DE102006047129A1 - Dioxane derivative useful as an liquid crystalline component in liquid crystalline media, which is useful in a reflective or transflective liquid crystal display element and an electrophoretic display element is new - Google Patents

Abstract

Dioxane derivative (I) is new. Dioxane derivative (I) of formula (R 1>-(A 1>-Z 1>) m-G-(Z 2>-A 2>) n-R 2>) is new. G : 2-methyl-5-(6-methyl-spiro[3.3]hept-2-yl)-[1,3]dioxane of formula (1) or 5-methyl-2-(6-methyl-spiro[3.3]hept-2-yl)-[1,3]dioxane of formula (2); R 1>, R 2>H, halo (F, Cl, Br, I) or optionally chiral alkyl or alkoxy with 1-15C (optionally substituted by halo, where one or more CH 2groups are substituted by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CH=CH-, -CH=CF-, -CF=CF-, -Ctriple boundC- or cyclobutane compound (3) of formula, where the heteroatoms are not directly connected together), -CN, -SCN, -NCS, -SF5, -SCF 3, -CF 3, -CF=CF 2, -CF 2CF 2CF 3, -OCF 3, -OCHF 2, -CF 2CH 2CF 3or -OCH 2CF 2CHFCF; A 1>, A 2>trans-1,4-cyclohexylene (where one or more non-adjacent CH 2groups are replaced by -O and/or -S- and one or more H atoms are replaced by F), 1,4-phenylene (where one or two CH groups are replaced by N and one or more H atoms are replaced by halo (F, Cl, Br, I), -CN, -CH 3, -CHF 2, -CH 2F, CF 3, -OCH 3, -OCHF 2or -OCF 3), bicyclo[1.1.1]pentan-1,3-diyl, bicyclo[2.2.2]-octan-1,4-diyl, spiro[3.3]heptan 2,6-diyl, naphthalin-2,6-diyl, naphthalin-2,7-diyl, decahydronaphthalin-2,6-diyl, 1,2,3,4-tetrahydronaphthalin 2,6-diyl, piperidin-1,4-diyl, phenanthren-2,7-diyl, fluoren-2,7-diyl, anthracen-2,6-diyl, anthracen-2,7-diyl, indan-2,5-diyl (where one or more H atoms are replaced by halo, preferably F), 1,4-cyclohexenylene or 1,3-cyclobutan-1,3-diyl; Z 1>, Z 2>-O-, -CH 2O-, -OCH 2-, -CO-O-, -O-CO-, -CF 2O-, -OCF 2-, -CF 2CF 2-, -CH 2CF 2-, -CF 2CH 2-, -CH 2CH 2-, -CH = CH-, -CH = CF-, -CF = CH-, -CF = CF-, -CF=CF-COO-, -O-CO-CF=CF-, -Ctriple boundC-, -CH 2CH 2CF 2O- or a single bond; and m, n : 0-3. Independent claims are also included for: (1) a liquid crystalline medium with at least two liquid crystalline component comprising (I); (2) a liquid crystal display element comprising liquid crystalline media; (3) a reflective or transflective liquid crystal display element comprising liquid crystalline media; (4) an electrophoretic display element comprising liquid crystalline media; (5) a spiro-diol compound of formula (II); and (6) the preparation of (I). [Image] [Image].

Description

The The present invention relates to dioxane derivatives having both a Dioxane ring as well as a spiro [3.3] heptyl group as a constituent of their basic structure their use as component (s) in liquid crystalline Media and liquid crystal and electro-optical display elements comprising these liquid-crystalline Media included.

The Dioxane derivatives of the invention can as component (s) of liquid-crystalline Media are used, especially for displays based on the principle the twisted cell, the guest-host effect, the effect of deformation aligned phases DAP or ECB (Electrically Controlled Birefringence), the IPS effect (in plane switching) or the effect of the dynamic one Scattering based.

The so far for substances used for this purpose always have certain disadvantages, For example, too little stability against the action of heat, light or electric fields, unfavorable elastic and / or dielectric properties.

Of the Invention was therefore the object of new stable compounds which are used as component (s) of liquid-crystalline media, in particular for TN, STN, IPS and TFT displays are suitable.

A Another object of the present invention was compounds to provide that have a low rotational viscosity, have a positive dielectric anisotropy Δε and are simple can be synthesized. In particular, by reducing the rotational viscosity should can realize significantly lower switching times.

Surprisingly it has been found that the dioxane derivatives according to the invention are excellently used as component (s) liquid-crystalline Media are suitable. With their help can be stable, liquid crystalline Media, especially suitable for TFT or STN displays.

By suitable choice of the ring members and / or the terminal substituents the physical properties of the dioxane derivatives according to the invention can be determined vary widely. For example, it is possible to use dioxane derivatives according to the invention with very small values of optical anisotropy or with low positive to strong positive values of dielectric anisotropy to obtain.

Especially the dioxane derivatives according to the invention are distinguished both by low levels of optical anisotropy and by unexpectedly low rotational viscosities.

liquid crystalline Media with very small values of optical anisotropy are in particular for reflective and transflective applications of importance, i. such applications, where the respective LCD no or only supportive backlight experiences.

With the provision of the dioxane derivatives according to the invention becomes complete in general, the range of liquid crystalline Substances that differ in different, application-related Aspects are suitable for the preparation of liquid-crystalline mixtures, considerably widened.

The Dioxane derivatives of the invention have a wide range of applications. Depending on the selection of the Substituents can these compounds serve as base materials from which liquid crystalline Media for the most part Part are composed. It can but also the dioxane derivatives according to the invention liquid crystalline Base materials from other classes of compounds are added, for example, the dielectric and / or optical anisotropy to influence such a dielectric and / or its threshold voltage and / or its viscosity to optimize.

The Dioxane derivatives of the invention are colorless in their pure state. Chemical, thermal and against light they are stable.

R¹, R² jeweils unabhängig voneinander, gleich oder verschieden H, Halogen (F, Cl, Br, I) oder einen linearen oder verzweigten, gegebenenfalls chiralen, unsubstituierten, ein- oder mehrfach durch Halogen substituierten Alkyl- oder Alkoxyrest mit 1 bis 15 C-Atomen, worin auch eine oder mehrere CH₂-Gruppen jeweils unabhängig voneinander durch -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CH=CH-, -CH=CF-, -CF=CF-, -C≡C- oder

so ersetzt sein können, dass Heteroatome nicht direkt miteinander verknüpft sind, -CN, -SCN, -NCS, -SF₅, -SCF₃, -CF₃, -CF=CF₂, -CF₂CF₂CF₃, -OCF₃, -OCHF₂, -CF₂CH₂CF₃ oder -OCH₂CF₂CHFCF₃,
A¹, A² jeweils unabhängig voneinander, gleich oder verschieden

