WO2018225522A1

WO2018225522A1 - Liquid crystal compound, and composition thereof

Info

Publication number: WO2018225522A1
Application number: PCT/JP2018/019966
Authority: WO
Inventors: 宗矩櫻井; 健太東條; 豊門本
Original assignee: Dic株式会社
Priority date: 2017-06-06
Filing date: 2018-05-24
Publication date: 2018-12-13
Also published as: CN110461852B; JPWO2018225522A1; JP6635228B2; CN110461852A

Abstract

Provided are: a compound represented by general formula (i); and a composition and a liquid crystal display element which use said compound. The compound represented by general formula (i) is obtained by reacting a compound represented by general formula (i-r2) with a compound represented by general formula (i-r1) in the presence of a transition metal catalyst and a base to obtain a compound represented by general formula (i-r3), and subsequently inducing an intramolecular reaction by using the base to deprotonate the -Yi3-H in the compound represented by general formula (i-r3) to generate an anion. According to the present invention, a compound exhibiting a high Tni and a large Δε, and a composition and a liquid crystal display element which use said compound can be provided. Furthermore, a method for producing the compound and a production intermediate of the compound can also be provided.

Description

Liquid crystal compound and composition thereof

The present invention relates to a compound having a condensed ring that is useful as an organic electronic material, medical pesticide, or a liquid crystal display element material, and a liquid crystal composition using these compounds.

Liquid crystal display elements are used in various measuring instruments, automobile panels, word processors, electronic notebooks, printers, computers, televisions, clocks, advertisement display boards, etc., including watches and calculators. Typical liquid crystal display methods include TN (twisted nematic) type, STN (super twisted nematic) type, vertical alignment type using TFT (thin film transistor), and IPS (in-plane switching) type. There is a drive system such as. The liquid crystal compositions used in these liquid crystal display elements are stable against external factors such as moisture, air, heat, and light, and the liquid crystal phase (nematic phase, smectic phase) in the widest possible temperature range centering on room temperature. Phase, blue phase, etc.), low viscosity, and low driving voltage. Furthermore, the liquid crystal composition is selected from several to several tens of kinds of compounds in order to optimize the dielectric anisotropy (Δε) and the refractive index anisotropy (Δn) according to the individual display elements, It is configured.

When the liquid crystal composition is used as a display element or the like, it is required to exhibit a stable nematic phase in a wide temperature range. In order to maintain a nematic phase in a wide temperature range, it is required that individual components constituting the liquid crystal composition have high miscibility with other components and have a high clearing point (T _ni ). . Moreover, when using a liquid crystal composition as a display element etc., it is calculated | required that a rotational viscosity coefficient ((gamma) ₁ ) is as low as possible. In order to obtain a low gamma ₁ liquid crystal composition There are various ways, big as one | [Delta] [epsilon] | It is known that a compound having a (extrapolated value). The reason for this will be described below. In order to reduce γ ₁ of the liquid crystal composition, it is effective to increase as much as possible the use amount of a nonpolar compound having | Δε | (extrapolated value) of almost 0 and showing a low γ ₁ (extrapolated value). It is. The Δε of the composition that is generally required is determined for each liquid crystal panel, and a polar compound having a large γ ₁ (extrapolated value) is added to give Δε. Therefore, by replacing the compound with a large | Δε | (extrapolated value), the amount of the nonpolar compound used can be increased, and as a result, a decrease in γ ₁ of the liquid crystal composition can be achieved.

Thus, there is a demand for the development of a compound that exhibits a high T _ni and a large | Δε | (extrapolated value). So far, the following compounds having a dibenzofuran structure have been reported, but there has been a problem that T _ni is not sufficiently large (Patent Documents 1 and 2).

Wherein R ¹ and R ² each independently represents an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, or an alkynyl group having 2 to 15 carbon atoms, Each independently represents 0 or 1)

German Patent Application Publication No. 102015002298 German Patent Application Publication No. 102015003411

The problem to be solved by the present invention is to provide a compound having a high T _ni and having a large Δε, and a liquid crystal composition and a liquid crystal display device comprising the compound as a constituent member.

In order to solve the above problems, the present inventors have studied various compounds, and as a result, have found that a compound having the following condensed ring can effectively solve the problems, and have completed the present invention.

The present invention has the general formula (i)

( ^Wherein , X ⁱ¹ and X ⁱ² each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a trifluoromethoxy group,
Y ⁱ¹ and Y ⁱ² each independently represent —O—, —S—, —SO—, —SOO—, —CF ₂ —, —CO—, ^—CX ⁱ³ X ⁱ⁴ —, wherein Y ⁱ¹ and Y any one or more of ⁱ² represents —O—, —S—, —SO—, —SOO—;
X ⁱ³ and X ⁱ⁴ each independently represent the same meaning as X ⁱ¹ ,
W ⁱ¹

(However, the black point in the formula represents the point of attachment to L ⁱ² or Y ⁱ² ),
W ⁱ² represents a single bond or —CL ⁱ⁹ L ⁱ¹⁰ —,
L ⁱ¹ , L ⁱ² , L ⁱ³ , L ⁱ⁴ , L ⁱ⁵ , L ⁱ⁶ , L ⁱ⁷ , L ⁱ⁸ , L ⁱ⁹ and L ⁱ¹⁰ are each independently a hydrogen atom, bromine atom, iodine atom, hydroxyl group, carbon number 1 To 15 alkyl groups, alkenyl groups of 2 to 15 carbon atoms, or

(Wherein R ⁱ¹ represents a hydrogen atom, a bromine atom, an iodine atom, a hydroxyl group, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, or carbon. Represents an alkenyloxy group having 2 to 15 atoms,
A ⁱ¹ represents (a) a 1,4-cyclohexylene group (one —CH ₂ — present in this group or two or more non-adjacent —CH ₂ — represents —O— or —S—). May be replaced.)
(B) 1,4-phenylene group (one —CH═ present in this group or two or more non-adjacent —CH═ may be replaced by —N═, present in this group) One hydrogen atom may be substituted with a fluorine atom.)
(C) 1,4-cyclohexenylene group, naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group ( A hydrogen atom present in these groups may be substituted with a fluorine atom, or present in a naphthalene-2,6-diyl group or a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group. One -CH = or two or more non-adjacent -CH = may be replaced by -N =.)
Represents a group selected from the group consisting of
Z ⁱ¹ represents —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —COO—, —OCO—, —CH ₂ CH ₂ —, —CF ₂ CF ₂ —, —CH ═CH—, —CF═CF—, —C≡C— or a single bond,
n ⁱ¹ represents 1 or 2, but when n ⁱ¹ represents 2 and a plurality of A ⁱ¹ and Z ⁱ¹ exist, they may be the same or different. )
One —CH ₂ — or adjacent group present in L ⁱ¹ , L ⁱ² , L ⁱ³ , L ⁱ⁴ , L ⁱ⁵ , L ⁱ⁶ , L ⁱ⁷ , L ⁱ⁸ , L ⁱ⁹ and L ⁱ¹⁰ Two or more —CH ₂ — that are not present may be replaced by —C≡C—, —O—, —S—, —COO—, —OCO— or —CO—, and may be an alkyl group or alkenyl. A hydrogen atom present in the group may be substituted with a fluorine atom. )
Represents a group represented by )
In addition, a liquid crystal composition containing the compound, a liquid crystal display device using the liquid crystal composition, a method for producing the compound, and an intermediate thereof are provided.

The compound represented by the general formula (i) provided by the present invention has a high clearing point (T _ni ). Therefore, a stable nematic phase can be exhibited in a wide temperature range by using the compound represented by the general formula (i) as a component of the liquid crystal composition. In addition, the compound represented by the general formula (i) provided by the present invention exhibits a large | Δε | and also has a high chemical stability. Therefore, by using the compound represented by the general formula (i) as a component of the liquid crystal composition, a liquid crystal composition exhibiting a low γ ₁ can be obtained. For this reason, it is very useful as a component of a liquid crystal composition for a liquid crystal display element that requires a high-speed response.

X ⁱ¹ and X ⁱ² each independently preferably represent a fluorine atom, and in order to exhibit a more negative Δε, it is more preferable that both X ⁱ¹ and X ⁱ² represent a fluorine atom.

Y ⁱ¹ and Y ⁱ² each independently preferably represent an oxygen atom or a sulfur atom, and it is more preferable that both Y ⁱ¹ and Y ⁱ² represent an oxygen atom or a sulfur atom in order to exhibit a more negative Δε. In order to improve long-term reliability when a liquid crystal display element is produced while exhibiting a large negative Δε, both are preferably oxygen atoms. is ^{preferably, Y i2} is -CH ₂ - - either ^{Y i1} and ^{Y i2} is -CH ₂ in the case of emphasizing gamma ₁ and more preferably from. In order to show a larger Δn, both are preferably sulfur atoms.

W ⁱ¹

(However, the black point in the formula represents the point of attachment to L ⁱ² or Y ⁱ² .)
It is preferable that when T _ni and γ ₁ are important

(However, the black point in the formula represents the point of attachment to L ⁱ² or Y ⁱ² .)
In order to increase the miscibility with other liquid crystal components.

(However, the black point in the formula represents the point of attachment to L ⁱ² or Y ⁱ² .)
It is more preferable that to show a large Δn

(However, the black point in the formula represents the point of attachment to L ⁱ² or Y ⁱ² .)
It is more preferable that

W ⁱ² preferably represents a single bond or —CH ₂ CH ₂ —.

L ⁱ¹ and L ⁱ² each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, or an alkenyl group having 2 to 15 carbon atoms. In order to reduce γ ₁ , An alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms is particularly preferable. Moreover, it is preferable that it is linear. In order to increase | Δε |, it is preferably an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms or 2 carbon atoms. Particularly preferred is an alkenyloxy group of 5 to 5. In order to increase the miscibility with other liquid crystal components, L ⁱ¹ and L ⁱ² are preferably different, and the alkoxy group or alkenyloxy group is preferably one of L ⁱ¹ and L ⁱ² , Is particularly preferably L ⁱ¹ . The hydrogen atom present in L ⁱ¹ and L ⁱ² may be substituted with a fluorine atom, but is preferably not substituted with a fluorine atom.

L ⁱ¹ and L ⁱ² are

Is preferably represented.

R ⁱ¹ is preferably an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms in order to reduce γ _1, and an alkyl group having 1 to 5 carbon atoms or the number of carbon atoms Particularly preferred are 2 to 5 alkenyl groups. Moreover, it is preferable that it is linear. In order to increase | Δε |, it is preferably an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms or 2 carbon atoms. Particularly preferred is an alkenyloxy group of 5 to 5. When there are a plurality of R ^{i1 s,} in order to increase the miscibility with other liquid crystal components, it is preferable that R ^i1s are different from each other, and any one of R ^{i1s having} a plurality of alkoxy groups or alkenyloxy groups exists. And the alkoxy group or alkenyloxy group is particularly preferably R ⁱ¹ in L ⁱ¹ . The hydrogen atom present in R ⁱ¹ may be substituted with a fluorine atom, but is preferably not substituted with a fluorine atom.

A ⁱ¹ is

It is preferable to represent a group selected from: Specifically, A ¹ is a trans-1,4-cyclohexylene group, an unsubstituted 1,4-phenylene group, a 2-fluoro-1,4-phenylene group, or a 3-fluoro group for decreasing γ _1. A 1,4-phenylene group is preferred, and a trans-1,4-cyclohexylene group is particularly preferred. In order to improve miscibility with other liquid crystal components, it may be a trans-1,4-cyclohexylene group, a 2-fluoro-1,4-phenylene group or a 3-fluoro-1,4-phenylene group. preferable. In order to increase T _ni , an unsubstituted 1,4-phenylene group, an unsubstituted 1,4-cyclohexylene group, a 1,4-cyclohexenylene group, or an unsubstituted naphthalene-2,6-diyl group It is preferable that In order to exhibit negatively large Δε, a 2-fluoro-1,4-phenylene group, a 3-fluoro-1,4-phenylene group, or a 2,3-difluoro-1,4-phenylene group is preferable. In order to achieve both miscibility with other liquid crystal components while exhibiting a negative Δε, the total number of fluorine atoms present in A ⁱ¹ is preferably 1 to 4, preferably 1 to 3. It is particularly preferred.

Z ⁱ¹ is preferably a single bond, —CH ₂ CH ₂ —, —CH ₂ O— or —OCH ₂ —, and preferably a single bond or —CH ₂ CH ₂ — in order to decrease γ _1. Is more preferable. In order to increase T _ni , a single bond, —COO—, —OCO—, —CH═CH— or —C≡C— is preferable, and a single bond, —CH═CH— or —C≡C— -Is more preferable. In order to improve miscibility with other liquid crystal components, a single bond, —CH ₂ CH ₂ —, —CH ₂ O— or —OCH ₂ — is preferable. In order to improve long-term reliability when a liquid crystal display device is used, a single bond is preferable.

When n ⁱ¹ represents 2, it is preferable that any one or more of a plurality of Z ⁱ¹ represent a single bond. n ⁱ¹ is preferably 1 when γ ₁ is important. When importance is attached to _Tni , it is preferably 2.

L ⁱ³ represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, or an alkenyloxy group having 2 to 15 carbon atoms. In order to reduce γ ₁ , an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms or 2 carbon atoms is preferable. Particularly preferred is an alkenyl group of ˜5. Moreover, it is preferable that it is linear.

When L ⁱ¹ represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, or an alkenyl group having 2 to 15 carbon atoms, L ⁱ³ is

Is preferably represented.

L ⁱ⁴ and L ⁱ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, or an alkenyl group having 2 to 15 carbon atoms, and more preferably a hydrogen atom.

L ⁱ⁶ and L ⁱ⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, or an alkenyl group having 2 to 15 carbon atoms. In order to reduce γ ₁ , An alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms is particularly preferable. Moreover, it is preferable that it is linear.
L ⁱ⁸ represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, or an alkenyloxy group having 2 to 15 carbon atoms. In order to reduce γ ₁ , an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms or 2 carbon atoms is preferable. Particularly preferred is an alkenyl group of ˜5. Moreover, it is preferable that it is linear.

When L ⁱ² represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, or an alkenyl group having 2 to 15 carbon atoms, L ⁱ⁸ is

Is preferably represented.

L ⁱ⁹ and L ⁱ¹⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, or an alkenyl group having 2 to 15 carbon atoms, and more preferably a hydrogen atom.

In the compound represented by the general formula (i)

In the case where a group represented by the formula (1) is present, the number of the groups is preferably 2 or less in order to increase the miscibility with other liquid crystal components. When there are two such groups in general formula (i), it is preferably present at the positions of L ⁱ¹ and L ⁱ² , L ⁱ¹ and L ⁱ⁸ , L ⁱ³ and L ⁱ² , or L ⁱ³ and L ^i8. . When two groups exist in the general formula (i), it is preferably present at the positions of L ⁱ¹ and L ⁱ² . In addition, in the compound represented by general formula (i), it does not become a structure where hetero atoms are directly bonded.
Of the general formula (i), compounds represented by the following general formulas (i-1) to (i-946) are preferable. Among them, particularly preferred compounds are (i-1), (i-2), (i-3), (i-4), (i-5), (i-6), (i-7), (I-8), (i-9), (i-10), (i-11), (i-12).

^{(Wherein, R i1} and ^{R i2} are the general formula (i) represents the same meaning as ^{R i1.)}

In the present invention, the compound represented by the general formula (i) is, for example, the general formula (i-r1)

( ^Wherein X ⁱ² , Y ⁱ² , W ⁱ¹ , L ⁱ² and L ⁱ⁵ represent the same meaning as X ⁱ² , Y ⁱ² , W ⁱ¹ , L ⁱ² and L ⁱ⁵ in general formula (i), respectively, but a plurality of X ⁱ² may be different even in the same,
R ⁱ³ and R ⁱ⁴ each independently represent a hydrogen atom, a methyl group, an ethyl group, or a propyl group, or R ⁱ³ and R ⁱ⁴ are bonded to each other to form a cyclic structure —CH ₂ —CH ₂ —, —CH ₂ -CH ₂ -CH _2- or -CH ₂ -C (CH ₃ ) ₂ -CH _2-
A broken line indicates that a bond may not exist or may exist. )
And a compound of the general formula (ir-2)

( ^Wherein X ⁱ¹ , Y ⁱ¹ , L ⁱ¹ , L ⁱ³ , L ⁱ⁴ and W ⁱ² represent the same meanings as X ⁱ¹ , Y ⁱ¹ , L ⁱ¹ , L ⁱ³ , L ⁱ⁴ and W ⁱ² in general formula (i), respectively. ,
X ⁱ³ represents a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, a p-toluenesulfonyloxy group, or a trifluoromethanesulfonyloxy group. )
Is reacted in the presence of a transition metal catalyst and a base to give a compound of the general formula (ir-3)

( ^Wherein X ⁱ¹ , X ⁱ² , Y ⁱ¹ , Y ⁱ² , W ⁱ¹ , W ⁱ² , L ⁱ¹ , L ⁱ² , L ⁱ³ , L ⁱ⁴ and L ⁱ⁵ are X ⁱ¹ , X ⁱ² , Y ⁱ¹ in the general formula (i)). , Y ⁱ² , W ⁱ¹ , W ⁱ² , L ⁱ¹ , L ⁱ² , L ⁱ³ , L ⁱ⁴ and L ⁱ⁵ each represent the same meaning, but a plurality of X ⁱ² may be the same or different,
A broken line indicates that a bond may not exist or may exist. )
Is obtained by deprotonating —Y ⁱ¹ —H in the general formula (i-r3) with a base to generate an anion, thereby causing an intramolecular reaction.
The compound represented by the general formula (i) is, for example, the general formula (i-r4)

( ^Where X ⁱ¹ , X ⁱ² , Y ⁱ¹ , Y ⁱ² , W ⁱ² , L ⁱ¹ , L ⁱ³ , L ⁱ⁴ and L ⁱ⁵ are X ⁱ¹ , X ⁱ² , Y ⁱ¹ , Y ⁱ² , W ⁱ² in the general formula (i)). , L ⁱ¹ , L ⁱ³ , L ⁱ⁴ and L ⁱ⁵ each have the same meaning,
L ⁱ¹¹ represents the same meaning as L ⁱ¹ . )
The compound represented by general formula (ir5) is deprotonated with an organometallic reagent and then reacted with bromine or iodine.

( ^Where X ⁱ¹ , X ⁱ² , Y ⁱ¹ , Y ⁱ² , W ⁱ² , L ⁱ¹ , L ⁱ³ , L ⁱ⁴ and L ⁱ⁵ are X ⁱ¹ , X ⁱ² , Y ⁱ¹ , Y ⁱ² , W ⁱ² in the general formula (i)). , L ⁱ¹ , L ⁱ³ , L ⁱ⁴ and L ⁱ⁵ each have the same meaning,
L ⁱ¹¹ represents the same meaning as L ⁱ¹ ,
X ⁱ³ represents a bromine atom or an iodine atom. )
To obtain a compound represented by the general formula (ir-6)

(Wherein ^{L i2} are as defined ^{L i2} in the general formula (i).)
Is reacted with a compound represented by general formula (ir-7) in the presence of a transition metal catalyst, a copper catalyst and a base.

( ^Where X ⁱ¹ , X ⁱ² , Y ⁱ¹ , Y ⁱ² , W ⁱ² , L ⁱ¹ , L ⁱ² , L ⁱ³ , L ^i4, and L ⁱ⁵ are X ⁱ¹ , X ⁱ² , Y ⁱ¹ , Y ⁱ² in general formula (i)). , W ⁱ² , L ⁱ¹ , L ⁱ² , L ⁱ³ , L ⁱ⁴ and L ⁱ⁵ respectively,
L ⁱ¹¹ represents the same meaning as L ⁱ¹ . )
After obtaining a compound represented by in, W ⁱ¹ By the -Y ⁱ² -L ⁱ¹¹ in the general formula (i-r7) to proceed deprotection reaction and intramolecular reaction by the presence of water acid simultaneously

(However, the black point in the formula represents the point of attachment to L ⁱ² or Y ⁱ² .)
It is obtained as represented by In addition, an addition reaction to the double bond of the compound causes W ⁱ¹ to

(However, the black point in the formula represents the point of attachment to L ⁱ² or Y ⁱ² .)
Can be obtained. More specifically, it can be produced as follows. Of course, the spirit and scope of the present invention are not limited by these production examples.
(Manufacturing method 1)

( ^Wherein L ⁱ¹ , L ⁱ² , X ⁱ¹ and X ⁱ² represent the same meaning as L ⁱ¹ , L ⁱ² , X ⁱ¹ and X ⁱ² in the general formula (i),
R ⁱ³ and R ⁱ⁴ each independently represent a hydrogen atom, a methyl group, an ethyl group, or a propyl group, or R ⁱ³ and R ⁱ⁴ are bonded to each other to form a cyclic structure —CH ₂ —CH ₂ —, —CH ₂ -CH ₂ -CH _2- or -CH ₂ -C (CH ₃ ) ₂ -CH _2-
L ⁱ¹¹ represents the same meaning as L ⁱ¹ ,
X ⁱ³ represents a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, a p-toluenesulfonyloxy group, a trifluoromethanesulfonyloxy group,
X ⁱ⁴ represents a chlorine atom, a bromine atom or an iodine atom,
X ⁱ⁵ represents a bromine atom or an iodine atom,
Y ⁱ³ represents —O— or —S—. )
A compound represented by general formula (S-3) is obtained by reacting a compound represented by general formula (S-1) with a compound represented by (S-2) in the presence of a transition metal catalyst and a base. Can do.
Any transition metal catalyst may be used as long as it allows the reaction to proceed suitably. Tetrakis (triphenylphosphine) palladium (0), palladium (II) acetate, bis (triphenylphosphine) palladium dichloride (II), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride or bis [di-tert-butyl (4-dimethylaminophenyl) phosphine] palladium (II) dichloride is preferred, Tetrakis (triphenylphosphine) palladium (0), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) or bis [di-tert-butyl (4-dimethylaminophenyl) phosphine] dichloride More preferably, it is palladium (II). Moreover, in order to advance reaction suitably, you may add phosphine-type ligands, such as a triphenylphosphine, as needed.

The reaction solvent to be used may be any as long as it allows the reaction to proceed suitably, but ether solvents such as tetrahydrofuran, diethyl ether and tert-butyl methyl ether, alcohol solvents such as methanol, ethanol and propanol, Aromatic solvents such as benzene, toluene and xylene are preferred, and tetrahydrofuran, ethanol and toluene are more preferred. Further, water may be used as necessary in order to allow the reaction to proceed appropriately.

Any base can be used as long as it allows the reaction to proceed suitably. Carbonates such as potassium carbonate, sodium carbonate and cesium carbonate; phosphates such as tripotassium phosphate and potassium dihydrogen phosphate; Are preferable, and potassium carbonate, cesium carbonate, and tripotassium phosphate are more preferable.

The reaction temperature may be any number of times as long as the reaction proceeds suitably, but is preferably from room temperature to the temperature at which the solvent used is refluxed, more preferably from 40 ° C to the temperature at which the solvent is refluxed. A temperature from 60 ° C. to the reflux of the solvent is particularly preferred.
The compound represented by the general formula (S-4) can be obtained by intramolecular reaction of the compound represented by the general formula (S-3). This intramolecular reaction can be performed by deprotonating —Y ⁱ³ —H of the general formula (S-3) with a base to generate an anion.
Examples of the base used in this case include metal hydrides, metal carbonates, metal phosphates, metal hydroxides, metal carboxylates, metal amides and metals, among which alkali metal hydrides and alkali metals. Phosphate, alkali metal phosphate, alkali metal carbonate, alkali metal hydroxide, alkali metal amide and alkali metal are preferred, and alkali metal phosphate, alkali metal hydride and alkali metal carbonate are more preferred. Lithium hydride, sodium hydride and potassium hydride as alkali metal hydrides, tripotassium phosphate as alkali metal phosphates, sodium carbonate, sodium bicarbonate, cesium carbonate, potassium carbonate as alkali metal carbonates And potassium hydrogen carbonate can be preferably mentioned.

