CH671233A5 - - Google Patents

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CH671233A5
CH671233A5 CH56087A CH56087A CH671233A5 CH 671233 A5 CH671233 A5 CH 671233A5 CH 56087 A CH56087 A CH 56087A CH 56087 A CH56087 A CH 56087A CH 671233 A5 CH671233 A5 CH 671233A5
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coo
ooc
crystalline
liquid
glass
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CH56087A
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German (de)
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Dietrich Prof Dr Demus
Wolfgang Wedler
Wolfgang Dr Weissflog
Siegmar Dr Diele
Gerhard Dr Pelzl
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Werk Fernsehelektronik Veb
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
    • C07D213/53—Nitrogen atoms
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/39—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by esterified hydroxy groups
    • C07C205/42—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by esterified hydroxy groups having nitro groups or esterified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
    • C07D317/54—Radicals substituted by oxygen 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
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
    • C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
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    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
    • C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
    • C09K19/2014—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups containing additionally a linking group other than -COO- or -OCO-, e.g. -CH2-CH2-, -CH=CH-, -C=C-; containing at least one additional carbon atom in the chain containing -COO- or -OCO- groups, e.g. -(CH2)m-COO-(CH2)n-
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    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/22—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and nitrogen atoms as chain links, e.g. Schiff bases
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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
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
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    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
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    • C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
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    • C09K2019/0477—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by the positioning of substituents on phenylene
    • C09K2019/0481—Phenylene substituted in meta position
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    • C09K2019/0485—Phenylene substituted in ortho position

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Liquid Crystal Substances (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
  • Pyridine Compounds (AREA)

Description

671 233 671 233

2 2nd

PATENTANSPRÜCHE 1. Glasartige, kristallin-flüssige 2-substituierte -1,4-bis-(4-substituierte-Benzoyloxy) -benzole der allgemeinen Formel r1~@~ COOVJVoocVTVR 1 PATENT CLAIMS 1. Glassy, crystalline liquid 2-substituted-1,4-bis- (4-substituted-benzoyloxy) -benzenes of the general formula r1 ~ @ ~ COOVJVoocVTVR 1

R4 R3 R4 R3

wobei in which

R1 = CnH2n+i;OCnH2„+i; mit n= 1-12 R1 = CnH2n + i; OCnH2 "+ i; with n = 1-12

R2 = R1, (CH2)m-CN mit m=0 bis 4, N02, Br, H R2 = R1, (CH2) m-CN with m = 0 to 4, N02, Br, H

OOC <!>-R OOC <!> - R

R3, R4 = H, CnH2n+1; OCnH2n+I; N02, CN R2+R3 = -0-CH2-0- R3, R4 = H, CnH2n + 1; OCnH2n + I; N02, CN R2 + R3 = -0-CH2-0-

-<£>' 0-' - <£> '0-'

"0: <v>; "0: <v>;

kylcyclohexanoyloxy) -2-methylbenzoesäure-(4-substituier-ter-phenylester) allein, in Gemischen untereinander oder mit anderen kristallin-flüssigen oder nicht kristallin-flüssigen Stoffen als anisotrope feste optische Medien sowie für ther-5 moelektrooptische Speicherdisplays bei Zimmertemperatur einzusetzen. kylcyclohexanoyloxy) -2-methylbenzoic acid (4-substituted-ter-phenyl ester) alone, in mixtures with one another or with other crystalline-liquid or non-crystalline-liquid substances as anisotropic solid optical media and for ther-5 moelectro-optical storage displays at room temperature.

Zur weiteren Verbesserung der Eigenschaften der einzusetzenden Gemische sind jedoch neue weitere Komponenten dringend erforderlich. However, further components are urgently required to further improve the properties of the mixtures to be used.

10 10th

Aufgabe der Erfindung ist das Finden von glasartigen kristallin-flüssigen Substanzen, deren Glastemperatur oberhalb der Zimmertemperatur liegt. The object of the invention is to find glass-like crystalline liquid substances whose glass temperature is above room temperature.

