JP2000355557A - Decahydronaphthalene derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound having at least one alkenyl group as a side chain and one or more trans-1,4-cyclohexylene groups, a wide nematic phase temperature range and a low refractive index anisotropy and useful for producing a liquid crystal composition capable of carrying out the low- voltage driving or high-speed response. SOLUTION: This compound is represented by formula I [R and R' are each a 1-12C alkyl or the like which may be substituted with F or a 1-7C alkoxy, cyano or the like; at least one is a 1-12C alkenyl which may be substituted with F or a 1-7C alkoxy, L and L' are each CH2CH2, a single bond or the like; m and n are each 0-2; the decahydronaphthalene ring is the trans- form; the 2,6-positions are the trans-configuration; the 1,4-positions of the cyclohexane ring are the trans-configuration], e.g. 2,6-di(3-butenyl)-trans- decahydronaphthalene. The compound represented by formula I is obtained by reacting a compound represented by formula III prepared by using a compound represented by formula II as a starting substance with a compound, etc., represented by formula IV several times and, as necessary, hydrolyzing and isomerizing the resultant compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel liquid crystalline compound, a decahydronaphthalene derivative, and a liquid crystal composition containing the same. These are useful for electro-optical liquid crystal displays, particularly as nematic liquid crystal materials having a wide temperature range.

[0002]

2. Description of the Related Art Liquid crystal display devices are used in various measuring instruments, such as watches and calculators, automobile panels, word processors, electronic notebooks, printers, computers, televisions, and the like. Typical liquid crystal display methods are TN (twisted nematic) type and S type.
TN (super twisted nematic) type, DS (dynamic light scattering) type,
There are GH (guest / host) type or FLC (ferroelectric liquid crystal), etc., and the driving method is generally multiplex driving instead of conventional static driving, and moreover, simple matrix method, recently active matrix method is practical. Has been

[0003] In accordance with these display methods and drive methods, various characteristics are required as liquid crystal materials. Above all, a wide temperature range is very important in most cases, but includes the maximum temperature of the nematic phase (T _NI ).
There and that a sufficiently high melting point (T _{C -N)} or smectic - nematic transition temperature (T _SN) contains the sufficiently low.

Also, compatibility with other liquid crystal compounds and general-purpose liquid crystal compositions is important. If the compatibility is poor, it is necessary to mix a very large number of liquid crystal compounds in order to avoid the risk of precipitation or phase separation, and the preparation of the composition requires a great deal of time and cost. I couldn't.

[0005] In addition, a sufficiently low driving voltage is also an important characteristic in many cases, and therefore, the threshold voltage (Vth) needs to be low.

Another important characteristic is that the response time is high. Therefore, it is required that the viscosity of the liquid crystal is as small as possible.

The refractive index anisotropy (Δn) is also an important characteristic, and various values are required depending on the display method. However, in the case of a liquid crystal element having a large cell thickness, which is easy to manufacture, the value is small. Values are often required.

To meet these demands, a large number of liquid crystal compounds have been synthesized so far, but not all of the problems have been solved, and liquid crystals having better properties for each of the above demands have not been solved. At present, compounds are required.

In general, a liquid crystal compound is structurally formed of a central skeleton (core) portion and side groups (side chains and polar groups). As the ring structure constituting the core portion, a 1,4-phenylene group (which may be substituted by fluorine) or a trans-
Including 1,4-cyclohexylene group, heteroaromatic ring such as pyridine-2,5-diyl group and pyrimidine-2,5-diyl group, dioxane-trans-1,4-diyl group and piperidine-1,4 -A saturated heterocyclic ring such as a diyl group,
Many are already known. However, usually a 1,4-phenylene group (which may be substituted by fluorine)
And a trans-1,4-cyclohexylene group and a small number of heteroaromatic rings, and a liquid crystal compound composed of these ring structures alone can sufficiently meet the required characteristics of a liquid crystal composition which is becoming increasingly sophisticated year by year. The fact is that it is gone.

It is known that the conversion of trans-1,4-cyclohexylene to trans-2,6-transdecahydronaphthylene improves liquid crystallinity. Moreover, since the trans-2,6-transdecahydronaphthylene group is a saturated ring containing no hetero atom such as an oxygen atom or a nitrogen atom, excellent stability can be expected. However, there have been few examples of trans-2,6-transdecahydronaphthalene derivatives reported so far, and their properties have been scarcely known.

Recently, we have 2- (3,5-difluoro-4-cyanophenyl) -trans-2,6-transdecahydronaphthalene derivative (A).

[0012]

Embedded image

Or a 2- (3,4,5-trifluorophenyl) -trans-2,6-transdecahydronaphthalene derivative (B)

[0014]

Embedded image

And other novel phenyldecahydronaphthalene derivatives which exhibit excellent liquid crystallinity, reduce threshold voltage (Vth), reduce refractive index anisotropy (Δn), and expand the temperature range of the nematic phase. It has excellent effect on other liquid crystal compounds and general-purpose liquid crystal compositions, and (A) is useful mainly for STN display, and (B) is useful mainly for TFT. Reported that there is.

In the liquid crystal compound, by introducing an alkenyl group instead of an alkyl group as a side chain,
It is known that it exhibits excellent effects such as improvement of liquid crystallinity, reduction of viscosity, and improvement of steepness (γ). We have:
For phenyldecahydronaphthalene derivatives such as (A) and (B), 2- (3,5-difluoro-4-cyanophenyl) -trans-2,6- in which an alkenyl group is introduced as a side chain instead of an alkyl group. Transdecahydronaphthalene derivative (C)

[0017]

Embedded image

Or (D) a 2- (3,4,5-trifluorophenyl) -trans-2,6-transdecahydronaphthalene derivative

[0019]

Embedded image

These phenyldecahydronaphthalene derivatives were synthesized, and it was reported that the liquid crystal properties were further improved as compared with (A) and (B).

On the other hand, in order to improve the liquid crystallinity, reduce the viscosity and reduce Δn, it is effective to introduce a trans-1,4-cyclohexylene group in addition to the decahydronaphthalene skeleton. I can imagine that it is a target. However, a liquid crystal compound having such a skeleton and having an alkenyl group as a side chain has not been known so far, including its production method.

[0022]

The problem to be solved by the present invention is to have at least one alkenyl group as a side chain and a trans-1,4-cyclohexylene group.
The present invention provides a novel liquid crystal compound which is a decahydronaphthalene derivative having at least one compound, and further using these compounds,
It has a wide nematic phase temperature range, low refractive index anisotropy, low voltage drive and high-speed response.
Another object of the present invention is to provide a liquid crystal composition suitable for driving N or TFT.

[0023]

According to the present invention, as means for solving the above problems, there are provided: General formula (I)

[0024]

Embedded image

(Wherein R and R ′ are each independently a fluorine atom or an alkyl group having 1 to 12 carbon atoms, an alkoxyl group which may be substituted by an alkoxyl group having 1 to 7 carbon atoms, An alkenyl group, an alkenyloxy group, an alkanoyloxy group or an alkoxycarbonyl group, or a cyano group, a cyanato group, a hydroxyl group or a carboxyl group, at least one of which is substituted by a fluorine atom or an alkoxyl group having 1 to 7 carbon atoms; L and L ′ each independently represent —CH ₂ CH ₂ —, —CH (CH ₃ ) C
H ₂ —, —CH ₂ CH (CH ₃ ) —, —CH ₂ O—, —OC
H ₂ —, —CF ₂ O—, —OCF ₂ —, —COO—, —O
CO-, -CH = CH-, -CF = CF-, -C≡C
_{-, - O (CH 2)} 3 -, - (CH 2) 3 O -, - (C
H ₂ ) ₄ -or a single bond, m and n each independently represent an integer of 0, 1 or 2; the decahydronaphthalene ring is in a trans form; And the 1,4-position of the cyclohexane ring is in a trans configuration. A decahydronaphthalene derivative represented by the formula: 2. In the general formula (I), L and L ′ are each independently —CH ₂ CH ₂ —, —CF ₂ O—, —OCF ₂ —,
2. The decahydronaphthalene derivative according to the above 1, wherein -CF = CF- or a single bond. 3. In the general formula (I), R and R ′ are each independently a fluorine atom or a carbon atom having 1 to 12 carbon atoms which may be substituted by an alkoxyl group having 1 to 7 carbon atoms.
Decahydro according to the above 1, wherein at least one of them represents an alkenyl group which may be substituted by a fluorine atom or an alkoxyl group having 1 to 7 carbon atoms. Naphthalene derivatives. 4. 2. The decahydronaphthalene derivative according to the above 1, wherein L and L ′ in formula (I) represent a single bond. 5. 2. The decahydronaphthalene derivative according to the above 1, wherein m + n represents 0, 1 or 2 in the general formula (I). 6. A liquid crystal composition containing the compound represented by the general formula (I) according to any one of the above 1 to 5. 7. 7. A liquid crystal device comprising the liquid crystal composition according to the above item 6 as a constituent element. Was found as a means for solving the above-mentioned problem.

