WO2012137694A1

WO2012137694A1 - Method for producing chalcogen-containing condensed polycyclic compound

Info

Publication number: WO2012137694A1
Application number: PCT/JP2012/058789
Authority: WO
Inventors: 康生宮田; 善丈鈴木
Original assignee: 住友化学株式会社
Priority date: 2011-04-04
Filing date: 2012-03-27
Publication date: 2012-10-11
Also published as: JP2012219015A; JP5708161B2; TW201245173A

Abstract

A chalcogen-containing condensed polycyclic compound (5) can be produced under mild reaction conditions by a production method that includes a step for obtaining an aromatic heterocyclic compound expressed by formula (2a) by reacting an aromatic heterocyclic compound expressed by formula (1a) and an N-halocarboxylic acid amide in the presence of water or alcohol.

Description

Method for producing chalcogen-containing fused polycyclic compound

The present invention relates to a process for producing a chalcogen-containing fused polycyclic compound.

As an organic semiconductor material useful in the field of organic electronics such as an organic thin film transistor, US2007 / 117793 proposes a chalcogen-containing condensed polycyclic compound, which includes a condensed polycyclic compound containing a disulfide bond as a transition metal catalyst. A production process is described in which it is heated at about 200 ° C. in the presence.
However, from an industrial viewpoint, a method for producing a chalcogen-containing condensed polycyclic compound under lower mild reaction conditions is required.

The present invention provides a method for producing a chalcogen-containing polycyclic compound under mild reaction conditions.
That is, the present invention provides the formula (1a)

The aromatic heterocyclic compound represented by the formula [Aromatic heterocyclic compound (1a)] is reacted with N-halocarboxylic acid amide in the presence of water or alcohol to give a compound of formula (2a)

A process for obtaining an aromatic heterocyclic compound [aromatic heterocyclic compound (2a)] represented by:
Aromatic heterocyclic compound (2a) and formula (3)

And an aromatic compound represented by the formula [Aromatic compound (3)]

A step of obtaining a compound [compound (4)] represented by formula (5) and reacting the compound (4) with an acid,

A method for producing a chalcogen-containing polycyclic compound (5) comprising the step of obtaining a chalcogen-containing polycyclic compound [chalcogen-containing polycyclic compound (5)] shown in FIG.
Here, in each formula, R ¹ represents an alkyl group having 1 to 20 carbon atoms, Z ¹ independently represents a sulfur atom or a selenium atom, and Z ² represents an oxygen atom, a sulfur atom or a selenium atom. R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, or 1 to carbon atoms which may have a substituent. 30 alkoxy groups, optionally substituted aryl groups having 6 to 30 carbon atoms, optionally substituted aralkyl groups having 7 to 30 carbon atoms, optionally having substituents A heteroaralkyl group having 5 to 30 carbon atoms, a heteroaryl group having 4 to 30 carbon atoms which may have a substituent, or a formula —Si (R ² ) ₃ (wherein R ² independently represents a substituent) An optionally substituted alkyl group having 1 to 30 carbon atoms or an optionally substituted aryl group having 6 to 30 carbon atoms). X ¹ represents a halogen atom, and X ² represents a leaving group.

Hereinafter, preferred embodiments of the present invention will be described in detail.
The aromatic heterocyclic compound (2a) can be obtained by reacting the aromatic heterocyclic compound (1a) with N-halocarboxylic acid amide in the presence of water or alcohol.
First, the aromatic heterocyclic compound (1a) will be described. R in the aromatic heterocyclic compound (1a) ¹ Represents an alkyl group having 1 to 20 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, 2-ethylhexyl Group, n-heptyl group, n-octyl group, 2-hexyloctyl group, n-nonyl group, n-decyl group, 2-hexyldecyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n -A tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and n-icosyl group are mentioned. Preferably methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl Group, n-octyl group, n-nonyl group and n-decyl group. More preferred are a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group, and particularly preferred are a methyl group, an ethyl group, an n-propyl group, and an n- A butyl group is mentioned.
Z in the aromatic heterocyclic compound (1a) ¹ Each independently represents a sulfur atom or a selenium atom. Z ¹ Is preferably a sulfur atom. Z ² Represents an oxygen atom, a sulfur atom or a selenium atom. Z ² Is preferably an oxygen atom or a sulfur atom, more preferably a sulfur atom.
In the method for producing an aromatic heterocyclic compound (2a) by reacting an aromatic heterocyclic compound (1a) with an N-halocarboxylic acid amide, the N-halocarboxylic acid amide used is

