WO2014010665A1 - Novel compound having negative dielectric anisotropy and having cyclic structure, method for producing same, liquid crystal composition and liquid crystal electrooptical element - Google Patents

Abstract

The purpose of the present invention is to provide a novel negative Δε function-developing cyclic structure-containing compound in which Δε is a large negative value, which is chemically stable, which has excellent compatibility with other liquid crystal materials or non-liquid crystal materials, and which is used to develop a liquid crystal compound capable of exhibiting a variety of characteristics such as rapid response, low viscosity, wide liquid crystal temperature range and high transparency by specifying a bonding group to a linking group; a method for producing this compound; and a liquid crystal composition and liquid crystal electrooptical element containing this compound. The present invention provides a compound represented by formula (1).

Description

Novel compound having a ring structure with negative dielectric anisotropy, method for producing the same, liquid crystal composition, and liquid crystal electro-optical element

The present invention relates to a novel compound having a novel ring structure that exhibits negative dielectric anisotropy (Δε) and a method for producing the same, and more specifically, 5,5,6,6-tetrafluoro-1,3. The present invention relates to a compound having a cyclohexadiene-1,4-diyl group, a method for producing the compound, a liquid crystal composition containing the compound, and a liquid crystal electro-optical element formed using the liquid crystal composition.

Liquid crystal electro-optical elements include mobile devices such as mobile phones and PDAs, display devices for OA devices such as copiers and personal computer monitors, display devices for home appliances such as liquid crystal televisions, clocks, calculators, measuring instruments, and automotive instruments. It is used for a wide range of applications such as cameras.
There are TN (twisted nematic) method, STN (super twisted nematic) method, or TN-based active matrix (TFT: thin film transistor) method, etc., and these drive methods include Δε ( A liquid crystal composition having a positive dielectric anisotropy is used. However, one of the drawbacks of these display methods is a narrow viewing angle.
Therefore, an IPS (in-plane switching) method or a VA (vertical alignment) method with improved viewing angle is often used as a driving method for large-sized liquid crystal electro-optic elements, among active matrix methods. A liquid crystal composition having a positive or negative Δε is used for the IPS mode, and a liquid crystal composition having a negative Δε is used for the VA mode.

Since it is difficult to satisfy all performances required for a liquid crystal electro-optical element with a single compound, a liquid crystal composition in which several liquid crystalline compounds having one or two or more specific excellent properties are usually combined Is used as a material showing a liquid crystal phase used in a liquid crystal electro-optical element.
In order to adjust a liquid crystal composition having a negative Δε, a liquid crystal compound having a negative Δε is indispensable, and a liquid crystal compound having a large absolute value of Δε is desired.
Δε is a value (Δε = ε∥−ε⊥) defined as the difference between the dielectric constant (ε∥) in the molecular major axis direction and the dielectric constant (ε⊥) in the minor molecular axis direction, and Δε is a negative dielectric constant. Is required to have a characteristic functional ring structure in which the value of ε⊥ is larger than that of ε∥.

In order to increase the value of ε⊥, it is effective to introduce an electron-withdrawing group such as fluorine in the side orientation of the liquid crystal molecule to increase the dipole moment in the minor axis direction.
The function-expressing ring structure having a negative Δε used for general purposes is limited to a structure in which an electron-withdrawing group such as fluorine is introduced into a side orientation such as a phenyl ring or a naphthalene ring.
For example, a compound represented by Formula (A) (see Patent Document 1) and a compound represented by Formula (B) (see Patent Document 2) having a 2,3-difluorophenylene group as a Δε negative function-expressing ring structure, A compound represented by the formula (C) in which a naphthalene ring has a Δε negative function-expressing ring structure (see Patent Document 3) is known.

JP-T-2-503441 Japanese Patent Laid-Open No. 10-176167 JP 2001-31597 A

Since the Δε negative function-expressing ring structure of the liquid crystal compound is limited, there is a limit to increase the variation of the Δε negative liquid crystal compound. The development of a new Δε-negative functional ring structure for the development of a novel Δε-negative liquid crystalline compound is awaited.
For this reason, the present invention is chemically stable, excellent in compatibility with other liquid crystal materials or non-liquid crystal materials, and has a high responsiveness, low viscosity, and a wide liquid crystal temperature range by designing a bonding group to the linking group. Another object of the present invention is to provide a new Δε negative function-expressing ring structure-containing compound having a large Δε in order to develop a liquid crystalline compound that can also have characteristics such as a high clearing point.
The present invention also provides a novel Δε negative function-expressing ring structure, a method for producing a compound incorporating the same, a liquid crystal composition suitable for obtaining a highly reliable liquid crystal electro-optic element, and a liquid crystal composition thereof. It is an object of the present invention to provide a liquid crystal electro-optical element used.

As a result of intensive studies, the present inventors have devised a 5,5,6,6-tetrafluoro-1,3-cyclohexadiene-1,4-diyl group as a new Δε negative function-expressing ring structure. We have succeeded in synthesizing a compound incorporating this new functional ring structure. This new Δε negative function-expressing ring structure showed a negative Δε, which was found to be useful as a Δε-negative function-expressing ring structure. The 5,5,6,6-tetrafluoro-1,3-cyclohexadiene-1,4-diyl group has a completely new structure and has not been synthesized. Therefore, the compound containing this function-expressing ring structure is a novel compound, and its production method is also novel.

The compound according to the present invention is represented by the following formula (1).

(1)
The symbol in Formula (1) shows the following meanings.
R ¹ and R ^{2 are} each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 18 carbon atoms, wherein one or more hydrogen atoms may be substituted with a halogen atom Well, an etheric oxygen atom (—O—) or a thioetheric sulfur atom (—S—) may be inserted between carbon-carbon atoms (C—C) or at the bond terminal of the group, and one or more —CH ₂ CH ₂ — may be substituted with —CH═CH— or —C≡C—.
A ¹ , A ² , A ³ , A ⁴ , A ⁵ and A ⁶ : independently of each other, trans-1,4-cyclohexylene group, 1,4-cyclohexenylene group, 1,3-cyclobutylene Group, 1,2-cyclopropylene group, naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group, or 1, 4-phenylene group, and in each of these groups, one or more hydrogen atoms may be substituted with a halogen atom, and one or two ═CH— may be substituted with a nitrogen atom. Alternatively, _two —CH ₂ — may be substituted with —O— or —S—.
Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ^{6 are} each independently a single bond or an alkylene group having 1 to 4 carbon atoms, in which one or more hydrogen atoms are One or more —CH ₂ — may be substituted with —O— or —S—, and one or more —CH ₂ CH ₂ — may be substituted with —CH═CH—. Alternatively, —C≡C— may be substituted, and one —CH ₂ CH ₂ — may be substituted with —COO— or —OCO—.
m, n, o, p, q and r: 0 or 1 independently of each other. However, 0 ≦ m + n + o + p + q + r ≦ 4.

The compound is preferably represented by the following formula (1-1).

(1-1)
The symbols in the formula have the following meanings.
R ¹¹ and R ^{21 are} each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 18 carbon atoms, wherein one or more hydrogen atoms may be substituted with a halogen atom In addition, —O— or —S— may be inserted between carbon-carbon atoms or at the bond terminal of the group, and one or more —CH ₂ CH ₂ — may be substituted with —CH═CH—. Also good.
A ¹¹ , A ²¹ , A ³¹ , A ⁴¹ , A ⁵¹ , and A ⁶¹ : each independently a trans-1,4-cyclohexylene group or a 1,4-phenylene group, One or more hydrogen atoms may be substituted with a halogen atom, one or two ═CH— may be substituted with a nitrogen atom, and one or two —CH ₂ — may be —O—. Alternatively, it may be substituted with -S-.
Z ¹¹ , Z ²¹ , Z ³¹ , Z ⁴¹ , Z ⁵¹ and Z ^{61 are} each independently a single bond or an alkylene group having 1 to 4 carbon atoms, in which one or more hydrogen atoms are One or more —CH ₂ — may be substituted with —O— or —S—, and one or more —CH ₂ CH ₂ — may be substituted with —CH═CH—. Alternatively, it may be substituted with -C≡C-.
m, n, o, p, q and r have the same meaning as described above.

The compound is more preferably represented by the following formula (1-2).

(1-2)
The symbols in the formula have the following meanings.
R ¹² and R ^{22 are} each independently an alkyl group having 1 to 10 carbon atoms, and one or more hydrogen atoms in the group may be substituted with a fluorine atom, and a carbon-carbon atom or —O— may be inserted at the bond terminal of the group, and one or more —CH ₂ CH ₂ — may be substituted with —CH═CH—.
A ¹² , A ²² , A ³² , A ⁴² , A ⁵² and A ⁶² : independently of each other, a trans-1,4-cyclohexylene group, 1,4-phenylene group or one or two hydrogen atoms 1,4-phenylene group substituted by a fluorine atom.
Z ¹² , Z ²² , Z ³² , Z ⁴² , Z ⁵² and Z ⁶² : independently of each other, a single bond, —CH ₂ CH ₂ —, —CH═CH—, —C≡C—, —CH ₂ O —, —OCH ₂ —, —CF ₂ CF ₂ —, —CF═CF—, —OCF ₂ —, —CF ₂ O—, —CH ₂ CH ₂ OCF ₂ —, —CF ₂ OCH ₂ CH ₂ —, — CF═CFCF ₂ O— or —OCF ₂ CF═CF—.

The present invention can provide the following method as an example of a method for producing the above compound.
The compound represented by the following formula (2) is cyclized to obtain a compound represented by the following formula (3), and then further hydrogenated to obtain a compound represented by the following formula (4). A method for producing a compound represented by formula (1), characterized in that the compound is represented by 1).

R ³ in the formula (2) is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and other symbols in each formula have the same meaning as the symbols in the formula (1).
Moreover, this invention provides the compound represented by said Formula (2), Formula (3), and Formula (4).

The present invention also provides a liquid crystal composition comprising the compound represented by the formula (1).

The present invention also provides a liquid crystal electro-optical element formed by sealing the liquid crystal composition between two substrates provided with electrodes.

Since the compound of the present invention has a novel Δε negative function-expressing ring structure, Δε is negatively large, and is useful for an operation mode utilizing vertical alignment. In addition, since the ring structure is a structure in which Δε is negatively large, the compound of the present invention has a feature that Δε is negatively large, but the ring group, substituent, and linking group constituting the compound are also included. By appropriately selecting the liquid crystal composition, various performances required for the liquid crystal element, specifically, for example, a liquid crystal composition satisfying a wide operating temperature range, a low operating voltage, high-speed response, chemical stability, etc. it can. In addition, when the liquid crystal composition is used in a liquid crystal element, it has excellent high-speed response over a wide temperature range and can be driven at a low voltage.
According to the production method of the present invention, a compound having 5,5,6,6-tetrafluoro-1,3-cyclohexadiene-1,4-diyl group, which is a new Δε negative function-expressing ring structure, has versatility. It is high and can be easily and efficiently produced easily and industrially.

The present invention will be described in more detail below.
In the present specification, a compound represented by the formula (1) is referred to as a compound (1), and compounds represented by other formulas are also described in the same manner.
In this specification, unless otherwise specified, the ^one closer to R ¹ in the formula (1) is always the first place, and the one closer to R ² is always the fourth place.
In the compounds of the present specification, —O— and / or —S— are not linked.
In this specification, “Δε is negatively large” means that Δε is negative and the absolute value thereof is large. That is, if the value of Δε is −1 and −2, -2 is “Δε is negatively larger”.
In the present invention, the bond described by the solid line in each formula includes all stereoisomers.
In the present specification, the liquid crystal electro-optical element is not limited to a display element, but various functional elements that use the electrical or optical characteristics of liquid crystal, such as a liquid crystal display element, a light control window, and an optical shutter. And elements used for applications such as a polarization conversion element and a variable focus lens.

In the formula (1) relating to the compound of the present invention, for R ¹ and R ² as defined above, the group in which one or more hydrogen atoms in the alkyl group are substituted with halogen atoms includes a fluoroalkyl group, chloro An alkyl group etc. are mentioned. As the halogen atom for substituting the hydrogen atom in the alkyl group, a fluorine atom is preferable.
Examples of the group in which —O— or —S— is inserted between C—C in the alkyl group include an alkoxyalkyl group or an alkylthioalkyl group, and —O— or —S— is inserted at the bond terminal of the group. Examples of the group include an alkoxy group and an alkylthio group.
Examples of the group in which —CH ₂ CH ₂ — in the alkyl group is substituted with —CH═CH— or —C≡C— include an alkenyl group and an alkynyl group.

In R ¹ and R ² , substitution of a hydrogen atom with a fluorine atom, insertion of —O— or —S— between C—C or at the bonding terminal of the group, and —CH═CH of —CH ₂ CH ₂ — Substitution with — or —C≡C— may be performed simultaneously on the same alkyl group.
Examples of the group in which substitution of a fluorine atom and insertion of —O— are simultaneously performed include a fluoroalkoxy group and a fluoroalkoxyalkyl group.
Examples of the group in which —CH═CH— or —C≡C— substitution and fluorine atom substitution are simultaneously performed include a fluoroalkenyl group and a fluoroalkynyl group.
Examples of the group in which substitution of —CH═CH— or —C≡C— and insertion of —O— or —S— between C—C are performed simultaneously include alkenyloxyalkyl group, alkynyloxyalkyl group, alkenyl A thioalkyl group and an alkynylthioalkyl group can be mentioned.
Examples of the group in which —CH═CH— or —C≡C— is substituted and —O— or —S— is inserted at the bonding end of the group include an alkenyloxy group, an alkynyloxy group, an alkenylthio group, and an alkynylthio group. Groups.
Further, groups in which fluorine atom substitution, —CH═CH— or —C≡C— substitution, and —O— or —S— insertion are performed simultaneously include fluoroalkenyloxy group, fluoroalkynyloxy group And a fluoroalkenylthio group.
These groups may be either linear or branched, but are preferably linear.

Among the above, R ¹ and R ² are preferably fluorine atoms and groups having 1 to 18 carbon atoms because reactivity and side reactions are less likely to occur.
Alkyl group, alkoxy group, alkoxyalkyl group, alkylthio group, alkylthioalkyl group, alkenyl group, alkenyloxy group, alkenyloxyalkyl group, alkenylthio group, fluoroalkyl group, fluoroalkoxy group, fluoroalkoxyalkyl group, fluoroalkenyl group or A fluoroalkenylthio group;

Among them, R ¹ and R ² are alkyl groups, alkoxy groups, alkoxyalkyl groups, alkenyl groups, alkenyloxy groups, alkenyloxyalkyl groups, fluoroalkyl groups, fluoroalkoxy groups, fluoroalkoxyalkyls having 1 to 10 carbon atoms. Group, a fluoroalkenyl group is more preferable, and an alkyl group, an alkoxy group, and an alkenyl group having 1 to 10 carbon atoms are particularly preferable.

Further, in A ¹ , A ² , A ³ , A ⁴ , A ^5, and A ⁶ in the formula (1) defined above, substitution of a hydrogen atom with a halogen atom, ═CH—to a nitrogen atom substituted, and, -CH ₂ - substituted Roh -O- or -S- to may be carried out simultaneously for the same group. As a halogen atom, a chlorine atom or a fluorine atom is preferable.

When A ¹ , A ² , A ³ , A ⁴ , A ⁵ and A ⁶ are 1,4-phenylene groups and further have a halogen atom as a substituent, a halogen atom to be substituted with one 1,4-phenylene group The number of is from 1 to 4, with 1 or 2 being preferred. In the case of a trans-1,4-cyclohexylene group and further having a halogen atom as a substituent, the number of halogen atoms is preferably 1 to 4. The halogen atom may be bonded to the 1st or 4th carbon atom of the cyclohexylene group.
Examples of the group in which one or two ═CH— in the 1,4-phenylene group are substituted with a nitrogen atom include a 2,5-pyrimidinylene group and a 2,5-pyridinylene group.
Examples of the group in which one or two —CH ₂ — in the trans-1,4-cyclohexylene group is substituted with —O— or —S— include a 1,3-dioxane-2,5-diyl group, A 1,3-dithian-2,5-diyl group may be mentioned.
Hereinafter, a 1,4-phenylene group substituted with at least one of a halogen atom and a nitrogen atom is referred to as a “substituted 1,4-phenylene group” and substituted with at least one of a halogen atom, —O— and —S—. The 1,4-cyclohexylene group thus prepared is referred to as “substituted trans-1,4-cyclohexylene group”.

Among them, A ¹ , A ² , A ³ , A ⁴ , A ⁵ and A ⁶ are trans-1,4-cyclohexylene group, 1,4-phenylene because of reactivity and availability of raw materials. A group, a substituted trans-1,4-cyclohexylene group, or a substituted 1,4-phenylene group is preferred.
Among these, a trans-1,4-cyclohexylene group, a 1,4-phenylene group, or a 1,4-phenylene group in which one or two hydrogen atoms in the group are substituted with fluorine atoms is more preferable. A 1,4-cyclohexylene group or a 1,4-phenylene group is particularly preferred.
When at least one of A ¹ , A ² , A ³ , A ⁴ , A ⁵ and A ⁶ of the compound (1) is a 2,3-difluoro-1,4-phenylene group or the following ring group, It is preferable because Δε of the compound is considered to be larger due to being negative.

In any of A ¹ , A ² , A ³ , A ⁴ , A ⁵ and A ⁶ , the one closer to R ¹ in the formula (1) is the first place, and the one closer to R ² is the fourth place.

In the compound (1), Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ have the same meaning as described above.
In addition, substitution of a hydrogen atom with a fluorine atom, substitution of —CH ₂ — with —O— or —S—, —CH═CH— of —CH ₂ CH ₂ —, —C≡C—, —COO— , —OCO— may be substituted simultaneously for the same group.
Examples of the alkylene group in which one or more hydrogen atoms in the group are substituted with fluorine atoms include —CF ₂ CF ₂ —, —CF ₂ CH ₂ —, —CH ₂ CF ₂ —, —CHFCH ₂ —, —CH ₂ CHF—, —CF ₂ CHF—, —CHFCF ₂ — and the like can be mentioned.
Examples of the alkylene group in which one or more —CH ₂ — in the group is substituted by —O— or —S— include —CH ₂ O—, —OCH ₂ —, —CH ₂ S—, —SCH ₂ — and the like. Is mentioned.
Further, groups in which the substitution of a hydrogen atom in a group with a fluorine atom and the substitution of —CH ₂ — in the group with —O— are performed simultaneously include —CF ₂ O—, —OCF ₂ — Etc.
The alkylene group in which one or more —CH ₂ CH ₂ — in the group is substituted with —CH═CH— or —C≡C— includes an alkenylene group or an alkynylene group. The alkenylene group or alkynylene group includes —CH═CH—, —CH═CH—CH ₂ —, —CH═CH—CH ₂ —CH ₂ —, —CH═CH—CH═CH—, —CH ₂ —CH. ═CH—CH ₂ —, —C≡C—, —C≡C—CH ₂ —, —C≡C—CH ₂ —CH ₂ —, —C≡C—C≡C—, —CH ₂ —C≡ C—CH ₂ — and the like can be mentioned. Further, double bonds and triple bonds may be mixed as in —CH═CH—C≡C—. These groups may be reversed.
Examples of groups in which —CH═CH— or —C≡C— and fluorine atoms are simultaneously substituted include —CF═CF—, —CF═CF—C≡C— and the like.
Examples of the group in which one —CH ₂ CH ₂ — is substituted with —COO— or —OCO— include —COO—, —OCO—, —CH ₂ CH ₂ —COO—, —CH ₂ CH ₂ -OCO- and the like.
When Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ or Z ⁶ in the formula (1) defined above is a single bond, the groups present on both sides of each group are directly Means to join. For example, when Z ¹ is a single bond and m and n are 1, A ¹ and A ² are directly bonded. When Z ¹ , Z ² and Z ³ are single bonds, m, n and o are 0 and p is 1, R ¹ and A ⁴ are directly bonded. The same applies to Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ .

Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ are preferably a single bond or an alkylene group having 1 to 4 carbon atoms from the viewpoint of ease of synthesis. One or more hydrogen atoms in the group may be substituted with a fluorine atom, and one or more —CH ₂ — in the group may be substituted with —O— or —S—. Two or more —CH ₂ CH ₂ — may be substituted with —CH═CH— or —C≡C—.
Among them, a single _{bond, -CH 2 CH 2 -, -} CH = CH -, - C≡C -, - CH 2 O -, - OCH 2 -, - CF 2 CF 2 -, - CF = CF -, - OCF ₂ —, —CF ₂ O—, —CH ₂ CH ₂ OCF ₂ —, or —CF ₂ OCH ₂ CH ₂ —, —CF═CFCF ₂ O—, —OCF ₂ CF═CF— are preferred.
In particular, a single bond, —CH ₂ CH ₂ —, —C≡C—, —CH ₂ O—, —OCH ₂ —, —OCF ₂ —, and —CF ₂ O— are preferable.

