JP2840981B2 - Liquid crystal compounds and compositions - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a liquid crystal compound useful as a ferroelectric liquid crystal material and a liquid crystal composition containing the liquid crystal compound.

[Related Art] In recent years, a display method using a ferroelectric liquid crystal as a new liquid crystal display element has been actively studied. This method uses a chiral smectic phase such as a chiral smectic C phase exhibiting ferroelectricity.

Many characteristics are required for ferroelectric liquid crystal materials used in ferroelectric liquid crystal display devices actually used, but at present, a single compound cannot satisfy such characteristics, It is necessary to use a ferroelectric liquid crystal composition obtained by mixing a liquid crystal compound or a non-liquid crystal compound.

Conventionally, as components of a chiral smectic C liquid crystal composition, optically active phenylbenzoate, optically active biphenyl, optically active phenylpyridine and optically active 5-alkyl-2- (4-alkoxyphenyl)
Liquid crystal compounds such as pyrimidines are known.

[Problems to be Solved by the Invention] However, when these are mixed to form a ferroelectric liquid crystal composition, it has not yet reached a region where it is completed to show practically excellent performance. Under these circumstances, practically more excellent liquid crystal compounds exhibiting the chiral smectic C phase are required.

Means for Solving the Problems The present inventors have conducted intensive studies on a liquid crystal compound exhibiting a chiral smectic C phase suitable for use in the above-mentioned applications, and as a result, a novel compound having a structure different from that of the related art has been obtained. The present inventors have found a liquid crystal compound and arrived at the present invention. That is, the present invention
General formula R ¹ -X ^1- (A ¹ -Y) _n -A ² -A ³ -X ² -R ² (1) [In the formula, R ¹ and R ² may have an asymmetric carbon. X ¹ is a good alkyl group having 1 to 18 carbon atoms (provided that at least ^one of R ¹ and R ² has an asymmetric carbon atom);
X ² is a direct bond, —O—, —S—, —OCO—, —COO— or —C≡C—, and Y is —C≡C— or —CH ₂ C
An H2-, A ^1, A ³ is of one to four fluorine atoms or 1
A 1,4-phenylene group which may be substituted with up to two chlorine atoms, bromine atoms, cyano groups or nitro groups,
² is And n is 0 or 1 (however, when n is 0,
X ¹ is always -C≡C-). ] And a ferroelectric liquid crystal composition containing at least one of the above compounds.

