JPH045278A - Optically active pyrimidine compound - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to novel optically active compounds.

The compound of the present invention can be used as an electro-optical element material by itself or in combination with other liquid crystal compounds.

[Conventional technology] Currently? α-crystalline display elements are widely used as various display elements due to their low voltage drive performance, 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 slow, on the order of several msec at most, and it has recently become clear that faster response can be obtained by using ferroelectric smectic liquid crystals. .

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

A typical example of this compound is 4-(4-n-decyloxybenzylideneamino)cinnamic acid-2-methylbutyl ester (hereinafter abbreviated as DOBAMBC) developed by Meyer et al., and its chiral smectic It is characterized by exhibiting ferroelectricity in the C phase (Journal de Physique (J., Phys 1).
que)36. L-69 (1975)).

Recently, N, A, Cf a r k et al. (Applied) Physics Letters (App 1. Phys.
s, Let t, ), 36. 899 (1980)
), in the DOBAMBC thin film cell, μs
With the discovery of high-speed response on the order of ec, ferroelectric smectic liquid crystals have been used not only for displays such as LCD televisions, but also for optical printer heads, optical Fourier transform elements, and light valves. It is attracting attention as a material that can be used as a material for intermediary devices such as electronics.

However, with the currently known ferroelectric liquid crystals, it is difficult to obtain one with a wide temperature range that can be used in practical use with a single composition, and by blending several types of materials, chiral smectic C phase Although methods have been used to expand the temperature range of ferroelectric liquid crystals, there are few types of ferroelectric liquid crystals and suitable compounding materials, and the performance is insufficient, so it has not yet been put into practical use.

The following compounds are known as phenyl esters of phenylpyrimidinecarboxylic acid.

(Japanese Unexamined Patent Publication No. 149669/1983).

(However, Y is n-hexyl group or n-octyl group,
Alternatively, it represents an n-decyl group, and C with a zero represents an asymmetric carbon atom. ) However, the previous compound was chiral smectic C.
The phase temperature range is high and narrow, making it difficult to use practically.

[Problems to be Solved by the Invention] The present invention solves the problems of the above-mentioned DOBAMBC and several compounds proposed subsequently, has excellent physical and chemical stability, and can be used alone or with other seven compounds. By mixing with other compounds, it provides an excellent compound that has a low and wide temperature range.

[Means for Solving the Problems] That is, the present invention has the general formula (I) (wherein R1 is an alkyl group having 6 to 18 carbon atoms,
R2 is an alkyl group having 1 to 12 carbon atoms, m is 0 or 1, n
is 0 or 1, and C marked with * represents an asymmetric carbon atom. ) provides an optically active pyrimidine compound represented by:

Unlike DOBAMBC, for example, the compound of the present invention is physically and chemically stable because it does not have a Schiff base, and when used alone or mixed with other compounds, it becomes a ferroelectric liquid crystal, has a low and wide temperature range, and has high-speed response. It has excellent characteristics.

The compound of the present invention can be produced, for example, by the method described below.

The optically active phenol compound represented by the general formula (II) (where m, n, R'' and C with * have the same meaning as in the formula (I)) is added to the optically active phenol compound represented by the general formula (m
) (Here, R1 has the same meaning as in formula (I).) It can be produced by reacting a carboxylic acid represented by the following formula or an acid chloride which is an active derivative of the carboxylic acid.

In the esterification reaction using carboxylic acid, dichlorohexyl carbodiimite (DCC) or the like is used as a dehydrating agent.
N as a carboxylic acid activation catalyst.

N-dimethyl-4-aminopyridine or the like is used, and chloroform, methylene chloride or the like is used as a solvent. The reaction temperature is 0 to 100°C, and the reaction time is 1 to 24 hours.

In the esterification reaction using acid chloride, a basic substance such as pyridine or triethylamine is used as a dehydrochlorination agent, and hexane, toluene, diethyl ether, etc. are used as a solvent. The reaction temperature is 0 to 130°C, and the reaction time is 1 to 24 hours.
After carrying out an esterification reaction of hensyloxybenzoic acid chloride with an optically active alcohol compound represented by the general formula (rV) (where m, n, R2 and C with * are the same as in formula (I)) , can be easily synthesized by hydrogenolysis of hensyl ether, which is a protective group.

The compound of general formula (III) is, for example, JP-A-62-29
It can be synthesized by a known method described in Japanese Patent No. 2767.

In the general formula (I), the alkyl group having 6 to 18 carbon atoms for R1 includes hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group,
Examples include linear or branched alkyl groups such as tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl. Further, as the alkyl group having 1 to 12 carbon atoms for R2, methyl group, ethyl group, propyl group, methyl group, pentyl group, hexyl group,
Examples include linear or branched alkyl groups such as heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group.

Representative examples of the optically active pyrimidine compound represented by the general formula (I) include the following compounds (1) to [phase].

That is, ■: 4- (5-dodecyloxypyrimidine-2-
yl)-benzoic acid-(R)-4-[1-(methoxycarbonyl)ethoxylponylcophenyl ester, ■: 4-(5-dodecyloxypyrimidine-2-
yl)-benzoic acid-(S)-4-[1-(butoxycarbonyl)ethoxylponylcophenyl ester, ■: 4-(5-dodecyloxypyrimidine-2-
yl)-benzoic acid-(R)-4-El-dodecyloxycarbonyl)ethoxylponylcophenyl ester, ■: 4-(5-)'decyloxypyrimidine-2
-yl)-benzoic acid-(S)-4-[1-(isopropoxycarbonyl)ethoxyluponylcophenyl ester, ■: 4-(5-hexyloxypyrimicin-2-yl)
-benzoic acid-(R)-4-[1-(butoxycarbonyl)ethoxycarbonyl coffeninoester, ■: 4-(5-dodecyloxypyrimidin-2-yl)-benzoic acid-(R)-4- [2-(ethoxycarbonyl)-1-methylethoxycarponylcophenyl ester, ■: 4-(5-octadecyloxypyrimidine-2
-yl)-benzoic acid-(R)-4-[2-()"decyloxycarbonyl)-1-methylethoxylponylcophenyl ester, ■: 4-(5-dodecyloxypyrimidin-2-yl) )-benzoic acid-(S)-4-[2-(,methoxycarbonyl)proboxycarponylcophenyl ester, ■: 4-(5-dodecyloxypyrimicin-2-
inolebenzoic acid-(R)-4-[2-(butoxycarbonyl)propoxycarbonyl]phenyl ester, [phase]: 4-(5-dodecyloxypyrimidine-
2yl)-benzoic acid-(R)-4-[3-(methoxycarbonyl)-2-methylbroboxycarbonylcophenyl ester, ■: 4-[5-(16-methylheptadecyloxypyrimidine)-2 -yl]-benzoic acid-(R)-4-
[1-(Methoxycarbonyl)ethoxyluponylcophenyl ester, @:4-(5-isopropoxybilymidin-2-yl)-benzoic acid-(R)-4-[2-(butoxycarbonyl)-1 -methylethoxycarbonyl]phenyl ester, @: 4-(5-tert-butyloxypyrimidin-2-yl)-benzoic acid-(R)-4-[1-(hexyloxysulfonyl)ethoxyluponylco Phenyl ester, @: 4-[5-(2,2-dimethyloctyloxypyrimidin)-2-yl)-benzoic 1m-(R)-4
-[1-(10-methylundecyloxycarbonyl)
ethoxycarbonyl]phenyl ester, ■:4-(5
-Cutyloxypyrimidin-2-yl)-benzoic acid-
(R)-4-[1-(2,2-dimethyloctyloxycarbonyl)ethoxycarbonyl]phenyl ester, @:4-<5-dodecyloxypyrimidin-2-yl)
-benzoic acid-(R)-4-[3-(butoxycarbonyl)-2-methylbroboxycarponylcophenyl ester Particularly preferred among these compounds are ■:4-(
5-dodecyloxypyrimidin-2-yl)-benzoic acid-(R)-4-[1-(methoxycarbonyl)ethoxycarbonyl]phenyl ester, ■: 4-(5-dodecyloxypyrimidine-2-
yl)-benzoic acid-(S)-4-[1-(butoxycarbonyl)ethoxyluponylcophenyl ester, ■2 4-(5-dodecyloxypyrimidin-2-yl)-benzoic acid-(S)- 4-[1-(isopropoxycarbonyl)ethoxycarbonyl]phenyl ester, ■: 4-(5-dodecyloxypyrimidin-2-yl)
-benzoic acid-(R)-4-[2-(ethoxycarbonyl)-1-methylethoxyluponylcophenyl ester, ■: 4-(5-dodecyloxypyrimidin-2-yl)
-benzoic acid-(S)-4-[2-(methoxycarbonyl)propoxycarbonyl]phenyl ester.

[Example] The present invention will be explained in more detail below with reference to Examples.

In addition, the measurement of phase transition temperature and phase identification in the examples were performed using DS
Fruit combing was performed by C measurement and polarized light microscopy observation. Cry represents a crystalline phase, SmC*a a smectic C phase, SmA a smectic A phase, Xl an unknown phase, and Iso an isotropic phase.

Example 1 4-(5-dodecyloxypyrimidin-2-yl)-benzoic acid-(R)-4-[1-(methoxycarbonyl)ethoxyluponylcophenyl ester was added to a 50 ml round bottom flask (R )-4-hydroxybenzoic acid-(1-methoxycarbonyl)ethyl 191 m
g (0,850 mmo 1 ) and 360 mg of 4-(5-dodecyloxypyrimidin-2-yl)-benzoic acid
(0,935 mmo 1) and N.

N-dimethyl-4-aminopyridine 10.4 mg (0,
085 mmol) and 20 ml of methylene chloride,
The mixture was stirred at 25°C. Add 193 mg (0°935 mmol) of dicyclohexylcarposiimide to this mixture,
Reactions were carried out three times for 18 h at 25 °C, then 10 ml of 5%
Washing with aqueous acetic acid solution was performed three times, and washing with 10 mff1 of water was performed again three times. After removing the organic solvent under reduced pressure,
Purified by silica gel column chromatography (solvent: methylene chloride/ether = 20/1 v/v),
110 mg of the target product was obtained by recrystallizing from hexane.
(0,190 mmol) was obtained. The yield was 22%.

The characteristic values of this compound were as follows.

'H-NMRCDCl2 δ [ppm] 0.88 (3
H, t), 1.2-1.6 (18H, m), 1
．． 65 (3H, d).

1.86 (2H, m), 3.79 (3H, S
), 4.14 (2H,t), 5°36
(l)t, q), 7.37 (2)1. d),
8゜19 (2)1. d), 8.29 (2H
,d), 8.50 (2H,S), 8.5
1 (2H, d)IRKBr disk wavelength [c
m=ko2900.2850, 1760, 1?20
, 1600.1570 , 1435.1270.111
5, 10?0,865,750 M5EI method m/e (relative intensity) 590 (M", 0.1), 559 (]),
487(2), 367 (10 Phase transition temperature [0C] DSC polarization microscope Cry i SmC* Jin SmA #
Is.

Example 2゜4-(5-)decyloxyvirimicin-2-yl)-
Benzoic acid-(S)-4-El-(butoxycarbonyl)ethoxycarbonylcophenyl ester In Example 1, in place of (R)-4-hydroxybenzoic acid-(1-methoxycarbonyl)ethyl, (S)
The desired product was obtained in the same manner as in Example 1 using ethyl-4-hydroxybenzoate (1-butoxycarbonyl). The yield was 6.3%.

The characteristic values of this compound were as follows.

' H-N M RCD C support 3 δ mouth 1) p
nl co0.89 (3H, t), 0.93 (3N,
t), 1.2-1.7 (25H, m).

1.86 (2H, m), 4.14 (2H, t)
, 4.19 (2H,t,), 5゜34(IN
, q), 7.36 (2H, d), 8.19 (2
H, d), 8.29 (2N, d), 8.50
(2H, S), 8.51 (2H, d) I RK
B r d i s k Wavelength [cm-'ko294
0.2900, 2850, 2830.1755.174
0.1730.1?15,1595.1570,154
0,1500,1435,1355,1270,120
0,1110,1055.880,865,765,7
50,735M5EI method m/e (relative intensity) 632 (Mゝ, 0.1), 487 (1),
367 (100) Phase transition temperature ['C] DSC polarizing microscope +8 Example 3゜4-(5-dodecyloxypyrimicin-2-yl)-benzoic acid-(S)-4-[1-(isopropoxycarbonyl) ) Ethoxyluponylcophenyl ester In Example 1, (S) in place of (R)-4-hydroxybenzoic acid-(1-methoxycarbonyl)ethyl
The desired product was obtained in the same manner as in Example 1 using ethyl-4-hydroxybenzoate (1-isopropoxycarbonyl). The yield was 8.3%.

The characteristic values of this compound were as follows.

H-NMRCDCJ! 3 δ [p pm co0.88
(3H, t), 1.2 to 1.6 (24H, m),
1. (33(3)1.d).

1.85 (2H, m), 4.14 (2H, t),
5.10 (IH, 5ept).

5.29 (IH, q), 7.35 (2H, d),
8.19 (2N, d), 8゜29 (2H, d)
, 8.50 (2H,S) , 8.51 (
2H, d) IRKBr disk wavelength [cm-'
ko2900.2840, 1?50, 1720, 1
600, 1570.1535, 1500, 143
0.1385, 1270, 1205, 1105, 106
5,1010.865.750M5Ef method m/e (relative intensity) 618 (M", 0.1), 559 (1),
487 (2), 367 (10 phase transition temperature [°C]
DSC polarizing microscope? 7 120 1
32 Cry ”:; SmC* Yu SmA #
Is.

Example 4 4-(5-dodecyloxypyrimidin-2-yl)-benzoic acid-(R)-4-[2-(ethoxycarbonyl)-
1-Methylethoxyluponylcophenyl ester In Example 1, (R)-4-hydroxybenzoic acid-(1-methoxycarbonyl)ethyl is replaced by (R)
The desired product was obtained in the same manner as in Example 1 using 4-hydroxybenzoic acid-[2-(ethoxycarbonyl)-1-methyl]ethyl. The yield was 44%.

The characteristic values of this compound were determined as follows.

' HN M RCD CJ! 3 δ[ppm]0
．． 88 (3H, t), 1.2-1.7 (24) 1.
m), 1.86 (2H, m).

2.65 (IH, dd), 2.80 (LH, dd)
, 4.12(21(,t).

4.14 (2N, q), 5.54 (1N, m
), 7.34 (2H, d), 8°12(
21(,d), 8.29(2H,d), 8.5
0(28,S), 8.51(2)1. d) IRKBr disk wavelength [cm-'] 2900
．． 2850, 1?10, 1600, 1570.1
540.1500.1435.1310.1270,1
200,1015,1050,1010.910.88
0.865.75MSEI method m/e (relative intensity) 618 (M", 0.1), 367 (100) Phase transition temperature ['C:] DSC polarizing microscope Cry
#SmC1: #SmA #15O Example 5 4-(5-dodecyloxypyrimidin-2-yl)-benzoic acid-(S)-4-[2-(methoxycarbonyl)broboxycarbonyl]phenyl ester Example 1, in place of (R)-4-hydroxybenzoic acid-(1-methoxycarbonyl)ethyl (S)
The desired product was obtained in the same manner as in Example 1 using -4-hydroxybenzoic acid-[2-(methoxycarbonyl)cobropyr. The yield was 38%.

The characteristic values of this compound were as follows.

' HN M RCD CJ13 δ [p pm
0.88 (3N, t), L-2~1.6 (21N
, m), 1.86 (2H, m).

2.98 (IH, m), 3.74 (3) 1. s),
4.14 (2ft, t), 4゜46 (2Lm
), 7.35 (2)1. d), 8.19
(2)1. d), 8.29(2)1. d),
8.50 (2N, s), 8.51 (2N, d)I
RKBr disk wavelength [cm-'] 2920.
2850, 1730.1605.1575.1545
．． 1505.1445.1330.1280,1210
,1165.1070,1015.870.75069
0M5 FAB method m/e (relative intensity) 605 (MH
”, 80), 604(M”, 5), 48
7 (30).

460 (25), 367 (100) Phase transition temperature ['C:] DSC polarizing microscope 112
C27158 Cry b SmC* # SmA #
Is.

Application Examples The optically active pyrimidine compound obtained in Example 1 was prepared by using polyimide as an alignment film, I To (Indium-T
The sample was sealed in a liquid crystal cell with a cell thickness of about 3 μm using an in-Ox i d e) film as an electrode, and was slowly cooled in an isotropic phase to obtain a uniform monodomain SmC* phase.

When the response time was determined from the peak of the polarization inversion current when an AC rectangular wave of ±IOV was applied, a high-speed response of 16 μs at 107° C. was obtained.

[Effects of the Invention] The compound of the present invention is physicochemically stable and has high-speed response in a low and wide temperature range, so it is extremely suitable as an electro-optical element material.

At the end, a table of examples of compounds of the invention is given.

Claims (1)

[Claims] (1) The following general formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (However, in the above formula, R^1 is an alkyl group with 6 to 18 carbon atoms, and R^2 is an alkyl group with 1 to 12 carbon atoms. alkyl group, m is 0 or 1
, n is 0 or 1, and C marked with * represents an asymmetric carbon atom. ) An optically active pyrimidine compound represented by