JPH0665259A - Silicon-containing optically active tetrahydrofuran drrivative, liquid crystal composition and liquid crystal display element comprising the same - Google Patents

Abstract

PURPOSE:To obtain a new compound, excellent in high-speed responsiveness, orienting properties and chemical stability and useful as a liquid crystal optical switching elements, etc., for display. CONSTITUTION:The objective compound of formula I [R<1> is 1-18C alkyl; X is single bond or O; ring A is (F-substituted)1,4-phenylene or trans-1,4- cyclohexylene; R<2> is 1-10C alkyl], e.g. (2R,4S)-2-(2-butyldimethylsilyl)ethyl-4-[4-(4- octyloxybenzoyloxy)phenyl]tetrahydrofuran. Furthermore, this compound of formula I is obtained by reacting a new compound of formula III (R<3> is H or 1-18C alkyl) with a compound of formula III in the presence of a condensing agent such as dicyclohexylcarbodiimide.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel silicon-containing optically active tetrahydrofuran derivative and a liquid crystal material containing the same, and more particularly to a ferroelectric liquid crystal display material excellent in responsiveness and memory property. is there.

[0002]

2. Description of the Related Art Liquid crystal display devices are widely used at present due to their excellent features (low voltage operation, low power consumption, thin display, can be used even in bright places and do not cause eye strain). However, the TN type, which is the most common display method among them, has a very slow response as compared with other light emitting display methods such as CRT, and obtains a display memory (memory effect) when the applied electric field is cut off. Therefore, there are many restrictions on the application to moving screens such as an optical shutter that requires high-speed response, a printer head, or a television that requires time-division driving, and it cannot be said that it is a suitable display method.

Recently, a display method using a ferroelectric liquid crystal has been reported. According to this, a high-speed response and a memory effect of 100 times or more that of a TN type liquid crystal can be obtained, so that it is expected as a next-generation liquid crystal display element. , Currently, research and development are actively underway.

The liquid crystal phase of the ferroelectric liquid crystal belongs to the tilt type chiral smectic phase, of which the chiral smectic C (hereinafter abbreviated as SC ^* ) phase has the lowest viscosity and is most desirable.

A large number of liquid crystal compounds exhibiting the SC ^* phase have already been synthesized and studied, but the SC ^* phase in the following conditions for use as a ferroelectric liquid crystal display device, that is, (a) a wide temperature range including room temperature. (B) In order to obtain good orientation, the SC ^* phase has an appropriate phase series on the high temperature side, and its helical pitch is large, and (c) it has an appropriate tilt angle. D) A compound that alone satisfies the requirements of low viscosity, (e) large spontaneous polarization to some extent, and (f) fast response is not known. Therefore, mix several or more compounds to make SC
^It must be used as a liquid crystal composition exhibiting a ^* phase (hereinafter, abbreviated as SC ^* liquid crystal composition).

SC ^{* A} liquid crystal composition is prepared by using an achiral compound and smectic C (hereinafter referred to as SC
Is omitted. ) A method of adding a dopant composed of an optically active compound to a matrix liquid crystal exhibiting a phase (hereinafter, abbreviated as SC matrix liquid crystal) as a so-called chiral dopant can obtain a composition having a lower viscosity and enables high-speed response. Therefore, it is general. A compound used as a chiral dopant does not necessarily have to exhibit an SC ^* phase or even a liquid crystal phase by itself, but it is possible to induce sufficient spontaneous polarization in a liquid crystal composition with a small amount of addition and to induce as a chiral dopant. It is necessary to exhibit properties such as a sufficiently large spiral pitch.

In order to induce a large spontaneous polarization as a chiral dopant, it is necessary that a group having a strong dipole moment is fixed as close as possible to the central skeleton (core) and asymmetric carbon of the compound molecule. This is already known. Based on such an idea, the inventors of the present invention formula (IV)

[0008]

[Chemical 3]

(In the formula, Mes represents a liquid crystal skeleton, and R represents an alkyl group.) An optically active lactone derivative represented by the formula is synthesized. This compound induces a sufficiently large spontaneous polarization with a small amount of addition and a high-speed response. It has been found that it is possible to prepare an SC ^* liquid crystal composition having a high property. (Page 16 of the 16th Liquid Crystal Symposium Proceedings and JP-A-2-286673)

[0010]

However, it is known that the spontaneous polarization of the composition should be small to some extent in order to obtain good switching characteristics such as memory property. There is a problem that the composition has an extremely large viscosity and the spontaneous polarization of the composition becomes too large to obtain a high-speed response.

The compound having a trialkylsilyl group introduced into the terminal group R of the compound represented by the general formula (IV) showed an improvement in spontaneous polarization, but no significant improvement in its viscosity.

Therefore, the present inventors have found that in order to obtain an optically active compound for chiral dopant having a lower viscosity, the compound represented by the general formula (V)

[0013]

[Chemical 4]

(In the formula, Mes represents a liquid crystal skeleton and R represents an alkyl group.) An optically active tetrahydrofuran derivative represented by the following formula was synthesized.
It was found that a composition having a lower viscosity than the compound represented by V) and capable of a fast response with smaller spontaneous polarization can be obtained. However, higher responsiveness than that obtained by the compound represented by the general formula (V) is desired.

The problem to be solved by the present invention is to provide an optically active tetrahydrofuran derivative in which a small amount of chiral dopant is added to a host liquid crystal to induce sufficient spontaneous polarization and a faster response is possible. Another object is to provide a ferroelectric liquid crystal display material and a display element using the same.

[0016]

In order to solve the above-mentioned problems, the present invention has the general formula (I)

[0017]

[Chemical 5]

(Wherein R ¹ represents a linear or branched alkyl group having 1 to 18 carbon atoms, and when R ¹ is a branched group, the compound of the general formula (I) is racemic. R ¹ represents a straight-chain alkyl group having 6 to 12 carbon atoms, X represents a single bond or —O—, and ring A represents 1 Represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group which may be substituted with one or two fluorine atoms.
R ² represents an alkyl group having 1 to 10 carbon atoms, preferably a linear alkyl group having 1 to 8 carbon atoms. The 2- and 4-positioned asymmetric carbon atoms of the tetrahydrofuran ring are each independently in the (R) or (S) configuration. The present invention provides an optically active tetrahydrofuran derivative containing silicon represented by the formula (1).

The present invention also provides a liquid crystal composition containing this compound. The liquid crystal composition of the present invention contains at least one compound represented by the general formula (I) as a constituent, and is particularly suitable for displaying a ferroelectric liquid crystal.

For ferroelectric liquid crystal displays, SC matrix liquid crystal containing at least one compound represented by the above general formula (I) as a part or all of the chiral dopant in the SC host liquid crystal as a main component ^. Liquid crystal compositions are suitable. Alternatively, by adding a small amount of the compound represented by the general formula (I) of the present invention to a nematic liquid crystal, the so-called reverse domain can be prevented as a TN type liquid crystal, or ST
It can also be used as an N-type liquid crystal.

The compound represented by the general formula (I) according to the present invention can be produced, for example, according to the following production method. That is, the general formula (VI)

[0022]

[Chemical 6]

An optically active lactone derivative containing silicon represented by the formula: wherein R ² has the same meaning as in formula (I) and R ³ represents an alkyl group having 1 to 18 carbon atoms. Is reduced with lithium aluminum hydride or the like to give an optically active 1,4-diol derivative.
By cyclizing this in the presence of an acid catalyst such as p-toluenesulfonic acid, the compound of the general formula (II)

[0024]

[Chemical 7]

An optically active tetrahydrofuran derivative represented by the formula (wherein R ² and R ³ have the same meanings as in formula (VI)) can be obtained. This is a mixture of a trans isomer and a cis isomer, and a compound represented by the general formula (VI) of the trans isomer is a compound represented by the general formula (II) of the cis isomer, and a compound of the general formula (VI) of the cis isomer. The compound represented by the formula () can be obtained by using a compound represented by the general formula (II) in the trans form as a main component.
These can be easily separated by a separation means such as ordinary column chromatography.

