U.S. patent application number 09/331058 was filed with the patent office on 2002-04-04 for difluorophenyl derivatives, liquid-crystal compounds, and liquid-crystal composition.
Invention is credited to KATO, TAKASHI, MATSUI, SHUICHI, MIYAZAWA, KAZUTOSHI, NAKAGAWA, ETSUO, TAKESHITA, FUSAYUKI.
Application Number | 20020038858 09/331058 |
Document ID | / |
Family ID | 18429262 |
Filed Date | 2002-04-04 |
United States Patent
Application |
20020038858 |
Kind Code |
A1 |
KATO, TAKASHI ; et
al. |
April 4, 2002 |
DIFLUOROPHENYL DERIVATIVES, LIQUID-CRYSTAL COMPOUNDS, AND
LIQUID-CRYSTAL COMPOSITION
Abstract
Disclosed are liquid crystalline compounds which (i) are
characterized in that the compounds have a wide temperature range
in which the compounds exhibit a liquid crystal phase, are low in
viscosity, and have a negative and high .DELTA..epsilon., (ii) are
readily mixed with other various liquid crystal materials even at
low temperatures, and (iii) are useful as component of liquid
crystal compositions suitable both for TFT type display mode and
IPS mode; and liquid crystal composition comprising the liquid
crystalline compound; the compounds are expressed by the general
formula (1) 1 wherein R.sup.1 represents an alkyl group having 1 to
15 carbon atoms; ring A.sup.1, ring A.sup.2, and ring A.sup.3
independently represent trans-1,4-cyclohexylene group,
trans-1,4-silacyclohexylene group, pyrimidine-2,5-diyl group,
pyridine-2,5-diyl group, 1,3-dioxane-2,5-diyl group,
tetrahydropyran-2,5-diyl group, 1,3-dithian-2,5-diyl group, or
tetrahydrothiopyran-2,5-diyl group, or 1,4-phenylene group in which
one or more hydrogen atoms on the six-membered ring may be replaced
by a halogen atom; X.sup.1, X.sup.2, and X.sup.3 independently
represent --(CH.sub.2).sub.4--, --(CH.sub.2).sub.3O--,
--O(CH.sub.2).sub.3--, or single bond; Y.sup.1 represents hydrogen
atom or an alkyl group having 1 to 15 carbon atoms; m and n are
independently 0 or 1; and any atom which constitutes this compound
may be replaced by its isotope.
Inventors: |
KATO, TAKASHI; (CHIBA,
JP) ; MATSUI, SHUICHI; (CHIBA, JP) ; MIYAZAWA,
KAZUTOSHI; (CHIBA, JP) ; TAKESHITA, FUSAYUKI;
(CHIBA, JP) ; NAKAGAWA, ETSUO; (CHIBA,
JP) |
Correspondence
Address: |
WENDEROTH LIND & PONACK
2033 K STREET NW SUITE 800
WASHINGTON
DC
20006
|
Family ID: |
18429262 |
Appl. No.: |
09/331058 |
Filed: |
June 16, 1999 |
PCT Filed: |
December 16, 1997 |
PCT NO: |
PCT/JP97/04633 |
Current U.S.
Class: |
252/299.63 ;
252/299.61; 252/299.66; 570/127; 570/129; 570/130; 570/131 |
Current CPC
Class: |
C07C 2601/14 20170501;
C09K 2019/3422 20130101; C09K 19/3003 20130101; C07C 43/225
20130101; C09K 19/3458 20130101; C07C 17/16 20130101; C09K 19/3066
20130101; C09K 2019/3027 20130101; C07C 17/263 20130101; C09K
19/3491 20130101; C09K 19/3402 20130101; C07B 59/001 20130101; C09K
19/0403 20130101; C09K 19/20 20130101; C07C 17/354 20130101; C09K
2019/0407 20130101; C07C 17/269 20130101; C09K 19/42 20130101; C09K
2323/00 20200801; C07C 17/2632 20130101; C07C 25/18 20130101; C07C
45/60 20130101; C09K 19/3444 20130101; Y10T 428/10 20150115; C07C
43/192 20130101; C07F 7/0896 20130101; C07C 45/513 20130101; C07C
17/12 20130101; C09K 19/14 20130101; C07C 25/24 20130101; C07C
17/12 20130101; C07C 25/18 20130101; C07C 17/16 20130101; C07C
22/00 20130101; C07C 17/263 20130101; C07C 25/18 20130101; C07C
17/2632 20130101; C07C 25/18 20130101; C07C 17/269 20130101; C07C
25/18 20130101; C07C 17/354 20130101; C07C 25/18 20130101; C07C
45/513 20130101; C07C 47/105 20130101; C07C 45/60 20130101; C07C
47/105 20130101 |
Class at
Publication: |
252/299.63 ;
252/299.61; 252/299.66; 570/127; 570/129; 570/130; 570/131 |
International
Class: |
C09K 019/30; C07C
025/13; C09K 019/34; C09K 019/42 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 16, 1996 |
JP |
8-353203 |
Claims
1. A liquid crystalline compound expressed by the general formula
(1) 947wherein R.sup.1 represents an alkyl group having 1 to 15
carbon atoms in which alkyl group, not-adjacent any methylene group
may be replaced by oxygen atom or vinylene group, and any hydrogen
atom in the alkyl group may be replaced by fluorine atom; ring
A.sup.1, ring A.sup.2, and ring A.sup.3 independently represent
trans-1,4-cyclohexylene group, trans-1,4-silacyclohexylene group,
pyrimidine-2,5-diyl group, pyridine-2,5-diyl group,
1,3-dioxane-2,5-diyl group, tetrahydropyran-2,5-diyl group,
1,3-dithian-2,5-diyl group, or tetrahydrothiopyran-2,5-diyl group,
or 1,4-phenylene group in which one or more hydrogen atoms on the
six-membered ring may be replaced by a halogen atom; X.sup.1,
X.sup.2, and X.sup.3 independently represent --(CH.sub.2).sub.4--,
--(CH.sub.2).sub.3O--, --O(CH.sub.2).sub.3--, or single bond;
Y.sup.1 represents hydrogen atom or an alkyl group having 1 to 15
carbon atoms in which alkyl group not-adjacent any methylene group
may be replaced by oxygen atom or vinylene group; m and n are
independently 0 or 1; and any atom which constitutes this compound
may be replaced by its isotope.
2. The liquid crystalline compound according to claim 1 wherein
ring A.sup.1 represents trans-1,4-cyclohexylene group, or
1,4-phenylene group in which one or more hydrogen atoms on the
six-membered ring may be replaced by fluorine atom; X.sup.1
represents --(CH.sub.2).sub.4-- or --(CH.sub.2).sub.3O--; and
either m and n are 0 in the general formula (1).
3. The liquid crystalline compound according to claim 1 wherein
ring A.sup.1 and ring A.sup.2 independently represent
trans-1,4-cyclohexylene group, or 1,4-phenylene group in which one
or more hydrogen atoms on the six-membered ring may be replaced by
fluorine atom; X.sup.1 represents --(CH.sub.2).sub.4-- or
--(CH.sub.2).sub.3O--; X.sup.2 represents single bond; and m is 1
and n is 0 in the general formula (1).
4. The liquid crystalline compound according to claim 1 wherein
ring A.sup.1 and ring A.sup.2 independently represent
trans-1,4-cyclohexylene group, or 1,4-phenylene group in which one
or more hydrogen atoms on the six-membered ring may be replaced by
fluorine atom; X.sup.2 represents --(CH.sub.2).sub.4-- or
--(CH.sub.2).sub.3O--; X.sup.1 represents single bond; and m is 1
and n is 0 in the general formula (1).
5. The liquid crystalline compound according to claim 1 wherein
ring A.sup.1, ring A.sup.2, and ring A.sup.3 independently
represent trans-1,4-cyclohexylene group, or 1,4-phenylene group in
which one or more hydrogen atoms on the six-membered ring may be
replaced by fluorine atom; XI represent --(CH.sub.2).sub.4-- or
--(CH.sub.2).sub.3O--; either X.sup.2 and X.sup.3 represent single
bond; and m is 1 and n is 1 in the general formula (1).
6. The liquid crystalline compound according to claim 1 wherein
ring A.sup.1, ring A.sup.2, and ring A.sup.3 independently
represent trans-1,4-cyclohexylene group, or 1,4-phenylene group in
which one or more hydrogen atoms on the six-membered ring may be
replaced by fluorine atom; X.sup.2 represents --(CH.sub.2).sub.4--
or --(CH.sub.2).sub.3O--; either X.sup.1 and X.sup.3 represent
single bond; and m is 1 and n is 1 in the general formula (1).
7. The liquid crystalline compound according to claim 1 wherein
ring A.sup.1, ring A.sup.2, and ring A.sup.3 independently
represent trans-1,4-cyclohexylene group, or 1,4-phenylene group in
which one or more hydrogen atoms on the six-membered ring may be
replaced by fluorine atom; X.sup.3 represents --(CH.sub.2).sub.4--
or --(CH.sub.2).sub.3O--; either X.sup.1 and X.sup.2 represent
single bond; and m is 1 and n is 1 in the general formula (1).
8. A liquid crystal composition comprising at least two components
and comprising at least one liquid crystalline compound expressed
by the general formula (1) 948wherein R' represents an alkyl group
having 1 to 15 carbon atoms in which alkyl group not-adjacent any
methylene group may be replaced by oxygen atom or vinylene group,
and any hydrogen atom in the alkyl group may be replaced by
fluorine atom; ring A.sup.1, ring A.sup.2, and ring A.sup.3
independently represent trans-1,4-cyclohexylene group,
trans-1,4-silacyclohexylene group, pyrimidine-2,5-diyl group,
pyridine-2,5-diyl group, 1,3-dioxane-2,5-diyl group,
tetrahydropyran-2,5-diyl group, 1,3-dithian-2,5-diyl group, or
tetrahydrothiopyran-2,5-diyl group, or 1,4-phenylene group in which
one or more hydrogen atoms on the six-membered ring may be replaced
by a halogen atom; X.sup.1, X.sup.2, and X.sup.3 independently
represent --(CH.sub.2).sub.4--, --(CH2 ).sub.3O--,
--O(CH.sub.2).sub.3--, or single bond; Y.sup.1 represents hydrogen
atom or an alkyl group having 1 to 15 carbon atoms in which alkyl
group not-adjacent any methylene group may be replaced by oxygen
atom or vinylene group; m and n are independently 0 or 1; and any
atom which constitutes this compound may be replaced by its
isotope.
9. A liquid crystal composition comprising, as a first component,
at least one liquid crystalline compound defined in any one of
claims 1 to 7, and comprising, as a second component, at least one
compound selected from the group consisting of the compounds
expressed by any one of the general formulas (2), (3), and (4)
949wherein R.sup.2 represents an alkyl group having 1 to 10 carbon
atoms in which alkyl group not-adjacent any methylene group may be
replaced by oxygen atom or vinylene group; and any hydrogen atom in
the alkyl group may be replaced by fluorine atom; Y.sup.2
represents fluorine atom, chlorine atom, --OCF.sub.3, --OCF.sub.2H,
--CF.sub.3, --CF.sub.2H, --CFH.sub.2, --OCF.sub.2CF.sub.2H, or
--OCF.sub.2CFHCF.sub.3; L.sup.1 and L.sup.2 independently represent
hydrogen atom or fluorine atom; Z.sup.1 and Z.sup.2 independently
represent 1,2-ethylene group, vinylene group, 1,4-butylene group,
--COO--, --CF.sub.2O--, --OCF.sub.2--, or single bond; ring B
represents trans-1,4-cyclohexylene group or 1,3-dioxane-2,5-diyl
group, or 1,4-phenylene group in which hydrogen atom may be
replaced by fluorine atom; ring C represents
trans-1,4-cyclohexylene group, or 1,4-phenylene group in which
hydrogen atom may be replaced by fluorine atom; and each atom which
constitutes those compounds may be replaced by its isotope.
10. A liquid crystal composition comprising, as a first component,
at least one liquid crystalline compound defined in any one of
claims 1 to 7, and comprising, as a second component, at least one
compound selected from the group consisting of the compounds
expressed by the general formula (5) or (6) 950wherein R.sup.3 and
R.sup.4 independently represent an alkyl group having 1 to 10
carbon atoms in which alkyl group not-adjacent any methylene group
may be replaced by oxygen atom or vinylene group, and any hydrogen
atom in the alkyl group may be replaced by fluorine atom; Y.sup.3
represents --CN or --C.ident.C--CN; ring D represents
trans-1,4-cyclohexylene group, 1,4-phenylene group,
pyrimidine-2,5-diyl group, or 1,3-dioxane-2,5-diyl group; ring E
represents trans-1,4-cyclohexylene group or pyrimidine-2,5-diyl
group, or 1,4-phenylene group in which hydrogen atom may be
replaced by fluorine atom; ring F represents
trans-1,4-cyclohexylene group or 1,4-phenylene group; Z.sup.3
represents 1,2-ethylene group, --COO--, or single bond; L.sup.3,
L.sup.4, and L.sup.5 independently represent hydrogen atom or
fluorine atom; a, b, and c are independently 0 or 1; and each atom
which constitutes those compounds may be replaced by its
isotope.
11. A liquid crystal composition comprising, as a first component,
at least one liquid crystalline compound defined in any one of
claims 1 to 7, comprising, as a second component, at least one
compound selected from the group consisting of the compounds
expressed by any one of the general formulas (2), (3), and (4), and
comprising, as a third component, at least one compound selected
from the group consisting of the compounds expressed by any one of
the general formulas (7), (8), and (9) 951wherein R.sup.5 and
R.sup.6 independently represent an alkyl group having 1 to 10
carbon atoms in which alkyl group not-adjacent any methylene group
may be replaced by oxygen atom or vinylene group, and any hydrogen
atom in the alkyl group may be replaced by fluorine atom; ring G,
ring I, and ring J independently represent trans-1,4-cyclohexylene
group or pyrimidine-2,5-diyl group, or 1,4-phenylene group in which
one or hydrogen atom may be replaced by fluorine atom; Z.sup.4 and
Z.sup.5 independently represent 1,2-ethylene group, vinylene group,
--COO--, --C.ident.HC--, or single bond; and each atom which
constitutes those compounds may be replaced by its isotope.
12. A liquid crystal composition comprising, as a first component,
at least one liquid crystalline compound defined in any one of
claims 1 to 7, and comprising, as a second component, at least one
compound selected from the group consisting of the compounds
expressed by any one of the general formulas (10), (11), and (12)
952wherein R.sup.7 and R.sup.8 independently represent an alkyl
group having 1 to 10 carbon atoms in which alkyl group not-adjacent
any methylene group may be replaced by oxygen atom or vinylene
group, and any hydrogen atom in the alkyl group may be replaced by
fluorine atom; ring K and ring M independently represent
trans-1,4-cyclohexylene or 1,4-phenylene; L.sup.6 and L.sup.7
independently represent hydrogen atom or fluorine atom, but in no
case simultaneously represent L.sup.6 and L.sup.7 hydrogen atom;
Z.sup.6 and Z.sup.7 independently represent --CH.sub.2CH.sub.2--,
--COO--, or single bond; and each atom which constitutes those
compounds may be replaced by its isotope.
13. A liquid crystal composition comprising, as a first component,
at least one liquid crystalline compound defined in any one of
claims 1 to 7, comprising, as a second component, at least one
compound selected from the group consisting of the compounds
expressed by any one of the general formulas (7), (8), and (9)
described above, and comprising, as a third component, at least one
compound selected from the group consisting of the compounds
expressed by any one of the general formulas (10), (11), and (12)
described above.
14. A liquid crystal composition comprising, as a first component,
at least one liquid crystalline compound defined in any one of
claims 1 to 7, comprising, as a second component, at least one
compound selected from the group consisting of the compounds
expressed by any one of the general formulas (2), (3), and (4)
described above, and comprising, as a third component, at least one
compound selected from the group consisting of the compounds
expressed by any one of the general formulas (7), (8), and (9)
described above.
15. A liquid crystal composition comprising, as a first component,
at least one liquid crystalline compound defined in any one of
claims 1 to 7, comprising, as a second component, at least one
compound selected from the group consisting of the compounds
expressed by the general formula (5) or (6) described above, and
comprising, as a third component, at least one compound selected
from the group consisting of the compounds expressed by any one of
the general formulas (7), (8), and (9) described above.
16. A liquid crystal composition comprising, as a first component,
at least one liquid crystalline compound defined in any one of
claims 1 to 7, comprising, as a second component, at least one
compound selected from the group consisting of the compounds
expressed by any one of the general formulas (2), (3), and (4)
described above, comprising, as a third component, at least one
compound selected from the group consisting of the compounds
expressed by the general formula (5) or (6) described above, and
comprising, as a fourth component, at least one component selected
from the group consisting of the compounds expressed by any one of
the general formulas (7), (8), and (9) described above.
17. A liquid crystal composition comprising at least one optically
active compound in addition to the liquid crystal composition
defined in any one of claims 8 to 16.
18. A liquid crystal display device fabricated by using the liquid
crystal composition defined in any one of claims 8 to 17.
Description
TECHNICAL FIELD
[0001] The present invention relates to liquid crystalline
compounds and liquid crystal compositions. More specifically, the
invention relates to novel liquid crystalline compounds
simultaneously having butylene group or propylenoxy group, and
2,3-difluorophenyl group in the compounds; to liquid crystal
compositions comprising the compound; and further to liquid crystal
display devices fabricated by using the liquid crystal
composition.
BACKGROUND ART
[0002] Display devices produced by employing optical anisotropy and
dielectric anisotropy which are characteristics of liquid
crystalline compounds (the term "liquid crystalline compounds" is
used in this specification as a general term for the compounds
which exhibit a liquid crystal phase and for the compounds which do
not exhibit a liquid crystal phase but are useful as component of
liquid crystal compositions) have widely been utilized for tabletop
calculators, word processors, and TV sets including watches, and
the demand for the devices are rising year after year.
[0003] Liquid crystal phase is broadly classified into nematic
phase, smectic phase, and cholesteric phase. Among them, nematic
phase has most widely been employed for display devices. As display
mode applied for liquid crystal display, TN (twisted nematic)
display mode, DS (dynamic scattering) display mode, guest-host
display mode, and DAP (Deformation of Aligned Phases) display mode
have been developed corresponding to electro-optic effects.
