JPH0674241B2 - New compound - Google Patents

Description

Detailed Description of the Invention

[Field of Industrial Application] The present invention relates to a novel compound having liquid crystallinity and capable of high-speed response. More specifically, in the field of optoelectronics, in particular, digital display devices such as calculators and watches, electro-optical shutters, electro-optical apertures, optical modulators, optical communication optical path changeover switches, memories, liquid crystal printer heads, variable focal length lenses, etc. The present invention relates to a novel compound having liquid crystallinity and capable of high-speed response, which is used as an electro-optical device. [Prior Art] Liquid crystals have already been 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, visual characteristics and the like. Therefore, recently, as a solution to these drawbacks, a display device using a ferroelectric chiral smectic C-phase (SmC ^* phase) liquid crystal capable of high-speed response has been proposed. However, even in these cases, there are problems that the temperature range in which the smectic C phase is exhibited is high and the chemical stability is lacking. Those having a ferroelectric SmC ^* phase which has a relatively low temperature range and is capable of high-speed response are also known (JP-A-55-21479, JP-A-60-235885, and JP-A-61-1). 22072, JP-A-61-24576, etc.), these compounds are difficult to manufacture and difficult to obtain at low cost. JP-A-63-107950 discloses a liquid crystal compound having a 2-methylbutyl group as an optically active group at the molecular end, such as one having the following structural formula. This liquid crystalline compound is inexpensive, has a chemically stable chemical structure, and exhibits a ferroelectric chiral smectic C phase in a temperature range including room temperature. However, this liquid crystal compound is not always sufficient in response speed to changes in the electric field. [Problems to be Solved by the Invention] The present invention is a relatively inexpensive and chemically stable liquid crystal compound, which is a novel high-speed compound showing a ferroelectric SmC ^* phase in a wide temperature range up to room temperature or lower. It is intended to provide a responsive liquid crystal compound. [Means for Solving the Problems] As a result of repeated studies to achieve the above-mentioned object, the present inventors used an optically active group that is industrially easily obtained as a raw material, It was found that a novel liquid crystal compound satisfying the above object can be obtained by introducing it into the structure, and the present invention has been completed 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 group having 1 to ⁵ carbon atoms,
Each may be the same or different, X ¹ and X ² are —O—, And R ² may be the same or different, R ² represents —H or —CH ₃ , R ³ represents a C1-20 alkylene chain, and R ⁴ represents Or And n is an integer of 0 to 5, m is an integer of 1 to 10, provided that when n is 1, m is not 1 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. Production method [1] R ¹ and R ⁵ are the same, and X ¹ is And X ² is And R ⁴ is Of a compound of formula (1) Synthesis of ester form 4'-Hydroxybiphenyl-4-carboxylic acid is reacted with carbobenzoxylcolide to form an ester, and the hydroxyl group is protected with a carbobenzoxy group. (2) Synthesis of acid chloride The ester obtained in (1) is reacted with an acid halogenating agent such as phosphorus pentachloride to obtain the desired acid chloride. (3) Synthesis of ester form The following formula The optically active alcohol represented by and the acid chloride obtained in (2) are reacted in a solvent such as tetrahydrofuran (THF) or pyridine to form an ester, thereby obtaining a target ester. Here, examples of the optically active alcohol that can be used in the production of the novel compound of the present invention include (R) -1-methylpropanol, (S) -1-methylpropanol, and (R) -1.
-Methylbutanol, (S) -1-methylbutanol,
(R) -1-methylheptanol, (S) -1-methylheptanol, (R) -3-methylpentanol,
(S) -3-methylpentanol, (R) -6-methyloctanol, (S) -6-methyloctanol,
(R) -4-methylhexanol, (S) -4-methylhexanol and the like can be mentioned. (4) Synthesis of hydroxy form The ester body obtained in (3) is brought into contact with a hydrogenolysis catalyst such as palladium carbon in a hydrogen gas atmosphere to hydrolyze to remove the carbobenzoxy group which is a protective group, and to give the desired hydroxy body. obtain. (5) Synthesis of bromo compound Alkoxylating the resulting hydroxy body with potassium carbonate (4), which Br-R ³ in a solvent such as acetone in -Br
Is reacted to form a monoether to obtain the desired bromo compound. Here, the formula Br-R ³ compound of -Br is specifically dibromomethane, dibromoethane, dibromopropane, dibromobutane, dibromopentane, dibromohexane, dibromo heptane, dibromooctane, dibromononane, dibromodecane, dibromo undecane, Dibromododecane, dibromotridecane, dibromotetradecane, dibromopentadecane, dibromohexadecane, dibromoheptadecane, dibromooctadecane, dibromononadecane, and dibromoeicosane. (6) Synthesis of alcohol 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 (5) is reacted with this to esterify, Obtain the desired alcohol. Where the expression The compound of is specifically dimethylolacetic acid and 2,2-
It is dimethylolpropionic acid. (7) The alcohol compound obtained in (6) is reacted with (R ¹ CO) ₂ O (anhydride) to form a diester, thereby obtaining the desired novel compound. Here, the compound of the formula (R ¹ CO) ₂ O is specifically acetic anhydride,
Examples include propionic anhydride, butyric anhydride, valeric anhydride, and hexanoic anhydride. Production method [2] R ¹ and R ⁵ are the same, and X ¹ is And X ² is And R ⁴ is Of a compound of formula (1) Synthesis of ester form 4-Hydroxybenzoic acid is reacted with carbobenzoxylcolide to form an ester, and the hydroxyl group is protected with a carbobenzoxy group. (2) Synthesis of acid chloride The ester obtained in (1) is reacted with an acid halogenating agent such as phosphorus pentachloride to obtain the desired acid chloride. (3) Synthesis of ester form The optically active alcohol and the acid chloride obtained in (2)
Esterification by reaction in a solvent such as THF or pyridine,
The target ester is obtained. The term “optically active alcohol” as used herein means the production method [1]-
It is the same as that shown in (3). (4) Synthesis of hydroxy form The ester body obtained in (3) is brought into contact with a hydrocracking catalyst such as palladium carbon in a hydrogen gas atmosphere to hydrolyze, and the carbobenzoxy group as a protecting group is eliminated to obtain the desired hydroxy body. . (5) Synthesis of ester form 4-hydroxy-benzoic acid benzyl ester in the presence of potassium carbonate, is reacted with Br-R ³ -Br in a solvent such as acetone and monoetherified, give the ester form of interest. Here, the Br-R ³ -Br say, production method (1) - (5) the same of the is the one shown in. (6) Synthesis of carboxylic acid derivative The ester form obtained in (5) is decomposed with a palladium carbon catalyst and hydrogen gas to obtain the desired carboxylic acid form. (7) Synthesis of bromo compound The carboxylic acid derivative obtained in (6) is reacted with an acid halogenating agent such as thionyl chloride in a solvent such as toluene to obtain an acid halide. The obtained acid halide and (4)
Hydroxy form obtained in And are reacted in a solvent such as THF in the presence of triethylamine for esterification to obtain the desired bromo compound. Then, as shown in the following reaction formula, the alcohol compound and the novel compound are sequentially synthesized by the same operation as in the production method [1] to obtain the desired novel compound. Production method [3] R ¹ and R ⁵ are the same, and X ¹ is And X ² is And R ⁴ is Of a compound of formula (1) Synthesis of bromo compound The carboxylic acid derivative obtained by the production method [2]-(6) is reacted with an acid halogenating agent such as thionyl chloride in a solvent such as toluene to obtain an acid halide. The obtained acid halide is a hydroxy compound obtained in Production Example [1]-(4)
And are reacted in a solvent such as THF in the presence of triethylamine for esterification to obtain the desired bromo compound. Then, as shown in the following reaction formula, the alcohol compound and the novel compound are sequentially synthesized by the same operation as in the production method [1] to obtain the desired novel compound. Production method [4] R ¹ and R ⁵ are the same, and X ¹ is And X ² is And R ⁴ is Of a compound of formula (1) Synthesis of 4'-hydroxybiphenyl-4-carboxylic acid benzyl ester (ester form) 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 for esterification to obtain the desired ester form. Next, as shown in the following reaction formula, the same operation as in the above production method is carried out to obtain an ester, a carboxylic acid derivative,
The bromo compound, the alcohol compound, and the novel compound are sequentially synthesized to obtain the desired novel compound. [Examples] Hereinafter, the present invention will be described based on Examples, but these Examples do not limit the scope of the present invention. The structure of the obtained compound was confirmed by NMR, IR, and elemental analysis, and the phase transition temperature was measured and the phase was confirmed.
