JP2003313166A - Acetylene compound, liquid crystal composition and liquid crystal element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a compound usable as a constituent component of a liquid crystal composition and effective for suppressing the lowering of an SA-SC* phase transition temperature and lowering of a tilt angle of the composition. <P>SOLUTION: This invention relates to an acetylene compound expressed by formula (1) (rings A and B are each pyridin-2,5-diyl group; ring C is 1,4- phenylene, trans-1,4-cyclohexylene or 2,6-naphthylene; R<SB>1</SB>and R<SB>2</SB>are each independently a 2-24C straight or branched-chain alkyl, a 2-24C straight or branched- chain alkoxyalkyl or a 2-24C straight or branched-chain unsaturated alkyl wherein a part of hydrogen atoms of the alkyl, alkoxyalkyl and unsaturated alkyl may be substituted with fluorine atoms; X<SB>1</SB>and X<SB>3</SB>are each independently a single bond, -O-, -COO- or -OCO- X<SB>2</SB>is a single bond, -COO- or -OCO-Y is H or a halogen atom; and (n) is 0 or 1), a liquid crystal composition containing the compound and a liquid crystal element produced by using the composition. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel acetylene compound. More specifically, it relates to a novel acetylene compound useful as a component of a liquid crystal composition used for a liquid crystal display device, a liquid crystal composition containing the compound, and a liquid crystal device using the liquid crystal composition.

[0002]

2. Description of the Related Art Liquid crystal display devices are used as displays for various purposes because they are thin and lightweight and have low power consumption.

Currently, a TN (twisted nematic) type display system is most widely used as a liquid crystal display device. This TN type display system is inferior in terms of response time to light emitting type devices (cathode tube, electroluminescence, plasma display, etc.).
STN with a twist angle of 180-270 ° (Super
Twisted nematic) display devices have also been developed, but the response time is still poor. Although various efforts have been made to improve the TN type display element having a short response time, it has not been realized yet.

However, in a new display system using a ferroelectric liquid crystal, which has been actively researched in recent years, there is a possibility that the response time is remarkably improved [NAClark].
Et al. Applied Phys. Lett., 36 , 899 (1980)].

This method is a method utilizing a chiral smectic phase such as a chiral smectic C phase exhibiting ferroelectricity. It is known that not only the chiral smectic C phase but also the chiral smectic F, G, H, I phases exhibiting ferroelectricity are ferroelectric liquid crystal phases. These smectic liquid crystal phases belong to the tilt-type chiral smectic phase, but practically, utilization of the chiral smectic C phase, which has low viscosity and is expected to have high-speed response, has been studied. .

In addition, research has recently been actively conducted on a display system using a chiral smectic CA phase (antiferroelectric phase) which is a higher-order phase of the chiral smectic C phase. (L. Chandani et al .; Jpn.J.App.Phys., 27.L719
(1988)] Various liquid crystal compounds exhibiting a tilt type smectic phase have been studied so far, and many compounds have already been searched and produced. However, many characteristics (fast response, orientation, high contrast ratio, threshold characteristics, memory stability, and temperature dependence of these characteristics required for application to the ferroelectric liquid crystal display element actually used Etc.), a ferroelectric liquid crystal composition obtained by mixing several liquid crystal compounds, which cannot be handled by one compound at present, is used.

As the tilt-based chiral smectic composition, not only a liquid crystal composition consisting only of a compound exhibiting a tilt-based chiral smectic liquid crystal phase but also a compound or composition exhibiting a non-chiral tilt-based smectic phase is a basic substance. As such, one or more compounds exhibiting a tilt-based chiral smectic phase can be mixed with these to obtain the whole as a tilt-based chiral smectic liquid crystal composition. Furthermore, a compound or composition having a tilt-based smectic phase is used as a basic substance, and one or more compounds that are optically active but do not exhibit a tilt-based chiral smectic liquid crystal phase are mixed to form a tilt-based chiral smectic liquid crystal composition as a whole. There is also a report [Mol.Cryst.Liq.Cryst., 89,327 (1982)].

In summary, one or more compounds that are optically active regardless of whether or not they exhibit a tilt-type chiral smectic liquid crystal phase are mixed with a non-chiral compound that exhibits a tilt-type smectic liquid crystal phase. Thus, it is understood that the tilt-based smectic liquid crystal composition can be formed.

As described above, various compounds can be used as the constituents of the liquid crystal composition, but practically, they exhibit a tilt type smectic phase or a chiral smectic phase in a wide temperature range including room temperature. Liquid crystal compounds or mixtures are preferred. Known components of these liquid crystal compositions include phenylbenzoate liquid crystal compounds, biphenyl liquid crystal compounds, phenylpyrimidine liquid crystal compounds and ester liquid crystal compounds.

However, liquid crystal compositions containing these compounds as constituents are still unsatisfactory in layer structure (ideally bookshelf structure) in smectic phase, viscosity and its temperature dependence, threshold characteristics, compatibility, etc. It is hard to say that it has sufficient characteristics.

For example, a tilt type smectic liquid crystal is
There is a problem that the liquid crystal response characteristics such as the response speed and the threshold characteristic have a large temperature dependency, so that the response characteristics in the low temperature range are deteriorated.

Therefore, under the present circumstances, in order to improve low temperature response characteristics, one or more kinds of liquid crystal compositions containing a low temperature response characteristic improving compound (mainly a compound having a relatively low molecular weight and a small polarity in the molecule) are used. I am adding. However, the addition of the low-temperature response property-improving compound changes the smectic A (S _A ) phase of the liquid crystal composition from the chiral smectic C.
(S _C ^*) phase or transition temperature (S _A -S _C ^* phase transition temperature) is lowered to the phase, the tilt angle to affect the liquid crystal display contrast (theta) is such to decrease problems are occurring .

[0013] in this way to at present liquid crystal compositions, it is desirable to suppress a decrease in the degradation or the tilt angle of the S _A -S _C ^* phase transition temperature by low-temperature response modifying compounds added.

[0014]

The object of the present invention is to improve the low temperature response characteristics when compounded in a smectic liquid crystal composition for practical application of a smectic liquid crystal element, while improving the low temperature response characteristics.
_A -S _C ^* phase compound decreases or suitable for suppressing a decrease in the tilt angle of the transition temperature and the compound crystal composition comprising, there is provided a liquid crystal device using the composition.

[0015]

As a result of intensive studies to solve the above problems, the inventors of the present invention found a certain acetylene compound and arrived at the present invention. That is,
The present invention relates to an acetylene compound represented by the general formula (1). Further, the present invention relates to a liquid crystal composition containing at least one acetylene compound represented by the general formula (1), and a liquid crystal device using the composition.

[0016]

[Chemical 11]

[Wherein, ring A and ring B are pyridine-2,
Represents a 5-diyl group, ring C represents a 1,4-phenylene group, trans-1,4-cyclohexylene group, 2,6-naphthylene group, and R ₁ and R ₂ each independently have 2 to 2 carbon atoms.
24 straight-chain or branched alkyl group, C2-C24 straight-chain or branched alkoxyalkyl group or C2-C2
24 represents a straight chain or branched unsaturated alkyl group, and some hydrogen atoms of the alkyl group, the alkoxyalkyl group and the unsaturated alkyl group may be replaced by fluorine atoms, and X ₁ and X ₃ are Each independently a single bond, -O
Represents —, —COO— or —OCO—, X ₂ represents a single bond, —COO— or —OCO—, Y represents a hydrogen atom or a halogen atom, and n is 0 or 1.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. In the acetylene compound represented by the general formula (1) of the present invention, ring A and ring B represent a pyridine-2,5-diyl group, ring C represents a 1,4-phenylene group and trans-1,4.
Represents a cyclohexylene group or a 2,6-naphthylene group,
n is 0 or 1. When n = 0, the acetylene compound represented by the general formula (1) of the present invention has a ring A and a ring B.
Is

[0019]

[Chemical 12]

Or

[0021]

[Chemical 13]

According to the structure, the following three types of structures are adopted.

[0023]

[Chemical 14]

It is preferably (1-A).

When n = 1, the acetylene compound represented by the general formula (1) of the present invention has the following 12 structures depending on the structures of ring A, ring B and ring C.

[0026]

[Chemical 15]

[0027]

[Chemical 16]

Preferably, (1-A1) and (1-A)
2), (1-A3), (1-D1), (1-D2) or (1-D3), and more preferably (1-A
1), (1-A3), (1-D1), or (1-D
3).

In the acetylene compound represented by the general formula (1) of the present invention, R ₁ and R ₂ are each independently a linear or branched alkyl group having 2 to 24 carbon atoms, or 2 to 24 carbon atoms.
Represents a linear or branched alkoxyalkyl group or a linear or branched unsaturated alkyl group having 2 to 24 carbon atoms. Further, some hydrogen atoms of the alkyl group, the alkoxyalkyl group and the unsaturated alkyl group may be replaced with fluorine atoms. The preferred carbon number of R ₁ and R ₂ is 4 to
It is 18, and more preferable carbon number is 5-16.

R ₁ and R ₂ preferably have 2 to 2 carbon atoms.
24 straight or branched alkyl groups or 2 to 2 carbon atoms
4 represents a straight chain or branched unsaturated alkyl group.