[0004] In recent years, coloring of liquid crystal displays has
rapidly been advanced, and thin film transistor (TFT) display mode
and super twisted nematic (STN) display mode are main streams in TN
display mode as display mode. On the other hand, CRT which is a
main stream of current television screen is expected to be replaced
by liquid crystal displays sooner or later. In order to realize the
replacement, liquid crystal displays must have display
characteristics comparable to those of CRT.
[0005] In the research and development of liquid crystal displays,
one's energies have been devoted to the improvement of response
speed, contrast, and viewing angle as important subject. Among
them, response speed and contrast became such an extent as equal to
those of CRT as a result of repeated improvements in TFT display
mode. However, a wide viewing angle comparable to that of CRT has
not yet been actualized, whereas some improvements such as an
improvement in the orientational direction of liquid crystal
molecules and the use of a phase difference plate have been made as
to viewing angle.
[0006] Although it is an active matrix mode similar to that of TFT
display mode, in-plane-switching (IPS) display mode which is
characterized in that comb type electrodes are formed only one side
of substrate is lately performed on the stage as a mode for
actualizing a wide viewing angle (G. Baur, Freiburger Arbeistagung
Flussigkristalle, Abstract No. 22 (1993) and M. Oh-e et al., ASIA
DISPLAY '95, 577 (1995)). When liquid crystalline compounds having
a negative dielectric anisotropy value (.DELTA..epsilon.) was used
in IPS display mode, a dramatically wide viewing angle was
obtained.
[0007] However, this IPS display mode has such a defect that
response speed is considerably low compared with conventional TFT
display mode or STN display mode. Then, liquid crystalline
compounds having a negative and high .DELTA..epsilon. and a low
viscosity are have been required in IPS display mode.
[0008] Also, since active matrix driving mode is employed in IPS
mode as described above, liquid crystalline compounds having a high
voltage holding ratio (V. H. R.) are more preferable.
[0009] Various compounds having a negative dielectric anisotropy
value are already known. In Laid-open Japanese Patent Publication
No. Hei 2-4724 and Tokuhyo (Laid-open Japanese WO publication) No.
Hei 2-503441, compounds having 2,3-difluoro-1,4-phenylene group in
their partial structure are disclosed as liquid crystal compound
having a negative .DELTA..epsilon..
[0010] It is considered that in the compounds having such partial
structure, fluorine atoms substituted at positions 2 and 3 act so
as to increase dipole moment in the direction of the minor axis of
molecules to make dipole moment of the major axis smaller than the
dipole moment in the direction of minor axis, and as the result,
the compounds come to have a negative dielectric anisotropy value.
However, compounds having such partial structure become slightly
narrow in their temperature range exhibiting a liquid crystal phase
compared with compounds in which hydrogen atoms of phenylene group
are not replaced by fluorine atoms, their miscibility with other
liquid crystalline compounds particularly at very low temperatures
can hardly be said to be excellent, and sometimes such phenomena
that smectic phase is developed and crystals are separated in
liquid crystal compositions in a low temperature region are
observed.
[0011] Compounds expressed by the following formula (a) are
described in Tokuhyo No. Hei 2-503441: 2
[0012] wherein R and R' represent an alkyl group and alkoxy group,
respectively.
[0013] Whereas structural formula of the compounds is described in
the publication mentioned above, physical properties and the likes
necessary for judging the utility of the compounds as liquid
crystalline compound are not described at all therein. Based on the
consideration by the present inventors, whereas an improvement in
miscibility by the compounds of the formula (a) described above
compared with compounds having no 1,2-ethylene group can be
surmised since the compounds of the formula (a) have 1,2-ethylene
group as bonding group in skeleton structure, their effect can not
be said to be sufficient.
DISCLOSURE OF THE INVENTION
[0014] An object of the present invention is to provide liquid
crystalline compounds which are wide particularly in temperature
range of liquid crystal phase, have a low viscosity, have a
negative and large .DELTA..epsilon., and are improved in solubility
at low temperatures; to provide liquid crystal compositions
comprising the compound; and to provide liquid crystal display
devices fabricated by using the liquid crystal composition, thereby
to overcome the problems in conventional technologies described
above.
[0015] Then, compounds expressed by the general formula (1) and
simultaneously having butylene group or propylenoxy group, and
2,3-difluoro-1,4-phenylene group in the structure of compounds were
diligently investigated by the present inventors. As the result of
the investigation, it has been found out that the compounds are
characterized in that they are wide in temperature range exhibiting
a liquid crystal phase, are low in viscosity, and have a negative
and large .DELTA..epsilon., as well as they are remarkably
excellent in miscibility at low temperatures, leading to the
accomplishment of the present invention.
[0016] That is, the present invention is summarized as follows:
[0017] [1] A liquid crystalline compound expressed by the general
formula (1) 3
[0018] wherein R.sup.1 represents an alkyl group having 1 to 15
carbon atoms in which alkyl group, not-adjacent any methylene group
may be replaced by oxygen atom or vinylene group, and any hydrogen
atom in the alkyl group may be replaced by fluorine atom; ring
A.sup.1, ring A.sup.2, and ring A.sup.3 independently represent
trans-1,4-cyclohexylene group, trans-1,4-silacyclohexylene group,
pyrimidine-2,5-diyl group, pyridine-2,5-diyl group,
1,3-dioxane-2,5-diyl group, tetrahydropyran-2,5-diyl group,
1,3-dithian-2,5-diyl group, or tetrahydrothiopyran-2,5-diyl group,
or 1,4-phenylene group in which one or more hydrogen atoms on the
six-membered ring may be replaced by a halogen atom; X.sup.1,
X.sup.2, and X.sup.3 independently represent --(CH.sub.2).sub.4--,
--(CH.sub.2).sub.3O--, --O(CH.sub.2).sub.3--, or single bond;
Y.sup.1 represents hydrogen atom or an alkyl group having 1 to 15
carbon atoms in which alkyl group not-adjacent any methylene group
may be replaced by oxygen atom or vinylene group; m and n are
independently 0 or 1; and any atom which constitutes this compound
may be replaced by its isotope.
[0019] [2] The liquid crystalline compound recited in paragraph [1]
above wherein ring Al represents trans-1,4-cyclohexylene group, or
1,4-phenylene group in which one or more hydrogen atoms on the
six-membered ring may be replaced by fluorine atom; X.sup.1
represents --(CH.sub.2).sub.4-- or --(CH.sub.2).sub.3O--; and
either m and n are 0 in the general formula (1).
[0020] [3] The liquid crystalline compound recited in paragraph [1]
above wherein ring A.sup.1 and ring A.sup.2 independently represent
trans-1,4-cyclohexylene group, or 1,4-phenylene group in which one
or more hydrogen atoms on the six-membered ring may be replaced by
fluorine atom; XI represents --(CH.sub.2).sub.4-- or
--(CH.sub.2).sub.3O--; X.sup.2 represents single bond; and m is 1
and n is 0 in the general formula (1).
[0021] [4] The liquid crystalline compound recited in paragraph [1]
above wherein ring A.sup.1 and ring A.sup.2 independently represent
trans-1,4-cyclohexylene group, or 1,4-phenylene group in which one
or more hydrogen atoms on the six-membered ring may be replaced by
fluorine atom; X.sup.2 represents --(CH.sub.2).sub.4-- or
--(CH.sub.2).sub.3O--; X.sup.1 represents single bond; and m is 1
and n is 0 in the general formula (1).
[0022] [5] The liquid crystalline compound recited in paragraph [1]
above wherein ring A.sup.1, ring A.sup.2, and ring A.sup.3
independently represent trans-1,4-cyclohexylene group, or
1,4-phenylene group in which one or more hydrogen atoms on the
six-membered ring may be replaced by fluorine atom; X.sup.1
represent --(CH.sub.2).sub.4-- or --(CH.sub.2).sub.3O--; either
X.sup.2 and X.sup.3 represent single bond; and m is 1 and n is 1 in
the general formula (1).
[0023] [6] The liquid crystalline compound recited in paragraph [1]
above wherein ring A.sup.1, ring A.sup.2, and ring A.sup.3
independently represent trans-1,4-cyclohexylene group, or
1,4-phenylene group in which one or more hydrogen atoms on the
six-membered ring may be replaced by fluorine atom; X.sup.2
represents --(CH.sub.2).sub.4-- or --(CH.sub.2).sub.3O--; either
X.sup.1 and X.sup.3 represent single bond; and m is 1 and n is 1 in
the general formula (1).
[0024] [7] The liquid crystalline compound recited in paragraph [1]
above wherein ring A.sup.1, ring A.sup.2, and ring A.sup.3
independently represent trans-1,4-cyclohexylene group, or
1,4-phenylene group in which one or more hydrogen atoms on the
six-membered ring may be replaced by fluorine atom; X.sup.3
represents --(CH.sub.2).sub.4-- or --(CH.sub.2).sub.3O--; either
X.sup.1 and X.sup.2 represent single bond; and m is 1 and n is 1 in
the general formula (1).
[0025] [8] A liquid crystal composition comprising at least two
components and comprising at least one liquid crystalline compound
expressed by the general formula (1) 4
[0026] wherein R.sup.1 represents an alkyl group having 1 to 15
carbon atoms in which alkyl group not-adjacent any methylene group
may be replaced by oxygen atom or vinylene group, and any hydrogen
atom in the alkyl group may be replaced by fluorine atom; ring
A.sup.1, ring A.sup.2, and ring A.sup.3 independently represent
trans-1,4-cyclohexylene group, trans-1,4-silacyclohexylene group,
pyrimidine-2,5-diyl group, pyridine-2,5-diyl group,
1,3-dioxane-2,5-diyl group, tetrahydropyran-2,5-diyl group,
1,3-dithian-2,5-diyl group, or tetrahydrothiopyran-2,5-diyl group,
or 1,4-phenylene group in which one or more hydrogen atoms on the
six-membered ring may be replaced by a halogen atom; X.sup.1,
X.sup.2, and X.sup.3 independently represent --(CH.sub.2).sub.4--,
--(CH.sub.2).sub.3O--, --O(CH.sub.2).sub.3--, or single bond;
Y.sup.1 represents hydrogen atom or an alkyl group having 1 to 15
carbon atoms in which alkyl group not-adjacent any methylene group
may be replaced by oxygen atom or vinylene group; m and n are
independently 0 or 1; and any atom which constitutes this compound
may be replaced by its isotope.
[0027] [9] A liquid crystal composition comprising, as a first
component, at least one liquid crystalline compound recited in any
one of paragraphs [1] to [7] above, and comprising, as a second
component, at least one compound selected from the group consisting
of the compounds expressed by any one of the general formulas (2),
(3), and (4) 5
[0028] wherein R.sup.2 represents an alkyl group having 1 to 10
carbon atoms in which alkyl group not-adjacent any methylene group
may be replaced by oxygen atom or vinylene group; and any hydrogen
atom in the alkyl group may be replaced by fluorine atom; Y.sup.2
represents fluorine atom, chlorine atom, --OCF.sub.3, --OCF.sub.2H,
--CF.sub.3, --CF.sub.2H, --CFH.sub.2, --OCF.sub.2CF.sub.2H, or
--OCF.sub.2CFHCF.sub.3; L.sup.1 and L.sup.2 independently represent
hydrogen atom or fluorine atom; Z.sup.1 and Z.sup.2 independently
represent 1,2-ethylene group, vinylene group, 1,4-butylene group,
--COO--, --CF.sub.2O--, --OCF.sub.2--, or single bond; ring B
represents trans-1,4-cyclohexylene group or 1,3-dioxane-2,5-diyl
group, or 1,4-phenylene group in which hydrogen atom may be
replaced by fluorine atom; ring C represents
trans-1,4-cyclohexylene group, or 1,4-phenylene group in which
hydrogen atom may be replaced by fluorine atom; and each atom which
constitutes those compounds may be replaced by its isotope.
[0029] [10] A liquid crystal composition comprising, as a first
component, at least one liquid crystalline compound recited in any
one of paragraphs [1] to [7] above, and comprising, as a second
component, at least one compound selected from the group consisting
of the compounds expressed by the general formula (5) or (6) 6
[0030] wherein R.sup.3 and R.sup.4 independently represent an alkyl
group having 1 to 10 carbon atoms in which alkyl group not-adjacent
any methylene group may be replaced by oxygen atom or vinylene
group, and any hydrogen atom in the alkyl group may be replaced by
fluorine atom; Y.sup.3 represents --CN or --C.ident.C--CN; ring D
represents trans-1,4-cyclohexylene group, 1,4-phenylene group,
pyrimidine-2,5-diyl group, or 1,3-dioxane-2,5-diyl group; ring E
represents trans-1,4-cyclohexylene group or pyrimidine-2,5-diyl
group, or 1,4-phenylene group in which hydrogen atom may be
replaced by fluorine atom; ring F represents
trans-1,4-cyclohexylene group or 1,4-phenylene group; Z.sup.3
represents 1,2-ethylene group, --COO--, or single bond; L.sup.3,
L.sup.4, and L.sup.5 independently represent hydrogen atom or
fluorine atom; a, b, and c are independently 0 or 1; and each atom
which constitutes those compounds may be replaced by its
isotope.
[0031] [11] A liquid crystal composition comprising, as a first
component, at least one liquid crystalline compound recited in any
one of paragraphs [1] to [7] above, comprising, as a second
component, at least one compound selected from the group consisting
of the compounds expressed by any one of the general formulas (2),
(3), and (4), and comprising, as a third component, at least one
compound selected from the group consisting of the compounds
expressed by any one of the general formulas (7), (8), and (9)
7
[0032] wherein R.sup.5 and R.sup.6 independently represent an alkyl
group having 1 to 10 carbon atoms in which alkyl group not-adjacent
any methylene group may be replaced by oxygen atom or vinylene
group, and any hydrogen atom in the alkyl group may be replaced by
fluorine atom; ring G, ring I, and ring J independently represent
trans-1,4-cyclohexylene group or pyrimidine-2,5-diyl group, or
1,4-phenylene group in which one hydrogen atom may be replaced by
fluorine atom; Z.sup.4 and Z.sup.5 independently represent
1,2-ethylene group, vinylene group, --COO--, --C.ident.--C--, or
single bond; and each atom which constitutes those compounds may be
replaced by its isotope.
[0033] [12] A liquid crystal composition comprising, as a first
component, at least one liquid crystalline compound recited in any
one of paragraphs [1] to [7] above, comprising, as a second
component, at least one compound selected from the group consisting
of the compounds expressed by any one of the general formulas (2),
(3), and (4), and comprising, as a third component, at least one
compound selected from the group consisting of the compounds
expressed by any one of the general formulas (10), (11), and (12)
8
[0034] wherein R.sup.7 and R.sup.8 independently represent an alkyl
group having 1 to 10 carbon atoms in which alkyl group not-adjacent
any methylene group may be replaced by oxygen atom or vinylene
group, and any hydrogen atom in the alkyl group may be replaced by
fluorine atom; ring K and ring M independently represent
trans-1,4-cyclohexylene or 1,4-phenylene; L.sup.6 and L.sup.7
independently represent hydrogen atom or fluorine atom, but in no
case simultaneously represent L.sup.6 and L.sup.7 hydrogen atom;
Z.sup.6 and Z.sup.7 independently represent --CH.sub.2CH.sub.2--,
--COO--, or single bond; and each atom which constitutes those
compounds may be replaced by its isotope.
[0035] [13] A liquid crystal composition comprising, as a first
component, at least one liquid crystalline compound recited in any
one of paragraphs [1] to [7] above, comprising, as a second
component, at least one compound selected from the group consisting
of the compounds expressed by any one of the general formulas (7),
(8), and (9) described above, and comprising, as a third component,
at least one compound selected from the group consisting of the
compounds expressed by any one of the general formulas (10), (11),
and (12) described above.
[0036] [14] A liquid crystal composition comprising, as a first
component, at least one liquid crystalline compound recited in any
one of paragraphs [1] to [7] above, comprising, as a second
component, at least one compound selected from the group consisting
of the compounds expressed by any one of the general formulas (2),
(3), and (4) described above, and comprising, as a third component,
at least one compound selected from the group consisting of the
compounds expressed by any one of the general formulas (7), (8),
and (9) described above.
[0037] [15] A liquid crystal composition comprising, as a first
component, at least one liquid crystalline compound recited in any
one of paragraphs [1] to [7] above, comprising, as a second
component, at least one compound selected from the group consisting
of the compounds expressed by the general formula (5) or (6)
described above, and comprising, as a third component, at least one
compound selected from the group consisting of the compounds
expressed by any one of the general formulas (7), (8), and (9)
described above.
[0038] [16] A liquid crystal composition comprising, as a first
component, at least one liquid crystalline compound recited in any
one of paragraphs [1] to [7] above, comprising, as a second
component, at least one compound selected from the group consisting
of the compounds expressed by any one of the general formulas (2),
(3), and (4) described above, comprising, as a third component, at
least one compound selected from the group consisting of the
compounds expressed by the general formula (5) or (6) described
above, and comprising, as a fourth component, at least one
component selected from the group consisting of the compounds
expressed by any one of the general formulas (7), (8), and (9)
described above.
[0039] [17] A liquid crystal composition comprising at least one
optically active compound in addition to the liquid crystal
composition recited in any one of paragraphs [8] to [16] above.
[0040] [18] A liquid crystal display device fabricated by using the
liquid crystal composition recited in any one of paragraphs [8] to
[17] above.
[0041] Liquid crystalline compounds of the present invention
expressed by the general formula (1) are two to four rings
compounds having butylene group or propylenoxy group, and
2,3-difluorophenyl group at the same time in the molecular
structure. As a matter of course, these liquid crystalline
compounds are extremely stable physically and chemically under the
environment in which liquid crystal display devices are used, and
the compounds are characterized in that they are wide in
temperature range exhibiting a liquid crystal phase, excellent in
solubility in liquid crystal compositions even at low temperatures,
and low in viscosity, and have a negative and large
.DELTA..epsilon..
[0042] As described in the section of BACKGROUND ART, whereas
compounds having 2,3-difluoro-1,4-phenylene group as a partial
structure are already disclosed in patent publications, it is a
fact discovered for the first time by the present inventors that
the compounds simultaneously having 1,4-butylene group or
propylenoxy group as bonding group and 2,3-difluoro-1,4-phenylene
group exhibit the characteristic described above, and it is
difficult to expect such fact from conventional technology.
