JP6681035B2 - Liquid crystal compound and composition thereof - Google Patents

Description

  The present invention relates to a compound having a condensed ring, which is useful as an organic electronic material or a medical or agricultural chemical, especially as a material for a liquid crystal display device, and a liquid crystal composition using the compound.

  The liquid crystal display device is used for various measuring instruments, automobile panels, word processors, electronic notebooks, printers, computers, televisions, clocks, advertisement display boards, etc., including clocks and calculators. Typical liquid crystal display systems are 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 composition used for these liquid crystal display elements is stable against external factors such as moisture, air, heat, and light, and also has a liquid crystal phase (nematic phase, smectic phase) in a wide temperature range centered at room temperature. Phase and blue phase), low viscosity, and low driving voltage are required. Further, the liquid crystal composition is selected from several kinds to several tens of kinds of compounds in order to make the dielectric anisotropy (Δε) and the refractive index anisotropy (Δn) have optimum values according to individual display elements, It is configured.

When the liquid crystal composition is used as a display device or the like, it is required to exhibit a stable nematic phase in a wide temperature range. In order to maintain the nematic phase in a wide temperature range, it is required that the individual components constituting the liquid crystal composition have high miscibility with other components and have a high clearing point (T _ni ). . Further, when the liquid crystal composition is used as a display device or the like, it is required that the rotational viscosity coefficient (γ ₁ ) is as low as possible. There are various methods for obtaining a liquid crystal composition having a low γ ₁ , and as one of them, it is known to use a compound having a large | Δε | (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 the amount of nonpolar compound having | Δε | (extrapolated value) of almost 0 and low γ ₁ (extrapolated value) as much as possible. Is. Δε of the composition generally required is determined for each liquid crystal panel, and a polar compound having a large γ ₁ (extrapolated value) is added to impart Δε. Therefore, the amount of the nonpolar compound used can be increased by replacing the compound with a large | Δε | (extrapolated value), and as a result, γ ₁ reduction of the liquid crystal composition can be achieved.

As described above, there is a demand for the development of a compound having a high T _ni and a large | Δε | (extrapolated value). The following compounds having a dibenzofuran structure have been reported so far, but there was a problem that T _ni was not sufficiently large (Patent Document 1 and Patent Document 2).

(In the formula, R ¹ and R ² each independently represent an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, an alkynyl group having 2 to 15 carbon atoms, and m and n are 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 a large Δε, and at the same time, to provide a liquid crystal composition and a liquid crystal display device containing the compound as a constituent member.

  In order to solve the above problems, the inventors of the present invention have studied various compounds, and as a result, have found that the 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)

(In the formula, 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 —, provided that Y ⁱ¹ and Y ^i. 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 ;
The broken line indicates that the bond may or may not exist,
If W ⁱ¹ is the absence of broken ^{lines, -CL i6 L i7 -CL i8 L} i9 -, - CL i6 L i7 -O -, - O-CL i8 L i9 -, - CL i6 L i7 -S -, - S -CL ⁱ⁸ L ⁱ⁹ -, or ^-CL i6 = ^{CL i8} - it represents,
When the broken line is present, it represents -CL ⁱ⁶ L ⁱ⁷ -CL ⁱ⁸ =, -O-CL ⁱ⁸ =, -S-CL ⁱ⁸ =,
W ⁱ² represents a single bond or —CL ⁱ¹⁰ L ⁱ¹¹ −,
L ⁱ¹ , L ⁱ² , L ⁱ³ , L ⁱ⁴ , L ⁱ⁵ , L ⁱ⁶ , L ⁱ⁷ , L ⁱ⁸ , L ⁱ⁹ , L ⁱ¹⁰ and L ⁱ¹¹ are each independently a hydrogen atom, a bromine atom, an ^iodine atom, a hydroxyl group or a carbon atom. An alkyl group having 1 to 15 atoms, an alkenyl group having 2 to 15 carbon atoms, or

(In the formula, R ⁱ¹ represents a hydrogen atom, a bromine atom, an iodine atom, a hydroxyl group, an alkyl group having 1 to 15 carbon atoms or an alkenyl group having 2 to 15 carbon atoms,
A ⁱ¹ is (a) a 1,4-cyclohexylene group (one —CH ₂ — present in this group or two or more —CH ₂ — which are not adjacent to each other is —O— or —S— It may be replaced.)
(B) 1,4-phenylene group (one —CH═ present in this group or two or more —CH═ which are not adjacent to each other may be replaced with —N═, and is present in this group) One hydrogen atom may be replaced 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 ( The hydrogen atom present in these groups may be replaced by a fluorine atom, and also present in the naphthalene-2,6-diyl group or the 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 is —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 are present, they may be the same or different. )
Represents a group represented by, and one -CH ₂ present in L ⁱ¹ , L ⁱ² , L ⁱ³ , L ⁱ⁴ , L ⁱ⁵ , L ⁱ⁶ , L ⁱ⁷ , L ⁱ⁸ , L ⁱ⁹ , L ⁱ¹⁰ and L ^i11. - or nonadjacent two or more -CH ₂ - is -C≡C -, - O -, - S -, - COO -, - OCO- or may be replaced by -CO-, also alkyl A hydrogen atom present in the group or alkenyl group may be replaced by a fluorine atom. )
Represents a group represented by. )
And 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.

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

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

It is preferable that Y ⁱ¹ and Y ⁱ² each independently 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 larger negative Δε. In order to improve long-term reliability of the liquid crystal display device 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 is preferably —CH ₂ O—, —OCH ₂ —, —CH ₂ CH ₂ —, —CH═CH—, —CH ₂ —CH =, or —OCH =, and T _ni and γ ₁ are important. _-CH 2 _CH 2 in the case of -, - CH = CH -, - CH 2 , more preferably -CH = a, in order to increase the miscibility with other liquid crystal components _-CH 2 CH ₂ - Is more preferable, and —CH═CH— and —CH ₂ —CH═ are more preferable in order to show a large Δn.

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

L ⁱ¹ and L ⁱ² each independently preferably represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms or an alkenyl group having 2 to 15 carbon atoms, and in order to lower γ ₁ , a carbon atom is preferable. It is preferably an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms. Further, it is preferably linear. In order to increase | Δε |, an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms is preferable, and an alkoxy group having 1 to 5 carbon atoms or 2 carbon atoms. Particularly preferably, it is an alkenyloxy group of -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 the alkenyloxy group is preferably one of L ⁱ¹ and L ⁱ² , and an alkoxy group. Alternatively, the alkenyloxy group 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.

In addition, L ⁱ¹ and L ⁱ² are

Is preferably represented.

