CA2093212A1 - Liquid-crystalline compounds - Google Patents

Abstract

Abstract Liquid-crystalline compounds of the formula I
I
in which.

R is H, an alkyl or alkenyl radical having 1 to 15 carbon atoms which is unsubstituted, monosubstituted by CN or CF3 or at least mono-substituted by halogen, it also being possible for one or more CH2 groups in these radicals each to be replaced, independently of one another, by -O-, -S-,

Description

~t~C~1~

Liquid-cryHtalline compounds The invention relate~ to liquid-crystalline compound~ of the formula I

R-(Al-Z1)~-[_ ~ ]~-Z-(A)o~W~(CH2):~Q~(CH2)t-y in which R is H, an alkyl or alkenyl radical having 1 to 15 carbon atoms which is unsubstituted, monosubstituted by CN or CF3 or at least mono-substituted by halogen, it also being possible for one or more C82 groups in these radicals each to be replaced, independently of one another, by -O-, -S-, - O -, -CO-, -CO-O-, -O-CO- or -O-CO-O- in such a way that oxygen atom~ ~ro not lin~od directly to one another, Z1 and Z are each, independently of one another, -C~zCB2-, -C~-C~-t -C.C- or a single bond, and one of the radicals Z~ and Z i9 alternatively -(C~2),- or -c~c8-ca2c82-, A and A1 are each, independently of one another, trans-1,4-cyclohexylene in which, in addi-tion,-one or two non-adjacent C~2 groups may bo replaced by -O-, or aro 1,4-phenylene which i8 un~ubstituted or monosubstituted or disubstituted by fluorine and/or Cl atoms and in which, in addition, one or two C~ groups may bo replaced by N, m i8 O, 1, 2 or 3, o and ~ is O, 1 or 2, where (8+0) is 2 2, 30 W is -O-, -COO- or a single bond, Q is -O-, -C8-CH- or a single bond, r is 1 to 7, t i~ O to 7, and Y is F, Cl, CF3, OCF3, CHFz, OC8F2 or OC~2F.

- 2 - ~ ~ ~3212 The invention furthermore relates to the use of these compounds as components of liquid-crystalline media, and to liquid-crystal and electro-optical display elements which contain the liquid-crystalline media S according to the invention.
The compounds of the formula I can be used a~
components of liquid-crystalline media, in particular for displays based on the principle of the twistQd cell, the guest-host ef~ect, tho offect of deformation of aligned phase~ or the effect of tynamic scattering.
The sub~tances employed hitherto for this purpose have certain disadvantagea, for example excessively high melting points, excessively low clearing points, inadequate stability toward~ the action of heat, light or electric fields, inadequate electrlcal re~istance, exces~ively hiqh temperaturo dependence of the thre~hold voltage, or unfavorable ela~tic and/or dielectric proporti~3.
In particular in displays of the supertwi~t type (STN) having twist angles of significantly greater than 220 or in displays having an activo matrix, the material~ employed hithorto have disadvantage3.
The invention had the obj~ct of finding novel stable liquid-crystalline or m sogcnic compounds which are suitablo a~ components of liquid-cry~talline media and at the same time, have, in particular, relatively low vi~co~ity and relatively high dielectric anisotropy ant high nematogeneity.
It has been found that compounds of the formula I are eminently suitable as component~ of liquid-crystalline media. In particular, they have relatively low vi~cosities and high nematogeneities. They can be used to obtain stable liquid-crystalline media havinq a broad mesophase range and advantageou~ values for the optical and dielectric anisotropy. These media furthermore have very qood low-temperature behaviour, ie.
excellent solubility in the conventional LC materials, at the same time occurrence of smectic phases being effectivel~ suppressed.
Liquid crystals of the formula CsHl; ~~oc6Hl 3 have already been di~closed in WO 8902425.
JP 59/155485-A2 m ntions a compound of the formula CqHg~~O~C4Hg Finally, EP 27B665 describe3 compounds of the formula Alkyl- ~ ~ O-CH2CH--Alkyl F
DE 31 36 624, DE 32 09 178 and DE 34 10 734 disclose compound~ of tho following formulao:

CsHI 1 -~O-C2Hs CsHll~O~CnH2n~.
n - 1 or 6 ~ F n - 5 or 7, CnH2ntl~~C2Hq~O~C~H2m~1 m - 1, 2, 6, 10 or 11-CsH~ }C2Hs JP 59/01,684 discloses 3-fluoro-4-substltuted 4-bicyclohexylbenzenes of the formula - 4 _ 2093~1~

R ~ ~ ~ (R, R' - CllO-alkyl).

5 803 A relates to esters of the general formula Alkyl- ~ COO-(CH2)ls~(CF2)s-1o~H

EP 0 360 521 A describes compounds of the general formula Alkyl-O-~}OCO-<~ (CO) ~/l-o-cH2- (CF2) 3~s--F
Cl WO 89/02 884 discloses trifluoromethyl ethers of the formula R- ~ ~ GCF3 Finally, DE-A 39 09 802 describë~ compounds of the formula ~30 (CH2) ncHF2 EP-A 0 168 683 discloses liquid crystals of the following formulae:

alkyl- ~ ~ O-(CH2)n-CH=CH-alkyl alkyl- ~ ~ ~ O-(CH2)n-CH=CH-alkyl The compounds of the formula I where Y = CF3 facilitate both STN display~ having a very steep electro-optical characteristic line and displays having an activematrix and excellent long-term 3tability. Compared with non-fluorinated-compounds, the compounds according to the invention have both higher ~ and higher ~1. Due to their - s - 20~
particularly favourable elastic propertie~, they are particularly suitable as components for TF~ mixture~ A
suitable choice of r and s allows the threshold voltages to be signif icantly reduced in di~plays of both types.
However, in view of the very wide variety of areas of application of such compounds, it was desirable to have available further compounds which have propertie~
precisely customised to the particular application~.
- In addition, the provision of compounds of the formula I very generally considerably broAdens the range of liquid-crystalline substance~ which ara suitable, from various applicational points of view, for the preparation of liquid-crystalline mixtures.
~he compound~ of the formula I havs a broad range of applications. Depending on the choice of substituents, ~he~e compounds can be used as ba~e materials from which liquid-cryst~llina media are predominantly composed;
however, it i~ also po~sible to ~dd co~poundr of th0 formula I to liquid-crystalline b~e materials from other classes of compound, in order, for example, to influence the dielectric and/or optical anlsotropy of a dielectric of this type and/or to optimize it8 threshold voltage and/or its viscosity.
In the pure state, the compounds of the formula I are colourless and form liquid-cry~talline mesophasQ~
in a temperatura range which is favor~bly located for electro-optical use. They re stable ch~ic~lly, thermally and to light.
The invention thus relate~ to the compounds of the formula I and to the use of thase compounds as components of liquid-crystalline media. The invention furthermore relates to liquid-crystalline media containing at least one compound of the formula I and to liquid-crystal display elements, in particular electro-optical display elements, which contain media of thistype.
Above and below, R, Al, A, zl, z, W, Q, Y, m, o, r and t are as defined above, unless expressly stated - 6 - ~ ~93~
otherwise. If A1 and A are a substituted 1,4-phenylene ring, the phenylene ring is preferably substituted in the 2-, 2,3- or 2,6-position by fluorine.
Z~ and Z are preferably a single bond or -C82CH2-.
If one of the radicalg Z1 and Z i9 - ( CH2 ) 2--(CH2)4- or -CH-CH-CHzCH2-, the other radical Zl or Z i~
preferably a sinqle bond.
PrefQrred compounds of thi~ typ~ conorm to the sub-formula I~
F

~ 3Z-~W_ (CH2) r~Q~ (CH2) t~Y I ~

in which Z is -(C~2)~- or -c~-ca-c~2c~2-, and R, r, t, L, W, Q and Y are a~ defined in for~ula I.
Preference i8 likewise given to co~pounds of the ~ub-formula I'' F
R_~Zl~~}Z~W~ (CH2) r~ (CH2) t--Y I ~ ~

in which L i8 B or F, and R, Z~, W, Q, Y, r and t are as defined in Claim 1. If t - O, Q i~ preferably a single bond.
Y may also be ~ if W ~ O or denotes a single bond.
In the following, for reasons of ~implicity, A'' i8 a 1,4-cyclohexylene radiGal, B i~ a radical of the formula ~
~' .
where L i8 preferably F. Y is preferably Fr Cl or CF3, and r and s are preferably 1, 2, 3 or 4. Q i9 preferably a single bond.
The compoundq of the formula I accordingly include compound~ of the sub-formulae ~ 7 ~ 2~3~
R-A" -A' ' -a-~ (cH2 ) r- (cH2 ) -Y I ' ' a R-A' ' -A' ' -3-W- (CH2 ) r~0~ (CH2 ): ~Y I ' ' b R-A' ' -Z:-A' ' -B-W--(CH2) r~ (CHz) -Y I ' ' c R-A' ~ -Z l -A' ' -B-W (CH2 ) r~0~ (CH2 ) -Y I ' ' d R-A' ' -A' ' -Z2-B-W- (CH2 ) r~ (Ci{2 ) ~-Y I ' ' e R-A' ' -A~ ' -Z2-B-W--(CH2 ) c~~ (CH2 ) ~-Y I ' ' f R-A' ' -Z' -A' ' -Z2-B-W- (CH2 ) r~ (CH2 ) c-Y I ' ' g R-A~ ~ -Zl-A~ ' -Z2-B-W- (CH2) r~O~ (CH2~ ~~Y I ~ ~ h Of the~e, particular preference is given to those of the sub-formulae I~a, I~b, I~e and I~f. In the compounds of the sub-formulae I~c to I~h, Z1 and Z are -CH2C~2-, -CH-CH- or -C.C-, preferably -CH2CH2-.
Particular preference i8 al80 given to the compound~ of the formuln LA, CnH2n~l~D~ (CH2) ~~ [~a] ~ - Z~ (A) 0~O~ (CH2) -(CH=CH)b-CF3 IA
in which n i8 0 to 7, D i8 -0~~ -C~=CH- or a single bond, a i8 1 to 5, b i3 0 or 1, and Z, A, o, and r are as defin~d in Claim 1.
Particularly preferred sub-formulae of compounds IA are - the compounds of the formula Ia CH3O- (CH2 ) ~~ [ ~ 9-Z- (A) o~O~(CH2)r-(CH=CH)b-CF3 Ia in which a Ls 1 to 5, b i8 0 or 1, ~ is 1 or 2 and A, Z, o and r are 8 defined in Claim l;
- the compound~ of the formula Ib cnH2~ - - [ - a Z ~A) 0~O~ (CH2) r~ ~CH=CH)~-CF3 Ib Ln which n i8 1 to 7, 8 is 1 or 2, b i3 0 or 1 and A, Z, o and r are as defined in Claim 1;
- the compound3 of the formula Ic, ~3~

L

R-(Al-Z;)~-[- ~ L Ic in which Ll is a, F or Cl, L2 i~ F or Cl, and R, Al, zl, z, m and g are a~ defined in Claim 1.
If R in the formula I i~ an alkyl radical and/or an alkoxy radical, this may be str~ight-chain or branched. It i~ preferably ~traight-chain, has 2, 3, 4, 5, 6 or 7 carbon atom~ and i8 accordingly preferably ethyl, propyl, butyl, pentyl, haxyl, heptyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy or heptoxy, further~ore methyl, octyl, nonyl, decyl, undecyl, d`odecyl, ~ridecyl, tetradecyl, pentadecyl, mothoxy, octoxy, nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy or tetradecoxy.
Oxa~lkyl i~ profor~bly straight-chain 2-oxapropyl (- methoxymethyl), 2- l~ ethoxymethyl) or 3-oxabutyl (~ 2-methoxyethyl)~ 2-, 3- or 4-oxapentyl, 2-, 3-, 4- or 5-oxah~xyl, 2-, 3-, 4-, S- or 6-ox~heptyl, 2-, 3-, 4-, 5-, 6- or 7-oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonyl, or 2-, 3-, 4-, 5-, 6-, 7-, a- or 9-oxadecyl.
If R is an alkenyl radical, it may be ~traight-chai~ or branched. It i preferably straiqht-chain and ha3 2 to 10 carbon atoms. Accordingly, it is in par-ticular ~inyl, prop-1-, or prop-2-enyl, but-l-, 2- or but-3-onyl, pent-1-, 2-, 3- or pent-4-enyl, hex-1-, 2-, 3-, 4- or hex-5-enyl, hept-1-, 2-, 3-, 4-, S- 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, or dec-1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or dec-9-enyl.
If R i~ an alkyl radical in which one ca2 group has been replaced by -O- and one has been replaced by -CO-, the~e are preferably adjacent. These thus contain an acyloxy group -CO-O- or an oxycarbonyl group -O-CO-.
These are preferably straight-chain and have 2 to 6 carbon atoms.

