) ethyl} cyclohexene No.244 4- (trans-4-n-butylcyclohexyl)
-{2- (4-Fluorophenyl) ethyl} cyclohexene No.245 4- (trans-4-n-pentylcyclohexyl)-{2- (4-fluorophenyl) ethyl} cyclohexene mp.17 ℃ clp.99 ℃ No .246 4- (trans-4-n-hexylcyclohexyl)-{2- (4-fluorophenyl) ethyl} cyclohexene No.247 4- (trans-4-n-heptylcyclohexyl)-{2- (4-fluoro Phenyl) ethyl} cyclohexene clp.100 ℃ No.248 4- (trans-4-n-octylcyclohexyl)-{2- (4-fluorophenyl) ethyl} cyclohexene No.249 4- (trans-4-n-nonyl Cyclohexyl)
-{2- (4-Fluorophenyl) ethyl} cyclohexene No.250 4- (trans-4-n-decylcyclohexyl)
-{2- (4-Fluorophenyl) ethyl} cyclohexene [I ac] having the formula Y = F was obtained.

No.251 4- (trans-4-methylcyclohexyl)-
{2- (3,4-Difluorophenyl) ethyl} cyclohexene No.252 4- (trans-4-ethylcyclohexyl)-
{2- (3,4-Difluorophenyl) ethyl} cyclohexene mp.26 ℃ clp.43 ℃ No.253 4- (trans-4-n-propylcyclohexyl)-{2- (3,4-difluorophenyl) ethyl } Cyclohexene mp.9 ℃ clp.71 ℃ No.254 4- (trans-4-n-butylcyclohexyl)
-{2- (3,4-Difluorophenyl) ethyl} cyclohexene No.255 4- (trans-4-n-pentylcyclohexyl)-{2- (3,4-difluorophenyl) ethyl} cyclohexene mp.13 ℃ clp .81 ℃ No.256 4- (trans-4-n-hexylcyclohexyl)-{2- (3,4-difluorophenyl) ethyl} cyclohexene No.257 4- (trans-4-n-heptylcyclohexyl)-{ 2- (3,4-Difluorophenyl) ethyl} cyclohexene No.258 4- (trans-4-n-octylcyclohexyl)-{2- (3,4-difluorophenyl) ethyl} cyclohexene No.259 4- (trans -4-n-nonylcyclohexyl)
-{2- (3,4-Difluorophenyl) ethyl} cyclohexene No.260 4- (trans-4-n-decylcyclohexyl)
-{2- (3,4-Difluorophenyl) ethyl} cyclohexene (Example 11) 4- {2- (trans-4-n-propylcyclohexyl) ethyl}-{2- (4-fluorophenyl) ethyl} cyclohexene [Synthesis of Compound No. 261 (Y = H, R = n-propyl in [I ad]]] 4- {2- (trans-n-propylcyclohexyl) cyclohexanone used in Example 9 was converted into 4- {2- (trans -4-n-Propylcyclohexyl) ethyl} cyclohexanone was replaced with 2- (4-fluorophenyl) ethyl bromide, and a method similar to that of Example 1 was obtained.

(Example 12) 4- (2- (trans-4-n-propylcyclohexyl) ethyl} cyclohexanone used in Example 11 was replaced with a suitable ethylcyclohexanone derivative to give 2- (4-fluorophenyl) ethyl bromide. The reaction was carried out and the following compound was obtained by the method according to Example 1. [(I ad is Y = H) No.262 4- {2- (trans-4-methylcyclohexyl) ethyl}-{2- (4-fluorophenyl) ethyl} cyclohexene No.263 4- {2- ( Trans-4-ethylcyclohexyl) ethyl}-{2- (4-fluorophenyl) ethyl} cyclohexene No.264 4- {2- (trans-4-n-butylcyclohexyl) ethyl}-{2- (4-fluoro Phenyl) ethyl} cyclohexene No.265 4- {2- (trans-4-n-pentylcyclohexyl) ethyl}-{2- (4-fluorophenyl) ethyl}
Cyclohexene No.266 4- {2- (trans-4-n-hexylcyclohexyl) ethyl}-{2- (4-fluorophenyl) ethyl}
Cyclohexene No.267 4- {2- (trans-4-n-heptylcyclohexyl) ethyl}-{2- (4-fluorophenyl) ethyl}
Cyclohexene No.268 4- {2- (trans-4-n-octylcyclohexyl) ethyl}-{2- (4-fluorophenyl) ethyl}
Cyclohexene No.269 4- {2- (trans-4-n-nonylcyclohexyl) ethyl}-{2- (4-fluorophenyl) ethyl} cyclohexene No.270 4- {2- (trans-4-n-decyl cyclohexyl) ethyl} - {2- (4-fluorophenyl) ethyl} cyclohexene ^- to give the following compounds of Y = F in [I ad] expression.

