JPH0840953A - Trifluoromethylbenzene derivative and liquid crystal composition - Google Patents

Abstract

PURPOSE:To obtain a new compound, useful as a composition component for a nematic liquid crystal display element or a ferroelectric liquid crystal display element and excellent in chemical stability. CONSTITUTION:This compound is expressed by formula I [R<1> is a 1-14C alkyl or alkoxyalkyl; R<1> is a 1-14C alkyl; A is formula II, etc., (L<1> and L<2> are each H or F); Y is a single bond, 0, etc.; Z is a single bond or 0; X is H, F, etc.], e.g. 3-trifluoromethyl-3'-fluoro-4,4''-dioctyloxyterphenyl. The compound of formula I is obtained by lithiating a compound of formula III with C4H4Li, then reacting the resultant compound with B(OCH3)3, treating the prepared boric acid ester derivative with aqueous hydrogen peroxide, thereby providing a compound of formula IV and then etherifying or esterifying the compound of formula IV. Since the obtained compound has an especially great negative DELTAepsilon, the composition is useful as a host material in a tau-Vmin mode method or a liquid crystal material such as a ferroelectric liquid crystal composition according to a high-frequency superposition method or an electrically controlled birefringence mode (ECB) type nematic liquid crystal composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel liquid crystal compound and a liquid crystal composition containing at least one kind of those liquid crystal compounds. More specifically,
The present invention is useful as a composition component for a nematic liquid crystal display device or a ferroelectric liquid crystal display device, and is a novel liquid crystalline compound having a trifluoromethylbenzene ring having excellent chemical stability and liquid crystallinity thereof. The present invention relates to a liquid crystal composition containing at least one compound.

[0002]

BACKGROUND ART A liquid crystal display device is of a light receiving type, so that eyes do not get tired.
Since it has excellent characteristics such as low power consumption and thin shape, it has been widely used for clocks, calculators, word processors, pocket TVs, etc., and recently has a large screen size or pixel count. It is applied to a large number of displays and is attracting attention as a display device to replace the CRT.

Most of these liquid crystal display devices make use of the electro-optical effect of a nematic liquid crystal phase, and the display system thereof is TN type (twisted nematic type), DSM type (dynamic scattering type), GH type ( Guest-host type).

Characteristics required for a display element include a driving temperature range, a threshold voltage (V _th ), a response time, visual characteristics, contrast, etc., and various characteristics required only by one item of liquid crystal compound. Since it is difficult to satisfy the characteristics, a composition satisfying the required performance has been obtained by mixing various liquid crystal substances and preparing a liquid crystal composition that makes the best use of the characteristics of each substance. . Therefore, in order to prepare a liquid crystal composition for practical use, various liquid crystal compounds having individual characteristics are required.
To obtain a wide operating temperature range, a material having a nematic phase in a wide temperature range, a material having a low crystal-nematic phase transition temperature (T _CN ) or a material having a high nematic phase-isotropic liquid transition temperature (T _NI ) is used. It is necessary to use a low-viscosity material for high-speed response, and a low-threshold voltage material for low-voltage driving. In addition, a material having a large refractive index anisotropy (Δn) or a material having a small refractive index anisotropy (Δn) is required for the viewing angle and the contrast depending on the purpose. Further, a liquid crystal used in a driving system using a recent TFT requires a material having a very high resistivity.

On the other hand, not a nematic phase but a ferroelectric liquid crystal [mainly chiral smectic C (chiral SmC)]
The display device using the phase is also actively researched. Ferroelectric liquid crystal [R. B. Meyer et al .; 36L-69 (1
975)]. A. Clark
Applied Phys. lett. , 36,
899 (1980)] is 100 to 1,000 times faster than a conventional nematic liquid crystal system,
Also, it has excellent basic characteristics such as having a memory property, and it is expected that the application of the liquid crystal display element will be expanded by this.

Regarding the preparation of liquid crystal compositions used for ferroelectric liquid crystal display devices, various smectic C (Sm
C) It is preferable that the SmC composition (SmC host) obtained by mixing the compound has one to several kinds of optically active compounds (chiral SmC phase, but it is not necessary to have them).
Chiral dopant) to prepare a ferroelectric liquid crystal composition [L. A. Veresev et
al. Mol. Cryst. Liq. Cryst. 8
9 327 (1982), H .; R. Brandet a
l. J. Physique 44 (Lett.) L-77
1 (1983)] is the mainstream.

The response time in a ferroelectric liquid crystal is τ = η /
E · Ps (τ is response time, η is viscosity, E is electric field, Ps is spontaneous polarization), and τ can be shortened by increasing Ps and decreasing η. However, practically, in addition to the response time, it is necessary to optimize various characteristics such as operating temperature range, viewing angle, contrast, etc. Therefore, as in the case of nematic liquid crystals, various compounds are mixed and the It has been attempted to optimize by making full use of the characteristics of the compound. Since the SmC host component occupies a large proportion in the ferroelectric liquid crystal composition and has a great influence on the characteristics of the ferroelectric liquid crystal composition, an excellent SmC host is required, and the characteristics of the SmC host are For example, the SmC temperature range is wide, the viscosity is low, the tilt angle is 22.5 ° when a chiral dopant is added, and the layer structure is a bookshelf or chevron type and is not twisted.

In recent years, as a method for realizing a practical ferroelectric liquid crystal display, the τ-V _min mode [P. W. H. Sarguy et al. , Ferr
olectrics, 122, 63 (1991),
P. W. Ross et al. , SID'92 Dig
est, 217 (1992), M.S. Koden et
al. , Euro Display '93], and in this mode, as an SmC host material for realizing low voltage driving and high-speed response, the dielectric anisotropy (Δε) has a large negative value and low viscosity. The development of certain materials is desired. As described above, in both nematic liquid crystal compositions and ferroelectric liquid crystal compositions, research and development of various compounds that can be effective components in producing them have been desired.

Dielectric anisotropy (Δ) of known liquid crystal compounds
Focusing on ε), there are many positive materials with large Δε that have been synthesized so far. However, △
Negative materials with small ε are

[Chemical 7] Although a large number of compounds such as, etc. have been put to practical use, there are very few negative materials with large Δε, and they are typical compounds.

Embedded image As can be seen from the above, most of the compounds have a cyano group introduced in the minor axis direction of the molecule, such as high viscosity, high melting point, chemically unstable, and poor compatibility when preparing a composition. It has drawbacks.

A negative material having a large Δε is, for example, an ECB type display device [J. Rb
ert, F.F. Clerc SID 80 Digest
Techn. Papers 30 (1980), J. Am.
Duchen Displays 73 (198)
6), H. Schad SID 82 Digest
Techn. Papers 244 (1982)], a material for adjusting the Δε value of the liquid crystal composition used for the TN or STN type, or a ferroelectric liquid crystal display device by the high frequency superposition method [J. M. Geary,
SID 85 Digest Techn. Paper
s 128 (1985), Y. Sato, et al.
SID 86 Digest Techn. Paper
s 348 (1986)], and the above-mentioned τ-
Used as a host material in the V _min mode method.

From these viewpoints, the present inventors aim to provide a liquid crystalline compound effective in the preparation of a liquid crystal composition for use in a liquid crystal display device, and electron-withdrawing to the side of the long axis of the molecule. By introducing a trifluoromethyl group, which has strong properties, and a fluorine atom into the structure, a compound predicted to increase the dielectric constant in the direction perpendicular to the molecular long axis (Δε becomes a large negative value) As a result of earnest research by designing, synthesizing these, producing each compound simple substance and a composition containing them, an extremely useful material as a liquid crystal composition component used in a nematic liquid crystal display device or a ferroelectric liquid crystal display device. Found. The present invention is based on such findings.

[0012]

DISCLOSURE OF THE INVENTION The present invention has the general formula,

[Chemical 9] (In the formula, R ^{1 is} an alkyl group or an alkoxyalkyl group having 1 to 14 carbon atoms, R ² is an alkyl group having 1 to 14 carbon atoms, and A is

[Chemical 10] L ¹ , L ² , L ³ and L ⁴ each independently represent a hydrogen atom or a fluorine atom, Y is a single bond,

[Chemical 11] , Z represents a single bond or -O-, and X represents a hydrogen atom or a fluorine atom. However, when X is a hydrogen atom, at least one of L ¹ , L ² , L ³ , and L ⁴ represents a fluorine atom, and when A contains a cyclohexane ring, Z represents a single bond, When R ¹ is an alkoxyalkyl group, Y represents a single bond), and provides a novel trifluoromethylbenzene derivative represented by the formula (1), and also contains at least one of these liquid crystal compounds. A characteristic liquid crystal composition is provided.

The synthetic route of the liquid crystalline compound according to the present invention will be explained below, and the present invention will be explained in detail with reference to Examples and the like. The synthetic routes are shown and described below, but they are examples only, and the examples together with the examples do not limit the present invention.

[Synthesis Route Diagram] Each symbol in the formula has the above-mentioned definition.

[0015]

[Chemical 12]

[0016]

[Chemical 13]

[0017]

Embedded image

[0018]

[Chemical 15]

[0019]

Embedded image

The synthetic route represented by the formula will be described below. The compound represented by the route 1 Formula 1 1 ～1- 6 are commercially available. The compound represented by the general formula 1 10 and 1 11,
It can be obtained by etherifying the compounds of the general formulas 1-4 and 1-5, respectively, using alkyl bromide (R ² Br) by a conventional method.

The general formula after lithiation with 1-1 compounds n- butyl lithium _{(C 4 H 9 Li),} N- formyl formula obtained by formylation with mill piperazine 1- 7 compound alkylmagnesium bromide (RMgBr) And then dehydration reaction or the general formula 1-2
A compound of general formula 1-8 is obtained by preparing a Grignard reagent of a compound, reacting it with an alkyl aldehyde (RCHO), and then subjecting it to a dehydration reaction. This para Jiyu carbonless (Pd / C) can be obtained formula 1 13 compounds if hydrogenation reaction in the presence of.