Erfindungsgemäss wurden als solche kristallin-flüssige 15 2-substituierte -l,4-bis-(4-substituierte-Benzoyloxy)-benzole der allgemeinen Formel According to the invention, 15 2-substituted-1,4-bis- (4-substituted-benzoyloxy) -benzenes of the general formula were crystalline-liquid as such

R R

20 20th

"-0-coo "-0-coo

W W

25 25th

X = CO; C =N-OOC; R5 = CnH2n+1 mitn=0 bis 4; X = CO; C = N-OOC; R5 = CnH2n + 1 with n = 0 to 4;

| 30 | 30th

R5 R5

CO-Y mit Y = Z'-(CH2)n-Z2 (Z1, Z2 = 0, S, NR5, CHR5, CO, CH = CH, -N=CR5-) n=0-10 ausserdem Z2 = Einfachbindung, OOC wobei wenn n = O bedeuten. CO-Y with Y = Z '- (CH2) n-Z2 (Z1, Z2 = 0, S, NR5, CHR5, CO, CH = CH, -N = CR5-) n = 0-10 also Z2 = single bond, OOC where if n = O.

2. Verwendung von glasartigen, kristallin-flüssigen 2-substituierten -1,4-bis- (4-substituierten-Benzoyloxy)-ben-zolen nach Anspruch 1, allein, in Gemischen untereinander oder mit anderen kristallin-flüssigen oder nicht kristallinflüssigen Stoffen als anisotrope feste optische Medien sowie für thermo-elektrooptische Speicherdisplays. 2. Use of glassy, crystalline-liquid 2-substituted-1,4-bis- (4-substituted-benzoyloxy) -benzenes according to claim 1, alone, in mixtures with one another or with other crystalline-liquid or non-crystalline-liquid substances as anisotropic solid optical media as well as for thermo-electro-optical storage displays.

R4 R3 wobei R4 R3 where

R1 = CnH2n+i; OCnH2n+1; n= 1-12, R1 = CnH2n + i; OCnH2n + 1; n = 1-12,

R2 = R1, (CH2)m-CN mit m = 0-4, N02, Br, H, R2 = R1, (CH2) m-CN with m = 0-4, N02, Br, H,

OOC OOC

-0-F -0-F

35 R3, R4 = H, CnH2n+1; OCnH2n+1; N02, CN R2+R3 = -0-CH2-0- 35 R3, R4 = H, CnH2n + 1; OCnH2n + 1; N02, CN R2 + R3 = -0-CH2-0-

A =< O A = <O

40 40

-0!0! ö -0! 0! ö

BESCHREIBUNG DESCRIPTION

Die Erfindung betrifft glasartige Flüssigkristalle, die als anisotrope feste optische Medien zur Herstellung optischer Bauteile, wie z.B. Kompensatoren, Prismen, Platten mit optischer Drehung, Polarisatoren sowie für thermoelektroopti-sche Speicherdisplays eingesetzt werden. The invention relates to glass-like liquid crystals which are used as anisotropic solid optical media for the production of optical components, e.g. Compensators, prisms, plates with optical rotation, polarizers and for thermo-electro-optical memory displays are used.

