JP2010180151A - Thiophene ring fused polycyclic aromatic compound - Google Patents

Abstract

An organic semiconductor compound that exhibits more stable and higher mobility as an organic electronic element material such as a light emitting element, a photoelectric conversion element, and a semiconductor, and a method for producing the same.
A thiophene ring-fused polycyclic aromatic compound represented by the formula (1a), (1b) or (1c).

[Wherein R ¹ , R ² , R ³ and R ⁴ are hydrogen; halogen; a hydrocarbon group, etc., and R ⁵ , R ^{5 ′} and R ⁶ are halogen; a hydrocarbon group, m and m 'Is an integer from 0 to 2, and n is an integer from 0 to 4. ]
[Selection figure] None

Description

  The present invention relates to a thiophene ring-fused polycyclic aromatic compound in which at least one terminal aromatic ring of a naphthacene skeleton is replaced with a thiophene ring.

A single crystal of rubrene (5,6,11,12-tetraphenylnaphthacene) is known to exhibit a higher mobility than polycrystalline silicon (Non-Patent Document 1: Sundar et al. Science, 2004). , 303, 1644), and is expected as an organic field effect transistor (OFET) material.
However, although rubrene exhibits high mobility in crystals, its mobility is unfortunately low enough that it cannot be used in the form of a thin film. In addition, rubrene is known to be chemically unstable and quickly decompose.

  Under the circumstances as described above, there is a need to provide an organic semiconductor compound that is chemically more stable and can exhibit high mobility in the form of a thin film.

  As a result of intensive studies to overcome the above problems, the present inventors have succeeded in synthesizing a compound in which at least one of the terminal aromatic rings of the naphthacene skeleton is replaced with a thiophene ring. Introducing a thiophene ring into the terminal aromatic ring of the naphthacene skeleton is expected to improve chemical stability and mobility.

That is, the present invention relates to the following thiophene ring-fused polycyclic aromatic compounds and uses thereof.
[1] A thiophene ring-fused polycyclic aromatic compound represented by the following formula (1a), (1b) or (1c).
[Wherein, R ¹ , R ² , R ³ and R ⁴ are each independently the same or different and are a hydrogen atom; a halogen atom; an optionally substituted C ₁ -C ₂₀ hydrocarbon; A C ₁ -C ₂₀ alkoxy group which may have a substituent; a C ₆ -C ₂₀ aryloxy group which may have a substituent; an amino group which may have a substituent; A silyl group which may have a group; a hydroxyl group; a thienyl group which may have a substituent; a pyridyl group which may have a substituent; and a furyl group which may have a substituent. ,
R ⁵ , R ^{5 ′,} and R ⁶ are each independently the same or different and are each a halogen atom; an optionally substituted C ₁ -C ₂₀ hydrocarbon group; A C ₁ -C ₂₀ alkoxy group which may have a substituent; a C ₆ -C ₂₀ aryloxy group which may have a substituent; an amino group which may have a substituent; a silyl which may have a substituent A group; a hydroxyl group; a thienyl group which may have a substituent, a pyridyl group which may have a substituent, a furyl group which may have a substituent,
m and m ′ are each independently the same or different and are an integer of 0 to 2, and n is an integer of 0 to 4. ]

[2] The thiophene ring-condensed polythene according to [1], wherein any one of R ¹ and R ² or R ³ and R ⁴ is a C _{6 to} C ₂₀ aryl group which may have a substituent. Ring aromatic compounds.
[3] The thiophene ring-fused polycyclic aromatic compound according to [1] or [2], wherein R ¹ and R ² are the same functional group, and R ³ and R ⁴ are the same functional group.
[4] The thiophene according to any one of [1] to [3], wherein R ¹ , R ² , R ³ and R ⁴ are a C _{6 to} C ₂₀ aryl group which may have a substituent. Fused polycyclic aromatic compounds.
[5] The thiophene ring-fused polycyclic aroma according to any one of [1] to [4], wherein R ¹ , R ² , R ³ and R ⁴ are a phenyl group which may have a substituent. Group compounds.
[6] The thiophene ring-fused polycyclic aromatic compound according to any one of [1] to [5], wherein R ¹ , R ² , R ³ and R ⁴ are phenyl groups.
[7] [ ¹ ] to [ ¹ ], wherein R ¹ and R ² are alkynyl groups which may have a substituent, and R ³ and R ⁴ are phenyl groups which may have a substituent. [3] The thiophene ring-fused polycyclic aromatic compound according to any one of [3].

[8] The thiophene ring-fused polycyclic aromatic compound according to any one of [1] to [7], which is represented by the following formula (1a ′), (1b ′), or (1c ′).
[Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{5 ′} have the same meaning as described above. ]

[9] The thiophene ring-fused polycyclic aromatic compound according to any one of [1] to [7], which is represented by the following formula (1a ″), (1b ″) or (1c ″).
[Wherein, R ¹ , R ² , R ³ and R ⁴ have the same meanings as described above. ]

[10] A composition comprising the thiophene ring-fused polycyclic aromatic compound according to any one of [1] to [9] and an organic solvent.
[11] The composition according to [10], further comprising a synthetic organic polymer.
[12] A thin film comprising the thiophene ring-fused polycyclic aromatic compound according to any one of [1] to [9].

  According to the present invention, there is provided a thiophene ring-fused polycyclic aromatic compound in which at least one of the terminal aromatic rings of the naphthacene skeleton is replaced with a thiophene ring. According to a preferred embodiment of the present invention, the thiophene ring-fused polycyclic aromatic compound of the present invention is expected to be chemically stable and exhibit high mobility. The thiophene ring-fused polycyclic aromatic compound of the present invention is suitably used, for example, as an organic field effect transistor material.

  Hereinafter, the thiophene ring-fused polycyclic aromatic compound of the present invention and uses thereof will be described in detail.

1. Thiophene ring condensed polycyclic aromatic compound The thiophene ring condensed polycyclic aromatic compound of the present invention is represented by the following formula (1a), (1b) or (1c).
[Wherein, R ¹ , R ² , R ³ and R ⁴ are each independently the same or different and are a hydrogen atom; a halogen atom; an optionally substituted C ₁ -C ₂₀ hydrocarbon; A C ₁ -C ₂₀ alkoxy group which may have a substituent; a C ₆ -C ₂₀ aryloxy group which may have a substituent; an amino group which may have a substituent; A silyl group which may have a group; a hydroxyl group; a thienyl group which may have a substituent; a pyridyl group which may have a substituent; and a furyl group which may have a substituent. ,
R ⁵ , R ^{5 ′,} and R ⁶ are each independently the same or different and are each a halogen atom; an optionally substituted C ₁ -C ₂₀ hydrocarbon group; A C ₁ -C ₂₀ alkoxy group which may have a substituent; a C ₆ -C ₂₀ aryloxy group which may have a substituent; an amino group which may have a substituent; a silyl which may have a substituent A group; a hydroxyl group; a thienyl group which may have a substituent, a pyridyl group which may have a substituent, a furyl group which may have a substituent,
m and m ′ are each independently the same or different and are an integer of 0 to 2, and n is an integer of 0 to 4. ]

  The thiophene ring-fused polycyclic aromatic compound of the present invention has a structure in which one or both of the terminal aromatic rings of the naphthacene skeleton are replaced with a thiophene ring. According to a preferred embodiment of the present invention, when the thiophene ring-fused polycyclic aromatic compound of the present invention is condensed with a thiophene ring, the chemical stability of the compound is enhanced, and when it is in the form of a thin film. Are also expected to express high mobility.

