JPH07138196A - Trifluoromethyl-substituted vinyl compound, its production, liquid crystal composition containing the same compound and liquid crystal light-modulating apparatus using the same composition - Google Patents

Abstract

PURPOSE:To provide a new trifluoromethyl-substituted vinyl compound useful as a liquid crystal composition for liquid crystal flat displays, etc., exhibiting a smectic A phase and excellent in physicochemical stability, low viscosity and refractive index anisopropy. CONSTITUTION:A compound of formula I [R<1> is (substituted) 1-14C alkyl; R<2> is H or halogen; R<3> is H or an electron-attracting group; X and Y are each a (substituted) aromatic ring, a (substituted) nonaromatic hydrocarbon homocycle, a (substituted) nonaroamtic heterocycle, etc.; Q<1> is single bond, an ether bond or an ester bond; Q<2> is a single bond, an ester bond, CidenticalC, CH=CH, Ch2CH2 or CH2O; m and are each 1 or 2], e.g. chloro-1-trifluoromethyl-2-(4'-heptyl-4- biphenyl)-ethylene. This compound of formula I is obtained by reacting a compound of formula II with a compound of formula III and then subjecting the resultant compound of formula IV to dehydration reaction.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel liquid crystal compound exhibiting a liquid crystal phase and having a low viscosity, and a liquid crystal composition containing at least one thereof.

[0002]

2. Description of the Related Art Liquid crystal compounds exhibit dielectric anisotropy and optical anisotropy in the liquid crystal phase. The liquid crystal phase includes a nematic liquid crystal phase, a smectic liquid crystal phase, a cholesteric liquid crystal phase, etc. Among them, applied products using the nematic liquid crystal phase are most widely put into practical use. In other words, applied products that utilize these characteristics have been expanded to light control glass, sign displays, and flat panel displays such as calculators, watches, and word processors, and their development has been remarkable over a wide range with recent advances in the electronics field. .
Dynamic scattering type (DS type), twisted nematic type (TN type), super twisted nematic type (STN type), guest-host type (GH
Type) etc. The liquid crystal materials used for these are naturally required to have physicochemical stability, particularly stability to heat, light, moisture, air and the like. Further, the liquid crystal material should exhibit a desired liquid crystal phase in a temperature range as wide as possible including room temperature, and physical properties such as an operating voltage and responsiveness according to the purpose must be satisfied at a practical level. That is, it is generally preferable that the threshold voltage and the saturation voltage necessary for driving the liquid crystal display element are as low as possible, and that the viscosity of the liquid crystal material is as low as possible in order to increase the response speed.

Other than nematic liquid crystals, liquid crystals having high utility in device technology include sulctic A (S _A ) liquid crystals and chiral smectic C * (S _c *) liquid crystals. The smectic A liquid crystal phase is the liquid crystal phase that appears most frequently among the smectic liquid crystal phases. The smectic A liquid crystal phase has a homeotropic (vertical) alignment state or a focal conic domain state. Since the focal conic domain and the homeotropic domain are optically different, they can be used for display devices. That is, when minute focal conic domains are distributed, light is strongly scattered and becomes a cloudy state. On the other hand, in the case of homeotropic domain, light is transmitted as it is,
It is transparent. The following two methods are considered as methods for obtaining the scattering domain. The first method is a voltage application method and the second method is a quenching method. That is, when a low frequency voltage of about 100 V is applied to the smectic A liquid crystal phase having high electric conductivity, a focal conic domain is obtained. This state is maintained for a long time even when the voltage is turned off. The latter second method is a method of obtaining a scattering domain by heating the smectic A liquid crystal above the clearing point and quenching it from the isotropic phase. Such a scattered document can be formed extremely locally by devising a hard surface, and an image with a very high resolution (high-quality image) can be obtained. For displays, materials with large positive Δε and large Δn for increasing display contrast are required. In addition, a material having light resistance is required because it is exposed to intense light.
As smectic A liquid crystal compounds, many examples of compounds have already been known. However, the present situation is that no single compound has yet been found to satisfy these required characteristics. Therefore, there is no choice but to satisfy the required characteristics as a composition by mixing several kinds of liquid crystal compounds having excellent physical and chemical stability and excellent specific physical properties to prepare a composition. It has excellent physical and chemical stability, and exhibits a smectic S _A phase in a wide temperature range including room temperature, with a large Δn
Alternatively, developing a single smectic A liquid crystal compound having a large positive Δε is extremely useful in constructing these smectic liquid crystal compositions.

[0004]

An object of the present invention is to provide a novel liquid crystal compound useful in developing such a practical liquid crystal composition.

[0005]

As a result of intensive studies to solve the above problems, the present inventors succeeded in synthesizing a novel compound represented by the formula (I), and It was found that I) shows an unexpectedly stable nematic phase and has a large refractive index anisotropy (Δn),
The present invention has been completed.

That is, the present invention is represented by the following general formula (I)

[0007]

[Chemical 8]

[In the formula, R ¹ represents an optionally substituted alkyl group having 1 to 14 carbon atoms, R ² represents a hydrogen atom or a halogen atom, and R ³ is selected from a hydrogen atom or an electron-withdrawing group. X and Y are the same or different and optionally substituted aromatic or non-aromatic carbocycles or heterocycles, and m and n are 1 respectively.
Or 2 is shown, Q ¹ is a single bond, an ether bond, an ester bond or a thioester bond, and Q ² is a single bond,
Ester bond,

[0009]

[Chemical 9]

[0010] _{-CH = CH -, - CH 2} CH 2 -, or an methyleneoxy bonds. ] A dioxaborinane-based compound represented by the above, a method for producing the same, a liquid crystal composition containing the compound, and a liquid crystal light modulator using the composition. In the general formula (I), R ¹ represents an optionally substituted alkyl group having 1 to 14 carbon atoms. The alkyl group may be linear or branched, and specifically, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-.
Octyl, n-nonyl, n-decyl, n-undecyl,
linear alkyl groups such as n-dodecyl, n-tridecyl, n-tetradecyl and isopropyl, isobutyl,
sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, 1-
Methylpentyl, 2-methylpentyl, 5-methylhexyl, 2,3,5-trimethylhexyl, 2,7,8-
Examples thereof include branched alkyl groups such as trimethyldecyl and 4-ethyl-5-methylnonyl. Among them, a linear alkyl group having 3 to 6 carbon atoms, such as propyl,
Butyl, pentyl and hexyl are preferred. Further, in these groups, for example, some or all of hydrogen atoms may be substituted with halogen.

R ² is a hydrogen atom or a halogen atom such as fluorine, chlorine, bromine or iodine. Of these, a hydrogen atom is preferable. R ³ represents one selected from a hydrogen atom or an electron withdrawing group. Examples of the electron-withdrawing group include a halogen atom, a cyano group, a CF ₃ group, a CHF ₂ group, a carboxylic acid ester group, a carboxylic acid group, a nitro group, an aldehyde group and a carbonyl group. Among these, F, Cl,
A halogen atom of Br and I, a cyano group, and a CF ₃ group are preferable. X and Y each represent an optionally substituted aromatic or non-aromatic carbon homocycle or heterocycle. A specific example is

[0012]

[Chemical 10]

There is a 5- to 6-membered ring with the following

[0014]

[Chemical 11]

Is preferred. Further, these rings may be substituted with a halogen, a cyano group or the like as a substituent,
A fluorine atom is particularly preferable as the halogen atom. Further, X and Y may be the same or different. m and n each represent 1 or 2. Q ¹ includes a single bond, an ether bond, an ester bond, and a thioester bond. In this case, the carboxylic acid ester bond and the thioester bond include a normal ester bond and a reverse ester bond, but any of them may be used. Q ² is a single bond, an ester bond,

[0016]

[Chemical 12]

[0017] _{-CH = CH-, CH 2 CH 2} -, or an methyleneoxy bonds. Also in this case, either a normal ester bond or a reverse ester bond may be used.

A preferred embodiment of the present invention is the following general formula (I ')

[0019]

[Chemical 13]

[In the formula, R ¹¹ represents a straight-chain alkyl group having 3 to 6 carbon atoms, and R ²¹ represents a halogen atom. ] It is a compound represented by these. INDUSTRIAL APPLICABILITY The compound of the present invention is stable to moisture, oxygen gas and light, has excellent physical and chemical stability such as excellent storage stability even in air and high voltage holding ratio, and is a stable smectic A liquid crystal. In addition to exhibiting a phase, it is characterized by a large refractive index anisotropy (Δn).

Therefore, the compound of the present invention is an additive effective for lowering the voltage of the liquid crystal composition with respect to the threshold voltage and the saturation voltage necessary for driving the liquid crystal display device and the like,
It can be used as a useful component in constructing a practical liquid crystal composition. The compound of the present invention can be used alone as a liquid crystal compound, and by adding it to another liquid crystal mixture, the liquid crystal activity of the other liquid crystal mixture can be enhanced. The liquid crystal compound of the present invention is excellent in compatibility with conventionally known liquid crystal compounds, for example, ester-based, ether-based, carbonyl-based, biphenyl-based, phenylcyclohexane-based, heterocyclic-based liquid crystal compounds, etc. A liquid crystal composition exhibiting excellent properties can be constructed by adding and blending the liquid crystal compound.