In order to lower γ ₁ , R ⁱ¹ is preferably an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, and an alkyl group having 1 to 5 carbon atoms or the number of carbon atoms. Particularly preferred are 2 to 5 alkenyl groups. Further, it is preferably linear. In order to increase | Δε |, an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms is preferable, and an alkoxy group having 1 to 5 carbon atoms or 2 carbon atoms. Particularly preferably, it is an alkenyloxy group of -5. When a plurality of R ^i1's are present, it is preferable that the R ^i1s are different from each other in order to increase the miscibility with other liquid crystal components, and the alkoxy group or the alkenyloxy group is one of the plurality of R ^i1s present. And it is particularly preferable that the alkoxy group or the alkenyloxy group is R ⁱ¹ in L ⁱ¹ . The hydrogen atom present in R ⁱ¹ may be replaced by a fluorine atom, but is preferably not replaced by 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 in order to reduce γ _1. A -1,4-phenylene group is preferable, and a trans-1,4-cyclohexylene group is particularly preferable. In order to improve the miscibility with other liquid crystal components, a trans-1,4-cyclohexylene group, a 2-fluoro-1,4-phenylene group or a 3-fluoro-1,4-phenylene group is preferable. 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 Is preferred. In order to show a large negative 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 compatibility with other liquid crystal components while exhibiting a large negative Δε, the total number of fluorine atoms present in A ⁱ¹ is preferably from 1 to 4, and from 1 to 3 It is particularly preferable that

Z ⁱ¹ is preferably a single bond, —CH ₂ CH ₂ —, —CH ₂ O— or —OCH ₂ — in order to reduce γ ₁ , and is a single bond or —CH ₂ CH ₂ —. 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. It is more preferable that it is −. In order to improve the miscibility with other liquid crystal components, it is preferably a single bond, —CH ₂ CH ₂ —, —CH ₂ O— or —OCH ₂ —. In order to improve long-term reliability of the liquid crystal display device, a single bond is preferable.

When n ⁱ¹ represents 2, it is preferable that one or more of a plurality of Z ⁱ¹ 's present represent a single bond. It is preferable that n ⁱ¹ is ₁ when γ ₁ is important. When T _ni is important, 2 is preferable.

L ⁱ³ may represent 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. Preferably, in order to lower γ ₁ , it is preferably an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, and an alkyl group having 1 to 5 carbon atoms or 2 carbon atoms. Particularly preferably, it is an alkenyl group of -5. Further, it is preferably linear.

L ⁱ¹ 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. If L ⁱ³ is

Is preferably represented.

L ⁱ⁴ and L ⁱ⁵ each independently preferably 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 are each independently 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 2 to 15 carbon atoms. The alkenyloxy group is preferably represented by, and in order to reduce γ ₁ , it is preferably an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, and 1 to 5 carbon atoms. Is particularly preferably an alkenyl group having 2 to 5 carbon atoms. Further, it is preferably linear.

L ⁱ⁸ or L ⁱ⁹ each independently 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 2 to 15 carbon atoms. The alkenyloxy group is preferably represented by, and in order to reduce γ ₁ , it is preferably an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, and 1 to 5 carbon atoms. Is particularly preferably an alkenyl group having 2 to 5 carbon atoms. Further, it is preferably 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, one of L ^{i8 and} L ⁱ⁹ is

Is preferably represented.

L ⁱ¹⁰ and L ⁱ¹¹ each independently represent preferably 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 formula (i)

When the group represented by is present, the number of the group is preferably 2 or less in order to improve the miscibility with other liquid crystal components. When two groups are present in the general formula (i), it is preferable that they are 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 are present in the general formula (i), they are preferably present at the positions of L ⁱ¹ and L ⁱ² . The compound represented by the general formula (i) does not have a structure in which heteroatoms are directly bonded to each other.
Among the general formula (i), each compound represented by the following general formula (i-1) to general formula (i-1000) is preferable. Among them, particularly preferable 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), (i-895), (i-896), (i-897), (i -898), (i-899), and (i-900).

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² have the same meanings as R ⁱ¹ in the general formula (i).)

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} is ^X i2 in the general formula ^{(i), Y i2, W} i1, but respectively ^{L i2} and ^{L i5} the same meaning, X presence of a plurality of ⁱ² may be the same or different,
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 - represents,
The broken line indicates that the bond may or may not exist. )
And a compound represented by the general formula (i-r2)

( ^Wherein X ⁱ¹ , Y ⁱ¹ , L ⁱ¹ , L ⁱ³ , L ⁱ⁴ and W ⁱ² have the same meanings as X ⁱ¹ , Y ⁱ¹ , L ⁱ¹ , L ⁱ³ , L ⁱ⁴ and W ⁱ² in the 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 compound represented by the general formula (i-r3) is obtained by reacting the compound in the presence of a transition metal catalyst and a base.

(In the formula, 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 respectively have the same meaning, but a plurality of X ⁱ² may be the same or different.
The broken line indicates that the bond may or may not exist. )
After the compound represented by the formula ( ¹ ) is obtained, it can be obtained by intramolecular reaction by deprotonating —Y ⁱ¹ —H in the general formula (i-r3) with a base to generate an anion. More specifically, it can be manufactured as follows. Of course, the spirit and application range of the present invention are not limited by these production examples.
(Manufacturing method 1)

^{(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} Represents
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 - represents,
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,
^Yi3 represents -O- or -S-. )
The compound represented by the general formula (S-2) can be obtained by boronizing the compound represented by the general formula (S-1). This boration can be performed by deprotonating with an organometallic reagent and then reacting with a trialkyl borate to give a boron compound.
The reaction solvent may be any one as long as it allows the reaction to proceed properly, 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, and examples of hydrocarbon solvents include pentane, hexane, cyclohexane, heptane, octane and the like. Of these, tetrahydrofuran is preferable.

  Examples of the organometallic reagent include n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, lithium diisopropylamide, lithium 2,2,4,4-tetramethylpiperidide, and the like. From the viewpoint of easy handling, n-butyllithium, sec-butyllithium and lithium diisopropylamide are preferable, and sec-butyllithium and lithium diisopropylamide, which can deprotonate efficiently, are more preferable. Further, at the time of deprotonation, a base such as potassium-t-butoxide or tetramethylethylenediamine may be used as an additive together with the above-mentioned organometallic reagent. The reaction temperature for deprotonation is preferably -100 ° C to -20 ° C, more preferably -78 ° C to -40 ° C.

As the trialkyl borate, it is preferable to use trimethyl borate, triethyl borate, tripropyl borate and triisopropyl borate, but trimethyl borate and triisopropyl borate are more preferable because of easy availability and handling. As the combination of the trialkyl borate and the organometallic reagent, any combination mentioned above is possible, but a combination of sec-butyllithium and trimethyl borate, and a combination of lithium diisopropylamide and triisopropyl borate are preferable, and lithium diisopropyl The combination of amide and triisopropyl borate is more preferred. The reaction temperature at the time of boration is preferably -100 ° C to -20 ° C, more preferably -78 ° C to -40 ° C.
To obtain the compound represented by the general formula (S-4) by reacting the compound represented by the general formula (S-2) with the compound represented by the (S-3) in the presence of a transition metal catalyst and a base. You can
The transition metal catalyst to be used may be any one as long as it allows the reaction to proceed properly, but tetrakis (triphenylphosphine) palladium (0), palladium (II) acetate, bis (triphenylphosphine) palladium dichloride are used. (II), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride or bis [di-tert-butyl (4-dimethylaminophenyl) phosphine] palladium (II) dichloride is preferable, Tetrakis (triphenylphosphine) palladium (0), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride or bis [di-tert-butyl (4-dimethylaminophenyl) phosphine] dichloride. More preferably, it is palladium (II). Further, in order to allow the reaction to proceed appropriately, a phosphine-based ligand such as triphenylphosphine may be added, if necessary.

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

  As the base to be used, any base may be used as long as it allows the reaction to proceed suitably, but carbonates such as potassium carbonate, sodium carbonate and cesium carbonate, and phosphates such as tripotassium phosphate and potassium dihydrogen phosphate. Are preferred, and potassium carbonate, cesium carbonate, and tripotassium phosphate are more preferred.

