JP2974805B2 - Optically active substance and liquid crystal composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel optically active substance having a .delta.-valerolactone ring in its structure and a ferroelectric liquid crystal composition containing the same.

[0002]

2. Description of the Related Art At present, liquid crystal widely used as a display material belongs to a nematic phase, and has characteristics such as a light-receiving type that does not cause eyestrain and extremely low power consumption. However, it has the drawbacks that the display is slow and the display becomes invisible depending on the viewing angle.

A display device using a ferroelectric liquid crystal as a device having characteristics of a nematic type liquid crystal that does not cause eyestrain and extremely low power consumption, and having a high-speed response and a high contrast comparable to a light emitting type display device. Printer heads are being considered.

[0004] Ferroelectric liquid crystal was first developed by Meyer (RBMey) in 1975.
er) etc. were first announced by (J.
Physique 36, L-69 (1975)), which has a chiral smectic C phase (hereinafter abbreviated as Sm ^* C phase), a typical example of which is p-decyloxybenzylidene-p'-amino- 2-methylbutylcinnamate (hereinafter abbreviated as DOBAMBC).

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However, most of the above-mentioned DOBAMBC and some of the ferroelectric liquid crystal materials proposed thereafter have a narrow ferroelectric temperature range (temperature range in which the Sm ^* C phase exists). It is difficult to use practically by itself. Therefore, in general, attempts have been made to mix various types of ferroelectric liquid crystals and extend the temperature range showing the Sm ^* C phase to the low temperature side and the high temperature side around room temperature. Further, for a printer head that requires an ultra-high-speed response, a ferroelectric liquid crystal having a spontaneous polarization larger than that of a conventionally developed ferroelectric liquid crystal is required.

An object of the present invention is to provide an optically active substance which is chemically stable, has no coloration, has excellent light stability, and exhibits a large spontaneous polarization when compounded in a liquid crystal composition. And to provide a liquid crystal composition comprising:

[0008]

That is, the gist of the present invention resides in an optically active substance having a δ-valerolactone ring represented by the general formula (1) and a liquid crystal composition containing at least one kind thereof.

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(Wherein R ₁ is independently a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkenyl group having 2 to 18 carbon atoms, 3 is a straight-chain or branched-chain alkoxyalkyl group having 1 to 18 carbon atoms in the alkyl portion, or one in which one or more of the hydrogen atoms is halogen-substituted and has an optically active group. In the case of having a structure which can be an optically active group or a racemic body, R ₂ is hydrogen, a methyl group, an ethyl group or a propyl group, X is a single bond, -O -, - CO ₂ - or -O
CO- indicates, Y is a single _{bond, -CO 2 -, - O -} , - CH
₂ O- or -OCH _2- , wherein A is

[0011]

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[0012] indicates, B, B 'and B "each represent hydrogen, halogen, a cyano group, a methyl group, a methoxy group or a trihalomethyl group, V is a single bond, -CH ₂ O -, - OCH
₂ -, - CO ₂ - or -OCO- indicates, * indicates that the carbon to which it is applied is an asymmetric carbon. )

In the optically active substance of the present invention, R ₁ in the general formula (1) is a linear or branched alkyl group having 4 to 14 carbon atoms, a linear or branched alkenyl group having 4 to 14 carbon atoms, Preferred are linear or branched alkoxyalkyl groups having 4 to 14 carbon atoms in the alkyl portion,
Examples of such linear alkyl groups include n-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, and n-tetradecyl groups And the like, and as the branched alkyl group,

-(CH ₂ ) _a C (CH ₃ ) H (CH ₂ ) _b CH ₃ (a is an integer of 0 to 10, b is an integer of 1 to 11, and 1 ≦ a
+ B ≦ 11. ) Can be exemplified. In the case of such a methyl-branched alkyl group, both those having optical activity and those having a racemic form can be suitably used.

[0015] Examples of those halogen-substituted straight-chain alkyl group is _{- (CH 2) k CWH (} CH 2) i CH 3 ( wherein W represents fluorine, chlorine or bromine, k and i are each 0 An integer of up to 12 and 2 ≦ k + i ≦ 12) can be exemplified as a preferable example, and it is more preferable that this is an optically active group.

As an example of a compound substituted by a halogen with a branched alkyl group, an alkyl group having a trifluoromethyl branch [-(CH ₂ ) _a C (CF ₃ ) H (CH ₂ ) _b CH ₃ ] can be exemplified. This is also more preferably an optically active group. (A and b represent the above-mentioned meaning.)

The linear alkoxyalkyl group includes-
(CH ₂ ) _c OC _j H _{2j + 1 The} branched chain alkoxyalkyl group _is- (CH ₂ ) _k C (CH ₃ ) H (CH ₂ ) _i OC _j H _{2j + 1-} (CH ₂ ) _k C ( _{OC j H 2j + 1) H} (CH 2) i CH 3 (j is an integer of 1 to 3, c is an integer of 4 to 14, k, i can illustrate representative.) the meaning of the above, the branched-chain In the case of an alkoxyalkyl group, it may be a racemic mixture or an optically active group. As A

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Can be exemplified as preferred. From the viewpoint of increasing the response speed of the liquid crystalline composition containing the optically active substance of the present invention, it is preferable to increase the dipole moment around the asymmetric carbon or to increase the rotation hindrance. In Y, a single bond,
-O- or -CO ₂ - is preferably, linearity of the molecule, from the viewpoint of Deeki of inclined liquid crystal phase by the induced dipole moment -CO ₂ -, - O -, - OCH ₂ - or - CH ₂
Preferably O-, a synthetic bookmarks single bond from the viewpoint of ease, -CO ₂ -, - O- or is preferably -CH ₂ O-, is.

X is preferably a single bond, -O-, -CO ₂ -or -OCO- from the viewpoint of easiness of synthesis, and V is the magnitude of dipole moment, rotation hindrance, and induction. -CO _2- , -OCO from the viewpoints of the ease of appearance of the tilted liquid crystal phase and the ease of synthesis due to the dipole moment
—, —OCH ₂ — or —CH ₂ O— is preferable.

The compound of the general formula (1) can be produced by the following method.・ When Y is -CO _2-

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The compound of the formula (2) can also be synthesized by the following method.

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When Y is -O-

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When Y is -OCH _2-

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The one that is considered to contribute the most to the development of spontaneous polarization or potential spontaneous polarization in a ferroelectric liquid crystal or a compound as a compound material for the ferroelectric liquid crystal is rotation around asymmetric carbon. Is considered to be a regulated large permanent dipole moment.

The optically active compound of the present invention represented by the general formula (1) has an asymmetric carbon fixed by a δ-valerolactone ring, which can be regarded as a part of mesogen.

In the case of a δ-valerolactone ring, without substitution, the energy difference between the pseudo-boat type and pseudo-chair type conformations is low at 0.54 kcal / mol, and it is said that the conformation changes easily. I have. (T.Philip, N.
L. Allinger, J. Am. Chem. Soc., 103 2151, '81)
When substituents are introduced at the 2- and 5-positions of δ-valerolactone, the substituents can easily assume a pseudo-boat form in the cis configuration,
It is presumed that the ans arrangement makes it easier to take the pseudo chair type.

At this time, in the pseudo chair type, a larger dipole moment is expected because the lactone bond is closer to a plane, but in the trans configuration, there is no asymmetry with respect to the rotation around the molecular long axis. Large spontaneous polarization cannot be expected.

However, 2,2 represented by the general formula (1)
When a 5,5-substituted δ-valerolactone is present, the δ-valerolactone ring tends to have a more planar structure due to the interaction of the substituents at the 5,5-positions, and thus the equilibrium largely shifts from a pseudo-boat type to a pseudo-chair type. It is thought that there is.

Further, by using 5,5-disubstitution, a large asymmetrical effect occurs because one substituent is located at an axial position where steric hindrance is greater with respect to rotation around the molecular long axis.
The result is a large spontaneous polarization. In other words, in the present invention, the use of the 5,5-disubstituted lactone has an excellent feature that the melting point is low while the conformation is fixed, and the optically active substance for ferroelectric liquid crystal having a large spontaneous polarization can be obtained. Having.

Some of the optically active substances of the present invention show a liquid crystal phase, and others do not show a liquid crystal phase by themselves.
Non-chiral liquid crystal or liquid crystal composition showing a phase sequence of isotropic phase-nematic phase-smectic A phase-smectic C phase or isotropic phase-nematic phase-smectic C phase, even though it does not show a liquid crystal phase by itself, It has the property of inducing a ferroelectric phase (chiral smectic C phase) when added in an amount of 1 to 90 mol% within a range that does not destroy the liquid crystallinity. Therefore, even those that do not exhibit a liquid crystal phase by themselves are useful as additives for the ferroelectric liquid crystal composition.

As a liquid crystal, for example, when a liquid crystal is used for a display device such as a display, it is more preferable to use a plurality of liquid crystal compounds or a mixture of these and a compound for compounding than to use a single liquid crystal compound. Advantageously, physical properties such as a temperature range (a temperature range showing ferroelectricity), a tilt angle, a helical pitch, a spontaneous polarization value, and a rotational viscosity can be changed.

The liquid crystal composition of the present invention may contain at least one optically active substance represented by the general formula (1), and may be mixed with a compound or composition exhibiting ferroelectricity. The above-mentioned non-chiral liquid crystal or liquid crystal composition may be contained, and the liquid crystal composition may be represented by a general formula
Preferred compounds that can be mixed with the optically active compound represented by formula (1) include the following.

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[0052]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the examples.

Reference Example 1 t-butyl es (S) -γ-butyrolactone-γ-carboxylate
Synthesis of Ter (S) -γ-butyrolactone-γ-carboxylic acid is DLCoffen
It was synthesized according to the method of J. Org. Chem., 1988, 53, p4780-4786. That is, while 147 g of L-glutamic acid was suspended in 500 ml of water and stirred vigorously, sodium nitrite was added thereto.
A solution of 104 g in 144 ml of water and 250 ml of 5.6 N hydrochloric acid were simultaneously added dropwise over 5 hours. During the addition, the reaction temperature was kept at 15-20 ° C. After completion of the dropwise addition, the mixture was stirred at room temperature overnight, and then water was distilled off under reduced pressure while keeping the temperature at not higher than 40 ° C., ethyl acetate was added, and the mixture was dried over magnesium sulfate.

