JP2840284B2 - New compound - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel compound having liquid crystallinity and capable of high-speed response. More specifically, in the field of optoelectronics, especially digital display devices such as calculators and watches, electro-optical shutters, electro-optical apertures, optical modulators,
The present invention relates to a novel compound having liquid crystallinity and capable of high-speed response, which is used as various electronic optical devices such as an optical communication optical path switch, a memory, a liquid crystal printer head, and a variable focal length lens.

[Related Art] Liquid crystals have already been used as various electro-optical elements, and are widely used for digital displays of calculators, watches and the like. Most of the conventional liquid crystal display devices use a nematic liquid crystal or a cholesteric liquid crystal, but these have problems in response, contrast, visual characteristics, and the like. Therefore, recently, a display device using a ferroelectric chiral smectic C-phase (SmC ^* phase) liquid crystal capable of high-speed response has been proposed to solve these disadvantages. However, also in these, there are problems such as a high temperature range in which a smectic C phase is exhibited and lack of chemical stability.

Ferroelectric SmC with relatively low temperature range and high-speed response ^*
Although those having a phase are also known (JP-A-55-21479, JP-A-60-235885, JP-A-61-22072, JP-A-61-24576, etc.) Is difficult to produce and difficult to obtain at low cost.

JP-A-63-107950 discloses liquid crystal compounds having a 2-methylbutyl group as an optically active group at the molecular terminal, such as those 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 electric field change.

[Problems to be solved by the invention]

The present invention provides a novel high-speed responsive liquid crystal compound that is a relatively inexpensive and chemically stable liquid crystal compound that exhibits a ferroelectric SmC ^* phase in a wide temperature range around room temperature or below room temperature. It is something to offer.

[Means for solving the problem]

The present inventors have conducted various studies to achieve the above object, and as a result, using an optically active group which is easily obtained industrially as a raw material, and introducing this optically active group into a specific chemical structure, the above object has been achieved. They have found that it is possible to obtain a satisfactory new liquid crystal compound, and have completed the present invention based on this finding.

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

(Wherein, R ¹ , R ² and R ³ represent —H, —CH ₃ , —OH, —OCH ₃ or —OCOCH ₃ , which may be the same or different, and R ⁴ and R ⁵ represent —CH _3, -OH, indicates -OCH ₃ or -OCOCH _3, which may be the same or different, R ⁶ is Wherein R ⁷ and R ⁸ represent -CH ₃ , -CN, -CF ₃ or a halogen atom, Y represents -O-, -COO- or -OCO-, and Z represents -COO-, -OCO -, - CH ₂ O- or -OCH ₂ - indicates, s and p is 0 or 1, m is an integer of 1 to 20, n, l and q are each an integer of 0, ^{C *} is Represents an asymmetric carbon. However, when n = 0, R ¹ , R ²
And R ³ are —OH, —OCH ₃ or —OCOCH ₃ , and p = q =
When it is 0, R ⁸ ≠ —CH ₃ . The novel compound of the present invention can be produced by using a compound known per se as a starting material. Examples of the method for producing the novel compound represented by the general formula and the comparative compound are shown below.

Production example [1] R ⁶ or less structure In the synthesis of the bromo form, the hydroxy form is phenoxided with potassium carbonate or the like, and the bromo form is added with Br in a solvent such as acetone.
-(CH ₂ ) _m -Br is reacted to give a monoether to obtain the desired bromo compound as shown in the above reaction formula.

Here Br- (CH ₂₎ a compound of _m -Br Specifically, the dibromomethane, dibromoethane, dibromopropane, dibromobutane, dibromopentane, dibromohexane,
Dibromoheptane, dibromooctane, dibromononane, dibromodecane, dibromoundecane, dibromododecane, dibromotridecane, dibromotetradecane,
Examples thereof include dibromopentadecane, dibromohexadecane, dibromoheptadecane, dibromooctadecane, dibromononadecane, and dibromoeicosane.

Synthesis of bromo bodies, Br- (CH _{2) m} -COOH is reacted with an acid halogenating agent such as thionyl chloride in a solvent such as toluene to give the acid halide. The obtained acid halide and the hydroxy compound are reacted in the presence of triethylamine.
The reaction is carried out in a solvent such as THF to carry out esterification to obtain the desired bromo compound as shown in the above reaction formula.

Here, the compound of Br— (CH ₂ ) _m —COOH is specifically bromoacetic acid, 3-bromopropionic acid, 4-bromobutanoic acid, 5-bromopentanoic acid, 6-bromohexanoic acid, 7-bromoheptane Acid, 8-bromooctanoic acid, 9
-Bromononanoic acid, 10-bromodecanoic acid, 11-bromoundecanoic acid, 12-bromododecanoic acid, 13-bromotridecanoic acid, 14-bromotetradecanoic acid, 15-bromopentadecanoic acid, 16-bromohexadecanoic acid, 17-bromohepta Decanoic acid, 18-bromooctadecanoic acid, 19-bromononadecanoic acid, 20-bromoeicosanoic acid, 21-bromoheneicosanoic acid and the like.

The target comparative compound is synthesized by reacting the carboxylic acid derivative A-COOH with a quaternary ammonium compound such as tetramethylammonium hydroxide in a solvent such as DMF to esterify the bromo compound.

As the carboxylic acid derivative, specifically, acetic acid,
Glycolic acid, pivalic acid, hydroxypivalic acid, dimethoxyacetic acid, 3-hydroxybutanoic acid, 2-hydroxy-2-methylbutanoic acid, 2-hydroxy-3-methylbutanoic acid, and the like.

Note that any ^one of R ^{1 to} R ⁵ is a carboxylic acid derivative.
When OCOCH ₃ is used, —OCOCH ₃ can be obtained by reacting a carboxylic acid derivative having a hydroxy group with acetic anhydride in a pyridine solvent.

As shown in the above reaction scheme, there are two methods for this esterification.

One reaction is to react 4'-hydroxybiphenyl-4-carboxylic acid and an optically active alcohol at a desired temperature in a solvent such as benzene in the presence of an esterification catalyst such as concentrated sulfuric acid. Obtain the ester form.

The other reaction is 4'-hydroxybiphenyl-4
Reacting the hydroxy group of the carboxylic acid with carbobenzoxychloride to esterify and protect as an ester. Next, the obtained ester is reacted with an acid halogenating agent such as phosphorus pentachloride to form an acid halide, and then poured into a solvent such as an optically active alcohol, THF, and pyridine, and reacted to obtain the desired ester. Get. Next, the ester is brought into contact with a hydrogenolysis catalyst such as palladium carbon in a hydrogen gas atmosphere to undergo hydrogenolysis, and a carbobenzoxy group as a protecting group is eliminated to obtain a target ester.

Optically active alcohol used here (+)-2-methylbutanol, (-)-2-methylbutanol, (+)-2-chlorobutanol, (-)-2
-Chlorobutanol, (+)-2-methylpentanol, (-)-2-methylpentanol, (+)-3-methylpentanol, (-)-3-methylpentanol,
(+)-4-methylhexanol, (-)-4-methylhexanol, (+)-2-chloropropanol,
(-)-2-chloropropanol, (+)-6-methyloctanol, (-)-6-methyloctanol,
(+)-2-cyanobutanol, (-)-2-cyanobutanol, (+)-2-butanol, (-)-2-butanol, (+)-2-pentanol, (-)-2-pen Tanol, (+)-2-octanol, (−)-2-octanol, (+)-1,1,1-trifluoro-2-octanol, (−)-1,1,1-trifluoro-2- Octanol, (+)-2-fluorooctanol, (-)-
2-fluorooctanol, (+)-2-fluorohexanol, (-)-2-fluorohexanol, (+)
-2-fluorononanol, (-)-2-fluorononanol, (+)-2-chloro-3-methylpentanol, (-)-2-chloro-3-methylpentanol and the like.

As shown in the above reaction formula, by reacting biphenyl-4,4'-diol with an optically active carboxylic acid,
Obtain the desired ester.

Here, the optically active carboxylic acid is specifically (+)
-2-methylbutanoic acid, (-)-2-methylbutanoic acid,
(+)-2-chlorobutanoic acid, (−)-2-chlorobutanoic acid, (+)-2-methylpentanoic acid, (−)-2-methylpentanoic acid, (+)-3-methylpentanoic acid,
(-)-3-methylpentanoic acid, (+)-4-methylhexanoic acid, (-)-4-methylhexanoic acid, (+)-2
-Chloropropanoic acid, (-)-2-chloropropanoic acid,
(+)-6-methyloctanoic acid, (−)-6 methyloctanoic acid, (+)-2-cyanobutanoic acid, (−)-2-cyanobutanoic acid, (+)-2-fluorooctanoic acid,
(-)-2-fluorooctanoic acid, (+)-2-chloro-3-methylpentanoic acid, (-)-2-chloro-3-methylpentanoic acid and the like.

As shown in the above reaction formula, the optically active alcohol is tosylated, and then reacted with biphenyl-4,4'-diol to obtain a desired ether compound.

Production example [2] R ⁶ or less structure As shown in the above reaction formula, the dibromoalkane and 4-hydroxybenzoic acid benzyl ester described above are
The reaction is performed in an appropriate solvent such as acetone in the presence of an alkali such as potassium carbonate to obtain an ether compound. Also, the synthesis of bromo bodies, Br- (CH _{2) m} -COOH is reacted with an acid halogenating agent such as thionyl chloride in a solvent such as toluene to give the acid halide. The obtained acid halide is reacted with benzyl 4-hydroxybenzoate in a solvent such as THF in the presence of triethylamine to give an ester to obtain a desired bromo compound.

Then, the protective group of the carboxyl group in the ether and ester is contacted with a hydrogenolysis catalyst such as palladium carbon in a hydrogen gas atmosphere to hydrogenolyze, and the carbobenzoxy group as a protective group is eliminated to give a carboxylic acid. Body. A halogenating agent such as thionyl chloride is added to the carboxylic acid compound and reacted in a solvent such as toluene to obtain an acid halide. Next, the acid halide is reacted with the ester in a solvent such as toluene in the presence of pyridine to obtain an ester. Then, as in Production Example [1], the ester and the carboxylic acid derivative A- COOH and
It is reacted with a quaternary ammonium compound such as tetramethylammonium hydroxide in a solvent such as DMF and esterified to obtain a desired novel compound.

