JPH0684355B2 - Pyrimidinophenyl ester derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention provides a novel liquid crystal compound.
The liquid crystal compound provided by the present invention is blended with a ferroelectric chiral smectic liquid crystal compound, and is used for producing an electro-optical device such as a liquid crystal display device, an optical shutter or the like utilizing an electro-optical effect.

[Conventional technology]

Many known liquid crystal compounds include a so-called nematic liquid crystal. This one is currently
Although it is mainly used for liquid crystal display devices, it is said that it is approaching the limit for increasing the display capacity.

Ferroelectric liquid crystals, which have high-speed response and memory properties, have attracted attention as next-generation liquid crystals and are being actively studied. Among them, (S) -2-methylbutyl p- (p-
n-decyloxybenzylideneamino) cinnamate (DO
BAMBC) is a well-known compound. However, since this compound has a high liquid crystallinity of 60 ° C. or higher, it is limited in temperature during use.

In order to obtain a ferroelectric chiral smectic liquid crystal that exhibits liquid crystallinity in a wide temperature range including room temperature, many efforts have been made to improve the performance by creating the compound itself or blending it.

The liquid crystal compound having 2-phenylpyrimidine, which has the same skeleton as the liquid crystal compound provided by the present invention, is H.ZA.
It is known that SCHKE published in 1975, Journal f.prakt.Chemie, Volume 317, page 617, but a ferroelectric chiral smectic liquid crystal compound in which an alkyl group is bonded to both sides of the skeleton through oxygen atoms is Not mentioned. It is desired to develop a ferroelectric chiral smectic liquid crystal compound having excellent performance.

[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.

[Means for solving problems]

The novel liquid crystal compound provided by the present invention is represented by the following general formula. That is, (In the formula, R is an alkyl group or an alkoxy group having a straight carbon chain, and R ^* is (R ₁ is a C ₁ -C ₅ alkyl group, R ₂ is a C ₁ -C ₄ alkyl group,
n represents an integer) and represents an optically active group having an asymmetric carbon atom in the chain. ).

The compound represented by the formula (I) has the formula (II) (Wherein R is the same as above) and a compound of formula (III) (In the formula, R ^* is the same as above), or a reactive derivative thereof.

The substituent R in the compound represented by the formula (II) used herein is a linear alkyl group or an alkoxy group, and is, for example, pentyl, hexyl, heptyl, octyl, nonyl, decanyl, undecyl, dodecyl, pentyloxy, Hexyloxy, heptyloxy, nonyloxy, decanyloxy, undecyloxy, dodecyloxy and the like can be mentioned. The substituent R ^* in the compound represented by the formula (III) is an optically active alkyl group having an asymmetric carbon atom. One of the elements directly bonded to the carbon atom is an oxygen atom, (R ₁ is a C ₁ -C ₅ alkyl group, R ₂ is a C ₁ -C ₄ alkyl group,
n is an integer), and the configuration around C ^* is S or R, and if these groups are exemplified, for example, (S)
(Or (R))-2-methoxybutyl, (S) (or (R))-2-ethoxybutyl, (S) (or (R))
-2-butoxybutyl, (S) (or (R))-2-methoxypropyl, (S) (or (R))-2-ethoxypropyl, (S) (or (R))-3-methoxybutyl , (S) (or (R))-3-ethoxypentyl and the like. In the reaction, both are appropriately used as a solvent (eg, ethyl acetate, methyl acetate, ethyl ether, tetrahydrofuran, dioxane, dimethylformamide, dimethyl sulfoxide, ethylene glycol dimethyl ether, etc.)
Dissolved in N, N'-dicyclohexylcarbodiimide,
It is carried out using a condensing agent such as thionyl chloride or phosphorus oxychloride. The reaction proceeds smoothly when a tertiary amine such as 4-dimethylaminopyridine, dimethylaniline or triethylamine is used in combination.

When the reactive derivative of the compound represented by the formula (III) is used, examples of the reactive derivative include an acid halide (for example, an acid chloride formed with thionyl chloride), an active ester (for example, p-nitrophenol), and a mixture. An acid anhydride (made of, for example, ethoxycarbonyl chloride) and the like can be mentioned, which are subjected to the reaction in the presence of a tertiary amine. The compound (II) used as a raw material is made from β-dimethylamino-α- (n-alkyl or alkoxy) acrolein and hydroxybenzamidine. On the other hand, the compound (III) is produced by using optically active lactic acid as a raw material and repeating chemical decoration to change the n. For example Carbon was increased by one by repeating this cycle. In other words, since an optically active alcohol in which n is increased by 1 is obtained, using this, for example, After reacting with hydroxyphenyl benzoic acid ester, after depyrinylation, the hydroxyl group is alkylated with alkyl halide (R ₂ X) and hydrolyzed. Can be obtained.

In addition, the raw material in the case where R ₁ in R ^* represents C _{1 to} C ₅ is prepared as follows.

The R ^* is norvaline R ₁ is C _2, R ^* R ₁ is C ₃ is set to each raw material norleucine, diazotized, and hydrolyzing the resulting diazo compound to obtain a α- hydroxy carboxylic acids Following the above example, after reacting with dihydropyran and then esterifying it, it is reduced to alcohol to form a reactive derivative (for example, p-toluenesulfonic acid) and then reacted with hydroxyphenyl benzoate. After depyranylation, the hydroxyl group is alkylated,
By hydrolyzing Can be obtained.

Most of the liquid crystal compounds of the present invention have a cholesteric phase over a wide temperature range and do not have a ferroelectric chiral smectic phase, but when blended with a ferroelectric liquid crystal compound or composition, the temperature of the Sc ^* phase is increased. The area can be expanded vertically and the responsiveness can be improved.

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

Example 1 Synthesis of (S) -2- {4 '-[4 "-(2-methoxy) butoxy] benzoyloxy} -5-n-octyloxypyrimidine: 1.0 g (0.0045 mol) of (S) -4. -(2-Methoxybutoxy) benzoic acid and 1.34 g (0.0045 mol) of 2- (4-
Hydroxy) phenyl-5-n-octyloxypyrimidine was dissolved in 30 ml of ethyl acetate, and 1.1 g (0.00
53 mol) of N, N'-dicyclohexylcarbodiimide and 50 mg (0.041 mmol) of 4-dimethylaminopyridine were added, and the mixture was reacted at room temperature for 7 hours. After completion, pour in water,
Extracted with ethyl acetate, 10% aqueous sodium hydroxide solution,
The extract was washed with water and saturated brine in that order, dried over magnesium sulfate, and concentrated. This was purified by silica gel column chromatography and recrystallized from ethanol to obtain 0.48 g of white crystals.

▲ 〔α〕 ²⁵ _D ▼ ＝ -12.0 ° (C 2.00, CHCl ₃ ) IRν _max cm ^-1 : 1740,1555,1470,1250,1100,1080,885,840,
780,760'H-NMR (CDCl ₃ , 60MHz) δ (ppm): 0.66 ~ 2.07 (m, 20H) 3.27 ~ 3.70 (s, 1H) 3.43 (s, 3H) 3.90 ~ 4.23 (m, 4H) 6.93 (d, 2H) 7.27 (d, 2H) 8.10 (d, 2H) 8.37 (d, 2H) 8.40 (s, 2H) The transition temperatures of this compound are shown below.

Example 2 Synthesis of (S) -2- {4 '-[4 "-(2-methoxy) butoxy] benzoyloxy} -5-n-octylpyrimidine: 0.4 g (0.0018 mol) of (S) -4- (2-Methoxy) butoxybenzoic acid, 0.54 g (0.0018 mol) 2- (4-hydroxy) phenyl-5-n-octylpyrimidine, 10
ml ethyl acetate, 0.41 g (0.002 mol) N, N'-dicyclohexylcarbodiimide and 20 mg (0.016 mmol)
4-dimethylaminopyridine was reacted at room temperature for 9 hours,
Following the same procedure as in Example 1, 0.2 g of white crystals was obtained.

▲ 〔α〕 ²⁵ _D ▼ ＝ -12.9 ° (C 1.52, CHCl ₃ ) IRν _max cm ^-1 : 1745,1610,1430,1260,1200,1165,1080 ′ H-NMR (CDCl ₃ , 60MHz) δ (ppm ): 0.70~2.00 (m, 20H) 2.80~2.43 (m, 2H) 3.33~3.67 (m, 1H) 3.43 (s, 3H, -OCH 3) 4.03 (d, 2H) 6.94 (d, 2H) 7.20 ( s, 2H) 7.27 (d, 2H) 8.10 (d, 2H) 8.43 (d, 2H) 8.55 (d, 2H) The transition temperatures of this compound are shown below.

Example 3 Synthesis of (S) -2- {4 ′-[4 ″-(2-ethoxy) propoxy] benzoyloxy} -5-n-octyloxypyrimidine: 0.5 g (0.0022 mol) of (S) -4 -(2-Ethoxy) propoxybenzoic acid, 0.67 g (0.0022 mol) of 2- (4-
Hydroxy) phenyl-5-n-octyloxypyrimidine, 18 ml of ethyl acetate, 0.51 g (0.0025 mol) of N, N '
-Dicyclohexylcarbodiimide and 30 mg (0.025 mmol) of 4-dimethylaminopyridine were reacted at room temperature for 23 hours, and then the same operation as in Example 1 was carried out to give 0.33.
White crystals of g were obtained.

▲ 〔α〕 ²⁵ _D ▼ ＝ -11.0 ° (C 2.00, CHCl ₃ ) IRν _max cm ^-1 : 1740,1470,1450,1250,1080,885,780,760 ′ H-NMR (CDCl ₃ , 60MHz) δ (ppm): 0.50 to 2.13 (m, 21H) 3.42 to 3.90 (m, 3H) 3.90 to 4.30 (m, 4H) 6.90 (d, 2H) 7.28 (d, 2H) 8.13 (d, 2H) 8.41 (d, 2H) 8.42 ( s, 2H) The transition temperature of this compound is shown below.

Example 4 Liquid crystal compound (S) -synthesized in the same manner as in Examples 1 to 3.
2- {4 '-[4 "-(2-methoxy) propoxy] benzoyloxy} -5-n-octerpyrimidine showed the following transition temperatures.

Example 5 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 enclosed in a 1.7 μm cell, a pulse waveform of ± 20 V was applied, and the minimum pulse width at which the display was switched was obtained.

As shown in the table, the temperature range of the Sc ^* phase can be increased or decreased by blending the compound A of the present invention in an appropriate amount. Further, a composition having a Ch phase on the SA phase can be obtained.

Further, it is also possible to improve the response speed, as in the case of the blend of the composition A and the compound of Example 4.

Reference Example 1 Synthesis of (S) -ethyl 4- (2-tetrahydropyranyloxy) butoxybenzoate: 1.6 g (0.033 mol) of 50% sodium hydride and 50 ml of dimethylformamide were stirred at room temperature to give 5 g ( 0.030
Mol) of ethyl 4-hydroxybenzoic acid ester, and after stirring for 30 minutes, 9.9 g (0.030 mol) of (S) -2-
Tetrahydropyranyloxybutoxy p-toluenesulfonic acid ester was added and stirred at 80 ° C. for 10 hours. After the completion, the mixture was poured into ice water, extracted with ethyl acetate, washed with 10% aqueous sodium hydroxide solution and then saturated brine, dried over magnesium sulfate, and concentrated to obtain 8.8 g of a crude product.

IRν _max cm ^-1 : 1720,1605,1515,1280 ~ 1250 (br), 1170,1
Reference Example 2 Synthesis of (S) -ethyl 4- (2-hydroxy) butoxybenzoic acid ester: 8.5 g (0.026 mol) of (S) -ethyl 4- (2-tetrahydropyranyloxy) butoxybenzoic acid ester 43
It was dissolved in ml of ethanol, 0.2 g (0.0011 mol) of p-toluenesulfonic acid monohydrate was added, and the mixture was refluxed for 3 hours.
After the completion, the reaction mixture was concentrated, water was added, the mixture was extracted with ethyl acetate, washed with water, dried over magnesium sulfate, and concentrated. By purifying this with silica gel column chromatography
3.4 g of white crystals were obtained.

IR ν _max cm ^-1 : 3600 ~ 3200 (br), 1710,1610,1515,1290 ~
1230 (br), 1170,1100,850,770 Reference Example 3 Synthesis of (S) -ethyl 4- (2-methoxy) butoxybenzoic acid ester: 0.44 g (0.0092 mol) of 50% sodium hydride, 15 ml of tetrahydrofuran at room temperature 2.0g (0.0084
Mol) of (S) -ethyl 4- (2-hydroxy) butoxybenzoic acid ester was added, and 0.2 g (0.0011 mol) was further added.
Hexamethylphosphoric triamide is added and stirred for 1 hour, then 1.43 g (0.01 mol) of methyl iodide is added and the temperature is 40 ° C.
It was stirred for 1.5 hours. After completion of the reaction, the mixture was poured into ice water, extracted with ethyl acetate, washed successively with 10% aqueous sodium hydroxide solution, water and saturated brine, dried over magnesium sulfate, and concentrated to obtain 1.9 g of a crude product.

IRν _max cm ^-1 : 1710,1605,1515,1280,1250,1170,1100,85
Reference Example 4 Synthesis of (S) -4- (2-methoxy) butoxybenzoic acid: 1.9 g (0.0075 mol) of (S) -ethyl 4- (2-methoxy) butoxybenzoic acid ester was dissolved in 10 ml of ethanol. , 5 ml of 10% aqueous sodium hydroxide solution was added and stirred for 30 minutes, acidified with hydrochloric acid, extracted with ethyl acetate, washed with aqueous sodium hydrogen carbonate solution, dried over magnesium sulfate and concentrated to 1.9 g.
An oily substance was obtained. To this, n-hexane was added for crystallization, which was collected by filtration, washed with n-hexane, and dried to obtain 1.2 g of the target compound.

IRν _max cm ^-1 : 3100 ~ 2500,1680,1605,1430,1300,1255,85
0,770 640'H-NMR (CDCl ₃ , 60MHz) δ (ppm): 0.87 to 1.37 (m, 3H) 1.37 to 1.93 (m, 2H) 3.27 to 3.63 (m, 1H) 3.43 (s, 3H) 4.00 (d , 2H) 6.87 (d, 2H) 7.97 (d, 2H) 9.87 (br, 1H) Reference Example 5 Synthesis of (S) -ethyl 4- (2-tetrahydropyranyloxy) propoxybenzoic acid ester: 1.0 g (0.021 Mol) 50% sodium hydride, 25 ml dimethylformamide, 3.2 g (0.019 mol) ethyl 4-
Hydroxybenzoic acid ester and 6.1 g (0.019 mol) of (S) -2-tetrahydropyranyloxypropoxy p
-Toluenesulfonic acid ester was reacted at 60 ° C for 8 hours, and the same operation as in Reference Example 1 was performed to obtain 5.0 g of a crude product.

IRν _max cm ^-1 : 1715,1610,1280,1255,1170,1120,1035,770 Reference Example 6 Synthesis of (S) -ethyl 4- (2-hydroxy) propoxybenzoic acid ester: 4.5 g (0.014 mol) (S) -ethyl 4- (2-tetrahydropyranyloxy) propoxybenzoic acid ester,
A mixture of 0.2 g (0.0011 mol) of p-toluenesulfonic acid monohydrate and 45 ml of methanol was refluxed for 1 hour, and then Reference Example 2 was used.
The same operation as the above was performed to obtain 2.2 g of a crude product.

IR ν _max cm ^-1 : 3600-3200 (br), 1710 (br), 1610,1515,
1300-1220 (br), 1170,1100,1030,770 Reference Example 7 Synthesis of (S) -4- (2-ethoxy) propoxybenzoic acid: 0.52 g (0.011 mol) of 50% sodium hydride and 15 ml of tetrahydrofuran 2.2g (0.0098mol) while stirring
Of (S) -ethyl 4- (2-hydroxy) propoxybenzoic acid ester and 0.2 g (0.0011 mol) of hexamethylphosphoric triamide were added, and 1 hour later, 1.8 g (0.012
(Mol) methyl iodide was added and the mixture was refluxed for 2 hours. After completion, the mixture was poured into ice water, extracted with ethyl acetate, washed with 10% aqueous sodium hydroxide solution and saturated saline, dried over magnesium sulfate, and concentrated. To this, 20 ml of ethanol was added to dissolve it, 10% aqueous sodium hydroxide solution was added, and the mixture was refluxed for 1 hour for hydrolysis. After completion, pour in ice water, extract with ethyl acetate, and perform the same operation as in the previous step 1.
4 g of oil was obtained. This was purified by silica gel column chromatography to obtain 0.76 g of product.

▲ 〔α〕 ²⁵ _D ▼ ＝ -14.3 ° (C 1.05, CHCl ₃ ) IRν _max cm ^-1 : 3300 to 2400 (br), 1690,1610,1460,1250,1
170,850,770'H-NMR (CDCl ₃ , 60MHz) δ (ppm): 0.70 ~ 1.90 (m, 6H) 3.40 ~ 4.23 (m, 5H) 6.90 (d, 2H) 8.03 (d, 2H) 11.70 (br, 1H)

 ─────────────────────────────────────────────────── ─── 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 general formula (In the formula, R is an alkyl group or an alkoxy group having a straight carbon chain, and R ^* is (R ₁ is a C ₁ -C ₅ alkyl group, R ₂ is a C ₁ -C ₄ alkyl group,
n represents an integer) and represents an optically active group having an asymmetric carbon atom in the chain. ] The pyrimidino phenyl ester derivative shown by these.