No.271 4- {2- (trans-4-methylcyclohexyl) ethyl}-{2- (3,4-difluorophenyl) ethyl} cyclohexene No.272 4- {2- (trans-4-ethylcyclohexyl) ethyl }-{2- (3,4-Difluorophenyl) ethyl} cyclohexene No.273 4- {2- (trans-4-n-propylcyclohexyl) ethyl}-{2- (3,4-difluorophenyl) ethyl} Cyclohexene mp.30.5 ℃ clp.61.1 ℃ No.274 4- {2- (trans-4-n-butylcyclohexyl) ethyl}-{2- (3,4-difluorophenyl) ethyl} cyclohexene No.275 4- { 2- (trans-4-n-pentylcyclohexyl) ethyl}-{2- (3,4-difluorophenyl) ethyl} cyclohexene No.276 4- {2- (trans-4-n-hexylcyclohexyl) ethyl}- {2- (3,4-Difluorophenyl) ethyl} silohexene No.277 4- {2- Trans-4-n-heptylcyclohexyl) ethyl}-{2- (3,4-difluorophenyl) ethyl} cyclohexene No.278 4- {2- (trans-4-n-octylcyclohexyl) ethyl}-{2- (3,4-Difluorophenyl) ethyl} cyclohexene No.279 4- {2- (trans-4-n-nonylcyclohexyl) ethyl}-{2- (3,4-difluorophenyl) ethyl} cyclohexene No.280 4 -{2- (trans-4-n-decylcyclohexyl) ethyl}-{2- (3,4-difluorophenyl) ethyl} cyclohexene (Example 13) 4-n-propyl- {2- (4-methoxyphenyl) ) Ethyl} cyclohexene [No.281 (in the formula [I ac] X ₁₁ ═CH ₃ O, R═nC
_{3 (} H ₇ )] The 2- (4-methylphenyl) ethyl bromide used in Example 1 was replaced with 2- (4-methoxyphenyl) ethyl bromide.
Further, 4- (trans-4-n-propylcyclohexyl) cyclohexanone was changed to 4-n-propylcyclohexanone, and a method similar to that of Example 1 was used.

