JPH11269153A - Optically active diphenylpyrimidine compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound as a rapidly responding liquid crystal compound manifesting a chemically more stable chiral smectic C phase within a wide temperature range at the neighbor of a room temperature, having a large spontaneous polarization, providing a low viscosity when added to a base liquid crystal. SOLUTION: This new compound is a compound of formula I [(m) is 1-16; (n) is 2-16; C* is an optically active asymmetric carbon], e.g. 2- 4-[(S)-3- fluorobutyl]phenyl}-5- 4-[(S)-2-fluoro-2-methylbutanolyloxy]phenyl}pyridine. The compound of formula I is prepared, for example, by subjecting an optically active phenol derivative of formula II to a condensation reaction with an optically active 2-fluoro-2-methylalkanoic acid of formula III. For example, 2- 4-[(S)-3-fluorobutyl]phenyl}-5-(4-hydroxyphenyl)pyrimidine or the like is cited as the derivative of formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optically active diphenylpyrimidine compound which can be used as a liquid crystal material which is a material for an optoelectronics device utilizing liquid crystal and electrochemimism, a method for producing the same, and
The present invention relates to a liquid crystal composition containing the optically active diphenylpyrimidine compound. Further, the present invention relates to an optically active phenol derivative corresponding to the intermediate raw material compound used for producing the optically active diphenylpyrimidine compound. The optically active diphenylpyrimidine compound of the present invention or a liquid crystal composition containing the same is used. Examples of this type of optoelectronics-related element include, for example, for display such as a liquid crystal television, an optical front head, an optical Examples include a Fourier transform element, a light valve, and the like.

[0002]

2. Description of the Related Art 4 Synthesized by RBMeyer et al. In 1975
Of ferroelectric liquid crystal represented by-(4-n-decyloxybenzylideneamino) cinnamic acid-2-methylbutyl ester (DOBAMBC) and NA Clar using this ferroelectric liquid crystal
k, et al. (App.Phys. Lett., 1980, 36,
899), high-speed response on the order of microseconds and the property that the orientation of liquid crystal molecules does not change even when the electric field is cut off (memory property)
Has been made possible. By using a display element using such a ferroelectric liquid crystal material, a liquid crystal television of a simple matrix system by multiplex driving without using a switching element or the like has become possible. The simple matrix type liquid crystal cell is much more advantageous than the active matrix type in terms of productivity, cost, reliability, and further increase in screen size.

In order for a ferroelectric liquid crystal material to be widely used as a display material, several physical properties are required. Among them, a basic one is a chiral smectic C phase in a wide temperature range near room temperature. It has a large spontaneous polarization and, in addition, is chemically stable.
Until now, many ferroelectric liquid crystal materials have been synthesized and proposed, but it is difficult to satisfy these physical properties with a single compound.Conventionally, multiple compounds having a chiral smectic C phase are mixed, or the base liquid crystal is mixed. Efforts have been made to obtain a liquid crystal material satisfying the above-mentioned physical properties by adding to the above.
When added to the base liquid crystal, good compatibility with the base liquid crystal is required in addition to the above physical properties.

The search for compounds satisfying such conditions has been advanced. For example, many fluorine-containing optically active compounds have been synthesized so far (Dyes and Chemicals, Vol. 39, No. 1,
See pages 6-17 (1994)). However, most of them do not sufficiently satisfy all required characteristics such as the magnitude of spontaneous polarization, liquid crystallinity, and viscosity when added to a base liquid crystal. Therefore, its application range had to be limited.

On the other hand, some of the fluorine-containing optically active compounds are in an acceptable range over all required characteristics, and have succeeded in obtaining a liquid crystal material having a wide application range by using them. For example, the present inventors have proposed the general formula (II
I):

Embedded image Wherein m represents an integer of 1 to 16, n represents an integer of 2 to 16, and C ^* represents an optically active asymmetric carbon. The compound alone exhibits a chiral smectic C phase in a wide temperature range, has a large spontaneous polarization, and by adding a small amount to the base liquid crystal, induces a sufficient spontaneous polarization and obtains a liquid crystal composition that responds at high speed. (Japanese Patent Application No. 9-70)
No. 925). Although there are proposals for ferroelectric liquid crystal materials exhibiting the excellent characteristics described above, while inducing the same degree of liquid crystallinity and spontaneous polarization, in addition,
There is still a need for compounds with lower viscosity and faster response.

[0006]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems, and an object of the present invention is to provide a chemically stable chiral smectic C over a wide temperature range near room temperature.
A new liquid crystalline compound that exhibits a phase, has a large spontaneous polarization, and has a low viscosity when added to a base liquid crystal and responds at a high speed, a method for producing the same, and a novel compound corresponding to an intermediate material required for the production. To provide. Also,
An object of the present invention is to provide a new liquid crystal composition containing the liquid crystal compound, which can be used for an optical switching element capable of high-speed driving.

[0007]

Means for Solving the Problems As a result of intensive studies and studies, the present inventors have found that ether oxygen present in a compound having two fluorine-containing asymmetric carbon atoms represented by the above general formula (III) is present. A novel compound obtained by converting ((2-fluoroalkyl) oxy group) into a methylene group (3-fluoroalkyl group) was synthesized, and its properties were evaluated. As a result, a compound represented by the general formula (III) was obtained. The present inventors have found that the liquid crystal composition has a lower viscosity and responds at a higher speed while inducing the same degree of liquid crystallinity and spontaneous polarization, thereby completing the present invention.

That is, the liquid crystalline compound of the present invention has the general formula (I):

Embedded image (Wherein, m represents an integer of 1 to 16, n represents an integer of 2 to 16, and C ^* represents an optically active asymmetric carbon). Also,
The present invention is a liquid crystal composition comprising at least one optically active diphenylpyrimidine compound represented by the general formula (I). In addition, another aspect of the present invention provides a compound represented by the following general formula (II) corresponding to an intermediate material used for producing the optically active diphenylpyrimidine compound represented by the general formula (I):

Embedded image (Wherein m represents an integer of 1 to 16, and C ^* represents an optically active asymmetric carbon), and an optically active phenol represented by the general formula (II) Derivatives and general formula (IV):

[0009]

Embedded image (Wherein n represents an integer of 2 to 16, and C ^* represents an optically active asymmetric carbon).
A method for producing an optically active diphenylpyrimidine compound represented by the general formula (I), which comprises condensing -methylalkanoic acid.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION First, the diphenylpyrimidine compound represented by the above formula (I), which is a liquid crystal compound of the present invention, will be described in more detail. The diphenylpyrimidine compound contains a skeleton of 2,5-diphenylpyrimidine as its core skeleton similarly to the compound represented by the general formula (III). 4- at the second position of pyrimidine
A (3-fluoroalkyl) phenyl group has a structure in which a 4- (2-fluoro-2-methylalkanoyl) phenyl group is substituted at the 5-position of pyrimidine, respectively. This compound has two asymmetric carbons, and specifically,
It has optical activity due to the absolute configuration of the fluoro group on the 3-fluoroalkyl group and the absolute configuration of the fluoro group on the 2-fluoro-2-methylalkanoyl group. For example, as the 3-fluoroalkyl group, (S) -3
-Fluorobutyl group is selected, and as a 2-fluoro-2-methylalkanoyl group, (S) -2-fluoro-2-
Specific examples of the compound represented by the general formula (I) for selecting a methylalkanoyl group include the following series of compounds.

2- [4-((S) -3-fluorobutyl) phenyl]
-5- [4-((S) -2-fluoro-2-methylbutanoyloxy) phenyl] pyrimidine 2- [4-((S) -3-fluorobutyl) phenyl] -5- [4-(( S)-
2-Fluoro-2-methylpentanoyloxy) phenyl] pyrimidine 2- [4-((S) -3-fluorobutyl) phenyl] -5- [4-((S)-
2-fluoro-2-methylhexanoyloxy) phenyl] pyrimidine 2- [4-((S) -3-fluorobutyl) phenyl] -5- [4-((S)-
2-fluoro-2-methylheptanoyloxy) phenyl] pyrimidine 2- [4-((S) -3-fluorobutyl) phenyl] -5- [4-((S)-
2-fluoro-2-methyloctanoyloxy) phenyl] pyrimidine 2- [4-((S) -3-fluorobutyl) phenyl] -5- [4-((S)-
2-fluoro-2-methylnonanoyloxy) phenyl] pyrimidine 2- [4-((S) -3-fluorobutyl) phenyl] -5- [4-((S)-
2-fluoro-2-methyldecanoyloxy) phenyl] pyrimidine 2- [4-((S) -3-fluorobutyl) phenyl] -5- [4-((S)-
2-Fluoro-2-methylundecanoyloxy) phenyl]
Pyrimidine 2- [4-((S) -3-fluorobutyl) phenyl] -5- [4-((S)-
2-Fluoro-2-methyldodecanoyloxy) phenyl] pyrimidine 2- [4-((S) -3-fluorobutyl) phenyl] -5- [4-((S)-
2-fluoro-2-methyltridecanoyloxy) phenyl]
Pyrimidine 2- [4-((S) -3-fluorobutyl) phenyl] -5- [4-((S)-
2-fluoro-2-methyltetradecanoyloxy) phenyl] pyrimidine 2- [4-((S) -3-fluorobutyl) phenyl] -5- [4-((S)-
2-fluoro-2-methylpentadecanoyloxy) phenyl] pyrimidine 2- [4-((S) -3-fluorobutyl) phenyl] -5- [4-((S)-
2-fluoro-2-methylhexadecanoyloxy) phenyl] pyrimidine 2- [4-((S) -3-fluorobutyl) phenyl] -5- [4-((S)-
2-Fluoro-2-methylheptadecanoyloxy) phenyl] pyrimidine 2- [4-((S) -3-fluorobutyl) phenyl] -5- [4-((S)-
2-Fluoro-2-methyloctadecanoyloxy) phenyl] pyrimidine