This was filtered and 20 g of an acid-type ion exchange resin (Amberlite IR-120B) was added to the filtrate to remove residual glutamic acid. Then, the mixture was filtered, the solvent was distilled off from the filtrate under reduced pressure, and the remaining water was removed by azeotropic distillation with benzene. Methylene chloride was added thereto, and the mixture was crystallized in a refrigerator to obtain 74 g of (S) -γ-butyrolactone-γ-carboxylic acid. This was suspended in 200 ml of ether, and 25 g of acid-type ion exchange resin (Amberlite IR-120B) was used.
And cooled to -20 ° C, isobutylene 60 ml (1.2 equivalents)
Was added and the mixture was stirred and reacted at 0 ° C. for 4 hours. After the reaction, the solid was filtered, and isobutylene and ether were distilled off from the filtrate, followed by distillation under reduced pressure to obtain (S) -γ-butyrolactone-γ-carboxylic acid t-butyl ester. (120 ~ 123 ℃ / 4mm
Hg, [α] _D (23.5 ° C.) = + 4.81 (C = 0.935, CHCl ₃ )

Example 1 (R) -2- (4'-octyloxybiphenyl-4-carboxy)-
Synthesis of 5,5-dimethyl-δ-valerolactone 5.2 g of β-hydroxyisovaleric acid and 15.2 g of acetylmalic acid monoethyl ester were dissolved in anhydrous methanol, and 0.14 g of sodium hydroxide was added thereto. A voltage of ± 20 V was applied for 5 hours to perform Kolbe electrolysis. After the reaction, 8 g of sodium hydroxide was added to the solution, 200 ml of a 1: 1 water / methanol solution was further added, and the mixture was left overnight at room temperature to hydrolyze. After distilling off most of the methanol in this solution,
The neutral component in the solution was extracted with diethyl ether, hydrochloric acid was added to the remaining aqueous alkali solution to adjust the pH to 1, sodium chloride was added until saturation, and the reaction product was extracted with chloroform. The obtained chloroform solution was washed with water and then dried over magnesium sulfate.Chloroform was distilled off under reduced pressure, and 8.3 g of the obtained crude product was treated with 150 ml of benzene.
The mixture was dissolved in l, and 0.1 g of p-toluenesulfonic acid was added, followed by refluxing for 5 hours. Then, the solution is cooled to room temperature and extracted with ether, and the extract is washed with a saturated aqueous solution of sodium hydrogen carbonate and then with water, and dried. The solvent is distilled off from the extract under reduced pressure to obtain a crude product. The obtained crude product was purified by silica gel column chromatography to obtain 5.2 g of (S) -2-hydroxy-5,5-dimethyl-δ-valerolactone.

0.2 g of this is 4'-octyloxybiphenyl
4-Suspension was suspended in 5 ml of dry benzene together with 0.25 g of carboxylic acid, 0.05 ml of diethyl azodicarboxylate and 0.3 g of triphenylphosphine were sequentially added, and the mixture was reacted overnight at room temperature. The reaction product solution was concentrated and purified by silica gel column chromatography to give (R) -2- (4'-octyloxybiphenyl-4-carboxy) -5,5-dimethyl-
0.3 g of δ-valerolactone was obtained. ^{1 HNMR = 8.12 (2Hd),} 7.
60 (4Hq), 6.98 (2Hd), 5.47 (1Hd, d), 4.02 (2H, t), 1.1 ~ 2.5
(18H, m), 0.90 (3H, t)

By using 3-hydroxypropionic acid, 3-ethyl-3-hydroxypentanoic acid or 3-propyl-3-hydroxyhexanoic acid instead of β-hydroxyisovaleric acid in the same manner as described above, A derivative in which R ₂ is a hydrogen atom, an ethyl group or a propyl group in the compound represented by 1) can be synthesized.

Further, in place of 4'-octyloxybiphenyl-4-carboxylic acid, linear alkoxybiphenyl-4-carboxylic acid having 1 to 7 or 9 to 18 carbon atoms, branched alkoxybiphenyl-4 having 3 to 18 carbon atoms, -Carboxylic acid, 1 to 1 carbon atoms
C1-C18 alkoxyalkyloxybiphenyl-4-carboxylic acid having 3 alkoxy groups, C2-C18
Linear or branched alkenyloxybiphenyl-
4-carboxylic acid, C1-C18 linear or branched alkylbiphenyl-4-carboxylic acid, C2-C18 linear or branched alkenylbiphenyl-4-carboxylic acid, C1-C3 C1 to C18 alkoxyalkylbiphenyl-4-carboxylic acid having an alkoxy group of a C1 to C18 linear or branched alkoxycarbonylbiphenyl-4-
Carboxylic acid, linear or branched alkenyloxycarbonylbiphenyl-4-carboxylic acid having 2 to 18 carbon atoms, alkoxyalkyloxycarbonylbiphenyl-4-carboxylic acid having 1 to 18 carbon atoms having an alkoxy group having 1 to 3 carbon atoms Acid, linear or branched alkylcarbonyloxybiphenyl-4-carboxylic acid having 1 to 18 carbon atoms, linear or branched alkenylcarbonyloxybiphenyl-4-carboxylic acid having 2 to 18 carbon atoms, 1 to 1 carbon atoms C1-C18 alkoxyalkylcarbonyloxybiphenyl-4-carboxylic acid having 3 alkoxy groups, halogen-substituted alkoxybiphenyl-4-carboxylic acid, halogen-substituted alkylbiphenyl-4-carboxylic acid, halogen-substituted alkoxycarbonylbiphenyl-4 -Carboxylic acid, halogen-substituted alkylcarbonyloxybiphenyl-4-cal Phosphate, or a halogen-substituted alkenyloxy-4-carboxylic acid,
Halogen-substituted alkoxyalkyloxybiphenyl-4-
By using a carboxylic acid in the same manner as described above, the general formula
In the compounds represented by (1), R ₁ is a linear or branched alkyl or alkenyl group, a C ₁ to C 18 alkoxyalkyl group having a C ₁ to C 3 alkoxy group, or a halogen-substituted group thereof. Wherein X is an ether bond, a single bond, a carbonyloxy group or an oxycarbonyl group, A is biphenyl, and Y is a carbonyloxy group.

