CA1082706A - Optically active compounds - Google Patents

Optically active compounds

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CA1082706A
CA1082706A CA297,450A CA297450A CA1082706A CA 1082706 A CA1082706 A CA 1082706A CA 297450 A CA297450 A CA 297450A CA 1082706 A CA1082706 A CA 1082706A
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Prior art keywords
pyrimidine
methyl
cyanophenyl
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straight
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French (fr)
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Arthur Boller
Marco Cereghetti
Hanspeter Scherrer
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F Hoffmann La Roche AG
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F Hoffmann La Roche AG
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • 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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  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Liquid Crystal Substances (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

ABSTRACT

Optically active pyrimidine derivatives of the general formula (I) wherein the symbol Z represents a group of the formula -(CH2)n- or -(CH2)n-O- in which n stands for an integer of 1 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 -CH-and their preparation.

The compounds of formula I are valuable components in liquid crystalline mixtures, particularly in combination with nematic components and are thus utilizable for electro-optic purposes.

Description

- 2 -, ., The present invention relates to optically active compounds. More paLticularly, the invention is concerned with optically active pyrimidine derivatives, 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 ~H3 ~ / \ ~ CN (I) wherein the symbol Z represents a group of the formula -(CH2)n- or -(CH2)n-~ in which n stands for an integer of 1 to 4 and each of the symbols X represents a nitrogen atom and each of the symbols Y represents -C~- or each of the symbols Y represents a nitrogen atcm and each of the syr~ols X represents -CH-.
' 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 ;r Cot/18.1.1978 .

I ~ - 3 - ~ '7Q~Y

undersoes 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 ~nown 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 ~he 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-l"-butylphenyl]-2-(4-cyanophenyl)--pyrimidine, r~25 5-[4'-(+)-3"-methyl-l'Y-pentylphenyl]-2-(4-cyanophenyl)--pyrimidine, , ~. . . - ~

, ~ , 4 ~ t7V ~

5-[4'-(+)-4"-methyl-1'~-hexylphenyl]-2-(4-cyanophenyl)--pyrimidine, 5-[4'-(+)-S"-methyl-l"-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-t4'-(+)-4"-methyl-1"-hexyloxyphenyl]-2-(4-cyanophenyl)--pyrimidine, 5-[4'-(+)-5"-methyl-1"-heptyloxyphenyl~-2-~4-cyanophenyl)--pyrimidine, 2-[4'-(+)-2"-methyl-1"-butylphenyl]-5-(4-cyanophenyl)--pyrimidine, 2-[4'-(+)-3"-methyl-1"-pentylphenyl3-5-(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-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. Especia71y preferred optically .. . .

!

'~ ' ' ' ' .

. ~ 7V~
active pyrimidine derivatives of this invention are those in which each of the symbols X represents -CH- 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 C2H5- CH - Z ~ / \ ~ Halogen (II) , 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 -CH- and each of the symbols Y represents a nitrogen atom, dehydrating a compound of the general formula ~H5- CH-Z ~ \ ~ C - NH2 (III) , wherein the sym~ol 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

,~ .

~. ;

- 6 ~ 7~

represents a nitrogen atom and each of the symbols Y represents -CH-, dehydrating a compound of the general formula C2H5-~H-Z ~ N ~ CH=N-OH (IV) , wherein the symbol Z has the significance given earlier, the starting materials of formulae II, III and I~ 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.

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, acetonitrile and the like. 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 oxy-chloride, phosphorus pentoxide, thionyl chloride, acetic -.:

7(~
anhydride and the like. The dehydration can be carried out in an inert organic solvent such as a hydrocarbon or halogenated hydrocarbon and the like, if necessary in the presence of a base such as sodium acetate, pyridine, triethanolamine and the S like. 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. Althoush 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 lS 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 fractional crystallisation of the resulting salts.

The compounds of formulae II, III and IV used as the _ starting materials are novel and also form part of the present invention.

