JPH0717616B2 - Pyrimidinylphenyl ester derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention provides the novel compound. Some compounds provide a liquid crystal compound that is blended with a ferroelectric liquid crystal compound or composition to improve its properties, and therefore are used in display elements or display devices that utilize the electro-optical effect of the liquid crystal compound. .

[Conventional technology]

As a liquid crystal compound exhibiting ferroelectricity, (S) -2-methylbutyl p- (pn-decyloxyphenylideneamino)
Cinnamate (DOBAMBC) is known. This Schiff base type liquid crystal compound has been the subject of research on ferroelectric liquid crystals, and various compounds have been synthesized. As an example A compound represented by the general formula [wherein X represents H, CI, CN, Y represents Cl, C ₂ H ₅ , and * represents an asymmetric carbon atom] is known.

However, compounds of this series are limited in use because they have a chiral smectic phase temperature higher than room temperature and lack chemical stability because they contain a Schiff base. As a compound that improves these drawbacks, A compound represented by the following structural formula was created and attracted attention.

Furthermore, the formula by Zaschke Horst, Srolle, Reinhard et al. Some compounds represented by the formula [m represents 1-11 and n represents 5-8] have been introduced (Z.Che
m.1975 15 (11) 441-3). However, among these, the ferroelectric chiral smectic liquid crystal compound is not described, nor is there any description suggesting it.

[Problems to be solved by the invention]

The present invention provides a novel liquid crystal compound,
A liquid crystal compound that is blended with 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, (In the formula, R ^* represents an alkyl group having an asymmetric carbon atom, and R represents a linear alkyl group or a linear alkoxy group.) [Means for Solving Problems] The compound represented by the general formula is prepared as follows. That is, the formula (I) (Wherein R ^* is the same as above) and the compound of the formula (II) (Wherein R is the same as above) is reacted in a solvent in the presence of a condensing agent to obtain the target compound.

Examples of the substituent R ^{* represented} by the formula (I) include (S) (or (R))-1-methylpropyl, and examples of the substituent R represented by the formula (II) include n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decanyl, n
-Hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decanyloxy and the like can be mentioned. The solvent used is methyl acetate, ethyl acetate,
Dioxane, tetrahydrofuran, N, N-dimethylformamide, dimethylsulfoxide, chloroform, methylene chloride, isopropyl ether, benzene, toluene and the like can be mentioned, and as the condensing agent, N, N′-dicyclohexylcarbodiimide, 1,1′-sulfinyldiamine Examples thereof include imidazole and 1,1′-carbonyldiimidazole. In the condensation, it is effective to use a tertiary amine such as 4-dimethylaminopyridine.

Further, as another method, the carboxyl group in the compound represented by the formula (I) is reacted with a reactive group such as an acid halide,
There is a method in which a mixed acid anhydride or an active ester is changed and then the compound represented by the formula (II) is reacted. As an example, by reacting a compound of formula (I) with thionyl chloride to form an acid chloride, and reacting with a compound of formula (II) in the presence of a tertiary amine such as pyridine or triethylamine. The compound can be obtained.

The raw material compounds used in the present invention are prepared 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 about 100 ° C. or higher, and as such, there are those having a strong magnetoelectric chiral smectic phase and those having no ferroelectric liquid crystal compound, Alternatively, by blending an appropriate amount in the composition, it is effective in expanding the temperature region of the Sc ^* phase vertically and increasing the response speed.

The present invention will be specifically described with reference to the following examples.

Example 1 Synthesis of (S) -2- {4 '-[4 "-(2-methyl) butyryloxy] benzoyloxy} phenyl-5-n-octyloxypyrimidine: 2.2 g (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 was dissolved in 25 ml of ethyl acetate to give 2.3 g (0.011 mol) of N, N'-dicyclohexylcarbodiimide and 0.1
2 g (0.098 mmol) of 4-dimethylaminopyridine was added, and the mixture was stirred at room temperature for 7 hours. After completion of the reaction, the mixture was poured into ice water, the organic layer was separated, further extracted with ethyl acetate, washed with 10% aqueous sodium hydroxide solution, water and saturated brine, dried over magnesium sulfate, and concentrated. This was purified by silica gel column chromatography and then recrystallized from ethanol to obtain 1.7 g of the target compound.

▲ [α] ²⁵ _D ▼ ＝ ＋ 9.90 ° (C = 2.19, CHCl ₃ ) IRν _max cm ^-1 : 1760,1740,1445, 1270,1205,1160, 1080,885,785 ′ H-NMR (CDCl ₃ , 60MHz ) Δ (ppm): 0.67 to 2.13 (m, 25H) 2.33 to 2.90 (m, 1H) 4.07 (t, 2H) 7.21 (d, 2H) 7.29 (d, 2H) 8.23 (d, 2H) 8.37 (s, 2H) 8.42 (d, 2H) The phase transition temperature of this compound is shown below.

Example 2 Synthesis of (S) -2- {4 ′-[4 ″-(2-methyl) butyryloxy] benzoyloxy} phenyl-5-n-octylpyrimidine: 1.5 g (0.0068 mol) of (S) -4 -(2-Methyl) butyryloxybenzoic acid, 2.0 g (0.0067 mol) of 2- (4-
Hydroxy) phenyl-5-n-octylpyrimidine,
Using 1.5 g (0.0073 mol) of N, N'-dicyclohexylcarbodiimide, 80 mg (0.066 mmol) of 4-dimethylaminopyridine and 20 ml of ethyl acetate, the reaction was carried out at room temperature for 10 hours, and the same procedure as in Example 1 was conducted. , 1.1 g of the target compound was obtained.

▲ [α] ²⁵ _D ▼ ＝ + 10.2 ° (C = 2.08, CHCl ₃ ) IRν _max cm ^-1 : 1760,1735,1430,1270,1200,1165, 1075 ′ H-NMR (CDCl ₃ , 60MHz) δ (Ppm): 0.60 to 1.93 (m, 2H) 2.27 to 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 shown below.

Reference Example A (S) -2- {4 '-[4 "-(2-methylbutoxy)
Synthesis of phenylcarbonyloxy] phenyl} -5-n-octylpyrimidine: 1.6 g (0.0077 mol) (s) -4- (2-methylbutoxy) benzoic acid, 2.3 g (0.0077 mol) 2- (4- (Hydroxy) phenyl-5-n-octylpyrimidine was dissolved in 25 ml of ethyl acetate and 1.9 g (0.0092 mol) of N, N'-dicyclohexylcarbodiimide and 90 mg (0.074 mmol) of 4-dimethylaminopyridine were added at room temperature. Stir for hours. After completion of the reaction, the mixture was poured into ice water, extracted with ethyl acetate, washed with 10% sodium hydroxide, then water, and finally with saturated saline, dried over magnesium sulfate, and concentrated. The product was purified by silica gel column chromatography and recrystallized from ethanol to obtain 1.3 g of the target compound.

▲ [α] ²⁵ _D ▼ ＝ ＋ 5.4 ° (C = 2.05, CHCl ₃ ) IRν _max cm ^-1 : 1735,1610,1435,1260,1200,1165, 1080,850,655 ′ H-NMR (CDCl ₃ , 60MHz ) Δ (ppm): 0.63 to 2.17 (m, 24H) 2.58 (t, 2H) 3.82 (d, 2H) 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 shown below.

Reference Example B (S) -2- {4 '-[4 "-(2-methylbutoxy)
Synthesis of phenylcarbonyloxy] phenyl} -5-n-octyloxypyrimidine: 2.2 g (0.0083 mol) (S) -4- (2-methylbutoxy) benzoic acid, 2.5 g (0.0083 mol) 2- (4 -Hydroxy) phenyl-5-n-octyloxypyrimidine,
25 ml of ethyl acetate, 1.9 g (0.0092 mol) of N, N'-dicyclohexylcarbodiimide and 0.1 g (0.00082 mol)
The same operation as in Example 1 was carried out using 4-dimethylaminopyridine to obtain 2.8 g of the target compound.

▲ [α] ²⁵ _D ▼ ＝ ＋ 5.0 ° (C = 2.10, CHCl ₃ ) IRν _max cm ^-1 : 1740,1605,1435, 1280,1250,1190, 1170,1080,1050 ′ H-NMR (CDCl ₃ , 60MHz) δ (ppm): 0.50 to 2.16 (m, 24H) 3.78 (d, 2H) 4.03 (t, 2H) 6.87 (d, 2H) 7.27 (d, 2H) 8.07 (d, 2H) 8.32 (d, 2H) 8.35 (s, 2H) The phase transition temperature of this compound is shown below.

Reference Example 1 Synthesis of benzyl ester of (S) -4- (2-methyl) butyryloxybenzoic acid: 4.5 g (0.044 mol) of (S) -2-methylbutyric acid and 10 g
(0.044 mol) of benzyl 4-hydroxybenzoate 50m
10 g (0.049 mol) of N, N'-dicyclohexylcarbodiimide and 0.54 g (0.44 mmol) of 4-dimethylaminopyridine were dissolved in 1 of ethyl acetate and added at room temperature to 18
Stir for hours. After completion of the reaction, the mixture was poured into water, the organic layer was separated, further extracted with ethyl acetate, washed with 10% aqueous sodium hydroxide solution, water and saturated brine in that order, dried over magnesium sulfate and concentrated. The residue was purified by silica gel column chromatography to obtain 9.3 g of the target compound.

Example 3 (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-heptylpyrimidine, 2.
0 g (0.0097 mol) of N, N-dicyclohexylcarbodiimide and 0.11 g (0.00090 mol) of 4-dimethylaminopyridine were 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 and concentrated. Then, silica gel column chromatography and recrystallization with ethanol were performed to obtain 0.57 g of the title compound.

▲ [α] ²⁵ _D ▼ ＝ ＋ 11.0 ° (C 2.06, CHCl ₃ ) IRν _max cm ^-1 : 1755,1740,1430, 1265,1190,1160, 1075 ′ H-NMR (CDCl ₃ , 60MHz) δ ( ppm): 0.67 to 2.03 (m, 18H) 2.33 to 2.80 (m, 3H) 7.11 (d, 2H) 7.21 (d, 2H) 8.12 (d, 2H) 8.38 (d, 2H) 8.48 (s, 2H) This The compound showed the following transition temperatures:

The obtained compound had good domain property when blended with the ferroelectric chiral smectic liquid crystal compound, and worked to widen the lower limit temperature of the SmC phase.

Example 4 The compounds of Examples 1, 2 and 4 were blended with the following ferroelectric liquid crystal composition A to compare the characteristics.

Composition A Here, the response speed was obtained by injecting into a 1.7 μm cell, applying a pulse waveform of ± 20 V, and determining the minimum pulse width at which the display switches.

As shown in the table, the temperature range of the Sc ^* phase can be broadened vertically by blending the compound A of the present invention in an appropriate amount. Further, as an example of the blend of the composition A and the compound of Example 4 shows, a composition having a Ch phase can be obtained.

Further, it is possible to increase the response speed as in the case of the blend of the composition A and the compound of Example 2.

IRν _max cm ^-1 : 1760,1720,1610, 1510,1270,1210, 1180,1100,1020, 760,700'H-NMR (CDCl ₃ , 60MHz) δ (ppm): 0.82 ~ 1.42 (m, 6H) 1.42 ~ 2.02 (m, 2H) 2.33 to 2.80 (m, 1H) 5.28 (s, 2H) 7.06 (d, 2H) 7.32 (s, 5H) 8.02 (d, 2H) Reference Example 2 (S) -4- (2- Synthesis of methyl) butyryloxybenzoic acid: 9.0 g (0.029 mol) of (S) -4- (2-methyl) butyryloxybenzoic acid benzyl ester and 0.9 g of palladium carbon were placed in 90 ml of ethanol for catalytic reduction. After 1 hour and 30 minutes, the insoluble matter was filtered off, and the filtrate was concentrated to obtain 6.3 g of the crude target compound.

IR ν _max cm ^-1 : 3200 to 2450 (br), 1770,1680,1605, 1430,1320,1295, 1210,1165,1105, 760,550'H-NMR (CDCl ₃ , 60MHz) δ (ppm): 0.83 to 1.43 (M, 6H) 1.43 to 2.13 (m, 2H) 2.33 to 2.87 (m, 1H) 7.13 (d, 2H) 8.08 (d, 2H) 10.40 (br, 1H) Reference Example 3 (S) -4- (2) Synthesis of -methyl) butyryloxybenzoic acid: 5 g (0.036 mol) of 4-hydroxybenzoic acid was dissolved in 30 ml of ethanol and 6 g (0.040 mol) of (S) -2- in the presence of 15 ml of 10% aqueous potassium hydroxide solution. (Methylbutyl bromide was added and the mixture was refluxed for 5 hours. After completion of the reaction, acidified with hydrochloric acid, and the precipitated crystals were 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, 5.7 g of β-dimethylamino-α-n-octyloxyacrolein in 40 ml. It was dissolved in ethanol, 28% sodium methylate methanol solution (19.3 g) was added thereto, and the mixture was refluxed for 8 hours. After the reaction was completed, it was poured into ice water, acidified with diluted sulfuric acid water, extracted with ethyl acetate, the extract layer was washed with saturated aqueous sodium hydrogen carbonate and saturated brine, dried over magnesium sulfate, and concentrated to give 7.1 g of an oily substance. Obtained. Recrystallization from n-hexane-ethanol gave 2.79 g of the desired compound.

IRν _max cm ^-1 : 3350 to 3050,1610, 1595,1435,1280, 1245,1175,790'H-NMR (CDCl ₃ , 60MHz) δ (ppm): 0.6 to 2.2 (m, 17H) 4.02 (t, 2H) 6.85 (d, 2H) 8.16 (d, 2H) 8.43 (s, 2H)

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Masaaki Taguchi 6-31-1, Kameido, Koto-ku, Tokyo Seiko Electronics Co., Ltd. (72) Takamasa Harada 6-31-1, Kameido, Koto-ku, Tokyo Seiko Electronics Industry Co., Ltd.

Claims (1)

[Claims] 1. A formula A cholesteric liquid crystalline pyrimidinyl phenyl ester derivative represented by the formula [wherein R ^* represents an alkyl group having an asymmetric carbon atom, and R represents a linear alkyl group or a linear alkoxy group].