Next, the compound represented by the general formula (II) is dealkylated by reacting it with aluminum chloride and dimethyl sulfide to obtain a phenol derivative of the general formula (III).

[0027]

[Chemical 8]

A compound represented by the formula (wherein R ² has the same meaning as in formula (II)) can be obtained.

Here, the general formula (II) and the general formula (II
The compounds I) are both novel compounds, and the present invention also provides these compounds as synthetic intermediates for the compounds represented by the general formula (I).

Next, the compound represented by the general formula (II) and the general formula (VII)

[0031]

[Chemical 9]

(Wherein R ¹ , X and ring A are represented by the general formula (I)
Has the same meaning as in. ) Is reacted with a carboxylic acid represented by the formula (1) in the presence of a condensing agent such as DCC (dicyclohexylcarbodiimide) to obtain the compound represented by the general formula (I) of the present invention. Alternatively, a carboxylic acid represented by the general formula (VII) is reacted with a chlorinating agent such as thionyl chloride to give an acid chloride, and this is reacted with a compound represented by the general formula (II) in the presence of a base catalyst. You can also get

Here, the carboxylic acid represented by the general formula (VII) is a compound well known as an intermediate for the production of liquid crystal compounds.

The optically active lactone derivative represented by the general formula (VI) is a compound which the present inventors have shown for the first time, and an optically active oxirane derivative having a cyano group represented by the following general formula (VIII): It can be obtained by reacting a Grignard reagent containing silicon, then hydrolyzing the cyano group, and cyclizing in the presence of an acid catalyst.

[0035]

[Chemical 10]

(In the formula, R ² and R ³ have the same meanings as in formula (II).) As described above, the compound represented by formula (I) of the present invention can be obtained. Each specific compound belonging to these can be confirmed by means such as phase transition temperature such as melting point, infrared absorption spectrum (IR), nuclear magnetic resonance spectrum (NMR), mass spectrum (MS) and the like.

Typical examples of the compounds represented by the general formula (I) thus obtained are shown in Table 1.

[0038]

[Table 1]

One of the excellent features of the compound represented by the general formula (I) of the present invention is that it can induce a sufficient degree of spontaneous polarization even when added in a small amount and enables a high-speed response. it can. For example, as shown in Examples described later, No. (I-1) or (I-
Table 2 below shows the spontaneous polarization and electro-optical response speed at 25 ° C. of each SC ^* liquid crystal composition comprising each compound of 5) and a phenylpyrimidine-based host liquid crystal exhibiting the SC phase.

[0040]

[Table 2] On the other hand, No. (V-1) or (V-5) represented by the general formula (V) having a similar structure to the compound represented by No. (I-1) or (I-5)

[0041]

[Chemical 11]

The spontaneous polarization and electro-optical response speed at 25 ° C. of the SC ^* liquid crystal composition comprising the compound of (1) and the same host liquid crystal as above are shown in Table 3 below.

[0043]

[Table 3] From Tables 2 and 3 above, the composition using the compound represented by the general formula (I) of the present invention is compared with the composition using the compound represented by the general formula (V) having a similar structure. It can be understood that the responsiveness is excellent even though the spontaneous polarization is the same or rather small. This is because the viscosity of the compound represented by the general formula (I) is
It is shown that it is smaller than the compound represented by the general formula (V). Although other ferroelectric liquid crystal compounds having a trialkylsilyl group as a terminal group are known, examples of compounds such as the compound of the general formula (I) of the present invention in which the introduction thereof reduces the viscosity of the compound are described below. unknown.

The compound represented by the general formula (I) of the present invention has an asymmetric carbon atom at each of the 2-position and 4-position of the tetrahydrofuran ring. When the absolute configurations of the asymmetric carbon atoms are the same, that is, (2S, 4S) or (2R, 4R), the tetrahydrofuran ring has the trans configuration. The absolute configurations are different from each other, that is, (2S, 4R) or (2R,
4S) has a cis configuration. In the compound having an optically active tetrahydrofuran ring such as the compound represented by the general formula (I) or the compound represented by the general formula (V), the cis compound is effective as the chiral dopant for the ferroelectric liquid crystal. Yes, the spontaneous polarization induced by the trans form is much smaller than that in the cis form. However,
It is difficult to selectively synthesize a cis-form compound in production, and a mixture of a cis-form and a trans-form is usually obtained.
Since the spontaneous polarization induced by the trans form is far smaller than that of the cis form, the spontaneous polarizations induced as a mixture do not cancel each other out, and it is possible to use the mixture as it is, but preferably the cis form is used. It is desirable to use them separately. However, it is not necessary to strictly separate and purification is easy.

As is clear from Table 1 above, the compound represented by the general formula (I) of the present invention alone does not exhibit a liquid crystal phase, and therefore can be used by adding it as a chiral dopant in the host liquid crystal. .

As described above, the compound represented by the general formula (I) induces a sufficiently large spontaneous polarization as compared with the conventionally known optically active liquid crystal compound having 2-methylbutanol as an asymmetric source. Therefore, a ferroelectric SC ^* liquid crystal composition capable of high-speed response can be obtained by adding about 1% by weight or more to the matrix liquid crystal.

The compound represented by the general formula (I) does not show a liquid crystal phase by itself, but it is contained in the liquid crystal composition in an amount of 1 to 10% by weight.
The degree of inclusion does not significantly affect the temperature range of the liquid crystal phase, particularly the SC ^* phase.

Generally, the temperature range of the chiral nematic (N ^* ) phase is narrowed or easily eliminated for an optically active compound which induces a large spontaneous polarization even when added in a small amount, and the temperature range of the smectic A (SA) phase is expanded. Many have a strong tendency to do so. When such a compound is used as a chiral dopant, the obtained SC ^* composition has a phase sequence of I (isotropic liquid phase) -SA (smectic A phase) -SC ^* from a high temperature range. Often. However, in the current alignment technology, the SC ^* liquid crystal composition has a high temperature range from IN ^*.
It is considered most desirable to show a phase sequence of -SA-SC ^* . Since the compound represented by the general formula (I) does not tend to narrow the temperature range of the N ^* phase of the liquid crystal composition or expand the temperature range of the SA phase, it is extremely easy to obtain the above desirable phase series. Is.

In order to obtain excellent orientation, the above I-
In addition to the N ^* -SA-SC ^* phase sequence, N ^* and SC ^* phases,
In particular, it is important that the spiral pitch in the N ^* phase is large. In the compound represented by the above general formula (V) or (IV), since the helix is strongly induced in the N ^* phase, the pitch becomes considerably small even when used in a small amount,
In order to improve the orientation, it was necessary to adjust the pitch by adding a considerable amount of an optically active compound as a chiral dopant in which the induced spiral direction is opposite. However, in the compound represented by the general formula (I) of the present invention, the helical pitch induced by the compound is considerably increased due to the introduction effect of the trialkylsilyl group. But that adjustment became easier.