• a) trans-1,4-Cyclohexylen, worin auch eine oder mehrere nicht benachbarte CH₂-Gruppen durch -O- und/oder -S-ersetzt sein können und worin auch ein oder mehrere H-Atome durch F ersetzt sein können,
• b) 1,4-Phenylen, worin eine oder zwei CH-Gruppen durch N ersetzt sein können und worin auch ein oder mehrere H-Atome durch Halogen (F, Cl, Br, I), -CN, -CH₃, -CHF₂, -CH₂F, -CF₃, -OCH₃, -OCHF₂ oder -OCF₃ ersetzt sein können,
• c) einen Rest aus der Gruppe Bicyclo[1.1.1]pentan-l,3-diyl, Bicyclo[2.2.2]-octan-1,4-diyl, Spiro[3.3]heptan-2,6-diyl, Naphthalin-2,6-diyl, Naphthalin-2,7-diyl, Decahydronaphthalin-2,6-diyl, 1,2,3,4-Tetrahydronaphthalin-2,6-diyl, Piperidin-1,4-diyl, Phenanthren-2,7-diyl, Fluoren-2,7-diyl, Anthracen-2,6-diyl, Anthracen-2,7-diyl und Indan-2,5-diyl, wobei ein H-Atom oder mehrere H-Atome durch Halogen, insbesondere F, ersetzt sein können,
• d) 1,4-Cyclohexenylen oder Cyclobutan-1,3-diyl,

Z¹, Z² jeweils unabhängig voneinander, gleich oder verschieden -O-, -CH₂O-, -OCH₂-, -CO-O-, -O-CO-, -CF₂O-, -OCF₂-, -CF₂CF₂-, -CH₂CF₂-, -CF₂CH₂-, -CH₂CH₂-, -CH=CH-, -CH=CF-, -CF=CH-, -CF=CF-, -CF=CF-COO-, -O-CO-CF=CF-, -C≡C-, -CH₂CH₂CF₂O- oder eine Einfachbindung, und
m, n unabhängig voneinander, gleich oder verschieden 0, 1, 2 oder 3, vorzugsweise m = 0, 1 oder 2 und n = 1 oder 2, besonders bevorzugt m = 0 oder 1 und n = 1 oder 2, und insbesondere m = 0 und n = 1 oder 2,
bedeuten.The present invention thus relates to dioxane derivatives of the formula I.

R ¹ , R ^{2 are} each independently, identically or differently H, halogen (F, Cl, Br, I) or a linear or branched, optionally chiral, unsubstituted, mono- or polysubstituted by halogen alkyl or alkoxy radical having 1 to 15 C atoms in which one or more CH ₂ groups are each independently denoted by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, - CH = CH-, -CH = CF-, -CF = CF-, -C≡C- or

may be replaced so that heteroatoms are not directly linked, -CN, -SCN, -NCS, -SF ₅ , -SCF ₃ , -CF ₃ , -CF = CF ₂ , -CF ₂ CF ₂ CF ₃ , -OCF ₃ , -OCHF ₂ , -CF ₂ CH ₂ CF ₃ or -OCH ₂ CF ₂ CHFCF ₃ ,
A ¹ , A ^{2 are} each independently, the same or different

• a) trans-1,4-cyclohexylene, in which also one or more non-adjacent CH ₂ groups may be replaced by -O- and / or -S-and in which also one or more H atoms may be replaced by F,
• b) 1,4-phenylene, in which one or two CH groups may be replaced by N and in which also one or more H atoms are represented by halogen (F, Cl, Br, I), -CN, -CH ₃ , -CHF ₂ , -CH ₂ F, -CF ₃ , -OCH ₃ , -OCHF ₂ or -OCF ₃ may be replaced,
• c) a radical from the group of bicyclo [1.1.1] pentane-1,3-diyl, bicyclo [2.2.2] octane-1,4-diyl, spiro [3.3] heptane-2,6-diyl, naphthalene 2,6-diyl, naphthalene-2,7-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, piperidine-1,4-diyl, phenanthrene-2, 7-diyl, fluoren-2,7-diyl, anthracene-2,6-diyl, anthracene-2,7-diyl and indan-2,5-diyl, where one or more H atoms are halogen, in particular F, can be replaced,
• d) 1,4-cyclohexenylene or cyclobutane-1,3-diyl,

Z ^1, Z ² are each independently identical or different and are -O-, -CH ₂ O-, -OCH ₂ -, -CO-O-, -O-CO-, -CF ₂ O-, -OCF ₂ -, -CF ₂ CF ₂ -, -CH ₂ CF ₂ -, -CF ₂ CH ₂ -, -CH ₂ CH ₂ -, -CH = CH-, -CH = CF-, -CF = CH-, -CF = CF -, -CF = CF-COO-, -O-CO-CF = CF-, -C≡C-, -CH ₂ CH ₂ CF ₂ O- or a single bond, and
m, n are independently, identically or differently 0, 1, 2 or 3, preferably m = 0, 1 or 2 and n = 1 or 2, more preferably m = 0 or 1 and n = 1 or 2, and especially m = 0 and n = 1 or 2,
mean.

One Another object of the present invention is the use of compounds of the formula I as component (s) in liquid-crystalline Media.

Also The present invention relates to liquid-crystalline media with at least two liquid-crystalline ones Components containing at least one compound of formula I.

object The present invention also relates to liquid crystal display elements, in particular electro-optical display elements, which serve as a dielectric an inventive, liquid crystalline Medium included.

Reflective and transflective liquid crystal display elements and other low birefringence liquid crystal displays Δn, so-called "low Δn mode displays", such as, for example, reflectors, are particularly preferred tive and transflective TN displays.

The Meaning of the formula I concludes all isotopes of the bound in the compounds of formula I chemical Elements. In enantiomerically pure or enriched form the compounds of the formula I are also suitable as chiral dopants and generally to achieve chiral mesophases.

Above and below, R ¹ , R ² , A ¹ , A ² , Z ¹ , Z ² , G, m and n have the meaning given, unless expressly stated otherwise. If the radicals A ¹ and A ² or Z ¹ and Z ² more than once, so they can assume independently of one another identical or different meanings.

und Verbindungen der Teilformel Ib

worin R¹, R², A¹, A², Z¹, Z², m und n die oben angegebenen Bedeutungen besitzen.Preferred compounds of the formula I are compounds of the partial formula Ia

and compounds of sub-formula Ib

wherein R ¹ , R ² , A ¹ , A ² , Z ¹ , Z ² , m and n have the meanings given above.

Preference is given to compounds of the formula I in which R ^{1 is} H or a linear alkyl radical having 1 to 10 C atoms.

Preference is likewise given to compounds of the formula I in which R ^{2 is} H, a linear alkoxy radical having 1 to 10 C atoms, -F, -Cl, -CF ₃ , -OCF ₃ , -OCHF ₂ , -CN, -NCS or -SF ₅ , more preferably -F, -CF ₃ , -OCF ₃ or -CN.

