JPH107598A - Alkenylcyclohexane derivative, liquid crystal composition and liquid crystal display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new liquid crystal compound composed of a specific compound having low viscosity and high elastic constant ratio and exhibiting excellent compatibility with other liquid crystal compound at a low temperature and useful for a liquid crystal display element. SOLUTION: This alkenylcyclohexane derivative is expressed by the formula I (R<1> and R<2> are each a straight or branched-chain 1-15C alkyl, etc.; rings A<1> to A<3> are each 1,4-cyclohexylene, etc., wherein one or more CH2 groups on the ring may be substituted with O, etc., Z<1> and Z<2> are each CH2 CH2 , etc.; Z<3> is (CH2 )4 , etc.; (m), (n) and (i) are each 0 or 1), e.g. a compound of the formula II (R<11> is H, etc.; (l) is an integer 0-6). The compound of the formula II can be produced e.g. by reacting a Wittig reagent of the formula III with a sodium alkoxide in tetrahydrofuran, reacting the resultant ylide compound with an aldehyde derivative of the formula IV, isomerizing the obtained E,Z-olefin mixture by reacting with benzenesulfinic acid and separating and purifying the E isomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention mainly relates to a novel liquid crystal compound which exhibits suitable physical properties in a liquid crystal composition for TN and STN, and a liquid crystal composition having suitable physical properties using the above-mentioned novel liquid crystal compound. About things.

[0002]

2. Description of the Related Art A liquid crystal display device utilizes optical anisotropy and dielectric anisotropy of a liquid crystal material, and is widely used in watches, calculators, word processors, televisions, and the like, and the demand thereof is increasing year by year. It is in. The liquid crystal phase is located between the solid phase and the liquid phase, and is roughly classified into a nematic phase, a smectic phase and a cholesteric phase. Among them, a display element utilizing a nematic phase is currently most widely used. On the other hand, a large number of display methods have been devised so far, but at present, three types, a twisted nematic (TN) type, a super twisted nematic (STN) type, and a thin film transistor (TFT) type, are mainly used. Among them, the super twisted nematic (STN) type is a system which is totally excellent as a simple matrix driven liquid crystal display element in many characteristics such as display capacity, response speed, viewing angle, gradation and the like. TF is also used for color displays.
The STN type has been widely spread on the market because of its economic characteristics that it can be produced at a lower cost than the T type. The properties of the liquid crystal compound required for these various types of liquid crystal display elements differ depending on the application, but all liquid crystal substances are stable against external environmental factors such as moisture, air, heat, and light. In addition, it is commonly required that the liquid crystal phase exhibit a liquid crystal phase in a temperature range as wide as possible around room temperature, have low viscosity, and have a low driving voltage. However, no single liquid crystal material satisfying these conditions has been found. The liquid crystal material used for the liquid crystal display element has a dielectric anisotropy value (△ ε), a refractive index anisotropy value (△ n), a viscosity and an elastic constant ratio K33 / K11 (K3
3: several to several tens of liquid crystal compounds and, if necessary, more in order to adjust various physical property values such as the value of 3: bend elastic constant, K11: splay elastic constant) to the optimum value required for each display element. It is used for a display device as a liquid crystal composition in which several kinds of non-liquid crystal compounds are mixed. For this reason, good compatibility with other liquid crystal compounds, particularly, low temperature compatibility is required in recent years in view of requirements for use in various environments.

In recent years, colorization of displays and diversification of use environments have been advanced, and liquid crystal compounds have low viscosity, a large elastic constant ratio K33 / K11, a wide temperature range of nematic phase, and a phase for other liquid crystal compounds. Solubility has become particularly required. The use of a low-viscosity liquid crystal compound enables a high-speed response of the liquid crystal display device and a large elastic constant ratio K3.
3 / K11 steeply changes the transmittance near the threshold voltage, and enables a liquid crystal display device with high contrast.
Further, the wide temperature range showing the nematic phase and the good compatibility allow the liquid crystal display element to be used in an environment where temperature changes are remarkable. The development of compounds emphasizing these characteristics has been actively carried out, and the following compounds (a) to (d) have been synthesized.

[0004]

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(Wherein R and R ′ each represent an alkyl group.) Compounds (a) (JP-A-61-83136) and (b) (JP-A-1-308239) have alkenyl or It has a 1,1-difluorovinyl group and has a relatively large elastic constant ratio. However, its bicyclohexane skeleton has strong smecticity, and its compatibility with other liquid crystal compounds, particularly low-temperature compatibility, is not sufficient. Further, the viscosity of the compound (b) is higher than that of the compound (a) due to the terminal fluorine atom, so that the compound (b) cannot be used for a liquid crystal composition aimed at high-speed response. On the other hand, a compound (c) having a structure in which a cyclohexane ring and a benzene ring are cross-linked with butane-1,4-diyl (JP-A-3-66632) or a structure in which a cyclohexane ring and a benzene ring are cross-linked with a butene-1,4-diyl group ( d) (JP-A-4-330019) has a relatively large elastic constant ratio, but according to the data described in the specification, the smectic property is remarkably strong, and the liquid crystal composition using the same has a smectic phase at low temperature. Is easy to express.
As described above, a liquid crystal compound satisfying the above-mentioned demand has not been found at present, and a compound having improved properties is expected.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel liquid crystal compound having a low viscosity, a large elastic constant ratio, and excellent compatibility with other known liquid crystal compounds, especially excellent low-temperature compatibility. And a liquid crystal display device using the same.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the compound (c) or (d) described in the section of the prior art has butane inserted as a bonding group. 1,4-diyl or butene-1,4-
Considering that the effect of inserting a diyl group was not sufficiently exhibited,
A compound having a skeleton structure in which two cyclohexane rings are crosslinked with a butane-1,4-diyl or butene-1,4-diyl group, and further having an alkenyl group as a substituent on the cyclohexane ring, and examining its physical properties. As a result, in addition to showing a nematic phase in a relatively wide temperature range, the viscosity is much lower than initially expected, and has a large elastic constant ratio, and further compatibility with other liquid crystal compounds,
In particular, it has been found that the compound has excellent low-temperature compatibility,
The present invention has been reached. The present invention has the following configuration. (1) General formula (1)

[0008]

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(Wherein R ¹ and R ² are linear or branched alkyl groups having 1 to 15 carbon atoms or 2 to 15 carbon atoms)
Wherein at least one of R ¹ and R ² is an alkenyl group, and in these groups, one or two or more non-adjacent methylene groups (—CH 2 —) are an oxygen atom, a sulfur atom or —C≡. The ring A ¹ , the ring A ² and the ring A ³ may be each independently substituted with one or more CH 2 groups on the ring with an oxygen atom or a sulfur atom. A 1,4-cyclohexylene group or a 1,4-phenylene group in which one or more CH groups on the ring may be substituted with a nitrogen atom, wherein Z ¹ and Z ² are each independently —CH ² CH 2 -, -CH2O-, -OCH2-,
—CH ＝ CH—, —C≡C— or a single bond, and Z ³
Is-(CH2) 4-, -CH = CH- (CH2) 2-, -C
H2-CH = CH-CH2- or-(CH2) 2-CH =
An alkenylcyclohexane derivative represented by CH-, wherein m, n and i are each independently 0 or 1.

(2) In the general formula (1), m = n =
The compound according to the above (1), wherein i = 0. (3) The compound according to the above (2), wherein in the general formula (1), R ¹ is an alkyl group, R ² is an alkenyl group, and Z ³ is — (CH 2) 4 —. (4) In the general formula (1), R ¹ is an alkyl group, R ²
Is an alkenyl group, and Z ³ is —CH ＝ CH— (CH 2)
The compound according to the above item (2), wherein 2- or-(CH2) 2-CH = CH-. (5) The compound according to the above (1), wherein m = 1 and n = i = 0 in the general formula (1). (6) The compound according to the above (5), wherein in the general formula (1), R ¹ is an alkyl group, R ² is an alkenyl group, and Z ³ is — (CH 2) 4 —. (7) In the general formula (1), R ¹ is an alkyl group, R ²
Is represented by an alkenyl group, and Z ³ is -CH = CH- (CH
2) The compound according to the above item (5), wherein 2- or-(CH2) 2-CH = CH-. (8) The compound according to the above item (1), wherein m = n = 1 and i = 0 in the general formula (1). (9) The compound according to the above item (8), wherein in the general formula (1), R ¹ is an alkyl group, R ² is an alkenyl group, and Z ³ is — (CH 2) 4 —. (10) In the general formula (1), R ¹ is an alkyl group, R ²
Is an alkenyl group, and Z ³ is —CH ＝ CH— (CH 2)
The compound according to the above item (8), wherein 2- or-(CH2) 2-CH = CH-

(11) A liquid crystal composition comprising at least two components, comprising at least one compound represented by the general formula (1). (12) As a first component, at least one kind of the alkenylcyclohexane derivative according to any of the above (1) to (10) is contained, and as a second component, a general formula (2):
(3) and (4)

[0012]

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(Wherein, R ³ represents an alkyl group having 1 to 10 carbon atoms; X ¹ represents F, Cl, OCF 3, OCF 2 H, CF
3 shows a CF2H or ^{CFH2, L 1, L 2,} L 3, and L ⁴ represent H or F independently of one another, Z4 and Z5 are independently from each other - (CH2) 2 -, - CH = CH-
Or a single bond, and a represents 1 or 2. A liquid crystal composition comprising at least one compound selected from the group consisting of: (13) As the first component, at least one kind of the alkenylcyclohexane derivative according to any of the above (1) to (10) is contained, and as the second component, the general formulas (5), (6), and (7) ), (8) and (9)

[0014]

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(Where R^FourIs F, an alkyl having 1 to 10 carbon atoms
A kill group or an alkenyl group having 2 to 10 carbon atoms;
One or more non-adjacent methyl groups in these groups
Group (-CH_Two-) Is replaced by oxygen atom (-O-)
Ring A may be trans-1,4-cyclo
Xylene group, 1,4-phenylene group, pyrimidine-2,
5-diyl group or 1,3-dioxane-2,5-dii
And ring B is trans-1,4-cyclohexyl
Group, 1,4-phenylene group or pyrimidine-2,5
-Diyl group, and ring C is trans-1,4-cyclo
A xylene group or a 1,4-phenylene group;⁶Is
-(CH2) 2-, -COO- or a single bond;^Five
And L⁶Represents H or F independently of each other, b and
And c independently represent 0 or 1;^FiveIs the carbon number
1 to 10 alkyl groups;⁷Indicates H or F
And d represents 0 or 1, and R⁶Is a group having 1 to 10 carbon atoms.
A ring group, and ring D and ring E are independently of each other
1,4-cyclohexylene group or 1,4-phenyl
Represents a nylene group; ⁷And Z⁸Are independently -CO
O- or a single bond, Z⁹Is COO- or -C≡
C-, L⁸And L⁹Are independently H or F
And X^TwoIs F, OCF3, OCF2H, CF3, CF2
H or CFH2, but X^TwoAre OCF3, OCF2H,
L for CF3, CF2H or CFH2⁸And L
⁹Each represents H, and e, f and g independently represent 0
Or 1 and R⁷And R⁸Are carbon numbers independently of each other
An alkyl group having 1 to 10 or an alkenyl having 2 to 10 carbon atoms
And represents one or more non-adjacent groups in these groups
Two or more methylene groups (-CH2-) have an oxygen atom (-O
-) May be substituted and the ring G is trans-
1,4-cyclohexylene group, 1,4-phenylene group
Or a pyrimidine-2,5-diyl group;
1,4-cyclohexylene group or 1,4-phenyl
Represents a nylene group;^TenIs -C≡C-, -COO-,-
(CH2) 2-, -CH = CH-C≡C- or a single bond
And Z¹¹Represents -COO- or a single bond;⁹And
And R^TenAre each independently an alkyl group having 1 to 10 carbon atoms.
Or an alkenyl group having 2 to 10 carbon atoms.
One or two or more non-adjacent arbitrary
Group (-CH_Two-) Is replaced by oxygen atom (-O-)
Ring I may be trans-1,4-cyclo
Xylene group, 1,4-phenylene group or pyrimidine-
A 2,5-diyl group; ring J is trans-1,4-
A cyclohexylene group, where one or more hydrogen atoms on the ring are replaced by F
An optionally substituted 1,4-phenylene group or pyrimi
A gin-2,5-diyl group, and ring K is trans-1,
A 4-cyclohexylene group or a 1,4-phenylene group
And Z¹²And Z¹⁴Are independently of each other -COO-,-
(CH2) 2- or a single bond;¹³Is -CH = CH
—, —C≡C—, —COO— or a single bond, and h is
Indicates 0 or 1. A compound selected from the group consisting of
Liquid crystal composition characterized by containing at least one kind of
Stuff.

(14) As the first component, the above (1) to
It contains at least one alkenylcyclohexane derivative according to any one of the above items (10), and as a part of the second component, at least a compound selected from the group consisting of the general formulas (2), (3) and (4). One kind is contained, and as other parts of the second component, general formulas (5), (6),
(7) A liquid crystal composition comprising at least one compound selected from the group consisting of (8) and (9). (15) A liquid crystal display device comprising the liquid crystal composition according to any one of the above (11) to (14).

In the first aspect of the present invention, preferred embodiments of the alkenylcyclohexane derivative represented by the general formula (1) are compounds represented by the following general formula groups (1-a) to (1-o). .

[0018]

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(Wherein the rings A ¹ , A ² , A ³ , R ¹ and Z ³ are the same as described above, and R ¹¹ is a hydrogen atom or a C 1 -C 1)
3 represents a linear or branched alkyl group;
Indicates an integer. In the compounds represented by the general formula groups (1-a) to (1-o), the alkenyl group corresponding to R ² in the general formula (1) includes 1E-alkenyl, 2Z-alkenyl, and 3E -Alkenyl and 4-alkenyl groups are preferred, and more specifically 1-ethenyl, 1E-propenyl, 1E-butenyl, 1E-pentenyl, 1E-hexenyl, 2Z-propenyl, 2-propenyl, 2Z-butenyl and 2Z-pentenyl A 2,2Z-hexenyl, 3-butenyl, 3E-pentenyl and 3E-hexenyl group are preferred.

The compounds represented by the above general formula groups (1-a) to (1-o) all have very low viscosity and show a large elastic constant ratio (K33 / K11). Among them, the bicyclic and tricyclic compounds represented by the general formulas (1-a) to (1-e) have extremely low viscosity, and when these compounds are added as components of the liquid crystal composition, Can be remarkably reduced without lowering the clearing point. Further, the tetracyclic compounds represented by the general formulas (1-f) to (1-o) have a wide nematic phase temperature range, and when this compound is added as a component of a liquid crystal composition, the viscosity increases. Without raising the clearing point alone. Further, in the compounds represented by the above general formula groups (1-a) to (1-o), compounds in which R ¹ is an alkenyl group and Z ³ is a butene-1,4-diyl group are all very low. It has a large elastic constant ratio (K33 / K11), and is characterized by having a remarkably low viscosity and a high clearing point as compared with a saturated compound having the same skeleton. As described above, the compound of the present invention has excellent characteristics, and it is possible to provide a liquid crystal composition and a liquid crystal display device having improved characteristics by using the compound of the present invention. As specific examples of the alkenylcyclohexane derivatives represented by the general formula groups (1-a) to (1-o), the following compound No. Compounds represented by 1 to 516 can be listed.

[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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The liquid crystal composition provided by the present invention is a composition containing at least one liquid crystal compound represented by the general formula (1). As other components added to the liquid crystal compound represented by the general formula (1), the above-mentioned general formulas (2) and (3)
And at least one compound selected from the group consisting of (4) and (4), and / or general formulas (5), (6), (7), (8) and (9) It is preferable to use at least one compound selected from the group (hereinafter, referred to as a second component B), and further includes a threshold voltage, a liquid crystal phase temperature range, a refractive index anisotropy value,
For the purpose of adjusting the dielectric anisotropy value, the viscosity and the like, another known liquid crystal compound can be mixed as the third component. Preferred examples of the compounds represented by the general formulas (2), (3) and (4) among the above-mentioned second A components include formulas (2-1) to (2-15) and (3-1), respectively. ) To (3-4)
8) and the compounds represented by (4-1) to (4-55).

[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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The compounds represented by the general formulas (2) to (4) have a positive dielectric anisotropy value and are very excellent in thermal stability and chemical stability. These compounds are used in an amount of 1 to 99% by weight based on the total weight of the liquid crystal composition, preferably 10 to 97% by weight, more preferably 4 to 97% by weight.
0 to 95% by weight. Preferred examples of the compounds represented by the general formulas (5), (6) and (7) among the second component B include formulas (5-1) to (5-24) and (6-), respectively.
Examples include compounds represented by 1) to (6-3) and formulas (7-1) to (7-17).

[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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The compounds represented by the general formulas (5) to (7) have a large positive dielectric anisotropy value and are used as a component of the liquid crystal composition, particularly for the purpose of reducing the threshold voltage. Is done. It is also used for the purpose of adjusting the viscosity, adjusting the refractive index anisotropy value, expanding the liquid crystal phase temperature range, and further improving the steepness. Among the second B components, preferred examples of the compounds represented by the general formulas (8) and (9) include formulas (8-1) to (8-8) and formulas (9-1) to (9-1), respectively. 9-16).

