Chroman compounds

Information

  • Patent Grant
  • 7955664
  • Patent Number
    7,955,664
  • Date Filed
    Tuesday, December 11, 2007
    17 years ago
  • Date Issued
    Tuesday, June 7, 2011
    13 years ago
Abstract
The chroman compounds of the formula I according to the invention R1-(A1-Z1)a—W1—(Z2-A2)b-Z3—W2—(Z4-A3)c-R2 in which R1, A1, A2, A3, W1, W2, Z1, Z2, Z3, Z4, a, b and c have the meanings indicated in claim 1, have two moieties W1 and W2 derived from chroman. The compounds are suitable as components of anisotropic switching media, as used, for example, in liquid-crystal display devices.
Description

The invention relates to compounds of the formula I

R1-(A1-Z1)a—W1—(Z2-A2)b-Z3—W2—(Z4-A3)c-R2  I

  • in which
  • W1, W2, independently of one another, denote a divalent group of the formula




embedded image


  • ring B denotes an unsaturated or partially saturated, six-membered ring in which one or two of the CH2 groups have been replaced by O, where no two O atoms are adjacent, and in which —CH2— may be replaced by —CHF—or —CF2— or ═CH— may be replaced by ═CF—,

  • L1, L2 and L3
    • each, independently of one another, denote H, Cl, F, CN or CF3,

  • R1, R2, independently of one another, denote H, Cl, F, CN, SCN, SF5, an alkyl radical having up to 15 C atoms which is unsubstituted, monosubstituted by CN or at least monosubstituted by halogen, where, in addition, one or more CH2 groups in these radicals may each be replaced, independently of one another, by —O—, —CH═CH—, —CF═CF—, —CF═CH—, —C≡C—, —S—, —CO—, —(CO)O—, —O(CO)— or —O(CO)O— in such a way that O atoms are not linked directly to one another,

  • A1, A2 and A3
    • each, independently of one another, denote
    • (a) a trans-1,4-cyclohexylene radical, in which, in addition, one or more non-adjacent CH2 groups may be replaced by —O— and/or —S—,
    • (b) a 1,4-phenylene radical, in which, in addition, one or two CH groups may be replaced by N,
    • (c) 1,4-cyclohexenylene,
    • (d) a radical from the group 1,3-bicyclo[1.1.1]pentylene, 1,4-bicyclo[2.2.2]octylene, cyclobut-1,3-diyl, spiro[3.3]heptane-2,6-diyl, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl,
    • where the radicals (a) to (d) may be substituted by one or more, in particular one or two, fluorine atoms,

  • Z1, Z2, Z3 and Z4
    • each, independently of one another, denote —(CO)O—, —O(CO)—, —CH2O—, —OCH2—, —CH2CH2—, —CH═CH—, —CH═CF—, —CF═CH—, —CF═CF—, —CHFCHF—, —CH2CHF—, —CHFCH2—, —C≡C—, —(CH2)4—, —CF2O—, —OCF2—, —C2F4—, —CH═CH—CH2CH2—, —CH2CH2OCF2— or a single bond, and

  • a, b, c, independently of one another, denote 0 or 1, where

  • a+b+c adopts the value 0, 1 or 2.



The invention furthermore relates to the use of these compounds as components of liquid-crystalline media and to liquid-crystal and electro-optical display elements which contain the liquid-crystalline media according to the invention.


The compounds of the formula I can be used as components of liquid-crystalline media, in particular for displays based on the principle of the twisted cell, the guest-host effect, the effect of deformation of aligned phases or the effect of dynamic scattering.


Documents WO 2006/040009, JP 2006199941 A and EP 14910612 disclose chroman derivatives which have only one moiety having the chroman structure.


The invention was thus based on the object of finding novel, stable compounds which are suitable as component(s) of liquid-crystalline media, in particular for TN, STN, IPS and for further active-matrix displays.


Especially in the area of compounds of very high polarity (Δε>20), which are basically advantageous for many display applications, the problem of the ever-lower solubility of the compounds is encountered. This limits the use of such compounds in practice. It is therefore also an aim to find novel, highly polar, mesogenic compounds which can at the same time be dissolved in highly polar liquid-crystal mixtures in high proportions by weight. The overall consideration of the solubility of all compounds involved crucially determines the tendency towards crystallisation at low temperatures and therefore determines the stability of the displays at temperatures at the lower end of the application range.


An object of the present invention was in addition to provide compounds which have high positive dielectric anisotropy Δε. In addition, the compounds according to the invention should be thermally and photochemically stable. Furthermore, the compounds according to the invention should be usable in liquid-crystalline mixtures in that they do not impair or even improve the liquid-crystalline phase ranges thereof. It is furthermore advantageous if the compounds according to the invention have the broadest possible nematic phase.


The compounds of the formula I are eminently suitable as components of liquid-crystal mixtures of positive dielectric anisotropy, in particular if particularly high polarity of the host mixture is important, as is the case, for example, in the production of liquid-crystal displays using blue phases (cf. WO 2004/046805 and H. Kikuchi et al. Nature Materials (2002) 1, 64-68). It has been found that the chroman derivatives according to the invention are eminently suitable as components of anisotropic electro-optical media. They can be used to obtain stable, mesogenic switching media, in particular suitable for TN-TFT, STN and IPS displays and displays based on blue phases. Owing to their properties, the compounds are particularly suitable for use in the fast-switching displays operated in the area of blue phases, particularly as constituent of polymer-stabilised media, as disclosed, for example, in document EP 1690914 A1. The compounds according to the invention are stable chemically, thermally and to (UV) light. They are colourless in the pure state. They are also distinguished by strongly positive dielectric anisotropies Δε, due to which lower threshold voltages are necessary on use in optical switching elements. A further advantage of the compounds according to the invention is the high polarity of the two substituted chroman rings.


In addition, the compounds according to the invention have a broad nematic phase range.


Through a suitable choice of the ring members and/or the terminal substituents, the physical properties of the liquid crystals according to the invention can be varied in broad ranges.


The provision of the chroman derivatives according to the invention very generally considerably broadens the range of compounds which are suitable from various applicational points of view for the preparation of liquid-crystalline mixtures.


In the mixture with suitable co-components, the compounds according to the invention form liquid-crystalline mesophases in a temperature range which is favourably located for electro-optical use. Liquid-crystalline media having broad nematic phase ranges can be prepared from the compounds according to the invention and further substances.


The chroman derivatives have a broad range of applications. Depending on the choice of substituents, these compounds can serve as base materials of which liquid-crystalline media are predominantly composed. However, it is also possible to add liquid-crystalline base materials from other classes of compound to the compounds according to the invention in order, for example, to modify the dielectric and/or optical anisotropy of a dielectric of this type and/or to optimise its working-temperature range.


The invention thus relates to the compounds of the formula I and to the use of these compounds as components of liquid-crystalline media. The invention furthermore relates to liquid-crystalline media comprising at least one compound of the formula I and to liquid-crystal display elements, in particular electro-optical display elements, which contain media of this type.


For the purposes of the present application, the numbering of the atom positions of the formula indicated for W1/2 is as follows:




embedded image


The free valence of ring B is located in position 2 or 3, that of the benzo ring is arranged in position 6 or 7. The substituent L3 is localised at the remaining position 6 or 7. The ring system is preferably simultaneously connected at the mutually opposite positions 2/6 or 3/7 to the radical of the structure of the formula I, formally resulting in the substitution patterns (1) and (2):




embedded image


In view of the following definitions, substitution pattern (1) is preferred.


Ring B encompasses the following ring structures and mirror images thereof, with the optional substitution by fluorine atoms not being shown:




embedded image


For the purposes of the present invention, all ring elements depicted are referred to for simplification as chroman rings and the associated compounds are referred to as chroman compounds. The compounds are therefore also referred to as bischromanyl derivatives. Ring B is partially saturated if it only contains the one double bond of the benzene ring. Ring B is referred to as unsaturated if it contains two double bonds.


Ring B is preferably not substituted by fluorine atoms. It preferably has precisely one oxygen atom. In the case where ring B has a second double bond, this is preferably arranged in the β-position (allyl position) to the oxygen atom. Ring B is preferably partially saturated.


The moieties W1 and W2 preferably have, independently of one another, the following meanings with the associated names:




embedded image


W1 and W2 particularly preferably adopt, independently of one another, the meaning of moiety (w10) or (w20), in particular (w10). W1 and W2 preferably adopt the same meaning. Likewise, W1 preferably adopts the meaning (w20) and W2 the meaning (w10).


The groups L1, L2 and L3 in the formula I and the sub-formulae are preferably H, Cl, F, CF3 or CN, particularly preferably H or F. At least one of the substituents L1, L2 and L3 is preferably not hydrogen. L3 preferably denotes F. L2 is preferably a hydrogen atom. L1 preferably denotes H or F.


For the group W2, L1 preferably denotes F; for the group W1, L1 preferably denotes H.


If they are not symmetrical, the ring systems indicated in groups (a) to (d) can be in both possible orientations. They are preferably arranged in such a way that the dipole of the ring is as far as possible aligned in the same direction and parallel with the same orientation to that of the chroman ring.


Z1, Z2 and Z4 preferably denote a single bond, —CH2CH2—, —CH═CH—, CH2O or —CF2O—, and in particular a single bond or —CH2CH2—.


Preferred meanings for Z3 are CH2CH2, CH2O or a single bond, particularly a single bond.


The sum of the indices a, b and c in the formula I should be 0, 1 or 2 and is preferably 0 or 1.


Preference is given to compounds of the formula I and of all sub-formulae in which A1, A2 and/or A3 denote cyclohexane-1,4-diyl, 1,3-dioxane-2,5-diyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, 1,4-phenylene which is mono- or disubstituted by F or furthermore a radical from the group under point (d), as defined for formula I.


A1, A2 and A3 particularly preferably denote a divalent group selected from the formulae:




embedded image


Z2, A2, b and Z3 together are preferably selected in such a way that the group —(Z2-A2)-Z3— does not denote a single bond.


R1 preferably denotes an alkyl radical having up to 15 C atoms which is unsubstituted, monosubstituted by CN or at least mono-substituted by halogen, where, in addition, one or more CH2 groups in these radicals may each be replaced, independently of one another, by —O—, —CH═CH—, —C≡C—, —S—, —CO—, —(CO)O—, —O(CO)—or —O(CO)O— in such a way that O atoms are not linked directly to one another.


R1 particularly preferably denotes alkyl, alkoxy, alkenyl or alkenyloxy having up to 7 C atoms and very particularly preferably 1-5 C alkyl or 2-5 C alkenyl.


R2 preferably denotes H, Cl, F, CN, SCN, SF5, an alkyl radical having up to 15 C atoms which is monosubstituted by CN or at least monosubstituted by halogen, where, in addition, one or more CH2 groups in these radicals may each be replaced, independently of one another, by —O—, —CH═CH—, —CF═CF—, —CF═CH—, —C≡C—, —S—, —CO—, —(CO)O—, —O(CO)— or —O(CO)O— in such a way that O atoms are not linked directly to one another.


R2 particularly preferably denotes H, Cl, F, CN, SCN, SF5, CF3, CHF2 or OCF3, very particularly preferably F, OCF3 or CN, of these in particular CN.


If R1/2 denotes an alkyl radical and/or an alkoxy radical, this may be straight-chain or branched. It is preferably straight-chain, has 1, 2, 3, 4, 5, 6 or 7 C atoms and accordingly preferably denotes methyl, ethyl, propyl, butyl, pentyl, heptyl, hexyl, ethoxy, propoxy, butoxy, pentoxy, hexyloxy or heptyloxy, furthermore octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy or tetradecyloxy.


If R1/2 denotes 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 2 to 10 C atoms. Accordingly, it denotes, 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, dec-1-, -2-, -3-, -4-, -5-, -6-, -7-, -8- or -9-enyl.


If R1/2 denotes 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 2 to 6 C atoms. Accordingly, they denote 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, butoxycarbonylmethyl, 2-(methoxycarbonyl)ethyl, 2-(ethoxycarbonyl)ethyl, 2-(propoxycarbonyl)ethyl, 3-(methoxycarbonyl)propyl, 3-(ethoxycarbonyl)propyl, 4-(methoxycarbonyl)butyl.


If R1/2 denotes 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 4 to 13 C atoms. Accordingly, it denotes in particular acryloyloxymethyl, 2-acryloyloxyethyl, 3-acryloyloxypropyl, 4-acryloyloxybutyl, 5-acryloyloxypentyl, 6-acryloyloxyhexyl, 7-acryloyloxyheptyl, 8-acryloyloxyoctyl, 9-acryloyloxynonyl, 10-acryloyloxydecyl, methacryloyloxymethyl, 2-methacryloyloxyethyl, 3-methacryloyloxypropyl, 4-methacryloyloxybutyl, 5-methacryloyloxypentyl, 6-methacryloyloxyhexyl, 7-methacryloyloxyheptyl, 8-methacryloyloxyoctyl, 9-methacryloyloxynonyl.


If R1/2 denotes an alkyl or alkenyl radical which is mono-substituted by CN, this radical is preferably straight-chain, and the substitution by CN is in the ω-position.


If R1/2 denotes an alkyl or alkenyl radical which is at least mono-substituted 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 ω-position.