In the compound (1) of the present invention, m, n, o, p, q and r have the same meaning as described above.
In addition, m, n, o, p, q, and r can be suitably selected according to the characteristics required for the compound.
For example, when importance is attached to the low viscosity of the compound (1) or the excellent compatibility of the compound with other liquid crystal materials or non-liquid crystal materials, it is preferable that 0 ≦ m + n + o + p + q + r ≦ 1. On the other hand, when emphasizing the high liquid crystal temperature range of the compound, it is preferable that 1 ≦ m + n + o + p + q + r ≦ 3.

As the compound (1) of the present invention, the compound (1-1) is preferable.

(1-1)
The symbols in the formula are as described above.

As the compound (1) of the present invention, the compound (1-2) is more preferred.

(1-2)
The symbols in the formula are as described above.

Preferable examples of compound (1) include the following compounds. In the following formulas, R ¹ , R ² , Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ have the same meaning as described above, and other symbols have the following meanings.
-Cy-: trans-1,4-cyclohexylene group.
-Phe-: 1,4-phenylene group optionally substituted by one or two fluorine atoms.
—Cd—: 5,5,6,6-tetrafluoro-1,3-cyclohexadiene-1,4-diyl group—Py (2) —:

-Py (3)-:

Bicyclic compounds (m + n + o + p + q + r = 1):
R ¹ -Ph-Z ² -Cd-R ²
R ¹ -Cy-Z ² -Cd-R ²
R ¹ -Py (2) -Z ² -Cd-R ²
R ¹ -Cd-Z ⁵ -Py (3) -R ²
R ¹ -Cd-Z ⁵ -Phe-R ²
R ¹ -Cd-Z ⁵ -Cy-R ²
R ¹ -Cd-Z ⁵ -Py (2) -R ²
R ¹ -Py (3) -Z ² -Cd-R ²

Tricyclic compound (m + n + o + p + q + r = 2):
R ¹ -Ph-Z ² -Ph-Z ³ -Cd-R ²
R ¹ -Cy-Z ² -Ph-Z ³ -Cd-R ²
R ¹ -Py (2) -Z ² -Ph-Z ³ -Cd-R ²
R ¹ -Py (3) -Z ² -Ph-Z ³ -Cd-R ²
R ¹ -Ph-Z ² -Cy-Z ³ -Cd-R ²
R ¹ -Cy-Z ² -Cy-Z ³ -Cd-R ²
R ¹ -Py (2) -Z ² -Cy-Z ³ -Cd-R ²
R ¹ -Py (3) -Z ² -Cy-Z ³ -Cd-R ²
R ¹ -Ph-Z ² -Py (2) -Z ³ -Cd-R ²
R ¹ -Ph-Z ² -Py (3) -Z ³ -Cd-R ²
R ¹ -Cy-Z ² -Py (2) -Z ³ -Cd-R ²
R ¹ -Cy-Z ² -Py (3) -Z ³ -Cd-R ²
R ¹ -Ph-Z ² -Cd-Z ⁵ -Ph-R ²
R ¹ -Ph-Z ² -Cd-Z ⁵ -Cy-R ²
R ¹ -Ph-Z ² -Cd-Z ⁵ -Py (2) -R ²
R ¹ -Ph-Z ² -Cd-Z ⁵ -Py (3) -R ²
R ¹ -Cy-Z ² -Cd-Z ⁵ -Cy-R ²
R ¹ -Cy-Z ² -Cd-Z ⁵ -Py (2) -R ²
R ¹ -Cy-Z ² -Cd-Z ⁵ -Py (3) -R ²

4-ring compound (m + n + o + p + q + r = 3):
R ¹ -Ph-Z ² -Ph-Z ³ -Ph-Z ⁴ -Cd-R ²
R ¹ -Cy-Z ² -Ph-Z ³ -Ph-Z ⁴ -Cd-R ²
R ¹ -Py (2) -Z ² -Ph-Z ³ -Ph-Z ⁴ -Cd-R ²
R ¹ -Py (3) -Z ² -Ph-Z ³ -Ph-Z ⁴ -Cd-R ²
R ¹ -Ph-Z ² -Cy-Z ³ -Ph-Z ⁴ -Cd-R ²
R ¹ -Ph-Z ² -Py (2) -Z ³ -Ph-Z ⁴ -Cd-R ²
R ¹ -Ph-Z ² -Py (3) -Z ³ -Ph-Z ⁴ -Cd-R ²
R ¹ -Ph-Z ² -Ph-Z ³ -Cy-Z ⁴ -Cd-R ²
R ¹ -Ph-Z ² -Ph-Z ³ -Py (2) -Z ⁴ -Cd-R ²
R ¹ -Ph-Z ² -Ph-Z ³ -Py (3) -Z ⁴ -Cd-R ²
R ¹ -Ph-Z ² -Cy-Z ³ -Py (2) -Z ⁴ -Cd-R ²
R ¹ -Ph-Z ² -Cy-Z ³ -Py (3) -Z ⁴ -Cd-R ²
R ¹ -Cy-Z ² -Cy-Z ³ -Ph-Z ⁴ -Cd-R ²
R ¹ -Cy-Z ² -Py (2) -Z ³ -Ph-Z ⁴ -Cd-R ²
R ¹ -Cy-Z ² -Py (3) -Z ³ -Ph-Z ⁴ -Cd-R ²
R ¹ -Cy-Z ² -Cy-Z ³ -Cy-Z ⁴ -Cd-R ²
R ¹ -Cy-Z ² -Cy-Z ³ -Py (2) -Z ⁴ -Cd-R ²
R ¹ -Cy-Z ² -Cy-Z ³ -Py (3) -Z ⁴ -Cd-R ²
R ¹ -Cy-Z ² -Ph-Z ³ -Cy-Z ⁴ -Cd-R ²
R ¹ -Cy-Z ² -Ph-Z ³ -Py (2) -Z ⁴ -Cd-R ²
R ¹ -Cy-Z ² -Ph-Z ³ -Py (3) -Z ⁴ -Cd-R ²

R ¹ -Ph-Z ² -Ph-Z ³ -Cd-Z ⁵ -Ph-R ²
R ¹ -Ph-Z ² -Cy-Z ³ -Cd-Z ⁵ -Ph-R ²
R ¹ -Ph-Z ² -Py (2) -Z ³ -Cd-Z ⁵ -Ph-R ²
R ¹ -Ph-Z ² -Py (3) -Z ³ -Cd-Z ⁵ -Ph-R ²
R ¹ -Ph-Z ² -Ph-Z ³ -Cd-Z ⁵ -Cy-R ²
R ¹ -Ph-Z ² -Ph-Z ³ -Cd-Z ⁵ -Py (2) -R ²
R ¹ -Ph-Z ² -Ph-Z ³ -Cd-Z ⁵ -Py (3) -R ²
R ¹ -Cy-Z ² -Ph-Z ³ -Cd-Z ⁵ -Ph-R ²
R ¹ -Py (2) -Z ² -Ph-Z ³ -Cd-Z ⁵ -Ph-R ²
R ¹ -Py (3) -Z ² -Ph-Z ³ -Cd-Z ⁵ -Ph-R ²
R ¹ -Cy-Z ² -Ph-Z ³ -Cd-Z ⁵ -Cy-R ²
R ¹ -Cy-Z ² -Ph-Z ³ -Cd-Z ⁵ -Py (2) -R ²
R ¹ -Cy-Z ² -Ph-Z ³ -Cd-Z ⁵ -Py (3) -R ²
R ¹ -Cy-Z ² -Cy-Z ³ -Cd-Z ⁵ -Ph-R ²
R ¹ -Cy-Z ² -Cy-Z ³ -Cd-Z ⁵ -Cy-R ²
R ¹ -Cy-Z ² -Cy-Z ³ -Cd-Z ⁵ -Py (2) -R ²
R ¹ -Cy-Z ² -Cy-Z ³ -Cd-Z ⁵ -Py (3) -R ²
R ¹ -Py (2) -Z ² -Cy-Z ³ -Cd-Z ⁵ -Ph-R ²
R ¹ -Py (2) -Z ² -Cy-Z ³ -Cd-Z ⁵ -Cy-R ²
R ¹ -Py (3) -Z ² -Cy-Z ³ -Cd-Z ⁵ -Ph-R ²
R ¹ -Py (3) -Z ² -Cy-Z ³ -Cd-Z ⁵ -Cy-R ²

R ¹ -Phe-Z ² -Py (2) -Z ³ -Phe-Z ⁵ -Cd-R ²
R ¹ -Phe-Z ² -Py (3) -Z ³ -Phe-Z ⁵ -Cd-R ²
R ¹ -Phe-Z ² -Cy-Z ³ -Cy-Z ⁵ -Cd-R ²
R ¹ -Phe-Z ² -Py (2) -Z ³ -Cy-Z ⁵ -Cd-R ²
R ¹ -Phe-Z ² -Py (3) -Z ³ -Cy-Z ⁵ -Cd-R ²
R ¹ -Py (2) -Z ² -Phe-Z ³ -Cy-Z ⁵ -Cd-R ²
R ¹ -Py (3) -Z ² -Phe-Z ³ -Cy-Z ⁵ -Cd-R ²
R ¹ -Cy-Z ² -Py (2) -Z ³ -Cy-Z ⁵ -Cd-R ²
R ¹ -Cy-Z ² -Py (3) -Z ³ -Cy-Z ⁵ -Cd-R ²
R ¹ -Py (2) -Z ² -Cy-Z ³ -Cy-Z ⁵ -Cd-R ²
R ¹ -Py (3) -Z ² -Cy-Z ³ -Cy-Z ⁵ -Cd-R ²
R ¹ -Phe-Z ² -Cy-Z ³ -Cd-Z ⁵ -Cy-R ²
R ¹ -Phe-Z ² -Py (2) -Z ³ -Cd-Z ⁵ -Cy-R ²
R ¹ -Phe-Z ² -Py (3) -Z ³ -Cd-Z ⁵ -Cy-R ²
R ¹ -Py (2) -Z ² -Phe-Z ³ -Cd-Z ⁵ -Cy-R ²
R ¹ -Py (3) -Z ² -Phe-Z ³ -Cd-Z ⁵ -Cy-R ²
R ¹ -Phe-Z ² -Cy-Z ³ -Cd-Z ⁵ -Py (2) -R ²
R ¹ -Phe-Z ² -Cy-Z ³ -Cd-Z ⁵ -Py (3) -R ²
R ¹ -Cy-Z ² -Py (2) -Z ³ -Cd-Z ⁵ -Cy-R ²
R ¹ -Cy-Z ² -Py (3) -Z ³ -Cd-Z ⁵ -Cy-R ²
R ¹ -Cy-Z ² -Py (2) -Z ³ -Cd-Z ⁵ -Phe-R ²
R ¹ -Cy-Z ² -Py (3) -Z ³ -Cd-Z ⁵ -Phe-R ²

5-ring compound (m + n + o + p + q + r = 4):
R ¹ -Ph-Z ¹ -Ph-Z ² -Ph-Z ³ -Ph-Z ⁴ -Cd-R ²
R ¹ -Ph-Z ¹ -Ph-Z ² -Ph-Z ³ -Cy-Z ⁴ -Cd-R ²
R ¹ -Ph-Z ¹ -Ph-Z ² -Ph-Z ³ -Py (2) -Z ⁴ -Cd-R ²
R ¹ -Ph-Z ¹ -Ph-Z ² -Ph-Z ³ -Py (3) -Z ⁴ -Cd-R ²
R ¹ -Ph-Z ¹ -Ph-Z ² -Cy-Z ³ -Ph-Z ⁴ -Cd-R ²
R ¹ -Ph-Z ¹ -Ph-Z ² -Py (2) -Z ³ -Ph-Z ⁴ -Cd-R ²
R ¹ -Ph-Z ¹ -Ph-Z ² -Py (3) -Z ³ -Ph-Z ⁴ -Cd-R ²
R ¹ -Z ¹ -Ph-Z ² -Cy-Z ³ -Ph-Z ⁴ -Ph-Z ⁵ -Cd-R ²
R ¹ -Z ¹ -Ph-Z ² -Py (2) -Z ³ -Ph-Z ⁴ -Ph-Z ⁵ -Cd-R ²
R ¹ -Z ¹ -Ph-Z ² -Py (3) -Z ³ -Ph-Z ⁴ -Ph-Z ⁵ -Cd-R ²
R ¹ -Cy-Z ¹ -Ph-Z ² -Ph-Z ³ -Ph-Z ⁴ -Cd-R ²
R ¹ -Py (2) -Z ¹ -Ph-Z ² -Ph-Z ³ -Ph-Z ⁴ -Cd-R ²
R ¹ -Py (3) -Z ¹ -Ph-Z ² -Ph-Z ³ -Ph-Z ⁴ -Cd-R ²
R ¹ -Ph-Z ¹ -Ph-Z ² -Cy-Z ³ -Cy-Z ⁴ -Cd-R ²
R ¹ -Ph-Z ¹ -Ph-Z ² -Py (2) -Z ³ -Cy-Z ⁴ -Cd-R ²
R ¹ -Ph-Z ¹ -Ph-Z ² -Py (3) -Z ³ -Cy-Z ⁴ -Cd-R ²
R ¹ -Ph-Z ¹ -Cy-Z ² -Ph-Z ³ -Cy-Z ⁴ -Cd-R ²
R ¹ -Ph-Z ¹ -Py (2) -Z ² -Ph-Z ³ -Cy-Z ⁴ -Cd-R ²
R ¹ -Ph-Z ¹ -Py (3) -Z ² -Ph-Z ³ -Cy-Z ⁴ -Cd-R ²

R ¹ -Z ¹ -Cy-Z ² -Ph-Z ³ -Ph-Z ⁴ -Cy-Z ⁵ -Cd-R ²
R ¹ -Z ¹ -Py (2) -Z ² -Ph-Z ³ -Ph-Z ⁴ -Cy-Z ⁵ -Cd-R ²
R ¹ -Z ¹ -Py (3) -Z ² -Ph-Z ³ -Ph-Z ⁴ -Cy-Z ⁵ -Cd-R ²
R ¹ -Ph-Z ¹ -Ph-Z ² -Cy-Z ³ -Py (2) -Z ⁴ -Cd-R ²
R ¹ -Ph-Z ¹ -Cy-Z ² -Ph-Z ³ -Py (2) -Z ⁴ -Cd-R ²
R ¹ -Cy-Z ¹ -Ph-Z ² -Ph-Z ³ -Py (2) -Z ⁴ -Cd-R ²
R ¹ -Ph-Z ¹ -Ph-Z ² -Cy-Z ³ -Py (3) -Z ⁴ -Cd-R ²
R ¹ -Ph-Z ¹ -Cy-Z ² -Ph-Z ³ -Py (3) -Z ⁴ -Cd-R ²
R ¹ -Cy-Z ¹ -Ph-Z ² -Ph-Z ³ -Py (3) -Z ⁴ -Cd-R ²
R ¹ -Cy-Z ¹ -Cy-Z ² -Cy-Z ³ -Cy-Z ⁴ -Cd-R ²
R ¹ -Cy-Z ¹ -Cy-Z ² -Cy-Z ³ -Ph-Z ⁴ -Cd-R ²
R ¹ -Cy-Z ¹ -Cy-Z ² -Cy-Z ³ -Py (2) -Z ⁴ -Cd-R ²
R ¹ -Cy-Z ¹ -Cy-Z ² -Cy-Z ³ -Py (3) -Z ⁴ -Cd-R ²
R ¹ -Cy-Z ¹ -Cy-Z ² -Ph-Z ³ -Cy-Z ⁴ -Cd-R ²
R ¹ -Cy-Z ¹ -Cy-Z ² -Py (2) -Z ³ -Cy-Z ⁴ -Cd-R ²
R ¹ -Cy-Z ¹ -Cy-Z ² -Py (3) -Z ³ -Cy-Z ⁴ -Cd-R ²
R ¹ -Cy-Z ¹ -Ph-Z ² -Cy-Z ³ -Cy-Z ⁴ -Cd-R ²
R ¹ -Cy-Z ¹ -Py (2) -Z ² -Cy-Z ³ -Cy-Z ⁴ -Cd-R ²
R ¹ -Cy-Z ¹ -Py (3) -Z ² -Cy-Z ³ -Cy-Z ⁴ -Cd-R ²

R ¹ -Ph-Z ¹ -Cy-Z ² -Cy-Z ³ -Cy-Z ⁴ -Cd-R ²
R ¹ -Py (2) -Z ¹ -Cy-Z ² -Cy-Z ³ -Cy-Z ⁴ -Cd-R ²
R ¹ -Py (3) -Z ¹ -Cy-Z ² -Cy-Z ³ -Cy-Z ⁴ -Cd-R ²
R ¹ -Cy-Z ¹ -Cy-Z ² -Ph-Z ³ -Ph-Z ⁴ -Cd-R ²
R ¹ -Cy-Z ¹ -Cy-Z ² -Py (2) -Z ³ -Ph-Z ⁴ -Cd-R ²
R ¹ -Cy-Z ¹ -Cy-Z ² -Py (3) -Z ³ -Ph-Z ⁴ -Cd-R ²
R ¹ -Cy-Z ¹ -Ph-Z ² -Cy-Z ³ -Ph-Z ⁴ -Cd-R ²
R ¹ -Cy-Z ¹ -Py (2) -Z ² -Cy-Z ³ -Ph-Z ⁴ -Cd-R ²
R ¹ -Cy-Z ¹ -Py (3) -Z ² -Cy-Z ³ -Ph-Z ⁴ -Cd-R ²
R ¹ -Ph-Z ¹ -Cy-Z ² -Cy-Z ³ -Ph-Z ⁴ -Cd-R ²
R ¹ -Py (2) -Z ¹ -Cy-Z ² -Cy-Z ³ -Ph-Z ⁴ -Cd-R ²
R ¹ -Py (3) -Z ¹ -Cy-Z ² -Cy-Z ³ -Ph-Z ⁴ -Cd-R ²
R ¹ -Cy-Z ¹ -Cy-Z ² -Ph-Z ³ -Py (2) -Z ⁴ -Cd-R ²
R ¹ -Cy-Z ¹ -Ph-Z ² -Cy-Z ³ -Py (2) -Z ⁴ -Cd-R ²
R ¹ -Ph-Z ¹ -Cy-Z ² -Cy-Z ³ -Py (2) -Z ⁴ -Cd-R ²
R ¹ -Cy-Z ¹ -Cy-Z ² -Ph-Z ³ -Py (3) -Z ⁴ -Cd-R ²
R ¹ -Cy-Z ¹ -Ph-Z ² -Cy-Z ³ -Py (3) -Z ⁴ -Cd-R ^{2
R 1 -Ph-Z 1 -Cy-} Z 2 -Cy-Z 3 -Py (3) -Z 4 -Cd-R 2
R ¹ -Ph-Z ¹ -Ph-Z ² -Ph-Z ³ -Cd-Z ⁵ -Ph-R ²
R ¹ -Ph-Z ¹ -Ph-Z ² -Ph-Z ³ -Cd-Z ⁵ -Cy-R ²
R ¹ -Ph-Z ¹ -Ph-Z ² -Ph-Z ³ -Cd-Z ⁵ -Py (2) -R ²
R ¹ -Ph-Z ¹ -Ph-Z ² -Ph-Z ³ -Cd-Z ⁵ -Py (3) -R ²