[0026]

DESCRIPTION OF THE PREFERRED EMBODIMENTS An example of the present invention will be described below.

According to the present invention, there is provided a compound represented by the general formula (I):

[0028]

Embedded image

There is provided a decahydronaphthalene derivative represented by the formula:

In the formula, R and R ′ are each independently a fluorine atom or an alkyl group having 1 to 12 carbon atoms, an alkoxyl group, an alkenyl group which may be substituted by an alkoxyl group having 1 to 7 carbon atoms, Represents an alkenyloxy group, an alkanoyloxy group or an alkoxycarbonyl group, or a cyano group, a cyanato group, a hydroxyl group, or a carboxyl group, at least one of which may be substituted with a fluorine atom or an alkoxyl group having 1 to 7 carbon atoms. Which is preferably an alkyl group having 1 to 12 carbon atoms, an alkoxyl group, an alkenyl group or an alkenyloxy group which may be substituted by a fluorine atom or an alkoxyl group having 1 to 7 carbon atoms, 7 linear alkyl group, linear alkoxyl having 1 to 6 carbon atoms Group or vinyl group, trans-1
-Propenyl group, 3-butenyl group, trans-3-pentenyl group, trans-2-propenyloxy group, trans-2-butenyloxy group, trans-4-pentenyloxy group, trans-4-hexenyloxy group, trifluoromethoxy A group, a difluoromethoxy group, a 2-fluoroethenyl group, a 2,2-difluoroethenyl group, a methoxyethyl group or a methoxyethoxy group is more preferable, and a linear alkyl group having 1 to 7 carbon atoms, or a vinyl group, Most preferred are a trans-1-propenyl group, a 3-butenyl group, a trans-3-pentenyl group, a 2-fluoroethenyl group or a 2,2-difluoroethenyl group. L and L ′ are each independently —CH ₂ CH ₂ —,
_{-CH (CH 3) CH 2 -} , - CH 2 CH (CH 3) -, -
_{CH 2 O -, - OCH 2} -, - CF 2 O -, - OCF 2 -,
-COO-, -OCO-, -CH = CH-, -CF = C
F -, - C≡C -, - O (CH 2) 3 -, - (CH 2) 3 O
—, — (CH ₂ ) ₄ — or a single bond, but —CH ₂ C
_{H 2 -, - CF 2 O} -, - OCF 2 -, - CF = CF- or a single bond, more preferably a single bond is particularly preferred. m and n each independently represent an integer of 0 to 2;
Is preferably 0 to 2, more preferably 0 or 1, and most preferably 1. The decahydronaphthalene ring is in the trans form, the 2,6-position is in the trans configuration, and the 1,4-position in the cyclohexane ring is in the trans configuration. In the general formula (I), R, R ′, L,
Depending on the choice of L ′, m and n, a wide variety of compounds are included, but among them, the general formulas (Ia) to (I)
z)

[0031]

Embedded image

[0032]

Embedded image

[0033]

Embedded image

[0034]

Embedded image

The compound represented by the general formula (I)
Compounds of the formulas (a) to (If) are more preferred,
The compounds of a) and (If) are most preferred. Where R
^a and R ^b each independently represent a fluorine atom or an alkyl group having 1 to 12 carbon atoms which may be substituted by an alkoxyl group having 1 to 7 carbon atoms, an alkoxyl group,
Represents an alkenyl group or an alkenyloxy group, at least one of which represents a fluorine atom or an alkenyl group which may be substituted by an alkoxyl group having 1 to 7 carbon atoms, and a linear alkyl group having 1 to 7 carbon atoms, Linear alkoxyl group having 1 to 6 carbon atoms or vinyl group, trans-1-propenyl group, trans-3-butenyl group, trans-3-pentenyl group, trans-2-propenyloxy group, trans-2-butenyloxy Group, trans-4-pentenyloxy group, trans-4-hexenyloxy group, trifluoromethoxy group, difluoromethoxy group, 2-fluoroethenyl group, 2,2-difluoroethenyl group, 2-methoxyethyl group or 2 -Methoxyethoxy group is more preferable, and linear alkyl group having 1 to 7 carbon atoms, Rui vinyl group, trans-1-
Most preferred are a propenyl group, a 3-butenyl group, a trans-3-pentenyl group, a 2-fluoroethenyl group or a 2,2-difluoroethenyl group.

The compound of the general formula (I) has the general formula (II)
a)

[0037]

Embedded image

(Wherein, R, L and m have the same meanings as in the general formula (I)).

For example, when L ′ is —CH ₂ CH ₂ — and n is 1, the general formula (IIa)

[0040]

Embedded image

(Wherein, R, L and m have the same meanings as in the general formula (I))

[0042]

Embedded image

By reacting with a Wittig reactant represented by the formula (I), followed by hydrolysis with an acid and, if necessary, isomerization of the resulting cis / trans mixture with a base.

[0044]

Embedded image

(Wherein, R, L and m have the same meanings as in the general formula (I)). By repeating the reaction with the Wittig reagent

[0046]

Embedded image

Wherein R, L and m have the same meaning as in formula (I). The obtained compound represented by the general formula (IIc) is reduced to give an alcohol form, which is halogenated with a halogenating agent such as thionyl halide, phosphorus halide and the like.

[0048]

Embedded image

(In the formula, X represents a halogen group, and R, L and m have the same meaning as in the general formula (I).)
Can be obtained. From the obtained compound represented by the general formula (IId)

[0050]

Embedded image

(Where M is MgCl, MgBr, Mg
Represents a metal or a metal salt such as I, Li, Cu, CuLi, etc., and R, L and m represent the same meaning as in the general formula (I). ) Is prepared,

[0052]

Embedded image

By dehydration, reacetalization, hydrogenation, and deacetalization.

[0054]

Embedded image

(Wherein, R, L and m have the same meaning as in formula (I)). The obtained compound represented by the general formula (IIf) is

[0056]

Embedded image

Or

[0058]

Embedded image

(Wherein R ″ represents a fluorine atom or an alkyl group which may be substituted by an alkoxyl group having 1 to 7 carbon atoms), and is reacted several times with a Wittig reagent represented by the following formula: And the resulting cis / trans mixture is isomerized if necessary.

[0060]

Embedded image

(Wherein, R, R ′, L and m have the same meaning as in formula (I)).

Compound (I) of the present invention thus produced
Are shown in Table 2 together with their phase transition temperatures.

[0063]

[Table 1] (In the table, Cr indicates a crystal phase, N indicates a nematic phase, and I indicates an isotropic liquid phase.) Excellent effects obtained by adding the compound of the general formula (I) to the liquid crystal composition. Is as follows.

Compound (I-4) shown in Table 1

[0065]

Embedded image

The host liquid crystal composition (H) has a wide nematic phase temperature range, is low in viscosity, and can be used for active matrix driving.

[0067]

Embedded image

To the liquid crystal composition (H-
4) was prepared. The maximum temperature of the nematic phase (T _NI )
Was 116.4 ° C. This (H-4) was allowed to stand at −20 ° C. for 4 weeks, but no crystal precipitation or phase separation was observed. The crystal was cooled to -60 ° C for crystallization, and its melting point ( _TCN ) was measured to be -3 ° C.

Next, (H-4) was converted to a T cell having a cell thickness of 6.0 μm.
A liquid crystal element was prepared by filling in an N cell, and its electro-optical characteristics were measured at 20 ° C., and the results were as follows. Threshold voltage (Vth) 2.31 V Response time (τ) 27.4 ms Steepness (γ) 1.29 Dielectric anisotropy (Δε) 3.2 Refractive index anisotropy (Δn) 0.081 H) The electro-optical properties alone are as follows. Nematic phase maximum temperature (T _NI ) 116.7 ° C. Melting point (T _CN ) 11 ° C. Threshold voltage (Vth) 2.14 V Response time (τ) 25.3 ms Steepness (γ) 1.23 Dielectric anisotropy ( Δε) 4.8 Refractive index anisotropy (Δn) 0.090 Accordingly, by adding 20% by weight of (I-4),
Δn could be significantly reduced. Also, the drop of T _NI is about 2 ° C., Vth and γ hardly change,
Further, τ could be suppressed to an increase of about 2 msec.
The T _CN measured after cooling and crystallizing was −3 ° C.
And can be lowered significantly more than (H),
It can be seen that (I-4) was well dissolved in the host liquid crystal.