1-alkyne (RC≡CH) was replaced with C ₄ H ₉ L
1-alkyne zinc chloride (RC≡C-Zn) obtained by reacting with zinc chloride (ZnCl ₄ ) after lithiation with i
Cl) formula 1-9 compound by tetrakistriphenylphosphine palladium [Pd _{(PPh 3) 4]} General formula 1- 3 compound in the presence and the coupling reaction is obtained a. This can be obtained formula 1 14 compounds if hydrogenation reaction in the presence of Pd / C.

The thus obtained general formulas 1-6 , 1
- 10, 1 11, 1 13 and 1 14 compounds, after lithiation with each _C 4 _H 9 Li, reacted with trimethyl borate _{[B (OCH 3) 3]} , then the general formula by hydrolyzing A boronic acid derivative represented by I-1 can be obtained.

The boronic acid derivative represented by the general formula I-1 obtained by the route 2 route 1, and a commercially available general formula 2 1 or 2 2 Compound P
d by coupling reaction under _{(PPh 3) 4} exists, the general formula 2-3 or 2-4 compound is obtained, respectively. These compounds can be obtained formula 2 5 compound of the general formula 1 6 or 1 to 10 to obtain a compound represented by formula I-1 the same method as in Route 1. With this compound, or with the general formula I-1
With a compound commercially available and general formula 2-6 compound by coupling reaction respectively, the general formula P-1 or P
A compound represented by -2 is obtained.

[0025] After the route lithiated 3 obtained by the route 2 Formula 2-1 or 2-2 compound with _C 4 _H 9 Li, general formula 3-1 compound by respectively coupling reaction, cyclohexene derivative 3- 2 or 3-3 compound. These compounds from formula 3-4 or 3-5 of the compound obtained by hydrogenating reaction in the presence of Pd / C, respectively, the path 2
In the general formula 2-3 or 2-4 a similar manner as the compound to obtain a compound represented by the general formula P-1, the compounds represented by the general formula P-3 is obtained. In addition, the general formula P
The compound represented by -4, the general formula 3 1 above 3-
As well as obtaining a 5 compound of the general formula 3-7 and a 2-6 compound was coupling reaction, it can then be synthesized by performing a hydrogenation reaction.

The path 4 path formula P-1 to P-4 compounds obtained in 2 and 3 can be represented by the general formula 4-1. Below, the general formula P-
Compounds 1 to P-4 are collectively represented by General Formula 4-1 and a method for synthesizing the compound of General Formula (1) of the present invention will be described.

The general formula after lithiation 4-1 compounds at _C 4 _H 9 Li, B a _{(OCH 3) 3} borate ester derivative obtained by the action of the treatment with hydrogen peroxide solution,
Formula 4-2 compound. This compound is R ¹ Br
In the general formula (1) by etherification by a conventional method or esterification with an acyl chloride (R ¹ COCl).

[Chemical 17] A compound represented by can be obtained. In addition, the general formula 4
- 1 compounds wherein Similarly sequentially lithiated, from the general formula 4-3 compound obtained by formylation in the same manner as obtaining the general formula 1 7 1 13 Compound in the path 1 in the general formula (1) A compound in which Y is represented by a single bond can be obtained.

[0028] The general formula 4-3 compounds chromium trioxide (Cr
Carboxylic acid derivative 4-obtained by oxidation reaction of O ₃ ) etc.
By esterifying the 5 compound with R ¹ OH, Y in the general formula (1) is

Embedded image A compound represented by can be obtained.

[0029] Formula Formula 4 7 compound reduced to the formula 4-6 compound obtained by chlorinating with thionyl chloride (SOCl ₂₎ with 4-3 compound sodium borohydride (NaBH ₄₎ is can get. This was hydrolyzed formula 4-8 compound obtained by cyanation with potassium cyanide in acid or alkali to synthesize formula 4-9 compounds of the general formula If reducing the compound lithium aluminum hydride (LiAlH ₄₎ 4 10 compound is obtained. General formulas general formula 4-6 compound 4- 10
N By performing any repeated route to the compound it is possible to obtain an arbitrary integer of general formula 4 11 compounds. When this is etherified with an alkyl iodide (R ³ I) in the presence of a phase transfer catalyst, Y in the general formula (1) is obtained.
It is possible to obtain a compound in which R is a single bond and R ¹ is an alkoxyalkyl group.

The path 5 commercial formula 5-1 compounds of the general formula obtained by etherification reaction between ^R 1 Br 5-2 compound of bromine (B
is brominated with r _2), the general formula 5-3 compound. Formula 5-2 or 5-3 compounds have the general formulas Formula 1 13 or 1 14 in the path 1 I-
In the same manner to obtain 1 compound can be a boronic acid derivative represented by the general formula 5-4.

[0031] The diazonium salt prepared the formula 5-5 compound is reacted with sodium nitrite (NaNO _2),
This is reacted with potassium iodide (KI) to give a compound of general formula 5-
After obtaining the 6 compounds in the same manner as the general formula 1- 3 in the route 1 to obtain a general formula I-1 compounds of the general formula 5
Nine compounds can be obtained. Boronic acid derivatives obtained by the above method 5-4 or 5-29 compounds Pd (PP
h ₃ ) _{4 in the} presence of the compound of formula 2-3 obtained by the route 2 in the presence of a compound of the formula (1) represented by a single bond or -O- You can

[0032] Similarly, to obtain the general formula 5-3 compound by coupling reaction with a boronic acid derivative 2-5 obtained in the path 2, the general formula Y is represented by -O- the compound of (1) be able to.

The present invention will be described in more detail below with reference to examples and the like. The abbreviations used in this specification have the following meanings. GTO: glass tube oven GLC: gas chromatography HPLC: high performance liquid chromatography TLC: thin layer chromatography IR: infrared absorption spectrum Mass: mass spectrometry b. p. : Boiling point C: Crystalline S _X : Unknown smectic phase S _B : Smectic B phase S _A : Smectic A phase Ne: Nematic phase I: Isotropic liquid? : Temperature unknown

[0034]

【Example】

 Example 1

[Chemical 19] A mixture of 15 g of 2-trifluoromethylphenol, 35.7 g of n-octyl bromide, 25.6 g of potassium carbonate and 200 cc of methyl ethyl ketone was stirred under reflux for 12 hours. The insoluble matter was removed from the reaction mixture by suction filtration, the filtrate was concentrated, extracted with ether, washed with water, dried over sodium sulfate, the solvent was distilled off, and the residue was distilled under reduced pressure. 22.2 g (87.4%) of trifluoromethyloctyloxybenzene was obtained. b.
p. 87-92 ° C / 0.3 torr, GLC 96.4
%, GC-Ms 274 (M ⁺ )

[0035]

Embedded image Bromine 1 was added to a solution of 20 g of 2-trifluoromethyloctyloxybenzene obtained in (a) above in 50 cc of chloroform.
2.8 g was added dropwise, and the mixture was stirred at room temperature for 5 hours. The reaction mixture was poured into a dilute aqueous solution of sodium hydroxide, extracted with chloroform, washed with water, dried over sodium sulfate, the solvent was distilled off, and the residue was distilled under reduced pressure to give 4-bromo-2- Trifluoromethyloctyloxybenzene 23.0 g
(89.1%) was obtained. b. p. 104-108 ° C /
0.15 torr, GLC 99.0%, GC-Ms
352 (M ⁺ -1) 354 (M ⁺ +1)

[0036]

[Chemical 21] 4-Bromo-2-obtained in (b) above under an argon atmosphere
A solution of 18 g of trifluoromethyloctyloxybenzene in 100 cc of tetrahydrofuran was cooled to -70 ° C., and then 1.6M n-butyllithium hexane solution 38
cc was added dropwise, and the mixture was stirred at the same temperature for 1 hour. Trimethyl borate (5.8 g) was added to this reaction mixture, and the mixture was gradually warmed to room temperature and stirred overnight. The reaction mixture was poured into a dilute hydrochloric acid aqueous solution, extracted with benzene, washed with water, dried over sodium sulfate, the solvent was distilled off, and the residue was recrystallized from hexane to give 4-octyloxy-3-trifluoro. 13.5 g (83.3%) of methylphenylboronic acid was obtained. HLC
98.7%, IR (disk) 3370 cm ^-1 (O
H)

[0037]

[Chemical formula 22] Pd (PPh ₃ ) ₄ [tetrakis (triphenylphosphine) palladium (0)] under an argon atmosphere.
27 g, 4-bromo-2-fluoroiodobenzene 6.
7 g of benzene 70 cc solution, 4-octyloxyphenylboronic acid 7.3 g of ethanol 70 cc solution and 2
A mixture of 70 cc of M sodium carbonate aqueous solution was added to 10
The mixture was stirred under reflux for hours. The reaction mixture was poured into water, extracted with benzene, washed with water, dried over sodium sulfate, the solvent was distilled off, and the residue was subjected to silica gel column chromatography using hexane-benzene (1: 1) as an eluent. And then distilled under reduced pressure with GTO to obtain 4'-bromo-2'-fluoro-4-octyloxybiphenyl 2.
5 g (29.8%) were obtained. b. p. 170-175
C / 0.15 torr) GLC97.0%, Mass
378 (M ⁺ -1) 380 (M ⁺ +1)

[0038]

[Chemical formula 23] Pd (PPh ₃ ) ₄ 0.29 g) under an argon atmosphere,
4'-Bromo-2'-fluoro-4-obtained in (d) above
Octyloxybiphenyl 1.5g benzene 15cc
A mixture of the solution, a solution of 1.5 g of 4-octyloxy-3-trifluoromethylphenylboronic acid obtained in (c) above in 15 cc of ethanol and 4 cc of 2M aqueous potassium carbonate solution was stirred under reflux for 18 hours. The reaction mixture was poured into water, extracted with benzene, washed with water, dried over sodium sulfate and the solvent was distilled off. The residue was hexane-benzene (20: 1 to 5: 1) as an eluent. Purified by silica gel column chromatography, and then recrystallized from a mixed solvent of methanol and acetone, and 2.0 g (88.5%) of 3-trifluoromethyl-3′-fluoro-4,4 ″ -dioctyloxyterphenyl. Got

The purity of the obtained compound was 99.
3% and 1 spot by TLC. In addition, it was confirmed that the substance obtained was the title compound from the result of IR measurement and the fact that a molecular ion peak was observed at 572 by Mass analysis and the relation of the raw materials used. Using a METTLER HOT STAGE FP-82, this compound was observed for phase change under a polarizing microscope. The results are shown in Table 4.