Example 14 The 2- (4-methylphenyl) ethyl bromide used in Example 1 was changed to a suitable phenethyl bromide derivative, and 4- (trans-4-n-propylcyclohexyl) cyclohexanone was changed to a suitable cyclohexanone derivative. Instead, the following compound was obtained by a method similar to that in Example 1. ([I ae]
In the formula, X ₁₁ = alkoxy) No. 282 4-ethyl- {2- (4-methoxyphenyl) ethyl} cyclohexene No.283 4-n-butyl- {2- (4-methoxyphenyl) ethyl} cyclohexene No.284 4-n-pentyl- {2- (4-methoxyphenyl)
Ethyl} cyclohexene No.285 4-n-hexyl- {2- (4-methoxyphenyl)
Ethyl} cyclohexene No.286 4-n-heptyl- {2- (4-methoxyphenyl)
Ethyl} cyclohexene No.287 4-n-octyl- {2- (4-methoxyphenyl)
Ethyl} cyclohexene No.288 4-n-nonyl- {2- (4-methoxyphenyl) ethyl} cyclohexene No.289 4-n-decyl- {2- (4-methoxyphenyl) ethyl} cyclohexene No.290 4- Ethyl- {2- (4-ethoxyphenyl) ethyl} cyclohexene No.291 4-n-propyl- {2- (4-ethoxyphenyl)
Ethyl} cyclohexene No.292 4-n-butyl- {2- (4-ethoxyphenyl) ethyl} cyclohexene No.293 4-n-pentyl- {2- (4-ethoxyphenyl)
Ethyl} cyclohexene No.294 4-n-hexyl- {2- (4-ethoxyphenyl)
Ethyl} cyclohexene No.295 4-n-heptyl- {2- (4-ethoxyphenyl)
Ethyl} cyclohexene No.296 4-n-octyl- {2- (4-ethoxyphenyl)
Ethyl} cyclohexene No.297 4-n-nonyl- {2- (4-ethoxyphenyl) ethyl} cyclohexene No.298 4-n-decyl- {2- (4-ethoxyphenyl) ethyl} cyclohexene No.299 4- Ethyl- {2- (4-n-propoxyphenyl)
Ethyl} cyclohexene No.300 4-n-propyl- {2- (4-n-propoxyphenyl) ethyl} cyclohexene No.301 4-n-butyl- {2- (4-n-propoxyphenyl) ethyl} cyclohexene No .302 4-n-pentyl- {2- (4-n-propoxyphenyl) ethyl} cyclohexene No.303 4-n-hexyl- {2- (4-n-propoxyphenyl) ethyl} cyclohexene No.304 4- n-Heptyl- {2- (4-n-propoxyphenyl) ethyl} cyclohexene No.305 4-n-octyl- {2- (4-n-propoxyphenyl) ethyl} cyclohexene No.306 4-n-nonyl- {2- (4-n-propoxyphenyl) ethyl} cyclohexene No.307 4-n-decyl- {2- (4-n-propoxyphenyl) ethyl} cyclohexene No.308 4-ethyl- {2- (4- n-Butyloxyphenyl) ethyl} cyclohexene No.309 4-n-propyl- {2- (4-n-butyloxyfuran Ethenyl) ethyl} cyclohexene No.310 4-n-butyl- {2- (4-n-butyloxyphenyl) ethyl} cyclohexene No.311 4-n-pentyl- {2- (4-n-butyloxyphenyl) Ethyl} cyclohexene No.312 4-n-hexyl- {2- (4-n-butyloxyphenyl) ethyl} cyclohexene No.313 4-n-heptyl- {2- (4-n-butyloxyphenyl) ethyl} Cyclohexene No.314 4-n-octyl- {2- (4-n-butyloxyphenyl) ethyl} cyclohexene No.315 4-n-nonyl- {2- (4-n-butyloxyphenyl) ethyl} cyclohexene No .316 4-n-decyl- {2- (4-n-butyloxyphenyl) ethyl} cyclohexene No.317 4-ethyl- {2- (4-n-pentyloxyphenyl) ethyl} cyclohexene No.318 4- n-Propyl- {2- (4-n-pentyloxyphenyl) ethyl} cyclohexene No.319 4-n-butyl Ru- {2- (4-n-pentyloxyphenyl) ethyl} cyclohexene No.320 4-n-pentyl- {2- (4-n-pentyloxyphenyl) ethyl} cyclohexene No.321 4-n-hexyl- {2- (4-n-Pentyloxyphenyl) ethyl} cyclohexene No.322 4-n-heptyl- {2- (4-n-pentyloxyphenyl) ethyl} cyclohexene No.323 4-n-octyl- {2 -(4-n-Pentyloxyphenyl) ethyl} cyclohexene No.324 4-n-nonyl- {2- (4-n-pentyloxyphenyl) ethyl} cyclohexene No.325 4-n-decyl- {2- ( 4-n-pentyloxyphenyl) ethyl} cyclohexene (Example 15) 4-n-propyl- {2- (4-fluorophenyl) ethyl} cyclohexene [No.326 (Y = H, R in the formula [I af]] = NC
_{3 (} H ₇ )] The 2- (4-methylphenyl) ethyl bromide used in Example 1 was replaced with 2- (4-fluorophenyl) ethyl bromide and 4- (trans-4-n-propylcyclohexyl).
Cyclohexanone was changed to 4-n-propylcyclohexanone, and the method described in Example 1 was applied.

Example 16 The 2- (4-methylphenyl) ethyl bromide used in Example 1 was used as a 2- (4-fluorophenyl) ethyl bromide derivative, and 4- (trans-4-n-propylcyclohexyl) cyclohexanone was used. The following compound was obtained by a method similar to that of Example 1 in place of the appropriate cyclohexanone derivative.

(Y = H in the formula [I af]) No.327 4-ethyl- {2- (4-fluorophenyl) ethyl} cyclohexene No.328 4-n-butyl- {2- (4-fluorophenyl) ethyl} Cyclohexene No.329 4-n-pentyl- {2- (4-fluorophenyl)
Ethyl} cyclohexene No.330 4-n-hexyl- {2- (4-fluorophenyl)
Ethyl} cyclohexene No.331 4-n-heptyl- {2- (4-fluorophenyl)
Ethyl} cyclohexene No.332 4-n-octyl- {2- (4-fluorophenyl)
Ethyl} cyclohexene No.333 4-n-nonyl- {2- (4-fluorophenyl) ethyl} cyclohexene No.334 4-n-decyl- {2- (4-fluorophenyl) ethyl} cyclohexene (Example 17) 4-n-Propyl- {2- (3,4-difluorophenyl) ethyl} cyclohexene [No.335 (Y = F in the formula [I af])]
Synthesis of 2- (4-methylphenyl) ethyl bromide used in Example 1 to 2- (3,4-difluorophenyl) ethyl bromide and 4- (trans-4-n-propylcyclohexyl) cyclohexanone to 4- Instead of n-propylcyclohexanone, it was obtained by the method according to Example 1.