The voltage holding ratio of this device at room temperature and at 80 ° C. was measured, and all were very good and could be used sufficiently for driving an active matrix.

Next, a compound (R) having a similar structure, but in which the ring structure constituting the core portion is a trans-1,4-cyclohexylene group

[0072]

Embedded image

Was added to (H) in the same amount (20% by weight) to prepare a nematic liquid crystal composition (HR). A liquid crystal element was prepared in the same manner, and its electro-optical characteristics were measured. The results were as follows. Nematic phase upper limit temperature (T _NI ) 102.8 ° C. Melting point (T _CN )-threshold voltage (Vth) 2.29 V Response time (τ) 22.4 ms Steepness (γ) 1.21 Dielectric anisotropy (Δε) 3.6 The refractive index anisotropy (Δn) 0.089 (HR) has an improved response as compared to (H-4), while T _NI has an improved response as compared to (H-4). It can be seen that it has decreased. Further, Δn of (HR) was almost the same as that of (H) and was not reduced.

Therefore, the compound (I-4) of the present invention has an effect superior to the conventional compound (R) in improving the nematic phase temperature range and preparing a liquid crystal composition having a low Δn. You can see that there is.

As described above, the compound of the general formula (I) is very useful for preparing (a) a liquid crystal composition having an improved nematic phase temperature range and (ii) a low Δn.

From the above, the compound of the general formula (I) can be suitably used as a mixture with another nematic liquid crystal compound for a field effect display cell of TN type or STN type. The present invention thus provides a compound of the general formula (I)
The present invention also provides a liquid crystal composition containing at least one kind of the compound represented by the formula (1) as a component thereof, and a liquid crystal element comprising the same as a component.

The compound (I-4) does not have a strong polar group in the molecule and can easily obtain a large specific resistance and a high voltage holding ratio, and is used as a component of a liquid crystal material for driving an active matrix. It is also possible.

The present invention also provides a liquid crystal composition containing at least one compound represented by the general formula (I) as a constituent component.

The composition provided by the present invention contains at least one compound represented by the general formula (I) as the first component, and particularly includes the following second to fourth components as other components. It is preferable to contain at least one kind.

That is, the second component is a so-called fluorine-based (halogen-based) p-type liquid crystal compound and has the following general formula (A)
1) to (A3).

[0081]

Embedded image

In the above formula, R ^b represents an alkyl group having 1 to 12 carbon atoms, which may be linear or have a methyl or ethyl branch and may be a 3- to 6-membered cyclic group. may have a structure, any -CH present in the group ₂ -
Is -O-, -CH = CH-, -CH = CF-, -CF =
CH—, —CF ＝ CF— or —C≡C— may be replaced, and any hydrogen atom present in the group may be replaced by a fluorine atom or a trifluoromethoxy group, A linear alkyl group of Formulas 2 to 7,
A linear 1-alkenyl group having 2 to 7 carbon atoms, a linear 3-alkenyl group having 4 to 7 carbon atoms, and 1 carbon atom having a terminal substituted by an alkoxyl group having 1 to 3 carbon atoms
~ 5 alkyl groups are preferred. When an asymmetric carbon is generated by branching, the compound may be optically active or racemic.

Ring A, ring B and ring C are each independently substituted with a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group and at least one fluorine atom. 1,4-
Phenylene group, naphthalene-2,6-diyl group optionally substituted with one or more fluorine atoms, tetrahydronaphthalene-2,6-diyl group optionally substituted with one or more fluorine atoms, fluorine atom A 1,4-cyclohexenylene group optionally substituted with 1,3
-Dioxane-trans-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl, but trans-1,4-cyclohexylene,
Transdecahydronaphthalene-trans-2,6-diyl group, naphthalene-2,6-diyl group optionally substituted by a fluorine atom or 1,4-optionally substituted by one or two fluorine atoms Phenylene groups are preferred. In particular, when ring B is a trans-1,4-cyclohexylene group or transdecahydronaphthalene-trans-
When it is a 2,6-diyl group, ring A is trans-1,
It is preferably a 4-cyclohexylene group, and when ring C is a trans-1,4-cyclohexylene group or transdecahydronaphthalene-trans-2,6-diyl group, ring B and ring A are trans-1 , 4-cyclohexylene. In (A3), ring A is preferably a trans-1,4-cyclohexylene group.

L ^a , L ^b and L ^c are linking groups, each independently being a single bond, an ethylene group (—CH ₂ CH
₂ -), 1,2-propylene group (-CH (CH ₃₎ CH ₂
- and _{-CH 2 CH (CH 3) -} ), 1,4- butylene group, -COO -, - OCO -, - OCF 2 -, - CF 2 O
-, -CH = CH-, -CH = CF-, -CF = CH
-, -CF = CF-, -C≡C- or -CH = NN =
CH— represents a single bond, an ethylene group, a 1,4-butylene group, —COO—, —OCF ₂ —, —CF ₂ O—, or —CF.
＝ CF— or —C≡C— is preferred, and a single bond or an ethylene group is particularly preferred. In (A2), at least one of them preferably represents a single bond in (A3).

Ring Z is an aromatic ring and has the following general formula (IX)
a) to (IXc).

[0086]

Embedded image

In the formula, Y ^{a to} Y ^j each independently represent a hydrogen atom or a fluorine atom.
At least one of Y ^a and Y ^b is preferably a fluorine atom, in (IXb), it is preferable that at least one Y ^d to Y ^f is a fluorine atom, in particular Y ^d is a fluorine atom Is more preferred.

[0088] end group P ^a represents a fluorine atom, a chlorine atom, trifluoromethoxy group, difluoromethoxy group, trifluoromethyl group or difluoromethyl group or a carbon atoms substituted by two or more fluorine atoms 2 or 3
Represents an alkoxyl group, an alkyl group, an alkenyl group or an alkenyloxy group, preferably a fluorine atom, a trifluoromethoxy group or a difluoromethoxy group, and particularly preferably a fluorine atom.

In (A2), the compound of the general formula (I) of the present invention is excluded.

The third component is a so-called cyano-based p-type liquid crystal compound, which is a compound represented by the following formulas (B1) to (B3).

[0091]

Embedded image

In the above formula, R ^c represents an alkyl group having 1 to 12 carbon atoms, which may be linear or have a methyl or ethyl branch, and may be a 3- to 6-membered cyclic group. may have a structure, any -CH present in the group ₂ -
Is -O-, -CH = CH-, -CH = CF-, -CF =
CH—, —CF ＝ CF— or —C≡C— may be replaced, and any hydrogen atom present in the group may be replaced by a fluorine atom or a trifluoromethoxy group, A linear alkyl group of Formulas 2 to 7,
A linear 1-alkenyl group having 2 to 7 carbon atoms, a linear 3-alkenyl group having 4 to 7 carbon atoms, and 1 carbon atom having a terminal substituted by an alkoxyl group having 1 to 3 carbon atoms
~ 5 alkyl groups are preferred. When an asymmetric carbon is generated by branching, the compound may be optically active or racemic.

Ring D, ring E and ring F are each independently substituted with a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group and at least one fluorine atom. 1,4-
Phenylene group, naphthalene-2,6-diyl group optionally substituted with one or more fluorine atoms, tetrahydronaphthalene-2,6-diyl group optionally substituted with one or more fluorine atoms, fluorine atom A 1,4-cyclohexenylene group optionally substituted with 1,3
-Dioxane-trans-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl, but trans-1,4-cyclohexylene,
Transdecahydronaphthalene-trans-2,6-diyl group, naphthalene-2,6-diyl group optionally substituted by a fluorine atom or 1,4-optionally substituted by one or two fluorine atoms Phenylene groups are preferred. In particular, when ring E is a trans-1,4-cyclohexylene group or transdecahydronaphthalene-trans-
When it is a 2,6-diyl group, ring D is trans-1,
It is preferably a 4-cyclohexylene group, and when ring F is a trans-1,4-cyclohexylene group or transdecahydronaphthalene-trans-2,6-diyl group, ring D and ring E are trans-1 , 4-cyclohexylene. In (B3), ring D is preferably a trans-1,4-cyclohexylene group.

