JPH0674240B2 - New compound - Google Patents

Description

The present invention relates to a novel compound having liquid crystallinity. More specifically, in the field of optoelectronics, especially digital display devices such as calculators and watches, electro-optical shutters, electro-optical apertures, optical modulators, optical communication optical path selector switches, memories, liquid crystal printer heads, variable focal length lenses, etc. The present invention relates to a novel compound having liquid crystallinity used as an electro-optical device.

[Conventional technology]

Liquid crystals are already used as various electro-optical elements,
Widely used for digital displays such as calculators and clocks. Most conventional liquid crystal display elements use nematic liquid crystal or cholesteric liquid crystal,
These have problems in terms of responsiveness, contrast, viewing angle characteristics, and the like. Therefore, recently, as a solution to these drawbacks, a display device using a ferroelectric chiral smectic C-phase (Sc ^* phase) liquid crystal capable of high-speed response has been proposed. However, even in these cases, smectic C
There are problems such as a high temperature range exhibiting a phase and lack of chemical stability. A material having a ferroelectric Sc ^* phase, which has a relatively low temperature range and is capable of high-speed response, is also known (JP-A-55-
21479, JP60-235885, JP61-22072
JP-A-61-24576, etc.), it is difficult to obtain these compounds at low cost.

[Problems to be solved by the invention]

The present invention provides a novel liquid crystal compound which is a relatively inexpensive and chemically stable liquid crystal compound and which exhibits a ferroelectric Sc ^* phase capable of high-speed response in a wide temperature range up to room temperature or lower. Is what you are trying to do.

[Means for solving problems]

As a result of repeated studies to achieve the above-mentioned objects, the present inventors used inexpensive 2-methylbutanol, which is industrially easily obtained, as a raw material for an optically active group, and made this optically active group a specific chemical structure. It was found that a novel liquid crystal compound satisfying the above object can be obtained by introducing the compound, and the present invention has been accomplished based on this finding.

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

(In the formula, R ₁ and R ₅ represent an alkyl chain having 1 to ₅ carbon atoms and may be the same or different, and X ₁ and X ₂ are -O-, R ₂ may be the same or different, R ₂ represents —H or —CH ₃ , R ₃ represents an alkyl chain having 1 to 20 carbon atoms, and R ₄ represents Or And C _* represents an asymmetric carbon. ) The novel compound of the present invention can be produced by using a compound known per se as a starting material. An example of the manufacturing method is shown below.

1) R ₁ and R ₅ in the general formula (1) are the same, and X ₁
But And X ₂ is And R ₄ is Of a compound of formula (II) (1) 4'-hydroxybiphenyl-4-carboxylic acid 2-methylbutyl ester (hydroxy form) Synthesis of 4'-hydroxybiphenyl-4-carboxylic acid and 2-methylbutanol are condensed in the presence of a dehydrating agent such as concentrated sulfuric acid to be esterified to obtain a target hydroxy compound.

(2) Bromo form Synthesis of (1) The hydroxy compound obtained in (1) is alkoxided with potassium carbonate or the like, reacted with Br-R ₃ -Br to form a monoether, and the desired bromo compound is obtained.

Here, the compound of formula Br-R ₃ -Br is specifically dibromomethane, dibromoethane, dibromopropane, dibromobutane, dibromopentane, dibromohexane, dibromoheptane, dibromooctane, dibromononane, dibromodecane, dibromoundecane, It is dibromododecane, dibromotridecane, dibromotetradecane, dibromopentadecane, dibromohexadecane, dibromoheptadecane, dibromooctadecane, dibromononadecane, dibromoicosane.

(3) Alcohol Synthesis of Is reacted with quaternary ammonium hydroxide such as tetramethylammonium hydroxide in a solvent such as dimethylformamide (DMF) to form a carboxylate, and the bromo compound obtained in (2) is reacted with this to esterify, Obtain the desired alcohol.

Where the expression The compounds are specifically dimethylolacetic acid and dimethylolpropionic acid.

(4) Synthesis of (3) The alcohol compound obtained in (3) is reacted with (R ₁ CO) ₂ O (anhydride) to form a diester to obtain the desired novel compound (II).

Here, the compound of the formula (R ₁ CO) ₂ O is specifically acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride, hexanoic anhydride and the like.

