JPH0517466A - Optically active tetrahydrofuran derivative - Google Patents

Abstract

PURPOSE:To provide a novel compound having a tetrahydrofuran ring and useful as the material for liquid crystals used for liquid crystal display elements or optoelectrical elements. CONSTITUTION:A compound of formula I (Rf is 1-2C fluoroalkyl; R<2>, R<3> are H, 1-15C alkyl, etc.; A is -COO-, -O-, single bond; B, Y are t COO), #CH,0&, etc.; * exhibits an asymmetric carbon; X<1>, X<2> are 1,4-phenylene, 2.5-pyridylene, etc.), e.g. (2S,3S,1'S)tetrahydro-3-butyl-2-[2',2',2'-trifluoro-1'-(4'''- hexyloxybiphenyl-4''-carboxy)ethyl]furan. The compound of formula I is produced by reacting a compound of formula: BzO-X<2>-COCl (Bz is benzyl) with a compound of formula II, removing the benzyl group from the reactional product and subsequently reacting the produced compound of formula III with a compound of formula: R<1>-A-X<1>-COCl in the presence of a base (e.g. pyridine) in a solvent such as toluene at 20-80 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optically active tetrahydrofuran derivative, and more particularly to a novel optically active tetrahydrofuran derivative useful as a liquid crystal material used in display devices or electro-optical devices.

[0002]

2. Description of the Related Art In recent years, the fields of use of liquid crystals such as various display elements, electro-optical devices, liquid crystal sensors, etc. have been remarkably expanding, and liquid crystal compounds having various structures have been proposed accordingly. In particular, the liquid crystal material used for the display element is currently a nematic liquid crystal, and a TN type or STN type simple matrix system using this or a TFT type active matrix system in which a thin film transistor is provided for each pixel. Is used. However, the driving force of nematic liquid crystal is based on the weak anisotropy of the dielectric constant of the liquid crystal material and the weak interaction with the electric field. Therefore, nematic liquid crystal has a drawback that the response speed is essentially slow (msec order). It is disadvantageous as a material for a large-screen display element that requires a response. On the other hand, the ferroelectric liquid crystal first synthesized by RB Meyer et al. In 1975 has a spontaneous polarization, which directly acts on the electric field, so that the driving force is large, and in 1980 Clark (NA
Clark) et al. Proposed a surface-stabilized ferroelectric liquid crystal device (SSFL).
In (CD), since its high-speed response on the order of μsec and its memory property have been announced, it has attracted attention and many ferroelectric liquid crystal compounds have been synthesized so far.

The response speed of a ferroelectric liquid crystal is τ = η / Ps ·
Known by E. Here, η indicates rotational viscosity, Ps indicates spontaneous polarization, and E indicates electric field strength. Therefore, in order to obtain high-speed response, a liquid crystal material having low viscosity and large spontaneous polarization has been a development target. Further, liquid crystal materials are required to have characteristics such as chemical stability and a wide operating temperature range, but it has been difficult to satisfy these characteristics with a single compound. Therefore, conventionally, a compound having a plurality of chiral smectic C phases (SmC ^* ) is mixed with each other, or an optically active compound is added to a host liquid crystal having a smectic C phase (SmC) having a low viscosity to obtain desired performance. Methods have been used to obtain ferroelectric liquid crystal compositions exhibiting the SmC ^* phase. In the latter case, the chiral dopant to be added may or may not have the SmC ^* phase itself, has good compatibility with the host liquid crystal, induces large spontaneous polarization, and has a high viscosity. Is required not to increase.

It is considered that spontaneous polarization occurs as a result of dipole moment perpendicular to the long axis of the molecule being controlled by free rotation around the long axis due to the influence of asymmetric carbon. Therefore, in order to increase the spontaneous polarization, the dipole part is brought closer to the skeleton called the core, the dipole part and the asymmetric carbon atom are brought closer, and a stereoscopically large substituent is attached to the asymmetric carbon to rotate the long axis. Attempts have been made to increase the spontaneous polarization by methods such as suppressing the free rotation of the. More recently, it has been reported that a compound having a structure in which a dipole moiety and an asymmetric carbon are directly linked to a 5-membered ring lactone effectively restrains free rotation and has a large spontaneous polarization (Japanese Journal o
f Applied Physics, Volume 29, No. 6, ppL981 to L983).

[0005]

DISCLOSURE OF THE INVENTION The present inventors introduced a fluoroalkyl group having a large electron-withdrawing group itself on an asymmetric carbon atom adjacent to such a tetrahydrofuran ring to further increase spontaneous activity. To provide a novel compound which has polarization and is chemically stable and exhibits liquid crystallinity per se, or which does not exhibit liquid crystallinity by itself, but is useful as a compounding component of a ferroelectric liquid crystal that induces large spontaneous polarization. We have earnestly studied.