In the above formula (1a), (1b) or (1c), R ¹ , R ² , R ³ and R ⁴ are each independently the same or different and have a hydrogen atom; a halogen atom; a substituent. which may be C ₁ -C ₂₀ hydrocarbon group; which may have a substituent group C ₁ -C ₂₀ alkoxy groups; which may have a substituent C ₆ -C ₂₀ aryloxy group; substituents An amino group which may have a substituent; a silyl group which may have a substituent; a hydroxyl group; a thienyl group which may have a substituent; a pyridyl group which may have a substituent; It is a furyl group which may have.

  In the present specification, the “halogen atom” is preferably fluorine, chlorine, bromine or iodine.

In the present specification, the hydrocarbon group of the “C ₁ -C ₂₀ hydrocarbon group” may be a saturated or unsaturated acyclic group, or a saturated or unsaturated cyclic group. When the C ₁ -C ₂₀ hydrocarbon group is acyclic, it may be linear or branched. The “C ₁ -C ₂₀ hydrocarbon group” includes a C ₁ -C ₂₀ alkyl group, a C ₂ -C ₂₀ alkenyl group, a C ₂ -C ₂₀ alkynyl group, a C ₄ -C ₂₀ alkyl dienyl group, a C _6- C ₁₈ aryl group, C ₇ -C ₂₀ alkylaryl group, C ₇ -C ₂₀ arylalkyl group, C ₄ -C ₂₀ cycloalkyl group, C ₄ -C ₂₀ cycloalkenyl group, (C ₃ ~C ₁₀ cycloalkyl) C ₁ -C ₁₀ alkyl groups and the like are included.

In the present specification, "C ₁ -C ₂₀ alkyl group" is preferably C ₁ -C ₁₂ alkyl group, more preferably a C ₁ -C ₁₀ alkyl group, C ₁ -C ₆ alkyl group More preferably. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, dodecanyl and the like.

In the present specification, "C ₂ -C ₂₀ alkenyl group" is preferably C ₂ -C ₁₀ alkenyl group, more preferably a C ₂ -C ₆ alkenyl group. Examples of alkenyl groups include, but are not limited to, vinyl, allyl, propenyl, isopropenyl, 2-methyl-1-propenyl, 2-methylallyl, 2-butenyl and the like.

In the present specification, "C ₂ -C ₂₀ alkynyl group" is preferably C ₂ -C ₁₀ alkynyl group, more preferably a C ₂ -C ₆ alkynyl group. Examples of alkynyl groups include, but are not limited to, ethynyl, propynyl, butynyl, and the like.

In the present specification, "C ₄ -C ₂₀ alkyldienyl group" is preferably C ₄ -C ₁₀ alkadienyl group, more preferably a C ₄ -C ₆ alkadienyl group. Examples of alkyldienyl groups include, but are not limited to, 1,3-butadienyl.

In the present specification, the “C ₆ -C ₁₈ aryl group” is preferably a C ₆ -C ₁₂ aryl group. Examples of the aryl group include, but are not limited to, phenyl, 1-naphthyl, 2-naphthyl, indenyl, biphenylyl, anthryl, phenanthryl and the like.

In the present specification, the “C ₇ -C ₂₀ alkylaryl group” is preferably a C ₇ -C ₁₂ alkylaryl group. Examples of alkylaryl groups include, but are not limited to, o-tolyl, m-tolyl, p-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, o-cumenyl, m -Cumenyl, p-cumenyl, mesityl and the like can be mentioned.

In the present specification, the “C ₇ -C ₂₀ arylalkyl group” is preferably a C ₇ -C ₁₂ arylalkyl group. Examples of arylalkyl groups include, but are not limited to, benzyl, phenethyl, diphenylmethyl, triphenylmethyl, 1-naphthylmethyl, 2-naphthylmethyl, 2,2-diphenylethyl, 3-phenylpropyl, 4-phenyl Examples include phenylbutyl and 5-phenylpentyl.

In the present specification, the “C ₄ -C ₂₀ cycloalkyl group” is preferably a C ₄ -C ₁₀ cycloalkyl group. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.

In the present specification, the “C ₄ -C ₂₀ cycloalkenyl group” is preferably a C ₄ -C ₁₀ cycloalkenyl group. Examples of cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and the like.

In the present specification, the “C ₁ -C ₂₀ alkoxy group” is preferably a C ₁ -C ₁₀ alkoxy group, and more preferably a C ₁ -C ₆ alkoxy group. Examples of the “C ₁ -C ₂₀ alkoxy group” include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, pentyloxy and the like.

In the present specification, the “C ₆ -C ₂₀ aryloxy group” is preferably a C ₆ -C ₁₀ aryloxy group. Examples of aryloxy groups include, but are not limited to, phenyloxy, naphthyloxy, biphenyloxy, and the like.

In this specification, the C ₁ -C ₂₀ hydrocarbon radical, is C ₁ -C ₂₀ alkoxy or C ₆ -C ₂₀ aryloxy group has a substituent, the substituent is a halogen atom, a hydroxyl group, Nitro group, optionally substituted amino group, optionally substituted silyl group, alkoxy group, aryloxy group, optionally substituted thienyl group, substituted It is preferably selected from the group consisting of an optionally pyridyl group and an optionally substituted furyl group. The number of these substituents may be 1 or 2 or more.

In the present specification, when an amino group, silyl group, thienyl group, pyridyl group or furyl group has a substituent, the substituent is a C _{1 to} C ₂₀ hydrocarbon group (among others, C _{1 to} C ₁₀ alkyl group, C ₂ -C ₁₀ alkenyl group, C ₂ -C ₁₀ alkynyl group, C ₆ -C ₁₈ aryl group is preferred), C ₁ ~C ₁₀ alkoxy group;. C ₆ -C ₁₀ aryloxy group, a hydroxyl group, it is preferably selected from C ₁ -C ₂₀ alkoxycarbonyl group, and a C ₆ -C group consisting ₂₀ aryloxycarbonyl group; C ₇ -C ₂₀ alkylaryl group. The number of these substituents may be 1 or 2 or more.

  In the present specification, examples of the “amino group which may have a substituent” include, but are not limited to, amino, dimethylamino, methylamino, methylphenylamino, phenylamino and the like. .

  In this specification, examples of “optionally substituted silyl group” include, but are not limited to, dimethylsilyl, diethylsilyl, trimethylsilyl, triethylsilyl, trimethoxysilyl, triethoxysilyl, diphenyl Mention may be made of methylsilyl, triphenylsilyl, triphenoxysilyl, dimethylmethoxysilyl, dimethylphenoxysilyl, methylmethoxyphenyl and the like.

  In this specification, examples of the “optionally substituted thienyl group” include methylthienyl, phenylthienyl, and thienyl oligomers (thiophene dimer, trimer, tetramer, 5 (Mer) and the like.

  In the present specification, examples of the “optionally substituted pyridyl group” include methylpyridyl, phenylpyridyl, bipyridyl and the like.

  In the present specification, examples of the “furyl group optionally having a substituent” include methylfuryl, phenylfuryl and the like.

In one embodiment of the present invention, it is preferable that any ^one of R ¹ and R ² , or R ³ and R ⁴ is a C _{6 to} C ₂₀ aryl group which may have a substituent. By having a C ₆ -C ₂₀ aryl group that may be present in any one of R ¹ and R ² , or R ³ and R ⁴ , the π-electron system spreads and π stacking is facilitated. The function as an effect transistor material is improved.

Alternatively, R ^1, R ^2, it is preferred that R ³ and R ⁴ are optionally C ₆ -C ₂₀ aryl group which may have a substituent. By having a C ₆ -C ₂₀ aryl group which may have a substituent in R ¹ , R ² , R ³ and R ⁴ , the π electron system spreads and π stacking is facilitated, and an organic field effect transistor material The function as a further improvement.

