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Definitions

• the present invention relates to cyclopenta [b] naphthalene derivatives, their use in liquid-crystalline or mesogenic media, liquid-crystalline or mesogenic media containing these derivatives, and electro-optical display elements containing these liquid-crystalline or mesogenic media.
• Liquid crystals have found a wide range of applications since the first commercially applicable liquid-crystalline compounds were found around 30 years ago.
• Known fields of application are, in particular, display displays for watches and pocket calculators, and large display boards, such as are used in train stations, airports and sports arenas.
• Other areas of application are displays of portable computers and navigation systems as well as video applications. Particularly for the latter applications, high demands are made on switching times and the contrast of the images.
• the spatial order of the molecules in a liquid crystal means that many of its properties are directional.
• the anisotropies in the optical, dielectric and elasto-mechanical behavior are of particular importance for use in liquid crystal displays.
• the molecules are oriented with their longitudinal axes perpendicular or parallel to the two plates of a capacitor, it has a different capacitance; the dielectric constant ⁇ of the liquid-crystalline medium is therefore different for the two orientations.
• dielectric positive Substances whose dielectric constant is greater when the longitudinal axes of the molecules are oriented perpendicular to the capacitor plates than when they are arranged in parallel are termed dielectric positive. Most of the liquid crystals used in conventional displays fall into this group.
• the dipole moment oriented along the longitudinal axis of the molecule is greater than the dipole moment oriented perpendicular to the longitudinal axis of the molecule.
• the orientation of the larger dipole moment along the longitudinal axis of the molecule also determines the orientation of the molecule in a field-free liquid crystal display.
• TN cells derived from the English: "twisted nematic", twisted nematic
• only about 5 to 10 ⁇ m thick liquid-crystalline layer is arranged between two flat glass plates, each with an electrically conductive, transparent layer of tin oxide or indium tin oxide as the electrode is vapor-deposited.
• a likewise transparent orientation layer which usually consists of a plastic (eg polyimides). It serves to use surface forces to move the longitudinal axes of the neighboring crystalline molecules in a preferred direction so that they lie flat in the voltage-free state with the same orientation flat or with the same small angle of attack on the inside of the display surface.
• a plastic eg polyimides
• On the outside of the display are two polarizing foils, which only allow linearly polarized light to enter and exit, in a certain ano glued on.
• VA-TFT displays derived from the English: “vertically aligned”
• R 1 is -F, -CN, -Cl, -CF 3 or, independently of R 2 , has one of the meanings listed for R 2 ;
• a 1 is 1,4-phenylene, 1,4-cyclohexylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, (1, 3) -thiazole-2,5-diyl, (1, 3) -Thiazol-2,4-diyl, where one or more hydrogens can also be substituted by F, (1, 3,4) thiadiazole-2,5-diyl;
• M 1 is a single bond, -C ⁇ C-, -CH 2 CH 2 -, -O-CO-, -CO-O-, -CO-, -OCH 2 -, -CH 2 0-, -O-CO -O-; and m is zero or one.
• the ⁇ of the compounds disclosed in this document is not sufficient to ensure satisfactory properties, for example in VA-TFT displays.
• An object of the present invention was to provide compounds with advantageous properties for use in liquid-crystalline media.
• -CH 2 F, -CHF 2 , -CF 3 , -OCH 3 , -OCH 2 F, -OCHF 2 or -OCF 3 can be substituted, 1, 4-cyclohexylene, 1, 4-cyclohexenylene or 1, 4-cyclohexadienylene , in which -CH 2 - can be replaced once or twice independently of one another by -O- or -S- such that heteroatoms are not directly adjacent, and which can be substituted once or more by halogen, 1,3-cyclo- butylene or bicyclo [2.2.2] octane,
• R is hydrogen, an unsubstituted, an alkyl-, alkoxy-, simply substituted by -CF 3 or at least monosubstituted by halogen,
• Alkenyl or alkynyl radical having 1 to 15 or 2 to 15 carbon atoms, one or more CH2 groups in these radicals each being independently of one another by —O-, -S-, -CO-, -COO-, -OCO - or -OCO-O- can be replaced so that heteroatoms are not directly adjacent, halogen, -CN, -SCN, -NCS, -SF 5 ,
• n 0, 1, 2 or 3 and L - L each independently of one another are hydrogen, an unsubstituted or an at least mono-substituted alkyl, alkoxy, alkenyl or alkynyl radical having 1 to 15 or 2 to 15 C atoms, one or more CH 2 -Groups can each independently be replaced by -O-, -S-, -CO-, -COO-, -OCO- or -OCO-O- so that heteroatoms are not directly adjacent, halogen, -CN, -SCN , -NCS, -SF 5 , -CF 3 , -OCF 3 , -OCHF 2> -OCH 2 F or - (ZA-) n -R,
• Another object of the present invention was to provide liquid-crystalline compounds, in particular for use in VA-TFT displays.
