JPH01299260A - Estr derivative - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (R<1> and R<2> are 1-18C alkyl; n is 1 or 2; * is optically active C). USE:Useful as a component for ferromagnetic liquid crystal compositions used for displays for liquid crystal televisions, etc., optical printer heads, optical Fourier transform elements, light valves, etc. Further useful for White Taylor type display element, cholesteric nematic phase transition type display element, etc., and also useful for heat write liquid crystal display elements, etc., as smectic liquid crystals. PREPARATION:The compound of formula I is prepared by reacting a phenolcarboxylic acid derivative of formula II with a naphtylacetic acid derivative of formula II in the presence of pyridine in a solvent such as dioxane at 50-150 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel optically active ester derivative, and more particularly to an optically active ester derivative useful as a ferroelectric liquid crystal.

(Prior Art) Since liquid crystal compounds have been used in electro-optical display devices, many liquid crystal compounds have been synthesized, and nematic liquid crystals or nematic-cholesteric liquid crystals can be used for twisted nematic mode display elements, display elements utilizing cholesteric-nematic phase transition phenomenon, or It is widely used in display devices that utilize the guest-host effect.

However, the response speed of these display elements is several meters at most.
It is on the order of ec, and this point is one of the reasons for narrowing the range of applications of liquid crystal display elements.

Recently, it has been found that when a liquid crystal exhibiting ferroelectric property, that is, a ferroelectric liquid crystal is used, a response can be obtained at a high speed on the order of μSeC.

Examples of conventionally known ferroelectric liquid crystals include 7!
p-(
Examples include @'-n-decyloxybenzylideneamine) cinnamic acid-comethylbutyl ester (hereinafter referred to as DOBAMBC)1, which has a ferroelectric property in its chiral smectic C phase (hereinafter referred to as "SmC"). It is characterized by showing gender (J, P
hysique.

J4 L-≦7 (fri75)).

N, A, C1ark and others are DOBAMB in /ri♂θ year.
Since discovering a high-speed response on the order of μSeC in a thin film cell using C (Apl) 1. ph3'5-Le
(/9♂O)Many studies have been conducted on the synthesis of ferroelectric liquid crystals, but at present, (1) they are not only in a liquid crystal state at room temperature, but also at low to high temperatures; (2) Stable against moisture, air, light, heat, etc.; (3) High dielectric constant, large spontaneous polarization, and low viscosity. There is no single ferroelectric liquid crystal compound that satisfies all of the physical requirements, such as ferroelectric liquid crystal compounds.The objective is achieved by using a composition that is a combination of several types of ferroelectric liquid crystal compounds.

(Problems to be Solved by the Invention) The present invention provides S which exhibits ferroelectric liquid crystal properties when mixed with other known liquid crystal compounds, either alone or in a mixture thereof.
The present invention provides a novel ester derivative having mC phase and good stability.

(Means for Solving the Problems) That is, the present invention has the following general formula [■] - (wherein R1 and R2 represent an alkyl group having a carbon number of 1♂, and n represents 1 or 2). The gist is the ester derivatives shown.

The present invention will be explained in detail below.

The nysten derivative of the present invention is represented by the general formula (1) above, and the carbon atom directly bonded to the naphthalene ring is an optically active carbon atom.

In the general formula CI), R1 and R2 have carbon numbers /-/
Examples of the alkyl group of r include 4 GOLr
i n -furovir, n-pentyl, n-hexyl, n
Examples include OW chain alkyl groups such as -heptyl, n-octyl, n-nonyl, n-7''yl, and n-undecyl.

Also, from the point of view of ferroelectric liquid crystallinity, n = J is better than n
== Preferable than /.

The ester derivative of the present invention can be obtained, for example, by the following reaction formula.

・・・・・・・・・・・・ [”D] ・・・・・・・・・ (E) (Reaction formula [B], [c], [D], I:E:] Inside, R
' Oyo U R2 has the same meaning as in the general formula (1). ) In the above reaction ("A), for example, in acetic acid,
It can be carried out using hydrobromic acid at temperatures of 10-120°C.

The reaction [B] can be carried out, for example, in a solvent such as benzene, toluene, or xylene using an acid catalyst such as concentrated sulfuric acid or p-toluenesulfonic acid at a temperature of j O%/jt 0°C.

The reaction [C] is carried out using a basic catalyst such as pyridine, triethylamine, potassium carbonate, or sodium carbonate in a solvent such as benzene, toluene, or xylene.
j Can be carried out at a temperature of 0°C.

The reaction [D] can be carried out using a chlorinating agent such as thionyl chloride at a temperature of 0-700'C.

The reaction (E) can be carried out, for example, in pyridine, an ether solvent such as dioxane or tetrahydrofuran, or an aromatic hydrocarbon solvent such as benzene, toluene, or xylene, or an amine deoxidizer such as pyridine, quinoline, or triethylamine. or in the presence of an inorganic deoxidizing agent such as sodium carbonate, potassium carbonate, sodium bicarbonate, etc.
It can be carried out at a temperature of 50°C.

Specific examples of the compounds of the present invention include the following.

The ester derivatives of the present invention can be used alone or as a mixture thereof, and can also be used in combination with suitable known liquid crystal compounds. The ester derivative of the present invention can be used alone or as a mixture of these liquid crystal compositions.

Such known liquid crystal compounds include ester, diester, azoxy, azo, Schiff, pyrimidine, biphenyl, phenylcyclohexane, cyclohexylcyclohexane, bicyclooctane, dioxane, benzene ring, cyclohexane ring, etc. Examples include polycyclic compound systems consisting of:

Furthermore, when forming a liquid crystal composition in the present invention, known additives such as dichroic dyes, light stabilizers, or thinners can be used in combination.

(Examples) Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples.

Example 1 In general formula [I], RLC0H19(n), R2=c
sHt t (n), synthesis of compounds with n = 2 (1) (+) -6-methoxy-α-methyl-naphthylacetic acid [[α] μ5 + t6° (C = / , CHC
Ig)]2Of to λj OCC of acetic acid and further 4
After adding Lr hydrobromic acid/00 cc and heating under reflux for 20 hours, the mixture was poured into water μi 0 CC. Salting out was carried out by adding common salt, and the precipitate was separated, washed with water, and dried to obtain carboxylic acid derivative 14!2 represented by the following formula.

(2) Carboxylic acid derivative 3 obtained in (1) above? ,n
-amyl alcohol/, G9. toluene! 0CC and p-toluenesulfonic acid! O2 was heated to reflux using a Dean-Stark reflux condenser, and the water produced was removed. After 10 hours of reaction, toluene was distilled off and cooled to obtain an ester derivative represented by the following formula 3. Got the tag.

f3) tI! -Hydroxybiphenyl-ψ-carboxylic acid 062♂2 was suspended in toluene rcc, and decanoyl chloride 0. ♂ CC and pyridine lr cc were added. After heating under reflux for r hours, a small amount of water was added and the solvent was distilled off, and the residue was extracted from the P side and washed with methanol to obtain an ester derivative O0≠12 represented by the following formula.

(4) Ester derivative obtained in (3) above 0.6≠2
and 10 cc of thionyl chloride and 10 cc of carbon tetrachloride.

Two drops of DMF were added. After heating under reflux for an hour, the solvent was distilled off under reduced pressure to obtain an ester derivative chloride.

A solution in which the entire amount of this chloride was dissolved in 6 cc of toluene,
The ester derivative O9!9 obtained in (2) above was added dropwise to a solution dissolved in 2 cc of pyridine and 1 cc of toluene. 3. At 60°C. After stirring in the evening, the mixture was poured into 20 cc of to% hydrochloric acid aqueous solution. After extraction with chloroform, the organic layer was washed successively with 10% aqueous hydrochloric acid, saturated aqueous sodium bicarbonate, and saturated brine, and then dried over Glauber's salt.

After chloroform was distilled off, the desired ester derivative represented by the following formula was obtained by purification using silica gel column chromatography in an amount of 0.33 t.The phase transition temperature of this (l, compound) was as follows.

(However, Cry is a crystalline phase, and SmC+ is a smectic C+
SmA indicates smectic A phase, Cj-h indicates cholesteric phase, and Iso indicates isotropic liquid. ) The ferroelectric properties of this compound are as follows.

Spontaneous polarization (P5)♂, ri7nC//c1ft(go
, t'C) Tilt angle (θ)22. ♂0 (R0,1℃) Response speed (τ) 374tBs (/D0,
0°C) Example 2 In the general formula CI), sHst (n), RLCI
Synthesis of compound with SHtt (n), n=2 Using belargonyl chloride in place of decanoyl chloride in Example 1, μ'-〇-belargonyloxybiphenyl-Hiro-carboxylic acid was obtained and 0.729% of this was used. Then, in the same manner as above, the desired ester derivative O1≠l? expressed by the following formula is obtained. I got it.

The phase transition temperature of this compound is as follows.

t'y, r”c ta♂, 3℃ /
31.6 °C/lA3.9 °C--→Ki-1→-11111→CrySmCSmA Ch I s.

A7J℃ Taj,ri'CI37.3℃ /1
12. ℃ Example 3 In formula CI+, RLC4H□9 (n), R2
=C5H1□(n), an example of the synthesis of a compound with n-thickness;
Decanoyloxybenzoic acid was obtained, and 0.63t of the target ester derivative represented by the following formula was obtained in the same manner as in Example 1 except that osat was used.

This compound had a melting point of 63.2°C.

(Effects of the Invention) The present compound is useful as a component for ferroelectric liquid crystal compositions used in displays such as liquid crystal televisions, optical printer heads, optical Fourier transform elements, light pulp, and the like. Since the present compound is an optically active substance, it is useful for White-Taylor type liquid crystal display elements, cholesteric nematic phase change type display elements, etc., and it is also useful as a smectic liquid crystal for thermal writing liquid crystal display elements, etc.

Sender: Mitsubishi Chemical Industries, Ltd. Representative Patent Attorney Hase - (1 other person)

Claims (1)

[Claims] The following general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
[I] Ester derivative represented by (wherein R^1 and R^2 represent an alkyl group having 1 to 18 carbon atoms, and n represents 1 or 2)