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WO1988009322A1 - Derives de cyclobutane - Google Patents

Derives de cyclobutane Download PDF

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Publication number
WO1988009322A1
WO1988009322A1 PCT/EP1988/000427 EP8800427W WO8809322A1 WO 1988009322 A1 WO1988009322 A1 WO 1988009322A1 EP 8800427 W EP8800427 W EP 8800427W WO 8809322 A1 WO8809322 A1 WO 8809322A1
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groups
trans
group
atoms
alkyl
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English (en)
Inventor
Eckehard V. Dehmlow
Rudolf Eidenschink
Ulrich Finkenzeller
Joachim Krause
Eike Poetsch
Stefan Schmidt
Georg Weber
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Merck Patent GmbH
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Merck Patent GmbH
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C07D213/30—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/18—Polycyclic aromatic halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3028—Cyclohexane rings in which at least two rings are linked by a carbon chain containing carbon to carbon single bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3066—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers
    • C09K19/3068—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers chain containing -COO- or -OCO- groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
    • C09K19/3444—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom the heterocyclic ring being a six-membered aromatic ring containing one nitrogen atom, e.g. pyridine
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
    • C09K19/345—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom the heterocyclic ring being a six-membered aromatic ring containing two nitrogen atoms
    • C09K19/3458—Uncondensed pyrimidines

