Cyclopenta[b]naphthalene derivatives

Abstract
The present invention relates to cyclopenta[b]naphthalene derivatives of the general formula (I) in which Z, A, n, R, L5 and L8 as (II) and (III) are as defined in Claim 1, to the use thereof in liquid-crystalline or mesogenic media, to liquid-crystalline or mesogenic media comprising at least one of these cyclopenta[b]naphthalene derivatives, and to electro-optical display elements containing these liquid-crystalline or mesogenic media.
Description

The present invention relates to cyclopenta[b]naphthalene derivatives, to the use thereof in liquid-crystalline or mesogenic media, to liquid-crystalline or mesogenic media comprising these derivatives, and to electro-optical display elements containing these liquid-crystalline or mesogenic media.


Liquid crystals have found widespread use since the first commercially usable liquid-crystalline compounds were found about 30 years ago. Known areas of application are, in particular, displays for watches and pocket calculators, and large display panels as used in railway stations, airports and sports arenas. Further areas of application are displays of portable computers and navigation systems and video applications. For the last-mentioned applications in particular, high demands are made of the response times and contrast of the images.


The spatial arrangement of the molecules in a liquid crystal has the effect that many of its properties are direction-dependent. Of particular importance for use in liquid-crystal displays are the optical, dielectric and elasto-mechanical anisotropies. Depending on whether the molecules are oriented with their longitudinal axes perpendicular or parallel to the two plates of a capacitor, the latter has a different capacitance; in other words, the dielectric constant c of the liquid-crystalline medium has different values for the two orientations. Substances whose dielectric constant is larger in the case of a perpendicular orientation of the longitudinal axes of the molecules to the capacitor plates than in the case of a parallel arrangement are referred to as dielectrically positive. Most liquid crystals used in conventional displays fall into this group.


Both the polarisability of the molecule and permanent dipole moments play a role for the dielectric anisotropy. On application of a voltage to the display, the longitudinal axis of the molecules orients itself in such a way that the larger of the dielectric constants becomes effective. The strength of the interaction with the electric field depends on the difference between the two constants. In the case of small differences, higher switching voltages are necessary than in the case of large differences. The incorporation of suitable polar groups, such as, for example, nitrile groups or fluorine, into the liquid-crystal molecules enables a broad range of working voltages to be achieved.


In the case of the liquid-crystalline molecules used in conventional liquid-crystal displays, the dipole moment oriented along the longitudinal axis of the molecules is larger than the dipole moment oriented perpendicular to the longitudinal axis of the molecules. The orientation of the larger dipole moment along the longitudinal axis of the molecule also determines the orientation of the molecule in a liquid-crystal display in the field-free state. In the most widespread TN (“twisted nematic”) cells, a liquid-crystalline layer with a thickness of only from about 5 to 10 μm is arranged between two flat glass plates, onto each of which an electrically conductive, trans-parent layer of tin oxide or indium tin oxide has been vapour-deposited as electrode. A likewise transparent alignment layer, which usually consists of a plastic (for example polyimides), is located between these films and the liquid-crystalline layer. This alignment layer serves to bring the longitudinal axes of the adjacent crystalline molecules into a preferential direction through surface forces in such a way that, in the voltage-free state, they lie uniformly on the inside of the display surface with the same orientation in a flat manner or with the same small tilt angle. Two polarisation films which only enable linear-polarised light to enter and escape are adhesively bonded to the outside of the display in a certain arrangement.


By means of liquid crystals in which the larger dipole moment is oriented parallel to the longitudinal axis of the molecule, very high-performance displays have already been developed. In most cases here, mixtures of from 5 to 20 components are used in order to achieve a sufficiently broad temperature range of the mesophase and short response times and low threshold voltages. However, difficulties are still caused by the strong viewing-angle dependence in liquid-crystal displays as are used, for example, for laptops. The best imaging quality can be achieved if the surface of the display is perpendicular to the viewing direction of the observer. If the display is tilted relative to the observation direction, the imaging quality drops drastically under certain circumstances. For greater comfort, attempts are being made to make the angle through which the display can be tilted from the viewing direction of an observer as large as possible. Attempts have recently been made to improve the viewing-angle dependence using liquid-crystalline compounds whose dipole moment perpendicular to the longitudinal axis of the molecules is larger than that parallel to the longitudinal axis of the molecule. In the field-free state, these molecules are oriented perpendicular to the glass surface of the display. In this way, it has been possible to achieve an improvement in the viewing-angle dependence. Displays of this type are known as VA-TFT (“vertically aligned”) displays.


DE 44 34 974 A1 discloses tricyclic compounds of the general formula
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in which the symbols and indices have the following meanings:


R1 is —F, —CN, —Cl, —CF3 or has, independently of R2, one of the meanings mentioned for R2;


R2 is H or a straight-chain or branched alkyl radical having from 1 to 20 carbon atoms (with or without an asymmetrical carbon atom), in which, in addition, one or more —CH2— groups (but not those bonded directly to the five-membered ring) may be replaced by —O—, —S—, —CH═CH—, —C≡C—, cyclo-propane-1,2-diyl, —Si(CH3)2—, 1,4-phenylene, 1,4-cyclohexylene, 1,3-cyclo-pentylene, 1,3-cyclobutylene, 1,3-dioxane-2,5-diyl, with the proviso that oxygen atoms and sulfur atoms must not be bonded directly, and in which, in addition, one or more H atoms of the alkyl radical may be substituted by F, Cl, Br or OR3, or an optically active or racemic group;


Ring B is
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A1 is 1,4-phenylene, 1,4-cyclohexylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, 1,3-thiazole-2,5-diyl, 1,3-thiazole-2,4-diyl, in which, in addition, one or more hydrogens may be substituted by F, 1,3,4-thiadiazole-2,5-diyl;


M1 is a single bond, —C≡C—, —CH2CH2—, —O—CO—, —CO—O—, —CO—, —OCH2—, —CH2O— or —O—CO—O—; and m is zero or one.


However, the Δε of the compounds disclosed in this document is not sufficient to ensure satisfactory properties, for example in VA-TFT displays.


Development in the area of liquid-crystalline materials is far from complete. In order to improve the properties of liquid-crystalline display elements, attempts are constantly being made to develop novel compounds which enable such displays to be optimised.


An object of the present invention was to provide compounds having advantageous properties for use in liquid-crystalline media.


This object is achieved in accordance with the invention by cyclopenta[b]-naphthalene derivatives of the general formula (I)
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in which:
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Z is in each case, independently of one another, a single bond, a double bond, —CF2O—, —OCF2—, —CH2CH2—, —CF2CF2—, —C(O)O—, —OC(O)—, —CH2O—, —OCH2—, —CF═CH—, —CH═CF—, —CF═CF—, —CH═CH—, —CH═CH— or —C≡C—,


A is in each case, independently of one another, 1 ,4-phenylene, in which ═CH— may be replaced once or twice by ═N—, and which may be monosubstituted to tetrasubstituted, independently of one another, by halogen (—F, —Cl, —Br, —I), —CN, —CH3, —CH2F, —CHF2, —CF3, —OCH3, —OCH2F, —OCHF2 or —OCF3, 1,4-cyclohexylene, 1,4-cyclohexenylene or 1,4-cyclohexadienylene, in which —CH2— may be replaced once or twice, independently of one another, by —O— or —S— in such a way that heteroatoms are not directly adjacent, and which may be monosubstituted or polysubstituted by halogen, or is 1,3-cyclobutylene or bicyclo[2.2.2]octane,


R is hydrogen, an alkyl, alkoxy, alkenyl or alkynyl radical having from 1 to 15 or 2 to 15 carbon atoms respectively which is unsubstituted, monosubstituted by —CF3 or at least monosubstituted by halogen, where, in addition, one or more CH2 groups in these radicals may each, independently of one another, be replaced by —O—, —S—, —CO—, —COO—, —OCO— or —OCO—O— in such a way that heteroatoms are not directly adjacent, halogen, —CN, —SCN, —NCS, —SF5, —CF3, —OCF3, —OCHF2 or —OCH2F,


n is 0, 1, 2 or 3, and


L1-L8 are each, independently of one another, hydrogen, an alkyl, alkoxy, alkenyl or alkynyl radical having from 1 to 15 or 2 to 15 carbon atoms respectively which is unsubstituted or at least mono-substituted by halogen, where, in addition, one or more CH2 groups in these radicals may each, independently of one another, be replaced by —O—, —S—, —CO—, —COO—, —OCO— or —OCO—O— in such a way that heteroatoms are not directly adjacent, halogen, —CN, —SCN, —NCS, —SF5, —CF3, —OCF3, —OCHF2, —OCH2F or -(Z-A-)n—R.


A further object of the present invention was to provide liquid-crystalline compounds, in particular for use in VA-TFT displays.


This object is achieved in accordance with the invention by the provision of cyclopenta[b]naphthalene derivatives of negative Δε.


The present invention thus relates, in particular, to cyclopenta[b]naphthalene derivatives of the general formulae (II) to (VI)
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Z is in each case, independently of one another, a single bond, a double bond, —CF2O—, —OCF2—, —CH2CH2—, —CF2CF2—, —C(O)O—, —OC(O)—, —CH2O—, —OCH2—, —CF═CH—, —CH═CF—, —CF═CF—, —CH═CH— or —C≡C—,


A is in each case, independently of one another, 1,4-phenylene, in which ═CH— may be replaced once or twice by ═N—, and which may be monosubstituted to tetrasubstituted, independently of one another, by halogen (—F, —Cl, —Br, —I), —CN, —CH3, —CH2F, —CHF2, —CF3, —OCH3, —OCH2F, —OCHF2 or —OCF3, 1,4-cyclohexylene, 1,4-cyclohexenylene or 1,4-cyclohexadienylene, in which —CH2— may be replaced once or twice, independently of one another, by —O— or —S— in such a way that heteroatoms are not directly adjacent, and which may be monosubstituted or polysubstituted by halogen, or is 1,3-cyclobutylene or bicyclo[2.2.2]octane,


R is hydrogen, an alkyl, alkoxy, alkenyl or alkynyl radical having from 1 to 15 or 2 to 15 carbon atoms respectively which is unsubstituted, monosubstituted by —CF3 or at least monosubstituted by halogen, where, in addition, one or more CH2 groups in these radicals may each, independently of one another, be replaced by —O—, —S—, —CO—, —COO—, —OCO— or —OCO—O— in such a way that heteroatoms are not directly adjacent, halogen, —CN, —SCN, —NCS, —SF5, —CF3, —OCF3, —OCHF2 or —OCH2F,


L2, L3 and L8 are each, independently of one another, hydrogen, an alkyl, alkoxy, alkenyl or alkynyl radical having from 1 to 15 or 2 to 15 carbon atoms respectively which is unsubstituted or at least mono-substituted by halogen, where, in addition, one or more CH2 groups in these radicals may each, independently of one another, be replaced by —O—, —S—, —CO—, —COO—, —OCO— or —OCO—O— in such a way that heteroatoms are not directly adjacent, halogen, —CN, —SCN, —NCS, —SF5, —CF3, —OCF3, —OCHF2, —OCH2F or -(Z-A-)n—R,


L4 and L6 are each, independently of one another, hydrogen, an alkyl, alkoxy, alkenyl or alkynyl radical having from 1 to 15 or 2 to 15 carbon atoms respectively which is at least monosubstituted by halogen, where, in addition, one or more CH2 groups in these radicals may each, independently of one another, be replaced by —O—, —S—, —CO—, —COO—, —OCO— or —OCO—O— in such a way that hetero-atoms are not directly adjacent, halogen, —CN, —SF5, —SCN, —NCS, —CF3, —OCF3, —OCHF2 or —OCH2F, preferably with the proviso that L4 and L6 cannot simultaneously be hydrogen, and


n is 0, 1, 2 or 3.