The liquid crystal mixture to which the compound of the present invention can be added is, for example, "Flusige Kristalle".
in Tabellen "I & II VEB Verla
g. Leipzig and "Liquid Crystal Device Handbook"
(Japan Society for the Advancement of Science, 142nd Edition, Nikkan Kogyo Shimbun)
Alternatively, the smectic liquid crystal described in “Full-color liquid crystal display technology” (Trikeps Publishing, edited by Trikeps Co., Ltd.) or the like, or a commercially available smectic liquid crystal compound can be used. In that case, the addition amount of the compound of the present invention is usually about 0.5% to 50%, preferably 5% to 20%.
%. The liquid crystal light modulation device in the present invention is a liquid crystal element and a display device using a liquid crystal composition, and specific examples thereof include a liquid crystal shutter, an optical phase filter and a display. Representative examples of the method for producing the compound represented by formula (I) of the present invention are described below. The present invention is not limited by these methods.

Production Example The following general formula (II)

[0024]

[Chemical 14]

[Wherein R ¹ , X, Y, m, n, Q ¹ and Q
² has the same meaning as above. ] And a skeleton component represented by the following general formula (III)

[0026]

[Chemical 15]

A compound represented by the formula [wherein R ² and R ³ have the same meaning as described above] is subjected to a Reformski reaction to produce a compound represented by the following general formula (IV), and the compound is dehydrated with acetic anhydride. By reacting, a compound represented by the general formula (I) is produced.

[0028]

[Chemical 16]

Here, the compound represented by the general formula (II) is produced, for example, as follows. The following general formula (V)

[0030]

[Chemical 17]

[Wherein, R ¹ , Q ¹ , Q ² , X and m have the same meanings as described above. ] From the compound represented by the following general formula (VI)

[0032]

[Chemical 18]

[In the formula, Y has the same meaning as described above. ]]

[0034]

[Chemical 19]

Further, a Reformatsky reagent (organozinc compound) derived from 1,1,1-trichloro-2,2,2-trifluoroethane is allowed to act on the above-mentioned skeleton component aldehyde compound, and then desalted or hydrogen, a hydroxyl group. The compound of the present invention is produced by subjecting the compound to acetylation and then a reduction reaction.

[0036]

[Chemical 20]

The representative production examples of the compound represented by formula (I) of the present invention have been described above, but the production methods are not limited to these. The object compound (I) of the present invention produced by the above-mentioned method is separated from the reaction solution by a commonly used separation and purification means such as extraction, phase transfer, column chromatography, liquid chromatography and recrystallization. It can be separated and purified.

[0038]

EXAMPLES The present invention will now be described in detail with reference to examples, but the invention is not limited thereto. Example 1 Production of the following compound

[0039]

[Chemical 21]

4'-Heptyl-4-biphenylcarboxylic acid (9.87 g) was dissolved in tetrahydrofuran (80 ml), and lithium aluminum hydride (2.51) was added.
g) was slowly added dropwise to a tetrahydrofuran (150 ml) suspension, and the mixture was stirred at room temperature for 1 hour. Then 1N-
HCl (300 ml) and ethyl ether (300 ml)
Then, the extraction operation is performed. Wash the ethyl ether layer with water (1
(00 ml) and the ethyl ether layer is dried over anhydrous sodium sulfate. The filtrate is distilled off under reduced pressure to obtain a residue.
Dichloromethane (440 ml) was added to and dissolved in this, and manganese dioxide (11.2 g) was slowly added at room temperature. After stirring for 1 hour, this is filtered and the filtrate is concentrated under reduced pressure, and crystals start to precipitate. Recrystallize with the minimum amount of solvent,
Light yellow crystals were obtained. Yield 11.2g, yield 91.8.
%.

[0041]

[Chemical formula 22]

DM was added to the above-mentioned aldehyde (10.3 g).
F (30 ml) was added and dissolved, 1,1,1-trichloro-2,2,2-trifluoroethane (10.3 g) and zinc (powder and granules 4.8 g each) were added, and the internal temperature was adjusted to 60 ° C. The mixture was stirred overnight. Acetic anhydride (9 ml) and zinc (5.2 g of granules) were added to this reaction solution, and the mixture was reacted at room temperature for 3 hours. The reaction solution was poured into 1N-HCl (300 ml) and extracted with ethyl acetate (300 ml). After washing with water (100 ml), anhydrous sodium sulfate is added to the ethyl acetate layer for drying. After the solvent was distilled off from this filtrate under reduced pressure, the residue was treated with silica gel (Wakogel C-300,
100 g) and developing and subjecting to column chromatography using n-hexane as an eluting solvent for purification. The target fraction is evaporated to dryness under reduced pressure. Yield 7.0 g, 50.0% yield. This dry solid (1.0 g) was recrystallized with acetonitrile (10 ml) aqueous solvent while hot to obtain white crystals (0.71 g). IR (kBr) _max cm ^-1 : 2921, 852,14
61, 1400, 1170, 1139 ¹ H-NMR (200 MHz, CDCl ₃ ) δ: 7.82 to 7.25 (8 H, dd, Dipheny).
1 H) 7.29 (1 H, S,