A compound having a partial structure represented by, for example, N-haloacetamide such as N-chloroacetamide, N-bromoacetamide, N-iodoacetamide, N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, etc. N-halophthalimide such as N-halosuccinimide, N-chlorophthalimide, N-bromophthalimide, N-iodophthalimide, 1,3-dichloro-5,5-dimethylhydantoin, 1,3-dibromo-5,5-dimethyl 1,3-dihalohydantoins such as hydantoin and 1,3-diiodo-5,5-dimethylhydantoin can be mentioned. Preferred N-halocarboxylic amides are N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, N-chlorophthalimide, N-bromophthalimide and N-iodophthalimide, and more preferred N-halocarboxylic amides are N -Bromosuccinimide.
The amount of N-halocarboxylic acid amide used is usually 0.5 to 15 moles, preferably 0.7 to 10 moles, more preferably 1 mole of the aromatic heterocyclic compound (1a). Is a ratio of 1 to 8 moles. If the amount of N-halocarboxylic acid amide used is too small, the reaction will not be completed, and if the amount used is too large, side reactions may proceed.
The N-halocarboxylic acid amide may be charged at once, or may be charged in a plurality of times according to the progress of the reaction.
The reaction between the aromatic heterocyclic compound (1a) and the N-halocarboxylic acid amide is carried out in the presence of water or alcohol. The reaction is usually performed in a solvent, and water or alcohol may be added to the solvent before the start of the reaction or may be added to the solvent after the start of the reaction. The amount of water or alcohol added is usually 1 to 1/200 times by weight, preferably 1/2 to 1/150 times by weight, more preferably 1/5 to 1/100 times by weight of the solvent. Examples of the alcohol include methanol, ethanol, isopropyl alcohol, and n-butyl alcohol.
Examples of the solvent include aliphatic hydrocarbons such as pentane, hexane and heptane, aromatic hydrocarbons such as toluene and xylene, halogenated carbonization such as methylene chloride, chloroform, 1,2-dichloroethane and 1,2-dichloropropane. Examples thereof include ethers such as hydrogen, diethyl ether, tetrahydrofuran, 1,4-dioxane, cyclopentyl methyl ether, and mixtures thereof. Moreover, you may use water or alcohol as a solvent.
The amount of the solvent to be used is generally 1 to 500 times by weight, preferably 2 to 300 times by weight, more preferably 5 to 200 times by weight with respect to the aromatic heterocyclic compound (1a). The reaction temperature is usually −78 ° C. to the boiling point of the solvent, preferably −40 ° C. to the boiling point of the solvent, more preferably 0 ° C. to the boiling point of the solvent. The reaction time can range from 1 minute to 96 hours. After completion of the reaction, the aromatic heterocyclic compound (2a) can be obtained by performing a general post-treatment and, if necessary, purifying by distillation, recrystallization, silica gel chromatography or the like.
Specific examples of the aromatic heterocyclic compound (1a) include the following compounds:

Specific examples of the aromatic heterocyclic compound (2a) include the following compounds:

Is mentioned.
Subsequently, the condensation reaction between the aromatic heterocyclic compound (2a) and the aromatic compound (3) will be described.
First, the aromatic compound (3) will be described in detail.
R in compound (3) ¹¹ , R ¹² , R ¹³ And R ¹⁴ Each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted alkoxy group having 1 to 30 carbon atoms, or an optionally substituted carbon group having 6 to 30 carbon atoms. An aryl group, an optionally substituted aralkyl group having 7 to 30 carbon atoms, an optionally substituted heteroaralkyl group having 5 to 30 carbon atoms, an optionally substituted heteroaryl group having 4 to 30 carbon atoms, Or -Si (R ² ) ₃ (R ² Each independently represents an optionally substituted alkyl group having 1 to 30 carbon atoms or an optionally substituted aryl group having 6 to 30 carbon atoms. The substituted silyl group represented by this is shown.
R ¹¹ , R ¹² , R ¹³ And R ¹⁴ The “alkyl group having 1 to 30 carbon atoms” in the “optionally substituted alkyl group having 1 to 30 carbon atoms” represented by the formula may be any of linear, branched, and cyclic. Specific examples of the alkyl group having 1 to 30 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, and neopentyl group. N-hexyl group, 2-ethylhexyl group, n-heptyl group, n-octyl group, 2-hexyloctyl group, n-nonyl group, n-decyl group, 2-hexyldecyl group, n-undecyl group, n- Dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-icosyl group, n-henicosyl group, n- Docosyl group, n-tricosyl group, n-tetracosyl group, n-pentacosyl group, n-hexacosyl group, n-heptacosyl group, n-octacosyl group, n-nonacosyl group Group, n-triacontyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and the like, preferably methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t -Butyl group, n-pentyl group, neopentyl group, n-hexyl group, 2-ethylhexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, 2-hexyldecyl group, n- Examples include undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and n-icosyl group. More preferably, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, 2 Ethylhexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, 2-hexyloctyl group, n-tetradecyl group, n -Alkyl groups having 1 to 16 carbon atoms such as pentadecyl group, n-hexadecyl group, cyclohexyl group, and cycloheptyl group.
Examples of the substituent of the “optionally substituted alkyl group having 1 to 30 carbon atoms” include a halogen atom and an alkoxy group having 1 to 30 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the alkoxy group having 1 to 30 carbon atoms include methoxy group, ethoxy group, n-propoxy group, n-butoxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, and n-octyloxy group. N-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group Group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group, n-icosyloxy group, n-henicosyloxy group, n-docosyloxy group, n-tricosyloxy group, n-tetracosyl group Oxy group, n-pentacosyloxy group, n-hexacosyloxy group, n-heptacosyloxy group, n-octacosyloxy group Group, n-nonacosyloxy group, n-triacontyloxy group and the like.
The substituent that the “optionally substituted alkyl group having 1 to 30 carbon atoms” has is preferably a fluorine atom. Examples of the fluorine-substituted alkyl group having 1 to 30 carbon atoms include a perfluorohexyl group, a perfluorooctyl group, a perfluorodecyl group, a perfluorododecyl group, and a perfluorotridecyl group.
R ¹¹ , R ¹² , R ¹³ And R ¹⁴ As the “alkoxy group having 1 to 30 carbon atoms” in the “optionally substituted alkoxy group having 1 to 30 carbon atoms” represented by the formula, for example, methoxy group, ethoxy group, n-propoxy group, n-butoxy Group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n -Tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group, n-icosyloxy group, n-henicosyloxy group, n-docosyloxy group, n-tricosyloxy group, n-tetracosyloxy group, n-pentacosyloxy group Shi group, n- hex cosyl group, n- hepta cosyl group, n- oct cosyl group, can be exemplified n- Nonakoshiruokishi group, and n- triacontyl group. Preferably, methoxy group, ethoxy group, n-propoxy group, n-butoxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n- Decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group , N-octadecyloxy group, n-nonadecyloxy group, n-icosyloxy group and the like, and alkoxy groups having 1 to 20 carbon atoms.
Examples of the substituent of the “optionally substituted alkoxy group having 1 to 30 carbon atoms” include halogen atoms such as fluorine atom, chlorine atom and bromine atom, alkoxy group having 1 to 30 carbon atoms, and 6 to 6 carbon atoms. Examples thereof include 30 aryl groups, 7 to 30 aralkyl groups, 4 to 30 heteroaryl groups, and 5 to 30 heteroaralkyl groups. The hydrogen atom contained in the substituent may be replaced with a fluorine atom. Examples of the aryl group having 6 to 30 carbon atoms include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. As the aralkyl group having 7 to 30 carbon atoms,

