JP7214497B2 - Method for producing cyclic compound - Google Patents

Description

The present invention relates to a method for producing a cyclic compound.

Organic electroluminescent elements (hereinafter also referred to as "light-emitting elements") can be suitably used for display and lighting applications. In recent years, materials for organic electroluminescent elements with long life and high luminous efficiency Development is in full swing.

A cyclic compound (hereinafter referred to as a cyclic compound) formed by connecting divalent aromatic hydrocarbon groups is expected as a material for a light-emitting device. A cyclic compound is obtained, for example, by reducing a precursor cyclic compound. Cyclic compounds are produced, for example, by cross-coupling raw material compounds in the presence of a transition metal complex, an inorganic base and a solvent (Non-Patent Documents 1 and 2).

J. Org. Chem. 2012, 77, 6624-6628 J. Am. Chem. Soc. 2011, 133, 15800-15802

However, in the above reaction, the yield of the target cyclic compound is not sufficient. Accordingly, an object of the present invention is to provide a method for obtaining a cyclic compound in high yield.

The present inventors have made intensive studies to solve the above problems, and as a result, have found that the yield of the cyclic compound is greatly improved by using an organic base as the base, and have completed the present invention. rice field.

That is, the present invention provides the following [1] to [8].

［式（Ｍ－１）中、ｍ′は、５以上１５以下の整数を表す。
Ａｒ^ａは、アリーレン基、２価の複素環基、又はシクロアルカジエンが有する２つのｓｐ^３炭素から水素原子を１個ずつ除いた基を表し、これらの基は置換基を有していてもよい。前記置換基が複数存在する場合、それらは互いに結合して、それぞれが結合する原子とともに環を形成していてもよい。複数存在するＡｒ^ａは、同一でも異なっていてもよい。但し、Ａｒ^ａの少なくとも一つは、シクロアルカジエンが有する２つのｓｐ^３炭素から水素原子を１個ずつ除いた基を表し、該基は置換基を有していてもよい。
Ｚ^１は、反応性基を表す。複数存在するＺ^１は、同一でも異なっていてもよい。］

［式（Ｍ－２）中、ｎ′は、１以上１０以下の整数を表す。
Ａｒ^ｂは、アリーレン基、２価の複素環基、又はシクロアルカジエンが有する２つのｓｐ^３炭素から水素原子を１個ずつ除いた基を表し、これらの基は置換基を有していてもよい。前記置換基が複数存在する場合、それらは互いに結合して、それぞれが結合する原子とともに環を形成していてもよい。Ａｒ^ｂが複数存在する場合、Ａｒ^ｂは同一でも異なっていてもよい。
Ｚ^２は、反応性基を表す。複数存在するＺ^２は、同一でも異なっていてもよい。］

［式（Ｍ）中、Ａｒ^ａ、Ａｒ^ｂ、ｍ′及びｎ′は前記Ａｒ^ａ、Ａｒ^ｂ、ｍ′及びｎ′と同じ意味を表す。]
［２］前記Ｚ^１及び前記Ｚ^２が、それぞれ独立に置換基Ａ群及び置換基Ｂ群からなる群から選ばれる基である、［１］に記載の輪状化合物の製造方法。
＜置換基Ａ群＞
塩素原子、臭素原子、ヨウ素原子、－Ｏ－Ｓ(＝Ｏ)_２Ｒ^Ｃ１（式中、Ｒ^Ｃ１は、アルキル基、シクロアルキル基又はアリール基を表し、これらの基は置換基を有していてもよい。）で表される基。
＜置換基Ｂ群＞
－Ｂ(ＯＲ^Ｃ２)_２（式中、Ｒ^Ｃ２は、水素原子、アルキル基、シクロアルキル基又はアリール基を表し、水素原子以外のこれらの基は置換基を有していてもよい。複数存在するＲ^Ｃ２は同一でも異なっていてもよく、互いに結合して、それぞれが結合する酸素原子と共に環構造を形成していてもよい。）で表される基。］
［３］前記有機塩基が第四級アンモニウム塩である、［１］又は［２］に記載の輪状化合物の製造方法。
［４］前記工程１を、前記遷移金属錯体、前記有機塩基及び配位子の存在下で行う、［１］～［３］のいずれか一項に記載の輪状化合物の製造方法。
［５］前記式（Ｍ－１）で表される化合物が、式（Ｍ－１Ａ）で表される化合物である、［１］～［４］のいずれかに一項に記載の輪状化合物の製造方法。

［式（Ｍ－１Ａ）中、Ｚ^１は前記Ｚ^１と同じ意味を表す。
ｍ、ｎ及びｉは、それぞれ独立に１以上の整数を表す。複数存在する、ｍ、ｎ及びｉは同一でも異なっていてもよい。
Ａｒ^ａ１及びＡｒ^ａ２は、それぞれ独立に単環若しくは縮合環のアリーレン基、又は単環若しくは縮合環の２価の複素環基を表し、これらの基は置換基を有していてもよい。複数存在するＡｒ^ａ１及びＡｒ^ａ２は同一でも異なっていてもよい。
Ｒ^Ａは、水酸基、アルコキシ基、シクロアルコキシ基、アリールオキシ基又は１価の複素環基を表し、これらの基は置換基を有していてもよい。複数存在するＲ^Ａは同一でも異なっていてもよい。
Ｅ^ａ及びＥ^ｂは、それぞれ独立に、水素原子、アルケニル基、シクロアルケニル基、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基、アリールオキシ基、１価の複素環基又は置換アミノ基を表し、水素原子以外のこれらの基は置換基を有していてもよい。複数存在するＥ^ａ及びＥ^ｂは、同一でも異なっていてもよく、互いに結合して、それぞれが結合する炭素原子とともに環を形成していてもよい。]
［６］前記式（Ｍ－２）で表される化合物が、式（Ｍ－２Ａ）で表される化合物である、［１］～［５］のいずれか一項に記載の輪状化合物の製造方法。

［式（Ｍ－２Ａ）中、Ｒ^Ａ、及びＺ^２は前記Ｒ^Ａ、及びＺ^２と同じ意味を表す。
ｋ、ｌ及びｊは、それぞれ独立に、０以上の整数を表す。但し、ｋ＋ｌは１以上の整数を表す。複数存在するｋ及びｊは、同一でも異なっていてもよい。
Ａｒ^ａ３及びＡｒ^ａ４は、それぞれ独立に、単環若しくは縮合環のアリーレン基、単環若しくは縮合環の２価の複素環基を表し、これらの基は置換基を有していてもよい。Ａｒ^ａ３が複数存在する場合、Ａｒ^ａ３は同一でも異なっていてもよい。複数存在するＡｒ^ａ４は同一でも異なっていてもよい。
Ｅ^ｃ及びＥ^ｄは、それぞれ独立に、水素原子、アルケニル基、シクロアルケニル基、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基、アリールオキシ基、１価の複素環基又は置換アミノ基を表し、水素原子以外のこれらの基は置換基を有していてもよい。複数存在する前記Ｅ^ｃ及びＥ^ｄは、同一でも異なっていてもよく、互いに結合して、それぞれが結合する炭素原子とともに環を形成していてもよい。]
［７］前記Ａｒ^ａ、Ａｒ^ｂ、Ａｒ^ａ１、Ａｒ^ａ２、Ａｒ^ａ３及びＡｒ^ａ４が置換基を有していてもよいアリーレン基である、［６］に記載の輪状化合物の製造方法。
［８］［１］～［７］のいずれか一項に記載の製造方法で得られた輪状化合物に対して還元反応を施す工程を備える、式（Ｍ′）で表される環状化合物の製造方法。

［式（Ｍ′）中、ｍ′及びｎ′は、前記ｍ′及びｎ′と同じ意味を表す。
Ａｒ^Ａ及びＡｒ^Ｂは、それぞれ独立に、単環若しくは縮合環のアリーレン基又は単環若しくは縮合環の２価の複素環基を表し、これらの基は置換基を有していてもよい。複数存在するＡｒ^Ａは、同一でも異なっていてもよい。Ａｒ^Ｂが複数存在する場合、Ａｒ^Ｂは同一でも異なっていてもよい。] [1] in the presence of a transition metal complex and an organic base,
Including step 1 of reacting a compound represented by formula (M-1) with a compound represented by formula (M-2),
A method for producing a cyclic compound represented by formula (M).

[In the formula (M-1), m′ represents an integer of 5 or more and 15 or less.
Ar ^a represents an arylene group, a divalent heterocyclic group, or a group obtained by removing one hydrogen atom from each of the two sp ³ carbons of cycloalkadiene, and these groups may have a substituent good. When there are multiple substituents, they may be bonded together to form a ring together with the atoms to which they are bonded. A plurality of Ar ^a may be the same or different. However, at least one of Ar ^a represents a group obtained by removing one hydrogen atom from each of two sp ³ carbons of cycloalkadiene, and the group may have a substituent.
Z ¹ represents a reactive group. A plurality of Z ¹ may be the same or different. ]

[In the formula (M-2), n′ represents an integer of 1 or more and 10 or less.
Ar ^b represents an arylene group, a divalent heterocyclic group, or a group obtained by removing one hydrogen atom from each of the two sp ³ carbons of cycloalkadiene, and these groups may have a substituent good. When there are multiple substituents, they may be bonded together to form a ring together with the atoms to which they are bonded. When multiple Ar ^b are present, the Ar ^b may be the same or different.
^Z2 represents a reactive group. A plurality of Z ² may be the same or different. ]

[In the formula (M), Ar ^a , Ar ^b , m′ and n′ have the same meaning as the above Ar ^a , Ar ^b , m′ and n′. ]
[2] The method for producing a cyclic compound according to [ ¹ ], wherein said Z1 and said Z2 ^are each independently a group selected from the group consisting of substituent group A and substituent group B.
<Substituent Group A>
chlorine atom, bromine atom, iodine atom, —O—S(=O) ₂ R ^C1 (wherein R ^C1 represents an alkyl group, a cycloalkyl group or an aryl group, and these groups have substituents; may be used.).
<Substituent Group B>
—B(OR ^C2 ) ₂ (In the formula, R ^C2 represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and these groups other than a hydrogen atom may have a substituent. R ^{2 C2} may be the same or different, and may be bonded to each other to form a ring structure together with the oxygen atoms to which they are bonded.). ]
[3] The method for producing a cyclic compound according to [1] or [2], wherein the organic base is a quaternary ammonium salt.
[4] The method for producing a cyclic compound according to any one of [1] to [3], wherein the step 1 is performed in the presence of the transition metal complex, the organic base and the ligand.
[5] The cyclic compound according to any one of [1] to [4], wherein the compound represented by formula (M-1) is a compound represented by formula (M-1A). Production method.