Glasartige Flüssigkristalle wurden bereits beschrieben [H. Kelker, R. Hätz: Handbook of Liquid Crystals, Verlag Chemie, Weinheim 1980; N. Kirov, M.P. Fontana, N. Afa-nasieva: Mol. Cryst. Liq. Cryst. 89, 193 (1982)]. Die Glastemperaturen sind sehr niedrig und liegen typischerweise weit unter 0 °C, z.B. für N-(o-hydroxy-p-methoxybenzyli-den) -p-butylanilin [M. Sorai, S. Seki: Bull. Chem. Soc. Japan 44, 2887 (1971); C.P. Johari: Phil. Magaz. B 46, 549 (1982)] bei —65 °C Substanzen mit derartig tiefen Glastemperaturen befinden sich bei Zimmertemperatur im gewöhnlichen kristallin-flüssigen (z.B. nematischen) Zustand oder sind kristallin-fest, weil sie nicht hinreichend lange unter die Schmelztemperatur unterkühlbar sind. Sie können demzufolge als anisotrope feste Medien oder für Speicherdisplays nicht verwendet werden. Es wurde bereits vorgeschlagen 3,3'-Sulfinyl- bzw. 3,3'-sulfonyl-di-(4 acyloxy-benzoesäure-ester), 4-[4-(4-substituierte Benzylidenamino)-naphthyl-(l)-azo] -benzoesäure-äthylester, Biphenyl-4,4'-bis- (4-carbo-nyl-oxybenzyliden-malonsäure -di-n-alkylester) oder 4-(4-Al- Glassy liquid crystals have already been described [H. Kelker, R. Hätz: Handbook of Liquid Crystals, Verlag Chemie, Weinheim 1980; N. Kirov, M.P. Fontana, N. Afa-nasieva: Mol. Cryst. Liq. Cryst. 89, 193 (1982)]. Glass temperatures are very low and are typically well below 0 ° C, e.g. for N- (o-hydroxy-p-methoxybenzylidene) -p-butylaniline [M. Sorai, S. Seki: Bull. Chem. Soc. Japan 44: 2887 (1971); C.P. Johari: Phil. Mag. B 46, 549 (1982)] at -65 ° C. Substances with such low glass temperatures are in the usual crystalline-liquid (e.g. nematic) state at room temperature or are crystalline-solid because they cannot be subcooled sufficiently long below the melting temperature. As a result, they cannot be used as anisotropic solid media or for storage displays. It has already been proposed 3,3'-sulfinyl or 3,3'-sulfonyl-di- (4 acyloxy-benzoic acid ester), 4- [4- (4-substituted benzylidenamino) -naphthyl- (l) -azo ] -benzoic acid ethyl ester, biphenyl-4,4'-bis- (4-carbo-nyl-oxybenzylidene-malonic acid -di-n-alkyl ester) or 4- (4-Al-

45 X = CO; C =N-OOC; R5 = CnH2n+1 mit n=0-4; 45 X = CO; C = N-OOC; R5 = CnH2n + 1 with n = 0-4;

R5 R5

CO-Y mit Y = Z,-(CH2)n-Z2 (Z1, Z2 = O, S, NR5, CHR5, CO, CH=CH, -N=CR5-) n=0-10 50 ausserdem Z2 = Einfachbindung, OOC bedeuten, gefunden. CO-Y with Y = Z, - (CH2) n-Z2 (Z1, Z2 = O, S, NR5, CHR5, CO, CH = CH, -N = CR5-) n = 0-10 50 also Z2 = single bond , OOC mean found.

Die Substanzen können allein, in Gemischen untereinander oder mit anderen kristallin-flüssigen oder nicht kristallinflüssigen Stoffen als glasartige nematische Flüssigkristalle mit Glastemperaturen oberhalb der Zimmertemperatur als 55 anisotrope feste optische Medien zur Herstellung optischer Bauteile wie Kompensatoren, Prismen, Platten mit optischer Drehung, Polarisatoren sowie für thermoelektrooptische Speicherdisplays eingesetzt werden. The substances can be used alone, in mixtures with one another or with other crystalline-liquid or non-crystalline-liquid substances as glass-like nematic liquid crystals with glass temperatures above room temperature as 55 anisotropic solid optical media for the production of optical components such as compensators, prisms, plates with optical rotation, polarizers and for thermo-electro-optical storage displays are used.

Durch Herstellung entsprechend orientierter Schichten 60 können aus diesem optischen Medium bei homogener Orientierung optische Kompensatoren, Prismen sowie unter Beifügung dichroitischer Farbstoffe Polarisatoren, bei verdrillter Orientierung Platten mit optischer Drehung sowie bei Benutzung entsprechender Zellen thermoelektrooptische Speicher-65 displays hergestellt werden. By producing appropriately oriented layers 60, optical compensators, prisms and, with the addition of dichroic dyes, polarizers, with twisted orientation, plates with optical rotation, and when using appropriate cells, thermo-electro-optical memory displays can be produced from this optical medium.

Die Synthese von Substanzen der Formel I erfolgt durch Acylierung geeigneter Zwischenprodukte. Dabei können die Molekülsegmente mit den Ringsystemen A und B nachein Substances of the formula I are synthesized by acylation of suitable intermediates. The molecular segments with the ring systems A and B can follow

3 3rd

671 233 671 233

ander in verschiedener Reihenfolge, aber auch gleichzeitig eingeführt werden. Eine Vielfalt von Verbindungen wird durch Veresterung von Derivaten der Formel II (mit Z1 = O, S, NR5) be introduced in different order, but also simultaneously. A variety of compounds is obtained by esterification of derivatives of the formula II (with Z1 = O, S, NR5)

H - Y H - Y

R R R R

mit den Säurechloriden III erhalten. 1 obtained with the acid chlorides III. 1

R R

l"0 -COO- (7)-OOC- 0- l "0 -COO- (7) -OOC- 0-

coc1 coc1

Die Acylierung der Hydrochinonderivate IV The acylation of the hydroquinone derivatives IV

ho-Q-oh ho-Q-oh

R R R R

mit den Säurechloriden V r1-0" COC1 with the acid chlorides V r1-0 "COC1

II II

10 10th

III III

15 15

20 20th

IV IV

25 25th

V30 V30

gelingt nach bekannten Methoden. succeeds according to known methods.

Auch die Acylierung eines trifunktionellen Derivates VI führt zu Verbindungen der allgemeinen Formel I. 35 The acylation of a trifunctional derivative VI also leads to compounds of the general formula I. 35

Ausführungsbeispiele Embodiments

Beispiele für die Herstellung Examples of manufacturing

Beispiel 1 example 1

0,01 Mol eines Derivates der Formel II werden in 100 ml abs. Toluol aufgenommen. 0,01 Mol des Säurechlorids III werden, gelöst in 50 ml Toluol, bei Raumtemperatur zugegeben. Man versetzt anschliessend unter Rühren mit 0,015 Mol Triethylamin, lässt 20 Std. stehen und erwärmt danach 30 Min auf 80 °C. Nach dem Abkühlen wird vom ausgefallenen Hydrochlorid abgesaugt, das Toluol im Vakuum abgezogen und der verbleibende Rückstand umkristallisiert. Geeignete Lösungsmittel sind z.B. Ethanol, n-Amylalkohol, Dioxan, Dimethylformamid, Ausbeuten: 43-68%. 0.01 mol of a derivative of formula II are abs in 100 ml. Toluene added. 0.01 mol of the acid chloride III, dissolved in 50 ml of toluene, is added at room temperature. 0.015 mol of triethylamine are then added with stirring, the mixture is left to stand for 20 hours and then heated to 80 ° C. for 30 minutes. After cooling, the hydrochloride which has precipitated is filtered off with suction, the toluene is stripped off in vacuo and the residue which remains is recrystallized. Suitable solvents are e.g. Ethanol, n-amyl alcohol, dioxane, dimethylformamide, yields: 43-68%.

Beispiel 2 Example 2

0,01 Mol Hydrochinon der Formel IV werden mit 0,02 Mol eines Säurechlorids V in Gegenwart von 0,03 Mol Triethylamin umgesetzt und, wie unter Beispiel 1 beschrieben, aufgearbeitet. Ausbeuten: 51-74%. 0.01 mol of hydroquinone of the formula IV are reacted with 0.02 mol of an acid chloride V in the presence of 0.03 mol of triethylamine and worked up as described in Example 1. Yields: 51-74%.

Beispiel 3 Example 3

0,01 Mol eines trifunktionellen Derivates der Formel VI werden mit 0,03 Mol eines Säurechlorids V in Gegenwart von 0,045 Mol Triethylamin zur Reaktion gebracht und analog Beispiel 1 aufgearbeitet. Ausbeuten: 39-57%. 0.01 mol of a trifunctional derivative of the formula VI are reacted with 0.03 mol of an acid chloride V in the presence of 0.045 mol of triethylamine and worked up analogously to Example 1. Yields: 39-57%.

Tab. 1 zeigt die Umwandlungstemperaturen (°C) einiger erfindungsgemässer Substanzen. Hierbei bedeuten: K = kristallin-fest S = smektisch N = nematisch is = isotrop-flüssig Tab. 1 shows the transition temperatures (° C) of some substances according to the invention. Here: K = crystalline solid S = smectic N = nematic is = isotropic liquid

Zahlen in Klammern bedeuten monotrope Umwandlungen. Numbers in parentheses mean monotropic conversions.

(Z2 in Y = O, S. NR5) CO- Y - H VI40 (Z2 in Y = O, p. NR5) CO-Y-H VI40

Tabelle 1 Table 1

C„H C "H

8 17 8 17

0^ 0 ^

COO COO

O >—OOC -0- 0C8H17 O> —OOC -0-0C8H17

R R

R R

-C00-(CH2)n^Ö^- -C00- (CH2) n ^ Ö ^ -

-COO -COO

-COO-CH, -COO-CH,

-0- -0-

(ch2)m-cn (ch2) m-cn

»0>-OcnH »0> -OcnH

2n+l n 2n + l n

!< ! <

S S

N is N is

O O

• •

91 - 91 -

(65) . (65).

1 1

• •

98 - 98 -

98 98

2 2nd

« «

73 - 73 -

80 80

3 3rd

• •

68 - 68 -

96 96

4 4th

• •

i o ok

CO CO

♦ (76) . ♦ (76).

f° f °

• •

107 . - 107. -

(50) . (50).

i 1 i 1

1 1

• •

91 - 91 -

(47) . (47).

L2 L2

• •

112 - 112 -

. (39) . . (39).

i i

85 - 85 -

120 120

2 2nd

92 - 92 -

117 117

671 233 671 233

Tabelle 1 (Fortsetzung) Table 1 (continued)

C8H170"*^^^~C00"*^^^~~°^C~^^y^""0C8Hl7 C8H170 "* ^^^ ~ C00" * ^^^ ~~ ° ^ C ~ ^^ y ^ "" 0C8Hl7

r n 1< r n 1 <

3 n is 3 n is

-coo-n=c- 0.c5h1jl ch, -coo-n = c- 0.c5h1jl ch,

-c=n-ooc- / o\ -C"5H1;L -c = n-ooc- / o \ -C "5H1; L

i w ch., i w ch.,

-ch=n-ooc- -ch = n-ooc-

-0-C5H -0-C5H

-coo-n=ch- 0 -oc6h -coo-n=ch- (!) -cn -coo-n = ch- 0 -oc6h -coo-n = ch- (!) -cn

-n=ch <E? -n = ch <E?

0 0

11 13 11 13

-COO -COO

-coo-ch2- -coo-ch2-

N0_ N0_

-coo-ch2- <5 -coo-ch2- <5

3 3rd

82 - 82 -

III III

4 4th

79 - 79 -

109 109

5 5

75 - 75 -

105 105

6 6

i i

CO CO

105 105

7 7

80 - 80 -

105 105

8 8th

84 - 84 -

104 104

9 9

93 - 93 -

104 104

10 10th

93 - 93 -

104 104

+ 1 + 1

4 4th

121 121

- . 152 -. 152

5 5

120 120

- . 153 -. 153

6 6

110 110

- . 153 -. 153

7 7

108 108

- . 152 -. 152

8 8th

99 99

151 151

9 9

99 99

- . 149 -. 149

10 10th

103 103

- . 148 -. 148

74 74

- - (.22) - - (.22)

58 58

- - (.17) - - (.17)

75 75

- - (.70) - - (.70)

87 87

- - .92 - - .92

110 110

- - (.65) - - (.65)

77 77

cn en • cn en •

1 1 1 1

108 108

- - (.80) - - (.80)

80 80

. 96 .112 . 96 .112

no, no,

671 233 671 233

Tabelle 1 (Fortsetzung) Table 1 (continued)

c8h17° ^coo^ooc-<^>oc8hi7 c8h17 ° ^ coo ^ ooc - <^> oc8hi7

R R

R n K SN R n K SN

t"G) t "G)

IS IS

-c00-ch2-ch=ch- 0 -n02 164 .195 - - -c00-ch2-ch = ch- 0 -n02 164 .195 - -

-c00-ch2-ch=ch- 0 107 - - . 130 -c00-ch2-ch = ch- 0 107 - -. 130

-c00~ch2-ch2-^ö^— cn 88 ( . 80) . 91 -c00 ~ ch2-ch2- ^ ö ^ - cn 88 (. 80). 91

-c00-ch2-ch2-0-(7)-cn 75 . 164 - - -c00-ch2-ch2-0- (7) -cn 75. 164 - -

-c00-ch2-chp-0-^~ö^ 76 - - 109 -c00-ch2-chp-0- ^ ~ ö ^ 76 - - 109

-co-nh-ch2 -© 121 - - 112) -co-nh-ch2 - © 121 - - 112)

-co-s-ch2-0 78 - - , 88 -co-s-ch2-0 78 - -, 88

-coo-ch- 0 134 . 151 - - -coo-ch- 0 134. 151 - -

ch3 ch3

-coo-ch2-ch2-n- 0 60 - - . 76 c2h5 -coo-ch2-ch2-n- 0 60 - -. 76 c2h5

-c00-ch2-^0^~br 95 (.61) . 121 -c00-ch2- ^ 0 ^ ~ br 95 (.61). 121

-c00-ch2-^~ö^-ch3 82 - . 113 -c00-ch2- ^ ~ ö ^ -ch3 82 -. 113

-c00-ch2-^"0^~ch(ch5)2 75 - . 95 -c00-ch2- ^ "0 ^ ~ ch (ch5) 2 75-. 95

-c00-ch2-<0v-0^ 99 - - . 112 -c00-ch2- <0v-0 ^ 99 - -. 112

-c00-ch2-/0\-0c8h17 " 78 - - . 80 -c00-ch2- / 0 \ -0c8h17 "78 - -. 80

och3 och3

-c00-ch2-/ h^ 75 - - . 86 -c00-ch2- / h ^ 75 - -. 86

85 - - (. 58) 85 - - (. 58)

671 233 671 233

Tabelle 2 Table 2

6 6

-COO- (^)-OQC- 0-r1 -COO- (^) - OQC- 0-r1

r<ö)-NO r <ö) -NO

COQCH, COQCH,

r1 r1

l< l <

s n s n

ch30 ch30

• •

219 219

- -

(. (.

151) 151)

c2h5° c2h5 °

« «

188 188

- -

(. (.

166) 166)

c3h7o c3h7o

• •

140 140

- - - -

• •

148 148

c4h9° c4h9 °

• •

134 134

(108) (108)

• •

155 155

c5h11° c5h11 °

• •

124 124

. 136 . 136

• •

149,5 149.5

c6h13° c6h13 °

• •

110 110

. 151, . 151,

5. 5.

154 154

c7h15° c7h15 °

• •

110 110

. 158, . 158,

5 - 5 -

- -

c8h17° c8h17 °

• •

96 96

. 163 . 163

- -

- -

c9h19° c9h19 °

• •

93 93

. 166 . 166

- -

- -

c10h21° c10h21 °

• •

87 87

. 168 . 168

- -

- -

c7h15 c7h15

• •

100 100

. 130 . 130

- -

- -

is is

Tabelle 3 Table 3

-COO- -OOC- 0-f -COO- -OOC- 0-f

NCOO-CH„ -CH„ -OOC- (~o\ -R1 NCOO-CH "-CH" -OOC- (~ o \ -R1

l< l <

N N

2 "2 is 2 "2 is

c4h9° c8h17° c4h9 ° c8h17 °

Beispiele für die Anwendung Examples of use

Beispiel I Die Substanz der Formel Example I The substance of the formula

133 96 133 96

(122) , 103 (122), 103

*7-0- * 7-0-

COO- COO-

<^Yooc-<2>-ocgh17 ' /~\ 'ch- <^ Yooc- <2> -ocgh17 '/ ~ \' ch-

-0-' -0- '

COO-CH, COO-CH,

N N

7 7

671 233 671 233

hat einen Schmelzpunkt von 70 °C und einen Klärpunkt von 94 °C. Sie wird auf etwa 100 °C, bis in den isotrop-flüssigen Bereich hinein, aufgeheizt. Danach erfolgt langsames Abkühlen auf Temperaturen um 80 °C. In diesem nematischen Zustand ist die molekulare Struktur durch Wandwirkungen sowie elektrische oder magnetische Felder orientierbar. Rasches Abkühlen auf Temperaturen von 0 bis 5 °C lässt die nematische Phase glasartig erstarren. Durch erneutes Erhitzen und Abkühlen in der schon beschriebenen Weise ist eine Änderung der Orientierung möglich. Die im Glaszustand fixierte Struktur der nematischen Phase ist über mehrere Monate stabil. has a melting point of 70 ° C and a clearing point of 94 ° C. It is heated to about 100 ° C, into the isotropic liquid area. This is followed by slow cooling to temperatures around 80 ° C. In this nematic state, the molecular structure can be oriented through wall effects as well as electrical or magnetic fields. Rapid cooling to temperatures from 0 to 5 ° C freezes the nematic phase like a glass. The orientation can be changed by heating and cooling again in the manner already described. The structure of the nematic phase, which is fixed in the glass state, is stable over several months.

Beispiel II Example II

Die Substanz aus Beispiel I wird mit der Substanz The substance from Example I is with the substance

H9C4 jQQ -COO- -CÛO-0 -0C7H15 H9C4 jQQ -COO- -CÛO-0 -0C7H15

CH CH

(Umwandlungstemperaturen dieses Stoffes: K 95 N 187 Is; unterkühlbar bis ca. 65 °C) gemischt. Das Mischungsverhältnis wurde so gewählt, dass der Stoff aus Beispiel I einen Molenbruch von 0,72 in diesem binären Gemisch besitzt. Die Mischung schmilzt im Temperaturintervall zwischen 50° und 72 °C zu einer nematischen Phase auf. Der Klärpunkt liegt bei 111 °C. Anschliessendes rasches Abkühlen mit dem Kühltisch führt zur Bildung eines getrübten, glasartigen Körpers, der im Polarisationsmikroskop das typische Texturbild einer nematischen Phase zeigt. Dieser glasartige Körper erweicht bei anwachsenden Temperaturen in einem Temperaturintervall zwischen 20 °C und 35 °C. Ein Auskristallisieren wurde nach etwa 2-3 Tagen beobachtet. (Transition temperatures of this substance: K 95 N 187 Is; subcoolable up to approx. 65 ° C) mixed. The mixing ratio was chosen so that the substance from Example I has a mole fraction of 0.72 in this binary mixture. The mixture melts to a nematic phase in the temperature range between 50 ° and 72 ° C. The clearing point is 111 ° C. Subsequent rapid cooling with the cooling table leads to the formation of a cloudy, glass-like body, which shows the typical texture image of a nematic phase in the polarizing microscope. This glass-like body softens with increasing temperatures in a temperature interval between 20 ° C and 35 ° C. Crystallization was observed after about 2-3 days.

Beispiel III Example III

Durch Zufügen von 1 % des dichroitischen Farbstoffes By adding 1% of the dichroic dye

°2N® N=N-(7)-N ' ° 2N® N = N- (7) -N '

/C2H5 / C2H5

CH2-CH2-0H CH2-CH2-0H

zu den Substanzen gemäss Beispiel 1 und 2 und bei homogen liegender Orientierung der Substanz zwischen zwei Glasscheiben oder anderes durchsichtiges Material entstehen farbige Polarisatoren, die linear polarisiertes rotes Licht er-20 zeugen bzw. in Senkrechtstellung linear polarisiertes rotes Licht absorbieren. to the substances according to Examples 1 and 2 and with a homogeneous orientation of the substance between two glass panes or other transparent material, colored polarizers are produced which produce linearly polarized red light or absorb linearly polarized red light in the vertical position.

Beispiel IV Example IV

Durch Einfüllen der Substanzen gemäss Beispiel 1, 2, 3 in 25 eine elektrooptische Zelle, die aus zwei mit einer elektrisch leitenden transparenten und passend strukturierten Schicht versehenen Glasscheiben in einem Abstand von 5 bis 30 um besteht, entsteht ein thermo-elektrooptisches Speicherdisplay, in dem einzelne Punkte oder grössere Flächen durch ei-30 nen Laser oder eine elektrische Heizung aus dem glasartigen Zustand in den gewöhnlichen nematischen Zustand aufgeheizt und umgeschaltet sowie anschliessend unter Beibehaltung des umgeschalteten Zustandes wieder in den Glaszustand gekühlt werden, so dass die eingegebene Information 35 gespeichert wird. By filling the substances according to Example 1, 2, 3 into 25 an electro-optical cell, which consists of two glass panes provided with an electrically conductive, transparent and suitably structured layer at a distance of 5 to 30 μm, a thermo-electro-optical memory display is created in which Individual points or larger areas are heated and switched over from the glass-like state into the usual nematic state by a laser or an electric heater and then cooled again while maintaining the switched state, so that the information 35 entered is stored.

C C.

CH56087A 1986-03-05 1987-02-12 CH671233A5 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DD28759386A DD247227A1 (en) 1986-03-05 1986-03-05 GLASSY NEMATIC LIQUID CRYSTALS

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DD274441B5 (en) * 1988-08-02 1993-11-04 Univ Halle Wittenberg LOW-MOLECULAR GLASS-FORMING MIXTURES WITH SMEKTICAL PHASES
DE4108627A1 (en) * 1991-03-16 1992-09-17 Basf Ag LIQUID CRYSTAL LINKS
DE4224083A1 (en) * 1992-07-22 1994-01-27 Basf Ag Defined, oligomeric liquid crystalline compounds with smectic liquid crystalline phases
DE4332733A1 (en) * 1993-09-25 1995-03-30 Basf Ag Liquid crystalline compounds
JP2006347893A (en) * 2005-06-13 2006-12-28 Hirosaki Univ New t type compound and liquid crystal composition containing the same compound
KR102393259B1 (en) 2014-02-14 2022-04-29 제온 코포레이션 Polymerizable compound, polymerizable composition, polymer, and optically anisotropic body
KR102535210B1 (en) 2015-12-29 2023-05-19 삼성전자주식회사 Polymerizable liquid crystal compound, composition for optical film, and optical film, antireflective film and display device including the same

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