Among them, R ¹ , R ² , R ³ and R ⁴ are preferably a phenyl group which may have a substituent, and particularly preferably a phenyl group. Such a compound is considered to have high mobility derived from the rubrene skeleton and chemical stability due to condensation of the thiophene ring.

In one embodiment of the present invention, R ¹ and R ² are preferably the same functional group, and R ³ and R ⁴ are preferably the same functional group. Since R ¹ and R ² , and R ³ and R ⁴ are the same functional group, synthesis is facilitated.

In another embodiment of the present invention, R ¹ and R ² are alkynyl groups which may have a substituent, and R ³ and R ⁴ are phenyl groups which may have a substituent. Preferably there is.

In the above formula (1a), (1b) or (1c), R ⁵ , R ^{5 ′} and R ⁶ are each independently of each other, the same or different, a halogen atom; an optionally substituted C _{1 to} C ₂₀ hydrocarbon group; C _{1 to} C ₂₀ alkoxy group which may have a substituent; C _{6 to} C ₂₀ aryloxy group which may have a substituent; An amino group which may have a substituent; a silyl group which may have a substituent; a hydroxyl group; a thienyl group which may have a substituent; a pyridyl group which may have a substituent; It is also a good furyl group.

In one embodiment of the present invention, R ⁵ , R ^{5 ′,} or R ⁶ has a conjugated substituent that extends the π-electron system, such as an alkenyl group that may have a substituent, or a substituent. An alkynyl group which may have a substituent, an aryl group which may have a substituent, a thienyl group which may have a substituent, a pyridyl group which may have a substituent, or a substituent. Good furyl groups are preferred.

  In the above formula, m and m ′ are integers of 0-2. Among these, 0 or 1 is preferable.

  In said formula, n is an integer of 0-4. Among these, n is preferably 0, 1 or 2.

In one Embodiment of this invention, it is preferable that the thiophene ring condensed polycyclic aromatic compound of this invention is a thing shown by following formula (1a '), (1b'), or (1c ').
[Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{5 ′} have the same meaning as described above. ]

As shown by the above formula, when the functional group R ⁵ is provided along the axis of the condensed ring skeleton, the π-electron system is easy to spread, and the physical properties can be controlled by the type of the substituent.

In another embodiment of the present invention, the thiophene ring-fused polycyclic aromatic compound of the present invention is represented by the following formula (1a ″), (1b ″) or (1c ″): preferable.
[Wherein, R ¹ , R ² , R ³ and R ⁴ have the same meanings as described above. ]

  As shown by the above formula, the synthesis is easy if the terminal aromatic ring does not have a substituent.

Specific examples of the thiophene ring-fused polycyclic aromatic compound of the present invention include the following compounds.
[Wherein, R represents an alkyl group. Me represents a methyl group, and iPr represents an isopropyl group. ]

2. Method for producing thiophene ring-fused polycyclic aromatic compound The thiophene ring-fused polycyclic aromatic compound of the present invention can be produced as follows.

For example, the compound represented by the above formula (1a) can be produced according to the following reaction scheme I.
[Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{6 ′} , m and m ′ are as defined above]. ]

First, an organometallic compound represented by L ¹ L ² MY ¹ Y ² such as bis (cyclopentadienyl) dichlorozirconium is allowed to act on the thiophene derivative (I) to produce metallacyclopentadiene (II). The production of metallacyclopentadiene from an organometallic compound represented by L ¹ L ² MY ¹ Y ² is described in, for example, T. Takahashi et al. J. Org. Chem. 1995, 60, 4444. The reaction proceeds under the same or approximate conditions.

  The amount of the organometallic compound used is preferably 0.5 to 10 equivalents, more preferably 1 to 5 equivalents, and still more preferably 1 to 3 equivalents of the thiophene derivative (I).

  The above reaction is preferably performed in a temperature range of −80 to 300 ° C., particularly preferably in a temperature range of 0 to 150 ° C. The pressure is in the range of 0.1 to 2500 bar, preferably in the range of 0.5 to 10 bar. The reaction can be carried out continuously or batchwise, in one step or more, in solution, suspension, gas phase or supercritical medium.

  As the reaction solvent, an aliphatic or aromatic solvent is used, and a polar solvent is preferably used. Ether solvents such as tetrahydrofuran or diethyl ether; halogenated hydrocarbons such as methylene chloride; halogenated aromatic hydrocarbons such as o-dichlorobenzene; amides such as N, N-dimethylformamide, and sulfoxides such as dimethyl sulfoxide. Used. Alternatively, aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene may be used as the aromatic solvent.

  Here, M represents a Group 3 to Group 5 or lanthanide series metal in the periodic table. M is preferably a group 4 or lanthanide series metal of the periodic table, more preferably a group 4 metal of the periodic table, that is, titanium, zirconium and hafnium.

L ¹ and L ² are independent of each other and are the same or different and represent an anionic ligand. The anionic ligand is preferably a delocalized cyclic η ⁵ -coordinated ligand, a C ₁ -C ₂₀ alkoxy group, a C ₆ -C ₂₀ aryloxy group or a dialkylamide group.

Among these, L ¹ and L ² are preferably delocalized cyclic η ⁵ -coordinate ligands. Examples of the delocalized cyclic η ⁵ -coordinated ligand are an unsubstituted cyclopentadienyl group and a substituted cyclopentadienyl group. This substituted cyclopentadienyl group includes, for example, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, n-butylcyclopentadienyl, t-butylcyclopentadienyl, dimethylcyclopentadienyl, Diethylcyclopentadienyl, diisopropylcyclopentadienyl, di-t-butylcyclopentadienyl, tetramethylcyclopentadienyl, indenyl group, 2-methylindenyl group, 2-methyl-4-phenylindenyl group, A tetrahydroindenyl group, a benzoindenyl group, a fluorenyl group, a benzofluorenyl group, a tetrahydrofluorenyl group and an octahydrofluorenyl group.

In the delocalized cyclic η ⁵ -coordinated ligand, one or more atoms of the delocalized cyclic π system may be substituted with a hetero atom. In addition to hydrogen, it may contain one or more heteroatoms such as elements of group 14 of the periodic table and / or elements of groups 15, 16 and 17 of the periodic table.

A delocalized cyclic η ⁵ -coordinated ligand, for example, a cyclopentadienyl group may be bridged by a central metal and one or more bridging ligands, which may be cyclic. Good. The bridging ligand, _{e.g., CH 2, CH 2 CH 2} , CH (CH 3) CH 2, CH (C 4 H 9) C (CH 3) 2, C (CH 3) 2, (CH 3) ₂ Si, (CH ₃ ) ₂ Ge, (CH ₃ ) ₂ Sn, (C ₆ H ₅ ) ₂ Si, (C ₆ H ₅ ) (CH ₃ ) Si, (C ₆ H ₅ ) ₂ Ge, (C ₆ H ₅ ) ₂ Sn, (CH ₂ ) ₄ Si, CH ₂ Si (CH ₃ ) ₂ , o-C ₆ H ₄ or 2, 2 ′-(C ₆ H ₄ ) ₂ .

