WO2008093879A1

WO2008093879A1 - Method for producing conjugated aromatic compound

Info

Publication number: WO2008093879A1
Application number: PCT/JP2008/051897
Authority: WO
Inventors: Seiji Oda; Takashi Kamikawa
Original assignee: Sumitomo Chemical Company, Limited
Priority date: 2007-02-01
Filing date: 2008-01-30
Publication date: 2008-08-07
Also published as: JP2008208121A; TW200846326A

Abstract

Disclosed is a method for producing a conjugated aromatic compound which is characterized in that an aromatic compound (A) wherein one or two leaving groups are bonded to an aromatic ring is reacted with an aromatic compound (A) having the same structure or an aromatic compound (B) having a structure different from that of the aromatic compound (A) wherein one or two leaving groups are bonded to an aromatic ring, in the presence of a catalytic amount of a divalent nickel compound, zinc and phenanthroline compound represented by the following formula (1). (1) (In the formula, R1, R2, R3, R4, R5 and R6 may be the same or different and represent an aryl group having 6-20 carbon atoms or the like, and R1, R2, R3, R4, R5 and R6 are not hydrogen atoms at the same time.)

Description

Method for producing conjugated aromatic compound

Technical field

The present invention relates to a method for producing a conjugated aromatic compound.

Light

Rice field

Background art

Macomole cu les 1992, 25, 1214-1223 discloses a homocoupling reaction of an aromatic dioctalogene compound in the presence of a zerovalent nickel compound. JP 2005-538154 discloses a force pulling reaction of an aromatic dihalogen compound using a catalytic amount of a zero-valent nickel complex with 2,2,1biviridine and 1,5-cyclocactogen as ligands. Has been.

Disclosure of the invention

'' The present invention

<1> An aromatic compound (A) in which one or two leaving groups are bonded to an aromatic ring, and an aromatic compound (A) having the same structure or the aromatic compound (A) An aromatic compound (B) in which one or two leaving groups structurally different from each other are bonded to an aromatic ring,

Catalytic amounts of divalent nickel compounds, zinc and formula (1):

(In the formula, RR ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different from each other, hydrogen atom, fluorine atom, alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms. , An aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms Or represents a cyano group. However, I ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are not hydrogen atoms at the same time. )

A process for producing a conjugated aromatic compound, which comprises reacting in the presence of a phenanthroline compound represented by the formula:

<2> The aromatic rings of the aromatic compound (A) and aromatic compound (B) are the same or different, and the benzene ring, biphenyl ring, naphthalene ring, fluorene ring, anthracene ring, phenanthrene ring, thiophene ring , A pyrrole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, an isoquinoline ring or a quinoxaline ring, and may be substituted with at least one group not participating in the reaction. Production method;

^{<3> R \ RR 3,} R 4, R 5 and R ⁶ are identical or different each represent a hydrogen atom, an alkyl group or Ariru group having 6 to 10 carbon atoms having 1 to 6 carbon atoms, the. Out At least one of which is an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, <1> or <2>.

<4> 1 ¹ and 1 ⁶ are the same group, R ² and R ⁵ are the same group, and R ³ and R ⁴ are the same group 1>, <2> or 3 A process for producing a conjugated aromatic compound according to claim 1;

<5> The method for producing a conjugated aromatic compound according to any one of <1> to <4>, wherein R ² and R ⁵ are the same aryl group having 6 to 10 carbon atoms;

6> The method for producing a conjugated aromatic compound according to 5>, wherein the aryl group having 6 to 10 carbon atoms is a phenyl group;

<7> The method for producing a conjugated aromatic compound according to <5> or <6>, wherein R ¹ , R ³ , R ⁴ and R ⁶ are hydrogen atoms;

<8> method of manufacturing R ¹ and R ⁶ and R ² and R ⁵ are the same alkyl group having 1 to 6 carbon atoms <1> - conjugated aromatic compound according to any one of <4>;

Walk in Ku 1 0> R ³ and R ⁴ are the same alkyl group having 1 to 6 carbon atoms; Ku 9> R ³ and R ⁴ are the production method of the conjugated aromatic compound according to walk 8> a hydrogen atom A process for producing a conjugated aromatic compound according to any one of 1> to <4>; <11> The method for producing a conjugated aromatic compound according to <10>, wherein 1 ¹ , 1 ⁶ , 1 ² and ¹⁵ are hydrogen atoms;

<12> The method for producing a conjugated aromatic compound according to any one of <1> to <11>, wherein the aromatic compound (A) is reacted with an aromatic compound (A) having the same structure as the aromatic compound (A);

<13> The aromatic compound (A) is represented by the formula (2):

(In the formula, A r ¹ represents an n-valent aromatic group, and the aromatic ring constituting the aromatic group is a benzene ring, a phenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring, a phenanthrene ring, a thiophene ring. , A pyrrolyl ring, a pyridine ring, a pyrimidine ring, a quinoline ring, an isoquinoline ring or a quinoxaline ring, and an aromatic ring which may be substituted with at least one group not participating in the reaction, X ¹ is Represents a leaving group, and n represents 1 or 2. When n is 2, X ¹ may be the same or different.

A process for producing a conjugated aromatic compound according to any one of 1 to 12 above;

<14> The aromatic compound (A) is represented by the formula (3)

(In the formula, A ² represents an amino group substituted with one or two hydrocarbon groups having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms. Here, the hydrocarbon group and the alkoxy group; The group is selected from the group consisting of a fluorine atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, and a cyano group. It may be substituted with at least one group.

R ⁷ is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 2 carbon atoms. ~ 20 represents an acyl group or cyano group, the alkyl group having 1 to 20 carbon atoms, the alkoxy group having 1 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, or the 6 to 2 carbon atoms. The aryloxy group of 0 and the acyl group having 2 to 20 carbon atoms include a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and a carbon number of 6 to 2 It may be substituted with at least one substituent selected from the group consisting of 0 aryloxy group. When R ⁷ is plural, R ⁷ may be the same group or different groups. Moreover, two adjacent R ^7s may be bonded to form a ring. X ² represents a chlorine atom, a bromine atom or an iodine atom. m represents 1 or 2, and k represents 4 1 m. )

The method for producing a conjugated aromatic compound according to any one of <1> to <12>, which is an aromatic compound represented by:

<15> aromatic compound has the formula (4)

(In the formula, A ³ represents an amino group substituted with one or two hydrocarbon groups having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms. Here, the hydrocarbon group and The alkoxy group includes a fluorine atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, and a cyan group. It may be substituted with at least one group selected from the group consisting of

R ⁸ is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or 2 carbon atoms. Represents an alkyl group having ˜20 or a cyano group, the alkyl group having 1 to 20 carbon atoms, the alkoxy group having 1 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, the carbon number An aryloxy group having 6 to 20 carbon atoms and a acyl group having 2 to 20 carbon atoms include a fluorine atom, a cyano group, and a carbon atom having 1 to 20 carbon atoms. It may be substituted with at least one substituent selected from the group consisting of a ruxoxy group, an aryl group having 6 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms. When R ⁸ is plural, R ⁸ may be the same group or different groups. Also, two adjacent R ⁸ may be bonded to form a ring.

X ³ represents a chlorine atom, a bromine atom or an iodine atom. j represents an integer of 0 to 3. A process for producing a conjugated aromatic compound according to any one of 1> to <12>, which is an aromatic compound represented by:

<16> The aromatic compound (A) is reacted with an aromatic compound (B) that is structurally different from the aromatic compound (A). <1> to 1 1> Method for the production of conjugated aromatic compounds of

<17> As the aromatic compound (A), the aromatic compound represented by the formula (2) described in <13> is used, and the aromatic compound (B) is structurally different from the aromatic compound (A). <13> an aromatic compound represented by formula (2), <14> an aromatic compound represented by formula (3), <15> a fragrance represented by formula (4) Group compounds or formula (5)

(Wherein a, b and c are the same or different and represent 0 or 1, and h represents an integer of 5 or more.

A r ² , A r ³ , A r ⁴ and A r ⁵ are the same or different and represent a divalent aromatic group. Here, the divalent aromatic group may be substituted with at least one substituent selected from the group consisting of the following (a2) to (e2).

(a 2) at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms An alkyl group having 1 to 20 carbon atoms which may be substituted with

(b2) at least one selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms An alkoxy group having 1 to 20 carbon atoms which may be substituted with one substituent;

(c 2) C 6-20 which may be substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1-20 carbon atoms and an aryloxy group having 6-10 carbon atoms Of the Aryl group;

(d2) carbon number that may be substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms 6-20 aryloxy groups; and

(e 2) at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms An acyl group having 2 to 20 carbon atoms which may be substituted with

Y ¹ and Y ² are the same or different, a single bond, - CO-, - S_〇 ₂ - one C (CH ₃₎ 2 one, one C (CF ₃₎ 2- or a fluorene one 9, 9 one Jiiru Represents a group.

Z ¹ and Z ² are the same or different and represent —O— or —S—. X ⁴ represents a chlorine atom, a bromine atom or an iodine atom. )

<1>-<11> and the manufacturing method of the conjugated aromatic compound in any one of <16> using the aromatic compound shown by;

<18> As the aromatic compound (A), the aromatic compound represented by the formula (3) described in 14> is used, and the aromatic compound (B) is structurally different from the aromatic compound (A). <13> Aromatic compound represented by formula (2), <14> Aromatic compound represented by formula (3), <15> Aromatic compound represented by formula (4), <15> A method for producing a conjugated aromatic compound according to any one of <1> to <11> and <16>, wherein the aromatic compound represented by formula (5) according to 17 or above is used;

<19> As the aromatic compound (A), the aromatic compound represented by the formula (4) described in <15> is used. As the aromatic compound (B), the structure of the aromatic compound (A) is The aromatic compound represented by formula (2) described in <13>, the aromatic compound represented by formula (3) described in 14>, and the formula (4) described in 15> Aromatic compounds shown or formula (5) according to <17> The method for producing a conjugated aromatic compound according to any one of <1> to <1 1> and <1 6>, wherein the aromatic compound represented by the formula:

<20> The leaving group is a chlorine atom, bromine atom, iodine atom, trifluoromethylsulfonyloxy group, alkylsulfonyloxy group having 1 to 6 carbon atoms, or arylsulfonyloxy group having 6 to 10 carbon atoms < A process for producing a conjugated aromatic compound according to any one of 1> to <19>;

<21> The method for producing a conjugated aromatic compound according to any one of <1> to <20>, wherein the divalent nickel compound is nickel halide;

<22> The method for producing a conjugated aromatic compound according to any one of <1> to <2> without substantially using a [tau] [tau] -type ligand; :

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different from each other, hydrogen atom, fluorine atom, alkyl group having 1 to 20 carbon atoms, carbon number 1 to 20 Represents an alkoxy group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, or a cyano group, provided that R ¹ R ² , RR ⁴ , R ⁵ and R ⁶ are not hydrogen atoms at the same time.)

A nickel complex obtained by contacting with a phenanthroline compound represented by the formula: BEST MODE FOR CARRYING OUT THE INVENTION

The aromatic compound (A) and the aromatic compound (B) are compounds having at least one aromatic ring and one or two leaving groups bonded to the aromatic ring.

The aromatic compound (B) is structurally different from the aromatic compound (A). Aromatic rings include aromatic hydrocarbon rings such as benzene ring, biphenyl ring, naphthalene ring, fluorene ring, anthracene ring, phenanthrene ring, thiophene ring, pyrrole ring, pyridin ring, pyrimidine ring, quinoline ring And aromatic heterocycles such as isoquinoline ring and quinoxaline ring. The aromatic ring may be substituted with at least one group that does not participate in the reaction, and specific examples of the group that does not participate in the reaction include the following (al) to (g 1). '

(a1) Selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms An alkyl group having 1 to 20 carbon atoms which may be substituted with at least one substituent selected from above;

(1) selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms An alkoxy group having 1 to 20 carbon atoms which may be substituted with at least one substituent;

(c1) carbon number 6 which may be substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms ~ 20 aryl groups;

(d1) carbon number 6 which may be substituted with at least one substituent selected from the group consisting of fluorine atom, cyano group, alkoxy group having 1 to 20 carbon atoms and aryloxy group having 6 to 20 carbon atoms ~ 20 aryloxy groups;

(el) at least one selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms An acyl group having 2 to 20 carbon atoms which may be substituted with a substituent;

(f 1) At least one selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms. An acyloxy group having 2 to 20 carbon atoms which may be substituted with one substituent;

(g 1) Selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms At least one An arylsulfonyl group having 6 to 20 carbon atoms which may be substituted with two substituents;

(hi) The following formula:

(In the formula, A ¹ represents an amino group substituted with one or two hydrocarbon groups having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms. Here, the hydrocarbon group and the alkoxy group Is at least selected from the group consisting of a fluorine atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms and a cyan group. It may be substituted with one group.)

A group represented by:

(i 1) Siano group;

(j 1) A fluorine atom.

Examples of the alkoxy group having 1 to 20 carbon atoms in (al) to (hi) include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert- Butoxy, n-pentyloxy, 2, 2-dimethylpropoxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n —Undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-tal decadecyloxy group , N-nonadecyloxy group, n-icosyloxy group and the like, and an alkoxy group having 1 to 6 carbon atoms is preferable.

As the aryl group having 6 to 20 carbon atoms in the above (a 1) to (! 11), a phenyl group, a 4-methylphenyl group, a 2-methylphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 3-phenanthryl group, Examples include 2-anthryl group.

Examples of the aryloxy group having 6 to 20 carbon atoms in (al) to (hi) include a phenoxy group, a 4-methylphenoxy group, a 2-methylphenoxy group, a 1-naphthyloxy group, Examples thereof include those composed of the above-mentioned aryl group having 6 to 20 carbon atoms such as 2-naphthyloxy group, 3-phenanthryloxy group, 2-anthryloxy group, and oxygen atom.

Examples of the alkyl group having 1 to 20 carbon atoms in (al) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a see-butyl group, a tert-butyl group, an n- Pentyl group, 2,2-dimethylpropyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, 2-methylpentyl group, n-octyl group, 2-ethylhexyl group N-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl Group, n-tal kutadecyl group, n-nonadecyl group, n-icosyl group and the like.

Examples of the acyl group having 2 to 20 carbon atoms in (el) and (hi) include an acetyl group, a propionyl group, a petityl group, an isoptylyl group, a benzoyl group, a 1-naphthoyl group, and a 2-naphthoyl group. There are 20 aliphatic or aromatic acyl groups.

Examples of the acyloxy group having 2 to 20 carbon atoms in (ί 1) include acetyloxy group, propionyloxy group, petityloxy group, isoptyryloxy group, benzoyloxy group, 1-naphthooxy group, 2-naphthooxy group, and the like. And those composed of an acyl group of 2 to 20 and an oxygen atom.

Examples of the arylsulfonyl group having 6 to 20 carbon atoms in the above (g l) include a phenylsulfonyl group and a p-toluenesulfonyl group.

Examples of the hydrocarbon group having 1 to 20 carbon atoms in (hi) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n —Pentyl group, 2,2-dimethylpropyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-year-octyl group, n-nonyl group, η-decyl group, η-undecyl group, η-dodecyl group, η-tridecyl group, η-tetradecyl group, η-pentadecyl group, η-hexadecyl group, η-heptadecyl group, η-octadecyl group, η-nonadecyl group, η-icosyl group Group, phenyl group, 1,3-butadiene 1,4-diyl, 'butane 1,4-diyl group, pentane-1,5-diyl group, p-phenyl-2-2,2 -'- diyl group, 0-xylylene group, and the like. Examples of the amino group substituted with one or two hydrocarbon groups having 1 to 20 carbon atoms include methylamino group, dimethylamino group, ethylamino group, jetylamino group, n-propylamino group, di-n-propylamino group, Isopropylamino group, Diisopropylamino group, n-Butylamino group, Di-n-Butylamino group, sec-Butylamino group, Di-sec-Ptylamino group, tert-Ptylamino group, G-tert-Butylamino group, n-Pentylamino group, 2, 2-dimethylpropylamino, n-hexylamino, cyclohexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamino, n-undecylamino, n-dodecylamino group, n- Torideshiruamino group, n- tetradecyl § amino group, _n - pen Yude Silamino group, n-hexadecylamino group, n-heptadecylamino group, n-octadecylamino group, n-nonadecylamino group, n-icosylamino group, pyrrolyl group, pyrrolidinyl group, piperidinyl group, carbazolyl group, dihydroindolyl group, And dihydroisoindolyl group.

(a1) includes, for example, an unsubstituted alkyl group having 1 to 20 carbon atoms and a trifluoromethyl group.

An alkyl group having 1 to 20 carbon atoms substituted with 1 or 2 or more fluorine atoms, an alkyl group having 1 to 20 carbon atoms substituted with an alkoxy group having 1 to 20 carbon atoms such as a methoxymethyl group, An alkyl group having 1 to 20 carbon atoms and substituted with a cyan group such as a methyl group is preferred.

(b 1) is preferably an unsubstituted alkoxy group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms substituted with an alkoxy group having 1 to 20 carbon atoms such as a methoxymethoxy group.

(c 1) is preferably an unsubstituted aryl group having 6 to 20 carbon atoms.

As (d 1), an unsubstituted aryloxy group having 6 to 20 carbon atoms is preferable.

(el) includes an unsubstituted acyl group having 2 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms substituted with an aryloxy group having 6 to 20 carbon atoms such as a phenoxybenzoyl group. preferable.

(f 1) includes, for example, an acyl having 2 to 20 carbon atoms substituted with an aryloxy group having 6 to 20 carbon atoms such as an unsubstituted asiloxy group having 2 to 20 carbon atoms or a phenoxybenzoyloxy group. An oxy group is preferred.

(1) is preferably an unsubstituted arylarylsulfonyl group having 6 to 20 carbon atoms. (hi) is preferably an isopropoxy group, 2, 2-dimethylpropoxy group, cyclohexyloxy group, jetylamino group or ^; n-dodecylamino group, and A ¹ is an isopropoxy group, 2 A group which is a 2-dimethylpropoxy group or a cyclohexyloxy group is more preferable.

As the group that does not participate in such a reaction, the above (a l), (b l), (e l) and (h i) are preferable.

As the leaving group, an alkylsulfonyloxy group having 1 to 6 carbon atoms such as a chlorine atom, a bromine atom, an iodine atom, a trifluoromethylsulfonyloxy group, a methanesulfonyloxy group, and an ethylsulfonyloxy group, Examples thereof include arylsulfonyloxy groups having 6 to 10 carbon atoms such as phenylsulfonyloxy group, p-methylphenylsulfonyloxy group, etc., preferably chlorine atom, bromine atom, iodine atom, chlorine atom A bromine atom is more preferable.

Specific examples of aromatic compounds include the formula (2):

(Hereinafter, abbreviated as “aromatic compound (2)”).

In formula (2), A r ¹ represents an n-valent aromatic group, and the aromatic ring constituting the aromatic group is a benzene ring, biphenyl ring, naphthalene ring, fluorene ring, anthracene ring, phenanthrene ring A thiophene ring, a pyrrole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, an isoquinoline ring or a quinoxaline ring, and an aromatic ring which may be substituted with at least one group not participating in the reaction. X ¹ represents a leaving group, and n represents 1 or 2. When n is 2, X ¹ may be the same or different.

Examples of the group not involved in the reaction include the same groups as described above.

Examples of the leaving group include the same as those described above, and a chlorine atom, a bromine atom, and an iodine atom are preferable, and a chlorine atom and a bromine atom are more preferable.

As aromatic compound (2), Chlorobenzene, bromobenzene, iodine benzene, 4-chlorofluorobenzene, 3-chloro fluorbenzene, 2-chlorofluorobenzene, 2-chlorotoluene, 2,5 dimethyl benzene, 2-ethylchlorobenzene, 3- n-propyl chloroform benzene, 4-isopropyl chlorobenzene, 5-n-butyl benzene, 2-isobutyl benzene, 3-sec-butyl benzene, 4 _ tert-butyl benzene, 5-(2,, (2-Dimethylpropyl) Chlorobenzene, 2-n-Hexylchlorobenzene, 4-Cyclohexylchlorobenzene, 4-Benzylchlorobenzene, 4-Chlorobenzenitol, 4-chloropiphenyl, 2-chlorobiphenyl, 4-chloropropyl Benzotrifluoride, 2—Black Benzotrifluoride, (4 Enyl) Asetonitoriru,

3-chloroanisole, 4-chloroanisole, 2,3-dimethoxychlorobenzene, 2,4-dimethoxychlorobenzene, 2,5-dimethoxychlorobenzene, 2-ethoxychlorobenzene, 3-n-propoxycyclobenzene, 4-isopropoxy N-butoxycyclobenzene, 5-tert-butoxycyclobenzene, 4-phenoxycyclobenzene, 4-benzyloxycyclobenzene, 4- (methoxymethyl) benzene, 4- (n —Butoxymethyl) black-opened benzene, 4- (methoxymethoxy) chlorobenzene, 4- (benzyloxymethoxy) black-opened benzene, 4 1 {2- (n-butoxy) ethoxy} black-opened benzene,

4-chloroacetophenone, 2-chloroacetophenone, 4-chloropropionone, 1-one (4-chlorophenenyl) —2, 2-dimethylpropanone, (4-chlorobenzophenyl) cyclo Xanthone, 4-Chronobenzophenone, p-Chronobenzoneacetone, 1-Chrono-Citon —4-I (Phenylsulfonyl) benzene, 4-Clo-Choylphenyl p-Tolyl Sulfone, 4-Chroomethyl-Benzenesulfonate Methyl, 3 —Methyl benzene sulfonate, 2-chloromethyl benzene, 4-ethyl benzene sulfonate, 4-chlorobenzene sulfonate (2,2-dimethylpropyl), 3-chlorobenzene sulfonate (2; 2-dimethylpropyl), 2-chlorobenzenesulfonic acid (2, 2-dimethylpropyl),

N, N-dimethyl-4 chlorosulfonamide, N, N-dimethyl-3 Benzenesulfonamide, N, N-dimethyl-2-chlorobenzene benzenesulfonamide, N, N-jetyl-4 monochlorobenzenesulfonamide,

1-chloronaphthalene, 2-bromothiophene, 5-bromo-1-3-thiolthiophene, 2-bromo-3-dodecylthiophene, 5-bromo-1-2,2, 1-pithiophene, 5-bromo-3-cyclohexylthiophene , 2-chloro-3-octylthiophene, 5-chloro-one 3-phenylthiophene, 1-methyl-1-5-chloro pyrrole, 1-hexylul 2-bromopyrrole, 1-octyl-5-chloro Pyrrole, 2-Chronic pyridine, 3-Clopyridine, 5-Monopyridine, 3-Methyl -1-2-Chloro-pyridine, 3-Hexyl-one 5-Clo-Cine pyridine, 5-Clo-Cidium 2, 2 ' —Pipyridine, 3,3 ′ —Dimethyl mono-5-chloro-2,2′—Bilylidine, 3,3′-Dioctyl 5-promo 2,2′—Pipyridine, 2-chloropyrimidine, 5-cyclopyrimidine, 2-— Bromopyri Gin, 5-Chronoquinoline, 8-Bromoquinoline, 2-Crocuoquinoline, 1-Crocuoisoquinoline, 4-Chloroisoquinoline, 8-Promoisoquinoline, 5_Promoisoquinoline, 4-Promo 2, 1, 3-benzo Thiadiazole, 7-Clocobenzoimidazole, 4-Clocobenzoimidazole, 5-Clocolate Quinoxaline, 5-Clocolate 2,3-Diphenylquinoxaline, 2-Bromoquinoxaline, 6-Promoquinoxaline,

1.3-dichlorobenzene, 1,4-dibromobenzene, 1,4-jodobenzene, 2,4-dichlorotoluene, 3,5-dibromotoluene, 2,5-jodetotoluene,

1. 3—Dichloro mouth 4-methoxybenzene, 1, 4 1 dib mouth mode 3-Methylbenzene, 1, 4-Jodo 3-methoxybenzene, 1, 3-Dichloro mouth 4-acetoxybenzene,

1.4—Jib mouth mode 3—acetoxybenzene, 1,3—Jodium—4-acetoxybenzen,

2,5-dichloro-4,1-phenoxybenzophenone, 1,4-dibu-mouthed MO 2-ethylbenzene, 1,4-dibromo-2-methoxybenzene, dimethyl 2,5-dibromoterephrate, 1, 4 1-jib mouth monaphthalene, 1, 1 '1-jib mouth monaphthalene, 4, 4'-biphenyl,

1.4-Dibu-Mouth Mo 2,5-Dihexyloxybenzene, 1-Bromo-4 Monochrome Benze 1 bromo 1 4 chlorotoluene, 1-bromo 1 -4 chloro opening _ 2 -propylbenzene, 2,5-dibromo 1 4'-phenoxybenzophenone, 2,5 -dibu mouth motiophene, 2,5-Dibu-Mouth Mo 3--Hexylthiophene, 2,5-Dibu-Mouth Mo 3-Dodecylthiophene, 5,5'-Georgh Mo 2,2, Ibithiophene, 2,5-Dib-Mouth Mo 3-Cyclohexylthiophene , 2,5-Dichloro 1-octylthiophene, 2,5-Dichloro-1-3-dithiophene, 1-methyl-2,5-dichloropyrrole, 1-hexyl-2,5-dibromopyrrole, 1— Octyl-, 2,5-dichloropyrrole, 2,5-dichlorodipyridine, 3,5-dichlorodipyridine, 2,5-dibromopyridine, 3-methyl-2,5-dichloropyridine, 3-hexyl-2,5-dichloro Mouth pyridine, 5,5'-dichloro- 2, 2 '1 Pypyridine, 3, 3' — Dimethyl 1, 5, 5 'Dicyclo 1, 2, 2' — Pypyridine, 3, 3 '— Dioctyl 1, 5, 5' One Dib, Mo 2, 2, 1 Biviridine, 2,5-Dichloropyrimidine, 2,5-Dibromopyrimidine, 5,8-Dichloroquinoline, 5,8-Dibu mouth moquinoline, 2,6-Dichloro mouth quinoline, 1,4-Dichloroisoquinoline, 5,8-Dibromoiso Quinoline, 4,7-Dibu-Mouth Mo 2,1,3-Benzothiadiazole, 4,7-Diclo-Mouth Benzoimidazole, 5,8-Diclo-Mouth Quinoxaline, 5,8-Dichloro-2,3-Diphenyl diquinoxaline 2, 6-jib mouth moquinoxaline,

2,7-Dibromo-1,9-dihexyl 9 H-fluorene, 2,7-Dibromo-1,9-dioctyl-9 H-fluorene, 2,7-Dibromo-9,9-didodecyl-9 H-fluorene, 2 , 7-dichloro-9, 9-dihexyl 1 9 H-fluorene, 2, 7-dichloro 1 9, 9-dioctyl 9 H-fluorene, 2, 7-dichloro 9, 9-didodecyl 9 H-fluorene, 2-bromo 7 —Chloro-9,9-dihexyl 9 H—fluorene, 2-bromo 1 7—black mouth—9, 9—dioctyl 9 H—fluorene, 2-bromo 7—black mouth 9, 9-didodecyl 9 H—fluorene, etc. Can be mentioned.