R ¹ -Ph-Z ¹ -Ph-Z ² -Cy-Z ³ -Cd-Z ⁵ -Ph-R ²
R ¹ -Ph-Z ¹ -Ph-Z ² -Py (2) -Z ⁵ -Cd-Z ⁴ -Ph-R ²
R ¹ -Ph-Z ¹ -Ph-Z ² -Py (3) -Z ⁵ -Cd-Z ⁴ -Ph-R ²
R ¹ -Ph-Z ¹ -Cy-Z ² -Ph-Z ³ -Cd-Z ⁵ -Ph-R ²
R ¹ -Ph-Z ¹ -Py (2) -Z ² -Ph-Z ³ -Cd-Z ⁵ -Ph-R ²
R ¹ -Ph-Z ¹ -Py (3) -Z ² -Ph-Z ³ -Cd-Z ⁵ -Ph-R ²
R ¹ -Cy-Z ¹ -Ph-Z ² -Ph-Z ³ -Cd-Z ⁵ -Ph-R ²
R ¹ -Py (2) -Z ¹ -Ph-Z ² -Ph-Z ³ -Cd-Z ⁵ -Ph-R ²
R ¹ -Py (3) -Z ¹ -Ph-Z ² -Ph-Z ³ -Cd-Z ⁵ -Ph-R ²
R ¹ -Ph-Z ¹ -Ph-Z ² -Cy-Z ³ -Cd-Z ⁵ -Cy-R ²
R ¹ -Ph-Z ¹ -Ph-Z ² -Py (2) -Z ³ -Cd-Z ⁵ -Cy-R ²
R ¹ -Ph-Z ¹ -Ph-Z ² -Py (3) -Z ³ -Cd-Z ⁵ -Cy-R ²
R ¹ -Ph-Z ¹ -Cy-Z ² -Ph-Z ³ -Cd-Z ⁵ -Cy-R ²
R ¹ -Ph-Z ¹ -Py (2) -Z ² -Ph-Z ³ -Cd-Z ⁵ -Cy-R ²
R ¹ -Ph-Z ¹ -Py (3) -Z ² -Ph-Z ³ -Cd-Z ⁵ -Cy-R ²
R ¹ -Cy-Z ¹ -Ph-Z ² -Ph-Z ³ -Cd-Z ⁵ -Cy-R ²
R ¹ -Py (2) -Z ¹ -Ph-Z ² -Ph-Z ³ -Cd-Z ⁵ -Cy-R ²
R ¹ -Py (3) -Z ¹ -Ph-Z ² -Ph-Z ³ -Cd-Z ⁵ -Cy-R ²
R ¹ -Ph-Z ¹ -Ph-Z ² -Cy-Z ³ -Cd-Z ⁵ -Py (2) -R ²
R ¹ -Ph-Z ¹ -Cy-Z ² -Ph-Z ³ -Cd-Z ⁵ -Py (2) -R ²
R ¹ -Cy-Z ¹ -Ph-Z ² -Ph-Z ³ -Cd-Z ⁵ -Py (2) -R ²
R ¹ -Ph-Z ¹ -Ph-Z ² -Cy-Z ³ -Cd-Z ⁵ -Py (3) -R ²
R ¹ -Ph-Z ¹ -Cy-Z ² -Ph-Z ³ -Cd-Z ⁵ -Py (3) -R ²
R ¹ -Cy-Z ¹ -Ph-Z ² -Ph-Z ³ -Cd-Z ⁵ -Py (3) -R ²

R ¹ -Cy-Z ¹ -Cy-Z ² -Cy-Z ³ -Cd-Z ⁵ -Cy-R ²
R ¹ -Cy-Z ¹ -Cy-Z ² -Cy-Z ³ -Cd-Z ⁵ -Ph-R ²
R ¹ -Cy-Z ¹ -Cy-Z ² -Cy-Z ³ -Cd-Z ⁵ -Py (2) -R ²
R ¹ -Cy-Z ¹ -Cy-Z ² -Cy-Z ³ -Cd-Z ⁵ -Py (3) -R ²
R ¹ -Cy-Z ¹ -Cy-Z ² -Ph-Z ³ -Cd-Z ⁵ -Cy-R ²
R ¹ -Cy-Z ¹ -Cy-Z ² -Py (2) -Z ³ -Cd-Z ⁵ -Cy-R ²
R ¹ -Cy-Z ¹ -Cy-Z ² -Py (3) -Z ³ -Cd-Z ⁵ -Cy-R ²
R ¹ -Cy-Z ¹ -Ph-Z ² -Cy-Z ³ -Cd-Z ⁵ -Cy-R ²
R ¹ -Cy-Z ¹ -Py (2) -Z ² -Cy-Z ³ -Cd-Z ⁵ -Cy-R ²
R ¹ -Cy-Z ¹ -Py (3) -Z ² -Cy-Z ³ -Cd-Z ⁵ -Cy-R ²
R ¹ -Ph-Z ¹ -Cy-Z ² -Cy-Z ³ -Cd-Z ⁵ -Cy-R ²
R ¹ -Py (2) -Z ¹ -Cy-Z ² -Cy-Z ³ -Cd-Z ⁵ -Cy-R ²
R ¹ -Py (3) -Z ¹ -Cy-Z ² -Cy-Z ³ -Cd-Z ⁵ -Cy-R ²
R ¹ -Cy-Z ¹ -Cy-Z ² -Ph-Z ³ -Cd-Z ⁵ -Ph-R ²
R ¹ -Cy-Z ¹ -Cy-Z ² -Py (2) -Z ³ -Cd-Z ⁵ -Ph-R ²
R ¹ -Cy-Z ¹ -Cy-Z ² -Py (3) -Z ³ -Cd-Z ⁵ -Ph-R ²
R ¹ -Cy-Z ¹ -Ph-Z ² -Cy-Z ³ -Cd-Z ⁵ -Ph-R ²
R ¹ -Cy-Z ¹ -Py (2) -Z ² -Cy-Z ³ -Cd-Z ⁵ -Ph-R ²
R ¹ -Cy-Z ¹ -Py (3) -Z ² -Cy-Z ³ -Cd-Z ⁵ -Ph-R ²
R ¹ -Ph-Z ¹ -Cy-Z ² -Cy-Z ³ -Cd-Z ⁵ -Ph-R ²
R ¹ -Py (2) -Z ¹ -Cy-Z ² -Cy-Z ³ -Cd-Z ⁵ -Ph-R ²
R ¹ -Py (3) -Z ¹ -Cy-Z ² -Cy-Z ³ -Cd-Z ⁵ -Ph-R ²
R ¹ -Cy-Z ¹ -Cy-Z ² -Ph-Z ³ -Cd-Z ⁵ -Py (2) -R ²
R ¹ -Cy-Z ¹ -Ph-Z ² -Cy-Z ³ -Cd-Z ⁵ -Py (2) -R ²
R ¹ -Ph-Z ¹ -Cy-Z ² -Cy-Z ³ -Cd-Z ⁵ -Py (2) -R ²
R ¹ -Cy-Z ¹ -Cy-Z ² -Ph-Z ³ -Cd-Z ⁵ -Py (3) -R ²
R ¹ -Cy-Z ¹ -Ph-Z ² -Cy-Z ³ -Cd-Z ⁵ -Py (3) -R ²
R ¹ -Ph-Z ¹ -Cy-Z ² -Cy-Z ³ -Cd-Z ⁵ -Py (3) -R ²

R ¹ -Z ¹ -Ph-Z ² -Ph-Z ³ -Cd-Z ⁵ -Ph-Ph-R ²
R ¹ -Z ¹ -Ph-Z ² -Ph-Z ³ -Cd-Z ⁵ -Ph-Cy-R ²
R ¹ -Z ¹ -Ph-Z ² -Ph-Z ³ -Cd-Z ⁵ -Ph-Py (2) -R ²
R ¹ -Z ¹ -Ph-Z ² -Ph-Z ³ -Cd-Z ⁵ -Ph-Py (3) -R ²
R ¹ -Z ¹ -Ph-Z ² -Ph-Z ³ -Cd-Z ⁵ -Cy-Ph-R ²
R ¹ -Z ¹ -Ph-Z ² -Ph-Z ³ -Cd-Z ⁵ -Py (2) -Ph-R ²
R ¹ -Z ¹ -Ph-Z ² -Ph-Z ³ -Cd-Z ⁵ -Py (3) -Ph-R ²
R ¹ -Z ¹ -Ph-Z ² -Cy-Z ³ -Cd-Z ⁵ -Ph-Ph-R ²
R ¹ -Z ¹ -Ph-Z ² -Py (2) -Z ³ -Cd-Z ⁵ -Ph-Ph-R ²
R ¹ -Z ¹ -Ph-Z ² -Py (3) -Z ³ -Cd-Z ⁵ -Ph-Ph-R ²
R ¹ -Z ¹ -Cy-Z ² -Ph-Z ³ -Cd-Z ⁵ -Ph-Ph-R ²
R ¹ -Z ¹ -Py (2) -Z ² -Ph-Z ³ -Cd-Z ⁵ -Ph-Ph-R ²
R ¹ -Z ¹ -Py (3) -Z ² -Ph-Z ³ -Cd-Z ⁵ -Ph-Ph-R ²
R ¹ -Z ¹ -Ph-Z ² -Ph-Z ³ -Cd-Z ⁵ -Cy-Cy-R ²
R ¹ -Z ¹ -Ph-Z ² -Ph-Z ³ -Cd-Z ⁵ -Py (2) -Cy-R ²
R ¹ -Z ¹ -Ph-Z ² -Ph-Z ³ -Cd-Z ⁵ -Py (3) -Cy-R ²
R ¹ -Z ¹ -Ph-Z ² -Cy-Z ³ -Cd-Z ⁵ -Ph-Cy-R ²
R ¹ -Z ¹ -Ph-Z ² -Py (2) -Z ³ -Cd-Z ⁵ -Ph-Cy-R ²
R ¹ -Z ¹ -Ph-Z ² -Py (3) -Z ³ -Cd-Z ⁵ -Ph-Cy-R ²
R ¹ -Z ¹ -Cy-Z ² -Ph-Z ³ -Cd-Z ⁵ -Ph-Cy-R ²
R ¹ -Z ¹ -Py (2) -Z ² -Ph-Z ³ -Cd-Z ⁵ -Ph-Cy-R ²
R ¹ -Z ¹ -Py (3) -Z ² -Ph-Z ³ -Cd-Z ⁵ -Ph-Cy-R ²
R ¹ -Z ¹ -Ph-Z ² -Ph-Z ³ -Cd-Z ⁵ -Cy-Py (2) -R ²
R ¹ -Z ¹ -Ph-Z ² -Cy-Z ³ -Cd-Z ⁵ -Ph-Py (2) -R ²
R ¹ -Z ¹ -Cy-Z ² -Ph-Z ³ -Cd-Z ⁵ -Ph-Py (2) -R ²
R ¹ -Z ¹ -Ph-Z ² -Ph-Z ³ -Cd-Z ⁵ -Cy-Py (3) -R ²
R ¹ -Z ¹ -Ph-Z ² -Cy-Z ³ -Cd-Z ⁵ -Ph-Py (3) -R ²
R ¹ -Z ¹ -Cy-Z ² -Ph-Z ³ -Cd-Z ⁵ -Ph-Py (3) -R ²

R ¹ -Z ¹ -Cy-Z ² -Cy-Z ³ -Cd-Z ⁵ -Cy-Cy-R ²
R ¹ -Z ¹ -Cy-Z ² -Cy-Z ³ -Cd-Z ⁵ -Cy-Ph-R ²
R ¹ -Z ¹ -Cy-Z ² -Cy-Z ³ -Cd-Z ⁵ -Cy-Py (2) -R ²
R ¹ -Z ¹ -Cy-Z ² -Cy-Z ³ -Cd-Z ⁵ -Cy-Py (3) -R ²
R ¹ -Z ¹ -Cy-Z ² -Cy-Z ³ -Cd-Z ⁵ -Ph-Cy-R ²
R ¹ -Z ¹ -Cy-Z ² -Cy-Z ³ -Cd-Z ⁵ -Py (2) -Cy-R ²
R ¹ -Z ¹ -Cy-Z ² -Cy-Z ³ -Cd-Z ⁵ -Py (3) -Cy-R ²
R ¹ -Z ¹ -Cy-Z ² -Cy-Z ³ -Cd-Z ⁵ -Ph-Ph-R ²
R ¹ -Z ¹ -Cy-Z ² -Cy-Z ³ -Cd-Z ⁵ -Py (2) -Ph-R ²
R ¹ -Z ¹ -Cy-Z ² -Cy-Z ³ -Cd-Z ⁵ -Py (3) -Ph-R ²
R ¹ -Z ¹ -Cy-Z ² -Ph-Z ³ -Cd-Z ⁵ -Cy-Ph-R ²
R ¹ -Z ¹ -Cy-Z ² -Py (2) -Z ³ -Cd-Z ⁵ -Cy-Ph-R ²
R ¹ -Z ¹ -Cy-Z ² -Py (3) -Z ³ -Cd-Z ⁵ -Cy-Ph-R ²
R ¹ -Z ¹ -Ph-Z ² -Cy-Z ³ -Cd-Z ⁵ -Cy-Ph-R ²
R ¹ -Z ¹ -Py (2) -Z ² -Cy-Z ³ -Cd-Z ⁵ -Cy-Ph-R ²
R ¹ -Z ¹ -Py (3) -Z ² -Cy-Z ³ -Cd-Z ⁵ -Cy-Ph-R ²
R ¹ -Z ¹ -Cy-Z ² -Cy-Z ³ -Cd-Z ⁵ -Ph-Py (2) -R ²
R ¹ -Z ¹ -Cy-Z ² -Ph-Z ³ -Cd-Z ⁵ -Cy-Py (2) -R ²
R ¹ -Z ¹ -Ph-Z ² -Cy-Z ³ -Cd-Z ⁵ -Cy-Py (2) -R ²
R ¹ -Z ¹ -Cy-Z ² -Cy-Z ³ -Cd-Z ⁵ -Ph-Py (3) -R ²
R ¹ -Z ¹ -Cy-Z ² -Ph-Z ³ -Cd-Z ⁵ -Cy-Py (3) -R ²
R ¹ -Z ¹ -Ph-Z ² -Cy-Z ³ -Cd-Z ⁵ -Cy-Py (3) -R ²

As a preferable production method of the compound (1) of the present invention as described above,
A production method in which the compound (2) is cyclized to give the compound (3), then further hydrogenated to give the compound (4), and then further dehydrated to give the compound (1). A series of reactions for obtaining the compound (1) by the above production method can be expressed as follows.

The symbols in each formula have the same meaning as described above.

The compound (2) can be synthesized, for example, as follows.

However, M in the formula is a metal atom or a group containing a metal atom. Other symbols have the same meaning as described above.

That is, the compound (5) is lithiated with methyllithium and reacted with the aldehyde of the compound (6) to obtain the compound (7). The double bond of compound (7) is ozonolyzed and converted to hemiacetal (8). The diketone (11) is obtained by reacting the compound (8) with the organometallic reagent (9) to convert it to the diol (10) and then oxidizing it. Compound (2) is synthesized by reacting diketone (11) with alkenyl magnesium chloride (12).
As M of the compound (9), MgI, MgBr, MgCl and Li are preferable, and MgBr is particularly preferable.

In the compound (2), in the case of the compound (2a) in which Z ⁴ , Z ⁵ and Z ⁶ are single bonds, q and r are 0, and R ² is an alkenyl group, a more advantageous method that can be synthesized in a short process is as follows: The method is mentioned.

However, R ⁴ in the formula represents an alkyl group having 1 to 4 carbon atoms, and other symbols have the same meaning as described above.

That is, a commercially available tetrafluorosuccinic acid ester (compound (13)) is reacted with an organometallic reagent represented by compound (14) to convert it to compound (15), and further represented by compound (12). The compound (2a) can be obtained by reacting with alkenyl magnesium chloride.
As M of the compound (14), MgI, MgBr, MgCl and Li are preferable, and among these, MgBr is preferable.

In the same manner as in the method of synthesizing compound (1) from compound (2a) from compound (2a), among compounds (1), Z ⁴ , Z ⁵ and Z ⁶ are single bonds, and q and r are A compound (1a) in which 0 and R ² are an alkyl group having 2 to 6 carbon atoms can also be synthesized.

Compound (3) is obtained by subjecting compound (2) to a ring-closing metathesis reaction. Ring closure metathesis reactions are described in the literature (Schwab, P .; France, MB; Ziller, JW; Grubbs, RH Angew. Chem. Int. Ed. 1995, 34, 2039., Nguyen, ST; Johnson, LK; Grubbs, RH; Ziller , JWJ Am. Chem. Soc. 1992, 114, 3974.). Solvents include aromatic hydrocarbon solvents such as benzene, toluene, xylene, and ethylbenzene, aliphatic hydrocarbon solvents such as pentane, hexane, heptane, and octane; tetrahydrofuran, diethyl ether, diisopropyl ether, dibutyl ether, and t-butylmethyl. Ether-based solvents such as ether and dimethoxyethane; petroleum ethers, halogen-based solvents such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, and parkrene, or a suitable mixed solvent of the above solvents can be used. Among these, halogen solvents such as methylene chloride and 1,2-dichloroethane, and aromatic hydrocarbon solvents such as benzene and toluene are preferable.
The transition metal catalyst is preferably a Grubbs catalyst, and the amount used is preferably 0.00001 equivalent to 10 equivalents, more preferably 0.001 equivalent to 1 equivalent, relative to 1 mol of the compound (2). More preferably, 0.01 to 0.2 equivalent is used.
The reaction temperature is preferably 0 to 150 ° C, more preferably 10 to 100 ° C.
The reaction time is preferably 0.1 to 72 hours, more preferably 1 to 48 hours.

Compound (4) is obtained by hydrogenating compound (3). The hydrogenation reaction is preferably carried out in a solvent using a heterogeneous catalyst. Solvents that can be used include aromatic hydrocarbon solvents such as benzene, toluene, xylene, and ethylbenzene; aliphatic hydrocarbon solvents such as pentane, hexane, heptane, and octane; such as ethyl acetate, methyl acetate, and propyl acetate. Ester solvents; alcohol solvents such as methanol and ethanol; ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as tetrahydrofuran, diethyl ether, dibutyl ether, t-butyl methyl ether, and dimethoxyethane; petroleum ethers or the aforementioned solvents A suitable mixed solvent or the like can be used. Among these, alcohol solvents such as methanol, ester solvents such as ethyl acetate, and mixed solvents of these solvents are preferable.

Examples of the heterogeneous catalyst that can be used in the production of the compound (4) include transition metal catalysts such as palladium carbon, rhodium carbon, ruthenium carbon, Raney nickel, and platinum oxide.
The amount of the catalyst used is preferably 0.01 to 1.0 times, more preferably 0.1 to 0.5 times the mass of the compound (3).
The reaction temperature is preferably −50 to 100 ° C., more preferably 0 to 40 ° C.
The reaction time is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

Compound (1) can be obtained by dehydrating compound (4).
As the dehydrating agent used in the dehydration reaction, phosphorus oxychloride, phosphorus pentachloride, sulfonyl chloride, sulfuryl chloride, or the like can be used.
The dehydration reaction can be carried out in a solvent if desired. Organic solvents include aromatic hydrocarbon solvents such as benzene, toluene, xylene and ethylbenzene, aliphatic hydrocarbon solvents such as pentane, hexane, heptane and octane; tetrahydrofuran, diethyl ether, diisopropyl ether, dibutyl ether and t-butyl. Ether solvents such as methyl ether and dimethoxyethane; petroleum ethers, halogen solvents such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, and parkrene, etc., or a suitable mixed solvent of the above solvents can be used. .
The dehydration reaction may be performed in the presence of a base. An inorganic base or an organic base can be used as the base. Examples of inorganic bases include alkali metals such as sodium metal and metal potassium and carbonates thereof, hydroxides, hydrides and metal cesium, alkaline earth metals such as metal aluminum and carbonates, hydroxides and hydrogen thereof. The monster is raised. Examples of the organic base include chain organic amines such as triethylamine and diisopropylamine, cyclic organic amines such as pyridine, morpholine, pyridine, quinoline and imidazole, and organic amines having a substituent in the ring.
The amount of dehydrating agent used is preferably 1.9 to 20 equivalents relative to the number of moles of compound (4), and the reaction temperature is preferably 0 to 200 ° C, more preferably 20 to 150 ° C.
The reaction time is preferably 0.5 to 72 hours, more preferably 1 to 24 hours.

Compound (2), Compound (3) and Compound (4) are useful as intermediates for synthesizing Compound (1). In the compound (2), the compound (3) and the compound (4), the definition of each group is as described above, and the preferred embodiment is the same as the compound (1).

In the compound (1), when synthesizing the compound (1b) in which Z ⁵ and Z ⁶ are single bonds, q and r are 0, and R ² is an alkoxy group, Z ⁵ and Z It is preferable to use the compound (2b) in which ⁶ is a single bond, q and r are 0, and R ² is a hydrogen atom because the target product is more easily obtained.

In the formula, R ⁵¹ represents a protecting group for OH group, R ⁶ represents an alkyl group having 1 to 10 carbon atoms, and other symbols have the same meaning as described above.

