JPH08165258A - Aromatic compound, production method and use thereof - Google Patents

Abstract

(57) [Abstract] [Purpose] To provide a liquid crystal compound. [Structure] General formula (1) (R represents hydrogen, fluorine, trifluoromethyl, trifluoromethoxy, cyano, an alkoxyalkyl group, etc.,
m is 0 or 1. R ² represents alkyl, alkenyl, alkynyl, alkoxyalkyl, hydrogen or fluorine.
A ¹ , A ² and A ³ represent phenyl, pyrimidyl and the like. ) An aromatic compound represented by.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an aromatic compound useful as a liquid crystal compound and a method for producing the same.

[0002]

2. Description of the Related Art At present, a TN (twisted nematic) type display system is most widely used as a liquid crystal display device.
This TN liquid crystal display has many advantages such as low driving voltage and low power consumption. However, in terms of response speed, it is inferior to light emitting display devices such as cathode-ray tubes, electroluminescence, and plasma displays. Although a new TN type display device having a twist angle of 180 to 270 ° has been developed, the response speed is still insufficient. In this way, various improvements have been made,
A TN type display element having a fast response speed has not been realized yet.
However, in a new display method using a ferroelectric liquid crystal, which has been actively researched recently, there is a possibility of significant improvement in response speed (Clark et al .; Applied. Ph.
ys. Lett., 36, 899 (1980)). This method is a chiral smectic C phase (hereinafter referred to as Sc *) that exhibits ferroelectricity.
It is a method of utilizing a chiral smectic phase such as. It is known that not only the Sc * phase but also the chiral smectic F, G, H, I phases exhibit ferroelectricity. Although many properties are required for the ferroelectric liquid crystal material used for the ferroelectric liquid crystal device actually used, at present, one compound cannot meet the requirements, and some properties are required. It is necessary to use a ferroelectric liquid crystal composition obtained by mixing a liquid crystal compound or a non-liquid crystal compound. Further, not only a ferroelectric liquid crystal composition consisting of a ferroelectric liquid crystal compound, but also JP-A-61-195
No. 187 discloses non-chiral smectic C, F,
A compound and a composition exhibiting a phase such as G, H, and I (hereinafter, abbreviated as a phase such as Sc) are used as a basic substance, and one or more ferroelectric liquid crystal compounds are mixed with the basic substance to obtain a ferroelectric property. It is reported to be obtained as a liquid crystal composition. Further S
There is also a report that a compound or composition exhibiting a phase such as c is used as a basic substance and one or more compounds that are optically active but do not exhibit a ferroelectric liquid crystal phase are mixed to form a ferroelectric liquid crystal composition as a whole. Seen (Mol. Cryst. Liq. Cry
st., 89, 327 (1982)). Collectively, it is understood that the ferroelectric liquid crystal composition can be formed by using one or more optically active compounds as a basic substance regardless of whether or not it exhibits a ferroelectric liquid crystal phase. However, conventionally known optically active substances have sufficient spontaneous polarization,
In addition, it is difficult to say that it is a low-viscosity material that can respond at high speed.

[0003]

In recent years, the use of liquid crystals has increased, and the development of liquid crystals having a new structure has been required. An object of the present invention is to provide an optically active compound useful as a low-viscosity liquid crystal material having sufficient spontaneous polarization and capable of responding at high speed and a component thereof, and a method for producing the same.

[0004]

Means for Solving the Problems The present inventors have
As a result of extensive studies to solve the above problem, the present invention has been achieved.
That is, the present invention has the general formula (1)(In the formula, R is a hydrogen atom, a fluorine atom, or trifluoromethyi.
Group, trifluoromethoxy group, cyano group, halogen atom
Saturated with 2 to 15 carbon atoms which may be substituted with
Unsaturated alkoxyalkyl group, 4-R¹− (Cycloa
Rukiru) group, 4-R¹A-(cycloalkenyl) group or
R¹-(O) m-, where R¹Is a halogen atom
A branched or straight-chain carbon atom which may be substituted with
15 alkyl, alkenyl or alkynyl groups
Indicated, m is 0 or 1. R ²Is a halogen atom
A branched or straight chain having 1 to 15 carbon atoms which may be substituted.
An alkyl group having 1 to 15 carbon atoms in the chain, an alkenyl group, or
Alkynyl group, charcoal optionally substituted with halogen atom
Saturated or unsaturated alkoxy alk having a prime number of 2 to 15
Group, hydrogen atom or fluorine atom. A¹, A²,
A³RespectivelyIndicates A¹Is a fused ring, p + q is 0 or 1.
Yes and A², A³Is a monocycle. A¹Is a monocycle
Then p + q is 1 or 2 and A when p + q is 2 ², A
³Are all monocyclic. Z is a fluorine atom or hydrogen atom
A child, p and q each represent 0 or 1, and u
And w each represent an integer of 0 to 3. Where R²But
C1-C15 which may be substituted with a halogen atom
A branched or straight chain alkyl group having 1 to 15 carbon atoms,
Substituted with a alkenyl or alkynyl group, halogen atom
Optionally saturated or unsaturated carbon atoms of 2 to 15
Rucoxyalkyl group or hydrogen atom, and R is a group
 R¹When-(O) m- is shown, A¹-(A²)_p−
(A³)_qBipheni whose benzene ring is entirely unsubstituted
Le, terphenyl, 2,6-naphthyl, pyrimidine-2
-Yl-phenyl, pyrimidin-5-yl-phenyl
There is no. ) An aromatic compound represented by
To provide.

The present invention will be described in detail below.
The compound represented by the general formula (1) has the general formula (2): (In the formula, R, A ¹ , A ² , A ³ , Z, p and q have the same meanings as described above.) And a general formula (4) R ² COR ″ (4) (formula Where R ² has the same meaning as described above, R ″ is a hydroxyl group,
Indicates OCOR ² or a halogen atom. The aromatic compound (1) (s is 1, t is 1) is obtained by reacting with a carboxylic acid represented by the formula (1). Or an alcohol compound (2) and the general formula (5) R ² —Y (5) (wherein R ² has the same meaning as described above, and Y represents a halogen atom or —SO ₂ R ″ ′, where R 2 "" Represents a lower alkyl group or an optionally substituted phenyl group.)
The aromatic compound (1) (s is 1, t is 0) can be obtained by reacting with an alkylating agent represented by. Further, a fluorinating agent is allowed to act on the alcohol compound (2) to fluorinate it, whereby the fluorine compound (3) can be obtained.

The alcohol compound (2) as a raw material can be produced by the following method.

First, the reaction between the alcohol compound represented by the general formula (2) and the carboxylic acid represented by the general formula (4) will be described. In the reaction of the alcohol compound (2) with the carboxylic acid (4), as the carboxylic acid (4), a carboxylic acid represented by R ² , an acid anhydride or acid chloride thereof, or an acid halide such as an acid bromide is used. To be done. Incidentally, these carboxylic acids (4) may be either a racemic body or an optically active body. When a solvent is used in the above reaction, examples of the solvent include tetrahydrofuran, ethyl ether, acetone,
Reaction of methyl ethyl ketone, toluene, benzene, chlorobenzene, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, dimethylformamide, hexane and other ethers, ketones, aliphatic or aromatic hydrocarbons, halogenated hydrocarbons, aprotic polar solvents, etc. Examples of the solvent include inert solvents, which may be used alone or as a mixture. The amount used is not particularly limited.

In the above reaction, when an acid anhydride or acid halide of an aliphatic carboxylic acid is used, the amount used is required to be at least 1 equivalent times the alcohol compound (2), and the upper limit is particularly limited. However, it is preferably 1.1 to 4 equivalent times.