SC used in a host liquid crystal to which the compound represented by the general formula (I) of the present invention is added as a dopant
Examples of the compound include the following general formula (A)

[0051]

[Chemical 12]

(Wherein R ^a and R ^b are linear or branched alkyl groups, alkoxyl groups, alkoxycarbonyl groups,
It represents an alkanoyloxy group or an alkoxycarbonyloxy group, which may be the same or different. ) Phenylbenzoate-based compounds and general formula (B)

[0053]

[Chemical 13]

A pyrimidine compound represented by the formula (wherein R ^a and R ^b have the same meanings as in the general formula (A)) and the like. In addition, the general formula (A),
General formula (C) including (B)

[0055]

[Chemical 14]

(In the formula, R ^a and R ^b have the same meanings as in the general formula (A), and the ring L and the ring M are 1, 4 respectively.
-Phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, pyridazine-3,6
Represents a -diyl group, a 1,3-dioxane-2,5-diyl group or a halogen-substituted product thereof, which may be the same or different, and Z ^a is -COO-, -O.
_{CO -, - CH 2 O -} , - OCH 2 -, - CH 2 CH 2 -,
Represents -C≡C or a single bond. The compound represented by () can be used for the same purpose. For the purpose of expanding the temperature range of the SC phase to a high temperature range, the general formula (D)

[0057]

[Chemical 15]

(Wherein R ^a and R ^b have the same meanings as in formula (A), and ring L, ring M and ring N have the same meanings as ring L and ring M in formula (C). Which may be the same or different from each other, Z ^a and Z ^b each have the same meaning as Z ^{a in the} general formula (C), and may be the same or different from each other). The represented tricyclic compounds can be used.

It is effective that these compounds are mixed and used as an SC liquid crystal composition, but it is only necessary to show the SC phase as the composition, and it is not always necessary for each compound to show the SC phase. .

By adding the compound represented by the general formula (I) of the present invention and, if necessary, other optically active compound as a chiral dopant to the SC liquid crystal composition thus obtained, a wide temperature range including room temperature can be easily obtained. A liquid crystal composition exhibiting an SC ^* phase in the range can be obtained.

An SC ^* liquid crystal composition obtained by adding the compound represented by the general formula (I) of the present invention to the above-mentioned SC host liquid crystal is formed as a thin film of about 1 to 20 μm between two transparent glass electrodes. By enclosing it, it can be used as a display cell. In order to obtain a good contrast, it is necessary to make the monodomain uniformly oriented, and many methods have been tried for this reason. In order to exhibit good orientation, it is necessary for the liquid crystal material to exhibit a phase sequence of IN ^* -SA-SC ^* from the high temperature side and to increase the helical pitch in the N ^* phase and SC ^* phase. However, as described above, when the compound of the general formula (I) of the present invention is used, it is easy to obtain such a composition.

[0062]

EXAMPLES The present invention will be specifically described below with reference to examples, but of course the gist and scope of application of the present invention are not limited to these examples.

The structure of each compound is NMR, IR, M
Confirmed by S and elemental analysis. The phase transition temperature was measured by using a polarization microscope equipped with a temperature control stage and a differential scanning calorimeter (DSC) together. (KBr) in IR
Means tableting, and (neat) means liquid film measurement. CDCl _{3 in} NMR represents a solvent, s is a singlet, d is a doublet, t is a triplet, and quintet is 5
The heavy line, m represents a multiple line, and, for example, dt represents a double triplet, and brd represents a wide line. M in MS
⁺ Represents a parent peak, and the numerical value in () represents the relative intensity of the peak. The phase transition temperature represents "° C", and all "%" in the composition represent "% by weight".

Reference Example Synthesis of Compound Represented by Formula (VI)

[0065]

[Chemical 16]

(I) (4S) -7,7-dimethyl-4
Synthesis of -Hydroxy 2- (4-methoxyphenyl) -7-silaundecanenitrile (4S) -4,5-epoxy-2- (4-methoxyphenyl) pentanenitrile (this compound is 4-methoxyphenylacetonitrile, (S) -1-chloro-2,
It is a diastereomer mixture of about 1/1 obtained by reacting 3-epoxypropane in the presence of a strong base. ) 2.
A THF solution of 30 g was cooled to −78 ° C., 215 mg of copper (I) iodide was added, and the mixture was stirred for 1 hour. Butylchloromethyldimethylsilane 2.8g, magnesium 495
mg, a Grignard reaction agent prepared from 5 ml of THF was added, and the temperature was raised to 0 ° C. After adding 20 ml of saturated ammonium chloride aqueous solution and filtering through Celite, the reaction product was extracted three times with 150 ml of ethyl acetate and the extract was concentrated, and the obtained residue was subjected to silica gel column chromatography (hexane / ethyl acetate = 5/1). ) Is used for separation and purification,
(2R, 4S) and (2S, 4S) -7,7-dimethyl-4-hydroxy-2- (4-methoxyphenyl) -7-
2.56 g (68% yield) of a 1: 1 mixture of silaundecane nitrile was obtained.

Non-polar component ¹ H NMR (CDCl ₃ ) δ-0.3 (s, 3
H), 0.40 to 0.52 (m, 3H), 0.57 to
0.65 (m, 1H), 0.88 (t, J = 6.9H
z, 3H), 1.21-1.36 (m, 4H), 1.4
2 to 1.51 (m, 2H), 1.78 (ddd, J = 1)
3.8, 10.6 and 4, 4 Hz, 1 H), 2.02
(Ddd, J = 13.8, 11.6 and 12.3H
z, 1H), 3.81 (s, 3H), 3.82-3.9.
0 (m, 1H), 4.14 (dd, J = 11.6 and
4.4 Hz, 1 H), 6.90 (d, J = 8.7 Hz,
2H), 7.28 (d, J = 8.7Hz, 2H)

Polar component ¹ H NMR (CDCl ₃ ) δ -0.06 (s, 3
H), 0.44 to 0.54 (m, 3H), 0.87
(T, J = 7.0 Hz, 3H), 1.19 to 1.34
(M, 4H), 1.36 to 1.44 (m, 2H), 1.
98 (ddd, J = 13.8, 10.1 and 3.2H
z, 1H), 2.07 (ddd, J = 13.8, 9.8)
and 5.3 Hz, 1 H), 3.23 to 3.32 (m,
1H), 3.81 (s, 3H), 4.03 (dd, J =
10.0 and 5.2 Hz, 1H), 6.90 (d,
8.7 Hz, 2 H), 7.28 (d, J = 8.7 Hz,
2H)

(Ii) (2S, 4S) and (2R, 4
Synthesis of S) -7,7-Dimethyl-2- (4-methoxyphenyl) -7-sila-4-undecanolide (4S) -7,7-Dimethyl-4 obtained in (i) above.
-Hydroxy 2- (4-methoxyphenyl) -7-silaundecanenitrile (mixture of diastereomers) 1.8
g, a mixed solution of 10 ml of a 3M aqueous sodium hydroxide solution and 30 ml of diethylene glycol was heated and stirred at 100 ° C. for 5 hours. After the reaction is completed, the pH of the reaction solution becomes 1 until 3
M hydrochloric acid was added, the reaction product was extracted with ethyl acetate, and the extract was concentrated. 10 mg of p-toluenesulfonic acid and 20 ml of toluene were added to the obtained residue, and the mixture was heated under reflux for 2 hours. The reaction solution was concentrated under reduced pressure, and the resulting residue was subjected to silica gel column chromatography (hexane / ethyl acetate = 5).
Separation and purification using (1/1) to obtain non-polar components (2S, 4
S) -7,7-Dimethyl-2- (4-methoxyphenyl) -7-sila-4-undecanolide (No. (VI-
Compound (1)) 515 mg (yield 29%) and polar component (2R, 4S) -7,7-dimethyl-2- (4-methoxyphenyl) -7-sila-4-undecanolide (No.
916 mg (yield 51%) of the compound of (VI-2) was obtained.