Z ¹ is preferably -CH ₂ CH ₂ -, -CH = CH-, -C≡C-, -CF ₂ CF ₂ -, -CF = CF-, -CF ₂ O-, -OCF ₂ - or a single bond, particularly preferably a single bond.

Z ² is preferably -CH ₂ CH ₂ -, -CH = CH-, -C≡C-, -CF ₂ CF ₂ -, -CF = CF-, -CF ₂ O-, -OCF ₂ - or a single bond, particularly preferably -CF ₂ O- or a single bond.

For the sake of simplicity, in the following Cyc is a 1,4-cyclohexylene radical, Che is a 1,4-cyclohexenylene radical, Dio is a 1,3-dioxane-2,5-diyl radical, Dit is a 1,3-dithiane-2,5-diyl radical, Phe is a 1,4-phenylene radical, Pyd is a pyridine-2,5-diyl radical, Pyr is a pyrimidine-2,5-diyl radical, Bco is a bicyclo- (2,2,2) -octylene radical, Dec is a decahydronaphthalene-2,6- diyl, Nap is a naphthalene-2,6-diyl or naphthalene-2,7-diyl radical, Thn is a 1,2,3,4-tetrahydronaphthalene-2,6-diyl radical, pip is a piperidine-l, 4-diyl radical, Phe a phenanthrene-2,7-diyl radical, Flu is a fluorene-2,7-diyl radical, Ant is an anthracene-2,6-diyl or anthracene-2,7-diyl radical and Ind is an indane-2,5-diyl radical, where Cyc and / or Phe can be unsubstituted or monosubstituted or polysubstituted by CH ₃ , Cl, F or CN.

A ¹ and A ^{2 are} preferably Phe, Cyc, Che, Pyd, Pyr or Dio, and particularly preferably Phe or Cyc.

Phe is preferable

The terms 1,3-dioxane-2,5-diyl and Dio each include the two positional isomers

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

worin R¹ und R² die oben angegebenen Bedeutungen besitzen und L¹, L², L³ und L⁴ unabhängig voneinander, gleich oder verschieden H oder F bedeuten.Particularly preferred compounds of formula Ia include the following formulas:

wherein R ¹ and R ^{2 have} the meanings given above and L ¹ , L ² , L ³ and L ⁴ independently, identically or differently mean H or F.

worin R¹ und R² die oben angegebenen Bedeutungen besitzen und L¹, L², L³ und L⁴ unabhängig voneinander, gleich oder verschieden H oder F bedeuten.Particularly preferred compounds of formula Ib include the following formulas:

wherein R ¹ and R ^{2 have} the meanings given above and L ¹ , L ² , L ³ and L ⁴ independently, identically or differently mean H or F.

Preference is given to compounds of the formulas Iaa to Iaf and Iba to Ibh in which R ^{1 is} H or a linear alkyl or alkoxy radical having 1 to 10 C atoms or alkenyl or alkenyloxy having 2 to 10 C atoms.

Also preferred are compounds of formula Iaa to Iaf and Iba to Ibh wherein R ² is -F, -CF _3, -OCF ₃ or -CN.

Particular preference is given to compounds of the formulas Iaa to Iaf and Iba to Ibh in which R ^{2 is} -F, -CF ₃ , -OCF ₃ or -CN, L ¹ , L ² , L ³ and L ^4, independently of one another, identical or different F or H mean.

worin R¹ die oben angegebene Bedeutung besitzt.Especially preferred are compounds of the formula Iaa and Iac. They include in particular the following formulas:

wherein R ^{1 has} the meaning given above.

worin R¹ die oben angegebene Bedeutung besitzt.Particular preference is furthermore given to compounds of the formula Iba and Ibd. They include in particular the following formulas:

wherein R ^{1 has} the meaning given above.

Preference is given to compounds of the formulas Iaa1 to Iaa9, Iac1 to Iac9, Iba1 to Iba9 and Ibd1 to Ibd9, in which R ^{1 is} H or a linear alkyl or alkoxy radical having 1 to 10 C atoms or alkenyl or alkenyloxy having 2 to 10 C, for example -Atomen, more preferably a linear alkyl radical having 1 to 10 carbon atoms, means.

If R ¹ and / or R ² in the above and following formulas denotes an alkyl radical, this may be straight-chain or branched. It is particularly preferably straight-chain, has 2, 3, 4, 5, 6 or 7 carbon atoms and thus means ethyl, propyl, butyl, pentyl, hexyl or heptyl, furthermore methyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl , Tetradecyl or pentadecyl.

If R ¹ and / or R ^{2 is} an alkyl radical in which a CH ₂ group has been replaced by -O-, this may be straight-chain or branched. It is preferably straight-chain and has 1 to 10 C atoms. Particularly preferably, the first CH ₂ group of this alkyl radical is replaced by -O-, so that the radical R ¹ and / or R ^{2 is} alkoxy and in particular methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy or Nonyloxy means.

Furthermore, a CH ₂ group can be replaced elsewhere by -O-, so that the radical R ¹ and / or R ^{2 is} preferably straight-chain 2-oxa propyl (= 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, 2-, 3-, 4-, 5-, 6 -, 7-, 8- or 9-oxadecyl.

If R ¹ and / or R ^{2 is} an alkyl radical in which one CH ₂ 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. It therefore means 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, Oct-1, 2-, 3- , 4-, 5-, 6- or oct-7-enyl, non-1-, 2-, 3-, 4-, 5-, 6-, 7- or non-8-enyl, Dec-1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or dec-9-enyl.

Preferred alkenyl groups are C ₂ -C ₇ -1E-alkenyl, C ₄ -C ₇ -EE-alkenyl, C ₅ -C ₇ -alkenyl, C ₆ -C ₇ -5-alkenyl, and C ₇ -6-alkenyl , more preferably C ₂ -C ₇ -1E-alkenyl, C ₄ -C ₇ -EE-alkenyl and C ₅ -C ₇ -alkenyl.

Examples particularly preferred alkenyl groups are vinyl, 1E-propenyl, 1E-butenyl, 1E-pentenyl, 1E-hexenyl, 1E-heptenyl, 3-butenyl, 3E-pentenyl, 3E-hexenyl, 3E-heptenyl, 4-pentenyl, 4Z-hexenyl, 4E-hexenyl, 4Z-heptenyl, 5-hexenyl and 6-heptenyl. Groups of up to 5 carbon atoms are in particular prefers.

If R ¹ and / or R ^{2 is} an alkyl radical in which one CH ₂ group has been replaced by -O- and one by -CO-, these are preferably adjacent. Thus, these include an acyloxy group -CO-O- or an oxycarbonyl group -O-CO-. These are particularly preferably straight-chain and have 2 to 6 C atoms.