[0043]

[Chemical formula 23]

[0044] _{2.65 (2H, t, -CH 2} -) 1.7
_{~1.6 (2H, m, -CH 2} -) 1.4~1.2 (8
_{H, m, -CH 2 -)} 0.88 (3H, t, -CH 3) Elemental analysis _{C 22 H 24 ClF 3 (Mw.380,88} )
Theoretical value: C, 69.38; H, 6.35 Actual phase value: C, 69.26; H, 6.38 Example 2 Production of the following compound

[0045]

[Chemical formula 24]

4-carboxy-4'-biphenol (4
2.8 g) was dissolved in tetrahydrofuran (400 ml), and lithium aluminum hydride (9.1) was added thereto.
g) is slowly added dropwise to a tetrahydrofuran (220 ml) suspension. Final stirring is performed while maintaining the internal temperature at 90 ° C. 1N-HCl (500 ml) was slowly added dropwise to this reaction solution to separate it into an organic layer and an aqueous layer. Ethyl acetate (500 ml) is added to this aqueous layer for extraction. The ethyl acetate layer and the organic layer are combined and the solvent is distilled off under reduced pressure to precipitate crystals. 1
A 0% potassium carbonate (500 ml) solution was added to remove unreacted raw materials, and the crystals were recrystallized from acetone while heating to give a primary crystal of 21.4.
g, 4.4 g of secondary crystals are obtained. Total yield 25.8g, total yield 6
4.5%.

[0047]

[Chemical 25]

Methylene chloride (320 ml) and tetrahydrofuran (200 mg) were added to the reduced product (25.8 g) of the preceding paragraph.
ml) and triethylamine (15.6 g) were added and dissolved, and p-propoxy-benzoic acid (27.7 g) was heated under reflux with thionyl chloride (140 ml) for 5 hours and concentrated under reduced pressure to obtain an acid chloride. A dichloromethane solution (50 ml) of the body is added dropwise at an internal temperature of 40 ° C. and the mixture is stirred. After stirring for about 4 hours, the mixture is washed with water (500 ml), the methylene chloride layer is separated, and dried under reduced pressure. The dried solid is dissolved in ethyl acetate (1.5 liter), and a 10% potassium carbonate (500 ml) solution is added to separate the layers. After the ethyl acetate layer was dried under reduced pressure, acetone (1 liter) was added while it was hot to recrystallize to obtain white needle crystals (27.2 g). Yield 58.6
%, About 10 g of mother liquor recovered product is obtained.

[0049]

[Chemical formula 26]

Methylene chloride (1 liter) was added to the above ester product (27.2 g) to dissolve it, and manganese dioxide was gradually added. The reaction was completed by the thin layer chromatography when 76 g was added, and therefore, filtration was carried out using Hyflo Supercel (50 g). After the filtrate was dried to dryness under reduced pressure, 8 g of the aldehyde compound synthesized from the mother liquor recovered product was combined by the same method and recrystallized with acetone (1 liter) while hot to give 24.3 g of the primary crystal and 6 of the secondary crystal. Obtained was 0.7 g. Total yield 31.0 g, total yield 66.7%.

[0051]

[Chemical 27]

DM was added to the above-mentioned aldehyde (31.0 g).
F (210 ml) was added and 1,1,1-trichloro-
2,2,2-Trifluoroethane (32.2 g) and zinc (powder and granules 8.43 g each) were added to carry out a final liquid reaction at an internal temperature of 50 ° C. Acetic anhydride (22 ml) and zinc dust (8.4 g) were added to this reaction, and the mixture was reacted at an internal temperature of 75 ° C for 2 hours.
¹ N-HCl (500 ml) and ethyl acetate (500 m
l) was added and extraction was performed. After washing with water (500 ml),
The residue distilled off under reduced pressure was subjected to silica gel (Wakogel C-3
00 500 g) and the target fraction to be purified by column chromatography using chloroform-n-hexane (1: 1) as a developing and eluting solution was distilled off under reduced pressure and recrystallized with chloroform while hot to give 22.7 g. Obtained. Yield 57.3%.

[0053]

[Chemical 28]

The above compound (19.0 g) was added to toluene (3
80 ml) to give sodium amide (11.26)
g) and t-butanol (21.39 g) were added and reacted at room temperature. After a while, an exothermic reaction started to occur and the internal temperature rose to 80 °. After stirring for about 1 hour, the precipitated crystals were collected by filtration and washed with silica gel (Wakogel C-300 30
0g) and developed, dichloroethane-n-as an elution solution
Purify by column chromatography using hexane (1: 1). 10.5 g of the target fraction was obtained. ¹ H-NM
As a result of R and IR, two kinds of the deesterified product of the above-mentioned compound and the compound in which both deesterification and dehydrochlorination occurred were recognized.

[0055]

[Chemical 29]

Example 3 Production of the following compound

[0057]

[Chemical 30]

The mixed compound (1.40 g) described above is dissolved in methylene chloride (28 ml), n-caproyl chloride (0.81 g) and triethylamine (0.76 g) are added, and the mixture is reacted at room temperature for 2 hours. Water (20
0 ml) and ethyl acetate (200 ml) are added for extraction. After washing with water (100 ml), anhydrous sodium sulfate is added to the upper layer to dry it, and this is filtered. The obtained filtrate was evaporated under reduced pressure, and the residue was treated with silica gel (Wakogel C-300 50 g) and developed.
The two components were isolated by purification by column chromatography using -hexane-acetone (100: 1). The target compound was obtained from the lower spot of thin layer chromatography. Yield 0.52g, yield 55.9%. ¹ H-NMR (200 MHz CDCl ₃ ) δ: 7.83 to 7.16 (4 H, dd, aromati
c H) 7.65 to 7.59 (4H, dd, aroma
tic H) 7.32 (1H, s,

[0059]

[Chemical 31]

2.58 (2H, t, --CH _2- ) 1.8
_{5~1.70 (2H, m, -CH 2} -) 1.45~1.
_{35 (2H, m, -CH 2} -) 0.94 (3H, t, -
CH ₃ ) Elemental analysis value C ₂₁ H ₂₀ O ₂ ClF ₃ (M.W. 396.8)
3) Theoretical value: C, 63.56; H, 5.08 Actual value: C, 63.50; H, 5.19

[0061]

[Chemical 32]

A trifluoromethylacetylene compound was obtained from the upper spot of thin layer chromatography. Yield 0.20
g, yield 20.8%. _{^{1 H-NMR (200MHZ CDCl 3}} ) δ: 7.61 (4H, s, aromatic H) 7.
60 to 7.16 (4H, dd aromatic H)
_{2.58 (2H, t, -CH 2} -) 1.85~1.70
_{(2H, m, -CH 2 -} ) 1.45~1.35 (4H,
m, aliphatic-CH _2- ), 0.94 (3
H, t, -CH ₃₎ Elemental analysis _{C 21 H 19 O 2 F 3} (M.W.360.37) and a theoretical: C, 69.99; H, 5.31 Found: C, 69. 24; H, 5.14 Example 4 Production of the following compound

[0063]

[Chemical 33]

P-Iodophenol (22.0 g) and n-amyl bromide (22.7 g) were added to DMF (110 m).
It is dissolved in 1), anhydrous potassium carbonate (20.5 g) is added, and the mixture is stirred at an internal temperature of 90 ° C. overnight. After that, water (300 ml) and ethyl acetate (300 ml) are added to the reaction solution for extraction. After washing with water (150 ml × 2), the ethyl acetate layer is dried over anhydrous sodium sulfate. The solvent was distilled off from this filtrate under reduced pressure to obtain a pale yellow oily substance (about 30 g).

[0065]

[Chemical 34]

3-methyl-1-butyne-3 was added to pn-amyloxy-iodobenzene (30 g) obtained in the preceding section.
-Ol (12.6 g) and diethylamine (120 m
1) was added, and bis (triphenylphosphine) palladium (II) chloride (0.70 g) and cuprous iodide (0.2
0 g) is reacted at an internal temperature of 80 ° C. for 2 hours. After the solvent was distilled off, the residue was converted to silica gel (Wakogel C-300,
200 g) and development, chloroform-n as elution solvent
Purify by column chromatography using hexane (1: 1). The target fraction was concentrated under reduced pressure to give a pale red-yellow oil (22.2 g). Toluene (300 ml) was added to this, sodium hydride (0.2 g) was added, and the reaction was carried out at 100 ° C. for 2 hours under a nitrogen stream.
The solvent was distilled off under reduced pressure to obtain a black oily substance. The residue was silica gel (Wako gel C-300, 200 g) and developed, and n-hexane-ethyl ether (1
Purify by column chromatography using 00: 1). The target fraction was evaporated under reduced pressure to give a pale yellow oil. Yield 8.9 g Yield 47.1%

[0067]

[Chemical 35]

¹ H-NMR (200 MHz CDCl ₃ ) δ: 7.43 to 6.80 (4 H, dd, aromati
c, H) 3.94 (2H, t, -CH 2 -O-) 2.9
8 (1H, S,

[0069]

[Chemical 36]

1.7 to 1.9, 1.3 to 1.5 (6H,
_{m, aliphatic, -CH 2 -)} , 0.92 (3
_{H, t, -CH 3) 4} -n- pentyloxy-4'-ethynyl benzene obtained in the previous section a (3.8 g) diethylamine (18 ml)
Dissolved in p-bromobenzaldehyde (4.4 g) and bis (triphenylphosphine) palladium chloride (I
I) (0.14 g) and cuprous iodide (40 mg) are reacted at an internal temperature of 60 ° C. for about 1.5 hours. After evaporating the solvent, the residue was washed with ethyl acetate (200 ml) and water (100 ml).
ml) is added and extraction is performed. After washing with water (100 ml), the ethyl acetate layer is dried over anhydrous sodium sulfate. The filtrate was concentrated under reduced pressure to dryness, and then recrystallized with a minimum amount of ethyl acetate under heating to obtain a white amorphous crystal (3.28 g). In addition, secondary crystals (0.82 g) were obtained from this mother liquor.
Got Total yield 4.10 g Total yield 70.2% ¹ H-NMR (200 MHz, CDCl ₃ ) δ: 10.0 (1 H, S, aldehyde, —CH
O) 7.87 to 7.62 (4H, dd, aromati
c, H) 7.50 to 6.86 (4H, dd, aroma)
tic, H) 3.98 (2H, t, -CH 2 -O-)
1.9-1.7 (2H, m, aliphatic, -C
H ₂ −) 1.5 to 1.3 (6H, m, aliphati
_{c, -CH 2 -), 0.94} (3H, t, -CH 3) DMF in the preceding aldehyde (4.0g) (40ml)
1,1,1-trichloro-2,2,2-trifluoroethane (5.1 g) and zinc (granulate and powder 1.1 each) were added.
g) was added and the reaction was carried out at an internal temperature of 60 ° C. for 2 days. Thereafter, acetic anhydride (10 ml) and 1.1 g of zinc dust were added to this reaction solution, and the reaction was carried out at the same temperature for 1.5 hours. 1N- in the reaction mixture
HCl (200 ml) and ethyl acetate (200 ml) are added for extraction. Anhydrous sodium sulfate is added to the ethyl acetate layer and dried. The filtrate was evaporated under reduced pressure, and the residue was silica gel (Wakogel C-300 100 g).
Then, the product is purified by column chromatography using chloroform-n-hexane (1: 3) as a developing and eluting solvent. The solvent was distilled off from the target fraction under reduced pressure to dryness, and the residue was recrystallized with n-hexane while heating to obtain white crystals. Yield 1.06 g, yield 43.6%.

[0071]

[Chemical 37]

¹ H-NMR (200 MHZ CDCl ₃ ) δ: 7.73 to 7.52 (4H, dd, aromati
c, H), 7.49 to 6.85 (4H, dd, arom
atic, H) 7.26 (1H, S,

[0073]

[Chemical 38]

[0074] _{3.97 (2H, t, -CH 2} -O-)
3.9 to 3.7 (2H, m, aliphatic, -C
H ₂ −) 1.5 to 1.3 (6H, m, aliphati
_{c, -CH 2 -), 0.94} (3H, t, -CH 3) Elemental analysis C ₂₂ H ₂₀ OClF ₃ (M.W.392.8
4) Theoretical value: C, 67.26; H, 5.13 Actual value: C, 67.20; H, 5.15 Example 5 Production method of the following compound

[0075]

[Chemical Formula 39]

4-Methyl-1-butyl-3-ol (6.31 g) and diethylamine (60 ml) were added to 4-bromo-4'-n-pentylbiphenyl (15.16 g), and bis (triphenylphosphine chloride was added. ) Palladium (II) (0.35 g) and cuprous iodide (0.10 g)
Was reacted at an internal temperature of 60 ° C. for 6 hours. After the solvent was distilled off, the residue was converted to silica gel (Wakogel C-300, 20
0 g) and column chromatography using chloroform as a developing and eluting solvent for purification. The target fraction is concentrated under reduced pressure to obtain a pale yellow oily substance (about 27 g). Toluene (350 ml) was added to this, sodium hydride (1.0 g) was added, and the reaction was carried out at 90 ° C. for 2 hours under a nitrogen stream. After the solvent was distilled off under reduced pressure, the residue was purified by column chromatography using silica gel (Wakogel C-300, 200 g), developed, and dichloroethane as an eluting solvent. Further purification by silica gel (Wakogel C-300, 100 g) column chromatography again gave a colorless oil.

[0077]

[Chemical 40]

¹ H-NMR (200 MHz CDCl ₃ ) δ: 7.54 (4H, S, aromatic, H) 7.
52 to 7.23 (4H, dd, aromatic, H)
3.11 (1H, S,

[0079]

[Chemical 41]

[0080] _{2.64 (2H, t, -CH 2} -) 1.7
_{5~1.60 (2H, m, -CH 2} -) 1.45~1.
_{25 (4H, m, -CH 2} -), 0.90 (3H, t,
-CH ₃₎ acetylene derivative obtained in the previous section a (5.1 g) was dissolved in diethylamine (20 ml), p-bromobenzaldehyde (3.78 g) and bis (triphenylphosphine) iodide and palladium (II) (160 mg) Cuprous oxide (43 mg) is reacted at an internal temperature of 60 ° C. for about 3 hours. After distilling off the solvent, chloroform (300 ml) was added to the residue.
And 1N-HCl (100 ml) were added for extraction. It is washed with water (100 ml) and the chloroform layer is dried by adding anhydrous sodium sulfate. Crystallization occurs when the solvent is distilled off under reduced pressure. Crystals were taken out by adding n-hexane and dried. Yield 5.1 g Yield 63.6%

[0081]

[Chemical 42]

The aldehyde derivative (2.10) obtained in the preceding section
DMF (20 ml) was added to g), 1,1,1-trichloro-2,2,2-trifluoroethane (2.24 g),
Add zinc (powder and granules 1.0g each) at an internal temperature of 60 ℃
Reacted for days. 1N-HCl (150 ml) was added to the reaction solution.
And ethyl acetate (200 ml) were added and extraction operation was performed. After washing with water (100 ml), anhydrous sodium sulfate is added to the ethyl acetate layer for drying. The filtrate was distilled off under reduced pressure and the residue was converted to silica gel (Wakogel C-300100).
g) and column chromatography using chloroform-n-hexane (1: 1) as a developing elution solvent for purification. The solvent was distilled off from the target fraction under reduced pressure, and the mixture was dried to recrystallize with n-hexane while heating to obtain white crystals. Total yield 0.60g Total yield 21.8%

[0083]

[Chemical 43]

¹ H-NMR (200 MHz CDCl ₃ ) δ: 7.75 to 7.57 (4 H, dd, aromati
c, H) 7.59 (4H, S, aromatic, H)
7.58-7.26 (4H, dd, aromatic,
H), 7.25 (1H, S,

[0085]

[Chemical 44]

[0086] _{2.65 (2H, t, -CH 2} -) 1.7
5 to 1.60 (2H, m, aliphatic, -CH
₂ −) 1.40 to 1.27 (4H, m, aliphat
_{ic, -CH 2 -) 0.90 (} 3H, t, -CH 3) Elemental analysis _{C 28 H 24 ClF 3 (M.W.452,94} ) theoretical: C, 74.25; H, 5 . 34 Measured value: C, 74.12; H, 5.35 Physical property measurement The phase transition temperature and the phase of the compounds obtained in the above Examples were judged by visual observation with a polarizing microscope and a differential scanning calorimeter (D).
SC) was also used. Further, Δn and Δε were measured according to the literature method. The results obtained are shown in Table 1.

[0087]

[Table 1]

[0088]

INDUSTRIAL APPLICABILITY The dihydronaphthalene derivative which is the compound of the present invention is a novel compound and is a useful component for preparing a liquid crystal composition used for a liquid crystal flat panel display or the like. The compounds of the present invention have high physical and chemical stability, exhibit a smectic A phase, and have a large refractive index anisotropy (Δn). Therefore, the compound is an additive effective for lowering the voltage of the liquid crystal composition with respect to the threshold voltage and the saturation voltage necessary for driving the liquid crystal display device, etc., and is useful in constructing a practical liquid crystal composition. It is provided as one ingredient. That is, it has good compatibility with many other liquid crystal compounds such as ester-based, ether-based, carbonyl-based, biphenyl-based, phenylcyclohexane-based, and heterocyclic-based liquid crystal compounds, and is added to a liquid crystal composition containing them. Therefore, other physical properties can be improved. As described above, the present invention provides a compound useful as one component in constructing a liquid crystal composition used for a liquid crystal flat panel display and the like, and also provides a practical liquid crystal composition containing at least one compound. It is a thing.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] February 24, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0034

[Correction method] Change

[Correction content]

[0034]

[Chemical 19]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0035

[Correction method] Change

[Correction content]

Further, a Reformatsky reagent (organozinc compound) derived from 1,1,1-trichloro-2,2,2-trifluoroethane is allowed to act on the above-mentioned skeleton component aldehyde compound, followed by dehydrochlorination and hydroxyl group conversion. The compound of the present invention is produced by subjecting to a reduction reaction after acetylation.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0041

[Correction method] Change

[Correction content]

[0041]

[Chemical formula 22]

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0052

[Correction method] Change

[Correction content]