Specific examples of aromatic compounds include the formula (3):

(Hereinafter abbreviated as “aromatic compound (3)”).

In formula (3), examples of A ² include the same groups as those described above for A ¹ , preferably a unsubstituted alkoxy group having 3 to 20 carbon atoms, and includes an isopropyl group, an isobutoxy group, and 2,2-dimethylpropoxy. And a cyclohexyloxy group are more preferred.

R ⁷ alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, and 2 to 20 carbon atoms. Examples of the acyl group are the same as those described above. R ⁷ is preferably a hydrogen atom, an unsubstituted alkyl group having 1 to 20 carbon atoms, or an unsubstituted alkoxy group having 1 to 20 carbon atoms.

X ² is preferably a chlorine atom or a bromine atom, and m is preferably 1.

Specific examples of the aromatic compound (3) include 2,5-dichloro-pentabenzenesulfonic acid isopyl pill, 2,5-dichlorocyclobenzene sulfonic acid isobutyl, 2,5-dichlorobenzenesulphonic acid (2,2-dimethyl). Propyl), 2,5-dichlorocyclohexane benzene sulfonate, n-octyl 2,5-dichlorobenzene sulfonate, n-pentadecyl 2,5-dichlorobenzene sulfonate, n-pentadecyl 2,5-dichlorobenzene sulfonate Icosyl, N, N—Jetyl 2,5-dichloro-benzenesulfonamide, N, N-diisopropyl-2,5-dichlorobenzenesulfonamide, N— (2,2-dimethylpropyl) 1,2,5-dichloro Benzenesulfonamide, N—n—dodecyl-2,5-dichlorobenzenesulfonamide, N—n—icosyl-2,5-dichlorobenzenesulfone Imide, 3,5-dichlorobenzene isopropyl sulfonate, isoptyl 3,5-dichlorobenzene sulfonate, 3,5-dichlorobenzene sulfonate (2,2-dimethylpropyl), cyclohexane 3,5-dichlorobenzene sulfonate Xyl, n-octyl 3,5-dichlorodibenzene sulfonate, 3,5-Dichlorodiphenylbenzenesulfonic acid! Pendecyl decyl, 3,5-dichlorobenzenesulfonic acid n-icosyl, N, N-jetyl-3,5-dichlorobenzenesulfonamide, N, N-diisopropyl , 5—Dichlorobenzenesulfonamide, N— (2, 2-dimethylpropyl) 1,3,5-Dichloro-benzenesulfonamide, N—n—dodecyl 1,3,5-dichlorobenzenesulfonamide, N—n—icosyl-3 , 5-dichlorobenzenesulfonate,

Isopropyl 2,5-dibromobenzenesulfonate, isobutyl 2,5-dibromobenzenesulfonate, 2,5-dibromobenzenesulfonate (2,2-dimethylpropyl), cyclohexyl 2,5-dibromobenzenesulfonate, 2 N-octyl 2,5-dibromobenzenesulfonate, n-pentadecyl 2,5-dibromobenzenesulfonate, n-icosyl 2,5-dibubutane, N, N-jetyl-2,5-dibromobenzenesulfonamide , N, N-diisopropyl-1,2,5-dibromobenzenesulfonamide, N- (2,2-dimethylpropyl) -1,2,5-dibromobenzenesulfonamide, N-n-dodecyl-2,5-dibromobenzenesulfonamide , N—n— ^ f Kosyl— 2,5—Dibu mouth Mobenzenesulfonamide, 3,5-Dibromobenzenesulfonic acid Sopropyl, 3, 5 Isobutyl butylbenzenesulfonate, 3,5-dibromobenzenesulfonic acid (2,2-dimethylpropyl), cyclohexyl 3,5-dibromobenzenesulfonic acid, 3,5-dibromobenzenesulfone Acid n-octyl, 3,5-dibromobenzenesulfonic acid n-pentadecyl, 3,5-dibromobenzenesulfonic acid n-icosyl, N, N-jetyl-3,5-dibromobenzenesulfonamide, N, N-diisopropyl _ 3 , 5-Dibromobenzenesulfonamide, N— (2,2-Dimethylpropyl) 1,3,5-Dibromobenzensulfonamide, N—n—dodecyl-3,5-dibromobenzenesulfonamide, N—n—icosyl— 3, 5-dibromobenzenesulfonamide,

2,5-Jodobenzenesulfonate isopropyl, 2,5-Jodobenzenesulfonate isobutyl, 2,5-Jodobenzenesulfonate (2,2-dimethylpropyl), 2,5-Jodobenzenesulfonate Xylyl, 2,5-Jodium benzenesulfonic acid n-octyl, 2,5-jodobenzenesulfonic acid n-pendedecyl, 2,5-jodobenzenesulfonic acid n-icosyl, N, N-jetyl 2,5-jodobenzenesulfonamide, N, N- Diisopropyl-1,2,5--Jodobenzenesulfonamide, N— (2,2-Dimethylpropyl) —2,5-—Jodobenzenesulfonamide, N—n—Dodecyl-2,5-—Jodobenzenesulfonamide, N—n— Icosyl 2,5-—Jodobenzenesulfonamide, 3,5-—Isopropylbenzenesulfonate, 3,5-Jodiumbenzene sulfonate, 3,5-Jodobenzenesulfonate (2,2-dimethylpropyl) ), 3, 5— cyclohexyl benzene sulfonate, 3, 5 — n-octyl benzene sulfonate, 3, 5— benzene benzene N-Pendecyl, sulfonic acid, n-icosyl sulfonate, N, N-jetyl, 3, 5-jodobenzenesulfonamide, N, N-diisopropyl-1,5-5-benzene Sulfonamide, N— (2,2-Dimethylpropyl) 1,3,5-Jodobenzensulfonamide, N—n—Dodecyl 1,3,5-Jodobenzenesulfonamide, N—n 1 ^ Γ Kosyl 3,5 1 Jo 1-dobenzenesulfonamide,

2,4-dichlorobenzene sulfonic acid (2,2-dimethylpropyl), 2,4-dibromobenzenesulfonic acid (2,2-dimethylpropyl), 2,4-jodobenzenesulfonic acid (2,2-dimethylpropyl) , 2,4-dichroic _ 5-methylbenzenesulfonic acid (2., 2-dimethylpropyl), 2,5-dichroic one 4-methylbenzenesulfonic acid (2, 2-dimethylpropyl), 2, 4-dibu Mouth 5—Methylbenzenesulfonic acid (2,2-dimethylpropyl), 2,5-Dib Mouth 4-methylbenzenesulfonic acid (2,2-dimethylpropyl), 2,4-Jodo—5-methylbenzenesulfonic acid (2,2-Dimethylpropyl), 2,5-Jodo-4-methylbenzenesulfonic acid (2,2-dimethylpropyl), 2,4-Dichloro-5-methoxybenzenesulfonic acid (2,2-Dimethylpropyl) ), 2,5-dichloro-4-methoxybenzenesulfonic acid (2,2-dimethylpropyl), 2,4 one-dib-mouthed 5-methoxybenzenesulfonic acid (2,2-dimethylpropyl), 2,5-dibromo — 4-Methoxybenzenesulfonic acid (2, 2-dimethylpropyl), 2, 4-di 1-Methoxybenzenesulfonic acid (2, 2-dimethylpropyl), 2,5-Jode 4-methoxybenzenesulfonic acid (2,2-dimethylpropyl), 1 (2,5 Benzenesulfonyl) pyrrolidine and the like.

Among them, 2,5-dichlorobenzenebenzene sulfonic acid (2,2-dimethylpropyl), 2,5-dichlorobenzenesulfonate isobutyl, 2,5-dichlorobenzenesulfonate hexyl, N, N-jetyl-2 , 5-Dichlorobenzene benzenesulfonamide and N-n-dodecyl-2, 5-dichlorobenzenesulfonamide, 2, 5-dibromobenzenesulfonic acid (2, 2-dimethylpropyl), 2,5-dibromobenzenesulfonic acid isobutyl 2,5-dibromobenzenesulfonic acid cyclohexyl, N, N-jetyl-2,5-dibromobenzenesulfonamide, Nn-dodecyl-2,5-dibromobenzenesulfonamide are preferred.

Specific examples of aromatic compounds include the formula (4):

(Hereinafter abbreviated as “aromatic compound (4)”).

In formula (4), examples of A ³ include the same as A ² above, and a unsubstituted alkoxy group having 3 to 20 carbon atoms is preferable, and an isopropyl group, an isobutoxy group, 2, 2-dimethylpropoxy A group and a hexyloxy group are more preferred.

R ⁸ is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and an acyl group having 2 to 20 carbon atoms. Are the same as those described above. R ⁸ is preferably a hydrogen atom, an unsubstituted alkyl group having 1 to 20 carbon atoms, or an unsubstituted alkoxy group having 1 to 20 carbon atoms. X ³ is preferably a chlorine atom or a bromine atom, and j is preferably 0.

Aromatic compounds (4) include: 4,4, -dichloropiphenyl-2,2'-dimethyl disulfonate, 4,4'-dichloropiphenyl-2-ru 2,2'-jetyl disulfonate, 4,4'-dichlorobiphenyl Diluene 2, 2 'Di (n-propyl) disulfate, 4, 4' — Dichlorobiphenyl di 2,2 'Diisopropyl monodisulfonate, 4, 4' — Dichloropihue Diru 2,2 'Didisulfonic acid di ( n-butyl), 4,4'-dichlorobiphenyl-2,2'diisobutyl disulfate, 4,4'-dichlorobiphenyl 2,2, di-disulfonate (2,2-dimethylpropyl), 4, 4, 2-dichlorobiphenyl 1, 2, 2 '— Dicyclohexyl disulfone, 4, 4' — Dichlorobiphenyl— 2, 2, — di (n-octyl) disulfonate, 4, 4 ′ — Dichloropiphenyl 2, 2, monodisulfonic acid di (n —Pentadecyl), 4, 4'-dichlorobiphenyl 1, 2, 2, —disulfonic acid di (n-icosyl),

N, N-dimethyl-4,4'-dichlorobiphenyl 2,2 'monodisulfonamide, N, N-jetyl 4,4, -dichloropiphenyl1,2,2, monodisulfonamide, N, N-di (n -Propyl) 1,4,4-dichlorobiphenyl-1,2,2, monodisulfonamide, N, N-diisopropyl-1,4,4, -dichlorobiphenyl-1,2,2, monodisulfonamide, N, N-di ( n-butyl) —4,4'-dichlorobiphenyl-1,2,2'-disulfonamide, N, N-diisobutylene 4,4'-dichloropiphenyl-1,2,2, monodisulfonamide, N-di (2, 2-Dimethylpropyl) 1, 4, 4-Dichloropifenil 2, 2, — Disulfonamide, N-di (n-octyl) -4, 4, Dichloropifenil 2, 2, '-Disulfonamide, N-di (n-dodecyl) -4,4, -dichloropiphenyl-1,2,2, -disulfo Amide, N-di (n-icosyl) -4, 4, Dichlorobiphenyl 1, 2, 2 'Disulfonamide, N, N-Diphenyl 1, 4, 4, Dichloropiphenyl 1, 2, 2'-Disulfonamide ,

3, 3 'mono-dimethyl-4, 4'-dichlorobiphenyl 1, 2, 2' monodisulfonic acid di (2, 2-dimethylpropyl), 5, 5, mono-dimethyl 4, 4'- dichloropiphenyl 1, 2, 2 , Di (2,2-dimethylpropyl) mono-disulfonate, 6, 6'-dimethyl-4,4'-dichloropropylene 2,2 'Di (2,2-dimethylpropyl) mono-disulfonate, 3, 3, 1 dimethoxy- 4, 4 '— Dichloropiphenyl _2, 2' 1. Disulfonic acid di (2, 2-dimethylpropyl), 5, 5, 1-dimethoxy-4, 4, Dichloropiphenyl-2, 2 '— Disulfonic acid di (2,2-dimethylpropyl), 6, 6'-dimethoxy-1,4,4'-dichlorobinitrone 2,2, di-disulfonic acid di (2,2-dimethylpropyl), 3,3'-diphenyl RU 4,4'-Dichloropiphenyl 1,2,2'-disulfonic acid di (2,2-dimethylpropyl), 3,3, -diacetyl-4,4'-dichlorobiphenyl 2,2'-disulphonic acid Di (2,2-dimethylpropyl), 5, 5, 1-diacetyl-1, 4, 4, Mouth Bifue two Lou 2, 2 'single disulfonate, di (2, 2-dimethylpropyl),