(2S, 4S) -7,7-Dimethyl-2-
(4-Methoxyphenyl) -7-sila-4-undecanolide (compound of No. (VI-1)) colorless oily substance [α] _D ²⁰ + 31.8 ° (c = 1.44, CHCl ₃ ) IR (neat ) 2960, 2930, 1770, 1
610, 1515, 1465, 1250, 1180, 1
035,1000,830,780,730cm ^{-1 1} H
NMR (CDCl ₃ ) δ −0.01 (s, 6H),
0.47 to 0.58 (m, 3H), 0.66 (ddd,
J = 14.1, 13.0, and4.5Hz, 1H),
0.89 (t, J = 7.0Hz, 3H), 1.23 ~
1.38 (m, 4H), 1.57 to 1.68 (m, 1
H), 1.73 to 1.83 (m, 1H), 2.36 (d
dd, J = 13.1, 9.4, and 5.7 Hz, 1
H), 2.45 (dt, J = 13.1 and 7.1H)
z, 1H), 3.80 (s, 3H), 3.84 (dd,
J = 9.4 and 6.9 Hz, 1H), 4.56 (m,
1H), 6.89 (d, J = 8.8Hz, 2H), 7.
20 (d, J = 8.8 Hz, 2H) MS m / z 334 (M ⁺ , 1), 116 (11),
115 (1009, 59 (51)

(2R, 4S) -7,7-dimethyl-2-
(4-Methoxyphenyl) -7-sila-4-undecanolide (compound of No. (VI-2)) colorless columnar crystal melting point 37 to 38 ° C [α] _D ²⁰ + 1.3 ° (c = 1.41, CHCl) ₃ ) IR (KBr) 2960, 2940, 1780, 16
15, 1520, 1440, 1250, 1180, 13
_{^{0,830,780cm -1 1 H NMR (CDCl 3}} ) δ -0.01 (s, 6
H), 0.49 to 0.60 (m, 3H), 0.67 (d
dd, J = 14.0, 13.1, and 4.4 Hz, 1
H), 0.89 (t, J = 6.9 Hz, 3H), 1.2
3 to 1.38 (m, 4H), 1.60 to 1.71 (m,
1H), 1.78 to 1.88 (m, 1H), 1.99
(Td, J = 12.6 and 10.4 Hz, 1H),
2.73 (ddd, J = 12.6, 8.7, and5.
5 Hz, 1 H), 3.80 (s, 3 H), 3.84 (d
d, J = 12.6 and 8.7 Hz, 1H), 4.37.
Up to 4.46 (m, 1H), 6.90 (d, J = 8.8H)
z, 2H), 7.21 (d, J = 8.8Hz, 2H) MS m / z 334 (M ⁺ , 1), 116 (11),
115 (100) Elemental analysis: Calculated as C ₁₉ H ₃₀ O ₃ Si: C, 68.22%; H, 9.04% Measured value: C, 68.02%; H, 9.20%

Example 1 Synthesis of compound represented by general formula (II) (1)

[0073]

[Chemical 17]

(1-a) Synthesis of (2R, 4S) -7,7-Dimethyl-2- (4-methoxyphenyl) -7-silaundecane-1,4-diol Obtained in Reference Example (2R, 4S) -7,7-Dimethyl-
To a solution of 900 mg of 2- (4-methoxyphenyl) -7-sila-4-undecanolide (compound of No. (VI-2)) in 5 ml of ether was added 100 mg of lithium aluminum hydride under ice cooling, and the mixture was stirred for 2 hours. 5 ml of 3M hydrochloric acid
Was added, the mixture was filtered through Celite, extracted with ethyl acetate, and the extract was concentrated. The obtained residue is separated and purified using silica gel column chromatography (hexane / ethyl acetate = 1/1) to give (2R, 4S) -7,7-dimethyl-2- (4-methoxyphenyl) -7-. 905 mg (yield 99%) of silaundecane-1,4-diol was obtained.

Oily substance [α] _D ²⁰ −11.2 ° (c = 1.32, CHCl ₃ ) IR (neat) 3330, 2950, 2920, 2
870, 1615, 1580, 1510, 1460, 1
300, 1250, 1180, 1040, 880, 83
_{^{0cm -1 1 H NMR (CDCl 3}} ) δ -0.07 (s, 6
H), 0.33 to 0.56 (m, 4H), 0.87
(T, J = 7.2 Hz, 3H), 1.21 to 1.33
(M, 4H), 1.39 (dd, J = 7.6 and 6.
4 Hz, 1 H), 1.41 (dd, J = 7.4 and
6.2 Hz, 1 H), 1.70 to 1.83 (m, 2
H), 2.96 to 3.05 (m, 1H), 3.36 to
3.42 (m, 1H), 3.72 (d, J = 6.6H
z, 1H), 3.79 (s, 3H), 6.87 (d, J
= 8.7 Hz, 2H), 7.15 (d, J = 8.7H)
z, 2H) MS m / z 338 (M ⁺ , 2), 151 (16),
148 (25), 147 (10), 136 (11), 1
35 (100), 134 (20), 121 (79), 1
17 (10)

(1-b) (2R, 4R) -2- (2-
Synthesis of butyldimethylsilyl) ethyl-4- (4-methoxyphenyl) tetrahydrofuran (compound of No. (II-1)) (2R, 4S) -7,7-dimethyl-obtained in (1-a) above. 2- (4-methoxyphenyl) -7-silaundecane-1,4-diol 703 mg (2.1 mmol), p-toluenesulfonic acid 20 mg toluene 10
The ml solution was heated to reflux for 1 hour. The reaction solution was concentrated and separated using silica gel column chromatography (hexane / ethyl acetate = 35/1), and then preparative high performance liquid chromatography (Tosoh, Silica-60, 2).
1.5 mm ID x 300 mm, hexane / ethyl acetate =
40/1) and separated and purified to obtain a non-polar component (2R,
4R) -2- (2-butyldimethylsilyl) ethyl-4
-(4-Methoxyphenyl) tetrahydrofuran (No.
(II-1) compound 545 mg (yield 82%), polar component (2S, 4R) -2- (2-butyldimethylsilyl) ethyl-4- (4-methoxyphenyl) tetrahydrofuran 77 mg (yield 12%) ) Got.

[0077] (2R, 4R)-2-(compound of No. (II-1)) (2-butyldimethylsilyl) ethyl-4- (4-methoxyphenyl) tetrahydrofuran oil [α] _D ²⁰ -13. 7 ° (c = 1.02, CHCl ₃ ) IR (neat) 2955, 2920, 2870, 1
610, 1515, 1465, 1300, 1250, 1
_{^{180,1040,880,830cm -1 1 H NMR (CDCl 3}} ) δ -0.02 (s, 6
H), 0.47 (ddd, J = 14.2, 13.0an
d4.5 Hz, 1H), 0.49 to 0.53 (m, 2
H), 0.61 (ddd, J = 14.2, 12.9an)
d4.6 Hz, 1H), 0.88 (t, J = 6.9H
z, 3H), 1.23 to 1.37 (m, 4H), 1.4
7 (tdd, 13.2, 6.7 and 4.6 Hz, 1
H), 1.63 (tdd, J = 13.2, 6.2 and)
4.6 Hz, 1 H, 1.98 (ddd, J = 12.
6, 8.8 and 6.3 Hz, 1H), 2.07 (d
t, J = 12.6 and 7.3 Hz, 1H), 3.37.
(Quintet, J = 7.8Hz, 1H), 3.67
(T, J = 8.2 Hz, 1 H), 3.79 (s, 3
H), 4.05 (quintet, J = 6.6 Hz, 1
H), 4.20 (dd, J = 8.5 and 7.2 Hz,
1H), 6.88 (d, J = 8.6Hz, 2H), 7.
17 (d, J = 8.6 Hz, 2H) MS m / z 320 (M ⁺ , trace), 263
(14), 177 (14), 121 (25), 115
(100) Elemental analysis: Calculated as C ₁₉ H ₃₂ O ₂ Si: C, 71.19%; H, 10.06% Actual value: C, 71.01%; H, 10.24%

Example 2 Synthesis of compound represented by general formula (II) (2)

[0079]

[Chemical 18]

(2-a) Synthesis of (2S, 4S) -7,7-dimethyl-2- (4-methoxyphenyl) -7-siladodecane-1,4-diol (2R, 4S) -7,7-Dimethyl-2- (4-methoxyphenyl) -7-silaundecane-1,4-diol was synthesized in the same manner as (2S,
4S) -7,7-Dimethyl-2- (4-methoxyphenyl) -7-sila-4-undecanolide 456 mg (1.
From 50 mmol), 441 mg (yield 95%) of (2S, 4S) -7,7-dimethyl-2- (4-methoxyphenyl) -7-silaundecane-1,4-diol was obtained.

