DD282237A5 - MIXTURES OF LATERAL BRANCHED MESOGENIC AND PROMESOGENIC CHIRAL NON-TRACEMIC SUBSTANCES - Google Patents

Abstract

The invention relates to the use of mesogenic and promesogenic nonracemic chiral substances in crystalline-liquid mixtures, in particular those with twisted structure, in optoelectronic components for the modulation of light and for the representation of numbers, characters and moving and still images. According to the invention, novel mesogenic and promesogenic nonracemic chiral substances of general formula I can be used in mixtures for optoelectronic components, in particular displays based on liquid crystals. Formula (I) {liquid crystals; Electro-optics; displays; nematic, smectic, chiral, mesogenic, promesogenic, substituted benzene derivatives; mixtures}

Description

in which

3 R ^J

R ¹ , R ² = R-, RO-, RCOO-, ROOC-, '.ialogen, HC-, SQ! -, F ₃ C-,

3 R = R

R ⁴ = -F, -Cl, -Or ", -OOC-R, -OOC-Cf (OCH ₃ ) -phenyl-

Q ⁵ - (with Z ¹ subst.) - 1,4-phenylene-Z ²

A ¹ , A ² , A ³ , A ⁴ (same or different) = 1,4-phenylene; 1,4-cyclohexylene; wherein one of the rings is also a phenylene ring in which one or more CH groups are replaced by N; a 1,4-cyclohexylene ring in which one or two non-adjacent CH ₂ groups are replaced by O and / or S; with Z ³ substit. 1,4-phenylene; Thiadiazole-2,5-diyl; 1,4-bicyclo (2.2.2) octylene; Piperidine-1,4-diyl can be

such as

Q ¹ , Q ² , Q ³ , Q ⁴ = single bond, -CH ₂ O-, -OCH ₂ -, -COO-, -OOC-, -CH ₂ CH ₂ -, -CsC-, substit. ethylene, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH ₂ -

Q ⁵ = -OOC -, - OCH ₂ -

Z ¹ , Z ² , Z ³ = halogen, -OCH ₃ , -CH ₃ -CN, -OC ₂ H ₅ , -H

Z ² = HaIOgOn ^ -CN ₁ -OC _n H _{2n +} VC _n H _{2n + 1} with η = 3 to 18

R, R ', R "= straight-chain or single-branched alkyl chain having 1 to 18 C atoms, in which any CH ₂ group is represented by -N-alkyl-phenyl- or 1,4-cyclohexylene, and in which also one or two are not adjacent CH ₂ groups may be replaced by O, S, -COO-, -C =C-,

p, q, r, s = 0.1

p + q + r + s = 1 to 3

such as

C * = nonracemic asymmetric carbon atom

mean,

is contained as a mixture component in addition to chiral or non-chiral substances.

Field of application of the invention

The invention relates to crystalline-liquid mixtures for optoelectronic components for modulating the light and for displaying numbers, characters and moving and still images.

Characteristic of the known solutions

Liquid crystals have already been proposed for a larger number of applications. Particular importance is attached to such types of liquid crystals which have a twisted structure, in particular the twisted nematic phases (cholesteric liquid crystals) and twisted smectic C phases (C * phases), both of which occur in chiral substances. Both twisted nematic and C * phases can be used in optoelectronic displays (E. Kaneko: Liquid Crystal TV Displays: Principles and Applications of Liquid Crystal Displays, KTK Scientific Publ. Tokyo 1987). Depending on the desired field of application displays of different types are used, which in turn requires substances with very specific properties. There are no single substances which even meet approximately the practical requirements with respect to temperature range of the mesophases, optical, electro-optical, dielectric and rheological properties. Therefore, in practice, only mixtures are used, which may consist of up to about 15 different components. The properties of the mixtures depend on the properties of the components used. In order to be able to optimally adapt the mixtures to specific requirements, a large number of individual components with very different properties are required. In order to find substances with altered properties, new classes of substances are constantly being included in liquid crystal chemistry. Particularly in the field of chiral substances, there is still a great need for mesogenic and promesogenic compounds of different molecular structure.

Object of the invention

The aim of the invention are mixtures with crystalline-liquid properties, in particular those with twisted structure, which are suitable for applications in optoelectronics.

Explanation of the essence of the invention

The object of the invention is to find suitable for the mixtures mentioned new chiral components. According to the invention, liquid-crystalline mixtures for optoelectronic components contain at least one mesogenic or promesogenic nonracemic chiral compound of the general formula I.

R ¹ KA ¹ Q ¹ ) - (- A ² O ² -) - / оУ (0 ³ -L ³ ) - (0 ⁴ -L ⁴ -) - R ² \ - 'P ^ч - -q yy ^ч rs

: -Г і-с *. ⁴

where R ¹ , R ² = R, RO, RCOO, ROOC, halogen, WC, SC '-: -, FC-,

3 '

t> ^J - τ? -

R ⁴ is -F, -Cl, -OR, -OOC-R ', -00C-c "" (0C ^T i _o) -phonyl-

-Q ⁵ - (with Z ¹ subst.) - l, 4-phenylene-Z ²

A ', A ² , A ³ , A ⁴ (same or different) = 1,4-phenylene; 1,4-cyclohexylene; wherein one of the rings is also a phenylene ring in which one or more CH groups are replaced by N; a 1,4-cyclohexylene ring in which one or two non-adjacent CH ₂ groups are replaced by O and / or S; with Z ³ substit. -1,4-phenylene, thiadiazole-2,5-diyl; 1,4-bicyclo (2.2.2) octylene; Piperidine-1,4-diyl can be

such as

Q ¹ , Q ² , Q ³ , Q ⁴ = single bond, -CH ₂ O-, -OCH ₂ -, -COO-, -OOC-, -CH ₂ CH ₂ -, -C = C-, substit. ethylene, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH ₂ -

Q ⁶ = -00C -, - OCH ₂ -

Z ', Z ² , Z ³ = halogen, -OCH ₃ , -CH ₂ , -OC ₂ H ₆ , -H

Z ² = halogen, K-CK-OC _n H _{2n +} I ₁ -C _n H _{2n +} I with η = 3 to 18

R, R ', R "= straight-chain or single-branched alkyl chain having 1 to 18 carbon atoms, in which any CH ₂ group can be replaced by -SCHNR-прпепуІ- or 1,4-cyclohexylene,

and in which also one or two non-adjacent CH ₂ groups can be replaced by O, S, -COO-, -C =C-.

ρ, q, r, s = 0,1

p + q + r + s = 1 to 3

such as

С · = nonracemic asymmetric carbon atom

mean,

as mixture components in addition to chiral or non-chiral substances.

The compounds according to the invention are chemically and thermally stable. Most of the new compounds have crystalline-liquid properties and the transition temperatures are in favorable temperature ranges. The substances show good miscibility with other typical crystalline-liquid substances and their mixtures. By adding the new compounds, chiral properties are induced in mixtures, whereby in the case of nematic phases or smectic C phases, twisted structures are formed.

The substances according to the invention can be prepared by the following general scheme:

PCI, R ² - U

The following tables list examples of the new substances. Where:

he = crystalline-solid

N * = chirally nematic (cholesteric)

S = smectic

is = isotropic-liquid

embodiments example 1

(R) -1 -hydroxyethylhydroquinone-bis-H-n-octyloxybenzoate) 1/1

In an Erlenmeyer flask, 2.0 mmol (1.23 g) of acetylhydroquinone-bis-n-octyloxybenzoate is dissolved in 15 ml of absolute THF.

With stirring and protective gas ⁰ C 0.1 mmol (27,6mg) (S) (O at -tetrahydro-3,3-diphenyl-1-methyl-1H, 3H-pyrrolo (c 1.2) 1.3 , 2) oxazaborol in 2m! absol. THF added. To the resulting solution, while stirring at 0 ⁰ C 2.0 mmol BH ₃ THF dissolved in lOmlabsol. THF, dropped for 10 minutes. After warming to room temperature, stir for an additional hour and then carefully hydrolyze with 2 ml of cold 2N HCl. After dilution with 50 ml of ether, the organic phase is separated and washed three times with 10 ml of 2N HCl, with 10 ml of saturated NaHCC solution and with 10 ml of water. The ehterische solution is dried over Na ₂ SO ₄ and the solvent distilled off on a rotary evaporator. Recrystallize from petrol (b.p.

60-85 ° C) gives Verbiondung 1/1 in a yield of 95% of theory.

1а] ²² Б78 = + 2.53 ° (с = 3.16, acetone) Enantiomeric purity: 71% ee Conversion behavior: he 58 N * 84is

Example 2

(S) -I-chloroethylhydroquinone-bis-M-n-hexyloxybenzoate) 2/2

2.0mmol (1.12g) of compound 1/2 are dissolved in 10ml absolute. CCI _{4 was} dissolved and added dropwise with stirring and cooling at 0 ° C. to a suspension of 2.0 mmol (0.42 g) of PCI5 in 5 ml of absolute CCI ₄ within 10 minutes after stirring for 12 hours at 0 to 5 ° C. with exclusion of humidity, the solution with 10 ml of CCI is diluted ₄ and filtered to remove small PCU residues. on a rotary evaporator, the solvent and the resulting POCI ₃ at 30 ⁰ C is distilled off. recrystallization of the crude product from petroleum (bp. 60 to 85 ° C) gives compound 2/2 in 80% yield of theory Conversion behavior: 57 N * 88is

Table 1

X XC H-CH ₃ R cr S _ Ν · is AsH Verb. HO п-С ₈ Н ₁₇ О- • 58 · _ 84 · 43.1 1.1 но П-СдНізО- • 74 · 96 · 1.2 но п-С _в Н _1Э - • 20- - ft 3.1 Cl RC ₈ H ₁₇ O- • 62- - 80 · 24.6 2.1 Cl п-СбНізО- • 57- 88 · 2.2 CH ₃ O nC ₈ H ₁₇ O- • 70- 86 · 3.1 CHjCOO- nC _e H ₍₇ O- • 52- 48) · 3.2

-COOnC _e H ₁₇ O-

56 ·

37.9

Δ ₈ Η = enthalpy of fusion in kJ / mol

Example 3

(R) -1-Methoxy-hydroxy-hydroquinone-bis (4-n-octyloxybenzoate) 3/1 1.0 mmol (0.61 g) of compound 1/1 are dissolved in 15 ml of absolute. Dioxane with 3.0 mmol (0.7 g) freshly precipitated, dried Ag ₂ O and 5.0 mmol (0.71 g) CH ₃ I and shaken under exclusion of light and moisture for 24 hours at room temperature. The mixture is then heated to 50 ^° C. for 8 hours. After dilution of the solution with 50 ml of ether, the residue is filtered off with suction and washed twice with 10 ml of ether. The solutions are combined and the solvent is distilled off on a rotary evaporator. Recrystallization of the crude product from η-hexane gives the ether 3/1 in a yield of 75%.

 Transformation behavior: he 70 N * 86is

Example 4

By adding the substances according to the invention to other crystalline liquid substances, chiral liquid crystal phases with a twisted structure are formed. This will be shown with reference to the following compilation, in which a non-chiral substance A is provided with additives of various substances according to the invention.

Comparative substance A:

_N _ / °° 12 ^Η 25

AsH - ί % A : he 50 Sc 86 S _A 98 is se " 78 50,2kJ / mol 95 he • 81.5 conversions: 95 • 48 • 78 95 • 49 • 71 2.1 90 • 50 • - 1.1 90 • 47.5 - _ 3.3 90 • 49 _ 2.1 • 48 1.1 3.3

N · 96-95-95-83 ·

IS

91 86

Claims (1)

Mixtures of laterally branched mesogenic and promesogenic chiral nonracemic substances, for optoelectronic components, characterized in that at least one mesogenic or promesogenic nonracemic chiral compound of the general formula I as mixture component R ¹ KA ¹ Q ¹ ) -CA ² Q ² -) - / oV (Q ³ -A ³ ) - (Q ⁴ -A ⁴ -) -R ^{2 h} i: - ^r4