JPH03218338A - Tranexamic acid derivative - Google Patents

Abstract

NEW MATERIAL:A tranexamic acid derivative expressed by formula l (R1 is 1-16C linear chain or branched saturated or unsaturated hydrocarbon residue, which may be replaced with halogen; R2 is H or methyl; R3 is formula II; P and (q) are each 0 or 1; (n) is 1-16). EXAMPLE:trans-4-(N,N-Limethylaminomethyl)cyclohexanecarboxylic acid 4''-(2- methylbutyloxycarbonyl)-4'-biphenylester. USE:Useful for thermally writing in liquid crystal element and element for display. The compound expressed by formula I exhibits liquid crystal phase in wide temperature region close to ambient temperature and alone used or properly blended with other smectic liquid crystal to simply and inexpensively provide a liquid crystal usable as thermally writing in liquid crystal element or liquid crystal element for display by applying a therm-optical effect in practical temperature region. PREPARATION:A compound expressed by formula III obtained by N-alkylation of tranexamic acid is subjected to a reaction with a compound expressed by formula IV to provide the compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application j] The present invention relates to a novel tranexamic acid derivative and a method for producing the same.

The compound provided by the present invention has liquid crystal properties and can be used for thermal writing liquid crystal devices and display liquid crystal devices.

[Jubei's technology] Among the known liquid crystal compounds, smectic liquid crystal or cholesteric liquid crystal exhibits a transparent liquid crystal structure.When a thin layer of smectic liquid crystal or cholesteric liquid crystal is partially heated and rapidly cooled, that part becomes an opaque liquid crystal that scatters light. The phenomenon of transition to structure is known as the thermo-optic effect of liquid crystals. Several liquid crystal elements have been proposed that take advantage of this phenomenon and write information by applying a partial temperature change to the liquid crystal cell and making that area opaque.6 Used in thermal writing liquid crystal elements, etc. The substance required to do so must be stable against moisture, air, and light, and must also have an appropriate phase transition temperature.

The appropriate phase transition temperature referred to here refers to a sufficiently wide temperature range including room temperature so that thermal writing is possible at room temperature and is not affected by storage temperature. It is hoped that the disease will not metastasize. Schiff-based liquid crystal materials, which are commonly used as light valve elements for projection displays, are susceptible to hydrolysis, and therefore have short lifespans and lack reliability in terms of moisture resistance6. As a compound, the general formula (however,
R represents an alkyl group. ), but all of these were insufficient in terms of the liquid crystal temperature range.

Furthermore, among many known liquid crystal compounds, there is one called nematic liquid crystal. This thing is
Although it currently constitutes the mainstream of compounds or compositions used in liquid crystal display devices, one of its disadvantages is that the response speed is slow, and a response speed of only a few msec can be obtained. Therefore, it is said that we are approaching the limit for increasing the size of the display.

To improve the drawbacks of conventional liquid crystal display elements, Clark and Lagauer proposed the use of bistable liquid crystals (Japanese Patent Laid-Open No. 56-1072).
No. 16). Liquid crystals with this bistability are called ferroelectric liquid crystals, and have attracted attention for their high-speed response and memory properties.Especially in recent years, studies have been active on their practical application, and practical ferroelectric liquid crystals have attracted attention. There is an urgent need to develop new materials.

In general, a ferroelectric liquid crystal is a compound having an optically active site and is expressed in a series of smectic phases having a molecular orientation in which the long axis of the molecule is tilted from the normal direction of the layer. Among them, the chiral smectic C (hereinafter abbreviated as S) phase is considered to be advantageous in practice because of its relatively low voltage operability.

In this way, ferroelectric liquid crystals have a very fast response speed due to their spontaneous polarization, and can create a bistable state with memory properties, and also have excellent viewing angles. It is left as a material for large-capacity, large-screen displays.

As such a ferroelectric liquid crystal, in 1975, R. B. M
4-(4-n-1decylbenzylideneamino)cinnamic acid-2-methylbutyl ester (hereinafter abbreviated as DOIIAMBC) synthesized by Eyer et al. is known (J. Physique 36 L-69 (19
75)).

This DOroAMBC contains a Schiff base in its structure, and therefore has a problem in its chemical stability. Therefore, various physically and chemically stable compounds have been searched for as ferroelectric liquid crystal materials, and currently 4-(4-n alkyloxyphenyl)-1-carboxylic acid-2-methylbutyl ester (hereinafter referred to as CN The main focus has shifted to the search for esdel-based compounds, including (abbreviated as ). However, ester compounds such as CN do not exhibit an S% phase, or even if they do, the temperature range in which they exhibit an Sc'' phase is narrow, and moreover, they exhibit different phase series when the liquid crystal is heated or cooled. Because it is a monotropic liquid crystal display, there are few that can withstand practical use (Liq
uid Crystals and OrderedF
luids 4 (1984)).

On the other hand, as a method for shifting the liquid crystal phase temperature range to a wider range including room temperature, introduction of a hetero ring such as a pyridine or pyrimidine ring or a cyclohexane ring is generally carried out, but the synthesis method is complicated.

In particular, when introducing a cyclohexane ring to improve liquid crystallinity, there are cases where smectic properties are lost due to the introduction of the cyclohexane ring, and separation of a mixture of cis-trans isomers of 1,4-disubstituted cyclohexane during the synthesis stage. Due to problems such as the need for operations, sufficient consideration had not been made.

On the other hand, tranexamic acid is a cyclohexane derivative and is widely used as a hemostatic agent.

However, it has not yet been used for any purpose other than as a medicine.

The present inventors investigated a liquid crystal compound using tranexamic acid as a raw material as a compound having a cyclohexane ring that is inexpensive, highly pure, and easily available.

First, Schiff base derivatives of tranexamic acid represented by the following formula (wherein R6 and R7 represent hydrocarbon residues) were synthesized, but it was found that these compounds did not exhibit liquid crystallinity.

[Problems to be Solved by the Invention] As a result of further investigation, it was discovered that phenyl ester compounds are compounds that exhibit stable liquid crystallinity as tranexamic acid derivatives. That is, an object of the present invention is to provide a novel tranexamic acid derivative having a wide liquid crystal temperature range and a method for producing the same.

Trans-1.4- Tranexamic acid is cheap and easy to obtain.
A novel liquid crystal compound is provided by using di-substituted cyclohexane as a raw material and alkylating the N-terminus and esterifying the C-terminus.

Furthermore, in the present invention, it is easy to change the type and length of the alkyl group at the N-terminus and the type of ester group at the C-terminus, thereby controlling the type and temperature range of the liquid crystal phase developed in the liquid crystal state. The present invention provides a liquid crystal compound that can be used as a liquid crystal compound, and a liquid crystal composition containing the same as at least one compounded component.

[Means for Solving the Problems] The compound provided by the present invention has the following formula: -fi formula (I) (I> [wherein R is a linear or branched chain having 1 to 16 carbon atoms] is a saturated or unsaturated hydrocarbon residue, which may be substituted with halogen.R2 is hydrogen or a methyl group, and R3 is the general formula (I])...- (■) In the formula, p.q is O or 1.n is an integer of 1 to 16, respectively.] The present invention relates to a novel tranexamic acid derivative represented by the following and a method for producing the same, and further relates to an intermediate of the tranexamic acid derivative and a method for producing the same. .

In the present invention, tranexamic acid is used as a raw material for trans-1,4-disubstituted cyclohexane, and by alkylating the 11 N Song terminal and esterifying the C terminal, it exhibits stable liquid crystallinity over a wide temperature range. succeeded in synthesizing the compound.

That is, upon alkylation of an amino group, liquid crystallinity changes depending on the type of alkyl substitution of the amino group. Regarding R1, it is a linear or branched saturated or unsaturated hydrocarbon residue having 1 to 16 carbon atoms, and a portion thereof may be substituted with halogen.

Particularly preferred are linear saturated alkyl residues and branched saturated or unsaturated hydrocarbon residues having asymmetric carbons, including asymmetric carbons.

When the number of carbon atoms exceeds 17, not only is it difficult to prepare the raw material manually, but also the thermal stability of the obtained tranexamic acid derivative as a liquid crystal compound becomes low. The number of carbon atoms is preferably 1 or 5 to 10.

R2 is hydrogen or a methyl group, and when it is hydrogen, the liquid crystal lagoonality range is wide and a smectic phase appears. A smectic phase also appears when it is a methyl group, but the liquid crystal temperature range is narrow.

l 2 That is, when R2 is hydrogen, SmA (smectic A phase) is extremely stable, and it is SmA regardless of the number of carbon atoms in R1, and appears in a wide temperature range from 35°C to 138°C, and R, If the number of carbon atoms in is too large, liquid crystallinity decreases.

On the other hand, when R2 is a methyl group, SmX (higher-order smectic phase) is likely to occur when R is a methyl group, and R,
As the chain length becomes longer, it tends to become SA phase or Sc phase.

In particular, R. When is a branched saturated or unsaturated hydrocarbon residue having an asymmetric carbon, it tends to exhibit an S♂ phase (and exhibits ferroelectric properties).

R3 is represented by general formula (II).

...-- (IT) E formula, p. q is 0 or l. n represents an integer from 1 to 16. 1 Regarding the influence of n in formula (II) in R3, n = 1 to 16, preferably 5 to 12, and n is 5
The liquid crystallinity worsens as the distance increases from ~8. Note that this alkyl group may be linear or branched, and may or may not have an asymmetric carbon atom.

Further, when q=0 (alkyl phenyl ether), the cholesteric property increases, but as n increases, the cholesteric property tends to decrease. q=1
(benzoic acid ester), smectic properties increase.

As a production method, N-alkyl R2 of tranexamic acid... (m) In the formula E, R is a linear or branched saturated or unsaturated hydrocarbon residue having 1 to 16 carbon atoms. , may be substituted with halogen. R2 is hydrogen or a methyl group. ] An intermediate represented by the formula (I
V) -. ] By dehydration condensation with the phenol derivative represented by the general formula (I)...
(I) [In the formula, R is a linear or branched saturated or unsaturated hydrocarbon residue having 1 to 16 carbon atoms, and may be substituted with halogen. R2 is hydrogen or a methyl group, and R3 is represented by the general formula (II) l 5 ...- (II) in the formula. p. q is O or 1. n represents an integer from 1 to 16. ] A tranexamic acid derivative represented by the following can be produced.

The synthesis method for N-alkyltranexamic acid represented by the general formula (nB) differs depending on the types of R1 and R2.

That is, a compound in which both R and R2 are methyl groups can be easily obtained by simply heating and refluxing tranexamic acid in water with formaldehyde and formic acid; In the case of the compound, the amino group is protected with a t-butyloxycarponyl group, etc., and then N-methylated using methyl iodide and sodium hydride, followed by deprotection of the t-butyloxycarponyl group. Thereafter, it can be obtained by alkylation using an alkyl bromide whose carbon number corresponds to R1 and sodium hydride.

Also. For compounds in which R2 is hydrogen, an amide is obtained by reacting tranexam 16 acid benzyl ester with an acid chloride having the number of carbon atoms corresponding to Rt, including the carbon of the carboxyl group, under basic conditions, and the carbonyl group of the amide is prepared using borane. It is obtained by selectively reducing , and then deprotecting the benzyl group by hydrogenolysis. The reaction formula is shown in Table 1 below.

(Left below) The compound represented by the general formula (IV) is obtained by condensing an alcohol or phenol derivative corresponding to 4-hydroxybenzoic acid or 4-(4°-hydroxyphenyl)benzoic acid using dianyl chloride or the like. Alternatively, it can be obtained by alkylating an alkyl bromide or alkyl tosylate corresponding to 4-hydroxyphenol or 4-(4°hydroxyphenyl)monophenol in the presence of a base.

Furthermore, it is necessary to introduce a protecting group such as pendyl ether into the hydroxyl group as appropriate during the synthesis. The reaction formula is shown in Table 2 below.

(The following is a blank space) The tranexamic acid derivative of the general formula (1) can be obtained by reacting the compound represented by the general formula (III) and the general formula (IV). Specifically, the condensation reaction is carried out in an appropriate solvent (for example, dichloromethane, carbon tetrachloride, benzene, etc.) using N.I. as a condensing agent. Using N'-dicyclohexyllupodiimide (hereinafter abbreviated as DCC), etc., or derivatizing the general formula (III) to an acid halide etc. using dianyl chloride etc., and converting the general formula (III) under basic conditions. There are methods such as applying (IV).

The compound produced by the method described above is purified by column chromatography and recrystallization.

N-alkyltranexamic acid represented by the general formula (V) H [where R4 is an alkyl group having 3 to 16 carbon atoms] is a 2 1 intermediate of the tranexamic acid derivative represented by the formula (I), and is a novel It is a compound. The manufacturing method is
Among the methods for producing the compound represented by the general formula (II1) described above, the method for producing the compound in which R2 is hydrogen will be explained in the same manner as the method for producing the compound represented by the general formula (II1).

General formula (Vl) C H 3 [However, R5 is represented by 1 alkyl group having 2 to 16 carbon atoms.N-methyl-N-alkyltranexamic acid is also an intermediate like the compound of general formula (V), and is a novel compound. It is a compound. The manufacturing method thereof is explained in the same manner as the manufacturing method of the compound represented by the general formula (ni) described above, in which R is an alkyl group having 2 to 16 carbon atoms and R2 is a methyl group. .

[Function 1] The compound of general formula N in the present invention (hereinafter blank) 2 2 ...-(I) is a tranexamic acid derivative that has a low melting point and exhibits very stable liquid crystallinity.

Having a stable liquid crystal phase in a wide temperature range close to room temperature is not only due to the low melting point effect due to the introduction of the cyclohexane ring, but also because the amino groups present between the methylene groups promote polarization of the molecules, resulting in liquid crystal alignment. It is presumed that this makes it easier to take.

In particular, some secondary amine compounds exhibit a smectic A-only phase arrangement over 100° C. (Table 3, Example 3.6). This is because intermolecular hydrogen bonds, as is known in compounds with amide bonds, have generally been thought to reduce liquid crystallinity, but hydrogen bonds in amino groups contribute to stabilizing the alignment of liquid crystal molecules. Conceivable.

Further, when R1 is a hydrocarbon residue having an asymmetric carbon, ferroelectricity is exhibited (Table 3, Examples 12 to 15). This is thought to be because the bond angle of the optically active group changes due to the influence of the nearby amino group, resulting in a steric structure favorable for the expression of ferroelectricity and stabilization.

The compound of the present invention has excellent durability and thermal stability like Joki, and can be used alone as a liquid element compound for thermal writing, a liquid crystal display element with excellent responsiveness and memory performance, etc. It is thought that it is useful to improve the response and expand the temperature range by blending it with a liquid crystal compound, or by blending it with already known ferroelectric liquid crystals.

[Examples] Hereinafter, the compounds of the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

Below, Cry. Ch. SIL. Sc. The Iso phase represents a crystal, cholesteric phase, smectic A phase, chiral smectic C phase, and isotropic liquid, respectively, and Sx represents a higher-order structure of the smectic phase. Also, r t. indicates thirst.

The compound of the present invention was purified by silica gel chromatography and recrystallization with alcohol, hexane, etc.

The measured values of phase transition points shown below may be slightly influenced by the purity of the material.

<Example 1> Synthesis of trans-4- (N.N-dimethylaminomethyl)cyclohexanecarboxylic acid 4''-(2-methylbutyl)-4''-biphenyl ester [1-11 trans-4- Synthesis of (N.N-dimethylaminomethyl)cyclohexanecarboxylic acid hydrochloride 4.72 g of tranexamic acid was dissolved in 5 ml of purified water,
5% formaldehyde aqueous solution 2.5mi! , formic acid 6.4
mβ was added, and the mixture was heated under reflux for 9 hours.

After further stirring at room temperature for 12 hours, 4.5 m of concentrated sulfuric acid was added,
The solvent was removed under reduced pressure.

30 mβ of toluene was added and distilled again under reduced pressure. After confirming that the odor had disappeared, ethyl ether was added and crystallized. Collect the crystals by filtration and obtain colorless scales of trans-4-
4.76 g (yield 7l.6%) of (N,N-dimethylaminomethyl)cyclohexanecarboxylic acid hydrochloride was obtained.

The obtained compound was analyzed by 'H-NMR. The structure was confirmed by IR.

(1-21 Synthesis of 4-(4'-hydroxyphenyl)benzoic acid 2-methylbutyl ester 4-(4'-hydroxyphenyl)benzoic acid 2.14
g, 5.4 mβ of 2-methylbutanol, and 57 mg of p-toluenesulfonic acid monohydrate were stirred at 120°C for 3 hours. After cooling, dilute with 50 ml of dichloromethane and add saturated aqueous sodium bicarbonate solution (20rr+j2). After sequentially washing with saturated brine (20 mI2), it was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure.

The obtained crystals were washed several times with cold hexane and then recrystallized from hexane to obtain 1.6 g (57%) of colorless needle-like 2-methylbutyl 4-(4°hydroxyphenyl)benzoate 26 ester. .

[1-31 Synthesis of title compound 532 mg of the compound synthesized in (1-1) and +1. −
21 568 mg of the compound synthesized in step 21 was added to dichloromethane 5
Dissolved in mI2 and added 495 mg of dicyclohexylluposiimide (hereinafter abbreviated as DCC) under water cooling.
The mixture was stirred for an hour and further stirred at room temperature overnight.

The solvent is distilled off under reduced pressure, 30 mβ of ethyl acetate is added, and the mixture is stirred for a while and then filtered. The obtained crystals are dichloromethane 3
Dissolve in 0 m I2 and filter off insoluble matter. The organic layer was dissolved in a saturated aqueous sodium bicarbonate solution (5 mβ) and a saturated saline solution (
After washing with 5mj2) and drying with magnesium sulfate, the solvent was distilled off under reduced pressure.

By recrystallizing from the obtained crude hexane,
202 mg (yield 22%) of the title compound as a colorless powder was obtained.

The structure of the obtained compound was confirmed by 'H-NMR and IR.

<Example 2>4-[trans-4'-(N.N-dimethylaminomethyl)cyclohexylluponyloxy]benzoic acid 4
Synthesis of ``-(2-methylbutyloxycarbonyl)phenyl ester (2-11 4-hydroxybenzoic acid 4'-(2-
Synthesis of methylbutyloxybenzoic acid (6.54 g) and carbon tetrachloride (4)
After heating under reflux for 3 hours with 12.5 g of thionyl chloride in 0 mβ, unreacted thionyl chloride and carbon tetrachloride were distilled off, dissolved in 1 OmJ2 of toluene, and mixed with 1.64 g of 2-methylbutyl alcohol in toluene. -viridine (4:1
) Add dropwise to 30 ml of solution and heat under reflux for 3 hours. After the reaction was completed, 30+nJ2 of ethyl acetate was added to the reaction solution, followed by purified water (30mJ2), 5% hydrochloric acid (30mJ2). Saturated sodium bicarbonate aqueous solution (30 mI2), saturated saline (
After sequentially washing with 30rnJ2), it was dried with magnesium sulfate. Ethyl acetate was distilled off, and this was separated by silica gel column chromatography using a 10:1 mixture of n-hexane and ethyl acetate as an eluent to give a colorless oil.
49g was obtained. Next, this oil was mixed with ethanol 15mβ
The mixture was heated under reflux for 1 hour in the presence of 6.75 g of cyclohexene and 0.45 g of palladium black. After filtering the reaction solution to remove palladium black, ethanol and cyclohexene were distilled off to give 2-methylbutyl 4-
Obtained 2.99 g of hydroxybenzoate (yield 93%)
].

Next, 0.80 g of p-penzyloxybenzoic acid was heated under reflux with 4.17 g of thionyl chloride in 15 mβ of carbon tetrachloride, and then unreacted thionyl chloride and carbon tetrachloride were distilled off. - Add a solution of 0.73 g of methylbutyl 4-hydroxybenzoate dissolved in 7 mβ of toluene, and then add 3.50 g of pyridine, and
Stir for hours. After the reaction is completed, 30% ethyl acetate is added. Orr
+i! and 5% hydrochloric acid (10 mff). Saturated sodium bicarbonate aqueous solution (10 mβ), saturated saline (102
After sequentially washing with 9 mJ2), it was dried with magnesium sulfate.

Ethyl acetate was distilled off and recrystallized from methanol to give 4'
- 0.89 g of (2-methylbutyloxycarbonyl)phenyl 4-penzyloxybenzoate was obtained. Next, dissolve this in 10.0 mff of ethanol, add 1.01 g of cyclohexene and 0.18 g of palladium black.
The mixture was heated under reflux for 1 hour in the presence of . After filtering the reaction solution to remove palladium black, ethanol and cyclohexene were distilled off, and 0.69 g of 4-hydroxybenzoic acid 4° (2-methylbutyl chloride) phenyl ester was obtained.
(yield: 60%).

(2-2) Synthesis of the title compound 266 mg of the compound synthesized in (1-1) and the compound synthesized in 12-1) were dissolved in 3 ml of dichloromethane, and 240 mg of DCC was added under water cooling, followed by the same procedure as in (1-3). The reaction was carried out using the method described above, and 259 mg (yield: 52%) of the title compound was obtained as a colorless powder by recrystallization from hexane.

The obtained compound was analyzed by 'H-NMR. Part 30 in IR The structure was confirmed.

<Example 3> Synthesis of trans-4-(N-hepdylaminomethyl)cyclohexanecarboxylic acid 4"-(2-methylbutyloxycarbonyl)-4°-biphenyl ester (3-11) Synthesis of aminomethyl hexanecarboxylic acid benzyl ester tosylate 4.72 g of tranexamic acid and 15 m of benzyl alcohol
β was suspended in 30 mβ of toluene, 6.84 g of p-toluenesulfonic acid was added, and the mixture was heated under reflux for 3 hours while removing water generated using a Dean-Stark apparatus.

After confirming that the reaction solution became transparent, it was cooled. The precipitated crystals were collected by filtration and recrystallized from ethanol to obtain 11.5 g (yield: 99%) of colorless needle-like tranexamic acid benzyl ester tosylate.

(3-2) Synthesis of l-lansu 4-(N-hebutanoylaminomethyl)cyclohexanecarboxylic acid benzyl ester (3.87 g of the compound synthesized in 3-11 was mixed with pyridine 40
After dissolving in mβ and adding hebutanoyl chloride dropwise while cooling with water, the mixture was returned to room temperature and stirred for 15 hours.

Add 100 mβ of dichloromethane, add 10% hydrochloric acid (30 m
I2x3). Saturated aqueous sodium bicarbonate solution (30 mI
2), washed successively with saturated brine (30 mi!), dried over magnesium sulfate, and then evaporated the solvent under reduced pressure.

The crude oil was recrystallized from ethyl acetate-hexane to obtain 2.83 g (yield: 79%) of colorless needle-shaped trans-4-(N-hebutanoylaminomethyl)cyclohexanecarboxylic acid benzyl ester.

(3-31 Synthesis of trans-4-(N-heptylaminomethyl)cyclohexanecarboxylic acid benzyl ester hydrochloride A 1 mol tetrahydrofuran solution of poran-tetrahydrofuran complex was added to 3rnJ2 at -20°C in a N2 stream (3
A solution of 5.4 g of the compound synthesized in -2) in tetrahydrofuran (30 mβ) was slowly added dropwise over 15 minutes.

After returning to room temperature and stirring for 30 minutes, the mixture was heated under reflux for 1.5 hours.

The reaction solution was cooled with water, and 6N hydrochloric acid was added dropwise in an amount of lomβ. After heating to drive out the generated hydrogen gas, the solvent was distilled off under reduced pressure.

50 mβ of ethyl acetate was added, washed with purified water (20 mβ x 2), dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. trans-4-(N-heptylaminomethyl) as a colorless powder by recrystallization from ethyl ether.
Cyclohexanecarboxylic acid benzyl ester hydrochloride 2.
0 g (yield 35%) was obtained.

+3-41 Synthesis of trans-4-(N-heptylaminomethyl)cyclohexanecarboxylic acid hydrochloride 1.14 g of the compound synthesized in 13-3) was dissolved in ethyl acetate l.
Dissolved in Omj2, 110 mg of palladium black,
1.5rnI2 of cyclohexene was added and the mixture was heated under reflux for 2.533 hours.

After cooling, the precipitated crystals and palladium black were collected by filtration.
The palladium black was dissolved in methanol and filtered off.

A colorless powder of trans-4- (N-
525 mg (yield: 60%) of heptylaminomethyl)cyclohexanecarboxylic acid hydrochloride was obtained.

The obtained compound was analyzed by 'H-NMR. The structure was confirmed by IR.

13-5) Synthesis of the title compound 376 mg of the compound synthesized in (3-4) and 402 mg of the compound synthesized in (1-21) were dissolved in 2 ml of dichloromethane, and 266 mg of DCC was added under water cooling.
The reaction was carried out in the same manner as above, and recrystallization from methanol yielded 70 mg of the title compound as a colorless powder (yield l
0%) was obtained.

The obtained compound was subjected to 'H-NMR. The structure was confirmed by IR.

<Example 4> 3 4 4-[trans-4'-(N-heptylaminomethyl)
cyclohexylbenzoic acid 4゜゜1 (
Synthesis of 2-methylbutyl (2-methylbutyl) phenyl ester (2-41)
642mg of the compound synthesized in 1) was added to 2r of dichloromethane.
ni! ．． Dissolved in water, add 291 mg of DCC under water cooling (
1-31, and recrystallization from methanol yielded 160 mg of the compound as a colorless powder (
A yield of 20%) was obtained.

The structure of the obtained compound was confirmed by 'H-NMR and IR.

<Example 5> Synthesis of trans-4-(N-decyl-N-methylaminomethyl)cyclohexanecarboxylic acid 4"-(2-methylbutyloxycarbonyl)-4"-biphenyl ester +5-11 trans-4-( Synthesis of cyclohexanecarboxylic acid (15.7 g of tranexamic acid was mixed with dioxane-water (2:
1) It was dissolved in 300 mI2, and under water cooling, 100 mJ2 of a 1 molar aqueous sodium hydroxide solution and a solution of 24.0 g of di-t-butyl dicarbonate in di-t-butyl dicarbonate (50 mβ) were added dropwise over 10 minutes.

After returning to room temperature and stirring for 2.5 hours, the reaction solution was heated to an external temperature of 50°C.
The solution was concentrated under reduced pressure to approximately 1/3 on an aqueous solution at ~60°C, and approximately 85 mβ of IN hydrochloric acid was added dropwise under water cooling to adjust the pH to 3-4. Extraction was carried out with ethyl acetate (80mJ2X3), and the organic layer was washed with purified water (30mI2) and saturated brine (30ml), dried over magnesium sulfate, and the solvent was distilled off under reduced pressure.The obtained crude crystals were diluted with isobrobyl ether. After washing, colorless powder trans-4 is obtained by recrystallization from ethyl acetate.
21.2 g (yield: 82%) of -(Nt-butyloxycarbonylaminomethyl)cyclohexanecarboxylic acid was obtained.

(5-2) Synthesis of trans-4-(N-t-butyloxycarbonyl-N-methylaminomethyl)cyclohexanecarboxylic acid methyl ester 4.1 g of the compound synthesized in (5-1) and 8rr of methyl iodide + J2 The solution was dissolved in DMF, and 1.9 g of 60% sodium hydride was added little by little while stirring slowly under water cooling.

After returning to room temperature and continuing stirring overnight, add 80ml of ethyl ether.
The mixture was diluted with β, and 5 ml of purified water was added dropwise while cooling with water. The organic layer was washed sequentially with purified water (20 m! -4-(N-t-butyl-N-methylaminomethyl)cyclohexanecarboxylic acid methyl ester 6.8 g (yield 10
0%) was obtained.

(5-3) Synthesis of trans-4-(N-decyl-N-methylaminomethyl)cy,chlorohexanecarboxylic acid methyl ester To 6.8 g of the compound synthesized in (5-2) was added a 4N hydrochloric acid monoacetic acid egol solution under water cooling. After adding 15+nI2 and stirring for 3715 minutes, the solvent was distilled off under reduced pressure, and it was confirmed that the irritating odor had disappeared.

The resulting crude trans-4-(N-methylaminomethyl)
DM cyclohexanecarboxylic acid methyl ester hydrochloride
2. Dissolve in F I Omβ and add triethylamine under water cooling.
2 mρ, 4.1 mI2 of decyl bromide were added. 60%
768 mg of sodium hydride was added little by little, and the mixture was heated at 80°C for 1 to 2 hours. After cooling, 80m of ethyl ether! 5 mfi of purified water was slowly added dropwise. The organic layer was purified with purified water (20 mI2). After washing successively with a saturated aqueous sodium hydrogen carbonate solution (20 mI2) and a saturated brine (20 mJ2), it was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure.

The obtained yellow oil was subjected to column chromatography using 50 g of silica gel, and ethyl acetate-hexane (
Trans-4-(N
-decyl-N-methylaminomethyl)cyclohexanecarboxylic acid methyl ester (3.2 g (yield: 61%)) was obtained.

38 {5-4) }Synthesis of 4-(N-decyl-N-methylaminomethyl)cyclohexanecarponide hydrochloride (3.2 g of the compound obtained in 5-31 was dissolved in 6N hydrochloric acid, Stir for hours.

The solvent was distilled off under reduced pressure to obtain 2.9 g (yield: 86%) of colorless powder trans-4-(N-decyl-N-methylaminomethyl)cyclohexanecarboxylic acid hydrochloride.

The obtained compound was subjected to 'H-NMR. The structure was confirmed by IR.

(5-5) Synthesis of the title compound 270 mg of the compound obtained in (5-4) and 221 mg of the compound obtained in (1-2) were dissolved in 2 mJ2 of dichloromethane, and 60 mg of DCCI and 4-pyrrolidinoviridine 1
2 mg was added and stirred at room temperature overnight. (70 mg (yield: 16%) of the title compound as a colorless powder was obtained by post-treatment in the same manner as in 1-31 and recrystallization from hexane.6 The structure of the obtained compound was confirmed by 'H-NMR and IR. did.

<Examples 6 to 9> By the above method, general formulas (I) with different alkyl chain lengths were prepared.
The compounds shown in Table 3 were synthesized, and the compounds shown in Table 3, 6 to 9, were obtained.

The structure of the obtained compound was confirmed by 'H-NMR and IR.

<Example 10> Synthesis of trans-4-(N.N-dimethylaminomethyl)cyclohexanecarboxylic acid 4"-(2-methylbutyloxy)-4°-biphenyl ester (10-11 4-(2-methylbutyloxy) Kishi)
-Synthesis of 4゜hydroxybiphenyl 1.86g of 4,4゜dihydroxybiphenyl was dissolved in 20mg of ethanol, and 617mg of potassium hydroxide was added.
and 1.31 ml of pendyl bromide were added, and the mixture was heated under reflux for 6 hours.

After cooling, the precipitated crystals were collected by filtration, dissolved again in hot acetone, and insoluble materials were filtered off.

The solvent in the acetone layer was distilled off under reduced pressure to obtain 1.37 g of 4-pendyloxy-4°-hydroxybiphenyl as a colorless powder.
(yield 50%).

4-pendyloxy-4゜-hydroxybiphenyl 31
9 mg was dissolved in DMF3mβ, 148 rn g of potassium hydroxide and 319 p-toluenesulfonic acid-2-methylbutyl ester prepared by a conventional method.
mg was added thereto, and the mixture was stirred for 4 hours while heating to 50°C. After cooling, 30 mβ of ethyl acetate was added, and the organic layer was diluted with purified water (l
OmI2X2). 1 0% hydrochloric acid (lomβ), saturated aqueous sodium bicarbonate solution (10mβ), saturated saline (3
0 mβ) and dried over magnesium sulfate.

The solvent was distilled off under reduced pressure, and recrystallization from ethanol yielded a colorless powder of 4-pendyloxy-4'-(2-
Methylbutyl biphenyl 450mg (yield 9
9%).

265 mg of 4-pendyloxy-4'-(2-methylbutyloxy)biphenyl was dissolved in 3 mβ of ethanol, 13 mg of palladium black and 0.4 mβ of chlorohexene were added, and the mixture was heated under reflux for 1 hour.

The palladium was removed by filtration, and the filtrate was concentrated to give a colorless powder of 4-(
192 mg (yield: 98%) of 2-methylbutyl-4°-hydroxybiphenyl was obtained.

(10-2) Synthesis of the title compound + 177 mg of the compound synthesized in 1-1.1 was dissolved in 3 ml of carbon tetrachloride, and 0.3 mβ of tinyl chloride and DMF were added.
One drop was added and heated under reflux for 1.5 hours. The solvent was distilled off under reduced pressure, and the solution was dissolved in 3mβ of toluene. TIO-1
2 m of pyridine for 192 mg of the compound synthesized in step 1! This was added dropwise to the solution under water cooling, and the mixture was further heated under reflux for 1 hour. After cooling, add 30rr+12 ethyl acetate and add purified water (10ml x 3).
, washed with saturated brine (10 ml!) and dried over magnesium sulfate. The crude crystals obtained by distilling off the solvent under reduced pressure were
Columnography was performed using 3 g of silica gel, and 3
% methanol-methylene chloride fraction was concentrated and recrystallized from methanol to obtain 151 mg (yield: 48%) of the title compound 42 in the form of colorless needles.

The obtained compound was subjected to 'H-NMR. The structure was confirmed by IR.

<Example 11>4-[trans-4'-(N.N-dimethylaminomethyl)cyclohexylbenzoic acid 4''
Synthesis of -(2-methylbutyloxy)phenyl ester (11-1) 4-(2-methylbutyloxy)
Synthesis of Phenol DM 400g of hydroquinone monobenzyl ether.
3.36 g of pulverized potassium hydroxide dissolved in F20m12 and 4.84 g of P-}luenesulfonic acid 2-methylbutyl ester prepared by a conventional method were added, and the mixture was stirred at room temperature for 3 hours.

Dilute with 50 m2 of ethyl acetate and add purified ice (30 mffx
2) Washed with 10% hydrochloric acid (30 mβ x 1), saturated sodium bicarbonate (30 mβ x 1), and saturated brine (30 mβ x 1), dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The obtained crude crystals were subjected to column chromatography using 55 g of silica gel, and 4.31 g of 4-(2-methylbutyloxy)phenylbenzyl ether as a colorless powder was obtained from the 2% ethyl acetate-hexane fraction (yield: 64 %
) was obtained.

4.31 g of the obtained 4-(2-methylbutyloxy)phenylbenzyl ether was mixed with 30 m of ethanol! Dissolved palladium black 2 1 6 mg and cyclohexene 8
mβ was added and the mixture was heated under reflux for 1 hour. After cooling, the palladium was filtered off, and the solvent was distilled off under reduced pressure to obtain 3.03 g of 4-(2-methylbutyloxy)phenol as a colorless oil (yield: 68
%) was obtained.

111-2) Synthesis of 4-hydroxybenzoic acid 4-(2-methylbutyloxy)phenyl ester 61 6 mg of 4-pendyloxybenzoic acid was dissolved in 10 mβ of carbon tetrachloride, and 1. Add Omβ and 1 drop of DMF,
The mixture was heated under reflux for 2.5 hours. Distill the solvent and add toluene 5
450 mg of 4-(2-methylbutyloxy)phenol dissolved in mβ in toluene-viridine (4:1) 1
It was added dropwise to 0 mβ under water cooling and further heated under reflux for 1 hour. After cooling, it was diluted with ethyl acetate (30 mj2) and purified water (l
Omj2x2). 10% hydrochloric acid (l Orr+J2)
, saturated sodium bicarbonate (10mj2) and saturated brine (10rr+12), and dried over magnesium sulfate.

The solvent was distilled off under reduced pressure and recrystallized from ethanol to obtain 4-benzyloxybenzoic acid 4°-(2-methylbutyloxy)phenyl ester 605 as colorless scales.
mg (yield 57%).

560 mg of the obtained ester was added to 5 m of ethanol.
It was dissolved in β, 28 mg of palladium black and 0.73+nI2 of cyclohexene were added, and the mixture was heated under reflux for 1 hour. The reaction solution was filtered, the solvent of the filtrate was distilled off under reduced pressure, and recrystallization from methanol yielded 430 mg of colorless needle-shaped 4-hydroxybenzoic acid 4'-(2-methylbutyloxy)phenyl ester (yield: 99%). %) was obtained.

(11-31 Synthesis of the title compound (333 mg of the compound synthesized in 1-11 and (II-2)
300mg of the compound synthesized in
The title compound 1 was obtained as colorless needles by esterification in the same manner as (10-2) using g and recrystallization from hexane.
49 mg (yield 32%) was obtained.

The obtained compound was subjected to 'H-NMR. The structure was confirmed by TR.

<Examples 12 to 15> Using the same method as in Example 5, compounds represented by the general formula (I) having an optically active group in R1 were synthesized, and the compounds shown in 12 to 15 in Table 3 were synthesized. I got it.

The structure of the obtained compound was confirmed by 'H-NMR and IR.

In addition, when the phase transition temperatures of the compounds of Examples 1 to 15 were measured, the results shown in Table 3 were obtained.

4 6 Also, the compounds of Examples 1 to 15 and Example 1.3.5
．． IR.12 intermediates. The results of 'H-NMR measurements are shown in Tables 4 and 5.

In addition, among the compounds of Examples 1 to 15, the spontaneous polarization of the compounds exhibiting chiral smectic C phase was measured, and the results are also listed in Table 3.

Spontaneous polarization was measured by the following method.

(Measurement of spontaneous polarization) After heating the compound to make it an isotropic liquid, it was injected into a 3.3 μm thick cell made of a glass plate with a transparent electrode coated with polyimide and subjected to a rubbing treatment. It gradually descended from the state of , and the chiral smectic C phase was oriented.

The temperature was further lowered from this state, and at a temperature 10°C lower than the transition temperature to the chiral smectic C phase, a triangular wave voltage application method (Miyasato et al., Japan) was applied.
ese Journal of Applied Ph.
ysics. Vol. 22, No. lO. p. L
661. (1983), the spontaneous polarization value was measured (applied voltage 30Vp-p.50Hz). (The following is a blank space) [Effects of the Invention] As exemplified above, the compound of the present invention exhibits a liquid crystal phase in a wide temperature range close to room temperature. Therefore, we can easily and inexpensively provide a new liquid crystal compound useful as a thermal writing liquid crystal element and a display liquid crystal element that apply the thermo-optic effect in a practical temperature range by being appropriately blended with other smectic liquid crystals. can do.

Claims (7)

[Claims] (1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(I
) [In the formula, R_1 is a linear or branched saturated or unsaturated hydrocarbon residue having 1 to 16 carbon atoms, and may be substituted with halogen. R_2 is hydrogen or a methyl group, R_2
3 is general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (II) In the formula, p and q each represent 0 or 1, and n represents an integer from 1 to 16. ] A tranexamic acid derivative represented by. (2) General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(III
) [In the formula, R_1 is a linear or branched saturated or unsaturated hydrocarbon residue having 1 to 16 carbon atoms, and may be substituted with halogen. R_2 is hydrogen or a methyl group. ] A compound or its salt represented by the general formula (IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(IV) [In the formula, p and q are 0 or 1, and n is 1 to Represents an integer of 16. ] The method for producing a tranexamic acid derivative according to claim (1), characterized in that a compound represented by these is reacted. (3) A liquid crystal device containing the tranexamic acid derivative according to claim (1) as at least one component. (4) General formula (V) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(V) N-alkyltranexamic acid represented by [where R_4 is an alkyl group having 3 to 16 carbon atoms]. (5) A claim characterized in that benzyl ester of tranexamic acid is reacted with an acid chloride under basic conditions to amidate it, the amide is reduced to an alkylamino group, and then the benzyl group is hydrogenolyzed ( 4) Method for producing N-alkyltranexamic acid. (6) General formula (VI) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(VI) N-methyl-N- [where R_5 is an alkyl group having 2 to 16 carbon atoms] Alkyltranexamic acid. (7) Tranexamic acid with a protected amino group is N-methylated using methyl iodide and sodium hydride, then deprotected, and then alkylated using an alkyl halide and sodium hydride. Claim (6)
A method for producing N-methyl-N-alkyltranexamic acid.