mp.3 ° C. (clp. −35 ° C.) (Example 18) The 2- (4-methylphenyl) ethyl bromide used in Example 1 was used as a 2- (3,4-difluorophenyl) ethyl bromide derivative, and 4 By replacing-(trans-4-n-propylcyclohexyl) cyclohexanone with a suitable cyclohexanone derivative, the following compound was obtained by the method according to Example 1. (Y = F in the formula [I af]) No.336 4-Ethyl- {2- (3,4-difluorophenyl)
Ethyl} cyclohexene No.337 4-n-butyl- {2- (3,4-difluorophenyl) ethyl} cyclohexene No.338 4-n-pentyl- {2- (3,4-difluorophenyl) ethyl} cyclohexene No .339 4-n-hexyl- {2- (3,4-difluorophenyl) ethyl} cyclohexene No.340 4-n-heptyl- {2- (3,4-difluorophenyl) ethyl} cyclohexene No.341 4- n-octyl- {2- (3,4-difluorophenyl) ethyl} cyclohexene No.342 4-n-nonyl- {2- (3,4-difluorophenyl) ethyl} cyclohexene No.343 4-n-decyl- {2- (3,4-Difluorophenyl) ethyl} cyclohexene (Example 19) 4- (trans-4-n-pentylcyclohexyl) -1- {2-
(4-Cyanophenyl) ethyl} cyclohexene {No.344
(Y = H, R = C ₅ H ₁₁ ) in the formula [I ba]} (i) of 4- (trans-4-n-pentylcyclohexyl) cyclohexylidene-2- (4-bromophenyl) ethane Synthetic 2- (4-bromophenyl) ethyltriphenylphosphonium bromide 26.3 g and 100 ml THF in a 500 ml three-necked flask, potassium tert-butoxide 5.6 g at -50 ℃
Was added. Stir for 1 hour at -50 ° C, then 4- (trans-4-
n-pentylcyclohexyl) cyclohexanone 10.0 g 5
0 ml THF solution was added dropwise. Then, the temperature was gradually raised to room temperature and the mixture was stirred for 10 hours. 300 ml of water was added to this, and the mixture was stirred and extracted with 200 ml of toluene. The organic layer was washed twice with 300 ml of water, dried over anhydrous magnesium sulfate and concentrated. To this, 300 ml of heptane was added and the precipitated crystals were filtered off and the filtrate was passed through a column filled with silica gel and concentrated. Recrystallization from a mixed solvent of alcohol and ethyl acetate and drying gave 10.1 g of the title compound. mp.73 ℃ (ii) 4- (trans-4-n-pentylcyclohexyl)-
Synthesis of 1- {2-4-bromophenyl) ethyl} cyclohexene Compound (8.0) obtained in (i) at 10 ° C. in a three-necked flask containing 6.6 g of metachloroperbenzoic acid, 5.3 g of potassium carbonate and 70 ml of chloroform. g of 30 ml chloroform solution was added dropwise. After stirring for 3 hours, the insoluble matter was removed by filtration, and 50 ml of an aqueous sodium thiosulfate solution was added thereto. After removing the aqueous layer, the mixture was washed with 50 ml of a 1N sodium hydroxide aqueous solution and washed with water until the washing liquid became neutral. It was dried over anhydrous magnesium sulfate and concentrated to obtain 8.9 g of an oily substance.

A 30 ml THF solution of this was placed in a 200 ml three-necked flask containing 29 ml of a 1 molar solution of lithium triethylborohydride.
It was added dropwise at 0 ° C. After stirring for 1 day, 100 ml water and 10 toluene
0 ml was added and the aqueous layer was removed. The organic layer was washed twice with 100 ml of water, dried over anhydrous magnesium sulfate and then concentrated.