Definitions

  • the invention relates to cyclobutane derivatives of the formula I.
  • R 1 and R 2 each independently
  • Alkyl group with 1-15 C atoms which also contains one or more CH 2 groups -, O atoms,
  • -CHCN- and / or -CH halogen groups can be replaced, two heteroatoms not being directly linked to one another, one of the radicals R 1 and R 2 also H, F, Cl, Br, NCS or CN,
  • a 1 , A 2 and A 3 each independently Q-, "OO ⁇ '0 * an 1,4-cyclohexylene group which is unsubstituted or mono- or polysubstituted by F and / or Cl atoms and / or CH 3 and / or CN groups, in which also one or two non-adjacent CH 2 Groups can be replaced by O atoms and / or S atoms, a 1,4-bicyclo (2,2,2) octylene group or an unsubstituted or substituted by F and / or Cl atoms and / or CH 3 and / or CN groups 1,4-phenylene group , in which one or more CH groups can also be replaced by N,
  • Z 1 and Z 2 each independently of one another -CO-O, -O-CO-, -CH 2 CH 2 -, -OCH 2 -, -CH 2 O-,
  • n 0, 1 or 2
  • n denotes 1 or 2 and at least two of the groups Z 1 and Z 2 are different from the simplification, and / or
  • Tetrahydropyran-2,5-diyl means, and / or at least one of the groups R 1 and R 2 alkyl VCH 2 -,
  • At least one of the groups Z 1 and Z 2 is -C ⁇ C-, and / or
  • radicals R 1 -A 1 and R 2 -A 3 3-halo-4-cyanophenyl, 3,5-dihalo-4-cyanophenyl or
  • 3,4-Dihalogenphenyl means, and / or
  • Z 1 and Z 2 each represent single bonds
  • a 1 is trans-1,4-cyclohexylene and A 2 and A 3 are each independently 1,4-phenylene or trans-1,4-cyclohexylene, and
  • Phe in the following means a 1,4-phenylene group, Cy a 1,4-cyclohexylene group, Dio a 1,3-dioxane-2,5-diyl group, Bi a bicyclo (2,2,2) octylene group, Pyd a pyridine-2,5-diyl group, Pip a piperidine-1,4-diyl group and Pyr a pyrimidine-2,5-diyl group, which groups may be unsubstituted or substituted.
  • Cb means in the following - ⁇ OO or OOC ⁇ -
  • the compounds of the formula I can be used as components of liquid-crystalline phases, in particular for displays which are based on the principle of the twisted cell (TN displays), the guest-host effect, the effect of the deformation of aligned phases or the effect of dynamic scattering .
  • the object of the invention was to find new stable liquid-crystalline or mesogenic compounds which are suitable as components of liquid-crystalline phases.
  • these compounds can serve as base materials from which liquid-crystalline phases are predominantly composed;
  • compounds of the formula I can serve as base materials from which liquid-crystalline phases are predominantly composed;
  • compounds of the formula I can serve as base materials from which liquid-crystalline phases are predominantly composed;
  • compounds of the formula I can serve as base materials from which liquid-crystalline phases are predominantly composed;
  • compounds of the formula I can serve as base materials from which liquid-crystalline phases are predominantly composed;
  • compounds of the formula I can serve as base materials from which liquid-crystalline phases are predominantly composed;
  • compounds of the formula I to liquid-crystalline base materials from other classes of compounds in order, for example, to optimize the dielectric and / or optical anisotropy or other parameters of such a dielectric.
  • the compounds of the formula I are also suitable as intermediates for the preparation of other substances which can be used as constituents of liquid-crystalline phases.
  • the compounds of the formula I are colorless in the pure state and form liquid-crystalline mesophases in a temperature range which is favorable for electro-optical use.
  • the invention thus relates to the compounds of the formula I and to the use of the compounds of the formula I as components of liquid-crystalline phases.
  • the invention further relates to liquid-crystalline phases containing at least one compound of the formula I and liquid-crystal display elements, in particular electro-optical display elements, which contain such phases.
  • the compounds of the formula I accordingly comprise compounds of the subforms I a to I n:
  • the group Cb can either be represented by a radical A 1 , A 2 or A 3 or be part of the radicals R 1 or R 2 .
  • preferred compounds of sub-formula I a include those of sub-formulas I aa to I ae:
  • I a and I b are preferred in the partial forms I c to I n, in which A 1 , A 2 and A 3 are Cy, Phe, Pyd or Pyr.
  • R 1 and / or R 2 if they do not contain the Cb group, preferably mean alkyl, alkoxy, oxaalkyl or perfluoroalkyl, one of the radicals R 1 and R 2 also preferably fluorine or cyano.
  • a 1 , A 2 and A 3 if they do not represent the Cb group, are preferably 1,4-phenylene, 1,4-cyclohexylene, dioxane-2,5-diyl, bicyclo (2,2,2) octylene, Pyridine-2,5-diyl or piperidinediyl, where these groups may be unsubstituted or laterally substituted by halogen atom (s) and / or CN and / or CH 3 groups.
  • a 1 , A 2 and A 3 are particularly preferably 1,4-phenylene, 2-fluoro-, 3-fluoro- or 2,3-difluoro-
  • Z 1 and Z 2 are preferably single bonds, -CH 2 CH 2 -,
  • Cb is preferred the cis-trans isomer mixture or the pure trans form, which is preferred, can be used.
  • R 1 and / or R 2 are an alkyl group with 1-15
  • C atoms mean in which a CH 2 group by ⁇ ⁇ ⁇ y ⁇ or - OOO is replaced and optionally further CH 2 groups by O atoms, -CO groups, -O-CO groups, -CO-O- groups, -O-COO groups, -CHCN and / or -CHHalogen- Group can be replaced, two heteroatoms not being directly linked to one another, these groups are preferably those of the following formulas A to J,
  • R-OOC-Cb-COO-J wherein R is alkyl, preferably straight-chain and having 1 to 9 carbon atoms, p is preferably 1 or 2, particularly preferably 1.
  • Particularly preferred compounds of the formula I are those of the sub-formula II,
  • R 3 and R 4 each independently of one another alkyl, alkoxy, alkoxyalkyl, alkanoyloxy or alkoxycarbonyl each having 1 to 12 carbon atoms or one of the radicals R 3 and R 4 also F, Cl, Br, CN or NCS,
  • n + o mean 0.1 or 2
  • R 4 means F, Cl, Br, CN or NCS.
  • Preferred compounds of the formula II are those of the sub-formulas IIa to IIm:
  • Particularly preferred among the compounds of partial formulas IIa to IIm are those of partial formulas IIa, Ilb, Ilc, IIg Ilh, Ili and IIj.
  • one of the radicals A 2 and A ° is preferably 2,3-
  • R 1 , R 2 , R 3 and / or R 4 are alkyl radicals in which, for example, an (alkoxy or oxaalkyl) CH 2 group can also be replaced by an O atom, they can be straight-chain or branched.
  • Preferred branched radicals R 1 and R 2 are isopropyl
  • 2-methylbutyl, isopentyl ( 3-methylbutyl), 2-methylpentyl, 3-methylpentyl, 2-ethylhexyl, 2-propylpentyl, 2-octyl, isopropoxy, 2-methylpropoxy, 2-methylbutoxy, 3-methylbutoxy, 2-methylpentoxy, 3-methylpentoxy, 2-ethylhexoxy, 1-methylhexoxy, 2-octyloxy, 2-oxa-3-methylbutyl, 3-oxa-4-methylpentyl, 4-methylhexyl, 2-nonyl, 2-decyl, 2-dodecyl, 6- Methyloctoxy, 6-methyloctanoyloxy, 5-methylheptyloxycarbonyl, 2-methylbutyryloxy, 3-methylvaleryloxy, 4-methylhexanoyloxy, 2-chloropropionyloxy, 2-chloro-3-methylbutyryloxy, 2-chloro-4-methylvaleryloxy, 2-chlor
  • the formulas I and II include racemates and also optically active enantiomers and enantiomer mixtures.
  • the compounds of the formulas I and II are prepared by methods known per se, as described in the literature (for example in the standard works such as Houben Weyl, Methods of Organic Chemistry, Georg-Thieme-Verlag, Stuttgart), namely under Reaction conditions which are known and suitable for the reactions mentioned. It is also possible to use variants which are known per se and are not mentioned here.
  • the starting materials can also be formed in situ in such a way that they are not isolated from the reaction mixture, but instead are immediately reacted further to give the compounds of the formulas I, II and III.
  • the starting materials containing the Cb group are either known (cf. B. Maillard et al. J. Chem. Soc, Perkin Trans. II, 1985, 443; M. Avram et al., Chem. Ber. 90, 1424 (1957 ); KB Wiberg et al., Tetrahedron 21, 2749 (1965); JA Caputo et al., J. Org. Chem. 33, 1959 (1968); NL Allinger et al., J. Org. Chem. 30, 1945 (1965)) or in analogy to known starting materials in a manner known per se.
  • compounds of the formula alkyl-Cb- (CH 2 ) p -X where p is 0 or a multiple of 1 and X is, for example, OH, COOH, halogen or an organometallic radical, are obtainable by customary malonate synthesis starting from 2-alkyl- 1,3-dihalopropanes and possibly subsequent conversion reactions or chain extension through the sequence reduction, bromination, conversion into the nitrile, saponification to carboxylic acid, reduction etc.
  • Suitable reactive derivatives of the carboxylic acids mentioned are, in particular, the acid halides, especially the chlorides and bromides, furthermore the anhydrides, azides or esters, in particular alkyl esters with 1-4 C atoms in the alkyl group.
  • Suitable reactive derivatives of the alcohols or phenols mentioned are in particular the corresponding metal alcoholates or phenolates, preferably an alkali metal such as Na or K.
  • the esterification is advantageously carried out in the presence of an inert solvent.
  • ethers such as diethyl ether, di-n-butyl ether, THF, dioxane or anisole, ketones such as acetone, butanone or cyclohexanone, amides such as DMF or phosphoric acid hexamethyltriamide, hydrocarbons such as benzene, toluene or xylene, halogenated hydrocarbons such as carbon tetrachloride or tetrachlorethylene and Sulfoxides such as dimethyl sulfoxide or sulfolane.
  • ethers such as diethyl ether, di-n-butyl ether, THF, dioxane or anisole
  • ketones such as acetone, butanone or cyclohexanone
  • amides such as DMF or phosphoric acid hexamethyltriamide
  • hydrocarbons such as benzene, tol
  • Water-immiscible solvents can at the same time advantageously be used for azeotropically distilling off the water formed during the esterification.
  • an excess of an organic base for example pyridine, quinoline or triethylamine, can also be used as a solvent for the esterification.
  • the esterification can also be carried out in the absence of a solvent, for example by simply heating the components in the presence of sodium acetate.
  • the reaction temperature is usually between -50 ° and + 250 °, preferably between -20 ° and + 80 °. At these temperatures, the esterification reactions are usually complete after 15 minutes to 48 hours. In particular, the reaction conditions for the esterification largely depend on the nature of the starting materials used.
  • a free carboxylic acid is usually reacted with a free alcohol or phenol in the presence of a strong acid, for example a mineral acid such as hydrochloric acid or sulfuric acid.
  • a preferred reaction mode is the reaction of an acid anhydride or in particular an acid chloride with an alcohol, preferably in a basic medium, the bases being, in particular, alkali metal hydroxides such as sodium or potassium hydroxide, alkali metal carbonates or hydrogen carbonates such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate or potassium hydrogen carbonate, alkali metal acetates such as Sodium or potassium acetate, alkaline earth metal hydroxides such as calcium hydroxide or organic bases such as triethylamine, pyridine, lutidine, collidine or quinoline are of importance.
  • a further preferred embodiment of the esterification is that the alcohol or the phenol is first converted into the sodium or potassium alcoholate or phenolate, for example by treatment with ethanolic sodium or potassium hydroxide solution, this is isolated and together with sodium bicarbonate or potassium carbonate with stirring in acetone or suspended in diethyl ether and added a solution of the acid chloride or anhydride in diethyl ether, acetone or DMF to this suspension, advantageously at temperatures between about -25 ° and + 20 °.
  • 1,3-dioxane-2,5-diyl group or a 1,3-dithiane-2,5-diyl group means) are expediently by reaction of a corresponding aldehyde with a corresponding 1,3-
  • Diol or a corresponding 1,3-dithiol (or one of its reactive derivatives) prepared preference as in the presence of an inert solvent such as benzene or toluene and / or a catalyst such as a strong acid such as sulfuric acid, benzene or p-toluenesulfonic acid, at temperatures between about 20 ° and about 150 °, preferably between 80 ° and 120 °.
  • Acetals are primarily suitable as reactive derivatives of the starting materials.
  • aldehydes 1,3-diols and 1,3-dithiols mentioned and their reactive derivatives are known, and in some cases they can be prepared without difficulty from standard compounds of organic chemistry from compounds known from the literature.
  • the aldehydes can be obtained by oxidation of corresponding alcohols or by reduction of corresponding carboxylic acids or their derivatives, the diols by reduction of corresponding diesters, and the dithiols by reaction of corresponding dihalides with NaSH.
  • Corresponding acid amides can be dehydrated to produce nitriles of the formulas I and II (in which R 1 or R 2 is CN).
  • the amides can be obtained, for example, from corresponding esters or acid halides by reaction with ammonia.
  • suitable water-releasing agents are inorganic acid chlorides such as SOCl 2 , PCl 5 , POCl 3 , SO 2 Cl 2 , COCl 2 , furthermore P 2 O 5 , P 2 S 5 , AlCl 3 (for example as a double compound with NaCl), aromatic sulfonic acids and Sulfonic acid halides.
  • nitriles of the formula I mentioned above can also be reacted with sulfamide, advantageously in an inert solvent such as tetramethyl sulfone at temperatures between about 80 ° and 150 °, preferably at 120 °. After the usual work-up, the nitriles can be isolated directly.
  • Alkyl group means in which one or two CH 2 groups are replaced by O atoms, or R 3 and / or R 4 is an alkoxy and / or alkoxyalkyl group, and / or in which Z 1 and / or Z 2 is an -OCH 2 —or a —CH 2 O group) can be obtained by etherification of corresponding hydroxyl compounds, preferably corresponding phenols, the hydroxyl compound advantageously first being converted into a corresponding metal derivative, for example by treatment with NaH, NaNH 2 , NaOH, KOH, Na 2 CO 3 or K 2 CO 3 is converted into the corresponding alkali metal alcoholate or alkali metal phenolate.
  • R 1 or R 2 or R 3 or R 4 is CN and / or A 1 and / or A 2 and / or A 3 is substituted by at least one CN group) corresponding chlorine or bromine compounds of the formula I or II are reacted with a cyanide, advantageously with a metal cyanide such as NaCN, KCN or Cu 2 (CN) 2 , for example in the presence of pyridine in an inert solvent such as DMF or N-methylpyrrolidone at temperatures between 20 ° and 200 °.
  • a metal cyanide such as NaCN, KCN or Cu 2 (CN) 2
  • Chlorine compounds of the formulas I and II can be corresponding aniline derivatives with sodium nitrite and either with tetrafluoroboric acid (to introduce an F atom) or with copper (I) chloride (to introduce a Cl atom) to the diazonium salts, which are then thermally decomposed at temperatures of 100 ° -140 °.
  • the compounds of the formula I or II in which one of the groups A 1 , A 2 or A 3 is 2,3-difluoro-1,4-phenylene can, starting from 1,2-difluorobenzene, by ortho-metalation and subsequent reaction with the corresponding electrophiles are produced.
  • Suitable reagents for ortho-metalation are e.g. Phenyllithium, lithium tetramethylpiperidide, n-, sec- or tert-butyllithium. These are at temperatures from -120 ° C to +50 ° C in an inert solvent, optionally with the addition of complexing agents, such as.
  • TEDA Tetramethylethylenediamine
  • HMPT hexamethylphosphoric triamide
  • DMPH or DMEH dimethylethyleneurea
  • transmetalating reagents such as potassium tert-butoxide, zinc bromide, or chlorotrialkyl orthotitanate with the 1,2-di-fluorobenzene 3-difluoro-1-alkyl (or -1-alkoxy) benzene implemented.
  • Suitable electrophiles are, for example, aldehydes, ketones, nitriles, epoxies, alkyl or alkyl halides, carboxylic acid derivatives such as esters, anhydrides, carbon dioxide or trialkyl borate.
  • the liquid-crystalline phases according to the invention consist of 2 to 15, preferably 3 to 12 components, including at least one compound of the formula I, II or III.
  • the other constituents are preferably selected from the nematic or nematogenic substances, in particular the known substances, from the classes of azoxybenzenes, benzylidene anilines, biphenyls, terphenyls, phenyl- or cyclohexylbenzoates, cyclohexanecarboxylic acid phenyl- or cyclohexyl esters, phenylcyclohexanes, cyclohexylbiphenyl, cyclohexylhexyl, cyclohexylhexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclo
  • L and E each a carbo- or heterocyclic ring system from that of 1,4-disubstituted benzene and cyclohexane rings, 4,4'-disubstituted biphenyl, phenylcyclohexane and cyclohexylcyclohexane systems, 2,5-disubstituted pyrimidine and 1,3-dioxane rings , 2,6-disubstituted naphthalene, di- and tetrahydronaphthalene,
  • CH N- -COO-Phe-COO or a CC single bond
  • Y halogen preferably chlorine, or CN
  • R 'and R are different from one another, one of these radicals usually being an alkyl or alkoxy group.
  • substituents usually being an alkyl or alkoxy group.
  • the phases according to the invention contain about 0.1 to 99, preferably 10 to 95%, of one or more compounds of the formula I or II.
  • dielectrics according to the invention containing 0.1 to 40, preferably 0.5 to 30%, of one or more compounds of the formula I or II.
  • optically active compounds of the formula I or II are also suitable as components of chirally-smectic liquid-crystalline phases.
  • these phases contain at least one other component with negative or small positive dielectric anisotropy in the achiral base mixture.
  • the dielectrics according to the invention are produced in a conventional manner. As a rule, the components are dissolved in one another, expediently at elevated temperature.
  • liquid-crystalline dielectrics according to the invention can be modified so that they can be used in all types of liquid-crystal display elements which have hitherto become known.
  • conductive salts preferably ethyl dimethyl dodecyl ammonium 4-hexyloxybenzoate, tetrabutylammonium tetraphenylboranate or complex salts of crown ethers (see, for example, I. Haller et al., Mol. Cryst. Liq. Cryst. Volume 24, pages 249-258 (1973)) to improve the conductivity, dichroic dyes for producing colored guest-host systems or substances for changing the dielectric anisotropy, the viscosity and / or the orientation of the nematic phases are added.
  • Such substances are e.g. in DE-OS 22 09 127, 22 40 854, 23 21 632, 23 38 281, 24 50 088, 26 37 430, 28 53 728 and 29 02 177.
  • the Grignard reagent is prepared by dropwise addition to 0.49 g of Mg chips in 10 ml of tetrahydrofuran .
  • Pd ° catalyst prepared from 0.74 g of 1,1'-bis (diphenylphosphino) ferrocene palladium dichloride (dppf) and 5.62 g (0.02 mol) of 4-bromo-1- (Trans-4'-propylcyclohexyl- (1)) - benzene in 10 ml of tetrahydrofuran and heated to gentle reflux for 16 hours. It is evaporated, mixed with diethyl ether and dilute aqueous ammonium chloride solution and the ethereal extract is chromatographed on silica gel after drying with hexane. The isomeric 1- (3-methylcyclobutyl) -2- [4- (trans-4-propylcyclohexyl) phenyl] ethane is obtained in a mixture.
  • the Grignard reagent is prepared from 5.62 g (0.02 mol) of 4-bromo-1- (trans-4'-propylcyclohexyl- (l)) - benzene in 10 ml of tetrahydrofuran with 0.49 g of magnesium shavings, as in Example 1 described, with reduced dppf catalyst and 3.54 g of 1-bromo-3-propylcyclobutane (L. Beard and A. Burger, J. Org. Chem.
  • trans-1,3-cyclobutanedicarboxylic acid Esterification of trans-1,3-cyclobutanedicarboxylic acid with p-n-pentylphenol analogously to Example 5 gives trans-1,3-cyclobutanedicarboxylic acid di (p-pentylphenyl ester), mp 74 °, K. 30 ° (monotropic).
  • trans-3- (p-propylphenyl) cyclobutane carboxylic acid prepared by coupling p-propyl bromobenzene with ethyl 3-iodocyclobutane carboxylate analogously to Example 4 and subsequent saponification with alcoholic potassium hydroxide solution
  • 1.25 g of 4-dimethylaminopyridine and 11, 2 g of p-fluorophenol in 150 ml of dichloromethane and 21 g of dicyclohexylcarbodiimide in 30 ml of dichloromethane are added dropwise and the mixture is subsequently stirred at room temperature for 15 hours.
  • trans-3- (p-propylphenyl) cyclobutanecarboxylic acid p-fluorophenyl ester
  • 0.1 mol of methoxy-2,3-difluorobenzene is metalated at -70 ° C. in 200 ml of THF in the presence of 0.1 mol of TMEDA with 0.105 mol of a 1.6 N solution of BuLi in hexane and after 3 hours at -70 ° C with 0.1 mol of 4-heptylcyclohexanone.
  • the reaction mixture is allowed to warm to room temperature, hydrolyzed with saturated NH 4 Cl solution, extracted with methyl tert-butyl ether and worked up as usual.
  • the product mixture is taken up in toluene and boiled in a water separator in the presence of 2 g of p-toluenesulfonic acid.
  • the toluene solution is then washed neutral with water, dried and mixed with 0.2 mol of 2,3-dichloro-5,6-dicyanobenzoquinone.
  • the mixture is boiled under reflux for 3 hours and the cooled reaction mixture is then passed over a short column of silica gel.
  • the product is purified by crystallization. 4'-Heptyl-2,3-di-fluoro-4-methoxybiphenyl is obtained.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Liquid Crystal Substances (AREA)
  • Pyridine Compounds (AREA)
  • Pyrane Compounds (AREA)
  • Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)

