EP1373434A1 - Fluorinated fluorene derivatives - Google Patents

Abstract

The invention relates to novel fluorinated fluorene derivatives with negative anisotropy of the dielectric constant, of formula 1, R<1> -(-A<1>-Z<1>-)k1-(A<2>-Z<2>-)k2-W-(-Z<3>-A3-)k3(-Z<4>-A<4>-)k4-R<2>, where W = partial formula (2), L<1>, L<2> independently = H, F, Cl, -CH2F, -CHF2, or -CF3, with the proviso that both L<1> and L<2> H, L<3>, L<4> independently = H or F and R<1>, R<2>, A<1>, A<2>, A<3>, A<4>, Z<1>, Z<2>, Z<3>, Z<4>, k1, k2, k3 and k4 have the given meanings. The invention further relates to liquid crystal media, optical and electro-optical display elements.

Description

 Fluorinated fluorene derivatives

The invention relates to fluorinated fluorene derivatives of the formula I which have a negative anisotropy of the dielectric constant (DK anisotropy),

R ¹ - (- A ¹ -Z ¹ -) _k1 - (- A ² -Z ² -) _k2 -W - (- Z ³ -A ³ -) _k3 - (- Z ⁴ -A ⁴ -) _k4 -R ² I

in the

w the group

means

L ¹ , L ² independently of one another are H, F, Cl, -CH ₂ F, -CHF ₂ or -CF _3, with the proviso that both L ¹ and L ² do not denote H,

L ³ , L ⁴ independently of one another H or F,

R ¹ , R ² independently of one another are H, halogen, -CN, -NCS, -SF ₅ or alkyl having 1 to 18 C atoms, in which one or two non-adjacent -CH ₂ groups are also represented by -O-, -S- , -CO-, -O-CO-, -CO-O-, -E- and / or -C≡C- can be replaced and / or wherein one or more H atoms are also replaced by halogen and / or -CN can be means

E CR ⁴ = CR ⁵ or CHR ⁴ -CHR ⁵ ,

R ⁴ , R ⁵ each independently of one another H, alkyl with 1-6

Is C atoms, F, Cl, CF ₃ or CN,

A ¹ , A ² , A ³ , A ⁴ each independently 1, 4-phenylene, in which one or more CH groups can be replaced by N, 1, 4-cyclohexylene, in which one or two are not adjacent CH ₂ groups can be replaced by O and / or S, 1,4-cyclohexenylene, 1,4-bicyclo (2,2,2) octylene, piperidin-1,4-diyl, naphthalene-2,6-diyl, Decahydronaphthalene-2,6-diyl or 1, 2, 3,4-tetrahydronaphthalene-2,6-diyl, where one or more H atoms may be substituted in the meanings given for A ¹ , A ² , A ³ , A ⁴ through halogen,

-CN and / or alkyl having 1 to 6 carbon atoms, in which one or more H atoms are halogen or -CN, and / or in which one or more non-adjacent -CH ₂ groups independently of one another by -CO-, -O -CO-, -CO-O-, -0-, -S-, -CH = CH- or -C≡C- can be replaced, and

Z ¹ , Z ² , Z ³ , Z ⁴ independently of one another -O-CO-, -CO-O-, -CH ₂ -0-,

-CF ₂ -0-, -0-CH ₂ -, -0-CF ₂ -, -C ₂ H ₄ -, -CH ₂ -CF ₂ -, -CF ₂ -CH ₂ -, -CF ₂ -CF ₂ -, -CH = CH-, -CF = CH-, -CH = CF-, -CF = CF-, -C≡C- or a single bond,

k1, k2, k3, k4 independently of one another represent 0, 1 or 2.

The invention further relates to liquid-crystalline media and to liquid-crystal and electro-optical display elements which contain the liquid-crystalline media according to the invention.

Fluorinated fluorene derivatives belonging to the group

in which XF or H have, are described in DE 197 20 289 as components of ferroelectric liquid crystal mixtures. For this purpose it is stated that more negative values of the dielectric anisotropy (Δε) can be obtained by admixing such compounds. The

Use in FLC mixtures for operation in inverse mode is mentioned as preferred. However, no values for individual substances or mixtures are given. There is still a great need for compounds and media with a strongly to very strongly negative dielectric anisotropy Δε, in particular those with a very high specific resistance with a wide mesophase range and low viscosity.

The object of the present invention is to provide new stable, liquid-crystalline or mesogenic compounds with strongly to very strongly negative DK anisotropy, which are suitable as components of liquid-crystalline media.

Further objects of the invention relate to the provision of liquid-crystalline media and optical and electro-optical display elements.

The first-mentioned object is achieved with fluorene derivatives of the formula I. It has been found that the compounds according to the invention are particularly suitable as components of liquid-crystalline media. With their help, stable liquid-crystalline media can be obtained that are particularly suitable for electro-optical LC displays. The fluorene derivatives according to the invention have strongly to very strongly negative Δε values. As a rule, these values are significantly lower than the Δε values of comparable compounds which only carry H atoms in the 1- and 8-positions of the fluorene group. In addition, the fluorene derivatives according to the invention have relatively low values of the optical anisotropy Δn and favorable mesophase ranges for use in electro-optical display elements. Furthermore, these compounds are also chemically, thermally and stable to light and are readily miscible with other liquid-crystalline substances.

With the provision of the fluorene derivatives according to the invention, the range of liquid-crystalline substances which are suitable for the production of liquid-crystalline mixtures from various application points of view is very broadly widened considerably.

In addition, the invention relates to a liquid-crystalline medium with two or more liquid-crystalline components, wherein the medium has at least one fluorene derivative according to the invention. The use of such fluorene derivatives allows the dielectric anisotropy of such media to be influenced in a targeted manner in the direction of negative Δε values, it being possible advantageously to achieve low viscosities. In addition, however, it is also possible to add one or more compounds according to the invention to liquid-crystalline media in order to specifically influence the optical anisotropy and / or the mesophase regions and / or the tilt angle of such media.

The compounds according to the invention 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 DAP (deformation of aligned phases), ECB (electrically controlled birefringence), CSH ( color super homeotropic), VA (vertically aligned), or IPS effect (in plane switching) or the effect of dynamic scattering.

Furthermore, the compounds according to the invention can be used as components of optically active inclined smectic (ferroelectric) liquid-crystalline media, in particular for displays based on the SSFLCD effect (Surface Stabilized Ferroelectric Liquid Crystal Display) from Clark and Lagerwall, but also on the DHF effect (Distorted Helix Formation) or the PSFLCD effect (Pitch Stabilized Ferroelectric Liquid Crystal Display), which is also called SBF effect (Short Pitch Bistable Ferroelectric).

Further objects of the invention are an optical display element which contains a liquid-crystalline medium according to the invention, and an electro-optical display element which contains a liquid-crystalline medium according to the invention as a dielectric. The display elements mentioned above are preferred.

Above and below, the groups, substituents and indices have W, R ¹ , R ² , E, R ⁴ , R ⁵ , L ¹ , L ² , L ³ , L ⁴ , Z ¹ , Z ² , Z ³ , Z ⁴ , A ¹ , A ² , A ³ , A ⁴ , k1, k2, k3 and k4 have the meaning given for formula I, unless expressly something else is noted. If a remainder occurs more than once, it can have the same or different meanings.

The meaning of the formula I includes all isotopes of the chemical elements bound in the compounds of the formula I. The compounds of the formula are suitable in enantiomerically pure or enriched form

I also as chiral dopants and generally to achieve chiral mesophases.

Preferred meanings of groups and substituents of the fluorene derivatives according to the invention are given below.

Preferred meanings of group W represent the sub-formulas W1 to W3:

Particularly preferred meanings of the sub-formula W1 are the sub-formulas W11 to W18:

Above and below, I = 0, 1 or 2, so that the group means -CH | F _3. , -CH ₂ F, -CHF ₂ or -CF ₃ . L preferably has the value 0 or 1, particularly preferably the value I = 0. If the index I occurs more than once in a formula, it can have the same or different meanings.

Particularly preferred meanings of the sub-formula W2 are the sub-formulas W21 to W28:

The sub-formula W2 and the corresponding sub-formulas W21 to W28 include in the event that the C atom of group V

HF is a chiral center, both the racemates and the enantiomerically pure or enriched forms.

Particularly preferred meanings of the sub-formulas W3 represent the sub-formulas W31 to W38:

W1, in particular W11 to, of the sub-formulas mentioned above

W18 and W3, in particular W31 to W38, are particularly preferred.

According to a first preferred embodiment of the invention, k1, k2, k3 and k4 have the value 0 and the compounds according to the invention therefore have the formula Ia

R ¹ -WR ² la

Preferably, at least one of the groups R ¹ or R ² , preferably R ¹ and R ² , independently of one another, has the meaning alkyl having 1 to 18 C atoms, in which also one or two non-adjacent —CH ₂ - groups and / or one or more H atoms can be replaced as indicated.

Compounds of the sub-formulas Ia1 to la10 are particularly preferred

R ¹ -W11-R ² Ia1

R ¹ -W13-R ² Ia2

R ¹ -W14-R ² Ia3

R ¹ -W16-R ² Ia4

R ¹ -W18-R ² Ia5

Let R ¹ -W31-R ²

R ¹ -W33-R ² Ia7

R ¹ -W34-R ² Ia8

R ¹ -W36-R ² Ia9

R ¹ -W38-R ² Ia10

with the meanings previously given for W11 to W38. According to a second preferred embodiment, at least one of the indices k1, k2, k3 and / or k4 has a non-zero value.

According to a preferred first variant, k1 = 1 and k2 = k3 = k4 = 0, so that the fluorene derivatives have the formula Ib

R ¹ - A ¹ -Z ¹ -W -R ² Ib.

According to a preferred second variant, k1 = k2 = 1 and k3 = k4 = 0, so that the fluorene derivatives have the formula Ic:

R ¹ -A ¹ -Z ¹ -A ² -Z ² - W -R ² Ic.

According to a preferred third variant, k1 = k3 = 1 and k2 = k4 = 0, so that the fluorene derivatives have the formula Id:

R ¹ -A ¹ -Z ¹ -W- Z ³ -A ³ -R ² Id.

Particularly preferred meanings of A, A, A and / or A ⁴ are, independently of one another, 1,4-phenylene, which can be substituted once, twice or three times by fluorine, trans-1,4-cyclohexylene and 1,3-dioxane -2,5- diyl, for the sake of simplicity the abbreviations Phe, Cyc or Dio are used below.

The term 1,3-dioxane-2,5-diyl encompasses the two positional isomers and

If, according to the second embodiment, the compounds contain a six-membered ring in addition to group W, the following compounds of sub-formulas Ib1 to Ib3 are preferred:

R ¹ -Cyc-Z ¹ -WR ² Ib1 R ¹ -Phe-Z ¹ -WR ^: Ib2 R ¹ -Dio-Z ¹ -WR ² Ib3

If, according to the second embodiment, the compounds contain two six-membered rings in addition to the group W, the following compounds of the sub-formulas Ic1 to Ic9 and Id1 to Id9 are preferred:

R ¹ -Cyc-Z ¹ -Cyc-Z ² -WR ² Ic1

R ¹ -Cyc-Z ¹ -Phe-Z ² -WR ² Ic2

R ¹ -Cyc-Z ¹ -Dio-Z ² -WR ² Ic3 R ¹ -Phe-Z ¹ -Cyc-Z ² -WR ² Ic4

R ¹ -Phe-Z ¹ -Phe-Z ² -WR ² Ic5

R ¹ -Phe-Z ¹ -Dio-Z ² -WR ² Ic6

R ¹ -Dio-Z ¹ -Cyc-Z ² -WR ² Ic7

R ¹ -Dio-Z ¹ -Phe-Z ² -WR ² Ic8 R ¹ -Dio-Z ¹ -Dio-Z ² -WR ² Ic9

R ¹ -Cyc-Z ¹ -WZ ³ -Cyc-R ² Id1

R ¹ -Cyc-Z ¹ -WZ ³ -Phe-R ² Id2

R ¹ -Cyc-Z ¹ -WZ ³ -Dio-R ² Id3

R ¹ -Phe-Z ¹ -WZ ³ -Cyc-R ² Id4

R ¹ -Phe-Z ¹ -WZ ³ -Phe-R ² Id5

R ¹ -Phe-Z ¹ -WZ ³ -Dio-R ² Id6

R ¹ -Dio-Z ¹ -WZ ³ -Cyc-R ² Id7

R ¹ -Dio-Z ¹ -WZ ³ -Phe-R ² Id8

R ¹ -Dio-Z ¹ -WZ ³ -Dio-R ² Id9

In addition to the group W, the compounds according to the second embodiment can also have three or more six-membered rings. If L ³ and L ⁴ H mean, those fluorene derivatives of the formula I are preferred in which R ¹ - (- A ¹ -Z ¹ -) _k (-A ² -Z ² -) _k2 - and - (- Z ³ -A ³ -) _k3 - (- Z ⁴ -A ⁴ -) _k4 -R ² are selected such that the fluorene derivative has a dielectric anisotropy Δε of less than or equal to -2.0, particularly preferably of less than or equal to -4, 0, very particularly preferably less than or equal to -5.0.

If L ³ or L ^{4 is} F and the other substituent is L ⁴ or L ³ H, preference is given to those fluorene derivatives of the formula I in which R ¹ _ (_ A -Z ¹ -) _k1 - (- A ² -Z ² -) _k2 - and - (- Z ³ -A ³ -) _k3 - (- Z ⁴ -A ⁴ -) _k4 -R ² are selected such that the fluorene derivative has a dielectric anisotropy Δε of less than or equal to -6.0 , particularly preferably less than or equal to -8.0, very particularly preferably less than or equal to -10.0.

If L ³ and L ^{4 are} F, those fluorene derivatives of the formula I are preferred in which R ¹ - (- A ¹ -Z ¹ -) _k r (-A ² -Z ² -) _k2 - and

- (- Z ³ -A ³ -) _k3 - (- Z ⁴ -A ⁴ -) _k4 -R ² are selected such that the fluorene derivative has a dielectric anisotropy Δε of less than or equal to -8.0, in particular less than or equal to -10.0, particularly preferably less than or equal to -12.0, very particularly preferably less than or equal to -15.0.

