JPS5841854A - 4'-(beta-alkyloxyethyl)-4-cyanobiphenyl - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formulaI(R is 1-9C straight-chain alkyl). EXAMPLE:4'-(beta-Methylxoyethyl)-4-cyanobiphenyl. USE:A liquid crystal composition. Having positive dielectric anisotropy, useful as a display element using a nematic liquid crystal, a color display element applying guest host effect, etc. PROCESS:An ethylene glycol mono-n-alkyl ether as a starting raw material is reacted with p-toluenesulfonyl chloride, and reacted with p-bromobiphenyl to give a 4'-(beta-alkyloxyethyl)-biphenyl. This compound is iodated to give a 4'- (beta-alkyloxyethyl)-4-iodobiphenyl, which is reacted with cupric cyanide, to give a compound shown by the formulaI.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel liquid crystal compound having positive dielectric anisotropy.

Liquid crystal materials exhibiting positive dielectric anisotropy are used in display devices that utilize nematic liquid crystals (so-called TI cells) that have a twisted liquid crystal alignment, and in color that utilizes the guest-host effect, by utilizing their chemical and dielectric anisotropy. It has applications in display elements. None of these liquid crystal materials can be used as a single compound in terms of performance, such as liquid crystal temperature range, threshold voltage, response speed, stability, etc., and for practical purposes, several types of liquid crystal compounds or non-liquid crystal compounds or Mixtures of liquid crystal compounds are used.

The present invention has excellent practical properties. The present invention provides a compound useful as a component constituting a liquid crystal composition with positive Il dielectric anisotropy.

That is, one compound of the present invention is represented by the following general formula.
-(β-alkyloxyethyl)ichiban-cyanobiphenyl (in the formula, R represents a linear alkyl group having 1 to 9 carbon atoms) When the compound of the present invention is added to a liquid crystal with negative dielectric anisotropy, It is possible to obtain a liquid crystal composition having a positive dielectric anisotropy, and in addition to a liquid crystal compound having a positive dielectric anisotropy, it is also possible to lower the threshold voltage of its electro-optical response.

The present inventors have previously identified ROCH, CI! as a compound having similar properties to the compound of the present invention. , o@-50M has been filed as Japanese Patent Application No. 515-142681, but the compound of the present invention has almost the same characteristics except for the lower viscosity.

The compound of formula (1) can be produced by the following process 11.

ROCHICMIOH mass ethylene glycol mono-n-alkyl ether (
Using 1) as a starting material, react 1) with P-toluenesulfonylchloride 9)' in dry pyridine to obtain β-alkyloxyethyl LP-toluenesulfonate (2) (first step)
4'-(β-alkyloxyethyl)-biphenyl (2) is obtained by a Grignard reaction of compound (2) with P-propyrobiphenyl (second step). - Heating with a poisonous acid 4'-(#
-al;□kyloxyethyl)-4- monodobiphenyl (ma) (third step). Finally, the target compound 4'-(β
-alkyl, ethyl) -4-cyanobiphenyl (
1) is obtained (4 steps of stripes).

A more detailed explanation will be given below by showing examples of its manufacture and use as Example '. .

Example 1 (Production of 4'-(β-methylocrytyl)-4-cyanobiphenyl) (First step) Ethylene glycol mono-methyl ether 399t (5
, 214 delta) Dried 9vinazine 160011j
K@Dissolve fC or below and cool to 9 and ζ.
) is added little by little so that the reaction temperature does not exceed 10°C.

After the addition is complete, remove the cold bath) After stirring at room temperature for 4 hours, add 11' of water and 11' of toluene.

Transfer the upper toluene layer to a separating funnel and add 6N-HCl.
Washed twice with Water 500 Ho I and then once with Water 500111. What if you wash it twice with 2N-NaOH water 3001nj, wash it four times with water SOOMZ, and distill off the toluene under reduced pressure? -) 511t of 7ethyl in β-methyl luenesulfonic acid was obtained.

(Second step) Metallic magnesium 14 is added to a well-dried 21-3-hole flask.
．． 6 # (0.6 mol) and thoroughly dry the inside of the container by blowing dry nitrogen gas, and add 4 smt of anhydrous ethyl ether.
and a trace amount of element. While stirring, a solution of P-bromobiphenyl 140# (0.6 mol) in soomz dry ethyl ether was gradually added while keeping the reaction temperature at 30-35°C, and after the addition, the mixture was allowed to react at the same temperature for 3 hours. , 30 of 216# (lj mol) of β-methyloxyxyl P-toluenesulfonate was heated to a boiling temperature of 3δ℃.
When a solution of 0111 in anhydrous ethyl ether is gradually added, reflux begins due to the heat of reaction. After addition, the internal temperature is 36 with a water pass.
Warm to ℃ and reflux for 2 hours. After the reaction is completed, cool and add 500 m of water.
1 and then 6M-HCl and Sr. The reaction solution was transferred to a separating funnel, extracted with toluene 5003117, separated into a toluene layer and an aqueous layer, and the aqueous layer was further mixed with toluene 1O
The toluene layer was extracted using cuaJ, the toluene layer was collected, the insoluble matter in the toluene layer was removed by suction filtration, and the toluene layer was
0mj g) Wash once with i-NaOH water, filter the toluene layer through a piece of pleated paper, and distill off the toluene under reduced pressure. This residue K Na0I110 # water aomzt ethanol 5
Add 001!11 and reflux for 30 minutes on a water path. Cool this mixture and add 300 g of toluene to water II.
Add 114 and transfer to a separatory funnel, and add 30
The solution was washed three times with 0111 water and the toluene was distilled off under reduced pressure. Then vacuum distillation 1), P 137-140°C/1,
If you collect a volume of 51111H#, you will get 34t of 4'-(β-
34t of methyloxethyl)-biphenyl (2) is obtained.

(Third step) In a 300-liter three-ring flask, add 34 JF (0,11! I mol) of 4'-(β-methyloxyethyl)biphenyl, 111 mjt of acetic acid, 3 Qmj of water, and ii 6.8 # of dihydric acid (093
84 mol), W element 17,9# (0,0104 mol),
Add 13 CO of carbon tetrachloride and 8 ml of concentrated sulfuric acid, stir, heat with a mantle heater, and react at 83°C under reflux for 3 hours. After the reaction is complete, cool to 70"C and add 10 mJ of 10-sodium thiosulfate water. After cooling to room temperature, the precipitated crystals were recrystallized with 3001j of ethyl alcohol to obtain 30t of 4'-(β-methyloxy7ethyl)-4-yokudobiphenyl(ma). The melting point of the substance is 97-99.4℃.

(Fourth step) 20t (0.59 mol) of 4'-(β-methyloxyethyl)-4-*udobiphenyl was added to a 200-liter three-ring flask.
and cupric cyanide 6.21 (0,688 mol),
Add 61mj' of DMIF, stir, and react under reflux at 49°C for 6 hours. After the reaction was completed, it was cooled to room temperature, 291 ammonia water 20M11 was added and stirred, and toluene 50M was added.
111 and 100 mj of water were added, and the reaction solution was filtered with suction.
The toluene layer of the P solution is washed with 614-hydrochloric acid, then with caustic soda water, and then further washed with water until it becomes neutral. After drying the toluene layer with lots of anhydrous sodium sulfate, the toluene layer was passed through an active alkaline layer, and the toluene was distilled off.
When the remaining crystalline substance is recrystallized with methanol 30!11j and dried separately from P, the target product 4'-(β-methyloxyethyl)ichiban-cyanobiphenyl 3t can be obtained. points) is 50. The N→I point measured and extrapolated from the mixture with 5°C and '-octyloxy-4-cyanobiphenyl was -6°C. (Iris-1 point cannot be measured with this compound alone), and the elemental analysis values of this compound are in good agreement with the calculated values as shown below.

Analysis value Calculated value (as C1, H,, No.) CBo,
8-80.98% He, 4% 6.37- M i5. IIJ 3,90'j Example 2 P- ) Obtain luenesulfone β-ethyl oxethyl.

In addition, in the second step reaction, 4'-(β-ethyloxyethyl)
-Biphenyl was obtained. The boiling point of this substance is 132℃~14
It was heated at 0°C/1.5 mmHt. Next, in the third step reaction, 4'-(β-ethyloxyethyl)-4-IT-tobi7
Huh? I was obtained, but the melting point of this product was F9. δ~80.5
It was ℃. In the fourth step of the reaction, the desired number '-(β-ethyloxyethyl)-4-cyanobiphenyl was obtained, which had a melting point (C-1 point) of 49.4 to 50.6°C. Further, the N-1 point obtained by measuring and extrapolating the mixture with 4'-octyloxy-4-cyanobiphenyl was -6°C. Furthermore, the elemental analysis values of this compound were in good agreement with the calculated values as shown below.

Analysis value Calculated value (as C,, H,, No.) CB1,1
My Ell, 24 饅■ 6.8 * 6.01 Summer 6. δ*s, Roti- The following compound can also be obtained in the same manner as in Examples 1 and 2.

1'-(7ethyl in β-puro)-4-cyanobiphenyl number 1. - (β-butyloxyethyl)-4-V
7novi7ea#+I-(β-pentyloxyethyl)-
4-cyanobiphenyl number'-(β-hexyloxyethyl)-4-cyanobi7yl+I-(β-heptyl-diethyl)-4-cyanobiphenyl+I-(β-octyloxyethyl)-4-cyano Biphenyl number ζ (β-nonyloxyethyl)-4-cyanobi 7 tool Example 3C
Usage example 1) The nematic liquid crystal temperature range (MR) of a liquid crystal composition consisting of 25 parts of Cf'' and ΣQ-CI is -10-72
, 3℃, 20″CK ff, 6 viscosity flea 1i2B,
Sap, dielectric anisotropy Δ##ill, 1 (@++ =
16. L g, = 4.4) and jtLt-k” thickness lO
The threshold voltage of the new TRI cell in Seiho is ζF2
v, Koi Akebono pressure is 2. It was MY.

When one of the compounds of the present invention is added to 80 parts of this composition, the MR of the liquid crystal composition is -15 to δ and 4°C.

viscosity! Trout is 3B! ! ' p y Δt is lja
, 8 (to = 18*@t = 3.1), and if this is sealed in the same cell as above, the threshold voltage at the edge is lJ? The L saturation voltage is 1pδV, which is 9.

Example 4 (Usage Example 2) Nematic liquid crystal temperature range (M, R
) is -10#63.3℃20' The viscosity Ws at CK is 4B, 1opH electric constant anisotropy Δ'' ha l g, 4 (#
,.

x 1 'F, l e k = 4.8) and this is 4A/thickness 1oPIa! Although the summer cell is Km, the threshold voltage is 1.5δV and the sum voltage is 2.2m.

The MR of the liquid crystal composition containing one of the compounds of the present invention in 80 parts of this composition was -IJs-49.1°C.

Is it 4? , 16Pe Δ@ is l! 5.4 (t,,=
19. True.

g, = a, s), and when this is newly inserted into the same cell as above, the threshold voltage is i, gav, and the saturation voltage is station δV, which is 9.

Example δ (Use example 3) A liquid crystal composition having the following composition was prepared.　　.

The anisotropy of the dielectric constant of this composition is negative (Δ value is about -1), and therefore it cannot be displayed in a 7M cell.

In addition to this, CM of Example 1 of the present invention, OCR, C3I, (
The properties and characteristics of the composition containing 20 parts of yCM are as follows, and it can be displayed on a 7M cell.

Clear point 50.1℃ 80 2.1 (mu, l = 8.1. Red = 5.
4) Threshold voltage 1,987 Saturation voltage 2. More than FQ'V

Claims (1)

[Claims] (In the above formula, R represents a straight-chain alkyl group having 1 to 90 carbon atoms)
4'-(β-alkyloxyethyl)-4 represented by
-Cyanobiphenyl. (2) 4-(β-alkyloxyethyl)-biphenyl is converted to 4′-(β-alkyloxyethyl)
-4-111-tobiphenyl. Next, it was dicyanated with cyanide No. 1 steel to form 4'-(β-
4'-(β-alkyloxyethyl)-4-
Method for producing cyanobiphenyl. (3) General formula % Formula % (R in the above formula represents a straight chain alkyl group having 1 to 9 carbon atoms)
4'-(β-alkyloxethyl)-4 represented by
−? / A liquid crystal composition having a characteristic of I\I with a small amount of anobiphenyl and one type of tomo.