For the purposes of the present invention, halogen denotes fluorine, chlorine, bromine or iodine, preferably Br, Cl or F, particularly preferably Cl or F, and in particular fluorine.


Compounds of the formula I which contain wing groups R1/2 which are suitable for polymerisation reactions are suitable for the preparation of mesogenic polymers, also in combination with other monomers. These polymers are suitable for the stabilisation of a mesophase which predominates under the polymerisation conditions.


Compounds of the formula I containing branched wing groups R1 may occasionally be of importance owing to still further improved solubility in the conventional liquid-crystalline base materials, but in particular as chiral dopants if they are optically active. The formula I encompasses both the racemates of these compounds and also the optical antipodes, and mixtures thereof. 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.


Branched groups of this type generally contain not more than one chain branch. Preferred branched radicals R 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, 1-methylheptyloxy.


In a preferred embodiment, the compounds of the formula I are characterised in that

  • c denotes 1,
  • Z4 denotes CF2O, and
  • A3 denotes a divalent group selected from the formulae




embedded image


Of the compounds of the formula I and of all sub-formulae, preference is given to those in which one or more of the radicals present therein have one of the preferred meanings indicated. Further preferred embodiments may be derived by the skilled person from the details of the example part and may be generalized for his purposes.


In the compounds of the formula I, preference is given to the stereoisomers in which the cyclohexane rings are trans-1,4-disubstituted. Those of the above-mentioned formulae which can contain a plurality of stereoisomers in each case encompass all possible stereoisomers.


Preferred smaller groups of compounds of the formula I are, in addition, those of the sub-formulae Ia to If

R1—W1—W2—R2  Ia
R1—W1—Z3—W2—R2  Ib
R1-A1-W1—W2—R2  Ic
R1—W1-A2-W2—R2  Id
R1—W1—W2-A3-R2  Ie
R1—W1—W2—Z4-A3-R2  If


The 1,4-cyclohexenylene group preferably has the following structures:




embedded image


The compounds of the formula I are prepared by methods known per se, as described in the literature (for example in the standard works, such as Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart), to be precise under reaction conditions which are known and suitable for the said reactions.


Use can also be made here of variants known per se which are not mentioned here in greater detail.


Starting from simple benzene derivatives, compounds of the formula I according to the invention can be prepared by the following methods.


The synthesis of the compounds of the formula I can be carried out, for example, using halogenated benzochromenes (compound 2), the preparation of which is described in document WO 2006/040009.




embedded image


Compounds of this type can either be reacted directly (for example by transition metal-catalysed arylation of ketones, malonates, olefins, etc., Scheme 1) or modified in a suitable manner for further reaction for the synthesis of the compounds of the formula I in accordance with the following schemes using standard transformations, as are known to the person skilled in the art and described in the literature (Houben Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Georg Thieme Verlag, Stuttgart, New York, 4th Edn. 1993).




embedded image


Thus, for example, metallation of compound 2 (for X═H: using LDA, BuLi, Schlosser base; for X=Hal: using Mg, iPrMgHal, etc.) and optionally transmetallation using, for example, zinc halides, gives, inter alia, the arylmetal compounds 7 (Scheme 2), which can be converted in a versatile manner into further novel synthetic building blocks (Scheme 3).




embedded image




embedded image


Versatile access to synthetic building blocks for linking to the cycloaliphatic ring B is available starting from salicylaldehydes 14, which are readily accessible, for example, by the method of Duff (J. C. Duff and E. J. Bills, J. Chem. Soc. (1932) 1987; (1934) 1305; J. C. Duff, ibid. (1941) 547; (1945) 276) from phenols using hexamethylenetetramine (Scheme 4).




embedded image


The condensation of the salicylaldehydes 14 with acrylonitrile analogously to L. D. Wise et al., J. Med. Chem. (1988) 31, 688-691 then gives carbonitriles (15), which can be modified in a manner familiar to the person skilled in the art in accordance with Scheme 5 and Scheme 6 to give a multiplicity of synthetic building blocks.




embedded image




embedded image


The following schemes show some preferred reactions of the synthetic building blocks described in Schemes 1 to 6 to give the target compounds of the formula I. Thus, directly linked bischromanyl derivatives can be obtained from the malonates 5 analogously to the synthesis of the chromans themselves (cf. WO 2006/040009) (Scheme 7).




embedded image


The compounds 25 here may also contain further rings A2 (at position 7), which are accessible in an analogous manner and can be converted into the corresponding end products 27a and 27b (Schemes 8a, 8b)




embedded image




embedded image


The diols 24 are likewise suitable for the synthesis of dioxanes (Scheme 9). Condensation of 24 with the aldehydes 16 (cf. Scheme 5) gives the compounds 28, which can be hydrogenated to give the saturated dioxanes 29.




embedded image


A possible synthetic route to compounds of the formula I containing a simple bridge Z3 between the chroman rings (i.e. without ring A2) is shown in Scheme 10. Thus, for example, the acetylene derivatives 18 can be reacted with the aryl halides 2 in a Negishi coupling to give the compounds 30a, which then, after hydrogenation, give the ethylene-bridged compounds 30b.




embedded image


Structural isomers of the salicylaldehydes 14 (cf. Scheme 4), which are accessible in an analogous manner and are likewise described in WO 2006/040009, can serve for the synthesis of benzo[1,3]dioxins 33 as shown in Scheme 11, for example through acetalisation using the aldehydes 8 as starting material (cf. Scheme 3).




embedded image


Scheme 12 shows the synthesis of chromans of type (w21) and (w20). Through Petasis reaction by the method of Q. Wang, M. G. Finn, Org. Lett. (2000) 2, 4063-4065, the compounds 35 can be used for the synthesis of α-substituted chroman compounds of type (w21) (chromenes), which can then be hydrogenated to give the chromans 37 (Scheme 12). The boronic acids 34 are obtained by hydroboration of the alkynes 4 (cf. Scheme 1) by processes known from the literature.




embedded image




embedded image


Isochromans can likewise be prepared starting from salicylaldehydes 35 (for example 41, Scheme 13). Here, the salicylaldehydes 35 are firstly reacted, for example, with trifluoromethanesulfonic anhydride to give the triflates 38, from which the stilbenes 39 can then be prepared in a Suzuki reaction with the boronic acids 34 (see above). After reduction of the aldehyde group to the alcohol 40, for example by reaction with sodium borohydride, the isochromans 41 can then be obtained by base-catalysed cyclisation by the method of R. G. F Giles et al., J. Chem. Soc. Perkin 1 (1984) 2389-2396.


An embodiment of the invention is therefore also a first process for the preparation of compounds of the formula I in which A2 is a dioxane ring and Z2 and Z3 are single bonds, which is characterised in that it includes a process step in which a compound of the formula II




embedded image



in which the radicals are as defined above for formula I, is reacted with an aldehyde of the formula III




embedded image



in which the radicals are as defined above for formula I, with formation of a dioxane ring. The process is preferably carried out in an organic solvent with acid catalysis. It is advantageous here continuously to remove the water formed from the reaction, for example by means of an adsorbent or by azeotropic distillation. The formula III is preferably that of compound 16 (Scheme 5).


A further embodiment of the invention is a second process for the preparation of compounds of the formula I in which b is 0 and Z3 is a single bond, which is characterised in that it includes a process step in which an oxetane compound of the formula IV




embedded image



in which the radicals are as defined above for formula I, is reacted with a bromobenzene derivative of the formula V




embedded image



in which the radicals are as defined above for formula I, to give a compound of the formula




embedded image



and, in a further process step, is converted into compounds of the formula I or a precursor thereof by cyclisation. The cyclisation is preferably effected by a strong base. The reaction is preferably carried out in an inert solvent. A suitable strong base is, for example, potassium hydride.


Further possible synthetic routes for chroman compounds are disclosed in document WO 2006/040009 on pages 42-52 and in the examples. The last-mentioned disclosures are incorporated here by way of reference.


The liquid-crystalline media according to the invention preferably comprise 2 to 40, in particular 4 to 30, components as further constituents besides one or more compounds according to the invention. These media very particularly preferably comprise 7 to 25 components besides one or more compounds according to the invention. These further constituents are preferably selected from nematic or nematogenic (monotropic or isotropic) substances, in particular substances from the classes of the azoxybenzenes, benzylideneanilines, biphenyls, terphenyls, phenyl or cyclohexyl benzoates, phenyl or cyclohexyl esters of cyclohexanecarboxylic acid, phenyl or cyclohexyl esters of cyclohexylbenzoic acid, phenyl or cyclohexyl esters of cyclohexylcyclohexanecarboxylic acid, cyclohexylphenyl esters of benzoic acid, of cyclohexanecarboxylic acid or of cyclohexylcyclohexanecarboxylic acid, phenylcyclohexanes, cyclohexylbiphenyls, phenylcyclohexylcyclohexanes, cyclohexylcyclohexanes, cyclohexylcyclohexylcyclohexanes, 1,4-biscyclohexylbenzenes, 4,4′-biscyclohexylbiphenyls, phenyl- or cyclohexylpyrimidines, phenyl- or cyclohexylpyridines, phenyl- or cyclohexyldioxanes, phenyl- or cyclohexyl-1,3-dithianes, 1,2-diphenylethanes, 1,2-dicyclohexylethanes, 1-phenyl-2-cyclohexylethanes, 1-cyclohexyl-2-(4-phenylcyclohexyl)ethanes, 1-cyclohexyl-2-biphenylylethanes, 1-phenyl-2-cyclohexylphenylethanes, optionally halogenated stilbenes, benzyl phenyl ethers, tolans and substituted cinnamic acids. The 1,4-phenylene groups in these compounds may also be fluorinated.


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

R′-L-E-R″  1
R′-L-COO-E-R″  2
R′-L-OOC-E-R″  3
R′-L-CH2CH2-E-R″  4
R′-L-C≡C-E-R″  5


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


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


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


In another smaller sub-group of the compounds of the formulae 1, 2, 3, 4 and 5, which is referred to as group B, R″ denotes —F, —Cl, —NCS or —(O)iCH3−(k+l)FkCll, where i is 0 or 1 and k+l is 1, 2 or 3; the compounds in which R″ has this meaning are referred to by the sub-formulae 1b, 2b, 3b, 4b and 5b. Particular preference is given to compounds of the sub-formulae 1b, 2b, 3b, 4b and 5b in which R″ has the meaning —F, —Cl, —NCS, —CF3, —OCHF2 or —OCF3.


In the compounds of the sub-formulae 1b, 2b, 3b, 4b and 5b, R′ has the meaning indicated for the compounds of the sub-formulae 1a-5a and is preferably alkyl, alkenyl, alkoxy or alkoxyalkyl.


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


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


Besides compounds of the formula I according to the invention, the media according to the invention preferably comprise one or more compounds selected from group A and/or group B and/or group C. The proportions by weight of the compounds from these groups in the media according to the invention are preferably


















group A:
0 to 90%, preferably 20 to 90%,




in particular 30 to 90%



group B:
0 to 80%, preferably 10 to 80%,




in particular 10 to 65%



group C:
0 to 80%, preferably 5 to 80%,




in particular 5 to 50%











where the sum of the proportions by weight of the compounds from groups A, B and C present in the media according to the invention is preferably 5 to 90% and in particular 10 to 90%.


The media according to the invention preferably comprise 1 to 40%, particularly preferably 5 to 30%, of compounds according to the invention. Preference is furthermore given to media comprising more than 40%, in particular 45 to 90%, of compounds according to the invention. The media preferably comprise two, three or four compounds according to the invention.


The media according to the invention are prepared in a manner conventional per se. In general, the components are dissolved in one another, advantageously at elevated temperature. By means of suitable additives, the liquid-crystalline phases in accordance with the invention can be modified in such a way that they can be used in all types of liquid-crystal display element that have been disclosed to date. Additives of this type are known to the person skilled in the art and are described in detail in the literature (H. Kelker/R. Hatz, Handbook of Liquid Crystals, Verlag Chemie, Weinheim, 1980). Polymer-stabilised media are generally subsequently subjected to polymerisation after mixing of the components. Furthermore, stabilisers, antioxidants, dyes or nanoparticles can be added.


The mixtures according to the invention are suitable for TN, STN, ECB, IPS or TN-TFT applications and in particular for applications with media in the blue phase. Particular preference is given to use in polymer-stabilised blue phases. Suitable polymeric constituents of the blue phases are mesogenic and non-mesogenic monomers, in particular mono- and diacrylates, which are polymerised in the mixture in such a way that they maintain the desired molecular structure in a broad temperature range.


The construction of the matrix display according to the invention from polarisers, electrode base plates and surface-treated electrodes corresponds to the usual design for displays of this type. The term usual design is broadly drawn here and also encompasses all derivatives and modifications of the matrix display, in particular also matrix display elements based on poly-Si TFTs.


The following examples are intended to explain the invention without limiting it. Above and below, percentage data denote percent by weight. All temperatures are indicated in degrees Celsius. M.p. denotes melting point, cl.p.=clearing point. Furthermore, C=crystalline state, N=nematic phase, S=smectic phase and I=isotropic phase. The data between these symbols represent the transition temperatures. Δn denotes optical anisotropy (589 nm, 20° C.), and the flow viscosity ν20 (mm2/sec) and the rotational viscosity γ1 [mPa·s] are each determined at 20° C.