[0062]

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[0063]

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The liquid crystal compositions used according to the invention are prepared in a manner which is conventional per se. Generally, a method of dissolving various components at a high temperature is used. Further, the liquid crystal composition of the present invention is improved and optimized by an appropriate additive depending on the intended use. Such additives are well known to those skilled in the art and are described in detail in the literature and the like. For example, a helical structure of a liquid crystal is induced to adjust a required twist angle, and a reverse twist (reverse twist) is obtained.
-Twist) is usually avoided by using a chiral doped material (c
GH mode, or a dichroic dye such as merocyanine, styryl, azo, azomethine, azoxy, quinophthalone, anthraquinone, and tetrazine. Used as a liquid crystal composition of
Etc. Further, NCAP formed by microencapsulating nematic liquid crystal or polymer network liquid crystal display device (PN) in which three-dimensional knitted polymer is formed in liquid crystal.
Polymer-dispersed liquid crystal display device (P
It can also be used as a liquid crystal composition for a DLCD) or a liquid crystal composition for a birefringence control (ECB) mode or a dynamic scattering (DS) mode. The following composition examples (composition examples 1 to 15) can be shown as nematic liquid crystal compositions containing the compound of the present invention.

[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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The method for producing the compound of the present invention will be described. A compound represented by the general formula (1-a) exemplified as a preferable compound: tetrahydrofuran (hereinafter referred to as TH) is added to a Wittig reagent (11) prepared from an alkyl halide according to the method described in ORGANIC REACTION VOL.
Y) is prepared by the action of a base such as sodium alkoxide or alkyllithium in F), and the aldehyde is reacted with the aldehyde derivative (10). Next, the resulting E, Z-olefin mixture (12) is
According to the method described in No. 30382, isomerization is carried out with benzenesulfinic acid or p-toluenesulfinic acid, and the E-isomer is separated and purified, whereby (1-a) can be produced. Alternatively, E, Z-olefin mixture (2) is prepared according to the method described in JP-B-6-62462.
An oxirane derivative (1) is reacted with m-chloroperbenzoic acid.
After 3), dibromotriphenylphosphorane is reacted to produce a dibromo compound (14). Dibromo compound (1
4) can refine | purify only an erythro body by recrystallization, and reduce it with metal zinc powder, and can manufacture (1-a).

[0081]

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(Wherein R ¹ represents a linear or branched alkyl group having 1 to 15 carbon atoms, R ¹¹ represents a hydrogen atom or a linear or branched alkyl group having 1 to 13 carbon atoms,
³ is-(CH2) 4-, -CH = CH- (CH2) 2-,-
CH2-CH = CH-CH2- or-(CH2) 2-CH
= CH-, and l represents an integer of 0 to 6. The aldehyde derivative (1) used as a raw material in the above operation
0) can be produced by the following operation. When Z ³ is-(CH 2) 4-: Ylide is prepared by reacting methoxymethyltriphenylphosphonium chloride with a base such as sodium alkoxide or alkyllithium in THF, and then preparing an ylide therefrom.
Compound (16) is produced by reacting the cyclohexanone derivative (15) described in (1). Compound (16)
An aldehyde derivative (10-1) having l = 0 can be produced by allowing a mineral acid such as hydrochloric acid or sulfuric acid or an organic acid such as formic acid, acetic acid or p-toluenesulfonic acid to act thereon.

Further, ylide is prepared by reacting ethyl diethylphosphinoacetate with a base such as sodium alkoxide or alkyllithium, and then reacted with cyclohexanone derivative (15) to produce compound (17). The compound (17) is hydrogen-reduced in the presence of a palladium carbon catalyst to give a compound (18), and then reduced with diisobutylaluminum hydride to produce an aldehyde derivative (10-2) having l = 1. Furthermore, [2-
(1,3-Dioxolan-2-yl) ethyl] triphenylphosphonium bromide is reacted with a base such as sodium alkoxide or alkyllithium to react a ylide prepared with a cyclohexanone derivative (15) to produce a compound (19). . Hydrogenating compound (19) in the presence of a palladium carbon catalyst to give compound (20)
After that, mineral acids such as hydrochloric acid and sulfuric acid or formic acid, acetic acid, p
-By the action of an organic acid such as toluenesulfonic acid,
= 2 aldehyde derivative (10-3) can be produced. l
= 3 to 6 are aldehyde derivatives (1
0-1) to (10-3) are used as synthesis raw materials, and the above-mentioned three types of carbon-enhancing reaction operations are repeated or operated in combination.

[0084]

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(Wherein R ¹ is the same as above) wherein Z ³ is — (CH 2) 2 —CH ＝ CH—: Wittig reagent synthesized according to the synthesis procedure described in JP-A-6-40968. The ylide prepared by reacting (23) with a base such as sodium alkoxide or alkyllithium was prepared from 1,4-cyclohexanedione monoethylene ketal (21) according to the synthesis procedure described in JP-B-4-30382. Formylcyclohexanone (22) is reacted to produce a butenylcyclohexanone derivative (24). The butenylcyclohexanone derivative (24) is isomerized according to the method described in JP-B-4-30382 or JP-B-6-62462 to purify only the E-butenyl derivative. Next, the aldehyde derivative (10-) was purified by subjecting (24) purified only to the E-butenyl derivative to the same carbon-enrichment operation as that for converting the cyclohexanone derivative (15) to the aldehyde derivative (10-1). 4) can be manufactured.

When Z ³ is —CH 2 —CH ＝ CH—CH 2 —: Ylide prepared by reacting ethyl diethylphosphinoacetate with a base such as sodium alkoxide or alkyllithium is treated with 1,4-cyclohexanedione monoethylene. Reaction of ketal (21) with compound (2)
5) is manufactured. The compound (25) is reduced with hydrogen in the presence of a palladium carbon catalyst, and subsequently reduced with diisopropylaluminum hydride to produce a compound (26). Compound (26) was added to Wittig reagent (2) synthesized according to the synthesis procedure described in JP-A-6-40968.
Compound (28) is produced by reacting ylide prepared by reacting 7) with a base such as sodium alkoxide or alkyllithium. A butenylcyclohexanone derivative (29) is produced by reacting compound (28) with a mineral acid such as hydrochloric acid or sulfuric acid or an organic acid such as formic acid, acetic acid or p-toluenesulfonic acid. Next, the butenyl cyclohexanone derivative (29) is subjected to the same carbon-enrichment operation as that for converting the cyclohexanone derivative (15) to the aldehyde derivative (10-1) to produce the aldehyde derivative (10-5). it can.

When Z ³ is —CH ＝ CH— (CH 2) 2 —: [2- (1,3-dioxolan-2-yl) ethyl] triphenylphosphonium bromide is treated with a base such as sodium alkoxide or alkyl lithium. 1,4-cyclohexanedione monoethylene ketal (21) is reacted with the prepared ylide to give compound (30)
To manufacture. Compound (30) is reduced with hydrogen in the presence of a palladium carbon catalyst, and subsequently treated with a mineral acid such as hydrochloric acid or sulfuric acid or an organic acid such as formic acid, acetic acid, p-toluenesulfonic acid, to thereby form cyclohexanone derivative (31). To manufacture. The cyclohexanone derivative (31) is disclosed in
No. 0968, the reaction was carried out with ylide prepared by reacting a base such as sodium alkoxide or alkyllithium with the Wittig reagent (32) synthesized according to the synthesis procedure described in No. 0968 to induce the compound (33).
No. 0382 or JP-B-6-62462, isomerization is carried out to obtain a Z-butenyl derivative. Then Z
The aldehyde derivative (10-6) is produced by subjecting the compound (33) consisting of only the -butenyl derivative to the same carbon-enrichment operation as in the conversion from the cyclohexanone derivative (15) to the aldehyde derivative (10-1). it can.

[0088]

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(In the formula, R ¹ and 1 are the same as described above.) In the compound represented by the general formula (1-a), R ¹ is an alkenyl group (1-a-a). Can be manufactured. After reducing 4-methoxycyclohexanecarboxylic acid (34) to an alcohol form with lithium aluminum hydride, a known method such as PJ Kocienski et al.
According to Org. Chem., 42, 353 (1977)), the compound is brominated with carbon tetrabromide-triphenylphosphine or hydrobromic acid to produce a bromide (35). Bromide (35) is OR
According to the method described in GANIC REACTION VOL.14, Chapter 3, it is reacted with triphenylphosphine to prepare a Wittig reagent (36), and then treated with a base such as sodium alkoxide or alkyllithium to prepare an ylide.
The compound (37) is produced by reacting the compound (31a) with the ylide. Further, compound (37)
To the aldehyde derivative (10-1) from the cyclohexanone derivative (15), followed by the same isomerization operation as in the production of the compound (1-a). Thus, compound (38) can be produced.
Next, the compound (38) is demethylated by reacting with boron tribromide in dichloromethane, and then treated with a suitable oxidizing agent such as sodium hypochlorite to induce the compound (39). Said cyclohexanone derivative (15)
Compound (40) is produced by the same carbon-increasing reaction as in the conversion to aldehyde derivative (10-1). Furthermore, compound (1-aa) can be produced by subjecting compound (40) to the same synthetic operation as in the production of compound (1-a). Z ³ is — (CH 2) 2 —CH ＝ CH—
Alternatively, those having —CH 2 —CH ＝ CH—CH 2 — can also be produced by appropriately selecting starting materials in the above reaction.

[0090]

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(Wherein R ¹¹ and R ¹² represent a hydrogen atom or a linear or branched alkyl group having 1 to 13 carbon atoms;
l and o each independently represent an integer of 0 to 6; In the compound represented by the formula (1-a), the compound of the formula (1-ab) wherein R ¹ is an alkynyl group can be produced by the following operation. The compound (41) produced by the same operation as in the case of the compound (40) according to the method described in JP-B-4-30382 is reacted with bromomethyltriphenylphosphine bromide and an ylide prepared from an appropriate base to give a compound (42). ), Potassium-t-butoxide is reacted to produce compound (43). Compound (43) can be treated with n-butyllithium and then reacted with alkyl bromide to produce compound (1-ab).

[0092]

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(Wherein R ¹¹ and R ¹² represent a hydrogen atom or a linear or branched alkyl group having 1 to 13 carbon atoms;
l and o each independently represent an integer of 0 to 6; The compound of the formula (1-ac) or the compound of the formula (1-ad) wherein R ¹ is an alkoxyalkyl group or an alkoxy group in the compound represented by the formula (1-a) is produced by the following operation. be able to. After reducing the compound (41) with lithium aluminum hydride to form an alcohol compound (44),
Acting on sodium hydride in dimethylformamide,
Then, the compound (1-ac) can be produced by reacting with an alkyl bromide. In addition, compound (1-ad) can also be produced using compound (41-a) as a synthesis raw material by the same operation as described above.

[0094]

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(Wherein R ¹¹ and R ¹² represent a hydrogen atom or a linear or branched alkyl group having 1 to 13 carbon atoms;
l and o each independently represent an integer of 0 to 6; The compound represented by the general formula (1-b) exemplified as a preferred compound can be produced by the following method. The compound (2) with respect to the cyclohexanone derivative (45)
Compound (46) is produced by performing the same operation as that for deriving compound (24), compound (29) and compound (33) from 1), and then the compound (46) is treated with the cyclohexanone derivative (15). The aldehyde derivative (47) can be produced by performing the same carbon enrichment reaction operation as in the conversion from the above) to the aldehyde derivative (10-1). Next, the aldehyde derivative (47) is subjected to a Wittig reaction with an alkyltriphenylphosphine halide in the same manner as in the production of the compound (1-a) to give the compound (1-b).
Can be manufactured.

[0096]

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(Wherein R ¹ , rings A ¹ and Z ³ are the same as described above, R ¹¹ represents a hydrogen atom or a linear or branched alkyl group having 1 to 13 carbon atoms, and l and o are A compound in which ring A ¹ is a 1,3-dioxane-2,5-diyl group: catalyzes a non-aqueous acidic ion exchange resin such as p-toluenesulfonic acid or Amberlyst By reacting the diol derivative (48) with the aldehyde derivative (22) or the diol derivative (50) with the aldehyde derivative (49), respectively.
-A) and compound (45-b) are produced.

[0098]

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(In the formula, R ¹ is the same as described above.) The compound represented by the general formula (1-c) as a preferred compound can be produced by the following method. Grignard reagent prepared from alkyl bromobenzene (51) according to a conventional method is reacted with acid chloride derivative (52) using iron (III) acetylacetonate as a catalyst to give compound (5).
3) is manufactured. Compound (53) is reduced with lithium aluminum hydride in THF using anhydrous aluminum chloride as a catalyst to give compound (54), and further demethylated with boron tribromide in dichloromethane. Compound (55) can be produced by treating with an oxidizing agent such as The compound (56) can be produced by reducing the compound (55) with hydrogen in the presence of a platinum-based or rhodium-based catalyst. Further, compound (1-c) can be produced by performing the same operation as producing compound (1-b) from cyclohexanone derivative (45) using compound (55) and compound (56) as raw materials.

[0100]

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(In the formula, R ¹ , R ¹¹ , ring A ¹ , Z ³ and 1 are the same as described above.) The compound represented by the general formula (1-d) as a preferred compound is prepared by the following method. Can be manufactured. An E, Z-olefin mixture (58) is produced by reacting an aldehyde derivative (22) with an ylide prepared by reacting a base such as sodium alkoxide or alkyllithium with a Wittig reagent represented by the formula (57). The mixture (58) was isomerized according to the method described in JP-B-4-30382 or JP-B-6-62462 to extract only the E-ethenyl derivative, and then the compound (1-b) was obtained from the cyclohexanone derivative (45). The compound (1-d) can be produced by performing the same operation as in the production of ()).

[0102]

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(In the formula, R ¹ , R ¹¹ , rings A ¹ , Z ³ and 1 are the same as described above.) The compound represented by the general formula (1-e) shown as a preferable compound is prepared by the following method. Can be manufactured. According to the method described in JP-B-4-30382, the compound (4
Compound (59) produced in the same manner as in 1) was reacted with bromomethyltriphenylphosphine bromide and an ylide prepared from an appropriate base to induce compound (60).
Compound (61) is produced by reacting potassium-t-butoxide. Compound (1-e) can be produced by treating compound (61) with n-butyllithium and then reacting compound (62).

[0104]

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(In the formula, R ¹ , R ¹¹ , rings A ¹ , Z ³ and 1 are the same as described above.) General formula groups (1-f) to (1)
For the compound represented by -n), an appropriate starting material is selected, and the reaction shown in the case of producing the compounds of the aforementioned general formula groups (1-a) to (1-e) or a known reaction thereto is performed. It can be manufactured by combining them. Further, other compounds included in the general formula (1) not listed above can also be produced by selecting appropriate starting materials and combining the above reactions or using a known reaction.

[0106]

The compound of the present invention has an extremely low viscosity,
And it has a large elastic constant ratio. Further, the compound of the present invention has compatibility with many other liquid crystal compounds, that is, existing liquid crystal compounds of ester type, Schiff base type, biphenyl type, phenylcyclohexane type, bicyclohexane type, heterocyclic type, and fluorine type. Very good, especially with good compatibility at low temperatures. Further, by adding the compound of the present invention as a component of the liquid crystal composition, it is possible to remarkably reduce only the viscosity while suppressing the decrease in the nematic liquid crystal phase temperature range.

[0107]

EXAMPLES Hereinafter, the production method and the use examples of the compound of the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. In each of the examples, Cr indicates a crystal, N indicates a nematic phase, S indicates a smectic phase, and Iso indicates an isotropic liquid, and the unit of the phase transition temperature is ° C. Example 1 1-ethenyl-4- (4- (trans-4-pentylcyclohexyl) butyl) cyclohexane (Compound No.
5) (In the general formula (1), m = n = i = 0, R ¹ = C 5 H ¹
1, Z ³ = — (CH ² ) 4 —, wherein R ² is an ethenyl group): In a 1-liter three-necked flask equipped with a stirrer, a thermometer and a nitrogen inlet tube, methoxy was added under a nitrogen atmosphere. 29.1 g of methyltriphenyl chloride (84.8
was dissolved in 200 ml of THF, and cooled to −30 ° C. or less with acetone-dry ice refrigerant. Then, 9.9 g (89.0 mmol) of potassium t-butoxide was added, and the mixture was stirred for 2 hours while maintaining the temperature at −30 ° C. or less. did. Then, a solution prepared by dissolving 20 g (65.2 mmol) of (4- (trans-4-pentylcyclohexyl) butyl) cyclohexanone described in JP-A-5-310605 in 50 ml of THF was added dropwise over 20 minutes while maintaining the same temperature. After that, the temperature was raised to room temperature over 1 hour, and the mixture was further stirred at room temperature for 4 hours. After the reaction was terminated by adding 200 ml of water to the reaction solution, extraction was performed twice with toluene (150 ml). The toluene layer was washed three times with water (100 ml),
After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure and concentrated. The concentrated residue was purified by silica gel chromatography using toluene as a developing solvent to obtain 19.8 g of yellow-brown crystals.

In a 500 ml eggplant-shaped flask equipped with a cooling tube, 19.8 g of the yellow-brown crystals obtained in the above operation were dissolved in 100 ml of toluene, and 16.5 g of 99% formic acid (36.5 g) was added.
(55.8 mmol) was added and the mixture was heated under reflux for 2 hours. After cooling the reaction solution to room temperature, 100 ml of water was added, and the organic layer was separated. Further, the aqueous layer was extracted with 100 ml of toluene and combined with the organic layer. The organic layer was washed with water (100 ml) 2
1 time with saturated aqueous sodium hydrogen carbonate solution (50 ml)
After further washing twice with water (100 ml) twice and drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure and concentrated to obtain 18.1 g of yellow-brown crystals. This is (4- (trans-4-pentylcyclohexyl) butyl) cyclohexylcarbaldehyde. 1H-NMR measurement results strongly supported the structure of this compound. δ ppm 2.86 (3H, s, OCH3), 5.7
3, (1H, bs)

In a 500 ml three-necked flask equipped with a stirrer, a thermometer and a nitrogen inlet tube, under a nitrogen atmosphere, 29.6 g of methyltriphenylphosphonium chloride (7
3.2 mmol) was dissolved in 200 ml of THF, and cooled to −30 ° C. or lower with an acetone-dry ice refrigerant.
8.6 g of potassium-t-butoxide (76.9 mmol
l) was added, and the mixture was stirred for 2 hours while maintaining the temperature at -30 ° C or lower. Then (4- (trans-4-pentylcyclohexyl) butyl) cyclohexylcarbaldehyde 18.1
g (56.3 mmol) in 50 ml of THF was added dropwise over 20 minutes while maintaining the same temperature.
The temperature was raised to room temperature over 1 hour, and the mixture was further stirred at room temperature for 4 hours. After the reaction was terminated by adding 200 ml of water to the reaction solution, extraction was performed twice with toluene (150 ml).
The toluene layer was washed three times with water (100 ml) and dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure.
Concentrated. The concentrated residue was purified by silica gel chromatography using heptane as a developing solvent to obtain colorless crystals (15.9).
g was obtained. The obtained crystal was purified by recrystallization from heptane, and 1-ethenyl-4- (4- (trans-4-pentylcyclohexyl) butyl) cyclohexane 7.2 was obtained.
g was obtained. - S53.3-54.1Iso - ¹ H-
NMR and GC-MS measurements strongly supported the structure of this compound. ¹ H-NMR: δ ppm 4.79-5.05 (2H,
m) 5.78 (1H, m) GC-MS: M ⁺ 318

Instead of (4- (trans-4-pentylcyclohexyl) butyl) cyclohexanone used in the above-mentioned production method, (4- (trans-4-alkylcyclohexyl) butyl) cyclohexanone having a different alkyl group chain length was used. By operating in accordance with the above-mentioned production method, compounds having the following numbers can be produced. 1-ethenyl-4- (4- (trans-4-methylcyclohexyl) butyl) cyclohexane (No. 1) 1-ethenyl-4- (4- (trans-4-ethylcyclohexyl) butyl) cyclohexane (No. 2)
Cr 34.2-35.0 Iso 1-ethenyl-4- (4- (trans-4-propylcyclohexyl) butyl) cyclohexane (No. 3)
S _B 44.5-45.1 Iso 1-ethenyl-4- (4- (trans-4-butylcyclohexyl) butyl) cyclohexane (No. 4) 1-ethenyl-4- (4- (trans-4-hexylcyclohexyl) butyl) Cyclohexane 1-ethenyl-4- (4- (trans-4-heptylcyclohexyl) butyl) cyclohexane (No. 6) 1-ethenyl-4- (4- (trans-4-octylcyclohexyl) butyl) cyclohexane 1-ethenyl- 4- (4- (trans-4-nonylcyclohexyl) butyl) cyclohexane 1-ethenyl-4- (4- (trans-4-decylcyclohexyl) butyl) cyclohexane

The following compounds can be produced according to the above production method. (E) -1-propenyl-4- (4- (trans-4-
Ethylcyclohexyl) butyl) cyclohexane (N
o.8) (E) -1-Propenyl-4- (4- (trans-4-
Propylcyclohexyl) butyl) cyclohexane (N
o.9) (E) -1-Propenyl-4- (4- (trans-4-
Butylcyclohexyl) butyl) cyclohexane (E) -1-propenyl-4- (4- (trans-4-
Pentylcyclohexyl) butyl) cyclohexane (N
o.10) (E) -1-butenyl-4- (4- (trans-4-ethylcyclohexyl) butyl) cyclohexane (No.
13) (E) -1-butenyl-4- (4- (trans-4-propylcyclohexyl) butyl) cyclohexane (N
o.14) (E) -1-butenyl-4- (4- (trans-4-butylcyclohexyl) butyl) cyclohexane (E) -1-butenyl-4- (4- (trans-4-pentylcyclohexyl) butyl ) Cyclohexane (N
o.15)

3-butenyl-4- (4- (trans-4
-Ethylcyclohexyl) butyl) cyclohexane (N
o.23) 3-Butenyl-4- (4- (trans-4-propylcyclohexyl) butyl) cyclohexane (No. 24) 3-butenyl-4- (4- (trans-4-butylcyclohexyl) butyl) cyclohexane 3 -Butenyl-4- (4- (trans-4-pentylcyclohexyl) butyl) cyclohexane (No. 25)

(E) -1-pentenyl-4- (4- (trans-4-ethylcyclohexyl) butyl) cyclohexane (No. 18) (E) -1-pentenyl-4- (4- (trans-4-
Propylcyclohexyl) butyl) cyclohexane (N
o.19) (E) -1-pentenyl-4- (4- (trans-4-
Butylcyclohexyl) butyl) cyclohexane (E) -1-pentenyl-4- (4- (trans-4-
Pentylcyclohexyl) butyl) cyclohexane (N
o.20) (E) -3-pentenyl-4- (4- (trans-4-
Ethylcyclohexyl) butyl) cyclohexane (N
o.28) (E) -3-pentenyl-4- (4- (trans-4-
Propylcyclohexyl) butyl) cyclohexane (N
o.29) (E) -3-pentenyl-4- (4- (trans-4-
Butylcyclohexyl) butyl) cyclohexane (E) -3-pentenyl-4- (4- (trans-4-
Pentylcyclohexyl) butyl) cyclohexane (N
o.30)

Example 2 1-ethenyl-4- (4- (trans-4-((E)-
3-pentenyl) cyclohexyl) butyl) cyclohexane (Compound No. 127) (m in general formula (1)
= N = i = 0, R ¹ is (E) -3-pentenyl group, Z ³ is — (CH ² ) 4 —, and R ² is ethenyl group): stirrer, thermometer and nitrogen inlet tube In a 1 liter three-necked flask equipped with a nitrogen atmosphere, 165.9 g (0.42 mol) of 1,3-dioxolan-2-yl) ethyl] triphenylphosphonium chloride was added in THF5.
100 ml, and acetone-dry ice refrigerant-
After cooling to 30 ° C or lower, 48.7 g (0.43 mol) of potassium-t-butoxide was added, and the mixture was stirred for 2 hours while maintaining at -30 ° C or lower. Subsequently, 50.0 g of 1,4-cyclohexanedione monoethylene ketal (0.3
A solution of 2 mol) dissolved in 150 ml of THF was added dropwise over 40 minutes while maintaining the same temperature, and then the temperature was raised to room temperature over 1 hour, followed by stirring at room temperature for 4 hours. After terminating the reaction by adding 300 ml of water to the reaction solution,
Extracted three times with toluene (300 ml). The toluene layer was washed three times with water (300 ml), dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure and concentrated. The concentrated residue was purified by silica gel chromatography using a mixed solvent of toluene / ethyl acetate = 2/1 as a developing solvent,
71.5 g of tan crystals were obtained.

In a 1-liter three-necked flask equipped with a stirrer, 71.5 g of the yellow-brown crystal obtained in the above operation was dissolved in 250 ml of a mixed solvent of toluene / ethanol = 1/1, and 5% -palladium carbon catalyst was added. 5.7 g was added, and catalytic hydrogen reduction was performed at room temperature under a hydrogen pressure of 5 to 10 kg / cm ² for 5 hours. The solvent was distilled off under reduced pressure from the reaction solution from which the catalyst was removed by filtration, and concentrated. The concentrated residue was dissolved in 300 ml of toluene in a 500 ml eggplant-shaped flask equipped with a condenser,
% Formic acid (82.8 g, 1.78 mol) was added, and the mixture was heated under reflux for 2 hours. After cooling the reaction solution to room temperature, water 30
0 ml was added, and the organic layer was separated. Further, the aqueous layer was extracted with 300 ml of toluene and combined with the organic layer. The organic layer was washed twice with water (300 ml), once with a saturated aqueous sodium hydrogen carbonate solution (100 ml), and twice with water (300 ml), and then dried over anhydrous magnesium sulfate. Concentration gave 41.2 g of tan crystals.
This is 4- (2-formylethane-1-yl) cyclohexanone. Under a nitrogen atmosphere, 175.6 g (0.34 mol) of (4-methoxycyclohexyl) methyltriphenylphosphine iodide was placed in a 1-liter three-necked flask equipped with a stirrer, a thermometer, and a nitrogen inlet tube.
After suspending in 500 ml of HF and cooling to −30 ° C. or lower with an acetone-dry ice refrigerant, 40.1 g ((0.36 mol) of potassium-t-butoxide was added, and
The mixture was stirred for 2 hours while maintaining the temperature at 0 ° C or lower. Next, 41.2 g (0.27 mol) of 4- (2-formylethane-1-yl) cyclohexanone obtained by the above operation was added to THF150.
The solution dissolved in ml was added dropwise over 40 minutes while maintaining the same temperature, then the temperature was raised to room temperature over 1 hour, and the mixture was further stirred at room temperature for 4 hours. After the reaction was terminated by adding 300 ml of water to the reaction solution, extraction was performed three times with toluene (300 ml). The toluene layer was washed three times with water (300 ml), dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure and concentrated. Concentrate residue is toluene / ethyl acetate =
Purification by silica gel chromatography using a 2/1 mixed solvent as a developing solvent gave 65.0 g of yellow-brown crystals. This is (4- (trans-4-methoxycyclohexyl)
— (E, Z) -3-butenyl) cyclohexanone.

In a 1-liter three-necked flask equipped with a stirrer, 65.0 g of (4- (trans-4-methoxycyclohexyl)-(E, Z) -3-butenyl) cyclohexanone obtained by the above operation was added with toluene. / Ethanol = 1 /
1 Dissolve in 250 ml of a mixed solvent, add 5.4 g of 5% -palladium carbon catalyst, and add hydrogen pressure of 5 to 10 kg / c at room temperature.
The catalytic hydrogen reduction was performed at m ² for 4 hours. The solvent was distilled off under reduced pressure from the reaction solution from which the catalyst was removed by filtration, and concentrated. The concentrated residue was purified by silica gel chromatography using a mixed solvent of toluene / ethyl acetate = 4/1 as a developing solvent, and further recrystallized from heptane to obtain 55.5 g of colorless crystals. This is (4- (trans-4-methoxycyclohexyl) butyl) cyclohexanone.

In a 1-liter three-necked flask equipped with a stirrer, thermometer and nitrogen inlet tube, under a nitrogen atmosphere,
3-Dioxolan-2-yl) ethyl] 117.7 g (0.30 mol) of triphenylphosphonium chloride was suspended in 500 ml of THF, cooled to −30 ° C. or lower with an acetone-dry ice refrigerant, and then potassium-t-butoxide 40 was dissolved. .1 g (0.36 mol) were added, and -3 was added.
The mixture was stirred for 2 hours while maintaining the temperature at 0 ° C or lower. Next, 55.5 g (0.21 m) of (4- (trans-4-methoxycyclohexyl) butyl) cyclohexanone obtained by the above operation was obtained.
ol) dissolved in 150 ml of THF was added dropwise over 40 minutes while maintaining the same temperature, and then the temperature was raised to room temperature over 1 hour, followed by stirring at room temperature for 4 hours. After the reaction was terminated by adding 300 ml of water to the reaction solution, extraction was performed three times with toluene (300 ml). The toluene layer was washed three times with water (300 ml), dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure and concentrated. The concentrated residue was dissolved in 250 ml of a toluene / ethanol = 1/1 mixed solvent in a 1-liter three-necked flask equipped with a stirrer,
4.5 g of 5% -palladium carbon catalyst was added, and catalytic hydrogen reduction was performed at room temperature under a hydrogen pressure of 5 to 10 kg / cm ² for 5 hours. The solvent was distilled off under reduced pressure from the reaction solution from which the catalyst was removed by filtration, and concentrated. The concentrated residue (66.9 g) was added to a 50
It was dissolved in 300 ml of toluene in a 0 ml eggplant-shaped flask, 53.0 g (1.14 mol) of 99% formic acid was added, and the mixture was heated under reflux for 2 hours. After cooling the reaction solution to room temperature, 300 ml of water was added, and the organic layer was separated. Further, the aqueous layer was extracted with 300 ml of toluene and combined with the organic layer. The organic layer was washed twice with water (300 ml), once with a saturated aqueous sodium hydrogen carbonate solution (100 ml), and further with water (30 ml).
0 ml), dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure.
5.1 g were obtained. This is (4- (trans-4-methoxycyclohexyl) butyl) cyclohexylpropyl aldehyde.

In a 500 ml three-necked flask equipped with a stirrer, thermometer and nitrogen inlet tube, under a nitrogen atmosphere, 86.4 g (0.24 g) of ethyltriphenylphosphine bromide.
3mol) was dissolved in 400ml of THF, and cooled to -30 ° C or lower with acetone-dry ice refrigerant. Then, 27.5g (0.25mol) of potassium-t-butoxide was added, and the mixture was stirred for 2 hours while maintaining at -30 ° C or lower. did. Then, 55.1 g of (4- (trans-4-methoxycyclohexyl) butyl) cyclohexylpropylaldehyde.
(0.18 mol) in 200 ml of THF was added dropwise over 30 minutes while maintaining the same temperature.
The temperature was raised to room temperature over time, and the mixture was further stirred at room temperature for 4 hours. After the reaction was terminated by adding 200 ml of water to the reaction solution, extraction was performed twice with toluene (200 ml). The toluene layer was washed three times with water (200 ml), dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure and concentrated. The concentrated residue was purified by silica gel chromatography using toluene as a developing solvent to obtain 48.7 g of tan crystals. This is trans-((E, Z) -3-pentenyl) -4- (4- (trans-4-methoxycyclohexyl) butyl) cyclohexane. The following isomerization operation was performed on this compound. That is, 1 equipped with a cooling pipe
In a liter eggplant-shaped flask, trans-((E,
Z) -3-pentenyl) -4- (4- (trans-4-
Methoxycyclohexyl) butyl) cyclohexane 4
8.7 g (0.15 mol) was dissolved in 200 ml of a 1/1 mixed solvent of toluene / ethanol, and 37.4 g (0.23 mol) of sodium benzenesulfinate and 6
38 ml of normal hydrochloric acid was added, and the mixture was heated under reflux for 10 hours. After cooling to room temperature, 200 ml of water was added to terminate the reaction, and then extracted twice with toluene (200 ml). The toluene layer was successively washed twice with water (200 ml), once with a saturated aqueous sodium hydrogen carbonate solution (150 ml), and twice with water (200 ml), dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Concentrated. The concentrated residue was purified by silica gel chromatography using toluene as a developing solvent, and then recrystallized from heptane to obtain 34.0 g of colorless crystals. This is transformer-((E)
-3-pentenyl) -4- (4- (trans-4-methoxycyclohexyl) butyl) cyclohexane.

In a 500 ml three-necked flask equipped with a stirrer, a thermometer and a nitrogen inlet tube, dichloromethane was cooled to −50 ° C. or less with an acetone-dry ice refrigerant under a nitrogen atmosphere, and then boron tribromide 45 was cooled. 0.2 g (0.18
mol), and 34.0 g of trans-((E) -3-pentenyl) -4- (4- (trans-4-methoxycyclohexyl) butyl) cyclohexane (0.
11 mol) in 100 ml of dichloromethane was added dropwise over 1 hour while maintaining the temperature at -50 ° C or lower. After completion of the dropwise addition, the temperature was gradually raised to room temperature over 2 hours, and the mixture was further stirred at room temperature for 8 hours. The reaction solution was added to ice water 50
After pouring into 0 ml, diethyl ether (300 m
Extracted twice in l). The extract layer was washed four times with water (250 ml), dried over anhydrous magnesium sulfate, the solvent was distilled off, and concentrated. The obtained concentrated residue (26.3 g) was placed in a 500 ml three-necked flask equipped with a stirrer, a thermometer and a nitrogen inlet tube under a nitrogen atmosphere in dichloromethane 20.
Dissolve in 0 ml, and 12.4 g (0.21 mol) of glacial acetic acid
, And while cooling in a water bath, the internal temperature is 10 to 15 ° C.
69.3 g of 12% aqueous hypochlorous acid solution while maintaining the
It was dropped over a minute. After the addition, the mixture was further stirred at room temperature for 3 hours, and 150 ml of water was added to the reaction solution to terminate the reaction. The dichloromethane layer was separated from the reaction solution, twice with water (200 ml), once with a saturated aqueous sodium hydrogen carbonate solution (150 ml), and further twice with water (200 ml).
After successively washing, the extract was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure and concentrated. The concentrated residue was purified by silica gel chromatography using toluene as a developing solvent, and then recrystallized from heptane to obtain 23.5 g of colorless crystals.
I got This results in 4- (4- (trans-4-((E)-
3-pentenyl) cyclohexyl) butyl) cyclohexanone.

In a 1-liter three-necked flask equipped with a stirrer, thermometer and nitrogen inlet tube, 34.4 g of methoxymethyltriphenylphosphonium chloride under a nitrogen atmosphere.
(100.5 mmol) dissolved in 200 ml of THF,
After cooling to −30 ° C. or lower with an acetone-dry ice refrigerant, 11.8 g of potassium-t-butoxide (105.
5 mmol), and the mixture was stirred for 2 hours while maintaining the temperature at -30 ° C or lower. Next, 4- (4- (trans-4-((E)
23.5 g (77.3 mmol) of -3-pentenyl) cyclohexyl) butyl) cyclohexanone in THF 70
The resulting solution was added dropwise over 20 minutes while maintaining the same temperature, then the temperature was raised to room temperature over 1 hour, and the mixture was further stirred at room temperature for 4 hours. After the reaction was terminated by adding 200 ml of water to the reaction solution, 2 ml of toluene (150 ml) was added.
Extracted times. The toluene layer was washed three times with water (100 ml), dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure and concentrated. The concentrated residue was purified by silica gel chromatography using toluene as a developing solvent to obtain 23.0 g of a tan crystal.

In a 500 ml eggplant-shaped flask equipped with a cooling tube, 23.0 g of the yellow-brown crystal obtained by the above operation was obtained.
Is dissolved in 100 ml of toluene, and 19.8 g of 99% formic acid is dissolved.
(43.0 mmol) was added and heated under reflux for 2 hours. After cooling the reaction solution to room temperature, 100 ml of water was added,
The organic layer was separated. The aqueous layer was extracted with 100 ml of toluene and combined with the organic layer. The organic layer was washed twice with water (100 ml), once with a saturated aqueous sodium hydrogen carbonate solution (50 ml), and twice with water (100 ml), and dried over anhydrous magnesium sulfate. And concentrated to obtain 22.1 g of tan crystals. This is 4- (4-
(Trans-4-((E) -3-pentenyl) cyclohexyl) butyl) cyclohexanecarbaldehyde.

In a 500 ml three-necked flask equipped with a stirrer, a thermometer and a nitrogen inlet tube, 36.6 g of methyltriphenylphosphonium iodide (9
0.44 mmol) was dissolved in 200 ml of THF, cooled to −30 ° C. or lower with an acetone-dry ice refrigerant, and then 10.7 g of potassium-t-butoxide (94.9 m) was added.
mol), and the mixture was stirred for 2 hours while maintaining at −30 ° C. or lower. Next, 4- (4- (trans-4-((E) -3)
-Pentenyl) cyclohexyl) butyl) cyclohexanecarbaldehyde 22.1 g (69.6 mmol) in 7
The solution dissolved in 0 ml of THF was kept at the same temperature for 2 hours.
After dropwise addition over 0 minutes, the temperature was raised to room temperature over 1 hour, and the mixture was further stirred at room temperature for 4 hours. Water 20 in the reaction solution
After 0 ml was added to terminate the reaction, toluene (15
0 ml). Water (100m)
After washing three times in 1) and drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure and concentrated. The concentrated residue was purified by silica gel chromatography using heptane as a developing solvent to obtain 18.7 g of colorless crystals. The obtained crystals were recrystallized from heptane and purified to give the title compound 1-.
Ethenyl-4- (4- (trans-4-((E) -3-
6.5 g of pentenyl) cyclohexyl) butyl) cyclohexane were obtained. ^The results of ¹ H-NMR and GC-MS strongly supported the structure of this compound. GC-MS: M ⁺ 316

By selecting various starting materials or reaction reagents, the following compounds can be produced by operating according to the above-mentioned production method. (E) -1-propenyl-4- (4- (trans-4-
((E) -3-pentenyl) cyclohexyl) butyl
Cyclohexane (No. 132) 2-propenyl-4- (4- (trans-4-((E)
-3-pentenyl) cyclohexyl) butyl) cyclohexane (E) -1-butenyl-4- (4- (trans-4-
((E) -3-pentenyl) cyclohexyl) butyl
Cyclohexane (No. 136) (Z) -2-butenyl-4- (4- (trans-4-
((E) -3-pentenyl) cyclohexyl) butyl
Cyclohexane 3-butenyl-4- (4- (trans-4-((E)-
3-pentenyl) cyclohexyl) butyl) cyclohexane (No. 141) (E) -1-pentenyl-4- (4- (trans-4-
((E) -3-pentenyl) cyclohexyl) butyl
Cyclohexane (No. 139) (Z) -2-pentenyl-4- (4- (trans-4-
((E) -3-pentenyl) cyclohexyl) butyl
Cyclohexane (E) -3-pentenyl-4- (4- (trans-4-
((E) -3-pentenyl) cyclohexyl) butyl
Cyclohexane (No. 142)

1-ethenyl-4- (4- (trans-4
-(1-ethenyl) cyclohexyl) butyl) cyclohexane (No. 122) (E) -1-propenyl-4- (4- (trans-4-
((E) -1-propenyl) cyclohexyl) butyl)
Cyclohexane (No. 128) 2-propenyl-4- (4- (trans-4- (2-propenyl) cyclohexyl) butyl) cyclohexane (E) -1-butenyl-4- (4- (trans-4-
((E) -1-butenyl) cyclohexyl) butyl) cyclohexane (No. 133) (Z) -2-butenyl-4- (4- (trans-4-
((Z) -2-butenyl) cyclohexyl) butyl) cyclohexane (E) -2-butenyl-4- (4- (trans-4-
((Z) -2-butenyl) cyclohexyl) butyl) cyclohexane (E) -2-butenyl-4- (4- (trans-4-
((E) -2-butenyl) cyclohexyl) butyl) cyclohexane

3-butenyl-4- (4- (trans-4
-(3-butenyl) cyclohexyl) butyl) cyclohexane (No. 140) (E) -1-pentenyl-4- (4- (trans-4-
((E) -1-pentenyl) cyclohexyl) butyl
Cyclohexane (No. 137) (Z) -2-pentenyl-4- (4- (trans-4-
((Z) -2-pentenyl) cyclohexyl) butyl
Cyclohexane (E) -2-pentenyl-4- (4- (trans-4-
((Z) -2-pentenyl) cyclohexyl) butyl
Cyclohexane (E) -2-pentenyl-4- (4- (trans-4-
((E) -2-pentenyl) cyclohexyl) butyl)
Cyclohexane

Example 3 trans- (1-ethenyl) -4-((E) -4- (trans-4-propylcyclohexyl) -1-butenyl) cyclohexane (Compound No. 94) (in the formula (I) m = n = i = 0, R 1 is n- propyl group, Z ³ is - (CH-2) 2CH = CH-, R ² is ethenyl group) preparation of a stirrer, a thermometer and a nitrogen inlet tube 50 g (0.20 mol) of (trans-4-propylcyclohexyl) -3-bromopropane in a 1 liter three-necked flask equipped with
69.1 g (0.26 mol) of triphenylphosphine
And a mixture of 30 ml of xylene was heated and stirred for 60 hours while maintaining the internal temperature at 130 ° C. The reaction mixture is then
After suspending in 0 ml of THF and cooling to −30 ° C. or lower with an acetone-dry ice refrigerant, 23.8 g (0.21 mol) of potassium t-butoxide was added, and
The mixture was stirred for 2 hours while maintaining the temperature at or below ℃. Then, 33.1 g (0.26 mol) of 4-formylcyclohexanone was added to T
The solution dissolved in 150 ml of HF was
After dropwise addition over 0 minutes, the temperature was raised to room temperature over 1 hour, and the mixture was further stirred at room temperature for 4 hours. Water 30 in the reaction solution
After 0 ml was added to terminate the reaction, toluene (30 ml) was added.
0 ml). Water (300m)
After washing three times in 1) and drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure and concentrated. The concentrated residue was purified by silica gel chromatography using toluene as a developing solvent to obtain 36.2 g of yellow-brown crystals.

In a 1-liter eggplant-shaped flask equipped with a cooling tube, 36.2 g of the reaction mixture obtained by the above operation was dissolved in 200 ml of a 1/1 mixed solvent of toluene / ethanol.
32.3 g of sodium benzenesulfinate and 32.8 ml of 6N hydrochloric acid were added, and the mixture was heated under reflux for 10 hours. After cooling to room temperature, 200 ml of water was added to terminate the reaction. The reaction solution was diluted with toluene (250 ml).
Extracted times. The toluene layer was washed successively twice with water (200 ml), once with a saturated aqueous sodium hydrogen carbonate solution (150 ml), and twice with water (200 ml), dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. did. The concentrated residue was purified by silica gel chromatography using toluene as a developing solvent, and then recrystallized from heptane to obtain 16.3 g of colorless crystals. This is 4-((E) -4-
(Trans-4-propylcyclohexyl) -1-butenyl) cyclohexanone.

In a 1-liter three-necked flask equipped with a stirrer, thermometer and nitrogen inlet tube, under a nitrogen atmosphere, methoxymethyltriphenylphosphonium chloride 26.3.
g (76.7 mmol) in 150 ml of THF,
After cooling to −30 ° C. or less with acetone-dry ice refrigerant, 9.0 g of potassium-t-butoxide (80.5 m
mol), and the mixture was stirred for 2 hours while maintaining at -30 ° C or lower. Then, 16.3 g (59.0 mmol) of 4-((E) -4- (trans-4-propylcyclohexyl) -1-butenyl) cyclohexanone was added to 70 ml of THF.
Was added dropwise over 20 minutes while maintaining the same temperature, the temperature was raised to room temperature over 1 hour, and the mixture was further stirred at room temperature for 4 hours. After 200 ml of water was added to the reaction solution to terminate the reaction, the mixture was extracted twice with toluene (150 ml). After washing the toluene layer three times with water (100 ml),
The extract was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and concentrated. The concentrated residue was purified by silica gel chromatography using toluene as a developing solvent to obtain yellow-brown crystals 15.3.
g was obtained.

In a 500 ml eggplant-shaped flask equipped with a cooling tube, 15.3 g of the yellow-brown crystals obtained in the above operation was dissolved in 100 ml of toluene, and 12.2 g of 99% formic acid was dissolved.
(263.0 mmol) was added and heated under reflux for 2 hours. After cooling the reaction solution to room temperature, 100 ml of water was added, and the organic layer was separated. Further, the aqueous layer is
Extracted with ml and combined with the organic layer. The organic layer was washed with water (100m
l) twice with a saturated aqueous sodium hydrogen carbonate solution (50 m
After washing once in 1) and twice with water (100 ml) in that order, the extract was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure and concentrated to obtain 13.9 g of yellow-brown crystals. This is 4-
((E) -4- (trans-4-propylcyclohexyl) -1-butenyl) cyclohexanecarbaldehyde.

In a 500 ml three-necked flask equipped with a stirrer, thermometer and nitrogen inlet tube, under a nitrogen atmosphere, 25.1 g of methyltriphenylphosphonium iodide (6.
2.1 mmol) was dissolved in 150 ml of THF and cooled to −30 ° C. or lower with an acetone-dry ice refrigerant.
7.3 g of potassium-t-butoxide (65.2 mmol
l) was added, and the mixture was stirred for 2 hours while maintaining the temperature at -30 ° C or lower. Then, 13.9 g (47.8 mmol) of 4-((E) -4- (trans-4-propylcyclohexyl) -1-butenyl) cyclohexanecarbaldehyde was added in 50 m.
Then, the solution dissolved in 1 l of THF was added dropwise over 20 minutes while maintaining the same temperature, then the temperature was raised to room temperature over 1 hour, and the mixture was further stirred at room temperature for 4 hours. After 200 ml of water was added to the reaction solution to terminate the reaction, toluene (150 ml) was added.
And extracted twice. The toluene layer was washed three times with water (100 ml), dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and concentrated. The concentrated residue was purified by silica gel chromatography using heptane as a developing solvent to obtain 12.3 g of colorless crystals. The obtained crystals were purified by recrystallization from heptane and purified to give the title compound trans- (1-ethenyl) -4-((E) -4- (trans-4-propylcyclohexyl) -1-butenyl) cyclohexane 3 .
7 g were obtained. ^The results of ¹ H-NMR and GC-MS strongly supported the structure of this compound. GC-MS: M ⁺ 288

(Trans-4-
The following compound is produced by operating according to the above production method using (trans-4-alkylcyclohexyl) -3-bromopropane having a different chain length of the alkyl group instead of (propylcyclohexyl) -3-bromopropane. it can. Trans- (1-ethenyl) -4-((E) -4- (trans-4-methylcyclohexyl) -1-butenyl)
Cyclohexane (No. 92) trans- (1-ethenyl) -4-((E) -4- (trans-4-ethylcyclohexyl) -1-butenyl)
Cyclohexane (No. 93) trans- (1-ethenyl) -4-((E) -4- (trans-4-butylcyclohexyl) -1-butenyl)
Cyclohexane trans- (1-ethenyl) -4-((E) -4- (trans-4-pentylcyclohexyl) -1-butenyl) cyclohexane (No. 95) trans- (1-ethenyl) -4-((E ) -4- (Trans-4-hexylcyclohexyl) -1-butenyl) cyclohexane trans- (1-ethenyl) -4-((E) -4- (trans-4-heptylcyclohexyl) -1-butenyl) cyclohexane ( No. 96) trans- (1-ethenyl) -4-((E) -4- (trans-4-octylcyclohexyl) -1-butenyl) cyclohexane trans- (1-ethenyl) -4-((E)- 4- (trans-4-nonylcyclohexyl) -1-butenyl)
Cyclohexane trans- (1-ethenyl) -4-((E) -4- (trans-4-decylcyclohexyl) -1-butenyl)
Cyclohexane

By selecting various starting materials or reaction reagents, the following compounds can be produced by operating according to the above-mentioned production method. Trans-((E) -1-propenyl) -4-((E)
-4- (trans-4-ethylcyclohexyl) -1-
Butenyl) cyclohexane (No. 98) trans-((E) -1-butenyl) -4-((E)-
4- (trans-4-ethylcyclohexyl) -1-butenyl) cyclohexane (No. 103) trans-((E) -1-pentenyl) -4-((E)
-4- (trans-4-ethylcyclohexyl) -1-
Butenyl) cyclohexane (No. 108) trans- (3-butenyl) -4-((E) -4- (trans-4-ethylcyclohexyl) -1-butenyl)
Cyclohexane (No. 113) trans-((E) -3-pentenyl) -4-((E)
-4- (trans-4-ethylcyclohexyl) -1-
Butenyl) cyclohexane (No. 118) trans-((E) -1-propenyl) -4-((E)
-4- (trans-4-propylcyclohexyl) -1
-Butenyl) cyclohexane (No. 99) trans-((E) -1-butenyl) -4-((E)-
4- (trans-4-propylcyclohexyl) -1-
Butenyl) cyclohexane (No. 104) trans-((E) -1-pentenyl) -4-((E)
-4- (trans-4-propylcyclohexyl) -1
-Butenyl) cyclohexane (No. 109)

Trans- (3-butenyl) -4-
((E) -4- (trans-4-propylcyclohexyl) -1-butenyl) cyclohexane (No. 114) trans-((E) -3-pentenyl) -4-((E)
-4- (trans-4-propylcyclohexyl) -1
-Butenyl) cyclohexane (No. 119) trans-((E) -1-propenyl) -4-((E)
-4- (trans-4-pentylcyclohexyl) -1
-Butenyl) cyclohexane (No. 100) trans-((E) -1-butenyl) -4-((E)-
4- (trans-4-pentylcyclohexyl) -1-
Butenyl) cyclohexane (No. 105) trans-((E) -1-pentenyl) -4-((E)
-4- (trans-4-pentylcyclohexyl) -1
-Butenyl) cyclohexane (No. 110) trans- (3-butenyl) -4-((E) -4- (trans-4-pentylcyclohexyl) -1-butenyl) cyclohexane (No. 115) trans-((E ) -3-pentenyl) -4-((E)
-4- (trans-4-pentylcyclohexyl) -1
-Butenyl) cyclohexane (No. 120)

Trans-((E) -1-propenyl)-
4-((E) -4- (trans-4-ethylcyclohexyl) -3-butenyl) cyclohexane (No. 38) trans-((E) -1-butenyl) -4-((E)-
4- (trans-4-ethylcyclohexyl) -3-butenyl) cyclohexane (No. 43) trans-((E) -1-pentenyl) -4-((E)
-4- (trans-4-ethylcyclohexyl) -3-
Butenyl) cyclohexane (No. 48) trans- (3-butenyl) -4-((E) -4- (trans-4-ethylcyclohexyl) -3-butenyl)
Cyclohexane (No. 53) trans-((E) -3-pentenyl) -4-((E)
-4- (trans-4-ethylcyclohexyl) -3-
Butenyl) cyclohexane (No. 58) trans-((E) -1-propenyl) -4-((E)
-4- (trans-4-propylcyclohexyl) -3
-Butenyl) cyclohexane (No. 39) trans-((E) -1-butenyl) -4-((E)-
4- (trans-4-propylcyclohexyl) -3-
Butenyl) cyclohexane (No. 44) trans-((E) -1-pentenyl) -4-((E)
-4- (trans-4-propylcyclohexyl) -3
-Butenyl) cyclohexane (No. 49)

Trans- (3-butenyl) -4-
((E) -4- (Trans-4-propylcyclohexyl) -3-butenyl) cyclohexane (No. 54) trans-((E) -3-pentenyl) -4-((E)
-4- (trans-4-propylcyclohexyl) -3
-Butenyl) cyclohexane (No. 59) trans-((E) -1-propenyl) -4-((E)
-4- (trans-4-pentylcyclohexyl) -3
-Butenyl) cyclohexane (No. 40) trans-((E) -1-butenyl) -4-((E)-
4- (trans-4-pentylcyclohexyl) -3-
Butenyl) cyclohexane (No. 45) trans-((E) -1-pentenyl) -4-((E)
-4- (trans-4-pentylcyclohexyl) -3
-Butenyl) cyclohexane (No. 50) trans- (3-butenyl) -4-((E) -4- (trans-4-pentylcyclohexyl) -3-butenyl) cyclohexane (No. 55) trans-((E ) -3-pentenyl) -4-((E)
-4- (trans-4-pentylcyclohexyl) -3
-Butenyl) cyclohexane (No. 60)

Trans-((E) -1-propenyl)-
4-((Z) -4- (trans-4-ethylcyclohexyl) -2-butenyl) cyclohexane (No. 68) trans-((E) -1-butenyl) -4-((Z)-
4- (trans-4-ethylcyclohexyl) -2-butenyl) cyclohexane (No. 73) trans-((E) -1-pentenyl) -4-((Z)
-4- (trans-4-ethylcyclohexyl) -2-
Butenyl) cyclohexane (No. 78) trans-4- (3-butenyl) -4-((Z) -4- (trans-4-ethylcyclohexyl) -2-butenyl)
Cyclohexane (No. 83) trans-((E) -3-pentenyl) -4-((Z)
-4- (trans-4-ethylcyclohexyl) -2-
Butenyl) cyclohexane (No. 88) trans-((E) -1-propenyl) -4-((Z)
-4- (trans-4-propylcyclohexyl) -2
-Butenyl) cyclohexane (No. 69) trans-((E) -1-butenyl) -4-((Z)-
4- (trans-4-propylcyclohexyl) -2-
Butenyl) cyclohexane (No. 74) trans-((E) -1-pentenyl) -4-((Z)
-4- (trans-4-propylcyclohexyl) -2
-Butenyl) cyclohexane (No. 79)

