GB1594085A - Optically active pyrimidine compounds liquid crystal compositions containing them and their use in electrooptical apparatus - Google Patents

Optically active pyrimidine compounds liquid crystal compositions containing them and their use in electrooptical apparatus Download PDF

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GB1594085A
GB1594085A GB10692/78A GB1069278A GB1594085A GB 1594085 A GB1594085 A GB 1594085A GB 10692/78 A GB10692/78 A GB 10692/78A GB 1069278 A GB1069278 A GB 1069278A GB 1594085 A GB1594085 A GB 1594085A
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pyrimidine
cyanophenyl
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/48—Preparation of compounds having groups
    • C07C41/50—Preparation of compounds having groups by reactions producing groups
    • C07C41/54—Preparation of compounds having groups by reactions producing groups by addition of compounds to unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
    • C07C45/515—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an acetalised, ketalised hemi-acetalised, or hemi-ketalised hydroxyl group
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    • C07C47/00—Compounds having —CHO groups
    • C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
    • C07C47/277—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing ether groups, groups, groups, or groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
    • C07C47/55—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
    • C09K19/345—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom the heterocyclic ring being a six-membered aromatic ring containing two nitrogen atoms
    • C09K19/3458—Uncondensed pyrimidines
    • C09K19/3463—Pyrimidine with a carbon chain containing at least one asymmetric carbon atom, i.e. optically active pyrimidines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers

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Description

(54) OPTICALLY ACTIVE PYRIMIDINE COMPOUNDS, LIQUID CRYSTAL COMPOSITIONS CONTAINING THEM AND THEIR USE IN ELECTROOPTICAL APPARATUS (71) WE, F. HOFFMANN-LA ROCHE & CO., AKTIENGESELLSCHAFT, a Swiss Company of 124-184 Grenzacherstrasse, Basle, Switzerland, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The present invention relates to optically active pyrimidine compounds, a process for the manufacture thereof, liquid crystalline mixtures for electro-optical purposes containing same and a process for the preparation of said liquid crystalline mixtures. The invention is also concerned with an electro-optical apparatus containing said pyrimidine derivatives or said liquid crystalline mixtures.
The optically active pyrimidine derivatives provided by the present invention have the following general formula
wherein the symbol Z represents a group of the formula HCH2)nor CH2)nO in which n stands for an integer of I to 4 and each of the symbols X represents a nitrogen atom and each of the symbols Y represents =CH- or each of the symbols Y represents a nitrogen atom and each of the symbols X represents CM-.
It is known that the addition of cholesteric compounds to a matrix of nematic liquid crystals with positive anisotropy of the dielectric constants leads to a cholesteric mixture which undergoes a cholesteric-nematic transition upon application of an electrical field. This phase transition is reversible and makes possible high switching speeds of the electro-optical apparatuses operated with such mixtures.
Hitherto known cholesteric compounds have the disadvantage of a usually only very narrow mesophase range and, as a rule, a low or even monotropic clearing point.
Surprisingly, it has now been found that the optically active pyrimidine derivatives of formula I possess not only a wide mesophase range but also a high clearing point, by means of which these properties of corresponding mixtures can likewise be improved drastically. Moreover, the optically active pyrimidine derivatives of formula I possess a strong positive anisotropy of the dielectric constants, which has a further favourable influence on the positive anisotropy of the dielectric constants of corresponding mixtures. Furthermore, the present optically active pyrimidine derivatives have a high chemical stability.
The mixtures which contain the optically active pyrimidine derivatives of formula I can also contain other pleochroitic colouring substances.
Examples of optically active pyrimidine derivatives of formula I are: 5 - [4' - (+) - 2" - methyl - 1" - butylphenyl] - 2 - (4 - cyanophenyl) pyrimidine, 5 - [4' - (+) - 3" - methyl - 1" - pentylphenyl] - 2 - (4 - cyanophenyl) pyrimidine, 5 - 14' - (+) - 4" - methyl - 1" - hexylphenyl] - 2 - (4 - cyanophenyl) pyrimidine, 5 - [4' (+) - 5" - methyl - 1" - heptylphenyl] - 2 - (4 cyanophenyl) - pyrimidine, 5 - [4' - (+) - 2" - methyl - 1" - butyloxyphenyl] - 2 - (4 - cyanophenyl) pyrimidine, 5 - [4' - (+) - 3" - methyl - 1" - pentyloxyphenyl] - 2 - (4 - cyanophenyl) - pyrimidine, 5 - [4' - (+) - 4" - methyl - 1" - hexyloxyphenyl] - 2 - (4 - cyanophenyl) pyrimidine, 5 - [4' - (+) - 5" - methyl - 1" - heptyloxyphenyll - 2 - (4 - cyanophenyl) - pyrimidine, 2 - [4' - (+) - 2" - methyl - 1" - butylphenyl] - 5 - (4 - cyanophenyl) pyrimidine, 2 - [4' - (+) - 3" - methyl - 1" - pentylphenyl] - 5 - (4 - cyanophenyl) pyrimidine, 2 - [4' - (+) - 4" - methyl - 1" - hexylphenyl] - 5 - (4 - cyanophenyl) pyrimidine, 2 - [4' - (+) - 5" - methyl - 1" - heptylphenyl] - 5 - (4 - cyanophenyl) - pyrimidine, 2 - [4' - (+) - 2" - methyl - 1" - butyloxyphenyll - 5 - (4 - cyanophenyl) pyrimidine, 2 - [4' - (+) - 3" - methyl - 1" - pentyloxyphenyl] - 5 - (4 - cyanophenyl) pyrimidine, 2 - [4' - (+) - 4" - methyl - 1" - hexyloxyphenyl] - 5 - (4 - cyanophenyl) pyrimidine, 2 - [4' - (+) - 5" - methyl - 1" - heptyloxyphenyl] - 5 - (4 - cyanophenyl) pyrimidine and their optical antipodes. Especially preferred optically active pyrimidine derivatives of this invention are those in which each of the symbols X represents -CM- and each of the symbols Y represents a nitrogen atom.
