JPH04230677A - Optically active gamma-lactone derivative - Google Patents

Abstract

PURPOSE:To provide the subject new compound exhibiting liquid crystal nature by itself or free from liquid crystal property by itself but capable of increasing the response speed of a liquid crystal composition, having high spontaneous polarization and chemical stability and free from color. CONSTITUTION:The objective compound is expressed by formula I (Rf is 1-2C fluoroalkyl; R<1> is 3-20C chain alkyl; R<2> and R<3> are H or 1-15C chain alkyl; A is -COO-, -O-, etc.; B is -OCH2-, single bond, etc.; Y is -CH2O-, -O-, etc.; X<1> and X<2> are group of formula II, formula III, etc.; * represents asymmetric carbon atom), e.g. (4R,1'R)-(2',2',2'-trifluoro-1'-hydroxyethyl)-4-butanolide. For example, a compound of formula I wherein B and Y are -COO- can be produced by reacting a compound of formula IV with a compound of formula Bz-X<2>-COCl (Bz is benzyl), debenzylating the resultant compound of formula V and reacting the product with a compound of formula R<1>-A-X<1>-COCl.

Description

Description: [0001] The present invention relates to a novel optically active γ-lactone derivative useful as a liquid crystal material used in display elements or electro-optical elements. [0002] In recent years, the fields of use of liquid crystals, such as various display elements, electro-optical devices, and liquid crystal sensors, have been expanding significantly, and liquid crystal compounds with various structures have been proposed accordingly. In particular, the main liquid crystal material used in display elements is currently nematic liquid crystal, which uses a TN type or STN type simple matrix type, and a TFT type active matrix type in which a thin film transistor is attached to each pixel. is used. However, since the driving force of nematic liquid crystals is based on the weak interaction between the dielectric constant anisotropy of the liquid crystal material and the electric field, nematic liquid crystals inherently have the disadvantage of slow response speed (on the order of msec), and are It was disadvantageous as a material for large-screen display elements that require response. In contrast, in 1975, Mayer (
R. B. Ferroelectric liquid crystals, which were first synthesized by N.A. In type ferroelectric liquid crystal device (SSFLCD), the μsec
Since announcing its high-speed response and memory properties, it has attracted attention, and many ferroelectric liquid crystal compounds have been synthesized. The response speed of ferroelectric liquid crystal is τ=η/Ps
・Known as E. Here, η indicates rotational viscosity, and P
s indicates spontaneous polarization, and E indicates electric field strength. from now,
In order to achieve high-speed response, the development goal has been to develop liquid crystal materials with low viscosity and high spontaneous polarization. Additionally, liquid crystal materials are required to have properties such as chemical stability and wide operating temperature range, but it has been difficult to satisfy these properties with a single compound. Therefore, conventionally, compounds having multiple chiral smectic C phases (SmC*) were mixed together, or compounds having a low viscosity smectic C phase (SmC*) were mixed together.
A method has been used to obtain a ferroelectric liquid crystal composition exhibiting an SmC* phase having desired performance by adding an optically active compound to a base liquid crystal having C). In the latter case, the chiral dopant to be added may or may not itself have an SmC* phase, has good compatibility with the host liquid crystal, and induces large spontaneous polarization. However, it is required not to increase the viscosity. [0006] Spontaneous polarization is thought to occur as a result of the free rotation of the dipole moment in the direction perpendicular to the long axis of the molecule being suppressed by the influence of the asymmetric carbon about the long axis. Therefore, in order to increase spontaneous polarization, 1) bring the dipole part closer to the skeletal part called the core, 2) bring the dipole part and the asymmetric carbon atom closer, 3) add a sterically large substituent to the asymmetric carbon. Attempts have been made to increase spontaneous polarization by adding a Furthermore, it has recently been reported that a compound with a structure in which a dipole moiety and an asymmetric carbon are directly connected to a five-membered ring lactone effectively restrains free rotation and has large spontaneous polarization (Japanese).
se Journal of Applied Phys.
sics, vol. 29, No. 6, ppL981-L983
). [0007] An object of the present invention is to introduce a fluoroalkyl group, which itself has a large electron-withdrawing property, onto the asymmetric carbon atom adjacent to such a five-membered ring lactone. It has a larger spontaneous polarization, is chemically stable, and exhibits liquid crystallinity by itself, or does not exhibit liquid crystallinity by itself, but is useful as a component of a ferroelectric liquid crystal that induces a large spontaneous polarization. , to provide new compounds. [Means for Solving the Problems] The present inventors have discovered that a specific γ
- It has been found that lactone derivatives are excellent dopants that either exhibit a liquid crystal phase when used alone or do not exhibit a liquid crystal phase when used alone, but can be expected to provide a high-speed response when used as a composition. The present invention was completed based on this knowledge. That is, the present invention provides general formula (I)
] [In the formula, Rf represents a fluoroalkyl group having 1 or 2 carbon atoms, R1 represents a linear or branched alkyl group having 3 to 20 carbon atoms, and R2 and R3 are each independently hydrogen or a fluoroalkyl group having 1 to 2 carbon atoms. 15 linear or branched alkyl groups,
A represents -COO-, -O- or a single bond, B represents -CO
O-, -OCO-, -CH2 O-, -OCH2 - or a single bond, Y represents -COO-, -CH2 O- or -O-, * represents an asymmetric carbon, X1 and X2
each independently represents [Formula 4]. The present invention provides an optically active γ-lactone derivative represented by the following. In the general formula (I), as mentioned above, Rf
represents a fluoroalkyl group having 1 or 2 carbon atoms, specifically a trifluoromethyl group, a difluoromethyl group, a chlorodifluoromethyl group, a pentafluoroethyl group, and preferably a trifluoromethyl group. R1 is a straight or branched alkyl group having 3 to 20 carbon atoms, such as 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
-octadecyl group, n-nonadecyl group, n-eicosyl group, etc. Among these, a branched alkyl group having an asymmetric carbon is an optically active group. Furthermore, R2 and R3 are each independently hydrogen or a straight or branched alkyl group having 1 to 15 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or a sec- Butyl group, ter
t-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,
Examples include n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, and n-pentadecyl group. The compound of general formula (I) according to the present invention can be produced by various methods, for example, by the following steps. In the case of B=-COO- and Y=-COO-: general formula (II) BzO-X2 -COCl

...(II) [wherein, X2 is the same as above, and B
z represents a benzyl group. ] The compound represented by the general formula (
III) [In the formula, Rf , R2 and R3 are the same as above. ] by reacting with a compound represented by the general formula (IV) [
[In the formula, Rf, Bz, X2, R2 and R3 are the same as above. ] is obtained. This reaction can be carried out in the presence of an organic base such as pyridine, triethylamine, etc. in a solvent such as toluene, benzene, methylene chloride, etc. at a temperature of -20°C to 80°C. Next, by removing the benzyl group in the resulting compound of general formula (IV) by a conventional method, the compound of general formula (V) [wherein Rf, X2, R2 and R3 are as defined above] is the same as ] is produced. This debenzylation reaction can be carried out, for example, by hydrogenolysis at normal pressure using an alcoholic solvent such as methanol, ethanol, propanol, or acetic acid in the presence of a Pd 2 /C catalyst. The compound of general formula (V) obtained as described above is converted into a compound of general formula (VI) R1 -A-X1 -COCl
...(VI) [wherein R1, A and X1 are the same as above. ] The compound of the above general formula (I) can be obtained by reacting with a compound represented by the formula (I). This reaction can be carried out in the presence of an organic base such as pyridine, triethylamine, etc. in a solvent such as toluene, benzene, methylene chloride, etc. at a temperature of -20°C to 80°C. Furthermore, B=-COO-, Y=-CH2O-
In the case of: general formula (VII) THPO-X2 -CH2Z
...(
VII) [In the formula, X2 is the same as above, THP represents a tetrahydropyranyl group, and Z represents chlorine, bromine, iodine or tosyl group. ] is reacted with the compound represented by the above general formula (III) to obtain the general formula (VIII) [wherein Rf, THP, It is. ] is obtained. This reaction can be carried out by reacting the compound of general formula (III) with an alkali metal hydride or a base such as sodium hydroxide or potassium hydroxide, and then adding the compound of general formula (VII). Next, the tetrahydropyranyl group in the obtained compound of general formula (VIII) is removed by a conventional method to obtain general formula (IX) [wherein Rf, X2, R2 and R3 is the same as above. ] is produced. This elimination of the tetrahydropyranyl group can be carried out using a solvent such as ether, tetrahydrofuran, chloroform, etc. in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, and para-toluenesulfonic acid. Next, the compound represented by the general formula (IX) obtained above is reacted with the compound represented by the above general formula (VI) to obtain the compound represented by the above general formula (I). This reaction can be carried out in the presence of an organic base such as pyridine, triethylamine, etc. in a solvent such as toluene, benzene, methylene chloride, etc. at a temperature of -20°C to 80°C. Further, in the case of B=-COO-, Y=-O-: general formula (X) THPO-X2 -I
・・・
- (X) [wherein THP and X2 are the same as above. ] is reacted with the compound represented by the above general formula (III) to obtain the general formula (XI) [wherein Rf, THP, It is. ] is obtained. This reaction is carried out by treating the compound of the general formula (III) with a base represented by an alkali metal hydride, then using cuprous iodide as a catalyst under reflux conditions of dimethylformamide, dimethyl sulfoxide, etc., and using the general formula (III). This can be carried out by reacting a compound represented by X). Next, the tetrahydropyranyl group in the obtained compound of general formula (XI) is removed by a conventional method to form general formula (XII) [where Rf, X2, R2 and R3 is the same as above. ] is produced. This elimination of the tetrahydropyranyl group can be carried out using a solvent such as ether, tetrahydrofuran, chloroform, etc. in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, and para-toluenesulfonic acid. Next, by reacting the obtained compound of general formula (XII) with the compound represented by general formula (VI) above, the compound of general formula (I) can be obtained. This reaction can be carried out in the presence of an organic base such as pyridine, triethylamine, etc. in a solvent such as toluene, benzene, methylene chloride, etc. at a temperature of -20°C to 80°C. [0023] Also, B=-CH2O-, Y=-COO
-: The compound represented by the above general formula (V) is represented by the general formula (XIII) R1-A-X1-CH2Z
... (XIII) [wherein R1, A, X1 and Z are the same as above. ] The compound of the above general formula (I) can be obtained by reacting with a compound represented by the formula (I). This reaction is carried out by reacting a compound of the general formula (V) with an alkali metal hydride or a base represented by sodium hydroxide or potassium hydroxide, and then reacting with the compound of the general formula (V).
This can be carried out by adding the compound XIII). [0024] Also, B=-OCH2-, Y=-COO
In the case of -: General formula (XIV) ZCH2 -X2 -COCl
... (XIV)
[In the formula, Z and X2 are the same as above. ] is reacted with the compound represented by the above general formula (III) to obtain the general formula (XV) [wherein Rf, Z, It is. ] is obtained. This reaction is
in a solvent such as toluene, benzene, methylene chloride, etc. in the presence of an organic base such as pyridine, triethylamine, etc.
It can be carried out at a temperature of 20°C to 80°C. Next, general formula (XVI)
R1-A-X1-OH
...(XVI) [wherein, R
1 , A and X1 are the same as above. ] is reacted with the above compound (XV) to obtain the compound of the above general formula (I). This reaction is expressed by the general formula (XVI
) can be reacted with an alkali metal hydride or a base represented by sodium hydroxide or potassium hydroxide, and then a compound of general formula (XV) is added thereto. Furthermore, in order to produce the compound of general formula (I) of the present invention, general formula (III) used as a raw material
The compounds can be prepared in a variety of ways. For example, when R2 = R3 = hydrogen: Furan is silylated to form the general formula (XVII): [In the formula, TMS represents a trimethylsilyl group. ] is obtained, and this compound is further trifluoroacetylated to obtain a compound represented by the general formula (XVIII). This reaction involves using a solvent such as tetrahydrofuran or diethyl ether, silylation using an organolithium compound such as n-butyllithium and trimethylsilyl chloride, and then trifluoroacetylation using the above-mentioned butyllithium and ethyl trifluoroacetate. This can be carried out at a temperature of -78°C to 0°C. The obtained compound of general formula (XVIII) is reduced by a conventional method to obtain a compound of general formula (XIX). This reaction can be carried out using, for example, sodium borohydride, lithium aluminum hydride, tin chloride, etc. as a reducing agent. The obtained compound of general formula (XIX) is acylated by reacting with acid chloride. Specifically, the acid chloride used as the acylating agent here includes acetyl chloride, propionyl chloride, isobutyroyl chloride, octanoyl chloride, benzoyl chloride, and the like. The resulting general formula (XX): [In the formula, R'CO represents an acyl group. ] By asymmetrically hydrolyzing the compound represented by the general formula (
XXI ) and (XXIa) Optically active alcohols and esters represented by the following formulas are obtained. As the enzyme used in this reaction, various so-called hydrolytic enzymes can be used, such as lipase PS, lipase MY, lipase OF, and cellulase. The above esters of general formula (XXIa) can be converted into alcohols of general formula (XXI) and enantiomeric alcohols by chemical hydrolysis and asymmetric hydrolysis with another enzyme. Next, the general formula (X
The alcohol represented by XI) is silylated to give the general formula (XXII): [In the formula, TBDMS represents a t-butyldimethylsilyl group. ] is obtained. This reaction can be carried out using t-butyldimethylsilyl chloride as the silylating agent. The obtained silyl derivative of general formula (XXII) is oxidized to obtain a compound represented by general formula (XXIII). In this reaction, as an oxidizing agent,
For example, it can be carried out using monoperoxyphthalic acid magnesium salt or hydrogen peroxide in a solvent such as acetic acid or chloroform. Furthermore, although a mixture of diastereomers is obtained in this reaction, these compounds can be easily separated by silica gel column chromatography. After separating the diastereomers of the general formula (XXIII) obtained, the diastereomers of the general formula (XXIII) are desilylated to form the general formula (XX
IV) A compound represented by the following formula is obtained. This desilylation reaction can be carried out by a conventional method, and can be carried out at 0°C in a tetrahydrofuran solvent using tetra-n-butylammonium fluoride as a catalyst. The obtained compound represented by general formula (XXIV) is hydrogenated to obtain the desired general formula (III).
A compound in which R2 and R3 are hydrogen is obtained. Hydrogenation can be carried out in a hydrogen atmosphere using, for example, ethanol, methanol, hexane, ethyl acetate, benzene, toluene, etc. as a solvent and using palladium charcoal as a catalyst. When R2 = alkyl group and R3 = H: the compound represented by the general formula (XXIII) is alkylated to obtain a compound represented by the general formula (XXV). This reaction can be carried out at -78°C using an organocopper reagent. Moreover, in this case, a diastereomer mixture is not obtained, and only one type of anti-isomer is produced. Next, by desilylating the obtained compound represented by the general formula (XXV), the desired general formula (X
XVI) A compound represented by the following formula can be obtained. This desilylation reaction can be carried out at 0° C. in a tetrahydrofuran solvent using tetra-n-butylammonium fluoride as a catalyst. Preferred compounds of the present invention include, for example, the following. [Chemical 23] [Chemical 24] [Chemical 25] [Chemical 26] [Chemical 27] [Chemical 28] [Chemical 29] [Chemical 30] [Examples] Next, the present invention will be explained based on the Examples. Although a more specific explanation will be given, the present invention is not limited thereto. Further, in each of the following examples, R and S of the optically active compound represented by the general formula (I) of the present invention were indicated based on the position number of the following formula. Example 1 (A) Synthesis of (4R,1'R)-(2',2',2'-trifluoro-1'-hydroxyethyl)-4-butanolide a) Furan 13.6g under nitrogen atmosphere
(200 mmol) to 150 ml of tetrahydrofuran, 1.5M n-butyllithium hexane solution 1
33 ml (200 mmol) was added dropwise at -20°C and reacted for 1 hour. Next, trimethylsilyl chloride 21.