[In formula (M-1A), Z ¹ has the same meaning as Z ¹ described above.
m, n and i each independently represent an integer of 1 or more. Multiple m, n and i may be the same or different.
Ar ^a1 and Ar ^a2 each independently represent a monocyclic or condensed ring arylene group or a monocyclic or condensed ring divalent heterocyclic group, and these groups may have a substituent. A plurality of Ar ^a1 and Ar ^a2 may be the same or different.
^RA represents a hydroxyl group, an alkoxy group, a cycloalkoxy group, an aryloxy group or a monovalent heterocyclic group, and these groups may have a substituent. Multiple ^RAs may be the same or different.
E ^a and E ^b are each independently a hydrogen atom, an alkenyl group, a cycloalkenyl group, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, or a substituted It represents an amino group, and these groups other than hydrogen atoms may have a substituent. A plurality of E ^a and E ^b may be the same or different, and may be bonded to each other to form a ring together with the carbon atoms to which they are bonded. ]
[6] Production of the cyclic compound according to any one of [1] to [5], wherein the compound represented by formula (M-2) is a compound represented by formula (M-2A). Method.

[In formula (M-2A), R ^A and Z ² have the same meanings as R ^A and Z ² described above.
k, l and j each independently represent an integer of 0 or more. However, k+l represents an integer of 1 or more. Multiple k and j may be the same or different.
Ar ^a3 and Ar ^a4 each independently represent a monocyclic or condensed ring arylene group or a monocyclic or condensed ring divalent heterocyclic group, and these groups may have a substituent. When multiple Ar ^a3 are present, the Ar ^a3 may be the same or different. A plurality of Ar ^a4 may be the same or different.
E ^c and E ^d are each independently a hydrogen atom, an alkenyl group, a cycloalkenyl group, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, or a substituted It represents an amino group, and these groups other than hydrogen atoms may have a substituent. A plurality of E ^c and E ^d may be the same or different, and may be bonded to each other to form a ring together with the carbon atoms to which they are bonded. ]
[7] The method for producing a cyclic compound according to [6], wherein the A ^a , Ar ^b , A ^a1 , A ^a2 , A ^a3 and A ^a4 are optionally substituted arylene groups.
[8] Production of a cyclic compound represented by formula (M′), comprising a step of subjecting the cyclic compound obtained by the production method according to any one of [1] to [7] to a reduction reaction. Method.

[In the formula (M'), m' and n' have the same meaning as the above m' and n'.
Ar 1 ^A and Ar 2 ^B each independently represent a monocyclic or condensed-ring arylene group or a monocyclic or condensed-ring divalent heterocyclic group, and these groups may have a substituent. A plurality of Ar ^A may be the same or different. When two or more Ar ^B are present, Ar ^B may be the same or different. ]

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the cyclic compound which can be manufactured with high yield can be provided. Moreover, preferred embodiments of the present invention further reduce the reaction time. Moreover, according to the present invention, it is possible to provide a method for producing a cyclic compound that can be produced at a high yield.

Preferred embodiments of the present invention are described in detail below.

<Description of common terms>
Terms commonly used in this specification have the following meanings unless otherwise specified.

A "cyclic compound" is a precursor for producing a cyclic compound and means a compound before a reduction reaction of the cyclic compound.

A "cyclic compound" represents a cyclic compound formed by connecting divalent aromatic hydrocarbon groups.

Me is a methyl group, Et is an ethyl group, Bu is a butyl group, i-Pr is an isopropyl group, and t-Bu is a tert-butyl group.

A hydrogen atom may be a deuterium atom or a protium atom.

In the formulas representing metal complexes, solid lines representing bonds between ligands and metals mean ionic bonds, covalent bonds or coordinate bonds.

The "alkyl group" may be either linear or branched. The number of carbon atoms in the linear alkyl group is generally 1-50, preferably 3-30, more preferably 4-20, not including the number of carbon atoms in the substituents. The number of carbon atoms in the branched alkyl group is generally 3-50, preferably 3-30, more preferably 4-20, not including the number of carbon atoms in the substituent.

The alkyl group may have a substituent, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, 2-butyl group, isobutyl group, tert-butyl group, pentyl group, isoamyl group, 2-ethylbutyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, 3-propylheptyl group, decyl group, 3,7-dimethyloctyl group, 2-ethyloctyl group, 2-hexyldecyl group, dodecyl group , and groups in which hydrogen atoms in these groups are substituted with cycloalkyl groups, alkoxy groups, cycloalkoxy groups, aryl groups, fluorine atoms, etc. (e.g., trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group , perfluorohexyl group, perfluorooctyl group, 3-phenylpropyl group, 3-(4-methylphenyl)propyl group, 3-(3,5-di-hexylphenyl)propyl group, 6-ethyloxyhexyl group) is mentioned.

The number of carbon atoms in the "cycloalkyl group" is usually 3 to 50, preferably 3 to 30, more preferably 4 to 20, not including the number of carbon atoms in substituents.

A cycloalkyl group may have a substituent, and examples thereof include a cyclohexyl group, a methylcyclohexyl group, and an ethylcyclohexyl group.

An "aryl group" means an atomic group remaining after removing one hydrogen atom directly bonded to a carbon atom constituting a ring from an aromatic hydrocarbon. The number of carbon atoms in the aryl group is generally 6-60, preferably 6-20, more preferably 6-10, not including the number of carbon atoms in the substituents.

The aryl group may have a substituent, for example, a phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, 1-pyrenyl group, 2 -pyrenyl group, 4-pyrenyl group, 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, 2-phenylphenyl group, 3-phenylphenyl group, 4-phenylphenyl group, and hydrogen atoms in these groups includes groups substituted with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a fluorine atom, or the like.

An "alkoxy group" may be either linear or branched. The straight-chain alkoxy group usually has 1 to 40 carbon atoms, preferably 4 to 10 carbon atoms, not including the carbon atoms of the substituents. The number of carbon atoms in the branched alkoxy group is usually 3-40, preferably 4-10, not including the number of carbon atoms in the substituents.

The alkoxy group may have a substituent, for example, a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butyloxy group, an isobutyloxy group, a tert-butyloxy group, a pentyloxy group, a hexyloxy group, A heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, a 3,7-dimethyloctyloxy group, a lauryloxy group, and hydrogen atoms in these groups are cycloalkyl groups, alkoxy groups, A cycloalkoxy group, an aryl group, a group substituted with a fluorine atom or the like can be mentioned.

The number of carbon atoms in the "cycloalkoxy group" is usually 3-40, preferably 4-10, not including the number of carbon atoms in the substituents.

A cycloalkoxy group may have a substituent, such as a cyclohexyloxy group.

The number of carbon atoms in the "aryloxy group" is usually 6-60, preferably 6-48, not including the number of carbon atoms in the substituents.

The aryloxy group may have a substituent, for example, phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 1-anthracenyloxy group, 9-anthracenyloxy group, 1- Pyrenyloxy groups and groups in which hydrogen atoms in these groups are substituted with alkyl groups, cycloalkyl groups, alkoxy groups, cycloalkoxy groups, fluorine atoms and the like are included.

A "p-valent heterocyclic group" (p represents an integer of 1 or more) refers to, from a heterocyclic compound, p hydrogen atoms directly bonded to the carbon atoms or heteroatoms constituting the ring. means the remaining atomic groups excluding the hydrogen atoms of Among p-valent heterocyclic groups, it is an atomic group remaining after removing p hydrogen atoms among the hydrogen atoms directly bonded to the carbon atoms or heteroatoms constituting the ring from the aromatic heterocyclic compound. A "p-valent aromatic heterocyclic group" is preferred.

“Aromatic heterocyclic compounds” include heterocyclic compounds such as oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinoline, carbazole, and dibenzophosphole. Compounds in which the ring itself exhibits aromaticity, and heterocycles such as phenoxazine, phenothiazine, dibenzoborol, dibenzosilole, benzopyran, etc., in which an aromatic ring is condensed even if the heterocycle itself does not exhibit aromaticity means a compound.

The number of carbon atoms in the monovalent heterocyclic group is usually 2-60, preferably 4-20, not including the number of carbon atoms in the substituents.
The monovalent heterocyclic group may have a substituent, for example, thienyl group, pyrrolyl group, furyl group, pyridyl group, piperidinyl group, quinolinyl group, isoquinolinyl group, pyrimidinyl group, triazinyl group, and these and a group in which a hydrogen atom in the group is substituted with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, or the like.

A "halogen atom" means a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The "amino group" may have a substituent, preferably a substituted amino group. As the substituent of the amino group, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group is preferable.
Substituted amino groups include, for example, dialkylamino groups, dicycloalkylamino groups and diarylamino groups.
Examples of amino groups include dimethylamino group, diethylamino group, diphenylamino group, bis(4-methylphenyl)amino group, bis(4-tert-butylphenyl)amino group, bis(3,5-di-tert- butylphenyl)amino group.

An "alkenyl group" may be either linear or branched. The straight-chain alkenyl group usually has 2 to 30 carbon atoms, preferably 3 to 20 carbon atoms, not including the carbon atoms of the substituents. The number of carbon atoms in the branched alkenyl group is usually 3-30, preferably 4-20, not including the number of carbon atoms in the substituents.