The reaction temperature may be any number as long as it allows the reaction to proceed suitably, but it is preferably from room temperature to the temperature at which the solvent used is refluxed, more preferably from 40 ° C. to the solvent reflux. It is particularly preferable that the temperature is from 60 ° C. to the reflux of the solvent.
The compound represented by the general formula (S-5) can be obtained by intramolecularly reacting the compound represented by the general formula (S-4). This intramolecular reaction can be carried out by deprotonating ^-Yi3- H of the general formula (S-4) 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. Phosphates, alkali metal phosphates, alkali metal carbonates, alkali metal hydroxides, alkali metal amides and alkali metals are preferred, and alkali metal phosphates, alkali metal hydrides and alkali metal carbonates are more preferred. As alkali metal hydrides, lithium hydride, sodium hydride and potassium hydride, as alkali metal phosphates, tripotassium phosphate, and as alkali metal carbonates, sodium carbonate, sodium hydrogen carbonate, cesium carbonate, potassium carbonate. And potassium hydrogen carbonate can be preferably mentioned respectively.

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

The reaction temperature may be in the reflux temperature range from the freezing point of the solvent, but is preferably 0 ° C to 150 ° C, more preferably 30 ° C to 120 ° C.
By halogenating the compound represented by the general formula (S-5), the compound represented by the general formula (S-6) can be obtained. This halogenation can be performed by deprotonating with an organometallic reagent and then reacting with bromine or iodine to form a halogen compound.
The reaction solvent may be any one as long as it allows the reaction to proceed properly, 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, and examples of hydrocarbon solvents include pentane, hexane, cyclohexane, heptane, octane and the like. Of these, tetrahydrofuran is preferable.

Examples of the organometallic reagent include n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, lithium diisopropylamide, lithium 2,2,4,4-tetramethylpiperidide, and the like. From the viewpoint of easy handling, n-butyllithium, sec-butyllithium and lithium diisopropylamide are preferable, and sec-butyllithium and lithium diisopropylamide, which can deprotonate efficiently, are more preferable. Further, at the time of deprotonation, a base such as potassium-t-butoxide or tetramethylethylenediamine may be used as an additive together with the above-mentioned organometallic reagent. The reaction temperature for deprotonation is preferably -100 ° C to -20 ° C, more preferably -78 ° C to -40 ° C.
To obtain a compound represented by the general formula (S-8) by reacting a compound represented by the general formula (S-6) with a compound represented by the (S-7) in the presence of a transition metal catalyst and a base. You can
The transition metal catalyst to be used may be any one as long as it allows the reaction to proceed properly, but tetrakis (triphenylphosphine) palladium (0), palladium (II) acetate, bis (triphenylphosphine) palladium dichloride are used. (II), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride or bis [di-tert-butyl (4-dimethylaminophenyl) phosphine] palladium (II) dichloride is preferable, Tetrakis (triphenylphosphine) palladium (0), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride or bis [di-tert-butyl (4-dimethylaminophenyl) phosphine] dichloride. More preferably, it is palladium (II). Further, in order to allow the reaction to proceed appropriately, a phosphine-based ligand such as triphenylphosphine may be added, if necessary.

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

  As the base to be used, any base may be used as long as it allows the reaction to proceed suitably, but carbonates such as potassium carbonate, sodium carbonate and cesium carbonate, and phosphates such as tripotassium phosphate and potassium dihydrogen phosphate. Are preferred, and potassium carbonate, cesium carbonate, and tripotassium phosphate are more preferred.

The reaction temperature may be any number as long as it allows the reaction to proceed suitably, but it is preferably from room temperature to the temperature at which the solvent used is refluxed, more preferably from 40 ° C. to the solvent reflux. It is particularly preferable that the temperature is from 60 ° C. to the reflux of the solvent.
(Manufacturing method 2)

^{(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 general formula (S-9) can be obtained by oxidizing the compound represented by general formula (S-5). This oxidation can be performed by deprotonating with an organometallic reagent, reacting with a trialkyl borate to give a boron compound, and then reacting with an oxidizing agent.
The reaction solvent may be any one as long as it allows the reaction to proceed properly, 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, and examples of hydrocarbon solvents include pentane, hexane, cyclohexane, heptane, octane and the like. Of these, tetrahydrofuran is preferable. Examples of the organometallic reagent include n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, lithium diisopropylamide, lithium 2,2,4,4-tetramerpiperidide, and the like. From the viewpoint of easy handling, n-butyllithium, sec-butyllithium and lithium diisopropylamide are preferable, and sec-butyllithium and lithium diisopropylamide, which can deprotonate efficiently, are more preferable. Further, at the time of deprotonation, a base such as potassium-t-butoxide or tetramethylethylenediamine may be used as an additive together with the above-mentioned organometallic reagent. The reaction temperature for deprotonation is preferably -100 ° C to -20 ° C, more preferably -78 ° C to -40 ° C.

  As the trialkyl borate, it is preferable to use trimethyl borate, triethyl borate, tripropyl borate and triisopropyl borate, but trimethyl borate and triisopropyl borate are more preferable because of easy availability and handling. As the combination of the trialkyl borate and the organometallic reagent, any combination mentioned above is possible, but a combination of sec-butyllithium and trimethyl borate, and a combination of lithium diisopropylamide and triisopropyl borate are preferable, and lithium diisopropyl The combination of amide and triisopropyl borate is more preferred. The reaction temperature at the time of boration 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 directly reacted with an oxidizing agent without isolation. Further, the obtained boron compound may be hydrolyzed into a boric acid compound and then reacted with an oxidizing agent.

  It is preferable to use hydrogen peroxide solution, peracetic acid, or formic acid as the oxidizing agent. The reaction temperature is preferably -78 ° C to 70 ° C, more preferably 0 ° C to 50 ° C. Further, the solvent may contain water during the reaction with the oxidizing agent.

The compound represented by general formula (S-11) can be obtained by reacting the compound represented by general formula (S-9) with the compound represented by general formula (S-10). This reaction can be carried out by reacting the hydroxyl group of the general formula (S-9) with the general formula (S-10) as a phenolate with a base. Examples of the base used in this case include metal hydrides, metal carbonates and metals. Examples thereof include phosphates, metal hydroxides, metal carboxylates, metal amides and metals. Among them, 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 the alkali metal hydride, tripotassium phosphate as the alkali metal phosphate, sodium carbonate, sodium hydrogen carbonate, cesium carbonate, potassium carbonate as the alkali metal carbonate. And potassium hydrogen carbonate can be preferably mentioned respectively.
Any reaction solvent may be used as long as it allows the reaction to proceed properly, but ether solvents, chlorine solvents, hydrocarbon solvents, aromatic solvents, polar solvents and the like can be preferably used. As the ether solvent, 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether, t-butyl methyl ether and the like, and as the chlorine solvent, dichloromethane, 1,2-dichloroethane, carbon tetrachloride and the like, As the hydrocarbon solvent, pentane, hexane, cyclohexane, heptane, octane, etc., as the aromatic solvent, benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, etc., and as the polar solvent, N, N-dimethylformamide, Preferable examples include N-methylpyrrolidone, dimethyl sulfoxide, sulfolane and the like. Among them, ether solvents such as tetrahydrofuran and diethyl ether and polar solvents such as N, N-dimethylformamide are more preferable. Further, each of the above solvents may be used alone, or two or more solvents may be mixed and used.