Production example [3] R ⁶ or less structure As shown in the above reaction formula, Br- (CH ₂ ) _m -Br is reacted with hydroquinone in the presence of an alkali such as potassium carbonate to obtain an ether compound. Also, Br- (CH ₂ ) _m -C
OOH is reacted with an acid halide such as thionyl chloride in a solvent such as toluene to obtain an acid halide. The obtained acid halide and hydroquinone are reacted in a solvent such as THF in the presence of triethylamine to esterify the compound, thereby obtaining a desired ester.

Next, the carboxylic acid derivative is acid chlorided with thionyl chloride or the like. The obtained acid chloride is reacted with the ether compound and the ester compound obtained above, respectively, in the presence of pyridine to obtain an ester compound. Thereafter, esterification with A-COOH is carried out in the same manner as in [1] to obtain the desired novel compound.

The optically active alcohol is reacted with biphenyl-4,4'-dicarboxylic acid in a solvent such as toluene in the presence of an esterification catalyst to obtain the desired ester.

After the optically active carboxylic acid is acid chlorided with thionyl chloride or the like, it is reacted with benzyl 4'-hydroxybiphenyl-4-carboxylate in the presence of pyridine to obtain an ester form. Next, the ester compound is hydrogenolyzed in a hydrogen gas atmosphere by reacting with a hydrogenolysis catalyst such as palladium carbon to remove the carbobenzoxy group as a protective group, thereby obtaining a desired carboxylic acid derivative.

4'-Hydroxybiphenyl-4-carboxylic acid benzyl ester is reacted with a compound obtained by tosylating an optically active alcohol in the presence of potassium carbonate or the like to obtain an ether compound. This ether compound is reacted with a hydrogenolysis catalyst such as palladium carbon in a hydrogen gas atmosphere to undergo hydrogenolysis, and the carbobenzoxy group as a protecting group is eliminated,
Obtain the desired compound.

Production example [4] R ⁶ or less structure When the same reaction as in Production Example [2] is performed, the target comparative compound is obtained.

As shown in the above reaction scheme, there are two methods for this esterification.

In one reaction, the desired ester is obtained by reacting 4-hydroxybenzoic acid with an optically active alcohol in a solvent such as toluene in the presence of an esterification catalyst such as concentrated sulfuric acid at a desired temperature.

In the other reaction, the hydroxy group of 4-hydroxybenzoic acid is reacted with carbon benzoxyl chloride to esterify and protect the ester form. Next, the obtained ester is reacted with an acid halogenating agent such as phosphorus pentachloride to form an acid chloride, which is then poured into a solvent such as an optically active alcohol, THF, or pyridine, and allowed to react. Get. Next, the ester is brought into contact with a hydrogenolysis catalyst such as palladium carbon in a hydrogen gas atmosphere to undergo hydrogenolysis, and the carbon benzoxy group as a protective group is eliminated to obtain the desired ester.

As shown in the above reaction formula, the optically active alcohol is tosylated, and this is reacted with hydroquinone to obtain the desired ether compound.

In the above way, Production example [5] R ⁶ or less structure By performing the same reaction as in Production Example [3] as shown in the following formula, the target comparative compound is obtained.

In the synthesis of the ester compound of Production Example [3], The desired compound is obtained by a similar reaction using terephthalic acid instead of

Production example [6] R ⁶ or less structure In the reaction of Production Example [2], the compound was obtained in Production Example [4] instead of the carboxylic acid compound and instead of the ester compound And subjecting the others to the same reaction to obtain the desired novel compound.

Production example [7] R ⁶ or less structure In place of the compound in the reaction of Production Example [3],
Obtained in Production Example [5] instead of the carboxylic acid derivative And subjecting the others to the same reaction to obtain the desired novel compound.

〔Example〕

Hereinafter, the present invention will be described based on examples, but these examples do not limit the scope of the present invention.

In addition, the structure of the obtained compound was confirmed by NMR, IR, and elemental analysis, and the measurement of the phase transition temperature and the confirmation of the phase were performed by DSC and a polarizing microscope, respectively. Furthermore, since the electric field response speed greatly changes with respect to the temperature (SmC ^{* the} temperature from the phase upper limit temperature (Tc) to the lower temperature), the measured temperature (T) is set to Tc-T for objective comparison. =
The measurement was carried out at the same temperature of 3 ° C. as follows.

Measurement of electric field response speed A compound is sandwiched between two 20 × 10 mm ITO substrates, the thickness is adjusted to 25 μm with a spacer, and an AC electric field E = 2 × 10 ⁶ V
/ m, and the response time of the change in transmitted light amount (0 → 90%) at that time was measured.

In addition, in the formula showing the phase transition behavior, each symbol has the following meaning.

Cry: Crystal, SmC ^* : Chiral smectic C liquid crystal phase, Sm
A: Smectic A liquid crystal phase, ISO: Isotropic liquid, Sm1, Sm2:
Unidentified smectic liquid crystal phase Example 1 (Comparative Example) (1) Synthesis of 4'-hydroxybiphenyl-4-carboxylic acid 2-methyl ester (hydroxy form (1)) 93 mmol of 4'-hydroxybiphenyl-4-carboxylic acid and 467 mmol of 2-methylbutanol were concentrated in 2 ml of concentrated sulfuric acid.
Was refluxed in 150 ml of benzene for 25 hours. After concentrating the reaction solution, it was recrystallized with a mixed solvent of toluene and hexane to obtain the desired hydroxy compound (1) of the following formula.
(Yield 98%, ▲ [α] ²³ _D ▼ = + 4.35 ° C (CHCl ₃ ) (2) Synthesis of 4 '-(8-bromooctyloxy) biphenyl-4-carboxylic acid 2-methylbutyl ester (bromo form (2)) Hydroxy form (1) obtained in (1) 10.5 mmol,
A solution of 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 (2) of the following formula. (Yield 82%,
▲ [α] ²³ _D ▼ = + 2.18 ° C (CHCl ₃ ) (3) 4 '-[8- (3-hydroxy-2,2-dimethylpropionyloxy) octyloxy] biphenyl-
Synthesis of 4-carboxylic acid 2-methylbutyl ester (alcohol (3)) 6.0 mmol of hydroxypivalic acid and 6.6 mmol of tetramethylammonium hydroxide (pentahydrate) in 50 ml of DMF
For 2 hours. Next, 6.2 mmol of the bromo compound (2) obtained in (2) was added and stirred for 6 hours. After adding 100 ml of water to the reaction solution, performing ether extraction, drying and concentration,
Purification by column chromatography gave the desired alcohol (3) of the following formula. (Yield 79%, ▲ [α]
²³ _D ▼ = ＋ 2.09 ゜ (CHCl ₃ ) The phase transition behavior of this compound was as follows. (Numbers are in ° C, the same applies hereinafter) The following table shows the elemental analysis values of this compound.

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

The electric field response speed of this compound was 400 μs at 10 ° C.

Example 2 (Comparative Example) Synthesis of 4 '-[8- (3-acetoxy-2,2-dipropionyloxy) octyloxy] biphenyl-4-carboxylic acid 2-methylbutyl ester A solution of 2.5 mmol of the alcohol (3) obtained in Example 1- (3) and 15 mmol of acetic anhydride in 5 ml of pyridine was added at room temperature to 1 ml.
Stir for 2 hours. The reaction solution was extracted with ether, and the ether layer was washed with HCl water, dried, concentrated, and purified by column chromatography to obtain the desired novel compound of the following formula. (Yield 93%, ▲ [α] ²³ _D ▼ = + 1.97 ゜ (CHCl ₃ ) The phase transition behavior of this compound was as follows.

The following table shows the elemental analysis values of this compound.

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

The electric field response speed of this compound was 420 μs at −11 ° C.

Example 3 (comparative example) (1) Synthesis of 4-carbobenzoxyoxybenzoic acid (ester (4)) To a solution of 4-hydroxybenzoic acid (55 mmol) and sodium hydroxide (65 mmol) in water (200 ml) was added dropwise carbobenzoxycyclolide (65 mmol) at an ice temperature. After stirring for 24 hours,
The precipitate was washed with water, filtered, dried and purified by column chromatography to obtain the desired ester (4) of the following formula. (99% yield) (2) Synthesis of 4-carbobenzoxyoxybenzoic acid chloride (acid chloride (5)) A solution of 27 mmol of the ester (4) obtained in (1) and 27 mmol of phosphorus pentachloride in 50 ml of ether at room temperature for 24 hours. Stirred for hours. After the reaction, the mixture was deethered, and the crystals were recrystallized from hexane to obtain the desired acid chloride (5) of the following formula. (57% yield) (3) Synthesis of 4-carbobenzoxyoxybenzoic acid 2-methylbutyl ester (ester (6)) Optically active 2-methylbutanol 20 mmol THF 20m
l, 40 ml of a solution of pyridine was cooled with ice, and a solution of the acid chloride (5) obtained in (2) in 16 mmol of THF 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 and concentrated, and then purified by column chromatography to obtain the desired ester (6) of the following formula. (73% yield) (4) Synthesis of 2-methylbutyl 4-hydroxybenzoyloxybenzoate (hydroxy form (7)) 10 mmol of the ester form (6) obtained in (3), 0.5 g of palladium carbon (5% catalyst) in acetic acid The ethyl solution was reacted in a hydrogen gas atmosphere for 4 hours. After the reaction, palladium carbon was filtered through a membrane filter, and the filtrate was concentrated and then purified by column chromatography to obtain the desired hydroxy compound (7) of the following formula. (95% yield) (5) Synthesis of benzyl 4- (12-bromododecyloxy) benzoate (ester (8)) Dibromododecane 150 mmol, 4-hydroxybenzoic acid benzyl ester 50 mmol, and potassium carbonate 0.
A solution of 3 mol of acetone in 500 ml was refluxed for 6 hours. After the reaction solution was filtered and concentrated, it was purified by column chromatography to obtain the desired ester (8). (Yield 82%) (6) Synthesis of 4- (12-bromododecyloxy) benzoic acid (carboxylic acid derivative (9)) Ethyl acetate 150 m of 100 g of the ester (8) obtained in (5) and 2.0 g of palladium carbon (5% catalyst)
The solution was stirred for 5 hours in the presence of hydrogen gas. The reaction solution was filtered and concentrated, and then purified by column chromatography to obtain the desired carboxylic acid derivative (9). (Yield 98%) (7) Synthesis of 4- [4 '-(12-bromododecyloxy) benzoyloxybenzoic acid 2-methylbutyl ester (bromo compound (10)) 50 mmol of the carboxylic acid derivative (9) obtained in (6) was stirred in 30 ml of toluene and 10 ml of thionyl chloride at 80 ° C. for 2 hours to obtain an acid chloride. Next, excess thionyl chloride and toluene were distilled off by drying under reduced pressure. A solution of 55 mmol of the hydroxy compound (7) obtained in (4) and 60 mmol of triethylamine in 200 ml of THF was stirred, and the THF solution of the acid chloride obtained earlier was added dropwise, followed by stirring for 8 hours. After the reaction, the mixture was extracted with ether, washed with HCl, dried, and concentrated, and then purified by column chromatography to obtain the desired bromo compound (10). (Yield 72%) (8) 4- [4 '-{12- (3-hydroxy-2,2-dimethylpropionyloxy) dodecyloxy} benzoyloxy] benzoic acid 2-methylbutyl ester (alcohol (11) ) Synthesis 18.0 mmol of hydroxypivalic acid and 20.0 mmol of tetramethylammonium hydroxide (pentahydrate) were added to DMF150.
Stirred in ml for 2 hours. Next, 18.0 mmol of the bromo compound (10) obtained in (7) was added and stirred for 6 hours. After the reaction, the mixture was subjected to ether extraction, drying, and concentration, and then purified by column chromatography to obtain an alcohol (11) as a target comparative compound. (Yield: 89%) The phase transition behavior of this compound was as follows.

