# Patent

## Title
Cyclopenta[b]naphthalene derivatives

## Abstract

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 at least one of these cyclopenta[b]naphthalene derivatives, and to electro-optical display elements containing these liquid-crystalline or mesogenic media.

## Background
This application is a divisional of U.S. Ser. No. 10/524,846, filed Feb. 18, 2005, now U.S. Pat. No. 7,291,366 which is a §371 National Stage of PCT EP03 08265, filed Jul. 28, 2003, and is incorporated by reference herein.


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 ε 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, transparent 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




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—, cyclopropane-1,2-diyl, —Si(CH3)2—, 1,4-phenylene, 1,4-cyclohexylene, 1,3-cyclopentylene, 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




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)




    
    
        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,
        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 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, —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)




    
    
        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 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, —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 heteroatoms 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 Ac 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.




in the general formulae (II) to (VI) are preferably





particularly preferably





and in particular





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,




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, 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)




in which Z, A, R, n, L1 to L8 and





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:




where the structural formulae (VIIa) and (VIIc) are particularly preferred.





in the general formulae (VII) to (XI) are preferably





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,




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-enyl.
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 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 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 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 (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.




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 cyclohexylpyrimidines, 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-phenylcyclohexyl)ethanes, 1-cyclohexyl-2-biphenylethanes, 1-phenyl-2-cyclohexylphenylethanes, 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




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), (VIII), (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:







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,





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 As, 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




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.




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.




9.0 g (29.7 mmol) of the keto ester 4 are added at 60° C. to 100 g of polyphosphoric acid. The temperature is subsequently increased to 120° C. for 4 hours. After cooling, the batch is added to ice and extracted with tert-butyl methyl (MTB) ether. Drying, evaporation and crystallisation gives the diketone 5.




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. 2/3 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




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.




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




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 hydrogencarbonate solution and deacidified. Drying, evaporation and chromatography on silica gel gives the protected ketone 9.




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.




Ring closure of the fluorinated ester 10 to give compound 11 is carried out as described in Example 1.




Reduction to the alkane 12 is carried out as described in Example 1.
Example 4




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




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




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.




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.








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




The conversion of the dihydronaphthalene derivative 21 into the naphthalene derivative 22 is carried out as already described in Example 5.
Example 8




The conversion of compound 20 into the dihydronaphthalene derivative 24 is carried out as already described in Examples 4 and 5.
Example 9







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




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.




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.




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.




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.




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




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.




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




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.




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.




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




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.)
Δε: −4.9 (ZLI 2857, 1 kHz, 20° C.)
Clearing point: 158.6° C. (ZLI 4792)
Example 14




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.




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.




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.




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
















 














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
















 














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.
C5H11



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—
C5H11



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—
C5H11







Bd. = single bond






Examples 54 to 77
















 














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
















 














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
















 














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
















 














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.
C5H11



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—
C5H11



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—
C5H11







Bd. = single bond






Examples 142 to 157
















 














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.
C4H9



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—
C4H9



156
OC2H5
F
F
—CF2CF2—
C3H7



157
OC2H5
F
F
—CF2CF2—
C5H11







Bd. = single bond






Examples 158 to 181
















 














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
















 














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
















 













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
















 













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
















 













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 bond






Examples 254 to 265
















 













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
















 













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
















 













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
















 












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
















 












Example
L1
L2
L3
L4
R





338
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
















 












Example
L1
L2
L3
L4
R





368
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
C6H13


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
















 












Example
L1
L2
L3
L4
R





398
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
















 












Example
L1
L2
L3
L4
R





428
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
















 














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
















 














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
















 














Example
L1
L2
L3
L4
R







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
















 














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
















 














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
















 














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
















 














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
















 














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
















 














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 formula (VII) to (XI)




wherein
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,
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 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, —OCH2F or -(Z-A-)n—R.

2. Cyclopenta[b]naphthalene derivatives according to claim 1, wherein

3. Cyclopenta[b]naphthalene derivatives according to claim 1, wherein A is

4. Cyclopenta[b]naphthalene derivatives according to claim 1, wherein L2 and L3, independently of one another, are identical or different and are hydrogen, halogen, —CN, —SCN, —NCS, —SF5, —CF3, —CHF2, —OCF3 or —OCHF2.

5. Cyclopenta[b]naphthalene derivatives according to claim 1, wherein L1 and L4, independently of one another, are identical or different and are hydrogen or fluorine.

6. Cyclopenta[b]naphthalene derivatives according to at least claim 1, wherein L5 and L6 are hydrogen.

7. Cyclopenta[b]naphthalene derivatives according to claim 1, wherein L1, L2, L3 and L4 are fluorine and L5 and L6 are hydrogen.

8. Cyclopenta[b]naphthalene derivatives of formula (VII) to (XI)




wherein
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,
n is 0, 1, 2 or 3, and
L1-L6 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 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, —OCH2F or -(Z-A-)n—R,
and L7's are F.

9. Cyclopental[b]naphthalene derivatives of formula (VII) to (XI)




wherein
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,
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 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, —OCH2F or -(Z-A-)n—R
wherein at least L8 is F.

10. Cyclopenta (b) napathalene derivatives according to claim 9, wherein both L8 are F.

11. Cyclopenta (b) napathalene derivatives according to claim 1, wherein

12. Cyclopenta (b) napathalene derivatives according to claim 1, wherein

13. Cyclopenta (b) napathalene derivatives according to claim 1, wherein

14. Cyclopenta (b) napathalene derivatives according to claim 1, wherein