The number of carbon atoms in the "cycloalkenyl group" is usually 3-30, preferably 4-20, not including the number of carbon atoms in the substituents.

Alkenyl groups and cycloalkenyl groups may have substituents, for example, vinyl group, 1-propenyl group, 2-propenyl group, 2-butenyl group, 3-butenyl group, 3-pentenyl group, 4- Pentenyl group, 1-hexenyl group, 5-hexenyl group, 7-octenyl group, and groups in which these groups have substituents.

An "alkynyl group" may be either linear or branched. The alkynyl group usually has 2 to 20 carbon atoms, preferably 3 to 20 carbon atoms, not including the carbon atoms of the substituents. The number of carbon atoms in the branched alkynyl group is usually 4-30, preferably 4-20, not including the carbon atoms of the substituents.

The number of carbon atoms in the "cycloalkynyl group" is usually 4-30, preferably 4-20, not including the carbon atoms of the substituents.

Alkynyl groups and cycloalkynyl groups may have substituents, for example, ethynyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, 3-pentynyl group, 4- A pentynyl group, a 1-hexynyl group, a 5-hexynyl group, and groups in which these groups have substituents are included.

An "arylene group" means an atomic group remaining after removing two hydrogen atoms directly bonded to carbon atoms constituting a ring from an aromatic hydrocarbon. The number of carbon atoms in the arylene group is usually 6-60, preferably 6-30, more preferably 6-18, not including the number of carbon atoms in the substituent.

The arylene group may have a substituent, for example, a phenylene group, a biphenyldiyl group, a naphthalenediyl group, an anthracenediyl group, a phenanthenediyl group, a dihydrophenanthenediyl group, a naphthacenediyl group, a fluorenediyl group, and a pyrenediyl group. , a perylenediyl group, a chrysenediyl group, and groups in which these groups have substituents, preferably groups represented by formulas (A-1) to (A-20). The arylene group includes groups in which multiple of these groups are bonded.

［式中、Ｒ及びＲ^aは、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アリール基又は１価の複素環基を表す。複数存在するＲ及びＲ^aは、各々、同一でも異なっていてもよく、Ｒ^a同士は互いに結合して、それぞれが結合する原子と共に環を形成していてもよい。］

[In the formula, R and R ^a each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group. A plurality of R and R ^a may be the same or different, and R ^a may be bonded to each other to form a ring together with the atoms to which they are bonded. ]

The number of carbon atoms in the divalent heterocyclic group is usually 2 to 60, preferably 3 to 20, more preferably 4 to 15, not including the number of carbon atoms in the substituents.

The divalent heterocyclic group may have a substituent, such as pyridine, diazabenzene, triazine, azanaphthalene, diazanaphthalene, carbazole, dibenzofuran, dibenzothiophene, dibenzosilole, phenoxazine, phenothiazine, acridine, dihydroacridine, furan, thiophene, azole, diazole, and triazole, preferably a divalent group excluding two hydrogen atoms among the hydrogen atoms directly bonded to the carbon atoms or heteroatoms constituting the ring. is a group represented by formulas (AA-1) to (AA-34). Divalent heterocyclic groups include groups in which multiple of these groups are bonded.

［式中、Ｒ及びＲ^aは、前記と同じ意味を表す。］

[In the formula, R and R ^a have the same meanings as described above. ]

The “crosslinking group” is a group capable of forming a new bond by subjecting it to heating, ultraviolet irradiation, near-ultraviolet irradiation, visible light irradiation, infrared irradiation, radical reaction, or the like. It is a group represented by any one of formulas (B-1) to (B-17). These groups may have a substituent.

"Substituent" means a halogen atom, a cyano group, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an amino group, a substituted amino group, an alkenyl group. , represents a cycloalkenyl group, an alkynyl group or a cycloalkynyl group, and these groups may further have a substituent. A substituent may be a bridging group. When a plurality of substituents are present, they may bond with each other to form a ring together with the atoms to which they are bonded, but preferably do not form a ring. In the present specification, when it is expressed that a certain group may have a substituent, it means that the group may have at least one group listed as the substituent. do.

(embodiment)
A method for producing a compound according to one embodiment of the present invention comprises reacting a compound represented by the formula (M-1) with a compound represented by the formula (M-2) in the presence of a transition metal complex and an organic base. A method for producing a compound represented by formula (M), comprising a step 1 of causing

The number of carbon atoms in the monocyclic arylene group in Ar ^a and Ar ^b is preferably 6, not including the number of carbon atoms in the substituents. The monocyclic arylene groups in Ar ^a and Ar ^b are preferably phenylene groups, more preferably groups represented by formulas (A-1) to (A-3), further preferably It is a group represented by formula (A-1).

The number of carbon atoms in the condensed ring arylene group in Ar ^a and Ar ^b is usually 7 to 60, not including the number of carbon atoms in the substituents. The number of carbon atoms in the condensed ring arylene group in Ar ^a and Ar ^b is preferably 8-40, more preferably 9-30, still more preferably 10-20. The condensed ring arylene group for Ar ^a and Ar ^b includes, for example, a naphthalenediyl group, anthracenediyl group, a phenanthenediyl group, a dihydrophenanthrenediyl group, a naphthacenediyl group, a fluorenediyl group, a spirobifluorenediyl group, and a pyrenediyl group. , a perylene diyl group or a chrysenediyl group. The condensed ring arylene group in Ar ^a and Ar ^b is preferably a phenylene group, a naphthalenediyl group, an anthracenediyl group, a fluorenediyl group, a pyrenediyl group, a perylenediyl group, or a chrysenediyl group, more preferably naphthalenediyl. group, anthracenediyl group or pyrenediyl group, more preferably naphthalenediyl group or pyrenediyl group, particularly preferably a group represented by formula (A-4) or formula (A-14), The group may have a substituent.

The number of carbon atoms in the monocyclic divalent heterocyclic group in Ar ^a and Ar ^b is preferably 2 to 5, not including the number of carbon atoms in the substituents. The monocyclic divalent heterocyclic group in Ar ^a and Ar ^b is directly bonded to a ring-constituting carbon atom or heteroatom from, for example, pyridine, diazabenzene, triazine, furan, thiophene, azole, diazole or triazole. divalent groups in which two hydrogen atoms are removed from among the hydrogen atoms in the group. These groups may have a substituent.

The number of carbon atoms in the condensed divalent heterocyclic group in Ar ^a and Ar ^b is usually 2 to 60, not including the number of carbon atoms in the substituents. The condensed divalent heterocyclic group for Ar ^a and Ar ^b includes, for example, azanaphthalene, diazanaphthalene, carbazole, dibenzofuran, dibenzothiophene, dibenzosilole, phenoxazine, phenothiazine, acridine or dihydroacridine. Divalent groups in which two hydrogen atoms are removed from the hydrogen atoms directly bonded to the constituent carbon atoms or heteroatoms are included. These groups may have a substituent.

The number of carbon atoms in the group obtained by removing one hydrogen atom from each of the two sp ³ carbons of the monocyclic cycloalkadiene in Ar ^a and Ar ^b is preferably 6, not including the number of carbon atoms in the substituent. be. The group obtained by removing one hydrogen atom each from two sp ³ carbon atoms of the monocyclic cycloalkadiene in Ar ^a and Ar ^b is preferably a group represented by formula (AA-01). This group may have a substituent.

[式中、Ｒ^Ａは、水酸基、アルコキシ基、シクロアルコキシ基、アリールオキシ基又は１価の複素環基を表し、これらの基は置換基を有していてもよい。複数存在するＲ^Ａは、同一でも異なっていてもよい。]

[In the formula, ^RA represents a hydroxyl group, an alkoxy group, a cycloalkoxy group, an aryloxy group or a monovalent heterocyclic group, and these groups may have a substituent. Multiple ^RAs may be the same or different. ]

The number of carbon atoms in the group obtained by removing one hydrogen atom from each of the two sp ³ carbons of the condensed ring cycloalkadiene in Ar ^a and Ar ^b is usually 7 to 60, not including the number of carbon atoms in substituents. is. A group obtained by removing one hydrogen atom from each of the two sp ³ carbons of the condensed ring cycloalkadiene in Ar ^a and Ar ^b is preferably represented by formulas (AA-02) to (AA-04). is a group. These groups may have a substituent.

[式中、Ｒ^Ａは前記Ｒ^Ａと同じ意味を表す。]

[In the formula, ^RA has the same meaning as ^RA above. ]

The substituents that Ar ^a and Ar ^b may have are preferably halogen atoms, alkyl groups, cycloalkyl groups, alkoxy groups, cycloalkoxy groups, aryl groups, monovalent heterocyclic groups or substituted amino groups. is. The substituent that Ar ^a and Ar ^b may have is more preferably an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a substituted amino group, more preferably an alkyl group, It is a cycloalkyl group or an aryl group. These groups may further have a substituent.

Since the synthesis of the cyclic compound represented by formula (M) is facilitated, when there are a plurality of substituents that may be possessed by Ar ^a and Ar ^b , they are bonded to each other and together with the atoms to which they are bonded, the ring It is preferred not to form

Ar ^a and Ar ^b are preferably monocyclic or condensed ring arylene groups because they facilitate the synthesis of the cyclic compound represented by formula (M). good.

m′ is preferably 7 or more and 13 or less, more preferably 7 or more and 11 or less, still more preferably 9 or more and 11 or less, because it facilitates the synthesis of the cyclic compound represented by formula (M). It is below.

n′ is preferably 1 or more and 8 or less, more preferably 1 or more and 5 or less, still more preferably 1 or more and 3, because it facilitates the synthesis of the cyclic compound represented by formula (M). It is below. n' may be smaller than m'.

Z ¹ and Z ² may each independently be a group selected from the group consisting of the substituent group A and the substituent group B. When Z ¹ is a group selected from the above substituent group A, Z ² is preferably a group selected from the above substituent group B. Moreover, when Z ¹ is a group selected from the above substituent group B, Z ² is preferably a group selected from the above substituent group A.