To this, 0.1 g of paratoluenesulfonic acid monohydrate and 50 ml of toluene were added, and the mixture was heated under reflux for 1 hour. At this time, water that azeotropically distilled out was removed using a water draining tube. 0.5N after cooling
50 ml of an aqueous sodium hydroxide solution and 50 ml of heptane were added, and the aqueous layer was removed. The extract was washed 3 times with 50 ml of saturated saline, dried over anhydrous magnesium sulfate, and concentrated. This was passed through a column filled with silica gel with a heptane solvent and heptane was distilled off to obtain 5.6 g of white crystals. The crystals were recrystallized from a mixed solvent of alcohol and heptane and dried to obtain 3.5 g of the title compound. The structure was confirmed by NMR.

mp.58 ℃ clp.121 ℃ (iii) 4- (trans-4-n-pentylcyclohexyl)
Synthesis of 1- (2- (4-cyanophenyl) ethyl) cyclohexene 3.5 g of the compound obtained in (ii) in a 100 ml three-necked flask,
Copper (I) cyanide (0.9 g) and DMF (30 ml) were added, and the mixture was heated under reflux for 24 hours. After allowing to cool, 20 ml of ammonia water and toluene
50 ml was added, the aqueous layer was removed, and the organic layer was filtered to remove insoluble materials. The filtrate was washed successively with 50 ml of 2N hydrochloric acid and 50 ml of a saturated aqueous solution of sodium hydrogen carbonate, and then washed with water until it became neutral. The extract was dried over anhydrous magnesium sulfate, the solvent was evaporated, and the residue was passed through a silica gel column with a 1: 1 mixed solvent of heptane and toluene. After concentration, recrystallization with heptane solvent and drying gave 1.5 g of the title compound. Structure is NM
Confirmed at R.

mp.70 ° C. clp.148 ° C. (Example 20) A method according to Example 19 in which 4- (trans-4-n-pentylcyclohexyl) cyclohexanone used in Example 19- (i) was replaced with a suitable cyclohexanone derivative. Then, the following compound was obtained.

(Y = H in the formula [Iba]) No. 345 4- (trans-4-ethylcyclohexyl)-
1- {2- (4-Cyanophenylethyl) cyclohexene No.346 4- (trans-4-n-propylcyclohexyl) -1- {2- (4-cyanophenyl) ethyl} cyclohexene No.347 4- (trans -4-n-butylcyclohexyl)
-1- {2- (4-Cyanophenyl) ethyl} cyclohexene No.348 4- (trans-4-n-hexylcyclohexyl) -1- {2- (4-cyanophenyl) ethyl} cyclohexene No.349 4- (Trans-4-n-heptylcyclohexyl) -1- {2- (4-cyanophenyl) ethyl} cyclohexene No.350 4- (trans-4-n-octylcyclohexyl) -1- {2- (4-cyano (Phenyl) ethyl} cyclohexene No.351 4- (trans-4-n-nonylcyclohexyl)
-1- {2- (4-cyanophenyl) ethyl} cyclohexene No.352 4- (trans-4-n-decylcyclohexyl)
-1- {2- (4-cyanophenyl) ethyl} cyclohexene No.353 4- {2- (trans-4-ethylcyclohexyl) ethyl} -1- {2- (4-cyanophenyl) ethyl} cyclohexene No. 354 4- {2- (trans-4-n-propylcyclohexyl) ethyl} -1- {2- (4-cyanophenyl) ethyl}
Cyclohexene [Ibb] The following compound with Y = H was obtained.

No.355 4- {2- (trans-4-n-butylcyclohexyl) ethyl} -1- {2- (4-cyanophenyl) ethyl} cyclohexene No.356 4- {2- (trans-4-n- Pentylcyclohexyl) ethyl} -1- {2- (4-cyanophenyl) ethyl}
Cyclohexene No.357 4- {2- (trans-4-n-hexylcyclohexyl) ethyl} -1- {2- (4-cyanophenyl) ethyl}
Cyclohexene No.358 4- {2- (trans-4-n-heptylcyclohexyl) ethyl} -1- {2- (4-cyanophenyl) ethyl}
Cyclohexene No.359 4- {2- (trans-4-n-octylcyclohexyl) ethyl} -1- {2- (4-cyanophenyl) ethyl}
Cyclohexene No.360 4- {2- (trans-4-n-nonylcyclohexyl) ethyl} -1- {2- (4-cyanophenyl) ethyl} cyclohexene No.361 4- {2- (trans-4-n -Decylcyclohexyl) ethyl} -1- {2- (4-cyanophenyl) ethyl} cyclohexene (Example 21) 4-n-pentyl-1- {2- (4-cyanophenyl) ethyl} cyclohexene (No.362 ) 4-n-was used in example 19 4- (trans--4-n-pentyl) cyclohexanone [No.362 ([I bc] _{Y = H, R = C 5} H 11) by the formula] It was obtained in the same manner as in Example 19 except that pentylcyclohexanone was used.