Trans- (3-butenyl) -4-
((Z) -4- (trans-4-propylcyclohexyl) -2-butenyl) cyclohexane (No. 84) trans-((E) -3-pentenyl) -4-((Z)
-4- (trans-4-propylcyclohexyl) -2
-Butenyl) cyclohexane (No. 89) trans-((E) -1-propenyl) -4-((Z)
-4- (trans-4-pentylcyclohexyl) -2
-Butenyl) cyclohexane (No. 70) trans-((E) -1-butenyl) -4-((Z)-
4- (trans-4-pentylcyclohexyl) -2-
Butenyl) cyclohexane (No. 75) trans-((E) -1-pentenyl) -4-((Z)
-4- (trans-4-pentylcyclohexyl) -2
-Butenyl) cyclohexane (No. 80) trans- (3-butenyl) -4-((Z) -4- (trans-4-pentylcyclohexyl) -2-butenyl) cyclohexane (No. 85) trans-((E ) -3-pentenyl) -4-((Z)
-4- (trans-4-pentylcyclohexyl) -2
-Butenyl) cyclohexane (No. 90)

Example 4 trans-1-ethenyl-4-((E) -4- (trans-4-ethenylcyclohexyl) -1-butenyl) cyclohexane (Compound No. 143) = N = i = 0, R ¹ is an ethenyl group, Z ³ is —CH ＝ CH— (CH 2) 2 —, and R ² is an ethenyl group): equipped with a stirrer, a thermometer, and a nitrogen inlet tube. In a 1-liter three-necked flask, under a nitrogen atmosphere, 59.1 g (172.0 mmol) of methoxymethyltriphenylphosphonium chloride was added to THF200.
dissolved in acetone, and -30 ° C with acetone-dry ice refrigerant
After cooling to below, potassium-t-butoxide 20.
3 g (181.0 mmol) was added, and the mixture was stirred for 2 hours while maintaining the temperature at -30 ° C or lower. Then, 35.0 g (133.0 mmol) of 4-((E) -4- (trans-4-methoxycyclohexyl) -3-butenyl) cyclohexanone produced by the operation described in Example 2 was added to 100 m of THF.
Then, the solution dissolved in 1 was dropped over 40 minutes while maintaining the same temperature, and then the temperature was raised to room temperature over 1 hour, and further stirred at room temperature for 4 hours. After the reaction was terminated by adding 200 ml of water to the reaction solution, 2 ml of toluene (200 ml) was added.
Extracted times. The toluene layer was washed twice with water (200 ml), dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and concentrated. The concentrated residue was purified by silica gel chromatography using toluene as a developing solvent to obtain 33.1 g of yellow-brown crystals.

In a 500 ml eggplant-shaped flask equipped with a cooling tube, 33.1 g of the yellow-brown crystal obtained by the above operation was obtained.
Is dissolved in 100 ml of toluene, and 27.2 g of 99% formic acid is dissolved.
(590.0 mmol), and the mixture was heated under reflux for 2 hours. After cooling the reaction solution to room temperature, 100 ml of water was added, and the organic layer was separated. Further, the aqueous layer is
Extracted with ml and combined with the organic layer. The organic layer was washed with water (150m
l) twice with a saturated aqueous sodium hydrogen carbonate solution (100 m
The mixture was washed once with 1) and twice with water (150 ml) successively, then dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure and concentrated to obtain 29.5 g of yellow-brown crystals. This is 4-
((E) -4- (trans-4-methoxycyclohexyl) -3-butenyl) cyclohexanecarbaldehyde.

In a 500 ml three-necked flask equipped with a stirrer, thermometer and nitrogen inlet tube, under a nitrogen atmosphere, 55.7 g of methyltriphenylphosphonium iodide (13
8.0 mmol) was dissolved in 250 ml of THF, and cooled to −30 ° C. or lower with an acetone-dry ice refrigerant.
16.3 g of potassium-t-butoxide (145.0 mm
ol) and stirred for 2 hours while maintaining the temperature at -30 ° C or lower. Then, 29.5 g (106.0 mmol) of 4-((E) -4- (trans-4-methoxycyclohexyl) -3-butenyl) cyclohexanecarbaldehyde was added to T.
The solution dissolved in 90 ml of HF is kept at the same temperature for 30 minutes.
After dropping over a period of time, the temperature was raised to room temperature over 1 hour, and the mixture was further stirred at room temperature for 4 hours. Water 200 in the reaction solution
After terminating the reaction by addition of toluene (150 ml
ml) twice. Water (100 ml) of toluene layer
, And dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure and concentrated. The concentrated residue was purified by silica gel chromatography using heptane as a developing solvent,
24.9 g of colorless crystals were obtained. The obtained crystal was recrystallized from heptane to obtain 15.4 g of colorless crystals. This is 1-ethenyl-4-((E) -4- (trans-4-methoxycyclohexyl) -3-butenyl) cyclohexane.

In a 500 ml three-necked flask equipped with a stirrer, a thermometer and a nitrogen inlet tube, 250 ml of dichloromethane was cooled to −50 ° C. or lower with an acetone-dry ice refrigerant under a nitrogen atmosphere, and then boron tribromide was added. 20.9g
(83.9 mmol) was added and 1-ethenyl-
15.4 g of 4-((E) -4- (trans-4-methoxycyclohexyl) -3-butenyl) cyclohexane
A solution of (55.9 mmol) dissolved in 100 ml of dichloromethane was added dropwise over 1 hour while maintaining at -50 ° C or lower. After completion of the dropping, the temperature was gradually raised to room temperature over 2 hours, and then the mixture was further stirred at room temperature for 8 hours. The reaction solution was poured into 500 ml of ice water, and extracted twice with diethyl ether (300 ml). Extract layer with water (250
ml), and dried over anhydrous magnesium sulfate. The solvent was distilled off and concentrated. The resulting concentrated residue (11.
1 g) was prepared with 5 equipped with a stirrer, thermometer and nitrogen inlet tube.
In a 00 ml three-necked flask, dissolved in 200 ml of dichloromethane under a nitrogen atmosphere, and 6.1 g of glacial acetic acid (10 g
After adding 1.9 mmol), the mixture was cooled in a water bath to maintain the internal temperature at 10 to 15 ° C.
4.3 g (55.2 mmol) were added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 3 hours, and 150 ml of water was added to the reaction solution to terminate the reaction. Separate the dichloromethane layer from the reaction solution and add water (200 ml)
Twice, saturated aqueous sodium hydrogen carbonate solution (150 ml)
After washing once with water and then twice with water (200 ml) sequentially, the extract was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure and concentrated. The concentrated residue was purified by silica gel chromatography using toluene as a developing solvent, and then recrystallized from heptane to obtain 8.0 g of colorless crystals. This is 4-
((E) -4- (trans-4-ethenylcyclohexyl) -1-butenyl) cyclohexanone.

In a 1-liter three-necked flask equipped with a stirrer, a thermometer and a nitrogen inlet tube, methoxymethyltriphenylphosphonium chloride 13.7 was added under a nitrogen atmosphere.
g (40.0 mmol) in 100 ml of THF,
After cooling to −30 ° C. or less under acetone-dry ice refrigerant, 4.7 g of potassium-t-butoxide (42.1 m
mol), and the mixture was stirred for 2 hours while maintaining at -30 ° C or lower. Then, a solution prepared by dissolving 8.0 g (30.8 mmol) of 4-((E) -4- (trans-4-ethenylcyclohexyl) -1-butenyl) cyclohexanone in 30 ml of THF took 20 minutes while maintaining the same temperature. After the dropwise addition, the temperature was raised to room temperature over 1 hour, and the mixture was further stirred at room temperature for 4 hours. After 200 ml of water was added to the reaction solution to terminate the reaction, the mixture was extracted twice with toluene (150 ml). The toluene layer was washed three times with water (100 ml), dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and concentrated. The concentrated residue was purified by silica gel chromatography using toluene as a developing solvent to obtain 7.5 g of yellow-brown crystals.

In a 300 ml eggplant-shaped flask equipped with a cooling tube, 7.5 g of the yellow-brown crystals obtained by the above operation were dissolved in 50 ml of toluene, and 6.3 g of 99% acid (135.
(0 mmol), and the mixture was refluxed for 2 hours. After cooling the reaction solution to room temperature, 100 ml of water was added, and the organic layer was separated. The aqueous layer was extracted with 100 ml of toluene and combined with the organic layer. The organic layer was washed with water (100 ml) 2
1 time with saturated aqueous sodium hydrogen carbonate solution (50 ml)
The mixture was successively washed twice with water (100 ml) twice, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure and concentrated to obtain 6.9 g of yellow-brown crystals. This is 4-((E)-
4- (trans-4-ethenylcyclohexyl) -1-
Butenyl) cyclohexylcarbaldehyde.

In a 500 ml three-necked flask equipped with a stirrer, a thermometer and a nitrogen inlet tube, 13.4 g of methyltriphenylphosphonium iodide (3
3.1 mmol) was dissolved in 60 ml of THF, cooled to −30 ° C. or lower with an acetone-dry ice refrigerant, and then 3.9 g (34.8 mmol) of potassium t-butoxide.
Was added and the mixture was stirred for 2 hours while maintaining the temperature at -30 ° C or lower.
Then 6.9 g (25.5 mmol) of 4-((E) -4- (trans-4-ethenylcyclohexyl) -1-butenyl) cyclohexylcarbaldehyde was added to 30 ml of T
After the solution dissolved in HF was added dropwise over 20 minutes while maintaining the same temperature, the temperature was raised to room temperature over 1 hour, and the mixture was further stirred at room temperature for 4 hours. After the reaction was terminated by adding 200 ml of water to the reaction solution, extraction was performed twice with toluene (150 ml). The toluene layer was washed three times with water (100 ml), dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and concentrated. The concentrated residue was purified by silica gel chromatography using heptane as a developing solvent to obtain 6.2 g of colorless crystals. The obtained crystals were purified by recrystallization from heptane to give the title compound trans-1-ethenyl-
2.8 g of 4-((E) -4- (trans-4-ethenylcyclohexyl) -1-butenyl) cyclohexane was obtained. ^The results of ¹ H-NMR and GC-MS strongly supported the structure of this compound. GC-MS M ⁺ 272

By selecting various starting materials or reaction reagents, the following compounds can be produced by operating according to the above-mentioned production method. Trans-1-ethenyl-4-((E) -4- (trans-4-((E) -1-propenyl) cyclohexyl)
-1-butenyl) cyclohexane (No. 144) trans-1-ethenyl-4-((E) -4- (trans-4-((E) -1-butenyl) cyclohexyl)-
1-butenyl) cyclohexane (No. 145) trans-1-ethenyl-4-((E) -4- (trans-4-((E) -1-pentenyl) cyclohexyl)
-1-butenyl) cyclohexane (No. 146) trans-1-ethenyl-4-((E) -4- (trans-4-((Z) -2-propenyl) cyclohexyl)
-1-butenyl) cyclohexane trans-1-ethenyl-4-((E) -4- (trans-4-((Z) -2-butenyl) cyclohexyl)-
1-butenyl) cyclohexane trans-1-ethenyl-4-((E) -4- (trans-4-((E) -3-butenyl) cyclohexyl)-
1-butenyl) cyclohexane (No. 147) trans-1-ethenyl-4-((E) -4- (trans-4-((E) -3-pentenyl) cyclohexyl)
-1-butenyl) cyclohexane (No. 148)

Trans-1-((E) -1-propenyl) -4-((E) -4- (trans-4-((E)-
1-propenyl) cyclohexyl) -1-butenyl) cyclohexane (No. 149) trans-1-((E) -1-propenyl) -4-
((E) -4- (trans-4-((E) -1-butenyl) cyclohexyl) -1-butenyl) cyclohexane (No. 150) trans-1-((E) -1-propenyl) -4-
((E) -4- (trans-4-((E) -1-pentenyl) cyclohexyl) -1-butenyl) cyclohexane (No. 151) trans-1-((E) -1-propenyl) -4-
((E) -4- (trans-4-((Z) -2-propenyl) cyclohexyl) -1-butenyl) cyclohexane trans-1-((E) -1-propenyl) -4-
((E) -4- (trans-4-((Z) -2-butenyl) cyclohexyl) -1-butenyl) cyclohexane trans-1-((E) -1-propenyl) -4-
((E) -4- (trans-4-((E) -3-butenyl) cyclohexyl) -1-butenyl) cyclohexane (No. 152) trans-1-((E) -1-propenyl) -4-
((E) -4- (trans-4-((E) -3-pentenyl) cyclohexyl) -1-butenyl) cyclohexane (No. 153)

Trans-1-((E) -3-butenyl)
-4-((E) -4- (trans-4-((E) -1-)
Propenyl) cyclohexyl) -1-butenyl) cyclohexane trans-1-((E) -3-butenyl) -4-
((E) -4- (trans-4-((E) -1-butenyl) cyclohexyl) -1-butenyl) cyclohexane trans-1-((E) -3-butenyl) -4-
((E) -4- (trans-4-((E) -1-pentenyl) cyclohexyl) -1-butenyl) cyclohexane trans-1-((E) -3-butenyl) -4-
((E) -4- (trans-4-((Z) -2-propenyl) cyclohexyl) -1-butenyl) cyclohexane trans-1-((E) -3-butenyl) -4-
((E) -4- (trans-4-((Z) -2-butenyl) cyclohexyl) -1-butenyl) cyclohexane trans-1-((E) -3-butenyl) -4-
((E) -4- (trans-4-((E) -3-butenyl) cyclohexyl) -1-butenyl) cyclohexane (No. 161) trans-1-((E) -3-butenyl) -4-
((E) -4- (trans-4-((E) -3-pentenyl) cyclohexyl) -1-butenyl) cyclohexane (No. 162)

Trans-1-((E) -3-pentenyl) -4-((E) -4- (trans-4-((E)-
1-propenyl) cyclohexyl) -1-butenyl) cyclohexane trans-1-((E) -3-pentenyl) -4-
((E) -4- (trans-4-((E) -1-butenyl) cyclohexyl) -1-butenyl) cyclohexane trans-1-((E) -3-pentenyl) -4-
((E) -4- (trans-4-((E) -1-pentenyl) cyclohexyl) -1-butenyl) cyclohexane trans-1-((E) -3-pentenyl) -4-
((E) -4- (trans-4-((Z) -2-propenyl) cyclohexyl) -1-butenyl) cyclohexane trans-1-((E) -3-pentenyl) -4-
((E) -4- (trans-4-((Z) -2-butenyl) cyclohexyl) -1-butenyl) cyclohexane trans-1-((E) -3-pentenyl) -4-
((E) -4- (trans-4-((E) -3-butenyl) cyclohexyl) -1-butenyl) cyclohexane trans-1-((E) -3-pentenyl) -4-
((E) -4- (trans-4-((E) -3-pentenyl) cyclohexyl) -1-butenyl) cyclohexane (No. 163)

Example 5 trans-1- (3-butenyl) -4- (4- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) butyl) cyclohexane (Compound No.
213) (In the general formula (I), m = 1, n = i = 0, ring A ¹ is ¹ , 4-cyclohexylene group, Z ¹ is a single bond, and R ¹ is n-
Preparation of propyl group, Z ³ is — (CH ² ) 4 — and R ² is 3-butenyl group): In a 1-liter three-necked flask equipped with a stirrer, a thermometer and a nitrogen inlet tube, a nitrogen atmosphere is used. Lower 1,3-dioxolan-2-yl) ethyl] triphenylphosphonium bromide 32.0 g (72.2 mm
ol) was suspended in 300 ml of THF, cooled to −30 ° C. or lower with an acetone-dry ice refrigerant, 8.5 g (75.8 mmol) of potassium-t-butoxide was added, and the mixture was maintained at −30 ° C. or lower for 2 hours. Stirred. Next, 20.0 g (55.6 mmol) of 4- (4- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) butyl) cyclohexanone was added to THF 50m.
The solution dissolved in 1 was added dropwise over 20 minutes while maintaining the same temperature, then the temperature was raised to room temperature over 1 hour, and the mixture was further stirred at room temperature for 4 hours. After the reaction was terminated by adding 200 ml of water to the reaction solution, 3 ml of toluene (150 ml) was added.
Extracted times. The toluene layer was washed three times with water (100 ml), dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure and concentrated. The concentrated residue was purified by silica gel chromatography using toluene as a developing solvent to obtain 20.7 g of yellow-brown crystals.

In a 1-liter three-necked flask equipped with a stirrer, 20.7 g of the yellow-brown crystals obtained in the above operation were dissolved in 150 ml of a mixed solvent of toluene / ethanol = 1/1, and 5% -palladium carbon catalyst was added. 1.9 g was added, and catalytic hydrogen reduction was performed at room temperature under a hydrogen pressure of 5 to 10 kg / cm ² for 5 hours. The solvent was distilled off under reduced pressure from the reaction solution from which the catalyst was removed by filtration, and concentrated. The concentrated residue was dissolved in 200 ml of toluene in a 300 ml eggplant-shaped flask equipped with a condenser, and 99%
% Formic acid (10.7 g, 23.0 mmol) was added, and the mixture was heated under reflux for 2 hours. After cooling the reaction solution to room temperature, water 10
0 ml was added and the organic layer was separated. Further, the aqueous layer was extracted with 200 ml of toluene and combined with the organic layer. The organic layer was washed twice with water (100 ml) twice, once with a saturated aqueous solution of sodium hydrogen carbonate (50 ml) and twice with water (100 ml), dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. And concentrated to give 15.2 g of tan crystals.
This is 4- (4- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) butyl) cyclohexylpropane-3-al.