In place of 4'-octyloxybiphenyl-4-carboxylic acid, linear or branched alkoxyphenyloxymethylphenyl-4-carboxylic acid having 1 to 18 carbon atoms, alkoxy group having 1 to 3 carbon atoms Having 1 to 18 carbon atoms
Alkoxyalkyloxyphenyloxymethylphenyl-4-carboxylic acid, linear or branched alkenyloxyphenyloxymethylphenyl having 2 to 18 carbon atoms
4-carboxylic acid, linear or branched alkylphenyloxymethylphenyl-4-carboxylic acid having 1 to 18 carbon atoms, alkoxyalkylphenyloxymethylphenyl having 1 to 18 carbon atoms having an alkoxy group having 1 to 3 carbon atoms -4-carboxylic acid, linear or branched alkenylphenyloxymethylphenyl-4-carboxylic acid having 2 to 18 carbon atoms, linear or branched alkoxycarbonylphenyloxymethylphenyl-4-carboxylic acid having 1 to 18 carbon atoms Carboxylic acid, carbon number 1-3
C1-C18 alkoxyalkyloxycarbonylphenyloxymethylphenyl-4 having an alkoxy group
-Carboxylic acid, linear or branched alkenyloxycarbonylphenyloxymethylphenyl-4-carboxylic acid having 2 to 18 carbon atoms, linear or branched alkylcarbonyloxyphenyloxymethylphenyl-4 having 1 to 18 carbon atoms -Carboxylic acid, alkoxyalkylcarbonyloxyphenyloxymethylphenyl-4-carboxylic acid having 1 to 18 carbon atoms having an alkoxy group having 1 to 3 carbon atoms, 2 carbon atoms
To 18 linear or branched alkenylcarbonyloxyphenyloxymethylphenyl-4-carboxylic acids, halogen-substituted alkoxyphenyloxymethylphenyl-4-
Using a carboxylic acid, a halogen-substituted alkoxycarbonylphenyloxymethylphenyl-4-carboxylic acid, a halogen-substituted alkenyloxyphenyloxymethylphenyl-4-carboxylic acid or a halogen-substituted alkoxyalkyloxyphenyloxymethylphenyl-4-carboxylic acid as described above In the same manner as described above, a derivative in which A in the compound represented by the general formula (1) is phenyloxymethylphenyl can be synthesized.

Further, 4'-octyloxybiphenyl-4-
A similar benzyloxyphenyl-4-carboxylic acid derivative in place of the phenyloxymethylphenyl-4-carboxylic acid derivative described above as a substitute for the carboxylic acid,
When a phenylcarbonyloxyphenyl-4-carboxylic acid derivative or a phenyloxycarbonylphenyl-4-carboxylic acid derivative is used, A in the compound represented by the general formula (1) is benzyloxyphenyl, phenylcarbonyloxyphenyl or phenyloxycarbonylphenyl. Can be synthesized. Similarly, when a similar alcohol derivative is used in place of the carboxylic acid derivative, the general formula
In (1), a compound in which Y is an ether bond can be synthesized.

Example 2 (S) -2- (4'-octyloxybiphenyl-4-carboxy)-
Synthesis of 5,5-dimethyl-δ-valerolactone (S) -γ-butyrolactonecarboxylic acid t-butyl ester 5 g
(27 mmol) was dissolved in 100 ml of dry THF, replaced with argon, cooled in a dry ice-acetone bath, and added with 3 ml of water.
Methyl magnesium magnesium bromide-ether solution 27 ml
(3 equivalents) was slowly added dropwise, and after the addition was completed,
The mixture was stirred for an hour to react. Then, water was slowly added dropwise, and the mixture was neutralized with 3N-hydrochloric acid, THF was distilled off under reduced pressure, extracted with ethyl acetate, and the extract was washed with dilute hydrochloric acid, then with saturated saline, and dried over magnesium sulfate. The solvent was distilled off from the dried solution, and the residue was purified by silica gel column chromatography to obtain 1.45 g of (S) -2,5-dihydroxy-5-methyl-hexanoic acid t-butyl ester.

This was dissolved in 50 ml of benzene, p-toluenesulfonic acid was added, and the mixture was refluxed for 5 hours. The obtained reaction product was purified by column chromatography to obtain 0.7 g of (S) -2-hydroxy-5. , 5-Dimethyl-δ-valerolactone was obtained.

This 0.1 g and 0.2 g of 4'-octyloxybiphenyl-4-carboxylic acid were dissolved in methylene chloride, 0.2 g of dicyclohexylcarbodiimide (DCC) and 0.05 g of dimethylaminopyridine were added, and the mixture was allowed to react at room temperature overnight. . The reaction solution after filtration was concentrated and purified by column chromatography to obtain 0.18 g of (S) -2- (4'-octyloxybiphenyl-4-carboxy) -5,5-dimethyl-δ-valerolactone. Was.
Its melting point was 128 ° C.

Example 3 (S) -2- (4'-octyloxybiphenyl-4-carboxy)-
Synthesis of 5,5-diethyl-δ-valerolactone A Grignard reagent was prepared from 5.16 g of magnesium and 29.3 g of ethyl bromide in 200 ml of THF. −γ
6.3 g of (S) -2,5-dihydroxy-5-ethyl-hexanoic acid in the same manner as in Example 2 except that the solution was added to a solution of 10 g of t-butyl carboxylate in 100 ml of THF.
The t-butyl ester was obtained.

This was dissolved in 150 ml of benzene, 0.2 g of p-toluenesulfonic acid was added, and the mixture was refluxed for 5 hours. The reaction product was purified by column chromatography to give (S) -2-hydroxy
4.7 g of -5,5-diethyl-δ-valerolactone was obtained. this
Except that 0.1 g was used, 0.19 g of (S)-
2- (4'-octyloxybiphenyl-4-carboxy) -5,5-
Diethyl-δ-valerolactone was obtained. Its melting point was 81.2 ° C.

