JPS6229555A - Dicyclohexylmethane derivative - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula (R<1> and R<2> are 1-10C aliphatic alkyl or alkoxy; l, m and n are 0 or 1). EXAMPLE:Ethyl trans-4-(trans-4-n-propylenecyclohexylmethyl)cyclohexanec ar boxyla te. USE:A liquid crystal composition having effect on reduction in threshold voltage and saturation voltage and improvement in visibility angle characteristics by mixing with another liquid crystal composition. PREPARATION:4,4'-Diphenylmethanedicarboxylic acid expressed by formula II is catalytically reduced and thermally isomerized to trans,trans-4,4'- dicyclohexylmethanedicarboxylic acid expressed by formula III, which is then reacted with an alcohol or phenol by the conventional method to afford the aimed compound expressed by formula I (m is 1).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a synchronohexylmethane derivative, which is a novel liquid crystal compound, and a liquid crystal composition containing the same.

The synchhexylmethane derivatives provided by the present invention can be used as a component of liquid crystal compositions.

[Conventional technology]

In recent years, liquid crystal displays (LCDs) have been widely used as a display method.

Liquid crystal for liquid crystal displays is stable against heat, light, moisture, etc., exhibits a liquid crystal phase over a wide temperature range centered around room temperature, has appropriate threshold voltage and saturation voltage, and has a voltage-transmittance ratio. Steepness of characteristics, wide viewing angle 9, etc. are required. Conventionally,
Liquid crystal compositions obtained by appropriately mixing various liquid crystal compounds and non-liquid crystal compounds are used.

[The problem that the invention attempts to solve]

However, there is still room for improvement in terms of threshold voltage, saturation voltage, steepness of voltage-transmittance characteristics, wide viewing angle υ, etc.

[Failure to solve the problem]

An object of the present invention is to provide a novel liquid crystal compound that can improve these problems and a liquid crystal composition containing the liquid crystal compound.

The present invention is based on the general formula [wherein R1 and R2 represent an aliphatic alkyl group having 1 to 10 carbon atoms or an alkoxy group, and R1 and R2 may be the same or different. Moreover, l, m and n represent O or 1. ] This relates to the socyclohexynormethane conductor represented by

The present invention also relates to a liquid crystal composition characterized by containing at least one isocyclohexylmethane derivative represented by the general formula (1). The expressed socyclopequinlemethane derivatives often exhibit liquid crystal properties even when used alone, are colorless, thermally, photo- and chemically stable, and have good compatibility with other liquid crystal compounds. Depending on the application, it can be mixed with other liquid crystal compounds or non-liquid crystal compounds and used as a liquid crystal composition.

In particular, when the nocyclohexylmethane derivative represented by the general formula (1) provided by the present invention is mixed with other liquid crystal compounds and used as a liquid crystal composition, when the isocyclohexylmethane derivative (1) is not mixed. It exhibits characteristics such as lower threshold voltage, lower saturation voltage, and wider viewing angle.

In general formula (1), R1 and R2 are methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-hegtyl, n-octyl, n-nonyl and n-decyl, and C1-10 aliphatic alkyl group including these various isomers; methoxy, ethoxy, n
-Glopoxy, n-butoxy, n-pentyloxy, n
-hexyloxy, n-hebutyloxy, n-octyloxy, n-nonyloxy, and n-decyloxy,
It is an aliphatic alkoxy group having 1 to 1° of carbon atoms, including various isomers thereof. Note that R1 and R2 may be the same or different.

As the isocyclohexylmethane derivative of general formula (1),
For example, the following compounds can be mentioned.

trans-4-(trans-4-n-propylcyclohexylmethyl)ethyl cyclohexanecarboxylate; trans-4-(trans-4-n-propylcyclohexylmethyl)n-butyl cyclohexanecarboxylate; trans-4-()trans- n-67thyl 4-〇-glopylcyclohexolmethyl)cyclohexanecarboxylate; trans-4-()trans-4-nf lopylcyclohexyl/l/butyl)n-heptylcyclohexanecarboxylate; trans-4 -(trans-4-n-propylcyclohexylmethyl)n-decyl cyclohexanecarboxylate; trans-4-(trans-4-ethylcyclohexylmethyl)n-propylcyclohexanecarboxylate; trans-4-(trans-4- n-hexyl cyclohexanecarboxylate; trans-4-()trans-4-pentylcyclohexylmethyl) cyclohexanecarboxylate; trans-4-(lance-4-hexylcyclohexylmethyl)cyclohexane Carboxylic acid, n-propyl; trans-4-(trans-4-hexylcyclo,
n-R-methyl) cyclohexanecarboxylate; trans-4-C trans-4-hexylcyclohexylmethyl) n-hedityl cyclohexanecarboxylate; trans-4: (trans-4-hebutylcyclohexylmethyl)cyclohexanecaldene Ethyl acid; trans-4-()trans-4-hebutylcyclohexylmethyl)cyclohexanecarboxylic acid n-butyl; trans-
n-hexyl 4-(1-trans-4-hegetylcyclohexylmethyl)cyclohexanoic acid; trans-
4-(1-lance-4-hebutylcyclohexylmethyl)cyclohexanecal? trans-4-(trans-4-n-propylcyclohexylmethyl)cyclohexanecarboxylic acid p-methylphenyl ester; trans-4-(trans-4-n-propylcyclohexylmethyl)cyclohexanecarboxylic acid p-ethyl Phenyl ester; trans-4-(trans-4
-n-f lobylcyclohexylmethyl)cyclohexanecarboxylic acid p-n-globylphenyl ester; trans-4-(trans-4-n-propylcyclohexylmethyl)cyclohexanecaldenate p-n-butylsuenyl ester; trans- 4-(trans-4-n-propylcyclohexylmethyl)cyclohexanecalgenic acid p-nl tylphenyl ester: trans-4-(
trans-4-n-propylcyclohexylmethyl)/
Clohexanecarboxylic acid p-n-hebutylphenyl ester; trans-4-(trans-4-n-propylcyclohexylmethyl)cyclohexanecaldenic acid p-n
-decylphenyl ester; trans-4-()trans-4-n-propylcyclohexylmethyl)cyclohexanecarboxylic acid p-n-hexylphenyl ester;
trans-4-(trans-4-n-propylcyclohexylmethyl)cyclohexanecarboxylic acid p-n-octylphenyl ester; trans-4-(trans-4
-n-propylcyclohexylmethyl)cyclohexanecarboxylic acid p-methoxyphenyl ester; trans-
4=(trans-4-n-7'robylcyclohexylmethyl)cyclohexanecarboxylic acid p-ethoxyphenyl ester; trans-4-()trans-4-n-7'robylcyclohexylmethyl)cyclohexanecarboxylic acid p-n -butoxyphenyl ester; trans-4-(
trans-4-n-propylcyclohexylmethyl)cyclohexanecarboxylic acid p-n-butoxyphenyl ester; trans-4-()trans-4-n-propylcyclohexylmethyl)cyclohexanecaldenic acid p-n
-ethyloxyphenyl ester; trans-4-(
) trans-4-n-propylcyclohexylmethyl) cyclohexanecaldene p-n-hegetyloxyphenyl ester;
n-pentylcyclohexylmethyl)cyclohexanecarboxylic acid p-ethoxyphenyl ester; trans-4
-(trans-4-n-methylcyclohexylmethyl)cyclohexanecarboxylic acid p-n-butoxyphenyl ester; trans-4-(trans-4-n-pentylcyclohexylmethyl)cyclohexanecarboxylic acid p
-n-pentyloxyphenyl ester; trans-
4-(trans-4-n-pentylcyclohexylmethyl)cyclohexanecarboxylic acid p-n-hexyloxyphenyl ester; trans-4-(trans-4-
n-heptylcyclohexylmethyl)cyclohexanecarboxylic acid p-methoxyphenyl ester; trans-4
-(trans-4-n-heptylcyclohexylmethyl)cyclohexanecarboxylic acid p-ethoxyphenyl ester;
-Globoxyphenyl ester; trans-4-(trans-4-n-heptylcyclohexylmethyl)cyclohexanecarboxylic acid p-n-pentyloxyphenyl ester; trans-4-(trans-4-n-heptylcyclohexylmethyl)cyclohexane carboxylic acid p
-ethylphenyl ester; trans-4-()trans-4-n-R methylcyclohexylmethyl)cyclohexanecarboxylic acid p-ethylphenyl ester; trans-4-(trans-4-n-hexylcyclohexylmethyl)so Chlohexanecal d? trans-4-(trans-4-n-butylcyclohexylmethyl)cyclohexanecarboxylic acid
-Ay-ruphenyl ene ter; trannu-4-(trans-4-n-butylcyclohexylmethyl)cyclohexanecargenic acid p-ethyl phenyl ene tel; trans, trans-4,4'-socyclohexylmethanesocarboxylic acid Noethyl; trans.

trans-4,4'-dicyclohexylmethanocarpic acid n-butyl; trans, trans-4,4'
-n-enthyl knocklohexylmethanesocarboxylic acid; trans, trans-4,4'-notuclohexylmethanedicarboxylic acid n-hegtyl; trans, trans-4,4'-dicyclohexylmethanenocarboxylate Trans, trans-4,4'-socyclohexylmethanocargenic acid p-n-butylphenyl ester; trans, trans-4,4'-socyclohexylmethanocargenic acid p#) Quinphenyl ester; trans, trans-4
,4'-ycyclohexylmethanedicarboxylic acid p-
Ethoxyphenyl ether; trans, trans-4,
4'-Socyclohexylmethanesocardenoic acid p-n
-Glopoxyphenyl ester; trans, trans-
4,4'-dicyclohegylmethaneducaldic acid nop
-n-butoxyphenyl ester; trans, trans-4,4'-nocyclohexylmethanesocargenic acid p-n-butoxyphenyl ester; trans,
trans-4,4'-notuclohexylmethanesocal,
trans.

trans-4,4'-nocyclohexylmethanesoca/l
'Menic acid tho p-n-octyloxyphenyl ester.

The socyclohexylmethane derivative having the general formula (1"l) can be produced, for example, by the following method.

(1) When l = rn = O ↓ 0 Trans-4-alkyl (or alkoxy) cyclohexanecarboxylic acid (a) is converted into a carboxylic acid chloride, and then reacted with benzene in the presence of aluminum chloride,
trans-4-alkyl(matahaalkoxy)cyclohexyl phenyl ketone (obtained by reducing bl (obtained by acetylation of cl (obtaining small). Then, oxidation with hypobromite soda, 4 -C-trans-4-alkyl(t-alkoxy)cyclohexynylmethyl]benzoic acid fel is obtained.After catalytic reduction of te13, thermal isomerization is performed to obtain cyclohexanecarboxylic acid (fl).(f) is obtained by a conventional method. The target compound (I) can be obtained by enuteration.

(If R>m=1, HOOC÷CHzOC00H(g1 4.4'-diphenylmethanesocargonic acid (g) After total catalytic reduction, it is thermally isomerized to Trannu, Trannu 4.4'-
Dicyclohexylmethanesocaldic acid (h) is obtained. (
The desired ester compound (I) can be obtained by reacting h) with alcohol or phenol in a conventional manner.

〔Example〕

The present invention will be explained in more detail by showing Examples and Usage Examples below.

Example 1 Production of n-pentyl trans-4-(trans-4-n-propylcyclohexylmethyl)cyclohexanecarboxylate (Rf of general formula (1) = n-propyl, R2 =
n-pentyl, l=m=n=o): (1)) Production of 7-nu-4-n-7'robin-hexyl phenyl ketone (R1=n-propyl of compound (b)).

Thionyl chloride (50 ml) was added to trans-4-n-7'rovylcyclohexanecarbic acid (26,1), heated under reflux for 1 hr, and then unreacted thionyl chloride was distilled off under reduced pressure. Benzene solution (1
5zt) was added dropwise to an AlCl33-benzene suspension while cooling with ice water. After standing at room temperature overnight, the mixture was poured into ice water and extracted with benzene and ether.

The extract was washed with diluted hydrochloric acid and further washed with water. After drying, it was concentrated and subjected to silica gel column chromatography K or ff to obtain 24.0 y of white crystals of ) lance-4-n-propylcyclohexyl phenyl ketone (IR (KBr
):2900, 2830, 1660, 1585
.

1435.1365, 1255, 1215, 1195,
945°690(7)].

+2+ Production of trans-4-n-propylcyclohexylphenylmethane (Rt of compound (C) = n-propyl).

trans-4-n-f lovylcyclohexylphenyl ketone c 24. KOH (27,21>, hydrazino hydrate (26,15K) and soethylene glycol (600K) were added to Oy) and heated under reflux for 7 hours. After cooling, the solution was added to 3.5g of water. The chloroform extract was dried, concentrated, subjected to silica gel column chromatography, and extracted with chloroform.
4-n-progylcyclohexylphenylmethane (colorless liquid) 20.81 was obtained (IR (KBr): 2900
, 2830, 1440, 730, 685].

+3) Production of 4-(trans-4-n-propylcyclohexylmethyl)acetophenone (R1 of compound (d)
= n-propyl).

Methylene chloride (80a) of Al1C113(15,3y)
! ) Add acetyl chloride < 9.4 to the suspension under cooling with ice water.
y) was added dropwise. Then, trans-4-n-propylcyclohexylphenylmethane (20,6y) was added dropwise. After stirring in ice water for 1 hr and at room temperature for 5.5 hr,
The mixture was poured into 00j' ice and extracted with methylene chloride. The extract was washed with saturated brine, dried, and concentrated. The concentrated solution was distilled under reduced pressure to obtain 4-(trans-4-n-propylcyclohexylmethyl)acetophenone (bp, 152~
156°C10,5aHy) CIR obtained 22.91
(KBr): 2900, 2830, 1670°160
0.1350,1255f”lfi].

(4) Production of 4-(trans-4-n-globylcyclohexylmethyl)benzoic acid (R1=n- of compound (e)
propyl).

Under ice water cooling, NaOH (50,5F) - water (280+
Bromine (19, Om/) was added dropwise to t). Then 4-
(trans-4-n-propylcyclohexylmethyl)
Acetophenone (22,9y)-soxane (130+
++t) was added dropwise. After stirring at room temperature for 3 hr, Na
H3O3(181)-water (190g+/) was added dropwise.

Then 12N HC/? (65 m/) was added dropwise to make it acidic. After stirring at room temperature for 0.5 hr, remove the insoluble matter.
22.9 y of colorless crystals of 4-()lanth-4-n-propylcyclohexylmethyl)benzoic acid were obtained (IR (KBr): 2900, 2830, 16
70, 1600.

1420.1315,1285,1175,940,7
45°54.5CM-1).

(5) Production of trans-4-(trans-4-n-propylcyclohexylmethyl)cyclohexanecarboxylic acid (R1 of compound (f) = n-propyl).

4-(trans-4-n-f lobylcyclohexylmethyl)benzoic acid <22.6 y), Pt02(0,2
5y) and acetic acid (80 ml) were placed in an autoclave (with glass container, 300 ml) ILC, and hydrogen (5y
0 kg/d) and heated and shaken at 70 to 90°C for 1.5 hours. After cooling, acetic acid (200we) and acetone (
400xi) was added, and the insoluble matter was filtered out. The crystals obtained by concentrating the solution were washed with water and dried. Next, this crystal was heated in an oil bath at 220°C under a nitrogen stream for 24 hours, and then recrystallized with ethanol.
5.8y of -n-propyrunclohexynormethyl)cyclohexanecarboxylic acid was obtained. After heating the FE liquid concentrate in an oil bath at 220'C under a nitrogen stream for 14.5 hours,
After recrystallizing with ethanol, an additional 4.5y was obtained. CIR (KBr): 2900.

28'30,1685,1445.1235'l'! −
” ].

(Production of n-pentyl C6 trans-4-(trans-4-n-norobylcyclohexylmethyl)cyclohexanecaldate (R'' in general formula (I) = n-propyl,
R2=n-pentyl, A=m=n=O).

trans-4-(trans-4-n-propylcyclohexylmethyl)cyclohexanecarbic acid c O,99
Thionyl chloride (10 doors/y) was added to the mixture and heated under reflux for 1 hour, and then unreacted thionyl chloride was distilled off under reduced pressure. Add n-pentanol and heat to 1.5 at 150°C.
Heated for hr. Benzene was added, washed with water, dried and concentrated. After purification by solitary column chromatography, it was recrystallized from ethanol (dry ice-ethanol cooling) to obtain trans-4-(trans-4-n).
-Globylcyclohexylmethyl) cyclohexanecarbic acid n-ethyl (colorless liquid) 0.45F was obtained Cm
p,: 10.0°C; IR (KBr): 2910,2
840゜1730.1445, 1170.1145〒-
'; NMR (C'DC13): 0.87 (3H, t
, J = 7.1 Hz), 0.90 C3H.

t, J = 7. IHz), 0.98-1.84
(29H, m), 1.84-2.01 (2H, m)
, 2.21 (l H,t.

t, , J=12.2Hz, J=3.7Hz),
4.04 (2H.

t, J = 6.6Hz) I) pm].

Examples 2 to 8 Other dicyclohexylmethane derivatives were synthesized according to the synthesis method described in Example 1 (6). Typical examples are shown in Table 1 (the derivative obtained in Example 1 is also shown).

Example 9 Production of di-n-pentyl trans,trans-4,4'-socyclohexylmethanesocarboxylate (general formula (I)
R1= R2= n-pentyl, 1=n=o, m=x
).

(1) Trannu, Trannu 4,4'-noklohexylmethandical? Production of phosphoric acid (h).

4.4'-sophenylmethanesocarboxylic acid, (5')(
21,0y) to NaOH(8,Oy)-water (80at
), added -5'ARu-C@ medium (6,9y''), and catalytic reduction (H2) initial pressure 60V4/mu, 70℃, 3h.
·)did. After the reaction, the catalyst was separated and the lachrymal fluid was acidified with hydrochloric acid to obtain 20.7 y of white crystals of 4,4'-nocyclohexylmethanesocarboxylic acid (after enuterization with diazomethane, the results of ganucloanalysis showed that cissis Body 51, Nnu trance body 40%,) Rannu trance body 9 Chi).

This mixture was heated at 200 to 220°C under a nitrogen stream for 47 hours.
After heating, the mixture was recrystallized from ethanol to obtain 8.8y of white crystals of tranne, tran 7, -4, 4'-knock hexylmethane ducaldic acid. The mother liquor concentrate was heated again at 200 to 220°C for 8 hours under a nitrogen stream, and then recrystallized from ethanol to further obtain 4.57 trans, trannu 4.4'-y cyclohexylmethanesicaltinic acid (mp
,: 270°C; IR (KBr) 2910.2840
,1680,1440,1415,1305°1255
．． 1215.1195ff-' ].

[=
Ox, : α, disease: = 1) Trannu, Trannu 4, 4'
-Socyclohexylmethanocarboxylic acid C1,01y
) was added with thionyl chloride (10 doors/), heated under reflux for 1 hour, and unreacted thionyl chloride was distilled off under reduced pressure. n-Pentanol CO, 70y) was added and heated at 150°C for 7J[] for 1 hour. Benzene (150
m/) and n-hexane (50e+/) were added, and the organic layer was washed with water, dried, and concentrated. The concentrate was purified by silica gel column chromatography and then recrystallized from n-hexane to obtain white crystals of di-n-pentyl trans,trans-4,4'-socyclohexylmethanesocarpine 51y. (mp,: 39.0-40.0°C;
IR (KBr): 2920, 2850, 1725°1445.1315, 1235, 1170, 1115.
1005 Tan-1; NMR (CD(J?3) 0.91
(6H, t, J = 6.42.04 (4H,
m), 2.21 (2H,t,t.

J = 1.2Hz, J = 3.4Hz), 4.04
(4H, t.

J = 6.8Hz) ppm: ].

Examples 10 to 14 Other dicyclohexylmethane derivatives were synthesized according to the synthesis method described in Example 9. Typical examples are shown in Table 1 (the derivative obtained in Example 9 is also shown).

Usage Example 1 Threshold voltage from the normal direction (0 direction) of the cell surface when a commercially available liquid crystal composition (manufactured by Merck & Co., Ltd.: ZL11565; trade name) is sealed in a TN cell with a cell thickness of 10 μm [VC90
%, O)) is 2.34 V, the saturation voltage [V(10chi, 0
)] was 3.26 V, and the threshold voltage [v (90, 40)] from the 40° direction from the normal was 1.81 V. That is, viewing angle dependence (V (90%, 0)/V
(90chi, 40)) was 1.29.

Trans-4- (trans-4-
(90%, O) = 2.09V of the composition obtained by dissolving 10 wtL% of n-pentyl (n-propylcyclohexylmethyl)cyclohexanecarboxylate.

■(10chi, O) = 2.92 V, V C9
0%, 40) = 1.66 V. Therefore,
Visual angle dependence (V(90%, 0°)/V(90%, 40°)
)] was 1.26.

Use Examples 2 to 4 In the same manner as in Use Example 1, various nocyclohexylmethane derivatives of the present invention were added to liquid crystal composition ZL11565.
A composition obtained by dissolving wt% was also measured. The results are shown in Table 2. (The results of Usage Example 1 are also described).

〔Effect of the invention〕

Many of the socyclohexylmethane derivatives provided by the present invention exhibit liquid crystal properties, and when mixed with other liquid crystal compositions, they have the effect of lowering threshold voltage and saturation voltage and improving viewing angle characteristics. There is.

Claims (2)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 and R^2 represent an aliphatic alkyl group or alkoxy group having 1 to 10 carbon atoms;
may be the same or different. Further, l, m and n represent 0 or 1. ] Synchronohexylmethane derivative. (2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 and R^2 represent an aliphatic alkyl group or alkoxy group having 1 to 10 carbon atoms,
may be the same or different. Further, l, m and n represent 0 or 1. A liquid crystal composition comprising at least one dicyclohexylmethane derivative represented by the following.