JPH0931026A - Deuterated optically active compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an optically active compound having a deuterated chemical structure and exhibiting an antiferroelectric phase. SOLUTION: This compound is an optically active compound of formula I (R<1> is a 1-18C alkyl; R<2> is a 1-10C linear alkyl; X is a single bond, -O-, -COO-, etc.; Y and Z are each single bond, -COO-; ring A, ring B, ring C are each 1,4-phenylene, trans-1,4-cyclohexylene, pyrimidine-2,5-diyl, etc.; n is 1 or 0; at least one of D<1> -D<6> is D and the others are H, * is an asymmetric carbon which has an absolute configuration of R or S), for example, (R)-4-[4-(4-octyloxyphenyl) phenylcarboxyl]benzoic acid-1-(methyl-<2> H3 )-heptyl-1,2,2-<2> H3 ) ester. The compound of formula I can be produced by carrying out the reaction of the corresponding carboxylic acid of formula II with an alcohol of formula III in the presence of a dehydrative condensing agent such as ethyl polyphosphate.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel deuterated optically active compound.

[0002]

2. Description of the Related Art Liquid crystal display devices are 1) low-voltage operable 2).
Since it has excellent features such as low power consumption, 3) thin display, and 4) light receiving type, TN method, STN method,
A guest-host method has been developed and put to practical use. However, a nematic liquid crystal that is widely used at present has a response speed of several mse.
It has a drawback as slow as c to several tens of msec, and is subject to various restrictions in application. In order to solve these problems, an STN method and an active matrix method using a thin layer transistor have been developed, but the STN type display element has excellent display quality such as display contrast and viewing angle. However, there are problems that high accuracy is required for controlling the cell gap and the tilt angle and that the response is rather slow.

Therefore, there is a demand for the development of a new liquid crystal display system having excellent responsiveness, and the optical response time is μse.
Attempts have been made to develop ferroelectric liquid crystals capable of realizing ultra-high-speed devices as short as c-orders. Ferroelectric liquid crystal was produced in 1975 by Meyer and others in DOBAMBC.
(P-decyloxybenzylidene-p-amino-2-methylbutylcinnamate) was first synthesized (Le
Journal de Physique, vol. 36, 19
75, L-69). Further, in 1980, the characteristics of display devices such as submicrosecond high-speed response of DOBAMBC and memory characteristics were reported by Clark and Lagwall, and ferroelectric liquid crystals have been receiving much attention [N. A. Clark, et al. , A
ppl. Phys. Lett. 36.899 (198
0)]. However, their method has many technical problems for practical use. Especially, there is no material showing ferroelectric liquid crystal at room temperature, and it is effective and practical for the alignment control of liquid crystal molecules which is indispensable for display. The method was not established either.
Since this report, various attempts have been made from both sides of liquid crystal materials / devices, prototype display devices utilizing switching between twisted two states have been produced, and high-speed electro-optical devices using the same have been disclosed, for example, in JP-A-56-107216. However, high contrast and proper threshold characteristics have not been obtained.

From this point of view, other switching methods have been searched and a transient scattering method has been proposed.
Then, in 1988, the present inventors reported a three-state switching method of a liquid crystal having a tristable state [A.
D. L. Chandani, T .; Hagiwara,
Y. Suzuki et al. , Japan. J. o
f Appl. Phys. , 27, (5), L729-
L732 (1988)].

The above-mentioned "having three states" means a liquid crystal electro-optical device in which a ferroelectric liquid crystal is sandwiched between a first electrode substrate and a second electrode substrate which is arranged with a predetermined gap. 1 is configured so that a voltage for forming an electric field is applied to the first and second electrode substrates, and when the voltage is applied as the triangular wave shown in FIG. 1A, the ferroelectric liquid crystal is formed as shown in FIG. 1D. However, the molecular orientation has a first stable state (in FIG. 1D) when no electric field is applied, and the second stable state in which the molecular orientation is different from the first stable state in one electric field direction when an electric field is applied. (In FIG. 1D), and further has a third molecular orientation stable state (in FIG. 1D) different from the first and second stable states with respect to the other electric field direction. The applicant of the present invention discloses a three-stable state, that is, a liquid crystal electro-optical device utilizing the three states.
No. 3-70212 and Japanese Patent Application Laid-Open No. Hei 2-15332.
Published as Issue 2.

The characteristics of the antiferroelectric liquid crystal exhibiting the tristable state will be described in more detail. Clark / Ragawell (Cla
In the surface-stabilized ferroelectric liquid crystal device proposed by rk-Lagawall, two stable liquid crystal molecules in which the ferroelectric liquid crystal molecules are uniformly aligned in one direction as shown in FIGS. 2A (a) and 2 (b) in the S * C phase. A state is shown, which is stabilized in one of the states depending on the direction of the applied electric field, and the state is maintained even when the electric field is cut off. However, in reality, the alignment state of the ferroelectric liquid crystal molecules shows a twisted two-state in which the director of the liquid crystal molecules is twisted, or the layer has a chevron structure in which the layers are bent. With the Sieblon layer structure, the switching angle becomes small, which causes low contrast, which is a major obstacle to practical use.

On the other hand, in the S * (3) phase in which the "anti" ferroelectric liquid crystal shows a tristable state, in the above liquid crystal electro-optical device,
When no electric field is applied, as shown in FIG. 2A, the molecules in each adjacent layer are tilted in opposite directions and arranged antiparallel, and the dipoles of the liquid crystal molecules cancel each other. Therefore, the spontaneous polarization is canceled in the entire liquid crystal layer. The liquid crystal phase showing this molecular arrangement corresponds to that in FIG. 1D. further,
When a voltage sufficiently higher than the threshold value of (+) or (−) is applied, the liquid crystal molecules shown in FIGS. 2B and 2C are tilted in the same direction and arranged in parallel. In this state, the dipoles of the molecules are also aligned in the same direction, so that spontaneous polarization occurs and a ferroelectric phase is formed. That is, in the S * (3) phase of the “anti” ferroelectric liquid crystal, the “anti” ferroelectric phase when there is no electric field and the two ferroelectric phases depending on the polarity of the applied electric field are stable, and the “anti” ferroelectric liquid crystal is stable. Switching between the three stable states is performed with a DC threshold value between the phase and the two ferroelectric phases. Due to the change in the liquid crystal molecule alignment accompanying this switching, the light transmittance changes with the double hysteresis shown in FIG. A memory effect can be realized by applying a bias voltage to the double hysteresis as shown in FIG. 3B and further superimposing a pulse voltage on the double hysteresis.

Further, by applying an electric field, the layer of the ferroelectric phase is stretched to form a Bookshelf structure. On the other hand, the "anti" ferroelectric phase in the third stable state has a similar bookshelf structure. Since the layer structure switching by the application of the electric field gives a dynamic shear to the liquid crystal layer, alignment defects are improved during driving, and good molecular alignment can be realized. In the "anti-" ferroelectric liquid crystal, image display is performed by using both the hysteresis on the plus side and the hysteresis on the minus side alternately, so that an afterimage phenomenon of an image due to accumulation of an internal electric field based on spontaneous polarization can be prevented.

As described above, the "anti" ferroelectric liquid crystal is
It can be said that this is a very useful liquid crystal compound capable of 1) high-speed response, 2) high contrast and a wide viewing angle, and 3) excellent alignment characteristics and a memory effect. Regarding the liquid crystal phase showing the tristable state of "anti" ferroelectric liquid crystal, 1) A.
D. L. Chandani et al., Japan
J. Appl. Phys., 28 , L-1265 (19).
89), 2) H. Orihara et al., Jap
anJ. Appl. Phys., 29 , L-333 (1
990), and the S * CA phase (AntiferroelectricSm) is associated with the "anti" ferroelectric property.
ectic C * phase). We have
This liquid crystal phase performs switching between tristable states and is defined as an S * (3) phase.

"Anti" ferroelectric phase S * (3) showing tristable state
Liquid crystal compounds having a phase sequence of are disclosed in Japanese Patent Application Laid-Open Nos. 1-331667, 1-316372,
There are JP-A-1-316339, JP-A-2-28128, and JP-A-1-213390, such as Ichihashi, and as a liquid crystal electro-optical device utilizing a tristable state, the present applicant has JP-A-2-40625. JP-A-2-153322
And Japanese Patent Application Laid-Open No. 2-173724. When applying “anti” ferroelectric liquid crystal to a liquid crystal display, it is difficult to satisfy all of 1) operating temperature range, 2) response speed, 3) spontaneous polarization, 4) hysteresis characteristics, etc. with a single liquid crystal. Usually, it is prepared as a mixed liquid crystal of more than ten kinds.

Therefore, the development of mainly antiferroelectric liquid crystal compounds having a large number of various liquid crystal characteristics has become an important subject for practical use of displays.

Deuterated liquid crystal compounds are disclosed in JP-A-6-
3129949 and Japanese Patent Laid-Open No. 7-10784 are reported. However, all of these liquid crystal compounds are non-optically active compounds and liquid crystal compounds exhibiting a nematic phase. As described above, a deuterated optically active compound that exhibits an antiferroelectric phase has not been reported yet.

[0013]

An object of the present invention is to provide a novel optically active compound having a deuterium-substituted chemical structure, which is different from the conventionally known liquid crystal compounds.

[0014]

The first aspect of the present invention is to provide the following general formula (I):

Embedded image (Wherein, R ¹ has 1 to 1 carbon atoms which may have a substituent.
8 is an alkyl group, R ² is a linear alkyl group having 1 to 10 carbon atoms, X is a single bond, —O—, —COO—,
-OCO- or -OCOO-, Y and Z are groups independently selected from the group consisting of a single bond and -COO-, and ring A, ring B and ring C are 1 or 2 fluorines. A 1,4-phenylene group which may be substituted with
Trans-1,4-cyclohexylene group, pyrimidine-
A group independently selected from the group consisting of a 2,5-diyl group, a pyridine-2,5-diyl group and a 2,6-naphthylene group, and n is an integer of 1 or 0,
D ¹ , D ² , D ³ , D ⁴ , D ⁵ and D ⁶ are at least one of these is deuterium and the rest is hydrogen, and the carbon marked with * is an asymmetric carbon, Its absolute configuration is R or S. )).

In the above formula, R ¹ is preferably a straight-chain alkyl group, more preferably having 6 to 14 carbon atoms. When n is 0, the compound represented by the general formula (I) becomes bicyclic, and the temperature range of the liquid crystal phase becomes narrower. Therefore, it is preferable that tricyclic, that is, n = 1. At least one of the linking groups Y and Z is -C.
OO- is preferred, and when the linking group Y is a single bond, at least one of ring A and ring B is 1,4.
It is preferably a -phenylene group, and when the linking group Z is a single bond, at least either ring B or ring C is preferably a 1,4-phenylene group.

The second aspect of the present invention is the following general formula (II) which is one of the important synthetic intermediates in the production of the optically active compound represented by the general formula (I).

Embedded image (In the formula, R ² is a linear alkyl group having 1 to 10 carbon atoms, ring C is a 1,4-phenylene group which may be substituted with 1 or 2 fluorines, and trans-1,4. A cyclohexylene group, a pyrimidine-2,5-diyl group, a pyridine-2,5-diyl group or a 2,6-naphthylene group, and D ¹ , D ² , D ³ , D ⁴ , D ⁵ and D ⁶ are , At least one of these is deuterium and the rest is hydrogen,
The carbon marked with is an asymmetric carbon and its absolute configuration is R or S. )).

The third aspect of the present invention relates to a liquid crystal composition comprising the optically active compound according to the first, second, third, fourth or fifth aspect.

A fourth aspect of the present invention relates to an antiferroelectric liquid crystal composition comprising the optically active compound according to any one of claims 1, 2, 3, 4 and 5.

The optically active compound represented by formula (I) of the present invention can be produced, for example, as follows.

Embedded image [In the formula, R ¹ , R ² , X, Y, Z, ring A, ring B, ring C,
n, D ¹ , D ² , D ³ , D ⁴ , D ⁵ , D ⁶ and * have the same meanings as in formula (I). ]

That is, the compound represented by the general formula (I) of the present invention is prepared by reacting the corresponding carboxylic acid represented by the general formula (III) with a dehydration condensation agent such as ethyl polyphosphate or dicyclohexylcarbodiimide. ) Or by converting the carboxylic acid represented by the general formula (III) into an acid halide and then reacting with the alcohol represented by the general formula (IV) in the presence of a base. You can

Here, the carboxylic acid represented by the general formula (III) is well known as a synthetic intermediate for liquid crystal compounds, and is easy to manufacture and obtain.

The optically active alcohol of the general formula (IV) has the general formula (IV ′)

[Chemical 6] [Wherein R ² and D ¹ , D ² , D ³ , D ⁴ , D ⁵ and D ⁶ have the same meanings as in formula (I). ] It can manufacture by carrying out the optical resolution of the racemic alcohol represented by these using an enzyme or an optical isomer separation column.

Further, a method of converting a racemic alcohol of the general formula (IV ') into an ester such as acetic acid or benzoic acid, and then optically resolving it using an enzyme or an optical isomer separation column, or a general formula (IV' It is also possible to produce the optically active alcohol of the general formula (IV) by a method such as conversion of the racemic alcohol of) to an ester such as an optically active carboxylic acid, followed by optical resolution such as recrystallization or column chromatography. it can.

As the method for producing the alcohol of the general formula (IV '), various methods can be mentioned depending on the types of D ¹ , D ² , D ³ , D ⁴ , D ⁵ and D ⁶ . For example, in the general formula (IV ′), when D ¹ is deuterium and D ² , D ³ , D ⁴ , D ⁵ and D ⁶ are hydrogen, the general formula (V)

[Chemical 7] [In the formula, R ² has the same meaning as in formula (I). ] The ketone represented by the following formula can be produced by reducing with a deuterated reducing agent such as LiAlD ₄ or NaBD ₄ .

In the general formula (IV '), when D ² , D ³ and D ⁴ are deuterium and D ¹ and D ⁵ and D ⁶ are hydrogen, the general formula (V
I)

Embedded image [In the formula, R ² has the same meaning as in formula (I), and Hal represents a chlorine, bromine, or iodine atom. A halide represented by] lithium, after the organometallic compound with magnesium, by reacting with acetaldehyde -d ₃ (CD ₃ CHO), it can be produced.

Further, methyl iodide-d ₃ (CD ₃ I) is used as an organometallic compound by using a halide such as lithium and magnesium, and then the compound of the general formula (VII) is used.

Embedded image [In the formula, R ² has the same meaning as in formula (I). ] It can manufacture by making the aldehyde represented by these react. If methyl iodide-d ₁ (CDH ₂ I) is used instead of methyl iodide-d ₃ , then the compound of general formula (IV ′)
In, a compound in which D ² is deuterium and D ¹ and D ³ , D ⁴ , D ⁵ and D ⁶ are hydrogen can be produced.

When D ¹ is hydrogen or deuterium and D ² , D ³ , D ⁴ , D ⁵ and D ⁶ are deuterium in the general formula (IV ′), the ketone represented by the general formula (V) is a base. Reacts with heavy water in the presence of

Embedded image [In the formula, R ² has the same meaning as in formula (I). ] After obtaining the ketone represented by the formula, LiAlH ₄ , Na
It can be produced by reduction with a deuterated reducing agent such as BH ₄ , LiAlD ₄ and NaBD ₄ .

Other than the above, various methods for producing the optically active compound represented by the general formula (I) include various methods depending on the types of the linking groups X, Y and Z and the rings A, B and C. For example, in the general formula (I), Z is -COO-
In this case, it can also be produced by the following method. That is, the alcohol represented by the general formula (IV ′) and the carboxylic acid represented by the following general formula (IX)

Embedded image [In the formula, ring C has the same meaning as in formula (I), and R ³ represents a hydroxyl-protecting group. ] Using a dehydration condensing agent or converting to an acid halide and then reacting in the presence of a base, the following general formula (X)

[Chemical 12] [In the formula, ring C and D ¹ , D ² , D ³ , D ⁴ , D ⁵ and D ⁶ have the same meanings as in formula (I), and R ³ represents a hydroxyl-protecting group. ] The compound shown by these is manufactured. R
Examples of the hydroxyl-protecting group represented by ³ include an arylmethyl group such as a benzyl group, a lower alkyl group such as a methyl group, a lower alkoxymethyl group such as a methoxymethyl group, an acyl group such as an acetyl group, and a lower group such as a methoxycarbonyl group. Examples thereof include an alkoxycarbonyl group and a terrahydropyranyl group.

The compound represented by the general formula (X) is optically resolved using an optical isomer separation column and then the protecting group is removed, or the protecting group is first removed and then the optical isomer separation column is used. Optical resolution is performed to produce a compound represented by the general formula (II).

The compound represented by the general formula (II) and the following general formula (XI)

Embedded image [In the formula, R ¹ , ring A, ring B, X, Y and n have the same meanings as in formula (I). ] By reacting a carboxylic acid represented by the following with a dehydration condensing agent such as dicyclohexylcarbodiimide, or a carboxylic acid (XI)
Is converted to an acid halide and then reacted with an optically active compound (II) in the presence of a base, whereby a compound in which Z is —COO— in the general formula (I) can be produced.

The carboxylic acid derivative represented by the general formula (XI) is well known as a synthetic intermediate for liquid crystal compounds and is easy to manufacture and obtain.

R ¹ , R ² and-in the compounds of the present invention
Specific examples of the (ring A-Y) n-ring BZ-ring C-are shown below, but the present invention is not limited thereto.

R ¹ is a methyl group which may have a substituent, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group,
Decyl group, undecyl group, dodecyl group, tridecyl group,
Examples include a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group and an octadecyl group. As the substituent, an alkyl group such as a methyl group, an ethyl group and a propyl group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group and a decyloxy group. Alkoxy group such as vinyl group,
Alkenyl groups such as 1-propenyl group and 1-butenyl group, alkynyl groups such as ethynyl group and 1-propynyl group, acetoxy group, ethanoyloxy group, propanoyloxy group, butanoyloxy group, pentanoyloxy group and hexa Examples thereof include an alkanoyl group such as a noyloxy group and halogen atoms such as fluorine and chlorine. However, when X is -O-, -OCO- or -OCOO-, it is preferable that the 1-position of R ¹ is not substituted with an alkoxyl group, an alkanoyl group or a halogen group.

Examples of R ¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group.

Examples of the-(ring A-Y) n-ring B-Z-ring C- are as follows. here

Embedded image The structure represented by

Embedded image Can be arbitrarily selected from the structures represented by

N is 1, Y is a single bond, and Z is --COO--.
(Ring A-Y) n-ring B-Z-ring C-

Embedded image And the like.

N is 1, Y is --COO--, and Z is a single bond-.
(Ring A-Y) n-ring B-Z-ring C-

Embedded image And the like.

N is 1, Y and Z are single bonds of-(ring A-
Y) n-ring B-Z-ring C-

Embedded image And the like.

As (-ring A-Y) n-ring B-Z-ring C- in which n is 1, Y and Z are -COO-,

Embedded image And the like.

As (-ring A-Y) n-ring B-Z-ring C- in which n is 1, Y and Z are -COO-,

Embedded image And the like.

The synthesis of Example 1 (1) 2-octanone-1,1,1,3,3 ² H ₅

[Chemical 21] Potassium t-butoxy (21.6 g, 0.19 mol)
2-octanone (12 ml,
76 mmol), benzene (22 ml) and tetrabutylammonium bromide (50 mg, 0.15 mmol) were added, and the mixture was stirred at room temperature overnight. After concentrating the organic layer, distillation (70
C./30 Torr) to obtain deuterated 2-octanone (7.2 g). This operation was repeated three times to obtain 2-octanone _{^{-1,1,1,3,3- 2 H 5 (1.9g, 18}} % yield, deuteration ratio of 97%) a.

[0042] ^{2-octanone-1,1,1,3,3-2}
Properties and physical properties of H ₅ Colorless oily substance ¹ H NMR (CDCl ₃ ) δ 0.91 (t, J = 6.7)
Hz, 3 H), 1.27 to 1.35 (m, 8 H),
1.55 to 1.68 (m, 2 H) IR (neat) 2930, 2860, 1710 cm ^-1 Mass m / z (relative intensity) 133 (M ⁺ , 7), 7
5 (10), 64 (17), 63 (97), 62 (2
1), 46 (100)

(2) 2-octanol-1,1,1,
Synthesis of 2,3,3- ² H ₆

Embedded image Lithium deuterium aluminum (0.3g, 7mmo
in diethyl ether (5ml) suspension of l) 2-octanone -1,1,1,3,3- ² H ₅ (1.9mg, 14m
A solution of (mol) in diethyl ether (2 ml) was added, and the mixture was stirred at room temperature for 12 hours. A 5% aqueous sodium hydroxide solution (3 ml) was added to the reaction solution, which was filtered through Celite, extracted with ether, and concentrated to give 2-octanol-1,1,1,2,3,3
3- ² H ₆ was obtained (crude product 1.6g, crude yield 84%).

2-octanol-1,1,1,2,3
3- ² H ₆ having properties and properties colorless oil _{^{1 H NMR (CDCl 3) δ0.90}} (t, J = 6.7
Hz, 3 H), 1.2 to 1.4 (m, 9 H) IR (neat) 3350, 2930, 2850, 22
10, 1460, 1380, 1160, 1050, 94
0 cm ^-1 Mass m / z (relative intensity) 118 (M ⁺ -H ₂ O,
3), 49 (100), 32 (15), 28 (57)

[0045] (3) 4-methoxybenzoic acid 1- (methyl - ² H ₃₎ - Synthesis of heptyl-1,2,2 ² H ₃

Embedded image 2-octanol -1,1,1,2,3,3- ² H ₆ (crude product 1.6g, 11.8mmol), 4- dimethylaminopyridine (1.4 g, 11.8 mmol) of triethylamine (10ml ) A solution of 4-methoxybenzoic acid chloride (2.0 g, 11.8 mmol) in dichloromethane (5 ml) was added to the solution, and the mixture was stirred overnight. Water was added to the reaction solution, which was extracted with dichloromethane and concentrated. The residue was subjected to silica gel column chromatography (hexane / ethyl acetate = 9).
Purification by / 1), 4-methoxybenzoic acid 1- (methyl - ² H ₃₎ - was obtained heptyl _{^{-1,2,2- 2 H 3 (2.3g, 72}} % yield). Further, the optical isomers were separated by high performance liquid chromatography (Daicel, CHIRALPAK AD. Hexane / 2-propanol = 150/1), and (R)-and (S) -4-methoxybenzoic acid 1
- (methyl - ² H ₃₎ - was obtained heptyl-1,2,2 ² H _3.

(R) -4-Methoxybenzoic acid 1-
(Methyl - ² H ₃₎ - ^{heptyl-1,2,2-2} Behavior of H ₃ and properties colorless oil [α] _D ²⁰ -37.9 ° _{(c = 1.05, CHCl 3)} 1 H NMR ( CDCl ₃ ) δ 0.87 (t, J = 7.0)
Hz, 3 H), 1.24 to 1.37 (m, 8 H),
3.85 (s, 3 H), 6.92 (d, J = 9.0 H
z, 2 H), 8.00 (d, J = 9.0 Hz, 2
H) IR (neat) 2930, 2850, 1710, 16
00, 1510, 1290, 1260, 1160, 11
00, 850, 770 cm ^-1 Mass m / z (relative intensity) 270 (M ⁺ , 13),
154 (18), 153 (61), 152 (74), 1
35 (100), 92 (17), 77 (20), 64
(10) Elemental analysis: Calculated _{C 16 H 18 D 6 O 3} : C, 71.0
7; H, 8.95%. Measured value: C, 71.14; H, 9.06% High resolution Mass: C ₁₆ H ₁₈ D ₆ O ₃ Calculated value: 2
70.2100 Found: 270.2090

(S) -4-Methoxybenzoic acid 1-
(Methyl - ² H ₃₎ - heptyl-1,2,2 ² H ₃ having properties and properties colorless oil [α] _D ²⁰ +37.1 DEG _{(c = 1.04, CHCl 3)} 1 H NMR (CDCl ₃ ) δ 0.87 (t, J = 7.0
Hz, 3 H), 1.24 to 1.37 (m, 8 H),
3.85 (s, 3 H), 6.92 (d, J = 9.0 H
z, 2 H), 8.00 (d, J = 9.0 Hz, 2
H) IR (neat) 2920, 2850, 1700, 16
00, 1510, 1290, 1250, 1160, 11
00, 1030, 840, 770 cm ^-1 Mass m / z (relative intensity) 270 (M ⁺ , 5), 1
53 (75), 152 (92), 135 (100), 9
2 (13), 77 (19) Elemental analysis: Calculated _{C 16 H 18 D 6 O 3} : C, 71.0
7; H, 8.95%. Measured value: C, 71.02; H, 9.04% High resolution Mass: C ₁₆ H ₁₈ D ₆ O ₃ Calculated value: 2
70.2100 Found: 270.2101

(4) (R) -4-hydroxybenzoic acid
1- (methyl - ² H ₃₎ - heptyl -1, 2,2
− Synthesis of ² H ₃

Embedded image (R)-4-methoxybenzoic acid 1- (methyl - ² H ₃₎
- heptyl -1,2,2- ² H ₃ (351mg, 1.3m
mol), dimethyl sulfide (0.66 ml, 9.1)
Aluminum chloride (606 mg, 4.6 mmol) was added to a dichloromethane (5 ml) solution of (mmol) at 0 ° C., and the mixture was stirred at room temperature for 3 days. 2M hydrochloric acid (15m
The l) was added, dichloromethane extract was concentrated, the residue was purified by silica gel thin layer chromatography (hexane / ethyl acetate = 9/1), (R ) 1- -4- hydroxybenzoic acid (methyl - ² H ₃₎ - heptyl -1,2,2- ² H ₃
(233 mg, yield 70%) was obtained.

