# Patent

## Title
Benzochromene derivatives

## Abstract

The present invention relates to benzochromene derivatives of the formula I




in which the various parameters are as defined in the text, and to liquid-crystal media which comprise these compounds, and to the use of the media in electro-optical displays, in particular in VAN LCDs.

## Background
The present invention relates to benzochromene derivatives, preferably mesogenic benzochromene derivatives, in particular liquid-crystalline benzochromene derivatives, and to liquid-crystalline media comprising these benzochromene derivatives. The present invention furthermore relates to liquid-crystal displays, in particular liquid-crystal displays addressed by means of an active matrix (AMDs or AM LCDs (“active matrix addressed liquid crystal displays”)) and very particularly so-called VAN (“vertically aligned nematic”) liquid-crystal displays, an embodiment of ECB (“electrically controlled birefringence”) liquid-crystal displays, in which nematic liquid crystals of negative dielectric anisotropy (Δε) are used.
In liquid-crystal displays of this type, the liquid crystals are used as dielectrics whose optical properties change reversibly on application of an electric voltage. Electro-optical displays which use liquid crystals as media are known to the person skilled in the art. These liquid-crystal displays use various electro-optical effects. The most common of these are the TN (“twisted nematic”) effect, with a homogeneous, virtually planar initial alignment of the liquid-crystal director and a nematic structure twisted by about 90°, the STN (“supertwisted nematic”) effect and the SBE (“super-twisted birefringence effect”) effect, with a nematic structure twisted by 180° or more. In these and similar electro-optical effects, liquid-crystalline media of positive dielectric anisotropy (Δε) are used.
Besides the said electro-optical effects, which require liquid-crystal media of positive dielectric anisotropy, there are other electro-optical effects which use liquid-crystal media of negative dielectric anisotropy, such as, for example, the ECB effect and its sub-forms DAP (“deformation of aligned phases”), VAN and CSH (“colour super homeotropics”).
An electro-optical effect having excellent, low, viewing-angle dependence of the contrast uses axially symmetric micropixels (ASMs). In this effect, the liquid crystal in each pixel is surrounded cylindrically by a polymer material. This mode is particularly suitable for combination with addressing through plasma channels. Thus, in particular, large-area PA (“plasma addressed”) LCDs having good viewing-angle dependence of the contrast can be achieved.
The IPS (“in plane switching”) effect, which has been increasingly employed recently, can use both dielectrically positive and dielectrically negative liquid-crystal media, similar to guest/host displays, which are able to employ dyes either in dielectrically positive or in dielectrically negative media, depending on the display mode used.
Since the operating voltage in liquid-crystal displays in general, i.e. including in displays based on these effects, should be as low as possible, use is made of liquid-crystal media having a large absolute value of the dielectric anisotropy, which generally predominantly and usually even very substantially consist of liquid-crystal compounds having a dielectric anisotropy having the corresponding sign, i.e. consist of compounds of positive dielectric anisotropy in the case of dielectrically positive media and of compounds of negative dielectric anisotropy in the case of dielectrically negative media. In the respective types of media (dielectrically positive or dielectrically negative), at most significant amounts of dielectrically neutral liquid-crystal compounds are typically employed. Liquid-crystal compounds having the sign of the dielectric anisotropy opposite to the dielectric anisotropy of the medium are generally employed in extremely small amounts, or not at all.
An exception here is formed by liquid-crystalline media for MIM (“metal-insulator-metal”) displays (Simmons, J. G., Phys. Rev. 155 No. 3, pp. 657-660 and Niwa, J. G. et al., SID 84 Digest, pp. 304-307, June 1984), in which the liquid-crystal media are addressed by means of an active matrix of thin-film transistors. In this type of addressing, which utilises the non-linear characteristic line of diode switching, it is not possible, in contrast to TFT displays, to charge a storage capacitor together with the electrodes of the liquid-crystal display elements (pixels). A reduction in the effect of voltage drop during the addressing cycle therefore requires the highest possible base value of the dielectric constant. In dielectrically positive media, as employed, for example, in MIM-TN displays, the dielectric constant perpendicular to the molecular axis (ε195) must therefore be as large as possible, since it determines the base capacitance of the pixel. To this end, as described, for example, in WO 93/01253, EP 0 663 502 and DE 195 21 483, compounds of negative dielectric anisotropy are simultaneously employed in addition to dielectrically positive compounds in the dielectrically positive liquid-crystal media.
A further exception is formed by STN displays in which, for example in accordance with DE 41 00 287, dielectrically positive liquid-crystal media comprising dielectrically negative liquid-crystal compounds are employed in order to increase the steepness of the electro-optical characteristic line.
The pixels of the liquid-crystal displays can be addressed directly, time-sequentially, i.e. in time multiplex mode, or by means of a matrix of active elements having nonlinear electric characteristic lines.
The most common AMDs to date use discrete active electronic switching elements, such as, for example, three-pole switching elements, such as MOS (“metal oxide silicon”) transistors or thin-film transistors (TFTs) or varistors or 2-pole switching elements, such as, for example, MIM (“metal insulator metal”) diodes, ring diodes or back-to-back diodes. In TFTs, various semiconductor materials, predominantly silicon, but also cadmium selenide, are used. In particular, amorphous silicon or polycrystalline silicon is used.
In accordance with the present application, preference is given to liquid-crystal displays having an electric field perpendicular to the liquid-crystal layer and liquid-crystal media of negative dielectric anisotropy (Δε<0). In these displays, the edge alignment of the liquid crystals is homeotropic. In the fully switched-through state, i.e. on application of a correspondingly high electric voltage, the liquid-crystal director is aligned parallel to the layer plane.
Cyclic lactones of the formula




    
    
        in which
        —X—Y— is —CO—O— or —O—CO—

are disclosed in JP 2001-026 587 (A). These compounds are characterised by broad smectic phases and are proposed for use in ferroelectric liquid-crystal mixtures in JP 2001-026 587 (A).

    
    


U.S. Pat. No. 5,648,021 discloses fluorinated phenanthrenes of the formula




and fluorinated 9,1 0-dihydrophenanthrenes of the formula





These also have broad smectic phases and are likewise proposed for use in ferroelectric liquid-crystal mixtures.
DE 100 64 995 presents fluorinated phenanthrenes of the formula




    
    
        in which
        L1 and L2 are each, independently of one another, H or F,
    
    


and proposes them for use in nematic liquid-crystal mixtures, in particular for ECB displays. The example compounds in which L1 and L2 are both H and which contain one alkyl end group and one alkoxy end group have an only slightly negative Δε, whereas the example compounds in which L1 and L2 are both F and which contain one alkoxy end group, although having a more negative Δε, generally have greater rotational viscosity, significantly lower solubility and in addition in most cases inadequate UV stability.
It is thus evident that there is both a demand for further mesogenic compounds and also, in particular, a demand for liquid-crystal media of negative dielectric anisotropy having a large absolute value of the dielectric anisotropy, a value of the optical anisotropy (Δn) corresponding to the particular application, a broad nematic phase, good stability to UV, heat and electric voltage and low rotational viscosity.
This is achieved through the use of the mesogenic compounds of the formula I according to the invention




    
    
        in which
        Y is —CO—, —CS—, —CH2—, —CF2— or —CHF—, preferably —CF2—,
        L1 and L2 are each, independently of one another, H, F, Cl or —CN, preferably H or F, preferably at least one of L1 and L2 is F, particularly preferably L1 and L2 are both F,
    
    






    
    
         are each, independently of one another, and, if present more than once, also independently of one another,
        (a) a trans-1,4-cyclohexylene radical, in which, in addition, one or two non-adjacent CH2 groups may be replaced by —O— and/or —S—,
        (b) a 1,4-cyclohexenylene radical,
        (c) a 1,4-phenylene radical, in which, in addition, one or two non-adjacent CH groups may be replaced by N, or
        (d) a radical selected from the group consisting of 1,4-bicyclo-[2.2.2]octylene, 1,3-bicyclo[1.1.1]pentylene, spiro[3.3]-heptane-2,4-diyl, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4-tetrahydro-naphthalene-2,6-diyl,
        preferably
    
    






    
    
        R1 and R2 are each, independently of one another, H, halogen, —CN, —SCN, —SF5, —CF3, —CHF2, —CH2F, —OCF3, —OCHF2, or an alkyl group having from 1 to 15 carbon atoms which is monosubstituted by CN or CF3 or at least monosubstituted by halogen and in which, in addition, one or more CH2 groups may each, independently of one another, be replaced by —O—, —S—, —CH=CH—, —CF=CF—, —CF═CH—, —CH═CF—,
    
    






    
    
         —CO—, —CO—O—, —O—CO— or —O—CO—O— in such a way that neither O nor S atoms are linked directly to one another,
        preferably one of
        R1 and R2 is alkyl or alkoxy having from 1 to 12 carbon atoms, alkoxyalkyl, alkenyl or alkenyloxy having from 2 to 12 carbon atoms and the other, independently of the first, is likewise alkyl or alkoxy having from 1 to 12 carbon atoms, alkoxyalkyl, alkenyl or alkenyloxy having from 2 to 12 carbon atoms or alternatively F, Cl, Br, —CN, —SCN, —SF5, —CF3, —CHF2, —CH2F, —OCF3 or —OCHF2,
        Z1 and Z2 are each, independently of one another, a single bond, —CH2—CH2—, —CF2—CF2—, —CF2—CH2—, —CH2—CF2—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—, —C≡C—, —COO—, —OCO—, —CH2O—, —OCH2—, —CF2O—, —OCF2—, or a combination of two of these groups, where no two O atoms are bonded to one another,
        preferably —(CH2)4—, —CH2—CH2—, —CF2—CF2—, —CH═CH—, —CF═CF—, —C≡C—, —CH2O—, —CF2O— or a single bond,
        particularly preferably —CH2O—, —CH2—CH2—, —CF2—CF2—, —CF═CF—, —CF2O— or a single bond, and
        n and m are each 0, 1 or 2, where
        n+m is 0, 1, 2 or 3, preferably 0, 1 or 2, particularly preferably 0 or 1,
        with the proviso that, if Y is —CO—, at least one of L1 and L2 is not H.
    
    


Particular preference is given to liquid-crystal compounds of the formula I of the sub-formulae 1-1 to 1-3




in which the parameters are as defined above under the formula I, and

    
    
        L1 and L2 are preferably both F.
    
    


Preference is given to compounds of the formula 1, preferably selected from the group consisting of the compounds of the formulae I-1 to I-3, in which
the sum n+m is 0 or 1, preferably 0.
A preferred embodiment is represented by the compounds of the formula I in which the sum n+m is 1 and preferably

    m or n is,






    Z2 is preferably —(CH2)4—, —CH2—CH2—, —CF2—CF2—, —CH═CH—, —CF═CF—, —C≡C—, —O—CH2—, —O—CF2— or a single bond, particularly preferably —O—CH2—, —CH2—CH2—, —CF2—CF2—, —CF═CF—, —O—CF2— or a single bond,


and L1, L2, R1 and R2 are as defined above under the formula I, and L1 and L2 are preferably both F.
Particular preference is given to compounds of the formula I, preferably selected from the group consisting of the compounds of the formulae I-1 to I-3, in which
n and m are both 0, and
L1, L2, R1 and R2 are as defined above under the corresponding formula, and L1 and L2 are preferably both F.
Compounds of the formula I containing branched wing groups R1 and/or R2 may occasionally be of importance owing to better solubility in the usual liquid-crystalline base materials, but in particular as chiral dopants if they are optically active. Smectic compounds of this type are suitable as components of ferroelectric materials. Compounds of the formula I having SA phases are suitable, for example, for thermally addressed displays.
If R1 and/or R2 is an alkyl radical and/or an alkoxy radical, this may be straight-chain or branched. It is preferably straight-chain, has 2, 3, 4, 5, 6 or 7 carbon atoms and accordingly is preferably ethyl, propyl, butyl, pentyl, hexyl, heptyl, ethoxy, propoxy, butoxy, pentoxy, hexyloxy or heptyloxy, furthermore methyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetra-decyl, pentadecyl, methoxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy or tetradecyloxy.
Oxaalkyl or alkoxyalkyl is preferably straight-chain 2-oxapropyl (=methoxy-methyl), 2-(=ethoxymethyl) or 3-oxabutyl (=2-methoxyethyl), 2-, 3- or 4-oxapentyl, 2-, 3-, 4- or 5-oxahexyl, 2-, 3-, 4-, 5- or 6-oxaheptyl, 2-, 3-, 4-, 5-, 6- or 7-oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonyl, or 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-oxadecyl.
If R1 and/or R2 is an alkyl radical in which one CH2 group has been replaced by —CH═CH—, this may be straight-chain or branched. It is preferably straight-chain and has from 2 to 10 carbon atoms. Accordingly, it is in particular vinyl, prop-1- or -2-enyl, but-1-, -2- or -3-enyl, pent-1-, -2-, -3- or -4-enyl, hex-1-, -2-, -3-, -4- or-5-enyl, hept-1-, -2-, -3-, -4-, -5-or -6-enyl, oct-1-, -2-, -3-, -4-, -5-, -6- or -7-enyl, non-1-, -2-, -3-, -4-, -5-, -6-, -7- or -8-enyl, or dec-1-, -2-, -3-, -4-, -5-, -6-, -7-, -8- or -9-enyl.
If R1 and/or R2 is an alkyl radical in which one CH2 group has been replaced by —O— and one has been replaced by —CO—, these are preferably adjacent. These thus contain an acyloxy group —CO—O— or an oxycarbonyl group —O—CO—. These are preferably straight-chain and have from 2 to 6 carbon atoms. Accordingly, they are in particular acetoxy, propionyloxy, butyryloxy, pentanoyloxy, hexanoyloxy, acetoxymethyl, propionyloxymethyl, butyryloxymethyl, pentanoyloxymethyl, 2-acetoxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 3-acetoxypropyl, 3-propionyloxypropyl, 4-acetoxybutyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, butoxyca rbonylmethyl, 2-(methoxyca rbonyl)ethyl, 2-(ethoxycarbonyl)ethyl, 2-(propoxycarbonyl)ethyl, 3-(methoxycarbonyl)propyl, 3-(ethoxycarbonyl)propyl or 4-(methoxycarbonyl)butyl.
If R1 and/or R2 is an alkyl radical 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, this may be straight-chain or branched. It is preferably straight-chain and has from 4 to 13 carbon atoms. Accordingly, it is in particular acryloyloxymethyl, 2-acryl-oyloxyethyl, 3-acryloyloxypropyl, 4-acryloyloxybutyl, 5-acryloyloxypentyl, 6-acryloyloxyhexyl, 7-acryloyloxyheptyl, 8-acryloyloxyoctyl, 9-acryloyloxy-nonyl, 10-acryloyloxydecyl, methacryloyloxymethyl, 2-methacryloyloxyethyl, 3-methacryloyloxypropyl, 4-methacryloyloxybutyl, 5-methacryloyloxypentyl, 6-methacryloyloxyhexyl, 7-methacryloyloxyheptyl, 8-methacryloyloxyoctyl or 9-methacryloyloxynonyl.

    
    
        If R1 and/or R2 is an alkyl or alkenyl radical which is monosubstituted by CN or CF3, this radical is preferably straight-chain. The substitution by CN or CF3 is in any desired position.
    
    


If R1 and/or R2 is an alkyl or alkenyl radical which is at least monosubstituted by halogen, this radical is 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. In the case of monosubstitution, the fluorine or chlorine substituent may be in any desired position, but is preferably in the o-position.
Branched groups generally contain not more than one chain branch. Preferred branched radicals R1 are isopropyl, 2-butyl (=1-methylpropyl), isobutyl (=2-methylpropyl), 2-methylbutyl, isopentyl (=3-methylbutyl), 2-methylpentyl, 3-methylpentyl, 2-ethylhexyl, 2-propylpentyl, isopropoxy, 2-methylpropoxy, 2-methylbutoxy, 3-methylbutoxy, 2-methylpentoxy, 3-methylpentoxy, 2-ethylhexyloxy, 1-methylhexyloxy and 1-methyl-heptyloxy.
If R1 and/or R2 is an alkyl radical in which two or more CH2 groups have been replaced by —O— and/or —CO—O—, this may be straight-chain or branched. It is preferably branched and has from 3 to 12 carbon atoms. Accordingly, it is in particular biscarboxymethyl, 2,2-biscarboxyethyl, 3,3-biscarboxypropyl, 4,4-biscarboxybutyl, 5,5-biscarboxypentyl, 6,6-bis-carboxyhexyl, 7,7-biscarboxyheptyl, 8,8-b isca rboxyoctyl, 9,9-biscarboxy-nonyl, 10,10-biscarboxydecyl, bis(methoxycarbonyl)methyl, 2,2-bis-(methoxycarbonyl)ethyl, 3,3-bis(methoxycarbonyl)propyl, 4,4-bis(methoxy-carbonyl)butyl, 5,5-bis(methoxycarbonyl)pentyl, 6,6-bis(methoxycarbonyl)-hexyl, 7,7-bis(methoxycarbonyl)heptyl, 8,8-bis(methoxycarbonyl)octyl, bis(ethoxycarbonyl)methyl, 2,2-bis(ethoxycarbonyl)ethyl, 3,3-bis(ethoxy-carbonyl)propyl, 4,4-bis(ethoxycarbonyl)butyl or 5,5-bis(ethoxycarbonyl)-hexyl.
Particular preference is given to compounds of the formula I in which n=0 or 1 and m=0 and R1 is methyl, ethyl, propyl, butyl, pentyl, vinyl, 1E-propenyl, 1E-butenyl or 1E-pentenyl, and to media comprising these compounds. Of these compounds, the alkyl-substituted compounds are particularly preferably employed.
The compounds of the formula I are prepared in accordance with the following schemes (Schemes I to XX).
The cyclic lactones can be prepared in accordance with Scheme I by intramolecular cyclisation of aryl phenyl esters which have been halogenated in a suitable manner by coupling reactions of the Ullmann type (Houben Weyl, Methoden der Organischen Chemie [Methods of Organic Chemistry], New York, 1993). They can alternatively be obtained by palladium-catalysed intramolecular cross-coupling reactions as shown in Scheme II and Scheme III.
Alternatively, the cross-coupling can also be carried out in a first step with the correspondingly protected phenols and carboxylic acid esters, as shown in Scheme IIIa using the example of a Negishi reaction (Negishi, E. et al., J. Org. Chem. (1977) 42, pp. 1821-1823).




in which, as in Schemes Ia to Id, II, III, IIIa, IV to XX, unless explicitly stated otherwise,

    R and R′ are each, independently of one another, as defined above for






     under the formula I, and


Hal is halogen, preferably Br or 1.
A: Hasan, I. et al., Chem. Rev. (2002), 102, pp. 1359-1469,
B: Hennings, D. D. et al., Org. Lett. (1999), 1, pp. 1205-1208.
The ester precursors are synthesised by standard reactions (Houben-Weyl) from commercially available 4-bromo-3-fluoro-1-iodobenzene or (in the case where R=methyl from 4-bromo-2-fluorotoluene, or from 4-bromo-2-fluorophenol (ABCR, Karlsruhe, Germany)).
Alkyl side chains are advantageously introduced into the precursors by Sonogashira coupling as shown in Scheme Ia.
Precursors containing alkoxy side chains are advantageously obtained in accordance with Scheme Ib.
The two types of intermediate obtained in accordance with Scheme Ia or Ib can, as shown in Scheme Ic by way of example for the alkyl compounds, be converted either into the phenol or into the carboxylic acid and subsequently esterified.












The bromophenol can be protected and converted into the boronic acid in accordance with Scheme Id for subsequent Suzuki couplings.








C: Bringmann, G. et al., Org. Synth. (2002), 79, pp. 72-83.




D: Alo, B. I. et al., J. Org. Chem. (1991), 56, pp. 3763-3768.
The lactones (Ia) can, as shown in Scheme IV, be converted, analogously to EP 1 061 113, into the benzochromenes (1b) or alternatively, using Lawesson's reagent followed by reaction with DAST, into the difluorobenzochromenes (1c) (Bunelle, W. H. et al., J. Org. Chem. (1990), 55, pp. 768-770).
Alternatively, the lactones (1a) can, in accordance with Scheme V (Ringom, R. and Bennecke, T., Acta. Chem. Scand. (1999), 53, pp. 41-47), be reacted with LiAlH4 in THF and subsequently reacted with DAST to give the fluorobenzochromenes (Id).
The above-mentioned alternative synthesis in which the cross-coupling is carried out in a first step with the correspondingly protected phenols and carboxylic acid esters is shown in Scheme IIIa on p. 16 using the example of a Negishi reaction.




in which

    PG is a protecting group,
    X is halogen, preferably Br,
    X1 and X2, independently of one another, are halogen,
    X1 is preferably Cl, Br or I, particularly preferably Br or I, very particularly preferably Br,
    R′′ is alkyl, preferably methyl, and


R and R′ are each, independently of one another, as defined above for Scheme I.
After removal of the protecting group, the lactones can be obtained, for example, by simple heating in an inert solvent or by treatment with an acid or base.








Compounds of the formula I in which




    
    
        are R1, R2,
    
    






    
    
         in which the
    
    






    
    
         rings may also be heterocyclic rings,

can be obtained in accordance with Schemes VI to XX.

    
    


















4-Bromo-3-fluoro-1-iodobenzene and 4-bromo-2-fluorophenol are likewise suitable as synthetic building blocks for a multiplicity of derivatives which can be converted into the corresponding target compounds analogously to the reaction sequences shown in Schemes I-V.
Cyclohexyl derivatives are obtained, for example, in accordance with Scheme X. Metallation of 4-bromo-3-fluoro-1-iodobenzene using n-butyllithium and addition onto cyclohexanones gives phenylcyclohexanols, from which 4-bromo-2-fluoro-1-cyclohexylbenzene derivatives are obtained after elimination of water and hydrogenation.




Aryl derivatives are obtained, for example, in accordance with Scheme XI. Direct Suzuki coupling of 4-bromo-3-fluoro-1-iodobenzene with the corresponding boronic acids enables the preparation of 1-aryl-4-bromo-2-fluoro derivatives.




Sonogashira coupling of 4-bromo-3-fluoro-1-iodobenzene with phenylacetylenes gives, as shown in Scheme XII, 4-bromo-2-fluorotolans. These can, as shown in Scheme XIII, either be hydrogenated to give ethylene-bridged compounds or converted into diketones by the method of V. O. Rogatchov, V. D. Filimonov, M. S. Yusubov, Synthesis (2001), 7, 1001-1003, from which tetrafluoroethylene-bridged compounds are obtained by reaction with sulfur tetrafluoride.








From 4-bromo-2-fluorophenol, hydroxyl compounds and triflates can be obtained as synthetic building blocks in accordance with Scheme XIV.
4-Bromo-2-fluorophenol is protected here using a suitable protecting group “PG” (for example benzyl); corresponding reaction in accordance with Schemes I to V and subsequent removal of the protecting group (for example by hydrogenation for benzyl as PG) enables the preparation of phenols and from these triflates (trifluoromethanesulfonates, TfO-).




in which, as in Schemes XV to XX,

    G is Y—O or O—Y, and
    Y is as defined above under the formula I.


The phenols obtained in this way can be converted into esters and ethers in accordance with Scheme XV.




    
    
        in which R, as in Schemes XVI to XX, is as defined for R1 under the formula I.
    
    


CF2O-bridged compounds are obtained in accordance with WO 02/48 073 and WO 01/64 667, as shown in Scheme XVI.




Suzuki coupling of the triflates obtained in accordance with Scheme XIV with etheneboronic acids enables the preparation of stilbenes (Scheme XVII).




Difluorostilbenes are accessible analogously by Stille reaction as described by L. Lu, D. J. Burton, Tetrahedron Lett. 1997, 38, 7673-7676, (Scheme XVIII).




Carbonylation of triflates by the method of S. Cacchi, P. G. Ciattini, E. Morera, G. Ortar, Tetrahedron Lett. (1986), 27, 3931-3934 gives carboxylic acid esters (Scheme XIX). After saponification to the corresponding carboxylic acids, reaction thereof with-phenols enables the preparation of, for example, phenyl esters.




The carboxylic acid esters obtained in accordance with Scheme XIX can be converted into difluorobenzyl ethers in accordance with WO 02/480 73 and WO 01/64 667, as shown in Scheme XX.




Examples of structures of preferred compounds of the formula I, in which R and R1 have the respective meaning given for R1 and R2 respectively under the formula I, are given on the following pages.

























































































































The liquid-crystal media according to the invention comprise one or more compounds of the formula I.
In a preferred embodiment, the liquid-crystal media in accordance with the present invention comprise

    a) one or more dielectrically negative compound(s) of the formula I






    
    
        in which
        Y is —CO—, —CS—, —CH2—, —CF2— or —CHF—, preferably —CF2—,
        L1 and L2 are each, independently of one another, H, F, Cl or —CN, preferably H or F, preferably at least one of L1 and L2 is F, particularly preferably L1 and L2 are both F,
    
    






    
    
         are each, independently of one another, and, if present more than once, also independently of one another,
        (a) a trans-1,4-cyclohexylene radical, in which, in addition, one or two non-adjacent CH2 groups may be replaced by —O— and/or —S—,
        (b) a 1,4-cyclohexenylene radical,
        (c) a 1,4-phenylene radical, in which, in addition, one or two non-adjacent CH groups may be replaced by N, or
        (d) a radical selected from the group consisting of 1,4-bicyclo[2.2.2]octylene, 1,3-bicyclo[1.1.1]pentylene, spiro[3.3]heptane-2,4-diyl, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl, preferably
    
    






    
    
        R1 and R2 are each, independently of one another, H, halogen, —CN, —SCN, —SF5, —CF3, —CHF2, —CH2F, —OCF3, —OCHF2, or an alkyl group having from 1 to 15 carbon atoms which is monosubstituted by CN or CF3 or at least monosubstituted by halogen and in which, in addition, one or more CH2 groups may each, independently of one another, be replaced by —O—, —S—, —CH═CH—, —CF═CF—, —CF=CH—, —CH═CF—,
    
    






    
    
         —CO—, —CO—O—, —O—CO— or —O—CO—O— in such a way that neither O nor S atoms are linked directly to one another,
        preferably one of
        R1 and R2 is alkyl or alkoxy having from 1 to 12 carbon atoms, alkoxyalkyl, alkenyl or alkenyloxy having from 2 to 12 carbon atoms and the other, independently of the first, is likewise alkyl or alkoxy having from 1 to 12 carbon atoms, alkoxyalkyl, alkenyl or alkenyloxy having from 2 to 12 carbon atoms or alternatively F, Cl, Br, —CN, —SCN, —SF5, —CF3, —CHF2, —CH2F, —OCF3 or —OCHF2,
        Z1 and Z2 are each, independently of one another, a single bond. —CH2—CH2—, —CF2—CF2—, —CF2—CH2—, —CH2—CF2—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—, —C≡C—, —COO—, —OCO—, —CH2O—, —OCH2—, —CF2O—, —OCF2—, or a combination of two of these groups, where no two O atoms are bonded to one another,
        preferably —(CH2)4—, —CH2—CH2—, —CF2—CF2—, —CH═CH—, —CF═CF—, —C≡C—, —CH2O—, —CF2O— or a single bond,
        particularly preferably —CH2O—, —CH2—CH2—, —CF2—CF2—, —CF═CF—, —CF2O— or a single bond, and
        n and m are each 0, 1 or 2, where
        n+m is 0, 1, 2 or 3, preferably 0, 1 or 2, particularly preferably 0 or 1,
    
    
    b) one or more dielectrically negative compound(s) of the formula II






    
    
        in which
        R21 and R22 are each, independently of one another, as defined above for R1 under the formula I,
        Z21 and Z22 are each, independently of one another, as defined above for Z1 under the formula I,
        at least one of the rings present
    
    






    
    
         preferably
    
    






    
    
         and
    
    






    
    
         is
    
    






    
    
         and the others are each, independently of one another,
    
    






preferably





    
    
        particularly preferably
    
    






    
    
         if present, is
    
    






very particularly preferably one of





    
    
         and, if present,
    
    










    
    
         preferably
    
    






    
    
        L21 and L22 are both C—F or one of the two is N and the other is C—F, preferably both are C—F, and
        I is 0, 1 or 2, preferably 0 or 1;

and optionally

    
    
    c) one or more dielectrically neutral compound(s) of the formula III






    
    
        in which
        R31 and R32 are each, independently of one another, as defined above for R1 under the formula I, and
        Z31, Z32 and Z33 are each, independently of one another, —CH2CH2—, —CH═CH—, —COO— or a single bond,
    
    






    
    
         are each, independently of one another,
    
    






    
    
        o and p, independently of one another, are 0 or 1, but preferably
        R31 and R32 are each, independently of one another, alkyl or alkoxy having 1-5 carbon atoms or alkenyl having 2-5 carbon atoms,
    
    






    
    
         are each, independently of one another,
    
    






    
    
         and very particularly preferably at least two of these rings are
    
    






    
    
         where very particularly preferably two adjacent rings, preferably
    
    






    
    
         are linked directly.
    
    


The liquid-crystal media preferably comprise one or more compounds of the formula I which do not contain a biphenyl unit.
The liquid-crystal media particularly preferably comprise one or more compounds of the formula I

    
    
        in which two adjacent rings, preferably
    
    






    
    
         are linked directly.
    
    


In a preferred embodiment, which may be identical with the embodiments just described, the liquid-crystal media comprise one or more compounds selected from the group consisting of the compounds of the formula I-3.
The liquid-crystal medium preferably comprises one or more compounds selected from the group consisting of the compounds of the formulae II-1 to II-3




in which

R21, R22, Z21, Z22,




and I are each as defined above under the formula II. R21 is preferably alkyl, preferably having 1-5 carbon atoms, R21 is preferably alkyl or alkoxy, preferably each having from 1 to 5 carbon atoms, and Z22 and Z21, if present, are preferably a single bond.

The liquid-crystal medium particularly preferably comprises one or more compounds selected from the group consisting of the compounds of the formulae III-1 to III-3:




in which R31, R32, R31, Z32 





are each as defined above under the formula III.

The liquid-crystal medium especially preferably comprises one or more compounds selected from the group consisting of the compounds of the formulae III-1a to III-1d, III-1e, III-2a to III-2g, III-3a to III-3d and III-4a:




in which n and m are each, independently of one another, from 1 to 5, and o and p are each, independently both thereof and of one another, from 0 to 3,





in which R31 and R32 are each as defined above under the formula III, preferably as defined above under the formula III-1, and the phenyl rings, in particular in the compounds III-2g and III-3c, may optionally be fluorinated, but not in such a way that the compounds are identical with those of the formula II and its sub-formulae. R31 is preferably n-alkyl having from 1 to 5 carbon atoms, particularly preferably having from 1 to 3 carbon atoms, and R32 is preferably n-alkyl or n-alkoxy having from 1 to 5 carbon atoms or alkenyl having from 2 to 5 carbon atoms. Of these, especial preference is given to compounds of the formulae III-1a to III-1d.

Preferred fluorinated compounds of the formulae III-2g and III-3c are the compounds of the formulae III-2g′ and III-3c′




in which R31 and R32 are each as defined above under the formula III, preferably as defined above under the formula III-2g or III-3c.

In the present application, unless expressly stated otherwise, the term compounds is taken to mean both one compound and a plurality of compounds.
The liquid-crystal media according to the invention preferably have nematic phases of in each case from at least −20° C. to 80° C., preferably from −30° C. to 85° C. and very particularly preferably from −40° C. to 100° C. The term “have a nematic phase” here is taken to mean firstly that no smectic phase and no crystallisation are observed at low temperatures at the corresponding temperature and secondly also that no clearing occurs on heating from the nematic phase. The investigation at low temperatures is carried out in a flow viscometer at the corresponding temperature and checked by storage in test cells having a layer thickness corresponding to the electro-optical application for at least 100 hours. The storage stability (tstore (T)) at the corresponding temperature (T) is quoted as the time up to which all three test cells show no change. At high temperatures, the clearing point is measured in capillaries by conventional methods.
Furthermore, the liquid-crystal media according to the invention are characterised by low optical anisotropy values.
The term “alkyl” preferably covers straight-chain and branched alkyl groups having from 1 to 7 carbon atoms, in particular the straight-chain groups methyl, ethyl, propyl, butyl, pentyl, hexyl and heptyl. Groups having from 2 to 5 carbon atoms are generally preferred.
The term “alkenyl” preferably covers straight-chain and branched alkenyl groups having from 2 to 7 carbon atoms, in particular the straight-chain groups. Particularly preferred alkenyl groups are C2- to C7-1 E-alkenyl, C4- to C7-3E-alkenyl, C5- to C7-4-alkenyl, C6- to C7-5-alkenyl and C7-6-alkenyl, in particular C2- to C7-1E-alkenyl, C4- to C7-3E-alkenyl and C5- to C7-4-alkenyl. Examples of further preferred alkenyl groups are vinyl, 1E-propenyl, 1E-butenyl, 1E-pentenyl, 1E-hexenyl, 1E-heptenyl, 3-butenyl, 3E-pentenyl, 3E-hexenyl, 3E-heptenyl, 4-pentenyl, 4Z-hexenyl, 4E-hexenyl, 4Z-heptenyl, 5-hexenyl, 6-heptenyl and the like. Groups having up to 5 carbon atoms are generally preferred.
The term “fluoroalkyl” preferably covers straight-chain groups having a terminal fluorine, i.e. fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluoro-butyl, 5-fluoropentyl, 6-fluorohexyl and 7-fluoroheptyl. However, other positions of the fluorine are not excluded.
The term “oxaalkyl” or “alkoxyalkyl” preferably covers straight-chain radicals of the formula CnH2n+1—O—(CH2)m, in which n and m are each, independently of one another, from 1 to 6. n is preferably 1 and m is preferably from 1 to 6.
Compounds containing a vinyl end group and compounds containing a methyl end group have low rotational viscosity.
In the present application, the term dielectrically positive compounds means compounds having a Δε of >1.5, dielectrically neutral compounds means those in which −1.5≦Δε≦1.5, and dielectrically negative compounds means those having a Δε of <−1.5. The dielectric anisotropy of the compounds is determined here by dissolving 10% of the compounds in a liquid-crystalline host and determining the capacitance of this mixture at 1 kHz in at least one test cell with a layer thickness of about 20 μm having a homeotropic surface alignment and at least one test cell with a layer thickness of about 20 μm having a homogeneous surface alignment. The measurement -voltage is typically from 0.5 V to 1.0 V, but is always less than the capacitive threshold of the respective liquid-crystal mixture.
The host mixture used for determining the applicationally relevant physical parameters is ZLI-4792 from Merck KGaA, Germany. As an exception, the determination of the dielectric anisotropy of dielectrically negative compounds is carried out using ZLI-2857, likewise from Merck KGaA, Germany. The values for the respective compound to be investigated are obtained from the change in the properties, for example the dielectric constants, of the host mixture after addition of the compound to be investigated and extrapolation to 100% of the compound employed.
The concentration employed for the compound to be investigated is 10%. If the solubility of the compound to be investigated is inadequate for this purpose, the concentration employed is, by way of exception, halved, i.e. reduced to 5%, 2.5%, etc., until the concentration is below the solubility limit.
The term threshold voltage usually relates to the optical threshold for 10% relative contrast (V10). In relation to the liquid-crystal mixtures of negative .dielectric anisotropy, however, the term threshold voltage is used in the present application for the capacitive threshold voltage (V0), also known as the Freedericksz threshold, unless explicitly stated otherwise.
All concentrations in this application, unless explicitly stated otherwise, are given in percent by weight and relate to the corresponding mixture as a whole. All physical properties are and have been determined in accordance with “Merck Liquid Crystals, Physical Properties of Liquid Crystals”, status November 1997, Merck KGaA, Germany, and apply to a temperature of 20° C., unless explicitly stated otherwise. An is determined at 589 nm and Δε at 1 kHz.
In the case of the liquid-crystal media of negative dielectric anisotropy, the threshold voltage was determined as the capacitive threshold V0 in cells with a liquid-crystal layer aligned homeotropically by means of lecithin.
The liquid-crystal media according to the invention may, if necessary, also comprise further additives and optionally also chiral dopants in the conventional amounts. The amount of these additives employed is in total from 0% to 10%, based on the amount of the mixture as a whole, preferably from 0.1% to 6%. The concentrations of the individual compounds employed are in each case preferably from 0.1 to 3%. The concentration of these and similar additives is not taken into account when indicating the concentrations and the concentration ranges of the liquid-crystal compounds in the liquid-crystal media.
The compositions consist of a plurality of compounds, preferably from 3 to 30, particularly preferably from 6 to 20 and very particularly preferably from 10 to 16 compounds, which are mixed in a conventional manner. In general, the desired amount of the components used in lesser amount is dissolved in the components making up the principal constituent, advantageously at elevated temperature. If the selected temperature is above the clearing point of the principal constituent, the completion of the dissolution process is particularly easy to observe. However, it is also possible to prepare the liquid-crystal mixtures in other conventional ways, for example using premixes or from a so-called “multibottle” system.
By means of suitable additives, the liquid-crystal phases according to the invention can be modified in such a way that they can be employed in any type of display and in particular of ECB display and IPS display that has been disclosed hitherto.
The examples below serve to illustrate the invention without representing a restriction. In the examples, the melting point T(C,N), the transition from the smectic (S) phase to the nematic (N) phase T(S,N) and the clearing point T(N,I) of a liquid-crystal substance are indicated in degrees Celsius. The various smectic phases are characterised by corresponding suffixes.
The percentages above and below are, unless explicitly stated otherwise, percent by weight, and the physical properties are the values at 20° C., unless explicitly stated otherwise.
All the temperature values indicated in this application are ° C. and all temperature differences are correspondingly differential degrees, unless explicitly stated otherwise.
In the synthesis examples and schemes, the abbreviations have the following meanings:
















BuLi
n-butyllithium,



DAST
diethylaminosulfur trifluoride,



DCC
dicyclohexylcarbodiimide,



DMAP
dimethylaminopyridine,



DMF
N,N-dimethylformamide,



dppf
1,1′-bis(diphenylphosphino)ferrocene,



dppp
1,3-bis(diphenylphosphino)propane,



LDA
lithium diisopropylamide,



MBT
MBT ether, methyl tert-butyl ether and



THF
tetrahydrofuran.










In the present application and in the examples below, the structures of the liquid-crystal compounds are indicated by means of acronyms, the transformation into chemical formulae taking place in accordance with Tables A and B below. All radicals CnH2n+1 and CmH2m+1 are straight-chain alkyl radicals having n and m carbon atoms respectively. The coding in Table B is self-evident. In Table A, only the acronym for the parent structure is indicated. In individual cases, the acronym for the parent structure is followed, separated by a hyphen, by a code for the substituents R1, R2, L1, L2 and L3:















Code for R1, R2, L1, L2, L3
R1
R2
L1
L2
L3







nm
CnH2n+1
CmH2m+1
H
H
H


nOm
CnH2n+1
OCmH2m+1
H
H
H


nO•m
OCnH2n+1
CmH2m+1
H
H
H


nmFF
CnH2n+1
CmH2m+1
F
H
F


nOmFF
CnH2n+1
OCmH2m+1
F
H
F


nO•mFF
OCnH2n+1
CmH2m+1
F
H
F


nO•OmFF
OCnH2n+1
OCmH2m+1
F
H
F


n
CnH2n+1
CN
H
H
H


nN•F
CnH2n+1
CN
F
H
H


nN•F•F
CnH2n+1
CN
F
F
H


nF
CnH2n+1
F
H
H
H


nF•F
CnH2n+1
F
F
H
H


nF•F•F
CnH2n+1
F
F
F
H


nCl
CnH2n+1
Cl
H
H
H


nCl•F
CnH2n+1
Cl
F
H
H


nCl•F•F
CnH2n+1
Cl
F
F
H


nmF
CnH2n+1
CmH2m+1
F
H
H


nCF3
CnH2n+1
CF3
H
H
H


nOCF3
CnH2n+1
OCF3
H
H
H


nOCF3•F
CnH2n+1
OCF3
F
H
H


nOCF3•F•F
CnH2n+1
OCF3
F
F
H


nOCF2
CnH2n+1
OCHF2
H
H
H


nOCF2•F•F
CnH2n+1
OCHF2
F
F
H


nS
CnH2n+1
NCS
H
H
H


rVsN
CrH2r+1—CH═CH—CsH2s—
CN
H
H
H


nEsN
CrH2r+1—O—CsH2s—
CN
H
H
H


nAm
CnH2n+1
COOCmH2m+1
H
H
H


nF•Cl
CnH2n+1
F
Cl
H
H
















TABLE A













 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 






















TABLE B













 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 

















EXAMPLES
The following examples are intended to explain the invention without limiting it. Above and below, percentages are percent by weight. All temperatures are indicated in degrees Celsius. An denotes the optical anisotropy (589 nm, 20° C.), Δε the dielectric anisotropy (1 kHz, 20° C.), H.R. the voltage holding ratio (at 100° C., after 5 minutes in the oven, 1 V). V10, V50 and V90 (the threshold voltage, mid-grey voltage and saturation voltage respectively) and V0 (the capacitive threshold voltage) were each determined at 20° C.
Substance Examples
Example 1
(4,7-Difluoro-8-methyl-3-pentyl-6H-benzo[c]chromen-6-one)
1.1 Preparation of 4-bromo-2-fluoro-1-pentylbenzene




190 g (0.600 mol) of 4-bromo-2-fluoro-1-iodobenzene and 65.3 ml of 1-pentyne were dissolved in a mixture of 900 ml of THF and 1.2 l of triethylamine and cooled to 10° C., and 1.14 g (6 mmol) of copper(I) iodide and 8.42 g (12 mmol) of bis(triphenylphosphine)palladium(II) chloride were added. The batch was stirred overnight at room temperature, water and MTB ether were subsequently added, and the mixture was stirred for a further 5 minutes. The reaction mixture was filtered through Celite® with suction, and the phases were separated. The aqueous phase was extracted twice with MTB ether, and the combined organic phases were washed three times with water, dried over sodium sulfate and evaporated under reduced pressure. The crude product was filtered through silica gel with n-heptane, giving 129 g of 4-bromo-2-fluoro-1-pent-1-ynylbenzene as a yellow liquid. Hydrogenation on palladium/activated carbon (10%) in THF gave 131 g (100%) of 4-bromo-2-fluoro-1-pentylbenzene as a yellow liquid.
1.2 Preparation of 6-bromo-2-fluoro-3-pentylphenol




132 g (0.583 mol) of 4-bromo-2-fluoro-1-pentylbenzene were dissolved in 900 ml of THF, and 295 ml of a 2 molar solution of LDA in THF were added dropwise at −70° C. After 1 hour, 65.9 ml (0.590 mol) of trimethyl borate were added, and the mixture was stirred for a further 1 hour and then acidified at −15° C. using 150 ml of 50 percent acetic acid. The batch was subsequently warmed to 30° C., and 139 ml (1.61 mol) of 35 percent hydrogen peroxide solution were added dropwise. After 1 hour, the mixture was diluted with water, and the organic phase was separated off. The combined organic phases were washed twice with ammonium iron(II) sulfate solution and once with water, dried over sodium sulfate and evaporated under reduced pressure.
Filtration of the crude product through silica gel with n-heptane/1-chlorobutane (3:1) gave 86.0 g (61% of theory) of 6-bromo-2-fluoro-3-pentylphenol as colourless crystals.
1.3 Preparation of 6-bromo-2-fluoro-3-methylbenzoic acid




50 ml (0.385 mol) of 4-bromo-2-fluorotoluene were dissolved in 750 ml of THF, and 231 ml (0.462 mol) of a 2 M solution of LDA in THF were added dropwise at −70° C. After 70 minutes, 37.2 g (0.846 mol) of carbon dioxide were passed in, and the batch was allowed to thaw. After acidification using conc. hydrochloric acid, the solution was extracted with MTB ether, and the combined organic phases were washed with water, dried over sodium sulfate and evaporated under reduced pressure. Crystallisation of the crude product from 1-chlorobutane gave 44.1 g (49%) of 6-bromo-2-fluoro-3-methylbenzoic acid as white crystals.
1.4 Preparation of 6-bromo-2-fluoro-3-pentylphenyl 6-bromo-2-fluoro-3-methylbenzoate




43.2 g (0.165 mol) of 6-bromo-2-fluoro-3-pentylphenol, 40.5 g (0.173 mol) of 6-bromo-2-fluoro-3-methylbenzoic acid and 3.52 g (29 mmol) of 4-(dimethylamino)pyridine were initially introduced in 300 ml of dichloro-methane, and a solution of 35.7 g (0.172 mol) of N,N-dicyclohexyl-carbodiimide in 80 ml of dichloromethane was added. The batch was stirred overnight at room temperature, and 4.16 g (33 mmol) of oxalic acid were subsequently added. After 1 hour, the precipitated solid was filtered off, and the filtrate was evaporated under reduced pressure. The crude product was filtered through silica gel with n-heptane/1-chlorobutane (1:1), giving 72.7 g (91% of theory) of 6-bromo-2-fluoro-3-pentylphenyl 6-bromo-2-fluoro-3-methylbenzoate as a colourless oil.
1.5 Preparation of 4,7-difluoro-8-methyl-3-pentyl-6H-benzo[c]chromen-6-one




56.2 g (118 mmol) of 6-bromo-2-fluoro-3-pentylphenyl 6-bromo-2-fluoro-3-methylbenzoate were dissolved in 650 ml of DMF, and the mixture was refluxed for 48 hours in the presence of 75.1 g (1.18 mmol) of copper powder. The mixture was subsequently diluted with water and extracted with ethyl acetate. The extracts were combined, dried over Na2SO4 and evaporated. The crude product was recrystallised from 1-chlorobutane, giving 9.60 g of the lactone as a colourless solid. This corresponds to a yield of 26%.
The physical properties of the compound are shown in the following table.
Examples 2 to 120 
The following are prepared analogously to Example 1:
















 















Phase







sequence

T*(N,I)/


No.
R1
R2
T/° C.
Δε*
° C.





 2
CH3
CH3
C 237 I




 3
CH3
C2H5


 4
CH3
n-C3H7


 5
CH3
n-C4H9


 1
CH3
n-C5H11
C 104 I
−17.8
22


 6
CH3
n-C6H13


 7
CH3
n-C7H15


 8
CH3
CH3O


 9
CH3
C2H5O


 10
CH3
n-C3H7O


 11
CH3
n-C4H9O


 12
CH3
CH2═CH


 13
CH3
E-CH3—CH═CH


 14
CH3
CH2═CH—O


 15
CH3
CH2═CH—CH2O


 16
C2H5
CH3


 17
C2H5
C2H5


 18
C2H5
n-C3H7


 19
C2H5
n-C4H9


 20
C2H5
n-C5H11


 21
C2H5
n-C6H13


 22
C2H5
n-C7H15


 23
C2H5
CH3O


 24
C2H5
C2H5O


 25
C2H5
n-C3H7O


 26
C2H5
n-C4H9O


 27
C2H5
CH2═CH


 28
C2H5
E-CH3—CH═CH


 29
C2H5
CH2═CH—O


 30
C2H5
CH2═CH—CH2O


 31
n-C3H7
CH3


 32
n-C3H7
C2H5


 33
n-C3H7
n-C3H7


 34
n-C3H7
n-C4H9


 35
n-C3H7
n-C5H11
C 103 I
−19.0
7


 36
n-C3H7
n-C6H13


 37
n-C3H7
n-C7H15


 38
n-C3H7
CH3O


 39
n-C3H7
C2H5O


 40
n-C3H7
n-C3H7O


 41
n-C3H7
n-C4H9O


 42
n-C3H7
CH2═CH


 43
n-C3H7
E-CH3—CH═CH


 44
n-C3H7
CH2═CH—O


 45
n-C3H7
CH2═CH—CH2O


 46
n-C4H9
CH3


 47
n-C4H9
C2H5


 48
n-C4H9
n-C3H7


 49
n-C4H9
n-C4H9


 50
n-C4H9
n-C5H11


 51
n-C4H9
n-C6H13


 52
n-C4H9
n-C7H15


 53
n-C4H9
CH3O


 54
n-C4H9
C2H5O


 55
n-C4H9
n-C3H7O


 56
n-C4H9
n-C4H9O


 57
n-C4H9
CH2═CH


 58
n-C4H9
E-CH3—CH═CH


 59
n-C4H9
CH2═CH—O


 60a
n-C4H9
CH2═CH—CH2O


 60b
n-C5H11
n-C4H9O
C 130 I
−23.5
57


 61
CH3O
CH3


 62
CH3O
C2H5


 63
CH3O
n-C3H7


 64
CH3O
n-C4H9


 65
CH3O
n-C5H11


 66
CH3O
n-C6H13


 67
CH3O
n-C7H15


 68
CH3O
CH3O


 69
CH3O
C2H5O


 70
CH3O
n-C3H7O


 71
CH3O
n-C4H9O


 72
CH3O
CH2═CH


 73
CH3O
E-CH3—CH═CH


 74
CH3O
CH2═CH—O


 75
CH3O
CH2═CH—CH2O


 76
C2H5O
CH3


 77
C2H5O
C2H5


 78
C2H5O
n-C3H7


 79
C2H5O
n-C4H9


 80
C2H5O
n-C5H11
C 137 I


 81
C2H5O
n-C6H13


 82
C2H5O
n-C7H15


 83
C2H5O
CH3O


 84
C2H5O
C2H5O


 85
C2H5O
n-C3H7O


 86
C2H5O
n-C4H9O


 87
C2H5O
CH2═CH


 88
C2H5O
E-CH3—CH═CH


 89
C2H5O
CH2═CH—O


 90
C2H5O
CH2═CH—CH2O


 91
CH2═CH
CH3


 92
CH2═CH
C2H5


 93
CH2═CH
n-C3H7


 94
CH2═CH
n-C4H9


 95
CH2═CH
n-C5H11


 96
CH2═CH
n-C6H13


 97
CH2═CH
n-C7H15


 98
CH2═CH
CH3O


 99
CH2═CH
C2H5O


100
CH2═CH
n-C3H7O


101
CH2═CH
n-C4H9O


102
CH2═CH
CH2═CH


103
CH2═CH
E-CH3—CH═CH


104
CH2═CH
CH2═CH—O


105
CH2═CH
CH2═CH—CH2O


106
CH2═CH—O
CH3


107
CH2═CH—O
C2H5


108
CH2═CH—O
n-C3H7


109
CH2═CH—O
n-C4H9


110
CH2═CH—O
n-C5H11


111
CH2═CH—O
n-C6H13


112
CH2═CH—O
n-C7H15


113
CH2═CH—O
CH3O


114
CH2═CH—O
C2H5O


115
CH2═CH—O
n-C3H7O


116
CH2═CH—O
n-C4H9O


117
CH2═CH—O
CH2═CH


118
CH2═CH—O
E-CH3—CH═CH


119
CH2═CH—O
CH2═CH—O


120
CH2═CH—O
CH2═CH—CH2O





Note:


*values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).






Example 121
(4,7-Difluoro-8-methyl-3-pentyl-6H-benzo[c]chromene)
Preparation of 4,7-difluoro-8-methyl-3-pentyl-6H-benzo[c]chromene




2.00 g (6.33 mmol) of the compound from Example 1 were dissolved in 12 ml of THF. 2.56 ml (23 mmol) of boron trifluoride/THF complex were added to this solution with ice-cooling. 12 ml of diethylene glycol dimethyl ether and, in portions, 0.58 g (15 mmol) of sodium borohydride were then added successively, and the mixture was stirred at room temperature (about 20° C.) for 16 hours. The reaction solution was hydrolysed using ice-water and extracted with MTB ether, and the extracts were combined and dried over Na2SO4 and evaporated. The crude product was recrystallised from n-heptane, giving 1.60 g of colourless crystals of the benzochromene. This corresponds to a yield of 83%.
Examples 122 to 240
The following are prepared analogously to Example 121:
















 















Phase







sequence

T*(N,I)/


No.
R1
R2
T/° C.
Δε*
° C.















122
CH3
CH3
C 110 I
−3.2
27


123
CH3
C2H5


124
CH3
n-C3H7


125
CH3
n-C4H9


121
CH3
n-C5H11
Tg −60 C
−3.1
6





42 I


126
CH3
n-C6H13


127
CH3
n-C7H15


128
CH3
CH3O


129
CH3
C2H5O


130
CH3
n-C3H7O


131
CH3
n-C4H9O


132
CH3
CH2═CH


133
CH3
E-CH3—CH═CH


134
CH3
CH2═CH—O


135
CH3
CH2═CH—CH2O


136
C2H5
CH3


137
C2H5
C2H5


138
C2H5
n-C3H7


139
C2H5
n-C4H9


140
C2H5
n-C5H11


141
C2H5
n-C6H13


142
C2H5
n-C7H15


143
C2H5
CH3O


144
C2H5
C2H5O


145
C2H5
n-C3H7O


146
C2H5
n-C4H9O


147
C2H5
CH2═CH


148
C2H5
E-CH3—CH═CH


149
C2H5
CH2═CH—O


150
C2H5
CH2═CH—CH2O


151
n-C3H7
CH3


152
n-C3H7
C2H5


153
n-C3H7
n-C3H7


154
n-C3H7
n-C4H9


155
n-C3H7
n-C5H11
C 34 I
−2.7


156
n-C3H7
n-C6H13


157
n-C3H7
n-C7H15


158
n-C3H7
CH3O


159
n-C3H7
C2H5O


160
n-C3H7
n-C3H7O


161
n-C3H7
n-C4H9O


162
n-C3H7
CH2═CH


163
n-C3H7
E-CH3—CH═CH


164
n-C3H7
CH2═CH—O


165
n-C3H7
CH2═CH—CH2O


166
n-C4H9
CH3


167
n-C4H9
C2H5


168
n-C4H9
n-C3H7


169
n-C4H9
n-C4H9


170
n-C4H9
n-C5H11


171
n-C4H9
n-C6H13


172
n-C4H9
n-C7H15


173
n-C4H9
CH3O


174
n-C4H9
C2H5O


175
n-C4H9
n-C3H7O


176
n-C4H9
n-C4H9O


177
n-C4H9
CH2═CH


178
n-C4H9
E-CH3—CH═CH


179
n-C4H9
CH2═CH—O


180a
n-C4H9
CH2═CH—CH2O


180b
n-C5H11
n-C4H9O


181
CH3O
CH3


182
CH3O
C2H5


183
CH3O
n-C3H7


184
CH3O
n-C4H9


185
CH3O
n-C5H11


186
CH3O
n-C6H13


187
CH3O
n-C7H15


188
CH3O
CH3O


189
CH3O
C2H5O


190
CH3O
n-C3H7O


191
CH3O
n-C4H9O


192
CH3O
CH2═CH


193
CH3O
E-CH3—CH═CH


194
CH3O
CH2═CH—O


195
CH3O
CH2═CH—CH2O


196
C2H5O
CH3


197
C2H5O
C2H5


198
C2H5O
n-C3H7


199
C2H5O
n-C4H9


200
C2H5O
n-C5H11
Tg −39 C
−6.5
39





55 N





(17.4) I


201
C2H5O
n-C6H13


202
C2H5O
n-C7H15


203
C2H5O
CH3O


204
C2H5O
C2H5O


205
C2H5O
n-C3H7O


206
C2H5O
n-C4H9O


207
C2H5O
CH2═CH


208
C2H5O
E-CH3—CH═CH


209
C2H5O
CH2═CH—O


210a
C2H5O
CH2═CH—CH2O


210b
n-C4H9O
n-C5H11


211
CH2═CH
CH3


212
CH2═CH
C2H5


213
CH2═CH
n-C3H7


214
CH2═CH
n-C4H9


215
CH2═CH
n-C5H11


216
CH2═CH
n-C6H13


217
CH2═CH
n-C7H15


218
CH2═CH
CH3O


219
CH2═CH
C2H5O


220
CH2═CH
n-C3H7O


221
CH2═CH
n-C4H9O


222
CH2═CH
CH2═CH


223
CH2═CH
E-CH3—CH═CH


224
CH2═CH
CH2═CH—O


225
CH2═CH
CH2═CH—CH2O


226
CH2═CH—O
CH3


227
CH2═CH—O
C2H5


228
CH2═CH—O
n-C3H7


229
CH2═CH—O
n-C4H9


230
CH2═CH—O
n-C5H11


231
CH2═CH—O
n-C6H13


232
CH2═CH—O
n-C7H15


233
CH2═CH—O
CH3O


234
CH2═CH—O
C2H5O


235
CH2═CH—O
n-C3H7O


236
CH2═CH—O
n-C4H9O


237
CH2═CH—O
CH2═CH


238
CH2═CH—O
E-CH3—CH═CH


239
CH2═CH—O
CH2═CH—O


240
CH2═CH—O
CH2═CH—CH2O





Note:


*values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).






Example 241
(8-Ethoxy-4,6,6,7-tetrafluoro-3-pentyl-6H-benzo[c]-chromene)
Preparation of 8-ethoxy-4,6,6,7-tetrafluoro-3-pentyl-6H-benzo[c]chromene




4.00 g (11.5 mmol) of the compound from Example 80 and 5.14 g (12.7 mmol) of Lawesson's reagent were dissolved in 60 ml of chlorobenzene, and the mixture was refluxed for 48 hours. The batch was subsequently evaporated and subjected to conventional purification, giving 2.90 g (8.00 mmol) of the corresponding thionolactone as an orange solid. This corresponds to a yield of 69%.
The thionolactone was dissolved in 40 ml of dichloromethane. 2.1 ml (16.1 mmol) of DAST were then added, and the mixture was stirred at about 20° C. for 16 hours and subjected to conventional purification. The crude product was purified via silica gel with a mixture of n-heptane/ethyl acetate (9:1) and recrystallised from ethanol, giving 0.46 9 of the difluorobenzochromene. This corresponds to a yield of 15%.
Examples 242 to 360
The following are prepared analogously to Example 241:
















 














Phase sequence



No.
R1
R2
T/° C.
Δε*





242
CH3
CH3




243
CH3
C2H5


244
CH3
n-C3H7


245
CH3
n-C4H9


246
CH3
n-C5H11


247
CH3
n-C6H13


248
CH3
n-C7H15


249
CH3
CH3O


250
CH3
C2H5O


251
CH3
n-C3H7O


252
CH3
n-C4H9O


253
CH3
CH2═CH


254
CH3
E-CH3—CH═CH


255
CH3
CH2═CH—O


256
CH3
CH2═CH—CH2O


257
C2H5
CH3


258
C2H5
C2H5


259
C2H5
n-C3H7


260
C2H5
n-C4H9


261
C2H5
n-C5H11


262
C2H5
n-C6H13


263
C2H5
n-C7H15


264
C2H5
CH3O


265
C2H5
C2H5O


266
C2H5
n-C3H7O


267
C2H5
n-C4H9O


268
C2H5
CH2═CH


269
C2H5
E-CH3—CH═CH


270
C2H5
CH2═CH—O


271
C2H5
CH2═CH—CH2O


272
n-C3H7
CH3


273
n-C3H7
C2H5


274
n-C3H7
n-C3H7


275
n-C3H7
n-C4H9


276
n-C3H7
n-C5H11
C 53 I
−10.4


277
n-C3H7
n-C6H13


278
n-C3H7
n-C7H15


279
n-C3H7
CH3O


280
n-C3H7
C2H5O


281
n-C3H7
n-C3H7O


282
n-C3H7
n-C4H9O


283
n-C3H7
CH2═CH


284
n-C3H7
E-CH3—CH═CH


285
n-C3H7
CH2═CH—O


286
n-C3H7
CH2═CH—CH2O


287
n-C4H9
CH3


288
n-C4H9
C2H5


289
n-C4H9
n-C3H7


290
n-C4H9
n-C4H9


291
n-C4H9
n-C5H11


292
n-C4H9
n-C6H13


293
n-C4H9
n-C7H15


294
n-C4H9
CH3O


295
n-C4H9
C2H5O


296
n-C4H9
n-C3H7O


297
n-C4H9
n-C4H9O


298
n-C4H9
CH2═CH


299
n-C4H9
E-CH3—CH═CH


300
n-C4H9
CH2═CH—O


301a
n-C4H9
CH2═CH—CH2O


301b
n-C5H11
n-C4H9O


302
CH3O
CH3


303
CH3O
C2H5


304
CH3O
n-C3H7


305
CH3O
n-C4H9


306
CH3O
n-C5H11


307
CH3O
n-C6H13


308
CH3O
n-C7H15


309
CH3O
CH3O


310
CH3O
C2H5O


311
CH3O
n-C3H7O


312
CH3O
n-C4H9O


313
CH3O
CH2═CH


314
CH3O
E-CH3—CH═CH


315
CH3O
CH2═CH—O


316
CH3O
CH2═CH—CH2O


317
C2H5O
CH3


318
C2H5O
C2H5


319
C2H5O
n-C3H7


320
C2H5O
n-C4H9


241
C2H5O
n-C5H11
C 85 I
−15.4


321
C2H5O
n-C6H13


322
C2H5O
n-C7H15


323
C2H5O
CH3O


324
C2H5O
C2H5O


325
C2H5O
n-C3H7O


326
C2H5O
n-C4H9O


327
C2H5O
CH2═CH


328
C2H5O
E-CH3—CH═CH


329
C2H5O
CH2═CH—O


330a
C2H5O
CH2═CH—CH2O


330b
n-C4H9O
n-C5H11


331
CH2═CH
CH3


332
CH2═CH
C2H5


333
CH2═CH
n-C3H7


334
CH2═CH
n-C4H9


335
CH2═CH
n-C5H11


336
CH2═CH
n-C6H13


337
CH2═CH
n-C7H15


338
CH2═CH
CH3O


339
CH2═CH
C2H5O


340
CH2═CH
n-C3H7O


341
CH2═CH
n-C4H9O


342
CH2═CH
CH2═CH


343
CH2═CH
E-CH3—CH═CH


344
CH2═CH
CH2═CH—O


345
CH2═CH
CH2═CH—CH2O


346
CH2═CH—O
CH3


347
CH2═CH—O
C2H5


348
CH2═CH—O
n-C3H7


349
CH2═CH—O
n-C4H9


350
CH2═CH—O
n-C5H11


351
CH2═CH—O
n-C6H13


352
CH2═CH—O
n-C7H15


353
CH2═CH—O
CH3O


354
CH2═CH—O
C2H5O


355
CH2═CH—O
n-C3H7O


356
CH2═CH—O
n-C4H9O


357
CH2═CH—O
CH2═CH


358
CH2═CH—O
E-CH3—CH═CH


359
CH2═CH—O
CH2═CH—O


360
CH2═CH—O
CH2═CH—CH2O





Note:


*values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).






Example 361a
(3-Butoxy-4,6,6,7-tetrafluoro-8-(4-pentylcyclohexyl)-6H-benzo[c]chromene)
361.1 Preparation of 4-bromo-2-fluoro-1-(4-pentylcyclohex-1-enyl)benzene




200 g (0.665 mol) of 1-bromo-3-fluoro-4-iodobenzene were dissolved in 800 ml of tetrahydrofuran, and 440 ml (0.698 mmol) of a 15 percent solution of n-butyllithium in hexane were added dropwise at −70° C. After 30 minutes, a solution of 117 g (0.698 mol) of 4-pentylcyclohexanone in 200 ml of tetrahydrofuran was added, and the batch was left to stirr for 60 minutes, hydrolysed using water and acidified using conc. hydrochloric acid. The organic phase was separated off, washed with water and dried over sodium sulfate, and the solvent was removed under reduced pressure. The crude product was subsequently dissolved in 1.4 l of toluene and, after addition of 6 g of toluenesulfonic acid, heated on a water separator until water of reaction was no longer separated off. The solution was washed with water and evaporated, and the residue was filtered through silica gel with n-heptane, giving 124 g (58%) of 4-bromo-2-fluoro-1-(4-pentylcyclohex-1-enyl)benzene as a yellow oil.
361.2 Preparation of 4-bromo-2-fluoro-1-(4-pentylcyclohexyl)benzene




124 g (0.382 mol) of 4-bromo-2-fluoro-1-(4-pentylcyclohex-1-enyl)benzene were hydrogenated to completion at 5 bar and 50° C. in tetrahydrofuran on platinum/activated carbon catalyst. Filtration and removal of the solvent under reduced pressure gave 114 g (80%) of a mixture of cis- and trans-4-bromo-2-fluoro-1-(4-pentylcyclohexyl)benzene as a yellow oil. For isomerisation, this was dissolved in 200 ml of dichloromethane and added dropwise to a suspension of 12.5 g (95.7 mmol) of aluminium chloride in 220 ml of dichloromethane. After 30 minutes, 300 ml of water were added, and the organic phase was separated off, washed with water and dried over sodium sulfate. The solvent was removed under reduced pressure, and the residue was filtered through silica gel with n-pentane, giving 85.2 g of crude product having a content of trans-4-bromo-2-fluoro-1-(4-pentyl-cyclohexyl)benzene of 52.8% and a content of cis-4-bromo-2-fluoro-1-(4-pentylcyclohexyl)benzene of 9.7% as a yellow liquid, which was employed in the next step without further purification.
361.3 Preparation of trans-6-bromo-2-fluoro-3-(4-pentylcyclohexyl)benzoic acid




85.2 g (0.163 mol) of the crude product from the preceding step were initially introduced in 400 ml of tetrahydrofuran at −70° C., and a solution of lithium diisopropylamide, prepared from 213 ml of 15 percent n-butyllithium in hexane and 46 ml (0.326 mmol) of diisopropylamine in 100 ml of tetrahydrofuran, was added dropwise. After 1 hour, 22.9 g (0.521 mol) of carbon dioxide were passed in. The batch was allowed to thaw, acidified using conc. hydrochloric acid and extracted twice with MTB ether. The combined organic phases were washed with water and dried over sodium sulfate, and the solvent was removed under reduced pressure. Crystallisation from n-heptane gave 17 g (28%) of trans-6-bromo-2-fluoro-3-(4-pentylcyclohexyl)benzoic acid as colourless crystals.
361.4 Preparation of methyl trans-6-bromo-2-fluoro-3-(4-pentylcyclohexyl)-benzoate




17.1 g (46.0 mmol) of trans-6-bromo-2-fluoro-3-(4-pentylcyclohexyl)-benzoic acid were dissolved in 70 ml of acetone, 7.66 g (55.4 mmol) of potassium carbonate and 3.14 ml (50.6 mmol) of methyl iodide were added, and the mixture was refluxed overnight. The batch was filtered, and the solvent was distilled off, giving 18 g (100%) of methyl 6-bromo-2-fluoro-3-(4-pentylcyclohexyl)benzoate as a colourless oil, which was reacted further without further purification.
361.5 Preparation of 1-bromo-4-butoxy-3-fluoro-2-(2-methoxyethoxy-methoxy)benzene




Analogously to Examples 841.1 and 841.4, 4-bromo-2-fluorophenol gave 6-bromo-3-butoxy-2-fluorophenol as a brown oil (80%, 2 steps).
60.4 ml (0.355 mol) of ethyldiisopropylamine were added with ice-cooling to 77.4 g (0.294 mol) of 6-bromo-3-butoxy-2-fluorophenol dissolved in 500 ml of dichloromethane, 40.3 ml (0.355 mol) of 2-methoxyethoxymethyl chloride were added dropwise, and the mixture was left to stirr overnight at room temperature. The batch was hydrolysed using water, extracted with dichloromethane and evaporated, and the crude product was filtered through silica gel with n-heptane/MTB ether (3:1), giving 103 g (99%) of 1-bromo-4-butoxy-3-fluoro-2-(2-methoxyethoxymethoxy)benzene as a yellow oil.
361.6 Preparation of 3-butoxy-4,7-difluoro-8-(4-pentylcyclohexyl)-benzo[c]chromen-6-one




16.4 g (0.046 mol) of 1-bromo-4-butoxy-3-fluoro-2-(2-methoxyethoxy-methoxy)benzene were dissolved in 20 ml of tetrahydrofuran, and 31.6 ml (0.052 mol) of a 15 percent solution of n-butyllithium in hexane were added at −70° C. After addition of a solution of 5.94 g (0.027 mol) of zinc bromide in 30 ml of tetrahydrofuran, the batch was allowed to thaw, and the resultant solution was added at the boiling point to a mixture of 18 g (0.046 mol) of methyl 6-bromo-2-fluoro-3-(4-pentylcyclohexyl)benzoate and 730 mg (1.00 mmol) of Pd(dppf)2Cl2 in 60 ml of tetrahydrofuran. The batch was refluxed for 4 hours, stirred overnight at room temperature, acidified using dilute hydrochloric acid and extracted with MTB ether. The combined organic phases were washed with water, dried over sodium sulfate and evaporated. The crude product was chromatographed over silica gel with n-pentane/MTB ether (3:1), giving 14.6 g (55%) of methyl 4′-butoxy-3,3′-difluoro-2′-(2-methoxyethoxymethoxy)-4-(4-pentylcyclohexyl)-biphenyl-2-carboxylate as a yellow oil. This was dissolved in 56 ml of tetrahydrofuran, 11 ml of conc. hydrochloric acid were added, and the mixture was stirred overnight at room temperature. The precipitated product was filtered off with suction, washed with ethyl acetate and dried, giving 7.6 g (68%) of 3-butoxy-4,7-difluoro-8-(4-pentylcyclohexyl)-benzo[c]chromen-6-one as colourless crystals.
361.7 Preparation of 3-butoxy-4,7-difluoro-8-(4-pentylcyclohexyl)-benzo[c]chromene-6-thione




11.7 g (25.6 mmol) of 3-butoxy-4,7-difluoro-8-(4-pentylcyclohexyl)-benzo[c]chromen-6-one and 11.4 g (28.2 mmol) of Lawesson's reagent were refluxed for 16 hours in 130 ml of chlorobenzene. The solution was subsequently filtered through silica gel and evaporated, and the crude product was purified by crystallisation from MTB ether, giving 7.9 g (65%) of 3-butoxy-4,7-difluoro-8-(4-pentylcyclohexyl)benzo[c]chromene-6-thione as yellow crystals.
361.8 Preparation of 3-butoxy-4,6,6,7-tetrafluoro-8-(4-pentylcyclohexyl)-6H-benzo[c]chromene




2.00 g (4.18 mmol) of 3-butoxy-4,7-difluoro-8-(4-pentylcyclohexyl)benzo-[c]chromene-6-thione were dissolved in 20 ml of dichloromethane and cooled to −70° C., 0.55 ml (20 mmol) of a 65 percent solution of hydrogen fluoride in pyridine was added, and a suspension of 2.56 g (8.36 mmol) of 1,3-dibromo-5,5-dimethylhydantoin in 12 ml of dichloromethane was added in portions. After 2 hours, the batch was allowed to thaw, and was neutralised using sat. sodium hydrogencarbonate solution and extracted with dichloromethane. The organic phases were washed with water, dried over sodium sulfate and evaporated, and the crude product was chromatographed over silica gel with heptane/toluene (1:2). Crystallisation from n-heptane gave 1.0 g (52%) of 3-butoxy-4,6,6,7-tetrafluoro-8-(4-pentylcyclohexyl)-6H-benzo[c]chromene as colourless crystals of melting point 99° C.
The compound exhibited the following phase behaviour: C 99° C. N 130.5° C. I and has an extrapolated clearing point of 148° C., and at 20° C. an extrapolated birefringence of 0.153 and an extrapolated dielectric anisotropy of −16.7.
Examples 361b and 362 to 390
The following are prepared analogously to Example 241 and Example 361a:
















 















Phase sequence

T*(N,I)/


No.
R1
R2
T/° C.
Δε*
° C.





361b
CH3
CH3





362
CH3
C2H5


363
CH3
n-C3H7


364
C2H5
CH3


365
C2H5
C2H5


366
C2H5
n-C3H7


367
n-C3H7
CH3


368
n-C3H7
C2H5


369
n-C3H7
n-C3H7


370
n-C3H7
n-C5H11


371
n-C5H11
n-C3H7


372
n-C5H11
n-C5H11


373
CH2═CH
CH3


374
CH2═CH
C2H5


375
CH2═CH
n-C3H7


376
CH2═CH
CH2═CH


377
CH3
CH2═CH


378
C2H5
CH2═CH


379
n-C3H7
CH2═CH


380
E-CH3—CH═CH
CH2═CH


381
E-CH3—CH═CH
E-CH3—CH═CH


382
CH3
CH3O


383
CH3
C2H5O


384
CH3
n-C3H7O


385
n-C3H7
CH3O


386
n-C3H7
C2H5O


387
n-C3H7
n-C3H7O


361a
n-C5H11
n-C4H9O
C 99 N 130.5 I
−16.7
148


388a
n-C4H9O
n-C5H11


388b
CH3O
CH3O


389
C2H5O
C2H5O


390
n-C3H7O
n-C3H7O





Note:


*values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).






Examples 391 to 420
The following are prepared analogously to Example 241 and Example 361a:
















 














Phase sequence



No.
R1
R2
T/° C.
Δε*





391
CH3
CH3




392
CH3
C2H5


393
CH3
n-C3H7


394
C2H5
CH3


395
C2H5
C2H5


396
C2H5
n-C3H7


397
n-C3H7
CH3


398
n-C3H7
C2H5


399
n-C3H7
n-C3H7


400
n-C3H7
n-C5H11


401
n-C5H11
n-C3H7


402
n-C5H11
n-C5H11


403
CH2═CH
CH3


404
CH2═CH
C2H5


405
CH2═CH
n-C3H7


406
CH2═CH
CH2═CH


407
CH3
CH2═CH


408
C2H5
CH2═CH


409
n-C3H7
CH2═CH


410
E-CH3—CH═CH
CH2═CH


411
E-CH3—CH═CH
E-CH3—CH═CH


412
CH3
CH3O


413
CH3
C2H5O


414
CH3
n-C3H7O


415
n-C3H7
CH3O


416
n-C3H7
C2H5O


417a
n-C3H7
n-C3H7O


417b
n-C5H11
n-C4H9O


417c
n-C4H9O
n-C5H11


418
CH3O
CH3O


419
C2H5O
C2H5O


420
n-C3H7O
n-C3H7O





Note:


*values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).






Examples 421 to 450 
The following are prepared analogously to Example 241 and Example 361a:
















 














Phase sequence



No.
R1
R2
T/° C.
Δε*





421
CH3
CH3




422
CH3
C2H5


423
CH3
n-C3H7


424
C2H5
CH3


425
C2H5
C2H5


426
C2H5
n-C3H7


427
n-C3H7
CH3


428
n-C3H7
C2H5


429
n-C3H7
n-C3H7


430
n-C3H7
n-C5H11


431
n-C5H11
n-C3H7


432
n-C5H11
n-C5H11


453
CH2═CH
CH3


434
CH2═CH
C2H5


435
CH2═CH
n-C3H7


436
CH2═CH
CH2═CH


437
CH3
CH2═CH


438
C2H5
CH2═CH


439
n-C3H7
CH2═CH


440
E-CH3—CH═CH
CH2═CH


441
E-CH3—CH═CH
E-CH3—CH═CH


442
CH3
CH3O


443
CH3
C2H5O


444
CH3
n-C3H7O


445
n-C3H7
CH3O


446
n-C3H7
C2H5O


447a
n-C3H7
n-C3H7O


447b
n-C5H11
n-C4H9O


447c
n-C4H9O
n-C5H11


448
CH3O
CH3O


449
C2H5O
C2H5O


450
n-C3H7O
n-C3H7O





Note:


*values extrapolated from 10% solution in ZLI-4792.






Examples 451 to 480
The following are prepared analogously to Example 241 and Example 361a:
















 














Phase sequence



No.
R1
R2
T/° C.
Δε*





451
CH3
CH3




452
CH3
C2H5


453
CH3
n-C3H7


454
C2H5
CH3


455
C2H5
C2H5


456
C2H5
n-C3H7


457
n-C3H7
CH3


458
n-C3H7
C2H5


459
n-C3H7
n-C3H7


460
n-C3H7
n-C5H11


461
n-C5H11
n-C3H7


462
n-C5H11
n-C5H11


463
CH2═CH
CH3


464
CH2═CH
C2H5


465
CH2═CH
n-C3H7


466
CH2═CH
CH2═CH


467
CH3
CH2═CH


468
C2H5
CH2═CH


469
n-C3H7
CH2═CH


470
E-CH3—CH═CH
CH2═CH


471
E-CH3—CH═CH
E-CH3—CH═CH


472
CH3
CH3O


473
CH3
C2H5O


474
CH3
n-C3H7O


475
n-C3H7
CH3O


476
n-C3H7
C2H5O


477a
n-C3H7
n-C3H7O


477b
n-C5H11
n-C4H9O


477c
n-C4H9O
n-C5H11


478
CH3O
CH3O


479
C2H5O
C2H5O


480
n-C3H7O
n-C3H7O





Note:


*values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).






Examples 481 to 510
The following are prepared analogously to Example 241 and Example 361a:
















 














Phase sequence



No.
R1
R2
T/° C.
Δε*





481
CH3
CH3




482
CH3
C2H5


483
CH3
n-C3H7


484
C2H5
CH3


485
C2H5
C2H5


486
C2H5
n-C3H7


487
n-C3H7
CH3


488
n-C3H7
C2H5


489
n-C3H7
n-C3H7


490
n-C3H7
n-C5H11


491
n-C5H11
n-C3H7


492
n-C5H11
n-C5H11


493
CH2═CH
CH3


494
CH2═CH
C2H5


495
CH2═CH
n-C3H7


496
CH2═CH
CH2═CH


497
CH3
CH2═CH


498
C2H5
CH2═CH


499
n-C3H7
CH2═CH


500
E-CH3—CH═CH
CH2═CH


501
E-CH3—CH═CH
E-CH3—CH═CH


502
CH3
CH3O


503
CH3
C2H5O


504
CH3
n-C3H7O


505
n-C3H7
CH3O


506
n-C3H7
C2H5O


507a
n-C3H7
n-C3H7O


507b
n-C5H11
n-C4H9O


507c
n-C4H9O
n-C5H11


508
CH3O
CH3O


509
C2H5O
C2H5O


510
n-C3H7O
n-C3H7O





Note:


*values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).






Examples 511 to 540
The following are prepared analogously to Example 241 and Example 361a:
















 














Phase sequence



No.
R1
R2
T/° C.
Δε*





511
CH3
CH3




512
CH3
C2H5


513
CH3
n-C3H7


514
C2H5
CH3


515
C2H5
C2H5


516
C2H5
n-C3H7


517
n-C3H7
CH3


518
n-C3H7
C2H5


519
n-C3H7
n-C3H7


520
n-C3H7
n-C5H11


521
n-C5H11
n-C3H7


522
n-C5H11
n-C5H11


523
CH2═CH
CH3


524
CH2═CH
C2H5


525
CH2═CH
n-C3H7


526
CH2═CH
CH2═CH


527
CH3
CH2═CH


528
C2H5
CH2═CH


529
n-C3H7
CH2═CH


530
E-CH3—CH═CH
CH2═CH


531
E-CH3—CH═CH
E-CH3—CH═CH


532
CH3
CH3O


533
CH3
C2H5O


534
CH3
n-C3H7O


535
n-C3H7
CH3O


536
n-C3H7
C2H5O


537a
n-C3H7
n-C3H7O


537b
n-C5H11
n-C4H9O


537c
n-C4H9O
n-C5H11


538
CH3O
CH3O


539
C2H5O
C2H5O


540
n-C3H7O
n-C3H7O





Note:


*values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).






Examples 541 to 570
The following are prepared analogously to Example 241 and Example 361a:
















 














Phase sequence



No.
R1
R2
T/° C.
Δε*





541
CH3
CH3




542
CH3
C2H5


543
CH3
n-C3H7


544
C2H5
CH3


545
C2H5
C2H5


546
C2H5
n-C3H7


547
n-C3H7
CH3


548
n-C3H7
C2H5


549
n-C3H7
n-C3H7


550
n-C3H7
n-C5H11


551
n-C5H11
n-C3H7


552
n-C5H11
n-C5H11


553
CH2═CH
CH3


554
CH2═CH
C2H5


555
CH2═CH
n-C3H7


556
CH2═CH
CH2═CH


557
CH3
CH2═CH


558
C2H5
CH2═CH


559
n-C3H7
CH2═CH


560
E-CH3—CH═CH
CH2═CH


561
E-CH3—CH═CH
E-CH3—CH═CH


562
CH3
CH3O


563
CH3
C2H5O


564
CH3
n-C3H7O


565
n-C3H7
CH3O


566
n-C3H7
C2H5O


567a
n-C3H7
n-C3H7O


567b
n-C5H11
n-C4H9O


567c
n-C4H9O
n-C5H11


568
CH3O
CH3O


569
C2H5O
C2H5O


570
n-C3H7O
n-C3H7O





Note:


*values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).






Examples 571 to 600
The following are prepared analogously to Example 241 and Example 361a:
















 














Phase sequence



No.
R1
R2
T/° C.
Δε*





571
CH3
CH3




572
CH3
C2H5


573
CH3
n-C3H7


574
C2H5
CH3


575
C2H5
C2H5


576
C2H5
n-C3H7


577
n-C3H7
CH3


578
n-C3H7
C2H5


579
n-C3H7
n-C3H7


580
n-C3H7
n-C5H11


581
n-C5H11
n-C3H7


582
n-C5H11
n-C5H11


583
CH2═CH
CH3


584
CH2═CH
C2H5


585
CH2═CH
n-C3H7


586
CH2═CH
CH2═CH


587
CH3
CH2═CH


588
C2H5
CH2═CH


589
n-C3H7
CH2═CH


590
E-CH3—CH═CH
CH2═CH


591
E-CH3—CH═CH
E-CH3—CH═CH


592
CH3
CH3O


593
CH3
C2H5O


594
CH3
n-C3H7O


595
n-C3H7
CH3O


596
n-C3H7
C2H5O


597a
n-C3H7
n-C3H7O


597b
n-C5H11
n-C4H9O


597c
n-C4H9O
n-C5H11


598
CH3O
CH3O


599
C2H5O
C2H5O


600
n-C3H7O
n-C3H7O





Note:


*values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).






Examples 601 to 630
The following are prepared analogously to Example 241 and Example 361a:
















 














Phase sequence



No.
R1
R2
T/° C.
Δε*





601
CH3
CH3




602
CH3
C2H5


603
CH3
n-C3H7


604
C2H5
CH3


605
C2H5
C2H5


606
C2H5
n-C3H7


607
n-C3H7
CH3


608
n-C3H7
C2H5


609
n-C3H7
n-C3H7


610
n-C3H7
n-C5H11


611
n-C5H11
n-C3H7


612
n-C5H11
n-C5H11


613
CH2═CH
CH3


614
CH2═CH
C2H5


615
CH2═CH
n-C3H7


616
CH2═CH
CH2═CH


617
CH3
CH2═CH


618
C2H5
CH2═CH


619
n-C3H7
CH2═CH


620
E-CH3—CH═CH
CH2═CH


621
E-CH3—CH═CH
E-CH3—CH═CH


622
CH3
CH3O


623
CH3
C2H5O


624
CH3
n-C3H7O


625
n-C3H7
CH3O


626
n-C3H7
C2H5O


627a
n-C3H7
n-C3H7O


627b
n-C5H11
n-C4H9O


527c
n-C4H9O
n-C5H11


628
CH3O
CH3O


629
C2H5O
C2H5O


630
n-C3H7O
n-C3H7O





Note:


*values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).






Examples 631 to 660
The following are prepared analogously to Example 241 and Example 361a:
















 














Phase






sequence


No.
R1
R2
T/° C.
Δε*





631
CH3
CH3




632
CH3
C2H5


633
CH3
n-C3H7


634
C2H5
CH3


635
C2H5
C2H5


636
C2H5
n-C3H7


637
n-C3H7
CH3


638
n-C3H7
C2H5


639
n-C3H7
n-C3H7


640
n-C3H7
n-C5H11


641
n-C5H11
n-C3H7


642
n-C5H11
n-C5H11


643
CH2═CH
CH3


644
CH2═CH
C2H5


645
CH2═CH
n-C3H7


646
CH2═CH
CH2═CH


677
CH3
CH2═CH


648
C2H5
CH2═CH


649
n-C3H7
CH2═CH


650
E-CH3—CH═CH
CH2═CH


651
E-CH3—CH═CH
E-CH3—CH═CH


652
CH3
CH3O


653
CH3
C2H5O


654
CH3
n-C3H7O


655
n-C3H7
CH3O


656
n-C3H7
C2H5O


657a
n-C3H7
n-C3H7O


657b
n-C5H11
n-C4H9O


5617c
n-C4H9O
n-C5H11


658
CH3O
CH3O


659
C2H5O
C2H5O


660
n-C3H7O
n-C3H7O





Note:


*values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).






Examples 661 to 690
The following are prepared analogously to Example 241 and Example 361a:
















 














Phase sequence



No.
R1
R2
T/° C.
Δε*





661
CH3
CH3




662
CH3
C2H5


663
CH3
n-C3H7


664
C2H5
CH3


665
C2H5
C2H5


666
C2H5
n-C3H7


667
n-C3H7
CH3


668
n-C3H7
C2H5


669
n-C3H7
n-C3H7


670
n-C3H7
n-C5H11


671
n-C5H11
n-C3H7


672
n-C5H11
n-C5H11


673
CH2═CH
CH3


674
CH2═CH
C2H5


675
CH2═CH
n-C3H7


676
CH2═CH
CH2═CH


677
CH3
CH2═CH


678
C2H5
CH2═CH


679
n-C3H7
CH2═CH


680
E-CH3—CH═CH
CH2═CH


681
E-CH3—CH═CH
E-CH3—CH═CH


682
CH3
CH3O


683
CH3
C2H5O


684
CH3
n-C3H7O


685
n-C3H7
CH3O


686
n-C3H7
C2H5O


687a
n-C3H7
n-C3H7O


687b
n-C5H11
n-C4H9O


687c
n-C4H9O
n-C5H11


688
CH3O
CH3O


689
C2H5O
C2H5O


690
n-C3H7O
n-C3H7O





Note:


*values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).






Examples 691 to 720
The following are prepared analogously to Example 241 and Example 361a:
















 














Phase sequence



No.
R1
R2
T/° C.
Δε*





691
CH3
CH3




692
CH3
C2H5


693
CH3
n-C3H7


694
C2H5
CH3


695
C2H5
C2H5


696
C2H5
n-C3H7


697
n-C3H7
CH3


698
n-C3H7
C2H5


699
n-C3H7
n-C3H7


700
n-C3H7
n-C5H11


701
n-C5H11
n-C3H7


702
n-C5H11
n-C5H11


703
CH2═CH
CH3


704
CH2═CH
C2H5


705
CH2═CH
n-C3H7


706
CH2═CH
CH2═CH


707
CH3
CH2═CH


708
C2H5
CH2═CH


709
n-C3H7
CH2═CH


710
E-CH3—CH═CH
CH2═CH


711
E-CH3—CH═CH
E-CH3—CH═CH


712
CH3
CH3O


713
CH3
C2H5O


714
CH3
n-C3H7O


715
n-C3H7
CH3O


716
n-C3H7
C2H5O


717a
n-C3H7
n-C3H7O


717b
n-C5H11
n-C4H9O


717c
n-C4H9O
n-C5H11


718
CH3O
CH3O


719
C2H5O
C2H5O


720
n-C3H7O
n-C3H7O





Note:


*values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).






Examples 721 to 750
The following are prepared analogously to Example 241 and Example 361a:
















 














Phase sequence



No.
R1
R2
T/° C.
Δε*





721
CH3
CH3




722
CH3
C2H5


723
CH3
n-C3H7


724
C2H5
CH3


725
C2H5
C2H5


726
C2H5
n-C3H7


727
n-C3H7
CH3


728
n-C3H7
C2H5


729
n-C3H7
n-C3H7


730
n-C3H7
n-C5H11


731
n-C5H11
n-C3H7


732
n-C5H11
n-C5H11


733
CH2═CH
CH3


734
CH2═CH
C2H5


735
CH2═CH
n-C3H7


736
CH2═CH
CH2═CH


737
CH3
CH2═CH


738
C2H5
CH2═CH


739
n-C3H7
CH2═CH


740
E-CH3—CH═CH
CH2═CH


741
E-CH3—CH═CH
E-CH3—CH═CH


742
CH3
CH3O


743
CH3
C2H5O


744
CH3
n-C3H7O


745
n-C3H7
CH3O


746
n-C3H7
C2H5O


747a
n-C3H7
n-C3H7O


747b
n-C5H11
n-C4H9O


747c
n-C4H9O
n-C5H11


748
CH3O
CH3O


749
C2H5O
C2H5O


750
n-C3H7O
n-C3H7O





Note:


*values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).






Examples 751 to 780
The following are prepared analogously to Example 241 and Example 361a:
















 














Phase sequence



No.
R1
R2
T/° C.
Δε*





751
CH3
CH3




752
CH3
C2H5


753
CH3
n-C3H7


754
C2H5
CH3


755
C2H5
C2H5


756
C2H5
n-C3H7


757
n-C3H7
CH3


758
n-C3H7
C2H5


759
n-C3H7
n-C3H7


760
n-C3H7
n-C5H11


761
n-C5H11
n-C3H7


762
n-C5H11
n-C5H11


763
CH2═CH
CH3


764
CH2═CH
C2H5


765
CH2═CH
n-C3H7


766
CH2═CH
CH2═CH


767
CH3
CH2═CH


768
C2H5
CH2═CH


769
n-C3H7
CH2═CH


770
E-CH3—CH═CH
CH2═CH


771
E-CH3—CH═CH
E-CH3—CH═CH


772
CH3
CH3O


773
CH3
C2H5O


774
CH3
n-C3H7O


775
n-C3H7
CH3O


776
n-C3H7
C2H5O


777a
n-C3H7
n-C3H7O


777b
n-C5H11
n-C4H9O


777c
n-C4H9O
n-C5H11


778
CH3O
CH3O


779
C2H5O
C2H5O


780
n-C3H7O
n-C3H7O





Note:


*values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).






Examples 781 to 810
The following are prepared analogously to Example 241 and Example 361a:
















 














Phase sequence



No.
R1
R2
T/° C.
Δε*





781
CH3
CH3




782
CH3
C2H5


783
CH3
n-C3H7


784
C2H5
CH3


785
C2H5
C2H5


786
C2H5
n-C3H7


787
n-C3H7
CH3


788
n-C3H7
C2H5


789
n-C3H7
n-C3H7


790
n-C3H7
n-C5H11


791
n-C5H11
n-C3H7


792
n-C5H11
n-C5H11


793
CH2═CH
CH3


794
CH2═CH
C2H5


795
CH2═CH
n-C3H7


796
CH2═CH
CH2═CH


797
CH3
CH2═CH


798
C2H5
CH2═CH


799
n-C3H7
CH2═CH


800
E-CH3—CH═CH
CH2═CH


801
E-CH3—CH═CH
E-CH3—CH═CH


802
CH3
CH3O


803
CH3
C2H5O


804
CH3
n-C3H7O


805
n-C3H7
CH3O


806
n-C3H7
C2H5O


807a
n-C3H7
n-C3H7O


807b
n-C5H11
n-C4H9O


807c
n-C4H9O
n-C5H11


808
CH3O
CH3O


809
C2H5O
C2H5O


810
n-C3H7O
n-C3H7O





Note:


*values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).






Examples 811 to 840
The following are prepared analogously to Example 241 and Example 361a:
















 














Phase sequence



No.
R1
R2
T/° C.
Δε*





811
CH3
CH3




812
CH3
C2H5


813
CH3
n-C3H7


814
C2H5
CH3


815
C2H5
C2H5


816
C2H5
n-C3H7


817
n-C3H7
CH3


818
n-C3H7
C2H5


819
n-C3H7
n-C3H7


820
n-C3H7
n-C5H11


821
n-C5H11
n-C3H7


822
n-C5H11
n-C5H11


823
CH2═CH
CH3


824
CH2═CH
C2H5


825
CH2═CH
n-C3H7


826
CH2═CH
CH2═CH


827
CH3
CH2═CH


828
C2H5
CH2═CH


829
n-C3H7
CH2═CH


830
E-CH3—CH═CH
CH2═CH


831
E-CH3—CH═CH
E-CH3—CH═CH


832
CH3
CH3O


833
CH3
C2H5O


834
CH3
n-C3H7O


835
n-C3H7
CH3O


836
n-C3H7
C2H5O


837a
n-C3H7
n-C3H7O


837b
n-C5H11
n-C4H9O


837c
n-C4H9O
n-C5H11


838
CH3O
CH3O


839
C2H5O
C2H5O


840
n-C3H7O
n-C3H7O





Note:


*values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).






Example 841
(8-Ethoxy-4,7-difluoro-3-benzyloxybenzo[c]chromen-6-one)
841.1 Preparation of 4-bromo-1-ethoxy-2-fluorobenzene




100 g (0.524 mol) of 4-bromo-2-fluorophenol and 66.7 g (0.612 mol) of ethyl bromide were dissolved in 2 1 of ethyl methyl ketone and refluxed for 24 hours in the presence of 185 g (1.34 mol) of potassium carbonate. The solution was subsequently filtered, the filtrate was evaporated, and the crude product was filtered through silica gel with n-hexane, giving 114 g (99% of theory) of 4-bromo-1-ethoxy-2-fluorobenzene as a colourless liquid.
841.2 Preparation of 6-bromo-3-ethoxy-2-fluorobenzoic acid




Analogously to the synthesis described above (under Example 1.3), 236 g of 4-bromo-1-ethoxy-2-fluorobenzene gave 190 g (64% of theory) of 6-bromo-3-ethoxy-2-fluorobenzoic acid as colourless crystals.
841.3 Preparation of 1-benzyloxy-4-bromo-2-fluorobenzene




Analogously to the synthesis described above (under Example 2.1 or 872.1), 250 g (1.31 mol) of 4-bromo-2-fluorophenol and 179 ml (1.51 mol) of benzyl bromide gave 366 g (97%) of 1-benzyloxy-4-bromo-2-fluorobenzene as colourless crystals.
841.4 Preparation of 3-benzyloxy-6-bromo-2-fluorophenol




Analogously to the synthesis described above (under Example 1.2), 366 g (1.27 mol) of 1-benzyloxy-4-bromo-2-fluorobenzene give 270 g (72% of theory) of 3-benzyloxy-6-bromo-2-fluorophenol as colourless crystals.
841.5 Preparation of 3-benzyloxy-6-bromo-2-fluorophenyl 6-bromo-3-ethoxy-2-fluorobenzoate




Analogously to the synthesis described above (under Example 1.4), 253 g (0.851 mol) of 3-benzyloxy-6-bromo-2-fluorophenol and 246 g (0.936 mol) of 6-bromo-3-ethoky-2-fluorobenzoic acid give 405 g (87% of theory) of 3-benzyloxy-6-bromo-2-fluorophenyl 6-bromo-3-ethoxy-2-fluorobenzoate as colourless crystals.
841.6 Preparation of 8-ethoxy-4,7-difluoro-3-benzyloxybenzo[c]chromen-6-one




103 g (0.188 mol) of 3-benzyloxy-6-bromo-2-fluorophenyl 6-bromo-3-ethoxy-2-fluorobenzoate were dissolved in 1 l of DMF and refluxed for 72 hours in the presence of 119 g (1.88 mol) of copper powder. The batch was subsequently diluted with water and extracted with ethyl acetate, and the combined extracts were dried over sodium sulfate and evaporated. Crystallisation of the crude product from THF gave 15 g (21% of theory) of 8-ethoxy-4,7-difluoro-3-benzyloxybenzo[c]chromen-6-one as pale-yellow crystals.
Examples 842 to 881
The following are prepared analogously to Example 841:
















 















Phase sequence

T*(N,I)/


No.
R1
R2
T/° C.
Δε*
° C.





842
CH3
CH3





843
CH3
C2H5


844
CH3
n-C3H7


845
C2H5
CH3


846
C2H5
C2H5


847
C2H5
n-C3H7


848
n-C3H7
CH3


849
n-C3H7
C2H5


850
n-C3H7
n-C3H7


851
n-C3H7
n-C5H11


852
n-C5H11
n-C3H7


853
n-C5H11
n-C5H11


854
CH2═CH
CH3


855
CH2═CH
C2H5


856
CH2═CH
n-C3H7


857
CH2═CH
CH2═CH


858
CH3
CH2═CH


859
C2H5
CH2═CH


860
n-C3H7
CH2═CH


861
E-CH3—CH═CH
CH2═CH


862
E-CH3—CH═CH
E-CH3—CH═CH


863
CH3
CH3O


864
CH3
C2H5O


865
CH3
n-C3H7O


866
n-C3H7
CH3O


867
n-C3H7
C2H5O


868a
n-C3H7
n-C3H7O


868b
n-C5H11
n-C4H9O


868c
n-C4H9O
n-C5H11


869
CH3O
CH3O


841
C2H5O
H


870
C2H5O
C2H5O


871
n-C3H7O
n-C3H7O





Note:


*values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).






Example 872
(8-Ethoxy-4,7-difluoro-3-(trans-4-vinylcyclohexylmethoxy)-6H-benzo[c]chromene)
872.1 Preparation of 8-ethoxy-4,7-difluoro-3-hydroxy-6H-benzo[c]chromene




2.00 g (5.24 mmol) of 3-benzyloxy-8-ethoxy-4,7-difluoro-6H-benzo[c]chromen-6-one, the compound of Example 841, were dissolved in 12 ml of THF, and 2.37 ml (23.0 mmol) of boron trifluoride/THF complex were added with ice-cooling. 24 ml of ethylene glycol dimethyl ether and then in portions 530 mg of sodium borohydride were subsequently added. The mixture was subsequently stirred at room temperature for 18 hours and then transferred onto ice. The mixture was subjected to conventional purification, giving 1.5 g (78% of theory) of 3-benzyloxy-8-ethoxy-4,7-difluoro-6H-benzo[c]chromene as colourless crystals. These were dissolved in THF, hydrogenated at a pressure of 1 bar in the presence of 0.6 g of Pd/C (5%), filtered and evaporated, giving 1.2 g (99% of theory) of 8-ethoxy-4,7-difluoro-3-hydroxy-6H-benzo[c]chromene as colourless crystals.
872.2 Preparation of 8-ethoxy-4,7-difluoro-3-(trans-4-vinylcyclohexyl-methoxy)-6H-benzo[c]chromene




1.2 g (4.32 mmol) of 8-ethoxy4,7-difluoro-3-hydroxy-6H-benzo[c]-chromene, 2.16 g (8.64 mmol) of (trans-4-vinylcyclohexyl)methyl iodide and 650 mg (5 mmol) of potassium carbonate were refluxed for 16 hours in 15 ml of acetone. The mixture was then -transferred into MTB ether and subjected to conventional purification, giving 460. mg (27% of theory) of 8-ethoxy-4,7-difluoro-3-(trans-4-vinylcyclohexylmethoxy)-6 H-benzo[c]-chromene as colourless crystals.
Examples 873-902
The following are prepared analogously to Example 872:





























Phase sequence

T*(N,I)/


No.
R1
R2
T/° C.
Δε*
° C.





873
CH3
CH3





874
CH3
C2H5


875
CH3
n-C3H7


876
C2H5
CH3


877
C2H5
C2H5


878
C2H5
n-C3H7


879
n-C3H7
CH3


880
n-C3H7
C2H5


881
n-C3H7
n-C3H7


882
n-C3H7
n-C5H11


883
n-C5H11
n-C3H7


884
n-C5H11
n-C5H11


885
CH2═CH
CH3


886
CH2═CH
C2H5


887
CH2═CH
n-C3H7


872
CH2═CH
C2H5O
C 123 N 167 I
−10.4
207


888
CH2═CH
CH2═CH


889
CH3
CH2═CH


890
C2H5
CH2═CH


891
n-C3H7
CH2═CH


892
E-CH3—CH═CH
CH2═CH


893
E-CH3—CH═CH
E-CH3—CH═CH


894
CH3
CH3O


895
CH3
C2H5O


896
CH3
n-C3H7O


897
n-C3H7
CH3O


898
n-C3H7
C2H5O


899a
n-C3H7
n-C3H7O


899b
n-C5H11
n-C4H9O
C 109 SA 157 N
−11.2
199





167.5 I


899c
n-C4H9O
n-C5H11


900
CH3O
CH3O


901
C2H5O
C2H5O


902
n-C3H7O
n-C3H7O





Note:


*values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).






Examples 903 to 934
The following are prepared analogously to Example 241 and Example 361a:
















 














Phase sequence



No.
R1
R2
T/° C.
Δε*





903
CH3
CH3




904
CH3
C2H5


905
CH3
n-C3H7


906
C2H5
CH3


907
C2H5
C2H5


908
C2H5
n-C3H7


909
n-C3H7
CH3


910
n-C3H7
C2H5


911
n-C3H7
n-C3H7


912
n-C3H7
n-C5H11


913
n-C5H11
n-C3H7


914
n-C5H11
n-C5H11


915
CH2═CH
CH3


916
CH2═CH
C2H5


917
CH2═CH
n-C3H7


918
CH2═CH
CH2═CH


919
CH3
CH2═CH


920
C2H5
CH2═CH


921
n-C3H7
CH2═CH


922
E-CH3—CH═CH
CH2═CH


923
E-CH3—CH═CH
E-CH3—CH═CH


924
CH3
CH3O


925
CH3
C2H5O


926
CH3
n-C3H7O


927
n-C3H7
CH3O


928
n-C3H7
C2H5O


929
n-C3H7
n-C3H7O


930
n-C5H11
n-C4H9O


931
n-C4H9O
n-C5H11


932
CH3O
CH3O


933
C2H5O
C2H5O


934
n-C3H7O
n-C3H7O





Note:


*values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).






Examples 935 to 966
The following are prepared analogously to Example 241 and Example 361a:
















 














Phase sequence



No.
R1
R2
T/° C.
Δε*





935
CH3
CH3




936
CH3
C2H5


937
CH3
n-C3H7


938
C2H5
CH3


939
C2H5
C2H5


940
C2H5
n-C3H7


941
n-C3H7
CH3


942
n-C3H7
C2H5


943
n-C3H7
n-C3H7


944
n-C3H7
n-C5H11


945
n-C5H11
n-C3H7


946
n-C5H11
n-C5H11


947
CH2═CH
CH3


948
CH2═CH
C2H5


949
CH2═CH
n-C3H7


950
CH2═CH
CH2═CH


951
CH3
CH2═CH


952
C2H5
CH2═CH


953
n-C3H7
CH2═CH


954
E-CH3—CH═CH
CH2═CH


955
E-CH3—CH═CH
E-CH3—CH═CH


956
CH3
CH3O


957
CH3
C2H5O


958
CH3
n-C3H7O


959
n-C3H7
CH3O


960
n-C3H7
C2H5O


961
n-C3H7
n-C3H7O


962
n-C5H11
n-C4H9O


963
n-C4H9O
n-C5H11


964
CH3O
CH3O


965
C2H5O
C2H5O


966
n-C3H7O
n-C3H7O





Note:


*values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).






Examples 967 to 998
The following are prepared analogously to Example 241 and Example 361a:
















 














Phase sequence



No.
R1
R2
T/° C.
Δε*





967
CH3
CH3




968
CH3
C2H5


969
CH3
n-C3H7


970
C2H5
CH3


971
C2H5
C2H5


972
C2H5
n-C3H7


973
n-C3H7
CH3


974
n-C3H7
C2H5


975
n-C3H7
n-C3H7


976
n-C3H7
n-C5H11


977
n-C5H11
n-C3H7


978
n-C5H11
n-C5H11


979
CH2═CH
CH3


980
CH2═CH
C2H5


981
CH2═CH
n-C3H7


982
CH2═CH
CH2═CH


983
CH3
CH2═CH


984
C2H5
CH2═CH


985
n-C3H7
CH2═CH


986
E-CH3—CH═CH
CH2═CH


987
E-CH3—CH═CH
E-CH3—CH═CH


988
CH3
CH3O


989
CH3
C2H5O


990
CH3
n-C3H7O


991
n-C3H7
CH3O


992
n-C3H7
C2H5O


993
n-C3H7
n-C3H7O


994
n-C5H11
n-C4H9O


995
n-C4H9O
n-C5H11


996
CH3O
CH3O


997
C2H5O
C2H5O


998
n-C3H7O
n-C3H7O





Note:


*values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).






Examples 999 to 1030
The following are prepared analogously to Example 241 and Example 361a:
















 














Phase sequence



No.
R1
R2
T/° C.
Δε*





 999
CH3
CH3




1000
CH3
C2H5


1001
CH3
n-C3H7


1002
C2H5
CH3


1003
C2H5
C2H5


1004
C2H5
n-C3H7


1005
n-C3H7
CH3


1006
n-C3H7
C2H5


1007
n-C3H7
n-C3H7


1008
n-C3H7
n-C5H11


1009
n-C5H11
n-C3H7


1010
n-C5H11
n-C5H11


1011
CH2═CH
CH3


1012
CH2═CH
C2H5


1013
CH2═CH
n-C3H7


1014
CH2═CH
CH2═CH


1015
CH3
CH2═CH


1016
C2H5
CH2═CH


1017
n-C3H7
CH2═CH


1018
E-CH3—CH═CH
CH2═CH


1019
E-CH3—CH═CH
E-CH3—CH═CH


1020
CH3
CH3O


1021
CH3
C2H5O


1022
CH3
n-C3H7O


1023
n-C3H7
CH3O


1024
n-C3H7
C2H5O


1025
n-C3H7
n-C3H7O


1026
n-C5H11
n-C4H9O
C 187 SA 230





N 230.4 I


1027
n-C4H9O
n-C5H11


1028
CH3O
CH3O


1029
C2H5O
C2H5O


1030
n-C3H7O
n-C3H7O





Note:


*values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).






Examples 1031 to 1062
The following are prepared analogously to Example 241 and Example 361a:
















 














Phase sequence



No.
R1
R2
T/° C.
Δε*





1031
CH3
CH3




1032
CH3
C2H5


1033
CH3
n-C3H7


1034
C2H5
CH3


1035
C2H5
C2H5


1036
C2H5
n-C3H7


1037
n-C3H7
CH3


1038
n-C3H7
C2H5


1039
n-C3H7
n-C3H7


1040
n-C3H7
n-C5H11


1041
n-C5H11
n-C3H7


1042
n-C5H11
n-C5H11


1043
CH2═CH
CH3


1044
CH2═CH
C2H5


1045
CH2═CH
n-C3H7


1046
CH2═CH
CH2═CH


1047
CH3
CH2═CH


1048
C2H5
CH2═CH


1049
n-C3H7
CH2═CH


1050
E-CH3—CH═CH
CH2═CH


1051
E-CH3—CH═CH
E-CH3—CH═CH


1052
CH3
CH3O


1053
CH3
C2H5O


1054
CH3
n-C3H7O


1055
n-C3H7
CH3O


1056
n-C3H7
C2H5O


1057
n-C3H7
n-C3H7O


1058
n-C5H11
n-C5H11O
C 151 SB 188





SA 191 I


1059
n-C4H9O
n-C5H11


1060
CH3O
CH3O


1061
C2H5O
C2H5O


1062
n-C3H7O
n-C3H7O





Note:


*values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).






Examples 1063 to 1093
The following are prepared analogously to Example 241 and Example 361a:
















 














Phase sequence



No.
R1
R2
T/° C.
Δε*





1063
CH3
CH3




1064
CH3
C2H5


1065
CH3
n-C3H7


1066
C2H5
CH3


1067
C2H5
C2H5


1068
C2H5
n-C3H7


1069
n-C3H7
CH3


1070
n-C3H7
C2H5


1071
n-C3H7
n-C3H7


1072
n-C3H7
n-C5H11


1073
n-C5H11
n-C3H7


1074
n-C5H11
n-C5H11


1075
CH2═CH
CH3


1076
CH2═CH
C2H5


1077
CH2═CH
n-C3H7


1078
CH2═CH
CH2═CH


1079
CH3
CH2═CH


1080
C2H5
CH2═CH


1081
n-C3H7
CH2═CH


1082
E-CH3—CH═CH
CH2═CH


1083
E-CH3—CH═CH
E-CH3—CH═CH


1084
CH3
CH3O


1085
CH3
C2H5O


1086
CH3
n-C3H7O


1087
n-C3H7
CH3O


1088
n-C3H7
C2H5O


1089
n-C3H7
n-C3H7O


1090
n-C4H9O
n-C5H11


1091
CH3O
CH3O


1092
C2H5O
C2H5O


1093
n-C3H7O
n-C3H7O





Note:


*values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).






Examples 1094 to 1125
The following are prepared analogously to Example 241 and Example 361a:
















 














Phase sequence



No.
R1
R2
T/° C.
Δε*





1094
CH3
CH3




1095
CH3
C2H5


1096
CH3
n-C3H7


1097
C2H5
CH3


1098
C2H5
C2H5


1099
C2H5
n-C3H7


1100
n-C3H7
CH3


1101
n-C3H7
C2H5


1102
n-C3H7
n-C3H7


1103
n-C3H7
n-C5H11


1104
n-C5H11
n-C3H7


1105
n-C5H11
n-C5H11


1106
CH2═CH
CH3


1107
CH2═CH
C2H5


1108
CH2═CH
n-C3H7


1109
CH2═CH
CH2═CH


1110
CH3
CH2═CH


1111
C2H5
CH2═CH


1112
n-C3H7
CH2═CH


1113
E-CH3—CH═CH
CH2═CH


1114
E-CH3—CH═CH
E-CH3—CH═CH


1115
CH3
CH3O


1116
CH3
C2H5O


1117
CH3
n-C3H7O


1118
n-C3H7
CH3O


1119
n-C3H7
C2H5O


1120
n-C3H7
n-C3H7O


1121
n-C5H11
n-C4H9O


1122
n-C4H9O
n-C5H11


1123
CH3O
CH3O


1124
C2H5O
C2H5O


1125
n-C3H7O
n-C3H7O





Note:


*values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).






Examples 1126 to 1157
The following are prepared analogously to Example 241 and Example 361a:




























Phase sequence



No.
R1
R2
T/° C.
Δε*





1126
CH3
CH3




1127
CH3
C2H5


1128
CH3
n-C3H7


1129
C2H5
CH3


1130
C2H5
C2H5


1131
C2H5
n-C3H7


1132
n-C3H7
CH3


1133
n-C3H7
C2H5


1134
n-C3H7
n-C3H7


1135
n-C3H7
n-C5H11


1136
n-C5H11
n-C3H7


1137
n-C5H11
n-C5H11


1138
CH2═CH
CH3


1139
CH2═CH
C2H5


1140
CH2═CH
n-C3H7


1141
CH2═CH
CH2═CH


1142
CH3
CH2═CH


1143
C2H5
CH2═CH


1144
n-C3H7
CH2═CH


1145
E-CH3—CH═CH
CH2═CH


1146
E-CH3—CH═CH
E-CH3—CH═CH


1147
CH3
CH3O


1148
CH3
C2H5O


1149
CH3
n-C3H7O


1150
n-C3H7
CH3O


1151
n-C3H7
C2H5O


1152
n-C3H7
n-C3H7O


1153
n-C5H11
n-C4H9O


1154
n-C4H9O
n-C5H11


1155
CH3O
CH3O


1156
C2H5O
C2H5O


1157
n-C3H7O
n-C3H7O





Note:


*values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).






Examples 1158 to 1190
The following are prepared analogously to Example 241 and Example 361a:
















 














Phase sequence



No.
R1
R2
T/° C.
Δε*





1158
CH3
CH3




1159
CH3
C2H5


1160
CH3
n-C3H7


1161
C2H5
CH3


1162
C2H5
C2H5


1163
C2H5
n-C3H7


1154
n-C3H7
CH3


1165
n-C3H7
C2H5


1166
n-C3H7
n-C3H7


1167
n-C3H7
n-C5H11


1168
n-C5H11
n-C3H7


1159
n-C5H11
n-C5H11


1170
CH2═CH
CH3


1171
CH2═CH
C2H5


1172
CH2═CH
n-C3H7


1173
CH2═CH
CH2═CH


1174
CH3
CH2═CH


1175
C2H5
CH2═CH


1176
n-C3H7
CH2═CH


1177
E-CH3—CH═CH
CH2═CH


1178
E-CH3—CH═CH
E-CH3—CH═CH


1179
CH3
CH3O


1180
CH3
C2H5O


1181
CH3
n-C3H7O


1182
n-C3H7
CH3O


1183
n-C3H7
C2H5O


1184
n-C3H7
n-C3H7O


1185
n-C5H11
n-C4H9O


1186
n-C4H9O
n-C5H11


1187
CH3O
CH3O


1188
C2H5O
C2H5O


1190
n-C3H7O
n-C3H7O





Note:


*values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).






Examples 1191 to 1222
The following are prepared analogously to Example 241 and Example 361a:
















 














Phase sequence



No.
R1
R2
T/° C.
Δε*





1191
CH3
CH3




1192
CH3
C2H5


1193
CH3
n-C3H7


1194
C2H5
CH3


1195
C2H5
C2H5


1196
C2H5
n-C3H7


1197
n-C3H7
CH3


1198
n-C3H7
C2H5


1199
n-C3H7
n-C3H7


1200
n-C3H7
n-C5H11


1201
n-C5H11
n-C3H7


1202
n-C5H11
n-C5H11


1203
CH2═CH
CH3


1204
CH2═CH
C2H5


1205
CH2═CH
n-C3H7


1206
CH2═CH
CH2═CH


1207
CH3
CH2═CH


1208
C2H5
CH2═CH


1209
n-C3H7
CH2═CH


1200
E-CH3—CH═CH
CH2═CH


1211
E-CH3—CH═CH
E-CH3—CH═CH


1212
CH3
CH3O


1213
CH3
C2H5O


1214
CH3
n-C3H7O


1215
n-C3H7
CH3O


1216
n-C3H7
C2H5O


1217
n-C3H7
n-C3H7O


1218
n-C5H11
n-C4H9O


1219
n-C4H9O
n-C5H11


1220
CH3O
CH3O


1221
C2H5O
C2H5O


1222
n-C3H7O
n-C3H7O





Note:


*values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).






Examples 1223 to 1254 
The following are prepared analogously to Example 241 and Example 361a:
















 














Phase sequence



No.
R1
R2
T/° C.
Δε*





1223
CH3
CH3




1224
CH3
C2H5


1225
CH3
n-C3H7


1226
C2H5
CH3


1227
C2H5
C2H5


1228
C2H5
n-C3H7


1229
n-C3H7
CH3


1230
n-C3H7
C2H5


1231
n-C3H7
n-C3H7


1232
n-C3H7
n-C5H11


1233
n-C5H11
n-C3H7


1234
n-C5H11
n-C5H11


1235
CH2═CH
CH3


1236
CH2═CH
C2H5


1237
CH2═CH
n-C3H7


1238
CH2═CH
CH2═CH


1239
CH3
CH2═CH


1240
C2H5
CH2═CH


1241
n-C3H7
CH2═CH


1242
E-CH3—CH═CH
CH2═CH


1243
E-CH3—CH═CH
E-CH3—CH═CH


1244
CH3
CH3O


1245
CH3
C2H5O


1246
CH3
n-C3H7O


1247
n-C3H7
CH3O


1248
n-C3H7
C2H5O


1249
n-C3H7
n-C3H7O


1250
n-C5H11
n-C4H9O


1251
n-C4H9O
n-C5H11


1252
CH3O
CH3O


1253
C2H5O
C2H5O


1254
n-C3H7O
n-C3H7O





Note:


*values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).






Examples 1255 to 1286
The following are prepared analogously to Example 241 and Example 361a:
















 














Phase sequence



No.
R1
R2
T/° C.
Δε*





1255
CH3
CH3




1256
CH3
C2H5


1257
CH3
n-C3H7


1258
C2H5
CH3


1259
C2H5
C2H5


1260
C2H5
n-C3H7


1261
n-C3H7
CH3


1262
n-C3H7
C2H5


1263
n-C3H7
n-C3H7


1264
n-C3H7
n-C5H11


1265
n-C5H11
n-C3H7


1266
n-C5H11
n-C5H11


1267
CH2═CH
CH3


1268
CH2═CH
C2H5


1269
CH2═CH
n-C3H7


1270
CH2═CH
CH2═CH


1271
CH3
CH2═CH


1272
C2H5
CH2═CH


1273
n-C3H7
CH2═CH


1274
E-CH3—CH═CH
CH2═CH


1275
E-CH3—CH═CH
E-CH3—CH═CH


1276
CH3
CH3O


1277
CH3
C2H5O


1278
CH3
n-C3H7O


1279
n-C3H7
CH3O


1280
n-C3H7
C2H5O


1281
n-C3H7
n-C3H7O


1252
n-C5H11
n-C4H9O


1283
n-C4H9O
n-C5H11


1284
CH3O
CH3O


1285
C2H5O
C2H5O


1286
n-C3H7O
n-C3H7O





Note:


*values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).






Examples 1287 to 1318
The following are prepared analogously to Example 241 and Example 361a:
















 














Phase sequence



No.
R1
R2
T/° C.
Δε*





1287
CH3
CH3




1288
CH3
C2H5


1289
CH3
n-C3H7


1290
C2H5
CH3


1291
C2H5
C2H5


1292
C2H5
n-C3H7


1293
n-C3H7
CH3


1294
n-C3H7
C2H5


1295
n-C3H7
n-C3H7


1296
n-C3H7
n-C5H11


1297
n-C5H11
n-C3H7


1298
n-C5H11
n-C5H11


1299
CH2═CH
CH3


1300
CH2═CH
C2H5


1301
CH2═CH
n-C3H7


1302
CH2═CH
CH2═CH


1303
CH3
CH2═CH


1304
C2H5
CH2═CH


1305
n-C3H7
CH2═CH


1306
E-CH3—CH═CH
CH2═CH


1307
E-CH3—CH═CH
E-CH3—CH═CH


1308
CH3
CH3O


1309
CH3
C2H5O


1310
CH3
n-C3H7O


1311
n-C3H7
CH3O


1312
n-C3H7
C2H5O


1313
n-C3H7
n-C3H7O


1314
n-C5H11
n-C4H9O


1315
n-C4H9O
n-C5H11


1316
CH3O
CH3O


1317
C2H5O
C2H5O


1318
n-C3H7O
n-C3H7O





Note:


*values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).






Examples 1319 to 1350
The following are prepared analogously to Example 241 and Example 361a:
















 














Phase sequence



No.
R1
R2
T/° C.
Δε*





1319
CH3
CH3




1320
CH3
C2H5


1321
CH3
n-C3H7


1322
C2H5
CH3


1323
C2H5
C2H5


1324
C2H5
n-C3H7


1325
n-C3H7
CH3


1326
n-C3H7
C2H5


1327
n-C3H7
n-C3H7


1328
n-C3H7
n-C5H11


1329
n-C5H11
n-C3H7


1330
n-C5H11
n-C5H11


1331
CH2═CH
CH3


1332
CH2═CH
C2H5


1333
CH2═CH
n-C3H7


1334
CH2═CH
CH2═CH


1335
CH3
CH2═CH


1336
C2H5
CH2═CH


1337
n-C3H7
CH2═CH


1338
E-CH3—CH═CH
CH2═CH


1339
E-CH3—CH═CH
E-CH3—CH═CH


1340
CH3
CH3O


1341
CH3
C2H5O


1342
CH3
n-C3H7O


1343
n-C3H7
CH3O


1344
n-C3H7
C2H5O


1345
n-C3H7
n-C3H7O


1346
n-C5H11
n-C4H9O
C 112 SA 149 I
−8.1


1347
n-C4H9O
n-C5H11


1348
CH3O
CH3O


1349
C2H5O
C2H5O


1350
n-C3H7O
n-C3H7O





Note:


*values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).






Examples 1351 to 1382
The following are prepared analogously to Example 241 and Example 361a:
















 














Phase sequence



No.
R1
R2
T/° C.
Δε*





1351
CH3
CH3




1352
CH3
C2H5


1353
CH3
n-C3H7


1354
C2H5
CH3


1355
C2H5
C2H5


1356
C2H5
n-C3H7


1357
n-C3H7
CH3


1358
n-C3H7
C2H5


1359
n-C3H7
n-C3H7


1360
n-C3H7
n-C5H11


1361
n-C5H11
n-C3H7


1362
n-C5H11
n-C5H11


1363
CH2═CH
CH3


1364
CH2═CH
C2H5


1365
CH2═CH
n-C3H7


1366
CH2═CH
CH2═CH


1367
CH3
CH2═CH


1368
C2H5
CH2═CH


1369
n-C3H7
CH2═CH


1370
E-CH3—CH═CH
CH2═CH


1371
E-CH3—CH═CH
E-CH3—CH═CH


1372
CH3
CH3O


1373
CH3
C2H5O


1374
CH3
n-C3H7O


1375
n-C3H7
CH3O


1376
n-C3H7
C2H5O


1377
n-C3H7
n-C3H7O


1378
n-C5H11
n-C4H9O


1379
n-C4H9O
n-C5H11


1380
CH3O
CH3O


1381
C2H5O
C2H5O


1382
n-C3H7O
n-C3H7O





Note:


*values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).






Examples 1383 to 1385
The following are prepared analogously to Example 241 and Example 361a:
















 














Phase sequence



No.
R1
R2
T/° C.
Δε*





1383
CH3
CH3




1384
CH3
C2H5


1385
CH3
n-C3H7


1386
C2H5
CH3


1387
C2H5
C2H5


1388
C2H5
n-C3H7


1389
n-C3H7
CH3


1390
n-C3H7
C2H5


1391
n-C3H7
n-C3H7


1392
n-C3H7
n-C5H11


1393
n-C5H11
n-C3H7


1394
n-C5H11
n-C5H11


1395
CH2═CH
CH3


1396
CH2═CH
C2H5


1397
CH2═CH
n-C3H7


1398
CH2═CH
CH2═CH


1399
CH3
CH2═CH


1400
C2H5
CH2═CH


1401
n-C3H7
CH2═CH


1402
E-CH3—CH═CH
CH2═CH


1403
E-CH3—CH═CH
E-CH3—CH═CH


1404
CH3
CH3O


1405
CH3
C2H5O


1406
CH3
n-C3H7O


1407
n-C3H7
CH3O


1408
n-C3H7
C2H5O


1409
n-C3H7
n-C3H7O


1410
n-C5H11
n-C4H9O


1411
n-C4H9O
n-C5H11


1412
CH3O
CH3O


1413
C2H5O
C2H5O


1414
n-C3H7O
n-C3H7O





Note:


*values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).






Examples 1415 to 1446
The following are prepared analogously to Example 241 and Example 361a:
















 














Phase sequence



No.
R1
R2
T/° C.
Δε*





1415
CH3
CH3




1416
CH3
C2H5


1417
CH3
n-C3H7


1418
C2H5
CH3


1419
C2H5
C2H5


1420
C2H5
n-C3H7


1421
n-C3H7
CH3


1422
n-C3H7
C2H5


1423
n-C3H7
n-C3H7


1424
n-C3H7
n-C5H11


1425
n-C5H11
n-C3H7


1426
n-C5H11
n-C5H11


1427
CH2═CH
CH3


1428
CH2═CH
C2H5


1429
CH2═CH
n-C3H7


1430
CH2═CH
CH2═CH


1431
CH3
CH2═CH


1432
C2H5
CH2═CH


1433
n-C3H7
CH2═CH


1434
E-CH3—CH═CH
CH2═CH


1435
E-CH3—CH═CH
E-CH3—CH═CH


1436
CH3
CH3O


1437
CH3
C2H5O


1438
CH3
n-C3H7O


1439
n-C3H7
CH3O


1440
n-C3H7
C2H5O


1441
n-C3H7
n-C3H7O


1442
n-C5H11
n-C4H9O


1443
n-C4H9O
n-C5H11


1444
CH3O
CH3O


1445
C2H5O
C2H5O


1446
n-C3H7O
n-C3H7O





Note:


*values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).






Examples 1447 to 1478
The following are prepared analogously to Example 241 and Example 361a:
















 














Phase sequence



No.
R1
R2
T/° C.
Δε*





1447
CH3
CH3




1448
CH3
C2H5


1449
CH3
n-C3H7


1450
C2H5
CH3


1451
C2H5
C2H5


1452
C2H5
n-C3H7


1453
n-C3H7
CH3


1454
n-C3H7
C2H5


1455
n-C3H7
n-C3H7


1456
n-C3H7
n-C5H11


1457
n-C5H11
n-C3H7


1458
n-C5H11
n-C5H11


1459
CH2═CH
CH3


1460
CH2═CH
C2H5


1461
CH2═CH
n-C3H7


1462
CH2═CH
CH2═CH


1463
CH3
CH2═CH


1464
C2H5
CH2═CH


1465
n-C3H7
CH2═CH


1466
E-CH3—CH═CH
CH2═CH


1467
E-CH3—CH═CH
E-CH3—CH═CH


1468
CH3
CH3O


1469
CH3
C2H5O


1470
CH3
n-C3H7O


1471
n-C3H7
CH3O


1472
n-C3H7
C2H5O


1473
n-C3H7
n-C3H7O


1474
n-C5H11
n-C4H9O


1475
n-C4H9O
n-C5H11


1476
CH3O
CH3O


1477
C2H5O
C2H5O


1478
n-C3H7O
n-C3H7O





Note:


*values extrapolated from 10% solution in ZLI-4792 or ZLI-2857 (Δε).






Mixture Examples
Liquid-crystalline mixtures are prepared and their applicational properties are investigated.
Example M-1
A liquid-crystal mixture having the composition indicated in the following table was prepared and investigated. It has the properties likewise shown in the table.











Composition











Compound
Abbre-
Conc./%



#
viation
by wt.
Physical properties














1
PCH-301
9.0
T(N, I) =
65.9° C.


2
PCH-302
9.0
ε⊥(20° C., 1 kHz) >
6.1


3
CCH-301
29.7
Δε(20° C., 1 kHz) >
−2.3


4
CCN-47
9.9


5
CCN-55
9.0


6
CBC-33F
4.5


7
CBC-53F
4.5


8
CBC-55F
4.5


9
CBC-33
4.5


10
CBC-53
5.4


11
BFFO-3-5FF
10.0


Σ

100.0









The liquid-crystal medium has very good applicational properties.
Example M-2
A liquid-crystal mixture having the composition indicated in the following table was prepared and investigated. It has the properties likewise shown in the table.











Composition









Com-











pound
Abbre-
Conc./%



#
viation
by wt.
Physical properties














1
PCH-301
9.0
T(N, I) =
76.9° C.


2
PCH-302
9.0
ε⊥(20° C., 1 kHz) >
5.4


3
CCH-301
29.7
Δε(20° C., 1 kHz) >
−1.9


4
CCN-47
9.9


5
CCN-55
9.0


6
CBC-33F
4.5


7
CBC-53F
4.5


8
CBC-55F
4.5


9
CBC-33
4.5


10
CBC-53
5.4


11
BHHO-3O-5FF
10.0


Σ

100.0









The liquid-crystal medium has very good applicational properties.
Example M-3
The mixture shown in the following table is prepared and investigated.











Composition









Com-











pound
Abbre-
Conc./%



#
viation
by wt.
Physical properties














1
PCH-304FF
16.0
T(N, I) =
70° C.


2
PCH-502FF
8.0
Δn(20° C., 589 nm) =
0.100


3
PCH-504FF
14.0
Δε(20° C., 1 kHz) >
−4.5


4
CCP-302FF
14.0


5
CCP-502FF
12.0


6
CCH-35
6.0


7
CC-3-V1
8.0


8
CCP-V-1
8.0


9
BCH-32
8.0


10
BFFO-3-5FF
3.0


11
BHHO-20-5FF
3.0


Σ

100.0









The liquid-crystal medium has excellent applicational properties.
Example M-4 
The mixture shown in the following table is prepared and investigated.











Composition









Com-











pound
Abbre-
Conc./%



#
viation
by wt.
Physical properties















1
PCH-304FF
7.0
T(N, I) =
95.5°
C.


2
CCP-402FF
2.0
Δn (20° C., 589
0.128





nm) =


3
CCP-303FF
7.0
Δε (20° C., 1
−3.2





kHz) >


4
BCH-202FF
11.0
k1 (20° C.) =
16.0
pN


5
BCH-302FF
11.0
k1/k3 (20° C.) =
0.94


6
PYP-2-3
10.0
γ1 (20° C.) =
154
mPa · s


7
PYP-2-4
10.0
tstore (−20° C.) >
1,000
h


8
CC-4-V
10.0
V0 (20° C.) =
2.28
V


9
CC-5-V
10.0


10
CC-3-V1
10.0


11
CCP-V-1
2.0


12
CCH-34
5.0


13
C-BHHO-
3.0



5-04FF


Σ

100.0









The liquid-crystal medium has excellent applicational properties, as is evident, for example, in comparison with the following comparative example (CM-1).
Comparative Example CM-1
The mixture shown in the following table, which comprises no compound according to the invention, is prepared and investigated.











Composition









Com-











pound
Abbre-
Conc./%



#
viation
by wt.
Physical properties















1
PCH-304FF
12.0
T(N, I) =
96°
C.


2
PCH-502FF
10.0
Δn (20° C., 589
0.126





nm) =


3
BCH-202FF
12.0
Δε (20° C., 1
−3.1





kHz) >


4
BCH-302FF
13.0
k1 (20° C.) =
15.0
pN


5
PYP-2-3
8.0
k1/k3 (20° C.) =
1.09


6
PYP-2-4
8.0
γ1 (20° C.) =
169
mPa · s


7
CC-4-V
13.0
tstore (−20° C.) >
1,000
h


8
CC-3-V1
9.0
V0 (20° C.) =
2.42
V


9
CCP-V-1
10.0


10
CCPC-33
3.0


11
CCPC-34
3.0


Σ

100.0









The liquid-crystal medium has similar values for the clearing point, the birefringence and the dielectric anisotropy to the medium of Example 4. However, it has significantly higher rotational viscosity and at the same time a higher threshold voltage and consequently has clearly inferior applicational properties.
Example M-5
The mixture shown in the following table is prepared and investigated.











Composition









Com-











pound
Abbre-
Conc./%



#
viation
by wt.
Physical properties















1
PCH-304FF
5.0
T(N, I) =
95.5°
C.


2
PCH-502FF
3.0
Δn (20° C., 589
0.129





nm) =


3
CCP-303FF
10.0
Δε (20° C., 1
−3.8





kHz) >


4
BCH-202FF
11.0
k1 (20° C.) =
15.7
pN


5
BCH-302FF
11.0
k1/k3 (20° C.) =
0.97


6
PYP-2-3
6.0
γ1 (20° C.) =
173
mPa · s


7
PYP-2-4
14.0
tstore (−20° C.) >
1,000
h


8
CC-4-V
15.0
V0 (20° C.) =
2.10
V


9
CC-3-V1
12.0


10
CCH-34
6.0


11
C-BHHO-
7.0



5-04FF



Σ

100.0









The liquid-crystal medium has excellent applicational properties, as is evident, for example, in comparison with the following comparative example (CM-2).
Comparative Example CM-2
The mixture shown in the following table, which comprises no compound according to the invention, is prepared and investigated.











Composition











Com-

Conc./%











pound
Abbre-
by



#
viation
wt
Physical properties















1
PCH-304FF
9.0
T(N, I) =
96°
C.


2
PCH-502FF
5.0
Δn (20° C., 589
0.1127





nm) =


3
CCP-302FF
8.0
Δε (20° C., 1
−3.7





kHz) >


4
CCP-402FF
9.0
k1 (20° C.) =
16.3
pN


5
BCH-2-02FF
12.0
k1/k3 (20° C.) =
0.97


6
BCH-3-02FF
12.0
γ1 (20° C.) =
179
mPa · s


7
PYP-2-3
9.0
tstore (−20° C.) =
950
h


8
PYP-2-4
9.0
V0 (20° C.) =
2.19
V


9
CC-4-V
13.0


10
CC-3-V1
11.0


11
CCH-35
2.0


Σ

100.0









The liquid-crystal medium has similar values for the clearing point, the birefringence and the dielectric anisotropy to the medium of Example 5. However, it has significantly higher rotational viscosity and at the same time a higher threshold voltage and consequently has less suitable applicational properties.

## Claims

1. A compound of formula I




wherein
Y is —CO—, —CS—, —CH2—, —CF2— or —CHF—,
L1 and L2 are each, independently of one another, H, F, Cl or —CN,




 are each, independently of one another, and, if present more than once, also independently of one another,
(a) a trans-1,4-cyclohexylene radical, in which, one or two non-adjacent CH2 groups are optionally replaced by —O— and/or —S—,
(b) a 1,4-cyclohexenylene radical,
(c) a 1,4-phenylene radical, in which, one or two non-adjacent CH groups are optionally replaced by N, or
(d) 1,4-bicyclo[2.2.2]octylene, 1,3-bicyclo[1.1.1]pentylene, spiro[3.3]heptane-2,4-diyl, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl,

R1 and R2 are each, independently of one another, H, halogen, —CN, —SCN, —SF5, —CF3, —CHF2, —CH2F, —OCF3, —OCHF2, or an alkyl group having 1 to 15 carbon atoms which is monosubstituted by CN or CF3 or at least monosubstituted by halogen, and in which one or more CH2 groups each, independently of one another, are optionally replaced by —O—, —S—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—,




 —CO—, —CO—O—, —O—CO— or —O—CO—O— in such a way that neither O nor S atoms are linked directly to one another,
Z1 and Z2 are each, independently of one another, —CH2—CH2—, —CF2—CF2—, —CF2—CH2—, —CH2—CF2—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—, —C═C—, —COO—, —OCO—, —CH2O—, —OCH2—, —CF2O—, or —OCF2—, or a combination of two of these groups, where no two O atoms are bonded to one another, and
n and m are each 0, 1 or 2, where
n+m is 0, 1, 2 or 3,
with the proviso that, if Y is —CO—, at least one of L1 and L2 is not H.

2. A compound according to claim 1, which is of formula I-1a, I-1b, I-2a, I-2b, I-3a or I-3b



wherein
L1 and L2 are each, independently of one another, H, F, Cl or —CN,




 are each, independently of one another, and, if present more than once, also independently of one another,
(a) a trans-1,4-cyclohexylene radical, in which, one or two non-adjacent CH2 groups are optionally replaced by —O— and/or —S—,
(b) a 1,4-cyclohexenylene radical,
(c) a 1,4-phenylene radical, in which, one or two non-adjacent CH groups are optionally replaced by N, or
(d) 1,4-bicyclo[2.2.2]octylene, 1,3-bicvclo[1.1.1]pentylene, spiro[3.3]heptane-2,4-diyl, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl,

R1 and R2 are each, independently of one another, H, halogen, —CN, —SCN, —SF5, —CF3, —CHF2, —CH2F, —OCF3, —OCHF2, or an alkyl group having 1 to 15 carbon atoms which is monosubstituted by CN or CF3 or at least monosubstituted by halogen, and in which one or more CH2 groups each, independently of one another, are optionally replaced by —O—, —S—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—,




 —CO—, —CO—O—, —O—CO— or —O—CO—O— in such a way that neither O nor S atoms are linked directly to one another,
Z1 and Z2 are each, independently of one another, —CH2—CH2—, —CF2—CF2—, —CF2—CH2—, —CH2—CF2—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—, —C≡C—, —COO—, —OCO—, —CH2O—, —OCH2—, —CF2O—, or —OCF2—, or a combination of two of these groups, where no two O atoms are bonded to one another, and
n and m are each 0, 1 or 2, where
n+m is 0, 1, 2 or 3.

3. A compound according to claim 1, wherein Y is —CF2—.

4. A compound according to claim 1, wherein L1 and L2 are both F.

5. A compound according to claim 1, wherein Z1 and Z2 are both a single bond.

6. A liquid-crystal medium, comprising one or more compounds of claim 1.

7. A liquid-crystal medium according to claim 6, comprising one or more dielectrically negative compound(s) of formula II



wherein
R21 and R22 are each, independently of one another, H, halogen, —CN, —SCN, —SF5, —CF3, —CHF2, —CH2F, —OCF3, —OCHF2, or an alkyl group having 1 to 15 carbon atoms which is monosubstituted by CN or CF3 or at least monosubstituted by halogen, and in which one or more CH2 groups each, independently of one another, are optionally replaced by —O—, —S—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—,




 —CO—, —CO—O—, —O—CO— or —O—CO—O— in such a way that neither O nor S atoms are linked directly to one another,
Z21 and Z22 are each, independently of one another, —CH2—CH2—, —CF2—CF2—, —CF2—CH2—, —CH2—CF2—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—, —C≡C—, —COO—, —OCO—, —CH2O—, —OCH2—, —CF2O—, or —COF2—, or a combination of two of these groups, where no two O atoms are bonded to one another,




 are each, independently of one another,




L1 and L2 are both C—F or one of the two is N and the other is C—F, and
I is 0 or 1.

8. A liquid-crystal medium according to claim 6, comprising one or more compound(s) of formula II-1



wherein
R21 and R22 are each, independently of one another, H, halogen, —CN, —SCN, —SF5, —CF3, —CHF2, —CH2F, —OCF3, —OCHF2, or an alkyl group having 1 to 15 carbon atoms which is monosubstituted by CN or CF3 or at least monosubstituted by halogen, and in which one or more CH2 groups each, independently of one another, are optionally replaced by —O—, —S—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—,




 —CO—, —CO—O—, —O—CO— or —O—CO—O— in such a way that neither O nor S atoms are linked directly to one another,
Z21 and Z22 are each, independently of one another, —CH2—CH2—, —CF2—CF2—, —CF2—CH2—, —CH2—CF2—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—, —C≡C—, —COO—, —OCO—, —CH2O—, —OCH2—, —CF2O—, or —OCF2—, or a combination of two of these groups, where no two O atoms are bonded to one another,




 is





and

I is 0 or 1.

9. An electro-optical display containing a liquid-crystal medium according to claim 6.

10. A display according to claim 9, which is a VAN LCD.

11. A compound according to claim 2, wherein L1 and L2 are both F.

12. A compound according to claim 2, wherein Z1 and Z2 are both a single bond.

13. A liquid-crystal medium, comprising one or more compounds of claim 2.

14. An electro-optical display containing a liquid-crystal medium according to claim 7.

15. A display according to claim 14, which is a VAN LCD.

16. An electro-optical display containing a liquid-crystal medium according to claim 8.

17. A display according to claim 6, which is a VAN LCD.

18. An electro-optical display containing a liquid-crystal medium according to claim 13.

19. A display according to claim 18, which is a VAN LCD.

20. A liquid-crystal medium, comprising one or more compounds of claim 1, wherein L1 and L2 are both F and Z1 and Z2 are both a single bond.