Specific examples of the groups represented by R ₁ and R ₂ include, for example, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n -Octyl group, n-nonyl group, n-decyl group, n
-Undecyl group, n-dodecyl group, n-tridecyl group,
n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group,
n-nonadecyl group, n-eicosyl group, n-heneicosyl group, n-docosyl group, n-tricosyl group, n-tetracosyl group, 1-methylethyl group, 1,1-dimethylethyl group, 1-methylpropyl group, 1-ethylpropyl group,
1-n-propylpropyl group, 1-methylbutyl group, 1
-Ethylbutyl group, 1-n-propylbutyl group, 1-n
-Butylbutyl group, 1-methylpentyl group, 1-ethylpentyl group, 1-n-propylpentyl group, 1-n-butylpentyl group, 1-n-pentylpentyl group, 1-methylhexyl group, 1-ethylhexyl group , 1-n-propylhexyl group, 1-n-butylhexyl group, 1-n-
Pentylhexyl group, 1-n-hexylhexyl group, 1
-Methylheptyl group, 1-ethylheptyl group, 1-n-
Propylheptyl group, 1-n-butylheptyl group, 1-
n-pentylheptyl group, 1-n-heptylheptyl group, 1-methyloctyl group, 1-ethyloctyl group, 1
-N-propyloctyl group, 1-n-butyloctyl group, 1-n-pentyloctyl group, 1-n-hexyloctyl group, 1-n-heptyloctyl group, 1-n-octyloctyl group, 1-methylnonyl Group, 1-ethylnonyl group, 1-n-propylnonyl group, 1-n-butylnonyl group, 1-n-pentylnonyl group, 1-n-hexylnonyl group, 1-n-heptylnonyl group, 1-n-octyl group Nonyl group, 1-n-nonylnonyl group, 1-methyldecyl group,

2-methylpropyl group, 2-methylbutyl group, 2-ethylbutyl group, 2-methylpentyl group, 2-
Ethyl pentyl group, 2-n-propyl pentyl group, 2-
Methylhexyl group, 2-ethylhexyl group, 2-n-propylhexyl group, 2-n-butylhexyl group, 2-methylheptyl group, 2-ethylheptyl group, 2-n-propylheptyl group, 2-n-butyl Heptyl group, 2-n-
Pentylheptyl group, 2-methyloctyl group, 2-ethyloctyl group, 2-n-propyloctyl group, 2-n-
Butyloctyl group, 2-n-pentyloctyl group, 2-
n-hexyloctyl group, 2-methylnonyl group, 2-ethylnonyl group, 2-n-propylnonyl group, 2-n-butylnonyl group, 2-n-pentylnonyl group, 2-n-hexylnonyl group, 2-n -Heptylnonyl group, 2-methyldecyl group, 2,3-dimethylbutyl group, 2,3,3-
Trimethylbutyl group, 3-methylbutyl group, 3-methylpentyl group, 3-ethylpentyl group, 4-methylpentyl group, 4-ethylhexyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 2, 4,4-Trimethylpentyl group, 2,3,3,4-tetramethylpentyl group, 3-methylhexyl group, 2,5-dimethylhexyl group, 3-ethylhexyl group, 3,5,5-trimethylhexyl group An alkyl group such as 4-methylhexyl group, 6-methylheptyl group, 3,7-dimethyloctyl group, 6-methyloctyl group,

2-methoxyethyl group, 3-methoxypropyl group, 4-methoxybutyl group, 5-methoxypentyl group, 6-methoxyhexyl group, 7-methoxyheptyl group, 8-methoxyoctyl group, 9-methoxynonyl group ,
10-methoxydecyl group, ethoxymethyl group, 2-ethoxyethyl group, 3-ethoxypropyl group, 4-ethoxybutyl group, 5-ethoxypentyl group, 6-ethoxyhexyl group, 7-ethoxyheptyl group, 8-ethoxyoctyl group Group, 9-ethoxynonyl group, 10-ethoxydecyl group, n-propyloxymethyl group, 2-n-propyloxyethyl group, 3-n-propyloxypropyl group, 4
-N-propyloxybutyl group, 5-n-propyloxypentyl group, 6-n-propyloxyhexyl group, 7
-N-propyloxyheptyl group, 8-n-propyloxyoctyl group, 9-n-propyloxynonyl group, 1
0-n-propyloxydecyl group, n-butyloxymethyl group, 2-n-butyloxyethyl group, 3-n-butyloxypropyl group, 4-n-butyloxybutyl group,
5-n-butyloxypentyl group, 6-n-butyloxyhexyl group, 7-n-butyloxyheptyl group, 8-
n-butyloxyoctyl group, 9-n-butyloxynonyl group, 10-n-butyloxydecyl group, n-pentyloxymethyl group, 2-n-pentyloxyethyl group,
3-n-pentyloxypropyl group, 4-n-pentyloxybutyl group, 5-n-pentyloxypentyl group,
6-n-pentyloxyhexyl group, 7-n-pentyloxyheptyl group, 8-n-pentyloxyoctyl group, 9-n-pentyloxynonyl group, 10-n-pentyloxydecyl group, n-hexyloxymethyl group Base, 2
-N-hexyloxyethyl group, 3-n-hexyloxypropyl group, 4-n-hexyloxybutyl group, 5-
n-hexyloxypentyl group, 6-n-hexyloxyhexyl group, 7-n-hexyloxyheptyl group, 8
-N-hexyloxyoctyl group, 9-n-hexyloxynonyl group, 10-n-hexyloxydecyl group, n
-Heptyloxymethyl group, 2-n-heptyloxyethyl group, 3-n-heptyloxypropyl group, 4-n-
Heptyloxybutyl group, 5-n-heptyloxypentyl group, 6-n-heptyloxyhexyl group, 7-n-
Heptyloxyheptyl group, 8-n-heptyloxyoctyl group, 9-n-heptyloxynonyl group, 10-n
-Heptyloxydecyl group,

Octyloxymethyl group, 2-n-octyloxyethyl group, 3-n-octyloxypropyl group, 4-n-octyloxybutyl group, 5-n-octyloxypentyl group, 6-n-octyloxy group Hexyl group, 7-n-octyloxyheptyl group, 8-n-octyloxyoctyl group, 9-n-octyloxynonyl group, 10-n-octyloxydecyl group, n-nonyloxymethyl group, 2-n- Nonyloxyethyl group, 3-n
-Nonyloxypropyl group, 4-n-nonyloxybutyl group, 5-n-nonyloxypentyl group, 6-n-nonyloxyhexyl group, 7-n-nonyloxyheptyl group, 8-n-nonyloxyoctyl group , 9-n-nonyloxynonyl group, 10-n-nonyloxydecyl group, n
-Decyloxymethyl group, 2-n-decyloxyethyl group, 3-n-decyloxypropyl group, 4-n-decyloxybutyl group, 5-n-decyloxypentyl group, 6
-N-decyloxyhexyl group, 7-n-decyloxyheptyl group, 8-n-decyloxyoctyl group, 9-n
-Decyloxynonyl group, 10-n-decyloxydecyl group, 2-n-undecyloxyethyl group, 4-n-undecyloxybutyl group, 6-n-undecyloxyhexyl group, 8-n-un Decyloxyoctyl group, 10
-N-undecyloxydecyl group, 2-n-dodecyloxyethyl group, 4-n-dodecyloxybutyl group, 6-
n-dodecyloxyhexyl group, 8-n-dodecyloxyoctyl group, 10-n-dodecyloxydecyl group, 1
-Methyl-2-methoxyethyl group, 1-methyl-2-ethoxyethyl group, 1-methyl-2-n-propyloxyethyl group, 1-methyl-2-n-butyloxyethyl group, 1-methyl-2 -N-pentyloxyethyl group, 1
-Methyl-2-n-hexyloxyethyl group, 1-methyl-2-n-heptyloxyethyl group, 1-methyl-2
-N-octyloxyethyl group, 1-methyl-2-n-
Nonyloxyethyl group, 1-methyl-2-n-decyloxyethyl group, 1-methyl-2-n-undecyloxyethyl group, 1-methyl-2-n-dodecyloxyethyl group, 2-methoxypropyl group 2-2-ethoxypropyl group, 2-n-propyloxypropyl group, 2-n-butyloxypropyl group, 2-n-pentyloxypropyl group, 2-n-hexyloxypropyl group, 2-n-heptyl Oxypropyl group, 2-n-octyloxypropyl group, 2-n-nonyloxypropyl group, 2-n-decyloxypropyl group, 2-n-undecyloxypropyl group, 2-n-dodecyloxypropyl group,

1-methyl-3-methoxypropyl group, 1
-Methyl-3-ethoxypropyl group, 1-methyl-3-
n-propyloxypropyl group, 1-methyl-3-n-
Butyloxypropyl group, 1-methyl-3-n-pentyloxypropyl group, 1-methyl-3-n-hexyloxypropyl group, 1-methyl-3-n-heptyloxypropyl group, 1-methyl-3- n-octyloxypropyl group, 1-methyl-3-n-nonyloxypropyl group, 1-methyl-3-n-decyloxypropyl group, 1
-Methyl-3-n-undecyloxypropyl group, 1-
Methyl-3-n-dodecyloxypropyl group, 3-methoxybutyl group, 3-ethoxybutyl group, 3-n-propyloxybutyl group, 3-n-butyloxybutyl group, 3
-N-pentyloxybutyl group, 3-n-hexyloxybutyl group, 3-n-heptyloxybutyl group, 3-n
-Octyloxybutyl group, 3-n-nonyloxybutyl group, 3-n-decyloxybutyl group, 3-n-undecyloxybutyl group, 3-n-dodecyloxybutyl group, isopropyloxymethyl group, 2- Isopropyloxyethyl group, 3-isopropyloxypropyl group, 4
-Isopropyloxybutyl group, 5-isopropyloxypentyl group, 6-isopropyloxyhexyl group, 7
-Isopropyloxyheptyl group, 8-isopropyloxyoctyl group, 9-isopropyloxynonyl group, 1
0-isopropyloxydecyl group, isobutyloxymethyl group, 2-isobutyloxyethyl group, 3-isobutyloxypropyl group, 4-isobutyloxybutyl group,
5-isobutyloxypentyl group, 6-isobutyloxyhexyl group, 7-isobutyloxyheptyl group, 8-
Isobutyloxyoctyl group, 9-isobutyloxynonyl group, 10-isobutyloxydecyl group, tert-butyloxymethyl group, 2-tert-butyloxyethyl group,
3-tert-butyloxypropyl group, 4-tert-butyloxybutyl group, 5-tert-butyloxypentyl group,
6-tert-butyloxyhexyl group, 7-tert-butyloxyheptyl group, 8-tert-butyloxyoctyl group, 9-tert-butyloxynonyl group, 10-tert-butyloxydecyl group,

(2-ethylbutyloxy) methyl group, 2
-(2'-ethylbutyloxy) ethyl group, 3- (2 '
-Ethylbutyloxy) propyl group, 4- (2'-ethylbutyloxy) butyl group, 5- (2'-ethylbutyloxy) pentyl group, 6- (2'-ethylbutyloxy) hexyl group, 7- ( 2'-ethylbutyloxy) heptyl group, 8- (2'-ethylbutyloxy) octyl group, 9- (2'-ethylbutyloxy) nonyl group, 10
-(2'-ethylbutyloxy) decyl group, (3-ethylpentyloxy) methyl group, 2- (3'-ethylpentyloxy) ethyl group, 3- (3'-ethylpentyloxy) propyl group, 4- (3'-ethylpentyloxy) butyl group, 5- (3'-ethylpentyloxy) pentyl group, 6- (3'-ethylpentyloxy) hexyl group, 7- (3'-ethylpentyloxy) heptyl group, 8- (3'-ethylpentyloxy) octyl group,
9- (3'-ethylpentyloxy) nonyl group, 10-
(3'-ethylpentyloxy) decyl group, 6- (1 '
-Methyl-n-heptyloxy) hexyl group, 4-
(1′-methyl-n-heptyloxy) butyl group, 2-
(2'-methoxyethoxy) ethyl group, 2- (2'-ethoxyethoxy) ethyl group, 2- (2'-n-propyloxyethoxy) ethyl group, 2- (2'-isopropyloxyethoxy) ethyl group, 2- (2'-n-butyloxyethoxy) ethyl group, 2- (2'-isobutyloxyethoxy) ethyl group, 2- (2'-tert-butyloxyethoxy) ethyl group, 2- (2'-n -Pentyloxyethoxy) ethyl group, 2- [2 '-(2 "-ethylbutyloxy) ethoxy] ethyl group, 2- (2'-n-hexyloxyethoxy) ethyl group, 2- [2'-(3 ”
-Ethylpentyloxy) ethoxy] ethyl group, 2-
(2'-n-heptyloxyethoxy) ethyl group, 2-
(2'-n-octyloxyethoxy) ethyl group, 2-
(2'-n-nonyloxyethoxy) ethyl group, 2-
(2'-n-decyloxyethoxy) ethyl group, 2-
(2'-n-undecyloxyethoxy) ethyl group, 2
-(2'-n-dodecyloxyethoxy) ethyl group,

2- [2 '-(2 "-methoxyethoxy)
Ethoxy] ethyl group, 2- [2 ′-(2 ″ -ethoxyethoxy) ethoxy] ethyl group, 2- [2 ′-(2 ″ -n)
-Propyloxyethoxy) ethoxy] ethyl group, 2-
[2 '-(2 "-isopropyloxyethoxy) ethoxy] ethyl group, 2- [2'-(2" -n-butyloxyethoxy) ethoxy] ethyl group, 2- [2 '-(2 "-
Isobutyloxyethoxy) ethoxy] ethyl group, 2-
[2 '-(2 "-tert-butyloxyethoxy) ethoxy] ethyl group, 2- {2'-[2"-(2 "'-ethylbutyloxy) ethoxy] ethoxy} ethyl group, 2-
[2 '-(2 "-n-pentyloxyethoxy) ethoxy] ethyl group, 2- [2'-(2" -n-hexyloxyethoxy) ethoxy] ethyl group, 2- {2 '-[2 "
-(3 "'-ethylpentyloxy) ethoxy] ethoxy} ethyl group, 2- [2'-(2" -n-heptyloxyethoxy) ethoxy] ethyl group, 2- [2 '-(2 "
-N-octyloxyethoxy) ethoxy] ethyl group,
2- [2 '-(2 "-n-nonyloxyethoxy) ethoxy] ethyl group, 2- [2'-(2" -n-decyloxyethoxy) ethoxy] ethyl group, 2- [2 '-(2 ”
-N-undecyloxyethoxy) ethoxy] ethyl group, 2- [2 '-(2 "-n-dodecyloxyethoxy) ethoxy] ethyl group, 2- {2'-[2"-
(2 "'-methoxyethoxy) ethoxy] ethoxy} ethyl group, 2- {2'-[2"-(2 "'-n-dodecyloxyethoxy) ethoxy] ethoxy} ethyl group, 2-
{2 '-{2 "-[2"'-(2-methoxyethoxy)
Ethoxy] ethoxy} ethoxy} ethyl group, 2- {2 ′
-{2 "-{2"'-[2- (2-methoxyethoxy)
Ethoxy] ethoxy} ethoxy} ethoxy} ethyl group,

1-methyl-2- (1'-methyl-2'-
Methoxyethoxy) ethyl group, 1-methyl-2- (1 '
-Methyl-2'-ethoxyethoxy) ethyl group, 1-methyl-2- (1'-methyl-2'-n-propyloxyethoxy) ethyl group, 1-methyl-2- (1'-methyl-2 ' -Isopropyloxyethoxy) ethyl group, 1-
Methyl-2- (1′-methyl-2′-n-butyloxyethoxy) ethyl group, 1-methyl-2- (1′-methyl-2′-isobutyloxyethoxy) ethyl group, 1-methyl-2- (1′-methyl-2′-tert-butyloxyethoxy) ethyl group, 1-methyl-2- (1′-methyl-2′-n-pentyloxyethoxy) ethyl group, 1-
Methyl-2- (1'-methyl-2'-n-hexyloxyethoxy) ethyl group, 1-methyl-2- (1'-methyl-2'-n-heptyloxyethoxy) ethyl group, 1
-Methyl-2- (1'-methyl-2'-n-octyloxyethoxy) ethyl group, 1-methyl-2- (1'-methyl-2'-n-nonyloxyethoxy) ethyl group, 1
-Methyl-2- (1'-methyl-2'-n-decyloxyethoxy) ethyl group, 1-methyl-2- (1'-methyl-2'-n-undecyloxyethoxy) ethyl group,
1-methyl-2- (1'-methyl-2'-n-dodecyloxyethoxy) ethyl group, 1-methyl-2- [1'-
Methyl-2 '-(1 "-methyl-2" -methoxyethoxy) ethoxy] ethyl group, 1-methyl-2- [1'-methyl-2'-(1 "-methyl-2" -ethoxyethoxy) ethoxy ] Ethyl group, 1-methyl-2- [1'-methyl-2 '-(1 "-methyl-2" -n-propyloxyethoxy) ethoxy] ethyl group, 1-methyl-2-
[1′-methyl-2 ′-(1 ″ -methyl-2 ″ -isopropyloxyethoxy) ethoxy] ethyl group, 1-methyl-2- [1′-methyl-2 ′-(1 ″ -methyl-2 ″)
-N-butyloxyethoxy) ethoxy] ethyl group, 1
-Methyl-2- [1'-methyl-2 '-(1 "-methyl-2" -isobutyloxyethoxy) ethoxy] ethyl group, 1-methyl-2- [1'-methyl-2'-(1 " −
Methyl-2 "-tert-butyloxyethoxy) ethoxy] ethyl group, 1-methyl-2- [1'-methyl-2 '
-(1 "-methyl-2" -n-pentyloxyethoxy) ethoxy] ethyl group, 1-methyl-2- [1'-methyl-2 '-(1 "-methyl-2" -n-hexyloxyethoxy) ) Ethoxy] ethyl group, 1-methyl-2-
[1'-methyl-2 '-(1 "-methyl-2" -n-heptyloxyethoxy) ethoxy] ethyl group, 1-methyl-2- [1'-methyl-2'-(1 "-methyl- 2 "
-N-octyloxyethoxy) ethoxy] ethyl group,
1-methyl-2- [1'-methyl-2 '-(1 "-methyl-2" -n-nonyloxyethoxy) ethoxy] ethyl group, 1-methyl-2- [1'-methyl-2'- (1 ”
-Methyl-2 "-n-decyloxyethoxy) ethoxy] ethyl group, 1-methyl-2- [1'-methyl-2 '
-(1 "-methyl-2" -n-undecyloxyethoxy) ethoxy] ethyl group, 1-methyl-2- [1'-methyl-2 '-(1 "-methyl-2" -n-dodecyloxy Ethoxy) ethoxy] ethyl group,

2-ethoxyethoxymethyl group, 2-n-
Butyloxyethoxymethyl group, 2-n-hexyloxyethoxymethyl group, 3-ethoxypropyloxymethyl group, 3-n-propyloxypropyloxymethyl group, 3-n-pentyloxypropyloxymethyl group,
3-n-hexyloxypropyloxymethyl group, 2-
Methoxy-1-methylethoxymethyl group, 2-ethoxy-1-methylethoxymethyl group, 2-n-butyloxy-1-methylethoxymethyl group, 4-methoxybutyloxymethyl group, 4-ethoxybutyloxymethyl group, 4
-N-butyloxybutyloxymethyl group, 2- (3 '
-Methoxypropyloxy) ethyl group, 2- (3'-ethoxypropyloxy) ethyl group, 2- (1'-methyl-2'-methoxyethoxy) ethyl group, 2- (1'-methyl-2'-ethoxy) Ethoxy) ethyl group, 2- (1 '
-Methyl-2'-n-butyloxyethoxy) ethyl group, 2- (4'-methoxybutyloxy) ethyl group, 2
-(4'-ethoxybutyloxy) ethyl group, 2-
[4 '-(2 "-ethylbutyloxy) butyloxy]
Ethyl group, 2- [4 '-(3 "-ethylpentyloxy) butyloxy] ethyl group, 3- (2'-methoxyethoxy) propyl group, 3- (2'-ethoxyethoxy)
Propyl group, 3- (2'-n-pentyloxyethoxy) propyl group, 3- (2'-n-hexyloxyethoxy) propyl group, 3- (3'-ethoxypropyloxy) propyl group, 3- (3 '-N-Propyloxypropyloxy) propyl group, 3- (3'-n-butyloxypropyloxy) propyl group, 3- (4'-ethoxybutyloxy) propyl group, 3- (5'-ethoxypentyloxy) ) Propyl group, 4- (2'-methoxyethoxy) butyl group, 4- (2'-ethoxyethoxy) butyl group, 4- (2'-isopropyloxyethoxy) butyl group, 4- (2'-isobutyloxyethoxy) ) Butyl group, 4- (2'-n-butyloxyethoxy) butyl group, 4- (2'-n-hexyloxyethoxy) butyl group, 4- (3'-n-propyloxypropoxy group) Oxy)
Butyl group, 4- (2'-n-propyloxy-1'-methylethoxy) butyl group, 4- [2 '-(2 "-methoxyethoxy) ethoxy] butyl group, 4- [2'-(2"
-N-butyloxyethoxy) ethoxy] butyl group, 4
-[2 '-(2 "-n-hexyloxyethoxy) ethoxy] butyl group, 5- (2'-n-hexyloxyethoxy) pentyl group, 2- [2'-(2" -n-butyloxyethoxy) ) Ethoxy] ethyl group,