According to the process provided by the present invention, the optically active pyrimidine derivatives of formula I are manufactured by (a) reacting a compound of the general formula
wherein the symbols X, Y and Z have the significance given earlier, with copper-(I) cyanide, sodium cyanide or potassium cyanide, or (b) for the manufacture of optically active pyrimidine derivatives of formula I in which each of the symbols X represents CM- and each of the symbols Y represents a nitrogen atom, dehydrating a compound of the general formula
wherein the symbol Z has the significance given earlier, or (c) for the manufacture of optically active pyrimidine derivatives of formula I in which- each of the symbols X represents a nitrogen atom and each of the symbols Y represents CM- dehydrating a compound of the general formula
wherein the symbol Z has the significance given earlier, the starting materials of formulae II, III and IV being used in optically active or racemic form and, when a racemic starting material of formula II, III or IV is used, a resulting racemate being separated into the optical antipodes. A preferred starting material is a compound of formula II, III or IV in which the symbol Z represents a group of the formula CH2)n or CH2)nO wherein n stands for 1.
In embodiment (a) of the foregoing process, a compound of formula II is reacted with copper-(I) cyanide, sodium cyanide or potassium cyanide. This reaction is conveniently carried out in an inert organic solvent such as ethyleneglycol, tetrahydrofuran, dimethylformamide, dimethyl sulphoxide, pyridine and acetonitrile. The temperature and pressure are not critical aspects of this reaction. The reaction is conveniently carried out at atmospheric pressure and a temperature between room temperature and the boiling point of the reaction mixture. The halogen atom present in the compound of formula II is preferably a bromine atom.
The dehydration of a compound of formula III in accordance with embodiment (b) of the foregoing process can be carried out using any suitable dehydrating agent such as phosphorus oxychloride, phosphorus pentoxide, thionyl chloride or acetic anhydride. The dehydration can be carried out in an inert organic solvent such as a hydrocarbon or halogenated hydrocarbon, if necessary in the presence of a base such as sodium acetate, pyridine, or triethanolamine. The dehydration can, however, also be carried out in the absence of an organic solvent.
The dehydration is conveniently carried out at the reflux temperature of the mixture. Although the pressure is not critical, the dehydration is preferably carried out at atmospheric pressure.
In embodiment (c) of the foregoing process, a compound of formula IV is dehydrated. The dehydration is conveniently carried out using acetic anhydride or using anhydrous sodium acetate in glacial acetic acid or also under the conditions described hereinbefore in connection with the dehydration of a compound of formula III. The dehydration is carried out at the reflux temperature of the mixture. Although the pressure is not critical, the dehydration is advantageously carried out at atmospheric pressure.
The cleavage of a racemate obtained into the optical antipodes can be carried out in a manner known per se; for example, by salt formation with an optically active acid or, after saponification of the cyano group, by salt formation with an optically active base and fraction crystallization of the resulting salts.
The compounds of formulae II, III and IV used as the starting materials are novel.
The novel compounds of formulae II, III and IV can be prepared in a manner known per se as illustrated by Formulae Schemes I to IV hereinafter for such compounds in which the halogen atom is a bromine atom and the symbol A represents a group of the formula
in which the symbol Z has the significance given earlier. Formula Scheme I
Formula Scheme II
Formula Scheme III
A eCHO &commat;3-P -CH2 OCH3 Cl NaH //CHOCH3 /0 A CH NC HC(OC2Hg)3 HCl/C /C2 H, O H BF3O(C2 H5)3 5 2 ) OH /OCH3 /C,,H HCl HN\\ 0 A CH OC2H5 C C CH(OC2Hg)2 H2N C2H5 H / H20 I NH3/Pressure CHOC2H5 HCIHN O /\// AC C C CHO + H2N NH2 NaOCH3 C H30H N 0 A < \t3 C - N H2 (III) Formula Scheme IV
Formula Scheme IV (continued)
MnO2 OHC t MffiA NH20H-HCI Pyridir.e
The optically active pynmdine derivatives of formula I are conveniently used in the form of mixtures with nematic substances; for example, with compounds of the general formula
wherein the symbol R6 represents a straight-chain alkyl group containing 2 to 8 carbon atoms, a straight-chain alkoxy group containing 4 to 7 carbon atoms, a straight-chain alkanoyloxy group containing 2 to 8 carbon atoms or a straight-chain alkylcarbonate group containing 2 to 11 carbon atoms, and/or with compounds of the general formula
wherein the symbol R, represents a straight-chain alkyl group containing 4 to 7 carbon atoms, or a straight-chain alkyl-carbonate group containing 2 to 11 carbon atoms, and/or with compounds of the general formula
wherein the symbol R8 represents a straight-chain alkyl group containing 4 to 8 carbon atoms, a straight-chain alkoxy group containing 5 to 8 carbon atoms, a straight-chain alkanoyloxy group containing 2 to 8 carbon atoms or a straight-chain alkylcarbonate group containing 3 to 11 carbon atoms, and/or with compounds of the general formula
wherein the symbol Rd represents a straight-chain alkyl group containing 4 to 8 carbon atoms, a straight-chain alkoxy group containing 4 to 8 carbon atoms, a straight-chain alkanoyloxy group containing 4 to 9 carbon atoms, or a straight-chain alkylcarbonate group containing 4 to 11 carbon atoms and n stands for 1 or 2, and/or with trans-cinnamic acid esters of the general formula
wherein the symbol R10 represents a straight-chain alkyl group containing 1 to 8 carbon atoms, and/or with compounds of the general formula
wherein one of the symbols R,l and R, > represents a cyano group and the other represents a straight-chain alkyl group containing 3 to 9 carbon atoms, a straight-chain alkoxy group containing 2 to 9 carbon atoms or a straight-chain alkanoyloxy group containing 2 to 9 carbon atoms, and/or with compounds of the general formula
wherein each of the symbols X represents a nitrogen atom and each of the symbols Y and Z represents =CH-- or each of the symbols Y represents a nitrogen atom and each of the symbols Y and Z represents =CH- or each of the symbols Z represents a nitrogen atom and each of the symbols X and Y represents =CH-- and one of the symbols R, and R2 represents cyano and the other represents a straight-chain alkyl group containing 1 to 7 carbon atoms, a straight-chain alkoxy group containing 1 to 7 carbon atoms or a straight-chain alkanoyloxy group containing 2 to 7 carbon atoms.
The optically active pyrimidine derivatives of formula I are present in nematic mixtures for electro-optical purposes in a weight ratio which preferably corresponds to the eutectic composition. The amount of an optically active pyrimidine derivative of formula I present in a nematic mixture is, however, generally between about 1 and about 40 percent by weight, preferably between 5 and 30 percent by weight and especially between about 5 and 15 percent by weight.
The invention also includes a process for the preparation of liquid crystalline mixtures, which comprises mixing one or more of the optically active pyrimidine derivatives of formula I with nematic substances.
Examples of preferred mixtures are the following, the percentages being expressed as mol percentages: 12.7% of P - [(p - n - Propylbenzyliden)aminolbenzonitrile, 34.5% of p - [(p n - butylbenzyliden)amino]benzonitrile, 46.9% of p - [(p - n - hexylbenzyliden)amino]benzonitrile and 5.4% of 5 - [4' - (+) - 2" - methyl - 1" - butoxyphenyl] 2 - (4 - cyanophenyl) - pyrimidine; clearing point 72.2".C; 11.2% of p-n-butylbenzoic acid p'-cyanophenyl ester, 12.5% of p-npentylbenzoic acid p'-cyclophenyl ester, 16.0% of p-n-hexyl-benzoic acid p'-cyanophenyl ester, 17.2% of p-n-heptylbenzoic acid p'-cyanophenyl ester, 11.9% of 5-npentyl-2-(4-cyanophenyl)-pyrimidine, 23.2% of 5-n-heptyl-2-(4-cyanophenyl)pryimidine and 7.3% of 5 - [4' - (+) - 2" - methyl - 1" - butyloxyphenyl] - 2 - (4 cyanophenyl) - pyrimidine; clearing point 65.60C; and 55.7% of 4-pentyl-4'-cyanobiphenyl, 33.2% of 4-pentyloxy-4'-cyanobiphenyl and 6.4% of 5 - [4' - (+) - 2" - methyl - 1" - butyloxyphenyl] - 2 - (4 cyanophenyl) - pyrimidine; clearing point 60.3"C.
The compounds of formula XI hereinbefore are described and claimed in our U.K. Patent Specification No. 151009 and can be obtained, for example, by reacting a compound of the general formula
wherein one of the symbols R3 and R4 represents a straight-chain alkyl group containing 1 to 7 carbon atoms, a straight-chain alkoxy group containing 1 to 7 carbon atoms, or a straight-chain alkanoyloxy group containing 2 to 7 carbon atoms and the other represents a halogen atom and the symbols X, Y and Z have the significance given earlier, with copper-(I) cyanide, sodium cyanide or potassium cyanide.
This reaction can be carried out in an analogous manner to that described earlier in connection with the reaction of a compound of formula II with copper-(l) cyanide, sodium cyanide or potassium cyanide.
The preparation of the compounds of formula XII can be carried out according to the disclosure of the unexamined German Patent Publication (DOS) No. 2641 724 and is illustrated in the following Formulae Schemes A to F for such compounds in which one of the symbols R3 and R4 represents a straight-chain alkyl group containing I to 7 carbon atoms and the other represents a bromine atom.
Formula Scheme A
Formula Scheme B
Br ECHO 8PO-CH20CH. P 3 3LI INaH Br vCH HC(OC2H5) 3 E3F3 O(C2H 5)2 OCH3 CH 8r - 0C2H5 NC Alkyl CH(OC2H5 ) 2 HO/H20 i)HCl/C2H5OH 2 2 )NH3 CHOC2H5 HCl.HN + /C - Alkyt CHO H2N :Hg B r < \t3A Ikyl (XIIb) Formula Scheme C
Alkyl XCHO 0 P CH OCH CI W NaH " -O CH3 Alkyl - CH HCinr H ) 1 --25 3 ,OCH3 3 CH Alkyl C2 H 5 CH(OC2Hs)2 iHe/H 20 CH-OC2H5 H N Alkyl--- CO + CHO H2N Y Alkyl \/\/ N\FOH POBr3 (Xllc) Al k y I Br Formula Scheme D
Bt < 3 fiCIL CH30CHC12 Br Mm C HO 1) NH2OH 2) Ac20 Br ffCN 1 ) HCI/C,HSOH 2) NH3 \//NHHCl C2H5OHC 81 " u Br NH2 + OHC NaOCH3 CH3OH (slid) 8 r oN3 Formula Scheme E
Alkyl mC N Alkyl V l 2) H OH Alkyl CH ,pNH OHC Alkyl C - Br NH2 + OHC \/ &verbar; NaOCH3 + CH30H (XIIe) Alkyl Formula Scheme F
Br 93 TiCIz, HCI, Br Mm CHO I Q)3-PQ-CH20CH C1o NaH Br HC(O C2H 5)3 II 8F3-O(C H ) Br H 5{;/;{;35 NC-Alkyl 20 CH(OC2H5)2 I)HCI/C,OH r H /H20 s I2)NH3 CH OC2Hg HCIHN Br I Br C + C -Alkyl CHO H2N NaOCH3 CH3OH (XlIf) B r Alkyl -- N The term "straight-chain alkyl group containing 1 to 7 carbon atoms" used in this specification means methyl, ethyl, n-propyl, n-nutyl, n-pentyl, n-hexyl and nheptyl. The term "straight-chain alkoxy group containing I to 7 carbon atoms" means methoxy, ethoxy, n-propoxy, n-butoxy, n-pentyloxy, n-hexyloxy and n heptyloxy. The term "straight-chain alkanoyloxy group containing 2 to 7 carbon atoms" means acetoxy n-propionyloxy, n-butyryloxy, n-valeryloxy, n-hexanoyloxy and n-heptanoyloxy.
The invention also includes electro-optical apparatus containing as optically active pyrimidine of formula I in liquid crystalline condition or containing a crystalline mixture of one or more optically active pyrimidine derivatives and nematic substances.
The following Examples illustrate the process provided by the present invention: Example 1.
1.9 g of 2 - [4' - (+) - 2" - methyl - 1" - butylphenyl] - 5 - (4 bromophenyl) - pyrimidine are heated at reflux for 21 hours in 50 ml of dimethylformamide with 2.5 g of copper-(I) cyanide (content 70%). After cooling, the mixture is stirred up with 25 ml of 10% aqueous ethylendiamine solution and subsequently extracted with methylene chloride. The extract is again washed with aqueous ethylenediamine solution and then several times with water until neutral.
The crude product obtained after evaporation is chromatographed on 150 g of silica gel with toluene/1% acetone. There are obtained firstly traces of starting material and then fractions containing pure 2 - [4' - (+) - 2" - methyl - 1" butylphenyl] - 5 - (4 - cyanophenyl) - pyrimidine.
The starting material can be prepared as follows: A solutoin of 15 g of l-(4-bromophenyl)-2-methoxyethylene in 150 ml of ethyl orthoformate is added dropwise at 00--50C to 5 g of boron trifluoride etherate in 200 ml of ethyl orthoformate. The mixture is stirred overnight, the mixture reaching room tempera.ure. The mixture is diluted with ether and washed with soda solution and then with water until neutral. The crude product obtained after evaporation yields, after recrystallisation from hexane, 4-bromophenyl-malonic triethyl monomethyl tetraacetal.
In order to partially hydrolyse the foregoing tetraacetal, 4.5 g thereof are dissolved in 10 ml of ethanol, treated with 0.5 ml of water and 1 drop of concentrated sulphuric acid, stirred overnight at 50"C and then worked-up in the usual manner. There is thus obtained crude 2-(4-bromophenyl)-3-ethoxyacrolein which is used in the next step in crude form.
To a sodium methylate solution prepared from 0.7 g of sodium in 25 ml of methanol are added firstly 2.5 g of crude 2-(4-bromophenyl)-3-ethoxyacrolein in 20 ml of methanol and then 2.4 g of 4 - (+) - 2' - methyl - 1' - butylbenzamidine hydrochloride. The mixture is heated at reflux overnight. Subsequently, the solvent is distilled off partially, the residue is treated with water and acidified with dilute hydrochloric acid. The precipitate is filtered off, washed thoroughly with water and ether and dried. The crude 2 - [4" - (+) - 2" - methyl - 1" - butylphenyl] - 5 (4 - bromophenyl) - pyrimidine is used in the process without further purification.
The following compounds can be manufactured in an analogous manner: 5 - [4' - (+) - 2" - methyl - 1" - butylphenyl] - 2 - (4 - cyanophenyl) pyrimidine, 5 - [4' - (+) - 3" - methyl - 1" - pentylphenyll - 2 - (4 - cyanophenyl) pyrimidine, 5 - [4' - (+) - 4" - methyl - 1" - hexylphenyl] - 2 - (4 - cyanophenyl) pyrimidine, 5 - [4' - (+) - 5" - methyl - 1" - heptylphenyl] - 2 - (4 - cyanophenyl) pyrimidine, 5 - [4' - (+) - 2" - methyl - 1" - butyloxyphenyl] - 2 - (4 - cyanophenyl) pyrimidine, 5 - [4' - (+) - 3" - methyl - 1" - pentyloxyphenyl] - 2 - (4 - cyanophenyl) - pyrimidine, 5 - [4' - (+) - 4" - methyl - 1" - hexyloxyphenyl] - 2 - (4 - cyanophenyl) pyrimidine of melting point 1210--1220C and clearing point 238.50C 5 - [4' - (+) - 5" - methyl - 1" - heptyloxyphenyl] - 2 - (4 - cyanophenyl) pyrimidine, 2 - [4' (+) - 3" - methyl - 1" - pentylphenyl] - 5 - (4 - cyanophenyl) pyrimidine, 2 - [4' - (+) - 4" - methyl - 1" - hexylphenyl] - 5 - (4 - cyanophenyl) - pyrimidine, 2 - [4' - (+) - 5" - methyl - 1" - heptylphenyl] - 5 - (4 - cyanophenyl) pyrimidine, 2 - [4' - (+) - 2" - methyl - 1" - butyloxyphenyl] - 5 - (4 - cyanophenyl) pyrimidine, 2 - [4' - (+) - 3" - methyl - I " - pentyloxyphenyl] - 5 - (4 - cyanophenyl) pyrimidine, 2 - [4' - (+) - 4" - methyl - 1" - hexyloxyphenyl] - 5 - (4 - cyanophenyl) pyrimidine and 2 - [4' - (+) - 5" - methyl - 1" - heptyloxyphenyll - 5 - (4 - cyanophenyl) - pyrimidine.
Example 2.
4.2 g of 4 - [5 - [4' - (+) - 2" - methyl - 1" - butyloxyphenyl] - 2 pyrimidyl] - benzoic acid amine are left at reflux for 1 hour while stirring in a mixture of 200 ml of ethylene chloride and 2.5 ml of phosphorus oxychloride. The mixture, diluted with ether, is washed with 2-N sodium hydroxide and then neutral with water. The organic phase is dried over sodium sulphate and evaporated to give 5 - [4' - (+) - 2" - methyl - 1" - butyloxyphenyl] - 2 - (4 cyanophenyl) - pyrimidine which is filtered through a short silica gel column and subsequently recrystallised from methylene chloride/methanol; melting point 149.90C; clearing point 233.8"C.
The starting material can be prepared as follows: Dry hydrochloric acid gas is passed while stirring at OOC for 3 hours into a solution of 88.6 g of methyl 4-cyanobenzoate in 190 ml of benzene and 70 ml of methanol. The mixture is left to stand at 5 C for 5 days and the separated imidoether is then filtered off. 178 g of this crude imidoether are suspended in 300 ml of methanol and the suspension is cooled to ca --400C, treated with 130 g of liquid ammonia and shaken at 70"C for 24 hours in an autoclave. After cooling the mixture to room temperature and discharging the ammonia, the crystallised-out product is filtered off under suction, the crystals are washed with hexane and dried overnight at 500C in a water-jet vacuum, there being obtained 4-amidinobenzoic acid amide hydrochloride.
46.07 g of 1 - [4' - (+) - 2" - methyl - I " - butyloxyphenyl] - 2 methoxyethylene are added dropwise to a solution, cooled in an ice-bath, of 2 ml of boron trifluoride etherate in 500 ml of ethyl orthoformate and the mixture is subsequently stirred at room temperature. After dilution with ether, extraction with I-N sodium hydroxide and water, drying over sodium sulphate and evaporation of the organic phase, there is obtained 4 - (+) - 2' - methyl - 1' butyloxyphenyl - malonic triethyl monomethyl tetraacetal.
7.33 g of 4 - (+) - 2' - methyl - 1' - butyloxyphenyl - malonic triethylmonomethyl tetraacetal are stirred overnight at 500C under nitrogen in 20 ml of ethanol with 0.72 ml of water and 2 drops of concentrated sulphuric acid. The mixture is diluted with ether and shaken out with aqueous sodium carbonate solution to separate the acidic (+) - 2 - methyl - butyloxyphenyl - malonaldehyde, which results as a byproduct, from neutral 2 - [4 - (+) - 2' - methyl - I ' butyloxyphenyll - 3 - ethoxyacrolein.
4.46 g of 2 - [4 - (+) - 2' - methyl - 1' - butyloxyphenyl] - 3 - ethoxyacrolein, 3.63 g of the aforementioned 4-amidinobenzoic acid amide hydrochloride and 0.0254 mol of sodium methylate (obtained by dissolving 0.584 g of sodium metal in methanol) are suspended in 250 ml of methanol and stirred overnight at room temperature under nitrogen. The yellow suspension is subsequently filtered under suction, washed with a small amount of ethanol and, for further purification, suspended in 1.4 litres of ether. The suspension is washed with water and again filtered. There is obtained difficultly soluble 4 - [5 - [4' - (+) - 2" - methyl - 1" butyloxyphenyl] - 2 - pyrimidinyl] - benzoic acid amide.
The following optically active pyrimidine derivatives can be manufactured in an analogous manner: 5 - [4' - (+)- 2" - Methyl - 1" - butylphenyll - 2 - (4 - cyanophenyl) pyrimidine, 5 - [4' - (+) - 3" - methyl - 1" - pentylphenyl] - 2 - (4 - cyanophenyl) pyrimidine, 5 - [4' - (+) - 4" - methyl - l"-hexylphenyl]- 2 - (4 - cyanophenyl) pyrimidine, 5 - [4' - (+) - 5" - methyl - 1" - heptylphenyl] - 2 - (4 - cyanophenyl) pyrimidine, 5 - [4' - (+) - 3" - methyl - 1" - pentyloxyphenyl] - 2 - (4 - cyanophenyl) pyrimidine, 5 - [4' - (+) - 4" - methyl - 1" - hexyloxyphenyl] - 2 - (4 - cyanophenyl) pyrimidine of melting point 1210-l220C and clearing point 238.5"C, and 5 - [4' - (+) - 5" - methyl - 1" - heptyloxyphenyl] - 2 - (4 - cyanophenyl) pyrimidine.
Example 3.
2.0 g of 5 - [4' - (+) - 2" - methyl - 1" - butyloxyphenyl] - 2 - (4 bromophenyl) - pyrimidine are heated at reflux for 30 hours with 3.15 g of cooper (I) cyanide in 100 ml of dimethylformamide. The mixture is cooled, 50 ml of 10% aqueous ethylenediamine solution are added thereto and the resulting mixture is stirred for a short period and then extracted with methylene chloride. The organic extract is again shaken with 30 ml of ethylene-diamine solution and then washed with water until neutral. The crude concentrate is chromatographed on silica gel with toluene/1% acetone. Recrystallization of the pure fractions from methanol/methylene chloride gives 5 - [4' - (+) - 2" - methyl - 1" - butyloxyphenyl] - 2 - (4 - cyanophenyl) - pyrimidine of melting point 149.50C and clearing point 233.5"C.
The starting material can be prepared as follows: 2.4 g of p-bromobenzamidene hydrochloride, obtained from p-bromobenzonitrile in the usual manner, are added to a solution of 0.7 g of sodium in 20 ml of methanol and then treated (as described in Example 2) with 2.5 g of crude 2 [4 - (2 - methylbutyloxy)phenyl] - 3 - ethoxyacrolein. The mixture is heated overnight at reflux, the solvent is subsequently distilled off partially and the residue is treated with ether. After acidification with dilute hydrochloric acid, the precipitate obtained is filtered off, washed thoroughly with water and ether and finally dried. The crude 5 - [4' - (+) - 2" - methyl - 1" - butyloxyphenyll - 2 (4 - bromophenyl) - pyrimidine is used in the process without further purification.
The following optically active pyrimidine derivatives can be manufactured in an analogous manner: 5 - [4' - (+) - 2" - Methyl - chloride. The extract is again washed with aqueous ethylenediamine solution and then several times with water until neutral. The crude product obtained after evaporation is chromatographed on 150 g of silica gel with toluene/1% acetone.
There are obtained firstly traces of starting material and then fractions containing pure 2 - (4 - n - hexylphenyl) - 5 - (4 - cyanophenyl) - pyrimidine. After recrystallisation from acetic ester, the product has a melting point of 121.5"C and a clearing point of 250"C.
The starting material can be obtained as follows: A solution of 15 g of l-(4-bromophenyl)-2-methoxyethylene in 150 ml of ethyl orthoformate is added dropwise at 00--50C to 5 g of boron trifluoride etherate in 200 ml of ethyl orthoformate. The mixture is stirred overnight and reaches room temperature. The mixture is then diluted with ether and washed firstly with soda solution and then with water until neutral. The crude product obtained after evaporation yields 4-bromophenyl-malonic triethyl monomethyl tetraacetal after recrystallisation from hexane.
In order to partially hydrolyse the foregoing acetal, 4.5 g thereof are dissolved in 10 ml of ethanol, the solution is treated with 0.5 ml of water and 1 drop of concentrated sulphuric acid and the mixture is stirred at 500C overnight and then worked-up in the usual manner. There is thus obtained crude 2-(4-bromophenyl)-3ethoxyacrolein which is used in the crude form.
To a sodium mcthylate solution prepared from 0.7 g of sodium in 25 ml of methanol are added firstly 2.5 g of crude 2-(4-bromophenyl)-3-ethoxyacrolein in 20 ml of methanol and then 2.4 g of 4-n-hexylbenzamidine hydrochloride. The mixture is heated to reflux overnight. Subsequently, the solvent is distilled off partially, the residue is treated with water and acidified with dilute hydrochloric acid. The resulting precipitate is filtered off, washed thoroughly with water and ether and dried. The crude 2-(4-n-hexylphenyl)-5-(4-bromophenyl)-pyrimidine of melting point 152.50-1560C is used in the process without further purification.
The following compounds were prepared in an analogous manner: Melting point Clearing point 2-(4-Ethylphenyl)-5 167Cl 67.50C -(4-cyanophenyl)-pyrimidine 2-(4-n-Propylphenyl)-5-(4cyanophenyl)-pyrimidine 167"C 278.50-2790C 2-(4-n-Butylphenyl)-5-(4-cyanophenyl)-pyrimidine 138.50C 2660-266.50C 2-(4-n-Pentylphenyl)-5-(4cyanophenyl)-pyrimidine 131.5"C 262.5 263 C 2-(4-n-Heptylphenyl)-5-(4cyanophenyl)-pyrimidine 121.5"C 245"--245.5"C Example B.
1.5 g of 5 - n - pentyl - 2 - (4' - bromo - 4 - biphenylyl- - pyrimidine are heated at reflux for 22 hours with 2.5 g of copper-(l) cyanide (content 70%) in 50 ml of dimethylformamide. After cooling, 25 ml of 10% aqueous ethylenediamine solution are added and, after stirring for a short time, the mixture is extracted with methylene chloride. The organic extract is shaken with a further 25 ml of ethylenediamine solution and then washed until neutral. The crude concentrate is chromatographed on silica gel with toluene/1% acetone. Recrystallisation of the pure fractions from ethyl acetate yields 5 - n - pentyl - 2 - (4' - cyano - 4 biphenylyl)- primidine of melting point 123.50--1240C and clearing point 204.5-2050C.
The starting material can be obtained as follows: 34.5 g of 4-bromobiphenyl in 164 ml of methylene chloride are treated at ca 2"C with 60.6 g of titanium tetrachloride. At the same temperature there are added dropwise over a period of 40 minutes 20.7 g of dichloromethyl methyl ether. The cooling means is removed and the mixture is left to stir at room temperature for 21 hours. The mixture is poured on to ice and the product is extracted with ether in the usual manner. Chromatography on silica gel using benzene for the elution gives firstly unreacted starting material and then 4'-bromo-4-biphenylaldehyde.
From 17.5 g of 4'-bromo-4-biphenylaldehyde and 4.4 g of hydroxylamine hydrochloride in 35 ml of methanol and 70 ml of pyridine there is obtained, after boiling under reflux, crude oxime, which is converted into the nitrile by heating for 15 hours in acetic anhydride. The mixture is concentrated as much as possible on a rotary evaporator. The residue is poured on to ice and dilute sodium hydroxide and the product is isolated with ether in the usual manner. After treatment with hexane, the 4'-bromo-4-cyanobiphenyl melts at ca 1500C.
Gaseous hydrochloric acid is passed into a mixture of 5.6 g of 4'-bromo-4cyanobiphenyl and 1 g of absolute ethanol in 25 ml of toluene until the mixture becomes saturated. After stirring for 3 days at room temperature, the precipitate is filtered off and washed with toluene. The residue is suspended while still moist in 5 ml of absolute ethanol and the suspension is treated with ca 1.3 g of ammonia in the form of a 10% ethanolic solution. After stirring for 3 days at room temperature, the precipitated 4'-bromo-4-biphenylamide hydrochloride is separated, washed with ether and dried.
5.8 g of n-pentyl-malonic tetraacetal are stirred at room temperature overnight in 10 ml of ethanol with 0.75 ml of water and 1 drop of concentrated sulphuric acid.
The mixture is then diluted with ether, extracted with sodium carbonate solution, washed neutral and evaporated.
1.42 g of the thus-obtained crude 2-n-pentyl-3-ethoxyacrolein are dissolved in a sodium ethylate solution (obtained from 580 mg of sodium in 40 ml of ethanol) and treated with 2.6 g of the aforementioned 4'-bromo-4-biphenylamidine hydrochloride. The mixture is stirred at room temperature for 3 days. After some of the solvent has been distilled off, water is added and the mixture is extracted with chloroform in the usual manner. Upon crystallization from ethanol, there is obtained 5 - n - pentyl - 2 - (4' - bromo -4 - biphenylyl) - pyrimidine in the form of needles of melting point 137"C and clearing point 197"C.
The following compounds were obtained in an analogous manner: 5 - n - Propyl - 2 - (4' - cyano - 4 - biphenylyl) - pyrimidine; melting point 125.60C; clearing point 275.7"C; 5 - n - butyl - 2 - (4' - cyano - 4 - biphenylyl) - pyrimidine; melting point 1120C; clearing point 262"C; 5 - n - hexyl - 2 - (4' - cyano - 4 - biphenylyl) - pyrimidine; melting point 108"C; clearing point 245"C; and 5 - n - heptyl - 2 - (4' - cyano - 4 - biphenylyl) - pyrimidine; melting point 110"C; clearing point 241.50C; WHAT WE CLAIM IS: 1. Optically active pyrimidine derivatives of the general formula
wherein the symbol Z represents a group of the formula CII2)n - or HCII2)nO in which n stands for an integer of I to 4 and each of the symbols X represents a nitrogen atom and each of the symbols Y represents =CH-- ot each of the symbols Y represents a nitrogen atom and each of the symbols X represents CII-.
2. 5 - 14' - (+) - 2" - Methyl - 1" - butylphenyll - 2 - (4 - cyanophenyl) pyrimidine and its optical antipode.
3. 5-[4' - (+) - 3" - Methyl - 1" - pentylphenyl] - 2 - (4 - cyanophenyl) pyrimidine and its optical antipode.
4. 5 - [4' - (+) - 4" - Methyl - I" - hexylphenyl] - 2 - (4 - cyanophenyl) pyrimidine and its optical antipode.
5. 5 - [4' - (+) - 5" - Methyl - I" - heptylphenyl] - 2 - (4 - cyanophenyl) pyrimidine and its optical antipode.
6. 5 - [4' - (+) - 2" - Methyl - 1" - butyloxyphenyl] - 2 - (4 - cyanophenyl) - pyrimidine and its optical antipode.
7. 5 - [4' - (+) - 3" - Methyl - I " - pentyloxyphenyl] - 2 - (4 cyanophenyl) - pyrimidine and its optical antipode.
8. 5 - [4' - (+) - 4" - Methyl - 1" - hexyloxyphenyl] - 2 - (4 - cyanophenyl) - pyrimidine and its optical antipode.
**WARNING** end of DESC field may overlap start of CLMS **.

Claims (41)

**WARNING** start of CLMS field may overlap end of DESC **. firstly unreacted starting material and then 4'-bromo-4-biphenylaldehyde. From 17.5 g of 4'-bromo-4-biphenylaldehyde and 4.4 g of hydroxylamine hydrochloride in 35 ml of methanol and 70 ml of pyridine there is obtained, after boiling under reflux, crude oxime, which is converted into the nitrile by heating for 15 hours in acetic anhydride. The mixture is concentrated as much as possible on a rotary evaporator. The residue is poured on to ice and dilute sodium hydroxide and the product is isolated with ether in the usual manner. After treatment with hexane, the 4'-bromo-4-cyanobiphenyl melts at ca 1500C. Gaseous hydrochloric acid is passed into a mixture of 5.6 g of 4'-bromo-4cyanobiphenyl and 1 g of absolute ethanol in 25 ml of toluene until the mixture becomes saturated. After stirring for 3 days at room temperature, the precipitate is filtered off and washed with toluene. The residue is suspended while still moist in 5 ml of absolute ethanol and the suspension is treated with ca 1.3 g of ammonia in the form of a 10% ethanolic solution. After stirring for 3 days at room temperature, the precipitated 4'-bromo-4-biphenylamide hydrochloride is separated, washed with ether and dried. 5.8 g of n-pentyl-malonic tetraacetal are stirred at room temperature overnight in 10 ml of ethanol with 0.75 ml of water and 1 drop of concentrated sulphuric acid. The mixture is then diluted with ether, extracted with sodium carbonate solution, washed neutral and evaporated.
1.42 g of the thus-obtained crude 2-n-pentyl-3-ethoxyacrolein are dissolved in a sodium ethylate solution (obtained from 580 mg of sodium in 40 ml of ethanol) and treated with 2.6 g of the aforementioned 4'-bromo-4-biphenylamidine hydrochloride. The mixture is stirred at room temperature for 3 days. After some of the solvent has been distilled off, water is added and the mixture is extracted with chloroform in the usual manner. Upon crystallization from ethanol, there is obtained 5 - n - pentyl - 2 - (4' - bromo -4 - biphenylyl) - pyrimidine in the form of needles of melting point 137"C and clearing point 197"C.
The following compounds were obtained in an analogous manner: 5 - n - Propyl - 2 - (4' - cyano - 4 - biphenylyl) - pyrimidine; melting point 125.60C; clearing point 275.7"C; 5 - n - butyl - 2 - (4' - cyano - 4 - biphenylyl) - pyrimidine; melting point 1120C; clearing point 262"C; 5 - n - hexyl - 2 - (4' - cyano - 4 - biphenylyl) - pyrimidine; melting point 108"C; clearing point 245"C; and 5 - n - heptyl - 2 - (4' - cyano - 4 - biphenylyl) - pyrimidine; melting point 110"C; clearing point 241.50C; WHAT WE CLAIM IS: 1. Optically active pyrimidine derivatives of the general formula
wherein the symbol Z represents a group of the formula CII2)n - or HCII2)nO in which n stands for an integer of I to 4 and each of the symbols X represents a nitrogen atom and each of the symbols Y represents =CH-- ot each of the symbols Y represents a nitrogen atom and each of the symbols X represents CII-.
2. 5 - 14' - (+) - 2" - Methyl - 1" - butylphenyll - 2 - (4 - cyanophenyl) pyrimidine and its optical antipode.
3. 5-[4' - (+) - 3" - Methyl - 1" - pentylphenyl] - 2 - (4 - cyanophenyl) pyrimidine and its optical antipode.
4. 5 - [4' - (+) - 4" - Methyl - I" - hexylphenyl] - 2 - (4 - cyanophenyl) pyrimidine and its optical antipode.
5. 5 - [4' - (+) - 5" - Methyl - I" - heptylphenyl] - 2 - (4 - cyanophenyl) pyrimidine and its optical antipode.
6. 5 - [4' - (+) - 2" - Methyl - 1" - butyloxyphenyl] - 2 - (4 - cyanophenyl) - pyrimidine and its optical antipode.
7. 5 - [4' - (+) - 3" - Methyl - I " - pentyloxyphenyl] - 2 - (4 cyanophenyl) - pyrimidine and its optical antipode.
8. 5 - [4' - (+) - 4" - Methyl - 1" - hexyloxyphenyl] - 2 - (4 - cyanophenyl) - pyrimidine and its optical antipode.
9. 5 - [4' - (+) - 5" - Methyl - I " - heptyloxyphenyl] - 2 - (4
cyanophenyl) - pyrimidine and its optical antipode.
10. 2 - [4' - (+) - 2" - Methyl - 1" - butylphenyl] - 5 - (4 - cyanophenyl) pyrimidine and its optical antipode.
11. 2 - [4' - (+) - 3" - Methyl - 1" - pentylphenyl] - 5 - (4 - cyanophenyl) - pyrimidine and its optical antipode.
12. 2 - [4' - (+) - 4" - Methyl - I" - hexylphenyl] - 5 - (4 - cyanophenyl) - pyrimidine and its optical antipode.
13. 2 - [4' - (+) - 5" - Methyl - 1" - heptylphenyl] .5 -(4 - cyanophenyl) - pyrimidine and its optical antipode.
14. 2 - [4' - (+) - 2" - Methyl - 1" - butyloxyphenyl] - 5 - (4 cyanophenyl) - pyrimidine and its optical antipode.
15. 2 - [4' - (+) - 3" - Methyl - I " - pentyloxyphenyl] - 5 - (4 cyanophenyl) - pyrimidine and its optical antipode.
16. 2 - [4' - (+) - 4" - Methyl - I " - hexyloxyphenyl] - 5 - (4 cyanophenyl) - pyrimidine and its optical antipode.
17. 2 - [4' - (+) - 5" - Methyl - I " - heptyloxyphenyl] - 5 - (4 cyanophenyl) - pyrimidine and its optical antipode.
18. A process for the manufacture of the optically active pyrimidine derivatives of formula I given in claim 1, which process comprises (a) reacting a compound of the general formula
ClH3 X' C2Hs C H-Z \// \ Halogen (Il) x = wherein the symbols X, Y and Z have the significance given in claim 1, with copper-(I) cyanide, sodium cyanide or potassium cyanide, or (b) for the manufacture of optically active pyrimidine derivatives of formula I in which each of the symbols X represents =CH-- and each of the symbols Y represents a nitrogen atom, dehydrating a compound of the general formula
wherein the symbol Z has the significance given in claim 1, or (c) for the manufacture of optically active pyrimidine derivatives of formula I in which each of the symbols X represents a nitrogen atom and each of the symbols Y represents =CH-- dehydrating a compound of the general formula
wherein the symbol Z has the significance given in claim 1, the starting materials of formulae II, III and IV being used in optical active or racemic form and, when a racemic starting material of formula II, III or IV is used, a resulting race mate being separated into the optical antipodes.
19. A process according to claim 18, wherein a compound of formula II in which each of the symbols X represents =CH-- and each of the symbols Y represents a nitrogen atom us used as the starting material.
20. A process according to claim 18 or claim 19, wherein a compound of formula 11, III or IV in which the symbol Z represents a group of the formula CH2(n or CH2)O wherein n stands for 1 is used as the starting material.
21. A process according to any one of claims 18 to 20 inclusive, wherein a compound of formula 11 is reacted with copper-(I) cyanide.
22. A process for the manufacture of the optically active pyrimidine derivatives of formula I given in claim 1, substantially as hereinbefore described with reference to any one of Examples 1 to 3.
23. An optically active pyrimidine derivative of formula I given in claim 1, when manufactured by the process claimed in any one of claims 18 to 22 inclusive or by an obvious chemical equivalent thereof.
24. A liquid crystalline mixture for electro-optical purposes which contains one or more optically active pyrimidine derivatives of formula I given in claim 1 and nematic substances.
25. A liquid crystalline mixture according to claim 24 which contains one or more of the optically active pyrimidine derivatives of formula I given in claim 1 and one or more compounds of the general formula
wherein the symbol Re represents a straight-chain alkyl group containing 2 to 8 carbon atoms, a straight-chain alkoxy group containing 4 to 7 carbon atoms, a straight-chain alkanoyloxy group containing 2 to 8 carbon atoms or a straight-chain alkylcarbonate group containing 2 to 11 carbon atoms, and/or one or more compounds of the general formula
wherein the symbol R7 represents a straight-chain alkyl group containing 4 to 7 carbon atoms, or a straight-chain alkylcarbonate group containing 2 to 11 carbon atoms, and/or one or more compounds of the general formula
wherein the symbol R8 represents a straight-chain alkyl group containing 4 to 8 carbon atoms, a straight-chain alkoxy group containing 5 to 8 carbon atoms, a straight-chain alkanoyloxy group containing 2 to 8 carbon atoms or a straight chain alkylcarbonate group containing 3 to 11 carbon atoms, and/or one or more compounds of the general formula
wherein the symbol Re represents a straight-chain alkyl group containing 4 to -8 carbon atoms, a straight-chain alkoxy group containing 4 to 8 carbon atoms, a straight-chain alkanoyloxy group -containing 4 to 9 carbon atoms, or a straight-chain alkylcarbonate group containing 4 to 11 carbon atoms and n stands for I or 2, and/or one or more trans-cinnamic acid esters;of the general formula
wherein the symbol R10 represents a straight-chain alkyl group containing 1 to 8 carbon atoms, and/or one or more compounds of the general formula
wherein one of the symbols R1, and R12 represents a cyano group and the other represents a straight-chain alkyl group containing 3 to 9 carbon atoms, a straight-chain alkoxy group containing 2 to 9 carbon atoms or a straight-chain alkanoyloxy group containing 2 to 9 carbon atoms, and/or one or more compounds of the general formula
wherein each of the symbols X represents a nitrogen atom and each of the symbols Y and Z represents =CH-- or each of the symbols Y represents a nitrogen atom and each of the symbols Y and Z represents =CH-- or each of the symbols Z represents a nitrogen atom and each of the symbols X and Y represents =CH-- and one of the symbols R1 and R2 represents cyano and the other represents a straight-chain alkyl group containing 1 to 7 carbon atoms, a straight-chain alkoxy group containing 1 to 7 carbon atoms or a straight-chain alkanoyloxy group containing 2 to 7 carbon atoms.
26. A liquid crystalline mixture according to claim 24 or claim 25 which contains p-[(p-n-propylbenzyliden)amino] benzonitrile, p-[(p-n-butylbenzyliden) amino]benzonitril, p-[(p-n-hexylbenzyliden)amino]benzonitrile and 5 - [4' - (+) 2" - methyl - 1" - butyloxyphenyll - 2 - (4 - cyanophenyl) - pyrimidine.
27. A liquid crystalline mixture according to claim 24 or claim 25 which contains p-n-butylbenzoic acid p'-cyanophenyl ester, p-n-pentylbenzoic acid p'cyanophenyl ester, p-n-hexylbenzoic acid p'-cyanophenyl ester, p-n-heptylbenzoic acid p'-cyanophenyl ester, 5-n-pentyl-2-(4-cyanophenyl)-pyrimidine, 5-nheptyl-2-(4-cyanophenyl)-pyrimidine and 5 - [4' - (+) - 2" - methyl - I " - butyloxyphenyl] - 2 - (4 - cyanophenyl) - pyrimidine.
28. A liquid crystalline mixture according to claim 24 or claim 25 which contains 4 - pentyl - 4' - cyanobiphenyl, 4 - pentyloxy - 4' - cyanobiphenyl and 5 - [4' - (+) - 2" - methyl - I" - butyloxyphenyll - 2 - (4 - cyanophenyl) - pyrimidine.
29. A process for the preparation of liquid crystalline mixtures, which process comprises mixing one or more of the optically active pyrimidine derivatives of formula I given in claim I with nematic substances.
30. A process according to claim 29, wherein one or more of the optically active pyrimidine derivatives of formula I given in claim I is/are mixed with one or more compounds of one or more of formulae V, Vl, VII, VIII, IX, X and XI given in claim 25.
31. A process according to claim 29 or claim 30, wherein p-[(p-n propylbenzyliden)amino]benzonitrile, p-[(p-n-butylbenzyliden)amino]benzonitrile, p-(p-n-hexylbenzyliden)amino]-benzonitrile and 5 - [4' - (+) - 2" methyl - 1" - butyloxyphenyl] - 2 - (4 - cyanophenyl) - pyrimidine are mixed.
32. A process according to claim 29 or claim 30, wherein p-n-butylbenzoic acid p '-cyanophenyl ester, p-n-pentylbenzoic acid p'-cyanophenyl ester, p-nhexylbenzoic acid p'-cyanophenyl ester, p-n-heptylbenzoic acid p'-cyanophenyl ester, 5-n-pentyl-2-(4-cyanophenyl)-pyrimidine, 5-n-heptyl-2-(4-cyanophenyl)pyrimidine and 5 - [4' - (+) - 2" - methyl - 1" - butyloxyphenyll - 2 - (4 cyanophenyl) - pyrimidine are mixed.
33. A process according to claim 29 or claim 30, wherein 4-pentyl-4'cyanobiphenyl, 4-pentyloxy-4'-cyanobiphenyl and 5 - [4' - (+) - 2" - methyl - 1" - butyloxyphenyll - 2 - (4 - cyanophenyl) - pyrimidine are mixed.
34. An electro-optical apparatus containing an optically active pyrimidine derivative of formula I given in claim tin liquid crystalline condition.
35. An electro-optical apparatus according to claim 34 containing an optically active pyrimidine derivative as set forth in any one of claims 2 to 17 in liquid crystalline condition.
36. An electro-optical apparatus containing a liquid crystralline mixture as set forth in any one of claims 24 to 28 inclusive.
37. An optically active pyrimidine of formula I substantially as described herein with reference to the Examples.
38. A process according to claim 18 substantially as described herein and exemplified.
39. A liquid crystalline mixture according to claim 24 substantially as described herein.
40. A process according to claim 29 substantially as described herein.
41. An electro-optical apparatus according to claim 34 and claim 36 substantially as described herein.
GB10692/78A 1977-03-18 1978-03-17 Optically active pyrimidine compounds liquid crystal compositions containing them and their use in electrooptical apparatus Expired GB1594085A (en)

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