It was performed by DSC and polarization microscope, respectively. In addition, the electric field response speed changes significantly with respect to the temperature (the temperature from the SmC ^* phase upper limit temperature (Tc) to how low the temperature side is), so the measured temperature is Tc = -2 ° C for an objective comparison. The measurements were made uniformly as follows. Measurement of electric field response speed A compound is sandwiched between two 20 × 10 mm ITO substrates and the thickness is adjusted to 25 μm with a spacer, and the AC electric field E = 2 × 10 ⁶ V / m
And the response time of the change in the amount of transmitted light (0 → 90%) was measured. In the formula showing the phase transition behavior, each symbol has the following meaning. Cry: crystalline state, SmC ^* : chiral smectic C phase liquid crystal state, SmA: smectic A phase liquid crystal state, Iso: isotropic liquid Example 1 1. [1] 4'-Carbobenzoxyoxybiphenyl-4
-Synthesis of carboxylic acid (ester (1)) 65 mmol of carbobenzoxylcolide was added dropwise to a 200 ml aqueous solution of 55 mmol of 4'-carbobenzoxyoxybiphenyl-4-carboxylic acid and 65 mmol of sodium hydroxide under ice temperature. After stirring for 24 hours, the precipitate was washed with water, filtered and dried,
Purification by column chromatography gave the desired ester form (1). (Yield 85%) 1. [2] 4'-Carbobenzoxyoxybiphenyl-4
-Synthesis of carboxylic acid chloride (acid chloride (2)) 1. A solution of 27 mmol of the ester (1) obtained in [1] and 27 mmol of phosphorus pentachloride in 50 ml of ether was stirred at room temperature for 24 hours. After the reaction, ether was removed, and the crystals were recrystallized from hexane to obtain the desired acid chloride (2). (Yield 89%) 1. [3] 4'-Carbobenzoxyoxybiphenyl-4
-Synthesis of carboxylic acid 1-methylbutyl ester (ester (3)) A solution of optically active 1-methylbutanol (20 mmol) in THF (20 ml) and pyridine (40 ml) was ice-cooled, and a solution of the acid chloride (2) (16 mmol in THF) obtained in 1. [2] was added dropwise. The temperature was gradually returned to room temperature and stirred for 8 hours. After the reaction, the mixture was extracted with ether, concentrated, and then purified by column chromatography to obtain the target ester form (3). (Yield 68%) 1. Synthesis of [4] 4'-hydroxybiphenyl-4-carboxylic acid 1-methylbutyl ester (hydroxy compound (4)) 1. An ethyl acetate solution containing 10 mmol of the ester (3) obtained in [3] and 0.5 g of palladium carbon (5% catalyst) was reacted in a hydrogen gas atmosphere for 4 hours. After the reaction, palladium carbon was filtered through a membrane filter, the filtrate was concentrated, and then purified by column chromatography to obtain the target hydroxy compound (4). (Yield 64%) 1. Synthesis of [5] 4 '-(12-bromododecyloxy) biphenyl-4-carboxylic acid 1-methylbutyl ester (bromo compound (5)) 1. A solution of 10.5 mmol of the hydroxy compound (4) obtained in [4], 21.1 mmol of dibromododecane, and 42.2 mmol of potassium carbonate in 50 ml of acetone was refluxed for 6 hours. The reaction solution was filtered and concentrated, and then purified by column chromatography to obtain the desired bromo compound (5). (Yield 82%, [α ▲] ²³ _D ▼ ＝
-13.3 ° (CHCl ₃ ) 1. [6] 4 ′-[12- (2,2-dimethylolpropionyloxy) dodecyloxy] biphenyl-4-carboxylic acid 1-methylbutyl ester (alcohol (6))
Synthesis of 6.0 mmol of 2,2-dimethylolpropionic acid and 6.6 mmol of tetramethylammonium hydroxide (pentahydrate) were stirred in 50 ml of DMF for 2 hours. Next, 6.0 mmol of the bromo compound (5) obtained in 1. [5] was added, and the mixture was stirred for 6 hours. 100 water in the reaction solution
After adding ml, the mixture was extracted with ether, dried and concentrated, and then purified by column chromatography to obtain the desired alcohol derivative (6). (Yield 76%, [α ▲] ²³ _D ▼ = -12.
