JPS6363666A - Pyrimidinylphenyl ester derivative - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I [R* is optical active alkyl containing asymmetric carbon; R is n-alkyl or alkoxy; A is group shown by formula II or -O-). EXAMPLE:(S)-2-{4'-[4''-(2-methyl) butyryloxy]benzoyloxy}phenyl-5-n-octyloxypyri midine. USE:Is a liquid crystal compound, has a cholesteric phase in a high-temperature range of >=about 100 deg.C, shows itself a ferroelectric chiral smectic phase or not, blended with a ferroelectric liquid crystal compound or composition to wide a temperature range of Sc* phase in higher and lower ranges or to make response rate high and used for making a display element or display device using electro-optical effects. PREPARATION:For example, a compound shown by formula III is reacted with a compound shown by formula IV in a solvent in the presence of condensation agent by the use of a tertiary amine such as 4-dimethylaminopyridine, etc., to give a compound shown by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention provides a novel liquid crystal compound that is blended into a ferroelectric liquid crystal compound or composition to improve its properties. Therefore, it can be used in display elements or display devices that utilize the electro-optic effect of liquid crystal compounds.

[Traditional technology]

As a liquid crystal compound exhibiting ferroelectricity, (S)-2=methylbutyl P-(p-n-decyloxyhenzylideneamino)
Cinnamate (DOB AF, IBC) is known. This Schiff base series liquid crystal compound has been the subject of research on ferroelectric liquid crystals, and various compounds have been synthesized.

As an example, [in the formula, X is H, C1, CN, Y is CL C211s-*
represents an asymmetric carbon atom] A compound represented by the formula -m is known.

However, the use of this series of compounds is limited because the temperature at which they exhibit a chiral smectic phase is higher than room temperature, and because they contain a Schiff base, they lack chemical stability. A compound shown by the following structural formula was created as a compound that improved on these drawbacks and attracted attention.

Furthermore, Zaschke Horst.

5tolle, Reinhard et al., the formula % formula % [where m is 1-11. n is 5 to 8] have been introduced (Z, Chem, 19
75 15 (11) 441-3) However, in these, ferroelectric chiral smectic liquid crystal compounds are not described, nor are there any descriptions suggesting such compounds.

[Problem that the invention seeks to solve]

The present invention provides a novel liquid crystal compound,
A liquid crystal compound that can be blended into a ferroelectric liquid crystal compound or composition to improve its properties, and the compound provided by the present invention is represented by the following general formula. That is, R2A-6-coo-o-b-R (in the formula, three are optically active alkyl groups having asymmetric carbon atoms, R is a linear alkyl group or a linear alkoxy group) , A represents -g-〇- or -0-) [Means for solving the problem] The compound represented by the above general formula provided by the present invention is produced as follows. That is, a compound represented by the formula (+) R-A-Q-COOH(1) (in the formula, R@ and A are the same as above) and a compound represented by the formula (n) +1O-Q-i-R(■) (in the formula The desired compound can be obtained by reacting the compound represented by (R is the same as above) in an appropriate solvent in the presence of a condensing agent.

Here, the W1 group R'' shown in formula (1) is (S) (or (R))-2-methylbutyl.

(S) (or (R)")-1-methylethyl, and the substituent R shown in formula (II) includes n-hexyl, n-hebutyl, n-octyl, n-nonyl,
Examples include n-decanyl, n-hexyloxy, n-hebutyloxy, n-octyloxy, n-nonyloxy, and n-decanyloxy. The solvents used are methyl acetate, ethyl acetate, dioxane, tetrahydrofuran, N,N-dimethylformamide, and dimethylsulfoxide.

Chloroform, methylene chloride, isopropyl ether,
Examples of condensing agents include benzene and toluene.
N,N'-dicyclohexylcarbodiimide, 1.1'
-sulfinyldiimidazole, 1,1'-carbonyldiimidazole, and the like. It is effective to use a tertiary amine such as 4-dimethylaminopyridine during the condensation.

Furthermore, as another method, the carboxyl group in the compound represented by formula (2) is changed to a reactive group, such as an acid halide, a mixed acid anhydride, or an active ester, and then reacted with the compound represented by formula (n). There is a way - for example,
A target compound is obtained by reacting a compound represented by formula (1) with thionyl chloride to convert it into an acid chloride, and reacting it with a compound represented by the following formula (II) in the presence of a tertiary amine such as lysine or triethylamine. Furthermore, the raw material compounds used in the present invention are produced according to the specific examples shown in Reference Examples.

The liquid crystal compound of the present invention has a cholesteric phase in a high temperature range of around 100° C. or higher, and some have a ferroelectric chiral smectic phase and some do not. Alternatively, by blending an appropriate amount into the composition, there is an effect of vertically expanding the temperature range of the Sc'' phase and increasing the response speed.

The present invention will be specifically explained below by describing examples.

Example 1 Synthesis of (S)-2-+4'-[4''-(2-methyl)butyryloxycopenzoyloxy)phenyl-5-n-octyloxypyrimidine: 2.2g (0,0099
mol) of (S)-4-(2-methyl)butyryloxybenzoic acid and 3°0 g (0,010 mol) of 2-(
4-Hydroxy)phenyl-5-n-octyloxypyrimidine in 251 ethyl acetate: 8 pieces, 2.3 g
(0,011 mol) of N,N'-dicyclohexylcarbodiimide and 0.12 g (0,098 mmol) of 4-dimethylaminopyridine were added and stirred at room temperature for 7 hours.
Go to ↑ and go to f. After the reaction was completed, the organic layer was separated into ice water, extracted with ethyl acetate, washed with a 10% aqueous sodium hydroxide solution, water, and saturated brine, dried over magnesium sulfate, and concentrated. This was purified by silica gel column chromatography and further recrystallized from ethanol to obtain 1.7 g of the target compound.

[α] =+9.90@ (C=2.19.CHCl
3) IR';',, cm-': 1760.1?40
．． 1445°1270.1205.1160°1080.885.785 HNMR (CDCIs, 60MHz) δ(1)I)J)
:0, 67~2. 13 (m, 25 H)2
．． 33-2.90 (m, LH) 4.07 (t, 2H) 7, 21 (d, 2H) 7,
29 (d, 2H)8, 23
(d, 2H)8, 37
(s, 213) 8, 42
(d, 2H) The positive transition temperature of this compound is shown below.

Cry-Sx-*Ch-1s.

Example 2 Synthesis of (S)-2-[4'-[4''-(2-methyl)butyryloxy]henzoyloxy)phenyl-5-n-octylpyrimidine: 1.5 g (0,0068 mol) of ( S)-4-(2-
methyl)butyryloxybenzoic acid, 2. 0g (0,
0067 mol) of 2-(4-hydroxy)phenyl-5
-n-octylpyrimidine, 1.5g (0,0073
mol) of N,N'-dicyclohexylcarbodiimide,
Using 80 μ (0,066 mmol) of 4-dimethylaminopyridine and 20+1 of ethyl acetate to
1.1 g by the same operation as Example 1.
The desired compound was obtained.

[α]-410,2° (C=2.08.CHCl5)
IR%), , cm-': 1760, 1735.14
30゜1270.1200.1165゜' HN M R (CD Cl s , 60 MHz
) δ (pPII): 0.60 to 1.93 (m, 2
H) 2.27-2.90 (m, 3H) 7.13 (d, 2H) 7.23 (d, 2H) 8.13 (d, 2H) 8.40 (d, 2H) 8.50 ( s, 2H) The phase transition temperature of this compound is described below.

Cry” Ch-41s.

Example 3 (S)-2-<4'-ra'-(2-methylbutoquino)
Synthesis of phenylcarbonyloxy]phenyl)-5-n-octylpyrimidine: 1.6 g (0,0077 mol) of (S)-4-(2-
Methylbutoxy)amic acid, alpha aromatic acid, 2.3g (0°007
7 mol) of 2-(4-hydroxy)phenyl-5-n-
Dissolve octylpyrimidine in 251 h ethyl acid,
．． 9 g (0,0092 mol) of N,N'-dicyclohexylcarbodiimide and 90 g (0,074 mmol) of 4-dimethylaminopyridine were added and stirred at room temperature for 17 hours.

After the reaction was completed, it was poured into ice water and extracted with ethyl acetate to give 10%
The mixture was washed with sodium hydroxide, then with water, and then with saturated brine, dried over magnesium sulfate, and concentrated. The product was purified by silica gel column chromatography and further recrystallized from ethanol to obtain 1.3 g of the target compound.

[α] =+5.4” (C=2.05.CIIC
1CllC13)IRVlaa': 1735.161
0,1435°1260.1200.1165°1080.850,655' HNMR (CDC13,60MH2) δ (ppm)
:0, 63~2. 17 (m, 24H)2
．． 58 (t, 2H)3, 8
2 (d, 2) ()6, 89
(d, 2H)7, 26
(d, 2H)8,. 03
(d, 2H)8, 41 (
d, 2H) 8, 52 (s,
2H) The phase transition temperature of this compound is described below.

Cry-ICh-=Is.

Example 4 (S)-2-(4'-[4''-(2-methylbutquin)
Synthesis of phenylcarbonyloxy]phenyl)-5-n-octyloxypyrimidine: 2.2g (0,008
2.5 g (0°0083 mol) of 2-(4-hydroxy)phenylene 5-n-octyloxypyrimidine, Ethyl acetate of 25-1, 1.9 g (0,0'0
92 mol) of N,N'-dicyclohexylcarbodiimide and 0.1 g (0,00082 mol) of 4-dimethylaminopyridine were carried out in the same manner as in Example 1 to obtain 2.8 g of the target compound. Obtained.

[ffi ==5.0' (C=2.10.ClC
l5) IRV',,,ca-":1740.16
05.1435゜1280.1250,1190゜11?0,1080.1050' H-NMR (CDCI3.60MHz>6 (pp
m): 0.50-2.16 (m, 24) 1) 3.78
(d, 2H) 4.03 (t, 2H) 6.87 (d, 2H) 7.27 (d, 2H38,07(d
, 2H) 8.32 (d, 2H) 8.35 (s, 2H) The phase transition temperature of this compound is shown below.

Cry = Ch-41s.

Reference Example 1 Synthesis of (S)-4-(2-methyl)butyryloxyamne, α-fragrant pendyl esteno C: 4.5 g (0,044 mol) of (S)-2-methylbutyric acid and 10 g (0 ,044 mol) of benzyl 4-hydroxybenzoate was added to 501 mol of ethyl acetate, and
g (0.049 mol) of N,N'-dicyclohexylcarbodiimide and 0.54 g (0.44 mmol) of 4-dimethylaminopyridine were added and stirred at room temperature for 18 hours. After completion of the reaction, the mixture was poured into water. The organic layer was separated, further extracted with ethyl acetate, and extracted with a 10% aqueous sodium hydroxide solution.

The mixture was washed successively with water and saturated brine, dried over magnesium sulfate, and then concentrated. The residue was purified by silica gel column chromatography to obtain 9.3 g of the target compound.

Example 5 (S)-4-(2-methylbutyryloxy)benzoic acid 4
- (1-(5-n-heptyl)pyrimidylphenyl ester 2 g (0,0090 mol) of (S)-4-(2-methylbutyryloxy)benzoic acid, 2.4 g (0,0089
mol) of 2-(4-hydroxyphenyl)-5-n-hebutylpyrimidine, 2.0 g (0,0097 mol) of N,N-dicyclohexylcarbodiimide and 0.0 g (0.0097 mol) of N,N-dicyclohexylcarbodiimide. l1
g (0,00090 mol) of 4-dimethylaminopyridine was stirred in 30 ml of ethyl acetate at room temperature for 8 hours.

The reaction mixture was poured into water, extracted with ethyl acetate, washed with water, dried, concentrated, and then subjected to silica gel column chromatography and recrystallization with ethanol. g
The following compounds were obtained.

[α] +11.0 (C2,06,CHCl3)IR
,9,,,cta-': 1755,1740,143
0゜1265.1190.1160゜' H-NMR (CDCIs, 60M)i 2) δ(p
pm): 0.67-2.03 (m, 18H) 2.33-2.80 (m, 3H) 1.11 (d, 2H) 7.21 (d, 211) 8, 12
(d, 2H)8. 3f3
(d, 2H) 8, 48
(s, 2H) This compound showed the following transition temperature.

The obtained compound had good domain properties when blended with a ferroelectric chiral smectinok liquid crystal compound, and served to expand the lower 1fA degree of the SmC phase.

Example 6 The compounds of Examples 1.2 and 4 were blended into the following ferroelectric liquid crystal composition A, and the properties were compared.

Here, the response speed is ±20V when injected into a 1.7μm cell.
A pulse waveform of

As shown in the table, by appropriately blending the compound of the present invention with Composition 58, it is possible to spread the Sc'' phase vertically. As shown in the blend example, it is possible to obtain a composition with a ch phase.

Furthermore, it is also possible to increase the response speed, as in the example of blending the compound of Example 2 into the proboscis.

IRJ,,,cs-': 1760. lT2O, 161
01510,1270,1210゜1180.1100,1020゜7+60.700' H-NMR (CDCit, 50MJ(2) δ(
ppm): θ+ 3'Z~l-42(m, 5H) L 42~2-02 <rn, 2H) 2.33~2
−8<1<m, it port 5.28 (
s, 2H) 7.06 (d, 2H) 7.32
(s, 5H) 8.02 (d, 2H) Reference Example 2 Synthesis of (S)-4-(2-methyl)butyryloxybenzoic acid: 9.0 g (0,029 mol) of (S)-4-( 2-Methyl) butyryloxyamne, alpha fragrant hensyl ester, 0
．． 9 g of palladium carbon was placed in 90S11 ethanol and catalytic reduction was performed. After 1 hour and 30 minutes, insoluble matter was filtered off, and the liquid was condensed to give 6.3 g of the crude target compound.

! R order, xCm-': 3200-2450 (br
).

1770.1680.1605゜1430.1320.1295゜1210.1165,1105゜760.550' HNMR (CD'CIs, 60MHz) δ(pp
m): 0.83~1-43 (m, 6M) 1, 43~2. 13 (m, 211) 2.33
~2.87 (m, IH) 7.13 (d, 2!I) 8.08
(d, 211) 10.40 (b
r, IH) Reference Example 3 Synthesis of (S)-4-(2-methyl)butyryloxybenzoin: 5 g (0,036 mol) of 4-hydroxyben, Y:!
, add 3011+1 FNO J to fragrant acid, 10
% potassium hydroxide aqueous solution, 6 g (0
,040 mol) of (S)-2-methylbutyl bromide was added, and the mixture was refluxed for 5 hours. After completion of the reaction, the precipitated crystals were acidified with hydrochloric acid, collected by filtration, washed and dried to obtain 3.1 g of the desired compound.

Reference Example 4 Synthesis of 2-(4-hydroxy)phenyl-5-n-octylpyrimidine: 4.32 g of 4-hydroxybenzamidine hydrochloride, 5
．． Dissolve 7 g of β-dimethylamino-α-n-octyloxyacrolein in 40 ml of ethanol, and add 19.3 g of 28% sodium methylate methanol solution to this.
was added and refluxed for 8 hours. After the completion of the reaction, the mixture was poured into ice water, made acidic with dilute sulfuric acid, extracted with ethyl acetate, and the extracted layer was washed with saturated aqueous sodium bicarbonate and saturated brine, and dried over magnesium sulfate. After that, it was concentrated to obtain 1 g of oily substance 7'. Recrystallization from n-hexane-ethanol gave 2.79 g of the target compound.

IR'>aa*am-': 3350-3050,161
0°1595.1435.1280°1245, 1175. 790' HNMR (CDC1s+ 60MHz) δ (
ppi): 0, 6-2. 2 (m, 17H
)4, 02 (t, 2H)6, 85
(d, 2H) 8, 16
(d, 2H)8, 43 (s, 2
H) Above

Claims (1)

[Claims] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ A pyrimidinyl phenyl ester derivative represented by an alkyl group or a linear alkoxy group,
A indicates ▲a mathematical formula, chemical formula, table, etc.▼or -O-)