JPH03151369A - Optically active compound - Google Patents

Abstract

NEW MATERIAL:An optically active compound of formula I (R<1> is 6-16C alkyl or alkoxy; R<2> is 2-3C alkyl or 1-4C haloalkyl; R<3> is 1-12C alkyl; * exhibits to be optically active. EXAMPLE:(R)-4-(5-tridecylpyrimidin-2-yl) benzoic acid 4-(2-ethoxycarbonyl-1- chloromethylethoxycarbonyl)phenyl ester. USE:Especially useful as a ferroelectric liquid crystal material exhibiting a chiral smectin C phase. The compound of formula I is physically and chemically stable and forms ferroelectric liquid crystals exhibiting their properties at lower temperature ranges and excellent high speed resposing properties when single or mixed with any other compound. PREPARATION:A: compound of formula II is reacted with a compound of formula III and subsequently subjected to a benzyl group-removing reaction. The prepared compound of formula IV is reacted with a compound of formula V to provide the compound of formula I.

Description

Detailed Description of the Invention A. Object of the Invention (Field of Industrial Application) The compound of the present invention is expected to be used as a liquid crystal compound, and in particular, it can be used as a ferroelectric liquid crystal material exhibiting a chiral smectic C phase. It is a compound useful as

(Prior Art) Currently, liquid crystal display elements are widely used as various display elements due to their low voltage drivability, low power consumption, small size, and thinness.

At present, most of the devices that have been put into practical use are TN (Twisted Nematic) using nematic liquid crystals.
It is a type display element. However, this display method has the disadvantage that the response time is on the order of msec and the response speed is slow. Recently, it has been found that faster response can be obtained by using ferroelectric smectic liquid crystals.

Ferroelectric smectic liquid crystal was developed by R.B. in 1975.

4-(4-n-
A typical example of this compound is decyloxybenzylidene amino) cinnamic acid-2-methylbutyl ester (hereinafter abbreviated as DOB AMB C), which exhibits ferroelectricity in the irral smectic C phase. (Journal de Physique (J, P) ly
sique)u, L-69 (1975)). recently,
N, A, C1ark et al. (Applied Physics Letters (Appl, Phys, Let t,
) once, 899 (1980)),
With the discovery of high-speed response on the μsec order in DOBAMBC's thin-film cells, ferroelectric smectic liquid crystals have been used not only for displays such as LCD televisions, but also for optical printer heads, by utilizing their high-speed response. It is attracting attention as a material that can be used for optical Fourier transform elements, light valves, and other optoelectronic cables.

(Problems to be Solved by the Invention) The present invention solves the problems of the above-mentioned DOBAMBC and some compounds proposed subsequently, and has excellent physical and chemical stability. By mixing with other compounds, a compound with a low temperature range and excellent high-speed response is provided.

1. Structure and Effects of the Invention (Means for Solving the Problems) The present inventors have conducted intensive studies to achieve the above object, and as a result, have completed the present invention.

That is, the present invention relates to the general formula (1) [However, in the above formula (1), R1 represents an alkyl group or an alkoxy group having 6 to 16 carbon atoms, and R2 represents an alkyl group having 2 to 16 carbon atoms.
-3 alkyl group or a haloalkyl group having 1 to 4 carbon atoms, R3 represents an alkyl group having 1 to 12 carbon atoms, and N represents optical activity.

] This is a novel optically active compound represented by

Optically active compounds according to the invention are, for example, D.

Because it does not have a Schiff base like BAMBC, physical
It is chemically stable, and when used alone or mixed with other compounds, it becomes a ferroelectric liquid crystal, has a low temperature range, and has excellent high-speed response.

In general formula (1), the alkyl group having 6 to 16 carbon atoms for R1 includes a hexyl group, a heptyl group, an octyl group,
Straight chain or branched alkyl groups such as nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, etc., and alkoxy groups include hexyloxy group, heptyloxy group, octyl group, etc. Examples include linear or branched alkyl groups such as oxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group, tridecyloxy group, tetradecyloxy group, pentadecyloxy group, and hexadecyloxy group. .

On the other hand, examples of the alkyl group having 2 to 3 carbon atoms in R2 include ethyl group, propyl group, and isopropyl group, and examples of the haloalkyl group having 1 to 4 carbon atoms include chloromethyl group, 2-chloroethyl group, dichloroethyl group, 3- Examples include chloropropyl group.

In addition, the alkyl group having 1 to 12 carbon atoms for R3 is a linear or branched alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, etc. can be exemplified.

(- Boat fishing production method) Compound (1) of the present invention can be produced by the method shown below. The reaction formula is illustrated below, in which R1,
R2 and R3 are the same as defined in general formula (1).

Note that the number in parentheses of the compound shown in the structural formula represents the compound in the upper row.

(2) (3) (4) (5) (6) In the reaction step (I), dicyclohexylcarbodiimide or the like is used as a dehydration condensation agent, and N is used as a catalyst.

This can be easily carried out by using an organic base such as N-dimethyl-4-aminopyridine and using methylene chloride, chloroform, etc. as a solvent. The reaction step (II) is a debenzylation step, which can be carried out by a known method. For example, using palladium-charcoal as a catalyst,
This can be easily carried out by using ethanol, acetic acid, etc. as a solvent and hydrogenating at normal pressure. Further, the reaction step (m) can be carried out in exactly the same manner as the reaction step (I), and can easily lead to the compound of formula (1), which is the target compound of the present invention.

The compound of formula (3) used in reaction step (I) is, for example,
Journal of the American Chemical Society (J, Am, Chem, Soc,) 9, L Yushidan, 5
It can be synthesized by the known method described in 856 (19B?). On the other hand, the formula (6
) can also be synthesized by the known method described in, for example, Japanese Patent Publication No. 55-6632.

(Example) The present invention will be explained in more detail with reference to Examples below. still,
Measurement of phase transition temperature and phase identification in Examples were carried out by DSC measurement and polarized light microscopy observation. Cry is a crystalline phase, S m C * is a chiral smectic C phase, SmA
represents a smectic phase, and IsO represents an isotropic phase.

(R)-4-(5-)lysosylpyrimidin-2-yl)
Preparation of benzoic acid-4-(2-ethoxycarbonyl-1-chloromethylethoxycarbonyl)phenyl ester (I) (R)-4-benzyloxybenzoic acid-2-ethoxycarbonyl-1-chloromethylethyl ester 4-benzyl Oxybenzoic acid 421mg (1°81mm
ol), (R)-3-hydroxy-4-chlorobutanoic acid ethyl ester 273 mg (1°64 mmol),
and N, N-dimethyl-4-amino and lysine 110
After dissolving mg (0.90 mmol 1) in 5 ml of methylene chloride at room temperature, 440 mg (2.1 mmol) of dicyclohexylcarbodiimide was added and the mixture was reacted under reflux for 5 hours.

After the reaction was completed, the precipitated solid was separated by filtration, washed with water, washed with a 5% acetic acid aqueous solution, washed with water, and then dried over anhydrous magnesium sulfate. After the desiccant was filtered off, methylene chloride was distilled off to obtain the crude target product.

This product was purified by silica gel chromatography and further recrystallized from hexane to obtain the desired (R).
-4-benzyloxybenzoic acid-2-ethoxycarbonyl-1-chloromethylethyl ester 480 mg (1
, 27 mmol) was obtained.

(n) Preparation of (R)-4-hydroxybenzoic acid-2-ethoxycarbonyl-1-chloromethylethyl ester (R)-4-benzyloxybenzoic acid-2-ethoxycarbonyl-1 obtained in (I) -460 mg (1,22 mmof) of chloromethyl ethyl ester to 5 m of acetic acid
After dissolving in 5% palladium-charcoal under a hydrogen atmosphere, the mixture was reacted for 3 hours at room temperature using 115 mg of 5% palladium-charcoal. Palladium-charcoal was filtered off, and acetic acid was distilled off under reduced pressure to obtain a crude target product.

This product was purified by silica gel chromatography to give an oily (R)-4-hydroxybenzoic acid-2-ethoxycarbonyl-1-chloromethylethyl ester of 300%
mg (1,05 tnmmol) was obtained.

(III) Production of (R)-4-(5-)lysosylpyrimidin-2-yl)benzoic acid-4-(2-ethoxycarbonyl-1-chloromethylethoxycarbonyl)phenyl ester obtained in (II) (R)-4-hydroxybenzoic acid-
2-ethoxycarbonyl-1-chloromethylethyl ester 280 mg (0,98 mmol) 5-tridecylpyrimidin-2-ylbenzoic acid 412 mg (1,08 m
mo 1) and N,N-di-dissolved, 263 mg of dicyclohexylcarbodiimide (1,27 mmo
1) was added, and the mixture was allowed to react at room temperature for 16 hours.

After the reaction was completed, the precipitated solid was separated by filtration, washed with water, washed with a 5% acetic acid aqueous solution, washed with water, and then dried over anhydrous magnesium sulfate. After the desiccant was filtered off, methylene chloride was distilled off to obtain the crude target product.

This product was purified by silica gel chromatography and further recrystallized from hexane to obtain the desired (R).
-4-(5-)lysosylpyrimidin-2-yl)benzoic acid-4-(2-ethoxycarbonyl-1-chloromethylethoxycarbonyl)phenyl ester 136 mg (
0.21mtnol) was obtained.

The characteristic values of this compound were as follows.

IH-NMR spectrum (CDC13, I) pm) 0.
88 (t, 3H), 1.22 (t, 3H), 1.24
-1.35 (m, 20H), 1°68 (m, 2H)
, 2.66 (t, 2N) , 2.92 (d, 2H) ,
3.88 (m, 2) 1), 4゜18 (c+,
2H), 5.67(m, IH), 7.35(d
, 2H) , 8.14 (d , 2) 1) , 8
.

30 (d, 2H), 8.58 (d, 2H), 8.69 (
S, 2H) IR spectrum (KB r disk, am-
')2900.2840.1740.1?10.148
0.1250.1200,760,755 mass spectrum (FAB method, m/e (relative intensity)) 651 (14, M
)1+), 650 (2, M+), 365 (100) Phase transition temperature (DSC, polarized light microscopy observation 2°C) (R)-4
-(5-)lysosylpyrimidin-2-yl)benzoic acid-
4-(2-Methoxycarbonyl-1-ethylethoxycarbonyl) phenyl ester In place of (R)-3-hydroxy-4-chlorobutanoic acid ethyl ester in Example 1, (R)-3-hydroxypentanoic acid methyl ester was used. (R)-4-(
5-) Lysosylpyrimidin-2-yl)benzoic acid-4-
(2-methoxycarbonyl-1-ethylethoxycarbonyl) phenyl ester 199 mg (0,32 mmo
l) was obtained.

The characteristic values of this compound were as follows.

IH-NMR spectrum (CDC13, pl) m) 0.
88 (t, 3N), 1.01 (t, 3H), 1.26
-1.35 (m, 208), 1° (38 (m, 2) 1
), 1.81(m, 2H), 2.65(t,
2H), 2.77(d, 2H), 3°68(
s, 3 days), 5.44 (m, IH), 7.34
(d, 2H), 8.13 (d, 2H), 8゜3
2(d,2)1), 8.58(d,2)1), 8.69
(s, 2H)! R spectrum (KBr de, Isk,
cm-')2920.2B60.1730.1440.
1260.1210.770,755 mass spectrum (
FAB method, m/e (relative intensity)) 617 (46, MH+
), 616 (4, M+), 365 (100) Phase transition temperature (DSC, @light microscope observation 1°C) Example 3 (S)-4-(5-tridecylpyrimidin-2-yl)
Benzoic acid-4-[2-methoxycarbonyl-1-(1-
Methylethyl)ethoxycarbonyl]phenyl ester Except for using (S)-3-hydroxy-4-methylpentanoic acid methyl ester ester instead of (R)-3-hydroxy-4-chlorobutanoic acid ethyl ester in Example 1. , (S)-4-(5-)lysosylpyrimidin-2-yl) by carrying out the same manner as in Example 1.
Benzoic acid-4-[2-methoxycarbonyl-1-(1-
170 mg (0.27 mmol) of methylethyl)ethoxycarbonyl]phenyl ester was obtained.

The characteristic values of this compound were as follows.

'H-NMR spectrum (CD C131ppIn) 0
．． 88 (t, 3H), 1.02 (d, 6H), 1.2
6-1.35 (m, 20H), 1゜68 (m, 2M
), 2.09(m, 1)1), 2.67(
t, 2H), 2.76(d, 2H), 3゜6
6 (s, 3H), 5.40 (m, IH),
7.34(,d, 2H), 8.13(d, 2H
), 8°31 (d, 2H), 8.58 (d, 2) 1
), 8.69 (s, 2M) IR spectrum ('KBr disk, cm-') 2870.2800.1?20.1
420.1250.1200,755,745 mass spectrum (EI method, m/e (relative intensity)) 630 (2, M
H+), 365 (100) Phase transition temperature (DSC, polarized light microscopy observation at 2°C) Example 4 (R)-4-(5-)lysosyloxypyrimidine-2-
yl)benzoic acid-4-(2-ethoxycarbonyl-1-
Chloromethylethoxycarbonyl)phenyl ester 5-dodecyloxypyrimidine-2-yl)benzoic acid in Example 1 was replaced with 5-dodecyloxypyrimidine-2-yl)benzoic acid.
(R)-4-(5-dodecyloxypyrimidin-2-yl)benzoic acid-4-(2-ethoxycarbonyl-2-yl)benzoic acid was used in the same manner as in Example 2. 104 mg (0.16 mmol) of 1-chloromethylethoxycarbonyl)phenyl ester was obtained.

The characteristic values of this compound were as follows.

Claims (1)

[Scope of Claims] [I] An optically active compound represented by the following general formula (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) [However, in the above formula (1), R^1 is the number of carbon atoms It represents an alkyl group or an alkoxy group having 6 to 16 carbon atoms, R^2 represents an alkyl group having 2 to 3 carbon atoms or a haloalkyl group having 1 to 4 carbon atoms, and R^3 represents an alkyl group having 1 to 12 carbon atoms. represents a group, and * represents optical activity. ]