[0043] In the compounds of the present invention, it is possible to
optionally adjust desired physical properties by selecting a proper
ring structure, bonding group, and lateral structure among molecule
constituting elements. Accordingly, novel liquid crystal
compositions and liquid crystal display devices having excellent
characteristics, specifically
[0044] 1) having a wide temperature range of liquid crystal
phase,
[0045] 2) being low in viscosity, and having a negative and large
.DELTA..epsilon.,
[0046] 3) separating no crystals and developing no smectic phase
even at very low temperatures,
[0047] 4) being physically and chemically stable, and being
possible to expand the temperature range of their usage, to drive
at a low voltage, and to realize a high speed response and high
contrast
[0048] can be provided by using the compound of the present
invention as component of liquid crystal compositions.
[0049] While any of the compounds of the present invention exhibits
preferable physical properties, liquid crystal compositions having
physical properties suitable for their use can be produced by using
the compound which is expressed by the general formula (1) in which
ring A.sup.1, ring A.sup.2, ring A.sup.3, X.sup.1, X.sup.2,
X.sup.3, m, and n are properly selected.
[0050] That is, when compounds having a negative and large
.DELTA..epsilon. are necessary, it is sufficient to suitably select
2,3-difluoro-1,4-phenylene group for any one of ring A.sup.1, ring
A.sup.2, ring A.sup.3, and when compounds having a high optical
anisotropy value are necessary, it is sufficient to select
compounds in which any one of ring A.sup.1, ring A.sup.2, and ring
A.sup.3 is 1,4-phenylene group, and every one of X.sup.1, X.sup.2,
and X.sup.3 is single bond. When compounds having their temperature
range of liquid crystal phase at high temperature side are
necessary, it is sufficient to suitably select three rings or four
rings compounds, and when compounds having their temperature range
of liquid crystal phase at low temperature side are necessary, it
is sufficient to suitably select two rings compounds,
respectively.
[0051] Compounds in which hydrogen atom on 1,4-phenylene group is
replaced by fluorine atom exhibit an excellent solubility at low
temperatures.
[0052] Compounds expressed by one of the following general formulas
(1-1) to (1-12) can be mentioned as particularly preferable ones
among the compounds expressed by the general formula (1): 9
[0053] wherein R.sup.1, ring A.sup.1, ring A.sup.2, ring A.sup.3,
and Y.sup.1 have the same meaning as described above.
[0054] In the compounds described above, while R.sup.1 represents
an alkoxy group, alkoxyalkyl group, alkenyl group, alkenyloxy
group, alkenyloxyalkyl group, or alkyloxyalkenyl group having 1 to
15 carbon atoms, particularly preferable groups among them are
methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl,
methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy,
octyloxy, methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl,
methoxyethyl, ethoxyethyl, propoxyethyl, methoxypropyl,
ethoxypropyl, propoxypropyl, vinyl, 1-propenyl, 2-propenyl,
1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl,
3-pentenyl, 4-pentenyl, 2-propenyloxy, 2-butenyloxy, 2-pentenyloxy,
4-pentynyloxy, methoxy-1-propenyl, methoxy-1-pentenyl, and
methoxy-3-pentenyl.
[0055] In the compounds described above, while Y.sup.1 represents
hydrogen atom, an alkyl group, alkoxy group, alkoxyalkyl group,
alkenyl group, alkenyloxy group, alkenyloxyalkyl group, or
alkyloxyalkenyl group having 1 to 15 carbon atoms, particularly
preferable groups among them are methyl, ethyl, propyl, butyl,
pentyl, hexyl, heptyl, octyl, methoxy, ethoxy, propoxy, butoxy,
pentyloxy, hexyloxy, heptyloxy, octyloxy, methoxymethyl,
ethoxymethyl, propoxymethyl, butoxymethyl, methoxyethyl,
ethoxyethyl, propoxyethyl, methoxypropyl, ethoxypropyl, and
propoxypropyl.
[0056] Liquid crystal compositions of the present invention are
described below. Liquid crystal compositions of the present
invention preferably comprise at least one compound expressed by
the general formula (1) in the ratio of 0.1 to 99.9% by weight to
develop excellent characteristics.
[0057] More preferably, the liquid crystal compositions provided by
the present invention are completed by mixing compounds selected
from the group consisting of the compounds expressed by one of the
general formulas (2) to (9) depending on the purposes of the liquid
crystal compositions in addition to the first component comprising
at least one compound expressed by the general formula (1).
[0058] The present invention recited in the paragraphs [12] and
[13] above are concerned with N type (having a negative
.DELTA..epsilon.) liquid crystal compositions. In the same way as P
type (having a positive .DELTA..epsilon.) liquid crystal
compositions, N type liquid crystal compositions can be driven by
various driving modes, for example, by IPS mode (In Plane Switching
Mode). The present invention recited in paragraphs [9], [10], [11],
[14], [15], and [16] are concerned with P type liquid crystal
compositions. It is possible to control elastic constants of liquid
crystal compositions and to improve the miscibility of the
compositions at low temperatures by adding a N type liquid
crystalline compound to P type liquid crystal compositions.
[0059] Following compounds can preferably be mentioned as ones used
in the liquid crystal compositions of the present invention and
expressed by one of the general formulas (2) to (4): 10
[0060] wherein R.sup.2 and Y.sup.2 have the same meaning as
described above.
[0061] Compounds expressed by one of the general formulas (2) to
(4) have a positive dielectric anisotropy value, are remarkably
excellent in thermal stability and chemical stability, and are
useful when liquid crystal compositions for TFT (AM-LCD) display
mode of which a high reliability such as a particularly high
voltage holding ratio or large specific resistivity is required are
produced.
[0062] When the liquid crystal compositions for TFT display mode
are produced, the compounds expressed by one of the general
formulas (2) to (4) can be used in the range of 0.1 to 99.9% by
weight based on the total amount of liquid crystal composition, and
the amount is preferably 10 to 97% by weight and more desirably 40
to 95% by weight. Also, the compositions may further comprise the
compound expressed by one of the general formulas (7) to (9) for
the purpose of adjusting viscosity. Even when liquid crystal
compositions for STN display mode or TN display mode are produced,
the compound expressed by one of the general formulas (2) to (4)
can be used. In this case, the amount of the compound to be used is
preferably less than 50% by weight.
[0063] As the compound used in the liquid crystal compositions of
the present invention expressed by the general formula (5) or (6),
the following compounds can preferably be mentioned: 11
[0064] wherein R.sup.3, R.sup.4, and Y.sup.3 have the same meaning
as described above.
[0065] Compounds expressed by one of the general formula (5) or (6)
have a positive and large dielectric anisotropy value, and are used
particularly for the purpose of lowering threshold voltage of
liquid crystal compositions. Also, they are used for the purpose of
adjusting optical anisotropy value, and widening nematic range such
as raising clearing point. Further, they are used even for the
purpose of improving the steepness of V-T curve of liquid crystal
compositions for STN display mode or TN display mode.
[0066] Compounds expressed by the general formula (5) or (6) are
useful when liquid crystal compositions particularly for STN
display mode or TN display mode are produced.
[0067] When the content of the compound expressed by the general
formula (5) or (6) in liquid crystal compositions is increased,
threshold voltage of liquid crystal compositions lowers but
viscosity increases. Accordingly, it is advantageous to use the
compound in a large amount since driving at a low voltage becomes
possible, so far as viscosity of liquid crystal compositions
satisfies required characteristics.
[0068] When liquid crystal compositions for STN display mode or TN
display mode are produced, the amount of the compound expressed by
the general formula (5) or (6) to be used is in the range of 0.1 to
99.9% by weight, preferably 10 to 97% by weight, and more desirably
40 to 95% by weight.
[0069] As the compounds used in the liquid crystal compositions of
the present invention and expressed by one of the general formulas
(7) to (9), the following compounds can preferably be mentioned.
12
[0070] wherein R.sup.5 and R.sup.6 have the same meaning as
described above.
[0071] Compounds expressed by one of the general formulas (7) to
(9) have a small absolute value of dielectric anisotropy, and are
close to neutral. Compounds expressed by the general formula (7)
are used principally for the purpose of adjusting viscosity and
adjusting optical anisotropy value of liquid crystal compositions.
Compounds expressed by the general formula (8) or (9) are used for
the purpose of widening nematic range such as raising clearing
point, or for the purpose of adjusting optical anisotropy
value.
[0072] When the content of the compound expressed by one of the
general formulas (7) to (9) in liquid crystal compositions is
increased, threshold voltage of liquid crystal compositions rises
but viscosity reduces. Accordingly, it is desirable to use the
compound in a large amount so far as threshold voltage of liquid
crystal compositions satisfies required characteristics. When
liquid crystal compositions for TFT are produced, the amount of the
compound expressed by one of the general formulas (7) to (9) to be
used is preferably less than 40% by weight and more desirably less
than 35% by weight. When liquid crystal compositions for STN
display mode or TN display mode are produced, the amount is
preferably less than 70% by weight and more desirably less than 60%
by weight.
[0073] As the compounds used in the liquid crystal compositions of
the present invention and expressed by one of the general formulas
(10) to (12), the following compounds can preferably be mentioned:
13
[0074] wherein R.sup.7 and R.sup.8 have the same meaning as
described above.
[0075] Compounds expressed by one of the general formulas (10) to
(12) have a negative dielectric anisotropy value. Compounds
expressed by the general formula (10) are two rings compounds, and
are used principally for the purpose of adjusting threshold
voltage, adjusting viscosity, or adjusting optical anisotropy
value. Compounds expressed by the general formula (11) are used for
the purpose of widening nematic range such as raising clearing
point, or for the purpose of adjusting optical anisotropy value.
Compounds expressed by the general formula (12) are used for the
purpose of widening nematic range as well as for the purpose of
lowering threshold voltage and for the purpose of increasing
optical anisotropy value.
[0076] Compounds expressed by one of the general formulas (10) to
(12) are used principally for N type (having a negative dielectric
anisotropy .DELTA..epsilon.) liquid crystal compositions. When the
amount of the compound to be used is increased, threshold voltage
of liquid crystal compositions lowers but viscosity increases.
Accordingly, it is desirable to use the compound in a small amount
so far as threshold voltage of liquid crystal compositions is
satisfied. However, since these compounds have an absolute value of
dielectric anisotropy value of lower than 5, when the amount of the
compound used is less than 40% by weight, driving at a low voltage
sometimes becomes impossible.
[0077] The amount of the compound expressed by one of the general
formulas (10) to (12) to be used in liquid crystal compositions is
preferably more than 40% by weight when liquid crystal compositions
for N type TFT are produced and the amount is more desirably 50 to
95% by weight.
[0078] Further, for the purpose of control the elastic constants of
liquid crystal compositions and regulating voltage-transmittance
curve (V-T curve), the compound expressed by one of the general
formulas (10) to (12) is sometimes added to P type (having positive
dielectric anisotropy .DELTA..epsilon.) liquid crystal
compositions. In such case, the amount of the compound expressed by
one of the general formulas (10) to (12) to be used in liquid
crystal compositions is preferably less than 30% by weight.
[0079] With the exception of such specific cases as liquid crystal
compositions for OCB (Optically Compensated Birefringence) mode and
the likes, an optically active compound is usually added to the
liquid crystal compositions of the present invention for the
purpose of inducing helical structure of liquid crystal composition
to adjust required twist angle and to prevent reverse twist. While
any known optically active compounds used for such purposes can be
added in the liquid crystal compositions of the present invention,
the following optically active compounds can be mentioned as
preferable examples: 14
[0080] These optically active compounds are usually added to liquid
crystal compositions of the present invention to adjust their pitch
of twist. The twist pitch is preferably adjusted in the range of 40
to 200 .mu.m in the case of liquid crystal compositions for TFT or
TN, and preferably adjusted in the range of 6 to 20 .mu.m in the
case of liquid crystal compositions for STN. In the case for
bistable TN mode, it is preferable to adjust the pitch in the range
of 1.5 to 4 .mu.m. Further, two or more kind of optically active
compounds may be added for the purpose of adjusting the dependency
of the pitch length on temperature.
[0081] Liquid crystal compositions of the present invention can be
produced by methods which are conventional by themselves.
Generally, a method in which various components are dissolved one
another at a high temperature has been adopted.
[0082] Further, the liquid crystal compositions of the present
invention can be used as ones for guest-host (GH) mode by adding a
dichroic dye such as merocyanine type, styryl type, azo type,
azomethine type, azoxy type, quinophthalone type, anthraquinone
type, and tetrazine type thereto. Alternatively, the liquid crystal
compositions can be used as NCAP which is prepared by the
microencapsulation of a nematic liquid crystal, or as liquid
crystal compositions for polymer dispersed liquid crystal display
devices (PDLCD) represented by polymer net work liquid crystal
display devices (PNLCD) prepared by forming a polymer of
three-dimensional reticulated structure in a liquid crystal. Still
further, the liquid crystal compositions of the present invention
can be used as ones for electrically controlled birefringence (ECB)
mode or dynamic scattering (DS) mode.
[0083] [Methods for producing compounds]
[0084] Compounds of the present invention expressed by the general
formula (1) can readily be produced by using ordinary chemical
procedures of organic synthesis. For instance, the compounds can
readily be synthesized by selecting proper known reactions
described in reference books such as Organic Synthesis, Organic
Reactions, and Shin-Jikken Kagaku Kouza (Course of New Chemical
Experiment), and magazines, and using the reactions in
combination.
[0085] When butylene group is introduced at the position of a
bonding group (X.sup.1, X.sup.2, and X.sup.3), the compounds can be
produced, for instance, by the following reaction paths.
[0086] In the following, MSG1 and MSG2 independently represent a
mesogen (a residue of organic compounds); Hal represents Cl, Br, or
I; ring A represents trans-1,4-cyclohexylene group, 1,4-phenylene
group in which one or more hydrogen atoms on the six-membered ring
may be replaced by a halogen atom, pyrimidine-2,5-diyl group,
pyridine-2,5-diyl group, 1,3-dioxane-2,5-diyl group,
tetrahydropyran-2,5-diyl group, 1,3-dithian-2,5-diyl group, or
tetrahydrothiopyran-2,5-diyl group; and Y.sup.1 have the same
meaning as described above.
[0087] That is, 2-(1,3-dioxane-2-yl)ethyltriphenylphosphonium
halide (12) and aldehyde derivative (11) are subjected to the
Wittig reaction in an ether type solvent such as tetrahydrofuran
(hereinafter abbreviated to THF) and diethyl ether in the presence
of a base such as sodium methylate, potassium-t-butoxide (t-BuOK),
and butyl lithium to obtain compound (13). Subsequently, aldehyde
derivative (14) can be obtained by subjecting compound (13) to
hydrogen reduction in a mixed solvent of toluene/Solmix in the
presence of a metal catalyst such as palladium/carbon and Raney
nickel, and then reacting with a mineral acid such as hydrochloric
acid and sulfuric acid, or an organic acid such as formic acid and
p-toluenesulfonic acid.
[0088] Further, in the same way as that wherein compound (13) is
obtained from compound (11), compound (16) can be obtained by
subjecting compound (14) and compound (15) to the Wittig reaction,
and aldehyde derivative (17) can be produced by reacting it with
the same acid as described above. Subsequently, derivative (19)
having butylene group can be produced by reacting Grignard reagent
(18) with compound (17) to conduct Grignard reaction, reacting it
with the same acid as described above to dehydrate, and further
subjecting to hydrogen reduction by using the same metal catalyst
as described above. 15
[0089] When propylenoxy group having ether bond is introduced at
the position of a bonding group (X.sup.1, X.sup.2, and X.sup.3),
the compounds can be produced, for instance, by the following
reaction paths.
[0090] Aldehyde derivative (14) is reacted with lithium aluminum
hydride in a solvent such as toluene, THF, and diethyl ether to
reduce thereby to obtain alcohol derivative (20). This alcohol
derivative (20) is reacted with hydrobromic acid to produce
compound (21). Compound (23) having ether bond can be produced by
reacting compound (21) with compound (22) in the presence of sodium
hydride. 16
[0091] When 2,3-difluoro-1,4-phenylene group is introduced to aring
structure portion, the compounds can be produced, for instance, by
the following reaction paths.
[0092] a) The case wherein the introduction portion is located at
position 4 relative to MSG1 of benzene derivative:
[0093] Compound (25) can be obtained by reacting difluorobenzene
derivative (24) with n-butyl lithium or sec-butyl lithium in an
ether type solvent such as THF and diethyl ether, reacting with
zinc chloride, and then reacting with 2,3-difluoro-1-bromobenzene
in the presence of a metal catalyst of palladium (0).
[0094] b) The case wherein it is introduced cyclohexanone
derivative having MSG1 at position 4:
[0095] Compound (28) can be produced by reacting compound (26) with
Grignard reagent (27) to conduct the Grignard reaction, dehydrating
by the same procedure as described above, and then subjecting to
hydrogen reduction. 17
[0096] Compounds in which ring A.sup.1, ring A.sup.2, and ring
A.sup.3 are silacyclohexane rings can be produced according to the
method disclosed in Laid-open Japanese Patent Publication No. Hei
7-70148, Laid-open Japanese Patent Publication No. 7-112990, and
Laid-open Japanese Patent Publication Nol Hei 7-149770.
[0097] Compounds of the present invention expressed by the general
formula (1) can be produced by selecting and using proper reactions
described above.
[0098] Any of the liquid crystalline compounds of the present
invention expressed by the general formula (1) thus obtained has
such characteristics that the temperature range in which the
compound exhibits a liquid crystal phase is wide, viscosity is low,
and .DELTA..epsilon. is negative and large, and the compound is
readily mixed with other various liquid crystal materials even at
low temperatures. Accordingly, the compound is remarkably excellent
as constituent of nematic liquid crystal compositions suitable for
TFT type display mode and IPS mode.
BEST MODE FOR CARRYING OUT THE INVENTION
[0099] Now, the present invention will be described in more detail
with reference to Examples. However, it should be understood that
the scope of the present invention is by no means restricted by
such specific Examples. In the Examples, the structure of compounds
was confirmed by nuclear magnetic resonance spectrum (hereinafter
abbreviated to .sup.1H-NMR) and mass spectrum (hereinafter
abbreviated to MS). In the data of .sup.1H-NMR in the Examples, t
indicates triplet, q: quartet, M: multiplet, and J: coupling
constant. In the data of MS, M.sup.+ indicates molecular ion peak.
Further, C indicates crystal, S.sub.A: smectic phase A, S.sub.B:
smectic phase B, N: nematic phase, and Iso: isotropic liquid phase,
and the unit of every phase transition temperature is .degree.
C.
