JPH02500274A - Liquid crystal derivatives of 2,5-disubstituted pyridines as components of liquid crystal materials and liquid crystal materials - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Liquid crystal derivatives of 2,5-disubstituted pyridines as components of liquid crystal materials and liquid crystal materials Technical field The present invention relates to a novel organic compound having liquid crystal properties, particularly as a component of a liquid crystal material. Liquid crystal derivatives of 2,5-disubstituted pyridines and liquid crystal materials used in electro-optical devices Regarding fees.

According to the invention, the display of alphanumeric information such as electronic watches and small calculators will find wide application on the electronic industry for.

Conventional technology Liquid crystal compound, i.e. the following formula, (wherein AIK has 3 to 8 carbon atoms) trans-4- Alkyl-(4-cyanophenyl)cyclohexane is well known (DE, c, 　2636684　). The material has a high critical voltage and twisting saturation voltage. This is due to the low anisotropic value of the dielectric constant Δε of the cyclohexane derivative. be.

In addition, liquid crystal compounds, i.e., the following formula (In the above formula, AIK has 4 to 8 carbon atoms) nophenyl)-5-(4-alkylphenyl)pyridine (SO, A, 71315 3) and the following formula, (in the above formula, AIM has 4 to 8 carbon atoms) 6-(4-alkylphenyl)-3-cyanopyridine (SLI, A, 7131 53) is also well known. These compounds exhibit high rotational viscosities within a wide range of nematic phases. It has a coefficient γ. Such a viscosity is important for the above liquid crystal materials in high-speed electro-optical devices. limit the application of

Liquid crystal material, i.e. the following formula, 5-alkyl- (in the above formula, AIK has 2 to 7 carbon atoms) 2-(4-cyanophenyl)pyridine is well known (SU, A, 67580 0). At high anisotropic values of dielectric constant, these compounds exhibit low values of fining temperature and and a narrow range of nematic phases. These properties of the compound lend it to a wide range of uses. precludes use of the liquid crystal material at operating temperatures.

In addition, liquid crystal compounds, i.e., the following formula, (wherein AIM has 1 to 6 carbon atoms) -4-alkylcyclohexyl)-4'-() lance-4-alkylcyclohexyl xyl) biphenyl (SU, A, 1055336) i lower formula, (in the upper formula, AIM has 2 to 6 carbon atoms) cyclohexyl)-phenyl-5-alkylpyridine (SO, A, 13 02682) is also well known. These compounds have high smectic-nematic conversion. characterized by a shifting temperature, which makes the application of liquid crystal materials containing these compounds Restrict.

Disclosure of invention Low rotational viscosity, smectic-nematic transition temperature, high dielectric constant anisotropy, and fining temperature A new liquid crystal derivative of 2゜5-disubstituted pyridine as a component of a liquid crystal material with and have a high nematic phase range and a low value of critical voltage, This book aims to provide liquid crystal materials characterized by ist action saturation voltage and small opening/closing times. This is the object of the invention.

The purpose is the following formula, R' Oyohi R'' represents an alkyl group having 1 to 12 carbon atoms, R3 is F, No2. 2,5-disubstituted pyridine represented by NH2,CN] This is achieved by providing novel liquid crystal derivatives of

A liquid crystal derivative of 2,5-disubstituted pyridine represented by:

(In the above formula, Rr and Rt represent alkyl having 1 to 12 carbon atoms) In addition, at least two types of liquid crystal components according to the present invention (at least among the liquid crystal components) One type is a liquid crystal derivative of 2,5-disubstituted pyridine of formula I). A liquid crystal material is also provided.

In this liquid crystal material, liquid crystal derivatives of 2,5-disubstituted pyridine of formulas 1 to xX Conveniently, the content is between 1 and 75% by weight.

A liquid crystal material with such a ratio of components has optimal properties.

Example The proposed compound can be used in small calculators, watches, external electro-optical devices, and large A wide range of applications that make it applicable to the production of liquid crystal materials used in devices that derive power from solar cells. It has spectral characteristics.

Compounds of formula (1) are synthesized by sequential chemical rearrangements. 2-methyl-5-lithium p The reaction of lysine with 4-alkylcyclohexanone requires subsequent dehydration and hydrogenation. to give 2-methyl-5-(trans-4-alkylcyclohexyl)pyridine. I can do it. The latter is converted to 2-cyano-5-(trans-4-alkylcyclohexyl) by standard methods. xyl)pyridine.

Method for synthesizing compounds of formula (I[I, XXI, XXII, XXI[[)0] is shown below.

3.6-Disubstituted 3゜4-dihydro-2H- by condensation of enamine and vinyl ketone Piperidino-2H-pyran is obtained, the latter being hydroxylated in aqueous alcoholic medium. By refluxing with silamine hydrochloride, 2,5-disubstituted pyridines IV, XV, XXI [[ or its intermediates, and the bromine is converted to the cyano group (I[I.

X■), substituted with an acrylonitrile group (XIX, XX, XX I), The nitro group is converted into an isothiocyano group (X■) by sequential chemical reactions. 2.5- Nitration of disubstituted pyridine produces compound ■.

■, x■ are obtained, and the reduction thereof yields aminopyridine Vl, IX.

X■ is obtained, from which fluorinated pyridine■, X, XIV, XVI, and cyanopyridine Lysine XI is synthesized.

Compounds of formula XXII are prepared by preparing oxymethylene-methyl-( Cyclization of the sodium salt of 4-alkylcyclohexyl)ketone and subsequent 2 of 6-(4-alkylcyclohexyl)-3-cyanopyridin-2-one -Conversion to chloro-3-cyano-6-(4-alkylcyclohexyl)pyridine In this case, the halogenated tl is reduced by catalytic hydration.

Compounds 2XXVI to XX■ are substituted 2-methoxy-2H- and ran, biryllium 1- by successive rearrangements to salts and pyridine derivatives (XXVI~XX~'l1l) dimethylamino-2-(4-alkylphenyl)-4-(4-alkoxy-3 -fluorobenzoyl)butadiene-1,3 (in the case of XXVI) or 1- Dimethylamino-2-(4-alkoxy-3-fluorophenyl)-4-(4- alkoxy or alkylbenzoyl)butadiene-1,3 (XX■~X In the case of X■) manufactured.

The liquid crystal material according to the present invention can be obtained by mixing at least two types of liquid crystal components according to the present invention. One of them is a 2,5-disubstituted pyridine of formula I-XXI [[ and is present in an amount of 1 to 75% by weight.

Mixing is carried out with heating until an isotropic phase forms, then cooled.

The other components of the liquid crystal material may be any compound selected from the following: biphenyls. derivatives of cyclohexane, dioxane, pyrimidine, alkyl (alkoxy) ) Benzoic acid and alkyl (alkoxy) of trans-cyclohexanecarboxylic acid ) phenyl ester, 4-() lance-4-alkyl-cyclohexyl) benzoin Alkylphenyl ester of acid, trans-4-alkyl-cyclohexanecal 4-(trans-4-alkylcyclohexyl)phenyl ester of bonic acid, 1.2-diphenylethane, l-cyclohexyl-2-phenylethane.

The amounts and ratios of the components in the two mixtures are chosen according to said properties of the liquid crystal material.

Specific embodiments of the invention are shown below. This is the 2,5-binary Explains the manufacturing method and characteristics of pyridine derivatives and the manufacturing method and characteristics of liquid crystal materials. I will clarify.

Example 1 2-cyano-5-(trans-4-hexylcyclohexyl)pyridine (I[a )Manufacturing of 1.1. 1-(2-methyl-5-pyridyl)-4-hexylcyclohexano Le (1, 1, a) A 0.504 molar solution of butyllithium in 400 ml of anhydrous ether was heated under a stream of argon. , of 2-methyl-5-bromopyridine in ether 500i at a temperature of -70 °C. 72.2 g (0.42 mol) of the solution are slowly added dropwise with good stirring.

The mixture was stirred for 1 hour at -70°C and 114 g (0.63 mol) solution of lohexanone was added at a reaction temperature of 170°C or higher. Add dropwise so that it does not rise. Continue stirring at this temperature for another hour and do not cool. Leave the reaction mixture at room temperature overnight. Then pour this mixture into 11 water and Separate the layer, wash twice with 300ml of water, and dehydrate with Na, SO. smell the ether The residue is distilled under vacuum (230°C/3mmHg) or re-distilled from acetone. crystallize. Isolate 73 g (63.3%) of compound 1.1a as a white powder ( m, p, >100°C). In the same manner, a compound represented by the following formula is produced ( 1.1b-f, b is R=CsH1°C is R=C,H,, d is R=C,H,, e is R=CtH+1. Is f R=CsHl? ). Yield of compounds 1.1b-f The rate is 63-65%.

1.2.2-Methyl-5-(4-hexylcyclohexen-1-yl)pyridine (1, 2a) Add 98 g of sulfuric acid to 57.7 g (0.21 mol) of compound 1.1a with stirring. Add (1 mol). Maintain reactant temperature below 80°C.

The mixture was stirred at said temperature for 0.5 h, cooled, poured onto ice, alkalized, The oil layer was extracted with chloroform, dried over sodium sulfate, and the chloroform was evaporated. and evaporate the residue under vacuum. 46g (85%) of 1.2a in the form of transparent oil isolated (b, p, 200°C/3 mmHg). The formula and characteristics are shown in Table 1. The other compounds 1.2b-f are prepared in the same manner. Yield of compounds 1.2b-f The percentage is 85-90%.

1.3. 2-Methyl-5-(cis/trans-4-hexylcyclohexyl) Pyridine (1,3a) 51.5g of 1.2a in 350d of absolute ethanol (0 , 2 mol) of 7 g of 5% Pd at 20 atm until hydrogen absorption is complete. Hydrogenate with hydrogen on /c (end of absorption monitored by GLC). Filter the precipitate The alcohol is evaporated and the residue is evaporated under vacuum. Compound 1.3 a45 ．． 1 g (87%) is isolated (b, p, 170°C/2 mmHg).

Actual measurement %: C83.51, H11.2, C+5HzJ.

Calculation %: C83,33, H11,27゜Other compounds 1.3b-f were similarly calculated. The properties are shown in Table 1. The yield of compounds 1.3b-f was 85-90%. be.

1.4. 2-hydroxymethyl-5-(cis- and trans-4-hexyl cyclohexyl)pyridine (1,4a) Compound 1.4a was prepared with hydrogen peroxide in acetic acid. 2-acetylhydroxymethyl-5-( Rearranged to cis/trans-4-hexylcyclohexyl)pyridine and not isolated. After evaporation of excess acetic anhydride at 100 ml, saponification was carried out with 10% aqueous alcohol alkali. was prepared with a yield of 65% by converting compound 1.3a into the N-0 derivative. Ru. Compound 1.4a is isolated (b, p, 205°C/1 mmHg). other Compounds 1.4b-f are prepared in the same manner. Its formula and characteristics are shown in Table 1. . The yield of other homologues 1.4b-f is 60-70%.

2-cyano-5-(trans-4-hexylcyclohexyl)pyridine (]Ia ) Compound in 40 ml (0.55 mol) of dioxane (freshly distilled) 2.6 g of finely ground selenic acid was added to a solution of 11.1 g (0.04 mol) of 1.4a. (0.02 mol) is added. Heat the reactants to 80°C, stir at high speed, and reduce the agitation. Continue to maintain the temperature for 2 hours. The reactants are then passed through the aluminum oxide layer. Filter and evaporate dioxane from the filtrate. Ethanol 100d, hydroxya Sodium hydroxide in 8 g (0.12 mol) of min-hydrochloric acid and 50 d of water 13. 3 g (0,033 mol) are added to the residue. The mixture was refluxed for 1 hour, then 00d and oxidize with dilute hydrochloric acid. Filter the amorphous precipitate and recrystallize from alcohol. and wash with hexane. 5-(trans-4-hexylcyclohexyl)-pyridi 4.4 g (38%) of ion-2-oxime was isolated and diluted with 20 d of dry chloroform. Then 5.9 g of phosphorus oxychloride are added and the mixture is refluxed for 1 hour. This reactant Pour into water, neutralize with a solution of sodium bicarbonate, wash the organic layer with water, 82□0. of The solvent is evaporated from the filtrate through a small column. Recrystallize the residue from hexane (4 times) and isolated 1 g of compound 11a (9.1 g).

TC-N = 35.3°C, TN-s = 49.4°C).

Actual measurement %: C80.01; H9.54, C+5HzJz.

Calculated %: C79,95; H9,69゜Other 2-cyano-5-(trans-4 -alkylcyclo and the final analytical data are shown in Table 1. At room temperature, the new formula ■ All of the compounds are white crystalline powders.

The structure of compound ① was identified by PMR spectrum.

The spectrum of compound ■ is obtained using a 3-spin ABX system (δl　pI)IllCCj! 4): 8.24 ()I4), 8.34 (Hs), 9.06 ( Hb).

The structure of compound (1) was also confirmed by CNMR.

The formulas and properties of the synthesized compounds 1.2, 1.3, 1.4, and II are shown in Table 1. show.

Table 1 a　C6H11200/3　- b CJt 201/20 - c C=)19 196/22 - d C5H,, 210/14 32 e CJ+s 197/2 36.5 b 135/2 170/2 c 145/2 175/2 d 168/2 215/8 □ a 35.3 49.4 80.01 9.54 C1, Hz-Nz 79.9 5 9.69b 68 25” 78.96 B, 82 C+sLo?jz 7 8.90 B, 82c 60.7 37° 79.14 9.25 Cl68! 2N! 79.29 9.15d 45.4 55.4 79.71 9.36 C+J2. Nz 79.64 9.44e 50.1 60.2 80.16 10.0I C, Hz peak 80.23 9.92f 49.0 57.9 80 ．． 5410.24 C2, HsJt 80.48 10.13 Electron of compound of formula (■) Five species with nematic phase over a wide temperature range to measure optical parameters Alternatively, a mixture of seven congeners was used. Rules for changes in properties of this series of homologues The characteristics of the mixture of five and seven homologs indicate that each homolog is sufficiently accurate. It should be taken into account that the properties of can be inferred.

In this regard, a mixture consisting of the following two components was prepared: Mixture A - 40 mol %2-cyano-5-(trans-4-amylcyclohexyl -(trans-4-heptylcyclohexyl)pyridine and H mixture B (ratio comparison) 4 0 mol% trans-4-amyl-(4-cyanophenyl)cyclohexyl Sun + 60 mol% trans-4-heptyl-(4-cyanophenyl)cyclohexyl Sun (DH, B, 2636684).

Fining temperature (TN-1), dielectric constant anisotropy, limiting voltage for mixtures A and B , and the twist action saturation voltage are shown in Table 2.

Δε=ε11−ε1 Anisotropy of dielectric constant at low temperature τ=0.95 (τ=T average - TN - 1."K) Ui, and U. □Limit voltage and twist action saturation voltage Cell thickness 10μ From Table 2, it can be seen that for the mixture of the new compound of formula (Mixture A), the clarification temperature was mixture of su-4-alkyl-(4-cyanophenyl)cyclohexane (mixture B ) is found to be higher. Furthermore, from Table 2, the limit voltage and twist of mixture A The working saturation voltages are 1.25 and 1.8, respectively, and U Lhr of mixture B and somewhat lower than U sat (Uzb- = 1.7 V.

U. , t=2.3V).

Examples 2 to 24 below illustrate the use of compounds H as components of liquid crystal materials produced by the method described above. Explain its use.

In Examples 2-24, the compositions are given in percent by weight.

Example 2 2-cyano-5-(trans-4-propylcyclohexyl)pyridine (Ilb ) −6 2-cyano-5-(trans-4-butylcyclohexyl) and lysine (Inc) -7 2-cyano-5-(trans-4-amylcyclohexyl)pyridine (Ild) −25 2-cyano-5-(trans-4-hexylcyclohexyl)pyridine (Ila ) −10 2-cyano-5-(trans-4-hebutylcyclohexyl)pyridine (Ile ) −35 2-cyano-5-(trans-4-octylcyclohexyl) and lysine (I[f ) −17 Regarding this liquid crystal material, Uth, = L15V, U. , t=1. 7 V, The range of the nematic phase is -5°C to +55°C.

Example 3 2-cyano-5-(trans-4-propylcyclohexyl)pyridine (nb) −10 2-cyano-5-(trans-4-amylcyclohexyl)pyridine (IId) −20 2-cyano-5-(trans-4-hebutylcyclohexyl)pyridine (Ice ) −23 4-amyl-4'-cyanobiphenyl-404-amyl-4''-cyano-P- Terphenyl -7Uth- = 1-3 V, U--z = 1.85V , the range of the nematic phase is -9 to +60°C.

Example 4 2-cyano-5-(trans-4-butylcyclohexyl)pyridine (I[c) −20 2-cyano-5-(trans-4-hexylcyclohexyl)pyridine (I[a ) −28 Trans-4-propyl (4-cyanophenyl)cyclohexane-25 trans-4-amyl-(4-cyanobiphenyl)cyclohexane-7 Uthr = 1.5V, U,, = 2. IV, the nematic phase ranges from -12 to + The temperature is 60°C.

Example 5 2-cyano-5-(trans-4-hexylcyclohexyl)pyridine (IIa ) −15 2-cyano-5-(trans-4-octylcyclohexyl) and lysine (If) −15 4'-ethoxyphenyl ester of trans-4-propylcyclohexanecarboxylic acid STER　-17.5trans-4-butylcyclohexanecarboxylic acid 4'-e Toxyphenyl ester -17.5 trans-4-amylcyclohexanecal 4'-Ethoxyphenyl ester of bonic acid -17,5 trans-hexylsic 4'-Ethoxyphenyl ester of lohexanecarboxylic acid -17,5 0,,, = 1.7 V, U,, t = 2.25 V, the range of the nematic phase is -6 to +60°C.

Example 6 2-cyano-5-(trans-4-propylcyclohexyl)pyridine (II) b) -5 trans-4-propyl-(4-cyanophenyl)cyclotrans-4-amyl -(4-cyanophenyl)cyclohexane -27 Trans-4-hebutyl-(4-cyanophenyl)cyclohexane-22 4-ethyl-4-() lance-4-amylcyclohexyl)biphenyl-12 4-()trans-4-propylcyclohexyl')-4'-(trans-4- propylcyclohexyl)biphenyl-12Uthr = 1.5 V, U, , L = 2. IV, the range of the nematic phase is -10 to +80°C.

Example 7 2-cyano-5-(trans-4-propylcyclohexyl)pyridine (nb) -10 2-cyano-5-(trans-4-butylcyclohexyl)pyridine (Inc) −15 2-cyano-5-() lance-4-amylcyclohexyl)pyridine (IIa) −20 2-cyano-5-(trans-4-hexylcyclohexyl)pyridine (IIa ) −15 2-cyano-5-(trans-4-hebutylcyclohexyl)pyridine (IIe ) −15 4-propyl-4'-() lance-4-amylcyclohexyl)biphenyl- 15 4-(trans-4-amylcyclohexyl)-4'-(trans-4-propyl) (cyclohexyl)biphenyl-10U=1.2V, U□t=1.7V, The range of the matic phase is -8 to +75°C.

Example 8 2-cyano-5-(trans-4-amylcyclohexyl)pyridine (nd) -3 Trans-4-propyl-(4-cyanophenyl)cyclohexane-24 trans-4-amyl-(4-cyanophenyl)cyclohexane-27 Trans-4-hebutyl-(4-cyanophenyl)cyclohexane-22 4-ethyl-4'-() lance-4-amylcyclohexane)biphenyl- 12 4-()trans-4-amylcyclohexyl)-4'-(trans-4-pro pyrucyclohexyl)biphenyl-12Uth-=1.6 V, U--L ""2.15V, the range of the nematic phase is -12 to +80°C.

Example 9 2-cyano-5-() lance-4-propylcyclohexyl)pyridine (Ilb ) −20 2-cyano-5-() lance-4-butylcyclohexyl)pyridine (IIc) −15 2-cyano-5-(trans-4-amylcyclohexyl)pyridine (II d ) −25 2-cyano-5-(trans-4-hebutylcyclohexyl)pyridine (I[a ) −20 4-amyl-4'-cyanobiphenyl -20Ut &, = 1.2 V, U -t=1.75V, the range of the nematic phase is -6 to +54°C.

Example 10 2-cyano-5-(trans-4-amylcyclohexyl)pyridine (Ild) −40 2-cyano-5-(trans-4-heptylcyclohexyl)pyridine (Ile ) −25 trans-4-butyloxy-(4-cyanophenyl)cyclohexane-35 7N-1=58℃, Uth-=1.3V, U-t=1.8V .

Example 11 2-cyano-5-(trans-4-butylcyclohexyl)pyridine ([c) -30 4-Butyl-4'-methoxyazoxybenzene-46,94-ethyl-4'- Methoxyazobenzene -23, IUth-=1.25V, U--t=1 ．． 75V, the nematic phase ranges from +5 to +66°C.

Example 12 4-amyl-4'-cyanobiphenyl-354-hexyloxy-4'-cya nobiphenyl-112-cyano-5-(trans-4-amylcyclohexyl ) Pyridine (lld)-32 2-cyano-5-(trans-4-hebutylcyclohexyl)pyridine (Ile ) −22 Uthr = 1.4 V, U, 1. = 1.85V, nematic phase range is -3 to +51°C.

Example 13 4-propylphenyl ester of 4'-methoxybenzoic acid 4'-methoxybenzoic acid 4-aminophenyl ester of acid 4'-hexanoyloxybenzoic acid 4-pro Pylphenyl ester-17 4-(4-propyl)-biphenyl ester of 4'-butylbenzoic acid -10 4-Propylbiphenyl ester of 4'-amylbenzoic acid 2-cyano-5-(to Lance-4-propylcyclohexyl)pyridine (I[b)-30 U,=1.5V, U□,=2. OV, nematic phase range from -2 to +61°C It is.

Example 14 2-cyano-5-(trans-4-amylcyclohexyl)pyridine (nd) -27 4-amyl-4″-cyano-p-terphenyl-84′-methoxybenzoic acid 4-Propylphenyl ester 4-amyl phenyl ester of 4'-methoxybenzoic acid Stell U=1.55V, U,,t=2.2V, nematic phase range is 0 to +55°C.

Example 15 4-Butyl-4'-methoxyazoxybenzene-33,54-ethyl-4'- Methoxyazoxybenzene -16,55-(4-cya, nophenol)-4- Amyl(thiobenzoate)-10 2-cyano-5-() lance-4-propylcyclohexyl)pyridine (IIb ) −20 2-cyano-5-(trans-4-butylcyclohexyl)pyridine (Ilc) −20 Uth-=1.4V, U--t=1.9V.

The range of the nematic phase is 0-64°C.

Example 16 4-Butyl-4'-methoxyazoxybenzene-26,84-ethyl-4'- Methoxyazoxybenzene 4'-cyanophene of -13,24-amylbenzoic acid 4'-cyanophenyl ester of 4-heptylbenzoic acid 2-cyano -5-(trans-4-butylcyclohexyl)pyridine (IIc) -20 2-cyano-5-(trans-4-amylcyclohexyl)pyridine (nd) -20 Uth-=1.4 V, U-t=1.85 V, the range of nematic phase is -2 〜+62°.

Example 17 2-cyano-5-(trans-4-heptylcyclohexyl)pyridine (ne) -3O N-(4-hexylbenzylidene)-4-cyanoaniline N-(4-propylbenzylidene) )-4-cyanoaniline Uth, = 1.5V, U, , = 2. IV.

The range of the nematic phase is -3 to +64°C.

Example 18 2-cyano-5-(trans-4-propylcyclohexyl)pyridine (Ilb ) −10 2-cyano-5-(trans-4-butylcyclohexyl)pyridine (IIc) -10 2-cyano-5-(trans-4-amylcyclohexyl)pyridine (nd) -25 4'-cyanophenyl ester of 4-butylbenzoic acid 4' of 4-amylbenzoic acid -cyanophenyl ester 4'-cyanophenyl ester of 4-hexylbenzoic acid Uth-=1.35V, U,□=1.7V, nematic phase range is 0 〜+53°C.

Example 19 4-amyl-4'-cyanobiphenyl-204-heptyl-4'-cyanobiphenyl phenyl-204-amyl-4″-cyano-P-terphenyl-102-cya No-5-(trans-4-amylcyclohexyl)pyridine (II d)-2 5 2-cyano-5-(trans-4-hebutylcyclohexyl)pyridine (I[e ) 25 U, h, = 1.3 V, U,, t = 1. T.V.

The range of the nematic phase is -1 to +66°C.

Example 20 4-propyloxy-4'-cyanobiphenyl-154-amyloxy-4' -Cyanobiphenyl -204-amyl-4''-cyano-p-terphenyl - 152-cyano-5-(trans-4-propylcyclohexyl)pyridine (I Ib) -20 2-cyano-5-(trans-4-butylcyclohexyl)pyridine (IIc) −30 ULh, = 1.25V, U,, L = 1.6V.

The range of the nematic phase is +4 to +70°C.

Example 21 2-cyano-5-(trans-4-hebutylcyclohexyl)pyridine (Ile ) −29,2 4-(2-methylbutyl)-1-(4-cyanophenyl)-cyclohexane- 0,8 N-(4-hexylbenzylidene)-4-cyanoaniline N-(4-propylbenzylidene) )-4-cyanoaniline 0th-=1.5 V, U--t= 2. IV, the range of the nematic phase is -5 to +67°C.

Example 22 4-propyloxy-4''-cyano-p-terphenyl 4-amyloxy-4' -biphenyl -204-amyl-4'-cyano-p-terphenyl -152 -Cyano-5-(trans-4-butylcyclohexyl)pyridine (IIc) −30 2-cyano-5-(trans-4-propylcyclohexyl)pyridine-19 4-(methoxyheptyl)-1-(4-cyanophenyl)cyclohexane-I Utb-=1.2V, U--c=1.55V, the range of nematic phase is +4 to +68°C.

Example 23 2-cyano-5-(trans-4-amylcyclohexyl)pyridine (nd) -20 2-cyano-5-(trans-4-hebutylcyclohexyl)pyridine (IIe ) −20 5-amyl-2-(4-cyanophenyl)pyridine-10trans-4-butyl 4-ethoxyphenyl ester of cyclohexanecarboxylic acid -25 4-ethoxyphenyl ester of trans-4-hexylcyclohexanecarboxylic acid Tell -15 4-cyanobiphenyl ester of trans-4-butylcyclohexanecarboxylic acid Le -10 Uthr = 1.5 V, U,, t = 2.　IV.

The range of the nematic phase is -9 to +71°C.

Example 24 2-cyano-5-(trans-4-amylcyclohexyl)pyridine (Ild) −25 5-amyl-2-(4-cyanophenyl)-1',3-dioxane-25 4-ethoxyphenyl ester of trans-4-butylcyclohexanecarboxylic acid Le-25 4-ethoxyphenyl ester of trans-4-hexylcyclohexanecarboxylic acid Tell -15 4-ethyl-4'-() lance-4-amyl)cyclohexylbiphenyl- 10 Uthr = 1.35V, Uiat = 1.7DV, nematic phase range is -11 to +67°C.

From Examples 2 to 24, it is clear that the compound of formula It can be seen that it has a Troll voltage.

These materials are suitable for use in electro-optical devices powered by solar cells.

Example 25 2-(4-cyanophenyl)-5-()trans-4-butylcyclohexyl)pi Production of lysine (II[a) 25.1. ) lance-1°-butyl-4-cyclohe Xylacetic aldehyde (25,1a) metal in anhydrous tetrahydrofuran 20 0.05 mol of trans-1-7" under reflux in a mixture of 0.05 mol of magnesium Chil-4-bromomethylcyclohexane is slowly added dropwise. magnesium After dissolution, the resulting solution was poured into 50 d of anhydrous tetrahydrofuran cooled to -40°C. 0.045 mol of N-methyl-N-formyl- Add dropwise. The reaction mixture was stirred at -20°C for 15-20 minutes and then Pour into 150 d of 5% hydrochloric acid that has been cooled to O''C.

Extraction with ether is then carried out and the extract is washed with a saturated aqueous solution of sodium chloride. Wash with water and dehydrate with sodium sulfate. Evaporate the ether and vacuum the residue Top evaporation isolates compound 25.1a in 73% yield (b.p. 85-87 °C/1 mn+Hg, IR spectrum vco1720cm-', PMR spectrum (ccfa).

δ． ppm): tO. 85 (J 6 Hz, CH3); mO. 97 ~ 1.85 (CH2.CH); dd 2.22 (J6 and 2 Hz , CH2CO); t 9.65 (J2 Hz, CHO)).

2,4-dinitrophenylhydrazone (from ethanol) is o+. p. = 11 It is 7-118°C.

Actual measurement %: C 59.45: H 7.38; N 15.36.

C+sHzhN40a Calculated %: C 59.65; H 7.23; N 15.46.

trans-1-alkyl-4-cyclohexyl acetic acid aldehyde (25.1b-d ) (b is R=CJt, C is R=CsH++, d is R=CbHls ) are manufactured in the same way.

Its characteristics are shown in Table 3.

25, 1b 51 69-71/1 105-10825, 1c 72 93 -95/　1　114-11825, 1d　70　139-142/　1　11 3-113.5 Compounds 25.1b,c are trans and cis isomers in a ratio of 7:3 It is produced from 1-alkyl-4-bromomethylcyclohexane, which is a mixture of It will be done.

25, 2. 1-/β-(4-trans-butylcyclohexyl)ethylenylpi Perazine (25.2a) 0.078 mol of anhydrous sodium sulfate was mixed with 0.086 mol of piperidine, -5 0.039 mol of 25.1a is added dropwise under a nitrogen atmosphere. this mixture Stir for 3 days at room temperature, filter off the precipitate, wash with hexane, and combine the filtrates and evaporate under vacuum. make it emit Compound 25.2a is isolated with a yield of 53% (bp = 139 ~141°C/3 mmHg.

Actual measurement %: N5.80 i C+dh+Nq, calculated %: N5.61; n: 0=1.4973, PMR spectrum (CCjl!., δ, ppm): t O. 85 (J6)tz, CHz).

mo. 97~1.85 (CHz, CH), m2.52~2.75 (CHz N), dd 4.10 (J 7 and 14Hz, CH=C), d 5 ．． 60 (J14Hz, C=C)IN)).

Similarly, the corresponding compound 1-/β-(4-trans-alkylcyclohexyl ) Ethylenyl/piperidines 25.2b-d were prepared, their characterization and final analysis The data are shown in Table 4.

Table 4 1 25.2b 75 118-120/1 6.132 25.2c 30 153-155/1 5.523 25.2 d 56 163-165/1 5.151 C16H29N 5.95 2°c, mountain 3N 5.31 3 C+qHs, N 5.05 25.3. 3-() lance-4-butylcyclohexyl)-6-(4-bro mophenyl)-3,4-dihydro-2-N-piperidino-2H-pyran (25, 3a) Compound 25.2 a　O,034mol, 1-acryloyl at 20''C under nitrogen atmosphere Mix with 0.037 mol of l-4-bromobenzene. Stir this mixture for 1 hour , leave for 24 hours. Then, it was cooled to -20"C and 10ml of methyl alcohol was added. I can do it. The precipitate is filtered off and dried under vacuum. Compound 25.3a was isolated in 87% yield. be done.

m, p, -93.5~95.5°c0 Actual measurement %: C67,67, H8,16, N3.08° + Cz Takayama 5BrNO calculation %: C67,81, H8,32, N3.04P M R Shetkul (CCI! a-δ, ppm): to, 90 (J6Hz, CH3).

mo, 95 to 2.12 (CH2, C), m2.45 to 3.07 (C), d4.27 (J8Hz.

NCHO), t 5.10 (3Hz, C=CH), S 7.31 (ArH) .

Uv spectrum A,, X (log and): 207 (4, 23), 25B (4,35) (95% ethanol).

The corresponding 3-(trans-4-alkylcyclohexyl)-6-(4 -bromophenyl) -3,4-dihydro is produced. Its characteristics and final analysis data Table 5 shows the data.

25.3b 93 102 66.96 B, 09 2.9425.3c 42 90 68.09 B, 31 2.7025.3d 79 59 6B, 58 8.49 2.7425.3 b CzsH3JrN0 67.25 8,1 3 3.1425.3c CzqHaoBrNO68,348,50,2,95 25, 3d CzsHaJrNo 68.84 B, 67 2.8725.4. 4-formyl-4-(trans-4-butylcyclohexyl)-1-(4-butylcyclohexyl) romophenyl)butanone (25,4a) In a solution of 0.074 mol of oxalic acid in 701 d of water was added 0.037 mol of compound 25.3a. and stir the mixture for 24 hours at 20°C. Then extract with ether The extract was washed with water and saturated sodium chloride, and dried over Na2SO4. , evaporate the solvent in vacuo.

Compound 25.4a is isolated with a yield of 77%. m, p, = 71~72℃ (hex Sun).

Actual measurement %: C64,4; H7,57; Br20.03; Cwt)lzJ roz calculation %: C64,12; H7,43; Br20.31 PMR smooth Cru (CCf4, δ, ppm): mo, 73 (J6Hz, CH3) 1 m0.85~2.12 (CJ, CH) 1m2.77~3.10 (CHzCO , Cl0), d7.50 and 7.75 (J9Hz, Arc), d9.5 2 (J2Hz, CHO) IR spectrum ν,. 1685 and 1720C IB-' (Vaseline oil) UV spectrum: λ,... (logε): 21 0(4,11), 258(4,25) (95% ethanol) In the same way, the corresponding 4-formyl-4-(trans-4-alkylcyclohexy )-1-(4-bromophenyl)butanone (25,4b-d) is produced. Ru. Its final analysis data and properties are shown in Table 6.

Table 6 1 25.4b 87 63.51? , 25 21.242 25.4c 9 2 72 64.69 7.39 19.413 25.4d 98 57 6 5.27 7.74 18.461 CzoHzJrOz 63.33 7.1 7 21.062 CzzH3+Br0z 64.86 7.67 19.61 3 CzsHxsBrOt 65.55 7.89 18.9625.5. 2 -(4-bromophenyl)-5-()trans-4-butylcyclohexyl)pyri Zin (25,5a) compound 25.4a 0.005 mol was dissolved in glacial acetic acid 15ad. 0.006 mol of triphenylmethylboron fluoride was added, and the mixture was stirred for 15 minutes. Reflux for a while, then cool the reaction mixture, dilute with anhydrous ether and filter off the precipitate. and dry under vacuum. 2-(4-bromophenyl)-5-() in 35% yield Lance-4-butylcyclohexyl)pyrylium boron fluoride is isolated. wood vinegar, acid 2-(4-bromophenyl)-5-() lance-4-butylcyclohetyl in 30d xyl) Beryllium boron fluoride 0.003 mol and ammonium acetate 0.05 The mole is refluxed for 2 hours and the acetic acid is evaporated under vacuum. Dilute the residue with water and add benzene The extract was washed with water, dried over sodium sulfate, and washed with a layer of silica gel (10 0/160.3 cm).

After solvent evaporation, the residue is CCI! , 4. Compound 25. with a yield of 92%. 5a is isolated. T, , = 155.2°C, TS-N = 160°C, T N-1 = 196.2°C Actual measurement %: C67.7B, N7.20. N3.78 ．． C+HzJrN calculation %: C67.74, N7.04. N3.76UV Spectrum: λ□X (logε): 208 (4, 35), 257 (4, 3 3).

284 (4; 32) (95% ethanol) PMR spectrum (CCj2a , δ, ppm): tO, 90 (J6H2, C) 13).

m0.95~2.12 (CHz, CB), m2.32~2.75 (C H-Py), m7.43-7.64 (ArH), d7.83 (J9Hz, 2-H, 6-H), d8.51 (J2Hz, 6-) 1) In the same way, 2-(4-bromophenyl)-5-(trans-4″-alkylcyclohetyl) xyl)pyridine (25,5b-d) are prepared. Its characteristics and final analysis data Table 7 shows the data.

Table 7 125.5b 80 - 171.4201.467.166.903.712 25.5c 81 151 164.0200.168.25? , 303.5 5325.5d N7 142 170.6193.369.11? , 543 ．． 401 CzoHzJrN 67.04 6.75 3.92 CzzHzs BrN 68.397.30 3.63 CzJzoBrN 68.997.5 5 3.525.6. 2-(4-cyanophenyl)-5-()lance-4- butylcyclohexyl)pyridine(II[a) compound 25.5 a 0.003 mol, copper cyanide 0.004 mol, and N-methylpyrrolidone 10rnIl. Mix and boil over reflux until initial compound 25.5a disappears (approximately 3 hours) . The reaction mixture is cooled to room temperature and poured into 20 ml of aqueous ammonia solution. Then salt Extraction with methylene chloride was performed, the extract was washed with water, dried over NazSOa, and acidified. Filter through aluminum chloride. Evaporate the solvent under vacuum and dissolve the residue in alcohol or and recrystallize from acetone. Compound ma is isolated with a yield of 70%.

TC-N = 124°C, TN-1 = 228°C1 actual measurement %: N8.81. c2□H26N! , Calculation %: N8.79 IR spectrum: V (CM): 2236 cm-'PMR spectrum (c cla, δ, ppm): to, 90(J6)1z, CB,).

mo, 95-2.12 (CHz, CH) 9m2.32-2.75 (CI-P y) 7.43-7.65 (ArH), d7.83 (J9Hz, 2-H, 6-H), s7.60 (3H, 4B), 7.65 (2°-H), 6'-H ), 8.08 (3”-H, 5’-H), d8.53 (6-H), (system AA' BB"), compounds 1) b-d are prepared in the same way.

The phase transition temperature and final analytical data for Compound II[b-d are shown in Table 8.

b CJt 123 237 9.31 Cz+HzaNz 9.20CC5H 1+ 113 228 8.36 CzsHzsNz 8.42 Conventional 2-(4 -cyanophenyl) -5-(4-alkylphenyl nyl)-5-() lance-4-alkylcyclohexyl)pyridine (I -d) phase transition temperature and rotational viscosity coefficient 71 & related comparative data are shown in Table 9. .

2-(4-cyanophenyl)-5-(4-alkylphenyl)pyridine and and 2-(4-cyanophenyl)-5-()trans-4-alkylcyclohexyl ) The values of binary mixtures B and D corresponding to the rotational viscosity coefficient γ of the homolog of pyridine. Calculate more.

Mixture B: 2-(4-cyanophenyl)-5-(4-alkylphenyl ) 10% by mass of pyridine and 90% by mass of mixture A, mixture D: 2-(4- cyanophenyl)-5-() lance-4-alkylcyclohexyl)pyridine 10% quality and mixture A9090 quality Compound A Nidoran-4-hebutyl-(4-cyanophenyl)cyclohexane 4 0 mol% and trans-4-hebutyl-(4-cyanophenyl)cyclohexa 60 mol%, T, = 1 poise (25°C) Table 9 c C5HI+ 76 232 1.280 11.80a 124 228 1.330 17.33b 123 237 1.170 4.81c 114 228 1.200 6.20 From Table 9, the purity of this new compound m a % d It can be seen that the clearing temperature TN-1 is comparable to that of conventional compounds. New compound 2-(4 -cyanophenyl)-5-()trans-4-alkylcyclohexyl)pyridine is the conventional compound 2-(4-cyanophenyl)-5-(4-alkylphenyl) It has a much smaller rotational viscosity coefficient than pyridine. 2-(4-cyanophenyl) =5-(trans-4-butylcyclohexyl)pyridine has a coefficient r1 at 25°C = 17.33 poise, while 2-(4-cyanophenyl)-5-(4 -butyl-phenyl)pyridine has a coefficient γ = 41.0 poise.

Example 26 Production of liquid crystal material by using ma-d according to the present invention 5-propyl-2-(4 -cyanophenyl)pyridine 1.0 g (10% by weight), 5-pentyl-2-(4 -cyanophenyl)pyridine 1.5 g (15% by mass), 2-cyano-5-heptyl 2.0 g (20% by mass) of ruphenylpyridine, trans-4'-propyl pyridine 1.5 g (15% by mass) of 4-ethoxyphenyl ester of lohexanecarboxylic acid , 4-ethoxyphenyl ester of trans-4'-butylcyclohexanecarboxylic acid 1.0g (10ft%) trans-4'-hexylcyclohexanecarbo 1.5 g (15% by mass) of 4-ethoxyphenyl ester of phosphoric acid, 2-/4-() Lance-4-pentylcyclohexyl)-phenyl/-5-ethylpyridine 0. 5g (5% it%), 2-/4-phenyl-5-(trans-4-pentylsic) Place 1.0g (10% by mass) of lohexyl)pyridine (I[Ic) in a container, etc. A liquid crystal material is produced by heating and stirring until an orthotropic phase forms, and then cooling. -15 Range of nematic phase from ~+75.1 °C and rotational viscosity T I = 1 at 25 °C ．． It has 47 bores.

The composition and properties of liquid crystal materials containing compounds of formulas a to d are shown in Table 10 below. Shown below.

Table 10 Examples Composition of liquid crystal material of the present invention Mass T, 25°C Nematic% Poise Phase range ℃ C3H, -<E>-Coo -@-oc mountain 15C mountain building coo %oc mountain 10 Table 10 (continued) Table 10 (continued) Table 10 (continued) C mountain-■-COO two C4H910 Table 10 (continued) Table 10 (continued) Example hα Composition of liquid crystal material of the present invention Mass rr’25°C nematic% Pore Phase range °C On C mountain ◇-Coo @0CJs 10C,)19-■-coo-@-@-cN sTable 10 (continued) CsHrt 1〇-CH■-CxHq　10Table 10 (continued) CsH+ + ← Σ(〉-coo-@　OCH310 From Table 10, formula m　a　 -d's new compound has a low rotational viscosity coefficient TI and a wide range of nenutics. It can be seen that a liquid crystal material having a phase can be obtained. This is a high-speed electro-optical device. This allows for the use of other materials.

Example 33 2-/4-()lanth-4-alkylcyclohexyl)-phenyl/-5-5- () Production of lance-4-alkylcyclohexyl)pyridine (IV) 33.1. 1-(3-dimethylaminopropionyl)-4-(trans-4 -pentylcyclohexyl)benzene (33,1d,)4-()lanse-4-pe cyclohexyl)acetophenone 0.13 mol, paraform 0.22 mol , and 0.13 mol of dimethylamine hydrochloride, 0.25 mol of concentrated hydrochloric acid d. Reflux 15 ml of anhydrous ethyl alcohol for 8-10 hours, cool, and add anhydrous acetate. Dilute with 100 d of water. Precipitated 1-(3-dimethylaminopropionyl)-4 -(4-transpentylcyclohexyl)phenylhydrochloride is filtered off, Dissolved in 200 d of water, alkalized with aqueous sodium hydroxide solution, methylene chloride Extract with The organic phase is dried over NazSOa and the solvent is evaporated.

The base isolated in 75% yield is carried forward to subsequent steps without analysis.

33.2. 1-(3-dimethylaminopropionyl)-4-(trans-4 -Iodine methylate of (pentylcyclohexyl)benzene (33,2d) Compound 33.1d O, 11 mol was dissolved in 110d of anhydrous methylene chloride, and 10° 0.18 mol of methyl iodide is added at C. Leave the reaction mixture in the dark for 2 days . The precipitate (compound 33.2d) was filtered off and anhydrous CHiCI! , wash with Z and air dry. . The yield is 98% and the resulting compound is taken to step 33.3 without analysis. Ku.

33.3 1-acryloyl-4-(4-) lance-4-pentylcyclohexy ) Benzene (33,3d) Compound 33.2d and methylene chloride. This suspension was stirred vigorously for 15 minutes. A solution of 13.2 g of KO) in 32 d of water is added dropwise to the suspension, and the mixture is further Mix for 10 minutes to completely dissolve the precipitate. Separate the organic layer and immerse the aqueous layer in CHzCI ! , t20d. Combine the organic extracts, wash with water, and add hydroquinone. Then, the resulting mixture was dehydrated with NazSOa and dried with 5i (h = 3 cm). Filter and evaporate the solvent under vacuum. Recrystallize the resulting precipitate to avoid decomposition. I moved on to the next step.

PMR spectrum (ccL, δ* ppm): tO, 86 (CH3).

m 1.0~2.0 (CHz and CH), ~2.65~2.78 (A r-OR), dd5.73 (J2Hz and JloHz, C=CHz) , dd6.29 (J2Hz and J17Hz, C=CHz), dd 7.08 (JloHz and J12Hz, C0CH), d7.14 (J 8Hz, 3-H, 5-H), d7.75 (J3Hz, 2-H, 6-H) .

1-Acryloyl-4-() lance-4-alkylcyclohexyl)benzene ( 33,3e-f) are also produced in the same manner.

33.4. 2-/4-() lance-4-pentylcyclohexyl)-phenylene l/-5-() lance-4-propylcyclohexyl)pyridine (IVb) 0.0375 mol of compound 33.3a to compound 25.2b at a temperature of 0 to 10°C□ Mix with 0.034 moles of O and 15 d of absolute ethanol.

The mixture was left at room temperature for 2 hours, cooled to 0"C, the precipitate was filtered off and dissolved in anhydrous ethanol. Wash with 10 d of water. The obtained pyran was dissolved in alcohol 90rd and hydroxy 0.14 mol of amine hydrochloride, 10 d of water, and 5 d of concentrated hydrochloric acid are added.

The reaction mixture is stirred and refluxed for 8 hours. 2/3 of this solvent volume is evaporated, Add 150 d of water to the residue and bring the mixture to a pH of about 8 at a temperature of 25-30"C. Alkalize with an aqueous solution of sodium hydroxide. Filter the precipitate, wash with water, and air dry. , benzene is dissolved and filtered through a layer of SiO□ (, h = 3 cm). from the filtrate Evaporate the medium. Pour the residue into acetone or CC/! , the yield was 70%. 2-/4-() lance-4-pentylcyclohexyl)-phenyl/-5-( ) 0.24 mol of lance-4-propylcyclohexyl)pyridine are isolated.

PMR spectrum (ccpa, δ, ppm): tl, 03 (J6Hz, CH3).

ml, 10-2.05 (CHz, CH), ~2.23-2.63 (CH-8 ), dd7.08 (J9Hz, 3'-H, 5'-H), dd7.29 (J8) 1z and J2Hz, 4-H).

d7.48 (J8Hz, 3-, H), d7.71 (J9Hz, 2'- H, 6'-H), 68.34 (J2Hz, 6-H).

monophenyl/-5-() lance-4-alkylcyclohexyl)pyridine (IV ) are also produced in a similar manner.

The compound of formula (IV) is a trans isomer. PMRC1 of the compound of formula (IV) 3 spectra are -P-80 Fourier spectra in the mode of proton spin relaxation. recorded with a trometer. 33.5ppm and 34.5ppm cyclohexa The signal from the ring carbon has double intensity. The characteristics of this signal are cyclo Corresponds to the trans configuration of the substituent within the hexane ring.

Table 11 below shows the formulas and properties of compounds lance-4-alkylcyclohexyl)-4'-() lance-4-alkylcyclohexyl) Biphenyl (So, A.

1055336) is shown.

Table 11 2 CJs C3) IV b CsH++ CJt 58 251 311 60CC2H5C3HI I d CJt C3HI + e CsH++ CsH++ 55 267 305 30f C5Ht C3 HI 155 220 325 105 Table 11 (continued) a CJs C3H? 144 191 315 134b CSH,, C3H ? 71 241 312 71c CzHs CsH+s 52 226 2 81 55d CJt CsH++ 86 205 297 92e CsH+ + CsH++ 70 252 307 55 Table 11 (continued) 18 9 1o 11 12 13 f C, H, C3H, 144202329127g CsH++ C2H550 20029999 Table 11 (continued) Yield 9% Actual measurement 9% Empirical formula Calculation 2% 69 86.30 10.37 C zsHsqN 86.31 10.0B59 86.51 1043 Cx1H 4sN 86.25 10.5172 H6, 3610, 43C,. H, N 8 6.27 10.3B70 86.42 10.40 C:l, H45N 86 ．． 25 10.5169 86.30 10.79 C: +J49N H6,2 110,747386,3110,17C2,H,,N 86.29 10.2 470 86.30 10.29 c. H,, N 86.27 10.38 table 11, the smetic-nematic transition temperature 'rs-N, the new value of formula IV a-g The lower limit of the nematic phase range of the reference compound is the conventionally well-known compound (SU, A, 10553 It can be seen that this is clearly lower than the Ts-N of 36). The clarification temperature of this new compound is higher than previously known compounds, i.e., this new compound has higher It has a wide range of nematic phases.

Table 12 below shows the composition and composition of the liquid crystal material containing the new derivative of pyridine. Show characteristics.

Table 12 34 C mountain - ■ - 0) CN 20 -20 +85.8 Table 12 (continued) Table 12 (continued) Table 12 (continued) Table 12 (continued) Table 12 (continued) Table 12 (continued) Table 12 (continued) Table 12 (continued) Table 12 (continued) Table 12 (continued) 49 C3B? -(E>-Qo-cy　10　-31-84.1CH20-■- coo-■-C mountain 10CH30-■-COO@CsH++ 20C,H,- @-N=co-@-ocn 23so C5H7-(E>-@-CN 13- 15-84.3 Table 12 (continued) In the example shown in Table 12, the use of the new pyridine derivative in 2) as a liquid crystal material component is the key. Electron with higher upper limit and lower lower limit of matic phase and for external use It is shown that it is possible to provide liquid crystal materials that are suitable for use in optical devices.

Example 52 2-/4-()lanth-4-alkylcyclohexyl)-3-fluorophenyl /-Production of 5-alkylpyridine (V) 52.1. 2-/4-(trans-4-propylcyclohexyl)-3-di Trophenyl/-5-ethylpyridine (Va) in 30 d of concentrated sulfuric acid cooled to 0°C 2-/4-()trans-4-propylcyclohexyl)-phenyl/-5-eth Add 1.01 g of potassium nitrate to a solution of 3.07 g (0.01 mol) of tilpyridine. (0.01 mol) was added slowly and the reactants were added until the initial compound disappeared ( 1 hour) at the above temperature. This reactant was poured into 100 g of ice and [0820% Alkalize with solution to pit approximately 8.

Extraction with benzene (2 x 50 m) was carried out, the organic layer was washed with water to make it neutral, and Si Filter through a layer of O□O (h=20). Evaporate the mother liquor in a rotary evaporator and remove the residue. Recrystallize from alcohol.

2.53 g of compound are isolated (72%). Rfo, 5 (benzene), wound p, 6 2°C, PMR spectrum (δr ppm, COCf!, 3): 0.85 ( 6H, tcHi); 1.2 to 1.90 (14B, b, s, C) It); 2.62(2)1. q.

7.60 (2H, b, HBr); 8.30 (IH, d, JM 2H2, H2); 8.4B (18, (r), IN 2H2, H ); 8.0B (IH, dd, Jo 8Hz, JH2H2IH6); 7. 48 (IH, dd, JM 2Hz, JP 0.6Hz, Hs).

Actual measurement %: C75,11; H8,12; N 8.00 CzzHzsNzO Z calculation %: C75,07; H8,01; N 7.95 Other compounds Vb-f are synthesized in the same way. Final analytical data, melting point and yield are shown in Table 13.

b 74 61 75.80 8.76 7.20c 79 53 76.19 8.70 7.12d 75 57 76.20 B, 59 7.13e 7 0 45 75.12 8.23 8.1Of 76 41 75.91 B, 70 7.41 Table 13 (continued) b　CzJizNzOz　75.86　8.55　7.35CCzsHzaNz Oz 76.23 8.68 7.10d CzsHs4NzOt 76.23 B, 68 7.10e CzzHzsNzOz 75.07 8.01 7. 95f CzaHszNzO□ 75.86 8.55 7.3652.2.　 2-/4-() lance-4-propylcyclohexyl)-3-aminophenyl /-3.52 g of compound V in 30 d of 5-ethylpyridine (VIa) alcohol (0.01 mol) of Ni/Re 1 g, 64% hydrazine 4d and N 0.1 g of aOH is added and the mixture is refluxed. First nitro derivative 52.1a The completion of the reaction is monitored chromatographically until it disappears (approximately 1 hour).

The reaction mixture is filtered, washed on the filter with alcohol and cooled.

2.52 g (78%) of compound Vla are isolated.

TS-N86°C, TN-+ 127°C2 actual measurement %: C82,3; H9,3 8; N 8.54 CzJsoNz, calculation %: C82,06; H9,38 ; N 8.69, other compounds Vlb-f are prepared in the same manner. Final analysis data The data, phase transition temperature, and yield are shown in Table 14.

b 76 80 128 82.16 9.80 B, 00c 79 102 146 92.20 9.81 7.5d 74 116 147 82.41 9.93 7.51e 76 69 105 82.20 9.25 8.7 Of? 8 60 113 82.31 9.64 7.96 Table 14 (continued) b C2, H34N! 82.23 9.78 7.9CCzsHzJz 82 ．． 36 9.95 7.6d C25Hff6N2 82.36 9.95 7 ．． 68e C22H3ON2 82.06 9.38 8.6952.3. 2 -/4- () lance-4-propylcyclohexyl)-3-fluorophenyl /-5-ethylpyridine (■a) at 0-5 °C,) Compound V in IBF, 30d A solution of 3.22 g (0.01 mol) of NaN0z in 820:M 0.69 g (0.01 mol) of the solution are slowly added dropwise with stirring.

Stirring was continued for at least 1 hour at the above temperature, the reactants were filtered, and cooled with ethyl alcohol 10%. Wash with water, dry on the filter, and wash with anhydrous ether. Dry residue to anhydrous The mixture is refluxed for 1 hour. then After cooling, the toluene solution was washed with saturated aqueous sodium solution, then with water, and the Filter the machine layer through 5i (h = 2 cm).

Evaporate the solvent on a rotary evaporator. The residue was recrystallized from acetone and chromatographed. Put it on the fu. 0.88 g (27%) of compound 1 is isolated.

Other compounds ~1[b-f are also prepared in the same manner. Compounds ■ Phase transition temperature of a to f and final analysis data are shown in Table 15.

Conventionally well-known 2-/4-() lance-4-alkylcyclohexyl)-phenyl/ -5-alkylpyridine and the new compound 2-/4-(trans-4-alkyl cyclohexyl)-3-fluorophenyl/-5-alkylpyridine (■a-f Table 16 shows comparative data of the phase transition temperature and nematic phase range ΔTH of

a CJs CJt 60.2 145.1 81.24 8.70 4.19 b CJs CsH++60.0 142.0 B1.36 9.23 4.0 0CCsH++CJt 52.9 144.6 B1.73 9.20 3.6 6d　C2H,C3H,,66,O151,081,659,403,90e　 C5Ht C, Hs 47.6 127.5 B1.24 8.59 4.28 f CsH++CJs 39.5 119.5 81.6Q 9.23 3.7 8a C, JzJF 81.19 B, 67 4.30 27b C24H3□ NF B1.54 9.12 3.96 25CCzsH:+JP 81.70 9.32 3.81 25d C25H2, NF 81.70 9.72 3 ．． 81 21e C22) 128 dejF 81.54 8.67 4.30 1 8f C24H3□NF B1.54 9.12 3.96 17a CzHs C3H? 50.8 87.7 174.4 86.4b CzHs C5L t65.8 78.0 168.0 90. Oc C5H, ICJ? 48.0 93.8 177.4 83.6d C3H? C5H,,37,093,5 179,0B5.5e C3H? CzHs 51.9 92.7 158.8 68-1r C, H,, C2H540,284,6153,168,5Tc- a・’CTN−+・”CΔT,”cl 8 9 10 a 60.2 145.1 84.9 b 60.0 142.0 82. O c 52.9 144.6 91.7 d 66.0 151.0 85. O e 47.6 127.5 79.9 f 39.5 119.5 80.0 From Table 16, it can be seen that there is no smectic phase in compounds ■a-f, and the new compound ■ It can be seen that the nematic phase range ΔTN of a-f is wider than the ΔTN of known compounds. Ru.

Table 17 shows the composition and properties of the liquid crystal material containing the new pyridine derivative of formula (■). vinegar.

Table 17 Table 17 (continued) Table 17 (continued) Table 17 (continued) Table 17 (continued) Example Nα Composition of liquid crystal material of the present invention Mass Nematic phase range % °C Table 17 (continued) Table 17 (continued) Table 17 (continued) As can be seen from Table 17, the new pyridine derivative of 2X1 as a liquid crystal material component Used in external electro-optical devices with a high upper limit and low lower limit of the nematic phase range. It is possible to provide a liquid crystal material convenient for use in

Example 62 2-/4-(trans-4-alkyl)-3-fluorophenyl/-5-/4- () Lance-4-alkylcyclohexyl)phenyl/-pyridine (X) 62.1. 2-/4-() lance-4-pentyl)-3-nitrophenyl/ -5-/4-() lance-4-ethylcyclohexyl)phenyl/pyridine (■ a) is prepared in the same way as for the preparation of compound Va with a yield of 75%.

Tc-y = 87.0°C, TN-1 = 168°C (from ethanol).

The PMR spectrum is the same as Va.

Actual measurement %: C77,81; H9,21; C3゜H4□N2O2 calculation %: C 77,88; H9,15, other compounds of formula (1) are also produced in the same manner as Va.

62.2. 2-/4-() lance-4-pentyl)-3-aminophenyl- 5-/4-() lance-4-ethylcyclohexyl)phenyl/pyridine (IX a) is prepared analogously to compound VIa with a yield of 90%.

TC-N = 98.1°C; TS-N = 135.0'C; TN-z = 212.4°C (from alcohol) actual measurement %, C83,36; Hlo, 19 ; C3°H,, N2 calculation %; C83,28; Hlo, other compounds of formula 25 ■ is also manufactured in the same manner as VIa.

62.3. 2-/4-() lance-4-pentyl)-3-fluorophenyl -5-/4-(trans-4-ethylcyclohexyl)phenyl/-pyridine ( Xa) is produced in the same manner as ①a.

Tc-N=104.6°C; Ts-+=312.2°C (alcohol ri) Actual measurement %; C82,73; H9,65, c. H,, HF calculation%, CB 2.71, H9,72 Other compounds of formula X are also produced in the same manner as ①a.

Example 63 2-(4-alkyl-3-fluorophenyl)-5-()rans-4-alkyl Production of cyclohexyl)pyridine (XIV) 63.1.2-(4-pentyl-3-nitrophenyl)-5-(trans-4 -Ethylcyclohexyl)pyridine (XUa) was prepared in the same manner as in ■ with a yield of 70%. Manufactured.

TC-, = 30°C, TN-t = 42°C (from ethanol) Actual measurement %: C7 5,75:H8,48 Other compounds of formula x■ are also prepared in the same manner as Va.

63.2. 2-(4-pentyl-3-aminophenyl)-5=(4-tran (su-4-ethylcyclohexyl) and lysine (XI[Ia) in the same manner as Vla. Produced with a yield of 92%.

Tc-N=63.1°C; TN-1=120°C (from ethanol) Actual %: C82,43: H9,56, CzJsaNz, calculation %: C82,23; H9,78, another compound of formula X■, is also prepared in the same manner as Vla.

63.3. 2-(4-pentyl-3-fluorophenyl)-5-(trans -4-Ethylcyclohexyl)pyridine (XIVa) is produced in the same manner as ■a. It will be done.

Ts-s = 120'C; TN-1 = 127°C1 actual measurement %: C81,4 6; H9,23, CzJsJF calculation %: CB1.54, H9,12, formula Other compounds of XIV are also produced in the same manner as ①a.

Example 64 2-(4-alkoxy-3-fluorophenyl)-5-(trans-4-al Production of (kylcyclohexyl)pyridine (XV) 64.1. 2-(4-hebutyloxy-3-fluorophenyl)-5-()ra ence-4-ethylcyclohexyl)pyridine (XVa) is 33.4. described in Manufactured in the same way. The yield is 38%.

Tc-5 = 53°C, TS-N = 122°C, TN-1 = 136°C1 actual Measured %: C78,60; H9,12, CzJsJOF, Calculated %: C78,5 5;H9,13 Other compounds of formula xV also include 33.4. It is manufactured as follows.

Example 65 2-p-/2-()trans-4-alkylcyclohexyl)ethyl/-3-fur Orophenyl/-5-alkylpyridine (XVI) 65.1. 2-/4-/2-()lance-4-butylcyclohexyl)ethyl /-3-nitrophenyl/-5-ethylpyridine (64,1a) is the same as Va. It is manufactured in the following manner.

m, p, = 75°C (ethanol) Actual measurement %: C76,25; H8,53, C25H:14N20Z Calculation %: C 76,10, H8,69 65,2,2-/4-/2-()lance-4-butylcyclohexyl)ethyl /-3-aminophenyl/-5-ethylpyridine (65,2a) is produced using Vi Same as a.

Ts-N=97. OoC, TN-1 = 116.0°C (from ethanol) actual measurement %: C82,50; Hlo, OO, CzsHzbNz calculation%: C82,3 6i　H9,95,65,3,2-/4-/2-(trans-4-butylsic ethyl)ethyl/-3-fluorophenyl/-5-ethylpyridine (XVI The production of a) is the same as ■a.

TC-N = 65°C; TN bow = 115°C5 actual measurement %: C81,75; H9 , 44, CzsHs4NF calculation %: C81, 70: H9, 32 example 66 Production of 5-alkyl-2-(4-isothiocyanophenyl)pyridine (X■) 66.1.5-pentyl-2-(4-nitrophenyl)pyridine (66,1a) Manufacturing of. This compound contains 1-β-alkylethylenylpiperidine and 1-acrylic Similarly to 25.3a to 25.5a from liloyl-4-nitrobenzene Manufactured.

ta, p, = 48 °C (from ethanol) PMR spectrum (C1,, δ, p pm): t 0.92 (C): +), m 1.62 (CHz), t 2 ．． 6 (CHzPy), d 8.45 (J2) 1z, Hz), b, s, 7. 55 (HβBT).

b, s, 8.15 () Iz, 6, 3.5) Other compounds 66.1be-e are also 25. 3. Produced in the same manner as 25.5a.

a CsH++ 48 34 71.21 6.8I C+J+, Nz0t? 1.09 6.71b C3B? 73 36 69.60 5.74 C1, Hl, N! O□ 69.48 5.82c C, Hv 19 40 70.38 6.19 C+sHt&Nz(h 70.29 6.29d CJ+3 49 41 71.82 6.82 C+JzoNzOz 71.81? , 09e CJ+s 46 3B? 2.37 7.61 C1*HtzNtCh 72 ．． 46 7.4366.2. 2-(4-aminophenyl)-5-pentylpi Lysine (66,2a) Ethanol 30d, 2-(4-nitrophenyl)-5-pentylpyridine (66 , 1a) 0.01 mole, 1 g of Ni/Re, 2.5 moles of hydrated hydrazine, and A mixture of 0.1 g of NaOH was added to the flask until the initial compound 66.1a disappeared. reflux within. The reaction mixture was filtered, cooled to -10 °C, and 2 0.0073 mol of -(4-aminophenyl)-5-pentylpyridine was isolated. (66.2a). Other compounds 66.2 b-e are prepared in the same manner. So The final analysis data and properties of are shown in Table 19.

a　CsHlI60　73　79.98　8.50　11.52b　C,H?　 112 7B 79.23 7.54 13.17c C=H* 93 76 79.64 8.01 12.35d C=HIs 59 80 80.36 B, 93 10.71e CJ+s 55 74 Bo, 41 9.22 10 ．． 37Table 19 (continued) Nos, experimental formula calculation 1% a CIbHzoNz 79.96 8.39 11.65b C1, H, 6N 279.20 7.60 13.20c C15) I, aNz 79.61 8 ．． 02 12.38d CI? H22N2 80.27 8.72 11.01 e　C,5HzaNz　80.55　9.01　10.4466.3. 5-pe ethyl-2-(4-isothiocyanophenyl) and lysine (XVI[a) 2-(4-aminophenyl)-5-pentylpyridine 66.2a0.02 mol Dissolved in 10 d of anhydrous benzene and added 2 moles of C520.0 and EtJ317. , this mixture is allowed to stand for 5 days. The precipitate is filtered off and washed with anhydrous ether. stirrer, Place the precipitate in a three-loaf flask fitted with a thermometer and addition funnel. Anhydrous chlorine at 0°C Put 20m of roform, Et, and 3d of N into a flask, then add ethyl chloroform. Add phorthate 3d dropwise. The reaction mixture was incubated at 0 °C for 10 min and at room temperature for 1 min. Mix for an hour, wash the chloroform layer with 1% HCj2, water, and dehydrate with Na, SO. After that, it is filtered through 5i (h (h = 2 cv). The mother liquor is evaporated in vacuo. let The residue is recrystallized from hexane. 5-pentyl-2-(4-isothio 0.0106 mol of cyanophenyl)pyridine are isolated with a yield of 53%.

Other compound XVmb-e is also prepared in the same manner. Its final analysis data and characteristics The properties are shown in Table 20.

Well-known compounds 4-alkyl-4'-isothiocyanobiphenyl and new compounds 5-Alkyl-2-(4-isothiocyanophenyl)pyridine (X■a-e ) is shown in Table 21. From Table 21, it is clear that this new compound The well-known compound 4-alkyl-4'-isothiocyanobiphenyl (MCLCLe tters, vol, 102+ No, 155.1984. R, Dabro wski.

J, Dziaduszek, T, 5zcucinski+”4- (tran (4'-n-alkylcyclohexyl) isothiocyanatobenzene, a new species It can be seen that the refining temperature is clearly higher than that of similar low melting point stable nematics.

Table 20 a Cs8 mouth 53 34.0 98.5 72.48 6.39 10.00b CJt 67 64.0 99.0? 1.01 5.36 11.20c C=H-5837,6100,071,596,0310,60d C? +(, ff 63 27.0 99.0 72.81 6.90 9.52e CJI s 70 26.0 99.0 73.46 7.29 9.14 Table 20 (continued) ) Nos, experimental formula calculation 9% a　C+J+@NzS　72.30　6.42　9.92b　C+5HzoNz S 70.83 5.55 11.01c C,)l+i, NzS 71.61 6.01 10.44d C+5HzoNzS 72.93 6.80 9. 45e C+JtJzS 73.51 7.14 9.02 Table 21 Table 22 shows liquid crystal materials comprising novel 2,5-disubstituted pyridine derivatives of formula xX1 The composition and properties of

Table 22 Table 22 (continued) Table 22 (continued) Table 22 (continued) Table 22 (continued) Table 22 (continued) Table 22 (continued) For example, α Composition, mass, nematic phase range % of liquid crystal material of the present invention °C Table 22 (continued) Table 22 (continued) Table 22 (continued) Csllt-■-Coo @0CtHs 10 From Table 22, the liquid crystal material components The use of novel pyridine derivatives of formula It can be seen that it is possible to provide a fee.

Example 76 2-/4-(4-cyanophenyl)-phenyl/-5-alkylpyridine (X■ )Manufacturing of ? 6.1. 2-/4-(4-bromophenyl)phenyl/-5-pentylpyri Production of gin (76,1a). This compound is 1-β-alkylethylenylbiperid and 4-acryloyl-4'-bromobiphenyl from 25.3 a to 25 ．． 5 Manufactured in the same manner as a.

Actual measurement %: C69,36; H5,91, CzzHzNBr calculation %: C69 ,48; H5,8376,2,2-/4-(cyanophenyl)phenyl/- Production of 5-pentylpyridine (X■a). By using 76.1a, this compound Manufactured in the same way as ■.

"r, -, ~90.1°C, TS-N = 162°C, TN-1 = 251° C measured %: C84,71; H6,65, C23H2□N2, calculated %: C8 4,63, H6,79 Other compounds of formula X■ are also prepared in the same manner as ma.

Example 77 5-Alkyl-2-/4-(2-E-cyanovinyl)phenyl/pyridine (X IX) production ? ? , 1. 5-propyl-2-/4-(2-E-carboxyvinyl)phenylene 2-(4-bromofyl)/pyridine hydrochloride (77,13) under argon flow phenyl)-5-propylpyridine 4.14 g (15 mmol), P (OC HffC6H4) 30.183g (0.6 mmol), Pd(OAc)z 0 ．． 0345g (0.15 mmol), EhN 7.651d, and acrylic 1.62 g (1,561 nl, 22.5 mol) of acid was placed in a reflux condenser, stirrer, and into a flask fitted with a gas outlet. Heat this flask to a boil, The contents are refluxed under argon vapor for 1 hour. Dissolve this reaction mixture in 100 d of water and filter through a glass filter, and acidify the filtrate with 10% hydrochloric acid to pH approximately 6. Shen Filter the precipitate and wash with water and acetone. When air-dried, 77.1a 4g (99% ) is isolated and this product is carried to subsequent steps without recrystallization or analysis. Ku.

77.2. 5-propyl-2-/4-(2-E-carboxyvinyl)phenylene /Hysodinamide (77,2a) methylene chloride 10J+21! Medium compound 77 ．． 1a 3.5 g (11.1 mmol) of phosphorus pentachloride is added to a mixture of 16.5 mmol) is added with stirring and stirring is continued for a further 3 hours. this reaction The mixture was slowly poured into aqueous ammonia at OoC, stirred for 1 hour, and the methylene chloride was removed. Evaporate. The precipitate was filtered off, washed with water and acetone, and 77.2b was purified in the same manner. isolated, m, p, = 238-241°C; 77.2c.

tm, p, = 235-240℃, 77.2d, m, p, = 230- 234℃ near 7.2e.

m, p, = 229-234°C. take this substance to the next stage without analyzing it .

77.3. 5-propyl-2-/4-(2-E-cyanovinyl)phenyl/ Pyridine (XIXa) Unpurified amide 77.2a 2.3 g (8.75 mmol) and oxy salt Phosphorus 10m! The mixture is refluxed for 2 hours and the excess phosphorous oxychloride is evaporated in vacuo. . Fifty grams of benzene is added to this residue, and the mixture is neutralized with aqueous ammonia while cooling.

The benzene layer was washed with water, dehydrated with anhydrous sodium sulfate, and SiO□ (h=2c+n ). Evaporate the benzene and recrystallize the residue from alcohol. Ru. 1.4 g (61%) of compound XIX is isolated.

PMR spectrum (CCl 4):mo, 85 (3H, CH:+); m1 ．． 3 to 1.6 (2H, CHz); t2.65 (2B, J = 6Hz, d, 5.95 (1B, J = 16.5Hz.

H &); d, 7.45 (IH, J=16.5Hz, J3): d, 7.5 5 (28, J = 8Hz, Hz, s); dd, 7.6 (1B, J, = 8Hz, Jetr""2H2,Hr) = dd, 7.7 (IH9JBr=8Hz, JB r=1)! z, HB); d, 8.05 (2H, J=8Hz, Hz6) :d8.55 (IH.

J=IHz+　Ha　).

Other compounds of 2XIXbe-e are prepared in the same manner.

The phase transition temperatures and final analytical data for compounds of formula XIXa-e are shown in Table 23.

The well-known compounds 4-alkyl-4'-(2-E-cyanovinyl)biphenyl and Comparative data on the phase transition temperatures of the new compounds of Formula XIX and Formula XIX are shown in Table 24.

Table 23 Table 23 (continued) Calculation % yield Nos, experimental formula CH% Table 24 From Table 24, it can be seen that the clarification temperature of the new compound of formula XIXa-e is higher than that of the well-known compound (Biul etyn Wojskowej Akademiitechnicznej, R OK XXX.

No. 6 (346) + 143 + 1981 lR, Dabrowsk i , E, Zy tynski, “Wlasnosc” ■ mezomorphiczne pochodnych 4-n-pentylo It can be seen that the value is clearly higher than that of "bifenylu").

Table 25 shows the composition and composition of liquid crystal materials comprising novel pyridine derivatives of formula XIXa-e. and characteristics.

Table 25 C mountain-σcoo-@-oc mountain 15 C Mountain - <E> - COO (◇ - OC Mountain 10CJlz [Yes] - coosha octus 15 Table 25 (continued) 80 C5H 1 R defense CN 20 -19-73.6CsH++ @Coo @ 0CsHfu 10 Table 25 (continued) Table 25 (continued) Table 25 (continued) Table 25 (continued) Table 25 (continued) From Table 25, the use of the new pyridine derivative of formula XIXb as a liquid crystal material component: It is possible to provide liquid crystal materials with a wide range of nematic phases and high fining temperatures. I understand that.

Example 85 2-/4-(2-E-cyanovinyl)phenyl/-5-(trans-4-al Production of (kylcyclohexyl)pyridine (XX) 85.1. 2-/4-(2-E-carboxyvinyl)phenyl/-5-() 4-propylcyclohexyl)pyridine hydrochloride 85.1a is produced similarly to 77.1a from 25.5b, without purification. Take it to the next stage.

85.2. 2-/4-(2-E-carboxyvinyl)phenyl/-5-() ence-4-propylcyclohexyl)pyridinamide (85,2a) is 77.2 It is produced in the same manner as a, and is carried to the next step without purification.

85.3. 2-/4-(2-E-cyanovinyl)phenyl/-5-(4-tra Preparation of (X-propylcyclohexyl)pyridine (XXa).

This compound is prepared similarly to XLXa.

Tc-N=133.0”C, TN-1=318°C (from ethanol) Actual % : C83,64; H7,81, C23H26Nt calculation %: C83,59; Other compounds of formula H7,93 χχ are also produced in the same manner as XIXa.

Example 86 2-/4-(2-E-cyanovinyl)phenyl/-5-(4-alkylphenyl ) Production of pyridine (XX I) 86.1. 2-/4-(2-E-cyanobi Production of nyl)phenyl/-5-(4-amylphenyl)pyridine (χχIa).

This compound is 2-(4-bromophenyl)-5-(4-amylphenyl)pyridi It is produced in the same manner as XLXa from

Te-5=136.1°C, TS-N=168.5°C, TN-1=31 0°C actual measurement %: C85,31; H6,73, CzsHzJz calculation %: C8 5,19; H6,86 Other compounds of formula XXI are also produced in the same manner as XIXa. Ru.

Example 87 2-(trans-4-alkylcyclohexyl)-5-cyanopyridine (XXI I) Production 87.1. ) lance-4-hexyl-4-acetylcyclohexane (87,1 a) is trans-4-hexylcyclohexanecarboxylic acid chloride with a yield of 79%. according to conventional methods than organomagnesium derivatives of lido and diethylmalonate. Manufactured. b, p, = 120°C/4 mmHgSn:' = 1.459 0. Based on the NMR”C spectrum, the cis:trans ratio is 87=1 to 7:1. It has been shown.

Other compounds 87.1 b-e are prepared in the same manner.

Substance, yield (%), boiling point, no: 87.1b, 74, 110'C/ 5mmHg, 1.4588; 87.1c, ? 9, 128° C/2 mmHg, 1.4579; 87.1d, 8B, 5, 8 6°C/2mmHg, 1.4556; 87.1e, 73.　135°C/2 mmHg, 1.4600° 87.2. 3-cyano-6-(trans-4-hexylcyclohexyl)pyri D-2-one (87,2a) Sodium 3.27g in 200d anhydrous ether (0.14 mol), compound 87.1a 29.6 g (0.14 mol) and ant A mixture consisting of 12.7 g (0.17 mol) of ethyl acid was heated to a boil while stirring. I can do it.

The resulting precipitate is filtered off, washed with 50% of anhydrous ether and dried under vacuum. Natoriu 31.8 g (87.7%) of mu salt are isolated. Said salt (31.8g, 0.1 2 mol) and 10.5 g (0.12 mol) of cyanacetamide were added to the dioxa Contains 5001d Hg, 3.5d acetic acid, and 5IIdl piperidine. and the mixture is stirred at room temperature for 5 hours. This mixture at 12 o'clock Reflux for a while, pour into nzoz and acidify with acetic acid. Filter the precipitate and add water and ethanol. Wash with water, air dry, and use in the next step without recrystallizing.

20 g (56%) of 87.2a are isolated. m, p, = 228°C (geo (from Kisan).

Other compounds 87.2b-e are prepared in the same manner.

Materials Yield % Melting point 1°C (from dioxane) 87.3. 2-chloro-3- Cyano-6-(trans-4-hexylcyclohexyl)pyridine (87,3a ) Compound 87.2a 18.2 g (0.06 mol) and PhPOCf z 120 for 3 hours while stirring a mixture comprising 25.4 g (0.13 mol) Heat to ~130°C. The reaction mixture was cooled to room temperature and mixed with an ice-water mixture of 200 g, stirred for 1 hour and alkalized to pH 9 with aqueous ammonia solution. precipitation Filter off, wash with water, dry and evaporate. 87.3a 14.8g (75%) isolated. b, p, = 220"C/2 mmHg, m, p, = 61. 9 °C (from hexane), other compounds 87.3 b-e were prepared in the same way. Ru.

Materials Yield % b, p, ”C/mmHg m, p, ’C87,4,2- () lance-4-hexylcyclohexyl)-5-cyanopyridine (xxIIa ) Compound 87.3a 14.8 g (0,048 mol), 10% Pd/C 1 g, 5.3 g (0.05 mol) of anhydrous soda, containing 200 m of anhydrous ethyl acetate. The mixture was heated at room temperature and 1 atm hydrogen pressure until the calculated amount of hydrogen was absorbed (approximately 1 atm). 0 hours) Hydrogenate. The reaction mixture was filtered, the solvent was evaporated under vacuum and the residue Silica gel column (column height 20CI11, silica gel 40/100, elution Purify by chromatography using liquid benzene:hexane (1:2). Compound XXIIa 7 g (54% yield) are isolated. Tc-5=36.3°C1Ts-s=41 ．． 5°C, 'rN-, = 60.4°c (hexane). Other compounds XXIIb -e is also produced in the same way.

The transition temperature and final analytical data for the compound 弐χXnb-f are shown in Table 26. this The structure of the compound is confirmed by PMR and NMR13C spectra. Compound X PMR spectrum of XIIa (CC/!, δ, ppm): 1.08-2. 85 (23H, m, CHx, CH (CHz), ); 7.28 (LH, a, J Ortho-87, Hs); 7.92 (18, dd, J Ortho-87.

H4); 8.8 (IH9S, H&).

Table 26 This method is used to measure the electro-optical parameters of well-known and new compounds. It is necessary to use mixtures of these substances. It is an individual conventionally well-known compound and the compound of formula This is because it has a tick phase. Mixtures of 3, 5, and 6 congeners can be degree range of mesophases, so that comparisons are convenient.

Therefore, a mixture consisting of the following three components was prepared.

Mixed MA: 2() lance-4-propylcyclohexyl)-5-cyano Pyridine 30 mol%, 2-()lans-4-pentylcyclohexyl)-5-cy Anopyridine 40 mol%, 2-() lance-4-hexylcyclohexyl)-5 -cyanopyridine 30 mol% Mixture B: 30 mol% 5-propyl-2-(4-cyanophenyl)pyridine, 5 -Pentyl-2-(4-cyanophenyl)pyridine 40 mol%, 5-hexyl -2-(4-cyanophenyl)pyridine 30 mol% Mixed hc: 30 mol of 2-(4-propylphenyl)-5-cyanopyridine %, 2-(4-pentylphenyl)-5-cyanopyridine 40 mol%, 2-(4 -hexylphenyl)-5-cyanopyridine 30 mol% The phase transition temperature, dielectric anisotropy, and electro-optical parameters of mixtures A, B, and C Table 27 shows related comparative data.

Properties of mixtures of liquid crystal compounds Table 27 (continued) Δε=ε, −ε, □Anisotropy of inductivity □Optical anisotropy Uth-, V□ Twist at transmission level 0.9 (first transmission is 1.0) Limit voltage of action U--t, V□ Saturation voltage of twist action at transmission level 0.1 U, V□Measurement voltage τ. FF, 115OFF time, after turning off the voltage until the transmission level of 0.9 is reached. time at 6μm cell thickness From Table 27, the rotational viscosity at 25°C of the mixture of this new compound (mixture A) γ, = 1-40 poise for mixture B (71 = 1.92 poise) and mixture CC r, = 3.50 poise).

Composition and properties of liquid crystal materials comprising novel pyridine derivatives of formula XXn as shown in Table 28 shows.

Table 28 Table 28 (continued) Table 28 (continued) Table 28 (continued) Table 28 (continued) Table 28 (continued) Nα Composition of liquid crystal material of the present invention Mass 71.25°C Nematic% Poise Phase range C Table 28 (continued) C&H 慴■-COO-@-0CJv 13 Table 28 (continued) Table 28 (continued) From Table 28, the use of the new pyridine derivative xxn as a liquid crystal material component has a rotational viscosity. A liquid with a small coefficient and a wide range of nematic phases, making it convenient for high-speed electro-optical devices. Make it possible to provide crystalline materials.

Example 97 2-(4-alkoxy-3-fluorophenyl)-5-alkylpyridine (X XII[) 97.1. 2-(4-hebutyloxy-3-fluorophenyl)-5-heb Chilpyridine (XXIIIa) This compound is a vinyl ketone corresponding to an enamine. After condensation of 33.4. Similarly, pyran and hydroxylamine hydrochloride It is produced by the reaction of

Yield is 65%. Tc-=A=28°C"T SA-1=49.1°C ( (from ethanol) Actual measurement %: C77,91; H9,43°CzsHsbNOF calculation %: C77 , 88; H9, 41 Other compounds of formula XXI[I are prepared in the same manner.

industrial applications The compound proposed here has a low steering voltage (steering voyage). liquid crystal materials, two-component liquid crystal materials with different steering voltages, and low viscosity nematic phase with a low lower limit. It has broad spectral properties that allow its use in the production of liquid crystal materials. this Their liquid crystal materials can power watches, small calculators, television screens, and solar cells, for example. Different electronic optics with static as well as dynamic control modes, such as devices, etc. Applications were found for academic equipment.

international search report Drobicchi ■Applicants: Vetrov, Vladimir Fedorovich ■Recipient: Varnik, Mikhail Ivanovich ■Person of request: Teytov, Victor Vasilyevich ■Applicants: Ivaschenko, Alexander Vasilyevich ■Person of request: Korotkova, Natalya Ivanovna ■Applicants Kovseyev, Evgeny Ivanovich ■Person Rabinovici, Arnold Zinowivici ■Person Bumagin, Nikolai Alexandrovich ■Delivery person: Andre Yukhova, Nonna Vetlovna ■Applicant: Beretskaya, Irina Vetlovna @Person Martuev, Sergey Dmitrievich Ruskoy Zheleznoy Drogya Day, 10. Kvarchila 79 Soviet Union , 123056. Moscow, Uritsa Vasilyevskaya.

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Claims (30)

[Claims] 1. The following formula as a liquid crystal material component ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ [In the above formula, if Y is R'▲There are mathematical formulas, chemical formulas, tables, etc.▼, Z is CN, ▲number There are formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, There are chemical formulas, tables, etc. ▼▲ There are mathematical formulas, chemical formulas, tables, etc. ▼▲ Mathematical formulas, chemical formulas, There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼; If Y is R' , Z is R2▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲There are mathematical formulas, chemical formulas, tables, etc. ▼、▲There are mathematical formulas, chemical formulas, tables, etc.▼、▲There are mathematical formulas, chemical formulas, tables, etc.▼ ,▲There are mathematical formulas, chemical formulas, tables, etc.▼▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Number There are formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, There are chemical formulas, tables, etc. ▼; If Y is -CN, Z is R'▲ mathematical formula, chemical formula , there are tables, etc. ▼; if Y is R'▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ , Z has ▲ mathematical formulas, chemical formulas, tables, etc. ▼, ▲ has mathematical formulas, chemical formulas, tables, etc. ▼ If Y is ▲There are mathematical formulas, chemical formulas, tables, etc., then Z is ▲Mathematical formulas, chemical formulas, tables, etc. There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼; R', R2 represent an alkyl group having 1 to 12 carbon atoms; R3 is F, N Liquid crystal induction of 2,5-disubstituted pyridine represented by [representing O2, NH2, CN] body. 2. The formula below, ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 1, which is represented by: 3. The formula below, ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 1, which is represented by: 4. The formula below, ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 1, which is represented by: 5. The formula below, ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 1, which is represented by: 6. The formula below, ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 1, which is represented by: 7. The formula below, ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 1, which is represented by: 8. The formula below, ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 1, which is represented by: 9. The formula below, ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 1, which is represented by: 10. The formula below, ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 1, which is represented by: 11. The formula below, ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 1, which is represented by: 12. The formula below, ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 1, which is represented by: 13. The formula below, ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 1, which is represented by: 14. The formula below, ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 1, which is represented by: 15. The formula below, ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 1, which is represented by: 16. The formula below, ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 1, which is represented by: 17. The formula below, ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 1, which is represented by: 18. The formula below, ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 1, which is represented by: 19. The formula below, ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 1, which is represented by: 20. The formula below, ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 1, which is represented by: 21. The formula below, ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 1, which is represented by: 22. The formula below, ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 1, which is represented by: 23. The formula below, ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 1, which is represented by: 24. The formula below, ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 1, which is represented by: 25. The formula below, ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 1, which is represented by: 26. The formula below, ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 1, which is represented by: 27. The formula below, ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 1, which is represented by: 28. The formula below, ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 1, which is represented by: 29. A liquid crystal material comprising at least two liquid crystal components, the liquid crystal component A liquid of 2,5-disubstituted pyridine, at least one of which is represented by the formula according to claim 1. A liquid crystal material characterized by being a crystalline derivative. 30. The content of the liquid crystal derivative of 2,5-disubstituted pyridine is 1 to 75% by mass. The liquid crystal material according to claim 2, characterized in that: