WO1989010356A1 - Pyridine derivatives - Google Patents

Pyridine derivatives Download PDF

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Publication number
WO1989010356A1
WO1989010356A1 PCT/EP1989/000408 EP8900408W WO8910356A1 WO 1989010356 A1 WO1989010356 A1 WO 1989010356A1 EP 8900408 W EP8900408 W EP 8900408W WO 8910356 A1 WO8910356 A1 WO 8910356A1
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Prior art keywords
trans
ester
pyridin
ethyl
acid
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PCT/EP1989/000408
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German (de)
French (fr)
Inventor
Andreas WÄCHTLER
Joachim Krause
Volker Reiffenrath
Ulrich Finkenzeller
Thomas Geelhaar
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MERCK Patent Gesellschaft mit beschränkter Haftung
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Publication of WO1989010356A1 publication Critical patent/WO1989010356A1/en
Priority to KR1019890702461A priority Critical patent/KR900700453A/en

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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
    • C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • 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
    • C07D213/60—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • 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
    • C07D213/60—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/65—One oxygen atom attached in position 3 or 5
    • 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
    • C07D213/60—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/70—Sulfur atoms
    • 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
    • C07D213/60—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
    • 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

Definitions

  • the invention relates to pyridine derivatives of the formula I.
  • R 1 is an alkyl radical with 1-15 C atoms or an alkenyl radical with 2-15 C atoms, in which
  • a CH 2 group can also be replaced by -O-, -CO-, -O-CO- or -CO-O-,
  • R 2 ei.ne of the meanings of R 1 or an optically active radical
  • R 3 is an alkyl group other than Y with 1 to
  • Cyc in the following means a 1,4-cyclohexylene group, Phe a 1,4-phenylene group and PheX one or more times by F and / or Cl atoms and / or CH 3 , - and / or CN groups substituted 1,4-phenylene group.
  • 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 ECB effect, the effect of the deformation Phases based on the effect of dynamic scattering or the SSFLC principle, or also for TFT or STN mixtures.
  • liquid crystalline phases are required which have very low viscosities and particularly advantageous elastic constants.
  • the object of the invention was to find new stable liquid-crystalline or mesogenic compounds which are suitable as components of liquid-crystalline phases.
  • the compounds of the formula I are particularly suitable as components of liquid-crystalline phases. In particular, they can be used to produce stable liquid-crystalline phases for high-information displays with short switching times. Furthermore, certain compounds of formula I are also suitable as components of ferroelectric liquid crystal phases, for example for displays based on the SSFLC principle. With the provision of the compounds of the formula I, the range of liquid-crystalline substances which are suitable for the preparation of liquid-crystalline mixtures from various technical aspects is also very broadly widened.
  • the compounds of formula I have a wide range of uses. Depending on the choice of the substituents, these compounds can serve as base materials from which liquid-crystalline phases are predominantly composed; However, it is also possible to add compounds of the formula I to liquid-crystalline base materials from other classes of compounds in order, for example, to optimize the electrical and / or optical anisotropy or other parameters of such a dielectric.
  • the compounds of 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. They are very stable chemically, thermally and against light.
  • 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 which contain such phases.
  • R 1 , Z 1 , n, Z, A, A 1 , m and R 2 have the meaning given, unless expressly stated otherwise.
  • the compounds of the formula I accordingly comprise compounds of the partial formula Ia (with two rings), Ib to Id (with three rings) and Ie to If (with four rings):
  • those of the sub-formulas Ia, Ib, Ic and Id are particularly preferred.
  • the preferred compounds of sub-formula Ia include those of sub-formulas Iaa to Iah:
  • the preferred compounds of sub-formula Ib include those of sub-formulas Iba to Ibj:
  • those of the sub-formulas Ibc, Ibd, Ibe, Ibh, Ibi and Ibj are particularly preferred.
  • the preferred compounds of sub-formula Ic include those of sub-formulas Ica to Icj:
  • the preferred compounds of sub-formula Id include those of sub-formulas Ida to Idd:
  • Z 1 preferably denotes a single bond
  • R 1 and R 2 are preferably alkyl, -O-alkyl, -OCO-
  • Alkyl or oxaalkyl Alkyl or oxaalkyl.
  • R 1 is particularly preferably alkyl and R 2 is alkyl, alkoxy or -OCO-alkyl.
  • alkenyl groups are preferred for R 1 and / or R 2 .
  • Substances of the formula I in which R 2 is an optically active radical of the formula are also particularly preferred
  • optically active residues is very particularly preferred:
  • Z 1 means -CH 2 CH 2 - or a single bond, preferably a single bond.
  • Cyc means a trans-1,4-cyclohexylene group
  • a 1 -O-CO-Phe.
  • Phe is preferably an unsubstituted 1,4-phenylene group, but can also be substituted one or more times, preferably once or twice, by F, Cl, CH 3 and / or CN. Mono substitution by fluorine is preferred, and di-substitution in the 2,3-position by fluorine is particularly preferred.
  • n is preferably 1 and m is preferably 0.
  • alkyl radicals in the groups R 1 and / or R2 can be straight-chain or branched. They are preferably straight-chain, have 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms and accordingly preferably denote methyl,
  • R 1 and / or R 2 are alkyl radicals in which one
  • Alkoxy or "Oxaalkyl” or two (“Alkoxyalkoxy” or “Dioxaalkyl”) CH2 groups are replaced by O atoms, they can be straight-chain or branched. They are preferably straight-chain, have 2, 3, 4, 5,
  • Branched groups of this type usually contain no more than one chain branch.
  • R 1 and / or R2 represent an alkenyl radical, this can be straight-chain or branched. It is preferably straight-chain and has 2 to 10 carbon atoms. Accordingly, it preferably means vinyl, prop-1- or prop-2-enyl, but-1-, 2- or but-3-enyl, pent-1-, 2-, 3- or pent-4-enyl, hex- 1-, 2-, 3-, 4- or hex-5-enyl, hept-1-, 2-, 3-, 4-, 5- or hept-6-enyl, oct-1-, 2-, 3 -, 4-, 5-, 6- or oct-7-enyl, non-1-, 2-, 3-, 4-, 5-, 6-, 7- or non-8-enyl, dec-1- , 2-, 3-, 4-, 5-, 6-, 7-, 8- or Dec-9-enyl.
  • J6 0149564 encompasses the general formula, no explicit examples are available.
  • JG 0149564 has a melting point of 85.1 ° and a clearing point of 92.9 °. In contrast, the
  • the mesophase range is thus 10 to 12 times wider for the compounds according to the invention than for the compounds described above.
  • the compounds Ig according to the invention are therefore much more suitable as components of liquid-crystalline phases.
  • the compounds of formula I 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), and under reaction conditions which are suitable for the implementations mentioned are known and suitable. One can make use of variants which are known per se and are not mentioned here.
  • Esters of the formula I can be obtained by esterifying corresponding carboxylic acids (or their reactive derivatives) with correspondingly 2-substituted pyridin-5-ols (or the reactive derivatives).
  • Suitable reactive derivatives of the carboxylic acids mentioned are, in particular, the acid halides, especially the chlorides and bromides, furthermore the anhydrides, azides and esters, in particular alkyl esters with 1-4 C atoms in the alkyl group.
  • Suitable reactive derivatives of the pyridin-5-ols mentioned are in particular the corresponding metal alcoholates, preferably an alkali metal such as Na or K.
  • the reactions are preferably carried out in toluene / pyridine, starting from the acid chloride, or also with DCC (dicyclohexylcarbodiimide) in the presence of catalytic amounts of DMAP (dimethylaminopyridine), starting from the carboxylic acid itself.
  • DCC diclohexylcarbodiimide
  • DMAP dimethylaminopyridine
  • Ethers of the formula I can be prepared by etherification of corresponding hydroxyl compounds, the hydroxyl compounds first being expediently 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 transferred.
  • This metal derivative can then be reacted with the corresponding alkyl halide, sulfonate or dialkyl sulfonate, advantageously in an inert solvent such as acetone, 1,2-dimethoxyethane, DMF or dimethyl sulfoxide or even an excess of aqueous or aqueous-alcoholic NaOH or KOH at temperatures between about 20 ° and 100 °.
  • the ethane derivatives can also be prepared by hydrogenating the corresponding alkenes.
  • the hydrogenations can be carried out by generally known methods.
  • the starting compounds are either known or can be prepared by simple reactions known from the literature.
  • the liquid-crystalline media according to the invention preferably contain 2 to 40, in particular 4 to 30, components as further constituents. These media very particularly preferably contain 7 to 25 components in addition to one or more compounds according to the invention.
  • These further constituents are preferably selected from nematic or nematogenic (monotropic or isotropic) substances, in particular substances from the classes of azoxybenzenes, benzylidene anilines, biphenyls, terphenyls, phenyl- or cyclohexylbenzoates, cyclohexane-carboxylic acid phenyl or cyclohexyl esters, phenyl or cyclohexyl esters cyclohexylbenzoic acid, phenyl or cyclohexyl esters of cyclohexylcyclohexanecarboxylic acid, cyclohexylphenyl of benzoic acid, of cyclohehexylphenyl of be
  • L and E which may be the same or different, each independently represent a bivalent radical from the group consisting of -Phe-, -Cyc-, -Phe-Phe-, -Phe- Cyc-, -Cyc-Cyc-, -Pyr-, -Dio-, -G-Phe- and -G-Cyc- as well as their mirror images formed group, whereby Phe unsubstituted or substituted by fluorine-substituted 1,4-phenylene, Cyc- 1,4-cyclohexylene or 1,4-cyclohexenylene, pyr pyrimidine-2,5-diyl or pyridine-2,5-diyl, dio 1,3-dioxane-2,5-diyl and G 2- (trans-1, 4-Cyclohexyl) ethyl, pyrimidine-2,5-diyl, pyridine-2
  • one of the radicals L and E is Cyc, Phe or Pyr.
  • E is preferably Cyc, Phe or Phe-Cyc.
  • the media according to the invention preferably contain one or more components selected from the compounds of the formulas 1, 2, 3, 4 and 5, in which L and E are selected from the group Cyc, Phe and Pyr and at the same time one or more components selected from the compounds of Formulas 1, 2, 3, 4 and 5, in which one of the radicals L and E is selected from the group Cyc, Phe and Pyr and the other radical is selected from the group -Phe-Phe-, -Phe-Cyc-, - Cyc-Cyc-, -G-Phe- and -G-Cyc-, and optionally one or more components selected from the compounds of the formulas 1, 2, 3, 4 and 5, in which the radicals L and E are selected from the group -Phe-Cyc-, -Cyc-Cyc-, -G-Phe- and -G-Cyc
  • R 'and R "in the compounds of sub-formulas 1a, 2a, 3a, 4a and 5a each independently represent alkyl, alkenyl, alkoxy, alkenyloxy or alkanoyloxy having up to 8 carbon atoms. Most of these compounds are R1 and R" different from one another, one of these radicals usually being alkyl or alkenyl.
  • R in the compounds of sub-formulas 1b, 2b, 3b, 4b and 5b, R "means -CN, -CF 3 , F, Cl or -NCS; R has the meaning given for the compounds of sub-formulas Ia to 5a and is preferably alkyl or Alkenyl, but also other variants of the proposed substituents in the compounds of the formulas 1, 2, 3, 4 and 5 are common. Many such substances or mixtures thereof are commercially available. All of these substances are obtainable by methods known from the literature or in analogy thereto .
  • the media according to the invention preferably also contain components from the group of compounds 1b, 2b, 3b, 4b and 5b (group 2), the proportions of which are preferably as follows are:
  • Group 1 20 to 90%, in particular 30 to 90%
  • group 2 10 to 80%, in particular 10 to 50%
  • the media according to the invention preferably contain 1 to 40%, particularly preferably 5 to 30%, of compounds according to the invention. Also preferred are media containing more than 40%, in particular 45 to 90% of compounds according to the invention.
  • the media preferably contain three, four or five compounds according to the invention.
  • the media according to the invention are produced in a conventional manner.
  • the components are dissolved in one another, advantageously at elevated temperature.
  • the liquid-crystalline phases 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.
  • Such additives are known to the person skilled in the art and are described in detail in the literature (H. Kelker / R. Hatz, Handbook of Liquid Crystals, Verlag Chemie, Weinheim, 1980).
  • pleochroic dyes can be added to produce colored guest-host systems or substances to change the dielectric anisotropy, the viscosity and / or the orientation of the nematic phases.
  • K crystalline solid state
  • S smectic phase (the index indicates the phase type)
  • N nematic state
  • Ch cholesteric phase
  • I isotropic phase.
  • trans-4- (trans-4-pentylcyclohexyl) cyclohexane carboxylic acid (2-pentylpyridin-5-yl) ester with K 31 ° S B 181 ° N 183.1 ° I is obtained.
  • trans-4- (trans 4-ethylcyclohexyl) cyclohexanecarboxylic acid (2-heptyl-pyridin-5-yl) ester trans-4- (trans-4-propylcyclohexyl) cyclohexanecarboxylic acid (2-heptyl-pyridin-5-yl) ester trans-4- (trans-4-butylcyclohexyl) cyclohexanecarboxylic acid (2-heptyl-pyridin-5-yl) ester trans-4- (trans-4-pentylcyclohexyl) cyclohexanecarboxylic acid (2-heptyl-pyridin-5-yl) ester trans-4- (trans-4-hexylcyclohexyl) cyclohexanecarboxylic acid (2-heptyl-pyridin-5-yl) ester trans-4- (trans-4-hexylcyclohexyl) cyclohe
  • trans-4-ethylcyclohexane carboxylic acid (2-methyl-pyridin-5-yl) ester mp. 34 ° trans-4-propylcyclohexane carboxylic acid (2-methyl-pyridin-5-yl) ester, mp. 40 °, cp. 0 ° trans-4-butylcyclohexane carboxylic acid (2-methyl-pyridin-5-yl) ester, mp. 41 °, cp. 20 ° trans-4-pentylcyclohexane carboxylic acid (2-methyl-pyridin-5-yl) ester, mp. 48 °, cp.
  • trans-4-ethylcyclohexanecarboxylic acid (2-hexyl-pyridin-5-yl) ester trans-4-propylcyclohexanecarboxylic acid (2-hexyl-pyridin-5-yl) ester trans-4-butylcyclohexanecarboxylic acid (2-hexyl-pyridine) - 5-yl) -ester trans-4-pentylcyclohexanecarboxylic acid- (2-hexyl-pyridine-5-yl) -ester trans-4-hexylcyclohexanecarboxylic acid- (2-hexyl-pyridin-5-yl) -ester trans-4-heptylcyclohexanecarboxylic acid - (2-hexyl-pyridin-5-yl) ester
  • trans-4-pentylcyclohexane carboxylic acid (2-methoxy-pyridin-5-yl) ester is obtained.
  • I trans-4- (trans-4-butylcyclohexyl) cyclohexylmethyl- ( 2-pentyl-pyridin-5-yl) ether
  • trans-4-heptylcyclohexyl) cyclohexylmethyl- (2-pentyl-pyridin-5-yl) ether
  • trans-4-octylcyclohexyl) trans
  • the following example relates to a liquid-crystalline phase according to the invention.
  • a liquid crystalline phase consisting of
  • trans-4- (trans-4-propylcyclohexyl) cyclohexane carboxylic acid (4-propylphenyl) ester 5% trans-4- (trans-4-propylcyclohexyl) cyclohexane carboxylic acid (2-pentylpyridin-5-yl) ester, 5% trans-4-trans-4-butylcyclohexyl) cyclohexanecarboxylic acid (4-propylphenyl) ester, 5% trans-4- (trans-4-butylcyclohexyl) cyclohexanecarboxylic acid (2-pentylpyridin-5-yl) ester,

Abstract

Compounds of formula (I), wherein A denotes a pyridine ring, are particularly useful as components of liquid-crystal.

Description

Pyridinderivate Pyridine derivatives
Die Erfindung betrifft Pyridinderivate der Formel IThe invention relates to pyridine derivatives of the formula I.
Figure imgf000003_0001
worin
Figure imgf000003_0001
wherein
R1 einen Alkylrest mit 1-15 C-Atomen oder einen Alkenylrest mit 2-15 C-Atomen, wobei in diesenR 1 is an alkyl radical with 1-15 C atoms or an alkenyl radical with 2-15 C atoms, in which
Resten auch eine CH2-Gruppe durch -O-, -CO-, -O-CO- oder -CO-O- ersetzt sein kann,A CH 2 group can also be replaced by -O-, -CO-, -O-CO- or -CO-O-,
R 2 ei.ne der Bedeutungen von R1 oder einen optisch aktiven RestR 2 ei.ne of the meanings of R 1 or an optically active radical
Figure imgf000003_0002
Figure imgf000003_0002
worinwherein
X -CO-O-, -O-CO-, -O-CO-O-, -CO-, -O-, -s-, -CH=CH-, -CH=CH-C00- oder eine Einfachbindung,X -CO-O-, -O-CO-, -O-CO-O-, -CO-, -O-, -s-, -CH = CH-, -CH = CH-C00- or a single bond,
Q Alkylen mit 1 bis 5 C-Atomen, worin auch eine nicht mit X verknüpfte CH2-Gruppe durch -O-, -CO-, -O-CO-, -CO-O- oder -CH=CH- ersetzt sein kann, oder eine Einfachbindung, Y CN, Halogen, Methyl oder Methoxy, undQ alkylene with 1 to 5 carbon atoms, in which a CH 2 group which is not linked to X can also be replaced by -O-, -CO-, -O-CO-, -CO-O- or -CH = CH- , or a single bond, Y CN, halogen, methyl or methoxy, and
R 3 eine von Y verschiedene Alkylgruppe mit 1 bisR 3 is an alkyl group other than Y with 1 to
15 C-Atomen, worin auch eine oder zwei nicht benachbarte CH2-Gruppen durch -O-, -CO-,15 carbon atoms, in which also one or two non-adjacent CH 2 groups by -O-, -CO-,
-O-CO-, -CO-O- und/oder -CH=CH- ersetzt sein können, bedeutet-O-CO-, -CO-O- and / or -CH = CH- can be replaced means
Z-A oder
Figure imgf000004_0001
ZA or
Figure imgf000004_0001
Figure imgf000004_0002
Figure imgf000004_0002
Z1 -CH2CH2 oder eine Einfachbindung,Z 1 -CH 2 CH 2 or a single bond,
A1 -O-CO-Phe-,A 1 -O-CO-Phe-,
Phe unsubstituiertes oder ein- oder mehrfach durch F- und/oder Cl-Atome und/oder CH3- und/oder CN-Gruppen substituiertes 1,4- Phenylen,Phe 1,4-phenylene which is unsubstituted or substituted one or more times by F and / or Cl atoms and / or CH 3 and / or CN groups,
n 0 oder 1n 0 or 1
undand
m 0 oder 1m 0 or 1
bedeutet,means
sowie die Verwendung dieser Verbindungen als Komponenten flüssigkristalliner Phasen. Der Einfachheit halber bedeuten im folgenden Cyc eine 1,4-Cyclohexylengruppe, Phe eine 1,4-Phenylengruppe und PheX eine durch F- und/oder Cl-Atome und/oder CH3,- und/oder CN-Gruppen ein- oder mehrfach substituierte 1,4¬Phenylengruppe.and the use of these compounds as components of liquid-crystalline phases. For the sake of simplicity, Cyc in the following means a 1,4-cyclohexylene group, Phe a 1,4-phenylene group and PheX one or more times by F and / or Cl atoms and / or CH 3 , - and / or CN groups substituted 1,4-phenylene group.
Die Verbindungen der Formel I können wie ähnliche Verbindungen als Komponenten flüssigkristalliner Phasen verwendet werden, insbesondere für Displays, die auf dem Prinzip der verdrillten Zelle (TN-Displays), dem Guest-Host-Effekt, dem ECB-Effekt, dem Effekt der Deformation aufgerichteter Phasen, dem Effekt der dynamischen Streuung oder dem SSFLC-Prinzip beruhen, oder auch für TFT- oder STN-Mischungen. Für hochinformative Flüssigkristall-Anzeigeelemente mit besonders kurzen Schaltzeiten werden flüssigkristalline Phasen benötigt, die sehr niedrige Viskositäten und besonders vorteilhafte elastische Konstanten aufweisen.Like similar compounds, 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 ECB effect, the effect of the deformation Phases based on the effect of dynamic scattering or the SSFLC principle, or also for TFT or STN mixtures. For highly informative liquid crystal display elements with particularly short switching times, liquid crystalline phases are required which have very low viscosities and particularly advantageous elastic constants.
Der Erfindung lag die Aufgabe zugrunde, neue stabile flüssigkristalline oder mesogene Verbindungen aufzufinden, die als Komponenten flüssigkristalliner Phasen geeignet sind.The object of the invention was to find new stable liquid-crystalline or mesogenic compounds which are suitable as components of liquid-crystalline phases.
Es wurde gefunden, daß die Verbindungen der Formel I als Komponenten flüssigkristalliner Phasen vorzüglich geeignet sind. Insbesondere sind mit ihrer Hilfe stabile flüssigkristalline Phasen für hochinformative Displays mit kurzen Schaltzeiten herstellbar. Ferner eignen sich bestimmte Verbindungen der Formel I, auch als Komponenten ferroelektrischer Flüssigkristallphasen beispielsweise für Displays nach dem SSFLC-Prinzip. Mit der Bereitstellung der Verbindungen der Formel I wird außerdem ganz allgemein die Palette der flüssigkristallinen Substanzen, die sich unter verschiedenen anwendungstechnischen Gesichtspunkten zur Herstellung flüssigkristalliner Gemische eignen, erheblich verbreitert.It has been found that the compounds of the formula I are particularly suitable as components of liquid-crystalline phases. In particular, they can be used to produce stable liquid-crystalline phases for high-information displays with short switching times. Furthermore, certain compounds of formula I are also suitable as components of ferroelectric liquid crystal phases, for example for displays based on the SSFLC principle. With the provision of the compounds of the formula I, the range of liquid-crystalline substances which are suitable for the preparation of liquid-crystalline mixtures from various technical aspects is also very broadly widened.
Die Verbindungen der Formel I besitzen einen breiten Anwendungsbereich. In Abhängigkeit von der Auswahl der Substituenten können diese Verbindungen als Basismaterialien dienen, aus denen flüssigkristalline Phasen zum überwiegenden Teil zusammengesetzt sind; es können aber auch Verbindungen der Formel I flüssigkristallinen Basismaterialien aus anderen Verbindungsklassen zugesetzt werden, um beispielsweise die dieelektrische und/ oder optische Anisotropie oder andere Parameter eines solchen Dielektrikums zu optimieren. Die Verbindungen .der Formel I eignen sich ferner als Zwischenprodukte zur Herstellung anderer Substanzen, die sich als Bestandteile flüssigkristalliner Phasen verwenden lassen.The compounds of formula I have a wide range of uses. Depending on the choice of the substituents, these compounds can serve as base materials from which liquid-crystalline phases are predominantly composed; However, it is also possible to add compounds of the formula I to liquid-crystalline base materials from other classes of compounds in order, for example, to optimize the electrical and / or optical anisotropy or other parameters of such a dielectric. The compounds of formula I are also suitable as intermediates for the preparation of other substances which can be used as constituents of liquid-crystalline phases.
Die Verbindungen der Formel I (m = 0) zeigen niedrigeThe compounds of formula I (m = 0) show lower ones
Werte für die Viskosität und vorteilhafte Werte der elastischen Konstanten für Anwendung in hochinformativen Displays wie z.B. für STN- oder TFT-Displays.Values for viscosity and advantageous values of elastic constants for use in high-information displays such as for STN or TFT displays.
Weiter sind Verbindungen der Formel, worin m = 1, hervorragend als Komponenten ferroelektrischer Flüssigkristallphasen geeignet.Furthermore, compounds of the formula in which m = 1 are outstandingly suitable as components of ferroelectric liquid crystal phases.
Die Verbindungen der Formel I sind in reinem Zustand farblos und bilden flüssigkristalline Mesophasen in einem für die elektrooptische Verwendung günstig gelegenen Temperaturbereich. Chemisch, thermisch und gegen Licht sind sie sehr stabil. Gegenstand der Erfindung sind somit die Verbindungen der Formel I sowie die Verwendung der Verbindungen der Formel I als Komponenten flüssigkristalliner Phasen. Gegenstand der Erfindung sind ferner flüssigkristalline Phasen mit einem Gehalt an mindestens eine Verbindung der Formel I sowie Flüssigkristallanzeigeelemente, die derartige Phasen enthalten.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. They are very stable chemically, thermally and against light. 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 which contain such phases.
Vor- und nachstehend haben R 1, Z1, n, Z, A, A1, m und R2 die angegebene Bedeutung, sofern nicht ausdrücklich etwas anderes vermerkt ist.Above and below, R 1 , Z 1 , n, Z, A, A 1 , m and R 2 have the meaning given, unless expressly stated otherwise.
Die Verbindungen der Formel I umfassen dementsprechend Verbindungen der Teilformel Ia (mit zwei Ringen), Ib bis Id (mit drei Ringen) und Ie bis If (mit vier Ringen):The compounds of the formula I accordingly comprise compounds of the partial formula Ia (with two rings), Ib to Id (with three rings) and Ie to If (with four rings):
R1-Cyc-Z-A-R2 Ia R1-Cyc-Cyc-Z-A-R2 IbR 1 -Cyc-ZAR 2 Ia R 1 -Cyc-Cyc-ZAR 2 Ib
R1-Cyc-Z1-Cyc-Z-A-R2 IcR 1 -Cyc-Z 1 -Cyc-ZAR 2 Ic
R1-Cyc-Z-A-A1-R2 IdR 1 -Cyc-ZAA 1 -R 2 Id
R1-Cyc-Cyc-Z-A-A1-R2 IeR 1 -Cyc-Cyc-ZAA 1 -R 2 Ie
R1-Cyc-Z1-Cyc-Z-A-A1-R2 IfR 1 -Cyc-Z 1 -Cyc-ZAA 1 -R 2 If
Darunter sind diejenigen der Teilformeln Ia, Ib, Ic und Id besonders bevorzugt.Among them, those of the sub-formulas Ia, Ib, Ic and Id are particularly preferred.
Die bevorzugten Verbindungen der Teilformel Ia umfassen solche der Teilformeln Iaa bis Iah:The preferred compounds of sub-formula Ia include those of sub-formulas Iaa to Iah:
Figure imgf000007_0001
Figure imgf000008_0001
Figure imgf000007_0001
Figure imgf000008_0001
Darunter sind diejenigen der Formeln Iaa, lac, lae, laf und Iah besonders bevorzugt.Among them, those of the formulas Iaa, lac, lae, laf and Iah are particularly preferred.
Die bevorzugten Verbindungen der Teilformel Ib umfassen solche der Teilformeln Iba bis Ibj:The preferred compounds of sub-formula Ib include those of sub-formulas Iba to Ibj:
Figure imgf000008_0002
Figure imgf000009_0001
Figure imgf000008_0002
Figure imgf000009_0001
Darunter sind diejenigen der Teilformeln Ibc, Ibd, Ibe, Ibh, Ibi und Ibj besonders bevorzugt.Among them, those of the sub-formulas Ibc, Ibd, Ibe, Ibh, Ibi and Ibj are particularly preferred.
Die bevorzugten Verbindungen der Teilformel Ic umfassen diejenigen der Teilformeln Ica bis Icj :The preferred compounds of sub-formula Ic include those of sub-formulas Ica to Icj:
Figure imgf000009_0002
Figure imgf000010_0002
Figure imgf000009_0002
Figure imgf000010_0002
Darunter sind diejenigen der Formeln Icc, Icd, leg und Ich besonders bevorzugt.Among them, those of the formulas Icc, Icd, leg and Ich are particularly preferred.
Die bevorzugten Verbindungen der Teilformel Id umfassen diejenigen der Teilformeln Ida bis Idd:The preferred compounds of sub-formula Id include those of sub-formulas Ida to Idd:
Figure imgf000010_0001
Figure imgf000011_0001
Figure imgf000010_0001
Figure imgf000011_0001
Darunter sind diejenigen der Fomeln Ida, Idg und Idh besonders bevorzugt.Among them, those of the formulas Ida, Idg and Idh are particularly preferred.
Die bevorzugten Verbindungen der Teilformeln Ie und If umfassen diejenigen der Teilformeln Iea bis Iec:The preferred compounds of the sub-formulas Ie and If include those of the sub-formulas Iea to Iec:
Figure imgf000011_0002
Figure imgf000011_0002
Darin bedeutet Z1 vorzugsweise eine Einfachbindung,Z 1 preferably denotes a single bond,
In den Verbindungen der vor- und nachstehenden Formeln bedeuten R 1 und R2 vorzugsweise Alkyl, -O-Alkyl, -OCO-In the compounds of the formulas above and below, R 1 and R 2 are preferably alkyl, -O-alkyl, -OCO-
Alkyl oder Oxaalkyl.Alkyl or oxaalkyl.
Besonders bevorzugt bedeutet R1 Alkyl und R2 Alkyl, Alkoxy oder -OCO-Alkyl.R 1 is particularly preferably alkyl and R 2 is alkyl, alkoxy or -OCO-alkyl.
Ferner sind für R 1 und/oder R2 Alkenylgruppen bevorzugt. Besonders bevorzugt sind auch Substanzen der Formel I, worin R 2 einen optisch aktiven Rest der FormelFurthermore, alkenyl groups are preferred for R 1 and / or R 2 . Substances of the formula I in which R 2 is an optically active radical of the formula are also particularly preferred
Figure imgf000012_0001
Figure imgf000012_0001
bedeutet, worinmeans what
X -CO-O-, -O-CO-, -O-CO-O-, -CO-, -O-, -S-, -CH=CH-, -CH=CH-COO- oder eine Einfachbindung,X -CO-O-, -O-CO-, -O-CO-O-, -CO-, -O-, -S-, -CH = CH-, -CH = CH-COO- or a single bond,
Q Alkylen mit 1 bis 5 C-Atomen, worin auch eine nicht mit X' verknüpfte CH2-Gruppe duch -O-, -CO-, -O-CO-, -CO-O- oder -CH=CH- ersetzt sein kann, oder eine Einfachbindung,Q alkylene with 1 to 5 carbon atoms, in which a CH 2 group which is not linked to X 'is also replaced by -O-, -CO-, -O-CO-, -CO-O- or -CH = CH- can, or a single bond,
Y CN, Halogen, Methyl oder Methoxy, undY CN, halogen, methyl or methoxy, and
R 3 eine von Y verschi.edene Alkylgruppe mi.t 1 bxs 15 C-Atomen, worin auch eine oder zwei nicht benachbarte CH2-Gruppen durch -O-, -CO-, -O-CO-, -CO-O- und/oder -CH=CH- ersetzt sein können,R 3 is an alkyl group different from Y with 1 bxs 15 C atoms, in which also one or two non-adjacent CH 2 groups are -O-, -CO-, -O-CO-, -CO-O- and / or -CH = CH- can be replaced,
bedeutet.means.
Folgende Gruppe von optisch aktiven Resten ist ganz besonders bevorzugt:The following group of optically active residues is very particularly preferred:
-O-CH2C*HF-Alkyl, -O-CO-C*HF-Alkyl , -O-CO-C*HCl-Alkyl , -CO-O-C*HCN-Alkyl , -O-C*CHCH3 -COO-Alkyl , -COO-C*HCH3 -COO- Alkyl , -O-C*HCH3 -Alkyl oder -O-CH2-C*HCH3-C2H5 . Z-A bedeutet in erster Linie bevorzugt
Figure imgf000013_0001
in zweiter Linie bevorzugt
Figure imgf000013_0002
-O-CH 2 C * HF-alkyl, -O-CO-C * HF-alkyl, -O-CO-C * HCl-alkyl, -CO-OC * HCN-alkyl, -OC * CHCH 3 -COO- Alkyl, -COO-C * HCH 3 -COO- alkyl, -OC * HCH 3 alkyl or -O-CH 2 -C * HCH 3 -C 2 H 5 . ZA primarily means preferred
Figure imgf000013_0001
preferred in the second place
Figure imgf000013_0002
Z1 bedeutet -CH2CH2- oder eine Einfachbindung, vorzugsweise eine Einfachbindung.Z 1 means -CH 2 CH 2 - or a single bond, preferably a single bond.
Falls Z-A = ist vorzugsweise R2 = -O-CO-
Figure imgf000013_0003
If ZA = preferably R 2 = -O-CO-
Figure imgf000013_0003
Alkyl und/oder vorzugsweiseAlkyl and / or preferably
m = 1 und/oder Z1 = -CH2CH2-.m = 1 and / or Z 1 = -CH 2 CH 2 -.
Cyc bedeutet eine trans-1,4-Cyclohexylengruppe undCyc means a trans-1,4-cyclohexylene group and
A1 = -O-CO-Phe.A 1 = -O-CO-Phe.
Phe ist vorzugsweise eine unsubstituierte 1,4-Phenylengruppe, kann aber auch ein- oder mehrfach, vorzugsweise ein- oder zweifach durch F, Cl, CH3 und/oder CN substituiert vorliegen. Bevorzugt ist eine Mono-Substitution durch Fluor, insbesondere bevorzugt ist eine Di-Substitution in 2,3-Position durch Fluor.Phe is preferably an unsubstituted 1,4-phenylene group, but can also be substituted one or more times, preferably once or twice, by F, Cl, CH 3 and / or CN. Mono substitution by fluorine is preferred, and di-substitution in the 2,3-position by fluorine is particularly preferred.
n bedeutet vorzugsweise 1 und m vorzugsweise 0.n is preferably 1 and m is preferably 0.
Die Alkylreste in den Gruppen R 1 und/oder R2 können geradkettig oder verzweigt sein. Vorzugsweise sind sie geradkettig, haben 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 oder 12 C-Atome und bedeuten demnach bevorzugt Methyl,The alkyl radicals in the groups R 1 and / or R2 can be straight-chain or branched. They are preferably straight-chain, have 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms and accordingly preferably denote methyl,
Ethyl, Propyl, Butyl, Pentyl, Hexyl, Heptyl, Octyl, Nonyl, Decyl, Undecyl oder Dodecyl, ferner Tridecyl,Ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl, furthermore tridecyl,
Tetradecyl oder Pentadecyl.
Figure imgf000014_0003
Tetradecyl or pentadecyl.
Figure imgf000014_0003
Insbesondere bevorzugt sind Verbindungen der Formel ICompounds of the formula I are particularly preferred
mit R = Methyl, m = 0 und Z-A = oder
Figure imgf000014_0002
Figure imgf000014_0001
with R = methyl, m = 0 and ZA = or
Figure imgf000014_0002
Figure imgf000014_0001
Falls R 1 und/oder R2 Alkylreste bedeuten, in denen eineIf R 1 and / or R 2 are alkyl radicals in which one
("Alkoxy" bzw. "Oxaalkyl") oder zwei ( "Alkoxyalkoxy" bzw. "Dioxaalkyl") CH2-Gruppen durch O-Atome ersetzt sind, so können sie geradkettig, oder verzweigt sein. Vorzugsweise sind sie geradkettig, haben 2, 3, 4, 5,("Alkoxy" or "Oxaalkyl") or two ("Alkoxyalkoxy" or "Dioxaalkyl") CH2 groups are replaced by O atoms, they can be straight-chain or branched. They are preferably straight-chain, have 2, 3, 4, 5,
6 oder 7 C-Atome und bedeuten demnach bevorzugt Ethoxy, Propoxy, Butoxy, Pentoxy, Hexoxy, Heptoxy, 2-Oxapropyl (= Methoxymethyl), 2- (= Ethoxymethyl) oder 3-Oxabutyl (= 2-Methoxyethyl), 2-, 3- oder 4-Oxapentyl, 2-, 3-, 4- oder 5-Oxahexyl, 2-, 3-, 4-, 5- oder 6-Oxaheptyl, ferner Methoxy, Octoxy, Nonoxy, Decoxy, 2-, 3-, 4-, 5-, 6- oder 7-Oxaoctyl, 2- , 3-, 4-, 5-, 6-, 7- oder 8-Oxanonyl, 2-, 3-, 4-, 5-, 6-, 7-, 8- oder 9-Oxadecyl, 1,3-Dioxabutyl (= Methoxymethoxy), 1,3-, 1,4- oder 2 ,4-Dioxapentyl, 1,3-,.1,4-, 1,5-, 2,4-, 2,5- oder 3 ,5-Dioxahexyl, 1,3-, 1,4-, 1,5-, 1,6-, 2,4-, 2,5-, 2,6-, 3,5-, 3,6- oder 4, 6-Dioxaheptyl.6 or 7 carbon atoms and therefore preferably mean ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, 2-oxapropyl (= methoxymethyl), 2- (= ethoxymethyl) or 3-oxabutyl (= 2-methoxyethyl), 2-, 3- or 4-oxapentyl, 2-, 3-, 4- or 5-oxahexyl, 2-, 3-, 4-, 5- or 6-oxaheptyl, also methoxy, octoxy, nonoxy, decoxy, 2-, 3- , 4-, 5-, 6- or 7-oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonyl, 2-, 3-, 4-, 5-, 6- , 7-, 8- or 9-oxadecyl, 1,3-dioxabutyl (= methoxymethoxy), 1,3-, 1,4- or 2,4-dioxapentyl, 1,3 - ,. 1,4-, 1, 5-, 2,4-, 2,5- or 3,5-dioxahexyl, 1,3-, 1,4-, 1,5-, 1,6-, 2,4-, 2,5-, 2nd , 6-, 3,5-, 3,6- or 4,6-dioxaheptyl.
Verbindungen der Formel I sowie der vor- und nachstehen- den Teilformeln mit verzweigten Flügelgruppen R 1 bzw. R2 können gelegentlich wegen einer besseren Löslichkeit in den üblichen flüssigkristallinen Basismaterialien vonCompounds of the formula I and the subformulas above and below with branched wing groups R 1 or R 2 can occasionally be used because of their better solubility in the customary liquid-crystalline base materials
Bedeutung sein. Verzweigte Gruppen dieser Art enthalten in der Regel nicht mehr als eine Kettenverzweigung. Bevorzugte verzweigte Reste R 2 und R1 sind Isopropyl, 2- Butyl (= 1-Methylpropyl), Isobutyl (= 2-Methylpropyl), 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, 1-Methylheptoxy, 2-Oxa-3-methylbutyl, 3-Oxa-4-methylpentyl, 2-Octyloxy, 2-Methyl-3-oxapentyl, 2-Methyl-3-oxa-hexyl.Be meaningful. Branched groups of this type usually contain no more than one chain branch. Preferred branched radicals R 2 and R 1 are isopropyl, 2-butyl (= 1-methylpropyl), isobutyl (= 2-methylpropyl), 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, 1-methylheptoxy, 2-oxa-3-methylbutyl, 3-oxa-4-methylpentyl, 2-octyloxy, 2-methyl-3-oxapentyl, 2-methyl-3- oxa-hexyl.
Falls R 1 und/oder R2 einen Alkenylrest bedeuten, so kann dieser geradkettig oder verzweigt sein. Vorzugsweise ist er geradkettig und hat 2 bis 10 C-Atome. Er bedeutet demnach bevorzugt Vinyl, Prop-1- oder Prop-2-enyl, But-1-, 2- oder But-3-enyl, Pent-1-, 2-, 3- oder Pent-4-enyl, Hex-1-, 2-, 3-, 4- oder Hex-5-enyl, Hept-1-, 2-, 3-, 4-, 5- oder Hept-6-enyl, Oct-1-, 2-, 3-, 4-, 5-, 6- oder Oct-7-enyl, Non-1-, 2-, 3-, 4-, 5-, 6-, 7- oder Non-8-enyl, Dec-1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- oder Dec-9-enyl.If R 1 and / or R2 represent an alkenyl radical, this can be straight-chain or branched. It is preferably straight-chain and has 2 to 10 carbon atoms. Accordingly, it preferably means vinyl, prop-1- or prop-2-enyl, but-1-, 2- or but-3-enyl, pent-1-, 2-, 3- or pent-4-enyl, hex- 1-, 2-, 3-, 4- or hex-5-enyl, hept-1-, 2-, 3-, 4-, 5- or hept-6-enyl, oct-1-, 2-, 3 -, 4-, 5-, 6- or oct-7-enyl, non-1-, 2-, 3-, 4-, 5-, 6-, 7- or non-8-enyl, dec-1- , 2-, 3-, 4-, 5-, 6-, 7-, 8- or Dec-9-enyl.
Besonders bevorzugt sind auch Verbindungen der Formel I mit folgender Struktur IgCompounds of the formula I with the following structure Ig are also particularly preferred
Figure imgf000015_0001
Figure imgf000015_0001
Diese Verbindu
Figure imgf000015_0002
ngen sind zwar in der J6 0149564 von der allgemeinen Formel umfaßt, jedoch sind keinerlei expli- zieten Beispiele vorhanden.This connection
Figure imgf000015_0002
Although J6 0149564 encompasses the general formula, no explicit examples are available.
Es wurde nun gefunden, daß die Verbindungen der Formel Ig niedrigere Schmelzpunkte, höhere Klärpunkte und damit eine wesentlich breitere Mesophase aufweisen als die in der J 60149564 aufgeführten Verbindungen, wie aus folgendem Vergleich zu sehen ist. (beschrieben in
Figure imgf000016_0001
It has now been found that the compounds of the formula Ig have lower melting points, higher clearing points and thus a much broader mesophase than the compounds listed in J 60149564, as can be seen from the following comparison. (described in
Figure imgf000016_0001
JG 0149564) hat einen Schmelzpunkt von 85,1° und einen Klärpunkt von 92.9°. Dagegen hat eine Verbindung derJG 0149564) has a melting point of 85.1 ° and a clearing point of 92.9 °. In contrast, the
Formel Ig z.B. einen
Figure imgf000016_0002
Formula Ig eg one
Figure imgf000016_0002