Any reaction solvent may be used as long as it allows the reaction to proceed suitably, but ether solvents, chlorine solvents, hydrocarbon solvents, aromatic solvents, polar solvents, and the like can be preferably used. Examples of ether solvents include 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether and t-butyl methyl ether, and examples of chlorine solvents include dichloromethane, 1,2-dichloroethane and carbon tetrachloride. Examples of hydrocarbon solvents include pentane, hexane, cyclohexane, heptane, and octane, examples of aromatic solvents include benzene, toluene, xylene, mesitylene, chlorobenzene, and dichlorobenzene, and examples of polar solvents include N, N-dimethylformamide, Preferable examples include N-methylpyrrolidone, dimethyl sulfoxide, and sulfolane. Of these, ether solvents such as tetrahydrofuran and diethyl ether and polar solvents such as N, N-dimethylformamide are more preferable. Moreover, each said solvent may be used independently, or 2 or more types of solvents may be mixed and used.

The reaction temperature can be from the freezing point of the solvent to the reflux temperature range, but is preferably 0 ° C to 150 ° C, more preferably 30 ° C to 120 ° C.

The compound represented by the general formula (S-5) can be obtained by oxidizing the compound represented by the general formula (S-4). This oxidation can be carried out by deprotonation with an organometallic reagent, reaction with a trialkyl borate to form a boron compound, and subsequent action of an oxidizing agent.
Any reaction solvent may be used as long as it allows the reaction to proceed suitably, and examples thereof include ether solvents and hydrocarbon solvents. Examples of ether solvents include 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether, and t-butyl methyl ether. Examples of hydrocarbon solvents include pentane, hexane, cyclohexane, heptane, and octane. Of these, tetrahydrofuran is preferred. Examples of the organometallic reagent include n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, lithium diisopropylamide and lithium 2,2,4,4-tetramerpiperidide. N-Butyllithium, sec-butyllithium, and lithium diisopropylamide are preferable from the viewpoint of ease of handling, and sec-butyllithium and lithium diisopropylamide that can be efficiently deprotonated are more preferable. In the deprotonation, a base such as potassium tert-butoxide or tetramethylethylenediamine may be used as an additive together with the organometallic reagent. The reaction temperature for deprotonation is preferably from −100 ° C. to −20 ° C., more preferably from −78 ° C. to −40 ° C.

As the trialkyl borate, trimethyl borate, triethyl borate, tripropyl borate and triisopropyl borate are preferably used, but trimethyl borate and triisopropyl borate are more preferred from the viewpoint of availability and handling. As the combination of trialkyl borate and organometallic reagent, any of the above-mentioned combinations are possible, but the combination of sec-butyl lithium and trimethyl borate, and the combination of lithium diisopropylamide and triisopropyl borate are preferable, and lithium diisopropyl A combination of amide and triisopropyl borate is more preferred. The reaction temperature during boriding is preferably -100 ° C to -20 ° C, more preferably -78 ° C to -40 ° C. The obtained boron compound may be isolated once or may be reacted with an oxidizing agent without isolation. Further, the obtained boron compound may be hydrolyzed and converted into a boric acid compound and then reacted with an oxidizing agent.

As the oxidizing agent, it is preferable to use hydrogen peroxide, peracetic acid or performic acid. The reaction temperature is preferably -78 ° C to 70 ° C, more preferably 0 ° C to 50 ° C. Moreover, water may be contained in the solvent at the time of reaction with an oxidizing agent.
The compound represented by the general formula (S-7) can be obtained by reacting the hydroxyl group of the general formula (S-5) with the base as a phenolate with the general formula (S-6).

Examples of the base used in this case include metal hydrides, metal carbonates, metal phosphates, metal hydroxides, metal carboxylates, metal amides and metals, among which alkali metal hydrides and alkali metals. Phosphate, alkali metal phosphate, alkali metal carbonate, alkali metal hydroxide, alkali metal amide and alkali metal are preferred, and alkali metal phosphate, alkali metal hydride and alkali metal carbonate are more preferred. Lithium hydride, sodium hydride and potassium hydride as alkali metal hydrides, tripotassium phosphate as alkali metal phosphates, sodium carbonate, sodium bicarbonate, cesium carbonate, potassium carbonate as alkali metal carbonates And potassium hydrogen carbonate can be preferably mentioned.
Any reaction solvent may be used as long as it allows the reaction to proceed suitably. Ether solvents, chlorine solvents, hydrocarbon solvents, aromatic solvents, polar solvents, and the like can be preferably used. Examples of ether solvents include 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether and t-butyl methyl ether, and examples of chlorine solvents include dichloromethane, 1,2-dichloroethane and carbon tetrachloride. Examples of hydrocarbon solvents include pentane, hexane, cyclohexane, heptane, and octane, examples of aromatic solvents include benzene, toluene, xylene, mesitylene, chlorobenzene, and dichlorobenzene, and examples of polar solvents include N, N-dimethylformamide, Preferable examples include N-methylpyrrolidone, dimethyl sulfoxide, and sulfolane. Of these, ether solvents such as tetrahydrofuran and diethyl ether and polar solvents such as N, N-dimethylformamide are more preferable. Moreover, each said solvent may be used independently, or 2 or more types of solvents may be mixed and used.

The reaction temperature can be in the range from the freezing point of the solvent to the reflux temperature, preferably from 0 ° C to 150 ° C, more preferably from 30 ° C to 120 ° C. The generated phenolate may be isolated once and then reacted with the compound represented by the general formula (S-5), or may be reacted without isolation, but it is not isolated for ease of work. It is better to react.
The compound represented by the general formula (S-8) can be obtained by halogenating the compound represented by the general formula (S-7). This halogenation can be performed by deprotonation with an organometallic reagent and then reacting with bromine or iodine to form a halogen compound.
Any reaction solvent may be used as long as it allows the reaction to proceed suitably, and examples thereof include ether solvents and hydrocarbon solvents. Examples of ether solvents include 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether, and t-butyl methyl ether. Examples of hydrocarbon solvents include pentane, hexane, cyclohexane, heptane, and octane. Of these, tetrahydrofuran is preferred.

Examples of organometallic reagents include n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, lithium diisopropylamide and lithium 2,2,4,4-tetramethylpiperidide. N-Butyllithium, sec-butyllithium, and lithium diisopropylamide are preferable from the viewpoint of ease of handling, and sec-butyllithium and lithium diisopropylamide that can be efficiently deprotonated are more preferable. In the deprotonation, a base such as potassium tert-butoxide or tetramethylethylenediamine may be used as an additive together with the organometallic reagent. The reaction temperature for deprotonation is preferably from −100 ° C. to −20 ° C., more preferably from −78 ° C. to −40 ° C.
A compound represented by general formula (S-10) by reacting a compound represented by general formula (S-8) with a compound represented by (S-9) in the presence of a transition metal catalyst, a copper catalyst and a base. Can be obtained.
Any transition metal catalyst may be used as long as it allows the reaction to proceed suitably. Tetrakis (triphenylphosphine) palladium (0), palladium (II) acetate, bis (triphenylphosphine) palladium dichloride (II), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride or bis [di-tert-butyl (4-dimethylaminophenyl) phosphine] palladium (II) dichloride is preferred, Tetrakis (triphenylphosphine) palladium (0), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) or bis [di-tert-butyl (4-dimethylaminophenyl) phosphine] dichloride More preferably, it is palladium (II). Moreover, in order to advance reaction suitably, you may add phosphine-type ligands, such as a triphenylphosphine, as needed.
Any copper catalyst may be used as long as it allows the reaction to proceed suitably, but copper (I) chloride, copper (I) bromide, copper iodide (I), copper acetate (I), etc. A monovalent copper catalyst is preferred, and copper (I) iodide is more preferred.

The reaction solvent to be used may be any as long as it allows the reaction to proceed suitably, but ether solvents such as tetrahydrofuran, diethyl ether and tert-butyl methyl ether, alcohol solvents such as methanol, ethanol and propanol, Aromatic solvents such as benzene, toluene and xylene, polar solvents such as N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide and sulfolane are preferred, and tetrahydrofuran, ethanol, toluene and N, N-dimethylformamide are more preferred. . Further, water may be used as necessary in order to allow the reaction to proceed appropriately.

Any base can be used as long as it allows the reaction to proceed appropriately. Triethylamine, diethylamine, ethylamine, trimethylamine, dimethylamine, methylamine, diisopropylethylamine, diisopropylamine, isopropylamine, N, N-tetra Preferred are amines such as methylethylenediamine, ethylenediamine, triethanolamine, diethanolamine, ethanolamine, carbonates such as potassium carbonate, sodium carbonate, cesium carbonate, phosphates such as tripotassium phosphate, potassium dihydrogen phosphate, triethylamine, Diethylamine, diisopropylethylamine, and diisopropylamine are more preferable.

The reaction temperature may be any number of times as long as the reaction proceeds suitably, but is preferably from room temperature to the temperature at which the solvent used is refluxed, more preferably from 40 ° C to the temperature at which the solvent is refluxed. A temperature from 60 ° C. to the reflux of the solvent is particularly preferred.

The compound represented by the general formula (S-11) can be obtained by simultaneously performing deprotection with an acid and intramolecular reaction in the presence of water in the compound represented by the general formula (S-10).

Any acid can be used as long as it allows the reaction to proceed suitably, but inorganic acids such as hydrochloric acid and sulfuric acid, sulfonic acids such as p-toluenesulfonic acid, and the like are preferable, and hydrochloric acid is more preferable.

As the solvent to be used, any solvent can be used as long as it allows the reaction to proceed suitably, but water-soluble solvents such as tetrahydrofuran, ethanol, methanol, isopropyl alcohol and the like are preferable.

The reaction temperature may be any temperature that allows the reaction to proceed suitably, but a temperature from room temperature to the boiling point of the solvent is preferred.

The compound represented by the general formula (S-12) can be obtained by reacting the compound represented by the general formula (S-11) with hydrogen gas in the presence of a metal catalyst in an organic solvent.

Any organic solvent may be used as long as it allows the reaction to proceed suitably, but ether solvents such as diisopropyl ether, diethyl ether, 1,4-dioxane or tetrahydrofuran, hexane, heptane, toluene or xylene, etc. Hydrocarbon solvents, alcohol solvents such as methanol, ethanol, propanol, isopropyl alcohol or butanol, and ester solvents such as ethyl acetate or butyl acetate are preferred, and tetrahydrofuran, hexane, heptane, toluene, ethanol or ethyl acetate are preferred. Moreover, it is also preferable to add acids, such as hydrochloric acid, acetic acid, or a sulfuric acid, as needed.

The reaction temperature may be any temperature that allows the reaction to proceed suitably, but is preferably 0 ° C. to 80 ° C., more preferably room temperature to 60 ° C.

The metal catalyst to be used may be any metal catalyst that allows the reaction to proceed suitably, but is preferably palladium carbon, ruthenium carbon, platinum black or platinum oxide, and more preferably palladium carbon.