The physical, physicochemical and electro-optical parameters are determined by generally known methods, as described, inter alia, in the brochure “Merck Liquid Crystals—Licristal®—Physical Properties of Liquid Crystals—Description of the Measurement Methods”, 1998, Merck KGaA, Darmstadt.


The dielectric anisotropy Δε of the individual substances is determined at 20° C. and 1 kHz. To this end, 5-10% by weight of the substance to be investigated are measured dissolved in the dielectrically positive mixture ZLI-4792 (Merck KGaA), and the measurement value is extrapolated to a concentration of 100%. The optical anisotropy Δn is determined at 20° C. and a wavelength of 589.3 nm, the rotational viscosity γi at 20° C., both likewise by linear extrapolation.


The following abbreviations are used above and below:

  • RT room temperature
  • MTB ether methyl tert-butyl ether
  • THF tetrahydrofuran
  • p-TsOH p-toluenesulfonic acid
  • DABCO 1,4-diazabicyclo[2.2.2]octane
  • Rf retention factor in chromatography
  • DIBAL-H diisobutylaluminium hydride
  • Pd (C) palladium on carbon (commercially available catalyst)







Example 1
6,6′-Difluoro-3′-propyl-3,4,3′,4′-tetrahydro-2H,2′H-[3,7′]bichromenyl-7-carbonitrile

The synthesis of 7-bromo-6-fluoro-3-propylchroman is carried out in accordance with WO 2006/040009.


1.1. 6-Fluoro-7-iodo-3-propylchroman



embedded image


10.6 g (38.8 mmol) of 7-bromo-6-fluoro-3-propylchroman are initially introduced in 100 ml of THF, and 27 ml (43.0 mmol) of a 15 percent solution of n-butyllithium in hexane are added dropwise. After 90 min, 10.0 g (39.4 mmol) of iodine, dissolved in 50 ml of THF, are added, the mixture is stirred for 1 h, and the cooling is removed. The batch is diluted with MTB ether, washed with water and with sat. sodium hydrogensulfite soln. and dried over sodium sulfate. The solvent is removed in vacuo, and the crude product is filtered through silica gel with heptane/toluene (4:1), giving 6-fluoro-7-iodo-3-propylchroman as a colourless solid, which is sufficiently pure for further reaction.


1.2. Diethyl 2-(6-fluoro-3-propylchroman-7-yl)malonate



embedded image


17.0 g (52.2 mmol) of anhydrous caesium carbonate, 700 mg (3.67 mmol) of copper(I) iodide and 700 mg (4.11 mmol) of o-phenylphenol are initially introduced under dry nitrogen, a solution of 11.4 g (33.5 mmol) of 6-fluoro-7-iodo-3-propylchroman and 16.0 g (100 mmol) of diethyl malonate in 150 ml of THF is added, and the mixture is heated under reflux overnight. MTB ether is subsequently added to the batch, which is washed with dil. hydrochloric acid and dried over sodium sulfate. The solvent is removed in vacuo, and the crude product is purified by chromatography on silica gel with heptane/ethyl acetate (4:1). The product fraction (Rf=0.55) is reacted without further purification.


1.3. 2-(6-Fluoro-3-propylchroman-7-yl)propane-1,3-diol



embedded image


8.7 g (21.1 mmol) of the diethyl 2-(6-fluoro-3-propylchroman-7-yl)malonate obtained under 1.2. are initially introduced in 60 ml of toluene, and 106 ml (106 mmol) of a 1 M solution of diisobutylaluminium hydride in toluene are added dropwise at 5° C. The batch is subsequently added to ice-cold sat. ammonium chloride soln., acidified using dil. hydrochloric acid and extracted with MTB ether. The combined org. phases are dried over sodium sulfate and evaporated. Chromatography of the crude product on silica gel with MTB ether/heptane (4:1) gives 2-(6-fluoro-3-propylchroman-7-yl)propane-1,3-diol as a colourless solid.



19F-NMR (377 MHz, CDCl3)


δ=−129.0 ppm (dd, J=6.4 Hz, J=10.3 Hz, 1F, Ar—F).


1.4. 6-Fluoro-7-oxetan-3-yl-3-propylchroman



embedded image


3.80 g (13.7 mmol) of 2-(6-fluoro-3-propylchroman-7-yl)propane-1,3-diol are dissolved in 70 ml of THF, and 8.7 ml (13.7 mmol) of a 15 percent solution of n-butyllithium in hexane are added at 0° C. After 30 min, 2.7 g (14.2 mmol) of p-toluenesulfonyl chloride in 30 ml of THF are added, and the mixture is stirred at RT for 1 h and re-cooled to 0° C. After addition of a further 8.7 ml (13.7 mmol) of a 15% solution of n-butyllithium in hexane, the cooling is removed, and the batch is heated under reflux for 4 h. The batch is subsequently diluted with MTB ether and washed with water. The org. phase is dried over sodium sulfate and evaporated, and the crude product is purified by chromatography on silica gel with heptane/ethyl acetate (3:2). The product fractions (Rf=0.5) are evaporated, and the product is used without further purification.


1.5. 3-(4-Bromo-2,5-difluorophenyl)-2-(6-fluoro-3-propylchroman-7-yl)propan-1-ol



embedded image


4.50 g (16.6 mmol) of 1,4-dibromo-2,6-difluorobenzene are dissolved in 70 ml of ether, and 11 ml (18 mmol) of a 15 percent solution of n-butyllithium in hexane are added at −70° C. After 30 min, a solution of 3.00 g (11.0 mmol) of 6-fluoro-7-oxetan-3-yl-3-propylchroman in 30 ml of ether is added dropwise, and, after 1 h, 1.5 ml (11.9 mmol) of boron trifluoride diethyl ether complex are carefully added. The batch is left to stir for 2 h at −78° C. and overnight at RT and hydrolysed using sat. ammonium chloride soln. The org. phase is separated off and washed with water and sat. sodium chloride soln. and dried over sodium sulfate. The solvent is removed in vacuo, and the residue is chromatographed on silica gel, firstly with toluene and then with toluene/ethyl acetate (2:1), giving 3-(4-bromo-2,5-difluorophenyl)-2-(6-fluoro-3-propylchroman-7-yl)propan-1-ol as a colourless solid.


1.6. 7-Bromo-6,6′-difluoro-3′-propyl-3,4,3′,4′-tetrahydro-2H,2′H-[3,7]bichromenyl



embedded image


1.2 g (10.5 mmol) of potassium hydride (35 percent in paraffin oil) are initially introduced in 40 ml of THF, and a solution of 4.50 g (8.12 mmol) of 3-(4-bromo-2,5-difluorophenyl)-2-(6-fluoro-3-propylchroman-7-yl)propan-1-ol in 20 ml of THF is added dropwise at 30° C. The batch is subsequently stirred at 60° C. for 4 h, a little ethanol is added, and the batch is diluted with MTB ether and washed with sat. sodium chloride soln. The org. phase is dried over sodium sulfate, the solvent is removed in vacuo, and the crude product is filtered through silica gel with toluene and recrystallised from heptane/ethyl acetate, giving 7-bromo-6,6′-difluoro-3′-propyl-3,4,3′,4′-tetrahydro-2H,2′H-[3,7′]-bichromenyl as colourless crystals.



19F-NMR (377 MHz, CDCl3)


δ=−119.4 ppm (dd, J=6.2 Hz, J=8.5 Hz, 1F, Ar—F), −129.6 (ddd, J=6.5 Hz, J=6.5 Hz, J=10.4 Hz, 1F, Ar—F).


1.7. 6,6′-Difluoro-3′-propyl-3,4,3′,4′-tetrahydro-2H,2′H-[3,7′]-bichromenyl-7-carbonitrile



embedded image


1.4 g (3.31 mmol) of 7-bromo-6,6′-difluoro-3′-propyl-3,4,3′,4′-tetrahydro-2H,2′H-[3,7′]bichromenyl are dissolved in 20 ml of THF, and 3 ml (4.8 mmol) of a 15 percent solution of n-butyl-lithium in hexane are added at −50° C. The batch is left to stir for 2 h at −70° C., and a solution of 0.9 g (5.00 mmol) of p-toluenesulfonyl cyanide in 10 ml of THF is subsequently added at such a rate that the temperature does not exceed −65° C. After 30 min, the batch is allowed to thaw, diluted with ether and washed with dil. hydrochloric acid. The org. phase is dried over sodium sulfate and evaporated, and the crude product is chromatographed on silica gel with heptane/toluene (2:3), giving 6,6′-difluoro-3′-propyl-3,4,3′,4′-tetrahydro-2H,2′H-[3,7]bichromenyl-7-carbonitrile as colourless crystals of m.p. 122° C.


Phase behaviour: C 122 N (59) I


Example 2
(R)-6,8-difluoro-3-[5-((R)-6-fluoro-3-pentylchroman-7-yl)-1,3-dioxan-2-yl]chroman-7-carbonitrile
2.1. 2-(6-Fluoro-3-pentylchroman-7-yl)propane-1,3-diol



embedded image


The preparation is carried out analogously to the synthesis of 2-(6-fluoro-3-propylchroman-7-yl)propane-1,3-diol described under 1.3.


2.2. 6,8-Difluoro-2H-chromene-3-carbaldehyde
2.2.1. 3,5-Difluorosalicylaldehyde



embedded image


260 g (2.00 mol) of 2,4-difluorophenol are dissolved in 1.6 l of trifluoroacetic acid, and 560 g (4.00 mol) of hexamethylenetetramine are added in portions. After 30 min, the batch is warmed to 75° C. and stirred overnight. 2 l of 40 percent sulfuric acid are subsequently added at RT, the mixture is left to stir for 2.5 h, 1.5 l of ice-water are added, and the mixture is stirred for a further 30 min. The deposited precipitate is separated off, washed with water and taken up in dichloromethane. The resultant solution is dried over sodium sulfate and evaporated, giving 3,5-difluorosalicylaldehyde as a beige solid.


2.2.2. 6,8-Difluoro-2H-chromene-3-carbonitrile



embedded image


84 g (0.531 mol) of 3,5-difluorosalicylaldehyde are dissolved in 850 ml of acrylonitrile, 1 g (8 mmol) of p-methoxyphenol and 18 g (0.16 mol) of DABCO are added, and the mixture is heated overnight at 75° C. The batch is evaporated, the residue is taken up in dichloromethane, and the solution is filtered through silica gel, giving 6,8-difluoro-2H-chromene-3-carbonitrile, which is sufficiently pure for further reactions.


2.2.3. 6,8-Difluoro-2H-chromene-3-carbaldehyde



embedded image


47.0 g (243 mmol) of 6,8-difluoro-2H-chromene-3-carbonitrile are dissolved in 300 ml of toluene, and 260 ml (260 mmol) of a 1 M solution of diisobutylaluminium hydride in toluene are added at −20° C. After 1 h, the batch is allowed to thaw, the solution is added to ice-cold dil. hydrochloric acid, and the mixture is left to stir vigorously for 2 h. The aqueous phase is separated off and extracted with MTB ether. The combined org. phases are washed with water, dried over sodium sulfate and evaporated, giving 6,8-difluoro-2H-chromene-3-carbaldehyde having a content of 99.0% (GC).


2.3. 6,8-Difluoro-3-[5-(6-fluoro-3-pentylchroman-7-yl)-1,3-dioxan-2-yl]-2H-chromene



embedded image


1.30 g (4.39 mmol) of 2-(6-fluoro-3-pentylchroman-7-yl)propane-1,3-diol and 900 mg (4.59 mmol) of 6,8-difluoro-2H-chromene-3-carbaldehyde are dissolved in 50 ml of dichloromethane and heated under reflux on a water separator for 5 h in the presence of 50 mg of p-toluenesulfonic acid. The solution is subsequently washed with sat. sodium hydrogencarbonate soln. and dried over sodium sulfate. The solvent is removed in vacuo, and the residue is recrystallised from heptane/toluene, giving 6,8-difluoro-3-[5-(6-fluoro-3-pentylchroman-7-yl)-1,3-dioxan-2-yl]-2H-chromene (trans:cis=80:20) as a colourless solid.


2.4. (R)-6,8-difluoro-3-[5-((R)-6-fluoro-3-pentylchroman-7-yl)-1,3-dioxan-2-yl]chroman



embedded image


6,8-Difluoro-3-[5-(6-fluoro-3-pentylchroman-7-yl)-1,3-dioxan-2-yl]-2H-chromene is hydrogenated to completion in THF on a palladium/active carbon catalyst. The solution is filtered and evaporated, and the residue is recrystallised from heptane, giving isomerically pure (R)-6,8-difluoro-3-[5-((R)-6-fluoro-3-pentylchroman-7-yl)-1,3-dioxan-2-yl]chroman as a colourless solid.



19F-NMR (377 MHz, CDCl3)


δ=−121.8 ppm (t, J=8.6 Hz, 1F, Ar—F), −128.4 (ddd, J=6.4 Hz, J=10.4 Hz, 1F, Ar—F), −133.1 (dd, J=1.5 Hz, J=10.8 Hz, 1F, Ar—F).