Example 4 (S) -2-hydroxy-5,5 was prepared in the same manner as in Example 3 except that 33 g of propyl bromide was used instead of ethyl bromide.
3.2 g of dipropyl-δ-valerolactone were obtained. This 0.
Except that 1 g was used, 0.15 g of (S) -2-
(4′-octyloxybiphenyl-4-carboxy) -5,5-dipropyl-δ-valerolactone was obtained. Its melting point is 65.9
° C.

Example 5 0.1 g of 2-hydroxy-5,5-diethyl-δ-valerolactone obtained in Example 3 and 0.2 g of 4′-octyloxy-3′-fluorobiphenyl-4-carboxylic acid were dried. Dissolved in benzene,
0.1 g of diethyl azodicarboxylate and 0.2 g of triphenylphosphine were added and reacted at room temperature overnight. After evaporating the solvent from the solution thus obtained, it was purified by column chromatography and 0.12 g of (R) -2- (4'-octyloxy-3'-
(Fluorobiphenyl-4-carboxy) -5,5-diethyl-δ
-Valerolactone was obtained. Its melting point was 74 ° C.

Example 6 0.1 g of 2-hydroxy-5,5-diethyl-δ-valerolactone obtained in Example 3 and 0.2 g of 2- (4-carboxyphenyl) -5-decyloxypyrimidine were used in Example 2 And purified by silica gel chromatography to give 0.07 g of
(S) -2- (5-decyloxy-2-pyrimidinophenyl-4-carboxy) -5,5-diethyl-δ-valerolactone was obtained.
Its melting point was 98 ° C.

Example 7 Example 7 was repeated except that the same amount of 2- (4-hydroxyphenyl) -5-octyloxy-pyrimidine was used instead of 4'-octyloxy-3'-fluorobiphenyl-4-carboxylic acid. (R) -2- (5-octyloxy-2-pyrimidinophenyl-4-oxy) 5,5-diethyl-δ-valerolactone 0.
06g was obtained. Its melting point was 95 ° C.

Example 8 The procedure of Example 5 was repeated except that 0.3 g of 4-octyloxy-3-cyanobenzoic acid was used instead of 0.2 g of 4'-octyloxy-3'-fluorobiphenyl-4-carboxylic acid. (R) -2- (4-
0.15 g of octyloxy-3-cyanophenylcarboxy) 5,5-diethyl-δ-valerolactone was obtained. This compound was oily at room temperature.

Example 9 (R) -2- (4'-octyloxybiphenyloxymethyl) -5,
5-dimethyl-δ-valerolactone and (2S) -2- (4′-octane
(Tyloxybiphenyloxymethyl) -5,5-dimethyl-δ
Synthesis of valerolactone 1.18 g of β-hydroxyisovaleric acid was dissolved in 50 ml of a 7% by weight hydrochloric acid-methanol solution and reacted at room temperature overnight. The solvent was distilled off from the solution after the reaction under reduced pressure to obtain crude β-hydroxyisovaleric acid methyl ester 1.3og. This is dissolved in diethyl ether, and 3,4-dihydro-2H-pyran
0.91 g and a catalytic amount of p-toluenesulfonic acid were added, and the mixture was reacted at room temperature with stirring overnight. The obtained reaction product solution is washed with a saturated aqueous solution of sodium hydrogen carbonate and then with water,
After drying over magnesium sulfate, the solvent is distilled off under reduced pressure to give crude β-dihydropyranyloxyisovalerate methyl ester.
1.98 g was obtained.

Next, 0.7 g of lithium aluminum hydride was suspended in 20 ml of diethyl ether, and 1.98 g of methyl β-dihydropyranyloxyisovalerate was added to diethyl ether.
A solution dissolved in 3 ml is slowly dropped into this suspension,
The reaction was allowed to proceed overnight at room temperature. The mixture was further heated to reflux for 1 hour, cooled, cooled, cooled with ice, added with 0.7 ml of water, 0.7 ml of 15% aqueous sodium hydroxide solution and 2.1 ml of water, stirred at room temperature for 1 hour, and then added with 20 ml of tetrahydrofuran. And further stirred at room temperature for 1 hour. The precipitated solid was separated by filtration, the solid was washed with 10 ml of tetrahydrofuran, the washing liquid was added to the filtrate, and the solvent was distilled off under reduced pressure from the combined filtrate and washing liquid to give crude 3-dihydropyranyloxy-. 1.32 g of 3-methylbutanol was obtained.

This was dissolved in dichloromethane (5 ml), carbon tetrabromide (3.76 g) was added thereto, and while stirring, a solution of triphenylphosphine (1.95 g) in dichloromethane (10 ml) was slowly added dropwise thereto, followed by stirring at room temperature for 2 hours. Reacted. The reaction product solution is placed in 200 ml of pentane, and the pentane layer is collected at an angle.The collected pentane solution is washed with a saturated aqueous solution of sodium hydrogen carbonate and then with water, dried over magnesium sulfate, and then the solvent is distilled off under reduced pressure. The residue was purified by distillation under reduced pressure to obtain 1.71 g of purified 3-dihydropyranyloxy-3-methylbutyl bromide.

Next, 0.17 g of sodium was added to dry ethanol 1
0 ml, and thereto was added 1.17 g of ethyl malonate, and 1.71 g of 3-dihydropyranyloxy-3-methylbutyl bromide was slowly added dropwise. After stirring at room temperature for 2 hours, the mixture was stirred at room temperature for 2 hours.
The reaction was refluxed for an hour. The reaction product solution was cooled to room temperature, the solid was filtered off, and the filtrate was dried. This dried product was dissolved in 30 ml of benzene, p-toluenesulfonic acid was added in a catalytic amount, and the mixture was refluxed for 3 hours. After the reaction, the reaction product solution was cooled to room temperature, washed with a saturated aqueous solution of sodium hydrogencarbonate, then with water, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude product. Purification by chromatography gave 0.47 g of ethyl 5,5-dimethyl-δ-valerolactone-2-carboxylate.

