1 (SUBST. - 4-ACYLOXY-CYCLOHEXYL) - 2 (4-ALKYLCYCLOHEXYL) ETHANE WITH LIQUIDCRYSTALLINE CHARACTERISTICS.
The invention is stated in requirements 1 to 3. Those stands in it, for mixtures with high clarifying temperatures to receive however at the same time favorable switching times. For the reaching of high clarifying temperatures one can add substances with an expanded linear ring system, whereby however also the viscosities and thus the switching times rise strongly (H. Kelker, R. Hatz: Handbook OF liquid Crystals, publishing house chemistry, Weinheim 1980).
A goal of the invention are substances, which ren the self-crowds of mixtures toward high Klärtemperatulo with at the same time favorable switching times beeinflussen.
Task of the invention is the Auffínden of l (Subst. - 4-acyloxy-cyclohexyl) -2 (4-alkylcyclohexyl) ethanen, the liquidcrystalline characteristics aufweisen.
It was found that connections of the general formula RI-COO @-CH2 - CH2 - @ - R2 wobeiRl= CnH2 n+1 - @, CnH2 n+1 - @, 1II CùH2n+lO-@, NC-@, CnH2n + i -, CnH2n+l CnH2n+ lCnH2n+l - with n, m = 1 to 10 to mean, liquidcrystalline characteristics show. In nematischen mixtures with an additive of the connections of the formula III in quantities from 5 to 40% the points of clarifying are importantly increased, without increasing the viscosity substantially, so that favorable switching times defnierten erim requirement 3 mixtures can in optoelektro40 aim werden.
niches elements used werden.
It is a very large number of crystalline-liquid, predominantly nematischen connections admits (D. Demus, H.
Demus, H. Waschke: Liquid crystals in tables, VEB German publishing house for Grundstoffíndustrie Leipzig, 2nd Aufl.
1976). None of the well-known connections possesses such characteristics, which would make a direct employment possible in opto-electronic elements in pure condition. It is however well-known that one can change the characteristics by mixing several connections in a way that Schmelzund clarifying temperatures, the threshold voltage, the dielectric and optical anisotropy, the viscosity and other characteristics an employment of the mixture in opto-electronic elements zulassen.
For the change of the characteristics of the mixtures one needs again and again new components, which improve the mixtures toward the direction demanded by the technical advancement. An important goal beDie most of the connections according to invention are in the pure condition smektisch, however in suitable mixtures nematisch and therefore for opto-electronic elements, e.g. on the basis of the TNP effect, verwendbar.
4s the connections according to invention are colorless and very stable opposite humidity, warmth and elektñschen Feldern.
The connections according to invention received by shifting of 4-Methoxyphenylessigsäure and substituted Benzenen as well as following reduction to a substituted Diphenylethen, which after Etherspaltung by Hochdruckhydrierung first to a substituted Dicyclohexyl ethan II hydrogenates and afterwards with a Säurechlorid to an l (4-Acyloxy-cyclohexyl) - 2 (4-alkylcyclohexyl) - ethan III are verestert. ° for example the connections can manufactured as follows werden.
The synthesis takes place according to the following pattern:
HO_@_CH2_CH2_@_R2 H2, HO--@-CH2 - CH2 - @-R2 I left + RI-@-COCI--, R'-@-COO-@_CH2 _CHz_@_Rz - > - = - @ - or @ - 1II 3,664,558 synthesis the 4 (4-Pentylcyclohexyl-ethyl) - cyclohexanols 11.
28 g (0.096 mol) become 4 [2 (4-Pentylcyclohexyl) - ethyl] - phenol solved in 300 ml absolute alcohol and with g RANEY nickel shifts. With 12,6 MPa (125 RKs) hydrogen printing and 15 'C the product is vibrated of about 10 hours in autoclaves, until no more decrease of pressure is to be observed. After cooling of the Reaktionsgef'åsses the catalyst is separated from the solvent and RST drop by drop is shifted. After good agitating the beginning is left at ambient temperature 12 h to stand, heated up then further 5 to 6 h under agitating in the Wasserbad. The cooled down reaction mixture is poured onto sulfur-sour ice water and as usual aufgearbeitet.
The Estcr III becomes from methanol up to the Konstanz Schmelzund phase transition temperatures umkristallisert.
For the characteristic of the new connections Tab gives. 1 sungsmittel at the rotation evaporator removes. After fraktiol0 the transformation temperatures of some substances of allgenierter distillation a constantly simmering, syrup-like become mean formula liquid erhalten.
The boiling point amounts to 180 AC with 27 Pa. The yields at hydrogenated product are with 75%.
Veresterung 2.82 g (0.01 mol) of the Cyclohexanols II become in 50 ml dry Pyridin with the äquimolaren quantity Säurechlorid an.
RI-COO-@-CH2-CH2-@-R2 table 1 verb. G 1 R2 K self-service N is 1 2 3 4 6 7 8 C4H90-- C4 Hç C4H90-@ C2 H5 C5H11O-@ C2 H5 C6HI30-@ C2 H5 C4H9-- CsHII C4H9-@ CsHII CN-@ C4 H9 C2Hs-@ - C5 H! I 44 - 126 66 - 134 58 - 117 64 - 118 34 183 - 187 - 103 - 143,169 - it mean: K - crystalline self-service - smektisch B N - nematisch is - isotropically table 2 gives the transformation temperatures einigêr to Vergleichssubstanzen with the general formula an.
RI-COO @-CH2 - CH2 - @ - R2 table 2 approx. verb. R) R2 9 C4 Hç @--@ - C2 H5 z., xth. _/CN-g@ CsH11 11 C4 H9 0-t/'Õ - C8 Hj7 xth. __/K S N is 99 - 223,118 - • 164 83 - • 122 for the statement of the favorable change of the self-crowds with the additive of the substances according to invention soli the following example serve:
The mixture A possesses the following composition:
4-ne-Propylcyclohexancarbonsäure -4-cyanphenylester 34.5 mol % 4-ne-Butylcyclohexancarbonsäure-4-cyanphenylcster 31.0 mol % 4-ne-Pentylcyclohexancarbonsäure-4-cyanphenylester 34.5 mol % to this mixture were added some by the er664 mentioned 558 findungsgemässen substances; 3 4 in Tab resulted the table. 3 arranged Eigenschaftsänderungen.
Verb. Mi A Klp. Fp. q U zs0 Z5o mol % E A D No. mol % (C) (C) (cP) (v°) (ms) (ms) (lam) m 6 8 - 100 72 10 14 31.1 1.3 90 227 24 90 84 38.3 - - - 90 84 - 1.6,290,500 22.5 90 83 35.1 - - - mean: Klp. - Point of clarifying Fp. - Fusion point ri - viscosity with 25 C Uo - threshold voltage 20 C, 500 cycles per second OE E5 Einschaltzcit U = 2 Uo, 20 C, 500 cycles per second z A5o - (fall time) fading time D - layer thickness for the examination of the increase of point of clarifying became consisting a mixture B of C3H “O O O CsH, t O B - CN 50 mol % - CN 50 mol % mol % of the substance No. 5 zugegeben.
Tab. the result table 4 verb shows 4. - No. mol % MiBmol % Klp.(C) the points of clarifying of the mixtures examined here behave according to a linear function of the Konzentration.
For two substances the fusion enthalpies were intended, their values in table 5 laid down sind.
Table verb. - Nr.
6 FH 22 16.55 kJ.mol I) these very small values of the fusion enthalpy bedeu3s ten eroe strong depression of the fusion points into Geml and thus a large existence range of the nematischen Phase.
- 100 43 90 54 C Nematic liquid crystalline mixtures, which can be used in optoelectronic components. Compounds are provided which influence the characteristics of mixtures in the direction of high clarification temperatures at simultaneous favorable switching times. It has been found that compounds of the general formula <IMAGE> <IMAGE> <IMAGE> <IMAGE> <IMAGE> R2 = CmH2m+1 wherein n, m=1 to 10 in nematic mixtures in quantities of 5 to 40% considerably increase the clarification points without significantly increasing the viscosity, so that favorable switching times are obtained. The new mixtures can be used for the production of optoelectronic components (displays) for watches, computers and other devices. 1. A nematic liquid crystalline mixture for use in optoelectronic components, comprising a mixture of nematic liquid crystalline compounds, together with at least one compound of the general formula ##STR18## wherein n, m=1 to 10, said at least one compound being contained in the mixture in quantities of 5 to 40% of the total nematic liquid crystalline mixture. 2. Nematic liquid crystalline mixture according to claim 1, wherein R.sub.1 signifies ##STR19## and R.sub.2 =C.sub.4 H.sub.9 --. 3. Nematic liquid crystalline mixture according to claim 1, wherein R.sub.1 signifies ##STR20## and R.sub.2 =C.sub.2 H.sub.5 --. 4. Nematic liquid crystalline mixture according to claim 1, wherein R.sub.1 signifies ##STR21## and R.sub.2 =C.sub.2 H.sub.5 --. 5. Nematic liquid crystalline mixture according to claim 1, wherein R.sub.1 signifies ##STR22## and R.sub.2 =C.sub.2 H.sub.5 --. 6. Nematic liquid crystalline mixture according to claim 1, wherein R.sub.1 signifies ##STR23## and R.sub.2 =C.sub.5 H.sub.11 --. 7. Nematic liquid crystalline mixture according to claim 1, wherein R.sub.1 signifies ##STR24## and R.sub.2 =C.sub.5 H.sub.11 --. 8. Nematic liquid crystalline mixture according to claim 1, wherein R.sub.1 signifies ##STR25## and R.sub.2 =C.sub.4 H.sub.9 --. 9. Nematic liquid crystalline mixture according to claim 1, wherein R.sub.1 signifies ##STR26## and R.sub.2 =C.sub.5 H.sub.11 --. 10. A compound of the general formula: ##STR27## wherein n, m=1 to 10, said compound, when added as a component to a nematic liquid crystalline mixture, providing a formulation in which the characteristics of said mixture are influenced and modified in the direction of high clarification temperatures and points, without substantially increasing the viscosity of the mixture, so that simultaneous favorable switching times are obtained.