Example 2

[Chemical formula 24] Under ice cooling, 2-fluoro-4-bromobiphenyl 10.5
g, anhydrous aluminum chloride 9.6 g and methylene chloride 1
12 g of n-octanoyl chloride in a mixture of 50 cc
10 cc of methylene chloride solution was added dropwise and stirred for 7 hours.
The reaction mixture was poured into a dilute hydrochloric acid aqueous solution, extracted with benzene, washed with water, dried over sodium sulfate, the solvent was distilled off, and the residue was recrystallized with acetone to obtain 2'-fluoro-
4'-bromo-heptylcarbonylbiphenyl 16.3
g (100%) was obtained. Mass376 (M ⁺ -1) 3
78 (M ⁺ +1)

[0041]

[Chemical 25] Under ice-cooling, a mixture of 16.3 g of 2'-fluoro-4'-bromo-heptylcarbonylbiphenyl obtained in (a) above and 90 cc of trifluoroacetic acid was added with 10 g of triethylsilane.
Was added and stirred at room temperature for 4 hours. The reaction mixture was poured into water, extracted with benzene, washed with water, dried over sodium sulfate, the solvent was distilled off, and the residue was distilled under reduced pressure with GTO to obtain 2'-fluoro-4'-. 12.1 g (77.1%) of bromo-4-octylbiphenyl was obtained. b. p. 1
50 ° C / 0.2 torr

[0042]

[Chemical formula 26] In Example 1- (c), 18 g of 4-bromo-2-trifluoromethyloctyloxybenzene was replaced with 18.5 g of 2'-fluoro-4'-bromo-4-octylbiphenyl obtained in (b) above. Example 1-
Operating in the same manner as in (c), 2'-fluoro-4-octyloxybiphenyl-4'-boronic acid 14.5 g (86.8)
%) Was obtained. HPLC 99.2%, IR (disk) 3
350 cm ^-1 (OH)

[0043]

[Chemical 27] In Example 1- (e), 1.5 g of 4'-bromo-2'-fluoro-4-octyloxybiphenyl and 3
In place of 1.5 g of trifluoromethyl-4-octyloxyphenylboronic acid, 1.4 g of 4-bromo-2-trifluoromethyloctyloxybenzene obtained in Example 1- (b) and the above (c) Obtained 2'-fluoro-4-octyloxybiphenyl-4'-boronic acid 1.
Using the same procedure as in Example 1- (e), except using 53 g, 1.25 g (56.6) of 3-trifluoromethyl-3′-fluoro-4-octyloxybiphenyl-4′-octylterphenyl. %) Was obtained.

The purity of the obtained compound was 99.
6%, 1 spot by TLC. In addition, it was confirmed that the substance obtained was a title compound from the result of IR measurement and the fact that a molecular ion peak was observed at 556 in Mass analysis and the relation of the raw materials used. Using a METTLER HOT STAGE FP-82, this compound was observed for phase change under a polarizing microscope. The results are shown in Table 4.

Example 3

[Chemical 28] In Example 1- (a), 1-g of 4-bromo-2-fluorophenol was used in place of 15 g of 2-trifluoromethylphenol, and otherwise the same as in Example 1- (a). 23.6 g (93.6%) of bromo-2-fluorooctyloxybenzene was obtained. b. p. 11
6 to 117 ° C./0.15 torr, GLC97.5%

[0046]

[Chemical 29] In Example 1- (c), 4-bromo-2-trifluoromethyloctyloxybenzene (18 g) was replaced with 4-bromo-2-fluorooctyloxybenzene (15.5 g) obtained in the above (a), and the others were used. The same operation as in Example 1- (c) was performed to obtain 7.5 g (54.7%) of 3-fluoro-4-octyloxyphenylboronic acid. HPLC9
2.5%, IR (disk) 3350 cm ^-1 (OH)

[0047]

Embedded image In Example 1- (d), 6.7 g of 4-bromo-2-fluoroiodobenzene and 7.3 g of 4-octyloxyphenylboronic acid were replaced by 6.3 g of 4-bromoiodobenzene and (b) above. 3-fluoro-4-
Using 7.8 g of octyloxyphenylboronic acid and otherwise operating in the same manner as in Example 1- (d), 6.1 g of 4'-bromo-3-fluoro-4-octyloxybiphenyl (7
2.2%) was obtained. GLC 97.7%

[0048]

[Chemical 31] In Example 1- (e), 4'-bromo-2'-fluoro-4-octyloxybiphenyl (1.5 g) was replaced with 4'-bromo-3-fluoro-4 obtained in (c) above.
-Octyloxybiphenyl was used in the same manner as in Example 1- (e) except that 1.5 g of 3-octyloxybiphenyl was used.
2.1 g (92.9%) of 3 ″ -fluoro-4,4 ″ -dioctyloxyterphenyl was obtained.

The purity of the obtained compound was 99.
7% and 1 spot by TLC. In addition, it was confirmed that the substance obtained was the title compound from the result of IR measurement and the fact that a molecular ion peak was observed at 572 by Mass analysis and the relation of the raw materials used. Using a METTLER HOT STAGE FP-82, this compound was observed for phase change under a polarizing microscope. The results are shown in Table 4.

Example 4

Embedded image 25 g of 4'-bromo-4-pentylbiphenyl to 2 g of magnesium activated by iodine under an argon atmosphere.
1/5 amount of 100 cc of tetrahydrofuran solution of was added and heated. After the reaction was started, the remaining solution was added dropwise, and the mixture was refluxed with stirring for 2 hours to prepare a Grignard reagent.

On the other hand, in an atmosphere of argon, a solution of 9.8 g of trimethyl borate in 20 cc of tetrahydrofuran was cooled to 0 ° C., the Grignard reagent prepared above was added dropwise, and the mixture was gradually returned to room temperature and stirred for 3 hours. The reaction mixture was hydrolyzed by adding ice-cooled 10% aqueous solution of sulfuric acid, extracted with benzene, washed with water, dried over sodium sulfate and the solvent was distilled off. The residue was recrystallized with hexane. -Heptylbiphenyl-4'-boronic acid 15.3 g (68.
6%) was obtained. HPLC 93.8%, IR (disk)
3350 cm ^-1 (OH)

[0052]

[Chemical 33] In Example 1- (d), 6.7 g of 4-bromo-2-fluoroiodobenzene and 7.3 g of 4-octyloxyphenylboronic acid were replaced with 5.4 g of 3-bromo-2-fluorobenzotrifluoride and the above. 2-Fluoro-3-trifluoromethyl-4 ″ -heptyl was prepared by the same procedure as in Example 1- (d) except that 8.6 g of 4-heptylbiphenyl-4′-boronic acid obtained in (a) was used. 8.9 g (96.7%) of terphenyl was obtained, GLC98.5.
%, Mass414 (M ⁺ )

[0053]

Embedded image 2-Fluoro-3 obtained in (b) above under an argon atmosphere
-Trifluoromethyl-4 "-heptyl terphenyl 3
4. A solution of 1.6 g of tetrahydrofuran in 30 cc was cooled to -70 ° C. and then 1.6 Mn-butyllithium in hexane was added.
4 cc was added dropwise, and the mixture was stirred at -10 ° C for 30 minutes. The reaction mixture was cooled to -40 ° C and trimethylborate 1.5c
c was added, and the mixture was stirred at 0 ° C for 30 minutes. Further, the reaction mixture cooled to −10 ° C. was added with 5 cc of 30% hydrogen peroxide solution.
Was added dropwise, the mixture was stirred at 0 ° C. for 1 hour, and then treated with a saturated sodium hydrogen sulfite solution. The reaction mixture was poured into water, extracted with ether, washed with water, dried over sodium sulfate, the solvent was distilled off, and the residue was mixed with hexane-benzene (4: 1 to 1: 1).
Purification by silica gel column chromatography using 1: 1) as an eluent to obtain 1.6 g (51.3%) of 2-fluoro-3-trifluoromethyl-4-hydroxy-4 ″ -heptylterphenyl. HPLC 99.1%,
Mass430 (M ⁺ )

[0054]

Embedded image Under ice-cooling, a solution of 1.46 g of 2-fluoro-3-trifluoromethyl-4-hydroxy-4 ″ -heptylterphenyl obtained in (c) above in 20 cc of dimethylformamide was added with 0.43 g of 60% sodium hydride and n. -Octyl bromide 0.79g was added one by one, and it stirred at room temperature all day and night.
The reaction mixture was poured into a dilute aqueous hydrochloric acid solution, extracted with ether, washed with water, dried over sodium sulfate and the solvent was distilled off. The residue was dissolved in hexane-benzene (4: 1 to 3: 1) as an eluent. Silica gel column chromatography, and then recrystallized from a mixed solvent of methanol and acetone to give 2-fluoro-3-trifluoromethyl-4-octyloxy-4 ″ -heptyl terphenyl 1.06 g.
(57.6%) was obtained.

The purity of the obtained compound was 99.
3% and 1 spot by TLC. In addition, it was confirmed from the results of IR measurement that a molecular ion peak was observed at 542 in Mass analysis, and that the substance obtained was the title compound from the relationship of the raw materials used. Using a METTLER HOT STAGE FP-82, this compound was observed for phase change under a polarizing microscope. The results are shown in Table 4.