Preference is given to cyclopenta[b]naphthalene derivatives of the general formulae (II), (III), (V) and (VI), and particular preference is given to cyclopenta[b]naphthalene derivatives of the general formulae (II) and (VI).


The compounds all have negative Δε and are therefore suitable, in particular, for use in VA-TFT displays. The compounds according to the invention preferably have a Δε of <−2 and particularly preferably a Δε of <−5. They exhibit very good compatibility with the conventional substances used in liquid-crystal mixtures for displays.


The substituents, preferably fluorine substituents, in the naphthalene structure and the electronegative atoms in ring B generate a dipole moment perpendicular to the longitudinal axis of the molecules, which can, if desired, be further strengthened by suitable substituents in the wing units -(Z-A-)n—R. In the field-free state, the compounds of the formulae (II) to (VI) orient themselves with their longitudinal axis of the molecules perpendicular to the treated or coated glass surface of the display.
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in the general formulae (II) to (VI) are preferably
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particularly preferably
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In the general formulae (II) to (VI), A are preferably, independently of one another, optionally substituted 1,4-phenylene, optionally substituted 1,4-cyclohexylene, in which —CH2— may be replaced once or twice by —O—, or optionally substituted 1,4-cyclohexenylene.


A are particularly preferably, independently of one another,
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Preferred groups Z in the compounds of the general formulae (II) to (VI) are each, independently of one another, a single bond, —CF2O—, —OCF2—, —CF2CF2—, —CH═CH—, —CF═CH—, —CH═CF— or —CF═CF—, particularly preferably a single bond, —CF2O—, —OCF2—, —CF2CF2—, —CF═CH—, —CH═CF— or —CF═CF—.


R, L2 and L3 in the general formulae (II) to (VI) may each, independently of one another, be an alkyl radical and/or an alkoxy radical having from 1 to 15 carbon atoms, which may be straight-chain or branched. It is preferably straight-chain, has 1, 2, 3, 4, 5, 6 or 7 carbon atoms and accordingly is preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy or heptyloxy.


R, L2 and L3 may each, independently of one another, be oxaalkyl, preferably straight-chain 2-oxapropyl(=methoxymethyl), 2-(=ethoxymethyl) or 3-oxabutyl(=methoxyethyl), 2-, 3- or 4-oxapentyl, 2-, 3-, 4- or 5-oxahexyl, 2-, 3-, 4-, 5- or 6-oxaheptyl.


R, L2 and L3 may each, independently of one another, be an alkenyl radical having from 2 to 15 carbon atoms, which may be straight-chain or branched. It is preferably straight-chain and has from 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, L2 and L3 may each, independently of one another, be an alkyl radical having from 1 to 15 carbon atoms in which one CH2 group has been replaced by —O— and one has been replaced by —CO—, where these are preferably adjacent. This thus contains an acyloxy group —CO—O— or an oxycarbonyl group —O—CO—. This is preferably straight-chain and has from 2 to 6 carbon atoms.


R, L2 and L3 may each, independently of one another, be an alkyl radical having from 1 to 15 carbon atoms in which one CH2 group has been replaced by unsubstituted or substituted —CH═CH— and an adjacent CH2 group has been replaced by CO or CO—O or O—CO, where this may be straight-chain or branched. It is preferably straight-chain and has from 4 to 13 carbon atoms.


R, L2 and L3 may each, independently of one another, be an alkyl radical having from 1 to 15 carbon atoms or alkenyl radical having from 2 to 15 carbon atoms, each of which is monosubstituted by —CN or —CF3, where these are preferably straight-chain. The substitution by —CN or —CF3 is possible in any desired position.


R, L2 and L3 may each, independently of one another, be an alkyl radical in which two or more CH2 groups have been replaced by —O— and/or —CO—O—, where this may be straight-chain or branched. It is preferably branched and has from 3 to 12 carbon atoms.


R, L2, L3, L4 and L6 may each, independently of one another, be an alkyl radical having from 1 to 15 carbon atoms or alkenyl radical having from 2 to 15 carbon atoms, each of which is at least monosubstituted by halogen, where these radicals are preferably straight-chain and halogen is preferably —F or —Cl. In the case of polysubstitution, halogen is preferably —F. The resultant radicals also include perfluorinated radicals, such as —CF3. In the case of monosubstitution, the fluorine or chlorine substituent can be in any desired position, but is preferably in the ω-position.


R in the general formulae (II) to (VI) is particularly preferably an alkyl radical, alkoxy radical or alkenyl radical having from 1 to 7 or 2 to 7 carbon atoms respectively.


L2 and L3 in the general formulae (II) to (VI) is preferably hydrogen, an alkyl radical, alkoxy radical or alkenyl radical having from 1 to 7 or 2 to 7 carbon atoms respectively or a halogen, particularly preferably hydrogen, an alkoxy radical having from 1 to 7 carbon atoms, fluorine or chlorine, and in particular fluorine.


L4 and L6 in the general formulae (II) to (VI) is preferably hydrogen, an alkyl radical, alkoxy radical or alkenyl radical having from 1 to 7 or 2 to 7 carbon atoms respectively, each of which is at least monosubstituted by halogen, or a halogen, particularly preferably —CF3, fluorine or chlorine, and in particular fluorine.


L8 in the general formulae (II) to (VI) is preferably fluorine.


Preferred compounds of the general formulae (II) to (VI) have no, one or two wing units ZA, i.e. n=0, 1 or 2, particularly preferably n=1.


A further object of the present invention was to provide compounds, in particular for use in mesogenic control media, where these control media are employed, in particular, in electro-optical light-control elements which are operated at a temperature at which the mesogenic control medium in the unaddressed state is in the isotropic phase.


This object is achieved in accordance with the invention by the provision of cyclopenta[b]naphthalene derivatives of positive Δε.


The present invention thus relates, in particular, to cyclopenta[b]naphthalene derivatives of the general formulae (VII) to (XI)
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in which Z, A, R, n, L1 to L8 and
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have the meanings indicated in relation to the formula (I).


Preference is given to cyclopenta[b]naphthalene derivatives of the general formulae (VII) and (XI), and particular preference is given to cyclopenta[b]-naphthalene derivatives of the general formula (VII).


The compounds of the formulae (VII) to (XI) all have positive Δε. The compounds of the formulae (VII) to (XI) according to the invention preferably have a Δε of >+10, particularly preferably a Δε of >+15 and in particular a Δε of >+20. They exhibit very good compatibility with the conventional substances used in mesogenic control media.


The cyclopenta[b]naphthalene derivatives of the general formula (VII) preferably have the following structural formulae:
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where the structural formulae (VIIa) and (VIIc) are particularly preferred.
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in the general formulae (VII) to (XI) are preferably particularly preferably
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In the general formulae (VII) to (XI), A are preferably, independently of one another, optionally substituted 1,4-phenylene, optionally substituted 1,4-cyclohexylene, in which —CH2— may be replaced once or twice by —O—, or optionally substituted 1,4-cyclohexenylene.


A are particularly preferably, independently of one another,
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Preferred groups Z in the compounds of the general formulae (VII) to (XI) are each, independently of one another, a single bond, —CF2O—, —OCF2—, —CF2CF2—, —CH═CH—, —CF═CH—, —CH═CF— or —CF═CF—, particularly preferably a single bond, —CF2O—, —OCF2—, —CF2CF2— or —CF═CF—.


R and L1 to L8 in the general formulae (VII) to (XI) may each, independently of one another, be an alkyl radical and/or an alkoxy radical having from 1 to 15 carbon atoms, which may be straight-chain or branched. It is preferably straight-chain, has 1, 2, 3, 4, 5, 6 or 7 carbon atoms and accordingly is preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy or heptoxy.


R and L1 to L8 in the general formulae (VII) to (XI) may each, independently of one another, be oxaalkyl, preferably straight-chain 2-oxapropyl(═methoxymethyl), 2-(=ethoxymethyl) or 3-oxabutyl(=methoxyethyl), 2-, 3- or 4-oxapentyl, 2-, 3-, 4- or 5-oxahexyl, 2-, 3-, 4-, 5- or 6-oxaheptyl.


R and L1 to L8 in the general formulae (VII) to (XI) may each, independently of one another, be an alkenyl radical having from 2 to 15 carbon atoms, which may be straight-chain or branched. It is preferably straight-chain and has from 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-eny


R and L1 to L8 in the general formulae (VII) to (XI) may each, independently of one another, be an alkyl radical having from 1 to 15 carbon atoms in which one CH2 group has been replaced by —O— and one has been replaced by —CO—, where these are preferably adjacent. This thus contains an acyloxy-group —CO—O— or an oxycarbonyl group —O—CO—. This is preferably straight-chain and has from 2 to 6 carbon atoms.


R and L1 to L8 in the general formulae (VII) to (XI) may each, independently of one another, be an alkyl radical having from 1 to 15 carbon atoms in which one CH2 group has been replaced by unsubstituted or substituted —CH═CH— and an adjacent CH2 group has been replaced by CO or CO—O or O—CO, where this may be straight-chain or branched. It is preferably straight-chain and has from 4 to 13 carbon atoms.


R and L1 to L8 in the general formulae (VII) to (XI) may each, independently of one another, be an alkyl radical having from 1 to 1.5 carbon atoms or alkenyl radical having from 2 to 15 carbon atoms, each of which is monosubstituted by —CN or —CF3, where these are preferably straight-chain. The substitution by —CN or —CF3 is possible in any desired position.


R and L1 to L8 in the general formulae (VII) to (XI) may each, independently of one another, be an alkyl radical in which two or more CH2 groups have been replaced by —O— and/or —CO—O—, where this may be straight-chain or branched. It is preferably branched and has from 3 to 12 carbon atoms.


R and L1 to L8 in the general formulae (VII) to (XI) may each, independently of one another, be an alkyl radical having from 1 to 15 carbon atoms or alkenyl radical having from 2 to 15 carbon atoms, each of which is at least monosubstituted by halogen, where these radicals are preferably straight-chain and halogen is preferably —F or —Cl. In the case of polysubstitution, halogen is preferably —F. The resultant radicals also include per-fluorinated radicals, such as —CF3. In the case of monosubstitution, the fluorine or chlorine substituent can be in any desired position, but is preferably in the co-position.