In the case of alkyl in the groups or substituents given above or below, in particular in R ¹ and / or R ² , the alkyl radical can be linear or branched. It preferably has 1, 2, 3, 4, 5, 6, 7 or 8 carbon atoms. It is preferably linear and therefore particularly means methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl.

R ¹ and / or R ² preferably denotes alkyl, alkenyl, alkoxy, alkenyloxy, oxaalkyl, oxaalkenyl, alkylcarbonyloxy or alkyloxycarbonyl.

In addition to the meanings given above in the case of alkyl, R ¹ and R ² as alkyl can also have more than 8 carbon atoms and therefore particularly mean nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl. Further preferred meanings of R ¹ and / or R ² are alkoxy. The alkoxy radical can be linear or branched. It is preferably linear and has 1, 2, 3, 4, 5, 6, 7 or 8 carbon atoms and therefore means especially methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy or octoxy, furthermore nonoxy, decoxy, Undecoxy, dodecoxy, tridecoxy or tetradecoxy.

Furthermore, R ¹ and / or R ^{2 are} preferably oxaalkyl. The rest can be linear or branched. It is preferably linear and means, for example, 2-oxapropyl (= methoxymethyl), 2- (= ethoxymethyl) or 3-oxabutyl (= 2-methoxyethyl), 2-, 3- or 4-oxapentyl, 2-, 3-, 4- or 5-oxahexyl, 2-, 3-, 4-, 5- or 6-oxaheptyl, 2-, 3-, 4-, 5-, 6- or 7-oxaoctyl, 2-, 3-, 4-, 5 -, 6-, 7- or 8-oxanonyl or 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-oxadecyl.

If R ¹ and / or R ^{2 represent} an alkenyl radical, this can be straight-chain or branched. It is preferably straight-chain and has 2 to 8 carbon atoms. Accordingly, it means especially vinyl, prop-1- or prop-2-enyl, but-1-, 2- or but-3-enyl, pent-1-, 2-, 3- or pent-4-enyl, hex- 1-, 2-, 3-, 4- or hex-5-enyl, hept-1-, 2-, 3-, 4-, 5- or hept-6-enyl or oct- 1-, 2-, 3 -, 4-, 5-, 6- or oct-7-enyl.

If R ¹ and / or R ^{2 represent} an alkenyloxy radical, this can be straight-chain or branched. It is preferably straight-chain and accordingly means in particular vinyloxy, prop-1 or prop-2-enyloxy, but-1-, 2- or but-3-enyloxy, pent-1-, 2-, 3- or pent-4- enyloxy, hex-1-, 2-, 3-, 4- or hex-5-enyloxy, hept-1-, 2-, 3-, 4-, 5- or hept-6-enyloxy or oct-1-, 2-, 3-, 4-, 5-, 6- or oct-7-enyloxy.

If R ¹ and / or R ^{2 represent} an oxaalkenyl radical, this can be straight-chain or branched. It is preferably straight-chain and is particularly preferably 3-oxabut-1-enyl (= methoxyvinyl), 2-oxabut-3-enyl (= vinyloxymethyl), 4-oxapent-1-enyl (= methoxyprop-1-enyl), 3- Oxapent-1-enyl (= ethoxyvinyl), 4-oxapent-2-enyl (= methoxyprop-2-enyI), 2-oxapent-3-enyl (= prop-1-enoxymethyl), 2-oxapent-4-enyl ( = Prop-2-enoxymethyl), 3-oxapent-4-enyl (= vinyloxyethyl), 3-oxahex-1-enyl, 4-oxahex-1-enyl, 5-oxahex-1-enyl, 4-oxahex-2- enyl, 5-oxahex-2-enyl, 2- Oxahex-3-enyl, 5-oxahex-3-enyl, 2-oxahex-4-enyl, 3-oxahex-4-enyl, 2-oxahex-5-enyl, 3-oxahex-5-enyl or 4-oxahex 5-enyl.

If R 1 and / or R ^{2 represent} an alkyl radical in which one CH ₂ group has been replaced by -O- and one has been replaced by -CO-, these are preferably adjacent. Thus they contain a carbonyloxy group

(Acyloxy group) -CO-O- or an oxycarbonyl group -O-CO-. These are preferably straight-chain and have 2 to 6 carbon atoms. Accordingly, they mean in particular acetyloxy, propionyloxy, butyryloxy, pentanoyloxy, hexanoyloxy, acetyloxymethyl, propionyloxymethyl, butyryloxymethyl, pentanoyloxymethyl, 2-acetyloxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 3-acetyloxypyloxy, 3-acetyloxionyloxy, 3 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.

Compounds of the formula I with branched wing groups R ¹ and / or R ² can occasionally be of importance because of their better solubility in the customary liquid-crystalline base materials, but in particular as chiral dopants if they are optically active. Smectic compounds of this type are particularly suitable as components for ferroelectric materials.

Branched groups of this type usually contain no more than one chain branch. Preferred chiral branched radicals R 1 and / or R ² are 2-butyl (= 1-methylpropyl), 2-methylbutyl, 2-methylpentyl, 3-methylpentyl, 2-ethylhexyl, 2-propylpentyl, 2-octyl, especially 2-methylbutyl, 2-methylbutoxy, 2-methylpentoxy, 3-methylpentoxy, 2-

Ethylhexoxy, 1-methylhexoxy, 1-methylheptyloxy, 2-octyloxy, 2-oxa-3-methylbutyl, 3-oxa-4-methylpentyl, 4-methylhexyl, 2-nonyl, 2-decyl, 2-dodecyl, 6-methoxyoctoxy, 6-methyloctoxy, 6-methyloctanoyloxy, 5-methylheptyloxycarbonyl, 2-methylbutyryloxy, 3-methylvaleroyloxy, 4-methylhexanoyloxy, 2-methyl-3-oxapentyl, 2-methyl-3-oxahexyl, 1- Methoxypropyl-2-oxy, 1-ethoxypropyl-2-oxy, 1-propoxypropyl-2-oxy, 1-butoxypropyl-2-oxy, 2-fluorooctyloxy, 2-fluorodecyloxy.

Preferred achiral branched radicals R 1 and / or R ² are isopropyl, isobutyl (= 2-methylpropyl), isopentyl (= 3-methylbutyl), isopropoxy, 2-methylpropoxy, 3-methylbutoxy.

Formula I includes both the racemates of these compounds and the optical antipodes and mixtures thereof.

In the case of the above meanings of R ¹ and R ² , in particular as alkyl, alkenyl, alkoxy, alkenyloxy, oxaalkyl, oxaalkenyl, alkylcarbonyloxy or alkyloxycarbonyl, one or more H atoms are preferably by halogen atoms, preferably by fluorine and / or chlorine , particularly preferably substituted by fluorine. 2 or more H atoms are preferably substituted by fluorine. In the radicals specified above, 2 or 3 H atoms in the terminal methyl group are particularly preferably substituted by fluorine, so that the radicals specified above have a -CHF ₂ or a -CF ₃ group. The entire radical R ¹ and / or R ² can also be perfluorinated.

Among the compounds of the formula I and the sub-formulas, preference is given to those in which at least one of the radicals contained therein has one of the preferred meanings indicated.

The compounds according to the invention are prepared by methods known per se from the literature, as are described in standard works on organic synthesis, for example Houben-Weyl, Methods of Organic Chemistry, Georg-Thieme-Verlag, Stuttgart. The preparation takes place under reaction conditions which are known and suitable for the reactions mentioned. It is also possible to use synthesis variants which are known per se and are not mentioned here in detail. If necessary, the starting and / or intermediate products can also be formed in situ, ie they are not isolated from the reaction mixture but are immediately reacted further. The synthesis of three compounds of the formulas Ia-W1, Ia-W2 and Ia-W3 according to the invention starting from the fluorenone compound of the formula Ila is given by way of example using reaction scheme 1. The compound la-W1 is formed using a suitable reducing agent, such as NaBH ₄ in the presence of AICl ₃ and tetrahydrofuran (THF) as the solvent.

In the synthesis of compounds of the formula Ia-W2, the mixture is first reduced and then fluorinated, for example using NaBH ₄ and then diethylaminosulfur trifluoride (DAST). Another possibility for synthesis runs in two stages over a phenyl sulfide. First the carbonyl compound (here the fluorenone) is reacted with phenylthiol with catalysis by boron trifluoride monohydrate and then reduced with triethylsilane. In the second stage, the phenyl sulfide obtained is fluorinated with nitrosonium tetrafluoroborate-pyridine-HF complex (Ch. York et al., Tetrahedron 52, 1996, 9-14).

To produce the 9,9-difluorofluorenes of the formula Ia-W3, the fluorenone compound of the formula Ila is first converted into the corresponding dithioketal, for example by reaction with ethane-1,2-dithiol in the presence of boron trifluoride. The dithioketal is then in

Presence of a fluorinating agent and an oxidizing agent oxidatively fluorodesulfurized. A compound which releases halonium equivalents is preferably used as the oxidizing agent. Exemplary oxidizing agents are N-bromosuccinimide, N-iodosuccinimide, 1, 3-dibromo-5,5-dimethylhydantoin and bromine. Also suitable are, for example, S0 ₂ CI ₂ , S0 ₂ CIF, nitrosonium and nitronium salts (Ch. York op. Cit.) And chloramine T. The nitrosonium and nitronium salts can optionally also be prepared in situ from suitable precursors, for example from inorganic or organic nitrites and / or nitrates. Conventional fluorinating agents can be used as fluorinating agents. The fluorinating agent is particularly preferably selected from the group formed by aliphatic and aromatic amine-hydrogen fluoride complexes, such as, for example, pyridine-hydrogen fluoride complexes, NEt ₃ * 3HF, melamine HF, polyvinylpyridine HF. The reaction conditions to be observed in the reactions mentioned are known per se to the person skilled in the art. As a rule, the reaction takes place at a temperature of -100 to + 50 ° C. Inert polar solvents or mixtures thereof are used as solvents, for example ethers or haloalkanes, such as diethyl ether, tetrahydrofuran or dichloromethane.

A suitable synthetic route for the preparation of the fluorenones of the formula IIa is given in reaction scheme 2. Accordingly, the synthesis takes place starting from the aromatic bromine of the formula Va via the corresponding boron compound IVa and cross-coupling it with the aromatic bromate of the formula Va 'to give the biphenyl compound of the formula purple, which is reacted with dimethyl carbonate to form the fluorenone (RD Chamber et al., JCS (C) 1968 , 2394).

in reaction schemes 1 and 2, R ¹ , R ² , L ¹ and L ^{2 have} the meanings given. The syntheses described are suitable not only for compounds of the formula Ia, which have been chosen here for the sake of clarity, but for all compounds of the formula I according to the invention.

Reaction scheme 1

+ ₄ / AICI ₃

la-W3

Reaction scheme 2

1. BuLi 2. (CH ₃ 0) ₂ CO 3. H ₃ 0+

lla The person skilled in the art can obtain further suitable synthesis possibilities by analogously using the syntheses shown in reaction schemes 1 to 8 of DE 197 20 289 A1.

Esters of the formula I can also be esterified by appropriate carboxylic acids (or their reactive derivatives) with alcohols or

Phenols (or their reactive derivatives) or by the DCC method (DCC = dicyclohexylcarbodiimide) can be obtained.

The corresponding carboxylic acids and alcohols are known or can be prepared analogously to known processes.

Suitable reactive derivatives of the carboxylic acids mentioned are, in particular, the acid halides, especially the chlorides and bromides, furthermore the anhydrides, azides or esters, in particular alkyl esters with 1-4 C atoms in the alkyl group.

Suitable reactive derivatives of the alcohols mentioned are in particular the corresponding metal alcoholates, preferably an alkali metal such as Na or K.

The esterification is advantageously carried out in the presence of an inert solvent. Particularly suitable are ethers such as diethyl ether, di-n-butyl ether, THF, dioxane or anisole, ketones such as acetone, butanone or cyclohexanone, amides such as DMF or phosphoric acid hexamethyltriamide, hydrocarbons such as benzene, toluene or xylene, halogenated hydrocarbons such as carbon tetrachloride or tetrachlorethylene and Sulfoxides such as dimethyl sulfoxide or sulfolane. Water-immiscible solvents can also be used advantageously for azeotropically distilling off the water formed during the esterification. Occasionally an excess of an organic base, e.g.

Pyridine, quinoline or triethylamine, are used as solvents for the esterification. The esterification can also be carried out in the absence of a solvent, for example simply by heating the components in the presence of sodium acetate. The reaction temperature is usually between -50 ° C and + 250 ° C, preferably between -20 ° C and + 80 ° C. At these temperatures, the esterification reactions are usually complete after 15 minutes to 48 hours.

In particular, the reaction conditions for the esterification largely depend on the nature of the starting materials used. For example, a free carboxylic acid is generally reacted with a free alcohol in the presence of a strong acid, for example a mineral acid such as hydrochloric acid or sulfuric acid. A preferred reaction is the reaction of an acid anhydride or, in particular, an acid chloride with an alcohol, preferably in a basic medium, the bases being, in particular, alkali metal hydroxides such as sodium or potassium hydroxide, alkali metal carbonates or hydrogen carbonates such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate or potassium hydrogen carbonate, alkali metal acetates such as sodium or potassium acetate, alkaline earth metal hydroxides such as calcium hydroxide or organic bases such as triethylamine, pyridine, lutidine, collidine or quinoline are important. Another preferred embodiment of the esterification is that the alcohol is first converted into the sodium or potassium alcoholate, e.g. by treatment with ethanoic sodium or potassium hydroxide solution, isolate this and react with an acid anhydride or in particular acid chloride.

In a further process for the preparation of the compounds of the formula I in which Z ¹ , Z ² , Z ³ or Z ^{4 are} -CH = CH-, an aryl halide is reacted with an olefin in the presence of a tertiary amine and a palladium catalyst (cf. RF Heck, Acc. Chem. Res. 12 (1979) 146). Suitable aryl halides are, for example, chlorides, bromides and iodides, in particular bromides and iodides. The tertiary amines required for the coupling reaction to succeed, such as triethylamine, are also suitable as solvents. Suitable palladium catalysts are, for example, its salts, in particular (Pd (II) acetate, with organic phosphorus (III) compounds, such as, for example, triarylphosphanes, in the presence or absence of an inert solvent at temperatures between about 0 ° C. and 150 ° C. , preferably between 20 ° C. and 100 ° C. Suitable solvents are, for example, nitriles such as acetonitrile or hydrocarbons such as benzene or toluene The aryl halides and olefins used as starting materials are numerous commercially available or can be prepared by processes known from the literature, for example by halogenation of corresponding parent compounds or by elimination reactions on corresponding alcohols or halides.