, '70~
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.

9- ~V~'~70~;

Formula Scheme I

A~3CHo
3 P - CH 2 CH 3 Cl ~NaH

A~3 / C H - OC H 3 C(C2 H5)3 BF3 O~C2H5)2 ~OCH3 A~ CH N C ~Br CH(C2 H5 )2 H~) / H 2 ¦ 1) HCI/C2 H50H :-~2)NH3 A~ ,~CH-OC2H5 HClHN~ ~Eir yc H 3 A~ ~a, (IIa) ~ - :
N

- 10- ~ 0 ~ormula Scheme II

B r ~3 C H0 NaH

~CH-OCH3 HC(OC2H5~3 E3F3- O~C2H 5)2 /OCH3 .
Br~3 CH NC~3A

2 S ) 2 ,H~/H20 ¦ 2 50H
~2 3NH3 Br~ 4~ 2HS HCI HN~

\/
NaOCH3 Br ~ \~3A (IIb) : ' . ' ~ ' ~,'- '' - - ' :. , ~ : ~ . ................. . -: , . .,' .

: ~ j'' ~ ' . .

7~3 Formula Scheme III

A ~ C H O

1 NaH

A~ ~CH-OCH3 NC ~ ~

HC10C2H5)3 . -1 ) HCIIC H OH
BF3 0(C2 H5)3 2 5 ~OCH3 A~ CH(OC2H5~2 H N~ 0~2H5 H / H20 ¦ N H3/Pressure A~ ~CHOC2H5 HCI HN~ ~C

CHO t H2N NH2 ~/CH3 A ~C N h~ C N H2 ( III ) .., . , . .

, :
.
: . . ' ~,;, ~ ' , :

7~

- Formula Scheme IV

HOCH2~CHo J~NaH

~ ~CH-OCH3 HOCH2~ CH

2 5 ) 3 3F3 0(C2H5)2 CH
HOCH2~ C\ C2 H5 C H t~C 2 H 5 )2 ~ CHOC2H5 HCI- HN

H O C.H 2~ C H O ~ ~A
\/
¦NaOCH3 J~ C~30H

HOCH2~ \>~--A

,~

"'' 70~

Formula Scheme IV (continued) OHC ~ N ~ A

¦ NH20H- HCl t Pyridin HO-N=CH ~ \ ~ A ~IV) The optically active pyrimidine derivatives of formula I
are conveniently used in the form of mixtures with nematic substances; for example, with compounds of the general formula S R6 ~ CH ~ ~ CN ~V) , wherein the sy~bol 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 - 10 alkanoyloxy group containins 2 to 8 carbon .

. .
: . , ` : ,., :

7~
atoms or a straight-chain alkylcarbonate group containing 2 to 11 carbon atoms, and/or with compounds of the general formula R7~=CH~CN (VI) , wherein the symbol R7 represents a straight-chain alkyl group containing 4 to 7 carbon atoms or a straight-chain al~yl-carbonate group containing 2 to 11 carbon atoms, 10 and/or with compounds of the general formula R~ ~ C00 ~ CN (VII) 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 alkyl-carbonate group containing 3 to 11 carbon atoms, 20 and/or with compounds of the general formula R9~C~ (VIII) .. ~ ~ -' .
. . .

- 15 ~ 1~7V~

, wherein the symbol Rg 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 alkyl-carbonate 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 10 ~ CH-CH-C00 ~ CN (IX) , wherein the symbol Rlo represents a straight-chain alkyl group containing 1 to 8 carbon atoms, and~or with compounds of the general formula R~ R~ (X) , wherein one of the symbols Rll 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 carbor. atoms, and/or with compounds of .he general formula ,"r -: . :
'' ' :
:" . ' ~:

- 16 - i ~

Rl ~ ~ ~ / \ ~ R2 (XI) Z X=Y

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 -C~ 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.