[0006]

As a result, the inventors of the present invention have found that a specific tetrahydrofuran derivative shows liquid crystallinity as a single product or does not show a liquid crystal phase as a single product, but has high-speed response when made into a composition. It has been found that they can be expected to be excellent dopants. The present invention has been completed based on such findings. That is, the present invention has the following general formula (I)

[0007]

[Chemical 3]

[In the formula, Rf represents a fluoroalkyl group having 1 or 2 carbon atoms, R ¹ represents a linear or branched alkyl group having 3 to 20 carbon atoms, and R ² and R ³ each independently represent hydrogen. Or a linear or branched alkyl group having 1 to 15 carbon atoms,
An alkenyl group or an aralkyl group having 7 to 10 carbon atoms having 2 to 15 carbon atoms, A is -COO -, - O- or a single bond, B is -COO -, - OCO -, - CH 2 O- ，
-OCH ₂ - or a single bond, Y is -COO -, - C
H ₂ O- or -O-, * represents an asymmetric carbon, X ¹
And X ² are independently

[0009]

[Chemical 4]

Is shown. ] The optically active tetrahydrofuran derivative represented by these is provided. In the general formula (I), Rf as described above represents a fluoroalkyl group having 1 or 2 carbon atoms, specifically, a trifluoromethyl group, a difluoromethyl group, a chlorodifluoromethyl group, a pentafluoroethyl group or the like. , And preferably a trifluoromethyl group.

R ¹ is a linear or branched alkyl group having 3 to 20 carbon atoms, for example, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group,
tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group,
n-decyl group, n-undecyl group, n-dodecyl group, n
-Tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-
Examples include octadecyl group, n-nonadecyl group, and n-eicosyl group. Among these, a branched chain alkyl group having an asymmetric carbon atom is an optically active group.

Further, R ² and R ³ are each independently hydrogen or a linear or branched alkyl group having 1 to 15 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, 1-methylbutyl group, n-hexyl group, n-heptyl group, 1-methylheptyl group, n-octyl group, 1-ethylheptyl group, 1-methyloctyl group, n-nonyl group, 1-ethyloctyl group, 1-methylnonyl group, n-decyl group, n-
Undecyl group, n-dodecyl group, n-tridecyl group, n
-Tetradecyl group, n-pentadecyl group and the like. The alkenyl group having 2 to 15 carbon atoms includes vinyl group, allyl group, 1-propenyl group, isopropenyl group,
1-butenyl group, 2-butenyl group, 2-methylallyl group, 1-pentenyl group, 1-hexenyl group, 1-heptenyl group, 1-octenyl group, 2-octenyl group, 1-nonenyl group, 2-nonenyl group, 1-decenyl group, 2-decenyl group, 1-undecenyl group, 2-undecenyl group, 1
-Dodecenyl group, 2-dodecenyl group, 1-tridecenyl group, 2-tridecenyl group, 1-tetradecenyl group, 2-
Examples thereof include a tetradecenyl group, a 1-pentadecenyl group and a 2-pentadecenyl group. Examples of the aralkyl group having 7 to 10 carbon atoms include benzyl group, phenethyl group, phenylpropyl group and phenylbutyl group.

The compound of formula (I) according to the present invention can be produced by various methods, for example, the following steps. (1) B = -COO- and Y = -COO- when: the following general formula (II) BzO-X ² -COCl wherein, X ² are as defined above, Bz is a benzyl group. ] The following general formula (III) represented by

[0014]

[Chemical 5]

[In the formula, Rf, R ² and R ³ are the same as described above. ] The compound represented by the following general formula (IV)

[0016]

[Chemical 6]

[Wherein Rf, Bz, X ² , R ² and R ³
Is the same as above. ] The compound represented by this is obtained. This reaction can be carried out in the presence of an organic base such as pyridine or triethylamine in a solvent such as toluene, benzene or methylene chloride at a temperature of -20 ° C to 80 ° C.
Next, the benzyl group in the obtained compound of the general formula (IV) is eliminated by a conventional method to give the following general formula (V)

[0018]

[Chemical 7]

[In the formula, Rf, X ² , R ² and R ³ are the same as described above. ] The compound represented by this is produced. This debenzylation reaction can be carried out, for example, by hydrogenolysis under atmospheric pressure using an alcoholic solvent such as methanol, ethanol, propanol or the like or acetic acid in the presence of a Pd / C catalyst. The compound of the general formula (V) obtained as described above is represented by the following general formula (VI) R ¹ -A-X ¹ -COCl [wherein R ¹ , A and X ¹ are the same as described above. ] The compound of the general formula (I) can be obtained by reacting with a compound represented by the formula This reaction is carried out in a solvent such as toluene, benzene or methylene chloride in the presence of an organic base such as pyridine or triethylamine.
It can be performed at a temperature of 20 ° C to 80 ° C.

(2) B = -COO-, Y = CH ₂ O-
For: the following general formula ^{(VII) THPO-X 2 -CH} 2 Z wherein, X ² are as defined above, THP represents a tetrahydropyranyl group, Z is chlorine, bromine, iodine or tosyl group Show. ] The compound represented by the following general formula (VIII) is reacted with the compound represented by the above general formula (III).

[0021]

[Chemical 8]

[Wherein Rf, THP, X ² , R ² and R
³ is the same as above. ] The compound represented by this is obtained.
This reaction can be carried out by reacting the compound represented by the general formula (III) with a base represented by alkali metal hydride, sodium hydroxide or potassium hydroxide, and then adding the compound represented by the general formula (VII). Then, the tetrahydropyranyl group in the obtained compound of the general formula (VIII) is eliminated by a conventional method to give the following general formula (IX)

[0023]

[Chemical 9]

[In the formula, Rf, X ² , R ² and R ³ are the same as described above. ] The compound represented by this is produced. The elimination of the tetrahydropyranyl group can be carried out in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid and paratoluenesulfonic acid, using a solvent such as ether, tetrahydrofuran or chloroform. Then, the obtained compound of the general formula (IX) is reacted with the compound represented by the general formula (VI) to obtain the compound of the general formula (I). This reaction can be carried out in the presence of an organic base such as pyridine or triethylamine in a solvent such as toluene, benzene or methylene chloride at a temperature of -20 ° C to 80 ° C.