They accordingly mean, in particular, acetyloxy, propionyloxy, butyryloxy, pentanoyloxy, hexanoyloxy, acetyloxymethyl, propionyloxymethyl, butyryloxymethyl, pentanoyloxymethyl, 2-acetyloxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 3-acetyloxypropyl, 3-propionyloxypropyl, 4-acetyloxybutyl, methoxycarbonyl, ethoxycarbonyl, Propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, butoxycarbonylmethyl, 2- (methoxycarbonyl) ethyl, 2- (ethoxycarbo nyl) ethyl, 2- (propoxycarbonyl) ethyl, 3- (methoxycarbonyl) propyl, 3- (ethoxycarbonyl) propyl and 4- (methoxycarbonyl) butyl.

If R ¹ and / or R ^{2 is} an alkyl radical in which one CH ₂ group is unsubstituted or substituted -CH = CH- and one adjacent CH ₂ group is -CO-, -CO-O- or -O-CO - Is replaced, it may be straight-chain or branched. Preferably, it is straight-chain and has 4 to 13 carbon atoms. It therefore particularly preferably means 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 and 9-methacryloyloxynonyl.

If R ¹ and / or R ² represents an easily by CN or CF ₃ alkyl or alkenyl radical, this radical is preferably straight-chain and the substitution by CN or CF ₃ in ω-position.

If R ¹ and / or R ^{2 is} an alkyl radical which is at least monosubstituted by halogen, this radical is preferably straight-chain. Halogen is preferably F or Cl. In the case of multiple substitution, halogen is preferably F. The resulting radicals also include perfluorinated radicals. For single substitution, the fluoro or chloro substituent may be in any position, but preferably in the ω position.

Compounds of the formula I with branched wing group R ¹ and / or R ² may occasionally be of importance because of a 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 useful as components of ferroelectric materials.

Branched groups of this type usually contain no more than one chain branch. Preferred branched radicals R ¹ and / or R ² 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-methylpentyloxy, 3-methylpentyloxy, 2-ethylhexyloxy, 1-methylhexyloxy and 1-methylheptyloxy.

formula I includes both the racemates of these compounds and the optical ones Antipodes and their mixtures.

Under the compounds of the formula I and the sub-formulas are those preferred in which at least one of the radicals contained therein has one of the preferred meanings given.

The Compounds of the formula I are prepared by methods known per se as described in the literature (e.g., in the standard works like Houben-Weyl, Methods of Organic Chemistry, Georg-Thieme-Verlag, Stuttgart) are described under reaction conditions that for the mentioned Reactions are known and suitable. You can do that by yourself known, not closer mentioned Make use of variants.

The Compounds of the formula I can e.g. according to the following reaction schemes or in analogy thereto getting produced. Further synthesis methods can be found in the Examples.

Scheme 1:

Scheme 2:

Scheme 3:

In Schemes 1 to 3, R ¹ , R ² , A ¹ , A ² , Z ¹ , Z ² , m and n are as defined above.

worin R¹, A¹, Z¹ und m die in Bezug auf Formel I angegebenen Bedeutungen besitzen.The present invention also relates to the spiro-diols of the following formula used in Schemes 1 and 2 as starting materials

wherein R ^1, A ^1, Z ¹ and m are as defined in relation to formula I.

The other starting materials are either known or can be used in Be prepared analogously to known compounds.

Possibly can the starting materials are also formed in situ, such that one do not isolate them from the reaction mixture, but continue immediately to the compounds of formula I.

The liquid-crystalline media according to the invention preferably contain, in addition to one or more compounds according to the invention, as further constituents 2 to 40, particularly preferably 4 to 30 components. In particular, these media contain, in addition to one or more compounds according to the invention 7 to 25 components. 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, cyclohexanecarboxylic acid phenyl or cyclohexyl esters, phenyl or cyclohexyl esters of cyclohexylbenzoic acid, Phenyl or cyclohexyl esters of cyclohexylcyclohexanecarboxylic acid, cyclohexylphenyl esters of benzoic acid, the Cyclohexanecarboxylic acid or cyclohexylcyclohexanecarboxylic acid, phenylcyclohexanes, cyclohexylbiphenyls, phenylcyclohexylcyclohexanes, cyclohexylcyclohexanes, cyclohexylcyclohexylcyclohexenes, 1,4-biscyclohexylbenzenes, 4,4'-biscyclohexylbiphenyls, phenyl- or cyclohexylpyrimidines, phenyl- or cyclohexylpyridines, phenyl- or cyclohexyldioxanes, phenyl- or cyclohexyl-1,3-dithiane, 1,2-diphenylethane, 1,2-dicyclohexylethane, 1-phenyl-2-cyclohexylethane, 1-cyclohexyl-2- (4-phenylcyclohexyl) ethane, 1-cyclohexyl-2 biphenylylethanes, 1-phenyl-2-cyclohexyl-phenylethanes, optionally halogenated stilbenes, benzylphenyl ethers, tolans and substituted cinnamic acids. The 1,4-phenylene groups in these compounds can also be fluorinated.

The most important compounds which may be used as further constituents of the media according to the invention can be characterized by the formulas 1, 2, 3, 4 and 5: R'-LE-R '' 1 R'-L-COO-E-R "2 R'-L-OOC-E-R "3 R'-L-CH ₂ CH ₂ -E-R "4 R'-LC≡CE-R "5

In the formulas 1, 2, 3, 4 and 5, L and E, the same or different could be, each independently each other is a bivalent radical from the group consisting of -Phe-, -Cyc-, -Phe-Phe-, -Phe-Cyc, -Cyc-Cyc, -Pyr-, -Dio, -G-Phe- and -G-Cyc- and their Mirror images formed group, where Phe unsubstituted or fluorine-substituted 1,4-phenylene, Cyc trans-1,4-cyclohexylene or 1,4-cyclohexenylene, pyr pyrimidine-2,5-diyl or pyridine-2,5-diyl, dio-1,3-dioxane-2,5-diyl and G is 2- (trans-1,4-cyclohexyl) -ethyl.

Preferably one of the radicals L and E is Cyc, Phe or Pyr. E is preferred Cyc, Phe or Phe-Cyc. Preferably, the media of the invention contain one or more components selected from the compounds of Formulas 1, 2, 3, 4 and 5, wherein 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 selected 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 multiple components selected from the compounds of the formulas 1, 2, 3, 4 and 5, wherein the radicals L and E selected are 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 having up to 8 C atoms, -F, -Cl, -CN, -NCS, - (O) _i CH _{3 - (k + 1)} F _k Cl _l , where i o or 1, k and l are independently, equal or different 0, 1, 2 or 3 and for the sum (k + l): 1 ≤ (k + l) ≤ 3.

R 'and R' 'are in a smaller subgroup the compounds of formulas 1, 2, 3, 4 and 5 are each independently Alkyl, alkenyl, alkoxy, alkoxyalkyl, alkenyloxy or alkanoyloxy with up to 8 carbon atoms. The following is this smaller subgroup Group A called and the compounds are with the sub-formulas 1a, 2a, 3a, 4a and 5a. For most of these compounds R 'and R' 'are different from each other, with one of these radicals is usually alkyl, alkenyl, alkoxy or alkoxyalkyl.