Two or more delocalized cyclic η ⁵ -coordinating ligands, for example, cyclopentadienyl groups, may be cyclic to each other, and may be cross-linked by one or more cross-linking groups. . Examples of the bridging group include CH ₂ , CH ₂ CH ₂ , CH (CH ₃ ) CH ₂ , CH (C ₄ H ₉ ) C (CH ₃ ) ₂ , C (CH ₃ ) ₂ , (CH ₃ ) ₂ Si. , (CH ₃ ) ₂ Ge, (CH ₃ ) ₂ Sn, (C ₆ H ₅ ) ₂ Si, (C ₆ H ₅ ) (CH ₃ ) Si, (C ₆ H ₅ ) ₂ Ge, (C ₆ H ₅ ) ₂ Sn, (CH ₂ ) ₄ Si, CH ₂ Si (CH ₃ ) ₂ , o-C ₆ H ₄ or 2, 2 ′-(C ₆ H ₄ ) ₂ .
Metallacyclopentadiene also includes compounds having two or more metallacyclopentadiene moieties. Such compounds are known as polynuclear metallocenes. The polynuclear metallocene may have any substitution pattern and any bridge form. The independent metallocene portions of the polynuclear metallocene may be the same or different. Examples of the polynuclear metallocene are described in, for example, EP-A-632063, JP-A-4-80214, JP-A-4-85310, and EP-A-654476.

Y ¹ and Y ² are each independently the same or different and are a leaving group. Examples of the leaving group include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, C ₁ -C ₂₀ alkyl group such as n-butyl group, and C ₆ -C ₂₀ aryl group such as phenyl group. included.

  Next, 2,3-diiodothiophene is reacted with metallacyclopentadiene (II) to form a thiophene ring to obtain a thiophene ring-containing hydrocarbon condensed ring (III). Typically, 2,3-diiodothiophene is added to the reaction mixture without isolating the metallacyclopentadiene (II).

  Reaction of metallacyclopentadiene such as zirconacyclopentadiene with 2,3-dihalothiophene in the presence of CuCl to form a thiophene ring is described in Takahashi et al. J. Am. Chem. Soc., 1996, 118, 5154-5155, and the reaction can proceed under the same or similar conditions.

  For example, the amount of 2,3-diiodothiophene used is preferably from 0.1 to 10 equivalents of metallacyclopentadiene (II), more preferably from 0.5 to 5 equivalents, still more preferably from 1 to 3 equivalents.

  Moreover, it is not restricted to CuCl, You may use a metal compound. The metal compound is preferably a metal compound of Groups 4 to 15 of the periodic table. The metal compound may be a salt such as CuCl or an organometallic complex.

Examples of the salt include CuX, NiX ₂ , PdX ₂ , ZnX ₂ , CrX ₂ , CrX ₃ , CoX ₂ , or BiX ₃ (wherein X represents a halogen atom such as a chlorine atom or a bromine atom). A metal salt such as

As the metal compound, an organometallic complex, particularly a nickel complex may be used. As an organometallic complex, a ligand such as a phosphine; an aromatic amine such as pyridine or bipyridine, or a ligand such as a halogen atom is coordinated to the central metal of Group 3 to 11 of the periodic table, preferably the central metal of Group 6 to 11 of the periodic table. What is doing is used preferably. The central metal is preferably so-called 4-6 coordination, and more preferably a metal of Group 10 of the periodic table. The phosphine is not limited, such as triphenylphosphine and methyldiphenylphosphine. Examples of the organometallic complex include bis (triphenylphosphine) dichloronickel, dichloro (2,2′-bipyridine) nickel, and PdCl ₂ (2,2′-bipyridine). The reaction of metallacyclopentadiene such as zirconacyclopentadiene with alkyne in the presence of a nickel phosphine complex to form a benzene ring is described in T. Takahashi et.al. J. Am. Chem. Soc., Vol. 121., No. 48, 1999, 11095.

  The above reaction is preferably performed in a temperature range of −80 to 300 ° C., particularly preferably in a temperature range of 0 to 150 ° C. The pressure is in the range of 0.1 to 2500 bar, preferably in the range of 0.5 to 10 bar.

  The same reaction solvent as that used in the above step can be used.

  The above reaction is preferably performed in the presence of a stabilizer for stabilizing the metal compound in a solvent. In particular, when the metal compound is a metal salt and the solvent is an organic solvent, the stabilizer stabilizes the metal salt in the organic solvent. Examples of the stabilizer include N, N′-dimethylpropylene urea (DMPU), hexamethylphosphoamide and the like.

  Next, the thiophene ring-condensed hydrocarbon condensed ring (III) is stirred and refluxed overnight in the presence of an oxidizing agent such as pyridinium chlorochromate (PCC) in the air to obtain a thiophene ring condensed naphthacenequinone (IV). Get.

Examples of the oxidizing agent include pyridinium chlorochromate, metal chlorides such as iron (III) chloride (FeCl ₃ ), t-butyl hydroperoxide (t-BuOOH), 2,3-dichloro-5,6-dicyano. -P-benzoquinone (DDQ) or the like may be used. As for the usage-amount of an oxidizing agent, about 1-10 equivalent is preferable.

  The above reaction is preferably performed in a temperature range of −80 to 300 ° C., particularly preferably in a temperature range of 0 to 150 ° C. The pressure is in the range of 0.1 to 2500 bar, preferably in the range of 0.5 to 10 bar.

  The same reaction solvent as that used in the above step can be used.

For example, when using metal chloride such as iron chloride (III) (FeCl ₃ ) and t-butyl hydroperoxide (t-BuOOH) instead of pyridinium chlorochromate, the reaction mixture is stirred under air, A thiophene-ring-condensed naphthacenequinone (IV) can be obtained by stirring and refluxing overnight in the presence of a strong base such as 1,8-diazabicyclo (5,4,0) undecene-7 (DBU).

  Instead of t-butyl hydroperoxide, DDQ may be used. The amount used is preferably 1 to 10 equivalents.

  As the metal chloride, copper chloride may be used in addition to iron (III) chloride. The amount of metal chloride used is preferably 1 to 10 equivalents.

  As the strong base, 1,8-diazabicyclo (5,4,0) undecene-7 (DBU) or dimethylpropylene urea may be used. The amount of strong base used is preferably 1 to 10 equivalents.

  The above reaction is preferably performed in a temperature range of −80 to 300 ° C., particularly preferably in a temperature range of 0 to 150 ° C. The pressure is in the range of 0.1 to 2500 bar, preferably in the range of 0.5 to 10 bar.

  The same reaction solvent as that used in the above step can be used.

Next, the thiophene ring-fused naphthacenequinone (IV) is reacted with the organolithium reagents R ¹ Li and R ² Li (wherein R ¹ and R ² have the same meanings as described above) to give a thiophene ring-containing compound ( V) is obtained.

  The amount of the organolithium reagent used is preferably 2 to 15 equivalents, more preferably 4 to 10 equivalents, and still more preferably 4 to 8 equivalents of the thiophene ring condensed naphthacenequinone (IV).

  The above reaction is preferably performed in a temperature range of room temperature to 200 ° C, and particularly preferably in a temperature range of 50 to 150 ° C. The pressure is preferably performed at atmospheric pressure. The reaction can be carried out continuously or batchwise, in one step or more, in solution, suspension, gas phase or supercritical medium. The same reaction solvent as that used in the above step is used. The reaction is preferably performed in a nitrogen atmosphere.

Next, the obtained thiophene ring-containing compound (V) is reacted in the presence of TiCl ₃ (THF) ₃ and aluminum magnesium hydride (LiAlH ₄ ) to obtain a thiophene ring condensed polycyclic aromatic compound (1a). be able to.

Tin chloride may be used instead of TiCl ₃ (THF) ₃ . The amount used is preferably 1 to 10 equivalents.

  Instead of magnesium aluminum hydride, lithium aluminum hydride may be used. The amount used is preferably 1 to 10 equivalents.

