JPH0491057A - Carboxylic acid ester compound and liquid crystalline compound - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R and R' are 3-20C alkyl or alkoxy, or 3-20C halogenated alkyl; X and Y are COO, CH2O or expressed by formula II, etc.; A and B are expressed by formula III, formula IV or formula V, etc.; (m) and (n) are 0-2 with a proviso that m=nnot equal to 0). EXAMPLE:4-[4'-(1'',2'',3'',4''-tetrahydro-6''-n-decyloxy-2'-naphthoylo xy)benzoyloxy] benzoic acid-1'''-methyl heptyl ester. USE:The objective compound is a liquid crystalline compound exhibiting a smectic phase and is useful as a liquid crystalline element having quick responsibility in a wide temperature range. PREPARATION:A mixture of a compound expressed by formula VI and alkoxyalkyl is refluxed with a metallic sodium or the like to obtain a compound expressed by formula VII, and made to react with a compound expressed by formula VIII, then with a compound expressed by formula XI through intermediates expressed by formula IX and formula X to afford the compound expressed by formula I in a case of X and Y are COO; A and B are expressed by formula III and (m) and (n) are 1.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to novel carboxylic acid ester compounds and liquid crystal compounds.

TECHNICAL BACKGROUND OF THE INVENTION Display devices using liquid crystal compounds that are currently widely used are usually driven in a TN (twisted nematic) mode.

However, when this method is adopted, in order to change the displayed image, it is necessary to change the position of the molecules of the liquid crystal compound in the element, which increases the driving time and changes the position of the molecules of the liquid crystal compound. There is a problem in that the voltage required for this purpose, that is, the power consumption increases.

A switching element using a ferroelectric liquid crystal compound is TN
Unlike a switching element using mode or STN mode, the switching element can be made to function simply by changing the orientation direction of the molecules of the liquid crystal compound, so that the switching time is greatly reduced. Furthermore, the spontaneous polarization (Ps) and electric field strength (
Since the value of PsXE given by E) is the effective energy intensity for changing the orientation direction of the molecules of the liquid crystal compound, power consumption is also extremely low. Since such ferroelectric liquid crystal compounds have two stable states, or bistability, depending on the direction of the applied electric field, their switching threshold characteristics are also very good, making them useful as display devices for moving images. Particularly suitable for use.

Problems with conventional technology When using such a liquid crystal compound in an optical switching device, for example, the liquid crystal compound must have an operating temperature range near or below room temperature, a wide operating temperature range, and a high switching speed. Many characteristics are required, such as being fast (fast) and having a switching threshold voltage within an appropriate range. Among these, the operating temperature range is a particularly important characteristic when putting liquid crystal compounds into practical use.

However, in the liquid crystal compounds known so far, for example, R, B, Meyer et al.
, , paper [Journal de Physique (J, d
e Phys, ) Volume 36, page L-69, 1975,
As described in the paper by Masaaki Taguchi and Takamasa Harada [Proceedings of the 11th Liquid Crystal Conference, p. 168, 1985, ferroelectric liquid crystal compounds generally have a narrow operating temperature and a wide operating temperature range. However, the operating temperature range is a high temperature range that does not include room temperature, and a liquid crystal compound that is practically satisfactory has not been obtained.

OBJECTS OF THE INVENTION The present invention aims to provide novel carboxylic acid ester compounds.

More specifically, it is an object of the present invention to provide a carboxylic acid ester compound that is particularly useful as a liquid crystal substance.

Another object of the present invention is to provide a novel liquid crystal compound.

Summary of the Invention The carboxylic acid ester compound of the present invention has the following formula: -20 alkoxy groups and halogenated alkyl groups having 3 to 2 carbon atoms, x and Y are independently -COO-1-OCO
-1, A and B each independently represent a group selected from the group consisting of, and m and n each independently represent an integer of 0 to 2. However, m and n never become 0 at the same time.

The liquid crystal compound according to the present invention is represented by the above formula [Il.

By using such carboxylic acid ester compounds as liquid crystal compounds, various devices with excellent properties such as a wide operating temperature range, high switching speed, extremely low power consumption, and stable contrast can be manufactured. be able to.

Detailed Description of the Invention Next, the carboxylic acid ester compound of the present invention will be specifically described.