Further, the (S) -3-fluorobutyl group, (S) -3-fluoropentyl group, (S)- 3-fluorohexyl group, (S) -3-fluoroheptyl group, (S) -3-fluorooctyl group, (S) -3-fluorononyl group, (S) -3-fluorodecyl group, (S)- 3-fluoroundecyl group, (S) -3-fluorododecyl group, (S) -3-fluorotridecyl group, (S) -3-fluorotetradecyl group, (S) -3-fluoropentadecyl group,
(S) -3-fluorohexadecyl group, (S) -3-fluoroheptadecyl group, (S) -3-fluorooctadecyl group, a series of compounds replaced with (S) -3-fluorononadecyl group, In addition, a compound group in which the absolute configuration of two asymmetric carbons of these compounds is independently changed from S to R is also included in the compound group represented by the general formula (I). In addition, in order to avoid unnecessary complication, the listing of specific compound names is omitted for these.

The compound represented by the general formula (I) has the general formula (II):

Embedded image (Wherein m represents an integer of 1 to 16, and C ^* represents an optically active asymmetric carbon) represented by the general formula (IV):

Embedded image (Wherein n represents an integer of 2 to 16, C ^* represents an optically active asymmetric carbon) and an optically active carboxylic acid as an intermediate material, and the latter is obtained by esterification with the former. be able to. This esterification is carried out, for example, by a method using a dehydrating condensing agent such as dicyclohexylcarbodiimide, or by converting a carboxylic acid of the general formula (IV) into an acid halide in advance using a halogenating agent such as thionyl chloride, It can be carried out by a method of reacting in the presence of a base.

The optically active carboxylic acid of the general formula (IV), which is an intermediate material, can be obtained from optically active 1,2-epoxy-2-methylalkane by the following known method.

Embedded image (In the formula, n represents an integer of 2 to 16, and C ^* represents an optically active asymmetric carbon.) That is, an amine-hydrogen fluoride complex or an optically active 1,2-epoxy-2-methylalkane is added The compound is reacted with silicon fluoride to form an optically active 2-fluoro-2-methyl-1-alkanol, and then oxidized with an oxidizing agent such as potassium permanganate to form an optically active carboxylic acid of the general formula (IV). An acid can be obtained (JP-A-2-235828, JP-A-3-4122)
No. 41 published patent publication).

On the other hand, the optically active phenol derivative represented by the general formula (II), which is another intermediate material, specifically includes a series of compounds described below, 2- [4-((S)- 3-fluorobutyl) phenyl] -5- (4-hydroxyphenyl) pyrimidine 2- [4-((S) -3-fluoropentyl) phenyl] -5- (4-hydroxyphenyl) pyrimidine 2- [4- ( (S) -3-fluorohexyl) phenyl] -5- (4-hydroxyphenyl) pyrimidine 2- [4-((S) -3-fluoroheptyl) phenyl] -5- (4-hydroxyphenyl) pyrimidine 2- [4-((S) -3-fluorooctyl) phenyl] -5- (4-hydroxyphenyl) pyrimidine 2- [4-((S) -3-fluorononyl) phenyl] -5- (4-hydroxyphenyl ) Pyrimidine 2- [4-((S) -3-fluorodecyl) phenyl] -5- (4-hydroxyphenyl) pyrimidine 2- [4-((S) -3-fluoroundecyl) phenyl] -5- (4-Hydroxyf Nyl) pyrimidine 2- [4-((S) -3-fluorododecyl) phenyl] -5- (4-hydroxyphenyl) pyrimidine 2- [4-((S) -3-fluorotridecyl) phenyl] -5 -(4-hydroxyphenyl) pyrimidine 2- [4-((S) -3-fluorotetradecyl) phenyl] -5- (4-
Hydroxyphenyl) pyrimidine 2- [4-((S) -3-fluoropentadecyl) phenyl] -5- (4-
Hydroxyphenyl) pyrimidine 2- [4-((S) -3-fluorohexadecyl) phenyl] -5- (4-
(Hydroxyphenyl) pyrimidine 2- [4-((S) -3-fluoroheptadecyl) phenyl] -5- (4-
Hydroxyphenyl) pyrimidine 2- [4-((S) -3-fluorooctadecyl) phenyl] -5- (4-
Hydroxyphenyl) pyrimidine 2- [4-((S) -3-fluorononadecyl) phenyl] -5- (4-hydroxyphenyl) pyrimidine, and the above compounds have an asymmetric carbon having an absolute configuration of S to R
A corresponding compound group instead of can be exemplified.

Here, the optically active phenol derivative represented by the general formula (II) can be obtained, for example, by the following method.

Embedded image (In the formula, m represents an integer of 1 to 16, and C ^* represents an optically active asymmetric carbon.)

That is, the optically active 4- (3-fluoroalkyl) benzonitrile represented by the general formula (V) is once converted into an amidine compound by reacting with hydrogen chloride and ammonia. Next, it can be synthesized by reacting the amidine compound with a vinylamidium salt represented by the formula (VI) in the presence of a base. The formula (VI) used
Is a vinylamide salt of 4-hydroxyphenylacetic acid and N,
The compound can be synthesized by the following reaction by reacting N-dimethylformamide and phosphorus oxychloride.

Embedded image

The optically active 4 represented by the general formula (V)
-(3-Fluoroalkyl) benzonitrile is obtained by reacting 4-methylbenzonitrile with an optically active 1,2-epoxyalkane in the presence of a strong base such as lithium diisopropylamide. By reacting such a fluorinating agent, it can be obtained by the following reaction route (see the specification of Japanese Patent Application No. 9-259515).

Embedded image

The number of m and n in the compound represented by the above general formula (I) has an influence on the physical properties such as the temperature range and the viscosity in which the compound can take a liquid crystal state. It is appropriately selected depending on the situation. In general, as the number of m and n in the compound represented by the general formula (I) increases, the viscosity increases, and the temperature range in which a liquid crystal state can be obtained tends to shift to a higher temperature side.

The compound represented by the general formula (I) of the present invention has a chiral smectic C phase or, when added to a liquid crystal composition, develops and stabilizes the chiral smectic C phase. Can be mixed with a chiral or achiral liquid crystal composition and used as a liquid crystal display material. In particular, phenylpyrimidine compounds, phenylpyridine compounds, biphenylpyridine compounds, biphenyl compounds, phenylcyclohexane compounds, benzoic acid phenylester compounds, biphenylcarboxylic acid phenylester compounds,
By adding to a base liquid crystal composed of a diphenylpyrimidine compound or the like or a mixture thereof, a liquid crystal display material showing a stable chiral smectic C phase in a wide temperature range and showing a spontaneous polarization of an appropriate size can be obtained. . When a liquid crystal composition is added to the base liquid crystal to form a liquid crystal composition, the compound represented by the general formula (I) in the present invention has a content of 1 to 60% by weight in the liquid crystal composition depending on the type of the base liquid crystal. Can be selected and added. When compounding the compound of the general formula (I), any one compound may be used alone or a plurality of compounds may be mixed. Is preferably selected within the range of 1 to 60% by weight in the liquid crystal composition.

Further, an optical switching element can be manufactured by enclosing the compound represented by the above general formula (I) of the present invention or a liquid crystal composition containing the compound in a cell having a transparent electrode.

[0022]

EXAMPLES The present invention will be specifically described below with reference to examples. Note that the present invention is not limited to these specific examples. The structures of the compounds shown in the following specific examples were confirmed to be the target compounds based on the results of NMR, IR, MS, and elemental analysis. (Neat) in the notation of the measurement result of IR indicates measurement by a liquid film. CDCl ₃ in the notation of NMR measurement results represents a solvent deuterated chloroform, s is a singlet, d is a doublet, t is a triplet, q is a quadruple, m represents a multiplet, J represents a binding constant. Also MS
Numerical values shown in parentheses in the notation of the measurement result indicate the relative intensity of the peak.

Reference Example 1 (S) -4- (3-Fluorononyl)
Synthesis of benzonitrile

Embedded image Diisopropylamine (4.4 ml, 31 mmol) in anhydrous THF
Butyllithium (1.6 M hexane solution, 19.5 ml, 31 mmol) was added to the solution (26 ml) at -78 ° C, and the mixture was stirred for 30 minutes.
4-Methylbenzonitrile (3.0 g, 26 mmol) in THF (5 m
l) The solution was added. After stirring for 30 minutes, a solution of (R) -1,2-epoxyoctane (3.3 g, 26 mmol) in THF (5 ml) was added, and the mixture was heated to room temperature and stirred for 2 hours. A saturated aqueous solution of sodium hydrogen carbonate was added to the reaction solution, extracted with ethyl acetate, washed with saturated saline and concentrated. The residue was subjected to silica gel column chromatography (hexane / ethyl acetate = 3).
/ 1) to give (R) -4- (3-hydroxynonyl) benzonitrile (3.4 g, 54%). Colorless oil [α] _D
²⁰ -16.5 ° (c 1.0, CHCl ₃ )

Next, (R) -4- (3-hydroxynonyl) benzonitrile (2.7 g, 11 mmol) in dichloromethane (85 m
l) In solution, add diethylaminosulfur trifluoride (8.7
ml, 66 mmol) and slowly warmed to room temperature. To the reaction solution was added a saturated aqueous solution of sodium hydrogen carbonate, extracted with ether, washed with saturated saline, and concentrated. The residue was purified by silica gel column chromatography (hexane / ethyl acetate = 10/1) to obtain (S) -4- (3-fluorononyl) benzonitrile (2.25 g, 83%). Colorless oil [α] _D ²⁰ +16.0 ° (c 1.1, CHCl ₃ )

Reference Example 2 (R) -4- (3-Fluorononyl)
Synthesis of Benzonitrile According to the reaction procedure and conditions described in Reference Example 1, (S) -1,2-epoxyoctane was used instead of (R) -1,2-epoxyoctane, and (R) -4- (3-Fluorononyl) benzonitrile (81%)
I got Colorless oil [α] _D ²⁰ -12.0 ° (c 1.0, CHCl ₃ )

Reference Example 3 Synthesis of (R) -4- (3-fluoroheptyl) benzonitrile In place of (R) -1,2-epoxyoctane, according to the reaction procedure and conditions described in Reference Example 1. Then, using (S) -1,2-epoxyhexane, (R) -4- (3-fluoroheptyl) benzonitrile was obtained. Colorless oil [α] _D ²⁰ -19.1 ° (c 1.0, CHCl ₃ )

Reference Example 4 Synthesis of (S) -4- (3-fluoroheptyl) benzonitrile In place of (R) -1,2-epoxyoctane, according to the reaction procedure and conditions described in Reference Example 1. Using (R) -1,2-epoxyhexane for (S) -4- (3-fluoroheptyl) benzonitrile (82
%). Colorless oil [α] _D ²⁰ +19.7 ° (c 0.8, CHCl ₃ )

Example 1 Synthesis of 2- [4-((S) -3-fluorononyl) phenyl] -5- (4-hydroxyphenyl) pyrimidine

Embedded image

A solution of (S) -4- (3-fluorononyl) benzonitrile (1.38 g, 5.6 mmol) synthesized in Reference Example 1 in dichloromethane (15 ml), ether (15 ml), and ethanol (1.6 ml) Was stirred at room temperature under a hydrogen chloride atmosphere for 4 days. After concentrating the reaction solution, ether (20 ml) was added to the residue, and the precipitate was separated by filtration and dried to obtain an imino ester hydrochloride as a white powder. This was dissolved in methanol (15 ml) and stirred at room temperature for 5 days under an ammonia atmosphere. After concentrating the reaction solution, ether (20 ml) was added to the residue, and the precipitate was separated by filtration and dried to obtain amidine hydrochloride as a pale yellow powder. This amidine hydrochloride and 2- (4-hydroxyphenyl)-
N, N, N ', N'-tetramethylviniaminidium chloride (1.
7 g, 6.6 mmol) was added to a sodium methoxide-methanol solution prepared from sodium (9.5 g) and methanol (20 ml), and the mixture was heated under reflux for one day. After evaporating the solvent under reduced pressure, 1 M hydrochloric acid was added to the residue, and the mixture was extracted with ethyl acetate and concentrated. The residue was purified by silica gel column chromatography (hexane / ethyl acetate = 2/1) and further recrystallized from ethanol to give 2- [4-((S) -3-fluorononyl).
Phenyl] -5- (4-hydroxyphenyl) pyrimidine (1.4
1 g, 81%). Colorless powder Melting point 101 ° C [α] _D ²⁰ + 12.1 ° (c 0.96, CHCl ₃ ) IR (KBr) 3250, 2925, 1610, 1580, 1440, 1260, 841,
795 cm ^{-1 1} H NMR (CDCl ₃ ) δ 0.68 (t, J = 7.0 Hz, 3 H), 1.32
-1.77 (m, 10 H), 1.77-2.10 (m, 2 H), 2.77 (ddd, 7.
1, 9.4, and 14.0 Hz, 1 H), 2.89, (ddd, J = 5.3, 9.
8, and 14.0 Hz, 1 H), 4.50 (dm, J = 49.1 Hz, 1 H),
5.38-5.47 (broad s, 1 H), 6.99 (d, J = 8.7 Hz, 2
H), 7.43 (d, J = 8.3 Hz, 2 H), 7.52 (d, J = 8.7 H
z, 2 H), 8.39 (d, J = 8.3 Hz, 2 H), 8.96 (s, 1 H) MS (m / z) 392 (M ⁺ , 100), 275 (35), 262 (49), 261 (9
9), 118 (22)

Example 2 Synthesis of 2- [4-((R) -3-fluorononyl) phenyl] -5- (4-hydroxyphenyl) pyrimidine In the same manner as in Example 1, ( 2- [4-((R) -3-fluorononyl) phenyl] -5- (4-hydroxyphenyl) pyrimidine was synthesized from (R) -4- (3-fluorononyl) benzonitrile (93% yield). . [Α] _D ²⁰ -12.0 ° (c 1.03, CHCl ₃ )

Example 3 Synthesis of 2- [4-((S) -3-fluoroheptyl) phenyl] -5- (4-hydroxyphenyl) pyrimidine

Embedded image

In the same manner as in Example 1, (S) -4-
From (3-fluoroheptyl) benzonitrile to 2- [4-((S) -3
-Fluoroheptyl) phenyl] -5- (4-hydroxyphenyl) pyrimidine was synthesized (80% yield). Colorless needles Melting point 125 ° C [α] _D ²⁰ + 13.7 ° (c 0.92, CHCl ₃ ) IR (KBr) 3040, 2930, 1610, 1590, 1520, 1430, 1280,
830 cm ^{-1 1} H NMR (CDCl ₃ ) δ 0.91 (t, J = 7.0 Hz, 3 H), 1.24
-2.08 (m, 8 H), 2.78 (ddd, 7.1, 9.4, and 13.9 Hz,
1H), 2.90, (ddd, J = 5.2, 9.4, and 13.9 Hz, 1 H),
4.50 (dm, J = 49.4 Hz, 1 H), 5.59 (broad s, 1 H),
6.99 (d, J = 8.7 Hz, 2 H), 7.34 (d, J = 8.3 Hz, 2
H), 7.51 (d, J = 8.7 Hz, 2 H), 8.38 (d, J = 8.3 H
z, 2 H), 8.96 (s, 1 H) MS (m / z) 364 (M ⁺ , 100), 275 (12), 262 (60), 261 (8
2), 118 (30) Elemental analysis: C ₂₃ H ₂₅ N ₂ F ₀ Calculated: C, 75.80; H, 6.91; N, 7.69%. Found: C, 75.61; H, 6.85; N, 7.58 %

Example 4 Synthesis of 2- [4-((R) -3-fluoroheptyl) phenyl] -5- (4-hydroxyphenyl) pyrimidine In the same manner as in Example 1, ( 2- [4-((R) -3-fluoroheptyl) phenyl] -5- (4-hydroxyphenyl) pyrimidine was synthesized from (R) -4- (3-fluoroheptyl) benzonitrile (yield 73%). . [Α] _D ²⁰ -13.7 ° (c 0.73, CHCl ₃ )

Example 5 2- [4-((S) -3-fluorononyl) phenyl] -5- [4-((S) -2-fluoro-2-methyldecanoyloxy) phenyl] pyrimidine Synthesis of

Embedded image

2- [4-((S) -3-fluorononyl) phenyl] -5- (4-hydroxyphenyl) pyrimidine (70 mg, 0.18 mmol) synthesized in Example 1, (S) -2- Fluoro-2-methyldecanoic acid (36 mg, 0.18 mmol) in dichloromethane (4 m
l) Add dicyclohexylcarbodiimide (58 mg,
0.28 mmol) and 4- (dimethylamino) pyridine (41 m
g, 0.33 mmol) and stirred at room temperature for 1 day. The reaction solution was filtered through celite, concentrated, and then the residue was purified by silica gel column chromatography (hexane / dichloromethane = 1/4 to dichloromethane). Further, recrystallization from hexane gave 2- [4-((S) -3-fluorononyl) phenyl].
This gave -5- [4-((S) -2-fluoro-2-methyldecanoyloxy) phenyl] pyrimidine (63 mg, 61%). Colorless powder Phase transition temperature Cr 117 ℃ SmC ^* 125 ℃ Iso IR (KBr) 2920, 2850, 1765, 1580, 1530, 1430, 1370,
1200, 1165, 1120, 1095, 850, 790 cm ^{-1 1} H NMR (CDCl ₃ ) δ 0.88 (t, J = 6.9 Hz, 3 H), 0.89
(t, J = 7.1 Hz, 3 H), 1.22-1.75 (m, 22 H), 1.75
(d, J = 21.1 Hz, 3 H), 1.78-2.15 (m, 4 H), 2.78 (d
dd, J = 9.1, 9.3, and 13.9 Hz, 1 H), 2.91 (ddd, J
= 5.3, 9.9, and 13.9 Hz, 1 H), 4.51 (dm, J = 49.3
Hz, 1 H), 7.28 (d, J = 8.6 Hz, 2 H), 7.35 (d, J =
8.3 Hz, 2 H), 7.66 (d, J = 8.6 Hz, 2 H), 8.41 (d,
J = 8.3 Hz, 2 H), 8.99 (s, 2 H) MS (m / z) 579 (M ⁺ +1, 38), 578 (M ⁺ , 100), 559 (23),
558 (56), 448 (43), 447 (65), 393 (31), 392 (97),
372 (21), 275 (23), 274 (12), 262 (38), 261 (73), 2
60 (14), 83 (11), 55 (11)

Example 6 2- [4-((S) -3-fluorononyl) phenyl] -5- [4-((S) -2-fluoro-2-methylheptanoyloxy) phenyl] pyrimidine Synthesis of 2- [4-((S)) obtained in Example 1 in the same manner as in Example 5.
3- [3-fluorononyl) phenyl] -5- (4-hydroxyphenyl) pyrimidine and (S) -2-fluoro-2-methylheptanoic acid to give 2- [4-((S) -3-fluorononyl) Phenyl] -5- [4
-((S) -2-Fluoro-2-methylheptanoyloxy) phenyl] pyrimidine was obtained. Colorless powder Phase transition temperature Cr 121 ℃ SmC ^* 127 ℃ Iso IR (KBr) 2920, 2850, 1765, 1580, 1530, 1430, 1370,
1230, 1200, 1165, 1120, 1085, 850, 790 cm- ^{1 1} H NMR (CDCl ₃ ) δ 0.88 (t J = 6.9 Hz, 3 H), 0.93
(t, J = 6.7 Hz, 3 H), 1.24-1.70 (m, 16 H), 1.75 (d,
J = 21.2 Hz, 3 H), 1.70-2.22 (m, 4 H), 2.77 (ddd,
J = 7.2, 9.0, and 13.9 Hz, 1 H), 2.92 (ddd, J =
5.4, 9.5, and 13.9 Hz, 1 H), 4.51 (dm, J = 4902 H
z, 1 H), 7.28 (d, J = 8.7 Jx, 2 H), 7.35 (d, J =
8.3 Hz, 2 H), 7.66 (d, J = 8.7 Hz, 2 H), 8.41 (d,
J = 8.3 Hz, 2 H), 8.99 (s, 2 H) MS (m / z) 537 (M ⁺ +1, 39), 536 (M ⁺ , 100), 516 (24),
406 (21), 405 (91), 275 (20), 262 (32), 261 (59),
260 (14), 97 (12), 55 (33)

[0037] (Example 7) 2- [4 - (( S) -3- fluorophenyl heptyl) phenyl] -5- [4 - ((S ) -2- fluoro-2-methyl De
Kanoiru oxy) By the same method as in Example 5 phenyl] pyrimidine obtained in Example 3 2- [4 - ((S )
3- [3-fluoroheptyl) phenyl] -5- (4-hydroxyphenyl) pyrimidine and (S) -2-fluoro-2-methyldecanoic acid to give 2- [4-((S) -3-fluoroheptyl) phenyl ]-Five-
[4-((S) -2-Fluoro-2- methyldecanoyloxy ) phenyl] pyrimidine was obtained. Colorless powder Phase transition temperature Cr 116 ℃ SmC ^* 122 ℃ Iso IR (KBr) 2920, 2850, 1770, 1580, 1530, 1435, 1375,
1200, 1165, 1120, 995, 855, 790 cm ^{-1 1} H NMR (CDCl ₃ ) δ 0.89 (t, J = 6.9 Hz, 3 H), 0.91
(t, J = 6.7 Hz, 3 H), 1.25-1.76 (m, 18 H), 1.75
(d, J = 21.2 Hz, 3 H), 1.78-2.25 (m, 4 H), 2.78 (d
dd, J = 7.3, 9.0, and 13.9 Hz, 1 H), 2.92 (ddd, J
= 5.6, 9.6, and 13.9 Hz, 1 H), 4.51 (dm, J = 49.2
Hz, 1 H), 7.28 (d, J = 8.7 Hz, 2 H), 7.36 (d, J =
8.3 Hz, 2 H), 7.66 (d, J = 8.7 Hz, 2 H), 8.41 (d,
J = 8.3 Hz, 2 H), 8.99 (s, 2 H) MS (m / z) 551 (M ⁺ +1, 25), 550 (M ⁺ , 62), 530 (13), 4
47 (19), 365 (28), 364 (100), 262 (19), 260 (40), 5
5 (11)

Example 8 Evaluation Example of Spontaneous Polarization and Response Speed 2- [4-((S) -3-fluorononyl) phenyl] -5- [4-((S)- 2-fluoro-2-methyldecanoyloxy) phenyl] pyrimidine was injected into a 3 μm thick cell with a transparent electrode coated with polyimide and rubbed, and a triangular wave of 30 Vp-p, 1 Hz was applied. When the spontaneous polarization was measured, it showed a value of -820 nC / cm ² at 120 ° C.

Next, a liquid crystal composition A (C) comprising 5-alkyl-2- (4-alkoxyphenyl) pyrimidine shown in Table 1 below
r 1 ℃ SmC 50 ℃ SmA 65 ℃ N 68 ℃ Iso), 2- [4-
5% by weight of ((S) -3-fluorononyl) phenyl] -5- [4-((S) -2-fluoro-2-methyldecanoyloxy) phenyl] pyrimidine was added to obtain a liquid crystal composition B. . The phase transition temperature of this liquid crystal composition B is SmC ^* 51 ° C SmA 68 ° C N ^* 69 ° C Iso
Met. Further, the liquid crystal composition B was injected into a 2.8 μm-thick cell with a transparent electrode coated with polyimide and subjected to a rubbing treatment, and a spontaneous polarization was measured by applying a 28 Vp-p, 100 Hz triangular wave. At 25 ° C., the value of −6.1 nC / cm ² . At that time, the response time τ (0-90) was 62.5 μs, and the tilt angle was 19.1 °.

[0040]

[Table 1]

Reference Example 2- (4-hexyloxyphenyl)
-5- [4-((S) -2-fluoro-2-methyldecanoyloxy) phenyl] pyrimidine was injected into a 3 μm-thick cell with a transparent electrode that had been coated with polyimide and rubbed, and 30
When a spontaneous polarization was measured by applying a Vp-p, 100 Hz triangular wave, it showed a value of −333 nC / cm ² at 120 ° C.

Next, a liquid crystal composition A (Cr 1 ° C. Sm) of Table 1 comprising 5-alkyl-2- (4-alkoxyphenyl) pyrimidine
5% by weight of 2- (4-hexyloxyphenyl) -5- [4-((S) -2-fluoro-2-methyldecanoyloxy) phenyl] pyrimidine in C 50 ° C SmA 65 ° C N 68 ° C Iso) % To give a liquid crystal composition C. The phase transition temperature of this liquid crystal composition C is S
mC ^* 54 ° C SmA 68 ° C N ^* 70 ° C Iso. The liquid crystal composition C was injected into a 2.8 μm-thick cell with a transparent electrode coated with polyimide and subjected to rubbing treatment, and was subjected to 28 Vp-p, 100 Hz.
When the spontaneous polarization was measured by applying a triangular wave of
Showed a value of −4.3 nC / cm ² . The response time τ (0
-90) was 170 μs, and the tilt angle was 21.4 °.

Comparing the evaluation results described in Example 8 and Reference Example above, the compound 2- [4-((S) -3-fluorononyl) phenyl]-of Example 5 represented by the general formula (I) was obtained. 5- [4-
((S) -2-fluoro-2-methyldecanoyloxy) phenyl] pyrimidine is 2- (4-hexyloxyphenyl) -5- [4-((S) -2-fluoro-2- Methyldecanoyloxy) phenyl] pyrimidine is shown to exhibit even higher spontaneous polarization. Concomitantly, the liquid crystal composition B has a higher spontaneous polarization than the liquid crystal composition C in the comparison between the liquid crystal composition B and the liquid crystal composition C in which these compounds are added to the liquid crystal composition A of the base liquid crystal. Indicates that
It can be seen that the value is in a range suitable for application to a liquid crystal display element and the like, and the obtained tilt angle is also in a proper range. Further, regarding the high-speed response, it can be seen that the liquid crystal composition B can respond more quickly than the liquid crystal composition C.

All compounds exhibit a stable chimeric smectic C phase in a wide temperature range near room temperature when a liquid crystal composition is prepared. As shown in the general formula (I),
It can be seen that the compound represented by the formula shows a chimeric smectic C phase in a wider temperature range than the compound shown in the reference example. In addition, in terms of chemical stability, the stability of each compound is sufficiently high. In general, the 3-fluoroalkyl group of the compound represented by the general formula (I) is different from the compound represented by the reference example. Than an alkyloxy group,
It is believed to provide higher stability.

[0045]

The optically active diphenylpyrimidine compound of the present invention exhibits a stable chiral smectic C phase and a large spontaneous polarization. In particular, when added to a base liquid crystal, an appropriate spontaneous polarization and tilt angle are induced. Thus, it is possible to provide a ferroelectric liquid crystal composition which responds at high speed. Ferroelectric liquid crystal compositions that combine these excellent properties are used as materials for optoelectronics-related devices that use liquid crystals and electochemism, such as optical printer heads, optical Fourier transform elements, and light valves for displays such as liquid crystal televisions. Useful.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor, Tanijiro Hiyama, 4-29-3-101, Kamizuruma, Sagamihara-shi, Kanagawa (72) Inventor, Atsushi Yoshizawa 3-35-3 Nishinaminami, Toda-shi, Saitama Japan Japan Co., Ltd. Inside Energy (72) Inventor Noriko Ise 3--17-35 Niisonanami, Toda City, Saitama Japan Inside Energy Co., Ltd.

Claims (4)

[Claims] 1. A compound of the general formula (I): (Wherein m represents an integer of 1 to 16, n represents an integer of 2 to 16, and C ^* represents an optically active asymmetric carbon). 2. A compound of the general formula (II): (Wherein m represents an integer of 1 to 16 and C ^* represents an optically active asymmetric carbon), and a phenol derivative of the general formula (IV): (Wherein n represents an integer of 2 to 16, and C ^* represents an optically active asymmetric carbon).
The method for producing an optically active diphenylpyrimidine compound represented by the general formula (I) according to claim 1, wherein -methylalkanoic acid is condensed. 3. A compound of the general formula (II): (Wherein m represents an integer of 1 to 16, and C ^* represents an optically active asymmetric carbon). 4. A liquid crystal composition comprising the optically active diphenylpyrimidine compound represented by the general formula (I) according to claim 1.