The electric field response speed of this compound was 130 μs at 36 ° C.

 The following table shows the elemental analysis values of this compound.

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

Example 4 (comparative example) (1) Synthesis of 4- [4 '-{12- (3-acetoxy-2,2-dimethylpropionyloxy) dodecyloxy} benzoyloxy] benzoic acid 2-methylbutyl ester Obtained in Example 3- (8) Alcohol body (11) 7.5
A solution of mmol and 45 mmol of acetic anhydride 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 aqueous HCl, dried and concentrated, and then purified by column chromatography to obtain the target comparative compound of the above formula. (Yield 96%) The phase transition behavior of this compound was as follows.

The electric field response speed of this compound was 180 μs at 10 ° C.

 The following table shows the elemental analysis values of this compound.

FIG. 7 shows the ¹ H-NMR spectrum of this compound, and FIG. 8 shows its IR spectrum.

Example 5 (Example) (1) 4'-carbon benzoxyoxybiphenyl 4-
Synthesis of carboxylic acid (ester compound (12)) To a solution of 4'-hydroxybiphenyl-4-carboxylic acid (55 mmol) and sodium hydroxide (65 mmol) in water (200 ml) was added dropwise carbobenzoxycyclolide (65 mmol) at an ice temperature. After stirring for 24 hours, the precipitate was washed with water, filtered, dried, and purified by column chromatography to obtain the desired ester (12) of the following formula. (85% yield) (2) 4'-carbon benzoxyoxybiphenyl-4
Synthesis of carboxylic acid chloride (acid chloride (13)) A solution of 27 mmol of the ester (12) 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, the product was deethered, and the crystals were recrystallized from hexane to obtain the desired acid chloride (13) of the following formula. (89% yield) (3) 4'-carbon benzoxyoxybiphenyl-4
Synthesis of -Carboxylic acid-2-methylbutyl ester (ester (14)) Optically active 2-methylbutanol 20 mmol THF20m
l, 40 ml of pyridine solution was cooled with ice, and a solution of 16 mmol of the acid chloride (13) obtained in (1) 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 and concentrated, and then purified by column chromatography to obtain the desired ester (14) of the following formula.
(70% yield) (4) 4'-bidroxybiphenyl-4-carboxylic acid 2
Synthesis of methyl butyl ester (hydroxy form (15)) A solution of 10 mmol of the ester form (14) obtained in (3) and 0.5 g of palladium carbon (5% catalyst) in ethyl acetate was reacted in a hydrogen gas atmosphere for 4 hours. Was. After the reaction, palladium carbon was filtered through a membrane filter, and the filtrate was concentrated and then purified by column chromatography to obtain the desired hydroxy compound (15). (98% yield) (5) Synthesis of 4 '-{4 "-(12-bromododecyloxy) benzoyloxy) biphenyl-4-carboxylic acid 2-methylbutyl ester (bromo compound (16)) 50 mmol of the carboxylic acid derivative (9) obtained in Example 3- (6) was dissolved in a solution of 30 ml of toluene and 10 ml of thionyl chloride.
The mixture was stirred at 80 ° C. for 2 hours to obtain an acid chloride. Next, excess thionyl chloride and toluene were distilled off under reduced pressure. A solution of 55 mmol of the hydroxy compound (15) obtained in (4) and 60 mmol of triethylamine in 200 ml of THF was stirred, and the THF solution of the acid chloride obtained earlier was added dropwise.
Stir for 8 hours. After the reaction, the mixture was subjected to ether extraction, washing with HCl water, drying and concentration, and then purified by column chromatography to obtain the desired bromo compound (16).
(Yield 67%) (6) 4 '-[4 "-{12- (3-hydroxy-2,2-dimerpropionyloxy) dodecyloxy} biphenyl-4-carboxylic acid 2-methylbutyl ester (alcohol ( 17)) Synthesis 18.0 mmol of hydroxypivalic acid and 20.0 mmol of tetramethylammonium hydroxide (pentahydrate) were added to DMF150.
Stirred in ml for 2 hours. Next, 18.0 mmol of the bromo compound (16) obtained in (5) 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 desired alcohol (17). (Yield: 71%) The phase transition behavior of this compound was as follows.

The electric field response speed of this compound was 370 μs at 84 ° C.

 The following table shows the elemental analysis values of this compound.

FIG. 9 shows the ¹ H-NMR spectrum of this compound, and FIG. 10 shows its IR spectrum.

Example 6 (Example) (1) 4 '-[4 "-｛12- (3-acetoxy-2,2-
Synthesis of dimethylpropionyloxy) dodecyloxy {benzoyloxy] biphenyl-4-carboxylic acid 2-methylbutyl ester A solution of 7.5 mmol of the alcohol (17) obtained in Example 5- (6) and 45 mmol of acetic anhydride in 5 ml of pyridine was used. 1 at room temperature
Stir for 2 hours. The reaction solution was extracted with ether, and the ether layer was washed with HCl water, dried and concentrated, and then purified by column chromatography to obtain the desired novel compound of the above formula. (Yield 93%) The phase transition behavior of this compound was as follows.

The electric field response speed of this compound was 380 μs at 81 ° C.

 The following table shows the elemental analysis values of this compound.

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

Example 7 (Example) (1) Synthesis of 4'-hydroxybiphenyl-4-carboxylic acid benzyl ester (ester (19)) 0.1 mol of 4'-hydroxybiphenyl-4-carboxylic acid and tetramethylammonium hydroxide (pentahydrate)
A 200 ml solution of 11 mol DMF 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 desired ester (18). (Yield 76%) (2) 4 '-(12-bromododecyloxy) biphenyl-4-carboxylic acid benzyl ester (ester (1
9)) Synthesis A solution of 70 mmol of the ester (18) obtained in (1), 0.21 mol of dibromododecane, and 0.4 mol of potassium carbonate in acetone 1 was refluxed for 6 hours. The reaction solution was filtered and concentrated, and then purified by column chromatography to obtain the desired ester (19). (Yield: 89%) (3) Synthesis of 4 '-(12-bromododecyloxy) biphenyl-4-carboxylic acid (carboxylic acid derivative (20)) Ethyl acetate (500 ml) containing 60 mmol of the ester (19) obtained in (2) and 2.0 g of palladium carbon (5% catalyst)
The solution was stirred under a hydrogen gas atmosphere for 24 hours. After the reaction, the reaction solution was filtered and concentrated, and purified by column chromatography to obtain the desired carboxylic acid derivative (20).
(Yield 98%) (4) Synthesis of 4- [4 ″-(12-bromododecyloxy) biphenylyl-4′-carbonyloxy] benzoic acid 2-methylbutyl ester (bromo compound (21)) 50 mmol of the carboxylic acid derivative (20) obtained in (3) was treated at 80 ° C. in a solution of 20 ml of toluene and 10 ml of thionyl chloride.
For 2 hours to obtain an acid chloride. Excess thionyl chloride and toluene were distilled off under reduced pressure. Next, Example 3-
A solution of 55 mmol of the hydroxy compound (7) obtained in (4) and 60 mmol of triethylamine in 200 ml of THF was stirred, and the THF solution of the acid chloride obtained above was added dropwise, and reacted for 8 hours. After the reaction, the mixture was extracted with ether, washed with aqueous HCl, dried, and concentrated, and then purified by column chromatography to obtain the desired bromo compound (21). (Yield 79
(5) 4- [4 "-{12- (3-hydroxy-2,2-dimethylpropionyloxy) dodecyloxy} biphenylyl-4'-carbonyloxy] benzoic acid 2-methylbutyl ester (alcohol (22 ) Synthesis 18.0 mmol of hydroxypivalic acid and 20.0 mmol of tetramethylammonium hydroxide (pentahydrate) were added to DMF150.
Stirred in ml for 2 hours. Next, 20.0 mmol of the bromo compound (21) obtained in (4) 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.
2) got. (Yield 76%) The phase transition behavior of this compound was as follows.

The electric field response speed of this compound was 80 μs at 115 ° C.

 The following table shows the elemental analysis values of this compound.

FIG. 13 shows the ¹ H-NMR spectrum of this compound, and FIG. 14 shows its IR spectrum.