• This object is achieved according to the invention by providing cyclopenta [b] naphthaiine derivatives with a negative ⁇ .
• the present invention thus relates in particular to cyclopenta [b] naphthalene derivatives of the general formulas (II) to (VI)
• Cyclohexadienylene in which -CH 2 - can be replaced once or twice independently of one another by -O- or -S- so that heteroatoms are not directly adjacent, and which can be substituted once or more by halogen, 1, 3-cyclo - butylene or bicyclo [2.2.2] octane,
• R is hydrogen, an unsubstituted, an alkyl, alkoxy, alkenyl or alkynyl radical with 1 to 15 or 2 to 15 carbon atoms which is simply substituted by -CF3 or at least monosubstituted by halogen, one or more CH 2 -Groups can each independently be replaced by -O-, -S-, -CO-, -COO-, -OCO- or -OCO-O- so that heteroatoms are not directly adjacent, halogen, -CN, -SCN , -NCS, -SF 5 , -CF 3 , -OCF3, -OCHF2 or -OCH 2 F,
• L 2 , L 3 , L 8 each independently of one another are hydrogen, an unsubstituted or at least one halogen-substituted alkyl, alkoxy, alkenyl or alkynyl radical having 1 to 15 or 2 to 15 carbon atoms, with these radicals also one or more CH2 groups independently of one another by -O-,
• n -R, L 4 , L 6 each independently of one another are hydrogen, an alkyl, alkoxy, alkenyl or alkynyl radical with 1 to 15 or 2 to 15 C atoms which is at least monosubstituted by halogen, one or more CH 2 - also being present in these radicals.
• Groups can each independently be replaced by -O-, -S-, -CO-, -COO-, -OCO- or -OCO-O- so that heteroatoms are not directly adjacent, halogen, -CN, -SF 5 , -SCN, -NCS, -CF 3 , -OCF 3 , -OCHF 2 or -OCH 2 F, preferably with the proviso that L 4 and L 6 must not be hydrogen at the same time, and
• n 0, 1, 2 or 3
• ), (V) and (VI) are preferred, and cyclopenta [b] naphthalene derivatives of the general formulas (II) and (VI) are particularly preferred.
• the compounds all have a negative ⁇ and are therefore particularly suitable for use in VA TFT displays.
• the compounds according to the invention preferably have a ⁇ ⁇ -2 and particularly preferably a ⁇ ⁇ -5. They show a very good compatibility with the usual substances used in liquid crystal mixtures for displays.
• substituents preferably fluorine substituents
• Naphthalene skeleton and the electronegative atoms in ring B generate a dipole moment perpendicular to the longitudinal axis of the molecule, which can optionally be further strengthened by suitable substituents in the wing units - (ZA-) n -R.
• the compounds of the formulas (II) to (VI) align with their longitudinal axis perpendicular to the treated or coated glass surface of the display. Preferred as general formulas (II) to (VI)
• A is preferably, independently of one another, optionally substituted 1,4-phenylene, optionally substituted 1,4-cyclohexylene, in which -CH 2 - can be replaced once or twice by -O-, or optionally substituted 1, 4-cyclohexenylene.
• A are particularly preferably independent of one another
• R, L 2 and L 3 in the general formulas (II) to (VI) can each independently of one another be an alkyl radical and / or an alkoxy radical having 1 to 15 carbon atoms, which can be straight-chain or branched. It is preferably straight-chain, has 1, 2, 3, 4, 5, 6 or 7 carbon atoms and is therefore preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyi, methoxy, ethoxy, propoxy, butoxy, pentoxy, Hexoxy or heptoxy.
• R, L 2 and L 3 can each independently be an alkenyl radical having 2 to 15 carbon atoms, which can be straight-chain or branched. It is preferably straight-chain and has 2 to 7 carbon atoms. Accordingly, it is preferably 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.