  The above reaction is preferably performed in a temperature range of −80 to 300 ° C., particularly preferably in a temperature range of 0 to 150 ° C. The pressure is in the range of 0.1 to 2500 bar, preferably in the range of 0.5 to 10 bar.

  The same reaction solvent as that used in the above step is used.

  After completion of the reaction, the desired thiophene ring-fused polycyclic aromatic compound (1a) can be isolated and purified from the reaction mixture by, for example, a chromatography method.

  The compound represented by the above formula (1b) can also be produced in the same manner as in the method for producing the compound represented by the above formula (1a). That is, the compound represented by the above formula (1b) is an isomer of the compound represented by the above formula (1a) (or the compound represented by the above formula (1a) is a compound represented by the above formula (1b). (As isomers), the target compound can be obtained by isolating and purifying each compound from the reaction product.

The compound represented by the above formula (1c) should be produced in the same manner as in Reaction Scheme I except that benzene derivative (I ′) is used as a starting compound instead of thiophene derivative (I). Can do. For example, the compound represented by the above formula (1c) can be produced according to the following reaction scheme II.
[Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{6 ′} , m, m ′ and n are as defined above] ]

  Each step in Reaction Scheme II can be carried out in the same manner as in Reaction Scheme I. Details are as shown in the examples, and those skilled in the art can appropriately select reaction conditions while referring to the examples.

3. Use of thiophene ring-fused polycyclic aromatic compound The thiophene ring-fused polycyclic aromatic compound of the present invention is soluble in an organic solvent and can be dissolved in an organic solvent and used as a composition.

  The organic solvent is not particularly limited as long as it can dissolve the thiophene ring-fused polycyclic aromatic compound of the present invention. For example, an aliphatic or aromatic solvent is used. Specifically, ether solvents such as tetrahydrofuran and diethyl ether; halogenated hydrocarbons such as methylene chloride; halogenated aromatic hydrocarbons such as o-dichlorobenzene; amides such as N, N-dimethylformamide, dimethyl sulfoxide and the like Preferred examples include sulfoxides of: aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene.

  The content of the thiophene ring-fused polycyclic aromatic compound in the composition of the present invention is not particularly limited, and is preferably in the range of about 1 to about 99% by weight, for example, 1 to 50% by weight with respect to the total weight of the composition. % Is more preferable, a range of 1 to 30% by weight is further preferable, and a range of 5 to 15% by weight is particularly preferable.

  The composition of the present invention may contain a synthetic organic polymer. The content of the synthetic organic polymer is not particularly limited, and is preferably in the range of about 0.01 to about 30% by weight, more preferably in the range of 0.01 to 10% by weight, based on the total weight of the composition, The range of 0.1 to 5% by weight is more preferable, and the range of 0.1 to 2% by weight is particularly preferable.

  The synthetic organic polymer used in the present invention includes thermoplastic polymers, thermosetting polymers, engineering plastics, conductive polymers and the like. The synthetic organic polymer may be a copolymer. Thermoplastic polymers include, for example, polyolefins such as polyethylene, polypropylene, polycycloolefin, ethylene-propylene copolymer, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyacrylic acid, polymethacrylic acid, polystyrene, polyamide, polyester, Polycarbonate and the like are included. Examples of the thermosetting polymer include phenol resin, urea resin, melamine resin, alkyd resin, unsaturated polyester resin, epoxy resin, silicon resin, and polyurethane resin. Engineering plastics include, for example, polyimide, polyphenylene oxide, polysulfone, and the like. The synthetic organic polymer may be a synthetic rubber such as styrene-butadiene, or a fluororesin such as polytetrafluoroethylene.

  Examples of the conductive polymer include conjugated polymers such as polyacetylene, polypyrrole, polyarylene vinylene, and polythienylene vinylene, or those obtained by doping them with an electron donating molecule or an electron accepting molecule. Furthermore, as the conductive polymer, a charge transfer complex comprising an electron donating molecule such as tetrathiafulvalene or bisethylenedithiotetrathiafulvalene, or a combination thereof with an electron accepting molecule such as tetracyanoquinodimethane or tetracyanoethylene. Is mentioned.

  The composition may further contain various additives. Examples of the additive include a plasticizer, an antistatic agent, a colorant, and a dopant. Furthermore, the composition may contain reinforcing materials such as glass fiber, carbon fiber, aramid fiber, boron fiber, and carbon nanotube.

  The composition can be in the form of fibers, films or sheets using methods known to those skilled in the art, including, but not limited to, melt spinning, spinning from solution, dry jet. There are wet spinning, extrusion, casting, and molding methods. The fibers, films or sheets can be further processed by rolling, stamping, secondary forming or other methods known to those skilled in the art.

  The composition of the present invention may contain other additives as long as the object of the present invention is not impaired.

Since the composition of the present invention is in the form of a solution, it can be applied onto a substrate using a coating method or a printing method such as an inkjet method, a screen printing method, or a gravure printing method. It can be in the form of
Thus, the thin film of this invention obtained can be used suitably as a thin film of various organic electronic devices. In particular, the thin film of the present invention contains the thiophene ring-fused polycyclic aromatic compound of the present invention and can exhibit high mobility, and thus is useful as a thin film of an organic field effect transistor, for example.

  EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not restrict | limited to the following Example.

All reactions were carried out using an anhydrous solvent under a nitrogen atmosphere unless otherwise specified. THF and ether were dehydrated using sodium / benzophenone system. Unless otherwise specified, commercially available products were used as they were without purification.
2,3-Diiodothiophene was synthesized according to Gronowitz, S .; Vilks, V. Arkiv foer Kemi. 1963, 21 (18), 191-199.
1,2-bis (3-phenyl-2-propynyl) benzene can be obtained from Takahashi, T .; Kitamura, M .; Shen, B .; Nakajima, KJ Am. Chem. Soc. 2000, 122, 12876-12877 or Takahashi. , T .; Li, S .; Huang, W .; Kong, F .; Nakajima, K .; Shen, B .; Ohe, T .; Kanno, KJ Org. Chem. 2006, 71, 7967-7977 Synthesized.

The following models were used for NMR.
NMR-JEOL JNM-AL300, Bruker ARX-400
NMR data was described according to the following notation.
¹ H NMR (400 MHz and 300 MHz):
The chemical shift of each sample is shown by δ value (ppm) when tetramethylsilane is used as an internal standard. The spin coupling constant is indicated by J value (Hz). Coupling patterns were abbreviated as singlet (s), doublet (d), triplet (t), quartet (q), multiplet (m), and broad (br). The NMR yield was determined using mesitylene as an internal standard.
¹³ C NMR (100 MHz and 75 MHz):
The chemical shift value of each sample was represented by a δ value (ppm) when chloroform (77.00 ppm) was used as an internal standard.

  For silica gel column chromatography, Merck silica gel 60 (230-400 mesh ASTM), Kanto Chemical Silica Gel 60 N (spherical, neutral, 40-100 μm) or Kanto Chemical Silica Gel 60 (40-63 μm) was used as a filler. Kiesel gel 60 PF254 was used for analytical thin layer chromatography.

[Example 1]
Production of thiophene ring condensed polycyclic aromatic compound 1
According to Reaction Scheme 1, thiophene ring-fused polycyclic aromatic compounds (6a) and (6b) were produced.