Example 8 (Example) (1) Synthesis of 4- [4 "-{12- (3-acetoxy-2,2-dimethylpropionyloxy) dodecyloxy} biphenylyl-4'-carbonyloxy] benzoic acid 2-methylbutyl ester In Example 7-5 A solution of 7.5 mmol of the obtained alcohol (22) and 45.0 mmol of acetic anhydride in 5 ml of pyridine was added at room temperature to 12 ml.
Stirred for hours. The reaction solution was extracted with ether, and the ether layer was separated.
After washing with HCl water, drying and concentration, purification was carried out by column chromatography to obtain the desired novel compound of the above formula. (Yield 98%) The phase transition behavior of this compound was as follows.

The electric field response speed of this compound was 75 μs at 103 ° C.

 The following table shows the elemental analysis values of this compound.

FIG. 15 shows the ¹ H-NMR spectrum of this compound, and FIG. 16 shows its IR spectrum.

Example 9 (comparative example) Synthesis of 4 '-[4 "-(12-acetoxydodecyloxy) benzoyloxy] biphenyl-4-carboxylic acid 2-methylbutyl ester 18.0 mmol of acetic acid and 18.0 mmol of tetramethylammonium hydroxide (pentahydrate) in 150 ml of DMF Then, the bromo compound (1) was obtained in Example 5- (5).
6) was added at 18.0 mmol, and the mixture was 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 desired novel compound of the above formula. (Yield: 88%) The phase transition behavior of this compound was as follows.

The electric field response speed of this compound was 150 μs at 70 ° C.

 The following table shows the elemental analysis values of this compound.

FIG. 17 shows the ¹ H-NMR spectrum of this compound, and FIG. 18 shows its IR spectrum.

Example 10 (Example) (1) Synthesis of 4 '-[4 "-{12- (dimethylpropionyloxy) dodecyloxy} benzoyloxy] biphenyl-4-carboxylic acid 2-methylbutyl ester 18.0 mmol of pivalic acid and tetramethylammonium hydroxide (5 water 18.0 mmol) was stirred in 150 ml of DMF for 2 hours, and then 18.0 mmol of the bromo compound (16) obtained in Example 5- (5) was added and stirred for 6 hours. After concentration, the concentrate was purified by column chromatography to obtain the desired novel compound of the above formula (yield: 88%) The phase transition behavior of this compound was as follows.

The electric field response speed of this compound was 80 μs at 96 ° C.

 The following table shows the elemental analysis values of this compound.

FIG. 19 shows the ¹ H-NMR spectrum of this compound, and FIG. 20 shows its IR spectrum.

Example 11 (Example) (1) 4 '-[4 "-{12- (2-hydroxyacetoxy) dodecyloxy} benzoyloxy] biphenyl-
Synthesis of 4-carboxylic acid 2-methylbutyl ester 18.0 mmol of glycolic acid and 18.0 mmol of tetramethylammonium hydroxide (pentahydrate) were dissolved in 150 ml of DMF.
Stirred for hours. Next, 18 mmol of the bromo compound (16) obtained in Example 5- (5) was added, and the mixture was 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 desired novel compound of the above formula. (Yield 80%) The phase transition behavior of this compound was as follows.

The electric field response speed of this compound was 20 μs at 89 ° C.

 The following table shows the elemental analysis values of this compound.

The ¹ H-NMR spectrum and IR spectrum of this compound are shown in FIG. 21 and FIG. 22, respectively.

Example 12 (Example) (1) Synthesis of 4 '-[4 "-{12- (2-acetoxymethylacetoxy) dodecyloxy} benzoyloxy] biphenyl-4-carboxylic acid 2-methylbutyl ester Alcohol obtained in Example 11- (1) A solution of 7.5 mmol of the isomer and 45.0 mmol of acetic anhydride in 5 ml of pyridine was added at room temperature to 12 ml.
Stirred for hours. The reaction solution was extracted with ether, and the ether layer was washed with diluted HCl water, dried and concentrated, and then purified by column chromatography to obtain the desired novel compound of the above formula. (Yield: 89%) The phase transition behavior of this compound was as follows.

The electric field response speed of this compound was 90 μs at 74 ° C.

 The following table shows the elemental analysis values of this compound.

The ¹ H-NMR spectrum and IR spectrum of this compound are shown in FIG. 23 and FIG. 24, respectively.

Example 13 (Example) 4 '-[4 "-{12- (2-hydroxybutanoyloxy) dodecyloxy} benzoyloxy] biphenyl-
Synthesis of 4-carboxylic acid 2-methylbutyl ester 18.0 mmol of 3-hydroxybutyric acid and 18.0 mmol of tetramethylammonium hydroxide (pentahydrate) were stirred in 150 ml of DMF for 2 hours. Next, Example 5- (5)
18 mmol of the bromo compound (16) obtained in (1) 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 desired novel compound of the above formula. (Yield: 78%) The phase transition behavior of this compound was as follows.

The electric field response speed of this compound was 30 μs at 92 ° C.

 The following table shows the elemental analysis values of this compound.

FIG. 25 shows the ¹ H-NMR spectrum of this compound, and FIG. 26 shows its IR spectrum.

Example 14 (Example) (1) Synthesis of 4 ′-[4 ″-{12- (2-acetoxybutanoyloxy) dodecyloxy} benzoyloxy] biphenyl-4-carboxylic acid 2-methylbutyl ester 7.5 mmol of the alcohol obtained in Example 13 Acetic anhydride 4
A solution of 5.0 mmol of pyridine in 5 ml was stirred at room temperature for 12 hours. The reaction solution was extracted with ether, the ether layer was washed with diluted HCl water, dried and concentrated, and then purified by column chromatography to obtain the desired novel compound of the above formula.
(Yield: 92%) The phase transition behavior of this compound was as follows.

The electric field response speed of this compound was 400 μs at 80 ° C.

 The following table shows the elemental analysis values of this compound.

The ¹ H-NMR spectrum and IR spectrum of this compound are shown in FIG. 27 and FIG. 28, respectively.

Example 15 (Example) 4 '-[4 "-{12- (2-hydroxy-2-methylbutanoyloxy) dodecyloxy} benzoyloxy]
Synthesis of biphenyl-4-carboxylic acid 2-methylbutyl ester 18.0 mmol of 2-hydroxy-2-methylbutyric acid and 18.0 mmol of tetramethylammonium hydroxide (pentahydrate) were stirred in 150 ml of DMF for 2 hours. Next, 18 mmol of the bromo compound (16) obtained in Example 5- (5) was added, and the mixture was 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 desired novel compound of the above formula. (Yield 87
%) The phase transition behavior of this compound was as follows.

The electric field response speed of this compound was 40 μs at 98 ° C.

 The following table shows the elemental analysis values of this compound.

The ¹ H-NMR spectrum of this compound is shown in FIG. 29, and the IR spectrum is shown in FIG.

Example 16 (Example) (1) Synthesis of 4 '-[4 "-{12- (2-acetoxy-2-methylbutanoyloxy) dodecyloxy} benzoyloxy] biphenyl-4-carboxylic acid 2-methylbutyl ester Obtained in Example 15. 7.5 mmol of alcohol and acetic anhydride 4
A solution of 5.0 mmol of pyridine in 5 ml was stirred at room temperature for 12 hours. The reaction solution was extracted with ether, the ether layer was washed with diluted HCl water, dried and concentrated, and then purified by column chromatography to obtain the desired novel compound of the above formula.
(Yield 90%) The phase transition behavior of this compound was as follows.

The electric field response speed of this compound was 80 μs at 88 ° C.

 The following table shows the elemental analysis values of this compound.

The ¹ H-NMR spectrum and IR spectrum of this compound are shown in FIG. 31 and FIG. 32, respectively.

Example 17 (Example) (1) Synthesis of 4 '-[4 "-{12- (2-hydroxy-3-methylbutanoyloxy) dodecyloxy} benzoyloxy] biphenyl-4-carboxylic acid 2-methylbutyl ester 2-hydroxy-3- 18.0 mmol of methylbutyric acid and 18.0 mmol of tetramethylammonium hydroxide (pentahydrate) were stirred in 150 ml of DMF for 2 hours. After the reaction, the mixture was extracted with ether, dried and concentrated, and then purified by column chromatography to obtain the desired novel compound of the above formula (yield: 83).
%) The phase transition behavior of this compound was as follows.

The electric field response speed of this compound was 60 μs at 94 ° C.

 The following table shows the elemental analysis values of this compound.

The ¹ H-NMR spectrum and IR spectrum of this compound are shown in FIG. 33 and FIG. 34, respectively.

Example 18 (Example) 4 '-[4 "-{12- (2-acetoxy-3-methylbutanoyloxy) dodecyloxy} benzoyloxy]
Synthesis of biphenyl-4-carboxylic acid 2-methylbutyl ester 7.5 mmol of alcohol obtained in Example 17 and acetic anhydride 4
A solution of 5.0 mmol of pyridine in 5 ml was stirred at room temperature for 12 hours. The reaction solution was extracted with ether, the ether layer was washed with diluted HCl water, dried and concentrated, and then purified by column chromatography to obtain the desired novel compound of the above formula.
(Yield: 89%) The phase transition behavior of this compound was as follows.

The electric field response speed of this compound was 50 μs at 86 ° C.

 The following table shows the elemental analysis values of this compound.

The ¹ H-NMR spectrum and IR spectrum of this compound are shown in FIG. 35 and FIG. 36, respectively.

Example 19 (Example) (1) 4 '-[4 "-{12- (2,2-dimethoxyacetoxydodecyloxy} benzoyloxy] biphenyl-
Synthesis of 4-carboxylic acid 2-methylbutyl ester 18.0 mmol of dimethoxyacetic acid and 18.0 mmol of tetramethylammonium hydroxide (pentahydrate) were stirred in 150 ml of DMF for 2 hours. Next, 18 mmol of the bromo compound (16) obtained in Example 5- (5) was added, and the mixture was 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 desired novel compound of the above formula. (Yield 63%) The phase transition behavior of this compound was as follows.

The electric field response speed of this compound was 200 μs at 17 ° C.

 The following table shows the elemental analysis values of this compound.

The ¹ H-NMR spectrum and IR spectrum of this compound are shown in FIG. 37 and FIG. 38, respectively.

