JPH02503436A - 2,3-difluorophenol derivative - 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] 2.3-difluorophenol derivative The present invention is based on the formula 1 [wherein R1 and R2 each independently represent 1 to 15 C atoms] an alkyl group having one CH2 group or 24 Non-adjacent CH, groups of 1H are -0-, -CO-, -CH=CH- and ( or) -C= may be replaced by C-, m is 1 or 2 , and Q is -co- or -CH,-]. It concerns a nol derivative.

For the sake of brevity, in the following description Cyc is a compound of the 1,4 formula 1 are the effects of liquid crystal phases, especially the twisted cell principle, guest-host effects, and deformation of aligned phases. Or it can be used as a component of the liquid crystal phase for displays based on the effect of dynamic scattering. can.

The compound represented by formula 1 is unique in that it has a clearly negative anisotropy in dielectric constant. Therefore, in an electric field, the compounds represented by formula 1 have their long axes pointing in the direction of this field. f! directly aligned. This effect is known and has been applied to various liquid crystal displays, For example, a light scattering type (dynamic scattering) liquid crystal cell or the so-called DAP type ( liquid crystal cells of the aligned phase deformation) or ECB type (electrically *Jalized birefringent Liquid crystal cells of the guest/host type (guest/host interaction) Used in crystalline cells to control optical transparency.

A large number of liquid crystal compounds with weak negative dielectric anisotropy have been synthesized to date. There is. On the other hand, liquid crystal compounds with large dielectric constants and negative anisotropy are still In addition, relatively little is known about this type of negative anisotropy with a large dielectric constant. Compounds with properties such as poor solubility in mixtures, high viscosity, high It has drawbacks such as low melting point and chemical instability. Therefore, it has negative attractive anisotropy. and to further improve the physical properties of mixtures for a very wide variety of electro-optical applications. There is a need for a different type of compound that allows this.

It has negative dielectric anisotropy and is bonded by carboxyl groups or covalent bonds. two or three rings and one or more side groups, such as halogen, The liquid crystal component having a cyano or nitro group is DE 2,240,864, DE 2,613,293, DE 2,835,662, DE 2,836,086 and EP 023,728.

In EP 084,194, the compounds according to the invention are included in the broad formula It is. However, in this EP 084.194, the formula according to the present invention is shown. None of the individual compounds described have been described, therefore this prior art From the technical knowledge, one skilled in the art can easily derive the synthesis of the compounds of the present invention, and The compound has an excellent memphasis range in a favorable position and has a low It has a large negative attraction at the same time as its viscosity; it should be recognized that it is remarkable in that it has anisotropy. I can't even do it.

Furthermore, a dibenzoic acid ester compound of 2,3-dichloro b-droquinone is known. [For example, J, Oro, Chem, 39. by Br1sto1 et al. 3138 pages (1974) *or Clanderman et al., J, ^-, Ch. esz, Soc, page 97.1585 (1975)], while this These compounds are monomodified or only have a very narrow membrane range. It is. Eidenschink et al., Angew, Che-, 89, 10 4-hydroxy-2,3-dichlorobenzoin, described on page 3 (1977) Ester compounds of acids have only a narrow membrane range.

4-Alkyl known from West German Patent Publication No. 2.933.563 -2,3-dichlorophenyl-4°-alkylbicyclohexyl-4-carvone Acid ester compounds cannot be used industrially due to their high viscosity .

The object of the present invention is to provide a safe material having a large negative anisotropy of dielectric constant and at the same time a low viscosity. The objective is to find stable liquid crystal compounds or mesogenic compounds.

It has been found that compounds of formula 1 are particularly suitable as components of liquid crystal phases.

In particular, these compounds have a wide membrane range and relatively low viscosity. It can be used to prepare stable liquid crystal phases.

Furthermore, by providing the compound represented by formula 1, from the viewpoint of various applications. , the range of liquid crystal substances suitable for the preparation of liquid crystal mixtures is quite substantially expanded considerably. .

Compounds of formula 1 have a wide range of uses. These compounds are based on the choice of substituents. By choosing the Ru.

However, the compound of formula 1 can also be used for liquid crystals from other groups of compounds. can be added to the substrate to improve the dielectric anisotropy and/or optical properties of such dielectrics, for example. anisotropy and/or viscosity and/or phase range and/or tilt angle can be changed.

Compounds of formula 1 can also be used as components of liquid crystal dielectrics. It is also suitable as an intermediate for the production of other substances that can be used.

The compound of formula 1 is colorless in its pure state and is preferred for electro-optical applications. The liquid crystal membrane is formed in the temperature range that is precisely located. These compounds It is very stable chemically, thermally and to light.

Thus, the present invention relates to compounds of formula 1, and a suitable carboxylic acid. acid or its reactive derivative with a suitable hydroxyl compound or its reactive derivative. The present invention relates to a method for producing a compound of formula 1, which is characterized in that it is reacted with a human body.