9 ° (CHCl ₃ )) 1. [7] Synthesis of 4 ′-[12- {2,2-bis (acetoxymethyl) propionyloxy} dodecyloxy] biphenyl-4-carboxylic acid 1-methylbutyl ester 1. A solution of 2.5 mmol of the alcohol (6) obtained in 6] and 15 mmol of acetic anhydride in 5 ml of pyridine was stirred at room temperature for 12 hours. The reaction solution was extracted with ether, the ether layer was washed with HCl water, dried, concentrated, and then purified by column chromatography to obtain the desired novel compound of the following formula. (yield
93%, [α ▲] ²³ _D ▼ ＝ -12.8 ° (CHCl ₃ ) The phase transition behavior of this compound was as follows. The electric field response speed of this compound was 60 μs at 8 ° C. 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. 1 and FIG. 2, respectively. Example 2 2. [1] Synthesis of 4-carbobenzoxyoxybenzoic acid (ester (7)) 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, the precipitate was washed with water, filtered, dried, and purified by column chromatography to obtain the target ester body (7). (Yield 99%) 2. [2] Synthesis of 4-carbobenzoxyoxybenzoic acid chloride (acid chloride (8)) 2. A solution of 27 mmol of the ester (7) obtained in [1] and 27 mmol of phosphorus pentachloride in 50 ml of ether was stirred at room temperature for 24 hours. After the reaction, ether was removed, and the crystal was recrystallized from hexane to obtain the desired acid chloride (8). (Yield 57%) 2. [3] Synthesis of 4-carbobenzoxyoxybenzoic acid 1-methylheptyl ester (ester (9)) 20 ml of optically active 1-methylheptanol 20 mmol THF,
A 40 ml solution of pyridine was ice-cooled, and a THF solution of 16 mmol of acid chloride (8) obtained in 2. [2] was added dropwise. The temperature was gradually returned to room temperature and stirred for 8 hours. After the reaction, ether extraction,
After concentration, purified by column chromatography,
The target ester (9) was obtained. (Yield 63%) 2. Synthesis of 4-hydroxybenzoic acid 1-methylheptyl ester (hydroxy compound (10)) 2. An ethyl acetate solution containing 10 mmol of the ester (9) obtained in [3] and 0.5 g of palladium carbon (5% catalyst) was reacted in a hydrogen gas atmosphere for 4 hours. After the reaction, palladium carbon was filtered through a membrane filter, the filtrate was concentrated, and then purified by column chromatography to obtain the target hydroxy compound (10). (Yield 64%) 2. Synthesis of [5] 4- (12-bromododecyloxy) benzoic acid benzyl ester (ester (11)) A solution of dibromododecane (150 mmol), 4-hydroxybenzoic acid benzyl ester (50 mmol) and potassium carbonate (0.3 mol) in acetone (500 ml) was refluxed for 6 hours. The reaction solution was filtered and concentrated, and then purified by column chromatography to obtain the target ester form (11). (Yield 82%) 2. Synthesis of [6] 4- (12-bromododecyloxy) benzoic acid (carboxylic acid derivative (12)) 2. A solution of 100 mmol of the ester (11) obtained in [5] and 2.0 g of palladium carbon (5% catalyst) in 150 ml of ethyl acetate was stirred in the presence of hydrogen gas for 5 hours. The reaction solution was filtered and concentrated, and then purified by column chromatography to obtain the desired carboxylic acid derivative (12). (yield
98%) 2. Synthesis of [7] 4- [4 '-(12-bromododecyloxy) benzoyloxy] benzoic acid 1-methylheptyl ester (bromo compound (13)) 2. 50 mmol of the carboxylic acid derivative (12) obtained in [6]
The mixture was stirred in a solution of 30 ml of toluene and 10 ml of thionyl chloride at 80 ° C. for 2 hours to give an acid chloride. Next, excess thionyl chloride and toluene were distilled off under reduced pressure. 2.
A solution of 55 mmol of the hydroxy form (10) obtained in [4] and 60 mmol of trietheramine in 200 ml of THF was stirred, then the THF solution of the acid chloride obtained above was added dropwise, and the mixture was stirred for 8 hours. After the reaction, ether extraction, washing with HCl water, drying,
After concentration and concentration, the product was purified by column chromatography to obtain the desired bromo compound (13). (Yield 86%,
[Α ▲] ²³ _D ▼ = -15.2 ° (CHCl ₃ )) 2. [8] 4- [4 '-{12- (2,2-dimethylolpropionyloxy) dodecyloxy} benzoyloxy]
Synthesis of 1-methylheptyl benzoate (alcohol (14)) 2,2-Dimethylolpropionic acid (18.0 mmol) and tetramethylammonium hydroxide (pentahydrate) (20.0 mmol) were added to DMF150.
Stir in ml for 2 hours. Next, 18.0 mmol of the bromo compound (13) obtained in 2. [7] was added and stirred for 6 hours. After the reaction
After extraction with ether, drying and concentration, the product was purified by column chromatography to obtain the desired alcohol (14)
Got (Yield 89%, [α ▲] ²³ _D ▼ ＝ -14.9 ° (CHC
l ₃ )) 2.

[9] 4- [4 '-[12- {2,2-bis (acetoxy
Methyl) propionyloxy} dodecyloxy] benzo
Iloxy] benzoic acid 1-methylheptyl ester
Synthesis2. 7.5 mmol of alcohol (14) obtained in [8] and anhydrous
A solution of 45 mmol of acetic acid in 5 ml of pyridine was stirred at room temperature for 12 hours.
It was The reaction solution was extracted with ether and the ether layer was washed with aqueous HCl.
After purification, drying and concentration, column chromatography
And purified to obtain the desired novel compound. (Yield 81
%, [Α ▲]^{twenty three} _D▼ ＝ -14.9 ° (CHCl₃)) The phase transition phenotype of this compound was as follows.The electric field response speed of this compound was 75 μs at −5 ° C. The elemental analysis values of this compound are shown in the following table.Of this compound¹The H-NMR spectrum is shown in FIG.
The tor is shown in FIG. Example 33. [1] 4'-Carbobenzoxyoxybiphenyl-4
-Carboxylic acid 1-methylheptyl ester (ester
Body (15)) synthesis20 ml of optically active 1-methylheptal 20 mmol THF,
A solution of 40 ml of lysine was ice-cooled to obtain the acid obtained in Example 1. [2].
A solution of 16 mmol of chloride (2) in THF was added dropwise. Temperature gradually
After returning to room temperature, the mixture was stirred for 8 hours. Reaction solution, ether extraction
After extraction and concentration, purification by column chromatography
The target ester form (15) was obtained. (Yield 88%) 3. [2] 4'-hydroxybiphenyl-4-carboxylic acid
 1-Methylheptyl ester (hydroxy form (16))
Synthesis of3. 10 mmol of ester (15) obtained in [1], Paradium
A solution of 0.5 g of mcarbon (5% catalyst) in ethyl acetate was added to hydrogen gas.
The reaction was carried out for 4 hours in the atmosphere. After the reaction, the membrane fi
Filter palladium carbon with a luther and concentrate the filtrate.
Then, purify by column chromatography, and then
A droxy body (16) was obtained. (Yield 98%) 3. [3] 4 '-[4 "-(12-bromododecyloxy)
Benzoyloxy] biphenyl-4-carboxylic acid 1-
Synthesis of methylheptyl ester (bromo compound (17))Example 2. Carboxylic acid derivative (12) obtained in [6] 50 mm
ol in a solution of 30 ml of toluene and 10 ml of thionyl chloride at 80 ° C.
And stirred for 2 hours to give the acid chloride. Then excess salt
Thionyl chloride and toluene were distilled off under reduced pressure.
3. 55 mmol of hydroxy compound (16) obtained in [2] and tri
A solution of 60 mmol of ethylamine in 200 ml of THF is stirred, then
The THF solution of the acid chloride obtained in was added dropwise and stirred for 8 hours.
It was After the reaction, ether extraction, washing with HCl water, drying,
And after concentration, it is purified by column chromatography.
The desired bromo compound (17) was obtained. (Yield 79%,
[Α ▲]^{twenty three} _D▼ ＝ -14.7 ° (CHCl₃)) 3. [4] 4 '-[4 "-{12- (2,2-dimethyl roll
Propionyloxy) dodecyloxy} benzoyl oxy
Ci] biphenyl-4-carboxylic acid 1-methylheptyl
Synthesis of steal (alcohol body (18))2,2-Dimethylolpropionic acid 18.0 mmol and hydroxide hydroxide
20.0 mmol of tramethylammonium (pentahydrate) was added to DMF150.
Stir in ml for 2 hours. Next, the block obtained in 3. [3]
18.0 mmol of the body (17) was added and stirred for 6 hours. After the reaction
After extraction with ether, drying and concentration, column chromatography
Purification by chromatography, the desired alcohol (18)
Got (Yield 71%, [α ▲]^{twenty three} _D▼ ＝ -14.5 ° (CHC
l₃)) 3. [5] 4 '-[4 "-[12- {2,2-bis (acetoxy)
Cimethyl) propionyloxy} dodecyloxy] ben
Zoyloxy] biphenyl-4-carboxylic acid 1-methyl
Synthesis of ruheptyl ester3. 7.5 mmol of alcohol (18) obtained in [4] and anhydrous
A solution of 45 mmol of acetic acid in 5 ml of pyridine was stirred at room temperature for 12 hours.
It was The reaction solution was extracted with ether and the ether layer was washed with aqueous HCl.
After purification, drying and concentration, column chromatography
And purified to obtain the desired novel compound. (Yield 78
%, [Α ▲]^{twenty three} _D▼ ＝ -14.1 ° (CHCl₃)) The phase shift of this compound was as follows.The electric field response speed of this compound was 42 μs at 86 ° C. The elemental analysis values of this compound are shown below and in the table.Of this compound¹The H-NMR spectrum is shown in FIG.
The tor is shown in FIG. Example 44. [1] 4'-hydroxybiphenyl-4-carboxylic acid
Synthesis of benzyl ester (ester form (19))0.1 mol of 4'-hydroxybiphenyl-4-carboxylic acid
And tetramethylammonium hydroxide (pentahydrate) 0.11mo
A solution of l of DMF in 200 ml was stirred for 2 hours. Next, benzyl bromide
0.1 mol was added and the mixture was stirred for 6 hours. After reaction, extract with ether
After column extraction, drying and concentration, column chromatography
The product was purified by filtration to obtain the desired ester form (19).
(Yield 76%) 4. [2] 4 '-(12-bromododecyloxy) bipheni
Lu-4-carboxylic acid benzyl ester (ester form
(20)) Synthesis4. 70 mmol of ester (19) obtained in [1], dibromo
Dodecane 0.21mol and potassium carbonate 0.4mol acetone
One solution was refluxed for 6 hours. The reaction solution was filtered and concentrated
After that, purify by column chromatography to obtain the target
An ester form (20) was obtained. (Yield 89%) 4. [3] 4 '-(12-bromododecyloxy) bipheni
Synthesis of ru-4-carboxylic acid (carboxylic acid derivative (21))4. 60 mmol of the ester (20) obtained in [2] and paradi
Umcarbon (5% catalyst) 2.0g ethyl acetate 500ml solution
Was stirred under a hydrogen gas atmosphere for 24 hours. After reaction, reaction liquid
Is filtered, concentrated, and purified by column chromatography
The desired carboxylic acid derivative (21) was obtained. (yield
98%) 4. [4] 4- [4 ″-(12-bromododecyloxy)-
4'-biphenylylcarbonyloxy [benzoic acid 1-
Synthesis of methylheptyl ester (bromo compound (22))4. 50 mmol of the carboxylic acid derivative (21) obtained in [3]
2 hours at 80 ° C in a solution of 20 ml of toluene and 10 ml of thionyl chloride.
The mixture was stirred for a while to give an acid chloride. Excess thionyl chloride and tolu
The ene was distilled off under reduced pressure. Next, in Example 2. [4]
The resulting hydroxy form (10) 55 mmol and triethylami
A solution of 60 mmol of THF in 200 ml of THF was stirred to obtain the acid chloride obtained above.
The THF solution of the product was added dropwise and reacted for 8 hours. After the reaction,
Ether extraction, washing with HCl water, drying, and concentration
After purification, column chromatography
A bromo compound (22) was obtained. (Yield 79%), [α ▲]^{twenty three} _D
▼ ＝ -14.7 ° (CHCl₃)) 4. [5] 4- [4 ″-{12- (2,2-dimethylol pro
Pionyloxy) dodecyloxy} -4'-biphenylyl
Lucarbonyloxy] benzoic acid 1-methylheptyl s
Ter (Synthesis of alcohol (23))2,2-Dimethylolpropionic acid 18.0 mmol and hydroxide hydroxide
20.0 mmol of tramethylammonium (pentahydrate) was added to DMF150.
Stir in ml for 2 hours. Next, the block obtained in 4. [4]
After adding 18.0 mmol of (22) moss and stirring for 6 hours,
Column extraction, drying, and concentration, followed by column chromatography.
Purify with Raffy to obtain the desired alcohol (23)
Obtained. (83% yield, [α ▲]^{twenty three} _D▼ ＝ -14.3 ° (CHC
l₃)) 4. [6] 4- [4 ″-[12- {2,2-bis (acetoxy
Methyl) propionyloxy} dodecyloxy] -4 '
-Biphenylylcarbonyloxy] benzoic acid 1-methyl
Synthesis of heptyl ester4. 7.5 mmol of alcohol (23) obtained in [5] and anhydrous
A solution of 45.0 mmol of acetic acid in 5 ml of pyridine was stirred at room temperature for 12 hours.
It was The reaction solution was extracted with ether and the ether layer was washed with aqueous HCl.
After purification, drying and concentration, column chromatography
And purified to obtain the desired novel compound. {Yield 98
%, [Α ▲]^{twenty three} _D▼ ＝ -14.4 ° (CHCl₃)) The phase transition behavior of this compound was as follows.The electric field response speed of this compound was 73 μs at 61 ° C. The elemental analysis values of this compound are shown in the following table.Of this compound¹The H-NMR spectrum is shown in FIG.
The tor is shown in FIG. Example 55. [1] 4-Carbonbenzoxyoxybenzoic acid 1-me
Synthesis of tylbutyl ester (ester (24))20 ml of optically active 1-methylbutanol 20 mmol THF,
The 40 ml solution of lysine was ice-cooled to obtain the acid obtained in Example 2. [2].
A solution of 16 mmol of chloride (8) in THF was added dropwise. Temperature gradually
After returning to room temperature, the mixture was stirred for 8 hours. After reaction, extract with ether
After extraction and concentration, purification by column chromatography
Then, the target ester form (24) was obtained. (Yield 71%) 5. [2] 4-Hydroxybenzoic acid 1-methylbutyl ether
Synthesis of stell (hydroxy form (25))5. 10 mmol of the ester (24) obtained in [1], Paradium
A solution of 0.5 g of mcarbon (5% catalyst) in ethyl acetate was added to hydrogen gas.
The reaction was carried out for 4 hours in the atmosphere. After the reaction, the membrane fi
Filter palladium carbon with a luther and concentrate the filtrate.