Oily substance [α] _D ²⁰ + 15.1 ° (c = 1.23, CHCl ₃ ) IR (neat) 3380, 2950, 2925, 1
722, 1615, 1465, 1250, 1180, 1
_{^{040,880,830cm -1 1 H NMR (CDCl 3}} ) δ -0.05 (s, 6
H), 0.38 (ddd, J = 14.0, 12.6an)
d4.9 Hz, 1H), 0.45 to 0.51 (m, 2
H), 0.58 (ddd, J = 14.0, 12.8an
d4.8 Hz, 1H), 0.88 (t, J = 7.0H
z, 3H), 1.20 to 1.53 (m, 6H), 1.6
6 (brds, 1H), 1.77 (quintet,
J = 7.3 Hz, 1H), 1.90 (ddd, J = 1)
4.1, 7.1 and 4.6 Hz, 1H), 3.00
(Quintet, J = 6.9 Hz, 1H), 3.56
Up to 3.62 (m, 1H), 3.68 to 3.82 (m, 2)
H), 3.79 (s, 3H), 6.88 (d, J = 8.
7Hz, 2H), 7.17 (d, J = 8.7Hz, 2
H) MS m / z 338 (M ⁺ , 2), 151 (16),
148 (27), 136 (11), 135 (100),
134 (18), 121 (77)

(2-b) (2R, 4S) -2- (2-
Synthesis of butyldimethylsilyl) ethyl-4- (4-methoxyphenyl) tetrahydrofuran (compound of No. (II-2)) (2R, 4R) -2- (2-butyldimethylsilyl) in the above (1-b). Similarly to the synthesis of ethyl-4- (4-methoxyphenyl) tetrahydrofuran, (2
S, 4S) -7,7-Dimethyl-2- (4-methoxyphenyl) -7-siladodecane-1,4-diol 384
From mg (1.1 mmol), the non-polar component (2R, 4
R) -2- (2-Butyldimethylsilyl) ethyl-4-
(4-methoxyphenyl) tetrahydrofuran 78 mg
(Yield 21%), polar component (2R, 4S) -2- (2-
Butyldimethylsilyl) ethyl-4- (4-methoxyphenyl) tetrahydrofuran (compound of No. (II-2)) 252 mg (yield 69%) was obtained.

Polar component (2R, 4S) -2- (2-butyldimethylsilyl) ethyl-4- (4-methoxyphenyl) tetrahydrofuran (Compound of No. (II-2)) Oily substance [α] _D ²⁰ +26 0.5 ° (c = 0.89, CHCl ₃ ) IR (neat) 2955, 2920, 2870, 1
610, 1515, 1465, 1385, 1250, 1
_{^{180,1040,880cm -1 1 H NMR (CDCl 3}} ) δ -0.20 (s, 6
H), 0.48 (ddd, J = 14.2, 13.0an
d4.5 Hz, 1H), 0.49 to 0.53 (m, 2
H), 0.62 (ddd, J = 14.2, 13.0, a
nd4.5Hz, 1H), 0.88 (t, J = 6.9H
z, 3H), 1.23 to 1.37 (m, 4H), 1.4
8 to 1.62 (m, 2H), 1.70 (tdd, J = 1
3.2, 6.1 and 4.6 Hz, 1H), 2.42
(Ddd, J = 12.2, 7.5 and 5.5 Hz, 1
H), 3.41 (dq, J = 10.3 and 7.9H)
z, 1H), 3.74 (t, J = 8.4Hz, 1H),
3,79 (s, 3H), 3.95 (dq, J = 9.6a
nd 6.1 Hz, 1H), 4.13 (t, J = 8.1H)
z, 1H), 6.85 (d, J = 8.7Hz, 2H),
7.17 (d, J = 8.7 Hz, 2H) MS m / z 320 (M ⁺ , trace), 263
(14), 177 (12), 121 (24), 115
(100) Elemental analysis: Calculated as C ₁₉ H ₃₂ O ₂ Si: C, 71.19%; H, 10.06% Actual value: C, 70.93%; H, 10.29%

Example 3 Synthesis of compound represented by general formula (III)

[0085]

[Chemical 19]

(3-a) (2R, 4R) -2- (2-
Synthesis of butyldimethylsilyl) ethyl-4- (4-hydroxyphenyl) tetrahydrofuran (compound of No. (III-1)) 0.8 ml of dimethyl sulfide was added to a solution of 1.37 g of aluminum chloride in 5 ml of dichloromethane, and Example 1 was further added. A solution of 550 mg of (2R, 4R) -2- (2-butyldimethylsilyl) ethyl-4- (4-methoxyphenyl) tetrahydrofuran obtained in 3 in 3 ml of dichloromethane was added, and the mixture was stirred at room temperature for 3 hours. After completion of the reaction, 5 ml of a saturated sodium hydrogen carbonate solution was added, the mixture was filtered through Celite, the reaction product was extracted with ethyl acetate, and the extract was concentrated. The obtained residue is separated and purified using silica gel column chromatography (hexane / ethyl acetate = 5/1),
202 mg (yield 94%) of (2R, 4R) -2- (2-butyldimethylsilyl) ethyl-4- (4-hydroxyphenyl) tetrahydrofuran was obtained. Colorless oily substance [α] _D ²⁰ -16.1 ° (c = 0.81, CHCl ₃ ) IR (neat) 3315, 2955, 2920, 1
870, 1615, 1515, 1450, 1380, 1
250,175,1045,880 cm ^{-1 1} H NMR (CDCl ₃ ) δ -0.03 (s, 6
H), 0.46 (ddd, J = 14.3, 13.0an
d4.5 Hz, 1H), 0.49 to 0.53 (m, 2
H), 0.61 (ddd, J = 14.3, 13.0an
d4.5Hz, 1H), 0.88 (t, J = 7.1H
z, 3H), 1.23 to 1.37 (m, 4H), 1.4
7 (tdd, 13.3, 11.3 and 6.7 Hz, 1
H), 1.63 (tdd, J = 13.3, 6.1 and
4.6 Hz, 1 H, 1.98 (ddd, J = 12.
6, 8.8 and 6.3 Hz, 1H), 2.06 (d
t, J = 12.6 and 7.4 Hz, 1H), 3.36
(Quintet, J = 7.8Hz, 1H), 3.67
(T, J = 8.2 Hz, 1H), 4.07 (quint
et, J = 6.6 Hz, 1H), 4.20 (dd, J =
8.5 and 7.5 Hz, 1H), 6.77 (d, J =
8.6 Hz, 2 H), 7.11 (d, J = 8.6 Hz,
2H) MS m / z 291 (M ⁺ -15, 2), 249 (1
7), 163 (16), 120 (14), 115 (10
0), 107 (26) Elemental analysis: as C ₁₈ H ₃₀ O ₂ Si Calculated value: C, 70.53%; H, 9.87% Measured value: C, 70.44%; H, 9.72%

(3-b) (2R, 4S) -2- (2-
Synthesis of butyldimethylsilyl) ethyl-4- (4-hydroxyphenyl) tetrahydrofuran (compound of No. (III-2)) (2R, 4R) -2- (2-butyldimethylsilyl) in the above (3-a). Similarly to the synthesis of ethyl-4- (4-hydroxyphenyl) tetrahydrofuran (compound of No. (III-1)), (2R, 4S) -2- (2
-Butyldimethylsilyl) ethyl-4- (4-methoxyphenyl) tetrahydrofuran 227 mg, (2
202 mg (yield 93%) of R, 4S) -2- (2-butyldimethylsilyl) ethyl-4- (4-hydroxyphenyl) tetrahydrofuran was obtained.

Colorless oily substance [α] _D ²⁰ + 15.7 ° (c = 0.98, CHCl ₃ ) IR (neat) 3300, 2950, 2925, 2
870, 1515, 1450, 1380, 145, 10
_{^{25,880cm -1 1 H NMR (CDCl 3}} ) δ -0.02 (s, 6
H), 0.48 (ddd, J = 14.1, 13.1, a
nd4.5Hz, 1H), 0.24 to 0.53 (m, 2
H), 0.62 (ddd, J = 14.1, 13.0an
d4.5Hz, 1H), 0.88 (t, J = 7.1H
z, 3H), 1.23 to 1.37 (m, 4H), 1.4
8 to 1.62 (m, 2H), 1.70 (tdd, J = 1
3.2, 6.0 and 4.6 Hz, 1H), 2.42
(Ddd, J = 12.5, 7.0 and 5.0 Hz, 1
H), 3.40 (dq, J = 10.3 and 7.9H)
z, 1H), 3.74 (t, J = 8.4Hz, 1H),
3.74 (t, J = 8.4 Hz, 1H), 3.95 (d
q, J = 9.6 and 6.0 Hz, 1H), 4.13
(T, J = 8.1 Hz, 1 H), 4.77 (brd
s, 1H), 6.78 (d, J = 8.6Hz, 2H),
7.12 (d, J = 8.6 Hz, 2H) MS m / z 291 (M ⁺ -15, 2), 249 (1
5), 163 (12), 120 (13), 115 (10
0), 107 (24)

(Example 4) (2R, 4R) -2- (2
-Butyldimethylsilyl) ethyl-4- [4- (4-octyloxybenzoyloxy) phenyl] tetrahydrofuran (Compound of No. (I-2))

[0090]

[Chemical 20]

(2R, 4R) obtained in the above (3-a)
-2- (2-butyldimethylsilyl) ethyl-4- (4
-Hydroxyphenyl) tetrahydrofuran 80 mg,
To a solution of 4-octyloxybenzoyl chloride (140 mg) in dichloromethane (5 ml) was added pyridine (0.1 ml), and the mixture was heated under reflux for 2 hours. After concentrating the reaction solution, silica gel column chromatography (hexane / ethyl acetate = 20 /
(2R, 4R) -2- (2
130 mg (yield 93%) of -butyldimethylsilyl) ethyl-4- [4- (4-octyloxybenzoyloxy)] tetrahydrofuran was obtained.

Oily substance [α] _D ²⁰ −10.9 ° (c = 1.19, CHCl ₃ ) IR (neat) 2950, 2920, 2850, 1
785, 1730, 1605, 1510, 1465, 1
255, 1165, 1065, 840 cm ^{-1 1} H NMR (CDCl ₃ ) δ -5.05 (s, 6
H), 0.48 (ddd, J = 14.2, 13.0an
d4.5 Hz, 1H), 0.50 to 0.54 (m, 2
H), 0.62 (ddd, J = 14.2, 13.0an
d4.5Hz, 1H), 0.89 (t, J = 7.1H)
z, 3H), 0.90 (t, J = 7.1 Hz, 3H),
1.24 to 1.41 (m, 12H), 1.42 to 1.5
7 (m, 3H), 1.65 (tdd.J = 13.2,
6.2 and 4.6 Hz, 1H), 1.79 to 1.86
(M, 2H), 2.02 (ddd, J = 12.6, 8.
9 and 6.4 Hz, 1H), 2.12 (dt, 12.
6 and 12.4 Hz, 1H), 3.41 to 3.48.
(M, 1H), 3.73 (t, J = 7.9 Hz, 1
H), 4.04 (t, J = 6.6 Hz, 2H), 4.0
3 to 4.12 (m, 1H), 4.22 (dd, J = 8.
6 and 7.2 Hz, 1 H), 6.97 (d, J = 9.
0Hz, 2H), 7.14 (d, J = 8.6Hz, 2
H), 7.30 (d, J = 8.6 Hz, 2H), 8.1
3 (d, J = 9.0 Hz, 2H), MS m / z 523 (M ⁺ -15, trace), 2
33 (100), 121 (47) Elemental analysis: Calculated as C ₃₃ H ₅₀ O ₄ Si: C, 73.56%; H, 9.35% Found: C, 73.56%; H, 9. 22%

Example 5 (2R, 4S) -2- (2
-Butyldimethylsilyl) ethyl-4- [4- (4-octyloxybenzoyloxy) phenyl] tetrahydrofuran (Compound of No. (I-1))

[0094]

[Chemical 21]

(2R, 4R) -2- in Example 4
(2-Butyldimethylsilyl) ethyl-4- [4- (4
(2R, 4S) -2 in a similar manner to the synthesis of -octyloxybenzoyloxy) phenyl] tetrahydrofuran.
-(2-Butyldimethylsilyl) ethyl-4- (4-hydroxyphenyl) tetrahydrofuran (No. (III
-2) compound) 60 mg, (2R, 4S) -2-
(2-Butyldimethylsilyl) ethyl-4- [4- (4
48 mg (yield 45%) of -octyloxybenzoyloxy) phenyl] tetrahydrofuran was obtained.

Oily substance [α] _D ²⁰ + 13.2 ° (c = 0.94, CHCl ₃ ) IR (neat) 2925, 2850, 1735, 1
605, 1510, 1250, 1165, 1070, 8
_{^{40cm -1 1 H NMR (CDCl 3}} ) δ -0.2 (s, 6
H), 0.45 to 0.54 (m, 3H), 0.63 (d
dd. J = 14.2, 13.0 and 4.5 Hz, 1
H), 0.88 (t, J = 7.1 Hz, 3H), 0.9
0 (t, J = 6.8 Hz, 3H), 1.23 to 1.41
(M, 12H), 1.44 to 1.59 (m, 3H),
1.62 (dt, J = 12.2 and 9.9 Hz, 1
H), 1.72 (tdd, J = 13.2, 6.1 and)
4.5Hz, 1H), 1.82 (quintet, J =
7.0 Hz, 2H), 2.47 (ddd, J = 12.
3,7.6 and 5.6 Hz, 1H), 3.48 (d
q, J = 10.1 and 7.9 Hz, 1H), 3.81
(T, J = 8.3 Hz, 1H), 3.96 (dq, J =
9.7 and 6.1 Hz, 1H), 4.04 (t, J =
6.6 Hz, 2 H), 4.16 (t, J = 8.2 Hz,
1H), 6.97 (d, J = 8.9Hz, 2H), 7.
14 (d, J = 8.6 Hz, 2H), 7.29 (d, J
= 8.6 Hz, 2H), 8.13 (d, J = 8.9H)
z, 2H) MS m / z 523 (M ⁺ -15, trace), 1
70 (17), 233 (100), 121 (33) Elemental analysis: C ₃₃ H ₅₀ O ₄ Si Calculated: C, 73.56%; H, 9.35% Found: C, 73.81% H, 9.35%

Example 6 (2R, 4R) -2- (2
-Butyldimethylsilyl) ethyl-4- [4- (3-fluoro-4-octyloxybenzoyloxy) phenyl] tetrahydrofuran (Compound of No. (I-4))

[0098]

[Chemical formula 22]

3-Fluoro-4-octyloxybenzoic acid 84 mg, dicyclohexylcarbodiimide (DC
C) 65 mg, 4- (N, N-dimethylamino) pyridine 5 mg in dichloromethane 5 ml solution, (2R, 4
R) -2- (2-Butyldimethylsilyl) ethyl-4-
(4-hydroxyphenyl) tetrahydrofuran (No.
(Compound of (III-1)) 80 mg was added, and the mixture was stirred at room temperature for 2 hours. After concentrating the reaction solution, silica gel column chromatography (hexane / ethyl acetate = 20/1)
Separated and purified using (2R, 4R) -2- (2-butyldimethylsilyl) ethyl-4- [4- (3-fluoro-4-octyloxybenzoyloxy) phenyl]
124 mg (yield 86%) of tetrahydrofuran was obtained.