(2-ethylhexyloxy) methyl group,
(3,5,5-trimethylhexyloxy) methyl group,
(3,7-Dimethyloctyloxy) methyl group, 2-
(2'-Ethylhexyloxy) ethyl group, 2-
(3 ', 5', 5'-trimethylhexyloxy) ethyl group, 2- (3 ', 7'-dimethyloctyloxy) ethyl group, 3- (2'-ethylhexyloxy) propyl group, 3- (3' , 5 ', 5'-Trimethylhexyloxy) propyl group, 3- (3', 7'-dimethyloctyloxy) propyl group, 4- (2'-ethylhexyloxy) butyl group, 4- (3 ', 5' , 5'-Trimethylhexyloxy) butyl group, 4- (3 ', 7'-dimethyloctyloxy) butyl group, 5- (2'-ethylhexyloxy) pentyl group, 5- (3', 5 ', 5' -Trimethylhexyloxy) pentyl group, 5- (3 ', 7'
-Dimethyloctyloxy) pentyl group, 6- (2'-
Ethylhexyloxy) hexyl group, 6- (3 ′,
5 ', 5'-trimethylhexyloxy) hexyl group,
An alkoxyalkyl group such as 6- (3 ′, 7′-dimethyloctyloxy) hexyl group,

2-propenyl group, 2-butenyl group, 3-
Butenyl group, 2-pentenyl group, 3-pentenyl group, 4
-Pentenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 2-heptenyl group, 3-heptenyl group, 4-heptenyl group, 5-heptenyl group, 6-heptenyl group, 2 -Octenyl group, 3
-Octenyl group, 4-octenyl group, 5-octenyl group, 6-octenyl group, 7-octenyl group, 2-nonenyl group, 3-nonenyl group, 4-nonenyl group, 5-nonenyl group, 6-nonenyl group, 7 -Nonenyl group, 8-nonenyl group, 2-decenyl group, 3-decenyl group, 4-decenyl group, 5-decenyl group, 6-decenyl group, 7-decenyl group, 8-decenyl group, 9-decenyl group, 3 , 7-Dimethyl-6-octenyl group, 3,7-dimethyloctene-
2,6-diyl group, 1-ethynyl group, 1-propynyl group, 1-butynyl group, 1-pentynyl group, 1-hexyl group, 1-heptynyl group, 1-octynyl group, 1-nonyl group, 1- An unsaturated alkyl group such as a decyl group, a 1-undecynyl group, a 1-dodecynyl group can be exemplified.

Further, for example, 2-fluoro-n-propyl group, 3-fluoro-n-propyl group, 1,3-difluoro-n-propyl group, 2,3-difluoro-n-propyl group, 2-fluoro -N-butyl group, 3-fluoro-n-butyl group, 4-fluoro-n-butyl group, 3-fluoro-2-methylpropyl group, 2,3-difluoro-
n-butyl group, 2,4-difluoro-n-butyl group,
3,4-difluoro-n-butyl group, 2-fluoro-n
-Pentyl group, 3-fluoro-n-pentyl group, 5-fluoro-n-pentyl group, 2,4-difluoro-n-pentyl group, 2,5-difluoro-n-pentyl group, 2-
Fluoro-3-methylbutyl group, 2-fluoro-n-hexyl group, 3-fluoro-n-hexyl group, 4-fluoro-n-hexyl group, 5-fluoro-n-hexyl group,
6-fluoro-n-hexyl group, 2-fluoro-n-heptyl group, 4-fluoro-n-heptyl group, 5-fluoro-n-heptyl group, 2-fluoro-n-octyl group,
3-fluoro-n-octyl group, 6-fluoro-n-octyl group, 4-fluoro-n-nonyl group, 7-fluoro-n-nonyl group, 3-fluoro-n-decyl group, 6-fluoro-n -Decyl group, 4-fluoro-n-dodecyl group, 8-fluoro-n-dodecyl group, 5-fluoro-n
-Tetradecyl group, 9-fluoro-n-tetradecyl group, 2-chloroethyl group, 3-chloro-n-propyl group, 2-chloro-n-butyl group, 4-chloro-n-butyl group, 2-chloro-n -Pentyl group, 5-chloro-n-
Pentyl group, 5-chloro-n-hexyl group, 4-chloro-n-heptyl group, 6-chloro-n-octyl group, 7-
Chloro-n-nonyl group, 3-chloro-n-decyl group, 8
-Chloro-n-dodecyl group,

N-perfluoropropyl group, n-perfluorobutyl group, n-perfluoropentyl group, n-perfluorohexyl group, n-perfluoroheptyl group,
n-perfluorooctyl group, n-perfluorononyl group, n-perfluorodecyl group, n-perfluoroundecyl group, n-perfluorododecyl group, n-perfluorotetradecyl group, 1-hydro-n- Perfluoropropyl group, 1-hydro-n-perfluorobutyl group, 1
-Hydro-n-perfluoropentyl group, 1-hydro-
n-perfluorohexyl group, 1-hydro-n-perfluoroheptyl group, 1-hydro-n-perfluorooctyl group, 1-hydro-n-perfluorononyl group, 1-
Hydro-n-perfluorodecyl group, 1-hydro-n-
Perfluoroundecyl group, 1-hydro-n-perfluorododecyl group, 1-hydro-n-perfluorotetradecyl group, 1,1-dihydro-n-perfluoropropyl group, 1,1-dihydro-n- Perfluorobutyl group,
1,1-dihydro-n-perfluoropentyl group, 1,
1-dihydro-3-pentafluoroethyl perfluoropentyl group, 1,1-dihydro-n-perfluorohexyl group, 1,1-dihydro-n-perfluoroheptyl group, 1,1-dihydro-n-perfluoro Octyl group,
1,1-dihydro-n-perfluorononyl group, 1,1
-Dihydro-n-perfluorodecyl group, 1,1-dihydro-n-perfluoroundecyl group, 1,1-dihydro-n-perfluorododecyl group, 1,1-dihydro-
n-perfluorotetradecyl group, 1,1-dihydro-
n-perfluoropentadecyl group, 1,1-dihydro-
n-perfluorohexadecyl group, 1,1,3-trihydro-n-perfluoropropyl group, 1,1,3-trihydro-n-perfluorobutyl group, 1,1,4-trihydro-n-perfluoro Butyl group, 1,1,4-trihydro-n-perfluoropentyl group, 1,1,5-trihydro-n-perfluoropentyl group, 1,1,3-
Trihydro-n-perfluorohexyl group, 1,1,6
-Trihydro-n-perfluorohexyl group, 1,1,
5-trihydro-n-perfluoroheptyl group, 1,
1,7-trihydro-n-perfluoroheptyl group,
1,1,8-trihydro-n-perfluorooctyl group, 1,1,9-trihydro-n-perfluorononyl group, 1,1,11-trihydro-n-perfluoroundecyl group,

2- (perfluoroethyl) ethyl group, 2
-(N-perfluoropropyl) ethyl group, 2- (n-
Perfluorobutyl) ethyl group, 2- (n-perfluoropentyl) ethyl group, 2- (n-perfluorohexyl) ethyl group, 2- (n-perfluoroheptyl) ethyl group, 2- (n-perfluoro) Octyl) ethyl group, 2
-(N-perfluorodecyl) ethyl group, 2- (n-perfluorononyl) ethyl group, 2- (n-perfluorododecyl) ethyl group, 2- (perfluoro-9'-methyldecyl) ethyl group, 2 -Trifluoromethylpropyl group, 3- (n-perfluoropropyl) propyl group, 3
-(N-perfluorobutyl) propyl group, 3- (n-
Perfluorohexyl) propyl group, 3- (n-perfluoroheptyl) propyl group, 3- (n-perfluorooctyl) propyl group, 3- (n-perfluorodecyl) propyl group, 3- (n-perfluoro) Dodecyl) propyl group, 4- (perfluoroethyl) butyl group, 4-
(N-perfluoropropyl) butyl group, 4- (n-perfluorobutyl) butyl group, 4- (n-perfluoropentyl) butyl group, 4- (n-perfluorohexyl) butyl group, 4- (n -Perfluoroheptyl) butyl group, 4- (n-perfluorooctyl) butyl group, 4
-(N-perfluorodecyl) butyl group, 4- (perfluoroisopropyl) butyl group, 5- (n-perfluoropropyl) pentyl group, 5- (n-perfluorobutyl) pentyl group, 5- (n- Perfluoropentyl) pentyl group, 5- (n-perfluorohexyl) pentyl group, 5- (n-perfluoroheptyl) pentyl group, 5
-(N-perfluorooctyl) pentyl group, 6- (perfluoroethyl) hexyl group, 6- (n-perfluoropropyl) hexyl group, 6- (n-perfluorobutyl) hexyl group, 6- (n- Perfluorohexyl) hexyl group, 6- (n-perfluoroheptyl) hexyl group, 6- (n-perfluorooctyl) hexyl group, 6
-(Perfluoroisopropyl) hexyl group, 6- (perfluoro-7'-methyloctyl) hexyl group, 7-
Substituted with a halogen atom such as (perfluoroethyl) heptyl group, 7- (n-perfluoropropyl) heptyl group, 7- (n-perfluorobutyl) heptyl group, 7- (n-perfluoropentyl) heptyl group An alkyl group,

2- (2'-trifluoromethylpropyloxy) ethyl group, 4- (2'-trifluoromethylpropyloxy) butyl group, 6- (2'-trifluoromethylpropyloxy) hexyl group, 8- (2'-trifluoromethylpropyloxy) octyl group, 2- (2 '
-Trifluoromethylbutyloxy) ethyl group, 4-
(2′-trifluoromethylbutyloxy) butyl group,
6- (2'-trifluoromethylbutyloxy) hexyl group, 8- (2'-trifluoromethylbutyloxy)
Octyl group, 2- (2'-trifluoromethylheptyloxy) ethyl group, 4- (2'-trifluoromethylheptyloxy) butyl group, 6- (2'-trifluoromethylheptyloxy) hexyl group, 8- (2'-trifluoromethylheptyloxy) octyl group, 2- (2 '
-Fluoroethyloxy) ethyl group, 4- (2'-fluoroethyloxy) butyl group, 6- (2'-fluoroethyloxy) hexyl group, 8- (2'-fluoroethyloxy) octyl group, 2- ( 2'-fluoro-n-propyloxy) ethyl group, 4- (2'-fluoro-n-propyloxy) butyl group, 6- (2'-fluoro-n-
Propyloxy) hexyl group, 8- (2'-fluoro-
n-propyloxy) octyl group, 2- (3'-fluoro-n-propyloxy) ethyl group, 4- (3'-fluoro-n-propyloxy) butyl group, 6- (3'-fluoro-n- Propyloxy) hexyl group, 8- (3 '
-Fluoro-n-propyloxy) octyl group, 2-
(3'-Fluoro-2'-methylpropyloxy) ethyl group, 4- (3'-fluoro-2'-methylpropyloxy) butyl group, 6- (3'-fluoro-2'-methylpropyloxy) hexyl Group, 8- (3'-fluoro-
2'-methylpropyloxy) octyl group, 2-
(2 ', 3'-difluoro-n-propyloxy) ethyl group, 4- (2', 3'-difluoro-n-propyloxy) butyl group, 6- (2 ', 3'-difluoro-n-
Propyloxy) hexyl group, 8- (2 ', 3'-difluoro-n-propyloxy) octyl group, 2- (2'
-Fluoro-n-butyloxy) ethyl group, 4- (2 '
-Fluoro-n-butyloxy) butyl group, 6- (2 '
-Fluoro-n-butyloxy) hexyl group, 8-
(2'-fluoro-n-butyloxy) octyl group,