A catalyst can be used in the above reaction, and examples of such a catalyst include dimethylaminopyridine,
4-pyrrolidinopyridine, triethylamine, tree n
-Butylamine, pyridine, collidine, imidazole,
Organic or inorganic basic substances such as sodium carbonate, sodium methylate, potassium hydrogen carbonate and the like can be mentioned. Further, an organic acid or an inorganic acid such as toluenesulfonic acid, methanesulfonic acid or sulfuric acid may be used as a catalyst. When using such a catalyst, for example, pyridine when an acid halide of a carboxylic acid is used as a raw material,
Triethylamine is preferably used. The amount of the catalyst used varies depending on the combination of the acid anhydride or acid halide of the carboxylic acid and the catalyst used, and is not necessarily specified. For example, when an acid halide is used, it is 1 equivalent times the acid halide. That is all.

When a carboxylic acid is used in the above reaction, the carboxylic acid is usually used in the presence of a condensing agent in an amount of 1 to 2 equivalents with respect to the alcohol compound (2) for dehydration condensation. Obtainable. As the condensing agent, carbodiimides such as N, N'-dicyclohexylcarbodiimide and N-cyclohexyl-N '-(4-diethylamino) cyclohexylcarbodiimide are preferably used, and if necessary, 4-dimethylaminopyridine, 4-pyrrolidino An organic base such as pyridine, pyridine or triethylamine is used in combination.
The amount of the condensing agent used is 1 to 1.5 equivalent times that of the carboxylic acid. When the organic base is used in combination, the amount of the condensing agent used is 0.01 to 0.2 equivalent times that of the condensing agent. is there.
The reaction temperature is usually -30 to 100 ° C, preferably -10 to 80 ° C. The reaction time is not particularly limited,
The time point when the raw material (2) disappears can be the end point of the reaction. After completion of the reaction, the aromatic compound (1) (provided that s = 1, t = 1) can be obtained in good yield by an ordinary separation means such as extraction, liquid separation, concentration, etc. It can also be purified by column chromatography, recrystallization and the like depending on the case.

Next, in the reaction of the alcohol compound (2) with the alkylating agent represented by the general formula (5), the alkylating agent used is a halogenated or sulfonated ester having a substituent R ² . It can be produced from the corresponding alcohol by a known method. The substituent R ² in the alkylating agent may be an optically active substance. The amount of the alkylating agent used is
The alcohol compound (2) may be optionally added in an amount of 1 equivalent or more, but is usually in the range of 1 to 5 equivalents.

The above reaction is usually carried out in the presence of a solvent,
Examples of the solvent used include tetrahydrofuran, ethyl ether, acetone, methyl ethyl ketone,
Toluene, benzene, chlorobenzene, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, hexane, dimethylformamide, dimethyl sulfoxide,
Hexamethylphosphorylamide, ethers such as N-methylpyrrolidone, ketones, aliphatic or aromatic hydrocarbons, halogenated hydrocarbons, aprotic polar solvents, and other solvents inert to the reaction may be used alone or as a mixture.
The amount of the solvent used is not particularly limited.

The above reaction is usually carried out in the presence of a basic substance. Examples of the basic substance include alkali metal hydrides such as sodium hydride and potassium hydride, alkali metal alkoxides such as lithium, sodium and potassium, alkali metal alcoholates such as sodium ethylate and sodium methylate, sodium carbonate and potassium carbonate. Alkali metal carbonates such as butyllithium, etc. The basic substance is required to be 1 equivalent times or more with respect to the alcohol compound (2), and the upper limit is not particularly limited, but it is usually 1.1 to 5 equivalent times. The reaction temperature is generally -50 to 120 ° C, preferably -30 to 100 ° C. The reaction time is not particularly limited, and the reaction can be terminated when the starting alcohol compound (2) disappears. After completion of the reaction, the desired aromatic compound represented by the general formula (1) can be isolated from the reaction mixture by a usual separation means, for example, operations such as extraction, liquid separation, concentration, etc. It can also be purified by chromatography, recrystallization and the like.

In the above alkylation reaction, when the substituent Y of the alkylating agent is an iodine atom, silver oxide may be used instead of the basic substance.
In this case, the silver oxide is the alcohol compound (2).
However, the upper limit is not particularly limited, but it is preferably 5 equivalents or more. When the alkylation reaction is carried out in the presence of silver oxide, the amount of the alkylating agent (provided that the substituent Y is an iodine atom) is arbitrarily 1 equivalent or more with respect to the raw material (2), but preferably, It is 2 to 10 equivalent times.

As a reaction solvent, an excess of an alkylating agent (provided that the substituent is an iodine atom) can be used as a solvent, and tetrahydrofuran, ethyl ether, dioxane, acetone, methyl ethyl ketone, benzene,
Solvents inert to the reaction such as ethers such as toluene and hexane, ketones, or hydrocarbon solvents may be used alone or as a mixture. The reaction temperature is usually 0 to 150 ° C,
It is preferably in the range of 20 to 100 ° C. The reaction time is usually 1 hour to 20 days. The aromatic compound (1) is taken out from the reaction mixture by removing the silver salt by filtration and then adding a usual post-treatment operation such as extraction, liquid separation, and concentration. If necessary, it can be purified by column chromatography or the like.

The method for obtaining the aromatic compound (1) from the alcohol compound (2) has been described above. The carboxylic acids (4) and the substituent R ² in the alkylating agent (5) used here are as follows. The thing is illustrated. Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, heptyl,
Octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, propenyl, 2-butenyl, 3-butenyl, 3-hexenyl, 2-butynyl, 3-hexynyl, cyclopropyl, 2,2-dimethylcyclopropyl, cyclope Methyl, cyclohexyl, octadecyl,
Nonadecyl, eicosyl, methoxymethyl, methoxyethyl, methoxypropyl, methoxybutyl, methoxypentyl, methoxyhexyl, methoxyheptyl, methoxyoctyl, methoxynonyl, methoxydecyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, ethoxypentyl, ethoxyhexyl. , Ethoxyheptyl, ethoxyoctyl, ethoxynonyl, ethoxydecyl, propoxymethyl, propoxyethyl, propoxypropyl, propoxybutyl, propoxypentyl, propoxyhexyl, propoxyheptyl, propoxyoctyl, propoxynonyl, propoxydecyl, butoxybutoxymethyl, butoxyethyl, Butoxypropyl, butoxybutyl, butoxypentyl, butoxyhexyl, but Shihepuchiru, butoxyethanol octyl,
Butoxynonyl, butoxydecyl, pentyloxymethyl, pentyloxyethyl, pentyloxypropyl, pentyloxybutyl, pentyloxypentyl,
Pentyloxyhexyl, Pentyloxyoctyl, Pentyloxynonyl, Pentyloxydecyl, Hexyloxymethyl, Hexyloxyethyl, Hexyloxypropyl, Hexyloxybutyl, Hexyloxypentyl, Hexyloxyhexyl, Hexyloxyheptyl, Hexyloxyoctyl, Hexyloxy Nonyl,
Hexyloxydecyl, heptyloxymethyl, heptyloxyethyl, heptyloxypropyl, heptyloxybutyl, heptyloxypentyl, heptyloxyhexyl, heptyloxyheptyl, heptyloxyoctyl, heptyloxynonyl, heptyloxydecyl, octyloxymethyl, octyloxymethyl Ethyl, octyloxypropyl, octyloxybutyl, octyloxypentyl, octyloxyhexyl, octyloxyheptyl, octyloxynonyl, octyloxyoctyl, decyloxymethyl, decyloxyethyl, decyloxypropyl, decyloxybutyl, decyloxypentyl, Decyloxyhexyl, decyloxyheptyl, 1-methylethyl, 1-methylpropyl,
1-methylbutyl, 1-methylpentyl, 1-methylhexyl, 1-methylheptyl, 1-methyloctyl, 1
-Methylnonyl, 1-methyldecyl, 2-methylpropyl, 2-methylbutyl, 2-methylpentyl, 2-methylhexyl, 2-methylheptyl, 2-methyloctyl, 2,3-dimethylbutyl, 2,3,3-trimethylbutyl, 3-methylpentyl, 2,3-dimethylpentyl, 2,4 -Dimethylpentyl, 2,3,3,4-tetramethylpentyl, 3-methylhexyl, 2,5-dimethylhexyl, 2-trihalomethylpropyl, 2-trihalomethylbutyl, 2-trihalomethylpentyl, 2-trihalomethylhexyl, 2-trihalomethylheptyl, 2-haloethyl, 2-halopropyl, 3-halopropyl, 3-halo-2-methylpropyl, 2,3-dihalopropyl, 2-halobutyl, 3-halobutyl, 4-halobutyl, 2,3-diha Robutyl, 2,4-dihalobutyl, 3,4-dihalobutyl, 2-halo 3-methylbutyl, 2-halo 3,3-dimethylbutyl, 2-halopentyl, 3-halopentyl, 4-halopentyl, 5-halopentyl, 2,4-dihalopentyl, 2,5-dihalopentyl, 2-halo-3-methylpentyl 2-Hello 4
-Methyl pentyl, 2-Halo 3-Monohalomethyl-4
-Methylpentyl, 2-halohexyl, 3-halohexyl, 4-halohexyl, 5-halohexyl, 6-halohexyl, 2-haloheptyl, 2-halooctyl (however, in the above exemplification, halo represents fluorine, chlorine or bromine) and the like.