Schmelzpunkt von 41° und einen Klärpunkt von 136.6°. Der Mesophasenbereich ist also bei den erfindungsgemäßen Verbindungen um den Faktor 10-12mal breiter als bei den vorbeschriebenen Verbindungen. Die erfindungsgemäßen Verbindungen Ig sind daher sehr viel besser als Komponenten flüssigkristalliner Phasen geeignet.Melting point of 41 ° and a clearing point of 136.6 °. The mesophase range is thus 10 to 12 times wider for the compounds according to the invention than for the compounds described above. The compounds Ig according to the invention are therefore much more suitable as components of liquid-crystalline phases.
Die Verbindungen der Formel I werden nach an sich bekannten Methoden hergestellt, wie sie in der Literatur (z.B. in den Standardwerken wie Houben Weyl, Methoden der Organischen Chemie, Georg-Thieme-Verlag, Stuttgart) beschrieben sind, und zwar unter Reaktionsbedingungen, die für die genannten Umsetzungen bekannt und geeignet sind. Dabei kann man von an sich bekannten, hier nicht erwähnten Varianten Gebrauch machen.The compounds of formula I 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), and under reaction conditions which are suitable for the implementations mentioned are known and suitable. One can make use of variants which are known per se and are not mentioned here.
Ester der Formel I können durch Veresterung entsprechender Carbonsäuren (oder ihren reaktionsfähigen Derivaten) mit entsprechend 2-substituierten Pyridin-5-olen (oder den reaktionsfähigen Derivaten) erhalten werden.Esters of the formula I can be obtained by esterifying corresponding carboxylic acids (or their reactive derivatives) with correspondingly 2-substituted pyridin-5-ols (or the reactive derivatives).
Als reaktionsfähige Derivate der genannten Carbonsäuren eignen sich insbesondere die Säurehalogenide, vor allem die Chloride und Bromide, ferner die Anhydride, Azide und Ester, insbesondere Alkylester mit 1-4 C-Atomen in der Alkylgruppe. Als reaktionsfähige Derivate der genannten Pyridin-5-olen kommen insbesondere die entsprechenden Metallalkoholate, vorzugsweise eines Alkalimetalls wie Na oder K, in Betracht.Suitable reactive derivatives of the carboxylic acids mentioned are, in particular, the acid halides, especially the chlorides and bromides, furthermore the anhydrides, azides and esters, in particular alkyl esters with 1-4 C atoms in the alkyl group. Suitable reactive derivatives of the pyridin-5-ols mentioned are in particular the corresponding metal alcoholates, preferably an alkali metal such as Na or K.
Die Umsetzungen werden vorzugsweise in Toluol/Pyridin, ausgehend vom Säurechlorid, oder auch mit DCC (Dicyclohexylcarbodiimid) in Gegenwart katalytischer Mengen DMAP (Dimethylaminopyridin) durchgeführt, ausgehend von der Carbonsäure selbst.The reactions are preferably carried out in toluene / pyridine, starting from the acid chloride, or also with DCC (dicyclohexylcarbodiimide) in the presence of catalytic amounts of DMAP (dimethylaminopyridine), starting from the carboxylic acid itself.
Ether der Formel I (worin Z = -CH2O-) sind durch Veretherung entsprechender Hydroxyverbindungen herstellbar, wobei die Hydroxyverbindungen zweckmäßig zunächst in ein entsprechendes Metallderivat, z.B. durch Behandeln mit NaH, NaNH2, NaOH, KOH, Na2CO3 oder K2CO3, überführt wird. Dieses Metallderivat kann dann mit dem entsprechenden Alkylhalogenid, -sulfonat oder Dialkylsulfonat umgesetzt werden, zweckmäßig in einem inerten Lösungsmittel wie Aceton, 1,2-Dimethoxyethan, DMF oder Dimethylsulfoxid oder auch einem Überschuß an wäßriger oder wäßrig-alkoholischer NaOH oder KOH bei Temperaturen zwischen etwa 20° und 100°.Ethers of the formula I (in which Z = -CH 2 O-) can be prepared by etherification of corresponding hydroxyl compounds, the hydroxyl compounds first being expediently 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 transferred. This metal derivative can then be reacted with the corresponding alkyl halide, sulfonate or dialkyl sulfonate, advantageously in an inert solvent such as acetone, 1,2-dimethoxyethane, DMF or dimethyl sulfoxide or even an excess of aqueous or aqueous-alcoholic NaOH or KOH at temperatures between about 20 ° and 100 °.
Verbindungen der Formel I mit Z-A =
Figure imgf000017_0001
sind beispielsweise erhältlich durch Umsetzung der entsprechenden 2-Methylpyridine mit dem entsprechenden Alkylierungsmittel in Gegenwart einer Base wie z.B. Lithiumdiisopropylamid.Compounds of formula I with ZA =
Figure imgf000017_0001
are obtainable, for example, by reacting the corresponding 2-methylpyridines with the corresponding alkylating agent in the presence of a base such as, for example, lithium diisopropylamide.
Die Ethanderivate können auch hergestellt werden durch Hydrierung der entsprechenden Alkene. Die Hydrierungen können nach allgemein bekannten Methoden durchgeführt werden. Die AusgangsVerbindungen sind entweder bekannt oder durch einfache, literaturbekannte Reaktionen herstellbar.The ethane derivatives can also be prepared by hydrogenating the corresponding alkenes. The hydrogenations can be carried out by generally known methods. The starting compounds are either known or can be prepared by simple reactions known from the literature.
Die erfindungsgemäßen flüssigkristallinen Medien enthalten vorzugsweise neben einer oder mehreren erfindungsgemäßen Verbindungen als weitere Bestandteile 2 bis 40, insbesondere 4 bis 30 Komponenten. Ganz besonders bevorzugt enthalten diese Medien neben einer oder mehreren erfindungsgemäßen Verbindungen 7 bis 25 Komponenten. Diese weiteren Bestandteile werden vorzugsweise ausgewählt aus nematisehen oder nematogenen (monotropen oder isotropen) Substanzen, insbesondere Substanzen aus den Klassen der Azoxybenzole, Benzylidenaniline, Biphenyle, Terphenyle, Phenyl- oder Cyclohexylbenzoate, Cyclohexan-carbonsäurephenyl- oder cyclohexyl-ester, Phenyl- oder Cyclohexylester der Cyclohexylbenzoesäure, Phenyl- oder Cyclohexylester der Cyclohexylcyclohexancarbonsäure, Cyclohexylphenylester der Benzoesäure, der Cyclohexancarbonsäure, bzw. der Cyclohexylcyclohexancarbonsäure, Phenylcyclohexane, Cyclohexylbiphenyle, Phenylcyclohexylcyclohexane, Cyclohexylcyclohexane, Cyclohexylcyclohexene, Cyclohexylcyclohexylcyclohexene, 1,4-Bis-cyclohexylbenzole, 4,4'-Bis-cyclohexylbiphenyle, Phenyl- oder Cyclohexylpyrimidine, Phenyl- oder Cyclohexylpyridine, Phenyl- oder Cyclohexyldioxane, Phenyl- oder Cyclohexyl-1,3-dithiane, 1,2-Diphenylethane, 1,2-Dicyclohexylethane, 1-Phenyl-2-cyclohexylethane, 1-Cyclohexyl-2-(4-phenyl-cyclohexyl)-ethane, 1-Cyclohexyl-2-biphenylylethane, 1-Phenyl-2-cyclohexylphenylethane, gegebenenfalls halogenierten Stilbene, Benzylphenylether, Tolane und substituierten Zimtsäuren. Die 1,4-Phenylengruppen in diesen Verbindungen können auch fluoriert sein.In addition to one or more compounds according to the invention, the liquid-crystalline media according to the invention preferably contain 2 to 40, in particular 4 to 30, components as further constituents. These media very particularly preferably contain 7 to 25 components in addition to one or more compounds according to the invention. These further constituents are preferably selected from nematic or nematogenic (monotropic or isotropic) substances, in particular substances from the classes of azoxybenzenes, benzylidene anilines, biphenyls, terphenyls, phenyl- or cyclohexylbenzoates, cyclohexane-carboxylic acid phenyl or cyclohexyl esters, phenyl or cyclohexyl esters cyclohexylbenzoic acid, phenyl or cyclohexyl esters of cyclohexylcyclohexanecarboxylic acid, cyclohexylphenyl of benzoic acid, of cyclohexanecarboxylic acid, or of cyclohexylcyclohexanecarboxylic acid, phenylcyclohexanes, cyclohexylbiphenyls, phenylcyclohexylcyclohexanes, cyclohexylcyclohexanes, cyclohexylcyclohexenes, cyclohexylcyclohexylcyclohexenes, 1,4-bis-cyclohexylbenzenes, 4,4'-bis-cyclohexylbiphenyls, Phenyl- or cyclohexylpyrimidines, phenyl- or cyclohexylpyridines, phenyl- or cyclohexyldioxanes, phenyl- or cyclohexyl-1,3-dithiane, 1,2-diphenylethane, 1,2-dicyclohexylethane, 1-phenyl-2-cyclohexylethane, 1-cyclohexyl- 2- (4-phenyl-cycl ohexyl) ethanes, 1-cyclohexyl-2-biphenylylethane, 1-phenyl-2-cyclohexylphenylethane, optionally halogenated stilbenes, benzylphenyl ether, tolanes and substituted cinnamic acids. The 1,4-phenylene groups in these compounds can also be fluorinated.
Die wichtigsten als weitere Bestandteile erfindungsgemäßer Medien in Frage kommenden Verbindungen lassen sich durch die Formeln 1, 2, 3, 4 und 5 charakterisieren: R' -L-E-R" 1The most important compounds which are suitable as further constituents of media according to the invention can be characterized by the formulas 1, 2, 3, 4 and 5: R '-LER "1
R ' -L-COO-E-R" 2R '-L-COO-E-R "2
R ' -L-OOC-E-R" 3R '-L-OOC-E-R "3
R ' -L-CH2CH2-E-R" 4R '-L-CH 2 CH 2 -ER "4
R ' -L-C≡C-E-R" 5R '-L-C≡C-E-R "5
In den Formeln 1, 2, 3, 4 und 5 bedeuten L und E, die gleich oder verschieden sein können, jeweils unabhängig voneinander einen bivalenten Rest aus der aus -Phe-, -Cyc-, -Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-, -Pyr-, -Dio-, -G-Phe- und -G-Cyc- sowie deren Spiegelbilder gebildeten Gruppe, wobei Phe unsubstituiertes oder durch Fluor substituiertes 1,4-Phenylen, Cyc trans-1,4-Cyclohexylen oder 1,4-Cyclohexenylen, Pyr Pyrimidin-2,5-diyl oder Pyridin-2, 5-diyl, Dio 1,3-Dioxan-2,5-diyl und G 2-(trans-1,4-Cyclohexyl)-ethyl, Pyrimidin-2,5-diyl, Pyridin-2,5-diyl oder 1,3-Dioxan-2,5-diyl bedeuten.In formulas 1, 2, 3, 4 and 5, L and E, which may be the same or different, each independently represent a bivalent radical from the group consisting of -Phe-, -Cyc-, -Phe-Phe-, -Phe- Cyc-, -Cyc-Cyc-, -Pyr-, -Dio-, -G-Phe- and -G-Cyc- as well as their mirror images formed group, whereby Phe unsubstituted or substituted by fluorine-substituted 1,4-phenylene, Cyc- 1,4-cyclohexylene or 1,4-cyclohexenylene, pyr pyrimidine-2,5-diyl or pyridine-2,5-diyl, dio 1,3-dioxane-2,5-diyl and G 2- (trans-1, 4-Cyclohexyl) ethyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl or 1,3-dioxane-2,5-diyl.
Vorzugsweise ist einer der Rest L und E Cyc, Phe oder Pyr. E ist vorzugsweise Cyc, Phe oder Phe-Cyc. Vorzugsweise enthalten die erfindungsgemäßen Medien eine oder mehrere Komponenten ausgewählt aus den Verbindungen der Formeln 1, 2, 3, 4 und 5, worin L und E ausgewählt sind aus der Gruppe Cyc, Phe und Pyr und gleichzeitig eine oder mehrere Komponenten ausgewählt aus den Verbindungen der Formeln 1, 2, 3, 4 und 5, worin einer der Reste L und E ausgewählt ist aus der Gruppe Cyc, Phe und Pyr und der andere Rest ausgewählt ist aus der Gruppe -Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-, -G-Phe- und -G-Cyc-, und gegebenenfalls eine oder mehrere Komponenten ausgewählt aus den Verbindungen der Formeln 1, 2, 3, 4 und 5, worin die Reste L und E ausgewählt sind aus der Gruppe -Phe-Cyc-, -Cyc-Cyc-, -G-Phe- und -G-Cyc-. R' und R" bedeuten in den Verbindungen der Teilformeln 1a, 2a, 3a, 4a und 5a jeweils unabhängig voneinander Alkyl, Alkenyl , Alkoxy, Alkenyloxy oder Alkanoyloxy mit bis zu 8 Kohlenstoffatomen. Bei den meisten dieser Ver- bindungen sind R1 und R" voneinander verschieden, wobei einer dieser Reste meist Alkyl oder Alkenyl ist. In den Verbindungen der Teilformeln 1b, 2b, 3b, 4b und 5b bedeutet R" -CN, -CF3, F, Cl oder -NCS; R hat dabei die bei den Verbindungen der Teilformeln la bis 5a angegebene Bedeutung und ist vorzugsweise Alkyl oder Alkenyl. Aber auch andere Varianten der vorgesehenen Substituenten in den Verbindungen der Formeln 1, 2, 3, 4 und 5 sind gebräuchlich. Viele solcher Substanzen oder auch Gemische davon sind im Handel erhältlich. Alle diese Substanzen sind nach literaturbekannten Methoden oder in Analogie dazu erhältlich.Preferably one of the radicals L and E is Cyc, Phe or Pyr. E is preferably Cyc, Phe or Phe-Cyc. The media according to the invention preferably contain one or more components selected from the compounds of the formulas 1, 2, 3, 4 and 5, in which L and E are selected from the group Cyc, Phe and Pyr and at the same time one or more components selected from the compounds of Formulas 1, 2, 3, 4 and 5, in which one of the radicals L and E is selected from the group Cyc, Phe and Pyr and the other radical is selected from the group -Phe-Phe-, -Phe-Cyc-, - Cyc-Cyc-, -G-Phe- and -G-Cyc-, and optionally one or more components selected from the compounds of the formulas 1, 2, 3, 4 and 5, in which the radicals L and E are selected from the group -Phe-Cyc-, -Cyc-Cyc-, -G-Phe- and -G-Cyc-. R 'and R "in the compounds of sub-formulas 1a, 2a, 3a, 4a and 5a each independently represent alkyl, alkenyl, alkoxy, alkenyloxy or alkanoyloxy having up to 8 carbon atoms. Most of these compounds are R1 and R" different from one another, one of these radicals usually being alkyl or alkenyl. In the compounds of sub-formulas 1b, 2b, 3b, 4b and 5b, R "means -CN, -CF 3 , F, Cl or -NCS; R has the meaning given for the compounds of sub-formulas Ia to 5a and is preferably alkyl or Alkenyl, but also other variants of the proposed substituents in the compounds of the formulas 1, 2, 3, 4 and 5 are common. Many such substances or mixtures thereof are commercially available. All of these substances are obtainable by methods known from the literature or in analogy thereto .
Die erfindungsgemäßen Medien enthalten vorzugsweise neben Komponenten aus der Gruppe der Verbindungen la, 2a, 3a, 4a und 5a (Gruppe 1) auch Komponenten aus der Gruppe der Verbindungen 1b, 2b, 3b, 4b und 5b (Gruppe 2), deren Anteile vorzugsweise wie folgt sind:In addition to components from the group of compounds Ia, 2a, 3a, 4a and 5a (group 1), the media according to the invention preferably also contain components from the group of compounds 1b, 2b, 3b, 4b and 5b (group 2), the proportions of which are preferably as follows are:
Gruppe 1: 20 bis 90 %, insbesondere 30 bis 90 %, Gruppe 2: 10 bis 80 %, insbesondere 10 bis 50 %,Group 1: 20 to 90%, in particular 30 to 90%, group 2: 10 to 80%, in particular 10 to 50%,
wobei die Summe der Anteile der erfindungsgemäßen Verbindüngen und der Verbindungen aus den Gruppen 1 und 2 bis zu 100 % ergeben.the sum of the proportions of the compounds according to the invention and of the compounds from groups 1 and 2 giving up to 100%.
Die erfindungsgemäßen Medien enthalten vorzugsweise 1 bis 40 %, insbesondere vorzugsweise 5 bis 30 % an erfindungsgemäßen Verbindungen. Weiterhin bevorzugt sind Medien, enthaltend mehr als 40 %, insbesondere 45 bis 90 % an erfindungegemäßen Verbindungen. Die Medien enthalten vorzugsweise drei, vier oder fünf erfindungsgemäße Verbindungen.The media according to the invention preferably contain 1 to 40%, particularly preferably 5 to 30%, of compounds according to the invention. Also preferred are media containing more than 40%, in particular 45 to 90% of compounds according to the invention. The media preferably contain three, four or five compounds according to the invention.
Die Herstellung der erfindungsgemäßen Medien erfolgt in an sich üblicher Weise. In der Regel werden die Komponenten ineinander gelöst, zweckmäßig bei erhöhter Temperatur. Durch geeignete Zusätze können die flüssigkristallinen Phasen nach der Erfindung so modifiziert werden, daß sie in allen bisher bekannt gewordenen Arten von Flüssigkristallanzeigeelementen verwendet werden können. Derartige Zusätze sind dem Fachmann bekannt und in der Literatur ausführlich beschrieben (H. Kelker/R. Hatz, Handbook of Liquid Crystals, Verlag Chemie, Weinheim, 1980 ) . Beispielsweise können pleochroitische Farbstoffe zur Herstellung farbiger Guest-Host-Systeme oder Substanzen zur Veränderung der dielektrischen Anisotropie, der Viskosität und/oder der Orientierung der nematischen Phasen zugesetzt werden.The media according to the invention are produced in a conventional manner. As a rule, the components are dissolved in one another, advantageously at elevated temperature. By means of suitable additives, the liquid-crystalline phases 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. Such additives are known to the person skilled in the art and are described in detail in the literature (H. Kelker / R. Hatz, Handbook of Liquid Crystals, Verlag Chemie, Weinheim, 1980). For example, pleochroic dyes can be added to produce colored guest-host systems or substances to change the dielectric anisotropy, the viscosity and / or the orientation of the nematic phases.
Die folgenden Beispiele sollen die Erfindung erläutern, ohne sie zu begrenzen, mp. = Schmelzpunkt, cp. = Klärpunkt. Vor- und nachstehend bedeuten Prozentangaben Gewichtsprozent; alle Temperaturen sind in Grad Celsius angegeben. "Übliche Aufarbeitung" bedeutet: man gibt Wasser hinzu, extrahiert mit Methylenchlorid, trennt ab, trocknet die organische Phase, dampft ein und reinigt das Produkt durch Kristallisation und/oder Chromatographie.The following examples are intended to illustrate the invention without limiting it, mp. = Melting point, cp. = Clearing point. Percentages above and below mean percentages by weight; all temperatures are given in degrees Celsius. "Conventional work-up" means: water is added, the mixture is extracted with methylene chloride, the mixture is separated off, the organic phase is dried, evaporated and the product is purified by crystallization and / or chromatography.
Es bedeuten ferner:It also means:
K: Kristallin-fester Zustand, S: smektische Phase (der Index kennzeichnet den Phasentyp), N: nematischer Zustand, Ch: cholesterische Phase, I: isotrope Phase.K: crystalline solid state, S: smectic phase (the index indicates the phase type), N: nematic state, Ch: cholesteric phase, I: isotropic phase.
Die zwischen zwei Symbolen stehende Zahl gibt die Umwandlungstemperatur in Grad Celsius an. Beispiel 1The number between two symbols indicates the transition temperature in degrees Celsius. example 1
Zu einer Suspension von 22,4 g trans-4-(trans-4-Pentylcyclohexyl)cyclohexancarbonsäure, 13,3 g 2-Pentyl-5-hydroxypyridin (Herstellung: Bei -50° gibt man zu einer Lösung von 53 g Diisopropylamin in 350 ml THF 320 ml einer 1,6 m Lösung von n-Butyllithium in Hexan, 27,3 g 2-Methyl-5-hydroxypyridin in 750 ml THF und 44,5 g 1-Brombutan. Man rührt noch 30 Min. und läßt das Reaktionsgemisch dann auf Raumtemperatur kommen, hydrolysiert und stellt mit HCl einen pH-Wert von etwa 6,5 ein. Die organische Phase wird abgetrennt und aufgearbeitet. Nach chromatographischer Reinigung (Hexan/ Kieselgel) erhält man 2-Pentyl-5-hydroxypyridin.) und einer katalytischen Menge Dimethylaminopyridin (DMAP) in 200 ml CH2Cl2 gibt man bei 0°-5° eine Lösung von 18.2 g DCC in 50 ml CH2Cl2. Anschließend rührt man 12 Stunden bei Raumtemperatur, filtriert den ausgefallenen Dicyclohexylharnstoff ab und arbeitet das Filtrat wie üblich auf. Nach Reinigung durch Chromatographie oder Kristallisation erhält man trans-4-(trans-4-Pentylcyclohexyl)-cyclohexancarbonsäure-(2-pentyl-pyridin-5-yl)-ester mit K 31° SB 181° N 183,1° I.To a suspension of 22.4 g of trans-4- (trans-4-pentylcyclohexyl) cyclohexane carboxylic acid, 13.3 g of 2-pentyl-5-hydroxypyridine (preparation: at -50 °, a solution of 53 g of diisopropylamine in 350 is added ml of THF 320 ml of a 1.6 m solution of n-butyllithium in hexane, 27.3 g of 2-methyl-5-hydroxypyridine in 750 ml of THF and 44.5 g of 1-bromobutane, and stirring is continued for 30 minutes The reaction mixture then comes to room temperature, hydrolyzed and adjusted to a pH of about 6.5 with HCl. The organic phase is separated off and worked up. After chromatographic purification (hexane / silica gel), 2-pentyl-5-hydroxypyridine is obtained.) And a catalytic amount of dimethylaminopyridine (DMAP) in 200 ml of CH 2 Cl 2 is added at 0 ° -5 ° to a solution of 18.2 g of DCC in 50 ml of CH 2 Cl 2 . The mixture is then stirred for 12 hours at room temperature, the precipitated dicyclohexylurea is filtered off and the filtrate is worked up as usual. After purification by chromatography or crystallization, trans-4- (trans-4-pentylcyclohexyl) cyclohexane carboxylic acid (2-pentylpyridin-5-yl) ester with K 31 ° S B 181 ° N 183.1 ° I is obtained.
Analog werden hergestellt:The following are produced analogously:
trans-4-(trans-4-Ethylcyclohexyl)cyclohexancarbonsäure- (2-pentyl-pyridin-5-yl)ester trans-4-(trans-4-Propylcyclohexyl)cyclohexancarbonsäure- (2-pentyl-pyridin-5-yl)ester, K 4° SB 170° N 180.8° I trans-4-(trans-4-Butylcyclohexyl)cyclohexancarbonsäure- (2-pentyl-pyridin-5-yl)ester, K 20° SB 178° N 179,3° I trans-4-(trans-4-Hexylcyclöhexyl)cyclohexancarbonsäure- (2-pentyl-pyridin-5-yl)ester trans-4-(trans-4-Heptylcyclohexyl)cyclohexancarbonsäure- (2-pentyl-pyridin-5-yl)ester trans-4-(trans-4-Ethylcyclohexyl)cyclohexancarbonsäure- (2-methyl-pyridin-5-yl)ester trans-4-(trans-4-Propylcyclohexyl)cyclohexancarbonsäure- (2-methyl-pyridin-5-yl)ester, K 80° SG (71°) N 204,8 I trans-4-(trans-4-Butylcyclohexyl)cyclohexancarbonsäure-(2-methyl-pyridin-5-yl)ester trans-4-(trans-4-Pentylcyclohexyl)cyclohexancarbonsäure-(2-methyl-pyridin-5-yl)ester trans-4-(trans-4-Hexylcyclohexyl)cyclohexancarbonsäure-(2-methyl-pyridin-5-yl)ester trans-4-(trans-4-Heptylcyclohexyl)cyclohexancarbonsäure-(2-methyl-pyridin-5-yl)estertrans-4- (trans-4-ethylcyclohexyl) cyclohexanecarboxylic acid (2-pentyl-pyridin-5-yl) ester trans-4- (trans-4-propylcyclohexyl) cyclohexanecarboxylic acid (2-pentyl-pyridin-5-yl) ester , K 4 ° S B 170 ° N 180.8 ° I trans-4- (trans-4-butylcyclohexyl) cyclohexane carboxylic acid (2-pentyl-pyridin-5-yl) ester, K 20 ° S B 178 ° N 179.3 ° I trans-4- (trans-4-hexylcyclohexyl) cyclohexanecarboxylic acid (2-pentyl-pyridin-5-yl) ester trans-4- (trans-4-heptylcyclohexyl) cyclohexanecarboxylic acid (2-pentyl-pyridin-5-yl) ester trans-4- (trans-4-ethylcyclohexyl) cyclohexanecarboxylic acid (2-methyl-pyridin-5-yl) ester trans-4- (trans-4-propylcyclohexyl) cyclohexanecarboxylic acid (2-methyl-pyridin-5-yl) ester , K 80 ° S G (71 °) N 204.8 I trans-4- (trans-4-butylcyclohexyl) cyclohexane carboxylic acid (2-methyl-pyridin-5-yl) ester trans-4- (trans-4-pentylcyclohexyl ) Cyclohexanecarboxylic acid (2-methyl-pyridin-5-yl) ester trans-4- (trans-4-Hexylcyclohexyl) cyclohexanecarboxylic acid (2-methyl-pyridin-5-yl) ester trans-4- (trans-4-heptylcyclohexyl ) cyclohexane carboxylic acid (2-methyl-pyridin-5-yl) ester