Oily substance [α] _D ²⁰ + 9.7 ° (c = 1.51, CHCl ₃ ) IR (neat) 2925, 1850, 1735, 1
615, 1515, 1430, 1280, 1185, 1
_{^{120,1065,830cm -1 1 H NMR (CDCl 3}} ) δ -0.00 (s, 6
H), 0.49 (ddd.J = 14.2, 13.0an)
d4.5 Hz, 1H), 0.51 to 0.55 (m, 2
H), 0.64 (ddd.J = 14.2, 13.0an
d4.5Hz, 1H), 0.90 (t, J = 7.1H
z, 3H), 0.91 (t, J = 6.7Hz, 3H),
1.26 to 1.43 (m, 12H), 1.45 to 1.5
5 (m, 1H), 1.66 (tdd, J = 13.3,
6.2 and 4.6Hz, 1H), 1.88 (quin)
tet, J = 7.1hz, 2H), 2.04 (ddd.
J = 12.7, 8.9, and 6.4 Hz, 1H),
2.13 (dt, J = 14.3 and 7.2 Hz, 1
H), 3.43 to 3.50 (m, 1H), 7.04.
(T, J = 8.3 Hz, 1H), 7.15 (d, J =
8.6 Hz, 2 H), 7.32 (dJ = 8.6 Hz,
2H), 7.91 (dd, J = 11.6 and 2.1H
z, 1H), 7.97 (ddd.J = 8.6, 2.1a)
nd1.2 Hz, 1H) MS m / z 541 (M ⁺ -15, 2), 499 (1
4), 252 (16), 251 (100), 115 (4
9) Elemental analysis: Calculated as C ₃₃ H ₄₉ FO ₄ Si: C, 71.18%; H, 8.87% Measured value: C, 71.36%; H, 8.90%

Example 7 (2R, 4S) -2- (2
-Butyldimethylsilyl) ethyl-4- [4- (3-fluoro-4-octyloxybenzoyloxy) phenyl] tetrahydrofuran (Compound of No. (I-3))

[0102]

[Chemical formula 23]

(2R, 4R) -2- in Example 6
(2-Butyldimethylsilyl) ethyl-4- [4- (3
In the same manner as in the synthesis of -fluoro-4-octyloxybenzoyloxy) phenyl] tetrahydrofuran (a compound of No. (I-4)), (2R, 4S) -2- (2-
Butyldimethylsilyl) ethyl-4- (4-hydroxyphenyl) tetrahydrofuran (compound of No. (III-2)) 60 mg, (2R, 4S) -2- (2-
91 mg (yield 82%) of butyldimethylsilyl) ethyl-4- [4- (3-fluoro-4-octyloxybenzoyloxy) phenyl] tetrahydrofuran was obtained.

Oily substance [α] _D ²⁰ + 10.6 ° (c = 0.94, CHCl ₃ ) IR (neat) 2925, 2850, 1735, 1
515, 1285, 1185, 1120, 1075, 8
_{^{30cm -1 1 H NMR (CDCl 3}} ) δ -0.02 (s, 6
H), 0.47 to 0.55 (m, 3H), 0.65 (d
dd, J = 14.2, 13.0 and 4,5 Hz, 1
H), 0.88 (t, J = 7.1 Hz, 3H), 0.8
9 (t, J = 6.7 Hz, 3H), 1.23 to 1.41
(M, 12H), 1.45 to 1.55 (m, 1H),
1.62 (dt, J = 12.2 and 9.9 Hz, 1
H), 1.72 (tdd, J = 13.2, 6.0 and
4.6Hz, 1H, 1.87 (quintet, J =
7.1 Hz, 2 H), 2.47 (ddd, J = 12.
6,7.6 and 5.5 Hz, 1H), 3.48 (d
q, J = 10.1 and 7.8 Hz, 1H), 3.81
(T, J = 8.2 Hz, 1H), 3.96 (dq, J =
9.6 and 6.3 Hz, 1H), 4.12 (t, J =
6.6Hz, 2H, 4.16 (t, 8.2Hz, 1
H), 7.02 (t, J = 8.3 Hz, 1H), 7.1
3 (d, J = 8.6 Hz, 2H), 7.30 (d, J =
8.6 Hz, 2H), 7.89 (dd, J = 11.6a
nd2.1Hz, 1H), 7.95 (ddd, 8.6,
2.1 and 1.2 Hz, 1H) MS m / z 541 (M ⁺ -15, 2), 499 (2
0), 252 (17), 251 (100), 139 (8)
5), 116 (10), 115 (94) Elemental analysis: C ₃₃ H ₄₉ FO ₄ Si Calculated: C, 71.18%; H, 8.87% Found: C, 71.33%; H , 8.96%

Example 8 (2R, 4R) -2- (2
-Butyldimethylsilyl) ethyl-4- [4- (trans-4-heptylcyclohexanecarbonyloxy) phenyl] tetrahydrofuran (compound of No. (I-6))

[0106]

[Chemical formula 24]

(2R, 4R) -2- in Example 4
(2-Butyldimethylsilyl) ethyl-4- [4- (4
-Octyloxybenzoyloxy) phenyl] tetrahydrofuran (compound of No. (I-2)) in the same manner as (2R, 4R) -2- (2-butyldimethylsilyl) ethyl-4- (4-hydroxy). Phenyl) tetrahydrofuran (compound of No. (III-1)) 60 m
g, 150 mg of trans-4-heptylcyclohexanecarbonyl chloride, (2R, 4R) -2- (2-butyldimethylsilyl) ethyl-4- [4- (trans-4
98 mg (yield 98%) of -heptylcyclohexanecarbonyloxy) phenyl] tetrahydrofuran was obtained.

Oily substance [α] _D ²⁰ -7.7 ° (c = 0.96, CHCl ₃ ) IR (neat) 2920, 2850, 1750, 1
_{^{445,1245,1120,830cm -1 1 H NMR (CDCl 3}} ) δ -0.03 (s, 6
H), 0.46 (ddd, J = 14.2, 13.0an
d4.5 Hz, 1H), 0.49 to 0.53 (m, 2
H), 0.60 (ddd, J = 14.2, 13.0an
d4.6 Hz, 1H), 0.88 (t, J = 7.1H
z, 3H), 0.89 (t, J = 6.7Hz, 3H),
0.91 to 1.02 (m, 2H), 1.16 to 1.36
(M, 17H), 1.42 to 1.67 (m, 4H),
1.87 (m, 2H), 1.99 (ddd, J = 12.
6, 8.9 and 6.4 Hz, 1H), 2.06 to 2.
17 (m, 3H), 2.46 (tt, J = 12.2an
d3.5Hz, 1H), 3.41 (quintet, J
= 7.6 Hz, 1H), 3.70 (t, J = 7.9H)
z, 1H), 4.06 (quintet, J = 6.6H)
z, 1H), 4.21 (dd, J = 8.6 and 7.2)
Hz, 1H), 6.99 (d, J = 8.6Hz, 2
H), 7.24 (d, J = 8.6 Hz, 2H) MS m / z 514 (M ⁺ , trace), 457.
(19), 116 (11), 115 (100), 111
(12), 97 (20) Elemental analysis: as C ₃₂ H ₅₄ O ₃ Si Calculated value: C, 74.65%; H, 10.57% Measured value: C, 74.94%; H, 10.39 %

Example 9 (2R, 4S) -2- (2
-Butyldimethylsilyl) ethyl-4- [4- (trans-4-heptylcyclohexanecarbonyloxy) phenyl] tetrahydrofuran (Compound of No. (I-5))

[0110]

[Chemical 25]

(2R, 4R) -2- in Example 4
(2-Butyldimethylsilyl) ethyl-4- [4- (4
-Octyloxybenzoyloxy) phenyl] tetrahydrofuran (compound of No. (I-2)) in the same manner as (2R, 4S) -2- (2-butyldimethylsilyl) ethyl-4- (4-hydroxy). Phenyl) tetrahydrofuran (compound of No. (III-2)) 60 mg
(0.20 mmol), more, (2R, 4S) -2-
98 mg of (2-butyldimethylsilyl) ethyl-4- [4- (trans-4-heptylcyclohexanecarbonyloxy) phenyl] tetrahydrofuran (yield 98
%) Was obtained.