Abstract

Dérivés de cyclobutane de formule (I), R1-A1-Z1-A2-(Z2-A3)n-R2, qui conviennent comme constituants de phases cristallines liquides.
PCT/EP1988/000427 1987-05-23 1988-05-18 Derives de cyclobutane Ceased WO1988009322A1 (fr)

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DE19873717484 DE3717484A1 (de) 1987-05-23 1987-05-23 Cyclobutanderivate
DEP3717484.3 1987-05-23

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0332006A1 (fr) * 1988-03-10 1989-09-13 MERCK PATENT GmbH Composition liquide cristalline smectique
EP0332007A1 (fr) * 1988-03-10 1989-09-13 MERCK PATENT GmbH Dérivés de la difluoro-2,3 hydroquinone
WO1989008688A1 (fr) * 1988-03-10 1989-09-21 MERCK Patent Gesellschaft mit beschränkter Haftung Derives de l'acide 2,3-difluorobenzoique
WO1989008687A1 (fr) * 1988-03-10 1989-09-21 MERCK Patent Gesellschaft mit beschränkter Haftung Difluoro-2,3 biphenyles
WO1992016483A1 (fr) * 1991-03-16 1992-10-01 MERCK Patent Gesellschaft mit beschränkter Haftung Derives de cyclobutane de methylene
WO1994012455A1 (fr) * 1992-11-21 1994-06-09 Merck Patent Gmbh Derives de cyclobutane-benzol
WO2007033732A1 (fr) * 2005-09-19 2007-03-29 Merck Patent Gmbh Composes de cyclobutane et de spiro[3.3]heptane
CN100400485C (zh) * 2002-12-02 2008-07-09 默克专利股份有限公司 环丁烷衍生物
US7888519B2 (en) 2003-05-27 2011-02-15 Merck Patent Gesellschaft Pyran compound or at least one derivative thereof