Example 5

Embedded image In Example 4- (a), 27.3 g of 4'-bromo-4-octyloxybiphenyl was used in place of 25 g of 4'-bromo-4-heptylbiphenyl, and Example 4 was otherwise used.
The same operation as in (a) was performed and 4-octyloxybiphenyl-
15.1 g (60.9%) of 4'-boronic acid was obtained. HP
LC95.9%, IR (disk) 3370cm
^-1 (OH)

[0057]

Embedded image In Example 1- (d), 6.7 g of 4-bromo-2-fluoroiodobenzene and 7.3 g of 4-octyloxyphenylboronic acid were replaced with 5.4 g of 3-bromo-2-fluorobenzotrifluoride and ( 4 obtained in a)
-Octyloxybiphenyl-4'-boronic acid 9.5 g
Was used in the same manner as in Example 1- (d) except that 9.1 g (92.2%) of 2-fluoro-3-trifluoromethyl-4 ″ -octyloxyterphenyl was obtained.
9.0%, Mass444 (M ⁺ ).

[0058]

[Chemical 38] In Example 4- (c), 2-fluoro-3-trifluoromethyl-4 "-heptylterphenyl was replaced with 3.0 g, and 2-fluoro-3-trifluoromethyl-4" obtained in (b) above. -Octyloxyterphenyl 3.19
g and using the same procedure as in Example 4- (c) except for 2-fluoro-3-trifluoromethyl-4-hydroxy-
2.23 g of 4 "-octyloxyterphenyl (67.
6%) was obtained. HPLC 98.3%, Mass460
(M ⁺ ), IR (disk) 3600 cm ⁻¹ (OH)

[0059]

[Chemical Formula 39] In Example 4- (d), 2-fluoro-3-trifluoromethyl-4-hydroxy-4 ″ -heptylterphenyl was replaced with 1.46 g, and 2-fluoro-3-trifluoro obtained in the above (c) was used. Methyl-4-hydroxy-4 "-
1.26 g (61.9%) of 2-fluoro-3-trifluoromethyl-4,4 ″ -dioctyloxyterphenyl was used in the same manner as in Example 4- (d) except that 1.56 g of octyloxyterphenyl was used. ) Got.

The purity of the obtained compound was 99.
6%, 1 spot by TLC. In addition, it was confirmed that the obtained substance was the title compound from the result of IR measurement and the fact that a molecular ion peak was observed at 572 in Mass analysis and the relation of the raw materials used. Using a METTLER HOT STAGE FP-82, this compound was observed for phase change under a polarizing microscope. The results are shown in Table 4.

Example 6

[Chemical 40] In Example 1- (d), 7.3 g of 4-octyloxyphenylboronic acid was replaced with 7.8 g of 3-fluoro-4-octyloxyphenylboronic acid obtained in Example 3- (b), and Was operated in the same manner as in Example 1- (d) to obtain 10.9 g (94.8%) of 4'-bromo-3,2'-difluoro-4-octyloxybiphenyl. GL
C 97.6%, Mass 396 (M ⁺ -1) 398 (M
⁺ +1)

[0062]

Embedded image In Example 1- (e), 4'-bromo-2'-fluoromethyl-4-octyloxybiphenyl (1.5 g) was replaced with 4'-bromo-3,2'-difluoro obtained in (a) above. Using 1.57 g of -4-octyloxybiphenyl and otherwise operating as in Example 1- (e), 3-trifluoromethyl-3 ', 3 "-difluoro-4,4" -dioctyloxyterphenyl 2 .16 g (92.7%)
I got

The purity of the obtained compound was 99.
4% and 1 spot by TLC. In addition, it was confirmed from the results of IR measurement that a molecular ion peak was observed at 590 by Mass analysis, and that the substance obtained was the title compound from the relationship of the raw materials used. Using a METTLER HOT STAGE FP-82, this compound was observed for phase change under a polarizing microscope. The results are shown in Table 4.

Example 7

Embedded image Under argon atmosphere, a solution of 102 g of o-difluorobenzene in 400 cc of tetrahydrofuran was cooled to -70 ° C., and then a hexane solution of 1.6 M n-butyllithium 6 was added.
50 cc was added dropwise, and the mixture was stirred at the same temperature for 1 hour. To this reaction mixture, 100 g of trimethyl borate was added dropwise, and the temperature was gradually returned to room temperature and stirred overnight. The reaction mixture was poured into a dilute hydrochloric acid aqueous solution, extracted with benzene, washed with water, dried over sodium sulfate, the solvent was distilled off, and the residue was recrystallized from hexane to obtain 81 g of 2,3-difluorophenylboronic acid.
(57.3%) was obtained. HPLC 96.9%) IR (d
isk) 3330 cm ^-1 (OH)

[0065]

[Chemical 43] Under an argon atmosphere, Pd (PPh ₃ ) ₄ 4.8 g, 4-
Bromooctyloxybenzene 23.9 g benzene 1
A mixture of 80 cc solution, 14.6 g of 2,3-difluorophenylboronic acid obtained in (a) above in 180 cc of ethanol and 180 cc of 2M aqueous sodium carbonate solution was stirred under reflux for 6 hours. The reaction mixture was poured into water, extracted with benzene, washed with water, dried over sodium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography using hexane as an eluent, and then decompressed. Distilled under GTO under 2 ', 3'-difluoro-4
-Octyloxybiphenyl 18.0 g (67.4%)
I got GLC96.3%, Mass318 (M ⁺ )

[0066]

[Chemical 44] In Example 1- (c), 18 g of 4-bromo-2-trifluoromethyloctyloxybenzene was replaced with 16.2 g of 2 ', 3'-difluoro-4-octyloxybiphenyl obtained in (b) above. , And other examples 1-
Operating in the same manner as in (c), 2 ', 3'-difluoro-4-octyloxybiphenyl-4'-boronic acid 14.7 g
(79.9%) was obtained. HPLC 98.9%, IR (d
isk) 3350 cm ^-1 (OH)

[0067]

Embedded image In Example 1- (e), 1.5 g of 4'-bromo-2'-fluoro-4-octyloxybiphenyl and 3
In place of 1.5 g of trifluoromethyl-4-octyloxyphenylboronic acid, 1.4 g of 4-bromo-2-trifluoromethyloctyloxybenzene obtained in Example 1- (b) and the above (c) Using 1.71 g of the obtained 2 ', 3'-difluoro-4-octyloxybiphenyl-4'-boronic acid, the same procedure as in Example 1- (e) was repeated except that 3-trifluoromethyl-2', 2.2 g of 3'-difluoro-4,4 "-dioctyloxyterphenyl
(94.0%) was obtained.

The purity of the obtained compound was 99.
1% and 1 spot by TLC. In addition, it was confirmed from the results of IR measurement that a molecular ion peak was observed at 590 by Mass analysis, and that the substance obtained was the title compound from the relationship of the raw materials used. Using a METTLER HOT STAGE FP-82, this compound was observed for phase change under a polarizing microscope. The results are shown in Table 4.

Example 8

Embedded image In Example 7- (b), 26.5 g of 4-iodooctylbenzene was used in place of 23.9 g of 4-bromooctyloxybenzene, and other operations were performed in the same manner as in Example 7- (b). 23.4 g (92.5%) of ′ -difluoro-4-octylbiphenyl was obtained. GLC96.3%,
Mass302 (M ⁺ )

[0070]

[Chemical 47] In Example 1- (c), 18 g of 4-bromo-2-trifluoromethyloctyloxybenzene was replaced with 15.4 g of 2 ′, 3′-difluoro-4-octylbiphenyl obtained in (a) above, Otherwise by performing the same procedure as in Example 1- (c), 13.6 g (77.3%) of 2 ', 3'-difluoro-4-octylbiphenyl-4'-boronic acid was obtained. HPLC 98.6%, IR (disk) 3350c
m ^-1 (OH)

[0071]

Embedded image In Example 1- (e), 1.5 g of 4'-bromo-2'-fluoro-4-octyloxybiphenyl and 3
In place of 1.5 g of trifluoromethyl-4-octyloxyphenylboronic acid, 1.4 g of 4-bromo-2-trifluoromethyloctyloxybenzene obtained in Example 1- (b) and (b) above Using the obtained 2 ', 3'-difluoro-4-octylbiphenyl-4'-boronic acid (1.63 g), the same procedure as in Example 1- (e) was repeated except that 3-trifluoromethyl-2', 3 was used. ′ -Difluoro-
4-octyloxy-4 ″ -octylterphenyl 1.
79 g (78.5%) were obtained.

The purity of the obtained compound was 99.
2% and 1 spot by TLC. In addition, it was confirmed that the substance obtained was a title compound from the result of IR measurement and the fact that a molecular ion peak was observed at 574 by Mass analysis and the relation of the raw materials used. Using a METTLER HOT STAGE FP-82, this compound was observed for phase change under a polarizing microscope. The results are shown in Table 4.

Example 9

[Chemical 49] In Example 1- (a), 2,3-difluorophenol was used instead of 15 g of 2-trifluoromethylphenol, and 2,3-difluoro was used in the same manner as in Example 1- (a). Octyloxybenzene 21.2
g (95.1%) were obtained. b. p. 83-84 ° C / 0.
15 torr, GLC 95.1%

[0074]

Embedded image In Example 1- (c), 12.3 g of 2,3-difluorooctyloxybenzene obtained in the above (a) was used instead of 18 g of 4-bromo-2-trifluoromethyloctyloxybenzene, and other examples were used. The same operation as 1- (c) was performed to obtain 12.3-g (84.1%) of 2,3-difluoro-4-octyloxyphenylboronic acid. HPLC9
9.9%, IR (disk) 3320 cm ^-1 (OH)

[0075]

[Chemical 51] In Example 1- (d), 6.7 g of 4-bromo-2-fluoroiodobenzene and 7.3 g of 4-octyloxyphenylboronic acid were replaced by 6.3 g of 4-bromoiodobenzene and (b) above. Using 2,3-difluoro-4-octyloxyphenylboronic acid (8.3 g), the same procedure as in Example 1- (d) was repeated except that 4'-bromo-2,3-difluoro-4-octyloxybiphenyl was used. 7.4 g (84.1%) was obtained. GTOb. p. 185
~ 190 ° C / 1.0 torr, GLC94.1%, Ma
ss396 (M ⁺ -1) 398 (M ⁺ +1)

[0076]

Embedded image In Example 1- (e), 4'-bromo-2'-fluoro-4-octyloxybiphenyl (1.5 g) was replaced with 4'-bromo-2,3-difluoro-4 obtained in (c) above. -Using 1.57 g of octyloxybiphenyl,
Others were operated similarly to Example 1- (e), and 2.1 g (95.9%) of 3-trifluoromethyl-2 ″, 3 ″ -difluoro-4,4 ″ -dioctyloxyterphenyl was obtained.

The purity of the obtained compound was 99.
7% and 1 spot by TLC. In addition, it was confirmed from the results of IR measurement that a molecular ion peak was observed at 590 by Mass analysis, and that the substance obtained was the title compound from the relationship of the raw materials used. Using a METTLER HOT STAGE FP-82, this compound was observed for phase change under a polarizing microscope. The results are shown in Table 4.

Example 10

Embedded image In Example 1- (d), 6.7 g of 4-bromo-2-fluoroiodobenzene and 7.3 g of 4-octyloxyphenylboronic acid were replaced with 5.4 g of 3-bromo-2-fluorobenzotrifluoride. Example 7-
Using 20.5 g of 2 ', 3'-difluoro-4-octyloxybiphenyl-4'-boronic acid obtained in (c) and using the same procedure as in Example 1- (d), 2,2',
3'-trifluoro-3-trifluoromethyl-4 "-
9.3 g (86.9%) of octyloxyterphenyl was obtained. GLC91.6%, Mass480 (M ⁺ )

[0079]

[Chemical 54] In Example 4- (c), 2,2 ', 3'-trifluoro-3 obtained in (a) above was replaced with 3.0 g of 2-fluoro-3-trifluoromethyl-4 "-heptylterphenyl. 3.5 g of -trifluoromethyl-4 "-octyloxyterphenyl was used, and 2,2 ', 3'-trifluoro-3-trifluoromethyl-4 was prepared by the same procedure as in Example 4- (c). 1.9 g (61.3%) of -hydroxy-4 "-octyloxyterphenyl was obtained. HPLC9
9.5%, Mass496 (M ⁺ ).

[0080]

[Chemical 55] In Example 4- (d), 2,2 ', obtained in the above (b), was used in place of 1.46 g of 2-fluoro-3-trifluoromethyl-4-hydroxy-4 "-heptylterphenyl.
3'-trifluoro-3-trifluoromethyl-4-hydroxy-4 "-octyloxyterphenyl 1.68
g and using the same procedure as in Example 4- (d),
2 ', 3'-trifluoro-3-trifluoromethyl-
4,4 "-Dioctyloxyterphenyl 0.66g
(32.0%) was obtained.

The purity of the obtained compound was 99.
5% and 1 spot by TLC. In addition, it was confirmed that the substance obtained was a title compound from the result of IR measurement and the fact that a molecular ion peak was observed at 608 by Mass analysis and the relation of the raw materials used. Using a METTLER HOT STAGE FP-82, this compound was observed for phase change under a polarizing microscope. The results are shown in Table 4.

Example 11

[Chemical 56] In Example 7- (b), 2-bromooctyloxybenzene was replaced with 23.9 g, and 4-bromo-butyloxybenzene 19.2 g was used. There was obtained 16.1 g (72.3%) of 3'-difluoro-4-butyloxybiphenyl. GLC9
8.5%, Mass262 (M ⁺ ).

[0083]

[Chemical 57] In Example 1- (c), 13.4 g of 2 ', 3'-difluoro-4-butyloxybiphenyl obtained in (a) above was used instead of 18 g of 4-bromo-2-trifluoromethyloctyloxybenzene. , Other examples 1- (c)
The same operation as in 2 ', 3'-difluoro-4-butyloxybiphenyl-4'-boronic acid 13.6 g (86.6)
%) Was obtained. HPLC 99.8%, IR (disk) 3
350 cm ^-1 (OH)

[0084]

Embedded image In Example 1- (d), 6.7 g of 4-bromo-2-fluoroiodobenzene and 7.3 g of 4-octyloxyphenylboronic acid were replaced with 5.4 g of 3-bromo-2-fluorobenzotrifluoride and the above. Using 2 ', 3'-difluoro-4-butyloxybiphenyl-4'-boronic acid 8.9 g obtained in (b), Example 1-
Operating in the same manner as in (d) 2,2 ', 3'-trifluoro
7.4 g (78.7%) of 3-trifluoromethyl-4 ″ -butyloxyterphenyl was obtained. GLC98.1
%, Mass424 (M ⁺ )

[0085]

Embedded image In Example 4- (c), 2,2 ', 3'-trifluoro-3 obtained in (c) above was replaced with 3.0 g of 2-fluoro-3-trifluoromethyl-4 "-heptylterphenyl. Using 3.05 g of -trifluoromethyl-4 "-butyloxyterphenyl, the same procedure as in Example 4- (c) is repeated except that 2,2 ', 3'-trifluoro-3-trifluoromethyl-4 is used. 1.5 g (47.3%) of -hydroxy-4 "-butyloxyterphenyl was obtained. IR (dis)
k) 3420 cm ^-1 (OH), Mass440
(M ⁺ )

[0086]

Embedded image In Example 4- (d), 1.46 g of 2-fluoro-3-trifluoromethyl-4-hydroxy-4 "-heptylterphenyl and 0.79 g of octyl bromide.
In place of 2,2 ', 3'-trifluoro-3-trifluoromethyl-4-hydroxy-4 "-obtained in (d) above.
Using 2.49 g of butyloxyterphenyl and 0.53 g of propyl bromide, the same procedure as in Example 4- (d) is repeated except that 2,2 ', 3'-trifluoro-3-trifluoromethyl-4 "-is used. 1.22 g (74.8%) of butyloxy-4-propyloxyterphenyl was obtained.

The purity of the obtained compound was 99.
It was 8%, and there was one spot by TLC. In addition, it was confirmed from the results of IR measurement and the fact that a molecular ion peak was observed at 482 in Mass analysis, and the substance obtained was the title compound from the relationship of the raw materials used. Using a METTLER HOT STAGE FP-82, this compound was observed for phase change under a polarizing microscope. The results are shown in Table 4.

Example 12

[Chemical formula 61] In Example 1- (d), 6.7 g of 4-bromo-2-fluoroiodobenzene and 7.3 g of 4-octyloxyphenylboronic acid were replaced with 5.4 g of 3-bromo-2-fluorobenzotrifluoride. Example 8-
Using 2 g of 2 ', 3'-difluoro-4-octylbiphenyl-4'-boronic acid obtained in (b), the same procedure as in Example 1- (d) was repeated except that 2,2', 3 was used. 9.1 g (88.3%) of'-trifluoro-3-trifluoromethyl-4 ″ -octylterphenyl was obtained. GLC9
0.6%, Mass464 (M ⁺ )

[0089]

Embedded image In Example 4- (c), 2,2 ', 3'-trifluoro-3 obtained in (a) above was replaced with 3.0 g of 2-fluoro-3-trifluoromethyl-4 "-heptylterphenyl. -Trifluoromethyl-4 "-octylterphenyl was used in the same manner as in Example 4- (c) except that 3.3 g of 2,2 ', 3'-trifluoro-3-trifluoromethyl-4- was used. 2.19 g (64.2%) of hydroxy-4 ″ -octylterphenyl were obtained. HPLC 99.4
%, Mass480 (M ⁺ )

[0090]

[Chemical formula 63] In Example 4- (d), 2,2 ', obtained in the above (b), was used in place of 1.46 g of 2-fluoro-3-trifluoromethyl-4-hydroxy-4 "-heptylterphenyl.
Using 1.63 g of 3'-trifluoro-3-trifluoromethyl-4-hydroxy-4 "-octylterphenyl, the same procedure as in Example 4- (d) was repeated except that 2,2 ',
3'-trifluoro-3-trifluoromethyl-4 "-
Octyl-4-octyloxyterphenyl 0.92g
(45.8%) was obtained.

The purity of the obtained compound was 99.
0% and 1 spot by TLC. In addition, it was confirmed that the substance obtained was a title compound from the result of IR measurement and the fact that a molecular ion peak was observed at 592 in Mass analysis and the relation of the raw materials used. Using a METTLER HOT STAGE FP-82, this compound was observed for phase change under a polarizing microscope. The results are shown in Table 4.

Example 13

[Chemical 64] In Example 7- (b), 20.6 g of 4-iodopropylbenzene was used instead of 23.9 g of 4-bromooctyloxybenzene, and the same procedure as in Example 7- (b) was repeated except that 2 ′, 3 was used. 18.0 g (92.8%) of'-difluoro-4-propylbiphenyl was obtained. GLC95.4%,
Mass232 (M ⁺ )

[0093]

Embedded image In Example 1- (c), 18 g of 4-bromo-2-trifluoromethyloctyloxybenzene was replaced with 11.8 g of 2 ′, 3′-difluoro-4-propylbiphenyl obtained in (a) above, Others were the same as in Example 1- (c), and 12.7 g (90.7%) of 2 ', 3'-difluoro-4-propylbiphenyl-4'-boronic acid was obtained. HPLC 96.3%, IR (disk) 3330c
m ^-1 (OH)

[0094]

[Chemical formula 66] In Example 1- (d), 6.7 g of 4-bromo-2-fluoroiodobenzene and 7.3 g of 4-octyloxyphenylboronic acid were replaced with 5.4 g of 3-bromo-2-fluorobenzotrifluoride and the above. 2 ', 3'-difluoro-4-propylbiphenyl-obtained in (b)
Using 4 g of 4'-boronic acid, other than Example 1- (d).
2,2 ', 3'-trifluoro-3-trifluoromethyl-4 "-propylterphenyl 7.1
g (81.1%) were obtained. GLC92.7%, Mass
394 (M ⁺ )

[0095]

Embedded image In Example 4- (c), 2,2 ', 3'-trifluoro-3 obtained in (c) above was replaced with 3.0 g of 2-fluoro-3-trifluoromethyl-4 "-heptylterphenyl. Using 2.84 g of -trifluoromethyl-4 "-propylterphenyl, the same procedure as in Example 4- (c) is repeated except that 2,2 ', 3'-trifluoro-3-trifluoromethyl-4- is used. 1.4 g (47.3%) of hydroxy-4 ″ -propyl terphenyl was obtained. IR (disk) 35
80 cm ^-1 (OH), Mass410 (M ⁺ )

[0096]

[Chemical 68] In Example 4- (d), 1.46 g of 2-fluoro-3-trifluoromethyl-4-hydroxy-4 "-heptylterphenyl and 0.79 g of octyl bromide.
2,2,3′-trifluoro-3-trifluoromethyl-4-hydroxy-4 ″ -obtained in the above (d)
Using 1.39 g of propyl terphenyl and 0.53 g of propyl bromide, the same operation as in Example 4- (d) is repeated except that 2,2 ', 3'-trifluoro-3-trifluoromethyl-4 "-propyl is used. 0.89 g (58.2%) of -4-propyloxyterphenyl was obtained.