9 2~g~
Accordingly, they are ln particular acetyloxy, propionyloxy, butyryloxy, pentanoyloxy, hexanoyloxy, acetyloxymethyl, propionyloxymethyl, butyryloxymethyl, pentanoyloxymethyl, 2-acetyloxyethyl, 2-propionyloxy-ethyl, 2-butyryloxyethyl, 3-acetyloxypropyl, 3-propionyl-oxypropyl, 4-acetyloxybutyl, methoxycarbonyl, ethoxycar-bonyl, propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxy-carbonylmethyl, butoxycarbonylmethyl, 2-(methoxycar-bonyl)ethyl, 2-(ethoxycarbonyl)ethyl, 2-(propoxycar-bonyl)ethyl, 3-(methoxycarbonyl)propyl, 3-(ethoxycar-bonyl)propyl or 4-~methoxycarbonyl)butyl.
If R i8 an alkenyl radical in which one C~2 group adjacent to the vinyl group has been replaced by C0 or C0-0 or 0-C0-, thi~ may be straiqht-cha~in or branched. It iff preferably straight-chain and ha~ 4 to 13 carbon atom~. Accordingly, it is in particular acryloyloxy-methyl, 2-acryloyloxyethyl, 3-acryloyloxypropyl, 4-acryloyloxybutyl, 5-acryloyloxypentyl, 6-acryloyloxy-hexyl, 7-acryloyloxyheptyl, 8- cryloyloxyoctyl, 9-acrylo-yloxynonyl, 10-acryloyloxydecyl, metb~cryloyloxymethyl, 2-mothacryloyloxyethyl, 3-meth~cryloyloxypropyl, 4-methacryloyloxy-butyl, 5-mothacryloyloxypentyl, 6-mothacryloyloxyhexyl, 7-mothacryloyloxyheptyl, 8-methacryloyloxyoctyl or 9-methacryloyloxynonyl.
If R i~ an alkyl or alkenyl radical which is ~oAorub~tituted by CN or CF3, thi~ radical is preferably straight-chain and the substitution by CN or CF3 i8 in the ~-po~ition.
If R i~ an alkyl or alkenyl radical which is at lea~t mono~ubstituted by halogen, this radical is prefer-ably straight-chain and halogen i~ preferably F or Cl. In the caRe of multiple substitution, halogen i~ preferably F. The resultant radicals also include perfluorinated radical~. In the case of monosubstitution, the fluorine or chlorine ~ubstituent may be in any desired po~ition, but is preferably in the ~-position.

- 10~
Compound-Q of the formulae I which contain wing groups R which are suitable for polymerisation reaction~
are suitable for the formation of liquid-cry~talline polymer~.
Compounds of the formula I containing branchsd wing groups R may occa ionally be of importance due to better solubility in the customary liquid-cry~talline base materials, but in particular as chiral dopants if they are optically acti~e. Smectlc compounds of this type are Auitable a~ component~ of ferroelectric materials.
Compound~ of the formula I having SA phase~ are suitable, for example, for thermally addre~ed display~.
Branched groups of this type generally contain not more than one chain br~nch. Preferred branched radical~ R are isopropyl, 2-butyl (~ methylpropyl), isobutyl (= 2-methylpropyl), 2-methylbutyl, isopentyl (= 3-methylbutyl), 2-methylpentyl, 3-methylpentyl, 2-ethylhexyl, 2-propylpentyl, isopropoxy, 2-methyl-propoxy, 2-methylbutoxy, 3-methylbutoxy, 2-methylpentoxy, 3-methylpentoxy, 2-ethylhexoxy, l-methylhexoxy and l-methylheptoxy.
If R is an alkyl radic~l in which two or more CH2 groups have been replaced by -0- and/or -C0-0-, this may be stra~ght-chain or branched. It i8 preferably branched and has 3 to 12 carbon atoms. Accordingly, it i~ in par-ticular biscarboxymethyl, 2,2-biscarboxyethyl, 3,3-biQ-carbo~ypropyl,4,4-biscarboxybutyl,5,5-biscarboxypantyl, 6,6-biscarboxyhexyl, 7,7-biscarboxyheptyl, 8,8-biscar-boxyoctyl, 9,9-biscarboxynonyl, 10,10-biscarboxydecyl, bi~(methoxycarbonyl)methyl, 2,2-bi~(methoxycarbonyl)-ethyl, 3,3-bis(methoxycarbonyl)propyl, 4,4-bis(methoxy-carbonyl)butyl, 5,5-bis(methoxycarbonyl)pentyl, 6,6-bis-(methoxycarbonyl)hexyl~ 7,7-bis(methoxycarbonyl)heptyl, 8,8-bis(methoxycarbonyl)octyl, bis(ethoxycarbonyl)methyl, 2,2-bis(ethoxycarbonyl)ethyl, 3,3-bis(ethoxycarbonyl)-propyl, 4,4-bis(ethoxycarbonyl)butyl or 5,5-bis(ethoxy-carbonyl)hexyl.

~ 2 ~ ~ 3 2 1 h Of these compounds of the formula I and the sub-formulae, those are preferred in which at least one of the radical~ present therein has one of the preferred meanings indicated.
S Some very particularly preferred ~maller groups of compounds are those of the sub-formulae Il to ISO, in which L is ~ or F, n ~ 1-14 and r and t are each 1-7.

R~O--(CH2) n~F ' Il F

R~O--(CH2) n--Cl I2 R~O--(cH2 ) n~CF3 I 3 R~CH2CH2~0--(CH2) _-F I4 R~CH2CH2~0--~CH2) n-Cl I5 L

R~CH2CH2~0--~CH2 ) n~CF3 I 6 R~COO--~ CH2 ) n--F I 7 B 9 ~3 s ~ ~

R~COO--(CH2 ) n-Cl I 8 R~COO--(CH2) n--CF3 I9 R~CH2CH2~COO- ~CH2) r--O~ (CH2) t-F I10 R~CH2CH2~COO- (CH2) r~O~ (CH2) t-Cl Ill R~CH2CH2~COO--~CH2) r~O~ ~CH2) t-CF3 I12 R~CH2CH2~ ~CH2 ) n~F I 13 -R~CH2CH2~ ~CH2) n--Cl I14 R~}CH2cH2~ (CH2) n~CF3 I15 ~ 13 - 2~93~
F

R~CH2CH2~ (CH2 ) n-CÆ2 I 16 R~}CH2c~32~ (cH2) n~CF3 I17 R~CH2CH2~CH2O (cH2) n-l~F I18 R~CH2CH2~CH20 (CH2), l-Cl Il9 R~CH2CH2~CH20~CH2)n ~--CF3 I20 .

R~CH2O (CH2) n l--F I21 F
R~H2O (CH2) n l-Cl I22 R_~CH2O (CH2 ) n- -CF3 I 2 3 - 14 ~ 3~2 R~O- (cH2) r~CF3 I24 R~O- (CH2) r-CH=CH-CF3 I25 R~O- ( CH2 ) r -CF3 I 2 6 R~(CH2) r~CF3 I27 R~ ~CH2) r~CF3 I28 ~(cH23 r~CF3 I29 R~ (cH2) r~CF3 I30 R~ (cH2) r~CF3 I31 R-(}(cH2) r~CF3 I32 R~CH2CH2~} (CH2) -CF3 I33 R~ ~CH2) 4~ (CH2) .-CF; I34 R~ (cH2) 4~ (cH2) r~CF3 I35 ~3~ ~

R~O- tCH2) ~-CH=C;{-CF3 I36 R~ (CH2 ) -CH=CH-_F3 I 37 R~ tCH2) r-CH=CH-CF3 , I38 R~(CH2) r-CH=CH-CF3 I39 R~{~(CH2) r-CH=CH-CF3 I40 R~)~(CH2) r-CH=CH-CF3 I41 R~ (CH2 ) r-CH=CH-CF3 I 4 2 R_~(CH2) r-CH=CH-CF3 I43 R_~CH2CH2 O tCH2) r-CH=CH-CF. I44 R~CH2CH2~ (CH2) -CH=CH-CF; I45 - 16- 20~3212 R~ (CH2) 4~} (CH2) c-CH=CH-CF3 I46 R~(CH2) 4~ (CH2)r-CH=CH-CF3 I47 R~OCH2CF, (L', L2 = H oder F) ~ I48 R~ ~OCH2 CF3 I 4 9 N
L

R{ ~OCH2CF; I50 L

- 17 - 2~3~
The compounds of the formula I are prepared by methods known per se, as described in the literature (for example in the standard works such as Houben-Weyl, Methoden der Organischen Chemie, Georg-Thieme-Verlag, Stuttgart, Vol. IX, pp. 867 ff), to be precise under reaction conditions which are known and suitable for the said reactions. U~e may also be made here of variants which are known per se, but are not de~cribed here in greater detail.
The compounds of the formula I according to ~he invention where W = -O- and A = ~ can be prepared, for example, by metalating a compound of the formula II
F

R ~ Zl ~ z ~ II

in which L is H or P, and R, Z1 and Z are a~ defined above, in accordance with the reaction ~cheme below, and sub~equently reacting the product with a suitable electrophile:

Scheme 1 F 1. n-3uLi/KOBu' R ~ Z- ~ Z ~
L 2. B(OMe)3 II 3. H2O2 F

Z ~ H

III
The compounds of the formula II where L = F are novel and are thus also the sub~ect-matter of the inven-tion. Furthermore, compounds of the formula III where L = F are a sub~ect-matter of the invention.

- 18 - 2~ 12 The invention furthenmore relate~ to liquid-cry3talline media containing at least one compound of the formula II.
The compounds of the formula I (W - -O- and A =
F

~ ) can be obtai.ned from the re~ultant phenol of the formula III by known etherification methods, for example by reaction with ~al-(C~2)~-Q-(CH2)~-Y (~al = I, Br or Cl) in acetone~R2CO3, optionally in the presence of catalytic amounts of RI.
The compounds according to the invention can al80 be obtained from the bromine derivative IV

IV
~r~O ~W-(c~2)r-Q-(cH2)t-Y
L
Further synthesi~ methods for the phenyl ethers according to the invention are obvious to a perCon skilled in the art. For example, appropriately 5-substituted 1,3-difluorobenzene compounds or mono-fluorinated analogues (L = H) can be converted to tha 2-O- ( C~2 ) r~Q~ (CH2)~-Y-1,3-difluoro com~ounds or mono-fluorinated analogues (L - H) in accordance with the above 20 scheme, and the radical R ~ z~ ~ z can sub~equently be introduced by reactions which are customary in liquid-cry~tallina chemistry (for example etherification or coupling, for example as described in the article E. Poetsch, Rontakte (Darmstadt) 1988 (2), p. 15).
~he compounds of the formula II can be prepared for example, by the following synthesis:

- 19 - ~93~
Scheme R ~ z: ~ CH2P~Phj ~ + OHC ~

R ~ Zl ~ CH=CH ~ L

l, H2~Pd-C

R ~ Zl ~ CH2CH2 ~ L

The synthesis of qome particularly preferred com-pounds is indicated in greater detail below:

- 20 - ~ ~ 9 ~
Sch me 3 (L = H or F~

F 1. -H20 R~}Z {~eO + Li~ -L 2. H2/Pd-C

F 1. n-BuLi R ~ Zl ~
L 2. 8(0Me)3 3. H202 R ~ Zl ~ oHL

Aceton ~ ClCHzCH2CH2F/K2CO3 R ~ z: ~ 0CH2CH2CH2F

- 21 - 2~93~2 Sche~e 4 (R~ZI~) 2-zn ul t rasound Br~OBz ~Luche et al. I F
Tetrahedron Lett.
1984, 3463) R~z; ~roBz H2 / Pd-C

