JP3402678B2 - Cyclohexane dimethyl derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to an electro-optical display material.
And useful cyclohexanedimethyl derivatives,
Wide liquid crystal temperature by mixing with the liquid crystal material
And has a small anisotropy (Δn) of the refractive index of the liquid crystal material.
The NI point can be raised while maintaining
It relates to a chlorohexanedimethyl derivative. [0002] BACKGROUND OF THE INVENTION Liquid Crystal Materials
The material properties required are water, light, heat stable,
Low voltage, in a liquid crystal state over a wide temperature range including room temperature
It is desirable. However, in general, a single liquid crystal
It is difficult to meet all the required performances with
By mixing liquid crystal compounds and compounds other than liquid crystal,
It has been used as a composition with better performance. Liquid crystal
The compound starts from the low-temperature side in the crystalline phase (C),
Nematic phase (N) via tick phase (S), higher
Shows isotropic liquid phase (I) on the warm side, where smectic
Phase (S) and nematic phase (N)
You. Liquid crystal material containing liquid crystal compound is wide including room temperature
It is necessary to show the liquid crystal phase in the temperature range.
The wide range allows for good display in a wide range of operating environments.
Indices are obtained. In particular, NI
Since the dot has a positive effect on the display on the high temperature side,
Liquid crystal material with high NI point when used in different environments
Is required. Further, the anisotropy of the refractive index of a liquid crystal material (hereinafter, referred to as the anisotropy)
Is simply "Δn") is the visual characteristic of the liquid crystal display
And the smaller the Δn, the better the visual characteristics.
Therefore, the liquid crystal material used must maintain a small Δn.
is there. For this reason, a nematic liquid crystal material is mixed with
To increase the NI point while widening the liquid crystal temperature range,
Also, a compound that does not increase Δn has been required. As a liquid crystal material having a high NI point, for example,
For example, JP-A-54-157541 and JP-A-56-1
No. 58751, JP-A-56-161352
, JP-A-57-18649, JP-A-57-95
933, JP 57-176943, JP
JP-A-58-10532, JP-A-58-124744
JP, JP-A-3-31248, JP-T-Hei 3-50
No. 0892, etc., alkylcyclohexylmethoxy group
Have been proposed. In these compounds
Has a high NI point and can be mixed with nematic liquid crystal materials.
In some cases, the NI point increases, but the NI point increases.
As the CI point becomes higher, the liquid crystal range temperature becomes narrower.
Therefore, there is a disadvantage that the characteristics on the low temperature side are deteriorated. Accordingly, an object of the present invention is to provide a nematic liquid crystal.
By mixing with the material, it has a wide liquid crystal temperature range,
The anisotropy (Δn) of the refractive index of the liquid crystal material is kept small.
Also, cyclohexane capable of increasing the NI point
It is to provide a dimethyl derivative. [0007] Means for Solving the Problems The present inventors have achieved the above object.
As a result of various studies in order to achieve
Mixing a xan dimethyl derivative with a nematic liquid crystal material
With a wide liquid crystal temperature range and a high NI point,
In addition, Δn increases when mixed with a liquid crystal material.
It was found that it was not possible. The present invention has been made based on the above findings.
In the formula [2] (same as the above [1])
Provide cyclohexanedimethyl derivative represented by (I)
Is what you do. [0009] Embedded image Hereinafter, the cyclohexanedimethyl derivative of the present invention will be described.
The conductor will be described in detail. In the above general formula (I), R₁And R_TwoRepresented by
As the alkyl group having 1 to 12 carbon atoms, for example, methyl
, Ethyl, n-propyl, isopropyl, n-butyl
, Isobutyl, sec-butyl, tert-butyl, n-pen
Butyl, 2-methylbutyl, 3-methylbutyl, n-hexyl
Syl, isohexyl, n-heptyl, isoheptyl, n
-Octyl, 2-ethylhexyl, isooctyl, 2-
Octyl, n-nonyl, isononyl, n-decyl, iso
Decyl, n-undecyl, isoundecyl, n-dodecy
And isododecyl. Also, a halogen atom represented by X and Y
For example, chlorine, fluorine, bromine and the like can be mentioned. Accordingly, the cyclohexanedimethyl of the present invention
As the derivatives, for example, the following [Chemical Formula 3] to [Chemical Formula 20]
Compound No. 1 to No. 18 and the like. [0014] Embedded image [0015] Embedded image [0016] Embedded image [0017] Embedded image [0018] Embedded image [0019] Embedded image [0020] Embedded image [0021] Embedded image [0022] Embedded image [0023] Embedded image [0024] Embedded image [0025] Embedded image[0026] Embedded image [0027] Embedded image [0028] Embedded image [0029] Embedded image [0030] Embedded image [0031] Embedded image The cyclohexanedimethyl derivative of the present invention
For example, 1,4-cyclohexanedimethanol
Using alkali metal hydride and alkyl halide
Alkyl etherification to give 4-alkoxymethylcyclohexyl
Synthesis of silmethanol
Etherification is carried out by a conventional method.
It can be manufactured by making The cyclohexanedimethyl derivative of the present invention
Is mixed with a well-known liquid crystal material (base liquid crystal),
The anisotropy (Δn) of the refractive index of the liquid crystal material is not changed.
The NI point can be raised. Examples of the compound constituting the mother liquid crystal are as follows.
For example, a compound shown in the following [Chemical formula 21] can be mentioned.
Liquid crystals are usually used by mixing several or more of these compounds.
It is what is done. [0035] Embedded imageThe cyclohexanedimethyl derivative of the present invention
The compounding amount is preferably based on 100 parts by weight of the mother liquid crystal.
Is 1 to 30 parts by weight. [0037] EXAMPLES The method for producing the compound of the present invention is described below by way of Examples.
And properties will be described in more detail. However, the present invention
Is not limited in any way by these examples.
No. Example 1: trans-4-n-propyl
Clohexanecarboxylic acid-trans-4- (4'-meth
(Xymethylcyclohexylmethoxy) phenyl ester
(Synthesis of Compound No. 1 of the above Chemical Formula 3) (1) trans-4-methoxymethylcyclohexylme
Synthesis of Tanol 65.5 g of sodium hydride (55% oily) was added to N, N '
-Dispersed in 11 g of dimethylformamide,
1,4-cyclohexanedimethanol 259.6 g
Was dissolved in 500 ml of N, N'-dimethylformamide.
The solution was added dropwise. After stirring at room temperature for 3 hours,
Left overnight. After that, methyl iodide 2
12.9 g of N, N'-dimethylformamide 100 m
solution was added dropwise and stirred at room temperature for 4 hours
After that, the precipitate was separated by filtration. After removing the solvent from the filtrate, add 1 liter of water.
Toluene was added and extracted with ethyl acetate. Drying, solvent removal
Thereafter, the product was developed with ethyl acetate / n-hexane (1/2).
Perform silica gel column treatment as an open solvent,
Trans-4-methoxymethylcyclohexyl methanol
122.2 g (51% yield) were obtained. (2) trans-1-methoxymethyl-4
-(4'-acetoxyphenoxy) methylcyclohexa
Synthesis The trans-4-methoxymethyl compound obtained in the above (1)
Clohexyl methanol 33.5 g, hydroquinone mono
25.9 g of acetate and 5 of triphenylphosphine
2.5 g was dissolved in 300 ml of dry diethyl ether.
Was. 40.4 g of diisopropyl azodicarboxylate
And stirred at room temperature for 4 hours.
The phosphine oxide was filtered off. Desolvate the filtrate and generate
Using ethyl acetate / n-hexane (2/8) as a developing solvent
And silica gel column treatment.
-1-methoxymethyl-4- (4'-acetoxypheno
Xy) 41.2 g of methylcyclohexane (83% yield)
I got (3) trans-4- (4'-methoxymeth
Synthesis of tylcyclohexyl) methoxyphenol Trans-1-methoxymethyl- obtained in the above (2)
4- (4'-acetoxyphenoxy) methylcyclohex
41.2 g of sun is 230 ml of ethanol and 50 ml of water
Of 85% potassium hydroxide 1
Add 4.0 g, heat to 75 ° C, and stir under reflux for 1 hour
did. After cooling, pour the reaction solution into 500 ml of diluted hydrochloric acid.
And the precipitate was filtered. Then precipitate until the washings are neutral.