Compound (2b) to compound (4b) can be synthesized in the same manner as compound (2) to compound (4).
From compound (4b) to compound (1b), the synthesis can proceed by appropriately protecting and deprotecting the OH group.
Examples of detailed synthesis including protection and deprotection include the following methods.

(4b)
↓

↓

↓

(16)
↓

(17)
↓

↓

(1b)
However, R ⁵² in the formula represents a protecting group for the OH group, and other symbols have the same meaning as described above.

That is, after protecting each of the two OH groups of the compound (4b), the R ⁵² group protecting the terminal OH group is deprotected. This OH group is oxidized to give ketone (16). A ketone (16) is reacted with an R ⁶ group-containing compound to obtain a compound (17) having a terminal alkoxy group. The R ⁵¹ group of compound (17) is also deprotected and dehydrated to synthesize compound (1b).

R ⁵¹ and R ⁵² are OH protecting groups. It is not particularly limited as long as it is a protective group for OH group, but it cannot be attached to two OH groups at the same time, cannot be removed under the same conditions, and cannot be removed when compound (17) is synthesized from compound (16). It is preferable that it is a protecting group that satisfies the condition. Examples of R ⁵¹ and R ⁵² include a benzyl group, p-methoxyphenylbenzyl group, methoxymethyl group, trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, acetyl group, benzoyl group, and trityl group. Of these, a t-butyldimethylsilyl group and an acetyl group are preferable because they are easy to handle. Furthermore, since it is easy to control the reaction, R ⁵¹ is particularly preferably an acetyl group, and R ⁵² is particularly preferably a t-butyldimethylsilyl group.

As a method for synthesizing compound (2b), the same method as compound (2) can be used, but the following method in which compound (7) and subsequent compounds are partially modified is also included.

(2b)
However, the symbols in the formula have the same meaning as described above.

The process until the compound (7) is obtained is the same as described above. Thereafter, the compound (7) is oxidized to obtain the compound (18). The double bond of compound (18) is ozonolyzed and converted to compound (19). Compound (2b) is synthesized by reacting compound (19) with alkenylmagnesium chloride (12).

The compound (1) of the present invention is useful as a liquid crystal compound. In the present invention, the liquid crystal compound means a compound that exhibits a liquid crystal phase and a compound that does not exhibit a liquid crystal phase but is useful as a constituent of a liquid crystal composition.

The present invention provides a liquid crystal composition comprising the compound (1) of the present invention. This liquid crystal composition is constituted by mixing the compound (1) of the present invention with other liquid crystal compounds or non-liquid crystal compounds (collectively referred to as “other compounds”).

The content of the compound (1) in the liquid crystal composition of the present invention can be appropriately changed depending on the purpose of use, the purpose of use, the type of other compounds, and the like. 5 to 80% by mass is preferable, and 2 to 50% by mass is particularly preferable. Moreover, you may contain 2 or more types of compounds (1) in a liquid-crystal composition by a use, a use purpose, etc. In that case, the total amount of the compound (1) is preferably 0.5 to 80% by mass, particularly preferably 2 to 50% by mass, based on the total amount of the liquid crystal composition.

Other compounds used in combination with the compound (1) include components for adjusting the refractive index anisotropy value, components for reducing the viscosity, components exhibiting liquid crystallinity at low temperatures, components for improving the dielectric anisotropy, and cholesteric A component for imparting properties, a component exhibiting dichroism, a component for imparting conductivity, and various other additives. These are appropriately selected depending on the application, required performance and the like, but usually those composed of a liquid crystal compound, a main component having a similar structure to the liquid crystal compound, and an additive component added if necessary.

In the liquid crystal composition of the present invention, the other compound is preferably a compound represented by the following formula (D) in which Δε is negative.
R ^d1 -A ^d1 -Z ^d1 -A ^d2 -Z ^d2- (A ^d3 ) m ^d -Z ^d3- (A ^d4 ) n ^d -R ^d2 (D)
(The symbols in the formula have the following meanings.
R ^d1 and R ^{d2 are} each independently an alkyl group having 1 to 10 carbon atoms, and in the alkyl group, one or more hydrogen atoms may be substituted with a fluorine atom, —O— may be inserted at the bond terminal of the group, and one or more —CH ₂ CH ₂ — may be substituted with —CH═CH—.
A ^d1 , A ^d2 , A ^d3 and A ^d4 : each independently a trans-1,4-cyclohexylene group or a 1,4-phenylene group, wherein one or more hydrogen atoms in the group are It may be substituted with a fluorine atom.
Z ^d1 , Z ^d2 and Z ^d3 : independently of each other, a single bond, —COO—, —C≡C—, —OCO—, —OCH ₂ —, —CH ₂ O— or —C ₂ H ₄ —.
m ^d and n ^d : 0 or 1 independently of each other.
However, one or more of A ^d1 , A ^d2 , A ^d3 and A ^d4 is a 2,3-difluoro-1,4-phenylene group. )

In the compound (D), for compound m ^d and n ^d are both 0 are compounds of the 2 rings, low viscosity, it is useful when requiring fast response of the device. It can also be used to adjust the threshold voltage and refractive index anisotropy.
In the compound (D), a compound in which one of m ^d and n ^d is 1 and the other is 0 is a tricyclic compound. Therefore, the clearing point is higher than that of the bicyclic compound, and the nematic phase This is useful for expanding the liquid crystal temperature range. It can also be used to adjust the refractive index anisotropy.
In the compound (D), a compound in which both m ^d and n ^d are 1 is a tetracyclic compound, and therefore has a particularly high clearing point, and thus is particularly useful for expanding the liquid crystal temperature range.

Preferable compounds (D) include the following compounds. In the following formulae, -Ph- represents a 1,4-phenylene group, -Ph (2F, 3F)-represents a 2,3-difluoro-1,4-phenylene group, and -Cy- has the same meaning as described above. Indicates.
R ^d1 -Cy-Ph (2F, 3F) -R ^d2
R ^d1 -Ph-Ph (2F, 3F) -R ^d2
R ^d1 -Ph-C≡C-Ph (2F, 3F) -R ^d2
R ^d1 -Cy-COO-Ph (2F, 3F) -R ^d2
R ^d1 -Cy-Cy-Ph (2F, 3F) -R ^d2
R ^d1 -Cy-Cy-C ₂ H ₄ -Ph (2F, 3F) -R ^d2
R ^d1 -Cy-Cy-COO-Ph (2F, 3F) -R ^d2
R ^d1 -Cy-Ph-Ph (2F, 3F) -R ^d2
R ^d1 -Cy-Ph-C ₂ H ₄ -Ph (2F, 3F) -R ^d2
R ^d1 -Cy-Ph-C≡C-Ph (2F, 3F) -R ^d2
R ^d1 -Cy-Ph (2F, 3F) -C≡C-Ph-R ^d2
R ^d1 -Cy-COO-Ph-C≡C-Ph (2F, 3F) -R ^d2
R ^d1 -Ph-Ph-Ph (2F, 3F) -R ^d2
R ^d1 -Ph-Ph (2F, 3F) -Ph-R ^d2
R ^d1 -Ph-Ph-COO-Ph (2F, 3F) -R ^d2

When the liquid crystal composition of the present invention contains the compound (D) from the viewpoint of negatively increasing Δε of the liquid crystal composition, the content of the compound (D) is 5 to 60 mass with respect to the total amount of the liquid crystal composition. % Is preferable, and 5 to 50% by mass is more preferable. When two or more types of compounds (D) are included, the total amount is preferably in the above range.

In the liquid crystal composition of the present invention, as the other compound, in addition to the compound (D), a compound represented by the following formula (E) having a small absolute value of Δε and close to neutrality is also preferable.
R ^e1 -A ^e1 -Z ^e1 -A ^e2 -Z ^e2- (A ^e3 ) m ^e -Z ^e3- (A ^e4 ) n ^e -Z ^e4 -R ^e2 (E)
(The symbols in the formula have the following meanings.
R ^e1 and R ^e2 : each independently an alkyl group having 1 to 10 carbon atoms, in which one or more hydrogen atoms may be substituted with a fluorine atom, —O— may be inserted at the bond terminal of the group, and one or more —CH ₂ CH ₂ — may be substituted with —CH═CH—.
A ^e1 , A ^e2 , A ^e3 and A ^e4 : independently of each other, a trans-1,4-cyclohexylene group, a pyrimidine-2,5-diyl group, or a 1,4-phenylene group, One or more hydrogen atoms therein may be substituted with fluorine atoms.
Z ^e1 , Z ^e2 , Z ^e3 and Z ^e4 : independently of each other, a single bond, —COO—, —C≡C—, —OCO—, —CH═CH— or —C ₂ H ₄ —.
m ^e and n ^e : 0 or 1 independently of each other. )

In the compound (E), a compound in which m ^e and n ^e are both 0 is a bicyclic compound, which is useful when the viscosity is low and high-speed response of the device is required. It can also be used to adjust the refractive index anisotropy.
In the compound (E), a one is 1 m ^e and n ^e, compounds other is 0, because it is a compound of three rings, a high clearing point compared to the compound of the 2 rings, a nematic phase This is useful for expanding the liquid crystal temperature range. It can also be used to adjust the refractive index anisotropy.
In the compound (E), for compound m ^e and n ^e are both 1 is the compound of 4 ring, because the clearing point is particularly high, is particularly useful for the expansion of the liquid crystal temperature range.

Preferable compounds (E) include the following compounds. In the following formulae, -Pm- represents a pyrimidine-2,5-diyl group, -Ph (3F)-represents a 3-fluoro-1,4-phenylene group, -Cy- and -Ph- Indicates the same meaning.
R ^e1 -Cy-Cy-R ^e2
R ^e1 -Cy-Cy-COO-R ^e2
R ^e1 -Cy-C ₂ H ₄ -Cy-R ^e2
R ^e1 -Cy-CH = CH-Cy-R ^e2
R ^e1 -Cy-Ph-R ^e2
R ^e1 -Cy-C ₂ H ₄ -Ph-R ^e2
R ^e1 -Cy-COO-Ph-R ^e2
R ^e1 -Ph-Ph-R ^e2
R ^e1 -Ph-C ₂ H ₄ -Ph-R ^e2
R ^e1 -Ph-COO-Ph-R ^e2
R ^e1 -Ph-C≡C-Ph-R ^e2
R ^e1 -Pm-Ph-R ^e2
R ^e1 -Cy-Cy-Ph-R ^e2
R ^e1 -Cy-CH = CH-Cy-Ph-R ^e2
R ^e1 -Cy-C ₂ H ₄ -Cy-Ph-R ^e2
R ^e1 -Cy-Cy-C ₂ H ₄ -Ph-R ^e2
R ^e1 -Cy-Ph-Ph-R ^{e2
_{R e1 -Cy-Ph-C 2}} H 4 -Ph-R e2
R ^e1 -Ph-Ph-Ph-R ^e2
R ^e1 -Ph-Ph (3F) -Ph-R ^e2
R ^e1 -Pm-Cy-Cy-R ^e2
R ^e1 -Pm-Ph-Cy-R ^e2
R ^e1 -Pm-Ph-Ph-R ^e2
R ^e1 -Ph-Pm-Ph-R ^e2
R ^e1 -Cy-Cy-COO-Ph-R ^e2
R ^e1 -Cy-Ph-COO-Ph-R ^e2
R ^e1 -Cy-COO-Ph-COO-Ph-R ^{e2
R e1 -Cy-Ph-C≡C-} Ph-R e2
R ^e1 -Cy-Ph (3F) -C≡C-Ph-R ^e2
R ^e1 -Cy-C ₂ H ₄ -Ph-C≡C-Ph-R ^e2
R ^e1 -Cy-C ₂ H ₄ -Ph (3F) -C≡C-Ph-R ^e2
R ^e1 -Cy-COO-Ph-C≡C-Ph-R ^e2
R ^e1 -Ph-COO-Ph-C≡C-Ph-R ^e2
R ^e1 -Ph-C≡C-Ph-C≡C-Ph-R ^e2
R ^e1 -Ph-C≡C-Ph (3F) -C≡C-Ph-R ^e2
R ^e1 -Ph-C≡C-Ph-COO-Ph-R ^e2
R ^e1 -Cy-Ph-Ph-Cy-R ^e2
R ^e1 -Cy-Ph (3F) -Ph-Cy-R ^e2
R ^e1 -Cy-Cy-Ph-Ph-R ^e2
R ^e1 -Cy-Ph-Ph-Ph-R ^e2
R ^e1 -Cy-Ph-Ph (3F) -Ph-R ^e2
R ^e1 -Cy-Cy-COO-Ph-Cy-R ^e2

When the liquid crystal composition of the present invention contains the compound (E) from the viewpoint of reducing the viscosity of the composition, the content of the compound (E) is 10 to 50% by mass with respect to the total amount of the liquid crystal composition. Is preferable, and 20 to 40% by mass is more preferable. When two or more types of compounds (E) are included, the total amount is preferably in the above range.

In the liquid crystal composition of the present invention, an optically active compound may be added in order to achieve uniform twist alignment. Although there is no restriction | limiting in particular as an optically active compound, For example, the compound marketed by names, such as CN, S-811, CB-15, is mentioned.

When adding an optically active compound, the addition amount is adjusted so that a desired helical pitch length can be obtained. The pitch length is preferably in the range of 40 to 200 μm for TFT and TN, 6 to 20 μm for STN, and 1.5 to 4 μm for bistable TN.

Examples of the liquid crystal composition of the present invention include the following. The symbols in Table 1 have the same meaning as described above. In addition, the hydrogen atom of each group may be substituted with a deuterium atom.

Furthermore, the present invention provides a liquid crystal electro-optical element that uses the liquid crystal composition as a constituent material of a liquid crystal layer. For example, a liquid crystal electro-optical element having an electro-optical element portion formed by sandwiching a liquid crystal layer formed by, for example, injecting the liquid crystal composition of the present invention into a liquid crystal cell between two substrates having electrodes. I will provide a. The liquid crystal composition of the present invention can be suitably used in liquid crystal electro-optical elements such as VA mode, IPS mode, and OCB mode regardless of passive driving or active driving. Among them, the liquid crystal composition of the present invention is particularly useful in a mode in which liquid crystal molecules such as OCB mode and VA mode are aligned perpendicular to the electrode.

As a typical liquid crystal element in which liquid crystal molecules are aligned perpendicularly to an electrode, a VA (vertical alignment) mode liquid crystal element can be given. In this VA mode liquid crystal electro-optical element, an undercoat layer such as SiO ₂ or Al ₂ O ₃ or a color filter layer is first formed on a substrate such as plastic or glass as necessary, and In ₂ O ₃ —SnO. _{2 A} film made of (ITO), SnO ₂ or the like is formed, and an electrode having a required pattern is formed by photolithography or the like. Next, if necessary, an overcoat layer of polyimide, polyamide, SiO ₂ , Al ₂ O ₃ or the like is formed and oriented. A sealing material is printed on this, and it arrange | positions so that an electrode surface may oppose a vertical direction or a horizontal direction, a periphery is sealed, a sealing material is hardened, and an empty cell is formed.

Further, the composition of the present invention is injected into an empty cell, and the injection port is sealed with a sealant to form a liquid crystal cell. If necessary, this liquid crystal cell is laminated with a polarizing plate, a color polarizing plate, a light source, a color filter, a transflective plate, a reflecting plate, a light guide plate, an ultraviolet cut filter, etc., printing characters, figures, etc., non-glare processing, etc. Thus, a liquid crystal electro-optical element can be obtained.

The above description describes the basic configuration and manufacturing method of the liquid crystal electro-optic element, and other configurations can be adopted. For example, a display element manufactured by a liquid crystal dropping method (ODF), a substrate using a two-layer electrode, a two-layer liquid crystal cell formed with a two-layer liquid crystal layer, a substrate using a reflective electrode, an active element such as a TFT, MIM, etc. Various configurations such as an active matrix element using an active matrix substrate on which are formed can be employed. In particular, the composition of the present invention is also suitable for active matrix devices such as TFT and MIM.

Further, the composition of the present invention uses an in-plane switching (IPS) type liquid crystal element that drives liquid crystal molecules in parallel to the substrate in a mode other than the VA type, that is, a horizontal electric field, and a polychromatic dye. It can be used in various ways such as a guest-host (GH) type liquid crystal element and a ferroelectric liquid crystal element. Furthermore, the composition of the present invention can be used not only for an electric writing method but also for a writing method using heat.

Hereinafter, the present invention will be described more specifically with reference to examples. The following examples are intended to illustrate the present invention without limiting the present invention.

The phase transition point of the compound of the present invention was measured as follows.
[Measurement of phase transition point]
A sample was placed on a hot plate of a melting point measuring apparatus equipped with a polarizing microscope, heated at 1 ° C./min, and the phase change was observed. In addition, using a differential scanning calorimeter (DSC 6220, manufactured by SII Nanotechnology Co., Ltd.), the temperature was raised at 1 ° C./min to confirm the phase change. C represents a crystalline phase, N represents a nematic phase, and I represents an isotropic phase.
The above physical property values were prepared by mixing 90% by mass of the liquid crystal composition “MLC-6608” manufactured by Merck & Co., Ltd. at a ratio of 10% by mass of the compound of the present invention, and using this liquid crystal composition. The measurement was performed by the following method.
[Measurement of liquid crystal clearing point (Tc)]
Place the liquid crystal composition on a hot plate of a melting point measuring apparatus equipped with a polarizing microscope, raise the temperature at 1 ° C./min, observe the phase change, measure the Tc of the liquid crystal composition, and extrapolate the measured value Was used to calculate the extrapolated value of Tc of the compound.
[Measurement of dielectric anisotropy (Δε)]
The liquid crystal composition was sealed between two glass cells (interval of 8 μm) subjected to horizontal alignment and vertical alignment treatment. A voltage of 100 mV was applied to this cell at 20 ° C., and the dielectric constant (∈⊥) in the minor axis direction of the liquid crystal molecules was measured using a horizontally aligned glass cell. Similarly, the dielectric constant (ε∥) in the major axis direction of liquid crystal molecules was measured using a vertically aligned glass cell. The dielectric anisotropy (Δε) of the compound was determined by obtaining Δε of the composition from the formula Δε = ε∥−ε⊥ and extrapolating.

[Reference Example 1] Synthesis of Compound (7-A)

In a 50 mL two-necked flask under an argon atmosphere, 4-bromo-3,3,4,4-tetrafluoro-1-butene (0.24 g, 1.20 mmol), trans-4- (4-propylcyclohexyl) benzaldehyde ( 0.66 g, 2.88 mmol) and THF (2.5 mL) were sequentially charged. After the reaction solution was cooled to -78 ° C, methyllithium (1.0 M ether solution, 2.6 mL) containing no lithium bromide was slowly added dropwise and stirred at -78 ° C for 2 hours. Then, after heating up a reaction solution to room temperature, saturated ammonium chloride aqueous solution was added and reaction was stopped. The reaction solution was extracted three times with ethyl acetate, and the collected organic layer was washed with a saturated aqueous sodium chloride solution and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 5: 1) to obtain the desired product, compound (7-A) (0.35 g, 1.06 mmol). Got. Yield 88%.
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = −128.06 (dd, J = 290.55, 20.78 Hz, 1F), -120.00 (dt, J = 290.55, 5.99 Hz, 1F), −114.09 (dd, J = 278.96 , 11.19 Hz, 1F), -113.06 (dd, J = 279.36,11.19Hz, 1F)

[Reference Example 2] Synthesis of Compound (8-A)

To a 50 mL eggplant-shaped flask, the compound (7-A) (0.24 g, 0.66 mmol) obtained in the same manner as above and methanol (6.6 mL) were added and cooled to -78 ° C. Thereafter, the mixture was vigorously stirred for 3 hours while flowing ozone into the reaction vessel. Thereafter, dimethyl sulfide (2.2 mL) was added to the reaction solution, and the reaction solution was allowed to warm to room temperature. After distilling off the solvent under reduced pressure, the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 5: 1), and the target product compound (8-A) (0.22 g, 0.61 mmol) was diastereomerized. Obtained as a mer mixture. Yield 92%.
Diastereomeric ratio = 72: 28.
Major isomer
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = −129.27 (d, J = 246.31 Hz, 1F), −128.60 (dd, J = 239.17, 12.03 Hz, 1F), −128.34 (d, J = 248.95 Hz, 1F), -120.90 to -120.30 (m, 1F).
Minor isomer
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = −136.87 (ddd, J = 244.06, 9.78, 4.89 Hz, 1F), −129.60 (d, J = 251.58 Hz, 1F), −126.43 (ddd, J = 232.02 , 17.30, 12.03 Hz, 1F), -125.12 (dt, J = 248.95, 9.78 Hz, 1F).