R~Z:~OH

Acetone J, ICH2CH2CH2Cl/K2CO3 R~z: ~OCH2CH2CH2Cl F

Schel~ 5 Br~OH ~ Br~OCH3 ultrasound ¦ (R~Z;~})2-Zn ?.~ Z ~

Phenyl ethers of the formula I are obtainable by etherification of corre~ponding hydroxyl compounds, preferably corresponding phenol~, the hydroxyl compound expediently fir~t being converted to a corresponding metal derivative, for example to the corre~ponding alkali metal alkoxide or alkali metal phenoxide by treatment with NaH, NaNH2, NaOH, XOH, Na2CO3 or R2CO3. This can then be reacted with the appropriate alkyl halide, alkyl sulfonate or dialkyl sulfate, expediently in an inert solvent, such as, for example, acetone, 1,2-dimethoxy-ethane, DMF or dimethyl sulfoxide, or altornatively with an excess of aqueou~ or agueous-alcoholic NaOH or KOH at temperature~ between about 20 and 100C.
Furthermore, the alkyl ethers may al~o be pre-pared by the method of Mitsunobu from the correcponding phenols a~d a hydroxyl compound in the presence of triphenylphosphine and diethyl azodicarboxylate (S. Bittner, Y. A~saf, Che~istry and Industry, 281 (1975); M.S. Manhas, W.H. Hoffman, B. Lal, A.K. ~ose, J. Chem. Soc. Perkin I, 461 (1975):

Sç~

R ~ ZI ~ Z ~ H ~ HO--(CH2)r-Q-(CH2)t-Y

PPh3 F
~n~Zl~Z~ (CH2) ~--(CH2) ~-Y
HsC20CN-NCOC2Hs L
Il 11 O O

The starting materials for the preparation processe~ are either known or can be prepared analogously to known compound~.
The compounds of the formula I~ where Z - -(CH2)~- can be prepared in accordance with the - 23 - ~ ~ ~3~
following scheme (n = 1-8):

Scb~e Z (L - H or F) R ~ C~Y,CH2-3r 1 chain extension by mean~ of malonic 1 ester~ via hydroly~is, decarboxyla-I tion, LiAlH~ reduction and subsequent 1 reaction with R~r A
R ~ ,~ H~ (CH2)~-Br Zn~r2/Li ultrasound (Luche et al., Tetrahedron Lett. 1984, 3463) [R ~ (CH2)4]2-Zn I

F ~ 1 Br ~ ~o-(C;~2) -y L PdII-Catalyst . L

R ~ (CH2)~ ~ R ~ (CH2)4 ~ -(CH2)n-Y I''' In the Pd(II)-catalysed coupling reaction, the target product ~ is either formed directly or a preCUr80r i8 formed into which the radical -O-(CH2)~-Q-lCHz)c-Y i8 introduced entirely analogously to the abovementioned methods for compounds of the formula I.
lS The phenyl esters of the formula I according to the invention ~Q - -COO-) are obtained from the compounds of the formula II in accordance with the following reaction scheme:

- 24 _ 2~932~'~
Scheme_ (L - H or F) R~Z:~Z~¢ ~ R~}Zl~}z~co2H
L 3. H20 L

1. R1OH, DMAP
R: = (CH2) n~X; 2. DCC, n = 1-8; if X = CF3, CHF2, CH2F 3 . (COOH) 2 n = 2-8; if X = F, Cl, OCF3, OCHF2 ~ .

R~ZI ~Z~CO2Rl The benzene derivatives of the formula I accord-ing to the invention, in which Q is a ~ingle bond, are obtained in accordance with the following schemes:

Scheme 9 ~L - ~ or F) F 1. BuLi, XOtBu R ~ Z1 ~ z ~ THF, -100 C
2. X~(CH2)n~Y

r Y = Cl, F, CF3, CHF2 R~Z ~}Z~(CH2) r~Y X = I or Br :l = 2-8 - 25 - ~fl~3~2 Sche~e 10 (L = H or F) FLiAlHq F
R ~ Z ~ Z ~ Co2H ~ R ~ Z ~ z ~ CH20H

1. DMS~/NaH F
-- ~ R~Zl~z~cH2-o- (cH2) n-l~Y
2. X~(CH2)n-l~Y L
(x = I or ar) The trifluoroalkyl and -alkanyl ethers of the formula R-~A1-ZI)~-[ ~ ]~-Z-A-o-(cH2)r-(c~=cH)ol-cF3 can be obtained by known etherification methods, for example by reacting 4-substituted phenols with Hal-(CHr)2-(CH=CH)Ol-CF3, where Hal is I, Br or Cl, in acetone and potassium carbonate, optionally in the presence of catalytic amounts of potassium iodide.
The etherification is advantageou~ly carried out in the presence of an inert solvent. Highly ~uitable solvents are, in particular, ethers, such as diethyl ether, di-n-butyl ether, THF, dioxane or anisole, ketones, such as acetone, butanone or cyclohexanone, hydrocarbons, such as benzene, toluene or xylene, or halogenated hydrocarbons, such as tetrachloromethane, dichloromethane or tetrachloroethylene.
The synthesis of the trifluoroal~yl and -alkenyl compounds according to the invention is shown in the following-schemes:

20 ScheD~ ll R-(Al-z~ [ ~ ]5-Z- (A) o~OH
NaOH PPh3/3r2 -NaBr Br-(cH2)r-cF3 ~ HO-(CH2)r-CF3 R-(A1-z1) _[ ~ ]s-z-(A)o-o-(cH2) -CF3 Sche~_12 R--tA~--Z' ) m~ t {~~ ] ~~Z--(A~ o~OH

Br-(Ch2)r-P~Ph3Bre Base Br-(C~2~-CH=C~-CF~ +
~ ~C-CF3 R-(A1-Zl) m~ 1~ ] ~~Z~ (A) o~O~ (CH2)p-CH=CH-CF3 Sche~e 13 R~(Al~ZI)m~[~ O ~]~ ~ L2(L1, L2: H or F) DEAD
PPh3 HO-(CH2) -CF3 R- (Al--zl ) m~ [ ~ ] ~~ (CH2)r--CF3 The compound~ of the formula Ic R-(A;-Z!)~-[ ~ ] Z ~ OCH2CF3 Ic can be obtained from the 4-bromo-2-fluorophenol-(2,2,2-trifluoroethyl) eth r IB, Br ~ OCH2CF3 IB (L = H or F) - 27 _ 2~3~
by the rea~tion of 4-bromo-2-fluoropheno~ide with 2,2,2-trifluoroethyl methylsulfonate in the pre~ence of 1,3-di-methyl-2-imidazolidinone (DMæU), a~ shown in Scheme 14.

ScheD~ 14 (L - ~ or F) Br ~ Na ) Br ~ ~2CF3 L DMEU L
Li/ZnCl2¦R-~A1-Z~) ~ Br ultrasound R-(Al~Zl)m ~ CH2CF3 Sche~ 15 Br ~ H2CF3 + R-~A;-Z-)~-[ ~ ],-Z ~ B~OH)2 F

Na2C03 F
~ R-(A~-Zl)~-[ ~ ],-Z ~ OCH2CF3 Pd-(0~-Cat. L

The liquid-crystalline media according to the $nvention prsferably contain 2 to 40, in particular 4 to 30, components as further constituents besides one or more compounds according to the invention. These media very particularly preferably contain 7 to 25 components besides one or more compounds according to the invention.
These further constituents are preferably selected from - 28 - ~ ~93~
nematic or nematogenic (monotropic or i~otropic) sub-stances, in particular substances from the clas~es of the azoxybenzene~, benzylideneaniline~, biphenyls, ter-phenyls, phenyl or cyclohexyl benzoates, phenyl or cyclohexyl esters of cyclohexanecarboxylic acid, phenyl or cyclohexyl esters of cyclohexylbenzoic acid, phenyl or cyclohexyl esters o cyclohexylcyclohexanecarboxylic acid, cyclohexylphenyl esters of benzoic acid, of cyclo-hexanecarboxylic acid and of cyclohexylcyclohexanecar-boxylic acid, phenylcyclohexane~, cyclohexylbiphenyls,phenylcyclohexylcyclohexanes, cyclohexylcyclohexanes, cyclohexylcyclohexylcyclohexenes, 1,4-bi~-cyclohexyl-benzene3, 4,4'-bis-cyclohexylbiphenyls, phenyl- or cyclohexylpyrimidines, phenyl- or cyclohexylpyridines, phenyl- or cyclohexyldioxane~, phenyl- or cyclohexyl-1,3-dithiane~, 1,2-diphenylethane~, 1,2-dicyclohexylethanes, l-phenyl-2-cyclohexylethanes, 1-cyclohexyl-2-(4-phenyl-cyclohexyl)ethane~, l-cyclohexyl-2-biphenylylethane~, l-phenyl-2-cyclohexylphenylethanesoptionallyhalogenated stilbene~, benzyl phenyl ethers, tolans and substituted cinnamic acids. The 1,4-phenylene groups in these com-pound~ may alJo be fluorinated.
The mo~t important compounds suitable a~ further constituent~ of ~edia according to the invention can be characteri~ed by the formulae l, 2, 3, 4 and 5:

R'-L-E-R~ 1 R'-L-~OO-~-R~ 2 R'-L-OOC-E-R~ 3 R'-L-C~2CH2-E-R~ 4 R'-L-C.C-~-R~ 5 In the formulae 1, 2, 3, 4 and S, L and ~, which may be identical or different, are in each case, inde-pendently of one another, a divalent radical from the group formed by -Phe-, -Cyc-, -Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-, -Pyr-, -Dio-, -G-Phe- and -G-Cyc- and their mirror images, where Phe is unsubstituted or fluorine-2~321~

~ubstituted 1,4-phenylene, Cyc i8 trans-1,4-cyclohexylone or 1,4-cyclohexenylone, Pyr i9 pyrimldino-2,5-diyl or pyridine-2,5-diyl, Dio i9 1,3-dioxane-2,5-diyl and G is 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 ~ i~ preferably Cyc, Ph~ or Pyr E i9 preferably Cye, Ph- or Ph~-Cye The media aeeording to the invention preferably contain on~
or more eomponent~ seleetod from tho eompounds of th~
formulae 1, 2, 3, 4 and 5 in whieh L and E are selectad from the group comprising Cye, Phe and Pyr and ~imul-taneously on0 or more eomponents s~l~et6d from the compound~ of the formula~ 1, 2, 3, 4 and 5 in which one of the radi~als L and E i8 selected from the group comprising Cye, Phe and Pyr and the ~othQr radical i8 seleeted from the group compri~ing -Phe-Phe~, -Phe-Cye-, -Cye-Cye-, -G-Phe- and -G-Cye-, and optionally one or more eomponents sel~etod fro~ tho eo~pound- of tho formul~e 1, 2, 3, 4 and 5 in whieh tho radieal~ L and E
ara seleeted from the group eomprising -Phe-Cyc-, -Cye-Cye-, -G-Phe- and -G-Cye-In a maller sub-group of the eo pound~ of th~
formulao 1, 2, 3, 4 and 5, R' and R" are in each case, indepondently of one another, alkyl, alk~nyl, alkoxy, alkoxyalkyl, zlkenyloxy or alkanoyloxy having up to 8 earbon atomJ Thi~ smaller sub-group is ealled group A
below, and tho eompounds are labelled with tho sub-formulae la, 2a, 3a, 4a and 5~. In most of th~ eom-pounda, R' and R~ are diff~rent from one anothor, one of th-~o radieals usually being alkyl, alkenyl, alkoxy or alkoxyalkyl In another smaller sub-group of the eompounds of the formulae 1, 2, 3, 4 and 5 whieh is known as group ~, R" i~ -F, -Cl, -NCS or -(O)1C~3~ F~Cll, where i is 0 or 1, and k+l is 1, 2 or 3; the eompounds in which R" has this meaning are labelled with the sub-formulae lb, 2b, 3b, 4b and 5b Particular preference is given to those compounds of the sub-formulae lb, 2b, 3b, 4b and 5b in _ 30 _ 20~32~ ~
whioh R" is -F, -Cl, -NCS, -CF3, -OC~F2 or -OCF3.
In the compound~ of the sub-formulae lb, 2b, 3b, 4b and 5b, R' i9 as defined for the compounds of the ~ub-formulae la-5a and is preferably alkyl, alkenyl, alkoxy or alkoxyalkyl.
In a further smaller sub-group of the compounds of the formulae 1, 2, 3, 4 and 5, R" i8 -CN; this sub-group i8 known as group C below, and the compound~ of this sub-group are correspondingly de~cribed by ~ub-formulae lc, 2c, 3c, 4c and Sc. In the compound~ of thesub-formulae lc, 2c, 3c, 4c and 5c, R~ i~ as defined for the compounds of the ~ub-formulae la-5a and i8 preferably alkyl, alkoxy or alkenyl.
In addition to the preferred compounds of groups A, ~ and C, other compounds of the farmul~e 1, 2, 1, 4 and 5 having other variants of the proposed substituents are al~o cuRtomary. All these sub~tances can be obtained by method~ which aro known fro~ the literaturo or analo-gou~ly thereto.
~esides compounds of the formula I according to the invention, the media according to the invention preferably contain one or more compound~ selectod from group A and/or group B and/or group C. The proportions by weight of the compound~ from the~e groups in the ~edia according to the invention are prefer~bly Group A: 0 to 90%, preferably 20 to 90%, in particular 30 to 90%
Group B: 0 to 80%, preferably 10 to 80%, in part.icular 10 to ~5%
Group C: 0 to 80%, preferably 5 to 80%, in particular 5 to 50%, the sum of the proportions by weight of the group A
and/or B and/or C compounds present in the particular media according to the invention preferably being ~ to 90% and in particular 10 to 90%.