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4408418C2 (de) * 1994-03-12 2003-04-24 Merck Patent Gmbh Flüssigkristalline Spiroverbindungen
DE19945889A1 (de) * 1998-09-29 2000-04-27 Merck Patent Gmbh Flüssigkristalline Verbindungen und Flüssigkristallines Medium
WO2004026991A1 (fr) * 2002-08-20 2004-04-01 Merck Patent Gmbh Milieu de cristaux liquides

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2155946A (en) * 1984-03-14 1985-10-02 Secr Defence Substituted cyclobutanes and their use in liquid crystal materials
JPS62201843A (ja) * 1986-02-28 1987-09-05 Kanto Kagaku Kk １，３−ジ置換シクロブタン化合物

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2155946A (en) * 1984-03-14 1985-10-02 Secr Defence Substituted cyclobutanes and their use in liquid crystal materials
JPS62201843A (ja) * 1986-02-28 1987-09-05 Kanto Kagaku Kk １，３−ジ置換シクロブタン化合物

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Chemical Abstracts, Band 109, Nr. 2, 11. Juli 1988, (Columbus, Ohio, US) siehe Seite 569, Zusammenfassung 14925m & JP-A-62201843 (KANTO CHEMICAL CO. INC.) 5. September 1987 *
Molecular Crystals & Liquid Crystals, Band 147, Juni 1987 (Montreux, CH) L.K.M. Chan et al.: "Synthesis and liquid crystal properties of compounds incorporating cyclobutane, spiro(3.3)heptane and dispiro(3.1.3.1)decane rings", Seiten 113-139 *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0332006A1 (fr) * 1988-03-10 1989-09-13 MERCK PATENT GmbH Composition liquide cristalline smectique
EP0332007A1 (fr) * 1988-03-10 1989-09-13 MERCK PATENT GmbH Dérivés de la difluoro-2,3 hydroquinone
WO1989008690A1 (fr) * 1988-03-10 1989-09-21 MERCK Patent Gesellschaft mit beschränkter Haftung Phase de cristaux liquides smectique
WO1989008688A1 (fr) * 1988-03-10 1989-09-21 MERCK Patent Gesellschaft mit beschränkter Haftung Derives de l'acide 2,3-difluorobenzoique
WO1989008687A1 (fr) * 1988-03-10 1989-09-21 MERCK Patent Gesellschaft mit beschränkter Haftung Difluoro-2,3 biphenyles
WO1989008637A1 (fr) * 1988-03-10 1989-09-21 MERCK Patent Gesellschaft mit beschränkter Haftung Derives de 2,3-difluorohydroquinone
WO1992016483A1 (fr) * 1991-03-16 1992-10-01 MERCK Patent Gesellschaft mit beschränkter Haftung Derives de cyclobutane de methylene
WO1994012455A1 (fr) * 1992-11-21 1994-06-09 Merck Patent Gmbh Derives de cyclobutane-benzol
US5445764A (en) * 1992-11-21 1995-08-29 Merck Patent Gesellschaft Mit Beschrankter Haftung Cyclobutane benzene derivatives
CN100400485C (zh) * 2002-12-02 2008-07-09 默克专利股份有限公司 环丁烷衍生物
US7888519B2 (en) 2003-05-27 2011-02-15 Merck Patent Gesellschaft Pyran compound or at least one derivative thereof
WO2007033732A1 (fr) * 2005-09-19 2007-03-29 Merck Patent Gmbh Composes de cyclobutane et de spiro[3.3]heptane
US7744968B2 (en) 2005-09-19 2010-06-29 Merck Patent Gmbh Cyclobutane and spiro[3.3]heptane compounds

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JPH01503387A (ja) 1989-11-16
DE3717484A1 (de) 1988-12-01
DE3890440D2 (en) 1989-06-15

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