Example 20 (Example) (1) Synthesis of 4'-carbobenzoxyoxybenzoic acid 3-methylpentyl ester (ester (23)) Optically active 3-methylpentanol 20 mmol THF2
A solution of 0 ml and 40 ml of pyridine were cooled on ice, and a solution of the acid chloride (5) obtained in Example 3- (2) in 16 mmol of THF 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 and concentrated, and then purified by column chromatography to obtain the desired ester (23). (Yield 77%) (2) Synthesis of 4-hydroxybenzoyloxybenzoic acid 3-methylpentyl ester (24) A solution of 10 mmol of the ester (23) obtained in (1) and 0.5 g of palladium carbon (5% catalyst) in ethyl acetate was reacted in a hydrogen gas atmosphere for 4 hours. After the reaction, palladium carbon was filtered through a membrane filter, concentrated and then purified by column chromatography to obtain the desired hydroxy compound (24). (Yield 97%) (3) Synthesis of 3-methylpentyl ester of 4- [4 ″-(12-bromododecyloxy) biphenylyl-4′-carbonyloxy] benzoic acid (25) Carboxylic acid derivative (20) obtained in Example 7- (3) 50.0
The mmol was stirred with a solution of 20 ml of toluene and 10 ml of thionyl chloride at 80 ° C. for 2 hours to give the acid chloride. Excess toluene and thionyl chloride were distilled off under reduced pressure. next,
A solution of 55 mmol of the hydroxy compound (24) obtained in (2) and 60 mmol of triethylamine in 200 ml of THF was stirred, the THF solution of the acid chloride obtained earlier was added dropwise, and the mixture was stirred for 8 hours. After the reaction, the mixture was extracted with ether, washed with diluted HCl water, dried and concentrated, and then purified by column chromatography to obtain the desired bromo compound (25). (Yield 75%) (4) 4- [4 ″-{12- (3-hydroxy-2,2-)
Synthesis of dimethylpropionyloxy) dodecyloxy {biphenylyl-4'-carbonyloxy] benzoic acid 3-methylpentyl ester (26) 18.0 mmol of hydroxypivalic acid and 18.0 mmol of tetramethylammonium hydroxide (pentahydrate) were added to DMF150.
Stirred in ml for 2 hours. Next, 18.0 mmol of the bromo compound (25) obtained in (3) was added, and the mixture was stirred for 6 hours. After the reaction,
After ether extraction, drying and concentration, the product is purified by column chromatography to obtain the desired alcohol (26)
I got (79% yield) The phase transition behavior of this compound was as follows.

The electric field response speed of this compound was 400 μs at 115 ° C.

 The following table shows the elemental analysis values of this compound.

The ¹ H-NMR spectrum and IR spectrum of this compound are shown in FIG. 39 and FIG. 40, respectively.

Example 21 (Example) 4- [4 ″-{12- (3-acetoxy-2,2-dimethylpropionyloxy) dodecyloxy} biphenylyl-
Synthesis of 4'-carbonyloxy] benzoic acid 3-methylpentyl ester (26) (1) Alcohol (26) obtained in Example 20- (4) (7.5)
A solution of 5 mmol of acetic anhydride and 45.0 mmol of acetic anhydride in 5 ml of pyridine was stirred at room temperature for 12 hours. The reaction solution was extracted with ether and diluted HC
After washing with water, drying and concentration, purification was performed by column chromatography to obtain the desired novel compound of the above formula. (Yield: 92%) The phase transition behavior of this compound was as follows.

The electric field response speed of this compound was 200 μs at 81 ° C.

 The following table shows the elemental analysis values of this compound.

The ¹ H-NMR spectrum and IR spectrum of this compound are shown in FIG. 41 and FIG. 42, respectively.

Example 22 (Example) (1) Synthesis of 4'-carbobenzoxyoxybenzoic acid 1-methylbutyl ester (ester (27)) Optically active 1-methylbutanol 20 mmol THF 20m
l, 40 ml of pyridine solution was cooled with ice, and a solution of 16 mmol of the acid chloride (5) obtained in Example 3- (2) in THF 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 and concentrated, and then purified by column chromatography to obtain the desired ester (27) of the above formula. (Yield 79%) (2) Synthesis of 1-methylbutyl 4-hydroxybenzoyloxybenzoate (28) A solution of 10 mmol of the ester (27) obtained in (1) and 0.5 g of palladium carbon (5% catalyst) in ethyl acetate was reacted in a hydrogen gas atmosphere for 4 hours. After the reaction, palladium carbon was filtered through a membrane filter, concentrated and then purified by column chromatography to obtain the desired hydroxy compound (28). (Yield 97%) (3) Synthesis of 1-methylbutyl 4- [4 ″-(12-bromododecyloxy) biphenylyl-4′-carbonyloxy] benzoate (29) Carboxylic acid derivative (20) obtained in Example 7- (3) 50.0
The mmol was stirred with a solution of 20 ml of toluene and 10 ml of thionyl chloride at 80 ° C. for 2 hours to give the acid chloride. Excess toluene and thionyl chloride were distilled off under reduced pressure. next,
A solution of 55 mmol of the hydroxy compound (28) obtained in (2) and 60 mmol of triethylamine in 200 ml of THF was stirred, the THF solution of the acid chloride obtained earlier was added dropwise, and the mixture was stirred for 8 hours. After the reaction, the mixture was subjected to ether extraction, washing with dilute HCl water, drying and concentration, and then purified by column chromatography to obtain the desired bromo compound (29). (Yield 71%) (4) 4- [4 ″-{12- (3-hydroxy-2,2-)
Synthesis of dimethylpropionyloxy) dodecyloxy {biphenylyl-4'-carbonyloxy] benzoic acid 1-methylbutyl ester (alcohol (30)) 18.0 mmol of hydroxypivalic acid and 18.0 mmol of tetramethylammonium hydroxide (pentahydrate) were added to DMF150.
Stirred in ml for 2 hours. Next, 18.0 mmol of the bromo compound (29) obtained in (3) was added and stirred for 6 hours. After the reaction,
After ether extraction, drying and concentration, purification was carried out by column chromatography to obtain the desired novel alcohol compound (30). (79% yield) The phase transition behavior of this compound was as follows.

The electric field response speed of this compound was 20 μs at 96 ° C.

 The following table shows the elemental analysis values of this compound.

FIG. 43 shows the ¹ H-NMR spectrum of this compound, and FIG. 44 shows its IR spectrum.

Example 23 (Example) 4- [4 ″-{12- (3-acetoxy-2,2-dimethylpropionyloxy) dodecyloxy} biphenylyl-
Synthesis of 4'-carbonyloxy] benzoic acid 1-methylbutyl ester (26) (1) The alcohol (30) 7.5 obtained in Example 22- (4)
A solution of 5 mmol of acetic anhydride and 45.0 mmol of acetic anhydride in 5 ml of pyridine was stirred at room temperature for 12 hours. The reaction solution was extracted with ether and diluted HC
After washing with water, drying and concentration, purification was performed by column chromatography to obtain the desired novel compound of the above formula. (Yield 90%) The phase transition behavior of this compound was as follows.

The electric field response speed of this compound was 50 μs at 39 ° C.

 The following table shows the elemental analysis values of this compound.

The ¹ H-NMR spectrum and IR spectrum of this compound are shown in FIG. 45 and FIG. 46, respectively.

Example 24 (Example) (1) Synthesis of 4'-carbobenzoxyoxybenzoic acid 2-fluorohexyl ester (ester (31)) Optically active 2-fluorohexanol 20 mmol TH
A solution of 20 ml of F and 40 ml of pyridine were cooled on ice, and a solution of 16 mmol of the acid chloride (5) obtained in Example 3- (2) in THF 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 and concentrated, and then purified by column chromatography to obtain the desired ester (31). (Yield 70%) (2) Synthesis of 4-hydroxybenzoyloxybenzoic acid 2-fluorohexyl ester (hydroxy form (32)) A solution of 10 mmol of the ester (31) obtained in (1) and 0.5 g of palladium carbon (5% catalyst) in ethyl acetate was reacted in a hydrogen gas atmosphere for 4 hours. After the reaction, the palladium carbon was filtered through a membrane filter, concentrated, and then purified by column chromatography to obtain the desired hydroxy compound (32). (Yield 97%) (3) Synthesis of 4- [4 ″-(12-bromododecyloxy) biphenyl-4′-carbonyloxy] benzoic acid 2-fluorohexyl ester (bromo compound (33)) Carboxylic acid derivative (20) obtained in Example 7- (3) 50.0
The mmol was stirred with a solution of 20 ml of toluene and 10 ml of thionyl chloride at 80 ° C. for 2 hours to give the acid chloride. Excess toluene and thionyl chloride were distilled off under reduced pressure. next,
A solution of 55 mmol of the hydroxy compound (32) obtained in (2) and 60 mmol of triethylamine in 200 ml of THF was stirred, the THF solution of the acid chloride obtained earlier was added dropwise, and the mixture was stirred for 8 hours. After the reaction, the mixture was extracted with ether, washed with diluted HCl water, dried and concentrated, and then purified by column chromatography to obtain the desired bromo compound (33). (Yield 80%) (4) 4- [4 "-{12- (3-hydroxy-2,2-dimethylpropionyloxy) dodecyloxy} biphenylyl-4'-carbonyloxy] benzoic acid 2-fluorohexyl ester ( Synthesis of alcohol (34) 18.0 mmol of hydroxypivalic acid and 18.0 mmol of tetramethylammonium hydroxide (pentahydrate) were added to DMF150.
Stirred in ml for 2 hours. Next, 18.0 mmol of the bromo compound (33) obtained in (3) was added and stirred for 6 hours. After the reaction,
After ether extraction, drying and concentration, the product is purified by column chromatography to obtain the desired alcohol (34)
I got (Yield: 72%) The phase transition behavior of this compound was as follows.

The electric field response speed of this compound was 60 μs at 117 ° C.

 The following table shows the elemental analysis values of this compound.

The ¹ H-NMR spectrum and IR spectrum of this compound are shown in FIG. 47 and FIG. 48, respectively.

Example 25 (Example) 4- [4 ″-{12- (3-acetoxy-2,2-dimethylpropionyloxy) dodecyloxy} biphenylyl-
Synthesis of [4'-carbonyloxy] benzoic acid 2-fluorohexyl ester (1) The alcohol (34) 7.5 obtained in Example 24- (4)
A solution of 5 mmol of acetic anhydride and 45.0 mmol of acetic anhydride in 5 ml of pyridine was stirred at room temperature for 12 hours. The reaction solution was extracted with ether and diluted HC
After washing with water, drying and concentration, purification was performed by column chromatography to obtain the desired novel compound of the above formula. (Yield: 92%) The phase transition behavior of this compound was as follows.

The electric field response speed of this compound was 220 μs at 87 ° C.

 The following table shows the elemental analysis values of this compound.

FIG. 49 shows the ¹ H-NMR spectrum of this compound, and FIG. 50 shows its IR spectrum.

Example 26 (Example) (1) Synthesis of 4'-carbobenzoxyoxobenzoic acid 2-fluoroheptyl ester (ester (35)) Optically active 2-fluoroheptanol 20 mmol TH
A solution of 20 ml of F and 40 ml of pyridine were cooled on ice, and a solution of 16 mmol of the acid chloride (5) obtained in Example 3- (2) in THF 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 and concentrated, and then purified by column chromatography to obtain the desired ester (35). (Yield 74%) (2) Synthesis of 4-hydroxybenzoyloxybenzoic acid 2-fluoroheptyl ester (hydroxy form (36)) A solution of 10 mmol of the ester (35) obtained in (1) and 0.5 g of palladium carbon (5% catalyst) in ethyl acetate was reacted in a hydrogen gas atmosphere for 4 hours. After the reaction, palladium carbon was filtered through a membrane filter, concentrated, and then purified by column chromatography to obtain the desired hydroxy compound (36). (Yield 95%) (3) Synthesis of 4- [4 ″-(12-bromododecyloxy) biphenyl-4′-carbonyloxy] benzoic acid 2-fluoroheptyl ester (bromo compound (37)) Carboxylic acid derivative (20) obtained in Example 7- (3) 50.0
The mmol was stirred with a solution of 20 ml of toluene and 10 ml of thionyl chloride at 80 ° C. for 2 hours to give the acid chloride. Excess toluene and thionyl chloride were distilled off under reduced pressure. next,
A solution of 55 mmol of the hydroxy compound (36) obtained in (2) and 60 mmol of triethylamine in 200 ml of THF was stirred, the THF solution of the acid chloride obtained earlier was added dropwise, and the mixture was stirred for 8 hours. After the reaction, the mixture was subjected to ether extraction, washing with dilute HCl water, drying and concentration, and then purified by column chromatography to obtain the desired bromo compound (37). (Yield 74%) (4) 4- [4 ″-{12- (3-hydroxy-2,2-dimethylpropionyloxy) dodecyloxy} biphenylyl-4′-carbonyloxy] benzoic acid 2-fluoroheptyl ester ( Synthesis of alcohol (38) 18.0 mmol of hydroxypivalic acid and 18.0 mmol of tetramethylammonium hydroxide (pentahydrate) were added to DMF150.
Stirred in ml for 2 hours. Next, 18.0 mmol of the bromo compound (37) obtained in (3) was added and stirred for 6 hours. After the reaction,
After ether extraction, drying and concentration, purification was carried out by column chromatography to obtain the desired novel compound, alcohol (38). (Yield: 75%) The phase transition behavior of this compound was as follows.

The electric field response speed of this compound was 80 μs at 124 ° C.

 The following table shows the elemental analysis values of this compound.

The ¹ H-NMR spectrum and IR spectrum of this compound are shown in FIG. 51 and FIG. 52, respectively.

Example 27 (Example) 4- [4 ″-{12- (3-acetoxy-2,2-dimethylpropionyloxy) dodecyloxy} biphenylyl-
Synthesis of 2-fluoroheptyl ester of 4'-carbonyloxy] benzoic acid (1) Alcohol (37) obtained in Example 26- (4) (7.5)
A solution of 5 mmol of acetic anhydride and 45.0 mmol of acetic anhydride in 5 ml of pyridine was stirred at room temperature for 12 hours. The reaction solution was extracted with ether and diluted HC
After washing with water, drying and concentration, purification was performed by column chromatography to obtain the desired novel compound of the above formula. (Yield: 82%) The phase transition behavior of this compound was as follows.

The electric field response speed of this compound was 50 μs at 99 ° C.

 The following table shows the elemental analysis values of this compound.

The ¹ H-NMR spectrum and IR spectrum of this compound are shown in FIG. 53 and FIG. 54, respectively.

Example 28 (Example) (1) Synthesis of 4'-carbobenzoxyoxobenzoic acid 2-fluorooctyl ester (ester (38)) Optically active 2-fluorooctanol 20 mmol TH
A solution of 20 ml of F and 40 ml of pyridine were cooled on ice, and a solution of 16 mmol of the acid chloride (5) obtained in Example 3- (2) in THF 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 and concentrated, and then purified by column chromatography to obtain the desired ester (38). (Yield 79%) (2) Synthesis of 4-hydroxybenzoyloxybenzoic acid 2-fluorooctyl ester (hydroxy form (39)) A solution of 10 mmol of the ester (38) obtained in (1) and 0.5 g of palladium carbon (5% catalyst) in ethyl acetate was reacted in a hydrogen gas atmosphere for 4 hours. After the reaction, palladium carbon was filtered through a membrane filter, concentrated and then purified by column chromatography to obtain the desired hydroxy compound (39). (Yield 98%) (3) Synthesis of 4- [4 ″-(12-bromododecyloxy) biphenylyl-4′-carbonyloxy] benzoic acid 2-fluorooctyl ester (bromo compound (40)) Carboxylic acid derivative (20) obtained in Example 7- (3) 50.0
The mmol was stirred with a solution of 20 ml of toluene and 10 ml of thionyl chloride at 80 ° C. for 2 hours to give the acid chloride. Excess toluene and thionyl chloride were distilled off under reduced pressure. next,
A solution of 55 mmol of the hydroxy compound (39) obtained in (2) and 60 mmol of triethylamine in 200 ml of THF was stirred, the THF solution of the acid chloride obtained earlier was added dropwise, and the mixture was stirred for 8 hours. After the reaction, the mixture was extracted with ether, washed with diluted HCl water, dried and concentrated, and then purified by column chromatography to obtain the desired bromo compound (40). (Yield 77%) (4) 4- [4 "-{12- (3-hydroxy-2,2-dimethylpropionyloxy) dodecyloxy} biphenylyl-4'-carbonyloxy] benzoic acid 2-fluorooctyl ester ( 41) Synthesis 18.0 mmol of hydroxypivalic acid and 18.0 mmol of tetramethylammonium hydroxide (pentahydrate) were added to DMF150.
Stirred in ml for 2 hours. Next, 18.0 mmol of the bromo compound (40) obtained in (3) was added and stirred for 6 hours. After the reaction,
After ether extraction, drying and concentration, the product was purified by column chromatography to obtain the desired alcohol (41)
I got (Yield 77%) The phase transition behavior of this compound was as follows.

The electric field response speed of this compound was 104 μs at 104 ° C.

 The following table shows the elemental analysis values of this compound.

The ¹ H-NMR spectrum and IR spectrum of this compound are shown in FIG. 55 and FIG. 56, respectively.

Example 29 (Example) 4- [4 ″-{12- (3-acetoxy-2,2-dimethylpropionyloxy) dodecyloxy} biphenylyl-
Synthesis of [4'-carbonyloxy] benzoic acid 2-fluorooctyl ester (1) Alcohol (41) 7.5 obtained in Example 28- (4)
A solution of 5 mmol of acetic anhydride and 45.0 mmol of acetic anhydride in 5 ml of pyridine was stirred at room temperature for 12 hours. The reaction solution was extracted with ether and diluted HC
After washing with water, drying and concentration, purification was performed by column chromatography to obtain the desired novel compound of the above formula. (79% yield) The phase transition behavior of this compound was as follows.

The electric field response speed of this compound was 40 μs at 92 ° C.

 The following table shows the elemental analysis values of this compound.

The ¹ H-NMR spectrum and IR spectrum of this compound are shown in FIG. 57 and FIG. 58, respectively.

Example 30 (Example) (1) 2-chloro-3-methylpentyl ester of 4'-carbobenzoxyoxobenzoic acid (ester (42))
Synthesis of A solution of 20 mmol of optically active 2-chloro-3-methylpentanol in 20 ml of THF and 40 ml of pyridine was ice-cooled.
A 16 mmol THF solution of the acid chloride (5) obtained in (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 and concentrated, and then purified by column chromatography to obtain the desired ester (42). (Yield 80%) (2) 4-Hydroxybenzoyloxybenzoic acid 2-chloro-3-methylpentyl ester (hydroxy form (4
3)) Synthesis A solution of 10 mmol of the ester (42) obtained in (1) and 0.5 g of palladium carbon (5% catalyst) in ethyl acetate was reacted in a hydrogen gas atmosphere for 4 hours. After the reaction, palladium carbon was filtered through a membrane filter, concentrated, and then purified by column chromatography to obtain the desired hydroxy compound (43). (Yield 98%) (3) Synthesis of 4- [4 ″-(12-bromododecyloxy) biphenylyl-4′-carbonyloxy] benzoic acid 2-chloro-3-methylpentyl ester (bromo compound (44)) Carboxylic acid derivative (20) obtained in Example 7- (3) 50.0
The mmol was stirred with a solution of 20 ml of toluene and 10 ml of thionyl chloride at 80 ° C. for 2 hours to give the acid chloride. Excess toluene and thionyl chloride were distilled off under reduced pressure. next,
A solution of 55 mmol of the hydroxy compound (43) obtained in (2) and 60 mmol of triethylamine in 200 ml of THF was stirred, the THF solution of the acid chloride obtained earlier was added dropwise, and the mixture was stirred for 8 hours. After the reaction, the mixture was subjected to ether extraction, dilute HCl aqueous washing, drying and concentration, and then purified by column chromatography to obtain the desired bromo compound (44). (Yield 87%) (4) 4- [4 "-{12- (3-hydroxy-2,2-dimethylpropionyloxy) dodecyloxy} biphenylyl-4'-carbonyloxy] benzoic acid 2-chloro-3- Methyl pentyl ester (alcohol (45))
Synthesis of 18.0 mmol of hydroxypivalic acid and 18.0 mmol of tetramethylammonium hydroxide (pentahydrate) were added to DMF150.
Stirred in ml for 2 hours. Next, 18.0 mmol of the bromo compound (44) obtained in (3) was added and stirred for 6 hours. After the reaction,
After ether extraction, drying and concentration, purification was carried out by column chromatography to obtain an alcoholic compound (45) which was a target novel compound. (Yield 87%) The phase transition behavior of this compound was as follows.