- 31 - 2~93~12 Th~ media according to the invention preferably contain 1 to ~0%, particularly preferably 5 to 30%, of compounds according to the invention. Further preferred media are those which contain more than 40%, in parti-cular 45 to 90%, of compounds according to the invention.
The media preferably contain three, four or five com-poundq according to the invention.
The media according to the invention are prepared in a manner which is customary per se. In general, the components are dissolved in one another, expediently at elevated temperature. By means of suit~ble additives, the liquid-cry~talline phase~ can be modified in accordance with the invention in a manner such that they can be u ed in all types of liquid-crystal di~play elements which have hitherto been disclosed. Additives of this type are known to tho~e skilled in the art and are described in detail in the literature (H. KelkertR. Hatz, ~andbook of Liguid Crystals, V~rlag Chemie, Weinheim, 1980). For example, pleochroic dyes can be added for the production of colored gue~t-host systems, or substance3 can be added to modify the dielectric anisotropy, the viscosity and/or the orientation of the nematic phases.
The examples below are intendet to illustrate the invention without representing a l;m;ta~ion. "C~tomary work-up" means that water i8 added, the mixture i3 extracted with methylene chloride, the organic phase i~
separated off, dried and evaporated, and the product is purified by crystallization and/or chromatography. Above and below, per cent data are per cent by weight. All temperature3 are given in degrees Celsius. m.p. is melting point and c.p. ~ clearing point. Furthermore, C - cry~talline state, N - nematic pha~e, S - smectic phase and I - i~otropic phase. The data between the~e symbol~ indicate the tran~ition temperatures. ~n is optical anisotropy (589 nm, 20C). The vi~cosity ~mm2/sec) wa~ determined at 20C.
The following abbreviations are used:

~93~

BuLi butyllithium DAST diethylaminosulfur trifluoride DCC dicyclohexylcarbodiimide DIBALH diisobutylaluminum hydride 5 DMAP 2-dimethylaminopyridine DDQ dichlorodicyanobenzoquinone POT potas~ium tertiary butoxide NH4Cl ammonium chlorido T~F tetrahydrofuran 10 TMæDA tetramothylethylenediamine pTSOH p-toluenesulfonic acid E~ple 1 F

a) H,C3 ~ -OH

26 mmol of n-BuLi are added dropwi~e nt -100C to a mixture comprising 26 mmol of 1-trans-4-(trans-4-n-pro-pylcyclohexyl)-cyclohexyl-3-fluorobenzene (prepared as described in scheme 1), 4.1 g of pota~sium tert.-butoxide and 60 ml of THF. After the ~ixture ha- been stirrod at -100C for one hour, 36 m~ol of trimethyl borate are added dropwiso at from -85 to -90C. The mixture is stirred for a further O.5 hour, and 42 mmol of acatic acid are thon added dropwis- at -20C. The mixture i9 sub-oquontly warmed to 30C, and 4.2 ml Of ~22 are added dropwi~e at this temperature, and the mixture i~ stirred at from 50 to 60C for 2 hour~. The mixture is allowed to cool to room temperature, and a 5% ~odium dithione solution is added. Phase separation and conventional work-up give the phenol.

b) H7C3 ~--OCH3 - 33 - 2~3212 The phenol obtained is reacted with methyl iodide in acetone under reflux in the pre~ence of pota~3~3ium carbonate to give the methyl ether. Conventional work-up and chromatography on ~ilica gel using hexane give the ether in pure form.
The following ethers of the formula R ~ Zl ~ Z ~ OCH3 are prepared analogously.

R ~ z~ ~ z_ CH3 ~
C2H5 ~_ n-C5HI ~ ~
CH30CH2 _~_ CH2~CHCH2CH2 ~
CH3 ~ H2CH2-CzHs ~}CH2CH2-n-C3H~ ~H2cH2_ n--CsHll ~CHzCH2-CH~OCH2 ~ CH2CH2-CH2--CHCH2CH2 ~ H2CH2-CH3 ~ H2CH2 ~
C2E{5 -~-CH2CH2 n--C3H7 ~CH2CH
n-CsHll ~CH2CH2~
CH30CH2 ~ CH2CH2 ~ }
CH2~CHCH2CH2 ~ CH2CY.

20~321~

R {~ Z ~} Z -_ _ CH3 ~ (CH2) C2 H5 ~ ( Cf~
n-C3H7 ~ (CH2) n~sHIl ~ (CH2) c~{3oCH2 ~ ~CH2) CH2-CHCH2CH2 ~ tCH2) ,~
Bxa~ 2 F

a) C3H7 ~ -OC~2C~2CH~

The fluorophenol prepared in` Example 1 a) i8 reacted with l-chloro-3-fluoropropane in boiling acetone S in the presenca of potas~ium carbonate and a catalytic amount of pota~ium iodlde to give the phenol ether.
Conventional work-up and chromatography on ~ilica gel u~ing hexane gives the ether in pure form.
F

b) C3H7 ~ H2CH2CH2Cl The fluorophenol prepared in Exzmple 1 a) i8 converted to the phenol ether using l-chloro-3-iodopro-pane ~nalogou~ly to ~xample 2 a).
The following compounds of the formula F

R ~ Zl ~ Z ~ H2CH2cH2Y

according to the invention are obtained analogously from the corresponding precur~ors:

_ 35 _ 2~

R ~Z: ~Z Y

CH3 ~1~ C:
C2H5 ~ F
C2Hs ~ C' n-C~ H3 ~ F
n--C4H3 ~ Cl n-C5HIl ~ F
n-CsHl ~ } Cl CH30CH2 -(~-- F
CH30CH2 ~ C ' CH25CEICH2CH2 ~ F
CHz-CHC~2~1z ~ Cl CH3 ~CH2CH2~ F
CH3 - ~CH2CH2~ Cl C2Hs _~CH2CH2~ F
C2H5 - (~'CH2C~12~ Cl n-C3H7 ~CH2CH2~ F
n-C3H7 {~CH2CH2~ Cl n--C4H9 ~ {~ H2CH2~ F
n-C~H~ {~CH2cH2~ Cl n--C:sHl 1 ~CH2CH2~ F
n-CsHIl ~CH2CH2~ Cl CH30CH2 ~CH2CH2{~ F
CH3OCH2 ~CH~CY~-(~ ^l CH2-CHCH2CH2 ~CEI2CH ~
CH~=CHCH2CH2 ~CH~CH~-~} C!

- 36 - ~0~12 Xx~

a) 8-C3~7 ~ ~

Two drop~ of bromine are added to a solution of 6.0 ~ of mAgnesium turning- in 60 ml of ether. A ~olution S of 48.2 g of 3,5-difluorobromobsnsQne in 60 ml of ether i9 sub~equently added dropwis~. The mixture i8 ~tirred for a further 0.5 hour, and a ~olution of 4~.5 g of 4-trans-~4-propylcyclohexyl)cyclohexanone in 50 ml of ether i8 then added dropwise to ths Grign~rd re~gent at 20-25C. The mixture i~ stirred for ~ further two hourY, poured into 500 ml of water, acidified~by mean~ of 30 ml of conc. hydrochloric acid and extract~d by sh~king with ether. ~he organic phase i8 evaporated to give a residue and ub~equ~ntly ref lux-d for 1 hour with 1,000 ~1 o~
toluene and 120 ml of 20% sulfuric ~cid.
Af ter phase ~ep~ration and neutralization by mean~ of saturated sodium bicarbonate 801ut~on ~ the product i8 hydrogenated at 1 bar and 609C u~ing 10 g of Pd/C (5%). Tho mixture i8 ub~equently filtered and evaporated. Flash chro~atography gives th~ purs product.
C 60 N 87.6 I, ~ - 3.3 F

b ~ C3 H, ~-OH

31 ml of n-BuLi (15% in hexane) are added drop-wise at from -65C to -70C to a mixture of 47 mmol of 4-,trans-(4-n-propylcyclohexyl)cyclohexyl-1-trans-(3,5-di-fluorobenzene), 50 mmol of TMEDA and 150 ml of T~F, and the mixture is ~tirred at -70C for a further hour. Then, 57 mmol of trimethyl borate are added dropwise at from -85 to -90C, followed by 65 mmol of acetic acid at -20C.

2 0 9 ~ 2 ~ ~

c ) C~H,~-OCH2CH2CH2F' The dif luorophenol is r~acted analogouQly to Example 2 a) with 1-chloro-3-fluoropropane to give the phenol ether.
F

d) C3H7 ~ ~2CH2CH2Cl Tha difluorophenol prepared in ~xample 4 b~ i9 reacted analogously to Example 2 b) with 1-chloro-3-iodo-propane. C 50 N 157.2 I, Q t ~ 5 . 7 -1~D1~ ~
F

a) C3H7 ~ H2CHlF

1 mmol of diethyl azodicarboxyl~te i3 addeddropwi~e at 0-10C to a solution comprising 1 mmol of 4-tran~-(4-n-propylcyclohexyl)cyclohe~yl-1-tran~-(3,5-di-fluorophenol), 1 mmol of triphenylpho2phine, 1 mmol of 2-fluoroothanol and 25 ml of T~F. The mixture i~ ~ubse-quently stirred at room temperature for a further hour and then 8ubjected to customary work-up. C 82 N 165.5 I, ac - 2.07.
F
b) C3H7 ~ ~3 F

1 mmol of 4-trans-(4-n-propylcyclohexyl)cyclo-hexyl-l-trans-(3,5-difluorophenol) i8 reacted with - 38 - 2 ~ 321 2 methanol ~nalogously to Example 4 a). C 41 N 151.8 I, 0.038.
The following compounds of the formula R ~ Z~- ~ Z ~ O-~CH2)~-Y:

according to tho invontion are obtained analogously from the corre~ponding pr~cur-or-:
R ~ Z~ ~ Z- n Y

CH3 ~ 1 H
CH3 ~r~ 1 F
CH3 ~ 1 `Cl CH3 ~ 2 F
CH3 ~ 2 Cl CH3 ~ 3 F
CH3 ~ 3 Cl CH3 .~ 4 F
CH3 ~ 4 Cl CH3 ~ 5 F
CH3 ~ 5 Cl C2H~ ~ 1 F
C2Hs ~ 1 Cl C2H5 ~r 2 F
C2Hs ~} 2 Cl C2Hs {~ 3 F
C2H5 ~ 3 Cl C2H5 {~ 4 F
C2H5 ~} 4 Cl C2Hs ~ 5 F
C2Hs ~ 5 Cl C3H7 ~r~ l :~ c 41 ~ ;~ , 3 39- 7~i332~

R ~2~ {~Z- n Y

n-C3H7 ~ 1 F
n--C3H7 {~ 1 Cl n-C3H~ ~ 2 Cl n~:3H7 ~ 2 F C 82 N 165. 5 I
n-C3H? ~} Cl n~C3H7 ~ 4 F
n-C3H7 ~ 4 Cl n-C3H7 ~ 5 F
n-C3H7 ~ 5 Cl~
n-C4Hg ~ 2 F
n-C~H9 ~ 2 Cl n-C~Hg ~ 3 F
n-(C~Hg ~ 3 Cl n-CsHll ~ 1 H C 43 N 154, 3 I
n-CsHl~ ~ 1 F
n-C5Hl. ~ 1 Cl n-C:5HIl ~ 2 F
n-C5Hll ~ 2 Cl n-C5Hll ~ F
n-CsHll ~ Cl n-CsHll {~ F
n-(C5Hll ~ Cl n-CsHll ~ F
n-CsH~ ~ S Cl ~ 40 ~ 2093212 R ~ Z:- ~ z- n Y

. ~
CH30CH2 ~ 2 F
CH30C.~l2 ~ 2 Cl CH30CH~ ~ 3 F
CH3 OCH2 ~ 3 C 1 CH2-CHCH2cH2 ~ 2 F
CH2=CHCH2CH2 ~} 2 Cl CH2=CHCH2CH2 ~ 3 F
CH2=CHCH2CH2 ~ 3 Cl e 5 a ) Cs Hm ~CH=CH~
F
78 m~ol of potassium tert.-butoxidQ, di~solved in 80 ml of THF, are added dropwise at -S-C to 78 mmol of 1-(4-(4-n-pentylcyclohexyl)cyclohe~yl)methylenetriphenyl-phosphonium iodide and 78 mmol of 3,5-difluorobenz-aldehyde, dissolved in 50 ml of THF. The mixture i8 sub-gequently stirred at the same temperature for lS minutes and at room temperature for a further 1.5 hour~. The reaction mixture is hydrolysed, neutrali~ed by means of hydrochloric acid and subsequently sub~ected to customary work-up.
F

b) CsH~ ~ CH=CH- ~ OCH2CH2CH2F

The product prepared in Example S a) i8 reacted with 1-chloro-3-fluoropropane analogou~ly to Example 3 c) to give the phenol ether.