L ^d , ^Le and L ^f are linking groups, each independently being a single bond, an ethylene group (—CH ₂ CH
₂ -), 1,2-propylene group (-CH (CH ₃₎ CH ₂
- and _{-CH 2 CH (CH 3) -} ), 1,4- butylene group, -COO -, - OCO -, - OCF 2 -, - CF 2 O
-, -CH = CH-, -CH = CF-, -CF = CH
-, - CF = CF -, - C≡C -, - OCH 2 -, - C
H ₂ O-, or represent a -CH = NN = CH-, a single bond, an ethylene _{group, -COO -, - OCF 2 -} , - CF 2 O
—, —CF ＝ CF— or —C≡C— is preferred, and a single bond, an ethylene group or —COO— is particularly preferred. In (B2), at least one of them is (B2)
In 3), at least two of them preferably represent a single bond.

Ring Y is an aromatic ring and has the following general formula (IX)
d) to (IXf).

[0096]

Embedded image

In the formula, Y ^{h to} Y ⁿ each independently represent a hydrogen atom or a fluorine atom, and in (IXe),
Y ⁿ and Y ^o are preferably hydrogen atoms. The terminal group Pa represents ^a cyano group (—CN), a cyanato group (—OCN) or —C≡CCN, and a cyano group is preferable.

In (B2), the compound of the general formula (I) of the present invention is excluded.

The fourth component has a dielectric anisotropy of about 0.
It is a so-called n-type liquid crystal, and has the following general formulas (C1) to (C
It consists of the compound shown in 3).

[0100]

Embedded image

In the above formula, R ^d and R ^e each independently represent an alkyl group having 1 to 12 carbon atoms, which may be linear or have a methyl or ethyl branch; may have a cyclic structure having 3 to 6-membered ring, any -CH ₂ present in the group - is -O -, - CH = CH-,
May be replaced by —CH ＝ CF—, —CF ＝ CH—, —CF ＝ CF— or —C≡C—, and any hydrogen atom present in the group is replaced by a fluorine atom or a trifluoromethoxy group , But may have 1 carbon atom
To 7 linear alkyl groups, 2 to 7 carbon atoms, linear 1
An alkenyl group, a linear 3-alkenyl group having 4 to 7 carbon atoms, a linear alkoxyl group having 1 to 3 carbon atoms, or 1 carbon atom having a terminal substituted by an alkoxyl group having 1 to 3 carbon atoms. 5 to 5 linear alkyl groups are preferred,
Further, at least one is a linear alkyl group having 1 to 7 carbon atoms, a linear 1-alkenyl group having 2 to 7 carbon atoms or a linear 3-alkenyl group having 4 to 7 carbon atoms. Particularly preferred.

Ring G, ring H, ring I and ring J each independently represent a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group, 1-2 fluorine atoms. 1,4-phenylene group which may be substituted by an atom or a methyl group, naphthalene-2 which may be substituted by one or more fluorine atoms,
6-diyl group, tetrahydronaphthalene-2,6-diyl group optionally substituted by 1 to 2 fluorine atoms, 1,4-cyclohexenylene optionally substituted by 1 to 2 fluorine atoms Group, 1,3-dioxane-
Represents a trans-2,5-diyl group, a pyrimidine-2,5-diyl group or a pyridine-2,5-diyl group, and in each compound, a trans-decahydronaphthalene-trans-2,6-diyl group; A naphthalene-2,6-diyl group which may be substituted by the above fluorine atom,
Tetrahydronaphthalene-2,6-diyl group optionally substituted by 1 to 2 fluorine atoms, 1,4-cyclohexenylene group optionally substituted by fluorine atom, 1,3-dioxane-trans- 2,5-diyl group, pyrimidine-2,5-diyl group or pyridine-
It is preferred that the number of 2,5-diyl groups is one or less, and the other rings are trans-1,4-cyclohexylene groups or 1,4, which may be substituted by one or two fluorine atoms or methyl groups. -Preferably a phenylene group.

L ^g , L ^h and L ⁱ are linking groups, each independently being a single bond, an ethylene group (—CH ₂ CH
₂ -), 1,2-propylene group (-CH (CH ₃₎ CH ₂
- and _{-CH 2 CH (CH 3) -} ), 1,4- butylene group, -COO -, - OCO -, - OCF 2 -, - CF 2 O
-, -CH = CH-, -CH = CF-, -CF = CH
-, -CF = CF-, -C≡C- or -CH = NN =
It represents a CH-, single bond, ethylene group, 1,4-butylene group, -COO -, - OCO -, - OCF 2 -, - CF 2
O-, -CF = CF-, -C≡C- or -CH = NN
ＣＨCH— is preferred, and in (C2), at least one of them preferably represents a single bond in (C3).

In the compound (C2), the compound of the formula (I) of the present invention is excluded.

The more preferred embodiment of (C1) can be represented by the following general formulas (C1a) to (C1h).

[0106]

Embedded image

In the above formulas, R ^f and R ^g are each independently a linear alkyl group having 1 to 7 carbon atoms, a linear 1-alkenyl group having 2 to 7 carbon atoms, -C7 straight-chain 3-alkenyl group, C1-C3 straight-chain alkoxyl group or C1-C5 straight-chain alkyl substituted at the terminal with an C1-C3 alkoxyl group At least one of which is a linear alkyl group having 1 to 7 carbon atoms, a linear 1-alkenyl group having 2 to 7 carbon atoms or a linear 3-alkenyl group having 4 to 7 carbon atoms Represents However, when ring G1 to ring G8 are aromatic rings,
The corresponding R ^f is a group represented by the corresponding R ^g when the ring H1 to the ring H8 are an aromatic ring except for a 1-alkenyl group and an alkoxyl group.
Excludes a 1-alkenyl group and an alkoxyl group.

Ring G1 and ring H1 each independently represent a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group,
1,4-phenylene group optionally substituted by two fluorine atoms or methyl groups, naphthalene-2,6-diyl group optionally substituted by one or more fluorine atoms, 1-2 fluorine atoms A tetrahydronaphthalene-2,6-diyl group optionally substituted with 1,4-cyclohexenylene group optionally substituted with 1 to 2 fluorine atoms, 1,3-dioxane-trans-
Represents a 2,5-diyl group, a pyrimidine-2,5-diyl group or a pyridine-2,5-diyl group, and in each compound, transdecahydronaphthalene-trans-2,
6-diyl group, naphthalene-2,6-diyl group optionally substituted by one or more fluorine atoms, tetrahydronaphthalene-2,6-diyl group optionally substituted by one or two fluorine atoms A 1,4-cyclohexenylene group optionally substituted by a fluorine atom, 1,3
-Dioxane-trans-2,5-diyl group, pyrimidine-2,5-diyl group or pyridine-2,5-diyl group is preferably one or less, in which case the other ring is trans-1,2 4-cyclohexylene group or 1
A 1,4-phenylene group which may be substituted by 2 to 2 fluorine atoms or methyl groups. Ring G2 and ring H2 each independently represent a trans-1,4-cyclohexylene group, transdecahydronaphthalene-trans-
2,6-diyl group, 1,4-phenylene group optionally substituted by 1 to 2 fluorine atoms or methyl groups, naphthalene-2,6-optionally substituted by 1 or more fluorine atoms Diyl group, tetrahydronaphthalene which may be substituted by 1 to 2 fluorine atoms
A 2,6-diyl group, a transdecahydronaphthalene-trans-2,6-diyl group, a naphthalene-2,6-diyl group optionally substituted by one or more fluorine atoms, Tetrahydronaphthalene which may be substituted by 1 to 2 fluorine atoms
The number of 2,6-diyl groups is preferably one or less, in which case the other ring may be substituted by a trans-1,4-cyclohexylene group or one or two fluorine atoms or methyl groups. 1,4-phenylene group.
Ring G3 and ring H3 are each independently a 1,4-phenylene group optionally substituted with 1 to 2 fluorine atoms or a methyl group, and a naphthalene-2 optionally substituted with 1 or more fluorine atoms. , 6-diyl group, 1
Represents a tetrahydronaphthalene-2,6-diyl group which may be substituted by two or more fluorine atoms, and a naphthalene-2,6-diyl group which may be substituted by one or more fluorine atoms in each compound It is preferable that the number of tetrahydronaphthalene-2,6-diyl groups which may be substituted by one or two fluorine atoms is one or less.

The more preferable form of (C2) can be represented by the following general formulas (C2a) to (C2m).