The optically active pyrimidine derivatives of formula I
are present in nematic mixtures for electro-optical purposes in a weig~t 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 S and 30 percent by weight and especially between about 5 and 15 percent by weight.

Examples of preferred mixtures are the following, the percentages being expressed as mol percentages:

12.7% of p-~(p-n-Propylbenzyliden)amino]benzonitrile, 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"-butyloxyphenyl]-2-(4-cyanophenyl)-pyrimidine;
clearing point 72.2C;

11.2~ of p-n-butylbenzoic acid p'-cyanophenyl ester, 12.5%
of p-n-pentylbenzoic acid p'-cyanophenyl ester, 16.0% of p-n-- -hexyl-benzoic acid p'-cyanophenyl ester, 17.2% of p-n-heptyl-benzoic acid p'-cyanophenyl ester, 11.9~ of 5-n-pentyl-2-(4--cyanophenyl)-pyrimidine, 23.2~ of 5-n-heptyl-2-(4-cyanophenyl)--pyrimidine and 7.3% of 5-[4~-~f)-2ll-methyl-l~-butyloxyphenyl]
-2-(4-cyanophenyl)-pyrimidine; clearing point Z5.6C; and 55.7% of 4-pentyl-4'-cyanobiphenyl, 33.2% of 4-pentyloxy--4'-cyanobiphenyl and 6.4% of 5-~4'-(~)-2"-methyl-1"-butyloxy-phenyl]-2-(4-cyanophenyl)-pyrimidine; clearing point 60.3C.

The compounds of formula XI hereinbefore are novel and can be obtained, for example, by reacting à compound of the seneral formula R3 ~ z X X ~ y ~ (XII) , wherein one of the symbols R3 and R4 represents a straight-chain alkyl group containing 1 to 7 carbor. atoms, a straight--chain alkoxy group containing 1 to 7 carbon .~

- .' , , . ' ' ~ , , .

- 18 _ ~ 7U 6 atoms or a straight-chain alkanoyloxy group containing 2 tG 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 descri~ed earlier in connection with the reaction of a compound of formula II with copper-(I) cyanide, sodium cyanide or potassium cyanide.

lOThe preparation of the compounds of formula XII can be effected according to the disclosure in the unexamined German Patent Publication (DOS) No 2641724 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 1 to 7 carbon atoms and the other represents a bromine atom.

.

,~

.

. : ~ , , .

- . : . . .

- 1 9 ~ 7 F~rmula Scheme A

A I k y I ~ CH O

~3-P -CH20CH3CI
~NaH

~ /fH-OCH3 AI kyl ~ ~CH

HC(OC2H5)~ , BF3 O(C2H5)2 1 ~ ~OCH3 ~ .

AlkY1~3cH OC2H5 NC~Br I H/H20 ¦ t)HCI/C21~50H
~2)N H3 ,~ ~CH -OC2H5 HCI HN~
A l k y l--~,=J~ C\ C H OH 2 N

\/
¦ N aOC H3 J~CH301~

A I ~yl ~ \~3Br (XIIa) N

.
. . . ~ ---,..

- 20- 1~7()6 Formula Scheme B

~r ~CH0 103- P -CH20C H3Cl ~NaH

3 r ~3 C H - OCH3 ( 2 533 BF3-0(C2H5J2 ~ ~ /OC H3 8 r ~3 C H N C ~AIkyl 2 5 ) 2 H~'IH 2 1 1 )HCIJC2H50H
~2 )NH~ :

,~ CHOC2H5 HCI HN ~
3 r ~=~C + ~C ~ Alkyl CHO H2N \=./
\/
. NaOCH j ar ~ \)~,3Alkyl (XIIb) ' - 2~ 706 Formula Scheme C

A l k y l ~CHO

¦ G~3 P -CH20CH3CI
~ NaH

All~yl ~ ~CH-OCH3 2 5 ) 3 3F3- O(C2 H5)2 ~OCH3 Alkyl ~-CH OC2H
CH(OC2H5~2 ¦ H IH20 .

A I k y l ~ ~ H - O C 2 H 5 H 2 N ~ ' Y

A l ky l ~ ~--OH

¦ POar3 (~IIc~ A I k y I ~ ~NN~--B~

. .

~Z7(~6 Schema D

~r ~3 ¦ TiC14 C H 30C HCl~

Br ~CHO

~ NH20H
2J Ac20 B r ~3CN

1 ) H Cl / C2H5 0 H
2) NH3 ,~ ~NH HCl C2H50HC~
e,~c C-Alkyl NH2 ~ OHC
/
yNaOCH3 ~ CH30H

X I 1 d B r ~(/ 3--Alky l - ~ ~
- - .

; ~ ' ' , . : ~, '' , , -Schema E

Al kyl ~C N

1 ) HCI/C2H50H
2) NH3 A l k y l ~ ~ C H3 0 H C~

\~C H3 Xll e Alkyl ~ 3Br . . . . . .... .
~ : , . . : ., 7()~

Schema F

B r ~3 TjCIL
l C H30C H C12 Br~3CHo ¦ 0 3 - PG>-CH 20C H 3Cl0 J, NaH

Br ~ ~CH-OCH3 ¦ C~O 2 5)3 3 2 5~2 OCH
B r ~3 CH NC -Alkyl CH~C2HS~2 ¦11HCIIC2H50H

e r ~3 + ~ -Alkyl YN aOC H3 ~ r ~ Alkyl ~ ! ' ' - 25 ~ 7V~

The term "straight-chain alkyl group containing 1 to 7 carbon atoms" used in this specification means methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl and n-heptyl. The term "straight-chain alkoxy group containing 1 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 following Examples illustrate the process provided by the present invention:

Example 1 1.9 g of 2-~4'-~+)-2"-methyl-1"-butylphenyl]-5-(4-bromo-phenyl)-pyrimidine are heated at reflux for 21 hours in S0 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 ethylenediamine 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 solution of 15 g of 1-(4-bromophenyl)-2-methoxyethylene in 150 ml of ethyl orthoformate is added dropwise at 0-5C to
5 g of boron trifluoride etherate in 200 ml of ethyl ortho-formate. The mixture is stirred overnight, the mixturereaching room temperature. The mixture is diluted with ether and washed with soda solution and then with water until neutral.
The crude product obtained after evaporation yields, a'ter recrystallisation from hexane, 4-bromophenol-malonic tetra-acetal. ~082706 ~ `

.~.

.
. .
- ~
.. . . . ~ .
.

~0~'~7(~
. 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 50C and then wor~ed-up in the usual manner.
There is thus obtained crude 2-(4-brGmophenyl)-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. ~he precipitate is filtered off, washed thoroughly with water and ether and dried. The crude 2-[4"-(+)-2"-methyl-1"-butyl-phenyl]-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"-~ethyl-1"-butylphenyl]-2-(4-cyar.ophenyl)--pyrimidine, 5-[4'-(+)-3"-methyl-1"-pentylphenyl]-2-(4-cyanophenyl)--pyrimidine, 5-[4'-(+)-4"-methyl-1"-hexylphenyl]-2-(4-cyanophenyl)--pyrimidine, 5-[4'-(+)-5"-methyl-1"-heptylpnenyl]-2-(4-cyanophenyl)--pyrimidine, ,.. ,, . ~ , . ~ . , ... , :
~ ' ' ' .

: ' ' , ' :

.