Next, 0.06 g of sodium borohydride was suspended in 2 ml of ethanol, and 5,5-dimethyl-δ-
A solution of 0.47 g of valerolactone-2-ethyl carboxylate dissolved in 2 ml of ethanol was slowly added dropwise, and the mixture was stirred at room temperature for 10 minutes, adjusted to pH 3 with 10% hydrochloric acid, and filtered to remove insoluble materials. The filtrate was dried to give crude 2-hydroxymethyl-
0.45 g of 5,5-dimethyl-δ-valerolactone was obtained.

This was dissolved in 2 ml of pyridine, 0.81 g of p-toluenesulfonic acid chloride was added, and the mixture was stirred and reacted at room temperature overnight. After the reaction, the resulting solution was poured into dilute hydrochloric acid while cooling with ice, and the reaction product was extracted with diethyl ether.
The extract was washed with dilute hydrochloric acid and then with water, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude product.The crude product was purified by silica gel column chromatography and 2-tosyloxymethyl-5,5-dimethyl 0.70 g of -δ-valerolactone was obtained.

This was dissolved in 10 ml of acetone, 0.48 g of sodium iodide was added, and the mixture was refluxed for 10 hours to react. After the reaction solution was evaporated to dryness under reduced pressure, the reaction product was extracted with diethyl ether, the extract was washed three times with water, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude product. 2-
Methyl-5,5-dimethyl-δ-valerolactone 0.60
g.

Next, 0.09 g of 60% sodium hydride was suspended in 5 ml of dimethylformamide, and a solution of 0.63 g of 4'-octyloxybiphenol dissolved in 5 ml of dimethylformamide was added thereto. The mixture was stirred at room temperature for 1 hour to react. I let it. To the resulting solution 2-methyl iodide-5,5-dimethyl-δ
0.60 g of valerolactone was added, and the mixture was reacted at room temperature with stirring for 2 days. The solution after the reaction was poured into ice water, and the reaction product was extracted with diethyl ether. The extract was washed three times with water, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography to give 2- (4'-octyloxybiphenyloxymethyl). -5,5-dimethyl-δ-valerolactone 0.58
g. Both components obtained by optical resolution of this by liquid chromatography were recrystallized with ethanol, respectively, and (R) -2-
0.20 g of (4'-octyloxybiphenyloxymethyl) -5,5-dimethyl-δ-valerolactone and (2S) -2- (4'-octyloxybiphenyloxymethyl) -5,5-dimethyl-δ-
Valerolactone was obtained in an amount of 0.11 g. All of these compounds exhibited the following phase transition behavior.

[0079]

(Equation 1)

By using 3-hydroxypropionic acid, 3-ethyl-3-hydroxypentanoic acid or 3-propyl-3-hydroxyhexanoic acid instead of β-hydroxyisovaleric acid in the same manner as described above, A derivative in which R ₂ is a hydrogen atom, an ethyl group or a propyl group in the compound represented by 1) can be synthesized.

Instead of 4'-octyloxybiphenol, a linear alkoxybiphenol having 1 to 7 or 9 to 18 carbon atoms, a branched alkoxybiphenol having 3 to 18 carbon atoms, or a carbon atom having an alkoxy group having 1 to 3 carbon atoms. Numbers 1-18
Of an alkoxyalkyloxybiphenol having 2 to 2 carbon atoms
18 straight-chain or branched-chain alkenyloxybiphenols, straight-chain or branched-chain alkyl biphenols having 1 to 18 carbon atoms, straight-chain or branched-chain alkenyl biphenols having 2 to 18 carbon atoms, alkoxy groups having 1 to 3 carbon atoms Having 1 to 18 carbon atoms, an alkoxyalkylbiphenol having 1 to 1 carbon atoms
18 straight-chain or branched-chain alkoxycarbonylbiphenols, straight-chain or branched-chain alkenyloxycarbonylbiphenols having 2 to 18 carbon atoms, alkoxyalkyloxycarbonylbiphenols having 1 to 18 carbon atoms having an alkoxy group having 1 to 3 carbon atoms A straight-chain or branched alkylcarbonyloxybiphenol having 1 to 18 carbon atoms, 2 to 18 carbon atoms
Linear or branched alkenylcarbonyloxybiphenol having 1 to 3 carbon atoms and having 1 to 3 carbon atoms
~ 18 alkoxyalkylcarbonyloxybiphenol, halogen-substituted alkoxybiphenol, halogen-substituted alkylbiphenol, halogen-substituted alkoxycarbonylbiphenol, halogen-substituted alkylcarbonyloxybiphenol, halogen-substituted alkenyloxybiphenol or halogen-substituted alkoxyalkyloxybiphenol and Similarly, in the compound represented by the general formula (1), R ₁ is a linear or branched alkyl group or alkenyl group,
3 is an alkoxyalkyl group having 1 to 18 carbon atoms having an alkoxy group or a halogen-substituted one thereof, wherein X is an ether bond, a single bond, a carbonyloxy group or an oxycarbonyl group, and A is biphenyl Y
Is a carbonyloxy group.