In a smaller subgroup of compounds of formulas 1, 2, 3, 4 and 5, other than group B, R '' is -F, -Cl, -NCS or - (O) _i CH ₃ - _{(k + 1)} F _k Cl _l , where i 0 or 1, k and l are independently, equal or different 0, 1, 2 or 3 and for the sum (k + l): 1 ≤ (k + l) ≤ 3. The compounds, in which R '' has this meaning are denoted by the sub-formulas 1 b, 2b, 3b, 4b and 5b. Particular preference is given to those compounds of the subformulae 1 b, 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 the subformulae 1 b, 2b, 3b, 4b and 5b R 'has the compounds the meaning of the sub-formulas 1a to 5a and is preferably Alkyl, alkenyl, alkoxy or alkoxyalkyl.

In another smaller subgroup of the compounds of formulas 1, 2, 3, 4 and 5, R "is -CN. This subgroup is referred to below as group C and the compounds of this subgroup are described in accordance 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 to 5a and is preferably alkyl, alkoxy or alkenyl.

Next the preferred compounds of groups A, B and C are also others Compounds of formulas 1, 2, 3, 4 and 5 with other variants of provided substituents in use. All these substances are according to literature methods or in analogy available.

In addition to compounds of the formula I according to the invention, the media according to the invention preferably comprise one or more compounds which are selected from groups A, B and / or C. The mass fractions of the compounds from these groups on the media according to the invention are preferably: Group A: preferably 0 to 90%, particularly preferably 20 to 90%, in particular 30 to 90%; Group B: preferably 0 to 80%, particularly preferably 10 to 80%, in particular 10 to 65%; Group C: preferably 0 to 80%, particularly preferably 5 to 80%, in particular 5 to 50%; wherein the sum of the mass fractions of the compounds of the groups A, B and / or C contained in the respective inventive media is preferably 5 to 90% and particularly preferably 10 to 90%.

The inventive media preferably contain 1 to 40%, more preferably 5 to 30 % of the compounds of the invention of formula I. Further preferred are media containing more as 40%, more preferably 45 to 90% of compounds of the invention of the formula I. The media preferably contain three, four or five compounds of the invention.

The Production of the Liquid-Crystal Mixtures According to the Invention takes place in per se usual Wise. In general, the desired Amount of components used in lesser amount in the Main component making up components solved, preferably at elevated temperature. It is also possible solutions of Components in an organic solvent, eg. In acetone, Chloroform or methanol, to mix and the solvent after mixing to remove again, for example by distillation. Farther Is it possible, the mixtures on other conventional Species, e.g. B. by using premixes, for. B. homolog mixtures or using so-called "multi-bottle" systems.

The Dielectrics can also further, known in the art and described in the literature additions contain. For example, you can 0 to 15%, preferably 0 to 10%, pleochroic dyes and / or chiral dopants are added. The individual, added Compounds are preferably added in concentrations of 0.01 to 6%, more preferably from 0.1 to 3% used. It will be however, the concentration data of the other constituents of the liquid-crystal mixtures So the liquid crystalline or mesogenic compounds, without consideration the concentration of these additives indicated.

The The following examples are intended to illustrate the invention without limiting it. In front- and below, percentages are by weight. All temperatures are given in degrees Celsius. Mp means melting point and Klp. = Clearing point. Furthermore, K = crystalline state, N = nematic phase, Sm = smectic phase and I = isotropic phase. The information between These symbols represent the transition temperatures dar. Δn means optical anisotropy (589 nm, 20 ° C) and Δε the dielectric anisotropy (1 kHz, 20 ° C).

The Δn and Δε values of Compounds of the invention are made by extrapolation from liquid crystalline mixtures obtained, which is 10% from the respective compound of the invention and 90% of the commercially available liquid crystal ZLI 4792 (Fa. Merck, Darmstadt).

"Usual processing" means: one gives optionally water added, extracted with methylene chloride, diethyl ether or toluene, separates, the organic phase is dried, evaporated and purifies the product by distillation under reduced pressure or crystallization and / or chromatography.

In front- and below the following abbreviations are used:

DCM dichloromethane DMF dimethylformamide MTB ether Methyl tert-butyl ether RT room temperature (about 20 ° C) THF tetrahydrofuran

example 1

346 ml (3.00 mol) of 1-pentene are dissolved in 3 l of diethyl ether and washed with 315 g (4.83 mol) of zinc and 15 g (80 mmol) of copper (II) acetate monohydrate added. Subsequently 370 ml (3.30 mol) of trichloroacetyl chloride are added dropwise to the batch, wherein the reaction mixture begins to boil. After 24 hours at Room temperature, the solids are separated and the filtrate washed with water, concentrated and passed through silica gel (pentane / DCM 3: 2). You get 365 g of a yellow oil (Salary: 64%).

430 mmol of the chlorinated cyclobutanone 7 (100 g (content 77%)) in 500 ml of acetic acid solved and added in portions with 100 g (1.5 mol) of zinc, leaving a temperature from 80 ° C not exceeded becomes. When the addition is complete, the batch is kept at 80 ° C. for a further 2 hours. After cooling At room temperature, the mixture is stirred with 500 ml of water and extracted with MTB ether. The combined organic phases become with water and saturated Washed sodium bicarbonate solution, dried over sodium sulfate and concentrated. You get 45.1 g of a yellow oil (Salary 78.7%).

930 g (2.6 mol) of the Wittig salt 10 and 292 g of the ketone 8 are in Suspended 2.5 l THF and at a temperature below 20 ° C in portions with 292 g (2.6 mol) of potassium tert-butoxide was added. The approach will be overnight stirred at room temperature. After the addition of water, it is acidified with hydrochloric acid and extracted with n-pentane. The organic phase is concentrated and treated with n-pentane over silica gel filtered. This gives 100.7 g (content 30%) of a yellow liquid.

Analogous to the above rule, the ketone 11 is prepared.

Analogous to the above protocol dechlorination to ketone 12 is performed.

100 ml of THF and 300 ml of dichloromethane are at a temperature of -10 ° C to -2 ° C with 30.0 Added ml (273 mmol) of titanium tetrachloride. Then be at -10 ° C 22.8 ml (150 mmol) diethyl malonate (13) and 24.0 g (95%, 150 mmol) of the ketone 12 in the reaction solution given. At a temperature below -5 ° C, 44.0 ml (546 mmol) Pyridine added dropwise to the batch. After 18 hours at Room temperature, the reaction mixture is mixed with 1500 ml of water. The organic phase is washed with water and concentrated. Of the Residue will over Silica gel (toluene / MTB ether 9: 1) filtered. This gives 45.3 g (89%, 91%) of the ester 14.

45.3 g (90%, 140 mmol) of the diester 14 is dissolved in THF on the palladium catalyst hydrogenated. The catalyst is separated off and the solution is concentrated. The residue obtained is used without further purification in the next stage. you receives 44.4 g (92%) of the saturated Esters 15.

Under Nitrogen becomes a suspension of 6.3 g (170 mmol) of lithium aluminum hydride in 100 ml of THF with a solution of 44.4 g (150 mmol) of the diester 15 in 100 ml of THF. there heated the approach to boiling. After completion of the addition, the approach 1 hour under reflux heated. At room temperature, the approach is careful with water and hydrochloric acid hydrolyzed. The reaction mixture is filtered through Celite. The organic Phase becomes with water and more saturated sodium bicarbonate washed and concentrated. You get 32.1 g (content 77.4%) of the diol 17.

8.0 g (77.4%, 29.1 mmol) of diol 17 and 9.0 g (132 mmol) of imidazole are dissolved under nitrogen in 60 ml of DMF and 11.4 ml (90.0 mmol) of chlorotrimethylsilane spiked and stirred overnight. The mixture is mixed with water and extracted with MTB ether. The organic phase is concentrated and the reverse was cleaned over silica gel. 5.5 g (90%) of the silyl ether 18 are obtained.

Synthesis path a), R = H:
16.0 g (77.4%, 58.3 mmol) of diol 17 and 9.3 g (58.0 mmol) of aldehyde 19 are dissolved in 100 ml of toluene, with 400 mg of p-toluenesulfonic acid (p-TsOH ) and heated under reflux at the water separator. The mixture is then washed with water and saturated sodium bicarbonate solution, concentrated and passed through silica gel (toluene / heptane). The product obtained is crystallized from heptane. This gives 5.7 g of dioxane 20 as colorless crystals of melting point 58 ° C.

Synthesis path b), R = SiMe ₃ :
Under nitrogen, a solution of 5.0 g (14.2 mmol) of the disilyl ether 18 in 60 ml of dichloromethane at -78 ° C with 0.4 ml (2.1 mmol) Trimethylsilyltrifluormethansulfonat added. Subsequently, a solution of 3.2 g (20.0 mmol) of the aldehyde 19 is added dropwise. After 2 hours at the low temperature, 2.0 ml of pyridine are added and the cooling is removed. After addition of 70 ml of saturated sodium bicarbonate solution, the aqueous phase is extracted with dichloromethane, the combined organic phases are dried over sodium sulfate and concentrated. The further purification is carried out in the manner described in synthesis route a). 3.2 g (64%) of compound 20 are obtained.
K 58 l,
Δε = 13.9 and
Δn = 0.0615.

Analogous Example 1 are made using the appropriate precursors the following compounds of the invention receive:

Examples 2-18

Examples 19-36

Examples 37-54

Examples 55-72

K 66 N (63,4) I,
Δε = 24,3 und
Δn = 0,0797.Analogously to Example 1, the following compound according to the invention is obtained using the corresponding precursor: Example 73

K 66 N (63,4) I,
Δε = 24.3 and
Δn = 0.0797.

Analogous Example 73 are using the appropriate precursors the following compounds of the invention receive:

Examples 74-90

Examples 91-108

Examples 109-126

Examples 127-144

For the examples 78 and 109, the following properties are determined:

Table 1

Example 145

Under nitrogen, the corresponding Grignard reagent is prepared in 75 ml of THF from 3.2 g (130 mmol) of magnesium turnings and 15.5 ml (130 mmol) of the bromide 2. Subsequently, a solution of the ketone 1 in 25 ml of THF is added to the reagent. The batch is heated to boiling for 1 hour. The cooled mixture is hydrolyzed, adjusted to pH 1 with hydrochloric acid and extracted with MTB ether. The organic phase is washed with saturated sodium bicarbonate solution and concentrated. The residue obtained is purified on silica gel (toluene). Yield: 22.0 g (68%)

Under Nitrogen becomes 14.4 g (40.0 mmol) of the alcohol 3 in 80 ml of dichloromethane and 17 ml of triethylamine dissolved and at 0 ° C with 4.1 ml (53.4 mmol) of methanesulfonyl chloride (MsCl). The approach is over Stirred at room temperature overnight. Subsequently the reaction mixture is added to water and diluted with n-heptane. The organic phase is concentrated and the residue obtained on silica gel given. The residue is used without further purification in the subsequent stage.

Unter Stickstoff werden 9,6 g (44,4 mmol) Pyridiniumchlorochromat (PCC), 1,2 g Natriumacetat und 6 g Celite suspendiert in 50 ml Dichlormethan aufgezogen und mit einer Lösung 9,4 g (36,7 mmol) des Alkohols 5 in 60 ml DCM versetzt. Nach Beendigung der Reaktion wird der Feststoff abgestemmt und mit DCM gewaschen. Das Eluat wird mit 1N Natronlauge und 2N Salzsäure gewaschen und eingeengt. Der erhaltene Rückstand wird über Kieselgel gegeben. Der Rückstand wird ohne weitere Reinigung in der Folgestufe eingesetzt.13.9 g of the crude alkene 4 is dissolved in THF and hydrogenated on the palladium catalyst. The hydrogenation solution is concentrated and the residue obtained is purified on silica gel. Yield: 9.7 g (88%)

Under nitrogen, 9.6 g (44.4 mmol) of pyridinium chlorochromate (PCC), 1.2 g of sodium acetate and 6 g of Celite suspended in 50 ml of dichloromethane and with a solution 9.4 g (36.7 mmol) of the alcohol. 5 in 60 ml DCM added. After completion of the reaction, the solid is triturated and washed with DCM. The eluate is washed with 1N sodium hydroxide solution and 2N hydrochloric acid and concentrated. The residue obtained is passed through silica gel. The residue is used without further purification in the subsequent stage.

The crude aldehyde 6 is dissolved in toluene, treated with p-toluenesulfonic acid and heated to boiling on a water. The cooled mixture is washed with saturated sodium bicarbonate solution and concentrated. The residue obtained is purified on silica gel and by crystallization from n-heptane. Yield: (30%)
K 70 I,
Δε = 14.3 and
Δn = 0.0322.

Analogous Example 145 are prepared using the appropriate precursors the following compounds of the invention receive:

Examples 146-162

Examples 163-180

Examples 181-198

Examples 199-216

The Compound of Example 201 is obtained as follows.

24.8 g (85 mmol) of the enol ether 7, 10 g (85 mmol) of 2-propyl-1,3-propanediol and 400 mg of p-toluenesulfonic acid are mixed with 100 ml of toluene and heated to boiling for 3 h on a water. The cooled batch is washed with sat. NaHCO ₃ sol. washed and concentrated. The crystals forming in the residue are isolated.

3.7 g (9.8 mmol) of the bromide 8 and 1.1 g (12.6 mmol) of copper cyanide mixed with 15 ml of N-methylpyrrolidone and heated to 140 ° C for 4 h. Of the cooled Approach is mixed with 100 ml of water and extracted with MTB ether. The organic phase is filtered, dried and concentrated. To Crystallization from ethanol at -20 ° C is the final cleaning mitttels HPLC.

The product has the following properties: K 69 S _H (53) N 73.4 I,
Δε = 26.2 and
Δn = 0.1120.

Examples 217-234

Examples 235-252

Examples 253-270

Examples 271-288

Example 289

Analogously to Example 73, the following compound according to the invention is obtained using the corresponding precursor:

in the individual, the synthesis is as follows.

346 ml (3.00 mol) of 1-pentene are dissolved in 3 l of diethyl ether and washed with 315 g (4.83 mol) of zinc and 15 g (80 mmol) of copper (II) acetate monohydrate added. Subsequently 70 ml (3.30 mol) of trichloroacetyl chloride are added dropwise to the batch, wherein the reaction mixture begins to boil., After 24 h at room temp. When the solids are separated and the filtrate is washed with water, narrowed and over Silica gel (Pen / DCM 3: 2). You get 365g of a yellow oil (content: 64%).

430 mmol of the chlorinated cyclobutanone 7 (100 g (content 77%)) in 500 ml of acetic acid solved and added in portions with 100 g (1.5 mol) of zinc, leaving a temperature from 80 ° C not exceeded becomes. After completion of the addition, the mixture is kept for 2 h at 80 ° C. After cooling on room temp. the mixture is stirred with 500 ml of water and extracted with MTB ether. The combined organic phases are with Water and sat. Sodium bicarbonate solution. washed, over sodium sulfate dried and concentrated. This gives 45.1 g of a yellow oil (content 78.7%).

930 g (2.6 mol) of the Wittig salt 10 and 292 g of the ketone 8 are in Suspended 2.5 l THF and at a temperature below 20 ° C in portions with 292 g (2.6 mol) of potassium tert-butoxide was added. The approach will be overnight at room temp. touched. After the addition of water, it is acidified with hydrochloric acid and extracted with n-pentane. The organic phase is concentrated and treated with n-Petnan on silica gel filtered. You get 100.7 g (content 30%) of a yellow liquid.

Analogous to the above protocol, the ketone 10 is prepared.

Analogous to the above protocol dechlorination to ketone 11 is performed.

In EV Dehmlow, S. Bueker Chem. Ber. 1993, 126, 2759-2764 describes vinyl acetate as starting material for the construction of a cyclobutyl ring. Thus, compounds of type 1 can be prepared via the described synthesis.
¹ H-NMR (CDCl _3, TMS): 7.33 (s, 5H, Ph); 4.52 (s, 2H, Ph-CH ₂ -O); 3.46 (d, J = 6.5Hz, 2H, O-CH ₂ -cyclobutyl), 3.10 and 2.98 (2m, 4H, 1-H ₂ and 3-H ₂ ); 2.60 (m _c, 1 H 6-H); 2.29 and 2.06 (2m _c , 4H, 5-H ₂ and 7-H ₂ ).

200 ml of THF and 600 ml of dichloromethane are at a temp. of -10 ° C to -2 ° C with 37.5 ml (340 mmol) of titanium tetrachloride. Then be at -10 ° C 28.6 ml (190 mmol) diethyl malonate (13) and 50.0 g (86.5%, 190 mmol) of the Ketone 12 in the reaction solution given. At a temp. Below -2 ° C, 55 ml (546 mmol) of pyridine drops are given in the approach. After 18 h at room temp. becomes the reaction mixture with 1500 ml of water. The organic Phase is washed with water and concentrated. The residue will over Silica gel (toluene / MTB ether 9: 1) filtered. You get 54.8 g (75%, 59%) of the ester 14.

54.8 g (75%, 110 mmol) of the diester 14 in THF on the palladium catalyst hydrogenated. The catalyst is separated off and the solution is concentrated. The residue obtained is used without further purification in the next stage. you receives 43.7 g (77%) of the saturated Esters 15.

30 g PCC (140 mmol) and 30 g Celite 545 are dissolved in 300 ml dichloromethane suspended and at T <25 ° C with 43.2 g (77%, 120 mmol) of the alcohol 15 dissolved in 200 ml of dichloromethane added. The approach is over Night stirred. The filtrate of the suspension is concentrated and the residue will over Silica gel (n-pentane / MTB ether 4: 1-1: 1). The residue is used without further purification in the next stage.

24.7 g (70 mmol) of methyl-triphenylphosphonium bromide are at 0 ° C with a solution of 7.2 g (60 mmol) of potassium tert-butoxide in 50 ml of THF. After 15 minutes at this temperature, 13.0 g (50 mmol) of the aldehyde 16 solved added in 50 ml of THF. After 18 h at RT, the mixture is mixed with water and with 1N hydrochloric acid adjusted to pH 6. The watery Phase is extracted with MTB ether. The organic phase is with Water washed over Dried sodium sulfate and concentrated. The residue is passed through silica gel (n-pentane / MTB ether 7: 3). The residue is used without further purification in the next stage.

A boiling suspension of 2.9 g (80 mmol) of lithium aluminum hydride in 50 ml of THF is added with a solution of 18 g (70%, 60 mmol) of malonate 17 in 50 ml of THF and subsequently 1 h under reflux held. The cooled Approach is hydrolyzed, acidified and diluted with MTB ether and over Celite sucked off. The organic phase is washed with water and sat. NaHCO.sub.3 solution. washed, dried and concentrated. The residue is used without further purification in the next stage.

10 g (90%, 50 mmol) of the diol 18, 15.5 g (50 mmol) of the aldehyde 19 and 400 mg of p-toluenesulfonic acid are mixed with 60 ml of toluene and heated for 1 h at Wasserabscheider. The cooled Approach over silica gel (Toluene). The product obtained is crystallized from n-heptane.

The product has the following properties:
K 75 N (54.3) I,
Δε = 22.3 and
Δn = 0.0964

For example 78

7.0 g (90% strength, 12 mmol) of the alkene 20 are dissolved in THF and hydrogenated on the palladium catalyst. The solution is then concentrated and the residue is passed through silica gel (toluene / n-heptane 1: 1). Further purification by crystallization from n-heptane. The product has the properties:
K 71 N (50.5) I,
Δε = 23.9 and
Δn = 0.0894.

Example 290

As an example of a compound of the formula I having two nonpolar end groups (with both R ¹ and R ^{2 being} alkyl or alkenyl), the preparation of the following compound is described.

Of the precursor The compound compound is prepared according to the following reaction scheme receive.

The further synthesis is carried out as follows.

