DD259873A1 - CRYSTALLINE-LIQUID MIXTURES - Google Patents

Abstract

The invention relates to the use of crystalline-liquid mixtures in optoelectronic components for the modulation of light and for the representation of numbers, characters and images. According to the invention, novel crystalline 3- and / or 9-substituted 1,5-diheterospiro- and 5,5! Undecanes of the general formula ## STR5 ## with X equi or different O, S in mixtures with one another and in mixtures with further crystalline-liquid as well as non-crystalline Liquid substances used in optoelectronic displays. formula

Description

R ¹ = H, CIi ₁ ,

in which

p2 " _π p5

R ³ = R ² and

cholesteryl,

R-

4 _

~ ^C m ^H 2rn + 1 »

= -COO-, -000-, -

ti

R ⁶ 'R

with R ⁶ , R ⁷ = H, CH ,,

ί ¹ , Cl or

CIT

m = 1-10 η = 0-2

mean,

in mixtures with each other and in mixtures with other crystalline-liquid and non-crystalline substances are used.

Field of application of the invention

The invention relates to novel crystalline-liquid mixtures for use in optoelectronic components, which serve as light valves and as displays for the representation of numbers, characters and figures in watches, computers, electronic devices and screens.

Characteristic of the known technical solutions

For some years, liquid crystals have been widely used in the manufacture of optoelectronic devices, which are reliable and have extremely low power consumption. Therefore, liquid crystal devices are particularly advantageous for all battery powered devices.

The displays are used for different purposes and must accordingly have different properties. There are ζ. 2. Over 15,000 crystalline liquid compounds (D.Demus, H. Dems, H. Zaschke, Liquid Crystalsin Tabellen, Leipzig 1974, Volume II, Leipzig 1984). However, none of these many compounds has anything close to the properties necessary for use in the optoelectronic devices. Therefore, only mixtures containing about 5 to 15 different components are used. The components influence their properties by their individual properties and their proportion in the mixture. In order to be able to influence mixtures in a targeted manner, new substances, which are supposed to belong to the most novel substance classes, are required time and again.

Object of the invention

The aim of the invention are optoelectronic components with a wide temperature range based on liquid crystals.

Explanation of the essence of the invention

The object of the invention are modified mixtures with high clearing temperatures and low birefringence. According to the invention, liquid-crystalline 3- and / or 9-substituted 1,5-diheterospiro [5,5] undecanes of the general formula

-ocx:

A B

R ¹ =

where R ~

R ² , R ² -Y- (CH ₂ ) _n - or -COOR ³ , R ⁴ . or -COOR ³ ,

the same or different O, S "H, CN,

H,. R ⁵ , R ⁵ O-, η

R ³ = R ² and YTW

\ '/

^r5

cholesteryl,

R ⁴ «R ⁵ , R

^{R = G} ra ^H

ra ^H 2rn-f

Y = -COO-, -00C-,

0 - C

» ^R7 = ^h »

^{or CIT}

m = 1-10

η = 0-2

mean,

in mixtures with each other and in mixtures with other crystalline-liquid and non-crystalline liquid substances in

optoelectronic displays used.

The substances are chemically and thermally stable and have very low values of birefringence Δη, which is advantageous for use in displays with a low angular dependence of the contrast.

The invention will be explained below with reference to 7 examples.

example 1

Substituted S-carbonyloxy-SS-subst.-i ^ -dioxaspiro-IB ^ J undecane of the general formula 5.

Synthesis scheme:

Ό- ^0Η

PCG

¹ O

HIGH,

COOEt

HIGH ₂ COOEt O-λ / COOEt

¹ OCIX

COOEt

1. 2 OH

2. 2H <5 0-r, COOH 0-COOH

CO

R ¹ - / ~~ V ^ Λ-COOH

R ² -OH

COOR '

embodiments

4- {4'-n-butyl-cyclohexyl) methyl-cyclohexanone [1.1]

The 4-subst. Cyclohexanones 1 were all obtained by oxidation of the cis-trans mixtures of corresponding cyclohexanols by means of PCC according to known methods ([J.C.Collins, N.W.Hess, F.J. Frank, Tetrahedron Lett. 1968, 33336]).