The purity of the obtained compound was 99.
3% and 1 spot by TLC. In addition, it was confirmed that the substance obtained was a title compound from the result of IR measurement and the fact that a molecular ion peak was observed at 452 in Mass analysis and the relation of the raw materials used. Using a METTLER HOT STAGE FP-82, this compound was observed for phase change under a polarizing microscope. The results are shown in Table 4.

Example 14

[Chemical 69] In Example 1- (e), 4-bromo-2-fluorooctyloxy obtained in Example 3- (a) was used instead of 1.5 g of 4'-bromo-2'-fluoro-4-octyloxybiphenyl. Using 1.2 g of benzene and otherwise operating as in Example 1- (e), 3-trifluoromethyl-
1.7 g (86.7%) of 3'-fluoro-4,4'-dioctyloxybiphenyl were obtained.

The purity of the obtained compound was 99.
7% and 1 spot by TLC. In addition, it was confirmed that the substance obtained was the title compound from the result of IR measurement and the fact that a molecular ion peak was recognized at 496 by Mass analysis and the relation of the raw materials used. Using a METTLER HOT STAGE FP-82, this compound was observed for phase change under a polarizing microscope. The results are shown in Table 4.

Example 15

Embedded image In Example 1- (d), 6.4 g of 4-bromo-2-fluoroiodobenzene was used in place of 5.4 g of 3-bromo-2-fluorobenzotrifluoride, and the others were the same as in Example 1- (d). Operate in the same manner
-Fluoro-4'-octyloxybiphenyl 8.0 g
(97.8%) was obtained. GLC96.8%, Mass
368 (M ⁺ )

[0101]

Embedded image In Example 4- (c), 3-trifluoromethyl-2-obtained in (a) above was replaced with 3.0 g of 2-fluoro-3-trifluoromethyl-4 ″ -heptylterphenyl.
Fluoro-4'-octyloxybiphenyl 2.65 g
And the same procedure as in Example 4- (c) except that 3-trifluoromethyl-2-fluoro-4-hydroxy-4 ′ was used.
-Octyloxybiphenyl 1.97 g (71.7%)
I got HPLC 96.2%, IR (disk) 332
0 cm ^-1 (OH), Mass384 (M ⁺ )

[0102]

Embedded image In Example 4- (d), 2-fluoro-3-trifluoromethyl-4-hydroxy-4 "-heptylterphenyl was replaced with 1.46 g, and 3-trifluoromethyl-2- obtained in (b) above was used. Fluoro-4-hydroxy-4'-
Using the same procedure as in Example 4- (d), except that 1.3 g of octyloxybiphenyl was used, 3-trifluoromethyl-2 was used.
0.94 g (56.0%) of -fluoro-4,4'-dioctyloxybiphenyl was obtained.

The purity of the obtained compound was 99.
3% and 1 spot by TLC. In addition, it was confirmed that the substance obtained was the title compound from the result of IR measurement and the fact that a molecular ion peak was recognized at 496 by Mass analysis and the relation of the raw materials used. Using a METTLER HOT STAGE FP-82, this compound was observed for phase change under a polarizing microscope. The results are shown in Table 4.

Example 16

Embedded image In Example 1- (e), 1.5 g of 4'-bromo-2'-fluoro-4-octyloxybiphenyl and 3
In place of 1.5 g of -trifluoromethyl-4-octyloxyphenylboronic acid, 1.4 g of 4-bromo-2-trifluoromethyloctyloxybenzene obtained in Example 1- (b) and Example 9- ( 2, obtained in b)
Using 1.35 g of 3-difluoro-4-octyloxyphenylboronic acid, the same procedure as in Example 1- (e) was repeated except that 3-trifluoromethyl-2 ', 3'-difluoro- was used.
4,4'-Dioctyloxybiphenyl 1.86 g (9
1.2%) was obtained.

The purity of the obtained compound was 99.
6%, 1 spot by TLC. In addition, it was confirmed that the obtained substance was the title compound from the result of IR measurement and the fact that a molecular ion peak was observed at 514 in Mass analysis and the relation of the raw materials used. Using a METTLER HOT STAGE FP-82, this compound was observed for phase change under a polarizing microscope. The results are shown in Table 4.

Example 17

[Chemical 74] In Example 1- (d), 6.7 g of 4-bromo-2-fluoroiodobenzene and 7.3 g of 4-octyloxyphenylboronic acid were replaced with 5.4 g of 3-bromo-2-fluorobenzotrifluoride F and the operation. Example 9-
Using 8.3 g of 2,3-difluoro-4-octyloxyphenyl-boronic acid obtained in (b), other than Example 1
The same operation as in (-d) was performed to obtain 8.6 g (95.7%) of 2,2 ', 3'-trifluoro-3-trifluoromethyl-4'-octyloxybiphenyl. GLC91.3
%, Mass 404 (M ⁺ )

[0107]

[Chemical 75] In Example 4- (c), 2,2 ', 3'-trifluoro-3 obtained in (a) above was replaced with 3.0 g of 2-fluoro-3-trifluoromethyl-4 "-heptylterphenyl. Using 2.9 g of -trifluoromethyl-4'-octyloxybiphenyl, the same procedure as in Example 4- (c) is repeated except that 2,2 ', 3'-trifluoro-3-trifluoromethyl-4- is used. 1.74 g (57.8%) of hydroxy-4′-octyloxybiphenyl was obtained HPLC 9.
8.9%, IR (neat) 3620 cm ^-1 , Mas
s 420 (M ⁺ )

[0108]

[Chemical 76] In Example 4- (d), 2,2 ', obtained in the above (b), was used in place of 1.46 g of 2-fluoro-3-trifluoromethyl-4-hydroxy-4 "-heptylterphenyl.
1.42 g of 3'-trifluoro-3-trifluoromethyl-4-hydroxy-4'-octyloxybiphenyl
And other operations were performed in the same manner as in Example 4- (d).
2 ', 3'-trifluoro-3-trifluoromethyl-
1,4 g of 4,4'-dioctyloxybiphenyl (6
6.1%) was obtained.

The purity of the obtained compound was 99.
5% and 1 spot by TLC. In addition, it was confirmed that the substance obtained was a title compound from the result of IR measurement and the fact that a molecular ion peak was observed at 532 in Mass analysis and the relation of the raw materials used. Using a METTLER HOT STAGE FP-82, this compound was observed for phase change under a polarizing microscope. The results are shown in Table 4.

Example 18

Embedded image Under ice-cooling, 1.5 g of 3-trifluoromethyl-2-fluoro-4-hydroxy-4'-octyloxybiphenyl obtained in Example 15- (b) and 0.6 g of n-octanoic acid.
0.93 g of N, N'-dicyclohexylcarbodiimide was added to a mixture consisting of 1 g, 50 mg of 4-dimethylaminopyridine and 30 cc of methylene chloride, and the mixture was stirred overnight at room temperature. The precipitate was removed from the reaction mixture by suction filtration,
After concentrating the filtrate, hexane-benzene (2: 1 to
Purified by silica gel column chromatography using 1: 1) as an eluent, and then recrystallized from a mixed solvent of acetone-methanol to give 3-trifluoromethyl-2-fluoro-.
1.3 g (65.3%) of 4-heptylcarbonyloxy-4'-octyloxybiphenyl was obtained.

The purity of the obtained compound was 99.
4% and 1 spot by TLC. In addition, it was confirmed that the substance obtained was the title compound from the result of IR measurement and the fact that a molecular ion peak was observed at 510 in Mass analysis and the relation of the raw materials used. Using a METTLER HOT STAGE FP-82, this compound was observed for phase change under a polarizing microscope. The results are shown in Table 4.

Example 19

Embedded image In Example 4- (a), 23 g of 4- (trans-4-pentylcyclohexyl) bromobenzene was used instead of 25 g of 4'-bromo-4-heptylbiphenyl, and otherwise the same as in Example 4- (a). Operate 4- (Trans-4
-Pentylcyclohexyl) phenylboronic acid 10.4
g (51.0%) was obtained. HPLC 99.7%

[0113]

Embedded image In Example 1- (d), 6.7 g of 4-bromo-2-fluoroiodobenzene and 7.3 g of 4-octyloxyphenylboronic acid were replaced with 5.4 g of 3-bromo-2-fluorobenzotrifluoride and the above. Using 4 g of 4- (trans-4-pentylcyclohexyl) phenylboronic acid obtained in (a), the same procedure as in Example 1- (d) was repeated except that 4 ′-(trans-4-pentylcyclohexyl) was used. 8.3 g (95.3%) of -3-trifluoromethyl-2-fluorobiphenyl was obtained. GLC 99.
7%, Mass 392 (M ⁺ )

[0114]

Embedded image In Example 4- (c), 3.0 g of 2-fluoro-3-trifluoromethyl-4 "-heptylterphenyl was replaced with 4 '-(trans-4-pentylcyclohexyl) -obtained in (b) above. 2.8 g of 3-trifluoromethyl-2-fluorobiphenyl was used, except for Example 4-
The same operation as in (c) was conducted to obtain 2.3 g (79.3) of 4 '-(trans-4-pentylcyclohexyl) -3-trifluoromethyl-2-fluoro-4-hydroxybiphenyl.
%) Was obtained. GLC 98.8%, IR (disk) 3
600 cm ^-1 (OH)

[0115]

[Chemical 81] In Example 4- (d), 1.46 g of 2-fluoro-3-trifluoromethyl-4-hydroxy-4 "-heptylterphenyl and 0.79 g of octyl bromide.
In place of 4 '-(trans-4-pentylcyclohexyl) -3-trifluoromethyl-2-obtained in (c) above.
Fluoro-4-hydroxybiphenyl (1.38 g) and propyl bromide (0.53 g) were used.
By the same procedure as in (d), 4 '-(trans-4-pentylcyclohexyl) -3-trifluoromethyl-2-fluoro-4-propyloxybiphenyl 1.01 g (6
6.4%).