[0025] (3) B = -COO-, if the Y = -O-: the following general formula (X) in THPO-X ² -I [wherein, THP and X ² are as defined above. ] The compound represented by the following general formula (XI) is reacted with the compound represented by the above general formula (III).

[0026]

[Chemical 10]

[Wherein Rf, THP, X ² , R ² and R
³ is the same as above. ] The compound represented by this is obtained.
This reaction is carried out by reacting a compound represented by the general formula (III) with a base typified by an alkali metal hydride, and then using cuprous iodide as a catalyst under reflux conditions such as dimethylformamide and dimethylsulfoxide. It can be carried out by reacting the compound represented by X). next,
If the tetrahydropyranyl group in the obtained compound of the general formula (XI) is eliminated by a conventional method, the following general formula (XII)

[0028]

[Chemical 11]

[In the formula, Rf, X ² , R ² and R ³ are the same as defined above. ] The compound represented by this is produced. The elimination of the tetrahydropyranyl group can be carried out in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid and paratoluenesulfonic acid, using a solvent such as ether, tetrahydrofuran or chloroform. Then, the obtained compound of the general formula (XII) is reacted with the compound represented by the general formula (VI) to obtain the compound of the general formula (I).
This reaction can be carried out in the presence of an organic base such as pyridine or triethylamine in a solvent such as toluene, benzene or methylene chloride at a temperature of -20 ° C to 80 ° C.

(4) When B = -CH ₂ O-, Y = -COO-: The compound represented by the above general formula (V) is converted into the following general formula (XI
II) R ¹ -A-X ¹ -CH ₂ Z [In the formula, R ¹ , A, X ¹ and Z are the same as defined above. ]
The compound of the above general formula (I) can be obtained by reacting with the compound represented by This reaction can be carried out by reacting the compound of the general formula (V) with an alkali metal hydride or a base represented by sodium hydroxide or potassium hydroxide, and then adding the compound of the general formula (XIII).

[0031] _{(5) B = -OCH 2 -} , Y = -COO- when: the following general formula (XIV) ZCH in ₂ -X ² -COCl [wherein, Z and X ² are as defined above. ] The compound represented by the following general formula (XV) is reacted with the compound represented by the above general formula (III).

[0032]

[Chemical 12]

[In the formula, Rf, Z, X ² , R ² and R ³ are the same as described above. ] The compound represented by this is obtained. This reaction can be carried out in the presence of an organic base such as pyridine or triethylamine in a solvent such as toluene, benzene or methylene chloride at a temperature of -20 ° C to 80 ° C. Next, the following general formula (XVI) R ¹ -A-X ¹ -OH [wherein R ¹ , A and X ¹ are the same as described above. ] The compound represented by the general formula (I) is obtained by reacting the compound represented by the formula (XV) with the compound represented by the formula (I). This reaction can be carried out by reacting the compound represented by the general formula (XVI) with a base represented by alkali metal hydride, sodium hydroxide or potassium hydroxide, and then adding the compound represented by the general formula (XV).

The compound of the general formula (III) used as a starting material for producing the compound of the general formula (I) of the present invention can be produced by various methods. Typical compounds of the general formula (III) include, for example, (2
R, 1'R) -tetrahydro-2- (2 ', 2', 2 '
-Trifluoro-1'-hydroxyethyl) furan;
(2S, 3S, 1'S) -Tetrahydro-3-methyl-
2- (2 ', 2', 2'-trifluoro-1'-hydroxyethyl) furan; (2R, 3R, 1'R) -tetrahydro-3-butyl-2- (2 ', 2', 2 '-Trifluoro-1'-hydroxyethyl)furan; (2S, 3
S, 1'R) -Tetrahydro-3-butyl-2-
(2 ', 2', 2'-Trifluoro-1'-hydroxyethyl) furan; (2S, 4S, 1'R) -Tetrahydro-4-benzyl-2- (2 ', 2', 2'-tri Fluoro-1′-hydroxyethyl) furan; (2S, 4
S, 1'R) -Tetrahydro-4-propyl-2-
(2 ', 2', 2'-Trifluoro-1'-hydroxyethyl) furan; (2S, 4S, 1'R) -Tetrahydro-4-allyl-2- (2 ', 2', 2'-tri Fluoro-1′-hydroxyethyl) furan and the like can be mentioned. Examples of the compound of the general formula (I) of the present invention include:

[0035]

[Chemical 13]

[0036]

[Chemical 14]

[0037]

[Chemical 15]

[0038]

[Chemical 16]

[0039]

[Chemical 17]

[0040]

[Chemical 18]

[0041]

[Chemical 19]

[0042]

[Chemical 20]

[0043]

[Chemical 21]

[0044]

[Chemical formula 22]

And the like.

[0046]

EXAMPLES The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited thereto. In each of the following examples, the general formula (I) of the present invention
The R and S representations of the optically active compound represented by

[0047]

[Chemical formula 23]

It carried out based on the position number of.