2) In the general formula (I), R ₁ and R ₅ are the same, and X ₁
But And X ₂ is And R ₄ is Of a compound of formula (III) (1) Hydroxy form Synthesis of 4-hydroxybenzoic acid and 2-methylbutanol are allowed to react with each other in the presence of a dehydrating agent such as concentrated sulfuric acid to be esterified to obtain a target hydroxy compound.

(2) Ester form Synthesis of 4-hydroxybenzoic acid is reacted with carbobenzoxylcolide to form an ester, and the hydroxy group is protected with a carbobenzoxy group.

(3) Acid chloride Synthesis of (2) The ester compound obtained in (2) is reacted with an acid halogenating agent such as phosphorus pentachloride to obtain the desired acid chloride.

(4) Ester form Synthesis of (1) The hydroxy compound obtained in (1) is reacted with the acid chloride obtained in (3) in a solvent such as THF or pyridine to esterify the compound to obtain the desired ester compound.

(5) Hydroxy form The ester obtained in (4) is hydrolyzed by contacting it with a hydrogenolysis catalyst such as palladium carbon in a hydrogen gas atmosphere to eliminate the carbobenzoxy group, which is a protective group. Get the body.

(6) Bromo form Synthesis of (5) The hydroxy compound obtained in (5) was alkoxylated with potassium carbonate etc., and this was added to Br-R ₃ -Br in a solvent such as acetone.
The resulting bromo compound is obtained by reacting with a monoether.

(7) Alcohol Synthesis Is reacted with quaternary ammonium hydroxide such as tetramethylammonium hydroxide in a solvent such as dimethylformamide (DMF) to form a carboxylate, and the bromo compound obtained in (6) is reacted with this to esterify, Obtain the desired alcohol.

(8) Synthesis of (7) The alcohol derivative obtained in (7) is reacted with (R ₁ CO) ₂ O) (an acid anhydride) to form a diester to obtain the desired novel compound (III).

3) In the general formula (1), R ₁ and R ₅ are the same, and X ₁
But And X ₂ is And R ₄ is Of compounds of formula (IV) (1) Ester form Synthesis of 4-hydroxybenzoic acid benzyl ester is reacted with Br-R ₃ -Br in a solvent such as acetone in the presence of potassium carbonate to form a monoether, thereby obtaining the desired ester form.

(2) Carboxylic acid derivative Synthesis of (1) The ester compound obtained in (1) is decomposed with a palladium carbon catalyst and hydrogen gas to obtain the desired carboxylic acid derivative.

(3) Bromo form Synthesis of (2) The carboxylic acid derivative obtained in (2) is reacted with an acid halogenating agent such as thionyl chloride in a solvent such as toluene to obtain the halide. Hydroxy form obtained by the method of (1) of the obtained acid halide and 1) And are reacted in a solvent such as THF in the presence of triethylamine for esterification to obtain the desired bromo compound.

(4) Alcohol Synthesis of Is reacted with a quaternary ammonium hydroxide such as tetramethylammonium hydroxide in a solvent such as DMF to form a carboxylate, and the bromo compound obtained in (3) is reacted with this to esterify the desired alcohol. Get the body.

(5) Synthesis of (4) The alcohol compound obtained in (4) is reacted with (R ₁ CO) ₂ O (anhydride) to form a diester to obtain the desired novel compound (IV).

4) In the general formula (I), R ₁ and R ₅ are the same, and X ₁
But And X ₂ is And R ₄ is Of the compound of formula (V) (1) 4'-Hydroxybiphenyl-4-carboxylic acid benzyl ester (ester form) Synthesis of 4'-hydroxybiphenyl-4-carboxylic acid is reacted with ammonium hydroxide in a solvent such as DMF to form a carboxylic acid salt, which is reacted with benzyl bromide to esterify,
The target ester is obtained.

Then, as shown in the following reaction formula, the ester compound, the carboxylic acid derivative, the bromo compound, the alcohol compound, and the new compound are sequentially synthesized by performing the same operation as in the above 3) to obtain the desired novel compound (V). obtain.

[Examples] Hereinafter, the present invention will be described in detail based on Examples, but the present invention is not limited thereto.

Example 1 Preparation of 4 '-[12- (2,2-diacetoxymethylpropionyloxy) dodecyloxy] biphenyl-4-carboxylic acid 2-methylbutyl ester (1) 4'-hydroxybiphenyl-4-carboxylic acid 2 -Synthesis of methyl butyl ester (hydroxy form) 93 mmol of 4'-hydroxybiphenyl-4-carboxylic acid and 467 mmol of 2-methylbutanol were refluxed in 150 ml of benzene for 25 hours in the presence of 2 ml of concentrated sulfuric acid. The reaction solution was concentrated and then recrystallized with a mixed solvent of toluene and hexane to obtain the desired hydroxy compound of the following formula. (Yield 98%, ▲ [α]
²³ _D ▼ ＝ ＋ 4.35 ° (CHCl ₃ )) (2) 4 '-(12-Bromododecyloxy) biphenyl-4-carboxylic acid 2-methylbutyl ester (bromo form)
Synthesis of 10.5 mmol of the hydroxy compound obtained in (1), 21.1 mmol of dibromododecane, 42.2 mmol of potassium carbonate in 50 ml of acetone
The solution was refluxed for 6 hours. The reaction solution was filtered, concentrated, and purified by column chromatography to obtain the desired bromo compound of the following formula. (Yield 90%, ▲ [α] ²³ _D ▼ ＝ ＋ 2.31
° (CHCl ₃ )) (3) Synthesis of 4 '-(12-dimethylolpropionyloxidedecyloxy) biphenyl-4-carboxylic acid 2-methylbutyl ester (alcohol) 6.0 mmol dimethylolpropionic acid and tetramethylammonium hydroxide (pentahydrate) ) 6.6 mmol was stirred in 50 ml DMF for 2 hours. Next, the bromo compound obtained in (2) 8.
5 mmol was added and stirred for 6 hours. 100 ml of water was added to the reaction solution, extracted with ether, dried, concentrated, and purified by column chromatography to obtain the desired alcohol compound of the following formula. (Yield 50%, ▲ [α] ²³ _D ▼ ＝ ＋ 2.1 °
(CHCl ₃ )) (4) Synthesis of 4 '-[12- (2,2-diacetoxymethylpropionyloxy) dodecyloxy] biphenyl-4-carboxylic acid 2-methylbutyl ester 2.5 mmol of alcohol obtained in (3) and acetic anhydride 15m
A 5 ml solution of pyridine in mol was stirred at room temperature for 12 hours. The reaction solution was extracted with ether, the ether layer was washed with HCl water, dried,
After concentration, the product was purified by column chromatography to obtain the desired novel compound of the following formula. (Yield 76%, ▲ [α]
²³ _D ▼ ＝ ＋ 2.10 ° (CHCl ₃ )) The phase transition behavior of this compound was as follows. In addition,
The following numerical values represent the phase transition temperature, and the unit is 0 ° C.

(Cry: Crystal, S _A : Smectic A phase liquid crystal state, Sc ^* : Chiral smectic C phase liquid crystal state, Iso: Isotropic liquid state) Elemental analysis values of this compound are shown in the following table.

The ¹ H-NMR spectrum and IR spectrum of this compound are shown in FIG. 1 and FIG. 2, respectively. ^In the measurement of ¹ H-NMR spectrum, CDCl ₃ was used as a solvent, and the peak at 0 ppm in the figure is a signal representing tetramethylsilane (TMS) (same in the following examples).

Example 2 Preparation of 4 '-[12- (2,2-dipropionyloxycimethylpropionyloxy) dodecyloxy] biphenyl-4-carboxylic acid 2-methylbutyl ester Alcohol obtained in (3) of Example 1 A solution of 2.5 mmol of isomer, 15 mmol of propionic anhydride and 5 ml of pyridine at room temperature
It was stirred for 2 hours. The reaction solution was extracted with ether and the ether layer was washed with H.
It was washed with Cl water, dried, concentrated, and purified by column chromatography to obtain the desired novel compound of the following formula.
(Yield 65%, ▲ [α] ²³ _D ▼ = + 2.05 ° (CHCl ₃ )) The phase transition behavior of this compound was as follows.

The elemental analysis values of this compound are shown in the following table.

The ¹ H-NMR spectrum and IR spectrum of this compound are shown in FIG. 3 and FIG. 4, respectively.

Example 3 Preparation of 4- [4 '-{12- (2,2-diacetoxymethylpropionyloxy) dodecyloxy} benzoyloxy] benzoic acid 2-methylbutyl ester (1) 4-Hydroxybenzoic acid 2-methylbutyl ester Synthesis of ester (hydroxy form) 0.29 mol of 4-hydroxybenzoic acid and 0.35 mol of (S)-(-)-2 methylbutanol were refluxed in 150 ml of toluene in the presence of 1 ml of concentrated sulfuric acid. The reaction solution was concentrated and then purified by column chromatography to obtain the target hydroxy compound of the following formula. (Yield 65%, ▲ [α] ²³ _D ▼ + 4.95 °
((CHCl ₃ )) (2) Synthesis of 4-carbobenzoxyoxybenzoic acid (ester form) 55 mmol of 4-hydroxybenzoic acid and 65 of sodium hydroxide
65 mmol of carbobenzoxylcolide was added dropwise to a 200 ml aqueous solution of mmol under ice temperature. After stirring for 24 hours, wash the precipitate with water,
Filtered, dried, purified by column chromatography,
The target ester compound of the following formula was obtained. (Yield 99%,
(mp181.9-183.1 ° C) (3) Synthesis of 4-carbobenzoxyoxybenzoic acid chloride (acid chloride) 27 mmol of ester obtained in (2) and phosphorus pentachloride
A solution of 27 mmol of 50 ml of ether was stirred at room temperature for 24 hours. After the reaction, deethering is performed, and the crystal is recrystallized from hexane,
The desired acid chloride of the following formula was obtained. (Yield 57%, m.
(p.65.5-67.4 ° C) (4) Synthesis of 4- (4'-carbobenzoxyoxydibenzoyloxy) benzoic acid 2-methylbutyl ester (ester form) 20 ml of the hydroxy form THF obtained in (1), pyridine 4
The 0 ml solution was ice-cooled, and the acid chloride obtained in (3) was 16 mmol.
THF solution was added dropwise. Gradually return the temperature to room temperature, and
Stir for hours. After the reaction, the mixture was extracted with ether, concentrated, and then purified by column chromatography to obtain the target ester of the following formula. (Yield 63%, mp64.4-65.4 ℃) (5) Synthesis of 4- (4'-hydroxybenzoyloxy) benzoic acid 2-methylbutyl ester (hydroxy form) 10 mmol of the ester form obtained in (4) and 0.5 g of palladium carbon (5% catalyst) in acetic acid ester solution Was reacted in a hydrogen gas atmosphere for 4 hours. After the reaction, palladium carbon was filtered through a membrane filter, concentrated and purified by column chromatography to obtain a target hydroxy compound of the following formula. (Yield 64%, mp90.8-92.6 ℃) (6) Synthesis of 4- [4 '-(12-bromododecyloxy) benzoyloxy] benzoic acid 2-methylbutyl ester (bromo form) 10.5 mmol of the hydroxy form obtained in (5), 21.1 mmol of dibromododecane, carbonic acid Acetone of potassium 42.2mmol 50mm
o The solution was refluxed for 6 hours. The reaction solution was filtered, concentrated, and purified by column chromatography to obtain the desired bromo compound of the following formula. (Yield 82%, ▲ [α] ²³ _D ▼ + 2.79
° ((CHCl ₃ )) (7) 4- [4 '-(12-Dimethylolproonyloxidedecyloxy) benzoyloxy] benzoic acid 2-methylbutyl ester (synthesis of alcohol) dimethylolpropionic acid 6.0 mmol and tetramethylammonium hydroxide ( 6.6 mmol of pentahydrate) was stirred in 50 ml of DMF for 2 hours. 100 ml of water was added to the reaction solution, extracted with ether, dried, concentrated, and purified by column chromatography to obtain the desired alcohol compound of the following formula.
(Yield 42%, ▲ [α] ²³ _D ▼ + 2.90 ° ((CHCl ₃ )) (8) Synthesis of 4 '-[12- (2,2-diacetoxymethylpropionyloxy) dodecyloxy] benzoyloxybenzoic acid 2-methylbutyl ester 2.5 mmol of alcohol obtained in (7) and acetic anhydride 15m
A 5 ml solution of pyridine in mol was stirred at room temperature for 12 hours. The reaction solution was extracted with ether, the ether layer was washed with HCl water, dried,
After concentration, the product was purified by column chromatography to obtain the desired novel compound (III) of the following formula. (70% yield, ▲
[Α] ²³ _D ▼ + 2.85 ° ((CHCl ₃ )) The phase transition behavior of this compound was as follows.

The elemental analysis values of this compound are shown in the following table.

The ¹ H-NMR spectrum and IR spectrum of this compound are shown in FIG. 5 and FIG. 6, respectively.

Example 4 Preparation of 4 '-[10- (2,2-diacetoxymethylpropionyloxy) dodecyloxy] biphenyl-4-carboxylic acid 2-methylbutyl ester (1) 4'-hydroxybiphenyl-4-carboxylic acid 2 -Synthesis of Methyl Butyl Ester (Hydroxy Form) The same hydroxy form was obtained by performing the same operation as in (1) of Example 1.

(2) 4 '(10-bromodecyloxy) biphenyl-4-
Synthesis of carboxylic acid 2-methylbutyl ester (bromo form) 30 mmol of the hydroxy compound obtained in (1), 60 mmol of dibromodecane, and 150 ml of potassium carbonate 120 mmol of acetone
The solution was refluxed for 6 hours. The reaction solution was filtered and concentrated, and then purified by column chromatography to obtain the desired bromo compound. (Yield 86%, ▲ [α] ²³ _D ▼ + 2.55 ° ((C
HCl ₃ )) (3) Synthesis of 4 '-(10-dimethylolpropionyloxydecyloxy) biphenyl-4-carboxylic acid 2-methylbutyl ester (alcohol) Dimethylolpropionic acid (18.0 mmol) and tetramethylammonium hydroxide (pentahydrate) (20.0 mmol) were stirred in DMF (100 ml) for 2 hours. 25.5 mmol of the bromo derivative obtained in (2) was added to the reaction mixture, and the mixture was stirred for 6 hours. Water as the reaction liquid
After adding 300 ml, extraction with ether, drying and concentration, purification by column chromatography was performed to obtain the desired alcohol. (Yield 70%, ▲ [α] ²³ _D ▼ +
2.09 ° ((CHCl ₃ )) (4) Synthesis of 4 '-[10- (2,2-diacetoxymethylpropionyloxy) dodecyloxy] biphenyl-4-carboxylic acid 2-methylbutyl ester (3) 7.5 mmol of alcohol and 45 m of acetic anhydride
A 5 ml solution of pyridine in mol was stirred at room temperature for 12 hours. The reaction solution was extracted with ether, the ether layer was washed with aqueous HCl, dried and concentrated, and then purified by column chromatography to obtain a target novel compound having the following structural formula.
(Yield 85%, ▲ [α] ²³ _D ▼ + 2.11 ° (CHCl ₃ )) The phase transition behavior of this compound was as follows.

The elemental analysis values of this compound are shown in the following table.

The ¹ H-NMR spectrum and IR spectrum of this compound are shown in FIG. 7 and FIG. 8, respectively.

Example 5 Preparation of 4 '-[4 "-{12- (2,2-diacetoxymethylpropionyloxy) dodecyloxy} benzoyloxy] biphenyl-4-carboxylic acid 2-methylbutyl ester (1) 4'-hydroxy Synthesis of biphenyl-4-carboxylic acid 2-methylbutyl ester (hydroxy form) The same operation as in (1) of Example 1 was performed to obtain the above hydroxy form.

(2) Synthesis of 4- (12-bromododecyloxy) benzoic acid benzyl ester (ester form) Dibromododecane 150 mmol, 4-hydroxybenzoic acid 50 mmo
l, and 6 ml of a solution of 0.1 mol of potassium carbonate in 500 ml of acetone
Reflux for hours. The reaction solution was filtered and concentrated, and then purified by column chromatography to obtain the target ester form. (Yield 82%, ▲ [α] ²³ _D ▼ + 2.55 ° (CHCl ₃ )) (3) Synthesis of 4- (12-bromododecyloxy) benzoic acid (carboxylic acid derivative) A solution of 100 mmol of the ester obtained in (2) and 2.0 g of palladium carbon (5% catalyst) in 150 ml of acetic ester was stirred in the presence of hydrogen gas for 5 hours. The reaction solution is filtered and concentrated, and then purified by column chromatography,
The desired carboxylic acid derivative was obtained. (Yield 98%) (4) Synthesis of 4 '-[4 "-(12-bromododecyloxy) benzoyloxy] biphenyl-4-carboxylic acid 2-methylbutyl ester (bromo form) 50 mmol of the carboxylic acid derivative obtained in (3) was stirred in 30 ml of toluene and 10 ml of thionyl chloride at 80 ° C. for 2 hours to give an acid chloride. Then, excess thionyl chloride and toluene were distilled off by vacuum drying. 55 mmol of the hydroxy compound obtained in (1) and 60 mmol of triethylamine
A 200 ml solution of THF was stirred and then the acid chloride obtained above was
The THF solution was added dropwise and stirred for 8 hours. After the reaction, extraction with ether, washing with HCl water, drying, and concentration were performed, followed by purification by column chromatography to obtain the desired bromo compound. ((Yield 73%, ▲ [α] ²³ _D ▼ + 2.3
3 ° (CHCl ₃ )) (5) Synthesis of 4 '-[4 "-(12-dimethylolpropionyloxidedecyloxy) benzoyloxy] biphenyl-4-carboxylic acid 2-methylbutyl ester (alcohol) Dimethylolpropionic acid (18.0 mmol) and tetramethylammonium hydroxide (pentahydrate) (20.0 mmol) were stirred in DMF (150 ml) for 2 hours. Next, the bromo form obtained in (4)
25.0 mmol was added and stirred for 6 hours. After the reaction, the product was extracted with ether, dried and concentrated, and then purified by column chromatography to obtain the desired alcohol.
((Yield 78%, ▲ [α] ²³ _D ▼ + 2.10 ° (CHCl ₃ )) (6) 4 '-[4 "-{12- (2,2-diacetoxymethylpropionyloxy) dodecyloxy} Synthesis of benzoyloxy] biphenyl-4-carboxylic acid 2-methylbutyl ester 7.5 mmol of alcohol obtained in (5) and 45 m of acetic anhydride
A 5 ml solution of pyridine in mol was stirred at room temperature for 12 hours. The reaction solution was extracted with ether, the ether layer was washed with aqueous HCl, dried and concentrated, and then purified by column chromatography to obtain the desired novel compound having the following structural formula.
(Yield 82%, ▲ [α] ²³ _D ▼ + 2.06 ° (CHCl ₃ )) The phase transition behavior of this compound was as follows.

The elemental analysis values of this compound are shown in the following table.

The ¹ H-NMR spectrum and IR spectrum of this compound are shown in FIG. 9 and FIG. 10, respectively.

Example 6 Preparation of 4- [4 ″-{12- (2,2-diacetoxymethylpropionyloxy) dodecyloxy} biphenyl-4′-carbonyloxy] benzoic acid 2-methylbutyl ester (1) 4-hydroxybenzoic acid Synthesis of acid 2-methylbutyl ester (hydroxy form) 90 mmol 4-hydroxybenzoic acid and 2-methylbutanol
360 mmol was subjected to dehydration reaction in 150 ml of toluene in the presence of 2 ml of concentrated sulfuric acid for 25 hours. The reaction solution was concentrated and then purified by column chromatography to obtain the target hydroxy compound. (Yield 95%, ▲ [α] ²³ _D ▼ + 4.85 ° (CHC
l ₃ )) (2) Synthesis of 4'-hydroxybiphenyl-4-carboxylic acid benzyl ester (ester form) 0.1 mol of 4'-hydroxybiphenyl-4-carboxylic acid and tetramethylammonium hydroxide (pentahydrate) 0.11mo
200 ml of DMF in 200 ml was stirred for 2 hours. Next, 0.1 mol of benzyl bromide was added and stirred for 6 hours. After the reaction, the mixture was extracted with ether, dried and concentrated, and then purified by column chromatography to obtain the target ester form. (Yield 76%) (3) Synthesis of 4 '-(12-bromododecyloxy) biphenyl-4-carboxylic acid benzyl ester (ester form) 70 mmol of the ester obtained in (2), 0.21 mol of dibromododecane, and 0.4 mol of potassium carbonate in acetone 1
The solution was refluxed for 6 hours. The reaction solution was filtered and concentrated, and then purified by column chromatography to obtain the target ester form.

(Yield 89%, ▲ [α] ²³ _D ▼ + 2.30 ° (CHCl ₃ )) (4) Synthesis of 4 '-(12-bromododecyloxy) biphenyl-4-carboxylic acid (carboxylic acid derivative) A solution of 60 mmol of the ester compound obtained in (3) and 2.0 g of palladium carbon (5% catalyst) in 500 ml of ethyl acetate was added,
The mixture was stirred in a hydrogen gas atmosphere for 24 hours. After the reaction, the mixture was filtered, concentrated, and purified by column chromatography to obtain the desired carboxylic acid derivative. (Yield 98%) (5) Synthesis of 4- [4 ″-(12-bromododecyloxy) biphenyl-4′-carbonyloxy] benzoic acid 2-methylbutyl ester (bromo form) 50 mmol of the carboxylic acid derivative obtained in (4) was stirred for 2 hours at 80 ° C. in a solution of 20 ml of toluene and 10 ml of thionyl chloride to give an acid chloride. Excess thionyl chloride and toluene were distilled off under reduced pressure. Next, 55 mmol of the hydroxy compound obtained in (1) and 60 mmol of toluethylamine
A solution of 200 ml of THF was stirred, the THF solution of the acid chloride obtained above was added dropwise, and the mixture was reacted for 8 hours. After the reaction, after performing ether extraction, washing with HCl water, drying, and concentration,
Purification by column chromatography gave the desired bromo compound. (Yield 82%, ▲ [α] ²³ _D ▼ + 2.09 ° (C
HCl ₃ )) (6) 4- [4 ″-(12-dimethylolpropionyloxidedecyloxy) biphenyl-4′-carbonyloxy] benzoic acid 2-methylbutyl ester (synthesis of alcohol) Dimethylolpropionic acid (18.0 mmol) and tetramethylammonium hydroxide (pentahydrate) (20.0 mmol) were stirred in DMF (150 ml) for 2 hours. Next, the bromo form obtained in (5)
20.0 mmol was added and the mixture was stirred for 6 hours. After the reaction, the product was extracted with ether, dried, and concentrated, and then purified by column chromatography to obtain a desired alcohol. (Yield 63%, ▲ [α] ²³ _D ▼ + 2.10 ° (CHCl ₃ )) (7) 4- [4 ″-{12- (2,2-diacetoxymethylpropionyloxy) dodecyloxy} biphenyl- 4'-
Carbonyloxy] benzoic acid 2-methylbutyl ester 7.5 mmol of alcohol obtained in (6) and acetic anhydride 45.
A solution of 0 mmol of pyridine in 5 ml was stirred at room temperature for 12 hours. The reaction solution was extracted with ether, and the ether layer was washed with aqueous HCl,
After drying and concentration, the residue was purified by column chromatography to obtain the desired novel compound having the following structural formula. (Yield 82%, ▲ [α] ²³ _D ▼ + 2.03 ° (CHCl ₃ )) The phase transition behavior of this compound was as follows.

The elemental analysis values of this compound are shown in the following table.

The ¹ H-NMR spectrum and IR spectrum of this compound are shown in FIG. 11 and FIG. 12, respectively.

〔The invention's effect〕

The novel compound of the present invention is an inexpensive and crystalline compound having a chemically stable chemical structure, and shows a ferroelectric Sc ^* phase capable of high-speed response in a wide temperature range up to room temperature. And electro-optics for various electro-optical devices such as digital displays for calculators and watches, electro-optical shutters, electro-optical apertures, optical modulators, optical communication optical path selector switches, memories, liquid crystal printer heads, variable focal length lenses, etc. It has high utility as an element and its industrial value is great.

[Brief description of drawings]

FIG. 1 is a chart of ¹ H-NMR spectrum of the compound obtained in Example 1. FIG. 2 is a chart of the IR spectrum of the compound obtained in Example 1. FIG. 3 is a chart of ¹ H-NMR spectrum of the compound obtained in Example 2. FIG. 4 is a chart of the IR spectrum of the compound obtained in Example 2. FIG. 5 is a chart of ¹ H-NMR spectrum of the compound obtained in Example 3. FIG. 6 is a chart of the IR spectrum of the compound obtained in Example 3. FIG. 7 is a chart of ¹ H-NMR spectrum of the compound obtained in Example 4. FIG. 8 is a chart of the IR spectrum of the compound obtained in Example 4. FIG. 9 is a chart of ¹ H-NMR spectrum of the compound obtained in Example 5. FIG. 10 is a chart of the IR spectrum of the compound obtained in Example 5. FIG. 11 is a chart of ¹ H-NMR spectrum of the compound obtained in Example 6. FIG. 12 is a chart of the IR spectrum of the compound obtained in Example 6.

Claims (1)

[Claims] 1. A general formula (In the formula, R ₁ and R ₅ represent an alkyl chain having 1 to ₅ carbon atoms and may be the same or different, and X ₁ and X ₂ are -O-, R ₂ may be the same or different, R ₂ represents —H or —CH ₃ , R ₃ represents an alkyl chain having 1 to 20 carbon atoms, and R ₄ represents Or And C _* represents an asymmetric carbon. ) A new compound represented by.