Examples of the carboxylic acids include halomethyl, 1-haloethyl, 1-halopropyl, 1-halobutyl, 1-halopentyl, 1-halohexyl, 1-haloheptyl, 1-halooctyl and the like in addition to the above-mentioned examples. These alkyl groups or alkoxyalkyl groups are linear, branched or cyclic, and when branched or cyclic, they may be optically active groups. Substituent R exemplified above
Among the carboxylic acids having ² , the optically active ones are
Obtained by oxidation of the corresponding alcohols, reductive deamination of amino acids, and some can be derived from optically active amino acids and optically active oxyacids, such as the following, either naturally occurring or obtained by resolution: . An optically active alkylating agent having a substituent R ² can be easily produced from a corresponding alcohol by a known method. Some of the alcohols are asymmetric metal catalysts of corresponding ketones or Obtained by asymmetric reduction with microorganisms or oxygen. Also, some can be derived from naturally occurring or optically active amino acids or optically active oxyacids obtained by optical resolution, such as: Alanine, valine, leucine,
Isoleucine, phenylalanine, threonine, arosreonine, homoserine, alloisoleucine, tert-leucine, 2-aminobutyric acid, norvaline, norleucine, ornithine, lysine, hydroxylysine, phenylglycine, aspartic acid, glutamic acid, mandelic acid, tropic acid, 3-hydroxyl. Butyric acid, malic acid, tartaric acid or isopropylmalic acid etc.

Further, the alcohol compound (2) can be converted into the fluorinated aromatic compound (1) by substituting a fluorine atom for a hydroxyl group using a fluorinating agent. Examples of the fluorinating agent to be used include hydrogen fluoride, its complex compounds, sulfur fluoride compounds, fluorinated olefins, and the like. Specifically, hydrogen fluoride-pyridine, hydrogen fluoride-triethylamine, sulfur tetrafluoride, Diethylamino sulfur trifluoride (DAST), morpholino sulfur trifluoride (mor
ph-DAST), 2-chloro-1,1,2-trifluoroethylene, hexafluoropropene and the like. These can be used alone, in a mixture, or in combination with diethylamine, diisopropylamine and morpholine. In the reaction between the alcohol compound represented by the general formula (2) and the fluorinating agent, the amount of the fluorinating agent used is
It is usually 1.0 to 5 equivalent times, preferably 1.0 to 2 equivalent times, relative to the alcohol. In addition, a solvent is usually used in this reaction, and it is preferable to use halogenated hydrocarbons or hydrocarbons. Specifically, hexane, benzene, toluene, dichloromethane, dichloroethane,
Use chlorobenzene etc. alone or in a mixture. The amount of these reaction solvents used is not particularly limited. The reaction temperature of this reaction is usually -70 to 100 ° C, preferably -40 to 50 ° C. After completion of the reaction, extraction,
The fluorinated aromatic compound (1) can be obtained by a usual post-treatment method such as distillation, recrystallization and column chromatography.

Specific examples of the compound (1) thus obtained include the following. 4 ″ -alkyl-4- (α-fluoroethyl) -p-terphenyl, 4 ″ -alkyloxy-4- (α-fluoroethyl) -p-terphenyl, 6-alkyl-2- {4- (α-fluoroethyl) -phenyl} naphthalene, 6-alkyloxy-2- { 4- (α-fluoroethyl) -phenyl} naphthalene, 6- (4-alkylphenyl)
-2- (α-Fluoroethyl) naphthalene, 6- (4-alkyloxyphenyl) -2- (α-fluoroethyl) naphthalene, 5-alkyl- {4- (α-fluoroethyl) -phenyl} pyridine, 5-alkyloxy- {4- (α-fluoroethyl) ) -Phenyl} pyridine,
2- (4-alkylphenyl) -5- (α-fluoroethyl) pyridine, 2- (4-alkyloxyphenyl)
-5- (α-Fluoroethyl) pyridine, 2-alkyl-5- {4- (α-fluoroethyl) -phenyl} pyridine, 2-alkyloxy-5- {4- (α-fluoroethyl) -phenyl} pyridine, 5- (4-alkylphenyl)- 2- (α-fluoroethyl) pyridine, 5- (4-alkyloxyphenyl) -2- (α-fluoroethyl) pyridine, 5-alkyl-2- {4 '-(α-fluoroethyl) -4-biphenylyl} pyridine, 5-alkyloxy-2- {4 '-(α-fluoroethyl)
-4-Biphenylyl} pyridine, 2- (4'-alkyl-4-biphenylyl) -5- (α-fluoroethyl) pyridine, 2- (4'-alkyloxy-4-biphenylyl) -5- (α-fluoroethyl) pyridine, 5- (4
-Alkylphenyl) -2- {4- (α-fluoroethyl) phenyl} pyridine, 5- (4-alkyloxyphenyl) -2- {4- (α-fluoroethyl) phenyl} pyridine, 2- (4-alkylphenyl)- 5- {4- (α-fluoroethyl) phenyl} pyridine, 2
-(4-alkyloxyphenyl) -5- {4- (α-fluoroethyl) phenyl} pyridine, 5-alkyl- {4- (α-fluoroethyl) -phenyl} pyrimidine, 5-alkyloxy- {4- (α-fluoroethyl) -phenyl} pyrimidine, 2- (4-alkylphenyl) -5- (α-fluoroethyl) pyrimidine, 2- (4-alkyloxyphenyl) -5- (α-fluoroethyl) pyrimidine, 2-alkyl-5- {4- (α-fluoroethyl) -phenyl} pyrimidine, 2-Alkyloxy-5- {4- (α-fluoroethyl) -phenyl} pyrimidine, 5- (4-alkylphenyl) -2- (α-fluoroethyl) pyrimidine, 5- (4-alkyloxyphenyl) -2- (α-fluoroethyl) Pyrimidine, 5-alkyl-2- α-Fluoroethyl) -4-biphenylyl} pyrimidine, 5-alkyloxy-2- {4 ′-(α-fluoroethyl) -4-biphenylyl} pyrimidine, 2- (4′-alkyl-4-biphenylyl) -5- (α-fluoroethyl) pyrimidine, 2- ( 4′-alkyloxy-4-biphenylyl) -5- (α-fluoroethyl) pyrimidine, 5- (4-alkylphenyl) -2- {4- (α-fluoroethyl) phenyl} pyrimidine, 5- (4-alkyloxyphenyl) -2 -{4- (α-Fluoroethyl) phenyl} pyrimidine, 2- (4-alkylphenyl) -5- {4- (α-fluoroethyl) phenyl} pyrimidine, 2- (4-alkyloxyphenyl) -5- {4- ( α-Fluoroethyl) phenyl} pyrimidine, 5-alkyl- {4- ( Over fluoroethyl) Feniru} pyrazine,
5-alkyloxy- {4- (α-fluoroethyl) -phenyl} pyrazine, 2- (4-alkylphenyl) -5- (α-fluoroethyl) pyrazine, 2- (4-alkyloxyphenyl) -5- (α-fluoroethyl) pyrazine, 5-alkyl-2- {4 '-(α-fluoroethyl) -4-biphenylyl} pyrazine, 5-alkyloxy-2- {4'-(α-fluoroethyl) -4-biphenylyl} pyrazine, 2- (4'-alkyl-4-biphenylyl) -5- (Α-fluoroethyl) pyrazine, 2
-(4'-Alkyloxy-4-biphenylyl) -5- (α-fluoroethyl) pyrazine, 5- (4-alkylphenyl) -2- {4- (α-fluoroethyl) phenyl} pyrazine, 5- (4-alkyloxyphenyl) -2- {4- (α-fluoroethyl) phenyl} pyrazine, 6- (4-alkylphenyl) -3- {4- (α-fluoroethyl) phenyl} pyridazine, 6- (4-alkyloxyphenyl) -3- {4 -(Α-Fluoroethyl) phenyl} pyridazine, 2- (6-alkylnaphthalene-2-yl) -5- (α-fluoroethyl) pyrimidine, 2- (6-alkyloxynaphthalene-2)
-Yl) -5- (α-fluoroethyl) pyrimidine, 5
-(6-alkyl naphthalene-2-yl) -2- (α
-Fluoroethyl) pyrimidine, 5- (6-alkyloxynaphthalen-2-yl) -2- (α-fluoroethyl) pyrimidine, 2-alkyl-5- {6- (α-fluoroethyl) naphthalen-2-yl) pyrimidine,
2-Alkyloxy-5- {6- (α-fluoroethyl) naphthalene-2-yl) pyrimidine, 5-alkyl-2- {6- (α-fluoroethyl) naphthalen-1-yl} pyrimidine, 5-alkyloxy-2- {6
-(Α-Fluoroethyl) naphthalene-1-yl} pyrimidine, 7-alkyl-3- {4- (α-fluoroethyl) -phenyl} isoquinoline, 7-alkyloxy-3- {4- (α-fluoroethyl) -phenyl} isoquinoline, 3- (4-alkyl- Phenyl) -7- (α
-Fluoroethyl) isoquinoline, 3- (4-alkyloxy-phenyl) -7- (α-fluoroethyl) isoquinoline, 6-alkyl-2- {4- (α-fluoroethyl) phenyl} quinoline, 6-alkyloxy-2- {4- (α-fluoroethyl) Phenyl} quinoline, 2
-(4-alkyl-phenyl) -6- (α-fluoroethyl) quinoline, 2- (4-alkyloxy-phenyl) -6- (α-fluoroethyl) quinoline, 3-alkyl-7- {4- (α-fluoroethyl) phenyl} quinoxaline, 3-alkyloxy-7- {4- (α-fluoroethyl) phenyl} quinoxaline, 2-alkyloxy-6- {4- (α-fluoroethyl) phenyl}
Quinazoline, 4′-alkyl-4- (α-fluoroethyl) -biphenyl, 4 ″ -alkyloxy-4- (α-fluoroethyl) -biphenyl, and compounds in which the phenyl group in the above compounds is substituted with 1 to 3 fluorine atoms. The above α-fluoro group is replaced with an alkyloxy group or an alkylcarbonyloxy group.