The hydrogen pressure at the time of reaction may be any as long as it allows the reaction to proceed suitably, but is preferably from atmospheric pressure to 0.5 MPa, and more preferably from 0.2 MPa to 0.5 MPa.
(Manufacturing method 2)

^(Wherein, ^{^{^{L i1, L i2, X i1}}} , X i2, Y i2 and ^{W i1} are the same meaning in the general formula (i) and ^{^{^{^{L i1, L i2, X i1}}}} , X i2, Y i2 and ^{W i1} Represent,
R ⁱ³ and R ⁱ⁴ each independently represent a hydrogen atom, a methyl group, an ethyl group, or a propyl group, or R ⁱ³ and R ⁱ⁴ are bonded to each other to form a cyclic structure —CH ₂ —CH ₂ —, —CH ₂ -CH ₂ -CH _2- or -CH ₂ -C (CH ₃ ) ₂ -CH _2-
X ⁱ³ represents a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, a p-toluenesulfonyloxy group, a trifluoromethanesulfonyloxy group,
X ⁱ⁴ represents a bromine atom or an iodine atom,
Y ⁱ³ represents —O— or —S—. )
The compound represented by the general formula (S-14) can be obtained by boronizing the compound represented by the general formula (S-13). This boronation can be performed by deprotonation with an organometallic reagent and then reacting with a trialkyl borate to form a boron compound.
Any reaction solvent may be used as long as it allows the reaction to proceed suitably, and examples thereof include ether solvents and hydrocarbon solvents. Examples of ether solvents include 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether, and t-butyl methyl ether. Examples of hydrocarbon solvents include pentane, hexane, cyclohexane, heptane, and octane. Of these, tetrahydrofuran is preferred.

Examples of organometallic reagents include n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, lithium diisopropylamide and lithium 2,2,4,4-tetramethylpiperidide. N-Butyllithium, sec-butyllithium and lithium diisopropylamide are preferred from the viewpoint of ease of handling, and sec-butyllithium and lithium diisopropylamide capable of efficient deprotonation are more preferred. In the deprotonation, a base such as potassium tert-butoxide or tetramethylethylenediamine may be used as an additive together with the organometallic reagent. The reaction temperature for deprotonation is preferably from −100 ° C. to −20 ° C., more preferably from −78 ° C. to −40 ° C.

As the trialkyl borate, trimethyl borate, triethyl borate, tripropyl borate and triisopropyl borate are preferably used, but trimethyl borate and triisopropyl borate are more preferred from the viewpoint of availability and handling. As the combination of trialkyl borate and organometallic reagent, any of the above-mentioned combinations are possible, but the combination of sec-butyl lithium and trimethyl borate, and the combination of lithium diisopropylamide and triisopropyl borate are preferable, and lithium diisopropyl A combination of amide and triisopropyl borate is more preferred. The reaction temperature during boriding is preferably -100 ° C to -20 ° C, more preferably -78 ° C to -40 ° C.
A compound represented by general formula (S-16) is obtained by reacting a compound represented by general formula (S-14) with a compound represented by (S-15) in the presence of a transition metal catalyst and a base. Can do.
Any transition metal catalyst may be used as long as it allows the reaction to proceed suitably. Tetrakis (triphenylphosphine) palladium (0), palladium (II) acetate, bis (triphenylphosphine) palladium dichloride (II), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride or bis [di-tert-butyl (4-dimethylaminophenyl) phosphine] palladium (II) dichloride is preferred, Tetrakis (triphenylphosphine) palladium (0), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) or bis [di-tert-butyl (4-dimethylaminophenyl) phosphine] dichloride More preferably, it is palladium (II). Moreover, in order to advance reaction suitably, you may add phosphine-type ligands, such as a triphenylphosphine, as needed.

The reaction temperature may be any number of times as long as the reaction proceeds suitably, but is preferably from room temperature to the temperature at which the solvent used is refluxed, more preferably from 40 ° C to the temperature at which the solvent is refluxed. A temperature from 60 ° C. to the reflux of the solvent is particularly preferred.
The compound represented by the general formula (S-17) can be obtained by intramolecular reaction of the compound represented by the general formula (S-16). This intramolecular reaction can be carried out by deprotonation of —Y ⁱ³ —H of the general formula (S-16) with a base to generate an anion.
Examples of the base used in this case include metal hydrides, metal carbonates, metal phosphates, metal hydroxides, metal carboxylates, metal amides and metals, among which alkali metal hydrides and alkali metals. Phosphate, alkali metal phosphate, alkali metal carbonate, alkali metal hydroxide, alkali metal amide and alkali metal are preferred, and alkali metal phosphate, alkali metal hydride and alkali metal carbonate are more preferred. Lithium hydride, sodium hydride and potassium hydride as alkali metal hydrides, tripotassium phosphate as alkali metal phosphates, sodium carbonate, sodium bicarbonate, cesium carbonate, potassium carbonate as alkali metal carbonates And potassium hydrogen carbonate can be preferably mentioned.

The reaction temperature can be in the range from the freezing point of the solvent to the reflux temperature, preferably from 0 ° C to 150 ° C, more preferably from 30 ° C to 120 ° C.
The compound represented by the general formula (S-18) can be obtained by halogenating the compound represented by the general formula (S-17). This halogenation can be performed by deprotonation with an organometallic reagent and then reacting with bromine or iodine to form a halogen compound.
Any reaction solvent may be used as long as it allows the reaction to proceed suitably, and examples thereof include ether solvents and hydrocarbon solvents. Examples of ether solvents include 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether, and t-butyl methyl ether. Examples of hydrocarbon solvents include pentane, hexane, cyclohexane, heptane, and octane. Of these, tetrahydrofuran is preferred.

Examples of organometallic reagents include n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, lithium diisopropylamide and lithium 2,2,4,4-tetramethylpiperidide. N-Butyllithium, sec-butyllithium, and lithium diisopropylamide are preferable from the viewpoint of ease of handling, and sec-butyllithium and lithium diisopropylamide that can be efficiently deprotonated are more preferable. In the deprotonation, a base such as potassium tert-butoxide or tetramethylethylenediamine may be used as an additive together with the organometallic reagent. The reaction temperature for deprotonation is preferably from −100 ° C. to −20 ° C., more preferably from −78 ° C. to −40 ° C.
A compound represented by general formula (S-20) is obtained by reacting a compound represented by general formula (S-18) with a compound represented by (S-19) in the presence of a transition metal catalyst and a base. Can do.
Any transition metal catalyst may be used as long as it allows the reaction to proceed suitably. Tetrakis (triphenylphosphine) palladium (0), palladium (II) acetate, bis (triphenylphosphine) palladium dichloride (II), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride or bis [di-tert-butyl (4-dimethylaminophenyl) phosphine] palladium (II) dichloride is preferred, Tetrakis (triphenylphosphine) palladium (0), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) or bis [di-tert-butyl (4-dimethylaminophenyl) phosphine] dichloride More preferably, it is palladium (II). Moreover, in order to advance reaction suitably, you may add phosphine-type ligands, such as a triphenylphosphine, as needed.

The reaction temperature may be any number of times as long as the reaction proceeds suitably, but is preferably from room temperature to the temperature at which the solvent used is refluxed, more preferably from 40 ° C to the temperature at which the solvent is refluxed. A temperature from 60 ° C. to the reflux of the solvent is particularly preferred.
(Manufacturing method 3)

^(Wherein, ^{^{L i2, X i1, X i2}} , Y i2 and ^{W i1} represent the same meaning in the general formula (i) and ^{^{^{L i2, X i1, X i2}}} , Y i2 and ^{W i1,}
X ⁱ⁵ represents chlorine, bromine, iodine, benzenesulfonyloxy group, p-toluenesulfonyloxy group, methanesulfonyloxy group or trifluoromethanesulfonyloxy group;
Y ⁱ³ represents —O— or —S—,
R ⁱ² represents an alkyl group having 1 to 15 carbon atoms or an alkenyl group having 2 to 15 carbon atoms. )
The compound represented by the general formula (S-21) can be obtained by oxidizing the compound represented by the general formula (S-17). This oxidation can be carried out by deprotonation with an organometallic reagent, reaction with a trialkyl borate to form a boron compound, and subsequent action of an oxidizing agent.
Any reaction solvent may be used as long as it allows the reaction to proceed suitably, and examples thereof include ether solvents and hydrocarbon solvents. Examples of ether solvents include 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether, and t-butyl methyl ether. Examples of hydrocarbon solvents include pentane, hexane, cyclohexane, heptane, and octane. Of these, tetrahydrofuran is preferred. Examples of the organometallic reagent include n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, lithium diisopropylamide and lithium 2,2,4,4-tetramerpiperidide. N-Butyllithium, sec-butyllithium, and lithium diisopropylamide are preferable from the viewpoint of ease of handling, and sec-butyllithium and lithium diisopropylamide that can be efficiently deprotonated are more preferable. In the deprotonation, a base such as potassium tert-butoxide or tetramethylethylenediamine may be used as an additive together with the organometallic reagent. The reaction temperature for deprotonation is preferably from −100 ° C. to −20 ° C., more preferably from −78 ° C. to −40 ° C.

As the oxidizing agent, hydrogen peroxide water, peracetic acid or performic acid is preferably used. The reaction temperature is preferably -78 ° C to 70 ° C, more preferably 0 ° C to 50 ° C. Moreover, water may be contained in the solvent at the time of reaction with an oxidizing agent.

The compound represented by the general formula (S-23) can be obtained by reacting the compound represented by the general formula (S-21) with the compound represented by the general formula (S-22). This reaction can be carried out by reacting the hydroxyl group of the general formula (S-21) with the base as a phenolate with the general formula (S-22). The base used in this case is a metal hydride, metal carbonate, metal Mention may be made of phosphates, metal hydroxides, metal carboxylates, metal amides and metals, among which alkali metal hydrides, alkali metal phosphates, alkali metal phosphates, alkali metal carbonates, alkali metals Hydroxides, alkali metal amides and alkali metals are preferred, and alkali metal phosphates, alkali metal hydrides and alkali metal carbonates are more preferred. Lithium hydride, sodium hydride and potassium hydride as alkali metal hydrides, tripotassium phosphate as alkali metal phosphates, sodium carbonate, sodium bicarbonate, cesium carbonate, potassium carbonate as alkali metal carbonates And potassium hydrogen carbonate can be preferably mentioned.
Any reaction solvent may be used as long as it allows the reaction to proceed suitably. Ether solvents, chlorine solvents, hydrocarbon solvents, aromatic solvents, polar solvents, and the like can be preferably used. Examples of ether solvents include 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether and t-butyl methyl ether, and examples of chlorine solvents include dichloromethane, 1,2-dichloroethane and carbon tetrachloride. Examples of hydrocarbon solvents include pentane, hexane, cyclohexane, heptane, and octane, examples of aromatic solvents include benzene, toluene, xylene, mesitylene, chlorobenzene, and dichlorobenzene, and examples of polar solvents include N, N-dimethylformamide, Preferable examples include N-methylpyrrolidone, dimethyl sulfoxide, and sulfolane. Of these, ether solvents such as tetrahydrofuran and diethyl ether and polar solvents such as N, N-dimethylformamide are more preferable. Moreover, each said solvent may be used independently, or 2 or more types of solvents may be mixed and used.

The reaction temperature can be in the range from the freezing point of the solvent to the reflux temperature, preferably from 0 ° C to 150 ° C, more preferably from 30 ° C to 120 ° C. The phenolate produced may be isolated once and then reacted with the compound represented by the general formula (S-22), or it may be reacted without isolation, but it is not isolated for ease of work. It is better to react.
(Manufacturing method 4)

(In the formula, L ⁱ¹ , L ⁱ² , X ⁱ¹ , X ⁱ² , Y ⁱ² and W ⁱ¹¹ have the same meaning as L ⁱ¹ , L ⁱ² , X ⁱ¹ , X ⁱ² , Y ⁱ² and W ⁱ¹ in the general formula (i)). Represent,
Y ⁱ³ represents —O— or —S—. )
The compound represented by the general formula (S-25) can be obtained by reacting the compound represented by the general formula (S-17) with the compound represented by the general formula (S-24). This reaction can be carried out by deprotonation with an organometallic reagent and reaction with general formula (S-24).
Any reaction solvent may be used as long as it allows the reaction to proceed suitably, and examples thereof include ether solvents and hydrocarbon solvents. Examples of ether solvents include 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether, and t-butyl methyl ether. Examples of hydrocarbon solvents include pentane, hexane, cyclohexane, heptane, and octane. Of these, tetrahydrofuran is preferred.
Examples of organometallic reagents include n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, lithium diisopropylamide and lithium 2,2,4,4-tetramethylpiperidide. N-Butyllithium, sec-butyllithium, and lithium diisopropylamide are preferable from the viewpoint of ease of handling, and sec-butyllithium and lithium diisopropylamide that can be efficiently deprotonated are more preferable. In the deprotonation, a base such as potassium tert-butoxide or tetramethylethylenediamine may be used as an additive together with the organometallic reagent. The reaction temperature for deprotonation is preferably from −100 ° C. to −20 ° C., more preferably from −78 ° C. to −40 ° C.