2.5. (R)-6,8-difluoro-3-[5-((R)-6-fluoro-3-pentylchroman-7-yl)-1,3-dioxan-2-yl]chroman-7-carbonitrile



embedded image


800 mg (1.68 mmol) of (R)-6,8-difluoro-3-[5-((R)-6-fluoro-3-pentylchroman-7-yl)-1,3-dioxan-2-yl]chroman are dissolved in 30 ml of THF, and 1.7 ml (2.38 mmol) of a 1.4 M solution of s-butyllithium in cyclohexane are added at −50° C. The batch is warmed at −25° C. for 5 min, left to stir at −70° C. for 2 h, and a solution of 400 mg (2.21 mmol) of p-toluenesulfonyl cyanide in 10 ml of THF is subsequently added at such a rate that the temperature does not exceed −65° C. After 1 h, the batch is allowed to thaw, diluted with ether and washed with dil. hydrochloric acid. The org. phase is dried over sodium sulfate and evaporated, and the crude product is chromatographed on silica gel with toluene, giving (R)-6,8-difluoro-3-[5-((R)-6-fluoro-3-pentylchroman-7-yl)-1,3-dioxan-2-yl]chroman-7-carbonitrile as colourless crystals of m.p. 111° C.


Phase behaviour: Tg 6 C 111 N 145 I


Δε 83


Δn 0.140


Example 3
6,8-Difluoro-3-[5-(6-fluoro-3-pentylchroman-7-yl)-1,3-dioxan-2-yl]-7-trifluoromethoxychroman



embedded image


The synthesis described under Example 2 gives 6,8-difluoro-3-[5-(6-fluoro-3-pentylchroman-7-yl)-1,3-dioxan-2-yl]-7-trifluoromethoxychroman as a colourless solid.


Phase behaviour: Tg −22 C 88 SmA 175 N (174.8) I



19F-NMR (377 MHz, CDCl3)


δ=−59.79 ppm (t, J=7.0 Hz, 3F, —OCF3), 128.4 (dd, J=6.4 Hz, J=10.3 Hz, 1F, Ar—F), 137.2 (mc, 1F, Ar—F), 146.8 (mc, 1F, Ar—F).


Δn 0.102


Example 4
7-Cyano-6,8-difluoro-3-[2-(6-fluoro-3-pentylchroman-7-yl)ethyl]-2H-chromene
4.1 6-Fluoro-3-pentylchroman-7-carbaldehyde



embedded image


15.5 g (51.5 mmol) of 7-bromo-6-fluoro-3-pentylchroman are dissolved in 85 ml of THF, and 35 ml (55.7 mmol) of a 15 percent solution of n-butyllithium in n-hexane are slowly added at −70° C. After 1 h, 6.3 ml (56.7 mmol) of N-formylpiperidine in 15 ml of THF are added dropwise, and the mixture is stirred for 1 h. The batch is subsequently allowed to thaw, added to water, acidified using dil. hydrochloric acid and extracted three times with MTB ether. The combined org. phases are washed with water and sat. sodium chloride soln. and dried over sodium sulfate, the solvent is removed in vacuo, and the residue is recrystallised from heptane at −25° C., giving 6-fluoro-3-pentylchroman-7-carbaldehyde as colourless crystals (Rf=0.4; 1-chlorobutane).


4.2 (6-Fluoro-3-pentylchroman-7-yl)methanol



embedded image


11.1 g (44.3 mmol) of 6-fluoro-3-pentylchroman-7-carbaldehyde are dissolved in 100 ml of ethanol, and 2.0 g (52.8 mmol) of sodium borohydride are added in portions. After 3 h, the batch is diluted with water and extracted three times with MTB ether. The combined org. phases are washed with sat. sodium chloride soln. and dried over sodium sulfate, the solvent is removed in vacuo, and the residue is filtered through silica gel with dichloromethane (Rf=0.3), giving (6-fluoro-3-pentylchroman-7-yl)methanol as a colourless solid.


4.3 7-Bromomethyl-6-fluoro-3-pentylchroman



embedded image


10.2 g (38.9 mmol) of triphenylphosphine are suspended in 80 ml of acetonitrile, and 2.0 ml (39.0 mmol) of bromine are added dropwise with ice cooling. A solution of 10.0 g (38.4 mmol) of (6-fluoro-3-pentylchroman-7-yl)methanol in 20 ml of acetonitrile is subsequently added, and the mixture is stirred overnight at room temp. After addition of water, the mixture is extracted three times with n-heptane, and the combined org. phases are washed with water and dried over sodium sulfate. The solvent is removed in vacuo, and the residue is filtered through silica gel with heptane/toluene (4:1), giving 7-bromomethyl-6-fluoro-3-pentylchroman as a colourless oil.



19F-NMR (377 MHz, CDCl3)


δ=−128.7 ppm (dd, J=6.7 Hz, J=9.7 Hz, 1F).


4.4 (6-Fluoro-3-pentylchroman-7-ylmethyl)triphenylphosphonium bromide



embedded image


11.0 g (34.9 mmol) of 7-bromomethyl-6-fluoro-3-pentylchroman and 9.20 g (35.1 mmol) of triphenylphosphine are dissolved in 70 ml of acetonitrile, and the mixture is stirred overnight at room temp. The batch is subsequently cooled to 0° C., and the precipitated (6-fluoro-3-pentylchroman-7-ylmethyl)triphenylphosphonium bromide is filtered off with suction and dried in vacuo.


4.5 6,8-Difluoro-3-[2-(6-fluoro-3-pentylchroman-7-yl)vinyl]-2H-chromene



embedded image


10.2 g (17.7 mmol) of (6-fluoro-3-pentylchroman-7-ylmethyl)triphenylphosphonium bromide are dissolved in 50 ml of THF, and 2.0 g (17.8 mmol) of potassium tert-butoxide are added with ice cooling. After 1 h, a solution of 6,8-difluoro-2H-chromene-3-carbaldehyde in 50 ml of THF is slowly added dropwise, and the batch is left to stir overnight at room temp. The solution is subsequently added to water, acidified using dil. hydrochloric acid and extracted three times with MTB ether. The combined org. phases are washed with sat. sodium chloride soln. and dried over sodium sulfate. The solvent is removed in vacuo, and the residue is chromatographed on silica gel with heptane/toluene (1:1) and recrystallised from heptane at −20° C., giving 6,8-difluoro-3-[2-(6-fluoro-3-pentylchroman-7-yl)vinyl]-2H-chromene as yellow crystals.



19F-NMR (377 MHz, CDCl3)


δ=−120.3 ppm (dt, J=2.1 Hz, J=8.3 Hz, 1F), −128.8 (dd, J=6.5 Hz, J=10.7 Hz, 1F), −133.9 (mc, therein: d, J=10.3 Hz, 1F).


4.6 6,8-Difluoro-3-[2-(6-fluoro-3-pentylchroman-7-yl)ethyl]-2H-chromene



embedded image


6,8-Difluoro-3-[2-(6-fluoro-3-pentylchroman-7-yl)vinyl]-2H-chromene is dissolved in THF and hydrogenated to completion on a palladium/active carbon catalyst. The catalyst is filtered off, the solution is evaporated, the residue is filtered through silica gel with toluene/heptane (3:2), and the crude product is recrystallised from n-heptane at −25° C., giving colourless crystals of m.p. 84° C.


4.7 7-Cyano-6,8-difluoro-3-[2-(6-fluoro-3-pentylchroman-7-yl)ethyl]-2H-chromene



embedded image


Analogously to Example 2, step 2.5., 6,8-difluoro-3-[2-(6-fluoro-3-pentylchroman-7-yl)vinyl]-2H-chromene gives 7-cyano-6,8-difluoro-3-[2-(6-fluoro-3-pentylchroman-7-yl)ethyl]-2H-chromene as a colourless solid.


Phase behaviour: C 70 Sm (17) I.


Δε 53


Δn 0.119


The following compounds are prepared analogously to Examples 1-4

R1-A1-W1-A2-W2—Z4-A3-R2

where the substituents adopt the meanings as shown in the table.