EXAMPLE 1
[0100] Preparation of
2,3-difluoro-1-propyl-4-(trans-4-(4-(trans-4-pentylc-
yclohexyl)butyl)cyclohexyl)benzene [Compound expressed by the
general formula (1) wherein R.sup.1 is pentyl group, ring A.sup.1
and ring A2 are trans-1,4-cyclohexylene group, X.sup.1 is butylene
group, X.sup.2 is single bond, Y.sup.1 is propyl group, m is 1, n
is 0 (Compound No. 20)]
[0101] First step
[0102] Under nitrogen gas stream, 52.3 g (2150 mmol) of magnesium
was added in 100 ml of THF, and a solution of 378 g (1960 mmol) of
2,3-difluoro-1-bromobenzene in 4.0 l of THF was added by drops
thereto so that the reaction temperature was maintained at about
50.degree. C. Further, after stirred at room temperature for 1
hour, a solution of 500 g (1630 mmol) of
4-(4-(trans-4-pentylcyclohexyl)butyl)cyclohexanone in 5.0 l of THF
was added by drops to the solution and stirred at 50 to 60.degree.
C. for 2 hours, and then 1.0 l of saturated aqueous ammonium
chloride solution was added to the solution to terminate the
reaction. The reaction mixture was filtered with Celite, the
solvent was distilled off under a reduced pressure, and then it was
extracted with 2.0 l of toluene. The organic layer was washed with
1.0 l of water thrice and dried over anhydrous magnesium sulfate.
After the anhydrous magnesium sulfate was removed by filtration,
23.7 g of p-toluenesulfonic acid monohydrate was added to the
filtrate and heated to reflux for 4 hours. The organic layer was
washed with 1.0 l of water thrice and dried over anhydrous
magnesium sulfate. The solvent was distilled off under a reduced
pressure, and the residue was subjected to silica gel column
chromatography (eluent: heptane) to obtain 436 g of a crude
1,2-difluoro-3-(4-(4-(trans-4-pentylcyclohexyl)-butyl)cyclohexene-1-yl)be-
nzene.
[0103] Second step
[0104] In 4.0 l of mixed solvent of toluene/Solmix (1/1) was
dissolved 436 g (1080 mmol) of the crude product obtained by the
procedures described above, 21.8 g of 5% by weight-palladium/carbon
catalyst was added thereto, and then they were stirred at room
temperature under the condition of a hydrogen gas pressure of 1 to
2 kg/cm.sup.2 for 6 hours. After the catalyst was removed by
filtration, the solvent was distilled off under a reduced pressure,
and the residue was subjected to silica gel column chromatography
(eluent: heptane) and recrystallized from heptane twice to obtain
114 g of 1,2-difluoro-3-(trans-4-(4-(trans-4-pentylcycloh-
exyl)butyl)cyclohexyl)benzene.
[0105] Third step
[0106] Under nitrogen gas stream, a solution prepared by dissolving
30.0 g (74.1 mmol) of
1,2-difluoro-3-(trans-4-(4-(trans-4-pentylcyclohexyl)butyl-
)cyclohexyl)benzene in 300 ml of THF was cooled down to -70.degree.
C., 88.9 ml of sec-butyl lithium (1.0M, cyclohexane solution) was
added by drops thereto while being maintained at the same
temperature, and stirred at the same temperature for further 2
hours. Subsequently, a suspension prepared by adding 9.98 g (88.9
mmol) of t-BuOK to 100 ml of THF was added by drops to the reaction
liquid while being maintained at the same temperature, and stirred
at the same temperature for further 1 hour. To the reaction liquid
was added by drops a solution of 15.1 g (88.9 mmol) of propyliodide
in 150 ml of THF while being maintained at the same temperature and
stirred at the same temperature for 5 hours. The reaction was
terminated by adding 200 ml of water to the reaction mixture, and
the solvent was distilled off under a reduced pressure.
Concentrated residue was extracted with 500 ml of toluene, and the
organic layer was washed with 200 ml of water thrice and dried over
anhydrous magnesium sulfate. The solvent was distilled off under a
reduced pressure, and the residue was subjected to silica gel
column chromatography (eluent: heptane) to obtain a crude
2,3-difluoro-1-propyl-4-(trans-4-(4-(trans-4-pentylcyclohe-
xyl)butyl)cyclohexyl)benzene. This crude product was recrystallized
from heptane thrice to obtain 5.40 g (yield 2.82%) of the subject
compound.
[0107] Phase transition temperature: C 40.2 S.sub.B 90.9 N 98.0
Iso
[0108] .sup.1H-NMR: .delta.: (ppm): 0.50.about.2.10 (m, 45H), 2.59
(t, 1H, J=7.3 Hz), 6.70.about.7.10 (m, 2H)
[0109] MS: m/e=446 (M.sup.+)
EXAMPLE 2
[0110] Preparation of
1-ethoxy-2,3-difluoro-4-(trans-4-(4-(trans-4-pentylc-
yclohexyl)butyl)cyclohexyl)benzene [Compound expressed by the
general formula (1) wherein R.sup.1 is pentyl group, either ring
A.sup.1 and ring A.sup.2 are trans-1,4-cyclohexylene group, X.sup.1
is butylene group, X.sup.2 is single bond, Y.sup.1 is ethoxy group,
m is 1, and n is 0 (Compound No. 23)]
[0111] First step
[0112] Under nitrogen gas stream, a solution of 60.0 g (148 mmol)
of
1,2-difluoro-3-(trans-4-(4-(trans-4-pentylcyclohexyl)butyl)-cyclohexyl)be-
nzene in 600 ml of THF was cooled down to -70.degree. C., 178 ml of
sec-butyl lithium (1.0M, cyclohexane solution) was added by drops
thereto while being maintained at the same temperature, and stirred
at the same temperature for 2 hours. Subsequently, a solution of
30.8 g (296 mmol) of trimethyl borate in 300 ml of THF was added by
drops thereto while being at the same temperature, and stirred at
the same temperature for further 2 hours. After the reaction
temperature was gradually raised up to room temperature, 88.9 g
(1480 mmol) of acetic acid was added, 134 g (1180 mmol) of 30%
hydrogen peroxide was added by drops, and then stirred at room
temperature for 3 hours. The reaction was terminated by adding 300
ml of saturated aqueous sodium thiosulfate solution to the reaction
mixture, and the solvent was distilled off under a reduced
pressure.
[0113] Concentrated residue was extracted with 500 ml of toluene
and 100 ml of diethyl ether, the organic layer was washed with 150
ml of saturated aqueous sodium thiosulfate solution twice and with
200 ml of water thrice, and dried over anhydrous magnesium sulfate.
The solvent was distilled off under a reduced pressure, and the
residue was recrystallized from toluene to obtain 40.0 g of
2,3-difluoro-4-(trans-4-(-
4-(trans-4-pentylcyclohexyl)butyl)cyclohexyl)phenol.
[0114] Second step
[0115] In 400 ml of N,N-dimethyl formamide (hereinafter abbreviated
to DMF), was dissolved 40.0 g (95.1 mmol) of
2,3-difluoro-4-(trans-4-(4-(tra-
ns-4-pentylcyclohexyl)butyl)cyclohexyl)phenol, and heated on a
water bath up to 50.degree. C. Oily 55% sodium hydride in an amount
of 4.97 g (114 mmol) was added thereto, stirred at the same
temperature for 10 minutes, and a solution of 15.5 g (142 mmol) of
ethyl bromide in 150 ml of DMF was added by drops. After finishing
of the dropping, the reaction temperature was raised up to
80.degree. C., and stirred at the same temperature for 5 hours.
After cooled down to room temperature, the reaction was terminated
by adding 500 ml of water to the reaction mixture, and it was
extracted with 1.0 l of toluene. The organic layer was washed with
500 ml of water thrice and dried over anhydrous magnesium sulfate.
The solvent was distilled off under a reduced pressure, and the
residue was subjected to silica gel column chromatography (eluent:
heptane) to obtain a crude
1-ethoxy-2,3-difluoro-4-(trans-4-(4-(trans-4-pentylcyclohexyl)-butyl)cycl-
ohexyl)benzene. This crude product was recrystallized from heptane
twice and from mixed solvent of heptane/ethanol (6/1) once to
obtain 10.3 g (yield 15.5%) of the subject compound.
[0116] Phase transition temperature: C 79.2 S.sub.A 94.5 N 125.5
Iso
[0117] .sup.1H-NMR: .delta.: (ppm): 0.50.about.2.05 (m, 41H), 2.73
(t, 1H, J=7.3 Hz), 4.09 (q, 2H, J=7.0 Hz), 6.50.about.7.00 (m,
2H)
[0118] MS: m/e =448 (M.sup.+)
EXAMPLE 3
[0119] Preparation of
1-ethoxy-2,3-difluoro-4-(4-(trans-4-(trans-4-propylc-
yclohexyl)cyclohexyl)butyl)benzene [Compound expressed by the
general formula (1) wherein R.sup.1 is propyl group, either ring
A.sup.1 and ring A.sup.2 are trans-1,4-cyclohexylene group, X.sup.1
is a covalent bond, X.sup.2 is butylene group, Y.sup.1 is ethoxy
group, m is 1, and n is 0 (Compound No. 94)]
[0120] First step
[0121] Under nitrogen gas stream, a mixture of 1330 g (2930 mmol)
of 2-(1,3-dioxane-2-yl)ethyltriphenylphosphonium bromide with 6.0 l
of THF was cooled down to -30.degree. C., and 303 g (2700 mmol) of
t-BuOK was added thereto and stirred for 1 hour. To this mixture
was added by drops a solution of 500 g (2250 mmol) of
4-(trans-4-propylcyclohexyl)cyclohexan- one in 3.0 l of THF while
being maintained at a temperature lower than -30.degree. C. After
finishing of the adding, the reaction temperature was gradually
raised up to room temperature and they were stirred for further 5
hours. The reaction mixture was filtered with Celite, the solvent
was distilled off under a reduced pressure, and the residue was
subjected to silica gel column chromatography (eluent: mixed
solvent of toluene/ethyl acetate=9/1) to obtain 652 g of a crude
2-(2-(4-(trans-4-propylcyclohexyl)-cyclohexylidene)-ethyl-1,3-dioxane.
[0122] Second step
[0123] In 6.5 l of mixed solvent of toluene/Solmix (1/1) was
dissolved 652 g (2030 mmol) of the crude product obtained by the
procedures described above, 32.6 g of 5% by weight-palladium/carbon
catalyst was added thereto, and then they were stirred at room
temperature under the condition of a hydrogen gas pressure of 1 to
2 kg/cm.sup.2 for 6 hours. After the catalyst was removed by
filtration, the solvent was distilled off under a reduced pressure,
and the residue was subjected to silica gel column chromatography
(eluent: toluene) and recrystallized from heptane to obtain 366 g
of 2-(2-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)eth-
yl)-1,3-dioxane.
[0124] Third step
[0125] In 3.0 l of toluene was dissolved 300 g (930 mmol) of the
2-(2-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)ethyl)-1,3-dioxane
obtained by the procedures described above, 428 g (9300 mmol) of
formic acid was added thereto, and they were heated to reflux for 4
hours. The reaction mixture was washed with 600 ml of saturated
aqueous sodium bicarbonate solution twice and with 1.0 l of water
five times, and the solvent was distilled off under a reduced
pressure to obtain 240 g of a crude
3-(trans-4-(trans-4-propylcyclohexyl)-cyclohexyl)propanal.
[0126] Fourth step
[0127] Under nitrogen gas stream, a mixture of 405 g (1180 mmol) of
methoxymethyltriphenyl-phosphonium chloride with 4.0 ml of THF was
cooled down to -30.degree. C., 122 g (1090 mmol) of t-BuOK was
added thereto, and they were stirred for 1 hour. To this mixture
was added by drops a solution of 240 g (907 mmol) of the crude
3-(trans-4-(trans-4-propylcyclo- hexyl)cyclohexyl)-propanal in 2.4
l of THF while being maintained at a temperature lower than
-30.degree. C. After finishing of the dropping, the reaction
temperature was gradually raised up to room temperature, and the
mixture was stirred for further 5 hours. The reaction mixture was
filtered with Celite, the solvent was distilled off under a reduced
pressure, and the residue was subjected to silica gel column
chromatography (eluent: heptane) to obtain 152 g of a crude
1-methoxy-4-(trans-4-(trans-4-propylcyclohexyl)-cyclohexyl)butene.
[0128] Fifth step
[0129] In 500 ml of toluene was dissolved 50.0 g (171 ml ) of the
crude
1-methoxy-4-(trans-4-(trans-4-propylcyclohexyl)-cyclohexyl)butene
obtained by the procedures in the fourth step, 78.7 g (1710 mmol)
of formic acid was added thereto, and then they were heated to
reflux for 4 hours. The reaction mixture was washed with 300 ml of
saturated aqueous sodium bicarbonate solution twice and with 500 ml
of water five times, and the solvent was distilled off under a
reduced pressure to obtain 45.1 g of a crude
4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)butanal.
[0130] Sixth step
[0131] Under nitrogen gas stream, a solution of 30.7 g (194 mmol)
of 1-ethoxy-2,3-difluorobenzene in 300 ml of THF was cooled down to
-70.degree. C., 194 ml of sec-butyl lithium (1.0M cyclohexane
solution) was added by drops thereto while being maintained at the
same temperature, and they were stirred at the same temperature for
2 hours. To this reaction mixture was added by drops a solution of
45.1 g (162 mmol) of the crude
4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)butana- l obtained
by the reaction in the fifth step in 450 ml of THF while being
maintained at the same temperature, and stirred for 2 hours.
Subsequently, they were raised up to -50.degree. C. and stirred for
2 hours. The reaction mixture was added to 200 ml of water to
terminate the reaction, the solvent was distilled off under a
reduced pressure, the residue was extracted with 500 ml of toluene,
and the organic layer was washed with 100 ml of water thrice, and
then dried over anhydrous magnesium sulfate. After the anhydrous
magnesium sulfate was removed by filtration, 2.83 g of
p-toluenesulfonic acid monohydrate was added to the filtrate, and
heated to reflux for 4 hours. The organic layer was washed with 200
ml of water thrice and then dried over anhydrous magnesium sulfate.
The solvent was distilled off under a reduced pressure and the
residue was subjected to silica gel column chromatography (eluent:
mixed solvent of heptane/toluene=7/3) to obtain 50.2 g of a crude
1-ethoxy-2,3-difluoro-4-(4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)-
-1-butenyl)benzene.
[0132] Seventh step
[0133] In 500 ml of mixed solvent of toluene/Solmix (1/1) was
dissolved 50.2 g (120 mmol) of the crude product obtained by the
procedures described above, 15.1 g of 5% by weight-palladium/carbon
catalyst was added thereto, and they were stirred at room
temperature under the condition of a hydrogen gas pressure of 1 to
2 kg/cm.sup.2 for 6 hours. After the catalyst was removed by
filtration, the solvent was distilled off under reduced pressure,
and the residue was subjected to silica gel column chromatography
(eluent: mixed solvent of heptane/toluene=7/3) to obtain a crude
1-ethoxy-2,3-difluoro-4-(4-(trans-4-(trans-4-propylcyclohe-
xyl)cyclohexyl)butyl)benzene. This crude product was recrystallized
from heptane twice to obtain 24.3 g (yield 9.90%) of the subject
compound.
[0134] Phase transition temperature: C 44.4 S.sub.A 107.2 N 129.0
Iso
[0135] .sup.1H-NMR: .delta.: (ppm): 0.45.about.2.10 (m, 36H), 2.58
(t, 2H, J=7.0 Hz), 4.09 (q, 2H, J=7.0 Hz), 6.50.about.7.00 (m,
2H)
[0136] MS: m/e =420 (M.sup.+)
EXAMPLE 4
[0137] Preparation of
3-(trans-4-(trans-4-propylcyclohexyl)-cyclohexyl)pro- pyl
2,3-difluoro-4-(2,3-difluoro-4-pentylphenyl)phenyl ether [Compound
expressed by the general formula (1) wherein R.sup.1 is propyl
group, either ring A.sup.1 and ring A.sup.2 are
trans-1,4-cyclohexylene group, ring A.sup.3 is
2,3-difluoro-1,4-phenylene group, either X.sup.1 and X.sup.3 are
single bond, X.sup.2 is propyloxylene group, Y.sup.1 is pentyl
group, m is 1, and n is 1 (Compound No. 237)]
[0138] First step
[0139] Under nitrogen gas stream, a solution of 400 g (1510 mmol)
of the crude
3-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)-propanal obtained
in the same manner as in the third step in Example 1 in 2.0 a of
THF was added by drops to a mixture which was prepared by adding
43.0 g (1130 mmol) of lithium aluminum hydride to 400 ml of THF
cooled down to a temperature lower than 5.degree. C., while being
maintained at the same temperature. After finishing of the adding,
they were stirred at room temperature for 6 hours. This reaction
mixture was gradually added to 500 ml of 2N aqueous sodium
hydroxide solution and stirred at 50.degree. C. for 30 minutes. The
reaction mixture was filtered with Celite, the solvent was
distilled off under a reduced pressure, and the residue was
extracted with 2.0 l of ethyl acetate. The organic layer was dried
over anhydrous magnesium sulfate, and the solvent was distilled off
under a reduced pressure to obtain 341 g of a crude
3-(trans-4-(trans-4-propylcyc- lohexyl)cyclohexyl)-propanol.
[0140] Second step
[0141] To 350 ml of xylene were added 341 g (1280 mmol) of the
crude 3-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)propanol
obtained by the procedures described above and 881 g (5120 mmol) of
47% hydrobromic acid, water was removed by azeotropic distillation,
and then the mixture was stirred at 150.degree. C. for 2 hours. To
the reaction mixture was added 1.0 l of toluene, and it was washed
with 300 ml of saturated aqueous sodium carbonate solution twice
and with 400 ml of water thrice, and then dried over anhydrous
magnesium sulfate. The solvent was distilled off under a reduced
pressure, and the residue was subjected to silica gel column
chromatography (eluent: heptane) to obtain 156 g of a crude
1-bromo-3-(trans-4-(trans-4-propylcyclohexyl)-cyclohexyl)propane.
[0142] Third step
[0143] Under nitrogen gas stream, 29.8 g (683 mmol) of 55% sodium
hydride was added to 100 ml of DMF and cooled with water, a
solution of 74.0 g (569 mmol) of 2,3-difluorophenol in 700 ml of
DMF was added by drops thereto, and they were stirred for 1 25
hour. To the reaction mixture was added by drops a solution of 156
g (474 mmol) of the crude
1-bromo-3-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)propane in
400 ml of mixed solvent of DMF/toluene (3/1), and then they were
stirred at 80.degree. C. for 3 hours. The reaction mixture was
added to 500 ml of water to terminate the reaction, and the organic
layer was separated, washed with 500 ml of water thrice, and then
dried over anhydrous magnesium sulfate. The solvent was distilled
off under a reduced pressure, and the residue was subjected to
silica gel column chromatography (eluent: heptane) and
recrystallized from heptane to obtain 101 g of
3-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)propyl
2,3-difluorophenyl ether.