The group represented by these is mentioned. Here, n1 represents an integer of 1 to 14, and n2 and n3 represent integers of 1 to 10. The heteroaryl group having 4 to 30 carbon atoms means a group in which at least one carbon atom contained in the aromatic ring of the aryl group is replaced by a hetero atom such as a nitrogen atom, an oxygen atom, a sulfur atom, or a selenium atom. For example, thienyl group, furyl group, thiazolyl group, thieno [3,2-b] thienyl group, fluoro [3,2-b] furyl group, thieno [3,2-b] furyl group, benzo [b] Examples include a thienyl group and a benzo [b] furyl group. As the heteroaryl group, a thienyl group, a thiazolyl group, a thieno [3,2-b] thienyl group, a benzo [b] thienyl group, and a benzo [b] furyl group are preferable. The heteroaralkyl group having 5 to 30 carbon atoms means a group in which at least one of carbon atoms contained in the aromatic ring of the aralkyl group is replaced with a hetero atom such as a nitrogen atom, an oxygen atom, a sulfur atom, or a selenium atom. As the heteroaralkyl group, for example, the formula

The group represented by these can be mentioned. Here, n4 represents an integer of 1 to 26, n5 represents an integer of 1 to 24, and n6 represents an integer of 1 to 22. More preferably, the formula

The group represented by these can be mentioned. Here, n4 represents an integer of 1 to 26, n5 represents an integer of 1 to 24, and n6 represents an integer of 1 to 22.
The substituent that the “optionally substituted alkoxy group having 1 to 30 carbon atoms” has is preferably a fluorine atom. Examples of the substituted alkoxy group having 1 to 30 carbon atoms include a perfluorohexyloxy group, a perfluorooctyloxy group, a perfluorodecyloxy group, a perfluorododecyloxy group, a perfluorotridecyloxy group, and a methoxyethoxyethoxy group. Groups.
R ¹¹ , R ¹² , R ¹³ And R ¹⁴ The “aryl group” of the “optionally substituted aryl group having 6 to 30 carbon atoms” represented by the formula is preferably monocyclic or bicyclic, more preferably a phenyl group, 1-naphthyl group, A 2-naphthyl group is mentioned.
Examples of the substituent of the “optionally substituted aryl group having 6 to 30 carbon atoms” include halogen atoms such as a fluorine atom, a chlorine atom, and a bromine atom, for example, an alkyl group having 1 to 20 carbon atoms, C1-C20 alkoxy group, C6-C20 aryl group, C7-C20 aralkyl group, C4-C20 heteroaryl group, and C5-C20 heteroaralkyl group Can do. The hydrogen atom contained in the substituent may be replaced with a fluorine atom. Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, 1-naphthyl group, and 2-naphthyl group. Examples of the substituted aryl group having 6 to 20 carbon atoms include perfluorophenyl. be able to. Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, and 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-octadecyl group, n-nonadecyl group Group, n-icosyl group, n-henicosyl group, n-docosyl group, n-tricosyl group, n-tetracosyl group, n-pentacosyl group, n-hexacosyl group, n-heptacosyl group, n-octacosyl group, n-nonacosyl group Group, and n-triacontyl group.
R ¹¹ , R ¹² , R ¹³ And R ¹⁴ As the substituent of the “optionally substituted aralkyl group having 7 to 30 carbon atoms” represented by the following, for example, a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom, an alkyl group having 1 to 20 carbon atoms, Examples thereof include an alkoxy group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a heteroaryl group having 4 to 20 carbon atoms, and a heteroaralkyl group having 5 to 20 carbon atoms. The hydrogen atom contained in the substituent alkyl group, alkoxy group, aralkyl group, heteroaryl group or heteroaralkyl group may be replaced by a fluorine atom.
The substituent of the “optionally substituted aralkyl group having 7 to 30 carbon atoms” is preferably a fluorine atom.
Examples of the “optionally substituted aralkyl group having 7 to 30 carbon atoms” include, for example, the formula

(Wherein n1 represents an integer of 1 to 24, and n2 and n3 represent an integer of 1 to 20), or an aralkyl group having 7 to 30 carbon atoms, or a formula

(Wherein n4 and n5 represent an integer of 1 to 24, and n6 represents an integer of 1 to 23), and an aralkyl group having a substituent of 7 to 30 carbon atoms.
R ¹¹ , R ¹² , R ¹³ And R ¹⁴ As the “optionally substituted heteroaryl group having 4 to 30 carbon atoms” represented by, for example, thienyl group, furyl group, thiazolyl group, thieno [3,2-b] thienyl group, fluoro [3, 2-b] furyl group, thieno [3,2-b] furyl group, benzo [b] thienyl group, benzo [b] furyl group. Preferred heteroaryl groups include thienyl group, thiazolyl group, thieno [3,2-b] thienyl group, benzo [b] thienyl group, benzo [b] furyl group.

The group represented by is preferable.
Examples of the substituent of the “optionally substituted heteroaryl group having 4 to 30 carbon atoms” include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, an alkyl group having 1 to 20 carbon atoms, and 1 carbon atom. Examples thereof include an alkoxy group having 20 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a heteroaryl group having 4 to 30 carbon atoms, and a heteroaralkyl group having 5 to 30 carbon atoms. The hydrogen atom contained in the substituent may be replaced with a fluorine atom.
Examples of the “optionally substituted heteroaryl group having 4 to 30 carbon atoms” include 2-thienyl group, 2-thieno [3,2-b] thienyl group, 2-benzo [b] thienyl group, 5-fluoro -2-thienyl group, 5-hexyl-2-thienyl, 4-hexyloxy-2-thienyl group, and the like.
Examples of the substituent of the “optionally substituted heteroaralkyl group having 5 to 30 carbon atoms” include, for example, a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, an alkyl group having 1 to 20 carbon atoms, and a carbon number of 1 Examples thereof include an alkoxy group having 20 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, a heteroaryl group having 4 to 30 carbon atoms, and a heteroaralkyl group having 5 to 20 carbon atoms. The hydrogen atom contained in the substituent may be replaced with a fluorine atom.
As the substituent of the “optionally substituted heteroaralkyl group having 5 to 30 carbon atoms”, a fluorine atom is preferable. Examples of the “optionally substituted heteroaralkyl group having 5 to 30 carbon atoms” include, for example,

The group represented by these can be mentioned. Here, n4 represents an integer of 1 to 26, n5 represents an integer of 1 to 24, and n6 represents an integer of 1 to 22.
R ¹¹ , R ¹² , R ¹³ And R ¹⁴ Formula -Si (R ² ) ₃ Is preferably a trialkylsilyl group having 3 to 30 carbon atoms which may have a fluorine atom, wherein the trialkylsilyl group is bonded to a silicon atom. A silyl group having a total of 3 to 30 carbon atoms in one alkyl group. Therefore, the maximum number of carbon atoms of one alkyl group bonded to a silicon atom is 28, which is an alkyl group having 1 to 30 carbon atoms which may be substituted with a fluorine atom. The trialkylsilyl group substituted with a fluorine atom means a group in which part or all of the hydrogen atoms in the alkyl group bonded to the silicon atom are replaced with fluorine atoms. Specific examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group, a tri (isopropyl) silyl group, a t-butyldimethylsilyl group, a dimethylhexylsilyl group, and a dimethyldodecylsilyl group.
X in the aromatic compound (3) ² Represents a leaving group. X ² May be any leaving group that allows the condensation reaction of the aromatic compound (3) and the aromatic heterocyclic compound (2a) to proceed.

Is preferred.
In formula (6), R ¹⁰ Each independently represents a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an aryloxy group having 6 to 20 carbon atoms; ¹⁰ May be the same or different, and two R ¹⁰ May combine to form a ring structure together with the boron atom.
R ¹⁰ Examples of the alkyl group having 1 to 10 carbon atoms represented by the formula: methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group Linear, branched, such as neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, and 1,2-dimethylpropyl group A linear or cyclic alkyl group is exemplified. R ¹⁰ Examples of the alkoxy group having 1 to 10 carbon atoms represented by: include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, and an n-hexanoxy group. R ¹⁰ Examples of the aryloxy group having 6 to 20 carbon atoms represented by the formula include a phenoxy group, a 1-naphthoxy group, and a 2-naphthoxy group.
2 R ¹⁰ Are bonded to form a ring structure with a boron atom, preferred examples include 1,3,2-dioxaborolane ring, 4,4,5,5-tetramethyl-1,3,2-dioxaborolane ring, Examples include 5-dimethyl-1,3,2-dioxaborinane ring, 1,3,2-benzodioxaborol ring, and 9-borabicyclo3,3,1-nonane ring.
As specific examples of the leaving group, in addition to the group represented by the formula (6), the formulas (7), (8) and (9)

And a leaving group as represented respectively.
In formula (7), R ²⁰ Each independently represents an alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, tert-butyl group, n -Pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-octyl group, and n-decyl group are mentioned. Preferred are a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-hexyl group, and more preferred are a methyl group, an ethyl group, an n-propyl group, and an n-butyl group. R in formula (7) ²⁰ May be different from each other, but are preferably the same.
In formula (8), X ³ Represents a halogen atom, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. A bromine atom and an iodine atom are preferable.
In formula (9), X ⁴ Represents a halogen atom, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. A bromine atom and an iodine atom are preferable.
In the aromatic compound (3), a compound having a group represented by the formula (6) as a leaving group can be produced by a conventional method. For example, 4th edition Experimental Chemistry Course 24 Organic Synthesis VI (The Chemical Society of Japan) Hen) can be manufactured by the method described on page 80.
In the aromatic compound (3), a compound having a group represented by the formula (7) as a leaving group can be produced by a conventional method. For example, 4th edition Experimental Chemistry Course 24 Organic Synthesis VI (The Chemical Society of Japan) Ed.) Can be produced by the method described on page 189.
In the aromatic compound (3), a compound having a group represented by the formula (8) as a leaving group can be produced by a conventional method. For example, 4th edition Experimental Chemistry Course 24 Organic Synthesis VI (The Chemical Society of Japan) Volume) and can be produced by the method described on page 43.
In the aromatic compound (3), a compound having a group represented by the formula (9) as a leaving group can be produced by a conventional method. For example, 4th edition Experimental Chemistry Course 25 Organic Synthesis VII (The Chemical Society of Japan) Volume) and can be manufactured by the method described on page 401.
Examples of the aromatic compound (3) include compounds represented by numbers (3-1) to (3-280) in Table 1.

The wavy line in Table 1 means a bond.
Specific examples of preferred aromatic compound (3) include numbers (3-1), (3-2), (3-3), (3-6), (3-8), (3-11), ( 3-13), (3-15), (3-16), (3-17), (3-20), (3-21), (3-24), (3-26), (3- 29), (3-32), (3-42), (3-43), (3-44), (3-45), (3-46), (3-47), (3-48) , (3-49), (3-50), (3-51), (3-52), (3-54), (3-56), (3-57), (3-59), ( 3-60), (3-61), (3-62), (3-63), (3-64), (3-65), (3-66), (3-67), (3- 68), (3-69), (3-70), (3-71), (3-72), (3-73), (3 74), (3-75), (3-76), (3-77), (3-78), (3-79), (3-80), (3-81), (3-83) , (3-84), (3-85), (3-86), (3-87), (3-88), (3-92), (3-95), (3-96), ( 3-97), (3-98), (3-99), (3-100), (3-101), (3-103), (3-104), (3-105), (3- 107), (3-109), (3-110), (3-112), (3-114), (3-124), (3-128), (3-129), (3-134) , (3-135), (3-137), (3-138), (3-139), (3-143), (3-147), (3-149), (3-151), ( 3-156), (3-159), (3- 64), (3-169), (3-177), (3-196), (3-197), (3-198), (3-201), (3-203), (3-205) , (3-207), (3-208), (3-210), (3-219), (3-225), (3-228), (3-234), (3-235), ( 3-237), (3-239), (3-246), (3-249), (3-251), (3-253), (3-259), (3-269), (3- 270), (3-271), (3-272), (3-274), (3-276), (3-278) and (3-280).
More preferred examples are numbers (3-1), (3-2), (3-3), (3-6), (3-42), (3-43), (3-44), (3 -45), (3-46), (3-47), (3-48), (3-49), (3-50), (3-51), (3-52), (3-54 ), (3-56), (3-57), (3-59), (3-64), (3-73), (3-78), (3-80), (3-92), (3-95), (3-101), (3-103), (3-104), (3-105), (3-107), (3-109), (3-110), (3 -112), (3-114), (3-124), (3-128), (3-129), (3-156), (3-196), (3-197), (3-269) ), (3-272), (3-274) and (3-276) It is in those represented.
X of aromatic compound (3) ² In the case of a group represented by the formula (6), this condensation reaction can be easily performed in a solution in the presence of a transition metal catalyst and a base, for example, in a temperature range of about 0 ° C. to 150 ° C. Can be advanced.
Examples of the transition metal catalyst used in the condensation reaction include a palladium catalyst or a nickel catalyst. As the palladium catalyst, a commercially available catalyst may be used, or a catalyst prepared by bringing a palladium compound and a phosphine compound into contact with each other in advance may be used. May be prepared in.
Examples of the palladium catalyst include tetrakis (triphenylphosphine) palladium (0), bis (acetate) bis (triphenylphosphine) palladium (II), bis [1,2-bis (diphenylphosphino) ethane] palladium (0 ), [1,2-bis (diphenylphosphino) ethane] dichloropalladium (II), dibromobis (triphenylphosphine) palladium (II), dichlorobis (dimethylphenylphosphine) palladium (II), dichlorobis (methyldiphenylphosphine) palladium (II), dichlorobis (tricyclohexylphosphine) palladium (II), dichlorobis (triethylphosphine) palladium (II), dichlorobis (triphenylphosphine) palladium (II), dichlorobi [Tris (2-methylphenyl) phosphine] palladium (II), tetrakis (methyldiphenylphosphine) palladium (0), tetrakis (tricyclohexylphosphine) palladium (0) and dichlorobis (1,1′-diphenylphosphinoferrocenyl) ) Palladium (II).
Examples of the palladium compound include tris (dibenzylideneacetone) dipalladium (0), tris (dibenzylideneacetone) dipalladium (0) · chloroform adduct, palladium (II) acetate, palladium (II) chloride, (bicyclo [2.2.1] Hepta-2,5-diene) dichloropalladium (II), (2,2′-bipyridyl) dichloropalladium (II), bis (acetonitrile) chloronitropalladium (II), bis (benzonitrile ) Dichloropalladium (II), bis (acetonitrile) dichloropalladium (II), dichloro (1,5-cyclooctadiene) palladium (II), dichloro (ethylenediamine) palladium (II), dichloro (N, N, N ′, N′-tetramethylenediamine) palladium (II), di Loro (1,10-phenanthroline) palladium (II), palladium (II) acetylacetonate, palladium (II) bromide, palladium (II) hexafluoroacetylacetonate, palladium (II) iodide, palladium (II) nitrate Palladium (II) sulfate and palladium (II) trifluoroacetate, preferably palladium (II) acetate, palladium (II) chloride and tris (dibenzylideneacetone) dipalladium (0). As such a palladium compound, a commercially available product can be used.
Examples of the phosphine compound include triphenylphosphine, tris (2-methylphenyl) phosphine, tris (3-methylphenyl) phosphine, tris (4-methylphenyl) phosphine, tris (pentafluorophenyl) phosphine, tris (4- Fluorophenyl) phosphine, tris (2-methoxyphenyl) phosphine, tris (3-methoxyphenyl) phosphine, tris (4-methoxyphenyl) phosphine, tris (2,4,6-trimethylphenyl) phosphine, tri (3-chlorophenyl) ) Phosphine, tri (4-chlorophenyl) phosphine, tri-n-butylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, 1,2-diphenylphosphinoethane, 1,3-diphenylphosphine Finopropane, 1,4-diphenylphosphinobutane, 1,2-dicyclohexylphosphinoethane, 1,3-dicyclohexylphosphinopropane, 1,4-dicyclohexylphosphinobutane, 1,2-dimethylphosphinoethane, 1, 3-dimethylphosphinopropane, 1,4-dimethylphosphinobutane, 1,2-diethylphosphinoethane, 1,3-diethylphosphinopropane, 1,4-diethylphosphinobutane, 1,2-diisopropylphosphino Ethane, 1,3-diisopropylphosphinopropane, 1,4-diisopropylphosphinobutane, tri-2-furylphosphine, 2- (dicyclohexylphosphino) biphenyl, 2- (di-tert-butylphosphino) biphenyl, 2 -Di-tert-butylphosph 2'-methylbiphenyl, 2- (dicyclohexylphosphino-2'-6'-dimethoxy, 1,1'-biphenyl, 2- (dicyclohexylphosphino) -2 '-(N, N-dimethylamino) biphenyl 2-dicyclohexylphosphino-2′-methyl-biphenyl, 2- (dicyclohexylphosphino) -2 ′, 4 ′, 6′-tri-isopropyl 1,1′-biphenyl, 1,1′-bis (diphenylphos (Fino) ferrocene and 1,1′-bis (di-isopropylphosphino) ferrocene As such phosphine compounds, commercially available ones may be used or those prepared according to known methods may be used. The amount of the phosphine compound used is usually 0.5 to 10 moles per mole of the palladium compound, preferably 1 Is the ratio of Le to 5 mol.
Examples of the nickel catalyst used in this condensation reaction include dichlorobis (1,1′-diphenylphosphinoferrocenyl) nickel (II), dichlorobis (diphenylphosphino) nickel (II), dichloronickel (II), and dichloride. An example is iodonickel (II).
The amount of the transition metal catalyst used is, for example, 0.0005 mol to 0.5 mol in terms of metal with respect to 1 mol of the aromatic compound (3).
This condensation reaction is preferably performed in a solvent. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, and xylene; ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, tert-butyl methyl ether, and ethylene glycol dimethyl ether; N, N-dimethylformamide Amides such as N, N-dimethylacetamide; dimethyl sulfoxide; N-methylpyrrolidone; 1,3-dimethyl-2-imidazolidinone; and water. A reaction solvent may be used independently and may be used in mixture of 2 or more types. The solvent is preferably used after deaeration. Alternatively, some or all of the compounds used in the reaction may be dissolved or suspended in the reaction solvent and then degassed by a method such as nitrogen bubbling. The amount of the reaction solvent to be used is, for example, 0.5 to 200 times by weight, preferably 2 to 100 times by weight, with respect to the aromatic heterocyclic compound (2a).
This condensation reaction is preferably performed in the presence of a base. Examples of the base include lithium hydroxide, sodium hydroxide, potassium hydroxide, thallium hydroxide, barium hydroxide, lithium methoxide, sodium methoxide, potassium methoxide, lithium ethoxide, sodium ethoxide, potassium ethoxide, Examples include sodium-tert-butoxide, potassium-tert-butoxide, lithium carbonate, sodium carbonate, potassium carbonate, thallium carbonate, cesium carbonate, sodium bicarbonate, potassium bicarbonate, sodium phosphate and potassium phosphate. The usage-amount of a base is a ratio of at least 0.5 mol with respect to 1 mol of aromatic compounds (3), Preferably, it is a ratio of at least 1 mol.
This condensation reaction may be performed in the presence of a phase transfer catalyst. Examples of the phase transfer catalyst include quaternary ammonium salts such as tetraalkyl ammonium halide, tetraalkyl ammonium hydrogen sulfate and tetraalkyl ammonium hydroxide, preferably tetra-n-butyl ammonium halide and An example is benzyltriethyl ammonium halide. Although the reaction atmosphere can be performed in the air, it is preferably performed under an inert gas such as nitrogen and argon in order to prevent deterioration of the catalyst used.
Examples of the reaction temperature of the condensation reaction include a range of 0 ° C to 150 ° C. Examples of the reaction time of the condensation reaction include a range of 1 minute to 96 hours. After completion of the condensation reaction, for example, the obtained reaction mixture and an aqueous ammonium chloride solution are mixed, and if necessary, an extraction process is performed by adding an organic solvent insoluble in water, and the obtained organic layer is concentrated and necessary. The compound (4) can be obtained by performing purification means such as column chromatography, distillation, recrystallization, and recycle gel permeation chromatography.
Examples of the compound (4) include compounds represented by numbers (4-1) to (4-445) in Table 2 and compounds represented by numbers (4-446) to (4-452) described later. Can do.

The wavy line in Table 2 means a bond.

Preferred specific examples of compound (4) are the numbers (4-1), (4-2), (4-3), (4-5), (4-6), (4-8), (4- 10), (4-16), (4-17), (4-18), (4-24), (4-28), (4-31), (4-35), (4-37) , (4-41), (4-42), (4-49), (4-51), (4-52), (4-56), (4-57), (4-58), ( 4-68), (4-73), (4-81), (4-82), (4-83), (4-84), (4-85), (4-86), (4- 87), (4-88), (4-89), (4-90), (4-91), (4-93), (4-94), (4-95), (4-96) , (4-98), (4-101), (4-103), (4-107), (4-108), (4 110), (4-112), (4-113), (4-114), (4-122), (4-127), (4-137), (4-140), (4-142) , (4-148), (4-150), (4-159), (4-160), (4-161), (4-166), (4-167), (4-177), ( 4-178), (4-181), (4-184), (4-186), (4-202), (4-203), (4-207), (4-212), (4- 213), (4-223), (4-225), (4-228), (4-230), (4-239), (4-243), (4-246), (4-248) , (4-257), (4-260), (4-269), (4-271), (4-279), (4-291), (4-298), (4-299) , (4-300), (4-302), (4-308), (4-314), (4-320), (4-321), (4-325), (4-327), ( 4-331), (4-332), (4-334), (4-341), (4-344), (4-350), (4-362), (4-375), (4- 376), (4-380), (4-381), (4-390), (4-393), (4-394), (4-398), (4-399), (4-404) , (4-410), (4-416), (4-434), (4-435), (4-436), (4-437), (4-439), (4-441), ( 4-442), (4-443) and (4-445).
More preferable examples are numbers (4-1), (4-2), (4-5), (4-6), (4-17), (4-18), (4-35), (4 -37), (4-81), (4-82), (4-83), (4-84), (4-85), (4-86), (4-87), (4-89) ), (4-90), (4-93), (4-96), (4-98), (4-103), (4-112), (4-140), (4-142), (4-148), (4-150), (4-159), (4-167), (4-177), (4-178), (4-181), (4-184), (4 -202), (4-203), (4-207), (4-223), (4-225), (4-230), (4-239), (4-298), (4-299) ), (4-300), (4-302), (4 308), (4-325), (4-327), (4-331), (4-332), (4-375), (4-376), (4-380), (4-381) , (4-399), (4-437), (4-439) and (4-441).
The chalcogen-containing condensed polycyclic compound (5) can be obtained by reacting the compound (4) with an acid. Specific examples of the acid include trifluoromethanesulfonic acid, methanesulfonic acid, sulfuric acid, phosphoric acid, a mixture of phosphoric acid and diphosphorus pentoxide, and hydrochloric acid. Preferred examples are trifluoromethanesulfonic acid, methanesulfonic acid, sulfuric acid and hydrochloric acid. The acid to be used may be diluted with water if necessary.
The compound (4) is directly added to the acid or diluted in a solvent such as chloroform and charged in a reaction vessel, and the reaction is carried out by stirring at about -20 ° C to 100 ° C for about 1 minute to 48 hours. At this time, a dehydrating agent such as diphosphorus pentoxide may be present. After completion of the reaction, for example, the reaction mixture may be mixed with water and the precipitated solid may be filtered, or after mixing with water, a solvent may be added as necessary, and the organic layer may be separated and concentrated. good. If necessary, the chalcogen-containing polycyclic compound (5) can be purified by ordinary purification means such as column chromatography, distillation, recrystallization, and recycle gel permeation chromatography.
The chalcogen-containing polycyclic compound (5) can also be obtained by reacting the compound (4) with an acid and then subjecting the resulting onium cation intermediate to a base treatment. In this case, after the reaction between the compound (4) and the acid, the mixture is mixed with water, and the precipitated solid is filtered and mixed with water, or mixed with water, and then the solvent is added to separate the organic layer. If necessary, a base such as an organic base such as pyridine or triethylamine is added to the onium cation intermediate obtained in the presence of a solvent, and the mixture is stirred at a temperature from 50 ° C. to the boiling point of the solvent, for example, for 1 minute to 48 hours. To do. Thereafter, a general post-treatment is performed, and if necessary, normal purification means such as column chromatography, distillation, recrystallization, recycle gel permeation chromatography, etc. are performed, so that the chalcogen-containing polycyclic compound (5) Can be obtained.
Examples of the chalcogen-containing condensed polycyclic compound (5) include compounds represented by numbers (5-1) to (5-452) in Table 3.