In the general formula (1), as the alkyl group having 1 to 18 carbon atoms which may have an asymmetric carbon atom of R ¹ and R ^2, a linear alkyl group (methyl group, ethyl group n-propyl group, n -Butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group,
n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-petadecyl group, n-hexadecyl group, n-heptadecyl group-octadecyl attachment, etc., branched alkyl group (isopropyl group, 1-methyl Propyl group, 1-methylbutyl group, 1-methylpentyl group, 1-methylhexyl group, 1-methylheptyl group, 1
-Methyloctyl group, 2-methylpropyl group, 2-methylbutyl group, 2-methylpentyl group, 2-methylhexyl group, 2-methylheptyl group, 2-methyloctyl group,
2-methylnonyl group, 2-methyldecyl group, 2-methylundecyl group, 2-methyldodecyl group, 2-methyltridecyl group, 2-methyltetradecyl group, 3-methylbutyl group, 3-methylpentyl group, 3- Methylhexyl group,
3-methylheptyl group, 3-methyloctyl group, 4-methylpentyl group, 4-methylhexyl group, 4-methylheptyl group, 4-methyloctyl group, 5-methylhexyl group, 5-methylheptyl group, 5- Methyloctyl group, 5
-Methylnonyl group, 5-methyldecyl group, 6-methylheptyl group, 6-methyloctyl group, 6-methylnonyl group, 6-methyldecyl group, 7-methyloctyl group, 7-
Methylnonyl group, 7-methyldecyl group, 8-methylnonyl group, 8-methyldecyl group, 9-methyldecyl group, 9-
Methylundecyl group), an alkyl group having a substituent [eg, an alkyl group substituted with F (fluorine atom) (2-fluoropropyl group, 2-fluorobutyl group,
-Fluoropentyl group, 2-fluorohexyl group, 2-
Fluoroheptyl group, 2-fluorooctyl group, 2-fluorononyl group, 2-fluorodecyl group, 2-fluoroundecyl group, 2-fluorododecyl group, 2-fluorotridecyl group, 2-fluorotetradecyl group, 3 -Fluoropropyl group, 4-fluorobutyl group, 5-fluoropentyl group, 6-fluorohexyl group, 7-fluoroheptyl group, 8-fluorooctyl group, 9-fluorononyl group, 10-fluorodecyl group, 11-fluoro Undecyl group, 12-fluorododecyl group, 2- (perfluoro-n
-Butyl) ethyl group, 2- (perfluoro-n-hexyl) ethyl group, 2- (perfluoro-n-octyl) ethyl group, 2- (perfluoro-n-decyl) ethyl group,
2-fluoro-3-methylbutyl group, 2-fluoro-3
-Methylpentyl group, 2-fluoro-4-methylpentyl group, etc .; alkyl group substituted by C1 (chlorine atom) (2-chloropropyl group, 2-chlorobutyl group, 2-chloropentyl group, 2-chlorohexyl) Group, 2-chloroheptyl group, 2-chlorooctyl group, 2-chlorononyl group, 2-chlorodecyl group, 2-chloroundecyl group, 2
-Chlorododecyl group, 2-chlorotridecyl group, 2-chlorotetradecyl group, 2-chloro-3-methylbutyl group, 2-chloro-3-methylpentyl group, 2-chloro-
An alkyl group substituted with an alkyloxy group (e.g., 4-methylpentyl group), an alkyloxy group (2-methoxypropyl group, 2-ethoxypropyl group, 2-propyloxypropyl group,
Butyloxypropyl group, 2-pentyloxypropyl group, 2-hexyloxypropyl group, 2-heptyloxypropyl group, 2-octyloxypropyl group, 2-nonyloxypropyl group, 2-decyloxypropyl group,
2- (2-methylbutyloxy) -propyl group, 2-isopropyloxypropyl group, 3-methoxybutyl group,
3-ethoxybutyl group, 3-propyloxybutyl group,
3-butyloxybutyl group, 3-pentyloxybutyl group, 3-hexyloxybutyl group, 3-heptyloxybutyl group, 3-octyloxybutyl group, 3-nonyloxybutyl group, 3-decyloxybutyl group, 3 − (2-
Methylbutyloxy) butyl group, 3-isopropyloxybutyl group, 4-methoxypentyl group, 4-ethoxypentyl group, 4-propyloxypentyl group, 4-butyloxypentyl group, 4-pentyloxypentyl group, 4
-Hexyloxypentyl group, 4-heptyloxypentyl group, 4-octyloxypentyl group, 4-nonyloxypentyl group, 4-decyloxypentyl group, 4-
(2-methylbutyloxy) pentyl group, 4- (2-methylpentyloxy) pentyl group, 4-isopropyloxypentyl group, etc.), optically active alkyl group (optically active 1-methylpropyl group, optically active) 1-methylbutyl group, optically active 1-methylpentyl group, optically active 1
-Methylhexyl group, optically active 1-methylheptyl group,
Optically active 1-methyloctyl group, optically active 2-methylbutyl group, optically active 2-methylpentyl group, optically active 2-
Methylhexyl group, optically active 2-methylheptyl group, optically active 2-methyloctyl group, optically active 2-methylnonyl group, optically active 2-methyldecyl group, optically active 2-methylundecyl group, optically active 2-methyldodecyl group Optically active 2-methyltridecyl group, optically active 2-methyltetradecyl group, optically active 3-methylpentyl group, optically active 3-methylhexyl group, optically active 3-methylheptyl group, optically active 3-methyloctyl group Optically active 4-methylhexyl group, optically active 4-methylheptyl group, optically active 4-methyloctyl group, optically active 5-methylheptyl group, optically active 5-methyloctyl group, optically active 5-methylnonyl group, optically active 5-methyldecyl group, optical activity 6
-Methyloctyl group, optically active 6-methylnonyl group, optically active 6-methyldecyl group, optically active 7-methylnonyl group, optically active 7-methyldecyl group, optically active 8-methyldecyl group, optically active 9-methylundecyl group, etc.) An optically active alkyl group having a substituent [for example, an optically active alkyl group substituted by F (fluorine atom) (an optically active 2-fluoropropyl group, an optically active 2-fluorobutyl group, an optically active 2-fluoropentyl group) An optically active 2-fluorohexyl group, an optically active 2-fluoroheptyl group,
Optically active 2-fluorooctyl group, optically active 2-fluorononyl group, optically active 2-fluorodecyl group, optically active 2-fluoroundecyl group, optically active 2-fluorododecyl group, optically active 2-fluorotridecyl group, Optically active 2-fluorotetradecyl group, optically active 2-fluoro-