In this way, stilbene derivatives can be produced, for example. The

Stilbenes can also be produced by reacting a 4-substituted benzaldehyde with a corresponding phosphorylide according to Wittig. However, tolanes of the formula I can also be prepared by using monosubstituted acetylene instead of the olefin (Synthesis 627 (1980) or Tetrahedron Lett. 27, 1171 (1986)).

Aryl halides can also be reacted with aryltin compounds to couple aromatics. These reactions are preferred with the addition of a catalyst such as e.g. a palladium (0) complex in inert solvents such as hydrocarbons at high temperatures, e.g. in boiling xylene, carried out under protective gas.

Couplings of alkynyl compounds with aryl halides can be analogous to that of A.O. King, E. Negishi, F.J. Villani and A. Silveira in J. Org. Chem. 43, 358 (1978).

Tolanes of the formula I, in which ∑ is Z ² , Z ³ or Z ⁴ —C ,C-, can also be prepared via the Fritsch-Buttenberg-Wiechell rearrangement (Ann. 279, 319, 1984), in which 1.1 -Diaryl-2-halogenethylenes are rearranged to diarylacetylenes in the presence of strong bases.

Tolanes of the formula I can also be prepared by brominating the corresponding stilbenes and then subjecting them to dehydrohalogenation. You can use known variants of this implementation, which are not mentioned here.

Ethers of the formula I can be obtained by etherification of corresponding hydroxyl compounds, preferably corresponding phenols, the hydroxyl compound advantageously first being converted into a corresponding metal derivative, for example by treatment with NaH, NaNH ₂ , NaOH, KOH, Na ₂ CO ₃ or K ₂ CO _{3 is converted} into the corresponding alkali metal alcoholate or alkali metal phenolate. This can then be reacted with the corresponding alkyl halide, sulfonate or dialkyl sulfate, advantageously in an inert solvent such as acetone, 1, 2-dimethoxyethane, DMF or dimethyl sulfoxide or with an excess of aqueous or aqueous-alcoholic NaOH or KOH

Temperatures between about 20 ° C and 100 ° C.

Corresponding aniline derivatives with sodium nitrite and either with tetrafluoroboric acid (for introducing an F atom) or with copper (I) chloride (for introducing a Cl atom) can be used to produce the laterally substituted fluorine or chlorine compounds of the formula I Diazonium salts are implemented, which are then thermally decomposed at temperatures of 100-140 ° C.

The connection of an aromatic nucleus to a non-aromatic nucleus or two non-aromatic nuclei is preferably obtained by condensation of an organolithium or magnesium compound with a ketone if there is to be an aliphatic group Z ¹ between the nuclei.

The organometallic compounds are prepared, for example, by metal-halogen exchange (for example according to Org. React. 6, 339-366 (1951)) between the corresponding halogen compound and an organolithium compound, preferably tert-butyllithium or lithium naphthalenide, or by conversion with magnesium shavings.

Two aromatic rings are preferably linked by Friedel-Crafts alkylation or acylation by reacting the corresponding aromatic compounds with Lewis acid catalysis. Suitable Lewis acids are, for example, SnCI _4l ZnCI ₂ , AICl ₃ and TiCI ₄ .

Furthermore, the linking of two aromatic rings by the Ullmann reaction (eg Synthesis 1974, 9) between aryl iodides with copper iodide, but preferably between an aryl-copper compound and an aryl iodide, or by the Gomberg-Bachmann reaction between an aryl diazonium salt and the corresponding aromatic compound (eg Org. React. 2, 224 (1944)).

The representation of the tolanes of the formula I is e.g. by reacting the corresponding aryl halides with an acetylide in a basic solvent with transition metal catalysis; Palladium catalysts can preferably be used here, in particular a mixture of bis (triphenylphosphine) palladium (II) chloride and copper iodide in piperidine as solvent.

In addition, the compounds of the formula I can be prepared by reducing a compound which otherwise corresponds to the formula I but contains one or more reducible groups and / or C — C bonds instead of H atoms.

Possible reducible groups are preferably carbonyl groups, in particular keto groups, furthermore, for example, free or esterified hydroxyl groups or aromatically bonded halogen atoms. Preferred starting materials for the reduction are compounds corresponding to the formula I, but instead of a cyclohexane ring a cyclohexene ring or cyclohexanone ring and / or instead of a -CH ₂ CH ₂ group a -CH = CH group and / or instead of a -CH ₂ group contain a -CO group and / or instead of an H atom a free or a functionally modified (eg in the form of its p-toluenesulfonate) OH group.

The reduction can be carried out, for example, by catalytic hydrogenation at temperatures between about 0 ° C. and about 200 ° C. and pressures between about 1 and 200 bar in an inert solvent, for example an alcohol such as methanol, ethanol or isopropanol, an ether such as tetrahydrofuran (THF) or dioxane, an ester such as ethyl acetate, a carboxylic acid such as acetic acid or a hydrocarbon such as cyclohexane. Suitable catalysts are suitably noble metals such as Pt or Pd, which can be used in the form of oxides (eg Pt0 ₂ , PdO), on a support (eg Pd on carbon, calcium carbonate or strontium carbonate) or in finely divided form. Ketones can also be prepared using the methods of Clemmensen (with zinc, amalgamated zinc or tin and hydrochloric acid, expediently in an aqueous alcoholic solution or in a heterogeneous phase with water / toluene at temperatures between about 80 and 120 ° C) or Wolff-Kishner (with hydrazine , expediently in the presence of alkali such as KOH or NaOH in a high-boiling solvent such as diethylene glycol or triethylene glycol at temperatures between about 100 and 200 ° C.) to give the corresponding compounds of the formula I, the alkyl groups and / or —CH ₂ CH ₂ -Bridges included, reduced.

Reductions with complex hydrides are also possible. For example, arylsulfonyloxy groups can be reductively removed with LiAIH ₄ , in particular p-toluenesulfonyloxymethyl groups can be reduced to methyl groups, advantageously in an inert solvent such as diethyl ether or THF at temperatures between about 0 and 100 ° C. Double bonds can be hydrogenated with NaBH ₄ or tributyltin hydride in methanol.

The starting materials are either known or can be prepared analogously to known compounds.

In addition to one or more compounds according to the invention, the liquid-crystalline media according to the invention preferably contain 2 to 40, in particular 4 to 30, components as further constituents. These media very particularly preferably contain 7 to 25 components in addition to 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 azoxybenzenes, benzylidene anilines, biphenyls, terphenyls, phenyl- or cyclohexylbenzoates, cyclohexanecarboxylic acid-phenyl- or cyclohexyl esters, phenyl- or cyclohexyl esters Cyclohexylbenzoic acid, phenyl or cyclohexyl ester of cyclohexylcyclohexane carboxylic acid, cyclohexyl phenyl ester of benzoic acid, cyclohexane carboxylic acid or cyclohexylcyclohexane carboxylic acid, phenyicyclohexanes, cyclohexylbiphenyls, phenylcyclohexylcyclohexanes, Cyclohexylcyclohexanes, cyclohexylcyclohexylcyclohexenes, 1,4-bis-cyclohexylbenzenes, 4,4'-bis-cyclohexylbiphenyls, phenyl- or cyclohexylpyrimidines, phenyl- or cyclohexylpyridines, phenyl- or cyclohexyldioxanes, phenyl- or 3-cyclohexyl-1 -dithiane, 1,2-diphenylethane, 1, 2-dicyclohexylethane, 1-phenyl-2-cyclohexylethane, 1-cyclohexyl-2- (4-phenyl-cyclohexyl) -ethane, 1-cyclohexyl-2-biphenylylethane, 1-phenyl -2- cyclohexylphenylethane, optionally halogenated stilbenes, benzylphenyl ether, tolanes and substituted cinnamic acids. The 1,4-phenylene groups in these compounds can also be fluorinated.

The most important as further components of media according to the invention in

Compounds in question can be characterized by formulas 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-CH ₂ CH ₂ -ER "4

R'-L-C≡C-E-R "5

in formulas 1, 2, 3, 4 and 5, L and E, which may be the same or different, each independently represent a bivalent radical from the group consisting of -Phe-, -Cyc-, -Phe-Phe-, -Phe- Cyc-, -Cyc-Cyc-, -Pyr-, -Dio-, -G-Phe- and -G-Cyc- as well as their mirror images formed group, whereby Phe unsubstituted or substituted by fluorine, 1,4-phenylene, Cyc trans- 1, 4-cyclohexylene or 1, 4-cyclohexylene, pyr pyrimidine-2-5-diyl or pyridine-2,5-diyl, dio 1, 3-dioxane-2,5-diyl and G 2- (trans-1, 4-Cyclohexyl) ethyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl or 1,3-dioxane-2,5-diyl.

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 contain one or more components selected from the compounds of the formulas 1, 2, 3, 4 and 5, in which L and E are selected from the group Cyc, Phe and Pyr and at the same time one or more components selected from the compounds of Formulas 1, 2, 3, 4 and 5, wherein one of the radicals L and E is selected from the group Cyc, Phe and Pyr and the other radical is selected from the group -Phe- Phe-, -Phe-Cyc-, -Cyc-Cyc-, -G- Phe- and -G-Cyc-, and optionally one or more components selected from the compounds of the formulas 1, 2, 3, 4 and 5, in which the radicals L and E are selected from the group -Phe-Cyc-, -Cyc -Cyc-, -G-Phe- and -G-Cyc-.

R 'and / or R "each independently represent alkyl, alkenyl, alkoxy, alkoxyalkyl, alkenyloxy or alkanoyloxy with up to 8 C atoms, -F, -Cl, -CN, -NCS, - (0) iCH _{3. ( k +} i) F _k CI |, where i are 0 or 1 and k and 1 are 1, 2 or 3.

In a smaller subgroup of the compounds of the formulas 1, 2, 3, 4 and 5, R 'and R "each independently represent alkyl, alkenyl, alkoxy, alkoxyalkyl, alkenyloxy or alkanoyloxy having up to 8 carbon atoms. In the following, this becomes smaller Subgroup called group A and the compounds are designated by the sub-formulas 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 subgroup of the compounds of the formulas 1, 2, 3, 4 and 5, referred to as group B, R "-F, -Cl, -NCS or - (0) ι CH _{3. (K +} i ₎ F _k Cl _! , where i is 0 or 1 and k and 1 are 1, 2 or 3; the compounds in which R "has this meaning are denoted by sub-formulas 1b, 2b, 3b, 4b and 5b. Particularly preferred are those compounds of the sub-formulas 1b, 2b, 3b, 4b and 5b in which R "has the meaning -F, -Cl, -NCS, -CF ₃ , -OCHF ₂ or -OCF ₃ .

In the compounds of partial formulas 1b, 2b, 3b, 4b and 5b, R 'has the meaning given for the compounds of partial formulas 1a-5a and is preferably alkyl, alkenyl, alkoxy or alkoxyalkyl.

In a further smaller subgroup of the compounds of the formulas 1, 2, 3, 4 and 5, R "means -CN; this subgroup is hereinafter referred to as group C and the compounds of this subgroup described accordingly with sub-formulas 1c, 2c, 3c, 4c and 5c. In the compounds of sub-formulas 1c, 2c, 3c, 4c and 5c, R 'has the meaning given for the compounds of sub-formulas 1a-5a and is preferably alkyl, alkoxy or alkenyl.

In addition to the preferred compounds of groups A, B and C, other compounds of the formulas 1, 2, 3, 4 and 5 with other variants of the proposed substituents are also common. All of these substances can be obtained by methods known from the literature or by analogy.

In addition to compounds of the formula I according to the invention, the media according to the invention preferably contain one or more compounds which are selected from group A and / or group B and / or group C. The mass fractions 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%

wherein the sum of the mass fractions of the compounds from groups A and / or B and / or C contained in the respective media according to the invention is preferably 5% -90% and in particular 10% to 90%.

The media according to the invention preferably contain 1 to 40%, particularly preferably 5 to 30% of the compounds according to the invention. Also preferred are media containing more than 40%, in particular 45 to 90%, of compounds according to the invention. The media preferably contain three, four or five compounds according to the invention. The liquid crystal mixtures which can be used according to the invention are prepared in a manner which is conventional per se. As a rule, the desired amount of the components used in a smaller amount is dissolved in the components which make up the main constituent, expediently at elevated temperature. It is also possible to mix solutions of the components in an organic solvent, for example in acetone, chloroform or methanol, and to remove the solvent after thorough mixing, for example by distillation. It is also possible to use the mixtures in other conventional ways, e.g. B. by using premixes, e.g. B. Homolog mixtures or using so-called "multi-bottle" systems.

The dielectrics can also contain further additives known to the person skilled in the art and described in the literature. For example, 0-15%, preferably 0-10%, pleochroic dyes and / or chiral dopants can be added. The individual added compounds are used in concentrations of 0.01 to 6%, preferably 0.1 to 3%. However, the concentration data for the other constituents of the liquid-crystal mixtures, ie the liquid-crystalline or mesogenic compounds, are given without taking into account the concentration of these additives.

The following examples are intended to illustrate the invention without limiting it. Percentages above and below mean percentages by weight. All temperatures are given in degrees Celsius.

