JPH0931459A - Novel ferroelectric liquid crystal composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new composition for liquid crystal display elements, etc., capable of carrying out low voltage driving in high speed responsiveness by using a compound having an unpaired electron such as a fluorine substituent group or nitrogen in a direction vertical to molecular long shaft and having a structure in which three rings are fixed in a plane state.

SOLUTION: This ferroelectric liquid crystal composition for liquid crystal element capable of carrying out low voltage driving in high speed responsiveness is obtained by including at least one kind of compound represented by formula I [E¹ to E⁶ are each N, CF or CH; G is CH₂CH₂ or CH=CH; R₁ and R₂ are each H or a 1-20C alkyl, a group of formula II (R³ to R⁵ are each a 1-16C alkyl, etc.; Q is -CH₂-O-, -CO-O- or a single bond) or a group of formula III (R⁶ and R⁷ are each same kind group as R³); M¹ and M² are each -CO-O-, -O-CO-, -CH₂O-, -CH₂CH₂-, -C≡C- or a single bond; A¹ and A² are each 1,4- phenylene in which one or more hydrogen atoms may be replaced with F, Cl and/or CN or pyrazin-2,5-yl, etc., in which one or two or more hydrogen atoms are replaced with F, Cl and/or CN].

COPYRIGHT: (C)1997,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel ferroelectric liquid crystal composition, more specifically, a ferroelectric liquid crystal composition which is driven at a low voltage and has a high switching speed, and a liquid crystal display device using the liquid crystal composition. It is about.

[0002]

2. Description of the Related Art At present, liquid crystal compositions have been put to practical use as display devices in watches, calculators, small televisions and the like.
The most widely used one is to use the nematic phase of liquid crystal, and its display method is TN type (twisted).
nematic) or STN type (super tw)
Called isted nematic). But TN
The mold is not suitable for large-capacity display because the contrast decreases as the number of lines increases. Furthermore, the TN type has a thin film transistor (TFT: Thin film) for each pixel.
The display characteristics are CRT (cathode ray t) due to the TFT driving method with a transistor
UB), and it has become possible to increase the capacity.
However, the manufacturing process is complicated, the yield is low, and the manufacturing cost is very high. Also, a large screen is difficult.

The STN system is a simple matrix, but the display characteristics are improved as compared with the TN type.
Compared with the TFT-TN method, it is still insufficient.
However, the manufacturing cost is low. In 1980, surface-stabilized ferroelectric liquid crystal (SSFL) by Clark and Ragawall
C) was discovered (NA Clark, ST Lag)
awall, Appl. Phys. Lett. , 36,
899, 1980) and attracted attention as a next-generation display material, and many studies have been conducted. This is because the ferroelectric liquid crystal has (1) high-speed response and (2) memory property that enables a large display capacity, and does not require an active element such as a thin film transistor, so that the manufacturing cost is relatively low. This is because. In addition, (3) it has a wide viewing angle, and is expected as a display device having a large screen and a large display capacity.

[0004]

Achieving high contrast is important in the practical application of display devices of ferroelectric liquid crystals. The reason why it is difficult to achieve the expected contrast in the ferroelectric liquid crystal is a zigzag defect in the smectic C phase, a decrease in the effective cone angle due to the chevron structure, and an insufficient memory property. Various proposals have been made as methods for achieving high contrast. For example, a method using an oblique deposition film as an alignment film,
There are a C1 uniform method using an alignment film having a high pretilt, a method using an AC electric field treatment or a pseudo bookshelf structure using a naphthalene compound, and a method using a material having a negative dielectric anisotropy. Among them, the method using a material with negative dielectric anisotropy (Δε) utilizes the property that liquid crystal molecules with negative Δε are parallel to the electrode substrate when a high-frequency electric field perpendicular to the electrode substrate is applied. Yes, AC
It is called the stabilizing effect.

In addition, Surguy (PWH Su
rguiy et al., Ferroelectrics, 122,
63, 1991) proposed a "method using a liquid crystal material having a negative dielectric anisotropy". This method is a promising method for achieving high contrast, and P.
W. Ross (Proc. SID, 217, 1992)
Is disclosed.

A material having a negative dielectric anisotropy has a τ-V characteristic in which the pulse width (τ) required for switching has a minimum value (τ-Vmin) as the voltage (V) increases. Surguy et al. Reported a driving method using this characteristic. This driving method is a method of switching when a voltage of | Vs−Vd | is applied, and not switching with | Vs + Vd | and | Vd |.

The driving voltage in this driving method is τ-V
It is determined by the min value. According to Surguy et al., The Vmin value is given by: Vmin = Emin * d = Ps * d / √3 * ε ₀ * Δε
* Sin ² θ Here, Emin is the minimum value of the electric field strength, d is the cell thickness, P
s is the spontaneous polarization, Δε is the dielectric anisotropy, and θ is the tilt angle of the liquid crystal material.

In consideration of biaxial anisotropy (δε), Towler et al.
Is getting the value of.

[0009]

[Equation 1] (Η: viscosity) (M. J. Towler et al., Liquid Crystal)
al, 11, 1992).

However, according to the report of Ross et al., The response speed of the ferroelectric liquid crystal material is still slow, and Vs + Vd is 55 as well.
Above V, it is still not practical. Therefore, development of a low-viscosity liquid crystal material having a sufficiently large absolute value of negative dielectric anisotropy and large spontaneous polarization is desired.

For this purpose, a patent has been filed for a ferroelectric composition suitable for driving utilizing the AC stabilization effect and driving utilizing the .tau.-Vmin characteristic (JP-A-1-168792, JP-A-1-168792). 306493, Japanese Patent Application Laid-Open No. 4-4290, Japanese Patent Publication No. 7-29990, Japanese Patent Publication No. 2-
503444 etc.).

However, the response speed and drive voltage have not been sufficient. It is considered that this is because the negative absolute value of Δε is not sufficient.

It is an object of the present invention to provide a ferroelectric liquid crystal composition having a negative value of Δε and capable of high speed response and low voltage driving, and a liquid crystal display device using the liquid crystal composition.

[0014]

According to the present invention, there is provided a ferroelectric liquid crystal containing a compound represented by the general formula (1). The compound represented by the general formula (1) has a fluorine substituent and an unpaired electron of nitrogen in the direction perpendicular to the long axis of the molecule, and moreover, the three rings are fixed in a plane and hinder the free rotation of each ring. Therefore, it is considered that a large negative dielectric anisotropy and a relatively low viscosity can be obtained.

[0015]

Embedded image [Wherein the symbols and subscripts have the following meanings: E ¹ ,
^{E 2, E 3, E 4} , E 5 and E ⁶ are, -N -, - CF- or is a -CH-, but include the following exceptions: E
¹ (E ⁴ ) is -N- or -CF-, then E ² and E ³
(E ⁵ and E ⁶⁾ must be -CH-; E ² and / or E ³ (E ⁵ and / or E ⁶⁾ are -CF-
When, E ¹ (E ⁴⁾ must be -CH-; E ²
When (E ⁵⁾ is -N-, E ¹ (E ⁴⁾ must be an -CH-, E ³ (E ⁶⁾ is -CH- or -CF-
It can be at; and at least one of E ⁶ from E ¹ must be -N- or -CF-; G is -C
H ₂ CH ₂ - or -CH = CH- and is; R ¹ and R ²
Are, independently of each other, hydrogen or a linear or branched alkyl group having 1 to 20 carbon atoms (which may or may not have asymmetric carbon), wherein one or more of -CH ₂ - group, -O -, - S -, - CO -, - C
H = CH -, - C≡C-, _{cyclopropane-1,2-diyl, -Si (CH 3) 2 -} , 1,4- phenylene, trans-1,4-cyclohexylene or trans-1,
It may be substituted with 3-cyclopentylene, provided that it is an oxygen atom and a sulfur atom (hereinafter referred to as chalcogen).
Are not directly bonded to each other, and one or more hydrogen atoms of the alkyl group are -F, -Cl, -Br or-.
It may be substituted with OR ³ , or R ¹ and R ²
Is any of the following chiral groups.

[0016]

Embedded image (Here, R < ³ >, R < ⁴ >, R < ⁵ >, R < ⁶ > and R < ⁷ > are, independently of each other, a linear or branched alkyl group having 1 to 16 carbon atoms (having an asymmetric carbon it is also be) not be, one or more -CH ₂ where - groups, -
O- or -CH = CH- may be substituted,
However, the oxygen atoms are not directly bonded to each other, and one or more hydrogen atoms of the alkyl group are -F or -C.
l may be substituted, or R ⁴ and R ⁵ are
When bonded to an oxirane system, a dioxolane system, a tetrahydrofuran system, a tetrahydropyran system, a butyrolactone system or a valerolactone system, they are combined together-
(CH _{2) 4} - or - (CH _{2) 5} - may be formed;
Q is _{-CH 2 -O -, - CO-} O- or a single bond); M ¹ and M ² are identical or different, -CO-O
-, - O-CO -, - CH 2 -O -, - O-CH 2 -, -
CH ₂ —CH ₂ —, —C≡C— or a single bond; A ¹
And A ² are the same or different, 1,4-phenylene in which one or more hydrogen atoms may be substituted with F, Cl and / or CN, 1 or 2 hydrogen atoms in F, Cl And / or pyrazine-2,5-diyl optionally substituted with CN, pyridazine-3,6-diyl optionally substituted with 1 or 2 hydrogen atoms by F, Cl and / or CN, Pyridine-2,5-diyl optionally substituted with one or more hydrogen atoms with F, Cl and / or CN, one or two hydrogen atoms substituted with F, Cl and / or CN Optionally pyrimidine-2,5-diyl, 1 or 2
Hydrogen atoms is CN and / or CH ₃ with an optionally substituted trans-1,4-cyclohexylene, 1,
3,4-thiadiazole-2,5-diyl, 1,3-dioxane-2,5-diyl, 1,3-dithiane-2,5
-Diyl, wherein one hydrogen atom is F, Cl and / or C
1,3-thiazole-2,4 which may be substituted by N
-Diyl, wherein one hydrogen atom is F, Cl and / or C
1,3-thiazole-2,5 which may be substituted by N
-Diyl, wherein one hydrogen atom is F, Cl and / or C
Thiophene-2,4-diyl optionally substituted with N, thiophen-2,5-diyl optionally substituted with one or two hydrogen atoms by F, Cl and / or CN, piperazine-1 , 4-diyl, piperazine-2,
5-diyl, one or more hydrogen atoms being F, Cl
And / or naphthalene-2,6-diyl optionally substituted with CN, bicyclo [2.2.2] optionally having one or more hydrogen atoms substituted with F, Cl and / or CN. Octane-1,4-diyl or 1,3-dioxaborinane-2,5-diyl;
n and m are 0 or 1, but the maximum of the sum is 1.

In the formula (I), R ¹ and R ² are linear or branched alkyl groups having 1 to 16 carbon atoms (which may or may not have asymmetric carbon atoms). , Wherein one or more —CH ₂ — groups are —O—, cyclopropane-1,2-diyl or —Si (CH ₃ ) ₂ —.
Optionally with the proviso that the chalcogens are not directly bonded to each other and one or more hydrogen atoms of the alkyl group are further substituted with F; R ¹ or R ² may be H , But not H at the same time;

In the formula (I), R ¹ and R ² are linear or branched alkyl groups having 1 to 10 carbon atoms,
Wherein at least two additional from ring -CH ₂ - are separated by a group one -CH ₂ - group is -Si (CH _{3) 2} -
Are particularly preferred.

The compound of the present invention has a large negative dielectric anisotropy, but it can be used as a chiral compound in the ferroelectric liquid crystal composition of the present invention by introducing a group having a chiral structure into this skeleton. However, since the spontaneous polarization value is not so high in the driving method using τ-Vmin, the amount thereof is limited when the compound of the general formula (I) is used as the chiral dopant.

Since a chiral compound generally has a high viscosity, it is preferable to use a chiral structure such as phenylpyrimidine having a low-viscosity skeleton which exhibits a high spontaneous polarization at a low concentration. Therefore, the compound of the general formula (I) of the present invention is preferably used non-chirally. When used as a chiral dopant, compounds in which R ¹ and / or R ² contain F are preferred.

Further, in order to lower the viscosity, m and n are preferably 0.

Compounds of formula (Ia) in which E ¹ and / or E ⁴ are —N— are preferred,

[Chemical formula 26] Of these, the following compounds:

Embedded image Is preferable because of its low viscosity. Particularly, the fluorine-substituted compounds of the formulas (Ia5) and (Ia6) are particularly preferable because of the large negative value of Δε.

Further preferred are compounds of formula (Ib) wherein E ² and / or E ⁵ are —N—

Embedded image Of these, the following compounds:

[Chemical 29]

Embedded image

[Chemical 31] Is preferred because of its low viscosity. Particularly, the fluorine-substituted compounds of the formulas (Ib5) to (Ib16) have a large negative value of Δε and are particularly preferable.

Further, E ¹ and / or E ⁴ are —CF—
A compound of formula (Ic) is

Embedded image Of these, the following compounds:

[Chemical 33] Is particularly preferred.

Further, E ¹ and E ⁴ are -CH-,
And, E ² , E ³ , E ⁵ and E ⁶ are —CH— or —CF.
-, But at least one is -CF-.
compounds of d) are preferred,

Embedded image Of these, the following compounds:

Embedded image

Embedded image

Embedded image Is particularly preferred.

Particularly preferred compounds of formula (I)
Examples include: 1,8-
Difluoro-2,7-dioctyloxyphenanthre
1,8-difluoro-2,7-dibutoxyphenane
Tren, 1,8-difluoro-2,7-dipentoxyf
Enanthrene, 1,8-difluoro-2,7-dihex
Luoxyphenanthrene, 1,8-difluoro-2,7
-Diheptyloxyphenanthrene, 1,8-difluor
B-2,7-dinonyloxyphenanthrene, 1,8-
Difluoro-2,7-didecyloxyphenanthrene,
1,8-difluoro-2,7-diundecyloxyphene
Nanthrene, 1,8-difluoro-2,7-didodecyl
Oxyphenanthrene, 1,8-difluoro-2-but
Xy-7-pentoxyphenanthrene, 1,8-diflu
Oro-2-butoxy-7-hexyloxyphenanthre
1,8-difluoro-2-butoxy-7-heptyl
Oxyphenanthrene, 1,8-difluoro-2-but
Xy-7-octyloxyphenanthrene, 1,8-di
Fluoro-2-butoxy-7-nonyloxyphenanthate
Len, 1,8-difluoro-2-pentoxy-7-pro
Poxyphenanthrene, 1,8-difluoro-2-pen
Toxy-7-hexyloxyoxyphenanthre 1,8
-Difluoro-2-pentoxy-7-heptyloxyf
Enanthrene, 1,8-difluoro-2-pentoxy-
7-octyloxyphenanthrene, 1,8-difluo
R-2-Pentoxy-7-nonyloxyphenanthre
1,8-difluoro-2-hexyloxy-7-propyl
Ropoxyphenanthrene, 1,8-difluoro-2-he
Xyloxy-7-heptyloxyphenanthrene 1,
8-difluoro-2-hexyloxy-7-octyl io
Xyphenanthrene, 1,8-difluoro-2-hexyl
Luoxy-7-nonyloxyphenanthrene, 1,8-
Difluoro-2-hexyloxy-7-decyloxyo
Xyphenanthrene, 1,8-difluoro-2-hexyl
Luoxy-7-dodecyloxyoxyphenanthrene,
1,8-difluoro-2-heptyloxy-7-propo
Xyphenanthrene, 1,8-difluoro-2-hepti
Luoxy-7-octyloxyphenanthrene, 1,8
-Difluoro-2-heptyloxy-7-nonyloxy
Phenanthrene, 1,8-difluoro-2-octyl io
Xy-7-ethoxyphenanthrene, 1,8-difluor
Ro-2-octyloxy-7-propoxyphenanthre
1,8-difluoro-2-octyloxy-7-no
Nyloxyphenanthrene, 1,8-difluoro-2-
Octyloxy-7-decyloxyoxyphenanthre
1,8-difluoro-2-nonyloxy-7-eth
Xyphenanthrene, 1,8-difluoro-2-nonyl
Oxy-7-propoxyphenanthrene, 1,8-diph
Luoro-2-nonyloxy-7-decyloxyphenane
Tren, 1,8-difluoro-2-decyloxy-7-
Methoxyphenanthrene, 1,8-difluoro-2-de
Syloxy-7-ethoxyphenanthrene, 1,8-di
Fluoro-2-decyloxy-7-propoxyphenane
Tren, 1,8-difluoro-2-decyloxy-7-
Butoxyphenanthrene, 1,8-difluoro-2-de
Syloxy-7-pentoxyphenanthrene, 1,8-
Difluoro-2-decyloxy-7-heptyloxyf
Enanthrene, 1-fluoro-2,7-dibutoxide
Nanthrene, 1-fluoro-2,7-dipentoxyphe
Nanthrene, 1-fluoro-2,7-dihexyloxy
Phenanthrene, 1-fluoro-2,7-diheptylo
Xyphenanthrene, 1-fluoro-2,7-diocty
Luoxyphenanthrene, 1-fluoro-2,7-dino
Nyloxyphenanthrene, 1-fluoro-2,7-di
Decyloxyphenanthrene, 1-fluoro-2,7-
Diundecyloxyphenanthrene, 1-fluoro-
2,7-didodecyloxyphenanthrene, 1-fluor
Ro-2-butoxy-7-pentoxyphenanthrene, 1
-Fluoro-2-butoxy-7-hexyloxyphena
Trene, 1-fluoro-2-butoxy-7-heptyl
Oxyphenanthrene, 1-fluoro-2-butoxy-
7-octyloxyphenanthrene, 1-fluoro-2
-Butoxy-7-nonyloxyphenanthrene, 1-f
Luoro-2-butoxy-7-decyloxyphenanthre
1-fluoro-2-pentoxy-7-hexyloxy
Ciphenanthrene, 1-fluoro-2-pentoxy-7
-Heptyloxyphenanthrene, 1-fluoro-2-
Pentoxy-7-octyloxyphenanthrene, 1-
Fluoro-2-pentoxy-7-nonyloxyphenane
Tren, 1-fluoro-2-hexyloxy-7-but
Xyphenanthrene, 1-fluoro-2-hexyloxy
Ci-7-pentoxyphenanthrene, 1-fluoro-2
-Hexyloxy-7-heptyloxyphenanthre
1-fluoro-2-hexyloxy-7-octyl
Oxyphenanthrene, 1-fluoro-2-hexyl
Xy-7-nonyloxyphenanthrene, 1-fluoro
-2-hexyloxy-7-decyloxyphenanthre
1-fluoro-2-heptyloxy-7-propoxy
Ciphenanthrene, 1-fluoro-2-heptyloxy
-7-butoxyphenanthrene, 1-fluoro-2-he
Butyloxy-7-pentoxyphenanthrene, 1-fu
Luoro-2-heptyloxy-7-octyloxyphene
Nanthrene, 1-fluoro-2-heptyloxy-7-
Nonyloxyphenanthrene, 1-fluoro-2-hep
Tyloxy-7-decyloxyphenanthrene, 1-f
Luoro-2-octyloxyphenanthrene, 1-full
Oro-2-octyloxy-7-propoxyphenanthate
Len, 1-fluoro-2-octyloxy-7-butoki
Ciphenanthrene, 1-fluoro-2-octyloxy
-7-Pentoxyphenanthrene, 1-Fluoro-2-
Octyloxy-7-hexyloxyphenanthrene,
1-Fluoro-2-octyloxy-7-octyloxy
Ciphenanthrene, 1-fluoro-2-octyloxy
-7-nonyloxyphenanthrene, 1-fluoro-2
-Octyloxy-7-decyloxyphenanthrene,
1-Fluoro-2-octyloxy-7-undecyl-o
Xyphenanthrene, 1-fluoro-2-nonyloxy
-7-propoxyphenanthrene, 1-fluoro-2-
Nonyloxy-7-butoxyphenanthrene, 1-flu
Oro-2-nonyloxy-7-pentoxyphenanthre
1-fluoro-2-nonyloxy-7-hexyl
Xyphenanthrene, 1-fluoro-2-nonyloxy
-7-heptyloxyphenanthrene, 1-fluoro-
2-nonyloxy-7-octyloxyphenanthre
1-fluoro-2-nonyloxy-7-decyloxy
Ciphenanthrene, 2,7-bis (hexyloxy)-
1,8-diazaphenanthrene, 2,7-bis (pento
Xy) -1,8-diazaphenanthrene, 2,7-bis
(Heptyloxy) -1,8-diazaphenanthrene,
2,7-bis (octyloxy) -1,8-diazafe
Nanthrene, 2,7-bis (nonyloxy) -1,8-
Diazaphenanthrene, 2,7-bis (decyloxy)
-1,8-diazaphenanthrene, 2,7-bis (un
Decyloxy) -1,8-diazaphenanthrene, 2,
7-bis (dodecyloxy) -1,8-diazaphenane
Tren, 2-butoxy-7-pentoxy-1,8-dia
The phenanthrene, 2-butoxy-7-hexyloxy
-1,8-diazaphenanthrene, 2-butoxy-7-
Heptyloxy-1,8-diazaphenanthrene, 2-
Butoxy-7-octyloxy-1,8-diazaphena
Tren, 2-butoxy-7-nonyloxy-1,8-
Diazaphenanthrene, 2-butoxy-7-decyloxy
Ci-1,8-diazaphenanthrene, 2-pentoxy-
7-hexyloxy-1,8-diazaphenanthrene,
2-Pentoxy-7-heptyloxy-1,8-diaza
Phenanthrene, 2-pentoxy-7-octyloxy
-1,8-diazaphenanthrene, 2-pentoxy-7
-Nonyloxy-1,8-diazaphenanthrene, 2-
Pentoxy-7-decyloxy-1,8-diazaphena
Trene, 2-hexyloxy-7-heptyloxy-
1,8-diazaphenanthrene, 2-hexyloxy-
7-octyloxy-1,8-diazaphenanthrene,
2-hexyloxy-7-nonyloxy-1,8-dia
Thephenanthrene, 2-hexyloxy-7-decyl-o
Xy-1,8-diazaphenanthrene, 2-hexyl
Xy-7- (4-butyldimethylsilyl) butoxy-
1,8-diazaphenanthrene, 2-hexyloxy-
1,8-diazaphenanthrene, 2-hexyloxy-
7-methyl-1,8-diazaphenanthrene, 2-hep
Tyloxy-7-octyloxy-1,8-diazafe
Nanthrene, 2-heptyloxy-7-nonyloxy-
1,8-diazaphenanthrene, 2-heptyloxy-
7-decyloxy-1,8-diazaphenanthrene, 2
-Heptyloxy-7- (6-methyl) octyloxy
-1,8-diazaphenanthrene, 2-octyloxy
-7-nonyloxy-1,8-diazaphenanthrene,
2-octyloxy-7-decyloxy-1,8-dia
The phenanthrene, 2-octyloxy-7-undec
Luoxy-1,8-diazaphenanthrene, 2-octyl
Luoxy-7-dodecyloxy-1,8-diazaphena
Tren, 2-octyloxy-7- (5-oxa) no
Nyloxy-1,8-diazaphenanthrene, 2-noni
Luoxy-7-decyloxy-1,8-diazaphenane
Tren, 2-nonyloxy-7-undecyloxy-
1,8-diazaphenanthrene, 2-nonyloxy-7
-Dodecyloxy-1,8-diazaphenanthrene, 2
-Decyloxy-7-undecyloxy-1,8-dia
The phenanthrene, 2-decyloxy-7-dodecyl o
Xy-1,8-diazaphenanthrene, 2-butoxy-
7-Pentoxy-1-azaphenanthrene, 2-butoki
Ci-7-hexyloxy-1-azaphenanthrene, 2
-Butoxy-7-heptyloxy-1-azaphenanthate
Len, 2-butoxy-7-octyloxy-1-azaf
Enanthrene, 2-butoxy-7-nonyloxy-1-
Azaphenanthrene, 2-butoxy-7-decyloxy
-1-Azaphenanthrene, 2-Pentoxy-7-hex
Syloxy-1-azaphenanthrene, 2-pentoxy
-7-heptyloxy-1-azaphenanthrene, 2-
Pentoxy-7-octyloxy-1-azaphenanth
Len, 2-pentoxy-7-nonyloxy-1-azaf
Enanthrene, 2-pentoxy-7-decyloxy-1
-Azaphenanthrene, 2-hexyloxy-7-hep
Tyloxy-1-azaphenanthrene, 2-hexylo
Xy-7-octyloxy-1-azaphenanthrene,
2-hexyloxy-7-nonyloxy-1-azafe
Nanthrene, 2-hexyloxy-7-decyloxy-
1-azaphenanthrene, 2-hexyloxy-7-
(4-Butyldimethylsilyl) butoxy-1 azaphena
Tren, 2-heptyloxy-7-octyloxy-
1-azaphenanthrene, 2-heptyloxy-7-no
Nyloxy-1-azaphenanthrene, 2-heptylo
Xy-7-decyloxy-1-azaphenanthrene, 2
-Heptyloxy-7- (6-methyl) octyloxy
-1-Azaphenanthrene, 2-octyloxy-7-
Nonyloxy-1-azaphenanthrene, 2-octyl
Oxy-7-decyloxy-1-azaphenanthrene,
2-octyloxy-7-undecyloxy-1-aza
Phenanthrene, 2-octyloxy-7-dodecylo
Xy-1-azaphenanthrene, 2-octyloxy-
7- (5-oxa) nonyloxy-1-azaphenanthate
Len, 2-nonyloxy-7-decyloxy-1-aza
Phenanthrene, 2-nonyloxy-7-undecylo
Xy-1-azaphenanthrene, 2-nonyloxy-7
-Dodecyloxy-1-azaphenanthrene, 2-decyl
Luoxy-7-undecyloxy-1-azaphenanthate
Len, 2-decyloxy-7-dodecyloxy-1-a
Thephenanthrene, 2-hexyloxy-7-pentoki
Ci-1-azaphenanthrene, 2-heptyloxy-7
-Hexyloxy-1-azaphenanthrene, 2-hep
Tyloxy-7-pentoxy-1-azaphenanthre
2-octyloxy-7-butoxy-1-azafe
Nanthrene, 2-octyloxy-7-pentoxy-1
-Azaphenanthrene, 2-octyloxy-7-hex
Syloxy-1-azaphenanthrene, 2-octylo
Xy-7-heptyloxy-1-azaphenanthrene,
2-nonyloxy-7-pentoxy-1-azaphenane
Tren, 2-nonyloxy-7-hexyloxy-1-
Azaphenanthrene, 2-nonyloxy-7-heptyl
Oxy-1-azaphenanthrene, 2-nonyloxy-
7-octyloxy-1-azaphenanthrene, 2-bu
Toxy-7-pentoxy-8-fluoro-1-azafe
Nanthrene, 2-butoxy-7-hexyloxy-8-
Fluoro-1-azaphenanthrene, 2-butoxy-7
-Heptyloxy-8-fluoro-1-azaphenanthate
Len, 2-butoxy-7-octyloxy-8-fluor
Ro-1-azaphenanthrene, 2-butoxy-7-noni
Luoxy-8-fluoro-1-azaphenanthrene, 2
-Butoxy-7-decyloxy-8-fluoro-1-a
The Phenanthrene, 2-Pentoxy-7-hexyloxy
Ci-8-fluoro-1-azaphenanthrene, 2-pen
Toxy-7-heptyloxy-8-fluoro-1-aza
Phenanthrene, 2-pentoxy-7-octyloxy
-8-Fluoro-1-azaphenanthrene, 2-pento
Xy-7-nonyloxy-8-fluoro-1-azafe
Nanthrene, 2-pentoxy-7-decyloxy-8-
Fluoro-1-azaphenanthrene, 2-hexyloxy
Ci-7-heptyloxy-8-fluoro-1-azafe
Nanthrene, 2,7-bis (hexyloxy) -8-fu
Luoro-1-azaphenanthrene, 2-hexyloxy
-7-octyloxy-8-fluoro-1-azaphena
Trene, 2-hexyloxy-7-nonyloxy-8
-Fluoro-1-azaphenanthrene, 2-hexylo
Xy-7-decyloxy-8-fluoro-1-azafe
Nanthrene, 2-hexyloxy-7- (4-butyldi)
Methylsilyl) butoxy-8-fluoro-1-azafe
Nanthrene, 2-heptyloxy-7-octyloxy
-8-Fluoro-1-azaphenanthrene, 2-hepti
Luoxy-7-nonyloxy-8-fluoro-1-aza
Phenanthrene, 2-heptyloxy-7-decyloxy
Ci-8-fluoro-1-azaphenanthrene, 2-hep
Tyloxy-7- (6-methyl) octyloxy-8-
Fluoro-1-azaphenanthrene, 2-octyloxy
Ci-7-nonyloxy-8-fluoro-1-azaphena
Trene, 2-octyloxy-7-decyloxy-8
-Fluoro-1-azaphenanthrene, 2-octyl io
Xy-7-undecyloxy-8-fluoro-1-aza
Phenanthrene, 2-octyloxy-7-dodecylo
Xy-8-fluoro-1-azaphenanthrene, 2-o
Cutyloxy-7- (5-oxa) nonyloxy-8-
Fluoro-1-azaphenanthrene, 2-nonyloxy
-7-decyloxy-8-fluoro-1-azaphenane
Tren, 2-nonyloxy-7-undecyloxy-8
-Fluoro-1-azaphenanthrene, 2-nonyloxy
Ci-7-dodecyloxy-8-fluoro-1-azafe
Nanthrene, 2-decyloxy-7-undecyloxy
-8-Fluoro-1-azaphenanthrene, 2-decyl
Oxy-7-dodecyloxy-8-fluoro-1-aza
Phenanthrene, 2-hexyloxy-7-pentoxy
-8-Fluoro-1-azaphenanthrene, 2-hepti
Luoxy-7-hexyl-8-fluoro-1-azafe
Nanthrene, 2-heptyloxy-7-pentoxy-8
-Fluoro-1-azaphenanthrene, 2-octyl io
Xy-7-butoxy-8-fluoro-1-azaphenane
Tren, 2-octyloxy-7-pentoxy-8-fur
Luoro-1-azaphenanthrene, 2-octyloxy
-7-hexyloxy-8-fluoro-1-azaphena
Tren, 2-octyloxy-7-heptyloxy-
8-fluoro-1-azaphenanthrene, 2-nonylo
Xy-7-pentoxy-8-fluoro-1-azaphena
Trene, 2-nonyloxy-7-hexyloxy-8
-Fluoro-1-azaphenanthrene, 2-nonyloxy
Ci-7-heptyloxy-8-fluoro-1-azafe
Nanthrene, 2-nonyloxy-7-octyloxy-
8-fluoro-1-azaphenanthrene, 2-hexyl
Oxy-8-fluoro-1-azaphenanthrene, 1,
8-difluoro-2,7-dioctyloxy-9,10
-Dihydrophenanthrene, 1,8-difluoro-2,
7-dibutoxy-9,10-dihydrophenanthrene,
1,8-difluoro-2,7-dipentoxy-9,10
-Dihydrophenanthrene, 1,8-difluoro-2,
7-dihexyloxy-9,10-dihydrophenanthate
Len, 1,8-difluoro-2,7-diheptyloxy
-9,10-dihydrophenanthrene, 1,8-diflu
Oro-2,7-dinonyloxy-9,10-dihydrof
Enanthrene, 1,8-difluoro-2,7-didecyl
Oxy-9,10-dihydrophenanthrene, 1,8-
Difluoro-2,7-diundecyloxy-9,10-
Dihydrophenanthrene, 1,8-difluoro-2,7
-Didodecyloxy-9,10-dihydrophenanthre
1,8-difluoro-2-butoxy-7-pentoxy
Ci-9,10-dihydrophenanthrene, 1,8-diph
Luoro-2-butoxy-7-hexyloxy-9,10
-Dihydrophenanthrene, 1,8-difluoro-2-
Butoxy-7-heptyloxy-9,10-dihydrof
Enanthrene, 1,8-difluoro-2-butoxy-7
-Octyloxy-9,10-dihydrophenanthre
1,8-difluoro-2-butoxy-7-nonylio
Xy-9,10-dihydrophenanthrene, 1,8-di
Fluoro-2-pentoxy-7-propoxy-9,10
-Dihydrophenanthrene, 1,8-difluoro-2-
Pentoxy-7-hexyloxy-9,10-dihydro
Phenanthrene, 1,8-difluoro-2-pentoxy
-7-Heptyloxy-9,10-dihydrophenant
Len, 1,8-difluoro-2-pentoxy-7-oct
Tyloxy-9,10-dihydrophenanthrene, 1,
8-difluoro-2-pentoxy-7-nonyloxy-
9,10-dihydrophenanthrene, 1,8-difluor
Ro-2-hexyloxy-7-propoxy-9,10-
Dihydrophenanthrene, 1,8-difluoro-2-he
Xyloxy-7-heptyloxy-9,10-dihydr
Lophenanthrene, 1,8-difluoro-2-hexyl
Oxy-7-octyloxy-9,10-dihydrofe
Nanthrene, 1,8-difluoro-2-hexyloxy
-7-nonyloxy-9,10-dihydrophenanthre
1,8-difluoro-2-hexyloxy-7-de
Syloxy-9,10-dihydrophenanthrene, 1,
8-difluoro-2-hexyloxy-7-dodecyl io
Xy-9,10-dihydrophenanthrene, 1,8-di
Fluoro-2-heptyloxy-7-propoxy-9,
10-dihydrophenanthrene, 1,8-difluoro-
2-heptyloxy-7-octyloxy-9,10-
Dihydrophenanthrene, 1,8-difluoro-2-he
Butyloxy-7-nonyloxy-9,10-dihydro
Phenanthrene, 1,8-difluoro-2-octyl io
Xy-7-ethoxy-9,10-dihydrophenanthre
1,8-difluoro-2-octyloxy-7-p
Ropoxy-9,10-dihydrophenanthrene, 1,8
-Difluoro-2-octyloxy-7-nonyloxy
-9,10-dihydrophenanthrene, 1,8-diflu
Oro-2-octyloxy-7-decyloxy-9,1
0-dihydrophenanthrene, 1,8-difluoro-2
-Nonyloxy-7-ethoxy-9,10-dihydrof
Enanthrene, 1,8-difluoro-2-nonyloxy
-7-propoxy-9,10-dihydrophenanthre
1,8-difluoro-2-nonyloxy-7-decyl
Luoxy-9,10-dihydrophenanthrene, 1,8
-Difluoro-2-decyloxy-7-methoxy-9,
10-dihydrophenanthrene, 1,8-difluoro-
2-decyloxy-7-ethoxy-9,10-dihydro
Phenanthrene, 1,8-difluoro-2-decyloxy
Ci-7-propoxy-9,10-dihydrophenanthre
1,8-difluoro-2-decyloxy-7-but
Xy-9,10-dihydrophenanthrene, 1,8-di
Fluoro-2-decyloxy-7-pentoxy-9,1
0-dihydrophenanthrene, 1,8-difluoro-2
-Decyloxy-7-heptyloxy-9,10-dihi
Drophenanthrene, 1-Fluoro-2,7-dibutoki
Ci-9,10-dihydrophenanthrene, 1-fluoro
-2,7-dipentoxy-9,10-dihydrophenane
Tren, 1-fluoro-2,7-dihexyloxy-
9,10-dihydrophenanthrene, 1-fluoro-
2,7-Diheptyloxy-9,10-dihydrophena
Trene, 1-fluoro-2,7-dioctyloxy-
9,10-dihydrophenanthrene, 1-fluoro-
2,7-dinonyloxy-9,10-dihydrophenane
Tren, 1-fluoro-2,7-didecyloxy-9,
10-dihydrophenanthrene, 1-fluoro-2,7
-Diundecyloxy-9,10-dihydrophenant
Len, 1-fluoro-2,7-didodecyloxy-9,
10-dihydrophenanthrene, 1-fluoro-2-bu
Toxy-7-pentoxy-9,10-dihydrophenane
Tren, 1-fluoro-2-butoxy-7-hexylo
Xy-9,10-dihydrophenanthrene, 1-fluor
R-2-butoxy-7-heptyloxy-9,10-di
Hydrophenanthrene, 1-fluoro-2-butoxy-
7-octyloxy-9,10-dihydrophenanthre
1-fluoro-2-butoxy-7-nonyloxy-
9,10-dihydrophenanthrene, 1-fluoro-2
-Butoxy-7-decyloxy-9,10-dihydrof
Enanthrene, 1-Fluoro-2-pentoxy-7-f
Xyloxy-9,10-dihydrophenanthrene, 1
-Fluoro-2-pentoxy-7-heptyloxy-
9,10-dihydrophenanthrene, 1-fluoro-2
-Pentoxy-7-octyloxy-9,10-dihydride
Lophenanthrene, 1-fluoro-2-pentoxy-7
-Nonyloxy-9,10-dihydrophenanthrene,
1-fluoro-2-hexyloxy-7-butoxy-
9,10-dihydrophenanthrene, 1-fluoro-2
-Hexyloxy-7-pentoxy-9,10-dihydr
Lophenanthrene, 1-fluoro-2-hexyloxy
-7-Heptyloxy-9,10-dihydrophenant
Len, 1-fluoro-2-hexyloxy-7-octyl
Luoxy-9,10-dihydrophenanthrene, 1-f
Luoro-2-hexyloxy-7-nonyloxy-9,
10-dihydrophenanthrene, 1-fluoro-2-he
Xyloxy-7-decyloxy-9,10-dihydro
Phenanthrene, 1-fluoro-2-heptyloxy-
7-propoxy-9,10-dihydrophenanthrene,
1-fluoro-2-heptyloxy-7-butoxy-
9,10-dihydrophenanthrene, 1-fluoro-2
-Heptyloxy-7-pentoxy-9,10-dihydr
Lophenanthrene, 1-fluoro-2-heptyloxy
-7-octyloxy-9,10-dihydrophenanthate
Len, 1-fluoro-2-heptyloxy-7-nonyl
Oxy-9,10-dihydrophenanthrene, 1-fur
Oro-2-heptyloxy-7-decyloxy-9,1
0-dihydrophenanthrene, 1-fluoro-2-octane
Tyloxy-7-propoxy-9,10-dihydrofe
Nanthrene, 1-Fluoro-2-octyloxy-7-
Butoxy-9,10-dihydrophenanthrene, 1-f
Luoro-2-octyloxy-7-pentoxy-9,1
0-dihydrophenanthrene, 1-fluoro-2-octane
Tyloxy-7-hexyloxy-9,10-dihydro
Phenanthrene, 1-fluoro-2-octyloxy-
7-octyloxy-9,10-dihydrophenanthre
1-fluoro-2-octyloxy-7-nonylio
Xy-9,10-dihydrophenanthrene, 1-fluor
Ro-2-octyloxy-7-decyloxy-9,10
-Dihydrophenanthrene, 1-fluoro-2-octyl
Luoxy-7-undecyloxy-9,10-dihydro
Phenanthrene, 1-fluoro-2-nonyloxy-7
-Propoxy-9,10-dihydrophenanthrene, 1
-Fluoro-2-nonyloxy-7-butoxy-9,1
0-dihydrophenanthrene, 1-fluoro-2-noni
Luoxy-7-pentoxy-9,10-dihydrophena
Trene, 1-fluoro-2-nonyloxy-7-hex
Syloxy-9,10-dihydrophenanthrene, 1-
Fluoro-2-nonyloxy-7-heptyloxy-
9,10-dihydrophenanthrene, 1-fluoro-2
-Nonyloxy-7-octyloxy-9,10-dihi
Drophenanthrene, 1-Fluoro-2-nonyloxy
-7-decyloxy-9,10-dihydrophenanthre
2,7-bis (pentoxy) 1,8-diaza-9,
10-dihydrophenanthrene, 2,7-bis (hepti
1,8-diaza-9,10-dihydrophena
Tren, 2,7-bis (octyloxy) 1,8-di
Aza-9,10-dihydrophenanthrene, 2,7-bi
Su (nonyloxy) 1,8-diaza-9,10-dihydr
Lophenanthrene, 2,7-bis (decyloxy) 1,
8-diaza-9,10-dihydrophenanthrene, 2,
7-bis (undecyloxy) 1,8-diaza-9,1
0-dihydrophenanthrene, 2,7-bis (dodecyl)
Oxy) 1,8-diaza-9,10-dihydrophenane
Tren, 2-butoxy-7-pentoxy-1,8-dia
The-9,10-dihydrophenanthrene, 2-butoxy
-7-Hexyloxy-1,8-diaza-9,10-di
Hydrophenanthrene, 2-butoxy-7-heptylo
Xy-1,8-diaza-9,10-dihydrophenanthate
Len, 2-butoxy-7-octyloxy-1,8-di
Aza-9,10-dihydrophenanthrene, 2-butoki
Ci-7-nonyloxy-1,8-diaza-9,10-di
Hydrophenanthrene, 2-butoxy-7-decyloxy
Ci-1,8-diaza-9,10-dihydrophenanthre
2-pentoxy-7-hexyloxy-1,8-di
Aza-9,10-dihydrophenanthrene, 2-pento
Xy-7-heptyloxy-1,8-diaza-9,10
-Dihydrophenanthrene, 2-pentoxy-7-oct
Tyloxy-1,8-diaza-9,10-dihydrofe
Nanthrene, 2-pentoxy-7-nonyloxy-1,
8-diaza-9,10-dihydrophenanthrene, 2-
Pentoxy-7-decyloxy-1,8-diaza-9,
10-dihydrophenanthrene, 2-hexyloxy-
7-heptyloxy-1,8-diaza-9,10-dihi
Drophenanthrene, 2-hexyloxy-7-octyl
Luoxy-1,8-diaza-9,10-dihydrophena
Trene, 2-hexyloxy-7-nonyloxy-
1,8-diaza-9,10-dihydrophenanthrene,
2-hexyloxy-7-decyloxy-1,8-dia
The-9,10-dihydrophenanthrene, 2-hexyl
Oxy-7- (4-butyldimethylsilyl) butoxy-
1,8-diaza-9,10-dihydrophenanthrene,
2-heptyloxy-7-octyloxy-1,8-di
Aza-9,10-dihydrophenanthrene, 2-hepti
Luoxy-7-nonyloxy-1,8-diaza-9,1
0-dihydrophenanthrene, 2-heptyloxy-7
-Decyloxy-1,8-diaza-9,10-dihydro
Phenanthrene, 2-heptyloxy-7- (6-methyl
Le) octyloxy-1,8-diaza-9,10-dihi
Drophenanthrene, 2-octyloxy-7-nonyl
Oxy-1,8-diaza-9,10-dihydrophenane
Tren, 2-octyloxy-7-decyloxy-1,
8-diaza-9,10-dihydrophenanthrene, 2-
Octyloxy-7-undecyloxy-1,8-dia
The-9,10-dihydrophenanthrene, 2-octyl
Oxy-7-dodecyloxy-1,8-diaza-9,1
0-dihydrophenanthrene, 2-octyloxy-7
-(5-oxa) nonyloxy-1,8-diaza-9,
10-dihydrophenanthrene, 2-nonyloxy-7
-Decyloxy-1,8-diaza-9,10-dihydro
Phenanthrene, 2-nonyloxy-7-undecylo
Xy-1,8-diaza-9,10-dihydrophenanthate
Len, 2-nonyloxy-7-dodecyloxy-1,8
-Diaza-9,10-dihydrophenanthrene, 2-de
Syloxy-7-undecyloxy-1,8-diaza-
9,10-dihydrophenanthrene, 2-decyloxy
-7-dodecyloxy-1,8-diaza-9,10-di
Hydrophenanthrene, 2-butoxy-7-pentoxy
-1-Aza-9,10-dihydrophenanthrene, 2-
Butoxy-7-hexyloxy-1-aza-9,10-
Dihydrophenanthrene, 2-butoxy-7-heptyl
Oxy-1-aza-9,10-dihydrophenanthre
2-butoxy-7-octyloxy-1-aza-
9,10-dihydrophenanthrene, 2-butoxy-7
-Nonyloxy-1-aza-9,10-dihydrophena
Trene, 2-butoxy-7-decyloxy-1-aza
-9,10-dihydrophenanthrene, 2-pentoxy
-7-Hexyloxy-1-aza-9,10-dihydro
Phenanthrene, 2-pentoxy-7-heptyloxy
-1-Aza-9,10-dihydrophenanthrene, 2-
Pentoxy-7-octyloxy-1-aza-9,10
-Dihydrophenanthrene, 2-pentoxy-7-noni
Luoxy-1-aza-9,10-dihydrophenanthre
2-pentoxy-7-decyloxy-1-aza-
9,10-dihydrophenanthrene, 2-hexyloxy
Ci-7-heptyloxy-1-aza-9,10-dihydr
Lophenanthrene, 2-hexyloxy-7-octyl
Oxy-1-aza-9,10-dihydrophenanthre
2-hexyloxy-7-nonyloxy-1-aza
-9,10-dihydrophenanthrene, 2-hexylo
Xy-7-decyloxy-1-aza-9,10-dihydr
Lophenanthrene, 2-hexyloxy-7- (4-bu
Cyldimethylsilyl) butoxy-1-aza-9,10-
Dihydrophenanthrene, 2-heptyloxy-7-o
Cutyloxy-1-aza-9,10-dihydrophenane
Tren, 2-heptyloxy-7-nonyloxy-1-
Aza-9,10-dihydrophenanthrene, 2-hepti
Luoxy-7-decyloxy-1-aza-9,10-di
Hydrophenanthrene, 2-heptyloxy-7- (6
-Methyl) octyloxy-1-aza-9,10-dihi
Drophenanthrene, 2-octyloxy-7-nonyl
Oxy-1-aza-9,10-dihydrophenanthre
2-octyloxy-7-decyloxy-1-aza
-9,10-dihydrophenanthrene, 2-octyl io
Xy-7-undecyloxy-1-aza-9,10-di
Hydrophenanthrene, 2-octyloxy-7-dode
Syloxy-1-aza-9,10-dihydrophenant
Len, 2-octyloxy-7- (5-oxa) nonyl
Oxy-1-aza-9,10-dihydrophenanthre
2-nonyloxy-7-decyloxy-1-aza-
9,10-dihydrophenanthrene, 2-nonyloxy
-7-Undecyloxy-1-aza-9,10-dihydr
Lophenanthrene, 2-nonyloxy-7-dodecyl io
Xyl-1-aza-9,10-dihydrophenanthrene,
2-decyloxy-7-undecyloxy-1-aza-
9,10-dihydrophenanthrene, 2-decyloxy
-7-dodecyloxy-1-aza-9,10-dihydro
Phenanthrene, 2-hexyloxy-7-pentoxy
-1-Aza-9,10-dihydrophenanthrene, 2-
Heptyloxy-7-hexyloxy-1-aza-9,
10-dihydrophenanthrene, 2-heptyloxy-
7-Pentoxy-1-aza-9,10-dihydrophena
Tren, 2-octyloxy-7-butoxy-1-a
The-9,10-dihydrophenanthrene, 2-octyl
Oxy-7-pentoxy-1-aza-9,10-dihydr
Lophenanthrene, 2-octyloxy-7-hexyl
Oxy-1-aza-9,10-dihydrophenanthre
2-octyloxy-7-heptyloxy-1-a
The-9,10-dihydrophenanthrene, 2-nonio
Xy-7-pentoxy-1-aza-9,10-dihydro
Phenanthrene, 2-nonyloxy-7-hexyloxy
Ci-1-aza-9,10-dihydrophenanthrene, 2
-Nonyloxy-7-heptyloxy-1-aza-9,
10-dihydrophenanthrene, 2-nonyloxy-7
-Octyloxy-1-aza-9,10-dihydrofe
Nanthrene, 2-butoxy-7-pentoxy-8-full
Oro-1-aza-9,10-dihydrophenanthrene,
2-butoxy-7-hexyloxy-8-fluoro-1
-Aza-9,10-dihydrophenanthrene, 2-but
Xy-7-heptyloxy-8-fluoro-1-aza-
9,10-dihydrophenanthrene, 2-butoxy-7
-Octyloxy-8-fluoro-1-aza-9,10
-Dihydrophenanthrene, 2-butoxy-7-nonyl
Oxy-8-fluoro-1-aza-9,10-dihydro
Phenanthrene, 2-butoxy-7-decyloxy-8
-Fluoro-1-aza-9,10-dihydrophenant
Len, 2-pentoxy-7-hexyloxy-8-fur
Oro-1-aza-9,10-dihydrophenanthrene,
2-Pentoxy-7-heptyloxy-8-fluoro-
1-aza-9,10-dihydrophenanthrene, 2-pe
Tonoxy-7-octyloxy-8-fluoro-1-a
The-9,10-dihydrophenanthrene, 2-pentoki
Ci-7-nonyloxy-8-fluoro-1-aza-9,
10-dihydrophenanthrene, 2-pentoxy-7-
Decyloxy-8-fluoro-1-aza-9,10-di
Hydrophenanthrene, 2-hexyloxy-7-hep
Tyloxy-8-fluoro-1-aza-9,10-dihi
Drophenanthrene, 2-hexyloxy-7-octyl
Luoxy-8-fluoro-1-aza-9,10-dihydr
Lophenanthrene, 2-hexyloxy-7-nonylio
Xy-8-fluoro-1-aza-9,10-dihydro
Enanthrene, 2-hexyloxy-7-decyloxy
-8-Fluoro-1-aza-9,10-dihydrophena
Trene, 2-hexyloxy-7- (4-butyldime
Tylsilyl) butoxy-8-fluoro-1-aza-9,
10-dihydrophenanthrene, 2-heptyloxy-
7-octyloxy-8-fluoro-1-aza-9,1
0-dihydrophenanthrene, 2-heptyloxy-7
-Nonyloxy-8-fluoro-1-aza-9,10-
Dihydrophenanthrene, 2-heptyloxy-7-de
Syloxy-8-fluoro-1-aza-9,10-dihi
Dorophenanthrene, 2-heptyloxy-7- (6-
Methyl) octyloxy-8-fluoro-1-aza-
9,10-dihydrophenanthrene, 2-octyloxy
Ci-7-nonyloxy-8-fluoro-1-aza-9,
10-dihydrophenanthrene, 2-octyloxy-
7-decyloxy-8-fluoro-1-aza-9,10
-Dihydrophenanthrene, 2-octyloxy-7-
Undecyloxy-8-fluoro-1-aza-9,10
-Dihydrophenanthrene, 2-octyloxy-7-
Dodecyloxy-8-fluoro-1-aza-9,10-
Dihydrophenanthrene, 2-octyloxy-7-
(5-Oxa) nonyloxy-8-fluoro-1-aza
-9,10-dihydrophenanthrene, 2-nonyloxy
Ci-7-decyloxy-8-fluoro-1-aza-9,
10-dihydrophenanthrene, 2-nonyloxy-7
-Undecyloxy-8-fluoro-1-aza-9,1
0-dihydrophenanthrene, 2-nonyloxy-7-
Dodecyloxy-8-fluoro-1-aza-9,10-
Dihydrophenanthrene, 2-decyloxy-7-un
Decyloxy-8-fluoro-1-aza-9,10-di
Hydrophenanthrene, 2-decyloxy-7-dodecyl
Luoxy-8-fluoro-1-aza-9,10-dihydr
Lophenanthrene, 2-hexyloxy-7-pentoki
Ci-8-fluoro-1-aza-9,10-dihydrofe
Nanthrene, 2-heptyloxy-7-hexyloxy
-8-Fluoro-1-aza-9,10-dihydrophena
Tren, 2-heptyloxy-7-pentoxy-8-
Fluoro-1-aza-9,10-dihydrophenanthre
2-octyloxy-7-butoxy-8-fluoro
-1-Aza-9,10-dihydrophenanthrene, 2-
Octyloxy-7-pentoxy-8-fluoro-1-
Aza-9,10-dihydrophenanthrene, 2-octyl
Luoxy-7-hexyloxy-8-fluoro-1-a
The-9,10-dihydrophenanthrene, 2-octyl
Oxy-7-heptyloxy-8-fluoro-1-aza
-9,10-dihydrophenanthrene, 2-nonyloxy
Ci-7-Pentoxy-8-fluoro-1-aza-9,1
0-dihydrophenanthrene, 2-nonyloxy-7-
Hexyloxy-8-fluoro-1-aza-9,10-
Dihydrophenanthrene, 2-nonyloxy-7-hep
Tyloxy-8-fluoro-1-aza-9,10-dihi
Drophenanthrene, 2-nonyloxy-7-octyl
Oxy-8-fluoro-1-aza-9,10-dihydro
Phenanthrene.

The compounds of formula (I) can be prepared according to standard textbooks relating to organic synthesis (eg Houben-Wey).
l), Methoden der Organischen Chemie, Georg-Thieme-Verlag, Stuttgart).

The preparation is carried out under reaction conditions which are known and suitable for the abovementioned reactions. Modifications known per se can also be carried out, but are not mentioned here in detail.

For example, for compounds containing a 1,4-cyclohexylene group and a 1,4-phenylene group, DE-
A2344732, 2450088, 2429093,
2502904, 2636684, 2701591 and 2752975; DE-A26441724 for compounds containing a pyrimidine-2,5-diyl group; DE-A4 for compounds containing a pyridine-2,5-diyl group.
022223 and EP-A 0 391 203; DE-A for compounds containing a pyridazine-3,6-diyl group
3231462; N. Miyaura, T. Yanagai, and A. Suzuki, Sy for the direct bond between an aromatic ring and an aromatic heterocycle.
nthetic Communications 11 (1981), 513-519, DE-
C3930663, MJSharp, W.Cheng, and V.Snieck
us, Tetrahedron Letters 28 (1987), 5093, GWGray,
J. Chem. Soc. Perkin Trans. II, 1989, 2041 and
Mol. Cryst. Liq. Cryst. 172 (1989), 165, 204 (199
1) 43 and 91, EP-A0449015, WO89 /
12039, WO89 / 03821; EP-A0354.
434;. -CH ₂ -CH ₂ - for compounds containing crosslinking, DE-A3201721; for compounds containing -C≡C- crosslinking, KojiSeto et al, Liquid Crystals 8
(1990) 861-870, respectively.

The production of disubstituted pyridines, disubstituted pyrazines, disubstituted pyrimidines and disubstituted pyridazines is
For example, in the series "The Chemistry of Heterocyclic Compounds"("The Chemi
stryof Heterocyclic Compounds ", A. Weissberger and
EC Taylor (editors) ”in the appropriate volume.

If desired, the starting materials may be prepared in situ and immediately added to the formula (I) without isolation from the reaction mixture.
Can also be converted into the compound of formula (I).

Schemes 1 and 2 are of type (Ia2)
Examples of synthetic routes for the compounds (1a4) and (Ia4) are shown. The same method can be used for other compounds of type (Ia).

The compound of type (Ic) can be prepared in principle as shown in scheme 3. By using an appropriate unit in the step of aldehyde or triphenylphosphine salt, an asymmetric structure (Ic
1) and (Ic2) can be obtained. In addition, one of the substituents R may be provided with a protecting group or a position-retaining property (eg benzoyl etc.) to provide a suitable point in the synthesis (eg step i).
(After) and removing this group and esterifying with R ¹ -substituted cyclohexanecarboxylic acid to give the type (Ic
The compound of 5) or (Ic6) can be obtained. Symmetrical (eg Ib4) and asymmetrical (eg Ib1) compounds of type (Ib) can be obtained eg as shown in Scheme 4. In the 1,2-substituted ether stage, the E / Z mixture obtained from step f can be used both in the photochemical cyclization (step g) and preferably in step h.

Scheme 5 shows an alternative route for compounds of type (Ia). Although a symmetric structure is outlined here, Scheme 5 is also particularly advantageous for asymmetric compounds.

Scheme 1

Embedded image a) NaOR in ROH b) H-C≡C-Tms, HN (iPr) ₂ , Pd (I
I) / Cu (I) catalyst, J. Organomet. Chem. 453 (1993)
2, Similar to C19 c) HN (Pr) 2, Pd (0) catalyst, J. Organome
t. Chem. 453 (1993) 2, C19 and similarly d) H ₂ / catalyst, (PN Rylander, Hydrogenation M
ethods, Academic Press, London, 1985, p.53) e) Pt / C; eg Zelinsky, Tietz, Berichte
62, 2869 (1929) f) For example, using 2,3-dichloro-5,6-dicyanobenzoquinone, as J. Chem. Soc. 1954, 3569.

Scheme 2

Embedded image a) H ₂ / catalyst, (PN Rylander, Hydrogenation M
ethods, Academic Press, London, 1985, p.53) b) Pt / C; eg Zelinsky, Tietz, Berichte
62, 2869 (1929) c) hγ / I ₂ ; For example, J. Am. Chem. Soc. 84, 436.
1 Similar to (1962) d) For example, using 2,3-dichloro-5,6-dicyanobenzoquinone, similar to J. Chem. Soc. 1954, 3569.

Scheme 3

Embedded image a) Base / RX b) 1. LDA 2. DMF 3. H ⁺ ； J. Org. Che
m. Same as 51, 3762 (1986) c) LiAlH ₄ (see Angew. Chem. 68, 601 (1956)) d) RC Larock, Comprehensive Organic Transfor
mations, VCH Publishers, New York, 1989, pp. 353
E) φ ₃ P; eg Org. Reactions 14, 388 (1965)
F) Org. Reactions 14, 270 (1965) g) H ₂ / catalyst, (PN Rylander, Hydrogenation M
ethods, Academic Press, London, 1985, p.23) h) Pt / catalyst; eg Zelinsky, Tietz, Ber. 6
2, 2869 (1929) i) hγ / I ₂ ; For example, J. Am. Chem. Soc. 84, 436
Same as 1 (1962).

Scheme 4

Embedded image a) Base / RX or R′X b) For example, J. Heterocyclic Chem. 3, 357 (1966)
Same as c) LiAlH ₄ (see Angew. Chem. 68, 601 (1956)) d) RC Larock, Comprehensive Organic Transfor
mations, VCH Publishers, New York, 1989, pp. 353
E) φ ₃ P; eg Org. Reactions 14, 388 (1965)
F) Org. Reactions 14, 270 (1965) g) hγ / I ₂ ; For example, J. Am. Chem. Soc. 84, 436.
1 (1962) and similar h) H ₂ / catalyst, (PN Rylander, Hydrogenation M
ethods, Academic Press, London, 1985, p.23) i) Pt / catalyst; eg Berichte 62, 2869 (1929).
Similar to j) For example, using 2,3-dichloro-5,6-dicyanobenzoquinone, similar to J. Chem. Soc. 1954, 3569.

Scheme 5

Embedded image a) TW Greene, Protective Groups in Organic S
ynthesis, J. Wiley, New York, (1981), pp.88-92 b) Base / RX or R'X c) For example, Houben-Weyl, Methoden der Organische
n Chemie (Method of Organic Chemistry) Thieme-Verlag Stuttgart,
Vol. 13 / 3a d) For example, as in EP-A354434 e) For example, J. Chem. Soc. Comm. 22, 582 (1965)
F) For example, N-bromosuccinimide; (Chem. Re
Views 43, 271 (1948)) g) For example, using sodium, Org. Syhth. Col
l. Vol. III, 157 (1955) h) For example, using 2,3-dichloro-5,6-dicyanobenzoquinone, as J. Chem. Soc. 1954, 3569.

The groups R ^1- (A ¹ -M ¹ ) _m and (M ² -A ² ) _n-
The synthesis of R ² , or a suitable reactive derivative thereof, or other suitable precursor of this group, can be carried out by methods known to those skilled in the art.

The production is carried out under known reaction conditions suitable for the reaction. Various refinements known per se can also be used, but are not mentioned here in detail.

For example, for compounds containing a 1,4-cyclohexylene group and a 1,4-phenylene group, DE-
A2344732, 2450088, 2429093,
2502904, 2636684, 2701591 and 2752975; DE-A26441724 for compounds containing a pyrimidine-2,5-diyl group; DE-A4 for compounds containing a pyridine-2,5-diyl group.
026233 and EP-A0391203; DE-A for compounds containing a pyridazine-3,6-diyl group.
3231462; 1,3,4-thiadiazole-2,5
EP-A30951 for compounds containing a diyl group
4; WO-A for naphthalene-2,6-diyl group
92/16500; Bicyclo [2.2.2] octane-
DE-A3710890 for 1,4-diyl groups;
For dioxaborinane-2,5-diyl groups, see K.S.
eto et al., Journal of the Chemical Society, Chemi
See cal Communications 1988, 56, respectively.

The production of disubstituted pyridines, disubstituted pyrazines, disubstituted pyrimidines and disubstituted pyridazines is
For example, in the series "The Chemistry of Heterocyclic Compounds"("The Chemi
stryof Heterocyclic Compounds ", A. Weissberger and
EC Taylor (editors) ”in the appropriate volume.

The dioxane derivative can be appropriately produced by reacting the corresponding aldehyde (or its reactive derivative) with the corresponding 1,3-diol (or its reactive derivative). The reaction is preferably carried out in the presence of an inert solvent such as benzene or toluene and / or in the presence of a catalyst such as a strong acid (eg sulfuric acid, benzenesulfonic acid or p-toluenesulfonic acid) from about 20 ° C to about 15 ° C.
It is carried out at a temperature of 0 ° C., preferably between 80 ° C. and 120 ° C. The mainly suitable reactive derivatives of the starting materials are the acetals.

Some of the above aldehydes and 1,3-diols and their derivatives are known and some can easily be prepared from compounds known from the literature by standard methods of organic chemistry. For example,
Aldehydes can be obtained by oxidation of the corresponding alcohols or reduction of nitriles or the corresponding carboxylic acids or derivatives thereof, and diols can be obtained by reduction of the corresponding diesters.

Compounds in which the aromatic ring is substituted by at least one fluorine atom are also prepared from the corresponding diazonium salts, for example by Balz and Schiema.
nn) and by substituting a fluorine atom for the diazonium group.

Regarding the direct bond between the aromatic ring and the aromatic heterocycle, for example, N. Miyaura, T. Yanagai, and A. Suzuk are mentioned.
i, Synthetic Communications 11 (1981), 513-519, D
E-C3930663, MJSharp, W.Cheng, V.Snieck
us, Tetrahedron Letters 28 (1987), 5093, GWGray,
J. Chem. Soc. Perkin Trans. II, 1989, 2041 and
Mol. Cryst. Liq. Cryst. 172 (1989), 165, 204 (199
1) 43 and 91, EP-A 0449015, WO-A
89/12039, WO-A 89/03821, EP-
A0354434;. -CH ₂ -CH ₂ - for compounds containing crosslinking, DE-A3201721; for compounds containing -C≡C- crosslinking, Koji Seto etal, Liquid Cr
See ystals 8 (1990) 861-870, respectively.

The ester of formula (I) is obtained by esterifying the corresponding carboxylic acid (or its reactive derivative) with an alcohol or phenol (or their reactive derivative) or by the DCCI method (DCCI =
Dicyclohexylcarbodiimide).

Corresponding carboxylic acids and alcohols or phenols are known and can be similarly prepared by known methods.

Particularly suitable reactive derivatives of the carboxylic acids are acid halides, especially chlorides and bromides,
Furthermore, acid anhydrides (for example mixed acid anhydrides), azides or esters (especially alkyl esters having 1-4 carbon atoms in the alkyl radical) are also suitable.

Particularly suitable reactive derivatives of the alcohols and phenols are the corresponding metals (especially alkali metals such as sodium or potassium) alkoxides or phenoxides.

The esterification is advantageously carried out in the presence of an inert solvent. Particularly suitable solvents are ethers (eg diethyl ether, di-n-butyl ether, TH
F, dioxane or anisole), ketones (eg acetone, butanone or cyclohexanone), amides (eg DMF or hexamethylphosphoric triamide), hydrocarbons (eg benzene, toluene or xylene), halogenated hydrocarbons (eg tetrachloromethane, Dichloromethane or tetrachloroethylene), and sulfoxides such as dimethyl sulfoxide or sulfolane.

The ethers of formula (I) can be obtained by etherification of the corresponding hydroxyl compounds, preferably the corresponding phenols. In this method, first, a hydroxyl compound is treated with NaH, NaNH ₂ , NaOH,
By treatment with KOH, Na ₂ CO ₃ or K ₂ CO ₃ , the corresponding metal derivative (eg corresponding alkali metal alkoxide or alkali metal phenoxide), as appropriate.
Convert to It is then treated with an inert solvent (eg acetone,
1,2-dimethoxy-ethane, DMF or dimethylsulfoxide), optionally with the corresponding alkyl halide, sulfonate or dialkyl sulphate, or in excess of aqueous or React with water / alcoholic NaOH or KOH.

For further synthesis of a particular group R ¹ , see the following references: EP-A0355008 for compounds containing silicon-containing side chains; EP-A0292954 and 0398155 for compounds containing cyclopropyl groups in the side chain. .

These compounds are contained in the liquid crystal at 1% to 80%.
%, Preferably 5% to 40%, the negative absolute value of Δε becomes large, which is preferable.

Further, a more preferable ferroelectric liquid crystal composition can be provided by combining the compound of the present invention with another compound having a negative Δε.

According to another aspect of the present invention, the present invention comprises the following general formula (II):

Embedded image [Wherein any one or more ═C—H groups on the aromatic ring are ═C—
Optionally substituted with F or = N-, R ₁ and R ₂
Independently of each other, (a) a hydrogen atom; (b) a carbon atom number 2
To 16 linear or branched alkyl groups, wherein one or two non-adjacent —CH ₂ — groups are —O—, —S.
-, -CO-, -CO-O-, -O-CO-, -CO-
S-, -S-CO-, -CH = CH-, -C≡C-,-
Si (CH _{3) 2} -, chiral epoxy group or -O-CO-
It may be substituted with O-, any hydrogen atom may be substituted with F, Cl or CN, or a plurality thereof, and the terminal methyl group may be substituted with a cyclopropyl group or a cyclohexyl group. Or (c)

Embedded image (Where n = 1 to 10) and Z ₁ and Z
₂ is a single bond, -O-, -CO-O- or -O-CO
− However, when R ₁ is (c), Z ₁ is not a single bond, and when R ₂ is (c), Z ₂ is not a single bond. ] The liquid crystal composition containing at least 1 type or more of the thiadiazole compound represented by these is provided. Preferably, the content of the compound of formula (II) in the composition is 1 to 50% by weight.

Specific examples of preferred compounds represented by the general formula (II) include:

Embedded image

Embedded image Is mentioned.

The present invention also provides the following general formula (III):

Embedded image [Wherein the symbols have the following meanings: R ¹ and R ² independently of each other are H or a straight-chain or branched-chain (with or without asymmetric carbon atom) alkyl having ^{1 to} 16 carbon atoms. Wherein one or two non-adjacent —CH ₂ — groups are —O—, —S—, —CO—, —CO—O—, —O—CO.
-, -CO-S-, -S-CO-, -O-CO-O-,
-CH = CH -, - C≡C- or -Si (CH _{3) 2} -
Optionally further substituted with one or more hydrogen atoms of the alkyl radical being F, Cl, Br or CN.
May be substituted by, or alternatively the following chiral groups:

Embedded image

Embedded image A ¹ , A ² , A ³ , and A ⁴ are the same or different, and 1,4-phenylene and pyrazine-2,5 in which one or two hydrogen atoms may be substituted by F −
Diyl, pyridazine-3,6-diyl, pyridine-2,
5-diyl or pyrimidine-2,5-diyl, trans-1,4-cyclohexylene in which one or two hydrogen atoms may be replaced by CN, or
1,3,4-thiadiazole-2,5-diyl, 1,3
-Dioxane-2,5-diyl, naphthalene-2,6-
Diyl, bicyclo [2.2.2] octane-1,4-diyl or 1,3-dioxaborinane-2,5-diyl; M ¹ , M ² , M ³ and M ⁴ are the same or different, and -O
-, -S-, -CO-, -CO-O-, -O-CO-,
-CO-S-, -S-CO-, -O-CO-O-, -C
_{H 2 -O -, - O-} CH 2 -, - CH 2 -CH 2 -, - CH
= CH- or ^{-C≡C-; R 3, R 4,} R 6, R 7
Are, independently of each other, H or linear or branched alkyl having 1 to 16 carbon atoms, or when R ³ and R ⁴ together are bonded to the dioxolane system as a substituent, (CH ₂ ) ₄ — or — (CH ₂ ) ₅ —; M ⁵
It is _{-CH 2 -O -, - CO-} O -, - O-CH 2 -, - O
-CO- or a single bond; k, l, m, n, o,
p, q, and r are 0 or 1, provided that the total of k + m + p + r is greater than 0 and less than 4], and a liquid crystal composition containing at least one fluoropyridine compound. Preferably formula (III) in the composition
The content of the compound is 1 to 50% by weight.

Specific examples of preferred compounds represented by the general formula (III) include:

Embedded image

[Chemical 51]

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image Is mentioned.

The present invention also includes the following general formula (IV):

Embedded image [In the formula, R ¹ and R ² are each independently H or a straight chain or branched chain (having or not having an asymmetric carbon atom) alkyl having 1 to 16 carbon atoms, wherein one or two non-adjacent -CH ₂ - groups are -O -, - S -, - CO
-, -CO-O-, -O-CO-, -CO-S-, -S
-CO-, -O-CO-O-, -CH = CH-, -C≡
C- or -Si (CH _{3) 2} - may be substituted by further 1 or more hydrogen atoms by F alkyl radicals, Cl, may be substituted by Br or CN, or also following chiral Basis:

Embedded image (Wherein R ³ , R ⁴ , R ⁶ and R ⁷ are, independently of each other, H or linear or branched alkyl having 1 to 16 carbon atoms, or R ³ and R ⁴ are taken together. When it is bonded to the dioxolane system as a substituent, it is — (CH ₂ ) ₄ — or — (CH ₂ ) ₅ —; M ⁵ is —CH ₂ —O—, —CO.
_{-O -, - O-CH 2} -, - O-CO- or a single bond) be either; A ¹ and A ^2, independently of one another, are each 1,4-phenylene, One or two CH groups present in this group may be replaced by N, or A ¹ and A ² are each 1,4-cyclohexylene and are present in this group One CH ₂ group or _two non-adjacent CH ₂ groups can also be replaced by O and / or S atoms, or A ¹ and A ² can each be piperidine-1,4-diyl. , 1,4-bicyclo (2,2,
2) Octylene, 1,3,4-thiadiazole-2,5
-Diyl, naphthalene-2,6-diyl or 1,2,
3,4-tetrahydronaphthalene-2,6-diyl, each of which is unsubstituted or has 1 or 2 F atoms and / or Cl atoms and / or CH ₃ groups and (Or) is substituted with a CN group, X ¹ and X ² are groups selected from hydrogen, F, Cl, CF ₃ and CN, but X ¹ and X ² are not hydrogen at the same time, Z ¹ and Z ² are each −
CO-O -, - O- CO -, - CH 2 CH 2 -, - OCH
_{2 -, - CH 2 O -} , - C≡C- or a single bond, m
And n are 0, 1 or 2, respectively, and (m
+ N) is 1 or 2], and a liquid crystal composition containing at least one difluorobenzene compound represented by the formula. Preferably, the content of the compound of formula (IV) in the composition is 1 to 50% by weight.

Specific examples of preferred compounds represented by the general formula (IV) include:

Embedded image

Embedded image

[Chemical formula 61]

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image Is mentioned.

The present invention also provides the following general formula (V):

Embedded image [Wherein X ³ is F, Cl, Br, CN, CF ₃ or an alkyloxy group having 1 to 12 carbon atoms, wherein one or more hydrogen atoms of the alkyloxy group are F, C
optionally substituted with 1 or CN, R ¹ is hydrogen or linear or branched alkyl having 1 to 16 carbons (with or without asymmetric carbon atoms), A 1
¹ , A ² , and A ³ are the same or different and each is a hydrogen atom
1,4 optionally substituted by 2 or 2
-Phenylene, pyrazine-2,5-diyl, pyridazine-3,6-diyl, pyridine-2,5-diyl or pyrimidine-2,5-diyl, one or two hydrogen atoms
Trans-1, optionally substituted by CN,
4-cyclohexylene, 1,3,4-thiadiazole-2,5-diyl, 1,3-dioxane-2,
5-diyl, naphthalene-2,6-diyl, bicyclo [2.2.2] octane-1,4-diyl or 1,3
- be a dioxaborinane-2,5-diyl; M ^1,
M ^2, M ^3, M ⁴ are identical or different, -O -, - S
-, -CO-, -CO-O-, -O-CO-, -CO-
S -, - S-CO - , - O-CO-O -, - CH 2 -O
_{-, - O-CH 2 -} , - CH 2 -CH 2 -, - CH = CH
-Or-C≡C-; k, l, m, n, o, p and q are 0 or 1, provided that the sum of l + n + p is 0.
And a liquid crystal composition containing at least one compound represented by the formula [4]. Preferably the content of compound of formula (V) in the composition is from 1 to 50
% By weight.

Specific examples of preferred compounds represented by the general formula (V) include:

Embedded image

Embedded image

Embedded image

Embedded image Is mentioned.

The present invention also provides the following general formula (VI):

Embedded image [Wherein, R or an alkyl group having a carbon number of 1 _{^{16 - (A 3) p -}} (M 4) is a _q -R ^2, R ¹ and R ² independently of one another, hydrogen or carbon atoms 1 to 16 A straight or branched chain (with or without asymmetric carbon atoms) alkyl, wherein one or two non-adjacent —CH ₂ — groups are —O—, —S—, —CO.
-, -CO-O-, -O-CO-, -CO-S-, -S
-CO-, -O-CO-O-, -CH = CH-, -C≡
C- or -Si (CH _{3) 2} - may be substituted by further 1 or more hydrogen atoms by F alkyl radicals, Cl, may be substituted by Br or CN, or also following chiral Basis:

Embedded image (Wherein R ³ , R ⁴ , R ⁶ and R ⁷ are, independently of each other, H or linear or branched alkyl having 1 to 16 carbon atoms, or R ³ and R ⁴ are taken together. When it is bonded to the dioxolane system as a substituent, it is — (CH ₂ ) ₄ — or — (CH ₂ ) ₅ —; M ⁵ is —CH ₂ —O—, —CO.
_{-O -, - O-CH 2} -, - O-CO- or a single bond) be either; A ^1, A ² and A ³ are identical or different, one or two hydrogen atoms Is optionally substituted by F, 1,4-phenylene, pyrazine-
2,5-diyl, pyridazine-3,6-diyl, pyridine-2,5-diyl or pyrimidine-2,5-diyl, trans-1 in which one or two hydrogen atoms may be replaced by CN. , 4-cyclohexylene, or 1,3,4-thiadiazole-2,5-diyl, 1,3-dioxane-2,5-diyl, naphthalene-2,6-diyl, bicyclo [2.2.2]. Octane
1,4-diyl or 1,3-dioxaborinane-2,
5-diyl; M ¹ , M ² , M ³ and M ⁴ are the same or different and are —O—, —S—, —CO—, —CO—O.
-, -O-CO-, -CO-S-, -S-CO-, -O
_{-CO-O -, - CH 2} -O -, - O-CH 2 -, - CH
_{2 -CH 2 -, - CH =} CH- or a -C≡C-;
k, l, m, n and o are 0 or 1, provided that l +
The total of n is more than 0 and less than 4], and a liquid crystal composition containing at least one compound represented by the formula. Preferably, the content of the compound of formula (VI) in the composition is 1 to 50% by weight.

Specific examples of preferred compounds represented by the general formula (VI) include:

Embedded image Is mentioned.

More preferably, the liquid crystal composition of the present invention is
In addition to the compounds of general formula (I) above,
One or more, preferably two or more, and particularly preferably at least three or more of each of the compounds represented by (VI) are contained. Further, preferably, in the liquid crystal composition of the present invention, the total content of the compounds represented by the general formulas (II) to (VI) is 30% or more, particularly preferably 50% of the whole liquid crystal composition. % Or more.

Further, in the ferroelectric liquid crystal display element,
The liquid crystal composition used is IN * -Sa- from the high temperature side.
Those having a Sc * phase sequence, a wide N * phase and a Sa phase, and a sufficiently long helical pitch in the N * phase and the Sc * phase are preferable because good orientation properties can be obtained (where I is equal to Direction, N * is a chiral nematic phase, Sa is a smectic A phase, and Sc * is a chiral smectic C phase).
In particular, the temperature range of the smectic A phase is 5 ° C or more. Therefore, in addition to the compound represented by the general formula (I), it is preferable to add another compound in order to obtain a liquid crystal composition having a preferable phase series. As such a compound, a low-viscosity compound that does not decrease the absolute value of Δε of the liquid crystal composition and does not increase the viscosity is preferable.

Therefore, the present invention includes a ferroelectric liquid crystal composition containing the compound represented by the general formula (I) and at least one phenylpyrimidine compound represented by the general formula (VII).

[0070]

[Chemical 76] [Wherein R ₁ and R ₂ are as defined for the general formula (I) above; ring A and ring B, independently of each other, represent a phenyl group or a cyclohexyl group; 0, 1 or 2, provided that o + p ≦ 2].

Preferred examples of such compounds include:

Embedded image

Embedded image [In the formula, R and R ′ are alkyl groups having 1 to 12 carbon atoms].

It is more preferable that the liquid crystal composition of the present invention has a negative Δε and an absolute value of 4 or more. Further, preferably, in the present invention, the pretilt angle of liquid crystal molecules at the liquid crystal / alignment film interface is 10 ° or less. A liquid crystal display device sandwiched between substrates is provided.

By using the compound of the general formula (I) of the present invention, the absolute value of the negative Δε of the ferroelectric liquid crystal can be increased. Conventionally, the spontaneous polarization value of the liquid crystal has been set low in order to lower the drive voltage. However, according to the present invention, the spontaneous polarization value can be increased and the response speed can be improved without increasing the drive voltage. In the present invention, the spontaneous polarization value is 1 to 30 nC / cm ² , preferably 5 to 20 nC / cm ² .

If the spontaneous polarization value is increased, sufficient contrast may not be obtained due to image sticking or poor memory property. Therefore, the ferroelectric liquid crystal composition of the present invention is a compound having a lone electron pair such as nitrogen, sulfur and oxygen and capable of taking in an ion, or a chain or cyclic compound having such a lone electron pair in the structure. It preferably contains at least one compound selected from macroethers.

Examples of such compounds include, among others, ethylene glycol dimethyl ether and triethylene glycol dimethyl ether, and crown ethers such as 12 crown 4, 15 crown 5, 18 crown 6 and derivatives thereof. In particular, the compound represented by the following structural formula is preferable because it has an effect of improving the alignment characteristics on the alignment film having a pretilt.

[0076]

Embedded image [In the formula, R ₁ and R ₂ have a non-adjacent -CH ₂ -group of -COO-, -CO-, -O-, -S- or -CH =
It is an alkyl group having 1 to 15 carbon atoms which may be substituted by CH- or an alkyl halide, hydrogen, cyclohexyl, phenyl or benzyl]. Among these,

Embedded image [Wherein, R is an alkyl group having 1 to 15 carbon atoms and n is a natural number of 1 to 10].

The content of these compounds in the liquid crystal composition of the present invention is 0.01 to 5%, preferably 0.1 to 2%.

The present invention will be described in more detail by the following examples.

[0079]

【Example】

Example 1 1,8-Difluoro-2,7-dioctyloxyphenanthrene 2-fluoro-3-octyloxybenzaldehyde (2-octyloxyfluorobenzene was reacted with lithium diisopropylamide in 50 ml THF, followed by N, 2.5 g of solution prepared by reacting with N-dimethylformamide) at 20 ° C.
Fluoro-3-octyloxybenzyl triphenylphosphonium bromide (prepared by the following reaction steps: 2
-Fluoro-3-octyloxybenzaldehyde and L
Reacting with iAlH ₄ in THF to give fluoro-3-
Octyloxybenzyl alcohol is obtained; which is reacted with triphenylphosphine / Br ₂ to give 2-fluoro-3-octyloxybenzyl bromide; which is reacted with triphenylphosphine in toluene) 5.6
g and potassium-t-butoxide 1.2 g THF 10
The mixture was allowed to react completely in 0 ml and added dropwise. When the reaction was complete, the mixture was adjusted to pH 5 with HCl, 500 ml of H ₂ O were added and the mixture was extracted 3 times with 100 ml of diethyl ether each time. By chromatography on silica gel with dichloromethane / heptane 1: 1 1,2-bis (2-fluoro-3-
Octyloxyphenyl) ethane was obtained as an E / Z mixture. Dissolve this in cyclohexane and add 4 mol% iodine.
And the mixture was stirred for 8 hours at 25 ° C in a quartz apparatus.
It was exposed to UV light for a period of time. Si with dichloromethane
O ₂ chromatography and recrystallization from acetonitrile gave 1.2 g of 1,8-difluoro-2,7-dioctyloxyphenanthrene as colorless crystals.

(Embodiment 2) In the same manner as in Embodiment 1,
8-difluoro-2,7-dihexyloxyphenanthrene was obtained. The phase sequence of the obtained compound was X 74 ° C. Sa 123 ° C. I. The phase transition temperature of the liquid crystal composition was measured by raising the temperature at 1 ° C./min under a polarizing microscope. The melting point was measured by raising the temperature at 1 ° C./min by differential scanning calorimetry (DSC).

This compound was converted into the following smectic liquid crystal composition (liquid crystal composition A):

Embedded image Liquid crystal composition B was prepared by adding 10% by weight to the solution, and the phase transition temperature and the dielectric anisotropy (Δε) were measured. The dielectric anisotropy (Δε) was measured by injecting the liquid crystal composition into a vertical alignment cell and a homogeneous alignment cell (manufactured by EHC, electrode interval 10 μm), and measuring each cell at 25 ° C. and 1 V at 20 KHz. The results are shown in Table 1.

Example 3 In the same manner as in Example 1,
2,7-bis (hexyloxy) -8-fluoro-1-
I got Azaphenanthrene. The phase sequence of the obtained compound was X 86 ° C. (80 Sa 84 ° C.) I.

This compound was added to liquid crystal composition A in an amount of 10% by weight to prepare liquid crystal composition C, and the phase transition temperature and dielectric anisotropy (Δε) were measured. The results are shown in Table 1.

(Comparative Example 1) The phase transition temperature and the dielectric anisotropy (Δε) of the liquid crystal composition A were measured in the same manner as in Example 2. The results are shown in Table 1.

[0085]

Table 1 Phase transition temperature Dielectric anisotropy Liquid crystal composition A Sc 62 Sa 77 N 82 I Δε = + 0.15 Liquid crystal composition B Sc 55 Sa 77 N 82 I Δε = −0.71 Liquid crystal composition C Sc 53 Sa 75 N 79 I Δε = −0.11 (Example 4) 1,8-difluoro-obtained in Example 2
FELIX 2,7-dihexyloxyphenanthrene
A liquid crystal composition D was obtained by adding 10% by weight to -M4851 / 000 (manufactured by Hoechst). The phase transition temperature and the dielectric anisotropy (Δε) of the liquid crystal composition D were measured in the same manner as in the examples. Table 2 shows the results.

2500 Lp of LQF100 (Nissan Chemical Industry) solution was spin-coated on a glass substrate with ITO.
m, and this film was baked at 200 ° C. for 1 hour to form a film. The coated film was rubbed in one direction with a nylon cloth, and then assembled so that the rubbing directions were parallel to each other with a 2.0 μm spacer interposed therebetween. Using this test cell,
The characteristics of the liquid crystal composition D were examined. ΤV of ferroelectric liquid crystal element
In the characteristics, the voltage Vmin that gives the minimum value τmin of the pulse width τ was measured by applying a monopolar pulse at 25 ° C. after injecting the liquid crystal composition into the above cell in the isotropic phase. Table 2 shows the results. The negative absolute value of Δε is large and Vmin is small.

(Comparative Example 2) Instead of the liquid crystal composition D, FE was used.
Using LIX-M4851 / 000 (manufactured by Hoechst), the dielectric anisotropy and τV characteristics were measured in the same manner as in Example 4. Table 2 shows the results.

[0088]

Table 2 τV Characteristics Dielectric Anisotropy Liquid Crystal Composition D Vmin = 30V, τmin = 28μs Δε = −1.30 FELIX-M4851 / 000 Vmin = 48V, τmin = 20μs Δε = −0.80 (Example 5 ) A liquid crystal composition E was prepared by adding the following compound to the liquid crystal composition A:

[Chemical formula 82] The phase transition temperature of this liquid crystal composition E, the spontaneous polarization value (Ps),
Table 3 shows the voltage (Vmin) at the minimum pulse width and the minimum pulse width (τmin).

[0089]

[Table 3] Phase transition temperature: X -5 Sc * 62.5 Sa 79.4 N *
83.3-85.0 IPs: 3.3 nC / cm ² Δε: −1.5 τmin: 20 μs Vmin: 33V (Comparative Example 3) A liquid crystal composition F was prepared by adding the following compound to the liquid crystal composition A.

[0090]

[Chemical 83] Table 4 shows the phase transition temperature, the spontaneous polarization value (Ps), the voltage at the minimum pulse width (Vmin) and the minimum pulse width (τmin) of the liquid crystal composition F.

[0091]

[Table 4] Phase transition temperature: X 6 Sc * 65.5 Sa 69.4 N *
74.5-75.0 IPs: 3.3 nC / cm ² Δε: −1.2 τmin: 24 μs Vmin: 51V Compared with the liquid crystal composition E of Example 5 according to the present invention, Vm
The value of in was high and the absolute value of Δε was small.

Example 6 A liquid crystal composition G having the following composition was produced.

[0093]

Embedded image

Embedded image Optical active bodies 1 and 2 were added to this liquid crystal composition G in the following weight ratios (%) to prepare liquid crystal compositions H and I.

[0094]

Embedded image Liquid crystal composition HG 98.5% Optically active substance 1 1.5% Liquid crystal composition IG 96.5% Optically active substance 2 3.5% Liquid crystal composition H phase transition temperature, spontaneous polarization value (Ps), Table 5 shows the voltage (Vmin) at the minimum pulse width and the minimum pulse width (τmin).

[0095]

[Table 5] Phase transition temperature: X <-40 Sc * 73.6 Sa 87.0
N * 94.0-97.0 I Ps: 14 nC / cm ² Δε: −5.5 τ min: 20 μs Vmin: 33V Phase transition temperature of liquid crystal composition I, spontaneous polarization value (Ps), voltage at minimum pulse width (Vmin) Table 6 shows the pulse width (τmin) of the minimum value.

[0096]

[Table 6] Phase transition temperature: X <-40 Sc * 74.1 Sa 94.0
N * 95.5-100.2 IPs: 13 nC / cm ² Δε: −5.6 τmin: 11 μs Vmin: 30V

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Lee Tsuji 1-3-2 Minamidai, Kawagoe City, Saitama Prefecture Hexton Industry Co., Ltd. Advanced Materials Technology Research Laboratory (72) Inventor Kazuya Nagao 1-3-2 Minamidai, Kawagoe City, Saitama Prefecture Hext Industry Co., Ltd., Advanced Materials Technology Laboratory (72) Inventor Reiner Wingen, Germany Day –65795 Hattersheim, Langen Heiner Weg 11 (72) Inventor, Barbara Hornung, Germany Day –63594 Hasselroth, Schlstraße 21 Ar (72) Inventor Jaffia Manello Federal Republic of Germany Day 65929 Frank Furt / Main, Zintlinger Bernstrasse 163

Claims (27)

[Claims] 1. Formula (I): [Wherein the symbols and subscripts have the following meanings: E ¹ ,
^{E 2, E 3, E 4} , E 5 and E ⁶ are, -N -, - CF- or is a -CH-, but include the following exceptions: E
¹ (E ⁴ ) is -N- or -CF-, then E ² and E ³
(E ⁵ and E ⁶⁾ must be -CH-; E ² and / or E ³ (E ⁵ and / or E ⁶⁾ are -CF-
When, E ¹ (E ⁴⁾ must be -CH-; E ²
When (E ⁵⁾ is -N-, E ¹ (E ⁴⁾ must be an -CH-, E ³ (E ⁶⁾ is -CH- or -CF-
It can be at; and at least one of E ⁶ from E ¹ must be -N- or -CF-; G is -C
H ₂ CH ₂ - or -CH = CH- and is; R ¹ and R ²
Are, independently of each other, hydrogen or a linear or branched alkyl group having 1 to 20 carbon atoms (which may or may not have asymmetric carbon), wherein one or more of -CH ₂ - group, -O -, - S -, - CO -, - C
H = CH -, - C≡C-, _{cyclopropane-1,2-diyl, -Si (CH 3) 2 -} , 1,4- phenylene, trans-1,4-cyclohexylene or trans-1,
It may be substituted with 3-cyclopentylene, provided that it is an oxygen atom and a sulfur atom (hereinafter referred to as chalcogen).
Are not directly bonded to each other, and one or more hydrogen atoms of the alkyl group are -F, -Cl, -Br or-.
It may be substituted with OR ³ , or R ¹ and R ²
Is one of the following chiral groups: (Here, R < ³ >, R < ⁴ >, R < ⁵ >, R < ⁶ > and R < ⁷ > are, independently of each other, a linear or branched alkyl group having 1 to 16 carbon atoms (having an asymmetric carbon it is also be) not be, one or more -CH ₂ where - groups, -
O- or -CH = CH- may be substituted,
However, the oxygen atoms are not directly bonded to each other, and one or more hydrogen atoms of the alkyl group are -F or -C.
l may be substituted, or R ⁴ and R ⁵ are
When bonded to an oxirane system, a dioxolane system, a tetrahydrofuran system, a tetrahydropyran system, a butyrolactone system or a valerolactone system, they are combined together-
(CH _{2) 4} - or - (CH _{2) 5} - may be formed;
Q is _{-CH 2 -O -, - CO-} O- or a single bond); M ¹ and M ² are identical or different, -CO-O
-, - O-CO -, - CH 2 -O -, - O-CH 2 -, -
CH ₂ —CH ₂ —, —C≡C— or a single bond; A ¹
And A ² are the same or different, 1,4-phenylene in which one or more hydrogen atoms may be substituted with F, Cl and / or CN, 1 or 2 hydrogen atoms in F, Cl And / or pyrazine-2,5-diyl optionally substituted with CN, pyridazine-3,6-diyl optionally substituted with 1 or 2 hydrogen atoms by F, Cl and / or CN, Pyridine-2,5-diyl optionally substituted with one or more hydrogen atoms with F, Cl and / or CN, one or two hydrogen atoms substituted with F, Cl and / or CN Optionally pyrimidine-2,5-diyl, 1 or 2
Hydrogen atoms is CN and / or CH ₃ with an optionally substituted trans-1,4-cyclohexylene, 1,
3,4-thiadiazole-2,5-diyl, 1,3-dioxane-2,5-diyl, 1,3-dithiane-2,5
-Diyl, wherein one hydrogen atom is F, Cl and / or C
1,3-thiazole-2,4 which may be substituted by N
-Diyl, wherein one hydrogen atom is F, Cl and / or C
1,3-thiazole-2,5 which may be substituted by N
-Diyl, wherein one hydrogen atom is F, Cl and / or C
Thiophene-2,4-diyl optionally substituted with N, thiophen-2,5-diyl optionally substituted with one or two hydrogen atoms by F, Cl and / or CN, piperazine-1 , 4-diyl, piperazine-2,
5-diyl, one or more hydrogen atoms being F, Cl
And / or naphthalene-2,6-diyl optionally substituted with CN, bicyclo [2.2.2] optionally having one or more hydrogen atoms substituted with F, Cl and / or CN. Octane-1,4-diyl or 1,3-dioxaborinane-2,5-diyl;
n and m are 0 or 1, but the maximum of the sum is 1.] A ferroelectric liquid crystal composition comprising at least one compound represented by the formula: 2. A group represented by the formula (I): Is the following group: [Claim 1] wherein E ¹ to E ⁶ are as defined for formula (I) in claim 1;
The ferroelectric liquid crystal composition according to the above. 3. The following Ia1 to Id14: [Chemical 6] [Chemical 7] Embedded image Embedded image Embedded image Embedded image The ferroelectric liquid crystal composition according to claim 1, which is selected from the group consisting of: 4. The ferroelectric liquid crystal composition according to claim 1, wherein Δε is negative. 5. The ferroelectric liquid crystal composition according to claim 1, wherein Δε is negative and its absolute value is 1 or more. 6. A liquid crystal composition according to claim 1, which comprises 1 to 80% by weight of at least one compound represented by the general formula (I). 7. Further, at least another one in which Δε is negative.
7. A compound containing a compound of a kind,
The ferroelectric liquid crystal composition according to any one of the above. 8. General formula (II): [Wherein any one or more ═C—H groups on the aromatic ring are ═C—
Optionally substituted with F or = N-, R ₁ and R ₂
Independently of each other, (a) a hydrogen atom; (b) a carbon atom number 2
To 16 linear or branched alkyl groups, wherein one or two non-adjacent —CH ₂ — groups are —O—, —S.
-, -CO-, -CO-O-, -O-CO-, -CO-
S-, -S-CO-, -CH = CH-, -C≡C-,-
Si (CH _{3) 2} -, chiral epoxy group or -O-CO-
It may be substituted with O-, any hydrogen atom may be substituted with F, Cl or CN, or a plurality thereof, and the terminal methyl group may be substituted with a cyclopropyl group or a cyclohexyl group. Or (c) embedded image (Where n = 1 to 10) and Z ₁ and Z
₂ is a single bond, -O-, -CO-O- or -O-CO
− However, when R ₁ is (c), Z ₁ is not a single bond, and when R ₂ is (c), Z ₂ is not a single bond; A ₁ is Or Or a single bond; X ₁ , X ₂ , X ₃ and X ₄ are each independently —N—, —CF— or —CH—. ] The at least 1 sort (s) of compound represented by these are contained, The ferroelectric liquid crystal composition of Claim 7 characterized by the above-mentioned. 9. A ferroelectric liquid crystal composition according to claim 8, which contains 1 to 50% by weight of the compound of the general formula (II). 10. General formula (III): [Wherein the symbols have the following meanings: R ¹ and R ² independently of each other are H or a straight-chain or branched-chain (with or without asymmetric carbon atom) alkyl having ^{1 to} 16 carbon atoms. Wherein one or two non-adjacent —CH ₂ — groups are —O—, —S—, —CO—, —CO—O—, —O—CO.
-, -CO-S-, -S-CO-, -O-CO-O-,
-CH = CH -, - C≡C- or -Si (CH _{3) 2} -
Optionally further substituted with one or more hydrogen atoms of the alkyl radical being F, Cl, Br or CN.
Optionally substituted by, or alternatively, the following chiral group: (Wherein R ³ , R ⁴ , R ⁶ and R ⁷ are, independently of each other, H or linear or branched alkyl having 1 to 16 carbon atoms, or R ³ and R ⁴ are taken together. When it is bonded to the dioxolane system as a substituent, it is — (CH ₂ ) ₄ — or — (CH ₂ ) ₅ —; M ⁵ is —CH ₂ —O—, —CO.
_{-O -, - O-CH 2} -, - O-CO- or a single bond) be ^{either; A 1, A 2, A} 3, A 4 are the same or different, one hydrogen atom or 1,4-phenylene, two of which may be substituted by F, pyrazine-
2,5-diyl, pyridazine-3,6-diyl, pyridine-2,5-diyl or pyrimidine-2,5-diyl, trans-1 in which one or two hydrogen atoms may be replaced by CN. , 4-cyclohexylene, or 1,3,4-thiadiazole-2,5-diyl, 1,3-dioxane-2,5-diyl, naphthalene-2,6-diyl, bicyclo [2.2.2]. Octane
1,4-diyl or 1,3-dioxaborinane-2,
5-diyl; M ¹ , M ² , M ³ and M ⁴ are the same or different and are —O—, —S—, —CO—, —CO—O—, —O.
-CO-, -CO-S-, -S-CO-, -O-CO-
_{O -, - CH 2 -O -} , - O-CH 2 -, - CH 2 -CH 2
-, -CH = CH- or -C≡C-; k, l,
m, n, o, p, q, r are 0 or 1, provided that k +
The sum of m + p + r is greater than 0 and less than 4], and at least one compound represented by the formula is contained in the ferroelectric liquid crystal composition. 11. A ferroelectric liquid crystal composition according to claim 10, containing 1 to 50% by weight of the compound of the general formula (III). 12. A compound represented by the general formula (IV): [In the formula, R ¹ and R ² are each independently H or a straight chain or branched chain (having or not having an asymmetric carbon atom) alkyl having 1 to 16 carbon atoms, wherein one or two non-adjacent -CH ₂ - groups are -O -, - S -, - CO
-, -CO-O-, -O-CO-, -CO-S-, -S
-CO-, -O-CO-O-, -CH = CH-, -C≡
C- or -Si (CH _{3) 2} - may be substituted by further 1 or more hydrogen atoms by F alkyl radicals, Cl, may be substituted by Br or CN, or also following chiral Group: (Wherein R ³ , R ⁴ , R ⁶ and R ⁷ are, independently of each other, H or linear or branched alkyl having 1 to 16 carbon atoms, or R ³ and R ⁴ are taken together. When it is bonded to the dioxolane system as a substituent, it is — (CH ₂ ) ₄ — or — (CH ₂ ) ₅ —; M ⁵ is —CH ₂ —O—, —CO.
_{-O -, - O-CH 2} -, - O-CO- or a single bond) be either; A ¹ and A ^2, independently of one another, are each 1,4-phenylene, One or two CH groups present in this group may be replaced by N, or A ¹ and A ² are each 1,4-cyclohexylene and are present in this group One CH ₂ group or _two non-adjacent CH ₂ groups can also be replaced by O and / or S atoms, or A ¹ and A ² can each be piperidine-1,4-diyl. , 1,4-bicyclo (2,2,
2) Octylene, 1,3,4-thiadiazole-2,5
-Diyl, naphthalene-2,6-diyl or 1,2,
3,4-tetrahydronaphthalene-2,6-diyl, each of which is unsubstituted or has 1 or 2 F atoms and / or Cl atoms and / or CH ₃ groups and (Or) is substituted with a CN group, X ¹ and X ² are groups selected from hydrogen, F, Cl, CF ₃ and CN, but X ¹ and X ² are not hydrogen at the same time, Z ¹ and Z ² are each −
CO-O -, - O- CO -, - CH 2 CH 2 -, - OCH
_{2 -, - CH 2 O -} , - C≡C- or a single bond, m
And n are 0, 1 or 2, respectively, and (m
+ N) is 1 or 2.] The ferroelectric liquid crystal composition according to claim 7, containing at least one compound represented by the formula. 13. The compound of general formula (IV) is contained in an amount of 1 to 50% by weight.
13. The ferroelectric liquid crystal composition according to claim 12, which contains. 14. General formula (V): [Wherein X ³ is F, Cl, Br, CN, CF ₃ or an alkyloxy group having 1 to 12 carbon atoms, wherein one or more hydrogen atoms of the alkyloxy group are F, C
optionally substituted with 1 or CN, R ¹ is hydrogen or linear or branched alkyl having 1 to 16 carbons (with or without asymmetric carbon atoms), A 1
¹ , A ² , and A ³ are the same or different and each is a hydrogen atom
1,4 optionally substituted by 2 or 2
-Phenylene, pyrazine-2,5-diyl, pyridazine-3,6-diyl, pyridine-2,5-diyl or pyrimidine-2,5-diyl, one or two hydrogen atoms
Trans-1, optionally substituted by CN,
4-cyclohexylene, 1,3,4-thiadiazole-2,5-diyl, 1,3-dioxane-2,
5-diyl, naphthalene-2,6-diyl, bicyclo [2.2.2] octane-1,4-diyl or 1,3
- be a dioxaborinane-2,5-diyl; M ^1,
M ^2, M ^3, M ⁴ are identical or different, -O -, - S
-, -CO-, -CO-O-, -O-CO-, -CO-
S -, - S-CO - , - O-CO-O -, - CH 2 -O
_{-, - O-CH 2 -} , - CH 2 -CH 2 -, - CH = CH
-Or-C≡C-; k, l, m, n, o, p and q are 0 or 1, provided that the sum of l + n + p is 0.
It is larger and is less than 4.] The ferroelectric liquid crystal composition according to claim 7, containing at least one compound represented by the formula. 15. 1 to 50% by weight of a compound of general formula (V)
The ferroelectric liquid crystal composition according to claim 14, wherein the ferroelectric liquid crystal composition is contained. 16. A compound represented by the general formula (VI): [Wherein, R or an alkyl group having a carbon number of 1 _{^{16 - (A 3) p -}} (M 4) is a _q -R ^2, R ¹ and R ² independently of one another, hydrogen or carbon atoms 1 to 16 A straight or branched chain (with or without asymmetric carbon atoms) alkyl, wherein one or two non-adjacent —CH ₂ — groups are —O—, —S—, —CO.
-, -CO-O-, -O-CO-, -CO-S-, -S
-CO-, -O-CO-O-, -CH = CH-, -C≡
C- or -Si (CH _{3) 2} - may be substituted by further 1 or more hydrogen atoms by F alkyl radicals, Cl, may be substituted by Br or CN, or also following chiral Group: embedded image (Wherein R ³ , R ⁴ , R ⁶ and R ⁷ are, independently of each other, H or linear or branched alkyl having 1 to 16 carbon atoms, or R ³ and R ⁴ are taken together. When it is bonded to the dioxolane system as a substituent, it is — (CH ₂ ) ₄ — or — (CH ₂ ) ₅ —; M ⁵ is —CH ₂ —O—, —CO.
_{-O -, - O-CH 2} -, - O-CO- or a single bond) be either; A ^1, A ² and A ³ are identical or different, one or two hydrogen atoms Is optionally substituted by F, 1,4-phenylene, pyrazine-
2,5-diyl, pyridazine-3,6-diyl, pyridine-2,5-diyl or pyrimidine-2,5-diyl, trans-1 in which one or two hydrogen atoms may be replaced by CN. , 4-cyclohexylene, or 1,3,4-thiadiazole-2,5-diyl, 1,3-dioxane-2,5-diyl, naphthalene-2,6-diyl, bicyclo [2.2.2]. Octane
1,4-diyl or 1,3-dioxaborinane-2,
5-diyl; M ¹ , M ² , M ³ and M ⁴ are the same or different and are —O—, —S—, —CO—, —CO—O.
-, -O-CO-, -CO-S-, -S-CO-, -O
_{-CO-O -, - CH 2} -O -, - O-CH 2 -, - CH
_{2 -CH 2 -, - CH =} CH- or a -C≡C-;
k, l, m, n, o, p and q are 0 or 1,
However, the sum of l + n + p is greater than 0 and less than 4.]
8. The ferroelectric liquid crystal composition according to claim 7, containing at least one compound represented by 17. The compound of general formula (VI) is contained in an amount of 1 to 50% by weight.
The ferroelectric liquid crystal composition according to claim 16, which contains. 18. Among the compounds of general formulas (II) to (VI),
The ferroelectric liquid crystal composition according to claim 7, which contains at least two kinds. 19. The ferroelectric liquid crystal composition according to claim 1, wherein Δε is negative and the absolute value is 2 or more. 20. The ferroelectric liquid crystal composition according to claim 1, wherein Δε is negative and the absolute value is 4 or more. 21. General formula (VII): [Wherein R ₁ and R ₂ are as defined for formula (I) in claim 1; ring A and ring B independently of one another represent a phenyl or cyclohexyl group; o and p are , 0, 1 or 2, provided that o + p
≦ 2] at least one phenylpyrimidine compound is contained.
21. The ferroelectric liquid crystal composition according to any one of 20. 22. The ferroelectric property according to claim 1, which has a phase series of an isotropic liquid phase, a nematic phase, a smectic A phase, and a smectic C phase from the high temperature side. Liquid crystal composition. 23. The ferroelectric liquid crystal composition according to claim 22, which has a temperature range of the smectic A phase of 5 ° C. or more. 24. The ferroelectric liquid crystal display device according to claim 1, wherein the value of spontaneous polarization is 1 to 30 nC / cm ² . 25. At least one selected from compounds having a lone electron pair such as nitrogen, sulfur and oxygen and capable of incorporating an ion, or a chain or cyclic macroether having the lone electron pair in its structure. 25. The ferroelectric liquid crystal composition according to claim 24, which contains 0.01 to 5% of one compound. 26. A liquid crystal device in which the liquid crystal composition according to any one of claims 1 to 25 is sandwiched between a pair of substrates on which two electrodes and an alignment control film are formed. 27. The pretilt angle of liquid crystal molecules at the liquid crystal / alignment film interface is 10 ° or less.
The ferroelectric liquid crystal composition according to claim 1.