Reference Example 1 (2S, 3S, 1'S) -Tetrahydro-3-butyl-
Synthesis of 2- (2 ', 2', 2'-trifluoro-1'-hydroxyethyl) furan

[0050]

[Chemical formula 24]

(A) Furan 13.6 g (2
(00 mmol) was added to 150 ml of tetrahydrofuran, and 133 ml (200 mmol) of a 1.5 mol / l n-butyllithium hexane solution was added.
The mixture was added dropwise at 20 ° C. and reacted for 1 hour. Next, 21.7 g (200 mmol) of trimethylsilyl chloride was added dropwise,
The mixture was stirred at -20 ° C for 1 hour. 1.5 mol / l n-
Butyl lithium hexane solution 133 ml (20
(0 mmol) was added and reacted at -20 ° C for 1 hour,
28.4 g (200 mmol) of ethyl trifluoroacetate was added dropwise at −78 ° C., 1 hour at −78 ° C., and 1 more at room temperature.
Reacted for hours. The reaction was stopped by adding 3N hydrochloric acid to the reaction solution, and the mixture was extracted with ethyl acetate. Then, it was washed successively with a saturated sodium hydrogen carbonate solution and a saturated saline solution, and dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure to obtain a crude product of furan derivative.

(B) To 100 ml of dry ethanol was added 2.3 g (60 mmol) of sodium borohydride, and the crude furan derivative product obtained in the above reaction was stirred at 0 ° C. for 3 days.
It was added dropwise over 0 minutes. After reacting at room temperature for 2 hours, ethanol was distilled off under reduced pressure, 3N hydrochloric acid was added to stop the reaction, and the mixture was extracted with ethyl acetate. Then, it was washed successively with saturated sodium hydrogen carbonate and saturated brine, and dried over anhydrous magnesium sulfate. After distilling off ethyl acetate under reduced pressure, distillation under reduced pressure was carried out to obtain 40.5 g (170 mmol) of an alcohol compound.

(C) To 200 ml of methylene chloride, 23.8 g (1) of the alcohol compound obtained by the above reaction (b)
(00 mmol) and 8.9 ml of pyridine (110 mmol) were added, 8.6 g (110 mmol) of acetyl chloride was added dropwise at 0 ° C., and the mixture was reacted at room temperature for 12 hours. Then, the reaction was stopped by adding 3N hydrochloric acid, and the mixture was extracted with methylene chloride. Then, saturated sodium hydrogen carbonate solution,
It was washed successively with distilled water and dried over anhydrous magnesium sulfate. After distilling off methylene chloride under reduced pressure, vacuum distillation was performed,
27.5 g (98 mmol) of the ester compound was obtained.

(D) To 1000 ml of distilled water was added 28.0 g (100 mmol) of the ester compound obtained by the above reaction, and the mixture was added to 40 ml in a mini jar fermenter.
Stir at ℃. 20 g of lipase PS was added and reacted for 20 hours. 3N hydrochloric acid was added, the reaction was stopped by cooling to 0 ° C., and the mixture was filtered through Celite. The filtrate was extracted with ethyl acetate, washed with saturated brine, dried over anhydrous magnesium sulfate, and ethyl acetate was evaporated under reduced pressure. Then, the product was separated and purified by silica gel column chromatography to obtain 11.7 g (49 mmol) of the optically active alcohol compound and 13.2 g (47 mmol) of the optically active ester compound. The optical purity of the obtained alcohol compound is 97.
It was 5% ee.

(E) 11.7 g (49 mmol) of the optically active alcohol compound obtained by the above reaction was added to 1 part of methylene chloride.
Dissolve in 00 ml, 4.0 g of imidazole (59
Mmol) and t-butyldimethylsilyl chloride 8.9 g
(59 mmol) was added at 0 ° C., the mixture was stirred for 15 minutes, and reacted at room temperature for 16 hours. Stop the reaction by adding distilled water,
Extracted with methylene chloride. Then, it was washed with distilled water and dried over anhydrous magnesium sulfate. After methylene chloride was distilled off under reduced pressure, the residue was separated and purified by column chromatography to obtain 16.6 g (47 mmol) of a silyl ether compound.

(F) The silyl ether compound 14.1 obtained by the above reaction was added to 120 ml of acetic acid under a nitrogen atmosphere.
g (40 mmol) and magnesium monoperoxyphthalate (23.2 g, 60 mmol) were added, and the mixture was heated at 80 ° C. for 12 hours.
Reacted for hours. After acetic acid was distilled off under reduced pressure, a saturated sodium hydrogen carbonate solution was added, and the mixture was extracted with ethyl acetate. Then, it was washed with saturated saline and dried over anhydrous magnesium sulfate. After distilling off ethyl acetate under reduced pressure, the residue was separated and purified by column chromatography to give 4.7 g (16 mmol) of (4S, 1 ′S) butenolide compound and (4R, 1 ′).
3.0 g (10 mmol) of S) butenolide compound was obtained.
Incidentally, 4.2 g (12 mmol) of the raw material was also recovered.

