JPH01242556A - Optically active liquid crystal compound - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (X is -COO- or -OCO-; Y is -COO-, -O- or direct bond; m and n are 1 or 2 and m+n is 2 or 3; R is >=4C alkyl; at least one of C3F7OCF(CF3) and R is optically active group). EXAMPLE:4''-Octyloxyphenyl 4'-(perfluoro-1-propyloxyethyl)carbonyloxy4- biphenylcarboxylate. USE:A liquid crystal material having great spontaneous polarization, excellent in chemical and light stability with high-speed responsiveness and capable of exhibiting ferroelectricity in a wider temperature range. PREPARATION:An optically active perfluoro-2-propyloxypropionic acid expressed by formula II is reacted with a chlorinating agent to provide an acid chloride, which is then reacted with a pyridine solution to afford the aimed compound expressed by formula I.

Description

[Detailed Description of the Invention] [Field of Applications] The present invention relates to an optically active liquid crystal compound that is currently widely used in practical use as a display method for liquid crystal display elements. There are two types: twisted nematic type (TN) and dynamic scattering type (DS). This is a display using a nematic liquid crystal cell that uses nematic liquid crystal as a generating component. One of the drawbacks of conventional nematic liquid crystal cells is their slow response speed, which is often criticized as being only possible on the order of a few milliseconds. This is one of the factors that limits the range of applications of nematic liquid crystal cells. In contrast, it has recently become clear that high-speed response can be obtained by using smectic liquid crystal cells.

It is said that some photoactive smectic liquid crystals exhibit ferroelectricity, and there is great interest in their applications. Ferroelectric liquid crystal was developed in 1975 by R.
, B., Mayer (R.B.

It was first synthesized by J. Meyer) et al.
6, page L69 (1975)), which is 4-(4'
-n-Tesyloxybenzylideneamino)-2-methylbutyl cinnamate (DOBAMBC) is a compound of ship base yarn with representative Shio 1j, ζl Shigakari') J!
, for example, in the chiral smectic C phase, it is characterized by the fact that there is one case in the city. Is that so? &,N,A. Kukuku (N, A,
C1ark) et al. [AppL Phys, Engineering 4θ11.] Volume 56,
No. 899 (1980) IK! Therefore, in the thin film cell of DOBAMBC, the quick response of only microsecond order is 4'n, and this is a missing point, and the ferroelectric liquid crystal has a fast response of 1'4: and memory. 1.2 It is attracting attention as a unique material that is used not only for display arrays in LCD TVs, but also for parts of optoelectronic/Ctronics related elements such as former printer heads, optical Fourier transform elements, and light valves. There is. strength,! 8-injection liquid crystal cell V
In this case, it is advantageous to use a material with a high induction rate and a large self-polarization because the cell can be driven faster, so it is desirable to develop forest materials with a large spontaneous polarization. In addition, in practice (1) some compounds themselves are stable, and furthermore,
It is essential to demonstrate the dielectric properties of gold over a wide temperature range centered around room temperature.

[Emission lν] is solved,! ：One task,】However,
DDBAIMBCfl, which 7-base type 11 two-base type, has a difficulty in terms of gas resistance to water and light, etc.
In addition, ferroelectricity k・ηmu1lengthψn! However, although it has a side temperature of about 5°C, it is not suitable for practical use.Therefore, as an α-crystalline material, it is physically and chemically stable. There are strong expectations for the realization of a material system with a spontaneous polarization of 7 or more.

The object of the present invention is to obtain a new liquid crystal compound that has excellent chemical stability, excellent photostability, large spontaneous polarization, and a wide temperature range of chiral smectic C phase. In addition, the present invention can be used to improve recitation speed response using the current Kuji active crystalline compound or a liquid crystal 1 simulant containing it? Does it have a liquid crystal element, etc.? This is what we are trying to provide.

[Solved by charging]! Means to do so]

Summary of the Invention W, -1'' The present invention (t) is an invention relating to an optically active liquid crystal compound, and is characterized by being a compound represented by the general formula 1 below.

[However, x 1-coo- group or 1d-OCO- group, Y
is -C0〇- group, -〇- group or direct bond,! 11. l
It shows the number of tl or 2, but m+n is 2 or 3 and it is 69R.
indicates an alkyl fund with carbon number of 4 or more, C3F70CF (
At least one of the CF3)- group or the group R is an optically active group. When this optically active compound, especially the perfluoro-1-glopyloxyethyl group, is optically active, it is possible to Since carbonyl group and CF3 group are bonded,
It has a very strong optical rotation. - Also, the central skeleton has an ester structure containing two or more benzene rings, and since there is a long-chain alkyl group (preferably 4 to 18 carbon atoms) at the end of the molecule, it itself has special characteristics as a synthetic compound. It is of course something to be said.

〔The production of chemical substances〕

The 11th compound vlJ of the general formula 1 of the present inventor can be synthesized, for example, according to the following method.

C3Izu, 0CF (Cl I Coot (→C3F70
CF(CFriCOC!→CsFr0CF(CFs)C
Congratulations on the successful manufacturing process on O06x+Y-R. First, optically active perfluorinated 2-globyloxyprobione (PPPA) is reacted with a chlorinating agent such as phthaloyl chloride, and then acid chloride is subjected to vacuum distillation. get. The toluene bath solution is reacted with a pyridine solution of a hydroxy compound, and the product is purified by silica gel column chromatography and further recrystallized if necessary.

When used for racemic perfluoro-2-propyloxyglobion Iff', the alkyl group R of the hydroxy compound is used on a compound having optical activity, and the compound of general formula l is prepared in the same manner. The present invention, which can be performed, and the present invention [Implemented L + LL, will be described more specifically, but the perpetrator 1 phase of the present invention is not limited by these implementation.

Example 1 2.1 t of 4'-hydroxy-4-biphenylcarboxylic acid
was dissolved in pyridine 65-, optically active perfluoro-2
-Roride 552t of propyloxypropionic acid
Dissolve in toluene 50- and gradually add 9-solution to 60-7
The mixture was stirred at 0°C for 3 hours, then allowed to stand for 3 hours, then water was added and extracted with ether. After drying, the solvent was distilled off. Thionyl chloride (10) was added to the residue and heated for 2 hours, excess thionyl chloride was distilled off under reduced pressure, and the entire residue was dissolved in toluene (30).
4-octyloxyphenol 2.32 and pyridine 30
- Gradually drop it into # solution and incubate at 55-65℃ for 10 hours, - After standing overnight, hydroxide) IJum water bath solution, then washed with water, and after drying, the solvent was distilled off to leave a residue. Column chromatography on silica gel (solvent: butane-chloroform)
The optically active compound (4'-(barfluoro-1)
-Propyloxyethyl9carbonyloxy-4-biphenyl-7rR-4''-octyloxyphenyl ester was obtained.

Next, this compound (■) was sealed in a transparent cell with a thickness fJ5 μm and observed under a polarizing microscope while applying a ±5 V, IHzLv electric field.6C1,6~9EL8CL7)
It was observed that Aiji L responded within the range. Other phase transitions/MIf: are shown in Table 1. Note that Cry is in a crystalline state and 5CI) is a chiral smectic C phase of a ferroelectric material, which indicates that at least a portion of it responds to the above electric field. SA is smectic physiognomy, N bone is chiral nematic phase,
o'! indicates that the phase exists, and - indicates that it does not exist. When I measured the total spontaneous polarization of the octopus compound using the triangular wave method, the value was 194 nC/-.

Example 2 Optically active compounds (1) and (2) were prepared in the same manner as in 111 except that 4-decyloxyphenol or 4-octylphenol was used.

1'fc4-octyloxy-4-biphenylcaryy
:y(H-a''-humanmixiphenyl, 4-hydroxybenzoic acid #!/, -4'-octyloxybiphenyl, 4-hydroxybenzoic acid-4'-decyloxypiphenyl or 4-hydroxybenzoic acid- HI production of optically active compounds using 41-octyloxyphenyl t was performed as follows.

Hydroxy compound 10 mmol total pyridine 35-35%, optically active perfluoro-2-7'' O-bioxypropionic acid chloride 55 ft toluene 50 tn
A solution dissolved in t was gradually added and stirred at 60 to 70°C for 3 hours. - After leaving it overnight, add all the water and extract with ether.
After drying, the solvent was distilled off. Diluted sodium hydroxide was washed with water, then dried, the solvent was distilled off, and the residue was purified using silica gel column chromatography (solvent: hexane-chloroform).
The phase transition temperatures of these compounds (shown in Table 1) are shown in parentheses. The above shows that is monotropic.

Implementation N6 5'1 MIIK1o% perfluoro-2-propyloxypropion song's enemy chloride 'K141, 'E7
'4-(2 instead of C4-octyloxyphenol)
Example 1 except that -methylbutoxy)phenol was used.
Optically active compound (2) was produced in the same manner as above. In addition, an optically active compound (1) was prepared in the same manner as in Example 1 using racemic perfluoro-2-propyloxypropionic acid and optically active a4-(2-methylbutoxy)phenol.

The phase transition temperatures of these compounds are shown in Table 1. t
However, the value of spontaneous polarization is 37nC/c1n2. (2) was 4.5 nC/an''. Therefore, it was clear that this method was effective in increasing the spontaneous polarization of the optically active perfluoro-1-propyloxyethercarbonyloxy group in +ti. J!: Bonki'' 4 Implementation procedure 1 except that 2.4 ft of hexyl 4-human 0-oxybenzoate was used to replace 4-octyloxyphenol.
Optically active compound 0: a'-(perfluoro-1-propyloxyethyl]carbonyloxy-4
-Biphenylcarbon If -4-hexyloxycarbonylphenyl ester? Obtained. The phase transition temperature of this compound is shown in Figure 1.

H-Conflict -・ -Mausoleum Bone t φ -← -Kikumoto 0 0 l 0 0 0 0 0 0 0
zsu(l w-v--(N C4v-y--1,] E C'l (N C'i v-w-y-v
-C'I C4 ('J Satoshi Toki O○■■■■ [Yes], →・■, Wholesale Implementation 9115 An optically active compound?A liquid crystal composition?iA is prepared by mixing it with the following Sumekdec liquid crystal compound. Tomo: The temperature range of the SC bone phase at this time was 21 to 62°C, which was a wide range, and the spontaneous polarization value was 83 nC/m2.

C3F of the compound of the present invention, OC%F (CF,) C'OO○coo ○0C
iHuy 2O7&jt part smectic liquid crystal compound C2HsCH (CH,,)CH2O○coo○0C8H
, 780 mtjr part [Effect of the invention] As explained above, if the present invention is applied to the 7c process, -soft type l''T
: By using the famous original liquid crystal compound, it is possible to provide a material with high spontaneous polarization that can be used as a display element and has a high-speed response. Is the Cg crystal phase of Caiflus mectinc lower than that of Cg? Show,! When mixed, it is possible to provide a material that exhibits chiral smectic C liquid crystalline phase change over a wide range of degrees.

Claims (1)

[Claims] 1. The following general formula I: ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] [However, X is -COO- group or -OCO- group, Y is -
COO- group, -O- group or direct bond, m and n are 1 or 2
m+n is 2 or 3, R represents an alkyl group having 4 or more carbon atoms, and C_3F_7OCF (CF
_3) An optically active liquid crystal compound characterized in that at least one of the - group and the group R is an optically active group.