A 3-methylbutyl group, an optically active 2-fluoro-3-methylpentyl group, an optically active 2-fluoro-4-methylpentyl group, an optically active alkyl group substituted by C1 (chlorine atom) (an optically active 2- Chloropropyl group, optically active 2-chlorobutyl group, optically active 2-chloropentyl group,
Optically active 2-chlorohexyl group, optically active 2-chloroheptyl group, optically active 2-chlorooctyl group, optically active 2
-Chlorononyl group, optically active 2-chlorodecyl group, optically active 2-chloroundecyl group, optically active 2-chlorodotesyl group, optically active 2-chlorotridecyl group, optically active 2
-Chlorotetradecyl group, optically active 2-chloro-3-methylbutyl group, optically active 2-chloro-3-methylpentyl group, optically active 2-chloro-4-methylpentyl group), and alkyloxy group. Optically active alkyl group (optically active 2-methoxypropyl group, optically active 2-
Ethoxypropyl group, optically active 2-propyloxypropyl group, optically active 2-butyloxypropyl group, optically active 2-pentyloxypropyl group, optically active 2-hexyloxypropyl group, optically active 2-heptyloxypropyl group, optical Active 2-octyloxypropyl group, optically active 2-nonyloxypropyl group, optically active 2-decyloxypropyl group, optically active 2- (2-methylbutyloxy) propyl group, optically active 2-isopropyloxypropyl group, optical Active 3-methoxybutyl group, optical activity 3
-Ethoxybutyl group, optically active 3-propyloxybutyl group, optically active 3-butyloxybutyl group, optically active 3
-Pentyloxybutyl group, optically active 3-hexyloxybutyl group, optically active 3-heptyloxybutyl group, optically active 3-octyloxybutyl group, optically active 3-nonyloxybutyl group, optically active 3-decyloxybutyl group Optically active 3- (2-methylbutyloxy) butyl group, optically active 3-isopropyloxybutyl group, optically active 4-methoxypentyl group, optically active 4-ethoxypentyl group, optically active 4-propyloxypentyl group, optical Active 4-butyloxypentyl group, optically active 4-pentyloxypentyl group, optically active 4-hexyloxypentyl group, optically active 4-heptyloxypentyl group, optically active 4-octyloxypentyl group, optically active 4-nonyloxy Pentyl group, optically active 4-decyloxypentyl group, optically active 4- ( - methylbutyloxy) pentyl group, such as optically active 4-isopropyloxy pentyl group), and optically active alkyl group substituted with a trifluoromethyl group (optically active 1-trifluoromethyl-butyl group,
Optically active 1-trifluoromethylpentyl group, optically active 1-trifluoromethylhexyl group, optically active 1-trifluoromethylheptyl group, optically active 1-trifluoromethyloctyl group, optically active 1-trifluoromethylnonyl group, optical Active 1-trifluoromethyldecyl group, optically active 1-trifluoromethylundecyl group, optically active 1-trifluoromethyldodecyl group, optically active 1-trifluoromethyl-2-methoxyethyl group, optically active 1-
Trifluoromethyl-2-ethoxyethyl group, optically active 1-trifluoromethyl-2-propyloxyethyl group, optically active 1-trifluoromethyl-2-butyloxyethyl group, optically active 1-trifluoromethyl-2- Pentyloxyethyl group, optically active 1-trifluoromethyl-2-hexyloxyethyl group, optically active 1-trifluoromethyl-2-isopropyloxyethyl group, optically active 1-trifluoromethyl-2- (1′-methyl Propyloxy) ethyl group, optically active 1-trifluoromethyl-2- (1′-methylbutyloxy) ethyl group, optically active 1-trifluoromethyl-2- (1′-methylpentyloxy) ethyl group, optically active 1-trifluoromethyl-2- (1′-methylhexyloxy) ethyl group, optically active 1-trifluoro L-methyl-2- (1'-methylheptyloxy) ethyl group, optically active 1-trifluoromethyl-2- (2'-methylbutyloxy) ethyl group, optically active 1-trifluoromethyl-3-methoxypropyl group, Optically active 1-trifluoromethyl-3-ethoxypropyl group, optically active 1-trifluoromethyl-3-propyloxypropyl group, optically active 1-trifluoromethyl-3-butyloxypropyl group, optically active 1-trifluoro Methyl-3-pentyloxypropyl group, optically active 1-trifluoromethyl-3-hexyloxypropyl group, optically active 1-trifluoromethyl-3-isopropyloxypropyl group, optically active 1-trifluoromethyl-3- ( A 1'-methylpropyloxy) propyl group,
Optically active 1-trifluoromethyl-3- (1'-methylbutyloxy) propyl group, optically active 1-trifluoromethyl-3- (1'-methylpentyloxy) propyl group, optically active 1-trifluoromethyl- 3- (1'-methylhexyloxy) propyl group, optically active 1-trifluoromethyl-3- (1'-methylheptyloxy) propyl group, optically active 1-trifluoromethyl-3-
(2'-methylbutyloxy) propyl group, optical activity 1
-Trifluoromethyl-4-methoxybutyl group, optically active 1-trifluoromethyl-4-ethoxybutyl group, optically active 1-trifluoromethyl-4-propyloxybutyl group, optically active 1-trifluoromethyl-4- Butyloxybutyl group, optically active 1-trifluoromethyl-4
-Pentyloxybutyl group, optically active 1-trifluoromethyl-4-hexyloxybutyl group, optically active 1-trifluoromethyl-4-isopropyloxybutyl group,
An optically active 1-trifluoromethyl-4- (1'-methylpropyloxy) butyl group, an optically active 1-trifluoromethyl-4- (1'-methylbutyloxy) butyl group,
Optically active 1-trifluoromethyl-4- (1'-methylpentyloxy) butyl group, optically active 1-trifluoromethyl-4- (1'-methylhexyloxy) butyl group, optically active 1-trifluoromethyl- 4- (1′-methylheptyloxy) butyl group, optically active 1-trifluoromethyl-4- (2′-methylbutyloxy) butyl group, etc., and optically active alkyl group substituted by cyano group (optically active 1-cyanobutyl group, optically active 1-cyanopentyl group, optically active 1-cyanohexyl group, optically active 1
A cyanoheptyl group, an optically active 1-cyanooctyl group,
Optically active 1-cyanononyl group, optically active 1-cyanodecyl group, optically active 1-cyanoundecyl group, optically active 1-
Cyanododecyl group) and the like).