mp.25 (clp.13) (Example 22) 4- (trans-4-n-pentylcyclohexyl) cyclohexanone used in Example 19 was replaced with a suitable cyclohexanone derivative, and the following compound was prepared according to the method of Example 19. Got

(Y = H in the formula [Ibc]) No.363 4-Ethyl-1- {2- (4-cyanophenyl) ethyl} cyclohexene No.364 4-n-Propyl-1- {2- (4-cyano Phenyl)
Ethyl} cyclohexene No.365 4-n-butyl-1- {2- (4-cyanophenyl) ethyl} cyclohexene No.366 4-n-hexyl-1- {2- (4-cyanophenyl)
Ethyl} cyclohexene No.367 4-n-heptyl-1- {2- (4-cyanophenyl)
Ethyl} cyclohexene No.368 4-n-octyl-1- {2- (4-cyanophenyl)
Ethyl} cyclohexene No.369 4-n-nonyl-1- {2- (4-cyanophenyl) ethyl} cyclohexene No.370 4-n-decyl-1- {2- (4-cyanophenyl) ethyl} cyclohexene ( Example 23) 4- (trans-4-n-pentylcyclohexyl) -1- {2-
(3-fluoro-4-cyanophenyl) ethyl} cyclohexene [Nanba371 ([I ba] expression at _{Y = F, R = C 5} H 11) ] (i) 4-(trans -4-n-pentyl cyclohexyl ) Synthesis of cyclohexylidene-2- (3-fluoro-4-bromophenyl) ethane 2- (3-fluoro-4-bromophenyl) ethyltriphenylphosphonium bromide 27.2 g and 100 ml THF 5
To a 00 ml three-necked flask, 5.6 g of potassium tert-butoxide was added at -50 ° C. Stir at -50 ℃ for 1 hour, 4-
A solution of 10.0 g of (trans-4-n-pentylcyclohexyl) cyclohexanone in 50 ml of THF was added dropwise. Then, the temperature was gradually raised to room temperature and the mixture was stirred for 10 hours. Water on this
300 ml was added and stirred, and extracted with 200 ml of toluene. The organic layer was washed twice with 300 ml of water, dried over anhydrous magnesium sulfate and concentrated. To this, 300 ml of heptane was added and the precipitated crystals were filtered off and the filtrate was passed through a column filled with silica gel and concentrated. The crystals were recrystallized from a mixed solvent of alcohol and ethyl acetate and dried to obtain 10.5 g of the title compound.

(Ii) 4- (trans-4-n-pentylcyclohexyl)-
Synthesis of 1- {2- (3-fluoro-4-bromophenyl) ethyl} cyclohexene In a three-necked flask containing 6.6 g of metachloroperbenzoic acid, 5.3 g of potassium carbonate and 70 ml of chloroform, at 10 ° C. at (i) A solution of 8.3 g of the obtained compound in 30 ml of chloroform was added dropwise. After stirring for 3 hours, remove insoluble matter by filtration,
To this was added 50 ml of aqueous sodium thiosulfate solution. After removing the aqueous layer, the mixture was washed with 50 ml of a 1N sodium hydroxide aqueous solution and washed with water until the washing liquid became neutral. It was dried over anhydrous magnesium sulfate and concentrated to obtain 9.2 g of an oily substance.

A 30 ml THF solution of this was placed in a 200 ml three-necked flask containing 29 ml of a 1 molar solution of lithium triethylborohydride.
It was added dropwise at 0 ° C. After stirring for 1 day, 100 ml water and 10 toluene
0 ml was added and the aqueous layer was removed. The organic layer was washed twice with 100 ml of water, dried over anhydrous magnesium sulfate and then concentrated.

To this, 0.1 g of paratoluenesulfonic acid monohydrate and 50 ml of toluene were added, and the mixture was heated under reflux for 1 hour. At this time, water that azeotropically distilled out was removed using a water draining tube. 0.5N after cooling
50 ml of an aqueous sodium hydroxide solution and 50 ml of heptane were added, and the aqueous layer was removed. The extract was washed 3 times with 50 ml of saturated saline, dried over anhydrous magnesium sulfate, and concentrated. This was passed through a column filled with silica gel with a heptane solvent and the heptane was distilled off to obtain 5.8 g of white crystals. The crystals were recrystallized from a mixed solvent of alcohol and heptane and dried to obtain 3.6 g of the title compound. The structure was confirmed by NMR.