[Reference Example 3] Synthesis of Compound (10-A)

A 50 mL two-necked flask under an argon atmosphere was charged with the compound (8-A) (0.21 g, 0.58 mmol) obtained in the same manner as above and THF (1.3 mL). To this reaction solution, ethylmagnesium bromide (THF solution) (1.2 mol / L, 3.1 mL, 3.72 mmol) was added dropwise at room temperature, followed by stirring for 14 hours. The reaction was stopped with a saturated aqueous ammonium chloride solution, and the organic layer was separated. The aqueous layer was washed three times with diethyl ether, and the collected organic layer was washed with a saturated aqueous sodium chloride solution and then dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off under reduced pressure, and the resulting crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 3: 1) to obtain the desired product, compound (10-A) (0.19 g, 0.49 mmol) was obtained as a mixture of diastereomers. Yield 80%.
Diastereomeric ratio = 73: 27.
Major isomer
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = −128.10 (dd, J = 276.02, 19.55 Hz, 1F), −128.45 to −127.64 (m, 1F), −119.49 (dd, J = 275.64, 7.52 Hz, 1F), -117.36 (d, J = 267.18Hz, 1F).
Minor isomer
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = -130.20 to -129.38 (m, 1F), -130.00 to -129.28 (m, 1F), -122.01 (d, J = 273.39Hz, 1F), -118.07 ( d, J = 268.50Hz, 1F).

[Reference Example 4] Synthesis of Compound (11-A)

Compound (10-A) (0.890 g, 2.3 mmol) obtained in the same manner as above was dissolved in nitromethane (11.5 mL). To this reaction solution was added sodium 2-iodobenzenesulfonate (0.15 g, 0.46 mmol) and Oxone ^(R) (2KHSO ₅ · KHSO ₄ · K ₂ SO ₄ , 2.55 g, 4.14 mmol), and the reaction solution was brought to 110 ° C. Heated and allowed to stir for 24 hours. The reaction solution was cooled to room temperature and filtered, and then the solvent was distilled off under reduced pressure. The crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 10: 1) to obtain the desired product compound (11-A) (0.64 g, 1.68 mmol). Yield 73%.
¹⁹ F NMR (CDCl _3, CFCl ₃ ) δ = -122.45 (s, 2F), -112.56 (s, 2F).

[Example 1] Synthesis of compound (2-A)

A 100 mL two-necked flask under an argon atmosphere was charged with the compound (11-A) (2.83 g, 7.30 mmol) obtained as described above and THF (14.6 mL). To this reaction solution, vinylmagnesium chloride (THF solution, 2.1 mol / L, 15.0 mL, 31.5 mmol) was added dropwise at room temperature, and then heated to reflux for 14 hours. The reaction solution was cooled to room temperature and the reaction was quenched with saturated aqueous ammonium chloride. The reaction solution was extracted three times with diethyl ether, and the collected organic layer was washed with a saturated aqueous sodium chloride solution and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 3: 2) to give compound (2-A) (3.18 g, 7.19 mmol) as a diastereomeric mixture. Got as. The yield is 98%.
Diastereomeric ratio = 63:37.
Major isomer
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = -118.56 (d, J = 276.02Hz, 1F), -117.50 (d, J = 275.64Hz, 1F), -115.03 (d, J = 278.28 Hz, 1F) , -114.06 (dt, J = 278.28, 87.81 Hz, 1F).
Minor isomer
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = -118.16 to -117.42 (m, 1F), -115.95 to -115.20 (m, 1F), -115.28 to -114.51 (m, 1F),-113.83 to -113.06 (m, 1F),

[Example 2] Synthesis of compound (3-A)

A 50 mL two-necked flask under an argon atmosphere was charged with the compound (2-A) (0.438 g, 0.99 mmol) obtained in the same manner as above and methylene chloride. Subsequently, second generation Grubbs catalyst (0.084 g, 0.10 mmol) was added and stirred at reflux temperature for 2 days. After the reaction solution was cooled to room temperature, the reaction solution was passed through silica gel. The obtained filtrate was concentrated under reduced pressure, and purified again by silica gel column chromatography (hexane: ethyl acetate = 2: 1) to give compound (3-A) (0.347 g, 0.84 mmol) as a diastereomeric mixture. Got as. Yield 85%.
Diastereomeric ratio = 63:37.
Major isomer
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = -118.49 (dd, J = 263.61, 17.30Hz, 1F), -122.55 (dd, J = 265.87, 19.55HZ, 1F), -129.40 (dd, J = 266.24 , 14.67Hz, 1F), -130.73 (dd, J = 265.87, 16.92Hz, 1F).
Minor isomer
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = -132.43 to -131.70 (m, 1F), -130.27 to -129.56 (m, 1F), -124.09 to -123.39 (m, 1F), -117.49 to -116.77 (m, 1F).

[Example 3] Synthesis of compound (4-A)

In a 50 mL two-necked flask under an argon atmosphere, palladium carbon (10%, 0.090 g, 0.07 mmol), methanol (3.5 mL), and the compound (3-A) (0.295 g, 0.71 mmol) obtained in the same manner as above were added. Prepared. The inside of the reaction vessel was replaced with hydrogen and stirred at room temperature for 24 hours. Thereafter, the reaction solution was passed through silica gel, and the filtrate was concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 2: 1) to obtain compound (4-A) (0.292 g, 0.70 mmol) as a mixture of diastereomers. Yield 99%.
Diastereomeric ratio = 63:37.
Major isomer
¹⁹ F NMR (CDCl _3, CFCl ₃ ) δ = -130.65 (dd, J = 266.24, 16.92Hz, 1F), -129.22 (dd, J = 265.87, 19.55Hz, 1F), -123.45 (dd, J = 265.87 , 19.55Hz, 1F), -119.37 (dd, J = 268.50, 16.92Hz, 1F).
Minor isomer
¹⁹ F NMR (CDCl _3, CFCl ₃ ) δ = -135.12 to -133.40 (m, 1F), -132.40 to -131.28 (m, 1F), -116.80 to -115.47 (m, 1F), -112.83 to -111.58 (m, 1F).

Example 4 Synthesis of Compound (1-A)

A 50 mL two-necked flask under an argon atmosphere was charged with the compound (4-A) (0.12 g, 0.29 mmol) obtained as described above and pyridine (8.6 mL). Thereafter, phosphorus oxychloride (2.86 mmol, 0.27 mL) was added dropwise at room temperature, and the reaction solution was heated to 90 ° C. and stirred for 24 hours. Again, the reaction solution was cooled to room temperature, and saturated ammonium chloride aqueous solution was added to stop the reaction. The reaction solution was extracted with ethyl acetate three times. The collected organic layer was washed with a saturated aqueous sodium chloride solution and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 10: 1) to obtain the target product compound (1-A) (0.080 g, 0.21 mmol) Was obtained (yield 73%).
¹⁹ F NMR (CDCl _3, CFCl ₃ ) δ = -122.30 to -122.28 (m, 2F), -126.67 to -126.651 (m, 2F).
Phase transition temperature C 105.9 ° C N 109.9 ° C I
This compound had Tc of 79.4 ° C. and Δε of −6.21. Since Δε was negative, it was confirmed that the 5,5,6,6-tetrafluoro-1,3-cyclohexadiene-1,4-diyl group of the present invention is a ring structure with a negative function of Δε. did it.

[Reference Example 5] Synthesis of Compound (7-B)

Compound (7-B) was synthesized in the same manner as in Reference Example 1 except that 4-ethylbenzaldehyde was used instead of trans-4- (4-propylcyclohexyl) benzaldehyde in Reference Example 1 (yield 91 %).
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = -127.89 (dd, J = 273.39, 17.30Hz, 1F), -120.13 (dt, J = 273.39, 7.14Hz, 1F), -114.01 (dd, J = 263.61 , 12.03Hz, 1F), -113.04 (dd, J = 263.61, 12.41Hz, 1F).

[Reference Example 6] Synthesis of Compound (8-B)

Compound (8-B) was synthesized in the same manner as in Reference Example 2 using Compound (7-B) obtained in the same manner as described above (yield 71%).
Diastereomeric ratio = 96: 4.
Major isomer
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = -129.34 (dd, J = 246.31, 7.52Hz, 1F), -128.98 to -128.32 (m, 1F), -128.741 to -128.053 (m, 1F),- 120.57 (dt, J = 239.17, 9.78Hz, 1F).
Minor isomer
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = -137.25 to -136.00 (m, 1F), -128.98 to -128.32 (m, 1F), -127.00 to -124.82 (m, 2F).

[Reference Example 7] Synthesis of Compound (10-B)

Compound (10-B) was prepared in the same manner as in Reference Example 3 except that compound (8-B) obtained in the same manner as described above was used as the starting material, and 4-propylphenylmagnesium bromide was used instead of ethylmagnesium bromide. Synthesized (yield 95%).
Diastereomeric ratio = 95: 5.
Major isomer
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = -128.176 to -128.092 (m, 1F), -127.443 to -127.365 (m, 1F), -117.294 (s, 1F), -116.567 (s, 1F).
Minor isomer
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = -129.93 to -116.95 (m, 4F).

[Reference Example 8] Synthesis of Compound (11-B)

Compound (11-B) was synthesized in the same manner as in Reference Example 4 using compound (10-B) obtained in the same manner as described above (yield 67%).
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = -113.36 (d, J = 12.41, 4F).

[Example 5] Synthesis of compound (2-B)

The compound (2-B) was synthesized in the same manner as in Example 1 using the compound (11-B) obtained in the same manner as described above as the raw material (yield 97%).
Diastereomeric ratio = 74: 26.
Major isomer
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = -112.33 (d, J = 277.90, 2F), -113.75 (d, J = 280.53, 2F)
Minor isomer
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = -112.38 (d, J = 273.39, 2F), -113.98 (d, J = 273.39, 2F)

[Example 6] Synthesis of compound (3-B)

The compound (3-B) was synthesized in the same manner as in Example 2 using the compound (2-B) obtained in the same manner as described above as the raw material (yield 57%).
Diastereomeric ratio = 100: 00.
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = -120.95 to -120.84 (m, 2F), -126.41 to -125.55 (m, 2F)

[Example 7] Synthesis of compound (4-B)

The compound (4-B) was synthesized in the same manner as in Example 3 using the compound (3-B) obtained in the same manner as described above as the raw material (yield 74%).
¹ H NMR (CFCl ₃ ) δ1.00 (t, J = 7.59 Hz, 3H), 1.29 (t, J = 7.19 Hz, 3H), 1.70 (sext., J = 7.59 Hz, 2H), 2.32-2.38 ( m, 2H), 2.57-2.71 (m, 2H), 2.57-2.63 (m, 2H), 2.63 (q, J = 7.59Hz, 2H), 2.71 (q, J = 7.59Hz, 2H), 7.24-7.30 (m, 4H), 7.55-7.558 (m, 4H).

[Example 8] Synthesis of compound (1-B)

Compound (1-B) was synthesized in the same manner as in Example 4 using compound (4-B) obtained in the same manner as described above as the raw material (yield 100%).
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = -121.62 (s, 4F).
Phase transition temperature C 80.4 ° C I
Tc of this compound was 52.3 ° C. and Δε was −5.8.

Δε of the compound (1-B) having a 5,5,6,6-tetrafluoro-1,3-cyclohexadiene-1,4-diyl group which is a Δε negative function-expressing ring structure of the present invention, The Δε of the compound (C1) having a 2,3-difluorophenyl-1,4-diyl group, which is the most commonly used Δε negative function expression ring structure, was compared (Table 2).

Compared with the compound (C1), the compound (1-B) showed a larger negative Δε. From this result, the Δε-negative function-expressing ring structure of the present invention, which is a strong Δε-negative function-expressing ring structure, is a 5,5,6,6-tetrafluoro-1,3-cyclohexadiene-1,4-diyl group. It was confirmed that.

[Reference Example 9] Synthesis of Compound (7-C)

Compound (7-C) was synthesized in the same manner as in Reference Example 1 except that 4- (4-propylphenyl) benzaldehyde was used instead of trans-4- (4-propylcyclohexyl) benzaldehyde in Reference Example 1. (Yield 87%).
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = -128.42 (dd, J = 275.64, 17.30Hz, 1F), -119.53 (d, J = 275.64Hz, 1F), -114.40 (dd, J = 265.87, 12.41 Hz, 1F), -112.71 (dd, J = 263.61, 12.41Hz, 1F).

[Reference Example 10] Synthesis of Compound (8-C)

The compound (8-C) was synthesized in the same manner as in Reference Example 2 using the compound (7-C) obtained in the same manner as above as the raw material (yield 92%).
Diastereomeric ratio = 71: 29.
Major isomer
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = -118.10 (d, J = 236.53, 1F), -129.00 to -124.00 (m, 3H).
Minor isomer
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = -136.41 to -114.32 (m, 4F).

[Reference Example 11] Synthesis of Compound (10-C)

Compound (10-C) was synthesized in the same manner as in Reference Example 3 using compound (8-C) obtained in the same manner as described above (yield 86%).
Diastereomeric ratio = 92: 8.
Major isomer
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = -117.10 (d, J = 275.64, 1F), -119.59 to -118.85 (m, 1F), -127.73 to -127.14 (m, 1F), -127.94 to- 127.88 (m, 1F).
Minor isomer
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = -118.124 to -117.391 (m, 1F), -121.69 (d, J = 273.39, 1F), -130.110 to -129.31 (m, 2F).

[Reference Example 12] Synthesis of Compound (11-C)

The compound (11-C) was synthesized in the same manner as in Reference Example 4 using the compound (10-C) obtained in the same manner as described above (yield 81%).
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = -122.74 (s, 2F), -112.28 (s, 2F).

Example 9 Synthesis of Compound (2-C) Compound (2-C) was synthesized in the same manner as in Example 1 except that compound (11-C) obtained in the same manner as described above was used as a raw material. Rate 57%).

Diastereomeric ratio = 55:45.
Major isomer
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = -118.44 (d, J = 278.28Hz, 1F), -117.41 (d, J = 275.64Hz, 1F), -114.80 (d, J = 278.28Hz, 1F) , -114.172 to -113.420 (m, 1F).
Minor isomer
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = -117.69 (dd, J = 287.68, 9.78Hz, 1F), -115.65 (dd, J = 280.05, 7.14Hz, 1F), -114.64 (dd, J = 280.53 , 9.78Hz, 1F), -113.35 (dd, J = 278.28, 7.14, 1F)

[Example 10] Synthesis of compound (3-C)

Compound (3-C) (yield 70%) was obtained in the same manner as in Example 2, using compound (2-C) obtained in the same manner as described above as the starting material.
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = -130.44 (dd, J = 268.50, 19.55Hz, 1F), -128.97 (dd, J = 266.24, 19.55Hz, 1F), -123.56 (dd, J = 268.50 , 19.55Hz, 1F), -119.53 (dd, J = 265.87, 16.92Hz, 1F).

[Example 11] Synthesis of compound (4-C)

The compound (4-C) was synthesized in the same manner as in Example 3 using the compound (3-C) obtained in the same manner as described above (yield 89%).
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = -135.17 to -112.86 (m, 4F).

[Example 12] Synthesis of compound (1-C)

Compound (1-C) was synthesized in the same manner as in Example 4 using Compound (4-C) obtained in the same manner as described above as the starting material (yield 46%).
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = -122.24 to -122.23 (m, 2F), -126.58 to -126.57 (m, 2F).
Phase transition temperature C 105.9 ° C N 109.9 ° C I
Tc of this compound was 89.4 ° C., and Δε was −6.2.

[Reference Example 13] Synthesis of Compound (15-A)

Under an argon atmosphere, THF (60 mL) and dimethyl tetrafluorosuccinate (6.68 g, 30 mmol) were charged into a 300 mL two-necked flask. After the reaction solution was cooled to −78 ° C., 4- (trans-4-propylcyclohexyl) phenylmagnesium bromide (1.0 M THF solution, 60 mL, 60 mmol) was slowly added dropwise. After stirring overnight at this temperature, an aqueous ammonium chloride solution was added to stop the reaction. The reaction solution was extracted 3 times with ethyl acetate, and then the organic layer was dried over anhydrous sodium sulfate. Filtration was performed and the filtrate was concentrated under reduced pressure. Thereafter, silica gel column chromatography was performed to obtain the target product compound (15-A) (10.0 g, 25.8 mmol) (yield 86%).
¹⁹ F NMR (CDCl ₃ CFCl ₃ ) δ = -121.09 (t, J = 4.89 Hz, 2F), -113.37 (t, J = 4.89 Hz, 2F).

[Example 13] Synthesis of compound (2a-A)

Under an argon atmosphere, a 300 mL two-necked flask was charged with diethyl ether (150 mL) and the compound (15-A) (5.83 g, 15 mmol) obtained in the same manner as described above. Subsequently, vinylmagnesium chloride (2.1 M THF solution, 26 mL, 54 mmol) was added dropwise at room temperature. The reaction solution was heated to 50 ° C. and stirred as it was overnight. The reaction solution was added to an aqueous ammonium chloride solution to stop the reaction, and then extracted three times with diethyl ether. To the collected organic layer, anhydrous sodium sulfate was added and dried, followed by filtration. After the filtrate was concentrated under reduced pressure, the target product compound (2a-A) (2.51 g, 5.70 mmol) (yield 38%) was obtained by silica gel column chromatography.
¹⁹ F NMR (CDCl ₃ CFCl ₃ ) δ = -116.39 (m, 2F), -114.16 (q, J = 265.41Hz, 2F);

[Example 14] Synthesis of compound (3a-A)

In a 100 mL two-necked flask under an argon atmosphere, the first generation Grubbs catalyst (0.66 g, 0.8 mmol), methylene chloride (55 mL), and the compound (2a-A) (3.52 g, 8 mmol) obtained in the same manner as above were added. Prepared. After stirring for 40 hours, the reaction solution was passed through silica gel. The obtained filtrate is concentrated under reduced pressure and then purified by silica gel column chromatography to obtain the desired product compound (3a-A) (2.34 g, 5.68 mmol) as a single diastereomer. (Yield 71%).
¹⁹ F NMR (CDCl ₃ CFCl ₃ ) δ = -132.10 (dd, J = 264.18, 19.55Hz, 1F), -130.73 (dd, J = 264.18, 19.55Hz, 1F), -122.24 (dd, J = 264.18, 17.30Hz, 1F), -166.02 (ddd, J = 264.18, 19.55, 7.14Hz, 1F).

[Example 15] Synthesis of compound (4a-A)

In a 100 mL two-necked flask under an argon atmosphere, palladium / carbon (10%, 0.85 g, 0.8 mmol), methanol (40 mL), and the compound (3a-A) (3.30 g, 8 mmol) obtained in the same manner as described above were used. ). After replacing argon in the reaction system with hydrogen, the mixture was stirred at room temperature for 2 days. The reaction solution was passed through silica gel, and the obtained filtrate was concentrated under reduced pressure to give compound (4a-A) (3.33 g, 8 mmol) as a single diastereomer (yield 100%).
Compound (4a-A) is the same compound as compound (4-A) of Example 2, but the product is obtained as a single diastereomer by using the production method of this example. be able to.
¹⁹ F NMR (CDCl ₃ CFCl ₃ ) δ = -134.95 (d, J = 246.31Hz, 1F), -132.48 (d, J = 251.20Hz, 1F), -117.68 (d, J = 258.72Hz, 1F), -113.65 (d, J = 270.76Hz, 1F).

[Reference Example 14] Synthesis of Compound (15-B)

Compound (15-B) was synthesized in the same manner as in Reference Example 13 except that 4-propylphenylmagnesium bromide was used instead of 4- (trans-4-propylcyclohexyl) phenylmagnesium bromide in Reference Example 13. (Yield 87%).
¹⁹ F NMR (CDCl ₃ CFCl ₃ ) δ = -121.08 (s, 2F), -113.35 (s, 2F).

[Example 16] Synthesis of compound (2a-B)

The compound (2a-B) was synthesized in the same manner as in Example 13 using the compound (15-B) obtained in the same manner as described above as the raw material (yield 40%).
¹⁹ F NMR (CDCl ₃ CFCl ₃ ) δ = -116.38 (d, J = 14.67 Hz, 2F), -114.14 (q, J = 265.14 Hz, 2F).

[Example 17] Synthesis of compound (3a-B)

Compound (3a-B) was synthesized in the same manner as in Example 14 using compound (2a-B) obtained in the same manner as described above as the starting material (yield 75%).
¹⁹ F NMR (CDCl ₃ CFCl ₃ ) δ = -132.08 (dd, J = 265.39, 19.55Hz, 1F), -130.64 (dd, J = 265.39, 17.11Hz, 1F), -122.25 (dd, J = 265.39, 17.11Hz, 1F), -116.11 (ddd, J = 265.39, 19.55, 4.89Hz, 1F).

[Example 18] Synthesis of compound (4a-B)

Compound (4a-B) was synthesized in the same manner as in Example 15 using compound (3a-B) obtained in the same manner as described above as the starting material (yield 99%).
¹⁹ F NMR (CDCl ₃ CFCl ₃ ) δ = -135.05 (d, J = 276.02 Hz, 1F), -132.63 (d, J = 258.72Hz, 1F), -117.79 (d, J = 258.72Hz, 1F), -113.74 (d, J = 273.02 Hz, 1F).

[Example 19] Synthesis of compound (1a-B)

(1a-B)
Compound (1a-B) was synthesized in the same manner as in Example 4 using compound (4a-B) obtained in the same manner as described above as the starting material (yield 83%).
¹⁹ F NMR (CDCl ₃ CFCl ₃ ) δ = -126.63 (d, J = 4.89 Hz, 2F), -123.30 (d, J = 7.52 Hz, 2F).
Tc of this compound was −93.6 ° C., and Δε was −5.8.

[Reference Example 15] Synthesis of Compound (18-A)

(18-A)
Compound (7-A) (2.22 g, 6.19 mmol) obtained in the same manner as in Reference Example 1 was dissolved in acetonitrile, and sodium 2-iodobenzenesulfonate (5 mol%) was added to this reaction solution as in Reference Example 4. ) And Oxone ^(R) (2KHSO ₅ · KHSO ₄ · K ₂ SO ₄ , 0.9 eq) were added, and the reaction solution was heated to 85 ° C. and reacted for 18 hours. Thereafter, cooling, filtration and purification were performed to obtain the target compound (18-A) (1.83 g, 5.13 mmol). Yield 83%.
¹ H NMR (CDCl ₃ ) δ = 0.91 (t, J = 7.19 Hz, 3H), 1.02 to 1.12 (m, 2H), 1.20 to 1.53 (m, 7H), 1.88 to 1.91 (m, 4H), 2.56 ( tt, J = 11.79, 3.20 Hz, 1H), 5.74 (d, J = 11.40 Hz 1H), 5.92 (dt, J = 17.19, 2.20 Hz, 1H), 6.13 (ddt, 17.19, 11.40, 10.49 Hz, 1H) , 7.35 (d, J = 8.79 Hz, 2H), 8.03 (d, J = 7.99 Hz 2H);
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = -114.69 (s, 2F), -113.97 (d, J = 10.49 Hz, 2F);
HRMS (FAB ⁺ ) calcd for C ₂₀ H ₂₅ F ₄ O (M ⁺ H): 357.1842, Found 357.1833.

[Reference Example 16] Synthesis of Compound (19-A)

(19-A)
Compound (19-A) (1.77 g, 4.70 mmol) was synthesized in the same manner as in Reference Example 2 using compound (18-A) (1.83 g, 5.13 mmol) obtained in the same manner as described above (yield) 92%).

[Example 20] Synthesis of compound (2b-A)

(2b-A)
In the same manner as in Example 1, vinylmagnesium chloride (diethyl ether solution, 4.0 eq) was added dropwise to the reaction solution charged with the compound (19-A) (1.77 g, 4.70 mmol) obtained in the same manner as above and diethyl ether. And then heated to reflux for 2 hours. Thereafter, cooling, filtration, and purification were performed to synthesize the target compound (2b-A) (0.68 g, 1.64 mmol) (yield 35%).
Diastereomer Mixture (dr = 62: 38);
¹ H NMR (CDCl ₃ ) δ = 0.90 (t, J = 7.19 Hz, 3H), 1.00 to 1.15 (m, 2H), 1.18 to 1.52 (m, 8 H), 1.75 to 1.95 (m, 5H), 2.50 (tt, J = 11.79, 3.20 Hz, 1H), 3.62 to 3.73 (m, 1H for mixture), 4.22 to 4.24 (m, 1H for minor isomer), 4.42 to 4.45 (m, 1H for major isomer), 4.55 to 4.65 (m, 1H for mixture), 5.35 to 5.55 (m, 4H for mixture), 5.88 to 6.02 (m, 1H for mixture), 6.55 to 6.68 (m, 1H for mixture), 7.24 (d, J = 7.99 Hz , 2H), 7.50 (d, J = 7.99 Hz, 2H);
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = -124.32 (ddd, J = 268.12, 19.55, 7.52 Hz, 1F for major isomer), -119.70 (dd, J = 278.28, 8.65 Hz, 1F for major isomer), -117.59 (dd, J = 278.28, 7.14 Hz, 1F for major isomer), -114.69 (dd, J = 275.64, 7.14 Hz, 1F for major isomer), -123.36 (ddd, J = 268.50, 16.92, 7.14 Hz, 1F for minor isomer),-118.18 (d, J = 278.28 Hz, 1F for minor isomer),-117.20 (dd, J = 278.28, 7.14 Hz, 1F for minor isomer),-113.16 (d, J = 275.64 Hz, 1F for minor isomer);
HRMS (EI ⁺ ) calcd for C ₂₃ H ₃₀ F ₄ O ₂ (M ⁺ ): 414.2182, Found 414.2192.

[Example 21] Synthesis of compound (3b-A)

(3b-A)
To a methylene chloride solution (17 mL) of Grubbs second generation catalyst (0.067 g, 0.079 mmol) at room temperature was added compound (2b-A) (0.68 g, 1.64 mmol) obtained in the same manner as described above, and the mixture was refluxed. And stirred for 24 hours. The reaction solution was passed through silica gel with ethyl acetate, and the resulting solution was concentrated under reduced pressure. Finally, the crude product was subjected to silica gel column chromatography to obtain compound (3b-A) in a yield of 87% (0.55 g, 1.42 mmol).
Diastereomer Mixture: ca. 1: 1
¹ H NMR (CDCl ₃ ) δ = 0.90 (t, J = 7.39 Hz, 3H), 0.96 to 1.05 (m, 2H), 1.18 to 1.49 (m, 7H), 1.84 to 1.91 (m, 4H), 2.44 to 2.52 (m, 1H), [2.23 (d, J = 8.79 Hz) and 2.33 (d, J = 8.79 Hz), 1H], 2.45 to 2.51 (m, 1H), [2.60 (d, J = 4.40 Hz) and 2.70 (s), 1H], 4.61-4,69 (m, 1H), 5.87-5.96 (m, 2H), 7.17 (d, J = 7.79 Hz, 2H), 7.35 (d, J = 7.79 Hz, 2H);
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = -137.32 (dt, J = 270.76, 14.67 Hz, 1F) and -129.54 (d, J = 260.98 Hz, 1F)], [-130.87 (d, J = 256.47 Hz, 1F) and -127.27 (d, J = 9.78 Hz, 1F)], [-129.71 (dd, J = 260.98, 9.78 Hz, 1F) and -127.14 (d, J = 7.52 Hz, 1F)], [ -118.24 (dd, J = 273.39, 12.03 Hz, 1F) and -124.57 (d, J = 263.61 Hz, 1F)];
HRMS (FAB ⁺ ) calcd for C ₂₁ H ₂₆ F ₄ O ₂ Na (M + Na): 409.1767, Found 409.1776.

[Example 22] Synthesis of compound (4b-A)

(4b-A)
Compound (3b-A) (0.55 g, 1.42 mmol) obtained in the same manner as described above was added at room temperature in the presence of palladium / carbon (10%, 0.15 g, 0.14 mmol) in a solvent of methanol (16 mL). After the reaction system was filled with hydrogen, the mixture was stirred at room temperature for 2 days. The reaction mixture was passed through silica gel with ethyl acetate, and the resulting solution was concentrated under reduced pressure to obtain the target product compound (4b-A) in a yield of 96%. (0.53g, 1.36mmol)
Less Polar
¹ H NMR (CDCl ₃ ) δ = 0.90 (t, J = 7.39 Hz, 3H), 1.00 to 1.10 (m, 2H), 1.18 to 1.49 (m, 7H), 1.81 to 1.98 (m, 6H), 2.34 to 2.39 (m, 2H), 2.44 to 2.51 (m, 2H), 2.74 to 2.81 (m, 1H) 4.27 (brs, 1H), 7.22 (d, J = 8.39 Hz, 2H), 7.50 (d, J = 8.39 Hz, 2H);
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = -135.22 to -134.51 (m, 1F), -127.50 (d, J = 268.50 Hz, 1F), -114.98 to -114.31 (m, 2F);
HRMS (FAB ⁺ ) calcd for C ₂₁ H ₂₈ F ₄ O ₂ (M ⁺ ): 388.2025, Found 388.2031.
More Polar
¹ H NMR δ = 0.81 (t, J = 7.19 Hz, 3H), 1.00 to 1.10 (m, 2H), 1.18 to 1.49 (m, 7H), 1.80 to 1.92 (m, 4H), 1.97 to 2.17 (m, 4H), 2.27 to 2.34 (m, 1H), 2.45 to 2.52 (m, 2H), 3.90 to 4.00 (m, 1H), 7.15 (d, J = 8.39 Hz, 2H), 7.43 (d, J = 7.59 Hz , 2H);
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = -136.18 (dm, J = 269.62 Hz, 1F), -128.85 (dtd, J = 257.60, 18.43, 9.40 Hz, 1F), -127.27 (dm, J = 257.60 Hz, 1F),-116.30 (d, J = 269.62 Hz, 1F);
HRMS (FAB ⁺ ) calcd for C ₂₁ H ₂₈ F ₄ O ₂ (M ⁺ ): 388.2025, Found 388.2030.

[Reference Example 17] Synthesis of Compound (16-A)

(16-A)

[Selective protection of secondary alcohol]

Compound (4b-A) (0.53 g, 1.36 mmol), imidazole (0.19 g, 2.79 mmol), trifluoromethanesulfonic acid obtained as described above in a mixed solvent of methylene chloride (14 mL) and DMF (1.4 mL) tert-Butyldimethylsilyl (TBSOTf) (1.0 mL, 4.34 mmol) was added, and the mixture was stirred for 1.5 hours under reflux conditions. Then, after adding water, extraction was performed 3 times using methylene chloride. The organic layer was dried using anhydrous sodium sulfate and filtered, and the resulting filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography to obtain a monosilyl ether in which only the secondary hydroxyl group was selectively protected with tert-butyldimethylsilyl (TBS) in a yield of 77%. (0.53g, 1.05mmol)
¹ H NMR (CDCl ₃ ) δ = 0.17 (s, 3H), 0.18 (s, 3H), 0.93 (t, J = 7.19 Hz, 3H), 0.97 (s, 9H), 1.06 to 1.13 (m, 2H) , 1.21 to 1.53 (m, 7H), 1.88 to 1.94 (m, 6H), 2.21 to 2.31 (m, 2H), 2.51 (tt, J = 12.20, 3.20 Hz, 1H), 2.57 (brs, 1H), 4.00 ~ 4.12 (m, 1H), 7.26 (d, J = 8.79 Hz, 2H), 7.48 (d, J = 7.59 Hz, 2H);
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = -136.58 (d, J = 272.26 Hz, 1F),-129.21 (dm, J = 253.83 Hz, 1F),-126.62 (d, J = 253.83 Hz, 1F) , -116.56 (d, J = 272.26 Hz, 1F);
HRMS (FAB ⁺ ) calcd for C ₂₇ H ₄₃ F ₄ O ₂ Si (M + H): 503.2968 Found 503.2972.

[Acetyl protection of tertiary alcohol]

In a methylene chloride (10 mL) solvent, TBS-protected monosilyl ether (0.53 g, 1.05 mmol) obtained in the same manner as above, DMAP (0.43 g, 3.52 mmol), acetic anhydride (0.44 mL, 4.65 mmol) were added, Stir for 1 day under reflux conditions. Then, water was added and extraction was performed 3 times using methylene chloride. The obtained organic layer was dried using anhydrous sodium sulfate and then filtered. After the filtrate was concentrated under reduced pressure conditions, the crude product was isolated and purified by silica gel column chromatography to obtain a cyclohexane derivative (yield 82%, 0.47 g, 0.86 mmol).
¹ H NMR (CDCl ₃ ) δ = 0.14 (s, 3H), 0.15 (s, 3H), 0.90 (t, J = 7.39 Hz, 3H), 0.94 (s, 9H), 0.98 to 1.09 (m, 2H) , 1.20 to 1.48 (m, 7H), 1.84 to 1.91 (m, 6H), 2.16 (s, 3H), 2.30 to 2.37 (m, 1H), 2.43 to 2.49 (m, 1H), 3.09 to 3.13 (m, 1H), 3.95 to 4.04 (m, 1H), 7.21 (d, J = 7.59 Hz, 2H), 7.30 (d, J = 7.59 Hz, 2H);
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = -135.10 (dm, J = 269.63 Hz, 1F), -130.86 (dm, J = 253.83 Hz, 1F), -125.79 (dm, J = 253.83 Hz, 1F) , -119.21 (dm, J = 269.63 Hz, 1F);
HRMS (FAB ⁺ ) calcd for C ₂₉ H ₄₄ F ₄ O ₃ Si (M ⁺ ): 544.2996, Found 544.2991.

[Deprotection of TBS group]

TBAF (1.0 M in THF, 1.7 mL, 1.7 mmol) was added dropwise to a cyclohexane derivative (0.47 g, 0.86 mmol) obtained in the same manner as above in a THF (9 mL) solvent, and the mixture was stirred at room temperature for 22 hours. Then, water was added and extraction was performed 3 times using diethyl ether. The obtained organic layer was dried using anhydrous sodium sulfate and then filtered. After the filtrate was concentrated under reduced pressure conditions, the crude product was isolated and purified by silica gel column chromatography to obtain a cyclohexanol derivative. (Yield 86%, 0.32 g, 0.74 mmol)
HRMS (FAB ⁺ ) calcd for C ₂₃ H ₃₀ F ₄ O ₃ (M ⁺ ): 430.2131, Found 430.2138.
More Polar
¹ H NMR (CDCl ₃ ) δ = 0.86 (t, J = 7.19 Hz, 3H), 0.98 to 1.08 (m, 2H), 1.17 to 1.47 (m, 7H), 1.73 to 1.80 (m, 1H), 1.84 1.90 (m, 4H), 2.10 to 2.14 (m, 2H), 2.16 (s, 3H), 2.32 to 2.40 (m, 1H), 2.43 to 2.49 (m, 1H), 3.12 to 3.19 (m, 1H), 4.01 ~ 4.12 (m, 1H), 7.21 (d, J = 8.39 Hz, 2H), 7.30 (d, J = 8.39 Hz, 2H);
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = -135.37 (dtd, J = 275.65, 16.92, 4.89 Hz, 1F), -131.05 (dtd, J = 251.20, 16.92, 4.89 Hz, 1F), -127.41 (dt , J = 251.20, 16.92 Hz, 1F), -119.49 (dt, J = 275.65, 16.92 Hz, 1F);
Less Polar
¹ H NMR (CDCl ₃ ) δ = 0.90 (t, J = 6.99 Hz, 3H), 0.99 to 1.09 (m, 2H), 1.18 to 1.92 (m, 7H), 1.85 to 1.92 (m, 4H), 1.96 to 2.00 (m, 1H), 2.14 (s, 3H), 2.44 to 2.50 (m, 3H), 2.83 to 3.01 (m, 2H), 4.24 (brs, 1H), 7.22 (d, J = 8.59 Hz, 2H) , 7.34 (d, J = 8.59 Hz, 2H);
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = -134.00 (d, J = 268.88 Hz, 1F), -127.51 (dt, J = 268.88, 14.67 Hz, 1F), -117.38 (d, J = 268.88 Hz, 1F), -116.24 (d, J = 268.88 Hz, 1F);

[IBS oxidation]

2-Iodobenzenesulfonic acid (IBS) precursor 2-iodo, as in Reference Example 4, with respect to the cyclohexanol derivative (0.32 g, 0.74 mmol) obtained as described above in a nitromethane (4 mL) solvent. Sodium benzenesulfonate (0.026 g, 0.085 mol) and Oxone ^(R) (2KHSO ₅ · KHSO ₄ · K ₂ SO ₄ , 0.9 eq) (0.68 g, 1.11 mol) were added, and the mixture was stirred at 110 ° C. for 11 hours. The reaction solution was passed through silica gel with ethyl acetate. After concentrating the obtained solution under reduced pressure conditions, the crude product was purified by silica gel column chromatography to obtain compound (16-A) (72% yield, 0.23 g, 0.53 mmol).
¹ H NMR (CDCl ₃ ) δ = 0.91 (t, J = 6.99 Hz, 3H), 1.00 to 1.10 (m, 2H), 1.20 to 1.50 (m, 7H), 1.86 to 1.92 (m, 4H), 2.17 ( s, 3H), 2.46 to 2.52 (m, 1H), 2.59 to 2.74 (m, 2H), 2.81 to 2.90 (m, 1H), 3.38 to 3.41 (m, 1H), 7.25 (d, J = 7.99 Hz, 2H), 7.32 (d, J = 7.99 Hz, 2H);
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = -136.00 (dm, J = 274.52 Hz, 1F), -131.29 (dm, J = 270.95 Hz, 1F), -121.30 (dd, J = 270.95, 14.29 Hz, 1F), -113.51 (dd, J = 274.52, 14.66 Hz, 1F);
HRMS (FAB ⁺ ) calcd for C ₂₃ H ₂₈ F ₄ O ₃ Na (M ⁺ Na): 451.1872, Found 451.1875.

[Reference Example 18] Synthesis of Compound (17-A)

(17-A)
In a DMF solvent, dimethyl sulfate (0.2 mL, 2.11 mmol) and potassium carbonate (1.14 g, 2.19 mmol) are added to the compound (16-A) (0.23 g, 0.53 mmol) obtained in the same manner as described above. Stir at room temperature for 17 hours. Then, water was added and extraction was performed 3 times using diethyl ether. The organic layer was dried using anhydrous sodium sulfate, filtered, and the obtained filtrate was concentrated under reduced pressure. The crude product was purified using silica gel column chromatography to obtain compound (17-A).
HRMS (FAB ⁺ ) calcd for C ₂₄ H ₃₁ F ₄ O ₃ (M + H): 443.2209, Found 443.2211.

[Example 23] Synthesis of compound (1b-A)

(1b-A)

To the crude product (reaction mixture) of the compound (17-A) obtained in the same manner as described above in methanol (10 mL), potassium carbonate (1.14 g, 8.24 mmol) was added and stirred at room temperature for 15 hours. . Then, water was added and methanol was distilled off under reduced pressure conditions. The resulting solution was extracted three times with diethyl ether. The organic layer was dried using anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure. After isolation and purification using silica gel column chromatography, phosphorus oxychloride (0.12 mL, 1.29 mmol) was added dropwise to the crude deacetylated product (reaction mixture) in pyridine (3 mL) solvent. And stirred at 90 ° C. for 10 hours. Water and 10% hydrochloric acid were added, and extraction was performed 3 times using diethyl ether. The organic layer was dried using anhydrous sodium sulfate and then filtered, and the filtrate was concentrated under reduced pressure to obtain 43 mg of a crude product. ¹⁹ F NMR confirmed the formation of 0.073 mmol of the desired compound (1b-A) in the crude product.
¹ H NMR (CDCl ₃ ) δ = 0.91 (t, J = 6.99 Hz, 3 H), 1.00 to 1.09 (m, 2H), 1.22 to 1.50 (m, 7H), 1.86 to 1.91 (m, 4H), 2.45 To 2.52 (m, 1H), 3.78 (s, 3H), 5.33 (d, J = 6.99 Hz, 1H), 6.31 (d, J = 6.99 Hz, 1H), 7.21 to 7.43 (m, 4H);
¹⁹ F NMR (CDCl ₃ , CFCl ₃ ) δ = -121.02 (s, 2F), -130.75 (s, 2F);
HRMS (FAB ⁺ ) calcd for C ₂₂ H ₂₆ F ₄ O (M +): 382.1920, Found 382.1913.

Based on the description in the examples and detailed description of the invention, the following compounds can be prepared. The compounds described in the examples are also included in the following compounds.
In the following formulae, -Ph (2F, 3F)-represents a 2,3-difluoro-1,4-phenylene group. -Cy-, -Ph-, -Py (2)-and -Py (3)-have the same meaning as described above.

Examples of the bicyclic compound (m + n + o + p + q + r = 1) include the following.
C ₃ H ₇ -Ph-Cd-C ₂ H ₅ compound (1a-B)
C ₄ H ₉ -Ph-CF ₂ O-Cd-OC ₂ H ₅
C ₅ H ₁₁ -Ph-Cd-OC ₂ H ₅
C ₃ H ₇ -Cy-Cd-C ₂ H ₅
CH ₂ = CH-Cy-Cd-C ₂ H ₅
C ₂ H ₅ -Py (2) -Cd-C ₂ H ₅
C ₃ H ₇ -Py (2) -Cd-OC ₂ H ₅
C ₃ H ₇ -Cd-Py (3) -C ₂ H ₅
C ₃ H ₇ -Cd-Py (3) -C ₂ H ₄ CH = CH ₂
CH ₃ -Cd-Ph-C ₅ H ₁₁
CH ₃ O-Cd-Ph-C ₄ H ₉
C ₃ H ₇ -Cd-Ph (2F, 3F) -OC ₂ H ₅
CH ₃ O-Cd-Cy-C ₅ H ₁₁
C ₃ H ₇ -Cd-Cy-C ₂ H ₅
C ₃ H ₇ -Cd-Py (2) -C ₂ H ₅
C ₄ H ₉ -Cd-Py (2) -C ₂ H ₄ CH = CH ₂
C ₃ H ₇ -Py (3) -Cd-C ₂ H ₅
CH ₂ = CHC ₂ H ₄ -Py (3) -Cd-OC ₂ H ₅

Examples of the tricyclic compound (m + n + o + p + q + r = 2) include the following.
C ₂ H ₅ -Ph-Ph-Cd-OC ₂ H ₅
C ₃ H ₇ -Ph-Ph-Cd-C ₂ H ₅ compound (1-C)
C ₄ H ₉ -Ph-Ph-CH ₂ O-Cd-OC ₂ H ₅
C ₅ H ₁₁ -Ph-C≡C-Ph-Cd-OC ₂ H ₅
C ₅ H ₁₁ -Ph-Ph (2F, 3F) -Cd-OC ₂ H ₅
C ₃ H ₇ -Cy-Ph-Cd-OCH ₃    Compound (1b-A)
C ₃ H ₇ -Cy-Ph-Cd-OC ₂ H ₅
C ₃ H ₇ -Cy-Ph-Cd-C ₂ H ₅ compound (1-A)
C ₃ H ₇ -Cy-Ph-CF ₂ O-Cd-C ₃ H _{7
C 4 H 9 -Cy-CH 2} CH 2 -Ph-Cd-C 2 H 5
CH = CHC ₂ H ₄ -Cy-Ph-Cd-C ₂ H ₅
C ₅ H ₁₁ -Cy-Ph (2F, 3F) -Cd-OC ₂ H ₅
C ₂ H ₅ -Py (2) -Ph-Cd-OCH ₃
C ₃ H ₇ -Py (2) -Ph-Cd-C ₂ H ₅
C ₄ H ₉ -Py (3) -Ph-Cd-OC ₂ H ₅
C ₅ H ₁₁ -Py (3) -Ph-Cd-CH = CH ₂

CH ₃ -Ph-Cy-Cd-C ₃ H ₇
C ₂ H ₅ -Ph-Cy-Cd-OCH ₃
C ₃ H ₇ -Cy-Cy-Cd-OC ₂ H ₅
CH = CHC ₂ H ₄ -Cy-Cy-Cd-OC ₂ H ₅
C ₅ H ₁₁ -Py (2) -Cy-Cd-C ₃ H ₇
CH ₃ -Py (2) -Cy-Cd-OCH ₃
CH ₂ = CH-Py (3) -Cy-Cd-OC ₂ H _{5
C 3 H 7 -Py (3)} -Cy-Cd-C 3 H 7
C ₄ H ₉ -Ph-Py (2) -Cd-OC ₂ H ₅
C ₅ H ₁₁ -Ph-Py (2) -Cd-OCH ₃
CH ₃ -Ph-Py (3) -Cd-OC ₂ H ₅
C ₂ H ₅ -Ph-Py (3) -Cd-OC ₂ H ₅
C ₃ H ₇ -Cy-Py (2) -Cd-OCH ₃
CH = CHC ₂ H ₄ -Cy-Py (2) -Cd-OC ₂ H ₅
C ₅ H ₁₁ -Cy-Py (3) -Cd-OCH ₃
CH ₃ -Cy-Py (3) -Cd-C ₂ H ₅

C ₂ H ₅ -Ph-Cd-Ph-C ₃ H ₇ compound (1-B)
C ₂ H ₅ -Ph-CH ₂ O-Cd-Ph-C ₄ H ₉
C ₂ H ₅ -Ph-Cd-OCH ₂ -Ph-C ₄ H ₉
C ₂ H ₅ -Ph-Cd-OCF ₂ -Ph-C ₅ H ₁₁
C ₂ H ₅ -Ph-Cd-Ph (2F, 3F) -C ₅ H ₁₁
C ₃ H ₇ -Ph-Cd-Ph-C ₂ H ₄ CH = CH ₂
C ₄ H ₉ -Ph-Cd-Cy-C ₅ H ₁₁
C ₅ H ₁₁ -Ph-Cd-Cy-OCH ₃
C ₅ H ₁₁ -Ph-CH ₂ O-Cd-Cy-CH ₃
CH ₃ -Ph (2F, 3F) -Cd-Py (2) -C ₂ H ₅
C ₂ H ₅ -Ph-Cd-Py (2) -C ₃ H ₇
C ₃ H ₇ -Ph-Cd-Py (3) -C ₄ H ₉
C ₄ H ₉ -Ph-Cd-Py (3) -OCH ₃
C ₅ H ₁₁ -Cy-Cd-Cy-C ₂ H ₅
CH ₃ -Cy-Cd-Cy-C ₂ H ₄ CH = CH ₂
C ₂ H ₅ -Cy-Cd-Py (2) -C ₅ H ₁₁
C ₃ H ₇ -Cy-Cd-Py (2) -CH _{3
C 4 H 9 -Cy-Cd-} Py (3) -OC 2 H 5
C ₅ H ₁₁ -Cy-Cd-Py (3) -C ₃ H ₇

Examples of the tetracyclic compound (m + n + o + p + q + r = 3) include the following.
C ₃ H ₇ -Ph-Ph-Ph-Cd-OC ₂ H _{5
C 3 H 7 -Ph-Ph-} Ph (2F, 3F) -Cd-OCH 3
CH = CHC ₂ H ₄ -Ph-Ph-Ph-Cd-OCH ₃
C ₅ H ₁₁ -Cy-Ph-Ph-Cd-OC ₂ H ₅
CH ₃ -Cy-Ph-Ph (2F, 3F) -Cd-OC ₂ H ₅
CH ₃ -Ph-Ph-Ph-Cd-OCH ₃
C ₂ H ₅ -Py (2) -Ph-Ph-Cd-C ₂ H ₅
C ₃ H ₇ -Py (2) -Ph-Ph-Cd-OC ₂ H ₅
C ₄ H ₉ -Py (3) -Ph-Ph-Cd-OC ₂ H ₅
C ₅ H ₁₁ -Py (2) -Ph-Ph-Cd-C ₃ H ₇
CH ₃ -Ph-Cy-Ph-Cd-OCH _{3
C 2 H 5 -Ph-Cy-} Ph-Cd-C 2 H 5
C ₃ H ₇ -Ph-Py (2) -Ph-Cd-OC ₂ H ₅
CH = CHC ₂ H ₄ -Ph-Py (2) -Ph-Cd-OC ₂ H ₅
C ₅ H ₁₁ -Ph-Py (3) -Ph-Cd-OCH ₃
CH ₃ O-Ph-Py (3) -Ph-Cd-C ₂ H ₅
C ₃ H ₇ -Ph-Ph-Cy-Cd-OC ₂ H ₅
C ₄ H ₉ -Ph-Ph-Cy-Cd-C ₃ H ₇
C ₅ H ₁₁ -Ph-Ph-Py (2) -Cd-OCH ₃
CH ₂ = CH-Ph-Ph-Py (2) -Cd-OC ₂ H ₅
C ₃ H ₇ -Ph-Ph-Py (3) -Cd-OC ₂ H _{5
C 4 H 9 -Ph-Ph-} Py (3) -Cd-C 3 H 7
C ₅ H ₁₁ -Ph-Cy-Py (2) -Cd-OCH ₃
CH ₃ -Ph-Cy-Py (2) -Cd-C ₂ H ₅
C ₂ H ₅ -Ph-Cy-Py (3) -Cd-C ₃ H ₇
C ₃ H ₇ -Ph-Cy-Py (3) -Cd-OC ₂ H ₅

C ₄ H ₉ -Cy-Cy-Ph-Cd-C ₂ H ₅
C ₄ H ₉ -Cy-Cy-Ph (2F, 3F) -Cd-OC ₂ H ₅
C ₅ H ₁₁ -Cy-Cy-Ph-Cd-OC ₂ H ₅
CH ₃ -Cy-Py (2) -Ph-Cd-OCH ₃
C ₂ H ₄ -Cy-Py (2) -Ph-Cd-C ₂ H ₅
C ₃ H ₇ -Cy-Py (2) -Ph-Cd-OC ₂ H ₅
C ₄ H ₉ -Cy-Py (2) -Ph-Cd-C ₃ H ₇
C ₅ H ₁₁ -Cy-Cy-Cy-Cd-OCH ₃
CH ₂ = CH-Cy-Cy-Cy-Cd-OC ₂ H ₅
C ₃ H ₇ -Cy-Cy-Py (2) -Cd-OCH ₃
C ₄ H ₉ -Cy-Cy-Py (2) -Cd-C ₂ H ₅
C ₅ H ₁₁ -Cy-Cy-Py (3) -Cd-OC ₂ H ₅
CH ₂ = CH-Cy-Cy-Py (3) -Cd-OC ₂ H ₅
C ₃ H ₇ -Cy-Ph-Cy-Cd-OCH ₃
CH = CHC ₂ H ₄ -Cy-Ph-Cy-Cd-OC ₂ H ₅
C ₅ H ₁₁ -Cy-Ph-Py (2) -Cd-OC ₂ H ₅
CH ₃ -Cy-Ph-Py (2) -Cd-C ₃ H ₇
C ₂ H ₅ -Cy-Ph-Py (3) -Cd-OCH ₃
C ₃ H ₇ -Cy-Ph-Py (3) -Cd-C ₂ H ₅

C ₄ H ₉ -Ph-Ph-Cd-Ph-C ₃ H ₇
C ₅ H ₁₁ -Ph-Ph-Cd-Ph-C ₂ H ₄ CH = CH ₂
CH ₃ -Ph-Cy-Cd-Ph-C ₅ H ₁₁
C ₂ H ₅ O-Ph-Cy-Cd-Ph-CH ₃
C ₃ H ₇ -Ph-Py (2) -Cd-Ph-C ₂ H ₅
C ₄ H ₉ -Ph-Py (2) -Cd-Ph-CH = CH ₂
C ₅ H ₁₁ -Ph-Py (3) -Cd-Ph-OC ₂ H ₅
CH ₃ -Ph-Py (3) -Cd-Ph-C ₃ H ₇
C ₂ H ₅ -Ph-Ph-Cd-Cy-C ₄ H ₉
C ₂ H ₅ O-Ph-Ph-Cd-Cy-C ₅ H ₁₁
C ₃ H ₇ -Ph-Ph-Cd-Py (2) -CH ₃
CH ₂ = CHC ₂ H ₄ -Ph-Ph-Cd-Py (2) -C ₂ H ₅
C ₅ H ₁₁ -Ph-Ph-Cd-Py (3) -C ₃ H ₇
CH ₃ -Ph-Ph-Cd-Py (3) -OC ₂ H ₅
C ₂ H ₅ -Cy-Ph-Cd-Ph-C ₃ H ₇
C ₃ H ₇ -Cy-Ph-Cd-Ph-OC ₂ H _{5
C 4 H 9 -Py (2)} -Ph-Cd-Ph-C 3 H 7
C ₅ H ₁₁ -Py (2) -Ph-Cd-Ph-C ₂ H ₄ CH = CH ₂
CH ₃ -Py (3) -Ph-Cd-Ph-C ₅ H ₁₁
C ₂ H ₅ O-Py (3) -Ph-Cd-Ph-C ₅ H ₁₁
C ₃ H ₇ -Cy-Ph (2F, 3F) -Cd-Cy-CH ₃
C ₄ H ₉ -Cy-Ph-Cd-Cy-OCH ₃
C ₅ H ₁₁ -Cy-Ph-Cd-Py (2) -OCH ₃
C ₅ H ₁₁ -Cy-Ph-Cd-Py (2) -C ₂ H ₅
CH ₃ -Cy-Ph-Cd-Py (3) -C ₃ H ₇
C ₂ H ₅ -Cy-Ph-Cd-Py (3) -C ₂ H ₄ CH = CH _{2
C 2 H 5 -Cy-Cy-} Cd-Ph-C 5 H 11
C ₃ H ₇ -Cy-Cy-Cd-Ph-OCH ₃
C ₄ H ₉ -Cy-Cy-Cd-Cy-C ₂ H ₅
C ₅ H ₁₁ -Cy-Cy-Cd-Cy-CH = CH ₂
CH ₃ -Cy-Cy-Cd-Py (2) -C ₃ H ₇
C ₂ H ₅ -Cy-Cy-Cd-Py (2) -OC ₂ H ₅
C ₃ H ₇ -Cy-Cy-Cd-Py (3) -C ₄ H ₉
CH ₂ = CHC ₂ H ₄ -Cy-Cy-Cd-Py (3) -C ₅ H ₁₁
C ₅ H ₁₁ -Py (2) -Cy-Cd-Ph-CH ₃
CH ₃ -Py (2) -Cy-Cd-Ph (2F, 3F) -OCH ₃
C ₂ H ₅ -Py (2) -Cy-Cd-Cy-OCH ₃
C ₂ H ₅ O-Py (2) -Cy-Cd-Cy-C ₂ H ₅
C ₃ H ₇ -Py (3) -Cy-Cd-Ph-C ₃ H ₇
C ₄ H ₉ -Py (3) -Cy-Cd-Ph-C ₂ H ₄ CH = CH ₂
C ₅ H ₁₁ -Py (3) -Cy-Cd-Cy-C ₃ H ₇
CH ₃ O-Py (3) -Cy-Cd-Cy-C ₄ H ₉

C ₂ H ₅ -Ph-Py (2) -Ph-Cd-OCH ₃
C ₃ H ₇ -Ph-Py (2) -Ph-Cd-C ₂ H ₅
C ₄ H ₉ -Ph-Py (2) -Ph-Cd-OC ₂ H ₅
C ₅ H ₁₁ -Ph-Py (2) -Ph-Cd-C ₃ H ₇
CH ₃ -Ph-Cy-Cy-Cd-OC ₂ H ₅
C ₂ H ₅ -Ph-Cy-Cy-Cd-C ₃ H ₇
C ₃ H ₇ -Ph-Py (2) -Cy-Cd-OCH ₃
C ₄ H ₉ -Ph-Py (2) -Cy-Cd-C ₂ H ₅
C ₅ H ₁₁ -Ph-Py (3) -Cy-Cd-OC ₂ H ₅
CH ₃ -Ph-Py (3) -Cy-Cd-C ₃ H ₇
C ₂ H ₅ -Py (2) -Ph-Cy-Cd-OCH ₃
C ₃ H ₇ -Py (2) -Ph-Cy-Cd-C ₂ H ₅
C ₄ H ₉ -Py (3) -Ph-Cy-Cd-OC ₂ H ₅
CH ₂ = CHC ₂ H ₄ -Py (2) -Ph-Cy-Cd-OC ₂ H ₅
C ₅ H ₁₁ -Cy-Py (2) -Cy-Cd-OCH ₃
CH ₃ -Cy-Py (2) -Cy-Cd-C ₂ H ₅
C ₂ H ₅ -Cy-Py (3) -Cy-Cd-OC ₂ H ₅
C ₃ H ₇ -Cy-Py (3) -Cy-Cd-C ₃ H ₇
C ₄ H ₉ -Py (2) -Cy-Cy-Cd-OCH ₃
CH ₂ = CHC ₂ H ₄ -Py (2) -Cy-Cy-Cd-OCH ₃
C ₅ H ₁₁ -Py (3) -Cy-Cy-Cd-OC ₂ H ₅
CH ₃ -Py (3) -Cy-Cy-Cd-C ₂ H ₅
C ₂ H ₅ -Ph-Cy-Cd-Cy-C ₃ H ₇
C ₂ H ₅ O-Ph-Cy-Cd-Cy-C ₃ H ₇
C ₃ H ₇ -Ph-Py (2) -Cd-Cy-C ₄ H ₉
C ₄ H ₉ -Ph-Py (2) -Cd-Cy-C ₂ H ₄ CH = CH ₂
C ₅ H ₁₁ -Ph-Py (2) -Cd-Cy-C ₅ H ₁₁
CH ₃ O-Ph-Py (2) -Cd-Cy-C ₅ H ₁₁
C ₂ H ₅ -Py (2) -Ph-Cd-Cy-CH ₃
C ₂ H ₅ O-Py (2) -Ph-Cd-Cy-C ₂ H ₅
C ₃ H ₇ -Py (3) -Ph-Cd-Cy-C ₃ H ₇
CH ₂ = CHC ₂ H ₄ -Py (3) -Ph-Cd-Cy-C ₄ H ₉
C ₅ H ₁₁ -Ph-Cy-Cd-Py (2) -C ₅ H ₁₁
CH ₂ = CH-Ph-Cy-Cd-Py (2) -CH ₃
C ₃ H ₇ -Ph-Cy-Cd-Py (3) -C ₂ H ₅
C ₂ H ₅ O-Ph-Cy-Cd-Py (3) -C ₃ H ₇
C ₃ H ₇ -Cy-Py (2) -Cd-Cy-C ₄ H ₉
C ₄ H ₉ -Cy-Py (2) -Cd-Cy-OCH ₃
C ₅ H ₁₁ -Cy-Py (3) -Cd-Cy-C ₂ H ₅
C ₅ H ₁₁ -Cy-Py (3) -Cd-Cy-OC ₂ H ₅
CH ₃ -Cy-Py (2) -Cd-Ph-C ₃ H ₇
CH ₂ = CH-Cy-Py (2) -Cd-Ph-C ₄ H ₉
C ₃ H ₇ -Cy-Py (2) -Cd-Ph-C ₅ H ₁₁
CH ₂ = CHC ₂ H ₄ -Cy-Py (2) -Cd-Ph-CH ₃

Examples of the pentacyclic compound (m + n + o + p + q + r = 4) include the following.
C ₃ H ₇ -Ph-Ph-Ph-Ph-Cd-OC ₂ H ₅
C ₄ H ₉ -Ph-Ph-Ph-Cy-Cd-OC ₂ H ₅
C ₅ H ₁₁ -Ph-Ph-Ph-Py (2) -Cd-OCH ₃
CH ₃ -Ph-Ph-Ph-Py (3) -Cd-OCH ₃
C ₂ H ₅ -Ph-Ph-Cy-Ph (2F, 3F) -Cd-OCH ₃
C ₃ H ₇ -Ph-Ph-Py (2) -Ph-Cd-OC ₂ H ₅
C ₄ H ₉ -Ph-Ph-Py (3) -Ph-Cd-OC ₂ H ₅
C ₅ H ₁₁ -Ph-Cy-Ph-Ph-Cd-OC ₂ H ₅
CH ₃ -Ph-Ph (2) -Ph-Ph-Cd-OCH ₃
C ₂ H ₅ -Ph-Py (3) -Ph-Ph-Cd-OC ₂ H ₅
C ₃ H ₇ -Cy-Ph-Ph-Ph-Cd-OC ₂ H ₅
C ₄ H ₉ -Py (2) -Ph-Ph-Ph-Cd-OC ₂ H ₅
C ₅ H ₁₁ -Py (3) -Ph-Ph-Ph-Cd-OC ₂ H ₅
CH ₃ -Ph-Ph-Cy-Cy-Cd-OCH ₃
C ₂ H ₅ -Ph-Ph-Py (2) -Cy-Cd-OCH ₃
C ₃ H ₇ -Ph-Ph-Py (3) -Cy-Cd-OC ₂ H ₅
C ₄ H ₉ -Ph-Cy-Ph-Cy-Cd-OC ₂ H ₅
C ₅ H ₁₁ -Ph-Py (2) -Ph-Cy-Cd-OCH ₃
CH ₃ -Ph-Py (3) -Ph-Cy-Cd-OCH ₃

C ₂ H ₅ -Cy-Ph-Ph-Cy-Cd-OCH ₃
C ₃ H ₇ -Cy-Py (2) -Ph-Cy-Cd-OCH ₃
C ₄ H ₉ -Cy-Py (3) -Ph-Cy-Cd-OC ₂ H ₅
C ₅ H ₁₁ -Ph-Ph-Cy-Py (2) -Cd-OC ₂ H ₅
CH ₃ -Ph-Cy-Ph-Py (2) -Cd-OC ₂ H ₅
C ₂ H ₅ -Cy-Ph-Ph-Py (2) -Cd-OCH ₃
C ₃ H ₇ -Ph-Ph-Cy-Py (3) -Cd-OC ₂ H ₅
C ₄ H ₉ -Ph-Cy-Ph-Py (3) -Cd-OC ₂ H ₅
C ₅ H ₁₁ -Cy-Ph-Ph-Py (3) -Cd-OC ₂ H ₅
CH ₃ -Cy-Cy-Cy-Cy-Cd-OC ₂ H ₅
C ₂ H ₅ -Cy-Cy-Cy-Ph-Cd-OC ₂ H ₅
C ₃ H ₇ -Cy-Cy-Cy-Py (2) -Cd-OC ₂ H ₅
C ₄ H ₉ -Cy-Cy-Cy-Py (3) -Cd-OC ₂ H ₅
C ₅ H ₁₁ -Cy-Cy-Ph-Cy-Cd-OCH ₃
CH ₃ -Cy-Cy-Py (2) -Cy-Cd-OC ₂ H ₅
C ₂ H ₅ -Cy-Cy-Py (3) -Cy-Cd-OC ₃ H ₇
C ₃ H ₇ -Cy-Ph-Cy-Cy-Cd-OC ₂ H ₅
C ₄ H ₉ -Cy-Py (2) -Cy-Cy-Cd-OC ₂ H ₅
C ₅ H ₁₁ -Cy-Py (3) -Cy-Cy-Cd-OCH ₃

CH ₃ -Ph-Cy-Cy-Cy-Cd-OCH ₃
C ₂ H ₅ -Py (2) -Cy-Cy-Cy-Cd-OCH ₃
C ₃ H ₇ -Py (2) -Cy-Cy-Cy-Cd-OC ₂ H ₅
C ₄ H ₉ -Cy-Cy-Ph-Ph-Cd-OC ₂ H ₅
C ₅ H ₁₁ -Cy-Cy-Py (2) -Ph (2F, 3F) -Cd-OC ₂ H ₅
CH ₃ -Cy-Cy-Py (3) -Ph-Cd-OC ₂ H ₅
C ₂ H ₅ -Cy-Ph-Cy-Ph-Cd-OCH ₃
C ₃ H ₇ -Cy-Py (2) -Cy-Ph-Cd-OCH ₃
C ₄ H ₉ -Cy-Py (3) -Cy-Ph-Cd-C ₂ H ₅
C ₅ H ₁₁ -Ph-Cy-Cy-Ph-Cd-OC ₂ H ₅
CH ₃ -Py (2) -Cy-Cy-Ph-Cd-OC ₂ H ₅
C ₂ H ₅ -Py (2) -Cy-Cy-Ph-Cd-OC ₂ H ₅
C ₃ H ₇ -Cy-Cy-Ph-Py (2) -Cd-OCH ₃
C ₄ H ₉ -Cy-Ph-Cy-Py (2) -Cd-OCH ₃
C ₅ H ₁₁ -Ph-Cy-Cy-Py (2) -Cd-OCH ₃
CH ₃ -Cy-Cy-Ph-Py (3) -Cd-OC ₂ H ₅
C ₂ H ₅ -Cy-Ph-Cy-Py (3) -Cd-OC ₂ H ₅
C ₃ H ₇ -Ph-Cy-Cy-Py (3) -Cd-OC ₂ H ₅
C ₄ H ₉ -Ph-Ph-Ph-Cd-Ph-C ₃ H ₇
C ₅ H ₁₁ -Ph-Ph-Ph (2F, 3F) -Cd-Cy-C ₄ H ₉
CH ₃ -Ph-Ph-Ph-Cd-Py (2) -C ₅ H ₁₁
C ₂ H ₅ -Ph-Ph-Ph-Cd-Py (3) -CH ₃

C ₃ H ₇ -Ph-Ph-Cy-Cd-Ph-C ₂ H ₅
C ₄ H ₉ -Ph-Ph-Py (2) -Cd-Ph-C ₂ H ₅
C ₅ H ₁₁ -Ph-Ph-Py (3) -Cd-Ph-C ₃ H ₇
CH ₃ -Ph-Cy-Ph-Cd-Ph-C ₄ H ₉
C ₂ H ₅ -Ph-Py (2) -Ph-Cd-Ph-C ₅ H ₁₁
C ₃ H ₇ -Ph-Py (3) -Ph-Cd-Ph-CH ₃
C ₄ H ₉ -Cy-Ph-Ph-Cd-Ph-C ₂ H ₅
C ₅ H ₁₁ -Py (2) -Ph-Ph-Cd-Ph-C ₃ H ₇
CH ₃ -Py (3) -Ph-Ph-Cd-Ph-C ₄ H ₉
C ₂ H ₅ -Ph-Ph-Cy-Cd-Cy-C ₅ H ₁₁
C ₃ H ₇ -Ph-Ph-Py (2) -Cd-Cy-C ₅ H ₁₁
C ₄ H ₉ -Ph-Ph-Py (3) -Cd-Cy-CH ₃
C ₅ H ₁₁ -Ph-Cy-Ph-Cd-Cy-C ₂ H ₅
CH ₃ -Ph-Py (2) -Ph-Cd-Cy-C ₃ H ₇
C ₂ H ₅ -Ph-Py (3) -Ph (2F, 3F) -Cd-Cy-C ₄ H ₉
C ₃ H ₇ -Cy-Ph-Ph-Cd-Cy-C ₅ H ₁₁
C ₄ H ₉ -Py (2) -Ph-Ph-Cd-Cy-CH ₃
C ₅ H ₁₁ -Py (3) -Ph-Ph-Cd-Cy-C ₂ H ₅
CH ₃ -Ph-Ph-Cy-Cd-Py (2) -C ₃ H ₇
C ₂ H ₅ -Ph-Cy-Ph-Cd-Py (2) -C ₄ H ₉
C ₃ H ₇ -Cy-Ph-Ph-Cd-Py (2) -C ₅ H ₁₁
C ₄ H ₉ -Ph-Ph-Cy-Cd-Py (3) -CH ₃
C ₅ H ₁₁ -Ph-Cy-Ph-Cd-Py (3) -C ₂ H ₅
CH ₃ -Cy-Ph-Ph-Cd-Py (3) -C ₃ H ₇

C ₂ H ₅ -Cy-Cy-Cy-Cd-Cy-C ₄ H ₉
C ₃ H ₇ -Cy-Cy-Cy-Cd-Ph-C ₅ H ₁₁
C ₄ H ₉ -Cy-Cy-Cy-Cd-Py (2) -CH ₃
C ₅ H ₁₁ -Cy-Cy-Cy-Cd-Py (3) -C ₂ H ₅
CH ₃ -Cy-Cy-Ph-Cd-Cy-C ₂ H ₅
C ₂ H ₅ -Cy-Cy-Py (2) -Cd-Cy-C ₃ H ₇
C ₃ H ₇ -Cy-Cy-Py (3) -Cd-Cy-C ₄ H ₉
C ₄ H ₉ -Cy-Ph-Cy-Cd-Cy-C ₅ H ₁₁
C ₅ H ₁₁ -Cy-Py (2) -Cy-Cd-Cy-CH ₃
CH ₃ -Cy-Py (2) -Cy-Cd-Cy-C ₂ H ₅
C ₂ H ₅ -Ph-Cy-Cy-Cd-Cy-C ₃ H ₇
C ₃ H ₇ -Py (2) -Cy-Cy-Cd-Cy-C ₄ H ₉
C ₄ H ₉ -Py (3) -Cy-Cy-Cd-Cy-C ₅ H ₁₁
C ₅ H ₁₁ -Cy-Cy-Ph-Cd-Ph-CH ₃
CH ₃ -Cy-Cy-Py (2) -Cd-Ph-C ₂ H ₅
C ₂ H ₅ -Cy-Cy-Py (3) -Cd-Ph-C ₃ H ₇
C ₃ H ₇ -Cy-Ph-Cy-Cd-Ph-C ₂ H ₅
C ₄ H ₉ -Cy-Py (2) -Cy-Cd-Ph-CH ₃
C ₅ H ₁₁ -Cy-Py (3) -Cy-Cd-Ph-C ₂ H ₅
CH ₃ -Ph-Cy-Cy-Cd-Ph-C ₃ H ₇
C ₂ H ₅ -Py (2) -Cy-Cy-Cd-Ph-C ₄ H ₉
C ₃ H ₇ -Py (3) -Cy-Cy-Cd-Ph-C ₅ H ₁₁
C ₄ H ₉ -Cy-Cy-Ph-Cd-Py (2) -CH ₃
C ₅ H ₁₁ -Cy-Ph-Cy-Cd-Py (2) -C ₂ H ₅
CH ₃ -Ph-Cy-Cy-Cd-Py (2) -C ₃ H ₇
C ₂ H ₅ -Cy-Cy-Ph-Cd-Py (3) -C ₄ H ₉
C ₃ H ₇ -Cy-Ph-Cy-Cd-Py (3) -C ₅ H ₁₁
C ₄ H ₉ -Ph-Cy-Cy-Cd-Py (3) -CH ₃

C ₅ H ₁₁ -Ph-Ph-Cd-Ph-Ph-C ₂ H ₅
CH ₃ -Ph-Ph-Cd-Ph-Cy-C ₃ H ₇
C ₂ H ₅ -Ph-Ph-Cd-Ph (2F, 3F) -Py (2) -C ₄ H ₉
C ₃ H ₇ -Ph-Ph-Cd-Ph-Py (3) -C ₅ H ₁₁
C ₄ H ₉ -Ph-Ph-Cd-Cy-Ph-CH ₃
C ₅ H ₁₁ -Ph-Ph-Cd-Py (2) -Ph-C ₂ H ₅
CH ₃ -Ph-Ph-Cd-Py (3) -Ph-C ₃ H ₇
C ₂ H ₅ -Ph-Cy-Cd-Ph-Ph-C ₄ H ₉
C ₃ H ₇ -Ph-Py (2) -Cd-Ph-Ph-C ₅ H ₁₁
C ₄ H ₉ -Ph-Py (3) -Cd-Ph-Ph-CH ₃
C ₅ H ₁₁ -Cy-Ph-Cd-Ph-Ph-C ₂ H ₅
CH ₃ -Py (2) -Ph-Cd-Ph-Ph-C ₃ H ₇
C ₂ H ₅ -Py (3) -Ph-Cd-Ph-Ph-C ₄ H ₉
C ₃ H ₇ -Ph-Ph-Cd-Cy-Cy-C ₂ H ₅
C ₄ H ₉ -Ph-Ph-Cd-Py (2) -Cy-C ₃ H ₇
C ₅ H ₁₁ -Ph-Ph-Cd-Py (3) -Cy-C ₄ H ₉
CH ₃ -Ph-Cy-Cd-Ph-Cy-C ₅ H ₁₁
C ₂ H ₅ -Ph-Py (2) -Cd-Ph-Cy-CH ₃
C ₃ H ₇ -Ph-Py (3) -Cd-Ph-Cy-C ₂ H ₅
C ₄ H ₉ -Cy-Ph-Cd-Ph-Cy-C ₃ H ₇
C ₅ H ₁₁ -Py (2) -Ph-Cd-Ph-Cy-C ₄ H ₉
CH ₃ -Py (3) -Ph-Cd-Ph-Cy-C ₅ H ₁₁
C ₂ H ₅ -Ph-Ph-Cd-Cy-Py (2) -C ₃ H ₇
C ₃ H ₇ -Ph-Cy-Cd-Ph-Py (2) -C ₄ H ₉
C ₄ H ₉ -Cy-Ph-Cd-Ph-Py (2) -C ₅ H ₁₁
C ₅ H ₁₁ -Ph-Ph-Cd-Cy-Py (3) -CH ₃
CH ₃ -Ph-Cy-Cd-Ph-Py (3) -C ₂ H ₅
C ₂ H ₅ -Cy-Ph-Cd-Ph-Py (3) -C ₃ H ₇

C ₃ H ₇ -Cy-Cy-Cd-Cy-Cy-C ₂ H ₅
C ₄ H ₉ -Cy-Cy-Cd-Cy-Ph-C ₃ H ₇
C ₅ H ₁₁ -Cy-Cy-Cd-Cy-Py (2) -C ₄ H ₉
CH ₃ -Cy-Cy-Cd-Cy-Py (3) -C ₅ H ₁₁
C ₂ H ₅ -Cy-Cy-Cd-Ph-Cy-CH ₃
C ₃ H ₇ -Cy-Cy-Cd-Py (2) -Cy-C ₂ H ₅
C ₄ H ₉ -Cy-Cy-Cd-Py (3) -Cy-C ₃ H ₇
C ₅ H ₁₁ -Cy-Cy-Cd-Ph-Ph-C ₄ H ₉
CH ₃ -Cy-Cy-Cd-Py (2) -Ph-C ₅ H ₁₁
C ₂ H ₅ -Cy-Cy-Cd-Py (3) -Ph-CH ₃
C ₃ H ₇ -Cy-Ph-Cd-Cy-Ph-C ₂ H ₅
C ₄ H ₉ -Cy-Py (2) -Cd-Cy-Ph-C ₃ H ₇
C ₅ H ₁₁ -Cy-Py (3) -Cd-Cy-Ph-C ₄ H ₉
CH ₃ -Ph-Cy-Cd-Cy-Ph-C ₅ H ₁₁
C ₂ H ₅ -Py (2) -Cy-Cd-Cy-Ph-CH ₃
C ₃ H ₇ -Py (3) -Cy-Cd-Cy-Ph-C ₂ H ₅
C ₃ H ₇ -Cy-Cy-Cd-Ph-Py (2) -C ₅ H ₁₁
C ₄ H ₉ -Cy-Ph-Cd-Cy-Py (2) -CH ₃
C ₅ H ₁₁ -Ph-Cy-Cd-Cy-Py (2) -C ₂ H ₅
CH ₃ -Cy-Cy-Cd-Ph-Py (3) -C ₃ H ₇
C ₂ H ₅ -Cy-Ph-Cd-Cy-Py (3) -C ₄ H ₉
C ₃ H ₇ -Ph-Cy-Cd-Cy-Py (3) -C ₅ H ₁₁

The compound of the present invention has a novel Δε negative function-expressing ring structure, and it has been found that Δε is negatively larger than that of a widely used compound having a 2,3-difluorophenyl group. Further, by appropriately selecting the ring group, substituent and linking group constituting the compound, the compound of the present invention can prepare a liquid crystal composition satisfying various performances required for a liquid crystal element such as a wide operating temperature range. it is conceivable that. Moreover, it turned out that the compound of this invention can be easily manufactured with the manufacturing method of this invention.

Claims (9)

1. A fluorine-containing compound represented by the following formula (1).
   

   

   (1)
   The symbol in Formula (1) shows the following meanings.
   R ¹ and R ^{2 are} each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 18 carbon atoms, wherein one or more hydrogen atoms may be substituted with a halogen atom In general, an etheric oxygen atom or a thioetheric sulfur atom may be inserted between carbon-carbon atoms or at the bond terminal of the group, and one or more —CH ₂ CH ₂ — may be —CH═CH— or —C It may be substituted with ≡C-.
   A ¹ , A ² , A ³ , A ⁴ , A ⁵ and A ⁶ : independently of each other, trans-1,4-cyclohexylene group, 1,4-cyclohexenylene group, 1,3-cyclobutylene Group, 1,2-cyclopropylene group, naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group, or 1, 4-phenylene group, and in each of these groups, one or more hydrogen atoms may be substituted with a halogen atom, and one or two ═CH— may be substituted with a nitrogen atom. Alternatively, _two —CH ₂ — may be substituted with an etheric oxygen atom or a thioetheric sulfur atom.
   Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ^{6 are} each independently a single bond or an alkylene group having 1 to 4 carbon atoms, in which one or more hydrogen atoms are It may be substituted with a fluorine atom, and one or more —CH ₂ — may be substituted with an etheric oxygen atom or a thioetheric sulfur atom. One or more —CH ₂ CH ₂ — may be substituted with —CH═CH— or —C≡C—, and one —CH ₂ CH ₂ — may be substituted with —COO— or —OCO—. May be.
   m, n, o, p, q and r: 0 or 1 independently of each other. However, 0 ≦ m + n + o + p + q + r ≦ 4.
2. The compound according to claim 1, which is a compound represented by the following formula (1-1).
   

   

   (1-1)
   The symbols in the formula have the following meanings.
   R ¹¹ and R ^{21 are} each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 18 carbon atoms, wherein one or more hydrogen atoms may be substituted with a halogen atom In addition, an etheric oxygen atom or a thioetheric sulfur atom may be inserted between carbon-carbon atoms or at the bond terminal of the group, and one or more —CH ₂ CH ₂ — is substituted with —CH═CH—. It may be.
   A ¹¹ , A ²¹ , A ³¹ , A ⁴¹ , A ⁵¹ , and A ⁶¹ : each independently a trans-1,4-cyclohexylene group or a 1,4-phenylene group, One or more hydrogen atoms may be substituted with a halogen atom, one or two ═CH— may be substituted with a nitrogen atom, and one or two —CH ₂ — is an etheric oxygen It may be substituted with an atom or a thioetheric sulfur atom.
   Z ¹¹ , Z ²¹ , Z ³¹ , Z ⁴¹ , Z ⁵¹ and Z ^{61 are} each independently a single bond or an alkylene group having 1 to 4 carbon atoms, and one or more hydrogen atoms in the alkylene group May be substituted with a fluorine atom, and one or more —CH ₂ — may be substituted with an etheric oxygen atom or a thioetheric sulfur atom, and one or more —CH ₂ CH ₂ — may be —CH It may be substituted with ═CH— or —C≡C—.
   m, n, o, p, q and r have the same meaning as described above.
3. The compound according to claim 1, which is a compound represented by the following formula (1-2).
   

   

   (1-2)
   The symbols in the formula have the following meanings.
   R ¹² and R ^{22 are} each independently an alkyl group having 1 to 10 carbon atoms, and one or more hydrogen atoms in the group may be substituted with a fluorine atom, and a carbon-carbon atom or An etheric oxygen atom may be inserted at the bond terminal of the group, and one or more —CH ₂ CH ₂ — may be substituted with —CH═CH—.
   A ¹² , A ²² , A ³² , A ⁴² , A ⁵² and A ⁶² : independently of each other, a trans-1,4-cyclohexylene group, 1,4-phenylene group or one or two hydrogen atoms 1,4-phenylene group substituted by a fluorine atom.
   Z ¹² , Z ²² , Z ³² , Z ⁴² , Z ⁵² and Z ⁶² : independently of each other, a single bond, —CH ₂ CH ₂ —, —CH═CH—, —C≡C—, —CH ₂ O —, —OCH ₂ —, —CF ₂ CF ₂ —, —CF═CF—, —OCF ₂ —, —CF ₂ O—, —CH ₂ CH ₂ OCF ₂ —, —CF ₂ OCH ₂ CH ₂ —, — CF═CFCF ₂ O— or —OCF ₂ CF═CF—.
4. The compound represented by the following formula (2) is cyclized to obtain a compound represented by the following formula (3), and then further hydrogenated to obtain a compound represented by the following formula (4). A method for producing a compound represented by formula (1), characterized in that the compound is represented by 1).
   

   

   R ³ in the formula (2) is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and other symbols in each formula have the same meaning as the symbols in the formula (1) according to claim 1.
5. A compound represented by the following formula (2). However, R ³ in the formula (2) is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and other symbols have the same meaning as the symbols in the formula (1) according to claim 1.
   

   

   (2)
6. A compound represented by the following formula (3). However, the symbol in Formula (3) shows the same meaning as the symbol in Formula (1) of Claim 1.
   

   

   (3)
7. A compound represented by the following formula (4). However, the symbol in Formula (4) shows the same meaning as the symbol in Formula (1) of Claim 1.
   

   

   (4)
8. A liquid crystal composition comprising the compound according to any one of claims 1 to 3.
9. A liquid crystal electro-optical element formed by sealing the liquid crystal composition according to claim 8 between two substrates on which electrodes are disposed.