Also, in place of 4′-octyloxybiphenol, a linear or branched alkoxyphenyloxymethylphenol having 1 to 18 carbon atoms, an alkoxyalkyl having 1 to 18 carbon atoms and having an alkoxy group having 1 to 3 carbon atoms. Oxyphenyloxymethyl phenol, linear or branched alkenyloxyphenyloxymethyl phenol having 2 to 18 carbon atoms, linear or branched alkyl phenyloxymethyl phenol having 1 to 18 carbon atoms, alkoxy having 1 to 3 carbon atoms C1-C18 alkoxyalkylphenyloxymethylphenol having a group, C2-C18 linear or branched alkenylphenyloxymethylphenol, C1-C18 linear or branched alkoxycarbonylphenyloxy Methylphenol, carbon number 1
C1-C18 alkoxyalkyloxycarbonylphenyloxymethylphenol having 3 alkoxy groups, C2-C18 linear or branched alkenyloxycarbonylphenyloxymethylphenol, C1-C18 linear or Branched-chain alkylcarbonyloxyphenyloxymethylphenol, alkoxyalkylcarbonyloxyphenyloxymethylphenyl-4-carboxylic acid having 1 to 18 carbon atoms having an alkoxy group having 1 to 3 carbon atoms, linear chain having 2 to 18 carbon atoms or Branched-chain alkenylcarbonyloxyphenyloxymethylphenol,
By using a halogen-substituted alkoxyphenyloxymethylphenol, a halogen-substituted alkoxycarbonylphenyloxymethylphenol, a halogen-substituted alkenyloxyphenyloxymethylphenol, or a halogen-substituted alkoxyalkyloxyphenyloxymethylphenol in the same manner as described above, A) wherein A is phenyloxymethylphenyl among the compounds represented by the formula (1) can be synthesized.

Further, when a similar benzyloxyphenol derivative, phenylcarbonyloxyphenol derivative or phenyloxycarbonylphenol derivative is used in place of the above-mentioned phenyloxymethylphenol derivative as a substitute for 4′-octyloxybiphenol, the general formula Compounds in which A is benzyloxyphenyl, phenylcarbonyloxyphenyl or phenyloxycarbonylphenyl among the compounds represented by (1) can be synthesized.

Example 10 (S) -2- (4'-octyloxybiphenyl-4-methyleneoxy
B) Synthesis of 5,5-dimethyl-δ-valerolactone (S) -2-hydroxy-5,5-dimethyl-δ- obtained in Example 1.
Using 0.2 g of valerolactone, 0.5 g of 4′-octyloxy-4-bromomethylbiphenyl was reacted with dimethylformamide using 0.06 g of 60% sodium hydride as a catalyst. After treating the obtained reaction solution with dilute hydrochloric acid, the reaction product is extracted with diethyl ether, the extract is washed with water, dried over magnesium sulfate, and then the ether is distilled off. Purify by chromatography to give (S) -2- (4'-octyloxybiphenyl-4
-Methyleneoxy) -5,5-dimethyl-δ-valerolactone
0.2 g was obtained. Its phase transition behavior was as follows.

[0085]

(Equation 2)

Instead of (S) -2-hydroxy-5,5-dimethyl-δ-valerolactone, (S) -2-hydroxy-δ-valerolactone, (S) -2-hydroxy-5,5-diethyl -Δ-valerolactone or (S) -2-hydroxy-5,5-dipropyl-δ
By using -valerolactone in the same manner as described above, a derivative in which R ₂ is a hydrogen atom, an ethyl group or a propyl group in the compound represented by the general formula (1) can be synthesized.

Further, in place of 4′-octyloxy-4-bromomethylbiphenyl, the octyloxy group part is a straight-chain alkoxy group having 1 to 7 or 9 to 18 carbon atoms,
To 18 branched alkoxy groups, a C1 to C18 alkoxyalkyloxy group having a C1 to C3 alkoxy group,
A linear or branched alkenyloxy group having 2 to 18 carbon atoms, a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkenyl group having 2 to 18 carbon atoms,
A C1-C18 alkoxyalkyl group having 3 alkoxy groups, a C1-C18 linear or branched alkoxycarbonyl group, a C2-C18 linear or branched alkenyloxycarbonyl group, A C1-18 alkoxyalkyloxycarbonyl group having an alkoxy group of the number 1 to 3, a C1-18 linear or branched alkylcarbonyloxy group, a C2-18 linear or branched An alkenylcarbonyloxy group, an alkoxyalkylcarbonyloxy group having 1 to 18 carbon atoms having an alkoxy group having 1 to 3 carbon atoms, a halogen-substituted alkoxy group, a halogen-substituted alkyl group, a halogen-substituted alkoxycarbonyl, a halogen-substituted alkylcarbonyloxy group, a halogen A substituted alkenyloxy group or a halogen-substituted alkoxyalkyloxy group Alkyl or alkenyl group R ₁ is a straight-chain or branched-chain in the compounds represented by the general formula (1) by the same manner as described above with reference to the carbon atoms which has an alkoxy group having 1 to 3 carbon atoms 1 ~ 18 alkoxyalkyl group or a halogen-substituted group thereof, wherein X is an ether bond, a single bond, a carbonyloxy group or an oxycarbonyl group, A is biphenyl and Y is a carbonyloxy group. Can be synthesized.

Further, by using a compound in which the biphenyl moiety is phenyloxymethylphenyl in place of 4′-octyloxy-4-bromomethylbiphenyl in the same manner as described above, the compound represented by the general formula (1) is obtained. A derivative in which A is phenyloxymethylphenyl can be synthesized. Further, when benzyloxyphenyl, phenylcarbonyloxyphenyl or phenyloxycarbonylphenyl is used instead of 4′-octyloxy-4-bromomethylbiphenyl, the general formula
Compounds in which A is benzyloxyphenyl, phenylcarbonyloxyphenyl or phenyloxycarbonylphenyl among the compounds represented by (1) can be synthesized.