- 2~ -7Vf~i 5-[4'-(+)-2"-methyl-1"-butyloxvphenyl]-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 121-122C and clearing point 238.5C, 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"-~utyloxyphenyl]-5-(4-cyanophenyl)--pyrimidine, 2-~4'-(+)-3"-methyl-1"-pentyloxyphenyl]-5-(4-cyanophenyl)--pyrimidine, 2-[4'-(+)-4"-methyl-1"-hexyloxyphenyl]-5-(4-cyanophenyl)--pyrimidine, and 2-[4'-(+)-5"-methyl-1"-heptyloxyphenyl]-5-(4-cyanophenyl)--pyrimidine.

Ex~mple 2 4.2 g of 4-/ 5-[4'-(+)-2"-methyl-1"-butyloxyphenyl]-2--pyrimidyl /-benzoic acid amide are left at reflux for 1 hour while stirring in a mixture of 200 ml of ethylene chloride and ., ' '.

' ~ (3~

2.5 ml of phosphorus oxychloride. The mixture, diluted with ether, is washed with 2-~ sodium hydroxide and then neutral with water. The organic phase is dried over sodium sulphate and evaporated to give 5-[4'-(+)-2"-methyl-l"-butyloxyphenyl]-S -2-(4-cyanophenyl)-pyrimidine which is filtered through a short silica gel column and subsequently recrystallised from methylene chloride/methanol; melting point 149.9C; clearing point 233.8C.

The starting material can be prepared as follows:

Dry hydrochloric acid gas is passed while stirring at 0C
for 3 hours into a soIution of 88.6 g of methyl 4-cyanobenzoate in l90 ml of benzene and 70 ml of methanol. The mixture is left to stand at 5C 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 -40C, treated with 130 g of liquid ammonia and shaken at 70C 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 drièd overnight at 50C in a water-jet vacuum, there being obtained 4-amidinobenzoic acid amide hydrochloride.

46.07 g of 1-[4'-(+)-2"-methyl-1"-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 ,~

- - 30 ~ 7~

room temperature. After dilution with ether, extraction with l-N sodium hydroxide and water, drying over sodium sulphate and evaporation of the organic phase, there is obtained 4-(+)-2'--methyl~ butyloxyphenyl-malonic tetraacetal.

7.33 g of 4-(+)-2'-methyl-1'-butyloxyphenyl-malonic tetraacetal are stirred overnight at 50C 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--l'-butyloxyphenyl]-3-ethoxyacrolein.

4.46 g of 2-[4-(+)-2'-methyl-1'-butyloxyphenyl]-3-ethoxy-acrolein, 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-rs- [4'-(+)-2"-methyl-1"--butyloxyphenyl]-2-pyrimidinyl_/-benzoic acid amide.

The following optically active pyrimidine derivati~-es can be manufactured in an analogous manner:

::. . . .
~.

~ . - 31 - ~ 7~

5-[4'-(+)-2"-Methyl-l"-butylphenyl]-2-(4-cyanophenyl)--pyrimidine, 5-[4'-(+)-3"-methyl-1"-pentylphenyl]-2-(4-cyanophenyl)--pyrimidine, ;5-[4'-(+)-4"-methyl-1"-hexylphenyl]-2-(4-cyanophenyl)--pyrimidine, 5-[4'-(+)-5"-methyl~ 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 121-122C and clearing point 238.SC, and 5-[4'-(+~-5"-methyl-1"-heptyloxyphenyl]-2-(4-cyanophenyl)--pyrimidine.

` .
Example 3 2.0 g of 5-~4'-(+)-2"-methyl-1"-butyloxyphenyl3-2-(4--bromophenyl)-pyrimidine are heated at reflux fGr 30 hours with 3.15 g of copper-(I) cyanide in 100 ml of dimethylIormamide.
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. Recrystallisation of the pure fractions from methanol/methylene chloride gives 5-[4'~ 2"-methyl-1"-butyl-. . .
. : ~
.'' "~ V~
oxyphenyl)-2-~4-cyanophenyl~-pyrimidine of melting point 149.5C
and clearing point 233.5C.

The starting material can be prepared as follows:

2.4 g of p-bromobenzamidine 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-t2-methyl-butyloxy)phenyl]-3-ethoxyacrolein. The mixture is heated overnight at reflux, the solvent is su~sequently 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"-butyloxy- -phenyl]-2-(4-bromophenyl)-pyrimidine is used in the process without further purification.

The following optically active pyrimidine derivati~es can be manufactured in an analogous manner:

5-[4'-(+)-2"-Methyl~ utylphenyl]-2-(4-cyanophenyl)--pyrimidine, 5-[4'-(+)-3"-methyl-1"-pentylphenyl]-2~(4-cyanophenyl)--pyrimidine, 5-[4'-(+)-4"-methyl-1"-hexylphenyl]-2-(4-cyanophenyl)--pyrimidine, 5-~4'-(+)-5l'-methyl-1"-heptylphenyll-2-(4-cyanophenyl)--pyrimidine, "

' . . ~ 33 ~ 1~ 7~

5-[4'-(+)-3"-methyl-1"-pentyloxyphenyl]-2-(4-cyanophenyl)--pyrimidine, 5 t4'-(+)-4"-methyl-1"-hexyloxyphenyl]-2-(4-cyanophenyl)--pyrimidine of melting point 121-122C and clearing point 238.5C, 5-[4'-(+)-5"-methyl-1"-heptyloxyphenyl]-2-(4-cyanophenyl)--pyrimidine, 2-[4'-(+)-2"-methyl-1"-butylphenyl]-5-(4-cyanophenyl)--pyrimidine, 2-~4'-(+)-3"-methyl-1"-pentylphenyl3-5-(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-1"-pentyloxyphenyl]-5-(4-cyanophenyl)--pyrimidine, 2-~4'-(+)-4"-methyl-1"-hexyloxyphenyl]-5-(4-cyanophenyl)--pyrimidine, and 2-[4'-(+)-5"-methyl-1"-heptyloxyphenyl]-5-(4-cyanophenyl)--pyrimidine.

The following Examples illustrate the preparation of the compounds of formula XI hereinbefore:

Exam~le A

,r 1.9 g of 2-(4-n-hexylphenyl)-5-(4-bromophenyl)-pyrimidine ''''"'`''~ : ~
": ~' ' ' ' ' .

, ,~ ' .

_ 34 _ 7~6 are heated at reflux for 21 hours in 50 ml of dimethylformamide with 2.5 g of copper-(I) cyanide (content 70~ fter cooling, the mixture is stirred with 25 ml of 10% aqueous ethylenediamine solution and subsequently extracted with methylene chloride.
The extract is again washed with aqueous ethylenedïamine 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 121.5C and a clearing point of 250C.

The starting material can be obtained as follows:

A solution of 15 g of 1-(4-bromophenyl)-2-methoxyethylene in 150 ml of ethyl orthoformate is added dropwise at 0-5C 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 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 50C overnight and then worked-up in the usual manner. There is thus obtained crude 2--(4-bromophenyl)-3-ethoxyacrolein which is used in the crude form.

.. .. . .
.
- , . .

- 35 ~ 7'0~

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-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-bromo-phenyl)-pyrimidine of melting point 152.5-156C is used in the process without further purification.

The following compounds were prepared in an analogous manner:

Melting point Clearing point 15 2-(4-Ethylphenyl)-5-(4-cyano-phenyl)-pyrimidine 167-167.5C 279-279.5C

2-(4-n-Propylphenyl)-5-(4--cyanophenyl)-pyrimidine167C 278.5-279C

2-(4-n-Butylphenyl)-5-(4-cya~o-phenyl)-pyrimidine 138.5C 266-266.5;C

2-(4-n-Pentylphenyl)-5-(4--cyanophenyl)-pyrimidine131.5C 262.5-263C

2-(4-n-Heptylphenyl)-5-(4--cyanophenyl)-pyrimidine121.5C 245-245.5C

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-(I) r cyanide (content 70%) in 50 ml of dimethylformamide. After ~: , ' , - 36 - i~ 7~

- 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)-pyrimidine of melttng point 123.5-124C and clearing point 204.5-205C.

The starting material can be obtained as follows:

34.5 g of 4-bromobiphenyl in 164 ml of methylene chloride are treated at ca 2C 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 l'eft 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 manne..
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 ,, . , : ., . ~ 37 ~ 1~27~ .

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'-brGmo-4-cyanobiphenyl melts at ca 150C.

Gaseous hydrochloric acid is passed into a mixture of 5.6 g of 4'-bromo-4-cyanobiphenyl and l 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 lO~
ethanolic solution. After stirring for 3 days at room temperature, the precipitated 4'-bromo-4-biphenylamidine hydro-chloride is separated, washed with ether and dried.

5.8 g of n-pentyl-malonic tetraacetal are stirred at room temperature overnight in lO 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-ethoxy-acrolein are dissolved in a sodium ethylate solution (obtainedfrom 580 mg of sodium in 40 ml of ethanol) and treated with 2.6 g of the aforementioned 4'-bromo-4-biphenylamidine hydro-chloride. The mixture is stirred at room temperature for 3 da~s. After some of the solvent has been distilled off, water is added and the mixture is extracted with chloroform in the usual manner. Upon crystallisation from ethanol, there is .
.
.

_ 33 - ~ 7~
.

obtained 5-n-pentyl-2-(4'-bromo-4-biphenylyl)-pyrimidine in the form of needles of melting point 137C and clearing point 197C~

The following compounds were obtained in an analogous manner:

5-n-2ropyl-2-(4'-cyano-4-biphenylyl)-pyrimidine; melting -point 125.6C; clearing point 275.7C;
5-n-butyl-2-(4'-cyano-4-biphenylyl)-pyrimidine; melting point 112C; clearing point 262C;
5-n-hexyl-2-(4'-cyano-4-biphenylyl)-pyrimidine; melting point 108C; clearing point 245C; and 5-n-heptyl-2-(4'-cyano-4-biphenylyl)-pyrimidine; melting point 110C; clearing point 241.5C.

.

Claims (26)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the manufacture of the optically active pyrimidine derivatives of the general formula:

(I) wherein the symbol Z represents a group of the formula -(CH2-n- or -(CH2)n-O- in which n stands for an integer of 1 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 -CH-, which process comprises (a) reacting a compound of the general formula (II) wherein the symbols X, Y and Z are as defined above, 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, de-hydrating a compound of the general formula (III) wherein the symbol Z has the significance given above, (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 (IV) wherein the symbol Z has the significance given above, 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.
2. A process according to claim 1, 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 is used as the starting material.
3. A process according to claim 1, wherein a compound of formula II, III or IV in which the symbol Z represents a group of the formula -(CH2)n- or -(CH2)n-O- wherein n stands for 1 is used as the starting material.
4. A process according to any one of claims 1 to 3 inclusive, wherein a compound of formula II is reacted with copper-(I) cyanide.
5. 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.
6. A liquid crystalline mixture for electro-optical purposes, 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 (V) 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 alkyl-carbonate group containing 2 to 11 carbon atoms, and/or one or more compounds of the general formula (VI) , 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 (VII) , 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 alkanoyl-oxy 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 (VIII) , wherein the symbol R9 represents a straight--chain alkyl group containins 4 to 8 carbon atoms, 2 straight-chain alkoxy group containing 4 to 8 carbon atoms, a straight-chain alkanoyl-oxy 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 one or more trans-cinnamic acid esters of the general formula (IX) , 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 (X) , wherein one of the symbols R11 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 (XI) , 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 X 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 a cyano group 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.
7. A liquid crystalline mixture according to claim 5 or claim 6 which contains p-[(p-n-propylbenzyliden)amino]benzo-nitrile, p-[(p-n-butylbenzyliden)amino]benzonitrile, p-[(p-n-hexylbenzyliden)amino]benzonitrile and 5-[4'-(+)-2"-methyl-1"-butyloxyphenyl]-2-[4-cyanophenyl)-pyrimidine.
8. A liquid crystalline mixture according to claim 5 or claim 6 which contains p-n-butylbenzoic acid p'-cyanophenyl ester, p-n-pentylbenzoic acid p'-cyanophenyl ester, p-n-hexyl-benzoic 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"-butyloxyphenyl]-2-(4-cyanophenyl)-pyrimidine.
9. A liquid crystalline mixture according to claim 5 or claim 6 which contains 4-pentyl-4'-cyanobiphenyl, 4-pentyl-oxy-4'-cyanobiphenyl and 5-[4'-(+)-2"-methyl-1"-butyloxyphenyl]-2-(4-cyanophenyl)-pyrimidine.
10. Optically active pyrimidine derivatives of the general formula (I) wherein the symbol Z represents a group of the formula -(CH2)n-or -(CH2)n-O- in which n stands for an integer of 1 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 repre-sents a nitrogen atom and each of the symbols X represents -CH-.
11. 5-[4'-(+)-2"-Methyl-1"-butylphenyl]-2-(4-cyano-phenyl)-pyrimidine and its optical antipode.
12. 5-[4'-(+)-3"-Methyl-1"-pentylphenyl]-2-(4-cyanophenyl)-pyrimidine and its optical antipode.
13. 5-[4'-(+)-4"-Methyl-1"-hexylphenyl]-2-(4-cyanophenyl)-pyrimidine and its optical antipode.
14. 5-[4'-(+)-5"-Methyl-1"-heptylphenyl]-2-(4-cyanophenyl)-pyrimidine and its optical antipode.
15. 5-[4'-(+)-2"-Methyl-1"-butyloxyphenyl]-2-(4-cyanophenyl)-pyrimidine and its optical antipode.
16. 5-[4'-(+)-3"-Methyl-1"-pentyloxyphenyl]-2-(4-cyanophenyl)-pyrimidine and its optical antipode.
17. 5-[4'-(+)-4"-Methyl-1"-hexyloxyphenyl]-2-(4-cyanophenyl)-pyrimidine and its optical antipode.
18. 5-[4'-(+)-5"-Methyl-1"-heptyloxyphenyl]-2-(4-cyanophenyl)-pyrimidine and its optical antipode.
19. 2-[4'-(+)-2"-Methyl-1"-butylphenyl]-5-(4-cyano-phenyl)-pyrimidine and its optical antipode.
20. 2-[4'-(+)-3"-Methyl-1"-pentylphenyl]-5-(4-cyano-phenyl)-pyrimidine and its optical antipode.
21. 2-[4'-(+)-4"-Methyl-1"-hexylphenyl]-5-(4-cyano-phenyl)-pyrimidine and its optical antipode.
22. 2-[4'-(+)-5"-Methyl-1"-heptylphenyl]-5-(4-cyano-phenyl)-pyrimidine and its optical antipode.
23. 2-[4'-(+)-2"-Methyl-1"-butyloxyphenyl]-5-(4-cyanophenyl)-pyrimidine and its optical antipode.
24. 2-[4'-(+)-3"-Methyl-1"-pentyloxyphenyl]-5-(4-cyanophenyl)-pyrimidine and its optical antipode.
25. 2-[4'-(+)-4"-Methyl-1"-hexyloxyphenyl]-5-(4-cyanophenyl)-pyrimidine and its optical antipode.
26. 2-[4'-(+)-5"-Methyl-1"-heptyloxyphenyl]-5-(4-cyanophenyl)-pyrimidine and its optical antipode.
CA297,450A 1977-03-18 1978-02-22 Optically active compounds Expired CA1082706A (en)

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