[0144] Fourth step
[0145] Under nitrogen gas stream, 101 g (267 mmol) of the
3-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)propyl
2,3-difluorophenyl ether obtained by the procedures described above
was dissolved in 1.0 l of THF and cooled down to -70.degree. C. To
this solution was added by drops 320 ml of sec-butyl lithium (1.0M,
cyclohexane solution) while being maintained at the same
temperature, and stirred at the same temperature for 2 hours. To
the reaction mixture was added by drops 640 ml of zinc chloride
(0.5M, THF solution), and stirred at the same temperature for 1
hour, the reaction temperature was gradually raised up to room
temperature, and they were stirred for 1 hour. To the reaction
mixture was added 1.00 g of tetrakis-(triphenylphosphine)palladium
(0), and a solution of 61.8 g (15.9 mmol) of
2,3-difluoro-1-bromobenzene in 600 ml of THF was added by drops
thereto, and heated to reflux for 3 hours. The reaction mixture was
added to 1.0 l of water to terminate the reaction, the solvent was
distilled off under a reduced pressure, and the residue was
extracted with 3.0 l of toluene. The organic layer was washed with
1.0 l of water thrice and dried over anhydrous magnesium sulfate.
The solvent was distilled off under a reduced pressure, and the
residue was subjected to silica gel column chromatography (eluent:
toluene) to obtain 55.3 g of a crude
3-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)- propyl
2,3-difluoro-4-(2,3-difluorophenyl)phenyl ether.
[0146] Fifth step
[0147] Under nitrogen gas stream, a solution prepared by dissolving
55.3 g (112 mmol) of the
3-(trans-4-(trans-4-propylcyclohexyl)-cyclohexyl)propyl
2,3-difluoro-4-(2,3-difluorophenyl)phenyl ether obtained by the
procedures described above in 550 ml of THF was cooled down to
-70.degree. C., and 134 ml of sec-butyl lithium (1.0M, cyclohexane
solution) was added by drops thereto while being maintained at the
same temperature and stirred at the same temperature for 2 hours.
To the reaction mixture added by drops a suspension which was
prepared by adding 15.0 g (134 mmol) of t-BuOK to 150 ml of THF,
while being maintained at the same temperature, and stirred at the
same temperature for further 1 hour. To the reaction mixture was
added by drops a solution of 26.5 g (134 mmol) of pentyliodide in
300 ml of THF while being maintained at the same temperature and
stirred at the same temperature for 5 hours. The reaction mixture
was added to 300 ml of water to terminate the reaction, and the
solvent was distilled off under a reduced pressure. The residue was
extracted with 700 ml of toluene, and the organic layer was washed
with 300 ml of water thrice and dried over anhydrous magnesium
sulfate. The solvent was distilled off under a reduced pressure,
and the residue was subjected to silica gel column chromatography
(eluent: mixed solvent of heptane/toluene=7/3) to obtain a crude
3-(trans-4-(trans-4-propylcyclo- hexyl)-propyl
2,3-difluoro-4-(2,3-difluoro-4-pentylphenyl)phenyl ether. This
crude product was recrystallized from heptane twice and from mixed
solvent of heptane/ethanol (4/1) once to obtain 10.2 to g (yield
1.21%) of the subject compound.
[0148] MS: m/e =560 (M.sup.+)
EXAMPLE 5
[0149] Preparation of
1-ethoxy-2,3-difluoro-4-(2,3-difluoro-4-(4-(trans-4--
(trans-4-propylcyclohexyl)cyclohexyl)butyl)phenyl)-benzene
[Compound expressed by the general formula (1) wherein R.sup.1 is
propyl group, either ring A.sup.1 and ring A.sup.2 are
trans-1,4-cyclohexylene group, ring A.sup.3 is
2,3-difluoro-1,4-phenylene group, either X.sup.1 and X.sup.3 are
single bond, X.sup.2 is butylene group, Y.sup.1 is ethoxy group, m
is 1, and n is 1 (Compound No. 238)]
[0150] First step
[0151] Under nitrogen gas stream, 8.05 g (331 mmol) of magnesium
was added to 20.0 ml of THF, and a solution of 58.1 g (301 mmol) of
2,3-difluoro-1-bromobenzene in 600 ml of THF was added by drops
thereto so that the reaction temperature was maintained at about
50.degree. C. and then stirred at room temperature for 1 hour. To
the reaction solution was added by drops a solution of 70.0 g (251
mmol) of the crude
4-(trans-4-(trans-4-propylcyclohexyl)-cyclohexyl)butanal obtained
by the same manner as in the fifth step of Example 1 in 700 ml of
THF, stirred at 50 to 60.degree. C. for 2 hours, and then 200 ml of
saturated aqueous ammonium chloride solution was added thereto to
terminate the reaction. The reaction mixture was filtered with
Celite, the solvent was distilled off under a reduced pressure, and
then the residue was extracted with 700 ml of toluene. The organic
layer was washed with 400 ml of water thrice and then dried over
anhydrous magnesium sulfate. After the anhydrous magnesium sulfate
was filtered off, 3.56 g of p-toluenesulfonic acid monohydrate was
added to the filtrate, and heated to reflux for 4 hours. The
organic layer was washed with 300 ml of water thrice and dried over
anhydrous magnesium sulfate. The solvent was distilled off under a
reduced pressure, and the residue was subjected to silica gel
column chromatography (eluent: heptane) to obtain 63.5 g of a crude
2,3-difluoro-4-(4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)-1-buteny-
l)benzene.
[0152] Second step
[0153] To 600 ml of mixed solvent of toluene/Solmix (1/1) was
dissolved 63.5 g (170 mmol) of the crude product obtained by the
procedures described above, 3.18 g of 5% by weight-palladium/carbon
catalyst was added thereto, and then they were stirred at room
temperature under the condition of a hydrogen gas pressure of 1 to
2 kg/cm.sup.2 for 6 hours. After the catalyst was removed from the
reaction mixture by filtration, the solvent was distilled off under
a reduced pressure, and the residue was subjected to silica gel
column chromatography (eluent: heptane) to obtain 60.0 g of a crude
2,3-difluoro-4-(4-(trans-4-(trans-4-propylcycloh-
exyl)cyclohexyl)butyl)benzene.
[0154] Third step
[0155] Under nitrogen gas stream, 60.0 g (159 mmol) of the crude
2,3-difluoro-4-(4-(trans-4-(trans-4-propylcyclohexyl)-cyclohexyl)butyl)be-
nzene was dissolved in 600 ml of THF, cooled down to -70.degree.
C., and 191 ml of sec-butyl lithium (1.0M, cyclohexane solution)
was added by drops thereto while being maintained at the same
temperature and stirred at the same temperature for 2 hours. To the
reaction mixture was added by drops a solution of 60.7 g (239 mmol)
of iodine in 600 ml of THF while being maintained at the same
temperature, the reaction temperature was gradually raised up to
room temperature, and then they were stirred for 30 minutes. The
reaction mixture was added to 300 ml of saturated aqueous sodium
thiosulfate solution to terminate the reaction, and the solvent was
distilled off under a reduced pressure. The residue was extracted
with 700 ml of toluene, and the organic layer was washed with 300
ml of saturated aqueous sodium thiosulfate solution twice and 200
ml of saturated aqueous sodium carbonate solution once, and 300 ml
of water thrice, and then dried over anhydrous magnesium sulfate.
The solvent was distilled off under a reduced pressure, and the
residue was subjected to silica gel column chromatography (eluent:
heptane) to obtain 72.5 g of a crude
2,3-difluoro-1-iodo-4-(4-(trans-4-(trans-4-propylcyclohexyl)-cycloh-
exyl)butyl)benzene.
[0156] Fourth step
[0157] Under nitrogen gas stream, a solution prepared by dissolving
9.46 g (59.8 mmol) of 2,3-difluoro-1-ethoxybenzene in 100 ml of THF
was cooled down to -70.degree. C., and 59.8 ml of sec-butyl lithium
(1.0M, cyclohexane solution) was added by drops thereto while being
maintained at the same temperature and stirred at the same
temperature for 2 hors. To the reaction mixture was added by drops
120 ml of zinc chloride (0.5M, THF solution), stirred at the same
temperature for 1 hour, the reaction temperature was gradually
raised up to room temperature, and they were stirred for further 1
hour. To the reaction mixture was added 1.00 g of
tetrakis(triphenylphosphine)palladium (0), and a solution of 25.0 g
(49.8 mmol) of the crude
2,3-difluoro-1-iodo-4-(4-(trans-4-(trans-4-propylcyclo-
hexyl)cyclohexyl)-butyl)benzene in 250 ml of THF was added by drops
thereto and heated to reflux for 3 hours. The reaction mixture was
added to 200 ml of water to terminate the reaction, the solvent was
distilled off under a reduced pressure, and the concentrated
residue was extracted with 500 ml of toluene. The organic layer was
washed with 300 ml of water thrice and dried over anhydrous
magnesium sulfate. The solvent was distilled off under a reduced
pressure, and the residue was subjected to silica gel column
chromatography (eluent: mixed solvent of heptane/toluene=7/3) to
obtain a crude 1-ethoxy-2,3-difluoro-4-(2,3-diflu-
oro-4-(4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)butyl)phenyl)benzen-
e. This crude product was recrystallized from heptane once and from
mixed solvent of heptane/ethanol (5/1) once to obtain 13.1 g (yield
28.3%) of the subject compound.
[0158] Phase transition temperature: C 89.5 N 193.2 Iso
[0159] .sup.1H-NMR: .delta.: (ppm): 0.40.about.2.10 (m, 36H), 2.70
(t, 2H, J=6.9 Hz), 4.17 (q, 2H, J=7.2 Hz), 6.60.about.7.20 (m,
4H)
[0160] MS: m/e =532 (M.sup.+)
[0161] Following the methods of Example 1 to 5, the following
compounds can be prepared:
1 R.sup.1 18 19 20 m n Y.sup.1 1 C.sub.3H.sub.7 21 0 0
C.sub.5H.sub.11 2 C.sub.5H.sub.11 22 0 0 C.sub.7H.sub.15 3
C.sub.7H.sub.15 23 0 0 C.sub.3H.sub.7 4 C.sub.3H.sub.7 24 0 0
OC.sub.2H.sub.5 5 C.sub.5H.sub.11O 25 0 0 OC.sub.4H.sub.9 6
C.sub.5H.sub.11 26 0 0 OC.sub.2H.sub.5 7 C.sub.3H.sub.7 27 0 0
C.sub.3H.sub.7 8 C.sub.5H.sub.11 28 0 0 C.sub.7H.sub.15 9
C.sub.7H.sub.15 29 0 0 C.sub.5H.sub.11 10 30 31 0 0 OC.sub.4H.sub.9
11 C.sub.5H.sub.11 32 0 0 OC.sub.2H.sub.5 12 C.sub.7H.sub.15 33 0 0
OCH.sub.3 13 C.sub.3H.sub.7 34 0 0 C.sub.7H.sub.15 14
C.sub.5H.sub.11 35 0 0 C.sub.5H.sub.11 15 C.sub.7H.sub.15 36 0 0
C.sub.3H.sub.7 16 C.sub.3H.sub.7 37 0 0 OC.sub.2H.sub.5 17
C.sub.5H.sub.11 38 0 0 OC.sub.4H.sub.9 18 C.sub.3H.sub.7O 39 0 0
OC.sub.5H.sub.11 19 C.sub.3H.sub.7 40 41 1 0 C.sub.5H.sub.11 20
C.sub.5H.sub.11 42 43 1 0 C.sub.3H.sub.7 C 40.2 S.sub.B 90.9 N 98.0
Iso 21 C.sub.3H.sub.7O 44 45 1 0 C.sub.7H.sub.15 22 C.sub.3H.sub.7
46 47 1 0 OC.sub.4H.sub.9 23 C.sub.5H.sub.11 48 49 1 0
OC.sub.2H.sub.5 C 79.2 S.sub.A 94.5 N 125.5 Iso 24 C.sub.7H.sub.15
50 51 1 0 OCH.sub.3 25 C.sub.3H.sub.7 52 53 1 0 C.sub.7H.sub.15 26
C.sub.5H.sub.11 54 55 1 0 C.sub.5H.sub.11 27 C.sub.7H.sub.15 56 57
1 0 C.sub.3H.sub.7 28 C.sub.3H.sub.7 58 59 1 0 OC.sub.4H.sub.9 29
C.sub.5H.sub.11 60 61 1 0 OC.sub.2H.sub.5 30 C.sub.5H.sub.11O 62 63
1 0 OCH.sub.3 31 C.sub.3H.sub.7 64 65 1 0 C.sub.5H.sub.11 32
C.sub.5H.sub.11 66 67 1 0 C.sub.3H.sub.7 33 68 69 70 1 0 CH.sub.3
34 C.sub.3H.sub.7 71 72 1 0 OC.sub.4H.sub.9 35 C.sub.5H.sub.11 73
74 1 0 OC.sub.2H.sub.5 36 C.sub.7H.sub.15 75 76 1 0 OC.sub.3H.sub.7
37 C.sub.3H.sub.7 77 78 1 0 C.sub.3H.sub.7 38 C.sub.5H.sub.11 79 80
1 0 C.sub.5H.sub.11 39 C.sub.2H.sub.5 81 82 1 0 C.sub.5H.sub.11 40
C.sub.3H.sub.7 83 84 1 0 OC.sub.4H.sub.9 41 C.sub.5H.sub.11 85 86 1
0 OC.sub.2H.sub.5 42 C.sub.6H.sub.13O 87 88 1 0 OCH.sub.3 43
C.sub.3H.sub.7 89 90 1 0 C.sub.5H.sub.11 44 C.sub.5H.sub.11 91 92 1
0 C.sub.3H.sub.7 45 C.sub.2H.sub.5O 93 94 1 0 C.sub.7H.sub.15 46
