JPS597122A - 4-substituted-(trans-4'-(trans-4"-(trans-4'''-alkylcyclohexyl) cyclohexyl)cyclohexyl)benzene - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (R and R' are H or 1-10C alkyl or alkoxyl). EXAMPLE:4-Methyl-{trans-4'-[trans-4''-( trans-4'''-ethylcyclohexyl )cyclohexyl]cyclohexyl} benzene. USE:A component in liquid crystal compositions, capable of exhibiting the liquid crystal phase within a wide temperature range and forming a nematic liquid crystal composition having a low viscosity, and stable to moisture, heat, light and air. PROCESS:4-Methoxybromobenzene is reacted with Mg to form a compound of formula II, which is then reacted with a compound of formula III to afford a compound of formula VI. The resultant compound of formula VI is then dehydrated and reduced in the presence of a Raney nickel catalyst, demethylated and catalytically reduced in the presence of an Ru/C catalyst to give a compound of formula V, which is then oxidized in a mixed solution of chromic acid with sufuric acid. A compound of formula VI is then dropped to the oxidation product, and the resultant product is then dehydrated and reduced with H2 in the presence of the Reney nickel catalyst to afford the aimed compound of formula I .

Description

[Detailed description of the invention] The present invention relates to a liquid crystal material and a composition containing the same.

Liquid crystal display elements utilize the optical anisotropy and dielectric anisotropy of liquid crystal materials, and iJTN is used as the display method.
Type, D'ms guest/host shop SDAP type, white.
There are various methods such as tiller type, and each method requires different properties of the liquid crystal material used. For example, depending on the type of display element, the dielectric anisotropy Δ
6 requires a positive value, a negative value, or an intermediate value is suitable. However, in any case, the liquid crystal material used must exhibit a liquid crystal phase over as wide a temperature range as possible, and be stable against moisture, heat, air, light, etc. At present, there is no single compound that satisfies all of these conditions, and the current state of affairs is to mix several types of liquid crystal compounds and non-liquid crystal compounds to obtain compounds that can be put to practical use.

In recent years, there has been a demand for liquid crystal display elements that operate over a wide temperature range, that is, from -30°C to about 90°C. In order to meet these demands, a liquid crystal compound that exhibits a liquid crystal phase over a wider temperature range and has low viscosity is required.

The developed FJA satisfies these requirements.

That is, 4-substituted-(trans-4'-[trans-4#-( ) Lance-
4"'-alkylcyclohexyl)cyclohexylcocyclohexyl)benzene.

The compound of the present invention, for example 4-methyl-(traethylcyclohexyl)cyclohexylcocyclohexyl)benzene, has a crystalline smectic point of 71.0°C, a smecticonematic point of 254°C, and a nematic clearing point of 293°C.
It exhibits a liquid crystal phase over a wide temperature range, making it an extremely suitable substance for creating low-viscosity nematic liquid crystal compositions with a wide liquid crystal temperature range by adding a small amount. Also moisture, heat, and light.

It is also stable in air.

Next, the manufacturing method of the present invention will be described. 4-Methoxybromobenzene is reacted with magnesium to form 4-methoxybenzene magnesium bromide, -1tK4-()U/Su4
'-alkylcyclohexyl)cyclohexanone is reacted with 4-methoxy-(4'-()lance-4#-alkylcyclohexyl)cyclo to give 1'-ol]benzene (■). This was dehydrated and 4-methoxy-(4
'-() lance-41-furkylcyclohexyl)cyclohexe/-11-yl]benzene (1M) is obtained.

This is reduced and recrystallized using Raney Ni as a catalyst to obtain 4-methoxy-[trans-a'-()trans-4'-furkylcyclohexyl)cyclohexanonebenze/(■). This was subjected to a demethylation reaction with hydrobromic acid to produce 4-hydroxy-[trans-4'-()trans-4#-alkyl/chlorohexyl)cyclohexanonepenze/(M).
get. Next, this is Ru/C! as a catalyst at 150℃
Catalytic reduction was carried out at 50Kg/- to give 4-[trans-4'
-() lance-41-alkylcyclohexyl)cyclohexylcocyclohexanol (■) is obtained. This was subjected to an oxidation reaction with a chromic acid-sulfuric acid mixture in acetone, and 4-[trans-4'-(trans-4'-alkylcyclohexyl)cyclohexylcocyclohexanone (I
t/).

Next, (trans) was added dropwise to the Grignard reagent which was reacted with 4-substituted-promobenzenogoldmagnesium.
-Substituted-1-(4'-()u/su4'-()lance-4''-alkylcyclohexyl)cyclohexylcocyclohexane-1〆-ol lpen/@) is obtained. When this is dehydrated, 4- substitution -(4'-() lance-4'-
() lance-4″-alkylcyclohexyl)cyclohexylconclohexen-1′-yl)benzene (n)
is obtained. This was reduced with Raney N1 catalyst, recrystallized, and the target product, 4-W#-(trans-4'-()lance-4'-(+-lance-4M-alkylcyclohexyl)cyclohexyl)cyclohexyl ) Pe/Zeno (1
).

The above is expressed as a chemical formula as follows.

HBr Hereinafter, the compounds of the present invention will be explained in more detail with reference to Examples.

Example 1. [4-Methyl-(trans-4'-()trans-4'-()trans-4'-ethylcyclohexyl)
cyclohexylcocyclohexyl) benzene In) 1.2 F (0,049 mol) of magnesium fragments were placed in a third flask, and 9.2 f (
0,049 mol) dissolved in tetrahydrofuran is slowly added dropwise while stirring while maintaining the reaction temperature at 30 to 35°C in a nitrogen stream. The reaction occurs, and in 3 hours, the magnesium is dissolved and becomes uniform. This yields 4-methoxyphenylmagnesium bromide. To this, 10.2 f (0,049 mol) of 4-(trans-4'-ethylcyclohexyl)cyclohexanone was dissolved in tetrahydrofuran to make 50-, and the reaction temperature was set to 5-10.
Drop as quickly as possible while keeping the temperature at °C. After dropping, 35℃
The mixture was heated to a temperature of 100.degree. C. and stirred for 30 minutes, then 3N hydrochloric acid (50°C) was added. Transfer the reaction solution to a separatory funnel and add 200 m of toluene to
After extraction, the combined toluene layers are washed with water until the washings become neutral, and then the toluene is distilled off under reduced pressure. The remaining oil is 4-methoxy-[1'-hydroxy-4'-()
lance-41-ethylcyclohexyl)cyclohexyl]benzene.

Add 6 tons of potassium hydrogen sulfate to this and heat to 160°C in a nitrogen stream.
Dehydrate for 2 hours. After cooling, 200 ml of toluene is added, and the potassium hydrogen sulfate is removed separately, and the toluene layer is washed with water until the washing liquid becomes neutral. Then, toluene was distilled off under reduced pressure,
The desired 4-methoxy-(4'-()lans-4l-ethylcyclohexyl)cyclohexen-1'-yl]ben/zene is obtained by recrystallizing the remaining oil with ethanol. This thing 7. Of Raney nickel catalyst 1.
It was dissolved in 120°C of ethanol along with Of, and catalytic reduction was carried out at normal pressure at 50°C to absorb 500°C of hydrogen. The catalyst is sent door to door and recrystallized as is. Since the obtained product is a mixture of cis and trans forms, recrystallization is repeated with ethanol to isolate the trans form. The obtained 4-methoxy-[trans-4'-()trans-41-ethylcyclohexyl)cyclohexyl]benzene 80F was dissolved in acetic acid 450- and hydrobromic acid (47%) 450- was added and refluxed for 30 hours.

After the reaction, the reaction mixture is cooled to precipitate crystals and separated, and the filtrate is recrystallized with ethanol to obtain 4-hydroxy-[trans-4'-(trans-41-ethylcyclohexyl)cyclohexyl]benzene.

Put 2Of this stuff into an autoclave and 40% ethanol.
Add 0- and add Ru103f at 180℃5QK9/ad
Perform catalytic reduction. The catalyst was separated and the solvent was distilled off under reduced pressure.
-(trans-4'-()trans-41-ethylcyclohexyl)cyclohexylcocyclohexanol is obtained. Add 31 grams of acetone to this, and add 14.5 grams of chromic anhydride and 23.6 grams of concentrated sulfuric acid while keeping the temperature between 0 and 3 degrees Celsius.
Add water to f and add 5ONtK dropwise over 2 hours. After the reaction is completed, excess oxidizing agent is decomposed by adding isopropyl alcohol, and sodium bicarbonate is added to neutralize the precipitate, and the filtrate is washed with acetone. Combine the washing with solution F, remove the acetone under reduced pressure, and add 500% of toluene.
Extract 3 times. After drying the combined toluene layers with sodium sulfate, the toluene was distilled off under reduced pressure, and fresh toluene 50
Recrystallize at −. The obtained 4-[trans-4'-()
U/Su 4r-ethylnchlorohexyl)cyclohexylcocyclohexyl 77 is heated and dried under vacuum. This thing 11
．． A solution of 6f dissolved in 100-tetrahydrofurano,
The Mf piece 1.22 was reacted with P-promotolue/in a nitrogen stream to form 4-methylbenzene/gnesium bromide, which was quickly dropped into the solution. After refluxing for 3 hours, the mixture was cooled, 3N hydrochloric acid was added, extracted with Toluev 300, and the water washing was repeated until the washings became neutral. The solvent was distilled off under reduced pressure, 4 tons of potassium hydrogen sulfate was added to the remaining oil, and the mixture was dehydrated at 160C for 2 hours under a nitrogen atmosphere. After cooling, potassium hydrogen sulfate was removed from each unit, 300% of toluene was added, and the mixture was washed with water. The solvent was distilled off under reduced pressure, and the product obtained by recrystallizing with fresh toluene fluoride was 4-methyl-(4'-() lance-4'-()
lance-r-ethylcyclohexyl)cyclohexylcocyclohexen-1'-yl)benzene. 3.2f of this product was dissolved in 300ml of toluene, 1.5f of Raney N1 catalyst was added, and catalytic reduction was carried out at room temperature and pressure, and the reaction was terminated at the point where the raw material disappeared using gas chromatography. After distilling off the solvent, recrystallization was repeated with toluene to obtain the target product, 4-methyl-(trans-4'-[trans-4'-
() lance-r-ethylcyclohexyl)cyclohexylcocyclohexyl)benzene was obtained. Yield o, 8t,
Yield 25%. Its crystal-smectic point is 71.0℃,
Smectic-nematic point is 254℃, neotic-
The clearing point was 293°C.

The following compounds can also be produced in the same manner as in Example 1.

4-ethyl-[trans-4'-()trans-4l-(
trans-r-ethylcyclohexyl) Schiftahexyl]cyclohexyl]benzene.

4-propyl-[trans-4'-()trans-4'-
() lance-C-ethylcyclohexyl)cyclohexyl]cyclohexyl]benzene.

4-methoxy-[trans-4'-()trans-4'-
() lance-r-ethylcyclobexyl)cyclohexyl]cyclohexyl]benzene.

Trans-4'-() Lance-4'-()U/Su4#
-xf-cyclohexyl,)cyclohexylcocyclohexylbenzene.

trans-4'-()trans-4'-(trans-C-
Propylcyclohexyl)cyclohexylcocyclohexylbenzene.

4-Methyl~[trans-4'-()trans-4'-(
trans-4''-7'ropylcyclohexyl)cyclohexyl]cyclohexyl]benzene.

4-ethyl-[trans-4'-()trans-4l-(
) lance-4''-7'ropylcyclohexyl)cyclohexyl]cyclohexyl]benzene.

4-propyl-[trans-4'-()trans-4'-
() lance-4''-/'ropylcyclohexyl)cyclohexyl]cyclohexyl]benzene.

4-Butyl-[trans-4'-(trans-4l-(
trans-4''-7'ropylcyclohexyl)cyclohexyl)schiftetrahexyl]benzene.

4-methoxy-[trans-4'-()trans-4'-
() lance-C-propylcyclohexyl)Schiftetrahexyl]cyclohexyl]benzene.

trans-4'-() lance-4'-() lance-r-
butylcyclohexyl)cyclohexylcocyclohexylbenzene.

4-Methyl-[trans-4'-()trans-4l-(
trans-4tn-butylcyclohexyl)cyclohexyl]cyclohexyl]benzene.

4-ethyl-[trans-4'-()trans-4l-(
trans-C-butylcyclohexyl)cyclohexyl]cyclohexyl]benzene.

4-propyl-[trans-4'-[)trans-4'-
() lance-r-butylcyclohexyl)cyclohexyl]cyclohexyl]benzene.

4-Butyl-[trans-4'-()trans-4l-(
): 7 nssu? -butylcyclohexyl)cyclohexyl]cyclohexyl]benzene.

4-pentyl-[trans-4'-[)trans-4'-
() lance-4''-butylcyclohexyl)cyclohexyl]cyclohexylybenzene.

Trans-4'-() Lance-4'-()U/Su4'
-pentylcyclohexyl)cyclohexylcocyclohexylbenzene.

4-Methyl-[trans-4'-()trans-4#-(
trans-41-pentylcyclohexyl)cyclohexyl]cyclohexyl]benzene.

4-ethyl-[trans-4-[trans-4f-()
lance-C-pentylcyclohexyl)cyclohexyl]cyclobexyl]benzene.

4-globiru [trans x-4'-() lance-4'
-() lance-r-pentylcyclohexyl)cyclohexyl]cyclohexyl]benzene.

4-Butyl-[trans-4'-()trans-4'-(
cyclohexyl]cyclohexyl]benzene.

4-pentyl-[trans-4'-()lance-4#-
() lance-41-pentylcyclohexyl)cyclohexyl]cyclohexyl]benze/.

4-methoxy-[trans-4'-()trans-4L(
):)41-pentylcyclohexyl)cyclohexylcocyclohexyl]be/zen.

Example 2 (use example) trans-4-globyl-(4/y-anophenyl)
Cyclohexane 289g trans-4-pentyl(4'-cyanophenyl)cyclohexane 42trans-4-hebutyl-(4'-cyanophenyl)cyclohexane/ The nematic liquid crystal temperature range of the liquid crystal composition with the composition of 30
~52°C. This liquid crystal composition was applied to a T cell with a cell thickness of 10 μm.
The operating threshold voltage of the tunno sealed in an N cell (twisted natural cell) is 1e53V.

The saturation voltage was 2.12 V”r.The viscosity was 20°C.
It was 23 cp.

5 parts of 4-methyl-(trans-4'-()lance-4#-()lance-41-ethylhexyl)cyclohexylcocyclohexyl)benzene of Example 1 of the present invention was added to 95 parts of the above liquid crystal composition. Expansion of the nematic liquid crystal temperature node HFi of the added liquid crystal composition from -3 to 61.5°C1.
, 2e) The viscosity at ℃ does not increase much at 25 cp, and when sealed in the above cell, the operating threshold voltage is 1.5 V and the saturation voltage is 2.1 V, making it possible to expand the nematic temperature range without increasing the voltage at all. did it.

that's all

Claims (2)

[Claims] (1) 4-substituted- represented by the general formula (in the above formula, R and y represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group)
(trans-47-[trans-4l-()uysu r
-Alkylcyclohexyl]cyclohexyl]cyclohexyl)benzene. (2) 4-substituted-(trans-4'-[trans-4'- () Lance-
1. A liquid crystal composition comprising at least one type of r-alkyl(r-alkyl(r-hexyl)(hexyl)((hexyl))(cyclohexyl)))(r-alkyl((r)hexyl)(r)(hexyl)(r)(r)hexyl)(r)(r)hexyl)((r)hexyl)((r)hexyl)((r)hexyl)))