(R) -4-Hydroxybenzoic acid 1-
(Methyl-^TwoH_Three) -Heptyl-1,2,2-^TwoH_ThreeProperties of
And physical properties colorless oily substance [α]_D ²⁰-36.6 ° (c = 1.07, CHCl_Three)¹ H NMR (CDCl_Three) Δ 0.87 (t, J = 6.8)
Hz, 3 H), 1.20 to 1.40 (m, 8 H),
5.60 (s, 1 H), 6.88 (d, J = 8.8 H
z, 2 H), 7.98 (d, J = 8.78 Hz, 2
H) IR (neat) 3350, 2920, 1680, 16
00, 1590, 1510, 1320, 1280, 12
30, 1160, 1100 cm^-1  Mass m / z (relative intensity) 256 (M⁺, 3), 1
40 (32), 139 (46), 138 (28), 12
1 (100), 118 (34), 65 (17) High resolution Mass: C₁₆H₁₈D₆O_ThreeCalculated as: 2
56.1944 Found: 2569.1944.

(5) (S) -4-hydroxybenzoic acid
1- (methyl - ² H ₃₎ - Synthesis of heptyl-1,2,2 ² H ₃

Embedded image (R) -4-Hydroxybenzoic acid 1- (methyl-
² H ₃₎ - heptyl-1,2,2 under the same conditions as the synthesis of ² H _3, (S) -4- methoxybenzoic acid 1- (methyl -
² H ₃₎ - heptyl -1,2,2- ² H ₃ (431mg,
Than 1.6mmol), (S) -4- hydroxy-benzoic acid 1- (methyl - ² H ₃₎ - ^{heptyl-1,2,2-2}
H ₃ (267 mg, 66% yield) was obtained.

(S) -4-Hydroxybenzoic acid 1-
(Methyl - ² H ₃₎ - heptyl-1,2,2 ² H ₃ having properties and properties colorless oil [α] _D ²⁰ +34.4 DEG _{(c = 1.42, CHCl 3)} 1 H NMR (CDCl ₃ ) δ 0.87 (t, J = 6.8)
Hz, 3 H), 1.20 to 1.40 (m, 8 H),
5.60 (s, 1 H), 6.88 (d, J = 8.8 H
z, 2 H), 7.98 (d, J = 8.78 Hz, 2
H) IR (neat) 3350, 2930, 1680, 16
00, 1590, 1510, 1320, 1280, 12
30, 1160, 1100 cm ^-1 Mass m / z (relative intensity) 256 (M ⁺ , 2), 1
40 (25), 139 (42), 138 (27), 12
1 (100), 118 (25), 93 (12), 65
(18) High resolution Mass: C ₁₆ H ₁₈ D ₆ O ₃ Calculated value: 2
56.1944 Found: 2569.1929.

(6) (R) -4- [4- (4-octyloxyphenyl) phenylcarboxy] benzoic acid 1-
(Methyl - ² H ₃₎ - Synthesis of heptyl-1,2,2 ² H ₃

[Chemical formula 26] (R)-4-hydroxybenzoic acid 1- (methyl - ² H ₃₎
- heptyl -1,2,2- ² H ₃ (201mg, 0.78
mmol), 4- (4-octyloxy) benzoic acid (2
A solution of dicyclohexylcarbodiimide (165 mg, 0.79 mmol) in dichloromethane (1 ml) was added to a solution of 55 mg, 0.78 mmol) and 4-dimethylaminopyridine (47 mg, 0.38 mmol) in dichloromethane (2 ml), and the mixture was stirred at room temperature for 2 days. . The reaction mixture was filtered through Celite, concentrated, and the residue was purified by silica gel column chromatography (hexane / ethyl acetate = 9/1) and recrystallized (hexane / ethyl acetate = 19 /).
1) and then (R) -4- [4- (4-octyloxyphenyl) phenylcarboxy] benzoic acid 1- (methyl-
² H ₃₎ - was obtained heptyl _{^{-1,2,2- 2 H 3 (279mg, 63}} % yield).

[0053] (R) -4- [4- (4- octyloxyphenyl) phenyl carboxy] benzoic acid 1 (methyl - ² H ₃₎ - heptyl-1,2,2 ² H ₃ having properties and properties colorless Powder [α] _D ²⁰ −22.7 ° (c = 1.00, CHCl ₃ ) ¹ H NMR (CDCl ₃ ) δ 0.88 (t, J = 6.9)
Hz, 3 H), 0.90 (t, J = 6.8 Hz, 3
H), 1.24 to 1.60 (m, 18 H), 1.81
(Tt, J = 6.6 and 6.9 Hz, 2 H),
4.02 (t, J = 6.6 Hz, 2 H), 7.01
(D, J = 8.8 Hz, 2 H), 7.31 (d, J =
8.8 Hz, 2 H), 7.60 (d, J = 8.8 H
z, 2 H), 7.70 (d, J = 8.6 Hz, 2
H), 8.13 (d, J = 8.8 Hz, 2 H), 8.
24 (d, J = 8.6 Hz, 2 H) IR (KBr) 2930, 2850, 1730, 171
0, 1600, 1290, 1270, 1190, 116
0, 1110, 1070, 820, 760 cm ^-1 Mass m / z (relative intensity) 564 (M ⁺ , 2), 3
10 (24), 309 (100), 197 (12) Elemental analysis: Calculated as C ₃₆ H ₄₀ D ₆ O ₅ : C, 76.5
6; H, 8.21%. Measured value: C, 76.62; H, 8.31% High resolution Mass: Calculated value as C ₃₆ H ₄₀ D ₆ O ₅ : 5
64.3719 Found: 564.3712.

[0054] Example 2 (S) -4- [4- ( 4- octyloxyphenyl) phenyl carboxy] benzoic acid 1 (methyl - ² H ₃₎ - Synthesis of heptyl-1,2,2 ² H ₃

Embedded image (R) -4- [4- (4- octyloxyphenyl) phenyl carboxy] benzoic acid 1 (methyl - ² H ₃₎ - ^{heptyl-1,2,2-2} Synthesis of H ₃ similar conditions,
(S) -4-Hydroxybenzoic acid 1- (methyl-
² H ₃₎ - heptyl -1,2,2- ² H ₃ (235mg,
0.91 mmol), (S) -4- [4- (4-octyloxyphenyl) phenylcarboxy] benzoic acid
1- (methyl - ² H ₃₎ - heptyl-1,2,2 ² H
₃ (287 mg, 56% yield) was obtained.

[0055] (S) -4- [4- (4- octyloxyphenyl) phenyl carboxy] benzoic acid 1 (methyl - ² H ₃₎ - heptyl-1,2,2 ² H ₃ having properties and properties colorless Powder [α] _D ²⁰ + 20.8 ° (c = 1.04, CHCl ₃ ) ¹ H NMR (CDCl ₃ ) δ 0.88 (t, J = 6.9)
Hz, 3 H), 0.90 (t, J = 6.8 Hz, 3
H), 1.24 to 1.60 (m, 18 H), 1.81
(Tt, J = 6.6 and 6.9 Hz, 2 H),
4.02 (t, J = 6.6 Hz, 2 H), 7.01
(D, J = 8.8 Hz, 2 H), 7.31 (d, J =
8.8 Hz, 2 H), 7.60 (d, J = 8.8 H
z, 2 H), 7.70 (d, J = 8.6 Hz, 2
H), 8.13 (d, J = 8.8 Hz, 2 H), 8.
24 (d, J = 8.6 Hz, 2 H) IR (KBr) 2930, 2850, 1730, 171
0, 1600, 1290, 1270, 1190, 116
0, 1110, 1070, 820, 760 cm ^-1 Mass m / z (relative intensity) 564 (M ⁺ , 2), 3
10 (23), 309 (100), 197 (13) Elemental analysis: Calculated as C ₃₆ H ₄₀ D ₆ O ₅ : C, 76.5
2; H, 8.34%. Measured value: C, 76.62; H, 8.31% High resolution Mass: Calculated value as C ₃₆ H ₄₀ D ₆ O ₅ : 5
64.3719 Found: 564.3701.