trans-4-(trans-4-Ethylcyclohexyl)cyclohexancarbonsäure- (2-ethyl-pyridin-5-yl)ester trans-4-(trans-4-Propylcyclohexyl)cyclohexancarbonsäure- (2-ethyl-pyridin-5-yl)ester trans-4-(trans-4-Butylcyclohexyl)cyclohexancarbonsäure- (2-ethyl-pyridin-5-yl)ester trans-4-(trans-4-Pentylcyclohexyl)cyclohexancarbonsäure-(2-ethyl-pyridin-5-yl)ester trans-4-(trans-4-Hexylcyclohexyl)cyclohexancarbonsäure- (2-ethyl-pyridin-5-yl)ester trans-4-(trans-4-Heptylcyclohexyl)cyclohexancarbonsäure- (2-ethyl-pyridin-5-yl)estertrans-4- (trans-4-ethylcyclohexyl) cyclohexane carboxylic acid (2-ethyl-pyridin-5-yl) ester trans-4- (trans-4-propylcyclohexyl) cyclohexane carboxylic acid (2-ethyl-pyridin-5-yl) ester trans-4- (trans-4-butylcyclohexyl) cyclohexane carboxylic acid (2-ethyl-pyridin-5-yl) ester trans-4- (trans-4-pentylcyclohexyl) cyclohexane carboxylic acid (2-ethyl-pyridin-5-yl) ester trans-4- (trans-4-Hexylcyclohexyl) cyclohexanecarboxylic acid (2-ethyl-pyridin-5-yl) ester trans-4- (trans-4-heptylcyclohexyl) cyclohexanecarboxylic acid (2-ethyl-pyridin-5-yl) ester
trans-4-(trans-4-Ethylcyclohexyl)cyclohexancarbonsäure-(2-propyl-pyridin-5-yl)ester trans-4-(trans-4-Propylcyclohexyl)cyclohexancarbonsäure-(2-propyl-pyridin-5-yl)ester trans-4-(trans-4-Butylcyclohexyl)cyclohexancarbonsäure-(2-propyl-pyridin-5-yl)ester trans-4-(trans-4-Pentylcyclohexyl)cyclohexancarbonsäure-(2-propyl-pyridin-5-yl)ester trans-4-(trans-4-Hexylcyclohexyl)cyclohexancarbonsäure-(2-propyl-pyridin-5-yl)ester trans-4-(trans-4-Heptylcyclohexyl)cyclohexancarbonsäure-(2-propyl-pyridin-5-yl)estertrans-4- (trans-4-ethylcyclohexyl) cyclohexanecarboxylic acid (2-propyl-pyridin-5-yl) ester trans-4- (trans-4-propylcyclohexyl) cyclohexanecarboxylic acid (2-propyl-pyridin-5-yl) ester trans-4- (trans-4-butylcyclohexyl) cyclohexanecarboxylic acid (2-propyl-pyridin-5-yl) ester trans-4- (trans-4-pentylcyclohexyl) cyclohexanecarboxylic acid (2-propyl-pyridin-5-yl) ester trans-4- (trans-4-hexylcyclohexyl) cyclohexanecarboxylic acid (2-propyl-pyridin-5-yl) ester trans-4- (trans-4-heptylcyclohexyl) cyclohexanecarboxylic acid (2-propyl-pyridin-5-yl) ester
trans-4-(trans-4-Ethylcyclohexyl)cyclohexancarbonsäure- (2-butyl-pyridin-5-yl)ester trans-4-(trans-4-Propylcyclohexyl)cyclohexancarbonsäure- (2-butyl-pyridin-5-yl)ester trans-4-(trans-4-Butylcyclohexyl)cyclohexancarbonsäure-(2-butyl-pyridin-5-yl)ester trans-4-(trans-4-Pentylcyclohexyl)cyclohexancarbonsäure- (2-butyl-pyridin-5-yl)ester trans-4-(trans-4-Hexylcyclohexyl)cyclohexancarbonsäure- (2-butyl-pyridin-5-yl)ester trans-4-(trans-4-Heptylcyclohexyl)cyclohexancarbonsäure- (2-butyl-pyridin-5-yl)estertrans-4- (trans-4-ethylcyclohexyl) cyclohexane carboxylic acid (2-butyl-pyridin-5-yl) ester trans-4- (trans-4-propylcyclohexyl) cyclohexane carboxylic acid (2-butyl-pyridin-5-yl) ester trans-4- (trans-4-butylcyclohexyl) cyclohexane carboxylic acid (2-butyl-pyridin-5-yl) ester trans-4- (trans-4-pentylcyclohexyl) cyclohexane carboxylic acid (2-butyl-pyridin-5-yl) ester trans-4- (trans-4-Hexylcyclohexyl) cyclohexanecarboxylic acid (2-butyl-pyridin-5-yl) ester trans-4- (trans-4-heptylcyclohexyl) cyclohexanecarboxylic acid (2-butyl-pyridin-5-yl) ester
trans-4-(trans-4-Ethylcyclohexyl)cyclohexancarbonsäure- (2-hexyl-pyridin-5-yl)ester trans-4-(trans-4-Propylcyclohexyl)cyclohexancarbonsäure- (2-hexyl-pyridin-5-yl)ester trans-4-(trans-4-Butylcyclohexyl)cyclohexancarbonsäure- (2-hexyl-pyridin-5-yl)ester trans-4-(trans-4-Pentylcyclohexyl)cyclohexancarbonsäure- (2-hexyl-pyridin-5-yl)ester trans-4-(trans-4-Hexylcyclohexyl)cyclohexancarbonsäure- (2-hexyl-pyridin-5-yl)ester trans-4-(trans-4-Heptylcyclohexyl)cyclohexancarbonsäure- (2-hexyl-pyridin-5-yl)estertrans-4- (trans-4-ethylcyclohexyl) cyclohexanecarboxylic acid (2-hexyl-pyridin-5-yl) ester trans-4- (trans-4-propylcyclohexyl) cyclohexanecarboxylic acid (2-hexyl-pyridin-5-yl) ester trans-4- (trans-4-butylcyclohexyl) cyclohexanecarboxylic acid (2-hexyl-pyridin-5-yl) ester trans-4- (trans-4-pentylcyclohexyl) cyclohexanecarboxylic acid (2-hexyl-pyridin-5-yl) ester trans-4- (trans-4-Hexylcyclohexyl) cyclohexanecarboxylic acid (2-hexyl-pyridin-5-yl) ester trans-4- (trans-4-Heptylcyclohexyl) cyclohexanecarboxylic acid (2-hexyl-pyridin-5-yl) ester
trans-4-(trans=4-Ethylcyclohexyl)cyclohexancarbonsäure- (2-heptyl-pyridin-5-yl)ester trans-4-(trans-4-Propylcyclohexyl)cyclohexancarbonsäure- (2-heptyl-pyridin-5-yl)ester trans-4-(trans-4-Butylcyclohexyl)cyclohexancarbonsäure- (2-heptyl-pyridin-5-yl)ester trans-4-(trans-4-Pentylcyclohexyl)cyclohexancarbonsäure- (2-heptyl-pyridin-5-yl)ester trans-4-(trans-4-Hexylcyclohexyl)cyclohexancarbonsäure- (2-heptyl-pyridin-5-yl)ester trans-4-(trans-4-Heptylcyclohexyl)cyclohexancarbonsäure(2-heptyl-pyridin-5-yl)estertrans-4- (trans = 4-ethylcyclohexyl) cyclohexanecarboxylic acid (2-heptyl-pyridin-5-yl) ester trans-4- (trans-4-propylcyclohexyl) cyclohexanecarboxylic acid (2-heptyl-pyridin-5-yl) ester trans-4- (trans-4-butylcyclohexyl) cyclohexanecarboxylic acid (2-heptyl-pyridin-5-yl) ester trans-4- (trans-4-pentylcyclohexyl) cyclohexanecarboxylic acid (2-heptyl-pyridin-5-yl) ester trans-4- (trans-4-hexylcyclohexyl) cyclohexanecarboxylic acid (2-heptyl-pyridin-5-yl) ester trans-4- (trans-4-heptylcyclohexyl) cyclohexanecarboxylic acid (2-heptyl-pyridin-5-yl) ester
trans-4-(trans-4-Ethylcyclohexylethyl)cyclohexancarbonsäure-(2-pentyl-pyridin-5-yl)ester trans-4-(trans-4-Propylcyclohexylethyl)cyclohexancarbonsäure-(2-pentyl-pyridin-5-yl)ester trans-4-(trans-4-Butylcyclohexylethyl)cyclohexancarbonsäure-(2-pentyl-pyridin-5-yl)ester trans-4-(trans-4-Pentylcyclohexylethyl)cyclohexancarbonsäure-(2-pentyl-pyridin-5-yl)ester trans-4-(trans-4-Hexylcyclohexylethyl)cyclohexancarbonsäure-(2-pentyl-pyridin-5-yl)ester trans-4-(trans-4-Heptylcyclohexylethyl)cyclohexancarbonsäure-(2-pentyl-pyridin-5-yl)estertrans-4- (trans-4-ethylcyclohexylethyl) cyclohexanecarboxylic acid (2-pentyl-pyridin-5-yl) ester trans-4- (trans-4-propylcyclohexylethyl) cyclohexanecarboxylic acid (2-pentyl-pyridin-5-yl) ester trans-4- (trans-4-butylcyclohexylethyl) cyclohexanecarboxylic acid (2-pentyl-pyridin-5-yl) ester trans-4- (trans-4-pentylcyclohexylethyl) cyclohexanecarboxylic acid (2-pentyl-pyridin-5-yl) ester trans-4- (trans-4-hexylcyclohexylethyl) cyclohexanecarboxylic acid (2-pentyl-pyridin-5-yl) ester trans-4- (trans-4-heptylcyclohexylethyl) cyclohexanecarboxylic acid (2-pentyl-pyridin-5-yl) ester
trans-4-(trans-4-Ethylcyclohexylethyl)cyclohexancarbonsäure-(2-methyl-pyridin-5-yl)ester trans-4-(trans-4-Propylcyclohexylethyl)cyclohexancarbonsäure-(2-methyl-pyridin-5-yl)ester trans-4-(trans-4-Butylcyclohexylethyl)cyclohexancarbonsäure-(2-methyl-pyridin-5-yl)ester trans-4-(trans-4-Pentylcyclohexylethyl)cyclohexancarbonsäure-(2-methyl-pyridin-5-yl)ester, mp. 98°, cp. 169,2° trans-4-(trans-4-Hexylcyclohexylethyl)cyclohexancarbonsäure-(2-methyl-pyridin-5-yl)ester trans-4-(trans-4-Heptylcyclohexylethyl)cyclohexancarbonsäure-(2-methyl-pcridin-5-yl)ester trans-4-(trans-4-Ethylcyclohexylethyl)cyclohexancarbonsäure-(2-ethyl-pyridin-5-yl)ester trans-4-(trans-4-Propylcyclohexylethyl)cyclohexancarbonsäure-(2-ethyl-pyridin-5-yl)ester trans-4-(trans-4-Butylcyclohexylethyl)cyclohexancarbonsäure-(2-ethyl-pyridin-5-yl)ester trans-4-(trans-4-Pentylcyclohexylethyl)cyclohexancarbonsäure-(2-ethyl-pyridin-5-yl)ester trans-4-(trans-4-Hexylcyclohexylethyl)cyclohexancarbonsäure-(2-ethyl-pyridin-5-yl)ester trans-4-(trans-4-Heptylcyclohexylethyl)cyclohexancarbonsäure-(2-ethyl-pyridin-5-yl)estertrans-4- (trans-4-ethylcyclohexylethyl) cyclohexanecarboxylic acid (2-methyl-pyridin-5-yl) ester trans-4- (trans-4-propylcyclohexylethyl) cyclohexanecarboxylic acid (2-methyl-pyridin-5-yl) ester trans-4- (trans-4-Butylcyclohexylethyl) cyclohexane carboxylic acid (2-methyl-pyridin-5-yl) ester trans-4- (trans-4-Pentylcyclohexylethyl) cyclohexane carboxylic acid (2-methyl-pyridin-5-yl) ester , mp. 98 °, cp. 169.2 ° trans-4- (trans-4-hexylcyclohexylethyl) cyclohexanecarboxylic acid (2-methyl-pyridin-5-yl) ester trans-4- (trans-4-heptylcyclohexylethyl) cyclohexanecarboxylic acid (2-methyl-pcridin-5) -yl) esters trans-4- (trans-4-ethylcyclohexylethyl) cyclohexanecarboxylic acid (2-ethyl-pyridin-5-yl) ester trans-4- (trans-4-propylcyclohexylethyl) cyclohexanecarboxylic acid (2-ethyl-pyridin-5-yl) ester trans-4- (trans-4-butylcyclohexylethyl) cyclohexanecarboxylic acid (2-ethyl-pyridin-5-yl) ester trans-4- (trans-4-pentylcyclohexylethyl) cyclohexanecarboxylic acid (2-ethyl-pyridin-5-yl) ester trans-4- (trans-4-Hexylcyclohexylethyl) cyclohexanecarboxylic acid (2-ethyl-pyridin-5-yl) ester trans-4- (trans-4-heptylcyclohexylethyl) cyclohexanecarboxylic acid (2-ethyl-pyridin-5-yl) ester
trans-4-(trans-4-Ethylcyclohexylethyl)cyclohexancarbonsäure-(2-propyl-pyridin-5-yl)ester trans-4-(trans-4-Propylcyclohexylethyl)cyclohexancarbonsäure-(2-propyl-pyridin-5-yl)ester trans-4-(trans-4-Butylcyclohexylethyl)cyclohexancarbonsäure-(2-propyl-pyridin-5-yl)ester trans-4-(trans-4-Pentylcyclohexylethyl)cyclohexancarbonsäure-(2-propyl-pyridin-5-yl)ester trans-4-(trans-4-Hexylcyclohexylethyl)cyclohexancarbonsäure-(2-propyl-pyridin-5-yl)ester trans-4-(trans-4-Heptylcyclohexylethyl)cyclohexancarbonsäure-(2-propyl-pyridin-5-yl)estertrans-4- (trans-4-Ethylcyclohexylethyl) cyclohexane carboxylic acid (2-propyl-pyridin-5-yl) ester trans-4- (trans-4-Propylcyclohexylethyl) cyclohexane carboxylic acid (2-propyl-pyridin-5-yl) ester trans-4- (trans-4-butylcyclohexylethyl) cyclohexanecarboxylic acid (2-propyl-pyridin-5-yl) ester trans-4- (trans-4-pentylcyclohexylethyl) cyclohexanecarboxylic acid (2-propyl-pyridin-5-yl) ester trans-4- (trans-4-Hexylcyclohexylethyl) cyclohexanecarboxylic acid (2-propyl-pyridin-5-yl) ester trans-4- (trans-4-heptylcyclohexylethyl) cyclohexanecarboxylic acid (2-propyl-pyridin-5-yl) ester
trans-4-(trans-4-Ethylcyclohexylethyl)cyclohexancarbonsäure-(2-butyl-pyridin-5-yl)ester trans-4-(trans-4-Propylcyclohexylethyl)cyclohexancarbonsäure-(2-butyl-pyridin-5-yl)ester trans-4-(trans-4-Butylcyclohexylethyl)cyclohexancarbonsäure-(2-butyl-pyridin-5-yl)ester trans-4-(trans-4-Pentylcyclohexylethyl)cyclohexancarbonsäure-(2-butyl-pyridin-5-yl)ester trans-4-(trans-4-Hexylcyclohexylethyl)cyclohexancarbonsäure-(2-butyl-pyridin-5-yl)ester trans-4-(trans-4-Heptylcyclohexylethyl)cyclohexancarbonsäure-(2-butyl-pyridin-5-yl)estertrans-4- (trans-4-ethylcyclohexylethyl) cyclohexanecarboxylic acid (2-butyl-pyridin-5-yl) ester trans-4- (trans-4-propylcyclohexylethyl) cyclohexanecarboxylic acid (2-butyl-pyridin-5-yl) ester trans-4- (trans-4-butylcyclohexylethyl) cyclohexane carboxylic acid (2-butyl-pyridin-5-yl) ester trans-4- (trans-4-Pentylcyclohexylethyl) cyclohexane carboxylic acid (2-butyl-pyridin-5-yl) ester trans-4- (trans-4-Hexylcyclohexylethyl) cyclohexane carboxylic acid (2-butyl-pyridin-5-yl) ester trans-4- (trans-4-heptylcyclohexylethyl) cyclohexane carboxylic acid (2-butyl-pyridin-5-yl) ester
trans-4-(trans-4-Ethylcyclohexylethyl)cyclohexancarbonsäure-(2-hexyl-pyridin-5-yl)ester trans-4-(trans-4-Propylcyclohexylethyl)cyclohexancarbonsäure-(2-hexyl-pyridin-5-yl)ester trans-4-(trans-4-Butylcyclohexylethyl)cyclohexancarbonsäure-(2-hexyl-pyridin-5-yl)ester trans-4-(trans-4-Pentylcyclohexylethyl)cyclohexancarbonsäure-(2-hexyl-pyridin-5-yl)ester trans-4-(trans-4-Hexylcyclohexylethyl)cyclohexancarbonsäure-(2-hexyl-pyridin-5-yl)ester trans-4-(trans-4-Heptylcyclohexylethyl)cyclohexancarbonsäure-(2-hexyl-pyridin-5-yl)estertrans-4- (trans-4-ethylcyclohexylethyl) cyclohexanecarboxylic acid (2-hexyl-pyridin-5-yl) ester trans-4- (trans-4-propylcyclohexylethyl) cyclohexanecarboxylic acid (2-hexyl-pyridin-5-yl) ester trans-4- (trans-4-butylcyclohexylethyl) cyclohexanecarboxylic acid (2-hexyl-pyridin-5-yl) ester trans-4- (trans-4-pentylcyclohexylethyl) cyclohexanecarboxylic acid (2-hexyl-pyridin-5-yl) ester trans-4- (trans-4-Hexylcyclohexylethyl) cyclohexanecarboxylic acid (2-hexyl-pyridin-5-yl) ester trans-4- (trans-4-Heptylcyclohexylethyl) cyclohexanecarboxylic acid (2-hexyl-pyridin-5-yl) ester
trans-4-(trans-4-Ethylcyclohexylethyl)cyclohexancarbonsäure-(2-heptyl-pyridin-5-yl)ester trans-4-(trans-4-Propylcyclohexylethyl)cyclohexancarbonsäure-(2-heptyl-pyridin-5-yl)ester trans-4-(trans-4-Butylcyclohexylethyl)cyclohexancarbonsäure-(2-heptyl-pyridin-5-yl)ester trans-4-(trans-4-Pentylcyclohexylethyl)cyclohexancarbonsäure-(2-heptyl-pyridin-5-yl)ester trans-4-(trans-4-Hexylcyclohexylethyl)cyclohexancarbonsäure-(2-heptyl-pyridin-5-yl)ester trans-4-(trans-4-Heptylcyclohexylethyl)cyclohexancarbonsäure-(2-heptyl-pyridin-5-yl)ester trans-4-Ethylcyclohexancarbonsäure-(2-pentyl-pyridin- 5-yl)-ester trans-4-Propylcyclohexancarbonsäure-(2-pentyl-pyridin- 5-yl)-ester, mp. 37°, cp. 38° trans-4-Butylcyclohexancarbonsäure-(2-pentyl-pyridin- 5-yl)-ester trans-4-Pentylcyclohexancarbonsäure-(2-pentyl-pyridin- 5-yl)-ester, mp. 16°, cp. 65° trans-4-Hexylcyclohexancarbonsäure-(2-pentyl-pyridin-5-yl)-ester trans-4-Heptylcyclohexancarbonsäure-(2-pentyl-pyridin- 5-yl)-ester trans-4-Octylcyclohexancarbonsäure-(2-pentyl-pyridin- 5-yl)-ester trans-4-Nonylcyclohexancarbonsäure-(2-pentyl-pyridin- 5-yl)-estertrans-4- (trans-4-ethylcyclohexylethyl) cyclohexanecarboxylic acid (2-heptyl-pyridin-5-yl) ester trans-4- (trans-4-propylcyclohexylethyl) cyclohexanecarboxylic acid (2-heptyl-pyridin-5-yl) ester trans-4- (trans-4-butylcyclohexylethyl) cyclohexanecarboxylic acid (2-heptyl-pyridin-5-yl) ester trans-4- (trans-4-pentylcyclohexylethyl) cyclohexanecarboxylic acid (2-heptyl-pyridin-5-yl) ester trans-4- (trans-4-Hexylcyclohexylethyl) cyclohexanecarboxylic acid (2-heptyl-pyridin-5-yl) ester trans-4- (trans-4-Heptylcyclohexylethyl) cyclohexanecarboxylic acid (2-heptyl-pyridin-5-yl) ester trans-4-ethylcyclohexanecarboxylic acid (2-pentyl-pyridin-5-yl) ester trans-4-propylcyclohexanecarboxylic acid (2-pentyl-pyridin-5-yl) ester, mp. 37 °, cp. 38 ° trans-4-butylcyclohexanecarboxylic acid (2-pentyl-pyridin-5-yl) ester trans-4-pentylcyclohexanecarboxylic acid (2-pentyl-pyridin-5-yl) ester, mp. 16 °, cp. 65 ° trans-4-hexylcyclohexanecarboxylic acid (2-pentyl-pyridin-5-yl) ester trans-4-heptylcyclohexanecarboxylic acid (2-pentyl-pyridin-5-yl) ester trans-4-octylcyclohexanecarboxylic acid (2-pentyl -pyridin- 5-yl) ester trans-4-nonylcyclohexane carboxylic acid (2-pentyl-pyridin-5-yl) ester
trans-4-Ethylcyclohexancarbonsäure-(2-methyl-pyridin- 5-yl)-ester, mp. 34° trans-4-Propylcyclohexancarbonsäure-(2-methyl-pyridin-5-yl)-ester, mp. 40°, cp. 0° trans-4-Butylcyclohexancarbonsäure-(2-methyl-pyridin- 5-yl)-ester, mp. 41°, cp. 20° trans-4-Pentylcyclohexancarbonsäure-(2-methyl-pyridin- 5-yl)-ester, mp. 48°, cp. 39° trans-4-Hexylcyclohexancarbonsäure-(2-methyl-pyridin- 5-yl)-ester trans-4-Heptylcyclohexancarbonsäure-(2-methyl-pyridin- 5-yl)-ester trans-4-Octylcyclohexancarbonsäure-(2-methyl-pyridin- 5-yl)-ester trans-4-Nonylcyclohexancarbonsäure-(2-methyl-pyridin- 5-yl)-ester trans-4-Decylcyclohexancarbonsäure-(2-methyl-pyridin-5-yl)-ester trans-4-Undecylcyclohexancarbonsäure-(2-methyl-pyridin-5-yl)-ester trans-4-Dodecylcyclohexancarbonsäure-(2-methyl-pyridin-5-yl)-estertrans-4-ethylcyclohexane carboxylic acid (2-methyl-pyridin-5-yl) ester, mp. 34 ° trans-4-propylcyclohexane carboxylic acid (2-methyl-pyridin-5-yl) ester, mp. 40 °, cp. 0 ° trans-4-butylcyclohexane carboxylic acid (2-methyl-pyridin-5-yl) ester, mp. 41 °, cp. 20 ° trans-4-pentylcyclohexane carboxylic acid (2-methyl-pyridin-5-yl) ester, mp. 48 °, cp. 39 ° trans-4-hexylcyclohexanecarboxylic acid (2-methyl-pyridin-5-yl) ester trans-4-heptylcyclohexanecarboxylic acid (2-methyl-pyridin-5-yl) ester trans-4-octylcyclohexanecarboxylic acid (2-methyl -pyridin-5-yl) ester trans-4-nonylcyclohexane carboxylic acid (2-methyl-pyridin-5-yl) ester trans-4-decylcyclohexanecarboxylic acid (2-methyl-pyridin-5-yl) ester trans-4-undecylcyclohexanecarboxylic acid (2-methyl-pyridin-5-yl) ester trans-4-dodecylcyclohexanecarboxylic acid (2-methyl-pyridine) -5-yl) ester
trans-4-Ethylcyclohexancarbonsäure-(2-ethyl-pyridin- 5-yl)-ester trans-4-Propylcyclohexancarbonsäure-(2-ethyl-pyridin-5-yl)-ester trans-4-Butylcyclohexancarbonsäure-(2-ethyl-pyridin- 5-yl)-ester trans-4-Pentylcyclohexancarbonsäure-(2-ethyl-pyridin- 5-yl)-ester trans-4-Hexylcyclohexancarbonsäure-(2-ethyl-pyridin- 5-yl)-ester trans-4-Heptylcyclohexancarbonsäure-(2-ethyl-pyridin- 5-yl)-ester trans-4-Octylcyclohexancarbonsäure-(2-ethyl-pyridin-5-yl)-ester trans-4-Nonylcyclohexancarbonsäure-(2-ethyl-pyridin- 5-yl)-ester trans-4-Decylcyclohexancarbonsäure-(2-ethyl-pyridin- 5-yl)-ester trans-4-Undecylcyclohexancarbonsäure-(2-ethyl-pyridin- 5-yl)-ester trans-4-Dodecylcyclohexancarbonsäure-(2-ethyl-pyridin- 5-yl)-estertrans-4-ethylcyclohexanecarboxylic acid (2-ethyl-pyridin-5-yl) ester trans-4-propylcyclohexanecarboxylic acid (2-ethyl-pyridin-5-yl) ester trans-4-butylcyclohexanecarboxylic acid (2-ethyl-pyridine) - 5-yl) -ester trans-4-pentylcyclohexanecarboxylic acid- (2-ethyl-pyridin-5-yl) -ester trans-4-hexylcyclohexanecarboxylic acid- (2-ethyl-pyridin-5-yl) ester trans-4-heptylcyclohexanecarboxylic acid - (2-ethyl-pyridin-5-yl) ester trans-4-octylcyclohexanecarboxylic acid- (2-ethyl-pyridin-5-yl) ester trans-4-nonylcyclohexanecarboxylic acid- (2-ethyl-pyridin-5-yl) -ester trans-4-decylcyclohexanecarboxylic acid- (2-ethyl-pyridin-5-yl) -ester trans-4-undecylcyclohexanecarboxylic acid- (2-ethyl-pyridin-5-yl) -ester trans-4-dodecylcyclohexanecarboxylic acid- (2-ethyl -pyridin-5-yl) ester
trans-4-Ethylcyclohexancarbonsäure-(2-propyl-pyridin-5-yl)-ester trans-4-Propylcyclohexancarbonsäure-(2-propyl-pyridin- 5-yl)-ester trans-4-Butylcyclohexancarbonsäure-(2-propyl-pyridin- 5-yl)-ester trans-4-Pentylcyclohexancarbonsäure-(2-propyl-pyridin- 5-yl)-ester trans-4-Hexylcyclohexancarbonsäure-(2-propyl-pyridin- 5-yl)-ester trans-4-Heptylcyclohexancarbonsäure-(2-propyl-pyridin- 5-yl)-ester trans-4-Octylcyclohexancarbonsäure-(2-propyl-pyridin-5-yl)-ester trans-4-Nonylcyclohexancarbonsäure-(2-propyl-pyridin- 5-yl)-ester trans-4-Decylcyclohexancarbonsäure-(2-propyl-pyridin- 5-yl)-ester trans-4-Undecylcyclohexancarbonsäure-(2-propyl-pyridin- 5-yl)-ester trans-4-Dodecylcyclohexancarbonsäure-(2-propyl-pyridin- 5-yl)-estertrans-4-ethylcyclohexanecarboxylic acid (2-propyl-pyridin-5-yl) ester trans-4-propylcyclohexanecarboxylic acid (2-propyl-pyridin-5-yl) ester trans-4-butylcyclohexanecarboxylic acid (2-propyl-pyridine-5-yl) ester trans-4-pentylcyclohexanecarboxylic acid (2-propyl-pyridine-5-yl) ester trans-4-hexylcyclohexanecarboxylic acid (2-propyl-pyridine) - 5-yl) -ester trans-4-heptylcyclohexanecarboxylic acid- (2-propyl-pyridin-5-yl) -ester trans-4-octylcyclohexanecarboxylic acid- (2-propyl-pyridin-5-yl) -ester trans-4-nonylcyclohexanecarboxylic acid - (2-propyl-pyridine-5-yl) -ester trans-4-decylcyclohexanecarboxylic acid- (2-propyl-pyridin-5-yl) -ester trans-4-undecylcyclohexanecarboxylic acid- (2-propyl-pyridin-5-yl) -ester trans-4-dodecylcyclohexane carboxylic acid (2-propyl-pyridin-5-yl) ester
trans-4-Ethylcyclohexancarbonsäure-(2-butyl-pyridin-5-yl)-ester trans-4-Propylcyclohexancarbonsäure-(2-butyl-pyridin- 5-yl)-ester trans-4-Butylcyclohexancarbonsäure-(2-butyl-pyridin- 5-yl)-ester trans-4-Pentylcyclohexancarbonsäure-(2-butyl-pyridin- 5-yl)-ester trans-4-Hexylcyclohexancarbonsäure-(2-butyl-pyridin- 5-yl)-ester trans-4-Heptylcyclohexancarbonsäure-(2-butyl-pyridin- 5-yl)-ester trans-4-Octylcyclohexancarbonsäure-(2-butyl-pyridin- 5-yl)-ester trans-4-Nonylcyclohexancarbonsäure-(2-butyl-pyridin-5-yl)-ester trans-4-Decylcyclohexancarbonsäure-(2-butyl-pyridin-5-yl)-ester trans-4-Undecylcyclohexancarbonsäure-(2-butyl-pyridin-5-yl)-ester trans-4-Dodecylcyclohexancarbonsäure-(2-butyl-pyridin-5-yl)-estertrans-4-ethylcyclohexanecarboxylic acid (2-butyl-pyridin-5-yl) ester trans-4-propylcyclohexanecarboxylic acid (2-butyl-pyridin-5-yl) ester trans-4-butylcyclohexanecarboxylic acid (2-butyl-pyridine) - 5-yl) -ester trans-4-pentylcyclohexanecarboxylic acid- (2-butyl-pyridine-5-yl) -ester trans-4-hexylcyclohexanecarboxylic acid- (2-butyl-pyridin-5-yl) ester trans-4-heptylcyclohexanecarboxylic acid - (2-Butyl-pyridin-5-yl) ester trans-4-octylcyclohexane carboxylic acid (2-butyl-pyridin-5-yl) ester trans-4-nonylcyclohexanecarboxylic acid (2-butyl-pyridin-5-yl) ester trans-4-decylcyclohexanecarboxylic acid (2-butyl-pyridin-5-yl) ester trans-4-undecylcyclohexanecarboxylic acid (2-butyl-pyridine) -5-yl) ester trans-4-dodecylcyclohexane carboxylic acid (2-butyl-pyridin-5-yl) ester