The carboxylic acid ester compound of the present invention has the following formula % formula % [1] However, in the formula [Il, R and Ro each independently represent an alkyl group having 3 to 20 carbon atoms; It represents one type of group selected from the group consisting of an alkoxy group and a halogenated alkyl group having 3 to 20 carbon atoms.

In the above formula [I], when R is an alkyl group having 3 to 20 carbon atoms, such alkyl group may be in any form of linear, branched or alicyclic form. However, the molecules of carboxylic acid esters in which R is a linear alkyl group exhibit excellent liquid crystallinity because they have a rigid structure in which the molecules extend straight. Such a linear alkyl group is preferably an alkyl group having 3 to 20 carbon atoms, and specific examples of such alkyl groups include hexyl group, heptyl group, octyl group, decyl group, and dodecyl group. group, tetradecyl group, hexadecyl group, octadecyl group, and the like.

Further, when R is a halogenated alkyl group having 3 to 20 carbon atoms, examples of the halogenated alkyl group include F
Mention may be made of groups substituted with halogen atoms such as SCQ, Br and I.

Further, when R is an alkoxy group having 3 to 20 carbon atoms, examples of such an alkoxy group include an alkoxy group having an alkyl group as described above. Specific examples of such alkoxy groups include hexoxy, heptoxy, octyloxy, decyloxy, dodecyloxy, tetradecyloxy, hebutadecyloxy, hexadecyloxy and octadecyloxy groups. can be mentioned.

When using the carboxylic acid ester compound of the present invention as a liquid crystal compound, compounds in which R in formula [I] is an alkoxy group are useful.

In addition, in the above formula [1], X and Y are each independently -COO-1-OCO
Represents a group selected from the group consisting of -1.

Among these groups, when the carboxylic acid ester compound of the present invention is used as a liquid crystal compound, in consideration of the properties as a liquid crystal composition, it represents a group selected from the following or a single bond. When this carboxylic acid ester compound is used as a liquid crystal compound, it is preferable that the molecular form of this compound has linearity. Therefore, as a liquid crystal compound, at least one of X and Y should be used. , preferably both are -0
It is desirable that it be 00-.

Further, in the above formula [1], it is preferable that A and B are each independently the following.

In addition, in formula [I], Ro has 3 to 2 carbon atoms.
It is a type of group selected from the group consisting of an alkyl group having 0 carbon atoms, an alkoxy group having 3 to 20 carbon atoms, and a halogenated alkyl group having 3 to 20 carbon atoms. Particularly when the carboxylic acid ester compound of the present invention is used as a liquid crystal compound, this Ro is a part of a hydrogen atom bonded to an alkyl group having 3 to 20 carbon atoms or a carbon atom constituting this alkyl group. is preferably an alkyl group substituted with a halogen atom, and it is particularly preferable that these alkyl groups or alkyl groups having a halogen atom have a branched form. Preferred examples of such an alkyl group or an alkyl group having a halogen atom include C2H5CF3 -CH-CaL3 and -ct+-CJ13.

In formula [1], the group represented by Ro can be introduced into formula [I] by, for example, an esterification reaction using a hydroxybenzoic acid alkyl ester. Among the hydroxybenzoic acid alkyl esters used in this ester reaction, for example, biochemically synthesized hydroxybenzoic acid alkyl esters are represented by the formula [1] because this compound has an asymmetric carbon (asymmetric carbon). The resulting liquid crystal compound exhibits optical activity. However, when such an alkyl ester compound is synthesized, for example, purely chemically, the d-isomer, which exhibits right-handed rotation, and the nine-isomer, which exhibits left-handed rotation, are produced in approximately equal proportions. By using such a hydroxybenzoic acid alkyl ester in which the d-form and the 9-form coexist in approximately the same ratio, the carboxylic acid ester compound represented by the formula [I] no longer exhibits optical rotation.
Becomes optically inactive. Therefore, in the carboxylic acid ester compound of the present invention, when Ro is a group having an asymmetric carbon, the liquid crystal compound represented by the formula [I] has d
It contains approximately the same proportions of Ro, which is the body, and Ro, which is the Q body. In order to contain the d-form and the Q-form in approximately the same proportions, for example, d-hydroxybenzoic acid alkyl ester and Q-hydroxybenzoic acid alkyl ester are prepared separately and used in a mixture of equal amounts. However, it is possible to prepare a hydroxybenzoic acid alkyl ester in which the d-form and the Q-form are mixed in almost the same proportion using a pure chemical method, and then use this hydroxybenzoic acid alkyl ester as it is. It is advantageous to adopt it.

In the above formula [T], m and n each independently represent an integer of 0 to 2. However, in the above formula [I], both m and n do not become 0 at the same time.

In particular, among these carboxylic acid ester compounds, liquid crystals of compounds in which m is 1 or 2 are particularly excellent.

Furthermore, in the above formula [I], the 1,2,3,4-tetrahydronaphthyl group includes 1234-tetrahydro-1,5-naphthyl group 1,2.
3.4-tetrahydro-1,6-naphthyl group 1,2.3
．． Mention may be made of the 4-tetrahydro-2,6-naphthyl group and the 12.3.4-tetrahydro-1,7-naphthyl group. Among these carboxylic acid ester compounds, when this ester compound is used as a liquid crystal compound, it is preferable that the entire molecule is linear,
Therefore, as a liquid crystal compound, a compound in which the tetrahydronaphthyl group is a 1.2.3.4-tetrahydro-2,6-naphthyl group is preferable.

Therefore, the carboxylic acid ester compound represented by the above formula [■] includes various compounds, but specifically, as a preferable example when using this carboxylic acid ester compound as a liquid crystal compound, the following formula Compounds represented by [1] to [16] can be mentioned.

(.-c16H33n-o\, 1=?==huge(]===
====1ゝ\COO8COO (g big 1:>Coo-C
)l(CH2) “CH.

CI+3 [1] [2] (n-Ca'+7)'Ic0O■COOGCOO-fi
H(CH2)-T-cH3H3 "3"(n-C7H,5)-0gcoTakukacoOGCOD-[
;H(C12TC)13C1+3 [4] [5] [11 pieces 13 ... [6] [12] ... [7 pieces LT'3 ... [13 pieces ■3 [8] Shir3 [14] [ 9] r3 [15] [10] r3 [16] The above carboxylic acid ester compounds can be produced by using a combination of known synthesis techniques.

For example, the above carboxylic acid ester compound can be synthesized according to the synthetic route shown below.

That is, for example, 6-n-alkoxynaphthalene-2
- Refluxing a mixture of an alkoxynaphthalenecarboxylic acid derivative such as a carboxylic acid and an alkoxyalkyl such as 1,2-ethoxyethane in the presence of metallic sodium or the like while dropping an alcohol such as inamyl alcohol. 123.4-tetrahydro-6
A naphthalenecarboxylic acid derivative in which one aromatic ring of the naphthalene ring is hydrogenated, such as -n-4-alkoxynaphthalene-2-carboxylic acid, can be obtained.

The naphthalenecarboxylic acid derivative thus obtained (i.e. 1
．． 4-N, N Reaction using an organic solvent such as '-dimethylaminopyridine and methylene chloride while dropping a solution of a halogenated hydrocarbon (e.g. methylene chloride) containing an imide compound such as N,N'-dicyclohexylcarbodiimide. According to
An ester of a naphthalenecarboxylic acid derivative and an aromatic ester compound having a hydroxyl group (for example, (4(6'-n-alkoxy-2'-naphthoyloxy)benzoic acid benzyl ester) is prepared as an example of the above compound). .

The ester obtained as above (i.e. 4(6'-n
-alkoxy-2'-naphthoyloxy)benzoic acid benzyl ester) in a polar solvent such as tetrahydrofuran and reduced using hydrogen gas in the presence of a reduction catalyst such as palladium/carbon, etc. Aromatic carboxylic acid derivatives (e.g. 4-(6°-n-alkoxy-2
°-naphthoyloxy)benzoic acid) can be obtained.

Halogenated hydrocarbons, including imide compounds such as NN'-dicyclohexylcarbodiimide, are then removed using a halogenated solvent such as methylene chloride in the presence of a petro compound such as 4-N'-dimethylaminopyridine. While dropping a solution (e.g. methylene chloride solution), an ester compound formed from e.g. hydroxybenzoic acid and an alcohol having a group corresponding to R' and an aromatic carboxylic acid derivative obtained in the above step (i.e. 4- (6°
-n-alkoxy-2°-naphthoyloxy)benzoic acid), the carboxylic acid ester compound of the present invention can be obtained.

As the alcohol having a group corresponding to R', an alcohol containing the d-isomer and the 9-isomer in approximately the same ratio is used.

Note that the above method is an example of a method for producing the carboxylic acid ester compound of the present invention, and the carboxylic acid ester compound of the present invention is not limited to this production method.

For example, among the carboxylic acid ester compounds of the present invention produced by the method described above, 4-
[1H NMR spectrum chart of 4-(1'', 2'', 3'', 4°''-tetrahydro-6°'-n-decyloxy-2''-naphthoyloxy)penzoyloxycobenzoic acid methylheptyl ester As shown in the figure.

...[2] In the above formula [2], the numbers 1 to 10 represent hydrogen atoms, and these numbers correspond to the numbers assigned to the peaks in FIG. 1. -Also, 4-(1', 2', 3°14°-tetrahydro-6°-n-decyloxy-2'-naphthoyloxy)benzoic acid methylheptyl ester represented by the following formula [6] )(-NMR
A chart of the spectrum is shown in FIG.

...[6] In the above formula [6], the numbers 1 to 10 represent hydrogen atoms, and these numbers correspond to the numbers assigned to the peaks in FIG. 2.

In addition, the following formula [4-(1°, 2°, 3'
, 4°-tetrahydro-6°-n-decyloxy-2'
A chart of the IH-NMR spectrum of -naphthoyloxy)benzoic acid trifluoromethylheptyl ester is shown in FIG.

...[14] In the above formula [14], the numbers 1 to 10 represent hydrogen atoms, and these numbers correspond to the numbers assigned to the peaks in FIG. 3.

For example, the carboxylic acid ester compound represented by formula [I] obtained as described above can be used as a raw material for synthesis of organic compounds, and can also be suitably used as a liquid crystal compound.

The carboxylic acid ester compounds of the present invention include compounds that exhibit liquid crystallinity by themselves and compounds that do not exhibit liquid crystallinity by themselves, but the above carboxylic acid ester compounds that do not exhibit liquid crystallinity exhibit other liquid crystallinity. By mixing with the compound,
It can be used as a liquid crystal composition.

Among the carboxylic acid ester compounds of the present invention, the following formula [2],
Compounds represented by [6 and [14] exhibit particularly excellent liquid crystal properties.

(n-c, oH2,)-o(near oo■COO◎CO[
)-fi:H(C)12)7C'l.

H3 [2]...[6co...[14] Among the carboxylic acid ester compounds of the present invention, formulas [2], [6] and [14] have particularly excellent properties as liquid crystals.
] Table 1 shows the phase transition temperature of the compound represented by. - In the present invention, Cry represents a crystalline phase, SmA represents a smectic A phase, and ISO represents an isotropic liquid.

Table 1 [2] 61℃ 117℃
[6] -49℃ 7
°C [14] 38 °C Among the carboxylic acid ester compounds represented by the above formula [I], as illustrated in Table 1, there are compounds that exhibit liquid crystallinity by themselves, and compounds that exhibit liquid crystallinity by themselves by mixing with other substances. There are compounds that exhibit liquid crystallinity.

Therefore, when using the carboxylic acid ester compound of the present invention as a liquid crystal compound, the carboxylic acid ester compound of the present invention can be used alone or in combination with other liquid crystal compounds. For example, the liquid crystal compound of the present invention, that is, the carboxylic acid ester compound, can be used as a main ingredient of a smectic liquid crystal composition, or as an auxiliary agent of a liquid crystal composition whose main ingredient is another liquid crystal compound exhibiting a smectic phase or a chiral smectic phase. I can do it. Furthermore, a liquid crystal composition exhibiting a chiral smectic phase can also be prepared by blending a compound exhibiting a chiral smectic phase with the liquid crystal compound of the present invention as a main agent or an auxiliary agent.

In addition, when preparing a liquid crystal composition using the liquid crystal compound of the present invention, in addition to the other liquid crystal compounds mentioned above, it is necessary to add, for example, a conductivity imparting agent and a life-enhancing agent to the usual liquid crystal composition. Additives that can be added may also be added.

By using the liquid crystal compound of the present invention in this manner, it is possible to prepare devices having excellent characteristics such as high-speed response, such as optical switching devices.

The liquid crystal compound of the present invention can be used for surface-stabilized ferroelectric liquid crystal elements,
It can be used for a helical variable strain type element, a hyper-scattering type element, a guest-host type element, a vertically aligned liquid crystal element, etc.

In addition to the above uses, the liquid crystal compound of the present invention is preferably used as a liquid crystal element such as an optical shutter or an optical switching element such as a liquid crystal printer, a piezoelectric element, or a pyroelectric element.

Effects of the Invention The present invention provides a novel carboxylic acid ester compound.

Since this novel carboxylic acid ester compound has a tetrahydronaphthalene ring, it exhibits a smectic phase and can be preferably used as a liquid crystal compound.

Furthermore, by blending the same and/or different types of liquid crystal compounds with the carboxylic acid ester compound of the present invention, the compound of the present invention can be used as a liquid crystal in a wide temperature range without impairing the liquid crystal properties of the compound of the present invention. be able to.

Therefore, by using such a liquid crystal compound or liquid crystal composition, a liquid crystal element having high-speed response over a wide temperature range can be obtained.

Furthermore, in a liquid crystal display manufactured using such a liquid crystal element, the scanning time can be significantly shortened.

Such a display can reduce power consumption and provide stable contrast.

Next, examples of the present invention will be shown, but the present invention is not limited to these examples.

Example 1 4-[4′-(1″ 2°°3°′,4″-tetrahydro-6″-n-decyloxy-2°-naphthoyloxy)benzoyloxy]benzoic acid-1″°-methyl First step of synthesis of heptyl ester 6-n-decyloxy-naphthalene-2-carboxylic acid 3
．． 86 g (11,8 mmol) and 130 ml of 1,2-jethoxyethane under nitrogen atmosphere.
While stirring at 20° C., 30 g (130 milligram atoms) of metallic sodium was added and the mixture was further heated to reflux temperature.

To this mixture, 10 g (114 mmol) of isoamyl alcohol was added dropwise over 1 hour, and the mixture was allowed to react under reflux for an additional 11 hours. After cooling to room temperature, remaining metallic sodium was decomposed by adding ethanol and ethanol, and then 20% hydrochloric acid was added to the reaction mixture to make it acidic.

After adding 100 ml of water to the reaction mixture, the organic phase was separated and further washed with water.

By concentrating the organic phase under reduced pressure, the solid 4.25
I got g. By recrystallizing this solid using toluene, 2.95 g of 1.2.3.4-tetrahydro-6-n decyloxynaphthalene-2-carboxylic acid was obtained.

2nd stage 1, 2, 3, 4-tetrahydro- obtained in the 1st stage
1.66 g (5 mmol) of 6-n-decyloxy-2-naphthalene-2-carboxylic acid and 1.14 g (5 mmol) of 4-hydroxybenzoic acid-1'-methyl-heptyl ester.
mmol) and 4-N,N-dimethylaminopyridine0
．． 2 ml of a methylene chloride solution containing 1.03 g (5 mmol) of N,N'-dicyclohexylcarbodiimide in a mixture of 12 g (1 mmol) and 2 mmol of methylene chloride.
1 was added dropwise at room temperature with stirring over 1 hour.

The mixture was further reacted at room temperature for 10 hours.

The reaction mixture was filtered and the resulting filtrate was concentrated.

By separating the concentrate using column chromatography, 4-(1', 2.3), which is a white solid, was obtained.

4′-tetrahydro-6°-n-decyloxy-2°-
Naphthoyloxy)benzoic acid benzyl ester 2.32
g (4.23 mmol) was obtained.

Third stage 4-(1', 2', 3', 4 obtained in the second stage
°-Tetrahydro-6°-n-decyloxy-2°-naphthoyloxy)benzoic acid benzyl ester 2.17 (
Hydrogen was bubbled into a mixture of 4 mmol), 1 g of 5% palladium/carbon, and 30 ml of tetrahydrofuran at room temperature and under normal pressure for 8 hours with stirring.

The reaction mixture was filtered using Celite as a filter aid,
Furthermore, the obtained filtrate was concentrated and a white solid, 4-(1
",2',3°,4°-tetrahydro-6-n-decyloxy-2'-naphthoyloxy)benzoic acid 1.59
g (3.52 mmol) was obtained.

Fourth stage: 0.45 g (] mmol) of 4-(1°, 2', 3'4'-tetrahydro-6'-n-decyloxy-2'-naphthoyloxy)benzoic acid obtained in the third stage; 4-Hydroxybenzoic acid-1°-methylheptyl ester 0.
A mixture of 21 g (1 mmol), 0.012 g (0.1 mmol) of 4-N,N-dimethylaminopyridine and 10 ml of methylene chloride contains 0.21 g (1 mmol) of N,N'-dicyclohexanecarbodiimide. 2 ml of methylene chloride solution was added dropwise over 1 hour at room temperature with stirring.

The mixture was further reacted at room temperature for 8 hours.

The reaction solution was filtered, and the resulting filtrate was concentrated. By separating the concentrated solution using column chromatography,
0.48 g of a colorless semi-solid was obtained.

The value of the FD-mass spectrum of this semi-solid is M/e
= 684.

Figure 1 shows a chart of the IH-NMR spectrum of this compound.From this result and the analysis result of the jH-NMR spectrum of this compound, this compound has the target 4-[4
-(1", 2", 3°', 4"-tetrahydro-6
It was identified as ''-n-decyloxy-2°-naphthoyloxy)benzoyloxy]benzoic acid-1°゛°-methylheptyl ester (exemplified compound [2]).

Example 2 4-(1°, 2°, 3′, 4′-tetrahydro-6-n
-Decyloxy-2'-naphthoyloxy)benzoic acid methylhebutyl ester 1,2゜3. obtained in the first step in Example 1 above.
4-tetrahydro-6-n-decyloxynaphthalene-
2-carboxylic acid 0.33 g (1 mmol) and 4-hydroxybenzoic acid methyl trifluoroheptyl ester 0
．． 30 g (1 mmol), 0.012 g (0.1 mmol) of 4-N,N-dimethylaminopyridine and 10 ml of methylene chloride was added with 0.2 g (1 2 ml of a methylene chloride solution containing 1 mmol) was added dropwise over 1 hour at room temperature with stirring.

The mixture was further reacted at room temperature for 8 hours.

The reaction mixture was filtered and the resulting filtrate was concentrated.

The concentrate was separated using column chromatography to obtain 0.53 g of a colorless semi-solid.

The value of the FD-mass spectrum of this semi-solid is M/e
= 562.

FIG. 2 shows a chart of the IH-NMR spectrum of this compound.

From this result and the analysis result of IH-NMR spectrum of this compound, this compound has the target 4-(1
It was identified as methylheptyl ester, 2', 3', 4'-tetrahydro-6'-n-decyloxy-2'-naphthoyloxy)benzoate (exemplified compound [6]).

Example 3 4-(1', 2', 3', 4-tetrahydro-6°-n
Synthesis of -decyloxy-2°-naphthoyloxy)benzoic acid trifluoromethylheptyl ester 1.2.3.4-tetrahydro-6-n-decyloxy-2-naphthalene obtained in the first step of Example 1 -2
-0.33 g (1 mmol) of carboxylic acid, 0.30 g (1 mmol) of 4-hydroxybenzoic acid trifluoromethyl-heptyl ester, and 0.012 g (0.1 mmol) of 4-N,N-dimethylaminopyridine. 21 g (1 mmol) of N,N'-dicyclohexylcarbodiimide Q in a mixture of 1 mmol) and 10 ml of methylene chloride.
2 ml of a methylene chloride solution containing the above was added dropwise over 1 hour at room temperature with stirring.

The mixture was further reacted at room temperature for 8 hours.

The reaction mixture was filtered and the resulting filtrate was concentrated.

By separating the concentrate using column chromatography, 0.58 g of a colorless viscous liquid was obtained.

The value of the FD-mass spectrum of this semi-solid is M/e=6
It was 18.

Figure 3 shows a chart of the IH-NMR spectrum of this compound.From this result and the analysis result of the jH-NMR spectrum of this compound, this compound has the target 4-(1
It was identified as trifluoromethylheptyl ester of 2', 3', 4'-tetrahydro-6'-n-decyloxy-2'-naphthoyloxy)benzoate (exemplified compound [14]).

[Brief explanation of drawings]

Figure 1 shows 4-[4'-(1°',
This is a chart of the XH-NMR spectrum of 2"3"4"-tetrahydro-6"-n-decyloxy-2"-naphthoyloxy)benzoyloxy]benzoic acid methylheptyl ester. FIG. 4-(1°12°, 3
', 4tetrahydro-6-n-decyloxy-2-naphthoyloxy)benzoic acid methylheptyl ester I
It is a chart of HNMR spectrum. Figure 3 shows 4-(1"12', 3
1 is a chart of an iH-NMR spectrum of trifluoromethylheptyl'4tetrahydro-6-n-decyloxy-2-naphthoyloxy)benzoate. Patent applicant Mitsui Petrochemical Industries Co., Ltd. Agent
Patent Attorney Shun Suzuki Partial Patent Office Procedural Amendment October 7, 1991 Commissioner Wataru Fukazawa 1990 Patent Application No. 207,084 8/1990
Patent application filed on March 3 (D) 2゜ Name of invention: Carboxylic acid ester compound and liquid crystal compound Relationship with the case of amended person Name of patent applicant: Mitsui Petrochemical Industries, Ltd. 4, Proxy address (postal code) 41) 3rd floor, Araku Building, 2-19-2 Nishigotanda, Tokyo Parts Ward [Telephone: 03 (3491) 31B1] As shown in the attached sheet (no changes to the content except for the matters stated in the phantom column of the amendment). Contents (A) The Detailed Description of the Invention column is amended as follows. (1) Add [It is a racemic mixture] after "Represented by [■]" on page 9, line 7 of the specification. (2) “3 to 20” stated in the 8th line from the bottom of page 12 of the specification
an alkyl group having 3 to 20 carbon atoms.
, preferably an alkyl group having 4 to 20 carbon atoms, and 3 to 20 carbon atoms, preferably 4 to 20 carbon atoms. (3) r4-N,N-dimethylaminopyridine J described on page 20, line 12 to line 13 of the specification is “
4-NN-dimethylaminopyridine”. (4) r4-N'- described in page 21, line 10 of the specification
"dimethylaminopyridine" is corrected to "r4-N, )l-dimethylaminopyridine". (5) The following statement shall be added after the bottom line of page 26 of the specification. In the present invention, the phase transition temperature is a value determined by thermal measurement using a DSC (differential scanning calorimeter) and phase transition temperature measurement using a polarizing microscope. or Cry-I sol
The presence or absence of crystallization was confirmed by leaving it for a maximum of 20 days. ” That’s all.

Claims (5)

[Claims] (1) Carboxylic acid ester compound characterized by being represented by the following formula [I]; ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] [However, in formula [I], R and R ' each independently represents an alkyl group having 3 to 20 carbon atoms, an alkoxy group having 3 to 20 carbon atoms, and 3 to 20 carbon atoms;
is a type of group selected from the group consisting of halogenated alkyl groups, and X and Y are each independently -COO-, -OCO
-, -CH_2CH_2-, -CH_2O-, -OCH
＿２−, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas,
There are chemical formulas, tables, etc. ▼ A group selected from the group consisting of and -S-S-, or a single bond Tables A and B are each independently ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ Mathematical formulas, chemical formulas ,
There are tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼
▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ Mathematical formulas, chemical formulas,
There are tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼
and ▲Mathematical formulas, chemical formulas, tables, etc.▼ Represents a group selected from the group consisting of, and m and n each independently represent an integer from 0 to 2 (provided that m and n are 0 at the same time) )]. (2) In the above formula [I], R' is ▲a mathematical formula, a chemical formula, a table, etc.▼, ▲a mathematical formula, a chemical formula,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
The carboxylic acid ester compound according to claim 1, wherein the carboxylic acid ester compound represents a group selected from the group consisting of: (3) A liquid crystal compound characterized by being represented by the following formula [I]; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ... [I] [However, in the formula [I], R and R' are , a type of group selected from the group consisting of an alkyl group having 3 to 20 carbon atoms, an alkoxy group having 3 to 20 carbon atoms, and a halogenated alkyl group having 3 to 20 carbon atoms, and X and Y are each independently, -COO-, -OCO
-, -CH_2CH_2-, -CH_2O-, -OCH
＿２−, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas,
There are chemical formulas, tables, etc. ▼ and -S-S- Represents a group selected from the group consisting of, or a single bond, A and B are each independently, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formula ,Chemical formula,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ Mathematical formulas,
There are chemical formulas, tables, etc. ▼ Represents a group selected from the group consisting of, and m and n each independently represent an integer from 0 to 2 (however, m and n cannot be 0 at the same time) ]. (4) In the above formula [I], R' is ▲a mathematical formula, a chemical formula, a table, etc.▼, ▲a mathematical formula, a chemical formula,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
3. The liquid crystal compound according to claim 3, wherein the liquid crystal compound represents a group selected from the group consisting of: (5) In the above formula [I], R is an alkoxy group, X is -COO-, A is a ▲ group having a numerical formula, chemical formula, table, etc. 4. The liquid crystal compound according to claim 3, wherein n is an integer of 0.