The product is washed with water to obtain the desired product, trans-4- (4'-methoxy).
Cimethylcyclohexyl) methoxyphenol 34.0
g (yield 96%, melting point 80 ° C.). (4) trans-4-n-propylcyclo
Hexanecarboxylic acid-trans-4- (4'-methoxy
Methylcyclohexylmethoxy) phenyl ester
Success The trans-4- (4'-methoxy) obtained in the above (3)
27.9 g of methylcyclohexylmethoxy) phenol
And trans-4-n-propylcyclohexanecarbo
Dissolve 20.6 g of acid in 270 ml of methylene chloride.
Here, N, N'-dicyclohexylcarbodiimide 25.
A solution of 0 g dissolved in 30 ml of methylene chloride was added dropwise.
Was. After stirring at room temperature for 3 hours, the precipitated N, N'-dicyclo
Hexyl urea was filtered off. After removing the solvent from the filtrate, the product is
Ethyl acetate / n-hexane (2/8) as a developing solvent
Perform Ricagel column treatment, then reconstitute with methanol
The crystals were crystallized to obtain 35.6 g (80% yield) of white crystals.
Was. The result of infrared spectroscopy analysis of the obtained white crystal is as follows:
It is as shown below, confirming that the white crystal is the target product
did. 2920cm^-1, 2850cm^-1, 1750cm^-1, 1
500cm^-1, 1460cm^-1, 1440cm^-1, 12
40cm^-1, 1190cm^-1, 1150cm^-1, 112
0cm^-1, 1040cm^-1, 890cm^-1, 830cm
^-1 The phase transition temperature of the obtained target product is as follows:
Where the NI point is high and the liquid crystal temperature range is
It had a remarkably broad characteristic of 76 ° C. CS point (82 ° C), SN point (95 ° C), NI point
(158 ° C) On the other hand, compound No. 1
Has the same structure except that the
As shown below, a comparative compound of the following [Chemical Formula 22]
Although the NI point is high, the liquid crystal temperature range is only 54 ° C.
It was only inferior as a crystalline material. [0045] Embedded image Example 2: trans-4-n-butylcycl
Rohexanecarboxylic acid-trans-4- (4'-methoxy)
Cimethylcyclohexylmethoxy) phenyl ester
(Synthesis of Compound No. 2 of the above Chemical Formula 4) The trans-4- (4'-meth) obtained in (3) of Example 1 was used.
5. Toximethylcyclohexylmethoxy) phenol
0 g and trans-4-n-butylcyclohexylcal
Dissolve 4.9 g of boric acid in 60 ml of methylene chloride.
5.5 g of N, N'-dicyclohexylcarbodiimide
Was dissolved in 6 ml of methylene chloride. room temperature
After stirring for 3 hours with N, N'-dicyclohexyl
Urea was filtered off. After removing the solvent from the filtrate, the product was extracted with ethyl acetate.
/ N-hexane (2/8) as a developing solvent, silica gel
Perform column treatment, then recrystallize with methanol.
5.6 g (56% yield) of white crystals were obtained. The result of infrared spectroscopy analysis of the obtained white crystal is as follows.
It is as shown below, confirming that the white crystal is the target product
did. 2920cm^-1, 2850cm^-1, 1750cm^-1, 1
600cm^-1, 1510cm^-1, 1440cm^-1, 12
40cm^-1, 1190cm^-1, 1150cm^-1, 112
0cm^-1, 1040cm^-1, 1000cm^-1, 840c
m^-1 The phase transition temperature of the obtained target is as follows:
Where the NI point is high and the liquid crystal temperature range is
It had a remarkably broad characteristic of 67 ° C. CN point (88 ° C), NI point (155 ° C) Example 3 trans-4-n-pentylici
Clohexanecarboxylic acid-trans-4- (4'-meth
(Xymethylcyclohexylmethoxy) phenyl ester
(Synthesis of Compound No. 3 of the above Chemical Formula 5) The trans-4- (4'-meth) obtained in (3) of Example 1 was used.
1. Toximethylcyclohexylmethoxy) phenol
5 g and trans-4-n-pentylcyclohexylca
Dissolve 2.2 g of rubonic acid in 30 ml of methylene chloride.
Here, N, N'-dicyclohexylcarbodiimide 2.3
g in 3 ml of methylene chloride was added dropwise. Room
After stirring at room temperature for 3 hours, N, N'-dicyclohexy
Luurea was filtered off. After removing the solvent from the filtrate, the product was washed with ethyl acetate.
/ N-hexane (2/8) as a developing solvent
And then recrystallized with methanol.
No, 3.3 g (75% yield) of white crystals were obtained. The result of infrared spectroscopy analysis of the obtained white crystal is as follows:
It is as shown below, confirming that the white crystal is the target product
did. 2910cm^-1, 2840cm^-1, 1750cm^-1, 1
580cm^-1, 1500cm^-1, 1460cm^-1, 12
40cm^-1, 1190cm^-1, 1150cm^-1, 112
0cm^-1, 1030cm^-1, 970cm^-1, 830cm
^-1 The phase transition temperature of the obtained target product is as follows:
Where the NI point is high and the liquid crystal temperature range is
It had a remarkably broad characteristic of 84 ° C. CS point (74 ° C), SN point (79 ° C), NI point
(158 ° C) Example 4: trans-4- (4'-methoxy)
Cimethylcyclohexylmethoxy) Benzoic acid-4-cyanophenyl ester (the above [Chemical formula 9]
Synthesis of compound No. 7) (1) trans-4- (4'-methoxymethylcyclohexane
Synthesis of (xylmethoxy) benzoic acid-methyl ester The trans-4-methoxymethol obtained in Example 1, (1)
3.16 g of tylcyclohexylmethanol, p-hydro
3.20 g of methyl xybenzoate and triphenylphosphine
5.51 g of ethylene oxide in 30 m of dry diethyl ether
l, and diisopropyl azodicarboxylate
4.25 g were added dropwise. After stirring at room temperature for 3 hours, a precipitate was formed.
Triphenylphosphine is filtered off, and the filtrate is desolvated.
Ethyl acetate / n-hexane (2/8) as eluent
The silica gel column treatment is performed as
S-4- (4'-methoxymethylcyclohexyl methoxy)
B) 5.41 g of benzoic acid-methyl ester (yield 92)
%). (2) trans-4- (4'-methoxymeth
Synthesis of tyl) cyclohexylmethoxybenzoic acid The trans-4- (4'-methoxy) obtained in the above (1)
Methylcyclohexylmethoxy) benzoic acid-methyles
Was dispersed in 40 ml of aqueous ethanol, and
1.84 g of 85% potassium hydroxide was added thereto, and
For 1 hour. After cooling, the reaction mixture was diluted with diluted hydrochloric acid 10
The mixture was poured into 0 ml, and the precipitate was filtered. Then the washing liquid becomes neutral
The precipitate was washed with water until the desired product, trans-4-
(4'-methoxymethylcyclohexylmethoxy) benzoate
4.8 g (93% yield) of perfumed acid were obtained. (3) trans-4- (4'-methoxymeth
Tylcyclohexylmethoxy) benzoic acid-4-cyanov
Synthesis of phenyl esters The trans-4- (4'-methoxy) obtained in the above (2)
4.0 g of methylcyclohexylmethoxy) benzoic acid
1.9 g of cyanophenol in 40 ml of methylene chloride
Dissolve and add N, N-dicyclohexylcarbodiimide
A solution of 3.5 g dissolved in 4 ml of methylene chloride was added dropwise.
did. After stirring at room temperature for 3 hours, the precipitated N, N'-disc
After filtering off the rohexyl urea and removing the solvent from the filtrate, the product is
Ethyl acetate / n-hexane (2/8) as a developing solvent
Ricagel column treatment was performed. Then reconstitute with ethanol
Crystallization was performed to obtain 4.9 g (yield 90%) of white crystals. The result of infrared spectroscopic analysis of the obtained white crystal is as follows.
It is as shown below, confirming that the white crystal is the target product
did. 2920cm^-1, 2850cm^-1, 2220cm^-1, 1
730cm^-11600cm^-1, 1500cm^-1, 14
60cm^-1, 1440cm^-1, 1250cm^-1, 120
0cm^-1, 1160cm^-1, 1100cm^-1, 1060
cm^-1, 1800cm^-1, 1000cm^-1, 880cm
^-1, 840cm^-1, 760cm^-1 The phase transition temperature of the obtained target product is as follows:
Where the NI point is high and the liquid crystal temperature range is
It had a remarkably broad characteristic of 55 ° C. CN point (136 ° C), NI point (191 ° C) Example 5: trans-4- (4'-methoxy)
Cimethylcyclohexylmethoxy) phenyl-4-cia
Benzoic acid ester (compound No. 8 of the above [Chemical Formula 10])
Synthesis of The trans-4- (4'-meth) obtained in (3) of Example 1 was used.
1. Toximethylcyclohexylmethoxy) phenol
5 g and 1.7 g of 4-cyanobenzoic acid were dissolved in methylene chloride 3
0 ml, and add N, N'-dicyclohexylca
2.3 g of rubodiimide was dissolved in 3 ml of methylene chloride
The solution was added dropwise. After stirring at room temperature for 3 hours, N,
N'-Dicyclohexylurea was filtered off. Desolvate the filtrate
Thereafter, the product was developed with ethyl acetate / n-hexane (1/2).
Perform silica gel column treatment as an open solvent, then
Recrystallize with tanol / ethyl acetate (2/1)
2.2 g (58% yield) of colored crystals were obtained. The result of infrared spectroscopy analysis of the obtained white crystal is as follows.
It is as shown below, confirming that the white crystal is the target product
did. 2920cm^-1, 2850cm^-1, 2230cm^-1, 1
730cm^-11600cm^-1, 1500cm^-1, 14
60cm^-1, 1270cm^-1, 1240cm^-1, 119
0cm^-1, 1080cm^-1, 1040cm^-1, 860c
m^-1, 840cm ^-1 The phase transition temperature of the obtained target product is as follows.
Where the NI point is high and the liquid crystal temperature range is
It had a remarkably wide characteristic of 133 ° C. CS point (62 ° C), SN point (146 ° C), NI point
(195 ° C) Example 6: 4- (trans-4'-methoxy)
Cimethylcyclohexylmethoxy) Benzoic acid-3,4-difluorophenyl ester (above
Synthesis of Compound No. 9 of [Formula 11] Trans-4- (4'-) synthesized in the same manner as in Example 3.
1. methoxymethylcyclohexylmethoxy) benzoic acid
65 g and 1.49 g of 3,4-difluorophenol
Dissolve in 27 ml of methylene chloride and add N, N-disc
2.36 g of rohexylcarbodiimide was added to methylene chloride 3
The solution dissolved in ml was dropped. After stirring at room temperature for 3 hours,
The precipitated N, N'-dicyclohexylurea was separated by filtration.
After removing the solvent from the filtrate, the product was purified with ethyl acetate / n-hexane.
Silica gel column treatment using (2/8) as the developing solvent
And then recrystallized from ethanol to give white crystals.
4 g (91% yield) were obtained. The result of infrared spectroscopy analysis of the obtained white crystal is as follows:
It is as shown below, confirming that the white crystal is the target product
did. 2920cm^-1, 2860cm^-1, 1730cm^-1, 1
600cm^-1, 1510cm^-1, 1460cm^-1, 12
40cm^-1, 1200cm^-1, 1170cm^-1, 114
0cm^-1, 1100cm^-1, 1050cm^-1, 1030
cm^-1, 830cm^-1 The phase transition temperature of the obtained target product is as follows:
Where the NI point is high and the liquid crystal temperature range is
It had a remarkably wide characteristic of 40 ° C. CN point (64 ° C), NI point (104 ° C) Example 7: 4-cyano-4 '-(4 "-me
Toximethylcyclohexylmethoxy) biphenyl (above
(Synthesis of Compound No. 10 of Chemical Formula 12) The trans-4-methoxymethol obtained in Example 1, (1)
5.22 g of tylcyclohexylmethanol, 4-cyano
5.86 g of -4'-hydroxybiphenyl and triphe
8.66 g of nylphosphine was added to dry diethyl ether 75
Dissolved in ml. Here, azodicarboxylic acid diisopropyl
6.67 g was added dropwise, and the mixture was stirred at room temperature for 3 hours and then precipitated.
Triphenylphosphine was filtered off. After removing the filtrate,
Dissolve the product in ethyl acetate / n-hexane (2/8)
Perform silica gel column treatment as a medium,
Then, 4.0 g of white crystals were obtained (yield: 40 g).
%). The results of infrared spectroscopy analysis of the obtained white crystals are as follows:
It is as shown below, confirming that the white crystal is the target product
did. 2920cm^-1, 2840cm^-1, 2210cm^-1, 1
600cm^-1, 1480cm^-1, 1460cm^-1, 12
90cm^-1, 1240cm^-1, 1170cm^-1, 111
0cm^-1, 1090cm^-1, 1060cm^-1, 830c
m^-1 The phase transition temperature of the obtained target product is as follows:
Where the NI point is high and the liquid crystal temperature range is
It had a remarkably wide characteristic of 63 ° C. CN point (125 ° C), NI point (188 ° C) Example 8: Trans-4- (trans-
4'-n-pentylcyclohexyl) cyclohexaneca
Rubonic acid-trans-4- (4'-methoxymethyl) cy
Clohexyl methoxyphenyl ester (above [Formula 1]
Synthesis of compound No. 15) of 7) The trans-4- (4'-meth) obtained in (3) of Example 1 was used.
1. Toximethylcyclohexylmethoxy) phenol
5 g and trans-4- (trans-4'-n-pliers
3.1 g of cyclohexyl) cyclohexanecarboxylic acid
Was dissolved in 30 ml of methylene chloride, and N, N'-diamine was added thereto.
2.3 g of cyclohexylcarbodiimide was added to methylene chloride.
A solution dissolved in 3 ml was added dropwise. Stir at room temperature for 3 hours
Thereafter, the precipitated N, N'-dicyclohexylurea was filtered off.
Was. After removing the solvent from the filtrate, the product was purified with ethyl acetate / n-hexaene.
(2/8) as a developing solvent for silica gel column treatment
And then re-use with ethanol / ethyl acetate (1/1).
Crystallization was performed to obtain 4.0 g of white crystals (78% yield).
Was. The result of infrared spectroscopy analysis of the obtained white crystal is as follows:
It is as shown below, confirming that the white crystal is the target product
did. 2910cm^-1, 2840cm^-1, 1740cm^-1, 1
590cm^-1, 1500cm^-1, 1450cm^-1, 12
40cm^-1, 1200cm^-1, 1130cm^-1, 111
0cm^-1, 1040cm^-1, 990cm^-1, 840cm
^-1 The phase transition temperature of the obtained target product is as follows:
Where the NI point is high and the liquid crystal temperature range is
It had a remarkably broad characteristic of 78 ° C. CS point (94 ° C), SN point (200 ° C), NI point
(272 ° C) Embodiment 9 As a STN liquid crystal material, a commercially available liquid crystal A is used as a mother liquid crystal, and
Properties when the compounds obtained in Examples 1 to 8 are added
The values are shown in the following [Table 1]. The commercially available liquid crystal A is shown in the following [Formula 23].
4-n-alkylcyclohexanecarboxy having composition
It is an acid alkoxyphenyl ester-based composition. <Composition of Commercial Liquid Crystal A> [0072] Embedded image [0073] [Table 1]As can be seen from Table 1 above, the compounds of the present invention
Point of the liquid crystal composition by adding
Greatly increases, and the anisotropy of the refractive index of the liquid crystal material
It can be seen that (Δn) hardly changes. [0075] The cyclohexanedimethyl derivative of the present invention
Is mixed with a nematic liquid crystal material,
Having a crystal temperature range and anisotropy of refractive index of liquid crystal material (Δn)
It is possible to raise the NI point while maintaining
It can be.

────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C07C 255/50 C07C 255/50 C09K 19/30 C09K 19/30 G02F 1/13 500 G02F 1/13 500 (72) Inventor Yamazaki Yuji 5-2-13-Shirahata, Urawa-shi, Saitama Asahi Denka Kogyo Co., Ltd. (56) References JP-A-57-176943 (JP, A) JP-A-1-157925 (JP, A) Table 3 −504018 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 43/21 C07C 43/225 C07C 69/75 C07C 69/753 C07C 69/92 C07C 255/50 C09K 19 / 30 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claim 1] A cyclohexanedimethyl derivative represented by the following general formula (I): Embedded image