"Conventional work-up" means: water is optionally added, extracted with methylene chloride, diethyl ether or toluene, the mixture is separated off, the organic phase is dried, evaporated and the product is purified by distillation under reduced pressure or crystallization and / or chromatography. embodiments

1. Synthesis of 2-butoxy-7-ethoxy-1,8,9,9-tetrafluorofluorene of the formula 8

8th

1.1 Preparation of 1-bromo-3-fluoro-4-butoxy-benzene (2)

0.315 mol of 4-bromo-2-fluorophenol (1), 1-butanol and triphenylphosphine were dissolved in 1000 ml of tetrahydrofuran and 0.315 mol of diisopropylazodicarboxylate was added dropwise at about 20 ° C. After stirring overnight, the solvent was distilled off on a rotary evaporator and the residue was worked up in the customary manner to give compound (2) in a yield of 95.6% of theory. .2 Preparation of the boron compound (3)

0.180 mol of n-butyllithium (as a 15% strength solution in n-hexane) was added dropwise to a solution of 0.162 mol of 1-bromo-3-fluoro-4-butoxybenzene (2) in 540 ml of diethyl ether at -70 ° C. After stirring for 30 minutes, 0.180 mol of trimethyl borate were added dropwise at -70 ° C. and stirring was continued for a further 30 minutes. The reaction mixture, which was heated to 20 ° C., was hydrolyzed with water, acidified with 2 molar hydrochloric acid and treated with methyl tert-butyl ether. It was worked up as usual to give compound (3) as a white solid.

1.3 Cross-coupling to 4-ethoxy-3,3'-difluoro-4'-butoxybiphenyl (5)

10 ml of tetrahydrofuran, 0.628 mmol of bis (triphenylphosphine) palladium dichloride and 0.630 mmol of hydrazinium hydroxide were added to 24.1 mmol of sodium metaborate octahydrate in 12.6 ml of H ₂ O.

Stirred for 5 minutes at room temperature. Then 32.1 mmol of the boron compound (3), 32.1 mmol of 1-bromo-3-fluoro-4-ethoxybenzene (4) (prepared analogously to Example 1.1) and 30 ml of tetrahydrofuran were added and the mixture was heated under reflux conditions for 6 hours , After cooling, the organic phase was separated off and worked up as usual.

1.4 Production of the Fluorenone Derivative (6)

60 mmol of 4-ethoxy-3,3'-difluoro-4'-butoxybiphenyl (5) are dissolved in 200 ml

Tetrahydrofuran submitted and cooled to -70 ° C. 120 mmol of a 1.6 M solution of n-butyllithium in hexane are added dropwise and the mixture is stirred at this temperature for 2 hours. 60 mmol of dimethyl carbonate are then added rapidly with vigorous stirring, the mixture is stirred for a further hour at -70 ° C., allowed to come to 0 ° C., hydrolyzed with dilute hydrochloric acid and worked up as usual. .5 Preparation of the dithioketal compound (7)

30 mmol of the fluorenone derivative (6) are dissolved in 100 ml of diethyl ether, mixed with 60 mmol of 1, 2-ethanediol and 45 mmol of boron trifluoride etherate and heated under reflux conditions overnight. After cooling, working up as usual. 27.5 mmol (92%) of the dithioketal (7) are obtained.

1.6 Oxidative fluorodesulfurization to the fluorene derivative (8).

11 mmol 1, 3-dibromo-5,5-dimethylhydantoin are dissolved in 50 ml dichloromethane and cooled to -70 ° C. 29 mmol of hydrogen fluoride in pyridine (65%) are added. 11 mmol of the dithioketal (7) dissolved in 50 ml of dichloromethane are added dropwise within 20 minutes and the temperature is raised to -60 ° C. after one hour. The reaction mixture is poured onto saturated sodium bicarbonate solution and then worked up as usual to obtain the fluorene derivative (8). (Δε = -21, 2, Δn = 0.204).

For comparison, 2-butoxy-7-ethoxy-9,9-difluorofluorene is measured for the difluorinated compound obtainable analogously: Δε = -9.1, Δn = 0.225.

Synthesis of 2-butoxy-7-ethoxy-1,8,9-trifluoro-9H-fluorene of the formula 9

20 mmol of the fluorenone compound (6) (obtainable according to Example 1.4) are dissolved in 100 ml of isopropanol and 8 mmol of sodium borohydride are added. The mixture is stirred for 3 hours at room temperature and worked as usual. The crude product is dissolved in 300 ml dichloromethane and cooled to 0 ° C. 20 mmol of diethylaminosulfur trifluoride are added dropwise and the mixture is worked up in the customary manner. The 9H-fluorene (9) is obtained. (Δε = -15.3, Δn = 0.214).

For comparison, 2-butoxy-7-ethoxy-9-fluoro-9H-fluorene was measured for the monofluorinated compound obtainable analogously: Δε = -4.7, Δn = 0.238.

Synthesis of 2-butoxy-7-ethoxy-1,8-difluoro-9.9H-fluorene of the formula 10

27 mmol of the fluorenone compound (6) (obtainable according to Example 1.4), 13 mmol of sodium borohydride and 74 mmol of aluminum chloride are suspended in 250 ml of tetrahydrofuran and heated under reflux conditions for 2 hours. After the usual work-up, 23.4 mmol (87%) of the 9.9H-fluorene (10) are obtained. (Δε = -8.7, Δn = 0.226).

For comparison, 2-butoxy-7-ethoxy-9.9H-fluorene was measured for the non-fluorinated compound obtainable analogously: Δε = -0.5, Δn = 0.253. , Synthesis of the 1,8,9,9-tetrafluorofluorene compound of the formula 20

.1 Preparation of 1-bromo-2 ', 3'-difluoro-4'-ethoxybiphenyl (13)

0.450 mol sodium metaborate are placed in 240 ml water. 0.012 mol of bis (triphenylphosphine) palladium (II) chloride, 0.6 mol of 4-bromo-1-iodobenzene (11) and 0.012 mol of hydrazinium hydrochloride are added and the mixture is stirred at about 20 ° C. for 5 min. After that

0.6 mol of 2,3-difluoro-4-ethoxyphenylboronic acid (12) dissolved in 600 ml of tetrahydrofuran is added and the mixture is heated under reflux for 4 hours, whereupon the compound of the formula 13 is obtained.

4.2 Preparation of the Boronic Acid Compound (14)

0.09 mol of 1-bromo-2 ', 3'-difluoro-4'-ethoxybiphenyl (13) are dissolved in 200 ml of diethyl ether and cooled to -70 ° C. 0.095 mol of butyllithium is added dropwise at this temperature and the mixture is stirred for 45 min. Then 0.1 mol of trimethyl borate is added, the mixture is stirred for 30 minutes and worked up as usual after warming up to about 20 ° C.

4.3 Preparation of the Terphenyl Compound (16)

0.047 mol 2 ', 3'-difluoro-4'-ethoxybiphenylboronic acid (14), 0.05 mol

1-bromo-3-fluoro-4-iodobenzene (15), 1 mmol of palladium acetate, 2 mmol of triphenylphosphine, 25 ml of saturated sodium carbonate solution, 20 ml of water and 100 ml of isopropanol are initially introduced and refluxed overnight. After the usual work-up, the terphenyl compound (16) is obtained.

4.4 Preparation of the compound of formula 18

The preparation is carried out analogously to Example 1.3 using the terphenyl compound (16) and 3-fluoro-4-ethoxyphenylboronic acid (17). 4.5 Preparation of the Fluorenone Compound (19)

The synthesis is carried out analogously to example 1.4 using the compound (18) obtained previously.

4.6 Preparation of the 1,8,9,9-tetrafluorofluorene compound (20)

The compound (20) is obtained in the last step analogously to Examples 1.5 and 1.6 by oxidative fluorodesulfurization of the compound (19) (Δε = -28.8, Δn = 0.282).

Analogously to Examples 1.1 to 1.6, in particular 1.5 and 1.6, fluorene compounds of the following formula are obtained:

R ¹ R ^

(21) -C ₃ H -C ₃ H ₇ -H -F

(23) -C ₃ H -C ₅ H ₁₁ -H -F

(24) -C ₃ H -OC ₂ H ₅ -H -F

(25) -C ₃ H -OC ₃ H ₇ -H -F

(26) -C ₃ H -OC ₄ Hg -H -F

(27) -C ₃ H -OC ₅ H ₁₁ -H -F

(28) -CHg -C ₃ H -H -F

(29) -C ₄ Hg -CHg -H -F

(31) -C ₄ Hg -OC ₂ H ₅ -H -F

(32) -C ₄ Hg -OC ₃ H ₇ -H -F

(33) -C ₄ Hg -OC ₄ Hg -H -F

(35) -C ₅ H ₁₁ -C ₃ H -H -F

(37) -C ₅ H ₁₁ -C ₅ H ₁₁ -H -F

(38) -C ₅ H ₁₁ -OC ₂ H ₅ -H -F

(39) -C ₅ H ₁₁ -OC ₃ H ₇ -H -F

(40) -C ₅ H ₁₁ -OC ₄ H ₉ -H -F

(41) -C ₅ H ₁₁ -OC ₅ H ₁₁ -H -F

(42) -CH = CH ₂ -C ₃ H -H -F

(44) -CH = CH ₂ -C ₅ H ₁₁ -H -F

(45) -CH = CH ₂ -CH = CH ₂ -H -F

(46) -CH = CH ₂ -CH = CH-CH ₃ -H -F

(47) -CH = CH ₂ -CH ₂ -CH = CH-CH ₃ -H -F

(48) -CH = CH ₂ -C ₂ H ₄ -CH ⁼ CH ₂ -H -F (49) -CH = CH ₂ -C ₂ H ₄ -CH ⁼ € H-CH ₃ -H -F

(50) -CH = CH ₂ -OC ₂ H ₅ -H -F

(51) -CH = CH ₂ -OC ₃ H ₇ -H -F

(52) -CH = CH ₂ -OC ₄ Hg -H -F

(53) -CH = CH ₂ -OC5H ₁₁ -H -F

(54) -CH = CH-CH ₃ -C ₃ H -H -F

(55) -CH = CH-CH ₃ -C ₄ Hg -H -F

(56) -CH = CH-CH ₃ -C ₅ H1 ₁ -H -F

(57) -CH = CH-CH ₃ -CH = CH ₂ -H -F

(58) -CH = CH-CH ₃ -CH = CH-CH ₃ -H -F

(59) -CH = CH-CH ₃ -CH ₂ -CH ⁼ CH-CH ₃ -H -F

(60) -CH = CH-CH ₃ -C ₂ H -CH ⁼ = CH ₂ -H -F

(61) -CH = CH-CH ₃ -C ₂ H ₄ -CH ⁼ = CH-CH ₃ -H -F

(62) -CH = CH-CH ₃ -OC ₂ H ₅ -H -F

(63) -CH = CH-CH ₃ -OC ₃ H ₇ -H -F

(64) -CH = CH-CH ₃ -OC ₄ Hg -H -F

(65) -CH = CH-CH ₃ -OC ₅ H11 -H -F

(66) -Cπ ₂ -CH ⁼ CH-CH ₃ -C ₃ H -H -F

(67) -CH ₂ -CH ⁼ CH-CH ₃ -C ₄ Hg -H -F

(69) -Cπ2-CH ⁼ CH-CH ₃ -CH = CH ₂ -H -F

(70) -Cπ ₂ -CH ⁼ CH-CH ₃ -CH = CH-CH ₃ -H -F

(71) -CH ₂ -CH = CH-CH ₃ -CH ₂ -CH = CH-CH ₃ -H -F

(72) -CH2 ^_ CH ⁼ CH-CH ₃ -C2H ₄ -CH ^: = CH ₂ -H -F

(73) -CH2-CH ⁼ CH-CH ₃ -C2H -CH ^: = CH-CH ₃ -H -F

(74) -CH ₂ -CH ⁼ CH-CH ₃ -OC ₂ H ₅ -H -F

(75) -CH ₂ -CH ⁼ CH-CH ₃ -OC ₃ H ₇ -H -F

(76) -CH2-CH ⁼ CH-CH ₃ -OC ₄ H ₉ -H -F

(77) -CH ₂ -CH = CH-CH ₃ -OC5H11 -H -F

(78) -C2H4-CH ⁼ CH ₂ -CsH -H -F

(79) -C2H ₄ -CH ⁼ CH2 -C Hg -H -F

(80) -C2H.4-CH-CH2 -C ₅ H11 -H -F

(81) -C2H ₄ -CH ⁼ CH2 -CH = CH ₂ -H -F

(83) -C2H4-CH ⁼ CH2 -CH ₂ -CH = = CH-CH ₃ -H -F

(84) -C ₂ H ₄ -CH ^=: CH2 -C2H -CH = CH ₂ -H -F (85) -C ₂ H ₄ -CH = = CH ₂ -C ₂ H -CH- CH-CH ₃ -H -F

(86) -C2H -CH = = CH ₂ -OC ₂ H ₅ -H -F

(87) -C ₂ H -CH ⁼ = CH ₂ -OC ₃ H ₇ -H -F

(88) -C ₂ H ₄ -CH ⁼ = CH ₂ -OC ₄ Hg -H -F

(89) -C2H -CH = = CH ₂ -OC ₅ Hn -H -F

(90) -C ₂ H ₄ -CH ⁼ = CH-CH ₃ -C ₃ H -H -F

(91) -C ₂ H ₄ -CH ^: = CH-CH ₃ -C ₄ Hg -H -F

(92) -C ₂ H ₄ -CH ^: = CH-CH ₃ -C ₅ H1 ₁ -H -F

(93) -C2H ₄ -CH ^: = CH-CH ₃ -CH = CH ₂ -H -F

(94) -C2H ₄ -CH ^: = CH-CH ₃ -CH = CH-CH ₃ -H -F

(95) -C2H -CH ^: = CH-CH ₃ -CH ₂ -CH ⁼ CH-CH ₃ -H -F

(96) -C ₂ H ₄ -CH ^: = CH-CH ₃ -C2H -CH ⁼ CH2 -H -F

(97) -C2H ₄ -CH ^: = CH-CH ₃ -C ₂ H ₄ -CH ⁼ CH-CH ₃ -H -F

(98) -C ₂ H ₄ -CH ^: = CH-CH ₃ -OC ₂ H ₅ -H -F

(99) -C ₂ H ₄ -CH ^: = CH-CH ₃ -OC ₃ H ₇ -H -F

(100) -C2H ₄ -CH ^: = CH-CH ₃ -OC ₄ Hg -H -F

(101) -C ₂ H ₄ -CH ^: = CH-CH ₃ -OC ₅ Hn -H -F

(103) -OC ₂ H ₅ -C ₄ H ₉ -H -F

(104) -OC2H5 -C ₅ H11 -H -F

(105) -OC ₂ H ₅ -OC ₂ H ₅ -H -F

(106) -OC ₂ H ₅ -OC ₃ H ₇ -H -F

(107) -OC2H5 -OC ₄ H ₉ -H -F

(108) -OC ₂ H ₅ -OC ₅ Hn -H -F

(109) -OC ₃ H ₇ -C ₃ H -H -F

(HD -OC ₃ H ₇ -C ₅ H11 -H -F

(112) -OC ₃ H ₇ -OC2H5 -H -F

(113) -OC ₃ H ₇ -OC ₃ H ₇ -H -F

(114) -OC ₃ H ₇ -OC ₄ Hg -H -F

(115) -OC ₃ H ₇ -OC ₅ H ₁ 1 -H -F

(116) -OC ₄ H ₉ -C ₃ H ₇ -H -F

(117) -OC ₄ Hg -C ₄ Hg -H -F

(118) -OC ₄ H ₉ -C5H11 -H -F

(119) -OC4H ₉ -OC ₂ H ₅ -H -F

(120) -OC ₄ H ₉ -OC ₃ H ₇ -H -F co o ro cn cn o cn o cn

WW (

o OoO oo

4. co cnJ 4-.)

1 X0 X - X1 cXo

4

t x 1 x I x t x I x I x I x I x I x I x I x I x I x I

X X X X X X X X X X X X xxxxxxxxx

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 "π" π τi "π" π τι τι -π n Ti m Ti ii Ti -π -π Ti -π Ti ii -π -π -π ti Ti -π Ti -n Ti -π - -π -π Ti -π o ω c ω ω ω co c co co c co c co co ω cc co co c co ccc ω c

(157) -OC ₂ H ₅ -OC5H11 -H -CF ₃

(158) -OC ₃ H ₇ -C ₃ H ₇ -H -CF ₃

(159) -OC ₃ H ₇ -C ₄ Hg -H -CF ₃

(160) -OC ₃ H ₇ -C ₅ H ₁₁ -H -CF ₃

(161) -OC ₃ H ₇ -OC ₂ H ₅ -H -CF ₃

(162) -OC ₃ H ₇ -OC ₃ H ₇ -H -CF ₃

(163) -OC ₃ H ₇ -OC ₄ Hg -H -CF ₃

(164) -OC ₃ H ₇ -OC ₅ H ₁₁ -H -CF ₃

(165) -OC ₄ H ₉ -C ₃ H ₇ -H -CF ₃

(166) -OC ₄ H ₉ -C ₄ Hg -H -CF ₃

(167) -OC ₄ H ₉ -C ₅ H ₁₁ -H -CF ₃

(168) -OC ₄ H ₉ -OC2H5 -H -CF ₃

(169) -OC ₄ H ₉ -OC ₃ H ₇ -H -CF ₃

(170) -OC ₄ H ₉ -OC ₄ Hg -H -CF ₃

(171) -OC ₄ H ₉ -OC ₅ Hn -H -CF ₃

(172) -OC ₅ Hn -C ₃ H ₇ -H -CF ₃

(173) -OC ₅ Hn -C ₄ Hg -H -CF ₃

(174) -OC ₅ H11 -C ₅ H ₁₁ -H -CF ₃

(175) -OCsHn -OC2H5 -H -CF ₃

(176) -OC ₅ Hn -OC ₃ H ₇ -H -CF ₃

(177) -OC ₅ H11 -OC ₄ H ₉ -H -CF ₃

(178) -OC ₅ Hn -OC ₅ H ₁₁ -H -CF ₃

(179) -C ₃ H ₇ -C ₃ H ₇ -F -CF ₃

(180) -C ₃ H ₇ -C ₄ Hg -F -CF ₃

(181) -C3H7 -C ₅ H ₁₁ -F -CF ₃

(182) -C ₃ H ₇ -OC ₂ H ₅ -F -CF ₃

(183) -C ₃ H ₇ -OC ₃ H ₇ -F -CF ₃

(184) -C ₃ H ₇ -OC ₄ H ₉ -F -CF ₃

(185) -C ₃ H ₇ -OC _s Hn -F -CF ₃

(186) -C ₄ H ₉ -C ₃ H ₇ -F -CF ₃

(187) -C ₄ Hg -C ₄ Hg -F -CF ₃

(188) -C ₄ H ₉ -C ₅ H1 ₁ -F -CF ₃

(189) -C ₄ H ₉ -OC2H5 -F -CF ₃

(190) -C ₄ H ₉ -OC ₃ H ₇ -F -CF ₃

(191) -C ₄ H ₉ -OC ₄ Hg -F -CF ₃

(192) -C ₄ Hg -OC ₅ H ₁₁ -F -CF ₃ (193) -C ₅ H ₁₁ -C ₃ H ₇ -F -CF ₃

(194) -C ₅ H ₁₁ -C ₄ H ₉ -F -CF ₃

(195) -C ₅ H ₁₁ -C5H ₁₁ -F -CF ₃

(196) -C ₅ H ₁₁ -OC ₂ H ₅ -F -CF ₃

(197) -C ₅ H ₁₁ -OC ₃ H ₇ -F -CF ₃

(198) -C ₅ H ₁₁ -OC ₄ Hg -F -CF ₃

(199) -C ₅ H ₁₁ -OC ₅ H ₁₁ -F -CF ₃

(200) -CH = CH ₂ -C ₃ H -F -CF ₃

(201) -CH = CH ₂ -CHg -F -CF ₃

(202) -CH = CH ₂ -C ₅ H ₁₁ -F -CF ₃

(203) -CH = CH ₂ -CH = CH ₂ -F -CF ₃

(204) -CH = CH ₂ -CH = CH-CH ₃ -F -CF ₃

(205) -CH = CH ₂ -CH ₂ -CH ⁼ CH-CH ₃ -F -CF ₃

(207) -CH = CH ₂ -C ₂ H ₄ -CH = CH-CH ₃ -F -CF ₃

(208) -CH = CH ₂ -OC ₂ H ₅ -F -CF ₃

(209) -CH = CH ₂ -OC ₃ H ₇ -F -CF ₃

(210) -CH = CH ₂ -OC ₄ Hg -F -CF ₃

(211) -CH = CH ₂ -OC ₅ H ₁₁ -F -CF ₃

(212) -CH = CH-CH ₃ -C ₃ H -F -CF ₃

(213) -CH = CH-CH ₃ -C ₄ Hg -F -CF ₃

(214) -CH = CH-CH ₃ -C ₅ H ₁₁ -F -CF ₃

(215) -CH = CH-CH ₃ -CH = CH ₂ -F -CF ₃

(216) -CH = CH-CH ₃ -CH = CH-CH ₃ -F -CF ₃

(217) -CH = CH-CH ₃ -CH ₂ -CH ⁼ CH-CH ₃ -F -CF ₃

(218) -CH = CH-CH ₃ -C ₂ H ₄ -CH ⁼ CH2 -F -CF ₃

(219) -CH = CH-CH ₃ -C ₂ H ₄ -CH ⁼ CH-CH ₃ -F -CF ₃

(220) -CH = CH-CH ₃ -OC ₂ H ₅ -F -CF ₃

(221) -CH = CH-CH ₃ -OC ₃ H ₇ -F -CF ₃

(222) -CH = CH-CH ₃ -OC ₄ Hg -F -CF ₃

(223) -CH = CH-CH ₃ -OC ₅ Hn -F -CF ₃

(224) -CH ₂ -CH ⁼ CH-CH ₃ -C ₃ H -F -CF ₃

(225) -CH ₂ -CH = CH-CH ₃ -CHg -F -CF ₃

(226) -CH ₂ -CH = CH-CH ₃ -C ₅ H ₁₁ -F -CF ₃

(227) -CH ₂ -CH = CH-CH ₃ -CH = CH ₂ -F -CF ₃

(228) -CH ₂ -CH = CH-CH ₃ -CH = CH-CH ₃ -F -CF ₃ (229) -CH ₂ -CH = CH-CH ₃ -CH ₂ -CH = <CH-CH ₃ -F -CF ₃

(230) -CH ₂ -CH ⁼ CH-CH ₃ -C ₂ H ₄ -CH ⁼ = CH ₂ -F -CF ₃

(231) -CH ₂ -CH = CH-CH ₃ -C2H ₄ -CH ⁼ = CH-CH ₃ -F -CF ₃

(232) -CH ₂ -CH ⁼ CH-CH ₃ -OC2H5 -F -CF ₃

(233) -CH2-CH ⁼ CH-CH ₃ -OC ₃ H ₇ -F -CF ₃

(234) -CH ₂ ^_ CH ⁼ CH-CH ₃ -OC ₄ Hg -F -CF ₃

(235) -CH ₂ -CH ⁼ CH-CH ₃ -OC5H11 -F -CF ₃

(236) -C ₂ H ₄ -CH ⁼ CH ₂ -C ₃ H -F -CF ₃

(239) -C2H -CH = CH ₂ -CH = CH ₂ -F -CF ₃

(240) -C2H4-CH ⁼ CH ₂ -CH = CH-CH ₃ -F -CF ₃

(241) -C ₂ H ₄ -CH ⁼ CH ₂ -CH ₂ -CH = CH-CH ₃ -F -CF ₃

(242) -C2H ₄ -CH ^: = CH ₂ -F -CF ₃

(243) -C2H ₄ -CH ⁼ CH2 -C2H ₄ -CH ^: = CH-CH ₃ -F -CF ₃

(244) -C ₂ H ₄ -CH ^{: =} CH ₂ -OC ₂ H ₅ -F -CF ₃

(245) -C2H ₄ -CH ⁼ CH2 -OC ₃ H ₇ -F -CF ₃

(246) -C2H ₄ -CH ⁼ CH2 -OC ₄ Hg -F -CF ₃

(247) -C ₂ H ₄ -CH ⁼ CH ₂ -OC ₅ H11 -F -CF ₃

(248) -C ₂ H ₄ -CH ⁼ CH-CH ₃ -C ₃ H -F -CF ₃

(249) -C ₂ H ₄ -CH ⁼ CH-CH ₃ -C ₄ Hg -F -CF ₃

(250) -C ₂ H ₄ -CH ⁼ CH-CH ₃ -C ₅ H11 -F -CF ₃

(251) -C ₂ H ₄ -CH ⁼ CH-CH ₃ -CH = CH ₂ -F -CF ₃

(252) -C2H ₄ -CH ⁼ CH-CH ₃ -CH = CH-CH ₃ -F -CF ₃

(253) -C ₂ H ₄ -CH ⁼ CH-CH ₃ -CH ₂ -CH = = CH-CH ₃ -F -CF ₃

(254) -C2H ₄ -CH ⁼ CH-CH ₃ -C ₂ H ₄ -CH = CH ₂ -F -CF ₃

(255) -C2H ₄ -CH = CH-CH ₃ -F -CF ₃

(256) -C ₂ H ₄ -CH ⁼ CH-CH ₃ -OC2H5 -F -CF ₃

(257) -C ₂ H ₄ -CH = CH-CH ₃ -OC ₃ H ₇ -F -CF ₃

(258) -C2H ₄ -CH ⁼ CH-CH ₃ -OC ₄ H ₉ -F -CF ₃

(259) -C2H ₄ -CH ⁼ CH-CH ₃ -OC ₅ Hn -F -CF ₃

(260) -OC ₂ H ₅ -C ₃ H -F -CF ₃

(261) -OC ₂ H ₅ -C ₄ Hg -F -CF ₃

(262) -OC2H5 -C5H11 -F -CF ₃ Δε = -17.4; .DELTA.n = 0.159

(263) -OC2H5 -OC ₂ H ₅ -F -CF ₃ oo cn cn o cn o cn

to to to to to to to to to to to to to to io to to to to to to to to to to to to to to

MD M3 MD MD M MD M MD oo ^ i σ _\ n ^ - θ ι— 'MD OO i σN Cn 4 ^ CO tO ι-- MD OO - l CJ _\ Cn 4 ^ C tO ι— »O MD OO OQ \ Cn 4 ^

4 os. 4o-. * o- 4o »- ωo coo coo ωo xxxxxxx

ό ό c 0o to0

~ X cXn

τι ~ π τι τι "π τι" π τι τι τι τι τι τι τι τι τι T | Tl T | TI TI TI TI TI TI TI TI I TI

I I I I I I I I

TI TI TI TI -Π TI TI TI TI TI TI O O O O O O O O O O O O O O O O O O O O O O O O

Tl Tl Tl co ω co c τoι cτoι cτoι cτoι cτoι cτoι cτoι cτoι cτoι c-on cτoι l Tl Tl cτoι cτoι T co co co o

co o ro ro cn cn o cn σ cn

1 T1 | T | T1 T1 T1 T | T | T | T | T1 T1 T | T | T1 T | "π τι -π τι τι τι τι τι τι τι T | T | T | T |

I

Tl Tl Tl Tl Tl Tl Tl Tl m T1 TI T1 T1 TI T1 TI T1 T1 T1 T1 Tl Tl Tl Tl Tl Tl Tl Tl

>>

H !'

