JPS5916855A - Trans-4"-alkyl-trans-octadecahydro-p-terphenyl-trans-4- carboxylic acid-4'''-halogenophenyl ester - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I (R is H, or 1-10C alkyl; X is F, or Cl). EXAMPLE:Trans-4''-propyl-trans-octadecahydro-p-terphenyl-trans-4-carbo xylic acid-4'''-fluorophenyl ester. USE:A liquid crystal substance showing a liquid crystal phase in a wide temperature range, having positive dielectric anisotropy. Showing high transparent point, having improved stability to water, heat, light, etc. Not changing a threshold value of voltage and saturated voltage considerably. PROCESS:A compound shown by the formula II is hydrogenated using a Raney- nickel catalyst to give a compound shown by the formula IV, which is halogenated to give a compound shown by the formula V, which is cyanided to give a compound shown by the formula VI, which is further hydrolyzed to give a compound shown by the formula VII. This compound is then reduced with metallic sodium to give a compound shown by the formula VIII, which is converted into an acid chloride, which is reacted with p-fluoro(or chloro)phenol in pyridine, to give a compound shown by the formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel liquid crystal material exhibiting a liquid crystal phase over a wide temperature range and having positive frame anisotropy, and a liquid crystal composition containing the same.

Display elements using liquid crystals have come to be widely used in watches, calculators, etc. This liquid crystal display element utilizes the properties of optical anisotropy and dielectric anisotropy of liquid crystal materials, and liquid crystal phases include nematic liquid crystal phase, smectic liquid crystal phase, and cholesteric liquid crystal phase, among which nematic liquid crystal is used. The one that has been put into practical use is the most widely used. That is, they include TN (twisted nematic) type, DS (dynamic scattering type), guest-host type, DAP type, etc., and the properties required of the liquid crystal materials used for each type are different.

However, in any case, it is desirable that the liquid crystal materials used in these display elements exhibit a liquid crystal phase over as wide a range as possible in nature, but at present there are no single materials that can satisfy such conditions. Instead, the current situation is to mix several types of liquid crystal substances or non-liquid crystal substances to obtain something that can be put to practical use. In addition, these materials must of course be stable against moisture, light, heat, air, etc., and furthermore: the threshold voltage and saturation voltage necessary to drive the display element must be as low as possible, and the response must be as low as possible. In order to increase the speed, it is desirable that the viscosity be as low as possible. By the way, in order to widen the liquid crystal temperature range toward high temperatures, it is necessary to use a liquid crystal substance with a high melting point as a component, but liquid crystal substances with a high melting point generally have a high viscosity, so the liquid crystal composition containing it also has a low viscosity. As a result, the response speed of liquid crystal display elements that can be used at high temperatures, for example, up to about 80° C., especially at low temperatures, tends to become significantly slower. However, the present inventors found a liquid crystal material with a high liquid crystal temperature range and low viscosity, and arrived at the present invention.

That is, the present invention provides a trans-4'-alkyl-trans-octadeca compound represented by the general formula (in the above formula, R represents hydrogen or an alkyl group having 1 to 10 carbon atoms, or represents either ? or OJ). Hydro-p-terphenyl-trans-4-carboxylic acid-4''-halochenophenyl ester and a liquid crystal composition containing the same.

The compounds of the present invention have a high clearing point, for example, one of the compounds of the present invention, trans-4#-propyl-trans-off-dab force hydro-p-terphenyl-trans-4
-C of carboxylic acid-4''-fluorophenyl ester
-S At 194.0℃, S -N point 220.6℃,
The N-i point exhibits a liquid crystal phase over a wide temperature range of 300 DEG C. or higher, and by adding it as a component of the composition, the clearing point can be raised without increasing the viscosity of the liquid crystal composition. Moreover, the anisotropy value of the compound of the present invention is about -1-'2, but the threshold voltage and saturation voltage of the composition are
Nothing changes. It also has good stability against moisture, heat, and light pressure.

Next, a method for producing the compound of the present invention will be described. 1. First, Fedalmagnesium bromide was prepared from bromobenzene and metallic magnesium, and it was reacted with 4=(trans-4'-alkylcyclohexyl)cyclohexanone to form 4'-(
trans-4'-alkylcyclohexyl)cyclohegypne-l-autobenzene (n). Next, this was dehydrated using potassium hydrogen sulfate as a catalyst and 4'-()lans-41-alkylcyclohexyl)/chlorohexene-1
'-yrubenzene (2) is obtained and then hydrogenated using a Raney nickel catalyst to obtain trans-4'-()trans-49-alkylcyclohexyl)cyclohexylbenzene (IV). This can also be obtained by directly hydrogenating (It) using Raney nickel. Next, the compound (trans) is halogenated with iodic acid or periodic acid to give 4-()lance-4#-alkylcyclohexyl)cyclohexyl]halogenopencene (V), which is converted into cupric cyanide. By cyanating with Next, this compound (head) was hydrolyzed in an aqueous potassium hydroxide solution-diethylene glycol system to form 4-()
Trans-4'-(trans-4'-alkylcyclohexyl)cyclohexyl J benzoic acid is produced. This benzoic acid derivative was reduced with metallic sodium in isoamyl alcohol to give trans-4#-alkyl-trans-octadecahydro-■]-terphenyl-trans-4-carboxylic acid (No.).

This was converted into acid chloride with thionyl chloride, and then 4-
When a halogenophenol is reacted in pyridine, the desired trans-41-alkyl-trans-octadecahydro-p-terphenyl-trans-4-carboxylic acid,
1#/-halogenophenyl ester (1) is obtained.

The above formula is represented by the chemical formula %() () (1) (RIX in the above formula is the same as above).The compounds of the present invention will be explained in more detail with reference to Examples below.

Example 1 [Production of trans-41-furobyl-trans-octadecahydro p-terphenyl-trans-4-carboxylic acid-4'''-fluorophenyl ester O] Magnesium shavings 3.6 t (0,148 mol) 3
Place bromobenzene 23.2F (0,
A solution of 148 cells) dissolved in tetrahydrofuran
When +d is slowly added dropwise while stirring in a N2 stream while maintaining the reaction temperature at 30 to 35°C, the reaction occurs, and in 3 hours the magnesium is dissolved and becomes homogeneous, producing phenylmagne/umbromide. This was added to 4-(trans-4'-propylcyclohexyl)7chlorhexano726.29 (0
, 118 mol) in tetrahydrofuran to give 50 d
l? : Add the solution dropwise as quickly as possible while keeping the reaction temperature below 10°C. After dropping, raise the temperature to 35℃ for 30 minutes.
Stir for a minute and then add 100 ml of 3N hydrochloric acid. The reaction solution was transferred to a separating funnel and extracted 3 times with 100 tnl of n-hegetane.The combined 7 layers of n-hebutane were washed with water until the washings became neutral, and then the n-hebutane was distilled off under reduced pressure. leave The remaining oil is (4'-()lance-41-propylcyclohexyl)/chlorohexane-1'-ol]benzene, and 19f of potassium hydrogen sulfate is added thereto, followed by dehydration at 170°C for 2 hours in a N2 stream. 200sd n after cooling
- After adding hebutane, potassium hydrogen sulfate is added separately and the n-hebutane layer is washed with water using a separating funnel until the washing liquid becomes neutral. Next, n-hebutane was distilled off under reduced pressure, and the remaining oil was
-The product obtained by recrystallizing from hebutane and acetone is (4-
() lance-41-propylcyclohexyl)cyclohexen-1'-yl]benzene. Dissolve this 7.5t in 500g of ethanol and use 362g of Raney nickel catalyst.
catalytic reduction is carried out by passing hydrogen at 50° C. and normal pressure. Both raw materials and products are tracked by gas chromatography,
The reduction reaction was terminated when the raw materials disappeared, that is, after 8 hours. The amount of hydrogen absorbed at this time was 800 d. After removing the catalyst, the solvent was distilled off under reduced pressure, and the remaining crystals were recrystallized with ethanol [trans-4'-()trans-4"-
I got cyclohexyl (hexyl) cyclohexyl. Dissolve this 1.4f in 50% of acetic acid and 0.0% of pure water.
9sd, @sulfuric acid 1.0+d, iodic acid 0.20f
A mixture of 0.50 r of iodine and 0.4 d of carbon tetrachloride was refluxed at 80°C for 5 hours. The reaction solution was cooled, the precipitated crystals were separated, and the crystals were recrystallized from n-hebutane to obtain 4-[trans-4'-()trans-41-
It is flovirunclohexyl]nclohexyl]iodoben7ane (V). This one shows a liquid crystal state, and a-S
The point is l19. o'c.

The S-N point was 139.2°C, and the N-■ point was 189.2°C. This 1.22 was dissolved in N,N'-dimethylformamide 50-, and cupric chloride α63 was added.
The reaction was carried out at 0°C for 4 hours. Add n-heptane 100-
Transfer to a separatory funnel, separate the liquid with 30 thiammonia water, then wash with water, wash with 6N hydrochloric acid, and further wash with water until the washing liquid becomes neutral. The solvent was distilled off under reduced pressure and the product obtained by recrystallizing from n-hebutane was 4-(trans-41-(trans-41-propylcyclohexyl)cyclohexyl)
It is benzonitrile. The yield is 0.4f, the yield is 45cm for the cyanation reaction, and its C-S point is 731℃
, El-N point was 81.1°C, and N-■ point was 242.5°C.

The 4-[trans-4'-()lance-/Ll 7'robin-hexyl)cyclohexyl]benzonitrile Set obtained as above was co-produced with a solution of 5v of potassium hydroxide in 10-g of water. Processed into ethylene glycol 100- and heated in a flask at 200°C for 7 hours. After the reaction was completed, it was cooled to room temperature, and 6NHO150− and water 1
Add oad. Filter the precipitated crystals and wash thoroughly with water. The thus obtained 4-[trans-4'-(trans-4'-furobylcyclohexyl)cyclohequinyl]benzoic acid (■) 3f was mixed with isoamyl alcohol 150
Stir with 0* and heat to 90°C. When metallic sodium 10F is added there, a violent reaction begins. While continuing the stirring and refluxing, an additional 80% of metallic sodium was added over 3 hours. The reaction solution gradually becomes homogeneous.

After the reaction is completed, the mixture is allowed to cool to 100°C. Isoamyl alcohol is distilled off while adding water little by little. Water is 1,51
added. Add 6N hydrochloric acid to LA' to make it completely acidic, then filter the precipitate and wash well with water. , it was recrystallized from acetic acid to obtain trans-4=globy-trans-octadecahydro p-terphenyl-trans-4-carboxylic acid (■
) was obtained. Yield 1.・N2. Yield: 63 cm. This material also exhibits liquid crystallinity, with an a-S point of approximately 170°C and an 8-N point of 28°C.
2°C, N-■ lighting 290-300°C (accompanied by decomposition).

0.52 of the carboxylic acid (■) thus prepared is heated to 80 DEG C. with thionyl chloride 10.

The reaction solution became homogeneous in 2 hours, and the reaction was continued for an additional 1.5 hours. Excess thionyl chloride is distilled off under reduced pressure. The oil that remains is the acid chloride. Separately, acid chloride was added to 4-fluorophenol (0.52 g) dissolved in pyridine (20 g), 100 g of toluene (AfK) was added, and the mixture was allowed to stand overnight.

In a separatory funnel, the toluene layer is washed first with 6N hydrochloric acid, then with 2N caustic soda solution, and finally with water until neutral. After drying it over anhydrous sodium sulfate, the toluene layer was distilled off under reduced pressure.

The precipitated crystals were recrystallized from ethanol and acetone to obtain the desired trans-4'-propyl-trans-octadecahydro-p-terphenyl-trans-4-carvone mg//-fluorophenyl ester. Ta. Yield o, 4y, yield 62%, its a-S point is 94
．． 0℃, 8-5 point is 220.6℃, N-1 point is 300℃
That was it.

In a similar manner, 4-[trans-4'-() lance-4'
If 4-[trans-4'-()trans-41-alkylcyclohexyl)cyclohexanone with another alkyl group is used instead of cyclohexanone (furobylcyclohexyl), the compound is also obtained.

trans-octadecahydro-p-terphenyl-trans-4-carboxylic acid-4''-fluorophenyl ester, trans-4''-methyl-trans-octadecahydro p-fulfhenyl-trans-4-carvone [-4”
'-fluorophenyl ester, trans-41-ethyl-trans-octatecahydro-p-terphenyl-trans-4-carboxylic acid 4//7-fluorophenyl ester, trans-41-butyl-trans-octadecahydro -p-terphenyl-trans-4-carboxylic acid-4'-fluorophenyl ester, trans-
41-Benchyltrans-octatecahydro p-terphenyl-trans-4-carboxylic acid 4W'-fluorophenyl ester, trans-41-hexyl-trans-octadecahydro-p-terphenyl-trans-4-carboxylic acid a/-fluorophenyl ester, trans-4'-heptyl-trans-octadecahydro-p-terphenyl-trans-4-carboxylic acid-4"
'-Fluorophenyl ester, trans-41-octyl-trans-octadecahydro-p-terphenyl-trans-4-carvone v 4m-fluorophether ester, trans-41-nonyl-trans-octadecahydro-p- Terphenyl-trans-4-carboxylic acid-4'''-fluorophenyl ester, trans-4'-decyl-trans-ocdadecahydro p-terphenyl-trans-4-carboxylic acid m-41//-fluorophenyl ester , trans-ocdadecahydro p-terphenyl-trans-4-carboxylic acid 41'
l j lorophenyl ester, trans-4'-methyl-trans-octadecahydro-p-terphenyl-trans-4-carboxylic acid-4"
'-Chlorophenyl ester, trans-4'-ethyl-trans-octadecahydro-p-terphenyl-trans-4-sulfo7ic acid-4"-chlorophenyl ester, trans-41-propyl-trans-octadecahydro p -terphenyl-trans-4-carvone M
-4M-chlorophenyl ester, aS point 106.0
℃, S-N point is 158.1℃, N-1 point is 296.6℃
.

trans-41-butyl-trans-octadecahydro-p-terphenyl-trans-4-carboxylic acid-4''
'-Chlorophenyl ester, trans-41-pentyl-trans-octatecahydro p-terphenyl-
trans-4=carboxylic acid-4/#-chlorophenyl ester, trans-4I-hexyl-trans-octadecahydro-p-5-ruphenyl-trans-4-carboxylic acid-4#/-chlorophenyl ester, trans-4
'-Hebutyl-thora/no-octatecahydro p-terphenyl-trans-4-carboxylic acid-4''-chlorophenyl ester, trans-41-octyl-thora/no-octatecahydro p-terphenyl-trans-4
-carboxylic acid 47//-chlorophenyl ester, trans-4#-nonyl-trans-octadecahydro-p
-terphenyl-trans-4-carboxylic acid 4/J/-
Chlo-cophenyl ester, trans-42-decyl-
Trans-octadecahydro-p-terphenyl-trans-4-carboxylic acid-4''-chlorophenyl ester, Example 2 (Application example) trans-4-propyl-(4'-cyanophenyl)
Cyclohexane 28% trans-4-pentyl-(4'-cyanophenyl)cyclohexane 42% trans-4-hebutyl-(4'-cyanophenyl)/
The nematic clearing point of a liquid crystal composition having a composition of 30% chlorohexane is 52°C. This liquid crystal composition was sealed in a TN cell (twisted nematic cell) with a cell thickness of 10 μm, and the operating threshold voltage was 1.53V and the saturation voltage was 2.12V. The viscosity was 23 cp at 20°C.

Trans-4 prepared in the example was added to 97 parts of this liquid crystal composition.
The nematic composition containing 3 parts of '-propyl-trans-octadecahydro-p-terphenyl-trans-4-carboxylic acid a/#-fluorophenyl ester has a nematic clearing point of 60°C and a threshold voltage of 1 .50V, the saturation voltage was 2.09V; and the viscosity was 23V at 20°C.
It was cp.

that's all

Claims (2)

[Claims] (1) trans-41-alkyl-trans-octadecahydro- represented by the general formula (in the above formula, R represents hydrogen or an argyl group having 1 to 10 carbon atoms, and represents either F or C1) p-terphenyl-to-5-4-carboxylic acid-1,1 cochenophenyl ester. (2) trans-41-alkyl-trans-octadecahyde represented by the general formula (in the above formula, R represents hydrogen or an alkyl group having 1 to 10 carbon atoms, and X represents either F or 07!) A liquid crystal composition containing at least one type of draw p-terphenyl-trans-4-carboxylic acid-4''-halogenophenyl ester.