JPH021482A - Heterocyclic compound and liquid crystal element using liquid crystal material containing the same compound - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [R<1> is alkyl or alkoxy; Q is group of formula II or III; A is bond, -O- or -OC(=0)-; X is halogen; n1, n2 and 4 are 0 or 1; n3 is 0-6; n1 and n2 are not 0 at the same time; C* is asymmetric carbon atom]. EXAMPLE:(S)-6-{4-(6-methyloctyloxy)phenyl}-3-octyl-1,2,4-triazine. USE:A liquid crystal material and liquid crystal element. PREPARATION:The compound of formula VI is produced by reacting a compound of formula IV or its salt with a compound of formula V (Y1 is acid residue). Some of the compounds of formula IV used as a starting raw material are novel substances.

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention (Industrial Application Field) The present invention relates to a novel heterocyclic compound and a liquid crystal element using a liquid crystal material containing the same.

(Prior Art) Liquid crystal elements are widely used in electro-optical devices such as wristwatches, calculators, displays for personal computers, and pocket color televisions. However, the electro-optical response time of currently used nematic liquid crystals is approximately 50
Since it is slow at m5ec, its use is limited in fields where high-speed response is required, and it is also reaching its limit in terms of display capacity.

On the other hand, since ferroelectric liquid crystals exhibit high-speed response on the μSeC scale, their practical use is expected to dramatically expand the applications of liquid crystal elements.

Ferroelectric liquid crystal materials originated in 1975 from the so-called DOBAMBC synthesized by R.B. Mayer et al.
975)) to this day. Ferroelectric liquid crystals are characterized by having a chiral smectic C phase (hereinafter abbreviated as Sc main phase), but in DOBAMBC, the temperature range of the Sc phase is as high as 73 to 93°C, making it difficult to use it alone for practical use. It is difficult. In addition, there is a Schiff base and carbon-carbon 2 in the molecule.
It also has problems with chemical stability because it contains heavy bonds.

From a practical standpoint, ferroelectric liquid crystals are primarily required to exhibit Se4 phase in a wide temperature range including room temperature and to have chemical stability. Recently, attention has been paid to this point, and efforts have been made to synthesize various ferroelectric liquid crystals, ie, ester, biphenyl, and pyrimidine liquid crystals.

However, although the above-mentioned materials have satisfactory chemical stability, it is difficult to obtain a single-composition ferroelectric liquid crystal having a wide temperature range for practical use. Therefore, as in the case of nematic liquid crystals that have already been put into practical use, a method is currently being used for ferroelectric liquid crystals to expand the temperature range of the Se4 phase by blending several types of materials. In addition to expanding the temperature range of the Se4 phase, blending is an important method for improving various physical properties, such as pitch, which affects electro-optic response and orientation.

However, the number of types of ferroelectric liquid crystals currently required for use in blending is very small compared to nematic liquid crystals, and it can be said that they are in an insufficient state.

In particular, there are only a few systems, such as phenylpyrimidine systems and ester systems, which exhibit the Sc main phase over a wide temperature range near -room temperature, and the degree of freedom in selection when performing blending is limited.

(Problems to be Solved by the Invention) As mentioned above, since there are very few types of ferroelectric liquid crystals used as blend materials, various physical properties necessary for liquid crystal elements, such as phase transition series of liquid crystal phase, It is very difficult to obtain a liquid crystal composition that satisfies all of the temperature range of the Se4 phase, the tilt angle, the pitch of the Δn1Sc* phase, the response time, etc.

The present invention utilizes a heterocyclic compound, which is a component of a liquid crystal composition useful for improving the above-mentioned physical properties, and a liquid crystal composition containing the same, by using a completely new petro ring as a skeleton structure. The purpose of the present invention is to provide a liquid crystal device with a high quality.

[Structure of the Invention] (Means for Solving the Problems) The present invention is based on the general formula (wherein, R is alkyl or alkoxy, n, nl,
n-2 and n4 are 0 or 1, n3 is an integer of 0 to 6, nl and 02 are not 0 at the same time, and C* represents an asymmetric carbon atom) and this heterocyclic compound. It relates to a liquid crystal element using a liquid crystal material containing a cyclic compound.

-Cost of clothes CI) The heterocyclic compound of the present invention represented by The thing is It can be produced by the following synthetic route.

or its salt 10 synthesis route 3 (II2-1) CU3-1) or its reactivity I or its reactive derivative + ■ Synthesis route 4 R1()CONHNH2 or its salt (If4-1) + (U5-2) or Salt or reactive derivative thereof (U4-2) (U5) The raw material compounds for synthesizing the target compound of this invention include novel compounds. These starting compounds can be produced by the following synthetic route.

■ Raw material synthesis route A Raw material synthesis route D (IID-1) (II, -2) (II5-2) or its salt Ho%coocu　3+　R1′Y.

R" O-QkeC00CH3 R" O0CONHNH2 (n4-1') or its salt raw material synthesis route E (I[2 Raw material synthesis route F HO-@) -C00CH3 (II, -1) -1' R, -4 Prevention C00CH3 (II, -2) R, ()CONHNH9 (IIF-3) or its salt raw material synthesis route G (Ifo-2) (IIP-5) [ (IIH-1) (II2-1') Above, synthesis In the formula showing the route, R' Q, A, X, nl
, R2, R3, and R4 each have the same meaning as before, YYYYYY and Yc 1ゝ 2ゝ A'C'D' E is an acid residue, Y' is a halogen, 1' R is an alkyl, R and RH is a protected hydroxy.

Preferred examples and explanations of the various definitions in this specification are detailed below.

Examples of the alkyl of R1 and the "alkyl"1' portion of alkoxy and the alkyl of R include straight-chain or branched alkyl having 1 to 20 carbon atoms, specifically methyl, ethyl, propyl, isopropyl, butyl,
Isobutyl, t-butyl, pentyl, isopentyl, neopentyl, t-pentyl, hexyl, isohexyl,
Examples include heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, and the like.

Examples of the halogens for X and Y include fluorine, chlorine, bromine, and iodine.

YYYY 1'2'A'C' D゛YE and YG
Acid residues include halogens (fluorine, chlorine, bromine, iodine), allenesulfonyloxy (benzenesulfonyloxy, tosyloxy, etc.), lower alkanesulfonyloxy (mesyloxy, ethanesulfonyloxy, etc.)
and acyloxy such as lower alkanoyloxy (acetyloxy, propionyloxy, etc.).

Examples of the protected hydroxy of R1 and RH include alkoxy (lower) alkoxy (benzyloxy, trityloxy, etc.).

The method for producing the object compound of this invention will be explained in detail below.

Synthetic route 1 Compound (I) can be produced by reacting compound (■, -1) or a salt thereof with compound (II, -2).

Examples of the salt of compound (n, -1) include hydrochloride and acetate.

The second reaction is carried out in the presence of acetic acid and its alkali metal salts (sodium acetate, potassium acetate, etc.).

This reaction is usually carried out in alcohol (methanol, ethanol, etc.), methylene chloride, mixtures thereof or other solvents that do not adversely affect the reaction.

The reaction is usually carried out at or under heating.

Compound (nl-1) includes a novel compound, and they can be produced by the method of raw material synthesis route B.

Compounds (II, -2) include novel compounds, which can be produced by methods to the raw material synthesis route or methods analogous thereto.

Synthetic route 2 Compound (1) is compound (II2-1) and compound (■2-
2) can be produced by reacting with.

This reaction can be carried out in the presence of an alkali metal hydride base (such as sodium hydride).

The reaction is carried out in dimethylformamide, tetrahydrofuran, dioxane, ethyl acetate, methylene chloride, mixtures thereof or other solvents that do not adversely affect the reaction.

This reaction is usually carried out under cooling or heating.

Compound (n2-1) includes a novel compound, and can be produced by a method combining raw material synthesis routes E and F or raw material synthesis routes G and H.

Synthetic route 3 Compound (I) is a compound (n2-1) and (■3-1)
or a reactive derivative thereof.

Examples of reactive derivatives of compound (n3-1) include acid halides (such as acid chloride), acid anhydrides, active amides, and active esters.

This reaction is usually carried out in water, alcohol (methanol, ethanol, etc.), methylene chloride, dimethylformamide, tetrahydrofuran, pyridine, mixtures thereof or other solvents that do not adversely affect the reaction.

The reaction temperature is not particularly limited, and the reaction is usually carried out under cooling or heating.

When compound (n3-1) is used in the form of a free acid, it is preferably carried out in the presence of a commonly used condensing agent (such as dicyclohexylcarbodiimide).

Synthetic route 4 Compound (1) is obtained by reacting compound (II4-1) or a salt thereof with compound (II4-2) or a reactive derivative thereof to form an N-acyl hydrazide, and then reacting with phosphorus pentasulfide. Can be manufactured by

Examples of the salt of compound (n4-1) include acid addition salts such as hydrochloride.

Examples of the reactive derivative of compound (II4-2) include those listed as the reactive derivative of compound (n3-1) in synthetic route 3.

This reaction is usually carried out in water, alcohol (methanol, ethanol, etc.), methylene chloride, dimethylformamide, tetrahydrofuran, pyridine, mixtures thereof or other solvents that do not adversely affect the reaction.

The reaction temperature is not particularly limited, and the reaction is usually carried out under cooling or heating.

When compound (II4-2) is used in the form of a free acid, it is preferably carried out in the presence of a commonly used condensing agent (such as dicyclohexylcarbodiimide).

Compound (n4-1) includes a new compound and can be produced by the methods of raw material compound synthesis routes B and C.

Synthetic route 5 Compound (1) is produced by reacting compound (II5-1) or a reactive derivative thereof with compound (n5-2) or a salt thereof to form an N-acyl hydrazide, and then reacting with phosphorus pentasulfide. can be manufactured.

This reaction is carried out similarly to the reaction described in Synthetic Route 4.

The method for producing the raw material compound will be explained in detail below.

Raw material synthesis route A Compound CU, -2') is obtained by adding compound (IIA-1) and compound (IIA-2) in the presence of a base (sodium hydride, potassium carbonate, etc.) in a solvent such as dimethylformamide. The compound (nA-3
), for example, a halogen (chlorine, bromine, etc.) is reacted in a mixture of ether and dioxane to form the compound (nA
-3) can be produced by leading to a compound (n, -2') which is a halide.

Raw material synthesis route B Compound (n-1) can be produced by reacting compound (IIB-1) or a reactive derivative thereof with hydrazine hydrate.

As the reactive derivative of compound (18-1), it is preferable to use a weakly active derivative such as methyl ester, ethyl ester, etc. in consideration of the high reactivity of hydrazine.

This reaction uses alcohol (methanol, ethanol, etc.)
It is carried out in a warm or heated room.

Raw material synthesis route C Compound (n4-1') or its salt is compound (no-
1) and compound (IIo-2) are reacted in the same manner as synthetic route 2 to produce compound (no-3), which is then reacted with hydrazine hydrate in the same manner as in raw material synthesis route B. can do.

The raw material synthesis route compound (II5-2) or its salt is the compound (nD-1
) and compound (IID-2) in the same manner as in synthetic route 2 to produce compound (■D-3), and further reacted with hydrazine hydrate in the same manner as in raw material synthesis route B. can be manufactured.

Raw material synthesis route E Compound (II2 1') can be produced by reacting compound (II, -1) and compound (IIE-1) in the same manner as in synthetic route 1.

Raw material synthesis route F Compound (n2-1') is obtained by protecting the hydroxy group of compound (IIF-1) with a benzyl group in a conventional manner, and then reacting it with hydrazine hydrate in the same manner as raw material synthesis route B. compound (■.

3), and then reacted with compound (IIF-4) in the same manner as in synthetic route 4 to form an N-acyl hydrazide, and then reacted with phosphorus pentasulfide to form compound (IIF-5).
It can be produced by subjecting the protected hydroxy group to an elimination reaction of the protecting group according to a conventional method.

Raw material synthesis route G Compound (IIo-2) can be obtained by reacting compound (II p -3) and compound (IIo-1) in the same manner as in synthetic route 1.

Raw material synthesis route H Compound (IIH-2) can be obtained by subjecting compound (IIH-, 1) to an elimination reaction of the protecting group at the protected hydroxy group according to a conventional method.

Production Example 1 (1) To a suspension of 60% sodium hydride (1.51 g) in dimethylformamide (30+++1), p
A solution of -hydroxyacetophenone (4.68 g) in dimethylformamide (15 ml) was gradually added dropwise, and the mixture was returned to room temperature and stirred for 30 minutes. (s)-e-methyloctyl-ph luenesulfonate (10.22 g) was added over 10 minutes and stirred on a 60° C. oil bath for 5 hours. Dimethylformamide was distilled off under reduced pressure, water and ether were added to the residue, and the ether layer was separated. The ether layer was washed with water, dried over magnesium sulfate, and the ether was distilled off under reduced pressure to obtain an oily residue. Add this to a silica gel column (150g
) and eluted with a mixed solvent of ether-〇-hexane (1:2) to obtain the desired (S)-4 as a pale yellow oil.
-([i-methyloctyloxy)acetophenone (8
, 87g) was obtained.

IR (film): 1673.1600.1570cl
'Mass m/z: 2[i2 (M'')NM
R(CDCI3)δ: 0.70 to 2.00 (17
11,n+), 2.55(311,s), 4.02(
211,t, J-711z), 6.93(211,d,
J-811z)-.

7.95 (21!, d, J-811z) (2) (S)
-4-(8-methyloctyloxy)acetophenone (
6,82g) was dissolved in a mixture of ether (30n+I) and dioxane (30+nl), and bromine (4,82g) was dissolved under water cooling with stirring.
57 g) was gradually added dropwise. Then cooled in water for 2 hours.
After stirring at room temperature for 1 hour, the reaction solution was poured into water and extracted with ether. After washing the ether layer with 5% aqueous sodium bicarbonate solution and water and drying with magnesium sulfate,
The mixture was concentrated to dryness under reduced pressure to obtain an oily crude product. This was applied to a silica gel column (300 g) and dissolved in a mixed solvent of n-hexane-ether (TO: 1) to obtain the oily target product (S)-2-bromo-4'-(G-methyl Octyloxy)acetophenone (G, 15 g) was obtained.

11? (Film): 1[i70.1595.1570
cm-'Mass mHz: 342 (M"+
2), 340 (M”)NMl?(CDCI
3) δ: 0.71-2.00 (1711, m),
4.08 (2+1.t, J-7112), 4.42 (2
+1. s), (i, 9B (211, d, J-8tlz)
, 8.02 (21+, d, J-8112) Production Example 2 (1) Production Example 1 - The following compound was obtained in the same manner as in (1).

(S)-4-(2-methylbutoxy)acetophenone I
R (film): 1670, l595.1570.15
03c "'Mass mHz: 20G (M÷)N
MR (CDCI 3 ) δ: 0.75 to 2.10 (9
1 (city), 2.42 (311°S), 3.70-4.
00 (2H, m), 6.98 (211, d, J-811
z), 7.95 (211, d, J=8Hz) (2) The following compound was obtained in the same manner as in Production Example 1-(2).

(S)-2-Bromo-4'-(2-methylbutoxy)acetophenone It? (Film): 1880.1595.1568.
1504cm-'Mass ra/z: 28fi(M
"+2), 284 (M") NMR (C
DCI3) δ: 0.80 to 2.20 (911
, m), 3.75-4.30 (211, m), 4.40
(211,S), 7.00(2+1.d, J-7112
), 8.20 (2+1.d, J-7112) Production Example 3 (1) Production Example 1 - The following compound was obtained in the same manner as in (1).

(S)-4-(4-methylhexyloxy)acetophenone II? (Film): 1070.1595.1570.
1500cm-'Mass mHz: 234(M
”) NMI? (CDCI 3) δ:
0.70-2.05 (1311, n+), 2.
50 (311, S), 4.02 (2)! ,t,J-71
12), 6.913 (2+1.d, J-8112), 7
．． 97 (21, d, 8112) (2) The following compound was obtained in the same manner as in Production Example 1-(2).

(S)-2-bromo-4'-(4-methylhexyloxy)acetophenone IR (film): 1680 (sh, ), 16
65, l590.1570.1500cm-' Mass mHz: 314 (M'' +2)
, 312 (M'') NMR (CDCI3) δ:
0.75-2.03 (1311, m), 4.03 (2
11, t, J”711z), 4.39 (2+1.
S), (i, 92 (211, d, J-711z), 7.
93 (211,d, J=711z) Production Example 4 4-hexylbenzoic acid (8.0g) in methanol (10
Concentrated sulfuric acid (0.70 g) was added to the solution (0 ml) and heated under reflux for 4 hours. After cooling, potassium carbonate (1.5 g) was added and the solvent was distilled off under reduced pressure. The residue was dissolved in ether, washed with water, dried over magnesium sulfate, and concentrated under reduced pressure (8
, 5 g) of an oil was obtained. Hydrazine hydrate (15.0 g) and ethanol (10 n+l) were added to this oil and stirred at too-tto°C for 14 hours. The reaction solution was cooled with water, and the precipitated white solid was collected by filtration, washed with water, and dried under reduced pressure to give colorless crystals of 4-hexylbenzohydrazide (7.8 g).
) was obtained.

JR (Nujol): 3270, I[120co
+-'NMR (CDCI3) δ: 0.87 (31
1, L, J=811z), 1. lO ~ 1.83 (811
, m), 2. [13 (211, L, J-711z), 4
．． 2~f3.0 (311, br), 7.22 (211,
d, J-811z), 7.70 (211, d, J-81
1z) Mass mHz: 220 (M'') Production Example 5 The following compound was obtained in the same manner as Production Example 4.

(1) 4-Hebutylbenzohydrazide IR (Nujol): 3200.1 (i50.1
600.1560.1540c '' NMR (CDCLI) δ: 0.89 (31
1, t, J-812), 1.10-1, H (1011,
n+), 2.65 (21!, t, J=711z),
3.40-4. GO (311ura ","), 7.26 (2+
1. d, J-811 illusion, 7.73 (2+1.d, J-8
11z) (2) 4-octylbenzohydrazide IR (Nujol): 3300.3180.16
45.1615.1560cl' NMI? (CDCI3)δ: 0.87 (311,
t, J-011z), 1.10 to 1.83 (12+1.
+n), 2. (i3(2+1.t, J-7112),
3.90-5.90 (311, br,), 7.25 (2
11, d, J-811z), 7.72 (2+1.d, J
-Mass mHz: 248 (M'') (3) 4-
Nonylbenzohydrazide IR (Nujol): 3250.1650.10
05cm-'NMR (CDCI3) δ: 0.87
(311, t, J-611z), 1.10-1.19 (
1411,l11), 2.63(2t(,L,J-7
11z), 4.20-5.40 (311, br,), 7
．． 20 (211, d, J-811z), 7.70 (2+
1. d.
A solution of methyl 4-hydroxybenzoate (6.1 g) in dimethylformamide (20~t) was added dropwise over 15 minutes. After stirring at room temperature for 1 hour, (s)-e-methyloctyl-p-
Toluenesulfonate (13.1 g) was added dropwise over 30 minutes, and the mixture was stirred at 50°C for 15 hours. Pour the reaction solution into ice water,
Extracted with ether. The organic layer was washed with water, dried over magnesium sulfate, and concentrated under reduced pressure to give an oily (S)-4-(6
-methyloctyloxy)benzoate was obtained. To this, hydrazine hydrate (14.4g) and ethanol (1
4-t) was added and stirred at 100-110°C for 16 hours.

The reaction solution was cooled, and the precipitated crystals were collected by filtration, washed with water, and dried to obtain (S)-4-(0-methyloctyloxy)benzohydrazide (8.9 g) as colorless crystals.

IR (Nujol): 3250.1650.16
00.1590.1560.1500c "' NMR (CDCI 3 ) δ: 0.60 ~ C00 (l
lill, m), l, 00-2.10 (llll+, +n
), 4.00 (211,t, J-7!Iz), 3. G
O ~ 4.50 (2H, br, ), 8.95 (2H, d,
J-8112), 7.50-7.95 (30°m) Mass mHz: 278 (M'') Production Example 7 The following compound was obtained in the same manner as Production Example 6.

(1) (S)-4-(4-methylhexyloxy)benzohydrazide IR (Nujol): 3250.1660.159
0.1570.1500cl' NMl? (CDCl2) δ: 0.70~t
, +o (en, +++), 1.10~2.10 (71
1, m), 4.00 (211, L, J-711z), 4
．． 13 (3i1.s), 6.90 (211, d, J=8
i1z), 7.73 (211, d, J-811z) Ma
ss tn/z: 250 (M”) (2) (S
)-4-(2-methylbutyloxy)benzohydrazide 11? (Nujol): 3270.1600.1
570.1520.1500c "I NMR (CDCI3) δ: 0.83-2.1
0(911,+n), 3.77-4.20(411,+
n), 6.93 (2+1.d, J-8112), 7. (
i3 (111, s), 7.75 (211, d, J-81
12) Mass mHz: 222 (M”) (3)
4-octyloxybenzohydrazide IR (Nujol
): 3300, 3150.1640.1610
．． 1570.1500cl' NMR (CDCI3) δ: 0.70~
1.03 (311, m), 1.03-2.10 (12!
1. ra), 3.97 (211,t, J=711z
), 3.53-4.50 (211, br, ), 6.90
(211,d, J=811z), 7.58(111,s
), 7.72 (2+1.d, J-8112) Production Example 8 (1) 60% sodium hydride (5.5 g) was suspended in dimethylformamide (30~t), and 4-
A solution of methyl hydroxybenzoate (17.5 g) in dimethylformamide (701) was added dropwise over 30 minutes. After gradually returning to room temperature, stirring for 1 hour, benzyl bromide (
25g) was added dropwise over 30 minutes. 6 hours at room temperature, then 6 hours
After stirring at 0° C. for 6 hours, the reaction solution was poured into water and extracted twice with ether, and the ether layer was collected and washed with water. After drying with magnesium sulfate, the mixture was concentrated to dryness under reduced pressure to obtain a crystalline crude product. This crude product was added to hydrazine hydrate (48 g
), add ethanol (201Wl) and boil at 90-100
The mixture was stirred at ℃ for 6 hours. The reaction solution was cooled with water, the precipitated white solid was collected by filtration, washed with water, and dried under reduced pressure to obtain 4-benzyloxybenzohydrazide (25.0 g) as a white crystalline powder.
I got it.

IR (Nujol): 3270, +630S+5
95.1570.1525cn+-' (2) The following compound was obtained in the same manner as in Example 7.

2-(4-benzyloxyphenyl)-5-octyl 1
．． 3. Production of 4-thiadiazole IR (Nujol): 1615.1590.15
30c "'NMR (CDCI 3 ) δ: 0.00~
1.00 (311, m), L, OO~2.00 (L2f
l, m), 3.12 (211, t, J-711z),
, 5.14 (211,s), 7.05 (2+1.d, J
-8+12) 1.7.23~7.57 (511, m),
7,90 (211, d, J=811z) Mass rn/z: 380 (M”) (3) 2-
(4-benzyloxyphenyl)-5-octyl-1,
Acetic acid (2 ml) to 3,4-thiadiazole (1,0 g)
, 47% hydrobromic acid (1 ml) was added, and the mixture was stirred at 60°C for 3 hours. The reaction solution was poured into ice water, extracted twice with methylene chloride, and the methylene chloride layer was collected and washed with water. After drying with magnesium sulfate, it was concentrated to dryness under reduced pressure to obtain an oily crude product. The crude product was applied to a silica gel column and eluted with a mixture of n-hexane and ether to give a white crystalline powder of 2-
(4-hydroxyphenyl)-5-octyl-1,3,
4-thiadiazole (0.55 g) was obtained.

IR (Nujol): 3050.1600.15
70.1510c+n-'NMI? (CDCI!)
δ: 0. BO~1.00 (311,m), 1.00~
2.10 (12H, m), 3.10 (2!1.t, J
=711z), 7.07(2H,d.

J-811z), 7.83 (21Ld, J-8tlz)
Mass mHz: 290 (M'') Production Example 9 Heptanohydrazide (4,33g) and p-hydroxyphenacylbromide (3,23g) were mixed with ethanol (6
0 ml) and acetic acid (20 ml), sodium acetate (2.71 g) was added thereto, and the mixture was heated under reflux for 10 hours.

After cooling, the reaction solution was concentrated under reduced pressure, and methylene chloride was added to the residue, which was washed with water. After drying with magnesium sulfate, the mixture was concentrated to dryness under reduced pressure to obtain a crude product. This was applied to a silica gel column (200 g) and eluted with a mixture of n-hexane and ether (3:1 to 1:1) to obtain the desired 3-hexyl-6-(4-hydroxyphenyl)- 1,2,4-)Ryazine (1,olg) was obtained as pale yellow crystals.

IR (Nujol): 3300 (sh,), 1
800.1580cm-'Mass mHz: 257
(M ”) NMR (CDCl2) δ: 0.8 g (
311, L, J-7112), 1.13-2.12 (8
11, m), 3.20 (211, t, J-711z),
7.18 (2+1.d, J-811z), 8.08 (2
11, d, J-811z), 9.05 (llI, s) Production Example 10 The following compound was produced in the same manner as Production Example 9.

(1) 3-ethyl-6-(4-hydroxyphenyl)-
1,2゜4-triazine 11? (Nujol): 1000.1582c"
'Mass IIIHz: 201(M'')NMR
(CDCI 3 ) δ: 1.45 (311, t, J-
7112), 3.15 (2+1゜q, J-711z),
7.00 (211, d, J-8112), 7.97 (2
+1. d, J-811z), 8.9G (lIl, 5) (2) 3-propyl-6-(4-hydroxyphenyl)
-1゜2.4-) Riazine IR (Nujol): 3300.1600.1
580co-'Mass Ia/z: 215(M
”) NMR (CDCI3) δ:
1.05 (311, t, J-7112), t, eo~
2.25 (211, m), 3.17 (2+1.L, J-
7112), 7.22 (2+1.d, J-811z),
8.05 (211, d, J-8 肚), 9.03 (lIl
, 5) (3) 3-butyl-6-(4-hydroxyphenyl)-1,2°4-triazine IR (Nujol): 1600.1580ci'
Mass adz: 229(M+)NMR
(CDCI3) δ: 0.98 (311,t, J-
7112), 1.24-2.13 (411, m), 3.
20(211,t, J=711z), 7.20(2+1
．． d, J=911 z ), 8.03 (2+1.d, J
-9112), 9.00(1+1.5)(4)3-octyl-6-(4-hydroxyphenyl)-1°2.4-
) Riazine IR (Nujol): 1800.1570cm-
'Mass IIIHz: 285(M'')NMR
(CDCI 3 ) δ: 0.7Q ~ 2.20 (15
11,m), 3.21(211,t, J=711z)
, 7.20 (211, d, J-911z), 8.06 (
2+1. d.

J-911z), 9.02 (111, s) Production Example 11 3-(4-benzyloxyphenyl)-6-hexyl-
1,2,4-)riazine (770II1g) was dissolved in acetic acid (
61), 47% hydrobromic acid (2 ml) was added thereto, and the mixture was heated and stirred on a 120° C. oil bath for 20 minutes. The reaction solution was poured into water and extracted twice with ether. The ethers were combined, washed with water, dried over magnesium sulfate, and concentrated to dryness under reduced pressure. The residue was applied to a silica gel column (20 g) and eluted with a mixed solvent of n-hexane-ether to obtain 3-(4-hydroxyphenyl)-6-hexyl-1,2,4-triazine (240 mg) as pale yellow crystals. Ta.

IR (Nujol): 1805.1585c+n
-'Mass m no z: 25701 + )N
MR(CDCI3)δ: 0.75-2.00(1
111,111), 3.00(211,t, J=71
1z), 7.06 (211, d, J=811z), 8.
46 (2+1.d.

J-811z), 8.58 (111,s) Production Example 12 4-benzyloxybenzohydrazide (4,85g)
, ■-bromooctane-2-one (2,07 g) and sodium acetate (0,18 g) were dissolved in ethanol (
The mixture was sequentially added to a mixed solvent of 30II+l) and acetic acid (10+nl), and heated and stirred on a 120°C oil bath for 7 hours. The reaction solution was concentrated to dryness under reduced pressure, and water and methylene chloride were added to the residue. The methylene chloride layer was separated, washed with water, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain an oily residue. This was applied to a silica gel column (15 g) and eluted with a mixed solvent of n-hexane and ether to obtain the desired 3-(4
-benzyloxyphenyl)-6-hexyl-1.2.
4. -) Riazine (1.0 g) was obtained as pale yellow crystals.

IR (Nujol): 11302.1580cm
-'Mass mHz: 347 (M'') NMR (
CDCI3) δ: 0.70-2.
00(ll11.m), 2.97(2+(,t,
J-8112), 5.14 (211, s), 7. L
O(211,d, J-811z)y, 45(5t1.m
), 8.46 (lit, s), 8.49 (2+1.d,
J-8112) Production Example 13 Lithium aluminum hydride (2.5 g) was suspended in dry ether (70 ml), and under water cooling, (2S, 38)-2
A solution of -chloro-3-methylpentanoic acid (9.5 g) in dry ether (30n+1) was slowly added dropwise. 2 at room temperature
After stirring for an hour, the mixture was heated under reflux for 20 minutes. Cool the reaction solution with water,
After decomposing excess reagent with water (10 ml), the precipitate was dissolved with 20% sulfuric acid (301). The ether layer was separated, washed with water, dried over magnesium sulfate, and concentrated under reduced pressure to obtain an oily crude product. This is distilled under reduced pressure (
b, p, 711m11g 65.5~[i7.0℃)
, (2S,3S)-2-chloro-3-methylpentanol (4.5 g) was obtained.

IR (Neat): 3350.1460.1380
cm-' Production Example 14 Add p-toluenesulfonyl chloride (5.9 g) little by little to a solution of (2S,3S)-2-chloro-8-methylpentanol (4,0g) in pyridine (+0ml) under water cooling and stirring. The mixture was further stirred at room temperature for 15 hours. The reaction solution was poured into ice water, acidified with hydrochloric acid, and then extracted twice with ether.

The ether layer was washed with water, dried over magnesium sulfate, and concentrated under reduced pressure to obtain an oily (2S,3S)-2-chloro-3-
Methylpentyl-p-toluenesulfonate (8.4g
) was obtained.

IR (Neat): 1590.1450.1360
, l170cm-' Production Example 15 60% sodium hydride (1.22g) was suspended in dimethylformamide (101), and a solution of methyl 4-hydroxybenzoate (4.4g) in dimethylformamide (10ml) was added to this under water cooling. was added dropwise over 15 minutes. After stirring at room temperature for 1 hour, (S)-5-methylhebutyl-p-toluenesulfonate (8.7 g) was added dropwise over 30 minutes. 50℃
After stirring for 15 hours, the reaction solution was poured into ice water and extracted with ether, and the organic layer was collected and washed with water. After drying with magnesium sulfate, it was concentrated under reduced pressure to obtain an oily (S)-4
-(5-methylhebutyloxy)methylbenzoate (8,
0g) was obtained. Add hydrazine hydrate (11.5 g) and ethanol (5 ml) to this and heat at 100 to 110°C.
Stirred for 5 hours. The reaction solution was cooled, and the precipitated crystals were collected by filtration, washed with water, and dried to obtain (S)-4-(5-methylhebutyloxy)benzoic acid hydrazide (7.5 g) as colorless crystals.

IR (Nujol): 3250, lG60.18
00.1570.1500cm-' Mass mHz: 204(M'')NMl?(C
DCI3) δ: 0.00 to 1.00 (611,
m), 1.00 to 2.20 (911, n+), 3.93
(211,t, J-1711z), 4.10-4.80
<211. br), f3.90 (2+1.d, J-
8+1z), 7.70 (211, d.

J=811z), 9.50 (Ill, s) Example 1 Octanohydrazide (1,84g), (S)-2-
Bromo-4'-(6-methyloctyloxy)acetophenone (1,71 g) and sodium acetate <0.
41g) in ethanol (15ml) and acetic acid (5ml).
) and heated and stirred on a 120°C oil bath for 2 hours. The reaction solution was concentrated to dryness under reduced pressure, and water and methylene chloride were added to the residue. The methylene chloride layer was separated, washed with water, and then dried over magnesium sulfate. The solvent was removed under reduced pressure to obtain an oily residue. Add this to a silica gel column (1
00g) and eluted with a mixed solvent of bovine san-ether to obtain the desired (S)-6-14-(B-methyloctyloxy)phenyl)-3-octyl-1,2,4
,-) riazine (0.32 g) was obtained as pale yellow crystals.

! R (Nujol): 1002, l578.15
10c "'Mass 1IHz: 411(M")
NMR (CDCI3) δ: 0.64-2.18
(321 (, m), 3.15 (21!, t, J
-711z), 4.05 (21!, t, J-711z)
, 7.06 (211, d.

J-8Hz), 8.08 (2H, d, J-8)1z),
8.94 (LH,s) Example 2 The following compound was obtained in the same manner as in Example 1.

(1) (S)-3-Butyl-6-(4-(4-methylhexyloxy)phenyl l-1,2,44 riazine I
R (Nujol): 1602.1570.151
0e ``'Mass mHz: 327 (M'') NM
R(CDCI3)δ: 0.78 to 2.10 (20
11, m), 3.16 (211, t, J-711
z), 4.01 (211, t, J-711z), 7.0
5(2+1.d.

J=711z), 8.06(211,d, J-711z
), 8.90 (111, s) (2) (S)-G-14
-(8-methyloctyloxy)phenyl)-3-benzene 1.2,4. -) Riazine IR (Nujol)
l[ioo, 1570.1508c+n-'Mass
mHz: 309 (M'') NMR (CDCI 3
) δ: 0.70 to 2.10 (2411, m), 3
．． 13 (2H, t, J-711z), 4.03 (2H,
t, J-7H2), 7.04 (2H, d.

J=8Hz), 8.07(2H,d,J-[(z),8
．． 92 (III, S) (3) (S)-8-14-(4
-methylhexyloxy)phenyl)-3-benzene 1.2.4-triazine IR (Nujol):
LGoo, 1570.1510cm-'Mass
mHz: 341 (M”) NMI? (CDC
I3) δ: 0.70 to 2.20 (2211
, m), 3.10 (2+1.t, J-7112),
4.04 (211,t, J-7112), 7.0(i(
2+(,d.

J=711z), 8.07(2+1.d, J-7112
), 8.94(111,3)(4)(S)-3-hexyl-(1-14-(4-methylhexyloxy)phenyl l-1,2,4-triazine IR (Nujol)
: 1600, l575.1510cm-'Mass
tn/z: 355 (M'') NMR (CDCI3
) δ: 0.70 to 2.20 (2411, m), 3.
18 (2+1.L, J-711Z), 4.08 (211
, L, J-711z), 7.07 (211,d.

J-711z), 8.08 (211,d, J-711z
), 8.95(III, 5)(5)(S)-3-heptyl-6-14-(6-methyloctyloxy)phenyl l-1,2,4-triazine IR (Nujol):
1602.1573.1510cm-'MilSS
mHz: 397 (M + )NM
R(CDCI3)δ: 0.70 to 2.10 (301
1, m), 3.13 (211, t, J-7112),
4.04 (211,t, J-711z), 7.0G (2
+1. d.

J=711z), 8.07(211,d, J-7112
), 8.90(111,5)(6)(S)-3-heptyl-6-14-(4-methylhexyloxy)phenyl l-1,2,4-)riazine IR (Nujol):
1800.1573.1507c111-'Mass
mHz: 389 (M'') NMR (CDCI 3
) δ: 0.70 to 2.20 (2611, m), 3
．． 14 (211,t, J-711z), 4.04 (21
+, t, J-7112), 7.05 (211, d.

J-711z), 8.06 (211,d, J-711z
), 8.92 (111, s) (7) (S)-e-14
-(4-Methylhexyloxy)phenyl 1-3-octyl-1,2,4,-)riazine IR (Nujol)
: 1800.1570.1510cm-'Mass
mHz: 383 (M'') NMR (CDCI 3
) δ: 0.65 to 2.10 (2811, m), 3
．． 14 (211,t, J-711z), 4.04 (21
, t, J-71(z), 7.05(2+1.d.

J-7II z), 8.07 (211, d, J-7
tlz), 8.92 (lH, s) (8) (S)-6-
[4-(2-methylbutoxy)phenyl)-3-octyl-1,2,4-)riazine IR (Nujol):
1803.1572.1510cn+-'Mass
mHz: 355 (M'') NMR (CDCI 3
) δ: 0.87 to 2.10 (2411, m), 3.
15 (211,t, J=711z), 3.88-4.1
6 (211, m), 7.04 (211, dJ=711z
), 8.07 (211, d, J-7112), 8.92
(LIl,s)(9)(S)-t+4-(8-methyloctyloxy)phenyl)-3-nonyl-1,2,4-
Triazine IR (Nujol): 1600.15
05cm-'Aass mHz: 425(M'')
NMR (CDCI3) δ: 0.85-2.10 (
3411,m), 3.13(211,t, J=7
11z), 4.04 (211,t, J-7112), 7
．． 06(2+1.d.

J-711z), 8.06 (211,d, J-711z
), 8.94(111,s) (10) (S)-3-decyl-0-+4-(6-methyloctyloxy)phenyl l-1,2,4-triazine 11? (Nujol)
: 11300.1570.1505cm-'Mas
s mHz: 439 (M + ) NMR (CD
CI3) δ: 0.70-2.10 (3f311.m)
, 3.1[1(211,t, J-711z), 4
．． 02 (211, t, J-71 [z), 7.04 (2+
1. d.

J-711z), 8.03 (21(, d, J-7Hz)
, 9.01 (111, s) (11) (S)-8-14
-(2-methylbutoxy)phenyl l-3-(4-octyloxyphenyl)-1,2,4-triazine IR (Nujol): 1605, 1578
, 1510c+n-word Mass mHz: 447
(M”) NMR (CDCI3) δ:
0.70-2.10 (2411,a), 3.75
~4.20 (411,m), 7.00~7.20 (41
1, m), 8.15 (2+1.d, J-811z), 8
．． 58 (211, d, J=811z), 9.00 (ll
l, s) (12) (S)-6-+4-(2-methylbutoxy)phenyl l-3-(4-octylphenyl)-
1,2,4-triazine IR (Nujol): 1
600.1570.1510c ``'Mass ta/z
: 431(M'')NMR(CDCI3)6
: 0.65-2.10 (2411, m), 2.7
0(211,t, J=711z), 3.75-4.10
(211, ra), 7.10 (211,6°J-811
z), 7.38 (211, d, J-8112), 8.1
4 (211, d, J-8112) 8.50 (211, d
, J=8Hz), 9.00(lit, s) (13) (
S)-0-+4-(0-methyloctyloxy)phenyll-3-(4-octyloxyphenyl)-1,2,
4-triazine IR (Nujol): 1600, ■570
, 1510c11-'Mass mHz: 503(M
”) NMR (CDCI3) δ: 0.8
8-2.10 (3211, m), 4.07 (211
, t, J-711z), 8.99-7.20 (41
1,1+1), 8.13(21+,d.

J-711z), I! , 55 (211, d, J=711
z), 8.98<111. s) Example 3 60% sodium hydride (110 mg) was suspended in dimethylformamide (LOML) and 3-hexyl-6-(4-hydroxyphenyl)-1,2,4 was added under stirring under water cooling.
-Triazine (a4amg) was added in portions. After further stirring for 10 minutes under water cooling, (s)-e-methyloctyl-p-toluenesulfonate (820 mg) was added, and the mixture was stirred at room temperature for 1.5 hours and further at 00°C for 1.5 hours. The reaction solution was poured into water (200 ml) and ether (1
The ether layer was collected and washed with water. After drying with magnesium sulfate, the mixture was concentrated to dryness under reduced pressure to obtain a crystalline crude product. Silica gel column (100
g) and elute with a mixed solvent of n-hexane-ether (7:l) to obtain the target (S)-3-hexyl-〇-1.
4-([i-methyloctyloxy)phenyl l-1,
2,4-triazine (480+ng) was obtained.

11? (Nujol): 1600cn+-'Ma
ss mHz: 383 (M'') NMR (CDCI
3) δ: 0.72-2.12 (2811, m)
, 3.17 (2+1.L, J-7112), 4.07
(211, L, J-711z), 7.07 (2+1.
d.

J=811z), 8.10(2+I,d, J-8112
), 8.92 (!!I,s) Example 4 The following compound was obtained in the same manner as in Example 2.

(1) (S)-3-ethyl-6-+4-(13-methyloctyloxy)phenyl l-1,2,4-triazine IR (Nujol): 1800c "'Mass
mHz: 327 (M'') NMR (CDCI 3
) δ: O, 09-1.98 (2011, m)
, 3.19 (211,Q, J-7112), 4. H
(211,t, J-7112), 7.07(211,d
.

J-811z), 8.05(21[, d, J-8t(z
), 8.91 (111, s) (2) (S)-8-14
-(6-methyloctyloxy)phenyl)-3-propyl-1,2,4-triazine 11? (Nujol)
: 1(i00cn+-'Mass IIl/z:
341(M”)NMI?(CDCI3)δ:
0.70-2.15 (2211, m), 3.14<
2H, t, J-711z), 4.05 (21Lt, J-
7tlz), 7.06(2+1.d.

J-811z), 8.1)8 (2H, d, J-8Hz)
, 11.93(III,s)(3) (S)-3-Butyl-6-(4-(6-methyloctyloxy)phenyl l-1,2,4-triazine IR (Nujol):
1603.1575cm-'Mass mHz: 3
55 (M'') NMR (CDCI3) δ: 0.
75-2.10 (2411, m), 3.18 (211
, t, J=811z), 4.05(2+1. t, J=
811z), 7.08(2+1.d.

J-811z), 8.10(211,d, J-811z
), 8.95 (111, s) Example 5 6-(4-hydroxyphenyl)-3-octyl-1,
2,4 triazine (1,00 g) in methylene chloride (2
Add (2S, 38)-2-chloro-3-methylpentanoic acid (0.55 g) and 4-pyrrolidinopyridine (0.1 Hg) and dicyclohexylcarbodiimide (0.78 g) to the solution (2S, 38), and cool to room temperature. Stirred for 15 hours.

Insoluble matters were removed by filtration, and the filtrate was washed successively with a 3% aqueous hydrochloric acid solution and a 5% aqueous sodium bicarbonate solution, then with water, dried over magnesium sulfate, and concentrated under reduced pressure to dryness. The residue was purified on a silica gel column (eluted with n-hexane-ether) to obtain the desired (2S, 38)-6-+4-(2-chloro-3-methylpentanoyloxy)phenyl)-3.
-Octyl-1,2,4-)riazine (0,39g)
I got it.

IR (C1l2CI2 solution): 1760.1
600cm-'Mass mHz: 417(M"
)N)lR(CDCI3)δ: 0.70-2.3
5 (2L11.I), LL? <211.1. J-71
12), 4.40 (111, d, J-7112), 7.
34 (211, d.

J-811z), 8.18(211,d, J-811z
), 8.98 (ill, s) Example 6 6-(4-hydroxyphenyl)-3-octyl-1,
2,4 triazine (0.90 g) was dissolved in methylene chloride (1
(s)-e-methyloctanoyl chloride (0.71 g) and triethylamine (0.41 g) were added to the mixture under water-cooling and stirring, and the mixture was stirred at the same temperature for 40 minutes.

Methylene chloride was added to the reaction solution, which was washed with a 5% aqueous hydrochloric acid solution, further washed with a 5% aqueous sodium bicarbonate solution, washed with water, dried over magnesium sulfate, and then concentrated to dryness under reduced pressure. The residue was applied to a silica gel column and eluted with a mixed solvent of n-hexane-ether to obtain the desired product (S)-8-14.
-(6-methyloctanoyloxy)phenyl)-3-
Octyl-1,2,4-triazine (0.73 g) was obtained.

11? (Nujol): 1743, 1000
cm-'Mass mHz: 425(M'')NM
I? (CDCl3)δ: 0.70-2.20(
3011, ff1), 2.62 (21t, t, J-7
112), 3.2L(2)1. t, J-711z), 7
．． :+4(211,d.

J-8Hz), 8.20 (2H, d, J-8Hz), 9
．． 00(111,8) Example 7 4-hexylbenzohydrazide (2.0 g) was dissolved in pyridine (15 ml), and (S)-6-methyloctanoyl chloride (1.77 g) was dissolved in 15 minutes under water cooling. dripping,
The mixture was stirred at room temperature for 0.5 hours and then at 80°C for 3 hours. After cooling the reaction solution to room temperature, phosphorus pentasulfide (10.0 g)
was added in three portions, stirred at 60°C for 0.5 hour, and further heated under reflux for 15 hours. The reaction solution was poured into ice water, adjusted to pH 2 or less with concentrated hydrochloric acid, and then extracted twice with ether. After washing the organic layer with water and drying with magnesium sulfate,
Concentration under reduced pressure gave a dark brown oil. The crude product was applied to a silica gel column and eluted with a mixture of n-hexane and ether to give a colorless oil (S)-2-(4-hexylphenyl)-5-(5-methylhebutyl)-1, 3,4-thiadiazole (1,81 g) was obtained.

11? (Nujol): 1000.1400cm
-'NMI? (CDCl3)δ: 0.70-1
．． 00 (911, m), 1.10-2.10 (1711
, n+), 2. (+3(211,t, J-711
z), 3.10 (211, t.

J=711z), 7.25(2+1.d, J-8112
), 2.83 (211, d, J-811z) Mass
III/Z: 358 (M'') Example 8 The following compound was obtained in the same manner as in Example 7.

(1) (S)-2-(4-hebutylphenyl)-5-
(5-Methylheptyl)-1,3,4-thiadiazole IR (Nujol): 1800.1400 cm-
'NMR (CDCI3) δ: 0.130-1.0
0 (911, m), 1.10-2.00 (1911, 1
5), 2.05 (211,1, J-7112), 3.
13 (2+1.1°J-711z), 7.26 (211
, d, J-811z), 7.87 (211, di-81
12) Mass mHz: 372 (M”) (2'
) (S)-2-(4-octylphenyl)-5-(5
-methylheptyl)-1,3,4-thiadiazole IR
(Nujol): 1600.1400cm-'N
MR(CDCI3)δ: 0.70-1.03(9
H, n+), 1.07 to 2.07 (2LH, +n),
2.67 (2H, t, J=711z), 3.13 (21
1, t, J-711z), 7.29 (211, d, J-
811z), 7.88(211,d, J-811z)M
ass mHz: 38B(M”)(3)(S)
-2-(4-nonylphenyl)-5-(5-methylhebutyl)-1,3,4-thiadiazole IR (Nujol
) : 1600.1400c11-'NMR(CD
CI3) δ: 0.57 to 1.00 (91
1, m), 1.00-2.03 (2311, m),
2.63 (211,t, J-711z), 3.10 (2
+1.1°J-711z), 7.25(211,d,
J-811z), 7.87(211,d, J-811z
)Mass mHz: 400(M”)(
4) (S)-2-(4-octylphenyl)-5-(
3-methylpentyl)-1,3,4-thiadiazole I
R (Nujol): 100011400cm-'
NMR (CDCI 3 ) δ: O, QO ~ 1.10 (
911, m), 1.10-2.10 (1711, m)
, 2.60<211. t, J”711z), 3.10(
2+1. t.

J-711z), 7.28 (21+, d, J-8112
), 7.80 (211, d, J-811z) Mass
mHz: 358(M”)(5)(S)-2-(
4-nonylphenyl)-5-(3-methylpentyl)-
1,3,4-thiadiazole IR (Nujol):
1600.1400cm-'NMR (CDCI3)
δ: 0.73 to 1.10 (911, +n), 1.10
~2.17 (+911.m), 2.67 (211,t
, J=711z), 3.13(2+1.t.

J-711z), 7.28(211,d, J=811z
), 7.83 (211, d, J-811z) Mass
mHz: 372 (M”) (6) (S)-2-hebutyl-5-14-([i-methyloctyloxy)phenyl l-1,3,4-thiadiazole IR (Nujol
): 1800.1570.1510c "'NM
R(CDCI3) δ: 0.60-1.
00(911,+n), 1.00~2.10(2111
, m), 3.10 (211, L, J-7Hz), 4
．． 00(2+1.t.

J-711Z), 6.95 (211, d, J-811z
), 7.87 (211, di-811z) Mass
rn/z: 402 (M”) (7) (S)
-2-octyl-5-+4-(6-methyloctyloxy)phenyll-1,3,4-thiadiazole IR(N
ujol): 11300.1570.1510c
m-'NMR (CDCI3) δ: 0.70-1.
05 (911, m), 1.05-2.10 (23+1.
n+), 3.13 (211, t, J-7112), 4
．． 03 (21+, t.

J=711z), 7.00(211,d, J-8112
), 7.90 (2+1.d, J-8112) Mass
mHz: 41B(M'') (8) (S)-2-nonyl-5-(4-(13-methyloctyloxy)phenyl l-1,3,4-thiadiazole IR (Nujol
): 1f300.1570.1510cl'NM
R(CDCI3)δ: 0.65-1.03(9)
1. +n), 1.03 to 2.17 (25H, m), 3
．． 12 (2H, t, J-7) 1z), 4.03 (21+
, t.

J-711z), 7.00 (2H, d, J-8Hz),
7.90 (211, d, J-811z) Mass mH
z: 430(M+)(9)(S)-2-heptyl-5-14-(4-methylhexyloxy)phenyl l
-1,3,4-thiadiazole IR (Nujol)
: IGoo, 1570.1510cm-'NMI? (
CDCI 3) δ: 0.70-1.00 (9!l, +
n), 1.00-2.00 (17H, l1l), 3.
10 (211, t, J-7112), 3.97 (211
,t.

J=711z), 8.95(211,d, J-811
z), 7.87 (2+1.d, J-8112) Mass
mHz: 374 (M”) (10) (S)-2
-Octyl-514-(4-methylhexyloxy)phenyl l-1,3,4-thiadiazole IR (Nujo
l): 1800.1570.1510c1'NM
R (CDC13) δ: 0.71-1.00 (911,
m), 1.00-2.00 (1911, m), 3.1
2 (211, t, J=711z), 4.02 (211,
L.

J-711z), 6.95(211,d, J=811z
), 7.86 (211, d, J-811z) Mass
mHz: 388 (M”) (11) (S)-5
-nonyl-2-+4-(4-methylhexyloxy)phenyl l-1,3,4-thiadiazole IR (Nujo
l): 1000.1570.1.510c+n-
'NMI? (CDCI) δ: 0.7Q ~1.
10 (911, m), 1.10-2.10 (211!,
m), 3.10 (211,-t, J-711z), 4
．． 00 (211,t.

J-711z), 13.90 (2+1.6.J-811
2), 7.90 (211, d, J=811z) Mass
rn/z: 402U” ) (12) (S)-2
-Octyl-5-(4-(2-methylbutoxy)phenyl)-1,3,4-thiadiazole IR (Nujol)
: 1600.157OS1510cm-'NMR
(CDCI3)δ: 0.70 to 2.10 (241
1,m), 3.10(211,t, J-711z
), 3.76-4.10 (211, IQ), 6.95 (
211, d.

J-811z), 7.87(211,d, J-811z
) Mass Ill/z: 360 (M + )
(13) (S)-2-(4-octyloxyphenyl)-5-(5-methylhebutyl)-1,3,4-thiadiazole IR (Nujol): I(too, 15
70.1510cm-'NMl? (CDCI3)δ
: 0.70-1.00 (911, m), 1.00-2
．． 00 (2111, m), 3.12 (2+1.t, J
-7112), 4.03 (211,t.

J-711z), (i, 98 (2H, d, J-8!1z
), 7.74 (211, d, J=811z) Mass
to/z: 402(M”)(14)(S)-2
-(4-octyloxyphenyl)-5-14-(G-
Methyloctyloxy)phenyl l-1,3,4-thiadiazole IR (Nujol): 1600.1570.1
510cm'NMR (CDCI3) δ: 0.80
~1.00(911,+n), 1.00~2.00(2
311, m), 4.03 (411, L, J-711
z), 0.98 (411, d.

J-811z), 7.93 (411,d, J-811z
)Mass mHz: 50g(M”)(
15) (S)-2-octylphenyl-5-(6-methyloctyloxyphenyl)-1,3,4-thiadiazole IR (Nujol): 1600.1570
．． 1510cI+1-'NMR (CDCIx) δ:
0.70-1. (13 (911, m), 1.03-2.
03 (2311, m), 2.68 (211, t, J-
7! Iz), 4.05 (2+1.t.

J-711z), 7.00 (2+1.d, J-8112
), 7.33 (211, d, J-811z) 7.95 (
211, d, J-811z), 7.98 (2+1.d,
J-8112) Mass mHz: 492 (M”
)(16) (S)-2-decyl-5-14-(G-methyloctyloxy)phenyl l-1,,3,4-thiadiazole IR (NujoD: 1G00.15
7(1,15LOcm-'NMR(CDCI3)δ
: 0.73~1.00 (911,n+), 1.00~
2.07 (2711, m), 3. io (2H,L,J
-711z), 4.03 (2H.

L, J-711z), li, 97(211,d, J-8
11z), 7.88 (2+1.d, J-8!lz) Mass mHz: 444 (M”) (17) (
S)-2-decyl-5-14-(4-methylhexyloxy)phenyl)-1,3,4-thiadiazole IR(
Nujol): 1600, 1570, 15
10cm-NMR (CDCI3) δ:
0.70-1.03 (911, m), 1.03-2.1
0 (2311, m), 3.10 (211, L
, J-711z), 4.0Q (211°t, J-711
z), 6.95 (211, d, J-811z), 7.8
8 (211, d, J-811z) Mass mHz: 41B (M”) (18)
(S)-2-(4-octyloxyphenyl)-5-
(3-Methylpentyl)-1,3,4-thiadiazole IR (Nujol): 1000.1570.15
10cl'NMR (CDCI3) δ: 0.70-1
．． 10 (911, m), 1.10-2.10 (1711
, n+), 3.13 (2+1.1.J-7112),
4.03(211,t,J=7)1z),(i,97(
2!1. d, J=811z), 7.90(2+1.d.

Hlz) Mass cm/z: 374 (M +) Example 9 2-(4-hydroxyphenyl)-5-octyl-1,
3,4-thiadiazole (0.5 g) was dissolved in pyridine (5 m
(S)-8-methyloctanoyl chloride (0.34 g) was added to the mixture under water-cooling and stirring, and the mixture was stirred at the same temperature for 1 hour and then at room temperature for 1 hour. The reaction solution was poured into ice water, acidified with hydrochloric acid, and then extracted twice with ether. The ether layer was washed with water, dried over magnesium sulfate, and concentrated to dryness under reduced pressure. The residue was applied to a silica gel column and eluted with a mixed solvent of n-hexane-ether to obtain a white crystalline powder (
S)-2-octyl-5-+4-(8-methyloctanoyloxy)phenyl l-1,3,4-thiadiazole (0.61 g) was obtained.

11? (Nujol): 1745.1590.1
580.1500eI11-'NMR (CDCI3)
δ: 0.70 to 1.00 (911, m),! , 00～
2.00 (21+1.m), 2. tiO(211,t
, J-7i1z), 3.17 (211, t.

J-711z), 7.22 (2+1.cl, J-111
1z), 8.00 (2+1.d, J-8112) Mas
s mHz: 430 (M'') Example 10 The following compound was obtained in the same manner as in Example 1.

(S)-2-octyl-5-14-(4-methylhexanoyl)phenyl l-1,3,4-thiadiazole IR
(Nujol): 1750.1595.1580
．． 1505 cm'NMR (CDCI3) δ: 0.
70-1.10 (911, m), 1.10-2.10 (
1711, n+), 2.57 (211, L, J-71
1z), 3.12 (211, L.

J=811z), 7.20(211,d, J-811z
), 7.95 (211, d, J-811z) Mass
Hlz: 402 (M'') Example 11 2-(4-hydroxyphenyl)-5-octyl-1,
3,4-thiadiazole (0,5 g) in methylene chloride (
10 ml) solution, (28,3S)-2-chloro-3
-Methylpentanoic acid (0.29 g), 4-pyrrolidinopyridine (50 ml) and dicyclohexylcarbodiimide (0.39 g) were added, and the mixture was stirred at room temperature for 16 hours.

Insoluble matters were removed by filtration, and the filtrate was washed successively with 3% aqueous hydrochloric acid and 5% aqueous sodium bicarbonate solution 7(k), then water, dried over magnesium sulfate, and concentrated to dryness under reduced pressure.The residue was applied to a silica gel column. The white crystalline powder (28,3S) was obtained by elution with a mixed solvent of n-hexane-ether.
-2-octyl-5-14-(2-chloro-3-methylpentanoyloxy)phenyl J-1,3,4-thiadiazole (0.2 g) was obtained.

IR (Nujol): 1755.1745.17
00.1680.1590cl' NMR (CDCI3) δ: 0.70-2.00 (2
411,m), 3.12(211,t, J=711z
), 4.37 (111, d, J-7112), 7.20
(2+1.dJ-811z), 8.05(211,d,
J-811z) Mass mHz: 422 (M
”) Example 12 The following compound was obtained in the same manner as in Example 6.

(S)-6-hexyl-3-14-(G-methyloctanoyloxy)phenyl l-1,2,4-triazine 1
17 (Nujol): 1755.1600.15
00cm-'Mass mHz: 397(M
+ ) NM! ? (CDCI3) δ
: 0.70-2.00 (26+1.m), 2.
58 (21L, t, J-711z), 2.97 (
2+1. t, J-month lz), 7.23 (2+1.d.

J-811z), 8.52 (111, S), 8.5G (
211,d, J=811z) Example 13 The following compound was obtained in the same manner as in Example 3.

(s)-e-hexyl-3-+4-(8-methyloctyloxy)phenyl-1,2,4-)riazine II? (Nujol): 1600.1580.1
505cm-'Mass mHz: 383(M"
) NMR (CDCI3) δ: 0.67-2.1G (2
811,m), 2.98<211. L, J=7
! Iz), 4.03 (211,t, J-711z), 7
．． 02(2+1.d.

J-811z), 8.45 (111,s), 8.47 (
211, d, J-811z) Example 14 60% sodium hydride (154 mg) was suspended in dimethylformamide (10 ml), and 3-hexyl-〇-(4-hydroxyphenyl)-1,2 was added under stirring while cooling with water. ,4-
1-Ryazine (901 mg) was added portionwise. After further stirring for 10 minutes under water cooling, (S)-5-methylhebutyl-p-toluenesulfonate (1,095g)
was added and stirred at room temperature for 1.5 hours and further at 60°C for 3 hours. The reaction solution was poured into water (300+nl) and ether (1
501X2), and the ether layer was collected and washed with water. After drying with magnesium sulfate, the mixture was concentrated to dryness under reduced pressure to obtain a crystalline crude product. The target (S)-a-hexyl-6-14-
(5-methylhebutyloxy)phenyl l-1,2,4
-) Lyazine (320B) was obtained.

IR (Nujol): 1600c+n-'Mas
s mHz: 389 (M'') NMR (CDCI
3) δ: 0.80 to 2.10 (26H, n+),
3.10 (2H, t, J-7) 1z), 4.05 (21
(, t, J-7Hz), 7.04 (211, d.

J-811z), 8. H (211, d, J-811z)
, 8.90 (111,8) Example 15 The following compound was obtained in the same manner as in Example 14.

(1) (S)-6i4-(5-methylhebutyloxy)phenyl)-3-octyl-1,2,4-triazine IR (Nujol): 1[ioocm-'Mas
s to/z: 397 (M'') NMR (CDCI
) δ: 0.87-2.05 (3011, m)
, 3.17 (211,L, J=711z), 4.04(
211, t, J-711z), 7.00 (21+, d.

J-811z), 8.01(211,d, J=811z
), 8.87 (Ill, s) (2) (2S, 3S) -
6-14-(2-chloro-3-methylpentyloxy)
phenyl)-3-octyl-1,2,4-1-riazine II? (Nujol): 1GOOc "'Mas
s mHz: 403 (M÷〉 NMl? (CDCI3) δ: 0.73
~2.2G(2411,+n), 3.15(211
, t , J = 7 l1z), 4.10-4.39 (
311, ll1), 7.04 (211, d.

J-811z), 8.03 (21+, d, J-8112
), 8.89 (111,s) Example 16 (S)-4-(5-Methylhebutyloxy)benzoic acid hydrazide (1.5 g) was dissolved in pyridine (1 flnl), and nonyl chloride (1, 1g) was added dropwise over 15 minutes, and the mixture was stirred at room temperature for 0.5 hours and then at 80°C for 2 hours. After cooling the reaction solution to room temperature, phosphorus pentasulfide (6.3 g
) was added in three portions, stirred at 60°C for 0.5 hour, and further heated under reflux for 15 hours. The reaction solution was poured into ice water, the pII was adjusted to 2 or less with concentrated hydrochloric acid, and then extracted twice with ether. The organic layer was washed with water, dried over magnesium sulfate, and concentrated under reduced pressure to obtain a dark brown oil. This crude product was applied to a silica gel column and eluted with a mixture of n-hexane and ether to give (S)-2-14-(5) pale yellow crystals.
-Methylhebutyloxy)phenyl 1-5-octyl-
1,'3,4-thiadiazole (L, 1 g) was obtained.

IR (Nujol): 1800cn+-'NMR
(CDCI3)δ: 0.70 to 1.00 (911
, m), 1.10-2.00 (21H, m), 3.1
0(211,t, J-71(z), 4.00(211,
t.

J=711z), 8.90(2+1.d, J-8112
), 7.80 (2+1.d, J-8112) Mass
mHz: 402 (M+) Example 17 2-(4-hydroxyphenyl)-5-octyl-1,
To a solution of 3,4-thiadiazole (0.7 g) in N,N-dimethylformamide (51) was added 60% sodium hydride (0, IL g) under water cooling, and the mixture was gradually warmed to room temperature.
Stirred for 1 hour. (2S, 3S)-2-chloro-3-
Methylpentyl-pt-luenesulfonate (0,7
7 g) was added thereto, and the mixture was stirred at 50°C for 8 hours. The reaction solution was poured into ice water and extracted twice with ether. The ether layer was washed with water, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain a slightly yellow solid. This crude product was applied to a silica gel column and eluted with a mixed solvent of n-hexane-ether to obtain white crystals (23,38)-2-+4 to (2-
Chloro-3-methylpentyloxy)phenyl)-5-
Octyl-1,3,4-thiadiazole (0,43g)
I got it.

IR (Nujol): 1t300cm-'NMR
(CDCI3) δ: 0.75 to 2.20 (25
11,n+), 3.1CI(211,1,J-711
2), 4.20 (2+1.S), 6.95 (2+
1. d, J-811z), 7.85 (211, d, J
-811z)Mass m/z: 408(M'')
Next, the phase transition temperatures of each compound are summarized in Tables 1 to 3.

In the table, C is a crystalline phase, S3 is an unidentified smectic phase, and Se
t means chiral smectic C phase, SA means smectic anthropomorphic phase, and rso means isotropic liquid phase.

(Hereinafter, blank space) (Hereinafter, blank space) Example 18 A liquid crystal composition (A) was prepared by mixing three types of compounds represented by the following structural formula in equimolar amounts.

The liquid crystal composition (A) has the phase transition temperature shown below,
It is not a ferroelectric liquid crystal composition because it is composed only of non-optically active substances.

C-2℃ S c*53℃ 5A85℃ N*69℃
Is.

Next, when 30 wt% of the compound of Example 2 (1) according to the present invention represented by the following structural formula was added to (A),
(Hereinafter, blank) Sc* phase appeared in a region including room temperature, and a ferroelectric liquid crystal composition CB) could be obtained. (In the formula, the (S) appended to C indicates that the asymmetric carbon atom is in the S-absolute configuration.) The phase transition temperature of this ferroelectric liquid crystal composition (B) is as follows. show.

C＜0℃ S c*42℃ 5A5B℃ N*8
0” CIs.

Furthermore, a liquid crystal cell was assembled using the liquid crystal composition (B) in the following manner.

First, as shown in the figure, a transparent electrode 3.2 is placed on a glass substrate 1.2.
4 was formed, a polyimide face was applied to the surface, and the surface was rubbed to form an alignment layer 5.6. After that, this glass substrate 1.2 was held with the rubbing layers facing each other at 2 μm intervals, and during this time A liquid crystal cell was prepared by filling the above liquid crystal composition (B). 7 is a sealing material. When two polarizing plates 8.9 were placed above and below this liquid crystal cell and an electric field was applied while maintaining the temperature at 25° C., it was confirmed that two states of display were produced depending on the polarity of the electric field. The response time at this time is ■300μ for voltage application of ±IOV.
It was See. Furthermore, the angle between the two states was 45'', an optimal value for birefringent display.

Furthermore, since both the N* phase and the SA phase were present on the high temperature side of the Sc* phase, it had excellent orientation, and monodomains could be easily formed over the entire orientation region.

Example 19 Similarly to Example 18, 30vt% of the compound of Example 3 according to the present invention represented by the following structural formula was added to the liquid crystal composition (A), and as in Example 18, a ferroelectric liquid crystal composition was obtained. I was able to obtain product (C). (Hereinafter, (S) appended to C in the formula represents that the asymmetric carbon atom has the S-absolute configuration.

) The phase transition temperature of this ferroelectric liquid crystal composition (C) is shown below.

C 0℃ Sc*82℃ SA 70℃ Is.

Furthermore, a cell similar to that of Example 18 was prepared using the above liquid crystal composition (C), and the response time to voltage application of ±10 V at room temperature was measured and found to be 520 μSee. Further, the angle between the two states was 28°.

Example 20 Similarly to Example 18, 30w of the compound of Example 2 (7) according to the present invention represented by the following structural formula was added to the liquid crystal composition (A).
When t% was added, a ferroelectric liquid crystal composition (D) could be obtained in the same manner as in Example 18. The phase transition temperature is shown below.

C 0 ℃ Sc book 80℃ SA 67
℃ Is.

Furthermore, a cell similar to that of Example 18 was prepared using the above liquid crystal composition (D), and the response time to the voltage application of ±1OV at room temperature was measured.
Met. Moreover, the angle between the two states was 32°.

Example 21 Similarly to Example 18, the compound of Example 8 (10) according to the present invention represented by the following structural formula was added to the liquid crystal composition (A).
When Vt% was added, a ferroelectric liquid crystal composition (E) could be obtained in the same manner as in Example 18. The phase transition temperature is shown below.

C<[l’CSc*　57℃　N*　61℃　ts.

Furthermore, a cell similar to that of Example 18 was prepared using the above liquid crystal composition (E), and the response time to voltage application of ±10 V at room temperature was measured and found to be 430 μSee. Moreover, the angle between the two states was 43°.

Example 22 Similarly to Example 18, the compound of Example 9 according to the present invention, which is represented by the following formula, was added to the liquid crystal composition (A) at 1Ovt%.
When added, a ferroelectric liquid crystal composition (F) could be obtained in the same manner as in Example 18. The phase transition temperature is shown below.

C (0℃ S c * 58℃ 5A62℃ N
Book 65℃rs.

Furthermore, a cell similar to that of Example 18 was prepared using the above liquid crystal composition (F), and the response time to voltage application of ±10 V at room temperature was measured and found to be 510 μsec. Also, the angle between the two states was 22''.

Example 23 Similarly to Example 18, 1 Ovt% of the compound of Example 6 according to the present invention represented by the following structural formula was added to the liquid crystal composition (A), and as in Example 18, a ferroelectric liquid crystal composition was obtained. I was able to obtain item (G). The phase transition temperature is shown below.

C<0℃ S c*60℃ 5ANG℃ N pieces
At 67 Is.

Furthermore, a cell similar to that of Example 18 was prepared using the above liquid crystal composition (G), and the response time to the voltage application of ±1OV at room temperature was measured and found to be 820 μsec.

Example 24 Similarly to Example 18, 5vt% of the compound of Example 11 according to the present invention represented by the following structural formula was added to the liquid crystal composition (A), and as in Example 18, a ferroelectric liquid crystal composition was obtained. Product (H) could be obtained. The phase transition temperature is shown below.

C-2℃ S c*52℃ 5A61℃ N*66℃
Further, using the above liquid crystal composition (H), a cell similar to that in Example 18 was prepared, and the voltage at room temperature was ±10V.
The response time to the applied voltage was measured and was 390μ
It was SeQ. Also, the angle between the two states was 45''.

Example 25 Similarly to Example 18, when 5 wt % of the compound of Example 5 according to the present invention represented by the following structural formula was added to the liquid crystal composition (A), a ferroelectric liquid crystal composition was obtained as in Example 18. I was able to obtain item (1). The phase transition temperature is shown below.

C-3℃ S c*53℃ 5A81℃ N 66℃
Is.

Furthermore, a cell similar to that of Example 18 was prepared using the above liquid crystal composition (1), and the response time to the application of a voltage of ±10 V at room temperature was measured and found to be 190 μSee. Further, the angle between the two states was 40@.

Example 26 Similarly to Example 18, 30 wt% of the compound of Example 14 according to the present invention represented by the following structural formula was added to the liquid crystal composition (A).
When added, a ferroelectric liquid crystal composition (J) could be obtained in the same manner as in Example 18. The phase transition temperature is shown below.

C (0℃　S　c*55℃　5A64℃　Is.

Furthermore, a cell similar to that of Example 18 was prepared using the liquid crystal composition (J), and the response time to the application of a voltage of ±10 V at room temperature was measured to be 700 μsec. Further, the angle between the two states was 38°.

Example 27 Similarly to Example 18, 5w of the compound of Example 15 (2) according to the present invention represented by the following structural formula was added to the liquid crystal composition (A).
When t% was added, a ferroelectric liquid crystal composition (K) could be obtained in the same manner as in Example 18. The phase transition temperature is shown below.

Cku0℃ S c*48℃ 5A82℃ N*
66℃ Is.

Furthermore, a cell similar to that of Example 18 was prepared using the above liquid crystal composition (K), and the response time to voltage application of ±10 V at room temperature was measured.
Met. Moreover, the angle between the two states was 31'.

Example 28 Similarly to Example 18, when 5 wt % of the compound of Example 17 according to the present invention represented by the following structural formula was added to the liquid crystal composition (A), a ferroelectric liquid crystal composition was obtained as in Example 18. I was able to obtain item (L). The phase transition temperature is shown below.

C＜0℃ S c*48℃ 5AIL℃ N*
65℃ Is.

Furthermore, a cell similar to that of Example 18 was prepared using the above liquid crystal composition (L), and the response time to voltage application of ±10 V at room temperature was measured.
Met. Further, the angle between the two states was 30@.

[Effect of the invention] As is clear from the above examples, when a liquid crystal composition is prepared using the heterocyclic compound of the present invention, its physical properties (phase transition series, Sc* phase temperature range, response time, tilt corners, etc.)
can be easily changed, and a liquid crystal composition with high responsiveness and high orientation can be easily provided. Therefore, a liquid crystal element using a liquid crystal composition containing the compound of the present invention can be widely used as a display device for electro-optical devices and the like.

[Brief explanation of the drawing]

The drawing is a cross-sectional view showing the structure of a liquid crystal element. 1.2...Glass substrate 3.4...Transparent electrode 5.6...Orientation layer 7...Sealing material 8.9...Polarizing plate

Claims (2)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1 is alkyl or alkoxy, Q is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, A is a bond, -O- or ▲ has a mathematical formula, chemical formula, table, etc. ▼, X is a halogen, n1, n2 and n4 are 0 or 1, n3 is an integer from 0 to 6, n1 and n2 are A heterocyclic compound represented by (C* represents an asymmetric carbon atom) which is also not 0. or ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, A is a bond, -O- or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, X is a halogen, n1, n2 and n4 are 0 or 1, n3 is an integer from 0 to 6, 1. A liquid crystal element comprising a liquid crystal material containing a heterocyclic compound represented by (n1 and n2 are not 0 at the same time, and C* represents an asymmetric carbon atom) sandwiched therein.