After purification, column chromatography
A hydroxy compound (25) was obtained. (Yield 99%) 5. [3] 4- [4 ″-(12-bromododecyloxy)-
4'-Biphenylylcarbonyloxy] benzoic acid 1-
Synthesis of methyl butyl ester (bromo compound (26))Example 4. Carboxylic acid derivative (21) obtained in [3] 50 mm
ol in a solution of 20 ml of toluene and 10 ml of thionyl chloride.
The mixture was stirred at 0 ° C for 2 hours to give an acid chloride. Excess thionyl chloride
And toluene were distilled off under reduced pressure. Then, in 5. [2]
The resulting hydroxy form (25) 55 mmol and triethylamido
A solution of 60 mmol of THF in 200 ml of THF was stirred to obtain the acid chloride obtained above.
The THF solution of the product was added dropwise and reacted for 8 hours. After the reaction,
Ether extraction, washing with HCl water, drying, and concentration
After purification, column chromatography
A bromo compound (26) was obtained. (Yield 73%, [α ▲]^{twenty three} _D▼
= -13.0 ° (CHCl₃)) 5. [4] 4- [4 ″-{12- (2,2-dimethylol pro
Pionyloxy) dodecyloxy} -4'-biphenylyl
Lucarbonyloxy] benzoic acid 1-methylbutyleth
Ter (Synthesis of alcohol (27))2,2-Dimethylolpropionic acid 18.0 mmol and hydroxide hydroxide
20.0 mmol of tramethylammonium (pentahydrate) was added to DMF150.
Stir in ml for 2 hours. Next, the block obtained in 5. [3]
18.0 mmol of the moth body (26) was added, and the mixture was stirred for 6 hours. After the reaction
After extraction with ether, drying and concentration, column chromatography
Purification by chromatography, the desired alcohol (27)
Got (Yield 67%, [α ▲]^{twenty three} _D▼ ＝ -12.8 ° (CHC
l₃)) 5. [5] 4- [4 ″-[12- {2,2-bis (acetoxy
Methyl) propionyloxy} dodecyloxy] -4 '
-Biphenylylcarbonyloxy] benzoic acid 1-methyl
Synthesis of rubutyl ester5. 7.5 mmol of alcohol (27) obtained in [4] and anhydrous
A solution of 45.0 mmol of acetic acid in 5 ml of pyridine was stirred at room temperature for 12 hours.
It was The reaction solution was extracted with ether and the ether layer was washed with aqueous HCl.
After purification, drying and concentration, column chromatography
And purified to obtain the desired novel compound. (Yield 96
%, [Α ▲]^{twenty three} _D▼ ＝ -12.8 ° (CHCl₃)) The phase transition behavior of this compound was as follows.The electric field response speed of this compound was 41 μs at 73.5 ° C. The elemental analysis values of this compound are shown in the following table.Of this compound¹The H-NMR spectrum is shown in FIG.
The tor is shown in FIG. Example 66. [1] 4'-Carbobenzoxyoxybiphenyl-4
-Carboxylic acid 3-methylpentyl ester (ester
Body (28)) synthesis20 ml of optically active 3-methylpentanol 20 mmol THF,
A 40 ml solution of pyridine was ice-cooled and obtained in Example 1. [2].
A solution of 16 mmol of acid chloride (2) in THF was added dropwise. Slow down the temperature
The mixture was returned to room temperature and stirred for 8 hours. After the reaction, ether
After extraction and concentration, purification by column chromatography
Then, the target ester form (28) was obtained. (Yield 89%) 6. [2] 4'-hydroxybiphenyl-4-carboxylic acid
 3-Methylpentyl ester (hydroxy form (29))
Synthesis of6. [1] 10 mmol of the obtained ester (28), palladium
A solution of 0.5 g of carbon (5% catalyst) in ethyl acetate was added to hydrogen gas.
The reaction was carried out in the atmosphere for 4 hours. After reaction, membrane fill
The palladium carbon was filtered using a filter and the filtrate was concentrated.
After purification by column chromatography,
A dodroxy body (29) was obtained. (Yield 96%) 6. [3] 4 '-[4 "-(12-bromododecyloxy)
Benzoyloxy] biphenyl-4-carboxylic acid 3-
Synthesis of methyl pentyl ester (bromo compound (30))Example 2. Carboxylic acid derivative (12) obtained in [6] 50 mm
ol in a solution of 30 ml of toluene and 10 ml of thionyl chloride at 80 ° C.
And stirred for 2 hours to give the acid chloride. Then excess salt
Thionyl chloride and toluene were distilled off under reduced pressure.
6. 55 mmol of hydroxy compound (29) obtained in [2] and tri
A solution of 60 mmol of ethylamine in 200 ml of THF is stirred, then
The THF solution of the acid chloride obtained in was added dropwise and stirred for 8 hours.
It was After the reaction, extract with ether, wash with HCl water, and dry.
After purification and concentration, purification by column chromatography
The desired bromo compound (30) was obtained. (80% yield,
[Α ▲]^{twenty three} _D▼ ＝ ＋ 2.79 ° (CHCl₃)) 6. [4] 4 '-[4 "-{12- (2,2-dimethylolprop
Ropionyloxy) dodecyloxy} benzoyloxy
Ci] biphenyl-4-carboxylic acid 3-methylpentyl
Esters (synthesis of alcohols (31)2,2-Dimethylolpropionic acid 18.0 mmol and hydroxide hydroxide
20.0 mmol of tramethylammonium (pentahydrate) was added to DMF150.
Stir in ml for 2 hours. Next, the block obtained in 6. [3]
18.0 mmol of the body (30) was added and stirred for 6 hours. After the reaction
After extraction with ether, drying and concentration, column chromatography
Purification by chromatography, the desired alcohol (31)
Got (Yield 76%), [α ▲]^{twenty three} _D▼ ＝ ＋ 2.71 ° (CHC
l₃)) 6. [5] 4 '-[4 "-[12- {2,2-bis (acetoxy)
Cimethyl) propionyloxy} dodecyloxy] ben
Zoyloxy] biphenyl-4-carboxylic acid 3-methyi
Synthesis of rupentyl ester6. 7.5 mmol of alcohol (31) obtained in [4] and anhydrous
A solution of 45.0 mmol of acetic acid in 5 ml of pyridine was stirred at room temperature for 12 hours.
It was The reaction solution was extracted with ether and the ether layer was washed with aqueous HCl.
After purification, drying and concentration, column chromatography
And purified to obtain the desired novel compound. (Yield 99
%, [Α ▲]^{twenty three} _D▼ ＝ ＋ 2.67 ° (CHCl₃)) The phase transition behavior of this compound was as follows.The electric field response speed of this compound was 110 μs at 58 ° C.
It was The elemental analysis values of this compound are shown in the following table.Of this compound¹The H-NMR spectrum is shown in Fig. 11, and the IR spectrum is
The tor is shown in FIG. Example 77. [1] 4 '-(10-Bromodecyloxy) biphenyl
-4-carboxylic acid benzyl ester (ester (3
2)) SynthesisExample 4. 70 mmol of the ester (19) obtained in [1], diester
Brominedecane 0.21 mol and potassium carbonate 0.4 mol
Ton 1 solution was refluxed for 6 hours. The reaction solution is filtered and concentrated
After purification, column chromatography
Was obtained (75% yield) 7. [2] 4 '-(10-bromodecyloxy) biphenyl
Synthesis of 4-carboxylic acid (carboxylic acid derivative (33))7. 60 mmol of ester (32) obtained in [1] and paradi
Umcarbon (5% catalyst) 2.0g ethyl acetate 500ml solution
Was stirred under a hydrogen gas atmosphere for 24 hours. After the reaction, filtration and
And concentrate, purify by column chromatography, and
A carboxylic acid derivative (33) was obtained. (Yield 98%) 7. [3] 4- [4 ″-(10-bromodecyloxy)-
4'-Biphenylylcarbonyloxy] benzoic acid 1-
Synthesis of methylheptyl ester (bromo compound (34))7. 50 mmol of the carboxylic acid derivative (35) obtained in [2]
2 hours at 80 ° C in a solution of 20 ml of toluene and 10 ml of thionyl chloride.
The mixture was stirred for a while to give an acid chloride. Excess thionyl chloride and tolu
The ene was distilled off under reduced pressure. Next, in Example 2. [4]
The resulting hydroxy form (10) 55 mmol and triethylami
A solution of 60 mmol of THF in 200 ml of THF was stirred to obtain the acid chloride obtained above.
The THF solution of the product was added dropwise and reacted for 8 hours. After the reaction,
Ether extraction, washing with HCl water, drying, and concentration
After purification, column chromatography
A bromo compound (34) was obtained. (Yield 69%, [α ▲]^{twenty three} _D▼
= -14.8 ° (CHCl₃)) 7. [4] 4- [4 ″-{10- & 2,2-dimethylol pro
Pionyloxy) decyloxy} -4'-biphenylyl
Carbonyloxy] benzoic acid 1-methylheptyl s
Synthesis of (tel) alcohols (35))2,2-Dimethylolpropionic acid 18.0 mmol and hydroxide hydroxide
20.0 mmol of tramethylammonium (pentahydrate) was added to DMF150.
Stir in ml for 2 hours. Next, the bromo obtained in 7. [3]
The body (34) (18.0 mmol) was added, and the mixture was stirred for 6 hours. After the reaction,
Column extraction, drying, and concentration, followed by column chromatography.
Purify with Raffy and obtain the desired alcohol (35)
Obtained. (83% yield, [α ▲]^{twenty three} _D▼ ＝ -14.7 ° [CHC
l₃)) 7. [5] 4 '-[4 "-[10- {2,2-bis (acetoxy)
Cimethyl) propionyloxy} decyloxy] -4 '
-Biphenylylcarbonyloxybenzoic acid 1-methyl
Synthesis of heptyl ester7. 7.5 mmol of alcohol (35) obtained in [4] and anhydrous
A solution of 45 mmol of acetic acid in 5 ml of pyridine was stirred at room temperature for 12 hours.
It was The reaction solution was extracted with ether and the ether layer was washed with aqueous HCl.
After purification, drying and concentration, column chromatography
And purified to obtain the desired novel compound. (Yield 78
%, [Α ▲]^{twenty three} _D▼ ＝ -14.6 ° (CHCl₃)) The phase transition behavior of this compound was as follows.The electric field response speed of this compound was 81 μs at 58 ° C. The elemental analysis values of this compound are shown in the following table.Of this compound¹The H-NMR spectrum is shown in Fig. 13, and the IR spectrum is
The tor is shown in FIG. Comparative Example 1(1) 4'-hydroxybiphenyl-4-carboxylic acid
2-methyl butyl ester (hydroxy compound (36))
Success93 'of 4'-hydroxybiphenyl-4-carboxylic acid
And 467 mmol of 2-methylbutanol in the presence of 2 ml of concentrated sulfuric acid,
Refluxed in 150 ml of benzene for 25 hours. The reaction solution was concentrated
After that, recrystallize with a mixed solvent of toluene and hexane for the purpose
A hydroxy compound (36) was obtained. (Yield 98%, [α
▲]^{twenty three} _D▼ ＝ ＋ 4.35 ° (CHCl₃)) (2) 4 '-(12-bromododecyloxy) biphenyl
-4-carboxylic acid 2-methylbutyl ester (bromo form
(37)) Synthesis10.5 mmol of hydroxy form (36) obtained in (1), dibromide
Acetone of mododecane 21.1 mmol, potassium carbonate 42.2 mmol
The 50 ml solution was refluxed for 6 hours. The reaction solution was filtered and concentrated
After that, purify by column chromatography to obtain the target
A bromo compound (37) was obtained. (Yield 90%, [α ▲]^{twenty three} _D▼ ＝
+ 2.31 ° (CHCl₃)) (3) 4 '-{12- (2,2-dimethylolpropionyl)
(Oxy) dodecyloxy} biphenyl-4-carboxylic acid
Combination of 2-methylbutyl ester (alcohol (38))
Success2,2-Dimethylolpropionic acid 6.0 mmol and hydroxylated tet
Lamethylammonium (pentahydrate) 6.6 mmol in DMF 50 ml
And stirred for 2 hours. Next, the bromo compound obtained in (2)
(37) 6.0 mmol was added and stirred for 6 hours. 100 water in the reaction solution
After adding ml, extract with ether, dry and concentrate,
Purify by Lamb chromatography to obtain the desired alcohol
To obtain a sol body (38). (Yield 50%, [α ▲]^{twenty three} _D▼ = +
2.11 ° (CHCl₃)) (4) 4 '-[12- {2,2-bis (acetoxymethyl)
Propionyloxy} dodecyloxy] biphenyl-4
-Synthesis of carboxylic acid 2-methylbutyl ester2.5 mmol of alcohol (38) obtained in (3) and anhydrous vinegar
A solution of 15 mmol of acid in 5 ml of pyridine was stirred at room temperature for 12 hours.
The reaction solution was extracted with ether, and the ether layer was washed with HCl water and dried.
After being dried and concentrated, purified by column chromatography
The desired novel compound was obtained. (Yield 76%, [α
▲]^{twenty three} _D▼ ＝ ＋ 2.10 ° (CHCl₃)) The phase transition behavior of this compound was as follows.The electric field response speed of this compound was 130 μs at 16 ° C. The elemental analysis values of this compound are shown in the following table.Comparative example 2(1) 4-Hydroxybenzoic acid 2-methylbutyl es
Synthesis of ter (hydroxy compound (39))0.29 mol of 4-hydroxybenzoic acid and (S)-(-)-2
-Methylbutanol (0.35 mol) in the presence of concentrated sulfuric acid (1 ml)
Refluxed in 150 ml of Ruen. After concentrating the reaction solution,
Purification by column chromatography and
Got a body (39). (65% yield, [α ▲]^{twenty three} _D▼ = + 4.9
5 ° (CHCl₃)) (2) 4-carbon benzoxyoxybenzoic acid (este
(40)) synthesis55 mmol of 4-hydroxybenzoic acid and 65 of sodium hydroxide
Carbobenzoxicyl chloride in 200 ml of water (mmol) under ice temperature
Lido 65 mmol was added dropwise. After stirring for 24 hours, wash the precipitate with water,
Filtered, dried, purified by column chromatography,
The target ester (40) was obtained. (Yield 99%, m.p.