<Step 1>
Preparation of 4,11-diphenyl-5,10-dihydroanthra [2,3-b] thiophene (3)

In a THF solution (5 mL) of bis (cyclopentadienyl) zirconium dichloride (Cp ₂ ZrCl ₂ ) (351 mg, 1.2 mmol) at −78 ° C., n-BuLi (1.57 M hexane solution, 1.53 mL, 2.4 mmol) was added and the mixture was stirred at −78 ° C. for 1 h.
After adding 1,2-bis (3-phenyl-2-propynyl) benzene (306 mg, 1.0 mmol) to the mixture, the mixture was allowed to warm to room temperature and stirred overnight.
After stirring overnight, to this mixture was added CuCl (196 mg, 2.0 mmol), DMPU (0.44 mL, 3.6 mmol) and 2,3-diiodothiophene (403 mg, 1.2 mmol) at 50 ° C. The mixture was further stirred for 24 hours.
A 3M aqueous HCl solution was added to the mixture and quenched to 0 ° C., followed by extraction with ethyl acetate. The organic phases were combined and washed with water, saturated aqueous sodium bicarbonate and brine. The resulting solution was dried over anhydrous sodium sulfate. The black viscous oil obtained by removing the solvent was purified by flash chromatography (silica gel, hexane: toluene = 10: 1 solution was used as eluent) to give the title compound (3) (197 mg, 197 mg, Yield 51%).
3: ¹ H NMR (CDCl ₃ , Me ₄ Si) δ 3.89 (s, 2 H), 3.90 (s, 2 H), 6.71 (d, J = 6 Hz, 1 H), 7.09-7.18 (m, 4 H), 7.22 (d, J = 5 Hz, 2 H), 7.41-7.59 (m, 9 H); ¹³ C NMR (CDCl ₃ , Me ₄ Si) δ34.5 (2 peaks were overlapped), 124.0, 126.0, 126.1, 126.95, 126.96, 127.3, 127.9, 128.4, 128.8, 129.0, 129.5, 130.0, 131.7, 132.1, 133.5, 134.4, 137.3, 137.5, 137.7, 139.1, 139.6, 139.7.HRMS calcd for C ₂₈ H ₂₀ S : 388.1286. Found: 388.1292.

<Step 2>
Preparation of 4,11-diphenylanthra [2,3-b] thiophene-5,10-dione (4) using PCC

In a solution of 4,11-diphenyl-5,10-dihydroanthra [2,3-b] thiophene (3) (127 mg, 0.33 mmol) in 1,2-dichloroethane (6 mL), pyridinium chlorochromate (PCC) A homogeneous fine powder mixture of (668 mg, 3.1 mmol) and Celite (1.5 g) was added.
The mixture was stirred at reflux overnight, then diluted with ether (5 mL) and filtered. The filter cake was washed twice with ether (5 mL), and the filtrate was concentrated under reduced pressure. The resulting brown solid material was purified by flash chromatography (silica gel, using chloroform as the eluent) to give the title compound (4) as a yellow solid (70 mg, 51% yield).
4: ¹ H NMR (CDCl ₃ , Me ₄ Si) δ7.01 (d, J = 5 Hz, 1 H), 7.33 (d, J = 8 Hz, 2 H), 7.39 (d, J = 8 Hz, 2 H), 7.50-7.58 (m, 7 H), 7.65-7.68 (m, 2 H), 8.07-8.10 (m, 2 H); ¹³ C NMR (CDCl ₃ , Me ₄ Si) δ 125.8, 126.4 , 126.8, 126.9, 127.1, 127.6, 127.8, 127.9, 128.1, 128.4, 128.7, 132.4, 133.5, 133.6, 134.3, 134.5, 139.2, 139.9, 140.7, 141.1, 143.6, 148.0, 184.0, 184.2.HRMS calcd for C ₂₈ H ₁₆ O ₂ S: 416.0871. Found: 416.0865.

<Process 2 '>
Preparation of 4,11-diphenylanthra [2,3-b] thiophene-5,10-dione (4) using FeCl ₃ and TBHP

In a pyridine solution (45 mL) of 4,11-diphenyl-5,10-dihydroanthra [2,3-b] thiophene (3) (3.42 g, 8.8 mmol), FeCl ₃ .6H ₂ O (95 mg, 0.35 mmol) was added and allowed to dissolve well before t-butyl hydroperoxide (TBHP) (70% aqueous solution, 7.3 mL, 52.8 mmol) was added. The reaction mixture was stirred at 80 ° C. for 3 hours. During this time air was entrained in the reaction mixture.
Next, 1,8-diazabicyclo [5.4.0] undic-7-ene (DBU) (5.25 mL, 35.2 mmol) was added. The reaction mixture was stirred and refluxed overnight, then 3M HCl aqueous solution was added, and the mixture was quenched and extracted with chloroform. The organic phases were combined and washed with water, saturated aqueous sodium bicarbonate and brine. The resulting solution was dried over anhydrous sodium sulfate. The black viscous oil obtained by removing the solvent was purified by flash chromatography (silica gel, using chloroform as the eluent) to give the title compound (4) as a yellow solid (2.48 mg, yield). 68%).

<Step 3-1>
Preparation of 4,5,10,11-tetraphenyl-5,10-dihydroanthra [2,3-b] thiophene-5,10-diol (5a)

Phenyllithium (1.08 M cyclohexane-diethyl) in ether solution (2 mL) of 4,11-diphenylanthra [2,3-b] thiophene-5,10-dione (83 mg, 0.2 mmol) at −78 ° C. Ether solution, 0.55 mL, 0.6 mmol) was added. The resulting solution was returned to room temperature and further stirred for 24 hours.
The mixture was quenched with saturated aqueous NH ₄ Cl and extracted with chloroform. The organic phases were combined and washed with water, saturated aqueous sodium bicarbonate and brine. The resulting solution was dried over anhydrous sodium sulfate. The residue obtained by removing the solvent was purified by silica gel chromatography (using chloroform as the eluent) to give the title compound (5a) as a colorless powder (105 mg, yield 92%).
5a: 1H NMR (CDCl3, Me4Si) δ4.30 (s, 1 H), 4.35 (s, 1 H), 6.09 (d, J = 8 Hz, 2 H), 6.19 (d, J = 8 Hz, 2 H), 6.38 (d, J = 6 Hz, 2 H), 6.74-6.79 (m, 2 H), 6.81-6.88 (m, 2 H), 6.98-7.18 (m, 19 H); 13C NMR (CDCl3 , Me4Si) δ75.1, 75.3, 124.5, 125.51, 125.54, 125.9 (2 peaks were overlapped), 126.0, 126.1 (2 peaks were overlapped), 126.5, 126.8, 127.1, 127.3, 127.4 (2 peaks were overlapped), 127.48 (2 peaks were overlapped), 127.52 (2 peaks were overlapped), 127.6, 127.8, 128.6, 128.7, 129.6, 130.1, 130.5, 130.6, 135.2, 135.7, 137.3, 137.6, 137.7 (2 peaks were overlapped), 140.4, 140.8 , 141.3, 144.5, 149.0, 149.2.HRMS calcd for C40H28O2S: 572.1810. Found: 572.1797.

