JPS61200971A - Phenylpyrimidine derivative - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I [A is group shown by the formula II (R is CnH2n+1, and n- or iso-alkyl which may contain asymmetric carbon; n is 1-16)]. EXAMPLE:(S)-2-(4'-Hydroxyphenyl)-5-[(6'-methyl-octyloxy)phenyl] pyrimidine. USE:An intermediate for synthesizing a liquid crystal compound, especially ferroelectric liquid crystal compound, having improved stability, showing a chiral smetic phase in a wide temperature range including normal temperature, having improved compatibility with other liquid crystal compounds, suitable as a blending material and useful for producing various liquid crystal compounds. PREPARATION:A benzamine derivative salt shown by the formula III is reacted with a compound shown by the formula IV [when X is 0, Y is 0-alkyl, and when X is group shown by the formula V, Y is N(CH3)3] in a solvent such as ethanol in the presence of a metallic alcoholate catalyst such as sodium methylate to give a compound shown by the formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention is used as an important intermediate for synthesizing liquid crystal compounds, especially ferroelectric liquid crystal compounds.

[Conventional technology]

Conventionally, as a liquid crystal compound, the formula (In the formula, X is H, CI, CN, Y is C1, CtH.

The * mark indicates an asymmetric carbon atom. ) or (Ferroelectrics・24 (198
0) 809-Mo1. Cryst, Lig, Crystal
, Letter (in the above three compounds, n is 9 or 10) was prepared by B, Eng, Ostrovskj-1, et al. However, these liquid crystal compounds
Problems are seen in the narrow temperature range in which the /7-mektic phase is exhibited and also in terms of stability.

[Solving the problem]

The present invention has been developed through intensive research to solve the problems in the conventional technology.The present invention has excellent stability, exhibits a chiral smectic phase over a wide temperature range including room temperature, and has excellent miscibility with other liquid crystal compounds. Therefore, the present invention provides a phenylpyrimidine derivative represented by formula (I), which is essential for producing various liquid crystal compounds suitable as blend materials.

[In the formula, A=-o-0-B, and the hill is the general formula C'A
HtyAl" 1 indicates a chain or branched alkyl group that may have an asymmetric carbon atom in the chain. n is an integer from 1 to 16.] ] The target compound of the present invention can be produced by the following chemical reaction formula: Synthesis method (where A is the same as above. When X is an oxygen atom, Y represents an O-alkyl group. , X is 9 (CH3), ・”cto
, o and e are Y H N (CHs 12 M & T) The compound represented by the formula CI) is a compound represented by the compound represented by the formula (2) and the salt compound of the benzamidine derivative represented by the formula (1). , alcohol/L/(e.g. methanol, ethanol, propanol, impropanol) toluene, benzene, N,N-dimethylformamide, dimethyl sulfoxide, ethylene glycol/L/, diethylene glycol μ dimethyl ether, tetrahydrofuran, etc. It is produced by reacting a metal acholate catalyst (e.g., sodium methylate, sodium ethylate, potassium-t-1 toxide) or an alkali metal (e.g., sodium, potassium) in a solvent of .

The raw material represented by the formula used here is, as shown in the reference example, a 4-hydroxyphenylacetic acid derivative and an alkyl group reacted in the presence of a basic condensing agent to form an alkoxyphenylacetic acid layer conductor. , can be obtained by reacting with Vilsmeier's reagent.Also, 1. Alternatively, A
.

Boiler IM, Cerghetti, M, 5c
hadt-and H,5cherrer,,Mo1
．． Cryst.

Lj-g, CJrst, +24 volumes 215-28
The raw material represented by formula (2) can also be produced by the method described on page 1 (1977).

Example 1゜IN-o-I At-p ¥B diphenyl 1-6-
((6'-methyloctyloxy)phenyl]pyrimidine synthesis reference example 3 obtained in the oily ■-]-dimethylamino-3
-dimethylimino-2-(4-(6-methyμoctyloxy)phenyl)propane-1 perchlorate 10f and 4
-Hydroxybenzamine hydrochloride (1.02 y) was suspended in dry ethanol/I/20, VC28% sodium methylate methanol solution (17.4 F) was added thereto, and the mixture was reacted under reflux for 10 hours. The mixture was poured into ice water, acidified with diluted hydrochloric acid, and the product was extracted with ethyl acetate, washed with water and brine, and the organic layer was dried over magnesium sulfate. The melt was distilled off to give an oily residue of 4.421. This product was separated by silica gel column chromatography and purified by recrystallization to give (St-2-(4'-hydroxyphenylene/L/)-5-((6'-methymuoctyI)
Leoquin 1 phenyl]pyrimidine 0.89F was obtained.

Engineering Ryl1maXffi, 1610. Bow 585.1
435・1250・1170'H-NMR (60MHz, CDCl, )5 (ppm
):0.5-2.10 (m-18H)8.87
(t, 2H) 6.801″ (d, 2H) 6.85 ((1, 2H) 7.35 (d, 2H) 8.08 (d, 2H1 8,75 (s12H) (Reference example 1) ( Synthesis of S)-4-(6-methyloctyloxy)phenylacetic acid ethyl ester 50% sodium hydride 2..56 f. dried N.N-
8. Dissolve 25fK of dimethylformamide and add 4-hydroxyphenylacetic acid ethyl ester. Dissolve Of in 15 ml of dry tetrahydrofuran and add
Stir for 40 minutes at room temperature and add 6)-6-methyl-
1-(4-trienulfonyloxy)octane 13
．． 15m of N・N-dimethylformamide dried for 8yr
1 and added thereto, and reacted at 80C for 8 hours with stirring. The reaction solution was poured into ice water, extracted with ethyl ether, washed with brine, dried over magnesium sulfate, and evaporated to give (S)-4-(s) as an oil of 12.681.
-methyloctyloxy)phenylacetic acid ethyl ester was obtained.

Engineering F,) maxcm-1: 1785 ・1610 bow 5
15・146011240-1175= (Reference Example 2) Synthesis of (S)-4-(6-methyloctyloxy)phenylacetic acid (S)-4-(6-methyloctyloxy 1phe= !V #acid ethiμ esthetics/' 12.68
1 with methanol-1v90mJ, sodium hydroxide 8.4
f and 22 ml of water, and the reaction was carried out under reflux for 2 hours. Thereafter, methanol was distilled off, the residual aroma was made acidic by adding diluted hydrochloric acid water, and the product was extracted with ethyl ether.

The ether lvN was washed with brine, dried over magnesium sulfate, and the ether was distilled off to obtain 11.18F of (S)-4-(6-methyloctyloxy)phenylacetic acid.

IFiVlmaxcm-1: 8600-2800-1
710-1515=1250'H-IMF (60MHz, CDC1,)5 (ppt
n): 0.5-2.20 (m bow?H) 8.52 (S
=2H) 8.92(t・2H) 6.80(d12H) ter/+1. o port 1 10.5 (broad s 1IH) (Reference example 3) (Sl -1-dimethylamino-3-dimethylimino-
Synthesis of 2-(4-(6-methyloctyloxy)phenyl]propene-1 perchlorate 13.8% of dried N,N-dimethylformamide was cooled to below 5C, and 17% of phosphorus oxychloride was added to it. 85 F is added to prepare the Pielsmeier reagent. To this is added (S)-4-(6
10.5 g of -methyloctyloxy)phenylacetic acid are added and the mixture is stirred at room temperature for 1 hour at 60r for 2 hours, then at
After reacting at 0C for 5 hours, the reaction solution was concentrated using an evaporator. 84mA of water with lingering scent! Add portionwise to decompose and add 168 ml of ethyl ether/V and 12.6'l of 70% sodium perchlorate.

From this reaction solution, (S'1-1-dimethy)I/= 3
=dimethylamino-2-(4-(6-methyloctyloxy)phenyl)propene-1, as it was difficult to extract the perchlorate, the reaction solution was subjected to the next reaction. .

Claims (1)

[Claims] Formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] (In the formula, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and R
is represented by the general formula CnH_2_n_+_1 and represents a chain or branched alkyl group which may have an asymmetric carbon atom in the chain. n represents an integer of 1 to 16. ) phenylpyrimidine derivatives.