The purity of the obtained compound is 99.
8% and 1 spot by TLC. In addition, it was confirmed from the results of IR measurement that a molecular ion peak was observed at 450 in Mass analysis, and that the substance obtained was the title compound from the relationship of the raw materials used. Using a METTLER HOT STAGE FP-82, this compound was observed for phase change under a polarizing microscope. The results are shown in Table 4.

Example 20

[Chemical formula 82] 4'obtained in Example 19- (b) under argon atmosphere
A solution of 3.0 g of-(trans-4-pentylcyclohexyl) -3-trifluoromethyl-2-fluorobiphenyl in 20 cc of tetrahydrofuran was cooled to -70 ° C, and then 6 cc of hexane solution of 1.6 Mn-butyllithium was added.
Was added dropwise, and the mixture was stirred at the same temperature for 2 hours. To this reaction mixture was added 1.2 cc of N-formylpiperidine, the temperature was gradually returned to room temperature, and the mixture was stirred overnight. The reaction mixture was poured into a dilute aqueous hydrochloric acid solution, extracted with benzene, washed with water, dried over sodium sulfate, the solvent was distilled off, and the residue was converted to hexane-benzene (3: 1 to 2: 1) as an eluent. Purified by silica gel column chromatography using 4 '-(trans-4-
Pentylcyclohexyl) -3-trifluoromethyl-
2-fluoro-4-formylbiphenyl 1.0 g (3
1.1%) was obtained. GLC 98.8%, IR (dis
k) 1700 cm ^-1 (C = O)

[0118]

[Chemical 83] Under an argon atmosphere, 15 cc of tetrahydrofuran was added to 1.15 g of ethyltriphenylphosphonium bromide, cooled to -5 ° C, treated with 0.45 g of potassium-t-butoxide, and further stirred at room temperature for 1 hour.
After the reaction mixture was cooled to -5 ° C, the 4 '-(trans-4-pentylcyclohexyl) -3 obtained in the above (a) was obtained.
A solution of 1.0 g of -trifluoromethyl-2-fluoro-4-formylbiphenyl in 10 cc of tetrahydrofuran was added dropwise, and the mixture was stirred at room temperature for one day. The reaction mixture was poured into water, extracted with ethyl acetate, washed with water, dried over sodium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography using hexane as an eluent. -(Trans-4-pentylcyclohexyl) -3
0.64 g of -trifluoromethyl-2-fluoro-4- (1-propenyl) biphenyl was obtained. Next, this compound was dissolved in 20 cc of ethyl acetate, 0.06 g of 10% palladium carbon was added, and hydrogenated at room temperature for 1 hour. The reaction mixture was filtered to remove palladium carbon, the filtrate was concentrated, and the residue was recrystallized from a mixed solvent of acetone-methanol to give 4 '-(trans-4-pentylcyclohexyl) -3-trifluoromethyl. -2
-Fluoro-4-propylbiphenyl 0.41 g (3
9.8%).

The purity of the obtained compound was 99.
2% and 1 spot by TLC. In addition, it was confirmed that the obtained substance was the title compound from the result of IR measurement and the fact that a molecular ion peak was observed at 434 by Mass analysis and the relation of the raw materials used. Using a METTLER HOT STAGE FP-82, this compound was observed for phase change under a polarizing microscope. The results are shown in Table 4.

Example 21

[Chemical 84] 4 '-(trans-4-pentylcyclohexyl) -3-trifluoromethyl-2-fluoro-4-formylbiphenyl 0.9 obtained in Example 20- (a) under ice cooling.
5 g, tetrahydrofuran 10 cc and ethanol 10
0.2 g of sodium borohydride was added to the solution consisting of cc, and the mixture was stirred under reflux for 7 hours. The reaction mixture was poured into a dilute aqueous hydrochloric acid solution, extracted with benzene, washed with water, dried over sodium sulfate, and the solvent was distilled off to give crude 4 '-(trans-4
-Pentylcyclohexyl) -3-trifluoromethyl-2-fluoro-4-hydroxymethylbiphenyl 0.
95 g were obtained. GLC 98.5%, IR (disk)
3320 cm ^-1 (OH)

[0121]

Embedded image 1.0 g of methyl iodide was added to a solution of 0.95 g of crude 4 '-(trans-4-pentylcyclohexyl) -3-trifluoromethyl-2-fluoro-4-hydroxymethylbiphenyl obtained in (a) above in 15 cc of tetrahydrofuran.
0.39 g of potassium hydroxide and 18-crown-69
5 mg was sequentially added, and the mixture was stirred at room temperature for 2 days. The reaction mixture was poured into water, extracted with benzene, washed with water, dried over sodium sulfate and the solvent was distilled off. The residue was hexane-benzene (10: 1 to 1: 1) as an eluent. Purify by silica gel column chromatography, then recrystallize with a mixed solvent of acetone-methanol to obtain 4 '-(trans-4.
-Pentylcyclohexyl) -3-trifluoromethyl-2-fluoro-4-methoxymethylbiphenyl 0.7
1 g (72.4%) was obtained.

The purity of the obtained compound was 99.
9% and 1 spot by TLC. In addition, it was confirmed that the obtained substance was the title compound from the result of IR measurement and the fact that a molecular ion peak was observed at 436 by Mass analysis and the relation of the raw materials used. Using a METTLER HOT STAGE FP-82, this compound was observed for phase change under a polarizing microscope. The results are shown in Table 4.

Example 22

[Chemical 86] Under an argon atmosphere, a solution of 3-bromo-2-fluorobenzotrifluoride (10 g) in tetrahydrofuran (40 cc) was cooled to -70 ° C., 1.6 M n-butyllithium in hexane (31 cc) was added dropwise, and the mixture was stirred at the same temperature for 1 hr. To this reaction mixture was added 10.3 g of pentylcyclohexylcyclohexanone and 50 cc of tetrahydrofuran.
The solution was added dropwise, and the temperature was gradually returned to room temperature with stirring. The reaction mixture was added to diluted hydrochloric acid aqueous solution and extracted with toluene,
Wash with water, dry over sodium sulfate and evaporate the solvent.
Toluene (350 cc) and p-toluenesulfonic acid (1.0 g) were added to the residue, and the mixture was refluxed and stirred for 3 hours using a test tube.
The reaction mixture was poured into water, extracted with toluene, washed with water, dried over sodium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography using hexane as an eluent, and then depressurized. Underneath, distilled with GTO 3
-Trifluoromethyl-2-fluoro- [4- (trans-4-pentylcyclohexyl) -cyclohexene-
1-yl] benzene (9.0 g, 55.2%) was obtained.
b. p. 165 ° C / 0.15 torr

[0124]

[Chemical 87] 3-trifluoromethyl-2-fluoro- [4- (trans-4-pentylcyclohexyl) obtained in (a) above
-Cyclohexen-1-yl] benzene 9.0 g, 10
% Palladium carbon 1.0 g and ethyl acetate 100 c
The mixture consisting of c was hydrogenated overnight at 5 atm.
The reaction mixture was filtered to remove palladium carbon, the filtrate was concentrated, and then the residue was dissolved in 50 cc of dimethyl sulfoxide under an argon atmosphere, 2.7 g of potassium t-butoxide was added to this solution, and the mixture was heated to 30 to 35 ° C. 5
Stirred for hours. The reaction mixture was poured into a dilute aqueous hydrochloric acid solution, extracted with benzene, washed with water, dried over sodium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography using hexane as an eluent. The crystals were recrystallized from acetone to give 5.4 g (5-trifluoromethyl-2-fluoro- [trans-4- (trans-4-pentylcyclohexyl) -cyclohexyl] benzene].
9.7%). GLC 98.7%

[0125]

Embedded image In Example 4- (c), 3-trifluoromethyl-2-obtained in (b) above was replaced with 3.0 g of 2-fluoro-3-trifluoromethyl-4 ″ -heptylterphenyl.
Fluoro- [trans-4- (trans-4-pentylcyclohexyl) -cyclohexyl] benzene 2.87
Using the same procedure as in Example 4- (c), but using 3-g, 3-trifluoromethyl-2-fluoro-4-hydroxy- [trans-4- (trans-4-pentylcyclohexyl) -cyclohexyl] benzene. 74g (58.2
%) Was obtained. HPLC 99.8%, IR (disk)
3380 cm ^-1 (OH)

[0126]

[Chemical 89] In Example 4- (d), 1.46 g of 2-fluoro-3-trifluoromethyl-4-hydroxy-4 "-heptylterphenyl and 0.79 g of octyl bromide.
In place of 3-trifluoromethyl-2 obtained in (c) above
-Fluoro-4-hydroxy- [trans-4- (trans-4-pentylcyclohexyl) -cyclohexyl] benzene 1.4 g and propyl bromide 0.5
Using 3-g, the same operation as in Example 4- (d) is repeated except that 3-trifluoromethyl-2-fluoro-4-propyloxy- [trans-4- (trans-4-pentylcyclohexyl) -cyclohexyl] benzene 1 is used. 0.07 g (6
9.5%).

The purity of the obtained compound was 99.
7% and 1 spot by TLC. In addition, it was confirmed that the substance obtained was a title compound from the result of IR measurement and the fact that a molecular ion peak was observed at 456 in Mass analysis and the relation of the raw materials used. Using a METTLER HOT STAGE FP-82, this compound was observed for phase change under a polarizing microscope. The results are shown in Table 4.