TABLE







Further example compounds
















R1
A1
W1
A2
W2
Z4
A3
R2


















1
C3H7



embedded image





embedded image




F





2
C3H7



embedded image





embedded image




CF3





3
C3H7



embedded image





embedded image




OCF3





4
C3H7



embedded image





embedded image




CN





5
C5H11



embedded image





embedded image




F





6
C5H11



embedded image





embedded image




CF3





7
C5H11



embedded image





embedded image




OCF3





8
C5H11



embedded image





embedded image




CN





9


embedded image





embedded image





embedded image




F





10


embedded image





embedded image





embedded image




CF3





11


embedded image





embedded image





embedded image




OCF3





12


embedded image





embedded image





embedded image




CN





13
C3H7



embedded image





embedded image




F





14
C3H7



embedded image





embedded image




CF3





15
C3H7



embedded image





embedded image




OCF3





16
C3H7



embedded image





embedded image




CN





17
C5H11



embedded image





embedded image




F





18
C5H11



embedded image





embedded image




CF3





19
C5H11



embedded image





embedded image




OCF3





20
C5H11



embedded image





embedded image




CN





21


embedded image





embedded image





embedded image




F





22


embedded image





embedded image





embedded image




CF3





23


embedded image





embedded image





embedded image




OCF3





24


embedded image





embedded image





embedded image




CN





25
C3H7



embedded image





embedded image




F





26
C3H7



embedded image





embedded image




CF3





27
C3H7



embedded image





embedded image




OCF3





28
C3H7



embedded image





embedded image




CN





29
C5H11



embedded image





embedded image




F





30
C5H11



embedded image





embedded image




CF3





31
C5H11



embedded image





embedded image




OCF3





32
C5H11



embedded image





embedded image




CN





33


embedded image





embedded image





embedded image




F





34


embedded image





embedded image





embedded image




CF3





35


embedded image





embedded image





embedded image




OCF3





36


embedded image





embedded image





embedded image




CN





37
C3H7



embedded image





embedded image




F





38
C3H7



embedded image





embedded image




CF3





39
C3H7



embedded image





embedded image




OCF3





40
C3H7



embedded image





embedded image




CN





41
C5H11



embedded image





embedded image




F





42
C5H11



embedded image





embedded image




CF3





43
C5H11



embedded image





embedded image




OCF3





44
C5H11



embedded image





embedded image




CN





45


embedded image





embedded image





embedded image




F





46


embedded image





embedded image





embedded image




CF3





47


embedded image





embedded image





embedded image




OCF3





48


embedded image





embedded image





embedded image




CN





49
C3H7



embedded image





embedded image




F





50
C3H7



embedded image





embedded image




CF3





51
C3H7



embedded image





embedded image




OCF3





52
C3H7



embedded image





embedded image




CN





53
C5H11



embedded image





embedded image




F





54
C5H11



embedded image





embedded image




CF3





55
C5H11



embedded image





embedded image




OCF3





56
C5H11



embedded image





embedded image




CN





57


embedded image





embedded image





embedded image




F





58


embedded image





embedded image





embedded image




CF3





59


embedded image





embedded image





embedded image




OCF3





60


embedded image





embedded image





embedded image




CN





61
C3H7



embedded image





embedded image




F





62
C3H7



embedded image





embedded image




CF3





63
C3H7



embedded image





embedded image




OCF3





64
C3H7



embedded image





embedded image




CN





65
C5H11



embedded image





embedded image




F





66
C5H11



embedded image





embedded image




CF3





67
C5H11



embedded image





embedded image




OCF3





68
C5H11



embedded image





embedded image




CN





69


embedded image





embedded image





embedded image




F





70


embedded image





embedded image





embedded image




CF3





71


embedded image





embedded image





embedded image




OCF3





72


embedded image





embedded image





embedded image




CN





73
C3H7



embedded image





embedded image




F





74
C3H7



embedded image





embedded image




CF3





75
C3H7



embedded image





embedded image




OCF3





76
C3H7



embedded image





embedded image




CN





77
C5H11



embedded image





embedded image




F





78
C5H11



embedded image





embedded image




CF3





79
C5H11



embedded image





embedded image




OCF3





80
C5H11



embedded image





embedded image




CN





81


embedded image





embedded image





embedded image




F





82


embedded image





embedded image





embedded image




CF3





83


embedded image





embedded image





embedded image




OCF3





84


embedded image





embedded image





embedded image




CN





85
C3H7



embedded image




embedded image




embedded image




F





86
C3H7



embedded image




embedded image




embedded image




CF3





87
C3H7



embedded image




embedded image




embedded image




OCF3





88
C3H7



embedded image




embedded image




embedded image




CN





89
C5H11



embedded image




embedded image




embedded image




F





90
C5H11



embedded image




embedded image




embedded image




CF3





91
C5H11



embedded image




embedded image




embedded image




OCF3





92
C5H11



embedded image




embedded image




embedded image




CN





93


embedded image





embedded image




embedded image




embedded image




F





94


embedded image





embedded image




embedded image




embedded image




CF3





95


embedded image





embedded image




embedded image




embedded image




OCF3





96


embedded image





embedded image




embedded image




embedded image




CN





97
C3H7



embedded image




embedded image




embedded image




F





98
C3H7



embedded image




embedded image




embedded image




CF3





99
C3H7



embedded image




embedded image




embedded image




OCF3





100
C3H7



embedded image




embedded image




embedded image




CN





101
C5H11



embedded image




embedded image




embedded image




F





102
C5H11



embedded image




embedded image




embedded image




CF3





103
C5H11



embedded image




embedded image




embedded image




OCF3





104
C5H11



embedded image




embedded image




embedded image




CN





105


embedded image





embedded image




embedded image




embedded image




F





106


embedded image





embedded image




embedded image




embedded image




CF3





107


embedded image





embedded image




embedded image




embedded image




OCF3





108


embedded image





embedded image




embedded image




embedded image




CN





109
C3H7



embedded image




embedded image




embedded image




F





110
C3H7



embedded image




embedded image




embedded image




CF3





111
C3H7



embedded image




embedded image




embedded image




OCF3





112
C3H7



embedded image




embedded image




embedded image




CN





113
C5H11



embedded image




embedded image




embedded image




F





114
C5H11



embedded image




embedded image




embedded image




CF3





115
C5H11



embedded image




embedded image




embedded image




OCF3





116
C5H11



embedded image




embedded image




embedded image




CN





117


embedded image





embedded image




embedded image




embedded image




F





118


embedded image





embedded image




embedded image




embedded image




CF3





119


embedded image





embedded image




embedded image




embedded image




OCF3





120


embedded image





embedded image




embedded image




embedded image




CN





121
C3H7



embedded image




embedded image




embedded image




F





122
C3H7



embedded image




embedded image




embedded image




CF3





123
C3H7



embedded image




embedded image




embedded image




OCF3





124
C3H7



embedded image




embedded image




embedded image




CN





125
C5H11



embedded image




embedded image




embedded image




F





126
C5H11



embedded image




embedded image




embedded image




CF3





127
C5H11



embedded image




embedded image




embedded image




OCF3





128
C5H11



embedded image




embedded image




embedded image




CN





129


embedded image





embedded image




embedded image




embedded image




F





130


embedded image





embedded image




embedded image




embedded image




CF3





131


embedded image





embedded image




embedded image




embedded image




OCF3





132


embedded image





embedded image




embedded image




embedded image




CN





133
C3H7



embedded image




embedded image




embedded image




F





134
C3H7



embedded image




embedded image




embedded image




CF3





135
C3H7



embedded image




embedded image




embedded image




OCF3





136
C3H7



embedded image




embedded image




embedded image




CN





137
C5H11



embedded image




embedded image




embedded image




F





138
C5H11



embedded image




embedded image




embedded image




CF3





139
C5H11



embedded image




embedded image




embedded image




OCF3





140
C5H11



embedded image




embedded image




embedded image




CN





141


embedded image





embedded image




embedded image




embedded image




F





142


embedded image





embedded image




embedded image




embedded image




CF3





143


embedded image





embedded image




embedded image




embedded image




OCF3





144


embedded image





embedded image




embedded image




embedded image




CN





145
C3H7



embedded image




embedded image




embedded image




F





146
C3H7



embedded image




embedded image




embedded image




CF3





147
C3H7



embedded image




embedded image




embedded image




OCF3





148
C3H7



embedded image




embedded image




embedded image




CN





149
C5H11



embedded image




embedded image




embedded image




F





150
C5H11



embedded image




embedded image




embedded image




CF3





151
C5H11



embedded image




embedded image




embedded image




OCF3





152
C5H11



embedded image




embedded image




embedded image




CN





153


embedded image





embedded image




embedded image




embedded image




F





154


embedded image





embedded image




embedded image




embedded image




CF3





155


embedded image





embedded image




embedded image




embedded image




OCF3





156


embedded image





embedded image




embedded image




embedded image




CN





157
C3H7



embedded image




embedded image




embedded image




F





158
C3H7



embedded image




embedded image




embedded image




CF3





159
C3H7



embedded image




embedded image




embedded image




OCF3





160
C3H7



embedded image




embedded image




embedded image




CN





161
C5H11



embedded image




embedded image




embedded image




F





162
C5H11



embedded image




embedded image




embedded image




CF3





163
C5H11



embedded image




embedded image




embedded image




OCF3





164
C5H11



embedded image




embedded image




embedded image




CN





165


embedded image





embedded image




embedded image




embedded image




F





166


embedded image





embedded image




embedded image




embedded image




CF3





167


embedded image





embedded image




embedded image




embedded image




OCF3





168


embedded image





embedded image




embedded image




embedded image




CN





169
C3H7


embedded image




embedded image





embedded image




F





170
C3H7


embedded image




embedded image





embedded image




CF3





171
C3H7


embedded image




embedded image





embedded image




OCF3





172
C3H7


embedded image




embedded image





embedded image




CN





173
C5H11


embedded image




embedded image





embedded image




F





174
C5H11


embedded image




embedded image





embedded image




CF3





175
C5H11


embedded image




embedded image





embedded image




OCF3





176
C5H11


embedded image




embedded image





embedded image




CN





177


embedded image




embedded image




embedded image





embedded image




F





178


embedded image




embedded image




embedded image





embedded image




CF3





179


embedded image




embedded image




embedded image





embedded image




OCF3





180


embedded image




embedded image




embedded image





embedded image




CN





181
C3H7


embedded image




embedded image





embedded image




F





182
C3H7


embedded image




embedded image





embedded image




CF3





183
C3H7


embedded image




embedded image





embedded image




OCF3





184
C3H7


embedded image




embedded image





embedded image




CN





185
C5H11


embedded image




embedded image





embedded image




F





186
C5H11


embedded image




embedded image





embedded image




CF3





187
C5H11


embedded image




embedded image





embedded image




OCF3





188
C5H11


embedded image




embedded image





embedded image




CN





189


embedded image




embedded image




embedded image





embedded image




F





190


embedded image




embedded image




embedded image





embedded image




CF3





191


embedded image




embedded image




embedded image





embedded image




OCF3





192


embedded image




embedded image




embedded image





embedded image




CN





193
C3H7


embedded image




embedded image





embedded image




F





194
C3H7


embedded image




embedded image





embedded image




CF3





195
C3H7


embedded image




embedded image





embedded image




OCF3





196
C3H7


embedded image




embedded image





embedded image




CN





197
C5H11


embedded image




embedded image





embedded image




F





198
C5H11


embedded image




embedded image





embedded image




CF3





199
C5H11


embedded image




embedded image





embedded image




OCF3





200
C5H11


embedded image




embedded image





embedded image




CN





201


embedded image




embedded image




embedded image





embedded image




F





202


embedded image




embedded image




embedded image





embedded image




CF3





203


embedded image




embedded image




embedded image





embedded image




OCF3





204


embedded image




embedded image




embedded image





embedded image




CN





205
C3H7


embedded image




embedded image





embedded image




F





206
C3H7


embedded image




embedded image





embedded image




CF3





207
C3H7


embedded image




embedded image





embedded image




OCF3





208
C3H7


embedded image




embedded image





embedded image




CN





209
C5H11


embedded image




embedded image





embedded image




F





210
C5H11


embedded image




embedded image





embedded image




CF3





211
C5H11


embedded image




embedded image





embedded image




OCF3





212
C5H11


embedded image




embedded image





embedded image




CN





213


embedded image




embedded image




embedded image





embedded image




F





214


embedded image




embedded image




embedded image





embedded image




CF3





215


embedded image




embedded image




embedded image





embedded image




OCF3





216


embedded image




embedded image




embedded image





embedded image




CN





217
C3H7


embedded image




embedded image





embedded image




F





218
C3H7


embedded image




embedded image





embedded image




CF3





219
C3H7


embedded image




embedded image





embedded image




OCF3





220
C3H7


embedded image




embedded image





embedded image




CN





221
C5H11


embedded image




embedded image





embedded image




F





222
C5H11


embedded image




embedded image





embedded image




CF3





223
C5H11


embedded image




embedded image





embedded image




OCF3





224
C5H11


embedded image




embedded image





embedded image




CN





225


embedded image




embedded image




embedded image





embedded image




F





226


embedded image




embedded image




embedded image





embedded image




CF3





227


embedded image




embedded image




embedded image





embedded image




OCF3





228


embedded image




embedded image




embedded image





embedded image




CN





229
C3H7


embedded image




embedded image





embedded image




F





230
C3H7


embedded image




embedded image





embedded image




CF3





231
C3H7


embedded image




embedded image





embedded image




OCF3





232
C3H7


embedded image




embedded image





embedded image




CN





233
C5H11


embedded image




embedded image





embedded image




F





234
C5H11


embedded image




embedded image





embedded image




CF3





235
C5H11


embedded image




embedded image





embedded image




OCF3





236
C5H11


embedded image




embedded image





embedded image




CN





237


embedded image




embedded image




embedded image





embedded image




F





238


embedded image




embedded image




embedded image





embedded image




CF3





239


embedded image




embedded image




embedded image





embedded image




OCF3





240


embedded image




embedded image




embedded image





embedded image




CN





241
C3H7


embedded image




embedded image





embedded image




F





242
C3H7


embedded image




embedded image





embedded image




CF3





243
C3H7


embedded image




embedded image





embedded image




OCF3





244
C3H7


embedded image




embedded image





embedded image




CN





245
C5H11


embedded image




embedded image





embedded image




