JPS61251672A - Liquid crystal compound - Google Patents

Abstract

NEW MATERIAL:The phenylpyrimidine derivative of formula I (R1 and R2 are 4-15C alkyl; either one of them contains asymmetric C atom in the chain). EXAMPLE:(S)-5-n-octyl-2-[4-(6-methyloctanoyl)phenyl]pyrimidine. USE:A liquid crystal compound having ferroelectric property and exhibits chiral nematic C phase over a wide temperature range including room temperature. It has excellent chemical stability. PREPARATION:The compound of formula I can be produced by dissolving the compound of formula II and the compound of formula III in dried ethanol, adding methanol solution of sodium methylate to the mixture to effect the reaction of the components and oxidizing the resultant compound of formula IV with an oxidizing agent such as chromic acid-sulfuric acid in a solvent such as water, pyridine, DMF, THF, etc.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to phenylpyrimidine derivatives,
The compound has use as a liquid crystal material.

(Prior art) As a liquid crystal compound exhibiting ferroelectricity, (8)-2-methylphthyl P-(P-n-desyloxypenozylide 7″ano)
Cinnamate (IJOBAMBC) is a well-known liquid crystal compound in the basic base series, which has been the subject of research on ferroelectric liquid crystals, and various compounds have been synthesized. That-
As an example, (where Xfl, B, Oj, O'N, Yij
C1, C, E, , *Indicates a uniform carbon atom. ] Compounds represented by the general formula are known. However, this series of compounds exhibits a chiral smectic phase at a temperature higher than room temperature, so they cannot be used as liquid crystal materials at room temperature, and because they are 7-base compounds, they are not susceptible to decomposition by moisture. It has disadvantages such as being easy to use. Compounds devised to improve these drawbacks are being touted. (Fsrroelectrica
(Vol. 24, p. 509 (s, 980)) This type of compound has attracted attention as a compound exhibiting a smectic CI phase over a wide m range including room temperature. It has been reported that a compound represented by the following formula (in which n represents 9 or 101 represents an asymmetric carbon atom) exhibits a chiral smectic phase within a range of 1 degree relatively close to room temperature.

Also, by E, ZAI30111n, Cn)1tn+t -04<':5-(4m)itm+
.

Some of the compounds represented by have been shown to exhibit a smectic phase.

(J, Prakt C!hemie, Volume 51.7 61
．． 7 (1,975)) 1, but there is no description or suggestion of chiral smectic liquid crystal compounds.

(Problems to be Solved by the Present Invention) The compounds provided by the present invention have the formula %formula% (wherein RI m R1 is an alkyl group of 04 to C0, and either one has an asymmetric structure in its chain. It is a new material with ferroelectric liquid crystal properties (containing carbon atoms), exhibits a natural smectic C phase in a wide temperature range including room temperature, and has excellent chemical stability. It has excellent electric field responsiveness and also has excellent miscibility with various other liquid crystal compounds. The present invention is
The present invention provides a liquid crystal compound.

Here, the substituent formula in the compound represented by formula (1) includes a linear alkyl group represented by OnH1n+, -, or the same as . However, R1 and R3 are never the same type of alkyl group.

Compounds represented by formulas (1) and (2) are methanol.

Lower alcohol solvents such as ethanol and isopropanol; aromatic solvents such as benzene and toluene.

Dimethylformamide, dimethyl sulfoxide.

Sodium methoxy7 in a solvent such as tetrahydro7
The reaction is carried out at room temperature or heated in the presence of a catalyst such as hydrogen, sodium chloride, sodium hydride, or metallic sodium.

(Means for Solving the Problems) The novel liquid crystal compound exhibiting a chiral smectic C phase provided by the present invention is produced as follows. That is, an outline of the chemical reaction is as follows.

(In the formula, R,, R, are the same as above) The thus obtained compound represented by the formula (3) is mixed with water, pyridine, dimethyl sulfoxide, dimethylformamide,
The target compound of the present invention can be obtained by oxidation using an oxidizing agent such as chromic acid-sulfuric acid monobichromic acid pyridinium salt or chromic acid-acetic acid in a solvent such as tetrahydrofuran or dioxane.

below! ! The present invention will be further explained in detail by describing examples.

Practical example 1 (A) (Japanese)-5-n-octyl-2-(it-(1,
-Hydroxy-6-methyloctyl)phenylcopy 11
Synthesis of Midine <8) -4-(1-hydrogine-6-methyloctylbenzamidine hydrochloride Q, 82t, β-n-,t) 0.56F of cutyl-α-dimethylaminoacrolein was added to 20% of dry ethanol. After dissolving.

28% sodium methylate, methanol solution 2, at
tt was added, and the mixture was reacted under reflux for 15 hours. After the reaction is complete,
The mixture was poured into ice water, acidified with hydrochloric acid, and the reaction product 6 was extracted with ethyl acetate. The ethyl acetate layer was washed with water and saturated brine, dried, and the solvent was distilled off. The obtained crude product was
Purified by silica gel chromatography and recrystallization, optically active 5-n-octyl-2-(a-(t-hydroxy-6-methyloctyl)phenyl)pyrimidine α64
? I got it.

Engineering RI/max''-': 5260,1595.ts
ssIaao, ao.

In-N MFI (60MHz, 0DcJ3)δ
(ppm): a 67 (s, 2 F) ao
5 (a, 2B) 7, 50 (d, 2 B) a, 77 (t, +B) 2.2-2.8 (m, ) (0) (S) -5-n-octyl n, -2 -(4-
Synthesis of (,6-methyloctanoyl)phenyl]pyrimidine Pyridinium dichromate CL 1.07 f and dried N,N-dimethylformamide 5- were charged. next,
(8)-5-n-octyl-'l-[4-(1-hydroxy-6-methyloctyl]phenyl]pyrimidine l dissolved in dry N,N-dimethylformamide 2-
It was slowly added dropwise to 1OBt1 at room temperature. After completion of the dropwise addition, the mixture was further reacted at room temperature for 2 hours. After completion of the C reaction, ether was added to dilute the mixture, insoluble matter was separated using a Hycross Purcel, and the reaction product was extracted with ether. The ether layer was washed with dilute hydrochloric acid and water, dried, and the solvent was distilled off. The obtained crude product was purified by silica gel chromatography and recrystallization to give (8) -5-n-octyl-2-
[4-(6-methyloctanoyl)phenyl]pyrimidine (LO28f) was obtained.

Engineering, R, v max""": t680.*6tQ,t
580'B-N, M, R, (60MHz, OL+C
! j3) δ (ppm): Cl3~2.2 (m,
50 E ) 2.64 (te 211) 5Os ((1,211) a lower (d, 2B) &55 (d, 2B) &66 (s, 2 H) Describe the phase transition temperature of this liquid crystal compound.

In addition, this liquid crystal compound was sandwiched between substrates subjected to uniaxial alignment treatment using PVA rubbing, and the liquid crystal layer thickness was set to 2.5 μm.
When a voltage of ±ZOV was applied and the response was measured under crossed Nicols, it showed a value of 200 μs at 61°C.

The raw material compounds used in the present invention are produced, for example, as follows.

C to P-brombenzaldehyde! nH1n+1 Mg
, *React the drug to obtain the compound shown. The obtained compound was diluted with acetic anhydride.
Acetylate the hydroxyl group with pyridine. Next, cyanide and other secondary steels are reacted in a solvent such as dimethylformamide, dimethyA/ After the reaction, ammonia is reacted to obtain the hydrochloride of the benzamidine derivative.

Alcohol (e.g. methanol,
ethanol] is reacted with an acid catalyst (e.g., F-)luenesulfonic acid, methanesulfonic acid) to form an acetal compound, which is then treated with dimethylformamide and a halogenating agent (e.g., thionyl chloride, phosphorus oxychloride, trichloromethylchloro). formate, phosphorus tribromide, etc.) to obtain Vilsmeier's reagent.

An example of the synthesis of the raw material compounds will be described below.

Reference Example 1 Synthesis of (0(S)-4-(t-acetoxy-6-methylophthyl)bromobenzene (S)-amylalcohol-"([α]"'-aa°cn
1-bromo-5-methylhebutane 142, metal magnesium 1.74 F, and dry tetrahydrofuran were used to prepare Gullignard reagent A.

This G11 Nyar reagent is used to convert 4-bromobenzaldehyde into dry tetra containing 5 atr and dorofuran 120.
- was added dropwise to the solution over 1 hour under ice cooling. After the dropwise addition was completed, the reaction was further continued for 6 hours at room temperature, and ammonium chloride was added to stop the reaction. The reaction product was extracted with ether,
After washing with ether rttta, water, and saturated brine, it was dried, and the solvent was distilled off. The resulting oily residue is pyridine 2
0-, and acetic anhydride was added under ice cooling to perform acetylation.

The reaction product was extracted with ether, and the ether layer was extracted with 2N hydrochloric acid, a saturated aqueous sodium bicarbonate solution, and water.

After washing successively with saturated brine, it was dried and the solvent was distilled off. The obtained oil was purified by column chromatography,
6.1 t of (S)-4-(1-acetoquine-6-methyloctyl)prombenzene was obtained.

■, R, jZmaXCM-1: 1.742, 1.6
0G, 1.240'B-NMR (60MHz,
0DOJ3) δ・(pl)m): 2.05(s, 5E)
5.68 (s, +H) 7, 22 (d, 2 E) 7, 52 (
d, 2B) Synthesis of (b)(S)-4-(t-acetoquic-6-methyloctyl]benzonitrile Dry N,N-dimethylformamide 50 at, (
s)-4-(i-acetoquic-6-methyloctyl)bromobenzene 2.4? , copper cyanide (L 755t
was added and reacted under reflux for 4 hours. After the reaction was completed, the reaction product was extracted with ether. The ether layer was washed with water and Japanese brine, dried, and the solvent was distilled off. The obtained residue,
It was purified by silica gel chromatography to obtain 1.1 t of optically active 4-(+-acetoxy-6-methyloctyl)benzonitrile.

Engineering, R, vmax--” = 2255.t742.
*6t5+ 240 "B-NMR (60MBz, 0IJOj,) δ (ppm
): 2.08 (t, 5)1) 5.79(t
, IB) 7,47 (d, 2B) 7,a2(tl, 2B) (c) (S) Synthesis of -4-(+-hydroxy-6-methyloctyl)benzamidine hydrochloride (S)-4- (1-acetoxy-6-methyloctyl)
Add 1 ft of benzonitrile and 20 ml of dry ethanol.

Dry hydrogen chloride gas was blown into this mixture under water cooling. After standing for two days and nights at im, the solvent and excess hydrogen chloride were distilled off under reduced pressure. The resulting residue was dissolved in dry ethanol 20-
dissolved in. Next, 10 liters of dry ethanol containing 1 vol of ammonia was slowly added at room temperature. After the addition, the mixture was left at room temperature for two days and nights. Excess ammonia and ethanol were distilled off to obtain -a-(+-hydroxy-6-methyloctyl)benzamidine hydrochloride 192.

■,R,vrmxcn'-"=5750~2 A 0
0'H-IJMR (60M11Z, IIMSO-4,)
δ (PPm) Near 52 (cl, 2) 1) 7.92 (
d, 2E) 9.5-11L6 (m, 5B) Reference Example 2 Synthesis of β-n-octyl-α-dimethylaminoacrolein (a) Synthesis of n-decylaldehyde diethylacetal n-decylaldehyde 127f was dehydrated. 250 m of steel, dehydrated benzene 100-P-toluenesulfonic acid 21. Of was refluxed in a flask equipped with a Soxhlet extractor and reacted for about 30 hours.

Benzene and ethanol were distilled off under reduced pressure, and the residue was extracted with ether. The ether was distilled off, and the residue was distilled under reduced pressure.

Obtained i11.27 jF (bp 106-108℃/
5 W E? ) (b) Synthesis of β-〇-octyl-α-dimethylaminoacrolein n-f 57t of diraldehyde diethyl acetal was dissolved in dichloroethane 4QfRt, and dimethylformamide aat and trichloromethylchloroformate (9
2 or higher) and Vilsmeier's reagent obtained by reacting 412 in dichloroethane 240-, while heating. After cooling, the reaction mixture was poured into water and made alkaline with an aqueous potassium carbonate solution, the solvent was distilled off, and the residue was distilled under reduced pressure.

Tokuii1 15. I t (bp I 67-170
℃15 BP) or more

Claims (1)

[Claims] Represented by the formula ▲ Numerical formulas, chemical formulas, tables, etc. Phenylpyrimidine derivative liquid crystal compound.