(181.9-183.1 ℃) (3) 4-Carbobenzoxyoxybenzoic acid chloride
Synthesis of (acid chloride (41))27 mmol of the ester (40) obtained in (2) and lithium pentachloride
A solution of 27 mmol of ether in 50 ml of ether was stirred at room temperature for 24 hours.
After the reaction, the product is deethered and the crystals are recrystallized from hexane.
The target acid chloride (41) was obtained. (Yield 57%, m.
(p.65.5-67.4 ℃) (4) 4- (4'-carbobenzoxyoxybenzoyl)
Oxy) benzoic acid 2-methylbutyl ester (este
(42)) synthesisThe hydroxy form (39) obtained in (1), THF 20 ml, pyri
The 40 ml gin solution was ice-cooled and the acid chloride (4
1) 16 mmol of THF solution was added dropwise. Gradually increase the temperature to room temperature
Then, the mixture was stirred for 8 hours. After the reaction, extract with ether and concentrate
After purification, column chromatography
The ester compound (42) was obtained. (Yield 63%, m.p.64.4-6
5.4 ℃) (5) 4- (4'-hydroxybenzoyloxy) benzo
Aromatic acid 2-methylbutyl ester (hydroxy compound (4
3)) Synthesis10 mmol of ester (42) obtained in (4), palladium
A solution of 0.5 g of carbon (5% catalyst) in ethyl acetate was added to hydrogen gas.
The reaction was carried out in the atmosphere for 4 hours. After reaction, membrane fill
Filter the palladium carbon and concentrate it.
Purification by column chromatography and
Got a body (43). (Yield 64%, m.p. 90.8-92.6 ° C) (6) 4- [4 '-(12-bromododecyloxy) ben
Zoyloxy] benzoic acid 2-methylbutyl ester
Synthesis of (bromo compound (44))10.5 mmol of hydroxy derivative (43) obtained in (5), dibromide
Acetone of mododecane 21.1 mmol, potassium carbonate 42.2 mmol
The 50 ml solution was refluxed for 6 hours. The reaction solution was filtered and concentrated
After that, purify by column chromatography to obtain the target
A bromo compound (44) was obtained. (Yield 82%, [α ▲]^{twenty three} _D▼ ＝
+ 2.79 ° (CHCl₃)) (7) 4- [4 '-{12- (2,2-dimethylolpropene
Onyloxy) dodecyloxy} benzoyloxy] ammonium
Benzoic acid 2-methylbutyl ester (alcohol ((4
5)) Synthesis2,2-Dimethylolpropionic acid 6.0 mmol and hydroxylated tet
Lamethylammonium (pentahydrate) 6.6 mmol in DMF 50 ml
And stirred for 2 hours. Next, the bromo compound (4
4) 6.0 mmol was added and stirred for 6 hours. 100 ml of water in the reaction solution
Was added to the mixture, extracted with ether, dried and concentrated.
Purification by column chromatography to obtain the desired alcohol
I got a le body (45). (Yield 42%, [α ▲]^{twenty three} _D▼ ＝ ＋ 2.9
0 ° (CHCl₃)) (8) 4 '-[12- {2,2-bis (acetoxymethyl)
Propionyloxy} dodecyloxy] benzoyl oxy
Synthesis of 2-benzoic acid benzoic acid2.5 mmol of alcohol (45) obtained in (7) and anhydrous vinegar
A solution of 15 mmol of acid in 5 ml of pyridine was stirred at room temperature for 12 hours.
The reaction solution was extracted with ether, and the ether layer was washed with HCl water and dried.
Dry and concentrate, then purify by column chromatography
Then, the target compound was obtained. (70% yield, [α ▲]^{twenty three}
_D▼ ＝ ＋ 2.85 ° (CHCl₃)) The phase transition behavior of this compound was as follows.The electric field response speed of this compound was 210 μs at 1 ° C. The elemental analysis values of this compound are shown in the following table.Comparative Example 3(1) 4'-hydroxybiphenyl-4-carboxylic acid
2-methyl butyl ester (hydroxy compound (36))
The same procedure as in Comparative Example 1 (1)
(6) was obtained.(2) 4- (12-bromododecyloxy) benzoic acid
Synthesis of benzyl ester (ester (46))Dibromododecane 150 mmol, 4-hydroxybenzoic acid
Benzyl ester 50 mmol and potassium carbonate 0.3 mol
A 500 ml ton solution was refluxed for 6 hours. The reaction solution is filtered and concentrated
After that, it was purified by column chromatography to
An ester form (46) was obtained. (Yield 82%, [α ▲]^{twenty three}
_D▼ ＝ ＋ 2.55 ° (CHCl₃)) (3) 4- (12-bromododecyloxy) benzoic acid
Synthesis of rubonic acid derivative (47)100 mmol of ester (46) obtained in (2) and paradi
Umcarbon (5% catalyst) 2.0g ethyl acetate 150ml solution
Was stirred for 5 hours in the presence of hydrogen gas. The reaction solution is filtered
Purify by column chromatography after filtration.
The desired carboxylic acid derivative (47) was obtained. (yield
98%) (4) 4 '-[4 "-(12-bromododecyloxy) be
Nazoyloxy] biphenyl-4-carboxylic acid 2-me
Synthesis of tylbutyl ester (bromo compound (48))50 mmol of the carboxylic acid derivative (47) obtained in (3) was added to
2 hours at 80 ° C in 30 ml of ruene and 10 ml of thionyl chloride
Stir to give the acid chloride. Then excess thionyl chloride and
Toluene was distilled off under reduced pressure. Obtained in (1)
Hydroxy body (36) 55mmol and triethylamine 60mm
Stir a solution of ol in 200 ml of THF, then add the acid chloride obtained above.
The THF solution of the product was added dropwise and stirred for 8 hours. After the reaction,
Tell extraction, washing with HCl water, drying, and concentration
After that, purify by column chromatography to obtain the target
A bromo compound (48) was obtained. (Yield 73%, [α ▲]^{twenty three} _D▼ ＝
+ 2.33 ° (CHCl₃)) (5) 4 '-[4 "-{12- (2,2-dimethylol pro
Pionyloxy) dodecyloxy} benzoyloxy]
Biphenyl-4-carboxylic acid 2-methylbutyl ester
Of alcohol (alcohol (49))2,2-Dimethylolpropionic acid 18.0 mmol and hydroxide hydroxide
20.0 mmol of tramethylammonium (pentahydrate) was added to DMF150.
Stir in ml for 2 hours. Next, the bromo obtained in (4)
The body (48) (18.0 mmol) was added, and the mixture was stirred for 6 hours. After the reaction,
Column extraction, drying, and concentration, followed by column chromatography.
Purify with Raffy and obtain the desired alcohol (49)
Obtained. (Yield 78% [α ▲]^{twenty three} _D▼ ＝ ＋ 2.10 ° (CHCl₃)) (6) 4 '-[4 "-[12- {2,2- {diacetoxime
Tyl) propionyloxy} dodecyloxy] benzoi
Luoxy] biphenyl-4-carboxylic acid 2-methylbutane
Synthesis of chill ester7.5 mmol of alcohol (49) obtained in (5) and anhydrous vinegar
A solution of 45 mmol of acid in 5 ml of pyridine was stirred at room temperature for 12 hours.
The reaction solution is extracted with ether, and the ether layer is washed with aqueous HCl.
Column, dried, concentrated and then subjected to column chromatography.
And purified to obtain the desired compound. (Yield 82%, [α
▲]^{twenty three} _D▼ ＝ ＋ 2.06 ° (CHCl₃)) The phase transition behavior of this compound was as follows.The electric field response speed of this compound was 150 μs at 90.0 ° C.
It was The elemental analysis values of this compound are shown in the following table.Comparative Example 4(1) 4-Hydroxybenzoic acid 2-methylbutyl es
Synthesis of ter (hydroxy body (50))90 mmol of 4-hydroxybenzoic acid and 2-methylbutanoic acid
25 mmol of toluene in 150 ml of toluene in the presence of 2 ml of concentrated sulfuric acid.
It was subjected to a dehydration reaction for an hour. After concentrating the reaction mixture,
Purified by chromatography, the desired hydroxy form
Got (50). (95% yield, [α ▲]^{twenty three} _D▼ ＝ ＋ 4.85 °
(CHCl₃)) (2) 4'-hydroxybiphenyl-4-carboxylic acid
Synthesis of benzyl ester (ester (51))0.1 mol of 4'-hydroxyphenyl-4-carboxylic acid and
Tetramethylammonium hydroxide (pentahydrate) 0.11mol
A 200 ml DMF solution of was stirred for 2 hours. Then benzyl bromide
0.1 mol was added and the mixture was stirred for 6 hours. After reaction, extract with ether
After column extraction, drying and concentration, column chromatography
The product was purified by filtration to obtain the desired ester form (51).
(Yield 76%) (3) 4 '-(12-bromododecyloxy) biphenyl
-4-carboxylic acid benzyl ester (ester (5
2)) Synthesis70 mmol of the ester (51) obtained in (2), dibromode
Acetone 1 with 0.21 mol of decane and 0.4 mol of potassium carbonate
The solution was refluxed for 6 hours. After filtering and concentrating the reaction solution,
Purify by column chromatography and
A tel form (52) was obtained. (Yield 89%) (4) 4 '-(12-bromododecyloxy) biphenyl
Synthesis of 4-carboxylic acid (carboxylic acid derivative (53))60 mmol of the ester form (52) obtained in (3) and Paradium
Solution of 2.0 g of mcarbon (5% catalyst) in 500 ml of ethyl acetate
Was stirred in a hydrogen gas atmosphere for 24 hours. After the reaction, filtration and
And concentrate, purify by column chromatography, and
A carboxylic acid derivative (53) was obtained. (Yield 98%) (5) 4- [4 ″-(12-bromododecyloxy) bif
Phenyl-4'-carbonyloxy] benzoic acid 2-methyi
Synthesis of rubutyl ester (bromo compound (54))50 mmol of the carboxylic acid derivative (53) obtained in (4) was added to
2 in 80 ml of a solution of 20 ml of ruene and 10 ml of thionyl chloride
Stir for a period of time to obtain the acid chloride. Excess thionyl chloride
Ruene was distilled off under reduced pressure. Then obtained in (1)
Hydroxy body (50) 55 mmol and triethylamine 60 mm
Stir a 200 ml solution of THF in THF to remove the acid chloride from the TH solution.
The F solution was added dropwise and reacted for 8 hours. After the reaction, ether
After extraction, washing with HCl water, drying, and concentration,
Purify by column chromatography and
I got a body (54). (Yield 82%, [α ▲]^{twenty three} _D▼ = + 2.0
9 ° (CHCl₃)) (6) 4- [4 ″-{12- (2,2-dimethylolpropene
Onyloxy) dodecyloxy} -4'-biphenylyl
Carbonyloxy] benzoic acid 2-methylbutyl ester
Of alcohol (alcohol (55))2,2-Dimethylolpropionic acid 18.0 mmol and hydroxide hydroxide
20.0 mmol of tramethylammonium (pentahydrate) was added to DMF150.
Stir in ml for 2 hours. Next, the bromo obtained in (5)
The body (54) (18.0 mmol) was added, and the mixture was stirred for 6 hours. After the reaction,
Column extraction, drying, and concentration, followed by column chromatography.
Purify with Raffy and obtain the desired alcohol (55)
Obtained. (Yield 63%, [α ▲]^{twenty three} _D▼ ＝ ＋ 2.10 ° (CHC
l₃)) (7) 4- [4 ″-[12- {2,2-bis (acetoxime
Tyl) propionyloxy} dodecyloxy] -4′-
Biphenylylcarbonyloxy] benzoic acid 2-methyl
Butyl ester synthesis7.5 mmol of alcohol (55) obtained in (6) and anhydrous vinegar
A solution of 45.0 mmol of acid in 5 ml of pyridine was stirred at room temperature for 12 hours.
It was The reaction solution was extracted with ether, and the ether layer was extracted with HCl water.
After washing, drying and concentrating, column chromatography
And purified to obtain the desired compound. (Yield 82%,
[Α ▲]^{twenty three} _D▼ ＝ ＋ 2.03 ° (CHCl₃)) The phase transition behavior of this compound was as follows.The electric field response speed of this compound was 140 μs at 93 ° C. The elemental analysis values of this compound are shown in the following table.[Effect of the Invention] The novel compound of the present invention is inexpensive and chemically stable.
A liquid crystal compound having a different chemical structure,
It shows the iral smectic C phase in a wide temperature range including room temperature.
However, the response speed to the electric field is extremely fast,
Which digital display, electronic optical shutter, electronic optical diaphragm
Optical modulator, optical communication optical path selector switch, memory, liquid
Crystal printer head, variable focal length lens, etc.
Highly useful as an electro-optical element for electro-optical devices
Having, its industrial value is great.

[Brief description of drawings]

FIG. 1, FIG. 3, FIG. 5, FIG. 7, FIG. 9, FIG. 11, FIG. 11 and FIG. 13 are Example 1, Example 2, Example 3, Example 4, and Example 5, respectively. 8 is a chart of ¹ H-NMR spectrum of the compounds obtained in Example 6 and Example 7. 2, FIG. 4, FIG. 6, FIG. 8, FIG. 8, FIG. 10, FIG. 12 and FIG. 14 are respectively Example 1, Example 2, Example 3, Example 4, Example 5 9 is a chart of IR spectra of the compounds obtained in Examples 6 and 7.

Claims (1)

[Claims] 1. A general formula (In the formula, R ¹ and R ⁵ represent an alkyl group having 1 to ⁵ carbon atoms,
Each may be the same or different, X ¹ and X ² are —O—, And R ² may be the same or different, R ² represents —H or —CH ³ , R ³ represents a C1-20 alkylene chain, and R ⁴ represents Or And n is an integer of 0 to 5, m is an integer of 1 to 10, provided that when n is 1, m is not 1 and C _* represents an asymmetric carbon. ) A new compound represented by.