[0110]

Embedded image

In the above formula, ring G1, ring G2, ring G3, ring H
1, ring H2 and ring H3 have the same meanings as described above, ring I1 has the same meaning as ring G1, ring I2 has the same meaning as ring G2, and ring I3 has the same meaning as ring G3. In each of the above compounds, a transdecahydronaphthalene-trans-2,6-diyl group, a naphthalene-2,6-diyl group which may be substituted by one or more fluorine atoms, 1-2 fluorine atoms A tetrahydronaphthalene-2,6-diyl group optionally substituted with a 1,4-cyclohexenylene group optionally substituted with a fluorine atom, a 1,3-dioxane-trans-2,5-diyl group, Pyrimidine-2,
It is preferable that the number of 5-diyl group or pyridine-2,5-diyl group is one or less, and in that case, the other ring is trans-1,4-cyclohexylene group or 1-2 fluorine atoms or methyl group. Is a 1,4-phenylene group which may be substituted by

Next, a more preferred embodiment of (C3) can be represented by the following general formulas (C3a) to (C3f).

[0113]

Embedded image

In the above formula, ring G1, ring G2, ring H1, ring H
2, Ring I1 and Ring I2 have the same meanings as described above, and Ring J1 has the same meaning as Ring G1 and Ring J2 has the same meaning as Ring G2. Further, in each of the above compounds, a transdecahydronaphthalene-trans-2,6-diyl group, a naphthalene which may be substituted with one or more fluorine atoms,
2,6-diyl group, tetrahydronaphthalene-2,6-diyl group optionally substituted by 1 to 2 fluorine atoms, 1,4-optionally substituted by fluorine atom
The number of cyclohexenylene groups, 1,3-dioxane-trans-2,5-diyl groups, pyrimidine-2,5-diyl groups or pyridine-2,5-diyl groups is preferably one or less. The other ring is trans-1,4-
A cyclohexylene group or a 1,4-phenylene group which may be substituted by one or two fluorine atoms or a methyl group.

[0115]

EXAMPLES Examples of the present invention are shown below to further explain the present invention. However, the present invention is not limited to these examples. Example 1 Synthesis of 2,6-di (3-butenyl) transdecahydronaphthalene (I-1)

[0116]

Embedded image

(1-a) Synthesis of transdecahydronaphthalene-2,6-dione 21 g of transdecahydronaphthalene-2,6-dione monoethylene acetal was dissolved in 110 mL of toluene, and 50 mL of formic acid was added thereto. Stirred. Water was added, the organic layer was separated, washed with water, saturated aqueous sodium bicarbonate solution and saturated saline in this order, dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain transdecahydronaphthalene-2,6-dione. 16 g of a pale yellow solid was obtained. (1-b) Synthesis of transdecahydronaphthalene-2,6-dicarbaldehyde The transdecahydronaphthalene- obtained in (1-a)
16 g of 2,6-dione tetrahydrofuran (THF)
An 80 mL solution was prepared by adding 72 g of methoxymethyltriphenylphosphonium chloride and 26 g of potassium t-butoxide to TH.
In a Wittig reagent prepared in F290 mL,
The solution was added dropwise while cooling to 10 ° C or lower. After returning to room temperature and stirring for 4 hours, water and hexane were added, the organic layer was separated, washed with water, and the solvent was distilled off. The obtained pale yellow oil was washed with TH
F in 90 mL, add 90 mL of 10% hydrochloric acid and add
Heated to reflux for an hour. After returning to room temperature, the organic layer was separated, and the aqueous layer was extracted with ethyl acetate. The organic layers were combined, washed with a saturated aqueous solution of sodium bicarbonate, water and saturated saline in this order, and the solvent was distilled off. The obtained pale yellow solid was treated with methanol 85m
L and cooled to 10 ° C. or lower, 10 mL of a 10% aqueous sodium hydroxide solution was added. After stirring for 2.5 hours, the temperature was returned to room temperature, the solvent was distilled off, the obtained pale yellow solid was washed with water, recrystallized from hexane, and 16 g of transdecahydronaphthalene-2,6-dicarbaldehyde white solid was obtained.
I got (1-c) Synthesis of 2,6-di (3-oxopropyl) transdecahydronaphthalene The transdecahydronaphthalene- obtained in (1-b)
The reaction of 16 g of 2,6-dicarbaldehyde with a Wittig reagent similar to that of (1-b) was further repeated twice to obtain 15 g of a pale yellow solid of 2,6-di (3-oxopropyl) transdecahydronaphthalene. I got (1-d) Synthesis of 2,6-di (3-butenyl) transdecahydronaphthalene THF85 of 15 g of 2,6-di (3-oxopropyl) transdecahydronaphthalene obtained in (1-c)
mL solution was added to methyltriphenylphosphonium iodide 6
0 g and 18 g of potassium t-butoxide in THF 30
In a Wittig reagent prepared in 0 mL solution, 1
The solution was added dropwise while cooling to 0 ° C or lower. After returning to room temperature and stirring for 4 hours, water and hexane were added, the organic layer was separated, washed with water, and the solvent was distilled off. Purification by silica gel column chromatography (hexane) gave 6 g of a colorless oil of 2,6-di (3-butenyl) transdecahydronaphthalene (I-1). Example 2 Synthesis of 2- (2-methoxy) ethoxy-6-vinyltransdecahydronaphthalene (I-2)

[0118]

Embedded image

(2-a) Synthesis of 6-hydroxytransdecahydronaphthalen-2-one ethylene acetal 21 g of transdecahydronaphthalene-2,6-dione monoethylene acetal was dissolved in 110 mL of methanol, and cooled to 10 ° C. or lower. While adding 4 g of sodium borohydride little by little, the mixture was stirred at room temperature for 1 hour. Water was added, extracted with ethyl acetate, washed with water and saturated saline in this order, dried over anhydrous sodium sulfate, and the solvent was distilled off.
19 g of a pale yellow oily product of hydroxytransdecahydronaphthalen-2-one ethylene acetal was obtained. (2-b) Synthesis of 6- (2-methoxyethoxy) transdecahydronaphthalen-2-one ethylene acetal 19 g of 6-hydroxytransdecahydronaphthalen-2-one ethylene acetal obtained in (2-a) , N-dimethylformamide (DMF) 95 mL in 60% sodium hydride 37 in 185 mL DMF.
g was suspended and added dropwise while cooling to 10 ° C. or lower. After returning to room temperature and stirring for 30 minutes, 33 g of 2-methoxyethyl iodide was added to DMF 70 m while cooling to 10 ° C. or lower.
The L solution was added dropwise. After heating and stirring at 50 ° C. for 8 hours, water and ethyl acetate were added, the organic layer was separated, washed with water and saturated saline, dried over anhydrous sodium sulfate, and the solvent was distilled off. Hexane)
Then, 11 g of a pale yellow oily substance of 6- (2-methoxyethoxy) transdecahydronaphthalen-2-one ethylene acetal was obtained. (2-c) Synthesis of 6- (2-methoxyethoxy) transdecahydronaphthalen-2-one 6- (2-methoxyethoxy) transdecahydronaphthalen-2-one ethylene acetal obtained in (2-b) 11 g was deacetalized in the same manner as in (1-a),
9 g of a white solid of 6- (2-methoxyethoxy) transdecahydronaphthalen-2-one was obtained. (2-d) Synthesis of 6- (2-methoxyethoxy) transdecahydronaphthalen-2-carbaldehyde 9 g of 6- (2-methoxyethoxy) transdecahydronaphthalen-2-one obtained in (2-c) To (1-
reacting with the same Wittig reagent as in b),
8 g of a white solid of (2-methoxyethoxy) transdecahydronaphthalene-2-carbaldehyde was obtained. (2-e) Synthesis of 2- (2-methoxy) ethoxy-6-vinyltransdecahydronaphthalene 8 g of 6- (2-methoxyethoxy) transdecahydronaphthalene-2-carbaldehyde obtained in (2-d)
Was reacted with the same Wittig reactant as (1-d) to obtain 3 g of 2- (2-methoxy) ethoxy-6-vinyltransdecahydronaphthalene (I-2) as a colorless oil. Example 3 Synthesis of 2- (2-methoxyethyl) -6- (trans-3-pentenyl) transdecahydronaphthalene (I-3)

[0120]

Embedded image

(3-a) Synthesis of 6- (2-methoxyethyl) transoctahydronaphthalen-2-one ethylene acetal In a suspension of 3 g of metallic magnesium in 15 mL of THF, 26 g of 2-methoxyethyl iodide was suspended. THF11
The 0 mL solution was added dropwise to prepare a Grignard reagent.
While cooling the solution to 10 ° C. or less, transdecahydronaphthalene-2,6-dione monoethylene acetal 20
g of THF (60 mL) was added dropwise, and the mixture was returned to room temperature and stirred for 1 hour. After adding a saturated ammonium chloride aqueous solution,
The organic layer was separated, washed with saturated saline, dried over anhydrous sodium sulfate, and the solvent was distilled off. The obtained oil was dissolved in toluene (120 mL), p-toluenesulfonic acid monohydrate (3 g) was added, and the mixture was heated and refluxed for 4 hours until there was no more distilled water in a device equipped with a water separator. In addition, the mixture was heated and refluxed for 4 hours until the distilled water disappeared. After cooling to room temperature, water was added, the organic layer was separated, washed with a saturated aqueous solution of sodium hydrogencarbonate, water and saturated saline in this order, dried over anhydrous sodium sulfate, and the solvent was distilled off. 9 g of a pale yellow oil of methoxyethyl) transoctahydronaphthalen-2-one ethylene acetal was obtained. (3-b) Synthesis of 6- (2-methoxyethyl) transdecahydronaphthalen-2-one ethylene acetal 6- (2-methoxyethyl) transoctahydronaphthalen-2-one obtained in (3-a) 9 g of ethylene acetal was dissolved in 50 mL of ethyl acetate, 1 g of 5% palladium-carbon was added, and hydrogenated at room temperature for 6 hours. The catalyst was filtered through celite, and the solvent was distilled off to obtain 9 g of 6- (2-methoxyethyl) transdecahydronaphthalen-2-one ethylene acetal as a pale yellow oil. (3-c) Synthesis of 6- (2-methoxyethyl) transdecahydronaphthalen-2-one 6- (2-methoxyethyl) transdecahydronaphthalen-2-one ethylene acetal obtained in (3-b) 9 g was deacetalized in the same manner as in (1-a) to give 6-
8 g of a white solid of (2-methoxyethyl) transdecahydronaphthalen-2-one was obtained. (3-d) Synthesis of 6- (2-methoxyethyl) transdecahydronaphthalen-2-carbaldehyde 8 g of 6- (2-methoxyethyl) transdecahydronaphthalen-2-one obtained in (3-c) To (1-b)
Reacts with the same Wittig reagent to form 6- (2-
Methoxyethyl) transdecahydronaphthalene-2-
8 g of a white solid of carbaldehyde was obtained. (3-e) Synthesis of 2- (2-methoxyethyl) -6- (3-oxopropyl) transdecahydronaphthalene 6- (2-methoxyethyl) transdecahydronaphthalene obtained in (3-d) The reaction of 8 g of 2-carbaldehyde with a Wittig reagent similar to (1-b) was repeated twice more to give 2- (2-methoxyethyl) -6.
9 g of a pale yellow solid of-(3-oxopropyl) transdecahydronaphthalene was obtained. (3-f) Synthesis of 2- (2-methoxyethyl) -6- (trans-3-pentenyl) transdecahydronaphthalene 2- (2-methoxyethyl) -6 obtained in (3-e)
A solution of 9 g of-(3-oxopropyl) transdecahydronaphthalene in 100 mL of THF was dropped into a Wittig reagent prepared from 18 g of ethyltriphenylphosphonium bromide and 6 g of potassium t-butoxide in 90 mL of THF while cooling to 10 ° C or lower. did. After returning to room temperature and stirring for 4 hours, water and hexane were added, and the organic layer was separated.
Washed with water and evaporated the solvent. The obtained pale yellow solid was dissolved in 90 mL of toluene, and 8 g of sodium benzenesulfinate monohydrate and 15 mL of 10% hydrochloric acid were added thereto to give 2
The mixture was refluxed for 0 hours. The organic layer was separated, washed with water, a saturated aqueous solution of sodium hydrogen carbonate and saturated saline in this order, dried over anhydrous sodium sulfate, and the solvent was distilled off. Purified by silica gel column chromatography (hexane), -70
The crystals were recrystallized from ethanol at a temperature of not more than C to give 3 g of a colorless oil of 2- (2-methoxyethyl) -6- (trans-3-pentenyl) transdecahydronaphthalene (I-3). Example 4 2- (trans-4-propylcyclohexyl) -6-vinyltransdecahydronaphthalene (I
Synthesis of -4)

[0122]

Embedded image

(4-a) 6- (trans-4-propylcyclohexyl) transdecahydronaphthalene-2-
Synthesis of carbaldehyde 28-g of 6- (trans-4-propylcyclohexyl) transdecahydronaphthalen-2-one (1-b)
To give 28 g of 6- (trans-4-propylcyclohexyl) transdecahydronaphthalene-2-carbaldehyde as a white solid. (4-b) Synthesis of 2- (trans-4-propylcyclohexyl) -6-vinyltransdecahydronaphthalene 6- (trans-4-propylcyclohexyl) transdecahydronaphthalene-2 obtained in (4-a) 28 g of carbaldehyde were reacted with the same Wittig reagent as in (1-d) to give 10 g of 2- (trans-4-propylcyclohexyl) -6-vinyltransdecahydronaphthalene (I-4) white solid. . Example 5 Synthesis of 2- (trans-4-propylcyclohexyl) -6- (trans-1-propenyl) transdecahydronaphthalene (I-5)

[0124]

Embedded image

6- (trans-4) obtained in (4-a)
-Propylcyclohexyl) transdecahydronaphthalene-2-carbaldehyde (12 g) was reacted with a Wittig reagent similar to (3-f), treated with benzenesulfinic acid, and treated with 2- (trans-4-propylcyclohexyl) -6- 4 g of a white solid of (trans-1-propenyl) transdecahydronaphthalene (I-5) was obtained. Example 6 Synthesis of 2- (trans-4-propylcyclohexyl) -6- (2,2-difluoroethenyl) transdecahydronaphthalene (I-6)

[0126]

Embedded image

The 6- (trans-4) obtained in (4-a)
-Propylcyclohexyl) decahydronaphthalene-2
8.0 g of carbaldehyde and 8.7 g of triphenylphosphine were added to diethylene glycol dimethyl ether (D
iglyme) A solution of 7.1 g of sodium chlorodifluoroacetate in 20 mL of Diglyme was added dropwise to the solution heated and stirred at 160 ° C in 10 mL for 30 minutes. After continuing heating for 2 hours, the mixture was allowed to cool to room temperature, water and hexane were added, the organic layer was separated, washed with 10% hydrochloric acid, a saturated aqueous solution of sodium carbonate and saturated brine in that order, and dried over anhydrous sodium sulfate. After that, the solvent was distilled off. Purification by silica gel column chromatography (hexane)
Recrystallized from ethanol at a temperature of below 2 ° C to give 2- (trans-
4-propylcyclohexyl) -6- (2,2-difluoroethenyl) transdecahydronaphthalene (I-
6) 0.6 g was obtained. Example 7 Synthesis of 2- (3-butenyl) -6- [difluoro- (trans-4-propylcyclohexyloxy) methyl] transdecahydronaphthalene (I-7)

[0128]

Embedded image

(7-a) Synthesis of 6- [difluoro- (trans-4-propylcyclohexyloxy) methyl] transdecahydronaphthalene-2-carbaldehyde 6- [difluoro- (trans-4-propylcyclohexyloxy) methyl 11 g of transdecahydronaphthalen-2-one is reacted with a Wittig reagent similar to (1-b) to give 6- [difluoro- (trans-4
-Propylcyclohexyloxy) methyl] transdecahydronaphthalene-2-carbaldehyde white solid 1
1 g was obtained. (7-b) Synthesis of 2- [difluoro- (trans-4-propylcyclohexyloxy) methyl] -6- (3-oxopropyl) transdecahydronaphthalene 6- [difluoro- obtained in (7-a) (Trans-
4-Propylcyclohexyloxy) methyl] transdecahydronaphthalene-2-carbaldehyde (11 g) was further repeated twice with the same Wittig reagent as in (1-b) to give 2- [difluoro- (trans-
4-propylcyclohexyloxy) methyl] -6
10 g of a white solid of (3-oxopropyl) transdecahydronaphthalene was obtained. (7-c) 2- (3-butenyl) -6- [difluoro-
Synthesis of (trans-4-propylcyclohexyloxy) methyl] transdecahydronaphthalene 2- [difluoro- (trans-) obtained in (7-b)
4-propylcyclohexyloxy) methyl] -6
10 g of (3-oxopropyl) transdecahydronaphthalene was reacted with a Wittig reagent similar to (1-d) to give 2- (3-butenyl) -6- [difluoro-
(Trans-4-propylcyclohexyloxy) methyl] transdecahydronaphthalene (I-7) was obtained as a white solid (5 g). Example 8 2- (trans-3-pentenyl) -6
[Difluoro- (trans-4-ethylcyclohexyl) methoxy] transdecahydronaphthalene (I-
8) Synthesis

[0130]

Embedded image

(8-a) Synthesis of 6- [difluoro- (trans-4-ethylcyclohexyl) methoxy] transdecahydronaphthalene-2-carbaldehyde 6- [difluoro- (trans-4-ethylcyclohexyl) methoxy] trans Decahydronaphthalene-2-
9 g of ON was reacted with the same Wittig reagent as in (1-b) to obtain 9 g of 6- [difluoro- (trans-4-ethylcyclohexyl) methoxy] transdecahydronaphthalene-2-carbaldehyde as a white solid. . (8-b) Synthesis of 2- [difluoro- (trans-4-ethylcyclohexyl) methoxy] transdecahydronaphthalene-6- (3-oxopropyl) transdecahydronaphthalene 6- obtained in (8-a) [Difluoro- (trans-
4-ethylcyclohexyl) methoxy] transdecahydronaphthalene-2-carbaldehyde (9 g) was obtained as (1-b)
The reaction with a Wittig reagent similar to that described above was repeated twice more to give 2- [difluoro- (trans-4-ethylcyclohexyl) methoxy] transdecahydronaphthalene-6- (3-oxopropyl) transdecahydronaphthalene in white 6 g of a solid were obtained. (8-c) 2- (trans-3-pentenyl) -6
Synthesis of [difluoro- (trans-4-ethylcyclohexyl) methoxy] transdecahydronaphthalene 2- [difluoro- (trans-) obtained in (8-b)
4-ethylcyclohexyl) methoxy] transdecahydronaphthalene-6- (3-oxopropyl) transdecahydronaphthalene 6 g was reacted with a Wittig reagent similar to (3-f), treated with benzenesulfinic acid to give 2- There was obtained 3 g of a white solid of (trans-3-pentenyl) -6- [difluoro- (trans-4-ethylcyclohexyl) methoxy] transdecahydronaphthalene (I-8). Example 9 2- (trans-4-propylcyclohexyl) -6- [2- (trans-4-vinylcyclohexyl) ethyl] transdecahydronaphthalene (I-
Synthesis of 9)

[0132]

Embedded image

(9-a) Synthesis of 2- (trans-4-propylcyclohexyl) -6- (2-oxoethyl) transdecahydronaphthalene 6- (trans-4-propylcyclohexyl) obtained in (4-a) ) 16 g of decahydronaphthalene-2-carbaldehyde were reacted with a Wittig reagent similar to (1-b) to give 2- (trans-4-propylcyclohexyl) -6- (2-oxoethyl) transdecahydronaphthalene. 16 g of a white solid was obtained. (9-b) Synthesis of 2- (trans-4-propylcyclohexyl) -6- (2-hydroxyethyl) transdecahydronaphthalene 2- (trans-4-propylcyclohexyl)-obtained in (9-a) 16-g of 6- (2-oxoethyl) transdecahydronaphthalene was reduced in the same manner as in (2-a) to give 2- (trans-4-propylcyclohexyl)-
14 g of a white solid of 6- (2-hydroxyethyl) transdecahydronaphthalene was obtained. (9-c) Synthesis of 2- (trans-4-propylcyclohexyl) -6- (2-bromoethyl) transdecahydronaphthalene 2- (trans-4-propylcyclohexyl) -6 obtained in (9-a) A solution of 14 g of-(2-oxoethyl) transdecahydronaphthalene cooled to 0 ° C in 80 mL of methylene chloride was added dropwise with a solution of 2 g of phosphorus tribromide in 20 mL of methylene chloride. After stirring at room temperature for 3 hours, water was added, the organic layer was separated, washed with a saturated aqueous solution of sodium bicarbonate, water and saturated saline in this order, dried over anhydrous sodium sulfate, and the solvent was distilled off. Purified by silica gel column chromatography (hexane) to give 2-
(Trans-4-propylcyclohexyl) -6- (2
Thus, 10 g of a pale yellow oily product of -bromoethyl) transdecahydronaphthalene was obtained. (9-d) 1- [2- [6- (trans-4-propylcyclohexyl) transoctahydronaphthalene-2
Synthesis of -yl] ethyl] -1-cyclohexen-4-one ethylene acetal From 10 g of 2- (trans-4-propylcyclohexyl) -6- (2-bromoethyl) transdecahydronaphthalene obtained in (9-c) A Grignard reagent is prepared and reacted in the same manner as in (3-a), and dehydrated and acetalized to give 1- [2- [6- (trans-4-).
Propylcyclohexyl) transoctahydronaphthalen-2-yl] ethyl] -1-cyclohexene-4-
6 g of a light yellow solid of on-ethylene acetal was obtained. (9-e) 1- [2- [6- (trans-4-propylcyclohexyl) transoctahydronaphthalene-2
Synthesis of -yl] ethyl] cyclohexane-4-one ethylene acetal 1- [2- [6- (trans-4) obtained in (9-d)
-Propylcyclohexyl) transoctahydronaphthalen-2-yl] ethyl] -1-cyclohexene-4
By hydrogenating 6 g of -one ethylene acetal in the same manner as in (3-b), 1- [2- [6- (trans-
4-propylcyclohexyl) transoctahydronaphthalen-2-yl] ethyl] cyclohexane-4-one 5 g of a white solid of ethylene acetal was obtained. (9-f) 1- [2- [6- (trans-4-propylcyclohexyl) transoctahydronaphthalene-2
Synthesis of -yl] ethyl] cyclohexane-4-one 1- [2- [6- (trans-4) obtained in (9-e)
-Propylcyclohexyl) transoctahydronaphthalen-2-yl] ethyl] cyclohexane-4-one 5 g of ethylene acetal was deacetalized in the same manner as (1-a) to give 1- [2- [6- (trans-4- Propylcyclohexyl) transoctahydronaphthalene-
4-g of 2-yl] ethyl] cyclohexane-4-one was obtained as a white solid. (9-g) 1- [2- [6- (trans-4-propylcyclohexyl) transoctahydronaphthalene-2
Synthesis of -yl] ethyl] cyclohexane-4-carbaldehyde 1- [2- [6- (trans-4) obtained in (9-f)
-Propylcyclohexyl) transoctahydronaphthalen-2-yl] ethyl] cyclohexane-4-one is reacted with a Wittig reagent similar to (1-b) to give 1- [2- [6- (trans-4 Thus, 4 g of a white solid of -propylcyclohexyl) transoctahydronaphthalen-2-yl] ethyl] cyclohexane-4-carbaldehyde was obtained. (9-h) Synthesis of 2- (trans-4-propylcyclohexyl) -6- [2- (trans-4-vinylcyclohexyl) ethyl] transdecahydronaphthalene 1- [2 obtained in (9-g) -[6- (trans-4
-Propylcyclohexyl) transoctahydronaphthalen-2-yl] ethyl] cyclohexane-4-carbaldehyde is reacted with a Wittig reagent similar to (1-d) to give 2- (trans-4-propylcyclohexyl)- 6- [2- (trans-4-vinylcyclohexyl) ethyl] transdecahydronaphthalene (I
-9) 1 g of a white solid was obtained. (Example 10) Preparation of liquid crystal composition (1) General-purpose p-type host liquid crystal composition (H)

[0134]

Embedded image

Was prepared. This (H) shows a nematic phase at 116.7 ° C. or lower, and its melting point is 11 ° C.
A liquid crystal element was prepared by filling (H) into a TN cell having a cell thickness of 6.0 μm, and the electro-optical characteristics at 20 ° C. were as follows. Threshold voltage (Vth) 2.14 V Response time (τ) 25.3 ms Steepness (γ) 1.23 Dielectric anisotropy (Δε) 4.8 Refractive index anisotropy (Δn) 0.090 80% by weight of this (H) and the compound (I-4) of the present invention obtained in Example 4.

[0136]

Embedded image

A liquid crystal composition (H-
4) was prepared. T _NI of the composition was 116.4 ° C.. This (H-4) was allowed to stand at −20 ° C. for 4 weeks, but no crystal precipitation or phase separation was observed. Also, -60
After cooling to ℃ and allowing it to crystallize, its T _CN was measured to be -3 ° C., which was much lower than (H), and (I-4) was well dissolved in the host liquid crystal. You can see that it is.

Next, (H-4) was converted to a T cell having a cell thickness of 6.0 μm.
A liquid crystal element was prepared by filling in an N cell, and its electro-optical characteristics were measured at 20 ° C., and the results were as follows. Threshold voltage (Vth) 2.31 V Response time (τ) 27.4 ms Steepness (γ) 1.29 Dielectric anisotropy (Δε) 3.2 Refractive index anisotropy (Δn) 0.081 (H) Is obtained by adding 20% by weight of (I-4).
The Δn was able to be reduced while suppressing the drop of T _NI to 4 ° C. Further, Vth and γ hardly changed, and their τ could be suppressed to an increase of about 5 ms.

The voltage holding ratio of this device at room temperature and 80 ° C. was measured, and it was found that each device was extremely good and could be used sufficiently for driving an active matrix. (Comparative Example) In Example 10, instead of (I-4),
Compound (R) having a similar structure, but the ring structure constituting the core portion is a trans-1,4-cyclohexylene group

[0140]

Embedded image

(H) was added in the same amount (20% by weight) to prepare a nematic liquid crystal composition (HR). A liquid crystal element was prepared in the same manner, and its electro-optical characteristics were measured. The results were as follows. Nematic phase upper limit temperature (T _NI ) 102.8 ° C. Melting point (T _CN )-threshold voltage (Vth) 2.29 V Response time (τ) 22.4 ms Steepness (γ) 1.21 Dielectric anisotropy (Δε) ) 3.6 Refractive index anisotropy (Δn) 0.089 (H−R) has a lower T _NI than (H−4) and a reduced nematic phase temperature range. Δn of (HR) is (H−
Δ 大 き く, Vth, and γ are (H−
There is almost no change as compared with 4), and the response is superior as compared with (H-4).

As described above, the compound of the general formula (I)
(A) improving the nematic phase temperature range and (b) Δ
It is very useful for preparing a liquid crystal composition having a low n.

The compound of the formula (I) does not have a strong polar group in the molecule, and can easily obtain a large specific resistance and a high voltage holding ratio, and is used as a component of a liquid crystal material for driving an active matrix. It is also possible. (Example 11) Preparation of liquid crystal composition (2) A liquid crystal composition (M) having the following composition was prepared.

4% by weight of 4-ethoxy-1- (trans-4-propylcyclohexyl) benzene 3% by weight of 4-methylphenyl trans-4-pentylcyclohexanecarboxylate 3% by weight of trans-4-propylcyclohexanecarboxylic acid 4-ethoxyphenyl 3% by weight trans-4- (4-methylphenyl) -trans-4'-vinylbicyclohexane 3% by weight trans-4-butyl-trans-4'-propylbicyclohexane 4% by weight trans -4-pentyl-trans-4'-
Vinyl bicyclohexane 3% by weight of 4,4'-bis (3-butenyl) bicyclohexane 4% by weight of 1- (4-propylphenyl) -2- (4-
Methylphenyl) ethyne 3% by weight of 1- (4-ethoxyphenyl) -2- (4-
Pentylphenyl) ethyne 3% by weight of 1,2-bis [4- (3-butenyl) phenyl] ethyne 4% by weight of 1- (4-ethylphenyl) ethynyl-4-
(Trans-4-propylcyclohexyl) benzene 3% by weight of 4- (trans-4-pentylcyclohexyl) -4'-ethylbiphenyl 3% by weight of 4- (trans-4-propylcyclohexyl) -1-cyanobenzene 4% by weight % Of 4- [trans-4- (trans-1-propenyl) cyclohexyl] -1-cyanobenzene 3% by weight of 4- [trans-4- (3-butenyl) cyclohexyl] -1-cyanobenzene 3% by weight 4'-pentyl-4-cyanobiphenyl 4% by weight 2- (4-cyanophenyl) -5-pentylpyrimidine 3% by weight 4-cyanophenyl 4-ethylbenzoate 3% by weight trans-4-pentylcyclohexanecarboxylic acid 3,4-difluorophenyl acid 4% by weight of 3-fluoro-4-cyano 4-butylbenzoate Eniru 3 wt% of 4- (trans-3-penten-1-yl)
3,5-difluoro-4-cyanophenyl benzoate 3% by weight of trans-4- (3-fluoro-4-cyanophenyl) -trans-4 '-(3-methoxypropyl) bicyclohexane 3% by weight of trans- 4- (3,4-difluorophenyl) -trans-4'-ethylbicyclohexane 4% by weight of trans-4- (3,4-difluorophenyl) -trans-4'-vinylbicyclohexane 4% by weight of trans- 4- (3,4,5-trifluorophenyl) -trans-4'-propylbicyclohexane 3% by weight of trans-4- [2- (3,4,5-trifluorophenyl) ethyl] -trans-4 '-Propylbicyclohexane 3% by weight of 4- (trans-4-propylcyclohexyl) -4'-cyanobiphenyl 4% by weight of 4- (tolane 3-fluoro-4-cyanophenyl benzoate 3% by weight of 4 '-(trans-4-propylcyclohexyl) -3,4,5-trifluorobiphenyl 3% by weight of 1- (3 , 4,5-trifluorophenyl)
T _NI ethynyl-4- (trans-4-propyl-cyclohexyl) benzene This (M) is 75.0 ° C., [Delta] n is 0.1
42. 90% of this (M) and (I-4) obtained in Example 1

[0145]

Embedded image

A liquid crystal composition (M-4) consisting of 10% was prepared. T _NI of this (M-4) is 111.0 ° C., [Delta] n was 0.055.

[0147]

The decahydronaphthalene derivative containing an alkenyl group, which is a novel compound of the present invention, is excellent in compatibility with general-purpose liquid crystal compounds or compositions at present, and particularly excellent in nematic liquid crystallinity. In addition, the addition can improve the nematic phase temperature range and obtain a liquid crystal composition having a low Δn. Therefore, a liquid crystal composition containing the same as a practical liquid crystal, especially a nematic liquid crystal temperature range is wide,
It is extremely useful for a liquid crystal display requiring a liquid crystal display material having a low Δn.

Continued on the front page (72) Inventor Haruyoshi Takatsu 3-6-27 Nakahara, Higashiyamato-shi, Tokyo F-term (reference) 4H006 AA01 AA03 AB64 4H027 BA01 BB04 BC05 BD02 BD04 BD07 BD08 BD24 CB01 CB02 CC04 CD04 CL01 CL04 CM01 CM04 CN04 CP04 CQ01 CQ02 CQ04 CT04 CW02 DM02 DM04

Claims (7)

[Claims] 1. A compound of the general formula (I) (Wherein, R and R ′ are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxyl group, an alkenyl group which may be substituted by a fluorine atom or an alkoxyl group having 1 to 7 carbon atoms, Represents an alkenyloxy group, an alkanoyloxy group or an alkoxycarbonyl group, or a cyano group, a cyanato group, a hydroxyl group or a carboxyl group, at least one of which may be substituted with a fluorine atom or an alkoxyl group having 1 to 7 carbon atoms. L and L ′ each independently represent —CH ₂ CH ₂ —, —CH (CH ₃ ) CH ₂ —, —CH
_{2 CH (CH 3) -,} - CH 2 O -, - OCH 2 -, - CF
_{2 O -, - OCF 2 -} , - COO -, - OCO -, - CH
= CH-, -CF = CF-, -C≡C-, -O (C
H ₂ ) ₃ —, — (CH ₂ ) ₃ O—, — (CH ₂ ) ₄ — or a single bond, m and n are each independently 0, 1
Or an integer of 2, wherein the decahydronaphthalene ring is in the trans form, the 2,6-position is in the trans configuration,
The 1,4-position of the cyclohexane ring is in the trans configuration. A decahydronaphthalene derivative represented by the formula: 2. In the general formula (I), L and L ′ are each independently —CH ₂ CH ₂ —, —CF ₂ O—,
OCF ₂ -, - CF = CF- or decahydronaphthalene derivative according to claim 1, wherein where represents a single bond. 3. In the general formula (I), R and R ′ are each independently a fluorine atom or a group having 1 to 7 carbon atoms.
Represents an alkyl group having 1 to 12 carbon atoms which may be substituted by an alkoxyl group, an alkoxyl group, an alkenyl group or an alkenyloxy group, at least one of which is substituted by a fluorine atom or an alkoxyl group having 1 to 7 carbon atoms. The decahydronaphthalene derivative according to claim 1, which represents an alkenyl group which may be substituted. 4. The decahydronaphthalene derivative according to claim 1, wherein in formula (I), L and L ′ represent a single bond. 5. In the general formula (I), m + n is 0, 1
Or the decahydronaphthalene derivative according to claim 1, which represents 2. 6. A liquid crystal composition comprising the compound represented by the general formula (I) according to claim 1. 7. A liquid crystal device comprising the liquid crystal composition according to claim 6 as a component.