F





246
C5H11


embedded image




embedded image





embedded image




CF3





247
C5H11


embedded image




embedded image





embedded image




OCF3





248
C5H11


embedded image




embedded image





embedded image




CN





249


embedded image




embedded image




embedded image





embedded image




F





250


embedded image




embedded image




embedded image





embedded image




CF3





251


embedded image




embedded image




embedded image





embedded image




OCF3





252


embedded image




embedded image




embedded image





embedded image




CN





253
C3H7


embedded image




embedded image





embedded image




F





254
C3H7


embedded image




embedded image





embedded image




CF3





255
C3H7


embedded image




embedded image





embedded image




OCF3





256
C3H7


embedded image




embedded image





embedded image




CN





257
C5H11


embedded image




embedded image





embedded image




F





258
C5H11


embedded image




embedded image





embedded image




CF3





259
C5H11


embedded image




embedded image





embedded image




OCF3





260
C5H11


embedded image




embedded image





embedded image




CN





261


embedded image




embedded image




embedded image





embedded image




F





262


embedded image




embedded image




embedded image





embedded image




CF3





263


embedded image




embedded image




embedded image





embedded image




OCF3





264


embedded image




embedded image




embedded image





embedded image




CN





265
C3H7


embedded image




embedded image





embedded image




F





266
C3H7


embedded image




embedded image





embedded image




CF3





267
C3H7


embedded image




embedded image





embedded image




OCF3





268
C3H7


embedded image




embedded image





embedded image




CN





269
C5H11


embedded image




embedded image





embedded image




F





270
C5H11


embedded image




embedded image





embedded image




CF3





271
C5H11


embedded image




embedded image





embedded image




OCF3





272
C5H11


embedded image




embedded image





embedded image




CN





273


embedded image




embedded image




embedded image





embedded image




F





274


embedded image




embedded image




embedded image





embedded image




CF3





275


embedded image




embedded image




embedded image





embedded image




OCF3





276


embedded image




embedded image




embedded image





embedded image




CN





277
C3H7


embedded image




embedded image





embedded image




F





278
C3H7


embedded image




embedded image





embedded image




CF3





279
C3H7


embedded image




embedded image





embedded image




OCF3





280
C3H7


embedded image




embedded image





embedded image




CN





281
C5H11


embedded image




embedded image





embedded image




F





282
C5H11


embedded image




embedded image





embedded image




CF3





283
C5H11


embedded image




embedded image





embedded image




OCF3





284
C5H11


embedded image




embedded image





embedded image




CN





285


embedded image




embedded image




embedded image





embedded image




F





286


embedded image




embedded image




embedded image





embedded image




CF3





287


embedded image




embedded image




embedded image





embedded image




OCF3





288


embedded image




embedded image




embedded image





embedded image




CN





289
C3H7


embedded image




embedded image





embedded image




F





290
C3H7


embedded image




embedded image





embedded image




CF3





291
C3H7


embedded image




embedded image





embedded image




OCF3





292
C3H7


embedded image




embedded image





embedded image




CN





293
C5H11


embedded image




embedded image





embedded image




F





294
C5H11


embedded image




embedded image





embedded image




CF3





295
C5H11


embedded image




embedded image





embedded image




OCF3





296
C5H11


embedded image




embedded image





embedded image




CN





297


embedded image




embedded image




embedded image





embedded image




F





298


embedded image




embedded image




embedded image





embedded image




CF3





299


embedded image




embedded image




embedded image





embedded image




OCF3





300


embedded image




embedded image




embedded image





embedded image




CN





301
C3H7


embedded image




embedded image





embedded image




F





302
C3H7


embedded image




embedded image





embedded image




CF3





303
C3H7


embedded image




embedded image





embedded image




OCF3





304
C3H7


embedded image




embedded image





embedded image




CN





305
C5H11


embedded image




embedded image





embedded image




F





306
C5H11


embedded image




embedded image





embedded image




CF3





307
C5H11


embedded image




embedded image





embedded image




OCF3





308
C5H11


embedded image




embedded image





embedded image




CN





309


embedded image




embedded image




embedded image





embedded image




F





310


embedded image




embedded image




embedded image





embedded image




CF3





311


embedded image




embedded image




embedded image





embedded image




OCF3





312


embedded image




embedded image




embedded image





embedded image




CN





313
C3H7


embedded image




embedded image





embedded image




F





314
C3H7


embedded image




embedded image





embedded image




CF3





315
C3H7


embedded image




embedded image





embedded image




OCF3





316
C3H7


embedded image




embedded image





embedded image




CN





317
C5H11


embedded image




embedded image





embedded image




F





318
C5H11


embedded image




embedded image





embedded image




CF3





319
C5H11


embedded image




embedded image





embedded image




OCF3





320
C5H11


embedded image




embedded image





embedded image




CN





321


embedded image




embedded image




embedded image





embedded image




F





322


embedded image




embedded image




embedded image





embedded image




CF3





323


embedded image




embedded image




embedded image





embedded image




OCF3





324


embedded image




embedded image




embedded image





embedded image




CN





325
C3H7


embedded image




embedded image





embedded image




F





326
C3H7


embedded image




embedded image





embedded image




CF3





327
C3H7


embedded image




embedded image





embedded image




OCF3





328
C3H7


embedded image




embedded image





embedded image




CN





329
C5H11


embedded image




embedded image





embedded image




F





330
C5H11


embedded image




embedded image





embedded image




CF3





331
C5H11


embedded image




embedded image





embedded image




OCF3





332
C5H11


embedded image




embedded image





embedded image




CN





333


embedded image




embedded image




embedded image





embedded image




F





334


embedded image




embedded image




embedded image





embedded image




CF3





335


embedded image




embedded image




embedded image





embedded image




OCF3





336


embedded image




embedded image




embedded image





embedded image




CN





337
C3H7



embedded image




embedded image




embedded image




F





338
C3H7



embedded image




embedded image




embedded image




CF3





339
C3H7



embedded image




embedded image




embedded image




OCF3





340
C3H7



embedded image




embedded image




embedded image




CN





341
C5H11



embedded image




embedded image




embedded image




F





342
C5H11



embedded image




embedded image




embedded image




CF3





343
C5H11



embedded image




embedded image




embedded image




OCF3





344
C5H11



embedded image




embedded image




embedded image




CN





345


embedded image





embedded image




embedded image




embedded image




F





346


embedded image





embedded image




embedded image




embedded image




CF3





347


embedded image





embedded image




embedded image




embedded image




OCF3





348


embedded image





embedded image




embedded image




embedded image




CN





349
C3H7



embedded image




embedded image




embedded image




F





350
C3H7



embedded image




embedded image




embedded image




CF3





351
C3H7



embedded image




embedded image




embedded image




OCF3





352
C3H7



embedded image




embedded image




embedded image




CN





353
C5H11



embedded image




embedded image




embedded image




F





354
C5H11



embedded image




embedded image




embedded image




CF3





355
C5H11



embedded image




embedded image




embedded image




OCF3





356
C5H11



embedded image




embedded image




embedded image




CN





357


embedded image





embedded image




embedded image




embedded image




F





358


embedded image





embedded image




embedded image




embedded image




CF3





359


embedded image





embedded image




embedded image




embedded image




OCF3





360


embedded image





embedded image




embedded image




embedded image




CN





361
C3H7



embedded image




embedded image




embedded image




F





362
C3H7



embedded image




embedded image




embedded image




CF3





363
C3H7



embedded image




embedded image




embedded image




OCF3





364
C3H7



embedded image




embedded image




embedded image




CN





365
C5H11



embedded image




embedded image




embedded image




F





366
C5H11



embedded image




embedded image




embedded image




CF3





367
C5H11



embedded image




embedded image




embedded image




OCF3





368
C5H11



embedded image




embedded image




embedded image




CN





369


embedded image





embedded image




embedded image




embedded image




F





370


embedded image





embedded image




embedded image




embedded image




CF3





371


embedded image





embedded image




embedded image




embedded image




OCF3





372


embedded image





embedded image




embedded image




embedded image




CN





373
C3H7



embedded image




embedded image




embedded image




F





374
C3H7



embedded image




embedded image




embedded image




CF3





375
C3H7



embedded image




embedded image




embedded image




OCF3





376
C3H7



embedded image




embedded image




embedded image




CN





377
C5H11



embedded image




embedded image




embedded image




F





378
C5H11



embedded image




embedded image




embedded image




CF3





379
C5H11



embedded image




embedded image




embedded image




OCF3





380
C5H11



embedded image




embedded image




embedded image




CN





381


embedded image





embedded image




embedded image




embedded image




F





382


embedded image





embedded image




embedded image




embedded image




CF3





383


embedded image





embedded image




embedded image




embedded image




OCF3





384


embedded image





embedded image




embedded image




embedded image




CN





385
C3H7



embedded image




embedded image




embedded image




F





386
C3H7



embedded image




embedded image




embedded image




CF3





387
C3H7



embedded image




embedded image




embedded image




OCF3





388
C3H7



embedded image




embedded image




embedded image




CN





389
C5H11



embedded image




embedded image




embedded image




F





390
C5H11



embedded image




embedded image




embedded image




CF3





391
C5H11



embedded image




embedded image




embedded image




OCF3





392
C5H11



embedded image




embedded image




embedded image




CN





393


embedded image





embedded image




embedded image




embedded image




F





394


embedded image





embedded image




embedded image




embedded image




CF3





395


embedded image





embedded image




embedded image




embedded image




OCF3





396


embedded image





embedded image




embedded image




embedded image




CN





397
C3H7



embedded image




embedded image




embedded image




F





398
C3H7



embedded image




embedded image




embedded image




CF3





399
C3H7



embedded image




embedded image




embedded image




OCF3





400
C3H7



embedded image




embedded image




embedded image




CN





401
C5H11



embedded image




embedded image




embedded image




F





402
C5H11



embedded image




embedded image




embedded image




CF3





403
C5H11



embedded image




embedded image




embedded image




OCF3





404
C5H11



embedded image




embedded image




embedded image




CN





405


embedded image





embedded image




embedded image




embedded image




F





406


embedded image





embedded image




embedded image




embedded image




CF3





407


embedded image





embedded image




embedded image




embedded image




OCF3





408


embedded image





embedded image




embedded image




embedded image




CN





409
C3H7



embedded image




embedded image




embedded image




F





410
C3H7



embedded image




embedded image




embedded image




CF3





411
C3H7



embedded image




embedded image




embedded image




OCF3





412
C3H7



embedded image




embedded image




embedded image




CN





413
C5H11



embedded image




embedded image




embedded image




F





414
C5H11



embedded image




embedded image




embedded image




CF3





415
C5H11



embedded image




embedded image




embedded image




OCF3





416
C5H11



embedded image




embedded image




embedded image




CN





417


embedded image





embedded image




embedded image




embedded image




F





418


embedded image





embedded image




embedded image




embedded image




CF3





419


embedded image





embedded image




embedded image




embedded image




OCF3





420


embedded image





embedded image




embedded image




embedded image




CN





421
C3H7



embedded image





embedded image





embedded image


F





422
C3H7



embedded image





embedded image





embedded image


CF3





423
C3H7



embedded image





embedded image





embedded image


OCF3





424
C3H7



embedded image





embedded image





embedded image


CN





425
C5H11



embedded image





embedded image





embedded image


F





426
C5H11



embedded image





embedded image





embedded image


CF3





427
C5H11



embedded image





embedded image





embedded image


OCF3





428
C5H11



embedded image





embedded image





embedded image


CN





429


embedded image





embedded image





embedded image





embedded image


F





430


embedded image





embedded image





embedded image





embedded image


CF3





431


embedded image





embedded image





embedded image





embedded image


OCF3





432


embedded image





embedded image





embedded image





embedded image


CN





433
C3H7



embedded image





embedded image





embedded image


F





434
C3H7



embedded image





embedded image





embedded image


CF3





435
C3H7



embedded image





embedded image





embedded image


OCF3





436
C3H7



embedded image





embedded image





embedded image


CN





437
C5H11



embedded image





embedded image





embedded image


F





438
C5H11



embedded image





embedded image





embedded image


CF3





439
C5H11



embedded image





embedded image





embedded image


OCF3





440
C5H11



embedded image





embedded image





embedded image


CN





441


embedded image





embedded image





embedded image





embedded image


F





442


embedded image





embedded image





embedded image





embedded image


CF3





443


embedded image





embedded image





embedded image





embedded image


OCF3





444


embedded image





embedded image





embedded image





embedded image


CN





445
C3H7



embedded image





embedded image





embedded image


F





446
C3H7



embedded image





embedded image





embedded image


CF3





447
C3H7



embedded image





embedded image





embedded image


OCF3





448
C3H7



embedded image





embedded image





embedded image


CN





449
C5H11



embedded image





embedded image





embedded image


F





450
C5H11



embedded image





embedded image





embedded image


CF3





451
C5H11



embedded image





embedded image





embedded image


OCF3





452
C5H11



embedded image





embedded image





embedded image


CN





453


embedded image





embedded image





embedded image





embedded image


F





454


embedded image





embedded image





embedded image





embedded image


CF3





455


embedded image





embedded image





embedded image





embedded image


OCF3





456


embedded image





embedded image





embedded image





embedded image


CN





457
C3H7



embedded image





embedded image





embedded image


F





458
C3H7



embedded image





embedded image





embedded image


CF3





459
C3H7



embedded image





embedded image





embedded image


OCF3





460
C3H7



embedded image





embedded image





embedded image


CN





461
C5H11



embedded image





embedded image





embedded image


F





462
C5H11



embedded image





embedded image





embedded image


CF3





463
C5H11



embedded image





embedded image





embedded image


OCF3





464
C5H11



embedded image





embedded image





embedded image


CN





465


embedded image





embedded image





embedded image





embedded image


F





466


embedded image





embedded image





embedded image





embedded image


CF3





467


embedded image





embedded image





embedded image





embedded image


OCF3





468


embedded image





embedded image





embedded image





embedded image


CN





469
C3H7



embedded image





embedded image





embedded image


F





470
C3H7



embedded image





embedded image





embedded image


CF3





471
C3H7



embedded image





embedded image