<Step 4-1>
Preparation of 4,5,10,11-tetraphenylanthra [2,3-b] thiophene (6a)

In a solution of TiCl ₃ (THF) ₃ (148 mg, 0.40 mmol) in THF (2 mL) at 0 ° C., magnesium aluminum hydride (LiAlH ₄ ) (7.6 mg, 0.2 mmol) was added and the mixture was added. Stir at 0 ° C. for 10 minutes. The resulting solution was subsequently stirred at reflux for 1 hour.
4,5,10,11-Tetraphenyl-5,10-dihydroanthra [2,3-b] thiophene-5,10-diol (5a) (57 mg, 0.1 mmol) was added to this solution, The mixture was refluxed for 1 hour.
Thereafter, MeOH (2 mL) was added to the mixture to quench, and extraction with ethyl acetate (2 mL) was performed. The organic phases were combined and washed with water, saturated aqueous sodium bicarbonate and brine. The resulting solution was dried over anhydrous sodium sulfate. The residue obtained by removing the solvent was purified by silica gel chromatography (hexane: toluene = 10: 1 was used as an eluent) to obtain a yellow solid substance. The yellow solid substance was recrystallized from hexane to obtain the title compound (6a) as a yellow solid (47 mg, yield 87%).
6a: 1H NMR (CDCl3, Me4Si) δ6.70 (d, J = 6 Hz, 1 H), 6.88-6.91 (m, 2 H), 6.95-7.09 (m, 18 H), 7.13-7.18 (m, 3H), 7.38-7.43 (m, 2H); 13C NMR (CDCl3, Me4Si) δ 124.3, 124.7, 124.8, 125.6, 126.0, 126.18, 126.21, 126.56, 126.60, 127.16, 127.22, 127.25, 127.8, 128.0 , 128.8, 128.9, 129.0, 130.1, 130.3, 130.4, 130.9, 132.5, 132.6, 134.4, 136.1, 137.6, 138.9, 141.1, 141.2, 141.4, 142.4, 143.2.HRMS calcd for C40H28O2S: 538.1755. Found: 538.1754.

<Step 3-2>
Preparation of 4,11-diphenyl-5,10-bis (trimethylsilylethynyl) anthra [2,3-b] thiophene (6b)

N-BuLi (1.55 M hexane solution, 323 μL, 0.5 mmol) was added to a hexane solution (2 mL) of trimethylsilylacetylene (69 μL, 0.5 mmol) at −78 ° C. The solution was returned to room temperature and subsequently stirred for 1 hour.
To this solution was added 4,11-diphenylanthra [2,3-b] thiophene-5,10-dione (4) (52 mg, 0.125 mmol) at -78 ° C. The mixture was returned to room temperature and refluxed overnight.
Thereafter, water was added to the mixture to quench it, SnCl ₂ (133 mg, 0.7 mmol) dissolved in 10% aqueous hydrochloric acid (0.5 mL) was added, and the mixture was stirred at room temperature for 3 hours.
After stirring, a saturated aqueous NH ₄ Cl solution was added to the mixture and quenched, followed by extraction with chloroform. The organic phases were combined and washed with water, saturated aqueous sodium bicarbonate and brine. The resulting solution was dried over anhydrous sodium sulfate. The residue obtained by removing the solvent was purified by silica gel chromatography (using chloroform as the eluent) to give the title compound (6b) as a red powder (50 mg, 70% yield).
6b: 1H NMR (CDCl3, Me4Si) δ0.15 (s, 9 H), 0.16 (s, 9 H), 7.00 (d, J = 6 Hz, 1 H), 7.31 (d, J = 6 Hz, 1 H), 7.48-7.60 (m, 12 H), 8.57-8.61 (m, 2 H); 13C NMR (CDCl3, Me4Si) δ0.002, 0.04, 102.63, 102.65, 113.8, 114.4, 117.4, 118.9, 124.4, 126.6, 126.8, 127.22, 127.24, 127.6, 127.8, 127.9, 128.1, 128.3, 128.7, 129.8, 130.6, 131.4, 133.3, 133.8, 133.9, 134.3, 139.3, 141.5, 142.2, 142.4.HRMS calcd for C40H28O2S: 578.1920. Found : 578.1932.

[Example 2]
Production of thiophene ring-fused polycyclic aromatic compounds 2
According to Reaction Scheme 2, a thiophene ring-fused polycyclic aromatic compound (12) was produced.

<Step 1>
Preparation of 5,9-diphenyl-4,10-dihydronaphtho [2,3-b: 6,7-b ′] dithiophene (mixture of two isomers) (9)

Cp ₂ ZrCl ₂ (351 mg, 1.2 mmol), n-BuLi (1.57 M in hexane, 1.53 mL, 2.4 mmol), 2,3-bis (3-phenyl-2-propynyl) thiophene (312 mg, 1.0 mmol), CuCl (196 mg, 2.0 mmol), DMPU (0.44 mL, 3.6 mmol), 2,3-diiodothiophene (403 mg, 1.2 mmol) and Similarly, the title compound (9) as a yellow solid was obtained (209 mg, 53% yield).
9: 1H NMR (CDCl3, Me4Si) δ3.86-3.90 (m, 4 H), 4.00-4.04 (m, 4 H), 6.77 (d, J = 5 Hz, 2 H), 6.89 (d, J = 5 Hz, 1 H), 6.90 (d, J = 6 Hz, 1 H), 7.06 (d, J = 5 Hz, 2 H), 7.22 (d, J = 5 Hz, 2 H), 7.37-7.41 ( m, 4 H), 7.44-7.59 (m, 16 H); 13C NMR (CDCl3, Me4Si) δ29.3, 29.4, 30.1, 30.2, 122.6 (2 peaks were overlapped), 123.8 (2 peaks were overlapped), 126.29 , 126.33, 126.66, 126.69, 127.3, 127.4, 127.9, 128.0, 128.5, 128.56, 128.61, 128.8, 128.9, 128.96, 129.00, 129.1, 129.17, 129.23, 129.60, 129.63, 133.4, 133.6, 133.8, 134.1, 134.7, 135.0 , 135.6, 135.9, 137.7, 137.9, 139.5, 139.7, 139.8, 139.9, 139.95, 140.02.HRMS calcd for C26H18S2: 394.0850. Found: 394.0849.

<Step 2>
Preparation of 5,9-diphenylnaphtho [2,3-b: 6,7-b ′] dithiophene-4,10-dione (mixture of two isomers) (10)

In a pyridine solution (3 mL) of 5,9-diphenyl-4,10-dihydronaphtho [2,3-b: 6,7-b ′] dithiophene (9) (51 mg, 0.13 mmol), FeCl ₃ (1 mg , 0.0052 mmol) was added and dissolved, followed by the addition of t-butyl hydroperoxide (TBHP) (70% aqueous solution, 106 μL, 0.78 mmol). The reaction mixture was stirred at 80 ° C. for 48 hours. During this time air was entrained in the reaction mixture.
DBU (78 μL, 0.52 mmol) was then added and the reaction mixture was stirred at reflux overnight.
After stirring overnight at reflux, 3M HCl aqueous solution was added to the mixture and quenched, followed by extraction with chloroform. The organic phases were combined and washed with water, saturated aqueous sodium bicarbonate and brine. The resulting solution was dried over anhydrous sodium sulfate. The black solid substance obtained by removing the solvent was purified by flash chromatography (silica gel, using chloroform as an eluent) to give the title compound (10) as a yellow solid (32 mg, yield 57). %).
10: 1H NMR (CDCl3, Me4Si) δ7.00-7.01 (m, 2 H), 7.33-7.35 (m, 4 H), 7.39-7.41 (m, 4 H), 7.50-7.52 (m, 4 H) , 7.53-7.60 (m, 14 H); 13C NMR (CDCl3, Me4Si) δ 125.90, 125.93, 126.1, 126.2, 126.7, 126.8, 127.18, 127.22, 127.47, 127.50, 127.70, 127.74, 127.77, 127.79, 127.8, 127.9, 128.40, 128.42, 128.72, 128.75, 132.56, 132.63, 133.9 (2 peaks were overlapped), 139.6, 139.8, 140.27, 140.33, 140.5, 140.6 (2 peaks were overlapped), 140.8, 143.27, 143.34, 143.6 (2 peaks were overlapped), 146.4, 146.7, 147.7, 148.0, 178.8, 179.1, 179.9, 180.2.HRMS calcd for C26H13O2S2 (M + -1): 421.0357. Found: 421.0364.