^" _-- o

00 - •

o co ro ro cn cn o cn o cn

CO LO CO CO CO CO CO CO CO CO J CO CO CO CO LO O CO CO CO O LO CO LO CO CO CO CO CO CO CO CO CO CO LO CO

Ch Ch Ch Ch Ch Ch Ch Ch Ch cn cn cn cn cn cn cn cn cn cn Φ. j- 4- j. 4- ^ 4- 4i 4- ω ω ω u ω ω

MD OO -J Ch Cn 4 ^ CO tO ι-- O MD OO -O Ch Cn 4 ^ CO tO ι— 'O MD OO -J Ch Cn 4 ^ <-O tO ι—> O MD OO -O Ch Cn 4 ^

I I I I I I I 1 I I I I I I I 1 I 1 I I I I I I I I I I 1 I I I

Oo c Oo Oo c Oo O O O O O O O O O o r o to o t oo r oo ro t oo r oo io o r oo r oo r oo to o r oo r oo t oo io o t oo o o o o o c on 4o. 4o-, ωo ωo coo roo ro o o o o ro r Xo r Xo r X X

X o ro t Xo J - X-1 - X4 - X ι J 4 Xk X 4 Xk X X X X X X X X X X X X X x x x x x x x x x x I I I I I

I ι I o o o o o o o o o o o o o o o o o o o o o

X X X x x x x x x x x x x x x x x X X X X X

II II II II II II II II II II II II II II II II M ö Ö II ö II II II OOOOOOOOOOOOOOOOOX ^ T x IXIXIXIX ι x ι x ι x ι x ι xix ι xi txo tox rxo rxo rxo rxo rxo rxo iox oooooooooooooxxxxxxxx XXXXX

Tl Tl Tl Tl Tl T | T | T | Tl T | Tl Tl τoι c τoι τoι c τoι

O O O O τι τι -n τι τι τι τι τι τι τι τι τι τι τι τι τι -π Tl Tl T | Tl Tl Tl T | Tl T | T | T |

Tl Tl Tl Tl co co co co

o ro ro cn cn o cn o cn

C 0J C0 C0 04 0J 0 C0 C0 J C UJ C0 C0 L0 C0 C0 C0 C0 C0 CO C0 C0 C0

VO J ^ O OO OO OO OO ∞ ∞ O OO OO OO vJ sJ ll sJ J sl -J l vO C (O ι— 'O MD OO -O Ch Cn 4 ^ CO t ι—' O MD OO -O Ch Cn 4> - CO tO i—> o

OOOO c On 4Ok 4Ok cOo

- x ^j . cxD xO '-xi ^ xj -xi cxn cxn cxn cxn - - _ _

O O O O O O O O O O O O O cOn cOn 4Ok cOn 4Ok cOo cOn 4Ok cOo tOo cOn 4Ok cOo rOo

- _X tXD _X CXD XJ -X (XO X üXl -X (XD Xl üXl

4 0

τ όι τι -όπ τι τöι ö- ό ό ό ό ό ό ö ö ö ό co co co co coπ cτoι cτoι cτoι cτoι cτoι c-oπ cτoι c-oπ cτoι cτoι cτoι c-oπ cτoιo

O O O O O O O O O O O O O O O O O O O O O O O O

T1 T1 T1 T | T1 T1 T1 T | T | T1 T | T1 T1 T | T1 T | T1 T1 T | T | T1 T1 T1 T | oi co o co co co co co co co co co co co co co co co co co co co co co

o co ro ro cn cn o cn o cn

(426) -CH = CH ₂ -CH ₂ -CH = CH-CH ₃ -H -F

(427) -CH = CH ₂ -C ₂ H ₄ -CH = CH ₂ -H -F

(428) -CH = CH ₂ -C ₂ H ₄ -CH = CH-CH ₃ -H -F

(429) -CH = CH ₂ -0C ₂ H ₅ -H -F

(430) -CH = CH ₂ -0C ₃ H ₇ -H -F (431) -CH = CH ₂ -OC ₄ H ₉ -H -F

(432) -CH = CH ₂ -OC ₅ Hn -H -F

(433) -CH = CH-CH ₃ -C ₃ H ₇ -H -F

(434) -CH = CH-CH ₃ -C ₄ H ₉ -H -F

(435) -CH = CH-CH ₃ -C ₅ Hn -H -F (436) -CH = CH-CH ₃ -CH = CH ₂ -H -F

(437) -CH = CH-CH ₃ -CH = CH-CH ₃ -H -F

(438) -CH = CH-CH ₃ -CH ₂ -CH = CH-CH ₃ -H -F

(439) -CH = CH-CH ₃ ^• -C ₂ H ₄ -CH = CH ₂ -H -F

(440) -CH = CH-CH ₃ -C ₂ H ₄ -CH = CH-CH ₃ -H -F (441) -CH = CH-CH ₃ -OC ₂ H ₅ -H -F

(442) -CH = CH-CH ₃ -OC ₃ H ₇ -H -F

(443) -CH = CH-CH ₃ -OC ₄ H ₉ -H -F

(444) -CH = CH-CH ₃ -OC ₅ Hn -H -F

(445) -CH ₂ -CH = CH-CH ₃ -C ₃ H ₇ -H -F (446) -CH ₂ -CH = CH-CH ₃ -C ₄ H ₉ -H -F

(447) -CH ₂ -CH = CH-CH ₃ -C ₅ Hn -H -F

(448) -CH ₂ -CH = CH-CH ₃ -CH = CH ₂ -H -F

(449) -CH ₂ -CH = CH-CH ₃ -CH = CH-CH ₃ -H -F

(450) -CH ₂ -CH = CH-CH ₃ -CH ₂ -CH = CH-CH ₃ -H -F (451) -CH ₂ -CH = CH-CH ₃ -C ₂ H ₄ -CH = CH ₂ -H -F

(452) -CH ₂ -CH = CH-CH ₃ -C ₂ H ₄ -CH = CH-CH ₃ -H -F

(453) -CH ₂ -CH = CH-CH ₃ -OC ₂ H ₅ -H -F

(454) -CH ₂ -CH = CH-CH ₃ -OC ₃ H ₇ -H -F

(455) -CH ₂ -CH = CH-CH ₃ -OC ₄ H ₉ -H -F (456) -CH ₂ -CH = CH-CH ₃ -OC ₅ Hn -H -F

(457) -C ₂ H ₄ -CH = CH ₂ -C ₃ H ₇ -H -F

(458) -C ₂ H ₄ -CH = CH ₂ -C ₄ H ₉ -H -F

(459) -C ₂ H ₄ -CH = CH ₂ -C ₅ Hn -H -F

(460) -C ₂ H ₄ -CH = CH ₂ -CH = CH ₂ -H -F (461) -C ₂ H ₄ -CH = CH ₂ -CH = CH-CH ₃ -H -F (462) -C ₂ H ₄ -CH = CH ₂ -CH ₂ -CH = CH-CH ₃ -H -F

(463) -C ₂ H ₄ -CH = CH ₂ -C ₂ H ₄ -CH = CH ₂ -H -F

(464) -C ₂ H ₄ -CH = CH ₂ -C ₂ H ₄ -CH = CH-CH ₃ -H -F

(465) -C ₂ H ₄ -CH = CH ₂ -OC ₂ H ₅ -H -F

(466) -C ₂ H ₄ -CH = CH ₂ -OC ₃ H ₇ -H -F (467) -C ₂ H ₄ -CH = CH ₂ -OC4H ₉ -H -F

(468) -C ₂ H ₄ -CH = CH ₂ -OC5H11 -H -F

(469) -C ₂ H ₄ -CH = CH-CH ₃ -C ₃ H ₇ -H -F

(470) -C ₂ H ₄ -CH = CH-CH ₃ -C ₄ H ₉ -H -F

(471) -C ₂ H ₄ -CH = CH-CH ₃ -C ₅ Hn -H -F (472) -C ₂ H ₄ -CH = CH-CH ₃ -CH = CH ₂ -H -F

(473) -C ₂ H ₄ -CH = CH-CH ₃ -CH = CH-CH ₃ -H -F

(474) -C ₂ H ₄ -CH = CH-CH ₃ -CH ₂ -CH = CH-CH ₃ -H -F

(475) -C ₂ H ₄ -CH = CH-CH ₃ -C ₂ H ₄ -CH = CH ₂ -H -F

(476) -C ₂ H ₄ -CH = CH-CH ₃ -C ₂ H ₄ -CH = CH-CH ₃ -H -F (477) -C ₂ H ₄ -CH = CH-CH ₃ -OC ₂ H ₅ -H -F

(478) -C ₂ H ₄ -CH = CH-CH ₃ -OC ₃ H ₇ -H -F

(479) -C ₂ H ₄ -CH = CH-CH ₃ -OC ₄ H ₉ -H -F

(480) -C ₂ H ₄ -CH = CH-CH ₃ -OC ₅ H ₁₁ -H -F (482) -OC ₂ H ₅ -C ₄ H ₉ -H -F

(484) τOC ₂ H ₅ -OC2H5 -H -F

(485) -OC ₂ H5 -OC ₃ H ₇ -H -F

(486) -OC ₂ H ₅ -OC ₄ H ₉ -H -F (487) -OC2H5 -OC ₅ Hn -H -F

(488) -OC ₃ H ₇ -C ₃ H ₇ -H -F

(489) -OC ₃ H ₇ -C ₄ H ₉ -H -F

(490) -OC ₃ H ₇ -C5H ₁₁ -H -F

(491) -OC ₃ H ₇ -OC2H ₅ -H -F (492) -OC ₃ H ₇ -OC ₃ H ₇ -H -F

(493) -OC ₃ H ₇ -OC ₄ H ₉ -H -F

(494) -OC ₃ H ₇ -OC ₅ Hn -H -F

(495) -OC ₄ H ₉ -C ₃ H ₇ -H -F

(496) -OC ₄ H ₉ -C ₄ H ₉ -H -F (497) -OC ₄ H ₉ -C ₅ Hn -H -F oo ro ro cn cn o cn o cn

cn cn cn cn cn cn cn cn cn cn cn cn cn cn cn cn cn cn cn cn cn cn cn cn cn cn cn cn cn cn cn cn cn cΛ cn cn 4 ^ -tk.

CO CO CO CO tO tO tO tO tO tO tO lO tO tO t— '> - »►_- ►— i> -. > -. > - », _- ►—»> - 'O O O O O O O O O O MD MD co to i—' θ MD oo -o; ch cn 4-. co to> - 'θ MD θo ^ j ch cn 4 ^ co to> -> o MD oo -. Ch cn 4 ^ <-o to> - 'O MD OO ό ö ό ό ό ό ό ό ö ö ό ό ö ό ό ό ö ό ό ό ö ό ό ö ό ö ö oooo XXXXXXXXX ok 4ok 4ok 4ok cX Xo cXo xxxxxxxxxc on con con con con ooι con 4 c Xn c Xn cXn cXn XXXXXXXXXXX

ό ό ό ό ό ό ό ό ό ό ό -i- con 4θ ό ό ό ό ^ ό ό ό ό ό -J-- ^ -i-- ° -J _r -. con 4θk coO r oo r

I I I I I I I I I I I I I x x x x x x x x x x x x x x X X X x x x x x x x x x x x x x x x x x x x

O O O O O O O O O O O O O O O O O O O O O O O O Ti Ti Ti Ti Ti Ti τι τι τι τι

Tl Tl T | T | Tl T | TI T1 T | T | T1 TI T | T | T | T1 T1 T1 T1 T | T1 T1 T | co o co co o co co co co co co co co co co co co co co co co co co

o co ro ro cn cn o cn o cn

cn cn cn cn cn cn cn cn cn cn cn cn cn

Ch Ch Ch Ch Ch Ch Ch Ch Ch Ch Cn Cn IΛ MD OO -O Ch Cn 4k. C tO>-> O MD OO -0 ι I

4 ok 4ok 4ok 4ok 4ok CoO CoO coo coo coo oo oo o o o o o o o o o o o o o o o o o o o o o o o X X X X C On mO cOn cOn cOn cOn cOn 4Ok 4Ok 4Ok 4Ok 4Ok 4Ok 4O cO cOoOOOOOOOO

C XD CXD CXO CXO CXD -XJ -X X x x x x x x x x x x x x x x x x x x x x x x x x

o o o o o o o o o

<°. M °. d- X- X O - cn 4 Ok c Oo t Oo

-4 cn - X c Xo - X4 c Xn c

Tl Tl Tl Tl Tl Tl Tl Tl x x x x x x x x x x x x x x x x x x x x x x x x

• T öτιl Tl, Tό-fll T-πl ό-π ό- _π τό ₁ -π ö- _π -ό _τl ό- _π ö-η τό _{1 1} ö ₁ ό- _r | ₁ ö ₁ - _π -öη -όη - _{π ιl} -ό _{π τι} - _π ö- _{I1 1} ό ₁ ό- | ₁ ό- _π ό-η -ö _π ό- _I1 τö ₁ ö- _{T |} - _{π ιl} - _n co oo co ω co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co

o o ro ro cn cn o cn o cn

CΛ cD>

OO cn -fc-

I I I I I I I I I I I I I I I 1 I I I I I I I I 1 I I I I I I | I I I I o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o

XXXXXXXX ^~ X ^~ X ^~~ X ^" XXXXXXXXXXXXXXXX cn cn cn cn cn cn k

11 II II II II II II II II II II II II II II II II II II II II II II X X X X X X X X o o o o o o o o o o o o o o o o o o o o o o o o o o

X X X X II ι X ι X ι X II ι x ι x ι x ι x ι x ι x ι x ι x ι rxo r Xo to X r Xo t Xo r Xo t Xo r Xo r Xo to X rXo rXo o o o o o o o o o o o o o o o

X c Xo c Xo c Xo c Xo c Xo c Xo c Xo c Xo c Xo c Xo Xo c Xo

I X X o I X o I X o

I I I I I I I 1

Tl T | Tl T | Tl Tl T | T | Tl T | T | Tl Tl Tl Tl Tl T | Tl T | T | Tl T | Tl Tl Tl T | T | T | tl

ö "τπι ττιι" Tl ö -π ό "n ö τι ό τι" n ö τ Tιl - Tπl τ Tlι ö - Tπl ö τ Tιl ό τ Tιl - Tπl - Tπl - Tπl ό -n ό -π -π ό - π -π -π ö -π ό -n ό -n ό-π -π -n ö-π -ti ό-n ö-n ό-n ό -n -n co co c-on ωτι cτoι cτoι cτoι ωτι co o co co o co co l co co T1 TI TI T1 TI TI T1 T1 TI T1 T1 TI TI TI TI Tl Tl T co co co co co co co co co co co co co co co Tl co co o co

o o ro ro cn cn o cn o cn

^ Ch θ C3 Ch Ch <Dh Ch Ch Ch Ch Ch Ch Ch <-h Ch Ch O \ 0 ^ 0 \ Q \ 0 \ 0 \ 0 \ O \ 0 \ 0 \ 0 C? \ 0 \ O \ 0 \ O \ 0 \ O \ 0 \ 4- 4-. C CO CO C CO CO CO CCC) tO tO tO tO tO tO tO tO i— »H- ^» > - i - - i - 'i -> ■ i -> • i ->> - i ι— - OOOO> - 'MD OO -. Ch Cn 4-k CO t> - * O MD OO -O Ch Cn 4-. CO tO> - ^» O MD OO -O. Ch Cn 4 ^ CO tO> - 'O MD OO -O Ch

O O O t o t oo t oo

X X X

ι iiiiiiiiiiiii ■ iiiiii ι iiiii

Tl Tl TI T1 T1 T1 TI TI T1 T1 TI T | T | T | Tl T1 T1 TI T1 TI TI TI TI TI TI T1 T1 TI TI Tl Tl Tl T |

llllllllllll IIIIIIII i IIIIIIIII o τι oτι oτι oτι oτι oτι oτι oτι oo cτoι cτoι o cτoι o cτoι o cτoι o cτoι o cτoι o c-oπ o cτoι o cτoι o τ oτ oι o cτoι o o cτoι o cτoι o cτoι o cτoι o cτoι o cτoι o cτoι ooooo co co ω ω ω co co c-oπ cτoι cτoι cτoι cτoι

co o ro cn cn o cn o cn

--o --j --4 - ~ j --j -! --4 -o ch Ch Ch h D> ^ cD> σN <- σ _\ nc ^

-O Ch Cn 4-k C tO> - '<MD OO --4 Ch Cn 4i- C tO> -' O MD OO -O Ch Cn 4 ^ C tJ> - 'O MD OO -O Ch Cn 4 ^ CO (O ppppp -p cpo cpo cpo cpo cpo ooooooooooooo o- oooooooooo

X X X X X X X X X X X a u O, ι cOn cOn cOn cOn cOn cOn 4Ok O O O O O O O O O O O O O O O O

CO CD CO CO -4 -4 x x x x x x x x X X

CO CXD CXO CXO CXO CXO -Xl -X- - ~ l -X0. c Xn c Xn c Xn c Xn

OO - -OO _' OOO - O - -O .O .O .. OOOOOOOOOOOOOOOOOOOOO OOOO

O _ O_ O_ O_ 2.-L. ^• ._. , ^« .. _ _ _ _ - - - - _{0 QQ 0} c oo r oo -L ^■ -J c On O c Oo r Oo -L- - Jp- - —r - UI 4k CJ tO -4-, -> - -4 c On 4Ok cOo tOo _ -J-_ * -4- ^< £ -J-- c on 4 ok c oo r oo XXX cn 4 co ro

X x _ ^< ° XXXX -i ^ω ^ X xxx _ ^< ° - ⁴ -4 cn XXXX - X * X - X _ ^β XXXX

—4 cn -> CD Ol -k co 4 c Xn - co -o. cn c

Tl Tl Tl T | Tl Tl T | Tl T | T | Tl Tl Tl T | Tl T | Tl Tl Tl Tl T | Tl Tl T | tl

I

Tl T | Tl T | Tl Tl TI -Π -Π TI TI τOι -Oπ τOι τOι τOι τOι Oτι Oτι τι Oτι Oτι O-π Oτι O-π Oτι τι O-π Oτι O-π Oτι Oτι Oτι Oτι Oτι Oτι

CO o ro ro cn cn o cn o cn

T | Tl T | T1 T1 T | T1 T1 T | T1 T1 T | TI T1 T | T | T1 T1 T | T1 T | TI TI T | T | T1 T | T1 T1 T | T1 T1 T1 T |

I I 1 I I I I I I I

T | T1 T1 T1 T1 T1 T | T1 T1 T1 T1 TI T1 TI TI TI T1 T1 TI T1 T1 TI TI T1 τι τι τι τι τι τι τι -π τι τι

co co 10 ro cn cn o cn o cn

ω oc oo c oo c oo c oo

- X1 - X4 - X4 - X4 - X4

τι τι τι τι τι τι -π τι τι τι τι τι τι τι τι TI T1 T1 T1 T1 TI T1 TI TI T1 TI TI TI TI c τoι coι c τoι c

co co ro ro cn cn o cn o cn

-J -0 -0 - -0 -0 -0 -0 -4 -0 -0 -0 l -0! -0 -0 -0 l -J -. -0 -0.

-O -O -o ch Ch Ch Ch Ch Ch Ch Ch Ch cn cn cn cn cn cn cn cn cn cn tO>-> CD MD OO -O Ch Cn -P-. '- t>-' CD MD OO - Ch Cn 4 ^ C t> - ^« O

O O O O O O O O O On cOn cOn cOn cOn 4Ok 4Ok 4Ok 4Ok 4Ok 4Ok cOo cOo c on 4ok 4ok coo coo coo too roo ro o C o to X - x -x-. -x. —X- —x- CxO CxO CxD CxD CxO CxO -x-4 --x4

- X coX CD —Xl -X4 —X i cXn cXn cXn cXn

O O O O O O O O O O O O O O O O O O O O O O c 0n c0n 40k c0n 40k c0o c0n 40k c0o r0o c0n 40k c0o ιo0 ^ -4- c0n 40 c0o r0o ^ -4- ^ -l-- c0n 40k

- X —X cXo —X cXo -X4 —X cXo -XM cXn -X cXo -X4 cXn - - X c Xo - Xi c Xn - ^β - X cXo c

Ooot | TOl OOOO c τoι c τoι c τO O oι c τ O oι OT c τoι Ol O Tl OOT | ι τOι τOι Oτι τOι τOι τOι -O co co ω co co co co τι τι τ π co co co co co co co co co co co

o ro ro cn cn o o cn

co co ro ro cn cn o cn o cn

oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo Ch n cn cn nc cn cn nnn 4 ^ -l ^ 4 ^ Ji- 4 ^ i 4 ^ 4i- -l ^ s. o O o CO o o co co co CO to to to to O MD Oθ - Ch Cn 4i- Cθ tO> - 'O O oo -O. Ch Cn 4 ^ - O (O> - »o MD oo -o Ch cn 4 ^ co t> - 'o Ό oo -o Ch cn

to O tÖo r6o 6666666666 X6666666666666666666 X6 X6 X6 X6

0 X X X -L r Xo r Xo r Xo r Xo ro t Xo rXo rXo ro rXo toX X || X II X II X II X II X II X II X II X II X II X II X II X II X II X II II II II II II

- ^ *} I o o o o ö ö ö ό ό ό ό ö ό ό ό ό p p o p o o o o o o o o o o o o o o o o

X X X X X X X X X X X X X X X X x i xi xi xi xi xi xi xi xi xi xi xi rxo rxo tox t Xo toX tX tXo tX

II II II II 11 II II II II II II II II II II 11

0 0 0 0 0 0 0 0 O O O O O O O O O O O O

O P P P O 0 0 0

X X X X- X X X X x x x x x x x x x x x x ■ X t X X X X X to ro X ro to X

O O O O O O O P P P P P x x x x x x x x x x x x

I I I I I I I I I I I I I I

X X X X X X X X X x x x x x x x x x x x x x x x x x x x x x x x x x x x

^{- -} ~ ~ ~ ^{- -} ~ - ~ ^{- - -} -π τι τι τι τι τι τι ~ π τι τι -η τι τι ι τι τι τι τι

o o ro ro n cn o cn o cn

oo oo

MD MD Ch cn oooooooooooooooor 6o t6o r6o r6o r6o r6o r6o r6o r 6o r6o r6o t6o r6o r6o r6o r6o r6o r6o r6o to6

4 ok 4 ok c oo oo c oo coo coo coo coo too too roo roo roo roo roo X

X 4X Xk 4Xk 4X Xk 4X X 4 Xk 4Xk 4Xk 4Xk 4Xk 4Xk 4Xk 4Xk 4Xk 4Xk 4Xk 4Xk I I 1 I I I I I I I I I I o X X X - X —X I —X l —X 4 o X o cXn cXn cXn cX o o o x o x o

II II II II II II II II II II II II II II II II II II II II

O O O O O O O O O O O O O O O O O O O O

X ι X ι X ι X ι X ι X ι X ι X ι X ι X ι X ι X i roX rXo rXo tXo rXo roX rXo rXo

O O O O O O O O O O O x x x x x x x x x x x x

,OIL

I I I I 1 I I I I I I I I I I I I I I I x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x

I I I I I I I

Tl Tl Tl Tl Tl Tl Tl T | T | T | Tl Tl T | Tl Tl T | Tl Tl TI TI TI T1 TI TI T1 TI T1 T1 T1 Tl Tl T | T | T | T | T |

o co ro ro cn cn o cn o cn

MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD O MD MD ^ MD MD MD MD MD MD MD 'MD MD OO OO OO <_ C (_O t tO tt tO lt tO tt> - > -> -> -, -> -> -> -> - ι— OOOOOOOOOO MD MD MD t> - O MD OO - Ch Cn 4 ^ C tO> - O MD OO - Ch Cn -. CO tO> - O MD OO -4 Ch Cn 4. C t> - O MD OO -

ooo con con con con ooooooooooo oo oo coo oo oo ooooooooooooot oo r oo r oo XXXX _ X.- _X_ —XXXXXXXXX -XI -XXXXO - - cn ooι co con con con con o ok 4o 4ok ok XI -4 -4 -4 -I cn cXn cXn -x—. -x-. -x— -x_ -x *. -x— -x- (xO CxO CxD CxD CxO

₀ O 4P - ^ t ■ Po _" Op pO PO PO θ .O-. OO θ, O. PO PO PO PO θO .O. .O. OOOOO .O. .O. OOOO cOn 4O _k cOo OOOOO

X τ— ^■ θ -r PPPP τ TOT "θ TPPPP - τ- τ- PPPP ^ü '

H- __. __. cfi 4- _- ro X X - - cn 4 co - - - - cπ 4k co ro -l- -> - -4- cn 4k X X X cn co

- cD -ixx __ - CD -4 -. - CD -4 _. _. -_ -_ - CO -4 XXX _. - CD -4 X _X X ro X cn - -4 cn - co -4 cn - co - 1 c Xn - I co

I

x x x x x x x x x x x x x x x x xxx x xx x x x x xxx x xxx x x

T | o Tl o Tl o Tl o Tl o Tl o Tl o T1 oT1 oTI oTI oT1 oo oo o ooo oooo -π TI TI TI TI TI TI TI TI TI TI TI TI T1 TI TI TI T1 TI TI T1 T1 T1 Tl

o o ro ro cn cn o cn o cn

MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD '^ O MD MD MD MD Ch θ θ Ch CCC Ch nn cn nnnnn 4 ^ 4 ^ - i ^ - ^ -r ^ 4 ^ 4 ^

_M l _{O \} υι JW t H θ MD OO -JC _h Cn 4 ^ CO t> - MD OO -4 Ch Cn 4i. C tO> - O MD OO -J Ch Cn 4 ^ CO

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 O _I_ O _ι_ _T _-. _T -L-. - _T - ^ -i- ^ -. -4-- -i_- _ _T ι_- _4-- cOΛ cOn cOn cOn cOn cOn cOn 4Ok 4Ok 4Ok 4Ok 4Ok 4Ok 4Ok cOo oOo GOo cOo cOo cOo cOo rOo roO roO rOo co -4 -t -4 -4 -4 -4 -4 χ χ χ χ χ χ χ χ χ χ χ χ χ χ χ χ χ χ χ χ χ χ χ χ

- - - - - - - 1 —1 —4 - 1 -4 - 4 - 4 cn cn cn cn

OOOOOOOOOOOOOOOOOOOOO OOOOOOOOOOOOOOO rOo OL τ—- ■ -Jj cOn 4O cOo rOo χ-4- OJ- τ —-- cOn Ok cOo rOo Ol- OJ- O-— cOn 4Ok cOo tOo O ■ - τ-J-- _Ok_ cOn 4 cOo rOo OJ- -L- τ-L- c0n 40k c0o r0o c xn _ ^» - ^■ - cxo —x4 cxn - ^< ° ^ - x cxo —xi cxn - ^« ° ^ —X cXo —Xi cXn - ^{β "} " —X cXo —X4 cXn -i ^< ° - ^, - x cxo —x4 0x1

C 4

τι τι ~ π τι τι τι Tl Tl TI X X X X X X X X X X X X X X X X X X X X X X X X X X

M 6 | T6 | T61 6T | T61 6T | 6T1 6T | 6T1 6T | 6T | 6TI 6T | 6T1 6T1 6T | 6T | 6T | 6T1 6T1 6T1 6T | 6T | 6T1 6T1 6T1 6T | 6T | 6T1 6T1 6T | 6 "TI 6TI 6T | 6T | 6T | co ω w ω ω co co oJ co ω ω w ω oo co co co co co co co co co co co co co co co co co co co co co co

co co ro ro cn cn o cn o cn

MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD ^ O VO MD MD MD MD MD MD MD MD MD ooooo MD MD MD MD MD MD MD MD MD ^ OO OO OO ∞ 00 00 00 00 00 00 -0 - -0 -0 -0 -J -J --4 --l --4 Ch ooooo MD 00 -4 Ch cn 4 ^ co to> - o MD oo -o ch cn 4i>. co to> - © vo oo -j Ch cn 4-k> tθ ι— O MD ω to i- o

ι ι ι ι ι ι ι ι ι ι ι ι ι

TI TI TI TI TI TI TI TI TI TI TI TI TI TI TI T | T | Tl T | T | Tl T | Tl | T | T | Tl T |

(1005) -CH ₂ -CH = CH-CH ₃ -C5H11 -F -CF ₃

(1007) -Cπ2-CH ^- CH-CH ₃ -CH = CH-CH ₃ -F -CF ₃

(1008) -Cπ2-CH ^- CH-CH ₃ -CH ₂ -CH = CH-CH ₃ -F -CF ₃

(1009) -Cπ ₂ -CH ^- CH-CH ₃ -C ₂ H ₄ -CH ^: = CH ₂ -F -CF ₃

(1010) -CH2-CH- CH-CH ₃ -C2H -CH ^: = CH-CH ₃ -F -CF ₃

(1011) -CH2-CH- CH-CH ₃ -OC2H5 -F -CF ₃

(1012) -CH2-CH-CH-CH ₃ -OC ₃ H ₇ -F -CF ₃

(1013) -CH2-CH ⁼ CH-CH ₃ -OC ₄ H ₉ -F -CF ₃

(1014) -CH ₂ -CH ⁼ CH-CH ₃ -OCsHn -F -CF ₃

(1016) -C2H ₄ -CH ⁼ CH ₂ -C ₄ Hg -F -CF ₃

(1018) -C2H ₄ -CH = CH ₂ -CH = CH ₂ -F -CF ₃

(1019) -C2H ₄ -CH ^- CH ₂ -CH = CH-CH ₃ -F -CF ₃

(1021) -C2H ₄ -CH ⁼ CH ₂ -C2H ₄ -CH ^: = CH ₂ -F -CF ₃

(1022) -C ₂ H -CH ^: = CH-CH ₃ -F -CF ₃

(1023) -C2H -CH ⁼ CH ₂ -OC ₂ H ₅ -F -CF ₃

(1024) -C2H4-CH ⁼ CH ₂ -OC ₃ H ₇ -F -CF ₃

(1026) -C2H ₄ -CH ⁼ CH ₂ -OC5H11 -F -CF ₃

(1027) -C ₂ H ₄ -CH ⁼ CH-CH ₃ -C ₃ H ₇ -F -CF ₃

(1028) -C ₂ H ₄ -CH ⁼ CH-CH ₃ -C ₄ Hg -F -CF ₃

(1030) -C ₂ H ₄ -CH = CH-CH ₃ -CH = CH ₂ -F -CF ₃

(1031) -C ₂ H -CH ⁼ CH-CH ₃ -CH = CH-CH ₃ -F -CF ₃

(1032) -CH ₂ -CH = = CH-CH ₃ -F -CF ₃

(1033) -C2H ₄ -CH ⁼ CH-CH ₃ -CH ₄ -CH = CH ₂ -F -CF ₃

(1035) -C2H ₄ -CH ⁼ CH-CH ₃ -OC ₂ H ₅ -F -CF ₃

(1036) -C2H ₄ -CH ⁼ CH-CH ₃ -OC ₃ H ₇ -F -CF ₃

(1039) -OC ₂ H ₅ -C ₃ H ₇ -F -CF ₃

(1040) -OC ₂ H ₅ -C Hg -F -CF ₃ co o ro 10 cn o cn o cn cn

i

OOOOOOOOOOOOOOOOOOOOO OOOOOOOOOOOOO o O JC OJ- _T J-- _T - ^ - _T _L-- _T _L- _T _i--. _T _L- _T - ⁴ _- cOn cOn cOn cOn cOn oOι cOn 4Ok 4Ok 4Ok 4Ok 4Ok 4Ok 4Ok cOo cOo cOo cOo cOo ωO coO tOo ιOo rOo rOo to o

CD co - ^j -4 -4 -. -4 -4 -4 χ χ χ χ ι χ χ χ χ χ χ χ χ χ χ χ χ χ χ χ χ χ χ χ χ

- - - - - - - co cD co co co cD co -4 -4 - 1 -1 -4 - 1 -ι cn cn cn cn c Xn

o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o

O -l- O-4- cn O cOo tOo O -> - _T -4-- _T —- cOn 4Pk cPo rPo O_ ■ O - * - - ^ - cOn 4O cPo tPo O-4- _T —- ■ - 4- cOn 4Ok cOo ro OJ- _T —-- _T —- ■ cn 4Ok cO c on o ro

- ^β —X CXD —XI CXn - ^{β "} ^ —X CXD -X4 CXΛ - ^β" ^ —xx -x4 xn - ^« ^ —xx -x4 xn - ^« ° - ¹ —xx -x4 cxn

T | T | T | T | Tl T | T | Tl T | Tl T | T | Tl T | T | Tl τι τι τι I

Tl Tl T | T | Tl Tl Tl Tl

ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι |

^T i ^T i ^T i ^T i ^{Ti T} i ^T i ^T i ^T io OOOOOOOOOOOOOOOOOOOOO OOOO τι τι τι τι τι -π τι τι τι τι τι τι τι τι τι τι τι τι τι τι ι τι τι

>>

T o

II II o "-1

O

--1 ü)

o co ro ro cn cn o cn o cn

t—> - oo O> - O MD 00 -o ooooooooooooooooooooo xxxxxxxxxxxx cn cn cn n cn II II II II II II II II II II II II XXXXXXXXXOOOOOOOOOOOO _ _ _ - -. >. rxo rxo rxo rxo rxo rxo rxo rxo rxo rxo rxo rxo

i I 1 1 1 1

Tl T | Tl Tl Tl Tl T | Tl Tl T | Tl Tl Tl Tl T | Tl T | Tl Tl Tl Tl Tl T | Tl Tl T | T | Tl T | T | Tl T | T | T | tl

Tl TJ T] T1 T1 TI T1 T1 T1 T1 T1 TI Tl Tl T | T | Tl Tl Tl Tl Tl T | Tl T | Tl "π τι -π τι τι τι τι τι τι τι

(1112) -CH-CH ⁼ CH-CH ₃ -C2H-CH-CH2 -F -F

(1113) -CH ₂ -CH = CH-CH ₃ -C2H ₄ -CH ⁼ CH-CH ₃ -F -F

(1114) -CH ₂ -CH = CH-CH ₃ -OC2H5 -F -F

(1116) -CH2 ^_ CH ⁼ CH-CH ₃ -OC ₄ Hg -F -F

(1117) -CH ₂ -CH = CH-CH ₃ -OC ₅ Hn -F -F

(1118) -C2H ₄ -CH ⁼ CH2 -C ₃ H -F -F

(1124) -C2H ₄ -CH ⁼ CH2 -OC ₃ H ₇ -F -F

(1125) -C ₂ H ₄ -CH ⁼ CH ₂ -OC ₄ Hg -F -F

(1126) -C ₂ H ₄ -CH ⁼ CH2 -OC ₅ H ₁₁ -F -F

(1127) -C ₂ H ₄ -CH ⁼ CH-CH ₃ -C ₃ H -F -F

(1128) -C ₂ H ₄ -CH ⁼ CH-CH ₃ -C ₄ Hg -F -F

(1129) -C ₂ H-CH ⁼ CH-CH ₃ -C ₅ H ₁₁ -F -F

(1130) -C ₂ H-CH ⁼ CH-CH ₃ -C ₂ H-CH ⁼ CH-CH ₃ -F -F

(1131) -C ₂ H ₄ -CH ⁼ CH-CH ₃ -OC ₂ H ₅ -F -F

(1132) -CH ₄ -CH = CH-CH ₃ -OC ₃ H ₇ -F -F

(1133) -C ₂ H-CH ⁼ CH-CH ₃ -OC ₄ Hg -F -F

(1134) -C ₂ H-CH ⁼ CH-CH ₃ -OC ₅ H ₁₁ -F -F

(1135) -OC ₂ H ₅ -OC2H5 -F -F

(1136) -OC ₂ H ₅ -OC ₃ H ₇ -F -F

(1137) -OC ₂ H ₅ -OC ₄ Hg -F -F

(1138) -OC ₂ H ₅ -OC ₅ H ₁₁ -F -F

(1139) -OC ₃ H ₇ -OC ₃ H ₇ -F -F

(1140) -OC ₃ H ₇ -OC ₄ Hg -F -F

(1141) -OC ₃ H ₇ -OC5H11 -F -F

(1142) -OC ₄ Hg -OC ₄ Hg -F -F

(1143) -OC ₄ Hg -OC ₅ H ₁₁ -F -F

(1144) -OC ₅ H ₁₁ -OC5H11 -F -F

(1145) -C ₃ H ₇ -C ₃ H -CF ₃ -CF ₃

(1146) -C ₃ H -CHg -CF ₃ -CF ₃

(1147) -C ₃ H ₇ -C5H11 -CF ₃ -CF ₃ co co ro ro cn cn o cn o cn

-J -4 -O Ch Ch Ch Ch Ch to> - MD OO -J Ch Cn

6 o 6o 6o o66o 6o 6o 6o 6o 6o ⁰ 6 ^{1 ü} 6n 6 6 cn 4k 4k co co co ro ro ro ro ro xx ^{, c} x ⁿ n ^ü 6n x ^{, ü} x '* 46k x-

- X cXo cXo —X ι -X4 -Xι cXn cXn cXn cXn

O O O O O O O O O O O O O O O O O O O O O O O O c on con 4ok con 4ok coo con 4ok coo roo con 4ok coo roo θ -4- con 4ok coo roo θ -4- τ -4-- c0n 40k c0o r0o.

- X —X cXo —X cXo -X4 —XXX i cXn —X cXo -X4 cXn - - x cxo -xt cxn - ^ω - x cxo -x4 cxn

-

6 TI 6TI 6-Π 6TΠ 6TI 6-Π 6TI -6Π 6TI 6TI T6I 6TI 6TI 6TI 6TI 6TI 6TI 6TI 6TI 6TI 6TI 6TI 6TI 6TI 6TI

I

0 Tl 0 Tl 0 Tl 0 Tl 0 0 Tl 0 Tl 0 Tl 6 Tl 6 Tl 6 Tl 6 Tl 6 Tl 6 Tl 6 Tl 6 Tl 6 T6I 6TI T6I 6TI 6TI 6TI 6TI 6TI 6TI co co co o co co co co co co co co co oo co co

Claims

claims

1. Fluorene derivatives of the formula I.

R ¹ - (- A ¹ -Z ¹ -) _k1 - (- A ² -Z ² -) _k2 -W - (- Z ³ -A ³ -) _k3 - (- Z ⁴ -A ⁴ -) _k4 -R ² I

in the

W the group

means

L ¹ , L ² independently of one another H, F, Cl, -CH ₂ F, -CHF ₂ or

-CF ₃ with the proviso that both L ¹ and L ² do not denote H,

L ³ , L ⁴ independently of one another H or F,

R ¹ , R ² independently of one another H, halogen, -CN, -NCS,

-SF ₅ or alkyl with 1 to 18 C atoms, in which one or two non-adjacent -CH ₂ groups are also represented by -O-, -S-, -CO-, -O-CO-, -CO-O-, -E- and / or -C≡C- can be replaced and / or in which one or more H atoms can also be replaced by halogen and / or -CN,

CR ⁴ = CR ⁵ or CHR ⁴ -CHR ⁵ ,

R ⁴ , R ⁵ each independently of one another H, alkyl with 1-6

Is C atoms, F, Cl, CF ₃ or CN,

A ¹ , A ² , A ³ , A ⁴ each independently of the other 1, 4-phenylene, in which one or more CH groups can be replaced by N, 1, 4-cyclohexylene, in which one or two are not adjacent CH ₂ groups can be replaced by O and / or S, 1,4-cyclohexenylene, 1,4-bicyclo (2,2,2) octylene, piperidine-1,4-diyl, naphthalene-2,6-diyl , Decahydronaphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl, one or more H atoms being substituted in the meanings given for A ¹ , A ² , A ³ , A ⁴ can by halogen, -CN and / or alkyl having 1 to 6 carbon atoms, wherein one or more H atoms by halogen or -CN, and / or wherein one or more non-adjacent -CH ₂ groups independently of one another by -CO -, -O-CO-, -CO-O-, -O-, -S-, -CH = CH- or -C≡C- can be replaced, and

Z ¹ , Z ² , Z ³ , Z ⁴ independently of one another -O-CO-, -CO-O-, -CH ₂ .0-, -CF ₂ -0-, -0-CH ₂ -, -O-CF2 -, -C ₂ H4-, -CH ₂ -CF ₂ -,

-CF ₂ -CH2-, -CF2-CF2-, -CH-CH-, -CF = CH-, -CH = CF-, -CF = CF-, -C≡C- or a single bond,

k1, k2, k3, k4 independently of one another represent 0, 1 or 2.

Fluorene derivatives according to claim 1, characterized by a group W selected from the group of sub-formulas

where I can have the values 0, 1 or 2.

3. fluorene derivatives according to any one of the preceding claims, characterized by the formula la

R ¹ -WR ² la

in which R ¹ , W, R ^{2 have} one of the meanings given in claims 1 or 2.

Fluorene derivatives according to claim 1 or 2, characterized by the formula Ib

R ¹ - A ¹ -Z ¹ AN -R "Ib

in which R ¹ , R ² , A ¹ , Z ¹ and W have one of the meanings given in Claim 1 or 2.

5. fluorene derivatives according to claim 1 or 2, characterized by the formula Ic or Id

R ¹ -A ¹ -Z ¹ -A ² -Z ² - W -R ² Ic

R ¹ _A ¹ -Z ¹ -W- Z ³ -A ³ -R ² Id

in which R ¹ , R ² , A ¹ , A ² , A ³ , ZZ ² , Z ³ and W have one of the meanings given in Claim 1 or 2.

, Fluorene derivatives according to one of the preceding claims, characterized in that

L ³ and L ⁴ mean H, and

_R ι _ (_ A ¹ -Z ¹ -) _k1 - (- A ² -Z ² -) _k2 - and

- (- Z ³ -A ³ -) _k3 - (- Z ⁴ -A ⁴ -) _k4 -R ²

are each selected from the meanings according to claim 1 such that the fluorene derivative has a dielectric anisotropy Δε of less than or equal to -2.0.

7. fluorene derivatives according to one of claims 1 to 5, characterized in that one of the substituents L ³ , l_ ⁴ F and the other substituent L ³ or L ⁴ H and

_R ¹ - (- A ¹ -Z ¹ -) _k1 - (- A ² -Z ² -) _k2 - and

_ (_ _Z ³ -A ³ -) _k3 - (- Z ⁴ -A ⁴ -) _k4 -R ²

are each selected from the meanings according to claim 1 such that the fluorene derivative has a dielectric anisotropy Δε of less than or equal to -6.0.

8. fluorene derivatives according to one of claims 1 to 5, characterized in that L ³ and L ⁴ F and

_R ¹ _ (_ A ¹ -Z ¹ -) _k1 - (- A ² -Z ² -) _k2 - and

- (- Z ³ -A ³ -) _k3 - (- Z ⁴ -A ⁴ -) _k4 -R ² are each selected from the meanings according to claim 1 such that the fluorene derivative has a dielectric anisotropy Δε of less than or equal to -8.0.

Liquid-crystalline medium with two or more liquid-crystalline components, characterized in that it contains at least one compound of the formula I according to one of Claims 1 to 8.

10. Optical display element, characterized in that it contains a liquid-crystalline medium according to claim 9.

11. Electro-optical display element, characterized in that it contains a liquid-crystalline medium as claimed in claim 9 as a dielectric.