In Examples 1 to 3, 4'-octyloxybiphenyl-4-carboxylic acid, 4'-octyloxybiphenol or 4'-octyloxy-4-bromomethylbiphenyl was replaced by one of biphenyl instead of the biphenyl group. One in which phenylene is a pyrimidinylene or pyridazinylene group, one in which a phenylene in a phenoxycarbonyloxyphenyl group is a pyrimidinylene or a pyridazinylene group, one in which one phenylene in a phenylcarbonyloxyphenyl group is a pyrimidinylene or a pyridazinylene group, a benzyloxyphenyl group Wherein one of the phenylenes is a pyrimidinylene or pyridazinylene group, and one in which the phenylene of the phenoxymethylphenyl group is a pyrimidinylene or a pyridazinylene group, is represented by the general formula (1). Is a single bond phenylene and pyrimidinylene or pyridazinylene group as A in the compounds, can be synthesized that bound carbonyloxy, oxycarbonyl, Mechirenokishi or oxymethylene group.

Example 11 The following compounds were mixed at the following mixing ratio to obtain a liquid crystal composition.

[0091]

Embedded image

[0092]

Embedded image

This composition shows the following phase transition:

[0094]

(Equation 3)

In the above description, Cryst indicates a crystal, SmC indicates a smectic C phase, N indicates a nematic phase, and a number near an arrow indicates a transition temperature (° C.) to the phase. This liquid crystal composition is not a ferroelectric liquid crystal and does not exhibit spontaneous polarization because it is composed only of a non-chiral compound.

By mixing 98 mol% of this composition with 2 mol% of the optically active substance obtained in Example 1, a ferroelectric liquid crystal composition was obtained. This ferroelectric liquid crystal composition exhibits an Sm ^* C phase in a temperature range from around room temperature to 60 ° C., an SmA phase at 60 to 69 ° C., a chiral nematic phase at 69 to 77 ° C., and an isotropic liquid at higher temperatures. It became.

Separately, a 2 μm-thick cell having a transparent electrode whose surface is rubbed and parallel-aligned by applying polyimide as an alignment agent is prepared, and this ferroelectric liquid crystal composition is injected into the cell. A ferroelectric liquid crystal device was produced.
This element was placed between two orthogonal polarizers, and an electric field was applied. It was observed that the intensity of the transmitted light changed with the application of ± 20 V.
Was 90 μsec.

Example 12 The following compounds obtained in Examples 2 to 8 were added in an amount of 2 mol% each to a liquid crystal mixture composed of the following non-chiral compounds.

[0099]

Embedded image

[0100]

Embedded image

The liquid crystal composition comprising the above non-chiral compound exhibits the following phase transition.

[0102]

(Equation 4)

The liquid crystal compositions to which the above compounds obtained in Examples 2 to 8 were respectively added were placed in an 8 μm cell, and the spontaneous polarization value at 25 ° C. was measured by a triangular wave method. The values are shown in Table 1 together with the phase transition behavior.

[0104]

[Table 1]

[0105]

As described above, the optically active substance of the present invention, which exhibits liquid crystallinity, exhibits high spontaneous polarization as a ferroelectric liquid crystal, has no coloring, and has excellent chemical stability such as hydrolysis resistance. It shows excellent performance with good light stability, and even if it does not show liquid crystallinity, it can be mixed with a non-ferroelectric liquid crystal composition to form a ferroelectric liquid crystal composition or as an additive. When used as a component in a liquid crystal composition, it enhances the spontaneous polarization of the composition and has an effect on improving the response speed. Without adding or blending, the composition is not colored, and the composition is chemically or light stable. The liquid crystal composition of the present invention exhibits an excellent property of not deteriorating the properties, and the liquid crystal composition of the present invention is also a composition having excellent performance as described above.

Continuation of the front page (56) References JP-A-59-164788 (JP, A) JP-A-1-199959 (JP, A) JP-A-2-294387 (JP, A) JP-A-3-20269 (JP) JP-A-3-72473 (JP, A) JP-A-3-95174 (JP, A) JP-A-3-128371 (JP, A) Chem. Soc. , Chem. Commun. , [5] (1991.3.1.) Pp. 311-312 (58) Fields investigated (Int. Cl. ⁶ , DB name) C07D 309/30 C07D 405/00-405/12 REGISTRY (STN) CA (STN)

Claims (2)

(57) [Claims] An optically active compound having a δ-valerolactone ring represented by the general formula (1). Embedded image ( Wherein , R ₁ is a straight-chain or branched-chain alkyl group having 4 to 18 carbon atoms, a straight-chain or branched-chain alkenyl group having 2 to 18 carbon atoms, a carbon atom having 1 to 3 carbon atoms in the alkoxy portion, A linear or branched alkoxyalkyl group of the formulas 1 to 18, or one of the hydrogen atoms among these substituents
One or be one that is halogen-substituted, if it is a structure that may have an optically active group shows what it may be a good racemic be optically active group, R ₂
Is a methyl group, an ethyl group or propyl group, X is a single bond, -O -, - CO ₂ - or -OCO- indicates, Y is a single _{bond, -CO 2 -, - O -} , - CH 2 O -Or -OCH ₂
And A represents And B, B ′ and B ″ each represent hydrogen, a halogen, a cyano group, a methyl group, a methoxy group or a trihalomethyl group, and V represents a single bond, —CH ₂ O—, —OCH ₂ , and —CO ₂ —. Or -OCO-, and * indicates that the carbon to which it is attached is an asymmetric carbon.) 2. A liquid crystal composition comprising at least one optically active substance according to claim 1.