25 g (106 mmol) of the ketone 6 and 67.2 g (196 mmol) of methoxymethyltriphenylphosphonium chloride suspended in 250 ml THF and at T <20 ° C with 11.9 g (106 mmol) of potassium tert-butoxide and 18 h at RT stirred. The approach is with ges. Ammonium chloride solution. offset and with 500 diluted with n-heptane. The organic phase is concentrated and the residue is passed through silica gel (n-heptane / toluene 1: 1). The product will be without further purification in the next stage implemented.

16 g of the product of the precursor are dissolved in 60 ml of toluene and mixed with 36 ml of formic acid and stirred at RT for 18 h. The mixture is then added to 200 ml of water. The aqueous phase was extracted with MTB ether, the organic phase with sat. NaHCO ₃ sol. washed and concentrated. The residue was used without further purification in the subsequent stage.

298 g (1.32 mol) stannous chloride, 300 g (1.32 mol) ethyl 4-bromocrotonate and 438 g (2.64 mol) of potassium iodide are placed in 3 l of water and at T <35 ° C with a 37% solution of formaldehyde in water. After 24 h, the approach with Extracted diethyl ether. The organic phase is concentrated and passed through silica gel (Toluene, toluene / MTB ether 1: 1). The residue is distilled in vacuo, bp 70 ° C.

208 g (24%, 346 mmol) of the ester 11 are dissolved in toluene and dissolved in a boiling suspension of 12.4 g (330 mmol) of lithium aluminum hydride in 100 ml of toluene and 1200 ml of THF. After heating for 1 h backflow and then cooling down The reaction was hydrolyzed with a hot solution of 93.2 g of sodium bicarbonate decahydrate in 30 ml of water. After stirring for 30 minutes, the solid is separated off. The filtrate is concentrated. The residue is without further purification used in the next stage.

4.1 g (80% strength, 32 mmol) of the diol 12, 16.6 g (50% strength, 31 mmol) of the aldehyde 8 and 360 mg of p-toluenesulfonic acid are mixed with 60 ml of toluene and 1 h the water to Boil boiling. The cooled mixture is passed through silica gel (toluene), the eluate is concentrated, the residue from n-heptane crystal lisiert, over basic AlO _x . given (toluene / n-heptane 1: 1) and recrystallized from n-heptane.

The product has the properties:
K 40 S _B 121 I,
Δε = 0.8 and
Δn = 0.0491.

Claims (16)

Dioxane derivatives of the formula I.

R ¹ , R ^{2 are} each independently, identically or differently H, halogen (F, Cl, Br, I) or a linear or branched, optionally chiral, unsubstituted, mono- or polysubstituted by halogen alkyl or alkoxy radical having 1 to 15 C atoms in which one or more CH ₂ groups are each independently denoted by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, - CH = CH-, -CH = CF-, -CF = CF-, -C≡C- or

may be replaced so that heteroatoms are not directly linked, -CN, -SCN, -NCS, -SF ₅ , -SCF ₃ , -CF ₃ , -CF = CF ₂ , -CF ₂ CF ₂ CF ₃ , -OCF ₃ , -OCHF ₂ , -CF ₂ CH ₂ CF ₃ or -OCH ₂ CF ₂ CHFCF ₃ , A ¹ , A ² each independently, the same or different a) trans-1,4-cyclohexylene, wherein also one or more not adjacent CH ₂ groups may be replaced by -O and / or -S- and wherein one or more H atoms may be replaced by F, wherein one or two CH groups may be replaced by N, b) 1,4-phenylene, and in which also one or more H atoms can be replaced by halogen (F, Cl, Br, I), -CN, -CH ₃ , -CHF ₂ , -CH ₂ F, CF ₃ , -OCH ₃ , -OCHF ₂ or - OCF ₃ may be replaced, c) a radical from the group bicyclo [1.1.1] pentane-1,3-diyl, bicyclo [2.2.2] octane-1,4-diyl, spiro [3.3] heptan-2, 6-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, piperidine-1,4- diyl, phenanthrene-2,7-diyl, fluorene 2,7-diyl, anthracene-2,6-diyl, anthracene-2,7-diyl and indane-2,5-diyl, where one or more H atoms may be replaced by halogen, in particular F, d) 1,4-cyclohexenylene or 1,3-cyclobutane-1,3-diyl, Z ¹ , Z ^{2 are} each, independently of one another, identical or different -O-, -CH ₂ O-, -OCH ₂ -, -CO- O, -O-CO-, -CF ₂ O-, -OCF ₂ -, -CF ₂ CF ₂ -, -CH ₂ CF ₂ -, -CF ₂ CH ₂ -, -CH ₂ CH ₂ -, -CH = CH-, -CH = CF-, -CF = CH-, -CF = CF-, -CF = CF-COO-, -O-CO-CF = CF-, -C≡C-, -CH ₂ CH ₂ CF ₂ O- or a single bond, and m, n are independently, identically or differently 0, 1, 2 or 3, mean. Compounds according to claim 1, characterized in that m = 0, 1 or 2 and n = 1 or 2 mean. Compounds according to claim 1 or 2, characterized in that m = 0 or 1 and n = 1 or 2 mean. Compounds according to one or more of claims 1 to 3, characterized in that G

Compounds according to one or more of claims 1 to 4, characterized in that G

Compounds according to one or more of claims 1 to 5, characterized in that they have one of the following formulas:

wherein R ¹ and R ^{2 have} the meanings given in claim 1 and L ¹ , L ² , L ³ and L ⁴ independently, identically or differently mean H or F. Compounds according to one or more of claims 1 to 6, characterized in that they have one of the following formulas:

wherein R ¹ and R ^{2 have} the meanings given in claim 1 and L ¹ , L ² , L ³ and L ⁴ independently, identically or differently mean H or F. Compounds according to at least one or more of claims 1 to 7, characterized in that R ^{1 is} H or a linear alkyl radical having 1 to 10 carbon atoms. Compounds according to at least one or more of claims 1 to 8, characterized in that R ^{2 is} H, a linear alkoxy radical having 1 to 10 C atoms, -F, -Cl, -CF ₃ , -OCF ₃ , -OCHF ₂ , - CN, -NCS or -SF ₅ means. Use of compounds of the formula I according to one or more of the claims 1 to 9 as component (s) in liquid crystalline Media. liquid-crystalline Medium with at least two liquid-crystalline Components, characterized in that there is at least one compound of the formula I according to one or more of the claims 1 to 9 contains. Liquid crystal display element, characterized in that it is a liquid-crystalline medium according to claim 11 contains. Reflective or transflective liquid crystal display element, characterized in that it is a liquid-crystalline medium according to claim 11 contains. Electro-optical display element, characterized that it is a liquid crystalline Medium according to claim 11 contains. Spiro-diols of the following formula

wherein R ¹ , A ¹ , Z ¹ and m have the meanings given in relation to formula I in claim 1. Process for the preparation of a compound of the formula I according to one or more of claims 1 to 9, characterized a spiro-diol according to claim 15 is used.