trans-4-Ethylcyclohexancarbonsäure-(2-hexyl-pyridin-5-yl)-ester trans-4-Propylcyclohexancarbonsäure-(2-hexyl-pyridin- 5-yl)-ester trans-4-Butylcyclohexancarbonsäure-(2-hexyl-pyridin- 5-yl)-ester trans-4-Pentylcyclohexancarbonsäure-(2-hexyl-pyridin- 5-yl)-ester trans-4-Hexylcyclohexancarbonsäure-(2-hexyl-pyridin- 5-yl)-ester trans-4-Heptylcyclohexancarbonsäure-(2-hexyl-pyridin-5-yl)-estertrans-4-ethylcyclohexanecarboxylic acid (2-hexyl-pyridin-5-yl) ester trans-4-propylcyclohexanecarboxylic acid (2-hexyl-pyridin-5-yl) ester trans-4-butylcyclohexanecarboxylic acid (2-hexyl-pyridine) - 5-yl) -ester trans-4-pentylcyclohexanecarboxylic acid- (2-hexyl-pyridine-5-yl) -ester trans-4-hexylcyclohexanecarboxylic acid- (2-hexyl-pyridin-5-yl) -ester trans-4-heptylcyclohexanecarboxylic acid - (2-hexyl-pyridin-5-yl) ester
trans-4-Ethylcyclohexancarbonsäure-(2-heptyl-pyridin- 5-yl)-ester trans-4-Propylcyclohexancarbonsäure-(2-heptyl-pyridin- 5-yl)-ester trans-4-Butylcyclohexancarbonsäure-(2-heptyl-pyridin- 5-yl)-ester trans-4-Pentylcyclohexancarbonsäure-(2-heptyl-pyridin- 5-yl)-ester trans-4-Hexylcyclohexancarbonsäure-(2-heptyl-pyridin-5-yl)-ester trans-4-Heptylcyclohexancarbonsäure-(2-heptyl-pyridin- 5-yl)-ester Beispiel 2trans-4-ethylcyclohexanecarboxylic acid (2-heptyl-pyridine-5-yl) ester trans-4-propylcyclohexanecarboxylic acid (2-heptyl-pyridin-5-yl) ester trans-4-butylcyclohexanecarboxylic acid (2-heptyl-pyridine) - 5-yl) -ester trans-4-pentylcyclohexanecarboxylic acid- (2-heptyl-pyridin-5-yl) -ester trans-4-hexylcyclohexanecarboxylic acid- (2-heptyl-pyridin-5-yl) ester trans-4-heptylcyclohexanecarboxylic acid - (2-heptyl-pyridin-5-yl) ester Example 2
Zu 0,1 mol trans-4-Pentylcyclohexancarbonsäure, 0,1 mol 5-Hydroxy-2-methoxy-pyridin (Darstellung analog R. Adams et al., J. Amer. Chem. Soc. 69, 1806-1808 (1947) und L. Rodes et al., Rev. CENIC, Cienc Fis (1973), 4 (1-2), 81-7, CA 84 745050x) und einer katalytischen Menge DMAP in 250 ml CH2Cl2 gibt man unter Feuchtigkeitsausschluß bei 0° eine Lösung von 0,1 mol DCC in CH2Cl2. Man rührt 12 Stunden bei Raumtemperatur, filtriert den Dicyclohexylharnstoff ab und arbeitet das Filtrat auf.To 0.1 mol of trans-4-pentylcyclohexane carboxylic acid, 0.1 mol of 5-hydroxy-2-methoxy-pyridine (representation analogous to R. Adams et al., J. Amer. Chem. Soc. 69, 1806-1808 (1947) and L. Rodes et al., Rev. CENIC, Cienc Fis (1973), 4 (1-2), 81-7, CA 84 745050x) and a catalytic amount of DMAP in 250 ml of CH 2 Cl 2 are added with exclusion of moisture 0 ° a solution of 0.1 mol DCC in CH 2 Cl 2 . The mixture is stirred for 12 hours at room temperature, the dicyclohexylurea is filtered off and the filtrate is worked up.
Nach Reinigung durch Chromatographie und/oder Kristallisation erhält man trans-4-Pentylcyclohexancarbonsäure-(2-methoxy-pyridin-5-yl)-ester.After purification by chromatography and / or crystallization, trans-4-pentylcyclohexane carboxylic acid (2-methoxy-pyridin-5-yl) ester is obtained.
Analog werden hergestellt:The following are produced analogously:
trans-4-Ethylcyclohexancarbonsäure-(2-methoxypyridin-5-yl)-ester trans-4-Propylcyclohexancarbonsäure-(2-methoxypyridin-5-yl)-ester trans-4-Butylcyclohexancarbonsäure-(2-methoxypyridin-5-yl)-estertrans-4-ethylcyclohexanecarboxylic acid (2-methoxypyridin-5-yl) ester trans-4-propylcyclohexanecarboxylic acid (2-methoxypyridin-5-yl) ester trans-4-butylcyclohexanecarboxylic acid (2-methoxypyridin-5-yl) - ester
trans-4-Ethylcyclohexancarbonsäure-(2-ethoxy-pyridin-5- yl)-ester trans-4-Propylcyclohexancarbonsäure-(2-ethoxy-pyridin-5- yl)-ester trans-4-Butylcyclohexancarbonsäure-(2-ethoxy-pyridin-5- yl)-ester trans-4-Pentylcyclohexancarbonsäure-(2-ethoxy-pyridin-5- yl)-ester trans-4-Ethylcyclohexancarbonsäure-(2-propoxypyridin-5-yl)-ester trans-4-Propylcyclohexancarbonsäure-(2-propoxypyridin-5-yl)-ester trans-4-Butylcyclohexancarbonsäure-(2-propoxypyridin-5-yl)-ester trans-4-Pentylcyclohexancarbonsäure-(2-propoxypyridin-5-yl)-estertrans-4-ethylcyclohexanecarboxylic acid (2-ethoxy-pyridin-5-yl) ester trans-4-propylcyclohexanecarboxylic acid (2-ethoxy-pyridin-5-yl) ester trans-4-butylcyclohexanecarboxylic acid (2-ethoxy-pyridine) -5-yl) ester trans-4-pentylcyclohexane carboxylic acid (2-ethoxy-pyridin-5-yl) ester trans-4-ethylcyclohexanecarboxylic acid (2-propoxypyridin-5-yl) ester trans-4-propylcyclohexanecarboxylic acid (2-propoxypyridin-5-yl) ester trans-4-butylcyclohexanecarboxylic acid (2-propoxypyridin-5-yl) - ester trans-4-pentylcyclohexane carboxylic acid (2-propoxypyridin-5-yl) ester
trans-4-Ethylcyclohexancarbonsäure-(2-butoxypyridin-5-yl)-ester trans-4-Propylcyclohexancarbonsäure-(2-butoxypyridin-5-yl)-ester trans-4-Butylcyclohexancarbonsäure-(2-butoxypyridin-5-yl)-ester trans-4-Pentylcyclohexancarbonsäure-(2-butoxypyridin-5-yl)-ester trans-4-Hexylcyclohexancarbonsäure-(2-butoxypyridin-5-yl)-ester trans-4-Heptylcyclohexancarbonsäure-(2-butoxypyridin-5-yl)-estertrans-4-ethylcyclohexanecarboxylic acid (2-butoxypyridin-5-yl) ester trans-4-propylcyclohexanecarboxylic acid (2-butoxypyridin-5-yl) ester trans-4-butylcyclohexanecarboxylic acid (2-butoxypyridin-5-yl) - ester trans-4-pentylcyclohexanecarboxylic acid (2-butoxypyridin-5-yl) ester trans-4-hexylcyclohexanecarboxylic acid (2-butoxypyridin-5-yl) ester trans-4-heptylcyclohexanecarboxylic acid (2-butoxypyridin-5-yl) -ester
trans-4-Ethylcyclohexancarbonsäure-(2-pentyloxypyridin-5-yl)-ester trans-4-Propylcyclohexancarbonsäure-(2-pentyloxypyridin-5-yl)-ester trans-4-Butylcyclohexancarbonsäure-(2-pentyloxypyridin-5-yl)-ester trans-4-Pentylcyclohexancarbonsäure-(2-pentyloxypyridin-5=yl)-ester trans-4-Hexylcyclohexancarbonsäure-(2-pentyloxypyridin-5-yl)-ester trans-4-Heptylcyclohexancarbonsäure-(2-pentyloxypyridin-5-yl)-ester trans-4-(trans-4-Ethylcyclohexylethyl)cyclohexancarbonsäure-(2-pentyloxy-pyridin-5-yl)ester trans-4-(trans-4-Propylcyclohexylethyl)cyclohexancarbonsäure-(2-pentyloxy-pyridin-5-yl)ester trans-4-(trans-4-Butylcyclohexylethyl)cyclohexancarbonsäure-(2-pentyloxy-pyridin-5-yl)ester trans-4-(trans-4-Pentylcyclohexylethyl)cyclohexancarbonsäure-(2-pentyloxy-pyridin-5-yl)ester trans-4-(trans-4-Hexylcyclohexylethyl)cyclohexancarbonsäure-(2-pentyloxy-pyridin-5-yl)ester trans-4-(trans-4-Heptylcyclohexylethyl)cyclohexancarbonsäure-(2-pentyloxy-pyridin-5-yl)estertrans-4-ethylcyclohexanecarboxylic acid (2-pentyloxypyridin-5-yl) ester trans-4-propylcyclohexanecarboxylic acid (2-pentyloxypyridin-5-yl) ester trans-4-butylcyclohexanecarboxylic acid (2-pentyloxypyridin-5-yl) - ester trans-4-pentylcyclohexanecarboxylic acid- (2-pentyloxypyridin-5 = yl) ester trans-4-hexylcyclohexanecarboxylic acid- (2-pentyloxypyridin-5-yl) ester trans-4-heptylcyclohexanecarboxylic acid- (2-pentyloxypyridin-5-yl) -ester trans-4- (trans-4-ethylcyclohexylethyl) cyclohexanecarboxylic acid (2-pentyloxy-pyridin-5-yl) ester trans-4- (trans-4-propylcyclohexylethyl) cyclohexanecarboxylic acid (2-pentyloxypyridin-5-yl) ester trans-4- (trans-4-butylcyclohexylethyl) cyclohexanecarboxylic acid (2-pentyloxypyridin-5-yl) ester trans-4- (trans-4-pentylcyclohexylethyl) cyclohexanecarboxylic acid (2-pentyloxypyridin-5-yl) ester trans-4- (trans-4-Hexylcyclohexylethyl) cyclohexanecarboxylic acid (2-pentyloxypyridin-5-yl) ester trans-4- (trans-4-Heptylcyclohexylethyl) cyclohexanecarboxylic acid (2-pentyloxypyridin-5-yl) ester
trans-4-(trans-4-Ethylcyclohexylethyl)cyclohexancarbonsäure-(2-methoxy-pyridin-5-yl)ester trans-4-(trans-4-Propylcyclohexylethyl)cyclohexancarbonsäure-(2-methoxy-pyridin-5-yl)ester trans-4-(trans-4-Butylcyclohexylethyl)cyclohexancarbonsäure-(2-methoxy-pyridin-5-yl)ester trans-4-(trans-4-Pentylcyclohexylethyl)cyclohexancarbonsäure-(2-methoxy-pyridin-5-yl)ester trans-4-(trans-4-Hexylcyclohexylethyl)cyclohexancarbonsäure-(2-methoxy-pyridin-5-yl)ester trans-4-(trans-4-Heptylcyclohexylethyl)cyclohexancarbonsäure-(2-methoxy-pyridin-5-yl)estertrans-4- (trans-4-Ethylcyclohexylethyl) cyclohexane carboxylic acid (2-methoxy-pyridin-5-yl) ester trans-4- (trans-4-Propylcyclohexylethyl) cyclohexane carboxylic acid (2-methoxy-pyridin-5-yl) ester trans-4- (trans-4-butylcyclohexylethyl) cyclohexane carboxylic acid (2-methoxy-pyridin-5-yl) ester trans-4- (trans-4-pentylcyclohexylethyl) cyclohexane carboxylic acid (2-methoxy-pyridin-5-yl) ester trans-4- (trans-4-Hexylcyclohexylethyl) cyclohexane carboxylic acid (2-methoxy-pyridin-5-yl) ester trans-4- (trans-4-Heptylcyclohexylethyl) cyclohexane carboxylic acid (2-methoxy-pyridin-5-yl) ester
trans-4-(trans-4-Ethylcyclohexylethyl)cyclohexancarbonsäure-(2-ethoxy-pyridin-5-yl)ester trans-4-(trans-4-Propylcyclohexylethyl)cyclohexancarbonsäure-(2-ethoxy-pyridin-5-yl)ester trans-4-(trans-4-Butylcyclohexylethyl)cyclohexancarbonsäure-(2-ethoxy-pyridin-5-yl)ester trans-4-(trans-4-Pentylcyclohexylethyl)cyclohexancarbonsäure-(2-ethoxy-pyridin-5-yl)ester trans-4-(trans-4-Hexylcyclohexylethyl)cyclohexancarbonsäure-(2-ethoxy-pyridin-5-yl)ester trans-4-(trans-4-Heptylcyclohexylethyl)cyclohexancarbonsäure-(2-ethoxy-pyridin-5-yl)estertrans-4- (trans-4-Ethylcyclohexylethyl) cyclohexanecarboxylic acid (2-ethoxypyridin-5-yl) ester trans-4- (trans-4-Propylcyclohexylethyl) cyclohexanecarboxylic acid (2-ethoxypyridin-5-yl) ester trans-4- (trans-4-butylcyclohexylethyl) cyclohexane carboxylic acid (2-ethoxy-pyridin-5-yl) ester trans-4- (trans-4-pentylcyclohexylethyl) cyclohexanecarboxylic acid (2-ethoxypyridin-5-yl) ester trans-4- (trans-4-hexylcyclohexylethyl) cyclohexanecarboxylic acid (2-ethoxypyridin-5-yl) ester trans-4- (trans-4-heptylcyclohexylethyl) cyclohexane carboxylic acid (2-ethoxy-pyridin-5-yl) ester
trans-4-(trans-4-Ethylcyclohexylethyl)cyclohexancarbonsäure-(2-propoxy-pyridin-5-yl)ester trans-4-(trans-4-Propylcyclohexylethyl)cyclohexancarbonsäure-(2-propoxy-pyridin-5-yl)ester trans-4-(trans-4-Butylcyclohexylethyl)cyclohexancarbonsäure-(2-propoxy-pyridin-5-yl)ester trans-4-(trans-4-Pentylcyclohexylethyl)cyclohexancarbonsäure-(2-propoxy-pyridin-5-yl)ester trans-4-(trans-4-Hexylcyclohexylethyl)cyclohexancarbonsäure-(2-propoxy-pyridin-5-yl)ester trans-4-(trans-4-Heptylcyclohexylethyl)cyclohexancarbonsäure-(2-propoxy-pyridin-5-yl)estertrans-4- (trans-4-ethylcyclohexylethyl) cyclohexanecarboxylic acid (2-propoxypyridin-5-yl) ester trans-4- (trans-4-propylcyclohexylethyl) cyclohexanecarboxylic acid (2-propoxypyridin-5-yl) ester trans-4- (trans-4-butylcyclohexylethyl) cyclohexanecarboxylic acid (2-propoxypyridin-5-yl) ester trans-4- (trans-4-pentylcyclohexylethyl) cyclohexanecarboxylic acid (2-propoxypyridin-5-yl) ester trans-4- (trans-4-Hexylcyclohexylethyl) cyclohexanecarboxylic acid (2-propoxypyridin-5-yl) ester trans-4- (trans-4-Heptylcyclohexylethyl) cyclohexanecarboxylic acid (2-propoxypyridin-5-yl) ester
trans-4-(trans-4-Ethylcyclohexylethyl)cyclohexancarbonsäure-(2-butoxy-pyridin-5-yl)-ster trans-4-(trans-4-Propylcyclohexylethyl)cyclohexancarbonsäure-(2-butoxy-pyridin-5-yl)ester trans-4-(trans-4-Butylcyclohexylethyl)cyclohexancarbonsäure-(2-butoxy-pyridin-5-yl)ester trans-4-(trans-4-Pentylcyclohexylethyl)cyclohexancarbonsäure-(2-butoxy-pyridin-5-yl)ester trans-4-(trans-4-Hexylcyclohexylethyl)cyclohexancarbonsäure-(2-butoxy-pyridin-5-yl)ester trans-4-(trans-4-Heptylcyclohexylethyl)cyclohexancarbonsäure-(2-butoxy-pyridin-5-yl)ester trans-4-(trans-4-Ethylcyclohexylethyl)cyclohexancarbon-säure-(2-hexyloxy-pyridin-5-yl)ester trans-4-(trans-4-Propylcyclohexylethyl)cyclohexancarbon-säure-(2-hexyloxy-pyridin-5-yl)ester trans-4-(trans-4-Butylcyclohexylethyl)cyclohexancarbon-säure-(2-hexyloxy-pyridin-5-yl)ester trans-4-(trans-4-Hexylcyclohexylethyl)cyclohexancarbon-säure-(2-hexyloxy-pyridin-5-yl)ester trans-4-(trans-4-Heptylcyclohexylethyl)cyclohexancarbon-säure-(2-hexyloxy-pyridin-5-yl)estertrans-4- (trans-4-ethylcyclohexylethyl) cyclohexanecarboxylic acid (2-butoxypyridin-5-yl) ester trans-4- (trans-4-propylcyclohexylethyl) cyclohexanecarboxylic acid (2-butoxypyridin-5-yl) ester trans-4- (trans-4-butylcyclohexylethyl) cyclohexanecarboxylic acid- (2-butoxypyridin-5-yl) ester trans-4- (trans-4-pentylcyclohexylethyl) cyclohexanecarboxylic acid- (2-butoxypyridin-5-yl) ester trans-4- (trans-4-hexylcyclohexylethyl) cyclohexanecarboxylic acid (2-butoxypyridin-5-yl) ester trans-4- (trans-4-heptylcyclohexylethyl) cyclohexanecarboxylic acid (2-butoxypyridin-5-yl) ester trans-4- (trans-4-ethylcyclohexylethyl) cyclohexane carboxylic acid (2-hexyloxy-pyridin-5-yl) ester trans-4- (trans-4-propylcyclohexylethyl) cyclohexane carboxylic acid (2-hexyloxy pyridine-5) -yl) ester trans-4- (trans-4-butylcyclohexylethyl) cyclohexanecarboxylic acid (2-hexyloxypyridin-5-yl) ester trans-4- (trans-4-hexylcyclohexylethyl) cyclohexanecarboxylic acid (2-hexyloxy -pyridin-5-yl) ester trans-4- (trans-4-heptylcyclohexylethyl) cyclohexane carboxylic acid (2-hexyloxypyridin-5-yl) ester
trans-4-(trans-4-Ethylcyclohexyl)cyclohexancarbonsäure- (2-pentyloxy-pyridin-5-yl)ester trans-4-(trans-4-Propylcyclohexyl)cyclohexancarbonsäure- (2-pentyloxy-pyridin-5-yl)ester trans-4-(trans-4-Butylcyclohexyl)cyclohexancarbonsäure- (2-pentyloxy-pyridin-5-yl)ester trans-4-(trans-4-Pentylcyclohexyl)cyclohexancarbonsäure- (2-pentyloxy-pyridin-5-yl)ester trans-4-(trans-4-Hexylcyclohexyl)cyclohexancarbonsäure- (2-pentyloxy-pyridin-5-yl)ester trans-4-(trans-4-Heptylcyclohexyl)cyclohexancarbonsäure- (2-pentyloxy-pyridin-5-yl)estertrans-4- (trans-4-ethylcyclohexyl) cyclohexanecarboxylic acid (2-pentyloxypyridin-5-yl) ester trans-4- (trans-4-propylcyclohexyl) cyclohexanecarboxylic acid (2-pentyloxypyridin-5-yl) ester trans-4- (trans-4-butylcyclohexyl) cyclohexanecarboxylic acid (2-pentyloxypyridin-5-yl) ester trans-4- (trans-4-pentylcyclohexyl) cyclohexanecarboxylic acid (2-pentyloxypyridin-5-yl) ester trans-4- (trans-4-Hexylcyclohexyl) cyclohexanecarboxylic acid (2-pentyloxypyridin-5-yl) ester trans-4- (trans-4-Heptylcyclohexyl) cyclohexanecarboxylic acid (2-pentyloxypyridin-5-yl) ester
trans-4-(trans-4-Ethylcyclohexyl)cyclohexancarbonsäure- (2-methoxy-pyridin-5-yl)ester trans-4-(trans-4-Propylcyclohexyl)cyclohexancarbonsäure- (2-methoxy-pyridin-5-yl)ester trans-4-(trans-4-Butylcyclohexyl)cyclohexancarbonsäure- (2-methoxy-pyridin-5-yl)ester trans-4-(trans-4-Pentylcyclohexyl)cyclohexancarbonsäure- (2-methoxy-pyridin-5-yl)ester trans-4-(trans-4-Hexylcyclohexyl)cyclohexancarbonsäure- (2-methoxy-pyridin-5-yl)ester trans-4-(trans-4-Heptylcyclohexyl)cyclohexancarbonsäure- (2-methoxy-pyridin-5-yl)estertrans-4- (trans-4-ethylcyclohexyl) cyclohexanecarboxylic acid (2-methoxy-pyridin-5-yl) ester trans-4- (trans-4-propylcyclohexyl) cyclohexanecarboxylic acid (2-methoxy-pyridin-5-yl) ester trans-4- (trans-4-butylcyclohexyl) cyclohexane carboxylic acid (2-methoxy-pyridin-5-yl) ester trans-4- (trans-4-pentylcyclohexyl) cyclohexane carboxylic acid (2-methoxy-pyridin-5-yl) ester trans-4- (trans-4-Hexylcyclohexyl) cyclohexanecarboxylic acid (2-methoxy-pyridin-5-yl) ester trans-4- (trans-4-Heptylcyclohexyl) cyclohexanecarboxylic acid (2-methoxy-pyridin-5-yl) ester
trans-4-(trans-4-Ethylcyclohexyl)cyclohexancarbonsäure- (2-ethoxy-pyridin-5-yl)ester trans-4-(trans-4-Propylcyclohexyl)cyclohexancarbonsäure- (2-ethoxy-pyridin-5-yl)ester trans-4-(trans-4-Butylcyclohexyl)cyclohexancarbonsäure-(2-ethoxy-pyridin-5-yl)ester trans-4-(trans-4-Pentylcyclohexyl)cyclohexancarbonsäure- (2-ethoxy-pyridin-5-yl)ester trans-4-(trans-4-Hexylcyclohexyl)cyclohexancarbonsäure- (2-ethoxy-pyridin-5-yl)ester trans-4-(trans-4-Heptylcyclohexyl)cyclohexancarbonsäure- (2-ethoxy-pyridin-5-yl)estertrans-4- (trans-4-ethylcyclohexyl) cyclohexanecarboxylic acid (2-ethoxypyridin-5-yl) ester trans-4- (trans-4-propylcyclohexyl) cyclohexanecarboxylic acid (2-ethoxypyridin-5-yl) ester trans-4- (trans-4-butylcyclohexyl) cyclohexanecarboxylic acid (2-ethoxypyridin-5-yl) ester trans-4- (trans-4-pentylcyclohexyl) cyclohexanecarboxylic acid (2-ethoxypyridin-5-yl) ester trans-4- (trans-4-Hexylcyclohexyl) cyclohexanecarboxylic acid (2-ethoxypyridin-5-yl) ester trans-4- (trans-4-heptylcyclohexyl) cyclohexanecarboxylic acid (2-ethoxypyridin-5-yl) ester
trans-4-(trans-4-Ethylcyclohexyl)cyclohexancarbonsäure-trans-4- (trans-4-ethylcyclohexyl) cyclohexanecarboxylic acid-
(2-propoxy-pyridin-5-yl)ester trans-4-(trans-4-Propylcyclohexyl)cyclohexancarbonsäure-(2-propoxy-pyridin-5-yl)ester trans-4-(trans-4-Butylcyclohexyl)cyclohexancarbonsäure-(2-propoxy-pyridin-5-yl) ester trans-4- (trans-4-propylcyclohexyl) cyclohexanecarboxylic acid- (2-propoxy-pyridin-5-yl) ester trans-4- (trans-4-butylcyclohexyl) cyclohexanecarboxylic acid-
(2-propoxy-pyridin-5-yl)ester trans-4-(trans-4-Pentylcyclohexyl)cyclohexancarbonsäure- (2-propoxy-pyridin-5-yl)ester trans-4-(trans-4-Hexylcyclohexyl)cyclohexancarbonsäure- (2-propoxy-pyridin-5-yl)ester trans-4-(trans-4-Heptylcyclohexyl)cyclohexancarbonsäure- (2-propoxy-pyridin-5-yl)ester(2-propoxy-pyridin-5-yl) ester trans-4- (trans-4-pentylcyclohexyl) cyclohexane carboxylic acid- (2-propoxy-pyridin-5-yl) ester trans-4- (trans-4-hexylcyclohexyl) cyclohexane carboxylic acid- (2-propoxy-pyridin-5-yl) ester trans-4- (trans-4-heptylcyclohexyl) cyclohexane carboxylic acid (2-propoxy-pyridin-5-yl) ester
trans-4-(trans-4-Ethylcyclohexyl)cyclohexancarbonsäure-(2-butoxy-pyridin-5-yl)ester trans-4-(trans-4-Propylcyclohexyl)cyclohexancarbonsäure- (2-butoxy-pyridin-5-yl)ester trans-4-(trans-4-Butylcyclohexyl)cyclohexancarbonsäure-(2-butoxy-pyridin-5-yl)ester trans-4-(trans-4-Pentylcyclohexyl)cyclohexancarbonsäure-(2-butoxy-pyridin-5-yl)ester trans-4-(trans-4-Hexylcyclohexyl)cyclohexancarbonsäure-(2-butoxy-pyridin-5-yl)ester trans-4-(trans-4-Heptylcyclohexyl)cyclohexancarbonsäure-(2-butoxy-pyridin-5-yl)estertrans-4- (trans-4-ethylcyclohexyl) cyclohexanecarboxylic acid (2-butoxypyridin-5-yl) ester trans-4- (trans-4-propylcyclohexyl) cyclohexanecarboxylic acid (2-butoxypyridin-5-yl) ester trans-4- (trans-4-butylcyclohexyl) cyclohexanecarboxylic acid (2-butoxypyridin-5-yl) ester trans-4- (trans-4-pentylcyclohexyl) cyclohexanecarboxylic acid (2-butoxypyridin-5-yl) ester trans-4- (trans-4-Hexylcyclohexyl) cyclohexanecarboxylic acid (2-butoxypyridin-5-yl) ester trans-4- (trans-4-Heptylcyclohexyl) cyclohexanecarboxylic acid (2-butoxypyridin-5-yl) ester
trans-4-(trans-4-Ethylcyclohexyl)cyclohexancarbonsäure-(2-hexyloxy-pyridin-5-yl)ester trans-4-(trans-4-Propylcyclohexyl)cyclohexancarbonsäure- (2-hexyloxy-pyridin-5-yl)ester trans-4-(trans-4-Butylcyclohexyl)cyclohexancarbonsäure- (2-hexyloxy-pyridin-5-yl)ester trans-4-(trans-4-Pentylcyclohexyl)cyclohexancarbonsäure- (2-hexyloxy-pyridin-5-yl)ester trans-4-(trans-4-Hexylcyclohexyl)cyclohexancarbonsäure- (2-hexyloxy-pyridin-5-yl)ester trans-4-(trans-4-Heptylcyclohexyl)cyclohexancarbonsäure- (2-hexyloxy-pyridin-5-yl)estertrans-4- (trans-4-ethylcyclohexyl) cyclohexanecarboxylic acid (2-hexyloxypyridin-5-yl) ester trans-4- (trans-4-propylcyclohexyl) cyclohexanecarboxylic acid (2-hexyloxypyridin-5-yl) ester trans-4- (trans-4-butylcyclohexyl) cyclohexanecarboxylic acid (2-hexyloxypyridin-5-yl) ester trans-4- (trans-4-pentylcyclohexyl) cyclohexanecarboxylic acid (2-hexyloxypyridin-5-yl) ester trans-4- (trans-4-Hexylcyclohexyl) cyclohexanecarboxylic acid (2-hexyloxypyridin-5-yl) ester trans-4- (trans-4-Heptylcyclohexyl) cyclohexanecarboxylic acid (2-hexyloxypyridin-5-yl) ester
trans-4-(trans-4-Ethylcyclohexyl)cyclohexancarbonsäure- (2-heptyloxy-pyridin-5-yl)ester trans-4-(trans-4-Propylcyclohexyl)cyclohexancarbonsäure- (2-heptyloxy-pyridin-5-yl)ester trans-4-(trans-4-Butylcyclohexyl)cyclohexancarbonsäure- (2-heptyloxy-pyridin-5-yl)ester trans-4-(trans-4-Pentylcyclohexyl)cyclohexancarbonsäure- (2-heptyloxy-pyridin-5-yl)ester trans-4-(trans-4-Hexylcyclohexyl)cyclohexancarbonsäure- (2-heptyloxy-pyridin-5-yl)ester trans-4-(trans-4-Heptylcyclohexyl)cyclohexancarbonsäure- (2-heptyloxy-pyridin-5-yl)ester Beispiel 3trans-4- (trans-4-ethylcyclohexyl) cyclohexanecarboxylic acid (2-heptyloxypyridin-5-yl) ester trans-4- (trans-4-propylcyclohexyl) cyclohexanecarboxylic acid (2-heptyloxypyridin-5-yl) ester trans-4- (trans-4-butylcyclohexyl) cyclohexanecarboxylic acid (2-heptyloxypyridin-5-yl) ester trans-4- (trans-4-pentylcyclohexyl) cyclohexanecarboxylic acid (2-heptyloxypyridin-5-yl) ester trans-4- (trans-4-Hexylcyclohexyl) cyclohexanecarboxylic acid (2-heptyloxypyridin-5-yl) ester trans-4- (trans-4-Heptylcyclohexyl) cyclohexanecarboxylic acid (2-heptyloxypyridin-5-yl) ester Example 3
a) 0,1 mol trans-4-(trans-4-Ethylcyclohexyl)cyclohexylmethyliodid, 13,8 g wasserfreies K2CO3, 0,1 mol 3- Hydroxy-6-methylpyridin und 1,1 g Benzyltriethylammoniumchlorid werden in 100 ml Methylethylketon 30 Stunden am Rückfluß erhitzt. Das Reaktionsgemisch wird mit Wasser versetzt und die organische Phase wie üblich aufgearbeitet. Nach Reinigung durch Kristallisation erhält mana) 0.1 mol of trans-4- (trans-4-ethylcyclohexyl) cyclohexylmethyl iodide, 13.8 g of anhydrous K 2 CO 3 , 0.1 mol of 3-hydroxy-6-methylpyridine and 1.1 g of benzyltriethylammonium chloride in 100 ml Methyl ethyl ketone heated to reflux for 30 hours. Water is added to the reaction mixture and the organic phase is worked up as usual. After cleaning by crystallization, one obtains
trans-4-(trans-4-Ethylcyclohexyl)cyclohexylmethyl(2-methyl-pyridin-5-yl)ether.trans-4- (trans-4-ethylcyclohexyl) cyclohexylmethyl (2-methyl-pyridin-5-yl) ether.
b) Man gibt bei -30 °C zu einer Lösung von Lithiumdiisopropylamid (1,44 g Diisopropylamin und 3 ml 1,6 N Butyllithium in Hexan) in 25 ml THF 1,83 g 1,3-Dimethyltetrahydro-2-(1H)-pyrimidinon (DMPU), 5,2 g des in a) hergestellten Pyridinethers und 1,81 g Brombutan. Anschließend rührt man das Reaktionsgemisch 12 Stunden unter langsamer Erwärmung auf Raumtemperatur. Nach üblicher Aufarbeitung erhält man trans-4-(trans-4-Ethylcyclohexyl)cyclohexylmethyl-(2-pentyl-pyridin-5-yl)-ether.b) 1.83 g of 1,3-dimethyltetrahydro-2- (1H) are added at -30 ° C. to a solution of lithium diisopropylamide (1.44 g of diisopropylamine and 3 ml of 1.6 N butyllithium in hexane) in 25 ml of THF. pyrimidinone (DMPU), 5.2 g of the pyridine ether prepared in a) and 1.81 g of bromobutane. The reaction mixture is then stirred for 12 hours while slowly warming to room temperature. After the usual work-up, trans-4- (trans-4-ethylcyclohexyl) cyclohexylmethyl (2-pentylpyridin-5-yl) ether is obtained.
Analog werden hergestellt:The following are produced analogously:
trans-(4-Propylcyclohexyl)cyclohexylmethyl-(2-methyl-pyridin-5-yl)ether, mp. 92°, cp. 148° trans-(4-Butylcyclohexyl)cyclohexylmethyl-(2-methyl-pyridin-5-yl)ether trans-(4-Pentylcyclohexyl)cyclohexylmethyl-(2-methyl-pyridin-5-yl)ether trans-(4-Hexylcyclohexyl)cyclohexylmethyl-(2-methyl-pyridin-5-yl)ether trans-(4-Heptylcyclohexyl)cyclohexylmethyl-(2-methyl-pyridin-5-yl)ether trans-(4-Octylcyclohexyl)cyclohexylmethyl-(2-methyl-pyridin-5-yl)ethertrans- (4-propylcyclohexyl) cyclohexylmethyl- (2-methyl-pyridin-5-yl) ether, mp. 92 °, cp. 148 ° trans- (4-butylcyclohexyl) cyclohexylmethyl (2-methyl-pyridin-5-yl) ether trans- (4-pentylcyclohexyl) cyclohexylmethyl (2-methyl-pyridin-5-yl) ether trans- (4-hexylcyclohexyl) cyclohexylmethyl- (2-methyl-pyridin-5-yl) ether trans- (4-heptylcyclohexyl) cyclohexylmethyl- (2-methyl-pyridin-5-yl) ether trans- (4-octylcyclohexyl) cyclohexylmethyl - (2-methyl-pyridin-5-yl) ether
trans-4-(trans-4-Propylcyclohexyl)cyclohexylmethyl-(2-pentyl-pyridin-5-yl)ether, K 59° SB 100° N 129.2 I trans-4-(trans-4-Butylcyclohexyl)cyclohexylmethyl-(2-pentyl-pyridin-5-yl)ether trans-4-(trans-4-Pentylcyclohexyl)cyclohexylmethyl-(2-pentyl-pyridin-5-yl)ether trans-4-(trans-4-Hexylcyclohexyl)cyclohexylmethyl-(2-pentyl-pyridin-5-yl)ether trans-4-(trans-4-Heptylcyclohexyl)cyclohexylmethyl-(2-pentyl-pyridin-5-yl)ether trans-4-(trans-4-Octylcyclohexyl)cyclohexylmethyl-(2-pentyl-pyridin-5-yl)ethertrans-4- (trans-4-propylcyclohexyl) cyclohexylmethyl- (2-pentyl-pyridin-5-yl) ether, K 59 ° S B 100 ° N 129.2 I trans-4- (trans-4-butylcyclohexyl) cyclohexylmethyl- ( 2-pentyl-pyridin-5-yl) ether trans-4- (trans-4-pentylcyclohexyl) cyclohexylmethyl- (2-pentyl-pyridin-5-yl) ether trans-4- (trans-4-hexylcyclohexyl) cyclohexylmethyl- ( 2-pentyl-pyridin-5-yl) ether trans-4- (trans-4-heptylcyclohexyl) cyclohexylmethyl- (2-pentyl-pyridin-5-yl) ether trans-4- (trans-4-octylcyclohexyl) cyclohexylmethyl- ( 2-pentyl-pyridin-5-yl) ether
trans-4-(trans-4-Ethylcyclohexyl)cyclohexylmethyl-(2-ethyl-pyridin-5-yl)ether trans-4-(trans-4-Propylcyclohexyl)cyclohexylmethyl-(2-ethyl-pyridin-5-yl)ether trans-4-(trans-4-Butylcyclohexyl)cyclohexylmethyl-(2- ethyl-pyridin-5-yl)ether trans-4-(trans-4-Pentylcyclohexyl)cyclohexylmethyl-(2- ethyl-pyridin-5-yl)ethertrans-4- (trans-4-ethylcyclohexyl) cyclohexylmethyl (2-ethyl-pyridin-5-yl) ether trans-4- (trans-4-propylcyclohexyl) cyclohexylmethyl (2-ethyl-pyridin-5-yl) ether trans-4- (trans-4-butylcyclohexyl) cyclohexylmethyl (2-ethyl-pyridin-5-yl) ether trans-4- (trans-4-pentylcyclohexyl) cyclohexylmethyl (2-ethyl-pyridin-5-yl) ether
trans-4-(trans-4-Ethylcyclohexyl)cyclohexylmethyl-(2- propyl-pyridin-5-yl)ether trans-4-(trans-4-Propylcyclohexyl)cyclohexylmethyl-(2- propyl-pyridin-5-yl)ether trans-4-(trans-4-Butylcyclohexyl)cyclohexylmethyl-(2-propyl-pyridin-5-yl)ether trans-4-(trans-4-Pentylcyclohexyl)cyclohexylmethyl-(2-propyl-pyridin-5-yl)ethertrans-4- (trans-4-ethylcyclohexyl) cyclohexylmethyl (2-propyl-pyridin-5-yl) ether trans-4- (trans-4-propylcyclohexyl) cyclohexylmethyl (2-propyl-pyridin-5-yl) ether trans-4- (trans-4-butylcyclohexyl) cyclohexylmethyl (2-propyl-pyridin-5-yl) ether trans-4- (trans-4-pentylcyclohexyl) cyclohexylmethyl (2-propyl-pyridin-5-yl) ether
trans-4-(trans-4-Ethylcyclohexyl)cyclohexylmethyl-(2-butyl-pyridin-5-yl)ether trans-4-(trans-4-Propylcyclohexyl)cyclohexylmethyl-(2-butyl-pyridin-5-yl)ether trans-4-(trans-4-Butylcyclohexyl)cyclohexylmethyl-(2-butyl-pyridin-5-yl)ether trans-4-(trans-4-Pentylcyclohexyl)cyclohexylmethyl-(2-butyl-pyridin-5-yl)ethertrans-4- (trans-4-ethylcyclohexyl) cyclohexylmethyl (2-butyl-pyridin-5-yl) ether trans-4- (trans-4-propylcyclohexyl) cyclohexylmethyl (2-butyl-pyridin-5-yl) ether trans-4- (trans-4-butylcyclohexyl) cyclohexylmethyl (2-butyl-pyridin-5-yl) ether trans-4- (trans-4-pentylcyclohexyl) cyclohexylmethyl (2-butyl-pyridin-5-yl) ether
trans-4-(trans-4-Ethylcyclohexyl)cyclohexylmethyl-(2-hexyl-pyridin-5-yl)ether trans-4-(trans-4-Propylcyclohexyl)cyclohexylmethyl-(2-hexyl-pyridin-5-yl)ether trans-4-(trans-4-Butylcyclohexyl)cyclohexylmethyl-(2-hexyl-pyridin-5-yl)ether trans-4-(trans-4-Pentylcyclohexyl)cyclohexylmethyl-(2-hexyl-pyridin-5-yl)ethertrans-4- (trans-4-ethylcyclohexyl) cyclohexylmethyl (2-hexyl-pyridin-5-yl) ether trans-4- (trans-4-propylcyclohexyl) cyclohexylmethyl (2-hexyl-pyridin-5-yl) ether trans-4- (trans-4-butylcyclohexyl) cyclohexylmethyl (2-hexyl-pyridin-5-yl) ether trans-4- (trans-4-pentylcyclohexyl) cyclohexylmethyl (2-hexyl-pyridin-5-yl) ether
trans-4-(trans-4-Ethylcyclohexyl)cyclohexylmethyl-(2-heptyl-pyridin-5-yl)ether trans-4-(trans-4-Propylcyclohexyl)cyclohexylmethyl-(2-heptyl-pyridin-5-yl)ether trans-4-(trans-4-Butylcyclohexyl)cyclohexylmethyl-(2-heptyl-pyridin-5-yl)ether trans-4-(trans-4-Pentylcyclohexyl)cyclohexylmethyl-(2-heptyl-pyridin-5-yl)ether trans-4-Ethylcyclohexylmethyl-(2-methylpyridin-5-yl)ether trans-4-Propylcyclohexylmethyl-(2-methylpyridin-5-yl)ether trans-4-Hexylcyclohexylmethyl-(2-methylpyridin-5-yl)ether trans-4-Heptylcyclohexylmethyl-(2-methylpyridin-5-yl)ether trans-4-Octylcyclohexylmethyl-(2-methylpyridin-5-yl)ether trans-4-Pentylcyclohexylmethyl-(2-methylpyridin-5-yl)ether trans-4-Ethylcyclohexylmethyl-(2-pentyl-pyridin-5-yl)-ether trans-4-Propylcyclohexylmethyl-(2-pentyl-pyridin-5-yl)-ether trans-4-Butylcyclohexylmethyl-(2-pentyl-pyridin-5-yl)-ether trans-4-Pentylcyclohexylmethyl-(2-pentyl-pyridin-5-yl)-ether trans-4-Hexylcyclohexylmethyl-(2-pentyl-pyridin-5-yl)-ether trans-4-Heptylcyclohexylmethyl-(2-pentyl-pyridin-5-yl)-ether trans-4-Ethylcyclohexylmethyl-(2-ethyl-pyridin-5-yl)-ether trans-4-Propylcyclohexylmethyl-(2-ethyl-pyridin-5-yl)-ether trans-4-Butylcyclohexylmethyl-(2-ethyl-pyridin-5-yl)- ether trans-4-Pentylcyclohexylmethyl-(2-ethyl-pyridin-5-yl)- ether trans-4-Hexylcyclohexylmethyl-(2-ethyl-pyridin-5-yl)-ether trans-4-Heptylcyclohexylmethyl-(2-ethyl-pyridin-5-yl)-ethertrans-4- (trans-4-ethylcyclohexyl) cyclohexylmethyl (2-heptyl-pyridin-5-yl) ether trans-4- (trans-4-propylcyclohexyl) cyclohexylmethyl (2-heptyl-pyridin-5-yl) ether trans-4- (trans-4-butylcyclohexyl) cyclohexylmethyl (2-heptyl-pyridin-5-yl) ether trans-4- (trans-4-pentylcyclohexyl) cyclohexylmethyl (2-heptyl-pyridin-5-yl) ether trans-4-ethylcyclohexylmethyl- (2-methylpyridin-5-yl) ether trans-4-propylcyclohexylmethyl- (2-methylpyridin-5-yl) ether trans-4-hexylcyclohexylmethyl- (2-methylpyridin-5-yl) ether trans- 4-heptylcyclohexylmethyl- (2-methylpyridin-5-yl) ether trans-4-octylcyclohexylmethyl- (2-methylpyridin-5-yl) ether trans-4-pentylcyclohexylmethyl- (2-methylpyridin-5-yl) ether trans-4- Ethylcyclohexylmethyl (2-pentylpyridin-5-yl) ether trans-4-propylcyclohexylmethyl (2-pentylpyridin-5-yl) ether trans-4-butylcyclohexylmethyl- (2-pentylpyridin-5-yl) ) ether trans-4-pentylcyclohexylmethyl- (2-pentyl-pyridin-5-yl) ether trans-4-hexylcyclohexylmethyl- (2-pentyl-pyridin-5-yl) ether trans-4-heptylcyclohexylmethyl- (2- pentyl-pyridin-5-yl) -ether trans-4-ethylcyclohexylmethyl- (2-ethyl-pyridin-5-yl) -ether trans-4-propylcyclohexylmethyl- (2-ethyl-pyridin-5-yl) -ether trans- 4-Butylcyclohexylmethyl- (2-ethyl-pyridin-5-yl) ether trans-4-Pentylcyclohexylmethyl- (2-ethyl-pyridin-5-yl) ether trans-4-hexylcyclohexylmethyl (2-ethyl-pyridin-5-yl) ether trans-4-heptylcyclohexylmethyl (2-ethyl-pyridin-5-yl) ether
trans-4-Ethylcyclohexylmethyl-(2-propyl-pyridin-5-yl)-ether trans-4-Propylcyclohexylmethyl-(2-propyl-pyridin-5-yl)-ether trans-4-Butylcyclohexylmethyl- ( 2-propyl-pyridin-5-yl ) -ether trans-4-Pentylcyclohexylmethyl- (2-propyl-pyridin-5-yl )-ether trans-4-Hexylcyclohexylmethyl-(2-propyl-pyridin-5-yl)-ether trans-4-Heptylcyclohexylmethyl-(2-propyl-pyridin-5-yl)-ethertrans-4-ethylcyclohexylmethyl (2-propyl-pyridin-5-yl) ether trans-4-propylcyclohexylmethyl (2-propyl-pyridin-5-yl) ether trans-4-butylcyclohexylmethyl (2-propyl-pyridine) -5-yl) ether trans-4-pentylcyclohexylmethyl- (2-propyl-pyridin-5-yl) ether trans-4-hexylcyclohexylmethyl- (2-propyl-pyridin-5-yl) ether trans-4-heptylcyclohexylmethyl - (2-propyl-pyridin-5-yl) ether
trans-4-Ethylcyclohexylmethyl-(2-butyl-pyridin-5-yl)-ether trans-4-Propylcyclohexylmethyl-(2-butyl-pyridin-5-yl)-ether trans-4-Butylcyclohexylmethyl-(2-butyl-pyridin-5-yl)-ether trans-4-Pentylcyclohexylmethyl-(2-butyl-pyridin-5-yl)- ether trans-4-Hexylcyclohexylmethyl-(2-butyl-pyridin-5-yl)-ether trans-4-Heptylcyclohexylmethyl-(2-butyl-pyridin-5-yl)-ethertrans-4-ethylcyclohexylmethyl (2-butyl-pyridin-5-yl) ether trans-4-propylcyclohexylmethyl (2-butyl-pyridin-5-yl) ether trans-4-butylcyclohexylmethyl (2-butyl-pyridine) -5-yl) ether trans-4-pentylcyclohexylmethyl- (2-butyl-pyridin-5-yl) ether trans-4-hexylcyclohexylmethyl- (2-butyl-pyridin-5-yl) ether trans-4-heptylcyclohexylmethyl - (2-butyl-pyridin-5-yl) ether
trans-4-Ethylcyclohexylmethyl-(2-hexyl-pyridin-5-yl)-ether trans-4-Propylcyclohexylmethyl-(2-hexyl-pyridin-5-yl)-ether trans-4-Butylcyclohexylmethyl-(2-hexyl-pyridin-5-yl)-ether trans-4-Pentylcyclohexylmethyl-(2-hexyl-pyridin-5-yl)-ether trans-4-Hexylcyclohexylmethyl-(2-hexyl-pyridin-5-yl)-ether trans-4-Heptylcyclohexylmethyl-(2-hexyl-pyridin-5-yl)- ethertrans-4-ethylcyclohexylmethyl (2-hexyl-pyridin-5-yl) ether trans-4-propylcyclohexylmethyl (2-hexyl-pyridin-5-yl) ether trans-4-butylcyclohexylmethyl (2-hexyl-pyridin-5-yl) ether trans-4-pentylcyclohexylmethyl (2-hexyl-pyridin-5-yl) ether trans-4-hexylcyclohexylmethyl (2-hexyl-pyridine) -5-yl) ether trans-4-heptylcyclohexylmethyl- (2-hexyl-pyridin-5-yl) ether
trans-4-Ethylcyclohexylmethyl-(2-heptyl-pyridin-5-yl)- ether trans-4-Propylcyclohexylmethyl-(2-heptyl-pyridin-5-yl)-ether trans-4-Butylcyclohexylmethyl-(2-heptyl-pyridin-5-yl)-ether trans-4-Pentylcyclohexylmethyl-(2-heptyl-pyridin-5-yl)-ether trans-4-Hexylcyclohexylmethyl-(2-heptyl-pyridin-5-yl)-ether trans-4-Heptylcyclohexylmethyl-(2-heptyl-pyridin-5-yl)-ethertrans-4-ethylcyclohexylmethyl- (2-heptyl-pyridin-5-yl) ether trans-4-propylcyclohexylmethyl- (2-heptyl-pyridin-5-yl) ether trans-4-butylcyclohexylmethyl- (2-heptyl-pyridine) -5-yl) ether trans-4-pentylcyclohexylmethyl- (2-heptyl-pyridin-5-yl) ether trans-4-hexylcyclohexylmethyl- (2-heptyl-pyridin-5-yl) ether trans-4-heptylcyclohexylmethyl - (2-heptyl-pyridin-5-yl) ether
Beispiel 4Example 4
0,1 m 5-Hydroxy-2-{2-[trans-4-(trans-4-pentylcyclohexylethyl)cyclohexyl] ethyl} -pyridin (Darstellung erfolgt z.B. durch Umsetzung von 2-Methyl-5-hydroxypyridin und trans-4-(trans-4-Pentylcyclohexylethyl)-cyclohexylmethyliodid analog Beispiel 1) werden in Methylethylketon in Gegenwart von 0,12 mol K2CO3 (wasserfrei) und 0,1 mol Brompentan 24 Stunden am Rückfluß erhitzt. Man arbeitet wie üblich auf und erhält nach chromatographischer Reinigung 5-Pentyloxy- 2-{2-[trans-4-(trans-4-pentylcyclohexylethyl)cyclohexyl]- ethyl}-pyridin, mit K 65° SQ (54°) Sß 142° I. Analog werden hergestellt:0.1 m 5-hydroxy-2- {2- [trans-4- (trans-4-pentylcyclohexylethyl) cyclohexyl] ethyl} pyridine (preparation is carried out, for example, by reacting 2-methyl-5-hydroxypyridine and trans-4- (Trans-4-pentylcyclohexylethyl) cyclohexylmethyl iodide analogous to Example 1) are heated in reflux in methyl ethyl ketone in the presence of 0.12 mol of K 2 CO 3 (anhydrous) and 0.1 mol of bromopentane. The mixture is worked up in the customary manner and, after chromatographic purification, 5-pentyloxy- 2- {2- [trans-4- (trans-4-pentylcyclohexylethyl) cyclohexyl] ethyl} pyridine, with K 65 ° S Q (54 °) S, is obtained ß 142 ° I. The following are produced analogously
5-Pentyloxy-2-{2-[trans-4-(trans-4-ethylcyclohexylethyl)-cyclohexyl] ethyl}-pyridin5-pentyloxy-2- {2- [trans-4- (trans-4-ethylcyclohexylethyl) cyclohexyl] ethyl} pyridine
5-Pentyloxy-2-{2-[trans-4-(trans-4-propylcyclohexylethyl)-cyclohexyl] ethyl}-pyridin5-pentyloxy-2- {2- [trans-4- (trans-4-propylcyclohexylethyl) cyclohexyl] ethyl} pyridine
5-Pentyloxy-2-{2-[trans-4-(trans-4-butylcyclohexylethyl)-cyclohexyl] ethyl}-pyridin5-pentyloxy-2- {2- [trans-4- (trans-4-butylcyclohexylethyl) cyclohexyl] ethyl} pyridine
5-Butoxy-2-{2-[trans-4-(trans-4-ethylcyclohexylethyl)-cyclohexyl] ethyl}-pyridin 5-Butoxy-2-{2-[trans-4-(trans-4-propylcyclohexylethyl)-cyclohexyl] ethyl}-pyridin5-butoxy-2- {2- [trans-4- (trans-4-ethylcyclohexylethyl) cyclohexyl] ethyl} pyridine 5-butoxy-2- {2- [trans-4- (trans-4-propylcyclohexylethyl) - cyclohexyl] ethyl} pyridine
5-Butoxy-2-{2-[trans-4-(trans-4-butylcyclohexylethyl)-cyclohexyl] ethyl}-pyridin5-butoxy-2- {2- [trans-4- (trans-4-butylcyclohexylethyl) cyclohexyl] ethyl} pyridine
5-Butoxy-2-{2-[trans-4-(trans-4-pentylcyclohexylethyl)-cyclohexyl] ethyl}-pyridin5-butoxy-2- {2- [trans-4- (trans-4-pentylcyclohexylethyl) cyclohexyl] ethyl} pyridine
5-Propoxy-2-{2-[trans-4-(trans-4-ethylcyclohexylethyl)-cyclohexyl] ethyl}-pyridin5-propoxy-2- {2- [trans-4- (trans-4-ethylcyclohexylethyl) cyclohexyl] ethyl} pyridine
5-Propoxy-2-{2-[trans-4-(trans-4-propylcyclohexylethyl)-cyclohexyl] ethyl}-pyridin 5-Propoxy-2-{2-[trans-4-(trans-4-butylcyclohexylethyl)-cyclohexyl] ethyl}-pyridin5-propoxy-2- {2- [trans-4- (trans-4-propylcyclohexylethyl) cyclohexyl] ethyl} pyridine 5-propoxy-2- {2- [trans-4- (trans-4-butylcyclohexylethyl) - cyclohexyl] ethyl} pyridine
5-Propoxy-2-{2-[trans-4-(trans-4-pentylcyclohexylethyl)-cyclohexyl] ethyl}-pyridin5-propoxy-2- {2- [trans-4- (trans-4-pentylcyclohexylethyl) cyclohexyl] ethyl} pyridine
5-Ethoxy-2-{2-[trans-4-(trans-4-ethylcyclohexylethyl)-cyclohexyl] ethyl}-pyridin5-ethoxy-2- {2- [trans-4- (trans-4-ethylcyclohexylethyl) cyclohexyl] ethyl} pyridine
5-Ethoxy-2-{2-[trans-4-(trans-4-propylcyclohexylethyl)-cyclohexyl] ethyl}-pyridin5-ethoxy-2- {2- [trans-4- (trans-4-propylcyclohexylethyl) cyclohexyl] ethyl} pyridine
5-Ethoxy-2-{2-[trans-4-(trans-4-butylcyclohexylethyl)-cyclohexyl] ethyl}-pyridin 5-Ethoxy-2-{2-[trans-4-(trans-4-pentylcyclohexylethyl)-cyclohexyl] ethyl} -pyridin 5-Methoxy-2-{2-[trans-4-(trans-4-ethylcyclohexylethyl)-cyclohexyl] ethyl}-pyridin5-ethoxy-2- {2- [trans-4- (trans-4-butylcyclohexylethyl) cyclohexyl] ethyl} pyridine 5-ethoxy-2- {2- [trans-4- (trans-4-pentylcyclohexylethyl) - cyclohexyl] ethyl} pyridine 5-methoxy-2- {2- [trans-4- (trans-4-ethylcyclohexylethyl) cyclohexyl] ethyl} pyridine
5-Methoxy-2-{2-[trans-4-(trans-4-propylcyclohexylethyl)-cyclohexyl] ethyl}-pyridin 5-Methoxy-2-{2-[trans-4-(trans-4-butylcyclohexylethyl)-cyclohexyl] ethyl}-pyridin5-methoxy-2- {2- [trans-4- (trans-4-propylcyclohexylethyl) cyclohexyl] ethyl} pyridine 5-methoxy-2- {2- [trans-4- (trans-4-butylcyclohexylethyl) - cyclohexyl] ethyl} pyridine
5-Methoxy-2-{2-[trans-4-(trans-4-pentylcyclohexylethyl)-cyclohexyl] ethyl}-pyridin5-methoxy-2- {2- [trans-4- (trans-4-pentylcyclohexylethyl) cyclohexyl] ethyl} pyridine
5-Hexyloxy-2-{2-[trans-4-(trans-4-ethylcyclohexylethyl)-cyclohexyl] ethyl}-pyridin5-Hexyloxy-2- {2- [trans-4- (trans-4-ethylcyclohexylethyl) cyclohexyl] ethyl} pyridine
5-Hexyloxy-2-{2-[trans-4-(trans-4-propylcyclohexylethyl)-cyclohexyl] ethyl}-pyridin5-Hexyloxy-2- {2- [trans-4- (trans-4-propylcyclohexylethyl) cyclohexyl] ethyl} pyridine
5-Hexyloxy-2-{2-[trans-4-(trans-4-butylcyclohexylethyl)-cyclohexyl] ethyl}-pyridin 5-Hexyloxy-2-{2-[trans-4-(trans-4-pentylcyclohexylethyl)-cyclohexyl]ethyl}-pyridin5-hexyloxy-2- {2- [trans-4- (trans-4-butylcyclohexylethyl) cyclohexyl] ethyl} pyridine 5-hexyloxy-2- {2- [trans-4- (trans-4-pentylcyclohexylethyl) - cyclohexyl] ethyl} pyridine
5-Heptyloxy-2-{2-[trans-4-(trans-4-ethylcyclohexylethyl)-cyclohexyl] ethyl}-pyridin5-heptyloxy-2- {2- [trans-4- (trans-4-ethylcyclohexylethyl) cyclohexyl] ethyl} pyridine
5-Heptyloxy-2-{2-[trans-4-(trans-4-propylcyclohexylethyl)-cyclohexyl] ethyl}-pyridin5-heptyloxy-2- {2- [trans-4- (trans-4-propylcyclohexylethyl) cyclohexyl] ethyl} pyridine
5-Heptyloxy-2-{2-[trans-4-(trans-4-butylcyclohexylethyl)-cyclohexyl] ethyl}-pyridin5-heptyloxy-2- {2- [trans-4- (trans-4-butylcyclohexylethyl) cyclohexyl] ethyl} pyridine
5-Heptyloxy-2-{2-[trans-4-(trans-4-pentylcyclohexylethyl)-cyclohexyl] ethyl}-pyridin5-heptyloxy-2- {2- [trans-4- (trans-4-pentylcyclohexylethyl) cyclohexyl] ethyl} pyridine
5-(2-Fluoroctyloxy)-2-{2-[trans-4-(trans-4-ethylcyclohexylethyl)-cyclohexyl]-ethyl}-pyridin5- (2-Fluoroctyloxy) -2- {2- [trans-4- (trans-4-ethylcyclohexylethyl) cyclohexyl] ethyl} pyridine
5-(2-Fluoroctyloxy)-2-{2-[trans-4-(trans-4-propylcyclohexylethyl)-cyclohexyl]-ethyl}-pyridin 5-(2-Fluoroctyloxy)-2-{2-[trans-4-(trans-4-propylcyclohexyl)cyclohexyl]-ethyl}-pyridin5- (2-Fluoroctyloxy) -2- {2- [trans-4- (trans-4-propylcyclohexylethyl) cyclohexyl] ethyl} pyridine 5- (2-Fluoroctyloxy) -2- {2- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] ethyl} pyridine
5-(2-Fluoroctyloxy)-2-{2-[trans-4-(trans-4-butylcyclohexyl)cyclohexyl]-ethyl}-pyridin 5-(2-Fluoroctyloxy)-2-{2-[trans-4-(trans-4-pentylcyclo- hexyl)cyclohexyl]-ethyl}-pyridin5- (2-Fluoroctyloxy) -2- {2- [trans-4- (trans-4-butylcyclohexyl) cyclohexyl] ethyl} pyridine 5- (2-Fluoroctyloxy) -2- {2- [trans-4- (trans-4-pentylcyclohexyl) cyclohexyl] ethyl} pyridine
5-(2-Fluoroctyloxy)-2-[2-(trans-4-ethylcyclohexyl)-ethyl]-pyridin5- (2-Fluoroctyloxy) -2- [2- (trans-4-ethylcyclohexyl) ethyl] pyridine
5-(2-Fluoroctyloxy)-2-[2-(trans-4-propylcyclohexyl)-ethyl]-pyridin5- (2-Fluoroctyloxy) -2- [2- (trans-4-propylcyclohexyl) ethyl] pyridine
5-(2-Fluoroctyloxy)-2-[2-(trans-4-butylcyclohexyl)-ethyl]-pyridin5- (2-Fluoroctyloxy) -2- [2- (trans-4-butylcyclohexyl) ethyl] pyridine
5-(2-Fluoroctyloxy)-2-[2-(trans-4-pentylcyclohexyl)-ethyl]-pyridin5- (2-Fluoroctyloxy) -2- [2- (trans-4-pentylcyclohexyl) ethyl] pyridine
5-Ethoxy-2-{2-[trans-4-(trans-4-propylcyclohexyl)-cyclohexyl] ethyl}-pyridin5-ethoxy-2- {2- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] ethyl} pyridine
5-Ethoxy-2-{2-[trans-4-(trans-4-butylcyclohexyl)-cyclohexyl] ethyl}-pyridin 5-Ethoxy-2-{2-[trans-4-(trans-4-pentylcyclohexyl)-cyclohexyl] ethyl}-pyridin5-ethoxy-2- {2- [trans-4- (trans-4-butylcyclohexyl) cyclohexyl] ethyl} pyridine 5-ethoxy-2- {2- [trans-4- (trans-4-pentylcyclohexyl) - cyclohexyl] ethyl} pyridine
5-Propoxy-2-{2-[trans-4-(trans-4-ethylcyclohexyl)-cyclohexyl] ethyl}-pyridin5-propoxy-2- {2- [trans-4- (trans-4-ethylcyclohexyl) cyclohexyl] ethyl} pyridine
5-Propoxy-2-{2-[trans-4-(trans-4-propylcyclohexyl)-cyclohexyl] ethyl}-pyridin 5-Propoxy-2-{2-[trans-4-(trans-4-pentylcyclohexyl)-cyclohexyl] ethyl}-pyridin5-propoxy-2- {2- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] ethyl} pyridine 5-propoxy-2- {2- [trans-4- (trans-4-pentylcyclohexyl) - cyclohexyl] ethyl} pyridine
5-Pentyloxy-2-{2-[trans-4-(trans-4-ethylcyclohexyl)-cyclohexyl] ethyl}-pyridin 5-Pentyloxy-2-{2-[trans-4-(trans-4-propylcyclohexyl)-cyclohexyl] ethyl}-pyridin 5-Pentyloxy-2-{2-[trans-4-(trans-4-butylcyclohexyl)-cyclohexyl] ethyl}-pyridin5-pentyloxy-2- {2- [trans-4- (trans-4-ethylcyclohexyl) cyclohexyl] ethyl} pyridine 5-pentyloxy-2- {2- [trans-4- (trans-4-propylcyclohexyl) - cyclohexyl] ethyl} pyridine 5-pentyloxy-2- {2- [trans-4- (trans-4-butylcyclohexyl) cyclohexyl] ethyl} pyridine
5-Pentyloxy-2-{2-[trans-4-(trans-4-pentylcyclohexyl)-cyclohexyl] ethyl}-pyridin5-pentyloxy-2- {2- [trans-4- (trans-4-pentylcyclohexyl) cyclohexyl] ethyl} pyridine
Beispiel 5Example 5
Zu einer Suspension von 0,1 mol 5-Hydroxy-2-[2-(trans-4-pentylcyclohexyl)ethyl]-pyridin (Darstellung analog Beispiel 1), 0,1 mol 4-Pentyloxybenzoesäure und einer katalytischen Menge DMAP in 200 ml CH2Cl2 gibt man bei 0°-5° eine Lösung von 18,2 g DCC in 50 ml CH2Cl2.To a suspension of 0.1 mol of 5-hydroxy-2- [2- (trans-4-pentylcyclohexyl) ethyl] pyridine (preparation analogous to Example 1), 0.1 mol of 4-pentyloxybenzoic acid and a catalytic amount of DMAP in 200 ml CH 2 Cl 2 is added at 0 ° -5 ° to a solution of 18.2 g DCC in 50 ml CH 2 Cl 2 .
Man rührt 12 Stunden bei Raumtemperatur, filtriert ab und arbeitet das Filtrat wie üblich auf. Nach Reinigung durch Kristallisation erhält man 4-Pentyloxy-benzoesäure-{2-[2-(trans-4-pentylcyclohexyl)ethyl]-pyridin-5-yl} ester.The mixture is stirred at room temperature for 12 hours, filtered off and the filtrate is worked up in the customary manner. After purification by crystallization, 4-pentyloxybenzoic acid {2- [2- (trans-4-pentylcyclohexyl) ethyl] pyridin-5-yl} ester is obtained.
Analog werden hergestellt:The following are produced analogously:
4-Pentyloxy-benzoesäure-{2-[2-(trans-4-ethylcyclohexyl)-ethyl]-pyridin-5-yl} ester4-Pentyloxy-benzoic acid {2- [2- (trans-4-ethylcyclohexyl) ethyl] pyridin-5-yl} ester
4-Pentyloxy-benzoesäure-{2-[2-(trans-4-propylcyclohexyl)-ethyl]-pyridin-5-yl} ester 4-Pentyloxy-benzoesäure-{2-[2-(trans-4-butylcyclohexyl)-ethyl]-pyridin-5-yl}ester4-pentyloxybenzoic acid {2- [2- (trans-4-propylcyclohexyl) ethyl] pyridin-5-yl} ester 4-pentyloxybenzoic acid {2- [2- (trans-4-butylcyclohexyl) - ethyl] pyridin-5-yl} ester
4-Pentyloxy-benzoesäure-{2-[2-(trans-4-hexylcyclohexyl)- ethyl]-pyridin-5-yl}ester4-Pentyloxy-benzoic acid {2- [2- (trans-4-hexylcyclohexyl) ethyl] pyridin-5-yl} ester
4-Pentyloxy-benzoesäure-{2-[2-(trans-4-heptylcyclohexyl)- ethyl]-pyridin-5-yl} ester4-Pentyloxy-benzoic acid {2- [2- (trans-4-heptylcyclohexyl) ethyl] pyridin-5-yl} ester
4-Butoxy-benzoesäure-{2-[2-(trans-4-ethylcyclohexyl)- ethyl]-pyridin-5-yl} ester4-Butoxy-benzoic acid {2- [2- (trans-4-ethylcyclohexyl) ethyl] pyridin-5-yl} ester