4, 4, — Dibromopiphenyl— 2, 2 ′ — Dimethyl disulfonate, 4, 4 ′ — Dibromo p-diphenyl 2, 2 ′ — Jetyl disulfonate, 4, 4 ′ One dibromobiphenyl 2, 2, — Disulfone Di (n-propyl) acid, 4, 4, 1-dibromobiphenyl 1, 2, 2 '— Diisopropyl disulfonate, 4, 4' — Dibromopiphenyl _ 2, 2 'Di (n-butyl) disulfonate, 4 , 4,1 dibromopiphenyl 2,2 'disobutyl monodisulfonate, 4, 4' —dibromobiphenyl 2,2 'di (2,2-dimethylpropyl) disulfonate, 4, 4' —dibromopiphenyl— 2,2'-dicyclohexyl disulfonate, 4,4'-dipromobiphenyl-2,2'di (n-octyl) disulfonate, 4,4'-dibromobiphenyl-2,2, disulfonic acid Di (n-pentadecyl), 4, 4, one di Mouthphenyl-2,2'-disulfonate (n-icosyl),

N, N—Dimethyl— 4,4 ′ Monodibromobiphenyl 2,2′—Disulfonamide, N, N—Jetyl 4,4 ′ Monodibromobiphenyl—2, 2 ′ Monodisulfonamide, N, N—Di ( n-propyl) 1,4,4'-dibromopiphenyl-2,2'-disulfonamide, N, N-diisopropyl-1,4,4'-dibromobiphenyl2,2'-disulfonamide, N, N-di ( n-Butyl) 1,4 'One dibromopiphenyl bis 2,2' One disulfonamide, N, N-Diisobutylene 4,4 'One dibromobiphenyl 2,2'-Disulfonamide, N-di (2,2-dimethylpropyl) —4, 4 '—Dibromobiphenyl, 2, 2' —Disulfonamide, N-di (n-year-old cutyl) —4, 4 '—Dibromobiphenol, 2, 2' —Disulfonamide, N-di (n-dodecyl) —4, 4 '—Dibromobiphenyl, 2, 2,-Disulfonamide, N-di (n-icosyl), 1, 4, 4 — —Dibromopifenil, 2, 2 , 1 disulfonamide, N, N-diphenyl-4, 4, -dibromobiphenyl 2, 2, 1 disulfonamide and the like.

Among them, 4,4′-dichlorobiphenyl 2,2,1, diisopropyl monosulfonate, 4,4′-dichlorobiphenyl-1,2,2′-disulfonate (2,2-dimethylpropyl), 4, 4, Preference is given to monodibromopiphenyl-1,2,2'diisopropyl disulfonate and 4,4,1-dibromopiphenyl-2,2'di (2,2-dimethylpropyl) disulfonate.

As the aromatic compound (2), a commercially available one may be used, or one produced according to a known method may be used.

Aromatic compound (3) is represented by formula (1 0) in the presence of a tertiary amine compound or pyridine compound:

(In the formula, R ⁷ , X ² , m and k have the same meaning as above.)

(Hereinafter abbreviated as compound (10)) and formula (11):

A ² — H (11)

(In the formula, A ² represents the same meaning as described above.)

(Hereinafter abbreviated as Compound (1 1)).

Compound (10) includes 2,5-dichlorobenzenesulfonic acid chloride, 3, 5— Examples include dichlorobenzenesulfonic acid chloride, 2,5-dibromobenzenesulfonic acid chloride, 3,5-dibromobenzenesulfonic acid chloride, and the like. As such a compound (10), those commercially available are usually used.

Compound (11) includes isopropanol, isobutanol, 2,2-dimethylpropanol, cyclohexanol, n-octanol, n-pentadecanol, n-icosanol, jetylamine, diisopropylamine, 2, 2-dimethyl. Examples include propylamine, n-dodecylamine, n-icosylamine and the like. As the compound (11), a commercially available compound is usually used.

The amount of the compound (11) used is usually 0.2 mol or more per 1 mol of the group represented by —so ₂ c 1 in the compound (10) ′, and there is no particular upper limit, and the compound (11) When is a liquid at the reaction temperature, a large excess amount may be used also as a reaction solvent. The amount of practical compounds (1 1), the compound (10) in the - relative to 1 mole of the group represented by S_〇 ₂ C 1, which is 0.5 to 2 moles.

Tertiary amine compounds include trimethylamine, triethylamine, tri (n-propyl) amine, tri (n-butyl) amine, disopropylethylamine, tri (n-octyl) amine, tri ( n-decyl) amine, triphenylamine, N, N-dimethylaniline, N, N, Ν ′, Ν′-tetramethylethylenediamine, Ν-methylpyrrolidine and the like. A commercially available tertiary amine compound is usually used. The amount of the tertiary amin compound used is usually 1 mol or more per 1 mol of the group represented by —S0 ₂ C 1 in the compound (10), and there is no particular upper limit. In the case of a liquid at the reaction temperature, a large excess amount may be used also as a reaction solvent. The amount of practical tertiary Amin compound, relative to 1 mole of the group represented in one S_〇 ₂ C 1 in compound (10) from 1 to 30 mol, preferably 1 to 20 moles, more preferably 1 to 10 moles.

Examples of pyridine compounds include pyridine and 4-dimethylaminopyridine. A commercially available pyridine compound is usually used. The amount of the pyridine compound used is usually 1 mol or more per 1 mol of the group represented by —S0 ₂ C 1 in the compound (10), There is no particular upper limit, and when the pyridine compound is liquid at the reaction temperature, a large excess amount may be used also as the reaction solvent. The amount of practical pyridine compound relative to 1 mole of the group represented in one S_〇 ₂ C 1 in compound (10), 1 to 30 mol, preferably 1 to 20 moles, more preferably 1 to 10 Is a mole.

The reaction of compound (10) and compound (11) is usually carried out by mixing compound (10), compound (11) and a tertiary amine compound or pyridine compound in the presence of a solvent. The mixing order is not particularly limited.

Solvents include aromatic hydrocarbon solvents such as toluene and xylene; ether solvents such as jetyl ether, tetrahydrofuran and 1,4-dioxane; dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylformamide Aprotic polar solvents such as N, N-dimethylacetamide, hexamethylphosphoric triamide; halogenated hydrocarbon solvents such as dichloromethane, chloroform, dichloroethane, chloroform, dichlorobenzene, etc. It is done. Further, as described above, when the compound (11), the tertiary amine compound or the pyridine compound is liquid at the reaction temperature, these may be used as the reaction solvent. These solvents may be used alone or in combination of two or more. The amount of solvent used is not particularly limited.

The reaction temperature between compound (10) and compound (11) is usually from 30 to 150 ° C, preferably from -10 to 70 ° C. The reaction time is usually 0.5 to 24 hours.

After completion of the reaction, for example, the reaction mixture is mixed with water or an aqueous acid solution, and if necessary, an aromatic hydrocarbon solvent such as toluene or xylene; an aliphatic hydrocarbon solvent such as hexane or heptane; dichloromethane, dichloroethane A halogenated hydrocarbon solvent such as black form; an organic solvent insoluble in water such as an ester solvent such as ethyl acetate, and extraction treatment to obtain an organic layer containing the aromatic compound (3) Can do. If necessary, the aromatic layer (3) can be taken out by washing the organic layer with water, an aqueous alkali solution or the like, if necessary, and then concentrating.

The aromatic compound (4) is a compound (10) in the method for producing the aromatic compound (3). Instead of Equation (12):

(Wherein R ⁸ , X ³ and j have the same meaning as above)

(Hereinafter abbreviated as Compound (12)), and in place of Compound (11), Formula (13):

A ³ ~~ H (13)

(Wherein A ³ represents the same meaning as described above.)

Can be produced in the same manner using the compound represented by the formula (hereinafter abbreviated as compound (13)).

The compounds (12) include 4, 4'-dichlorobiphenyl-2,2, monodisulfonic acid dichloride, 4,4 'monodibromopiphenyl-2,2'monodisulfonic acid dichloride, 3,3' monodimethyl-4 , 4, 1, Dichlorobiphenyl 1, 2, 2, — Disulfonic acid dichloride, 5, 5 '— Dimethyl-4, 4' — Dichlorobiphenyl— 2, 2 'Monodisulfonic acid dichloride, 6, 6' — Dimethyl 4 , 4 '— Dichlorobiphenyl 1, 2, 2' — Disulfonic acid dichloride, 3, 3 'Dimethyl 4, 4,' — Dichlorobiphenyl 1, 2, 2 '— Disulfonic dichloride, 5, 5' — Dimethoxy 4 , 4 '-Dichloropiphenyl 2-Lu, 2' Mono-disulfonic acid dichloride, 6, 6, -Dimethoxy- 4,4 '-Dichloropiphenyl mono- 2, 2' -Disulfonic dichloride, 3, 3 'Di-Diphenyl 4, 4' -Dichlorobiphenyl 2 2, 2 '' Monodisulfonic acid dichloride, 3, 3 '' Didiacetyl- 4, 4 '— Dichloropiphenyl-2-2, 2, monodisulfonic acid dichloride, 5, 5''Didiacetylmono-4,4'-dichloropiphenyl-2,2''Disulfone Acid dichloride, 6, 6'-diacetyl-4,4'-dichlorobiphenyl 2,2 'monodisulfonic acid dichloride, etc., and 4,4'-dichlorobi Preference is given to phenyl 2,2'-disulfonic acid dichloride and 4,4'-dibromobiphenyl 2,2'-disulfonic acid dichloride. As such a compound (12), a commercially available compound may be used. For example, Bu l l. S 0 c. Ch i m. F r., 4, 49 (1 931), 1047-1049, etc. Those produced according to the known methods described in 1) may be used.

Examples of the compound (13) include those similar to the compound (11), and those commercially available are usually used. '

Specific examples of aromatic compounds include the formula (5):

(Hereinafter abbreviated as “aromatic compound (5)”).

In formula (5), h is preferably an integer of 10 or more.

The Ar ^2, Ar ^3, A r ⁴ and A r ⁵ in the divalent aromatic group, 1, 3-off Eniren group, 1, 4 _ phenylene group, 4, 4, One Bifue two Lou 1, 1 '— Divalent monocyclic aromatic group such as diyl group; naphthalene 1,3-diyl group, naphthalene 1,1,4-diyl group, naphthalene 1,5-diyl group, naphthalene 1,6 -Divalent condensed aromatics such as diyl group, naphthalene 1,1,7 diyl group, naphthalene 1,2,6-diyl group, naphthalene 1,2,7-diyl group, 9H-fluorene 1,2,7-diyl group Group: pyridine-1,2,5-diyl, pyridine-1,2,6-diyl, quinoxaline-1,2,6-diyl, thiophene-1,2,5-diyl, 2,2'-bithiophene1,5,5 '1 diyl group, 1 pyrrole 2, 5 1 diyl group, 2, 2'—biviridine 1 5, 5' —diirile group, pyrimidine 1 2,5-diylile group, key Norin-1, 5, 8-diyl, quinoline 1, 2, 6-diyl, isoquinoline 1, 1, 4-diyl, isoquinoline-5,8-diyl, 2, 1, 3 _benzothiadiazole-4, 7- And divalent heteroaromatic groups such as diyl group, benzoimidazole-4,7-diyl group, quinoxaline-1,5,8-diyl group, quinoxaline-1,2,6-diyl group, and the like. Of these, divalent monocyclic aromatic groups and divalent condensed aromatic groups are preferred, such as 1,4-monophenylene group, naphthalene-1, More preferred are 4-diyl group, naphthalene-1,5-diyl group, naphthalene-2,6-diyl group and naphthalene-2,7-diyl group.

Such a divalent aromatic group may be substituted with at least one substituent selected from the group consisting of the following (a 2) to (e 2).

(b 2) at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms An alkoxy group having 1 to 20 carbon atoms which may be substituted with

(c2) carbon number optionally substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 10 carbon atoms The aryl group of

(d2) carbon atoms that may be substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms An aryloxy group of

an alkoxy group having 1 to 20 carbon atoms in (a2) to (e 2), an aryl group having 6 to 20 carbon atoms

Examples of the aryl group, the aryl group having 6 to 20 carbon atoms, the alkyl group having 1 to 20 carbon atoms, and the acyl group having 2 to 20 carbon atoms are the same as those described above.

Examples of (a 2) include the same as the above (al). (B 2) is the same as (b 2) above. Examples of (c 2) include the same as the above (cl). Examples of (d2) include the same as (dl). Examples of (e 2) include the same as (el). X ⁴ is preferably a chlorine atom or a bromine atom.

Specific examples of the aromatic compound (5) include compounds shown below, compounds in which the chlorine atoms at both ends of the compounds shown below are replaced by bromine atoms, and the like. In the following formula, h represents the same meaning as described above.

As the aromatic compound (5), one produced according to a known method such as Japanese Patent No. 2,745,727 may be used, or a commercially available one may be used. Examples of commercially available products include SUMIKAEXEL PES manufactured by Sumitomo Chemical Co., Ltd.

As the aromatic compound (5), those having a polystyrene equivalent weight average molecular weight of 2,000 or more are preferably used, and those having a weight average molecular weight of 3,000 or more are more preferred.

The invention of the present application comprises reacting an aromatic compound (A) with an aromatic compound (A) having the same structure or an aromatic compound (B) structurally different from the aromatic compound (A). It is.