R in the general formulae (VII) to (XI) is particularly preferably an alkyl radical, alkoxy radical or alkenyl radical having from 1 to 7 or 2 to 7 carbon atoms respectively, in particular an alkyl radical having from 1 to 7 carbon atoms.


L2 and L3 in the general formulae (VII) to (XI) is preferably, independently of one another, identical or different and is hydrogen, halogen, —CN, —SCN, —NCS, —SF5, —CF3, —CHF2, —OCF3 or —OCHF2, particularly preferably hydrogen, fluorine, —CF3 or —OCF3. In particular, however, L2 and/or L3 is not hydrogen.


L1 and L4 in the general formulae (VII) to (XI) is preferably, independently of one another, identical or different and is hydrogen or fluorine. Particularly preferably, however, L1=L4=H or L1=L4=F.


L5 and L6 in the general formulae (VII) to (XI) is preferably hydrogen.


Particular preference is given to compounds of the general formulae (VII) to (XI) in which L1=L2=L3=L4=F and L5=L6=H.


Preferred compounds of the general formulae (VII) to (XI) have no, one or two wing units ZA, i.e. n=0, 1 or 2, particularly preferably n=1.


The compounds of the general formulae (I), (II) to (VI) and (VII) to (XI) are prepared by methods known per se, as described in the literature (for example in the standard works, such as Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart), to be precise under reaction conditions which are known and are suitable for the said reactions. Use can be made here of variants known per se, which are not mentioned here in greater detail.


If desired, the starting materials can also be formed in situ by not isolating them from the reaction mixture, but instead immediately converting them further into the compounds of the general formulae (I) to (XI).


The syntheses of various polysubstituted naphthalene derivatives which are used to build up the five-membered ring are described by way of example in the examples. The starting substances are obtainable by generally accessible literature procedures or commercially. The reactions described should likewise be regarded as known from the literature.


An illustrative synthesis for building up the five-membered ring is shown below. The synthesis can be adapted to the particular desired compounds of the general formulae (I) to (XI) through the choice of suitable starting materials.
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Starting from the 3-bromonaphthalene a, reaction with an α,β-unsaturated aldehyde b in the presence of lithium diisopropylamide (LDA) gives compound c. This reacts with palladium catalysis in the presence of triethylamine with ring closure to give the ketone d. From the ketone d and 1,3-propanedithiol in the presence of BF3/diethyl ether, the corresponding dithiane e is obtained. This is reacted with 1,3-dibromo-5,5-dimethylhydantoin (DBH) and HF in pyridine to give the cyclopenta[b]naphthalene derivative f. Elimination of HBr in the presence of diazabicycloundecene (DBU) gives the cyclopenta[b]naphthalene derivative g. The cyclopenta[b]naphthalene derivative g is hydrogenated on the palladium/carbon catalyst in a hydrogen atmosphere to give the cyclopenta[b]naphthalene derivative h.


The reactions described should only be regarded as illustrative. The person skilled in the art can carry out corresponding variations of the syntheses described and also follow other suitable synthetic routes in order to obtain compounds of the formulae (I) to (XI).


As already mentioned, the compounds of the general formulae (I) to (XI) can be used in liquid-crystalline media.


The present invention therefore also relates to a liquid-crystalline medium comprising at least two liquid-crystalline compounds, comprising at least one compound of the general formulae (I) to (XI).


The present invention also relates to liquid-crystalline media comprising from 2 to 40, preferably from 4 to 30, components as further constituents besides one or more compounds of the formulae (I), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX), (X) and/or (XI) according to the invention. These media particularly preferably comprise from 7 to 25 components besides 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 the azoxybenzenes, benzylideneanilines, biphenyls, terphenyls, phenyl or cyclohexyl benzoates, phenyl or cyclohexyl esters of cyclohexanecarboxylic acid, phenyl or cyclohexyl esters of cyclohexylbenzoic acid, phenyl or cyclohexyl esters of cyclohexylcyclohexanecarboxylic acid, cyclohexylphenyl esters of benzoic acid, of cyclohexanecarboxylic acid or of cyclohexylcyclohexanecarboxylic acid, phenylcyclohexanes, cyclohexylbiphenyls, phenylcyclohexylcyclohexanes, cyclohexylcyclohexanes, cyclohexylcyclohexylcyclohexenes, 1,4-biscyclohexylbenzenes, 4′,4′-biscyclohexylbiphenyls, phenyl- or cyclo-hexylpyrimidines, phenyl- or cyclohexylpyridines, phenyl- or cyclohexyldioxanes, phenyl- or cyclohexyl-1,3-dithianes, 1,2-diphenylethanes, 1,2-dicyclohexylethanes, 1-phenyl-2-cyclohexylethanes, 1-cyclohexyl-2-(4-phenyl-cyclohexyl)ethanes, 1-cyclohexyl-2-biphenylethanes, 1-phenyl-2-cyclohexyl-phenylethanes, optionally halogenated stilbenes, benzyl phenyl ethers, tolans and substituted cinnamic acids. The 1,4-phenylene groups in these compounds may also be fluorinated.


The most important compounds suitable as further constituents of media according to the invention can be characterised by the formulae (1), (2), (3), (4) and (5):

R′-L-E-R″  (1)
R′-L-COO-E-R″  (2)
R′-L-OOC-E-R″  (3)
R′-L-CH2CH2-E-R″  (4)
R′-L-CF2O-E-R″  (5)


In the formulae (1), (2), (3), (4) and (5), L and E, which may be identical or different, are each, independently of one another, a divalent radical from the group formed by -Phe-, -Cyc-, -Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-, -Pyr-, -Dio-, -G-Phe- and -G-Cyc- and their mirror images, where Phe is unsubstituted or fluorine-substituted 1,4-phenylene, Cyc is trans-1,4-cyclohexylene or 1,4-cyclohexylene, Pyr is pyrimidine-2,5-diyl or pyridine-2,5-diyl, Dio is 1,3-dioxane-2,5-diyl, and G is 2-(trans-1,4-cyclohexyl)ethyl.


One of the radicals L and E is preferably Cyc or Phe. E is preferably Cyc, Phe or Phe-Cyc. The media according to the invention preferably comprise one or more components selected from the compounds of the formulae (1), (2), (3), (4) and (5) in which L and E are selected from the group consisting of Cyc and Phe and simultaneously one or more components selected from the compounds of the formulae (1), (2), (3), (4) and (5) in which one of the radicals L and E is selected from the group consisting of Cyc and Phe and the other radical is selected from the group consisting of -Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-, -G-Phe- and -G-Cyc-, and optionally one or more components selected from the compounds of the formulae (1), (2), (3), (4) and (5) in which the radicals L and E are selected from the group consisting of -Phe-Cyc-, -Cyc-Cyc-, -G-Phe- and -G-Cyc-.


In a smaller sub-group of the compounds of the formulae (1), (2), (3), (4) and (5), R′ and R″ are each, independently of one another, alkyl, alkenyl, alkoxy, alkoxyalkyl, alkenyloxy or alkanoyloxy having up to 8 carbon atoms. This smaller sub-group is called group A below, and the compounds are referred to by the sub-formulae (1a), (2a), (3a), (4a) and (5a). In most of these compounds, R′ and R″ are different from one another, one of these radicals usually being alkyl, alkenyl, alkoxy or alkoxyalkyl.


In another smaller sub-group of the compounds of the formulae (1), (2), (3), (4) and (5), which is referred to as group B, E is
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In the compounds of group B, which are referred to by the sub-formulae (1b), (2b), (3b), (4b) and (5b), R′ and R″ are as defined for the compounds of the sub-formulae (1a) to (5a) and are preferably alkyl, alkenyl, alkoxy or alkoxyalkyl.


In a further smaller sub-group of the compounds of the formulae (1), (2), (3), (4) and (5), R″ is —CN; this sub-group is referred to below as group C, and the compounds of this sub-group are correspondingly described by sub-formulae (1c), (2c), (3c), (4c) and (5c). In the compounds of the sub-formulae (1c), (2c), (3c), (4c) and (5c), R′ is as defined for the compounds of the sub-formulae (1a) to (5a) and is preferably alkyl, alkenyl, alkoxy or alkoxyalkyl.


Besides the preferred compounds of groups A, B and C, other compounds of the formulae (1), (2), (3), (4) and (5) having other variants of the proposed substituents are also customary. All these substances are obtainable by methods which are known from the literature or analogously thereto.


Besides the compounds of the general formulae (I), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX), (X) and/or (XI) according to the invention, the media according to the invention preferably comprise one or more compounds from groups A, B and/or C. The proportions by weight of the compounds from these groups in the media according to the invention are:


group A: from 0 to 90%, preferably from 20 to 90%, in particular from 30 to 90%


group B: from 0 to 80%, preferably from 10 to 80%, in particular from 10 to 70%


group C: from 0 to 80%, preferably from 5 to 80%, in particular from 5 to 50%.


The media according to the invention preferably comprise from 1 to 40%, particularly preferably from 5 to 30%, of the compounds of the formulae (I), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX), (X) and/or (XI) according to the invention. Preference is furthermore given to media comprising more than 40%, in particular from 45 to 90%, of compounds of the formulae (I), (II), (III), (IV), (V), (VI), (VII), (VII), (IX), (X) and/or (XI) according to the invention. The media preferably comprise three, four or five compounds of the formulae (I), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX), (X) and/or (XI) according to the invention.


Examples of the compounds of the formulae (1), (2), (3), (4) and (5) are the compounds listed below:
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where R1, R2, independently of one another, —CnH2n+1 or —OCnH2n+1, and n=1 to 8, and L1, L2, independently of one another, —H or —F.
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where m, n, independently of one another, from 1 to 8.


The media according to the invention are prepared in a manner conventional per se. In general, the components are dissolved in one another, advantageously at elevated temperature. By means of suitable additives, the liquid-crystalline phases of the present invention can be modified in such a way that they can be used in all types of liquid-crystal display elements that have been disclosed hitherto. Additives of this type 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 for the preparation of coloured guest-host systems or substances can be added in order to modify the dielectric anisotropy, the viscosity and/or the orientation of the nematic phases.


Owing to their negative Δε, the compounds of the formulae (II) to (VI) are particularly suitable for use in VA-TFT displays.


The present invention therefore also relates to electro-optical liquid-crystal display elements containing a liquid-crystalline medium according to the invention.


Owing to their high positive Δε, the compounds of the formulae (VII) to (XI) are particularly suitable for use in mesogenic control media, these control media being employed, in particular, in electro-optical light-control elements which are operated at a temperature at which the mesogenic control medium in the unaddressed 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 polarisation of the light and a mesogenic control medium, where the light-control element is operated at a temperature at which the mesogenic control medium in the unaddressed state is in the isotropic phase, and which are characterised in that the mesogenic control medium comprises one or more compounds of the formulae (VII) to (XI).