DM was added to the above-mentioned aldehyde (31.0 g).
F (210 ml) was added and 1,1,1-trichloro-
2,2,2-Trifluoroethane (32.2 g) and zinc (powder and granules 8.43 g each) were added to carry out a final liquid reaction at an internal temperature of 50 ° C. Acetic anhydride (22 ml) and zinc dust (8.4 g) were added to this reaction, and the mixture was reacted at an internal temperature of 75 ° C for 2 hours.
1N-HCl (500 ml) and ethyl acetate (500 m
l) was added and extraction was performed. After washing with water (500 ml),
The residue distilled off under reduced pressure was subjected to silica gel (Wakogel C-3
00 500 g) and the target fraction to be purified by column chromatography using chloroform-n-hexane (1: 1) as a developing and eluting solution was distilled off under reduced pressure and recrystallized with chloroform while hot to give 22.7 g. Obtained. Yield 57.3%.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0061

[Correction method] Change

[Correction content]

[0061]

[Chemical 32]

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0065

[Correction method] Change

[Correction content]

[0065]

[Chemical 34]

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0067

[Correction method] Change

[Correction content]

[0067]

[Chemical 35]

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0071

[Correction method] Change

[Correction content]

[0071]

[Chemical 37]

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0077

[Correction method] Change

[Correction content]

[0077]

[Chemical 40]

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0088

[Correction method] Change

[Correction content]

[0088]

The trifluoromethyl derivative which is the compound of the present invention is a novel compound, and is a useful component for preparing a liquid crystal composition used for a liquid crystal flat panel display or the like. The compounds of the present invention have high physical and chemical stability, exhibit a smectic A phase, and have a large refractive index anisotropy (Δn). Therefore, the compound is an additive effective for lowering the voltage of the liquid crystal composition with respect to the threshold voltage and the saturation voltage necessary for driving the liquid crystal display device, etc., and is useful in constructing a practical liquid crystal composition. It is provided as one ingredient. That is, it has good compatibility with many other liquid crystal compounds such as ester-based, ether-based, carbonyl-based, biphenyl-based, phenylcyclohexane-based, and heterocyclic-based liquid crystal compounds, and is added to a liquid crystal composition containing them. Therefore, other physical properties can be improved. In constructing a liquid crystal composition used for a liquid crystal flat panel display as described above, the present invention provides a compound useful as one component, and also provides a practical liquid crystal composition containing at least one compound. It is a thing.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C07C 67/08 69/63 9279-4H 69/92 255/31 255/32 C07D 239/26 239 / 28 239/34 C09K 19/12 19/18 9279-4H 19/20 19/30 19/34 G02F 1/13 500

Claims (10)

[Claims] 1. The following general formula (I): [In the formula, R ¹ represents an optionally substituted alkyl group having 1 to 14 carbon atoms, R ² represents a hydrogen atom or a halogen atom, and R ³ represents a hydrogen atom or an electron-withdrawing group. X and Y are the same or different and optionally substituted aromatic or non-aromatic carbon homocycle or heterocycle, m and n are 1 or 2, respectively, and Q ¹ is a single bond. , An ether bond or an ester bond, Q ² is a single bond, an ester bond, or _{-CH = CH -, - CH 2} CH 2 -, or an methyleneoxy bonds. ] A trifluoromethyl-substituted vinyl compound represented by: 2. The compound according to claim 1, wherein R ¹ is a linear alkyl group having 3 to 6 carbon atoms. 3. R ³ is a hydrogen atom, a halogen atom, or CF
The compound according to claim 1, which is one of _three groups and a cyano group. 4. The compound according to claim 1, wherein X, Y and Z are each an aromatic or non-aromatic 5- or 6-membered ring. 5. X and Y are respectively represented by: The compound according to claim 4, which is 6. R ¹ is a linear alkyl group having 3 to 6 carbon atoms, R ² is a hydrogen atom, R ³ is a halogen atom, m is 1 or 2, and n is 1, Q ¹ is a single bond, an ether bond or an ester bond, and Q ²
Is a single bond or The compound according to claim 1, which is 7. The compound according to claim 1, wherein at least one of X and Y is a benzene ring substituted with a halogen atom. 8. The following general formula (II): [Wherein R ¹ , X, Y, Z, m, n, Q ¹ and Q ² have the same meanings as in claim 1. ] The skeleton component or its derivative represented by the following general formula (III) [In the formula, R ² and R ³ have the same meanings as described above. ] By reacting a compound represented by the following general formula (IV) The method for producing a compound according to claim 1, wherein the compound represented by the formula (1) is produced and the compound is dehydrated. 9. At least one of the compounds according to claim 1.
A liquid crystal composition comprising a seed. 10. A liquid crystal light modulation device comprising the liquid crystal composition according to claim 9 arranged between at least a pair of substrates.