Example 23

[Chemical 90] In Example 20- (a), 4 '-(trans-4-
Pentylcyclohexyl) -3-trifluoromethyl-
Example 22-in place of 3.0 g of 2-fluorobiphenyl
The same as in Example 20- (a) except that 3.0 g of 3-trifluoromethyl-2-fluoro- [trans-4- (trans-4-pentylcyclohexyl) -cyclohexyl] benzene obtained in (b) was used. To 3-trifluoromethyl-2-fluoro-4-formyl- [trans-4- (trans-4-pentylcyclohexyl)-
1.0 g (31.1%) of cyclohexyl] benzene was obtained. GLC 97.9%, IR (disk) 1700c
m ^-1 (C = O)

[0129]

Embedded image In Example 20- (b), 4 '-(trans-4-
Pentylcyclohexyl) -3-trifluoromethyl-
3-Trifluoromethyl-2-fluoro-4-formyl- [trans-4- (trans-4 was obtained in the above (a) in place of 1.0 g of 2-fluoro-4-formylbiphenyl.
-Pentylcyclohexyl) -cyclohexyl] benzene was used in the same manner as in Example 20- (b) except that 1.0 g of 3-trifluoromethyl-2-fluoro-4-propyl- [trans-4- (trans- was used. 0.5 g of 4-pentylcyclohexyl) -cyclohexyl] benzene was obtained.

The purity of the obtained compound was 99.
6%, 1 spot by TLC. In addition, it was confirmed that the substance obtained was the title compound from the result of IR measurement and the fact that a molecular ion peak was observed at 440 by Mass analysis and the relation of the raw materials used. Using a METTLER HOT STAGE FP-82, this compound was observed for phase change under a polarizing microscope. The results are shown in Table 4.

Example 24

Embedded image In Example 21- (a), 4 '-(trans-4-
Pentylcyclohexyl) -3-trifluoromethyl-
3-Trifluoromethyl-2-fluoro-4-formyl- [trans-4-, which was obtained in Example 23- (a), was used instead of 0.95 g of 2-fluoro-4-formylbiphenyl.
0.95 g of (trans-4-pentylcyclohexyl) -cyclohexyl] benzene was used, and the others were used in Example 21-
The same operation as in (a) was performed to obtain 0.95 g (100%) of 3-trifluoromethyl-2-fluoro-4-hydroxymethyl- [trans-4- (trans-4-pentylcyclohexyl) -cyclohexyl] benzene. . GLC
95.9%, IR (disk) 3320 cm ^-1 (O
H)

[0132]

Embedded image In Example 21- (b), 4 '-(trans-4-
Pentylcyclohexyl) -3-trifluoromethyl-
2-fluoro-4-hydroxymethylbiphenyl 0.9
5 g was replaced with 3-trifluoromethyl-2-fluoro-4-hydroxymethyl- [trans-obtained in (a) above.
4- (trans-4-pentylcyclohexyl) -cyclohexyl] benzene (0.95 g) was used with the exception of Example 2
Operate in the same manner as 1- (b) and 3-trifluoromethyl-2
-Fluoro-4-methoxymethyl- [trans-4-
0.8 g (81.6%) of (trans-4-pentylcyclohexyl) -cyclohexyl] benzene was obtained.

The purity of the obtained compound is 99.
7% and 1 spot by TLC. In addition, it was confirmed that the obtained substance was the title compound from the result of IR measurement and the fact that a molecular ion peak was observed at 442 by Mass analysis and the relation of the raw materials used. Using a METTLER HOT STAGE FP-82, this compound was observed for phase change under a polarizing microscope. The results are shown in Table 4.

Example 25 Table 1 shows the dielectric anisotropy (Δε) of the example compounds calculated by the following method. Using a vertical alignment cell (manufactured by EHC, orientation agent: hexadecyltrimethylammonium bromide) and a horizontal alignment cell (manufactured by EHC, orientation agent: Hitachi Chemical Polyimide LX-1400), each of the empty cell capacitances C _{1 and} C ₂ for General Ra
It was measured by a 1620A type capacitance bridge manufactured by Dio (± 0.5 V, 1 KHz sine wave). Next, the measurement sample was enclosed in two types of cells, and the electrostatic capacities C _{3 and} C ₄ of the vertical alignment cell and the horizontal alignment cell were measured in the same manner as described above, and Δε was calculated from the following formula. Δε = [C ₃ / C ₁ ]-[C ₄ / C ₂ ]

[0135]

[Table 1]

These compounds are negative materials having a large Δε and can be used as component materials for imparting a desired Δε when a liquid crystal composition is prepared.

Example 26

Embedded image A base liquid crystal (B-1) composed of the above four kinds of phenylpyrimidine compounds was prepared.

The phase transition temperature is shown below.

[0139]

Embedded image A chiral Sc composition (M-1) composed of a matrix liquid crystal (B-1) 96.7 wt% and an optically active compound (D-1) 3.3 wt% was prepared.

Chiral Sc composition (M-1) 90 wt%
Obtained in Example 12

[Chemical 96] 10 wt% was added to prepare a chiral Sc composition (M-2). Each of the prepared compositions was coated with polyimide and injected into a 2 μm gap liquid crystal cell (manufactured by EHC) prepared from a glass substrate with a transparent electrode, which was subjected to a rubbing treatment, to prepare each liquid crystal element. A test material was prepared by sandwiching it between two polarizing plates, and ± 5 V / μm, 2
Applying a rectangular wave of 00Hz, change τ from the change of transmitted light intensity.
(Response time), Ps (spontaneous polarization) by the Sawyer-Tower method, and θ (tilt angle) were measured from the movement angle of the extinction position when the polarity of the applied voltage was reversed. Furthermore, the phase transition temperature and Δε (see Example 25) were measured. The results are shown in Table 2.

[0141]

[Table 2] As shown in Table 2, the chiral Sc composition (M-
Compared with 1), in the chiral Sc composition (M-2) to which the compound of the present invention was added, the temperature range of the chiral Sc phase was greatly expanded and θ was widened in spite of τ being large.
It can be seen that is almost unchanged. Also, at most 1
It can be seen that Δε is negatively increased only by adding 0 wt%.

Example 27 ZLI-1132, a commercially available nematic liquid crystal composition.
90% by weight (manufactured by Merck & Co.) of Example 19

Embedded image Nematic liquid crystal composition (M-3) consisting of 10 wt%
Was prepared and various physical properties of ZLI-1132 and the composition M-3 were measured. Table 3 shows the results.

[0143]

[Table 3] [Delta] n is used Abbe refractometer (Atago Co., Ltd.), while circulating the 25 ° C. constant-temperature water, and measuring the refractive index of ordinary ray (n ₀₎ and extraordinary refractive index of the (n _e), wherein [Delta] n = n _e -n _o
I asked from.

V _th and V _sat are TN-oriented cells (EH
The sample was sealed in a C company, cell thickness: 9 μm, rubbing angle: 90 °), and this was installed in the photometric part of a spectrophotometer (Hitachi 320 type), and polarization filters were applied to the incident light side and the outgoing light side of the cell. Is installed so as to be in a normally white state (a state in which light is transmitted when no voltage is applied), and a function generator (made by Hewlett Packard)
3311A type), a 1 KHz rectangular wave voltage is applied to the cell, the light transmittance characteristic with respect to the applied voltage is measured at a measurement light wavelength of 550 nm, and the voltage when the transmittance is 90% is V _th , 10 The voltage when showing% was measured as V _sat .

As shown in Table 3, the addition of the compound of the present invention hardly changed T _NI (transition temperature from a nematic phase to an isotropic liquid) and τ (response time), but V _th (threshold value) It can be seen that the voltage) and V _sat (saturation voltage) have decreased. This means that the use of the compound of the present invention enables lower voltage driving. Further, Δn (refractive index anisotropy) is also reduced.

[0146]

INDUSTRIAL APPLICABILITY As described above, the trifluoromethylbenzene derivative according to the present invention is a useful material for preparing a liquid crystal composition having desired characteristics in preparing the liquid crystal composition. Yes, especially large negative Δε
Therefore, it has an extremely excellent effect as a liquid crystal material such as a ferroelectric liquid crystal composition for τ-V _min mode or a high frequency superposition method, and an ECB type nematic liquid crystal composition. .

[0147]

[Table 4]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication location C07C 69/63 9546-4H 69/76 A 9546-4H 69/94 9546-4H C09K 19/12 9279 -4H 19/30 9279-4H 19/44 9279-4H 19/46 9279-4H G02F 1/19 501

Claims (2)

[Claims] 1. A compound of the general formula (In the formula, R ¹ represents an alkyl group or an alkoxyalkyl group having 1 to 14 carbon atoms, R ² represents an alkyl group having 1 to 14 carbon atoms, and A represents Wherein L ¹ , L ² , L ³ and L ⁴ each independently represent a hydrogen atom or a fluorine atom, Y is a single bond, and , Z represents a single bond or -O-, and X represents a hydrogen atom or a fluorine atom. However, when X is a hydrogen atom, at least one of L ¹ , L ² , L ³ , and L ⁴ represents a fluorine atom, and when A is a structure containing a cyclohexane ring, Z is a single bond. In which R ¹ represents an alkoxyalkyl group, Y represents a single bond). 2. A general formula: (In the formula, R ¹ represents an alkyl group or an alkoxyalkyl group having 1 to 14 carbon atoms, R ² represents an alkyl group having 1 to 14 carbon atoms, and A represents Wherein L ¹ , L ² , L ³ and L ⁴ each independently represent a hydrogen atom or a fluorine atom, Y is a single bond, , Z represents a single bond or -O-, and X represents a hydrogen atom or a fluorine atom. However, when X is a hydrogen atom, at least one of L ¹ , L ² , L ³ , and L ⁴ represents a fluorine atom, and when A is a structure containing a cyclohexane ring, Z is a single bond. And when R ¹ is an alkoxyalkyl group, Y represents a single bond), a liquid crystal composition comprising at least one trifluoromethylbenzene derivative.