JPS61215375A - Benzoic acid pyrimidinylphenyl ester derivative - Google Patents

Abstract

NEW MATERIAL:A benzoic acid pyrimidinylphenyl ester derivative shown by the formula I (R1 and R2 are 5-15C alkyl, and one or R1 and R2 contains asymmetric carbon atom in chain). EXAMPLE:(S)-4-n-octyloxybenzoic acid 4'-[5'-(6'-methyloctyl)-2-pyrimidinyl]phenyl ester. USE:A chiral smetic liquid crystal compound having ferroelectricity, or a material to be blended with other various liquid crystal compounds, showing a chiral smetic phase in a wide temperature range including room temperature, having improved chemical stability and high response properties of electric field. PREPARATION:For example, a compound shown by the formula II or its reactive derivative is reacted with a compound shown by the formula III in a solvent such as tetrahydrofuran, etc., by the use of a condensation agent such as dicyclohexylcarbodiimide, etc., in the presence of a tertiary amine as a catalyst, to give a compound shown by the formula I.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a new chemical substance, and more specifically, the present invention relates to a new chemical substance that can be used by itself as a ferroelectric chiral smectic liquid crystal compound, and can also be mixed with various other liquid crystal compounds. The present invention relates to a benzoic acid pyrimidinyl phenyl ester compound which is also useful as a material.

[Summary of the invention]

The compound provided by the present invention is a benzoic acid compound of the formula 1 (wherein RI, u, is a C5-01 alkyl group, one of which has an asymmetric carbon atom in the chain). It is a pyrimidinyl phenyl ester derivative.

This compound is a ferroelectric liquid crystal compound that exhibits a chiral smectic phase in a wide temperature range including room temperature, has superior chemical stability, and has high electric field responsiveness. It also has excellent mixing properties.

[Conventional technology]

(s)-2-Methylbutyl p-(pn-decyloxybenzylidene aminococinnamate (DOBAMBO)) is known as a liquid crystal compound exhibiting ferroelectricity.

This thick 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 Kin, 01.C!N, Y is at, O
,H,,4 has no:=:2;2;58゜7. ．． 6, 7
6°, 7°, and this series of compounds cannot be used as liquid crystal materials at room temperature because the temperature at which they exhibit a chiral smectic phase is higher than room temperature, and because they are Schiff base compounds, they cannot be used as liquid crystal materials. It has disadvantages t', such as being susceptible to decomposition. (Ferroelactrias Vol. 24, p. 309 (1980)) is known as a compound devised to improve these.

This type of compound has attracted attention as a compound that exhibits a smectic C phase over a wide temperature range including room temperature. Furthermore, B. Eng. Ostrowsky reported that a compound represented by the formula % (in which n is 9 or 10t-) exhibits a chiral smectic phase in a temperature range relatively close to room temperature.

Also, by H, zasahke, 0n-rk+t O-Q-p-c m H@m+
.

Some of the compounds represented by are introduced as exhibiting a smectic phase. (J, Prekt(!h
emie 317 617 (1975) However, in these, chiral smectic liquid crystal compounds are neither described nor suggested.

[Problems to be solved by the present invention]

The compounds provided by the present invention are benzoic acid pyrimidinyl phenyl esters having the formula % (wherein R1eR1 is a C1-o1 alkyl group, one of which has an asymmetric carbon atom in the chain). It is a rust conductor.

This compound is a ferroelectric liquid crystal compound that exhibits a chiral smectic phase in a wide temperature range including room temperature, has excellent chemical stability, and has high electric field responsiveness, and can be mixed with various other liquid crystal compounds. It also has excellent sex.

[Measures to Solve the Problems] The compound provided by the present invention is produced as follows. That is, it is produced by reacting (a) R, -0-Q-COOH or a reactive derivative thereof with) 10-Q-p-R1. (In the formula, R1e and R1 are the same as above.) Here, a solvent such as tetrahydrofuran, dichloromethane, chloroform, ethyl acetate, pyridine, etc. is used, a condensing agent such as dicyclohexylcarbodiimide, ', HDQ@, etc. is used, and a catalyst is as tertiary amines (e.g. dimethylaminopyridine, pyridine, triethylamine, etc.) t-
The reaction is carried out at room temperature to the reflux temperature of the solvent.

In addition, in the case of acid tetralide, acid bromide (made from thionyl chloride, thionyl bromide and the corresponding acid) as a reactive derivative at the carboxyl group, in addition to the above solvents, benzene, toluene, dimethylformamide,
Dimethyl sulfoxide can be used, and in addition to the above-mentioned tertiary amine, sodium hydroxide, potassium hydroxide, etc. can be used as a condensing agent. Furthermore, the fragrance material of the present invention can also be produced by the following method. That is, ゛(b)
11Io-Q-coon or its unreactive derivative in the carboxyl group is reacted with HO-0-p-Rt to form HO-0-C
oo-0-G)-R, 't'' After preparing the compound, R, 7 is reacted with the compound shown.

(Rs e Rt is the same as above. X is a halogen atom,
Indicates tosyl group and metal group. ) Here, HO-Q-aooH or its reactive derivative at the carboxyl group' and HO-0-
The reaction with p-R1 is carried out as described in (a) above. In this way, -HO-0-Co
A compound represented by o-0-p-Rt was obtained, and R, -
The object compound of the present invention can be obtained by condensing the compound represented by X. During condensation, it is preferable to use a condensing agent such as sodium, potassium, potassium carbonate, or sodium carbonate.

Since the compound provided by the present invention contains an asymmetric carbon atom in its molecule, it has a pair of optical antipodes, and both of these compounds are included in the object compound of the present invention, and their steric The arrangement is uniquely determined by that of the compound used as the i family.

Example 1゜(S-4-n-octyloxybenzoic acid, 4/-(s/
Synthesis of -(6'-methyloctyl)-2-pyrimidinyl]phenyl ester (s)-4(5-(6-methyloctyl)-2-pyrimidinylraphenol 186 f, 4-n-octyloxybenzoic acid Q, 8 f, 3 mji of dry pyridine was added, and after dissolving, N,N'-dicyclohexylcarbodiimide 0.71 P, 4-dimethylaminopyridine 11 br
twit was added, and the mixture was reacted at room temperature for 15 hours.

After the reaction was completed, the mixture was poured into ice water, acidified with hydrochloric acid, and the reaction product was extracted with ethyl acetate. The ethyl acetate layer was diluted with 2N, HCl.
The mixture was washed with water, saturated sodium bicarbonate solution, and then water until neutral, then dried, and ethyl acetate was distilled off.

The obtained crude product was purified by gold silica gel chromatography and recrystallization to obtain 4'-(5'-(6-methyloctyl)-2-pyrimidinyl (L9F) (s)-4-n-octyloxybenzoate. ] Phenyl ester obtained.

Engineering Rvvaaxom”: 1740.1615.14
37゜1260.1205,1175゜'H-N, MR (60MHz, CD0l,) δ (pp
m): (lL4-2.1 (m, 22 H)16
4 (t, 21) 4.04 (t, 2H) L9B (d, 21N) 7.55 (1, 2H) a17t (a, zH) a52 (cl, 2H) 11L63 (13,2111) Phase transition temperature implementation Example Z (s)-4-(6-methyloctyloxy) 4'-(5'-n-octyl-2-pyrimidinyl benzoate)
Synthesis of phenyl ester or (S) 4-(6-methyloctyloxy)benzoic acid 1.39F obtained from P-luenesulfonic acid ester of (s)-6-canine tyloctan-1-ol and P-hydroxybenzoic acid. , 4-(5-n-octyl-2-
Pyrimidinyl laphenol 1.5 F.

Anhydrous chloroform 15- was added.

Next, 4-dimethylaminopyridine CLO64f.

Dicyclohexylcarbodiimide 1.08fi sword mouth,
The reaction was carried out at room temperature for 15 hours. After the reaction was completed, the precipitate was separated from P and the product was extracted with chloroform. The chloroform layer was washed with water, 2N hydrochloric acid, and water, dried, and then all of the chloroform was distilled off. The obtained crude product was purified by silica gel chromatography and recrystallization to obtain 4'-(5'-n-octyl-2-pyrimidinyl)phenyl (s)-4-(6-methyloctyloxy)benzoate. Esther 2. I got o2fk.

Engineering Rν,,, Qm″: 1750,1602,158
51550.1515.1455'H-NMR (60MHz, CDCl, )δ(p
yn): CL 6-2.1 (m, 32H
) 2.60 (t, 2H) 4.02 (t, 2H) 6.98 ((L, 2H) 7.38 (d, 2H) a20 (d, 2H) as7 ((1, 2H) a64 (8 , 2H) The raw material compound used in the present invention is produced as follows.

- Describe an example.

(Synthesis of (8)-7-methylnonan-1-ol:
(s) -2-methylbutan-1-ol ([α1m-
5, a°) tosylation, then malonic acid ester synthesis,
Through saponification, decarburization, and reduction, (s)-4-methylhexan-1-ol was obtained, which was then prochlorinated with Grignard reagent! (s) obtained by coupling reaction with 4-acetyloxyiodide butane -7-
By saponifying the acetyl ester of methylnonan-1-ol, (s)-7-methylnonan-1-ol is obtained.

(b)(sJ -4-(5-(6-methyloctyl)-
Synthesis of 2-pyrimidinyl]phenol: (s)-7-methylnonane- obtained in (a) above
1-ol was protinated to prepare Grignard reagent'. This was reacted with ethyl orthoformate (8
) -8-Methyldecyl aldehyde diethyl acetal was obtained. It was then reacted with Vilsmeier's reagent prepared from trichloromethyl chloroformate and N,N-dimethylformamide to obtain (S)-θ-dimethylamino-α-(6-methyloctyloxy)acrolein. This product was prepared by reacting with p-hydroxybenzamidine hydrochloride (R)-4-(5-(
6-Methyoctyl)-2-pyridinyl]phenol is obtained.

(c) (8) Synthesis of -6-methyloctan-1-ol (814-methylhexane-1-ol obtained in (a) above)
It was produced using the malonic acid ester synthesis method, followed by saponification, decarboxylation, and reduction.

As shown in the examples above, the compounds of the present invention support the Sc" phase in a temperature range higher than room temperature, and the
``It is an effective compound in obtaining a chiral smectic liquid crystal composition having a phase.

that's all

Claims (1)

[Claims] A benzoic acid pyrimidinyl phenyl ester derivative represented by the formula ▲ Numerical formula, chemical formula, table, etc. ▼. (In the formula, R_1 and R_2 are C_5 to C_1_5 alkyl groups, and either one has an asymmetric carbon atom in the chain.)