A compound represented by the general formula (S-26) can be obtained by dehydrating the compound represented by the general formula (S-25). Examples of the dehydration method include a method of heating in the presence of an acid. Examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid, and potassium bisulfate, organic acids such as acetic acid, trifluoroacetic acid, and p-toluenesulfonic acid, and Lewis acids such as boron trifluoride. Alternatively, as a dehydration method, the hydroxyl group can be reacted with p-toluenesulfonic acid chloride, trifluoromethanesulfonic acid chloride, triphosgene, etc. to convert it to a leaving group, and then dehydrated by performing an elimination reaction.
The compound represented by the general formula (S-27) can be obtained by reacting the compound represented by the general formula (S-26) with hydrogen gas in an organic solvent in the presence of a metal catalyst.

The hydrogen pressure at the time of reaction may be any as long as it allows the reaction to proceed suitably, but is preferably from atmospheric pressure to 0.5 MPa, and more preferably from 0.2 MPa to 0.5 MPa.
(Manufacturing method 5)

^(Wherein, ^{^{L i2, X i1, X i2}} , Y i2 and ^{W i1} represent the same meaning in the general formula (i) and ^{^{^{L i2, X i1, X i2}}} , Y i2 and ^{W i1,}
R ⁱ³ represents an alkyl group having 1 to 15 carbon atoms or an alkenyl group having 2 to 15 carbon atoms, and one —CH ₂ — or two or more non-adjacent ones present in the alkyl group or alkenyl group. —CH ₂ — may be replaced by —C≡C—, —O—, —S—, —COO—, —OCO— or —CO—, and the hydrogen atom present in the alkyl or alkenyl group is fluorine. May be substituted with atoms,
X ⁱ⁴ represents a bromine atom or an iodine atom,
X ⁱ⁵ represents a chlorine atom or a bromine atom,
Y ⁱ³ represents —O— or —S—. )
The compound represented by the general formula (S-29) can be obtained by reacting the compound represented by the general formula (S-18) with the compound represented by (S-28) in the presence of a transition metal catalyst. .
Any transition metal catalyst may be used as long as it allows the reaction to proceed suitably. Bis (triphenylphosphine) nickel (II) dichloride, [1,2-bis (diphenylphosphino) dichloride, Ethane] nickel (II), dichloride [1,2-bis (diphenylphosphino) propane] nickel (II), [1,1′-bis (diphenylphosphino) ferrocene] nickel (II), tetrakis ( Triphenylphosphine) palladium (0), palladium (II) acetate, bis (triphenylphosphine) palladium (II) dichloride, [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) or dichloride Bis [di-tert-butyl (4-dimethylaminophenyl) phosphine] palladium (II) chloride is preferred. Tetrakis (triphenylphosphine) palladium (0), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II), tris (dibenzylideneacetone) palladium (0) or bis [dichloride More preferred is -tert-butyl (4-dimethylaminophenyl) phosphine] palladium (II). Moreover, in order to advance reaction suitably, you may add phosphine-type ligands, such as a triphenylphosphine, as needed.

The reaction solvent to be used may be any as long as it allows the reaction to proceed suitably, but ether solvents such as tetrahydrofuran, diethyl ether and tert-butyl methyl ether, alcohol solvents such as methanol, ethanol and propanol, Aromatic solvents such as benzene, toluene and xylene are preferred, and tetrahydrofuran, ethanol and toluene are more preferred.

Thus, as a preferable representative example of the compound that can be used by mixing with the compound represented by the general formula (i), in the composition provided by the present invention, as the first component, the general formula (i At least one compound represented by formula (1), but it is preferable to contain at least one of the following second to fourth components as other components.

That is, the second component is a so-called n-type liquid crystal compound having a negative dielectric anisotropy, and examples thereof include compounds represented by the following general formulas (LC3) to (LC5).

^(Wherein, represents an alkyl group of ^{^{^{R LC31, R LC32, R LC41}}} , R LC42, R LC51 and ^{R LC52} is 1 to 15 carbon atoms independently, one in the alkyl group or two or more —CH ₂ — may be substituted with —O—, —CH═CH—, —CO—, —OCO—, —COO— or —C≡C— so that the oxygen atom is not directly adjacent. one or more hydrogen atoms in the group may be optionally substituted by a halogen ^{^{^{^{atom, a LC31, a LC32, a}}}} LC41, a LC42, a LC51 and ^{a LC52} each independently any of the following Structure

(In the structure, one or more —CH ₂ — in the cyclohexylene group may be substituted with an oxygen atom, and one or more —CH— in the 1,4-phenylene group is Any one of which may be substituted with a nitrogen atom, and one or more hydrogen atoms in the structure may be substituted with a fluorine atom, a chlorine atom, —CF ₃ or —OCF ₃ ). indicates ^{^{^{^{whether, Z LC31, Z LC32, Z}}}} LC41, Z LC42, Z LC51 and ^{Z LC51} each independently represent a single bond, -CH = CH -, - C≡C -, - CH 2 CH 2 -, - ( CH ₂ ) ₄ —, —COO—, —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or —CF ₂ O—, Z ⁵ represents —CH ₂ — or an oxygen atom, and X ^LC41 represents ^Represents a hydrogen atom or a fluorine atom, m ^LC31 , m ^{L ^{^{^{C32, m LC41, m LC42,}}}} m LC51 and ^{m LC52} each independently represent ^{^{^{0 ~ 3, m LC31 + m}}} LC32, m LC41 + m LC42 and ^{^m} LC51 ⁺ ^m ^LC52 is 1, 2 or ^{3, A LC31} ~ When a plurality of A ^LC52 and Z ^LC31 to Z ^LC52 are present, they may be the same or different. )
R ^LC31 to R ^LC52 are each independently preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms. Most preferably,

(In the formula, it shall be bonded to the ring structure at the right end.)
A ^LC31 to A ^LC52 each independently preferably has the following structure:

Z ^LC31 to Z ^LC51 each independently has a single bond, —CH ₂ O—, ^{—COO—, —OCO—} , —CH ₂ CH ₂ —, —CF ₂ O—, —OCF ₂ — or —OCH ₂ —. preferable.

General formula (LC3) is the following general formula (LC3-a) and general formula (LC3-b)

(Wherein R ^LC31 , R ^LC32 , A ^LC31 and Z ^LC31 each independently represent the same meaning as R ^LC31 , R ^LC32 , A ^LC31 and Z ^LC31 in the general formula (LC3), and X ^LC3b1 to X ^LC3b6 are Represents a hydrogen atom or a fluorine atom, and at least one of X ^LC3b1 and X ^LC3b2 or X ^LC3b3 and X ^LC3b4 represents a fluorine atom, m ^LC3a1 is 1, 2 or 3, and m ^LC3b1 is 0 or In the case where a plurality of A ^LC31 and Z ^LC31 are present, they may be the same or different, provided that they are represented by the general formula (LC3-b) in the general formula (LC3-a) Or a compound selected from the group of compounds represented by the formula: Rukoto is preferable.
R ^LC31 and R ^LC32 each independently represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 2 to 7 carbon atoms. Is preferably represented.

A ^LC31 preferably represents a 1,4-phenylene group, a trans-1,4-cyclohexylene group, a tetrahydropyran-2,5-diyl group, or a 1,3-dioxane-2,5-diyl group. , 4-phenylene group and trans-1,4-cyclohexylene group are more preferable.

Z ^LC31 is a single _{bond, -CH 2 O -, - COO} -, - OCO -, - CH 2 CH 2 - is preferred to represent, and more preferably a single bond.

The general formula (LC3-a) preferably represents the following general formula (LC3-a1) to general formula (LC3-a4).

(In the formula, R ^LC31 and R ^LC32 each independently represent the same meaning as R ^LC31 and R ^LC32 in General Formula (LC3).)
R ^LC31 and R ^LC32 are each independently preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms, and R ^LC31 has 1 carbon atom. More preferably, it represents an alkyl group of ^˜7 , and R ^LC32 represents an alkoxy group of 1 to 7 carbon atoms.

The general formula (LC3-b) is preferably represented by the following general formula (LC3-b1) to general formula (LC3-b12). The general formula (LC3-b1), the general formula (LC3-b6), the general formula (LC3-b8) and general formula (LC3-b11) are more preferable, general formula (LC3-b1) and general formula (LC3-b6) are more preferable, and general formula (LC3-b1) is Most preferably it represents.

(In the formula, R ^LC31 and R ^LC32 each independently represent the same meaning as R ^LC31 and R ^LC32 in General Formula (LC3).)
R ^LC31 and R ^LC32 are each independently preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms, and R ^LC31 has 2 carbon atoms. Or an alkyl group having 3 carbon atoms, and more preferably R ^LC32 represents an alkyl group having 2 carbon atoms.

General formula (LC4) is general formula (LC4-a) to general formula (LC4-c), and general formula (LC5) is general formula (LC5-a) to general formula (LC5-c).

^{^(Wherein, R} ^LC41, R ^LC42 and ^{X LC41} each independently represent the same meaning as ^{^R LC41,} ^R ^LC42 and ^{X LC41} in the general formula ^{(LC4), R LC51} and ^{R LC52} is the general independently It represents the same meaning as ^{R LC51} and ^{R LC52} in formula ^{^{^{(LC5), Z LC4a1, Z}}} LC4b1, Z LC4c1, Z LC5a1, Z LC5b1 and ^{Z LC5c1} each independently represent a single bond, -CH = CH -, - C≡ C—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —COO—, —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or —CF ₂ O—. More preferably, it is one or more compounds selected from the group consisting of the following compounds.

^{^R ^LC41,} R LC42, R ^LC51 and ^{R LC52} each independently represents an alkyl group of 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, the number alkenyl group or a carbon atom of 2 to 7 carbon atoms 2 It preferably represents ˜7 alkenyloxy groups.

Z ^LC4a1 to Z ^LC5c1 each independently preferably represents a single bond, —CH ₂ O—, ^{—COO—, —OCO—} , —CH ₂ CH ₂ —, and more preferably represents a single bond.

The third component is a so-called nonpolar liquid crystal compound having a dielectric anisotropy of about 0, and examples thereof include compounds represented by the following general formula (LC6).

( ^Wherein R ^LC61 and R ^LC62 each independently represents an alkyl group having 1 to 15 carbon atoms, and one or more of —CH ₂ — in the alkyl group is not directly adjacent to an oxygen atom. And may be substituted with —O—, —CH═CH—, —CO—, —OCO—, —COO— or —C≡C—, and one or more hydrogen atoms in the alkyl group ^May be optionally halogen-substituted, and A ^LC61 to A ^LC63 each independently represent

(In the structure, one or more —CH ₂ CH ₂ — in the cyclohexylene group may be substituted with —CH═CH—, —CF ₂ O—, —OCF ₂ —, ^-One or two or more CH groups in the phenylene group may be substituted with a nitrogen atom), and Z ^LC61 and Z ^LC62 each independently represent a single bond, —CH═CH—, Represents —C≡C—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —COO—, —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or —CF ₂ O—, m ^Lc6 represents 0-3. However, the compounds represented by general formula (LC1) to general formula (LC5) and general formula (i) are excluded. )
R ^LC61 and R ^LC62 are each independently preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms. Most preferably,

(In the formula, it shall be bonded to the ring structure at the right end.)
A ^LC61 to A ^LC63 each independently preferably has the following structure:

Z ^LC61 and Z ^LC62 are each independently ^preferably a single bond, —CH ₂ CH ₂ —, ^—COO— , —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or —CF ₂ O—.