(G) 1.0 g (10 mmol) of cuprous chloride in 10 ml of tetrahydrofuran under a nitrogen atmosphere.
Then, 12.5 ml (20 mmol) of 1.6 M n-butyllithium hexane solution was slowly added dropwise at -78 ° C, and the temperature was -78 ° C for 30 minutes, room temperature for 5 minutes, and further -7.
The reaction was carried out at 8 ° C for 30 minutes. Trifluoroborane-ether complex (2.8 g, 20 mmol) was added, and the mixture was stirred at -78 ° C for 30 minutes.
It was stirred for a minute. Then, obtained by the above reaction (4S,
A solution of 1.5 g (5 mmol) of 1'S) butenolide compound in tetrahydrofuran (2 ml) was added dropwise, and -7
The reaction was carried out at 8 ° C for 2 hours. The reaction was stopped by adding dilute aqueous ammonia, and the mixture was extracted with ethyl acetate. The extract was washed successively with a sodium thiosulfate solution and saturated saline, and dried over anhydrous magnesium sulfate. The ethyl acetate was distilled off under reduced pressure, and the residue was separated and purified by silica gel column chromatography to obtain 1.5 g (4.3 mmol) of an alkylated compound.

(H) Sodium borohydride was added to a mixed solvent of 5 ml of tetrahydrofuran and 5 ml of diethylene glycol dimethyl ether under a nitrogen atmosphere.
0.11 g (2.8 mmol) was added, the mixture was stirred at 0 ° C., and 5.3 ml (42 mmol) of trifluoroborane-diethyl ether complex was added. Then, a tetrahydrofuran solution (3 ml) of 0.5 g (1.4 mmol) of the alkylated compound obtained in the above reaction was added dropwise, the mixture was reacted at 0 ° C. for 1 hour, and further refluxed for 1.5 hours. The reaction was stopped by adding distilled water, and the mixture was extracted with ether. The extract was washed with saturated saline and dried over anhydrous magnesium sulfate. Ether was distilled off under reduced pressure and 0.42 g of a tetrahydrofuran compound was obtained by separating and purifying by silica gel column chromatography.
1.2 mmol) was obtained.

(I) 0.42 g (1.2 mmol) of the tetrahydrofuran compound obtained in the above reaction was added to a mixed solvent of 3 ml of tetrahydrofuran and 2 ml of methanol, and then 0.31 g of tetra-n-butylammonium fluoride. (1.2 mmol) and added at 0 ° C for 3
The reaction was carried out for 0 minutes at room temperature for 4 days. The reaction was stopped by adding distilled water, and the mixture was extracted with ether. Next, it was washed with saturated saline and dried over anhydrous magnesium sulfate. After the ether was distilled off under reduced pressure, the residue was purified by silica gel column chromatography and (2S, 3S, 1'S) -tetrahydro-3-butyl-2- (2 ', 2', 2'-trifluoro-1'-).
0.25 g (1.1 mmol) of hydroxyethyl) furan was obtained.

The physical properties of the obtained compound are shown below. Molecular formula: C ₁₀ H ₁₇ F ₃ O ₂ ¹ H-NMR (proton nuclear magnetic resonance method); δ (ppm) 0.90 (t, J = 6.5 Hz, 3 H) 1.22 to 1.44 (m, 5H) 1.45 to 1.77 (m, 2H) 2.03 to 2.17 (m, 1H) 2.28 to 2.43 (m, 1H) 2.81 (d, J = 5.6Hz, 1H) 3.74-3.93 (m, 3H) 4.06 (ddq, J = 4.7, 5.6, 7.5Hz,
1 H) ¹⁹ F-NMR (nuclear magnetic resonance method using isotope fluorine, reference: CFCl ₃ ); δ (ppm) −6.03 (d, J = 7.4 Hz) IR (infrared absorption: cm ⁻¹ ) 3350, 1470, 1285, 1120, 1060 Mass spectrum m / e (M ⁺ +1) Calculated value 227.1259 Measured value 227.1270 [α] ²⁶ _D = + 31.9 ° (C (concentration) = 1.08, solvent:
methanol)

Reference Example 2 (2R, 3R, 1'S) -Tetrahydro-3-butyl-
Synthesis of 2- (2 ', 2', 2'-trifluoro-1'-hydroxyethyl) furan

[0062]

[Chemical 25]

(A) Obtained in Reference Example 1 (f) (4R,
The same procedure as in Reference Example 1 (g) was performed using 1.3 g (4.2 mmol) of the 1'S) butenolide compound to obtain 0.77 g (2.2 mmol) of the alkylated compound.

(B) Using 1.9 g (5.3 mmol) of the alkylated compound obtained in the above reaction, the same operation as in Reference Example 1 (h) was carried out to obtain 1.3 g (3.
9 mmol) was obtained.

(C) Using the tetrahydrofuran compound (1.3 g, 3.9 mmol) obtained in the above reaction, Reference Example 1
The same operation as in (i) is performed, and (2R, 3R, 1'S)-
Tetrahydro-3-butyl-2- (2 ', 2', 2'-
Trifluoro-1'-hydroxyethyl) furan 0.87
g (3.8 mmol) was obtained.

The physical properties of the obtained compound are shown below. Molecular formula: C ₁₀ H ₁₇ F ₃ O ₂ ¹ H-NMR; δ (ppm) 0.91 (t, J = 6.5 Hz, 3H) 1.22 to 1.73 (m, 7H) 2.07 to 2 .24 (m, 2H) 3.11 (d, J = 10.3 Hz, 1H) 3.68 to 3.72 (m, 1H) 3.77 to 4.07 (m, 3H) ¹⁹ F-NMR ( Standard: CFCl ₃ ); δ (ppm) −78.40 (d, J = 7.5 Hz) IR (cm ⁻¹ ) 3450, 1470, 1280, 11
70,1130 Mass spectrometry m / e (M ⁺ +1) Calculated value 227.1259 Measured value 227.1266 [α] _D ²⁶ = -45.3 ° (C = 1.06, methanol)

Example 1 (2S, 3S, 1'S) -Tetrahydro-3-butyl-
2- [2 ', 2', 2'-trifluoro-1'-
Synthesis of (4 "'-hexyloxybiphenyl-4" -carbonyloxy) ethyl] furan

[0068]

[Chemical formula 26]

0.57 g (1.8 mmol) of 4'-hexyloxy-4-biphenylcarboxylic acid chloride and Reference Example 1
(2S, 3S, 1'S) -tetrahydro-3 obtained in
-Butyl-2- (2 ', 2', 2'-trifluoro-
1'-hydroxyethyl) furan 0.34 g (1.5 mmol) in toluene solution 5 ml anhydrous pyridine 1
After adding milliliter, the reaction was carried out at room temperature for 18 hours. The reaction was stopped by adding 3N hydrochloric acid to the reaction solution, and the mixture was extracted with ether. Then, it was washed successively with a saturated sodium hydrogen carbonate solution and a saturated saline solution, and dried over anhydrous magnesium sulfate. After the ether was distilled off under reduced pressure, the residue was purified by silica gel column chromatography to obtain the desired compound (2S, 3S, 1'S) -tetrahydro-3-butyl-
2- [2 ', 2', 2'-trifluoro-1'-
0.53 g (1.0 mmol) of (4 ″ ′-hexyloxybiphenyl-4 ″ -carbonyloxy) ethyl] furan was obtained.

The physical properties of the obtained compound are shown below. Molecular formula: C ₂₉ H ₃₇ F ₃ O ₄ ¹ H-NMR; δ (ppm) 0.83 (t, J = 6.9 Hz, 3H) 0.92 (t, J = 7.3 Hz, 3H) 1.18 ~ 1.70 (m, 14H) 1.76 ~ 1.89 (m, 2H) 2.03 ~ 2.18 (m, 1H) 2.22 ~ 2.36 (m, 1H) 3.83 ~ 3 .91 (m, 2H) 3.97 to 4.08 (m, 1H) 4.01 (t, J = 6.5Hz, 2H) 5.62 (dq, J = 6.5Hz, 7.0Hz, 3H ) 6.99 (d, J = 8.7 Hz, 2H) 7.57 (d, J = 8.8 Hz, 2H) 7.66 (d, J = 8.5 Hz, 2H) 8.11 (d, J = 8.5 Hz, 2H) ¹⁹ F-NMR (reference: CFCl ₃ ); δ (ppm) −7 4.10 (d, J = 7.1 Hz) IR (cm ⁻¹ ) 1740, 1605, 1500, 1250, 1180 ，
1035 Mass spectrometry m / e (M ⁺ ) Calculated value 506.2644 Measured value 506.2644 [α] ²⁶ _D = -23.2 ° (C = 1.05, CHCl ₃ ).

Example 2 (2S, 3S, 1'S) -Tetrahydro-3-butyl-
2- [2 ', 2', 2'-trifluoro-1'-
Synthesis of (4 "'-heptylbiphenyl-4" -carbonyloxy) ethyl] furan

[0072]

[Chemical 27]

0.57 g (1.8 mmol) of 4'-heptyl-4-biphenylcarboxylic acid chloride and (2S, 3S, 1'S) -tetrahydro-3-butyl-2- (obtained in Reference Example 1). Using 0.34 g (1.5 mmol) of 2 ', 2', 2'-trifluoro-1'-hydroxyethyl) furan, the same operation as in Example 1 was carried out to obtain the target compound (2S, 3S, 1'S) -Tetrahydro-3-butyl-
2- [2 ', 2', 2'-trifluoro-1'-
0.57 g (1.1 mmol) of (4 ″ ′-heptylbiphenyl-4 ″ -carbonyloxy) ethyl] furan was obtained.

The physical properties of the obtained compound are shown below. Molecular _{formula: C 30 H 39 F 3 O} 3 1 H-NMR; δ (ppm) 0.79~0.98 (m, 6H) 1.17~1.46 (m, 13H) 1.50~1.73 (m, 4H) 2.03 to 2.18 (m, 1H) 2.23 to 2.39 (m, 1H) 2.66 (t, J = 7.7Hz, 2H) 3.82 to 3.93 (m, 2H) 4.03 to 4.11 (m, 1H) 5.63 (dq, J = 6.2, 7.1Hz, 1H) 7.29 (d, J = 8.2Hz, 2H) 7 .55 (d, J = 8.1 Hz, 2H) 7.69 (d, J = 8.6 Hz, 2H) 8.13 (d, J = 8.6 Hz, 2H) ¹⁹ F-NMR (reference: CFCl ₃ ); Δ (ppm) −74.13 (d, J = 7.0 Hz) IR (cm ⁻¹ ) 1740, 1610, 1500, 1255, 1180,
1095 mass spectrometry m / e (M ⁺ ) calculated value 504.2851 measured value 504.2857 [α] ²⁷ _D = -22.6 ° (C = 1.05, CHCl ₃ ).