The wavy line in Table 3 means a bond.

Specific examples of preferable chalcogen-containing fused polycyclic compound (5) include numbers (5-1), (5-2), (5-3), (5-5), (5-6), (5- 8), (5-10), (5-35), (5-37), (5-41), (5-42), (5-49), (5-51), (5-52) , (5-56), (5-57), (5-58), (5-68), (5-73), (5-81), (5-82), (5-83), ( 5-84), (5-85), (5-86), (5-87), (5-88), (5-89), (5-90), (5-91), (5- 93), (5-94), (5-95), (5-96), (5-98), (5-101), (5-103), (5-107), (5-108) , (5-110), (5-112), (5-113), (5-114), ( -177), (5-178), (5-181), (5-184), (5-186), (5-202), (5-203), (5-207), (5-212) ), (5-213), (5-223), (5-225), (5-228), (5-230), (5-239), (5-243), (5-246), (5-248), (5-257), (5-260), (5-269), (5-271), (5-279), (5-291), (5-298), (5 -299), (5-300), (5-302), (5-325), (5-327), (5-331), (5-332), (5-334), (5-341) ), (5-344), (5-350), (5-362), (5-375), (5-376), (5-380), (5-381), (5-398) , (5-399), (5-404), it is represented by (5-410) and (5-416).
More preferred examples are numbers (5-1), (5-2), (5-5), (5-6), (5-35), (5-37), (5-81), (5 -82), (5-83), (5-84), (5-85), (5-86), (5-87), (5-89), (5-90), (5-93) ), (5-96), (5-98), (5-103), (5-112), (5-177), (5-178), (5-181), (5-184), (5-202), (5-203), (5-207), (5-223), (5-225), (5-230), (5-239), (5-298), (5 -299), (5-300), (5-302), (5-325), (5-327), (5-331), (5-332), (5-375), (5-376) ), (5-380), (5-381) and It is represented by (5-399).

Hereinafter, the present invention will be described more specifically with reference to examples.
<Synthesis 1 of 2,5-dibromo-3,4-dimethylsulfinylthiophene>

N-bromosuccinimide (3.85 g, 21.6 mmol) was added to a dioxane (267 mL) solution of 3,4-dimethylsulfanylthiophene (2.50 g, 14.2 mmol) at room temperature, and the mixture was stirred for 6 hours. Thereafter, N-bromosuccinimide (0.96 g, 5.39 mmol) was further added and stirred for 2 hours. Water (115 mL) and N-bromosuccinimide (3.85 g, 21.6 mmol) were added to the reaction solution, and the mixture was stirred at the same temperature for 2 hours. Thereafter, N-bromosuccinimide (3.85 g, 21.6 mmol) was further added, and the mixture was stirred for 4 hours and 30 minutes. After completion of the reaction, the reaction mixture was added to a saturated aqueous sodium carbonate solution (150 mL), and the organic layer was extracted with ethyl acetate. The extract was washed with water and saturated brine, dried over magnesium sulfate, and the solvent was distilled off with an evaporator. The obtained crude product was purified with a silica gel column (developing solvent: chloroform-ethyl acetate) to obtain 0.73 g of 2,5-dibromo-3,4-dimethylsulfinylthiophene. (14% yield)
¹ H-NMR (CDCl ₃ , δ ppm): 3.21 (s, 2.4H), 3.09 (s, 3.6H)
<Synthesis 2 of 2,5-dibromo-3,4-dimethylsulfinylthiophene>

N-bromosuccinimide (336 mg, 1.89 mmol) was added to a solution of 3,4-dimethylsulfanylthiophene (83 mg, 0.47 mmol) in dioxane (11.6 mL) and water (5.0 mL) at room temperature for 4 hours. Stir for minutes. Thereafter, N-bromosuccinimide (168 mg, 0.95 mmol) was further added and stirred for 2 hours. A part of the reaction solution was taken, treated with a saturated aqueous sodium carbonate solution, and the organic layer was subjected to GC analysis. As a result, formation of 2,5-dibromo-3,4-dimethylsulfinylthiophene was confirmed.
<Synthesis of 2,5-bis (4-n-hexylphenyl) -3,4-dimethylsulfinylthiophene>