embedded image


OCF3





472
C3H7



embedded image





embedded image





embedded image


CN





473
C5H11



embedded image





embedded image





embedded image


F





474
C5H11



embedded image





embedded image





embedded image


CF3





475
C5H11



embedded image





embedded image





embedded image


OCF3





476
C5H11



embedded image





embedded image





embedded image


CN





477


embedded image





embedded image





embedded image





embedded image


F





478


embedded image





embedded image





embedded image





embedded image


CF3





479


embedded image





embedded image





embedded image





embedded image


OCF3





480


embedded image





embedded image





embedded image





embedded image


CN





481
C3H7



embedded image





embedded image





embedded image


F





482
C3H7



embedded image





embedded image





embedded image


CF3





483
C3H7



embedded image





embedded image





embedded image


OCF3





484
C3H7



embedded image





embedded image





embedded image


CN





485
C5H11



embedded image





embedded image





embedded image


F





486
C5H11



embedded image





embedded image





embedded image


CF3





487
C5H11



embedded image





embedded image





embedded image


OCF3





488
C5H11



embedded image





embedded image





embedded image


CN





489


embedded image





embedded image





embedded image





embedded image


F





490


embedded image





embedded image





embedded image





embedded image


CF3





491


embedded image





embedded image





embedded image





embedded image


OCF3





492


embedded image





embedded image





embedded image





embedded image


CN





493
C3H7



embedded image





embedded image





embedded image


F





494
C3H7



embedded image





embedded image





embedded image


CF3





495
C3H7



embedded image





embedded image





embedded image


OCF3





496
C3H7



embedded image





embedded image





embedded image


CN





497
C5H11



embedded image





embedded image





embedded image


F





498
C5H11



embedded image





embedded image





embedded image


CF3





499
C5H11



embedded image





embedded image





embedded image


OCF3





500
C5H11



embedded image





embedded image





embedded image


CN





501


embedded image





embedded image





embedded image





embedded image


F





502


embedded image





embedded image





embedded image





embedded image


CF3





503


embedded image





embedded image





embedded image





embedded image


OCF3





504


embedded image





embedded image





embedded image





embedded image


CN





505
C3H7



embedded image




embedded image




embedded image




F





506
C3H7



embedded image




embedded image




embedded image




CF3





507
C3H7



embedded image




embedded image




embedded image




OCF3





508
C3H7



embedded image




embedded image




embedded image




CN





509
C5H11



embedded image




embedded image




embedded image




F





510
C5H11



embedded image




embedded image




embedded image




CF3





511
C5H11



embedded image




embedded image




embedded image




OCF3





512
C5H11



embedded image




embedded image




embedded image




CN





513


embedded image





embedded image




embedded image




embedded image




F





514


embedded image





embedded image




embedded image




embedded image




CF3





515


embedded image





embedded image




embedded image




embedded image




OCF3





516


embedded image





embedded image




embedded image




embedded image




CN





517
C3H7



embedded image




embedded image




embedded image




F





518
C3H7



embedded image




embedded image




embedded image




CF3





519
C3H7



embedded image




embedded image




embedded image




OCF3





520
C3H7



embedded image




embedded image




embedded image




CN





521
C5H11



embedded image




embedded image




embedded image




F





522
C5H11



embedded image




embedded image




embedded image




CF3





523
C5H11



embedded image




embedded image




embedded image




OCF3





524
C5H11



embedded image




embedded image




embedded image




CN





525


embedded image





embedded image




embedded image




embedded image




F





526


embedded image





embedded image




embedded image




embedded image




CF3





527


embedded image





embedded image




embedded image




embedded image




OCF3





528


embedded image





embedded image




embedded image




embedded image




CN





529
C3H7



embedded image




embedded image




embedded image




F





530
C3H7



embedded image




embedded image




embedded image




CF3





531
C3H7



embedded image




embedded image




embedded image




OCF3





532
C3H7



embedded image




embedded image




embedded image




CN





533
C5H11



embedded image




embedded image




embedded image




F





534
C5H11



embedded image




embedded image




embedded image




CF3





535
C5H11



embedded image




embedded image




embedded image




OCF3





536
C5H11



embedded image




embedded image




embedded image




CN





537


embedded image





embedded image




embedded image




embedded image




F





538


embedded image





embedded image




embedded image




embedded image




CF3





539


embedded image





embedded image




embedded image




embedded image




OCF3





540


embedded image





embedded image




embedded image




embedded image




CN





541
C3H7



embedded image




embedded image




embedded image




F





542
C3H7



embedded image




embedded image




embedded image




CF3





543
C3H7



embedded image




embedded image




embedded image




OCF3





544
C3H7



embedded image




embedded image




embedded image




CN





545
C5H11



embedded image




embedded image




embedded image




F





546
C5H11



embedded image




embedded image




embedded image




CF3





547
C5H11



embedded image




embedded image




embedded image




OCF3





548
C5H11



embedded image




embedded image




embedded image




CN





549


embedded image





embedded image




embedded image




embedded image




F





550


embedded image





embedded image




embedded image




embedded image




CF3





551


embedded image





embedded image




embedded image




embedded image




OCF3





552


embedded image





embedded image




embedded image




embedded image




CN





553
C3H7



embedded image




embedded image




embedded image




F





554
C3H7



embedded image




embedded image




embedded image




CF3





555
C3H7



embedded image




embedded image




embedded image




OCF3





556
C3H7



embedded image




embedded image




embedded image




CN





557
C5H11



embedded image




embedded image




embedded image




F





558
C5H11



embedded image




embedded image




embedded image




CF3





559
C5H11



embedded image




embedded image




embedded image




OCF3





560
C5H11



embedded image




embedded image




embedded image




CN





561


embedded image





embedded image




embedded image




embedded image




F





562


embedded image





embedded image




embedded image




embedded image




CF3





563


embedded image





embedded image




embedded image




embedded image




OCF3





564


embedded image





embedded image




embedded image




embedded image




CN





565
C3H7



embedded image




embedded image




embedded image




F





566
C3H7



embedded image




embedded image




embedded image




CF3





567
C3H7



embedded image




embedded image




embedded image




OCF3





568
C3H7



embedded image




embedded image




embedded image




CN





569
C5H11



embedded image




embedded image




embedded image




F





570
C5H11



embedded image




embedded image




embedded image




CF3





571
C5H11



embedded image




embedded image




embedded image




OCF3





572
C5H11



embedded image




embedded image




embedded image




CN





573


embedded image





embedded image




embedded image




embedded image




F





574


embedded image





embedded image




embedded image




embedded image




CF3





575


embedded image





embedded image




embedded image




embedded image




OCF3





576


embedded image





embedded image




embedded image




embedded image




CN





577
C3H7



embedded image




embedded image




embedded image




F





578
C3H7



embedded image




embedded image




embedded image




CF3





579
C3H7



embedded image




embedded image




embedded image




OCF3





580
C3H7



embedded image




embedded image




embedded image




CN





581
C5H11



embedded image




embedded image




embedded image




F





582
C5H11



embedded image




embedded image




embedded image




CF3





583
C5H11



embedded image




embedded image




embedded image




OCF3





584
C5H11



embedded image




embedded image




embedded image




CN





585


embedded image





embedded image




embedded image




embedded image




F





586


embedded image





embedded image




embedded image




embedded image




CF3





587


embedded image





embedded image




embedded image




embedded image




OCF3





588


embedded image





embedded image




embedded image




embedded image




CN





589
C3H7



embedded image





embedded image





embedded image


F





590
C3H7



embedded image





embedded image





embedded image


CF3





591
C3H7



embedded image





embedded image





embedded image


OCF3





592
C3H7



embedded image





embedded image





embedded image


CN





593
C5H11



embedded image





embedded image





embedded image


F





594
C5H11



embedded image





embedded image





embedded image


CF3





595
C5H11



embedded image





embedded image





embedded image


OCF3





596
C5H11



embedded image





embedded image





embedded image


CN





597


embedded image





embedded image





embedded image





embedded image


F





598


embedded image





embedded image





embedded image





embedded image


CF3





599


embedded image





embedded image





embedded image





embedded image


OCF3





600


embedded image





embedded image





embedded image





embedded image


CN





601
C3H7



embedded image





embedded image





embedded image


F





602
C3H7



embedded image





embedded image





embedded image


CF3





603
C3H7



embedded image





embedded image





embedded image


OCF3





604
C3H7



embedded image





embedded image





embedded image


CN





605
C5H11



embedded image





embedded image





embedded image


F





606
C5H11



embedded image





embedded image





embedded image


CF3





607
C5H11



embedded image





embedded image





embedded image


OCF3





608
C5H11



embedded image





embedded image





embedded image


CN





609


embedded image





embedded image





embedded image





embedded image


F





610


embedded image





embedded image





embedded image





embedded image


CF3





611


embedded image





embedded image





embedded image





embedded image


OCF3





612


embedded image





embedded image





embedded image





embedded image


CN





613
C3H7



embedded image





embedded image





embedded image


F





614
C3H7



embedded image





embedded image





embedded image


CF3





615
C3H7



embedded image





embedded image





embedded image


OCF3





616
C3H7



embedded image





embedded image





embedded image


CN





617
C5H11



embedded image





embedded image





embedded image


F





618
C5H11



embedded image





embedded image





embedded image


CF3





619
C5H11



embedded image





embedded image





embedded image


OCF3





620
C5H11



embedded image





embedded image





embedded image


CN





621


embedded image





embedded image





embedded image





embedded image


F





622


embedded image





embedded image





embedded image





embedded image


CF3





623


embedded image





embedded image





embedded image





embedded image


OCF3





624


embedded image





embedded image





embedded image





embedded image


CN





625
C3H7



embedded image





embedded image





embedded image


F





626
C3H7



embedded image





embedded image





embedded image


CF3





627
C3H7



embedded image





embedded image





embedded image


OCF3





628
C3H7



embedded image





embedded image





embedded image


CN





629
C5H11



embedded image





embedded image





embedded image


F





630
C5H11



embedded image





embedded image





embedded image


CF3





631
C5H11



embedded image





embedded image





embedded image


OCF3





632
C5H11



embedded image





embedded image





embedded image


CN





633


embedded image





embedded image





embedded image





embedded image


F





634


embedded image





embedded image





embedded image





embedded image


CF3





635


embedded image





embedded image





embedded image





embedded image


OCF3





636


embedded image





embedded image





embedded image





embedded image


CN





637
C3H7



embedded image





embedded image





embedded image


F





638
C3H7



embedded image





embedded image





embedded image


CF3





639
C3H7



embedded image





embedded image





embedded image


OCF3





640
C3H7



embedded image





embedded image





embedded image


CN





641
C5H11



embedded image





embedded image





embedded image


F





642
C5H11



embedded image





embedded image





embedded image


CF3





643
C5H11



embedded image





embedded image





embedded image


OCF3





644
C5H11



embedded image





embedded image





embedded image


CN





645


embedded image





embedded image





embedded image





embedded image


F





646


embedded image





embedded image





embedded image





embedded image


CF3





647


embedded image





embedded image





embedded image





embedded image


OCF3





648


embedded image





embedded image





embedded image





embedded image


CN





649
C3H7



embedded image





embedded image





embedded image


F





650
C3H7



embedded image





embedded image





embedded image


CF3





651
C3H7



embedded image





embedded image





embedded image


OCF3





652
C3H7



embedded image





embedded image





embedded image


CN





653
C5H11



embedded image





embedded image





embedded image


F





654
C5H11



embedded image





embedded image





embedded image


CF3





655
C5H11



embedded image





embedded image





embedded image


OCF3





656
C5H11



embedded image





embedded image





embedded image


CN





657


embedded image





embedded image





embedded image





embedded image


F





658


embedded image





embedded image





embedded image





embedded image


CF3





659


embedded image





embedded image





embedded image





embedded image


OCF3





660


embedded image





embedded image





embedded image





embedded image


CN





661
C3H7



embedded image





embedded image





embedded image


F





662
C3H7



embedded image





embedded image





embedded image


CF3





663
C3H7



embedded image





embedded image





embedded image


OCF3





664
C3H7



embedded image





embedded image





embedded image


CN





665
C5H11



embedded image





embedded image





embedded image


F





666
C5H11



embedded image





embedded image





embedded image


CF3





667
C5H11



embedded image





embedded image





embedded image


OCF3





668
C5H11



embedded image





embedded image





embedded image


CN





669


embedded image





embedded image





embedded image





embedded image


F





670


embedded image





embedded image





embedded image





embedded image


CF3





671


embedded image





embedded image





embedded image





embedded image


OCF3





672


embedded image





embedded image





embedded image





embedded image


CN





673
C3H7


embedded image




embedded image





embedded image




F





674
C3H7


embedded image




embedded image





embedded image




CF3





675
C3H7


embedded image




embedded image





embedded image




OCF3





676
C3H7


embedded image




embedded image





embedded image




CN





677
C5H11


embedded image




embedded image





embedded image




F





678
C5H11


embedded image




embedded image





embedded image




CF3





679
C5H11


embedded image




embedded image





embedded image




OCF3





680
C5H11


embedded image




embedded image





embedded image




CN





681


embedded image




embedded image




embedded image





embedded image




F





682


embedded image




embedded image




embedded image





embedded image




CF3





683


embedded image




embedded image




embedded image





embedded image




OCF3





684


embedded image




embedded image




embedded image





embedded image




CN





685
C3H7


embedded image




embedded image





embedded image




F





686
C3H7


embedded image




embedded image





embedded image




CF3





687
C3H7


embedded image




embedded image





embedded image




OCF3





688
C3H7


embedded image




embedded image





embedded image




CN





689
C5H11


embedded image




embedded image





embedded image




F





690
C5H11


embedded image




embedded image





embedded image




CF3





691
C5H11


embedded image




embedded image





embedded image




OCF3





692
C5H11


embedded image




embedded image





embedded image




CN





693


embedded image




embedded image




embedded image





embedded image




F





694


embedded image




embedded image




embedded image





embedded image




CF3





695


embedded image




embedded image




embedded image





embedded image




OCF3





696


embedded image




embedded image




embedded image





embedded image




CN





697
C3H7


embedded image




embedded image