Furthermore, the invention relates to the use of compounds of formula 1 as components of liquid crystal phases. Ru. Furthermore, the present invention provides a liquid crystal phase containing at least one compound of formula 1 and The present invention relates to a liquid crystal display element containing this type of phase. This type of phase is particularly It has advantageous elastic constants and is particularly suitable for TFT mixtures due to its low Δε/ε value. It's suitable.

In the above and below descriptions, R], R2 and m are not explicitly explained separately. shall have the meaning set forth above.

Therefore, the compound of formula l has the dependent formula a and more R-CyC-COO-Phe The two rings of F2-R2 engineering aR'-CVC-CH20-PheFz-R2I b Compounds with and dependent formulas 1c and JdR'-Cyc-Cyc-COO-Ph eF2-R2ICRS-Cyc-Cyc-CH,0-PheF2-R" It includes compounds having three rings of ld.

Among these compounds, compounds of the subformula 1a and IC are particularly preferred.

In the compounds mentioned above and below, R+ and R″2 are preferably alkyl or or alkoxy.

- More preferred compounds include one in which one of the groups R1 and R2 is alknyl or oxa Compounds of the formulas above and below that are alkyl (e.g. alkoxymethyl) Ru.

In the above and below formulas, R1 and R2 preferably represent 2 to 12 C atoms. children, especially 3 to 10 C atoms.

One or two CH groups in R2 and R2 may be substituted, Preferably, only one CH2 group is replaced by -〇- or =CH-CH- is being given.

In the above and below formulas, R1 and R2 are preferably alkyl, alkyl, xy or other oxaalkyl groups, and also alkyl groups (including one or two CM, the group is replaced by 10H-CH- ).

If the groups R1 and HQ are an alkyl group [one CH present in this group, the group has 0 atoms] May also be substituted (such as alkoxy or oxaalkyl) Rui has two fI! :II CH2 groups are alkoxyalkoxy or may be substituted by 0 atoms like dioxaalkyl] , these may be linear or branched, preferably the alkyl group is , is linear and has 2.3.4.5.6 or 7 C atoms. Therefore, good Preferably, ethyl, 10-pill, butyl, pentyl, hexyl, he1-tyl, ethoxy cy, 10boxy, butoxy, pentoxy, hexoxy or heboxy, and Additionally, methyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl ole, tetradecyl, pentadecyl, methoxy, octoxy, tunoxy, decoxy , undecoxy, dodecoxy, tridecoxy or tetradecyl.

Oxaalkyl is preferably linear 2-oxypropyl (=methoxymethyl ), 2-(=ethoxymethyl) or 3-oxabutyl (=2-methoxyethyl) ), 2-23- or 4-oxapentyl, 2-53-14- or 5-oxapentyl sahexyl, 2-13-14-15- or 6-oxaoctyl, 2-53-1 4-55-16- or 7-oxaoctyl, 2-13-14-25-16-2 7- or 8-oxanonyl, 2-13-14-15-6-17-8- or 9 -Oxadecyl, 1,3-dioxabutyl (=methoxymethoxy), 1.3- 11.4-or 2,4-dioxapentyl, 1,3-11,4-11.5-2 ．． 4-12.5- or 3.5-dioxahexyl, 1.3-1i, a +, 1.5-11, 6-12, 4-22.5-52.6-23.5-13.6-ma or 4,6-dioxa.

The groups R1 and R2 are alkyl groups and the CH2 group present in this group is -C When 1 is replaced by l(=CH-, the trans-form is preferred, This alkenyl may be either straight-chain or branched. Preferably & well, that is linear and has 2 to 10 C atoms. Therefore, it is vinyl, prog-1-enyl or 10-but-2-enyl, vodo-1-enyl, Boudot-2-enyl or Boudot-3-enyl, bent-1-nonyl, bent-2- Enyl, bent-3-enyl ta! i Pent-4-enyl, hex-1-e nyl, hex-2-enyl, hex-3-enyl, hex-4-enyl or Kis-5-enyl, hept-1-enyl, hept-2-enyl, he-1-3-enyl nyl, he1-4-enyl, he1-5-enyl or he1-6-enyl, o ct-1-enyl, oct-2-enyl, oct-3-nonyl, oct-4-enyl oct-5-enyl, oct-6-enyl or oct-7-enyl, non-1-enyl, non-2-enyl, non-3-enyl, non-4-enyl, non-enyl Non-5-enyl, non-6-enyl, non-7-enyl are non-8-enyl , dec-1-nonyl, de9-2-enyl, dec-3-enyl, dec-4-nonyl , dec-5-enyl, dec-6-enyl, dec-7-enyl, dec-8-enyl Or dec-9-enyl.

Due to its high solubility in commonly used liquid crystal substrate materials, branched side groups R1 and Compounds of formula 1 having R2 and R2 are optionally of interest, and in particular these If the compound is optically active, it is important as a chiral doping substance. be. This type of smectate compound is suitable as a component for ferroelectric materials. ing.

Branched groups of this type generally contain no more than one chain branch. good Preferred branched groups R1 and/or R2 are yn-10-pyl, 2-butyl ( = 1-methyl 10 pils), isobutyl (= 2-methyl 10 pils), 2-methylbutyl methyl, impentyl (=3-methylbutyl), 2-methylpentyl, 3-methyl Pentyl, 2-ethylhexyl, 2-70virpentyl, in-10boxy, 2- Methyl 10poxy, 2-methylbutoxy, 3-methylbutoxy, 2-methylpene Toxy, 3-methylpentoxy, 2-ethylhexoxy, l-methylhexoxy , 1-toxy to 1-methyl, 2-oxa-3-methylbutyl, 3-oxa-4-methyl Tylpentyl, 4-methylhexyl, 2-nonyl, 2-decyl, 2-dodecyl, and 6-methyloctoxy.

Formula 1 represents the racemic and optical antipodes of these compounds, as well as mixtures thereof. It includes compounds.

Among the compounds of formula 1 and formulas la to Id, at least one of the groups present therein Preference is given to compounds in which has one of the preferred meanings mentioned above.

Compounds of formula 1 have the structure M [e.g. Houben-Weyl's He-thode n der Organischen Cheiie, Geor g -Thieie-Verlag, Stuttgart The above reaction can be carried out by methods known per se, such as those described above, and in particular for MN. 6 which are known in the art and prepared under suitable reaction conditions. Variants not described but known per se can also be used. .

If necessary, the starting material can be removed without isolating it from the reaction mixture. Instead of M-contact, the reaction system is further reacted to form the formula compound. It can also be formed within.

Compounds of formula I can be obtained starting from 1,2-difluorobenzene.

A compound of M person, a! xI7 method [for example, ^, s, ttoe, etc.: J, Che Il, Soc, Chell, Co1n, 22.582 (1965)] Metallized and reacted with a suitable electrophile. The procedure for this reaction can be found, for example. obtained in this method using tertiary butyl hydroperoxide as the electronic reagent. 2,3-difluorobenzene was used. Rho-4-R2-phenol can be obtained. optionally tetramethylethyle complex agents such as hexamethyl phosphate triamide (THEOA) or hexamethyl phosphate triamide (add coiplexing agen B and add an inert solvent such as diethyl Ether, tetrahydrofuran, dimethoxyethane, tertiary butyl methyl ether or dioxane, hydrocarbons such as hexane, heptane, cyclohexane, 1,2-difluorocarbon in benzene or toluene or mixtures of these solvents. 1-R2-2,3-difluorobenzene at -100°C to +50°C. , preferably at a temperature of -78°C to 0°C, phenyllithium, lithium tetramethyl React with lupiperidine, n-2 secondary- or tertiary-butyllithium.

The lithium 2,3-difluorophenyl compound has a temperature of -100°C to 0°C, preferably React with a suitable electrophile at -50°C. Suitable electrophiles are aldehydes, Getone, nitrile, epoxide, carvone W! i derivatives such as esters, anhydrides substance or halide, haloformate or carbon dioxide.

Lithium 2,3-diphthalate for reaction with aliphatic or aromatic halides Fluorophenyl compounds are transmetallized and bonded via transition-metal catalysis. Ru. Salmon 2,3-difluorophenyl compounds (for example, West German Published Patent Application No. 3,63 2,410) or titanium 2,3-difluorophenyl compounds (e.g. 3,736,489) is particularly suitable for this purpose. Ru.

Compounds of formula 1 can be prepared using alcohols or phenols (or reactive derivatives thereof). to esterify the corresponding carboxylic acid (or its reactive derivative) using Therefore, it can be obtained.

Suitable reactive derivatives of the carboxylic acids mentioned above are in particular acyl halides, especially carboxylic acids. lorides and bromides, as well as anhydrides such as mixed acid anhydrides, azides or is an ester, especially an alkyl ester having 1 to 4 C atoms in the alkyl group. Ru.

Suitable reactive derivatives of the alcohols or phenols mentioned above are particularly preferred. is the corresponding metal alcoholate or fer of an alkali metal such as Ha or K. rate.

The esterification is advantageously carried out in the presence of an inert solvent. very suitable Solvents include, in particular, ethers such as ethyl ether, di-n-butyl ether, THF, dioxane or anisole, getones such as acetone, butanone or is cyclohexanone, amides such as DHF or hexamethylphosphoric triamide , hydrocarbons such as benzene, toluene or xylene, halogenated hydrocarbons, etc. For example carbon tetrachloride or tetrachloroethylene and sulfoxides such as dimethyl Tylsulfoxide or sulfolane. Advantageously, the formed during esterification Water-immiscible solvents can be used simultaneously to remove water by co-distillation. can. Optionally, as a solvent for the esterification, an excess of organic base e.g. It is also possible to use pyridine, quinoline or triethylamine. ester oxidation can also be done in the absence of a solvent, for example by simply adding the ingredients to the presence of sodium acetate. The reaction temperature, which can also be carried out by heating in the presence of ~+250°, preferably between -20° and +80°. to these temperatures In this case, the esterification reaction is generally completed after 15 minutes to 48 hours.

In detail, the reaction conditions for esterification depend substantially on the nature of the starting materials used. do. That is, the reaction between a free carboxylic acid and a free alcohol or phenol is , generally in the presence of a strong acid such as hydrochloric acid or a mineral acid such as arsenic acid.

A preferred reaction operation is acid anhydride, preferably in a basic medium! ! v or especially acid chloride 0 important bases are reacting the ride with alcohols, especially alkali metals. hydroxides such as sodium hydroxide or potassium hydroxide, alkali metal carbon Acid salts or bicarbonates such as sodium carbonate, sodium bicarbonate, potassium carbonate Also potassium bicarbonate, alkali metal acetates such as sodium acetate or acetic acid. Potassium, alkaline earth metal hydroxides such as calcium hydroxide or organic salts With groups such as triethylamine, pyridine, lutidine, collidine or quinoline be. To carry out yet another preferred esterification, first the alcohol or For example, the phenol can be dissolved in ethanolic sodium hydroxide or potassium hydroxide solution. Sodium alcoholates or ferulates or potassium by treatment with liquid Convert this alcoholate or ferrate to alcoholate or ferrate. Isolate the salt and combine it with sodium bicarbonate or potassium carbonate. , suspended in acetone or polyethyl ether with stirring, then added to diethyl ether. A solution of the acyl chloride or acid anhydride in gel, acetone or DHF is The stake? Add to the tJ solution preferably at a temperature between about -25° and +20°.

The methyl ether compound of formula 1 can be prepared by known etherification reactions, e.g. [In the formula, zA is Kano, OHe, SH or SHe (In the formula, He is a monovalent If the metal cation is Haj, it is a halogen atom, preferably chlorine or bromine. A compound with the formula In the presence of the compound [wherein zB is -CH2-Haj] and a base, rIi can be produced by reaction. The groups R1 and R2 are of formula 1 The reaction conditions for these ether syntheses have the significance shown in the case of this type. These are the conditions commonly used for the reaction. The solvent used must be polar, non- solvents such as dimethyl sulfoxide, N,N-dimethylformamide or or N-methylpyrrolidone, and the base used is preferably a weak acid alkali Potassium metal salts such as sodium acetate, potassium carbonate or sodium carbonate The 0 reaction is carried out at a temperature between 0°C and the boiling point of the lowest boiling component of the reaction mixture. I can. It is particularly advantageous to use temperatures between 60 and 120°C It turned out that.

Some of the starting materials are known, and some are well known in the field of synthetic organic chemistry. It can be produced in the same manner as known compounds.

The liquid-crystalline phase according to the invention is preferably composed of one or more compounds according to the invention. In addition, other components are 2 to 40 @, 4 to 30 at @! ! Contains the ingredients of do. Very particularly preferably, these phases contain one or more of the inventive In addition to the compound, it contains 7 to 2511 components. These ingredients are preferably , nematic or nematic (monotropic or intropic) ) substances, especially azoxybenzene, benzylideneaniline, biphenyl, terphenate phenyl, phenyl or cyclohexyl benzoate, phenyl or cyclohexyl cyclohexanecarboxylate to phenyl or cyclohexylcyclo xyl benzoate, phenyl or cyclohexylcyclohexylcyclohexyl Sancarboxylate, cyclohexylphenylbenzoate, cyclohexane Carboxylate or cyclohexyl cyclohexane carboxylate, Nylcyclohexane, cyclohexylbiphenyl, phenylcyclohexylcyclohexane lohexane, cyclohexylcyclohexane, cyclohexylcyclohexene, cyclohexylcyclohexylcyclohexene, 1,4- and sucyclohexyl Benzene, 4.4"-bis-cyclohexylbiphenyl, phenyl- or cyclo lohexyl-pyrimidine, phenyl- or cyclohexylpyridine, phenyl - or cyclohexyl-dioxane, phenyl- or cyclohexyl-1, 3-dithiazo, 1,2-diphenylethane, 1,2-dicyclohexylethane, 1-phenyl-2-cyclohexylethane, 1-cyclohexyl-2-(4-phenyl) phenylcyclohexyl)-ethane, 1-cyclohexyl-2-biphenylethane , 1-phenyl-2-cyclohexylphenylethane, optionally halogen substituted stilbenes, benzylphenyl ethers, tolanes and substituted cinnamon It is a substance selected from the group of acids, etc.

The 1,4-phenylene group in these compounds may also be fluorinated. .

Of particular interest are compounds of formula 1.2.3.4 and 5.

R'-L-E-R"-L-COO- ER” 2R’-L-00C-E-R” 31’-L-C) 12cHy-E-R” 　　　　　　　　　　　　　　　　　　 　 5 In these formulas l, 2.3.4 and 5, and E are the same or different are mutually independently -Phe-, -Cyc-, -Phe-Phe-, respectively. -Phe-Cyc-+-Cyc-Cyc-1-Pyr-, -Dio-, -G-P hi- and -G-Cyc- and their enantiomers [wherein Phe is unsubstituted] squid or fluorine-substituted-1,4-cyclohexylene or 1,4-cyclohexe nylene, Pyr is pyrimidine-2,5-diyl or pyridine-2,5- diyl, Dio is 1,3-dioxane-2,5-diyl, and G is 2-(trans-1,4-cyclohexyl)-ethyl, pyrimidine-2,5-di yl, pyridine-2,5-diyl or 1,3-dioxane-2,5-diyl is a divalent group from the group consisting of

One of the bases and E is preferably Cyc, Phet or Pyrte. . In the present invention, E is preferably Cyc, Phe or Phe-Cyc. The liquid crystal phase according to formulas 1, 2.3.4 and 5 [wherein and E are selected from the group consisting of CyC, phe and Pyr] one or more components selected from formulas 1.2.3.4 and 1.2.3.4 and at the same time and 5 [wherein the group and one of E consist of Cyc, Phe and Pyr] and the other group is -Phe-Phe-1-Phe- Consisting of Cyc-, -Cyc-Cyc-, -G-Phe- and -G-Cyc- one or more compounds selected from the group and optionally formulas 1.2.3.4 and 5 [wherein the group and E are - Phe-Cyc-, -Cyc-Cyc-, -G-Phe- and -G-Cyc- 111 or its compounds selected from the group consisting of Contains more ingredients.

In a preferred subgroup of compounds of formulas 1, 2.3.4 and 5, Ro and and R" are, independently of each other, alkyl each having up to 8 carbon atoms, is alkenyl, alkoxy, alknyloxy or alkanoyloxy ( Group l), in most of these compounds Ro and Ro are mutually and one of these groups is usually alkyl or alkenyl.

In another preferred subgroup 1 of compounds of formulas 1.2.3.4 and 5, R ” is -CM, -CFs, F, CI or -NCS, while R is group have the meaning indicated in the case of the compounds of formula 1 and are preferably alkyl or Compounds of formulas 1.2.3.4 and 5 are Other variations of the permutations shown in are also tubular. of this type Many substances, or alternatively mixtures of these substances, are commercially available. child All of these substances are prepared using methods known from the literature or similar to these methods. It can be obtained by the following method.

In addition to the components from group I, the liquid-crystalline phase according to the invention preferably also contains components from group I. - Contains ingredients from 12.

These ratios are preferably as follows.

Glue 71: 20-90%, especially 30-90% Group 2: 10-80%, especially 10-50% compounds of the invention and added thereto compounds of groups I and 2 The total percentage of things is 100%.

The liquid crystal phase according to the invention is preferably 1 to 40%, particularly preferably 40% % or more, especially from 45 to 90%, of the compound of the invention. This liquid crystal phase preferably contains 3.4 or 511 compounds of the invention.

The phases according to the invention are produced in a manner customary per se.

Generally, the components are dissolved in each other, preferably at elevated temperatures. 3i! proper accompaniment By means of additives, the liquid crystal phases according to the present invention can be made to can be modified so that it can be used for all types of liquid crystal display elements. Can be done. Such additives are known to those skilled in the art and are [H, elker/R.

Hatz: ) landbook of Liquid Crysta ls % Verlao Cheg+ie.

Weinheil, 1980]. For example, colored game Polychromatic dyes can be added to host the host system or nemate addition of substances that modify the dielectric anisotropy, viscosity and/or orientation of the dicic phase. I can do it.

The following examples are intended to illustrate the invention; Light is not limited.

1, p, = melting point, c, p, = clearing point, in the above and below descriptions , % means % by weight and temperatures are given in all. “By the usual method In the process El'', water is added, the mixture is extracted with methylene chloride, the organic phase is separated, Dry and evaporate the product, then crystallize and/or chromatograph the product. It means more refined.

Additionally, the abbreviations have the following meanings:

C: Crystalline solid state, S nismectic phase (index indicates phase type) ), N: nematic state, Ch: cholesteric phase, isotropic phase, two types of symbols The numbers in between indicate the conversion temperature ('C).

■ indicates the melting point. indicates the clearing point, temperature is in °C.

Example 1 2.3-difluoro-4-ethylphenol [in tetrahydrofuran (THF)] 0-difluoride in the presence of potassium tert-butyrate at -90-100° Reacting lobenzene with butyllithium, ethyl bromide/1,3-dimethyltetra Potassium compounds using hydro-2-<IH)-pyrimidinone (DI4PU) 2,3-difluoroethylbenzene was isolated and remetallized. and react with N-formylpiperidine to form an aldehyde, Baeyer - oxidize it to obtain the formate by the method of V i l I l Jer. can be produced from O-difluorobenzene by subsequent hydrolysis. ] 0.1 mol, potassium carbonate 0.1 mol and trans-4-hentyl- 0.1 mol of 1-bromomethylcyclohexane was added to 100 i of dimethylformamide. Heat at 120° for 15 hours in a microwave oven. Inorganic salts are removed and Pa1 is virtually evaporated to dryness. and the residue is taken up in dichloromethane, washed with water and dried. Contains solvent to remove trans-(4-pentylcyclohexyl)methoxy-2,3 -difluoro-4-ethylbenzene is obtained.

Similarly, the following compounds are produced.

trans-(4-pentylcyclohexyl)methoxy-2,3-difluoro-4 -propylbenzenetrans-(4-pentylcyclohexyl)methoxy-2, 3-difluoro-4-butylbenzene trans-(4-pentylcyclohexyl ) Methoxy-2,3-difluoro-4-pentylbenzene.

trans-(4-pentylcyclohexyl)methoxy-2,3-difluoro-4 -heptylbenzene 2.3-difluoro-4-ethylbenzene trans-(4- butylcyclohexyl)methoxy-2,3-difluoro-4-propylbenzene trans-(4-butylcyclohexyl)methoxy-2,3-difluoro-4- butylbenzenetrans-(4-butylcyclohexyl)methoxy-2,3-di Fluoro-4-pentylbenzenetrans-(4-butylcyclohexyl)meth xy-12,3-difluoro-4-hebutylbenzenetrans-(4-butylsiloxy) (chlorohexyl)methoxy-2,3-difluoro-4-methoxymethylbenzene Lance-(4-butylcyclohexyl)methoxy-2,3-difluoro-4-butyl Do-3-enylbenzene trans-(4-10 pylcyclohexyl)methoxy- 2,3-difluoro-4-ethylbenzene trans-(4-propylcyclohexyl sil)methoxy-2,3-difluoro-4-propylbenzenetrans-(4- propylcyclohexyl)methoxy-2,3-difluoro-4-butylbenzene trans-(4-propylcyclohexyl)methoxytrans-(4-propyl cyclohexyl)methoxy-2,3-difluoro-4-hebutylbenzenetran Su-(4-propylcyclohexyl)methoxy-2,3-difluoro-4-meth oxymethylbenzenetrans-(4-10 pylcyclohexyl)methoxy-2, 3-difluoro-4-boudo-3-enylbenzenetrans-4-(trans-4 -10 pyrcyclohexyl)cyclohexylmethoxy-2,3-difluoro-4 -ethylbenzene trans-4-(trans-4-propylcyclohexyl)cyclohexylmeth xy-2,3-difluoro-4-10pyrubenzene trans-4-(trans-4-10 pylcyclohexyl)cyclohexylmeth Toxy-2,3-difluoro-4-butylbenzene trans-4-(trans-4-10 pylcyclohexyl)cyclohexylmeth xy-2,3-difluoro-4-pentylbenzene trans-4-(trans-4-10 pylcyclohexyl)cyclohexylmeth xy-2,3-difluoro-4-ethylbenzene trans-4-(trans-4-propylcyclohexyl)cyclohexylmeth xy-2,3-difluoro-4-methoxymethylbenzene trans-4-(trans-4-10 pylcyclohexyl)cyclohexylmeth xy-2,3-difluoro-4-budo-3-ethylbenzene Example 2 Lithiation of 0-difluorobenzene and reaction with octanal, dehydration and By hydrogenation 2,3-difluorooctylbenzene was obtained and in the above example 4-octyl-2,3-difluoro Obtain lophenol.

0.1 mole of this phenol, 0 trans-4-butylcyclohexanecarboxylic acid ．． 1 mole of 4-dimethylaminopyridine and 0.01 mole of dichloromethane dicyclohexylcarbodiimide in dichloromethane 30- A 0.1 molar solution was added at 10° with stirring and the mixture was then stirred at room temperature. Stir for 15 hours. The mixture was suction-filtered through silica gel to remove the solvent. and 2,3-difluoro-4-octylphenyltrans-4-butylsic Lohexanoate is obtained as a residue.

Similarly, the following compounds are produced.

2.3-difluoro-4-pentylphenyltrans-4-pentylcyclohexyl Sanoate ■=13, ■c=28.5 2.3-difluoro-4-10pylphenyltrans-4-pentylcyclohexyl Sanoate 2.3-difluoro-4-to-1 tylphenyltrans-4-pentylcyclohexyl Sanoate 2.3-difluoro-4-butoxymethyltrans-4-pentylcyclohexa noate 2.3-difluoro-4-10poxymethyltrans-4-pentylcyclohexyl Sanoate 2.3-difluoro-4-(budo-3-enyl)phenyltrans-4-pentyl Lecyclohexanoate Example 3 2,3-difluoro-4-pentylphenol was obtained in the same manner as in Example 2 and trans-4-(trans-4-pentylcyclohexyl)cyclohexanecal Esterify using bonic acid. By treatment in a conventional manner, 2,3-diflu oro-4-pentylphenyltrans-4-trans-4-pentylcyclohe xyl) cyclohexanoate is obtained.

Similarly, the following compounds are produced.

2.3-difluoro-4-pentylphenyltrans=4-(trans-4-propylene) Lopylcyclohexyl) cyclohexanoate; Tc=180 2.3-difluoro-4-ethylphenyl trans-4-(trans-4-10 Pyrcyclohexyl) cyclohexanoate 2.3-difluoro-4-propylphenyltrans-4-(trans-4-propylphenyl) Lopylcyclohexyl) cyclohexanoate 2,3-difluoro-4-butylphenyltrans-4-(trans-4-10 Pyrcyclohexyl) cyclohexanoate 2.3-difluoro-4-to-1 tylphenyl trans-4-(trans-4-propylene) Lopylcyclohexyl) cyclohexanoate 2.3-difluoro-4-ethylphenyltrans-4-(trans-4-pro Pyrcyclohexyl) cyclohexanoate 2.3-difluoro-4-propylphenyltrans-4-(trans-4-propylphenyl) Lopylcyclohexyl) cyclohexanoate 2.3-difluoro-4-butylphenyl trans-4-(trans-4-pro Pyrcyclohexyl) cyclohexanoate Example 4 Butyllithium/'potassium tertiary butyrate was used in the same manner as in Example 1. 0-difluorobenzene was metallized and reacted with ethoxyethylworomide. 2,3-difluoroethoxyethylbenzene was isolated and purified via aldehyde. 2,3-difluoro-4-ethoxyethylphenol is then obtained. Carbonated power trimethylformamide (DMF) as a solvent. trans-4-(trans-4-pentylcyclohexyl)-1-bromomethylcyclo 1-[trans-4-(trans -4-pentylcyclohexyl)cyclohexyl]methoxy-2,3-difluoro Lo-4-ethoxyethylbenzene is obtained.

Similarly, the following compounds are produced.

1-[trans-4-(trans-4-propylcyclohexyl)cyclohexy ]methoxy-2,3-diflu 1-[trans-4-(trans-4-propyl cyclohexyl)cyclohexyl]methoxy2,3-difluoro-4-ethoxy dimethylbenzene l-[trans-4-(trans-4-propylcyclohexyl)cyclohexy ]methoxy-2,3-difluoro-4-10boxymethylbenzene 1-[-trans-4-(trans-4-propylcyclohexyl)cyclohexyl sil]methoxy-2,3-difluoro-4-butoxymethylbenzene 1-[trans-4-(trans-4-pentylcyclohexyl)cyclohexy ]methoxy-2,3-difluoro-4-ethylbenzene 1-[trans-4-(trans-4-pentylcyclohexyl)cyclohexy ]Methoxy2,3-difluoro-4-propylbenzene 1-[trans-4-(trans-4-pentylcyclohexyl)cyclohexy ]Methoxy2,3-difluoro-4-butylbenzene 1-[trans-4-(trans-4-pentylcyclohexyl)cyclohexy ]methoxy-2,3-difluoro-4-pentylbenzene Example 5 Butyllithium/tetramethylethylenediamine in THF at -70 to -80° Using (THED^). - Lithiation of difluorobenzene and solid state React with carbon dioxide and use lithium alanate to reduce the acid and alcohol by converting to tosylate and reacting with sodium pentalate. 2,3-difluoropentyloxymethylbenzene is obtained. As described in Example 1 In this way, phenol is obtained therefrom and trans-4-10 pylcyclohexyl 2,3-diphthalate is then obtained by esterification using sancarboxylic acid. fluoro-4-pentyloxymethylphenoltrans-4-10bicyclohe Obtain xanoate.

Similarly, the following compounds are obtained.

2.3-difluoro-4-(hex-2-enyl)phenyltrans-4-10 Virucyclohexanoate 2,3-difluoro-4-pentylphenyltrans -4-ethylcyclohexanoate 2.3-difluoro-4-pentylphenyltrans-4-butylcyclohexa noate 2.3-difluoro-4-pentylphenyltrans-4-hebutylcyclohex Sanoate 2.3-difluoro-4-(bent-2-enyl)phenyltrans-4-buty cyclohexanoate 2,3-difluoro-4-(hex-2-enyl)phenyl Nyltrans-4-butylcyclohexanoate 2,3-difluoro-4-pene Tylphenyltrans-4-pentylcyclohexanoate 2.3-difluoro-4-hexylphenyltrans-4-pentylcyclohexyl Sanoate 2.3-difluoro-4-heptylphenyltrans-4-pentylcyclohexyl Sanoate 2.3-difluoro-4-octylphenyltrans-4-pentylcyclohexyl Sanoate Example 6 10 d of a 20% solution of diisobutylaluminum hydride in hexane was added to 0.01 mole of hexane and 5-hexane and the mixture was heated at 50' Warm for an hour.

The mixture was then cooled to 25'' and a 15% J solution of butyllithium in hexane was added. 6.3ij and 30 minutes later 2,3-diphenyl dissolved in tetrahydrofuran 15- fluoro-4-(trans-4-pentylcyclohexyl)methoxybenzylbro Mide is added and the mixture is refluxed for 12 hours. treated with 2,3-difluoro rho-4-(trans-4-pentylcyclohexyl)methoxy-trans-hep To-2-nonylbenzene is obtained.

The required benzyl bromide is 2,3-difluoro-(trans-4-pentyl cyclohexyl)methoxybenzene, lithiation, N-holemylpiveridi reduction of aldehydes using sodium borohydride and benzyl amines. It is produced by the reaction of alcohol with dibromotriphenylphosphorane.

Similarly, the following compounds are produced.

2.3-difluoro-4-(trans-pentylcyclohexyl)methoxypene Toxy-methylbenzene 2,3-difluoro-4-(trans-pentylcyclo hexyl) methoxyhexoxy-methylbenzene 2,3-difluoro-4-(trifluoro) lance-pentylcyclohexyl)methoxy to 1toxymethylbenzene 2.3 -difluoro-4-(trans-pentylcyclohexyl)methoxypentylbe Nzen 2.3-difluoro-4-(trans-pentylcyclohexyl)methoxyhexyl silbenzene 2.3-difluoro-4-(trans-pentylcyclohexyl)methoxyhep tilbenzene The following examples relate to liquid crystal phases according to the invention.

Example A P-trans-4-ethylcyclohexylbenzonitrile 10% P-) Lance-4-butylcyclohexylbenzonitrile 10% 4-cyano-4-fluorophenyl P-ethylbenzoate 5% 4-cyano-4-fluorophenyl p-propyl benzoate 5% 4-cyano-3-fluorophenyl p-pentyl benzoate 5% trans, trans-4-ethoxy-4°-pentylcyclohexylcyclohexyl Sun 15% p-methoxyphenyltrans-4-propylcyclohexanecarboxylate 　5% p-methoxyphenyltrans-4-butylcyclohexanecarboxylate 5% p-ethoxyphenyltrans-4-butylcyclohexanecarboxylate 5% p-Ethoxyphenyltrans-4-pentylcyclohexanecarboxylate 　5% p-methoxyphenyltrans-4-pentylcyclohexanecarboxylate 　5% 2.3-difluoro-4-pentyloxymethylphenyltrans-4-10pi cyclohexanoate 5% p-propylphenyl trans-4-(trans -4-Propylcyclohexyl)-cyclohexanecarboxylate 5% p-pentylphenyl trans-4-(trans-4-10 pylcyclohexyl )-Cyclohexane carboxylate 5% p-propylphenyltrans-4-(trans-4-butylcyclohexyl) -cyclohexanecarboxy2,3-difluoro-4-pentylphenyltran Su-4-(trans-4-pentylcyclohexyl)cyclohexanoate 5 % The liquid crystalline nematic phase consisting of shows a good variety of properties.

international search report international search report EPB9DDiε7 “TE'---1Yu---r) +++++eEmp self-excuse-mm--11-self-Pr1 +y cheer 111 awate-IItkpmmmmm&-+1-mockery--Monichi■鼈鼈鼈黶|1mw 5tdfma% )l-hat wv sg eas*-m uw c god-Pamw CN’rm UD F hw m + 噌l-l gentleman T1w--p-01Fwy II +++ 6s +117-1m tlwm e edition--1-11181or fly-d m

Claims (5)

[Claims] 1. Formula I ▲There are mathematical formulas, chemical formulas, tables, etc.▼I [wherein R1 and R2 each independently represent 1 to 15 C atoms] It is an alkyl group having one CH2 group or two CH2 groups present in this group. Non-adjacent CH groups of -O-, -CO-, -CH=CH- and (or )-C≡C-, m is 1 or 2, and , Q is -CO- or -CH2-]. conductor. 2. formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ A difluorophenol or its reactive derivative with the formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ esterification using cyclohexanecarboxylic acid or its reactive derivatives Or formulas▲Mathematical formulas, chemical formulas, tables, etc.▼ etherification using hydroxyl compounds or their reactive derivatives. A method for producing a 2,3-difluorophenol derivative according to claim 1. 3. 3. Use of a derivative according to claim 1 as a component of a liquid-crystalline phase. 4. wherein at least one component is a derivative according to claim 1. A liquid crystal phase that has at least two types of liquid crystal components. 5. An electro-optical table comprising the liquid crystal phase according to claim 4 as a dielectric material. display element.