JPS58222042A - 4-(trans-4-alkylcyclohexyl)-1-(4-(trans-4- alkyloxymethylcyclohexyl)phenyl)cyclohexene - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (R1 and R2 are 1-8C alkyl). EXAMPLE:4-( trans-4-Propylcyclohexyl )-1-[4-( trans-4-methyloxymethylcyclohexyl)phenyl]cyclohexene. USE:Useful as one component in liquid crystal compositions, with a clear point as high as 280 deg.C or above, effective for increasing the clear point, and having improved stability and compatibility with another liquid crystal compound. PROCESS:Methyl trans-4-phenylcyclohexanecarboxylate of formula II as a starting raw material is reduced as shown in the reaction formula, and the resultant reduction product is then reacted with p-toluenesulfonyl chloride, an alcoholate and further iodine and iodic acid to give a compound of formula III, which is then converted into the compound of formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel liquid crystal compounds useful as electro-optic display materials.

The liquid crystal currently widely used as a display element is a nematic liquid crystal, but there are various display methods.They can be roughly divided into TN type (twisted nematic type), DS type (dynamic scattering type), and DAP type (electric field control type). Birefringent type), PC type (cholesteric-nematic phase transition type), G using dichroic dye
Type II (guest-host type) is a typical example. However, at present, there is no single compound of liquid crystal materials used in any of these display elements that can withstand practical use in terms of properties such as liquid crystal temperature range, operating voltage, response performance, etc.; At present, in some cases, compounds suitable for practical use are obtained by mixing about 20 types of liquid crystal compounds.

The object of the present invention is to provide a compound useful as a component of a stable liquid crystal composition that has excellent performance that can withstand such practical uses.

That is, the compound of the present invention is a compound represented by the following general formula.

R, OCR, Kari/"(/HR2(+1 (However, in the above formula, R1 and R2 represent an alkyl group having 1 to 8 carbon atoms) The compound of the formula 0) of the present invention has a clearing point (N-I points) is 28
It is a novel liquid crystal compound with excellent stability that has the effect of raising the clearing point of the composition when mixed with a compound having a low N-I point because it is as high as 0°C or higher. This compound has excellent compatibility with other liquid crystal compounds, such as piphenyl-based, ester-based, azoxy-based monocyclohexylcarboxylic acid ester, phenylpyrimidine-based, phenylclohexane-based, and phenylmetadioxane-based liquid crystals. It is mixed with other compounds and used as several types of systems I'''-.

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

■(OCR2＜纂）H2=di〉(shoulder)R10CH2()○(vl R10CH2(KA○-I) (1111 First, the known substance methyl trans-4-phenylclohexanecarboxylate (W, S).

Johnson et al., J.A.C., 8, 67, 1045 (1
945)) (+1 is lithium aluminum hydride (L
r AIH4) by reducing with a reducing agent such as trans-4
- Obtain phenyl alcohol.

It is reacted with p-)luenesulfonyl chloride in dry pyridine to give p-toluenesulfonic acid (trans-4-phenylchlorohequinylmethel) ester (ffl).

The reaction of this (l with alcoholade) produces trans-4-alkyloxymethyl-1-phenylclohexane (V).
get. Compound tv> is prepared by heating with iodine and iodic acid in a solvent to prepare trans-4-alkyloxymethyl-1-(4'-iothophenyl)cyclohexane tv.
I), the target compound (Natsu) is obtained by reacting the compound (Vl) with the lithium compound lance-4-alkylcyclohexynyl)cyclohexanone using a solution of n-butyllithium hechitin.

The details of the production method and properties of the compound of the present invention, as well as its use as a liquid crystal material, will be explained below with reference to Examples.

Example 1 (4-() lance-4-propylcyclohexyl)-1
-(Production of 4-(trans-4-methylokinemethylcyclohexynyl)phenylconclohexene) First step: 11.1f (0,293 mol) of lithium aluminum hydride (2-dried tetrahydrofuran (THF) 420
- was added and stirred vigorously, and methyl trans-4-phenylcyclohexanecarboxylate (1) 64. Of
A solution of (0,298 mol) dissolved in THF'70- is added dropwise while keeping the reaction temperature below 20'C. After completion of the dropwise addition, the mixture was heated to 55°C, reacted for 2 hours, and cooled.

Next, add ethyl acetate 12- and water 100rnt, and then add 1
When 350-8-thiosulfuric acid is added, the mixture is separated into two layers: a tetrahydrofuran layer and an aqueous layer. Add 200% of n-hebutane, transfer to a separatory funnel, wash with 500% of water, then wash with 500% of a 2% aqueous sodium carbonate solution, and further wash with water until the aqueous layer becomes neutral.

Heptane and THF were distilled off and the solid remaining in the pot was evaporated with heptane 2
Recrystallize with o-, separate the crystals, and dry the crystals to obtain 4-phenyl-cyclohexynlumether 7 /I/ co-/L/+
1151.4 r was obtained. Melting point 47.3-48.5
℃.

Second stage Compound obtained in the first stage (1150t (6,268
mole) was dissolved in 110 cc of dry pyridine and cooled to below 5°C, to which 50 mol of p-) luenesulfonic acid chloride was added.
．． 1? A solution of (0,263 mol) dissolved in 70 ml of dry toluene was added dropwise little by little from the dropping funnel so that the reaction temperature did not exceed 10°C. When the addition was completed, the cold bath was removed and the mixture was stirred at room temperature for 4 hours, after which 100% of water and 300% of toluene were added and stirred. Transfer the toluene layer to a separatory funnel and 6N-1'ICI! Wash twice with 100 - of water, then once with 200 - of water, and then wash with 1 of 2N-N aOH water.
Wash twice with 00- and then four times with water 200-.

Toluene was distilled off under reduced pressure, and the resulting crystals were dissolved in toluene 90%.
m7! When the crystals were recrystallized from and dried, p-)luenesulfonic acid (trans-4-phenylonchlorohexylmethyl)ester 1ff) 77t was obtained. Melting point: 108.0-108.7°C.

3rd step Methyl alcohol 250- is stirred at room temperature +
Every 9th place, metal sodium 17-. 4 f (0,
755 moles) is added in small amounts to make Suthorium Metkind. After the metallic sodium pieces are gone, the compound obtained in the second stage (ff) 200 f
A solution of (0,581 mol) dissolved in 600 ml of dry toluene was gradually added dropwise to the solution while maintaining the internal temperature within the range of 50 to 60°C. After the dropwise addition was completed, the mixture was refluxed for 4 hours, then cooled, 201 nl of water was added thereto, and the mixture was transferred to a separating vessel, and the toluene layer was washed with water until the aqueous layer became neutral. After toluene was distilled off under reduced pressure, 1009 of su-4-methyloxymethyl-1-phenylclohexane (V) having a boiling point of 105-b was obtained by distillation under reduced pressure.

Fourth stage! Compound fil obtained in a three-stage three-roof flask
10 Of (0,490 mol), acetic acid 344-1 water 9
Add 1 mes iodic acid 20.6.9 (0.117 mol), iodine 54.59 (0.215 mol), carbon tetrachloride 40 rnl, and concentrated sulfuric acid 14 me, stir, heat with a mantle heater, and reflux for 3 hours. . After the reaction was completed, the mixture was cooled to room temperature and 10% aqueous sodium thiosulfate was added to eliminate the color of excess iodine (approximately 15 cc). n-hebutane 20C) m7! The n-hebutane layer was washed with water until the aqueous layer became neutral, the n-hebutane was distilled off under reduced pressure, the residue was dissolved in 50 td of n-hexane, and -1
After standing at 0 to -20°C for 12 hours, the resulting crystals were separated and dried to give trans-4-methyloxymethyl-1-(
4'-iodophenyl)cyclohexane (v1181.
39 was obtained. Melting point: 40.3-42.3°C.

5th Step 'In a 500-three-necked flask, add the compound (
1127,7f (0,084 mol) and dried toluene 60g were added and stirred at 20°C to dissolve. Add 6.3 mj (0,100 mol) of a commercially available 1.67 N n-butyllithium hexane solution to the solution at a temperature of 20 to 25°C.
It was added dropwise over about 10 minutes while maintaining the temperature. When the dripping is finished, 25
After keeping at ℃ for 30 minutes, cool to 5℃ and! -()lance-4-propylcyclohexyl)cyclohexanone 19
．． A solution of 5f (0,088 mol) dissolved in 30 ml of dry toluene was added dropwise through the dropping funnel while ensuring that the internal temperature did not exceed 10°C. After dropping, the mixture was kept at 45°C for 30 minutes, cooled, and 30 parts of water and 60 parts of 6N hydrochloric acid were added. Separate this and add acidic sulfuric acid power 9 (KHSO3) 3 y to the organic layer.
is added and heated to distill off the solvent and concentrate until the liquid temperature reaches 1.10°C, during which the dehydrogenation reaction proceeds. After the reaction, the organic layer was cooled and transferred to a separatory funnel, and the organic layer was washed three times with water. The solvent was distilled off, and the residue was recrystallized from ethyl acetate in a freezer. After drying in Sawabetsu, the target compound (1) was obtained. )15
I got f. The C-8 point of this product was 208.0°C, the SN point was 234.1°C, and the N-I point was 280°C or higher.

Moreover, the elemental analysis values of this product are in good agreement with the calculated values as shown below.

Actual value book) Calculated value + (as C29H440)
CB5.20 85.23 H10,8210,85 Example 2.3 Preparation of sodium ethoxide or potassium bromine using ethyl alcohol or divinyl alcohol in place of methyl alcohol in the third step of Example U. oxide was obtained, and it was reacted with p-)luenesulfonic acid (trans-4-phenylcyclohexylmethyl) ester in the same manner as in Example 1 at 112-115°C/1.5°C, respectively.
-ng or 127~b and 4-( )-7-4-propylcyclohexyl)-1-(4-()lance-4-ethyloxymethylcyclohexyl)phenylcocyclohexene and 4-()lance-4-propylcyclohexyl)-
1-(4-()lans-4-propyloxymethylcyclohexynyl)phenylconclohexene was obtained. The former's C-8 score was 163.

The SN point was 243°C, the NI point was 280°C or higher, the latter C-S point was 138°C, the SN point was 267°C, and the NI point was 280°C or higher.

Example 4 (Usage example) The liquid crystal temperature range (MR) of the liquid crystal composition consisting of 09 parts of C5H1, (EΣ)IN3B, is -3 to 5
The viscosity η20 at 2.5°C and 20°C is 23 cpt, and the dielectric constant anisotropy Δε is 11.3 (ε, , = 16.2, ε =
4.9), when 1 is sealed in a TN cell with a cell thickness of 10 μm, the threshold voltage is 1.5 V and the saturation voltage is 2.2 V.
Met. This composition contains 4.7% of CH30CH2 (ROHI(Y()(◇-C3H7)
The MR of the liquid crystal composition to which 6 parts was added spreads from -3 to 61.5°C, η20 is 24.8 Cp, and Δt is 10.6 (
'+1 = 15.4, ε = 4.8), and the threshold voltage when sealed in the same cell as above is 1°60v1
The saturation voltage was 2.29V.

that's all

Claims (2)

[Claims] (1) 4-(trans-4-alkylinchlorohexyl)-1-( represented by the general formula % formula % () (in the above formula, R1 and R2 represent an alkyl group having 1 to 8 carbon atoms) 4-() lance-4-alkyloxymethylcyclohexyl)phenylcocyclohexene. (2) 4-(trans-4-alkylinchlorohexyl)-1-(4 A liquid crystal composition containing at least one type of -() lance-4-alkyloxymethylcyclohexyl)phenylcocyclohexene.