Of these, preferred are alkyl groups having 4 to 10 carbon atoms which may have an asymmetric carbon atom (provided that R ¹ ,
At least one of R ² has an asymmetric carbon atom).

In the general formula (1), X ¹ and X ² are preferably a direct bond, —O—, or —C≡C—.

Y is, -C≡C- or -CH ₂ CH ₂ -.

A ¹ and A ³ are preferably 1,4-phenylene groups which may be substituted by 1 to 4 fluorine atoms.

 n is 0 or 1.

Specific examples of the liquid crystal compound represented by the general formula (1) include compounds having groups as shown in Tables 1 to 6.

In Table-1 and Table-2, each symbol represents the following groups, respectively (however, in the following groups, * represents optical activity). Es; -OCO- (r); represents a racemic form.

-; Represents a direct bond.

The compound included in the general formula (1) can be synthesized, for example, through the following steps. [In the following formula, R ¹ , R ² and X ¹ are the same as those in the general formula (1). ] That is, the compound of the general formula (2) is converted to 3-methyl 1-
After reacting butyl-3-ol with trimethylamine in an inert gas atmosphere using a zero-valent or divalent palladium catalyst to obtain a compound of the general formula (3), sodium hydroxide powder in anhydrous toluene is added. By acting
The compound of the general formula (4) can be obtained. By reacting the compound of the general formula (4) with the compound of the general formula (5) in triethylamine under an inert gas atmosphere using a zero-valent or divalent palladium catalyst, the compound of the general formula ( The compound of 1a) can be obtained.

 Alternatively, it can be synthesized through the following steps.

That is, the compound of the general formula (5) is converted to 3-methyl-1-
After reacting with butyn-3-ol and trimethylamine in an inert gas atmosphere using a zero-valent or divalent palladium catalyst to obtain a compound of the general formula (6), sodium hydroxide powder in anhydrous toluene is added. By acting
The compound of the general formula (7) can be obtained. By reacting the compound of the general formula (7) and the compound of the general formula (2) in triethylamine under an inert gas atmosphere using a zero-valent or divalent palladium catalyst, the compound of the present invention represented by the general formula ( The compound of 1a) can be obtained.

The compound of the general formula (2), which is a raw material of the compound (1a), can be synthesized, for example, through the following steps.

X ¹ is -O-.

That is, the compound of the general formula (2-1) can be obtained by alkylating the compound of the general formula (8) with an alkylating agent (for example, an alkyl halide).

X ¹ is -OCO-.

That is, the compound of the general formula (2-2) can be obtained by deriving the compound of the formula (9) into the corresponding acid chloride and then esterifying the compound with an alcohol.

X ¹ is a direct bond.

That is, the compound of the general formula (2-3) can be obtained by reacting the compound of the general formula (11) with the compound of the formula (10) and then adding hydrogen using a platinum catalyst.

The compound of the general formula (5), which is a raw material of the above compound, can be synthesized, for example, through the following steps.

That is, the compound of the general formula (14) can be obtained by allowing benzoyl chloride (13) to act on the compound of the general formula (8). Cross-coupling the compound of the general formula (14) with the compound of the formula (15) in an inert gas atmosphere in the presence of a base (eg, sodium carbonate) using a zero-valent or divalent palladium catalyst or a nickel catalyst. Thus, the compound of the general formula (16) can be obtained. The compound of the general formula (16) can be halogenated to obtain a compound of the general formula (17). The compound of the general formula (18) can be obtained by hydrolyzing the compound of the general formula (17) with a base (for example, sodium hydroxide). General formula (1
By reacting the compound of 8) with an alkylating agent (for example, an alkyl halide) in the presence of a base (for example, sodium hydroxide), a compound of the general formula (5) can be obtained.

That is, by alkylating the compound of the general formula (8) with an alkylating agent (eg, an alkyl halide),
The compound of the general formula (19) can be obtained. General formula (1
Grignard reagent (2)
By adjusting 0) and reacting with a compound of the general formula (21) using a palladium catalyst, a compound of the general formula (5 ′) can be obtained.

That is, the compound of the general formula (1b) can be obtained by hydrogenating the compound of the general formula (1a) obtained in (I) using palladium carbon as a catalyst.

The liquid crystal is generally used as a liquid crystal composition composed of two or more components, and the liquid crystal compound of the present invention can also be used as a component of the liquid crystal composition. The liquid crystal composition includes a smectic liquid crystal, for example, a smectic liquid crystal having no optically active site [2-p-alkyloxyphenyl-5-alkylpyrimidine, 2-p-alkylphenyl-5-alkyloxypyrimidine, 2-p-alkanoyl. Oxyphenyl-5-alkylpyrimidine, 2-p-alkyloxycarbonylphenyl-5-alkylpyrimidine, 2
-P-alkylphenyl-5-p-alkyloxyoxyphenylpyrimidine, 2-p-alkyloxy-m-
Fluorophenyl-5-alkylpyrimidine, 2-p-
Alkyloxyphenyl-5- (trans-4-alkylcyclohexyl) pyrimidine, 2-p-alkyloxyphenyl-5-alkylpyrimidine, 2-p-alkyloxy-m-fluorophenyl-5-alkylpyrimidine, 2-p- (P'-alkylphenyl) phenyl-5
-Alkylpyrimidine, 2-p-alkylphenyl-5
-P-alkylphenylpyrimidine, p-alkyloxyphenyl-5-alkylpicolinate, 2-p-alkyloxyphenyl-5-alkyloxypyrazine,
-P-alkylphenyl-5-alkylpyrimidine, 2
-P-alkyloxyphenyl-5-alkyloxylimidine, 2-p-alkoxyphenyl-5-alkyloxypyrimidine, 4-alkyloxy-4'-biphenylcarboxylic acid-p '-(alkyloxycarbonyl) phenyl ester, 4-alkyloxy-4'-biphenylcarboxylic acid-alkyl ester and / or ferroelectric liquid crystal [optically active 4-alkyloxy-4'-biphenylcarboxylic acid-p '-(2-methylbutyloxycarbonyl) phenyl] Ester, optically active 4-n-alkyloxy-4'-biphenylcarboxylic acid-2-methylbutyl ester, optically active p-alkyloxybenzylidene-p'-amino-2-chloropropylcinnamate,
Optically active p-alkyloxybenzylidene-p'-amino-2-methylbutylcinnamate] and / or ordinary chiral smectic liquid crystal [optically active 4- (p
-Alkyloxybiphenyl-p'-oxycarbonyl) -4 '-(2-methylbutyloxycarbonyl) cyclohexane, optically active pn-alkyloxybenzylidene-p'-(2-methylbutyloxycarbonyl)
Aniline etc.]. Further, it may contain a chiral compound having no liquid crystallinity and / or a dichroic dye, for example, an anthraquinone dye or an azo dye.

A liquid crystal composition exhibiting ferroelectricity causes an optical switching phenomenon when a voltage is applied, and a display element having a fast response utilizing this phenomenon can be produced (for example, JP-A-56-107216,
JP-A-59-118744, NA Clark (NACl
ark), ST Lagerwal
l); Applied Physics Letter
sics Letter) 36 , 899 (1980), etc.].

The liquid crystal composition of the present invention has a cell spacing of 0.5 to 10 μm.
m, preferably 0.5 to 3 μm in a liquid crystal cell,
By installing a polarizer on both sides, it can be used as an optical switching element (display element).

The above-mentioned liquid crystal cell can be manufactured by providing a transparent electrode and bonding two glass substrates whose surfaces are subjected to an alignment treatment with a spacer interposed therebetween.

Examples of the spacer include alumina beads, glass fibers, and polyimide films. As the orientation treatment method, a usual orientation treatment, for example, a polyimide film, a rubbing treatment, a SiO oblique deposition, or the like can be applied.

EXAMPLES Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited thereto.

Example 1 Production of Compound No. 1 in Table 1 40.00 g of the following compound (a) and 12.64 g of 3-methyl-1-butyn-3-ol were placed in 15 ml of triethylamine. Using 176 mg of bistriphenylphosphine palladium chloride and 44 mg of copper iodide as a catalyst, the mixture was stirred at room temperature under a nitrogen atmosphere for 4.5 hours. After completion of the reaction, triethylamine was removed, and the mixture was extracted with hexane. The hexane layer was washed with 1N hydrochloric acid and water, and then hexane was removed under reduced pressure to obtain 45.36 g of the following compound (b) as an oil.

The above compound (b) (45.36 g) was dissolved in anhydrous toluene (1 L), and powdered sodium hydroxide (10.00 g) was added.
Stirred for hours. After the completion of the reaction, toluene was removed, and the mixture was extracted with ether. After washing with water, the ether was removed under reduced pressure to obtain 22.88 g of the following compound (c) as an oil.

30.00 g of o-fluoro-p-iodophenol was dissolved in 300 ml of anhydrous toluene, 16 ml of pyridine was added, and the mixture was stirred at room temperature. To this, 17.6 ml of benzoyl chloride was added dropwise over 15 minutes, and the mixture was stirred at room temperature for 24 hours. The reaction mixture was washed sequentially with water, 1N hydrochloric acid, a saturated aqueous solution of sodium hydrogen carbonate and water, and then toluene was distilled off. The obtained solid was recrystallized from methanol to obtain 38.20 g of p-benzoyloxy-m-fluoroiodobenzene.

12.80 g of p-benzoyloxy-m-fluoroiodobenzene was dissolved in 50 ml of toluene, 25 ml of a 2M aqueous sodium hydrogen carbonate solution was added, and the mixture was stirred at room temperature. Under an inert gas atmosphere, 860 mg of tetrakistriphenylphosphine palladium and 5.00 g of phenylboric acid in ethanol 30
Then, the mixture was heated and refluxed for 5 hours. After cooling, stop the reaction with 3 ml of 30% hydrogen peroxide solution, extract with toluene, wash with water,
The toluene was distilled off. The obtained solid was recrystallized from hexane to obtain 7.00 g of the following compound (d).

2.80 g of the compound (d) obtained in was dissolved in 35 ml of acetic acid, and 1 ml of sulfuric acid, 550 mg of metaperiodic acid and 1.20 g of iodine were added thereto, followed by stirring at 90 ° C. for 10 hours. After cooling, the reaction mixture was poured into 200 ml of ice water, excess iodine was reduced with sodium hydrogen sulfite, and the precipitated solid was filtered. This was recrystallized from toluene to obtain 1.70 g of the following compound (e).

1.70 g of the compound (e) obtained in
And 490 mg of sodium hydroxide was added thereto.
The mixture was heated under reflux for an hour. After cooling, the ethanol is distilled off,
The obtained solid was dissolved in 40 ml of water. Carbon dioxide gas was blown into this solution, and the precipitated solid was filtered to obtain 1.20 g of the following compound (f).

5.00 g of the compound (f) obtained in
-Toluenesulfonic acid-2-methylbutyl ester 3.78
g and potassium hydroxide 1.07 g were dissolved in dry ethanol 50 ml, and the mixture was heated under reflux for 22 hours. After the completion of the reaction, the ethanol was removed and extracted with toluene. After washing with water, toluene was removed under reduced pressure and recrystallized from methanol to obtain 4.70 g of the following compound (g).

0.86 g of the compound (c) obtained in the above, and 1.50 g of the compound (g) obtained in 50 ml of triethylamine, using 14 mg of dichlorobistriphenylphosphine palladium palladium and 4 mg of copper (I) iodide as catalysts under a nitrogen atmosphere at room temperature. For 3 hours. After completion of the reaction, triethylamine was removed, and the mixture was extracted with toluene. After washing with 1N hydrochloric acid, washing with water and purification on a silica gel column, recrystallization four times with ethanol gave white crystals of the compound of the present invention in Table-1.
0.69 g of No. 1 compound was obtained. The structure of the compound was confirmed by NMR (nuclear magnetic resonance spectrum analysis), MS (mass spectrometry), IR (infrared absorption spectrum analysis) and elemental analysis. IR spectrum, H-NMR spectrum and F
FIG. 1, FIG. 2 and FIG.
Shown in the figure.

Elemental analysis value: Theoretical value (%) Actual value (%) C: 78.16 C: 78.27 H: 7.14 H: 7.01 F: 7.98 F: 8.04 Example 2 Production of compound No. 7 in Table 1 o-fluoro- 10.40 g of potassium hydroxide was added to a solution of 40.00 g of p-iodophenol and 41.00 g of optically active p-toluenesulfonic acid-2-methylbutyl ester in 500 ml of dry ethanol, and the mixture was stirred for 7 hours.
After completion of the reaction, the ethanol was removed under reduced pressure, and extracted with toluene. After washing the toluene layer with water, toluene was removed to obtain 50.00 g of the following compound (b) as an oil.

20.00 g of the compound (h) obtained in
6.00 g of butyn-3-ol was added to 150 ml of triethylamine.
Medium, dichlorobistriphenylphosphine palladium 13
The mixture was stirred at room temperature for 7 hours under a nitrogen atmosphere using 7 mg and 34 mg of copper iodide as catalysts. After the completion of the reaction, toluethylamine was removed and extracted with hexane. The hexane layer was washed with 1N hydrochloric acid and washed with water, and then hexane was removed under reduced pressure to obtain 16.40 g of the following compound (i) as an oil.

The above compound (i) (16.40 g) was dissolved in anhydrous toluene (350 ml), powdered sodium hydroxide (2.50 g) was added, and the mixture was heated under reflux for 1 hour. After the completion of the reaction, toluene was removed, and the mixture was extracted with ether. After washing with water, the ether was removed under reduced pressure to obtain 11.30 g of the following compound (j) as an oil.

After stirring 5.00 g of the compound (f) obtained in Example 1 and 0.76 g of sodium hydroxide dissolved in a small amount of water in 50 ml of dimethyl sulfoxide for 30 minutes, 3.15 g of hexyl bromide was added. Stir for 9 hours. After completion of the reaction, extraction was performed with toluene. The toluene layer was washed with water and recrystallized from hexane to obtain 4.57 g of the following compound (k).

0.78 g of the compound (j) obtained in the above and 1.50 g of the compound (k) obtained in 50 ml of triethylamine under nitrogen atmosphere at room temperature using 13 mg of dichlorobistriphenylphosphine palladium and 4 mg of copper (I) iodide as catalysts. Stir for 3.5 hours. After completion of the reaction, triethylamine was removed, and the mixture was extracted with toluene. Washing the toluene layer with 1N aqueous hydrochloric acid,
After washing with water, the product was purified by a silica gel column and recrystallized four times with ethanol to obtain 0.68 g of the compound of the present invention of No. 7 in Table 1 as white crystals. The IR, H-NMR and F-NMR spectra of the above compound are shown in FIGS. 4, 5 and 6, respectively.

Elemental analysis value: Theoretical value (%) Actual value (%) C: 78.16 C: 78.09 H: 7.14 H: 7.23 F: 7.98 F: 8.12 Example 3 Production of No. 3 compound in Table 1 Example 1 Using the obtained compound (c) (0.90 g) and the racemic p-toluenesulfonic acid-2-methylbutyl ester in place of the optically active p-toluenesulfonic acid-2-methylbutyl ester, the compounds of Example 1 1.50 g of a racemic (g ′) having the following structure obtained through the same operation.
The same operation as in Example 1 To obtain No. 3 in Table 1, which is the compound of the present invention.
0.90 g of the compound was obtained.

Example 4 Production of Compound No. 9 in Table 1 Racemic body (j ') having the following structure obtained through the same operation as in Example 2 0.80 g of the compound (k) obtained in Example 2 was reacted with 1.50 g under the same conditions as in Example 2 to obtain 0.80 g of the compound of the present invention, No. 9 in Table 1 in Table 1.

Example 5 Production of Compound No. 65 in Table-2 Compound (h) obtained in Example 2 (8.00) and 70 ml of an ether solution of Grignard reagent prepared from magnesium and
Under an inert gas atmosphere using 70 ml of a dried tetrahydrofuran solution of 7.39 g of 2,5-dibromopyridine and 182 mg of dichlorobisdiphenylphosphinobutan palladium as a catalyst.
Stir at room temperature for 5 hours. The reaction was stopped with water, the reaction mixture was extracted with ether, washed with 1N hydrochloric acid and water, and then the ether was removed. Then, by recrystallization with methanol,
1.00 g of the following compound (1) was obtained.

Using 0.65 g of the compound (c) obtained in Example 1 and 1.00 g of the above compound (1) in 50 ml of triethylamine, using 10 mg of dichlorobistriphenylphosphine palladium, 3 mg of copper (I) iodide and 15 mg of triphenylphosphine as catalysts. The mixture was heated under reflux in a nitrogen atmosphere for 5 hours. After completion of the reaction, triethylamine was removed, and the mixture was extracted with toluene. After washing the toluene layer with 1N hydrochloric acid water and water,
The product was purified by a silica gel column and recrystallized four times with ethanol to obtain 0.50 g of the compound of the present invention as white crystals, No. 65 in Table 2, which is the compound of the present invention. The IR, H-NMR and F-NMR spectra of the above compound are shown in FIGS. 7, 8 and 9, respectively.

Elemental analysis: Theoretical (%) Actual (%) C: 75.47 C: 75.31 H: 6.92 H: 7.03 N: 2.94 N: 2.81 F: 7.97 F: 7.95 Example 6 Compound of No.71 in Table-2 Production of the following compound (a) from 15.00 g and magnesium 120 ml of the prepared Grignard reagent in ether solution and 2,5
13.20 g of dibromopyridine in 120 ml of a dry tetrahydrofuran solution was reacted for 5 hours at room temperature under a nitrogen atmosphere using 338 mg of dichlorobisdiphenylphosphinobutanpalladium as a catalyst. The reaction was quenched with water, the reaction mixture was extracted with ether, washed with 1N hydrochloric acid and water in that order, and the ether was distilled off. The obtained solid was recrystallized from methanol to obtain 9.00 g of the following compound (m).

Using 1.50 g of the above compound (m) and 0.88 g of the compound (j) obtained in Example 2 as catalysts, 15 mg of dichlorobistriphenylphosphine palladium, 4 mg of copper (I) iodide and 23 mg of triphenylphosphine in 50 ml of triethylamine were used as catalysts. The mixture was heated under reflux in a nitrogen atmosphere for 4 hours. After completion of the reaction, triethylamine was removed, and the mixture was extracted with toluene.
The toluene layer was washed successively with 1N hydrochloric acid and water, purified by a silica gel column, and recrystallized four times with ethanol to obtain 0.56 g of the white crystalline compound of the present invention, No. 71 in Table 2, which is the compound of the present invention. Was. IR spectrum of the above compound, H-N
The MR spectrum and the F-NMR spectrum were
This is shown in FIG. 11, FIG. 11 and FIG.

Elemental analysis: Theoretical value (%) Actual value (%) C: 75.47 C: 75.38 H: 6.92 H: 6.95 N: 2.94 N: 2.84 F: 7.97 F: 7.99 Example 7 Compound of No. 67 in Table-2 The racemic product obtained through the same operation as in Example 2 using racemic p-toluenesulfonic acid-2-methylbutyl ester instead of optically active p-toluenesulfonic acid-2-methylbutyl ester 1.30 g of a racemic (1 ′) having the following structure, which was obtained through the same operation as in Example 5 using p-2-methylbutyloxy-m-fluoroiodobenzene, and the compound obtained in Example 1. (C) 0.8
By reacting 5 g under the same conditions as in Example 5, 0.90 g of the compound of the present invention, No. 67 in Table 2, was obtained.

Example 8 Production of Compound No. 73 in Table-2 1.50 g of compound (m) obtained in Example 6 and Example 4
By reacting 0.90 g of the compound (j ') used in Example 2 under the same conditions as in Example 6, 0.70 g of the compound of the present invention, No. 73 in Table 2, was obtained.

Example 9 Production of Compound No. 72 in Table-2 0.20 g of the compound No. 71 in Table-2 obtained in Example 6 was dissolved in 20 ml of ethanol, and 0.10 g of 5% palladium carbon was used as a catalyst. , And hydrogenation was performed at normal pressure under a hydrogen atmosphere. After completion of the reaction, the catalyst was removed by filtration, and then ethanol was removed. Then, by dissolving in hexane and separating and purifying with a silica gel column,
0.10 g of the compound of the present invention, No. 72 in Table 2, was obtained. The IR spectrum, H-NMR spectrum and F-NMR spectrum of the above compound are shown in FIGS. 13, 14 and 15, respectively.

Elemental analysis: Theoretical value (%) Actual value (%) C: 74.85 C: 74.71 H: 7.69 H: 7.73 N: 2.91 N: 3.03 F: 7.90 F: 8.11 Compounds obtained in Examples 1 to 9 Are shown in Table-3.

In Table 3, each symbol is as follows.

Cry; crystalline phase S _A ; smectic A phase S _C ^* ; chiral smectic C phase S _C ; smectic C phase N _em ^* ; chiral nematic phase N _em ; nematic phase Iso; isotropic liquid phase. Effect of the Invention] The present invention provides novel chiral smectic C liquid crystals, and these smectic liquid crystals have the following remarkable characteristics.

(1) The liquid crystal composition is required to have a negative dielectric efficiency anisotropy, but the chiral smectic C liquid crystal of the present invention has an electron-withdrawing halogen atom bonded and / or a nitrogen atom in the minor axis direction of the molecule. The dielectric anisotropy is negative,
It is very useful as a component for making the dielectric anisotropy of the liquid crystal composition negative.

(2) Among the chiral smectic C liquid crystals of the present invention, those having a fluorine atom bonded thereto are chiral smectic C liquid crystals.
Since there is no other smectic phase on the lower temperature side than the phase, the temperature range of the chiral smectic C phase can be expanded by mixing, which is very useful.

(3) Among the chiral smectic C liquid crystals of the present invention, those having no ester bond have low viscosity.

(4) Since the molecules are rigid, the orientation is very good.

(5) Good stability to light, heat and moisture.

(6) Those having no smectic A phase between the chiral smectic C phase and the nematic phase have a large tilt angle and are very useful as a component for adjusting the tilt angle.

Due to the above effects, the liquid crystal compound of the present invention is a very useful substance in developing a practical ferroelectric chiral smectic liquid crystal composition.

[Brief description of the drawings]

FIG. 1, FIG. 2 and FIG. 3 show IR, H-NMR and F-NMR spectra of the compound obtained in Example 1, respectively.
FIGS. 4, 5 and 6 show the IR, H-NMR and F-NMR spectra of the compound obtained in Example 2, respectively.
FIGS. 7, 8 and 9 show the IR, H-NMR and F-NMR spectra of the compound obtained in Example 5, respectively.
FIG. 10, FIG. 11 and FIG. 12 show IR, H-NMR and F-NMR spectra of the compound obtained in Example 6, respectively.
FIGS. 13, 14 and 15 show the IR, H-NMR and F-NMR spectra of the compound obtained in Example 9, respectively.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07D 213/30 C07D 213/30 237/08 237/08 C09K 19/34 C09K 19/34 19/42 19/42 G02F 1/13 500 G02F 1 / 13 500 Examiner Osamu Sato (56) References JP-A-2-265985 (JP, A) JP-A-2-264745 (JP, A) JP-A-2-258736 (JP, A) (58) Field (Int.Cl. ⁶ , DB name) C07C 25 / 18,25 / 24,43 / 20,69 / 94 C07D 213 / 24,213 / 30,237 / 08 C09K 19 / 34,19 / 42 G02F 1/13 CA (STN )

Claims (2)

(57) [Claims] 1. A general formula ^{R 1 -X 1 - (A 1} -Y) in ^{n-A 2 -A 3 -X 2} -R 2 (1) [wherein, R ^1, R ² is an asymmetric carbon an alkyl group having 1 to 18 carbon atoms which may have (although, of R ^1, R ^2, having at least either the asymmetric carbon atoms), X ^1,
X ² is a direct bond, —O—, —S—, —OCO—, —COO— or —C≡C—, and Y is —C≡C— or —CH 2 C
An H2-, A ^1, A ³ is of one to four fluorine atoms or 1
A 1,4-phenylene group which may be substituted with up to two chlorine atoms, bromine atoms, cyano groups or nitro groups,
² is And n is 0 or 1 (however, when n is 0, X ¹ is always -C≡C-). ] The liquid crystal compound shown by these. 2. A ferroelectric liquid crystal composition comprising at least one liquid crystal compound according to claim 1.