Example 3 (2R, 3R, 1'S) -Tetrahydro-3-butyl-
2- [2 ', 2', 2'-trifluoro-1'-
Synthesis of (4 "'-hexyloxybiphenyl-4" -carbonyloxy) ethyl] furan

[0076]

[Chemical 28]

0.61 g (1.9 mmol) of 4'-hexyloxy-4-biphenylcarboxylic acid chloride and Reference Example 2
(2R, 3R, 1'S) -tetrahydro-3 obtained in
-Butyl-2- (2 ', 2', 2'-trifluoro-
The same operation as in Example 1 was carried out using 0.37 g (1.6 mmol) of 1′-hydroxyethyl) furan to obtain the target compound (2R, 3R, 1 ′S) -tetrahydro-3-butyl-2. -[2 ', 2', 2'-trifluoro-1'-
0.68 g (1.3 mmol) of (4 ″ ′-hexyloxybiphenyl-4 ″ -carbonyloxy) ethyl] furan was obtained.

The physical properties of the obtained compound are shown below. Molecular _{formula: C 29 H 37 F 3 O} 4 1 H-NMR; δ (ppm) 0.84~1.02 (m, 6H) 1.21~1.70 (m, 13H) 1.75~1.89 (m, 2H) 1.97 to 2.17 (m, 2H) 3.80 to 4.08 (m, 3H) 4.01 (t, J = 6.5Hz, 2H) 5.59 (dq, J = 2.9, 7.3 Hz, 1H) 6.99 (d, J = 8.8 Hz, 2H) 7.56 (d, J = 8.7 Hz, 2H) 7.66 (d, J = 8.6 Hz , 2H) 8.16 (d, J = 8.6 Hz, 2H) ¹⁹ F-NMR (reference: CFCl ₃ ); δ (ppm) −4.03 (d = 7.3 Hz) IR (cm ⁻¹ ) 1730 , 1610, 1500, 1260, 1180,
1090 mass spectrometry m / e (M ⁺ ) calculated value 506.2644 measured value 506.2641 [α] ²⁷ _D = −75.0 ° (C = 1.05, CHCl ₃ ).

Example 4 (2S, 3S, 1'S) -Tetrahydro-3-butyl-
2- [2 ', 2', 2'-trifluoro-1'-
Synthesis of (4 "'-hexyloxybiphenyl-4" -methyleneoxy) ethyl] furan

[0080]

[Chemical 29]

Obtained in Reference Example 1 (2S, 3S, 1 ')
S) -Tetrahydro-3-butyl-2- (2 ', 2',
2'-trifluoro-1'-hydroxyethyl) furan
A solution of 0.34 g (1.5 mmol) of tetrahydrofuran (3 ml) was added to 0.07 g of 60% sodium hydride (
A solution of (1.8 mmol) in tetrahydrofuran (5 ml) was added dropwise at 0 ° C. under a nitrogen atmosphere, and the mixture was stirred for 30 minutes. Next, a mixed solution of 0.55 g (1.8 mmol) of 4'-chloromethyl-4-hexyloxybiphenyl in tetrahydrofuran (5 milliliters) and dimethyl sulfoxide (5 milliliters) was added dropwise at room temperature and reacted for 5 days. The reaction solution was quenched with 1N hydrochloric acid, and extracted with ether. Then, it was washed with saturated saline and dried over anhydrous magnesium sulfate. After distilling off the ether under reduced pressure, the residue was purified by silica gel column chromatography to obtain the desired compound (2S, 3S, 1'S) -tetrahydro-3-butyl-2- [2 ', 2', 2'-trifluoro. 0.68 g of -1 '-(4'''-hexyloxybiphenyl-4''-methyleneoxy) ethyl] furan
(1.4 mmol) was obtained.

The physical properties of the obtained compound are shown below. Molecular _{formula: C 29 H 39 F 3 O} 3 1 H-NMR; δ (ppm) 0.80~0.99 (m, 6H) 1.18~1.65 (m, 13H) 1.76~1.88 (m, 2H) 1.98 to 2.16 (m, 1H) 2.27 to 2.42 (m, 1H) 3.78 to 3.95 (m, 4H) 3.99 (t, J = 6 .6 Hz, 2H) 4.68 (d, J = 11.1 Hz, 1H) 4.86 (d, J = 11.1 Hz, 1H) 6.96 (d, J = 8.8 Hz, 2H) 7.38 (d, J = 8.2 Hz, 2H) 7.51 (d, J = 8.6 Hz, 2H) 7.54 (d, J = 7.9 Hz, 2H) ¹⁹ F-NMR (reference: CFCl ₃ ); δ (ppm) −73.95 (d, J = 7.1 Hz) IR (cm ⁻¹ ) 1610, 1505, 1270, 1250, 1170 mass spectrometry m / e (M ⁺ ) calculated value 492.2851 measured value 492. 2867 [α] ²⁸ _D = + 11.8 ° (C = 1.08, CHCl ₃ ).

Example 5 (2S, 3S, 1'S) -Tetrahydro-3-butyl-
2- [2 ', 2', 2'-trifluoro-1'-
Synthesis of (4 "'-octyloxybiphenyl-4" -methyleneoxy) ethyl] furan

[0084]

[Chemical 30]

Obtained in Reference Example 1 (2S, 3S, 1 '
S) -Tetrahydro-3-butyl-2- (2 ', 2',
2'-trifluoro-1'-hydroxyethyl) furan
0.23 g (1.0 mmol) and 4'-bromomethyl-4-
Using 0.45 g (1.2 mmol) of octyloxybiphenyl and performing the same operation as in Example 4, (2S, 3S, 1'S) -tetrahydro-3-butyl- which is the target compound.
2- [2 ', 2', 2'-trifluoro-1'-
0.51 g (0.9 mmol) of (4 ″ ′-octyloxybiphenyl-4 ″ -methyleneoxy) ethyl] furan was obtained.