Oily substance [α] _D ²⁰ + 12.4 ° (c = 1.19, CHCl ₃ ) IR (neat) 2920,2850,1750,1
505, 1450, 1375, 1245, 1165, 1
_{^{120,830cm -1 1 H NMR (CDCl 3}} ) δ -0.03 (s, 6
H), 0.43 to 0.53 (m, 3H), 0.62 (d
dd, J = 14.2, 13.0 and 4.5 Hz, 1
H), 0.88 (t, J = 7.1 Hz, 3H), 0.8
9 (t, J = 6.7 Hz, 3H), 0.92 to 1.02
(M, 2H), 1.18 to 1.37 (m, 18H),
1.49 to 1.63 (m, 3H), 1.70 (tdd,
J = 13.2, 6.2 and 4.5 Hz, 1H), 1.
82-1.90 (m, 2H), 2.08-2.16
(M, 2H), 2.41-2.50 (m, 2H), 3.
45 (dq, J = 10.0 and 7.9 Hz, 1H),
3.78 (t, J = 8.3 Hz, 1H), 3.94 (d
q, J = 9.6 and 6.1 Hz, 1H), 4.13
(T, J = 8.2 Hz, 1H), 6.99 (d, J =
8.5 Hz, 2 H), 7.23 (d, J = 8.5 Hz,
2H) MS m / z 514 (M ⁺ , trace), 457.
(21), 208 (10), 116 (11), 115
(100), 111 (14), 97 (23) Elemental analysis: Calculated as C ₃₂ H ₅₄ O ₃ Si: C, 74.65%; H, 10.57% Actual value: C, 74.39%; H, 10.62%

Example 10 Preparation of SC ^* Liquid Crystal Composition A base liquid crystal (B-1) having an SC phase having the following composition was prepared.

[0114]

[Chemical formula 26]

The phase transition temperature of this host liquid crystal was as follows. Cr12.5 SC55.5 SA64.5 N70 I (The phase transition temperature represents the phase transition temperature between the phase on the left side and the phase on the right side of the numeral, for example, Cr12.5 SC is between the crystalline phase and the smectic C phase Has a phase transition temperature of 12.5 ° C. The same shall apply hereinafter.)

An SC ^* liquid crystal composition (M-1) comprising 95% of the base liquid crystal (B-1) and 5% of the compound of No. (I-1) of Example 1 was prepared. The phase transition temperature was as follows. SC ^* 47.5 SA63.5 N ^* 66.5 I Melting point was not clear.

Similarly, the base liquid crystals (B-1) 90 to 95
% And each of No. (I-1) to (I-6) compounds in an amount of 5 to 10%, SC ^* liquid crystal composition (M-2) to
(M-9) was prepared. The phase transition temperatures are summarized in Table 4.

[0118]

[Table 4] Moreover, the melting point was unclear in all cases.

Example 10 Production of Liquid Crystal Display Element and Measurement of Electro-Optical Properties The SC ^* liquid crystal composition (M-1) obtained in Example 9 was heated to an isotropic liquid (I) phase, This was filled in a glass cell composed of two transparent electrode plates (having a polyimide coating-orientation treatment by rubbing) having a thickness of about 2 μm to prepare a display element. When this was gradually cooled to room temperature, uniformly oriented SC ^* phase cells were obtained. A rectangular wave of 50 Hz with an electric field strength of 10 V _pp / μm was applied to this cell, and its electro-optical response speed was measured.
A high-speed response of 125 μsec at ℃ was confirmed. At this time, the tilt angle was 17.0 °, and the contrast was very good. Also, this spontaneous polarization is -1.87 nC / cm ²
Met.

Similarly, SC ^* liquid crystal composition (M-2)
To (M-9) were used to manufacture liquid crystal display devices, and their spontaneous polarization and electro-optical response speed were measured. The results are shown in Table 5 together.

[0121]

[Table 5] (In the table, * indicates that the absolute value of spontaneous polarization is 0.01 nC / cm ² or less.)

Comparative Example Preparation of SC ^* Liquid Crystal Composition Containing Compound of General Formula (V) and Measurement of Electro-Optical Properties No. having a structure similar to No. (I-1) and (I-5) .
(V-1) and (V-5)

[0123]

[Chemical 27]

SC ^* liquid crystal compositions (H-1), (H-2), (H-7) and () each consisting of 5 to 10% of the compound of the above and 90 to 95% of the same base liquid crystal (B-1) as above. H-8) was prepared respectively. The phase transition temperature is also shown in Table 4 above.

Next, using these SC ^* liquid crystal compositions, a liquid crystal display device was prepared in the same manner as in Example 10, and its electro-optical characteristics were measured. The results are also shown in Table 5 above.

SC ^* Liquid crystal compositions (H-1), (H-
2), (H-7) and (H-8) are compared with SC ^* liquid crystal compositions (M-1), (M-2), (M-7) and (M-8), respectively. The compound of the general formula (I) of the present invention has a relatively fast response although the spontaneous polarization induced by the compound of the general formula (V) is similar to or slightly smaller than that of the compound of the general formula (V). it is obvious.

[0127]

INDUSTRIAL APPLICABILITY The optically active tetrahydrofuran derivative containing silicon represented by the general formula (I) of the present invention induces sufficient spontaneous polarization at a high speed by adding a small amount as a so-called chiral dopant to other host liquid crystals. It is possible to provide a liquid crystal composition capable of responding, obtaining a good alignment property, and having a wide liquid crystal phase temperature range.

Further, the compound of the general formula (I) of the present invention is
It is very practical because it can be easily produced industrially, is colorless, and has excellent chemical stability against water and light. Furthermore, the chiral smectic liquid crystal composition of the present invention can realize a high-speed response on the order of 50 μsec, and is extremely useful as an optical switching element for display.

Continuation of the front page (72) Inventor Hijiro Hiujiro 4-29-3-101 Kamizuruma, Sagamihara City, Kanagawa Prefecture (72) Inventor Tetsuo Kusumoto 1-9-2-102 Minamidai, Sagamihara City, Kanagawa Prefecture (72) Inventor Sato Kenichi 35-11 Kamimizo, Sagamihara-shi, Kanagawa (72) Inventor Akiko Nakayama 1380-K-702 Yamazaki-cho, Machida-shi, Tokyo

Claims (5)

[Claims] 1. A compound represented by the general formula (I): (In the formula, R ¹ represents an alkyl group having 1 to 18 carbon atoms, X represents a single bond or —O—, and ring A is a 1,4-phenylene group or trans which may be substituted by a fluorine atom. Represents a -1,4-cyclohexylene group, R ²
Represents an alkyl group having 1 to 10 carbon atoms, and the asymmetric carbon atoms at the 2-position and 4-position of the tetrahydrofuran ring are each independently in the (R) or (S) configuration. ) An optically active tetrahydrofuran derivative containing silicon represented by: 2. A liquid crystal composition containing the compound represented by formula (I) according to claim 1. 3. The liquid crystal composition according to claim 2, which exhibits a ferroelectric chiral smectic phase. 4. A liquid crystal display device using the liquid crystal composition according to claim 2. 5. A compound represented by the general formula (II): (In the formula, R ³ represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, R ² represents an alkyl group having 1 to 10 carbon atoms, and an asymmetric carbon atom at the 2-position and 4-position of the tetrahydrofuran ring. Are each independently in the (R) or (S) configuration.) An optically active tetrahydrofuran derivative containing silicon.