A group selected from Substituent Group A is preferably a bromine atom, an iodine atom or a group represented by —OS(=O) ₂ R ^C1 .

The group represented by -B(OR ^C2 ) ₂ includes, for example, groups represented by formulas (W-1) to (W-10).

<Compounds Represented by Formula (M-1A) and Formula (M-1B)>
The compound represented by the formula (M-1) is preferably the compound represented by the formula (M-1A), since it facilitates the synthesis of the cyclic compound represented by the formula (M).

Ar ^a1 and Ar ^a2 are preferably monocyclic or condensed ring arylene groups because they facilitate the synthesis of the cyclic compound represented by formula (M). good.

Examples and preferred ranges of the monocyclic or condensed-ring arylene group for Ar ^a1 and Ar ^a2 are the same as those for the monocyclic or condensed-ring arylene group for Ar ^a and Ar ^b .

m is preferably 1 or more and 4 or less, more preferably 2 or more and 4 or less, still more preferably 2, since the yield of the cyclic compound represented by formula (M) is improved. Multiple m's are preferably the same.

n is preferably 1 or more and 4 or less, more preferably 1 or more and 2 or less, still more preferably 1, because the yield of the cyclic compound represented by formula (M) is improved. A plurality of n's are preferably the same.

i is preferably 1 because it improves the yield of the cyclic compound represented by formula (M). A plurality of i's are preferably the same.

R ^A is preferably a hydroxyl group, an alkoxy group, a cycloalkoxy group or an aryloxy group, more preferably a hydroxyl group or an alkoxy group, because it facilitates the synthesis of the cyclic compound represented by the formula (M). and more preferably an alkoxy group.

E ^a and E ^b are preferably hydrogen atoms or bonded to each other to form a ring together with the carbon atom to which they are bonded, since this facilitates the synthesis of the cyclic compound represented by formula (M). , and more preferably a hydrogen atom.

The compound represented by formula (M-1A) is preferably the compound represented by formula (M-1B), since the yield of the cyclic compound represented by formula (M) is improved.

［式（Ｍ－１Ｂ）中、ｍ、ｎ、ｉ、Ａｒ^ａ１、Ａｒ^ａ２、Ｒ^Ａ及びＺ^１は前記ｍ、ｎ、ｉ、Ａｒ^ａ１、Ａｒ^ａ２、Ｒ^Ａ及びＺ^１と同じ意味を表す。]

[In the formula (M-1B), m, n, i, Ar ^a1 , Ar ^a2 , R ^A and Z ¹ have the same meanings as the above m, n, i, Ar ^a1 , Ar ^a2 , R ^A and Z ¹ . ]

<Compounds Represented by Formula (M-2A) and Formula (M-2B)>
The compound represented by formula (M-2) is preferably the compound represented by formula (M-2A), since the compound represented by formula (M) can be easily synthesized.

Ar ^a3 and Ar ^a4 are preferably monocyclic or condensed ring arylene groups, since this facilitates the synthesis of the cyclic compound represented by formula (M). good.

Examples and preferred ranges of the monocyclic or condensed-ring arylene group for Ar ^a3 and Ar ^a4 are the same as those for the monocyclic or condensed-ring arylene group for Ar ^a and Ar ^b .

k is preferably 0 or more and 2 or less, more preferably 0 or 1, still more preferably 0, since the yield of the cyclic compound represented by formula (M) is improved. Multiple k's are preferably the same.

l is preferably 1 or more and 3 or less, more preferably 1 or 2, still more preferably 1, since the yield of the cyclic compound represented by formula (M) is improved.

j is preferably 0 or 1 because the yield of the cyclic compound represented by formula (M) is improved. A plurality of j's are preferably the same.

E ^c and E ^d are preferably hydrogen atoms or bonded to each other to form a ring together with the carbon atom to which they are bonded, since this facilitates the synthesis of the cyclic compound represented by formula (M). .

The compound represented by formula (M-2A) is preferably the compound represented by formula (M-2B), since the yield of the cyclic compound represented by formula (M) is improved.

［式中、ｋ、ｌ、ｊ、Ａｒ^ａ３、Ａｒ^ａ４、Ｒ^Ａ及びＺ^２は前記ｋ、ｌ、ｊ、Ａｒ^ａ３、Ａｒ^ａ４、Ｒ^Ａ及びＺ^２と同じ意味を表す。]

[In the formula, k, l, j, A ^a3 , A ^a4 , R ^A and Z ² have the same meanings as k, l, j, A ^a3 , A ^a4 , R ^A and Z ² . ]

<Cyclic Compound Represented by Formula (M′)>
A cyclic compound represented by the formula (M') can be synthesized by reducing the compound represented by the formula (M).

Ar 1 ^A and Ar 2 ^B are preferably monocyclic or condensed ring arylene groups, since this facilitates the synthesis of the cyclic compound represented by formula (M′). good too.

Examples and preferred ranges of the monocyclic or condensed-ring arylene group in Ar ^A and Ar ^B are the same as those of the monocyclic or condensed-ring arylene group in Ar ^a and Ar ^b .

Examples of the cyclic compound represented by the formula (M′) produced using the cyclic compound represented by the formula (M) are represented by formulas (1A-01) to (1A-33). compound.

<Method for Producing Compound Represented by Formula (M)>
A more detailed method for producing the compound represented by formula (M) will be described. As the compound represented by formula (M-1), the compound represented by formula (M-1-1) is used, and as the cyclic compound represented by formula (M), compound (M-1-2) is used. A manufacturing method will be described as an example. The compound represented by formula (M-1-2) is, for example, a compound represented by formula (M-1-1) and a compound represented by formula (M-2) in the presence of a transition metal complex and an organic base. It can be synthesized by the following scheme using the compound obtained.

［式中、Ａｒ^ｂ、Ｒ^Ａ、Ｚ^１、及びｎ’は、前記Ａｒ^ｂ、Ｒ^Ａ、Ｚ^１、及びｎ’と同じ意味を表す。］

[wherein ^{Ar b} , RA , Z ¹ and n′ have the same meanings as the above Ar ^b , ^RA , Z ¹ and n′ . ]

(Step 1)
In step 1, the compound represented by the formula (M-1-1) is prepared, for example, by J. Org. Chem. 2012, 77, 6624-6628 and J. Am. Chem. Soc. It can be synthesized by the method described in et al.

In step 1, the amount of the compound represented by formula (M-2) used is preferably 0.8 to 2.0 to the total amount of the compound represented by formula (M-1-1). It is 0 molar equivalents, more preferably 0.9 to 1.5 molar equivalents, still more preferably 0.9 to 1.1 molar equivalents.

In step 1, the transition metal complex is preferably a palladium complex. Palladium complexes include, for example, [tris(dibenzylideneacetone)]dipalladium, bis(dibenzylideneacetone)palladium, dichlorobis(triphenylphosphine)palladium, dichlorobis(tris-o-methoxyphenylphosphine)palladium, palladium chloride, acetic acid palladium, bis(benzonitrile)dichloropalladium, [tetrakis(triphenylphosphine)]palladium. The transition metal complexes are preferably [tris(dibenzylideneacetone)]dipalladium, palladium acetate, dichlorobis(triphenylphosphine)palladium, dichlorobis(tris-o-methoxyphenylphosphine)palladium, [tetrakis(triphenylphosphine)] Palladium. The transition metal complex is more preferably [tris(dibenzylideneacetone)]dipalladium, palladium acetate, dichlorobis(triphenylphosphine)palladium, dichlorobis(tris-o-methoxyphenylphosphine)palladium, and more preferably [ tris(dibenzylideneacetone)]dipalladium and palladium acetate, and particularly preferred is [tris(dibenzylideneacetone)]dipalladium.

The amount of the transition metal complex used is preferably 0.00001 to 3 molar equivalents, more preferably 0.00005, relative to the total amount of substances of the compound represented by formula (M-1-1). to 1 molar equivalent, more preferably 0.0001 to 0.5 molar equivalent. A transition metal complex may be used individually by 1 type, or may use 2 or more types together.

In step 1, the transition metal complex may be used by mixing with a ligand such as a phosphine ligand. Phosphine ligands include, for example, 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, (4-dimethylaminophenyl) Di-tert-butylphosphine, 2-(di-tert-butylphosphino)biphenyl, 2-(dicyclohexylphosphino)-2'-(dimethylamino)biphenyl, dicyclohexyl (2',4',6'-triisopropyl -3,6-dimethoxy-[1,1′-biphenyl]-2-yl)phosphine, 2-dicyclohexylphosphino-2′,6′-diisopropoxybiphenyl, triphenylphosphine, tri-o-tolylphosphine, Tri-tert-butylphosphine, tricyclohexylphosphine, and di-tert-butylphenylphosphine. The phosphine ligand is preferably 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl.

In step 1, the amount of the ligand used is preferably 0.5 to 20 molar equivalents, preferably 1 to 10 molar equivalents, more preferably 1 to 5 molar equivalents. A ligand may be used individually by 1 type, or may use 2 or more types together.

In step 1, the organic base is preferably a quaternary ammonium salt. The quaternary ammonium salt is preferably a compound represented by formula (X).

［式（Ｘ）中、Ｒ^ｍは、置換基を有していてもよいアルキル基を表す。複数存在するＲ^ｍは、同一でも異なっていてもよい。]

[In the formula (X), R ^m represents an optionally substituted alkyl group. Multiple R ^m may be the same or different. ]

R ^m is preferably an ethyl group or a butyl group, more preferably a butyl group, since it improves the yield of the cyclic compound represented by formula (M).

Examples of compounds represented by formula (X) include tetrabutylammonium hydroxide, tetraethylammonium hydroxide, and tetramethylammonium hydroxide. The compound represented by formula (X) is preferably tetrabutylammonium hydroxide or tetraethylammonium hydroxide, more preferably tetrabutylammonium hydroxide.