2,5-Dibromo-3,4-dimethylsulfinylthiophene (0.08 g, 0.2 mmol) is dissolved in 9 mL of THF, and 4-n-hexyl-1- (4,4,5,5- Add tetramethyl-1,3,2-dioxaborolan-2-yl) benzene (0.17 g, 0.6 mmol) and aqueous cesium carbonate (2.0 M, 2.9 mL). The resulting mixture is bubbled with nitrogen at room temperature, PdCl ₂ (dppf) (0.09 g, 0.01 mmol) is added, and the mixture is further heated to 80 ° C. and stirred for 16 hours. After cooling the resulting reaction liquid to room temperature, an aqueous ammonium chloride solution is added to separate it into an organic layer and an aqueous layer. The aqueous layer is extracted with THF and mixed with the organic layer. The combined organic layers are washed with water, saturated aqueous sodium chloride solution, then dried over magnesium sulfate and concentrated to give the crude product. The resulting crude product is fractionated using thin layer chromatography to obtain 2,5-bis (4′-n-hexylphenyl) -3,4-dimethylsulfinylthiophene having the following spectrum.
¹ H-NMR (CDCl ₃ , δ ppm): 7.45 (d, J = 8.1 Hz, 2.5H), 7.36 (d, J = 8.1 Hz, 1.5H), 7.28-7 .24 (m, 4H), 3.28 (s, 2.3H), 3.09 (s, 3.7H), 2.70-2.63 (m, 4H), 1.70-1.53 (M, 4H), 1.42-1.28 (m, 12H), 0.92-0.87 (m, 6H)
Synthesis of bis (5-hexylbenzo [4,5] thieno) [3,2-c: 2 ′, 3′-e] thiophene

2,5-bis (4′-n-hexylphenyl) -3,4-dimethylsulfinylthiophene (0.30 g, 0.6 mmol), and P ₂ O ₅ (0.03 g, 0.2 mmol) were added to trifluoromethanesulfone. Dissolve in 10.3 mL of acid to obtain a reaction solution. The solution is heated to 50 ° C., stirred at the same temperature for 3 hours, and then cooled to room temperature to obtain a reaction solution. The reaction solution is added to 103 mL of water, and the precipitated solid is filtered. The obtained solid is washed with water, and a solution obtained by dissolving in 90 mL of pyridine is heated and stirred for 10 hours under reflux. Cool the solution to room temperature and add water and chloroform. The obtained organic layer and aqueous layer are separated, and the organic layer is dried over magnesium sulfate and concentrated to obtain a crude product. By purifying the resulting crude product using a silica gel column and gel permeation chromatography, bis (5-hexylbenzo [4,5] thieno) [3,2-c: 2 ′, having the following spectrum: 3′-e] thiophene is obtained.
¹ H-NMR (CDCl ₃ , δ ppm): 7.65 (d, J = 7.3 Hz, 2H), 7.57 (d, J = 1.0 Hz, 2H), 7.19 (dd, J = 7) .3, 1.0 Hz, 2H), 2.73 (t, J = 7.0 Hz, 4H), 1.73-1.63 (m, 4H), 1.40-1.29 (m, 12H) 0.90 (t, J = 6.8 Hz, 6H)

The production method of the present invention makes it possible to produce a chalcogen-containing condensed polycyclic compound useful for organic semiconductor materials and the like under mild conditions.

Claims

Formula (1a)

Is reacted with an N-halocarboxylic acid amide in the presence of water or alcohol to give a compound of formula (2a)

Obtaining an aromatic heterocyclic compound (2a) represented by:
Aromatic heterocyclic compound (2a) and formula (3)

Is reacted with an aromatic compound (3) represented by formula (4)

A step of obtaining a compound (4) represented by formula (5) and reacting the compound (4) with an acid to give a compound of formula (5)

The manufacturing method of a chalcogen condensed polycyclic compound (5) including the process of obtaining the chalcogen condensed polycyclic compound (5) shown by these.
(In each formula, R 1 represents an alkyl group having 1 to 20 carbon atoms, Z 1 independently represents a sulfur atom or a selenium atom, and Z 2 represents an oxygen atom, a sulfur atom or a selenium atom. R 11 , R 12 , R 13 and R 14 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted alkoxy group having 1 to 30 carbon atoms, or a substituted group. An optionally substituted aryl group having 6 to 30 carbon atoms, an optionally substituted aralkyl group having 7 to 30 carbon atoms, an optionally substituted heteroaryl group having 4 to 30 carbon atoms, and an optionally substituted carbon A heteroaralkyl group of 5 to 30 or the formula —Si (R 2 ) 3 (wherein R 2 is each independently an optionally substituted alkyl group of 1 to 30 carbon atoms or an optionally substituted carbon number) Represents 6 to 30 aryl groups.) .X 1 showing a substituted silyl group represented represents a halogen atom, X 2 represents a leaving group.)
The method according to claim 1, wherein Z 1 and Z 2 are both sulfur atoms.
The method according to claim 1, wherein the N-halocarboxylic acid amide is N-halosuccinimide.
Formula (1a)

Formula (2a) in which an aromatic heterocyclic compound represented by the formula (1a) and an N-halocarboxylic acid amide are reacted in the presence of water or alcohol

The manufacturing method of the aromatic heterocyclic compound (2a) represented by these.
(In each formula, R 1 represents an alkyl group having 1 to 20 carbon atoms, Z 1 independently represents a sulfur atom or a selenium atom, Z 2 represents an oxygen atom, a sulfur atom or a selenium atom, and X 1 Represents a halogen atom.)
The method according to claim 4, wherein Z 1 and Z 2 are both sulfur atoms.
The method according to claim 4, wherein the N-halocarboxylic acid amide is N-halosuccinimide.