7 g (200 mmol) was added dropwise and stirred at -20°C for 1 hour. 1.5M n-butyllithium hexane solution 13
After adding 3 ml (200 mmol) and reacting at -20°C for 1 hour, ethyl trifluoroacetate was added at -78°C.
4 g (200 mmol) was added dropwise, and the mixture was heated at -78°C for 1 hour.
The reaction was continued for an additional 1 hour at room temperature. 3N hydrochloric acid was added to this reaction solution to stop the reaction, and the mixture was extracted with ethyl acetate. Next, it was washed successively with saturated sodium hydrogen carbonate solution and saturated brine, and dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure to obtain a crude product of a furan derivative. (b) 2.3 g (60 mmol) of sodium borohydride was added to 100 ml of dry ethanol, and the crude product of the furan derivative obtained in the above reaction was added dropwise at 0° C. over 30 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 ethyl acetate was distilled off under reduced pressure, vacuum distillation was performed to obtain 40.5 g (170 mmol) of an alcohol compound. (c) Add the above (b) to 200 ml of methylene chloride.
) and 8.9 ml (110 mmol) of pyridine were added, and 8.6 g (110 mmol) of acetyl chloride was added dropwise at 0°C, followed by reaction at room temperature for 12 hours. . Then, 3N hydrochloric acid was added to stop the reaction, and the mixture was extracted with methylene chloride. Thereafter, it was sequentially cleaned with saturated sodium hydrogen carbonate solution and distilled water, and dried over anhydrous magnesium sulfate. After removing methylene chloride under reduced pressure, vacuum distillation was performed to obtain acetate 27
．． 5 g (98 mmol) were obtained. (d) 28.0 g (100 mmol) of the acetate obtained by the above reaction in 1000 ml of distilled water
was added and kept at 40°C in a mini jar fermenter. 20 g of lipase PS was added and reacted for 20 hours. 3N hydrochloric acid was added to stop the reaction at 0° C., and the mixture was filtered through Celite. The extract was extracted with ethyl acetate, washed with saturated brine, dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. Next, the optically active alcohol 1 was separated and purified by silica gel column chromatography.
1.7 g (49 mmol) and optically active acetate 13
．． 2 g (47 mmol) were obtained. The optical purity of the obtained alcohol was 97.5%e. e. Met. (e) 11.7 g (49 mmol) of the optically active alcohol obtained in the above reaction was mixed with 100 g of methylene chloride.
4.0 g (59 mmol) of imidazole dissolved in ml
of t-butyldimethylsilyl chloride at 0°C.
9 g (59 mmol) was added and reacted at room temperature for 16 hours. Next, the reaction was stopped by adding 3N hydrochloric acid, extracted with methylene chloride, washed successively with saturated sodium bicarbonate solution and distilled water, and dried over anhydrous magnesium sulfate. After distilling off methylene chloride under reduced pressure, it was separated and purified by column chromatography to obtain silyl ether 16.6
g (47 mmol) was obtained. (f) Under a nitrogen atmosphere, 14.1 g (40 mmol) of the silyl ether obtained in the above reaction and 23.0 g of magnesium monoperoxyphthalate were added to 120 ml of acetic acid.
2 g (60 mmol) was added, and the mixture was reacted at 80° C. for 12 hours. After acetic acid was distilled off under reduced pressure, saturated sodium hydrogen carbonate solution was added, and the mixture was extracted with ethyl acetate. Then, it was washed with saturated brine and dried over anhydrous magnesium sulfate. After distilling off ethyl acetate under reduced pressure, it was separated and purified by column chromatography to obtain 4.7 g (1
6 mmol) and (4S,1'R) body 3.0 g (10
mmol) was obtained. Additionally, 4.2 g (12 mmol) of raw material was also recovered. (g) (4R,1) obtained by the above reaction
'R) compound 3.0 g (10 mmol) was added to a mixed solvent of 10 ml of tetrahydrofuran and methanol 5 ml, and 0.26 g of tetra-n-butylammonium fluoride (
1 mmol) was added at 0°C and reacted for 10 hours. Distilled water was added to stop the reaction, and the mixture was extracted with ethyl acetate. After washing with distilled water, it was dried over anhydrous magnesium sulfate, ethyl acetate was distilled off under reduced pressure, and then purified by silica gel column chromatography to obtain 1.7 g (9.5 mmol) of alcohol. (h) 0.53 g (2.9 mmol) of the alcohol obtained by the above reaction was added to 10 ml of ethanol, and a reaction was carried out under a hydrogen atmosphere using 0.05 g of 10% palladium charcoal as a catalyst. After removing the catalyst by filtration, ethanol is distilled off under reduced pressure and separated and purified by silica gel column chromatography to obtain the desired product (
4R,1'R)-(2',2',2'-trifluoro-
1'-Hydroxyethyl)-4-butanolide 0.47g
(2.6 mmol) was obtained. (B) (4R,1'R)-4-[2',2
',2'-trifluoro-1'-(4''-decyloxybiphenyl-4''-carbonyloxy)ethyl]-4
Synthesis of -butanolide [Chemical formula 33] 0.99 g (2.7 mmol) of 4'-decyloxy-4-biphenylcarboxylic acid chloride and (4R
,1'R)-4-(2',2',2'-trifluoro-
1'-Hydroxyethyl)-4-butanolide 0.41g
2 ml of anhydrous pyridine was added to 5 ml of a toluene solution of (2.2 mmol) and reacted at room temperature for 14 hours. 3N hydrochloric acid was added to this reaction solution to stop the reaction, and the mixture was extracted with ether. Then, it was washed successively with saturated sodium hydrogen carbonate and saturated brine, and dried over anhydrous magnesium sulfate. After distilling off the ether under reduced pressure, the target compound (4R,1'R)-4-[2',
2',2'-trifluoro-1'-(4''-decyloxybiphenyl-4''-carbonyloxy)ethyl]-4
-0.95 g of butanolide was obtained. The physical properties of the obtained compound are shown below. Molecular formula: C29H35F3 O5 1H-NMR; σ (ppm) 0.89 (t, J = 6.6Hz, 3H); 1.22~
1.57 (m, 14H); 1.76-1.87 (m, 2
H); 2.40-2.71 (m, 4H); 4.01 (t
, J=6.5Hz, 2H); 4.96(dt, J=4
．． 0.7.0Hz, 1H); 5.94 (dq, J=4
．． 0,7.0Hz,1H); 7.00(d,J=
8.8Hz, 2H); 7.56 (d, J=8.8Hz
, 2H); 7.66 (d, J=8.5Hz, 2H)
;8.08 (d, J=8.5Hz, 2H) 19F-NMR (reference CFCl3); σ (ppm
)−74.31 (d, J=6.9Hz)IR(
cm-1) 1800, 1745, 1600, 1500,
1190,1030 Mass spectrometry m/e (M+) Calculated value 520.2437 Actual value 520.2469 [α]25D = -70.0° (c = 1.07, C
HCl3 ) Example 2 (4S,1'R)-4-[2',2',2'-trifluoro-1'-(4'''-decyloxybiphenyl-4''
-Carbonyloxy)ethyl]-4-butanolide [Chemical formula 34] 0.78 g (2.1 mmol) of 4'-decyloxy-4-biphenylcarboxylic acid chloride and (4S
,1'R)-4-(2',2',2'-trifluoro-
1'-hydroxyethyl)-4-butanolide 0.32g
2 ml of anhydrous pyridine was added to 5 ml of a toluene solution of (1.7 mmol) and reacted at room temperature for 16 hours. Next, the same post-treatment and purification as in Example 1(B) were performed to obtain the target compound (4S,1'R)-4-[2',2',2'
0.2 g of -trifluoro-1'-(4''-decyloxybiphenyl-4''-carbonyloxy)ethyl]-4-butanolide was obtained. The physical properties of the obtained compound are shown below. Molecular formula: C29H35F3O5 1H-NMR; σ (ppm) 0.89 (t, J = 6.4Hz, 3H); 1.20~
1.59 (m, 14H); 1.76-1.87 (m, 2
H); 2.09-2.27 (m, 1H); 2.43
~2.60 (m, 3H); 4.01 (t, J=6.5H
z, 2H); 5.01 (dt, J=3.5, 7.3H
z, 1H); 5.71 (dq, J=3.5, 6.7H
z, 1H); 7.00 (d, J=8.7Hz, 2H
); 7.56 (d, J=8.7Hz, 2H); 7.6
7 (d, J = 8.4Hz, 2H); 8.12 (d, J
=8.5Hz, 2H) 19F-NMR (reference CFCl3); σ (ppm
)−74.12 (d, J=6.8Hz)IR(
cm-1) 1780, 1740, 1605, 1500,
1190,1030 Mass spectrometry m/e (M+) Calculated value 520.2437 Actual value 520.2408 [α]27D = -31.5° (c = 1.01, CHC
Example 3 (4R,1'R)-4-[2',2',2'-trifluoro-1'-[4''-(4''''-decyloxybiphenyl-4''') Synthesis of -carbonyloxy)phenyl-1”-carbonyloxy]ethyl]-4-butanolide [Chemical formula 3
5. a) 0.59 g (2.4 mmol) of 4-benzyloxybenzoic acid chloride and (4R,1'R)-
2 ml of anhydrous pyridine was added to 5 ml of a toluene solution containing 0.37 g (2.0 mmol) of 4-(2',2',2'-trifluoro-1-hydroxymethyl)-4-butanolide, and the mixture was reacted at room temperature for 16 hours. I let it happen. 3N hydrochloric acid was added to this reaction solution to stop the reaction, and the mixture was extracted with ether. Then, it was washed successively with saturated sodium hydrogen carbonate and saturated brine, and dried over anhydrous magnesium sulfate. After distilling off the ether under reduced pressure, it was separated and purified by silica gel column chromatography to obtain 0.66 g of benzyl ether compound.
I got it. b) Add 0.1 g of 10% palladium-charcoal to a solution of the compound obtained in a) above in a mixed solvent of 5 ml of toluene and 5 ml of ethanol, and hydrogenolyze it at room temperature under a hydrogen atmosphere. was carried out for 27 hours. Thereafter, the reaction solution was filtered and the solvent was distilled off under reduced pressure, followed by separation and purification by silica gel column chromatography to obtain 0.48 g of an alcohol compound. c) 0.31 g of the compound obtained in b) above
(1.0 mmol) and 0.45 g (1.2 mmol) of 4'-decyloxy-4-biphenylcarboxylic acid chloride.
Add 2 ml of anhydrous pyridine to 5 ml of toluene solution of
The reaction was allowed to proceed at room temperature for 15 hours. 3N hydrochloric acid was added to this reaction solution to stop the reaction, and the mixture was extracted with ether. Then,
Washed sequentially with saturated sodium bicarbonate and saturated saline,
It was dried with anhydrous magnesium sulfate. After distilling off the ether under reduced pressure, the target compound was purified by silica gel column chromatography and recrystallization from ethanol.
4R,1'R)-4-[2',2',2'-trifluoro-1'-[4"-(4""-decyloxybiphenyl-4"'-carbonyloxy)phenyl-1"- 0.51 g of carbonyloxy]ethyl]-4-butanolide was obtained. The physical properties of the obtained compound are shown below. Molecular formula: C36H39F3O7 1H-NMR; σ (ppm) 0.89 (t, J =6.3Hz, 3H); 1.21~
1.66 (m, 14H); 1.77-1.94 (m, 2
H); 2.40-2.73 (m, 4H); 4.02 (t
, J=6.5Hz, 2H); 4.95(dt, J=4
．． 1,6.9Hz,1H);5.93(dq,J=4
．． 0.6.8Hz, 1H); 7.01 (d, J=8.
6Hz, 2H); 7.39 (d, J=8.6Hz,
2H); 7.60 (d, J=8.6Hz, 2H); 7
．． 71 (d, J = 8.3Hz, 2H); 8.15 (d
, J=8.7Hz, 2H); 8.23(d, J=8.
4Hz, 2H) 19F-NMR (Reference CFCl3
); σ(ppm)-74.32 (d, J=
6.9Hz) IR (cm-1) 1800, 1740,
1605,1505,1190,1070 Mass spectrometry m/e (M+) Calculated value 640.2648 Actual value 640.2673 [α]25D = -37.3° (c = 1.03, CHC
Example 4 (4R,1'R)-4-[2',2',2'-trifluoro-1'-[4"-(4"'-decyloxybiphenyl-4"") Synthesis of -methyleneoxy)phenyl-1”-carbonyloxy]ethyl]-4-butanolide [Chemical formula 36
0.48 g of the compound obtained in Example 3b)
(1.6 mmol) in THF (3 ml) at 60%
Sodium hydride 0.08 g (1.9 mmol) T
Add dropwise to HF (5 ml) solution at 0°C under nitrogen atmosphere,
Stirred for 0 minutes. Next, 0.68 g (1.9 mmol) of 4'-chloromethyl-4-decyloxybiphenyl was added to THF (5 ml).
- A mixed solution of dimethyl sulfoxide (10 ml) was added dropwise, and the mixture was stirred at 0°C for 30 minutes. The reaction was further carried out at 60°C for 24 hours. The reaction was stopped by adding 1N hydrochloric acid to the reaction solution, and the mixture was extracted with ether. Then, it was washed with saturated brine and dried over anhydrous magnesium sulfate. After distilling off the ether under reduced pressure, the target compound (4R,1'R)-4-[2',2',2'-trifluoro-1 was purified by silica gel column chromatography and recrystallization from ethanol. '-[4"-(4"'-decyloxybiphenyl-4""-methyleneoxy)phenyl-1"-carbonyloxy]ethyl]-4-butanolide 0.27 g
I got it. The physical properties of the obtained compound are shown below. Molecular formula: C36H41F3O6 1H-NMR; σ (ppm) 0.89 (t, J = 6.5Hz, 3H); 1.18~
1.59 (m, 14H); 1.75-1.86 (m, 2
H); 2.37-2.66 (m, 4H); 4.00 (t
, J=6.5Hz, 2H); 4.93(dt, J=4
．． 0,7.2Hz,1H);5.17(s,2H);
5.89 (dq, J=4.0, 7.0Hz, 1H);
6.97 (d, J = 8.7Hz, 2H); 7.05 (
d, J=8.9Hz, 2H); 7.46(d, J=8
．． 2Hz, 2H); 7.52 (d, J=8.8Hz
, 2H); 7.59 (d, J=8.2Hz, 2H);
8.01 (d, J = 8.9Hz, 2H) 19F-NMR (reference CFCl3); σ (ppm
)-74.35 (d, J=7.0Hz)IR(
cm-1) 1800, 1785, 1750, 1610,
1505,1190,1030 Mass spectrometry m/e (M+) Calculated value 626.2855 Actual value 626.2849 [α]26D = -39.7° (c = 0.96, CHC
Example 5 (4S,1'R)-4-[2',2',2'-trifluoro-1'-[4''-(4''''-decyloxybiphenyl-4''') Synthesis of -carbonyloxy)phenyl-1”-carbonyloxy]ethyl]-4-butanolide [Chemical formula 3
7] (4S, 1'R)-4-(2', 2', 2
Using 0.32 g (1.7 mmol) of '-trifluoro-1'-hydroxyethyl)-4-butanolide, esterification, debenzylation, and esterification reactions were carried out in the same manner as in Example 3. It is a compound (4S,1
'R)-4-[2',2',2'-trifluoro-1'
-[4"-(4""-decyloxybiphenyl-4"'
0.58 g of -carbonyloxy)phenyl-1''-carbonyloxy]ethyl]-4-butanolide was obtained. The physical properties of the obtained compound are shown below. Molecular formula: C36H39F3O7 1 H-NMR; σ (ppm) 0.89 (t, J=6.6Hz, 3H); 1.20~
1.59 (m, 14H); 1.76-1.90 (m, 2
H); 2.08-2.27 (m, 1H); 2.44-2
．． 63 (m, 3H); 4.02 (t, J=6.6Hz
, 2H); 5.00 (dt, J=3.8, 7.2Hz
, 1H); 5.70 (dq, J=3.8, 6.8Hz
, 1H); 7.01 (d, J=8.8Hz, 2H);
7.39 (d, J = 8.8Hz, 2H); 7.60 (
d, J=8.8Hz, 2H); 7.71(d, J=8
．． 6Hz, 2H); 8.19 (d, J=8.8Hz
, 2H); 8.24 (d, J = 8.5Hz, 2H) 19F-NMR (reference CFCl3); σ (ppm
)-74.09 (d, J=6.8Hz)IR(
cm-1) 1790, 1740, 1605, 1505,
1185,1070 Mass spectrometry m/e (M+) Calculated value 640.2648 Actual value 640.2648 [α]27D = -21.3° (c = 1.01, CHC
13) Example 6 (a) (3R,4R,1'R)-3-butyl-(2',
2',2'-trifluoro-1'-hydroxyethyl)
Synthesis of -4-butanolide [Chemical formula 38] Under nitrogen atmosphere, 10 m of tetrahydrofuran
1.9 g (10 mmol) of cuprous chloride was added to -7
1.6M n-butyllithium hexane solution 1 at 8°C
Slowly drop 2.5 ml (20 mmol) of -7
React at 8°C for 30 minutes, at room temperature for 5 minutes, and at -78°C for 30 minutes. 2.8g of trifluoroborane ether complex at -78℃
(20 mmol) was added and stirred at -78°C for 30 minutes. Next, (4R, 1'R) obtained in Example 1(A)(f)
) 1.5 g (5 mmol) of tetrahydrofuran (2
ml) solution was added dropwise and reacted at -78°C for 2 hours. The reaction was stopped by adding diluted aqueous ammonia, and the mixture was extracted with ethyl acetate. It was washed successively with sodium thiosulfate solution and saturated brine, and dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, and the residue was separated and purified using silica gel column chromatography to obtain 1.5 g (4.3 mmol) of an alkylated product. 1.5 g of alkylated product obtained in the above reaction
(4.3 mmol) was subjected to a desilylation reaction in the same manner as in Example 1 (A) (g) to obtain the desired (3R, 4R,
1'R)-3-butyl-(2',2',2'-trifluoro-1'-hydroxyethyl)-4-butanolide1.
0 g (4.1 mmol) was obtained. (b) (3R,4R,1'R)-3-butyl-4-[2',2',2'-trifluoro-1'-(
Synthesis of 4""-decyloxybiphenyl-4"'-carbonyloxy)ethyl]-4-butanolide [Chemical formula 39] (3R, 4R, 1'R) obtained in (a) above
-3-Butyl-4-(2',2',2'-trifluoro-1'-hydroxyethyl)-4-butanolide 0.26
g (1.1 mmol) and performed the same operation as in Example 1(B) to obtain the target compound (3R,4R,1'R)-3-
Butyl-4-[2',2',2'-trifluoro-1'
0.45 g of -(4''''-decyloxybiphenyl-4'''-carbonyloxy)ethyl]-4-butanolide was obtained. Physical properties of the obtained compound are shown below. Molecular formula: C33H43F3O5 1H -NMR; σ (ppm) 0.82-0.99 (m, 6H); 1.18-1.58
(m, 20H); 1.76-1.87 (m, 2H); 2
．． 26 (dd, J=4.3, 17.2Hz, 1H);
2.62-2.77 (m, 1H); 2.80 (dd, J
=9.3, 17.3Hz, 1H); 4.01(t, J
=6.5Hz, 2H); 4.61(dd, J=4.3
, 4.3Hz, 1H); 5.82 (dq, J=4.7
, 6.8Hz, 1H); 7.00 (d, J=8.8H
z, 2H); 7.56 (d, J=8.7Hz, 2H
); 7.67 (d, J=8.4Hz, 2H); 8.0
8 (d, J = 8.4Hz, 2H) 19F-NMR (reference CFCl3); σ (ppm
)-73.93 (d, J=6.9Hz)IR(
cm-1) 1790, 1750, 1605, 1500,
1190,1080 Mass spectrometry m/e (M+) Calculated value 576.3063 Actual value 576.3020 [α]26D =+45.5° (c=1.04,C
HCl3) Example 7 (3R,4R,1'R)-3-butyl-4-[2',2
',2'-trifluoro-1'-(4"'-decyloxybiphenyl-4""-methyleneoxy)ethyl]-4
-Synthesis of butanolide [Chemical formula 40] (3R,4R,1'R)-3-butyl-4
A solution of 0.26 g (1.1 mmol) of -(2',2',2'-trifluoro-1'-hydroxyethyl)-4-butanolide in THF (3 ml) was added to 0.05 g (1 ml) of 60% sodium hydride. .3 mmol) in THF (5 ml) under a nitrogen atmosphere at 0°C, and the mixture was stirred for 30 minutes. Next, 0.43 g (1.2 mmol) of 4'-chloromethyl-4-decyloxyrubiphenyl was added to THF (5 ml).
A mixed solution of dimethyl sulfoxide (10 ml) was added dropwise at room temperature, and the mixture was reacted at 60° C. for 24 hours. 1 in this reaction solution
The reaction was stopped by adding N-hydrochloric acid and extracted with ether. Then, it was washed with saturated brine and dried over anhydrous magnesium sulfate. After distilling off the ether under reduced pressure, the target compound (3R, 4R, 1'R) was purified by silica gel column chromatography and recrystallization from ethanol.
)-3-Butyl-4-[2',2',2'-trifluoro-1'-(4"'-decyloxybiphenyl-4""
-methyleneoxy)ethyl]-4-butanolide 0.24
I got g. The physical properties of the obtained compound are shown below. Molecular formula: C33H45F3O4 1H-NMR; σ (ppm) 0.80-0.98 (m, 6H); 1.14-1.60
(m, 20H); 1.74-1.86 (m, 2H); 2
．． 13 (dd, J=2.5, 17.2Hz, 1H);
2.58-2.72 (m, 1H); 2.76 (dd, J
=9.5, 17.3Hz, 1H); 3.98(t, J
=6.5Hz, 2H); 4.11(dq, J=2.4
, 7.2Hz, 1H); 4.42 (dd, J=2.4
, 2.4Hz, 1H); 4.63 (d, J=10.7
Hz, 1H); 4.85 (d, J=10.6Hz, 1
H); 6.95 (d, J=8.8Hz, 2H); 7.
33 (d, J=8.2Hz, 2H); 7.50 (d,
J=8.8Hz, 2H); 7.55(d, J=8.2
Hz, 2H) 19F-NMR (reference CFCl3); σ (ppm
)-73.39 (d, J=7.1Hz)IR(
cm-1) 1790, 1610, 1505, 1170,
1060 Mass spectrometry m/e (M+) Calculated value 562.3270 Actual value 562.3268 [α]26D = +4.6° (c = 1.01, CHCl
3) Example 8 (3R,4R,1'R)-3-butyl-4-[2',2
Synthesis of ',2'-trifluoro-1'-[4"-(4""-decyloxybiphenyl-4"'-carbonyloxy)phenyl-1"-carbonyloxy]ethyl]-4-butanolide [Chemical formula 41 ] (3R,4R,1'R)-3-butyl-4
-[2',2',2'-trifluoro-1'-hydroxyethyl)-4-butanolide 0.26 g (1.1 mmol) was used in the same manner as in Example 3, and the target compound was obtained. (3R,4R,1'R)-3-butyl-4-[2
',2',2'-trifluoro-1'-[4"-(4"
``-decyloxybiphenyl-4''-carbonyloxy)phenyl-1''-carbonyloxy]ethyl]-4
-0.15 g of butanolide was obtained. The physical properties of the obtained compound are shown below. Molecular formula: C40H47F3O7 1H-NMR; σ (ppm) 0.77-0.99 (m, 6H); 1.12-1.72
(m, 20H); 1.76-1.87 (m, 2H); 2
．． 27 (dd, J=4.5, 17.3Hz, 1H);
2.56-2.76 (m, 1H); 2.79 (dd, J
=9.3, 17.4Hz, 1H); 4.02(t, J
=6.5Hz, 2H); 4.61(dd, J=4.4
, 4.4Hz, 1H); 5.81 (dq, J=4.8
, 6.8Hz, 1H); 7.01 (d, J=8.7H
z, 2H); 7.40 (d, J=8.7Hz, 2H
); 7.60 (d, J=8.7Hz, 2H); 7.7
1 (d, J = 8.4Hz, 2H); 8.15 (d, J
=8.7Hz,2H);8.24(d,J=8.4H
z, 2H); 19F-NMR (reference CFCl3); σ (ppm
)-73.91 (d, J=6.8Hz)IR(
cm-1) 1800, 1740, 1600, 1500,
1185,1070 Mass spectrometry m/e (M+) Calculated value 696.3274 Actual value 696.3254 [α]26D = +25.9° (c = 1.01, CHC
13) The phase transition temperatures of the compounds synthesized in Examples 1 to 8 were as shown in Table 1 based on DSC measurement and observation using a polarizing microscope. [Table 1] [0080] In the table, Cryst represents a crystal phase, and Is
o represents isotropic phase and SmA represents smectic A phase. Effects of the Invention The optically active γ-lactone derivative of the present invention is a novel compound that is chemically stable, has no coloration, and has excellent photostability, and exhibits liquid crystallinity or can be used alone. Although it does not exhibit liquid crystallinity, it is useful as a compounding component of ferroelectric liquid crystals that induces large spontaneous polarization and can improve high-speed response when used as a composition.

Claims (1)

[Claims] Claim 1: General formula (I) [In the formula, Rf represents a fluoroalkyl group having 1 or 2 carbon atoms, R1 represents a straight chain or branched alkyl group having 3 to 20 carbon atoms, R2 and R3 each independently represent hydrogen or a straight or branched alkyl group having 1 to 15 carbon atoms,
A represents -COO-, -O- or a single bond, B represents -CO
O-, -OCO-, -CH2 O-, -OCH2 - or a single bond, Y represents -COO-, -CH2 O- or -O-, * represents an asymmetric carbon, X1 and X2
each independently represents [Chemical formula 2]. ] An optically active γ-lactone derivative represented by: