US 4,961,876 AGrant
Liquid Crystalline Ferroelectric Derivatives of Branched Acyclic Alpha-Chlorocarboxylic Acids
Issue Date:1990-10-09
•8 Claims
Abstract
Liquid crystalline ferroelectric derivatives of branched acyclic alpha-chlorocarboxylic acids of the general formula I ##STR1## wherein n=0 or 1; m=0 or 1, o=0 or 1; p=0 or 1 The inventive substances by themselves, in mixtures with one another as well as with other liquid crystalline substances or substances which are not liquid crystalline, can form liquid crystalline ferroelectric phases, which make them suitable for use in displays. X=--COO--, --OOC--, or --CH.sub.2 --CH.sub.2 -- Y=X, --CH.sub.2 --, --N.dbd.N--, or --N.dbd.N(O)--, ##STR2## It was discovered that, by reacting chiral alpha-chlorocarboxylic acids or alpha-chlorocarboxylic acid chlorides or bromides, synthesized from natural alpha-amino acids by reaction with nitric and hydrochloric acids, with appropriate hydroxy compounds directly or in the presence of strongly dehydrating substances, preferably carbodiimides, liquid crystalline ferroelectric substances of the general formula I are formed.
Metadata
Assignee
- VEB Werk fuer Fernsehelektronik im VEB Kombinat Mikroelektronik
Inventors
- Dietrich Demus
- Horst Zaschke
- Wolfgang Weissflog
- Kristina Mohr
- Saskia Kohler
- Kerstin Worm
Application Information
Application Number:US 2459620
Filing Date:1988-09-15
Priority Date:1985-08-26
Art Unit:223
Classifications
IPC:
C09K 1920
Field of Search:
560252350141;145299.01;299.6;299.61;299.63;299.64;299.65;299.66;299.67;299.68350 S
Patent Drawings
This patent does not have any drawings.
Description
BACKGROUND OF THE INVENTION AND RELATED ART STATEMENT
The invention relates to novel liquid crystalline ferroelectric derivatives of branched acyclic alpha-chlorocarboxylic acids.
Liquid crystalline ferroelectric compounds are described in the literature. They are optically active compounds, which are predominantly derivatives of the optically active amyl alcohols and optically active alpha-chloropropanols (P. Keller, S. Juge, L. Liebert, L. Strzelecki: C.R. Acad. Sci., Ser. 282 C, 639 (1976); P. Keller: Ann. Phys. 139-44 (1978); M. V. Loseva, B. I. Ostrowskii, A. Z. Rabinovich, A. S. Sonin, B. A. Strukov, N. I. Chernova: Pis'ma Zh. Eksp. Teor. Fiz. 28, 404 (1978); A. Hallsby, M. Nilsson, B. Otterholm: Mol. Cryst. Liq. Cryst. 82, 61-8 (1982); P. Keller: Ferroelectrics 1984; J. W. Goodby, T. M. Leslie: Mol. Cryst. Liq. Cryst. 110, 175 (1984). However, when used in displays with memory properties, these substances have a series of disadvantages, such as very high melting temperatures, instability towards heat, light or chemical influences or very low dipole moments, which bring about low values for the spontaneous polarization.
It is an object of the invention to find substances, which exhibit good stability towards heat, light and chemical influences, have low melting points and show sufficiently high dipole moments.
SUMMARY OF THE INVENTION
It has now been discovered that liquid crystalline ferroelectric derivatives of branched acyclic alpha-chlorocarboxylic acids of the general formula ##STR3## are suitable for depicting numerals, symbols and illustrations in rapidly switching displays in optoelectronics.
The inventive liquid crystalline ferroelectric derivatives of branched acyclic alpha-chlorocarboxylic acids are obtained by the reaction of chiral alpha-chlorocarboxylic acids or alpha-chlorocarboxylic acid chlorides or bromides, synthesized from natural amino acids by reaction with nitric acid and hydrochloric acid, with appropriate hydroxy compounds directly or in the presence of strongly dehydrating substances, preferably carbodiimides such as dicyclohexylcarbodiimide, 1-(3-dimethylaminopropyl)-3-ethyl-carbodiimide methiodide or 1-(3-dimethylaminopropyl)-3-ethyl-carbodiimide-metho-p-toludisolfonate.
The alpha-chlorocarboxylic acid chlorides are esterified with the appropriate hydroxy compounds by the Schotten-Baumann or von Einhorn method.
As alpha-chlorocarboxylic acids, preferably the derivatives, obtained from the natural amino acids L-valine, L-leucine and L-isoleucine by reaction with nitric acid and hydrochloric acid, are suitable. However, the chlorocarboxylic acids, obtainable from the optically active antipodes D-valine, D-leucine and D-isoleucine, can also be used. These compounds can be synthesized according to known procedures, for example, see E. FISCHER, H. SCHEIBLER: Ber. Dtsch. Chem. Ges. 41, 889 (1908); P. KARRER, M. RENHARD: J. Biol. Chem. 28, 497 (1946); P. KARRER, H. RESCHOFSKY, W. KAASE: Helv. Chim. Acta 30, 271 (1947).
The hydroxy compounds are fragments of liquid crystalline substances, which themselves do not have to be liquid crystalline and can be synthesized according to known procedures (cf. references in D. Demus and H. Zaschke "Flussige Kristalle in Tabellen II" (Liquid Crystals In Tables II), Leipzig, 1984). In the process, the chirality of the alpha-chlorocarboxylic grouping is retained and, surprisingly, the yield, when the process is carried out by reacting alpha-chlorocarboxylic acids with the hydroxy compounds in the presence of strongly dehydrating agents, is approximately twice as high (40-60%) as when the process is carried out by first of all reacting to form the alpha-chlorocarboxylic acid chlorides and subsequently esterifying. The substances are colorless, chemically and thermally very stable and, due to the chloro substituent directly at the chiral center, have a high dipole moment and, with that, a high spontaneous polarization.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The invention is explained in greater detail in the following by means of synthesis examples.
EXAMPLE 1
(S)-(+)-1-(4-n-Alkoxy-benzoyloxy)-4-(2-chloro-3-methylbutyryloxy)-biphenyls
A. (S)-(+)-2-chloro-3-methylbutyric acid
L-(+)-valine (10 g, 0.085 moles), 1 g urea, 30 mL concentrated hydrochloric acid and 15 mL concentrated nitric acid are shaken for about 30-60 minutes in a flask, until the evolution of nitrogen has ended. After that, the reaction batch is heated for 45 minutes at 70.degree. to 80.degree. C. in a water bath (complete dissolution with foaming, separation of a yellow oil). After cooling, the mixture is extracted with ether, the ether extract is washed several times with cold water, dried over calcium chloride, the solvent is evaporated off in a rotary evaporator and the residue is fractionally distilled under vacuum.
Yield: 3.2 g (28% of the theoretical).
Boiling point: 125.degree.-126.degree. C./4.25 kPa.
B. (S)-(+)-2-Chloro-3-methylbutyryl chloride
(S)-(+)-2-chloro-3-methylbutyric acid (20 g, 0.147 moles) and 13 g PCl.sub.3 are shaken for 12 hours in a flask and subsequently heated for 1 hour on the water bath. The reaction mixture is distilled at atmospheric pressure.
Yield: 5.4 g (27% of the theoretical).
Boiling point 144.degree.-146.degree. C.
If, as halogen transferring agent, a 5-fold amount of SOCl.sub.2 is used and the batch is heated for 2 hours at 50.degree. to 60.degree. C. on the water bath, 12.2 g of (S)-(+)-2-chloro-3-methylbutyryl chloride (60% of the theoretical amount) are obtained.
C. (S)-(+)-1-(4-n-Alkoxy-benzoyloxy)-4-(2-chloro-3-methylbutyryloxy)biphenyls
To the solution of 0.005 moles of 1-(4-n-alkoxy-benzoyloxy)-4-hydroxy-biphenyl, 0.6 mL of triethylamine and 50 mL of absolute toluene, 0.77 g (0.005 moles) of (S)-(+)-2-chloro-3-methyl-butyryl chloride are added. The mixture is allowed to stand for a day at room temperature and subsequently heated for 1 hour at 80.degree. C. on the water bath. After filtering off the precipitate formed, the solvent is distilled off and the residue is recrystallized several times from ethanol/water. The yields are 50 to 60% of the theoretical. The liquid crystalline melting behavior is given in the Tables.
EXAMPLE 2
(S)-(+)-1-(4-n-Alkoxy-benzoyloxy)-4-(4-(2-chloro-3-methylbutyryloxybenzoylo xy)-benzene
A. (S)-(+)-4-(2-chloro-3-methyl-butyryloxy)-benzoic acid
4-Hydroxybenzoic acid (8.9 g, 0.065 moles) is dissolved in 20 mL of absolute pyridine and 10 g (0.065 moles) of (S)-(+)-2-chloro-3-methylbutyryl chloride are added dropwise with stirring at 0.degree. to 5.degree. C. The mixture is allowed to stand for 4 hours at room temperature and then poured onto ice/conc. HCl (200 g/30 mL). The precipitate is filtered off with suction and washed several times with dilute HCl and water. The residue is recrystallized from methanol/water.
Yield: 11.7 g (70% of the theoretical).
Melting point: 150.degree.-151.degree. C.
B. (S)-(+)-1-(4-n-alkoxy-benzoyloxy)-4-(4-(2-chloro-3-methyl-butyryloxy)-benz oyloxy)-benzene
To 0.003 moles of 1-(4-n-alkyloxy-benzoyloxy)-4-hydroxybenzene, dissolved in 30 mL of toluene and 0.6 mL (0.004 moles) of triethylamine, (S)-(+)-4-(2-chloro-3-methyl-butyryloxy)-benzoyl chloride, synthesized by reacting 0.8 g (0.003 moles) of (S)-(+)-4-(2-chloro-3-methyl-butyryloxy)-benzoic acid with 3 mL SOCl.sub.2, is added dropwise as crude product. The mixture is allowed to stand for 1 day at room temperature and then heated briefly to 80.degree. C. (water bath temperature). Subsequently, the precipitate is filtered off, the mother liquor is concentrated and the residue remaining is recrystallized several times from ethanol/water.
The yields are 55 to 60% of the theoretical amount.
EXAMPLE 3
(S)-(+)-1-(4-n-Alkoxy-benzoyloxy)-4-(4-(2-chloro-3-methyl-pentanoyloxy)-ben zoyloxy)-benzene
A. (S)-2-Chloro-3-methylpentanoic acid
To 20 g (0.150 moles) of L-(+)-isoleucine and 2 g of urea, 60 mL concentrated HCl and 30 mL concentrated HNO.sub.3 are added at room temperature. The mixture is subsequently heated for 1 hour at 80.degree. C. and then for 1 hour at 50.degree. C. on a water bath (complete dissolution of the acid with heavy foaming). After cooling, the solution is extracted with ether several times, the ether extract is washed with water and dried over calcium chloride, the solvent is distilled off in a rotary evaporator and the residue is fractionated under vacuum.
Yield: 6.7 g (29% of the theoretical)
Boiling point: 136.degree.-139.degree. C./3.47 kPa
EXAMPLE 4
A. (S)-2-Chloro-4-methyl-pentanoic acid
L-(+)-Leucine (10 g, 0.076 moles) is mixed with 24 mL of concentrated HCl and 10 mL of concentrated HNO.sub.3 with the addition of 2 g of urea and subsequently heated for 1 hour at 80.degree. C. and then for 1 hour at 50.degree. C. on a water bath (complete dissolution of the acid with heavy foaming). After cooling, the solution is extracted with ether several times, the ether extract is washed with water and dried over calcium chloride, the solvent is distilled off in a rotary evaporator and the residue is fractionally distilled under vacuum.
Yield: 4.1 g (36% of the theoretical).
Boiling point: 136.degree.-137.degree. C., 3.99 kPa.
B. Esterification in the Presence of Dicyclohexylcarbodiimide (DCC)
While stirring, 1.5 g (0.01 moles) of (S)-2-chloro-3-methylpentanoic acid, 2.06 g (0.01 moles) of DCC, 0.12 g (0.001 moles) of 4-dimethylaminopyridine (DMAP) and an amount of 1-(4-n-alkoxy-benzoyloxy)-4-hydroxy-benzene corresponding to 0.01 moles are added to 50 mL of ether. The mixture is allowed to stand 2-3 days at room temperature. The N,N'-dicyclohexylurea formed is then filtered off with suction. The mother liquor is washed several times with water and dried over sodium sulfate. The solvent is then distilled off in a rotary evaporator and the residue is recrystallized several times from methanol.
Yield: 40-50% of the theoretical.
C. Esterification in the Presence of Water-Soluble Carbodiimide
To a solution of 0.3 g (0.0021 moles) of (S)-2-chloro-3-methylpentanoic acid, 0.003 moles of 1-(4-n-alkyloxy-benzoyloxy)-4-hydroxybenzene and 0.01 g DMAP in 50 mL of absolute CH.sub.2 Cl.sub.2 in a flask, 0.69 g (0.0025 moles) of 1-(3-dimethylaminopropyl)-3-ethyl-carbodiimide tosylate in 30 mL of absolute CH.sub.2 Cl.sub.2 is added dropwise with stirring and cooling in ice. After standing for 2-3 days at room temperature, the reaction batch is washed several times with water and dried over sodium sulfate. The solvent is then evaporated off in a rotary evaporator and the residue is recrystallized several times from n-hexane/acetic acid.
Yield: 50-60% of the theoretical
The following Tables 1-6 show the transition temperatures of inventive substances.
In the Tables:
K=the crystalline, solid state
S.sub.C =the ferroelectric smectic C phase
S.sub.A, S.sub.B, S.sub.G =Smectic A, B, G phases
CH=cholesterinic phase
Is=isotropic liquid phase
N=nematic phase
The temperatures are given in .degree.C.
In the following Table 11, substances with their transition points are given. They were combined into different mixtures, the transition temperatures of which were then determined.
Mixtures produced:
Mixture 1
The mixture consists of:
Mixture 2
The mixture consists of
Mixture 3
The mixture consists of
Mixture 4
The mixture consists of
Mixture 5
The mixture consists of
Mixture 6
The mixture consists of
Mixture 7
The mixture consists of
Mixture 8
The mixture consists of
All mixtures have ferroelectric phases, which are stable at room temperature or at somewhat higher temperatures.
Claims
We claim:
1. Liquid crystalline ferroelectric compounds of the formula ##STR64## wherein R.sup.1 is (CH.sub.3).sub.2 CH--, (CH.sub.3).sub.2 CHCH.sub.2 -- or C.sub.2 H.sub.5 CH(CH.sub.3)-- and l is an integer 1 to 12.
2. Liquid crystalline ferroelectric compounds as defined in claim 1, in which R.sup.1 is C.sub.2 H.sub.5 CH(CH.sub.3).
3. A liquid crystalline ferroelectric compound as defined in claim 1, in which R.sup.1 is (CH.sub.3).sub.2 CH-- and l is 10.
4. Liquid crystalline ferroelectric compounds as defined in claim 1, in which R.sub.1 is (CH.sub.3).sub.2 CH--.
5. In an opto-electronic display containing at least one liquid crystal compound, the improvement in which at least one of said compounds is according to claim 2.
6. In an opto-electronic display containing at least one liquid crystal compound, the improvement in which at least one of said compounds is according to claim 1.
7. In an opto-electronic display containing at least one liquid crystal compound, the improvement in which at least one of said compounds is according to claim 3.
8. In an opto-electronic display containing at least one liquid crystal compound, the improvement in which at least one of said compounds is according to claim 4.
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