As a specific example of reacting the aromatic compound (A) with the aromatic compound (A) having the same structure as this,

When using aromatic compound (2) as aromatic compound (A);

When aromatic compound (3) is used as aromatic compound (A);

Examples of the aromatic compound (A) include a case where the aromatic compound (4) is used.

As a specific example in the case of reacting an aromatic compound (A) with an aromatic compound (B) structurally different from the aromatic compound (A),

When aromatic compound (A) is used as aromatic compound (A), and aromatic compound (2) is structurally different from aromatic compound (A) as aromatic compound (B);

When using aromatic compound (2) as aromatic compound (A) and using aromatic compound (3) structurally different from aromatic compound (A) as aromatic compound (B); When using aromatic compound (2) as aromatic compound (A) and using aromatic compound (4) structurally different from aromatic compound (A) as aromatic compound (B)

When aromatic compound (A) is used as aromatic compound (A) and aromatic compound (5) is structurally different from aromatic compound (A) as aromatic compound (B)

When aromatic compound (A) is used as aromatic compound (A), and aromatic compound (2) is used as aromatic compound (B), which is structurally different from aromatic compound (A)

When using aromatic compound (3) as aromatic compound (A), and using aromatic compound (3) structurally different from aromatic compound (A) as aromatic compound (B)

When aromatic compound (A) is used as aromatic compound (A), and aromatic compound (4) is used as aromatic compound (B), which is structurally different from aromatic compound (A)

When using aromatic compound (4) as aromatic compound (A) and using aromatic compound (2) structurally different from aromatic compound (A) as aromatic compound (B)

When aromatic compound (4) is used as aromatic compound (A), and aromatic compound (3) structurally different from aromatic compound (A) is used as aromatic compound (B)

When aromatic compound (4) is used as aromatic compound (A), and aromatic compound (4) structurally different from aromatic compound (A) is used as aromatic compound (B)

When aromatic compound (A) is used as aromatic compound (A), and aromatic compound (5) is structurally different from aromatic compound (A) as aromatic compound (B); Can be mentioned.

Examples of divalent nickel compounds include nickel fluorides such as nickel fluoride, nickel chloride, nickel bromide and nickel iodide, nickel carboxylates such as nickel formate and nickel acetate, nickel sulfate, nickel carbonate, nickel nitrate, nickel Examples thereof include cetylacetonate, (dimethoxyethane) chloride nickel and the like, and nickel halide is preferable.

The amount of the divalent nickel compound used is a catalytic amount. If the amount used is too small, a conjugated aromatic compound having a small molecular weight is likely to be obtained. If the amount used is too large, post-treatment after the polymerization reaction will occur. The amount of divalent nickel compound used is usually 0.001 to 0.8 mol, preferably 0.0 mol, per 1 mol of all aromatic compounds used. 1 to 0.4 mol.

As zinc, commercially available products are usually used. The shape is not particularly limited, but usually powdered zinc is used. The amount used is usually 1 mol or more with respect to 1 mol of all aromatic compounds to be used, and the upper limit is not particularly limited, but if it is too much, post-treatment after the polymerization reaction becomes complicated, Since it tends to be disadvantageous economically, it is practically 10 moles or less, preferably 5 moles or less.

Formula (1):

Wherein R ¹ R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different, respectively, in the formula of the phenantorin phosphorus compound (hereinafter abbreviated as phenantorin compound (1)), Hydrogen atom, fluorine atom, alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, and acyl having 2 to 20 carbon atoms Represents a group or a cyan group, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are not simultaneously hydrogen atoms.

Examples of alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aryloxy groups having 6 to 20 carbon atoms, and acyl groups having 2 to 20 carbon atoms The thing similar to what was mentioned above is mentioned. .

RK R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and each is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, of which at least Preference is given to the phenanthroline compound (1) in which one is an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms.

R \ R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and each represents a hydrogen atom, Preference is given to the phenantorin phosphorus compound (1), which is a methyl group or a phenyl group, at least one of which is a methyl group or a phenyl group.

Preference is given to the phenantorin phosphorus compound (1), wherein R ¹ and R ⁶ are the same group, R ² and R ⁵ are the same group, and R ³ and R ⁴ are the same group.

R ¹ and R ⁶ are the same group, R ² and R ⁵ are the same aryl group having 6 to 10 carbon atoms,

A phenantorin phosphorus compound in which R ³ and R ⁴ are the same group (1), R ¹ , R ² , R ⁵ and R ⁶ are the same alkyl group having 1 to 6 carbon atoms, and R ³ and R ⁴ are The same group of phenanthroline compounds (1) and R ¹ , R ² , R ⁵ and R ⁶ are the same group, and R ³ and R ⁴ are the same alkyl group having 1 to 6 carbon atoms. Oral phosphorus compounds (1) are more preferred, R ¹ and R ⁶ are the same group, R ² and R ⁵ are phenyl groups, and R ³ and R ⁴ are the same groups. ), R ¹ , R ² , R ⁵ and R ⁶ are methyl groups, and R ³ and R ⁴ are the same group. Phosphorus compound (1) and R ¹ , R ² , R ⁵ and R ⁶ are are the same group, R ³ and R ⁴ are methyl groups Fuenanto port phosphorus compound (1) is more preferable, R ^1, R ^3, R ⁴ and R ^e are hydrogen atom, R ² and R ⁵ Phenantorporin compounds in which is a phenyl group 1), R ¹ and R ² and R ⁵ and R ⁶ is a methyl group, Fuenanto port phosphorus compounds R ³ and R ⁴ is a hydrogen atom (1) and R ¹ and R ² and R ⁵ and R ^A phenantorin phosphorus compound (1) in which ⁶ is a hydrogen atom and R ³ and R ⁴ are methyl groups is particularly preferred.

The phenanthroline compounds (1) include 5-methyl-1,10-phenanthroline, 4-methyl-1,1,10-phenantorin, 5,6-dimethyl-1,1,10-phenantorin, 4,7 1-dimethyl-1,10-phenantorin, 3,8-dimethyl-1,10-phenantorin, 4,7-diphenyl2,10-phenantorin, 3,8-di-t 61 "1; -butyl —1, 10—Phenant mouth phosphorus, 4, 7—Di-tert-butyl-1,10—Phenant mouth phosphorus, 3, 4, 7,8—Tetramethyl mono 1,10—Phenant mouth phosphorus, 2,9-dimethyl — 1, 10—Phenant mouth phosphorus, 2,9 1-dimethyl-4,7—Diphenyl bis 1,10—Phenant mouth phosphorus, 5, 6—Dimethoxy 1,10—Phenant mouth phosphorus, 4, 7—Dimethoxy 1,10 —Phenant mouth ring, 4, 7—Diphenoxy 1, 10— Examples include phenanthroline, 5—methyl-1,10—phenantorin, 4-methyl-1,10—phenantorin, 5, 6—methyl-1,10—phenantorin, 4,7 dimethyl-1,10— Phenant mouth phosphorus, 3, 8—Dimethyl-1, 10—Phenant mouth phosphorus, 4, 7—Diphenyl bis 1,10—Phenant mouth phosphorus, 3, 4, 7, 8—Tetramethyl 1,10—Phenant mouth phosphorus Is preferred.

As the phenantorporin compound (1), a commercially available one may be used. For example, a known method described in Journal of Heterocyclic Chemistry, 18, 641 (1981), etc. may be used. You may use what was manufactured similarly.

The amount of the phenantorin phosphorus compound (1) to be used is generally 0.2 to 2 mol, preferably 0.5 to 1.7 mol, per 1 mol of the divalent nickel compound.

A nickel complex in which a phenanthroline compound (1) is coordinated is prepared by previously bringing a phenantorin compound (1) into contact with a divalent nickel compound, and the prepared nickel complex is used as it is or after being isolated. Also good. The nickel complex is usually prepared in a solvent described later, and it can be determined that the nickel complex has been prepared by changing the hue of the reaction mixture.

This reaction is usually performed in the presence of a solvent. The solvent may be any solvent that can dissolve the aromatic compound to be used and the conjugated aromatic compound to be produced. Specific examples of such solvents include aromatic hydrocarbon solvents such as toluene and xylene; ether solvents such as tetrahydrofuran and 1,4-dioxane; dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N , N-dimethylacetamide, aprotic polar solvents such as hexamethylphosphoric triamide; halogenated hydrocarbon solvents such as dichloromethane and dichloroethane. Such solvents may be used alone or in combination of two or more. Of these, ether solvents and aprotic polar solvents are preferable, and tetrahydrofuran, dimethyl sulfoxide, N-methyl-1-pyrrolidone and N, N-dimethylacetamide are more preferable. If the amount of the solvent used is too large, a conjugated aromatic compound having a small molecular weight is likely to be obtained, and if it is too small, the properties of the reaction mixture are likely to deteriorate. The amount is usually 1 to 200 parts by weight, preferably 5 to 100 parts by weight, based on 1 part by weight of all the aromatic compounds.

The reaction is usually carried out by mixing an aromatic compound, a divalent nickel compound, zinc and a phenanthrolin compound (1) under an atmosphere of an inert gas such as nitrogen gas. The reaction temperature is usually 0 to 2500, preferably 30 to 100 ° C. The reaction time is usually 0.5 to 48 hours.

In order to increase the reaction rate, halide salts may be used. Specific examples thereof include sodium halides such as sodium fluoride, sodium chloride, sodium odorant sodium and sodium iodide, potassium fluoride, potassium chloride. Potassium halides such as potassium bromide and potassium iodide, tetraethylammonium fluoride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium bromide, etc. And halogenated ammonium, sodium halide is preferred, and sodium iodide is more preferred. The amount used is usually from 0.001 to 1 mol, preferably from 0.05 to 0.2 mol, based on 1 mol of all aromatic compounds used.

In this reaction, it is preferable that substantially no π-type ligand is used.

This reaction yields a conjugated aromatic compound, which has at least one aromatic ring and has a delocalized π-electron system in part or all of the molecule. Means a compound.

When the produced conjugated aromatic compound is a polymer, for example, after completion of the reaction, the reaction mixture is mixed with a solvent that does not dissolve or hardly dissolves the produced conjugated aromatic compound. The compound can be precipitated and the precipitated conjugated aromatic compound can be removed by filtration from the reaction mixture. After mixing the produced conjugated aromatic compound with a solvent that does not dissolve or difficult to dissolve, and a reaction mixture, an aqueous solution of an acid such as hydrochloric acid is added, and the precipitated conjugated aromatic compound is separated from the reaction mixture by filtration. Also good. The molecular weight and structure of the obtained conjugated aromatic compound can be analyzed by ordinary analytical means such as gel permeation chromatography and NMR. A solution that does not dissolve the resulting conjugated aromatic compound. Examples of the medium or the solvent difficult to dissolve include water, methanol, ethanol, and acetonitrile, and water and methanol are preferable.

When the produced conjugated aromatic compound is not a polymer, for example, after completion of the reaction, the produced conjugated aromatic compound can be taken out by concentrating the reaction mixture. The extracted conjugated aromatic compound may be further purified by ordinary purification means such as column chromatography, distillation, recrystallization and the like.

Specific examples of the resulting conjugated aromatic compound are shown below.

An aromatic compound (A) is reacted with an aromatic compound (A) having the same structure as the aromatic compound (A). If used, the following formula (20):

Ar ¹ to Ar ¹ (20)

(A r ¹ represents the same meaning as above.)

Is obtained.

As the conjugated aromatic compound represented by the formula (20),

Biphenyl, 4, 4, difluorobiphenyl, 3, 3 'difluorobiphenyl, 2, 2' difluoropiphenyl, 2, 2 '— dimethylbiphenyl, 2, 2', 5 , 5 '— Tetramethylbiphenyl, 2, 2, 1-Detylbiphenyl, 3, 3' Di-n-propylpiphenyl, 4, 4 '— Diisopropylbiphenyl, 5, 5' — Di n-Butylbi 'Phenyl, 2, 2'-diisobutylbiphenyl, 3, 3, di-sec-butyl biphenyl, 4, 4' zi-tert-butyl biphenyl, 5, 5 'mono-bis (2,2-dimethylpropyl) piphenyl, 2 , 2'-zi n-hexylbiphenyl, 4,4, -dicyclohexylbiphenyl, 4,4'-dibenzylbiphenyl, 4,4 'monodisianobiphenyl, 4, 4'-bis (trifluoro Methyl) biphenyl, 2,2'-bis (trifluoromethyl) pihue Le, 4, 4 'single-bis (Shianomechiru) Bifueeru,

3, 3 '— Dimethoxypiphenyl, 4, 4' — Dimethoxypiphenyl, 2, 2 ', 3, 3'-tetramethoxybiphenyl, 2, 2', 4, 4 '— Tetramethoxypiphenyl, 2, 2 ', 5,5'-tetramethoxybiphenyl, 2,2'-diethoxypiphenyl, 3,3'-di-n-propoxypiphenyl, 4, 4, -diisopropoxypiphenyl, 5, 5, -g n-butoxybiphenyl, 4,4'-di-tert-butoxypiphenyl, 4,4,1-diphenoxypiphenyl, 4,4, -dibenzyloxypiphenyl, 4, 4'-bis ( (Methoxymethyl) piphenyl, 4, 4, —bis (n-butoxymethyl) piphenyl, 4, 4, —bis (methoxymethoxy) piphenyl, 4, 4, —bis (benzyloxymethoxy) biphenyl, 4, 4 '—Bis {2— (n-butoxy) ethoxy} pifenyl,

4,4'-diacetylbiphenyl, 4,4, -dibenzoylbiphenyl, 4,4, -bis (phenylsulfonyl) piphenyl, biphenyl 4,4 'dimethyl monodisulfonate, pi Phenyl 4,4'-diethyl sulfonate, p-phenyl 4,4'-di (2,2-dimethylpropyl) disulfonate, biphenyl 3,3, di-disulfonate (2,2-dimethyl pill) , 1, 1 '— Pinaphthalene, 2, 2, 1 Pichiophene, 3, 3, ー Dihexyl, 5, 5, 1 Bitiophene, 1, 1' 1 Dimethyl-5, 5 'Bipyrrole, 2, 2' — Bi Pyridine, 3, 3 'Dimethyl-2, 2, 1 Biviridine, 3, 3, 1 Dihexyl— 5, 5' Bibipyridine, 2, 2 '—Bibirimidine, 5, 5' —Pyquinoline, 1, 1 '— Biisoquinoline, 4, 4, 1 bis (2, 1, 3—benzothiadiazole), 7, 7, 1 bis (ben Zomidazole) and the like.

An aromatic compound (A) is reacted with an aromatic compound (A) having the same structure, and n is 2 as the aromatic compound (A). When compound (2) is used, the following formula (21):

(A r ¹ represents the same meaning as above.)

A conjugated aromatic compound having a repeating unit represented by is obtained. Such conjugated aromatic compounds usually contain 2 to 10,000 repeating units represented by the formula (21), and the weight average molecular weight in terms of polystyrene is usually 500 to 3,000,000. Specific examples of the repeating unit represented by the formula (21) include a repeating unit represented by the following formula (21 a) d).

When the aromatic compound (A) is reacted with the aromatic compound (A) having the same structure as this, when the aromatic compound (3) is used as the aromatic compound (A) The following formula (22):

(A ² , R ⁷ , k and m have the same meaning as above.)

A conjugated aromatic compound having a repeating unit represented by is obtained. Such conjugated aromatic compounds usually contain 2 to: L 0,000 repeating units represented by the formula (22), and the weight average molecular weight in terms of polystyrene is usually 500 to 3,000,000. is there.

Specific examples of the repeating unit represented by the formula (22) include the following formulas (22 a) to (22 e) The repeating unit indicated by

When the aromatic compound (A) is reacted with an aromatic compound (A) having the same structure as this, when the aromatic compound (4) is used as the aromatic compound (A) The following formula (23):

A conjugated aromatic compound having a repeating unit represented by is obtained. Such conjugated aromatic compounds usually contain 2 to 10,000 repeating units represented by the formula (23), and the weight average molecular weight in terms of polystyrene is usually 1,000 to 6,000,000. is there.

Specific examples of the repeating unit represented by the formula (23) include the repeating units represented by the following formulas (23a) to (23d).

In the case of reacting an aromatic compound (A) with a structurally different aromatic compound (B), using the aromatic compound (2) as the aromatic compound (A), the aromatic compound ( When the aromatic compound (5) is used as B), the repeating unit represented by the formula (21) and the following formula (24):

The conjugated aromatic compound containing the segment shown by this is obtained. The weight average molecular weight in terms of polystyrene of the conjugated aromatic compound is usually 3,000 to 3,000,000.

Specific examples of the segment represented by the formula (24) include the segments represented by the following formulas (24 a) to (24 x). In the following formula, h represents the same meaning as described above, and is preferably 10 or more.

The conjugated aromatic compound containing the repeating unit represented by the formula (21) and the segment represented by the formula (24) is any one of the repeating units represented by the above formulas (21 a) to (21 d). One repeating unit and the segments represented by the formulas (24a) to (24x) And a conjugated aromatic compound containing any one of the above segments. Specific examples thereof include conjugated aromatic compounds represented by the following (I 1 1) to (I 1 16). Here, in the following formula, h represents the same meaning as described above, and p represents an integer of 2 or more.

In the case of reacting an aromatic compound (A) with a structurally different aromatic compound (B), using the aromatic compound (3) as the aromatic compound (A), the aromatic compound ( When aromatic compound (5) ′ is used as B), a conjugated aromatic compound containing a repeating unit represented by the formula (22) and a segment represented by the formula (24) is obtained. The polystyrene-reduced weight average molecular weight of the conjugated aromatic compound is usually 3,000 to 3,000,000. The amount of the repeating unit represented by the formula (22) in the conjugated aromatic compound is preferably 5% by weight or more and 95% by weight or less, more preferably 30% by weight or more and 90% by weight or less, and the formula (24 4 ) Is preferably 5% by weight or more and 95% by weight or less, more preferably 10% by weight or more and 70% by weight or less.

The conjugated aromatic compound containing the repeating unit represented by the formula (22) and the segment represented by the formula (24) may be any one of the repeating units represented by the formulas (22 a) to (22 e). Examples thereof include conjugated aromatic compounds comprising one repeating unit and any one of the segments represented by the formulas (24a) to (24x). Specific examples include conjugated aromatic compounds represented by the following (I 1 -1) to (I 1-9). Here, in the following formula, h represents the same meaning as above, and p represents an integer of 2 or more.

A reaction in which an aromatic compound (A) and a structurally different aromatic compound (B) are reacted, wherein the aromatic compound (A) is used as the aromatic compound (A), and the aromatic compound (A) When the aromatic compound (5) is used as B), a conjugated aromatic compound containing a repeating unit represented by the formula (23) and a segment represented by the formula (24) is obtained. The polystyrene-reduced weight average molecular weight of the conjugated aromatic compound is usually 3,000 to 3,000,000. The amount of the repeating unit represented by the formula (23) in the conjugated aromatic compound is preferably 5% by weight or more and 95% by weight or less, more preferably 30% by weight or more and 90% by weight or less, and the formula (24 4 ) Is preferably 5% by weight or more and 95% by weight or less, more preferably 10% by weight or more and 70% by weight or less.

The conjugated aromatic compound containing the repeating unit represented by the formula (23) and the segment represented by the formula (24) may be any one of the repeating units represented by the above formulas (23 a) to (23 d). Examples thereof include a conjugated aromatic compound containing one repeating unit and any one of the segments represented by the formulas (24a) to (24x). Specific examples include conjugated aromatic compounds represented by the following (III I :!) to (III I 6). Here, in the following formula, h represents the same meaning as above, and p represents an integer of 2 or more.

In the case of reacting an aromatic compound (A) with a structurally different aromatic compound (B), using the aromatic compound (2) as the aromatic compound (A), the aromatic compound ( When the aromatic compound (3) is used as B), a conjugated aromatic compound containing the repeating unit represented by the formula (21) and the repeating unit represented by the formula (22) is obtained. The polystyrene-reduced weight average molecular weight of the conjugated aromatic compound is usually 1,000 to 2,000,000. The amount of the repeating unit represented by the formula (21) in the conjugated aromatic compound is preferably 1% by weight or more and 99% by weight or less, and the amount of the repeating unit represented by the formula (22) is 1% by weight or more, 99 weight% or less is preferable.

Examples of the common aromatic compound containing the repeating unit represented by the formula (21) and the repeating unit represented by the formula (22) include any of the repeating units represented by the formulas (21 a) to (21 d). Examples thereof include conjugated aromatic compounds containing one repeating unit and any one of the repeating units represented by the formulas (22a) to (22e). Specific examples include conjugated aromatic compounds represented by the following (IV-1) to (IV-4).

In the case of reacting an aromatic compound (A) with a structurally different aromatic compound (B), using the aromatic compound (2) as the aromatic compound (A), the aromatic compound ( When the aromatic compound (4) is used as B), a conjugated aromatic compound containing the repeating unit represented by the formula (21) and the repeating unit represented by the formula (23) is obtained. The polystyrene-reduced weight average molecular weight of the conjugated aromatic compound is usually 000 to 2,000,000. The amount of the repeating unit represented by the formula (21) in the conjugated aromatic compound is preferably 1% by weight or more and 99% by weight or less, and the amount of the repeating unit represented by the formula (23) is 1% by weight or more, 99 weight% or less is preferable.

Examples of the co-aromatic compound containing the repeating unit represented by the formula (21) and the repeating unit represented by the formula (23) include any of the repeating units represented by the formulas (21 a) to (21 d). Examples thereof include conjugated aromatic compounds containing one repeating unit and any one of the repeating units represented by the formulas (23a) to (23d). Specifically

The content of each repeating unit in the conjugated aromatic compound containing two or more types of repeating units can be adjusted by appropriately adjusting the amount of the aromatic compound used.

The conjugated aromatic compound containing the repeating unit represented by the formula (22) or the formula (23) can be used as a raw material for synthesizing a polymer electrolyte for a solid polymer type fuel cell. The weight average molecular weight of is 2,000 to 1,000,000, more preferably 3,000 to 800,000. Example

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. When the resulting conjugated aromatic compound was not a polymer, it was analyzed by gas chromatography internal standard method, and the yield was calculated from the result. When the obtained conjugated aromatic compound is a polymer, it is analyzed by gel permeation chromatography (hereinafter abbreviated as GPC) (analysis conditions are as follows). Average molecular weight (Mw) and number average molecular weight (Mn) were calculated.

GP C measuring device: C TO— 1 OA (manufactured by Shimadzu Corporation)

Column: TSK— GEL (manufactured by Tosohichi Corporation)

Column temperature: 40 ° C

Mobile phase: Odory lithium-containing N, N-dimethylacetamide (Odory lithium concentration: 10m mo 1 / dm ³ )

Flow rate: 0.5mL / min

Detection wavelength: 300 nm

2,4,9 g of 2,2-dimethylpropanol was dissolved in 145 g of pyridine. to this,

Add 100 g of 2,5-dichlorobenzenesulfonic acid chloride at 0 ° C, and at room temperature for 1 hour Stir and react. To the reaction mixture, 74 mL of ethyl acetate and 740 mL of 2mo 1% hydrochloric acid were added, stirred for 30 minutes, and allowed to stand to separate the organic layer. The separated organic layer was washed with 740 mL of water, 74 OmL of a 10 wt% aqueous potassium carbonate solution, and further saturated. 74 OmL of brine, and then the solvent was distilled off under reduced pressure. The residue was purified by silica gel force ram chromatography (solvent: black mouth form). The solvent was distilled off from the resulting eluate under reduced pressure. The residue was dissolved in 97 mL of hexane at 65 ° C. and then cooled to room temperature. The precipitated solid was separated by filtration. The separated solid was dried to obtain 99.4 g of a white solid of 2,5-dichlorobenzenebenzenesulfonic acid (2,2-dimethylpropyl). Yield: 82.1%.

¹ H-NMR (CDC 1 ₃ > δ (p pm)): 0.97 (s, 9H), 3. 78 (s, 2 H), 7. 52-7. 53 (c, 2H), 8. 07 (d, 1 H)

Mass spectrum (mZz): 297 (M ⁺ )

In a glass reaction vessel equipped with a cooling device, in a nitrogen atmosphere at room temperature, nickel bromide 50 mg, 3, 4, 7, 8-tetramethyl mono 1,10-phenantine phosphorus 54 mg, zinc powder 9 8 mg, N -A solution obtained by dissolving 4 mL of methyl-2-pyrrolidone and 227 mg of 2,5-dichlorobenzene sulfonic acid (2,2-dimethylpropyl) in 1 mL of N-methyl-2-pyrrolidone was added. The resulting mixture was reacted at 70 ° C for 4 hours to obtain the following formula (i)

The reaction mixture containing the conjugated aromatic compound which consists only of repeating units shown by was obtained. The Mw of the conjugated aromatic compound was 44,000, and the Mn was 21,000. Comparative Example 1>

In Example 1, 3, 4, 7, 8—tetramethyl mono-1,10-phenanthrin 5 The reaction was conducted in the same manner as in Example 1 except that 36 mg of 2,2′-pipyridine was used instead of 4 mg, and a reaction mixture containing a conjugated aromatic compound consisting only of the repeating unit represented by the formula (i) I got a thing. The Mw of the conjugated aromatic compound was 25,000 and Mn was 13,000. <Reference Example 2>

2,2-Dimethylpropanol 25.2 g was dissolved in tetrahydrofuran 20 OmL. To this, 151.6 mL of n-butyl lithium in hexane (1.57M) was added dropwise at 0 ° C. Thereafter, the mixture was stirred at room temperature for 1 hour to prepare a solution containing lithium 2,2-dimethylpropoxide. Lithium 2,2-dimethylpropoxide prepared at 0 ° C in a solution obtained by dissolving 40 g of 4,4'-dichloropiphenyl-2,2 'monodisulfonic acid dichloride in 30 OmL of tetrahydrofuran A solution containing was added dropwise. Thereafter, the mixture was stirred and reacted at room temperature for 1 hour. After the reaction mixture was concentrated, ethyl acetate 100 OmL and 2 mo 1 / L¾100 OmL were added to the residue and stirred for 30 minutes. After standing, the organic layer was separated. The separated organic layer was washed with 100 OmL of saturated brine, and the solvent was distilled off under reduced pressure. The concentrated residue was purified by silica gel chromatography (solvent; Kuroguchi Form). The solvent was removed from the eluate obtained under reduced pressure. The residue was dissolved in 50 OmL of toluene at 70 ° C and then cooled to room temperature. The precipitated solid was separated by filtration. The separated solid was dried to obtain 31.2 g of a white solid of 4,4, -dichlorobiphenyl 2,2′-disulfonic acid di (2,2-dimethylpropyl). Yield: 62.6%.

1 H-NMR (CDC 1 ₃ , δ (p pm)): 0.92 (s, 18 H), 3. 69-3.

86 (c, 4H), 7. 34- 7. 37 (c, 2 H), 7. 59-7. 62 (c, 2H), 8. 03-8. 04 (c, 2H)

Mass spectrum (mZz): 451 (M-CsHn) <Example 2>

In a glass reaction vessel equipped with a cooling device, at room temperature under a nitrogen atmosphere, nickel bromide 8 mg, 4, 7-Diphenyl 2-, 10-Phenant mouth phosphorus 14 mg, Zinc powder 72 mg, Ν, Ν— Dimethylacetamide 2 mL and 4, 4'-dichlorobiphenyl-2, 2 '— Disulfonate (2 , 2-dimethylpropyl) 366] 118 in 3 mL of 1 ^ N-dimethylacetamide was added. The resulting mixture was reacted at 70 ° C for 4 hours to obtain the following formula (ii)

The reaction mixture containing the conjugated aromatic compound which consists only of repeating units shown by was obtained. The Mw of the conjugated aromatic compound was 288,000 and Mn was 89,000. Comparative Example 2>

In Example 2, the reaction was carried out in the same manner as in Example 2 except that 7 mg of 2,2′-pipyridine was used instead of 14 mg of 4,7-diphenyl-1,10-phenantorin, and the above formula (ii) A reaction mixture containing a conjugated aromatic compound consisting only of repeating units represented by the formula (1) was obtained. The Mw of the synergistic aromatic compound was 70,000, and Mn was 28,000.

In a glass reaction vessel equipped with a cooling device, at room temperature under a nitrogen atmosphere, nickel bromide 15 mg, 4, 7-diphenyl 2,10-phenantine phosphorus 28 mg, zinc powder 76 mg, 4, 4'-dichloro A solution obtained by dissolving 66 mg of diphenyl-2,2′-disulfonic acid di (2,2-dimethylpropyl) 3 in 3 mL of N, N-dimethylacetamide and the following formula (iii)

A solution obtained by dissolving 206] 118 in 2 mL of ^^ N-dimethylacetamide (Sumitomo Chemical Co., Ltd .; Mw 94, 00 0, Mn 40, 000: measured under the above analytical conditions) Was added. Thereafter, a polymerization reaction is carried out at 70 ° C for 4 hours, and the repeating unit represented by the above formula (ii) and the following formula

A reaction mixture containing a conjugated aromatic compound consisting of the segment represented by The Mw of the conjugated aromatic compound was 276,000 and Mn was 91,000.

In a glass reaction vessel equipped with a cooling device, in a nitrogen atmosphere at room temperature, nickel bromide 1 lm g, 4,7-diphenyl-1,10-phenanthrin 2 lmg, zinc powder 74 mg, 4, 4 ' —Dichloropiphenyl— 2,2 ′ monodisulfonic acid di (2,2-dimethylpropyl) 3 66 mg of N, N-dimethylacetamide dissolved in 3 mL and the following formula

(Mw 60, 000, Mn 32, 000: measured under the above analytical conditions) 10 Omg dissolved in 2 mL of N, N-dimethylacetamide was added. It was. The obtained mixture was reacted at 70 for 4 hours, and the repeating unit represented by the above formula U i) and the following formula

A reaction mixture containing a conjugated aromatic compound consisting of the segment represented by The Mw of the conjugated aromatic compound was 348,000, and Mn was 127,000. <Example 5>

In Example 4, instead of the polyphenylsulfone 1 O Omg represented by the formula U V), the following formula (V)

(Mw 5, 900, Mn 3, 9 ° 0: measured under the above analytical conditions) The reaction was carried out in the same manner as in Example 4 except that 206 mg was used, and the recursion represented by the above formula (ii) was carried out. Return unit and following formula

A reaction mixture containing a conjugated aromatic compound consisting of the segment represented by The Mw of the conjugated aromatic compound was 567,000, and Mn was 140,000.

In a glass reaction vessel equipped with a cooling device, in a nitrogen atmosphere at room temperature, nickel bromide 46 mg, 4, 7-diphenyl 1,10-phenant phosphorus 84 mg, zinc powder 92 mg, 2, 5-dichloro 4 '-Phenoxybenzophenone 24 Omg and N, N-dimethylacetamide 5mL were added. The resulting mixture is reacted at 70 ° C for 4 hours.

The reaction mixture containing the conjugated aromatic compound which consists only of repeating units shown by was obtained. The Mw of the conjugated aromatic compound was 154,000, and the Mn was 36,000. Example 7>

In Example 6, 2,5-dichloro-1,4-decyloxybenzene (212 mg) was replaced with 5 mL of N, N-dimethylacetamide instead of 24 Omg The reaction was carried out in the same manner as in Example 6 except that 3 mL of N-methyl-2-pyrrolidone was used.

A reaction mixture containing a conjugated aromatic compound consisting only of repeating units represented by the formula (1) was obtained. The Mw of the conjugated aromatic compound was 32,000, and the Mn was 15,000. <Example 8>

In Example 6, 3,4,7,8-tetramethyl mono-1,10-phenanthrine 6 Omg was replaced with 2,5-dichloromono-1,10-phenanthrine 84 mg instead of 84 mg 4,7-diphenyl mono 4, Monophenoxybenzophenone 24, 7-dichloro-9,9-didodecyl 9 H-fluorene 462 mg instead of 5 mg N, N-dimethylacetamide 5 mL N, N-dimethylacetate Use a mixed solvent of amide 3.5 mL and toluene 1.5 mL The reaction was carried out in the same manner as in Example 6 except that

The reaction mixture containing the conjugated aromatic compound which consists only of repeating units shown by was obtained. The Mw of the conjugated aromatic compound was 343,000, and the Mn was 75,000.

<Example 9> '

To a glass reaction vessel equipped with a cooling device was added 15 mg of nickel bromide, 3, 4, 7, 8-tetramethyl-1,10-phenanthrine 2 Omg and 92 mg of zinc powder at room temperature under a nitrogen atmosphere. . To the obtained mixture, 89 mg of 4-necked toluene and 5 mL of N-methyl-2-pyrrolidone were added at room temperature. The obtained mixture was reacted at 70 ° C. for 2 hours to obtain a reaction mixture containing 4,4 ′ monodimethylbiphenyl. The yield of 4,4′-dimethylbiphenyl was 55 mg.

In Example 9, 3, 4, 7, 8—tetramethyl-1,1,10-phenanthrin 2

The reaction was conducted in the same manner except that 28 mg of 4,7-diphenyl-1,10-phenantorin was used in place of Omg to obtain a reaction mixture containing 4,4′-dimethylbiphenyl. The yield of 4,4'-dimethylbiphenyl was 49 mg. <Example 11>

In Example 9, the same reaction was carried out except that 17 mg of 5,6-dimethyl-1,10-phenanthrine was used instead of 2,4,7,8-tetramethyl-1,10-phenanthrine 2 Omg. And a reaction mixture containing 4,4′-dimethylpiphenyl was obtained. The yield of 4,4'-dimethylbifuel was 57 mg. <Example 1 2>

In Example 9, the same procedure except that 6 mg of 5,4-methyl-1,10-phenanthorin was used instead of 3,4,7,8-tetramethyl-1,10-phenantorin 2 Omg. The reaction was conducted to obtain a reaction mixture containing 4,4′-dimethylbiphenyl. The yield of 4,4'-dimethylbiphenyl was 49 mg.

In Example 9 ′, the reaction was carried out in the same manner except that 3,4,7,8-tetramethyl-1,10-phenanthorin 2 Omg was replaced by 2,2′-biviridine 13 mg, and 4,4 ′ A reaction mixture containing dimethylbiphenyl was obtained. The yield of 4,4′-dimethylbiphenyl was 36 mg.

In Example 9, instead of 89 mg of 4-chloro toluene 4 1 chloroadisol 1 0

A reaction was carried out in the same manner except that Omg was used to obtain a reaction mixture containing 4,4′-dimethoxypiphenyl. The yield of 4,4'-dimethoxybiphenyl was 58 mg.

In Example 9, 3, 4, 7, 8—tetramethyl-1,10—phenantorin 2

Reaction was carried out in the same manner except that 7 mg of 5,6-dimethyl-1,10-phenanthrine was substituted for Omg instead of 4 mg of 4-chloroaluminol and 10 Omg of toluene was replaced with 89 mg of 4-chloromouth. A reaction mixture containing 4′-dimethoxypiphenyl was obtained. The yield of 4,4'-dimethoxybiphenyl was 56m.

<Example 1 5> The reaction was carried out in the same manner as in Example 9 except that 3-chloroanisole 10 Omg was used in place of 89 mg of 4-monochlorotoluene to obtain a reaction mixture containing 3,3′-dimethoxybiphenyl. The yield of 3,3′-dimethoxybiphenyl was 69 mg. <Example 16>

In Example 9, instead of 3, 4, 7, 8-tetramethyl-1,10-phenantorin 2 Omg, 28 mg of 4,7-diphenyl-1,10-phenantorin was substituted with 28 mg of 4-cloantorin 89 mg The reaction was carried out in the same manner except that 10 mg of 3-chloroanisole was used in place of 1, to obtain a reaction mixture containing 3,3, -dimethoxypiphenyl. The yield of 3,3, -dimethyloxybiphenyl was 64 mg.

In Example 9, instead of 3, 4, 7, 8-tetramethyl-1,10-phenantine phosphorus 2 Omg, 17 mg of 5,6-dimethyl-1,10-phenantorin, 4 mg of monochlorotoluene 89 mg A reaction mixture containing 3,3′-dimethoxybiphenyl was obtained in the same manner except that 100 mg of 3-chloroanisole was used instead. The yield of 3,3'-dimethyoxyphenyl was 66 mg.

In Example 9, 3, 4, 7, 8—tetramethyl mono-1,10-phenanthrin 2

The reaction was carried out in the same manner, except that 16 mg of 5-methyl-1,10-phenanthral was substituted for Omg, and 3-chloroazol 10 Omg was substituted for 89 mg of 4-chlorotoluene. A reaction mixture containing dimethoxybiphenyl was obtained. The yield of 3,3'-dimethylbiphenyl was 66 mg.

<Example 19> In Example 9, the reaction was carried out in the same manner except that 108 mg of 4′-chloroacetophenone was used in place of 89 mg of 4-chlorotoluene, and a reaction mixture containing 4,4′-diacetylbiphenyl was obtained. Obtained. The yield of 4, 4'-diacetyl bifuel was 79 mg. <Example 20>

In Example 9, instead of 3,4,7,8-tetramethyl-1,10-phenantorin 2 O.mg, 28 mg of 4,7-diphenyl-1,10-phenantorin, and 89 mg of 4-clotoltoluene The reaction was carried out in the same manner except that 108 mg of 4′-chloroacetophenone was used instead of 4 to obtain a reaction mixture containing 4,4′-diacetylbiphenyl. The yield of 4,4′-diacetylbiphenyl was 76 mg.

In Example 9, 3,4,7,8-tetramethyl_1,10-phenantorin 2 Omg instead of 5,6 1-dimethyl-1,10-phenantorin 17 mg was replaced with 4-clotoluene 89 mg The reaction was carried out in the same manner except that 108 mg of 4′-chloroacetophenone was used to obtain a reaction mixture containing 4,4,1-diacetylpiphenyl. The yield of 4,4'-diacetylbiphenyl was 74 mg.

In Example 9, 3, 4, 7, 8-tetramethyl mono-1,10-phenantorporin 2

The reaction was carried out in the same manner except that 4-methyl-1,10-phenanthrine 16 mg was used instead of Omg, and 4'-chloroacetophenone 108 mg was used instead of 4-chlorotoluene 89 mg. A reaction mixture containing 1-diacetylpiphenyl was obtained. The yield of 4,4'-diacetyl pphenyl was 76 m.

<Example 23> In Example 9, the reaction was carried out in the same manner except that 9 lmg of 4-chloro-fluobenzene was used instead of 89 mg of 4-chloro-toluene, and a reaction containing 4,4′-difluorobiphenyl was performed. A reaction mixture was obtained. The yield of 4,4′-difluorobiphenyl was 6 lmg. <Example 24>

In Example 9, instead of 3, 4, 7, 8-tetramethyl-1,10-phenanthrine 2 Omg, 28 mg of 4,7-diphenyl-1,10-phenanthrine was replaced with 89 mg of 4-chlorotoluene. Instead, the reaction was conducted in the same manner except that 9 lmg of 4-chlorofluorobenzene was used to obtain a reaction mixture containing 4,4′-difluoropiphenyl. The yield of 4,4'-difluorobiphenyl was 55 mg.

In Example 9, 3,4,7,8-tetramethyl-1,10-phenantorin 2 Omg instead of 5,6 monodimethyl-1,10-phenantorin 17 mg was replaced with 4-monochlorotoluene 89 mg The reaction was carried out in the same manner except that 91 mg of 4-chlorofluorobenzene was used, and a reaction mixture containing 4,4, -difluorobiphenyl was obtained. The yield of 4,4'-difluoropiphenyl was 57 mg.

