JPS61268673A - 2-pyrimidinecarboxylate derivative - Google Patents

Abstract

NEW MATERIAL:A 2-pyrimidine carboxylate derivative expressed by formula I [X<2> represents X<3>, formula II or formula III; X<1>, X<3> and X<4> represent alkyl, formula IV or formula V (j-n are respectively 1-10) and both X<1> and X<4> represent alkoxyl, F, Cl, Br or CN; ring A represents formula VI, formula VII or formula VIII (Y represents F, Cl, Br or CN); ring B and ring C represent formula VI, formula IX (W represents F, Cl, Br, etc.), etc.]. EXAMPLE:4-Pentylphenyl 5-(4-pentyloxyphenyl)-2-pyrimidinecarboxylate. USE:A component of a liquid crystal composition, which increases DELTAepsilon and/or DELTAn of the liquid crystal composition. PREPARATION:For example, a methylisothiourea compound is reacted with a perchlorate expressed by formula X,. followed by cyclization and oxidation, and the resultant compound is reacted with NaCH, followed by the hydrolysis and condensation through dehydration, to obtain the compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to novel organic compounds, and more particularly to compounds useful as components of liquid crystal compositions, and to compositions containing the compounds.

[Technology background]

Liquid crystal display devices are made of liquid crystal compounds and /'1! Bamboo liquid crystal compositions are used in various display devices by utilizing properties such as dielectric anisotropy and refractive index anisotropy in the liquid crystal phase. These displays are liquid crystal display elements that apply the electro-optic effect of liquid crystals, or devices that apply the thermo-optic effect and other optical effects of liquid crystals. Together with advances in electronics, twisted nematic effects, guest-host A large number of liquid crystal compounds are used in liquid crystal display devices that utilize electric field effects. These liquid crystal materials are used as a single compound, but several types of liquid crystal compounds or non-liquid crystal compounds are used as a mixture in view of their characteristics such as liquid crystal temperature range, operating voltage, response performance, etc.

Recently, there has been a growing demand for liquid crystal display elements that can be driven at particularly low voltages. There is a demand for liquid crystal compositions with a large

When using a liquid crystal compound and/or liquid crystal composition in a cell having an electrode, often a cell having a transparent electrode and having a liquid crystal compound and/or liquid crystal composition between opposing electrodes, and controlling the liquid crystal display with voltage. The following is observed.

Dielectric anisotropy value of liquid crystal compound and/or liquid crystal composition (
ΔC=ε/−1, hereinafter abbreviated as Δε. ) is positive and large, it is possible to lower the driving voltage of cells with the same spacing between opposing electrodes.

Optical anisotropy value of liquid crystal compound and Xi or liquid crystal composition (
When Δnmin/"'l (hereinafter abbreviated as Δn) is large, unevenness in density or color is unlikely to occur in the display of parts where the spacing between opposing electrodes is partially different within the cell. Other properties In this case, the light transmittance can be increased by reducing the distance between the opposing electrodes of the cell.Furthermore, by reducing the distance between the opposing electrodes of the cell, the electric field strength can be increased and the response time can be shortened.

[Problem that the invention seeks to solve]

An object of the present invention is to provide a compound useful as a component of a liquid crystal compound and a liquid crystal composition containing the compound. It is another object of the present invention to provide.

(Structure of the Invention) The present invention provides a 2-pyrimidine carboxylate derivative and a liquid crystal composition containing 18 or more types of the compound, wherein the compound has a group selected from XX4 in the general formula, and Xi , X3 and X4 are each an alkyl group having 1 to 10 carbon atoms, -CjH+j-0-Ckc
2 to +1 and -CIHu-0-CmH2y1-0-
Indicates a group selected from CnH2n+1, with %t, m in 1%
and n each represent an integer from 1 to 10, Xi and X4 each represent a group selected from a group selected from %F%Ct, Br and -CN, a frucoxyl group having 1 to 10 carbon atoms, Y Vi, F%C1, Br
and 10N, W and 2 represent 2%C25Br and -C, respectively.
Indicates a group selected from N. ) is a 2-pyrimidine carboxylate derivative represented by

An example of the method for producing the compound of the present invention can be shown by the following reaction formula. In the formula, Xl, Xl, ÷, -
8 and X4 are each as described above. M in the ceremony
e is a methyl group (in the formula, DCC represents N,N'-dicyclohexylcarbondiimide, and DMAP represents 4-dimethylaminopyridine). The above reaction formula will be explained below.

Methylisothiourea compound (can be I sulfate, hydrochloride, etc.) and perchlorate (1)″f: cyclization reaction in the presence of a base (e.g. sodium methoxide, pyridine, sodium hydroxide, etc.) , pyrimidine compound (f
obtain f). Next, the methylthio group of the compound L W + is converted into a methanesulfonyl group using hydrogen peroxide to obtain a compound (ma). Then, from compound V and sodium cyanide, 2-cyano-pyrimidine derivative (VI)t
- get. Compound (1) is then hydrolyzed using an aqueous NaOH solution to obtain a 2-pyrimidinecarboxylic acid derivative (2). Next, compound (■) and a compound having a hydroxyl group (■a%
lb, %'Ic) to form 2 of the compound of the present invention by dehydration condensation.
-pyrimidine carboxylate derivatives (Ia, ■b, I
c).

In the above general formula and reaction formula, Xi, Xl and X4 can each represent the following.

The substituents are methyl, -, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl for straight chain alkyl groups, and halogen for branched alkyl groups. 1so-propyl-11-methylglopyru, 2-methylpropyl-51-methylbutyl-12-methylbutyl-13-methylbutyl-51-
Examples include methylbenzene, 1-ethylpentyl-12-methylbenzene, and 1-methylhexyl-12-ethylhexyl-11-methylbutylnato.

XI and X4 can each be a methoxy group, methoxyethyl, -, ethoxyethyl-nato, or an alkyl group containing an oxygen atom, and can be F, 01% Br 5-CN.

An example of a compound with a hydroxyl group (the above-mentioned compound W) is:
As HO-X', methanol, ethanol, 1-glopanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptatool, 1-octatool, 1
-nonyl alcohol, 1-decanol, etc., and give an example of HOQ X3 as HO8X':
bj! ::-4-)f-ruphenol, 4-ethylphenol, 4-propylphenol, 4"-butylphenol, 4-pentylphenol, 4-hexylphenol, 4-hebutylphenol, 4-octylphenol, 4
-nonylphenol, 4-decylphenol, 4-methoxyphenol, 4-ethoxyphenol, 4-7'rokyloxyphenol, 4-butyloxyphenol,
4-pentyloxyphenol, 4-hexyloxyphenol, 4-hebutyloxyphenol, 4-octyloxyphenol, 4-nonyloxyphenol, 4
-decyloxyphenol, 4-ethoxyethyloxyphenol, 4-methoxymethylphenol, 4-fluorophenol, 4-chlorophenol, 4-bromophenol 1.4-cyanophenol, 3.4-difluorophenol, 3.4- Dichlorophenol, 3-fluoro-4-cyanphenol, 2,4-fluorophenol, 3-chloro-4-fluorophenol, etc. can be shown.

Nol, 4-ethylcyclohexanol, 4-propylcyclohexanol, 4-butylschifftetrahexanol,
4-pentylcyclohexanol, 4-hexylcyclohexanol, 4-hebutylcyclohexanol, 4-
Octylcyclohexanol 1.4-nonylcyclohexanol, 4-decylcyclohexanol, 4-methoxycyclohexanol, 4-ethoxycyclohexanol, 4-7"ropyloxycyclohexanol, 4-butyloxycyclohexanol, 4-pentyloxy Cyclohexanol, 4-hexyloxycyclohexanol, 4-hebutyloxycyclohexanol, 4-octyloxycyclohexanol, 4-nonyloxycyclohexanol, 4-decyloxycyclo-xanol, 4-ethoxyethyloxycyclohexanol, 4
-methoxymethylcyclohexanol, 4-fluorocyclohexanol, 4-/rolocyclohexanol, 4
-bromocyclohexanol, 4-cyanocyclohexanol, 2,4-difluorocyclohexanol, 3+
4-') fluorocyclohexanol, 3.4-dichlorocyclohexanol, 3-fluoro-4-cyanocyclohexanol, 3-chloro-4-fluorocyclohexanol, and the like.

methanol, 5-propyl-2-pyrimidinol, 5-butyl-2-pyrimidinol, 5-pentyl-2-pyrimidinol, 5-
Hexyl-2-pyrimidinol, 5-hebutyl-2-pyrimidinol, 5-octyl-2-pyrimidinol, 5
-nonyl-2-pyrimidinol, 5-decyl-2-pyrimidinol, 5-methoxy-2-pyrimidinol, 5-
Ethoxy-2-pyrimidinol, 5-propyloxy-
2-pyrimidinol, 5-butyloxy-2-pyrimidinol, 5-pentyloxy-'l, -hymidinol, 5-hexyloxy-pyrimidinol, 5-hebutyloxy-2-pyrimidinol, 5-octyloxy-2 -pyrimidinol, 5-nonyloxy-2-pyrimidinol, 5-decyloxy-2-pyrimidinol,
5-ethoxyethyloxy-2-pyrimidinol, 5-
Methoxymethyl-2-pyrimidinol, 5-fluoro-
2-pyrimidinol, 5-chloro-2-pyrimidinol, 5-bromo-2-pyrimidinol, 5-cyano-2-
Examples include pyrimidinol, 4,5-difluoro-2-pyrimidinol, 4-chloro-5-7kyF rho-2-pyrimidinol, 4-fluoro-5-cyano-2-pyrimidinol, and the like.

cinol, 2-ethyl-5-pyrimidinol, 2-propyl-5-pyrimidinol, 2-butyl-5-pyrimidinol, 2-pentyl-5-! pyrimidinol, 2-hexyl-5-pyrimidinol,
2-hebutyl-5-pyrimidinol, 2-octyl-5
-pyrimidinol, 2-nonyl-5-pyrimidinol,
2-decyl-5-pyrimidinol, 2-methoxy-5-
pyrimidinol, 2-ethoxy-5-pyrimidinol,
2-propyloxy-5-pyrimidinol, 2-butyloxy-5-pyrimidinol, 2-pentyloxy-5
-pyrimidinol, 2-hexyloxy-5-pyrimidinol, 2-hebutyloxy-5-pyrimidinol, 2
-octyloxy-5-pyrimidinol, 2-nonyloxy-5-pyrimidinol, 2-decyloxy-5-pyrimidinol, 2-ethoxyethyloxy-5-pyrimidinol, 2-methoxymethyl-5-pyrimidinol,
2-fluoro-5-pyrimidinol, 2-chloro-5-
Pyrimidinol, 2-bromo-5-pyrimidinol, 2
-cyano-5-pyrimidinol, 2-cyano-4-chloro-5-pyrimidinol, 2-butyl-4-fluoro-
5-pyrimidinol and the like can be shown.

4-substituted phenol 4 or 4- in HO() xs
Substituted transcyclohexanol in which the 2nd and/or 3rd positions are each substituted with a group selected from F, C1%Br and -CN can be used, and 5-substituted -2
-pyrimidinol or 2-substituted-5-pyrimidinol substituted at the 4-position with a group selected from F%Ct%Br and -CN, respectively, can be used.

As HO (Ginzo) (4-1 replaced-)trans-cyclohexyl)-trans-cyclohexanol, 4-(2-substituted-5-pyrimidinyl)-7enol, 4-(5-substituted-2-pyrimidinyl)-7enol, 2- (4-substituted phenyl)-5-pyrimidinol, 5-(4-substituted phenyl)-2-pyrimidinol, 4-(2-substituted-5-pyrimidinyl)-trans-cyclohexanol, 4-(5-substituted-2- pyrimidinyl)-trans-cyclohexanol, 2-(4-substituted-)trans-cyclohexyl)-5-pyrimidinol, 5-(4-substituted-)trans-cyclohexyl)-2-pyrimidinol, 2-(2-substituted-)trans-cyclohexyl)-2-pyrimidinol, 5-pyrimidinyl)-5-pyrimidinol, 2-(5-substituted-2-pyrimidinyl)-5-pyrimidinol, 5-(5-substituted-2-pyrimidinyl)-2-pyrimidinol, 5-(2-substituted-5- pyrimidinyl)-2-pyrimidinol. HO (benzene skeleton showing -B- and/or 10- of 8 and Xxs, respectively
Maku is the 2nd and/or 3rd position of the trans-cyclohexane skeleton, or the 4th position of the pyrimidine skeleton, respectively.
%C1, Br and -CN can be used.

Examples of liquid crystal compositions according to the present invention in which one or more of compounds 1a, Ib, and IcvN represented by the above formulas are added include other types of liquid crystal compounds. Namely, examples thereof include Schiff base compounds, azoxy compounds, azoxybenzene compounds, ester compounds, biphenyl compounds, phenylcyclohexane compounds, and phenylpyrimidine compounds.

〔Effect of the invention〕

The compound of the present invention can increase Δε and/or Δn of the liquid crystal composition by using it as a component of the liquid crystal composition. The compound of the present invention has good stability against heat, light, electricity, air, moisture, etc. By using the compound of the present invention as a component of a liquid crystal composition, the clearing point in the liquid crystal temperature range of the liquid crystal composition can be raised to a much higher temperature.

(Examples) The present invention will be explained below with reference to Examples.The present invention is not limited to these Examples.

Example 1 4-Pentylphenyl-5-(4-pentyloxyphenyl)-2-pyrimidinecarboxylate sulfate methylisothiourea (1) 11.2 y (0,0
4mot) and 1-dimethylamino-3-dimethylimmonio 2-(4-pentyloxy7enyl)-propene-(1)-perchlorate (11) 1O,8F(0,0
28 mot) was added to 200 g of pyridine and heated to 90°C, and then a sodium methoxide-methanol solution separately prepared from 1.2 f (0,052 mot) of sodium and 150 ml of methanol was added dropwise, followed by heating under reflux for 2.5 hours.

Next, after dissolving the reaction solution in 500 ml of toluene,
N-hydrochloric acid 300xl, 2N-sodium hydroxide aqueous solution 3
It was washed in the following order: 00ba, and then washed with water until the washing solution became neutral. The toluene phase was then dried over magnesium sulfate,
Concentrate under reduced pressure to obtain crude crystals of 7.2 f'. Next, this crystal was recrystallized using methanol to give 2-methylthio-
5-(4-pentyloxyphenyl)pyrimidine (IV
) 5.2f (yield 65%) was obtained. The crystalline smectic point (CC-8 point) of compound (1) was 58.8°C, and the smectic clearing point (SI point) was 65.9°C.

Next, compound ①8. θ! (0,0105 mot) was dissolved in 20 g of acetic acid and 30% hydrogen peroxide solution was slowly added dropwise while stirring at room temperature. Next, all the crystals produced were separated and recrystallized using methanol to obtain 2-methanesulfonyl-5-(4-pentyloxyphenyl)pyrimidine (V
) 1.8N (yield 55%).

Then compound V 1.89 (0,006 mot) and sodium cyanide 0.275 F (0,006 m (1
Add t) to 5 Ml of dimethyl sulfoxide and heat at 100°C.
I stirred it for an hour. 15 d of drained water was added. Next, the resulting crystals were separated from each other and recrystallized using ethanol to obtain 2-cyano-5-(4-pentyloxyphenyl)pyrimidine (to) 0-7 IC yield (447%).The melting point of compound (1) was 100. 'C was shown.

Then compound ■Q, 7t (0,0026mot)e
The mixture was added to a 2N-hydroxide aqueous solution and heated under reflux for 16 hours. After cooling, 2N salt a was gradually added to adjust the pH of the liquid.
was set to 2. Next, the deposited precipitate was separated into ocher-colored crude crystals, which were recrystallized using ethanol to obtain 5-(4-pentyloxyphenyl)pyrimidine-2-carboxylic acid (
VIo, 4f (yield 54%) was obtained.

Then compound ■0.4 f (L4mrnot'') and 4-pentylphenol (■b) 0.4 f (2
, 4tnm□l) in 20 wl of dichloromethane and 0.2f of 4-dimethylaminopyridine and N,N'
-dicyclohexylcarbodiimide 0.3F (1.5m
m□t) was added and stirred at room temperature for 5 hours. Next, the dichloromethane solution from which the produced urea was separated was dried over magnesium sulfate, and the dichloromethane was evaporated under reduced pressure to obtain crude crystals. Then, it was recrystallized from ethanol to give 4-pentylphenyl-5-(4-pentyloxyphenyl)-
2-pyrimidinecarboxylate) (Ib) 0.1
f (0.24 mmol, yield 17%) was obtained.

Crystal-smectic point (C-S point) of this compound Ib
is 155.1℃, smectic-clearing point (S-I point fd
It showed 185.2°C. Elemental analysis value is C near 2.1%,
H: 7.5%, (calculated value by C, month, N, O, is C near 2.1g%)
, H near, 46%).

Example 2 (Usage Example) Nematic-transparent (N-4) liquid crystal composition (4) consisting of
) point is 52.1℃, dielectric anisotropy ΔC is 112 (ε/=
15.9, t±-4,7), refractive index anisotropy Δn is 0.1
19 (n7=1.609, nL-1,490).

Example 11 of the present invention was added to 95 parts by weight of this liquid crystal composition.
7) The N-1 point of the liquid crystal composition containing 5 parts by weight of 4-pentylphenyl-5-(4-pentyloxyphenyl)-2-pyrimidinecarboxylate is 55.6°C, Δε is 11.5, and Δn is It showed 0.124.

that's all Patent issuer Chisso Co., Ltd.

Claims (2)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, -X^2 is -X^3, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ X^1, X^3 and X^4 each have 1 to 10 carbon atoms;
alkyl group, -C_jH_2_j-O-C_kC_2
_k_+_1 and -C_lH_2_l-O-C_mH
represents a group selected from _2_m-O-C_nH_2_n_+_1, j, k, l, m and n each represent an integer of 1 to 10, X^1 and X^4 each represent an alkoxyl group having 1 to 10 carbon atoms, Can be a group selected from F, Cl, Br and -CN, ▲ has mathematical formulas, chemical formulas, tables, etc. ▼ has ▲ mathematical formulas, chemical formulas, tables, etc. ▼, ▲ has mathematical formulas, chemical formulas, tables, etc. Indicates a group selected from ▼ and ▲ where there are mathematical formulas, chemical formulas, tables, etc., Y is F,
Indicates a group selected from Cl, Br, and -CN, and ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and ▲There are mathematical formulas, chemical formulas, tables, etc.▼ are respectively ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas ,Chemical formula,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas, There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ W and Z each represent a group selected from F, Cl, Br and -CN. ) A 2-pyrimidine carboxylate derivative represented by: (2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, -X^2 is -X^3, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼X^4 and ▲ Mathematical formulas, chemical formulas, tables, etc. represents a group selected from ▼, where X^1, X^3 and X^4 each have 1 to 10 carbon atoms.
alkyl group, -C_jH_2_j-O-C_kC_2
_k_+_1 and -C_lH_2_l-O-C_mH
represents a group selected from _2_m-O-C_nH_2_n_+_1, j, k, l, m and n each represent an integer of 1 to 10, X^1 and X^4 each represent an alkoxyl group having 1 to 10 carbon atoms, Can be a group selected from F, Cl, Br and -CN, ▲ has mathematical formulas, chemical formulas, tables, etc. ▼ has ▲ mathematical formulas, chemical formulas, tables, etc. ▼, ▲ has mathematical formulas, chemical formulas, tables, etc. Indicates a group selected from ▼ and ▲ where there are mathematical formulas, chemical formulas, tables, etc., Y is F,
Indicates a group selected from Cl, Br, and -CN, and ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and ▲There are mathematical formulas, chemical formulas, tables, etc.▼ are respectively ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas , chemical formulas, tables, etc.▼, ▲mathematical formulas,
There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲There are mathematical formulas, chemical formulas, tables, etc.▼and▲Mathematical formulas, chemical formulas , tables, etc. ▼ Indicates the group selected from ▼, W and Z are respectively F, Cl, Br and -C
Indicates a group selected from N. ) A liquid crystal composition containing one or more 2-pyrimidine carboxylate derivatives represented by the following.