4-Butoxy-benzoesäure-{2-[2-(trans-4-propylcyclohexyl)- ethyl]-pyridin-5-yl} ester 4-Butoxy-benzoesäure-{2-[2-(trans-4-butylcyclohexyl)- ethyl]-pyridin-5-yl} ester4-Butoxy-benzoic acid {2- [2- (trans-4-propylcyclohexyl) ethyl] pyridin-5-yl} ester 4-Butoxy-benzoic acid {2- [2- (trans-4-butylcyclohexyl) ethyl] pyridin-5-yl} ester
4-Butoxy-benzoesäure-{2-[2-(trans-4-pentylcyclohexyl)-ethyl]-pyridin-5-yl} ester 4-Butoxy-benzoesäure-{2-[2-(trans-4-hexylcyclohexyl)-ethyl]-pyridin-5-yl} ester4-butoxy-benzoic acid- {2- [2- (trans-4-pentylcyclohexyl) ethyl] pyridin-5-yl} ester of 4-butoxy-benzoic acid- {2- [2- (trans-4-hexylcyclohexyl) - ethyl] pyridin-5-yl} ester
4-Butoxy-benzoesäure-{2-[2-(trans-4-heptylcyclohexyl)-ethyl]-pyridin-5-yl} ester4-Butoxy-benzoic acid {2- [2- (trans-4-heptylcyclohexyl) ethyl] pyridin-5-yl} ester
4-Propoxy-benzoesäure-{2-[2-(trans-4-ethylcyclohexyl)-ethyl]-pyridin-5-yl} ester4-Propoxy-benzoic acid {2- [2- (trans-4-ethylcyclohexyl) ethyl] pyridin-5-yl} ester
4-Propoxy-benzoesäure-{2-[2-(trans-4-propylcyclohexyl)-ethyl]-pyridin-5-yl} ester4-Propoxy-benzoic acid {2- [2- (trans-4-propylcyclohexyl) ethyl] pyridin-5-yl} ester
4-Propoxy-benzoesäure-{2-[2-(trans-4-butylcyclohexyl)-ethyl]-pyridin-5-yl} ester 4-Propoxy-benzoesäure-{2-[2-(trans-4-pentylcyclohexyl)-ethyl]-pyridin-5-yl} ester4-Propoxy-benzoic acid {2- [2- (trans-4-butylcyclohexyl) ethyl] pyridin-5-yl} ester of 4-propoxy-benzoic acid {2- [2- (trans-4-pentylcyclohexyl) - ethyl] pyridin-5-yl} ester
4-Propoxy-benzoesäure-{2-[2-(trans-4-hexylcyclohexyl)-ethyl]-pyridin-5-yl} ester4-Propoxy-benzoic acid {2- [2- (trans-4-hexylcyclohexyl) ethyl] pyridin-5-yl} ester
4-Propoxy-benzoesäure-{2-[2-(trans-4-heptylcyclohexyl)-ethyl]-pyridin-5-yl} ester4-Propoxy-benzoic acid {2- [2- (trans-4-heptylcyclohexyl) ethyl] pyridin-5-yl} ester
4-Ethoxy-benzoesäure-{2-[2-(trans-4-ethylcyclohexyl)-ethyl]-pyridin-5-yl} ester4-Ethoxy-benzoic acid {2- [2- (trans-4-ethylcyclohexyl) ethyl] pyridin-5-yl} ester
4-Ethoxy-benzoesäure-{2-[2-(trans-4-propylcyclohexyl)-ethyl]-pyridin-5-yl} ester 4-Ethoxy-benzoesäure-{2-[2-(trans-4-butylcyclohexyl)-ethyl]-pyridin-5-yl} ester4-Ethoxy-benzoic acid {2- [2- (trans-4-propylcyclohexyl) ethyl] pyridin-5-yl} ester of 4-ethoxy-benzoic acid {2- [2- (trans-4-butylcyclohexyl) - ethyl] pyridin-5-yl} ester
4-Ethoxy-benzoesäure-{2-[2-(trans-4-pentylcyclohexyl)-ethyl]-pyridin-5-yl} ester4-Ethoxy-benzoic acid {2- [2- (trans-4-pentylcyclohexyl) ethyl] pyridin-5-yl} ester
4-Ethoxy-benzoesäure-{2-[2-(trans-4-hexylcyclohexyl)-ethyl]-pyridin-5-yl} ester4-Ethoxy-benzoic acid {2- [2- (trans-4-hexylcyclohexyl) ethyl] pyridin-5-yl} ester
4-Ethoxy-benzoesäure-{2-[2-(trans-4-heptylcyclohexyl)-ethyl]-pyridin-5-yl} ester 4-Hexyloxy-benzoesäure-{2-[2-(trans-4-ethylcyclohexyl)-ethyl]-pyridin-5-yl} ester4-Ethoxy-benzoic acid {2- [2- (trans-4-heptylcyclohexyl) ethyl] pyridin-5-yl} ester 4-Hexyloxy-benzoic acid {2- [2- (trans-4-ethylcyclohexyl) ethyl] pyridin-5-yl} ester
4-Hexyloxy-benzoesäure-{2-[2-(trans-4-propylcyclohexyl)-ethyl]-pyridin-5-yl} ester 4-Hexyloxy-benzoesäure-{2-[2-(trans-4-butylcyclohexyl)-ethyl]-pyridin-5-yl} ester4-Hexyloxy-benzoic acid- {2- [2- (trans-4-propylcyclohexyl) ethyl] pyridin-5-yl} ester of 4-hexyloxy-benzoic acid- {2- [2- (trans-4-butylcyclohexyl) - ethyl] pyridin-5-yl} ester
4-Hexyloxy-benzoesäure-{2-[2-(trans-4-pentylcyclohexyl)-ethyl]-pyridin-5-yl} ester4-Hexyloxy-benzoic acid {2- [2- (trans-4-pentylcyclohexyl) ethyl] pyridin-5-yl} ester
4-Hexyloxy-benzoesäure-{2-[2-(trans-4-hexylcyclohexyl)-ethyl]-pyridin-5-yl} ester4-Hexyloxy-benzoic acid {2- [2- (trans-4-hexylcyclohexyl) ethyl] pyridin-5-yl} ester
4-Hexyloxy-benzoesäure-{2-[2-(trans-4-heptylcyclohexyl)-ethyl]-pyridin-5-yl}ester4-Hexyloxy-benzoic acid {2- [2- (trans-4-heptylcyclohexyl) ethyl] pyridin-5-yl} ester
4-Heptyloxy-benzoesäure-{2-[2-(trans-4-ethylcyclohexyl)-ethyl]-pyridin-5-yl}ester 4-Heptyloxy-benzoesäure-{2-[2-(trans-4-propylcyclohexyl)-ethyl]-pyridin-5-yl} ester4-heptyloxybenzoic acid {2- [2- (trans-4-ethylcyclohexyl) ethyl] pyridin-5-yl} ester 4-heptyloxybenzoic acid {2- [2- (trans-4-propylcyclohexyl) - ethyl] pyridin-5-yl} ester
4-Heptyloxy-benzoesäure-{2-[2-(trans-4-butylcyclohexyl)-ethyl]-pyridin-5-yl} ester4-heptyloxy benzoic acid {2- [2- (trans-4-butylcyclohexyl) ethyl] pyridin-5-yl} ester
4-Heptyloxy-benzoesäure-{2-[2-(trans-4-pentylcyclohexyl)-ethyl]-pyridin-5-yl} ester4-heptyloxybenzoic acid {2- [2- (trans-4-pentylcyclohexyl) ethyl] pyridin-5-yl} ester
4-Heptyloxy-benzoesäure-{2-[2-(trans-4-hexylcyclohexyl)-ethyl]-pyridin-5-yl}ester4-heptyloxybenzoic acid {2- [2- (trans-4-hexylcyclohexyl) ethyl] pyridin-5-yl} ester
4-Heptyloxy-benzoesäure-{2-[2-(trans-4-heptylcyclohexyl)-ethyl]-pyridin-5-yl}ester4-Heptyloxy-benzoic acid {2- [2- (trans-4-heptylcyclohexyl) ethyl] pyridin-5-yl} ester
4-Octyloxy-benzoesäure-{2-[2-(trans-4-propylcyclohexyl)- ethyl]-pyridin-5-yl} ester4-Octyloxy-benzoic acid {2- [2- (trans-4-propylcyclohexyl) ethyl] pyridin-5-yl} ester
4-Octyloxy-benzoesäure-{2-[2-(trans-4-butylcyclohexyl)- ethyl]-pyridin-5-yl} ester4-Octyloxy-benzoic acid {2- [2- (trans-4-butylcyclohexyl) ethyl] pyridin-5-yl} ester
4-Octyloxy-benzoesäure-{2-[2-(trans-4-pentylcyclohexyl)- ethyl]-pyridin-5-yl} ester 4-Octyloxy-benzoesäure-{2-[2-(trans-4-hexylcyclohexyl)- ethyl]-pyridin-5-yl} ester4-Octyloxy-benzoic acid {2- [2- (trans-4-pentylcyclohexyl) ethyl] pyridin-5-yl} ester 4-Octyloxy-benzoic acid {2- [2- (trans-4-hexylcyclohexyl) ethyl] pyridin-5-yl} ester
4-Octyloxy-benzoesäure-{2-[2-(trans-4-heptylcyclohexyl)- ethyl]-pyridin-5-yl} ester, K 63° S (54°) SC 112° SA 134° N 144° I4-Octyloxy-benzoic acid {2- [2- (trans-4-heptylcyclohexyl) ethyl] pyridin-5-yl} ester, K 63 ° S (54 °) S C 112 ° S A 134 ° N 144 ° I.
4-(2-Fluoroctyloxy)benzoesäure-{2-[2-(trans-4-ethylcyclohexyl)ethyl]-pyridin-5-yl} ester4- (2-Fluoroctyloxy) benzoic acid {2- [2- (trans-4-ethylcyclohexyl) ethyl] pyridin-5-yl} ester
4-(2-Fluoroctyloxy)benzoesäure-{2-[2-(trans-4-propylcyclohexyl)ethyl]-pyridin-5-yl} ester 4-(2-Fluoroctyloxy)benzoesäure-{2-[2-(trans-4-butylcyclohexyl)ethyl]-pyridin-5-yl} ester4- (2-Fluoroctyloxy) benzoic acid {2- [2- (trans-4-propylcyclohexyl) ethyl] pyridin-5-yl} ester 4- (2-fluoroctyloxy) benzoic acid {2- [2- (trans- 4-butylcyclohexyl) ethyl] pyridin-5-yl} ester
4-(2-Fluoroctyloxy)benzoesäure-{2-[2-(trans-4-pentylcyclohexyl)ethyl]-pyridin-5-yl} ester4- (2-Fluoroctyloxy) benzoic acid {2- [2- (trans-4-pentylcyclohexyl) ethyl] pyridin-5-yl} ester
4-(2-Fluoroctyloxy)benzoesäure-{2-[2-(trans-4-hexylcyclohexyl)ethyl]-pyridin-5-yl} ester4- (2-Fluoroctyloxy) benzoic acid {2- [2- (trans-4-hexylcyclohexyl) ethyl] pyridin-5-yl} ester
Beispiel 6Example 6
Analog Beispiel 5 erhält man durch Umsetzung von 5-Hydroxy-2-[2-(trans-4-pentylcyclohexyl)ethyl]-pyridin und Propionsäure 5-Propylcarbonyloxy-2-[2-(trans-4-pentylcyclohexyl) ethyl]-pyridin.Analogously to Example 5, reaction of 5-hydroxy-2- [2- (trans-4-pentylcyclohexyl) ethyl] pyridine and propionic acid gives 5-propylcarbonyloxy-2- [2- (trans-4-pentylcyclohexyl) ethyl] pyridine .
Analog werden hergestellt:The following are produced analogously:
5-Propylcarbonyloxy-2-[2-(trans-4-ethylcyclohexyl)ethyl]-pyridin5-propylcarbonyloxy-2- [2- (trans-4-ethylcyclohexyl) ethyl] pyridine
5-Propylcarbonyloxy-2-[2-(trans-4-propylcyclohexyl)ethyl]-pyridin5-propylcarbonyloxy-2- [2- (trans-4-propylcyclohexyl) ethyl] pyridine
5-Propylcarbonyloxy-2-[2-(trans-4-butylcyclohexyl)ethyl]-pyridin 5-Ethylcarbonyloxy-2-[2-(trans-4-ethylcyclohexyl)ethyl]-pyridin5-propylcarbonyloxy-2- [2- (trans-4-butylcyclohexyl) ethyl] pyridine 5-ethylcarbonyloxy-2- [2- (trans-4-ethylcyclohexyl) ethyl] pyridine
5-Ethylcarbonyloxy-2-[2-(trans-4-propylcyclohexyl)ethyl]-pyridin 5-Ethylcarbonyloxy-2-[2-(trans-4-butylcyclohexyl)ethyl]-pyridin5-ethylcarbonyloxy-2- [2- (trans-4-propylcyclohexyl) ethyl] pyridine 5-ethylcarbonyloxy-2- [2- (trans-4-butylcyclohexyl) ethyl] pyridine
5-Ethylcarbonyloxy-2-[2-(trans-4-pentylcyclohexyl)ethyl]-pyridin5-ethylcarbonyloxy-2- [2- (trans-4-pentylcyclohexyl) ethyl] pyridine
5-Butylcarbonyloxy-2-[2-(trans-4-ethylcyclohexyl)ethyl]-pyridin5-butylcarbonyloxy-2- [2- (trans-4-ethylcyclohexyl) ethyl] pyridine
5-Butylcarbonyloxy-2-[2-(trans-4-propylcyclohexyl)ethyl]- pyridin5-butylcarbonyloxy-2- [2- (trans-4-propylcyclohexyl) ethyl] pyridine
5-Butylcarbonyloxy-2-[2-(trans-4-butylcyclohexyl)ethyl]-pyridin 5-Butylcarbonyloxy-2-[2-(trans-4-pentylcyclohexyl)ethyl]-pyridin5-butylcarbonyloxy-2- [2- (trans-4-butylcyclohexyl) ethyl] pyridine 5-butylcarbonyloxy-2- [2- (trans-4-pentylcyclohexyl) ethyl] pyridine
5-Pentylcarbonyloxy-2-[2-(trans-4-ethylcyclohexyl)ethyl]-pyridin5-pentylcarbonyloxy-2- [2- (trans-4-ethylcyclohexyl) ethyl] pyridine
5-Pentylcarbonyloxy-2-[2-(trans-4-propylcyclohexyl)ethyl]-pyridin5-pentylcarbonyloxy-2- [2- (trans-4-propylcyclohexyl) ethyl] pyridine
5-Pentylcarbonyloxy-2-[2-(trans-4-butylcyclohexyl)ethyl]-pyridin5-pentylcarbonyloxy-2- [2- (trans-4-butylcyclohexyl) ethyl] pyridine
5-Pentylcarbonyloxy-2-[2-(trans-4-pentylcyclohexyl)ethyl]-pyridin5-pentylcarbonyloxy-2- [2- (trans-4-pentylcyclohexyl) ethyl] pyridine
5-Pentylcarbonyloxy-2-{2-[trans-4-(trans-4-ethylcyclohexyl)cyclohexyl] ethyl}pyridin5-pentylcarbonyloxy-2- {2- [trans-4- (trans-4-ethylcyclohexyl) cyclohexyl] ethyl} pyridine
5-Pentylcarbonyloxy-2-{2-[trans-4-(trans-4-propylcyclohexyl)cyclohexyl] ethyl}pyridin 5-Pentylcarbonyloxy-2-{2-[trans-4-(trans-4-butylcyclohexyl)cyclohexyl] ethyl}pyridin5-pentylcarbonyloxy-2- {2- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] ethyl} pyridine 5-pentylcarbonyloxy-2- {2- [trans-4- (trans-4-butylcyclohexyl) cyclohexyl] ethyl } pyridine
5-Pentylcarbonyloxy-2-{2-[trans-4-(trans-4-pentylcyclohexyl)cyclohexyl] ethyl}pyridin 5-Butylcarbonyloxy-2-{2-[trans-4-(trans-4-ethylcyclohexyl)cyclohexyl] ethyl}pyridin5-pentylcarbonyloxy-2- {2- [trans-4- (trans-4-pentylcyclohexyl) cyclohexyl] ethyl} pyridine 5-butylcarbonyloxy-2- {2- [trans-4- (trans-4-ethylcyclohexyl) cyclohexyl] ethyl} pyridine
5-Butylcarbonyloxy-2-{2-[trans-4-(trans-4-propylcyclohexyl)cyclohexyl] ethyl}pyridin 5-Butylcarbonyloxy-2-{2-[trans-4-(trans-4-butylcyclohexyl)cyclohexyl] ethyl}pyridin5-butylcarbonyloxy-2- {2- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] ethyl} pyridine 5-butylcarbonyloxy-2- {2- [trans-4- (trans-4-butylcyclohexyl) cyclohexyl] ethyl } pyridine
5-Butylcarbonyloxy-2-{2-[trans-4-(trans-4-pentylcyclohexyl)cyclohexyl] ethyl}pyridin5-butylcarbonyloxy-2- {2- [trans-4- (trans-4-pentylcyclohexyl) cyclohexyl] ethyl} pyridine
5-Propylcarbonyloxy-2-{2-[trans-4-(trans-4-ethylcyclohexyl)cyclohexyl] ethyl}pyridin5-propylcarbonyloxy-2- {2- [trans-4- (trans-4-ethylcyclohexyl) cyclohexyl] ethyl} pyridine
5-Propylcarbonyloxy-2-{2-[trans-4-(trans-4-propylcyclohexyl)cyclohexyl] ethyl}pyridin, K 68° SB 160° N 173.7 I 5-Propylcarbonyloxy-2-{2-[trans-4-(trans-4-butylcyclohexyl)cyclohexyl] ethyl}pyridin 5-Propylcarbonyloxy-2-{2-[trans-4-(trans-4-pentylcyclohexyl)cyclohexyl] ethyl}pyridin5-Propylcarbonyloxy-2- {2- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] ethyl} pyridine, K 68 ° S B 160 ° N 173.7 I 5-propylcarbonyloxy-2- {2- [trans-4 - (trans-4-butylcyclohexyl) cyclohexyl] ethyl} pyridine 5-propylcarbonyloxy-2- {2- [trans-4- (trans-4-pentylcyclohexyl) cyclohexyl] ethyl} pyridine
5-Ethylcarbonyloxy-2-{2-[trans-4-(trans-4-ethylcyclohexyl)cyclohexyl] ethyl}pyridin5-ethylcarbonyloxy-2- {2- [trans-4- (trans-4-ethylcyclohexyl) cyclohexyl] ethyl} pyridine
5-Ethylcarbonyloxy-2-{2-[trans-4-(trans-4-propylcyclohexyl)cyclohexyl] ethyl}pyridin5-ethylcarbonyloxy-2- {2- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] ethyl} pyridine
5-Ethylcarbonyloxy-2-{2-[trans-4-(trans-4-butylcyclohexyl)cyclohexyl] ethyl}pyridin5-ethylcarbonyloxy-2- {2- [trans-4- (trans-4-butylcyclohexyl) cyclohexyl] ethyl} pyridine
5-Ethylcarbonyloxy-2-{2-[trans-4-(trans-4-pentylcyclohexyl)cyclohexyl] ethyl}pyridin5-ethylcarbonyloxy-2- {2- [trans-4- (trans-4-pentylcyclohexyl) cyclohexyl] ethyl} pyridine
5-Methylcarbonyloxy-2-{2-[trans-4-(trans-4-ethylcyclohexyl)cyclohexyl] ethyl}pyridin5-methylcarbonyloxy-2- {2- [trans-4- (trans-4-ethylcyclohexyl) cyclohexyl] ethyl} pyridine
5-Methylcarbonyloxy-2-{2-[trans-4-(trans-4-propylcyclohexyl)cyclohexyl] ethyl}pyridin, K 115° SB 147° N 156,8° 5-Methylcarbonyloxy-2-{2-[trans-4-(trans-4-butylcyclohexyl)cyclohexyl] ethyl} pyridin5-methylcarbonyloxy-2- {2- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] ethyl} pyridine, K 115 ° S B 147 ° N 156.8 ° 5-methylcarbonyloxy-2- {2- [trans -4- (trans-4-butylcyclohexyl) cyclohexyl] ethyl} pyridine
5-Methylcarbonyloxy-2-{2-[trans-4-(trans-4-pentylcyclohexyl)cyclohexyl] ethyl} pyridin Beispiel 75-methylcarbonyloxy-2- {2- [trans-4- (trans-4-pentylcyclohexyl) cyclohexyl] ethyl} pyridine Example 7
Durch selektive Alkylierung von 2-Methyl-5-pentyl-pyridin mit Lithiumdiisopropylamid in THF bei -30° (analog Bsp. 3b) mit trans-4-(trans-4-Ethylcyclohexylethyl)-cyclohexylmethyliodid erhält man 5-Pentyl-2-[trans-4-(trans-4-ethylcyclohexylethyl)-cyclohexylethyl] -pyridin.Selective alkylation of 2-methyl-5-pentylpyridine with lithium diisopropylamide in THF at -30 ° (analogously to Example 3b) with trans-4- (trans-4-ethylcyclohexylethyl) cyclohexylmethyl iodide gives 5-pentyl-2- [ trans-4- (trans-4-ethylcyclohexylethyl) cyclohexylethyl] pyridine.
Analog werden hergestellt:The following are produced analogously:
5-Butyl-2-[trans-4-(trans-4-ethylcyclohexylethyl)-cyclohexylethyl)-pyridin 5-Propyl-2-[trans-4-(trans-4-ethylcyclohexylethyl)-cyclohexylethyl)-pyridin5-butyl-2- [trans-4- (trans-4-ethylcyclohexylethyl) cyclohexylethyl) pyridine 5-propyl-2- [trans-4- (trans-4-ethylcyclohexylethyl) cyclohexylethyl) pyridine
5-Ethyl-2-[trans-4-(trans-4-ethylcyclohexylethyl)-cyclohexylethyl)-pyridin 5-Hexyl-2-[trans-4-(trans-4-ethylcyclohexylethyl)-cyclohexylethyl)-pyridin5-ethyl-2- [trans-4- (trans-4-ethylcyclohexylethyl) cyclohexylethyl) pyridine 5-hexyl-2- [trans-4- (trans-4-ethylcyclohexylethyl) cyclohexylethyl) pyridine
5-Heptyl-2-[trans-4-(trans-4-ethylcyclohexylethyl)-cyclohexylethyl ) -pyridin5-heptyl-2- [trans-4- (trans-4-ethylcyclohexylethyl) cyclohexylethyl) pyridine
5-Ethyl-2-[trans-4-(trans-4-propylcyclohexylethyl)-cyclohexylethyl)-pyridin 5-Propyl-2-[trans-4-(trans-4-propylcyclohexylethyl)-cyclohexylethyl)-pyridin5-ethyl-2- [trans-4- (trans-4-propylcyclohexylethyl) cyclohexylethyl) pyridine 5-propyl-2- [trans-4- (trans-4-propylcyclohexylethyl) cyclohexylethyl) pyridine
5-Butyl-2-[trans-4-(trans-4-propylcyclohexylethyl)-cyclohexylethyl)-pyridin 5-Pentyl-2-[trans-4-(trans-4-propylcyclohexylethyl)-cyclohexylethyl)-pyridin5-butyl-2- [trans-4- (trans-4-propylcyclohexylethyl) cyclohexylethyl) pyridine 5-pentyl-2- [trans-4- (trans-4-propylcyclohexylethyl) cyclohexylethyl) pyridine
5-Hexyl-2-[trans-4-(trans-4-propylcyclohexylethyl)-cyclohexylethyl)-pyridin5-Hexyl-2- [trans-4- (trans-4-propylcyclohexylethyl) cyclohexylethyl) pyridine
5-Heptyl-2-[trans-4-(trans-4-propylcyclohexylethyl)-cyclohexylethyl)-pyridin 5-Ethyl-2- trans-4-(trans-4-butylcyclohexylethyl)-cyclohexylethyl -pyridin 5-Propyl-2-[trans-4-(trans-4-butylcyclohexylethyl)-cyclohexylethyl -py[idin 5-Butyl-2- trans-4-(trans-4-butylcyclohexylethyl)-cyclohexylethyl -pyridin 5-Pentyl-2-[trans-4-(trans-4-butylcyclohexylethyl)-cyclohexylethyl -pyridin 5-Hexyl-2- trans-4-(trans-4-butylcyclohexylethyl)-cyclohexylethyl -pyridin 5-Heptyl-2 [trans-4-(trans-4-butylcyclohexylethyl)-cyclohexylethyl -pyridin5-heptyl-2- [trans-4- (trans-4-propylcyclohexylethyl) cyclohexylethyl) pyridine 5-ethyl-2-trans-4- (trans-4-butylcyclohexylethyl) cyclohexylethyl pyridine 5-propyl-2- [trans-4- (trans-4-butylcyclohexylethyl) cyclohexylethyl-py [idin 5-butyl-2 - trans-4- (trans-4-butylcyclohexylethyl) -cyclohexylethyl-pyridine 5-pentyl-2- [trans-4- (trans-4-butylcyclohexylethyl) -cyclohexylethyl-pyridine 5-hexyl-2-trans-4- (trans -4-butylcyclohexylethyl) cyclohexylethyl pyridine 5-heptyl-2 [trans-4- (trans-4-butylcyclohexylethyl) cyclohexylethyl pyridine
5-Ethyl-2- trans-4-(trans-4-pentylcyclohexylethyl)-cyclohexylethyl -pyridin 5-Propyl-2-[trans-4-(trans-4-pentylcyclohexylethyl)-cyclohexylethyl -pyridin 5-Butyl-2- trans-4-(trans-4-pentylcyclohexylethyl)-cyclohexylethyl -pyridin 5-Pentyl-2-[trans-4-(trans-4-pentylcyclohexylethyl)-cyclohexylethyl -pyridin 5-Hexyl-2- trans-4-(trans-4-pentylcyclohexylethyl)-cyclohexylethyl -pyridin 5-Heptyl-2-[trans-4-(trans-4-pentylcyclohexylethyl)-cyclohexylethyl -pyridin5-ethyl-2-trans-4- (trans-4-pentylcyclohexylethyl) cyclohexylethyl pyridine 5-propyl-2- [trans-4- (trans-4-pentylcyclohexylethyl) cyclohexylethyl pyridine 5-butyl-2-trans -4- (trans-4-pentylcyclohexylethyl) cyclohexylethyl pyridine 5-pentyl-2- [trans-4- (trans-4-pentylcyclohexylethyl) cyclohexylethyl pyridine 5-hexyl-2-trans-4- (trans-4 -pentylcyclohexylethyl) -cyclohexylethyl-pyridine 5-heptyl-2- [trans-4- (trans-4-pentylcyclohexylethyl) -cyclohexylethyl-pyridine
5-Ethyl-2-[trans-4-(trans-4-ethylcyclohexyl)-cyclohexylethyl)-pyridin5-ethyl-2- [trans-4- (trans-4-ethylcyclohexyl) cyclohexylethyl) pyridine
5-Propyl-2-[trans-4-(trans-4-ethylcyclohexyl)-cyclohexylethyl)-pyridin5-propyl-2- [trans-4- (trans-4-ethylcyclohexyl) cyclohexylethyl) pyridine
5-Butyl-2-[trans-4-(trans-4-ethylcyclohexyl)-cyclohexylethyl)-pyridin5-butyl-2- [trans-4- (trans-4-ethylcyclohexyl) cyclohexylethyl) pyridine
5-Pentyl-2-[trans-4-(trans-4-ethylcyclohexyl)-cyclohexylethyl)-pyridin 5-Ethyl-2-[trans-4-(trans-4-propylcyclohexyl)-cyclohexylethyl)-pyridin, K 41° SB 131° N 136,6 I5-pentyl-2- [trans-4- (trans-4-ethylcyclohexyl) cyclohexylethyl) pyridine 5-ethyl-2- [trans-4- (trans-4-propylcyclohexyl) cyclohexylethyl) pyridine, K 41 ° S B 131 ° N 136.6 I
5-Propyl-2-[trans-4-(trans-4-propylcyclohexyl)-cyclohexylethyl)-pyridin 5-Butyl-2-[trans-4-(trans-4-propylcyclohexyl)-cyclohexylethyl)-pyridin, K 13° SB 135° I5-propyl-2- [trans-4- (trans-4-propylcyclohexyl) cyclohexylethyl) pyridine 5-butyl-2- [trans-4- (trans-4-propylcyclohexyl) cyclohexylethyl) pyridine, K 13 ° S B 135 ° I
5-Pentyl-2-[trans-4-(trans-4-propylcyclohexyl)-cyclohexylethyl)-pyridin5-pentyl-2- [trans-4- (trans-4-propylcyclohexyl) cyclohexylethyl) pyridine
5-Ethyl-2-[trans-4-(trans-4-butylcyclohexyl)-cyclohexylethyl)-pyridin5-ethyl-2- [trans-4- (trans-4-butylcyclohexyl) cyclohexylethyl) pyridine
5-Propyl-2-[trans-4-(trans-4-butylcyclohexyl)-cyclohexylethyl)-pyridin5-propyl-2- [trans-4- (trans-4-butylcyclohexyl) cyclohexylethyl) pyridine
5-Butyl-2-[trans-4-(trans-4-butylcyclohexyl)-cyclohexylethyl)-pyridin 5-Pentyl-2-[trans-4-(trans-4-butylcyclohexyl)-cyclohexylethyl)-pyridin5-butyl-2- [trans-4- (trans-4-butylcyclohexyl) cyclohexylethyl) pyridine 5-pentyl-2- [trans-4- (trans-4-butylcyclohexyl) cyclohexylethyl) pyridine
5-Ethyl-2-[trans-4-(trans-4-pentylcyclohexyl)-cyclohexylethyl)-pyridin5-ethyl-2- [trans-4- (trans-4-pentylcyclohexyl) cyclohexylethyl) pyridine
5-Propyl-2-[trans-4-(trans-4-pentylcyclohexyl)-cyclohexylethyl)-pyridin5-propyl-2- [trans-4- (trans-4-pentylcyclohexyl) cyclohexylethyl) pyridine
5-Butyl-2-[trans-4-(trans-4-pentylcyclohexyl)-cyclohexylethyl)-pyridin5-butyl-2- [trans-4- (trans-4-pentylcyclohexyl) cyclohexylethyl) pyridine
5-Pentyl-2-[trans-4-(trans-4-pentylcyclohexyl)-cyclohexylethyl)-pyridin5-pentyl-2- [trans-4- (trans-4-pentylcyclohexyl) cyclohexylethyl) pyridine
Folgendes Beispiel betrefft eine erfindungsgemäße flüssigkristalline Phase.The following example relates to a liquid-crystalline phase according to the invention.
Beispiel A:Example A:
Eine flüssigkristalline Phase, bestehend ausA liquid crystalline phase consisting of
12 % 4-(trans-4-Propylcyclohexyl)-benzonitril, 8 % 4-(trans-4-Butylcyclohexyl)-benzonitril, 13 % trans-4(4-Ethoxyphenyl)-1-propylcyclohexan, 11 % trans-4-(4-Butoxyphenyl)-1-propylcyclohexan,12% 4- (trans-4-propylcyclohexyl) benzonitrile, 8% 4- (trans-4-butylcyclohexyl) benzonitrile, 13% trans-4 (4-ethoxyphenyl) -1-propylcyclohexane, 11% trans-4- (4-butoxyphenyl) -1-propylcyclohexane,
8 % trans-4-(4-Ethoxyphenyl)-1-butylcyclohexan,8% trans-4- (4-ethoxyphenyl) -1-butylcyclohexane,
9 % trans-4-(4-Methoxyphenyl)-1-pentylcyclohexan, 5 % trans-4-(4-Ethoxyphenyl)-1-pentylcyclohexan,9% trans-4- (4-methoxyphenyl) -1-pentylcyclohexane, 5% trans-4- (4-ethoxyphenyl) -1-pentylcyclohexane,
5 % trans-4-(trans-4-Propylcyclohexyl)cyclohexancarbonsäure-(4-propylphenyl)ester, 5 % trans-4-(trans-4-Propylcyclohexyl)cyclohexancarbonsäure-(2-pentylpyridin-5-yl)ester, 5 % trans-4-trans-4-Butylcyclohexyl)cyclohexancarbonsäure-(4-propylphenyl)ester, 5 % trans-4-(trans-4-Butylcyclohexyl)cyclohexancarbonsäure-(2-pentylpyridin-5-yl)ester,5% trans-4- (trans-4-propylcyclohexyl) cyclohexane carboxylic acid (4-propylphenyl) ester, 5% trans-4- (trans-4-propylcyclohexyl) cyclohexane carboxylic acid (2-pentylpyridin-5-yl) ester, 5% trans-4-trans-4-butylcyclohexyl) cyclohexanecarboxylic acid (4-propylphenyl) ester, 5% trans-4- (trans-4-butylcyclohexyl) cyclohexanecarboxylic acid (2-pentylpyridin-5-yl) ester,
4 % 4,4"-Bis-(trans-4-propylcyclohexyl)-biphenyl, 5 % 4,4'-Bis-(trans-4-pentylcyclohexyl)-biphenyl und4% 4,4 "-bis (trans-4-propylcyclohexyl) biphenyl, 5% 4,4'-bis (trans-4-pentylcyclohexyl) biphenyl and
5 % 4-(trans-4-Pentylcyclohexyl)-4'-(trans-4-propylcyclohexyl)-biphenyl5% 4- (trans-4-pentylcyclohexyl) -4 '- (trans-4-propylcyclohexyl) biphenyl
hat einen Klärpunkt von 90° und eine Viskosität von 19 mm2/s (bei 20°). has a clearing point of 90 ° and a viscosity of 19 mm 2 / s (at 20 °).

Claims

Patentansprüche Claims
1. Pyridinderivate der Formel I1. Pyridine derivatives of the formula I.
Figure imgf000058_0001
worin
Figure imgf000058_0001
wherein
R 1 einen Alkylrest mit 1-15 C-Atomen oder einen Alkenylrest mit 2-15 C-Atomen, wobei in diesen Resten auch eine CH2-Gruppe durch -O-, -CO-, -O-CO- oder -CO-O- ersetzt sein kann,R 1 is an alkyl radical with 1-15 C atoms or an alkenyl radical with 2-15 C atoms, in which radicals a CH 2 group is also represented by -O-, -CO-, -O-CO- or -CO- O- can be replaced
R 2 eine der Bedeutungen von R1 oder einen optisch aktiven RestR 2 has one of the meanings of R 1 or an optically active radical
Figure imgf000058_0002
Figure imgf000058_0002
worinwherein
X -CO-O-, -O-CO-, -O-CO-O-, -CO-, -O-, -S-,X -CO-O-, -O-CO-, -O-CO-O-, -CO-, -O-, -S-,
-CH=CH-, -CH=CH-COO- oder eine Einfachbindung,-CH = CH-, -CH = CH-COO- or a single bond,
Q Alkylen mit 1 bis 5 C-Atomen, worin auch eine nicht mit X verknüpfte CH2-Gruppe durch -O-, -CO-, -O-CO-, -CO-O- oder -CH=CH- ersetzt sein kann, oder eine Einfachbindung, Y CN, Halogen, Methyl oder Methoxy, undQ alkylene with 1 to 5 carbon atoms, in which a CH 2 group which is not linked to X can also be replaced by -O-, -CO-, -O-CO-, -CO-O- or -CH = CH- , or a single bond, Y CN, halogen, methyl or methoxy, and
R3 eine von Y verschiedene Alkylgruppe mitR 3 has an alkyl group other than Y.
1 bis 15 C-Atomen, worin auch eine oder zwei nicht benachbarte CH2-Gruppen durch1 to 15 carbon atoms, where also one or two non-adjacent CH 2 groups by
-O-, -CO-, -O-CO-, -CO-O- und/oder -CH=CH- ersetzt sein können, bedeutet,-O-, -CO-, -O-CO-, -CO-O- and / or -CH = CH- can be replaced, means
Z-AZ-A
Figure imgf000059_0001
Figure imgf000059_0001
Z1 -CH2CH2 oder eine Einfachbindung,Z 1 -CH 2 CH 2 or a single bond,
A1 -O-CO-Phe-,A 1 -O-CO-Phe-,
Phe unsubstituiertes oder ein- oder mehrfach durch F- und/oder Cl-Atome und/oder CH3- und/oder CN-Gruppen substituiertes 1,4- Phenylen,Phe 1,4-phenylene which is unsubstituted or substituted one or more times by F and / or Cl atoms and / or CH 3 and / or CN groups,
n 0 oder 1n 0 or 1
undand
m 0 oder 1m 0 or 1
bedeutet.means.
2. Verwendung der Verbindungen der Formel I nach Anspruch 1 als Komponenten flüssigkristalliner Phasen. 2. Use of the compounds of formula I according to claim 1 as components of liquid-crystalline phases.
3. Flussigkristalline Phase mit mindestens zwei flüssigkristallinen Komponenten, dadurch gekennzeichnet, daß mindestens eine Komponente eine Verbindung der Formel I ist.3. liquid crystalline phase with at least two liquid crystalline components, characterized in that at least one component is a compound of formula I.
4. Flüssigkristallanzeigeelement, dadurch gekennzeichnet, daß es eine Phase nach Anspruch 3 enthält. 4. Liquid crystal display element, characterized in that it contains a phase according to claim 3.
PCT/EP1989/000408 1988-04-28 1989-04-15 Pyridine derivatives WO1989010356A1 (en)

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US5145601A (en) * 1990-06-25 1992-09-08 The University Of Colorado Foundation Inc. Ferroelectric liquid crystals with nicotinic acid cores
CN104108726A (en) * 2013-04-16 2014-10-22 中国石油化工股份有限公司 Silicoaluminophosphate molecular sieve with high silica-alumina ratio and CHA structure, and synthetic method thereof

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GB8921519D0 (en) * 1989-09-22 1989-11-08 Merck Patent Gmbh Pyridine derivatives
CN101130466B (en) 2006-08-23 2011-05-04 中国科学院大连化学物理研究所 Method of start working of fluidization catalytic reaction device for preparing low carbon olefinic hydrocarbon

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Publication number Priority date Publication date Assignee Title
EP0056501A2 (en) * 1981-01-19 1982-07-28 MERCK PATENT GmbH Liquid crystal mixture
GB2092169A (en) * 1980-12-16 1982-08-11 Brown Boveri Bbc & Co Ltd Liquid crystal mixtures comprising weakly polar non-cyano components and strongly polar cyano components
EP0164721A2 (en) * 1984-06-13 1985-12-18 Chisso Corporation Novel liquid crystal compound and liquid crystal composition containing same
EP0168683A2 (en) * 1984-07-16 1986-01-22 F. Hoffmann-La Roche Ag Liquid crystals with alkenyl or alkenyloxy groups

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Publication number Priority date Publication date Assignee Title
GB2092169A (en) * 1980-12-16 1982-08-11 Brown Boveri Bbc & Co Ltd Liquid crystal mixtures comprising weakly polar non-cyano components and strongly polar cyano components
EP0056501A2 (en) * 1981-01-19 1982-07-28 MERCK PATENT GmbH Liquid crystal mixture
EP0164721A2 (en) * 1984-06-13 1985-12-18 Chisso Corporation Novel liquid crystal compound and liquid crystal composition containing same
EP0168683A2 (en) * 1984-07-16 1986-01-22 F. Hoffmann-La Roche Ag Liquid crystals with alkenyl or alkenyloxy groups

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5145601A (en) * 1990-06-25 1992-09-08 The University Of Colorado Foundation Inc. Ferroelectric liquid crystals with nicotinic acid cores
CN104108726A (en) * 2013-04-16 2014-10-22 中国石油化工股份有限公司 Silicoaluminophosphate molecular sieve with high silica-alumina ratio and CHA structure, and synthetic method thereof

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