Further, in the above compounds, the alkyl group, alkyloxy group, and alkylcarbonyloxy substituted with a halogen atom, and the alkenyl group and alkenyloxy group which may be substituted with halogen, respectively, have been replaced. It is a compound. Here, alkyl and alkenyl represent an alkyl group having 1 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms. Examples of such substituents include propyl, butyl, pentyl,
Hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl,
Decenyl, undecenyl, dodecenyl, methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, pentyloxymethyl, hexyloxymethyl, heptyloxymethyl, octyloxymethyl, nonyloxymethyl, decyloxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl. , Butoxyethyl, pentyloxyethyl, hexyloxyethyl, heptyloxyethyl, octyloxyethyl, nonyloxyethyl, decyloxyethylmethoxypropyl, ethoxypropyl, propoxypropyl, butoxypropyl, pentyloxypropyl, hexyloxypropyl, heptyloxypropyl , Octyloxypropyl, nonyloxypropyl, decyloxypropylmethoxybutyl, ethoxybutyl, Ropoxybutyl, butoxybutyl, pentyloxybutyl, hexyloxybutyl, heptyloxybutyl, octyloxybutyl, nonyloxybutyl, decyloxybutylmethoxypentyl, ethoxypentyl, propoxypentyl, butoxypentyl, pentyloxypentyl, hexyloxypentyl, heptyloxy. Examples thereof include pentyl, octyloxypentyl, and halogen-substituted compounds.

[0021]

The compound of the present invention is a low-viscosity liquid crystal material,
Not only useful as a chiral dopant, but also a pesticide,
It can also be used in the field of medicine. Further, according to the method of the present invention, the optically active compound (1) can be industrially advantageously produced.

[0022]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

Reference Example 1 (2-Acetylnaphthalen-6-yl) amidine hydrochloride 7.9 g (32 mmol), β-dimethylamino-α
7.8 g (40 mmol) of decyloxyacrolein, 11.4 g of 20% sodium ethoxide and 120 g of ethanol were charged, and the mixture was reacted at 80 ° C. for 7 hours. After completion of the reaction, the reaction mixture was poured into ethyl acetate-water and the layers were separated, and the obtained organic layer was added with 5% hydrochloric acid, water and 5%.
The extract is washed with aqueous sodium hydrogen carbonate and saturated brine and dried over magnesium sulfate. The residue obtained by concentration under reduced pressure is purified by silica gel column chromatography to obtain 8.9 g (yield 68%) of 5-decyloxy-2- (2-acetylnaphthalen-6-yl) pyrimidine. Next, in a solution of 5-decyloxy-2- (2-acetylnaphthalen-6-yl) pyrimidine 8.1 g (20 mmol), tetrahydrofuran 80 ml and ethanol 20 ml, 1.1 g (30) of sodium borohydride was added.
Mmol) at 20 ° C., and the mixture is reacted at the same temperature for 5 hours. After the reaction was completed, the reaction mixture was poured into water, extracted with ethyl acetate, and the organic layer was separated.
Wash with water, 5% aqueous sodium hydrogen carbonate and saturated brine, and dry over magnesium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (eluent: toluene-ethyl acetate) to give 5-decyloxy-
7.7 g (yield 95%) of 2- (2- (1-hydroxyethyl) naphthalen-6-yl) pyrimidine are obtained. Next, 7.3 g of 5-decyloxy-2- (2- (1-hydroxyethyl) naphthalen-6-yl) pyrimidine (1
8 mmol), 5 g of acetic anhydride, and 50 g of pyridine are charged, and the mixture is reacted at 50 ° C. for 4 hours. After completion of the reaction, the reaction solution is poured into 50 ml of water, adjusted to pH 3 with 5% aqueous HCl, and extracted with 100 ml of ethyl acetate. The organic layer is washed with water and then concentrated under reduced pressure to give 5-decyloxy-2- (2
7.8 g (yield 97%) of-(1-acetoxyethyl) naphthalen-6-yl) pyrimidine are obtained. 7.2 g (16 mmol) of 5-decyloxy-2- (2- (1-acetoxyethyl) naphthalen-6-yl) pyrimidine was added to 200 ml of 0.3M phosphate buffer (pH 7.0),
Add to a mixture of 15 ml of chloroform and 2.0 g of Pseudomonas lipase (lipase "P" Amano) and stir vigorously at 30 to 35 ° C for 60 hours. The resulting mixture is extracted with 200 ml of toluene, the organic layer is washed with water and then concentrated under reduced pressure. The residue was separated by silica gel column chromatography (eluent: toluene-ethyl acetate), and (R) -5-decyloxy-2- (2- (1-hydroxyethyl) naphthalen-6-yl) pyrimidine 2.
4 g (yield 37%) [α] _D ²⁰ = -15.2 ° (c =
1, chloroform) and (S) -5-decyloxy-
4.2 g (59% yield) of 2- (2- (1-acetoxyethyl) naphthalen-6-yl) pyrimidine are obtained.

Reference Example 2 4-Acetyl-4'-amidinobiphenyl hydrochloride 8.
8 g (32 mmol), β-dimethylamino-α-decyloxyacrolein 7.8 g (40 mmol), 20
% Sodium ethoxide 11.4 g and ethanol 1
Charge 50 g and react at 80 ° C. for 10 hours. After completion of the reaction, the reaction mixture is poured into ethyl acetate-water and the organic layer is separated, and the obtained organic layer is washed with 5% hydrochloric acid, water, 5% aqueous sodium hydrogen carbonate and saturated brine, and dried over magnesium sulfate. The residue obtained by concentration under reduced pressure is purified by silica gel column chromatography to obtain 9.0 g of 5-decyloxy-2- (4′-acetylbiphenyl-4-yl) pyrimidine (yield 65%). Then, 5-decyloxy-2- (4'-acetylbiphenyl-4-yl) pyrimidine 8.6 g (20 mmol), tetrahydrofuran 80 ml and ethanol 2
Sodium borohydride (1.5 g, 40 mmol) was added to 0 ml of the solution at 20 ° C., and the mixture was reacted at the same temperature for 4 hours. After the reaction was completed, the reaction mixture was poured into water, extracted with ethyl acetate, and the organic layer was separated.
Wash with water, 5% aqueous sodium hydrogen carbonate and saturated brine, and dry over magnesium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (eluent: toluene-ethyl acetate) to give 5-decyloxy-
2- (4 '-(1-hydroxyethyl) biphenyl-4
-8% (yield) pyrimidine (94% yield) is obtained.
Next, 7.8 g of 5-decyloxy-2- (4 '-(1-hydroxyethyl) biphenyl-4-yl) pyrimidine
(18 mmol), 6 g of acetic anhydride, 50 g of pyridine, and 40 g of toluene are charged and reacted at 50 ° C. for 4 hours.
After completion of the reaction, the reaction solution is poured into 50 ml of water, adjusted to pH 3 with 5% aqueous HCl, and extracted with 100 ml of ethyl acetate. The organic layer is washed with water and then concentrated under reduced pressure to obtain 8.2 g (yield 96%) of 5-decyloxy-2- (4 '-(1-acetoxyethyl) biphenyl-4-yl) pyrimidine. 5-decyloxy-2- (4 '-(1-acetoxyethyl) biphenyl-4-yl) pyrimidine 7.6
g (16 mmol) with 0.3 M phosphate buffer (pH
7.0) 200 ml, chloroform 15 ml, and Pseudomonas lipase (lipase "P" Amano) 3.
Add to 0 g of the mixture and stir vigorously at 30-35 ° C. for 60 hours. The resulting mixture is extracted with 200 ml of toluene, the organic layer is washed with water and then concentrated under reduced pressure. The residue was subjected to silica gel column chromatography (eluent: toluene-
(R) -5-decyloxy-2
-(4 '-(1-hydroxyethyl) biphenyl-4-yl) pyrimidine 2,6 g (yield 38%) [α] _D ²⁰ =
-14.4 ° (c = 1, chloroform) and (S)-
4.3 g (yield 57%) of 5-decyloxy-2- (4 '-(1-acetoxyethyl) biphenyl-4-yl) pyrimidine is obtained.

Reference Example 3 4-Acetylphenylamidine hydrochloride 6.4 g (32
Mmol), N- (3- (dimethylamino) -2- (4
-Decyloxyphenyl) -2-propenylidene-methylmethanaminium chloride 18.3 g (40 mmol), 20% sodium ethoxide 11.4 g and ethanol 120 g are charged and reacted at 70 ° C for 8 hours. After completion of the reaction, the reaction mixture was poured into ethyl acetate-water and the layers were separated, and the obtained organic layer was added with 5% hydrochloric acid, water and 5%.
The extract is washed with aqueous sodium hydrogen carbonate and saturated brine and dried over magnesium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography to give 5- (4-decyloxyphenyl) -2- (4-acetylphenyl) pyrimidine 9.8 g (yield 71%).
Get. Next, 5- (4-decyloxyphenyl)-
2- (4-acetylphenyl) pyrimidine 8.6 g
1.5 g of sodium borohydride in a solution of (20 mmol), 50 ml of dichloromethane and 50 ml of ethanol.
(40 mmol) is added at 20 ° C., and the mixture is reacted at the same temperature for 5 hours. After the reaction was completed, the reaction mixture was poured into water, extracted with ethyl acetate, and the organic layer was separated. The obtained organic layer was washed with 5% hydrochloric acid, water, 5% aqueous sodium hydrogen carbonate and saturated brine, and dried over magnesium sulfate. To do. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (eluent: toluene-ethyl acetate) to give 5- (4-decyloxyphenyl) -2- (4- (1-hydroxyethyl) phenyl). 8.1 g (yield 95%) of pyrimidine are obtained. Then, 5- (4-decyloxyphenyl) -2- (4- (1-hydroxyethyl) phenyl) pyrimidine 7.8 g (18 mmol), acetic anhydride 5 g, pyridine 5
Charge 0 g and react at 50 ° C. for 4 hours. After the reaction was completed, the reaction solution was poured into 50 ml of water and pH was adjusted with 5% HCl water.
After setting to 3, extract with 100 ml of ethyl acetate. The organic layer is washed with water and then concentrated under reduced pressure to obtain 8.1 g of 5- (4-decyloxyphenyl) -2- (4- (1-acetoxyethyl) phenyl) pyrimidine (yield 95%). 5- (4-decyloxyphenyl) -2- (4-
(1-acetoxyethyl) phenyl) pyrimidine 7.6
g (16 mmol) with 0.3 M phosphate buffer (pH
7.5) 250 ml, chloroform 15 ml, and
Pseudomonas lipase (lipase "P" Amano)
Add to 3.0 g of the mixture and stir vigorously at 30-35 ° C. for 70 hours. The resulting mixture is 200 ml of toluene
The organic layer is washed with water and then concentrated under reduced pressure. The residue was separated by silica gel column chromatography (eluent: toluene-ethyl acetate), and (R) -5- (4-decyloxyphenyl) -2- (4- (1-hydroxyethyl) phenyl) pyrimidine 2.9 g. (Yield 38%)
[Α] _D ²⁰ = -14.6 ° (c = 1, chloroform) and (S) -5- (4-decyloxyphenyl) -2- (4- (1-acetoxyethyl) phenyl) pyrimidine 4.3 g (Yield 56%) is obtained.

Example 1 1.8 g (5 mM) of (S) -5-decyloxy-2- (4- (1-hydroxyethyl) phenyl) pyrimidine (1-2) was placed in a reactor equipped with a stirrer and a thermometer. And 20 ml of dichloromethane are charged, 1.0 g (6 mM) of diethylamino sulfur trifluoride is added at -50 ° C, and the mixture is stirred for 30 minutes. Then, the reaction mixture is poured into water and extracted with toluene. The organic layer is washed with water and then concentrated under reduced pressure. The obtained residue is purified by silica gel column chromatography (eluent: toluene-hexane) to give (R) -5-decyloxy-2- (4- (1-fluoroethyl) phenyl) pyrimidine (1-1) 1. This gives 0.5 g (yield 86%).
Phase change: K- (34 ° C) -Sc- (74 ° C) -I, clearing point 62 ° C (R) -5-decyloxy-2- (4- (1-fluoro) was carried out in the same manner as in this example. Ethyl) phenyl)
Pyrimidine, (S) -5-decyloxy-2- (4- (1-fluoroethyl) -2-fluorophenyl) pyrimidine, (S) -2-decyloxy-5- (4- (1-
Fluoroethyl) phenyl) pyrimidine, 2-decyloxyphenyl-5- (1-fluoroethyl) pyrimidine, (S) -5-decyloxy-2- (4- (1-fluoroethyl) -3-fluorophenyl) pyrimidine,
(S) -5-decyloxy-2- (4- (1-fluoroethyl) -2-fluorophenyl) pyrimidine, (S)
2-decyloxy-5- (4- (1-fluoroethyl) -3-fluorophenyl) pyrimidine and 5-trifluoromethoxy-2- (4- (1-fluoroethyl) phenyl) pyrimidine can be synthesized. .

Example 2 2.2 g of (R) -5-decyloxy-2- (4 '-(1-hydroxyethyl) biphenyl-4-yl) pyrimidine (2-2) was placed in a reactor equipped with a stirrer and a thermometer. And 40 ml of dichloromethane are charged, 1.0 g of diethylamino sulfur trifluoride is added at -50 ° C, and the mixture is stirred for 30 minutes.
Then, the reaction mixture is poured into water and extracted with toluene. The organic layer is washed with water and then concentrated under reduced pressure. The obtained residue is purified by silica gel column chromatography (eluent: toluene-hexane) to give (S) -5-decyloxy-
This gives 1.8 g (81% yield) of 2- (4 ′-(1-fluoroethyl) biphenyl-4-yl) pyrimidine (2-1). Clearing point 62 ° C. (S) -5- (4-decyloxyphenyl) -2- (4- (1-fluoroethyl) phenyl) pyrimidine, (S) -5- (4-decyloxy-3) in the same manner as in this example. -Fluorophenyl) -2- (4- (1-fluoroethyl) phenyl) pyrimidine, (S) -5-decyloxy-2- (2- (1-fluoroethyl) naphthalene-6
-Yl) pyrimidine, (S) -5-decyl-2- (4 '
-(1-Fluoroethyl) biphenyl-4-yl) pyrimidine, 5- (4-decylphenyl) -2- (4- (1
-Fluoroethyl) phenyl) pyrimidine, (S) -2
-Decyloxy-5- (4 '-(1-fluoroethyl)
Biphenyl-4-yl) pyridine, (S) -5- (4-decyloxyphenyl) -2- (4- (1-fluoroethyl) phenyl) pyrazine, (S) -3- (4-decyloxyphenyl) -6 -(4- (1-fluoroethyl)
Phenyl) pyridazine, 5- (4-decyloxyphenyl) -3- (4- (1-fluoroethyl) phenyl) -1,2,4-thiadiazole, (S) -5- (4-trifluoromethoxyphenyl) -2- (4- (1-Fluoroethyl) phenyl) pyrimidine, (S) -5- (4-fluorophenyl) -2- (4- (1-fluoroethyl))
Phenyl) pyrimidine, (S) -5- (4-cyanophenyl) -2- (4- (1-fluoroethyl) phenyl)
Pyrimidine, 5- (4-propoxyphenyl) -2-
(4- (1-Fluoroethyl) phenyl) pyrimidine can be synthesized.

Example 3 In a reactor equipped with a stirrer and a thermometer, (R) -5-decyloxy-2- (4- (1-hydroxyethyl) -2,
3-difluorophenyl) pyrimidine (2-3) 2.0
Charge g (5 mM) and 40 ml of dichloromethane, and
Diethylamino trifluoride 1.0 g (6 m
Add M) and stir for 30 minutes. Thereafter, the reaction mixture was poured into water, extracted with 100 ml of toluene, the organic layer was washed with water, concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (eluent: toluene-hexane) to give 5-decyloxy- This gives 2- (4- (1-fluoroethyl) -2,3-difluorophenyl) pyrimidine (1-3).

Example 4 (R)-(4'- was added to a reactor equipped with a stirrer and a thermometer.
2.0 g of decyloxy-2,3-difluoro)-(4- (1-hydroxyethyl)) biphenyl (2-4) and 40 ml of dichloromethane were charged and diethylamino trifluoride 1.0 g (6 mM) was added at -50 ° C. And stir for 50 minutes. Then, the reaction mixture is poured into water and extracted with toluene. The organic layer is washed with water and then concentrated under reduced pressure. The resulting residue is subjected to silica gel column chromatography (eluent:
If purified with (toluene-hexane), (S)-(4 '
-Decyloxy-2,3-difluoro)-(4- (1-fluoroethyl)) biphenyl (1-4) is obtained. In the same manner as in this example, (S) -4′-decyloxy- (4
-(1-fluoroethyl)) biphenyl, (S) -4 '
-Decyloxy- (4- (1-fluoroethyl)) terphenyl, (S) -6-decyloxy-2- (4- (1
-Fluoroethyl) phenyl) naphthalene, (S) -6
-(4-decyloxyphenyl) -2- (1-fluoroethyl) naphthalene, (S) -4'-decyloxy-3'-fluoro- (4- (1-fluoroethyl)) terphenyl, (S) -6- (4- Decyloxy-2,3-difluorophenyl) -2- (1-fluoroethyl) naphthalene, (R)-(4'-octyloxy-2,3-
Difluoro)-(4- (1-fluoroethyl)) biphenyl, (S) -4'-fluoro- (4- (1-fluoroethyl)) biphenyl, (S) -4'-fluoro- (4
-(1-fluoroethyl)) terphenyl, (S)-
3 ', 4'-difluoro- (4- (1-fluoroethyl)) biphenyl, (S) -4'-trifluoromethoxy- (4- (1-fluoroethyl)) biphenyl,
(S) -4 '-(4-Propylcyclohexyl)-(4
-(1-Fluoroethyl)) biphenyl can be synthesized.

Example 5 An optically active reactor was equipped with a stirrer and a thermometer.
(4-decyloxyphenyl) -3- (4- (1-hydr
Roxyethyl) phenyl) -1,2,4-tiasiazo
(2-5) 0.44 g (1 mmol), iodinated hex
40 ml of sill 10 ml and silver oxide 2.8 g (12 mmol)
Stir at ~ 50 ° C for 80 hours. After completion of the reaction, filtration, acetic acid
Wash with ethyl. The filtrate is concentrated under reduced pressure and the residue obtained
Is purified by silica gel column chromatography
Thus, the optically active 5- (4-decyloxyphene
) -3- (4- (1-hexyloxyethyl) phenyl
Le) -1, 2, 4-thiadiazole (1-5) 0.27
g (51% yield), [α]_D ²⁰= -6.1 ° (c = 1,
Chloroform). In the same manner as this example, 5-
(4-decyloxy-3-fluorophenyl) -3-
(4- (1-ethoxyethyl) phenyl) -1,2,4
-Thiadiazole 5-nonyl-3- (4- (1-butyl
Oxyethyl) phenyl) -1,2,4-thiodiazo
Can be synthesized.

Example 6 0.43 g (1 mmol) of optically active (R) -5-decyloxy-2- (4 '-(1-hydroxyethyl) biphenyl-4-yl) pyrimidine (2-6), 1 g of triethylamine and Charge 15 g of dichloromethane,
10 g of 0.2 g (2 mmol) of propionyl chloride
After dropping below 0 ° C, 1 hour at 0-10 ° C, 20-30
React for 2 hours at ℃. After completion of the reaction, the reaction mixture was poured into ice water and the organic layer was separated, and the obtained organic layer was added with 5% hydrochloric acid,
Wash with water, 5% aqueous sodium hydrogen carbonate and saturated brine, and dry over magnesium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography to give optically active (R) -5-decyloxy-2-
0.46 g (yield 96%) of (4 '-(1-propionyloxyethyl) biphenyl-4-yl) pyrimidine (1-6) is obtained. In the same manner as this example, (R) -5-
Decyloxy-2- (4 '-(1-acetyloxyethyl) biphenyl-4-yl) pyrimidine, (S) -5-
Decyloxy-2- (4 '-(1-acetyloxyethyl) biphenyl-4-yl) pyrimidine, (R) -5
Decyloxy-2- (4 '-(1-α-chloropropionyloxyethyl) biphenyl-4-yl) pyrimidine, (S) -5- (4-decyloxyphenyl) -2-
(4- (1-acetyloxyethyl) phenyl) pyrimidine can be synthesized.