<Step 3>
Preparation of 4,5,9,10-tetraphenylnaphtho [2,3-b: 6,7-b ′] dithiophene-4,10-diol (mixture of two isomers) (11)

5,9-diphenylnaphtho [2,3-b: 6,7-b ′] dithiophene-4,10-dione (10) (85 mg, 0.2 mmol), phenyllithium (1.08 M cyclohexane-diethyl ether solution) , 0.55 mL, 0.6 mmol) was used in the same manner as in Step 3-1 of Example 1 to obtain the title compound (11) as a gray solid (112 mg, yield 97%).
11: 1H NMR (CDCl3, Me4Si) δ4.48 (s, 1 H), 4.55 (s, 1 H), 4.66 (s, 1 H), 4.78 (s, 1 H), 6.15 (d, J = 8 Hz, 1 H), 6.21-6.26 (m, 4 H), 6.30 (d, J = 8 Hz, 1 H), 6.44 (d, J = 6 Hz, 1 H), 6.48 (d, J = 6 Hz , 1 H), 6.77-6.87 (m, 8 H), 6.95-7.19 (m, 36 H); 13C NMR (CDCl3, Me4Si) δ74.0, 74.3, 74.4, 74.7, 124.28, 124.29, 124.9 (2 peaks were overlapped), 125.0 (4 peaks were overlapped), 125.2 (2 peaks were overlapped), 125.3, 125.4, 125.50, 125.54, 125.86, 125.88, 125.90 (2 peaks were overlapped), 125.92, 126.37, 126.42, 126.55, 126.58, 126.85, 126.87, 126.89, 127.0, 127.2, 127.29, 127.35 (3 peaks were overlapped), 127.44 (2 peaks were overlapped), 127.45 (2 peaks were overlapped), 127.5 (2 peaks were overlapped), 127.8 (2 peaks were overlapped ), 129.56, 129.59, 130.08, 130.10, 130.26, 130.30, 130.5 (2 peaks were overlapped), 136.00, 136.05, 136.5, 136.6, 137.5, 137.6, 137.8, 138.0, 138.7, 138.9, 139.8, 139.9, 140.3, 140.4, 141.2, 141.4, 143.2, 143.5, 144.5, 144.6, 147.7, 147.9, 148.7, 148.9.HRMS calcd for C38H26O2S2: 578.1374. Found: 578.1372.

<Step 4>
Preparation of 4,5,9,10-tetraphenylnaphtho [2,3-b: 6,7-b ′] dithiophene (mixture of two isomers) (12)

4,5,9,10-tetraphenylnaphtho [2,3-b: 6,7-b ′] dithiophene-4,10-diol (11) (100 mg, 0.17 mmol), TiCl 3 (THF) 3 (257 mg, 0.69 mmol) and magnesium aluminum hydride (LiAlH ₄ ) (14 mg, 0.35 mmol) were obtained in the same manner as in Step 4-1 of Example 1 to obtain the title compound (12) (84 mg, yield). 89%).
12: 1H NMR (CDCl3, Me4Si) δ6.76 (d, J = 6 Hz, 2 H), 6.77 (d, J = 6 Hz, 2 H), 6.99-7.04 (m, 20 H), 7.06-7.14 (m, 20 H), 7.165 (d, J = 6 Hz, 2 H), 7.174 (d, J = 6 Hz, 2 H); 13C NMR (CDCl3, Me4Si) δ 124.47, 124.52, 125.9, 126.1, 126.5, 126.6, 127.2, 127.3, 127.6, 127.79, 127.82, 128.3, 128.6, 130.6, 130.7, 131.3, 131.4, 132.4, 133.6, 133.8, 135.0, 138.4, 138.6, 141.0, 141.2, 141.7, 142.0 (2 peaks were overlapped ), 142.4 (2 peaks were overlapped), 142.8. HRMS calcd for C26H18S2: 544.1319. Found: 544.1320.

  As described above, the desired thiophene ring-fused polycyclic aromatic compound can be obtained as a mixture of two types of isomers. Each isomer can be easily isolated from the mixture by chromatographic methods.

  The thiophene ring-fused polycyclic aromatic compound of the present invention can be used as an organic electronic device material such as a light emitting device, a photoelectric conversion device, and a semiconductor. The thin film containing the thiophene ring-fused polycyclic aromatic compound of the present invention can be used as an organic field effect transistor element or the like.

Sundar et al., Science, 2004, 303, 1644

Claims (12)

A thiophene ring-fused polycyclic aromatic compound represented by the following formula (1a), (1b) or (1c).
[Wherein, R ¹ , R ² , R ³ and R ⁴ are each independently the same or different and are a hydrogen atom; a halogen atom; an optionally substituted C ₁ -C ₂₀ hydrocarbon; A C ₁ -C ₂₀ alkoxy group which may have a substituent; a C ₆ -C ₂₀ aryloxy group which may have a substituent; an amino group which may have a substituent; A silyl group which may have a group; a hydroxyl group; a thienyl group which may have a substituent; a pyridyl group which may have a substituent; and a furyl group which may have a substituent. ,
R ⁵ , R ^{5 ′,} and R ⁶ are each independently the same or different and are each a halogen atom; an optionally substituted C ₁ -C ₂₀ hydrocarbon group; A C ₁ -C ₂₀ alkoxy group which may have a substituent; a C ₆ -C ₂₀ aryloxy group which may have a substituent; an amino group which may have a substituent; a silyl which may have a substituent A group; a hydroxyl group; a thienyl group which may have a substituent, a pyridyl group which may have a substituent, a furyl group which may have a substituent,
m and m ′ are each independently the same or different and are an integer of 0 to 2, and n is an integer of 0 to 4. ] The thiophene ring-fused polycyclic aromatic according to claim 1, wherein any one of R ¹ and R ² or R ³ and R ⁴ is a C ₆ -C ₂₀ aryl group which may have a substituent. Compound. The thiophene ring condensed polycyclic aromatic compound according to claim 1 or 2, wherein R ¹ and R ² are the same functional group, and R ³ and R ⁴ are the same functional group. R ^1, R ^2, R ³ and R ⁴ are optionally C ₆ -C ₂₀ aryl group which may have a substituent, a thiophene fused polycyclic aromatic according to any one of claims 1 to 3 Compound. The thiophene ring condensed polycyclic aromatic compound according to any one of claims 1 to 4, wherein R ¹ , R ² , R ³ and R ⁴ are a phenyl group which may have a substituent. R ^1, R ^2, R ³ and R ⁴ is a phenyl group, a thiophene-fused polycyclic aromatic compound according to any one of claims 1 to 5. R ¹ and R ² are alkynyl groups which may have a substituent, and R ³ and R ⁴ are phenyl groups which may have a substituent. The thiophene ring-fused polycyclic aromatic compound according to item 1. The thiophene ring condensed polycyclic aromatic compound according to any one of claims 1 to 7, which is represented by the following formula (1a '), (1b') or (1c ').
[Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{5 ′} have the same meaning as described above. ] The thiophene ring condensed polycyclic aromatic compound according to any one of claims 1 to 7, which is represented by the following formula (1a ''), (1b '') or (1c '').
[Wherein, R ¹ , R ² , R ³ and R ⁴ have the same meanings as described above. ]   The composition containing the thiophene ring condensed polycyclic aromatic compound and organic solvent of any one of Claims 1-9.   The composition of claim 10 further comprising a synthetic organic polymer.   The thin film containing the thiophene ring condensed polycyclic aromatic compound of any one of Claims 1-9.