The reaction temperature may be in the reflux temperature range from the freezing point of the solvent, but is preferably 0 ° C to 150 ° C, more preferably 30 ° C to 120 ° C. In addition, the produced phenolate may be isolated once and then reacted with the compound represented by the general formula (S-5), or may be reacted without isolation. It is better to react.
(Manufacturing method 3)

(In the formula, L ⁱ¹ , L ⁱ² , X ⁱ¹ , X ⁱ² , Y ^i2, and W ⁱ¹¹ have the same meanings as L ⁱ¹ , L ⁱ² , X ⁱ¹ , X ⁱ² , Y ^i2, and W ⁱ¹ in the general formula (i). Represents
^Yi3 represents -O- or -S-. )
The compound represented by the general formula (S-5) can be obtained by reacting the compound represented by the general formula (S-5) with the compound represented by the general formula (S-11). This reaction can be carried out by deprotonating with an organometallic reagent and then reacting with the general formula (S-11).
The reaction solvent may be any one as long as it allows the reaction to proceed properly, 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, and examples of hydrocarbon solvents include pentane, hexane, cyclohexane, heptane, octane and the like. Of these, tetrahydrofuran is preferable.
Examples of the organometallic reagent include n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, lithium diisopropylamide, lithium 2,2,4,4-tetramethylpiperidide, and the like. From the viewpoint of easy handling, n-butyllithium, sec-butyllithium and lithium diisopropylamide are preferable, and sec-butyllithium and lithium diisopropylamide, which can deprotonate efficiently, are more preferable. Further, at the time of deprotonation, a base such as potassium-t-butoxide or tetramethylethylenediamine may be used as an additive together with the above-mentioned organometallic reagent. The reaction temperature for deprotonation is preferably -100 ° C to -20 ° C, more preferably -78 ° C to -40 ° C.

The compound represented by general formula (S-13) can be obtained by dehydrating the compound represented by general formula (S-12). 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 method of dehydration, the hydroxyl group may be reacted with p-toluenesulfonic acid chloride, trifluoromethanesulfonic acid chloride, triphosgene or the like to convert into a leaving group, and then the elimination reaction may be performed to perform dehydration.
The compound represented by the general formula (S-14) can be obtained by reacting the compound represented by the general formula (S-13) with hydrogen gas in the presence of a metal catalyst in an organic solvent.

  The organic solvent used may be any as long as it allows the reaction to proceed properly, but it is an ether solvent such as diisopropyl ether, diethyl ether, 1,4-dioxane or tetrahydrofuran, hexane, heptane, toluene or xylene. The hydrocarbon-based solvent, the alcohol-based solvent such as methanol, ethanol, propanol, isopropyl alcohol or butanol and the ester-based solvent such as ethyl acetate or butyl acetate are preferable, and tetrahydrofuran, hexane, heptane, toluene, ethanol or ethyl acetate is preferable. It is also preferable to add an acid such as hydrochloric acid, acetic acid or sulfuric acid, if necessary.

  The reaction temperature may be any temperature as long as it allows the reaction to proceed properly, but is preferably 0 ° C. to 80 ° C., more preferably room temperature to 60 ° C.

  The metal catalyst used may be any one as long as it allows the reaction to proceed properly, but palladium carbon, ruthenium carbon, platinum black or platinum oxide is preferable, and palladium carbon is more preferable.

The hydrogen pressure at the time of reaction may be any as long as it allows the reaction to proceed appropriately, but it is preferably from atmospheric pressure to 0.5 MPa, more preferably from 0.2 MPa to 0.5 MPa.
(Manufacturing method 4)

^{(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 — present in the alkyl group or alkenyl group or two or more non-adjacent groups. —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 replaced by an atom,
X ⁱ⁴ represents a bromine atom or an iodine atom,
X ⁱ⁵ represents a chlorine atom or a bromine atom,
^Yi3 represents -O- or -S-. )
The compound represented by general formula (S-16) can be obtained by reacting the compound represented by general formula (S-6) with the compound represented by (S-15) in the presence of a transition metal catalyst. .
Any transition metal catalyst may be used as long as it allows the reaction to proceed appropriately, and bis (triphenylphosphine) nickel (II) dichloride, [1,2-bis (diphenylphosphino) dichloride] Ethane] nickel (II), [1,2-bis (diphenylphosphino) propane] nickel (II) dichloride, [1,1′-bis (diphenylphosphino) ferrocene] nickel (II) dichloride, tetrakis ( Triphenylphosphine) palladium (0), palladium (II) acetate, bis (triphenylphosphine) palladium (II) dichloride, [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride or dichloride. Bis [di-tert-butyl (4-dimethylaminophenyl) phosphine] palladium (II) chloride is preferred. Specifically, tetrakis (triphenylphosphine) palladium (0), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride, tris (dibenzylideneacetone) palladium (0) or bis [dichloride dichloride. More preferably, it is -tert-butyl (4-dimethylaminophenyl) phosphine] palladium (II). Further, in order to allow the reaction to proceed appropriately, a phosphine-based ligand such as triphenylphosphine may be added, if necessary.

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

The reaction temperature may be any number as long as it allows the reaction to proceed suitably, but it is preferably from room temperature to the temperature at which the solvent used is refluxed, more preferably from 40 ° C. to the solvent reflux. It is particularly preferable that the temperature is from 60 ° C. to the reflux of the solvent.
(Manufacturing method 5)

^(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 - represents,
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, an iodine atom, a methanesulfonyloxy group, a p-toluenesulfonyloxy group, a trifluoromethanesulfonyloxy group or a hydroxyl group,
^Yi3 represents -O- or -S-. )
Obtaining a compound represented by the general formula (S-19) by reacting a compound represented by the general formula (S-17) with a compound represented by (S-18) in the presence of a transition metal catalyst and a base. You can
The transition metal catalyst to be used may be any one as long as it allows the reaction to proceed properly, but tetrakis (triphenylphosphine) palladium (0), palladium (II) acetate, bis (triphenylphosphine) palladium dichloride are used. (II), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride or bis [di-tert-butyl (4-dimethylaminophenyl) phosphine] palladium (II) dichloride is preferable, Tetrakis (triphenylphosphine) palladium (0), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride or bis [di-tert-butyl (4-dimethylaminophenyl) phosphine] dichloride. More preferably, it is palladium (II). Further, in order to allow the reaction to proceed appropriately, a phosphine-based ligand such as triphenylphosphine may be added, if necessary.

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

  As the base to be used, any base may be used as long as it allows the reaction to proceed suitably, but carbonates such as potassium carbonate, sodium carbonate and cesium carbonate, and phosphates such as tripotassium phosphate and potassium dihydrogen phosphate. Are preferred, and potassium carbonate, cesium carbonate, and tripotassium phosphate are more preferred.

The reaction temperature may be any number as long as it allows the reaction to proceed suitably, but it is preferably from room temperature to the temperature at which the solvent used is refluxed, more preferably from 40 ° C. to the solvent reflux. It is particularly preferable that the temperature is from 60 ° C. to the reflux of the solvent.
The compound represented by the general formula (S-20) can be obtained by intramolecularly reacting the compound represented by the general formula (S-19). This intramolecular reaction can be carried out by deprotonating ^-Yi3- H of the general formula (S-19) 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. Phosphates, alkali metal phosphates, alkali metal carbonates, alkali metal hydroxides, alkali metal amides and alkali metals are preferred, and alkali metal phosphates, alkali metal hydrides and alkali metal carbonates are more preferred. As alkali metal hydrides, lithium hydride, sodium hydride and potassium hydride, as alkali metal phosphates, tripotassium phosphate, and as alkali metal carbonates, sodium carbonate, sodium hydrogen carbonate, cesium carbonate, potassium carbonate. And potassium hydrogen carbonate can be preferably mentioned respectively.