[0056] Synthesis of Example 3 (1) 2-octanol-1,1,1,3,3 ² H ₅

Embedded image 2-octanol -1,1,1,2,3,3- synthesis similar conditions ² H _6, 2-octanone -1,1,1,3,
_{^{3- 2 H 5 (2.0g, 16mmol}} ) of lithium aluminum hydride (0.3 g, 7.9 mmol) from 2-
Octanol-1,1,1,3,3 ² H ₅ was obtained (crude product 1.7 g, crude yield 79%).

2-Octanol-1,1,1,3,3-
Properties and physical properties of ² H ₅ Colorless oily substance ¹ H NMR (CDCl ₃ ) δ 0.88 (t, J = 6.7)
Hz, 3 H), 1.2 to 1.5 (m, 9 H), 3.7
6 (broad s, 1 H), IR (neat) 335
0, 2930, 2850, 2210, 1460, 116
0,1050 cm ^-1 Mass m / z (relative intensity) 117 (M ⁺ -H ₂ O,
2), 48 (100)

[0058] (2) 4-methoxybenzoic acid 1- (methyl - ² H ₃₎ - Synthesis of ^heptyl-2,2-2 H ₂

[Chemical 29] 4-methoxybenzoic acid 1- (methyl - ² H ₃₎ - ^{heptyl-1,2,2-2} Synthesis of H ₃ similar conditions, 2-octanol-1,1,1,3,3 ² H ₅ (crude product 1.7
g, 12.4 mmol) to 4-methoxybenzoic acid 1
- (methyl - ² H ₃₎ - ^heptyl-2,2-2 H ₂ (2.0
g, yield 60%). Further, the optical isomers were separated by high performance liquid chromatography (Daicel Corp., CHIRALPAK AD, hexane / 2-propanol = 150/1), and (R)-and (S) -4-methoxybenzoic acid 1- (methyl-). ² H ₃₎ - was obtained ^heptyl-2,2-2 H _2.

[0059] (R) 1--4-methoxybenzoic acid (methyl - ² H ₃₎ - ^heptyl-2,2-2 H ₂ having properties and properties colorless oil [α] _D ²⁰ -39.4 ° (c = 1.02, CHCl ₃ ) ¹ H NMR (CDCl ₃ ) δ0.87 (t, J = 7.0)
Hz, 3 H), 1.22 to 1.43 (m, 8 H),
3.86 (s, 3 H), 5.10 (broad s, 1
H), 6.92 (d, J = 9.0 Hz, 2 H),
8.00 (d, J = 9.0 Hz, 2 H) IR (neat) 2930, 2850, 1700, 16
00, 1510, 1280, 1260, 1160, 11
00, 1030, 850, 770 cm ^-1 Mass m / z (relative intensity) 269 (M ⁺ , 22),
154 (19), 153 (58), 152 (74), 1
36 (12), 135 (100), 92 (13), 77
(15), 43 (20), 41 (19) Elemental analysis: Calculated _{C 16 H 19 D 5 O 3} : C, 71.3
4; H, 8.98%. Measured value: C, 71.50; H, 9.11% High resolution Mass: C ₁₆ H ₁₉ D ₅ O ₃ Calculated value: 2
69.2037 Found: 269.2025.

[0060] (S) 1--4-methoxybenzoic acid (methyl - ² H ₃₎ - ^heptyl-2,2-2 Behavior of H ₂ and properties colorless oil [α] _D ²⁰ +38.8 DEG (c = 1.29, CHCl ₃ ) ¹ H NMR (CDCl ₃ ) δ 0.87 (t, J = 7.0)
Hz, 3 H), 1.22 to 1.43 (m, 8 H),
3.86 (s, 3 H), 5.10 (broad s, 1
H), 6.92 (d, J = 9.0 Hz, 2 H),
8.00 (d, J = 9.0 Hz, 2 H) IR (neat) 2930, 2850, 1700, 16
00, 1510, 1280, 1260, 1160, 11
00, 1030, 840, 770 cm ^-1 Mass m / z (relative intensity) 270 (M ⁺ +1,1
1), 269 (M ⁺ , 27), 154 (19), 153
(52), 152 (68), 136 (12), 135
(100), 92 (11), 77 (13), 43 (1
5), 41 (14) Elemental analysis: Calculated _{C 16 H 19 D 5 O 3} : C, 71.3
4; H, 8.98%. Measured value: C, 71.36; H, 9.09% High resolution Mass: C ₁₆ H ₁₉ D ₅ O ₃ Calculated value: 2
69.2037 Found: 269.2046.

(3) (R) -4-hydroxybenzoic acid
1- (methyl - ² H ₃₎ - Synthesis of ^heptyl-2,2-2 H ₂

Embedded image (R) -4-Hydroxybenzoic acid 1- (methyl-
² H ₃₎ - heptyl-1,2,2 under the same conditions as the synthesis of ² H _3, (R) -4- methoxybenzoic acid 1- (methyl -
² H ₃₎ - heptyl -2,2- _² H ² (298mg, 1.1
mmol), (R) -4-hydroxybenzoic acid 1
- (methyl - ² H ₃₎ - ^heptyl-2,2-2 H ₂ (173
mg, yield 62%) was obtained.

(R) -4-Hydroxybenzoic acid 1-
(Methyl-^TwoH_Three) -Heptyl-2,2-^TwoH_TwoProperties and things
Colorless oily substance [α]_D ²⁰-39.3 ° (c = 1.03, CHCl 3_Three)¹ H NMR (CDCl_Three) Δ 0.87 (t, J = 7.0)
Hz, 3 H), 1.24 to 1.42 (m, 8 H),
5.10 (broad s, 1 H), 5.58 (s, 1
 H), 6.87 (d, J = 8.8 Hz, 2 H),
7.94 (d, J = 8.8 Hz, 2 H) IR (neat) 3350, 2930, 2850, 16
80, 1600, 1590, 1510, 1440, 13
50, 1310, 1280, 1230, 1160, 11
00, 1010, 850, 770, 700, 610 cm
^-1  Mass m / z (relative intensity) 255 (M⁺, 2), 1
40 (21), 139 (40), 138 (27), 12
2 (11), 121 (100), 117 (21), 93
(12), 65 (17) High resolution Mass: C_FifteenH₁₇D_FiveO_ThreeCalculated as: 2
55.1881 Found: 255.1862

(4) (S) -4-hydroxybenzoic acid
1- (methyl - ² H ₃₎ - Synthesis of ^heptyl-2,2-2 H ₂

[Chemical 31] (R) -4-Hydroxybenzoic acid 1- (methyl-
² H ₃₎ - heptyl-1,2,2 under the same conditions as the synthesis of ² H _3, (S) -4- methoxybenzoic acid 1- (methyl -
² H ₃₎ - heptyl -2,2- _² H ² (325mg, 1.2
mmol), (S) -4-hydroxybenzoic acid 1
- (methyl - ² H ₃₎ - ^heptyl-2,2-2 H ₂ (193
mg, yield 63%).

(S) -4-Hydroxybenzoic acid 1-
(Methyl - ² H ₃₎ - ^heptyl-2,2-2 H ₂ having properties and properties colorless oil [α] _D ²⁰ +34.6 DEG _{(c = 1.09, CHCl 3)} 1 H NMR (CDCl 3) δ 0.87 (t, J = 7.0
Hz, 3 H), 1.24 to 1.42 (m, 8 H),
5.10 (broad s, 1 H), 5.58 (s, 1
H), 6.87 (d, J = 8.8 Hz, 2 H),
7.94 (d, J = 8.8 Hz, 2 H) IR (neat) 3350, 2930, 2850, 16
80, 1600, 1590, 1510, 1440, 13
50, 1310, 1280, 1230, 1160, 11
00, 1010, 850, 770, 700, 610 cm
^-1 Mass m / z (relative intensity) 255 (M ⁺ , 2), 1
40 (21), 139 (41), 138 (26), 12
2 (11), 121 (100), 117 (20), 93
(12), 65 (17) High resolution Mass: C ₁₅ H ₁₇ D ₅ O ₃ Calculated value: 2
55.1881 Found: 255.1873

(5) (R) -4- [4- (4-octyloxyphenyl) phenylcarboxy] benzoic acid 1-
(Methyl - ² H ₃₎ - Synthesis of ^heptyl-2,2-2 H ₂

Embedded image (R) -4- [4- (4- octyloxyphenyl) phenyl carboxy] benzoic acid 1 (methyl - ² H ₃₎ - ^{heptyl-1,2,2-2} Synthesis of H ₃ similar conditions,
(R) -4-Hydroxybenzoic acid 1- (methyl-
² H ₃₎ - heptyl -2,2- _² H ² (156mg, 0.6
1 mmol), (R) -4- [4- (4-octyloxyphenyl) phenylcarboxy] benzoic acid 1-
(Methyl - ² H ₃₎ - ^heptyl-2,2-2 H ₂ (177m
g, yield 52%).

[0066] (R) -4- [4- (4- octyloxyphenyl) phenyl carboxy] benzoic acid 1 (methyl - ² H ₃₎ - ^heptyl-2,2-2 H ₂ Properties and Physical Properties colorless powder [ α] _D ²⁰ −21.0 ° (c = 0.59, CHCl ₃ ) ¹ H NMR (CDCl ₃ ) δ 0.88 (t, J = 6.9
Hz, 3 H), 0.90 (t, J = 6.8 Hz, 3
H), 1.24 to 1.60 (m, 18 H), 1.81
(Tt, J = 6.6 and 6.9 Hz, 2 H),
4.02 (t, J = 6.6 Hz, 2 H), 5.14
(Broad s, 1 H), 7.01 (d, J = 8.8).
Hz, 2 H), 7.31 (d, J = 8.8 Hz, 2
H), 7.61 (d, J = 8.8 Hz, 2 H), 7.
70 (d, J = 8.6 Hz, 2 H), 8.12 (d,
J = 8.8 Hz, 2 H), 8.23 (d, J = 8.6
Hz, 2 H) IR (KBr) 2930, 2850, 1730, 171
0, 1600, 1520, 1500, 1460, 135
0, 1270, 1190, 1160, 1110, 107
0, 1010, 890, 820, 760, 690 cm ^-1 Mass m / z (relative intensity) 563 (M ⁺ , 4), 3
10 (23), 309 (100), 197 (11) Elemental analysis: Calculated as C ₃₆ H ₄₁ D ₅ O ₅ : C, 76.6
9; H, 8.22%. Actual value: C, 76.82; H, 8.39% High resolution Mass: Calculated value as C ₃₆ H ₄₁ D ₅ O ₅ : 5
63.365 Found: 563.3667.

[0067] Example 4 (S) -4- [4- ( 4- octyloxyphenyl) phenyl carboxy] benzoic acid 1 (methyl - ² H ₃₎ - Synthesis of ^heptyl-2,2-2 H ₂

[Chemical 33] (R) -4- [4- (4- octyloxyphenyl) phenyl carboxy] benzoic acid 1 (methyl - ² H ₃₎ - ^{heptyl-1,2,2-2} Synthesis of H ₃ similar conditions,
(S) -4-Hydroxybenzoic acid 1- (methyl-
² H ₃₎ - heptyl -2,2- _² H ² (172mg, 0.6
7 mmol), (S) -4- [4- (4-octyloxyphenyl) phenylcarboxy] benzoic acid 1-
(Methyl - ² H ₃₎ - ^heptyl-2,2-2 H ₂ (240 m
g, yield 64%).

[0068] (S) -4- [4- (4- octyloxyphenyl) phenyl carboxy] benzoic acid 1 (methyl - ² H ₃₎ - ^heptyl-2,2-2 H ₂ Properties and Physical Properties colorless powder [ α] _D ²⁰ + 29.0 ° (c = 1.00, CHCl ₃ ) ¹ H NMR (CDCl ₃ ) δ 0.88 (t, J = 6.9
Hz, 3 H), 0.90 (t, J = 6.8 Hz, 3
H), 1.24 to 1.60 (m, 18 H), 1.81
(Tt, J = 6.6 and 6.9 Hz, 2 H),
4.02 (t, J = 6.6 Hz, 2 H), 5.14
(Broad s, 1 H), 7.01 (d, J = 8.8).
Hz, 2 H), 7.31 (d, J = 8.8 Hz, 2
H), 7.61 (d, J = 8.8 Hz, 2 H), 7.
70 (d, J = 8.6 Hz, 2 H), 8.12 (d,
J = 8.8 Hz, 2 H), 8.23 (d, J = 8.6
Hz, 2 H) IR (KBr) 2930, 2850, 1730, 171
0, 1600, 1520, 1500, 1460, 135
0, 1270, 1190, 1160, 1110, 107
0, 1010, 890, 820, 760, 690 cm ^-1 Mass m / z (relative intensity) 563 (M ⁺ , 3), 3
10 (23), 309 (100), 197 (11) Elemental analysis: Calculated as C ₃₆ H ₄₁ D ₅ O ₅ : C, 76.6
9; H, 8.22%. Actual value: C, 76.84; H, 8.34% High resolution Mass: C ₃₆ H ₄₁ D ₅ O ₅ Calculated value: 5
63.3657 Found: 5633664.

[0069] Example 5 (1) ^{2-octanol-2-2} H Synthesis of

Embedded image 2-octanol -1,1,1,2,3,3- synthesis similar conditions ² H _6, 2- octanone (2.0 g, 16m
mol) lithium aluminum deuteride (0.3 g,
From 7.7 mmol), ^{2-octanol-2-2} H
(1.8 g of crude product, 86% crude yield) was obtained.

Properties and Properties of ² -Octanol-2-2H Colorless oily substance ¹ H NMR (CDCl ₃ ) δ0.88 (t, J = 6.7)
Hz, 3 H), 1.17 (s, 3 H), 1.2-1.
5 (m, 11H) IR (neat) 3350, 2930, 2850, 14
60, 1370, 1200, 1140, 940 cm ^-1 Mass m / z (relative intensity) 116 (M ⁺ -Me,
5), 133 (M ⁺ -H ₂ O, 5), 98 (10), 56
(15), 55 (12), 48 (100), 41 (1
3)

[0071] (2) 4-methoxybenzoic acid ^{1-methylheptyl-1-2} H Synthesis of

Embedded image 4-methoxybenzoic acid 1- (methyl - ² H ₃₎ - ^{heptyl-1,2,2-2} synthesis and under similar conditions of H _3, ^{2-octanol-2-2} H (crude product 1.7 g, 12.7 mm
From ol) 4-methoxybenzoic acid 1-methylheptyl -1- ² H (2.5g, 74% yield). further,
High performance liquid chromatography (Daicel, CHIRA)
LPAK AD. Hexane / 2-propanol = 150
/) And the optical isomers are separated, and (R)-and (S)-
4-methoxybenzoate ^{1-methylheptyl-1-2} H
I got

Properties and physical properties of (R) -4-methoxybenzoic acid 1-methylheptyl- ^1-2 H Colorless oily substance [α] _D ²⁰ -39.1 ° (c = 1.51, CHCl ₃ ) ¹ H NMR (CDCl ₃ ) δ 0.87 (t, J = 7.0
Hz, 3 H), 1.30 (s, 3 H), 1.22
1.44 (m, 8 H), 1.54 to 1.62 (m, 1
H), 1.66 to 1.76 (m, 1 H), 6.92
(D, J = 9.0 Hz, 2 H), 8.00 (d, J =
9.0 Hz, 2 H) IR (neat) 2930, 2850, 1710, 16
00, 1510, 1290, 1260, 1170, 11
00, 1030, 850, 770 cm ^-1 Mass m / z (relative intensity) 265 (M ⁺ , 4), 1
53 (26), 152 (100), 135 (73), 7
7 (12), 41 (10) High resolution Mass: C ₁₆ H ₂₃ DO ₃ Calculated value: 26
5.1786, measured value: 265.1783

[0073] (S)-4-methoxybenzoic acid ^{1-methylheptyl-1-2} H having properties and properties colorless oil ^{_{[α] D 20 + 39.4 °}} (c = 1.38, CHCl 3) 1 H NMR (CDCl ₃ ) δ 0.87 (t, J = 7.0
Hz, 3 H), 1.30 (s, 3 H), 1.22
1.44 (m, 8 H), 1.54 to 1.62 (m, 1
H), 1.66 to 1.76 (m, 1 H), 6.92
(D, J = 9.0 Hz, 2 H), 8.00 (d, J =
9.0 Hz, 2 H) IR (neat) 2930, 2850, 1710, 16
00, 1510, 1290, 1260, 1170, 11
00, 1030, 850, 770 cm ^-1 Mass m / z (relative intensity) 265 (M ⁺ , 4), 1
53 (25), 152 (100), 135 (69), 7
7 (11) Elemental analysis: Calculated as C ₁₆ H ₂₃ DO ₃ : C, 72.4
2; H, 9.12% Actual value: C, 71.54; H, 8.89% High resolution Mass: C ₁₆ H ₂₃ DO ₃ Calculated value: 26
5.1786, measured value: 265.1775

(3) (R) -4-hydroxybenzoic acid
Synthesis of ^{1-methyl-heptyl-1-2} H

Embedded image (R) -4-Hydroxybenzoic acid 1- (methyl-
² H ₃₎ - heptyl-1,2,2 ² H ₃ Synthesis and similar conditions, from (R)-4-methoxybenzoic acid 1-methylheptyl -1- ² H (388mg, 1.5mmol) ,
(R)-4-hydroxyformamide acid 1-methylheptyl -1- ² H (212mg, 58% yield).

[0075] (R)-4-hydroxybenzoic acid ^{1-methylheptyl-1-2} H having properties and properties colorless oil [α] _D ²⁰ -37.6 ° _{(c = 0.80, CHCl 3)} 1 H NMR (CDCl ₃ ) δ 0.87 (t, J = 7.0
Hz, 3 H), 1.31 (s, 3 H), 1.22
1.44 (m, 8 H), 1.51 to 1.62 (m, 1
H), 1.67 to 1.76 (m, 1 H), 5.71
(S, 1H) 6.86 (d, J = 8.8 Hz, 2 H), 7.95
(D, J = 8.8 Hz, 2 H) IR (neat) 3350, 2930, 2860, 16
80, 1600, 1510, 1440, 1320, 12
80, 1230, 1160, 1120, 1100, 85
0,770 cm ^-1 Mass m / z (relative intensity) 251 (M ⁺ , 2), 1
39 (49), 138 (50), 121 (100), 1
13 (23), 93 (12), 71 (10), 70 (1
1), 65 (17), 56 (11), 43 (13), 4
1 (16), 39 (13) High resolution Mass: C ₁₅ H ₁₇ D ₅ O ₃ Calculated value: 2
51.1630 Found: 251.1647.

(4) (S) -4-hydroxybenzoic acid
Synthesis of ^{1-methyl-heptyl-1-2} H

Embedded image (R) -4-Hydroxybenzoic acid 1- (methyl-
² H ₃₎ - heptyl-1,2,2 ² H ₃ Synthesis and similar conditions, from (S)-4-methoxybenzoic acid 1-methylheptyl -1- ² H (380mg, 1.4mmol) ,
(S)-4-hydroxyformamide acid 1-methylheptyl -1- ² H (212mg, 59% yield).

[0077] (S)-4-hydroxybenzoic acid ^{1-methylheptyl-1-2} H having properties and properties colorless oil [α] _D ²⁰ +39.2 DEG _{(c = 0.79, CHCl 3)} 1 H NMR (CDCl ₃ ) δ 0.87 (t, J = 7.0
Hz, 3 H), 1.31 (s, 3 H), 1.22
1.44 (m, 8 H), 1.51 to 1.62 (m, 1
H), 1.67 to 1.76 (m, 1 H), 5.71
(S, 1 H), 6.86 (d, J = 8.8 Hz, 2
H), 7.95 (d, J = 8.8 Hz, 2 H), IR
(Neat) 3350, 2930, 2860, 168
0, 1600, 1510, 1440, 1320, 128
0, 1230, 1160, 1120, 1100, 85
0,770 cm ^-1 Mass m / z (relative intensity) 251 (M ⁺ , 2), 1
39 (48), 138 (50), 121 (100), 1
13 (23), 93 (11), 71 (12), 70 (1
4), 65 (15), 57 (10), 56 (13), 4
3 (49), 41 (14), 39 (11) High resolution Mass: C ₁₅ H ₁₇ D ₅ O ₃ Calculated value: 2
51.1630, found: 251.1628,

(5) (R) -4- [4- (4-octyloxyphenyl) phenylcarboxy] benzoic acid 1-
Synthesis of methyl ^heptyl-1-2 H

Embedded image (R)-4-[4- (4-octyloxy phenyl) phenyl carboxy] benzoic acid 1 (methyl - ² H ₃₎ -
Synthesis and similar conditions of heptyl-1,2,2 ² H _3,
(R)-4-hydroxybenzoic acid 1-methylheptyl -1- ² H (181mg, 0.72mmol) from,
(R) -4- [4- (4-octyloxyphenyl) phenylcarboxy] benzoic acid 1-methylheptyl-1
- was obtained ² H (233mg, 58% yield).

[0079] (R)-4-[4- (4-octyloxy phenyl) phenyl carboxy] properties of benzoic acid ^{1-methylheptyl-1-2} H and properties colorless powder [α] _D ²⁰ -21.2 ° ( c = 0.58, CHCl ₃ ) ¹ H NMR (CDCl ₃ ) δ 0.88 (t, J = 6.9
Hz, 3 H), 0.90 (t, J = 6.8 Hz, 3
H), 1.34 (s, 3 H), 1.22 to 1.54
(M, 18 H), 1.56 to 1.64 (m, 1 H),
1.16 to 1.77 (m, 1 H), 1.81 (tt,
J = 6.6 and 6.9 Hz, 2 H), 4.02
(T, J = 6.6 Hz, 2 H), 5.14 (broa
ds, 1 H), 7.01 (d, J = 8.8 Hz, 2
H), 7.31 (d, J = 8.8 Hz, 2 H), 7.
60 (d, J = 8.8 Hz, 2 H), 7.70 (d,
J = 8.6 Hz, 2 H), 8.13 (d, J = 8.8)
Hz, 2 H), 8.23 (d, J = 8.6 Hz, 2
H) IR (KBr) 2940, 2850, 1730, 171
0, 1600, 1310, 1290, 1270, 119
0, 1160, 1110, 1070, 820, 760c
m ^-1 Mass m / z (relative intensity) 559 (M ⁺ , 4), 3
10 (23), 309 (100), 197 (11), 4
3 (14), 41 (11) Elemental analysis: Calculated as C ₃₆ H ₄₅ DO ₅ : C, 77.2
5; H, 8.28%, measured value: C, 77.00; H, 8.48%, high resolution Mass: C ₃₆ H ₄₅ DO ₅ calculated value: 55
9.3404, measured value: 559.3401.

Example 6 1-methylheptyl-1 (S) -4- [4- (4-octyloxyphenyl) phenylcarboxy] benzoate
- ² H Synthesis of

Embedded image (R)-4-[4- (4-octyloxy phenyl) phenyl carboxy] benzoic acid 1 (methyl - ² H ₃₎ -
Synthesis and similar conditions of heptyl-1,2,2 ² H _3,
(S)-4-hydroxybenzoic acid 1-methylheptyl -1- ² H (202mg, 0.8mmol) from,
(S) -4- [4- (4-octyloxyphenyl) phenylcarboxy] benzoic acid 1-methylheptyl-1
- was obtained ² H (336mg, 75% yield).

[0081] (S)-4-[4- (4-octyloxy phenyl) phenyl carboxy] properties of benzoic acid ^{1-methylheptyl-1-2} H and properties colorless powder [α] _D ²⁰ +22.4 DEG (c = 0.90, CHCl ₃ ) ¹ H NMR (CDCl ₃ ) δ 0.88 (t, J = 6.9
Hz, 3 H), 0.90 (t, J = 6.8 Hz, 3
H), 1.34 (s, 3 H), 1.22 to 1.54
(M, 18 H), 1.56 to 1.64 (m, 1 H),
1.16 to 1.77 (m, 1 H), 1.81 (tt,
J = 6.6 and 6.9 Hz, 2 H), 4.02
(T, J = 6.6 Hz, 2 H), 5.14 (broa
ds, 1 H), 7.01 (d, J = 8.8 Hz, 2
H), 7.31 (d, J = 8.8 Hz, 2 H), 7.
60 (d, J = 8.8 Hz, 2 H), 7.70 (d,
J = 8.6 Hz, 2 H), 8.13 (d, J = 8.8)
Hz, 2 H), 8.23 (d, J = 8.6 Hz, 2
H) IR (KBr) 2940, 2850, 1730, 171
0, 1600, 1310, 1290, 1270, 119
0, 1160, 1110, 1070, 820, 760c
m ^-1 Mass m / z (relative intensity) 559 (M ⁺ , 4), 3
10 (23), 309 (100), 197 (10), 4
3 (11) Elemental analysis: Calculated as C ₃₆ H ₄₅ DO ₅ : C, 77.2
5; H, 8.28%, measured value: C, 77.32; H, 8.36%, high resolution Mass: C ₃₆ H ₄₅ DO ₅ calculated value: 55
9.3404, measured value: 559.3400.

The optically active compounds of Examples 1, 3, and 6 were injected into a cell having a thickness of 2 μm and made of glass with a transparent electrode which was coated with polyimide and rubbed, and the phase transition temperature was observed by a polarization microscope with a hot stage. Are as shown in Table 1 (the upper row shows the phase transition temperature observed when the temperature is raised, and the lower row shows the phase transition temperature observed when the temperature is lowered).

[0083]

[Table 1]

Example 7 A liquid crystal cell having a cell thickness of 2.0 μm having a rubbing-treated polyimide alignment film on an ITO electrode substrate was added to the liquid crystal compound (R) -4- [4- (4- Octyloxyphenyl) phenylcarboxy] benzoic acid 1-
(Methyl - ² H ₃₎ - heptyl-1,2,2 ² H ₃ the Is
A liquid crystal thin film cell was prepared by filling in the tropic phase. The prepared liquid crystal cell is placed in a polarizing microscope with a photomultiplier in which two polarizing plates are orthogonal to each other so as to have a dark field at a voltage of 0V. This liquid crystal cell is
Gradually cool to the SA phase with a temperature gradient of 1 to 1.0 ° C./1 minute. After further cooling, a triangular wave voltage of ± 40 V and 1 Hz shown in FIG. 4A is applied in the temperature range of 117 ° C. to 35 ° C. A hysteresis as shown in FIG. 4B was obtained from the relationship between the applied voltage and the transmittance at 80 ° C. 0
The dark state is maintained from V → + V _3, and the bright state is obtained after a steep rise at + V ₃ . + 40V → + V to ₄ keeps the bright state, suddenly become a dark state at + V _4. Keeping the dark state to 0V → -V _3, it becomes bright state after a steep rising at -V _3. −
40V → -V up to ₄ keeps the bright state, become suddenly dark state at -V _4. When the applied voltage was changed from + 40V to −40V, it was observed that the state was changed to three states of bright → dark → bright with switching, and it was confirmed that there are three stable alignment states of liquid crystal molecules. .

Example 8 A liquid crystal cell having a cell thickness of 2.0 μm having a rubbing-treated polyimide alignment film on an ITO electrode substrate was added to the liquid crystal compound (R) -4- [4- (4- Octyloxyphenyl) phenylcarboxy] benzoic acid 1-
(Methyl - ² H ₃₎ - Isot ^heptyl-2,2-2 H ₂
A liquid crystal thin film cell was prepared by filling in the ropic phase. The prepared liquid crystal cell is placed in a polarizing microscope with a photomultiplier in which two polarizing plates are orthogonal to each other so as to have a dark field at a voltage of 0V. This liquid crystal cell is
Gradually cool to SA phase with a temperature gradient of ˜1.0 ° C./1 min. After further cooling, a triangular wave voltage of ± 40 V and 1 Hz shown in FIG. 4A is applied in the temperature range of 117 ° C. to 40 ° C. A hysteresis as shown in FIG. 4C was obtained from the relationship between the applied voltage and the transmittance at 80 ° C. 0V
→ + to V ₃ keeps the dark state, the bright state after a steep rising at + V _3. Keep the bright state from + 40V to + V ₄ ,
A sudden dark state occurs at + V ₄ . Keeping the dark state to 0V → -V _3, it becomes bright state after a steep rising at -V _3. -40
The bright state is maintained from V → −V ₄ , and the dark state is rapidly changed at −V ₄ . When the applied voltage changes from + 40V to -40V,
It was observed that the state changed to three states of bright → dark → bright accompanied by switching, and it was confirmed that there are three stable alignment states of liquid crystal molecules.

Example 9 A liquid crystal cell having a cell thickness of 2.0 μm having a rubbing-treated polyimide alignment film on an ITO electrode substrate was added to the liquid crystal compound (R) -4- [4- (4- the octyloxyphenyl) phenyl carboxy] benzoic acid ^{1-methylheptyl-1-2} H was charged in Isotropic phase to prepare a liquid crystal thin film cell. The prepared liquid crystal cell is placed in a polarizing microscope with a photomultiplier in which two polarizing plates are orthogonal to each other so as to have a dark field at a voltage of 0V. This liquid crystal cell is gradually cooled to the SA phase with a temperature gradient of 0.1 to 1.0 ° C./1 minute. Further cooling, in the temperature range of 118 ℃ ~ 38 ℃, Figure 4 (a)
The triangular wave voltage of ± 40 V and 1 Hz shown in is applied. 80
A hysteresis as shown in FIG. 4D was obtained from the relationship between the applied voltage and the transmittance at ° C. 0V → + to V ₃ keeps the dark state, the bright state after a steep rising at + V _3. +4
0V → + V to ₄ keeps the bright state, suddenly become a dark state at + V _4. Keeping the dark state to 0V → -V _3, it becomes bright state after a steep rising at -V _3. -40V → -V up to ₄ keeps the bright state, it becomes suddenly dark state at -V _4. Applied voltage is +
When changing from 40V to -40V, it was observed that there were three states of bright → dark → bright with switching, and it was confirmed that there are three stable alignment states of liquid crystal molecules.

[0087]

[Effect] The present invention can provide a novel deuterated optically active compound and a novel liquid crystal using the same.

[Brief description of drawings]

FIG. 1A shows optical response characteristics of an applied triangular wave, B is a commercially available nematic liquid crystal, C is a two-state liquid crystal, and D is a three-state liquid crystal.

FIG. 2 shows (a), (b) and (c) three stable alignment states of liquid crystal molecules when no electric field is applied.

FIG. 3 is a graph showing hysteresis of tristable liquid crystal, in which the horizontal axis represents applied voltage and the vertical axis represents transmittance (%).

FIG. 4A shows a triangular wave voltage of ± 40 V 1 Hz. (B) is a liquid crystal thin film cell prepared in Example 7
Shows hysteresis at ° C. (C) shows the hysteresis at 80 ° C. of the liquid crystal thin film cell prepared in Example 8. (D) is 8 of the liquid crystal thin film cell prepared in Example 9.
Shows hysteresis at 0 ° C.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location C09K 19/20 9279-4H C09K 19/20 19/30 9279-4H 19/30 19/34 9279-4H 19 / 34 G02F 1/13 500 G02F 1/13 500 // C07M 5:00 7:00 (72) Inventor Tetsuo Kusumoto 1-9-2-102 Minamidai, Sagamihara City, Kanagawa Prefecture (72) Inventor Hijiro Hiyama Sagamihara, Kanagawa Prefecture 4-29-3-101 Ichikami Tsuruma (72) Inventor Kenichi Sato 35-11 Kamimizo, Sagamihara City, Kanagawa Prefecture

Claims (8)

[Claims] 1. A compound represented by the following general formula (I) (Wherein, R ¹ has 1 to 1 carbon atoms which may have a substituent.
8 is an alkyl group, R ² is a linear alkyl group having 1 to 10 carbon atoms, X is a single bond, —O—, —COO—,
-OCO- or -OCOO-, Y and Z are groups independently selected from the group consisting of a single bond and -COO-, and ring A, ring B and ring C are 1 or 2 fluorines. A 1,4-phenylene group which may be substituted with
Trans-1,4-cyclohexylene group, pyrimidine-
A group independently selected from the group consisting of a 2,5-diyl group, a pyridine-2,5-diyl group and a 2,6-naphthylene group, and n is an integer of 1 or 0,
D ¹ , D ² , D ³ , D ⁴ , D ⁵ and D ⁶ are at least one of these is deuterium and the rest is hydrogen, and the carbon marked with * is an asymmetric carbon, Its absolute configuration is R or S. An optically active compound represented by the formula: 2. The optically active compound according to claim 1, wherein n is 1 in the general formula (I). 3. The optically active compound according to claim 2, wherein in the general formula (I), ring C is a 1,4-phenylene group or a 2,6-naphthylene group which may be substituted with one or two fluorines. Compound. 4. The optically active compound according to claim 3, wherein Z in the general formula (I) is —COO—. 5. The optically active compound according to claim 4, wherein X in the general formula (I) is a single bond or —O—. 6. A liquid crystal composition containing the optically active compound according to claim 1, 2, 3, 4 or 5. 7. An antiferroelectric liquid crystal composition containing the optically active compound according to claim 1. 8. The following general formula (II): (In the formula, R ² is a linear alkyl group having 1 to 10 carbon atoms, ring C is a 1,4-phenylene group which may be substituted with 1 or 2 fluorines, and trans-1,4. A cyclohexylene group, a pyrimidine-2,5-diyl group, a pyridine-2,5-diyl group or a 2,6-naphthylene group, and D ¹ , D ² , D ³ , D ⁴ , D ⁵ and D ⁶ are , At least one of these is deuterium and the rest is hydrogen,
The carbon marked with is an asymmetric carbon and its absolute configuration is R or S. An optically active compound represented by the formula: