JPWO2019035408A1 - Method for producing compound - Google Patents

Abstract

The present invention provides a compound (ia) having a group represented by a partial structure (A), a partial structure (AI), a partial structure (D) or a partial structure (DI), a partial structure (Y), and a partial structure (Y). (F, Cl)), compound (ib) having a group represented by partial structure (Y (Cl, F)) or partial structure (Y (Cl, Cl)) in the presence of a transition metal catalyst. By doing so, the group represented by the partial structure (A), the partial structure (AI), the partial structure (D) or the partial structure (DI), the partial structure (Y), and the partial structure (Y (F, Cl)) And a group represented by a partial structure (Y (Cl, F)) or a partial structure (Y (Cl, Cl)).

Description

  The present invention provides a method for producing a compound having a tetrahydropyran-2,5-diyl group or a 1,3-dioxane-2,5-diyl group and a 4-alkoxy-2,3-difluorophenyl group in a molecular structure. The present invention relates to a liquid crystal composition using the compound and a display element using the liquid crystal composition.

  It is said that the liquid crystal compound and the additives used in the TFT liquid crystal material preferably have as high a purity as possible as well as not containing impurities that cause image sticking to the display. The VA (vertical alignment) type, the PSA (polymer sustained alignment) type, and the n-FFS (fringe field switching) type liquid crystal display devices, which are types of TFT liquid crystal display devices, have an n-type liquid crystal having a negative dielectric anisotropy. A composition is used. In particular, in a liquid crystal display device using an n-type liquid crystal composition, a metal impurity contained in the composition greatly affects the quality of the display device. The content is required. Examples of the metal impurities contained in the compound include those derived from the used palladium catalyst when the compound is produced by a coupling reaction using a palladium catalyst.

  A compound having a tetrahydropyran-2,5-diyl group or a 1,3-dioxane-2,5-diyl group in a molecular structure is a general compound as a constituent material of p-type and n-type liquid crystal compositions. However, when an intermediate having a tetrahydropyran ring or a dioxane ring is used for a coupling reaction using a palladium catalyst, when the obtained compound is added to an n-type liquid crystal composition to produce a liquid crystal panel, a long term There was a problem that seizure was likely to occur by use. This is considered to be due to the fact that the palladium used in the reaction was coordinated to the oxygen atom on the tetrahydropyran ring or dioxane ring, could not be completely removed in the purification step, and remained as an impurity. . Therefore, it is a compound that is conventionally added to an n-type liquid crystal composition in which the influence of a metal impurity on a display element is particularly large, and a tetrahydropyran-2,5-diyl group or 1,3-dioxane-2, In the production of a compound having a 5-diyl group, an intermediate having a tetrahydropyran-2,5-diyl group or a 1,3-dioxane-2,5-diyl group is used for a coupling reaction in the presence of a palladium catalyst. Was avoided.

  A compound having a tetrahydropyran-2,5-diyl group or a 1,3-dioxane-2,5-diyl group and a 4-alkoxy-2,3-difluorophenyl group in a molecular structure is converted into an n-type liquid crystal composition. Is a compound useful as a constituent material of an n-type liquid crystal composition because of its high solubility and a large negative dielectric anisotropy. Due to concerns about quality deterioration due to the palladium-derived metal impurities, the compound forms a tetrahydropyran ring after performing a coupling reaction and removing palladium-derived impurities at a stage before forming a tetrahydropyran ring. A method has been adopted (Non-Patent Document 2). However, in the production method, the impurity removal efficiency by recrystallization in each intermediate is low because the crystallinity of the intermediate is low, or purification by recrystallization cannot be performed because the intermediate is a liquid, and the final compound obtained is There was a problem that the purity was lowered. When a liquid crystal panel is manufactured using a low-purity compound, burning may occur or unevenness may occur over a long period of use, which may reduce the quality of display products. . Therefore, a tetrahydropyran-2,5-diyl group or a 1,3-dioxane-2,5-diyl group and a 4-alkoxy-2,3-difluorophenyl group are included in the molecular structure to solve such a problem. Development of a method for producing a liquid crystal compound having a negative dielectric anisotropy having a tetrahydropyran-2,5-diyl group or a 1,3-dioxane-2,5-diyl group in a molecular structure, such as a compound having the compound, is required. Had been.

JP 2017-75095 A

European Journal of Organic Chemistry, 2008, Issue 20, pages 3479-3487. Molecular Crystals and Liquid Crystals, 2011, 542, 16 / [538] -27 [549].

  The problem to be solved by the present invention is to easily prepare a liquid crystal compound having a negative dielectric anisotropy having a tetrahydropyran-2,5-diyl group or a 1,3-dioxane-2,5-diyl group in a molecular structure. Another object of the present invention is to provide a production method for obtaining high purity. Further, a liquid crystal composition using the compound and a display element using the liquid crystal composition are provided.

  The present inventors have conducted intensive studies to solve the above-described problems, and as a result, have developed a specific manufacturing method. That is, the present invention relates to a compound having one or more groups selected from the groups represented by partial structure (A), partial structure (AI), partial structure (D) and partial structure (DI) (Ia) and a group represented by the above partial structure (Y), partial structure (Y (F, Cl)), partial structure (Y (Cl, F)) and partial structure (Y (Cl, Cl)) (A), partial structure (AI), partial structure (D) by coupling with compound (ib) having one or two or more groups selected from And one or more groups selected from groups represented by a partial structure (DI), a partial structure (Y), a partial structure (Y (F, Cl)), and a partial structure (Y (Cl, F) )) And one or more groups selected from the groups represented by the partial structure (Y (Cl, Cl)) A method for producing compound (i) having the same, a liquid crystal composition using the compound, a display element using the liquid crystal composition, a personal computer, a smartphone, a television, a monitor, a drone, a digital signage, and an electronic device using the same. Blackboards, home appliances, vending machines, ticket vending machines, ticket gates, portable devices, control devices, manufacturing equipment, automatic teller machines, cash registers, car navigation systems, game machines, decorative equipment, stage equipment, on-board monitors, transport equipment, Provides automobiles, railways, linear motor cars, aircraft, ships and spacecraft.

  Since the production method of the present invention can be produced with a small number of steps and with high purity, a tetrahydropyran-2,5-diyl group or 1,3-dioxane-2,5- It is useful as a method for producing a liquid crystal compound having a diyl group and a negative dielectric anisotropy. Further, the compound produced by the production method of the present invention is useful as a material for a liquid crystal display device.

  The manufacturing method according to the present invention includes the following partial structure (A), partial structure (AI), partial structure (D) and partial structure (DI).

And one or more groups selected from the groups represented by the following partial structures (Y), partial structures (Y (F, Cl)), partial structures (Y (Cl, F)) and partial structures ( Y (Cl, Cl))

A method for producing a compound (i) having one or more groups selected from the groups represented by the following formulas, wherein the partial structure (A), the partial structure (AI), the partial structure (D) and Compound (ia) having one or more groups selected from the group represented by partial structure (DI), the above partial structure (Y), partial structure (Y (F, Cl)), partial structure Compound (ib) having one or more groups selected from groups represented by (Y (Cl, F)) and partial structure (Y (Cl, Cl)) in the presence of a transition metal catalyst , Produced by a coupling reaction.

  As the compound (i), the following general formula (I)

(Wherein, R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, or one —CH ₂ — or two or more non-adjacent —CH ₂ — Represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by -O-, -CH = CH-, -CF = CF- or -C≡C-; May be substituted with a fluorine atom, and A ⁰ represents a group represented by partial structure (A), partial structure (AI), partial structure (D) or partial structure (DI); ^Y is moiety (Y), the partial structure (Y (F, Cl)) , the partial structure (Y (Cl, F)) or a partial structure (Y (Cl, Cl)) represents a group represented by, ^{a 1} , ^A 2, ^{A 3} and ^{A 4} each independently 1,4-phenylene group, 1,4-cyclohexylene group, It represents a tiger tetrahydropyran-2,5-diyl group or 1,3-dioxane-2,5-diyl group, optionally substituted by these groups or is unsubstituted or 1 or more substituents L ¹ When there are a plurality of A ^1, they may be the same or different. When there are a plurality of A ^2, they may be the same or different. When there are a plurality of A ^3, May be the same or different, and when a plurality of A ⁴ are present, they may be the same or different, and L ¹ is a fluorine atom, a chlorine atom, or one —CH ₂ — Two or more non-adjacent —CH ₂ — each having 1 to 20 carbon atoms which may be independently substituted by —O—, —CH ＝ CH—, —CF ＝ CF— or —C≡C— Represents a linear or branched alkyl group of Any hydrogen atom in the group may be substituted by a fluorine ^{atom, Z 1, Z 2, Z} 3 and ^{Z 4} are each independently _{-OCH 2 -, - CH 2 O} -, - CH 2 CH 2 - _{, -COO -, - OCO -,} - CF 2 O -, - OCF 2 -, - CH = CH -, - CF = CF -, - C≡C- or represents a single bond, ^{Z 1} there are a plurality of In those cases, they may be the same or different. When there are a plurality of Z ^2, they may be the same or different. When there are a plurality of Z ^3, they may be the same or different. And when a plurality of Z ⁴ are present, they may be the same or different, and m1, m3 and m4 each independently represent an integer of 0 to 3, and m2 represents an integer of 1 to 3. Where m1 + m2 + m3 + m4 represents an integer of 1 to 3. ) Is preferable.

In the general formula (I), R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, or one —CH ₂ — or two or more non-adjacent —CH ₂ — Independently represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by -O-, -CH = CH-, -CF = CF- or -C≡C-. Any hydrogen atom in the alkyl group may be replaced by a fluorine atom. From the viewpoints of storage stability, solubility, liquid crystallinity, dielectric anisotropy and refractive index anisotropy when added to the n-type liquid crystal composition, R ¹ and R ² each independently represent one —CH _2- or two or more non-adjacent —CH ₂ — may be each independently substituted by —O—, —CH ＝ CH—, —CF ＝ CF— or —C≡C—. Preferably represents a linear alkyl group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, and R ¹ and R ² each independently represent one —CH ₂ — or More preferably, two or more non-adjacent —CH ₂ — represent a linear alkyl group having 1 to 6 carbon atoms which may be independently substituted by —O— or —CH ＝ CH—. , ^{R 1} is one -CH ₂ - may have been replaced by -CH = CH- charcoal From atoms 1 represents a linear alkyl group having 6, ^{R 2} is one -CH ₂ - or nonadjacent two or more -CH ₂ - are each independently -O- or -CH = CH More preferably represents a straight-chain alkyl group having 1 to 6 carbon atoms which may be substituted by —, and R ¹ represents a straight-chain alkyl group having 1 to 6 carbon atoms or a straight-chain alkyl group having 2 to 6 carbon atoms. R ² represents a linear alkyl group having 1 to 6 carbon atoms, a linear alkoxy group having 1 to 5 carbon atoms, a linear alkenyl group having 2 to 6 carbon atoms, Even more preferably, it represents a straight-chain alkenyloxy group having 2 to 5 atoms, R ¹ represents a straight-chain alkyl group having 1 to 6 carbon atoms, and R ² represents a straight-chain alkyl group having 1 to 5 carbon atoms. It is particularly preferred to represent a symmetrical alkoxy group.

In the general formula (I), A ⁰ represents a group represented by the partial structure (A), the partial structure (AI), the partial structure (D) or the partial structure (DI). Availability of raw materials ease, from the standpoint of ease and liquid synthetic, A ⁰ is preferably a group represented by the partial structure (A), the partial structure (AI) or a partial structure (D), A ⁰ More preferably represents a group represented by the partial structure (A) or the partial structure (AI), and particularly preferably represents a group represented by the partial structure (A).

In the general formula (I), A ^Y represents a partial structure (Y), a partial structure (Y (F, Cl)), a partial structure (Y (Cl, F)) or a partial structure (Y (Cl, Cl)). Represents a group to be formed. A ^Y preferably represents a group represented by the partial structure (Y) from the viewpoints of availability of raw materials, ease of synthesis, and liquid crystallinity.

In the general formula (I), A ¹ , A ² , A ³ and A ⁴ are each independently 1,4-phenylene, 1,4-cyclohexylene, tetrahydropyran-2,5-diyl or 1, Represents a 3-dioxane-2,5-diyl group, which may be unsubstituted or substituted by one or more substituents L ¹ , and when a plurality of A ¹ are present, they are the same. May be the same or different when there are a plurality of A ^{2, and} they may be the same or different when there are a plurality of A ³ ; ^{When a} plurality of ⁴ exist, they may be the same or different. From the viewpoints of availability of raw materials, ease of synthesis and liquid crystallinity, A ¹ , A ² , A ³ and A ⁴ are each independently represented by the following formulas (A-1) to (A-9)

And preferably represents a group selected from the formulas (A-1) to (A-5), (A-8) and (A-9). More preferably, it represents a group selected from the formulas (A-1) to (A-5), and more preferably, it represents a group selected from the formulas (A-1) to (A-4). More preferably, it is particularly preferable to represent a group selected from the above formula (A-1), formula (A-3) or formula (A-4).

In the general formula (I), L ¹ is a fluorine atom, a chlorine atom, or one —CH ₂ —not adjacent to two or more —CH ₂ — each independently represents —O—, —CH ＝ CH -Represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by -CF = CF- or -C≡C-, and any hydrogen atom in the alkyl group is a fluorine atom May be replaced by From the viewpoints of availability of raw materials, ease of synthesis, and liquid crystallinity, L ¹ may be a fluorine atom, a chlorine atom, or one —CH ₂ — may be replaced by —O— Represents preferably a linear alkyl group having 1 to 6 carbon atoms which may be substituted by a fluorine atom, and L ¹ represents a fluorine atom, a chlorine atom, or one -CH _2- More preferably, any hydrogen atom in the group which may be substituted by O- represents a linear alkyl group having 1 to 3 carbon atoms which may be substituted by a fluorine atom, and L ¹ is a fluorine atom, a chlorine atom, a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, more preferably represent a trifluoromethoxy group or a pentafluoroethoxy group, L ¹ is still more preferably represent a fluorine atom or a chlorine atom L ¹ is and particularly preferably a fluorine atom.

In the general formula (I), Z ¹ , Z ² , Z ³ and Z ⁴ are each independently -OCH _2- , -CH ₂ O-, -CH ₂ CH _2- , -COO-, -OCO-,-. CF ₂ O—, —OCF ₂ —, —CH ＝ CH—, —CF ＝ CF—, —C≡C—, or a single bond. When a plurality of Z ¹ are present, they are different even if they are the same. When there are a plurality of Z ^2, they may be the same or different. When there are a plurality of Z ^3, they may be the same or different, and there are a plurality of Z ⁴ In that case, they may be the same or different. From the viewpoints of liquid crystal properties and physical properties when formed into a display element, Z ¹ , Z ² , Z ³ and Z ⁴ are each independently —OCH ₂ —, —CH ₂ O—, —CH ₂ CH ₂ —, and —COO. —, —OCO—, —CF ₂ O—, —OCF ₂ — or a single bond, and Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent —OCH ₂ —, —CH ₂ O _{-, - CH 2 CH 2 -} , - CF 2 O -, - OCF 2 - or is more preferably a single ^{bond, Z 1, Z 2, Z} 3 and ^{Z 4} are each independently -OCH ₂ -, _{-CH 2 O -, - CH 2} CH 2 - or more preferably a single ^{bond, Z 1, Z 2, Z} 3 and ^{Z 4} each independently are _-CH 2 CH ₂ - or a single bond There still more ^{preferably, Z 1, Z 2, Z} 3 and ^{Z 4} are particularly good may represent a single bond Arbitrariness.

  In the general formula (I), m1, m3 and m4 each independently represent an integer of 0 to 3. From the viewpoint of availability of raw materials, ease of synthesis, and liquid crystallinity, m1, m3, and m4 each preferably independently represent 0, 1, or 2, and m1, m3, and m4 each independently represent 0 or More preferably, it represents 1, and particularly preferably m1, m3 and m4 represent 0.

  In the general formula (I), m2 represents an integer of 1 to 3, and m1 + m2 + m3 + m4 represents an integer of 1 to 3. From the viewpoints of availability of raw materials, ease of synthesis, and liquid crystallinity, m2 preferably represents 1 or 2, and m2 particularly preferably represents 1. m1 + m2 + m3 + m4 preferably represents 1 or 2, and m1 + m2 + m3 + m4 particularly preferably represents 1.

  As the compound (ia), the following general formula (IA)

(Wherein, R ¹ , A ⁰ , A ¹ , A ² , Z ¹ , Z ² , m1 and m2 represent the same meaning as in the general formula (I), and X ¹ represents a fluorine atom, a chlorine atom, a bromine atom, an iodine Atom, trifluoromethanesulfonyloxy group, methanesulfonyloxy group or group selected from p-toluenesulfonyloxy group or dihydroxyboryl group, linear or branched alkoxyboryl group having 2 to 20 carbon atoms or 1 to carbon atoms 20 represents a group selected from cyclic alkoxyboryl groups.).

In the general formula (IA), preferable conditions for R ¹ , A ⁰ , A ¹ , A ² , Z ¹ , Z ² , m1 and m2 are the same as those in the general formula (I).

  In the present invention, the dihydroxyboryl group is represented by the following formula (XB-1)

And a linear or branched alkoxyboryl group having 2 to 20 carbon atoms is represented by the following formula (XB-2)

(Wherein, R ^XB1 and R ^XB2 each independently represent a linear or branched alkyl group having 2 to 20 carbon atoms), and a cyclic group having 1 to 20 carbon atoms. The alkoxyboryl group is represented by the following formula (XB-3)

( ^Wherein , ring A ^XB1 represents a ring structure formed by —O—B—O— and an alkylene group having 1 to 20 carbon atoms). Examples of the linear or branched alkoxyboryl group having 2 to 20 carbon atoms include a dimethoxyboryl group represented by the following formula (XB-2-1) and a diethoxyboryl group represented by the following formula (XB-2-2) A dipropoxyboryl group represented by the formula (XB-2-3), a diisopropoxyboryl group represented by the formula (XB-2-4), and a dipropoxyboryl group represented by the formula (XB-2-5). tert-butyloxyboryl group

Is mentioned. Examples of the cyclic alkoxyboryl group having 1 to 20 carbon atoms include a 1,3,2-dioxaborolan-2-yl group represented by the following formula (XB-3-1) and a formula (XB-3-2) ), A 4,5-dimethyl-1,3,2-dioxaborolan-2-yl group represented by the formula (XB-3-3). Yl group, 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl group represented by the formula (XB-3-4), represented by the formula (XB-3-5) Hexahydro-5,5-dimethyl-4,6-methano-1,3,2-benzodioxaborolan-2-yl group and hexahydro-3a, 5 represented by the formula (XB-3-6) 5-trimethyl-4,6-methano-1,3,2-benzodioxaborolan-2-yl group And the like.

In the general formula (IA), X ¹ represents a group selected from a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a trifluoromethanesulfonyloxy group, a methanesulfonyloxy group, a p-toluenesulfonyloxy group, a dihydroxyboryl group, and a carbon atom. Represents a group selected from a linear or branched alkoxyboryl group having 2 to 20 carbon atoms or a cyclic alkoxyboryl group having 1 to 20 carbon atoms. From the viewpoints of availability of raw materials and ease of synthesis, X ¹ is a group selected from a chlorine atom, a bromine atom, an iodine atom, or a trifluoromethanesulfonyloxy group or a dihydroxyboryl group, and a straight chain having 2 to 5 carbon atoms. Or a group selected from a branched alkoxyboryl group or a cyclic alkoxyboryl group having 1 to 10 carbon atoms, and X ¹ is a group selected from a chlorine atom, a bromine atom, an iodine atom and a trifluoromethanesulfonyloxy group. It is more preferable that X ¹ represents a group selected from a bromine atom, an iodine atom and a trifluoromethanesulfonyloxy group, and it is particularly preferable that X ¹ represents a bromine atom.

  As the compound (ib), a compound represented by the following general formula (IB)

(Where A ³ , A ⁴ , A ^Y , Z ³ , Z ⁴ , m 3, m ⁴ and R ² represent the same meaning as in the general formula (I), and X ² represents a fluorine atom, a chlorine atom, a bromine atom, an iodine Atom, trifluoromethanesulfonyloxy group, methanesulfonyloxy group or group selected from p-toluenesulfonyloxy group or dihydroxyboryl group, linear or branched alkoxyboryl group having 2 to 20 carbon atoms or 1 to carbon atoms And X ¹ represents a group selected from a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a trifluoromethanesulfonyloxy group, a methanesulfonyloxy group, and a p-toluenesulfonyloxy group. when referring to, X ² is a dihydroxyboryl group, having 2 to 20 carbon atoms linear or branched Arukokishibo Represents a group or a group selected from cyclic Arukokishiboriru group having a carbon number of 1 to 20, X ¹ is a dihydroxyboryl group, a linear or branched Arukokishiboriru group or a carbon atom number of from 2 to 20 carbon atoms X ² represents a group selected from a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a trifluoromethanesulfonyloxy group, a methanesulfonyloxy group and a p-toluenesulfonyloxy group when representing a group selected from 20 cyclic alkoxyboryl groups. Is preferable.).

In the general formula (IB), preferable conditions of A ³ , A ⁴ , A ^Y , Z ³ , Z ⁴ , m3, m4 and R ² are the same as those in the general formula (I).

In the general formula (IB), X ² is a group selected from a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a trifluoromethanesulfonyloxy group, a methanesulfonyloxy group, a p-toluenesulfonyloxy group, a dihydroxyboryl group, and a carbon atom. Represents a group selected from a linear or branched alkoxyboryl group having 2 to 20 carbon atoms or a cyclic alkoxyboryl group having 1 to 20 carbon atoms, wherein X ¹ is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, X ² represents a dihydroxyboryl group, a linear or branched alkoxyboryl group having 2 to 20 carbon atoms or a carbon atom when it represents a group selected from a methanesulfonyloxy group, a methanesulfonyloxy group and a p-toluenesulfonyloxy group. Table represents groups selected from the cyclic alkoxyboryl groups of Formulas 1 to 20 When representing the group X ¹ is selected from a dihydroxy boryl group, a linear or branched Arukokishiboriru group or 1 to 20 carbon atoms cyclic Arukokishiboriru group having from 2 carbon atoms 20, X ² is fluorine atom, Represents a group selected from a chlorine atom, a bromine atom, an iodine atom, a trifluoromethanesulfonyloxy group, a methanesulfonyloxy group and a p-toluenesulfonyloxy group. From the viewpoints of availability of raw materials and ease of synthesis, X ² is a group selected from a chlorine atom, a bromine atom, an iodine atom, or a trifluoromethanesulfonyloxy group or a dihydroxyboryl group, and a straight chain having 2 to 5 carbon atoms. Or a group selected from a branched alkoxyboryl group or a cyclic alkoxyboryl group having 1 to 10 carbon atoms, and X ² is a dihydroxyboryl group, a linear or branched alkoxyboryl group having 2 to 5 carbon atoms. More preferably, X ² represents a dihydroxyboryl group, a linear dialkoxyboryl group having 2 or 4 carbon atoms, or a group having 6 carbon atoms. Represents a group selected from a branched dialkoxyboryl group, and a cyclic alkoxyboryl group having 2 to 6 carbon atoms. Mashiku, ^{X 2} is a dihydroxyboryl group, dimethoxy boryl group, Jietokishiboriru group, diisopropoxy boryl group, 1,3,2-dioxaborolan-2-yl group, 4-methyl-1,3,2-dioxaborolan-2- An yl group, a 4,5-dimethyl-1,3,2-dioxaborolan-2-yl group or a group selected from 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl group It is even more preferred that X ² represents a dihydroxyboryl group.

  As the compound represented by the general formula (I), the following general formula (Ii)

(In the formula, R ¹¹ and R ²¹ are each independently one -CH ₂ -or two or more non-adjacent -CH ₂ -are each independently -O-, -CH = CH-,- CF = CF- or may be substituted by -C≡C-, arbitrary hydrogen atom in the radicals represents a linear alkyl group having from good 1 -C be substituted by a fluorine atom 10, a ⁰¹ Is the following formula (A0-i-1) or formula (A0-i-2)

A ¹¹ , A ²¹ , A ³¹ and A ⁴¹ are each independently a group represented by the following formulas (A-i-1) to (A-i-9)

(Wherein L ¹¹ is a fluorine atom, a chlorine atom, or a carbon atom in which one —CH ₂ — may be replaced by —O—, and any hydrogen atom in the group may be replaced by a fluorine atom. Represents a straight-chain alkyl group having 1 to 6 atoms.) When a plurality of A ¹¹ are present, they may be the same or different, and when a plurality of A ²¹ is present, they may be the same or different and if the a ³¹ there are a plurality thereof may be the same or different and they if a ⁴¹ there are a plurality optionally be the same or different Z ¹¹ , Z ²¹ , Z ³¹ and Z ⁴¹ each independently represent -OCH _2- , -CH ₂ O-, -CH ₂ CH _2- , -COO-, -OCO-, -CF ₂ O- , -OCF ₂ - or represents a single ^{bond, Z 11} is They If the number present may be the same or different and they if Z ²¹ there are a plurality may be the same or different and they if Z ³¹ there are a plurality in the same When a plurality of Z ⁴¹ are present, they may be the same or different, and m11, m31 and m41 each independently represent 0, 1 or 2, and m21 represents 1 or 2 Where m11 + m21 + m31 + m41 represents 1, 2 or 3. The compound represented by the following general formula (IA-i) is preferable as the compound (ia) (the compound represented by the general formula (IA)).

(Wherein, R ¹¹ , A ⁰¹ , A ¹¹ , A ²¹ , Z ¹¹ , Z ²¹ , m11 and m21 represent the same meaning as in the general formula (Ii), and X ¹¹ represents a chlorine atom, a bromine atom, an iodine atom. Or a group selected from a trifluoromethanesulfonyloxy group or a dihydroxyboryl group, a linear or branched alkoxyboryl group having 2 to 5 carbon atoms, or a cyclic alkoxyboryl group having 1 to 10 carbon atoms. The compound represented by the following general formula (IB-i) is preferable as the compound (ib) (the compound represented by the general formula (IB)).

(Wherein, A ³¹ , A ⁴¹ , Z ³¹ , Z ⁴¹ , m31, m41 and R ²¹ represent the same meaning as in the general formula (I-i), and X ²¹ represents a chlorine atom, a bromine atom, an iodine atom or trifluoromethane. X ¹¹ represents a group selected from a sulfonyloxy group or a dihydroxyboryl group, a linear or branched alkoxyboryl group having 2 to 5 carbon atoms or a cyclic alkoxyboryl group having 1 to 10 carbon atoms; Represents a group selected from a chlorine atom, a bromine atom, an iodine atom or a trifluoromethanesulfonyloxy group, X ²¹ represents a dihydroxyboryl group, a linear or branched alkoxyboryl group having 2 to 5 carbon atoms or a carbon atom number; X ¹¹ represents a group selected from cyclic alkoxyboryl groups having 1 to 10; X ¹¹ represents a dihydroxyboryl group; X ²¹ represents a group selected from a chlorine atom, a bromine atom, an iodine atom or a trifluoromethanesulfonyloxy group when representing a group selected from a chain or branched alkoxyboryl group or a cyclic alkoxyboryl group having 1 to 10 carbon atoms. Is preferable.

  The compound represented by the general formula (I) includes the following general formula (Ii-1)

(Wherein, R ¹¹¹ and R ²¹¹ are each independently one -CH ₂ -or two or more non-adjacent -CH _2- , each independently substituted by -O- or -CH = CH- ^Represents a straight-chain alkyl group having 1 to 6 carbon atoms, and A ⁰¹¹ represents the following formula (A0-i-1-1) or (A0-i-1-2)

^A211 and ^A311 are each independently a group represented by the following formulas (Ai-1-1) to (Ai-1-5) or (Ai-1-8). ) Or formula (A-i-1-9)

(In the formula, L ¹¹¹ is a fluorine atom, a chlorine atom, or a carbon atom in which one —CH ₂ — may be replaced by —O—, and any hydrogen atom in the group may be replaced by a fluorine atom. Represents a straight-chain alkyl group having 1 to 3 atoms.) When a plurality of A ²¹¹ are present, they may be the same or different, and when a plurality of A ³¹¹ exist, They may be the same or different, and Z ²¹¹ and Z ³¹¹ are each independently —OCH ₂ —, —CH ₂ O—, —CH ₂ CH ₂ —, —CF ₂ O—, —OCF ₂ Or represents a single bond, when a plurality of Z ²¹¹ are present, they may be the same or different, and when a plurality of Z ³¹¹ are present, they may be the same or different, and m311 is Each represents 0, 1, or 2 independently , M211 represents an 1 or 2, M211 + M311 represents 1 or 2. The compound represented by the following general formula (IA-i-1) is more preferable.

(Wherein, R ¹¹¹ , A ⁰¹¹ , A ²¹¹ , Z ²¹¹ and m211 represent the same meaning as in the general formula (I-i-1), and X ¹¹¹ represents a chlorine atom, a bromine atom, an iodine atom or a trifluoromethanesulfonyloxy group. The compound represented by the following general formula (IB-i-1) is more preferable as the compound represented by the general formula (IB).

(Wherein, A ³¹¹ , Z ³¹¹ , m311 and R ²¹¹ represent the same meaning as in the general formula (I-i-1), and X ²¹¹ represents a dihydroxyboryl group, a linear or branched group having 2 to 5 carbon atoms. And a group selected from an alkoxyboryl group and a cyclic alkoxyboryl group having 1 to 10 carbon atoms.).

  As a compound represented by the general formula (I), the following general formula (Ii-11)

(Wherein, R ¹¹¹¹ represents a linear alkyl group having 1 to 6 carbon atoms in which one —CH ₂ — may be substituted by —CH ＝ CH—, and R ²¹¹¹ represents one —CH _{2 —} - or nonadjacent two or more -CH 2 _- represents each independently -O- or -CH = CH- is also a good 1 -C 6 substituted by a straight-chain alkyl group, a ⁰¹¹¹ is represented by the following formula (A0-i-11-1) or formula (A0-i-11-2)

^A2111 represents a group represented by the following formula ( ^Ai -11-1) to formula (Ai-11-5)

( ^Wherein L ¹¹¹¹ represents a fluorine atom, a chlorine atom, a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a trifluoromethoxy group or a pentafluoroethoxy group.) ²¹¹¹ they if there exist a plurality may be different even in the ^{same, Z 2111} is _{-OCH 2 -, - CH 2 O} -, - CH 2 CH 2 - or represents a single ^{bond, Z 2111} are multiple When present, they may be the same or different and m2111 represents 1 or 2. The compound represented by the following general formula (IA-i-11) is more preferable as the compound represented by the general formula (IA).

(Wherein, R ¹¹¹¹ , A ⁰¹¹¹ , A ²¹¹¹ , Z ^2111, and m ²¹¹¹ represent the same meaning as in the general formula (Ii-11), and X ¹¹¹¹ represents a chlorine, bromine atom, iodine atom, or trifluoromethanesulfonyloxy group. The compound represented by the following general formula (IB-i-11) is more preferable.

(Wherein, R ²¹¹¹ represents the same meaning as in the general formula (Ii-11), and X ²¹¹¹ represents a dihydroxyboryl group, a dimethoxyboryl group, a diethoxyboryl group, a diisopropoxyboryl group, a 1,3,2-dioxaborolane- 2-yl group, 4-methyl-1,3,2-dioxaborolan-2-yl group, 4,5-dimethyl-1,3,2-dioxaborolan-2-yl group or 4,4,5,5-tetra And a group selected from a group selected from methyl-1,3,2-dioxaborolan-2-yl groups.).

  As the compound represented by the general formula (I), the following general formula (Ii-111)

(Wherein, R ¹¹¹¹¹ represents a linear alkyl group having 1 to 6 carbon atoms or a linear alkenyl group having 2 to 5 carbon atoms, and R ²¹¹¹¹ represents a linear alkoxy group having 1 to 5 carbon atoms.) Or a linear alkenyloxy group having 2 to 5 carbon atoms). Particularly preferred as the compound represented by the general formula (IA) is a compound represented by the following general formula (IA-i-111) )

(Wherein, R ¹¹¹¹¹ represents the same meaning as in the general formula ( ^Ii -111), and X ¹¹¹¹¹ represents a bromine atom), and is particularly preferably a compound represented by the general formula (IB) Is represented by the following general formula (IB-i-111)

(Wherein, R ²¹¹¹¹ represents the same meaning as in the general formula ( ^Ii -111), and X ²¹¹¹¹ represents a dihydroxyboryl group or 4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2- A compound represented by the following formula: is particularly preferable. Further, the compound represented by the general formula (I) includes a compound represented by the following general formula (Ii-112)

(Wherein, R ¹¹¹¹² represents a linear alkyl group having 1 to 5 carbon atoms or a linear alkenyl group having 2 to 5 carbon atoms, and R ²¹¹¹² represents a linear alkoxy group having 1 to 5 carbon atoms. Or a straight-chain alkenyloxy group having 2 to 5 carbon atoms). Particularly preferred as the compound represented by the general formula (IA) is a compound represented by the following general formula (IA-i-112) )

(In the formula, R ¹¹¹¹² has the same meaning as in the general formula (I-i-112), and X ¹¹¹¹² represents a group selected from a chlorine atom, a bromine atom and an iodine atom.) As the compound represented by the general formula (IB), the following general formula (IB-i-112)

(Wherein, R ²¹¹¹² represents the same meaning as in general formula (I-i-112), and X ²¹¹¹² represents a dihydroxyboryl group or 4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2- A compound represented by the following formula: is particularly preferable. The compound represented by the general formula (I) includes the following general formula (I-i-113)

(Wherein, R ¹¹¹¹³ represents a linear alkyl group or linear alkenyl group having 2 to 5 carbon atoms having 1 to 5 carbon atoms, R ²¹¹¹³ is a straight chain alkoxy group having 1 to 5 carbon atoms Or a straight-chain alkenyloxy group having 2 to 5 carbon atoms). Particularly preferred as the compound represented by the general formula (IA) is a compound represented by the following general formula (IA-i-113) )

(In the formula, R ¹¹¹¹³ represents the same meaning as in the general formula (I-i-113), and X ¹¹¹¹³ represents a group selected from a chlorine atom, a bromine atom and an iodine atom.) As the compound represented by the general formula (IB), the following general formula (IB-i-113)

(Wherein, R ²¹¹¹³ represents the same meaning as in general formula (I-i-113), and X ²¹¹¹³ represents a dihydroxyboryl group or 4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2- A compound represented by the following formula: is particularly preferable. Further, the compound represented by the general formula (I) includes the following general formula (I-i-114)

(Wherein, R ¹¹¹¹⁴ represents a linear alkyl group having 1 to 5 carbon atoms or a linear alkenyl group having 2 to 5 carbon atoms, and R ²¹¹¹⁴ represents a linear alkoxy group having 1 to 5 carbon atoms.) Or a straight-chain alkenyloxy group having 2 to 5 carbon atoms), and particularly preferably a compound represented by the following general formula (IA-i-114). )

(In the formula, R ¹¹¹¹⁴ represents the same meaning as in the general formula (I-i-114), and X ¹¹¹¹⁴ represents a group selected from a chlorine atom, a bromine atom and an iodine atom.) As the compound represented by the general formula (IB), the following general formula (IB-i-114)

( ^Wherein , R ²¹¹¹⁴ represents the same meaning as in general formula (I-i-114), and X ²¹¹¹⁴ represents a dihydroxyboryl group or 4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2- A compound represented by the following formula: is particularly preferable. Further, the compound represented by the general formula (I) includes the following general formula (Ii-115)

(Wherein, R ¹¹¹¹⁵ represents a linear alkyl group having 1 to 5 carbon atoms or a linear alkenyl group having 2 to 5 carbon atoms, and R ²¹¹¹⁵ represents a linear alkoxy group having 1 to 5 carbon atoms. Or a straight-chain alkenyloxy group having 2 to 5 carbon atoms), and particularly preferably a compound represented by the following general formula (IA-i-115). )

(Wherein, R ¹¹¹¹⁵ represents the same meaning as in formula (I-i-115), and X ¹¹¹¹⁵ represents a group selected from a chlorine atom, a bromine atom and an iodine atom.) As the compound represented by the general formula (IB), the following general formula (IB-i-115)

(Wherein, R ²¹¹¹⁵ represents the same meaning as in formula (I-i-115), and X ²¹¹¹⁵ represents a dihydroxyboryl group or 4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2- A compound represented by the following formula: is particularly preferable.

  Specific examples of the compound represented by the general formula (I) include compounds represented by the following general formulas (IE-1) to (IE-360)

(Wherein, R ^1E represents a linear alkyl group having 1 to 6 carbon atoms or a linear alkenyl group having 2 to 6 carbon atoms, and R ^2E represents a linear alkyl group having 1 to 6 carbon atoms.) A linear alkoxy group having 1 to 5 carbon atoms, a linear alkenyl group having 2 to 6 carbon atoms or a linear alkenyloxy group having 2 to 5 carbon atoms.) preferable.

  Specific examples of the compound represented by the general formula (IA) include compounds represented by the following general formulas (IA-E-1) to (IA-E-180)

(Wherein, R ^1E represents a linear alkyl group having 1 to 6 carbon atoms or a linear alkenyl group having 2 to 6 carbon atoms, and X ^1E represents chlorine, bromine atom, iodine atom or trifluoromethanesulfonyloxy) Represents a group selected from groups).

  Specific examples of the compound represented by the general formula (IB) include compounds represented by the following general formulas (IB-E-1) to (IB-E-15)

(Wherein, R ^2E is a linear alkyl group having 1 to 6 carbon atoms, a linear alkoxy group having 1 to 5 carbon atoms, a linear alkenyl group having 2 to 6 carbon atoms or 2 carbon atoms. To 5 represents a linear alkenyloxy group, and X ^2E is selected from a dihydroxyboryl group, a linear or branched alkoxyboryl group having 2 to 5 carbon atoms and a cyclic alkoxyboryl group having 1 to 10 carbon atoms. Represents a group selected from groups).

  More specifically, as the compound represented by the general formula (I), the compounds represented by the following formulas (I-1) to (I-270)

The compound represented by is preferred.

  As the reaction between the compound (ia) and the compound (ib), a method using a transition metal compound is preferable. The transition metal compound is preferably a compound containing a Group 8 to Group 11 element, and is a compound containing iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver or gold. More preferably, from the viewpoint of yield, availability and cost, a compound containing iron, nickel, palladium or copper is particularly preferable. Specific examples of iron-containing compounds include tris (2,4-pentanedionato) iron (III), tris (hexafluoroacetylacetonato) iron (III), iron (II) acetate, and iron (III) stearate. , Tris (trifluoro-2,4-pentanedionato) iron (III), tris (dibenzoylmethanato) iron (III), tricarbonyl (cyclooctatetraene) iron, pentacarbonyliron, nonacarbonyldiiron, dodeca Iron (II) chloride, iron (III) chloride, iron (III) chloride, 1,2-phenylenebis [diphenyl] phosphine iron complex, cyclopentadienyliron (II) dicarbonyl dimer, iron (III) nitrate, iron, trifluoro Iron (II) methanesulfonate, Iron (III) trifluoromethanesulfonate, Iron (III) p-toluenesulfonate , Ammonium iron (II) sulfate, iron (II) sulfate, ammonium iron (III) sulfate, iron (II) bromide, iron (III) bromide, iron (III) acetylacetonate, iron (III) trifluoroacetylacetate Nart, iron (III) fluoride, ferrocene derivatives and the like. Specific examples of the compound containing nickel include [1,3-bis (diphenylphosphino) propane] nickel (II) dichloride, bis (triphenylphosphine) nickel (II) dichloride, and [1,2-bis (diphenylphosphino) dichloride. Fino) ethane] nickel (II) dichloride, [1,1′-bis (diphenylphosphino) ferrocene] nickel (II) dichloride, bis (1,5-cyclooctadiene) nickel (0), [1,3- Bis (2,6-diisopropylphenyl) imidazole-2-ylidene] triphenylphosphine nickel (II) dichloride, bromo [(2,6-pyridinediyl) bis (3-methyl-1-imidazolyl-2-ylidene)] nickel Bromide, bis (tricyclohexylphosphine) nickel (II) dichloride , Chlorobis [dicyclohexyl (phenyl) phosphino] (o-tolyl) nickel (II), bis (2,4-pentanedionato) nickel (II), nickel chloride (II), nickel (II) nitrate, nickel, nickel ( II) Acetylacetonate, [1,2-bis (diphenylphosphino) ethane] dichloronickel (II), [1,1′-bis (diphenylphosphino) ferrocene] dichloronickel (II), [1,3- Bis (diphenylphosphino) propane] dichloronickel (II), bis (triphenylphosphine) nickel (II) dichloride, nickel (II) fluoride, potassium hexafluoronickel (IV), nickel (II) iodide, sulfuric acid Nickel (II), Nickel (II) chloride Ether complex, nickel bromide (II), nickel (II) acetate, and the like. Specific examples of the compound containing palladium include palladium (II) acetate, allyl palladium (II) chloride (dimer), bis (dibenzylideneacetone) palladium (0), bis (triphenylphosphine) palladium (II) dichloride, (Benzonitrile) palladium (II) dichloride, bis (acetonitrile) palladium (II) dichloride, [1,2-bis (diphenylphosphino) ethane] palladium (II) dichloride, bis (2,4-pentanedionato) palladium (II), bis (tri-o-tolylphosphine) palladium (II) dichloride, bis (triphenylphosphine) palladium (II) diacetate, bis (tricyclohexylphosphine) palladium (II) dichloride, [1,1′-bis (Gife Ruphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct, [1,1′-bis (di-tert-butylphosphino) ferrocene] palladium (II) dichloride, bis (tri-tert-butylphosphine) palladium (0) , Bis [1,2-bis (diphenylphosphino) ethane] palladium (0), bis [di-tert-butyl (4-dimethylaminophenyl) phosphine] palladium (0), chloro [[1,3-bis ( 2,6-diisopropylphenyl) imidazole-2-ylidene] (N, N-dimethylbenzylamine) palladium (II)], chloro [[1,3-bis (2,6-diisopropylphenyl) imidazole-2-ylidene] (Acetanilide) palladium (II)], chloro [[1,3-bi (2,6-diisopropylphenyl) imidazole-2-ylidene] (N, N-dimethyl-3,5-dimethoxybenzylamine) palladium (II)], chloro [(tri-tert-butylphosphine) -2- ( 2-aminobiphenyl)] palladium (II), [di-tert-butyl (chloro) phosphine] palladium (II) dichloride (dimer), dihydrogen di-μ-chlorotetrakis (di-tert-butylphosphinite) diparadate Di-μ-chlorobis [5-chloro-2-[(4-chlorophenyl) (hydroxyimino) methyl] phenyl] palladium (II) dimer, di-μ-chlorobis [5-hydroxy-2- [1- (hydroxy Imino) ethyl] phenyl] palladium (II) dimer, di-μ-chlorobis [2- [ (Dimethylamino) methyl] phenyl-C, N] dipalladium (II), di-μ-chlorobis [2-[(dimethylamino) methyl] -4,6-dimethoxyphenyl-C, N] dipalladium (II) , Di-μ-chlorobis (2′-amino-1,1′-biphenyl-2-yl-C, N) dipalladium (II), palladium (II) chloride, palladium, palladium / carbon, palladium (II) ( π-cinnamyl) chloride (dimer), palladium / alumina, sodium tetrachloropalladium (II), tetrakis (triphenylphosphine) palladium (0), tris (dibenzylideneacetone) dipalladium (0), tetrakis (acetonitrile) palladium (II) bis (trifluoromethanesulfonate), (ethylenediamine) para Ium (II) chloride, chloro [(1,2,5,6-η) -1,5-cyclooctadiene] (2,2-dimethylpropyl) palladium, chloro (1,5-cyclooctadiene) methylpalladium (II), dichloro (1,5-cyclooctadiene) palladium (II), dichlorobis (tricyclohexylphosphine) palladium (II), tris (dibenzylideneacetone) dipalladium (0), palladium (II) trifluoroacetate, Palladium (II) acetylacetonate, 1,1'-bis (diisopropylphosphino) ferrocenepalladium dichloride, bis [(dicyclohexyl) (4-dimethylaminophenyl) phosphine] palladium (II) chloride, [1,1'-bis (Dicyclohexylphosphino) ferrocene] dichloro Palladium (II), [1,2-bis (diphenylphosphino) ethane] dichloropalladium (II), [1,1′-bis (diphenylphosphino) ferrocene] dichloropalladium (II), [1,1′- Bis (di-tert-butylphosphino) ferrocene] dichloropalladium (II), bis (tricyclohexylphosphine) palladium (0), palladium (II) chloride, palladium (II) nitrate, palladium (II) sulfate, palladium bromide (II), palladium (II) fluoride and the like. Specific examples of the copper-containing compound include copper (I) acetate, bis (1,3-propanediamine) copper (II) dichloride, bis (8-quinolinolato) copper (II), and bis (2,4-pentanedio). Nato) copper (II), copper (I) cyanide, copper (II) acetate, copper (II) tetrafluoroborate, di-μ-hydroxo-bis [(N, N, N ′, N′-tetramethylethylenediamine ) Copper (II)] chloride, dichloro (1,10-phenanthroline) copper (II), tetralithium copper (II) dilithium, copper (II) trifluoromethanesulfonate, copper (I) trifluoromethanesulfonate benzene complex, tetrakis (Acetonitrile) copper (I) hexafluorophosphate, tetrakis (acetonitrile) copper (I) tetrafluoroborate, copper chloride (I Copper (II) chloride, copper (I) bromide, copper (II) nitrate, copper, fluorotris (triphenylphosphine) copper (I), copper (I) iodide, copper (II) sulfate, copper bromide (II) and the like. These compounds may be hydrates or may be derivatized.

  The addition amount of the transition metal compound is preferably from 0.00001 equivalent to 10 equivalents, more preferably from 0.0001 equivalent to 1 equivalent, based on the compound (ia) from the viewpoints of cost, yield, and ease of purification. More preferably, it is more preferably 0.001 to 0.5 equivalent, and particularly preferably 0.01 to 0.1 equivalent. Further, it is preferably from 0.00001 equivalent to 10 equivalent, more preferably from 0.0001 equivalent to 1 equivalent, and more preferably from 0.001 equivalent to 0.5 equivalent based on compound (ib). It is particularly preferably 0.01 to 0.1 equivalent.

  In the production of the compound (i), the addition amount of the compound (ib) is preferably 0.1 equivalent to 10 equivalents to the compound (ia) from the viewpoint of cost, yield, and ease of purification. , More preferably from 0.5 to 2 equivalents, even more preferably from 0.8 to 1.2 equivalents, and particularly preferably from 0.9 to 1.1 equivalents.

  In the production of the compound (i), the mixing order of the compound (ia), the compound (ib) and the transition metal compound is selected from the viewpoints of control of the reaction temperature, workability, yield, and purity of the obtained compound. ) And a transition metal compound, a compound (ib) is added, or to a mixture containing a compound (ia) and a compound (ib), a transition metal compound is added, or a compound (ib) and a transition metal are added. It is preferable to add the compound (ia) to the mixture containing the compound, or to add the mixture of the compound (ia) and the compound (ib) to the transition metal compound, and to contain the compound (ia) and the transition metal compound. The compound (ib) is added to the mixture, or the transition metal compound is added to the mixture containing the compound (ia) and the compound (ib), or Compound (ia) and compound mixture is more preferable to add the (ib), to a mixture containing the compound (ia) a transition metal compound, it is particularly preferable to add a compound (ib).

  In the production of compound (i), it is preferable to further use a base. The base is preferably an inorganic base or an organic base. As the inorganic base, metal hydroxide, metal acetate, metal formate, metal oxalate, metal phosphate, metal hydrogen phosphate, metal carbonate, metal bicarbonate, ammonia and the like are preferable. Alkali metals, alkaline earth metals and magnesium are preferred, specifically potassium carbonate, potassium phosphate, ammonia, aluminum hydroxide, barium hydrate, caustic barite, barium hydroxide, bismuth hydroxide, cadmium hydroxide, Cesium hydroxide, calcium hydroxide, cerium hydroxide, chromium hydroxide, cobalt hydroxide, copper hydroxide, ferric hydrate, iron hydroxide, lithium hydroxide, magnesium hydroxide, manganese hydroxide, nickel hydroxide , Potassium hydroxide, sodium hydroxide, sodium hypochlorite, strontium hydroxide, thallium hydroxide, triuium hydroxide , Sodium acetate, sodium aluminum sulfate, sodium ammonium phosphate, sodium hydrogen carbonate, sodium carbonate, calcium acetate, calcium carbonate, calcium formate, thallium acetate, potassium acetate, sodium phosphate, calcium phosphate, magnesium phosphate, potassium hydrogen carbonate, formic acid Potassium, potassium oxalate, ammonium bicarbonate, ammonium carbonate, ammonium formate, ammonium sulfate are exemplified. As the organic base, primary amines, secondary amines, tertiary amines, aromatic amines and salts thereof are preferable, and specifically, methylamine, ethylamine, propylamine, butylamine, pentylamine, isopropylamine, dimethyl Amine, N-ethylmethylamine, N-methylpropylamine, N-butylmethylamine, N-methylpentylamine, diethylamine, N-ethylpropylamine, N-butylethylamine, N-ethylpentylamine, dipropylamine, diisopropyl Amine, trimethylamine, triethylamine, tripropylamine, triisopropylamine, N, N-diisopropylmethylamine, N, N-diisopropylethylamine, tributylamine, pyrrolidine, piperidine, N-methylpyrrolidine, N Methylpiperidine, morpholine, pyridine, N-methylpyridine, 2-chloropyridine, 2-bromopyridine, pyrimidine, quinoline, acridine, N, N-dimethyl-4-aminopyridine, picoline, bipyridine, 2,6-lutidine, chloro Examples include pyridinium chromate and pyridinium paratoluenesulfonate.

  In the production of compound (i), the amount of the base to be added is preferably 0.1 equivalent to 20 equivalents relative to compound (ia) from the viewpoint of cost, yield and ease of purification. It is more preferably from 5 to 5 equivalents, further preferably from 0.8 to 3 equivalents, and particularly preferably from 1 to 2 equivalents. Further, a base may be used as a solvent, or a base may be used as a part of the solvent.

  In the production of the compound (i), from the viewpoint of the yield and the purity of the obtained compound, the reaction is preferably carried out under air or under an inert gas atmosphere, and particularly preferably under an inert gas atmosphere. Examples of the inert gas include nitrogen and argon.

  In the production of the compound (i), a solvent is preferably used for the reaction, and an organic solvent and / or water is more preferably used from the viewpoint of control of the reaction temperature, workability, yield, and purity of the obtained compound. It is particularly preferable to use an organic solvent or a mixture of an organic solvent and water. Examples of the organic solvent include aliphatic hydrocarbons, aromatic hydrocarbons, aromatic amines, aliphatic amines, ethers, alcohols, halogenated solvents, esters, ketones, amides, and the like. As the organic solvent, specifically, chloroform, carbon tetrachloride, dichloromethane, 1,2-dichloroethane, 1,2-dichloroethylene, 1,1,2,2-tetrachloroethane, trichloroethylene, 1-chlorobutane, carbon disulfide, Acetone, acetonitrile, benzonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, diethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether, Diethylene glycol diethyl ether, o-dichlorobenzene, xylene, o-xylene, p-xylene, m-xylene, chlorobenzene, isobutyl acetate, isopropyl acetate , Isoamyl acetate, ethyl acetate, butyl acetate, propyl acetate, pentyl acetate, methyl acetate, 2-methoxyethyl acetate, hexamethylphosphoric triamide, tris (dimethylamino) phosphine, cyclohexanone, 1,4-dioxane, dichloromethane, styrene , Tetrachloroethylene, tetrahydrofuran, pyridine, 1-methyl-2-pyrrolidinone, 1,1,1-trichloroethane, toluene, hexane, pentane, cyclohexane, cyclopentane, heptane, benzene, methyl isobutyl ketone, tert-butyl methyl ether, methyl ethyl ketone, Methyl cyclohexanone, methyl butyl ketone, diethyl ketone, gasoline, coal tar naphtha, petroleum ether, petroleum naphtha, petroleum benzine, turpentine, mineral spirits Doors and the like. When a mixture of an organic solvent and water is used, a phase transfer catalyst may be added. Examples of the phase transfer catalyst include benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, polyoxyethylene (10) octyl phenyl ether [Triton X-100], polyoxyethylene (20) sorbitan monopalmitate [Tween 40], and sorbitan mono. Palmitate [Span 40] and the like.

  In the production of the compound (i), the reaction temperature is preferably from −20 ° C. to 250 ° C., and from 0 ° C. to 200 ° C., from the viewpoint of control of the reaction temperature, workability, time, yield, and purity of the obtained compound. The temperature is more preferably from room temperature to 150 ° C., and particularly preferably from 50 ° C. to 130 ° C.

  In the production of compound (i), after the reaction, the reaction solution is mixed with a poor solvent to precipitate the desired product as a solid, and a crude product of the desired product is obtained. After adding an organic solvent and performing liquid separation treatment, the solvent may be distilled off to obtain a crude product of the desired product.

  It is preferable to further purify the compound (i) obtained as a crude product. In the purification step, it is preferable to use a purification agent. Examples of the purifying agent include silica gel, alumina, activated carbon, activated clay, celite, zeolite, mesoporous silica, carbon nanotube, carbon nanohorn, bincho charcoal, charcoal, graphene, ion exchange resin, acid clay, silicon dioxide, diatomaceous earth, perlite, and cellulose. , Organic polymers, porous gels and the like. From the viewpoint of workability, yield, and purity of the obtained compound, it is preferable to use silica gel and / or alumina, and it is particularly preferable to use silica gel. Further, recrystallization may be further performed.

  When an organic solvent is used in the production of compound (i), the organic solvent is preferably concentrated under reduced pressure.

  Methods for determining the purity of compound (i) include liquid chromatography, gas chromatography, gel permeation chromatography, nuclear magnetic resonance spectroscopy, and the like. The purity of the compound (i) is selected from liquid chromatography (UV detector, 210 nm) or gas chromatography in view of the balance between the quality of the compound, the quality of the display product when a liquid crystal panel is manufactured, and the manufacturing cost of the compound. (FID detector), it is preferably from 95.00% to 100.00%, more preferably from 98.00% to 100.00%, and more preferably from 99.00% to 100.00%. Is still more preferable, and it is still more preferable that it is 99.50% to 99.99%, and it is especially preferable that it is 99.90% to 99.99%.

  Inductively coupled plasma mass spectrometry (ICP-MS) is preferred as a method for determining the metal impurity content of compound (i). In view of the difficulty of image sticking when a liquid crystal panel is manufactured by adding the obtained compound (i) to an n-type liquid crystal composition, the content of metal impurities in the compound (i) is determined by inductively coupled plasma mass spectrometry. Using (ICP-MS), the content is preferably from 0.00 ppt to 1.00 ppm, more preferably from 0.00 ppt to 100 ppb, still more preferably from 0.01 ppt to 10.0 ppb, and It is still more preferably from 0.01 ppt to 1.00 ppb, particularly preferably from 0.01 ppt to 100 ppt.

  Included in compound (i), compound (ia), compound (ib), compound represented by general formula (X1), compound represented by general formula (X2) and compound represented by general formula (X1) The 1,4-cyclohexylene group, the tetrahydropyran-2,5-diyl group and the 1,3-dioxane-2,5-diyl group may be either a cis form or a trans form, or a mixture of both. However, from the viewpoint of liquid crystallinity, the trans-form is preferably the main component, the proportion of the trans-form is more preferably 90% or more, and the proportion of the trans-form is 95% or more. More preferably, the ratio of the trans form is even more preferably 99% or more, and particularly preferably, the ratio of the trans form is 99.9% or more.

  Compound (i) produced by the production method of the present invention is preferably added to various compositions, more preferably to a liquid crystal composition. Since the compound (i) produced by the production method of the present invention has a low metal impurity content, it should be added to an n-type liquid crystal composition in which the metal impurities contained in the composition greatly affect the quality of the display element. Is particularly preferred.

  When the compound (i) produced by the production method of the present invention is added to an n-type liquid crystal composition, the n-type liquid crystal composition has the following general formula (X1)

(Wherein, R ³ and R ⁴ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, or one —CH ₂ — or two or more non-adjacent —CH ₂ — —O—, —CH ＝ CH—, —CF ＝ CF— or —C≡C— represents a linear alkyl group having 1 to 6 carbon atoms which may be substituted by any one of the alkyl groups. The hydrogen atom may be substituted by a fluorine atom, and A ⁵ and A ⁶ each independently represent a 1,4-phenylene group or a 1,4-cyclohexylene group, but these groups are unsubstituted or It may be substituted by one or more substituents L ^X1 , and when there are a plurality of A ^5, they may be the same or different, and when there are a plurality of A ^6, they may be the same or different L ^X1 represents a fluorine atom, Z ⁵ and Z -OCH ₂ ⁶ are each independently _{-, - CH 2 O -,} - CH 2 CH 2 -, - CF 2 O -, - OCF 2 -, - C≡C- or represents a single bond, is ^{Z 5} When a plurality of Z ⁶ are present, they may be the same or different. When a plurality of Z ⁶ exist, they may be the same or different, and m5 and m6 are each independently an integer of 0 to 3. Wherein m5 + m6 represents an integer of 0 to 3.), and as the compound represented by the general formula (X1), the following general formula (X1-E-1) From the general formula (X1-E-9)

(Wherein, R ^3E represents a linear alkyl group having 1 to 6 carbon atoms or a linear alkenyl group having 2 to 6 carbon atoms, and R ^4E represents a linear alkyl group having 1 to 6 carbon atoms.) A straight-chain alkoxy group having 1 to 5 carbon atoms, a straight-chain alkenyl group having 2 to 6 carbon atoms or a straight-chain alkenyloxy group having 2 to 5 carbon atoms.) More preferred.

  When the compound (i) produced by the production method of the present invention is added to an n-type liquid crystal composition, the n-type liquid crystal composition has the following general formula (X2)

(Wherein, R ⁵ and R ⁶ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, or one —CH ₂ — or two or more non-adjacent —CH ₂ — —O—, —CH ＝ CH—, —CF ＝ CF— or —C≡C— represents a linear alkyl group having 1 to 6 carbon atoms which may be substituted by any one of the alkyl groups. The hydrogen atom may be substituted by a fluorine atom, and A ⁷ and A ⁸ each independently represent a 1,4-phenylene group or a 1,4-cyclohexylene group, but these groups are unsubstituted or It may be substituted by one or more substituents L ^X2 , and when A ⁷ is present in plurals, they may be the same or different, L ^X2 represents a fluorine atom, and Z ⁷ represents —OCH ₂ —. _{, -CH 2 O -, - CH} 2 CH 2 -, - CF 2 O -, - It represents OCF ₂ —, —C≡C— or a single bond, and when a plurality of Z ⁷ are present, they may be the same or different, and m 7 each independently represents an integer of 0 to 3. The compound represented by the general formula (X2) is preferably a compound represented by the following general formula (X2-E-1).

(Wherein, R ^5E is a linear alkyl group having 1 to 6 carbon atoms, a linear alkoxy group having 1 to 5 carbon atoms, a linear alkenyl group having 2 to 6 carbon atoms, or 2 carbon atoms) Represents a linear alkenyloxy group having 1 to 5 carbon atoms, and R ^6E represents a linear alkyl group having 1 to 6 carbon atoms, a linear alkoxy group having 1 to 5 carbon atoms, and a straight chain having 2 to 6 carbon atoms. A alkenyl group or a linear alkenyloxy group having 2 to 5 carbon atoms.).

  When the compound (i) produced by the production method of the present invention is added to an n-type liquid crystal composition, the n-type liquid crystal composition has the following general formula (X3)

(Wherein, R ⁷ is each independently a hydrogen atom, or one -CH ₂ -or two or more non-adjacent -CH ₂ -are each independently -O-, -COO-,- OCO -, - CH = CH - , - CF = CF- or -C≡C- represents a linear or branched alkyl group having 25 good 1 -C be replaced by, ^{a 9} is 1,4 Represents a phenylene group, a 1,4-cyclohexylene group or a 1,3-dioxane-2,5-diyl group, these groups being unsubstituted or substituted by one or more substituents L ^X3 It is good, if the a ⁹ there are a plurality thereof may be different even in the same, L ^X3 is fluorine atom, or one -CH 2 _- not adjacent two or more -CH ₂ - Each independently has 1 to 20 carbon atoms which may be substituted by -O-. Represents a linear or branched alkyl group, ^{Z 8} is _{-OCH 2 -, - CH 2 O} -, - CH 2 CH 2 -, - COO -, - OCO -, - COO-CH 2 CH 2 -, - Represents OCO-CH ₂ CH ₂ —, —CH ₂ CH ₂ —COO—, —CH ₂ CH ₂ —OCO— or a single bond, and when a plurality of Z ⁸ are present, they may be the same or different And m8 each independently represents an integer of 0 to 3.), and the compound represented by the general formula (X3) includes a compound represented by the following general formula (X3-E- From 1) to general formula (X3-E-3)

(Wherein, R ^7E represents a straight-chain alkyl group having 1 to 20 carbon atoms).

Hereinafter, an example of the step of obtaining the compound (i) by the production method of the present invention will be described.
(Production method 1) Production of compound represented by the following general formula (I-is)

(Wherein, R ¹¹ , R ²¹ , A ¹¹ , A ²¹ , A ³¹ , A ⁴¹ , Z ¹¹ , Z ²¹ , Z ³¹ , Z ⁴¹ , m11, m21, m31 and m41 are represented by the general formula (Ii) represents the same ^{meaning, X 11} have the same meanings as in the formula ^{(IA-i), X 21} have the same meanings as those in formula (IB-i).)
The compound represented by the general formula (I-is) can be obtained by reacting the compound represented by the general formula (IA-is) with the compound represented by the general formula (IB-is). Examples of the reaction include, for example, a method of cross-coupling in the presence of a metal catalyst and a base. Specific examples of the metal catalyst include [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride, palladium (II) acetate, tetrakis (triphenylphosphine) palladium (0) and the like. Specific examples of the base include potassium carbonate, potassium phosphate, cesium carbonate and the like. The reaction conditions include, for example, Metal-Catalyzed Cross-Coupling Reactions (authored by Armin de Meijere and Francois Diedrich, Wiley-VCH), Palladium Reagents and Catalysts: New Persist. Cross-Coupling Reactions: A Practical Guide (Topics in Current Chemistry) (S.L. a, E. Shiragawa, K. Tamao, Springer) and the like.

  Reaction conditions other than those described above include, for example, Experimental Chemistry Course (edited by The Chemical Society of Japan, published by Maruzen Co., Ltd.), Organic Synthesis (A John Wiley & Sons, Inc., Publication), and Beilstein Handbook of Chemical Research- Organischen Chemie, Springer-Verlag Berlin and Heidelberg GmbH & Co. K), Fiesers' Reagents for Organic Synthesis, etc. in John Wiley & Sons, Inc. acts Service, American Chemical Society, and Reaxys (Elsevier Ltd.).

  Further, a reaction solvent can be appropriately used in the above step. Specific examples of the solvent include ethanol, tetrahydrofuran, toluene, dichloromethane, water and the like. When the reaction is carried out in a two-phase system of an organic solvent and water, a phase transfer catalyst can be added. Specific examples of the phase transfer catalyst include benzyltrimethylammonium bromide and tetrabutylammonium bromide.

  In addition, purification can be performed as necessary in the above step. Examples of the purification method include chromatography, recrystallization, distillation, sublimation, reprecipitation, adsorption, and liquid separation. Specific examples of the purifying agent include silica gel, alumina, activated carbon and the like.

Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited to these examples. Further, “%” in the compositions of the following Examples and Comparative Examples means “% by mass”. When handling a substance unstable to oxygen and / or moisture in each step, it is preferable to perform the operation in an inert gas such as nitrogen gas or argon gas. In addition to the operations specifically described below, if necessary, operations such as quenching, liquid separation / extraction, neutralization, washing, separation, purification, drying, and concentration of the reaction that are usually performed by those skilled in the art. May be performed.
(GC analysis conditions)
Column: Agilent Technologies, J & W Column DB-1HT, 15m x 0.25mm x 0.10m
Temperature program: 100 ° C (1 minute)-(20 ° C / min)-250 ° C-(10 ° C / min) -380 ° C-(7 ° C / min)-400 ° C (2.64 minutes)
Inlet temperature: 350 ° C
Detector temperature: 400 ° C
(LC analysis conditions)
Column: Waters ACQUITY UPLC BEH C18, 2.1 × 100 mm, 1.7 μm
Elution solvent: acetonitrile / water (90:10), acetonitrile / water (85:15), 0.1% formic acid-acetonitrile / water (90:10) or 0.1% formic acid-acetonitrile / water (70:30)
Flow rate: 0.4 mL / min
Detector: UV (PDA)
Column oven: 40 ° C
(Example 1) Production of compound represented by formula (I-1)

The compound represented by the formula (I-1-1) was produced by the method described in European Journal of Organic Chemistry, 2008, No. 20, page 3479-3487. Under a nitrogen atmosphere, 2.0 g of the compound represented by the formula (I-1-1), 1.5 g of potassium carbonate, 20 mL of ethanol, and 0.1 g of tetrakis (triphenylphosphine) palladium (0) were added to the reaction vessel. While heating under reflux, a solution in which 1.4 g of the compound represented by the formula (I-1-2) was dissolved in 4 mL of ethanol was added dropwise. After heating under reflux for 8 hours, the mixture was cooled and the reaction solution was poured into water. The mixture was extracted with toluene and washed sequentially with water and brine. The toluene was distilled off under reduced pressure. Purification was performed by column chromatography (silica gel, hexane) and recrystallization (acetone / methanol) to obtain 1.8 g of a compound represented by the formula (I-1).
GC purity: 99.92%
Pd content (ICP-MS): 0.1 ppt
LC-MS: 361 [M + 1]
(Example 2) Production of compound represented by formula (I-2)

The compound represented by the formula (I-2-1) was produced by the method described in DE 102009018067A1. Under a nitrogen atmosphere, 2.0 g of the compound represented by the formula (I-2-1), 1.9 g of the compound represented by the formula (I-2-2), 2.3 g of potassium phosphate, and 10 mL of tetrahydrofuran were placed in a reaction vessel. Then, 10 mL of water, and 0.1 g of [1,1'-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct were added, and the mixture was refluxed for 8 hours. Cooled and poured the reaction into water. The mixture was extracted with toluene and washed sequentially with water and brine. The toluene was distilled off under reduced pressure. Purification was performed by column chromatography (silica gel, hexane) and recrystallization (ethanol) to obtain 1.7 g of a compound represented by the formula (I-2).
GC purity: 99.91%
Pd content (ICP-MS): 0.3 ppt
LC-MS: 359 [M + 1]
(Example 3) Production of compound represented by formula (I-3)

  Under a nitrogen atmosphere, 2.0 g of the compound represented by the formula (I-3-1) and 10 mL of tetrahydrofuran were added to the reaction vessel. After cooling to -20 ° C, 1.0 g of potassium tert-butoxide was added. At −20 ° C., a solution in which 1.4 g of the compound represented by the formula (I-3-2) was dissolved in 5 mL of tetrahydrofuran was added dropwise, and the mixture was stirred for 3 hours. After warming to room temperature, water was added. The mixture was extracted with toluene and washed sequentially with water and brine. By purifying by column chromatography (silica gel, hexane), 1.8 g of a compound represented by the formula (I-3-3) was obtained.

  Under a nitrogen atmosphere, 1.8 g of the compound represented by the formula (I-3-3), 1.2 g of the compound represented by the formula (I-3-4), 1.2 g of potassium carbonate, 20 mL of ethanol and 0.1 g of tetrakis (triphenylphosphine) palladium (0) was added, and the mixture was refluxed for 8 hours. Cooled and poured the reaction into water. The mixture was extracted with toluene and washed sequentially with water and brine. Purification was performed by column chromatography (silica gel, hexane) to obtain 1.8 g of a compound represented by the formula (I-3-5).

Under a nitrogen atmosphere, 1.8 g of the compound represented by the formula (I-3-5), 18 mL of tetrahydrofuran, and 0.2 g of 5% palladium / carbon were added to a pressure vessel. The mixture was stirred at a hydrogen pressure of 0.5 MPa for 8 hours. After the reaction solution was filtered through celite, the solvent was distilled off under reduced pressure. Purification was performed by column chromatography (silica gel, hexane) and recrystallization (ethanol) to obtain 1.4 g of a compound represented by the formula (I-3).
GC purity: 99.95%
Pd content (ICP-MS): 5.0 ppt
LC-MS: 375 [M + 1]
(Example 4) Production of compound represented by formula (I-4)

The compound represented by the formula (I-4-4) was produced by the method described in CN1026559533A. In Example 3, the compound represented by the formula (I-3-1) was replaced with the compound represented by the formula (I-4-1), and the compound represented by the formula (I-3-4) was substituted by the compound represented by the formula (I-I). A compound represented by the formula (I-4) was produced in the same manner except that the compound represented by -4-4) was used.
GC purity: 99.86%
Pd content (ICP-MS): 25 ppt
LC-MS: 449 [M + 1]
(Example 5) Production of compound represented by formula (I-5)

  Under a nitrogen atmosphere, 0.2 g of magnesium and 1 mL of tetrahydrofuran were added to the reaction vessel. A solution in which 2.0 g of the compound represented by the formula (I-5-1) was dissolved in 10 mL of tetrahydrofuran was added dropwise to prepare a Grignard reagent. Carbon dioxide was introduced and the mixture was stirred for 3 hours. 5% hydrochloric acid was added dropwise, and the mixture was extracted with ethyl acetate. Washed with water and brine. After drying over sodium sulfate, the solvent was distilled off and the residue was dried under reduced pressure to obtain 1.6 g of a compound represented by the formula (I-5-2).

  Under a nitrogen atmosphere, 1.6 g of the compound represented by the formula (I-5-2) and 20 mL of dichloromethane were added to the reaction vessel. 1.0 g of oxalic acid chloride was added dropwise, and the mixture was refluxed for 5 hours. By evaporating the solvent, 1.6 g of a compound represented by the formula (I-5-3) was obtained.

  Under a nitrogen atmosphere, 1.6 g of the compound represented by the formula (I-5-3), 0.8 g of 1,3-propanedithiol, 1.7 g of trifluoromethanesulfonic acid, and 20 mL of toluene were added to the reaction vessel, and the mixture was heated at 100 ° C. The mixture was heated under reflux for 3 hours. After cooling, diisopropyl ether was added and the crystals were filtered. The obtained crystals were dried under reduced pressure to obtain 2.2 g of a compound represented by the formula (I-5-4).

  Under a nitrogen atmosphere, 0.8 g of the compound represented by the formula (I-5-5), 2 mL of dichloromethane, and 2.3 g of triethylamine were added to the reaction vessel. While cooling to -70 ° C, a solution in which 2.2 g of the compound represented by the formula (I-5-4) was dissolved in 6 mL of dichloromethane was added dropwise, and the mixture was stirred for 1 hour. While cooling to −70 ° C., 1.5 g of triethylamine hydrogen trifluoride was added dropwise and stirred for 1 hour. While cooling to -70 ° C, 0.7 g of bromine was added dropwise and stirred for 1 hour. The temperature was raised to room temperature, and an aqueous solution of sodium hydrogen carbonate was added. The mixture was extracted with toluene and washed sequentially with water and brine. Purification was performed by column chromatography (silica gel, hexane) to obtain 1.4 g of a compound represented by the formula (I-5-6).

  Under a nitrogen atmosphere, 0.1 g of magnesium and 0.2 mL of tetrahydrofuran were added to the reaction vessel. A solution in which 1.4 g of the compound represented by the formula (I-5-6) was dissolved in 4 mL of tetrahydrofuran was added to prepare a Grignard reagent. 0.4 g of trimethyl borate was added dropwise and stirred for 1 hour. 10 mL of 10% hydrochloric acid was added dropwise. The mixture was extracted with ethyl acetate and washed sequentially with water and brine. By evaporating the solvent, 1.2 g of a compound represented by the formula (I-5-7) was obtained.

Under a nitrogen atmosphere, 1.2 g of the compound represented by the formula (I-5-7), 0.7 g of the compound represented by the formula (I-5-8), 0.6 g of potassium carbonate, 10 mL of ethanol and 0.1 g of dichlorobis (triphenylphosphine) palladium (II) was added, and the mixture was refluxed for 8 hours. Cooled and poured the reaction into water. The mixture was extracted with toluene and washed sequentially with water and brine. Purification was performed by column chromatography (silica gel, toluene / hexane) and recrystallization (toluene / ethanol) to obtain 1.8 g of a compound represented by the formula (I-5).
GC purity: 99.85%
Pd content (ICP-MS): 40 ppt
LC-MS: 519 [M + 1]
(Example 6) Production of compound represented by formula (I-82)

The compound represented by the formula (I-82-1) was produced by the method described in European Journal of Organic Chemistry, 2008, No. 20, page 3479-3487. Under a nitrogen atmosphere, 3.0 g of the compound represented by the formula (I-82-1), 1.7 g of the compound represented by the formula (I-82-2), 1.7 g of potassium carbonate, 15 mL of tetrahydrofuran were placed in a reaction vessel. 10 mL of water and 0.2 g of tetrakis (triphenylphosphine) palladium (0) were added, and the mixture was heated under reflux for 8 hours. Cooled and poured the reaction into water. The mixture was extracted with toluene and washed sequentially with water and brine. Purification was performed by column chromatography (silica gel, toluene / hexane) and recrystallization (toluene / ethanol) to obtain 2.0 g of a compound represented by the formula (I-82).
GC purity: 99.92%
Pd content (ICP-MS): 120 ppt
LC-MS: 449 [M + 1]
(Example 7) Production of compound represented by formula (I-121)

  1.8 mL of the compound represented by the formula (I-121-2) and 40 mL of toluene were added to the reaction vessel. A solution in which 2.8 mL of dipropylamine was dissolved in 10 mL of toluene was added dropwise, and the mixture was refluxed for 14 hours. After the solvent was distilled off, 25 mL of methanol and 10 mL of toluene were added. A solution in which 3.9 g of the compound represented by the formula (I-121-1) was dissolved in 15 mL of toluene was added dropwise, and the mixture was heated and stirred at 50 ° C for 8 hours. After sequentially washing with 5% hydrochloric acid, water and brine, purification was performed by column chromatography (silica gel, toluene / hexane) to obtain 4.6 g of a compound represented by the formula (I-121-3).

  To the reaction vessel, 4.6 g of the compound represented by the formula (I-121-3), 2.0 g of zinc chloride, 20 mL of toluene, 15 mL of formic acid, and 15 mL of acetic acid were added. 12 mL of 1,1,3,3-tetramethyldisiloxane was added dropwise, and the mixture was stirred at room temperature for 8 hours. The reaction solution was poured into water and washed sequentially with 5% hydrochloric acid, water and brine. Purification was performed by column chromatography (silica gel, toluene) and recrystallization (acetone / methanol) to obtain 2.3 g of a compound represented by the formula (I-121-4).

Under a nitrogen atmosphere, 2.3 g of the compound represented by the formula (I-121-4), 1.6 g of potassium carbonate, 20 mL of ethanol, and 0.1 g of tetrakis (triphenylphosphine) palladium (0) were added to a reaction vessel. While heating under reflux, a solution in which 1.5 g of the compound represented by the formula (I-121-5) was dissolved in 4 mL of ethanol was added dropwise. After heating under reflux for 8 hours, the mixture was cooled and the reaction solution was poured into water. The mixture was extracted with toluene and washed sequentially with water and brine. The toluene was distilled off under reduced pressure. Purification was performed by column chromatography (silica gel, hexane) and recrystallization (acetone / methanol) to obtain 1.8 g of a compound represented by the formula (I-121).
GC purity: 99.92%
Pd content (ICP-MS): 0.1 ppt
LC-MS: 379 [M + 1]
(Example 8) Production of compound represented by formula (I-151)

  To the reaction vessel, 4.9 g of the compound represented by the formula (I-151-1) and 30 mL of toluene were added. A solution in which 4.0 mL of dipropylamine was dissolved in 10 mL of toluene was added dropwise, and the mixture was refluxed for 14 hours. After the solvent was distilled off, 30 mL of methanol and 20 mL of toluene were added. A solution in which 2.9 mL of the compound represented by the formula (I-151-2) was dissolved in 10 mL of toluene was added dropwise, and the mixture was heated and stirred at 50 ° C. for 10 hours. After sequentially washing with 5% hydrochloric acid, water and brine, purification was performed by column chromatography (silica gel, toluene / hexane) to obtain 5.3 g of a compound represented by the formula (I-151-3).

  To the reaction vessel, 5.3 g of the compound represented by the formula (I-151-3), 3.3 g of zinc chloride, 40 mL of toluene, 30 mL of formic acid, and 30 mL of acetic acid were added. 22 mL of 1,1,3,3-tetramethyldisiloxane and 1.6 mL of methanesulfonic acid were sequentially added dropwise, and the mixture was stirred at room temperature for 14 hours. The reaction solution was poured into water and washed sequentially with 5% hydrochloric acid, water and brine. Purification was performed by column chromatography (silica gel, toluene) and recrystallization (acetone / methanol) to obtain 3.3 g of a compound represented by the formula (I-151-4).

Under a nitrogen atmosphere, 3.3 g of the compound represented by the formula (I-151-4), 2.4 g of potassium carbonate, 30 mL of ethanol, and 0.2 g of tetrakis (triphenylphosphine) palladium (0) were added to a reaction vessel. While heating and refluxing, a solution in which 2.6 g of the compound represented by the formula (I-121-5) was dissolved in 6 mL of ethanol was added dropwise. After heating under reflux for 8 hours, the mixture was cooled and the reaction solution was poured into water. The mixture was extracted with toluene and washed sequentially with water and brine. The toluene was distilled off under reduced pressure. Purification was performed by column chromatography (silica gel, hexane) and recrystallization (acetone / methanol) to obtain 2.8 g of a compound represented by the formula (I-151).
GC purity: 99.91%
Pd content (ICP-MS): 0.1 ppt
LC-MS: 361 [M + 1]
(Example 9) Production of compound represented by formula (I-181)

A compound represented by the formula (I-181) was prepared in the same manner as in Example 8 except that the compound represented by the formula (I-151-1) was replaced with the compound represented by the formula (I-181-1). Was prepared.
GC purity: 99.93%
Pd content (ICP-MS): 0.2 ppt
LC-MS: 379 [M + 1]
(Example 10) Production of compound represented by formula (I-211)

In Example 7, a compound represented by the formula (I-211) was prepared in the same manner except that the compound represented by the formula (I-121-1) was replaced with a compound represented by the formula (I-211-1). Was prepared.
GC purity: 99.93%
Pd content (ICP-MS): 0.1 ppt
LC-MS: 379 [M + 1]
(Example 11) Production of compound represented by formula (I-241)

A compound represented by the formula (I-241) was prepared in the same manner as in Example 8, except that the compound represented by the formula (I-151-1) was replaced with the compound represented by the formula (I-241-1). Was prepared.
GC purity: 99.93%
Pd content (ICP-MS): 0.3 ppt
LC-MS: 379 [M + 1]
(Comparative Example 1) Production of compound represented by formula (I-1R)

  It was prepared by the method described in Molecular Crystals and Liquid Crystals, 2011, vol. 542, pp. 16-27. To the reaction vessel were added 5.0 g of the compound represented by the formula (I-1R-1), 3.1 g of aluminum (III) chloride, and 20 mL of dichloromethane. Under ice cooling, 3.2 g of 3-chloropropionyl chloride was added, and the mixture was stirred for 1 hour. The reaction vessel was poured into 20 mL of 10% hydrochloric acid, and the organic layer was sequentially washed with a 10% aqueous sodium hydroxide solution and water. After drying over magnesium sulfate, the solvent was distilled off. Purification was performed by recrystallization (hexane) to obtain 6.2 g of a compound represented by the formula (I-1R-2).

  5.0 g of the compound represented by the formula (I-1R-2) and 20 mL of tetrahydrofuran were added to the reaction vessel. 10 mL of a 10% aqueous sodium hydroxide solution was added, and the mixture was heated and stirred at 50 ° C. for 1 hour. The mixture was extracted with 50 mL of toluene and washed with water. After drying over magnesium sulfate, the solvent was distilled off. Purification was performed by recrystallization (hexane) to obtain 3.2 g of a compound represented by the formula (I-1R-3).

  To the reaction vessel, 6.3 g of the compound represented by the formula (I-1R-3) and 50 mL of toluene were added. 2.5 g of diisopropylamine was added, and the mixture was heated and stirred at 80 ° C. for 10 hours. After cooling to room temperature, 200 mL of water was added. The organic layer was sequentially washed with 100 mL of 10% hydrochloric acid and water. After drying over magnesium sulfate, the solvent was distilled off. Purification was performed by recrystallization (hexane) to obtain 20.3 g of a compound represented by the formula (I-1R-4).

10.0 g of the compound represented by the formula (I-1R-4) and 100 mL of acetic acid were added to the reaction vessel. 3.6 g of zinc (II) chloride and 16.9 g of triethylsilane were added, and the mixture was stirred at 25 ° C for 10 hours. 200 mL of water was added, and extracted with toluene. The organic layer was washed sequentially with 10% hydrochloric acid and water. After drying over magnesium sulfate, the solvent was distilled off. Purification was performed by column chromatography (silica gel, hexane) and recrystallization (ethyl acetate) to obtain 7.3 g of a compound represented by the formula (I-1R).
GC purity: 99.73%
LC-MS: 361 [M + 1]
(Comparative Example 2) Production of compound represented by formula (I-2R)

  It was prepared by the method described in Molecular Crystals and Liquid Crystals, 2014, vol. 593, pp. 61-77. To the reaction vessel, 4.8 g of the compound represented by the formula (I-2R-2), 5.7 g of the compound represented by the formula (I-2R-1), and 20 mL of toluene were added. 0.2 g of dipropylamine and 3 mL of methanol were added, and the mixture was heated and stirred at 40 ° C. for 12 hours. After cooling, 10 mL of water was added, and the mixture was extracted with 30 mL of ethyl acetate. The organic layer was washed with brine and dried over magnesium sulfate, and then the solvent was distilled off to obtain 7.3 g of a compound represented by the formula (I-2R-3).

  To the reaction vessel, 7.3 g of the compound represented by the formula (I-2R-3) and 30 mL of toluene were added. At 0 ° C., 7.0 g of triethylsilane were added. 9.6 g of trifluoroacetic acid was added dropwise. The mixture was heated to room temperature and stirred for 7 hours. 3 mL of acetone was added, and the reaction solution was poured into a 20% aqueous sodium hydrogen carbonate solution. Extracted with toluene and washed with water. After drying over magnesium sulfate, the solvent was distilled off. Purification was performed by column chromatography (silica gel, heptane / ethyl acetate (20: 1)) to obtain 7.4 g of a compound represented by the formula (I-2R-4).

  7.4 g of the compound represented by the formula (I-2R-4) and 25 mL of chloroform were added to the reaction vessel. While cooling with ice, 3.4 g of trimethyliodosilane was added dropwise, and the mixture was stirred at 10 ° C. or lower for 5 hours. The reaction solution was poured into a 5% aqueous sodium hydrogen carbonate solution, and the organic layer was washed with water. After drying over magnesium sulfate, the solvent was distilled off. Purification was performed by column chromatography (silica gel, heptane / ethyl acetate (2: 1)) to obtain 1.6 g of a compound represented by the formula (I-2R-5).

  14.5 g of the compound represented by the formula (I-2R-5) and 140 mL of dichloromethane were added to the reaction vessel. 26.0 g of iodobenzene diacetate and 0.7 g of TEMPO were added, and the mixture was stirred at room temperature for 3 hours. The reaction solution was poured into a 10% aqueous sodium hydrogen carbonate solution and extracted with ethyl acetate. Insolubles were removed by filtration, and the organic layer was washed with brine. After drying over magnesium sulfate, the solvent was distilled off. Purification was performed by column chromatography (silica gel, heptane / ethyl acetate (4: 1)) to obtain 8.7 g of a compound represented by the formula (I-2R-6).

14.1 g of ethyltriphenylphosphonium bromide and 50 mL of tetrahydrofuran were added to the reaction vessel. At −40 ° C., 18 mL of a LDA (2M) / tetrahydrofuran solution was added dropwise, and the mixture was stirred for 30 minutes. Stirred at 0 ° C. for another hour. After cooling to −50 ° C., a solution in which 8.7 g of the compound represented by the formula (I-2R-6) was dissolved in 50 mL of tetrahydrofuran was added dropwise, and the mixture was stirred for 30 minutes. 22 mL of a phenyllithium (1.6 M) / dibutyl ether solution was added dropwise, and the mixture was stirred for 30 minutes. 5 g of tert-butyl alcohol and 10 mL of tetrahydrofuran were added dropwise. The temperature was raised to 0 ° C., and 100 mL of water and 100 mL of saline were added. The mixture was extracted with 200 mL of toluene, and the organic layer was washed sequentially with 10% hydrochloric acid, brine, 5% aqueous sodium hydrogen carbonate solution and brine. After drying over magnesium sulfate, the solvent was distilled off. Purification was performed by column chromatography (silica gel, heptane / ethyl acetate (10: 1)) and recrystallization (ethanol) to obtain 4.7 g of a compound represented by the formula (I-2R).
GC purity: 99.76%
LC-MS: 359 [M + 1]
(Comparative Example 3) Production of compound represented by formula (I-121R)

The compound represented by the formula (I-121R) was produced by the method described in Synthesis Example 1 of JP-A-2017-75095.
GC purity: 99.58%
LC-MS: 379 [M + 1]
(Comparative Example 4) Production of compound represented by formula (I-151R)

The compound represented by the formula (I-151R-1) was produced by the method described in Molecular Crystals and Liquid Crystals, 2011, vol. 542, 16 / [538] -27 [549].
GC purity: 99.76%
LC-MS: 361 [M + 1]
(Comparative Example 5) Production of compound represented by formula (I-181R)

The compound represented by the formula (I-181R) was produced by the method described in Synthesis Example 3 of JP-A-2017-75095.
GC purity: 99.71%
LC-MS: 379 [M + 1]
(Comparative Example 6) Production of compound represented by formula (I-211R)

The compound represented by the formula (I-211R) was produced by the method described in Synthesis Example 2 of JP-A-2017-75095.
GC purity: 99.74%
LC-MS: 379 [M + 1]
(Comparative Example 7) Production of compound represented by formula (I-241R)

The compound represented by the formula (I-241R) was produced by the method described in Synthesis Example 2 of JP-A-2017-75095.
GC purity: 99.77%
LC-MS: 379 [M + 1]
From the above results, in the production methods described in Examples 1 to 11, high-purity formulas (I-1) to (I-5), (I-82), Compounds represented by Formula (I-121), Formula (I-151), Formula (I-181), Formula (I-211), and Formula (I-241) were obtained. On the other hand, in the production methods described in Comparative Examples 1 to 7, the purity of the obtained compound was lower in the ordinary purification method than in the production methods described in Examples 1 to 11. Formula (I-1R), Formula (I-2R), Formula (I-121R), Formula (I-151R), Formula (I-181R), Formula (I-211R), and Formula (I-241R) Formula (I-1), Formula (I-2), Formula (I-121), Formula (I-151), Formula (I-181), Formula (I-211) and Formula (I-211) The same purification procedure was performed to make the compound represented by -241) and the purification conditions uniform.
(Comparative Example 8) Production of compound represented by formula (I-1R2) The compound represented by formula (I-1R) produced in Comparative Example 1 was subjected to column chromatography (silica gel, hexane) and recrystallization (acetone). / Methanol) to obtain a compound represented by the formula (I-1R2).
GC purity: 99.82%
LC-MS: 361 [M + 1]
(Comparative Example 9) Production of compound represented by formula (I-2R2) The compound represented by formula (I-2R) produced in Comparative Example 2 was subjected to column chromatography (silica gel, hexane) and recrystallization (ethanol). ) To obtain a compound represented by the formula (I-2R2).
GC purity: 99.85%
LC-MS: 359 [M + 1]
(Comparative Example 10) Production of compound represented by formula (I-121R2) For the compound represented by formula (I-121R) produced in Comparative Example 3, column chromatography (silica gel, hexane) and recrystallization (ethanol) ) To obtain a compound represented by the formula (I-121R2).
GC purity: 99.86%
LC-MS: 379 [M + 1]
(Comparative Example 11) Production of compound represented by formula (I-151R2) For the compound represented by formula (I-151R) produced in Comparative Example 4, column chromatography (silica gel, hexane) and recrystallization (ethanol) ) To obtain a compound represented by the formula (I-151R2).
GC purity: 99.88%
LC-MS: 361 [M + 1]
(Comparative Example 12) Production of compound represented by formula (I-181R2) For the compound represented by formula (I-181R) produced in Comparative Example 5, column chromatography (silica gel, hexane) and recrystallization (ethanol) ) To obtain a compound represented by the formula (I-181R2).
GC purity: 99.86%
LC-MS: 379 [M + 1]
(Comparative Example 13) Production of compound represented by formula (I-211R2) Column chromatography (silica gel, hexane) and recrystallization (ethanol) of the compound represented by formula (I-211R) produced in Comparative Example 6 ) To obtain a compound represented by the formula (I-211R2).
GC purity: 99.85%
LC-MS: 379 [M + 1]
(Comparative Example 14) Production of compound represented by formula (I-241R2) For the compound represented by formula (I-241R) produced in Comparative Example 7, column chromatography (silica gel, hexane) and recrystallization (ethanol) ) To obtain a compound represented by the formula (I-241R2).
GC purity: 99.88%
LC-MS: 379 [M + 1]
(Examples 12 to 22, Comparative Examples 15 to 28)
The compounds produced in Examples 1 to 11 and Comparative Examples 1 to 14 were used as compounds to be evaluated. A liquid crystal composition was prepared by mixing the following compounds at the component ratios shown in the following table, and was designated as parent liquid crystal (X10).

  15 parts by weight of the compound to be evaluated and 0.2 part by weight of the following compound (X3-E-1-1) were added to 100 parts by weight of the base liquid crystal (X10) to prepare a liquid crystal composition to be evaluated. .

  A first substrate (common electrode substrate) having a transparent electrode layer composed of a transparent common electrode and a color filter layer, and a second substrate (pixel) having a pixel electrode layer having a transparent pixel electrode driven by an active element (Electrode substrate). In the pixel electrode substrate, each pixel electrode was obtained by etching ITO so that the pixel electrode had a slit having no electrode in order to divide the orientation of liquid crystal molecules. A vertical alignment film material containing a polyimide precursor is applied to each of the common electrode substrate and the pixel electrode substrate by a spin coating method, and the applied film is heated at 200 ° C., so that the polyimide precursor in the vertical alignment film material is removed. After curing, a vertical alignment film of 100 nm ± 20 nm was formed on the surface of each substrate. As a material for forming a vertical alignment film, a polyimide solution containing 3% of a polyimide precursor (trade name: JALS2131-R6, manufactured by JSR) was used. After the liquid crystal composition to be evaluated was sandwiched between the common electrode substrate and the pixel electrode substrate on which the vertical alignment film was formed, the sealing material was cured to form a liquid crystal composition layer. At this time, the thickness of the liquid crystal composition layer was set to 3.0 μm using a spacer having a thickness of 3.0 μm. The following table shows the relationship between the compound to be evaluated and the liquid crystal display device.

With respect to the display elements of Examples 12 to 22 and Comparative Examples 15 to 28, burn-in evaluation was performed. In the burn-in evaluation, after a predetermined fixed pattern was displayed in the display area for 1000 hours, the level of the afterimage of the fixed pattern when the entire screen was uniformly displayed was visually evaluated by the following four-step evaluation.
A +: No afterimage A-: Very little afterimage on a part of screen B +: Level with acceptable afterimage with some afterimage B-: Level with some afterimage but acceptable with some afterimage C: Unacceptable with some afterimage level

  The display elements of Comparative Examples 15 to 28 have the same structure, respectively, from Formula (I-1) to Formula (I-5), Formula (I-82), Formula (I-121), and Formula (I-151). , More image sticking was observed as compared with a display element using the compounds represented by the formulas (I-181), (I-211) and (I-241). Formula (I-1R), Formula (I-2R), Formula (I-121R), Formula (I-151R), Formula (I-181R), Formula (I-181R) synthesized by the methods described in Comparative Examples 1 to 14. (I-211R), Formula (I-241R), Formula (I-1R2), Formula (I-2R2), Formula (I-121R2), Formula (I-151R2), Formula (I-181R2), Formula (I-181R2) It is considered that a trace amount of impurities contained in the compounds represented by the formula (I-211R2) and the formula (I-241R2) influences. Thus, it can be seen that the production method of the present invention has high purity of the obtained compound. In addition, it can be seen that a display element manufactured using the compound manufactured by the manufacturing method of the present invention hardly causes image sticking.

  From the above results, since the production method of the present invention can be produced with a small number of steps and with high purity, the tetrahydropyran-2,5-diyl group or 1,3-dioxane It is useful as a method for producing a compound having a -2,5-diyl group and a 4-alkoxy-2,3-difluorophenyl group. Further, the compound produced by the production method of the present invention is useful as a material for a liquid crystal display device.

Claims (20)

The following partial structure (A), partial structure (AI), partial structure (D) and partial structure (DI)

And one or more groups selected from the groups represented by the following partial structures (Y), partial structures (Y (F, Cl)), partial structures (Y (Cl, F)) and partial structures ( Y (Cl, Cl))

A method for producing a compound (i) having one or more groups selected from the groups represented by the following formulas, wherein the partial structure (A), the partial structure (AI), the partial structure (D) and Compound (ia) having one or more groups selected from the group represented by partial structure (DI), the above partial structure (Y), partial structure (Y (F, Cl)), partial structure Compound (ib) having one or more groups selected from groups represented by (Y (Cl, F)) and partial structure (Y (Cl, Cl)) in the presence of a transition metal catalyst And manufacturing by coupling. Compound (i) has the following general formula (I)

(Wherein, R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, or one —CH ₂ — or two or more non-adjacent —CH ₂ — Represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by -O-, -CH = CH-, -CF = CF- or -C≡C-; May be substituted with a fluorine atom, and A ⁰ represents a group represented by partial structure (A), partial structure (AI), partial structure (D) or partial structure (DI); ^Y is moiety (Y), the partial structure (Y (F, Cl)) , the partial structure (Y (Cl, F)) or a partial structure (Y (Cl, Cl)) represents a group represented by, ^{a 1} , ^A 2, ^{A 3} and ^{A 4} each independently 1,4-phenylene group, 1,4-cyclohexylene group, It represents a tiger tetrahydropyran-2,5-diyl group or 1,3-dioxane-2,5-diyl group, optionally substituted by these groups or is unsubstituted or 1 or more substituents L ¹ When there are a plurality of A ^1, they may be the same or different. When there are a plurality of A ^2, they may be the same or different. When there are a plurality of A ^3, May be the same or different, and when a plurality of A ⁴ are present, they may be the same or different, and L ¹ is a fluorine atom, a chlorine atom, or one —CH ₂ — Two or more non-adjacent —CH ₂ — each having 1 to 20 carbon atoms which may be independently substituted by —O—, —CH ＝ CH—, —CF ＝ CF— or —C≡C— Represents a linear or branched alkyl group of Any hydrogen atom in the group may be substituted by a fluorine ^{atom, Z 1, Z 2, Z} 3 and ^{Z 4} are each independently _{-OCH 2 -, - CH 2 O} -, - CH 2 CH 2 - _{, -COO -, - OCO -,} - CF 2 O -, - OCF 2 -, - CH = CH -, - CF = CF -, - C≡C- or represents a single bond, ^{Z 1} there are a plurality of In those cases, they may be the same or different. When there are a plurality of Z ^2, they may be the same or different. When there are a plurality of Z ^3, they may be the same or different. And when a plurality of Z ⁴ are present, they may be the same or different, and m1, m3 and m4 each independently represent an integer of 0 to 3, and m2 represents an integer of 1 to 3. Where m1 + m2 + m3 + m4 represents an integer of 1 to 3. Wherein the compound (ia) is represented by the following general formula (IA)

(Wherein, R ¹ , A ⁰ , A ¹ , A ² , Z ¹ , Z ² , m1 and m2 represent the same meaning as in the general formula (I), and X ¹ represents a fluorine atom, a chlorine atom, a bromine atom, an iodine Atom, trifluoromethanesulfonyloxy group, methanesulfonyloxy group or group selected from p-toluenesulfonyloxy group or dihydroxyboryl group, linear or branched alkoxyboryl group having 2 to 20 carbon atoms or 1 to carbon atoms 20 represents a group selected from cyclic alkoxyboryl groups.) Wherein the compound (ib) is represented by the following general formula (IB)

(Where A ³ , A ⁴ , A ^Y , Z ³ , Z ⁴ , m 3, m ⁴ and R ² represent the same meaning as in the general formula (I), and X ² represents a fluorine atom, a chlorine atom, a bromine atom, an iodine Atom, trifluoromethanesulfonyloxy group, methanesulfonyloxy group or group selected from p-toluenesulfonyloxy group or dihydroxyboryl group, linear or branched alkoxyboryl group having 2 to 20 carbon atoms or 1 to carbon atoms And X ¹ represents a group selected from a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a trifluoromethanesulfonyloxy group, a methanesulfonyloxy group, and a p-toluenesulfonyloxy group. when referring to, X ² is a dihydroxyboryl group, having 2 to 20 carbon atoms linear or branched Arukokishibo Represents a group or a group selected from cyclic Arukokishiboriru group having a carbon number of 1 to 20, X ¹ is a dihydroxyboryl group, a linear or branched Arukokishiboriru group or a carbon atom number of from 2 to 20 carbon atoms X ² represents a group selected from a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a trifluoromethanesulfonyloxy group, a methanesulfonyloxy group and a p-toluenesulfonyloxy group when representing a group selected from 20 cyclic alkoxyboryl groups. The production method according to claim 1, wherein the compound is represented by the following formula: Compound (i) is represented by the following general formula (Ii)

(In the formula, R ¹¹ and R ²¹ are each independently one -CH ₂ -or two or more non-adjacent -CH ₂ -are each independently -O-, -CH = CH-,- CF = CF- or may be substituted by -C≡C-, arbitrary hydrogen atom in the radicals represents a linear alkyl group having from good 1 -C be substituted by a fluorine atom 10, a ⁰¹ Is the following formula (A0-i-1) or formula (A0-i-2)

A ¹¹ , A ²¹ , A ³¹ and A ⁴¹ are each independently a group represented by the following formulas (A-i-1) to (A-i-9)

(Wherein L ¹¹ is a fluorine atom, a chlorine atom, or a carbon atom in which one —CH ₂ — may be replaced by —O—, and any hydrogen atom in the group may be replaced by a fluorine atom. Represents a straight-chain alkyl group having 1 to 6 atoms.) When a plurality of A ¹¹ are present, they may be the same or different, and when a plurality of A ²¹ is present, they may be the same or different and if the a ³¹ there are a plurality thereof may be the same or different and they if a ⁴¹ there are a plurality optionally be the same or different Z ¹¹ , Z ²¹ , Z ³¹ and Z ⁴¹ each independently represent -OCH _2- , -CH ₂ O-, -CH ₂ CH _2- , -COO-, -OCO-, -CF ₂ O- , -OCF ₂ - or represents a single ^{bond, Z 11} is They If the number present may be the same or different and they if Z ²¹ there are a plurality may be the same or different and they if Z ³¹ there are a plurality in the same When a plurality of Z ⁴¹ are present, they may be the same or different, and m11, m31 and m41 each independently represent 0, 1 or 2, and m21 represents 1 or 2 Where m11 + m21 + m31 + m41 represents 1, 2 or 3. Wherein the compound (ia) is represented by the following general formula (IA-i)

(Wherein, R ¹¹ , A ⁰¹ , A ¹¹ , A ²¹ , Z ¹¹ , Z ²¹ , m11 and m21 represent the same meaning as in the general formula (Ii), and X ¹¹ represents a chlorine atom, a bromine atom, an iodine atom Or a group selected from a trifluoromethanesulfonyloxy group or a dihydroxyboryl group, a linear or branched alkoxyboryl group having 2 to 5 carbon atoms, or a cyclic alkoxyboryl group having 1 to 10 carbon atoms. Wherein the compound (ib) is represented by the following general formula (IB-i)

(Wherein, A ³¹ , A ⁴¹ , Z ³¹ , Z ⁴¹ , m31, m41 and R ²¹ represent the same meaning as in the general formula (I-i), and X ²¹ represents a chlorine atom, a bromine atom, an iodine atom or trifluoromethane. X ¹¹ represents a group selected from a sulfonyloxy group or a dihydroxyboryl group, a linear or branched alkoxyboryl group having 2 to 5 carbon atoms or a cyclic alkoxyboryl group having 1 to 10 carbon atoms; Represents a group selected from a chlorine atom, a bromine atom, an iodine atom or a trifluoromethanesulfonyloxy group, X ²¹ represents a dihydroxyboryl group, a linear or branched alkoxyboryl group having 2 to 5 carbon atoms or a carbon atom number; X ¹¹ represents a group selected from cyclic alkoxyboryl groups having 1 to 10; X ¹¹ represents a dihydroxyboryl group; X ²¹ represents a group selected from a chlorine atom, a bromine atom, an iodine atom or a trifluoromethanesulfonyloxy group when representing a group selected from a chain or branched alkoxyboryl group or a cyclic alkoxyboryl group having 1 to 10 carbon atoms. The method according to claim 1, wherein the compound is a compound represented by the following formula: Compound (i) has the following general formula (Ii-111)

(Wherein, R ¹¹¹¹¹ represents a linear alkyl group having 1 to 5 carbon atoms or a linear alkenyl group having 2 to 5 carbon atoms, and R ²¹¹¹¹ represents a linear alkoxy group having 1 to 5 carbon atoms.) Or a linear alkenyloxy group having 2 to 5 carbon atoms), wherein the compound (ia) is represented by the following general formula (IA-i-111)

(Wherein, R ¹¹¹¹¹ has the same meaning as in formula (I-i-111), and X ¹¹¹¹¹ represents a group selected from a chlorine atom, a bromine atom and an iodine atom). (Ib) has the following general formula (IB-i-111)

(Wherein, R ²¹¹¹¹ represents the same meaning as in the general formula ( ^Ii -111), and X ²¹¹¹¹ represents a dihydroxyboryl group or 4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2- The compound according to any one of claims 1 to 3, which is a compound represented by the following formula: Compound (i) has the following general formula (I-i-112)

(Wherein, R ¹¹¹¹² represents a linear alkyl group having 1 to 5 carbon atoms or a linear alkenyl group having 2 to 5 carbon atoms, and R ²¹¹¹² represents a linear alkoxy group having 1 to 5 carbon atoms. Or a linear alkenyloxy group having 2 to 5 carbon atoms.) Wherein the compound (ia) is represented by the following general formula (IA-i-112)

(Wherein, R ¹¹¹¹² has the same meaning as in formula (I-i-112), and X ¹¹¹¹² represents a group selected from a chlorine atom, a bromine atom and an iodine atom.) (Ib) has the following general formula (IB-i-112)

(Wherein, R ²¹¹¹² represents the same meaning as in general formula (I-i-112), and X ²¹¹¹² represents a dihydroxyboryl group or 4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2- The compound according to any one of claims 1 to 3, which is a compound represented by the following formula: Compound (i) has the following general formula (Ii-113)

(Wherein, R ¹¹¹¹³ represents a linear alkyl group or linear alkenyl group having 2 to 5 carbon atoms having 1 to 5 carbon atoms, R ²¹¹¹³ is a straight chain alkoxy group having 1 to 5 carbon atoms Or a linear alkenyloxy group having 2 to 5 carbon atoms.) Wherein the compound (ia) is represented by the following general formula (IA-i-113)

( ^Wherein R ¹¹¹¹³ has the same meaning as in formula (I-i-113), and X ¹¹¹¹³ represents a group selected from a chlorine atom, a bromine atom and an iodine atom). (Ib) has the following general formula (IB-i-113)

(Wherein, R ²¹¹¹³ represents the same meaning as in general formula (I-i-113), and X ²¹¹¹³ represents a dihydroxyboryl group or 4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2- The compound according to any one of claims 1 to 3, which is a compound represented by the following formula: Compound (i) has the following general formula (I-i-114)

(Wherein, R ¹¹¹¹⁴ represents a linear alkyl group having 1 to 5 carbon atoms or a linear alkenyl group having 2 to 5 carbon atoms, and R ²¹¹¹⁴ represents a linear alkoxy group having 1 to 5 carbon atoms.) Or a linear alkenyloxy group having 2 to 5 carbon atoms), wherein the compound (ia) is represented by the following general formula (IA-i-114)

(Wherein, R ¹¹¹¹⁴ represents the same meaning as in formula (I-i-114), and X ¹¹¹¹⁴ represents a group selected from a chlorine atom, a bromine atom and an iodine atom). (Ib) has the following general formula (IB-i-114)

( ^Wherein , R ²¹¹¹⁴ represents the same meaning as in general formula (I-i-114), and X ²¹¹¹⁴ represents a dihydroxyboryl group or 4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2- The compound according to any one of claims 1 to 3, which is a compound represented by the following formula: Compound (i) has the following general formula (Ii-115)

(Wherein, R ¹¹¹¹⁵ represents a linear alkyl group having 1 to 5 carbon atoms or a linear alkenyl group having 2 to 5 carbon atoms, and R ²¹¹¹⁵ represents a linear alkoxy group having 1 to 5 carbon atoms. Or a linear alkenyloxy group having 2 to 5 carbon atoms), wherein the compound (ia) is represented by the following general formula (IA-i-115)

(Wherein, R ¹¹¹¹⁵ represents the same meaning as in formula (I-i-115), and X ¹¹¹¹⁵ represents a group selected from a chlorine atom, a bromine atom and an iodine atom.) (Ib) has the following general formula (IB-i-115)

(Wherein, R ²¹¹¹⁵ represents the same meaning as in the general formula ( ^Ii -115), and X ²¹¹¹⁵ represents a dihydroxyboryl group or 4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2- The compound according to any one of claims 1 to 3, which is a compound represented by the following formula:   A compound having one or more groups selected from the groups represented by partial structure (A), partial structure (AI), partial structure (D) and partial structure (DI) according to claim 1 ( ia), a partial structure (Y), a partial structure (Y (F, Cl)), a partial structure (Y (Cl, F)) and a group represented by the partial structure (Y (Cl, Cl)) A mixture containing a compound (ib) having one or more groups to be obtained and a transition metal compound.   9. A production method, wherein the compound produced by the production method according to any one of claims 1 to 8 is purified using silica gel.   A production method characterized by purifying a compound produced by the production method according to any one of claims 1 to 8 or 10 by recrystallization.   12. A step of removing an organic solvent from a mixture containing the compound and the organic solvent produced by the production method according to any one of claims 1 to 8, 10, and 11 by concentrating the mixture under reduced pressure. The manufacturing method characterized by including.   The production according to any one of claims 1 to 8, wherein the compound (ib) is added to a mixture containing the compound (ia) and the transition metal compound. Method.   A composition comprising the compound (i) produced by the production method according to any one of claims 1 to 8 and 10 to 13. The compound (i) produced by the production method according to any one of claims 1 to 8, and claims 10 to 13, and the following general formula (X1)

(Wherein, R ³ and R ⁴ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, or one —CH ₂ — or two or more non-adjacent —CH ₂ — —O—, —CH ＝ CH—, —CF ＝ CF— or —C≡C— represents a linear alkyl group having 1 to 6 carbon atoms which may be substituted by any one of the alkyl groups. The hydrogen atom may be substituted by a fluorine atom, and A ⁵ and A ⁶ each independently represent a 1,4-phenylene group or a 1,4-cyclohexylene group, but these groups are unsubstituted or It may be substituted by one or more substituents L ^X1 , and when there are a plurality of A ^5, they may be the same or different, and when there are a plurality of A ^6, they may be the same or different L ^X1 represents a fluorine atom, Z ⁵ and Z -OCH ₂ ⁶ are each independently _{-, - CH 2 O -,} - CH 2 CH 2 -, - CF 2 O -, - OCF 2 -, - C≡C- or represents a single bond, is ^{Z 5} When a plurality of Z ⁶ are present, they may be the same or different. When a plurality of Z ⁶ exist, they may be the same or different, and m5 and m6 are each independently an integer of 0 to 3. Wherein m5 + m6 represents an integer of 0 to 3.). A compound (i) produced by the production method according to any one of claims 1 to 8, and claims 10 to 13, and a compound represented by the following general formula (X2)

(Wherein, R ⁵ and R ⁶ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, or one —CH ₂ — or two or more non-adjacent —CH ₂ — —O—, —CH ＝ CH—, —CF ＝ CF— or —C≡C— represents a linear alkyl group having 1 to 6 carbon atoms which may be substituted by any one of the alkyl groups. The hydrogen atom may be substituted by a fluorine atom, and A ⁷ and A ⁸ each independently represent a 1,4-phenylene group or a 1,4-cyclohexylene group, but these groups are unsubstituted or It may be substituted by one or more substituents L ^X2 , and when A ⁷ is present in plurals, they may be the same or different, L ^X2 represents a fluorine atom, and Z ⁷ represents —OCH ₂ —. _{, -CH 2 O -, - CH} 2 CH 2 -, - CF 2 O -, - It represents OCF ₂ —, —C≡C— or a single bond, and when a plurality of Z ⁷ are present, they may be the same or different, and m 7 each independently represents an integer of 0 to 3. The composition according to claim 14 or 15, comprising a compound represented by the formula: The compound (i) produced by the production method according to any one of claims 1 to 8, and claims 10 to 13, and the following general formula (X3)

(Wherein, R ⁷ is each independently a hydrogen atom, or one -CH ₂ -or two or more non-adjacent -CH ₂ -are each independently -O-, -COO-,- OCO -, - CH = CH - , - CF = CF- or -C≡C- represents a linear or branched alkyl group having 25 good 1 -C be replaced by, ^{a 9} is 1,4 Represents a phenylene group, a 1,4-cyclohexylene group or a 1,3-dioxane-2,5-diyl group, these groups being unsubstituted or substituted by one or more substituents L ^X3 It is good, if the a ⁹ there are a plurality thereof may be different even in the same, L ^X3 is fluorine atom, or one -CH 2 _- not adjacent two or more -CH ₂ - Each independently has 1 to 20 carbon atoms which may be substituted by -O-. Represents a linear or branched alkyl group, ^{Z 8} is _{-OCH 2 -, - CH 2 O} -, - CH 2 CH 2 -, - COO -, - OCO -, - COO-CH 2 CH 2 -, - Represents OCO-CH ₂ CH ₂ —, —CH ₂ CH ₂ —COO—, —CH ₂ CH ₂ —OCO— or a single bond, and when a plurality of Z ⁸ are present, they may be the same or different And m8 independently represents an integer of 0 to 3.) The compound of any one of claims 14 to 16.   An n-type liquid crystal material comprising the composition according to any one of claims 14 to 17.   A display element using the composition or the n-type liquid crystal material according to any one of claims 14 to 17.   20. A personal computer, a smartphone, a television, a monitor, a drone, a digital signage, an electronic blackboard, a home appliance, a vending machine using the composition according to any one of claims 14 to 19, an n-type liquid crystal material or a display element. , Ticket vending machines, ticket gates, portable equipment, control equipment, manufacturing equipment, automatic teller machines, cash registers, car navigation systems, game machines, decorative equipment, stage equipment, on-board monitors, transport equipment, automobiles, railways, linear motor cars , Aircraft, ships and spacecraft.