In a 1-liter three-necked flask equipped with a stirrer, a thermometer and a nitrogen inlet tube, under a nitrogen atmosphere, 19.9 g of methyltriphenylphosphine iodide (49.
1 mmol) was suspended in 60 ml of THF, and acetone-
After cooling to −30 ° C. or lower with a dry ice refrigerant, potassium-t-butoxide (5.8 g, 51.6 mmol) was added, and the mixture was stirred for 2 hours while maintaining the temperature at −30 ° C. or lower. Then, the 4- (4- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) obtained by the above operation is obtained.
15.2 g of butyl) cyclohexylpropane-3-al
A solution of (51.6 mmol) dissolved in 50 ml of THF was added dropwise over 15 minutes while maintaining the same temperature, then the temperature was raised to room temperature over 1 hour, and the mixture was further stirred at room temperature for 4 hours. After the reaction was terminated by adding water 100 to the reaction solution, the mixture was extracted three times with toluene (100 ml). The toluene layer was washed three times with water (100 ml), dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and concentrated. The concentrated residue was purified by silica gel chromatography using heptane as a developing solvent, and further purified by recrystallization from heptane to obtain 5.5 g of colorless crystals. This is the title compound trans-1- (3-butenyl) -4- (4-
(Trans-4- (trans-4-propylcyclohexyl) cyclohexyl) butyl) cyclohexane. ^The results of ¹ H-NMR and GC-MS strongly supported the structure of this compound. GC-MS: M ⁺ 272

In the above production method, 4- (4- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) butyl) cyclohexanone was replaced with 4- (4- (trans-4) −
The following compounds can be produced by using (trans-4-alkylcyclohexyl) cyclohexyl) butyl) cyclohexanone and operating according to the above production method. Trans-1- (3-butenyl) -4- (4- (trans-4- (trans-4-ethylcyclohexyl) cyclohexyl) butyl) cyclohexane (No. 212) trans-1- (3-butenyl) -4- (4- (trans-4- (trans-4-butylcyclohexyl) cyclohexyl) butyl) cyclohexane trans-1- (3-butenyl) -4- (4- (trans-4- (trans-4-pentylcyclohexyl) cyclohexyl) ) Butyl) cyclohexane (No. 21)
4) trans-1- (3-butenyl) -4- (4- (trans-4- (trans-4-hexylcyclohexyl) cyclohexyl) butyl) cyclohexane trans-1- (3-butenyl) -4- (4- (Trans-4- (trans-4-heptylcyclohexyl) cyclohexyl) butyl) cyclohexane trans-1- (3-butenyl) -4- (4- (trans-4- (trans-4-octylcyclohexyl) cyclohexyl) butyl) Cyclohexane trans-1- (3-butenyl) -4- (4- (trans-4- (trans-4-nonylcyclohexyl) cyclohexyl) butyl) cyclohexane trans-1- (3-butenyl) -4- (4- ( Trans-4- (trans-4-decylcyclohexyl) cyclohexyl) buty ) Cyclohexane

Trans-1-ethenyl-4- (4- (trans-4- (trans-4-ethylcyclohexyl)
Cyclohexyl) butyl) cyclohexane (No. 20
0) trans-1-ethenyl-4- (4- (trans-4-
(Trans-4-propylcyclohexyl) cyclohexyl) butyl) cyclohexane (No. 201) trans-1-ethenyl-4- (4- (trans-4-
(Trans-4-pentylcyclohexyl) cyclohexyl) butyl) cyclohexane (No. 202) trans-1-((E) -1-propenyl) -4- (4
-(Trans-4- (trans-4-ethylcyclohexyl) cyclohexyl) butyl) cyclohexane (N
o.203) trans-1-((E) -1-propenyl) -4- (4
-(Trans-4- (trans-4-propylcyclohexyl) cyclohexyl) butyl) cyclohexane (N
o.204) trans-1-((E) -1-propenyl) -4- (4
-(Trans-4- (trans-4-pentylcyclohexyl) cyclohexyl) butyl) cyclohexane (N
o.205) trans-1-((E) -3-pentenyl) -4- (4
-(Trans-4- (trans-4-ethylcyclohexyl) cyclohexyl) butyl) cyclohexane (N
o.215) trans-1-((E) -3-pentenyl) -4- (4
-(Trans-4- (trans-4-propylcyclohexyl) cyclohexyl) butyl) cyclohexane (N
o.216) trans-1-((E) -3-pentenyl) -4- (4
-(Trans-4- (trans-4-pentylcyclohexyl) cyclohexyl) butyl) cyclohexane (N
o.217)

Example 6 trans-1-ethenyl-4-((E) -4- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) -1-butenyl) cyclohexane (Compound No. 237) In the formula (I), m = 1, n = i = 0, ring A ¹ is 1,4-cyclohexylene group, Z ¹ is a single bond, and R ¹ is n-
Propyl group, Z ³ is - (CH2) 2-CH = CH-, R ² is ethenyl group): Prepared stirrer, in a three-necked 2 liter flask equipped with a thermometer and a nitrogen inlet tube,
Under a nitrogen atmosphere, 1- (trans-4- (trans-4-
Propylcyclohexyl) cyclohexyl) propyltriphenylphosphine iodide 164.6 g (258.
0 mmol) was suspended in 500 ml of THF, cooled to −30 ° C. or lower with an acetone-dry ice refrigerant, and then 30.4 g of potassium-t-butoxide (271.0 mmol) was added.
l) was added, and the mixture was stirred for 2 hours while maintaining the temperature at -30 ° C or lower. Then 25.0 g of 4-formylcyclohexanone
A solution of (198 mmol) dissolved in 100 ml of THF was added dropwise over 50 minutes while maintaining the same temperature, and then the temperature was raised to room temperature over 1 hour, followed by stirring at room temperature for 4 hours. After the reaction was terminated by adding 500 ml of water to the reaction solution, three extractions were performed with toluene (300 ml). The toluene layer was washed three times with water (500 ml), dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and concentrated. The concentrated residue was directly purified by silica gel chromatography using toluene as a developing solvent, and 63.1 g of yellow-brown crystals were obtained.
I got

In a 1-liter eggplant-shaped flask equipped with a cooling tube, 63.1 g of the yellow-brown crystals obtained in the above operation were dissolved in 400 ml of a 1/1 mixed solvent of toluene / ethanol.
After adding 43.3 g of sodium benzenesulfinate and 44.0 ml of 6N hydrochloric acid, the mixture was refluxed with heating for 10 hours. After cooling the reaction solution to room temperature, 300 ml of water was added to terminate the reaction. The reaction solution was toluene (300 m
Extracted twice in l). The toluene layer was successively washed twice with water (200 ml), once with a saturated aqueous solution of sodium hydrogen carbonate (250 ml), twice with water (300 ml), dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. And concentrated. The concentrated residue was purified by silica gel chromatography using toluene as a developing solvent, and then recrystallized from heptane to obtain 43.5 g of colorless crystals. This is 4-
((E) -4- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) -1-butenyl) cyclohexanone.

In a 1-liter three-necked flask equipped with a stirrer, thermometer and nitrogen inlet tube, under a nitrogen atmosphere, methoxymethyltriphenylphosphonium chloride 53.9.
g (157.0 mmol) was dissolved in 200 ml of THF, cooled to −30 ° C. or lower with an acetone-dry ice refrigerant, and then 18.5 g of potassium-t-butoxide (16 g) was added.
5.0 mmol) and stirred for 2 hours while maintaining the temperature at -30 ° C or lower. Then, 4-((E) -4- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) -1-butenyl) cyclohexanone
A solution prepared by dissolving 5 g (121.0 mmol) in 150 ml of THF was added dropwise over 50 minutes while maintaining the same temperature, and then the temperature was raised to room temperature over 1 hour, followed by stirring at room temperature for 4 hours. After the reaction was terminated by adding 300 ml of water to the reaction solution, extraction was performed twice with toluene (250 ml). After washing the toluene layer three times with water (200 ml),
The extract was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and concentrated. The concentrated residue was purified by silica gel chromatography using toluene as a developing solvent to give yellow-brown crystals.
3 g were obtained.

In a 1-liter eggplant-shaped flask equipped with a condenser, 40.3 g of the yellow-brown crystals obtained by the above operation were dissolved in 300 ml of toluene, and 24.6 g of 99% formic acid (5
35.0 l) was added, and the mixture was heated under reflux for 2 hours. After cooling the reaction solution to room temperature, 200 ml of water was added, and the organic layer was separated. Further, the aqueous layer was extracted with 300 ml of toluene and combined with the organic layer. The organic phase is washed with water (200 ml) 2
1 time with saturated aqueous sodium hydrogen carbonate solution (150 ml)
The solution was washed successively twice with water and water (200 ml),
After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the mixture was concentrated to obtain 35.8 g of yellow-brown crystals. This is 4-
((E) -4- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) -1-butenyl) cyclohexylcarbaldehyde.

In a 1-liter three-necked flask equipped with a stirrer, a thermometer, and a nitrogen inlet tube, under a nitrogen atmosphere, 50.6 g (12
5.0 mmol) was dissolved in 200 ml of THF, and cooled to −30 ° C. or lower with an acetone-dry ice refrigerant.
Potassium-t-butoxide 14.7 g (131.0 mm
ol) and stirred for 2 hours while maintaining the temperature at -30 ° C or lower. Next, 4-((E) -4- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) -1-butenyl) cyclohexylcarbaldehyde 3
A solution of 5.8 g (96.3 mmol) dissolved in 100 ml of THF was added dropwise over 30 minutes while maintaining the same temperature. After that, the temperature was raised to room temperature over 1 hour, and the mixture was further stirred at room temperature for 4 hours. . After the reaction was terminated by adding 200 ml of water to the reaction solution, extraction was performed twice with toluene (250 ml). The toluene layer was washed three times with water (200 ml), dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and concentrated. The concentrated residue was purified by silica gel chromatography using heptane as a developing solvent to obtain colorless crystals 3
1.7 g were obtained. The obtained crystals were purified by recrystallization from heptane, and the title compound, trans-1-ethenyl-4-((E) -4- (trans-4- (trans-4)
-Propylcyclohexyl) cyclohexyl) -1-butenyl) cyclohexane was obtained. ¹ H-NMR and G
The results of C-MS strongly supported the structure of the compound. GC-MS: M ⁺ 370

The 1- (trans-4) used in the above production method was used.
1- (trans-4-yl) having a different chain length of an alkyl group instead of-(trans-4-propylcyclohexyl) cyclohexyl) propyltriphenylphosphine iodide
The following compounds can be produced by using (trans-4-alkylcyclohexyl) cyclohexyl) propyltriphenylphosphine iodide and operating according to the above production method. Trans-1-ethenyl-4-((E) -4- (trans-4- (trans-4-methylcyclohexyl) cyclohexyl) -1-butenyl) cyclohexane trans-1-ethenyl-4-((E) -4 -(Trans-4- (trans-4-ethylcyclohexyl) cyclohexyl) -1-butenyl) cyclohexane (No.
236) trans-1-ethenyl-4-((E) -4- (trans-4- (trans-4-butylcyclohexyl) cyclohexyl) -1-butenyl) cyclohexane trans-1-ethenyl-4-((E) -4- (trans-4- (trans-4-pentylcyclohexyl) cyclohexyl) -1-butenyl) cyclohexane (N
o.238) trans-1-ethenyl-4-((E) -4- (trans-4- (trans-4-hexylcyclohexyl) cyclohexyl) -1-butenyl) cyclohexane trans-1-ethenyl-4-(( E) -4- (Trans-4- (trans-4-heptylcyclohexyl) cyclohexyl) -1-butenyl) cyclohexane trans-1-ethenyl-4-((E) -4- (trans-4- (trans-4 -Octylcyclohexyl) cyclohexyl) -1-butenyl) cyclohexane trans-1-ethenyl-4-((E) -4- (trans-4- (trans-4-nonylcyclohexyl) cyclohexyl) -1-butenyl) cyclohexane trans- 1-ethenyl-4-((E) -4- (trans-4- (trans-4-dec Cyclohexyl) cyclohexyl) -1-butenyl) cyclohexane

The following compounds can be produced by selecting various starting materials or reaction reagents in the above-mentioned production method and operating according to the above-mentioned production method. Trans-1-((E) -1-propenyl) -4-
((E) -4- (trans-4- (trans-4-ethylcyclohexyl) cyclohexyl) -1-butenyl)
Cyclohexane (No. 239) trans-1-((E) -1-propenyl) -4-
((E) -4- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) -1-butenyl) cyclohexane (No. 240) trans-1-((E) -1-propenyl) -4-
((E) -4- (trans-4- (trans-4-pentylcyclohexyl) cyclohexyl) -1-butenyl) cyclohexane (No. 241) trans-1-((E) -1-butenyl) -4-
((E) -4- (trans-4- (trans-4-ethylcyclohexyl) cyclohexyl) -1-butenyl)
Cyclohexane (No. 242) trans-1-((E) -1-butenyl) -4-
((E) -4- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) -1-butenyl) cyclohexane (No. 243) trans-1-((E) -1-butenyl) -4-
((E) -4- (trans-4- (trans-4-pentylcyclohexyl) cyclohexyl) -1-butenyl) cyclohexane (No. 244)

Trans-1- (3-butenyl) -4-
((E) -4- (trans-4- (trans-4-ethylcyclohexyl) cyclohexyl) -1-butenyl)
Cyclohexane (No. 248) trans-1- (3-butenyl) -4-((E) -4-
(Trans-4- (trans-4-propylcyclohexyl) cyclohexyl) -1-butenyl) cyclohexane (No. 249) trans-1- (3-butenyl) -4-((E) -4-
(Trans-4- (trans-4-pentylcyclohexyl) cyclohexyl) -1-butenyl) cyclohexane (No. 250) trans-1-((E) -3-pentenyl) -4-
((E) -4- (trans-4- (trans-4-ethylcyclohexyl) cyclohexyl) -1-butenyl)
Cyclohexane (No. 251) trans-1-((E) -3-pentenyl) -4-
((E) -4- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) -1-butenyl) cyclohexane (No. 252) trans-1-((E) -3-pentenyl) -4-
((E) -4- (trans-4- (trans-4-pentylcyclohexyl) cyclohexyl) -1-butenyl) cyclohexane (No. 253)

Trans-1-ethenyl-4-((E)-
4- (trans-4- (trans-4-ethylcyclohexyl) cyclohexyl) -3-butenyl) cyclohexane (No. 218) trans-1-ethenyl-4-((E) -4- (trans-4- (trans -4-propylcyclohexyl) cyclohexyl) -3-butenyl) cyclohexane (N
o.219) trans-1-ethenyl-4-((E) -4- (trans-4- (trans-4-pentylcyclohexyl) cyclohexyl) -3-butenyl) cyclohexane (N
o.220)

Trans-1-((E) -1-propenyl) -4-((E) -4- (trans-4- (trans-4-ethylcyclohexyl) cyclohexyl) -3-
Butenyl) cyclohexane (No. 221) trans-1-((E) -1-propenyl) -4-
((E) -4- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) -3-butenyl) cyclohexane (No. 222) trans-1-((E) -1-propenyl) -4-
((E) -4- (trans-4- (trans-4-pentylcyclohexyl) cyclohexyl) -3-butenyl) cyclohexane (No. 223) trans-1-((E) -1-butenyl) -4-
((E) -4- (trans-4- (trans-4-ethylcyclohexyl) cyclohexyl) -3-butenyl)
Cyclohexane (No. 224) trans-1-((E) -1-butenyl) -4-
((E) -4- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) -3-butenyl) cyclohexane (No. 225) trans-1-((E) -1-butenyl) -4-
((E) -4- (trans-4- (trans-4-pentylcyclohexyl) cyclohexyl) -3-butenyl) cyclohexane (No. 226)

Trans-1- (3-butenyl) -4-
((E) -4- (trans-4- (trans-4-ethylcyclohexyl) cyclohexyl) -3-butenyl)
Cyclohexane (No. 230) trans-1- (3-butenyl) -4-((E) -4-
(Trans-4- (trans-4-propylcyclohexyl) cyclohexyl) -3-butenyl) cyclohexane (No. 231) trans-1- (3-butenyl) -4-((E) -4-
(Trans-4- (trans-4-pentylcyclohexyl) cyclohexyl) -3-butenyl) cyclohexane (No. 232) trans-1-((E) -3-pentenyl) -4-
((E) -4- (trans-4- (trans-4-ethylcyclohexyl) cyclohexyl) -3-butenyl)
Cyclohexane (No. 233) trans-1-((E) -3-pentenyl) -4-
((E) -4- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) -3-butenyl) cyclohexane (No. 234) trans-1-((E) -3-pentenyl) -4-
((E) -4- (trans-4- (trans-4-pentylcyclohexyl) cyclohexyl) -3-butenyl) cyclohexane (No. 235)

Example 7 trans-1-ethenyl-4-((E) -4-((E)
-2- (trans-4- (trans-4-propylcyclohexyl) ethenyl) cyclohexyl) -3-butenyl) cyclohexane (Compound No. 307) (In the general formula (I), m = 1, n = i = 0, ring A ¹ is a 1,4-cyclohexylene group, Z ¹ is —CH ＝ CH—,
R ¹ is n- propyl group, Z ³ is -CH = CH- (CH2) 2
-, Wherein R ² is an ethenyl group): trans-4-propylcyclohexylmethyl iodide under a nitrogen atmosphere in a 1 liter three-necked flask equipped with a stirrer, thermometer and nitrogen inlet tube. 6g (71.2mmo
l) was suspended in 200 ml of THF, cooled to -30 ° C or lower with an acetone-dry ice refrigerant, and then potassium-
8.4 g (74.7 mmol) of t-butoxide was added, and the mixture was stirred for 2 hours while maintaining at -30 ° C or lower. Next, 4-((E) -4-) produced by the method described in Example 4
15.0 g of (trans-4-ethenylcyclohexyl) -1-butenyl) cyclohexylcarbaldehyde (5
A solution prepared by dissolving (4.7 mmol) in 60 ml of THF was added dropwise over 15 minutes while maintaining the same temperature, then the temperature was raised to room temperature over 30 minutes, and the mixture was further stirred at room temperature for 4 hours. After 100 ml of water was added to the reaction solution to terminate the reaction, the mixture was extracted three times with toluene (150 ml). The toluene layer was washed three times with water (100 ml), dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and concentrated. The concentrated residue was purified by silica gel chromatography using heptane as a developing solvent to obtain 13.7 g of colorless crystals.

In a 500 ml eggplant-shaped flask equipped with a cooling tube, 13.7 g of the colorless crystals obtained by the above operation were dissolved in 100 ml of a 1/1 mixed solvent of toluene / ethanol. 8.6 ml of normal hydrochloric acid was added, and the mixture was heated under reflux for 10 hours. After cooling the reaction solution to room temperature, 100 ml of water was added to terminate the reaction. The reaction solution was extracted twice with toluene (100 ml). The toluene layer was washed twice with water (100 ml),
The extract was washed once with a saturated aqueous sodium hydrogen carbonate solution (50 ml) and then twice with water (100 ml), dried over anhydrous magnesium sulfate, concentrated under reduced pressure to remove the solvent, and concentrated.
After the concentrated residue was purified by silica gel chromatography using heptane as a developing solvent, recrystallization from heptane was repeated to give trans-1-, the colorless crystalline title compound.
2.1 g of ethenyl-4-((E) -4-((E) -2- (trans-4- (trans-4-propylcyclohexyl) ethenyl) cyclohexyl) -3-butenyl) cyclohexane was obtained. ^The results of ¹ H-NMR and GC-MS strongly supported the structure of this compound. GC-MS: M ⁺ 396

The procedure was carried out according to the above-mentioned production method, using trans-4-alkylcyclohexylmethyl iodide having a different alkyl group in place of trans-4-propylcyclohexylmethyl iodide used in the above production method. The following compounds can be prepared: Trans-1-ethenyl-4-((E) -4-((E)
-2- (trans-4- (trans-4-methylcyclohexyl) ethenyl) cyclohexyl) -3-butenyl) cyclohexane trans-1-ethenyl-4-((E) -4-((E)
-2- (trans-4- (trans-4-ethylcyclohexyl) ethenyl) cyclohexyl) -3-butenyl) cyclohexane (No. 306) trans-1-ethenyl-4-((E) -4-((E)
-2- (trans-4- (trans-4-butylcyclohexyl) ethenyl) cyclohexyl) -3-butenyl) cyclohexane trans-1-ethenyl-4-((E) -4-((E)
-2- (trans-4- (trans-4-pentylcyclohexyl) ethenyl) cyclohexyl) -3-butenyl) cyclohexane trans-1-ethenyl-4-((E) -4-((E)
-2- (trans-4- (trans-4-hexylcyclohexyl) ethenyl) cyclohexyl) -3-butenyl) cyclohexane

Trans-1-ethenyl-4-((E)-
4-((E) -2- (trans-4- (trans-4-
Heptylcyclohexyl) ethenyl) cyclohexyl)
-3-butenyl) cyclohexane trans-1-ethenyl-4-((E) -4-((E)
-2- (trans-4- (trans-4-octylcyclohexyl) ethenyl) cyclohexyl) -3-butenyl) cyclohexane trans-1-ethenyl-4-((E) -4-((E)
-2- (trans-4- (trans-4-nonylcyclohexyl) ethenyl) cyclohexyl) -3-butenyl) cyclohexane trans-1-ethenyl-4-((E) -4-((E)
-2- (trans-4- (trans-4-decylcyclohexyl) ethenyl) cyclohexyl) -3-butenyl) cyclohexane

The following compounds can be produced by selecting various starting materials or reaction reagents in the above-mentioned production method and operating according to the above-mentioned production method. Trans-1-((E) -1-propenyl) -4-
((E) -4-((E) -2- (trans-4- (trans-4-ethylcyclohexyl) ethenyl) cyclohexyl) -3-butenyl) cyclohexane trans-1-((E) -1-propenyl) -4-
((E) -4-((E) -2- (trans-4- (trans-4-propylcyclohexyl) ethenyl) cyclohexyl) -3-butenyl) cyclohexane trans-1-((E) -1-propenyl) -4-
((E) -4-((E) -2- (trans-4- (trans-4-pentylcyclohexyl) ethenyl) cyclohexyl) -3-butenyl) cyclohexane trans-1-((E) -1-butenyl) -4-
((E) -4-((E) -2- (trans-4- (trans-4-ethylcyclohexyl) ethenyl) cyclohexyl) -3-butenyl) cyclohexane trans-1-((E) -1-butenyl) -4-
((E) -4-((E) -2- (trans-4- (trans-4-propylcyclohexyl) ethenyl) cyclohexyl) -3-butenyl) cyclohexane

Trans-1-((E) -1-butenyl)
-4-((E) -4-((E) -2- (trans-4-
(Trans-4-pentylcyclohexyl) ethenyl)
Cyclohexyl) -3-butenyl) cyclohexane trans-1- (3-butenyl) -4-((E) -4-
((E) -2- (trans-4- (trans-4-ethylcyclohexyl) ethenyl) cyclohexyl) -3-
(Butenyl) cyclohexane trans-1- (3-butenyl) -4-((E) -4-
((E) -2- (trans-4- (trans-4-propylcyclohexyl) ethenyl) cyclohexyl) -3
-Butenyl) cyclohexane trans-1- (3-butenyl) -4-((E) -4-
((E) -2- (trans-4- (trans-4-pentylcyclohexyl) ethenyl) cyclohexyl) -3
-Butenyl) cyclohexane trans-1-((E) -3-pentenyl) -4-
((E) -4-((E) -2- (trans-4- (trans-4-ethylcyclohexyl) ethenyl) cyclohexyl) -3-butenyl) cyclohexane trans-1-((E) -3-pentenyl) -4-
((E) -4-((E) -2- (trans-4- (trans-4-propylcyclohexyl) ethenyl) cyclohexyl) -3-butenyl) cyclohexane trans-1-((E) -3-pentenyl) -4-
((E) -4-((E) -2- (trans-4- (trans-4-pentylcyclohexyl) ethenyl) cyclohexyl) -3-butenyl) cyclohexane

Trans-1-ethenyl-4-((E)-
4-((E) -2- (trans-4- (trans-4-
Ethylcyclohexyl) ethenyl) cyclohexyl)-
1-butenyl) cyclohexane trans-1-ethenyl-4-((E) -4-((E)
-2- (trans-4- (trans-4-propylcyclohexyl) ethenyl) cyclohexyl) -1-butenyl) cyclohexane trans-1-ethenyl-4-((E) -4-((E)
-2- (trans-4- (trans-4-pentylcyclohexyl) ethenyl) cyclohexyl) -1-butenyl) cyclohexane trans-1-((E) -1-propenyl) -4-
((E) -4-((E) -2- (trans-4- (trans-4-ethylcyclohexyl) ethenyl) cyclohexyl) -1-butenyl) cyclohexane (No. 30)
8) trans-1-((E) -1-propenyl) -4-
((E) -4-((E) -2- (trans-4- (trans-4-propylcyclohexyl) ethenyl) cyclohexyl) -1-butenyl) cyclohexane (No. 3)
09)

Trans-1-((E) -1-propenyl) -4-((E) -4-((E) -2- (trans-
4- (trans-4-pentylcyclohexyl) ethenyl) cyclohexyl) -1-butenyl) cyclohexane trans-1-((E) -1-butenyl) -4-
((E) -4-((E) -2- (trans-4- (trans-4-ethylcyclohexyl) ethenyl) cyclohexyl) -1-butenyl) cyclohexane trans-1-((E) -1-butenyl) -4-
((E) -4-((E) -2- (trans-4- (trans-4-propylcyclohexyl) ethenyl) cyclohexyl) -1-butenyl) cyclohexane trans-1-((E) -1-butenyl) -4-
((E) -4-((E) -2- (trans-4- (trans-4-pentylcyclohexyl) ethenyl) cyclohexyl) -1-butenyl) cyclohexane trans-1- (3-butenyl) -4- ( (E) -4-
((E) -2- (trans-4- (trans-4-ethylcyclohexyl) ethenyl) cyclohexyl) -1-
Butenyl) cyclohexane (No. 310)

Trans-1- (3-butenyl) -4-
((E) -4-((E) -2- (trans-4- (trans-4-propylcyclohexyl) ethenyl) cyclohexyl) -1-butenyl) cyclohexane trans-1- (3-butenyl) -4- ( (E) -4-
((E) -2- (trans-4- (trans-4-pentylcyclohexyl) ethenyl) cyclohexyl) -1
-Butenyl) cyclohexane trans-1-((E) -3-pentenyl) -4-
((E) -4-((E) -2- (trans-4- (trans-4-ethylcyclohexyl) ethenyl) cyclohexyl) -1-butenyl) cyclohexane trans-1-((E) -3-pentenyl) -4-
((E) -4-((E) -2- (trans-4- (trans-4-propylcyclohexyl) ethenyl) cyclohexyl) -1-butenyl) cyclohexane (No. 3)
11) trans-1-((E) -3-pentenyl) -4-
((E) -4-((E) -2- (trans-4- (trans-4-pentylcyclohexyl) ethenyl) cyclohexyl) -1-butenyl) cyclohexane

Example 8 (Use Example 1) 4- (trans-4-propylcyclohexyl) benzonitrile 24% (weight, the same applies hereinafter) 4- (trans-4-pentylcyclohexyl) benzonitrile 36% 4- (trans The clearing point (Cp) of a nematic liquid crystal composition having a composition of -4-heptylcyclohexyl) benzonitrile 25% 4- (4-propylphenyl) benzonitrile 15% is 7
2.4 ° C. This liquid crystal composition was treated with a TN having a cell thickness of 9 μm.
The operation threshold voltage (V _th ) of the cell sealed in a cell (twisted nematic cell) is 1.78 V, and the dielectric anisotropy value (△
ε) is +11.0, and the refractive index anisotropy value (Δn) is 0.13.
7, and the viscosity at 20 ° C. (η ₂₀ ) is 27.0 mPa
-It was s. This liquid crystal composition was treated as a mother liquid crystal (hereinafter referred to as mother liquid crystal A).
And 85 parts by weight of 1-
Ethenyl-4- (4- (trans-4-pentylcyclohexyl) butyl) cyclohexane (Compound No. 5)
15 parts by weight were mixed. As a result of measuring the physical properties of this mixture, Cp: 71.5 ° C., V _th : 1.78 V, Δε:
9.4, Δn: 0.120, η ₂₀ : 20.1 mPa · s
Met. This composition was left in a freezer at −20 ° C. for 40 days, but no precipitation of crystals was observed.

Example 9 (Using Example 2) 85 parts by weight of the mother liquid crystal A shown in Example 8 and 1-ethenyl-4- (4- (trans-4-propylcyclohexyl) butyl) shown in Example 1 Cyclohexane (compound N
o. 3) 15 parts by weight were mixed. As a result of measuring the physical properties of this mixture, Cp: 65.7 ° C., V _th : 1.76.
V, Δε: 9.3, Δn: 0.121, η ₂₀ : 19.8
mPa · s. This composition was left in a freezer at −20 ° C. for 40 days, but no precipitation of crystals was observed.

COMPARATIVE EXAMPLE As a compound to be compared with the compound of the present invention, trans-4- (trans-4- (3 (E (I)), a compound described in JP-A-61-83136 described in the section of the prior art, was used. )-
Pentenyl) cyclohexyl) propylcyclohexane (a-1) and trans-4- (trans-4- (1
(E) -Pentenyl) cyclohexyl) ethylcyclohexane (a-2) was synthesized according to the method described in the publication.

[0177]

Embedded image

Liquid crystal compositions were prepared by mixing 85 parts by weight of the mother liquid crystal A with 15 parts by weight of the compounds (a-1) and (a-2), and measured for physical properties. Further, for the purpose of judging the compatibility, each prepared liquid crystal composition was left in a freezer at −20 ° C., and the time from the start of the standing until a crystal (solid) precipitated in the liquid crystal composition was measured. Table 1 shows the physical property values together with the measurement results of Example 9.

[0179]

[Table 1]

As can be seen from Table 1, the compound of the present invention (N
o. The composition using (3) has a very low viscosity in spite of the high clearing point, and its viscosity is reduced by about 30% from that of the base liquid crystal A by adding 15% to the base liquid crystal.
It turns out that 3) is a very excellent compound as a thickener. Also, the elastic constant ratio has a slightly larger value than the compositions using the compounds (a-1) and (a-2). Further, regarding the compatibility, in the liquid crystal composition prepared from the compounds (a-1) and (a-2), precipitation of crystals (solid) was observed within 3 weeks in a freezer at −20 ° C. No crystal precipitation was observed in the liquid crystal composition prepared from the compound of the present invention for 40 days or more, indicating that the compound of the present invention exhibits very good low-temperature compatibility. As described in the section of the prior art, since the liquid crystal compound is usually used as a liquid crystal composition, its compatibility is an important property. This is the most important characteristic in a liquid crystal display element used for a vehicle or the like. As can be seen from the above comparative test, the compound of the present invention has remarkably excellent low-temperature compatibility, shows a large elastic constant ratio, and has a very low viscosity, which is a feature not found in other compounds having a similar structure. Having.

Use Examples of Compounds of the Invention (Use examples 3 to 2)
2) is shown below. The compounds in the following use examples are indicated by abbreviations according to the rules shown in the following table. Further, T _NI described in the use examples is a nematic-isotropic liquid transition temperature (° C.), η
Indicates a viscosity (mPa · s), Δn indicates a refractive index anisotropy value, Δε indicates a dielectric anisotropy value, and Vth indicates a threshold voltage (V).

[0182]

[Table 2]

Use Example 3 V-H4H-2 (Compound No. 2) 5.0% 1V2-BEB (F, F) -C 5.0% 3-HB-C 25.0% 1-BTB-35 0.0% 2-BTB-1 10.0% 3-HH-4 6.0% 3-HHB-1 11.0% 3-HHB-3 9.0% 3-H2BTB-2 4.0% 3- H2BTB-3 4.0% 3-H2BTB-4 4.0% 3-HB (F) TB-2 6.0% 3-HB (F) TB-3 6.0% T _NI = 87.8 (° C.) ) Η = 15.0 (mPa · s) Δn = 0.161 Δε = 7.1 V _th = 2.10 (V)

Use Example 4 V-H4H-2 (Compound No. 2) 4.0% V-H4H-3 (Compound No. 3) 4.0% V-H4H-5 (Compound No. 5) 2.0 % V2-HB-C 12.0% 1V2-HB-C 12.0% 3-HB-C 24.0% 3-HB (F) -C 5.0% 2-BTB-1 2.0% 3 -HH-4 4.0% 2-HHB-C 3.0% 3-HHB-C 6.0% 3-HB (F) TB-2 8.0% 3-H2BTB-2 5.0% 3- H2BTB-3 5.0% 3-H2BTB-4 4.0% T _NI = 85.2 (° C.) η = 18.2 (mPa · s) Δn = 0.152 Δε = 8.6 V _th = 2. 00 (V)

Usage Example 5 V-H4H-5 (Compound No. 5) 3.0% 2O1-BEB (F) -C 5.0% 3O1-BEB (F) -C 15.0% 4O1-BEB (F ) -C 13.0% 5O1-BEB (F) -C 13.0% 2-HHB (F) -C 15.0% 3-HHB (F) -C 15.0% 3-HB (F) TB -2 4.0% 3-HB (F) TB-3 4.0% 3-HB (F) TB-4 4.0% 3-HHB-1 5.0% 3-HHB-O1 4.0% T _NI = 89.0 (° C.) η = 86.0 (mPa · s) Δn = 0.147 Δε = 30.8 V _th = 0.86 (V)

Use Example 6 V-H4H-2 (Compound No. 2) 5.0% V-H4H-3 (Compound No. 3) 5.0% 5-PyB-F 4.0% 3-PyB (F 1.)-F 4.0% 2-BB-C 5.0% 4-BB-C 4.0% 5-BB-C 5.0% 2-PyB-2 2.0% 3-PyB-2 0% 4-PyB-2 2.0% 6-PyB-O5 3.0% 6-PyB-O6 3.0% 3-PyBB-F 6.0% 4-PyBB-F 6.0% 5-PyBB -F 6.0% 3-HHB-1 6.0% 3-HHB-3 4.0% 2-H2BTB-2 4.0% 2-H2BTB-3 4.0% 2-H2BTB-4 5.0 % 3-H2BTB-2 5.0% 3-H2BTB-3 5.0% 3-H2BTB-4 5.0% T NI = 87.6 (℃) η = 30.2 (mPa s) Δn = 0.192 Δε = 6.0 V th = 2.35 (V)

Use Example 7 V-H4H-3 (Compound No. 3) 4.0% 3-DB-C 10.0% 4-DB-C 10.0% 2-BEB-C 12.0% 3- BEB-C 4.0% 3-PyB (F) -F 6.0% 3-HEB-O4 4.0% 4-HEB-O2 6.0% 5-HEB-O1 6.0% 3-HEB- O2 5.0% 5-HEB-O2 4.0% 5-HEB-5 5.0% 4-HEB-5 5.0% 10-BEB-2 4.0% 3-HHB-1 6.0% 3-HHEBB-C 3.0% 3-HBEBB-C 3.0% 5-HBEBB-C 3.0% T _NI = 68.4 (° C.) η = 37.9 (mPa · s) Δn = 0. 119 Δε = 11.4 V _th = 1.31 (V)

Use Example 8 V-H4H-3 (Compound No. 3) 5.0% V-H4H-5 (Compound No. 5) 2.0% 3-HB-C 18.0% 7-HB-C 3.0% 1O1-HB-C 10.0% 3-HB (F) -C 10.0% 2-PyB-2 2.0% 3-PyB-2 2.0% 4-PyB-2 2. 0% 1O1-HH-3 3.0% 2-BTB-O1 7.0% 3-HHB-1 7.0% 3-HHB-F 4.0% 3-HHB-O1 4.0% 3-HHB -3 5.0% 3-H2BTB-2 3.0% 3-H2BTB-3 3.0% 2-PyBH-3 4.0% 3-PyBH-3 3.0% 3-PyBB-2 3.0 % T _NI = 76.2 (° C.) η = 16.9 (mPa · s) Δn = 0.137 Δε = 7.9 V _th = 1.77 (V)

Use Example 9 V-H4H-3 (Compound No. 3) 5.0% 2O1-BEB (F) -C 5.0% 3O1-BEB (F) -C 12.0% 5O1-BEB (F ) -C 4.0% 1V2-BEB (F, F) -C 10.0% 3-HH-EMe 5.0% 3-HB-O2 15.0% 7-HEB-F 3.0% 3- HHEB-F 3.0% 5-HHEB-F 3.0% 3-HBEB-F 4.0% 2O1-HBEB (F) -C 2.0% 3-HBEB (F, F) -C 4.0 % 3-HHB-F 4.0% 3-HHB-O1 4.0% 3-HHB-3 13.0% 3-HEBEB-F 2.0% 3-HEBEB-1 2.0% T _NI = 73 9.9 (° C.) η = 34.1 (mPa · s) Δn = 0.107 Δε = 23.4 V _th = 0.99 (V)

Use Example 10 V-H4H-2 (Compound No. 2) 4.0% 2O1-BEB (F) -C 5.0% 3O1-BEB (F) -C 12.0% 5O1-BEB (F ) -C 4.0% 1V2-BEB (F, F) -C 16.0% 3-HB-O2 6.0% 3-HH-4 3.0% 3-HHB-F 3.0% 3- HHB-1 8.0% 3-HHB-O1 4.0% 3-HBEB-F 4.0% 3-HHEB-F 7.0% 5-HHEB-F 7.0% 3-H2BTB-2 4. 0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0% 3-HB (F) TB-2 5.0% T _NI = 90.1 (° C.) η = 40.6 (mPa · s) Δn = 0.142 Δε = 28.1 V _th = 1.00 (V)

Use Example 11 V-H4H-2 (Compound No. 2) 5.0% V-H4H-3 (Compound No. 3) 4.0% V-H4H-5 (Compound No. 5) 3.0 % 2-BEB-C 12.0% 3-BEB-C 4.0% 4-BEB-C 6.0% 3-HB-C 28.0% 3-HEB-O4 5.0% 4-HEB- O2 4.0% 5-HEB-O1 4.0% 3-HEB-O2 6.0% 5-HEB-O2 5.0% 3-HHB-1 10.0% 3-HHB-O1 4.0% T _NI = 61.2 (° C.) η = 22.7 (mPa · s) Δn = 0.108 Δε = 9.8 V _th = 1.36 (V)

Use Example 12 V-H4H-3 (Compound No. 3) 5.0% 2-BEB-C 10.0% 5-BB-C 12.0% 7-BB-C 7.0% 1- BTB-3 7.0% 2-BTB-1 10.0% 10-BEB-2 5.0% 10-BEB-5 12.0% 2-HHB-1 4.0% 3-HHB-F 0% 3-HHB-1 7.0% 3-HHB-O1 4.0% 3-HHB-3 13.0% T _NI = 66.9 (° C.) η = 17.8 (mPa · s) Δn = 0.156 Δε = 5.9 V _th = 1.87 (V)

Use Example 13 V-H4H-3 (Compound No. 3) 4.0% 3-HB (F) -C 5.0% 2O1-BEB (F) -C 5.0% 3O1-BEB (F 4.)-C 10.0% V-HB-C 10.0% 1V-HB-C 10.0% 2-BTB-O1 8.0% 3-HB-O2 8.0% V2-HH-3 0% V-HH-4 5.0% V-HHB-1 10.0% 1V2-HBB-2 10.0% 3-HHB-1 10.0% T _NI = 65.3 (° C.) η = 17 0.2 (mPa · s) Δn = 0.126 Δε = 9.4 V _th = 1.47 (V)

Use Example 14 V-H4H-2 (Compound No. 2) 5.0% V-H4H-3 (Compound No. 3) 5.0% V-H4H-5 (Compound No. 5) 3.0 % 2-HHB (F) -F 15.0% 3-HHB (F) -F 15.0% 5-HHB (F) -F 15.0% 2-H2HB (F) -F 8.8% 3 -H2HB (F) -F 4.4% 5-H2HB (F) -F 8.8% 2-HBB (F) -F 5.0% 3-HBB (F) -F 5.0% 5-HBB (F) -F 10.0% T _NI = 89.4 (° C.) η = 21.3 (mPa · s) Δn = 0.083 Δε = 4.4 V _th = 2.37 (V)

Use Example 15 V-H4H-2 (Compound No. 2) 6.0% 7-HB (F) -F 5.0% 5-H2B (F) -F 5.0% 3-HH-4 2.0% 3-HB-O2 7.0% 2-HHB (F) -F 10.0% 3-HHB (F) -F 10.0% 5-HHB (F) -F 10.0% 3 -H2HB (F) -F 5.0% 2-HBB (F) -F 3.0% 3-HBB (F) -F 3.0% 5-HBB (F) -F 6.0% 2-H2BB (F) -F 5.0% 3-H2BB (F) -F 6.0% 3-HHB-1 8.0% 3-HHB-O1 5.0% 3-HHB-3 4.0% T _NI = 86.3 (° C.) η = 18.9 (mPa · s) Δn = 0.091 Δε = 3.2 V _th = 2.69 (V)

Use Example 16 V-H4H-5 (Compound No. 5) 3.0% 7-HB (F, F) -F 3.0% 3-HB-O2 4.0% 2-HHB (F) -F 10.0% 3-HHB (F) -F 10.0% 5-HHB (F) -F 10.0% 2-HBB (F) -F 9.0% 3-HBB (F) -F 9.0% 5-HBB (F) -F 16.0% 2-HBB-F 4.0% 3-HBB-F 4.0% 5-HBB-F 3.0% 3-HBB (F, F ) -F 5.0% 5-HBB (F, F) -F 10.0% T _NI = 85.8 (° C.) η = 25.1 (mPa · s) Δn = 0.115 Δε = 5.6 V _th = 2.03 (V)

Use Example 17 V-H4H-3 (Compound No. 3) 5.0% 7-HB (F, F) -F 4.0% 3-H2HB (F, F) -F 12.0% 4 -H2HB (F, F) -F 10.0% 5-H2HB (F, F) -F 10.0% 3-HHB (F, F) -F 5.0% 4-HHB (F, F)- F 5.0% 3-HH2B (F, F) -F 15.0% 5-HH2B (F, F) -F 10.0% 3-HBB (F, F) -F 12.0% 5-HBB (F, F) -F 12.0% T _NI = 70.9 (° C.) η = 25.7 (mPa · s) Δn = 0.083 Δε = 8.1 V _th = 1.63 (V)

Use Example 18 V-H4H-3 (Compound No. 3) 3.0% 3-HB-CL 10.0% 5-HB-CL 4.0% 7-HB-CL 4.0% 1001- HH-5 2.0% 2-HBB (F) -F 8.0% 3-HBB (F) -F 8.0% 5-HBB (F) -F 14.0% 4-HHB-CL 0% 5-HHB-CL 8.0% 3-H2HB (F) -CL 4.0% 3-HBB (F, F) -F 10.0% 5-H2BB (F, F) -F 9.0 % 3-HB (F) VB-2 4.0% 3-HB (F) VB-3 4.0% T _NI = 90.8 (° C.) η = 20.5 (mPa · s) Δn = 0. 129 Δε = 4.9 V _th = 2.32 (V)

Use Example 19 V-H4H-2 (Compound No. 2) 4.0% 3-HHB (F, F) -F 7.0% 3-H2HB (F, F) -F 8.0% 4 -H2HB (F, F) -F 8.0% 5-H2HB (F, F) -F 8.0% 3-HBB (F, F) -F 21.0% 5-HBB (F, F)- F 20.0% 3-H2BB (F, F) -F 10.0% 5-HHBB (F, F) -F 3.0% 5-HHEBB-F 2.0% 3-HH2BB (F, F) −F 3.0% 1O1-HBBH-4 2.0% 1O1-HBBH-5 4.0% T _NI = 91.6 (° C.) η = 33.2 (mPa · s) Δn = 0.112 Δε = 8.7 V _th = 1.79 (V)

Use Example 20 V-H4H-2 (Compound No. 2) 5.0% V-H4H-3 (Compound No. 3) 5.0% 5-HB-F 5.0% 6-HB-F 6.0% 7-HB-F 7.0% 2-HHB-OCF3 7.0% 3-HHB-OCF3 11.0% 4-HHB-OCF3 7.0% 5-HHB-OCF3 5.0% 3 -HH2B-OCF3 4.0% 5-HH2B-OCF3 4.0% 3-HHB (F, F) -OCF3 5.0% 3-HBB (F) -F 10.0% 5-HBB (F)- F 10.0% 3-HH2B (F) -F 3.0% 3-HB (F) BH-3 3.0% 5-HBBH-3 3.0% T _NI = 91.2 (° C.) η = 15.8 (mPa · s) Δn = 0.093 Δε = 4.4 V _th = 2.43 (V)

Use Example 21 V-H4H-3 (Compound No. 3) 3.0% 2-HHB (F) -F 2.0% 3-HHB (F) -F 2.0% 5-HHB (F ) -F 2.0% 2-HBB (F) -F 6.0% 3-HBB (F) -F 6.0% 5-HBB (F) -F 10.0% 2-H2BB (F)- F 9.0% 3-H2BB (F) -F 9.0% 3-HBB (F, F) -F 25.0% 5-HBB (F, F) -F 19.0% 101-HBBH-4 2.0% 1O1-HBBH-5 5.0% T _NI = 89.7 (° C.) η = 32.8 (mPa · s) Δn = 0.132 Δε = 7.2 V _th = 1.92 (V )

Use Example 22 V-H4H-2 (Compound No. 2) 2.0% V-H4H-5 (Compound No. 5) 2.0% 3-H2HB (F, F) -F 6.0% 4-H2HB (F, F) -F 5.0% 5-H2HB (F, F) -F 5.0% 3-HH2B (F, F) -F 5.0% 3-HBB (F, F) -F 20.0% 5-HBB (F, F) -F 23.0% 3-HBEB (F, F) -F 4.0% 4-HBEB (F, F) -F 2.0% 5- HBEB (F, F) -F 2.0% 3-HHEB (F, F) -F 15.0% 4-HHEB (F, F) -F 4.0% 5-HHEB (F, F) -F 5.0% T _NI = 73.2 (° C.) η = 32.4 (mPa · s) Δn = 0.097 Δε = 11.1 V _th = 1.35 (V)

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location C09K 19/42 C09K 19/42 G02F 1/13 500 G02F 1/13 500 (72) Inventor Norihisa Hachiya 2-5-5 Aobadai, Ichihara City, Chiba Prefecture (72) Inventor Etsuo Nakagawa 8890 Goi, Ichihara City, Chiba Prefecture

Claims (15)

[Claims] 1. A compound of the general formula (1) (Wherein R ¹ and R ² are linear or branched and have 1 to 1 carbon atoms)
15 represents an alkyl group or an alkenyl group having 2 to 15 carbon atoms, wherein at least one of R ¹ and R ² is an alkenyl group, and in these groups, one or two or more non-adjacent CH 2 groups are represented by an oxygen atom, a sulfur atom, Atom or -C≡C-
A ring A ¹ , a ring A ² and a ring A ³
Is independently a 1,4-cyclohexylene group in which one or more CH2 groups on the ring may be substituted by an oxygen atom or a sulfur atom, or one or more CH groups on the ring is a nitrogen atom Represents an optionally substituted 1,4-phenylene group, and Z ¹ and Z ² are each independently —CH ² CH 2 —, —C
H2O -, - OCH2 -, - CH = CH -, - C≡C- or a single bond, Z ³ is - (CH2) 4 -, - CH = C
H- (CH2) 2-, -CH2-CH = CH-CH2- or-(CH2) 2-CH = CH-, m, n and i
Are independently 0 or 1). 2. In the general formula (1), m = n = i = 0
The compound according to claim 1, which is 3. The compound according to claim ² , wherein in the general formula (1), R ¹ is an alkyl group, R ² is an alkenyl group, and Z ³ is — (CH 2) 4 —. 4. In the general formula (1), R ¹ is an alkyl group, R ² is an alkenyl group, and Z ³ is —CH ＝ CH—
The compound according to claim 2, wherein (CH2) 2- or-(CH2) 2-CH = CH-. 5. In the general formula (1), m = 1 and n = i =
The compound according to claim 1, which is 0. 6. The compound according to claim 5, wherein in formula (1), R ¹ is an alkyl group, R ² is an alkenyl group, and Z ³ is — (CH 2) 4 —. 7. In the general formula (1), R ¹ represents an alkyl group, R ² represents an alkenyl group, and Z ³ represents —CH ＝ CH—.
The compound according to claim 5, wherein (CH2) 2- or-(CH2) 2-CH = CH-. 8. In the general formula (1), m = n = 1 and i =
The compound according to claim 1, which is 0. 9. The compound according to claim 8, wherein in the general formula (1), R ¹ represents an alkyl group, R ² represents an alkenyl group, and Z ³ represents — (CH 2) 4 —. 10. In the general formula (1), R ¹ represents an alkyl group, R ² represents an alkenyl group, and Z ³ represents —CH ＝ CH—.
9. The compound according to claim 8, wherein (CH2) 2- or-(CH2) 2-CH = CH-. 11. A liquid crystal composition comprising at least two components, comprising at least one compound represented by the general formula (1). 12. A composition comprising at least one alkenylcyclohexane derivative according to claim 1 as a first component, and a compound represented by the following general formula (2):
(3) and (4) (Wherein, R ³ represents an alkyl group having 1 to 10 carbon atoms, X ₁
Is F, Cl, OCF3, OCF2H, CF3, indicates CF2H or ^{CFH2, L 1, L 2,} L 3, and L ⁴ represent H or F independently of one another, Z4 and Z5 independently of one another -(CH2) 2-, -CH = CH- or a single bond, and a represents 1 or 2. A liquid crystal composition comprising at least one compound selected from the group consisting of: 13. A first component comprising at least one alkenylcyclohexane derivative according to claim 1 and a second component comprising a compound represented by the general formula (5):
(6), (7), (8) and (9) (Wherein, R ⁴ represents F, an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and in these groups, one or two or more non-adjacent methylene groups (-C
H2-) may be substituted by an oxygen atom (-O-), and ring A is trans-1,4-cyclohexylene, 1,4-phenylene, pyrimidine-2,5-diyl or 1, A 3-dioxane-2,5-diyl group; ring B is a trans-1,4-cyclohexylene group;
1,4-phenylene group or pyrimidine-2,5-diyl group, ring C represents trans-1,4-cyclohexylene group or 1,4-phenylene group, and Z ⁶ represents-(C
H2) 2 -, - COO- or a single bond, L ⁵ and L ⁶ represents H or F independently of one another, b and c represents 0 or 1, independently of one another, R ⁵ is a carbon L ⁷ represents H or F, d represents 0 or 1, R ⁶ represents an alkyl group having 1 to 10 carbon atoms, and ring D and ring E are independent of each other. Represents a trans-1,4-cyclohexylene group or a 1,4-phenylene group, Z ⁷ and Z ⁸ each independently represent —COO— or a single bond;
Z ⁹ represents —COO— or —C≡C—, and L ⁸ and L
⁹ independently represents H or F, X ² represents F, OCF
3, OCF2H, CF3, show CF2H or CFH2, X ² is OCF3, OCF2H, CF3, L ⁸ and L ⁹ when showing a CF2H or CFH2 both indicates H,
e, f and g each independently represent 0 or 1; R ⁷ and R ⁸ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms; In the group, one or more non-adjacent two or more methylene groups (-CH2-) may be substituted by an oxygen atom (-O-), and ring G is a trans-1,4-cyclohexylene group, 1,4 -Phenylene group or pyrimidine-
Represents a 2,5-diyl group, ring H represents a trans-1,4-cyclohexylene group or 1,4-phenylene group,
Z ¹⁰ is -C≡C -, - COO -, - (CH2) 2 -, - C
H = CH—C≡C— or a single bond, and Z ¹¹ is —CO
R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and one or two non-adjacent groups in these groups The above methylene group (—CH ₂ —) may be substituted by an oxygen atom (—O—), and the ring I is a trans-1,4-cyclohexylene group, 1,4-phenylene group or pyrimidine-2, A 5-diyl group; ring J is trans-1,4-
A cyclohexylene group, a 1,4-phenylene group or a pyrimidine-2,5-diyl group in which one or more hydrogen atoms on the ring may be substituted by F, and a ring K is trans-
Represents a 1,4-cyclohexylene group or a 1,4-phenylene group, and Z ¹² and Z ¹⁴ are each independently —COO
—, — (CH 2) 2 — or a single bond, and Z ¹³ is —CH
＝ CH—, —C≡C—, —COO— or a single bond, and h represents 0 or 1. A liquid crystal composition comprising at least one compound selected from the group consisting of: 14. The first component contains at least one alkenylcyclohexane derivative according to any one of claims 1 to 10, and as a part of the second component, the general formulas (2), (3) and (4). ), At least one compound selected from the group consisting of the general formulas (5), (6), (7), (8) and (9). At least one compound selected
A liquid crystal composition characterized by containing various types. 15. A liquid crystal display device comprising the liquid crystal composition according to claim 11.