Thus, from 2.8 g (0.011 mol) of 4- (4'-n-butylcyclohexyl) methylcyclohexanol and 10 g (0.046 mol) of PCC in 30 ml of methylene chloride, after conventional work-up and two-fold fractional vacuum distillation 2.1 g (76, 4% of theory) the cyclohexanone 1.1.

Bp: 132-134 T / 0.027 KPa (cis-trans mixture)

9- (4'-n-butyl-cyclohexyl) -methyl-1,5-dioxaspiro [5.5] undecane-3-carboxylic acid [4.1] 2.5 g (0.01 mol) of 4- (4'-n-butyl) cyclohexyl) -methylcyclohexanone, 2.4 g (0.011 mol) of diethyl bis-hydroxymethylmalonate and 100 mg of p-toluenesulphonic acid are heated in 100 ml of benzene on a water separator until the end of the reaction. After cooling, washed with 5% NaHCO ₃ solution and H ₂ O, dried over sodium sulfate and the solvent was distilled off. The remaining crude oil [2.1] is saponified to [3.1] without further purification. For this purpose, it is refluxed with 2.24 g (0.04 mol) of powdered KOH for 4 hours in 40 ml of methanol and 2 ml of water. Subsequently, methanol is completely distilled off and the solid residue washed with a little ethyl acetate. Thereafter, slurried in 80 ml of ethyl acetate and cooled to -10 ⁰ C. At this temperature neutralize with 10% hydrochloric acid against Congo red indicator with vigorous stirring. The phases are immediately separated, the organic phase is washed with water and dried over Na ₂ SO ₄ . After removal of the solvent, 3.3 g (83.33% of theory) of crude acid 3.1, which is decarboxylated without further purification by heating to 150 ° C. in a vacuum of 0.27-0.4 kPa to 4.1. The product obtained is recrystallized from n-heptane.

Yield: 1.2 g (34.1% of theory, based on cyclohexanone 1.1)

Mp: 156-160 ⁰ C

9- (4'-n-butylcyclohexyl) -methyl-1 _/ 5-dioxaspiro [5.5] undecane-3-carboxylic acid 4 "-cyanophenyl ester [5.1] 0.28g (0.8 mmol) 9- (4'-n- Butylcyclohexyl) -methyl-1,5-dioxaspiro [5.5] undecane-3-carboxylic acid, 0.1 g (0.8 mmol) 4-cyanophenol, 0.3 g (1 mmol) of 10-dimethylaminopropyl-S-ethyl-carbodiimide methiodide and 50 mg of DMAP are dissolved in 10 ml of methylene chloride at room temperature and allowed to stand for 24 hours after vigorous stirring, diluted with 50 ml of methylene chloride, washed 3 × with 30 ml of H2O and once with 30 ml of 5% NaHCO3 solution, over Na ₂ SO ₄ and, after removal of the solvent from ethanol, fractionally crystallized to constant point in the clearing point. Yield: 0.3 g (82.8% of theory) after recrystallization

Hri Q)

I O ο W • ft • » • ( • * β ί I ιη ι ι ! t I I tn tn ι * ο CVl CO * _ [ in "\ tn • ι fr- 1 t I ! I I · " • τ- • τ · · CTi ο CO CM «CO ΛΟ < O τ ™ LfS tn in τ o OJ T " cn fr- ^ p j in in tn τ ™ cn I τ- in cn CO * ¹ ρ 9 • 0 T "* • I τ- O (Λ O tn I T-. α τ o VD , '' CO in τ- VD OJ τ CO O tn tn Ϊ Ι ο fr- CO CO V O t- V 117 Tv-V ο ιη · r- τ- VO τ- τ- in · O 127 • • • » • • O cn 108 * cn W • cn cn 0 W cn 8th C ^ O O in ι T "W in τ- I I τ- T- O O O VD O ^K cn τ- τ- Q Q from O fr- I X  G00 O VD O VD O CM W O CM O ' O) [O (OJ ι I Ξ! S t I I 1 1 jla! ^! O O O I .oj; η [oil η 6 ^s , I coji IfO] I / \ O

CM

in

OJ o

tn

tn

in

in

VjD «

in

CO

in

O 5

cn tn

cn

VD O

in

VD O

£ 3

tn

Where:

K = crystalline-liquid

S = smectic phase

N = nematic phase

I = isotropic-liquid

The numbers between the phases mean transformation temperatures in ⁰ C.

Example 2

S-Subst.-S-carbonyloxy-subst.-i ^ -dioxaspirotö.SIundecane of the general formula 10 Synthetic Scheme:

.COOEt .CH ₉ OH

/ LiAlH 8 /

.COOEt.

_R 8 _CH / LiAlH 2 _{} R} 8 _CH /

₆ COOEt CH ₂ OH

11

1) OH ^θ

2) Η®

.9

R ² -0H

C 0OR ² 10

Diethyl (4-n-butylcyclohexyl) -methyl-malonate [6.1]

To a hot Alkoholatiösung, prepared from 4,6g (0.2 mol) of sodium in 150 ml of molecular sieve-dried ethanol, 32 g (0.2 mol) of diethyl malonate are added dropwise. With constant reflux then 49g (0.21 mol) of 4-n-butylcyclohexylmethyibromide are added dropwise and heated under reflux for 20h. Subsequently, the main amount of the alcohol is distilled off while stirring while stirring. The deposited sodium bromide is dissolved after cooling in just required amount of ice water and the organic phase separated. After extracting the aqueous phase twice with ether, the organic phases are dried, the solvent is removed and the resulting crude oil is purified by distillation. Yield: 34.4 g (55% of theory) bp: 160-162 ° C / 0.16 kPa (cis-trans mixture)

2- (4-n-butylcyclohexyl) -methyl-propane-1,2-diol [7.1]

46.8 g ((0.15 mol) of diethyl (4-n-butylcyclohexyl) -methylmalonate are reduced with 9.5 g (0.25 mol) of lithium alanate in 300 ml of absolute ether at room temperature (water cooling). Dissolve the organic salts with 25% sulfuric acid, the organic phase is separated and the aqueous phase is extracted by ether three times The combined ether extracts are washed with water and 5% NaHCO ₃ solution and dried over Na ₂ S (Ii After distilling ether is obtained after single recrystallization from η-hexane 13g (38% of theory) crystalline liquid Diol 7.1 (K70S1111) A sample which has been recrystallised several times from η-hexane has the characteristic K71 S 115.51 3-n-IMonyl-1,5- dioxaspiro [5.5] undecane-9-carboxylic acid [9.2]

4.68 g (0.03 mol) of cyclohexane-1-carboxylic acid methyl ester, 6.67 g (0.033 mol) of 2-n-nonylpropane-1,3-diol and 250 mg of p-toluenesulfonic acid are heated in 100 ml of benzene on a water separator until the end of the Reaction. After cooling, washing with 2.5% NaHCO ₃ solution and water, drying over Na ₂ SO ₄ and'Removal of the solvent gives the crude Sn-nonyl-i ^ -Dioxaspirotö.Slundecan g-carboxylic acid methyl ester [8.2 ]. This is heated without further purification, together with 3.36 g (0.06 mol) of powdered KOH, 60 ml of methanol and 3 ml of H ₂ O for three hours under reflux. Subsequently, will

Methanol largely distilled off and the remaining white-yellow solid residue slurried after washing in a little ethyl acetate in 100 ml of ethyl acetate, cooled to 0 ° C to -10 ⁰ C, and neutralized while maintaining this temperature and stirring with 5% HCl against Congo Red. The free acid 9.2, after phase separation, extraction of the aqueous phase with 20ml of ethyl acetate,

Drying of the ethyl acetate extracts and distilling off the solvent as a rapidly crystallizing, light brown oil.

Recrystallization twice from n-heptane gives the uniformly melting acid 3.2.

Yield: 5.8 g (56.8% of theory)

Mp: 65-66 ° C

3-n-Nonyl-1,5-dioxaspiro [5.5] undecane-9-carboxylic acid 4 '- (5 "-n-heptyl-pyrimidyl-2) -phenyl ester [10.7]

0.27 g (0.8 mmol) of S-n-nonyl-LS-dioxaspiro IS. Ω-butanediol-carboxylic acid, 0.21 g (0.8 mmol) of 4- (5'-n-heptyl-pyrimidyl-2) -phenol,

0.3 g (ImMoI) of i-O-dimethylaminopropyU-S-ethylcarbodiimide-methiodide and 50 mg of DMAP are prepared as described for 5.1,

implemented.

After LUmkristallisation obtained 0.4 g (86.51% d.Th.) IO.7.

3- (4'-n-butylcyclohexyl) -methyl-9-n-pentyl-1,5-dio) caspiro [5.5] undecane [11.5]

0.75 g (0.0033 mol) of 2- (4'-n-butylcyclohexyl) -methyl-propane-1,3-diol, 0.5 g (0.003 mol) of 4-n-pentyl-cyclohexanone and 50 mg

p-Toluenesulfonic acid are heated in 50 ml of benzene on a water separator until the reaction is complete. After cooling, it is washed with 5% NaHCO ₃ solution and water, dried over Na ₂ SO ₄ and the solvent is distilled off. The oily residue is crystallized in MeOH / EtOH (2: 1). By repeated fractional crystallization from "the same solvent mixture to Klärpunktkonstanz to obtain the pure liquid crystalline isomers.

Yield: 0.63 g (55.55% of theory) after recrystallization

9- (4'-n-butylcyclohexyl) -methyl-3-n-nonyl-1,5-dioxaspiro [5.5] undecane [11.18]

1 g (0.004 mol) of 4- (4'-n-butylcyclohexyl) -methylcyclohexanone, 0.85 g (0.0042 mol) of 2-n-nonyl-propane-1,3-diol and 50 mg

p-Toluenesulfonic acid are reacted and worked up in 50 ml of benzene as described for 11.5.

After LUmkristallisation obtained 0.8 g (46.12% of theory) 11.18.

Table 2

" ⁸ OO * ⁰⁰ *

9.1 11-C ₄ H 10 * 1 nC ^ B

10.2 11-C ₄ E

10.3 n-C ^ i

9.2 11-C ₉ H ₁₉

10.4 HC ₉ H ₁₉

10.5 11-C ₉ H ₁₉

1006 HC ₉ H ₁₉

1007 11-C ₉ H ₁₉

10.8 HC ₉ H ₁₉

10.9 11-C ₀ HL _n .

-CH _n -

, CN

-Gholesteryl

^S 2 i ³ 1

.153-154. -. -. - -

74

.144 .158, 164 .207,5 _f

.124 - - (.100,5). .58 (. 33).

₆ 65-66 - - -

.87 »99 .109,5 0I3I

.76 - - .100.5 "101

.98 ~ - .101,5.

.96 .138,5 Choi.150

ο 76-77. (45.5) - -.

Table 3

R '

" ¹ B

11.1

CN

- / "" V-CN

-CH ₂ HQy-HC ₄ H ₉

11.13 n-C

11014 HC ₄ H ₉ -Q) -

11015 n-C.Hq-

11.16 HC ₅ H ₁₁ -

11.17 11-CcH _-10 -

11.18 HC ₉ H ₁₉

11.19 H-

CH,

CH,

CH,

CH,

-CH ₂ - -CH,

-CH ₂ -QhH-

. (12)

♦ 62.5 -

♦ 83. 94

♦ 95.5 -. 95.5 -

ο 84. (70) .119 (.104). 82, 170. 85 ·, 168.5. 82.5 ο 59. 99 .62. 70.5 .76 '. 84

oil

example

S-Subst.-ii-carbonyloxy-subst.-i ^ -dithia spiro [5.5] undecane of the general formula Synthetic scheme

CH ₂ OH

2 Tos-Cl pyridine

R ⁸ -CH

R ⁸ .-

1) (MH ₂ ) ₂ CS

/ CH ₂ -SH

-COOEt

- / V ~ Vc003t '

1, OH

2. H

R ⁸ ~ (^ ⁵ Y ~ Vc00H

15

R ² -0H

COOR '

Sn-Hexyl-i-dithiaspyrot S. slundecane-S-carboxylic acid ethyl ester [14] To a refluxing solution of 0.11 mole (18.6 g) of ethyl cyclohexane-1-carboxylate and 200 mg of p-toluenesulfonic acid in 300 ml Benzene is slowly added dropwise with stirring within one hour 19.2 g (0.1 mol) of 2-n-hexyl-propane-1,3-dithiol. The mixture is heated to boiling for an hour, cooled, washed with 100 ml of 5% NaHCO ₃ solution and 100 ml H ₂ O, dried over Na ₂ SO 4 and the solvent was distilled off on a rotary evaporator. The residue is distilled in a bulb tube.

Yield: 32.5 g (95% of theory)

Bp: 160-170 ° C / 10.7 Pa

3-n-Hexyl-1,5-dithiaspiro [5,5] undecane-9-carboxylic acid [15] 34,3g (0,1 MoDS-n-hexyl-i ^ -dithiaspiro ^ siudecane-g-carboxylic acid ethyl ester, 50ml H ₂ O and 44.8 g (0.8 mol) of KOH are heated to boiling point in methanol for about 30 minutes, the solvent is distilled off on a rotary evaporator, the residue is distilled off in approx.

Dissolved 1.51 of water and acidified with dilute HCl while cooling with ice. The resulting precipitate is filtered off with suction, washed neutral with water and recrystallized from benzene / n-hexane.

Yield: 28.3 g (90% of theory)

Mp: 126 ° C

S-n-hexyl-l-S-dithiaspiroIS ^ jundecan-g-carboxylic acid cholesteryl ester [16.11]

3.16 g (0.01 mol) of Sn-hexyl-1-dithiaspiroI-1-lundecane-g-carboxylic acid, 3.80 g (0.01 mol) of cholesterol, 100 mg of DMAP and 3.27 g (0.011 mol) of 10-dimethylaminopropyl O-S Ethylcarbodiimidmethiodid be in 50ml abs. Dissolved CH ₂ Cl ₂ and stirred for 12 h at room temperature. After working up and recrystallization from methanol / acetone, 5.2 g (75% of theory) of melting point and clear point pure product were obtained.

Table 4:

COOR '

R '

15. a-Cg 16.1 HC ₆ 16.2 HC ₆ 1 * 6.3 H-C. 16.4 H-Cg 16.5 HC _g 16 * 6 HC ₁ . ; ^H 13 ~ ^H > ^H 13 "O ⁿ " ^C 5 ^H 11 ; ^H 13 · - <§) - ^0G 4 ^H 9 i ^H 13 ^ ®> ~ ^C 5 ^H 11 ; ^H 13 -Jq) - ™ B ₁₃ -CH ₂ -QC ₄ H ₉ > ^H 13 - <O> - <OV ^C 6 ^H 13

-16.9 nC ₆ H ₁₃

16.10 H-C ^ H.-

ο

16.11 HC ^ PK ₀

-Cholesteryl ♦ 5

.126 »-

, 58 (B 47) -. 97 -

. (30)

, 81 - - "(29)

, 55.106 .122.3 *

.117- -

123

• 82 - - .163

, 86 .117,2 .133

, 95, 133, o 149

, 80 .159.5 Ch183

table

,8th

R ^c

-HC ₆ H ₁₃ -HC ₆ H ₁₃ -HC ₆ H ₁₃

-HC ₈ H ₁₇

CH,

, 22nd (17)

113

, <70 .B 113.5. ο ο 46.

Table 6:

R '

-GH,

_β Β 119

Example 4

S-cyano-S-subst.-S-carbonyloxy-subst.-i ^ -dioxaspirotB.BIundecane of the general formula

Synthesis scheme:

R ⁸ -CHT

GOOEt

HGHO K ₂ CO ₃

,8th

CN

R ⁸ -C ~CH _o 0H, ά

GOOEt

CN

RC-CH ₀ OH

CH ₂ OH

-COOEt

1 · OH 2 «H

19

R *

23

R ⁸

R ⁸ NC

-GOOH

-GOORr

2-n-hexyl-2-hydroxymethyl-cyanoacetic acid ethyl ester [18]

197 g (1 mol) of ethyl 2-n-hexyl cyanoacetate are mixed with 120 ml of 35% formalin, ₂ g of K ₂ CO ₃ and 700 ml of methanol and stirred for two hours at room temperature. The reaction solution is diluted with 21% water and extracted with 3 × 500 ml of ether. After thorough drying over Na ₂ SO ₄ WiTd distilled off the solvent. There are obtained 226g (100% of theory) of crude product.

2-cyano-2-n-hexylpropane-1,3-diol [19]

22.6 g (0.1 mol) of ethyl 2-n-hexyl-2-hydroxymethylcyanoacetate (crude product) are dissolved in 200 ml of absolute methanol. With stirring and cooling, 19 g (0.5 mol) of NaBH ₄ I in small portions at 15 ° C to 22 ° C are added within 2 hours. The solution is stirred for 8 hours at room temperature and then the solvent is distilled off on a rotary evaporator.

The residue is mixed with 500 ml of 10% HCl and 300 ml of ether and shaken vigorously. After separation of the ether phase wifd three more times etherified and the organic phases washed with 200 ml of saturated NaCl solution. After drying over Na ₂ SO ₄ , the solvent is distilled off and the residue is recrystallized from η-hexane.

Yield: 12.5 g (67% of theory) '

Mp: 68 ° C

S-cyano-S-n-hexyl-i-dioxaspirotB.Slundecan-g-carboxylic acid ethyl ester [20]

18.6 g (0.1 mol) of 2-cyano-2-n-hexylpropane-1,3-diol, 16.9 g (0.1 mol) of ethyl cyclohexane-1-carboxylate and 200 mg of p-toluenesulfonic acid are dissolved in 500 ml of benzene Hour heated at reflux on the water. After cooling, the reaction mixture is washed with 200 ml of 5% NaHCO ₃ solution and 200 ml of water, dried over Na ₂ SO ₄ and the solvent distilled off on a reaction evaporator. The residue is recrystallized from n-pentane.

Yield: 25.2 g (75% of theory)

3-cyano-3-n "hej (yl-1,5-dioxaspiro [5.5] undecane-9-carboxylic acid [21]

16.8 g (0.05 mol) of S-cyano-Sn-hexyl-1-dioxaspirot S. Silundecan ^ -carboxylic acid ethyl ester and 16.8 g (0.3 mol) of KOH are heated to boiling in 600 ml of methanol for 30 minutes. The solvent is distilled off on a rotary evaporator, the residue dissolved in 500 ml of water and acidified with ice cooling after overlaying with 300 ml of ethyl acetate with 20% sulfuric acid against Congo red under vigorous shaking. The organic phase is washed immediately with 100 ml of saturated sodium chloride solution, dried over Na ₂ SO ₄ and concentrated on a rotary evaporator. The residue is recrystallized from η-hexane.

Yield: 11.5 g (75% of theory)

3-cyano-3-n-hexyl-1,5-dioxaspiro [5.5] undecane-9-carboxylic acid (4 "-n-hexyI-biphenyl-4'-yl) ester [22.2] 3.09g (0, 01 mol) of S-cyano-Sn-hexyl-IS-dioxaspiroto.Slundecan-g-carboxylic acid, 2.44 g (0.01 mol) of 4'-n-hexyl-4-hydroxybiphenyl, 100 mg of DMAP and 3.27 g (0.011 mol i-fS-dimethyl-aminopropyl-S-ethyl-carbodiimide methiodide are dissolved in 50 ml of absolute methylene chloride and stirred at room temperature for 12 hours For work-up, dilute with 100 ml of methylene chloride, four times with 100 ml of water each, once with 100 ml of 5% NaHCO ₃ Washed solution and again with 100 ml of water, dried over Na ₂ SO ₄ and the solvent distilled off on a rotary evaporator The residue is recrystallized from methanol until 'clearing point constancy.

table 7;

R ⁸

XII) O COOR '

21. -HC ₆ I 20. -n-Cgl 22.1 -n-Cgl 22o2 -n-Cgl 22 ο 3 -nC ₆ I 22o4 -n-Cgl 22.5 -n-Cgl 22o6 -nC _r I

22.7 -Xi-C ₆ H ₁₃

-H .157 - -

OC ₄ H ₉ .134- -. (ΙΟΙ)

- cholesteryl .129. (127) - .127. (99) -. , 131 - -

Table 8:

R '

> C

- ^r

CH,

.70-71 ο (66)

Example 5

The following tables give examples of the substances according to the invention with their transformation temperatures.

Table 9:

Verb.

11.10 - -

mi 1

5 * 1 -COO

.82 .170 - - - • 85 »168,5 - - - - · .126,5 - - (.103,2-116,5).

Table 10:

Verb,

10 * 2-.COO- (O) -CN .123.2 11 * 9 - / h \ -CT. (104)

(.101,5)

119

Table 11:

^C 6 ^H 13

r-S

-c; x> COO-R

Verb,

16.8 16.9

) -OOC-Z ^ -OC ₄ H ₉ .81,5 - -. - - .162,5

.86 .93.5 .117.2 .133

-C ₆ H ₁₃

At some substances according to the invention, the optical birefringence Δη was measured for light of wavelength 589 nm at 20 ⁰ C, and the enthalpy of fusion ΔΗ.

Substance-No.

Δη

ΔΗ / kJ mol "

11.10 11.11 5.1 10.2 11.9 16.8 16.9

0.0570 0.0280

The measured birefringence is very low. The likewise relatively low enthalpies of fusion in mixtures signifi- cantly reduce the melting point as well as high solubility of the substances, which very much complies with the application.

Example 6

The influence of some substances according to the invention on the clearing point and the viscosity η of a base mixture can be taken from the following table: A mixture (Mi 24) consists of:

3 ^H 7 "VV"' ^G00 "aQ) ~ C ₄ H ₉ -ZiN-COO - ^) N-ON

22.4

20.2 mol-05 22.4 mol- #

13.3 mol ~ 21,7 mol%

Their properties are changed as follows:

Wed 24 N. M. mol% No. _ 100 - 10 90 11:10 10 90 11:11 10 90 16.9 10 90 16.8

Cl.p.. ⁰ C

KIp.-increase K

68 - 76 8th 83 15 78.8 10.8 85.5 17.5

The substances according to the invention markedly increase the clearing points of base mixtures.

Example 7

The influence of some substances according to the invention on the change of the electro-optical properties of a mixture was tested.

The measurements were carried out in electro-optical cells with twisted nematic structure (Schadt-Helfrich cells). For this purpose, mixture 3 was used, consisting of:

65

35 mol%

mi3 N. mol% U ₀ U τΐ ⁰ τ ⁵⁰ d mol% No. _. [V] [V] [mj IMJ [Μη-ι] 100 _ 10 6.2 12.4 37 75 10 90 11:10 10 6.8 13.6 28 83 10 90 11:11 10 7.2 14.4 60 75 10 90 16.8 , 2.49 4.98 73 73 10

U ₀ = threshold voltage U = operating voltage

τΐ ⁰ and Ta ⁰ are the arrival or Abklingzeiteii the effect after turning on or off the electric field, with a change of

optical transparency by 50%.

Claims (1)

Invention claim: Crystalline liquid mixtures for optoelectronic components, characterized in that liquid-crystalline 3- and / or 9-substituted 1,5-diheterospiro [5.5] undecane of the general formula B = R ⁴ ' ) _n - or -COOR ³ , or -COOR ³ , = identical or different, 0 »S,