• R, L 2 and L 3 can each independently be an alkyl radical having 1 to 15 carbon atoms, in which one CH 2 group is replaced by -O- and one by -CO-, these preferably being adjacent. Thus, this contains an acyloxy group -CO-O- or an oxycarbonyl group -O-CO-. This is preferably straight-chain and has 2 to 6 carbon atoms.
• R, L 2 and L 3 can each independently be an alkyl radical having 1 to 15 C atoms or an alkenyl radical having 2 to 15 C atoms which is simply substituted by - CN or -CF 3 , these preferably being straight-chain. The substitution by -CN or -CF 3 is possible in any position.
• R, L 2 and L 3 can each independently be an alkyl radical in which two or more CH 2 groups are replaced by -O- and / or -CO-O-, which can be straight-chain or branched. It is preferably branched and has 3 to 12 carbon atoms.
• R, L 2 , L 3 , L 4 and L 6 can each independently be an at least monosubstituted alkyl radical having 1 to 15 carbon atoms or an alkenyl radical having 2 to 15 carbon atoms, these radicals preferably being straight-chain and halogen is preferably -F or -Cl. In the case of multiple substitution, halogen is preferably -F.
• the resulting residues also include perfluorinated residues such as -CF 3 .
• the fluorine or chlorine substituent can be in any position, preferably in the ⁇ position.
• R in the general formulas (II) to (VI) is particularly preferably an alkyl radical, alkoxy radical or alkenyl radical having 1 to 7 or 2 to 7 C atoms.
• L 2 and L 3 in the general formulas (II) to (VI) are preferably hydrogen, an alkyl radical, alkoxy radical or alkenyl radical having 1 to 7 or 2 to 7 carbon atoms or a halogen, particularly preferably hydrogen
• Alkoxy radical with 1 to 7 carbon atoms fluorine or chlorine, and in particular fluorine.
• L 4 and L 6 in the general formulas (II) to (VI) are preferably hydrogen, an at least monosubstituted by halogen
• L 8 in the general formulas (II) to (VI) is preferably fluorine.
• Another object of the present invention was to provide connections, in particular for use in mesogenic control media, these control media being used in particular in electro-optical light control elements which are operated at a temperature at which the mesogenic control medium is used. uncontrolled state in the isotropic phase.
• This object is achieved according to the invention by providing cyclopenta [b] naphthalene derivatives with a positive ⁇ .
• the present invention thus relates in particular to cyclopenta [b] naphthalene derivatives of the general formulas (VII) to (XI)
• Cyclopenta [b] naphthalene derivatives of the general formulas (VII) and (XI) are preferred, and cyclopenta [b] naphthalene derivatives of the general formula (VII) are particularly preferred.
• the compounds of the formulas (VII) to (XI) all have a positive ⁇ .
• the compounds of the formulas (VII) to (XI) according to the invention preferably have a ⁇ > +10, particularly preferably a ⁇ > +15 and in particular a ⁇ > +20. They show very good compatibility with the usual substances used in mesogenic control media.
• cyclopenta [b] naphthalene derivatives of the general formula (VII) preferably have the following structural formulas:
• A is preferably, independently of one another, optionally substituted 1,4-phenylene, optionally substituted 1,4-cyclohexylene, in which -CH 2 - can be replaced once or twice by -O-, or optionally substituted 1,4-cyclohexenylene.
• A are particularly preferably independent of one another
• Preferred groups Z in the compounds of the general formulas (VII) to (XI) are each, independently of one another, a single bond, -CF 2 O-,
• R and L 1 to L 8 in the general formulas (VII) to (XI) can each independently be an alkyl radical and / or an alkoxy radical having 1 to 15 carbon atoms, which can be straight-chain or branched. It is preferably straight-chain, has 1, 2, 3, 4, 5, 6 or 7 carbon atoms and is therefore preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, methoxy, ethoxy, propoxy, butoxy, pentoxy, Hexoxy or heptoxy.
• R and L 1 to L 8 in the general formulas (VII) to (XI) can each independently be an alkenyl radical having 2 to 15 C atoms, which can be straight-chain or branched. It is preferably straight-chain and has 2 to 7 carbon atoms. Accordingly, it is preferably 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.
• R and L 1 to L 8 in the general formulas (VII) to (XI) can each independently be an alkyl radical having 1 to 15 carbon atoms, in which one CH 2 group is defined by -O- and one by -CO- is replaced, which are preferably adjacent. Thus, this contains an acyloxy group -CO-O- or an oxycarbonyl group -O-CO-. This is preferably straight-chain and has 2 to 6 carbon atoms.
• R and L 1 to L 8 in the general formulas (VII) to (XI) can each, independently of one another, be an alkyl radical having 1 to 15 C atoms or monkenyl radical having 2 to 15 C atoms which is simply substituted by -CN or -CF 3 , which are preferably straight-chain. The substitution by -CN or -CF 3 is possible in any position.
• R and L 1 to L 8 in the general formulas (VII) to (XI) can each independently be an alkyl radical in which two or more CH 2 groups have been replaced by -O- and / or -CO-O-, which can be straight-chain or branched. It is preferably branched and has 3 to 12 carbon atoms.
• R and L 1 to L 8 in the general formulas (VII) to (XI) can each independently be an at least monosubstituted alkyl radical having 1 to 15 carbon atoms or alkenyl radical having 2 to 15 carbon atoms, these radicals are preferably straight-chain and halogen is preferably -F or -CI. In the case of multiple substitution, halogen is preferably -F.
• the resulting residues also include perfluorinated residues such as -CF 3 .
• the fluorine or chlorine substituent can be in any position, preferably in the ⁇ position.
• R in the general formulas (VII) to (XI) is particularly preferably an alkyl radical, alkoxy radical or alkenyl radical having 1 to 7 or 2 to 7 C atoms, in particular an alkyl radical having 1 to 7 C atoms.
• L 2 and L 3 in the general formulas (VII) to (XI) are preferably, independently of one another, identical or different, hydrogen, halogen, -CN, -SCN, -NCS, -SF 5 , -CF 3 , -CHF 2l -OCF 3 or -OCHF 2 , particularly preferably hydrogen, fluorine, -CF 3 or -OCF 3 .
• L 2 and / or L 3 is not hydrogen.
• L 1 and L 4 in the general formulas (VII) to (XI) are preferably, independently of one another, identical or different, hydrogen or fluorine.
• L 5 and L 6 in the general formulas (VII) to (XI) are preferably hydrogen.
• the starting materials can also be formed in situ in such a way that they are not isolated from the reaction mixture, but instead are immediately reacted further to give the compounds of the general formulas (I) to (XI).
• the examples describe the syntheses of various poly-substituted naphthalene derivatives that are used to construct the five-membered ring.
• the starting substances can be obtained according to generally accessible literature regulations or are commercially available.
• the reactions described are also to be regarded as known from the literature.
• An exemplary synthesis of the structure of the five-membered ring is shown below. The synthesis can be adapted to the desired compounds of the general formulas (I) to (XI) by the choice of suitable starting products.
• compound c is obtained by reaction with the ⁇ , ⁇ -unsaturated aldehyde b in the presence of lithium diisopropylamide (LDA). This reacts with palladium catalysis in the presence of triethylamine with ring closure to the ketone d. From the ketone d and 1,3-propanedithioI in the presence of BF 3 -diethyl ether receive corresponding Dithian e. This is converted with 1, 3-dibromo-5,5-dimethylhydantoin (DBH) and HF in pyridine to the cyclopenta [b] naphthalene derivative f.
• DSA lithium diisopropylamide
• the compounds of the general formulas (I) to (XI) can be used in liquid-crystalline media.
• the present invention therefore also relates to a liquid-crystalline medium with at least two liquid-crystalline compounds containing at least one compound of the general formulas (I) to (XI).
• the present invention also relates to liquid-crystalline media comprising, in addition to one or more compounds of the formulas (I), (II), (III), (IV), (V), (VI), (VII), (VIII), ( IX), (X) and / or (XI) as further constituents 2 to 40, preferably 4 to 30 components.
• These media particularly preferably contain 7 to 25 components in addition to one or more compounds according to the invention.
• nematic or nematogenic (monotropic or isotropic) substances 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, cyclohexanecarboxylic acid phenyl- or -cyclohexyl esters, phenyl- or
• L and E which may be the same or different, each independently represent a divalent 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 by fluorine substituted 1, 4-phenylene, cyc trans-1, 4-cyclohexylene or 1, 4-cyclohexylene, pyr pyrimidine-2,5-diyl or pyridine-2,5-diyl, dio 1, 3-dioxane-2, 5-diyl and G signify 2- (trans-1, 4-cyclohexyl) ethyl.
• one of the residues L and E is Cyc or Phe.
• 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 and Phe and simultaneously one or more components selected from the compounds of the formulas (1), (2), (3), (4) and (5), wherein one of the radicals L and E is selected from the group Cyc and Phe 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-
• Compounds of the sub-formulas (1a) to (5a) have the meaning indicated and are preferably alkyl, alkenyl, alkoxy or alkoxyalkyl.
• R "-CN In a further smaller subgroup of the compounds of the formulas (1), (2), (3), (4) and (5), R "-CN; this subgroup is hereinafter referred to as group C and the compounds of this subgroup are correspondingly referred to as partial formulas (1c), (2c), (3c), (4c) and (5c) above.
• R 1 meaning given for the compounds of the sub-formulas (1a) to (5a) and is preferably alkyl, alkenyl, alkoxy or alkoxyalkyl.
• the media according to the invention contain and / or (XI) preferably one or more compounds from groups A, B and / or C.
• the mass fractions of the compounds from these groups in the media according to the invention are:
• Group A 0 to 90%, preferably 20 to 90%, in particular 30 to 90%
• Group B 0 to 80%, preferably 10 to 80%, in particular 10 to 70%
• Group C 0 to 80%, preferably 5 to 80 %, especially 5 to 50%.
• the media according to the invention preferably contain 1 to 40%, particularly preferably 5 to 30%, of the compounds of the formulas (I), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX), (X) and / or (XI).
• the media preferably contain three, four or five compounds according to the invention of the formulas (I), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX), ( X) and / or (XI).
• the media according to the invention are produced in a conventional manner.
• the components are dissolved in one another, expediently at elevated temperature.
• liquid crystalline phases of the present invention are modified so that they can be used in all previously known types of liquid crystal display elements.
• 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 for producing colored guest-host systems or substances for changing the dielectric anisotropy, the viscosity and / or the orientation of the nematic phases can be added.
• the compounds of the formulas (II) to (VI) are particularly suitable for use in VA-TFT displays because of their negative ⁇ .
• the present invention therefore also relates to electro-optical liquid crystal display elements containing a liquid crystalline medium according to the invention.
• the compounds of the formulas (VII) to (XI) are particularly suitable for use in mesogenic control media, these control media being used in particular in electro-optical light control elements which are operated at a temperature at which the mesogenic control medium is not controlled state is in the isotropic phase.
• the present invention therefore also relates to electro-optical light control elements, as disclosed for example in DE 102 17 273 A1, which contain an electrode arrangement, at least one element for polarizing the light and a mesogenic control medium, the light control element being operated at a temperature at which the mesogenic control medium is present in the isotropic phase in the uncontrolled state, and which are characterized in that the mesogenic control medium contains one or more compounds of the formulas (VII) to (XI).
• the starting substances can be obtained according to generally available literature regulations or can be obtained commercially.
• the reactions described are known from the literature.
• a solution of 20.0 g (98.5 mmol) of the aldehyde 1 in 100 ml of THF is mixed with 200 ml (100 mmol) of a 0.5 M solution of the zinc compound 2 in THF.
• the cooling is removed after 30 minutes.
• the thawed batch is mixed with water, acidified with 1 N HCl solution and with tert. Butylmethyl (MTB) ether extracted. After drying, concentrating and chromatography on silica gel, the hydroxyester 3 is obtained.
• keto ester 4 9.0 g (29.7 mmol) of keto ester 4 are added to 100 g of polyphosphoric acid at 60 ° C. The temperature is then raised to 120 ° C. for 4 hours. After cooling, the mixture is poured onto ice and tert. Butylmethyl (MTB) ether extracted. After drying, concentration and crystallization, the diketone 5 is obtained.
• MTB Butylmethyl
• the batch is heated to 140 ° C. until nitrogen evolution has ended.
• a solution of 10 g (26.4 mmol) of the protected ketone 9 in 60 ml of dichloromethane is at -75 ° C in a suspension of 30.2 g (105.2 mmol) of 1,3-dibromo-5,5-dimethylhydantoin in 60 ml of dichloromethane and 120 ml of a 65% solution of hydrogen fluoride in pyridine.
• the mixture is slowly heated to 0 ° C. for 3 hours and added to 1500 ml of an ice-cooled 2N sodium hydroxide solution, to which 120 ml of a 39% sodium hydrogen sulfite solution have been added.
• the pH is adjusted to 8 and the aqueous phase is extracted with methylene chloride. After drying, concentration and chromatography on silica gel, the fluorinated ester 10 is obtained.
• the fluorinated ester 10 is ring-closed to the compound 11 as described in Example 1.
• Example 5 The reduction of the compound 11 to the alcohol 13 and the subsequent elimination of water to the dihydronaphthalene derivative 14 are carried out as described in Example 2.
• Example 5 The reduction of the compound 11 to the alcohol 13 and the subsequent elimination of water to the dihydronaphthalene derivative 14 are carried out as described in Example 2.
• a solution of 9 g (34.2 mmol) of the dihydronaphthalene derivative 14 in 50 ml of THF is slowly added to a suspension of 4.5 g (40.1 mmol) of potassium tert-butoxide in 50 ml of THF and then overnight Reflux heated.
• the cooled mixture is diluted with water and extracted with diethyl ether. After drying, concentrating and chromatography on silica gel, the naphthalene 15 is obtained.
• the hydroxyester 3 is reacted in dimethylformamide (DMF) at 120 ° C for four hours in the presence of potassium carbonate with benzyl bromide. After cooling, the mixture is poured onto ice water and tert. Butylmethyl (MTB) ether extracted. After drying, concentration and crystallization, the ester 25 is obtained.
• DMF dimethylformamide
• MTB Butylmethyl
• the ether 27 dissolved in THF is reacted on palladium / carbon catalyst in a hydrogen atmosphere. After concentration and chromatography on silica gel, the hydroxy compound 28 is obtained.
• the ketone 29 is reacted in methanol at 0 to 20 ° C for four hours with iodobenzene diacetate and KOH.
• the hydroxyketone 30 is obtained.
• the fluorinated hydroxy compound 32 is mixed with pyridine and POCI 3 with ice cooling. Then alcohol is added. The Reaction takes four hours at 60 ° C. After cooling, the mixture is poured onto ice water and tert. Butylmethyl (MTB) ether extracted. After drying, concentration and crystallization, the unsaturated fluorinated compound 33 is obtained.
• MTB Butylmethyl
• the corresponding Grignard compound is prepared from 48.0 g (200 mmol) of the aromatic 34, 4.8 g (200 mmol) of magnesium and 200 ml of toluene / THF (4: 1). 22.5 g (100 mmol) of zinc bromide are then introduced. After 1 hour, 57.6 g (200 mmol) of the aldehyde 35 in 50 ml of solvent are added. After a further 2 hours, the batch is mixed with water and acidified with dil. HCl solution. The aqueous phase is extracted three times with MTB ether. After drying, concentration and chromatography, 60.4 g of the ester 36 are obtained.
• a suspension of 18.0 g (136 mmol) of aluminum chloride in 50 ml of dichloromethane is mixed with a solution of the acid chloride 38 in 50 ml of dichloromethane at -25 ° C.
• the batch is kept at a temperature below -12 ° C. until complete conversion (TLC).
• the reaction is then stopped by carefully adding water (50 ml).
• the resulting solid is brought into solution using an HCl solution.
• the aqueous phase is extracted twice with dichloromethane, the organic Phase dried and concentrated. After chromatography, 30.2 g of diketone 39 are obtained.
• cyclopenta [b] naphthalene derivative 46 6.0 g (14.1 mmol) of the cyclopenta [b] naphthalene derivative 46 are dissolved in 50 ml of dichloromethane, with 2.4 ml (16.0 mmol) of 1, 8-diazabicyclo [5.4.0] - undec-7- en (DBU) are added and the mixture is stirred at room temperature until the starting material is completely converted. The mixture is washed with water and saturated sodium chloride solution, concentrated and chromatographed. The cyclopenta [b] naphthalene derivative 47 is isolated.
• DBU 1, 8-diazabicyclo [5.4.0] - undec-7- en
• ⁇ n and ⁇ values of the compound according to the invention were obtained by extrapolation from liquid-crystalline mixtures, which are 5% from the compound according to the invention and 95% from one of the two commercially available liquid crystal mixtures ZLI 4792 and ZLI 2857 (Merck, Darmstadt) passed.
• a solution of 20.0 g (62.1 mmol) of naphthalene 41 in 100 ml of diethyl ether is mixed at -75 ° C with 38.0 ml of a t7-butyllithium solution in ⁇ -hexane and stirred for 1 hour.
• 11.2 g (62.1 mmol) of the aldehyde 49 in 50 ml of diethyl ether are then added and the mixture is stirred overnight.
• the batch is mixed with water.
• the aqueous phase is extracted with diethyl ether, the organic phase is dried and concentrated. After chromatography, 21.2 g of the allyl alcohol 50 are obtained.

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