The invention is explained in greater detail below with reference to working examples, but without being restricted thereby.







EXAMPLES

The starting substances can be obtained by generally accessible literature procedures or commercially. The reactions described are known from the literature.


A) Preparation of the Naphthalene Derivatives


Example 1



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200 ml (100 mmol) of a 0.5 M solution of the zinc compound 2 in THF are added at −75° C. to a solution of 20.0 g (98.5 mmol) of the aldehyde 1 in 100 ml of THF. After 30 minutes, the cooling is removed. Water is added to the thawed batch, which is acidified using 1 N HCl solution and extracted with tert-butyl methyl (MTB) ether. Drying, evaporation and chromatography on silica gel gives the hydroxy ester 3.
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A solution of 10.0 g (32.7 mmol) of the hydroxy ester 3 is added at room temperature to a suspension of 40.0 mmol of pyridinium chlorochromate (PCC) on 50 g of Celite® in 150 ml of dichloromethane. When the reaction is complete (TLC), the batch is filtered, and the filter cake is washed with methylene chloride. Evaporation and chromatography on silica gel gives the keto ester 4.
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9.0 g (29.7 mmol) of the keto ester 4 are added at 60° C. to 100 g of poly-phosphoric acid. The temperature is subsequently increased to 120° C for 4 hours. After cooling, the batch is added to ice and extracted with tertbutyl methyl (MTB) ether. Drying, evaporation and crystallisation gives the diketone 5.
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5.0 g (19.5 mmol) of the diketone 5 are dissolved in 5 ml of ethanol, 3 ml of 100% hydrazinium hydroxide and 0.5 ml of water are added, and the mixture is refluxed for 30 minutes. A solution of 800 mg of sodium in 15 ml of ethanol is subsequently added to the reaction vessel. The batch is heated at 140° C. until the evolution of nitrogen is complete. ⅔ of the ethanol is subsequently distilled off. The residue is diluted with 50 ml of water and extracted with ether. The extract is washed with 10% KOH, 5% HCl and 30% sodium hydrogensulfite solution. Drying, evaporation and chromatography on silica gel gives the tetrahydronaphthalene 6.


Example 2



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8.0 g (31.1 mmol) of the diketone 5 are dissolved in 150 ml of ethanol, and 2.4 g (65.0 mmol) of sodium borohydride are added in portions. When the reaction is complete (TLC), the batch is hydrolysed using water, the ethanol is removed under reduced pressure, and the residue is taken up in water and extracted with toluene. After evaporation, the product is employed in the next step without further purification.
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10.0 g (38.3 mmol) of the diol 7 are dissolved in 200 ml of toluene, 1 g of p-toluenesulfonic acid is added, and the mixture is refluxed until the separation of water is complete. Evaporation and filtration through silica gel gives the naphthalene derivative 8.


Example 3



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30 ml of boron trifluoride/diethyl ether complex are added under nitrogen to a solution of 15.0 g (49.5 mmol) of the keto ester 4 and 8.4 ml (100 mmol) of the dithiol in 150 ml of dichloromethane, and the mixture is stirred overnight. The batch is slowly added to saturated sodium hydrogen-carbonate solution and deacidified. Drying, evaporation and chromatography on silica gel gives the protected ketone 9.
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A solution of 10 g (26.4 mmol) of the protected ketone 9 in 60 ml of dichloromethane is added at −75° C. to 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 batch is slowly warmed to 0° C. over the course of 3 hours and added to 1500 ml of ice-cooled 2 N sodium hydroxide solution to which 120 ml of a 39% sodium hydrogensulfite solution have been added. The pH is adjusted to 8, and the aqueous phase is extracted with methylene chloride. Drying, evaporation and chromatography on silica gel gives the fluorinated ester 10.
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Ring closure of the fluorinated ester 10 to give compound 11 is carried out as described in Example 1.
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Reduction to the alkane 12 is carried out as described in Example 1.


Example 4



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Reduction of compound 11 to the alcohol 13 and subsequent elimination of water to give the dihydronaphthalene derivative 14 are carried out as described in Example 2.


Example 5



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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 the mixture is subsequently refluxed overnight. The cooled batch is diluted with water and extracted with diethyl ether. Drying, evaporation and chromatography on silica gel gives the naphthalene 15.


Example 6



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22 ml of a 2 M lithium diisopropylamide (LDA) solution are added at −78° C. to a solution of 6.8 g (21.4 mmol) of the keto ester 4 in 80 ml of THF. After 1 hour, 2.6 g (24.0 mmol) of chlorotrimethylsilane are added. After thawing, the solvents are removed under reduced pressure, and the residue is employed in the subsequent step without further purification.
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4.9 g (19.8 mmol) of N-fluoropyridinium triflate are added to a solution of 5 g of the crude enol ether 16, and the mixture is refluxed overnight. The solvent is removed under reduced pressure, and the residue is purified by chromatography on silica gel, giving the fluorinated product 17.
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The conversions of the fluorinated product 17 into the dihydronaphthalene derivative 21 are carried out as already described in Examples 3 and 4.


Example 7



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The conversion of the dihydronaphthalene derivative 21 into the naphthalene derivative 22 is carried out as already described in Example 5.


Example 8



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The conversion of compound 20 into the dihydronaphthalene derivative 24 is carried out as already described in Examples 4 and 5.


Example 9



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The hydroxy ester 3 is reacted with benzyl bromide in dimethylformamide (DMF) in the presence of potassium carbonate for four hours at 120° C. After cooling, the batch is added to ice-water and extracted with tert-butyl methyl (MTB) ether. Drying, evaporation and crystallisation gives the ester 25.


The conversion of the ester 25 into the ketone 26 and the reduction thereof to the ether 27 takes place as described in Example 1.


The ether 27 dissolved in THF is reacted on palladium/carbon catalyst in a hydrogen atmosphere. Evaporation and chromatography on silica gel gives the hydroxyl compound 28.


The conversion of the hydroxyl compound 28 into the ketone 29 is carried out as described in Example 1.


The ketone 29 is reacted with iodobenzene diacetate and KOH in methanol for four hours at from 0 to 20° C., giving the hydroxy ketone 30.


The conversion of the hydroxy ketone 30 into the dithiolane 31 and the conversion thereof into the fluorinated hydroxyl compound 32 take place as described in Example 3.


The fluorinated hydroxyl compound 32 is mixed with pyridine and POCl3 with ice cooling. Alcohol is subsequently added. The reaction is carried out for four hours at 60° C. After cooling, the batch is added to ice-water and extracted with tert-butyl methyl (MTB) ether. Drying, evaporation and crystallisation gives the unsaturated fluorinated compound 33.


Example 10



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48.0 g (200 mmol) of the aromatic compound 34, 4.8 g (200 mmol) of magnesium and 200 ml of toluene/THF (4:1) are used to prepare the corresponding Grignard compound. 22.5 g (100 mmol) of zinc bromide are subsequently 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, water is added to the batch, and the latter is acidified with dil. HCl solution. The aqueous phase is extracted three times with MTB ether. Drying, evaporation and chromatography gives 60.4 g of the ester 36.
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A solution of 50 g (124 mmol) of the ester 36 in 100 ml of dichloromethane is added at room temperature to a suspension of 40.0 g (186 mmol) of pyridinium chlorochromate (PCC) and 80 g of Celite in 300 ml of dichloromethane, and the mixture is stirred until conversion is complete (TLC). Filtration, evaporation and chromatography gives 47.1 g of the oxo ester 37.
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45 g (113 mol) of the ester 37 are refluxed for 20 hours with a solution of 20 g of potassium hydroxide in 50 ml of water and 150 ml of ethanol. The alcohol is subsequently removed, and the residue is taken up with water and acidified using HCl solution. The aqueous phase is extracted three times with MTB ether. The organic phase is dried and evaporated. 20 ml of thionyl chloride are added to the residue, and the mixture is refluxed until the evolution of gas is complete. Excess thionyl chloride is distilled off, and the residue is employed in the next step without further purification.


A solution of the acid chloride 38 in 50 ml of dichloromethane is added at −25° C. to a suspension of 18.0 g (136 mmol) of aluminium chloride in 50 ml of dichloromethane. The batch is held at a temperature below −12° C. until conversion is complete (TLC). The reaction is subsequently terminated by careful addition of water (50 ml). The precipitated solid is dissolved by means of HCl solution. The aqueous phase is extracted twice with dichloromethane, and the organic phase is dried and evaporated. Chromatography gives 30.2 g of the diketone 39.
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30.0 g (84.8 mmol) of the diketone 39 are dissolved in 150 ml of ethanol, and 6.3 g (170 mmol) of sodium borohydride are added in portions. When the reaction is complete (TLC), the batch is hydrolysed using water, the ethanol is removed under reduced pressure, and the residue is taken up in water and extracted with toluene. After evaporation, the product is employed in the next step without further purification.
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The crude diol 40 is dissolved in 200 ml of toluene, 2 g of p-toluenesulfonic acid are added, and the mixture is refluxed until the separation of water is complete. Evaporation and filtration through silica gel gives 24.7 g of the naphthalene 41.


B) Preparation of the Cyclopenta[b]Naphthalene Derivatives


Example 11



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A solution of 13.5 g (60.0 mmol) of the bromofluoronaphthalene 7 in 10 ml of THF is added at −75° C. to 27.0 ml of a solution, diluted with 100 ml of THF, of 2 N lithium diisopropylamide (LDA) in cyclohexane/ethylbenzene/THF (52.4 mmol). After 2 hours at the low temperature, 8.5 g (47.3 mmol) of the aldehyde 42 in 10 ml of THF are added. After 30 minutes, the cooling is removed, and 100 ml of 1 N HCl are added to the batch at 20° C. Extraction of the aqueous phase, drying of the organic phase, evaporation and chromatography gives the allyl alcohol 43.
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35.0 g (86.6 mmol) of the allyl alcohol 43, 5.5 g of bis(tri-o-tolylphosphine)-palladium dichloride and 50 ml of triethylamine are dissolved in 390 ml of acetonitrile, and the mixture is warmed at 90° C. until the allyl alcohol has reacted completely. The cooled batch is added to water. Extraction, drying, evaporation and chromatography gives the ketone 44.


Example 12



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10.0 g (30.8 mmol) of the ketone 44 and 3.2 ml (31.0 mmol) of propanedithiol are dissolved in 50 ml of dichloromethane, and 7.0 ml of boron trifluoride/diethyl ether complex are added at from 6 to 7° C., and the mixture is subsequently stirred overnight at room temperature. The batch is added to 10 ml of saturated sodium hydrogencarbonate solution and stirred until the evolution of gas is complete. After extraction of the aqueous phase, drying of the organic phase, evaporation and filtration through silica gel, the resultant residue is employed in the next step without further purification.
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10.0 g of the crude thioketal 45 dissolved in 30 ml of dichloromethane are slowly added at −75° C. to a mixture of 28.6 g (100 mmol) of 1,3-dibromo-5,5-dimethylhydantoin (DBH), 80 ml of a 65% solution of hydrogen fluoride in pyridine and 50 ml of dichloromethane. The batch is subsequently stirred overnight at room temperature. The reaction mixture is added to ice-cooled hydrogen sulfite solution and deacidified using saturated sodium hydrogencarbonate solution and sodium hydroxide solution. Extraction, drying, evaporation, re-washing with water, chromatography and crystallisation from hexane gives the cyclopenta[b]naphthalene derivative 46.
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6.0 g (14.1 mmol) of the cyclopenta[b]naphthalene derivative 46 are dissolved in 50 ml of dichloromethane, 2.4 ml (16.0 mmol) of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) are added, and the mixture is stirred at room temperature until the starting material has reacted completely. The batch is washed with water and saturated sodium chloride solution, evaporated and subjected to chromatography. The cyclopenta[b]naphthalene derivative 47 is isolated.


Example 13



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4.0 g (11.6 mmol) of the cyclopenta[b]naphthalene derivative 47 are dissolved in 50 ml of THF and hydrogenated at room temperature and atmospheric pressure on a palladium catalyst. Evaporation, chromatography on silica gel and crystallisation gives the cyclopenta[b]naphthalene derivative 48.


The Δn and Δε values of the compound according to the invention were obtained by extrapolation from liquid-crystalline mixtures consisting of 5% of the compound according to the invention and 95% of one of the two commercially available liquid-crystal mixtures ZLI 4792 and ZLI 2857 (Merck, Darmstadt).


Δn: 0.1418 (ZLI 4792, 589 nm, 20° C.)


ΔεF: 4.9 (ZLI 2857, 1 kHz, 20° C.)


Clearing point: 158.6° C. (ZLI 4792)


Example 14



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38.0 ml of an n-butyllithium solution in n-hexane are added at −75° C. to a solution of 20.0 g (62.1 mmol) of the naphthalene 41 in 100 ml of diethyl ether, and the mixture is stirred for 1 hour. 11.2 g (62.1 mmol) of the aldehyde 49 in 50 ml of diethyl ether are subsequently added, and the mixture is stirred overnight. Water is added to the batch. The aqueous phase is extracted with diethyl ether, and the organic phase is dried and evaporated. Chromatography gives 21.2 g of the allyl alcohol 50.
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20.0 g (47.2 mmol) of the allyl alcohol 50 are dissolved in 175 ml of acetonitrile and 25 ml of triethylamine, 2.5 g of bis-tri-o-tolylphosphinepalladium(II) chloride are added, and the mixture is warmed at 90° C. until the starting material has disappeared (HPLC). The batch is subsequently added to saturated sodium chloride solution. Extraction with MTB ether, drying, evaporation and chromatography on silica gel gives 10.5 g of the ketone 51.
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10.0 g (29.2 mmol) of the ketone 51 are dissolved in 75 ml of ethanol, and 3.2 g (86 mmol) of sodium borohydride are added in portions. When the reaction is complete (TLC), the batch is hydrolysed using water, the ethanol is removed under reduced pressure, and the residue is taken up in water and extracted with toluene. After evaporation, the product is employed in the next step without further purification. The crude alcohol is dissolved in 100 ml of toluene, 1 g of p-toluenesulfonic acid is added, and the mixture is refluxed until the separation of water is complete. Evaporation and filtration through silica gel gives 8.5 of the naphthalene 52.
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8.0 g (25.5 mmol) of the naphthalene 52 are dissolved in 50 ml of THF and hydrogenated on a palladium catalyst. Evaporation and chromatography on silica gel gives 7.9 g of the hydrogenated substance 53.


The following compounds are prepared analogously to Examples 1 to 14 or analogously to known synthetic steps:


Examples 15 to 29



















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Example
L3
L4
L5
Z
R















15
H
H
F
Bd.
CH3


16
H
F
F
Bd.
C2H5


17
H
F
F
Bd.
C3H7


18
F
F
F
Bd.
C3H7


19
F
F
F
Bd.
C4H9


20
OC2H5
F
F
Bd.
C3H7


21
OC2H5
F
F
Bd.
C5H11


22
H
H
F
—CF2CF2
CH3


23
H
H
F
—CF2CF2
C3H7


24
H
F
F
—CF2CF2
C2H5


25
H
F
F
—CF2CF2
C3H7


26
F
F
F
—CF2CF2
C3H7


27
F
F
F
—CF2CF2
C4H9


28
OC2H5
F
F
—CF2CF2
C3H7


29
OC2H5
F
F
—CF2CF2
C5H11







Bd. = single bond







Examples 30 to 53



















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Example
L3
L4
L5
Z
R















30
H
H
F
Bd.
CH3


31
H
H
F
Bd.
C3H7


32
H
F
F
Bd.
C2H5


33
H
F
F
Bd.
C3H7


34
F
F
F
Bd.
C3H7


35
F
F
F
Bd.
C4H9


36
OC2H5
F
F
Bd.
C3H7


37
OC2H5
F
F
Bd.
C5 H11


38
H
H
F
—CF2O—
CH3


39
H
H
F
—CF2O—
C3H7


40
H
F
F
—CF2O—
C2H5


41
H
F
F
—CF2O—
C3H7


42
F
F
F
—CF2O—
C3H7


43
F
F
F
—CF2O—
C4H9


44
OC2H5
F
F
—CF2O—
C3H7


45
OC2H5
F
F
—CF2O—
C5 H11


46
H
H
F
—CF2CF2
CH3


47
H
H
F
—CF2CF2
C3H7


48
H
F
F
—CF2CF2
C2H5


49
H
F
F
—CF2CF2
C3H7


50
F
F
F
—CF2CF2
C3H7


51
F
F
F
—CF2CF2
C4H9


52
OC2H5
F
F
—CF2CF2
C3H7


53
OC2H5
F
F
—CF2CF2
C5 H11







Bd. = single band







Examples 54 to 77



















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Example
L3
L4
L5
Z
R















54
H
H
F
Bd.
CH3


55
H
H
F
Bd.
C3H7


56
H
F
F
Bd.
C2H5


57
H
F
F
Bd.
C3H7


58
F
F
F
Bd.
C3H7


59
F
F
F
Bd.
C4H9


60
OC2H5
F
F
Bd.
C3H7


61
OC2H5
F
F
Bd.
C5H11


62
H
H
F
—CF2O—
CH3


63
H
H
F
—CF2O—
C3H7


64
H
F
F
—CF2O—
C2H5


65
H
F
F
—CF2O—
C3H7


66
F
F
F
—CF2O—
C3H7


67
F
F
F
—CF2O—
C4H9


68
OC2H5
F
F
—CF2O—
C3H7


69
OC2H5
F
F
—CF2O—
C5H11


70
H
H
F
—CF2CF2
CH3


71
H
H
F
—CF2CF2
C3H7


72
H
F
F
—CF2CF2
C2H5


73
H
F
F
—CF2CF2
C3H7


74
F
F
F
—CF2CF2
C3H7


75
F
F
F
—CF2CF2
C4H9


76
OC2H5
F
F
—CF2CF2
C3H7


77
OC2H5
F
F
—CF2CF2
C5H11







Bd. = single bond







Examples 78 to 93



















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Example
L3
L4
L5
Z
R















78
H
H
F
Bd.
CH3


79
H
H
F
Bd.
C3H7


80
H
F
F
Bd.
C2H5


81
H
F
F
Bd.
C3H7


82
F
F
F
Bd.
C3H7


83
F
F
F
Bd.
C4H9


84
OC2H5
F
F
Bd.
C3H7


85
OC2H5
F
F
Bd.
C5H11


86
H
H
F
—CF2CF2
CH3


87
H
H
F
—CF2CF2
C3H7


88
H
F
F
—CF2CF2
C2H5


89
H
F
F
—CF2CF2
C3H7


90
F
F
F
—CF2CF2
C3H7


91
F
F
F
—CF2CF2
C4H9


92
OC2H5
F
F
—CF2CF2
C3H7


93
OC2H5
F
F
—CF2CF2
C5H11







Bd. = single bond







Examples 94 to 117



















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Example
L3
L4
L5
Z
R















94
H
H
F
Bd.
CH3


95
H
H
F
Bd.
C3H7


96
H
F
F
Bd.
C2H5


97
H
F
F
Bd.
C3H7


98
F
F
F
Bd.
C3H7


99
F
F
F
Bd.
C4H9


100
OC2H5
F
F
Bd.
C3H7


101
OC2H5
F
F
Bd.
C5H11


102
H
H
F
—CF2O—
CH3


103
H
H
F
—CF2O—
C3H7


104
H
F
F
—CF2O—
C2H5


105
H
F
F
—CF2O—
C3H7


106
F
F
F
—CF2O—
C3H7


107
F
F
F
—CF2O—
C4H9


108
OC2H5
F
F
—CF2O—
C3H7


109
OC2H5
F
F
—CF2O—
C5H11


110
H
H
F
—CF2CF2
CH3


111
H
H
F
—CF2CF2
C3H7


112
H
F
F
—CF2CF2
C2H5


113
H
F
F
—CF2CF2
C3H7


114
F
F
F
—CF2CF2
C3H7


115
F
F
F
—CF2CF2
C4H9


116
OC2H5
F
F
—CF2CF2
C3H7


117
OC2H5
F
F
—CF2CF2
C5H11







Bd. = single bond







Examples 118 to 141



















embedded image

















Example
L3
L4
L5
Z
R















118
H
H
F
Bd.
CH3


119
H
H
F
Bd.
C3H7


120
H
F
F
Bd.
C2H5


121
H
F
F
Bd.
C3H7


122
F
F
F
Bd.
C3H7


123
F
F
F
Bd.
C4H9


124
OC2H5
F
F
Bd.
C3H7


125
OC2H5
F
F
Bd.
C5hd 11


126
H
H
F
—CF2O—
CH3


127
H
H
F
—CF2O—
C3H7


128
H
F
F
—CF2O—
C2H5


129
H
F
F
—CF2O—
C3H7


130
F
F
F
—CF2O—
C3H7


131
F
F
F
—CF2O—
C4H9


132
OC2H5
F
F
—CF2O—
C3H7


133
OC2H5
F
F
—CF2O—
C5hd 11


134
H
H
F
—CF2CF2
CH3


135
H
H
F
—CF2CF2
C3H7


136
H
F
F
—CF2CF2
C2H5


137
H
F
F
—CF2CF2
C3H7


138
F
F
F
—CF2CF2
C3H7


139
F
F
F
—CF2CF2
C4H9


140
OC2H5
F
F
—CF2CF2
C3H7


141
OC2H5
F
F
—CF2CF2
C5hd 11







Bd. = single bond







Examples 142 to 157



















embedded image

















Example
L3
L4
L5
Z
R















142
H
H
H
Bd.
CH3


143
H
H
H
Bd.
C3H7


144
H
F
F
Bd.
C2H5


145
H
F
F
Bd.
C3H7


146
F
F
F
Bd.
C3H7


147
F
F
F
Bd.
C49


148
OC2H5
F
F
Bd.
C3H7


149
OC2H5
F
F
Bd.
C5H11


150
H
H
H
—CF2CF2
CH3


151
H
H
H
—CF2CF2
C3H7


152
H
F
F
—CF2CF2
C2H5


153
H
F
F
—CF2CF2
C3H7


154
F
F
F
—CF2CF2
C3H7


155
F
F
F
—CF2CF2
C49


156
OC2H5
F
F
—CF2CF2
C3H7


157
OC2H5
F
F
—CF2CF2
C5H11







Bd. = single bond







Examples 158 to 181



















embedded image

















Example
L3
L4
L5
Z
R















158
H
H
H
Bd.
CH3


159
H
H
H
Bd.
C3H7


160
H
F
F
Bd.
C2H5


161
H
F
F
Bd.
C3H7


162
F
F
F
Bd.
C3H7


163
F
F
F
Bd.
C4H9


164
OC2H5
F
F
Bd.
C3H7


165
OC2H5
F
F
Bd.
C5H11


166
H
H
H
—CF2O—
CH3


167
H
H
H
—CF2O—
C3H7


168
H
F
F
—CF2O—
C2H5


169
H
F
F
—CF2O—
C3H7


170
F
F
F
—CF2O—
C3H7


171
F
F
F
—CF2O—
C4H9


172
OC2H5
F
F
—CF2O—
C3H7


173
OC2H5
F
F
—CF2O—
C5H11


174
H
H
H
—CF2CF2
CH3


175
H
H
H
—CF2CF2
C3H7


176
H
F
F
—CF2CF2
C2H5


177
H
F
F
—CF2CF2
C3H7


178
F
F
F
—CF2CF2
C3H7


179
F
F
F
—CF2CF2
C4H9


180
OC2H5
F
F
—CF2CF2
C3H7


181
OC2H5
F
F
—CF2CF2
C5H11







Bd. = single bond







Examples 182 to 205



















embedded image

















Example
L3
L4
L5
Z
R















182
H
H
H
Bd.
CH3


183
H
H
H
Bd.
C3H7


184
H
F
F
Bd.
C2H5


185
H
F
F
Bd.
C3H7


186
F
F
F
Bd.
C3H7


187
F
F
F
Bd.
C4H9


188
OC2H5
F
F
Bd.
C3H7


189
OC2H5
F
F
Bd.
C5H11


190
H
H
H
—CF2O—
CH3


191
H
H
H
—CF2O—
C3H7


192
H
F
F
—CF2O—
C2H5


193
H
F
F
—CF2O—
C3H7


194
F
F
F
—CF2O—
C3H7


195
F
F
F
—CF2O—
C4H9


196
OC2H5
F
F
—CF2O—
C3H7


197
OC2H5
F
F
—CF2O—
C5H11


198
H
H
H
—CF2CF2
CH3


199
H
H
H
—CF2CF2
C3H7


200
H
F
F
—CF2CF2
C2H5


201
H
F
F
—CF2CF2
C3H7


202
F
F
F
—CF2CF2
C3H7


203
F
F
F
—CF2CF2
C4H9


204
OC2H5
F
F
—CF2CF2
C3H7


205
OC2H5
F
F
—CF2CF2
C5H11







Bd. = single bond







Examples 206 to 217



















embedded image


















Example
L3
L4
L5
L6
Z
R
















206
H
H
H
H
Bd.
CH3


207
H
H
H
H
Bd.
C3H7


208
H
H
F
F
Bd.
C2H5


209
H
H
F
F
Bd.
C3H7


210
F
F
F
F
Bd.
C3H7


211
F
F
F
F
Bd.
C4H9


212
H
H
H
H
—CF2CF2
CH3


213
H
H
H
H
—CF2CF2
C3H7


214
H
H
F
F
—CF2CF2
C2H5


215
H
H
F
F
—CF2CF2
C3H7


216
F
F
F
F
—CF2CF2
C3H7


217
F
F
F
F
—CF2CF2
C4H9







Bd. = single bond







Examples 218 to 235



















embedded image


















Example
L3
L4
L5
L6
Z
R
















218
H
H
H
H
Bd.
CH3


219
H
H
H
H
Bd.
C3H7


220
H
H
F
F
Bd.
C2H5


221
H
H
F
F
Bd.
C3H7


222
F
F
F
F
Bd.
C3H7


223
F
F
F
F
Bd.
C4H9


224
H
H
H
H
—CF2O—
CH3


225
H
H
H
H
—CF2O—
C3H7


226
H
H
F
F
—CF2O—
C2H5


227
H
H
F
F
—CF2O—
C3H7


228
F
F
F
F
—CF2O—
C3H7


229
F
F
F
F
—CF2O—
C4H9


230
H
H
H
H
—CF2CF2
CH3


231
H
H
H
H
—CF2CF2
C3H7


232
H
H
F
F
—CF2CF2
C2H5


233
H
H
F
F
—CF2CF2
C3H7


234
F
F
F
F
—CF2CF2
C3H7


235
F
F
F
F
—CF2CF2
C4H9







Bd. = single bond







Examples 236 to 253



















embedded image


















Example
L3
L4
L5
L6
Z
R
















236
H
H
H
H
Bd.
CH3


237
H
H
H
H
Bd.
C3H7


238
H
H
F
F
Bd.
C2H5


239
H
H
F
F
Bd.
C3H7


240
F
F
F
F
Bd.
C3H7


241
F
F
F
F
Bd.
C4H9


242
H
H
H
H
—CF2O—
CH3


243
H
H
H
H
—CF2O—
C3H7


244
H
H
F
F
—CF2O—
C2H5


245
H
H
F
F
—CF2O—
C3H7


246
F
F
F
F
—CF2O—
C3H7


247
F
F
F
F
—CF2O—
C4H9


248
H
H
H
H
—CF2CF2
CH3


249
H
H
H
H
—CF2CF2
C3H7


250
H
H
F
F
—CF2CF2
C2H5


251
H
H
F
F
—CF2CF2
C3H7


252
F
F
F
F
—CF2CF2
C3H7


253
F
F
F
F
—CF2CF2
C4H9







Bd. = single band







Examples 254 to 265



















embedded image


















Example
L3
L4
L5
L6
Z
R
















254
H
H
H
H
Bd.
CH3


255
H
H
H
H
Bd.
C3H7


256
H
H
F
F
Bd.
C2H5


257
H
H
F
F
Bd.
C3H7


258
F
F
F
F
Bd.
C3H7


259
F
F
F
F
Bd.
C4H9


260
H
H
H
H
—CF2CF2
CH3


261
H
H
H
H
—CF2CF2
C3H7


262
H
H
F
F
—CF2CF2
C2H5


263
H
H
F
F
—CF2CF2
C3H7


264
F
F
F
F
—CF2CF2
C3H7


265
F
F
F
F
—CF2CF2
C4H9







Bd. = single bond







Examples 266 to 283



















embedded image


















Example
L3
L4
L5
L6
Z
R
















266
H
H
H
H
Bd.
CH3


267
H
H
H
H
Bd.
C3H7


268
H
H
F
F
Bd.
C2H5


269
H
H
F
F
Bd.
C3H7


270
F
F
F
F
Bd.
C3H7


271
F
F
F
F
Bd.
C4H9


272
H
H
H
H
—CF2O—
CH3


273
H
H
H
H
—CF2O—
C3H7


274
H
H
F
F
—CF2O—
C2H5


275
H
H
F
F
—CF2O—
C3H7


276
F
F
F
F
—CF2O—
C3H7


277
F
F
F
F
—CF2O—
C4H9


278
H
H
H
H
—CF2CF2
CH3


279
H
H
H
H
—CF2CF2
C3H7


280
H
H
F
F
—CF2CF2
C2H5


281
H
H
F
F
—CF2CF2
C3H7


282
F
F
F
F
—CF2CF2
C3H7


283
F
F
F
F
—CF2CF2
C4H9







Bd. = single bond







Examples 284 to 301



















embedded image


















Example
L3
L4
L5
L6
Z
R
















284
H
H
H
H
Bd.
CH3


285
H
H
H
H
Bd.
C3H7


286
H
H
F
F
Bd.
C2H5


287
H
H
F
F
Bd.
C3H7


288
F
F
F
F
Bd.
C3H7


289
F
F
F
F
Bd.
C4H9


290
H
H
H
H
—CF2O—
CH3


291
H
H
H
H
—CF2O—
C3H7


292
H
H
F
F
—CF2O—
C2H5


293
H
H
F
F
—CF2O—
C3H7


294
F
F
F
F
—CF2O—
C3H7


295
F
F
F
F
—CF2O—
C4H9


296
H
H
H
H
—CF2CF2
CH3


297
H
H
H
H
—CF2CF2
C3H7


298
H
H
F
F
—CF2CF2
C2H5


299
H
H
F
F
—CF2CF2
C3H7


300
F
F
F
F
—CF2CF2
C3H7


301
F
F
F
F
—CF2CF2
C4H9







Bd. = single bond














TABLE 1










Δε and Δn values for substances of individual examples









Example




No.
Δε
Δn












17
−6.3
0.143


18
−8.0
0.143


20
−7.3
0.166


79
−3.9
0.127


81
−9.1
0.117


82
−10.2
0.121


143
−3.3
0.091


145
−11.8
0.081


146
−9.2
0.081


207
−2.2
0.128


209
−9.6
0.115


210
−6.9
0.106


255
−3.0
0.095


257
−10.3
0.079


258
−7.9
0.079









Examples 302 to 337



















embedded image

















Example
L1
L2
L3
L4
R















302
H
F
H
H
CH3


303
H
F
H
H
C3H7


304
H
F
H
H
C5H11


305
H
F
F
H
C2H5


306
H
F
F
H
C3H7


307
H
F
F
H
C6H13


308
F
F
F
F
CH3


309
F
F
F
F
C3H7


310
F
F
F
F
C5H11


311
H
CF3
H
H
C2H5


312
H
CF3
H
H
C3H7


313
H
CF3
H
H
C6H13


314
H
OCF3
H
H
CH3


315
H
OCF3
H
H
C3H7


316
H
OCF3
H
H
C5H11


317
H
CN
H
H
C2H5


318
H
CN
H
H
C3H7


319
H
CN
H
H
C6H13


320
H
CF3
F
H
C2H5


321
H
CF3
F
H
C3H7


322
H
CF3
F
H
C6H13


323
H
OCF3
F
H
CH3


324
H
OCF3
F
H
C3H7


325
H
OCF3
F
H
C5H11


326
H
CF3
CF3
H
C2H5


327
H
CF3
CF3
H
C3H7


328
H
CF3
CF3
H
C6H13


329
H
CF3
OCF3
H
CH3


330
H
CF3
OCF3
H
C3H7


331
H
CF3
OCF3
H
C5H11


332
H
OCF3
OCF3
H
C2H5


333
H
OCF3
OCF3
H
C3H7


334
H
OCF3
OCF3
H
C6H13


335
H
CN
CN
H
C2H5


336
H
CN
CN
H
C3H7


337
H
CN
CN
H
C6H13
















TABLE 2










Δε and Δn values for substances of individual examples









Example




No.
Δε
Δn





306
12.9
0.179


309
17.0
0.158


312
12.7
0.160


321
23.2
0.159


324
12.4
0.172


327
31.4
0.159


330
19.7
0.143


333
17.4
0.158









Examples 338 to 367



















embedded image

















Example
L1
L2
L3
L4
R















302
H
F
H
H
CH3


339
H
F
H
H
C3H7


340
H
F
H
H
C5H11


341
H
F
F
H
C2H5


342
H
F
F
H
C3H7


343
H
F
F
H
C6H13


344
F
F
F
F
CH3


345
F
F
F
F
C3H7


346
F
F
F
F
C5H11


347
H
CF3
H
H
C2H5


348
H
CF3
H
H
C3H7


349
H
CF3
H
H
C6H13


350
H
OCF3
H
H
CH3


351
H
OCF3
H
H
C3H7


352
H
OCF3
H
H
C5H11


353
H
CF3
F
H
C2H5


354
H
CF3
F
H
C3H7


355
H
CF3
F
H
C6H13


356
H
OCF3
F
H
CH3


357
H
OCF3
F
H
C3H7


358
H
OCF3
F
H
C5H11


359
H
CF3
CF3
H
C2H5


360
H
CF3
CF3
H
C3H7


361
H
CF3
CF3
H
C6H13


362
H
CF3
OCF3
H
CH3


363
H
CF3
OCF3
H
C3H7


364
H
CF3
OCF3
H
C5H11


365
H
OCF3
OCF3
H
C2H5


366
H
OCF3
OCF3
H
C3H7


367
H
OCF3
OCF3
H
C6H13









Examples 368 to 397



















embedded image

















Example
L1
L2
L3
L4
R















302
H
F
H
H
CH3


369
H
F
H
H
C3H7


370
H
F
H
H
C5H11


371
H
F
F
H
C2H5


372
H
F
F
H
C3H7


373
H
F
F
H
C6H13


374
F
F
F
F
CH3


375
F
F
F
F
C3H7


376
F
F
F
F
C5H11


377
H
CF3
H
H
C2H5


378
H
CF3
H
H
C3H7


379
H
CF3
H
H
C6H13


380
H
OCF3
H
H
CH3


381
H
OCF3
H
H
C3H7


382
H
OCF3
H
H
C5H11


383
H
CF3
F
H
C2H5


384
H
CF3
F
H
C3H7


385
H
CF3
F
H
C6H13


386
H
OCF3
F
H
CH3


387
H
OCF3
F
H
C3H7


388
H
OCF3
F
H
C5H11


389
H
CF3
CF3
H
C2H5


390
H
CF3
CF3
H
C3H7


391
H
CF3
CF3
H
C6H11


392
H
CF3
OCF3
H
CH3


393
H
CF3
OCF3
H
C3H7


394
H
CF3
OCF3
H
C5H11


395
H
OCF3
OCF3
H
C2H5


396
H
OCF3
OCF3
H
C3H7


397
H
OCF3
OCF3
H
C6H13









Examples 398 to 427



















embedded image

















Example
L1
L2
L3
L4
R















302
H
F
H
H
CH3


399
H
F
H
H
C3H7


400
H
F
H
H
C5H11


401
H
F
F
H
C2H5


402
H
F
F
H
C3H7


403
H
F
F
H
C6H13


404
F
F
F
F
CH3


405
F
F
F
F
C3H7


406
F
F
F
F
C5H11


407
H
CF3
H
H
C2H5


408
H
CF3
H
H
C3H7


409
H
CF3
H
H
C6H13


410
H
OCF3
H
H
CH3


411
H
OCF3
H
H
C3H7


412
H
OCF3
H
H
C5H11


413
H
CF3
F
H
C2H5


414
H
CF3
F
H
C3H7


415
H
CF3
F
H
C6H13


416
H
OCF3
F
H
CH3


417
H
OCF3
F
H
C3H7


418
H
OCF3
F
H
C5H11


419
H
CF3
CF3
H
C2H5


420
H
CF3
CF3
H
C3H7


421
H
CF3
CF3
H
C6H13


422
H
CF3
OCF3
H
CH3


423
H
CF3
OCF3
H
C3H7


424
H
CF3
OCF3
H
C5H11


425
H
OCF3
OCF3
H
C2H5


426
H
OCF3
OCF3
H
C3H7


427
H
OCF3
OCF3
H
C6H13









Examples 428 to 457



















embedded image

















Example
L1
L2
L3
L4
R















302
H
F
H
H
CH3


429
H
F
H
H
C3H7


430
H
F
H
H
C5H11


431
H
F
F
H
C2H5


432
H
F
F
H
C3H7


433
H
F
F
H
C6H13


434
F
F
F
F
CH3


435
F
F
F
F
C3H7


436
F
F
F
F
C5H11


437
H
CF3
H
H
C2H5


438
H
CF3
H
H
C3H7


439
H
CF3
H
H
C6H13


440
H
OCF3
H
H
CH3


441
H
OCF3
H
H
C3H7


442
H
OCF3
H
H
C5H11


443
H
CF3
F
H
C2H5


444
H
CF3
F
H
C3H7


445
H
CF3
F
H
C6H13


446
H
OCF3
F
H
CH3


447
H
OCF3
F
H
C3H7


448
H
OCF3
F
H
C5H11


449
H
CF3
CF3
H
C2H5


450
H
CF3
CF3
H
C3H7


451
H
CF3
CF3
H
C6H13


452
H
CF3
OCF3
H
CH3


453
H
CF3
OCF3
H
C3H7


454
H
CF3
OCF3
H
C5H11


455
H
OCF3
OCF3
H
C2H5


456
H
OCF3
OCF3
H
C3H7


457
H
OCF3
OCF3
H
C6H13









Examples 458 to 487



















embedded image

















Example
L1
L2
L3
L4
R















458
H
F
H
H
CH3


459
H
F
H
H
C3H7


460
H
F
H
H
C5H11


461
H
F
F
H
C2H5


462
H
F
F
H
C3H7


463
H
F
F
H
C6H13


464
F
F
F
F
CH3


465
F
F
F
F
C3H7


466
F
F
F
F
C5H11


467
H
CF3
H
H
C2H5


468
H
CF3
H
H
C3H7


469
H
CF3
H
H
C6H13


470
H
OCF3
H
H
CH3


471
H
OCF3
H
H
C3H7


472
H
OCF3
H
H
C5H11


473
H
CF3
F
H
C2H5


474
H
CF3
F
H
C3H7


475
H
CF3
F
H
C6H13


476
H
OCF3
F
H
CH3


477
H
OCF3
F
H
C3H7


478
H
OCF3
F
H
C5H11


479
H
CF3
CF3
H
C2H5


480
H
CF3
CF3
H
C3H7


481
H
CF3
CF3
H
C6H13


482
H
CF3
OCF3
H
CH3


483
H
CF3
OCF3
H
C3H7


484
H
CF3
OCF3
H
C5H11


485
H
OCF3
OCF3
H
C2H5


486
H
OCF3
OCF3
H
C3H7


487
H
OCF3
OCF3
H
C6H13









Examples 488 to 517



















embedded image

















Example
L1
L2
L3
L4
R















488
H
F
H
H
CH3


489
H
F
H
H
C3H7


490
H
F
H
H
C5H11


491
H
F
F
H
C2H5


492
H
F
F
H
C3H7


493
H
F
F
H
C6H13


494
F
F
F
F
CH3


495
F
F
F
F
C3H7


496
F
F
F
F
C5H11


497
H
CF3
H
H
C2H5


498
H
CF3
H
H
C3H7


499
H
CF3
H
H
C6H13


500
H
OCF3
H
H
CH3


501
H
OCF3
H
H
C3H7


502
H
OCF3
H
H
C5H11


503
H
CF3
F
H
C2H5


504
H
CF3
F
H
C3H7


505
H
CF3
F
H
C6H13


506
H
OCF3
F
H
CH3


507
H
OCF3
F
H
C3H7


508
H
OCF3
F
H
C5H11


509
H
CF3
CF3
H
C2H5


510
H
CF3
CF3
H
C3H7


511
H
CF3
CF3
H
C6H13


512
H
CF3
OCF3
H
CH3


513
H
CF3
OCF3
H
C3H7


514
H
CF3
OCF3
H
C5H11


515
H
OCF3
OCF3
H
C2H5


516
H
OCF3
OCF3
H
C3H7


517
H
OCF3
OCF3
H
C6H13









Examples 518 to 547



















embedded image

















Example
L1
L2
L3
L4
R















458
H
F
H
H
CH3


518
H
F
H
H
CH3


519
H
F
H
H
C3H7


520
H
F
H
H
C5H11


521
H
F
F
H
C2H5


522
H
F
F
H
C3H7


523
H
F
F
H
C6H13


524
F
F
F
F
CH3


525
F
F
F
F
C3H7


526
F
F
F
F
C5H11


527
H
CF3
H
H
C2H5


528
H
CF3
H
H
C3H7


529
H
CF3
H
H
C6H13


530
H
OCF3
H
H
CH3


531
H
OCF3
H
H
C3H7


532
H
OCF3
H
H
C5H11


533
H
CF3
F
H
C2H5


534
H
CF3
F
H
C3H7


535
H
CF3
F
H
C6H13


536
H
OCF3
F
H
CH3


537
H
OCF3
F
H
C3H7


538
H
OCF3
F
H
C5H11


539
H
CF3
CF3
H
C2H5


540
H
CF3
CF3
H
C3H7


541
H
CF3
CF3
H
C6H13


542
H
CF3
OCF3
H
CH3


543
H
CF3
OCF3
H
C3H7


544
H
CF3
OCF3
H
C5H11


545
H
OCF3
OCF3
H
C2H5


546
H
OCF3
OCF3
H
C3H7


547
H
OCF3
OCF3
H
C6H13









Examples 548 to 577



















embedded image

















Example
L1
L2
L3
L4
R















548
H
F
H
H
CH3


549
H
F
H
H
C3H7


550
H
F
H
H
C5H11


551
H
F
F
H
C2H5


552
H
F
F
H
C3H7


553
H
F
F
H
C6H13


554
F
F
F
F
CH3


555
F
F
F
F
C3H7


556
F
F
F
F
C5H11


557
H
CF3
H
H
C2H5


558
H
CF3
H
H
C3H7


559
H
CF3
H
H
C6H13


560
H
OCF3
H
H
CH3


561
H
OCF3
H
H
C3H7


562
H
OCF3
H
H
C5H11


563
H
CF3
F
H
C2H5


564
H
CF3
F
H
C3H7


565
H
CF3
F
H
C6H13


566
H
OCF3
F
H
CH3


567
H
OCF3
F
H
C3H7


568
H
OCF3
F
H
C5H11


569
H
CF3
CF3
H
C2H5


570
H
CF3
CF3
H
C3H7


571
H
CF3
CF3
H
C6H13


572
H
CF3
OCF3
H
CH3


573
H
CF3
OCF3
H
C3H7


574
H
CF3
OCF3
H
C5H11


575
H
OCF3
OCF3
H
C2H5


576
H
OCF3
OCF3
H
C3H7


577
H
OCF3
OCF3
H
C6H13









Examples 578 to 607



















embedded image

















Example
L1
L2
L3
L4
R















578
H
F
H
H
CH3


579
H
F
H
H
C3H7


580
H
F
H
H
C5H11


581
H
F
F
H
C2H5


582
H
F
F
H
C3H7


583
H
F
F
H
C6H13


584
F
F
F
F
CH3


585
F
F
F
F
C3H7


586
F
F
F
F
C5H11


587
H
CF3
H
H
C2H5


588
H
CF3
H
H
C3H7


589
H
CF3
H
H
C6H13


590
H
OCF3
H
H
CH3


591
H
OCF3
H
H
C3H7


592
H
OCF3
H
H
C5H11


593
H
CF3
F
H
C2H5


594
H
CF3
F
H
C3H7


595
H
CF3
F
H
C6H13


596
H
OCF3
F
H
CH3


597
H
OCF3
F
H
C3H7


598
H
OCF3
F
H
C5H11


599
H
CF3
CF3
H
C2H5


600
H
CF3
CF3
H
C3H7


601
H
CF3
CF3
H
C6H13


602
H
CF3
OCF3
H
CH3


603
H
CF3
OCF3
H
C3H7


604
H
CF3
OCF3
H
C5H11


605
H
OCF3
OCF3
H
C2H5


606
H
OCF3
OCF3
H
C3H7


607
H
OCF3
OCF3
H
C6H13









Examples 608 to 637



















embedded image

















Example
L1
L2
L3
L4
R















608
H
F
H
H
CH3


609
H
F
H
H
C3H7


610
H
F
H
H
C5H11


611
H
F
F
H
C2H5


612
H
F
F
H
C3H7


613
H
F
F
H
C6H13


614
F
F
F
F
CH3


615
F
F
F
F
C3H7


616
F
F
F
F
C5H11


617
H
CF3
H
H
C2H5


618
H
CF3
H
H
C3H7


619
H
CF3
H
H
C6H13


620
H
OCF3
H
H
CH3


621
H
OCF3
H
H
C3H7


622
H
OCF3
H
H
C5H11


623
H
CF3
F
H
C2H5


624
H
CF3
F
H
C3H7


625
H
CF3
F
H
C6H13


626
H
OCF3
F
H
CH3


627
H
OCF3
F
H
C3H7


628
H
OCF3
F
H
C5H11


629
H
CF3
CF3
H
C2H5


630
H
CF3
CF3
H
C3H7


631
H
CF3
CF3
H
C6H13


632
H
CF3
OCF3
H
CH3


633
H
CF3
OCF3
H
C3H7


634
H
CF3
OCF3
H
C5H11


635
H
OCF3
OCF3
H
C2H5


636
H
OCF3
OCF3
H
C3H7


637
H
OCF3
OCF3
H
C6H13









Examples 638 to 667



















embedded image

















Example
L1
L2
L3
L4
R















638
H
F
H
H
CH3


639
H
F
H
H
C3H7


640
H
F
H
H
C5H11


641
H
F
F
H
C2H5


642
H
F
F
H
C3H7


643
H
F
F
H
C6H13


644
F
F
F
F
CH3


645
F
F
F
F
C3H7


646
F
F
F
F
C5H11


647
H
CF3
H
H
C2H5


648
H
CF3
H
H
C3H7


649
H
CF3
H
H
C6H13


650
H
OCF3
H
H
CH3


651
H
OCF3
H
H
C3H7


652
H
OCF3
H
H
C5H11


653
H
CF3
F
H
C2H5


654
H
CF3
F
H
C3H7


655
H
CF3
F
H
C6H13


656
H
OCF3
F
H
CH3


657
H
OCF3
F
H
C3H7


658
H
OCF3
F
H
C5H11


659
H
CF3
CF3
H
C2H5


660
H
CF3
CF3
H
C3H7


661
H
CF3
CF3
H
C6H13


662
H
CF3
OCF3
H
CH3


663
H
CF3
OCF3
H
C3H7


664
H
CF3
OCF3
H
C5H11


665
H
OCF3
OCF3
H
C2H5


666
H
OCF3
OCF3
H
C3H7


667
H
OCF3
OCF3
H
C6H13









Examples 668 to 697



















embedded image

















Example
L1
L2
L3
L4
R















668
H
F
H
H
CH3


669
H
F
H
H
C3H7


670
H
F
H
H
C5H11


671
H
F
F
H
C2H5


672
H
F
F
H
C3H7


673
H
F
F
H
C6H13


674
F
F
F
F
CH3


675
F
F
F
F
C3H7


676
F
F
F
F
C5H11


677
H
CF3
H
H
C2H5


678
H
CF3
H
H
C3H7


679
H
CF3
H
H
C6H13


680
H
OCF3
H
H
CH3


681
H
OCF3
H
H
C3H7


682
H
OCF3
H
H
C5H11


683
H
CF3
F
H
C2H5


684
H
CF3
F
H
C3H7


685
H
CF3
F
H
C6H13


686
H
OCF3
F
H
CH3


687
H
OCF3
F
H
C3H7


688
H
OCF3
F
H
C5H11


689
H
CF3
CF3
H
C2H5


690
H
CF3
CF3
H
C3H7


691
H
CF3
CF3
H
C6H13


692
H
CF3
OCF3
H
CH3


693
H
CF3
OCF3
H
C3H7


694
H
CF3
OCF3
H
C5H11


695
H
OCF3
OCF3
H
C2H5


696
H
OCF3
OCF3
H
C3H7


697
H
OCF3
OCF3
H
C6H13









Examples 698 to 727



















embedded image

















Example
L1
L2
L3
L4
R















698
H
F
H
H
CH3


699
H
F
H
H
C3H7


700
H
F
H
H
C5H11


701
H
F
F
H
C2H5


702
H
F
F
H
C3H7


703
H
F
F
H
C6H13


704
F
F
F
F
CH3


705
F
F
F
F
C3H7


706
F
F
F
F
C5H11


707
H
CF3
H
H
C2H5


708
H
CF3
H
H
C3H7


709
H
CF3
H
H
C6H13


710
H
OCF3
H
H
CH3


711
H
OCF3
H
H
C3H7


712
H
OCF3
H
H
C5H11


713
H
CF3
F
H
C2H5


714
H
CF3
F
H
C3H7


715
H
CF3
F
H
C6H13


716
H
OCF3
F
H
CH3


717
H
OCF3
F
H
C3H7


718
H
OCF3
F
H
C5H11


719
H
CF3
CF3
H
C2H5


720
H
CF3
CF3
H
C3H7


721
H
CF3
CF3
H
C6H13


722
H
CF3
OCF3
H
CH3


723
H
CF3
OCF3
H
C3H7


724
H
CF3
OCF3
H
C5H11


725
H
OCF3
OCF3
H
C2H5


726
H
OCF3
OCF3
H
C3H7


727
H
OCF3
OCF3
H
C6H13








Claims
  • 1. Cyclopenta[b]naphthalene derivatives of the general formula (I)
  • 2. Cyclopenta[b]naphthalene derivatives according to claim 1 selected from the general formulae (II) to (VI)
  • 3. Cyclopenta[b]naphthalene derivatives according to claim 2, characterised in that B is
  • 4. Cyclopenta[b]naphthalene derivatives according to claim 2, characterised in that A is
  • 5. Cyclopenta[b]naphthalene derivatives according to claim 2, characterised in that L2 and L3, independently of one another, are hydrogen, an alkoxy radical having from 1 to 7 carbon atoms, fluorine or chlorine.
  • 6. Cyclopenta[b]naphthalene derivatives according to claim 2, characterised in that L4 and L6, independently of one another, are —CF3, fluorine or chlorine.
  • 7. Cyclopenta[b]naphthalene derivatives according to claim 1, selected from the general formulae (VII) to (X)
  • 8. Cyclopenta[b]naphthalene derivatives according to claim 7, characterised in that B is
  • 9. Cyclopenta[b]naphthalene derivatives according to claim 7, characterised in that A is
  • 10. Cyclopenta[b]naphthalene derivatives according to claim 7, characterised in that L2 and L3, independently of one another, are identical or different and are hydrogen, halogen, —CN, —SCN, —NCS, —SF5, —CF3, —CHF2, —OCF3 or —OCHF2.
  • 11. Cyclopenta[b]naphthalene derivatives according to claim 7, characterised in that L1 and L4, independently of one another, are identical or different and are hydrogen or fluorine.
  • 12. Cyclopenta[b]naphthalene derivatives according to claim 7, characterised in that L5 and L6 are hydrogen.
  • 13. Cyclopenta[b]naphthalene derivatives according to claim 7, characterised in that L1, L2, L3 and L4 are fluorine and L5 and L6 are hydrogen.
  • 14. Cyclopenta[b]naphthalene derivatives according to claim 1, characterised in that Z is a single bond, —CF2O—, —OCF2—, —CF2CF2—, —CH═CH—, —CF═CH—, —CH═CF— or —CF═CF—.
  • 15. Cyclopenta[b]naphthalene derivatives according to claim 1, characterised in that R is an alkyl radical, alkoxy radical or alkenyl radical having from 1 to 7 or 2 to 7 carbon atoms respectively.
  • 16. Use of cyclopenta[b]naphthalene derivatives according to claim 1 in liquid-crystalline media.
  • 17. Liquid-crystalline medium comprising at least two liquid-crystalline compounds, characterised in that it comprises at least one cyclopenta[b]naphthalene derivative according to claim 1.
  • 18. Electro-optical display element containing a liquid-crystalline medium according to claim 17.
  • 19. Mesogenic medium, characterised in that it comprises at least one cyclopenta[b]naphthalene derivative according to claim 7.
  • 20. Electro-optical light-control element which contains an electrode arrangement, at least one element for polarisation of the light and a mesogenic control medium, where the light-control element is operated at a temperature at which the mesogenic control medium in the unaddressed state is in the isotropic phase, characterised in that the mesogenic control medium comprises at least one cyclopenta[b]naphthalene derivative according to claim 7.
Priority Claims (2)
Number Date Country Kind
102 38 999.3 Aug 2002 DE national
103 24 843.9 Jun 2003 DE national
PCT Information
Filing Document Filing Date Country Kind 371c Date
PCT/EP03/08285 7/28/2003 WO 2/18/2005