(Iii) 4- (trans-4-n-pentylcyclohexyl)
Synthesis of -1- (2- (3-fluoro-4-cyanophenyl) ethyl) cyclohexene 3.6 g of the compound obtained in (ii) in a 100 ml three-necked flask,
Copper (I) cyanide (0.9 g) and DMF (30 ml) were added, and the mixture was heated under reflux for 24 hours. After allowing to cool, 20 ml of ammonia water and toluene
50 ml was added, the aqueous layer was removed, and the organic layer was filtered to remove insoluble materials. The filtrate was washed successively with 50 ml of 2N hydrochloric acid and 50 ml of a saturated aqueous solution of sodium hydrogen carbonate, and then washed with water until it became neutral. The extract was dried over anhydrous magnesium sulfate, the solvent was evaporated, and the residue was passed through a silica gel column with a 1: 1 mixed solvent of heptane and toluene. After concentration, it was recrystallized from a heptane solvent and dried to obtain 1.6 g of the title compound. Structure is NM
Confirmed at R.

(Example 24) The 2- (4-bromophenyl) ethyltriphenylphosphonium bromide used in Example 19 was converted into 2- (3-fluoro-4-
By replacing bromophenyl) ethyltriphenylphosphonium bromide with 4- (trans-4-n-pentylcyclohexyl) cyclohexanone by a suitable cyclohexanone derivative, the following compound was obtained by the method according to Example 19. (Y = F in the formula [I ba]) No.372 4- (trans-4-ethylcyclohexyl)-
1- {2- (3-Fluoro-4-cyanophenylethyl) cyclohexene No.373 4- (trans-4-n-propylcyclohexyl) -1- {2- (3-fluoro-4-cyanophenyl) ethyl} Cyclohexene No.374 4- (trans-4-n-butylcyclohexyl)
-1- {2- (3-Fluoro-4-cyanophenyl) ethyl} cyclohexene No.375 4- (trans-4-n-hexylcyclohexyl) -1- {2- (3-fluoro-4-cyanophenyl) Ethyl} cyclohexene No.376 4- (trans-4-n-heptylcyclohexyl) -1- {2- (3-fluoro-4-cyanophenyl) ethyl} cyclohexene No.377 4- (trans-4-n-octyl Cyclohexyl) -1- {2- (3-fluoro-4-cyanophenyl) ethyl} cyclohexene No.378 4- (trans-4-n-nonylcyclohexyl)
-1- {2- (3-Fluoro-4-cyanophenyl) ethyl} cyclohexene No.379 4- (trans-4-n-decylcyclohexyl)
-1- {2- (3-Fluoro-4-cyanophenyl) ethyl} cyclohexene [Ibb] The following compound having Y = F was obtained.

No.380 4- {2- (trans-4-ethylcyclohexyl) ethyl} -1- {2- (3-fluoro-4-cyanophenylethyl} cyclohexene No.381 4- {2- (trans-4-n -Propylcyclohexyl) ethyl} -1- {2- (3-fluoro-4-cyanophenyl) ethyl} cyclohexene No.382 4- {2- (trans-4-n-butylcyclohexyl) ethyl} -1- {2 -(3-Fluoro-4-cyanophenyl) ethyl} cyclohexene No.383 4- {2- (trans-4-n-pentylcyclohexyl) ethyl} -1- {2- (3-fluoro-4-cyanophenyl) Ethyl} cyclohexene No.384 4- {2- (trans-4-n-hexylcyclohexyl) ethyl} -1- {2- (3-fluoro-4-cyanophenyl) ethyl} cyclohexene No.385 4- {2- (Trans-4-n-heptylcyclohexyl) ethyl} -1- {2- (3-fluoro-4-cyanophenyl) Tyl} cyclohexene No.386 4- {2- (trans-4-n-octylcyclohexyl) ethyl} -1- {2- (3-fluoro-4-cyanophenyl) ethyl} cyclohexene No.387 4- {2- (Trans-4-n-nonylcyclohexyl) ethyl} -1- {2- (3-fluoro-4-cyanophenyl) ethyl} cyclohexene No.388 4- {2- (trans-4-n-decylcyclohexyl) ethyl } -1- {2- (3-Fluoro-4-cyanophenyl) ethyl} cyclohexene (Example 25) The 2- (4-bromophenyl) ethyltriphenylphosphonium bromide used in Example 19 was converted into 2- (3- Fluoro-4-
By replacing bromophenyl) ethyltriphenylphosphonium bromide with 4- (trans-4-n-pentylcyclohexyl) cyclohexanone by a suitable cyclohexanone derivative, the following compound was obtained by the method according to Example 19. (Y = F in the formula [Ibc]) No.389 4-Ethyl-1- {2- (3-fluoro-4-cyanophenyl) ethyl} cyclohexene No.390 4-n-Propyl-1- {2- (3-Fluoro-4-cyanophenyl) ethyl} cyclohexene No.391 4-n-butyl-1- {2- (3-fluoro-4-cyanophenyl) ethyl} cyclohexene No.392 4-n-pentyl-1 -{2- (3-Fluoro-4-cyanophenyl) ethyl} cyclohexene No.393 4-n-hexyl-1- {2- (3-fluoro-4-cyanophenyl) ethyl} cyclohexene No.394 4-n -Heptyl-1- {2- (3-fluoro-4-cyanophenyl) ethyl} cyclohexene No.395 4-n-octyl-1- {2- (3-fluoro-4-cyanophenyl) ethyl} cyclohexene No. 396 4-n-nonyl-1- {2- (3-fluoro-4-cyanophenyl) ethyl} cyclohexene No.397 4-n-decyl-1- {2- (3-fluoro-4-cyanophenyl Ethyl} cyclohexene (Example 26) (Example of use) Of the liquid crystal composition A consisting of 52.3 ° C., Δε of 10.7, Δ
n was 0.119 and the viscosity at 20 ° C. was 22 cp. In 85 parts by weight of this liquid crystal composition A, the compound shown in Example 1 (No.
Of the novel liquid crystal composition obtained by adding 15 parts by weight of 1) clp.
Increased to 62.6 ° C and the viscosity at 20 ° C dropped to 21 cp.
Further, this liquid crystal composition maintained a nematic phase without depositing crystals and the like even when left standing at -20 ° C for 40 days.

(Examples 27 to 32) Liquid crystal composition A (85 parts by weight) contains the compound of the present invention [I].
A novel liquid crystal composition was obtained by adding 15 parts by weight of each of the compounds of the formula. The clp. Of the obtained composition is shown in Table 1.

[Effects of the Invention] The compound of the present invention exhibits a wide liquid crystal phase and has good compatibility with existing liquid crystal compounds, so that the liquid crystal phase temperature range of the liquid crystal composition can be widened, and the operation of the liquid crystal display device can be improved. The temperature range can be extended.

Further, since it is very stable against environmental factors, it can be used for various liquid crystal display devices.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location C09K 19/30 9279-4H 19/42 9279-4H // G02F 1/13 500

Claims (11)

[Claims] 1. A general formula (In the formula [I], R represents an alkyl group having 1 to 10 carbon atoms,
X represents an alkyl group or an alkoxy group having 1 to 10 carbon atoms, a cyano group, a bromine atom or a fluorine atom, and Y
Represents a hydrogen atom or a fluorine atom, m is 0 or 1, and n is 0 or 1. ) The cyclohexenyl ethane compound shown by these. 2. General formula The cyclohexenylethane compound according to claim 1, which is represented by (wherein X ₁₁ is an alkyl group or an alkoxy group having 1 to 10 carbon atoms, and the other is the same as the formula (I)). 3. General formula The cyclohexenylethane compound according to claim 1, wherein X ₁₁ is an alkyl group or alkoxy group having 1 to 10 carbon atoms, and R and Y are the same as those in the formula [I]. 4. A general formula The cyclohexenylethane compound according to claim 1, wherein R and Y are the same as those in the formula [I]. 5. A general formula The cyclohexenylethane compound according to claim 1, wherein R and Y are the same as those in the formula [I]. 6. A general formula The cyclohexenylethane compound according to claim 1, wherein R and Y are the same as those in the formula [I]. 7. General formula The cyclohexenylethane compound according to claim 1, wherein R and Y are the same as those in the formula [I]. 8. General formula The cyclohexenylethane compound according to claim 1, wherein X ₁₁ is an alkyl group or alkoxy group having 1 to 10 carbon atoms, and R is the same as in the formula [I]. 9. General formula The cyclohexenylethane compound according to claim 1, wherein R and Y are the same as those in the formula [I]. 10. General formula The cyclohexenylethane compound according to claim 1, wherein R and Y are the same as those in the formula [I]. 11. A liquid crystal composition comprising at least two components, at least one of which is the cyclohexenylethane compound according to claim 1.