The amount of the organic base used is preferably 0.1 to 30 molar equivalents, more preferably 0.5 to It is 20 molar equivalents, more preferably 1 to 10 molar equivalents. An organic base may be used individually by 1 type, or may use 2 or more types together.

In step 1, the organic base may be used as it is, but is preferably used as an aqueous solution. In step 1, the proportion of water when the organic base is used as an aqueous solution is generally preferably 1 to 500 parts by mass, more preferably 5 to 200 parts by mass, and more preferably 5 to 200 parts by mass relative to 1 part by mass of the organic base. It is preferably 10 to 100 parts by mass. When the proportion of water is 1 to 500 parts by weight per 1 part by weight of the organic base, the reaction time of step 1 is shortened and the yield of the desired cyclic compound is increased.

In step 1, the reaction is preferably carried out in a solvent. In step 1, the solvent includes, for example, alcoholic solvents such as methanol, ethanol, propanol, ethylene glycol, glycerin, 2-methoxyethanol and 2-ethoxyethanol; diethyl ether, tetrahydrofuran (THF), dioxane, cyclopentyl methyl ether and ether solvents such as diglyme; halogen solvents such as methylene chloride and chloroform; nitrile solvents such as acetonitrile and benzonitrile; hydrocarbon solvents such as hexane, decalin, toluene, xylene and mesitylene; Amide solvents such as N,N-dimethylacetamide; acetone, dimethylsulfoxide, and water.

The amount of the solvent to be used is preferably 1 to 2000 parts by mass, more preferably 50 to 1500 parts by mass, based on 1 part by mass of the compound represented by formula (M-1-1). It is preferably 100 to 1000 parts by mass. A solvent may be used individually by 1 type, or may use 2 or more types together.

In step 1, the reaction temperature is preferably 0°C to 200°C, more preferably 50°C to 150°C.
In step 1, the reaction time is preferably 0.5 hours to 24 hours, more preferably 1 hour to 12 hours, still more preferably 1 hour to 8 hours.

<Method for Producing Compound Represented by Formula (M′)>
A method for producing the compound represented by formula (M') will be described. Using the compound represented by formula (M-1-2) as the cyclic compound represented by formula (M) and producing compound (M-1-3) as the cyclic compound represented by formula (M') How to do this will be explained as an example. The compound represented by formula (M-1-3) can be synthesized, for example, by using the compound represented by formula (M-1-2) according to the following scheme.

In step 2, the compound represented by formula (M-1-3) can be synthesized by aromatizing the compound represented by formula (M-1-2). More specifically, the compound represented by formula (M-1-3) can be synthesized by converting the cyclohexadienyl skeleton portion in the compound represented by formula (M-1-2) to a benzene ring. .

As a method for aromatizing the compound represented by formula (M-1-2), for example, a method of carrying out a reduction reaction and then carrying out an oxidation reaction can be mentioned. For example, by using a reducing agent, ^RA is first eliminated and the hydrogenation reaction proceeds. After that, by performing an oxidation treatment, the cyclohexadienyl skeleton portion is converted to a benzene ring.

In step 2, as the reduction reaction, for example, by using a reducing agent, ^RA is first desorbed and the dehydrogenation reaction proceeds. By subsequently performing an oxidation treatment, the cyclohexadienyl ring portion is converted to a benzene ring.

Examples of the reducing agent used in step 2 include sodium naphthalenide and lithium naphthalenide.

In step 2, the amount of the reducing agent used is generally preferably 1 to 500 molar equivalents, preferably 10 to 300 molar equivalents, more preferably 20 to 200 molar equivalents.

In step 2, the reduction reaction is preferably carried out in a solvent. Examples and preferred ranges of solvents in step 2 are the same as examples and preferred ranges of solvents in step 1. A solvent may be used individually by 1 type, or may use 2 or more types together.

In step 2, the amount of the solvent used is generally 1 to 1000 parts by mass, preferably 10 to 500 parts by mass, based on 1 part by mass of the compound represented by formula (1-1-3). , more preferably 50 to 500 parts by mass.

In step 2, the reaction temperature for the reduction reaction is in the range of -100°C to 0°C.
In step 2, the reaction time for the reduction reaction is 0.5 hours to 24 hours.

The oxidizing agent used in step 2 includes quinones such as chloranil, o-chloranil, 2,3-dichloro-5,6-dicyano-p-benzoquinone, and iodine.

In step 2, the amount of the oxidizing agent used is generally 1 to 500 molar equivalents, preferably 1 to 100 molar equivalents, relative to the total amount of the compound represented by formula (M-1-3). and more preferably 1 to 50 molar equivalents.

In step 2, the oxidation reaction is preferably carried out in a solvent. Examples and preferred ranges of solvents in step 2 are the same as examples and preferred ranges of solvents in step 1. A solvent may be used individually by 1 type, or may use 2 or more types together.

In step 2, the amount of the solvent used is generally 1 to 1000 parts by mass, preferably 10 to 500 parts by mass, based on 1 part by mass of the compound represented by formula (M-1-3). , more preferably 50 to 500 parts by mass.

In step 2, the reaction temperature for the oxidation reaction is in the range of -100°C to 0°C.
In step 2, the reaction time for the oxidation reaction is 0.5 hours to 24 hours.

The compounds, catalysts and solvents used in each reaction described in <Method for Producing Cyclic Compound> may be used alone or in combination of two or more.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples.

LC-MS was measured by the following method.
A measurement sample was dissolved in chloroform or tetrahydrofuran to a concentration of about 2 mg/mL, and about 1 μL was injected into an LC-MS (manufactured by Agilent, trade names: 1290 Infinity LC and 6230 TOF LC/MS). The mobile phase for LC-MS was acetonitrile and tetrahydrofuran with varying ratios and flowed at a flow rate of 1.0 mL/min. The column used was SUMIPAX ODS Z-CLUE (manufactured by Sumika Chemical Analysis Service, inner diameter: 4.6 mm, length: 250 mm, particle size: 3 µm).

NMR was measured by the following method.
5 to 10 mg of a measurement sample was added to about 0.5 mL of heavy chloroform (CDCl ₃ ), heavy tetrahydrofuran, heavy dimethylsulfoxide, heavy acetone, heavy N,N-dimethylformamide, heavy toluene, heavy methanol, heavy ethanol, heavy 2-propanol. Alternatively, it was dissolved in methylene dichloride and measured using an NMR apparatus (manufactured by Agilent, trade name: INOVA300, or manufactured by JEOL RESONANCE, trade name: JNM-ECZ400S/L1). Trimethylsilane was used as an internal standard.

High performance liquid chromatography (HPLC) area percentage values were used as an index of compound purity. Unless otherwise specified, this value is a value based on the absorbance for ultraviolet light with a wavelength of 254 nm using HPLC (manufactured by Shimadzu Corporation, trade name: LC-20A). At this time, the compound to be measured was dissolved in tetrahydrofuran or chloroform to a concentration of 0.01 to 0.2% by mass, and 1 to 10 μL of the solution was injected into the HPLC depending on the concentration. Acetonitrile/tetrahydrofuran was used as the mobile phase for HPLC while changing the ratio from 100/0 to 0/100 (volume ratio), and flowed at a flow rate of 1.0 mL/min. The column used was SUMIPAX ODS Z-CLUE (manufactured by Sumika Chemical Analysis Service, inner diameter: 4.6 mm, length: 250 mm, particle size: 3 μm) or an ODS column with equivalent performance. A photodiode array detector (manufactured by Shimadzu Corporation, trade name: SPD-M20A) was used as the detector.

<Synthesis Example 1> Synthesis of compound EM-01

After creating a nitrogen gas atmosphere in the reaction vessel, 4-methoxyphenol (15.5 g) and methanol (311 mL) were added, and the mixture was stirred at room temperature (25° C., hereinafter the same) for 30 minutes. After that, the mixture was cooled to 0°C, iodobenzene diacetate (40.0 g) was added, and the mixture was stirred at 0°C for 3 hours. After that, the temperature of the obtained reaction solution was raised to room temperature, then an aqueous potassium hydroxide solution and dichloromethane were added, and the mixture was stirred at room temperature. After that, the aqueous layer was separated, and the organic layer was washed with deionized water. Anhydrous magnesium sulfate was added to the resulting organic layer, followed by filtration and concentration to obtain compound EM-01 (19.1 g). The HPLC area percentage value of compound EM-01 was 95.0% or more.

¹ H-NMR (CD ₂ Cl ₂ , 400 MHz): δ (ppm) = 3.36 (6H, s), 6.27 (2H, d), 6.82 (2H, d)

<Synthesis Example 2> Synthesis of compound EM-02

After creating a nitrogen gas atmosphere in the reaction vessel, 1,4-dibromobenzene (34.0 g) and tetrahydrofuran (386 mL) were added, and the mixture was cooled to -70°C. After that, n-butyllithium (1.6 mol/L hexane solution) (86 mL) was added dropwise over 30 minutes. After that, compound EM-01 (19.1 g) was added and stirred at -70°C for 2 hours. Thereafter, methanol was added dropwise, and the resulting reaction solution was warmed to room temperature, acetic acid and acetone were added, and the mixture was stirred at room temperature for 1 hour. After that, ion-exchanged water and ethyl acetate were added, and the mixture was stirred at room temperature. After that, the aqueous layer was separated, and the organic layer was washed with deionized water. After adding anhydrous magnesium sulfate to the obtained organic layer, the mixture was filtered and concentrated to obtain a solid. The resulting solid was washed with hexane to obtain compound EM-02 (23.0 g). The HPLC area percentage value of compound EM-02 was 93.0% or more.