Example 7 Optically active (R) -5- (4-decyloxyphenyl)
-2- (4- (1-hydroxyethyl) phenyl) pyri
Midine (2-7) 0.43 g (1 mmol), iodinated
15 ml of butyl and 3.5 g (15 mmol) of silver oxide
Stir at 35 ° C. for 90 hours. After completion of the reaction, filtration and acetic acid extraction are performed.
Wash with chill. The filtrate is concentrated under reduced pressure and the resulting residue is
Purify by silica gel column chromatography.
With, the optically active 5- (4- (5-butoxy-1-
Methyl-1-hexyl) phenyl) -2-decyloxy
0.24 g of pyrimidine (1-7) (yield 56%),
[Α] _D ²⁰= -8.7 ° (c = 1, chloroform) was obtained.
It

Example 8 Optically active 2-decyloxy-5- (4 '-(1-hydroxyethyl) biphenyl-4-yl) -pyridine (2
-2) 0.43 g (1 mmol), pyridine 10 ml
Then, 15 g of dichloromethane is charged, 0.25 g (2 mmol) of α-chloropropionyl chloride is added dropwise at 10 ° C. or lower, and then the mixture is reacted at 0 to 10 ° C. for 1 hour and 20 to 30 ° C. for 2 hours. After completion of the reaction, the reaction mixture was poured into ice water and the organic layer was separated, and the obtained organic layer was added with 5% hydrochloric acid, water and 5%.
% Sodium bicarbonate solution and saturated saline solution, and dried with magnesium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography to give optically active 2-decyloxy-5- (4 '-(1-
α-chloropropionyloxyethyl) biphenyl-4
-Yl) -pyridine (1-8) is obtained. In the same manner as in this example, (S) -5- (4-decyloxy-3-fluorophenyl) -2- (4- (1-acetyloxyethyl) phenyl) pyrimidine, (S) -5-decyloxy-2- ( 2- (1-acetyloxyfluoroethyl) naphthalene-6-yl) pyrimidine, (R) -5-decyl-2- (4 '-(1-propionyloxyethyl) biphenyl-4-yl) pyrimidine, 5- (4-decylphenyl)- 2- (4- (1-hexanoyloxyethyl)
Phenyl) pyrimidine, (S) -2-decyloxy-5
-(4 '-(1-acetyloxyethyl) biphenyl-4-yl) pyridine, (R) -5- (4-decyloxyphenyl) -2- (4- (1-acetyloxyethyl))
Phenyl) pyrazine, (R) -3- (4-decyloxyphenyl) -6- (4- (1-α-chloropropionyloxyethyl) phenyl) pyridazine, 5- (4-decyloxyphenyl) -3- ( 4- (1-Acetyloxyethyl) phenyl) -1,2,4-thiadiazole can be synthesized.

Example 9 0.39 g (1 mmol) of optically active 2- (4-decyloxy-2,3-difluorophenyl) -6- (1-hydroxyethyl) naphthalene (2-9), 10 ml of ethyl iodide, oxidation 2.8 g (12 mmol) of silver was stirred at room temperature for 100 hours. After completion of the reaction, filtration and washing with ethyl acetate are performed. The filtrate was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography to give optically active 2- (4-decyloxy-2,3-difluorophenyl) -6- (1-ethoxyethyl) naphthalene (1-9). To get In the same manner as this example, (S)
-4'-decyloxy-2 ', 3'-difluoro- (4
-(1-methoxyethyl)) biphenyl, (S) -4 '
-Decyloxy-2 ', 3'-difluoro- (4- (1
-(2-fluoroethoxy) ethyl)) terphenyl,
(S) -6-decyloxy-2- (4- (1-butyloxyethyl) phenyl) naphthalene, (S) -6- (4
-Decyloxy-2,3-difluorophenyl) -2- (1-hexyloxyethyl) naphthalene, (S)-
4'-decyloxy-3'-fluoro- (4- (1-ethoxyethyl)) terphenyl, (S) -6- (4-decyloxy-2,3-difluorophenyl) -2- (1
-(2-butenyloxy) ethyl) naphthalene, (R)
-(4 '-(3-hexenyloxy))-2', 3'-
Difluoro)-(4- (1-butoxyethyl)) biphenyl, (S) -4′-fluoro-3′fluoro- (4-
(1-hexyloxyethyl)) biphenyl, (S)-
3 ', 4'-difluoro- (4- (1-ethoxyethyl)) terphenyl, (S) -3', 4'-difluoro- (4- (1-butoxyethyl)) biphenyl, (S)
-4'-trifluoromethoxy- (4- (1-octyloxyethyl)) biphenyl and (S) -4 '-(4-propylcyclohexyl)-(4- (1-ethoxyethyl)) biphenyl can be synthesized. .

Example 10 0.43 g (1 mmol) of optically active (R) -5-decyloxy-2- (4 '-(1-hydroxyethyl) biphenyl-4-yl) pyrimidine (2-10), 8 mL of tetrahydrofuran And hexamethylphosphorylamide dissolved in 2 mL, and potassium hydride 0,06 g at 0 ° C
(1, 5 mmol) is added, and the mixture is reacted at the same temperature for 2 hours and further at room temperature for 5 hours. Next, ethyl iodide 0.
47 g (3 mmol) was added and the mixture was kept at 0 ° C for 5 hours at 30 ° C.
React for 5 hours. After completion of the reaction, the reaction solution is poured into ice water and extracted with ethyl acetate. In the same manner, post-treatment and purification are performed. Optically active (R) -5-decyloxy-2- (4 '
-(1-Ethoxyethyl) biphenyl-4-yl) pyrimidine (1-10) is obtained.

Example 11 5-decyloxy-2- (4 '-(1-hydroxyethyl) biphenyl-4-yl) pyrimidine (2-11)
To a mixed solution of 0.43 g (1 mmol), pyridine 3 ml and toluene 3 ml, at (25) to 30 ° C. (-)-2,2
-0.2 g (1, 5 mmol) of dimethylcyclopropanecarboxylic acid chloride (5-2) is added. After that, the reaction is performed at the same temperature for 4 hours. After completion of the reaction, the reaction solution is poured into ice water and extracted with 30 ml of toluene. The organic layer is washed with aqueous hydrochloric acid, water, and aqueous sodium hydrogen carbonate, concentrated, and purified by chromatography to give optically active 5-decyloxy-
2- (4 '-(1- (2,2-Dimethylcyclopropanecarbonyloxy) ethyl) biphenyl-4-yl) pyrimidine is obtained.

Example 12 Optically active (R) -5- (4-decyloxyphenyl)
0.43 g (1 mmol) of 2- (4- (1-hydroxyethyl) phenyl) pyrimidine (2-12) was dissolved in 5 mL of tetrahydrofuran and 2 mL of hexamethylphosphorylamide, and 0.08 g of potassium hydride was added at 10 ° C.
(1 mmol) is added, and the mixture is reacted at the same temperature for 2 hours and further at room temperature for 5 hours. Next, 0.4 g (2 mmol) of ethoxypropyl tosylate is added and reacted at 25 to 30 ° C. for 5 hours and at 40 ° C. for 5 hours. After completion of the reaction, the reaction solution is poured into ice water and extracted with ethyl acetate. Similarly, the following optically active (R) -5- (4-decyloxyphenyl) -2- (4- (1-ethoxypropyloxyethyl) phenyl) pyrimidine (1-12) is obtained by post-treatment and purification.
Get.

Example 13 The following compounds were mixed in the ratio shown in Table-1 to prepare a liquid crystal matrix composition (Ia). The compounds obtained in the present invention were mixed in this composition in respective proportions to obtain ferroelectric liquid crystal compositions shown in Table 2. The physical properties are shown in Table 2. [Measurement of Physical Properties of Liquid Crystal] The composition was sandwiched between two glass substrates each having a transparent electrode and a polyimide alignment film applied on the glass substrates so as to have a gap of 2 μm. A liquid crystal element was produced by disposing two polarizing plates on the outer sides of the respective polarizing plates with the polarization plane rotated by 90 °. At this time, the polarization axis on the light incident side was set so as to match the rubbing direction of the polyimide alignment film. Next, using these liquid crystal elements, phase series, spontaneous polarization, tilt angle,
The response speed was measured. By applying a voltage of ± 20 V, the optical response was detected and the response speed was measured. Spontaneous polarization is J
pn. J. Appl. Phys. Volume 22, 661 (19
It was calculated using the triangular wave method described in 93). A rectangular wave voltage of 10 V / μm is applied to the liquid crystal element placed on the sample table, and the sample table is rotated to measure the angles θ1 and θ2 at which the extinction position corresponds to each electric field and polarity. Half of the angle difference was obtained as the tilt angle. The response time is such that when light is incident on the liquid crystal element and applied to a rectangular wave of +/− 10 V / μm, the light transmittance of the liquid crystal element when the polarity is inverted is 10
The time required to change from 100% to 90%. Furthermore, the electric field dependence of the response time (τ-V characteristic) was measured to evaluate the performance as an inverse mode liquid crystal material. Here, the response time is the minimum pulse width with which a good switching state can be obtained when a monopolar pulse is applied. The τ-V characteristic was evaluated as follows. That is, the liquid crystal device has a duty ratio of 1:40 as shown in FIG.
Apply a monopolar pulse of 0 to switch,
After detecting the change in the amount of transmitted light at that time with a photomultiplier tube, current-voltage conversion was performed and input to an oscilloscope for observation. A good switching state can be obtained in a certain electric field, that is, the minimum pulse width that can maintain the memory property
The minimum pulse width for the applied electric field was used. Here, the memory property cannot be maintained means that the contrast ratio between the two stable states decreases. In this way, the minimum pulse width was plotted against the applied electric field to obtain the τ-V characteristic. The minimum width of the applied electric field in the τ-V characteristic was Emin, and the pulse width at that time was τmin.

[0039]

[Table 1]

[0040]

[Table 2]

Example 14 Phase Change of Compound of the Present Invention (R) -5-decyloxy-2- (4 '-(1-hydroxyethyl) biphenyl-4-yl) pyrimidine (2
-6): K- (138 ° C) -SA- (143 ° C) -Ch
-(166 ° C) -I * (S) -5-decyloxy-2- (4 '-(1-acetyloxyethyl) biphenyl-4-yl) pyrimidine:
K- (88 ° C) -Sc- (102 ° C) -SA- (119
C) -I. (R) -5- (4-decyloxyphenyl) -2-
(4- (1-hydroxyethyl) phenyl) pyrimidine (2-7): K- (149 ° C) -SA- (194 ° C)-
I. (S) -5- (4-decyloxyphenyl) -2-
(4- (1-acetyloxyethyl) phenyl) pyrimidine: K- (85 ° C) -Sc- (90 ° C) -SA- (1
22 ° C.)-I. (R) -5-decyloxy-2- (2- (1-hydroxyethyl) naphthalen-6-yl) pyrimidine: K-
(84 ° C.)-SA- (102 ° C.)-I. (S) -5-decyloxy-2- (2- (1-acetyloxyethyl) naphthalen-6-yl) pyrimidine:
K- (21 ° C) -Sc- (33 ° C) -SA- (45 ° C)
-I * (R) -5-decyloxy-2- (4- (1-fluoroethyl) phenyl) pyrimidine (1-1): K- (8
2 ° C) -I

[0042]

[Table 3]

[Brief description of drawings]

FIG. 1 is a schematic view of an example of a display device using a ferroelectric liquid crystal.

FIG. 2 is a diagram showing a waveform applied to a liquid crystal element in order to evaluate (τ-V characteristic).

[Explanation of symbols] 1 polarizing plate 2 glass substrate 3 transparent electrode 4 insulating alignment film 5 ferroelectric liquid crystal layer 6 spacer

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C07C 43/174 69/63 9546-4H 69/94 255/49 C07D 213/26 213/30 213 / 64 215/12 215/20 217/14 217/16 237/08 237/30 239/26 239/74 241/12 285/10 C09K 19/30 19/32 19/34 9279-4H G02F 1/13 500

Claims (8)

[Claims] 1. A general formula (1)(In the formula, R is a hydrogen atom, a fluorine atom, or trifluoromethyi.
Group, trifluoromethoxy group, cyano group, halogen atom
Saturated with 2 to 15 carbon atoms which may be substituted with
Unsaturated alkoxyalkyl group, 4-R¹− (Cycloa
Rukiru) group, 4-R¹A-(cycloalkenyl) group or
R¹-(O) m-, where R¹Is a halogen atom
A branched or straight-chain carbon atom which may be substituted with
15 alkyl, alkenyl or alkynyl groups
Indicated, m is 0 or 1. R ²Is a halogen atom
A branched or straight chain having 1 to 15 carbon atoms which may be substituted.
An alkyl group having 1 to 15 carbon atoms in the chain, an alkenyl group, or
Alkynyl group, charcoal optionally substituted with halogen atom
Saturated or unsaturated alkoxy alk having a prime number of 2 to 15
Group, hydrogen atom or fluorine atom. A¹, A²,
A³RespectivelyIndicates A¹Is a fused ring, p + q is 0 or 1.
Yes and A², A³Is a monocycle. A¹Is a monocycle
Then p + q is 1 or 2 and A when p + q is 2 ², A
³Are all monocyclic. Z is a fluorine atom or hydrogen atom
A child, p and q each represent 0 or 1, and u
And w each represent an integer of 0 to 3. Where R²But
C1-C15 which may be substituted with a halogen atom
A branched or straight chain alkyl group having 1 to 15 carbon atoms,
Substituted with a alkenyl or alkynyl group, halogen atom
Optionally saturated or unsaturated carbon atoms of 2 to 15
Rucoxyalkyl group or hydrogen atom, and R is a group
 R¹When-(O) m- is shown, A¹-(A²)_p−
(A³)_qBipheni whose benzene ring is entirely unsubstituted
Le, terphenyl, 2,6-naphthyl, pyrimidine-2
-Yl-phenyl, pyrimidin-5-yl-phenyl
There is no. ) An aromatic compound represented by. 2. General formula (2) (In the formula, R, A ¹ , A ² , A ³ , Z, p and q have the same meanings as described above). 3. A general formula (3) (In the formula, R, A ¹ , A ² , A ³ , Z, p and q have the same meanings as described above). 4. An alcohol compound represented by the general formula (2) according to claim 2 and a general formula (4) R ² COR ″ (4) (wherein R ² has the same meaning as described above, R ″ Is a hydroxyl group,
Indicates OCOR ² or a halogen atom. And a carboxylic acid represented by the formula (1) is reacted with the compound represented by the general formula (1), wherein s is 1 and t is 1. 5. An alcohol compound represented by the general formula (2) according to claim 2 and a general formula (5) R ² —Y (5) (wherein R ² has the same meaning as described above, and Y represents A halogen atom or —SO ₂ R ″ ′, wherein R ″ ′ represents a lower alkyl group or an optionally substituted phenyl group). In the compound represented by the general formula (1), s
Is 1, and t is 0. 6. An optically active form of the compound according to claim 1, 2 or 3. 7. A liquid crystal composition comprising at least one aromatic compound represented by the general formula [1] as a blending component. 8. A liquid crystal device using the liquid crystal composition according to claim 7.