In Example 9, 3, 4, 7, 8-tetramethyl mono-1,10-phenantorporin 2

The same reaction was carried out except that 4 mg of 4-methyl-1,10-phenantine phosphorus instead of Omg was used, and 9 lmg of 4-chlorochlorobenzene was substituted for 89 mg of 4-chlorotoluene. A reaction mixture containing robiphenyl was obtained. The yield of 4,4′-difluorobiphenyl was 57 mg.

<Example 27> In Example 9, the reaction was carried out in the same manner except that 96 mg of 4-chlorobenzoic benzonitrile was used instead of 89 mg of 4-chlorotoluene, to obtain a reaction mixture containing 4,4′-dicyanobiphenyl. It was. The yield of 4,4′-dicyanobiphenyl was 57 mg. <Example 28>

In Example 9, the reaction was carried out in the same manner except that 4-chloro-11- (methoxymethyl) benzene 11 Omg was used instead of 89 mg of 4-chlorotoluene, and 4,4′-bis (methoxymethyl) piphenyl was used. A reaction mixture containing was obtained. The yield of 4,4, -bis (methoxymethyl) biphenyl was 68 mg.

In Example 9, in place of 3, 4, 7, 7, 8-tetramethyl-1,10-phenantorin 2 Omg, 17 mg of 5,6-dimethyl-1,10-phenantorin was replaced with 89 mg of 4-clotoluene toluene. The reaction was carried out in the same manner except that 11 Omg of 4-chloro (methoxymethyl) benzene was used, and a reaction mixture containing 4,4′-monobis (methoxymethyl) biphenyl was obtained. The yield of 4,4'-bis (methoxymethyl) biphenyl was 68 mg.

In Example 9, 3,4,7,8-tetramethyl-1,10-phenantorin 2 Omg instead of 5-methyl-1,10-phenantorin 16 mg, 4-chlorotoluene 89 mg instead of 4-chloro Mouth (methoxymethyl) benzene 11 Omg was used in the same manner to obtain a reaction mixture containing 4,4′-bis (methoxymethyl) piphenyl. The yield of 4,4′-bis (methoxymethyl) bifuel was 65 mg. <Example 31>

In Example 9, 2-bromothiophene 1 1 instead of 89 mg of toluene 4 × The reaction was carried out in the same manner except that 4 mg was used, and a reaction mixture containing 2,2′-one-pithiophene was obtained. The yield of 2,2'-one-pichiophene was 45 mg.

In Example 9, 3, 4, 7, 8—tetramethyl-1, 1 0—phenantorin 2

Reacts in the same manner except that 4, 7-diphenyl rosin 1, 10 0-phenantorin 2 8 mg was used instead of Omg, and 2-momotiophene 1 1 4 mg was used instead of 4-chlorotoluene 8 9 mg. To obtain a reaction mixture containing 2,2′-bithiophene. The yield of 2, 2, and -pichiophene was 43 mg. Example 3 3>

In Example 9, instead of 3, 4, 7, 8-tetramethyl-1,10-phenantine phosphorus 2 Omg, 5-methyl-1,10-phenantine phosphorus 16 mg was replaced with 4-chlorotoluene 8 9 mg. The reaction was carried out in the same manner except that 2-bromothiophene 1 1 4 mg was used, and a reaction mixture containing 2,2′-one-pithiophene was obtained. The yield of 2,2'-one-pichiophene was 42 mg.

In Example 9, 3, 4, 7, 8—tetramethyl-1,10—phenantoracin 2 Omg instead of 2,2′-bibilysin 1 3 mg, The reaction was carried out in the same manner except that 4 mg of promothiophene 1 1 was used, and a reaction mixture containing 2,2′-pichiofen was obtained. The yield of 2, 2 '-pitiophene was 25 mg.

In a glass reaction vessel equipped with a cooling device, at room temperature under a nitrogen atmosphere, nickel bromide 8 mg,

4, 7-Difenil 1, 1 0-Phenant mouth phosphorus 14mg and N, N-dimethylase 2 mL of toamide was added. The resulting mixture was an ocher slurry. The slurry was heated to 70 ° C. to obtain a green uniform solution containing a nickel complex.

In a glass reaction vessel equipped with a cooling apparatus, in a nitrogen atmosphere at room temperature, a solution containing the nickel complex obtained in Example 34 above, 72 mg of zinc powder, and 4,4′-dichloropifenil, 2, 2 ′ disulfonic acid disulfate 366 mg of (2,2-dimethylpropyl) was added. The obtained mixture was reacted at 70 ° C. for 4 hours to obtain a reaction mixture containing a conjugated aromatic compound consisting only of the repeating unit represented by the above formula (ii). The Mw of the conjugated aromatic compound was 143,000 and Mn was 48,000. Industrial applicability

According to the present invention, a conjugated aromatic compound can be produced more advantageously.

Claims

The scope of the claims

1. An aromatic compound (A) in which one or two leaving groups are bonded to an aromatic ring and an aromatic compound (A) having the same structure or the aromatic compound (A) An aromatic compound (B) in which one or two structurally different leaving groups are bonded to an aromatic ring, and a catalytic amount of a divalent nickel compound, zinc and formula (1):

(In the formula, RR ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different from each other, hydrogen atom, fluorine atom, alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms. Represents an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms or a cyano group, provided that RR ² , R ³ , R ⁴ , R ⁵ and R ⁶ Are not hydrogen atoms at the same time.)

A process for producing a conjugated aromatic compound, wherein the reaction is carried out in the presence of a phenanthroline compound represented by the formula:

2. The aromatic rings of the aromatic compound (A) and aromatic compound (B) are the same or different, and the benzene ring, biphenyl ring, naphthalene ring, fluorene ring, anthracene ring, phenanthrene ring, thiophene ring, pyrone ring The conjugated aromatic group according to claim 1, which is a monocyclic ring, a pyridine ring, a pyrimidine ring, a quinoline ring, an isoquinoline ring or a quinoxaline ring, and may be substituted with at least one group not participating in the reaction. Compound production method.

3. RK R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and each is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, The method for producing a conjugated aromatic compound according to claim 1, wherein at least one of them is an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms.

4. The conjugated aromatic compound according to claim ¹ , wherein R ¹ and R ⁶ are the same group, R ² and R ⁵ are the same group, and R ³ and R ⁴ are the same group. Manufacturing method.

5. The method for producing a conjugated aromatic compound according to claim 4, wherein R ² and R ⁵ are the same aryl group having 6 to 10 carbon atoms.

6. The method for producing a conjugated aromatic compound according to claim 5, wherein the aryl group having 6 to 10 carbon atoms is a phenyl group.

7. The method for producing a synergistic aromatic compound according to claim ⁶ , wherein R ¹ , R ³ , R ⁴ and R ⁶ are hydrogen atoms.

8. The method for producing a conjugated aromatic compound according to claim 4, wherein R ¹ , R ⁶ , R ² and R ⁵ are the same alkyl group having 1 to 6 carbon atoms.

9. The method for producing a conjugated aromatic compound according to claim 8, wherein R ³ and R ⁴ are hydrogen atoms.

10. The method for producing a conjugated aromatic compound according to claim ^{4, wherein} R ³ and R ⁴ are the same alkyl group having 1 to 6 carbon atoms.

11. The method for producing a synergistic aromatic compound according to claim 10, wherein R ¹ , R ⁶ , R ² and R ⁵ are hydrogen atoms.

12. The method for producing a conjugated aromatic compound according to claim 1, wherein the aromatic compound (A) is reacted with the aromatic compound (A) having the same structure as the aromatic compound (A).

13. Aromatic compound (A) has the formula (2):

(In the formula, A r ¹ represents an n-valent aromatic group, and the aromatic ring constituting the aromatic group is a benzene ring, biphenyl ring, naphthalene ring, fluorene ring, anthracene ring, phenanthrene ring, A phen ring, a pyrrole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, an isoquinoline ring or a quinoxaline ring, and an aromatic ring which may be substituted with at least one group not involved in the reaction, X ¹ is Represents a leaving group, and n represents 1 or 2. When n is 2, X ¹ may be the same or different. The method for producing a conjugated aromatic compound according to claim 12, which is an aromatic compound represented by the following formula.

1 4. The aromatic compound (A) has the formula (3)

(In the formula, A ² represents an amino group substituted with one or two hydrocarbon groups having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms. Here, the hydrocarbon group and The alkoxy group includes a fluorine atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, and It may be substituted with at least one group selected from the group consisting of a cyano group.

R ⁷ is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Represents a C2-C20 acyl group or cyano group, the C1-C20 alkyl group, the C1-C20 alkoxy group, the C6-C20 aryl group, The aryloxy group having 6 to 20 carbon atoms and the aforementioned acyl group having 2 to 2 carbon atoms are a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. And may be substituted with at least one substituent selected from the group consisting of aryloxy groups having 6 to 20 carbon atoms. When R ⁷ is plural, R ⁷ may be the same group or different groups. Moreover, two adjacent R ^7s may be bonded to form a ring. X ² represents a chlorine atom, a bromine atom or an iodine atom. m represents 1 or 2, and k represents 4—m. )

The method for producing a conjugated aromatic compound according to claim 12, which is an aromatic compound represented by the following formula.

1 5. The aromatic compound has the formula (4)

(In the formula, A ³ represents an amino group substituted by one or two hydrocarbon groups having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms. And an alkoxy group include a fluorine atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, and a cyano group. It may be substituted with at least one group selected from the group consisting of groups.

R ⁸ is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or 2 carbon atoms. Represents an alkyl group having 2 to 20 carbon atoms or a cyan group, the alkyl group having 1 to 20 carbon atoms, the alkoxy group having 1 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, The aryl group having 6 to 20 carbon atoms and the acyl group having 20 to 20 carbon atoms are a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, and an alkyl group having 6 to 20 carbon atoms. And may be substituted with at least one substituent selected from the group consisting of an aryl group and a C6-C20 aryloxy group. When R ⁸ is plural, R ⁸ may be the same group or different groups. Also, two adjacent R ⁸ may be bonded to form a ring.

X ³ represents a chlorine atom, a bromine atom or an iodine atom. j represents an integer of 0 to 3. The method for producing a conjugated aromatic compound according to claim 12, which is an aromatic compound represented by the following formula:

16. The method for producing a conjugated aromatic compound according to claim 1, wherein the aromatic compound (A) is reacted with an aromatic compound (B) structurally different from the aromatic compound (A). .

1 7. As the aromatic compound (A), the aromatic compound represented by the formula (2) described in claim 13 is used, and the aromatic compound (B) is used as the aromatic compound (A). Is structural An aromatic compound represented by the formula (2) according to claim 13 according to claim 13, an aromatic compound represented by the formula (3) according to claim 14; Aromatic compound represented by formula (4) or formula (5) described in paragraph 15

(a2) at least one selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms An alkyl group having 1 to 20 carbon atoms which may be substituted with one substituent;

(d2) carbon atoms that may be substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms An aryloxy group of

Y ¹ and Y ² are the same or different, a single bond, - CO-, - S_〇 _{_{2 -, -C (CH 3)}} 2 —, — C (CF ₃ ) .2— or a fluorene 9, 9-diyl group.

Z ¹ and Z ² are the same or different and represent —〇1 or —S—. X ⁴ represents a chlorine atom, a bromine atom or an iodine atom. )

17. The method for producing a conjugated aromatic compound according to claim 16, wherein an aromatic compound represented by the formula is used.

18. As the aromatic compound (A), the aromatic compound represented by the formula (3) described in claim 14 is used, and as the aromatic compound (B), the aromatic compound (A) is a structure. The aromatic compound represented by the formula (2) described in claim 13 according to claim 13, the aromatic compound represented by formula (3) described in claim 14, and claim 15. The conjugated aromatic compound according to claim 16 using the aromatic compound represented by formula (4) according to claim 16 or the aromatic compound represented by formula (5) according to claim 17. Manufacturing method.

19. As the aromatic compound (A), an aromatic compound represented by the formula (4) described in claim 15 is used. As the aromatic compound (B), the aromatic compound (A) is a structure. The aromatic compound represented by the formula (2) described in claim 13 according to claim 13, the aromatic compound represented by formula (3) described in claim 14, and claim 15. The conjugated aromatic compound according to claim 16 using the aromatic compound represented by formula (4) according to claim 16 or the aromatic compound represented by formula (5) according to claim 17. Production method.

20. The leaving group is a chlorine atom, bromine atom, iodine atom, trifluoromethylsulfonyloxy group, alkylsulfonyloxy group having 1 to 6 carbon atoms, or arylsulfonyloxy group having 6 to 10 carbon atoms. The method for producing a conjugated aromatic compound according to claim 1, wherein

21. The method for producing a conjugated aromatic compound according to claim 1, wherein the divalent nickel compound is nickel halide.

22. The method for producing a conjugated aromatic compound according to claim 1, wherein substantially no π-type ligand is used.

23. Divalent dieckel compounds and formula (1):

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different from each other, hydrogen atom, fluorine atom, alkyl group having 1 to 20 carbon atoms, carbon number 1 to 20 An alkoxy group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, or a cyano group, provided that R ¹ R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are not hydrogen atoms at the same time.)

The nickel complex obtained by making it contact with the phenanthroline compound shown by this.