C.sub.3H.sub.7 95 96 1 0 OC.sub.2H.sub.5 47 C.sub.5H.sub.11 97 98 1
0 OC.sub.4H.sub.9 48 C.sub.7H.sub.15 99 100 1 0 OCH.sub.3 49
C.sub.3H.sub.7 101 102 1 0 C.sub.3H.sub.7 50 C.sub.5H.sub.11 103
104 1 0 C.sub.5H.sub.11 51 105 106 107 1 0 C.sub.2H.sub.5 52
C.sub.3H.sub.7 108 109 1 0 OC.sub.4H.sub.9 53 C.sub.5H.sub.11 110
111 1 0 OC.sub.3H.sub.7 54 C.sub.7H.sub.15 112 113 1 0
OC.sub.2H.sub.5 55 C.sub.5H.sub.11 114 115 1 0 C.sub.3H.sub.7 56
C.sub.3H.sub.7 116 117 1 0 C.sub.5H.sub.11 57 C.sub.5H.sub.11O 118
119 1 0 C.sub.3H.sub.7 58 C.sub.3H.sub.7 120 121 1 0
OC.sub.2H.sub.5 59 C.sub.5H.sub.11 122 123 1 0 OC.sub.4H.sub.9 60
124 125 126 1 0 OC.sub.3H.sub.7 61 C.sub.3H.sub.7 127 128 1 0
C.sub.7H.sub.15 62 C.sub.5H.sub.11 129 130 1 0 C.sub.3H.sub.7 63
C.sub.7H.sub.15 131 132 1 0 C.sub.5H.sub.11 64 C.sub.3H.sub.7 133
134 1 0 OC.sub.2H.sub.5 65 C.sub.5H.sub.11 135 136 1 0
OC.sub.4H.sub.9 66 137 138 139 1 0 OCH.sub.3 67 C.sub.3H.sub.7 140
141 1 0 C.sub.5H.sub.11 68 C.sub.5H.sub.11 142 143 1 0
C.sub.3H.sub.7 69 C.sub.7H.sub.15 144 145 1 0 C.sub.2H.sub.5 70
C.sub.3H.sub.7 146 147 1 0 OC.sub.2H.sub.9 71 C.sub.5H.sub.11 148
149 1 0 OC.sub.3H.sub.7 72 C.sub.7H.sub.15 150 151 1 0
OC.sub.4H.sub.9 73 C.sub.3H.sub.7 152 153 1 0 C.sub.3H.sub.7 74
C.sub.5H.sub.11 154 155 1 0 C.sub.5H.sub.11 75 C.sub.5H.sub.11 156
157 1 0 C.sub.3H.sub.7 76 C.sub.3H.sub.7 158 159 1 0
OC.sub.2H.sub.5 77 C.sub.3H.sub.7 160 161 1 0 OC.sub.3H.sub.7 78
C.sub.7H.sub.15 162 163 1 0 OC.sub.3H.sub.7 79 C.sub.3H.sub.7 164
165 1 0 C.sub.5H.sub.11 80 C.sub.5H.sub.11 166 167 1 0
C.sub.3H.sub.7 81 C.sub.7H.sub.15 168 169 1 0 C.sub.5H.sub.11 82
C.sub.3H.sub.7 170 171 1 0 OC.sub.2H.sub.5 83 C.sub.5H.sub.11 172
173 1 0 OC.sub.4H.sub.9 84 174 175 176 1 0 OC.sub.2H.sub.5 85
C.sub.3H.sub.7 177 178 1 0 C.sub.3H.sub.7 86 C.sub.5H.sub.11 179
180 1 0 C.sub.5H.sub.11 87 C.sub.5H.sub.11 181 182 1 0
C.sub.3H.sub.7 88 C.sub.3H.sub.7 183 184 1 0 OC.sub.2H.sub.5 89
C.sub.5H.sub.11 185 186 1 0 OC.sub.4H.sub.9 90 C.sub.7H.sub.15 187
188 1 0 OC.sub.2H.sub.5 91 C.sub.3H.sub.7 189 190 1 0
C.sub.3H.sub.7 92 C.sub.5H.sub.11 191 192 1 0 C.sub.3H.sub.7 93 193
194 195 1 0 C.sub.5H.sub.11 94 C.sub.3H.sub.7 196 197 1 0
OC.sub.2H.sub.5 C 44.4 S.sub.A 107.2 N 129.0 Iso 95 C.sub.5H.sub.11
198 199 1 0 OC.sub.4H.sub.9 96 C.sub.5H.sub.11 200 201 1 0
OC.sub.2H.sub.5 97 C.sub.3H.sub.7 202 203 1 0 C.sub.3H.sub.7 98
C.sub.5H.sub.11O 204 205 1 0 C.sub.5H.sub.11 99 C.sub.7H.sub.15 206
207 1 0 C.sub.7H.sub.15 100 C.sub.3H.sub.7 208 209 1 0
OC.sub.4H.sub.9 101 C.sub.5H.sub.11 210 211 1 0 OC.sub.2H.sub.5 102
C.sub.5H.sub.11 212 213 1 0 OC.sub.3H.sub.7 103 C.sub.3H.sub.7 214
215 1 0 C.sub.5H.sub.11 104 C.sub.5H.sub.11 216 217 1 0
C.sub.3H.sub.7 105 C.sub.7H.sub.15 218 219 1 0 CH.sub.3 106
C.sub.3H.sub.7 220 221 1 0 OC.sub.2H.sub.5 107 C.sub.5H.sub.11 222
223 1 0 OC.sub.4H.sub.9 108 C.sub.2H.sub.5O 224 225 1 0 OCH.sub.3
109 C.sub.3H.sub.7 226 227 1 0 C.sub.3H.sub.7 110 C.sub.5H.sub.11
228 229 1 0 C.sub.5H.sub.11 111 C.sub.5H.sub.11 230 231 1 0
C.sub.3H.sub.7 112 C.sub.3H.sub.7O 232 233 1 0 OC.sub.4H.sub.9 113
C.sub.5H.sub.11 234 235 1 0 OC.sub.2H.sub.5 114 C.sub.7H.sub.15 236
237 1 0 OCH.sub.3 115 C.sub.3H.sub.7 238 239 1 0 C.sub.7H.sub.15
116 C.sub.5H.sub.11 240 241 1 0 C.sub.3H.sub.7 117 242 243 244 1 0
C.sub.5H.sub.11 118 C.sub.3H.sub.7 245 246 1 0 OC.sub.2H.sub.5 119
C.sub.5H.sub.11O 247 248 1 0 OC.sub.4H.sub.9 120 C.sub.5H.sub.11
249 250 1 0 OC.sub.3H.sub.7 121 C.sub.3H.sub.7 251 252 1 0
C.sub.5H.sub.11 122 C.sub.5H.sub.11 253 254 1 0 C.sub.3H.sub.7 123
C.sub.7H.sub.15 255 256 1 0 C.sub.2H.sub.5 124 257 258 259 1 0
OC.sub.2H.sub.5 125 C.sub.5H.sub.11 260 261 1 0 OC.sub.4H.sub.9 126
C.sub.7H.sub.15 262 263 1 0 OC.sub.3H.sub.7 127 C.sub.3H.sub.7 264
265 1 0 C.sub.4H.sub.9 128 C.sub.5H.sub.11 266 267 1 0
C.sub.3H.sub.7 129 C.sub.5H.sub.11O 268 269 1 0 C.sub.5H.sub.11 130
C.sub.5H.sub.11 270 271 1 0 OC.sub.4H.sub.9 131 C.sub.5H.sub.11 272
273 1 0 OC.sub.2H.sub.5 132 C.sub.7H.sub.15 274 275 1 0 OCH.sub.3
133 C.sub.3H.sub.7 276 277 1 0 C.sub.3H.sub.7 134 C.sub.5H.sub.11
278 279 1 0 C.sub.2H.sub.5 135 C.sub.7H.sub.15 280 281 1 0
C.sub.5H.sub.11 136 C.sub.3H.sub.7 282 283 1 0 OC.sub.2H.sub.5 137
C.sub.5H.sub.11 284 285 1 0 OC.sub.4H.sub.9 138 C.sub.5H.sub.11 286
287 1 0 OC.sub.3H.sub.7 139 C.sub.3H.sub.7 288 289 1 0
C.sub.5H.sub.11 140 290 291 292 1 0 C.sub.3H.sub.7 141
C.sub.3H.sub.7O 293 294 1 0 C.sub.7H.sub.15 142 C.sub.3H.sub.7 295
296 1 0 OC.sub.2H.sub.5 143 C.sub.5H.sub.11 297 298 1 0
OC.sub.3H.sub.7 144 C.sub.7H.sub.15 299 300 1 0 OC.sub.4H.sub.9 145
C.sub.3H.sub.7 301 302 303 1 1 C.sub.5H.sub.11 146 C.sub.5H.sub.11
304 305 306 1 1 C.sub.3H.sub.7 147 C.sub.3H.sub.7O 307 308 309 1 1
C.sub.7H.sub.15 148 C.sub.3H.sub.7 310 311 312 1 1 OC.sub.4H.sub.9
149 C.sub.5H.sub.11 313 314 315 1 1 OC.sub.2H.sub.5 150 316 317 318
319 1 1 OCH.sub.3 151 C.sub.3H.sub.7 320 321 322 1 1
C.sub.7H.sub.15 152 C.sub.5H.sub.11 323 324 325 1 1 C.sub.5H.sub.11
153 C.sub.7H.sub.15 326 327 328 1 1 C.sub.3H.sub.7 154
C.sub.3H.sub.7 329 330 331 1 1 OC.sub.4H.sub.9 155 C.sub.5H.sub.11
332 333 334 1 1 OC.sub.2H.sub.5 156 C.sub.7H.sub.15 335 336 337 1 1
OCH.sub.3 157 C.sub.3H.sub.7 338 339 340 1 1 C.sub.2H.sub.5 158
C.sub.5H.sub.11 341 342 343 1 1 C.sub.3H.sub.7 159 C.sub.5H.sub.11O
344 345 346 1 1 C.sub.5H.sub.11 160 C.sub.3H.sub.7 347 348 349 1 1
OC.sub.2H.sub.5 161 C.sub.5H.sub.11 350 351 352 1 1 OC.sub.4H.sub.9
162 C.sub.7H.sub.15 353 354 355 1 1 OC.sub.3H.sub.7 163
C.sub.3H.sub.7 356 357 358 1 1 C.sub.3H.sub.7 164 C.sub.5H.sub.11
359 360 361 1 1 C.sub.5H.sub.11 165 C.sub.3H.sub.7 362 363 364 1 1
C.sub.7H.sub.15 166 365 366 367 368 1 1 OCH.sub.3 167
C.sub.5H.sub.11 369 370 371 1 1 OC.sub.2H.sub.5 168 C.sub.7H.sub.15
372 373 374 1 1 OC.sub.3H.sub.7 169 C.sub.3H.sub.7 375 376 377 1 1
C.sub.7H.sub.15 170 C.sub.5H.sub.11 378 379 380 1 1 C.sub.5H.sub.11
171 C.sub.7H.sub.15 381 382 383 1 1 C.sub.3H.sub.7 172
C.sub.3H.sub.7 384 385 386 1 1 OC.sub.4H.sub.9 173 C.sub.5H.sub.11O
387 388 389 1 1 OC.sub.2H.sub.5 174 C.sub.7H.sub.15 390 391 392 1 1
OC.sub.3H.sub.7 175 C.sub.3H.sub.7O 393 394 395 1 1 C.sub.2H.sub.5
176 C.sub.5H.sub.11 396 397 398 1 1 C.sub.3H.sub.7 177
C.sub.5H.sub.11 399 400 401 1 1 C.sub.5H.sub.11 178 C.sub.3H.sub.7
402 403 404 1 1 OC.sub.2H.sub.5 179 C.sub.5H.sub.11 405 406 407 1 1
OC.sub.3H.sub.7 180 C.sub.3H.sub.7O 408 409 410 1 1 OC.sub.4H.sub.9
181 C.sub.3H.sub.7 411 412 413 1 1 C.sub.3H.sub.7 182
C.sub.5H.sub.11 414 415 416 1 1 C.sub.7H.sub.15 183 417 418 419 420
1 1 C.sub.5H.sub.11 184 C.sub.3H.sub.7O 421 422 423 1 1 OCH.sub.3
185 C.sub.5H.sub.11 424 425 426 1 1 OC.sub.2H.sub.5 186
C.sub.7H.sub.15 427 428 429 1 1 OC.sub.3H.sub.7 187 C.sub.3H.sub.7
430 431 432 1 1 C.sub.7H.sub.15 188 C.sub.5H.sub.11 433 434 435 1 1
C.sub.5H.sub.11 189 C.sub.7H.sub.15 436 437 438 1 1 C.sub.3H.sub.7
190 C.sub.3H.sub.7 439 440 441 1 1 OC.sub.4H.sub.9 191
C.sub.5H.sub.11 442 443 444 1 1 OC.sub.2H.sub.5 192 C.sub.7H.sub.15
445 446 447 1 1 OC.sub.3H.sub.7 193 C.sub.3H.sub.7 448 449 450 1 1
C.sub.2H.sub.5 194 C.sub.5H.sub.11O 451 452 453 1 1 C.sub.3H.sub.7
195 C.sub.5H.sub.11 454 455 456 1 1 C.sub.5H.sub.11 196
C.sub.3H.sub.7 457 458 459 1 1 OC.sub.2H.sub.5 197 C.sub.5H.sub.11
460 461 462 1 1 OC.sub.3H.sub.7 198 C.sub.3H.sub.7O 463 464 465 1 1
OC.sub.4H.sub.9 199 C.sub.3H.sub.7 466 467 468 1 1 C.sub.7H.sub.15
200 C.sub.5H.sub.11 469 470 471 1 1 C.sub.3H.sub.7 201 472 473 474
475 1 1 C.sub.5H.sub.11 202 C.sub.3H.sub.7 476 477 478 1 1
OC.sub.3H.sub.7 203 C.sub.5H.sub.11 479 480 481 1 1 OC.sub.2H.sub.5
204 C.sub.7H.sub.15 482 483 484 1 1 OC.sub.4H.sub.9 205
C.sub.3H.sub.7 485 486 487 1 1 C.sub.7H.sub.15 206 C.sub.5H.sub.11O
488 489 490 1 1 C.sub.5H.sub.11 207 C.sub.7H.sub.15 491 492 493 1 1
C.sub.3H.sub.7 208 C.sub.3H.sub.7 494 495 496 1 1 OC.sub.2H.sub.5
209 C.sub.5H.sub.11 497 498 499 1 1 OCH.sub.3 210 C.sub.7H.sub.15
500 501 502 1 1 OC.sub.3H.sub.7 211 C.sub.3H.sub.7 503 504 505 1 1
C.sub.2H.sub.5 212 C.sub.5H.sub.11 506 507 508 1 1 C.sub.3H.sub.7
213 C.sub.3H.sub.7O 509 510 511 1 1 C.sub.5H.sub.11 214
C.sub.5H.sub.11 512 513 514 1 1 OC.sub.2H.sub.5 215 C.sub.5H.sub.11
515 516 517 1 1 OC.sub.4H.sub.9 216 C.sub.3H.sub.7O 518 519 520 1 1
OC.sub.3H.sub.7 217 C.sub.3H.sub.7 521 522 523 1 1 C.sub.3H.sub.7
218 C.sub.5H.sub.11 524 525 526 1 1 C.sub.3H.sub.7 219 527 528 529
530 1 1 C.sub.5H.sub.11 220 C.sub.5H.sub.11 531 532 533 1 1
OC.sub.2H.sub.5 221 C.sub.5H.sub.11 534 535 536 1 1 OC.sub.3H.sub.7
222 C.sub.5H.sub.11 537 538 539 1 1 OC.sub.4H.sub.9 223
C.sub.3H.sub.7 540 541 542 1 1 C.sub.3H.sub.7 224 C.sub.5H.sub.11O
543 544 545 1 1 C.sub.5H.sub.11 225 C.sub.7H.sub.15 546 547 548 1 1
C.sub.7H.sub.15 226 C.sub.3H.sub.7 549 550 551 1 1 OC.sub.4H.sub.9
227 C.sub.5H.sub.11 552 553 554 1 1 OC.sub.2H.sub.5 228
C.sub.5H.sub.11 555 556 557 1 1 OC.sub.3H.sub.7 229 C.sub.3H.sub.7
558 559 560 1 1 C.sub.5H.sub.11 230 C.sub.5H.sub.11O 561 562 563 1
1 C.sub.3H.sub.7 231 C.sub.7H.sub.15 564 565 566 1 1 CH.sub.3 232
C.sub.3H.sub.7 567 568 569 1 1 OC.sub.2H.sub.5 233 C.sub.5H.sub.11
570 571 572 1 1 OC.sub.4H.sub.9 234 C.sub.2H.sub.5O 573 574 575 1 1
OCH.sub.3 235 C.sub.3H.sub.7 576 577 578 1 1 C.sub.3H.sub.7 236
C.sub.5H.sub.11 579 580 581 1 1 C.sub.3H.sub.7 237 C.sub.3H.sub.7
582 583 584 1 1 C.sub.5H.sub.11 238 C.sub.3H.sub.7 585 586 587 1 1
OC.sub.2H.sub.5 C 89.5 N 193.2 Iso 239 C.sub.5H.sub.11 588 589 590
1 1 OC.sub.3H.sub.7 240 591 592 593 594 1 1 OC.sub.4H.sub.9 241
C.sub.3H.sub.7 595 596 597 1 1 C.sub.3H.sub.7 242 C.sub.5H.sub.11O
598 599 600 1 1 C.sub.5H.sub.11 243 C.sub.7H.sub.15 601 602 603 1 1
C.sub.7H.sub.15 244 C.sub.3H.sub.7 604 605 606 1 1 OC.sub.3H.sub.7
245 C.sub.5H.sub.11 607 608 609 1 1 OC.sub.2H.sub.5 246
C.sub.5H.sub.11 610 611 612 1 1 OC.sub.4H.sub.9 247 C.sub.3H.sub.7
613 614 615 1 1 C.sub.5H.sub.11 248 C.sub.5H.sub.11O 616 617 618 1
1 CH.sub.3 249 C.sub.7H.sub.15 619 620 621 1 1 C.sub.3H.sub.7 250
C.sub.3H.sub.7 622 623 624 1 1 OCH.sub.3 251 C.sub.5H.sub.11 625
626 627 1 1 OC.sub.2H.sub.5 252 C.sub.2H.sub.5O 628 629 630 1 1
OC.sub.4H.sub.9 253 C.sub.3H.sub.7 631 632 633 1 1 C.sub.3H.sub.7
254 C.sub.5H.sub.11 634 635 636 1 1 CH.sub.3 255 637 638 639 640 1
1 C.sub.5H.sub.11 256 C.sub.3H.sub.7 641 642 643 1 1
OC.sub.2H.sub.5 257 C.sub.5H.sub.11 644 645 646 1 1 OC.sub.3H.sub.7
258 C.sub.5H.sub.11 647 648 649 1 1 OC.sub.4H.sub.9 259
C.sub.3H.sub.7 650 651 652 1 1 C.sub.3H.sub.7 260 C.sub.5H.sub.11
653 654 655 1 1 C.sub.5H.sub.11 261 C.sub.7H.sub.15 656 657 658 1 1
C.sub.7H.sub.15 262 C.sub.3H.sub.7 659 660 661 1 1 OC.sub.2H.sub.5
263 C.sub.5H.sub.11 662 663 664 1 1
OC.sub.3H.sub.7 264 C.sub.5H.sub.11O 665 666 667 1 1
OC.sub.4H.sub.9 265 C.sub.3H.sub.7 668 669 670 1 1 C.sub.5H.sub.11
266 C.sub.5H.sub.11O 671 672 673 1 1 C.sub.3H.sub.7 267
C.sub.7H.sub.15 674 675 676 1 1 C.sub.3H.sub.7 268 C.sub.3H.sub.7O
677 678 679 1 1 OCH.sub.3 269 C.sub.5H.sub.11 680 681 682 1 1
OC.sub.4H.sub.9 270 C.sub.2H.sub.5 683 684 685 1 1 OC.sub.2H.sub.5
271 C.sub.2H.sub.5 686 687 688 1 1 C.sub.3H.sub.7 272
C.sub.5H.sub.11 689 690 691 1 1 C.sub.3H.sub.7 273 692 693 694 695
1 1 C.sub.7H.sub.15 274 C.sub.3H.sub.7 696 697 698 1 1
OC.sub.2H.sub.5 275 C.sub.5H.sub.11 699 700 701 1 1 OC.sub.3H.sub.7
276 C.sub.7H.sub.15 702 703 704 1 1 OC.sub.4H.sub.9 277
C.sub.3H.sub.7 705 706 707 1 1 C.sub.3H.sub.7 278 C.sub.5H.sub.11
708 709 710 1 1 C.sub.5H.sub.11 279 C.sub.7H.sub.15 711 712 713 1 1
CH.sub.3 280 C.sub.5H.sub.11O 714 715 716 1 1 OC.sub.2H.sub.5 281
C.sub.5H.sub.11 717 718 719 1 1 OC.sub.4H.sub.9 282 C.sub.3H.sub.7
720 721 722 1 1 OC.sub.3H.sub.7 283 C.sub.3H.sub.7 723 724 725 1 1
C.sub.5H.sub.11 284 C.sub.5H.sub.11O 726 727 728 1 1 C.sub.3H.sub.7
285 C.sub.5H.sub.11 729 730 731 1 1 C.sub.5H.sub.11 286
C.sub.3H.sub.7O 732 733 734 1 1 OC.sub.4H.sub.9 287 C.sub.3H.sub.7
735 736 737 1 1 OCH.sub.3 288 C.sub.5H.sub.11 738 739 740 1 1
OC.sub.2H.sub.5 289 C.sub.3H.sub.7 741 0 0 C.sub.3H.sub.7 290
C.sub.5H.sub.11 742 0 0 OC.sub.2H.sub.5 291 C.sub.3H.sub.7O 743 0 0
OC.sub.3H.sub.7 292 C.sub.3H.sub.7 744 0 0 C.sub.3H.sub.7 293
C.sub.5H.sub.11 745 0 0 OC.sub.2H.sub.5 294 C.sub.7H.sub.15 746 0 0
OCH.sub.3 295 C.sub.3H.sub.7 747 0 0 C.sub.7H.sub.15 296
C.sub.2H.sub.5O 748 0 0 C.sub.5H.sub.11 297 C.sub.5H.sub.11 749 0 0
OC.sub.4H.sub.9 298 750 751 0 0 OC.sub.4H.sub.9 299 C.sub.5H.sub.11
752 0 0 C.sub.3H.sub.7 300 C.sub.5H.sub.11O 753 0 0 OCH.sub.3 301
C.sub.3H.sub.7 754 0 0 OC.sub.2H.sub.5 302 C.sub.5H.sub.11 755 0 0
C.sub.3H.sub.7 303 C.sub.3H.sub.7 756 0 0 CH.sub.3 304
C.sub.3H.sub.7 757 0 0 C.sub.5H.sub.11 305 C.sub.5H.sub.11 758 0 0
OC.sub.2H.sub.5 306 C.sub.7H.sub.15O 759 0 0 OC.sub.3H.sub.7 307
C.sub.3H.sub.7 760 761 1 0 C.sub.5H.sub.11 308 C.sub.5H.sub.11O 762
763 1 0 OC.sub.2H.sub.5 309 C.sub.3H.sub.7 764 765 1 0
C.sub.3H.sub.7 310 766 767 768 1 0 C.sub.3H.sub.7 311
C.sub.5H.sub.11 769 770 1 0 OC.sub.2H.sub.5 312 C.sub.7H.sub.15 771
772 1 0 C.sub.3H.sub.7 313 C.sub.3H.sub.7 773 774 1 0
C.sub.7H.sub.15 314 C.sub.2H.sub.5O 775 776 1 0 C.sub.5H.sub.11 315
C.sub.5H.sub.11 777 778 1 0 OC.sub.4H.sub.9 316 C.sub.3H.sub.7 779
780 1 0 OC.sub.2H.sub.5 317 C.sub.5H.sub.11O 781 782 1 0
C.sub.3H.sub.7 318 C.sub.5H.sub.11 783 784 1 0 OCH.sub.3 319
C.sub.3H.sub.7 785 786 1 0 OC.sub.2H.sub.5 320 C.sub.5H.sub.11 787
788 1 0 C.sub.3H.sub.7 321 C.sub.3H.sub.7 789 790 1 0
OC.sub.3H.sub.7 322 C.sub.4H.sub.9 791 792 1 0 C.sub.5H.sub.11 323
C.sub.5H.sub.11 793 794 1 0 OC.sub.2H.sub.5 324 C.sub.7H.sub.15O
795 796 1 0 CH.sub.3 325 C.sub.5H.sub.11 797 798 1 0
OC.sub.3H.sub.7 326 C.sub.3H.sub.7 799 800 1 0 OC.sub.2H.sub.5 327
C.sub.5H.sub.11 801 802 1 0 C.sub.3H.sub.7 328 C.sub.3H.sub.7 803
804 1 0 C.sub.3H.sub.7 329 C.sub.3H.sub.7O 805 806 1 0
C.sub.7H.sub.15 330 C.sub.7H.sub.15 807 808 1 0 OCH.sub.3 331
C.sub.3H.sub.7 809 810 1 0 OC.sub.2H.sub.5 332 811 812 813 1 0
C.sub.5H.sub.11 333 C.sub.5H.sub.11 814 815 1 0 OCH.sub.3 334
C.sub.2H.sub.5O 816 817 1 0 OC.sub.4H.sub.9 335 C.sub.5H.sub.11 818
819 1 0 C.sub.3H.sub.7 336 C.sub.3H.sub.7 820 821 1 0
OC.sub.4H.sub.9 337 C.sub.5H.sub.11 822 823 1 0 OC.sub.2H.sub.5 338
C.sub.5H.sub.11 824 825 1 0 C.sub.3H.sub.7 339 C.sub.3H.sub.7 826
827 1 0 C.sub.5H.sub.11 340 C.sub.5H.sub.11O 828 829 1 0 CH.sub.3
341 C.sub.3H.sub.7 830 831 1 0 OC.sub.2H.sub.5 342 C.sub.7H.sub.15O
832 833 1 0 OC.sub.3H.sub.7 343 C.sub.5H.sub.11 834 835 836 1 1
C.sub.3H.sub.7 344 C.sub.2H.sub.5O 837 838 839 1 1 OC.sub.2H.sub.5
345 C.sub.3H.sub.7 840 841 842 1 1 OC.sub.4H.sub.9 346 843 844 845
846 1 1 C.sub.3H.sub.7 347 C.sub.5H.sub.11O 847 848 849 1 1
OC.sub.2H.sub.5 348 C.sub.7H.sub.15 850 851 852 1 1 C.sub.5H.sub.11
349 C.sub.5H.sub.11 853 854 855 1 1 C.sub.7H.sub.15 350
C.sub.3H.sub.7 856 857 858 1 1 C.sub.5H.sub.11 351 C.sub.5H.sub.11
859 860 861 1 1 C.sub.3H.sub.7 352 C.sub.3H.sub.7 862 863 864 1 1
OC.sub.2H.sub.5 353 C.sub.5H.sub.11O 865 866 867 1 1 C.sub.3H.sub.7
354 C.sub.4H.sub.9 868 869 870 1 1 OC.sub.3H.sub.7 355
C.sub.3H.sub.7 871 872 873 1 1 OC.sub.2H.sub.5 356 C.sub.5H.sub.11
874 875 876 1 1 C.sub.3H.sub.7 357 C.sub.3H.sub.7 877 878 879 1 1
OCH.sub.3 358 C.sub.3H.sub.7O 880 881 882 1 1 C.sub.5H.sub.11 359
C.sub.5H.sub.11 883 884 885 1 1 OC.sub.2H.sub.5 360
C.sub.7H.sub.15O 886 887 888 1 1 CH.sub.3 361 C.sub.3H.sub.7 889
890 1 0 C.sub.3H.sub.7 362 C.sub.5H.sub.11O 891 892 1 0
OC.sub.2H.sub.5 363 C.sub.3H.sub.7 893 894 895 1 1 C.sub.3H.sub.7
364 896 897 898 899 1 1 C.sub.5H.sub.11 365 C.sub.5H.sub.11 900 901
1 0 OC.sub.2H.sub.5 366 C.sub.7H.sub.15 902 903 1 0 C.sub.3H.sub.7
367 C.sub.3H.sub.7 904 905 906 1 1 OC.sub.2H.sub.5 368
C.sub.2H.sub.5O 907 908 909 1 1 C.sub.5H.sub.11 369 C.sub.5H.sub.11
910 911 912 1 1 OC.sub.2H.sub.5 370 C.sub.3H.sub.7 913 914 1 0
C.sub.7H.sub.15 371 C.sub.5H.sub.11O 915 916 1 0 C.sub.3H.sub.7 372
C.sub.5H.sub.11 917 918 919 1 1 OCH.sub.3 373 C.sub.3H.sub.7 920
921 1 0 CH.sub.3 374 C.sub.5H.sub.11 922 923 924 1 1 C.sub.3H.sub.7
375 C.sub.3H.sub.7 925 926 1 0 OC.sub.3H.sub.7 376 C.sub.4H.sub.9
927 928 929 1 1 C.sub.5H.sub.11 377 C.sub.5H.sub.11 930 931 932 1 1
OC.sub.2H.sub.5 378 C.sub.7H.sub.15O 933 934 1 0
OC.sub.4H.sub.9
[0162] As nematic liquid crystal compositions comprising the liquid
crystalline compound of the present invention produced by such
methods as described above, the following Composition Examples (Use
Examples 1 through 30) can be shown. In this connection, compounds
in the Composition Examples are designated by abbreviation
according to the definition shown in Table 1. Further, when the
hydrogen atom of trans-1,4-cyclohexylene in the following partial
structure was replaced by deuterium (heavy hydrogen) at positions
Q.sub.1, Q.sub.2, and Q3, it is designated by symbol H [1D, 2D,
3D], and when replaced by deuterium at positions Q.sub.5, Q.sub.6,
and Q.sub.7, it is designated by symbol H [5D, 6D, 7D]. In other
words, the positions where deuterium substituted are indicated by
the numeral in the bracket [ ].
[0163] In the Composition Examples (Use Examples), "%" means % by
weight unless otherwise specified, and "part" means part by weight
of an optically active compound based on 100 parts by weight of
liquid crystal composition.
[0164] Determination of viscosity (.eta.) was conducted at 20.0C,
and determination of each of optical anisotropy (.DELTA.n),
dielectric anisotropy (.DELTA..epsilon.), threshold voltage (Vth),
and twist pitch (P) was conducted at 25.0.degree. C.
2TABLE 1 R-(A.sub.1)-Z.sub.1 . . . -Z.sub.n-(A.sub.n)-X 1) Left
side terminal group R- Symbol CH.sub.2n+1-- n- C.sub.nH.sub.2n+O--
nO- C.sub.nH.sub.2n+1OC.sub.mH.sub.2m-- nOm- CH.sub.2.dbd.CH-- V-
CH.sub.2=CHC.sub.nH.sub.2n-- Vn- C.sub.nH.sub.2n+1CH.dbd.CHC.sub-
.mH.sub.2m-- nVm-
C.sub.nH.sub.2n+1CH.dbd.CHC.sub.mH.sub.2mCH.dbd.C-
HC.sub.kH.sub.2k-- nVmVk- 2) Ring structure --(A.sub.1)--,
--(A.sub.n)-- Symbol 935 B 936 (B)F 937 B(2F,3F) 938 B(F,F) 939 H
940 Py 941 D 942 Ch 3) Bonding group --Z.sub.1--, --Z.sub.n--
Symbol --C.sub.2H.sub.4-- 2 --C.sub.4H.sub.8-- 4 --COO-- E
--C.ident.C-- T --CH.dbd.CH-- V --CF.sub.2O-- CF2O --OCF.sub.2--
OCF2 4) Right side terminal group -X Symbol --F --F --Cl --CL --CN
--C --CF.sub.3 --CF3 --OCF.sub.3 --OCF3 --OCF.sub.2H --OCF2H
--C.sub.nH.sub.2n+1 -n --OC.sub.nH.sub.2n+1 --On --COOCH.sub.3 -EMe
--C.sub.nH.sub.2nCH.dbd.CH.sub.2 -nV --C.sub.mH.sub.2mCH.dbd.CHC.s-
ub.nH.sub.2n+1 -mVn --C.sub.mH.sub.2mCH.dbd.CHC.sub.nH.sub.2nF
-mVnF --CH.dbd.CF.sub.2 --VFF --C.sub.nH.sub.2nCH.dbd.CF.su- b.2
-nVFF --C.ident.C--CN -TC 5) Example of designation Example 1
3-H2B(F,F)B(F)--F 943 Example 2 3-HB(F)TB-2 944 Example 3
1V2-BEB(F,F)--C 945 946 Use Example 1 5-H4HB(2F, 3F)-3 (No. 20)
15.0% 3-HEB-O4 23.4% 4-HEB-O2 17.6% 5-HEB-O1 17.6% 3-HEB-O2 14.7%
5-HEB-O2 11.7% T.sub.NI = 77.0 (.degree. C.) .DELTA..epsilon. =
-1.5 Use Example 2 5-H4HB(2F, 3F)-O2 (No. 23) 15.0% 3-HEB-O4 23.4%
4-HEB-O2 17.6% 5-HEB-O1 17.6% 3-HEB-O2 14.7% 5-HEB-O2 11.7%
T.sub.NI = 81.8 (.degree. C.) .DELTA..epsilon. = -2.1 Use Example 3
3-HH4B(2F, 3F)-O2 (No. 94) 15.0% 3-HEB-O4 23.4% 4-HEB-O2 17.6%
5-HEB-O1 17.6% 3-HEB-O2 14.7% 5-HEB-O2 11.7% T.sub.NI = 81.0
(.degree. C.) .DELTA..epsilon. = -1.9 Use Example 4 3-HH4B(2F,
3F)B(2F, 3F)-O2 (No. 238) 15.0% 3-HEB-O4 23.4% 4-HEB-O2 17.6%
5-HEB-O1 17.6% 3-HEB-O2 14.7% 5-HEB-O2 11.7% T.sub.NI = 90.2
(.degree. C.) .DELTA..epsilon. = -2.3 Use Example 5 3-HH4B(2F,
3F)-O2 (No. 94) 10.0% 1V2-BEB(F, F)-C 5.0% 3-HB-C 25.0% 1-BTB-3
5.0% 2-BTB-1 10.0% 3-HH-4 6.0% 3-HHB-1 11.0% 3-HHB-3 4.0% 3-H2BTB-2
4.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0% 3-HB(F)TB-2 6.0% 3-HB(F)TB-3
6.0% CM33 0.8 part T.sub.NI = 90.3 (.degree. C.) .eta. = 17.8
(mPa.multidot.s) .DELTA.n = 0.165 .DELTA..epsilon. = 6.5 V.sub.th =
2.18 (V) P = 11.3 .mu.m Use Example 6 5-H4HB(2F, 3F)-3 (No. 20)
7.0% V2-HB-C 12.0% 1V2-HB-C 12.0% 3-HB-C 15.0% 3-H[1D, 2D, 3D]-C
9.0% 3-HB(F)-C 5.0% 2-BTB-1 2.0% 3-HH-4 4.0% 3-HH-VFF 6.0% 2-H[1D,
2D, 3D]HB-C 3.0% 3-HHB-C 6.0% 3-HB(F)TB-2 5.0% 3-H2BTB-2 5.0%
3-H2BTB-3 5.0% 3-H2BTB-4 4.0% T.sub.NI =87.3 (.degree. C.) .eta. =
19.9 (mPa.multidot.s) .DELTA.n = 0.154 .DELTA..epsilon. = 8.5
V.sub.th = 2.05 (V) Use Example 7 5-H4HB(2F, 3F)-O2 (No. 23) 5.0%
2O1-BEB(F)-C 5.0% 3O1-BEB(F)-C 15.0% 4O1-BEB(F)-C 13.0%
5O1-BEB(F)-C 13.0% 2-HHB(F)-C 15.0% 3-HHB(F)-C 15.0% 3-HB(F)TB-2
4.0% 3-HB(F)TB-3 4.0% 3-HB(F)TB-4 4.0% 3-HHB-1 3.0% 3-HHB-O1 4.0%
T.sub.NI = 88.4 (.degree. C.) .eta. = 88.0 (mPa.multidot.s)
.DELTA.n = 0.149 .DELTA..epsilon. = 30.6 V.sub.th = 0.90(V) Use
Example 8 3-HH4B(2F, 3F)-O2 (No. 94) 6.0% 5-PyB-F 4.0% 3-PyB(F)-F
4.0% 2-BB-C 5.0% 4-BB-C 4.0% 5-BB-C 5.0% 2-PyB-2 2.0% 3-PyB-2 2.0%
4-PyB-2 2.0% 6-PyB-O5 3.0% 6-PyB-O6 3.0% 6-PyB-O7 3.0% 6-PyB-O8
3.0% 3-PyBB-F 6.0% 4-PyBB-F 6.0% 5-PyBB-F 6.0% 3-HHB-3 8.0%
2-H2BTB-2 4.0% 2-H2BTB-3 4.0% 2-H2BTB-4 5.0% 3-H2BTB-2 5.0%
3-H2BTB-3 5.0% 3-H2BTB-4 5.0% T.sub.NI = 90.8 (.degree. C.) .eta. =
36.4 (mPa.multidot.s) .DELTA.n = 0.201 .DELTA..epsilon. = 6.1
V.sub.th = 2.31 (V) Use Example 9 5-H4HB(2F, 3F)-3 (No. 20) 4.0%
3-HH4B(2F, 3F)-O2 (No. 94) 3.0% 3-DB-C 10.0% 4-DB-C 10.0% 2-BEB-C
12.0% 3-BEB-C 4.0% 3-PyB(F)-F 6.0% 3-HEB-O4 8.0% 4-HEB-O2 6.0%
5-HEB-O1 6.0% 3-HEB-O2 5.0% 5-HEB-5 5.0% 4-HEB-5 5.0% 1O-BEB-2 4.0%
3-HHB-1 3.0% 3-HHEBB-C 3.0% 3-HBEBB-C 3.0% 5-HBEBB-C 3.0% T.sub.NI
= 68.1 (.degree. C.) .eta. = 40.5 (mPa.multidot.s) .DELTA.n = 0.121
.DELTA..epsilon. = 11.1 V.sub.th = 1.35 (V9 Use Example 10
5-H4HB(2F, 3F)-3 (No. 20) 4.0% 5-H4HB(2F, 5F)-O2 (No. 23) 4.0%
3-HH4B(2F, 3F)-O2 (No. 94) 4.0% 3-HH4B(2F, 3F)B(2F, 3F)-O2 (No.
238) 4.0% 3-HB-C 18.0% 7-HB-C 3.0% 1O1-HB-C 10.0% 3-HB(F)-C 10.0%
2-PyB-2 2.0% 3-PyB-2 2.0% 4-PyB-2 2.0% 1O1-HH-3 7.0% 2-BTB-O1 7.0%
3-HHB-1 2.0% 3-HHB-F 2.0% 3-HHB-O1 3.0% 3-H2BTB-2 3.0% 3-H2BTB-3
3.0% 2-PyBH-3 4.0% 3-PyBH-3 3.0% 3-PyBB-2 3.0% T.sub.NI = 72.1
(.degree. C.) .eta. = 23.2 (mPa.multidot.s) .DELTA.n = 0.140
.DELTA..epsilon. = 7.1 V.sub.th = 1.90 (V) Use Example 11
5-H4HB(2F, 3F)-3 (No. 20) 10.0% 2O1-BEB(F)-C 5.0% 3O1-BEB(F)-C
12.0% 5O1-BEB(F)-C 4.0% 1V2-BEB(F, F)-C 10.0% 3-HH-EMe 10.0%
3-HB-O2 18.0% 7-HEB-F 2.0% 3-HHEB-F 2.0% 5-HHEB-F 2.0% 3-HBEB-F
4.0% 2O1-HBEB(F)-C 2.0% 3-HB(F)EB(F)-C 2.0% 3-HBEB(F, F)-C 2.0%
3-HHB-F 4.0% 3-HHB-O1 4.0% 3-HHB-3 3.0% 3-HEBEB-F 2.0% 3-HEBEB-1
2.0% T.sub.NI = 70.0 (.degree. C.) .eta. = 38.0 (mPa.multidot.s)
.DELTA.n = 0.112 .DELTA..epsilon. = 23.0 V.sub.th = 1.04 (V) Use
Example 12 3-HH4B(2F, 3F)-O2 (No. 94) 7.0% 5-BEB(F)-C 5.0% V-HB-C
14.0% 5-PyB-C 6.0% 4-BB-3 10.0% 8-HH-2V 10.0% 5-HH-V 6.0% V-HHB-1
7.0% V2-HHB-1 15.0% 3-HHB-1 5.0% 1V2-HBB-2 10.0% 3-HHEBH-3 5.0%
T.sub.NI = 90.1 (.degree. C.) .eta. = 17.9 (mPa.multidot.s)
.DELTA.n = 0.115 .DELTA..epsilon. = 4.8 V.sub.th = 2.37 (V) Use
Example 13 5-H4HB(2F, 3F)-3 (No. 20) 5.0% 5-H4HB(2F, 5F)-O2 (No.
23) 5.0% 2O1-BEB(F)-C 5.0% 3O1-BEB(F)-C 12.0% 5O1-BEB(F)-C 4.0%
1V2-BEB(F, F)-C 16.0% 3-HB-O2 10.0% 3-HH-4 3.0% 3-HHB-F 3.0%
3-HHB-O1 2.0% 3-HBEB-F 4.0% 3-HHEB-F 7.0% 5-HHEB-F 7.0% 3-H2BTB-2
4.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0% 3-HB(F)TB-2 5.0% T.sub.NI = 84.7
(.degree. C.) .eta. = 43.2 (mPa.multidot.s) .DELTA.n = 0.140
.DELTA..epsilon. = 27.5 V.sub.th = 1.06 (V) Use Example 14
3-HH4B(2F, 3F)-O2 (No. 94) 5.0% 3-HH3OB(2F, 3F)B(2F, 3F)-5 (No.
237) 4.0% 2-BEB-C 12.0% 3-BEB-C 4.0% 4-BEB-C 6.0% 3-HB-C 28.0%
3-HEB-O4 12.0% 4-HEB-O2 8.0% 5-HEB-O1 8.0% 3-HEB-O2 6.0% 3-HHB-1
3.0% 3-HHB-O1 4.0% T.sub.NI = 65.1 (.degree. C.) .eta. = 29.1
(mPa.multidot.s) .DELTA.n = 0.116 .DELTA..epsilon. = 9.2 V.sub.th =
1.43 (V) Use Example 15 5-H4HB(2F, 3F)-3 (No. 20) 5.0% 2-BEB-C
10.0% 5-BB-C 12.0% 7-BB-C 7.0% 1-BTB-3 7.0% 2-BTB-1 10.0% 1O-BEB-2
10.0% 1O-BEB-5 12.0% 2-HHB-1 4.0% 3-HHB-F 4.0% 3-HHB-1 7.0%
3-HHB-O1 4.0% 3-HHB-3 8.0% T.sub.NI = 63.4 (.degree. C.) .eta. =
21.2 (mPa.multidot.s) .DELTA.n = 0.160 .DELTA..epsilon. = 6.2
V.sub.th = 1.82 (V) Use Example 16 5-H4HB(2F, 3F)-3 (No. 20) 5.0%
5-H4HB(2F, 3F)-O2 (No. 23) 5.0% 3-HH4B(2F, 3F)-O2 (No. 94) 5.0%
1V2-BEB(F, F)-C 8.0% 3-HB-C 10.0% V2V-HB-C 14.0% V2V-HH-3 14.0%
3-HB-O2 4.0% 3-HHB-1 10.0% 3-HHB-3 5.0% 3-HB(F)TB-2 4.0%
3-HB(F)TB-3 4.0% 3-H2BTB-2 4.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0%
T.sub.NI = 98.1 (.degree. C.) .eta. = 20.8 (mPa.multidot.s)
.DELTA.n = 0.130 .DELTA..epsilon. = 7.2 V.sub.th = 2.18 (V) Use
Example 17 5-H4HB(2F, 3F)-O2 (No. 23) 5.0% 3-HH4B(2F, 3F)-O2 (No.
94) 5.0% 5-BTB(F)TB-3 10.0% V2-HB-TC 10.0% 3-HB-TC 10.0% 3-HB-C
10.0% 5-HB-C 7.0% 5-BB-C 3.0% 2-BTB-1 10.0% 2-BTB-O1 5.0% 3-HH-4
5.0% 3-HHB-3 11.0% 3-H2BTB-2 3.0% 3-H2BTB-3 3.0% 3-HB(F)TB-2 3.0%
T.sub.NI = 92.8 (.degree. C.) .eta. = 16.7 (mPa.multidot.s)
.DELTA.n = 0.203 .DELTA..epsilon. = 6.3 V.sub.th = 2.15 (V) Use
Example 18 5-H4HB(2F, 3F)-3 (No. 20) 10.0% 2-HHB(F)-F 17.0%
3-HHB(F)-F 17.0% 5-HHB(F)-F 16.0% 2-H2HB(F)-F 10.0% 3-H2HB(F)-F
5.0% 2-HBB(F)-F 6.0% 3-HBB(F)-F 6.0% 5-HBB(F)-F 13.0% CN 0.3 part
T.sub.NI = 100.8 (.degree. C.) .eta. = 27.3 (mPa.multidot.s)
.DELTA.n = 0.094 .DELTA..epsilon. = 4.6 V.sub.th = 2.25 (V) p = 81
.mu.m Use Example 19 5-H4HB(2F, 3F)-O2 (No. 23) 6.0% 7-HB(F)-F 5.0%
5-H2B(F)-F 5.0% 3-HB-O2 10.0% 3-HH-4 2.0% 3-HH[5D, 6D, 7D]-4 3.0%
2-HHB(F)-F 10.0% 3-HHB(F)-F 10.0% 5-HH[5D, 6D, 7D]B(F)-F 10.0%
3-H2HB(F)-F 5.0% 2-HBB(F)-F 3.0% 3-HBB(F)-F 3.0% 5-HBB(F)-F 6.0%
2-H2BB(F)-F 5.0% 3-H2BB(F)-F 6.0% 3-HHB- 1 2.0% 3-HHB-O1 5.0%
3-HHB-3 4.0% T.sub.NI = 83.9 (.degree. C.) .eta. = 19.9
(mPa.multidot.s) .DELTA.n = 0.091 .DELTA..epsilon. = 3.0 V.sub.th =
2.69 (V) Use Example 20 5-H4HB(2F, 3F)-O2 (No. 23) 5.0% 3-HH4B(2F,
3F)-O2 (No. 94) 5.0% 7-HB(F, F)-F 3.0% 3-HB-O2 7.0% 2-HHB(F)-F
10.0% 3-HHB(F)-F 10.0% 2-HBB(F)-F 9.0% 3-HBB(F)-F 9.0% 5-HBB(F)-F
16.0% 2-HBB-F 4.0% 3-HBB-F 4.0% 5-HBB-F 3.0% 3-HBB(F, F)-F 5.0%
5-HBB(F, F)-F 10.0% T.sub.NI = 85.5 (.degree. C.) .eta. = 27.9
(mPa.multidot.s) .DELTA.n = 0.116 .DELTA..epsilon. = 5.4 V.sub.th =
2.03 (V) Use Example 21 5-H4HB(2F, 3F)-3 (No. 20) 5.0% 5-H4HB(2F,
3F)-O2 (No. 23) 5.0% 3-HH4B(2F, 3F)-O2 (No. 94) 5.0% 7-HB(F, F)-F
3.0% 3-H2HB(F, F)-F 12.0% 4-H2HB(F, F)-F 10.0% 5-H2HB(F, F)-F 10.0%
3-HHB(F, F)-F 5.0% 4-HHB(F, F)-F 5.0% 3-HH2B(F, F)-F 10.0% 3-HBB(F,
F)-F 12.0% 5-HBB(F, F)-F 12.0% 3-HBCF2OB(F, F)-F 6.0% T.sub.NI =
72.1 (.degree. C.) .eta. = 29.5 (mPa.multidot.s) .DELTA.n = 0.087
.DELTA..epsilon. = 8.1 V.sub.th = 1.61 (V) Use Example 22
5-H4HB(2F, 3F)-O2 (No. 23) 4.0% 3-HH4B(2F, 3F)-O2 (No. 94) 3.0%
3-HH4B(2F, 3F)B(2F, 3F)-O2 (No. 238) 3.0% 7-HB(F, F)-F 5.0%
3-H2HB(F, F)-F 12.0% 3-HHB(F, F)-F 10.0% 4-HHB(F, F)-F 5.0%
3-HBB(F, F)-F 10.0% 3-HHEB(F, F)-F 10.0% 4-HHEB(F, F)-F 3.0%
5-HHEB(F, F)-F 3.0% 2-HBEB(F, F)-F 3.0% 3-HBEB(F, F)-F 5.0%
5-HBEB(F, F)-F 3.0% 3-HDB(F, F)-F 15.0% 3-HHBB(F, F)-F 6.0%
T.sub.NI = 77.8 (.degree. C.) .eta. = 37.5 (mPa.multidot.s)
.DELTA.n = 0.087 .DELTA..epsilon. = 12.4 V.sub.th = 1.44 (V) Use
Example 23 5-H4HB(2F, 3F)-O2 (No. 23) 7.0% 3-HH3OB(2F, 3F)B(2F,
3F)-5 (No. 237) 3.0% 3-HB-CL 10.0% 5-HB-CL 4.0% 7-HB-CL 4.0%
1O1-HH-5 3.0% 2-HBB(F)-F 8.0% 3-HBB(F)-F 8.0% 5-HBB(F)-F 14.0%
4-HHB-CL 8.0% 3-H2HB(F)-CL 4.0% 3-HBB(F, F)-F 10.0% 5-H2BB(F, F)-F
9.0% 3-HB(F)VB-2 4.0% 3-HB(F)VB-3 4.0% T.sub.NI = 91.2 (.degree.
C.) .eta. = 24.9 (mPa.multidot.s) .DELTA.n = 0.125 .DELTA..epsilon.
= 4.3 V.sub.th = 2.39 (V) Use Example 24 3-HH4B(2F, 3F)-O2 (No. 94)
8.0% 3-HH3OB(2F, 3F)B(2F, 3F)-5 (No. 237) 4.0% 3-HHB(F, F)-F 9.0%
3-H2HB(F, F)-F 8.0% 4-H2HB(F, F)-F 8.0% 3-HBB(F, F)-F 21.0%
5-HBB(F, F)-F 20.0% 3-H2BB(F, F)-F 10.0% 5-HHBB(F, F)-F 3.0%
5-HHEBB-F 2.0% 3-HH2BB(F, F)-F 3.0% 1O1-HBBH-4 4.0% T.sub.NI = 95.6
(.degree. C.) .eta. = 39.8 (mPa.multidot.s) .DELTA.n = 0.116
.DELTA..epsilon. = 8.4 V.sub.th = 1.82 (V) Use Example 25
3-HH4B(2F, 3F)-O2 (No. 94) 7.0% 5-HB-F 12.0% 6-HB-F 9.0% 7-HB-F
5.0% 2-HHB-OCF3 7.0% 3-HHB-OCF3 7.0% 4-HHB-OCF3 7.0% 3-HH2B-OCF3
4.0% 5-HH2B-OCF3 4.0% 3-HHB(F, F)-OCF3 5.0% 3-HBB(F)-F 10.0%
5-HBB(F)-F 10.0% 3-HH2B(F)-F 3.0% 3-HB(F)BH-3 3.0% 5-HBBH-3 3.0%
3-HHB(F, F)-OCF2H 4.0% T.sub.NI = 85.5 (.degree. C.) .eta. = 18.0
(mPa.multidot.s) .DELTA.n = 0.094 .DELTA..epsilon. = 4.1 V.sub.th =
2.45 (V) Use Example 26 5-H4HB(2F, 3F)-3 (No. 20) 5.0% 5-H4HB(2F,
3F)-O2 (No. 23) 5.0% 5-H4HB(F, F)-F 7.0% 5-H4HB-OCF3 5.0% 3-H4HB(F,
F)-CF3 8.0% 5-H4HB(F,F)-CF3 10.0% 3-HB-CL 6.0% 5-HB-CL 4.0%
2-H2BB(F)-F 5.0% 3-H2BB(F)-F 10.0% 5-HVHB(F, F)-F 5.0% 3-HHB-OCF3
5.0% 3-H2HB-OCF3 5.0% V-HHB(F)-F 5.0% 3-HHB(F)-F 5.0% 5-HHEB-OCF3
2.0% 3-HBEB(F, F)-F 5.0% 5-HH-V2F 3.0% T.sub.NI = 68.2 (.degree.
C.) .eta. = 27.6 (mPa.multidot.s) .DELTA.n = 0.094 .DELTA..epsilon.
= 8.0 V.sub.th = 1.78 (V) Use Example 27 5-H4HB(2F, 3F)-3 (No. 20)
15.0% 3-HEB-O4 23.0% 4-HEB-O2 18.0% 5-HEB-O1 18.0% 3-HEB-O2 14.0%
5-HEB-O2 12.0% T.sub.NI = 77.0 (.degree. C.) .DELTA.n = 0.087
.DELTA..epsilon. = -1.5 Use Example 28 5-H4HB(2F, 3F)-3 (No. 20)
5.0% 3-HH4B(2F, 3F)B(2F, 3F)-O2 (No. 238) 15.0% 3-HB-O2 10.0%
3-HB-O4 10.0% 3-HH-4 2.0% 5-HH-2 3.0% 3-HEB-O4 15.0% 4-HEB-O2 12.0%
5-HEB-O1 12.0% 3-HEB-O2 9.0% 5-HEB-O2 7.0% T.sub.NI = 81.9
(.degree. C.) .DELTA.n = 0.090 .DELTA..epsilon. = -2.6 Use Example
29 3-HH4B(2F, 3F)-O2 (No. 94) 15.0% 3-HB-O2 15.0% 3-HB-O4 10.0%
3-HEB-O4 10.0% 4-HEB-O2 7.0% 5-HEB-O1 7.0% 3-HEB-O2 6.0% 5-HEB-O2
5.0% 3-HB(2F, 3F)-O2 7.0% 5-HHB(2F, 3F)-O2 5.0% 5-HBB(2F, 3F)-2
5.0% 5-HBB(2F, 3F)-O2 4.0% 5-BB(2F, 3F)B-3 4.0% T.sub.NI = 77.2
(.degree. C.) .DELTA.n = 0.105 .DELTA..epsilon. = -3.1 Use Example
30 5-H4HB(2F, 3F)-3 (No. 20) 15.0% 5-H4HB(2F, 3F)-O2 (No. 23) 10.0%
3-HH4B(2F, 3F)-O2 (No. 94) 15.0% 3-HH4B(2F, 3F)-B(2F, 3F)-O2 (No.
238) 5.0% 3-H4B(2F, 3F)-O2 (No. 4) 5.0% 3-HB(2F, 3F)-O2 20.0%
5-HHB(2F, 3F)-O2 10.0% 5-HHB(2F, 3F)-1O1 5.0% 5-HBB(2F, 3F)-2 10.0%
5-HBB(2F, 3F)-1O1 5.0% Use Example 31 5-H4HB(2F, 3F)-O2 (No. 23)
10.0% 3-HH4B(2F, 3F)-O2 (No. 94) 10.0% 3-H4B(2F, 3F)B(2F, 3F)-O3
(No. 77) 10.0% 5-HH4HB(2F, 3F)-O2 (No. 220) 5.0% 2-HHB(F)-F 2.0%
3-HHB(F)-F 2.0% 5-HHB(F)-F 2.0% 2-HBB(F)-F 6.0% 3-HBB(F)-F 6.0%
5-HBB(F)-F 10.0% 2-H2BB(F)-F 9.0% 3-H2BB(F)-F 9.0% 3-HBB(F, F)-F
14.0% 1O1-HBBH-4 5.0% Use Example 32 3-H4B(2F, 3F)-O2 (No. 4) 7.0%
3-HH3OB(2F, 3F)-3 (No. 91) 4.0% 5-HH4HB(2F, 3F)-O2 (No. 220) 3.0%
5-HB-CL 12.0% 3-HH-4 3.0% 3-HB-O2 17.0% 3-H2HB(F, F)-F 4.0%
3-HHB(F, F)-F 8.0% 3-HBB(F, F)-F 6.0% 2-HHB(F)-F 5.0% 3-HHB(F)-F
5.0% 5-HHB(F)-F 5.0% 2-H2HB(F)-F 2.0% 3-H2HB(F)-F 1.0% 5-H2HB(F)-F
2.0% 3-HHBB(F, F)-F 4.0% 3-HBCF2OB-OCF3 4.0% 5-HBCF2OB(F, F)-CF3
4.0% 3-HHB-O1 4.0% Use Example 33 3-H4B(2F, 3F)-O2 (No. 4) 5.0%
3-HH3OB(2F, 3F)-3 (No. 91) 8.0% 1V2-BEB(F, F)-C 6.0% 3-HB-C 23.0%
2-BTB-1 10.0% 5-HH-VFF 20.0% 1-BHH-VFF 8.0% 1-BHH-2VFF 3.0%
3-H2BTB-2 5.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0% 3-HHB-1 4.0% Use
Example 34 5-H3OB(2F, 3F)-O2 (No. 6) 5.0% 5-H4HB(2F, 3F)-O2 (No.
23) 15.0% 3-H4B(2F, 3F)B(2F, 3F)-O3 (No. 77) 5.0% 2-HB-C 5.0%
3-HB-C 17.0% 3-HB-O2 5.0% 2-BTB-1 3.0% 3-HHB-1 2.0% 3-HHB-F 4.0%
3-HHB-O1 5.0% 3-HHEB-F 4.0% 5-HHEB-F 4.0% 2-HHB(F)-F 7.0%
3-HHB(F)-F 7.0% 5-HHB(F)-F 7.0% 3-HHB(F, F)-F 5.0%
[0165] As will be understood from the Examples described above, the
compounds of the present invention, that is, any two to four rings
compounds having butylene group or propylenoxy group, and
2,3-difluorophenyl group at the same time have the following
characteristics:
[0166] 1) The compounds are wide in temperature range of exhibiting
a liquid crystal phase, and are extremely high in capability of
developing nematic phase.
[0167] 2) Improvement in response speed in IPS mode is noticed with
the compounds, since the compounds have a negative and high
.DELTA..epsilon..
[0168] 3) A low viscosity, low threshold voltage, and improvement
in response speed are noticed with the compounds.
[0169] 4) Separation of crystals or development of smectic phase is
not observed with the compounds even at very low temperatures, and
stabilized nematic liquid crystal compositions can be produced from
the compounds.
INDUSTRIAL APPLICABILITY
[0170] Compounds of the present invention exhibit the
characteristics described in 1) to 4) above, are stable against
outside environment, and can provide novel liquid crystal
compositions and liquid crystal display devices by which
realization of expansion of temperature range of use, driving at a
low voltage, and a high speed response is possible.
* * * * *