General formula (LC6) is changed from general formula (LC6-a) to general formula (LC6-m)

( ^Wherein R ^LC61 and R ^LC62 are each independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or 2 to 7 carbon atoms) It is more preferable that it is 1 type, or 2 or more types of compounds chosen from the group which consists of a compound represented by this.

The fourth component is a so-called p-type liquid crystal compound having a positive dielectric anisotropy, and examples thereof include compounds represented by the following general formulas (LC1) and (LC2).

( ^Wherein R ^LC11 and R ^LC21 each independently represents an alkyl group having 1 to 15 carbon atoms, and one or more of —CH ₂ — in the alkyl group is not directly adjacent to an oxygen atom. And may be substituted with —O—, —CH═CH—, —CO—, —OCO—, —COO— or —C≡C—, and one or more hydrogen atoms in the alkyl group ^May be optionally substituted with a halogen atom, and A ^LC11 and A ^LC21 are each independently any one of the following structures:

(In the structure, one or more —CH ₂ — in the cyclohexylene group may be substituted with an oxygen atom, and one or more —CH— in the 1,4-phenylene group may be substituted. May be substituted with a nitrogen atom, and one or more hydrogen atoms in the structure may be substituted with a fluorine atom, a chlorine atom, —CF ₃ or —OCF ₃ ). ^{^{^{represents, X LC11, X LC12, X}}} LC21 ~ X LC23 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a -CF ₃ or -OCF ^{_3, Y LC11} and ^{Y LC21} are each independently a hydrogen atom, fluorine atom, a chlorine atom, a cyano _group, -CF _3, represents -OCH 2 F, -OCHF ₂ or -OCF ^{_3, Z LC11} and ^{Z LC21} each independently represent a single bond, -CH = CH -, - CF = CF- _{_{_{_{-C≡C -, - CH 2 CH 2}}}} -, - (CH 2) 4 -, - OCH 2 -, - CH 2 O -, - OCF 2 -, - CF 2 O -, - COO- or -OCO- ^{M LC11} and m ^LC21 each independently represents an integer of 1 to 4, and when there are a plurality of A ^LC11 , A ^LC21 , Z ^LC11 and Z ^LC21 , they may be the same or different. good. )
R ^LC11 and R ^LC21 are each independently preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms, and an alkyl group having 1 to 5 carbon atoms. Group, an alkoxy group having 1 to 5 carbon atoms, and an alkenyl group having 2 to 5 carbon atoms are more preferable, and a straight chain is more preferable, and the alkenyl group most preferably represents the following structure.

(In the formula, it shall be bonded to the ring structure at the right end.)
A ^LC11 and A ^LC21 each independently preferably have the following structure.

Y ^LC11 and Y ^LC21 are each independently preferably a fluorine atom, a cyano group, —CF ₃ or —OCF ₃ , preferably a fluorine atom or —OCF ₃ , and particularly preferably a fluorine atom.

Z ^LC11 and Z ^LC21 are ^preferably a single bond, —CH ₂ CH ₂ —, ^{—COO—, —OCO—} , —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or —CF ₂ O— , —CH ₂ CH ₂ —, —OCH ₂ —, —OCF ₂ — or —CF ₂ O— are preferred, and a single bond, —OCH ₂ — or —CF ₂ O— is more preferred.

m ^LC11 and m ^LC21 are preferably 1, 2 or 3, preferably 1 or 2 when emphasizing storage stability at low temperature and response speed, and 2 or 3 for improving the upper limit of the nematic phase upper limit temperature. Is preferred.

General formula (LC1) is represented by the following general formula (LC1-a) to general formula (LC1-c)

^{^{^{(Wherein, R LC11, Y LC11, X}}} LC11 and ^{X LC12} each independently represent the same meaning as ^R ^{^LC11,} Y ^LC11, ^X LC11 and ^{X LC12} in the general formula ^{^{(LC1), A LC1a1, A}} LC1a2 and A ^LC1b1 represents a trans-1,4-cyclohexylene group, a tetrahydropyran-2,5-diyl group, or a 1,3-dioxane-2,5-diyl group, and ^XLC1b1 , ^XLC1b2 , ^XLC1c1 to ^XLC1c4 Are each independently a hydrogen atom, a fluorine atom, a chlorine atom, —CF ₃ or —OCF ₃ ), and are preferably one or more compounds selected from the group consisting of compounds represented by:

R ^LC11 is preferably independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkyl group having 1 to 5 carbon atoms, carbon An alkoxy group having 1 to 5 atoms and an alkenyl group having 2 to 5 carbon atoms are more preferable.

X ^LC11 to X ^LC1c4 are each independently preferably a hydrogen atom or a fluorine atom.

Y ^LC11 is preferably independently a fluorine atom, —CF ₃ or —OCF ₃ .

The general formula (LC1) is changed from the following general formula (LC1-d) to the general formula (LC1-m).

^{^{^{(Wherein, R LC11, Y LC11, X}}} LC11 and ^{X LC12} each independently represent the same meaning as ^R ^{^LC11,} Y ^LC11, ^X LC11 and ^{X LC12} in the general formula ^{^{(LC1), A LC1d1, A}} LC1f1, A ^LC1g1 , A ^LC1j1 , A ^LC1k1 , A ^LC1k2 , A ^LC1m1 to A ^LC1m3 are 1,4-phenylene group, trans-1,4-cyclohexylene group, tetrahydropyran-2,5-diyl group, 1,3- It represents dioxane-2,5-diyl ^{^{^{^{group, X LC1d1, X LC1d2, X}}}} LC1f1, X LC1f2, X LC1g1, X LC1g2, X LC1h1, X LC1h2, X LC1i1, X LC1i2, X LC1j1 ~ X LC1j4, X LC1k1, ^X ^LC1k2, X ^LC1 Each ¹ and ^{X LC1m2} independently a hydrogen atom, a fluorine atom, a chlorine atom, a -CF ₃ or _{^{^{^{-OCF 3, Z LC1d1, Z LC1e1}}}} , Z LC1j1, Z LC1k1, Z LC1m1 each independently represent a single bond, —CH═CH—, —CF═CF—, —C≡C—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, — CF ₂ O—, —COO— or —OCO— is preferred), and it is preferably one or more compounds selected from the group consisting of compounds represented by:

X ^LC11 to X ^LC1m2 are each independently preferably a hydrogen atom or a fluorine atom.

Y ^LC11 is preferably independently a fluorine atom, —CF ₃ or —OCF ₃ .

Z ^LC1d1 to Z ^LC1m1 are each independently preferably —CF ₂ O— or —OCH ₂ —.
The general formula (LC2) is changed from the following general formula (LC2-a) to the general formula (LC2-g).

( ^Wherein R ^LC21 , Y ^LC21 , X ^LC21 to X ^LC23 each independently represents the same meaning as R ^LC21 , Y ^LC21 , X ^LC21 to X ^LC23 in the general formula (LC2), and X ^LC2d1 to X ^LC2d4 , X ^LC2e1 to X ^LC2e4 , X ^LC2f1 to X ^LC2f4 and X ^LC2g1 to X ^LC2g4 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, —CF ₃ or —OCF ₃ , and Z ^LC2a1 , Z ^LC2b1 , Z ^LC2c1 , Z ^LC2d1 , Z ^LC2e1 , Z ^LC2f1 and Z ^LC2g1 are each independently a single bond, —CH═CH—, ^{—CF═CF—} , ^—C≡C— , —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O—, —COO— or Represents —OCO—, and is preferably one or more compounds selected from the group consisting of compounds represented by:

R ^LC21 is preferably independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkyl group having 1 to 5 carbon atoms, carbon An alkoxy group having 1 to 5 atoms and an alkenyl group having 2 to 5 carbon atoms are more preferable.

X ^LC21 to X ^LC2g4 are each independently preferably a hydrogen atom or a fluorine atom,
Y ^LC21 is preferably each independently a fluorine atom, —CF ₃ or —OCF ₃ .

Z ^LC2a1 to Z ^LC2g4 are each independently preferably —CF ₂ O— or —OCH ₂ —. The composition of the present invention preferably does not contain a compound having a structure in which oxygen atoms such as a peracid (—CO—OO—) structure are bonded in the molecule.

When emphasizing the reliability and long-term stability of the composition, the content of the compound having a carbonyl group is preferably 5% or less, more preferably 3% or less with respect to the total mass of the composition. Preferably, it is more preferably 1% or less, and most preferably not substantially contained.

When importance is attached to the stability by UV irradiation, the content of the compound substituted with chlorine atoms is preferably 15% or less, preferably 10% or less, based on the total mass of the composition. % Or less, preferably 5% or less, more preferably 3% or less, and still more preferably substantially not contained.

In order to suppress deterioration due to oxidation of the composition, it is preferable to reduce the content of the compound having a cyclohexenylene group as a ring structure, and the content of the compound having a cyclohexenylene group as the total mass of the composition. On the other hand, it is preferably 10% or less, preferably 8% or less, more preferably 5% or less, preferably 3% or less, and still more preferably not contained.

When emphasizing improvements of improvement and T _NI viscosity, that a hydrogen atom to reduce the content of the compound having the optionally substituted 2-methyl-1,4-diyl group halogen in the molecule The content of the compound having a 2-methylbenzene-1,4-diyl group in the molecule is preferably 10% or less, more preferably 8% or less with respect to the total mass of the composition. It is preferably 5% or less, more preferably 3% or less, and still more preferably substantially not contained.

“Substantially not contained” in the present application means that it is not contained except for an unintentionally contained product.

When the compound contained in the composition of the first embodiment of the present invention has an alkenyl group as a side chain, when the alkenyl group is bonded to cyclohexane, the alkenyl group has 2 to 5 carbon atoms. When the alkenyl group is bonded to benzene, the number of carbon atoms of the alkenyl group is preferably 4 to 5, and the unsaturated bond of the alkenyl group and benzene are directly bonded. Preferably not.

The average elastic constant (K _AVG ) of the liquid crystal composition used in the present invention is preferably 10 to 25, and the lower limit thereof is preferably 10, preferably 10.5, preferably 11 and preferably 11.5. , 12 is preferable, 12.3 is preferable, 12.5 is preferable, 12.8 is preferable, 13 is preferable, 13.3 is preferable, 13.5 is preferable, 13.8 is preferable, 14 is preferable, 14 .3 is preferred, 14.5 is preferred, 14.8 is preferred, 15 is preferred, 15.3 is preferred, 15.5 is preferred, 15.8 is preferred, 16 is preferred, 16.3 is preferred, 16 .5, 16.8 is preferable, 17 is preferable, 17.3 is preferable, 17.5 is preferable, 17.8 is preferable, and 18 is preferable. 25 is preferable, 24.5 is preferable, 24 is preferable, 23.5 is preferable, 23 is preferable, 22.8 is preferable, 22.5 is preferable, 22.3 is preferable, 22 is preferable, and 21.8 is 21.5 is preferred, 21.3 is preferred, 21 is preferred, 20.8 is preferred, 20.5 is preferred, 20.3 is preferred, 20 is preferred, 19.8 is preferred, 19.5 is preferred 19.3 is preferred, 19 is preferred, 18.8 is preferred, 18.5 is preferred, 18.3 is preferred, 18 is preferred, 17.8 is preferred, 17.5 is preferred, 17.3 is preferred 17 is preferable. When importance is placed on reducing power consumption, it is effective to reduce the amount of light from the backlight, and it is preferable to improve the light transmittance of the liquid crystal display element. For this purpose, the value of K _AVG should be set low. preferable. It is preferable to set a higher value of K _AVG in the case of emphasizing improved response speed. The liquid crystal composition of the present invention has a refractive index anisotropy (Δn) at 20 ° C. of 0.08 to 0.14, more preferably 0.09 to 0.13, and 0.09 to 0.12. Particularly preferred. More specifically, it is preferably 0.10 to 0.13 when dealing with a thin cell gap, and preferably 0.08 to 0.10 when dealing with a thick cell gap.

The liquid crystal composition of the present invention has a viscosity (η) at 20 ° C. of 10 to 30 mPa · s, more preferably 10 to 25 mPa · s, and particularly preferably 10 to 22 mPa · s.

The liquid crystal composition of the present invention has a rotational viscosity (γ ₁ ) at 20 ° C. of 60 to 200 mPa · s, more preferably 60 to 120 mPa · s, and particularly preferably 60 to 100 mPa · s. .

The liquid crystal composition of the present invention has a nematic phase-isotropic liquid phase transition temperature (T _ni ) of 60 ° C. to 120 ° C., more preferably 70 ° C. to 100 ° C., and particularly preferably 70 ° C. to 85 ° C. In addition, it is preferable to show a nematic liquid crystal at 20 ° C.

The liquid crystal composition of the present invention may contain a normal nematic liquid crystal, a smectic liquid crystal, a cholesteric liquid crystal, an antioxidant, an ultraviolet absorber, an infrared absorber, a polymerizable monomer, or a light stabilizer in addition to the above-described compounds. Good. The liquid crystal display device using the liquid crystal composition containing the compound of the present invention is useful for achieving both high-speed response and suppression of display failure, and is particularly useful for a liquid crystal display device for active matrix driving. The present invention can be applied to liquid crystal display elements in various modes such as a mode, a PSVA mode, a PSA mode, an IPS mode, an FFS mode, or an ECB mode.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Further, “%” in the compositions of the following Examples and Comparative Examples means “% by mass”. The phase transition temperature was measured using a polarizing microscope equipped with a temperature control stage and a differential scanning calorimeter (DSC).

T _n-i nematic phase - represents the transition temperature of the isotropic phase.

The following abbreviations are used in compound descriptions.
THF: tetrahydrofuran LDA: lithium diisopropylamide Me: methyl group, Et: ethyl group, Pr: n-propyl group, Bu: n-butyl group,
Pent: n-pentyl group (Examples 1 and 2) Synthesis of compounds 1-8-203 and 2-8-203

(Synthesis of Compound 1-2-20)
Under a nitrogen atmosphere, in a reaction vessel equipped with a stirrer, thermometer, dropping funnel, and condenser, 3-fluoro-2-hydroxychlorobenzene (50.0 g), bis (ditertiary butyl (4-dimethylaminophenyl) phosphine) Palladium (II) chloride complex (6.0 g), THF (350 ml) and 2M aqueous cesium carbonate solution (340 ml) were added, and the temperature was raised to 60 ° C. with stirring. Compound 1-2 (75.8 g) previously dissolved in THF (200 ml) was added dropwise to the reaction mixture. After stirring at 60 ° C. for 7 hours, heating was stopped and the solution temperature was returned to room temperature. Then 10% hydrochloric acid (500 ml) was added. The organic layer was separated and the aqueous layer was re-extracted with toluene (200 ml). The combined organic layers were washed with water and saturated brine in that order, dried over anhydrous sodium sulfate. After concentrating the resulting solution, a solution dissolved by adding hexane (150 ml) and toluene (150 ml) was passed through a column packed with silica gel (30 g). The obtained column passing solution was concentrated, and recrystallization was repeated using a toluene / hexane mixed solvent to obtain compound 1-2-20 (46.0 g).

(Synthesis of Compound 1-3-20)
Under a nitrogen atmosphere, sodium hydride (60% mineral oil dispersion) (5.4 g) and DMF (54 ml) were added to a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a condenser, and ice-cooled while stirring. did. Compound 1-2-20 (30.0 g) previously dissolved in DMF (150 ml) was added dropwise thereto. Thereafter, the temperature was returned to room temperature, and the solution temperature was heated to 50 ° C. over 1 hour. Thereafter, the solution temperature was further heated to 105 ° C. over 1.5 hours. After stirring at 105 ° C. for 4 hours, the solution temperature was cooled to 10 ° C. or lower. Water (200 ml) was added to the reaction solution. The crystals were filtered, washed with methanol and dried in vacuo. A solution in which toluene (300 ml) was added and dissolved in the obtained crystal was passed through a column packed with silica gel (20 g), and further toluene (200 ml) was passed. The resulting column passage solution was concentrated to obtain compound 1-3-20 (28.6 g).

(Synthesis of Compound 1-4-20)
Under a nitrogen atmosphere, Compound 1-3-20 (30.1 g) was dissolved in THF (300 ml) in a reaction vessel equipped with a stirrer, a thermometer, and a dropping funnel, and cooled to -70 ° C. 1.6M butyllithium / hexane solution (90.0 ml) was added dropwise at −70 ° C. and stirred for 1 hour, then triisopropyl borate (29.7 g) was added dropwise at −70 ° C. and stirred for 1 hour. did. The reaction mixture was warmed to room temperature, 10% hydrochloric acid (150 ml) and hexane (100 ml) were added and stirred, and the resulting organic layers were combined, washed with water and saturated brine, and anhydrous sodium sulfate. And dried. The obtained solution was concentrated to obtain 29.5 g. While stirring the resulting solid in THF (150 ml) and sodium hydrogen carbonate (0.42 g), 30% aqueous hydrogen peroxide (14.9 g) was added dropwise at room temperature and stirred for 12 hours. The solution temperature was cooled to 0 ° C. and 15% aqueous sodium thiosulfate solution (150 ml) was added. The organic layer was separated, and the aqueous layer was extracted with ethyl acetate (100 ml). The obtained organic layers were combined, washed with water and saturated brine, and dried over anhydrous sodium sulfate. The resulting solution was concentrated to give compound 1-4-20 (26.2 g).

(Synthesis of Compound 1-5-20)
Under a nitrogen atmosphere, in a reaction vessel equipped with a stirrer, thermometer, dropping funnel, and condenser, compound 1-4-20 (5.3 g), chloromethyl methyl ether (2.4 g), sodium hydride (60% Mineral oil dispersion) (1.2 g) and THF (20 ml) were added and stirred. After stirring at 60 ° C. for 1.5 hours, the solution temperature was cooled to 10 ° C. or lower. Water (20 ml) and ethyl acetate (20 ml) were added to the reaction solution. The organic layer was separated and the aqueous layer was re-extracted with ethyl acetate (30 ml). The combined organic layers were washed with water and saturated brine in that order, dried over anhydrous sodium sulfate. The obtained solution was concentrated to obtain a crude product of compound 1-5-20 (6.9 g).

(Synthesis of Compound 1-6-20)
Under a nitrogen atmosphere, Compound 1-5-20 (4.7 g) was dissolved in THF (56 ml) in a reaction vessel equipped with a stirrer, a thermometer, and a dropping funnel, and cooled to -70 ° C. A 1.6M butyllithium / hexane solution (10.0 ml) was added dropwise at -70 ° C, stirred for 1 hour, and the temperature was raised to -20 ° C. After cooling to −70 ° C. again, iodine (4.7 g) previously dissolved in THF (15 ml) was added dropwise at −70 ° C. and stirred for 1 hour. The reaction mixture was warmed to room temperature, 20% aqueous sodium sulfite solution (100 ml) and hexane (100 ml) were added and stirred, and the resulting organic layers were combined, washed with water and saturated brine, Sodium sulfate was added and dried. The resulting solution was concentrated to give compound 1-6-20 (6.4 g).
(Synthesis of Compound 1-7-203)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a condenser tube under a nitrogen atmosphere, compound 1-6-20 (6.3 g), bis (triphenylphosphine) palladium (II) dichloride (270.0 mg) 1-pentyne (1.8 ml) was added dropwise at room temperature to copper iodide (145 mg) dissolved in THF (350 ml) and 1N aqueous ammonia (35 mL) and stirred, and then the reaction temperature was raised to 45 ° C. did. After stirring at 45 ° C. for 2 hours, ethyl acetate (100 ml) was added. The organic layer was separated and the aqueous layer was re-extracted with ethyl acetate (50 ml). The combined organic layers were washed with water and saturated brine in that order, dried over anhydrous sodium sulfate. After concentration of the resulting solution, compound 1-7-203 (5.7 g) was obtained.

(Synthesis of Compound 1-8-203)
In a reaction vessel equipped with a stirrer, thermometer, and dropping funnel in a nitrogen atmosphere, compound 1-7-203 (6.0 g) was dissolved in THF (60 ml) and isopropyl alcohol (20 ml), and 10% hydrochloric acid ( 40 ml) was added dropwise. The reaction temperature was raised to 55 ° C. and stirred for 5 hours. After returning to room temperature, ethyl acetate (100 ml) was added, washed with water and saturated brine, and dried over anhydrous sodium sulfate. The obtained solution was concentrated to obtain a crude product (6.6 g). The obtained crude product was purified by silica gel chromatography, and then recrystallization was repeated using an ethanol / ethyl acetate mixed solvent to obtain compound 1-8-203 (3.2 g). The phase transition temperature is Cr106Iso.
(Synthesis of Compound 2-8-203)
Under a nitrogen atmosphere, compound 1-8-203 (1.5 g), 10% palladium carbon (150 mg) was dissolved in THF (9.0 ml) and methanol (6 ml) in a reaction vessel equipped with a stirrer, and a hydrogen atmosphere It was. After returning to a nitrogen atmosphere, the catalyst is filtered off. The resulting solution was concentrated and purified by silica gel chromatography. Compound 2-8-203 (0.9 g) was obtained by repeated recrystallization using a mixed solvent of ethanol / ethyl acetate. The phase transition temperature is Cr74Iso.
Examples 3 to 324 Synthesis of Compound 1-8-0 to Compound 4-8-808 Using the same reaction as in Example 1 and Example 2, and if necessary, a method based on a known method, Example 3 (Compound 1-8-0) to Example 324 (Compound 4-8-808) were synthesized.

Example 325 Preparation of Liquid Crystal Composition-1
Host liquid crystal (H) showing the following physical properties
Was prepared. All the values are actually measured values.

T _n-i (nematic phase - isotropic liquid phase transition temperature): 73.8 ° C.
Δε (dielectric anisotropy at 25 ° C.): −2.79
Δn (refractive index anisotropy at 25 ° C.): 0.101
γ ₁ (rotational viscosity coefficient at 25 ° C.): 118
A liquid crystal composition (MA) comprising 90% of the base liquid crystal (H) and 10% of the compound (1-8-203) obtained in Example 1 was prepared. _{T n-i,} [Delta] [epsilon], based on the amount of change from the Δn and gamma ₁ value measured maternal liquid crystal compound obtained in Example 1 of the composition (M-A) (1-8-203 The extrapolated value of each physical property value of) was as follows.

Extrapolation _T n-i: 70.8 ℃
Extrapolation Δε: -14.6
Extrapolation Δn: 0.246
Extrapolation γ ₁ : 362 mPa · s
Further, the prepared liquid crystal composition (MA) maintained a uniform nematic liquid crystal state for one month or more at room temperature.

Furthermore, the liquid crystal display device manufactured using the liquid crystal composition (MA) showed excellent display characteristics, maintained stable display characteristics for a long time, and showed high reliability.

(Example 326) Preparation of liquid crystal composition-2
A liquid crystal composition (MB) comprising 90% of the base liquid crystal (H) and 10% of the compound (1-8-203) obtained in Example 2 was prepared. From this composition (M-B), the extrapolated _{T n-i} of the compound obtained in Example 2 (1-8-203), extrapolated [Delta] [epsilon], extrapolation [Delta] n, the extrapolation gamma ₁ values below It is as follows.

Extrapolation _T n-i: 38.9 ℃
Extrapolation Δε: −17.9
Extrapolation Δn: 0.198
Extrapolation γ ₁ : 372 mPa · s
Further, the prepared liquid crystal composition (MB) maintained a uniform nematic liquid crystal state for one month or more at room temperature.

Furthermore, the liquid crystal display device manufactured using the liquid crystal composition (MB) exhibited excellent display characteristics, maintained stable display characteristics over a long period of time, and exhibited high reliability.

Comparative Example 1 Preparation of Liquid Crystal Composition-3
A liquid crystal composition (MC) comprising 85% of the base liquid crystal (H) and 15% of the following compound (A) was prepared.

From this composition (M-C), extrapolated T _n-i, extrapolated [Delta] [epsilon], extrapolation [Delta] n, the extrapolation gamma ₁ value of the compound (A) is as follows.

Extrapolation _T n-i: 18.3 ℃
Extrapolation Δε: −15.7
Extrapolation Δn: 0.184
Extrapolation γ ₁ : 241 mPa · s
While Δε is comparable when comparing the results of Example 325, it found to be T _n-i and Δn is small, when compared T _n-i, that Δn and Δε is less apparent as in Example 326.

Comparative Example 2 Preparation of Liquid Crystal Composition-4
A liquid crystal composition (MD) comprising 85% of the base liquid crystal (H) and 15% of the following compound (B) was prepared.

From this composition (M-D), the extrapolated T _n-i, extrapolated [Delta] [epsilon], extrapolation [Delta] n, the extrapolation gamma ₁ value of the compound (B) is as follows.

Extrapolation T _n−i : 3.2 ° C.
Extrapolation Δε: -9.7
Extrapolation Δn: 0.073
Extrapolation γ ₁ : 94 mPa · s
Comparing the above results with Example 325 and Example 326, it can be seen that | Δε | is significantly smaller and T _n−i is also significantly lower.

Claims

Formula (i)

( Wherein , X i1 and X i2 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a trifluoromethoxy group,
Y i1 and Y i2 each independently represent —O—, —S—, —SO—, —SOO—, —CF 2 —, —CO—, —CX i3 X i4 —, wherein Y i1 and Y any one or more of i2 represents —O—, —S—, —SO—, —SOO—;
X i3 and X i4 each independently represent the same meaning as X i1 ,
W i1

(However, the black point in the formula represents the point of attachment to L i2 or Y i2 ),
W i2 represents a single bond or —CL i9 L i10 —,
L i1 , L i2 , L i3 , L i4 , L i5 , L i6 , L i7 , L i8 , L i9 and L i10 are each independently a hydrogen atom, bromine atom, iodine atom, hydroxyl group, carbon number 1 To 15 alkyl groups, alkenyl groups of 2 to 15 carbon atoms, or

(Wherein R i1 represents a hydrogen atom, a bromine atom, an iodine atom, a hydroxyl group, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, or carbon. Represents an alkenyloxy group having 2 to 15 atoms,
A i1 represents (a) a 1,4-cyclohexylene group (one —CH 2 — present in this group or two or more non-adjacent —CH 2 — represents —O— or —S—). May be replaced.)
(B) 1,4-phenylene group (one —CH═ present in this group or two or more non-adjacent —CH═ may be replaced by —N═, present in this group) One hydrogen atom may be substituted with a fluorine atom.)
(C) 1,4-cyclohexenylene group, naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group ( A hydrogen atom present in these groups may be substituted with a fluorine atom, or present in a naphthalene-2,6-diyl group or a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group. One -CH = or two or more non-adjacent -CH = may be replaced by -N =.)
Represents a group selected from the group consisting of
Z i1 represents —CH 2 O—, —OCH 2 —, —CF 2 O—, —OCF 2 —, —COO—, —OCO—, —CH 2 CH 2 —, —CF 2 CF 2 —, —CH ═CH—, —CF═CF—, —C≡C— or a single bond,
n i1 represents 1 or 2, but when n i1 represents 2 and a plurality of A i1 and Z i1 exist, they may be the same or different. )
One —CH 2 — or adjacent group present in L i1 , L i2 , L i3 , L i4 , L i5 , L i6 , L i7 , L i8 , L i9 and L i10 Two or more —CH 2 — that are not present may be replaced by —C≡C—, —O—, —S—, —COO—, —OCO— or —CO—, and may be an alkyl group or alkenyl. A hydrogen atom present in the group may be substituted with a fluorine atom. )
Represents a group represented by )
A compound represented by
In the general formula (i), at least one of L i1 , L i2 , L i3 , L i4 , L i5 , L i6 , L i7 , L i8 , L i9 and L i10 is

And A i1 is

The compound according to claim 1, which represents a group selected from:
In the general formula (i), at least one of L i1 , L i2 , L i3 , L i4 , L i5 , L i6 , L i7 , L i8 , L i9 and L i10 is

The compound according to claim 1 , wherein at least one of Z i1 represents —CH 2 O—, —OCH 2 —, —CH 2 CH 2 —, or a single bond.
The compound according to claims 1 to 3, wherein in the general formula (i), Y i1 and Y i2 each represent -O-.
The compound according to claims 1 to 4, wherein, in the general formula (i), X i1 and X i2 each represent a fluorine atom.
In the general formula (i), L i1 , L i2 , L i3 and L i8 are each independently a hydrogen atom, a bromine atom, an iodine atom, a hydroxyl group, an alkyl group having 1 to 15 carbon atoms, or from 1 carbon atom. 15 represents an alkoxy group, an alkenyl group having 2 to 15 carbon atoms, or an alkenyloxy group having 2 to 15 carbon atoms, and L i4 , L i5 , L i6 , L i7 , L i9 and L i10 are each independently The compound according to claims 1 to 5, which represents a hydrogen atom.
The compound according to any one of claims 1 to 6, wherein in the general formula (i), W i1 represents -CH 2 CH 2 -or -CH = CH-.
The compound according to any one of claims 1 to 7, wherein in formula (i), W i2 represents a single bond.
A composition comprising one or more of the compounds according to claims 1 to 8.
A liquid crystal display device using the composition according to claim 9.
Formula (i-r3)

( Wherein X i1 , X i2 , Y i1 , Y i2 , W i1 , W i2 , L i1 , L i2 , L i3 , L i4 and L i5 are X i1 , X i2 , Y i1 in the general formula (i)). Y i2 , W i1 , W i2 , L i1 , L i2 , L i3 , L i4 and L i5 each have the same meaning, but a plurality of X i2 may be the same or different.)
A method for producing a compound represented by the general formula (i), wherein —Y i1 —H in the compound represented by formula (1) is deprotonated with a base to generate an anion to cause an intramolecular reaction.
Formula (i-r1)

( Wherein X i2 , Y i2 , W i1 , L i2 and L i5 represent the same meaning as X i2 , Y i2 , W i1 , L i2 and L i5 in general formula (i), respectively, but a plurality of X i2 may be different even in the same,
R i3 and R i4 each independently represent a hydrogen atom, a methyl group, an ethyl group, or a propyl group, or R i3 and R i4 are bonded to each other to form a cyclic structure —CH 2 —CH 2 —, —CH It represents 2- CH 2 —CH 2 — or —CH 2 —C (CH 3 ) 2 —CH 2 —. )
And a compound of the general formula (ir-2)

( Wherein X i1 , Y i1 , L i1 , L i3 , L i4 and W i2 represent the same meanings as X i1 , Y i1 , L i1 , L i3 , L i4 and W i2 in general formula (i), respectively. ,
X i3 represents a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, a p-toluenesulfonyloxy group, or a trifluoromethanesulfonyloxy group. )
The production method according to claim 11, wherein the compound represented by general formula (i-r3) is obtained by reacting the compound represented by general formula (i-r3) in the presence of a transition metal catalyst and a base.
Formula (i-r3)

( Wherein X i1 , X i2 , Y i1 , Y i2 , W i1 , W i2 , L i1 , L i2 , L i3 , L i4 and L i5 are X i1 , X i2 , Y i1 in the general formula (i)). Y i2 , W i1 , W i2 , L i1 , L i2 , L i3 , L i4 and L i5 each have the same meaning, but a plurality of X i2 may be the same or different.)
A compound represented by
Formula (i-r1)

( Wherein X i2 , Y i2 , W i1 , L i2 and L i5 represent the same meaning as X i2 , Y i2 , W i1 , L i2 and L i5 in general formula (i), respectively, but a plurality of X i2 may be different even in the same,
R i3 and R i4 each independently represent a hydrogen atom, a methyl group, an ethyl group, or a propyl group, or R i3 and R i4 are bonded to each other to form a cyclic structure —CH 2 —CH 2 —, —CH 2 -CH 2 -CH 2- or -CH 2 -C (CH 3 ) 2 -CH 2-
A broken line indicates that a bond may not exist or may exist. )
A compound represented by
In formula (i), W i1 is

(However, the black point in the formula represents the point of attachment to L i2 or Y i2 .)
In the general formula (i), W i1 is an addition reaction to the double bond of the compound represented by

(However, the black point in the formula represents the point of attachment to L i2 or Y i2 .)
The manufacturing method of the compound represented by these.
Formula (ir-7)

( Where X i1 , X i2 , Y i1 , Y i2 , W i2 , L i1 , L i2 , L i3 , L i4, and L i5 are X i1 , X i2 , Y i1 , Y i2 in general formula (i)). , W i2 , L i1 , L i2 , L i3 , L i4 and L i5 respectively,
L i11 represents the same meaning as L i1 . )
In formula (i), W i1 is represented by the general formula (i) in which —Y i2 -L i11 in the compound represented by

(However, the black point in the formula represents the point of attachment to L i2 or Y i2 .)
The manufacturing method of the compound represented by these.
Formula (i-r5)

( Where X i1 , X i2 , Y i1 , Y i2 , W i2 , L i1 , L i3 , L i4 and L i5 are X i1 , X i2 , Y i1 , Y i2 , W i2 in the general formula (i)). , L i1 , L i3 , L i4 and L i5 each have the same meaning,
L i11 represents the same meaning as L i1 ,
X i3 represents a bromine atom or an iodine atom. )
And a compound represented by the general formula (ir-6)

(Wherein L i2 are as defined L i2 in the general formula (i).)
By reacting a compound represented by general formula (ir-7) in the presence of a transition metal catalyst, a copper catalyst and a base.

( Where X i1 , X i2 , Y i1 , Y i2 , W i2 , L i1 , L i2 , L i3 , L i4, and L i5 are X i1 , X i2 , Y i1 , Y i2 in general formula (i)). , W i2 , L i1 , L i2 , L i3 , L i4 and L i5 respectively,
L i11 represents the same meaning as L i1 . )
The manufacturing method of the compound represented by these.
General formula (i-r4)

( Where X i1 , X i2 , Y i1 , Y i2 , W i2 , L i1 , L i3 , L i4 and L i5 are X i1 , X i2 , Y i1 , Y i2 , W i2 in the general formula (i)). , L i1 , L i3 , L i4 and L i5 each have the same meaning,
L i11 represents the same meaning as L i1 . )
The compound represented by general formula (ir5) is obtained by deprotonation with an organometallic reagent and then reacting with bromine or iodine.

( Where X i1 , X i2 , Y i1 , Y i2 , W i2 , L i1 , L i3 , L i4 and L i5 are X i1 , X i2 , Y i1 , Y i2 , W i2 in the general formula (i)). , L i1 , L i3 , L i4 and L i5 each have the same meaning,
L i11 represents the same meaning as L i1 ,
X i3 represents a bromine atom or an iodine atom. )
The manufacturing method of the compound represented by these.
Formula (ir-7)

( Where X i1 , X i2 , Y i1 , Y i2 , W i2 , L i1 , L i2 , L i3 , L i4, and L i5 are X i1 , X i2 , Y i1 , Y i2 in general formula (i)). , W i2 , L i1 , L i2 , L i3 , L i4 and L i5 respectively,
L i11 represents the same meaning as L i1 . )
A compound represented by
Formula (i-r5)

( Where X i1 , X i2 , Y i1 , Y i2 , W i2 , L i1 , L i3 , L i4 and L i5 are X i1 , X i2 , Y i1 , Y i2 , W i2 in the general formula (i)). , L i1 , L i3 , L i4 and L i5 each have the same meaning,
L i11 represents the same meaning as L i1 ,
X i3 represents a bromine atom or an iodine atom. )
A compound represented by
General formula (i-r4)

( Where X i1 , X i2 , Y i1 , Y i2 , W i2 , L i1 , L i3 , L i4 and L i5 are X i1 , X i2 , Y i1 , Y i2 , W i2 in the general formula (i)). , L i1 , L i3 , L i4 and L i5 each have the same meaning,
L i11 represents the same meaning as L i1 . )
A compound represented by