F 20932~2 n-CsHm {~)~CH=CH~OCH2CH2CH2Cl The product prepared in Example S a) is reacted with l-chloro-3-iodopropane analogously to Ex~mple 3 d) to give the phenol ether.
The following compounds of the formula R ~ Zl ~ Z ~ -oc82cH2cH2y according to the invention are obtainsd analogously from the corresponding precursors of the formula II (L - F):
R ~ Zl ~ z_ Y

CH3 ~ H=CH- F
CH3 ~ H=CH- Cl C2H5 ~ H-CH- F
CzH5 ~ -CH- Cl n-C3H~ ~ ~ CH=CH- F
n-C3H7 ~ ~ CH--CH- Cl n-C~Hg ~ ~ CH=CH- F
n-C~Hg ~ ~ =CH- Cl CR30CHz ~ H=CH- F
CH30CH2 ~ H=CH- Cl CH2-CHCH2CH2 ~ CH=CH- F
CH2-CHCH2CH2 ~ CH=CH- Cl ~ aL~ 6 a) n-C5H~l ~ ~ CH2CH

- 42 - ~ ~ ~3212 9 mmol of the product from Example 5 a) are dissolved in 30 ml of THF, 0.3 g of 4% Pd-C i8 added, and the mixture i9 hydrogenated. The cataly~t is subsequently filtered off, and the filtrate i~ evaporated in Yacuo to give a residue. This i9 chromatographed on a silica gel column using pentane.
An analogQus reaction gives n-C3H7 ~ CH2C.~2- ~ , C 52 N 9S.1 I, a 6 ~ 4.7.

b) n--C5~ ~ ~ C~2CH2 ~ 2CH2Ci2F

The product obtained in ~xample 6 a) is reacted with l-chloro-3-fluoropropane an~logously to gxaople 3 c).

C) r~-csE~ 2cH2~~ CH C~ Cl ~ ho product prepared in Example 6 al i~
reacted with 1-chloro-3-iodopropane analogously to Example 3 d) to give the phenol ethcr.
The following compounds of tha formula R ~ ~ -ocH2cH2cH2y F

are obtained analogously from the corre~ponding precur-~ors of the formula II (L ~ F):

43 ~93212 R ~ZI ~Z Y

.
CH3 ~ CU2C 2- F
C~3 ~~C~2C 2 C1 C2H5 ~ C12CH2- F
C2H5 _~-C~2CK2- C1 n C3H7 ~CH2CH2- F
n-C3H~ ~CH2CH2- C1 n-C4H9 -<~CH2CH2- F
n--C~H9 -~-<~CH2CH2- C1 CH30CH2 ~CH2CH2- F
CH30CH2 _~ - CH2CH2 - C1 CH2=~CHCH2CH2 {~CH2CH2- F
CH2 CHC~2CH2 {~GCH2CH2- C1 ~1~ 7 F F
a) CsH~CH2) 4-8r + 3r-(~ ~CsHIl~(CH2) 4-<~
F F
ll.S g of anhydrou~ zinc bromide and th~n 1.4 g of lithium granules are added to 0.1 mol of 4-(4-(n-pen-tylcyclohexyl)cyclohexylbutyl bromide in 150 ml of a ~olvent mixture compri~ing T~F/toluene tl:4). The mixture i8 treated with ultrasound for 4 hours at between 0C and 10C under argon and with stirring. The organozinc compound produced i9 treated with 0.1 mol of 3,5-di-fluoro-l-dibromobenzene and 2 mol~ of l,l'-bi~(diphenyl-phosphino)ferrocenepalladium(II) dichloride, the ultra-~ound bath and the cooling are removed, and the mixture is ~tirred at room temperature for 24 hour~. 100 ml of ~ 44 ~ 22~321~
saturated N~,Cl solution are added with stirrin~, the organic phase is separated off, and the aqueous phase i9 extracted with toluene. The combined organic extracts are dried, evaporated and chromatographed on 8ilica gel.

b) C;~m ~ ~ (CH2)~ ~ -OH

The reaction of the difluorobenzen~ with ~uLi and trimethyl borate to give the difluorophenol i8 carried out analogou ly to Example 1.

c) CsHIl~ (cH2) 4~-OCHzCH2C~2F

Th~ difluorophonol from ~x3mpl~ 7 b~ is re~cted with l-chloro-3-fluoropropane analogously to Example 3 c) to give the phenol ether.

d) C~HIl ~ (CHz) ~-OCH2CH~CH2Cl The product fro~ Exa~plo 7 ~ reacted with l-chloro-3-iodopropane analogouJly to Exa~ple 3 d).
The following compound~ of the formula R~zl:~z-~cHzcH2cH2y:
L

according to the invention are obtained analogously from the corresponding precur~or~ of the formula II (L - ~ or F) ~ 45 ~ 2~93212 R ~Zl~Z- L Y

.
CH3 ~(CH2)~ H F
CH3 ~ (CH2) 4~ H Cl CH3 ~ (CH2) ~ F Cl c2~s ~ (CH2~ 4~ H F
C2H5 ~--~CH2) 4~ F F
n~3H7 ~ (CH2) 4-(~ H F
n~3H7 ~ (CH2) ~ H Cl n C3H7 ~ (CH2) 4~ F Cl n~Hg ~ (CH2) q~ F F
n--CjHg ~ (CH2) ~ ~ F Cl n--CsH 1 ~(CH2)q~ H F
n-CSH ' ~ (CH2 ) 4~ F F
n-CSH i ~--(cH2)4{~ F Cl CH3OCH2 ~ (CH2) 4~ H F
CH30CH2 ~ (cli2) q~3~ F F
CH2=cHcH2cH2 ~ (CH2) q~ H F
CH2=CHCH2cH2 ~ (CH2) q~ F F
CH2=CHCH2CH2 ~ (CH2) 4-<~ F Cl 13~1~ 8 n-CsHI1 ~ < ~ COOCH2CH2F

26 ml of 2-fluoroethanol and 0.1 g of DMAP are added to a suspension of 26 mmol of 4-trans-(4-pentyl-cyclohexyl)cyclohexyl-l-trans-3,5-difluorobenzoic acid S (prepared as described in scheme 7) in 160 ml of di-chloromethane. A solution of 6.6 g of DCC in 40 ml of dichloromethAno i~ then added dropwise with stirring. The - 46 - ~093212 mixture i9 stirred overnight at room temperature. Oxalic acid is added, the mixture is stirred for a further hour, chromatographed using hexane and recrystallised. C 63 N
148.8 I
S The following compounds of the formula:

~ ~ -COOR' are obtained an~logou31y:
R L R' C2H5 H CH2CHiF
n~3H7 ~ CH2CH2F
n-C~H~ H CH2CH2F
n-CsH~l H CH2CH2F

CH2=CHCH2CH2 H CH2CH2F
CHI F C~2CH2F

n-C3H~ F CH2CH2F
n-C4H9 F CH2CH2F

CH2~CHCH2CHz F CH2CH2F
CH3 F CH2CH2Cl C2H5 F CH2CH2Cl n.-C3H7 F CH2CH2Cl n-CsH1~ F CH2CH2Cl CH30CH2 F CH2CH2Cl 2(J932~2 R L R' CH3 F CH2CH2CH2Cl C2H5 F CH2CH2CH2Cl n-C3H, F CH2CH2CH2Cl n-C5H:i F CH2CH2CH2Cl C 58 N 102 I
CH3OCH2 F CH2CH2CH2Cl CH2=CHCH2CH2 F CH2CH2CH2Cl C2H5 F CH2cH2cH2cF3 n-C3H, F CH2CH2CH2CF3 n--CsH ~ F CH2CH2CI~2CF3 C 65 N 86. 9 I
CH3ocH2 F CH2CH2CH2CF3 CH2=CHCH2CH2 F CH2CH2CH2CF3 C2~5 F CH2CH2OCF3 n-C3H~ F CH2CH20CF3 n-c5H-~ 1 F CH2CH2OCF3 CH3ocH2 F CHzCH2OCF3 CH2=CHCH2CH2 F CH2CH20CF3 C2Hs F CH2CH2CHF2 n-C3H7 F CH2CH2CHF2 n-CsHll F CH2cH2cHF2 CH3ocH2 F CH2CH2CHF2 ~9~

~2 n~CsHm ~2 H ~ n-CsHIs ~ CHzOH

F A
n-C,HII m~CH20CH2CH2CH2Cl - B F
A suspension of 50 mmol of 4-tranY-(4-pentyl-cyclohexyl)cyclohexyl-l-tran~-3,5-~difluorobenzoic acid) in 150 ml of THF i8 added dropwise to a suspension o S S0 mmol of lithium aluminum hydrids in 50 ml of T~P. The mixture is subsequently refluxed for a further 1 hour with stirring. The mixture i~ cooled i~n an ice bath and hydrolysed by addition of 6 ml of 10% NaHC03 solution.
12 ml of 20% sodium hydroxide solution are added, and the organi~ ph~se i~ soparated off, dried and ~vaporated.
A ~olution of 28 mmol of the difluorobenzyl alcohol A in 90 ml of ~HF is added to a 301ution of 30 mmol of sodium hydrid~ in 30 ml of DMS0. 31 mmol of 3-chloro-1-iodopropane are then added, and the mixture i8 stirred overnight at 50C. Hydroly~is and conventional work-up give the ether B.
The following compounds of the formula -R~{ ~H20 (CH2 ) n~Y:

are obtained analogously:

_ 49 _ 2~93212 R L n Y

C2Hs H 2 Cl C2Hs H 3 Cl C2H5 F 2 Cl C2H5 F 3 Cl C2Hs H 2 F
CzHs H 3 F
C2Hj F 2 r C2Hs F 3 F' C2Hs H 2 CF3 C2Hs F 3 CF3 n-C3H7 H 2 F
n-C3H7 F 2 F
n~C3~ H 2 Cl n-C3H~ F 2 Cl n-C3H7 H 2 OCF3 n-C3H7 F 2 OCF3 n-c3H7 H 2 CHF2 n--C3H7 F 2 CHF2 n-C3H7 H 2 CF3 n-C3H7 F 2 CF3 - 50 ~ 3 '~ ~ 2 R L n Y

n~sHI I H 2 Cl n~sHIl H 2 F
n-CsH~ ~ F 2 F
n~5Hl ~ H 2 CF3 n~sHm F 2 CF3 n~jH~l ~ 3 F
n-C5HI ~ F 3 Cl n~,HI 1 F 3 CF;

~sapç~Le lQ

H7C3~0-C~2CH2CH2CF3 14.5 g (0.065 mol) of 4-(4-propylcyclohexyl)-cyclohexanol are di~solved in 15 ml of T~F, and 12.; g (0.065 mol) of trifluorobutyl bromide, 1.~ g of cetyl-trLmethyl~mmonium bromlde, 5.2 g (0.13 mol) of ~odium hydroxide solution and 0.3 ml of water are added ~ucce~-~ively. The mixture i~ stirred overnight at 70C. The mixture i~ sub~equently allowed to cool to room tempera-ture and i~ taken up in diethyl ether. Conventionalextractive work-up qive~ the ~ther, which i~ purified by chromatography on ~ilica gel (hexane:ethyl acetate -9:1). C 10 S~ 47 I.
The following trifluoroalkyl ether~ of the formula R-[ ~ l.-Z ~ ~CH2)r-CF, are prepared analogou~ly:

1 - 2~32 ~ 2 R ~ z ~ -o-~CH2),-CF~

C2H5 _~ ~ OCH2CH2CF~
n-C3H, ~ OCH2CHzCE'3 n-C5~l. ~} C)CH2CH2CF, CH3C~2 _< ~ 3,, OCH2CH2CF, CH2--CH CHaCH2 ~ OCH2CH2CF~
C2~5 ~ OCH2CH2C~aCF3 n-C~H~ ~ OC~zCH2CH2CF3 n-cs~ ~, OCH2CH2CR2CF~
CH30C~ ~ OCH2CHzC~2CF3 C~2 = CH CHaC~2 ~ OCH2C~2C~2CF3 C2H5 ~ cH2cR2c~2c~I2cF3 n-C3H7 ~ OCH2C~2C~2CR2CF3 n-C5Hll. ~ OCH2CH2CH2C~12CF~
CH30a~2 _< ~ , OCR2CH2CH2CH2CF3 CH2--CH CH2CH2 ~ OCX2CH2CH,CH2CF3 ~a~yle 11 Br-~CH2)2-P-Ph38re + C-CF3 3r-CH2-CH-CH-C~3 11.5 g of potassium tert.-butoxide are added in portions at 0-10C to a ~uspen~ion of 0.1 mol of Wittig salt in 200 ml of THF. Trifluoroacetald~hyde gas is subseguently pas~ed in at the 8amo temperature until the orange ylide suspension has become colourless. The mixture i8 subsequently stirred at room temperature for 24 hours, poured into water, neutralised and extracted a nu~ber of times with toluene, and the toluene extract is dried, evaporated and filtered on silica gel using hexane.

52 - ~ ~93~

C;H~- ~ ~ ~CH2CH=CH~

0.065 mol of 4-(4-propylcyclohexyl)cyclohexanol~
15 ml of THF, 0.065 mol of 1,1,1-trifluoro-4-bromobut-2-ene, 1.2 g of cetyltrimethylammonium bromide, 0.13 mol of sodium hydroxide solution and 0~3 ml of water are S reacted analoqously to ~x~mple 1.
The following trifluoroalkenyl ether~ of the fonmula R-t ~ -],-Z ~ -O-(CH2) -CH~H-CF3 are prepared analogou~ly:

R _~ ~ ] J_Z_~ - O - (CH2 ) r -CH=CH-CF3 _. _ CzH5 ~ OCH2CH = CHCF3 n-C~H9 ~ OCH2CH = CHCF3 n-CsHll ~ OCH2CH = CHCF3 CH30CH2 ~ ~ OCH2CH = CHCF3 CH2 = CHCH2CH2 ~ OCH2CH = CHCF3 CzHs ~ ~ OCH~C:-~CH = CHC-3 n-C~H7 ~ CCH~C:i~CH = CHC~ 3 n~CsHII - ~ OCH~CHaCH = CHCr 3 CH30CH2 ~-- CCH2--H~CH = CHCFl CH2 ~ CHCH2CH2 ~ CCH~CH~CH = CHC~3 ~ample 12 CsH~ 0-(CHz)3-CF3 0.102 mol of diethyl azodicarboxylate i~ added dropwise with cooling to 0.1 mol of 4-(4-pentylcyclohex-~ 53 ~ 2~93212 yl)phenol, 0.102 mol of triphenylphosphine and 0.1 mol oftrifluorohutan-4-ol in 250 ml of tetrahydrofuran at room temperature. The mixture i~ subsequently stirred over-night. The mixture is evaporated and the residue is S filtered on silica gel using toluene.
The following trifluoroalkyl ethers of the formula - R-[ ~ ~-Z-(A)o-O-(CH2),-CF3 are prepared analogoUsly:

- 54 - 2~3212 R
- t O-) ,-2- (~) J- - (CH2) _r~ 3 C2H5 ~ ~

n-C5H,~ OCH2CF3 C 50 I

CH30CH2 ~ OC~2CF3 C~2 ~ CHcH2cH2 J~3_ OCH2CF, C2H5 ~ OcH2cH2cF3 n-C3H~ ~ OCH2CH2CF3 n-CsH~ _ OCH2CH2CF3 CH30CH2 _~3_ OCH2CH2Cr 3 C~l2 ' C~IcH2cH2 ~} OcH2cH2cF3 --C3~ _~F OcH2cH2cF3 FF

n--C5H~ OcH2cH2cF3 C2H5 _~,F OCH2CH2CH~CF3 C 50 I

n-C3H7 ~ OCH2CH2C~12CF3 n-C~H9 ~ OCH2CH2CH2CF3 CH30(CH2 -~- 0cH2c~2c~l2cF3 C~2 ' CHCH2CH2 _<~_ OCH2CH2CH~CF3 n~H~ ~ OCH2CH2CH2CF3 n~CSHl 1 _~;_ OCH2CH2CH2Cr 3 - 55 - ~ 3212 R[ {} ~ ,-Z- (A): - -O- (CH2 ) -CF3 C2Hs ~ OCH2CH2CH2CH2CF3 n-C3H7 -~ OCH2CH2CH2CH~CF, n-CsH~l (~ OCH2CH2CH2CH2CF3 CH3OCH2 ~<~ OCH2CH2CH2CH2CF3 CH2 = CHcH2cH2 ~ OCH2CH2CH2CH2CF3 n-C3H7 ~ OCH2CH2CH2CH2CF3 n-CsHll ~ F OCH2CH2CH2CH2CF3 C2Hs ~ } OCH2CF3 n-C3H7 ~ OCH2CF3 n-CsHll ~ OCH2CF3 C 10,7 I
CH3OCH2 ~ } OCH2CF3 CH2 = CHcH2cH2 ~ OCH2CF3 CH3CH20~}~} OCH2CF3 CH3CH2CH2CH20 ~ OCH2CF3 n-C3H7 -~ OCH2CF3 F

n-CsH~ OCH2CF3 - 56 - 2~932 ~ 2 R ~ -Z- (A) ~- -O- (CH2 ) r-CF7 _ _ _ C2H5 -@--<~ OCH2CH2CF3 n-C3H. ~} CCH2CH2CF3 n-CsHl ~ } OCH2CH2CF3 CH3OCH2 ~} OCH2CH2CF3 CH2 = CHcH2cH2 -~ } OCH2CH2CF, CH3CH20 ~} OCH2CH2CF3 CH3CH2CH2CH20 ~ OCH2CH2CF3 n-c3H7 F OCH2CH2CF3 n-CsH~ , OCH2CH2CF3 C2H5 ~ OCH2CH2CH2CF3 n-C3H7 ~}<~ OCH2CH2CH2CFj n-CsHll ~<~ OCH2CH2CH2CF3 CH3OCH2 ~<~ OCH2CH2CH2CF3 CH2 = CHcH2cH2 ~ OCH2CH2CH2CF3 CH3CH20 ~ OCH2CH2CH2CF3 CH3CH2CH2CH20 ~ OCEI2CH2CH2CF3 n-C3H7 -<~ OCH2CH2CH2CF3 FF

n-CsH~ OCH2CH2CH2CF3 ~932~2 R_ _~] ,-Z- (A) ~- -O- (CH2) -CF~
C2H~ ~ OcH2cH2cH2c~2cF3 n-C3H, -/~@- CCHzCH2CH2C.~ F3 n-C5H~; -~ OCH2CH2CH2CH2CF3 CH3OCH2(~(~} OCH2CH2CH2CH2CF3 CH2 - CHCH2CH2 ~}~ OcH2cH2cH2cH2cF3 CH3CH20 ~ OCH2CH2CH2CH2CF3 CH3CH2CH2CH20 ~} OCH2CH2CH2CH2CF3 n-C3H7 ~ OCH2CH2CH2CH2CF3 F
n-CsHll ~ OCH2CH,CH2al2CF3 C2Hs ~}<~ OCH2CF3 n-C3H7 -<~(~ OCH2CF3 K ' 00 ~3170 SA: 3~;
n-CsHl i(~(~} OCH2CF3 CH3OCH2 3(~ OCH2CF3 CH2 S CHCH2CH2 ~<~} OCH2CF3 - 58 - ~ 3 ~ ~ 2 R - [-~] ,-Z- (A) ,- -O- ~CH2) ~-CF3 C2 H5 _~H2CH2CF, .l-C3H~ OCH2CH2CF3 n-C5H~ } OCH2CH2CF3 CH3OCH2~} OCH2CH2CF3 CH2 = CHcH2cH2 ~}~ OCHzCH2CF3 n-C3H~ ~ OCH2CH2CF3 CH2 = CHCH2CH2 -~ OCH2CH2CF3 c2H5 G ~ ocH~cH2cH2cF3 n-C3H7~~<~ OCH2CH2CH2CF3 n-CsHl: <~ OCH2CH2CH2CF3 CH3OCH2~<~ } OCH2CH2CH2CF3 CH2 - CHCH2CH2 ~OE~ OCH2CH2CH2CF3 n-C3H~ -~ OCH2CH2CH2CF3 n-CsHll ~ OCH2CH2CH2CF3 2~93~

R - [ -~ ], -Z- (A) ,- -O- ~CHz ) ,-CF;
. .
C2Hs ~} OCH2CH2CH2CH2CF3 n-C3H, -~(~ OCH2CH2CH2CH2CF3 n-CsH:: ~}<~} OCH2CH2C~2CH2CF3 CH3OCH2 ~<~} OCH2CHzCH2CH2CF3 CH2 = CHCH2CH2 ~ OCH2CH2CH2CH2CF3 n-C3H, ~ OCH2CH2CH2CH2CF3 F
n-C3H7 ~ QCH2CH2CH2CH2CF3 n-C5H~ OCX2CH2CH2CH2CF3 n-CsHl 1 ~}~ OCH2CH2CH2CH2CF3 C2H5 <~}(~ OCH2CF3 n-C3H7 ~ OCH2CF3 n-CsHl 1 ~ OCH2CF3 CH3OCH2 ~}<~ OCH2CF3 CH2 ~ CHCH2CH2 ~}~} OCH2CF3 - 60 ~ 3212 - ~ -a I g-Z- (A) - -O- ~CH2) ,-CF3 n-C ~ } OCH~CH2CF3 n-C,H; ~~ OCH2CH2CF3 CH30CH2 ~} OCH2CH2CF, CH2 = CHcH2cH2 ~ OCH2CH2CF3 n-C3H~ {~ OCH2CH2CF3 n-C;Hl 1~~<~~ OCH2CH2CF3 C2Hs ~_ OCH2CH2CH2CF3 n-C3H7 ~ OCH2CH2CH2CF3 n-CsHIl ~ OCH2CH2CH2CF3 CH3OCH2 ~ OCH2CH2CH2CF3 CH2 S CHcH2cH2 ~ OCH2CH2CH2CF3 n-C3H~ ~ OCH2CH2CH2CF3 n-CsHll ~ F OCH2CH2CH2CF3 F K 61 S3~56) N 145,2 I, ~n - O, 096 CH3OCH2 ~ OCH2CH2CH2CF3 2~3~

R ~ Z- (A) - -O- (CH2) -CFl n-C3H, ~<~ OCH2CH,CH2CH,CF3 n-CsH ~ OCH2CHzCH2CH2CF3 CH3OCH2 ~ OCH2CH2CH2CH2CF3 CH2 = CHcH2cH2 ~ } OCH2CH2CH2CH2CF3 F

n-C3H7 ~ OCH2CH~CH2CH2CF3 C2Hs -<~CH2CH2~ OCH2CF3 n-C3H~ ~CH2CH2~ OCH2CF3 n-CsHIl -~CH2CH2~ OCH2CF3 x 66 Sg 166 CH3OCH2 ~H2CH2~ OCH2CF3 CH2 = CHcH2cH2 -~CH2CH2~ OCH2CF3 C2Hs ~CH2CH2~ OcH2cF3 FF

n-C3H7 ~H2CH2~ OCH2CF3 n-C3H7 ~}CH2CH2~ OCH2CF3 C2Hs ~}CH2CH2~ OCH2CH2CF3 n-C3H7 ~CH2CH2~ OCH2CH2CF3 n-CsHll ~}CH2CH2~ OCH2CH2CF3 CH3OCH2~CH2CH2-~ OCH2CH2CF3 - 62 - ~932 R - [-O-j ,-Z- (A) - -O- (CH2) -CF3 CH2 = CHcH2cH2 ~ cH2cH2 ~ OCH~CH2CF3 n-CsHIl ~CH2CH2~ OCH2CH2CF3 CH3OCH2CH2 ~CR2CH2~ OCH2CH2CF3 C2Hs ~ CH2CH2~ OCH2CH2CH2CF3 n-C3H7 ~CH2CH2-(~} OCH2CH2CH2CF3 n-CsHll ~CH2CH2-<~} OCH2CH2CH2CF3 CH3OCH2 ~CH2CH2-<~} OCH2CH2CH2CF3 CH2 = CHCH2CH2 ~ }CH2CH2-(~ OCH2CH2CH2CF3 CH2 ~ CHcH2cH2 ~CH2CH2~ OCH2CH2CH2CF3 FF

n ~3H7~ -CH2CH2 ~ OCH2CH2CH2CF3 F

C2Hs~-CH2CH2~} OCH2CH2CH2CH2CF3 n-C3H7~CH2CH2~} OCH2CH2CH2CH2CF3 n~Cs~ CH2CH2~ OCH2CH2CH2CH2CF3 CH3OCH2~CH2CH2-<~} OCHzCH2CH2CH2CF3 CH2 =CHcH2cH2 -<~CH2CH2~ OCHzCH2CH2CH2CF3 - 63 ~ 32~2 R -[{)-],-2-(A) - -O-(CH2)r-CF3 --n-C3H~~CH2CH ~ )CH2CH2CH2CH2CF3 n-C5Hll~CH2CH2~ OCH2CH2CH2CH2CF3 n-CsHIl~CH2C~{2~ OCH2CH2CH2CH2CF3 C2Hs~}(CH2)4~ OCH2CF3 n-C3H7~ ~cH2) 4~} OCH2CF3 n-CsHll~ (CH2~ 4~} OCH2CF3 CH30CH2~ (CH2) 4~ OCH2CF3 CH2 = CHCH2CH2 ~} ~CH2) 4~ OCH2CF3 n-C3H7~} ~CH2) 4~- OCH2CF3 F
n-CsH~CH2) 4~ OCH2CF3 C2H5~ (CH2) 4~} OCH2CH2CF3 n-C3H7 - ~ (CH2) 4~} OCH2CH2CF3 n-CsHll ~ ~CH2) 4~} OCH2CH2CF3 CH3OCH2 {~ ~CH2) 4~} OCH2CH2CF3 CH2 = CHCH~CH2 ~ ~C~2 ) 4~} OCH2CH2CF3 CH3OCH2CH2 ~} (CH2) 4~ OCH2CH2CF3 F

- 64 ~ 93212 R - [ ~ ' ,-Z- (A) - -O- (CH2 ) .-CF3 C2Hs ~} (cH2) 4~ OCH~CH2CH2CFj n-C3H, ~ (CH2) q~} OCH~C~12CH2CF3 n-C;H~L ~ ~CH2~ ~} OCH2CHzCH2CF3 CH3OCH2 ~ ~cH2) q~} OCH2CH2CH2CF3 CH2 = CHc~2cH2 ~ ~CH2) ~ OCH2CH2CH2CF3 n-C3H7 ~} (CH2) 4~ OCH2CH2CH2CF3 n-C5HLl ~ ~CH2) 4~ ` OCH2CH2CH2CF3 C2H5 ~} ~CH2) ~ OCH2CH2CH2CH2CF3 n C3H7 ~} ~CH2) 4~} OCH2CH2CH2CH2CF3 n-CsHL; ~ ~CH2) 4~ OCH2CH2CH2CH2CF3 CH3OCH2 ~ (CH2) 4~ OCH2CH2CH2CH2CF3 CH2 -- CHcH2cH2 ~ ~CH2) 4~} OcH2cH2cH2cH2cF3 C2Hs ~ ~CH2) 4~ OCH2CH2CH2CH2CF3 F

n-C3H7~ ~CH2) 4~ OCH2CH2CH2CH2CF3 F
n--CsH~CH2 ) 4~ OCH2CH2CH2CH2CF3 - 65 - 2~932~2 Exz~e 1~

CsH ~OCH2CH=CH-CF, 0.1 mol sf 4-(4-pentylcyclohexyl)phenol and 0.1 mol of 1,1,1-trifluoro-4-bromobut-2-ene are reacted analogously to Example 3.
The following trifluoroalkenyl ether~ of the formula R- 1~] ,-Z- (A) 0-O- (CH2) ~-CH=CH-CF3 are prepared analogously.

R ~ -1 ,-Z- (A~ O~ O- (CH2) ~-CH=CH-CF3 C2Hs ~)~ OCH2CH=CHCF3 n-C3H7 ~ OCH2CH=CHCF3 n-C4Hg ~} OCH2CH=CHCF3 CH3OCH2 ~ OCH2CH=CHCF3 CH2 = CHCH2CH2 ~} OCH2CH=CHCF3 C2Hs ~ )'' OCH2CH2CH=CHCF3 n-C3H7 ~ OCH2CH2CH=CHCF3 n-CsH~ ocH2cH2cH=cHcFi CH3OCH2 ~ OCH2CH2CH=CHCF3 CH2 = CHcH2cH2 ~} OCH2CH2CH=CHCF3 n-C3H7 ~ OCH2CH2CH=CHCF3 F

n-CsHl ~ GCH2CH2CH=CHCF3 66- 20~32~2 R - [ ~; ,-Z- (A) - -O- (CH2) -CH=CH-CF~
. . .. _ . ~_ . .
C2Hs ~(~3~ OCH~CH=CHCF3 n-C3H, ~ OCH2CH=CHCF3 n-CsHI ~ ~ OCH2CH=CHCF3 CH30CH2 ~ OCH2CH=CHCF3 CH2 - CHcH2cH2 ~ OCH2CH=CHCF3 CH3CH20 --~- OCH2CH~CHCF3 CH3CH2CH20 ~ OCH2CH=CHCF3 n-C3H7 ~ OCH2eH=CHCF3 F

n_C5Hll ~ OCH2CH=CHCF3 C2Hs _~_ OCH2CH2CH=CHCF3 n-C3H7 ~ OCH2CH2CH-CHCF3 n-C5Hll ~ OCH2CH2CH=CHCF3 CH3OCH2 ~ OCH2CH2CH-CHCF3 CH2 = CHcH2cH2 ~} OCH2CH2CH=CHCF3 CH3CH20 ~ OCH2CH2CH=CHCF3 CH3CH2CH2CH20 ~ OCH2CH2CH=CHCF3 C2Hs ~_ OCH2CH2CH=CHCF3 n-C3H~ ~ OCH2CH2CH=CHCF3 - 67 - ~93212 R - [ {>- ~ 5-Z- (A) ,- -O- (CH~ ) -CH=CH-CF3 n-C4Hg ~
~ OCH2CH2CH=CHCF3 CH3OCH2 ~ OCH2CH2CH=CHCF3 CH2 = CHcH2cH2 ~ OCH2CH2CH=CHCF3 CH2 = CHcH2cH2 ~ OCH2CH2CH=CHCF3 C2H5 ~} OCH2CH=CHCF3 n-C3H7 ~ OCH2CH=CKCF3 n-CsHI ~ ~ OCH2CH=CHCF3 CH3OCH2 ~ OCH2CH=CHCF3 CH2 = CHcH2cH2 ~ OCH2CH=CHCF3 n-C3H7 ~)~ OCH2CH=CHCF3 il-CsH~i ~ OCH2CH=CHCF3 C2H5 ~ OCH2CH2CH=CHCF3 n-C3H7 ~ OCH2CH2CH=CHCF3 n-CsHl 1 ~ OCH2CH2CH=CHCF3 CH3OCH2<} OCH2CH2CH=CHCF3 CH2 = CHCH2CH2 ~ OCH2CH2CH=CHCF3 - 68 - ~ J! ~ i3 21 ~

R ~ ;~~3] ~~Z~ (A) a~ ~O~ (CH2) r-CH=CH-CF3 n-CsH~: ~ OCH2CH2CH=CHCF3 F
CH30CH2CH~ ~ OCH2CH2CH=CHCF3 C2Hs ~ _ OCH2CH-CHCF3 n-C3H7 ~ OCHzCH=CHCF3 n-CsHll ~ OCH2CH=CHCF3 CH3OCH2 ~ OCH2CH=CHCF3 CH2 = CHcH2cH2 -< ~ OCH2CH=CHCF3 n-C3H7 ~ OCH2CHSCHCF3 F
n-CsH~ OCH2CH=CHCF3 C2Hs ~ OCH2CH2CHSCHCF3 n-C3H7 ~} OCH2C~l2CH-C~lCF3 n-C5HIl , ~ OCH2CH2CH=CHCF3 CH3OCH2 ~ OCH2CH2CHSCHCF3 CH2 = CHcH2cH2 ~ OCH2CH2CH=CHCF3 n-C3H, ~ OCH2CH2CH=CHCF3 R - [ ~ ~ ,-Z- (A) c~ -O- (CH2 ) ~-CH=CH-CF3 . _ _ n-CjH ~ OCH2CH2CH=ClICF3 F

CH3OCH2CH2 ~ OCH2CR2CH-CHCF3 C2H5~CH2CH2~ OCH2CH~CHCF3 n-C3H7~CH2CH2-~} OCH2CH=CHCF3 n-CsHIl~CH2CH2~ OCH2CH=CHCF3 CH3OCH2~CH2CH2~ OCH2CH=CHCF3 CH2 = CHCH2CH2 ~CH2CE~2~} OCH2CH=CHCF3 C2Hs~CH2CH2~ OCH2CHlCH=CHCF3 n-C3H7~H2CH2~ OC~2CH2CH~CHCF3 n-CsH~CH2CH2~ OCH2CH2CH~CF3 CH3OCH2-<~CH2CH2~} OCH2CH2CH-CHCF3 CHz = CHCH2CH2 ~CH2CHz~ OCH2CH2CH=CHCF3 C2Hs~ (CH2)~ ~ OCH2CH=CHCF3 n-C3H7~ ~CH2) 4~ OCH2CH=CHCF3 n~sHll~cH2) ~} OCH2CH=CHCF3 CH30CH2~ (CH2) ~-~ OCH2CH=CHCF3 CH2 = CHcH2cH2 ~} (CHz) ~ OCH2CH=CHCF3 _ 70 - 2!D~321`~

R ~ ],-Z- (A) ,- --O--(CH2) ~-CHaCH-CF3 -C2Hs~} (CH2) 4~ OC~12CH2CH=CHCF3 n-C3H7~} (CH2 ) q~ OCH2CH2CH=CHCF3 n-CsHll~ (CH2) ~ OCH2CH2CH=CHCF3 CH3OCH2~} (CH2) 4~} OCH2CH2CH'CHCF3 CH2 - CHcH2cH2 ~ ~CH2~ ~} OCH2CH2CH=CHCF3 C2H5~ (CH2) 44~; OCH2CH2CH=CHCF3 F
n-C3H~(CH2) 4~ OCH2CH2CH=CHCF3 n{:sHl 1~ (CH2 ) 4 ~ OCH2CH2CH~CHCF3 F
CH3OCH2~ (CH2 ) 4 ~ OCH2CH2CH=CHCF3 CH2 =CHcH2cH2 ~ (CH2 ) 4~ OCH2CH2CH=CHCF3 ~ 71 - ~09~212 ~1~ v~

H7C3- ~ 0C~2CF3 a) 8r ~ H2CF3 0.085 mol of 4-bromo-2-fluorophenol are dissol~ed in 100 ml of 1,3-dimethyl-2-imidazolidinone, the ~olution S i~ heated to 140-C and 0.09 ml of 2,2,2-trifluoroethyl methylsulfonste i~ added dropwi~e. The solution i8 stirred at 140-C for 24 hours. 500 ml of ice water are ~ubsequently added, and the product i8 ~3ub~ected to conventional work-up.
F

b) H3C7 ~ H2CF3 O.05 ml of tran~-n-propylcyclohexylphenylboric acid, 20 ml of toluene, 10 ml of ethanol, 0.030 mol of sodium carbonate and 0.86 mmol of tetrakisttriphenyl-pho~phine)p~ dium(0) are added to 0.015 mol of 4-bromo-2-fluorophenol 2,2,2-trifluoroethyl ether, and the mixture is refluxed for 2 hours. 100 ml of petroleum ether (40-80-) are added, and the product is sub~ected to conventional work-up. C 81 SB 101 S~ 133 N 139 . 6 I, ~n - 0.152.
The following compounds of the formula R~OCH2CF3 L3 Li are prepared analo~ously:

- 72 - ~3321 R L: L2 L-C2Hs H H H
C~H5 H F F K 86 I, ~ 0,111 C2Hs F H H K 7C N ~62, 4~ r,~ 0 137 C~Hs F F F K 96 I, Qn - ~0,105 n-ClH7 F H H K 8q N lOq, 6 t, l~n - ' 0,152 n~H7 F F F K sa I, ~ 0,111 n-C~H7 H F F xasr,~- ~0,120 n-C~H~ H H H
n--C5HI~ F H H K 65 N 108, ~ 0,142 n-C5H~I F F F K 90 I"~ 0,113 n-C5HIl H F F KilN ~78,2) I, ~-~0,119 CH,OCH2 H H H
CH,OCH2 F H H
CH,OCH2 F F F
CH~-CHCH~CH2 F F F

~uuqple 15 F

C3H7~H2CF3 n) ~r ~ H2CF3 F
2,2,2-Trifluoroethyl methylsulfonate i~ added dropw$~e at 140-C to 0.085 mol of 4-bromo-2,6-difluoro-phenol analogou~ly to Example 14 a).

C3H7~$~)CH2CF;

2~93212 1.2 g of zinc chloride and 0.14 g of lithium granules are added to 0.01 mol of trans-4-n-propylcyclo-hexyl bromide in 15 ml of a solvent mixture compri~ing T~F and toluene (1:4). The mixture i8 treated with ultrasound for 4 hours at between 0 and 10C under a protective gas and with ~tirring. The organozinc compound obtained i8 treated with 0.01 mol of 4-bromo-2,6-di-fluorophenol 2,2,2-trifluoroethyl ~thor and 2 mol~ of l,l'-bis~diphenylpho~phino)ferro~enepall~dium(II) dichlorid~, the ultrasound bath and tho cooling are removed, and the mixture is stirred at room temperature for 24 hour~. 10 ml of ~aturated ammonium chloride solution are added, and the organic phase i separated off and subjected to customary work-up. C S I, lS ~n ~ 0.038.
The following compounds of the formula F

R-~ ~ ]' ~ H2CF3 ar- prepared analogously:

- 74 _ ~0~3~ ~ ~

R s L
.
n-C2Hs l H
n-C2Hs 1 F
n-C2Hs 2 H C 65 Sll 91 N l~9. 9 ~ 0. 093 n-C2Hs 2 F C 65 N 100.2 ~ 0.084 Il--C3H7 1 H
n-C3H7 1 F
n-C3H7 2 H
n--C3H~ 2 F C 69 N l~tO I; ~1 - ~O. 092 n-C5Hll 1 H
n-CsHll 1 F
n-CSHll 2 H C 62 59 92 N lSl.7 ~: ~ ~0,09 n-C5HIl 2 F C 60 N 137.~ 0.006 CH2'CHCH2CH2 1 H
C~l2-CHCH2CH2 1 F
C~l2~CHCH2C~2 2 H
CH2~CHCH2C~2 2 F

~32~2 xample ~

O
H7C3 ~ ~ -OCH2CF, o F
a) H7c3{ )- ~
F
0.035 mol of 3,5-difluorobenzaldehyde, 0.35 mol of propanediol and 3.5 g of p-toluenesulfonic ~cid are dissolved in 500 ml of toluene and boiled on a water separator.
F

b) H'C3 { ~ OH
F
O.044 mol of the dioxane derivativQ frsm Example 16 a) i8 dissolved in 130 ml of ab~olute THF, and the solution i~ cooled to -70C. 51 mmol of n-3uLi are subsequently added dropwi~e. The mixture is ~tirred at -70C for 0.5 hour, and 51 mmol of trim~thyl borate are thcn added dropwise to the reaction mixture. The mixture i~ then allowed to warm to -20C, and 5 ml of acetic acid are added in portions. Finally, 132 mmol of ~22 are added dropwise to the reaction mixture at a temperature of 30-35C. The mixture i~ subsequently subjected to cu~tomary work-up.

O
c ) H7C3~ OcH2cF3 F
23 mmol of sodium hydride are suspended in lO ml of DMEU, and 23 mmol of the phenol derivative from Example 16 b) in 20 ml of DMEU are ~ubsequently added dropwi~e. The mixture i~ subsequently stirred at 45C for 1 hour. 25 mmol of 2,2,2-trifluoroethyl methylsulfonate - 76 _ 2~ 2~2 in 5 ml of DMEU are added dropwise to the reaction mixture at 140C, and the mixture is stirred at 140-C for 5 hours. After hydrolysi~3, the reaction mixture is acidified and sub~ected to customary work-up.
C 27 I; a6 = 15.76; an = +0.038 The followinq compounds of the formula R--(Al--Z: ) m~OCH2CF3 are prepared analogously:

R (A ~Z ) ~ Ll ~ L2 .----C2Hs { ~ H H
o C2Hs { ~ H F
o C2Hs { ~ F F

- 77 ~

~( ( A ~ r L-C
n-C3H. { >_ H .

n-C3H, {~ H F

n~C4H3 {~ H H

n-C~ H9 { ~ H ~ F

n~CqHg {~ F F

n-CsHl { ~_ H H

n~CsHl: { >_ H F

n-CjHl: {~ F F

n-C6Hl 3 {~~ H H

n-C6H 3 {>_ H F

n-C6H: 3 {~_ F F

~as32l2 R ( ~A - 7 ) ~

. ~

: s { ~

n-C,Hls { )~ H F

n-C7H~s {)~ F F

n--C3H7 { >~ H H

n-C3H7 ~X~ H ,.

n-c3H7 {~ F F

n-CsHl 1 {X~ H H

n-CsHl 1 {o~ H F

n-CsHll {X~ F F

_ 7~ 3~1~
~ample 17 F
H C~ { ~CC:~2 CF
F

13 mmol of 2-[2,6-difluoro-4-hydroxyphenyl]-5-pentylpyrimidine are reacted analogously to Example 16 c) with 13 mmol of sodium hydride in 300 ml of DMEU and 25 mmol of 2,2,2-trifluoroethyl methylsulfonate.
C 66 I; ~ = 18.49; ~n - 0.106 ThP following compounds of the formula r<
R-(A'~Z )m ~ OCH2CF.

are obtained analogously.

R ~Al-Z:) T L2 :
N

C2H4 ~ ~- .{ H
N
N

C2H4 ~ ~ H F
N
N

C2H4 {)- T F
N
N

n-C3H7 ~ ~ H H
N
N

n-C3H7 { ~ H F
N
N

n-C3H7 { ~ F
~J

- 80 _ ~ w~

R (A:-Z: ) ., L: L2 H~
N

n-C~Hg _,~N H F
N

n-C4H~ F F
N
N

n-C;H~ H H

n-CsH., _<~ N H
N

n-C6Hl 3_~ N H H
N
n-C6Hl 3_~ N H
N

n-C6Hl 3 ~ )~
N

n-C~Hls ~;~ H H
N

n-C7Hls ~N H
N

;\T
n-C~Hl s{

~93212 R (A --Z! ) .r L: L2 _ ~-C3`U~

n-C3H, -C )~ H F

n-C3H N F E`

n-C5H!: ~ ~ H H

n-CjH!: N H F

n-CsHll N F F

Claims (22)

Patent claims

1. Liquid-crystalline compounds of the formula I

I

in which R is H, an alkyl or alkenyl radical having 1 to 15 carbon atoms which is unsubstituted, monosubstituted by CN or CF3 or at least mono-substituted by halogen, it also being possible for one or more CH2 groups in these radicals each to be replaced, independently of one another, by -O-, -S-, , -CO-, -CO-O-, -O-CO- or -O-CO-O- in such a way that oxygen atoms are not linked directly to one another, Z1 and Z are each, independently of one another, -CH2CH2-, -CH=CH-, -C=C- or a single bond, and one of the radicals Z1 and Z in alternatively -(CH2)4- or -CH=CH-CH2CH2-, A and A1 are each, independently of one another, trans-1,4-cyclohexylene in which, in addi-tion, one or two non-adjacent CH2 groups may be replaced by -O-, or are 1,4-phenylene which is unsubstituted or monosubstituted or disubstituted by fluorine and/or C1 atoms and in which, in addition, one or two CH groups may be replaced by N, m is 0, 1, 2 or 3, o and s is 0, 1 or 2, where (s+o) is ? 2, W is -O-, -COO- or a single bond, Q is -O-, -CH=CH- or a single bond, r is 1 to 7, t is 0 to 7, and Y is F, C1, CF3, OCF3, CHF2, OCHF2 or OCH2F.

2. Compounds of the formula I in which the ring adjacent to W-( CH2)r-Q-(CH2)t-Y is

3. Compounds of the formula I'' I'' in which L is H or F, and R, Z1, Z, W, Y, r and t are as defined in Claim 1.

4. Compounds of the formula IA

IA

in which n is 0 to 7, D is -O-, -CH=CH- or a single bond, a is 1 to 5, b is 0 or 1, and Z, A, o, r and 9 are as defined in Claim 1.

5. Compounds of the formula Ia Ia in which a is 1 to 5, b is 0 or 1, 9 is 1 or 2, and A, Z, o and r are as defined in Claim 1.

6. Compounds of the formula Ib I Ib in which n is 1 to 7, s is 1 or 2, b is 0 or 1, and A, Z, o and r are as defined in Claim 1.

7. Compounds of the formula Ic Ic in which L1 is H, F or Cl, L2 is F or Cl, and R, A1, z1, Z, m and s are as defined in Claim 1.

8. Compounds of the formula II

II

in which L is F, and R, Z1 and Z are as defined in Claim 1.

9. Compounds of the formula III

III

in which L is F, and R, Z1 and Z are as defined in Claim 1.

10. Compounds of the formula Ib according to Claim 6, characterised in that s = 2 and Z is a single bond.

11. Compounds of the formula Ib according to Claim 6, characterised in that s = 1 and A z 1,4-phenylene.

12. Compounds of the formula Ib according to Claim 10, characterised in that Z is a single bond.

13. Compounds of the formula Ib according to Claim 10, characterised in that Z is -(CH2)2-.

14. Compounds of the formula Ib according to Claim 10, characterised in that Z is - (CH2)4-.

15. Compounds of ths formula IV

IV
in which L, W, Q, Y, r and t are as defined in Claim 1.

16. Compounds of the formula IB

IB

in which L is H or F.

17. Process for the preparation of the compounds IB

IB

in which L is H or F, characterised in that 4-bromo-2-fluorophenoxide or 4-bromo-2,6-difluorophenoxide is reacted with 2,2,2-trifluoroethyl methylsulfonate in the presence of 1,3-dimethyl-2-imidazolidinone.

18. Use of compounds of the formulae I, II and III as components of liquid-crystalline media.

19. Liquid-crystalline medium having at least two liquid-crystalline components, characterised in that it contains at least one compound of the formula I.

20. Liquid-crystalline medium having at least two liquid-crystalline components, characterised in that it contains at least one compound of the formula II.

21. Liquid-crystal display element, characterised in that it contains a liquid-crystalline medium according to Claim 19 or 20.

22. Electro-optical display element, characterised in that it contains, as dielectric, a liquid-crystalline medium according to Claim 19 or 20.