The electric field response speed of this compound was 20 μs at 99 ° C.

 The following table shows the elemental analysis values of this compound.

The ¹ H-NMR spectrum and IR spectrum of this compound are shown in FIG. 59 and FIG. 60, respectively.

Example 31 (Example) 4- [4 ″-{12- (3-acetoxy-2,2-dimethylpropionyloxy) dodecyloxy} biphenylyl-
Synthesis of 4'-carbonyloxy] benzoic acid 2-chloro-3-methylpentyl ester A solution of 7.5 mmol of the alcohol (45) obtained in Example 30- (4) and 45.0 mmol of acetic anhydride in 5 ml of pyridine for 12 hours at room temperature. Stirred. The reaction solution was extracted with ether, washed with diluted HCl water, dried and concentrated, and then purified by column chromatography to obtain the desired novel compound of the above formula. (Yield: 89%) The phase transition behavior of this compound was as follows.

The electric field response speed of this compound was 30 μs at 79 ° C.

 The following table shows the elemental analysis values of this compound.

The ¹ H-NMR spectrum and IR spectrum of this compound are shown in FIG. 61 and FIG. 62, respectively.

Example 32 (Example) (1) Synthesis of 4- (2-methylbutoxy) phenol (hydroxy form 46)) P-Toluenesulfonic acid 2-methylbutyl ester 20 obtained by tosylation of optically active 2-methylbutanol
N-butanol suspension of 100 mmol of sodium hydroxide and 10 ml of water + n
A 20 ml solution of butanol was added dropwise, followed by stirring at 120 ° C for 8 hours. Water was added to the reaction solution, and the mixture was extracted with ether, dried, concentrated, and purified by column chromatography to obtain the desired hydroxy compound (46). (Yield 72%) (2) Synthesis of 4- (2-methylbutoxy) phenyl ester of 4 '-(12-bromododecyloxy) biphenyl-4-carboxylic acid (bromo compound (47)) Carboxylic acid derivative (20) obtained in Example 7- (3) 50.0
The mmol was stirred with a solution of 20 ml of toluene and 10 ml of thionyl chloride at 80 ° C. for 2 hours to give the acid chloride. Excess toluene and thionyl chloride were distilled off under reduced pressure. next,
A solution of 55 mmol of the hydroxy compound (46) obtained in (1) and 60 mmol of triethylamine in 200 ml of THF was stirred, and the THF solution of the acid chloride obtained earlier was added dropwise, followed by stirring for 8 hours. After the reaction, the mixture was extracted with ether, washed with diluted HCl water, dried and concentrated, and then purified by column chromatography to obtain the desired bromo compound (47). (Yield 80%) (3) 4 '-[12- (3-hydroxy-2,2-dimethylpropionyloxy) dodecyloxy] biphenyl-4
-Synthesis of carboxylic acid 4- (2-methylbutoxy) phenyl ester (alcohol (48)) 18.0 mmol of hydroxypivalic acid and 18.0 mmol of tetramethylammonium hydroxide (pentahydrate) were added to DMF150.
Stirred in ml for 2 hours. Next, 18.0 mmol of the bromo compound (47) obtained in (2) was added and stirred for 6 hours. After the reaction,
After ether extraction, drying and concentration, the product is purified by column chromatography and the desired alcohol (48)
I got (Yield 81%) The phase transition behavior of this compound was as follows.

The electric field response speed of this compound was 320 μs at 82 ° C.

 The following table shows the elemental analysis values of this compound.

The ¹ H-NMR spectrum and IR spectrum of this compound are shown in FIG. 63 and FIG. 64, respectively.

Example 33 (Example) Synthesis of 4 '-[12- (3-acetoxy-2,2-dimethylpropionyloxy) dodecyloxy] biphenyl-4-carboxylic acid 4- (2-methylbutoxy) phenyl ester Obtained in Example 32- (3). A solution of 7.5 mmol of the alcohol (49) and 45.0 mmol of acetic anhydride in 5 ml of pyridine was stirred at room temperature for 12 hours. The reaction solution was extracted with ether, washed with diluted HCl water, dried and concentrated, and then purified by column chromatography to obtain the desired novel compound of the above formula. (Yield: 92%) The phase transition behavior of this compound was as follows.

The electric field response speed of this compound was 460 μs at 114 ° C.

 The following table shows the elemental analysis values of this compound.

FIG. 65 shows the ¹ H-NMR spectrum of this compound, and FIG. 66 shows its IR spectrum.

Example 34 (Example) (1) Synthesis of 4- (2-fluorooctyloxy) phenol (hydroxy form (50)) 20 mmol of p-toluenesulfonic acid 2-fluorooctyl ester and 40 mmol of hydroquinone obtained by tosylation of optically active 2-fluorooctanol
Add 100 mmol of sodium hydroxide to a butanol suspension
After dropwise adding 0 ml + 20 ml of n-butanol solution, the mixture was stirred at 120 ° C for 8 hours. Water was added to the reaction solution, which was extracted with ether, dried, concentrated, and purified by column chromatography to obtain the desired hydroxy compound (50) of the above formula. (Yield 62%) (2) 4 '-(12-bromododecyloxy) biphenyl-4-carboxylic acid 4- (2-fluorooctyloxy)
Synthesis of phenyl ester (bromo compound (51)) Carboxylic acid derivative (20) obtained in Example 7- (3) 50.0
The mmol was stirred with a solution of 20 ml of toluene and 10 ml of thionyl chloride at 80 ° C. for 2 hours to give the acid chloride. Excess toluene and thionyl chloride were distilled off under reduced pressure. next,
A solution of 55 mmol of the hydroxy compound (50) obtained in (1) and 60 mmol of triethylamine in 200 ml of THF was stirred, the THF solution of the acid chloride obtained earlier was added dropwise, and the mixture was stirred for 8 hours. After the reaction, the mixture was extracted with ether, washed with diluted HCl water, dried and concentrated, and then purified by column chromatography to obtain the desired bromo compound (51). (Yield 74%) (3) 4 '-[12- (3-hydroxy-2,2-dimethylpropionyloxy) dodecyloxy] biphenyl-4
Synthesis of carboxylic acid 4- (2-fluorooctyloxy) phenyl ester (alcohol (52)) 18.0 mmol of hydroxypivalic acid and 18.0 mmol of tetramethylammonium hydroxide (pentahydrate) were added to DMF150.
Stirred in ml for 2 hours. Next, 18.0 mmol of the bromo compound (51) obtained in (2) was added and stirred for 6 hours. After the reaction,
After ether extraction, drying and concentration, purification was carried out by column chromatography to obtain the desired novel compound, alcohol (52). (Yield: 78%) The phase transition behavior of this compound was as follows.

The electric field response speed of this compound was 20 μs at 136 ° C.

 The following table shows the elemental analysis values of this compound.

FIG. 67 shows the ¹ H-NMR spectrum of this compound, and FIG. 68 shows its IR spectrum.

Example 35 (Example) Synthesis of 4 '-[12- (3-acetoxy-2,2-dimethylpropionyloxy) dodecyloxy] biphenyl-4-carboxylic acid 4- (2-fluorooctyloxy) phenyl ester (1) Example 34- (3) Alcohol (52) obtained in 7.5
A solution of 5 mmol of acetic anhydride and 45.0 mmol of acetic anhydride in 5 ml of pyridine was stirred at room temperature for 12 hours. The reaction solution was extracted with ether and diluted HC
After washing with water, drying and concentration, purification was performed by column chromatography to obtain the desired novel compound of the above formula. (Yield: 92%) The phase transition behavior of this compound was as follows.

The electric field response speed of this compound was 10 μs at 119 ° C.

 The following table shows the elemental analysis values of this compound.

The ¹ H-NMR spectrum and IR spectrum of this compound are shown in FIG. 69 and FIG. 70, respectively.

Example 36 (Example) (1) Synthesis of 4- (2-methylbutyryloxy) phenol (hydroxy form (53)) 1 ml of concentrated sulfuric acid was added to a solution of 50 mmol of optically active 2-methylbutanoic acid and 100 mmol of hydroquinone in 150 ml of toluene, and the mixture was refluxed for 3 hours. After concentration, the residue was purified by column chromatography to obtain the desired hydroxy compound (53). (Yield 73%) (2) Synthesis of 4- (2-methylbutyryloxy) phenyl ester of 4 '-(12-bromododecyloxy) biphenyl-4-carboxylic acid (bromo compound (54)) Carboxylic acid derivative (20) obtained in Example 7- (3) 50.0
The mmol was stirred with a solution of 20 ml of toluene and 10 ml of thionyl chloride at 80 ° C. for 2 hours to give the acid chloride. Excess toluene and thionyl chloride were distilled off under reduced pressure. next,
A solution of 55 mmol of the hydroxy form (53) obtained in (1) and 60 mmol of triethylamine in 200 ml of THF was stirred, the THF solution of the acid chloride obtained earlier was added dropwise, and the mixture was stirred for 8 hours. After the reaction, the mixture was extracted with ether, washed with diluted HCl water, dried and concentrated, and then purified by column chromatography to obtain the desired bromo compound (54). (3) 4 '-[12- (3-hydroxy-2,2-dimethylpropionyloxy) dodecyloxy] biphenyl-4 (79% yield)
Synthesis of carboxylic acid 4- (2-methylbutyryloxy) phenyl ester (alcohol (55)) 18.0 mmol of hydroxypivalic acid and 18.0 mmol of tetramethylammonium hydroxide (pentahydrate) were added to DMF150.
Stirred in ml for 2 hours. Next, 18.0 mmol of the bromo compound (54) obtained in (2) was added and stirred for 6 hours. After the reaction,
After ether extraction, drying and concentration, purification was carried out by column chromatography to obtain the desired novel compound, alcohol (55). (Yield: 78%) The phase transition behavior of this compound was as follows.

The electric field response speed of this compound was 126 μs at 20 μs.

 The following table shows the elemental analysis values of this compound.

The ¹ H-NMR spectrum and IR spectrum of this compound are shown in FIG. 71 and FIG. 72, respectively.

Example 37 (Example) Synthesis of 4 '-[12- (3-acetoxy-2,2-dimethylpropionyloxy) dodecyloxy] biphenyl-4-carboxylic acid 4- (2-methylbutyryloxy) phenyl ester (1) Example 36- (3 7.5) The alcohol form obtained in ()
A solution of 5 mmol of acetic anhydride and 45.0 mmol of acetic anhydride in 5 ml of pyridine was stirred at room temperature for 12 hours. The reaction solution was extracted with ether and diluted HC
After washing with water, drying and concentration, purification was performed by column chromatography to obtain a novel compound represented by the above formula. (Yield: 92%) The phase transition behavior of this compound was as follows.

The electric field response speed of this compound was 190 μs at 116 ° C.

 The following table shows the elemental analysis values of this compound.

The ¹ H-NMR spectrum and IR spectrum of this compound are shown in FIG. 73 and FIG. 74, respectively.

Example 38 (Example) (1) 4'-Carbobenzoxybiphenyl-4-carboxylic acid 1-methylheptyl ester (ester (56))
Synthesis of Optically active 1-methylheptanol 20 mmol THF2
A solution of 0 ml and 40 ml of pyridine was cooled on ice, and a solution of 16 mmol of the acid chloride (13) obtained in Example 5- (2) in THF 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 and concentrated, and then purified by column chromatography to obtain the desired ester (56).
(Yield 69%) (2) 4'-hydroxybiphenyl-4-carboxylic acid 1
Synthesis of methylheptyl ester (hydroxy form (57)) A solution of 10 mmol of the ester (56) obtained in (1) and 0.5 g of palladium carbon (5% catalyst) in ethyl acetate 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 the desired hydroxy compound (57). (Yield 97%) (3) Synthesis of 4- (12-bromododecanoyloxy) benzoic acid benzyl ester (ester (58)) 50 mmol of 12-bromododecanoic acid was stirred with a solution of 20 ml of toluene and 10 ml of thionyl chloride at 80 ° C. for 2 hours to obtain an acid chloride. Excess toluene and thionyl chloride were distilled off under reduced pressure. Next, 55 mmol of 4-hydroxybenzoic acid benzyl ester and triethylamine
A solution of 60 mmol of THF in 200 ml of THF was stirred, the THF solution of the acid chloride obtained above was added dropwise, and the mixture was stirred for 8 hours. After the reaction, after ether extraction, washing with dilute HCl water, drying and concentration,
Purification by column chromatography gave the desired ester (58). (Yield 90%) (4) Synthesis of 4- (12-bromododecanoyloxy) benzoic acid (carboxylic acid derivative (59)) 50 mmol of the ester (58) obtained in (3) and 2.0 g of palladium carbon (5% catalyst) in 500 ml of ethyl acetate
The solution was stirred under a hydrogen gas atmosphere for 24 hours. After the reaction, filtration and concentration, purification by column chromatography,
The desired carboxylic acid derivative (59) was obtained. (Yield 99
%) (5) 4 '-[4 "-(12-bromododecanoyloxy) biphenyl-4'-carbonyloxy] benzoic acid-
Synthesis of 1-methylheptyl ester (bromo compound (60)) Carboxylic acid derivative (9) obtained in Example 3- (6) 50.0
The mmol was stirred with a solution of 20 ml of toluene and 10 ml of thionyl chloride at 80 ° C. for 2 hours to give the acid chloride. Excess toluene and thionyl chloride were distilled off under reduced pressure. next,
A solution of 55 mmol of the hydroxy compound (57) obtained in (1) and 60 mmol of triethylamine in 200 ml of THF was stirred, the THF solution of the acid chloride obtained earlier was added dropwise, and the mixture was stirred for 8 hours. After the reaction, ether extraction, washing with dilute HCl water, drying and concentration were performed, followed by purification by column chromatography.
The desired bromo compound (60) was obtained. (Yield 89%) (6) 4 '-[4 "-{12- (2,2-dimethylpropionyloxy) dodecanoyloxy} benzoyloxy]
Synthesis of biphenyl-4-carboxylic acid 1-methylheptyl ester 18.0 mmol of pivalic acid and 18.0 mmol of tetramethylammonium hydroxide (pentahydrate) were stirred in 150 ml of DMF. Next, 18.0 mmol of the bromo compound (60) obtained in (5) 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 desired novel compound, alcohol. (Yield: 72%) The phase transition behavior of this compound was as follows.

The electric field response speed of this compound was 110 μs at 43 ° C.

 The following table shows the elemental analysis values of this compound.

The ¹ H-NMR spectrum and IR spectrum of this compound are shown in FIG. 75 and FIG. 76, respectively.

Example 39 (comparative example) 4- {4- (12-propionyloxidedecyloxy)
Synthesis of benzoyloxy 2-benzoic acid 2-methylbutyl ester (1) 35.0 mmol of propionic acid and 35 mmol of tetramethylammonium hydroxide (pentahydrate) were stirred in 100 ml of DMF for 1 hour. Next, 25 mmol of the bromo compound (10) obtained in (7) of Example 3 was added, and the mixture was stirred for 10 hours. After the reaction, the mixture was extracted with ether, dried and concentrated, and then purified by column chromatography to obtain the desired novel compound of the above formula. (Yield: 88%) The phase transition behavior of this compound was as follows.

The electric field response speed of this compound was 220 μs at 12 ° C.

 The following table shows the elemental analysis values of this compound.

The ¹ H-NMR spectrum and IR spectrum of this compound are shown in FIG. 77 and FIG. 78, respectively.

〔The invention's effect〕

The novel compound of the present invention is an inexpensive and liquid crystalline compound having a chemically stable chemical structure and exhibits a strongly inducible chiral smectic C phase in a wide temperature range around room temperature or below room temperature, Extremely fast response speed to various electronic optical devices such as digital displays such as calculators and watches, electro-optical shutters, electro-optical apertures, optical modulators, optical communication optical path switching switches, memories, liquid crystal printer heads, and focal length variable lenses. It has high utility as an electro-optical element for use, and its industrial value is great.

[Brief description of the drawings]

FIG. 1, FIG. 3, FIG. 5, FIG. 7, FIG. 9, FIG.
FIG. 13, FIG. 15, FIG. 17, FIG. 19, FIG. 21, FIG. 23, FIG.
FIG. 27, FIG. 29, FIG. 31, FIG. 33, FIG. 35, FIG.
FIG. 39, FIG. 41, FIG. 43, FIG. 45, FIG. 47, FIG.
Figures, 51, 53, 55, 57, 59, 61
Fig. 63, Fig. 65, Fig. 67, Fig. 69, Fig. 71, Fig. 73
FIG. 75, FIG. 75, and FIG. 77 show Example 1, Example 2, Example 3, Example 4, Example 5, Example 6, Example 7, Example 8, Example 9, Example 10, Example 11, and Example 1, respectively.
2, Example 13, Example 14, Example 15, Example 16, Example 17, Example 18, Example 19, Example 2
0, Example 21, Example 22, Example 23, Example 24, Example 25, Example 26, Example 27, Example 2
8, Example 29, Example 30, Example 31, Example 32, Example 33, Example 34, Example 35, Example 3
6 is a chart of the ¹ H-NMR spectrum of the compounds obtained in Examples 6, 37, 38 and 39. FIG. 2, FIG. 4, FIG. 6, FIG. 8, FIG. 10, FIG.
FIG. 14, FIG. 16, FIG. 18, FIG. 20, FIG. 22, FIG. 24, FIG.
FIG. 28, FIG. 30, FIG. 32, FIG. 34, FIG. 36, FIG.
FIG. 40, FIG. 42, FIG. 44, FIG. 46, FIG. 48, FIG.
Figures, 52, 54, 56, 58, 60, 62
FIG. 64, FIG. 66, FIG. 68, FIG. 70, FIG. 72, FIG.
FIG. 76, FIG. 76, and FIG. 78 show Example 1, Example 2, Example 3, Example 4, Example 5, Example 6, Example 7, Example 8, Example 9, Example 10, Example 11, and Example 1, respectively.
2, Example 13, Example 14, Example 15, Example 16, Example 17, Example 18, Example 19, Example 2
0, Example 21, Example 22, Example 23, Example 24, Example 25, Example 26, Example 27, Example 2
8, Example 29, Example 30, Example 31, Example 32, Example 33, Example 34, Example 35, Example 3
6 is a chart showing the IR spectrum chart of the compounds obtained in Examples 6, 37, 38 and 39.

Claims (2)

(57) [Claims] (1) General formula (Wherein, R ¹ , R ² and R ³ represent —H, —CH ₃ , —OH, —OCH ₃ or —OCOCH ₃ , which may be the same or different, and R ⁴ and R ⁵ represent —CH _3, -OH, indicates -OCH ₃ or -OCOCH _3, which may be the same or different, R ⁶ is Wherein R ⁷ and R ⁸ represent -CH ₃ , -CN, -CF ₃ or a halogen atom, Y represents -O-, -COO- or -OCO-, and Z represents -COO-, -OCO -, - CH ₂ O- or -OCH ₂ - indicates, s and p is 0 or 1, m is an integer of 1 to 20, n, l and q are each an integer of 0, ^{C *} is Represents an asymmetric carbon. However, when n = 0, R ¹ , R ² and R ³ are —OH, —OCH ₃ or —OCOCH ₃ , and p = q = 0
In the formula, R ⁸ ≠ —CH ₃ . ) A novel compound represented by In the general formula, R ⁸ is —CH ₃ , Y is —COO—,
2. The method according to claim 1, wherein s is 0, 1 is 1, p is 0, and q is 1.
A novel compound as described.