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

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

The compound represented by the general formula (S-21) can be obtained by oxidizing the compound represented by the general formula (S-20). This oxidation can be performed by deprotonating with an organometallic reagent, reacting with a trialkyl borate to give a boron compound, and then reacting with an oxidizing agent.
The reaction solvent may be any one as long as it allows the reaction to proceed properly, 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, and examples of hydrocarbon solvents include pentane, hexane, cyclohexane, heptane, octane and the like. Of these, tetrahydrofuran is preferable. Examples of the organometallic reagent include n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, lithium diisopropylamide, lithium 2,2,4,4-tetramerpiperidide, and the like. From the viewpoint of easy handling, n-butyllithium, sec-butyllithium and lithium diisopropylamide are preferable, and sec-butyllithium and lithium diisopropylamide, which can deprotonate efficiently, are more preferable. Further, at the time of deprotonation, a base such as potassium-t-butoxide or tetramethylethylenediamine may be used as an additive together with the above-mentioned organometallic reagent. The reaction temperature for deprotonation is preferably -100 ° C to -20 ° C, more preferably -78 ° C to -40 ° C.

  As the trialkyl borate, it is preferable to use trimethyl borate, triethyl borate, tripropyl borate and triisopropyl borate, but trimethyl borate and triisopropyl borate are more preferable because of easy availability and handling. As the combination of the trialkyl borate and the organometallic reagent, any combination mentioned above is possible, but a combination of sec-butyllithium and trimethyl borate, and a combination of lithium diisopropylamide and triisopropyl borate are preferable, and lithium diisopropyl The combination of amide and triisopropyl borate is more preferred. The reaction temperature at the time of boration 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 directly reacted with an oxidizing agent without isolation. Further, the obtained boron compound may be hydrolyzed into a boric acid compound and then reacted with an oxidizing agent.

  It is preferable to use hydrogen peroxide solution, peracetic acid, or formic acid as the oxidizing agent. The reaction temperature is preferably -78 ° C to 70 ° C, more preferably 0 ° C to 50 ° C. Further, the solvent may contain water during the reaction with the oxidizing agent.

The compound represented by the general formula (S-23) is obtained by reacting the compound represented by the general formula (S-21) with the compound represented by the general formula (S-22). It is possible to use several reactions by the choice of the substituent of X ⁱ⁴ in -22).

When a compound in which X ⁱ⁴ represents a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, a p-toluenesulfonyloxy group or a trifluoromethanesulfonyloxy group is used, the hydroxyl group of the general formula (S-21) is phenolated with a base. The method of reacting with General formula (S-22) can be used as. 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. Phosphates, alkali metal phosphates, alkali metal carbonates, alkali metal 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 the alkali metal hydride, tripotassium phosphate as the alkali metal phosphate, sodium carbonate, sodium hydrogen carbonate, cesium carbonate, potassium carbonate as the alkali metal carbonate. And potassium hydrogen carbonate can be preferably mentioned respectively.

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

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

When X ⁱ⁴ represents a hydroxyl group, it is possible to use the Mitsunobu reaction. The Mitsunobu reaction is a reaction in which an alcohol and various nucleophiles having active protons are condensed by dehydration, and triphenylphosphine is used in combination with an azodicarboxylic acid derivative or a maleic acid derivative. Specifically, the compound represented by the general formula (S-21) is reacted with the alcohol derivative represented by the general formula (S-22) in the presence of a tri-substituted phosphine derivative and an azodicarboxylic acid derivative. A compound represented by (S-23) is obtained.

  Examples of the tri-substituted phosphine derivative include trialkylphosphine and triphenylphosphine, with triphenylphosphine being preferred. Further, various compounds are used as the azodicarboxylic acid derivative, and it is possible to use a maleic acid derivative in place of the azodicarboxylic acid derivative, but a combination of triphenylphosphine and the azodicarboxylic acid derivative can be used because of easy handling. Is desirable. Examples of the azodicarboxylic acid derivative include diethyl azodicarboxylate, diisopropyl azodicarboxylate, tetramethyl azodicarboxamide, tetrapropyl azodicarboxamide, and 1,1 ′-(azodicarbonyl) dipiperidine, which are available. Diethyl azodicarboxylate and diisopropyl azodicarboxylate are preferred for their ease of use, and diisopropyl azodicarboxylate is more preferred for their ease of handling.

  As the reaction solvent, any solvent may be used as long as it allows the reaction to proceed appropriately, but ether solvents, chlorine solvents, hydrocarbon solvents, aromatic solvents and the like can be preferably used. As the ether solvent, 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether, t-butyl methyl ether and the like, and as the chlorine solvent, dichloromethane, 1,2-dichloroethane, carbon tetrachloride and the like, Preferable examples of the hydrocarbon solvent include pentane, hexane, cyclohexane, heptane and octane, and examples of the aromatic solvent include benzene, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene. Among them, ether solvents such as tetrahydrofuran and aromatic solvents such as toluene are more preferable. Further, each of the above solvents may be used alone, or two or more solvents may be mixed and used.

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

  The compound represented by general formula (S-24) can be obtained by subjecting the compound represented by general formula (S-23) to sigmatropic rearrangement.

  Any reaction solvent may be used as long as it allows the reaction to proceed properly, but ether solvents, chlorine solvents, hydrocarbon solvents, aromatic solvents, polar solvents and the like can be preferably used. As the ether solvent, 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether, t-butyl methyl ether and the like, and as the chlorine solvent, dichloromethane, 1,2-dichloroethane, carbon tetrachloride and the like, As the hydrocarbon solvent, pentane, hexane, cyclohexane, heptane, octane, etc., as the aromatic solvent, benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, etc., and as the polar solvent, N, N-diethylaniline, Preferable examples include N, N-dimethylaniline, N, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide and sulfolane. Among them, polar solvents such as N, N-diethylaniline and N, N-dimethylaniline are more preferable. Further, each of the above solvents may be used alone, or two or more solvents may be mixed and used.

  The reaction temperature may be in the reflux temperature range from the freezing point of the solvent, but is preferably 100 ° C to 250 ° C, more preferably 150 ° C to 250 ° C.

  The compound represented by the general formula (S-25) can be obtained by reacting the compound represented by the general formula (S-24) with hydrogen gas in the presence of a metal catalyst in an organic solvent.

  The organic solvent used may be any as long as it allows the reaction to proceed properly, but it is an ether solvent such as diisopropyl ether, diethyl ether, 1,4-dioxane or tetrahydrofuran, hexane, heptane, toluene or xylene. The hydrocarbon-based solvent, the alcohol-based solvent such as methanol, ethanol, propanol, isopropyl alcohol or butanol and the ester-based solvent such as ethyl acetate or butyl acetate are preferable, and tetrahydrofuran, hexane, heptane, toluene, ethanol or ethyl acetate is preferable. It is also preferable to add an acid such as hydrochloric acid, acetic acid or sulfuric acid, if necessary.

  The reaction temperature may be any temperature as long as it allows the reaction to proceed properly, but is preferably 0 ° C. to 80 ° C., more preferably room temperature to 60 ° C.

  The metal catalyst used may be any one as long as it allows the reaction to proceed properly, but palladium carbon, ruthenium carbon, platinum black or platinum oxide is preferable, and palladium carbon is more preferable.

  The hydrogen pressure at the time of reaction may be any as long as it allows the reaction to proceed appropriately, but it is preferably from atmospheric pressure to 0.5 MPa, more preferably from 0.2 MPa to 0.5 MPa.

  Thus, as a preferable representative example of the compound which can be used by mixing with the compound represented by the general formula (i), in the composition provided by the present invention, the first component is the general formula (i). ) At least one compound represented by the formula (1) is contained, and it is particularly preferable that at least one kind selected from the following second to fourth components is contained 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 ^{R LC31, R LC32, R LC41} , R LC42, alkyl groups ^{R LC51} and ^{R LC52} is 1-15 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— such that the oxygen atom is not directly adjacent to the alkyl group. 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 The structure of

(One of the structures during cyclohexylene or two or more -CH 2 _- may be substituted with an oxygen atom, one or two or more of 1,4-phenylene group -CH- is nitrogen atom may be substituted with, also, one or more hydrogen atoms are fluorine atoms in the structure, a chlorine atom, may be substituted with -CF ₃ or -OCF _3.) either It 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-a represents, ^{Z 5} is -CH ₂ - represents an or an oxygen ^{atom, X LC41} is ^Represents a hydrogen atom or a fluorine atom, m ^LC31 , m ^{L C32, m LC41, m LC42,} m LC51 and ^{m LC52} represent each independently ^{0~3, m LC31 + m LC32,} m LC41 + m LC42 and ^m LC51 ^{+ m LC52} is 1, 2 or ^{3, A LC31} ~ When there are a plurality of A ^LC52 and Z ^{LC31 to} Z ^LC52 , 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. The alkenyl group has the following structure. Most preferably

(In the formula, the ring structure is bound at the right end.)
A ^{LC31 to} A ^LC52 each independently have the following structure,

Z ^LC31 ~Z ^LC51 each independently represent a single _{bond, -CH 2 O -, - COO} -, - OCO -, - CH 2 CH 2 -, - CF 2 O -, - OCF 2 - or -OCH ₂ - is preferable.

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

(In the formula, 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 represent A hydrogen atom or a fluorine atom is represented, but at least one combination 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). A compound selected from the group: 1) or two or more compounds selected from the group of compounds represented by Rukoto is preferable.
R ^LC31 and R ^LC32 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 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, a 1,3-dioxane-2,5-diyl group, or 1 , 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 the 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. It is more preferable that R ^LC32 represents an alkyl group having 1 to 7 carbon atoms and R ^LC32 represents an alkoxy group having 1 to 7 carbon atoms.

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

(In the formula, R ^LC31 and R ^LC32 each independently represent the same meaning as R ^LC31 and R ^LC32 in the 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. It is more preferable that R ^LC32 represents an alkyl group having 3 or 3 carbon atoms and R ^LC32 represents an alkyl group having 2 carbon atoms.

  General formula (LC4) is from general formula (LC4-a) to general formula (LC4-c), and general formula (LC5) is from 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 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 -, - expressed in or an _{-CF 2} O-) - OCF 2. More preferably, it is one or more compounds selected from the group consisting of

^{R LC41,} R LC42, R ^LC51 and ^{R LC52} each independently represents an alkyl group having 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 is preferable to represent the alkenyloxy group of ~ 7.

It is preferable that Z ^{LC4a1 to} Z ^LC5c1 each independently represent a single bond, —CH ₂ O—, ^{—COO—, —OCO—} , or —CH ₂ CH ₂ —, and more preferably 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).

(In the formula, R ^LC61 and R ^LC62 each independently represent an alkyl group having 1 to 15 carbon atoms, and one or two or more —CH ₂ — in the alkyl group are not directly adjacent to an oxygen atom. As described above, it 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 halogen, and A ^{LC61 to} A ^LC63 are each independently the following:

(One of the structures during cyclohexylene or more _-CH 2 CH ₂ - is _{-CH = CH -, - CF 2} O -, - OCF 2 - may be substituted with 1,4 ^-One or more CH groups in the phenylene group may be substituted with a nitrogen atom.), ^ZLC61 and ^ZLC62 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-a represents, m ^Lc6 represents 0 to 3. However, the compounds represented by the general formulas (LC1) to (LC5) and the 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. The alkenyl group has the following structure. Most preferably

(In the formula, the ring structure is bound at the right end.)
A ^{LC61 to} A ^LC63 each independently preferably have the following structure,

Z ^LC61 and ^{Z LC62} each independently represent a single _{bond, -CH 2 CH 2 -, -} COO -, - OCH 2 -, - CH 2 O -, - OCF 2 - or _-CF 2 O-are preferred.

  The general formula (LC6) includes the general formula (LC6-a) to the general formula (LC6-m).

(In the formula, 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 the compound is one or more compounds selected from the group consisting of compounds represented by the formula (1).

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

(In the formula, R ^LC11 and R ^LC21 each independently represent an alkyl group having 1 to 15 carbon atoms, and one or two or more —CH ₂ — in the alkyl group are not directly adjacent to an oxygen atom. As described above, it 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 each independently represent one of the structures below.

(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 is substituted by a nitrogen atom, also one or more hydrogen atoms are fluorine atoms in the structure, a chlorine atom, may be substituted with -CF ₃ or -OCF _3.) the ^{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- And m ^LC11 and m ^LC21 each independently represent 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, an alkenyl group having 2 to 7 carbon atoms, and an alkyl group having 1 to 5 carbon atoms. A group, an alkoxy group having 1 to 5 carbon atoms, and an alkenyl group having 2 to 5 carbon atoms are more preferable, a straight chain is further preferable, and the following structure is most preferable as the alkenyl group.

(In the formula, the ring structure is bound at the right end.)
A ^LC11 and A ^LC21 each independently preferably have the following structure.

Y ^LC11 and Y ^LC21 each independently represent 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} is a single _{bond, -CH 2 CH 2 -, -} COO -, - OCO -, - OCH 2 -, - CH 2 O -, - OCF 2 - or _-CF 2 O-are more preferably a single bond _{, -CH 2 CH 2 -, -} OCH 2 -, - OCF 2 - or _-CF 2 O-is preferably a single bond, -OCH ₂ - or _-CF 2 O-are more preferred.

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

  The general formula (LC1) includes 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, a 1,3-dioxane-2,5-diyl group, and is X ^LC1b1 , X ^LC1b2 , X ^{LC1c1 to} X ^LC1c4. Each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, —CF ₃ or —OCF ₃ ), and is preferably one or more compounds selected from the group consisting of compounds represented by:

R ^LC11 is independently preferably 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, and an alkyl group having 1 to 5 carbon atoms or 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 preferably each independently a hydrogen atom or a fluorine atom.

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

  In addition, the general formula (LC1) is 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- 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 preferable, and one or more compounds selected from the group consisting of compounds represented by

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

^{XLC11 to XLC1m2} are preferably each independently a hydrogen atom or a fluorine atom.

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

Z ^LC1d1 ~Z ^LC1m1 is _-CF 2 O each independently -, - OCH ₂ - is preferred.
The general formula (LC2) includes the following general formula (LC2-a) to the general formula (LC2-g).

(In the formula, R ^LC21 , Y ^LC21 , and X ^{LC21 to} X ^LC23 each independently represent 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 ~X LC2e4, X LC2f1 ~X} LC2f4 and ^X LC2g1 ^{~X LC2g4} are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a -CF ₃ or _{^{-OCF 3, Z LC2a1, Z LC2b1}} , Z LC2c1, ^{Z LC2d1,} Z LC2e1, Z ^LC2f1 and ^{Z LC2g1} 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- also Represents -OCO-), and is preferably one or two or more compounds selected from the group consisting of compounds represented by:

R ^LC21 is independently preferably 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, and an alkyl group having 1 to 5 carbon atoms or 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 each independently a fluorine atom, -CF ₃ or -OCF ₃ are preferred.

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

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

  When importance is attached to the stability by UV irradiation, the content of the compound in which the chlorine atom is substituted is preferably 15% or less, and more preferably 10% or less with respect to the total mass of the composition. % Or less, preferably 5% or less, more preferably 3% or less, and further preferably substantially not contained.

  In order to suppress the deterioration of the composition due to oxidation, 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 to the total mass of the composition. On the other hand, it is preferably 10% or less, more preferably 8% or less, further preferably 5% or less, more preferably 3% or less, and further preferably substantially 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 Is preferable, and the content of the compound having the 2-methylbenzene-1,4-diyl group in the molecule is preferably 10% or less, and 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 further preferably substantially not contained.

  In the present application, "substantially free from" means not containing except an unintended inclusion.

  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 alkenyl group preferably has 4 to 5 carbon atoms, and the unsaturated bond of the alkenyl group and benzene are directly bonded to each other. Preferably not.

The average elastic constant (K _AVG ) of the liquid crystal composition used in the present invention is preferably 10 to 25, but the lower limit value thereof is preferably 10, preferably 10.5, preferably 11 and 11.5. , 12 is preferred, 12.3 is preferred, 12.5 is preferred, 12.8 is preferred, 13 is preferred, 13.3 is preferred, 13.5 is preferred, 13.8 is preferred, 14 is preferred, 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 is preferable, 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 preferred, 24.5 is preferred, 24 is preferred, 23.5 is preferred, 23 is preferred, 22.8 is preferred, 22.5 is preferred, 22.3 is preferred, 22 is preferred, 21.8 is Preferably, 21.5 is preferable, 21.3 is preferable, 21 is preferable, 20.8 is preferable, 20.5 is preferable, 20.3 is preferable, 20 is preferable, 19.8 is preferable, and 19.5 is preferable. Preferably, 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, and 17.3 is preferred. 17 is preferable. When emphasizing power reduction, it is effective to suppress the amount of light of the backlight, it is preferred that the liquid crystal display device to improve the light transmittance, it To achieve this the set lower value of K _AVG preferable. When the improvement of the response speed is important, it is preferable to set the value of K _AVG higher. 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 it corresponds to a thin cell gap, and 0.08 to 0.10 when it corresponds to 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., particularly preferably 70 ° C. to 85 ° C. In addition, it preferably exhibits 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 compounds. Good. A liquid crystal display device using a liquid crystal composition containing the compound of the present invention is useful for achieving both high-speed response and suppression of display defects, and is particularly useful for an active matrix driving liquid crystal display device. It can be applied to liquid crystal display elements of various modes such as mode, PSVA mode, PSA mode, IPS mode, FFS mode, ECB mode and the like.

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

T _n-i represents a nematic phase-isotropic phase transition temperature.

The following abbreviations are used in the description of compounds.
THF: tetrahydrofuran LDA: lithium diisopropylamide Me: methyl group, Et: ethyl group, Pr: n-propyl group, Bu: n-butyl group,
Pent: n-Pentyl Group (Example 1) Synthesis of Compound 1-2-5

(Synthesis of Compound 1-2-5)
Under a nitrogen atmosphere, LDA (15.8 g) and THF (120 ml) were added to a reaction vessel equipped with a stirrer, a thermometer and a dropping funnel, and cooled to -15 ° C. A 1.6 M butyllithium / hexane solution (86.7 ml) was added dropwise at -15 ° C., the mixture was stirred for 1 hour, and then compound 1-1-5 (25.0 g) previously dissolved in THF (25 ml). ) And triisopropyl borate (29.4 g) were simultaneously added dropwise at -5 ° C, and the mixture was stirred for 1 hour. The reaction mixture was heated to 0 ° C., 10% hydrochloric acid (120 ml) was added and the mixture was stirred, and the organic layer was separated. Further, the aqueous layer was extracted with toluene (100 ml). The obtained organic layers were combined, washed with water and saturated brine, dried over anhydrous sodium sulfate, and dried. The resulting solution was concentrated to obtain a crude compound 2 (31.0 g). Compound 1-2-5 (16.4 g) was obtained by recrystallizing using a hexane / ethyl acetate mixed solvent.
(Examples 2 to 18) Synthesis of compound 1-2-0 to compound 4-2-8 Example 2 (using the same reaction as in Example 1 and, if necessary, a method in accordance with a known method, Compound 1-2-0) to Example 18 (Compound 3-2-8) were synthesized.

(Example 19) Synthesis of compound 1-5-5

(Synthesis of Compound 1-4-5)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a condenser under a nitrogen atmosphere, 3-fluoro-2-hydroxychlorobenzene (6.1 g), bis (ditertiarybutyl (4-dimethylaminophenyl) phosphine) Palladium (II) chloride complex (0.88 g), THF (50 ml) and 2M cesium carbonate aqueous solution (40 ml) were added, and the temperature was raised to 60 ° C. with stirring. Compound 1-3-5 (15.2 g) previously dissolved in THF (45 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 (50 ml) was added. The organic layer was separated, and the aqueous layer was reextracted with toluene (50 ml). After the obtained organic layers were combined, they were washed with water and saturated brine in that order, and anhydrous sodium sulfate was added to dry them. After concentrating the obtained solution, toluene (40 ml) was added and dissolved, and the solution was passed through a column packed with silica gel (10 g), and then toluene (60 ml) was passed through. The resulting column passing solution was concentrated to obtain compound 1-4-5 (17.6 g).

(Synthesis of Compound 1-5-5)
Under a nitrogen atmosphere, sodium hydride (60% mineral oil dispersion) (2.5 g) and DMF (30 ml) were added to a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a cooling tube, and ice-cooled with stirring. did. Compound 1-4-5 (17.6 g) previously dissolved in DMF (90 ml) was added dropwise thereto. Then, the temperature was returned to room temperature and the solution temperature was heated to 50 ° C. over 1 hour. Then, the solution temperature was heated to 105 ° C. over another 1.5 hours. After stirring at 105 ° C for 8 hours, the solution temperature was cooled to 10 ° C or lower. Water (250 ml) was added to the reaction solution. The crystals were filtered, washed with methanol and dried under vacuum. Toluene (17 ml) was added to the obtained crystals and dissolved, and the solution was passed through a column packed with silica gel (10 g), and then toluene (60 ml) was passed through. The resulting column passing solution was concentrated to obtain compound 1-5-5 (7.2 g).
(Example 20) Synthesis of compound 1-7-205

(Synthesis of Compound 1-6-5)
Compound 1-5-5 was obtained in the same manner as in Example 19.

  Under a nitrogen atmosphere, diisopropylamine (3.3 g) and THF (30 ml) were added to a reaction vessel equipped with a stirrer, a thermometer and a dropping funnel, and cooled to -10 ° C. A 1.6 M butyllithium / hexane solution (17.7 ml) was added dropwise at -10 ° C, the mixture was stirred for 1 hour, and then compound 1-5-5 (7.2 g) previously dissolved in THF (25 ml). ) And triisopropyl borate (6.1 g) were simultaneously added dropwise at −10 ° C., and the mixture was stirred for 1 hour. The reaction mixture was heated to 0 ° C., 10% hydrochloric acid (100 ml) was added and the mixture was stirred, and the organic layer was separated. The organic layer was added to a reaction vessel equipped with a stirrer, a thermometer, and a dropping funnel, and 30% hydrogen peroxide solution (10 ml) was added dropwise. After stirring at room temperature for 1 hour, the solution temperature was cooled to 0 ° C., and a 15% sodium thiosulfate aqueous solution (100 ml) was added. The organic layer was separated, and the aqueous layer was extracted with toluene (50 ml). The obtained organic layers were combined, washed with water and saturated brine, dried over anhydrous sodium sulfate, and dried. The obtained solution was concentrated to give compound 1-6-5 (7.3 g).

(Synthesis of Compound 1-7-205)
Under a nitrogen atmosphere, in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a condenser, compound 1-6-5 (5.0 g), ethyl iodide (2.5 g), cesium carbonate (5.4 g). And DMF (15 ml) were added and heated to 60 ° C. with stirring. After stirring at 60 ° C for 1.5 hours, the solution temperature was cooled to 10 ° C or lower. Water (50 ml) and toluene (30 ml) were added to the reaction solution. The organic layer was separated, and the aqueous layer was reextracted with toluene (30 ml). After the obtained organic layers were combined, they were washed with water and saturated brine in that order, and anhydrous sodium sulfate was added to dry them. After concentrating the obtained solution, hexane / toluene mixed solvent (volume ratio 1/1) (20 ml) was added and dissolved at 50 ° C. The solution was packed with silica gel (5.5 g) and heated to 50 ° C. Then, a mixed solvent of hexane / toluene (volume ratio 1/1) (30 ml) was passed. The obtained column passing solution was concentrated to obtain a crude product of compound 1-7-205 (5.0 g). Compound 1-7-205 (1.0 g) was obtained by repeating recrystallization using an acetone / methanol mixed solvent. The phase transition temperature is Cr87Iso.
(Examples 21 to 181) Synthesis of compound 1-5-0 to compound 3-7-808 Using a reaction similar to that in Example 19, Example 20, and, if necessary, a method according to a known method, Example 21 (Compound 1-5-0) to Example 351 (Compound 4-7-808) were synthesized.

(Example 352) Preparation of liquid crystal composition-1
Host liquid crystal (H) showing the following physical properties
Was prepared. All values are 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) consisting of 97% of the base liquid crystal (H) and 3% of the compound (1-7-205) obtained in Example 1 was prepared. The values of T _n-i , Δε, Δn and γ ₁ of this composition (MA) were measured, and based on the amount of change from the host liquid crystal, the compound (1-7-205) obtained in Example 1 was used. The extrapolated value of each physical property value in () was as follows.

Extrapolation Tn _-i : 23.8 degreeC.
Extrapolation Δε: -14.6
Extrapolation Δn: 0.167
Extrapolation γ ₁ : 376 mPa · s
The prepared liquid crystal composition (MA) maintained a uniform nematic liquid crystal state for one month or more at room temperature.

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

(Example 353) Preparation of liquid crystal composition-2
A liquid crystal composition (MB) consisting of 95% of the base liquid crystal (H) and 5% of the compound (1-7-405) obtained in Example 60 was prepared. From this composition (MB), the values of extrapolation T _n-i , extrapolation Δε, extrapolation Δn, and extrapolation γ ₁ of the compound (1-7-405) obtained in Example 60 were as follows. It is as follows.

Extrapolation T _n-i : 21.8 ° C
Extrapolation Δε: -14.0
Extrapolation Δn: 0.158
Extrapolation γ ₁ : 360 mPa · s
Moreover, the prepared liquid crystal composition (MB) maintained a uniform nematic liquid crystal state for one month or more at room temperature.

  Further, the liquid crystal display device produced using the liquid crystal composition (MB) showed excellent display characteristics, maintained stable display characteristics for a long period of time, and showed 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 compound (A) shown below was prepared.

From this composition (MC), the values of extrapolation T _n-i , extrapolation Δε, extrapolation Δn, and extrapolation γ ₁ of the compound (A) are as follows.

Extrapolation Tn _-i : 18.3 degreeC.
Extrapolation Δε: -15.7
Extrapolation Δn: 0.184
Extrapolation γ ₁ : 241 mPa · s
Comparing the above results with Example 352 and Example 353, it can be seen that Δn is similar, but T _n-i is low.

(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 the composition (MD), the values of extrapolation T _n-i , extrapolation Δε, extrapolation Δn, and extrapolation γ ₁ of the compound (B) are as follows.

Extrapolation Tn _-i : 3.2 degreeC.
Extrapolation Δε: -9.7
Extrapolation Δn: 0.073
Extrapolation γ ₁ : 94 mPa · s
Comparing the above results with Example 352 and Example 353, it can be seen that | Δε | is significantly reduced and T _n−i is also significantly low.

Claims (7)

General formula (i)

(In the formula, X ⁱ¹ and X ⁱ² each represent a fluorine atom,
Y ⁱ¹ and Y ⁱ² each independently represent -O-,
W ⁱ¹ represents —CH ₂ CH ₂ —,
W ⁱ² represents a single bond,
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 , and one —CH ₂ present in L ⁱ¹ and L ^i2. - or nonadjacent two or more -CH 2 _- may be replaced by -O-, Further, the hydrogen atoms present in the alkyl or alkenyl group may be substituted by a fluorine atom,
L ⁱ³ , L ⁱ⁴ and L ⁱ⁵ each independently represent a hydrogen atom . )
The compound represented by. In the general formula (i), L ⁱ¹ and L ⁱ² are each independently 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, and the number of carbon atoms. The compound according to claim 1 , which represents 2 to 15 alkenyloxy groups. A composition containing one kind or two or more kinds of the compound according to claim 1 or 2 . A liquid crystal display device using the composition according to claim 3 . General formula (i-r3)

(In the formula, X ⁱ¹ , X ⁱ² , Y ⁱ² , W ⁱ¹ , W ⁱ² , L ⁱ¹ , L ⁱ² , L ⁱ³ , L ^i4, and L ⁱ⁵ are X ⁱ¹ , X ⁱ² , Y ⁱ¹ , and Y i in the general formula (i). ⁱ² , W ⁱ¹ , W ⁱ² , L ⁱ¹ , L ⁱ² , L ⁱ³ , L ^i4, and L ⁱ⁵ have the same meanings, respectively.)
Process for preparing a compound which is due to reaction molecules, represented by the general formula (i) ^- OH group in the compound in represented by the O produced is deprotonated by a base. General formula (i-r1)

^(Wherein, X ^{i2, Y i2,} W ^{i1, L i2} and ^{L i5} is ^X i2 in the general formula ^{(i), Y i2, W} i1, L and ⁱ² and ^{L i5} represent the same meanings, respectively,
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 - represents,
The broken line indicates that the bond may or may not exist. )
And a compound represented by the general formula (i-r2)

^{(Wherein, X i1, L i1, L i3} , L i4 and ^{W i2} general formula (i) in the ^{X i1, L i1, L i3} , L i4 and ^{W i2} represent the same meanings, 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 5 , wherein the compound represented by the formula (i-r3) is obtained by reacting the compound represented by the formula (1) in the presence of a transition metal catalyst and a base. General formula (i-r3)

(In the formula, X ⁱ¹ , X ⁱ² , Y ⁱ² , W ⁱ¹ , W ⁱ² , L ⁱ¹ , L ⁱ² , L ⁱ³ , L ^i4, and L ⁱ⁵ are X ⁱ¹ , X ⁱ² , Y ⁱ² , and W in the general formula (i). ⁱ¹ , W ⁱ² , L ⁱ¹ , L ⁱ² , L ⁱ³ , L ^i4, and L ⁱ⁵ have the same meanings.)
The compound represented by.