embedded image




F





698
C3H7


embedded image




embedded image





embedded image




CF3





699
C3H7


embedded image




embedded image





embedded image




OCF3





700
C3H7


embedded image




embedded image





embedded image




CN





701
C5H11


embedded image




embedded image





embedded image




F





702
C5H11


embedded image




embedded image





embedded image




CF3





703
C5H11


embedded image




embedded image





embedded image




OCF3





704
C5H11


embedded image




embedded image





embedded image




CN





705


embedded image




embedded image




embedded image





embedded image




F





706


embedded image




embedded image




embedded image





embedded image




CF3





707


embedded image




embedded image




embedded image





embedded image




OCF3





708


embedded image




embedded image




embedded image





embedded image




CN





709
C3H7


embedded image




embedded image





embedded image




F





710
C3H7


embedded image




embedded image





embedded image




CF3





711
C3H7


embedded image




embedded image





embedded image




OCF3





712
C3H7


embedded image




embedded image





embedded image




CN





713
C5H11


embedded image




embedded image





embedded image




F





714
C5H11


embedded image




embedded image





embedded image




CF3





715
C5H11


embedded image




embedded image





embedded image




OCF3





716
C5H11


embedded image




embedded image





embedded image




CN





717


embedded image




embedded image




embedded image





embedded image




F





718


embedded image




embedded image




embedded image





embedded image




CF3





719


embedded image




embedded image




embedded image





embedded image




OCF3





720


embedded image




embedded image




embedded image





embedded image




CN





721
C3H7


embedded image




embedded image





embedded image




F





722
C3H7


embedded image




embedded image





embedded image




CF3





723
C3H7


embedded image




embedded image





embedded image




OCF3





724
C3H7


embedded image




embedded image





embedded image




CN





725
C5H11


embedded image




embedded image





embedded image




F





726
C5H11


embedded image




embedded image





embedded image




CF3





727
C5H11


embedded image




embedded image





embedded image




OCF3





728
C5H11


embedded image




embedded image





embedded image




CN





729


embedded image




embedded image




embedded image





embedded image




F





730


embedded image




embedded image




embedded image





embedded image




CF3





731


embedded image




embedded image




embedded image





embedded image




OCF3





732


embedded image




embedded image




embedded image





embedded image




CN





733
C3H7


embedded image




embedded image





embedded image




F





734
C3H7


embedded image




embedded image





embedded image




CF3





735
C3H7


embedded image




embedded image





embedded image




OCF3





736
C3H7


embedded image




embedded image





embedded image




CN





737
C5H11


embedded image




embedded image





embedded image




F





738
C5H11


embedded image




embedded image





embedded image




CF3





739
C5H11


embedded image




embedded image





embedded image




OCF3





740
C5H11


embedded image




embedded image





embedded image




CN





741


embedded image




embedded image




embedded image





embedded image




F





742


embedded image




embedded image




embedded image





embedded image




CF3





743


embedded image




embedded image




embedded image





embedded image




OCF3





744


embedded image




embedded image




embedded image





embedded image




CN





745
C3H7


embedded image




embedded image





embedded image




F





746
C3H7


embedded image




embedded image





embedded image




CF3





747
C3H7


embedded image




embedded image





embedded image




OCF3





748
C3H7


embedded image




embedded image





embedded image




CN





749
C5H11


embedded image




embedded image





embedded image




F





750
C5H11


embedded image




embedded image





embedded image




CF3





751
C5H11


embedded image




embedded image





embedded image




OCF3





752
C5H11


embedded image




embedded image





embedded image




CN





753


embedded image




embedded image




embedded image





embedded image




F





754


embedded image




embedded image




embedded image





embedded image




CF3





755


embedded image




embedded image




embedded image





embedded image




OCF3





756


embedded image




embedded image




embedded image





embedded image




CN





757
C3H7



embedded image





embedded image




embedded image




embedded image


F





758
C3H7



embedded image





embedded image




embedded image




embedded image


CF3





759
C3H7



embedded image





embedded image




embedded image




embedded image


OCF3





760
C3H7



embedded image





embedded image




embedded image




embedded image


CN





761
C5H11



embedded image





embedded image




embedded image




embedded image


F





762
C5H11



embedded image





embedded image




embedded image




embedded image


CF3





763
C5H11



embedded image





embedded image




embedded image




embedded image


OCF3





764
C5H11



embedded image





embedded image




embedded image




embedded image


CN





765


embedded image





embedded image





embedded image




embedded image




embedded image


F





766


embedded image





embedded image





embedded image




embedded image




embedded image


CF3





767


embedded image





embedded image





embedded image




embedded image




embedded image


OCF3





768


embedded image





embedded image





embedded image




embedded image




embedded image


CN





769
C3H7



embedded image





embedded image




embedded image




embedded image


F





770
C3H7



embedded image





embedded image




embedded image




embedded image


CF3





771
C3H7



embedded image





embedded image




embedded image




embedded image


OCF3





772
C3H7



embedded image





embedded image




embedded image




embedded image


CN





773
C5H11



embedded image





embedded image




embedded image




embedded image


F





774
C5H11



embedded image





embedded image




embedded image




embedded image


CF3





775
C5H11



embedded image





embedded image




embedded image




embedded image


OCF3





776
C5H11



embedded image





embedded image




embedded image




embedded image


CN





777


embedded image





embedded image





embedded image




embedded image




embedded image


F





778


embedded image





embedded image





embedded image




embedded image




embedded image


CF3





779


embedded image





embedded image





embedded image




embedded image




embedded image


OCF3





780


embedded image





embedded image





embedded image




embedded image




embedded image


CN





781
C3H7



embedded image





embedded image




embedded image




embedded image


F





782
C3H7



embedded image





embedded image




embedded image




embedded image


CF3





783
C3H7



embedded image





embedded image




embedded image




embedded image


OCF3





784
C3H7



embedded image





embedded image




embedded image




embedded image


CN





785
C5H11



embedded image





embedded image




embedded image




embedded image


F





786
C5H11



embedded image





embedded image




embedded image




embedded image


CF3





787
C5H11



embedded image





embedded image




embedded image




embedded image


OCF3





788
C5H11



embedded image





embedded image




embedded image




embedded image


CN





789


embedded image





embedded image





embedded image




embedded image




embedded image


F





790


embedded image





embedded image





embedded image




embedded image




embedded image


CF3





791


embedded image





embedded image





embedded image




embedded image




embedded image


OCF3





792


embedded image





embedded image





embedded image




embedded image




embedded image


CN





793
C3H7



embedded image





embedded image




embedded image




embedded image


F





794
C3H7



embedded image





embedded image




embedded image




embedded image


CF3





795
C3H7



embedded image





embedded image




embedded image




embedded image


OCF3





796
C3H7



embedded image





embedded image




embedded image




embedded image


CN





797
C5H11



embedded image





embedded image




embedded image




embedded image


F





798
C5H11



embedded image





embedded image




embedded image




embedded image


CF3





799
C5H11



embedded image





embedded image




embedded image




embedded image


OCF3





800
C5H11



embedded image





embedded image




embedded image




embedded image


CN





801


embedded image





embedded image





embedded image




embedded image




embedded image


F





802


embedded image





embedded image





embedded image




embedded image




embedded image


CF3





803


embedded image





embedded image





embedded image




embedded image




embedded image


OCF3





804


embedded image





embedded image





embedded image




embedded image




embedded image


CN





805
C3H7



embedded image





embedded image




embedded image




embedded image


F





806
C3H7



embedded image





embedded image




embedded image




embedded image


CF3





807
C3H7



embedded image





embedded image




embedded image




embedded image


OCF3





808
C3H7



embedded image





embedded image




embedded image




embedded image


CN





809
C5H11



embedded image





embedded image




embedded image




embedded image


F





810
C5H11



embedded image





embedded image




embedded image




embedded image


CF3





811
C5H11



embedded image





embedded image




embedded image




embedded image


OCF3





812
C5H11



embedded image





embedded image




embedded image




embedded image


CN





813


embedded image





embedded image





embedded image




embedded image




embedded image


F





814


embedded image





embedded image





embedded image




embedded image




embedded image


CF3





815


embedded image





embedded image





embedded image




embedded image




embedded image


OCF3





816


embedded image





embedded image





embedded image




embedded image




embedded image


CN





817
C3H7



embedded image





embedded image




embedded image




embedded image


F





818
C3H7



embedded image





embedded image




embedded image




embedded image


CF3





819
C3H7



embedded image





embedded image




embedded image




embedded image


OCF3





820
C3H7



embedded image





embedded image




embedded image




embedded image


CN





821
C5H11



embedded image





embedded image




embedded image




embedded image


F





822
C5H11



embedded image





embedded image




embedded image




embedded image


CF3





823
C5H11



embedded image





embedded image




embedded image




embedded image


OCF3





824
C5H11



embedded image





embedded image




embedded image




embedded image


CN





825


embedded image





embedded image





embedded image




embedded image




embedded image


F





826


embedded image





embedded image





embedded image




embedded image




embedded image


CF3





827


embedded image





embedded image





embedded image




embedded image




embedded image


OCF3





828


embedded image





embedded image





embedded image




embedded image




embedded image


CN





829
C3H7



embedded image





embedded image




embedded image




embedded image


F





830
C3H7



embedded image





embedded image




embedded image




embedded image


CF3





831
C3H7



embedded image





embedded image




embedded image




embedded image


OCF3





832
C3H7



embedded image





embedded image




embedded image




embedded image


CN





833
C5H11



embedded image





embedded image




embedded image




embedded image


F





834
C5H11



embedded image





embedded image




embedded image




embedded image


CF3





835
C5H11



embedded image





embedded image




embedded image




embedded image


OCF3





836
C5H11



embedded image





embedded image




embedded image




embedded image


CN





837


embedded image





embedded image





embedded image




embedded image




embedded image


F





838


embedded image





embedded image





embedded image




embedded image




embedded image


CF3





839


embedded image





embedded image





embedded image




embedded image




embedded image


OCF3





840


embedded image





embedded image





embedded image




embedded image




embedded image


CN









Further combinations of the embodiments and variants of the invention arise from the following claims.

Claims
  • 1. A compound of formula I R1-(A1-Z1)a—W1—(Z2-A2)b-Z3—W2—(Z4-A3)c-R2  I
  • 2. A compound according to claim 1, wherein W1, W2, are each, independently of one another, a structural element selected from the part-structures (w10), (w11), (w20) and (w21):
  • 3. A compound according to claim 2, wherein W1, W2, are each independently of one another, a structural element selected from the part-structures (w10) and (w20).
  • 4. A compound according to claim 1, wherein R1 is an alkyl radical having up to 15 C atoms which is unsubstituted, monosubstituted by CN, or at least monosubstituted by halogen, where, in addition, one or more CH2 groups are each optionally replaced, independently of one another, by —O—, —CH═CH—, —C≡C—, —S—, —CO—, —(CO)O—, —O(CO)— or —O(CO)O— in such a way that O atoms are not linked directly to one another.
  • 5. A compound according to claim 1, wherein R2 is Cl, F, CN, SCN, SF5, or an alkyl radical having up to 15 C atoms which is monosubstituted by CN or at least monosubstituted by halogen, where, in addition, one or more CH2 groups in the alkyl radical are each optionally replaced, independently of one another, by —O—, —CH═CH—, —CF═CF—, —CF═CH—, —C≡C—, —S—, —CO—, —(CO)O—, —O(CO)— or —O(CO)O— in such a way that O atoms are not linked directly to one another.
  • 6. A compound according to claim 1, wherein the sum of the indices, a+b+c, is 1.
  • 7. A compound according to claim 1, wherein A1, A2 and A3 are each, independently of one another, a divalent group selected from the formulae:
  • 8. A compound according to claim 1, wherein Z1, Z2, Z3 and Z4 are each, independently of one another, a single bond, —CH2CH2—, —CH═CH—, —CH2O— or —CF2O—.
  • 9. A compound according to claim 1, wherein c denotes 1,Z4 denotes CF2O, andA3 denotes a divalent group of the formula
  • 10. A process for the preparation of a compound according to claim 1, in which A2 is a dioxane ring and Z2 and Z3 are single bonds, said process comprising: reacting a compound of formula II
  • 11. A process for the preparation of a compound according to claim 1, in which b is 0 and Z3 is a single bond, said process comprising: reacting an oxetane compound of formula IV
  • 12. A method of using of one or more compounds of the formula I according to claim 1 which comprises using one or more of said compounds as components in a liquid-crystalline medium.
  • 13. A liquid-crystalline medium comprising at least two components, wherein said medium comprises at least one compound according to claim 1.
  • 14. A liquid-crystalline medium according to claim 13, wherein said medium is polymer-stabilized in a blue phase.
  • 15. An electro-optical display element comprising a dielectric, wherein said dielectric is a medium according to claim 13.
  • 16. A compound according to claim 1, wherein W1, W2, are each, independently of one another, a structural element selected from the part-structures (w10), (w11), (w20) and (w21):
  • 17. A compound of formula I R1-(A1-Z1)a—W1—(Z2-A2)b-Z3—W2—(Z4-A3)c-R2  I
  • 18. A compound of formula I R1-(A1-Z1)a—W1—(Z2-A2)b-Z3—W2—(Z4-A3)c-R2  I
  • 19. A compound of formula I R1-(A1-Z1)a—W1—(Z2-A2)b-Z3—W2—(Z4-A3)c-R2  I
  • 20. A compound according to claim 19, wherein W1, W2, are each independently of one another, a structural element selected from the part-structures (w10) and (w20).
  • 21. A compound according to claim 19, wherein R1 is an alkyl radical having up to 15 C atoms which is unsubstituted, monosubstituted by CN, or at least monosubstituted by halogen, where, in addition, one or more CH2 groups are each optionally replaced, independently of one another, by —O—, —CH═CH—, —C≡C—, —S—, —CO—, —(CO)O—, —O(CO)— or —O(CO)O— in such a way that O atoms are not linked directly to one another.
  • 22. A compound according to claim 19, wherein R2 is H, Cl, F, CN, SCN, SF5, or an alkyl radical having up to 15 C atoms which is monosubstituted by CN or at least monosubstituted by halogen, where, in addition, one or more CH2 groups in the alkyl radical are each optionally replaced, independently of one another, by —O—, —CH═CH—, —CF═CF—, —CF═CH—, —C≡C—, —S—, —CO—, —(CO)O—, —O(CO)— or —O(CO)O— in such a way that O atoms are not linked directly to one another.
  • 23. A compound according to claim 19, wherein W1, W2, are each, independently of one another, a structural element selected from the part-structures (w10), (w11), (w20) and (w21):
  • 24. A compound according to claim 19, wherein L1, L2, and L3 are each independently H or F.
Priority Claims (1)
Number Date Country Kind
10 2007 004 699 Jan 2007 DE national
PCT Information
Filing Document Filing Date Country Kind 371c Date
PCT/EP2007/010815 12/11/2007 WO 00 7/30/2009
Publishing Document Publishing Date Country Kind
WO2008/092491 8/7/2008 WO A
Foreign Referenced Citations (12)
Number Date Country
102008004891 Aug 2008 DE
1491612 Dec 2004 EP
1690917 Aug 2006 EP
2006199941 Aug 2006 JP
2006199941 Aug 2006 JP
2004046805 Jun 2004 WO
2006012965 Feb 2006 WO
2006040009 Apr 2006 WO
2006079406 Aug 2006 WO
2006125511 Nov 2006 WO
PCTEP2007010815 Apr 2008 WO
2008092491 Aug 2008 WO
Related Publications (1)
Number Date Country
20100102274 A1 Apr 2010 US