The physical properties of the obtained compound are shown below. Molecular _{formula: C 31 H 43 F 3 O} 3 1 H-NMR; δ (ppm) 0.81~0.97 (m, 6H) 1.17~1.64 (m, 17H) 1.76~1.89 (m, 2H) 2.00 to 2.15 (m, 1H) 2.28 to 2.41 (m, 1H) 3.73 to 3.93 (m, 4H) 3.99 (t, J = 6 .6 Hz, 2H) 4.68 (d, J = 11.1 Hz, 1H) 4.87 (d, J = 11.1 Hz, 1H) 6.97 (d, J = 8.8 Hz, 2H) 7.38 (d, J = 8.2 Hz, 2H) 7.51 (d, J = 8.5 Hz, 2H) 7.54 (d, J = 8.0 Hz, 2H) ¹⁹ F-NMR (reference: CFCl ₃ ); δ (ppm) −73.95 (d, J = 7.2 Hz) IR (cm ⁻¹ ) 1610, 1505, 1275, 1250, 1170,
1050 mass spectrometry m / e (M ⁺ ) calculated value 520.3164 actual value 520.3152 [α] ²⁴ _D = + 11.2 ° (C = 1.13, CHCl ₃ ).

Example 6 (2R, 3R, 1'S) -Tetrahydro-3-butyl-
2- [2 ', 2', 2'-trifluoro-1'-
Synthesis of (4 "'-hexyloxybiphenyl-4" -methyleneoxy) ethyl] furan

[0088]

[Chemical 31]

(2R, 3R, 1'obtained in Reference Example 2)
S) -Tetrahydro-3-butyl-2- (2 ', 2',
2'-trifluoro-1'-hydroxyethyl) furan
0.37 g (1.6 mmol) and 4'-chloromethyl-4-
Using 0.58 g (1.9 mmol) of hexyloxybiphenyl, the same operation as in Example 4 was carried out to obtain the desired compound (2R, 3R, 1 ′S) -tetrahydro-3-butyl-
2- [2 ', 2', 2'-trifluoro-1'-
0.70 g (1.4 mmol) of (4 ″ ′-hexyloxybiphenyl-4 ″ -methyleneoxy) ethyl] furan was obtained.

The physical properties of the obtained compound are shown below. Molecular formula: C ₂₉ H ₃₉ F ₃ O ₃ ¹ H-NMR; δ (ppm) 0.79 (t, J = 6.8 Hz, 3 H) 0.91 (t, J = 6.9 Hz, 3 H) 1.01 ~ 1.62 (m, 13H) 1.74 ~ 1.87 (m, 2H) 1.94 ~ 2.12 (m, 2H) 3.65 ~ 3.75 (m, 2H) 3.83 ~ 3 .92 (m, 2H) 4.00 (t, J = 6.6Hz, 2H) 4.63 (d, J = 11.7Hz, 1H) 4.96 (d, J = 11.7Hz, 1H) 6 .97 (d, J = 8.8Hz, 2H) 7.40 (d, J = 8.2Hz, 2H) 7.51 (d, J = 8.7Hz, 2H) 7.56 (d, J = 8 .3 Hz, 2 H) ¹⁹ F-NMR (reference: CFCl ₃ ); δ (ppm) −72.75 (d, J = 7.2 Hz) IR (cm ⁻¹ ) 1610, 1505, 1275, 1160, 1035 mass spectrometry m / e (M ⁺ ) calculated value 4922.851 measured value 4922864 [α] ²⁵ _D = -44.7 ° (C = 1.03, CHCl ₃ ).

[0091]

INDUSTRIAL APPLICABILITY The optically active tetrahydrofuran derivative of the present invention is a novel compound that is chemically stable, has no coloration, and is excellent in light stability, and has fast response.
Therefore, the optically active tetrahydrofuran derivative of the present invention can improve the high-speed response particularly when formed into a composition, and is useful as a compounding component of a ferroelectric liquid crystal that induces large spontaneous polarization.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Mitsunori Takeda 4 Towada, Kamisu-cho, Kashima-gun, Ibaraki Kashima Ishi Oil Co., Ltd. Kashima Refinery

Claims (1)

Claims: 1. The following general formula (I): [In the formula, Rf represents a fluoroalkyl group having 1 or 2 carbon atoms, R ¹ represents a linear or branched alkyl group having 3 to 20 carbon atoms, and R ² and R ³ each independently represent hydrogen or carbon number. 1 to 15 straight chain or branched chain alkyl group, 2 to 1 carbon atoms
5 represents an alkenyl group having 5 to 7 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, A represents —COO—, —O— or a single bond, and B represents —COO—, —OCO—, —CH ₂ O—, —OCH ₂ −
Or a single bond, Y represents —COO—, —CH ₂ O— or —O—, * represents an asymmetric carbon, and X ¹ and X ² are each independently Indicates. ] The optically active tetrahydrofuran derivative represented by these.