2- (3'-fluoro-n-butyloxy) ethyl group, 4- (3'-fluoro-n-butyloxy) butyl group, 6- (3'-fluoro-n-butyloxy) hexyl group, 8- (3'-fluoro-n-butyloxy) octyl group, 2- (4'-fluoro-n-butyloxy) ethyl group, 4- (4'-fluoro-n-butyloxy) butyl group, 6- (4'-fluoro -N-butyloxy) hexyl group, 8- (4'-fluoro-n-butyloxy) octyl group, 2- (2 ', 3'-difluoro-n-butyloxy) ethyl group, 4- (2', 3'- Difluoro-n-butyloxy) butyl group, 6- (2 ′,
3'-difluoro-n-butyloxy) hexyl group, 8
-(2 ', 3'-difluoro-n-butyloxy) octyl group, perfluoro (2-n-hexyloxyethyl) group, 1,1-dihydro-perfluoro (2-methoxyethyl) group, 1,1- Dihydro-perfluoro (3-
n-propyloxypropyl) group, 1,1-dihydro-
Perfluoro (2-ethoxyethyl) group, 1,1-dihydro-perfluoro (2-n-pentyloxyethyl)
Group, 2- (2'-n-perfluorobutyloxyethoxy) ethyl group, 3- (n-perfluorobutyloxy)
-3,3-Difluoroethyl group, 4- (1,1,7-trihydro-n-perfluoroheptyloxy) butyl group, 2- (n-perfluoropropyloxy) -2-trifluoromethyl-2-fluoro Ethyl group, 2- (2 '
-Trichloromethylpropyloxy) ethyl group, 4-
(2'-trichloromethylpropyloxy) butyl group,
6- (2'-trichloromethylpropyloxy) hexyl group, 8- (2'-trichloromethylpropyloxy)
Octyl group, 2- (2'-trichloromethylbutyloxy) ethyl group, 4- (2'-trichloromethylbutyloxy) butyl group, 6- (2'-trichloromethylbutyloxy) hexyl group, 8- (2 ' -Trichloromethylbutyloxy) octyl group, 2- (2'-trichloromethylheptyloxy) ethyl group, 4- (2'-trichloromethylheptyloxy) butyl group, 6- (2'-trichloromethylheptyloxy) hexyl group , 8- (2'-
Trichloromethylheptyloxy) octyl group, 2-
(2'-chloroethoxy) ethyl group, 4- (2'-chloroethoxy) butyl group, 6- (2'-chloroethoxy)
Hexyl group, 8- (2'-chloroethoxy) octyl group,

2- (2'-chloro-n-propyloxy) ethyl group, 4- (2'-chloro-n-propyloxy) butyl group, 6- (2'-chloro-n-propyloxy) hexyl group , 8- (2'-chloro-n-propyloxy) octyl group, 2- (3'-chloro-n-propyloxy) ethyl group, 4- (3'-chloro-n-propyloxy) butyl group, 6 -(3'-chloro-n-propyloxy) hexyl group, 8- (3'-chloro-n-propyloxy) octyl group, 2- (3'-chloro-2'-methylpropyloxy) ethyl group, 4 -(3'-chloro-
2'-methylpropyloxy) butyl group, 6- (3'-
Chloro-2'-methylpropyloxy) hexyl group, 8
-(3'-chloro-2'-methylpropyloxy) octyl group, 2- (2 ', 3'-dichloro-n-propyloxy) ethyl group, 4- (2', 3'-dichloro-n-propyl) (Oxy) butyl group, 6- (2 ', 3'-dichloro-n-propyloxy) hexyl group, 8- (2', 3 '
-Dichloro-n-propyloxy) octyl group, 2-
(2'-chloro-n-butyloxy) ethyl group, 4-
(2'-chloro-n-butyloxy) butyl group, 6-
(2'-chloro-n-butyloxy) hexyl group, 8-
(2'-chloro-n-butyloxy) octyl group, 2-
(3'-chloro-n-butyloxy) ethyl group, 4-
(3'-chloro-n-butyloxy) butyl group, 6-
(3'-chloro-n-butyloxy) hexyl group, 8-
(3'-chloro-n-butyloxy) octyl group, 2-
(4'-chloro-n-butyloxy) ethyl group, 4-
(4'-chloro-n-butyloxy) butyl group, 6-
(4'-chloro-n-butyloxy) hexyl group, 8-
(4'-chloro-n-butyloxy) octyl group, 2-
(2 ', 3'-dichloro-n-butyloxy) ethyl group, 4- (2', 3'-dichloro-n-butyloxy)
Butyl group, 6- (2 ', 3'-dichloro-n-butyloxy) hexyl group, 8- (2', 3'-dichloro-n-
(Butyloxy) octyl group and other alkoxyalkyl groups substituted with a halogen atom, 3-n-perfluoropropyl-2-propenyl group, 3-n-perfluorobutyl-
2-propenyl group, 3-n-perfluoropentyl-2
-Propenyl group, 3-n-perfluorohexyl-2-
An unsaturated alkyl group substituted with a halogen atom such as a propenyl group, a 3-n-perfluoroheptyl-2-propenyl group and a 3-n-perfluorooctyl-2-propenyl group can be mentioned.

R ₁ and R ₂ may have an asymmetric carbon, and the asymmetric carbon may be optically active or non-optically active.

X ₁ and X ₃ are each independently a single bond,
It represents O-, -COO- or -OCO-, preferably -O-, -COO- or -OCO-, more preferably -O- or -COO-. X ₂ represents a single bond, —COO— or —OCO—, and preferably
It is a single bond or -COO-, more preferably a single bond.

Y represents a hydrogen atom or a halogen atom, preferably a hydrogen atom, a fluorine atom or a chlorine atom, and more preferably a hydrogen atom or a fluorine atom. When Y is a halogen atom, the substitution position is
It is preferably ortho to X ₃ .

Specific examples of the acetylene compound represented by the general formula (1) of the present invention include compounds shown in Table 1 below. In the table, X ₁ , X ₂ , X ₃
"-" In represents a single bond, the substitution position of Y is ortho to X ₃ , and Citro, HCitro, C
in vitro ', HC intro', Gera, -Ph-,-
CycH- and -Nap- represent the following groups.

Citro (CH ₃ ) ₂ C = CH (C
_{H 2) 2 CH (CH 3} ) CH 2 CH 2 - HCitro (CH 3) 2 CH (CH 2) 3 CH (C
_{H 3) CH 2 CH 2 -} Citro '(CH 3) 2 C = CH (CH 2) 2 CH (C
_{H 3) CH 2 - HCitro '} (CH 3) 2 CH (CH 2) 3 CH (C
_{H 3) CH 2 - Gera (} CH 3) 2 C = CH (CH 2) 2 C (C
H ₃₎ = CHCH ₂ - -Ph-

[0053]

[Chemical 17]

-CycH-

[0055]

[Chemical 18]

-Nap-

[0057]

[Chemical 19]

[0058]

[Table 1]

[0059]

[Table 2]

[0060]

[Table 3]

[0061]

[Table 4]

[0062]

[Table 5]

[0063]

[Table 6]

[0064]

[Table 7]

[0065]

[Table 8]

The acetylene compound represented by the general formula (1) of the present invention can be produced, for example, by the steps shown below.

-Production of acetylene compound-

[0068]

[Chemical 20]

When n = 0, a pyridine compound represented by the general formula (5) (X represents a halogen atom such as a bromine atom or an iodine atom or a leaving group such as a trifluoromethanesulfonyloxy group) and a general formula The acetylene compound represented by (6) is converted into a palladium catalyst [for example, palladium / carbon,
Dichlorobis (triphenylphosphine) palladium,
Tetrakis (triphenylphosphine) palladium],
In the presence of copper iodide, triphenylphosphine and a base (for example, an inorganic base such as sodium carbonate and potassium carbonate, an organic base such as triethylamine and diisopropylamine), the compound of the general formula (1 The acetylene compound represented by -A) can be produced.

The acetylene compound represented by the general formula (6) is a halogenated pyridine derivative represented by the general formula (7) (X 'represents a halogen atom such as chlorine atom, bromine atom or iodine atom). And 3-methyl-1-butyn-3-ol represented by the general formula (8) with a palladium catalyst [eg,
Palladium / carbon, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium], copper iodide, triphenylphosphine and bases (for example, inorganic bases such as sodium carbonate and potassium carbonate, organics such as triethylamine and diisopropylamine) The acetylene compound represented by the general formula (9) can be produced by reacting the acetylene compound represented by the general formula (9) in the presence of a base) at room temperature or at room temperature or higher. , Potassium hydroxide, sodium hydroxide) at room temperature or higher.

Further, by using a protecting group, the compound represented by the general formula (1) can be similarly produced by the steps shown below.

[0072]

[Chemical 21]

For example, a pyridine compound represented by the general formula (5) (X represents a halogen atom such as a bromine atom or an iodine atom or a leaving group such as a trifluoromethanesulfonyloxy group) and a general formula (6 ′) An acetylene compound represented by (R 'represents a lower alkyl group such as a methyl group or an ethyl group) with a palladium catalyst [eg, palladium / carbon, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium], Copper iodide, triphenylphosphine and bases (eg,
In the presence of an inorganic base such as sodium carbonate or potassium carbonate, or an organic base such as triethylamine or diisopropylamine, the reaction is carried out at room temperature or at a temperature higher than room temperature to obtain an acetylene compound represented by the general formula (1-A ′). . Next, the compound represented by the general formula (1-A ′) is hydrolyzed under basic or acidic conditions and then subjected to acidic conditions to obtain the acetylene-containing carboxylic acid compound represented by the general formula (10). . Furthermore, the acetylene-containing carboxylic acid compound represented by the general formula (10) and the general formula (11) [in the formula,
n represents 0 or 1, when n = 0, X ₃ is a single bond, and when n = 1, X ₃ is a single bond, —O—, —COO.
-Or -OCO-] is reacted to give ring A and ring B in the general formula (1).

[0074]

[Chemical formula 22]

In the general formula (1-where X ₂ is --COO--
The acetylene compound represented by A ″) can be produced.

The reaction of the acetylene-containing carboxylic acid compound represented by the general formula (10) with the alcohol compound represented by the general formula (11) is carried out by using the acetylene-containing carboxylic acid compound represented by the general formula (10). A halogenating agent such as thionyl chloride or oxalyl chloride is used to prepare an acetylene carboxylic acid halide, and then the compound represented by the general formula (11)
A method of reacting the alcohol compound represented by the formula (11) with a base (for example, triethylamine or pyridine), the N-containing acetylene carboxylic acid compound represented by the formula (10) and the alcohol compound represented by the formula (11). , N'-
A method of dehydration condensation in the presence of a dehydration condensation agent such as dicyclohexylcarbodiimide (hereinafter abbreviated as DCC) and a catalyst (eg, 4-N, N-dimethylaminopyridine, 4-pyrrolidinopyridine), the general formula (10) A method of reacting the acetylene-containing carboxylic acid compound represented by the formula (11) with an alcohol compound represented by the general formula (11) in the presence of diethylazodicarboxylic acid (hereinafter abbreviated as DEAD) and triphenylphosphine. it can.

When n = 1, X ₂ is a single bond, and ring C is a 1,4-phenylene group, it can be produced by the steps shown below.

[0078]

[Chemical formula 23]

That is, the acetylene compound represented by the general formula (12) and the pyridine compound represented by the general formula (13) (X is a halogen atom such as a bromine atom or an iodine atom or a elimination of a trifluoromethanesulfonyloxy group or the like). Represents a group) with a palladium catalyst [eg, palladium / carbon, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium], copper iodide, triphenylphosphine and a base (eg,
In the presence of an inorganic base such as sodium carbonate or potassium carbonate, or an organic base such as triethylamine or diisopropylamine, the reaction is performed at room temperature or at a temperature of room temperature or higher to obtain the acetylene compound represented by the general formula (14).
Next, a phenylboronic acid derivative represented by the general formula (15) (Y is a hydrogen atom or a halogen atom such as a fluorine atom or a chlorine atom) and an acetylene compound represented by the general formula (14) are mixed with a palladium catalyst [eg, , Palladium / carbon, tetrakis (triphenylphosphine) palladium] and a base (for example, an inorganic base such as sodium carbonate or potassium carbonate, an organic base such as triethylamine or diisopropylamine) at room temperature or a temperature higher than room temperature. Therefore, in the general formula (1-A1), X
_An acetylene compound (1-A1 ′) in which ₂ is a single bond can be produced.

The phenylboronic acid derivative represented by the general formula (15) is a halogenated benzene derivative represented by the general formula (16) (X ″ represents a halogen atom such as a bromine atom or an iodine atom). After adjusting the Grignard reagent from
It can be produced by allowing a borate ester such as trimethyl borate to act and hydrolyzing it under acidic conditions.

The acetylene compound represented by the general formula (1) of the present invention includes a compound which exhibits liquid crystallinity by itself and a compound which does not exhibit liquid crystallinity. Further, as a compound exhibiting liquid crystallinity, there are a compound exhibiting a smectic C phase (hereinafter abbreviated as Sc phase) and a compound not exhibiting Sc phase. The compound exhibiting the Sc phase shows a compound exhibiting a chiral smectic C phase (hereinafter abbreviated as Sc ^* phase) and the Sc phase but does not exhibit the Sc ^* phase depending on the presence or absence of the optically active asymmetric carbon of R ₁ or R _2. There is a compound. Each of these compounds can be effectively used as a constituent component of a liquid crystal composition.

Next, the liquid crystal composition of the present invention will be described.
It The liquid crystal composition generally comprises two or more components,
The liquid crystal composition of the present invention has, as an essential component, the acetone of the present invention.
It contains at least one type of thylene compound. Book
The liquid crystal composition of the invention is preferably a chiral smear.
A liquid crystal composition showing a phase of Ctic C, F, G, H, I, etc.
And more preferably Sc^* Liquid crystal composition exhibiting a phase
Is. Sc of the present invention ^* The liquid crystal composition exhibiting a phase is the present invention.
Acetylene compound, other than the acetylene compound of the present invention
Chiral or non-chiral smectic C phase (hereinafter S
c^* Phase or abbreviated as Sc phase)
And a combination of compounds selected from optically active compounds
Which is a composition prepared by
It contains at least one len compound.

The liquid crystal compound showing the Sc ^* phase other than the acetylene compound of the present invention is not particularly limited, and examples thereof include an optically active phenylbenzoate liquid crystal compound and an optically active biphenylbenzoate liquid crystal compound.
Optically active naphthalene liquid crystal compound, optically active phenylnaphthalene liquid crystal compound, optically active tolan liquid crystal compound,
Examples thereof include an optically active phenylpyrimidine liquid crystal compound, an optically active naphthylpyrimidine liquid crystal compound, and an optically active tetralin liquid crystal compound. The liquid crystal compound showing an Sc phase other than the acetylene compound of the present invention is not particularly limited, but for example, a non-optically active phenylbenzoate liquid crystal compound, a non-optically active biphenylbenzoate liquid crystal compound, a non-optically active naphthalene liquid crystal compound. Liquid crystal compounds, non-optically active phenylnaphthalene-based liquid crystal compounds, non-optically active tolan-based liquid crystal compounds, delinquentally active phenylpyrimidine-based liquid crystal compounds, non-optically active naphthylpyrimidine-based liquid crystal compounds, non-optically active tetralin-based liquid crystal compounds can be mentioned. . Sc other than the acetylene compound of the present invention
Specific examples of the compound exhibiting the ^* phase or the Sc phase include compounds represented by the following general formulas (2) to (4).

[0084]

[Chemical formula 24]

[Wherein, R ₂₁ , R ₂₂ , R ₃₁ R ₃₂ , R ₄₁ and R ₄₂ are each independently a straight chain having 3 to 24 carbon atoms which may have an optically active asymmetric carbon, or A branched alkyl group, a linear or branched alkoxyalkyl group having 3 to 24 carbon atoms or a linear or branched unsaturated alkyl group having 3 to 24 carbon atoms, represented by X ₂₁ , X ₂₂ , X ₃₁ , X ₃₂ , X _41, and X ₄₂ are each independently a single bond, —O— or —COO.
In the compounds represented by the general formulas (2), (3) and (4), R ₂₁ , R ₂₂ , R ₃₁ R ₃₂ , R ₄₁ and R ₄₂ are each independently an optically active asymmetric group. A linear or branched alkyl group having 3 to 24 carbon atoms which may have carbon, and 3 carbon atoms
To a straight-chain or branched alkoxyalkyl group having 24 to 24 carbon atoms or a straight-chain or branched unsaturated alkyl group having 3 to 24 carbon atoms, preferably having 3 to 20 carbon atoms which may have an optically active asymmetric carbon atom. It represents a linear or branched alkyl group, or a linear or branched alkoxyalkyl group having 3 to 20 carbon atoms which may have an optically active asymmetric carbon.
Specific examples of R ₂₁ , R ₂₂ , R ₃₁ R ₃₂ , R ₄₁ and R ₄₂ include, for example, the halogen atoms listed as specific examples of R ₁ and R ₂ of the acetylene compound represented by the general formula (1). Mention may be made of unsubstituted linear or branched alkyl groups, alkoxyalkyl groups, unsaturated alkyl groups.

In the compounds represented by the general formulas (2), (3) and (4), X ₂₁ , X ₂₂ , X ₃₁ , X ₃₂ , X ₄₁ and X ₄₂ are each independently a single bond or --O. -Or-C
Represents OO-. X ₂₁ and X ₃₁ are preferably —COO.
Represents a group or a —O— group, X ₄₁ preferably represents a single bond or a —O— group, and X ₂₂ , X ₃₂ , and X ₄₂ preferably represent a —COO— group or a —O— group. .

The compounds represented by the general formulas (2) and (4) can be produced, for example, according to the method described in JP-A-62-10045 or JP-A-63-233932. The compound represented by the general formula (3) is
For example, it can be produced according to the operation described in JP-A-60-32748.

The optically active compound, which does not exhibit liquid crystallinity by itself, is mixed with a liquid crystal compound exhibiting the Sc phase or a liquid crystal composition exhibiting the Sc phase to give S.
Compounds with the ability to develop the c ^* phase are shown. The optically active compound other than the optically active compound of the present invention is not particularly limited, and examples thereof include an optically active phenylbenzoate-based non-liquid crystal compound, an optically active biphenylbenzoate-based non-liquid crystal compound, an optically active naphthalene-based non-liquid crystal compound. , An optically active phenylnaphthalene-based non-liquid crystal compound, an optically active tolan-based non-liquid crystal compound, an optically active phenylpyrimidine-based non-liquid crystal compound, an optically active naphthylpyrimidine-based non-liquid crystal compound, and an optically active tetralin-based non-liquid crystal compound.

In the liquid crystal composition of the present invention, in addition to the above-mentioned essential components, a nematic liquid crystal compound showing no Sc phase as an optional component, a compound having no liquid crystallinity other than the optically active compound of the present invention (for example, , Anthraquinone dyes, azo dyes, and other dichroic dyes, and conductivity-imparting agents, life-improving agents, and the like). The content of the acetylene compound of the present invention in the liquid crystal composition of the present invention is not particularly limited, but is usually 1 to 90% by weight, preferably 1 to 60% by weight.

At least one acetylene compound of the present invention is used.
The liquid crystal composition containing the seed is superior in the liquid crystal temperature range and the tilt angle as compared with the conventional liquid crystal composition.

Next, the liquid crystal element of the present invention will be described. The liquid crystal element of the present invention comprises the liquid crystal composition of the present invention arranged between a pair of electrode substrates. FIG. 1 is a schematic cross-sectional view showing an example of a liquid crystal element having a chiral smectic phase for explaining the configuration of a liquid crystal element utilizing ferroelectricity. The liquid crystal element is configured by disposing a liquid crystal layer 1 exhibiting a chiral smectic phase between a pair of substrates 2 each provided with a transparent electrode 3 and an insulating alignment control layer 4, and setting the layer thickness with a spacer 5. A pair of transparent electrodes 3 are connected via a lead wire 6 so that a voltage can be applied from a power source 7. Further, the pair of substrates 2 is sandwiched by the pair of polarizing plates 8 arranged in the crossed Nicols state, and the light source 9 is arranged on the outer side of one side thereof. As the material of the substrate 2, glass such as soda lime glass, borosilicate glass, polycarbonate, polyether sulfone,
A transparent polymer such as polyacrylate may be used. As the transparent electrode 3 provided on the two substrates 2, for example, I
n ₂ O ₃ , SnO ₂ or ITO (indium, tin,
A transparent electrode made of a thin film of oxide; Indium Tin Oxide) can be used.

The insulating orientation control layer 4 is for rubbing a polymer thin film such as polyimide with a flocked cloth such as nylon, acetate or rayon to orient the liquid crystal. Examples of the material of the insulating orientation control layer 4 include silicon nitride, hydrogen-containing silicon nitride, silicon carbide, hydrogen-containing silicon carbide, silicon oxide, boron nitride, and hydrogen-containing boron nitride. , Cerium oxide, aluminum oxide, zirconium oxide, inorganic material insulating layer such as titanium oxide and magnesium fluoride, polyvinyl alcohol, polyimide, polyamide imide, polyester imide, polyether imide,
Organics such as polyether ketone, polyether ether ketone, polyether sulfone, polyparaxylene, polyester, polycarbonate, polyvinyl acetal, polyvinyl chloride, polyvinyl acetate, polyamide, polystyrene, cellulose resin, melamine resin, urea resin, acrylic resin The insulating orientation control layer may be an insulating orientation control layer having a two-layer structure in which an organic insulation layer is formed on an inorganic insulation layer, or an insulation orientation control layer composed of only an inorganic insulation layer or an organic insulation layer. May be.

When the insulating orientation control layer is an inorganic insulating layer, it can be formed by a vapor deposition method or the like. In the case of an organic insulating layer, an organic insulating layer material or a solution of its precursor is applied by a spinner coating method, a penetration coating method, a screen printing method, a spray coating method, a roll coating method, or the like,
It can be formed by removing the solvent under predetermined conditions (for example, under heating) and baking it if desired. When forming the organic insulating layer, if necessary, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-
Glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropylmethyldiethoxysilane, γ-
Glycidyloxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-
Methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, N-β-
(Aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl)-
Surface treatment is performed using a silane coupling agent such as γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and γ-aminopropyltriethoxysilane, and then an organic insulating layer material or a precursor thereof. May be applied. The layer thickness of the insulating orientation control layer 4 is
Usually, 10 angstrom to 1 μm, preferably 1
0 to 3000 angstroms, more preferably 1
It is 0 to 1000 angstroms.

The two substrates 2 are held by the spacer 5 at arbitrary intervals. For example, silica beads or alumina beads having a predetermined diameter are sandwiched between the substrates 2 as spacers, and the two substrates 2 are hermetically sealed with a sealant (for example, an epoxy-based adhesive) so that the spacers are spaced at arbitrary intervals. Can be kept. Further, a polymer film or glass fiber may be used as the spacer. A liquid crystal exhibiting a chiral smectic phase is sealed between the two substrates. The liquid crystal layer 1 is generally set to have a thickness of 0.5 to 20 μm, preferably 1 to 5 μm, and more preferably 1 to 3 μm. The transparent electrode 3 is connected to an external power source 7 by a lead wire. Further, on the outside of the substrate 2, a pair of polarizing plates 8 whose polarization axes are, for example, in a crossed Nicols state are arranged. The example of FIG. 1 is a transmissive type, and includes a light source 9. Further, the liquid crystal element using the liquid crystal composition of the present invention can be applied not only as the transmissive element shown in (FIG. 1) but also as a reflective element.

The display system of the liquid crystal device using the liquid crystal composition of the present invention is not particularly limited,
For example, (a) helical variable distortion type, (b) SSFLC (surface stabilized ferro-electric liquid crystal) type, (c) TSM (transient scattering mode) type, (d) G-H ( Guest-host) type and (e) field sequential color type display systems can be used.

The method for driving a liquid crystal element using the liquid crystal composition of the present invention may be a passive type such as a segment type or a simple matrix type, a TFT (thin film transistor) type, a MIM (metal-insulator-metal) type. ) Type or the like may be used. Further, the acetylene compound and the liquid crystal composition containing the compound of the present invention are used in fields other than the liquid crystal device for display (for example, electronic materials such as nonlinear optical functional devices and capacitor materials, limiters, memories, amplifiers, modulators). Can be applied to electronic elements such as, heat, light, pressure, mechanical deformation and the like and voltage conversion elements and sensors, power generation elements such as thermoelectric power generation elements, spatial light modulation elements, and photoconductive materials.

[0097]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. The symbols I, S _A , S in the examples and tables
c ^* and C have the following meanings. I: Isotropic liquid S _A : Smectic A phase Sc ^* : Chiral smectic C phase C: Crystal phase Further, the measurement in each example was performed according to the method described below. Phase transition temperature: measured using a polarization microscope equipped with a temperature control device. Tilt angle: A rectangular wave of ± 20 V and 1 Hz was applied to the liquid crystal element, and the angles (2θ) of the extinction positions at two points were visually determined under a polarization microscope and calculated (2θ / 2). When this value is 22.5 °, the bright / dark contrast due to the switching of the ferroelectric liquid crystal becomes the best.

Preparation Example 1: Preparation of 2-n-nonyloxy-5-aminopyridine 7.59 g (189.8 m) of sodium hydride (60 wt% mineral oil suspension) washed with 50 ml of hexane.
80 g of N, N-dimethylformamide was added to
-Hydroxynonane 23.73 g (164.8 mmol)
Was added dropwise over 10 minutes, the temperature was raised to 80 ° C., and the mixture was heated with stirring for 3 hours until foaming was completed. Then, the mixture was cooled to room temperature and dissolved in 120 g of N, N-dimethylformamide 2
-Chloro-5-nitropyridine 24.98 g (157.
6 mmol) was added dropwise with a dropping funnel over 1.5 hours.
The mixture was again heated to 80 ° C. and stirred for 3 hours. The reaction mixture was cooled to room temperature, the insoluble material was filtered off, toluene and water were added to the filtrate, and the mixture was washed with water. The toluene layer was dehydrated with magnesium sulfate, toluene was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to give 2-n-nonyloxy-5-nitropyridine as an orange solid 23.5.
7 g was obtained. Next, a mixture of 23.57 g of 2-n-nonyloxy-5-nitropyridine, 2.35 g of 5% Pd / carbon (containing 50% by weight of water) and 75 g of ethanol was stirred under a hydrogen atmosphere at room temperature for 5 hours. Then 5% Pd
/ Carbon was filtered off, and ethanol was distilled off from the filtrate under reduced pressure to obtain 20.27 g of 2-n-nonyloxy-5-aminopyridine as brown crystals.

Preparation Example 2: Preparation of 2-n-nonyloxy-5-iodopyridine 2-n-nonyloxy-5-aminopyridine 19.81
g (76.7 mmol) and 36% hydrochloric acid water 24.10 g
(237.7 mmol) in a mixture of 3 under ice cooling.
5.48 g of sodium nitrite dissolved in 0 g of water (7
9.4 mmol) was added dropwise with a dropping funnel over 30 minutes. After stirring under ice cooling for 3 hours, 39.49 g (219.8 mmol) of potassium iodide dissolved in 50 g of water was added dropwise under ice cooling. After completion of dropping, the temperature was raised to room temperature and the mixture was stirred for 4 hours. Then add 300 ml of hexane and stir for 30 minutes.
The organic component was extracted. After washing with water, the hexane layer was dehydrated with magnesium sulfate and hexane was distilled off under reduced pressure. Purify by silica gel column chromatography, and use 2-n-nonyloxy-5-iodopyridine as a brown liquid 1
2.10 g was obtained.

Production Example 3: Production of 6-chloronicotinic acid ethyl ester 6.47 g (123.6 mm) of 6-chloronicotinic acid
ol), 22.17 g of thionyl chloride (186.3 mmo)
A mixture consisting of 1) and 100 g of toluene was heated to 60 ° C., one drop of N, N-dimethylformamide was added, and the mixture was heated with stirring at 60 ° C. for 6 hours. Then, the mixture was cooled to room temperature, and excess thionyl chloride and toluene were distilled off under reduced pressure. Then, 26.41 g of ethanol (574.
1 mmol) and 50 g of toluene were added, the mixture was cooled in an ice bath, and a triethylamine-toluene solution (12.48) was added.
(g: triethylamine, 20 g: toluene) was added dropwise over 20 minutes. After the dropping, the temperature was raised to room temperature and after stirring for 2 hours,
The insoluble matter was filtered off. The filtrate was washed with water, the toluene layer was dehydrated with magnesium sulfate, and toluene was distilled off under reduced pressure to give 6-
Chloronicotinic acid ethyl ester as brown liquid 2
0.38 g was obtained.

Production Example 4: Preparation of 6- (3-hydroxy-3-methyl-1-butynyl) nicotinic acid ethyl ester 16.00 g (8
6.2 mmol), 3-methyl-1-butyn-3-ol 8.73 g (103.8 mmol), triphenylphosphine 0.569 g (2.17 mmol), copper iodide 0.081 g (0.43 mmol), dichlorobis. (Triphenylphosphine) palladium 0.302 g (0.
43 mmol) and 40 g of triethylamine were heated to 60 ° C. under a nitrogen atmosphere, aged for 1 hour, and then the temperature was raised to 70 ° C. After stirring at 70 ° C. for 17 hours, the mixture was cooled to room temperature. Thereafter, the insoluble matter was filtered, the insoluble matter was washed with 100 ml of toluene, and triethylamine and toluene were distilled off from the filtrate under reduced pressure. Next, add 100 ml each of toluene and distilled water, separate, wash with water,
It was dehydrated with magnesium sulfate and toluene was distilled off under reduced pressure to obtain 6- (3-hydroxy-3-methyl-1-butynyl) nicotinic acid ethyl ester as a brown oily substance.
1.42 g was obtained.

Production Example 5: Production of 6-ethynylnicotinic acid ethyl ester 6- (3-hydroxy-3-methyl-1-butynyl) nicotinic acid ethyl ester 21.25 g (91.2 mmo)
l), 1.71 g (30.5 mmol) of potassium hydroxide
A mixture of 140 g of toluene and 140 g of toluene was heated and stirred under a nitrogen atmosphere at a toluene reflux temperature for 10 hours, and then cooled to room temperature. Next, the insoluble matter was filtered off, and toluene was distilled off from the filtrate under reduced pressure. Then, the product was purified by silica gel column chromatography to obtain 5.25 g of 6-ethynylnicotinic acid ethyl ester as brown crystals.

Production Example 6: Preparation of 6-[(2'-n-nonyloxy-5'-pyridinyl) ethynyl] nicotinic acid ethyl ester 2-n-nonyloxy-5-iodopyridine 5.20 g
(15.0 mmol), 6-ethynyl nicotinic acid ethyl ester 2.63 g (15.0 mmol), triphenylphosphine 0.197 g (0.75 mmol), copper iodide 0.053 g (0.28 mmol) dichlorobis.
(Triphenylphosphine) palladium 0.199g
A mixture of (0.28 mmol) and 55 g of triethylamine was heated with stirring under a nitrogen atmosphere at 60 ° C. for 2 hours, and cooled to room temperature. After that, the insoluble matter was filtered, the insoluble matter was washed with 200 ml of toluene, and then triethylamine and toluene were distilled off from the filtrate under reduced pressure. Next, toluene and distilled water were added and the mixture was washed with water, the toluene layer was dehydrated with magnesium sulfate, and then the toluene was distilled off under reduced pressure. After that, it was purified by silica gel column chromatography, and 6
5.92 g of-[(2'-n-nonyloxy-5'-pyridinyl) ethynyl] nicotinic acid ethyl ester was obtained as yellow crystals.

Production Example 7: Production of 6-[(2'-n-nonyloxy-5'-pyridinyl) ethynyl] nicotinic acid 6-[(2'-n-nonyloxy-5'-pyridinyl)
Ethynyl] nicotinic acid ethyl ester 5.55 g (1
4.1 mmol), 3.80 g of potassium hydroxide (57.6)
mmol), 20 g of ethanol and 20 g of distilled water are heated and stirred at the reflux temperature of ethanol for 3.5 hours and cooled to room temperature, and 10.0 g of 36 wt% hydrochloric acid aqueous solution is added.
Was added dropwise over 30 minutes. Then stir at room temperature for 1 hour,
The precipitate was filtered and washed with water. The precipitate was dissolved in 1 l of ethyl acetate, washed with water, the ethyl acetate layer was dried over magnesium sulfate, and the ethyl acetate was distilled off under reduced pressure. 20 ml of hexane was added to the residue and the solid matter was collected by filtration to give 6-
2.41 g of [(2'-n-nonyloxy-5'-pyridinyl) ethynyl] nicotinic acid was obtained as a light brown solid.

Example 1: Preparation of Exemplified Compound 5 6-[(2'-n-nonyloxy-5'-pyridinyl)
[Ethynyl] nicotinic acid 364 mg, n-decanol 19
After stirring a mixture of 3 mg, 0.258 g of DCC, 0.069 g of 4-N, N-dimethylaminopyridine and 8 g of dichloromethane at room temperature for 2 hours, toluene was added, insoluble materials were filtered off, and then the filtrate was concentrated under reduced pressure. Toluene was distilled off. Then, the product was purified by silica gel column chromatography, and the obtained solid was recrystallized twice with methanol / ethanol to give Exemplified Compound 5 as pale yellow crystals.
2 mg was obtained. The phase transition temperature (° C) of this compound is shown below. C-I: 71

Example 2: Preparation of Exemplified Compound 6 6-[(2'-n-nonyloxy-5'-pyridinyl)
[Ethynyl] nicotinic acid 366 mg, n-nonaneol 2
00 mg, DCC 0.256 g, 4-N, N-dimethylaminopyridine 0.066 g and dichloromethane 7 g
The mixture consisting of was stirred at room temperature for 2 hours, toluene was added, the insoluble matter was filtered off, and the toluene was distilled off from the filtrate under reduced pressure. After that, the product was purified by silica gel column chromatography, and the obtained solid was recrystallized twice with methanol / ethanol to give Exemplified Compound 6 as a pale yellow crystal.
66 mg was obtained. The phase transition temperature (° C) of this compound is shown below. C-I: 70

Reference Example 1: Preparation of Liquid Crystal Composition The following compound groups were mixed in the ratios shown below, and the mixture was heated to 100 ° C.
Then, the mixture was heated and melted in order to prepare a liquid crystal composition (ferroelectric liquid crystal).

[0108]

[Chemical 25]

Example 3 Preparation of Liquid Crystal Composition A liquid crystal composition was prepared by adding 15% by weight of Exemplified Compound 5 produced in Example 1 to the liquid crystal composition prepared in Reference Example 1.

Reference Example 2: Preparation of Liquid Crystal Composition A liquid crystal composition was prepared by adding 15% by weight of the following compound to the liquid crystal composition prepared in Reference Example 1.

[0111]

[Chemical formula 26]

Example 4 Preparation of Liquid Crystal Element Two 1.1 mm thick glass plates were prepared, an ITO film was formed on each glass plate and surface treatment was performed. An insulating orientation control layer (CRD-8616 manufactured by Sumitomo Bakelite Co., Ltd.) was spin-coated on the glass plate with the ITO film, and after film formation, baking was performed at 90 ° C. for 5 minutes and 200 ° C. for 30 minutes. This alignment film was rubbed, and silica beads having an average particle size of 1.9 μm were scattered on one glass plate. Then, a glass plate was laminated using a sealant to prepare a cell so that the rubbing axes were antiparallel to each other. The cell was heated to 120 ° C and heated (1
20 ° C.) was injected with the liquid crystal composition prepared in Example 3,
Then, the liquid crystal element was manufactured by cooling to room temperature at a rate of 10 ° C./minute. When this liquid crystal element was sandwiched between two polarizing plates arranged in a crossed Nicols state and a rectangular wave of ± 20 V and 10 Hz was applied, a clear switching phenomenon was observed. In addition, a good uniform alignment state was observed under a polarizing microscope, and alignment defects such as zigzag defects were not observed. The S _A -S _C ^* phase transition temperature and tilt angle of this liquid crystal element are summarized in Table 2.

Comparative Example 1: The composition prepared in Reference Example 2 was heated to 120 ° C. in a cell prepared in the same manner as in Example 4, the heated (120 ° C.) liquid crystal composition was injected, and then the liquid crystal composition was injected. A liquid crystal element was manufactured by cooling to room temperature at a rate of 10 ° C./minute. When this liquid crystal element was sandwiched between two polarizing plates arranged in a crossed Nicols state and a rectangular wave of ± 20 V and 10 Hz was applied, a clear switching phenomenon was observed. In addition, a good uniform alignment state was observed under a polarizing microscope, and alignment defects such as zigzag defects were not observed. The S _A -S _C ^* phase transition temperature and tilt angle of this liquid crystal element are summarized in Table 2.

[0114]

[Table 9]

Comparison between Example 4 and Comparative Example 1 shown in Table 2 shows that the use of the acetylene compound of the present invention as a constituent of the liquid crystal composition significantly improves the S _A -S _C ^* phase transition temperature. It turns out that it is possible. Further, it can be seen that the tilt angle can be greatly expanded.

[0116]

According to the present invention, it is possible to provide an acetylene compound useful as a constituent component of a liquid crystal composition.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view of an example of a liquid crystal element using a liquid crystal exhibiting a chiral smectic phase.

[Explanation of symbols]

1: Liquid crystal layer 2 having chiral smectic phase 2: Substrate 3: Transparent electrode 4: Insulating orientation control layer 5: Spacer 6: Lead wire 7: Power supply 8: Polarizing plate 9: Light source I _O : Incident light I: Transmitted light

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yoshiyuki Toya             580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals, Inc.             Inside the company (72) Inventor Masakatsu Nakatsuka             580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals, Inc.             Inside the company F-term (reference) 4C055 AA01 BA02 BA06 BA25 BA42                       BB02 CA02 CA06 CA25 CA57                       CB02 DA01 EA01                 4H027 BA03 BD02 BD18 CC07 DB05                       DK05 DK07 DK08

Claims (8)

[Claims] 1. An acetylene compound represented by the following general formula (1). [Chemical 1] [Wherein, ring A and ring B represent a pyridine-2,5-diyl group, ring C represents a 1,4-phenylene group, trans-1,4
Represents a cyclohexylene group or a 2,6-naphthylene group,
R ₁ and R ₂ are each independently a linear or branched alkyl group having 2 to 24 carbon atoms, a linear or branched alkoxyalkyl group having 2 to 24 carbon atoms, or a linear or branched unsaturated alkyl group having 2 to 24 carbon atoms. And a part of hydrogen atoms of the alkyl group, the alkoxyalkyl group and the unsaturated alkyl group may be replaced by a fluorine atom, X ₁
And X ₃ are each independently a single bond, —O—, —COO.
Represents a — or —OCO—, X ₂ represents a single bond, —COO—
Or -OCO-, Y represents a hydrogen atom or a halogen atom, and n is 0 or 1.] 2. In the general formula (1), ring A is And the ring B is The acetylene compound according to claim 1, which is represented by: 3. In the general formula (1), ring A is And the ring B is The acetylene compound according to claim 1, which is represented by: 4. In the general formula (1), ring A is And the ring B is The acetylene compound according to claim 1, which is represented by: 5. The ring A in the general formula (1) is And ring B is The acetylene compound according to claim 1, which is represented by: 6. A liquid crystal composition comprising at least one acetylene compound according to claim 1. 7. An acetylene compound according to claim 1 and at least one of the following general formulas (2), (3) and (4):
7. The liquid crystal composition according to claim 6, containing at least one compound represented by [Chemical 10] [In the formula, R ₂₁ , R ₂₂ , R ₃₁ R ₃₂ , R ₄₁ and R ₄₂ are each independently a linear or branched alkyl group having 3 to 24 carbon atoms which may have an optically active asymmetric carbon atom. , Carbon number 3
To a linear or branched alkoxyalkyl group having 24 to 24 or a linear or branched unsaturated alkyl group having 3 to 24 carbon atoms, X ₂₁ , X ₂₂ , X ₃₁ , X ₃₂ , X ₄₁ and X ₄₂ are each independently Represents a single bond, -O- or -COO-] 8. A liquid crystal device using the liquid crystal composition according to claim 6 or 7.