1H ^- NMR _{( CD2Cl2} , 400MHz): 2.45 (1H, s), 6.25 (2H, d), 6.86 (2H, d), 7.36 (2H, d), 7.52 (2H, d)

<Synthesis Example 3> Synthesis of compound EM-03

After creating a nitrogen gas atmosphere in the reaction vessel, 1-bromo-4-chlorobenzene (49.0 g) and tetrahydrofuran (600 mL) were added, and the mixture was cooled to -70°C. After that, n-butyllithium (1.6 M hexane solution) (156 mL) was added dropwise over 1 hour. After that, compound EM-02 (20.0 g) was added and stirred at -70°C for 2 hours. Thereafter, methanol was added dropwise, and the resulting reaction solution was warmed to room temperature, ion-exchanged water and ethyl acetate were added, and the mixture was stirred at room temperature. After that, the aqueous layer was separated, and the organic layer was washed with deionized water. Anhydrous magnesium sulfate was added to the resulting organic layer, followed by filtration and concentration to obtain compound EM-03 (24.0 g).

LC-MS (ESI, positive): m/z=376[M] ⁺

<Synthesis Example 4> Synthesis of compound EM-04

After creating a nitrogen gas atmosphere in the reaction vessel, sodium hydride (60% by mass, dispersed in liquid paraffin) (6.4 g) and tetrahydrofuran (400 mL) were added and cooled to 0°C. After that, a solution of compound EM-03 (20.0 g) dissolved in tetrahydrofuran (100 mL) was added dropwise, and the mixture was stirred at 0° C. for 30 minutes. After that, methyl iodide (37.5 g) was added and stirred at 45°C for 14 hours. Ion-exchanged water and ethyl acetate were added, and the mixture was stirred at room temperature. After that, the aqueous layer was separated, and the organic layer was washed with deionized water. After adding anhydrous magnesium sulfate to the obtained organic layer, the mixture was filtered and concentrated to obtain a solid. The resulting solid was crystallized using 2-propanol and dried at 50° C. under reduced pressure to obtain compound EM-04 (11.4 g). The HPLC area percentage value of compound EM-04 was 99.0% or more.

1H ^- NMR (CD2Cl2, 400MHz): 3.39 (6H, s), 6.08 (4H, s), _{7.24-7.32 (} 6H, m), 7.44 (2H, d)

<Synthesis Example 5> Synthesis of compound EM-06

Compound EM-05 was synthesized according to the method described in Non-Patent Document 1 and Non-Patent Document 2.

After making the inside of the reaction vessel a nitrogen gas atmosphere, compound EM-05 (8.0 g), bis(pinacolato)diboron (9.9 g), palladium acetate (80 mg), 2-dicyclohexylphosphino-2′,4′, 6′-Triisopropylbiphenyl (339 mg), potassium acetate (6.9 g) and 1,2-dimethoxyethane (120 mL) were added and stirred at 80° C. for 4 hours. Thereafter, the obtained reaction solution was cooled to room temperature and then filtered through a filter covered with celite. After that, toluene and ion-exchanged water were added, and the aqueous layer was separated. The organic layer was washed with ion-exchanged water, anhydrous magnesium sulfate and activated carbon were added to the obtained organic layer, and the mixture was filtered and concentrated to obtain a solid. The resulting solid was crystallized using a mixed solvent of toluene and acetonitrile, and dried at 50° C. under reduced pressure to obtain compound EM-06 (6.9 g). The HPLC area percentage value of compound EM-06 was 99.5% or more.

¹ H-NMR (CD ₂ Cl ₂ , 400 MHz): δ(ppm) = 3.41 (3H, s), 6.08 (2H, s), 7.37 (2H, d), 7.69 (2H, d)

<Synthesis Example 6> Synthesis of compound EM-07

After making the inside of the reaction vessel a nitrogen gas atmosphere, compound EM-04 (8.1 g), compound EM-06 (5.4 g), toluene (270 mL), mesylate [(di(1-adamantyl)-n-butyl Phosphine)-2-(2′-amino-1,1′-biphenyl)]palladium (36 mg) and 20 mass % tetrabutylammonium hydroxide aqueous solution (64 g) were added, and the mixture was stirred at 90° C. for 3 hours. Thereafter, the obtained reaction solution was cooled to room temperature and then filtered through a filter covered with celite. After the resulting filtrate was washed with ion-exchanged water, the resulting organic layer was dried over anhydrous magnesium sulfate and filtered. A solid was obtained by concentrating the obtained filtrate under reduced pressure. The resulting solid was purified by silica gel column chromatography (mixed solvent of hexane and ethyl acetate) and dried at 50° C. under reduced pressure to obtain compound EM-07 (6.7 g). The HPLC area percentage value of compound EM-07 was 97.0% or higher.

¹ H-NMR (CD ₂ Cl ₂ , 400 MHz): δ (ppm) = 3.42 (9H, s), 6.05 (2H, d), 6.13 (4H, d), 7.28 (2H, d), 7.36 (2H, d), 7.43 (2H, d), 7.49 (2H, d), 7.56 (4H, d)

<Synthesis Example 7> Synthesis of compound EM-08

After making the inside of the reaction vessel a nitrogen gas atmosphere, compound EM-07 (6.5 g), bis(pinacolato)diboron (3.8 g), palladium acetate (46 mg), 2-dicyclohexylphosphino-2′,4′, 6′-Triisopropylbiphenyl (197 mg), potassium acetate (2.8 g) and 1,2-dimethoxyethane (195 mL) were added and stirred at 80° C. for 5 hours. Thereafter, the obtained reaction solution was cooled to room temperature and then filtered through a filter covered with celite. After that, toluene and ion-exchanged water were added, and the aqueous layer was separated. The organic layer was washed with ion-exchanged water, anhydrous magnesium sulfate and activated carbon were added to the obtained organic layer, and the mixture was filtered and concentrated to obtain a solid. The resulting solid was crystallized using a mixed solvent of toluene and acetonitrile, and dried at 50° C. under reduced pressure to obtain compound EM-08 (6.5 g). The HPLC area percentage value of compound EM-08 was 99.0% or more.

¹ H-NMR (CD ₂ Cl ₂ , 400 MHz): δ (ppm) = 3.45 (9H, s), 6.11-6.15 (6H, m), 7.41-7.49 (6H, m), 7.55 (4H, m), 7.70 (2H,d)

<Synthesis Example 8> Synthesis of compound EM-09

After creating a nitrogen gas atmosphere in the reaction vessel, 1,4-dibromobenzene (29.8 g) and tetrahydrofuran (250 mL) were added, and the mixture was cooled to -70°C. After that, n-butyllithium (1.6 mol/L hexane solution) (77 mL) was added dropwise over 1 hour. After that, 1,4-naphthoquinone (5.0 g) was added and stirred at -70°C for 2 hours. Thereafter, methanol was added dropwise, and the resulting reaction solution was warmed to room temperature, ion-exchanged water and ethyl acetate were added, and the mixture was stirred at room temperature. After that, the aqueous layer was separated, and the organic layer was washed with deionized water. Anhydrous magnesium sulfate was added to the resulting organic layer, followed by filtration and concentration to obtain compound EM-09 (14.9 g).

LC-MS (ESI, positive): m/z=470[M] ⁺

<Synthesis Example 9> Synthesis of compound EM-10

After creating a nitrogen gas atmosphere in the reactor, sodium hydride (60%, dispersed in liquid paraffin) (3.3 g) and tetrahydrofuran (264 mL) were added and cooled to 0°C. After that, a solution of compound EM-09 (13.2 g) dissolved in tetrahydrofuran (66 mL) was added dropwise, and the mixture was stirred at 0° C. for 30 minutes. After that, methyl iodide (19.8 g) was added and stirred at 45°C for 14 hours. Ion-exchanged water and ethyl acetate were added, and the mixture was stirred at room temperature. After that, the aqueous layer was separated, and the organic layer was washed with deionized water. After adding anhydrous magnesium sulfate to the obtained organic layer, the mixture was filtered and concentrated to obtain a solid. The resulting solid was crystallized using a mixed solvent of toluene and 2-propanol, and dried at 50° C. under reduced pressure to obtain compound EM-10 (8.1 g). The HPLC area percentage value of compound EM-10 was 99.0% or more.

¹ H-NMR (CD ₂ Cl ₂ , 400 MHz): δ(ppm) = 3.16 (3H, s), 6.09 (1H, s), 7.16 (2H, d), 7.37 (4H, m)

<Example 1> Synthesis of compound EM-11

After making the inside of the reaction vessel a nitrogen gas atmosphere, compound EM-08 (500 mg), compound EM-10 (218 mg), toluene (250 mL), [tris(dibenzylideneacetone)] dipalladium (9.5 mg), 2- Dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (14.3 mg) and 2 mass % tetrabutylammonium hydroxide aqueous solution (16.9 g) were added and stirred at 90° C. for 3 hours. Thereafter, the obtained reaction solution was cooled to room temperature and then filtered through a filter covered with celite. As a result of analyzing the organic layer by HPLC (high performance liquid chromatography), it was found that the desired product, EM-11, was produced in a yield of 87%. After the obtained filtrate was washed with ion-exchanged water, the obtained organic layer was dried with anhydrous magnesium sulfate and activated carbon, and filtered. A solid was obtained by concentrating the obtained filtrate under reduced pressure. The resulting solid was crystallized using a mixed solvent of toluene and 2-propanol, and dried at 50° C. under reduced pressure to obtain compound EM-11 (390 mg). The HPLC area percentage value of compound EM-11 was 96.0% or more and the yield was 74%.

¹ H-NMR (CD ₂ Cl ₂ , 400 MHz): δ(ppm) = 3.17 (3H, s), 3.40 (9H, s), 6.10 (7H, m), 7.35-7.46 (18H, m)
LC-MS (ESI, positive): m/z=1210[M] ⁺

<Example 2> Synthesis of compound EM-13

After making the inside of the reaction vessel a nitrogen gas atmosphere, compound EM-08 (500 mg), 1,4-dibromonaphthalene (123 mg), toluene (250 mL), [tris(dibenzylideneacetone)]dipalladium (9.5 mg), 2-Dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (14.3 mg) and 2% by mass aqueous tetrabutylammonium hydroxide solution (16.9 g) were added and stirred at 90° C. for 3 hours. Thereafter, the obtained reaction solution was cooled to room temperature and then filtered through a filter covered with celite. As a result of analyzing the organic layer by HPLC (high performance liquid chromatography), it was found that the desired product, EM-13, was produced in a yield of 88%. After the obtained filtrate was washed with ion-exchanged water, the obtained organic layer was dried with anhydrous magnesium sulfate and activated carbon, and filtered. A solid was obtained by concentrating the obtained filtrate under reduced pressure. The resulting solid was crystallized using a mixed solvent of toluene and 2-propanol, and dried at 50° C. under reduced pressure to obtain compound EM-13 (360 mg). The HPLC area percentage value of compound EM-13 was 96.0% or more and the yield was 84%.

¹ H-NMR (CD ₂ Cl ₂ , 400 MHz): δ(ppm) = 3.40-3.51 (9H, m), 6.07-6.26 (6H, m), 7.40-7.60 (15H, m)
LC-MS (ESI, positive): m/z=996[M] ⁺

<Example 3> Synthesis of compound EM-15

After making the inside of the reaction vessel a nitrogen gas atmosphere, compound EM-08 (500 mg), 1,6-dibromopyrene (155 mg), toluene (250 mL), [tris(dibenzylideneacetone)] dipalladium (9.5 mg), 2-Dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (14.3 mg) and 2% by mass aqueous tetrabutylammonium hydroxide solution (16.9 g) were added and stirred at 90° C. for 3 hours. Thereafter, the obtained reaction solution was cooled to room temperature and then filtered through a filter covered with celite. As a result of analyzing the organic layer by HPLC (high performance liquid chromatography), the desired product, EM-15, was produced in a yield of 79%. After the obtained filtrate was washed with ion-exchanged water, the obtained organic layer was dried with anhydrous magnesium sulfate and activated carbon, and filtered. A solid was obtained by concentrating the obtained filtrate under reduced pressure. The resulting solid was crystallized using a mixed solvent of toluene and 2-propanol, and dried at 50° C. under reduced pressure to obtain compound EM-15 (330 mg). The HPLC area percentage value of compound EM-15 was 95.0% or more and the yield was 70%.

¹ H-NMR (CD ₂ Cl ₂ , 400 MHz): δ (ppm) = 3.27-3.54 (9H, m), 6.02-6.28 (6H, m), 7.37-7.55 (13H, m), 7.98-8.20 (3H , m)
LC-MS (ESI, positive): m/z=1070[M] ⁺

<Example 4> Synthesis of compound EM-16

After making the inside of the reaction vessel a nitrogen gas atmosphere, compound EM-08 (200 mg), 2,7-dibromopyrene (62 mg), toluene (100 mL), [tris(dibenzylideneacetone)]dipalladium (3.8 mg), 2-Dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (5.7 mg) and 2 mass % aqueous tetrabutylammonium hydroxide solution (16.9 g) were added, and the mixture was stirred at 90° C. for 3 hours. Thereafter, the obtained reaction solution was cooled to room temperature and then filtered through a filter covered with celite. As a result of analyzing the organic layer by HPLC (high performance liquid chromatography), the desired product, EM-16, was produced in a yield of 91%. After the obtained filtrate was washed with ion-exchanged water, the obtained organic layer was dried with anhydrous magnesium sulfate and activated carbon, and filtered. A solid was obtained by concentrating the obtained filtrate under reduced pressure. The resulting solid was crystallized using a mixed solvent of toluene and 2-propanol, and dried at 50° C. under reduced pressure to obtain compound EM-16 (135 mg). The HPLC area percentage value of compound EM-16 was 95.0% or more and the yield was 72%.

1H ^- NMR (CD2Cl2, 400MHz): _{3.23-3.51 (} 9H, m), 6.07-6.14 (4H, m), 6.28-6.31 (2H, m), 7.26 (2H, d), 7.37-7.56 (10H, m), 7.81 (2H, d), 8.15 (2H, s), 8.40 (2H, s)
LC-MS (ESI, positive): m/z=1070[M] ⁺

<Example 5> Synthesis of compound EM-17

After making the inside of the reaction vessel a nitrogen gas atmosphere, compound EM-08 (500 mg), 1,4-dibromobenzene (101 mg), toluene (250 mL), [tris(dibenzylideneacetone)]dipalladium (9.5 mg), 2-Dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (14.3 mg) and 2% by mass aqueous tetrabutylammonium hydroxide solution (16.9 g) were added and stirred at 90° C. for 3 hours. Thereafter, the obtained reaction solution was cooled to room temperature and then filtered through a filter covered with celite. As a result of analyzing the organic layer by HPLC (high performance liquid chromatography), it was found that the desired product, EM-17, was produced in a yield of 89%. After the obtained filtrate was washed with ion-exchanged water, the obtained organic layer was dried with anhydrous magnesium sulfate and activated carbon, and filtered. A solid was obtained by concentrating the obtained filtrate under reduced pressure. The resulting solid was crystallized using a mixed solvent of toluene and 2-propanol, and dried at 50° C. under reduced pressure to obtain compound EM-17 (315 mg). The HPLC area percentage value of compound EM-17 was 96.0% or more and the yield was 77%.

LC-MS (ESI, positive): m/z=946[M] ⁺

<Comparative Example 1> Synthesis of compound EM-11

After making the inside of the reaction vessel a nitrogen gas atmosphere, compound EM-08 (500 mg), compound EM-10 (218 mg), toluene (250 mL), [tris(dibenzylideneacetone)] dipalladium (9.5 mg), 2- Dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (14.3 mg), methyltri-n-octylammonium chloride (66 mg) as a phase transfer catalyst and 5% by mass sodium carbonate aqueous solution were added and stirred at 90° C. for 12 hours. Thereafter, the obtained reaction solution was cooled to room temperature and then filtered through a filter covered with celite. As a result of analyzing the organic layer by HPLC (high performance liquid chromatography), the desired product, EM-11, was produced in a yield of 52%. After the obtained filtrate was washed with ion-exchanged water, the obtained organic layer was dried with anhydrous magnesium sulfate and activated carbon, and filtered. A solid was obtained by concentrating the obtained filtrate under reduced pressure. The resulting solid was crystallized using silica gel column chromatography (mixed solvent of hexane and ethyl acetate) and a mixed solvent of toluene and 2-propanol, and then dried under reduced pressure at 50°C to obtain compound EM-11 ( 171 mg). The HPLC area percentage value of compound EM-11 was 96.0% or more and the yield was 33%.

<Comparative Example 2> Synthesis of compound EM-17

After making the inside of the reaction vessel a nitrogen gas atmosphere, compound EM-08 (500 mg), 1,4-dibromobenzene (101 mg), toluene (250 mL), [tris(dibenzylideneacetone)]dipalladium (9.5 mg), 2-Dicyclohexylphosphino-2',6'-dimethoxybiphenyl (14.3 mg), methyltri-n-octylammonium chloride (66 mg) as a phase transfer catalyst and 5 wt% sodium carbonate aqueous solution were added and stirred at 90°C for 12 hours. bottom. Thereafter, the obtained reaction solution was cooled to room temperature and then filtered through a filter covered with celite. As a result of analyzing the organic layer by HPLC (high performance liquid chromatography), the desired product, EM-17, was produced in a yield of 55%. After the obtained filtrate was washed with ion-exchanged water, the obtained organic layer was dried with anhydrous magnesium sulfate and activated carbon, and filtered. A solid was obtained by concentrating the obtained filtrate under reduced pressure. The resulting solid was crystallized using silica gel column chromatography (mixed solvent of hexane and ethyl acetate) and a mixed solvent of toluene and 2-propanol, and then dried under reduced pressure at 50°C to obtain compound EM-17 ( 138 mg). The HPLC area percentage value of compound EM-17 was 96.0% or more and the yield was 34%.

<Comparative Example 3> Synthesis of compound EM-17

After making the inside of the reaction vessel a nitrogen gas atmosphere, compound EM-08 (500 mg), 1,4-dibromobenzene (101 mg), toluene (250 mL), [tris(dibenzylideneacetone)]dipalladium (9.5 mg), 2-Dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (14.3 mg) and 5 mass % sodium carbonate aqueous solution were added, and the mixture was stirred at 90° C. for 12 hours. Thereafter, the obtained reaction solution was cooled to room temperature and then filtered through a filter covered with celite. As a result of analyzing the organic layer by HPLC (high performance liquid chromatography), it was found that the desired product, EM-17, was produced in a yield of 38%. After the obtained filtrate was washed with ion-exchanged water, the obtained organic layer was dried with anhydrous magnesium sulfate and activated carbon, and filtered. A solid was obtained by concentrating the obtained filtrate under reduced pressure. The resulting solid was crystallized using silica gel column chromatography (mixed solvent of hexane and ethyl acetate) and a mixed solvent of toluene and 2-propanol, and then dried under reduced pressure at 50°C to obtain compound EM-17 ( 41 mg). The HPLC area percentage value of compound EM-17 was 96.0% or more and the yield was 10%.

<Comparative Example 4> Synthesis of Compound EM-11 After the reaction vessel was filled with a nitrogen gas atmosphere, compound EM-08 (500 mg), 1,4-dibromobenzene (101 mg), N,N-dimethylformamide (125 mL), [Tris(dibenzylideneacetone)]dipalladium (9.5 mg), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (14.3 mg) and 5% by mass potassium phosphate aqueous solution were added, and the mixture was heated at 140° C. for 12 hours. Stirred for an hour. Thereafter, the obtained reaction solution was cooled to room temperature and then filtered through a filter covered with celite. As a result of analyzing the organic layer by HPLC (high performance liquid chromatography), the desired product, EM-11, was produced in a yield of 33%. After the obtained filtrate was washed with toluene and ion-exchanged water, the obtained organic layer was dried with anhydrous magnesium sulfate and activated carbon, and filtered. A solid was obtained by concentrating the obtained filtrate under reduced pressure. The resulting solid was crystallized using silica gel column chromatography (mixed solvent of hexane and ethyl acetate) and a mixed solvent of toluene and 2-propanol, and then dried under reduced pressure at 50°C to obtain compound EM-11 ( 57 mg). The HPLC area percentage value of compound EM-11 was 96.0% or more and the yield was 14%.

<Example 6> Synthesis of compound EM-12

After the inside of the reaction vessel was replaced with a nitrogen gas atmosphere, naphthalene (1.6 g), metallic sodium (346 mg) and tetrahydrofuran (29 mL) were added and stirred at 0°C for 6 hours to prepare a sodium naphthalenide solution.

Subsequently, after the reaction vessel was filled with a nitrogen gas atmosphere, compound EM-11 (198 mg) and tetrahydrofuran (24 mL) were added, and the mixture was cooled to -70°C. After that, the sodium naphthalenide solution prepared earlier was added, and the mixture was stirred at -70°C for 2 hours. After that, iodine was added, the temperature of the obtained reaction solution was raised to room temperature, ion-exchanged water and dichloromethane were added, and the mixture was stirred at room temperature. After that, the aqueous layer was separated, and the organic layer was washed with deionized water. The resulting organic layer was dried with anhydrous magnesium sulfate and activated carbon and filtered. A solid was obtained by concentrating the obtained filtrate under reduced pressure. Further, the resulting solid was washed with methanol to obtain a crude form of compound EM-12.

Subsequently, after the reaction vessel was filled with a nitrogen gas atmosphere, the obtained crude compound EM-12, 2,3-dichloro-5,6-dicyano-p-benzoquinone (107 mg) and chlorobenzene (20 mL) were added. and 70° C. for 5 hours. After that, the resulting reaction solution was cooled to room temperature, ion-exchanged water and dichloromethane were added, and the mixture was stirred at room temperature. After that, the aqueous layer was separated, and the organic layer was washed with deionized water. The resulting organic layer was dried over anhydrous magnesium sulfate and filtered. A solid was obtained by concentrating the obtained filtrate under reduced pressure. The obtained solid was purified by silica gel column chromatography (dichloromethane), further crystallized using a mixed solvent of toluene, 2-propanol and methanol, and dried under reduced pressure at 50° C. to obtain compound EM-12. (36 mg) was obtained. The HPLC area percentage value of compound EM-12 was greater than 97.0%.

LC-MS (ESI, positive): m/z=962[M] ⁺

The maximum peak wavelength of the emission spectrum of compound EM-12 was 468 nm.

<Example 7> Synthesis of compound EM-14

After the inside of the reaction vessel was replaced with a nitrogen gas atmosphere, naphthalene (0.7 g), metallic sodium (149 mg) and tetrahydrofuran (10 mL) were added and stirred at 0°C for 6 hours to prepare a sodium naphthalenide solution.

Subsequently, after the reaction vessel was filled with a nitrogen gas atmosphere, compound EM-13 (70 mg) and tetrahydrofuran (10 mL) were added, and the mixture was cooled to -70°C. After that, the sodium naphthalenide solution prepared earlier was added, and the mixture was stirred at -70°C for 2 hours. After that, iodine was added, the temperature of the obtained reaction solution was raised to room temperature, ion-exchanged water and dichloromethane were added, and the mixture was stirred at room temperature. After that, the aqueous layer was separated, and the organic layer was washed with deionized water. The resulting organic layer was dried with anhydrous magnesium sulfate and activated carbon and filtered. A solid was obtained by concentrating the obtained filtrate under reduced pressure. Further, the obtained solid was washed with methanol to obtain a crude form of compound EM-14.

Subsequently, after the reaction vessel was filled with a nitrogen gas atmosphere, the obtained crude compound EM-14, 2,3-dichloro-5,6-dicyano-p-benzoquinone (46 mg) and chlorobenzene (8 mL) were added. , and 70° C. for 4 hours. After that, the resulting reaction solution was cooled to room temperature, ion-exchanged water and dichloromethane were added, and the mixture was stirred at room temperature. After that, the aqueous layer was separated, and the organic layer was washed with deionized water. The resulting organic layer was dried over anhydrous magnesium sulfate and filtered. A solid was obtained by concentrating the obtained filtrate under reduced pressure. The resulting solid was purified by silica gel column chromatography (dichloromethane), crystallized using a mixed solvent of toluene, 2-propanol and methanol, and dried at 50° C. under reduced pressure to give compound EM-14. (12 mg) was obtained. The HPLC area percentage value of compound EM-14 was greater than 96.0%.

LC-MS (ESI, positive): m/z=810[M] ⁺

The maximum peak wavelength of the emission spectrum of compound EM-14 was 474 nm.

Table 1 shows that the product yields produced using the production method of the present invention are excellent.

Claims (6)

In the presence of a palladium complex and a quaternary ammonium salt represented by formula (X) ,
Including step 1 of reacting a compound represented by formula (M-1) with a compound represented by formula (M-2),
A method for producing a cyclic compound represented by formula (M).

[In Formula (X), Rm represents an optionally substituted alkyl group. Multiple R ^m may be the same or different. ]

[In the formula (M-1), m′ represents an integer of 5 or more and 15 or less.
Ar ^a represents an arylene group, a divalent heterocyclic group, or a group obtained by removing one hydrogen atom from each of the two sp ³ carbons of cycloalkadiene, and these groups may have a substituent good. When there are multiple substituents, they may be bonded together to form a ring together with the atoms to which they are bonded. A plurality of Ar ^a may be the same or different. However, at least one of Ar ^a represents a group obtained by removing one hydrogen atom from each of two sp ³ carbons of cycloalkadiene, and the group may have a substituent.
Z ¹ represents a substituent group A consisting of a chlorine atom, a bromine atom and an iodine atom, and -B(OR ^C2 ) ₂ (wherein R ^C2 represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, These groups other than a hydrogen atom may have a substituent, and multiple R ^{2 C2} may be the same or different, and are bonded to each other to form a ring structure together with the oxygen atom to which they are bonded. ) is selected from the substituent group B consisting of groups represented by A plurality of Z ¹ may be the same or different. ]

[In the formula (M-2), n′ represents an integer of 1 or more and 10 or less.
Ar ^b represents an arylene group, a divalent heterocyclic group, or a group obtained by removing one hydrogen atom from each of the two sp ³ carbons of cycloalkadiene, and these groups may have a substituent good. When there are multiple substituents, they may be bonded together to form a ring together with the atoms to which they are bonded. When multiple Ar ^b are present, the Ar ^b may be the same or different.
Z ² is selected from the substituent group A and the substituent group B, and when Z ¹ is a group selected from the substituent group A, Z ² is a group selected from the substituent group B , Z ¹ is a group selected from the above substituent group B, Z ² is a group selected from the above substituent group A. A plurality of Z ² may be the same or different. ]

[In the formula (M), Ar ^a , Ar ^b , m′ and n′ have the same meaning as the above Ar ^a , Ar ^b , m′ and n′. ] 2. The method for producing a cyclic compound according to claim 1 , wherein said step 1 is carried out in the presence of said palladium complex, said quaternary ammonium salt and a ligand. 3. The method for producing a cyclic compound according to claim 1, wherein the compound represented by formula (M-1) is a compound represented by formula (M-1A).

[In formula (M-1A), Z ¹ has the same meaning as Z ¹ described above.
m, n and i each independently represent an integer of 1 or more. Multiple m, n and i may be the same or different.
Ar ^a1 and Ar ^a2 each independently represent a monocyclic or condensed ring arylene group or a monocyclic or condensed ring divalent heterocyclic group, and these groups may have a substituent. A plurality of Ar ^a1 and Ar ^a2 may be the same or different.
^RA represents a hydroxyl group, an alkoxy group, a cycloalkoxy group, an aryloxy group or a monovalent heterocyclic group, and these groups may have a substituent. Multiple ^RAs may be the same or different.
E ^a and E ^b are each independently a hydrogen atom, an alkenyl group, a cycloalkenyl group, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, or a substituted It represents an amino group, and these groups other than hydrogen atoms may have a substituent. A plurality of E ^a and E ^b may be the same or different, and may be bonded to each other to form a ring together with the carbon atoms to which they are bonded. ] The method for producing a cyclic compound according to any one of claims 1 to 3 , wherein the compound represented by formula (M-2) is a compound represented by formula (M-2A).

[In formula (M-2A), R ^A and Z ² have the same meanings as R ^A and Z ² described above.
k, l and j each independently represent an integer of 0 or more. However, k+l represents an integer of 1 or more. Multiple k and j may be the same or different.
Ar ^a3 and Ar ^a4 each independently represent a monocyclic or condensed ring arylene group or a monocyclic or condensed ring divalent heterocyclic group, and these groups may have a substituent. When multiple Ar ^a3 are present, the Ar ^a3 may be the same or different. A plurality of Ar ^a4 may be the same or different.
E ^c and E ^d are each independently a hydrogen atom, an alkenyl group, a cycloalkenyl group, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, or a substituted It represents an amino group, and these groups other than hydrogen atoms may have a substituent. A plurality of E ^c and E ^d may be the same or different, and may be bonded to each other to form a ring together with the carbon atoms to which they are bonded. ] 5. The method for producing a cyclic compound according to claim 4 , wherein said A ^a , Ar ^b , A ^a1 , A ^a2 , A ^a3 and A ^a4 are optionally substituted arylene groups. A method for producing a cyclic compound represented by the formula (M′), comprising a step of subjecting the cyclic compound obtained by the production method according to any one of claims 1 to 5 to a reduction reaction.

[In the formula (M'), m' and n' have the same meaning as the above m' and n'.
Ar 1 ^A and Ar 2 ^B each independently represent a monocyclic or condensed-ring arylene group or a monocyclic or condensed-ring divalent heterocyclic group, and these groups may have a substituent. A plurality of Ar ^A may be the same or different. When two or more Ar ^B are present, Ar ^B may be the same or different. ]